TWI602873B - Resin composition - Google Patents

Description

Resin composition

The present invention relates to a resin composition. Further, it is a sheet-like laminate including the resin composition, a multilayer printed wiring board, and a semiconductor device.

In recent years, due to the evolution of miniaturization and high performance of electronic equipment, it has been sought to stratify, thicken, and increase the density in a build-up layer of a multilayer printed wiring board.

Look for a variety of methods for this. For example, Patent Document 1 discloses that a filler is surface-treated with a decane-based or titanium-based coupling agent. However, there is no description about bis(alkoxydecane)amine.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-224644

In order to solve the problem, the present invention provides a resin composition capable of forming a plated conductor layer having sufficient peel strength, in which not only the arithmetic mean roughness of the surface of the insulating layer is low, but also the root mean square roughness in the wet roughening step. The degree is also small.

In order to solve the above problems, the inventors of the present invention have carefully reviewed and reviewed the results, and the resin composition is characterized in that it contains an epoxy resin, a hardener, and an inorganic filler which is surface-treated with bis(alkoxydecane)amine. this invention.

That is, the present invention is intended to contain the following contents.

[1] A resin composition characterized by an epoxy resin, a hardener, and an inorganic filler surface-treated with bis(alkoxydecane)amine.

[2] The resin composition according to the above [1], wherein the bis(alkoxydecane)amine contains a secondary amine group.

[3] The resin composition according to the above [1] or [2], wherein the bis(alkoxydecane)amine has a molecular weight of from 260 to 2,000.

[4] The resin composition according to any one of the above [1] to [3] wherein the bis(alkoxydecane)amine is bis(trimethoxydecylpropyl)amine.

[5] The resin composition according to any one of the above [1] to [4] wherein the inorganic filler has an average particle diameter of 0.01 to 5 μm.

[6] The resin composition according to any one of the above [1] to [5] wherein the inorganic filler is cerium oxide.

[7] The resin composition according to any one of the above [1] to [6] wherein, when the nonvolatile content in the resin composition is 100% by mass, the content of the inorganic filler is 30 to 90% by mass. .

[8] The resin composition according to any one of the above [1] to [7], wherein the bis(alkoxydecane)amine is surface-treated at 0.05 to 5 parts by mass based on 100 parts by mass of the inorganic filler. deal with.

[9] The resin composition according to any one of the above [1] to [8] wherein the inorganic filler has a carbon amount per unit surface area of 0.05 to 1 mg/m ² .

[10] The resin composition according to any one of the above [1] to [9], 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 300 nm or less. The square root roughness is 500 nm or less.

[11] The resin composition according to any one of the above [1] to [10] wherein the resin layer is cured to form an insulating layer, the surface of the insulating layer is roughened, and the conductor layer obtained after plating is The peeling strength of the insulating layer was 0.35 kgf/cm or more.

[12] The resin composition according to any one of the above [1] to [11], which is a resin composition for a build-up layer of a multilayer printed wiring board.

[13] A sheet-like laminate comprising the resin composition according to any one of the above [1] to [12].

[14] A multilayer printed wiring board characterized in that an insulating layer is formed by a cured product of the resin composition according to any one of [1] to [12].

[15] A semiconductor device characterized by using the multilayer printed wiring board of the above [14].

By using a resin composition containing an epoxy resin, a hardener, and an inorganic filler surface-treated with bis(alkoxydecane)amine, it is possible to provide an arithmetic mean roughness of the surface of the insulating layer in the wet roughening step. The resin composition is low in degree and the root mean square roughness is also low, and a resin composition of a plated conductor layer having sufficient peel strength can be formed thereon.

The present invention relates to a resin composition characterized by comprising a resin composition comprising an epoxy resin, a hardener, and an inorganic filler surface-treated with bis(alkoxydecane)amine. Hereinafter, the resin composition will be described in detail.

<Epoxy resin>

The epoxy resin used in the present invention is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol AF epoxy resin. Phenolic novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthene ether type epoxy resin, glycidylamine type epoxy resin, Glycidyl epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, fluorene epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic Epoxy resin, heterocyclic epoxy resin , an epoxy resin containing a spiral ring, a dicyclopentadiene type epoxy resin, a cyclohexane dimethanol type epoxy resin, a trimethylol type epoxy resin, a halogenated epoxy resin, or the like. These may be used in combination of one type or two or more types.

Among them, from the viewpoints of improving heat resistance, improving insulation reliability, and improving peel strength, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin are used. Resin, biphenyl type epoxy resin, naphthene ether type epoxy resin, glycidyl ester type epoxy resin, dicyclopentadiene type epoxy resin, fluorene type epoxy resin or epoxy resin having butadiene structure It is preferable to select one or more kinds, and it is more preferable to use a bisphenol A type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, or a dicyclopentadiene type epoxy resin. Specific examples include bisphenol A type epoxy resin ("Epikote 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin ("JER806H" and "YL983U" manufactured by Mitsubishi Chemical Corporation). Naphthalene type 2-functional epoxy resin ("HP4032", "HP4032D", "HP4032SS", "EXA4032SS" made by DIC), and naphthalene type 4-functional epoxy resin (HP4700" and "HP4710" manufactured by DIC Corporation ), a naphthol type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Co., Ltd.), an epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.), and Epoxy resin of benzene structure ("NC3000H", "NC3000L", "NC3100" made by Nippon Kayaku Co., Ltd., "YX4000", "YX4000H", "YX4000HK", "YL6121" manufactured by Mitsubishi Chemical Corporation) Epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), "Naphthalene ether" epoxy resin (EXA-7310, "EXA-7311", "EXA-7311L", "EXA7311-" G3"), glycidyl ester epoxy Resin ("NA711", "EX721", "R540" manufactured by Nagasechemtex Co., Ltd.).

The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule, and a liquid epoxy resin and a solid epoxy resin are preferably used in combination. The liquid epoxy resin preferably has two or more epoxy groups in one molecule, and is preferably an aromatic epoxy resin which is liquid at a temperature of 20 ° C, and the solid epoxy resin has three or more in one molecule. The epoxy group is preferably an aromatic epoxy resin which is solid at a temperature of 20 °C. Further, the term "aromatic epoxy resin" as used in the present invention means an epoxy resin having an aromatic ring structure in the molecule. When a liquid epoxy resin and a solid epoxy resin are used together with an epoxy resin, when the resin composition is used in the form of a film, it is possible to have moderate flexibility, improve handleability, or lower the cured product of the resin composition. From the viewpoint of surface roughness, the mass ratio of the blending ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.1 to 1:2, and is in the range of 1:0.3 to 1:1.8. Preferably, the range of 1:0.6 to 1:1.5 is more preferable.

Liquid epoxy resin is preferably bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, glycidyl ester epoxy resin or naphthalene epoxy resin, bisphenol A A type epoxy resin, a bisphenol F type epoxy resin, or a naphthalene type epoxy resin is preferred. One or two of these may be combined and used. The solid epoxy resin is a tetrafunctional naphthalene epoxy resin, a cresol novolac epoxy resin, a dicyclopentadiene epoxy resin, a trisphenol epoxy resin, a naphthol epoxy resin, a fluorene epoxy resin, Biphenyl type epoxy resin or naphthene ether type epoxy resin is preferred, and naphthol type epoxy resin Or a biphenyl type epoxy resin is preferred. One type or two or more types may be used in combination.

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 content in the resin composition is 100% by mass, the content of the epoxy resin is 3 to 40% by mass. % is better, 5 to 35 mass% is better, and 10 to 30 mass% is better.

<hardener>

The curing agent to be used in the present invention is not particularly limited, and examples thereof include a phenol-based curing agent, an active ester-based curing agent, a cyanate-based curing agent, a benzoxazine-based curing agent, and an acid anhydride-based curing agent. In view of the fact that the roughness (Ra value) and the root mean square roughness (Rq value) are lowered, it is preferred to use one or more selected from the group consisting of a phenolic curing agent, an active ester curing agent, and a cyanate curing agent. It is preferred to use one or more selected from the group consisting of an active ester-based curing agent and a cyanate-based curing agent, and more preferably an active ester-based curing agent. These may be used in combination of one type or two or more types.

The phenolic curing agent is not particularly limited, but a biphenyl type curing agent, a naphthalene type curing agent, a phenol novolak type curing agent, a naphthene ether type curing agent, and a triazine skeleton phenol type curing agent are preferred. Specifically, for example, MEH-7700, MEH-7810, MEH-7851 (made by Megumi Kasei Co., Ltd.), naphthalene type hardener, NHN, CBN, and GPH (manufactured by Nippon Kayaku Co., Ltd.) ), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (Nippon Steel Chemical Co., Ltd.), EXB9500 (DIC), phenol phenolic type hardener TD2090 (DIC ( (manufactured by DIC), EXB-6000 (manufactured by DIC Co., Ltd.), a phenolic curing agent containing a triazine skeleton, LA3018, LA7052, LA7054, LA1356 (manufactured by DIC Co., Ltd.). One type or two or more types may be used in combination.

The active ester-based curing agent is not particularly limited, but generally has two or more high reactivity activities in one molecule such as a phenol ester, a thiophenol ester, an N-hydroxylamine, or an ester of a heterocyclic hydroxy compound. The ester group compound is preferred. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a sulfuric acid compound with a hydroxy compound and/or a thiol compound. Particularly, 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-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is preferred. good. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, p-citric acid, and pyroic acid. The phenolic compound or naphthol compound is hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, Phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2, 6-Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, 1,3,5-benzenetriol, benzenetriol, dicyclopentadiene diphenol, phenol novolac Wait. One or two or more kinds of the active ester-based curing agents can be used. As the active ester-based curing agent, an active ester-based curing agent disclosed in JP-A-2004-277460 or a commercially available product can be used. As a commercially available active ester-based curing agent, an active ester-based curing agent containing a dicyclopentadiene diphenol structure, an active ester-based curing agent containing a naphthalene structure, and an active ester of an acetylated phenolic phenolic aldehyde. The hardening agent, the active ester-based curing agent of benzophenone-based phenol phenolic acid, and the like are preferable, and in general, the active ester-based curing agent containing a dicyclopentadiene diphenol structure is preferable from the viewpoint of improving the peel strength. Specifically, the structure containing the dicyclopentadiene diphenol is EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (manufactured by DIC Co., Ltd., active base equivalent: about 223), and an active ester of bisphenol phenolic acetate. The hardener is DC808 (manufactured by Mitsubishi Chemical Corporation, active base equivalent: about 149), and the active ester-based hardener of benzophenone of phenol novolac is YLH1026 (manufactured by Mitsubishi Chemical Corporation, having an active base equivalent of about 200). YLH1030 (manufactured by Mitsubishi Chemical Corporation, active base equivalent: about 201), YLH1048 (manufactured by Mitsubishi Chemical Corporation, active base equivalent: about 245), and the like.

As the active ester-based curing agent containing a dicyclopentadiene diphenol structure, a compound of the following formula (1) can be more specifically exemplified.

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

From the viewpoint of lowering the dielectric loss and improving the heat resistance, it is preferable that R is a naphthyl group, and on the other hand, k is preferably 0, and n is preferably 0.25 to 1.5.

The cyanate-based curing agent is not particularly limited, and examples thereof include a phenolic type (phenol novolak type, alkyl phenol novolak type, etc.) cyanate type. Hardener, dicyclopentadiene type cyanate curing agent, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate curing agent, and partial triazineization prepolymerization Things and so on. The weight average molecular weight of the cyanate-based curing agent is not particularly limited, but 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 (oligomer (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) a polyfunctional cyanate resin induced by a bifunctional cyanate resin such as ether, a phenol novolac, a cresol novolak, a phenol resin containing a dicyclopentadiene structure, or the like, and a cyanate resin such as a partial triazine A polymer or the like can be used in combination of one or two of them. The cyanate resin sold in the market is a phenol novolac type polyfunctional cyanate resin represented by the following formula (2) (manufactured by Lonza Japan Co., Ltd.) , PT30, cyanate ester equivalent 124), a part or all of the bisphenol A dicyanate represented by the following formula (3), which is triazine-formed to form a terpolymer prepolymer (manufactured by Lonza Japan Co., Ltd., BA230, cyanate ester equivalent: 232), a cyanate resin (manufactured by Lonza Japan Co., Ltd., DT-4000, DT-7000) containing a dicyclopentadiene structure represented by the following formula (4).

[In the formula, n is an average value expressed by any numerical value (0 to 20 is preferable)].

(where n is the average value expressed as a value from 0 to 5).

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

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 anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)- 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyrogallanoic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride , oxyphthalic anhydride, 3,3'-4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro) -2,5-dioxy-3-furanyl)-naphthalene[1,2-C]furan-1,3-dione, ethylene glycol bis(dehydrated trimellitate), styrene and Malay Styrene after acid copolymerization. A polymer type acid anhydride such as maleic acid resin.

The resin composition of the present invention has a ratio of the total number of epoxy groups of the epoxy resin to the total of the reactive groups of the curing agent from the viewpoint of improving the mechanical strength or water resistance of the cured product of the resin composition. : 0.2~1:2 is better, preferably 1:0.3~1:1.5, and more preferably 1:0.4~1:1. The total number of epoxy groups of the epoxy resin present in the resin composition is obtained by dividing the solid mass of each epoxy resin by the value of the epoxy equivalent as the total value of all the epoxy resins, and the so-called hardener reaction. The total number of bases is the value obtained by dividing the solid content of each hardener by the equivalent of the reactive base as the total of all the hardeners.

<Inorganic fillers surface treated with bis(alkoxydecane)amine>

The bis(alkoxydecane)amine of the inorganic filler surface-treated with bis(alkoxydecane)amine used in the present invention is not particularly limited, and may be a bis(alkoxy group) having an amine group and an alkoxy group. Decane) amine. From the viewpoint of preserving the balance between stability and reactivity in the varnish resin, it is preferred that the amine group is a quaternary amine group. From the viewpoint of improving the peel strength, it is preferred that the alkoxy group having 2 to 3 atoms per alkoxy group is used. Further, the alkoxy group may also be a modified one.

The molecular weight of the bis(alkoxydecane)amine is preferably 260 or more, more preferably 280 or more, and still more preferably 300 or more from the viewpoint of suppressing volatilization during surface treatment or drying. On the other hand, from the viewpoint of appropriate reactivity, it is preferably 2,000 or less, more preferably 1700 or less, still more preferably 1400 or less. The commercially available product is "KBM666P" (bis(trimethoxydecylpropyl)amine, molecular weight 341) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The inorganic filler to be surface-treated with bis(alkoxydecane)amine used in the present invention is not particularly limited, and examples thereof include cerium oxide, aluminum, barium sulfate, talc, clay, mica powder, aluminum hydroxide, and magnesium hydroxide. Calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium acidate, barium zirconate, calcium zirconate, and the like. Among them, cerium oxide such as amorphous cerium oxide, pulverized cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide, spherical cerium oxide, etc., preferably The molten cerium oxide and the spherical cerium oxide which reduce the surface roughness of the insulating layer are preferred, and the spherical molten cerium oxide is more preferable. One type or two or more types may be used in combination.

The average particle diameter of the inorganic filler is not particularly limited, and the upper limit of the average particle diameter of the inorganic filler is preferably 5 μm or less and 4 μm or less from the viewpoint of forming a low roughness on the surface of the insulating layer and forming a fine line. Preferably, it is preferably 3 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.8 μm or less, and particularly preferably 0.6 μm or less. On the other hand, when the lower limit of the average particle diameter of the inorganic filler is from the resin composition to the varnish resin, the viscosity of the varnish increases and the workability is prevented from decreasing, preferably 0.01 μm or more, and 0.03 μm or more. 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 diffraction by laser. Determine by scattering method. Specifically by laser diffraction. In the scattering type particle size distribution measuring apparatus, the particle size distribution of the inorganic filler is prepared on a volume basis, and the median diameter can be measured as an average particle diameter. It is preferred to use an inorganic filler to be dispersed in water via ultrasonic waves. As a laser diffraction. As the scattering type particle size distribution measuring apparatus, LA-750 or the like manufactured by Horiba, Ltd. can be used.

The content of the inorganic filler is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is preferably 90% by mass or less from the viewpoint of preventing the cured product from becoming brittle or preventing the peel strength from being lowered. It is preferably 85 mass% or less, more preferably 80 mass% or less, and still more preferably 75 mass% or less. On the other hand, from the viewpoint of lowering the thermal expansion coefficient of the cured product, it is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more.

Inorganic filler material surface treated with bis(alkoxydecane)amine The amount of the surface treatment is not particularly limited, and it is preferred that the bis(alkoxydecane)amine is surface-treated at 0.05 to 5 parts by mass, and preferably 0.1 to 4 parts by mass, based on 100 parts by mass of the inorganic filler. It is more preferable to perform surface treatment with 0.2 to 3 parts by mass, and it is more preferable to perform surface treatment with 0.3 to 2 parts by mass.

Further, in the inorganic filler surface-treated with bis(alkoxydecane)amine, by analyzing the surface composition of the inorganic filler, the presence of carbon atoms is confirmed, and the amount of carbon per unit surface area of the inorganic filler can be determined. . For the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

Specifically, a sufficient amount of MEK was added as a solvent to the inorganic filler surface-treated with bis(alkoxydecane)amine, and ultrasonically washed at 25 ° C for 5 minutes. After removing the supernatant liquid and drying the solid content, the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. For the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The amount of carbon per unit surface area of the inorganic filler is 0.05 mg/m from the viewpoint of improving the dispersibility of the inorganic filler or the arithmetic mean roughness and root mean square roughness after the wet roughening step of the cured product. More preferably, m ² or more is preferably 0.1 mg/m ² or more, more preferably 0.15 mg/m ² or more, still more preferably 0.2 mg/m ² or more. On the other hand, from the viewpoint of preventing the melt viscosity of the varnish resin or the increase in the melt viscosity of the film form, it is preferably 1 mg/m ² or less, more preferably 0.75 mg/m ² or less, and preferably 0.5 mg/m ² or less. Better.

An inorganic filler surface-treated with bis(alkoxydecane)amine after surface treatment of the inorganic filler by bis(alkoxydecane)amine It is preferably added to the resin composition. At this time, the dispersibility of the inorganic filler can be further improved.

The surface treatment method of the inorganic filler which is surface-treated with bis(alkoxydecane)amine is not particularly limited, and examples thereof include a dry method or a wet method. In the dry method, the inorganic filler is placed in a rotary mixer, and an alcohol solution or an aqueous solution of bis(alkoxydecane)amine is dropped or sprayed while stirring, and then stirred, and classified by a sieve. Thereafter, it can be obtained by dehydrating condensation of bis(alkoxydecane)amine with an inorganic filler by heating. In the wet method, a slurry of an inorganic filler and an organic solvent is added while stirring, and bis(alkoxydecane)amine is added, and after stirring, it is filtered, dried, and classified by a sieve. Thereafter, it can be obtained by dehydrating and condensing a bis(alkoxydecane)amine with an inorganic filler by heating. Further, an overall blending method in which a bis(alkoxydecane)amine is added to the resin composition may be used.

<hardening accelerator>

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

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. An amine compound such as ginseng (dimethylaminomethyl) phenol or 1,8-difluorenebicyclo(5,4,0)-undecene (hereinafter abbreviated as DBU). Combinable One type or two or more types are used.

The lanthanide hardening accelerator is not particularly limited, and examples thereof include dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl hydrazine, and 1-(o-toluene).胍, dimethyl hydrazine, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentylmethyl hydrazine, 1,5,7-triazabicyclo[4.4.0] sunflower-5-ene, 7-A 1,-,5,7-triazabicyclo[4.4.0] syl-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecane guanidine 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-toluene)biguanide, and the like. These may be used in combination of one type or two or more types.

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-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole , 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4- Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate 2,4-Diamine-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamine-6-[2'-undecylimidazole -(1')]-ethyl-s-triazine, 2,4-diamine-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s Triazine, 2,4-diamine-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine iso-cyanuric acid adduct, 2-phenylimidazole Cyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a]benzimidazole, 1-dodecyl-2-methyl An imidazole compound such as benzyl-3-benzylimidazole, 2-methylimidazoline or 2-phenylimidazoline, and an imidazole compound and an epoxy resin adduct. These may be used in combination of one type or two or more types.

The oxime-based hardening accelerator is not particularly limited, and examples thereof include triphenylphosphine, bismuth borate compound, tetraphenylphosphonium tetraphenylboronic acid, n-butylphosphonium tetraphenylboronic acid, and tetrabutyl samarium alkanoate. (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. These may be used in combination of one type or two or more types.

In the resin composition of the present invention, the content of the curing accelerator (excluding the metal-based hardening accelerator) is preferably in the range of 0.005 to 1% by mass in the case where the non-volatile content in the resin composition is 100% by mass. A range of 0.01 to 0.5% by mass is preferred. Within this range, thermal hardening can be made more efficient and the preservation stability of the varnish resin can be improved.

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 organic cobalt complexes such as cobalt(II) acetate, cobalt(III) acetate, and copper (II) copper pyruvate. Organic zinc complex such as zinc acetylate (II), organic iron complex such as iron(III) pyruvate, and organic nickel complex of nickel(II) acetate An organic manganese complex such as acetaminophen (II) pyruvate or the like. Examples of the organic metal salt include zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used in combination of one type or two or more types.

In the resin composition of the present invention, a metal-based hardening accelerator When the amount of the non-volatile component in the resin composition is 100% by mass, the content of the metal from the metal-based curing catalyst is preferably in the range of 25 to 500 ppm, and preferably in the range of 40 to 200 ppm. In this range, the adhesion to the surface of the insulating layer not only forms an excellent conductor layer, but also improves the storage stability of the varnish resin.

<Thermoplastic resin>

In the resin composition of the present invention, by further containing a thermoplastic resin, the mechanical strength of the cured product can be improved, and the film forming ability for use in the form of the film can be further improved. Examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyimine resin, a polyamide amide resin, a polyether phthalimide resin, a polyfluorene resin, a polyether oxime resin, and a polycondensation. The phenyl ether resin, the polycarbonate resin, the polyether ether ketone resin, and the polyester resin are particularly preferably a phenoxy resin or a polyvinyl acetal resin. These thermoplastic resins may be used singly or in combination of two or more. The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000. Further, in the present invention, the weight average molecular weight is measured by gel permeation chromatography (GPC) (in terms of polystyrene). For the weight average molecular weight measured by the GPC method, LC-9A/RID-6A manufactured by Shimadzu Corporation was used as a measuring device, and Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. was used. The column, chloroform, etc. were used as the mobile phase, and the column temperature was measured at 40 ° C, and was calculated using a standard polystyrene calibration line.

The resin composition of the present invention is used in combination with a thermoplastic resin The content of the thermoplastic resin in the resin composition is not particularly limited, and is preferably 100% by mass based on the nonvolatile content of the resin composition, preferably 0.1 to 10% by mass, and preferably 0.5 to 5% by mass. When it is in this range, the film forming ability or the effect of improving the mechanical strength can be exerted, and the increase in the melt viscosity or the roughness of the surface of the insulating layer after the wet roughening step can be reduced.

<Rubber Particles>

Further, by containing the rubber particles, the resin composition of the present invention can improve the plating peel strength, improve the drilling processability, reduce the dielectric loss, and obtain the effect of stress relaxation. The rubber particles obtained by use in the present invention are not dissolved in the organic solvent to be used, for example, when the varnish of the resin composition is prepared, and are not compatible with an epoxy resin or the like. Therefore, the rubber particles are present in a varnish of the resin composition of the present invention in a dispersed state. In such a rubber particle, the molecular weight of the rubber component is generally increased to such an extent that it is not dissolved in an organic solvent or a resin, and is prepared in a particulate form.

Preferable examples of the rubber particles which can be used in the present invention include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and propylene rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer, for example, a shell layer of an outer layer is composed of a glassy polymer, a core layer of an inner layer is composed of a rubbery polymer, or an outer layer. The shell layer is composed of a glassy polymer, the intermediate layer is composed of a rubbery polymer, and the core layer is composed of a glassy polymer. Glassy polymer layer, for example, methyl methacrylate It is composed of a polymer or the like, and the rubber-like polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Two or more types of rubber particles can be used in combination. Specific examples of the core-shell type rubber particles include Staphy Lloyd AC3832, AC3816N, AC3401N, IM-401 modified 7-17 (trade name, Gantsu Chemical Co., Ltd.), Metablen KW-4426 (trade name, Mitsubishi Rayon) ))). Specific examples of the crosslinked styrene butadiene rubber (NBR) particles are XER-91 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles are XSK-500 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the propylene rubber particles are 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 to be blended is preferably in the range of 0.005 to 1 μm, 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 an ultrasonic wave or the like in a suitable organic solvent, and a particle size distribution of the rubber particles is produced on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). The median diameter was measured as the average particle diameter.

The content of the rubber particles is preferably from 0.05 to 10% by mass, more preferably from 0.5 to 5% by mass, based on 100% by mass of the nonvolatile matter in the resin composition.

<flammable agent>

The resin composition of the present invention is further imparted by containing a flame retardant Flame retardant. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyoxygen-based flame retardant, and a metal hydroxide. Examples of the organophosphorus-based flame retardant include a phenanthroline phosphorus compound such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., and a phosphorus-containing benzoxazine compound such as HFB-2006M manufactured by Showa Polymer Co., Ltd. , Ajinomoto Fine-Techno (share) made by Reofos30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, Beixing Chemical Industry Co., Ltd. Phosphate compound of TPPO, PPQ, Claliant Co., Ltd., PX200 manufactured by Daeba Chemical Co., Ltd., FX289, FX305, TX0712, etc. made by Nippon Steel Chemical Co., Ltd. A phosphorus-containing phenoxy resin such as ERF001 manufactured by Nippon Steel Chemical Co., Ltd., or a phosphorus-containing epoxy resin such as YL7613 manufactured by Mitsubishi Chemical Corporation. Examples of organic nitrogen-containing phosphorus compounds include phosphate phthalamide compounds such as SP670 and SP703 manufactured by Shikoku Chemicals Co., Ltd., SPB100 manufactured by Otsuka Chemical Co., Ltd., SPE100, and FP-series manufactured by Fushimi Pharmaceutical Co., Ltd. Such as phosphazene compounds and the like. Examples of the metal hydroxide include magnesium hydroxide such as UD65, UD650, and UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308, and B-made by Baiya Industrial Co., Ltd. 303, aluminum hydroxide, etc. such as UFH-20.

The content of the flame retardant is preferably from 0.5 to 10% by mass, and more preferably from 1 to 5% by mass, based on 100% by mass of the nonvolatile component in the resin composition.

<Other ingredients>

The resin composition of the present invention may be blended with other components as needed in order not to hinder the effects of the present invention. Examples of the other component include an ethylene benzyl compound, a propylene compound, a maleic imine compound, a thermosetting resin such as a blocked isocyanate compound, an organic filler such as a cerium powder, a nylon powder, or a fluorine powder, and ORBEN, BENTON. Adhesive imparting agent such as tackifier, polyfluorene-based, fluorine-based or polymeric antifoaming agent or leveling agent, imidazole-based, thiazole-based, triazole-based or decane coupling agent, and anthraquinone . Blue, phthalocyanine. Green, iodine. A coloring agent such as green, disazo yellow or carbon black, a decane coupling agent, a titanate coupling agent, a surface treatment agent such as a decazane compound, or the like. Further, when the surface treatment agent is used, the bis(alkoxydecane)amine is co-bonded to the surface of the inorganic filler through the surface treatment agent.

The resin composition of the present invention may be appropriately mixed with the above components, and may be mixed by a three-roller, a ball mill, a bead mill, a sand mixer or the like, or a stirring method such as an ultra-mixer or a planetary mixer, as the case requires. Mix or mix to make adjustments. Further, by adding an organic solvent, it can be adjusted even if it is a varnish resin.

In the resin composition of the present invention, since the arithmetic mean roughness of the surface of the insulating layer is low and the root mean square roughness is small in the wet roughening step, a plated conductor layer having sufficient peeling strength can be formed, so that in the multilayer layer In the manufacture of a printed wiring board, a resin composition for forming an insulating layer (a resin composition for an insulating layer of a multilayer printed wiring board) can be suitably used, and it is more suitable to cooperate as a resin for forming a conductor layer by plating. The composition is used (resin group for insulating layer of a multilayer printed wiring board formed by plating to form a conductor layer) Adult) That is, it is suitable as a resin composition for layering of a multilayer printed wiring board.

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

The upper limit of the arithmetic mean roughness (Ra value) is preferably 300 nm or less for the transmission loss of the electronic signal, preferably 250 nm or less, more preferably 230 nm or less, more preferably 210 nm or less, and 190 nm or less. More preferably, it is particularly excellent below 170 nm, particularly excellent below 160 M, and particularly excellent below 150 nm. The lower limit of the arithmetic mean roughness (Ra value) is preferably 10 nm or more, more preferably 20 nm or more, more preferably 30 nm or more, more preferably 40 nm or more, and more preferably 50 nm or more from the viewpoint of stable peel strength. good.

Since the root mean square roughness (Rq value) reflects the local state of the surface of the insulating layer, it was found that by understanding the Rq value, it was confirmed that a smooth insulating layer surface was formed in a minute range. The upper limit of the root mean square roughness (Rq value) forms a smooth surface of the insulating layer in a small range, preferably 500 nm or less, more preferably 450 nm or less, more preferably 400 nm or less, and even more preferably 350 nm or less. It is particularly good below 300 nm, especially below 250 nm, and even better below 200 nm. The lower limit of the root mean square roughness (Rq value) is preferably 20 nm or more, more preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more from the viewpoint of stable peel strength. More than 60nm is especially good.

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 peeling strength (peeling strength) of the plated conductor layer described later. >The method of measurement described is to be mastered.

The peeling strength is preferably 0.35 kgf/cm or more, and preferably 0.4 kgf/cm or more, because the insulating layer and the conductor layer are sufficiently in close contact with each other. It is preferably 0.45 kgf/cm or more, more preferably 0.48 kgf/cm or more. The upper limit of the peel strength is preferably as high as possible, and is not particularly limited, and is generally 1.5 kgf/cm or less.

The use of the resin composition of the present invention is not particularly limited, and it can be used for a sheet-like laminate such as a film or a prepreg, a circuit board (for laminate use, multilayer printed wiring board use, etc.), a solder resist, a filler, and A resin composition such as a grain-forming material, a semiconductor sealing material, a hole-filling resin, or a component-embedded resin is widely used as an essential component. Although the resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, it is generally industrially preferable to use a sheet-like laminate such as a film or a prepreg. The softening point of the resin composition is preferably from 40 to 150 ° C from the viewpoint of lamination property of the sheet-like laminate.

<Sheet laminate]

(following the film)

The adhesive film of the present invention is a method known to the art leader, for example, by dissolving a resin composition in an organic solvent to prepare a varnish resin. The varnish resin is applied to a support by a die coater, and is dried by heating or blowing hot air to form an organic resin layer, thereby producing a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and ethyl acetate, butyl acetate, celecoxib acetate, propylene glycol monomethyl ether acetate, and carbitol acetic acid. Acetate such as ester, carbitol, butyl carbitol, etc., aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, A guanamine-based solvent such as N-methylpyrrolidone. Two or more types of organic solvents can be used in combination.

The drying condition is not particularly limited, and the content of the organic solvent in the resin composition layer is 10% by mass or less, and 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 varnish containing 30 to 60% by mass of the organic solvent is dried at 50 to 150 ° C for about 3 to 10 minutes. A resin composition layer is formed.

The thickness of the resin composition layer formed in the film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the circuit substrate having the conductor layer is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm. From the viewpoint of film formation, it is preferably 15 to 80 μm.

Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, and polyesters such as polyethylene terephthalate (hereinafter abbreviated as "PET") and polyethylene naphthalate. Film, polycarbonate Various plastic films such as films and polyimide films. Further, a release paper, a metal foil such as a copper foil or an aluminum foil, or the like can also be used. Among them, from the viewpoint of diversity, a plastic film is preferred, and a polyethylene terephthalate film is preferred. The support and the protective film described later may be subjected to a surface treatment such as a dry process or a corona treatment. Further, a mold release agent such as a polyoxymethylene resin release agent, an alkyd resin release agent, or a fluororesin release agent may be applied to the release treatment.

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

The support of the resin composition layer has no adhesive surface, and the protective film can be laminated according to the support. The thickness of the protective film is not particularly limited and is, for example, 1 to 40 μm. Adhesion or flaws of dust or the like on the surface of the resin composition layer can be prevented by laminating the protective film. The film can then be crimped to the collector.

(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 produced by semi-curing by heating. In other words, the resin composition of the present invention is a state prepreg immersed in a sheet-like reinforcing substrate. As the flaky reinforcing substrate, a fiber for prepreg such as glass cloth or aromatic polyamide fiber can be used as a fiber formed of a usual fiber. Further, it is preferred to form a prepreg in the support.

The hot melt method is not only an organic solvent in which the resin composition is dissolved, but is deposited on a sheet-like reinforcing substrate by sputtering on a support, or directly applied to a sheet-like reinforcing substrate by a die coater. Manufacturing prepreg The method. Further, the solvent method and the film are dissolved in an organic solvent to prepare a varnish resin in the same manner, and the varnish is impregnated with the flaky reinforcing substrate, and the varnish resin is immersed in the flaky reinforcing substrate to be impregnated. This is a method of post-drying. Further, the adhesive film was prepared by continuous thermal lamination under heating and pressing conditions on both sides of the sheet-like reinforcing substrate. A support or a protective film or the like can also be used in the same manner as the adhesive film.

<Multilayer printed wiring board using sheet-like laminate material>

Next, an example of a method of manufacturing a multilayer printed wiring board using the prepared sheet-like laminate material as described above will be described.

First, the sheet-like laminate is laminated (laminated) on one side or both sides of the circuit board using a vacuum laminator. The substrate used for the circuit board is, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or the like. Further, the circuit board here is a conductor layer (circuit) formed by processing a pattern on one side or both sides of the substrate as described above. Further, a multilayer printed wiring board formed by alternately laminating a conductor layer and an insulating layer, and a single-sided or double-sided pattern of the outermost layer of the multilayer printed wiring board is patterned to form a conductor layer (circuit), which is also included in the so-called circuit substrate. . Further, the surface of the conductor layer may be subjected to pre-roughening treatment by blackening treatment, copper etching, or the like.

In the above lamination, when the sheet-like laminate has a protective film, after removing the protective film, if necessary, the sheet-like laminate and the circuit substrate are heated in advance, and the sheet-like laminate is pressurized and heated to be laminated on the circuit. Substrate. The sheet-like laminate of the present invention is suitably used in a method of laminating a circuit substrate under reduced pressure by vacuum lamination. The conditions for lamination are not particularly limited. For example, the pressing temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressing pressure (laminating pressure) is preferably 1 to 11 kgf/cm ² (9.8 × 10 ⁴ ~ 107.9 × 10 ⁴ N/m ² ), the pressing time (lamination time) is preferably 5 to 180 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less. Further, the lamination method may be a batch type or a roll continuous type. Vacuum lamination can be carried out using a commercially available vacuum laminator. As a commercially available vacuum laminating machine, for example, Vacuum Applicator manufactured by Nichigo-Morton Co., Ltd., vacuum pressurizing laminator manufactured by Nihon Seiki Co., Ltd., Hiroshi Industrials Roller Dry Coatinger, Hitachi Air Ishi (stock) vacuum laminating machine, etc.

After the sheet-like laminate is laminated on the circuit board, after cooling to room temperature, the support is peeled off when the support is peeled off, and a cured product is formed by thermally curing the resin composition, whereby an insulating layer can be formed on the circuit board. The conditions of the heat curing are appropriately selected depending on the kind and content of the resin component in the resin composition, and are preferably from 20 minutes to 180 minutes at 150 ° C to 220 ° C, more preferably from 30 to 120 minutes at 160 ° C to 210 ° C. The range of choices. After the formation of the insulating layer, the support is not peeled off before hardening, and may be peeled off as necessary.

Further, the sheet-like laminate may be laminated on one side or both sides of the circuit board using a vacuum press. A lamination step of heating and pressurization under reduced pressure can be carried out using a general vacuum hot stamping machine. For example, pressing is performed from the side of the support layer by a metal plate such as a heated SUS plate. The press condition is such that the degree of pressure reduction is usually 1 × 10 ^-2 MPa or less, preferably 1 × 10 ^-3 MPa or less. Although heating and pressurization may be performed in one stage, it is preferable to perform separation by two or more conditions from the viewpoint of controlling the bleeding of the resin. For example, it is preferable to apply a one-stage press to a temperature of 70 to 150 ° C, a pressure of 1 to 15 kgf/cm ² , a two-stage press for a temperature of 150 to 200 ° C, and a pressure of 1 to 40 kgf/cm ² . . The time of each stage is preferably 30 to 120 minutes. An insulating layer can be formed on the circuit substrate by thermally hardening the resin composition layer. 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.

Next, the insulating layer formed on the circuit substrate is subjected to a hole-cutting process to form a through hole and a through hole. The burrowing process is performed by a well-known method such as drilling, laser, plasma, etc., and may be combined according to the situation, and the laser is processed by a laser such as a carbon dioxide gas laser or a YAG laser. The most general method. When the support is not peeled off before the hole-cutting process, peeling is performed here.

Next, the surface of the insulating layer is roughened. The dry roughening treatment is, for example, a plasma treatment, and the wet roughening treatment is exemplified by a swelling treatment of an expansion liquid, a roughening treatment by an oxidizing agent, and a method of neutralizing a neutralization liquid. In the wet roughening treatment, it is preferable to form a convex and concave fixing on the surface of the insulating layer, and to remove the dross in the through hole. The insulating layer is immersed in an expansion liquid at 50 to 80 ° C for 5 to 20 minutes (preferably 55 to 70 ° C for 8 to 15 minutes) by expansion treatment of the expansion liquid. Examples of the swelling liquid include an alkali solution, a surfactant solution, and the like, and an alkali solution is preferred. Examples of the alkali solution include sodium hydroxide solution and hydrogen and oxygen. Calcium solution, etc. Examples of the commercially available swelling liquid include Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, and the like manufactured by Atotech Japan Co., Ltd. The oxidizing agent is subjected to roughening treatment to immerse the insulating layer at 60 to 80 ° C for 10 to 30 minutes (preferably at 70 to 80 ° C for 15 to 25 minutes) by immersing in an oxidizing agent solution. Examples of the oxidizing agent include an alkaline permanganic acid solution of calcium permanganate or sodium permanganate dissolved in an aqueous sodium hydroxide solution, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. Further, the concentration of the 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. An alkaline permanganic acid solution such as Conpact CP, Dozing Solution Securiganth P, and the like. The neutralization solution is neutralized at 30 to 50 ° C for 3 to 10 minutes (preferably 3 to 8 minutes at 35 to 45 ° C) by immersion in a neutralizing solution. The neutralization solution is preferably an acidic aqueous solution, and as a commercial product, Deduction Solution manufactured by Atotech Japan Co., Ltd. can be cited. Securiganth P.

Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. For dry plating, a well-known method such as vapor deposition, sputtering, or ion deposition can be used. The wet plating method combines electroless plating and electrolytic plating to form a conductor layer, and the conductor layer is a method of forming a reverse-pattern plating resist to form a conductor layer only by electroless plating. Subsequent pattern formation methods, for example, using a substractive method, a semi-additive method, etc., which are well known to those skilled in the art, repeat the above-described series of steps in a plurality of times to make the layering become a multi-stage Laminated multilayer printed wiring boards. The invention is suitable for use in the buildup of multilayer printed wiring boards because of low roughness and high peeling.

<semiconductor device>

A semiconductor device can be fabricated using the multilayer printed wiring board of the present invention. In the conductive portion of the multilayer printed wiring board of the present invention, a semiconductor device can be fabricated by mounting a semiconductor wafer. The so-called "conducting portion" can be "the portion that conducts electrical signals on a multilayer printed wiring board". This portion can be a surface and can be used for the embedded portion. Further, the semiconductor wafer is not particularly limited as a circuit element using a semiconductor as a material.

The method of mounting the semiconductor wafer in the manufacture of the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can effectively function, and specific examples thereof include a wire bonding method, a flip chip mounting method, and a pass-through method. A method of mounting bumps (BBUL), a method of mounting via an anisotropic conductive film (ACF), a method of mounting via a non-conductive film (NCF), and the like.

Example

The invention will be specifically described below by way of examples, but the invention is not limited to the examples. And "parts" means parts by mass.

<Measurement method. Evaluation method>

First, explain the various measurement methods. Evaluation method.

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

(1) Basic processing of the inner layer circuit substrate

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

(2) followed by lamination of the film

The adhesive film produced in the examples and the comparative examples was laminated on both sides of the inner layer circuit board using a batch type vacuum pressure bonding machine MVLP-500 (trade name, manufactured by a famous machine). The lamination was carried out under reduced pressure for 30 seconds to bring the gas pressure to 13 hPa or less, and thereafter 30 seconds at 100 ° C and a pressure of 0.74 MPa by pressing.

(3) Hardening of resin composition

The laminated film was cured at 100 ° C for 30 minutes, and the resin composition was cured at 180 ° C for 30 minutes to form an insulating layer, after which the PET film was peeled off.

(4) roughening treatment

The insulating layer inner layer circuit substrate was immersed in Atotech Japan's Swelling Dip Securiganth P (ethylene glycol ether, sodium hydroxide aqueous solution) containing diethylene glycol monobutyl ether, and 10 minutes at 80 ° C. Expansion fluid. Secondly, the Concentrate of Atotech Japan is immersed. Compact P (KMnO4: 60g/L, NaOH: 40g/L in water), 20° at 80°C The roughening liquid. Finally, impregnate Atotech Japan's Reduction solution. Securiganth P (aqueous solution of sulfuric acid) was neutralized at 40 ° C for 5 minutes. 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 order to form a circuit on the surface of the insulating layer, the inner layer circuit board was immersed in a solution for electroless plating containing PdCl ₂ at 40 ° C for 5 minutes, and then, the electroless copper plating solution was immersed at 25 ° C for 20 minutes. After annealing at 150 ° C for 30 minutes, annealing treatment was performed to form an etching resist, and after forming by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, the annealing treatment was carried out at 200 ° C for 60 minutes. The peel strength (peel strength) of the plated conductor layer of this circuit board was measured.

[Measurement of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) after roughening]

The Ra value and the Rq value were determined from a VSI contact mode and a 50-fold lens using a non-contact type surface roughness meter (WYKO NT3300 manufactured by VEECO Instruments) by a measurement range of 121 μm × 92 μm. Further, the measurement was performed by obtaining an average value of 10 points.

[Measurement of Peel Strength (Peel Strength) of Plated Conductor Layer]

Cutting a portion of a conductor layer of a circuit board with a width of 10 mm and a length of 100 mm The strip was clamped by a gripper (T.S.E., AUTOCOM type tester AC-50C-SL), and stripped at a distance of 50 mm/min in the vertical direction at room temperature of 35 mm. The weight of time (kgf/cm).

[Inorganic filler after use]

With respect to the inorganic filler 1: spherical cerium oxide ("SFP-130MC" manufactured by Electrochemical Industry Co., Ltd., average particle diameter: 0.6 μm), 100 parts, bis(alkoxydecane)amine (Shin-Etsu Chemical Co., Ltd.) The "KBM666P", molecular weight 341) was treated with 0.5 part of the surface, and the amount of carbon per unit surface area was 0.24 mg/m ² .

Inorganic filler 2: A spherical cerium oxide ("SFP-130MC" manufactured by Electrochemical Industry Co., Ltd., average particle diameter: 0.6 μm) which has not been surface-treated.

With respect to the inorganic filler 3: spherical cerium oxide ("SFP-130MC_" manufactured by Electrochemical Industry Co., Ltd., average particle diameter: 0.6 μm) 100 parts, phenylamine decane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") Molecular weight 255) The amount of carbon per unit surface area of the latter was 0.30 mg/m ² with 0.5 part surface treatment.

With respect to the inorganic filler 4: 100 parts of spherical cerium oxide ("SFP-130MC" manufactured by Electrochemical Industry Co., Ltd., average particle diameter: 0.6 μm), epoxy decane (Shin-Etsu Chemical Co., Ltd., "KBM403", The molecular weight of 236) was 0.5 parts by surface, and the amount of carbon per unit surface area of the latter was 0.19 mg/m ² .

With respect to the inorganic filler 5: 100 parts of spherical cerium oxide ("SO-C1" manufactured by ADMATECHS, average particle diameter: 0.24 μm), bis(alkoxydecane)amine (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM666P", molecular weight 341) The surface amount of carbon per unit surface area of the latter was 1.03 mg/m ² with 1.0 part of the surface.

With respect to the inorganic filler 6 : 100 parts of spherical cerium oxide ("SO-C1" manufactured by ADMATECHS, average particle diameter: 0.24 μm), bis(alkoxydecane)amine (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM666P", molecular weight 341) The amount of carbon per unit surface area of the latter was 2.06 mg/m ² with 2.0 parts of surface treatment.

In relation to the inorganic filler 7: spherical cerium oxide ("SFP-130MC" manufactured by Electrochemical Industry Co., Ltd., average particle diameter: 0.6 μm), 100 parts, bis(alkoxydecane)amine (Shin-Etsu Chemical Co., Ltd.) "KBM666P", molecular weight 341) The amount of carbon per unit surface area of the latter was 0.40 mg/m ^{2 in a} surface treatment of 0.8 parts.

<Example 1>

10 parts of naphthalene type epoxy resin ("HP4032SS" manufactured by DIC Co., Ltd.), liquid bisphenol type epoxy resin (ZX1059, manufactured by Nippon Steel Chemical Co., Ltd.), bisphenol A type and bisphenol F type 1:1 mixed product) 5 parts, naphthol type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Co., Ltd.) 20 parts, phenoxy resin (weight average molecular weight 35000, Mitsubishi Chemical Corporation) YL7553BH30", a 1:1 solution of 30% by mass of MEK and cyclohexanone in a nonvolatile content) was placed in 50 parts of a solvent naphtha, stirred and heated to dissolve, and then cooled at room temperature. Next, an active ester compound ("HPC8000-65T" manufactured by DIC), an active ester equivalent of 223, a toluene solution having a solid content of 65%, and 10 parts of a prepolymer of bisphenol A dicyanate (Lonza Japan) )system" 20 parts of a phenol novolac type polyfunctional cyanate resin ("3030" manufactured by Lonza Japan Co., Ltd.) and a cyanate ester equivalent of about 133, BA230S75", a Cyanate ester equivalent of about 232, and a nonvolatile content of MEK solution of 20% by mass. 10 parts of MEK solution containing 85% by mass of non-volatile matter), 4 parts of rubber particles (manufactured by Gantsu Chemical Co., Ltd., StaphyLloyd AC3816N) were placed in a solvent naphtha 16 parts and allowed to swell at room temperature for 12 hours, and a flame retardant was added ( "HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxy-10-phosphaphenanthrene-10-oxide, average particle size 1 μm) Parts, hardening accelerator (4-dimethylaminopyridine, MEK solution with a solid content of 4% by mass) 0.5 parts, hardening accelerator (Tokyo Chemical Co., Ltd., cobalt (III) acetoacetate, solid content 1 mass 4.5 parts of % MEK solution), and further 150 parts of the inorganic filler 1 were mixed, and uniformly dispersed in a rotary mixer to obtain a varnish resin. Next, the varnish resin was uniformly coated on a die coater on a release surface of a polyethylene terephthalate film ("AL5" manufactured by LINTEC Co., Ltd., thickness: 38 μm) which was subjected to an alkyd-based release treatment. The coating was applied to a thickness of 40 μm after drying the resin composition layer, and dried at 80 to 110 ° C (average 95 ° C) for 5 minutes to obtain a film.

<Example 2>

10 parts of naphthalene type epoxy resin ("HP4032SS" manufactured by DIC Co., Ltd.), liquid bisphenol type epoxy resin (ZX1059, manufactured by Nippon Steel Chemical Co., Ltd.), bisphenol A type and bisphenol F type 1:1 mixed product) 5 parts, naphthol type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Co., Ltd.) 20 parts, phenoxy resin (weight average molecular weight 35000, Mitsubishi Chemical Corporation) YL7553BH30", a non-volatile content of 30% by mass of a 1:1 solution of MEK and cyclohexanone) 5 parts in a solvent 50 parts of naphtha was stirred and heated to dissolve, and then cooled to room temperature. Next, an active ester compound ("HPC8000-65T" manufactured by DIC), an active ester equivalent of 223, a toluene solution having a solid content of 65%, and 10 parts of a prepolymer of bisphenol A dicyanate (Lonza Japan) 20 parts of "BA230S75", MEK solution having a cyanate ester equivalent of about 232 and a nonvolatile content of 75% by mass), phenol novolac type polyfunctional cyanate resin ("3030" manufactured by Lonza Japan Co., Ltd., cyanate equivalent) About 133, a non-volatile 85 mass% MEK solution) 10 parts, rubber particles (Gantsu Chemical Co., StaphyLloyd AC3816N) 4 parts in solvent naphtha 16 parts at room temperature for 12 hours to expand, adding flame retardant (HCA-HQ), 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxy-10-phosphaphenanthrene-10-oxide, average particle size 1 μm 3 parts, hardening accelerator (4-dimethylaminopyridine, MEK solution with a solid content of 4% by mass) 0.5 parts, hardening accelerator (Tokyo Chemical Co., Ltd., cobalt (III) acetylpyruvate, solid content 4.5 parts of a 1% by mass MEK solution, and further 120 parts of the inorganic filler 5 were mixed and uniformly dispersed in a rotary mixer to obtain a varnish resin.

<Example 3>

5 parts of a naphthalene type epoxy resin ("HP4032SS" manufactured by DIC Co., Ltd.), a liquid bisphenol type epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type and bisphenol F type) 1:1 mixed product) 5 parts, crystalline bifunctional epoxy resin ("XX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185) 10 parts, biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) "NC3000H", epoxy equivalent of about 288) 20 parts, phenoxy resin (weight average molecular weight 35000, three 20 parts of "YL7553BH30" manufactured by Rigaku Chemical Co., Ltd., and a 1:1 solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass) were stirred and dissolved in 50 parts of solvent naphtha, and then cooled to room temperature. Next, a triazine-based phenolic curing agent (MEK solution of 60% solid content of "LA-7054" having a hydroxyl equivalent of 125 by DIC) was used, and a naphthalene type hardener (Nippon Steel Chemical Co., Ltd.) ) 15 parts of "SN-485" hydroxyl group equivalent of 215 of 60% solids in MEK solution), rubber particles (Gantsu Chemicals Co., Ltd., StaphyLloyd AC3816N) 4 parts in solvent naphtha 16 parts at room temperature 12 Inflated in an hour, and added a flame retardant (HCA-HQ, 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxy-10-phosphaphenanthrene-10, manufactured by Sanguang Co., Ltd. - part of an oxide, an average particle diameter of 1 μm), a hardening accelerator (4-dimethylaminopyridine, a MEK solution having a solid content of 4% by mass) of 0.5 part, and further mixing 120 parts of the inorganic filler 6 to be evenly mixed by a rotary mixer Disperse into a varnish resin.

<Example 4>

Liquid bisphenol type epoxy resin (ZX1059 made by Nippon Steel Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type), 10 parts of crystalline 2-functional epoxy resin (Mitsubishi) Chemical (stock) "YX4000HK", epoxy equivalent of about 185) 5 parts, dicyclopentadiene type epoxy resin ("HP7200H" manufactured by DIC), epoxy equivalent of about 275), phenoxy resin ( 15 parts by weight of molecular weight 35000, "YL7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., and a 1:1 solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass) 15 parts of the solvent naphtha was stirred and heated and dissolved. Cool until room temperature. Next, add an active ester compound (DICC) "HPC8000-65T" 40 parts of active ester equivalent 223, 65% solids in toluene solution, flame retardant (HCA-HQ, 10-(2,5-dihydroxyphenyl)-10-hydrogen group, manufactured by Sanguang Co., Ltd. -9-oxy-10-phosphaphenanthrene-10-oxide, average particle diameter 1 μm) 3 parts, hardening accelerator (4-dimethylaminopyridine, MEK solution having a solid content of 4% by mass) 3.5 parts, and further mixed 150 parts of the inorganic filler 7 was uniformly dispersed by a rotary mixer to obtain a varnish resin.

<Comparative Example 1>

A varnish resin was produced in the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 2. Next, an adhesive film was obtained in exactly the same manner as in Example 1.

<Comparative Example 2>

A varnish resin was produced in the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 3. Next, an adhesive film was obtained in exactly the same manner as in Example 1.

<Comparative Example 3>

A varnish resin was produced in the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 4. Next, an adhesive film was obtained in exactly the same manner as in Example 1.

The results are shown in Table 1.

From the results of Table 1, it was found that the resin composition of the example obtained a sufficient peel strength value at a low arithmetic mean roughness and a low root mean square roughness. Further, since the Rq value reflects the local state of the surface of the insulating layer, a dense rough surface is formed by the decrease in the Rq value. On the other hand, in the comparative example, the arithmetic mean roughness and the root mean square roughness become large, and the peel strength also becomes a small value.

Industrial availability

The present invention provides a resin composition capable of forming a plated conductor layer having sufficient peel strength, in which not only the arithmetic mean roughness of the surface of the insulating layer is low but also the root mean square roughness is small in the wet roughening step. Further, it is provided by using such a sheet-like laminate, a multilayer printed wiring board, or a semiconductor device. Further, it is provided in an electronic product such as a computer, a mobile phone, a digital camera, or a television, or a vehicle such as a locomotive, a car, a train, a ship, or an airplane.

Claims (15)

A resin composition characterized by comprising an epoxy resin, a hardener, and an inorganic filler surface-treated with bis(alkoxydecane)amine. The resin composition of claim 1, wherein the bis(alkoxydecane)amine comprises a secondary amine group. The resin composition of claim 1 or 2, wherein the bis(alkoxydecane)amine has a molecular weight of from 260 to 2,000. The resin composition of claim 1, wherein the bis(alkoxydecane)amine is bis(trimethoxydecylpropyl)amine. The resin composition of claim 1, wherein the inorganic filler has an average particle diameter of 0.01 to 5 μm. The resin composition of claim 1, wherein the inorganic filler is cerium oxide. In the resin composition of claim 1, wherein the non-volatile content in the resin composition is 100% by mass, the content of the inorganic filler is from 30 to 90% by mass. The resin composition of claim 1, wherein the bis(alkoxydecane)amine is surface-treated at 0.05 to 5 parts by mass based on 100 parts by mass of the inorganic filler. The resin composition of claim 1, wherein the inorganic filler has a carbon amount per unit surface area of 0.05 to 1 mg/m ² . The resin composition of claim 1, which is obtained by curing the resin composition to form an insulating layer, and roughening the surface of the insulating layer to have an arithmetic mean roughness of 300 nm or less and a root mean square roughness of 500 nm or less. The resin composition of claim 1, which is obtained by curing a resin composition to form an insulating layer, roughening the surface of the insulating layer, and having a peeling strength of the conductor layer and the insulating layer after plating is 0.35 kgf/cm or more. The resin composition of claim 1, which is a resin composition for a build-up layer of a multilayer printed wiring board. A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 12. A multilayer printed wiring board characterized in that an insulating layer is formed by the cured product of the resin composition of any one of claims 1 to 12. A semiconductor device characterized by the use of a multilayer printed wiring board of claim 14.