KR20120126019A - Resin composition - Google Patents

Abstract

PURPOSE: A resin composition with enhanced dielectric tangent, coefficient of thermal expansion and fire retardant characteristics is provided to have enough peeling strength and to maintain fire retardance and thermal expansion. CONSTITUTION: A resin composition contains an epoxy resin and phosphorous atom-containing active ester curing agent, and inorganic filler. The phosphorous atom-containing active ester curing agent is obtained from a condensation reaction between the phosphorous atom - containing hydroxy compound and carboxylic acid compound. If the resin composition has 100 mass% of non-volatile matte, 1-15 mass% of active phosphorous atom-containing active ester curing agent is contained. If the non-volatile matter among the resin composition is 100 mass%, 0.05-3 mass% of phosphorus is contained in the resin composition. The active ester curing agent is selected from a group composed of one or more compositions represented by chemical formula (1) to (3).

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. Moreover, it is related with the adhesive film, prepreg, multilayer printed wiring board, and semiconductor device containing the said resin composition.

In recent years, miniaturization and high performance of electronic devices have progressed, and in a multilayer printed wiring board, a buildup layer has been multilayered, and wiring refinement | miniaturization and high density were calculated | required.

Various attempts have been made to this. For example, Patent Document 1 discloses a resin composition containing an epoxy resin and an active ester resin. It is described that the insulating layer formed by these compositions can satisfy both dielectric properties and heat resistance. However, the performance was not necessarily satisfactory.

Patent Document 1: Japanese Patent Publication No. 2009-235165

The problem to be solved by the present invention is a resin composition capable of forming a plating conductor layer having a small arithmetic mean roughness on the surface of the insulating layer in a wet roughening process while maintaining dielectric tangent, thermal expansion coefficient, and flame retardancy, and having sufficient peeling strength. To provide.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors came to complete this invention in the resin composition containing an epoxy resin and a specific active ester hardening | curing agent.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin and an active ester curing agent containing (B) a phosphorus atom.

[2] The resin composition according to the above [1], wherein an active ester curing agent containing a phosphorus atom is obtained from a condensation reaction between a carboxylic acid compound and a phosphorus atom-containing hydroxy compound.

[3] The active ester curing agent containing a phosphorus atom (B) is represented by one or more selected from the group consisting of the following general formulas (1) to (3): the above-mentioned [1] or [2] Resin composition.

(In formula, R may be an alkyl group, an alkenyl group, an aralkyl group, an aryl group, and may have a substituent. R1 is an alkyl group containing a phosphorus atom, an alkenyl group containing a phosphorus atom, an aral containing a phosphorus atom. And a carboxyl group, an aryl group containing a phosphorus atom, a phosphazene skeleton, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, and may have a substituent. A hydroxyl group, a phenyl group, and a naphthyl group, and two R 2 's may be bonded to each other to form a cyclic group. N represents 1 to 10.)

(Wherein R4 is an alkyl group containing a phosphorus atom, an alkenyl group containing a phosphorus atom, an aralkyl group containing a phosphorus atom, an aryl group containing a phosphorus atom, a phosphazene skeleton, 9,10-dihydro-9- Oxa-10-phosphaphenanthrene 10-oxide may be mentioned and may have a substituent R3 may be an alkyl group, an alkenyl group, an aralkyl group, an aryl group, and may have a substituent R5 is hydrogen, Hydroxyl group, phenyl group, naphthyl group, n represents 1 to 10.)

(In formula, R <6> can mention an alkyl group, an alkenyl group, an aralkyl group, and an aryl group, and may have a substituent. R <7> represents the benzoyl group which may be substituted. N represents 1-10.)

[4] When the nonvolatile content in the resin composition is 100% by mass, the active ester curing agent containing (B) phosphorus atoms is 1 to 15% by mass, to any one of the above [1] to [3]. The resin composition described.

[5] The resin composition according to any one of the above [1] to [4], wherein the phosphorus content in the resin composition is 0.05 to 3 mass% when the nonvolatile content in the resin composition is 100 mass%.

[6] The resin composition according to any one of the above [1] to [5], further comprising (C) an inorganic filler.

[7] The resin composition according to any one of the above [1] to [6], further comprising (E) a curing agent.

[8] The ratio between the total number of epoxy groups of (A) epoxy resin and the total number of active ester curing agents containing atoms (B) and reactors of (E) curing agents is 1: 0.2 to 2. The resin composition in any one of 1]-[7].

[9] The resin composition is cured to form an insulating layer, and the peeling strength of the conductor layer and the insulating layer obtained by roughening and plating the surface of the insulating layer is 0.36 kgf / cm to 1.0 kgf / cm, and the resin composition is cured by The arithmetic mean roughness after forming an insulating layer and roughening the surface of the insulating layer is 10 nm-200 nm, and the average thermal expansion coefficient from 25 degreeC to 150 degreeC after hardening a resin composition and forming an insulating layer is 5 ppm-25 ppm. The resin composition as described in any one of said [1]-[8] characterized by the above-mentioned.

[10] An adhesive film, wherein the resin composition according to any one of [1] to [9] is layered on a support.

[11] A prepreg in which the resin composition according to any one of [1] to [9] is impregnated in a sheet-like reinforcing base material.

[12] A multilayer printed wiring board in which an insulating layer is formed of a cured product of the resin composition according to any one of [1] to [9].

[13] A semiconductor device comprising the multilayer printed wiring board according to [12] above.

By using a resin composition containing an epoxy resin and a specific active ester resin, a plating conductor layer having a small arithmetic mean roughness on the surface of the insulating layer in a wet roughening process while maintaining dielectric tangent, thermal expansion coefficient, and flame retardancy, and having sufficient peeling strength It was possible to provide a resin composition capable of forming a resin.

This invention is a resin composition characterized by containing the active ester hardening | curing agent containing (A) epoxy resin and (B) phosphorus atom.

&Lt; (A) Epoxy resin >

Although it does not specifically limit as an epoxy resin used for this invention, Bisphenol-A epoxy resin, Bisphenol F-type epoxy resin, Bisphenol S-type epoxy resin, Bisphenol AF-type epoxy resin, Phenol novolak-type epoxy resin, tert- butyl- Catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure Epoxy resin which has, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro ring containing epoxy resin, a cyclohexane dimethanol type epoxy resin, a trimethylol type epoxy resin, a halogenated epoxy resin, etc. are mentioned. These can also be used 1 type or in combination or 2 or more types.

Among them, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, butadiene structure from the viewpoint of improving heat resistance, improving insulation reliability, and improving adhesion to metal foil. Epoxy resins are preferred. Specifically, for example, bisphenol A type epoxy resin ("Epicoat 828EL", "YL980" by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin ("jER806H", "YL983U" by Mitsubishi Chemical Corporation), Naphthalene type bifunctional epoxy resin ("HP4032", "HP4032D", "HP4032SS" by DIC Corporation), naphthalene type four-functional epoxy resin ("HP4700", "HP4710" by DIC Corporation), naphthol type epoxy resin (Doto Chemical Co., Ltd. product "ESN-475V"), epoxy resin (butadiene chemical industry make "PB-3600") which has butadiene structure, epoxy resin (bihon structure) of Nippon Kayaku Co., Ltd. Manufacturing "NC3000H", "NC3000L", "NC3100", Mitsubishi Chemical Co., Ltd. "YX4000", "YX4000H", "YX4000HK", "YL6121"), Anthracene-type Epoxy Resin (Mitsubishi Chemical Co., Ltd. "YX8800" ), Naphthylene ether type epoxy resin ("EXA-7310", "EXA-7311", "EXA-7311L", "EXA7311-G3" by DIC Corporation), etc. are mentioned.

Although an epoxy resin may use 2 or more types together, it is preferable to contain the epoxy resin which has two or more epoxy groups in one molecule. In addition, an epoxy resin having two or more epoxy groups in one molecule and a liquid aromatic epoxy resin at a temperature of 20 ° C., and three or more epoxy groups in one molecule, and a solid aromatic epoxy resin at a temperature of 20 ° C. The containing embodiment is more preferable. In addition, the aromatic epoxy resin in this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator. When using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, when using a resin composition in the form of an adhesive film, the compounding ratio (the point which has moderate flexibility or the hardened | cured material of a resin composition has the appropriate breaking strength) The liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 2 by mass, more preferably 1: 0.3 to 1.8, and still more preferably 1: 0.6 to 1.5.

In the resin composition of this invention, when the non-volatile component in a resin composition is 100 mass% from a viewpoint of improving the mechanical strength and water resistance of the hardened | cured material of a resin composition, it is preferable that content of an epoxy resin is 3-40 mass%. It is more preferable that it is 5-35 mass%, and it is still more preferable that it is 10-30 mass%.

<(B) Active ester curing agent containing phosphorus atom>

The active ester curing agent containing the phosphorus atom (B) used in the present invention is not particularly limited as long as it has a phosphorus atom. Examples thereof include a phenol ester compound containing a phosphorus atom, a thiophenol ester compound containing a phosphorus atom, N-hydroxyamine ester compound containing a phosphorus atom, the compound in which the heterocyclic hydroxy group containing a phosphorus atom is esterified, benzoylate of a phosphazene phenol resin, 9,10- dihydro-9-oxa-10-force It has an ester group with high reaction activity, such as a phenyphene 10-oxide type | mold benzoylide, and says having the hardening effect of an epoxy resin. Especially, the compound which has 2 or more active ester group in one molecule is preferable.

Especially, the active ester compound containing the phosphorus atom obtained from the carboxylic acid compound containing a phosphorus atom, and the hydroxy compound which has a phosphorus atom, and the phosphorus atom obtained from the carboxylic compound and hydroxy compound containing a phosphorus atom are contained. An active ester compound containing a phosphorus atom obtained from an active ester compound or a carboxylic acid compound and a hydroxy compound containing a phosphorus atom is preferably used, but particularly from the viewpoints of improving heat resistance, lowering arithmetic mean roughness and improving peeling strength. The active ester compound containing the phosphorus atom obtained from the carboxylic acid compound and the hydroxy compound containing a phosphorus atom, or the active ester compound containing the phosphorus atom obtained from the hydroxy compound containing a carboxylic acid compound and a phosphorus atom is more preferable. Desirable And, an active ester compound containing a phosphorus atom derived from the carboxylic acid compound and phosphorous atom-containing hydroxy compound from the viewpoint of production stability is more preferred. And the active ester compound containing the phosphorus atom obtained from the phenol compound or naphthol compound containing a carboxylic acid compound and a phosphorus atom is more preferable. And, more preferably, an active ester compound containing a phosphorus atom having two or more active ester groups in one molecule obtained from an aromatic compound having a carboxylic acid compound and a phenolic hydroxyl group containing a phosphorus atom, at least two or more Particularly preferred are active ester compounds containing phosphorus atoms having two or more active ester groups in one molecule obtained from a compound having a carboxylic acid in one molecule and an aromatic compound having a phenolic hydroxyl group containing a phosphorus atom. It may also be linear or multi-branched. Moreover, if the compound which has at least 2 or more carboxylic acids in one molecule is a compound containing an aliphatic chain, compatibility with an epoxy resin can be made high, and if it is a compound which has an aromatic ring, heat resistance can be made high.

Specific 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. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable from the viewpoint of heat resistance improvement. These can also be used 1 type or in combination or 2 or more types. Moreover, all may contain the phosphorus atom.

Specific examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolak, phosphazene, 9,10-dihydro-9-oxa-10-phosphapé Nanthrene 10-oxide etc. are mentioned. Especially, from the viewpoint of heat resistance improvement and solubility improvement, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, benzenetriol, dicyclopenta Dienyldiphenol, phenol novolac, phosphazene, 9,10-dihydro-9-oxa-10-phosphafaphenanthrene 10-oxide is preferred, catechol, α-naphthol, β-naphthol, 1,5- Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, benzenetriol, Dicyclopentadienyldiphenol, phenol novolac, phosphazene, 9,10-dihydro-9-oxa-10-force Phenanthrene 10-oxide is more preferred, and α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone , Trihydroxy benzophenone, tetrahydroxy benzophenone, dicyclopentadienyl diphenol, phenol novolak, phosphazene, 9,10-dihydro-9-oxa-10-phosphafaphenanthrene 10-oxide is more preferable. Α-naphthol, β-naphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, phenol novolak, phosphazene, 9,10-dihydro-9 Much more preferred is -oxa-10-phosphaphenanthrene 10-oxide, α-naphthol, β-naphthol, dicyclopentadienyldiphenol, phenol novolac, phosphazene, 9,10-dihydro-9-oxa Particular preference is given to -10-phosphaphenanthrene 10-oxide, α-naphthol, β-naphthol, dicyclopentadienyldiphenol, A spa Zen, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide Transistor Pape I is particularly preferred. These can also be used 1 type or in combination or 2 or more types. Moreover, all may contain the phosphorus atom.

More specifically, the following general formula (1), the following general formula (2), and the following general formula (3) are mentioned.

(In formula, R may be an alkyl group, an alkenyl group, an aralkyl group, an aryl group, and may have a substituent. R1 is an alkyl group containing a phosphorus atom, an alkenyl group containing a phosphorus atom, an aral containing a phosphorus atom. And a carboxyl group, an aryl group containing a phosphorus atom, a phosphazene skeleton, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, and may have a substituent. A hydroxyl group, a phenyl group, and a naphthyl group, and two R 2 's may be bonded to each other to form a cyclic group. N represents 1 to 10.)

(Wherein R4 is an alkyl group containing a phosphorus atom, an alkenyl group containing a phosphorus atom, an aralkyl group containing a phosphorus atom, an aryl group containing a phosphorus atom, a phosphazene skeleton, 9,10-dihydro-9- Oxa-10-phosphaphenanthrene 10-oxide may be mentioned and may have a substituent R3 may be an alkyl group, an alkenyl group, an aralkyl group, an aryl group, and may have a substituent R5 is hydrogen, Hydroxyl group, phenyl group, naphthyl group, n represents 1 to 10.)

(In formula, R <6> can mention an alkyl group, an alkenyl group, an aralkyl group, and an aryl group, and may have a substituent. R <7> represents the benzoyl group which may be substituted. N represents 1-10.)

In particular, R is preferably a phenyl group, a naphthyl group, or an acetyl group. R1 is preferably a phosphazene skeleton. R2 is preferably a hydrogen or hydroxy group. R 4 is preferably 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide. R 5 is preferably hydrogen or a hydroxy group. 2-9 are preferable and, as for n, 3-8 are more preferable.

More specifically, what is represented by following formula (4) and following formula (5) is mentioned.

(Wherein R2 and n are the same as above).

(Wherein R3, R5 and n are the same as above).

As an active ester hardening | curing agent containing a commercially available phosphorus atom, the benzoylide of phosphazene-type phenol resin, the benzoylide of 9,10-dihydro-9-oxa-10-phosphazanthrene 10-oxide type, etc. are mentioned. Can be. Specific examples thereof include YLH1437 (manufactured by Mitsubishi Chemical Corporation, formula (4)), and EXB9401-65BK (manufactured by Mitsubishi Chemical Corporation, formula (3)).

There is no restriction | limiting in particular in the manufacturing method of the active ester hardening | curing agent containing a phosphorus atom, Although it can manufacture by a well-known method, Specifically, it can obtain by the condensation reaction of a carboxylic acid compound and a hydroxy compound, What is obtained by the condensation reaction of an acid compound and a phosphorus atom containing hydroxy compound is suitable at the point of manufacture stability. Especially, the phenol of (b) is used for (a) carboxylic acid compound or its halide, (b) hydroxy compound, and (c) aromatic monohydroxy compound with respect to 1 mol of carboxyl groups or acid halide groups of (a). It is preferable to have a structure obtained by making a hydroxyl group react with 0.05-1 mol and (c) in the ratio which becomes 0-0.95 mol.

(B) 1-15 mass% is preferable with respect to 100 mass% of non volatile matters in a resin composition from a viewpoint that content of the active ester hardening | curing agent containing a phosphorus atom can express low arithmetic mean roughness and high peeling strength, 10 mass% is more preferable, and 1.5-8 mass% is more preferable.

In addition, in view of expressing flame retardancy, when the active ester curing agent containing (B) phosphorus atom is 100 mass%, the phosphorus content in the active ester curing agent containing (B) phosphorus atom is preferably 2 to 15 mass%. 3 to 13 mass% is more preferable, and 4 to 11 mass% is more preferable. Moreover, 0.05-3 mass% is preferable with respect to 100 mass% of non volatile matters in a resin composition, and, as for phosphorus content in a resin composition, it is more preferable that it is 0.1-3 mass%.

The peeling strength of the conductor layer and the insulating layer obtained by curing the resin composition of the present invention, forming an insulating layer, roughening the surface of the insulating layer and plating, and measuring the peeling strength (pilling strength) of the plating conductor layer described later. And evaluation> can be grasped by the measuring method described.

The upper limit of the peeling strength is preferably 0.6 kgf / cm or less, more preferably 0.7 kgf / cm or less, still more preferably 0.8 kgf / cm or less, and even more preferably 1.0 kgf / cm or less. The lower limit of the peeling strength is preferably 0.36 kgf / cm or more, more preferably 0.38 kgf / cm or more, and even more preferably 0.40 kgf / cm or more.

The arithmetic mean roughness (Ra value) after hardening the resin composition of this invention, forming an insulating layer, and roughening the surface of the insulating layer is described in <Measurement and evaluation of arithmetic mean roughness (Ra value) after a roughening> mentioned later. It can grasp by a measuring method.

The upper limit of arithmetic mean roughness (Ra value) is preferably 200 nm or less, more preferably 180 nm or less, further preferably 150 nm or less. 50 nm or more is preferable, 30 nm or more is more preferable, and 10 nm or more of the lower limit of arithmetic mean roughness (Ra value) is more preferable.

The average thermal expansion rate from 25 degreeC to 150 degreeC after hardening the resin composition of this invention and forming an insulation layer can be grasped | ascertained by the evaluation method as described in <measurement and evaluation of thermal expansion rate> mentioned later.

25 ppm or less is preferable and, as for the upper limit of an average thermal expansion coefficient, 23 ppm or less is more preferable. The lower limit of the average thermal expansion rate is even more preferably 10 ppm or more, particularly preferably 5 ppm or more.

The dielectric tangent of the hardened | cured material of the resin composition of this invention can be grasped | ascertained by the measuring method as described in <measurement and evaluation of a dielectric tangent> mentioned later.

The upper limit of the dielectric tangent of the cured product of the resin composition of the present invention is preferably 0.0055 or less, and more preferably 0.0050 or less. The lower limit of the dielectric tangent of the cured product of the resin composition of the present invention is preferably 0.002 or more, more preferably 0.0015 or more, and still more preferably 0.001 or more.

<(C) inorganic filler>

The resin composition of this invention can further reduce the thermal expansion rate of an insulating layer by containing an inorganic filler further. The inorganic filler is not particularly limited, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, titanic acid Strontium, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Especially, silica is preferable. Moreover, silica, such as amorphous silica, crushed silica, fused silica, crystalline silica, synthetic silica, and hollow silica, is preferable and fused silica is more preferable. Moreover, a spherical thing is preferable as silica. These can also be used 1 type or in combination or 2 or more types. Commercially available spherical fused silicas include "SOC2" and "SOC1" manufactured by Admatechs.

The average particle diameter of the inorganic filler is not particularly limited, but the upper limit of the average particle diameter of the inorganic filler is preferably 5 μm or less, more preferably 3 μm or less, further preferably 1 μm or less from the viewpoint of forming fine wiring on the insulating layer. More preferably 0.7 μm or less, particularly preferably 0.5 μm or less, particularly preferably 0.4 μm or less, particularly preferably 0.3 μm or less. On the other hand, the lower limit of the average particle diameter of the inorganic filler is preferably 0.01 μm or more, and more preferably 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from rising and the handleability of the epoxy resin composition being a varnish. It is preferable, 0.05 micrometer or more is more preferable, 0.07 micrometer or more is especially preferable, and 0.1 micrometer or more is especially preferable. The average particle diameter of the said inorganic filler can be measured by the laser diffraction scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median size thereof can be measured by making the average particle diameter. The measurement sample can use preferably what disperse | distributed the inorganic filler in water according to the ultrasonic wave. As the laser diffraction particle size distribution measuring apparatus, LA-500, 750, 950, etc. manufactured by Horiba Corporation can be used.

The inorganic filler in this invention is surface-treated with surface treatment agents, such as an epoxy silane coupling agent, an aminosilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, and a titanate coupling agent. It is preferable to improve the moisture resistance. These can also be used 1 type or in combination or 2 or more types. Specifically, as a surface treating agent, aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-2 (aminoethyl) aminopropyltrimethoxy Aminosilane-based coupling agents such as silane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4- Epoxy silane coupling agents such as epoxycyclohexyl) ethyltrimethoxysilane, mercaptosilane-based coupling agents such as mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane, methyltrimethoxysilane and octadecyltrimeth Silane coupling agents such as oxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane, hexamethyldisilazane, hexaphenyldisilazane, trisilazane, ci Organosilazane compounds such as rotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, butyl titanate dimer, titanium octylene glycolate, diisopropoxycitanebis (triethanolami ), Thihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n -Butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) tita Nate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyltrioctanoyl titanate, isopropyltricumylphenyl titanate, isopropyl triisostearo Ilty Nitrate, isopropyl isostearoyl diacrylate, isopropyl dimethacrylic isostaroyl titanate, isopropyl tri (dioctylphosphate) titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl Titanate coupling agents, such as a tris (dioctyl pyrophosphate) titanate and an isopropyl tri (N-amide ethyl amino amino) titanate, etc. are mentioned. Among these, the aminosilane-based coupling agent is preferred because it is excellent in moisture resistance, dispersibility, properties of a cured product, and the like.

When content of an inorganic filler is mix | blended when the non volatile component in a resin composition is 100 mass%, it changes also with the characteristic calculated | required by a resin composition, It is preferable that it is 20-85 mass%, and 30-80 mass% is More preferably, 35-75 mass% is more preferable. When there is too little content of an inorganic filler, there exists a tendency for the thermal expansion rate of hardened | cured material to become high, and when content is too large, there exists a tendency for hardened | cured material to become weak and a peeling strength to fall.

<(D) Curing accelerator>

The resin composition of this invention can harden an epoxy resin and a hardening | curing agent efficiently by further containing a hardening accelerator. Although it does not specifically limit as a hardening accelerator, An amine hardening accelerator, a guanidine-type hardening accelerator, an imidazole series hardening accelerator, a phosphonium-type hardening accelerator, a metal-type hardening accelerator, etc. are mentioned. These can also be used 1 type or in combination or 2 or more types.

Although it does not specifically limit as an amine hardening accelerator, Trialkylamine, such as a triethylamine and a tributylamine, 4-dimethylaminopyridine, benzyl dimethylamine, 2,4,6,-tris (dimethylaminomethyl) phenol And amine compounds such as 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). These can also be used 1 type or in combination or 2 or more types.

Although it does not specifically limit as a guanidine-type hardening accelerator, Dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, Diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4 .0] deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide , 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide, and the like. These can also be used 1 type or in combination or 2 or more types.

Although it does not specifically limit as an imidazole series hardening accelerator, 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethylimidazole, 2-ethyl- 4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2 -Methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenyl Imidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2' Undecyl imidazolyl (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl- s-triazine, to 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]- -s-triazineisocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 hydroxymethyl Imidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, And an adduct of an imidazole compound such as 2-phenylimidazoline and an imidazole compound and an epoxy resin. These can also be used 1 type or in combination or 2 or more types.

Although it does not specifically limit as a phosphonium-type hardening accelerator, Triphenylphosphine, a phosphonium borate compound, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, tetrabutyl phosphonium decanoate, (4 -Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc. are mentioned. These can also be used 1 type or in combination or 2 or more types.

In the resin composition of this invention, when content of a hardening accelerator (except a metal type hardening accelerator) is 100 mass% of non volatile components in a resin composition, the range of 0.005-1 mass% is preferable, and 0.01-0.5 The range of mass% is more preferable. If it is less than 0.005 mass%, hardening will be delayed and a thermosetting time will need long, and if it exceeds 1 mass%, the storage stability of a resin composition will tend to fall.

Although it does not specifically limit as a metal type hardening accelerator, The organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic iron complexes such as an organic zinc complex, iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate and zinc stearate. These can also be used 1 type or in combination or 2 or more types.

In the resin composition of this invention, when the addition amount of a metal-type hardening accelerator makes the non volatile component in a resin composition 100 mass%, the content of metal is 25-500 ppm with respect to a metal-based hardening catalyst, and 40-200 is preferable. The range of ppm is more preferable. If it is less than 25 ppm, formation of the conductor layer excellent in adhesiveness to the insulating layer surface of low arithmetic mean roughness will become difficult, and when it exceeds 500 ppm, it will become the tendency for the storage stability and insulation of a resin composition to fall.

<(E) Curing Agent>

The resin composition of this invention can improve insulation and a mechanical characteristic by further containing a hardening | curing agent. (E) Although it does not specifically limit as a hardening | curing agent, A phenolic hardening | curing agent, a naphthol hardening | curing agent, an active ester hardening | curing agent (except the active ester hardening | curing agent containing a phosphorus atom), a benzoxazine type hardening | curing agent, a cyanate ester type hardening | curing agent And an acid anhydride-based curing agents, and the like, and cyanate ester curing agents and active ester curing agents (except for active ester curing agents containing phosphorus atoms) are preferred from the viewpoint of lowering the dielectric tangent. These can also be used 1 type or in combination or 2 or more types.

Although there is no restriction | limiting in particular as a phenol type hardening | curing agent and a naphthol type hardening | curing agent, The phenol type hardening | curing agent which has a novolak structure, and the naphthol type hardening | curing agent which has a novolak structure is mentioned, A phenol novolak resin, a triazine skeleton containing phenol novolak resin, Naphthol novolak resin, naphthol aralkyl type resin, a triazine skeleton containing naphthol resin, and a biphenyl aralkyl type phenol resin are preferable. Commercially available products are biphenyl aralkyl type phenol resins "MEH-7700", "MEH-7810", "MEH-7851", "MEH7851-4H" (made by Meiwa Kasei Co., Ltd.), "GPH" (Nihon Kayaku) "NHN", "CBN" (manufactured by Nihon Kayaku Co., Ltd.), and naphthol aralkyl type resins "SN170", "SN180", "SN190", "SN475", "as a naphthol novolak resin" SN485 "," SN495 "," SN395 "," SN375 "(manufactured by Tohwa Kasei Co., Ltd.)," TD2090 "(manufactured by DIC Corporation), phenol novolac resin" LA3018 "as phenol novolak resin , "LA7052", "LA7054", "LA1356" (manufactured by DIC Corporation), and the like. These can also use together 1 type (s) or 2 or more types.

The active ester curing agent (except for the active ester curing agent containing a phosphorus atom) is not particularly limited, but generally phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy, etc. The compound which has two or more ester groups with high reaction activity, such as ester of a compound, in one molecule is used preferably. It is preferable that the said active ester type hardening | curing agent is obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound, a hydroxy compound, and / or a thiol compound. In particular, from the viewpoint of improving the heat resistance, an active ester curing agent (except for an active ester curing agent containing a phosphorus atom), which is obtained from a carboxylic acid compound and a hydroxy compound, is preferable, and a carboxylic acid compound and a phenol compound and / Or an active ester curing agent (except for an active ester curing agent containing a phosphorus atom) obtained from a naphthol compound. 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. As the phenol compound or naphthol compound, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, trihydroxy Benzophenone, tetrahydroxy benzophenone, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolac and the like. The active ester type hardener can use 1 type (s) or 2 or more types. As the active ester curing agent (except for the active ester curing agent containing a phosphorus atom), the active ester curing agent disclosed in Japanese Patent Laid-Open No. 2004-277460 (however, the active ester curing agent containing a phosphorus atom) Excluded) or a commercially available one can also be used. Commercially available active ester curing agents (except for active ester curing agents containing phosphorus atoms) include dicyclopentadienyldiphenol structures, acetylates of phenol novolacs, and benzoylides of phenol novolacs. Etc. are preferable, and it is more preferable to contain the dicyclopentadienyl diphenol structure especially. Specifically, it contains a dicyclopentadienyldiphenol structure, EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (DIC Co., Ltd. product, active group equivalent approximately 223), DC808 (as acetylate of phenol novolak) YLH1026 (Japan epoxy resin Co., Ltd. production, activator equivalent approximately 200), YLH1030 (Japan Epoxy Resin Co., Ltd. production, activator equivalent weight) 201), YLH1048 (made by Japan Epoxy Resin Co., Ltd., about 245 equivalents of active groups), etc. Among these, EXB9460S is preferable from a viewpoint of varnish storage stability and the thermal expansion coefficient of hardened | cured material.

Specific examples of the active ester curing agent containing the dicyclopentadienyldiphenol structure (excluding the active ester curing agent containing a phosphorus atom) include those of the following formula (6).

(In formula, R is a phenyl group and a naphthyl group, k represents 0 or 1, and n is 0.05-2.5 as an average of a repeating unit.)

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

Although there is no restriction | limiting in particular as a benzoxazine type hardening | curing agent, As a specific example, F-a, P-d (made by Shikoku Chemical Co., Ltd.), HFB2006M (made by Showa Polymer Co., Ltd.), etc. are mentioned.

Although there is no restriction | limiting in particular as a cyanate ester type hardening | curing agent, Novolak-type (phenol novolak-type, alkylphenol novolak-type, etc.) cyanate ester type hardening | curing agent, dicyclopentadiene type cyanate ester type hardening | curing agent, bisphenol-type (bisphenol A Type, bisphenol F type, bisphenol S type and the like) and cyanate ester-based curing agents and prepolymers in which these are partially triazineized. Although the weight average molecular weight of a cyanate ester hardening | curing agent is not specifically limited, 500-4500 are preferable and 600-3000 are more preferable. Specific examples of the cyanate ester curing agent include, for example, bisphenol A dicyanate, polyphenolcyanate (oligo (3-methylene-1,5-phenylenecyanate), 4,4'-methylenebis (2,6) -Dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4 -Cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4- Polyfunctional cyanate resins derived from bifunctional cyanate resins such as cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, phenol novolac, cresol novolac, dicyclopentadiene structure-containing phenol resin, And triazines in which these cyanate resins are partially triazine, etc. These may be used alone or in combination of two or more thereof. As a cyanate ester resin marketed, the phenol novolak-type polyfunctional cyanate ester resin (Lonza Japan Co., Ltd. product, PT30, cyanate equivalent weight 124) represented by following formula (7), and following formula (8) A part or all of the bisphenol A dicyanate represented by) is triazine-ized prepolymer (Tronza Japan Co., Ltd. product, BA230, cyanate equivalent weight 232), and the dicyclopentadiene structure represented by following formula (9) Containing cyanate ester resin (Lonza Japan Co., Ltd. product, DT-4000, DT-7000), etc. are mentioned.

[In Formula (7), n represents an arbitrary number (preferably 0 to 20) as an average value.]

(N shows the number of 0-5 as an average value in Formula (9).)

Although it does not specifically limit as an acid anhydride type hardening | curing agent, A phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydro phthalic anhydride, a methylnamic acid anhydride, hydrogenated methylnadic acid anhydride, a trialkyl Tetrahydro phthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimelli anhydride Acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-di Phenylsulfontetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- C] furan-1,3-dione, ethylene glycol bis (anhydrotrimelitate), styrene and horses A styrene copolymer acid is?, And the like of the polymer-type acid anhydride, such as maleic acid resin.

In the resin composition of this invention, from the viewpoint of improving the mechanical strength and water resistance of the hardened | cured material of a resin composition, the active ester hardening | curing agent containing the total number of epoxy groups of (A) epoxy resin, and (B) phosphorus atom, and (E) hardening | curing agent The ratio between the total number of reactors is preferably 1: 0.2 to 2, more preferably 1: 0.3 to 1.5, and still more preferably 1: 0.4 to 1. On the other hand, the total number of epoxy groups of the epoxy resin present in the resin composition is the value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the total number of all the epoxy resins. The value divided by equivalent is the sum total for all curing agents.

<(F) Thermoplastic Resin>

The mechanical composition of hardened | cured material can be improved by further containing (F) thermoplastic resin in the resin composition of this invention, and also the film forming ability at the time of using in the form of an adhesive film can also be improved further. Such thermoplastic resins include phenoxy resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyether sulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, polyesters Resin can be mentioned. These thermoplastic resins may be used independently, respectively and may be used in combination of 2 or more type. It is preferable that the weight average molecular weight of a thermoplastic resin is the range of 5000-200000. When smaller than this range, there exists a tendency for the effect of film forming ability and mechanical strength improvement not to be fully exhibited, and when larger than this range, compatibility with cyanate ester resin and a naphthol type epoxy resin will not be enough, and the surface unevenness after hardening will be There exists a tendency which becomes large and becomes difficult to form a high-density fine wiring. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). As for the weight average molecular weight by GPC method, Shodex K-800P / K-804L / K made by Showa Denko Co., Ltd. as a column using LC-9A / RID-6A by Shimadzu Corporation as a measuring apparatus specifically, -804L can be measured at the column temperature of 40 degreeC using chloroform etc. as a mobile phase, and can be computed using the analytical curve of standard polystyrene.

When mix | blending (F) thermoplastic resin with the resin composition of this invention, content of the thermoplastic resin in a resin composition is not specifically limited, 0.1-10 mass% is preferable with respect to 100 mass% of non volatile matters in a resin composition, 1 5 mass% is more preferable. When the content of the thermoplastic resin is too small, the film forming ability and the effect of improving the mechanical strength tend not to be exhibited. When the content of the thermoplastic resin is excessively large, the arithmetic mean roughness of the surface of the insulating layer after the increase in the melt viscosity and the wet roughening process tends to be increased. have.

<(G) rubber particle>

The resin composition of this invention can improve plating peeling strength by further containing (G) rubber particle, and can also improve the drillability, the fall of dielectric tangent, and the stress relaxation effect. The rubber particles that can be used in the present invention are, for example, insoluble in organic solvents used in preparing varnishes of the resin composition, and incompatible with cyanate ester resins, epoxy resins, and the like, which are essential components. Therefore, the said rubber particle exists in a dispersion state in the varnish of the resin composition of this invention. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level that does not dissolve in an organic solvent or resin and making it particulate.

Preferred examples of the rubber particles that can be used in the present invention include core-shell rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrenebutadiene rubber particles, acrylic rubber particles and the like. The core-shell rubber particles are rubber particles having a core layer and a shell layer. For example, the shell layer of the outer layer is made of glassy polymer, and the inner layer core layer is made of rubbery polymer, or the shell layer of the outer layer is made of glassy polymer. And a three-layer structure in which the intermediate layer is composed of a rubbery polymer and the core layer is composed of a glassy polymer. The glassy polymer layer is composed of, for example, a polymer of methyl methacrylate and the like, and the rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber). A rubber particle can also be used in combination of 2 or more type. Specific examples of the core-shell rubber particles include Stapiroid AC3832, AC3816N, IM-401, IM-401 1, IM-401 7-17 (trade name, manufactured by KANSU Hwasung Co., Ltd.), metablen (metablen) ) KW-4426 (brand name, Mitsubishi Rayon Co., Ltd.) is mentioned. Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include metablene W300A (average particle size 0.1 μm) and W450A (average particle size 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

The average particle diameter of the rubber particle to mix | blend becomes like this. Preferably it is the range of 0.005-1 micrometer, More preferably, it is the range of 0.2-0.6 micrometer. The average particle diameter of the rubber particles used in the present invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and the particle size distribution of the rubber particles is prepared on a mass basis using a rich particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). It can measure by making the magnitude | size of an intermediate value an average particle diameter.

Content of rubber particle | grains becomes like this. Preferably it is 1-10 mass% with respect to 100 mass% of non volatile matters in a resin composition, More preferably, it is 2-5 mass%.

<(H) flame retardant>

The resin composition of this invention can provide a flame retardance by containing a (H) flame retardant further. Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides, and the like. As organophosphorus flame retardants, phosphorus-containing benzoxazine compounds such as phenanthrene-type phosphorus compounds such as HCA, HCA-HQ and HCA-NQ manufactured by Sanko Co., Ltd., and HFB-2006M manufactured by Showa Polymer Co., Ltd., Ajinomoto Fine Leopard 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TPPO of Techno Co., Ltd. Phosphoric Acid Ester Compounds such as PPQ, Clariant Co., Ltd. OP930, Daihachi Chemical Co., Ltd., PX200, Phosphorus-containing epoxy resins such as Toto Chemical Co., Ltd., FX289, FX305, TX0712, Doto Chemical Co., Ltd. Phosphorus containing phenoxy resins, such as manufactured ERF001, Phosphorus containing epoxy resins, such as YL7613 by Japan Epoxy Resin Co., Ltd., etc. are mentioned. Examples of the organic nitrogen-containing phosphorus compounds include phosphate ester amide compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., SPB100, SPE100, SPH-100, SPS-100 and Fushimi Co., Ltd. Phosphazene compounds, such as FP-series by the pharmaceutical company, etc. are mentioned. As a metal hydroxide, magnesium hydroxide, such as UD65, UD650, UD653 made by Ube Materials, Ltd., B-30, B-325, B-315, B-308, B- made by Tomoe Industries, Ltd. Aluminum hydroxide, such as 303 and UFH-20, etc. are mentioned.

<Other Ingredients>

Another component can be mix | blended with the resin composition of this invention as needed in the range which does not impair the effect of this invention. Other components include thermosetting resins such as vinyl benzyl compounds, acrylic compounds, maleimide compounds, block isocyanate compounds, organic fillers such as silicone powder, nylon powder, and fluorine powder, thickeners such as olben and benton, silicones, fluorine and polymers. Adhesion-imparting agents, such as an antifoamer or a leveling agent, an imidazole series, a thiazole series, a triazole series, and a silane coupling agent, coloring agents, such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black, etc. are mentioned.

The preparation method of the resin composition of this invention is not specifically limited, For example, the method of adding a solvent etc. as needed and mixing using a rotary mixer etc. are mentioned.

Although the use of the resin composition of this invention is not specifically limited, Resin, such as an insulating film, such as an adhesive film and a prepreg, a circuit board, a soldering resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole filling resin, and a part embedding resin The composition can be widely used for the necessary use. Especially, in manufacture of a multilayer printed wiring board, it can use suitably as a resin composition (resin composition for insulating layers of a multilayer printed wiring board) for forming an insulation layer, and it is a resin composition for forming a conductor layer by plating (by plating It can be used more suitably as a resin composition for insulating layers of the multilayer printed wiring board which forms a conductor layer, and can be used more suitably as a resin composition (resin composition for buildup layers of a multilayer printed wiring board) for forming a buildup layer. Although the resin composition of this invention can be apply | coated to a circuit board in a varnish state, and an insulating layer can be formed, it is industrially generally used in the form of sheet-like laminated materials, such as an adhesive film and a prepreg. As for the softening point of a resin composition, 40-150 degreeC is preferable from a lamination property of a sheet-like laminated material.

&Lt; Adhesive film &

The adhesive film of this invention prepares the resin varnish which melt | dissolved the resin composition in the organic solvent, the method known to a person skilled in the art, and apply | coats this resin varnish to a support body using a die coater etc., and also it heats or hot air sprays, etc. It can manufacture by drying an organic solvent and forming a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, acetic acid esters such as propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, and butyl carbox. Aromatic hydrocarbons, such as carbitols, such as a beitol, toluene, and xylene, amide solvents, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, etc. are mentioned. The organic solvent can also be used in combination of 2 or more type.

Although drying conditions are not specifically limited, It drys so that content of the organic solvent to a resin composition layer may be 10 mass% or less, Preferably it is 5 mass% or less. Although it changes also with the amount of the organic solvent in a varnish, and the boiling point of an organic solvent, a resin composition layer can be formed by drying the varnish containing 30-60 mass% organic solvent about 50 to 150 degreeC for 3 to 10 minutes, for example.

It is preferable to make the thickness of the resin composition layer formed in an adhesive film more than the thickness of a conductor layer. Since the thickness of the conductor layer which a circuit board has normally is a range of 5-70 micrometers, it is preferable that a resin composition layer has a thickness of 10-100 micrometers.

Examples of the support include a film of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, a polyethylene terephthalate (hereinafter may be abbreviated as "PET"), a film of polyester such as polyethylene naphthalate, a polycarbonate film, a polyimide film Various plastic films, such as these, are mentioned. Moreover, release paper, copper foil, metal foil, such as aluminum foil, can also be used. Surface treatments, such as a MAD process and a corona treatment, may be given to the support body and the protective film mentioned later. Moreover, the mold release process may be performed with mold release agents, such as a silicone resin mold release agent, an alkyd resin mold release agent, and a fluororesin mold release agent.

Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

The protective film based on a support body can be further laminated | stacked on the surface in which the support body of a resin composition layer is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating | stacking a protective film, adhesion | attachment and a damage | wound of dirt etc. to the surface of a resin composition layer can be prevented. The adhesive film may be rolled up and stored in a roll shape.

<Multilayer printed wiring board using adhesive film>

Next, an example of the method of manufacturing a multilayer printed wiring board using the adhesive film manufactured as mentioned above is demonstrated.

First, an adhesive film is laminated on one side or both sides of a circuit board using a vacuum laminator. As a board | substrate used for a circuit board, a glass epoxy board | substrate, a metal board | substrate, a polyester board | substrate, a polyimide board | substrate, BT resin board | substrate, a thermosetting polyphenylene ether board | substrate, etc. are mentioned, for example. In addition, a circuit board means here that the conductor layer (circuit) pattern-processed was formed in one side or both surfaces of the above board | substrates. In the multilayer printed wiring board formed by alternately stacking the conductor layer and the insulating layer, the circuit board referred to herein includes one or both of the outermost layers of the multilayer printed wiring board as a patterned conductor layer (circuit). . Moreover, the roughening process may be previously performed by the blackening process, copper etching, etc. on the conductor layer surface.

In the said laminate, when an adhesive film has a protective film, after removing the said protective film, an adhesive film and a circuit board are preheated as needed, and it crimp | bonds to a circuit board, pressing and heating an adhesive film. In the adhesive film of this invention, the method of laminating to a circuit board under reduced pressure by the vacuum lamination method is used preferably. The conditions of the laminate are not particularly limited, but for example, the crimping temperature (lamination 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 ), and is preferably laminated under a reduced pressure of 20 mmHg (26.7 hPa) or less. In addition, the method of lamination may be batch type or continuous in a roll. Vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, Nichigo Morton Co., Ltd. vacuum vacuum applicator, manufactured by Meiki Co., Ltd., vacuum pressurized laminator, Hitachi Industries Co., Ltd. roll type dry coater, Hitachi AIC Co., Ltd. vacuum laminator, etc. Can be mentioned.

In addition, the lamination process for heating and pressurizing under reduced pressure may be performed using a general vacuum hot press. For example, it can carry out by pressing metal plates, such as a heated SUS board, from the support layer side. The press conditions are 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 step, it is preferable to divide the conditions into two or more steps from the viewpoint of controlling the bleeding of the resin. For example, the first stage press has a temperature of 70-150 ° C., the pressure ranges from 1-15 kgf / cm ² , and the second stage press has a temperature of 150-200 ° C. and a pressure of 1-40 kgf / cm ² . It is preferable to carry out in the range. The time for each step is preferably performed at 30 to 120 minutes. Commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Corporation), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

After laminating | stacking an adhesive film to a circuit board and cooling to near room temperature, when peeling a support body, an insulating layer can be formed in a circuit board by peeling and thermosetting. Although the conditions of thermosetting may be suitably selected according to the kind, content, etc. of the resin component in a resin composition, Preferably it is 20 to 180 minutes at 150 degreeC-220 degreeC, More preferably, it is 30 to 120 minutes at 160 degreeC-210 degreeC Is selected from the range of.

After forming an insulating layer, when a support body is not peeled off before hardening, it peels here. Subsequently, as necessary, through holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. For example, the punching can be performed by a known method such as a drill, a laser, a plasma, or a combination of these methods as necessary. The punching by a laser such as a carbon dioxide laser or a YAG laser is the most common method. .

Subsequently, a conductor layer is formed on an insulating layer by dry plating or wet plating. As dry plating, well-known methods, such as vapor deposition, sputtering, and ion plating, can be used. In the case of wet plating, an uneven anchor is formed on the surface of the insulating layer by performing swelling treatment with swelling liquid, roughening treatment with oxidizing agent and neutralization treatment with neutralizing liquid in this order. The swelling treatment by the swelling liquid is performed by immersing the insulating layer in the swelling liquid for 5 to 20 minutes at 50 to 80 ° C. Examples of the swelling solution include an alkali solution, a surfactant solution, and the like, and preferably an alkaline solution. Examples of the alkali solution include sodium hydroxide solution and potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securiganth P (Swelling Dip Securiganth S) manufactured by Atotech Japan Co., Ltd., and the like. The roughening treatment by the oxidizing agent is carried out by immersing the insulating layer in the oxidizing agent solution for 10 to 30 minutes at 60 ° C to 80 ° C. Examples of the oxidizing agent include alkaline permanganate solutions in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, and nitric acid. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd. and Dosing Solution Securigans P. Neutralization treatment by neutralizing liquid is performed by immersing in neutralizing liquid for 3 to 10 minutes at 30-50 degreeC. As a neutralization liquid, an acidic aqueous solution is preferable, and as a commercial item, the reduction solution Securigans P of Atotech Japan Co., Ltd. product is mentioned.

Subsequently, a conductive layer is formed by a combination of electroless plating and electrolytic plating. In addition, a plating resist of a pattern opposite to the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method of pattern formation after that, the subtractive method, the semiadditive method, etc. which are well-known to a person skilled in the art can be used, for example.

<Prepreg>

The prepreg of this invention can be manufactured by impregnating the resin composition of this invention with the sheet-like reinforcement base material which consists of fibers by a hot melt method or the solvent method, and heating and semi-hardening. That is, it can be set as the prepreg which becomes the state which the resin composition of this invention impregnated the sheet-like reinforcement base material which consists of fibers. As a sheet-like reinforcement base material which consists of a fiber, what consists of fibers commonly used as prepreg fiber, such as glass cross and aramid fiber, can be used, for example.

The hot melt method does not dissolve the resin in an organic solvent but coats it on a coated paper having good peelability with the resin, and laminates it on a sheet-like reinforcing substrate, or a sheet-type reinforcing substrate by a die coater without dissolving the resin in an organic solvent. It is a method of manufacturing a prepreg by apply | coating directly to a. The solvent method is a method of dissolving the resin in an organic solvent in the same manner as in the adhesive film to prepare a resin varnish, immersing the sheet-like reinforcing substrate in the varnish, impregnating the resin varnish into the sheet-like reinforcing substrate, and then drying.

<Multilayer printed wiring board using prepreg>

Next, an example of the method of manufacturing a multilayer printed wiring board using the prepreg manufactured as mentioned above is demonstrated. One sheet or several sheets of the prepreg of the present invention are stacked on a circuit board, if necessary, sandwiched with a metal plate with a release film interposed therebetween, and vacuum press lamination under pressure and heating conditions. Pressurization and heating conditions, Preferably, the pressure is 5-40 kgf / cm <^2> (49 * 10 <^4> -492 * 10 <^4> N / m <^2> ), and temperature is 20-100 minutes at 120-200 degreeC. Moreover, it is also possible to heat-harden, after laminating | stacking a prepreg to a circuit board by the vacuum lamination method similarly to an adhesive film. Then, after roughening the surface of the prepreg hardened | cured similarly to the method described above, a conductor layer can be formed by plating and a multilayer printed wiring board can be manufactured.

<Semiconductor Device>

A semiconductor device can be manufactured by using the multilayer printed wiring board of this invention. A semiconductor device can be manufactured by mounting a semiconductor chip in the conductive part of the multilayer printed wiring board of this invention. A "conduction site" is a place where electric signals are transmitted in a multilayer printed wiring board, and the place may be either a surface or a buried place. In addition, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting a semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the wire bonding method, the flip chip mounting method, and the bump-free buildup layer (BBUL) ), A mounting method by an anisotropic conductive film (ACF), a mounting method by a non-conductive film (NCF), etc. are mentioned.

The "mounting method by a bumpless build-up layer (BBUL)" means the "mounting method which embeds a semiconductor chip directly into the recessed part of a multilayer printed wiring board, and connects the semiconductor chip and the wiring on a printed wiring board", Furthermore, the following BBUL method It is largely divided into 1) and BBUL method 2).

BBUL method 1) A mounting method for mounting a semiconductor chip in a recess of a multilayer printed wiring board using an underfill agent

BBUL method 2) A mounting method for mounting a semiconductor chip in a recess of a multilayer printed wiring board using an adhesive film or a prepreg

BBUL method 1) specifically includes the following steps.

Process 1) The thing which removed the conductor layer from both surfaces of a multilayer printed wiring board is provided, and a through hole is formed by a laser and a mechanical drill.

Step 2) An adhesive tape is attached to one side of the multilayer printed wiring board and arranged so as to fix the bottom surface of the semiconductor chip on the adhesive tape in the through hole. It is preferable to make the semiconductor chip at this time lower than the height of a through-hole.

Step 3) The semiconductor chip is fixed to the through hole by injecting and filling an underfill agent into the gap between the through hole and the semiconductor chip.

Step 4) After that, the adhesive tape is peeled off to expose the bottom surface of the semiconductor chip.

Process 5) The adhesive film or prepreg of this invention is laminated on the bottom surface side of a semiconductor chip, and a semiconductor chip is coat | covered.

Step 6) After curing the adhesive film or prepreg, a hole is drilled by a laser, the bonding pad on the bottom surface of the semiconductor chip is exposed, and wiring is performed by performing the roughening treatment, electroless plating, and electrolytic plating described above. Connect with. If necessary, an adhesive film or prepreg may be further laminated.

BBUL method 2) specifically includes the following steps.

Process 1) A photoresist film is formed on the conductor layers of both surfaces of a multilayer printed wiring board, and an opening part is formed only in one side of a photoresist film by the photolithographic method.

Process 2) The conductor layer exposed to the opening part is removed by etching liquid, the insulating layer is exposed, and then the resist films on both sides are removed.

Step 3) Using a laser or a drill, all exposed insulating layers are removed to drill holes to form recesses. The energy of the laser is preferably a laser whose energy can be adjusted to lower the laser absorption of copper and increase the laser absorption of the insulating layer, and more preferably a carbon dioxide laser. By using such a laser, a laser can remove only an insulating layer, without penetrating the conductor layer of the facing surface of the opening part of a conductor layer.

Step 4) The bottom surface of the semiconductor chip is placed in the recess toward the opening side, the adhesive film or prepreg of the present invention is laminated from the side of the opening, and the semiconductor chip is covered to fill the gap between the semiconductor chip and the recess. It is preferable to make the semiconductor chip at this time lower than the height of a recessed part.

Process 5) After hardening an adhesive film or a prepreg, it makes a hole with a laser and exposes the bonding pad of the bottom surface of a semiconductor chip.

Step 6) Wiring is connected by performing the roughening process, electroless plating, and electrolytic plating disclosed above, and further laminating an adhesive film or prepreg as necessary.

Among the semiconductor chip mounting methods, since the semiconductor device is miniaturized, transmission loss is reduced, and solder is not used, the thermal history is not applied to the semiconductor chip, and further, distortion of the solder and resin can be generated in the future. In view of the absence, a mounting method using a bumpless build-up layer (BBUL) is preferable, BBUL method 1) and BBUL method 2) are more preferable, and BBUL method 2) is more preferable.

<Examples>

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples.

<Measurement method and evaluation method>

First, various measurement methods and evaluation methods are described.

<Preparation of the sample for measuring peeling strength and arithmetic mean roughness (Ra value)>

(1) base treatment of inner layer circuit board

Both sides of glass cloth base material epoxy resin double-sided copper clad laminated board (18μm thickness of copper foil, substrate thickness 0.3mm, Matsushita Electric Corporation R5715ES) which formed inner layer circuit manufactured by MEC.CO., LTD. CZ8100 1um etching was performed to perform a roughening treatment of the copper surface.

(2) Laminate of adhesive film

The adhesive film produced by the Example and the comparative example was laminated on both surfaces of an inner layer circuit board using the batch type vacuum pressurization laminator MVLP-500 (made by Meiki Corporation). Lamination was performed by depressurizing for 30 second and making atmospheric pressure 13 hPa or less, and then pressing at 100 degreeC and pressure 0.74 Mpa for 30 second.

(3) curing of the resin composition

The laminated adhesive film was cured at 100 ° C. for 30 minutes, followed by curing conditions at 180 ° C. for 30 minutes, and the PET film was peeled off to form an insulating layer.

(4) coordination treatment

The inner circuit board having the insulating layer formed therein was swelled with diethylene glycol monobutyl ether-containing swelling dip Securigans P (glycol ether, aqueous solution of sodium hydroxide) of Atotech Japan Co., Ltd. for 10 minutes at 60 ° C. It was immersed, and then, it was immersed in Atotech Japan Co., Ltd. condensate compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) for 20 minutes at 80 degreeC, and finally Atotech Japan as a neutralizing liquid. It was immersed for 5 minutes at 40 degreeC in reduction solution Securigans P (glyoxal, the aqueous solution of sulfuric acid). After drying 30 minutes at 80 degreeC, the arithmetic mean roughness (Ra value) was measured with respect to the insulating layer surface after this roughening process.

(5) Plating by semi additive method

In order to form a circuit on the insulating layer surface, the inner circuit board was immersed for 5 minutes at 40 ° C in an electroless plating solution containing PdCl ₂ , and then immersed for 20 minutes at 25 ° C in an electroless copper plating solution. After the annealing treatment was performed by heating at 150 ° C. for 30 minutes, an etching resistor was formed, and after forming the pattern by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 35 ± 5 μm. The annealing treatment was then performed at 200 ° C. for 60 minutes. The peeling strength (pilling strength) of the plating conductor layer was measured for this circuit board.

<Measurement and evaluation of peeling strength (pilling strength) of the plated conductor layer>

Into the conductor layer of the circuit board, a partial sheath having a width of 10 mm and a length of 100 mm is placed, and one end is peeled off and held by a gripper (TSE, Inc., Autocom Tester AC-50C-SL), at a speed of 50 mm / min at room temperature in the vertical direction. The load (kgf / cm) when 35 mm was peeled off was measured.

<Measurement and evaluation of arithmetic mean roughness (Ra value) after harmony>

Ra value was calculated | required using the non-contact surface roughness machine (WYKO NT3300 by Vico Instruments Co., Ltd.) by the numerical value obtained by making a measurement range 121 micrometer x 92 micrometers with a VSI contact mode and a 50x lens. And it measured by obtaining the average value of ten points.

Measurement and Evaluation of Average Coefficient of Thermal Expansion

The adhesive film obtained by the Example and the comparative example was heat-hardened by heating at 200 degreeC for 90 minutes, and the sheet-form hardened | cured material was obtained by peeling a PET film. The hardened | cured material was cut into the test piece of about 5 mm in width and about 15 mm in length, and the thermomechanical analysis was performed by the tensile weighting method using the thermomechanical analyzer Thermo Plus TMA 8310 (made by Rigaku Corporation). After mounting a test piece to the said apparatus, it measured continuously twice under the measurement conditions of a load of 1g and a temperature increase rate of 5 degree-C / min. In the second measurement, the average thermal expansion coefficient (ppm) from 25 ° C to 150 ° C was calculated.

Measurement and Evaluation of Dielectric Tangents

The adhesive film obtained by the Example and the comparative example was thermosetted by heating at 200 degreeC for 90 minutes, and the support body was peeled off, and the sheet-like hardened | cured material was obtained. The hardened | cured material was cut out to length 80mm and width 2mm, and it was set as the evaluation sample. About this evaluation sample, the dielectric tangent was measured at the measurement frequency of 5.8 GHz and the measurement temperature of 23 degreeC by the cavity resonance perturbation method using the HP8362B apparatus by Agilent Technologies. Two test pieces were measured and the average value was computed.

<Evaluation of flame retardancy>

Batch-type vacuum pressurized laminator MVLP-500 on both surfaces of the base material from which the copper foil of the copper clad laminated board (Hitachi Kasei Co., Ltd. product "679-FG") of the board | substrate thickness 0.2mm was etched off the adhesive film 40 micrometers created by the Example and the comparative example. It laminated on both surfaces of the laminated board using (MEIKI Co., Ltd. brand name). Lamination was performed by depressurizing for 30 second and making atmospheric pressure 13 hPa or less, and then pressing at 100 degreeC and pressure 0.74 Mpa for 30 second. After peeling off PET film of a support body, 40 micrometers of adhesive films were laminated on both surfaces on the same conditions again. Thereafter, the PET film was peeled off and thermosetted at 200 ° C. for 90 minutes to obtain a sample for a flame retardant test. The cut surface was cut into 12.7 mm in width and 127 mm in length, and the cut surface was ground with a grinder (RotoPol-22, manufactured by Strers). With the above five samples as one set, the flame-retardant test was done according to UL94 vertical flame-retardant test. It was set as "(circle)" when there were all five samples remaining after flame contact for 10 second, and it was set as "x" when there was no sample remaining after flame contact for 10 seconds.

&Lt; Example 1 >

6 parts by mass of naphthalene type epoxy resin (Epoxy equivalent 144, DIC Corporation "EXA-4032SS") and 12 parts by mass of bixylenol type epoxy resin (Epoxy equivalent 190, Mitsubishi Chemical Corporation "YX4000HK") 9 mass parts of type epoxy resins (epoxy equivalent about 290, Nippon Kayaku Co., Ltd. product "NC3000H") were melt | dissolved by stirring, stirring 4 mass parts of methyl ethyl ketone (MEK), and 25 mass parts of solvent naphtha. After cooling to room temperature, phosphorus-containing active ester curing agent (benzoyl esterified product of phosphazene-based phenol resin; YLH1437 manufactured by Mitsubishi Chemical Co., Ltd., esterification rate of about 83%, active group equivalent weight of about 332, P content of 9wt%, nonvolatile content 60 9 parts by mass of a mass% MEK solution), 45 parts by mass of an active ester curing agent (DIC Co., Ltd. product "EXB9460S-65T", a toluene solution of 65% by mass of nonvolatile matter having an active group equivalent of about 223), 4- as a curing accelerator. 5 parts by mass of a MEK solution of 5% by mass of dimethylaminopyridine and 160 parts by mass of spherical silica ("DOC-Tech" "SOC2" surface-treated with aminosilane and an average particle diameter of 0.5 μm) were mixed, and a high speed rotary mixer The varnish of the thermosetting resin composition was produced by disperse | distributing uniformly.

Subsequently, the resin composition varnish is uniformly coated with a die coater so that the thickness of the resin composition layer after drying is 40 μm on a release surface of a polyethylene terephthalate film (thickness 38 μm, hereinafter referred to as PET film) subjected to an alkyd type release treatment. It apply | coated and dried at 80-110 degreeC (average 95 degreeC) for 5 minutes (amount of residual solvent in resin composition layer: about 2 mass%). Next, it wound up in roll form, bonding a 15-micrometer-thick polypropylene film to the surface of a resin composition layer. The roll-shaped adhesive film was slit to a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 × 336 mm.

<Example 2>

8 parts by weight of naphthalene type epoxy resin (Epoxy equivalent 144, DIC Corporation "EXA-4032SS") and 10 parts by mass of bixylenol type epoxy resin (Epoxy equivalent 190, Mitsubishi Chemical Corporation "YX4000HK"), modified naphthalene 9 parts by mass of a type epoxy resin (about 330 epoxy equivalent, "ESN-475V" manufactured by Nippon Steel Chemical Co., Ltd.) 4 parts by mass of methyl ethyl ketone (MEK), 25 parts by mass of solvent naphtha It was dissolved by heating with stirring. After cooling to room temperature, phosphorus-containing active ester curing agent (benzoyl esterified product of phosphazene-based phenol resin; YLH1437 manufactured by Mitsubishi Chemical Co., Ltd., about 83% esterification rate, about 332 equivalents of active group, non-volatile content of P content 9wt% 60 9 parts by mass of a mass% MEK solution, 42 parts by mass of an active ester curing agent ("EXB9460S-65T" manufactured by DIC Corp., a toluene solution of 65% by mass of a nonvolatile matter having an active group equivalent of about 223) and a phenoxy resin (weight 5 mass parts of 5 mass% MEK solution of 4-dimethylaminopyridine as a hardening accelerator, 5 mass parts of average molecular weight 35000, MEK of 30 mass% of non volatile matters "YL7553BH30" non-volatile content manufactured by Mitsubishi Chemical Corporation, and 5 mass parts 2 parts by weight of starpyroids (manufactured by Gansu Chemical Co., Ltd., IM-401) as 8 parts by weight of a solvent naphtha at room temperature for 12 hours at room temperature and spherical silica (manufactured by Adomatech Co., Ltd.) Surface-treated with aminosilane And 150 mass parts of average particle diameters were mixed, it was disperse | distributed uniformly by the high speed rotary mixer, and the varnish of the thermosetting resin composition was produced. Subsequently, an adhesive film was obtained in exactly the same manner as in Example 1 using this resin composition varnish.

<Example 3>

8 parts by weight of naphthalene type epoxy resin (Epoxy equivalent 144, DIC Corporation "EXA-4032SS") and 10 parts by mass of bixylenol type epoxy resin (Epoxy equivalent 190, Mitsubishi Chemical Corporation "YX4000HK"), modified naphthalene 9 mass parts of type | mold epoxy resins (epoxy equivalent about 330, "ESN-475V" by Shin-Nitetsu Chemical Co., Ltd.) were melt | dissolved by stirring, stirring 4 mass parts of methyl ethyl ketone (MEK), and 25 mass parts of solvent naphtha. After cooling to room temperature, phosphorus-containing active ester curing agent (benzoyl esterified product of phosphazene-based phenol resin; YLH1437 manufactured by Mitsubishi Chemical Co., Ltd., about 83% esterification rate, about 332 equivalents of active group, non-volatile content of P content 9wt% 60 9 parts by mass of a mass% MEK solution), and 30 parts by mass of a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Co., Ltd., about 232 cyanate equivalent, MEK solution of 75% by mass of nonvolatile matter) 5 parts by mass of a novolak-type polyfunctional cyanate ester resin ("PT30" manufactured by Lonza Japan Co., Ltd., cyanate equivalent weight about 124, 80 mass% of non volatile matters), phenoxy resin (weight average molecular weight 35000, Mitsubishi Chemical 1 mass solution of MEK and cyclohexanone of 30 mass% of non volatile matters manufactured by "YL7553BH30", 0.7 mass part of 5 mass% MEK solution of 4-dimethylaminopyridine as a hardening accelerator, and cobalt (III) Acetyl Acetonate (Tokyo Hwaseong Co., Ltd.) 4.5 mass parts of 1 mass% MEK solution and 2 mass parts of staphyloid (Kantsu Chemical Co., Ltd. make, IM-401) as 1 mass% of manufacture), and fixed and swelled by 8 mass parts of solvent naphtha at room temperature for 12 hours. And 150 parts by mass of spherical silica ("Coma" manufactured by Adomatech Co., Ltd.) with an aminosilane and an average particle diameter of 0.5 µm were mixed and uniformly dispersed with a high speed rotary mixer to produce a varnish of a thermosetting resin composition. . Subsequently, an adhesive film was obtained in exactly the same manner as in Example 1 using this resin composition varnish.

<Example 4>

20 parts by mass of biphenyl-type epoxy resin (Epoxy equivalent approximately 290, Nihon Kayaku Co., Ltd. "NC3000H"), 20 parts by mass of bisphenol A type epoxy resin (Epoxy equivalent 187, Mitsubishi Chemical Corporation "828 US") It melt | dissolved by stirring, stirring 10 mass parts of methyl ethyl ketone (MEK). After cooling to room temperature, phosphorus-containing active ester curing agent (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide system; manufactured by DIC Corporation, EXB9401-65BK, equivalent to about 274 active groups) 20 parts by mass of a non-volatile matter 65 mass% MIBK solution having a P content of 3 wt%, and additionally an active ester curing agent ("EXB9460S-65T" manufactured by DIC Corporation, a toluene solution having a non-volatile content of 65 mass% of an active group equivalent of about 223) 30 5 parts by mass of a triazine-containing cresol novolak resin ("LA3018-50P" manufactured by DIC Corporation, a phenol equivalent of about 151, a 2-methoxypropanol solution having a nonvolatile content of 50% by mass), and 4-dimethyl as a curing accelerator. 3 parts by mass of a 5% by mass MEK solution of aminopyridine and 220 parts by mass of spherical silica ("Coma" manufactured by Adomatech Co., Ltd.) with aminosilane and an average particle diameter of 0.5 μm) were mixed with a high speed rotary mixer. It disperse | distributed so that the varnish of the thermosetting resin composition was produced. Subsequently, an adhesive film was obtained in exactly the same manner as in Example 1 using this resin composition varnish.

&Lt; Comparative Example 1 &

In Example 1, phosphorus containing active ester hardening | curing agent (benzoyl esterified substance of phosphazene-type phenol resin; YLH1437 by Mitsubishi Chemical Corporation, esterification rate about 83%, active group equivalent about 332, non-volatile matter 60 mass of P content 9wt% 9 parts by mass of phosphazene-based phenolic resin (phenol equivalent 250, manufactured by Otsuka Chemical Co., Ltd. "SPH-100", P content 12wt%, nonvolatile matter 60% by mass MEK solution) to 6.5 parts by mass A resin composition varnish was produced except in the same manner. Subsequently, an adhesive film was obtained in exactly the same manner as in Example 1 using this resin composition varnish.

Comparative Example 2

In Example 3, phosphorus containing active ester hardening | curing agent (benzoyl esterified substance of phosphazene-type phenol resin; YLH1437 by Mitsubishi Chemical Co., Ltd., about 83% of esterification ratio, about 332 active group equivalent, 60 mass of non volatile matters of 9 wt% of P content. 4 parts by mass of a phosphazene-based flame retardant ("SPS-100" manufactured by Otsuka Chemical Co., Ltd., no active group, P content 13wt%) without heat addition and 9 parts by mass of MEK solution) A resin composition varnish was produced in exactly the same manner except for. Subsequently, an adhesive film was obtained in exactly the same manner as in Example 1 using this resin composition varnish.

&Lt; Comparative Example 3 &

In Example 1, phosphorus containing active ester hardening | curing agent (benzoyl esterified substance of phosphazene-type phenol resin; YLH1437 by Mitsubishi Chemical Corporation, esterification rate about 83%, active group equivalent about 332, non-volatile matter 60 mass of P content 9wt% 45 parts by mass of an active ester curing agent (EXB9460S-65T manufactured by DIC Corporation, a nonvolatile matter 65% by mass of a nonvolatile matter having an active group equivalent of about 223) was used without the use of 9 parts by mass of 9% by mass of MEK solution). A resin composition varnish was produced in exactly the same manner except for doing the same. Subsequently, an adhesive film was obtained in exactly the same manner as in Example 1 using this resin composition varnish.

The results are shown in Table 1.

From the results of Table 1, it can be seen that the resin compositions of Examples 1 to 4 can obtain a sufficient peeling strength at low arithmetic mean roughness, have a low dielectric tangent and excellent flame retardancy. On the other hand, in Comparative Example 3 in which no active ester curing agent containing a phosphorus atom was added, flame retardancy could not be obtained. Moreover, in the phosphorus containing flame retardant (phosphazene phenol resin) which has a phenolic hydroxyl group like the comparative example 1, arithmetic mean roughness became large and peeling strength also fell. Furthermore, when a non-crosslinking type phosphazene flame retardant was used as in Comparative Example 2, the arithmetic mean roughness increased.

It was possible to provide a resin composition capable of forming a plated conductor layer having a small arithmetic mean roughness on the surface of the insulating layer in a wet roughening process and having sufficient peeling strength while maintaining dielectric properties and thermal expansion coefficient. Moreover, the adhesive film, the prepreg, the multilayer printed wiring board, and the semiconductor device using this can be provided. Furthermore, electric appliances such as computers, mobile phones, digital cameras, and TVs equipped with them, and vehicles such as motorcycles, automobiles, trams, ships, and aircrafts can be provided.

Claims (13)

A resin composition comprising (A) an epoxy resin and an active ester curing agent containing (B) phosphorus atoms. The resin composition according to claim 1, wherein (B) an active ester curing agent containing a phosphorus atom is obtained from a condensation reaction between a carboxylic acid compound and a phosphorus atom-containing hydroxy compound. The resin composition according to claim 1 or 2, wherein the active ester curing agent containing a phosphorus atom (B) is represented by one or more selected from the group consisting of the following general formulas (1) to (3):

(In formula, R may be an alkyl group, an alkenyl group, an aralkyl group, an aryl group, and may have a substituent. R1 is an alkyl group containing a phosphorus atom, an alkenyl group containing a phosphorus atom, an aral containing a phosphorus atom. And a carboxyl group, an aryl group containing a phosphorus atom, a phosphazene skeleton, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, and may have a substituent. A hydroxyl group, a phenyl group, and a naphthyl group, and two R 2 groups may be bonded to each other to form a cyclic group, n represents 1 to 10.

(Wherein R4 is an alkyl group containing a phosphorus atom, an alkenyl group containing a phosphorus atom, an aralkyl group containing a phosphorus atom, an aryl group containing a phosphorus atom, a phosphazene skeleton, 9,10-dihydro-9- Oxa-10-phosphaphenanthrene 10-oxide may be mentioned and may have a substituent R3 may be an alkyl group, an alkenyl group, an aralkyl group, an aryl group, and may have a substituent R5 is hydrogen, Hydroxyl group, phenyl group, naphthyl group, n represents 1 to 10.)

(In formula, R <6> can mention an alkyl group, an alkenyl group, an aralkyl group, and an aryl group, and may have a substituent. R <7> represents the benzoyl group which may be substituted. N represents 1-10.) The resin composition according to claim 1 or 2, wherein when the nonvolatile content in the resin composition is 100 mass%, the active ester curing agent containing (B) phosphorus atoms is 1 to 15 mass%. The phosphorus content in a resin composition is 0.05-3 mass%, when the non-volatile content in a resin composition is 100 mass%, The resin composition of Claim 1 or 2 characterized by the above-mentioned. (C) Inorganic filler is contained further, The resin composition of Claim 1 or 2 characterized by the above-mentioned. (E) Curing agent is further contained, The resin composition of Claim 1 or 2 characterized by the above-mentioned. The ratio between the total number of epoxy groups of (A) epoxy resin and the total number of active ester curing agents (B) containing phosphorus atoms and reactors of (E) curing agents is 1: 0.2 to 2, Resin composition. 3. The peeling strength of the conductor layer and the insulating layer obtained by curing the resin composition to form an insulating layer, roughening and plating the surface of the insulating layer is 0.36 kgf / cm to 1.0 kgf / cm. The arithmetic mean roughness after hardening a resin composition and forming an insulating layer, and roughening the surface of the insulating layer is 10 nm-200 nm, The average from 25 degreeC to 150 degreeC after hardening a resin composition and forming an insulating layer The thermal expansion coefficient is 5 ppm-25 ppm, The resin composition characterized by the above-mentioned. The adhesive film in which the resin composition of Claim 1 or 2 was layered on the support body. The prepreg in which the resin composition of Claim 1 or 2 was impregnated in the sheet-like reinforcement base material. The multilayer printed wiring board with which the insulating layer was formed with the hardened | cured material of the resin composition of Claim 1 or 2. The multilayer printed wiring board of Claim 12 is used, The semiconductor device characterized by the above-mentioned.