TWI572663B - Resin composition - Google Patents

Description

Resin composition

The present invention relates to specific resin compositions. Further, the resin composition, the adhesive film, the prepreg, the multilayer printed wiring board, and the semiconductor device are contained.

In recent years, in the development of miniaturization and high performance of electronic equipment, multi-layer printed wiring boards have been demanding stratification of a build-up layer, miniaturization of wiring, and high density.

A variety of combinations have been made for this. For example, Patent Document 1 discloses a resin composition containing an organic-inorganic hybrid. It has been described that such compositions increase the glass transition point. Further, general blending is also studied in Patent Documents 2 to 4. However, this performance is not absolutely satisfactory.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-95901

[Patent Document 2] Japanese Patent No. 4674730

[Patent Document 3] Japanese Patent No. 4686750

[Patent Document 4] Japanese Patent No. 4782870

The problem to be solved by the present invention is to provide a low arithmetic mean roughness (Ra value) of the surface of the insulating layer after not only the wet roughening step, and even a low root mean square roughness (Rq value), the plated conductor The layer also exhibits a novel resin composition of relatively high peel strength.

The inventors of the present invention have found that the result of the hard work can be solved by a resin composition containing (A) an epoxy resin, (B) a hardener, and (C) an inorganic filler which has been surface-treated with an epoxy resin. The present invention has been accomplished in view of the above problems.

That is, the present invention contains the following.

[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler which is surface-treated with an epoxy resin.

[2] The resin composition according to the above [1], wherein (C) the surface-treated inorganic filler is 100% by mass of the inorganic filler with 0.05 to 3% by mass of the epoxy resin. By.

[3] A resin composition according to the above [1] or [2], wherein (C) The average temperature of the surface of the inorganic filler which is surface-treated with the epoxy resin is 20 to 100 ° C.

[4] The resin composition according to the above [1] or [2], wherein (C) the inorganic filler having a surface treated with an epoxy resin has a maximum temperature of 50 ° when surface-treated with the epoxy resin. 150 ° C.

[5] The resin composition according to any one of the above [1] to [4] wherein (C) the epoxy resin which is subjected to an inorganic filler which is surface-treated with an epoxy resin is a liquid epoxy resin.

[6] The resin composition according to the above [5], wherein the liquid epoxy resin has a viscosity at 25 ° C of 0.01 to 50 Pa. s.

[7] The resin composition according to any one of the above [1] to [6] wherein (C) the epoxy resin which is subjected to the surface treatment of the epoxy resin is selected from the group consisting of naphthalene type epoxy resins, One or more of the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a glycerin type epoxy resin, and a p-amine phenol type epoxy resin.

[8] The resin composition according to any one of the above [1] to [7] wherein (C) the inorganic filler surface-treated with the epoxy resin is further selected from the group consisting of a decane coupling agent, an alkoxy decane, One or more surface treatments of the group consisting of an alkoxy oligomer, an aluminum coupling agent, a titanium coupling agent, and a zirconium coupling agent.

[9] The resin composition according to any one of the above [1] to [8] further comprising (D) a curing accelerator.

[10] The resin composition according to any one of the above [1] to [9] further comprising (E) a thermoplastic resin.

[11] The resin composition according to any one of the above [1] to [10] further comprising (F) rubber particles.

[12] The resin composition according to any one of the above [1] to [11] further comprising (G) a flame retardant.

[13] The resin composition according to any one of the above [1] to [12] wherein the insulating layer is formed by curing the resin composition, and the arithmetic mean roughness after roughening the surface of the insulating layer is from 10 nm to 330 nm. The root mean square roughness is 10 to 480 nm, and the peeling strength of the conductor layer and the insulating layer obtained by plating the surface of the roughened insulating layer is 0.4 kgf/cm to 1.0 kgf/cm.

[14] An adhesive film obtained by forming a resin composition according to any one of the above [1] to [13] as a resin composition layer on a support.

[15] The adhesive film according to [14] above, wherein the resin composition layer has a minimum melt viscosity of 500 to 14,000 poise.

[16] A prepreg obtained by impregnating the resin composition according to any one of the above [1] to [13] into a sheet-like reinforcing substrate.

[17] A multilayer printed wiring board formed by forming an insulating layer of a cured product of the resin composition according to any one of the above [1] to [13].

[18] A semiconductor device characterized by using the multilayer printed wiring board of the above [17].

By using it characterized by containing (A) epoxy resin, (B) a hardener and (C) a resin composition of an inorganic filler which is surface-treated with an epoxy resin, which provides a low arithmetic mean roughness (Ra value) of the surface of the insulating layer not only after the wet roughening step And even if it is a low root mean square roughness (Rq value), the plated conductor layer exhibits a relatively high peel strength novel resin composition.

The present invention is characterized by comprising a resin composition of (A) an epoxy resin, (B) a hardener, and (C) an inorganic filler which is surface-treated with an epoxy resin.

<(A) Epoxy Resin>

The epoxy resin used in the present invention is not particularly limited, and examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and a bisphenol AF type epoxy resin. Phenolic novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthyl ether type epoxy resin, glycidylamine type ring Oxygen resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy Resin, epoxy resin containing a spiro ring, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, and the like. These may be used alone or in combination of two or more.

Among these, bisphenol A type ring is obtained from the viewpoint of improvement in heat resistance, improvement in insulation reliability, and adhesion to metal foil. An oxygen resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, a stretch naphthyl ether type epoxy resin, and an epoxy resin having a butadiene structure are preferred. Specific examples include bisphenol A type epoxy resin ("Epikote 828 EL" manufactured by Mitsubishi Chemical Corporation, "YL 980"), and bisphenol F type epoxy resin ("JER806H" manufactured by Mitsubishi Chemical Corporation). "YL983U"), naphthalene type 2-functional epoxy resin ("HP4032", "HP4032D", "HP4032SS" made by DIC), and naphthalene type 4-functional epoxy resin (HP4700" and "HP4710" "), naphthol type epoxy resin ("ESN-475V" manufactured by Tohto Kasei Co., Ltd.), epoxy resin having a butadiene structure ("PB-3600" and "Epolead PB" manufactured by Daicel Chemical Industry Co., Ltd.) ), an epoxy resin having a biphenyl structure ("NC 3000H", "NC 3000L", "NC 3100" manufactured by Nippon Kayaku Co., Ltd., "YX 4000" and "YX 4000H" manufactured by Mitsubishi Chemical Corporation. "YX 4000HK", "YL6121"), cyclohexanedimethanol type epoxy resin ("ZX1658" manufactured by Nippon Steel Chemical Co., Ltd.), and biphenyl dimethanol type epoxy resin (Nippon Steel Chemical Co., Ltd.) "TX-0934"), benzodiazepine epoxy resin ("TX-0929" manufactured by Nippon Steel Chemical Co., Ltd.), and propylene glycol epoxy resin ("PG-207" manufactured by Nippon Steel Chemical Co., Ltd.) ), alicyclic epoxy resin (Daicel) Chemical Industry Co., Ltd. "CELLOXIDE 2021P", "CELLOXIDE 2081", "CELLOXIDE 3000", "CELLOXIDE 2000", "EHPE3150", "Epolead GT400", "CELLVENUS"), methyl group with alicyclic epoxy group Acrylate ("CYCLOMER M100" manufactured by Daicel Chemical Industry Co., Ltd.), with methyl epoxypropyl group Acrylate ("M-GMA" manufactured by Daicel Chemical Industry Co., Ltd.), bismuth epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), and glycerin epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd.) ZX1542"), a naphthyl ether type epoxy resin ("EXA-7310", "EXA-7311", "EXA-7311L", "EXA7311-G3" made by DIC).

The epoxy resin may be used in combination of two or more kinds, and it is preferable to contain an epoxy resin having two or more epoxy groups in one molecule. Further, it is used in combination with an epoxy resin having two or more epoxy groups in one molecule, a liquid epoxy resin at a temperature of 20 ° C, and three or more epoxy groups in one molecule, and a temperature of 20 The aspect of the aromatic epoxy resin which is solid at ° C is more preferable. Further, the term "aromatic epoxy resin" as used in the present invention means an epoxy resin having an aromatic ring structure in its molecule. When a liquid epoxy resin or a solid epoxy resin is used as the epoxy resin, the resin composition has moderate flexibility when used as a film, or the cured product of the resin composition has moderate fracture strength. In view of the blending ratio (liquid epoxy resin: solid epoxy resin), the mass ratio is preferably in the range of 1:0.1 to 1:2, and preferably in the range of 1:0.3 to 1:1.8. The range of 1:0.6~1:1.5 is particularly good.

In the resin composition of the present invention, from the viewpoint of improving the mechanical strength or water resistance of the cured product of the resin composition, when the nonvolatile component in the resin composition is 100% by mass, the content of the epoxy resin is 3 to 40. The mass % is preferably, preferably 5 to 35 mass%, and particularly preferably 10 to 30 mass%.

<(B) hardener>

The curing agent to be used in the present invention is not particularly limited, and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate-based curing agent. A phenolic curing agent, a naphthol-based curing agent, an active ester-based curing agent or a cyanate-based curing agent is preferred as the agent or the acid anhydride-based curing agent. These may be used alone or in combination of two or more.

The phenolic curing agent and the naphthol-based curing agent are not particularly limited, and examples thereof include a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure, and a phenol-based novolak resin containing three. The phenolic novolak resin, the naphthol novolak resin, the naphthol aralkyl resin, and the triazine skeleton of the azine skeleton are preferably a naphthol resin or a biphenyl aralkyl phenol resin. As a commercially available product, examples of the biphenyl aralkyl type phenol resin include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH7851-4H" (made by Megumi Kasei Co., Ltd.). "GPH" (manufactured by Nippon Kayaku Co., Ltd.), as a naphthol novolak resin, "NHN" or "CBN" (manufactured by Nippon Kayaku Co., Ltd.), and examples of the naphthol aralkyl type resin include "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN395", "SN375" (made by Toki Kasei Co., Ltd.), as a phenolic novolak resin, " TD2090" (made by DIC), phenolic novolac resin "LA3018", "LA7052", "LA7054", "LA1356" (made by DIC), etc. containing a triazine skeleton. These may be used alone or in combination of two or more.

The active ester-based curing agent is not particularly limited, and generally has two or more reactions in one molecule using phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds. A compound having a high activity of an ester group is preferred. The active ester-based curing agent 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. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester system obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is preferred. The hardener is better. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and A. Bisphenol 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 Diphenol, phenolic novolac, etc. The active ester-based curing agent may be used alone or in combination of two or more. As the active ester-based curing agent, an active ester-based curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available one may be used. As a commercially available active ester-based curing agent, a dicyclopentadiene diol structure, a phenolic novolac acetonide, a phenolic novolac benzyl hydrazide, or the like is preferable, and a dicyclopentan group is contained. The diene diphenol constructor is better. Specifically, as a structure containing a dicyclopentadiene diphenol, it can be enumerated EXB 9451, EXB 9460, EXB 9460S-65T, HPC-8000-65T (manufactured by DIC Co., Ltd., active base equivalent: 223), and as the acetal compound of the phenolic novolac, DC808 (manufactured by Mitsubishi Chemical Corporation) The reactive base equivalent is about 149), and the benzyl hydrazide of the phenolic novolak can be exemplified by YLH1026 (manufactured by Mitsubishi Chemical Corporation, active base equivalent: about 200), YLH1030 (manufactured by Mitsubishi Chemical Corporation, and active base equivalent of about 201). YLH1048 (manufactured by Mitsubishi Chemical Corporation, active base equivalent: about 245), and the like, wherein HPC-8000-65T is preferred from the viewpoints of storage stability of the varnish and thermal expansion rate of the cured product.

The active ester-based curing agent containing a dicyclopentadiene diphenol structure is more specifically a compound of the following formula (1).

(wherein R represents phenyl, naphthyl, k represents 0 or 1, and n is an average of 0.05 to 2.5 in repeating units)

From the viewpoint of lowering the dielectric tangent and improving the heat resistance, R is preferably a naphthyl group. On the other hand, k is preferably 0, and n is preferably 0.25 to 1.5.

The benzoxazine-based curing agent is not particularly limited, and specific examples thereof include F-a, P-d (manufactured by Shikoku Chemical Co., Ltd.), and HFB2006M (manufactured by Showa Polymer Co., Ltd.).

The cyanate-based curing agent is not particularly limited and can be listed. A novolac type (phenolic novolak type, an alkylphenol type novolak type, etc.) cyanate type curing agent, a dicyclopentadiene type cyanate type curing agent, a bisphenol type (bisphenol A type, bisphenol) F-type, bisphenol S type, etc.) cyanate-based curing agent, and a part of the triazine-based prepolymer. The weight average molecular weight of the cyanate-based curing agent is not particularly limited, and is preferably 500 to 4,500, more preferably 600 to 3,000. Specific examples of the cyanate-based curing agent include bisphenol A dicyanate and polyphenol cyanate (oligo(3-methylene-1,5-phenylene), 4). 4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2, 2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) ether a bifunctional cyanate resin, a phenol novolak, a cresol novolak, a polyfunctional cyanate resin derived from a phenol resin containing a dicyclopentadiene structure, or the like, and a part of the cyanate resin A triazine-based prepolymer, etc. These may be used singly or in combination of two or more. The commercially available cyanate resin may be a phenolic novolak type polyfunctional cyanate represented by the following formula (2). Resin (manufactured by Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), or a part or all of the bisphenol A dicyanate represented by the following formula (3) becomes a pre-triazine-formed trimer. Gather (manufactured by Lonza Japan Co., Ltd., BA230, cyanate equivalent 232), cyanate resin containing a dicyclopentadiene structure represented by the following formula (4) (manufactured by Lonza Japan Co., Ltd., DT-4000, DT- 7000) and so on.

[wherein, n represents an arbitrary number (preferably 0 to 20) as an average value]

(where n represents 0 to 5 as the average value)

The acid anhydride-based curing agent is not particularly limited, and examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. , Methyl Nadic acid anhydride, hydrogenated methyl nadic acid anhydride, three Alkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-di-oxytetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2 -dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, diphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxyl- 3-furyl)-naphthyl [1,2-C]furan-1,3-dione, ethylene glycol bis(benzene trimellitic anhydride), styrene and maleic acid copolymerized styrene. A polymer type acid anhydride such as maleic acid resin.

In the resin composition of the present invention, from the viewpoint of improving the mechanical strength or water resistance of the cured product of the resin composition, (A) the total number of epoxy groups of epoxy resins and (B) the total number of reactive groups of hardeners The ratio is preferably 1:0.2~1:2, preferably 1:0.3~1:1.5, and 1:0.4~1:1. Further, the total number of epoxy groups of the epoxy resin present in the resin composition is a value obtained by dividing the solid content content of each epoxy resin by the value of the epoxy equivalent, and the total epoxy resin is added. The total number of reactive groups of the agent is the total value of the total hardeners divided by the mass of the solid content of each hardener divided by the value of the reactive base equivalent.

In the resin composition of the present invention, when the non-volatile component in the resin composition is 100% by mass, the hardener content is 3 to 30, from the viewpoint of improving the mechanical strength or water resistance of the cured product of the resin composition. The mass % is preferably, preferably 5 to 25% by mass, and particularly preferably 7 to 20% by mass.

<(C) Inorganic filler material treated with epoxy resin surface>

The inorganic filler used in the present invention is not particularly limited, and examples thereof include cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, and magnesium carbonate. Magnesium oxide, boron nitride, aluminum borate, barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among them, cerium oxide is preferred. Further, it is preferable to use cerium oxide such as amorphous cerium oxide, pulverized cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide or hollow cerium oxide to melt cerium oxide. Further, it is preferable that the cerium oxide is spherical. These may be used alone or in combination of two or more. As a commercially available spherical molten cerium oxide, "SOC2" and "SOC1" manufactured by Admatechs can be cited.

The average particle diameter of the inorganic filler is not particularly limited, and is preferably 5 μm or less from the viewpoint of fine wiring formation on the insulating layer, preferably 3 μm or less, more preferably 1 μm or less, and 0.7 μm or less. More preferably, it is more preferably 0.5 μm or less, more preferably 0.4 μm or less, and particularly preferably 0.3 μm or less. On the other hand, when the epoxy resin composition is used as the resin varnish, the average particle diameter of the inorganic filler is preferably 0.01 μm or more, and 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from increasing and the workability being lowered. Preferably, it is preferably 0.05 μm or more, more preferably 0.07 μm or more, and particularly preferably 0.1 μm or more. The average particle size of the above inorganic filler is based on the Mie scattering theory and can be diffracted by laser. Determined by scattering method. Specifically, the laser diffraction type particle size distribution measuring apparatus has a particle size distribution of the inorganic filler which is prepared on a volume basis, and the median diameter can be measured as an average particle diameter. Determination of the sample, can be used to fill the inorganic The material is preferably dispersed by ultrasonic waves in the water. As the laser diffraction type particle size distribution measuring apparatus, LA-500, 750, 950, etc., manufactured by Horiba, Ltd., can be used.

The epoxy resin used for the surface treatment of the inorganic filler is not particularly limited, and a liquid epoxy resin is preferred from the viewpoint of uniform surface treatment. As a liquid epoxy resin, the viscosity at 25 ° C is 0.01 ~ 50Pa. s is better, with 0.05~35Pa. s is better. For the measurement of the viscosity, an E-type viscometer (RE-80 manufactured by Toki Sangyo Co., Ltd.) was used, and the liquid epoxy resin was metered to about 0.2 ml using a syringe in a device adjusted to 25 ° C. 5 to 20 rpm rotation number measurement. Further, from the viewpoint of obtaining an inorganic filler and a high reaction rate, a polyfunctional epoxy resin is preferred, and a polyfunctional epoxy resin having an epoxy equivalent of 50 to 300 is more preferable. The term "polyfunctional epoxy resin" as used herein refers to an epoxy resin having two or more epoxy groups in one molecule. Further, the epoxy equivalent (g/eq) means a value obtained by dividing the average molecular weight by the number of epoxy groups per molecule. Specific examples of the epoxy resin include a naphthalene epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a glycerin epoxy resin, and a p-amine phenol epoxy resin. Phenyl type epoxy resin, epoxy propyl methacrylate resin, epoxy propyl acrylate resin, cyclohexane dimethanol type epoxy resin, biphenyl dimethanol type epoxy resin, benzene dimethanol type ring An oxy resin, a propylene glycol type epoxy resin, an alicyclic epoxy resin, a methacrylate having an alicyclic epoxy group, a methacrylate having a methyl epoxy propyl group, or the like. Among them, a group consisting of a naphthalene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a glycerin type epoxy resin, and a p-amine phenol type epoxy resin It is better to choose more than one.

As a method of surface-treating an inorganic filler by an epoxy resin, the method of stirring an inorganic filler for 5 to 30 minutes by spraying an epoxy resin, and carrying out an inorganic filler is mentioned. At this time, in order to facilitate the spraying of the epoxy resin, the viscosity dissolved in the organic solvent can be adjusted. Further, from the viewpoint of efficiently performing surface treatment, the average temperature at the time of surface treatment of the epoxy resin is preferably 20 ° C or higher, more preferably 25 ° C or higher, and even more preferably 30 ° C or higher. More preferably above 35 ° C, especially above 40 ° C, especially above 45 ° C. On the other hand, from the viewpoint of preventing deterioration of the epoxy resin, the average temperature at the time of surface treatment of the epoxy resin is preferably 100 ° C or less, more preferably 95 ° C or less, and even more preferably 90 ° C or less. . Further, from the viewpoint of sufficiently performing surface treatment, the highest temperature at the time of surface treatment is preferably 50 ° C or more, more preferably 55 ° C or more, more preferably 60 ° C or more, and even more preferably 65 ° or more. It is especially good at 70 ° C or above. On the other hand, from the viewpoint of preventing deterioration of the epoxy resin, the maximum temperature at which the epoxy resin is subjected to surface treatment is preferably 150 ° C or less, more preferably 140 ° C or less, and 130 ° C or less. Good, more preferably below 120 °C, especially below 110 °C, especially below 105 °C. Examples of the agitator include a rotary mixer, a tumbler mixer, a rocking mixer, a vibrating fluidized bed, a powder dryer, and the like, and it is preferable to use a rotary mixer in view of simplicity and feasibility. As the rotary mixer, a Henschel type mixer can be cited.

The content of the epoxy resin is relative to the inorganic filler from the viewpoint of improving the dispersibility of the resin varnish and improving the coverage of the inorganic filler. 100% by mass of the material is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, more preferably 0.15% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.25% by mass or more. 0.3% by mass or more is particularly preferable. In addition, from the viewpoint of effective surface treatment to suppress the increase in viscosity, the surface treatment is preferably 3% by mass or less, more preferably 2.8 mass% or less, more preferably 2.6 mass% or less, and still more preferably 2.4 mass% or less. More preferably, it is particularly preferably 2.2% by mass or less, and particularly preferably 2% by mass or less.

(C) When the content of the inorganic filler in the surface of the epoxy resin is blended, when the nonvolatile component in the resin composition is 100% by mass, from the viewpoint of lowering the thermal expansion ratio of the cured product, 20% by mass or more is more preferable, more preferably 30% by mass or more, still more preferably 40% by mass or more, and even more preferably 50% by mass or more. In addition, from the viewpoint of improving the mechanical properties of the cured product, it is preferably 85 mass% or less, more preferably 80 mass% or less, more preferably 75 mass% or less, and still more preferably 70 mass% or less.

The inorganic filler is preferably an inorganic filler which is surface-treated with a decazane compound from the viewpoint of improving the dispersibility of the resin varnish, reducing the arithmetic mean roughness, and reducing the root mean square roughness. After surface treatment with a decazane compound, it is advantageous to improve the dispersibility and improve the affinity with the conductor layer by surface treatment with an epoxy resin. Examples of the guanidinium compound include hexamethyldiazepine, 1,3-divinyl-1,1,3,3-tetramethyldiazepine, octamethyltrioxane, and six ( T-butyl)dioxane, hexabutyldiazepine, hexaoctyldioxane, 1,3-diethyltetramethyldiazepine, 1,3-di-n-octyl Tetramethyldiazane, 1,3- Diphenyltetramethyldiazepine, 1,3-dimethyltetraphenyldiazepine, 1,3-diethyltetramethyldiazepine, 1,1,3,3-tetra Phenyl-1,3-dimethyldiazepine, 1,3-dipropyltetramethyldiazepine, hexamethylcyclotriazane, hexaphenyldioxane, dimethyl Aminotrimethyl decazane, triazane, cyclotriazane, 1,1,3,3,5,5-hexamethylcyclotriazane, especially hexamethyldifluorene Azane is preferred. One type or two or more types can be used in combination. As the spherical molten cerium oxide which is surface-treated with hexamethyldioxane, "SC 2050-SQ" manufactured by Admatechs Co., Ltd. is mentioned.

The amount of the cerium alkane compound to be treated is preferably from 0.001 to 0.3% by mass, preferably from 0.005 to 0.2% by mass, more preferably from 0.01 to 0.1, based on 100% by mass of the inorganic filler. The mass % is better, and it is even better at 0.02 to 0.04% by mass.

(C) From the viewpoint of improving hydrophobicity and further improving dispersibility by reacting with an unreacted stanol group by an epoxy resin surface-treated inorganic filler, a decane coupling agent or alkoxy group is selected. One or more types of surface treatments consisting of decane, an alkoxy oligomer, an aluminum coupling agent, a titanium coupling agent, and a zirconium coupling agent are preferred. This surface treatment can be directly surface-treated with (C) an inorganic filler surface treated with an epoxy resin, or added to a resin varnish.

As the decane coupling agent, an epoxy decane coupling agent, an amino decane coupling agent, a mercapto decane coupling agent, or the like can be used. These may be used alone or in combination of two or more. Specific examples thereof include glycidoxypropyltrimethoxydecane, glycidoxypropyltriethoxydecane, glycidoxypropylmethyldiethoxydecane, and epoxypropyl group. Butyl trimethoxy sulfonium An epoxy decane coupling agent such as an alkane or a (3,4-epoxycyclohexyl)ethyltrimethoxydecane, an amine propyl methoxy decane, an amine propyl triethoxy decane, or an N-phenyl group Amino decane coupling agent such as 3-aminopropyltrimethoxydecane, N-2 (aminoethyl)aminopropyltrimethoxydecane, mercaptopropyltrimethoxydecane, mercaptopropyltriethoxydecane A quinone-based coupling agent.

As the alkoxydecane, methyltrimethoxydecane, octadecyltrimethoxydecane, phenyltrimethoxydecane, propylene propyleneoxypropyltrimethoxydecane, imidazolium, triazine decane, or the like can be used. These may be used alone or in combination of two or more.

The alkoxy oligomer refers to a low molecular weight resin having a combined organic group and an alkoxycarbenyl group, and examples thereof include a methyl group-containing alkoxy oligomer, a phenyl group-containing alkoxy oligomer, and a a methyl/phenyl alkoxy oligomer, an epoxy group-containing alkoxy oligomer, a mercapto group-containing alkoxy oligomer, an amine group-containing alkoxy oligomer, and an acrylic group-containing Alkoxy oligomer, methacryl group-containing alkoxy oligomer, ureido group-containing alkoxy oligomer, isocyanate group-containing alkoxy oligomer, vinyl group-containing alkoxy oligo Polymer, etc. These may be used alone or in combination of two or more. Specifically, the alkoxy oligomer can be represented by the structure of the following general formula (5).

In the formula (5), R1, R2, and R3 are each independently a carbon number of 1 The linear or branched alkyl group of ~10 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched chain having 1 to 4 carbon atoms, and more preferably A. Further, a group, an ethyl group and a propyl group are more preferably a methyl group or an ethyl group. In the formula (5), X may be a lower alkyl group, a glycidoxyalkyl group, an amine alkyl group, a mercaptoalkyl group, an acryloxyalkyl group, a methacryloxyalkyl group, a urethane group or an isocyanate. Alkyl, vinyl alkyl, glycidoxypropyl, amine propyl, N-2-(aminoethyl)-3-aminopropyl, N-phenyl-3-aminopropyl, methyl Acryloxypropyl, acryloxypropyl, decylpropyl, ureido, isocyanate propyl is preferred, glycidoxypropyl, amine propyl, N-2-(aminoethyl) --3-aminopropyl, N-phenyl-3-aminopropyl, decylpropyl, preferably with aminopropyl, N-2-(aminoethyl)-3-aminopropyl, N-benzene More preferably, the base-3-aminopropyl group. In the formula (5), n is an integer of 2 to 10, preferably an integer of 2 to 8, more preferably an integer of 2 to 6, more preferably an integer of 3 to 5.

Examples of the aluminum-based coupling agent include aluminum isopropyl ester, single second butoxy aluminum diisopropyl acid ester, aluminum second butyrate, aluminum alcohol ester, and ethyl acetoacetate aluminum diisopropyl acid. Ester, aluminum ginseng (ethyl acetamidine acetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetonate bis (ethyl acetamidine acetate), aluminum ginseng (B Anthraquinone acetate, oxidized cyclic aluminum isopropyl acid ester, oxidized cyclic aluminum isopropyl acid ester, oxidized cyclic aluminum stearic acid, oxidized cyclic aluminum octanoate, oxidized cyclic aluminum stearic acid, and the like. These may be used alone or in combination of two or more.

Examples of the titanium-based coupling agent include a butyl titanate dimer, a titanium octene glycolate, and a diisopropoxy titanium bis (triethanolamine). (triethanolaminato)), dihydroxy titanium dilactate, dihydroxy bis(ammonium lactate) titanium, bis(dioctyl pyrophosphate) extended ethyl titanate, bis(dioctyl pyrophosphate) oxygen Acetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetrakis(2-ethylhexyl) titanate, tetraisopropyl bis (di) Octyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetrakis(2,2-diallyloxymethyl-1-butyl) bis (double Tridecyl phosphite titanate, isopropyl trioctyl decyl titanate, isopropyl triisopropyl phenyl titanate, isopropyl triisostearyl titanate, isopropyl Isostearyl propylene acrylate titanate, isopropyl dimethyl propylene decyl isostearyl titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl hydrazine Alkylbenzenesulfonyl titanate, isopropyl ginseng (dioctyl pyrophosphate) titanate, isopropyl tris(N-decylamineethyl.aminoethyl) titanate, and the like. These may be used alone or in combination of two or more.

Examples of the zirconium coupling agent include zirconium IV (2,2-bis(2-propionic acid methyl) butyrate, neodecanoate), and zirconium IV (2,2-bis ( 2-methyl acrylate) butyrate, stilbene (dodecyl benzyl sulfonate), zirconium IV (2,2-bis(2-methyl acrylate) butyrate, ginseng (dioctyl) phosphate Ester), zirconium IV (2,2-bis(2-methyl acrylate) butyrate, ginseng 2-methyl 2-methyl acrylate), zirconium IV-bis(2,2-bis(2-methyl acrylate) Butyrate, bis-amino benzoate), zirconium IV (2,2-bis(2-methyl acrylate) butyrate, ginseng (diisooctyl) pyrophosphate), zirconium IV (2) , 2-bis(2-methyl acrylate) butyrate, ginseng 2-propionate (Propenoate), zirconium IV (2,2-bis(2-methyl acrylate) butyrate, ginseng (2-extended ethyldiamino)ethanol ester), zirconium IV, bis(2,2-bis(2-methyl acrylate) butyl Acid ester, bis(3-mercaptopropionate), zirconium IV (2,2-bis(2-methyl acrylate) butyrate, bis(2-amino)phenylate) Zirconium IV (2,2-bis(2-methyl acrylate) butyrate, ginseng (diisooctyl) pyrophosphate), N-substituted methacryl decyl decylamine adduct, zirconium IV (2- Ethyl, methyl 2-acrylate)-1,3-propane dioctylate, cyclobis 2,2-(di-2-methyl acrylate) butyrate, p-phosphate (zinc)肆-2,2-(bis-2-methyl acrylate) butyrate, ditridecylhydrogen phosphite 2 molar addition, etc. These may be used alone or in combination of two or more.

The resin composition of the present invention is cured to form an insulating layer, and the surface of the insulating layer is roughened, and the peeling strength of the conductor layer and the insulating layer obtained by plating is determined by the peel strength of the plated conductor layer (Peel Strength) described later. The measurement method described in the measurement > can be grasped.

The peeling strength is preferably 0.8 kgf/cm or less, more preferably 0.9 kgf/cm or less, still more preferably 1.0 kgf/cm or less, and still more preferably 1.5 kgf/cm or less. Further, the peel strength is preferably 0.4 kgf/cm or more, more preferably 0.5 kgf/cm or more.

The resin composition of the present invention is cured to form an insulating layer, and the arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) of the surface of the insulating layer after roughening treatment are determined by the following <roughening Measurement of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) > The measurement method described can be grasped.

The arithmetic mean roughness (Ra value) is preferably 330 nm or less, more preferably 300 nm or less, more preferably 250 nm or less, more preferably 220 nm or less, and 200 nm or less, in order to reduce the transmission loss of the electrical signal. More preferably, it is particularly good at 180 nm or less. On the other hand, the arithmetic mean roughness (Ra value) is preferably 10 nm or more, more preferably 20 nm or more, more preferably 30 nm or more, and even more preferably 40 nm or more, from the viewpoint of improving the peel strength, 50 nm. The above is yet better.

The root mean square roughness (Rq value) has been found to be a surface of the insulating layer which is finely smoothed by the Rq value in order to reflect the local state of the surface of the insulating layer. The Rq value is preferably 480 nm or less, more preferably 460 nm or less, more preferably 440 nm or less, more preferably 420 nm or less, more preferably 400 nm or less, and even more preferably 380 nm or less in order to form a smooth insulating layer surface. Good, with 360nm or less and then excellent, with 340nm or less as the best. On the other hand, the root mean square roughness (Rq value) is preferably 10 nm or more, more preferably 30 nm or more, more preferably 50 nm or more, and even more preferably 70 nm or more, from the viewpoint of improving the peel strength. More than 90nm and then even better.

The extension of the cured product of the resin composition of the present invention can be grasped by the measurement method described in <Measurement of Extension> to be described later. The operability of the cured product can be improved by increasing the elongation, and from the viewpoint of preventing cracks or cracks, it is preferably 2.4% or more, more preferably 2.6% or more, more preferably 2.8% or more, and more preferably 3.0% or more. Better again. On the other hand, from the viewpoint of lowering the thermal expansion rate of the cured product, it is preferably 5% or less, and 4% or less. Better.

The lowest melt viscosity of the resin composition layer of the adhesive film of the present invention can be grasped by the measurement method described in <Measurement of the lowest melt viscosity> described later. From the viewpoint of improving the lamination property of the film, improving the embedding property, and suppressing the bleeding, it is preferably 500 to 14000 poise, more preferably 1000 to 13,000 poise, more preferably 2000 to 12,000 poise, and more preferably 3000 to 11,000 poise. It is especially good at 4000~10000poise.

<(D) hardening accelerator>

Further, by the resin composition of the present invention, the epoxy resin and the curing agent can be efficiently cured by further containing a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include an amine-based curing accelerator, a lanthanum-based curing accelerator, an imidazole-based curing accelerator, a lanthanum-based curing accelerator, and a metal-based curing accelerator. These may be used alone or in combination of two or more.

The amine-based curing accelerator is not particularly limited, and examples thereof include a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4. 6,6--(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene (hereinafter abbreviated as DBU), and the like. These may be used alone or in combination of two or more.

The oxime-based hardening accelerator is not particularly limited, and examples thereof include dicyandiamide, 1-methylanthracene, 1-ethylanthracene, 1-cyclohexylfluorene, 1-phenylanthracene, and 1-(o-methylphenyl). ) hydrazine, dimethyl hydrazine, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0] tens-5-ene, 7 -methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 1-methyl Biguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allyl biguanide, 1-phenylbiguanide, 1-(o-methylphenyl)biguanide, and the like. These may be used alone or in combination of two or more.

The imidazole-based hardening accelerator is not particularly limited, and examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4. -methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 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-undecyl imidazolium (Imidazolium) trimellitate, 1-cyanoethyl-2-phenyl Imidazolium 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 isocyano cyanide Acid addition product, 2-phenylimidazole iso-cyanuric acid addition product, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 hydroxymethylimidazole, 2,3-dihydro-1H- Imidazole compound of pyrrole [1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. And an adduct of an imidazole compound and an epoxy resin. These may be used alone or in combination of two or more.

The oxime-based hardening accelerator is not particularly limited, and examples thereof include triphenylphosphine, bismuth borate compound, and tetraphenylphosphonium tetraphenylborate. Ester, n-butyl phosphotetraphenyl borate, tetrabutyl decanoate, (4-methylphenyl) triphenylsulfonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl Triphenylsulfonium thiocyanate and the like. These may be used alone or in combination of two or more.

In the resin composition of the present invention, the content of the hardening accelerator (excluding the metal-based hardening accelerator) is preferably in the range of 0.005 to 1% by mass, and 0.01% by mass in the non-volatile content in the resin composition. A range of ~0.5% by mass is more preferable. When it is less than 0.005 mass%, the hardening-to-late heat-hardening time tends to become long, and when it exceeds 1 mass%, the storage stability of the resin composition tends to be lowered.

The metal-based curing accelerator is not particularly limited, and examples thereof include organometallic complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include cobalt (II) acetoacetate, an organic cobalt complex such as cobalt (III) acetoacetate, and copper (II) acetoacetate. Organic copper complex, organic zinc complex such as zinc (II) acetamidine pyruvate, organic iron complex such as iron (III) acetoacetate, nickel (II) acetoacetate, etc. An organic manganese complex such as an organic nickel complex or manganese (II) acetoacetate or the like. Specific examples of the organic metal salt include zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.

In the resin composition of the present invention, when the amount of the metal-based hardening accelerator added is 100% by mass in the resin composition, the content of the metal-based curing catalyst metal is preferably in the range of 25 to 500 ppm. It is preferably in the range of 40 to 200 ppm. When less than 25ppm, there is When the adhesion to the surface of the insulating layer having a low arithmetic mean roughness is excellent, the conductor layer tends to be difficult, and when it exceeds 500 ppm, the storage stability and the insulating property of the resin composition tend to be lowered.

<(E) Thermoplastic Resin>

Further, the resin composition of the present invention may further contain (E) a thermoplastic resin to increase the mechanical strength of the cured product, and further improve the film forming ability when used in the form of a film. Examples of such a thermoplastic resin include a phenoxy resin, a polyimine resin, a polyamidoximine resin, a polyether quinone resin, a polyfluorene resin, a polyether oxime resin, and a polyphenylene ether. Resin, polycarbonate resin, polyether ether ketone resin, polyester resin. These thermoplastic resins may be used singly or in combination of two or more kinds. The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000 from the viewpoint of improving the film forming ability or mechanical strength and improving the compatibility of the resin varnish. The weight average molecular weight of the present invention is also measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). The weight average molecular weight of the GPC method, specifically, the LC-9A/RID-6A manufactured by Shimadzu Corporation and the Shodex K-800P/K-804L manufactured by Showa Denko Co., Ltd. /K-804L, using chloroform as a mobile phase, and measuring at a column temperature of 40 ° C, can be calculated using a calibration curve of standard polystyrene.

In the resin composition of the present invention, when the (E) thermoplastic resin is blended, the content of the thermoplastic resin in the resin composition is not particularly limited, and is 100% by mass based on the nonvolatile content in the resin composition. It is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass. When the content of the thermoplastic resin is too small, the effect of improving the film forming ability or the mechanical strength tends not to be exhibited. When the amount is too large, the melt viscosity increases and the arithmetic mean roughness of the surface of the insulating layer after the wet roughening step tends to increase.

<(F) rubber particles>

Further, by including the (F) rubber particles, the resin composition of the present invention can improve the plating peel strength, improve the piercing processability, and lower the dielectric tangent, and can also obtain a stress relaxation effect. The rubber particles used in the present invention are not dissolved in an organic solvent when the resin composition varnish is prepared, and are also incompatible with a cyanate resin or an epoxy resin which is an essential component. Therefore, the rubber particles are present in a dispersed state in the varnish of the resin composition of the present invention. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it cannot be dissolved in an organic solvent or a resin.

Preferable examples of the rubber particles obtained by using the present invention include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylonitrile-based rubber particles. . The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, the shell layer of the outer layer is composed of a glassy polymer, and the core layer of the inner layer is composed of a rubber polymer. The structure or the outer shell layer is composed of a glassy polymer, the intermediate layer is composed of a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer. a glassy polymer layer, for example, a polymer of methyl methacrylate or the like The rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber) or the like. Two or more types of rubber particles may be used in combination.

Specific examples of the core-shell type rubber particles include STAPHYLOID AC 3832, AC 3816N, IM-401, and IM-401, 7-17 (trade name, Ganzi Chemical Co., Ltd.), and METABLEN KW-4426 ( Trade name, Mitsubishi Rayon (share) system). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (having an average particle diameter of 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the acrylonitrile-based rubber particles include METABLEN W300A (average particle diameter: 0.1 μm) and W450A (average particle diameter: 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

The average particle diameter of the rubber particles is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles used in the present invention can be measured by a dynamic light scattering method. For example, the rubber particles are uniformly dispersed by ultrasonic waves or the like in a suitable organic solvent, and the particle size distribution of the rubber particles is prepared on a mass basis using a thick particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). This median diameter was measured as an average particle diameter.

The content of the rubber particles is 100% by mass, preferably 1 to 10% by mass, and more preferably 2 to 5% by mass based on the nonvolatile content in the resin composition.

<(G) flame retardant>

The resin composition of the present invention can further impart flame retardancy by containing (G) a flame retardant. Examples of the flame retardant include an organic phosphorus-based flame retardant, a nitrogen-containing phosphorus compound, a nitrogen compound, a polysulfonium-based flame retardant, and a metal hydroxide. Examples of the organic phosphorus-based flame retardant include phenanthroline phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., and phosphorus-containing benzenes such as HFB-2006M manufactured by Showa Polymer Co., Ltd. Oxazine compound, Ajinomoto Fine-Techno (REOFOS30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, Beixing Chemical Industry Co., Ltd. TPPO, PPQ, Clariant (OP) OP930, Da Ba Chemical (share) PX200 phosphate compound, Dongdu Huacheng (share) FX289, FX305, TX0712 and other phosphorus-containing epoxy resin, A phosphorus-containing phenoxy resin such as ERF001 manufactured by Dongdu Chemical Co., Ltd., or a phosphorus-containing epoxy resin such as YL7613 manufactured by Nippon Epoxy Resin Co., Ltd. Specific examples of the phosphorus compound containing an organic nitrogen include a phosphate phthalamide compound such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., and SPB100, SPE100, and FOS by Otsuka Chemical Co., Ltd. An even phosphorus-nitrogen compound such as FP-series manufactured by the company. Specific examples of the metal hydroxide include magnesium hydroxide such as UD65, UD650, and UD653 manufactured by Ube Materials Co., Ltd., and B-30, B-325, B-315, and B manufactured by Ba Industrial Co., Ltd. -308, B-303, UFH-20, etc., such as aluminum hydroxide.

The content of the flame retardant, the non-volatile content in the resin composition When it is 100% by mass, it is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 8% by mass, even more preferably in the range of 1 to 6% by mass.

<Other ingredients>

In the resin composition of the present invention, other components may be blended if necessary without departing from the effects of the present invention. Examples of the other component include an organic filler such as a vinyl benzyl compound, an acrylonitrile compound, a maleimide compound, a thermosetting resin of a blocked isocyanate compound, a strontium powder, an aurant powder, and a fluorine powder. Adbens such as Orben and Benton, polyfluorene, fluorine, or polymeric defoamers or leveling agents, imidazoles, thiazoles, triazoles, decane couplings, etc. Force imparting agent, phthalocyanine. Blue, turnip. Green, iodine. A coloring agent such as iodine green, disazo yellow, carbon black, or the like.

The preparation method of the resin composition of the present invention is not particularly limited, and examples thereof include a mixing method in which a blending component is added to a solvent or the like, and a mixing method using a rotary mixer or the like is required.

The use of the resin composition of the present invention is not particularly limited, and it can be used for a sheet-like laminate material such as a film or a prepreg, a wiring board (a laminate, a multilayer printed wiring board, etc.), solder resist, and A filler, a wafer bonding material, a semiconductor sealing material, a filling resin, a component-embedded resin, and the like are widely used as a resin composition as an essential use. Among them, the multilayer printed wiring board can be suitably used as a resin composition for forming an insulating layer, and can be suitably used as a resin composition for forming a conductor layer by plating. The resin composition of the present invention can be coated in a varnish state The insulating layer is formed on the wiring board. However, it is generally preferred to use a sheet-like laminate of a film, a prepreg or the like in the industry. From the viewpoint of the softening point of the resin composition and the lamination property of the sheet-like laminate, 40 to 150 ° C is preferable.

<Next film>

The adhesive film of the present invention is prepared by a person skilled in the art by a known method, for example, by dissolving a resin composition in an organic solvent to prepare a resin varnish which can be applied to a support by using a die coater or the like. The organic solvent is dried by heating or blowing hot air to form a resin composition layer. Thereby, the resin composition can be used to produce a formed film as a resin composition layer on the support.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol B. Acetate such as acid ester, cellosolve, carbitol such as butyl carbitol, aromatic hydrocarbon such as toluene or xylene, dimethylformamide, dimethylacetamide, N a guanamine-based solvent such as methylpyrrolidone. The organic solvent may be used in combination of two or more kinds.

The drying conditions are not particularly limited, and the organic solvent content of the resin composition layer is 10% by mass or less, preferably 5% by mass or less. The amount of the organic solvent in the varnish varies depending on the boiling point of the organic solvent. For example, the resin composition can be dried at 50 to 150 ° C for 3 to 10 minutes by using a varnish containing 30 to 60% by mass of an organic solvent. An adhesive film forming a formed layer on the support.

The thickness of the resin composition layer formed by the subsequent film is preferably greater than or equal to the thickness of the conductor layer. Since the thickness of the conductor layer having the wiring board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm, and more preferably has a thickness of 20 to 80 μm.

Examples of the support include a film of a polyolefin such as polyethylene, polypropylene, or polyvinyl chloride, a polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), or a polyester such as polyethylene naphthalate. Various plastic films such as film, polycarbonate film, and polyimide film. A release paper, a metal foil such as a copper foil or an aluminum foil, or the like can also be used. A surface treatment such as a median absolute error process or a corona treatment may be performed on the support and the protective film described later. Further, a release agent such as a polyoxymethylene resin release agent, an alkyd resin release agent, or a fluororesin release agent may be used as a mold release treatment.

The thickness of the support is not particularly limited, and is preferably 10 to 150 μm, more preferably 25 to 50 μm.

The protective film according to the support may be further laminated on the surface of the resin composition layer where the support is not adhered. The thickness of the protective film is not particularly limited and is, for example, 1 to 40 μm. By laminating the protective film, adhesion or scratches to the surface of the resin composition layer such as dust or the like can be prevented. The film can then be wound into a roll for storage.

<Using a multilayer printed wiring board with a film>

Next, an example of a method of manufacturing a multilayer printed wiring board using the adhesive film manufactured as described above will be described.

First, the film is laminated to the film using a vacuum laminator. One or both sides of the board. Examples of the substrate used for the wiring board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Further, the term "wiring board" as used herein refers to a conductor layer (circuit) which has been formed on one side or both sides of the substrate as described above. Further, a multilayer printed wiring board in which a conductor layer and an insulating layer are laminated to each other, and a single-sided or double-sided layer of the outermost layer of the multilayer printed wiring board is a patterned conductor layer (circuit), and is also included in the wiring layer. board. In addition to the surface of the conductor layer, pre-roughening treatment may be performed by blackening treatment, copper etching, or the like.

After the above-mentioned lamination, when the protective film is removed after the film has a protective film, if necessary, the film and the wiring board are preheated, and the film is pressed against the wiring board while being pressurized and heated. In the adhesive film of the present invention, a method of laminating to a wiring board by vacuum lamination under reduced pressure is suitably used. The conditions for the lamination are not particularly limited. For example, the crimping temperature (laminating temperature) is preferably 70 to 140 ° C, and the crimping pressure is preferably 1 to 11 kgf/cm ² (9.8 × 10 ⁴ to 107.9 × 10). ⁴ N/m ² ), it is preferred to laminate the air pressure under a reduced pressure of 20 mmHg (26.7 hPa) or less. Moreover, the method of laminating may be a batch type or a continuous type of rolls. Vacuum lamination can be carried out using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, Nikkei can be cited. A vacuum presser manufactured by Morton Co., Ltd., a vacuum press laminator manufactured by Nihon Seiki Co., Ltd., a roll dryer of Hitachi Industries, and a vacuum laminator made of Hitachi AIC.

Further, the laminating step of heating and pressurizing under reduced pressure may be carried out using a general vacuum hot press. For example, a metal plate such as a heated SUS plate may be pressed from the side of the support layer. Under reduced pressure, the degree of pressure reduction is reduced to usually 1 × 10 ^-2 MPa or less, preferably 1 × 10 ^-3 MPa or less. The heating and the pressurization may be carried out in one step, but it is preferably carried out in a condition of dividing into two or more stages from the viewpoint of controlling the bleeding of the resin. For example, the first stage is pressurized at a temperature of 70 to 150 ° C and a pressure of 1 to 15 kgf / cm ² ; the second stage of pressure, with a temperature of 150 to 200 ° C, a pressure of 1 to 40 kgf / The range of cm ² is preferably performed. The time of each stage is preferably 30 to 120 minutes. As a commercially available vacuum hot press, for example, MNPC-V-750-5-200 (manufactured by Nippon Seiki Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like can be cited.

After the subsequent film is laminated on the wiring board, after cooling to near room temperature, the support is peeled off when the support is peeled off, and an insulating layer can be formed on the wiring board by thermal curing. The conditions of the heat curing may be appropriately selected in accordance with the kind and content of the resin component in the resin composition, and preferably selected from 150 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably from 160 ° C to 210 ° C. ~120 minutes range.

After the formation of the insulating layer, the support is not peeled off before the curing. Then, if necessary, the insulating layer formed on the wiring board is drilled to form a via hole and a via hole. Drilling, for example, by well-known methods such as perforation, laser, plasma, etc., may be performed in combination with such methods, but laser drilling such as carbon dioxide gas laser and YAG laser is the most common method. .

Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As dry plating, vapor deposition, sputtering, ion plating, etc. can be used. The method of public knowledge. In the wet plating, the fixing anchor is formed in the order of swelling of the surface of the insulating layer by swelling treatment of the swelling liquid, roughening treatment by the oxidizing agent, and neutralization treatment by the neutralizing liquid. The swelling treatment of the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 to 80 ° C for 5 to 20 minutes, preferably at 55 to 65 ° C for 5 to 10 minutes. The swelling solution may, for example, be an alkali solution or a surfactant solution, and is preferably an alkali solution. Examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. As a commercially available swelling liquid, for example, Swelling Dip manufactured by Atotech Japan Co., Ltd. can be cited. SecuriganthP (Swelling Dip Securiganth P), Swelling Dip. Securiganth SBU (Swelling Dip Securiganth SBU) and the like. The oxidizing agent is roughened, and the insulating layer is immersed in the oxidizing agent solution at 60 ° C to 80 ° C for 10 minutes to 30 minutes, preferably at 70 to 80 ° C for 10 to 20 minutes. Examples of the oxidizing agent include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, or the like. Further, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by weight. As a commercially available oxidizing agent, for example, Concentrate manufactured by Atotech Japan Co., Ltd. may be mentioned. Compact CP, Dosing Solution. Alkaline permanganic acid solution such as SecuriganthP. The mixture is neutralized by a neutralizing solution, and immersed in a neutralizing solution at 30 to 50 ° C for 3 to 10 minutes, preferably at 35 to 45 ° C for 3 to 8 minutes. As the neutralizing liquid, an acidic aqueous solution is preferred, and as a commercial product, a reduction solution manufactured by Atotech Japan Co., Ltd. may be mentioned. SecuriganthP.

Secondly, combining electroless plating and electrolytic plating to form a conductor Floor. Further, the conductor layer is formed of a reverse-plated plating resist, and the conductor layer can be formed only by electroless plating. As a pattern forming method thereafter, for example, a subtraction method, a semi-addition method, or the like which is well known to those skilled in the art can be used.

<prepreg>

In the prepreg of the present invention, the resin composition of the present invention is impregnated into a sheet-like reinforcing substrate by a hot melt method or a solvent method, and can be semi-cured by heating. That is, the resin composition of the present invention can be used as a prepreg impregnated on a sheet-like reinforcing substrate. As the sheet-like reinforcing base material, for example, a fiber which is commonly used as a fiber for prepreg such as glass cloth or amide fiber can be used.

The hot melt method is not a method of dissolving a resin in an organic solvent, but is applied to a coated paper having good releasability to the resin, and is laminated on a sheet-like reinforcing substrate, or is not dissolved in an organic solvent. Instead, it is directly applied to a sheet-like reinforcing substrate or the like by a die coater, and is a method for producing a prepreg. In the solvent method, a resin is dissolved in an organic solvent to prepare a resin varnish, and a sheet-like reinforcing substrate is immersed in the varnish, and the resin varnish is immersed in a sheet-like reinforcing substrate, followed by drying.

<Multilayer printed wiring board using prepreg>

Next, an example of a method of manufacturing a multilayer printed wiring board using the prepreg produced as described above will be described. One piece of the prepreg of the present invention or a plurality of pieces of the prepreg are overlapped on the wiring board as needed, and the metal sheet is clamped through the release film to pressurize. The laminate was vacuum-pressed under heating. Pressurized. The heating condition is preferably from 5 to 40 kgf/cm ² (49 × 10 ⁴ to 392 × 10 ⁴ N/m ² ) at a temperature of from 120 to 200 ° C for 20 to 100 minutes. Further, similarly to the film, the prepreg is laminated to the wiring board by vacuum lamination, and may be heat-hardened. Then, after roughening the surface of the cured prepreg in the same manner as described above, a multilayer printed wiring board in which the conductor layer is formed by plating can be produced.

<semiconductor device>

A semiconductor device can be manufactured using the multilayer printed wiring board of the present invention. At the conduction of the multilayer printed wiring board of the present invention, a semiconductor device can be manufactured by mounting a semiconductor wafer. The term "conducting point" means "where electrical signals are transmitted through a multilayer printed wiring board", and it does not matter whether it is a surface or an embedded place. Further, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

In the method of mounting a semiconductor wafer in the manufacture of the semiconductor device of the present invention, the semiconductor wafer is not particularly limited as long as it can effectively function, and specifically, a wire bonding mounting method, a swap wafer mounting method, and a bump-free method are exemplified. A method of mounting a buildup layer (BBUL), a method of mounting an anisotropic conductive film (ACF), a method of mounting a non-conductive film (NCF), and the like.

The "mounting method by the bump-free deposition layer (BBUL)" means a method of "mounting a semiconductor wafer directly in a concave portion of a multilayer printed wiring board and connecting the semiconductor wafer to a wiring on the printed wiring board", and further With the following BBUL method 1), BBUL method 2) The installation method is quite different.

BBUL method 1) mounting method for mounting a semiconductor wafer on a recess of a multilayer printed wiring board using an underfill

BBUL method 2) is a method of mounting a semiconductor wafer on a recess of a multilayer printed wiring board using a film or a prepreg

BBUL method 1) specifically includes the following steps.

Step 1) A person who removes the conductor layer from both sides of the multilayer printed wiring board is provided, and a through hole is formed by laser or mechanical perforation.

Step 2) Attaching the adhesive tape to one surface of the multilayer printed wiring board, such as fixing the bottom surface of the semiconductor wafer to the adhesive tape and arranging it in the through hole. The semiconductor wafer at this time is preferably lower than the height of the through hole.

Step 3) Injecting an underfill into the gap between the through hole and the semiconductor wafer, and fixing the semiconductor wafer to the through hole by filling.

Step 4) Then peeling off the tape to expose the bottom surface of the semiconductor wafer.

Step 5) The adhesive film or prepreg of the present invention is laminated on the bottom surface side of the semiconductor wafer to coat the semiconductor wafer.

Step 6) After hardening the film or the prepreg, the bonding pads on the bottom surface of the semiconductor wafer are exposed by laser drilling to perform the above-mentioned roughening treatment, electroless plating, electrolytic plating, Connect to the wiring. The film or prepreg may be further laminated if necessary.

BBUL method 2) specifically includes the following steps.

Step 1) forming a photoresist on the conductor layer on both sides of the multilayer printed wiring board In the film, an opening portion is formed only on one side of the photoresist film by a photolithography method.

Step 2) The conductor layer exposed to the opening is removed by an etching solution to expose the insulating layer, and then the double-sided photoresist film is removed.

Step 3) Using the laser or perforation, the exposed insulating layer is completely removed and drilled to form a recess. The energy of the laser can be adjusted to a laser that reduces the laser absorption rate of copper and increases the laser absorption rate of the insulating layer, and the carbon dioxide gas is better. By using such a laser, the laser does not penetrate the conductor layer opposite to the opening of the conductor layer, but only the insulating layer can be removed.

Step 4) The bottom surface of the semiconductor wafer is placed on the opening side in the concave portion, and the adhesive film or the prepreg of the present invention is laminated on the side of the opening to cover the semiconductor wafer, and the gap between the semiconductor wafer and the concave portion is embedded. At this time, the semiconductor wafer is preferably lower in height than the concave portion.

Step 5) After hardening the film or prepreg, the bonding pads on the bottom surface of the semiconductor wafer are exposed by laser drilling.

Step 6) The wiring is connected by performing the above-described roughening treatment, electroless plating, electrolytic plating, and further laminating the film or prepreg if necessary.

Even in the method of mounting a semiconductor wafer, from the viewpoint of downsizing of the semiconductor device and reduction of transmission loss, or the fact that the heat history is not applied to the semiconductor wafer without soldering, and the deformation of the solder and the resin does not occur in the future, It is preferable to use a bumpless buildup layer (BBUL) mounting method, preferably BBUL method 1), BBUL method 2), and BBUL method 2).

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples.

<Measurement method. Evaluation method>

First of all, various methods of measurement. The evaluation method will be described.

<Preparation of sample for measurement of peel strength, arithmetic mean roughness (Ra value), and root mean square roughness (Rq value)>

(1) Primer treatment of inner wiring board

The double-sided etching of the glass cloth substrate epoxy double-sided copper-clad laminate (the thickness of the copper foil of 18 μm, the thickness of the substrate of 0.3 mm, and the R5715ES made by Matsushita Electric Works) through the inner layer circuit is 1 um on the MEC (share) The CZ8100 is used to roughen the copper surface.

(2) followed by lamination of the film

The film formed in Examples 1 to 7 and Comparative Examples 1 to 3 was laminated using a batch vacuum pressure laminator MVLP-500 (trade name of a famous machine) to laminate the inner wiring board. surface. The lamination was carried out by lowering the pressure of the pressure for 30 seconds to 13 hPa or less, followed by pressurization at 30 seconds, 100 ° C, and a pressure of 0.74 MPa.

(3) Hardening of resin composition

In Examples 1 to 6 and Comparative Examples 1 to 3, after peeling off the PET film from the laminated film, the resin composition was cured at 100 ° C for 30 minutes and further at 180 ° C for 30 minutes. After the Example 7 was thermally cured under the same conditions, the PET film was peeled off.

(4) roughening treatment

In Examples 1 to 6 and Comparative Examples 1 to 3, an inner layer wiring board in which an insulating layer was formed, and Swelling Dip Securiganth P containing diethylene glycol monobutyl ether in Atotech Japan (shares) of a swelling liquid was used. The alcohol ether and aqueous sodium hydroxide solution were immersed at 60 ° C for 5 minutes, and the work was carried out as a roughening liquid, Concentrate in Atotech Japan. CompactP (KMnO4: 60g/L, NaOH: 40g/L aqueous solution) was immersed at 80 ° C for 15 minutes, and finally used as a neutralizing solution in Atotech Japan's Reduction Solution. Securiganth P (aqueous solution of glyoxal, sulfuric acid) was immersed at 40 ° C for 5 minutes. In Example 7, the solution was immersed in a swelling solution at 60 ° C for 10 minutes, immersed in a roughening solution at 80 ° C for 20 minutes, and immersed in a neutralizing solution at 40 ° C for 5 minutes. Then, after drying at 80 ° C for 30 minutes, the surface of the insulating layer after the roughening treatment was measured for arithmetic mean roughness (Ra value) and root mean square roughness (Rq value).

(5) Plating by semi-additive method

In Examples 1 to 6 and Comparative Examples 1 to 3, in order to form a circuit on the surface of the insulating layer, the inner wiring board was immersed in a solution for electroless plating containing PdCl ₂ at 40 ° C for 5 minutes, followed by electroless copper plating. The dressing was immersed at 25 ° C for 20 minutes. After heating at 150 ° C for 30 minutes and tempering treatment, an etching resistance was formed, and after patterning by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 35 ± 5 μm. Next, the tempering treatment was carried out at 200 ° C for 60 minutes. The wiring board was measured for peel strength of the plated conductor layer.

<Measurement of Peel Strength of Plated Conductor Layer>

In the conductor layer of the wiring board, a notch having a width of 10 mm and a length of 100 mm is added, and the one end is peeled off and clamped by a holder (T.S. E, Auto com type testing machine AC-50C-SL). The load (kgf/cm) when peeling 35 mm in the vertical direction was measured at a rate of 50 mm/min at room temperature.

<Measurement of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) after roughening>

Using a non-contact surface roughness meter (WYKO NT3300, manufactured by Veeco Instruments Co., Ltd.), the Ra value and the Rq value were obtained from the VSI contact mode and the 50-fold lens by using the measurement range as 121 μm × 92 μm. Then, the average value of 10 points was randomly determined from each.

<Measurement of extension>

The adhesive films of Examples 1 to 7 and Comparative Examples 1 to 3 were cured by heat hardening at 190 ° C for 90 minutes. According to JIS K 7127, a dumbbell shape was cut out from the cured product to prepare a test piece, and peeled off. The PET film was subjected to a tensile test using a tensile tester RTC-1250A manufactured by ORIENTEC Co., Ltd., and the elongation at break was measured.

<Measurement of the lowest melt viscosity>

The melt viscosity of the resin composition layer was measured by the film formed in Examples 1 to 7 and Comparative Examples 1 to 3. Use (share) U. B. The Rheosol-G3000 manufactured by M Company uses a parallel plate with a resin content of 1 g and a diameter of 18 mm, and the measurement conditions are from a starting temperature of 60 ° C to 200 ° C at a temperature increase rate of 5 ° C / min, a measurement temperature interval of 2.5 ° C, and a vibration of 1 Hz / deg. The melt viscosity was measured.

<Manufacturing Example 1>

100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter 0.5 μm) was placed in a Henschel type mixer, and 2.5 parts by mass of a liquid polyfunctional epoxy resin (DIC) was sprayed. "HP4032 SS", a naphthalene type epoxy resin, a solution having a viscosity of 32 Pa.s at 25 ° C, an epoxy equivalent of 144, and a nonvolatile content of 80% by mass of methyl ethyl ketone (hereinafter referred to as "MEK") The product 1 was prepared by stirring spherical cerium oxide for 10 minutes. The maximum temperature reached during surface treatment is about 80 ° C and the average temperature is about 70 ° C.

<Manufacturing Example 2>

100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle size 0.5 μm) was put into Henschel type mixed powder 2 parts by mass of liquid polyfunctional epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, p-amine phenol epoxy resin, viscosity at 25 ° C of 0.6 Pa.s, epoxy equivalent of 95, non-aqueous) The oxidized component of 80% by mass of the MEK solution was stirred for 10 minutes to prepare the product 2. The maximum temperature reached during surface treatment is about 65 ° C and the average temperature is about 60 ° C.

<Manufacturing Example 3>

100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter 0.5 μm) was placed in a Henschel type mixer, and 2.7 parts by mass of a liquid polyfunctional epoxy resin was sprayed (new "ZX1059", bisphenol A type epoxy resin and bisphenol F type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd., having a viscosity of 2.3 Pa.s at 25 ° C, an epoxy equivalent of 165, and a non-volatile content of 75 % by mass of MEK Solution) The spherical cerium oxide was stirred for 10 minutes to prepare a product 3. The maximum temperature reached during surface treatment is about 80 ° C and the average temperature is about 65 ° C.

<Manufacturing Example 4>

100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter 0.5 μm) was placed in a Henschel type mixer, and 2 parts by mass of a liquid polyfunctional epoxy resin was sprayed (new Nippon Steel Chemical Co., Ltd. "ZX1542", glycerin type epoxy resin, MEK solution having a viscosity of 0.08 Pa.s at 25 ° C, an epoxy equivalent of 240, and a nonvolatile content of 80% by mass) while stirring spherical cerium oxide 10 After a minute, spray 0.3 The mass fraction (methyltrimethoxydecane) ("MTMS-A" manufactured by Tama Chemical Co., Ltd.) was stirred for 5 minutes to prepare a product 4. The maximum temperature reached during surface treatment is about 90 ° C and the average temperature is about 75 ° C.

<Manufacturing Example 5>

100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter 0.5 μm) was placed in a Henschel type mixer, and 2 parts by mass of a liquid polyfunctional epoxy resin (DIC) was sprayed. "HP 4032 SS", a naphthalene type epoxy resin, a viscosity of 32 Pa.s at 25 ° C, an epoxy equivalent of 144, and a MEK solution of 80% by mass of a nonvolatile component) after stirring the spherical cerium oxide for 10 minutes While spraying 0.6 parts by mass of an oligomer containing N-phenyl-3-aminopropyl alkoxy group (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25 ° C of 1000 mm ² /s), it was stirred for 5 minutes. Manufacturing 5. The maximum temperature reached during surface treatment is about 95 ° C and the average temperature is about 85 ° C.

<Manufacturing Example 6>

100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter: 0.5 μm) was placed in a Henschel type mixer, and 0.6 parts by mass of an epoxy group-containing decane coupling agent was sprayed ( Shin-Etsu Chemical Co., Ltd. "KBM 403") was stirred for 5 minutes to prepare a product 6. The maximum temperature reached during surface treatment is about 70 ° C and the average temperature is about 60 ° C.

<Example 1>

5 parts by mass of a naphthalene type epoxy resin (epoxy equivalent 144, "HP4700" manufactured by DIC Co., Ltd.), and 14 parts by mass of a liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, Mitsubishi Chemical Corporation) "jER828 EL"), 14 parts by mass of a biphenyl type epoxy resin (epoxy equivalent 269, manufactured by Nippon Chemical Co., Ltd. "NC3000H") was heated while stirring in 30 parts by mass of solvent naphtha. Dissolved and then cooled to room temperature. In the mixed solution, 1.5 parts by mass of rubber particles (manufactured by GANTSU Co., Ltd., STAPHYLOID AC3816N) was allowed to stand and swelled in 6 parts by mass of solvent naphtha at 12 hours and 20° C., and then the product 1 was further added. Further, 5 parts by mass of a flame retardant ("HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphophene-10-" was added. The oxides, having an average particle diameter of 1 μm, were kneaded by three rolls to be uniformly dispersed. Furthermore, 10 parts by mass of a phenolic novolak-based curing agent ("LA-7054" manufactured by DIC Co., Ltd.) and a methyl ethyl ketone (hereinafter referred to as "60% by mass" of a nonvolatile component of the phenolic hydroxyl group equivalent 124 are mixed. MEK") solution), 10 parts by mass of naphthalene phenol resin (phenolic hydroxyl equivalent 215, "SN485" manufactured by Nippon Steel Chemical Co., Ltd., 60% by mass of MEK solution of nonvolatile matter), and 7 parts by mass of phenoxy Base resin (weight average molecular weight 35000, "YL7553" manufactured by Mitsubishi Chemical Corporation, MEK and cyclohexanone 1:1 solution of 30% by mass of nonvolatile matter), and 2 parts by mass of 4-dimethylamine as hardening accelerator A 5% by mass MEK solution of pyridine and 4 parts by mass of methyl ethyl ketone (MEK) were uniformly dispersed in a rotary mixer to obtain a resin varnish. Next, the resin varnish is removed from the alkyd system. The release surface of the polyethylene terephthalate film (thickness: 38 μm) was uniformly applied by a die coater so that the thickness of the resin composition layer after drying became 40 μm to 80 to 110 ° C (average 95). It was dried under ° C for 5 minutes (the amount of residual solvent in the resin composition layer: about 2% by mass). Next, a polypropylene film having a thickness of 15 μm was bonded to the surface of the resin composition layer while being wound into a roll. The roll-shaped film was slit to a width of 507 mm to obtain a film having a sheet size of 507 × 336 mm.

<Example 2>

A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article 2. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain a film.

<Example 3>

A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article of manufacture 3. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain a film.

<Example 4>

A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article 4. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain a film.

<Example 5>

A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article 5 of manufacture. Then, using such a resin varnish, it carried out in exactly the same manner as Example 1, and the adhesive film was obtained.

<Example 6>

In addition to the resin varnish of Example 1, 0.6 parts by mass of an alkoxy oligomer containing N-phenyl-3-aminopropyl (manufactured by Shin-Etsu Chemical Co., Ltd.) at a viscosity of 1000 mm ² /s at 25 ° C was further added. After that, the rest of the resin varnish was produced in exactly the same manner. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain a film.

<Example 7>

15 parts by mass of a naphthalene type epoxy resin (epoxy equivalent 144, "HP4032 SS" manufactured by DIC Co., Ltd.), 2 parts by mass of a bixylenol type epoxy resin (epoxy equivalent 190, Mitsubishi Chemical) (YX4000 HK), 18 parts by mass of modified naphthalene epoxy resin (epoxy equivalent: about 330, "ESN475V" manufactured by Nippon Steel Chemical Co., Ltd.) in 25 parts by mass of solvent naphtha It was dissolved by heating while stirring, and then cooled to room temperature. In the mixed solution, 1.5 parts by mass of rubber particles (manufactured by GANTSU Co., Ltd., STAPHYLOID AC3816N) was allowed to stand and swelled in 6 parts by mass of solvent naphtha at 12 hours and 20° C., and further 160 parts by mass of the product 5 was mixed. Further, 3 parts by mass of a flame retardant ("HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenone-10-" was added. Oxide, average particle size 1 Μm), kneaded in 3 rolls to make it evenly dispersed. Furthermore, 20 parts by mass of an active ester-based curing agent (active base equivalent of about 223, "DICC" "HPC-8000-65T", non-volatile content of 65 mass% in toluene), and 30 parts by mass of bisphenol A dicyandiamide were added. Prepolymer of acid ester ("BA230S75" manufactured by Lonza Japan Co., Ltd., MEK solution having a cyanate equivalent of about 232 and a nonvolatile content of 75 mass%), 10 parts by mass of phenoxy resin (weight average molecular weight: 35,000, Mitsubishi Chemical Corporation) (YL7553), a non-volatile content of 30% by mass of MEK and a cyclohexanone 1:1 solution, and 1 part by mass of a 4% by mass MEK solution of 4-dimethylaminopyridine as a hardening accelerator 4 parts by mass of a 1 mass% MEK solution of cobalt (III) acetamidine pyruvate (manufactured by Tokyo Chemical Industry Co., Ltd.) was uniformly dispersed in a rotary mixer to obtain a resin varnish. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain a film.

<Comparative Example 1>

A resin varnish was produced in the same manner except that the product 1 of Example 1 was changed to 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter: 0.5 μm). Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain a film.

<Comparative Example 2>

The product 1 of Example 1 was changed to 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter 0.5). A resin varnish was produced in the same manner except that 2 parts by mass of epoxy resin (epoxy equivalent 144, "HP4032 SS" manufactured by DIC) was added in addition to μm). Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain a film.

<Comparative Example 3>

A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article of manufacture 6. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain a film.

The results are shown in Table 1.

From the results of Table 1, the resin compositions of Examples 1 to 7, It is understood that a low arithmetic mean roughness and a low root mean square roughness are obtained to obtain a sufficient peel strength. Further, it is understood that the extension can be improved to improve the operability. Further, it is understood that the melt viscosity is lowered to improve the workability of the film. Further, the Rq value reflects a state of the surface of the insulating layer, and it is understood that a fine rough surface is caused by a decrease in the Rq value. On the other hand, in Comparative Examples 1 to 3, the arithmetic mean roughness and the root mean square roughness were large, and the plating expansion peeling strength was remarkably changed to a small value.

[Industrial availability]

The present invention provides a plating conductor layer which exhibits a relatively high arithmetic mean roughness (Ra value) of the surface of the insulating layer after the wet roughening step, and even if it is a low root mean square roughness (Rq value) A novel resin composition of peel strength. Further, it is possible to provide a laminate film, a prepreg, a multilayer printed wiring board, and a semiconductor device. Further, it can be installed in computers, mobile phones, digital cameras, televisions, and other electrical products or motorcycles, automobiles, electric cars, ships, aircraft, and the like.

Claims (19)

A resin composition for an insulating layer of a multilayer printed wiring board, characterized by comprising (A) an epoxy resin, (B) a naphthol-based curing agent, an active ester-based curing agent, and a cyanate-based curing agent. One or more kinds of curing agents and (C) an inorganic filler which is surface-treated with a liquid epoxy resin, wherein the non-volatile content of the resin composition is 100% by mass, and the component (A) is contained in an amount of 3 to 40% by mass. (B) component 3 to 30% by mass and (C) component 20 to 85% by mass. The resin composition of claim 1, wherein (A) the epoxy resin comprises a liquid epoxy resin and a solid epoxy resin, and the liquid epoxy resin: solid epoxy resin mass ratio (liquid epoxy) Resin: solid epoxy resin) is in the range of 1:0.1 to 1:2. The resin composition of claim 1, wherein (C) the inorganic filler material treated with the surface of the liquid epoxy resin is surface-treated with 0.05% by mass of the liquid epoxy resin relative to 100% by mass of the inorganic filler. By. The resin composition of claim 1, wherein (C) the inorganic filler surface-treated with the liquid epoxy resin has an average temperature of 20 to 100 ° C when the liquid epoxy resin is surface-treated. The resin composition of claim 1, wherein (C) the inorganic filler having a surface treated with the liquid epoxy resin has a maximum temperature of 50 to 150 ° C when surface-treated with the liquid epoxy resin. The resin composition of claim 1, wherein the liquid epoxy resin has a viscosity at 25 ° C of 0.01 to 50 Pa‧s. The resin composition of claim 1, wherein (C) the liquid epoxy resin which is subjected to the surface treatment of the liquid epoxy resin is selected from the group consisting of a naphthalene type epoxy resin and a bisphenol A type epoxy resin. One or more of the group consisting of a bisphenol F type epoxy resin, a glycerin type epoxy resin, and a p-amine phenol type epoxy resin. The resin composition of claim 1, wherein (C) the inorganic filler surface treated with the liquid epoxy resin is further selected from the group consisting of a decane coupling agent, an alkoxy decane, an alkoxy oligo, and an aluminum olefin. One or more surface treatments of the group consisting of a mixture, a titanium coupling agent, and a zirconium coupling agent. The resin composition of claim 1, which further contains (D) a hardening accelerator. The resin composition of claim 1, which further contains (E) a thermoplastic resin. The resin composition of claim 1, which further contains (F) rubber particles. The resin composition of claim 1, which further contains (G) a flame retardant. The resin composition of claim 1, which is formed by hardening a resin composition to form an insulating layer, and roughening the surface of the insulating layer to have an arithmetic mean roughness of 10 nm to 330 nm and a root mean square roughness of 10 to 480 nm, and The peeling strength of the conductor layer and the insulating layer obtained by plating the surface of the insulating layer subjected to the roughening treatment is 0.4 kgf/cm to 1.0 kgf/cm. The resin composition of claim 1 which is used for forming an insulating layer of a multilayer printed wiring board. An adhesive film formed by forming a resin composition according to any one of claims 1 to 14 as a resin composition layer on a support. The adhesive film of claim 15, wherein the resin composition layer has a minimum melt viscosity of 500 to 14000 poise. A prepreg obtained by impregnating a resin composition according to any one of claims 1 to 14 into a sheet-like reinforcing substrate. A multilayer printed wiring board formed by forming a heat insulating layer of a resin composition according to any one of claims 1 to 14. A semiconductor device characterized by using the multilayer printed wiring board of claim 18.