Resin composition

Abstract

To provide a resin composition which has a low weight reduction rate, has excellent thin-film formability, can suppress cissing of a resin composition on a coating surface, can suppress separation of a resin in a resin composition layer, and can lower an average linear thermal expansion coefficient (CTE) of a cured product of the resin composition.SOLUTION: A resin composition contains (A) an epoxy resin, (B) an organic solvent, (C) a modified polydialkylsiloxane compound, (D) an inorganic filler, and (E) a curing agent, wherein the component (C) is a compound having a polydialkylsiloxane structure, and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure, and an average linear thermal expansion coefficient of a cured product of the resin composition is less than 20 ppm / K in the range of 25°C to 150°C.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition. Further, the present invention relates to a resin sheet, a circuit board, and a semiconductor device having a resin composition layer containing the resin composition.

Background Art

[0002] As a manufacturing technique for printed wiring boards, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately laminated is known (for example, Patent Documents 1 to 4). In the manufacturing method by the build-up method, generally, the insulating layer is formed by curing a resin composition.

[0003] Various methods are known as methods for forming the insulating layer. Among them, the slit coating method is advantageous in several respects.

[0004] For example, since the slit coating method can perform coating with a small amount of coating liquid, it is advantageous for cost reduction. The amount of the coating liquid required for the slit coating method is, for example, about 1 / 5 to 1 / 10 compared with the spin coating method. Further, there are no particular restrictions on the slit nozzles used for coating, and those commercially available from a plurality of manufacturers can be used.

[0005] In addition, in the curtain coating method, since the coating liquid comes into contact with the air and the solvent volatilizes, the viscosity changes and the formed film thickness changes. On the other hand, in the slit coating method, since the coating liquid is in a closed system until it is discharged from the nozzle, the viscosity does not change and a uniform film thickness can be formed.

[0006] In addition, in the lamination method, there is a problem that bleeding of the resin occurs. In the spin coating method, since the substrate (wafer) end is covered with the resin, cleaning of the end is required. In the curtain coating method, there is a problem that the coating liquid penetrates into the cross section of the substrate. On the other hand, in the slit coating method, since the coating width can be controlled, bleeding does not occur and it is possible not to apply to the end. Further, it is also possible to apply up to the end of the substrate without the coating liquid penetrating into the cross section.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0008] However, when forming an insulating layer by applying a resin composition, nozzle clogging may occur due to drying of the nozzle of a coating device such as a slit coater. The likelihood of this nozzle clogging can be predicted by quantifying the ease of nozzle drying. The ease of nozzle drying correlates, for example, with the amount of weight loss when the resin composition is left at room temperature.

[0009] Also, when a resin composition containing an inorganic filler is put into and used in a coating device, it is necessary to adjust the viscosity to an appropriate value according to the type of coating device. For example, if the viscosity is too high, it becomes difficult to smoothly discharge the resin composition from the coating device, and the film thickness uniformity and thin film formability may decrease. On the other hand, if the viscosity is too low, the resin composition can be smoothly discharged from the coating device, but repelling of the resin composition may occur on the coating surface.

[0010] Furthermore, when using a resin composition containing an inorganic filler, the inorganic filler and the resin in the resin composition layer may separate in the vacuum drying step after coating. More specifically, in the cross-section of the dried resin composition layer, there may be a region where the inorganic filler is absent and only the resin is present.

[0011] Furthermore, when the cured product of this resin composition was evaluated, it was surprisingly found that the coefficient of linear thermal expansion (CTE) decreased. This is considered to be due to the fact that the resin does not separate and the inorganic filler is uniformly present in the resin composition layer, so that the stress caused by the thermal expansion of the resin is not concentrated but dispersed, and the strain during thermal expansion is suppressed.

[0012] An object of the present invention is to provide a resin composition having a low weight loss rate, excellent thin film formability, capable of suppressing the peeling of the resin composition on the coating surface, capable of suppressing the separation of the resin in the resin composition layer, and capable of reducing the average coefficient of linear thermal expansion (CTE) of the cured product of the resin composition. [Means for Solving the Problems]

[0013] In order to achieve the object of the present invention, the present inventors have intensively studied solvents, viscosities, etc. As a result, a resin composition containing (A) an epoxy resin, (B) an organic solvent, (C) a modified polydialkylsiloxane compound, (D) an inorganic filler, and (E) a curing agent, wherein the component (C) has a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure. Surprisingly, the resin composition can suppress the clogging of the nozzle due to the drying of the nozzle, can suppress the peeling of the resin composition on the coating surface, can suppress the separation of the resin in the resin composition layer, and can reduce the average coefficient of linear thermal expansion (CTE) of the cured product of the resin composition. Based on this finding, the present invention has been completed.

[0014] That is, the present invention includes the following contents. [1] A resin composition containing (A) an epoxy resin, (B) an organic solvent, (C) a modified polydialkylsiloxane compound, (D) an inorganic filler, and (E) a curing agent, wherein the component (C) is a compound having a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure, A resin composition in which the average linear thermal expansion coefficient (CTE) of the cured product is less than 20 ppm / K in the range from 25°C to 150°C. [2] The resin composition according to [1], wherein the two alkyl groups of the polydialkylsiloxane structure are each independently an alkyl group having 1 to 5 carbon atoms. [3] The resin composition according to [1] or [2], wherein at least one of the two alkyl groups is a methyl group. [4] The content of component (B) is 10% by mass or more and 35% by mass or less when the total amount of the resin composition is 100% by mass. [5] The resin composition according to [1], wherein the content of component (C) is 0.03% by mass or more and 0.15% by mass or less when the non-volatile components in the resin composition are 100% by mass. [6] The resin composition according to [4], wherein the ratio of the content of component (C) to the content of component (B) is 0.1% or more and 1% or less. [7] The resin composition according to any one of [1] to [5], wherein component (D) contains both an active ester-based curing agent and a phenol-based curing agent. [8] The resin composition according to any one of [1] to [7], wherein the viscosity measured using an E-type viscometer under the conditions of 25°C and 100 rpm is 3 mPa·s or more and 1,000 mPa·s or less. [9] A sheet-like laminated material containing the resin composition according to any one of [1] to [8].

[10] A resin sheet having a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [8].

[11] A circuit board containing a cured product of the resin composition according to any one of [1] to [8].

[12] A circuit board containing a cured product of the resin composition according to any one of [1] to [8].

[12] The cured product of the resin composition is the circuit board according to

[11] , which is formed from the resin composition by a method selected from the group consisting of a roll coating method, a spray coating method, a spin coating method, a bar coating method, a slit coating method, a curtain coating method, and a dipping method.

[13] A semiconductor device including the circuit board according to

[11] or

[12] . [Advantages of the Invention]

[0015] According to the present invention, there can be provided a resin composition having a low weight loss rate, excellent thin film formability, capable of suppressing the repellency of the resin composition on the coating surface, capable of suppressing the separation of the resin in the resin composition layer, and reducing the average linear thermal expansion coefficient (CTE) of the cured product of the resin composition, a resin sheet having a resin composition layer formed from the resin composition, a circuit board including the cured product of the resin composition, and a semiconductor device. [Embodiments for Carrying Out the Invention]

[0016] Hereinafter, the present invention will be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0017] [Resin Composition] The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) an organic solvent, (C) a modified polydialkylsiloxane compound, (D) an inorganic filler, and (E) a curing agent, and the component (C) is a compound having a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure, and the average linear thermal expansion coefficient (CTE) of the cured product of the resin composition is less than 20 ppm / K in the range from 25°C to 150°C. Such a resin composition can suppress the clogging of the nozzle due to the drying of the nozzle, suppress the repellency of the resin composition on the coating surface, suppress the separation of the resin in the resin composition layer, and reduce the average linear thermal expansion coefficient (CTE) of the cured product of the resin composition. The average linear thermal expansion coefficient (CTE) of the cured product of the resin composition of the present invention is less than 20 ppm / K in the range from 25°C (298 K) to 150°C (423 K), preferably 19 ppm / K or less, more preferably 18 ppm / K or less, and particularly preferably 17 ppm / K or less. The lower limit can be, for example, 1 ppm / K or more, 3 ppm / K or more, 5 ppm / K or more, etc. The average linear thermal expansion coefficient is calculated based on the thermal expansion rate measured according to the method described in the examples below. The viscosity of the resin composition of the present invention, measured using an E-type viscometer under the conditions of 25°C and 100 rpm, is 3 mPa·s or more and 1,000 mPa·s or less, preferably 5 mPa·s or more, more preferably 10 mPa·s or more, still more preferably 30 mPa·s or more, and particularly preferably 50 mPa·s or more. The upper limit of the viscosity can be 5,000 mPa·s or less, preferably 4,000 mPa·s or less, more preferably 3,000 mPa·s or less, still more preferably 2,000 mPa·s or less, even more preferably 1,500 mPa·s or less, yet even more preferably 1,000 mPa·s or less, and particularly preferably 800 mPa·s or less.

[0018] In addition to (A) an epoxy resin, (B) an organic solvent, (C) a modified polydialkylsiloxane compound, (D) an inorganic filler, and (E) a curing agent, the resin composition may contain, for example, (F) a thermoplastic resin, (G) a curing accelerator, and (H) other additives. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

[0019] <(A) Epoxy Resin> The resin composition of the present invention contains (A) an epoxy resin. By containing (A) an epoxy resin in the resin composition, a cured product having good mechanical strength and insulation reliability can be obtained. (A) The epoxy resin may be used alone or in combination of two or more.

[0020] (A) Examples of the epoxy resin include a bixylenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolak type epoxy resin, a phenol novolak type epoxy resin, a tert-butyl-catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl cyclohexane type epoxy resin, an alkyldiglycidyl ether type epoxy resin, a cresol novolak type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, an isocyanurate type epoxy resin, a phenolphthalimide type epoxy resin, etc. The (A) epoxy resin may be used alone or in combination of two or more.

[0021] The resin composition preferably contains, as the (A) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more with respect to 100% by mass of the (A) epoxy resin.

[0022] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition of the present invention, as the (A) epoxy resin, may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. Among them, from the viewpoint of remarkably obtaining the effects of the present invention, it is preferable to contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0023] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

[0024] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, epoxy resin having a butadiene structure, glycidyl cyclohexane type epoxy resin, phenol phthalimide type epoxy resin, and alkyldiglycidyl ether type epoxy resin are preferable.

[0025] Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL", "825", "Epicoat 828EL" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolak-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD" (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Corporation; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YED216D" (alkyl diglycidyl ether-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These may be used alone or in combination of two or more types.

[0026] As the solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferable, a solid epoxy resin having three or more epoxy groups in one molecule is more preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0027] Examples of the solid epoxy resin include a biphenol-type epoxy resin, a naphthalene-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol AF-type epoxy resin, and a tetraphenylethane-type epoxy resin. Among them, a biphenyl-type epoxy resin is preferred, and a biphenyl-type epoxy resin is more preferred.

[0028] Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (tetrafunctional naphthalene-type epoxy resin), "N-690" (cresol novolak-type epoxy resin), "N-695" (cresol novolak-type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene-type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-type epoxy resin), "NC7000L" (naphthol novolak-type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthalene-type epoxy resin), "ESN485" (naphthol novolak-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF-type epoxy resin), "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR-991S" (phenolphthalimide-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and the like. These may be used alone or in combination of two or more.

[0029] (A) When using a combination of a liquid epoxy resin and a solid epoxy resin as the epoxy resin, their quantitative ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5 in terms of mass ratio. When the quantitative ratio of the liquid epoxy resin and the solid epoxy resin is within such a range, the desired effects of the present invention can be remarkably obtained.

[0030] (A) The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 3,000 g / eq., still more preferably 80 g / eq. to 2,000 g / eq., and even more preferably 110 g / eq. to 1,000 g / eq. By being within this range, a cured product with sufficient crosslink density of the resin composition can be obtained. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0031] (A) From the viewpoint of remarkably obtaining the desired effects of the present invention, the weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the epoxy resin can be measured as a value in terms of polystyrene conversion by the gel permeation chromatography (GPC) method.

[0032] The content of the (A) epoxy resin in the resin composition, from the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability, when the non-volatile components in the resin composition are 100% by mass, can be preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 13% by mass or more, and particularly preferably 15% by mass or more. The upper limit of the content, when the non-volatile components in the resin composition are 100% by mass, can be preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

[0033] In the present invention, unless otherwise specified, the content of each component in the resin composition is a value based on 100% by mass of the non-volatile components in the resin composition. The non-volatile components mean the entire non-volatile components excluding the solvent in the resin composition.

[0034] Also, from the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the (A) epoxy resin in the resin composition, when the resin components in the resin composition are 100% by mass, is preferably 30% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, and particularly preferably 55% by mass or more. The upper limit of the content, when the resin components in the resin composition are 100% by mass, can be preferably 75% by mass or less, more preferably 70% by mass or less, and particularly preferably 65% by mass or less.

[0035] Note that the resin components refer to the components obtained by excluding the inorganic filler described below from the non-volatile components constituting the resin composition.

[0036] <(B) Organic Solvent> The resin composition of the present invention contains a (B) organic solvent. The (B) organic solvent described here is composed of skeleton atoms selected from carbon atoms and oxygen atoms and hydrogen atoms as non-skeleton atoms, and may further have an amide bond (>N-CO-), a urea bond (>N-CO-N<), or a cyano group (-CN) in the molecule separately from the skeleton atoms, and does not contain a triple bond between carbons or a double bond between carbons (excluding the bonds constituting the aromatic ring), and is a liquid compound having a boiling point of 250°C or lower (a compound that is liquid at normal temperature (25°C)). In addition, the (B) organic solvent described here does not include those corresponding to the (A) epoxy resin or the (E) curing agent. In the present specification, the boiling point refers to the boiling point under normal pressure (1 atm; 760 mmHg) (i.e., the standard boiling point). The (B) organic solvent may be used alone or in combination of two or more.

[0037] (B) Examples of the organic solvent include aromatic solvents and non-aromatic solvents. An organic solvent with a boiling point of less than 130°C is referred to as a low-boiling organic solvent, and an organic solvent with a boiling point of 130°C or higher is referred to as a high-boiling organic solvent.

[0038] An aromatic solvent is a solvent that contains an aromatic ring in the molecule. Examples of the aromatic solvent include C 6-8 aromatic hydrocarbons such as benzene (boiling point 80°C), toluene (boiling point 110°C), o-xylene (boiling point 144°C), m-xylene (boiling point 139°C), p-xylene (boiling point 138°C), ethylbenzene (boiling point 136°C), etc., C9 aromatic hydrocarbons such as 1,2,3-trimethylbenzene (boiling point 176°C), 1,3,5-trimethylbenzene (boiling point 165°C), 1,2,4-trimethylbenzene (boiling point 169°C), 4-ethyltoluene (boiling point 161°C), 3-ethyltoluene (boiling point 160°C), 2-ethyltoluene (boiling point 166°C), isopropylbenzene (boiling point 152°C), n-propylbenzene (boiling point 159°C), indane (boiling point 176°C), etc., C 10 aromatic hydrocarbons such as n-butylbenzene (boiling point 183°C), isobutylbenzene (boiling point 172°C), sec-butylbenzene (boiling point 173°C), tert-butylbenzene (boiling point 169°C), 1,2-diethylbenzene (boiling point 184°C), 1,3-diethylbenzene (boiling point 181°C), 1,4-diethylbenzene (boiling point 183°C), 3-ethyl-o-xylene (boiling point 194°C), 4-ethyl-o-xylene (boiling point 190°C), 2-ethyl-p-xylene (boiling point 187°C), 1-methyl-2-isopropylbenzene (boiling point 178°C), 1-methyl-3-isopropylbenzene (boiling point 175°C), 1-methyl-4-isopropylbenzene (boiling point 177°C), 1,2,3,5-tetramethylbenzene (boiling point 198°C), 1,2,3,4-tetrahydronaphthalene (boiling point 207°C), etc., C 11 aromatic hydrocarbons such as 1,3-dimethyl-4-isopropylbenzene (boiling point 199°C), 1-ethyl-4-isopropylbenzene (boiling point 197°C), etc., C 12Aromatic hydrocarbon solvents such as aromatic hydrocarbons; Aromatic ketone solvents such as acetophenone (boiling point 202 °C); Aromatic alcohol solvents such as benzyl alcohol (boiling point 205 °C), phenethyl alcohol (boiling point 219 - 221 °C); Aromatic ether solvents such as anisole (boiling point 154 °C), phenetole (boiling point 169 °C); Aromatic ester solvents such as methyl benzoate (boiling point 198 - 200 °C), ethyl benzoate (boiling point 211 - 213 °C), etc. can be mentioned.

[0039] As the aromatic solvent, it is preferable to include aromatic hydrocarbon solvents. In one embodiment, the aromatic solvent is C 6-8 It is more preferable to contain aromatic hydrocarbons, and it is more preferable to contain an aromatic solvent selected from C9 aromatic hydrocarbons and C 10 aromatic hydrocarbons.

[0040] As the aromatic solvent, commercially available aromatic mixed solvents may be used. Examples of commercially available aromatic mixed solvents include "Ipzol 100" (initial boiling point 159 °C, dry point 172 °C, aromatic 99% or more), "Ipzol 150" (initial boiling point 184 °C, dry point 205 °C, aromatic 99% or more) manufactured by Idemitsu Kosan Co., Ltd., "Swazol 1000" (initial boiling point 163 °C, dry point 175 °C, aromatic 100%), "Swazol 1500" (initial boiling point 182 °C, dry point 206 °C, aromatic 98%) manufactured by Maruzen Petrochemical Co., Ltd., "Solvent #100" (initial boiling point 150 °C, dry point 185 °C), "Solvent #150" (initial boiling point 180 °C, dry point 215 °C) manufactured by Sankyo Chemical Co., etc.

[0041] The non - aromatic solvent is a solvent that does not contain an aromatic ring in the molecule. Examples of non - aromatic solvents include glycol solvents, glycol ether solvents, glycol ether ester solvents, aliphatic hydrocarbon solvents, aliphatic ketone solvents, aliphatic ester solvents, aliphatic ether solvents, aliphatic alcohol solvents, nitrile solvents, amide solvents, urea solvents, etc.

[0042] Examples of glycol solvents include ethylene glycol (boiling point 197°C), diethylene glycol (boiling point 244°C), propylene glycol (boiling point 188°C), dipropylene glycol (boiling point 232°C), trimethylene glycol (boiling point 211 - 217°C), and the like.

[0043] Examples of glycol ether solvents include cellosolves such as ethylene glycol monomethyl ether (also known as methyl cellosolve) (boiling point 124°C), ethylene glycol monoethyl ether (also known as cellosolve) (boiling point 135°C), ethylene glycol monopropyl ether (also known as propyl cellosolve) (boiling point 151°C), ethylene glycol monobutyl ether (also known as butyl cellosolve) (boiling point 171°C), ethylene glycol monoisobutyl ether (also known as isobutyl cellosolve) (boiling point 160°C), ethylene glycol mono-tert-butyl ether (also known as tert-butyl cellosolve) (boiling point 152°C), ethylene glycol monohexyl ether (boiling point 208°C), etc.; carbitols such as diethylene glycol monomethyl ether (also known as methyl carbitol) (boiling point 193°C), diethylene glycol monoethyl ether (also known as carbitol) (boiling point 196°C), diethylene glycol monopropyl ether (also known as propyl carbitol) (boiling point 212 - 216°C), diethylene glycol monobutyl ether (DB) (also known as butyl carbitol) (boiling point 230°C), etc.; propylene glycol ethers such as propylene glycol monomethyl ether (PGM) (boiling point 120°C), propylene glycol monoethyl ether (boiling point 132°C), propylene glycol monopropyl ether (boiling point 150°C), propylene glycol monobutyl ether (boiling point 170°C), etc.; dipropylene glycol ethers such as dipropylene glycol monomethyl ether (boiling point 188°C), dipropylene glycol monoethyl ether (boiling point 198°C), dipropylene glycol monopropyl ether (boiling point 210°C), dipropylene glycol monobutyl ether (boiling point 215°C), etc.

[0044] Examples of glycol ether ester solvents include cellosolve esters such as ethylene glycol monomethyl ether acetate (also known as methyl cellosolve acetate) (boiling point 145°C), ethylene glycol monoethyl ether acetate (also known as cellosolve acetate) (boiling point 156°C), ethylene glycol monobutyl ether acetate (also known as butyl cellosolve acetate) (boiling point 191°C); carbitol esters such as diethylene glycol monoethyl ether acetate (EDGAc) (also known as carbitol acetate) (boiling point 217°C), diethylene glycol monobutyl ether acetate (also known as butyl carbitol acetate) (boiling point 247°C); propylene glycol ether esters such as propylene glycol monomethyl ether acetate (PGMEA) (boiling point 146°C), propylene glycol monoethyl ether acetate (boiling point 160°C); dipropylene glycol ether esters such as dipropylene glycol monomethyl ether acetate (boiling point 200°C), etc.

[0045] Examples of aliphatic hydrocarbon solvents include n-pentane (boiling point 36°C), n-hexane (boiling point 69°C), 2-methylpentane (also known as isohexane) (boiling point 60 - 62°C), n-heptane (boiling point 98°C), n-octane (boiling point 125°C), cyclopentane (boiling point 49°C), cyclohexane (boiling point 81°C), methylcyclohexane (boiling point 101°C), ethylcyclohexane (boiling point 132°C), etc.

[0046] Examples of aliphatic ketone solvents include aliphatic acyclic ketones such as acetone (boiling point 56°C), methyl ethyl ketone (MEK) (boiling point 79°C), diethyl ketone (boiling point 101°C), 2-pentanone (boiling point 101°C), methyl isobutyl ketone (boiling point 116°C), 2-hexanone (boiling point 127°C), 2-heptanone (MAK) (boiling point 151°C), diisobutyl ketone (boiling point 168°C); aliphatic cyclic ketones such as cyclopentanone (boiling point 131°C), cyclohexanone (Anone) (boiling point 155°C), 2-methylcyclohexanone (boiling point 162°C), etc.

[0047] Aliphatic ester solvents are non-aromatic solvents having an ester structure that does not fall under glycol ether ester solvents. For example, fatty acid alkyl esters such as methyl acetate (boiling point 57 °C), ethyl acetate (boiling point 77 °C), n-propyl acetate (boiling point 96 °C), isopropyl acetate (boiling point 89 °C), n-butyl acetate (boiling point 126 °C), isobutyl acetate (boiling point 118 °C), sec-butyl acetate (boiling point 112 °C), tert-butyl acetate (boiling point 97 °C), n-pentyl acetate (boiling point 149 °C), isopentyl acetate (boiling point 142 °C), ethyl propionate (boiling point 99 °C), propyl propionate (boiling point 122 °C), isopropyl propionate (boiling point 108 °C); hydroxy acid alkyl esters such as methyl lactate (boiling point 144 - 145 °C), ethyl lactate (boiling point 151 - 155 °C), butyl lactate (boiling point 185 - 187 °C); keto acid alkyl esters such as methyl acetoacetate (boiling point 170 °C), ethyl acetoacetate (boiling point 184 °C); lactones such as γ-butyrolactone (GBL) (boiling point 204 °C) and the like can be mentioned.

[0048] Aliphatic ether solvents are non-aromatic solvents having an ether structure that does not fall under glycol ether solvents and glycol ether ester solvents. For example, aliphatic acyclic ethers such as diethyl ether (boiling point 34 °C), diisopropyl ether (boiling point 68 °C), methyl tert-butyl ether (boiling point 55 °C); aliphatic cyclic ethers such as tetrahydrofuran (boiling point 66 °C), 1,4-dioxane (boiling point 101 °C), 1,3-dioxolane (boiling point 75 °C) and the like can be mentioned.

[0049] Aliphatic alcohol solvents are non-aromatic solvents with an alcohol structure that do not fall under glycol solvents and glycol ether solvents. For example, aliphatic acyclic alcohols such as methanol (boiling point 64 °C), ethanol (boiling point 78 °C), n-propanol (boiling point 97 °C), isopropanol (boiling point 82 °C), n-butyl alcohol (boiling point 117 °C), isobutyl alcohol (boiling point 108 °C), sec-butyl alcohol (boiling point 99 °C), tert-butyl alcohol (boiling point 82 °C), n-pentyl alcohol (boiling point 138 °C), isopentyl alcohol (boiling point 131 °C), sec-pentyl alcohol (boiling point 119 °C), tert-pentyl alcohol (boiling point 102 °C), neopentyl alcohol (boiling point 113 °C), n-hexyl alcohol (boiling point 157 °C), n-heptyl alcohol (boiling point 175 °C), isoheptyl alcohol (boiling point 159 °C), n-octyl alcohol (boiling point 195 °C), 2-ethylhexyl alcohol (boiling point 184 °C); and aliphatic cyclic alcohols such as cyclohexanol (boiling point 161 °C) can be mentioned.

[0050] Examples of nitrile solvents include acetonitrile (boiling point 82 °C), propionitrile (boiling point 97 °C), etc.

[0051] Examples of amide solvents include acyclic amides such as N,N-dimethylformamide (DMF) (boiling point 153 °C), N,N-dimethylacetamide (DMA) (boiling point 165 °C); and cyclic amides such as N-methyl-2-pyrrolidone (NMP) (boiling point 202 °C), etc.

[0052] Examples of urea solvents include acyclic ureas such as tetramethylurea (boiling point 176 °C); and cyclic ureas such as 1,3-dimethyl-2-imidazolidinone (DMI) (boiling point 220 °C), N,N'-dimethylpropyleneurea (DMPU) (boiling point 246 °C), etc.

[0053] The non-aromatic solvent preferably includes a non-aromatic solvent selected from glycol ether solvents, glycol ether ester solvents, aliphatic ester solvents, and aliphatic ketone solvents.

[0054] When the total components in the resin composition are 100% by mass, the content of the (B) organic solvent in the resin composition preferably has a lower limit of 9.5% by mass or more, more preferably 10% by mass or more, still more preferably 10.5% by mass or more, even more preferably 11% by mass or more, still more preferably 11.5% by mass or more, particularly preferably 12% by mass or more, and most preferably 13% by mass or more, and an upper limit of preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, even more preferably 40% by mass or less, particularly preferably 35% by mass or less.

[0055] The ratio of the low-boiling organic solvent (Low) to the high-boiling organic solvent (High) in the (B) organic solvent can preferably be 0.18 or more, more preferably 0.3 or more, even more preferably 0.6 or more, and particularly preferably 1 or more, and can preferably be 6 or less, more preferably 5 or less, even more preferably 4 or less, and particularly preferably 3 or less.

[0056] <(C) Modified polydialkylsiloxane compound> The resin composition of the present invention contains a (C) modified polydialkylsiloxane compound. The (C) modified polydialkylsiloxane compound may be used alone or in combination of two or more in any ratio. The (C) modified dialkylsiloxane compound does not contain a fluorine atom and does not contain a curing-reactive group. The (C) modified dialkylsiloxane compound may contain a cyclic structure.

[0057] The (C) modified polydialkylsiloxane compound is, for example, a compound having a modified structure selected from the group consisting of a polydialkylsiloxane structure, a polyester chain bonded to the polydialkylsiloxane structure, and a polyether chain. Specifically, for example, the (C) modified polydialkylsiloxane compound is represented by the following general formula (I).

[0058] [Chemical Formula] Here, R 1 ~R 9 may be the same or different and each represents a hydrocarbon group having 1 to 8 carbon atoms, R 10 represents a group selected from the group consisting of a polyether-containing group and a polyester-containing group, and x represents the repeating number of siloxane units [R 7 R 8 SiO] (typically a dialkylsiloxane unit), and y represents the repeating number of siloxane units [R 9 R 10 SiO]. These siloxane units may be block-arranged or randomly arranged.

[0059] R 1 ~R 9 Examples of the hydrocarbon group having 1 to 8 carbon atoms represented by include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. The hydrocarbon group having 1 to 8 carbon atoms represented by R 1 ~R 9 may all be alkyl groups, or a part thereof may be a phenyl group. Among these, methyl group, ethyl group, propyl group, isopropyl group, (alkyl group having 1 to 3 carbon atoms) are preferable, and methyl group is more preferable.

[0060] For the polydialkylsiloxane structure [R 7 R 8 SiO]x, the two alkyl groups R 7 R 8may each independently be an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, or a neopentyl group. The two alkyl groups R 7 R 8 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms. Among these, a linear alkyl group is preferred, and a methyl group or an ethyl group is more preferred. Among them, the (C) modified polydialkylsiloxane compound has at least one of the two alkyl groups R 7 R 8 preferably being a methyl group.

[0061] The polydialkylsiloxane structure [R 7 R 8 SiO]x is, for example, polydimethylsiloxane, polymethylethylsiloxane, polymethylalkylsiloxane, polydiethylsiloxane, or polyethylalkylsiloxane, and is preferably polydimethylsiloxane, polymethylethylsiloxane, or polymethylalkylsiloxane.

[0062] The modified structure bonded to the polydialkylsiloxane structure is at least one selected from the group consisting of a polyester chain and a polyether chain.

[0063] When the modified structure consists of a polyether chain, the (C) modified polydialkylsiloxane compound is a polyether-modified polydialkylsiloxane. In the general formula (I), R 10 is -(CH2) i -O-[CH2CHR 11 -O] j -R 12 (wherein R 11 represents a hydrogen atom or a methyl group, R 12 represents an alkyl group or an aralkyl group, i represents a number from 1 to 6, and j represents a number from 3 to 300.) It is a polyether-containing group represented by

[0064] Methylene group (CH2) i The repeating number i of is from 1 to 6, but from the viewpoint of heat resistance, 1 to 3 is appropriate.

[0065] Polyether chain [CH2CHR 11 -O] j Specifically, it is ethylene oxide (EO) and propylene oxide (PO). The repeating number j of ethylene oxide (EO) units or propylene oxide (PO) units is about 3 to 300, for example, it may be about 5 to 100, and preferably it may be about 10 to 30.

[0066] R 12 Examples of the alkyl group represented by include a methyl group, an ethyl group, and a propyl group, and examples of the aralkyl group include a benzyl group and a phenethyl group.

[0067] The polyether-modified polydialkylsiloxane can be synthesized by a known synthesis method. Also, as commercially available products, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-320, BYK-325, BYK-331, BYK-337, BYK-333, BYK-341 (all manufactured by BYK-Chemie Japan), KF-351A, KF-352A, KF-353 (manufactured by Shin-Etsu Silicone Co., Ltd.), etc. can be mentioned.

[0068] Also, when the modified structure consists of a polyester chain, the (C) modified polydialkylsiloxane compound is a polyester-modified polydialkylsiloxane. In the above general formula (I), R 10 is -(CH2) k -O-[CO-R 13 -CO-O-R 14 -O] l -R 15 (Here, R 13 and R 14may be the same or different and each represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and R 15 represents an alkyl group or an aralkyl group, k represents a number from 1 to 6, and l represents a number from 3 to 300. ) is a polyester-containing group represented by

[0069] Methylene group (CH2) k The repeating number k of is from 1 to 6, but from the viewpoint of heat resistance, 1 to 3 is appropriate.

[0070] R 13 As the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R, any group for which the corresponding carboxylic acid (or its ester or anhydride) is available may be used. Examples include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and the like. Further, as the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R, any group for which the corresponding glycol is available may be used. Examples include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and the like. 14

[0071] Polyester chain [CO-R 13 -CO-O-R 14 -O] l The repeating number l of is about 3 to 300, and may be, for example, about 5 to 100, and preferably may be about 10 to 30.

[0072] R 15 Examples of the alkyl group represented by R include a methyl group, an ethyl group, a propyl group, etc., and examples of the aralkyl group include a benzyl group, a phenethyl group, etc.

[0073] Further, as the polyester chain, in addition to the above [CO-R 13 -CO-O-R 14 -O] l those obtained by polymerization of hydroxycarboxylic acids or ring-opening polymerization of cyclic lactones may also be used.

[0074] The polyester-modified polydialkylsiloxane can be synthesized by a known synthesis method. Also, as commercially available products, BYK-310, BYK-314, BYK-315 (manufactured by BYK-Chemie Japan), X-22-715 (manufactured by Shin-Etsu Silicone), etc. can be mentioned.

[0075] (C) The bonding position of the modified structure in the modified polydialkylsiloxane compound is not particularly limited, and it may be at the end of the chain structure formed by the polydialkylsiloxane structure or in the middle of the chain. Also, the number of modified structures in the polydialkylsiloxane structure is not particularly limited, and one or more may be sufficient.

[0076] From the viewpoint of obtaining the effects of the present invention well, when the non-volatile components in the resin composition are 100% by mass, the content of the (C) modified polydialkylsiloxane compound in the resin composition can preferably be 0.01% by mass or more, more preferably 0.02% by mass or more, and particularly preferably 0.03% by mass or more. The upper limit of the content can preferably be 0.3% by mass or less, more preferably 0.25% by mass or less, further preferably 0.2% by mass or less, and particularly preferably 0.15% by mass or less when the non-volatile components in the resin composition are 100% by mass.

[0077] Also, from the viewpoint of obtaining the effects of the present invention well, when the resin components in the resin composition are 100% by mass, the content of the (C) modified polydialkylsiloxane compound in the resin composition can preferably be 0.04% by mass or more, more preferably 0.06% by mass or more, further preferably 0.08% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit of the content can preferably be 0.55% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.45% by mass or less when the resin components in the resin composition are 100% by mass.

[0078] The ratio of the content of component (C) to the content of component (B) ((C) component / (B) component) can preferably be 0.06% or more, more preferably 0.08% or more, and particularly preferably 0.1% or more. The upper limit of this ratio is preferably 1.5% or less, more preferably 1.3% or less, and particularly preferably 1% or less.

[0079] As the content of component (C), when the total of components (A) and (B) is 100% by mass, it can preferably be 0.06% by mass or more, more preferably 0.08% by mass or more, and particularly preferably 0.1% by mass or more, and can preferably be 0.37 or less, more preferably 0.36% by mass or less, and particularly preferably 0.35% by mass or less.

[0080] <(D) Inorganic filler> The resin composition of the present invention contains (D) an inorganic filler. (D) The inorganic filler may be used alone or in combination of two or more in any ratio.

[0081] As the material of (D) the inorganic filler, an inorganic compound is used. Examples of the material of (D) 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, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, etc. Also, (D) the inorganic filler is preferably spherical silica.

[0082] (D) Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka Co., Ltd.; and "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation.

[0083] (D) The average particle diameter of the inorganic filler can preferably be 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, even more preferably 2 μm or less, and particularly preferably 1.5 μm or less. The lower limit of the average particle diameter can preferably be 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more.

[0084] (D) The specific surface area of the inorganic filler is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, still more preferably 1 m 2 / g or more, and particularly preferably 3 m 2 / g or more. The upper limit of the specific surface area can preferably be 100 m 2 / g or less, more preferably 70 m 2 / g or less, still more preferably 50 m 2 / g or less, even more preferably 30 m 2 / g or less, and particularly preferably 10 m 2 / g or less.

[0085] (D) The surface of the inorganic filler is preferably heat-treated. From the viewpoint of suppressing breakage (cutting) due to collision between particles, the treatment temperature is, for example, in the range of 50°C to 100°C, preferably 70°C to 80°C, and the treatment time is, for example, in the range of 0.5 hours to 3 hours, preferably 1 hour to 3 hours.

[0086] (D) The inorganic filler is preferably treated with a surface treatment agent from the viewpoints of improving moisture resistance and dispersibility. The treatment with the surface treatment agent is preferably carried out simultaneously with the heat treatment described above. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazane compounds, titanate-based coupling agents, and the like. Further, the surface treatment agent may be used alone or in any combination of two or more kinds.

[0087] Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane), "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc., all manufactured by Shin-Etsu Chemical Co., Ltd.

[0088] From the viewpoint of improving the dispersibility of the (D) inorganic filler, the degree of surface treatment with the surface treatment agent preferably falls within a predetermined range. Specifically, it is preferably surface-treated with 0.2% by mass to 5% by mass of the surface treatment agent, more preferably 0.2% by mass to 3% by mass, and even more preferably 0.3% by mass to 2% by mass, based on 100% by mass of the (D) inorganic filler.

[0089] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the (D) inorganic filler is 0.02 mg / m 2The above is preferable, 0.1 mg / m 2 The above is more preferable, 0.2 mg / m 2 The above is even more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, 1.0 mg / m 2 The following is preferable, 0.8 mg / m 2 The following is more preferable, 0.5 mg / m 2 The following is even more preferable. The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 °C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. etc. can be used.

[0090] When the content of the (D) inorganic filler in the resin composition is based on 100% by mass of the non-volatile components in the resin composition, it can preferably be 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, and particularly preferably 75% by mass or less. The lower limit of the content can, for example, be 10% by mass or more, 25% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 65% by mass or more, and particularly preferably 70% by mass or more when the non-volatile components in the resin composition are 100% by mass.

[0091] <(E) curing agent> The resin composition of the present invention contains an (E) curing agent. The (E) curing agent may be used alone or in any combination of two or more. The (E) curing agent may have a function of reacting with the (A) epoxy resin to cause curing.

[0092] (E) As the curing agent, for example, active ester-based curing agents, phenolic curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and thiol-based curing agents, etc. can be mentioned. For example, the (E) curing agent may contain both an active ester-based curing agent and a phenolic curing agent. In one embodiment, from the viewpoint of further suppressing the dielectric loss tangent, it is particularly preferable that the (E) curing agent contains an active ester-based curing agent. Also, in one embodiment, from the viewpoint of further improving the curability, it is particularly preferable that the (E) curing agent contains a phenolic curing agent.

[0093] As the active ester-based curing agent, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are generally preferably used. The active ester compound is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, etc. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0094] As the active ester-based curing agent, specifically, dicyclopentadiene-type active ester compounds, naphthalene-type active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolak, and active ester compounds containing a benzoylated product of phenol novolak are preferred. Among them, it is more preferable that it is at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred.

[0095] Commercially available products of the active ester-based curing agent include, as the active ester compound containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); as the active ester compound containing a naphthalene structure, "HP-B-8151-62T", "EXB-8100L-65T", "EXB-9416-70BK", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); as the phosphorus-containing active ester compound, "EXB9401" (manufactured by DIC Corporation), as the active ester compound which is an acetylated product of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation), as the active ester compound which is a benzoylated product of phenol novolak, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), as the active ester compound containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Inc.), etc.

[0096] As a phenolic curing agent, from the viewpoints of heat resistance and water resistance, a phenolic curing agent having a novolak structure is preferable. Further, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenolic curing agent is preferable, and a phenolic curing agent containing a triazine skeleton is more preferable. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a phenolic novolak resin containing a triazine skeleton is preferable. Specific examples of the phenolic curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd., "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "KA-1160" manufactured by DIC Corporation, etc.

[0097] Examples of the carbodiimide-based curing agent include curing agents having one or more, preferably two or more carbodiimide structures in one molecule, such as aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xilylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly(methylenebiscyclohexylene carbodiimide), and poly(isophorone carbodiimide); and aromatic polycarbodiimides such as poly(phenylene carbodiimide), poly(naphthylene carbodiimide), poly(tolylene carbodiimide), poly(methyldiisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), poly(diisopropylphenylene carbodiimide), poly(xylylene carbodiimide), poly(tetramethylxylylene carbodiimide), poly(methylenediphenylene carbodiimide), and poly[methylenebis(methylphenylene) carbodiimide].

[0098] Examples of commercially available carbodiimide-based curing agents include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; "Stabaxol P", "Stabaxol P400", "Highcadil 510", etc. manufactured by Rhein Chemie.

[0099] Examples of the acid anhydride-based curing agent include curing agents having one or more acid anhydride groups in one molecule, and curing agents having two or more acid anhydride groups in one molecule are preferred. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as styrene-maleic acid resin copolymerized from styrene and maleic acid. Commercially available products of the acid anhydride-based curing agent include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Rika Co., Ltd., "YH-306", "YH-307" manufactured by Mitsubishi Chemical Corporation, "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd., and "EF-30", "EF-40", "EF-60", "EF-80" manufactured by Cray Valley Co., Ltd.

[0100] The amine-based curing agent may be a curing agent having one or more, preferably two or more, amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propane. propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. As the amine-based curing agent, commercially available products may be used, and examples thereof include "SEIKACURE-S" manufactured by Seika Corporation, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0101] Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0102] Examples of the cyanate ester curing agent include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; prepolymers in which part of these cyanate resins is triazine-formed; and the like. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins), "BA230", "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazine-formed to become trimers), etc. manufactured by Lonza Japan Co., Ltd.

[0103] Examples of the thiol curing agent include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl)isocyanurate, and the like.

[0104] (E) The reactive group equivalent of the curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., still more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactive group equivalent is the mass of the (E) curing agent per equivalent of the reactive group.

[0105] The molar ratio of the total epoxy groups of the (A) epoxy resin to the total reactive groups of the (B) curing agent in the resin composition (number of moles of epoxy groups: number of moles of reactive groups) is preferably in the range of 1:0.2 to 1:2, more preferably in the range of 1:0.3 to 1:1.5, and even more preferably in the range of 1:0.4 to 1:1.

[0106] When the content of the non-volatile components in the resin composition is taken as 100% by mass, the content of the (E) curing agent in the resin composition is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 12% by mass or less. The lower limit can be 0% by mass or more, 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 8% by mass or more.

[0107] When the resin components in the resin composition are taken as 100% by mass, the content of the (E) curing agent in the resin composition is preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less, and particularly preferably 38% by mass or less. The lower limit can be 0.1% by mass or more, 1% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, and particularly preferably 35% by mass or more.

[0108] The mass ratio of the (E) curing agent to the (A) epoxy resin in the resin composition ((E) curing agent / (A) epoxy resin) can be preferably 0.01 or more, more preferably 0.05 or more, and particularly preferably 0.1 or more. The upper limit of the content can be preferably 2 or less, more preferably 1.2 or less, and particularly preferably 0.7 or less.

[0109] When the non-volatile components in the resin composition are taken as 100% by mass, the total content of the (A) epoxy resin and the (E) curing agent in the resin composition can be preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more. The upper limit of the total content can be preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0110] (E) When an active ester-based curing agent is included as the curing agent, the content rate of the active ester-based curing agent in the resin composition, when the non-volatile components in the resin composition are 100% by mass, from the viewpoint of further suppressing the dielectric loss tangent, is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 6% by mass or more, particularly preferably 9% by mass or more, and when the resin components in the resin composition are 100% by mass, it can be preferably 25% by mass or more, more preferably 28% by mass or more, still more preferably 30% by mass or more, particularly preferably 32% by mass or more.

[0111] Also, the lower limit of the content of the active ester-based curing agent in the resin composition, when the (E) curing agent in the resin composition is 100% by mass, from the viewpoint of further suppressing the dielectric loss tangent, can be preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 85% by mass or more.

[0112] (E) When a phenolic curing agent is included as the curing agent, the content rate of the phenolic curing agent in the resin composition, when the non-volatile components in the resin composition are 100% by mass, from the viewpoint of further improving the curability, can be preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and from the viewpoint of further suppressing the dielectric loss tangent, can be preferably 1.5% by mass or less, more preferably 1% by mass or less.

[0113] (E) When a phenolic curing agent is included as the curing agent, the content rate of the phenolic curing agent in the resin composition, when the resin components in the resin composition are 100% by mass, from the viewpoint of further improving the curability, can be preferably 3.0% by mass or more, more preferably 3.3% by mass or more, and from the viewpoint of further suppressing the dielectric loss tangent, can be preferably 4.0% by mass or less, more preferably 3.5% by mass or less.

[0114] (E) When a carbodiimide-based curing agent is included as the curing agent, the content of the carbodiimide-based curing agent in the resin composition, when the non-volatile components in the resin composition are 100% by mass, from the viewpoint of further improving the curability, may preferably be 0.1% by mass or more, more preferably 0.2% by mass or more, and from the viewpoint of further suppressing the dielectric loss tangent, may preferably be 0.5% by mass or less, more preferably 0.3% by mass or less.

[0115] (E) When a carbodiimide-based curing agent is included as the curing agent, the content of the carbodiimide-based curing agent in the resin composition, when the resin components in the resin composition are 100% by mass, from the viewpoint of further improving the curability, may preferably be 0.5% by mass or more, more preferably 0.8% by mass or more, and from the viewpoint of further suppressing the dielectric loss tangent, may preferably be 1.2% by mass or less, more preferably 0.9% by mass or less.

[0116] <(F) Thermoplastic resin> The resin composition of the present invention may further contain (F) a thermoplastic resin as an optional component. The (F) thermoplastic resin described here is a component other than those corresponding to the above-described (A) epoxy resin and (E) curing agent.

[0117] Examples of the (F) thermoplastic resin include polyimide resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, and the like. In one embodiment, the (F) thermoplastic resin preferably contains a thermoplastic resin selected from the group consisting of polyimide resin and phenoxy resin, and more preferably contains phenoxy resin. Further, the thermoplastic resin may be used alone or in combination of two or more.

[0118] Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Lica Coat SN20" and "Lica Coat PN20" manufactured by Nippon Rika Kasei Co., Ltd., and the like.

[0119] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0120] Specific examples of the phenoxy resin include "1256" and "4250" (both are bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical Corporation; "YX8100" (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation, "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX7200B35", "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482" manufactured by Mitsubishi Chemical Corporation, and the like.

[0121] Examples of the polyvinyl acetal resin include, for example, polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Kabushiki Kaisha; the Esrec BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series manufactured by Sekisui Chemical Co., Ltd.; and the like.

[0122] Examples of polyolefin resins include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; polyolefin polymers such as polypropylene and ethylene-propylene block copolymer, etc.

[0123] Examples of polybutadiene resins include, for example, resins containing a hydrogenated polybutadiene backbone, hydroxy group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, polyphenylene ether-polybutadiene resins, etc.

[0124] Specific examples of polyamideimide resins include "Vylon Max HR11NN" and "Vylon Max HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins also include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane backbone) manufactured by Hitachi Chemical Co., Ltd.

[0125] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., etc.

[0126] Specific examples of polysulfone resins include polysulfones "P1700", "P3500", etc. manufactured by Solvay Advanced Polymers, LLC.

[0127] Specific examples of polyphenylene ether resins include "NORYL SA90" manufactured by SABIC, etc. Specific examples of polyetherimide resins include "ULTEM" manufactured by GE, etc.

[0128] Examples of the polycarbonate resin include hydroxy group-containing carbonate resin, phenolic hydroxyl group-containing carbonate resin, carboxy group-containing carbonate resin, acid anhydride group-containing carbonate resin, isocyanate group-containing carbonate resin, urethane group-containing carbonate resin, and the like. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd., and the like. Specific examples of the polyetheretherketone resin include "Sumipro EK" manufactured by Sumitomo Chemical Company, and the like.

[0129] Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethylene terephthalate resin, and the like.

[0130] (F) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, from the viewpoint of obtaining the effects of the present invention significantly, and is preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less.

[0131] When the content of the nonvolatile components in the resin composition is 100% by mass, the content of the (F) thermoplastic resin in the resin composition is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, even more preferably 1% by mass or less, particularly preferably 0.8% by mass or less, from the viewpoint of obtaining the desired effects of the present invention significantly. The lower limit of the content may be, for example, 0% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, and the like.

[0132] When the content rate of the (F) thermoplastic resin in the resin composition is based on 100% by mass of the resin components in the resin composition, from the viewpoint of remarkably obtaining the desired effects of the present invention, it may preferably be 4% by mass or less, more preferably 3.5% by mass or less, still more preferably 3% by mass or less, even more preferably 2.7% by mass or less, and particularly preferably 0.8% by mass or less. The lower limit of the content may be, for example, 0% by mass or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, 2.5% by mass or more, etc.

[0133] <(G) Curing accelerator> The resin composition of the present invention may contain (G) a curing accelerator as an optional component. The (G) curing accelerator has a function as a curing catalyst that accelerates the curing of the (A) epoxy resin.

[0134] Examples of the (G) curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, and the like. The (G) curing accelerator preferably contains a curing accelerator selected from imidazole-based curing accelerators and amine-based curing accelerators. The (G) curing accelerator may be used alone or in combination of two or more.

[0135] Examples of phosphorus-based curing accelerators include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine·triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine·p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine;Examples of aromatic phosphines include dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenylether, and the like.;

[0136] Examples of urea-based curing accelerators include, for example, 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; aromatic dimethylureas such as 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N’,N’-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N’,N’-dimethylurea) [toluene bisdimethylurea], etc.

[0137] Examples of guanidine-based curing accelerators include, for example, 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]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc.

[0138] Examples of imidazole-based curing accelerators include imidazole compounds such as 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-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

[0139] Commercially available products may be used as the imidazole-based curing accelerator. Examples include "1B2PZ", "2MZA-PW", "2PHZ-PW", "C11Z-A" manufactured by Shikoku Kasei Kogyo Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0140] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, etc. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(4) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(4) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc.

[0141] Examples of amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc.

[0142] Commercially available products may be used as the amine-based hardening accelerator. For example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc. may be mentioned.

[0143] When the non-volatile components in the resin composition are 100% by mass, the content of the (G) hardening accelerator in the resin composition is preferably 5% by mass or less, more preferably 0.3% by mass or less, still more preferably 0.25% by mass or less, even more preferably 0.2% by mass or less, and particularly preferably 0.15% by mass or less. The lower limit of the content may be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.03% by mass or more, etc.

[0144] When the resin component in the resin composition is 100% by mass, the content of the (G) curing accelerator in the resin composition is preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.7% by mass or less, even more preferably 0.6% by mass or less, and particularly preferably 0.5% by mass or less. The lower limit of the content can be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.03% by mass or more, etc.

[0145] <(H) Other Additives> The resin composition of the present invention may further contain any other additives as non-volatile components. Examples of such additives include rubber particles such as organic fillers; radical polymerizable compounds having ethylenically unsaturated bonds; radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; thermosetting resins other than epoxy resins such as epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, melamine resins, and silicone resins; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as benton and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic-based flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers, etc. Other additives may be used alone or in combination of two or more in any ratio. The content of other additives can be appropriately set by those skilled in the art.

[0146] <Method for Producing Resin Composition> The resin composition of the present invention can be produced, for example, by adding (A) an epoxy resin, (B) an organic solvent, (C) a modified polydialkylsiloxane compound, (D) an inorganic filler, and (E) a curing agent, and, if necessary, (F) a thermoplastic resin, (G) a curing accelerator, and (H) other additives to an arbitrary preparation container in an arbitrary order and / or partially or entirely simultaneously and mixing them. Also, during the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or throughout the process.

[0147] Also, during or after the process of adding and mixing each component, the resin composition may be stirred or shaken using a stirring device such as a mixer or a shaking device to be uniformly dispersed. Also, defoaming may be performed under low-pressure conditions such as under vacuum simultaneously with the stirring or shaking.

[0148] <Properties of Resin Composition> The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) an organic solvent, (C) a modified polydialkylsiloxane compound, (D) an inorganic filler, and (E) a curing agent. The component (C) is a compound having a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure. The viscosity measured using an E-type viscometer under the conditions of 25°C and 50 rpm is 3 mPa·s to 1,000 mPa·s. By using such a resin composition, clogging of the nozzle due to drying of the nozzle can be suppressed, repellency of the resin composition on the coating surface can be suppressed, separation of the resin in the resin composition layer can also be suppressed, and the average linear thermal expansion coefficient (CTE) of the cured product of the resin composition can be reduced.

[0149] In one embodiment, the resin composition of the present invention may have a feature of suppressing clogging of the nozzle due to drying of the nozzle. In one embodiment, as in Examples 1 to 8 below, when the varnish-like resin composition of the present invention is measured for weight loss at 25°C for 30 minutes using a differential thermal-thermogravimetric simultaneous measurement apparatus (TG-DTA apparatus), it is preferable that the weight loss rate after 30 minutes is less than 10%. In one embodiment, the resin composition of the present invention may have a feature of suppressing clogging of the nozzle due to drying of the nozzle and suppressing repelling of the resin composition on the coating surface. In one embodiment, as in Examples 1 to 8 below, when the varnish-like resin composition of the present invention is introduced into a slit coater and a slit coating is performed on a glass plate so that the film thickness becomes 25 μm to form a coating film, when the thickness of the entire substrate after drying the coating film is measured, the variation in the thickness difference (X direction) between the coating start point and the central point, and the end point, and the variation in the thickness difference (Y direction) between the center and the left and right of the slit coater, it is preferable that the thickness difference is less than 5 μm. In one embodiment, the resin composition of the present invention may have a feature of suppressing separation of the resin in the resin composition after coating and having good thin film formability. In one embodiment, as in Examples 1 to 8 below, in the measurement of the thickness of the entire substrate after drying the coating film, it is preferable that the average film thickness is 25 μm ± 2 μm.

[0150] In one embodiment, the resin composition of the present invention can reduce the average linear thermal expansion coefficient (CTE) of the cured product of the resin composition. For example, when a cured product is formed using the resin composition of the present invention as in Examples 1 to 8 below, the average linear thermal expansion coefficient (CTE) of the cured product in the range from 25°C (298 K) to 150°C (423 K) is less than 20 ppm / K, preferably 19 ppm / K or less, more preferably 18 ppm / K or less, particularly preferably 17 ppm / K, and the lower limit can be, for example, 1 ppm / K or more, 3 ppm / K or more, 5 ppm / K or more, etc. The average linear thermal expansion coefficient is calculated based on the thermal expansion rate measured according to the method described in the examples below.

[0151] <Use of the resin composition> The resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (for example, a resin composition for an insulating layer of a printed wiring board), and can be more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (for example, a resin composition for an interlayer insulating layer of a printed wiring board). The resin composition of the present invention can also be suitably used when the printed wiring board is a component-embedded circuit board. The resin composition of the present invention can also be suitably used as a resin composition for forming an insulating layer of a redistribution substrate of a semiconductor package (for example, a resin composition for an insulating layer of a redistribution substrate). In the present invention, the printed wiring board and the redistribution substrate are collectively referred to as a "circuit board", and therefore the resin composition of the present invention can be suitably used for an insulating layer of a circuit board.

[0152] The resin composition of the present invention can also be widely used in applications where a resin composition is required, such as resin sheets, sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, and the like.

[0153] <Sheet-like laminated material> It is preferable to apply and use the resin composition of the present invention in a varnish state, but it may also be used in the form of a sheet-like laminated material containing the resin composition.

[0154] As the sheet-like laminated material, the following resin sheets and prepregs are preferable.

[0155] In one embodiment, the resin sheet has a support and a resin composition layer provided on the support.

[0156] The thickness of the resin composition layer varies depending on the application, and may be appropriately determined according to the application. For example, from the viewpoints of thinning the printed wiring board and providing a cured product having excellent insulation even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be, for example, 1 μm or more, 5 μm or more, 10 μm or more, etc.

[0157] Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

[0158] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0159] When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferred. As the copper foil, a foil made of single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0160] The support may be subjected to matting treatment, corona treatment, or antistatic treatment on the surface that joins the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface that joins the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. As the support with a release layer, a commercially available product may be used. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin-based release agent, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc.

[0161] The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferable, and a range of 10 μm to 60 μm is more preferable. When using a support with a release layer, it is preferable that the total thickness of the support with a release layer is within the above range.

[0162] When using a metal foil as the support, a metal foil with a support substrate, in which a support substrate that can be peeled off is laminated on a thin metal foil, may be used. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer provided on the support substrate, and a metal foil provided on the release layer. When using a metal foil with a support substrate as the support, the resin composition layer is provided on the metal foil.

[0163] In the metal foil with a support substrate, examples of the material of the support substrate include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, etc. When using a copper foil as the support substrate, it may be an electrolytic copper foil or a rolled copper foil. Further, the release layer is not particularly limited as long as the metal foil can be peeled off from the support substrate. Examples thereof include an alloy layer of elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic film, etc.

[0164] In the metal foil with a support substrate, as the material of the metal foil, for example, copper foil and copper alloy foil are preferable.

[0165] In the metal foil with a support substrate, the thickness of the support substrate is preferably in the range of 10 μm to 150 μm, more preferably in the range of 10 μm to 100 μm. Also, the thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

[0166] In one embodiment, the resin sheet may further include any layer as needed. Examples of such an arbitrary layer include a protective film similar to the support provided on the surface of the resin composition layer that is not joined to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust and the like and scratches on the surface of the resin composition layer.

[0167] The resin sheet can be manufactured, for example, by directly using a liquid resin composition or by preparing a resin varnish in which the resin composition is dissolved in an organic solvent, applying this onto a support using a die coater or the like, and further drying to form a resin composition layer.

[0168] Examples of the organic solvent include the same ones as those described as components of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0169] Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but drying is carried out so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it also varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% by mass to 60% by mass of the organic solvent, a resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0170] The resin sheet can be stored by being wound into a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0171] In one embodiment, the prepreg is formed by impregnating a sheet-shaped fiber base material with the resin composition of the present invention.

[0172] The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the circuit board, the thickness of the sheet-shaped fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited. Usually, it is 10 μm or more.

[0173] The prepreg can be manufactured by known methods such as the hot melt method and the solvent method.

[0174] The thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.

[0175] The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board). The sheet-like laminated material of the present invention can also be suitably used for forming an insulating layer of a redistribution substrate of a semiconductor package (for the insulating layer of a redistribution substrate). That is, the sheet-like laminated material of the present invention can be suitably used as an insulating layer for a circuit board.

[0176] [Circuit Board] The circuit board of the present invention includes a cured product (for example, an insulating layer) obtained by curing the above resin composition. The cured product of the resin composition is preferably formed from the above resin composition by a method selected from the group consisting of a roll coating method, a spray coating method, a spin coating method, a bar coating method, a slit coating method, a curtain coating method, and a dipping method. Among them, the slit coating method is preferable. In the slit coating method, a varnish-like resin composition is introduced into a slit coater, and the varnish-like resin composition is applied onto a support to form a resin composition layer (so-called coating film). The present invention also provides such a circuit board, that is, a circuit board including a cured product of the resin composition of the present invention.

[0177] <Printed Wiring Board> In one embodiment, the circuit board of the present invention is a printed wiring board. The printed wiring board can be manufactured, for example, by a method including the following steps (i) to (iii) using the resin composition of the present invention. (i) A step of applying a resin composition onto a substrate to form a coating film (ii) A step of drying the coating film (iii) A step of thermally curing the coating film to form an insulating layer

[0178] Step (i) is a step of applying a resin composition onto a substrate to form a coating film.

[0179] The "substrate" used in step (i) is a member that serves as the substrate of a printed wiring board. Examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, glass substrates, wafers (semiconductor wafers such as silicon wafers, glass wafers), and the like. Further, the substrate may have a conductor layer on one or both of its surfaces, and this conductor layer may be pattern-processed. An inner layer substrate having a conductor layer (circuit) formed on one or both surfaces of the substrate may be referred to as an "inner layer circuit board". Also, when manufacturing a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the "substrate" as referred to in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate with components embedded therein may be used.

[0180] The application of the resin composition onto the substrate can be carried out, for example, by a roll coating method, a spray coating method, a spin coating method, a bar coating method, a slit coating method, a curtain coating method, or a dipping method. Among these, it is preferable to apply the resin composition by the slit coating method.

[0181] From the viewpoint of thin film formation, the thickness of the coating film formed in step (i) is preferably 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, even more preferably 40 μm or less, and particularly preferably 30 μm or less. The resin composition of the present invention is particularly useful in the formation of a thin film of 50 μm or less by the slit coating method, where clogging of the nozzle due to drying of the nozzle becomes a significant problem. The lower limit of the thickness of the coating film is not particularly limited, but can be, for example, 0.1 μm or more, 0.5 μm or more, 1 μm or more, 3 μm or more, 5 μm or more, 10 μm or more, etc.

[0182] Step (ii) is a step of drying the coating film. The drying conditions of the resin composition are not particularly limited, and the conditions usually employed when forming the insulating layer of a printed wiring board may be used.

[0183] The drying of the coating film in step (ii) can be carried out, for example, by evacuation, reduced pressure, heating, hot air blowing, or a combination thereof, and it is preferable to perform vacuum drying (including reduced pressure drying) and / or drying by heating. By drying the coating film in step (ii), the content of the organic solvent in the resin composition is preferably 10% by mass or less, more preferably 5% by mass or less.

[0184] In step (ii), when the coating film is vacuum dried, the air pressure is preferably 500 Pa or less, more preferably 200 Pa or less. The vacuum drying time is not particularly limited, but is preferably 30 seconds to 30 minutes, more preferably 30 seconds to 10 minutes.

[0185] In step (ii), when the coating film is dried by heating, the heat drying temperature is preferably 50°C or higher and lower than 200°C, more preferably 50°C or higher and lower than 150°C, still more preferably 50°C or higher and lower than 140°C, even more preferably 70°C or higher and lower than 130°C, and particularly preferably 80°C or higher and lower than 120°C. The heat drying time for maintaining the above heat drying temperature is preferably 1 minute to 30 minutes, more preferably 1 minute to 10 minutes, still more preferably 1 minute to 5 minutes.

[0186] In the drying of the coating film in step (ii), it is particularly preferable to perform vacuum drying before drying by heating.

[0187] Step (iii) is a step of thermosetting the coating film to form an insulating layer. The thermosetting conditions of the resin composition are not particularly limited, and the conditions usually employed when forming an insulating layer of a printed wiring board may be used.

[0188] Also, the printed wiring board may be manufactured, for example, by a method including the following steps (I) and (II) using the above resin sheet. (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is joined to the inner layer substrate (II) A step of curing (for example, thermosetting) the resin composition layer to form an insulating layer

[0189] The "inner layer substrate" used in step (I) may be the member serving as the substrate of the printed wiring board described in step (1) above. Since the details are the same as those described in step (i) above, the description here is omitted.

[0190] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll). Note that the thermocompression bonding member may be pressed directly against the resin sheet, or may be pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate.

[0191] The lamination of the inner layer substrate and the resin sheet may be carried out by the vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C; the thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa; and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination can preferably be carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

[0192] The lamination can be carried out by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nippon Materials Co., Ltd., a batch type vacuum pressurized laminator, and the like.

[0193] After lamination, under normal pressure (atmospheric pressure), for example, by pressing the heat-sealing member from the support side, a smoothing process of the laminated resin sheet may be performed. The pressing conditions for the smoothing process can be the same as the heat-sealing conditions for the above lamination. The smoothing process can be performed by a commercially available laminator. Note that the lamination and the smoothing process may be continuously performed using the above commercially available vacuum laminator.

[0194] The support may be removed between step (I) and step (II), or may be removed after step (II). Note that when a metal foil is used as the support, a conductor layer may be formed using the metal foil without peeling the support. Also, when a metal foil with a support substrate is used as the support, the support substrate (and the release layer) may be peeled off. And a conductor layer can be formed using the metal foil.

[0195] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and the conditions usually employed when forming an insulating layer of a printed wiring board may be used.

[0196] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition, etc. In one embodiment, the curing temperature is preferably 140°C to 250°C, more preferably 150°C to 240°C, and even more preferably 170°C to 230°C. The curing time can be preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and even more preferably 15 minutes to 120 minutes.

[0197] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 140°C, preferably 60°C to 135°C, more preferably 70°C to 130°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0198] When manufacturing a printed wiring board, the following steps may be further performed: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art and used in the manufacture of printed wiring boards. When removing the support after step (II), the removal of the support may be carried out between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board.

[0199] In another embodiment, the printed wiring board of the present invention can be manufactured using the above-described prepreg. The manufacturing method is basically the same as the case of using a resin sheet.

[0200] Step (III) is a step of drilling holes in the insulating layer, by which holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, a laser, a plasma, etc., according to the composition of the resin composition used for forming the insulating layer. The dimensions and shapes of the holes may be appropriately determined according to the design of the printed wiring board.

[0201] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), removal of smear (desmear) is also carried out. The procedures and conditions for the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer 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.

[0202] The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution. Preferably, it is an alkaline solution, and as the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Security P" and "Swelling Dip Security SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited, but for example, it can be performed by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0203] The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan Co., Ltd.

[0204] Also, as the neutralizing liquid used for the roughening treatment, an acidic aqueous solution is preferable, and examples of commercially available products include "Reduction Solution Security P" manufactured by Atotech Japan Co., Ltd.

[0205] The treatment with the neutralizing liquid can be performed by immersing the treated surface, which has been roughened with the oxidizing agent, in the neutralizing liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with the oxidizing agent in the neutralizing liquid at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0206] In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and still more preferably 200 nm or less. The lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and still more preferably 50 nm or more. Further, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and still more preferably 200 nm or less. The lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and still more preferably 50 nm or more. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter.

[0207] Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferable, and a single metal layer of copper is still more preferable.

[0208] The conductor layer may have a single-layer structure or a multi-layer 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 multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

[0209] The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0210] In one embodiment, the conductor layer may be formed by plating. For example, a plating seed layer can be formed on the surface of the insulating layer by electroless plating, and then a conductor layer having a desired wiring pattern can be formed by plating on the formed plating seed layer according to a conventional known technique such as a semi-additive method or a full-additive method. From the viewpoint of manufacturing simplicity, it is preferably formed by the semi-additive method. Hereinafter, an example of forming the conductor layer by the semi-additive method will be shown.

[0211] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer by electroplating on the exposed plating seed layer, the mask pattern is removed. Then, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0212] In other embodiments, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably carried out between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is carried out to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as the modified semi-additive method.

[0213] The metal foil can be manufactured by a known method such as an electrolytic method or a rolling method, for example. Examples of commercially available metal foils include HLP foil, JXUT-III foil manufactured by JX Metals, 3EC-III foil, TP-III foil manufactured by Mitsui Metals, and the like.

[0214] Alternatively, as described above, when a metal foil or a metal foil with a support substrate is used as the support of the resin sheet, the conductor layer may be formed using the metal foil.

[0215] <Rewiring Substrate of Semiconductor Package> In one embodiment, the circuit board of the present invention is a rewiring substrate of a semiconductor package. Hereinafter, an explanation will be given in accordance with the manufacturing method of the semiconductor package.

[0216] The semiconductor package includes a cured product of the resin composition of the present invention as an insulating layer of the rewiring substrate. Note that the semiconductor package may include a cured product of the resin composition of the present invention as a sealing layer.

[0217] The semiconductor package can be manufactured, for example, by a method including the following steps (1) to (6) using the resin composition or resin sheet of the present invention. The resin composition or resin sheet of the present invention may be used to form the rewiring formation layer in step (5) (specifically, the insulating layer for forming the rewiring substrate) or the sealing layer in step (3). Hereinafter, an example of forming the sealing layer and the rewiring formation layer using the resin composition and the resin sheet is shown. However, the technology for forming the sealing layer and the rewiring formation layer of the semiconductor package is known, and those skilled in the art can manufacture the semiconductor package according to the known technology using the resin composition and the resin sheet of the present invention. (1) Step of laminating a temporary fixing film on a base material (2) Step of temporarily fixing a semiconductor chip on the temporary fixing film (3) Step of forming a sealing layer on the semiconductor chip (4) Step of peeling the base material and the temporary fixing film from the semiconductor chip (5) Step of forming a rewiring formation layer as an insulating layer on the surface of the base material and the temporary fixing film of the semiconductor chip from which they are peeled, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring formation layer

[0218] - Step (1) - The material used for the base material is not particularly limited. Examples of the base material include semiconductor wafers such as silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates impregnated with epoxy resins or the like in glass fibers and subjected to thermosetting treatment (for example, FR-4 substrates); substrates made of bismaleimide triazine resin (BT resin), and the like.

[0219] The material of the temporary fixing film is not particularly limited as long as it can be peeled from the semiconductor chip in step (4) and can temporarily fix the semiconductor chip. Commercially available products can be used as the temporary fixing film. Examples of commercially available products include Rivar Alpha manufactured by Nitto Denko Corporation.

[0220] - Step (2) - The temporary fixing of the semiconductor chip can be performed using known devices such as a flip chip bonder or a die bonder. The layout and the number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production quantity of the target semiconductor package, etc. For example, they can be temporarily fixed by arranging them in a matrix form with multiple rows and multiple columns.

[0221] - Step (3) - The resin composition layer of the resin sheet of the present invention is laminated on the semiconductor chip, or the resin composition of the present invention is applied on the semiconductor chip and cured (for example, thermally cured) to form a sealing layer.

[0222] For example, the lamination of the semiconductor chip and the resin sheet can be performed by heat - pressure bonding the resin sheet to the semiconductor chip from the support side after removing the protective film of the resin sheet. Examples of the member for heat - pressure bonding the resin sheet to the semiconductor chip (hereinafter also referred to as "heat - pressure bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (such as a SUS roll). It is preferable to press through an elastic material such as heat - resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the semiconductor chip instead of pressing the heat - pressure bonding member directly against the resin sheet. The lamination of the semiconductor chip and the resin sheet may be carried out by the vacuum lamination method, and the lamination conditions are the same as the lamination conditions described in relation to the manufacturing method of the printed wiring board, and the preferable ranges are also the same.

[0223] After lamination, the resin composition is thermally cured to form a sealing layer. The thermal curing conditions are the same as the thermal curing conditions described in relation to the manufacturing method of the printed wiring board.

[0224] The support of the resin sheet may be peeled off after laminating and thermally curing the resin sheet on the semiconductor chip, or the support may be peeled off before laminating the resin sheet on the semiconductor chip.

[0225] In the case of forming a sealing layer by applying the resin composition of the present invention, since it is the same as the content described in the above steps (i) to (iii) of the printed wiring board, the description here is omitted.

[0226] - Step (4)- The method of peeling the base material and the temporary fixing film can be appropriately changed according to the material of the temporary fixing film, etc. For example, there are a method of heating and foaming (or expanding) the temporary fixing film for peeling, and a method of irradiating ultraviolet rays from the base material side to reduce the adhesive force of the temporary fixing film for peeling.

[0227] In the method of heating and foaming (or expanding) the temporary fixing film for peeling, the heating conditions are usually 100 to 250 °C for 1 to 90 seconds or 5 to 15 minutes. Also, in the method of irradiating ultraviolet rays from the base material side to reduce the adhesive force of the temporary fixing film for peeling, the irradiation amount of ultraviolet rays is usually 10 mJ / cm 2 ~1000 mJ / cm 2 is.

[0228] - Step (5)- A redistribution formation layer (insulating layer of the redistribution substrate) is formed using the resin composition and resin sheet of the present invention.

[0229] After forming the redistribution formation layer, in order to layer-connect the semiconductor chip and the conductor layer described later, via holes may be formed in the redistribution formation layer. The via holes may be formed by a known method according to the material of the redistribution formation layer.

[0230] - Step (6)- The formation of the conductor layer on the redistribution formation layer may be carried out in the same manner as step (V) described in relation to the manufacturing method of the printed wiring board. Note that steps (5) and (6) may be repeated to alternately stack (build up) the conductor layer (redistribution layer) and the redistribution formation layer (insulating layer).

[0231] In manufacturing a semiconductor package, the following steps may be further implemented: (7) forming a solder resist layer on a conductor layer (redistribution layer); (8) forming bumps; and (9) dicing and singulating a plurality of semiconductor packages into individual semiconductor packages. These steps may be implemented according to various methods known to those skilled in the art and used in the manufacture of semiconductor packages.

[0232] By forming a redistribution layer (insulating layer) using the resin composition and resin sheet of the present invention, which are excellent in surface flatness and plating adhesion and can provide an insulating layer with a low relative dielectric constant to reduce transmission loss, a semiconductor package with extremely low transmission loss can be realized regardless of whether it is a Fan-In type package or a Fan-Out type package. In one embodiment, the semiconductor package of the present invention is a Fan-Out type package. The resin composition and resin sheet of the present invention can be applied regardless of whether they are a Fan-Out panel level package (FOPLP) or a Fan-Out wafer level package (FOWLP). In one embodiment, the semiconductor package of the present invention is a Fan-Out panel level package (FOPLP) or a Fan-Out wafer level package (FOWLP).

[0233] [Semiconductor Device] The semiconductor device of the present invention includes the circuit board of the present invention (for example, a printed wiring board). The circuit board includes a cured product of the resin composition of the present invention. The semiconductor device of the present invention can be manufactured using the circuit board of the present invention.

[0234] Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and airplanes).

[0235] The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) on the conductive portions of a printed wiring board. The "conductive portion" means "a portion for transmitting an electrical signal in a printed wiring board", and the location thereof may be either on the surface or an embedded portion. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

[0236] The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, wire bonding mounting method, flip chip mounting method, mounting method using a bump-less build-up layer (BBUL), mounting method using an anisotropic conductive film (ACF), mounting method using a non-conductive film (NCF), etc. can be mentioned. Here, the "mounting method using a bump-less build-up layer (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and the wiring on the printed wiring board are connected".

Example

[0237] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "mass%", respectively, unless otherwise specified. The temperature conditions, pressure conditions, and humidity conditions in the case of no particular designation are room temperature (25 ° C) and atmospheric pressure (1 atm).

[0238] [Production of resin sheet] First, the resin sheets of the examples and comparative examples will be described. The resin sheet is an example of the sheet-like laminated material of the present invention.

[0239] <Example 1> To 10 parts of a biphenyl type epoxy resin (“NC-3000L” manufactured by Nippon Kayaku Co., Ltd.), add 15 parts of a naphthalene type epoxy resin (“HP4032SS” manufactured by DIC Corporation), 35 parts of a naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel Chemical & Material Co., Ltd.), 10 parts of a bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical & Material Co., Ltd.), 0.3 part of a solution of polyether-modified polymethylalkylsiloxane (“BYK-300” manufactured by BYK-Chemie GmbH, a xylene / ethylbenzene / isobutyl alcohol solution with a solid content of 52% by mass), 60 parts of an active ester type curing agent (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution with a solid content of 65% by mass), 2 parts of a carbodiimide type curing agent (“Carbodilite V-03” manufactured by Nisshinbo Chemical Inc., a toluene solution with a solid content of 50% by mass), 8 parts of a phenolic curing agent containing a triazine skeleton (“LA-3018-50P” manufactured by DIC Corporation, with a hydroxyl equivalent of approximately 151 and a solid content of 50% in a 1-methoxy-2-propanol solution), 10 parts of a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, a solution of Anone (cyclohexanone) / MEK (methyl ethyl ketone) (1:1) with a solid content of 30% by mass), 0.5 part of 4-dimethylaminopyridine (“DMAP” manufactured by Tokyo Chemical Industry Co., Ltd.), 30 parts of an aliphatic ketone type low-boiling solvent (“methyl ethyl ketone (MEK)” manufactured by Junsei Chemical Co., Ltd., boiling point 79°C), and 165 parts of an aromatic type high-boiling solvent (“Ipzol 150” manufactured by Idemitsu Kosan Co., Ltd., initial boiling point 184°C, dry point 205°C). Mix them and stir at room temperature until a uniform solution is obtained. To the mixed solution, add 310 parts of a solid inorganic filler surface-treated with an aminosilane type coupling agent “KBM573” (average particle size 0.5 μm, “SO-C2” manufactured by Admatechs Co., Ltd.) and disperse it uniformly with a high-speed rotating mixer to obtain a varnish-like resin composition (resin varnish). A PET film with an alkyd resin type release layer (“AL5” manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. The resin varnish was uniformly applied onto the release layer of the support so that the thickness of the dried resin composition layer would be 40 μm, and it was dried at 80 to 120°C (average 100°C) for 5 minutes to produce a resin sheet.

[0240] <Example 2> A resin varnish was prepared in the same manner as in Example 1, except that 165 parts of the aromatic high-boiling solvent "Ipzol 150" in Example 1 was changed to 30 parts.

[0241] <Example 3> A resin varnish was prepared in the same manner as in Example 1, except that 165 parts of the aromatic high-boiling solvent "Ipzol 150" in Example 1 was changed to 5 parts.

[0242] <Example 4> A resin varnish was prepared in the same manner as in Example 1, except that 0.3 part of the solution of polyether-modified polymethylalkylsiloxane "BYK-300" in Example 1 was changed to 0.9 part.

[0243] <Example 5> A resin varnish was prepared in the same manner as in Example 1, except that 10 parts of the biphenyl-type epoxy resin "NC-3000L" in Example 1 was changed to 0 part, 15 parts of the naphthalene-type epoxy resin "HP4032SS" was changed to 25 parts, 35 parts of the naphthalene-type epoxy resin "ESN475V" was changed to 45 parts, and 10 parts of the bisphenol-type epoxy resin "ZX1059" was changed to 0 part.

[0244] <Example 6> A resin varnish was prepared in the same manner as in Example 1, except that 0.3 part of the solution of polyether-modified polymethylalkylsiloxane "BYK-300" in Example 1 was changed to 0.3 part of a solution of polyether-modified polymethylalkylsiloxane (manufactured by BYK Chemie "BYK-320", a solution of mineral spirit / 1-methoxy-2-propyl acetate / 1,2,4-trimethylbenzene with a solid content of 52% by mass).

[0245] <Example 7> A resin varnish was prepared in the same manner as in Example 1, except that 0.3 part of the solution of polyether-modified polymethylalkylsiloxane "BYK-300" in Example 1 was changed to 0.6 part of a solution of polyester-modified polydimethylsiloxane (manufactured by BYK Chemie "BYK-310", a solution of xylene / ethylbenzene / toluene with a solid content of 25% by mass).

[0246] <Example 8>

[0247] <Comparative Example 1>

[0248] <Comparative Example 2>

[0249] <Comparative Example 3>

[0250] <Comparative Example 4> Except that 0.3 part of the solution of polyether-modified polymethylalkylsiloxane “BYK-300” in Example 1 was changed to 0.2 part of polyether-modified siloxane (“BYK-ET3061” manufactured by BYK Chemie, solid content 94% by mass), a resin varnish was prepared in the same manner as in Example 1, and a resin sheet was produced. The polyether-modified siloxane is an example of the (C’) modified polysiloxane compound. The (C’) modified polysiloxane compound is a compound having a polysiloxane structure, a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polysiloxane structure.

[0251] Subsequently, various measurements were performed using the varnish-like resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4 (hereinafter simply referred to as the varnish-like resin compositions). Hereinafter, the methods and results of various measurements will be described.

[0252] [1. Measurement of Viscosity] The viscosity of the varnish-like resin composition was measured using an E-type viscometer (“RE80 type viscometer” manufactured by Toki Sangyo Co., Ltd.) under the conditions of a measurement temperature of 25 ° C, a rotor of 1.34 ° × R24, an amount of the varnish-like resin composition of 1.2 ml, and a rotation speed of 100 rpm for 2 minutes.

[0253] [2. Evaluation of Peeling Defects after Coating] The varnish-like resin composition was put into a slit coater (manufactured by Condo Co.), and one slit coat was applied onto a glass plate so that the film thickness became 25 μm. The glass plate on which the coating film was formed by slit coating was vacuum dried for 1 minute, then dried on a hot plate at 100 ° C for 3 minutes, and further heated at 180 ° C for 40 minutes using an oven to produce a substrate for evaluation (evaluation sample A). When measuring the thickness of the entire evaluation sample A, those with a thickness difference of less than 5 μm were evaluated as “○”, and those with a thickness difference of 5 μm or more were evaluated as “×”. Here, the thickness difference includes variations in the coating start point, intermediate point, and end point (X direction), and variations in the left, right, and center of the coater (Y direction), and both are measured and judged.

[0254] [3. Evaluation of Thin Film Formability] When the average film thickness of Evaluation Sample A was 25 μm ± 2 μm, it was evaluated as "〇", and when it was not, it was evaluated as "×".

[0255] [4. Weight loss after 30 minutes at room temperature] 50 mg of the varnish-like resin composition was measured for weight loss at 25°C for 30 minutes using a differential thermal - thermogravimetric simultaneous measurement device (TG - DTA device) ("STA200" manufactured by Hitachi High - Tech Corporation). When the weight loss after 30 minutes was less than 10%, it was evaluated as "〇", and when it was 10% or more, it was evaluated as "×".

[0256] [5. Calculation of the average linear thermal expansion coefficient (CTE)] The varnish - like resin composition was put into a slit coater (manufactured by Condor), and one slit coat was applied onto a polyimide film ("Upilex" manufactured by UBE Industries, Ltd.) so that the film thickness became 25 μm. The polyimide film with the coating film formed by slit coating was dried in vacuum for 1 minute, and then dried on a hot plate at 100°C for 3 minutes. After heating at 200°C for 90 minutes to thermally cure the coating film, the polyimide film was peeled off to obtain a cured product for evaluation (Evaluation Sample B). Evaluation Sample B was cut into pieces with a width of about 5 mm and a length of about 15 mm to obtain test pieces (Evaluation Sample C). For Evaluation Sample C, thermomechanical analysis was performed by the tensile loading method using a thermomechanical analyzer ("Thermo Plus TMA8310" manufactured by Rigaku Corporation). Specifically, after attaching Evaluation Sample C to the thermomechanical analyzer, the thermal expansion rate was measured continuously twice under the measurement conditions of a load of 1 g and a heating rate of 5°C / min. Then, based on the measurement result of the second time, the average linear thermal expansion coefficient (ppm / K) from 25°C (298 K) to 150°C (423 K) was calculated. When the average linear thermal expansion coefficient was less than 20 ppm / K, it was evaluated as "〇", and when it was 20 ppm / K or more, it was evaluated as "×".

[0257] [6. Uniformity of the cross - section after vacuum drying] Using a convergent ion beam apparatus (FIB apparatus) (Hitachi High-Tech Corporation's FIB-SEM composite apparatus "Ethos NX5000"), cross-sectional observation of the resin portion of the evaluation substrate A was carried out. An area where only resin exists and no inorganic filler exists in the cross-section (in other words, the resin area) was observed. When a resin area with a size of 1 μm or more in diameter exists, it was evaluated that the resin was separated in the resin composition layer and "×" was described. When the resin area does not exist, it was evaluated that the resin was not separated in the resin composition layer and the inorganic filler was uniformly dispersed, and "〇" was described.

[0258]

Table 1

Claims

1. (A) An epoxy resin, (B) an organic solvent, (C) a modified polydialkylsiloxane compound, (D) an inorganic filler, and (E) a resin composition containing a curing agent, The component (C) is a compound having a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure, The average linear thermal expansion coefficient (CTE) of the cured product of the resin composition is less than 20 ppm / K in the range from 25°C to 150°C, Resin composition.

2. The two alkyl groups of the polydialkylsiloxane structure are each independently an alkyl group having 1 to 5 carbon atoms, The resin composition according to Claim 1.

3. At least one of the two alkyl groups is a methyl group, The resin composition according to Claim 2.

4. When the total amount of the resin composition is 100% by mass, the content of the component (B) is 10% by mass or more and 35% by mass or less, When the non-volatile components in the resin composition are 100% by mass, the content of the component (C) is 0.03% by mass or more and 0.15% by mass or less, The resin composition according to Claim 1.

5. The ratio of the content of the component (C) to the content of the component (B) is 0.1% or more and 1% or less, The resin composition according to Claim 4.

6. When the non-volatile components in the resin composition are 100% by mass, the content of the component (D) is 60% by mass or more and 80% by mass or less, The resin composition according to Claim 1.

7. The component (E) contains both an active ester-based curing agent and a phenol-based curing agent, The resin composition according to Claim 1.

8. The viscosity measured using an E-type viscometer under the conditions of 25°C and 100 rpm is 3 mPa·s or more and 1,000 mPa·s or less, The resin composition according to any one of Claims 1 to 7.

9. Containing the resin composition according to any one of Claims 1 to 7, Sheet-like laminated material.

10. Having a support and a resin composition layer formed from the resin composition according to any one of Claims 1 to 7 provided on the support, Resin sheet.

11. Containing the cured product of the resin composition according to any one of Claims 1 to 7, Circuit board.

12. The cured product of the resin composition is formed from the resin composition by a method selected from the group consisting of a roll coating method, a spray coating method, a spin coating method, a bar coating method, a slit coating method, a curtain coating method, and a dipping method. The circuit board according to claim 11.

13. Including the circuit board according to claim 12, A semiconductor device.

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