JP6823807B2 - Resin composition, prepreg, metal foil laminated board, resin sheet, and printed wiring board - Google Patents

Description

The present invention relates to resin compositions, prepregs, metal foil-clad laminates, resin sheets, and printed wiring boards.

In recent years, as semiconductor packages widely used in electronic devices, communication devices, personal computers, etc. have become more sophisticated and smaller, the high integration and high-density mounting of each component for semiconductor packages has accelerated in recent years. ing. Along with this, the warp of the semiconductor plastic package caused by the difference in the coefficient of thermal expansion between the semiconductor element and the printed wiring board for the semiconductor plastic package has become a problem, and various measures have been taken.

One of the countermeasures is to reduce the thermal expansion of the insulating layer used for the printed wiring board. This is a method of suppressing warpage by bringing the coefficient of thermal expansion of a printed wiring board close to the coefficient of thermal expansion of a semiconductor element, and is currently being actively pursued (see, for example, Patent Documents 1 to 3).

As a method of suppressing the warp of the semiconductor plastic package, in addition to the low thermal expansion of the printed wiring board, the rigidity of the laminated board is increased (high rigidity) and the glass transition temperature of the laminated board is increased (high Tg). (See, for example, Patent Documents 4 and 5).

Japanese Unexamined Patent Publication No. 2013-216884 Japanese Patent No. 3173332 Japanese Unexamined Patent Publication No. 2009-035728 Japanese Unexamined Patent Publication No. 2013-001807 Japanese Unexamined Patent Publication No. 2011-178992

However, the low thermal expansion of the printed wiring board by the conventional method described in Patent Documents 1 to 3 is already approaching the limit, and further low thermal expansion is difficult.

High rigidity of the laminated board is achieved by highly filling the resin composition used for the laminated board with a filler or by using an inorganic filler having a high elastic modulus such as alumina. However, there is a problem that the high filling of the filler deteriorates the moldability of the laminated plate, and the use of an inorganic filler such as alumina deteriorates the coefficient of thermal expansion of the laminated plate. Therefore, increasing the rigidity of the laminated board has not sufficiently achieved the suppression of warpage of the semiconductor plastic package.

In addition, the method of increasing the Tg of the laminated board improves the elastic modulus at the time of reflow, and is therefore effective in reducing the warp of the semiconductor plastic package. However, the method based on high Tg causes deterioration of moisture absorption and heat resistance due to an increase in crosslink density and generation of voids due to deterioration of moldability. Therefore, it is practically used in the field of electronic materials where extremely high reliability is required. Often problematic. Therefore, a method for solving these problems is desired.

Furthermore, the insulating layer of the printed wiring board is also required to have a high elastic modulus maintenance rate, moisture absorption and heat resistance, high copper foil peel strength, desmear resistance, and excellent chemical resistance. However, no resin composition has been reported that provides a cured product that can satisfy all of these problems.

The present invention has been made in view of the above problems, and a resin composition that gives a cured product having excellent copper foil peel strength and plating peel strength, and a prepreg and a metal foil-clad laminate using the resin composition. , Resin sheets, and printed wiring boards.

The present inventors have conducted diligent studies in order to solve the above problems. As a result, they have found that the above problems can be solved by having a predetermined epoxy resin (A), and have completed the present invention.

That is, the present invention is as follows.
[1]
Epoxy resin (A) represented by the following formula (1) and
Cyanate ester compound (B), containing,
Among the group consisting of the naphthol aralkyl type cyanate ester compound represented by the following formula (2) and the biphenyl aralkyl type cyanate ester compound represented by the following formula (3), the cyanate ester compound (B) is represented by the following formula (2). Containing any one or more ,
Resin composition.
(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R _{3 to} R ₆ each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. , X are independent of each other
Ethyleneoxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, or 2 to 15 carbon atoms Indicates an alkylene group, where n is n> 0
Is. )
(In the equation, R ₇ independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of ₁ to 50.)
(In the formula, R ₈ independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 to 50.)
[2]
The epoxy equivalent of the epoxy resin (A) is 250 to 850 g / eq. Is,
The resin composition according to [1].
[3]
The epoxy equivalent of the epoxy resin (A) is 350 to 550 g / eq. Is,
The resin composition according to [1] or [2].
[4]
The content of the epoxy resin (A) is 1 to 90 parts by mass with respect to 100 parts by mass of the resin solid content.
The resin composition according to any one of [1] to [3].
[5]
Further, it contains a filler (C),
The resin composition according to any one of [1] to [4] .
[6]
Further, any one of the group consisting of an epoxy resin other than the epoxy resin represented by the general formula (1), a maleimide compound, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. Contains more than seeds,
The resin composition according to any one of [1] to [ 5] .
[7]
The content of the filler (C) is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content.
The resin composition according to [5] or [6] .
[8]
With the base material
The resin composition according to any one of [1] to [7] , which is impregnated or coated on the base material.
Prepreg.
[9]
The prepreg according to [8] in which at least one sheet is laminated,
The prepreg has metal foils arranged on one or both sides of the prepreg.
Metal leaf-clad laminate.
[10]
With the support
The resin composition according to any one of [1] to [7] , which is arranged on the surface of the support.
Laminated resin sheet.
[11]
A resin sheet containing the resin composition according to any one of [1] to [7] .
[12]
Insulation layer and
It has a conductor layer formed on the surface of the insulating layer and
The insulating layer contains the resin composition according to any one of [1] to [7] .
Printed wiring board.

According to the present invention, a resin composition that gives a cured product having excellent copper foil peel strength and plating peel strength, and a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board using the resin composition are provided. Can also be provided.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited thereto, and various modifications are made without departing from the gist thereof. Is possible. In the present embodiment, the “resin solid content” refers to a component of the resin composition excluding the filler and the solvent, and the “resin solid content 100 parts by mass” refers to the resin composition, unless otherwise specified. It means that the total of the components excluding the filler and the solvent in the product is 100 parts by mass.

[Resin composition]
The resin composition of the present embodiment contains an epoxy resin (A) represented by the following formula (1) and a cyanate ester compound (B).
(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R _{3 to} R ₆ each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. , X are independently ethyleneoxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group. , Or an alkylene group having 2 to 15 carbon atoms, where n is n> 0).

[Epoxy resin (A)]
The epoxy resin (A) is a compound represented by the above formula (1), and has one or more bisphenol A type structural units and one or more hydrocarbon-based structural units in the molecule. By using the epoxy resin (A) composed of such a bisphenol A type structural unit and a hydrocarbon-based structural unit, the copper foil peel strength and the plating peel strength of the obtained cured product tend to be improved.

Here, in the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. Of these, a methyl group is preferable.

R _{3 to} R ₆ independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. Of these, a hydrogen atom is preferable.

X is ethylene group, ethyleneoxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, or carbon. It shows an alkylene group having 3 to 15 atoms. Of these, an ethylene group is preferable.

n represents a natural number, preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 5.

In addition, a commercially available epoxy resin (A) can also be used. Examples of commercially available products include, but are not limited to, EPICLON EXA-4850-150 (manufactured by DIC Corporation), EPICLON EXA-4816 (manufactured by DIC Corporation), and the like. These may be used alone or in combination of two or more.

The content of the epoxy resin (A) is preferably 1 to 90 parts by mass, preferably 10 to 80 parts by mass, and more preferably 20 to 70 parts by mass with respect to 100 parts by mass of the resin solid content. , More preferably 30 to 60 parts by mass. When the content of the epoxy resin (A) is within the above range, the copper foil peel strength and the plating peel strength of the obtained cured product tend to be further improved.

The epoxy equivalent of the epoxy resin (A) is preferably 250 to 800 g / eq. More preferably, 250 to 550 g / eq. And more preferably 350-550 g / eq. And even more preferably, 410-550 g / eq. Is. When the epoxy equivalent of the epoxy resin (A) is within the above range, the copper foil peel strength and the plating peel strength of the obtained cured product tend to be further improved. In particular, the epoxy equivalent of the epoxy resin (A) is 410-550 g / eq. Therefore, the water absorption rate tends to be lower.

[Cyanic acid ester compound (B)]
The cyanate ester compound (B) is not particularly limited, but for example, a naphthol aralkyl type cyanate ester compound represented by the following formula (2), a biphenyl aralkyl type cyanate ester compound represented by the following formula (3), and a bis. (3,5-dimethyl4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-disyanatobenzene, 1,4-disyanatobenzene, 1,3,5-trisianatobenzene, 1,3-disianatonaphthalene, 1,4-disianatonaphthalene, 1,6-disianatonaphthalene, 1,8-disianatonaphthalene, 2,6-disianatonaphthalene, 2,7-disianatonaphthalene, 1, 3,6-Trisianatonaphthalene, 4,4'-disianatobiphenyl, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, and 2, 2'-bis (4-cyanatophenyl) propane; prepolymers of these cyanate esters and the like can be mentioned. Among these, any one or more of the group consisting of the naphthol aralkyl type cyanate ester compound represented by the following formula (2) and the biphenyl aralkyl type cyanate ester compound represented by the following formula (3) shall be contained. Is preferable. By using such a cyanate ester compound, the copper foil peel strength and the plating peel strength of the obtained cured product tend to be further improved. The cyanate ester compound (B) may be used alone or in combination of two or more.
(In the equation, R ₇ independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of ₁ to 50.)
(In the formula, R ₈ independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 to 50.)

In the formula (2), R ₇ independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. Further, in the formula (2), n ₁ represents an integer of 1 to 50, preferably 1 to 10, and more preferably 1 to 6.

In the formula (3), R ₈ independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. Further, in the formula (3), n ₃ represents an integer of 1 to 50, preferably 1 to 10, and more preferably 1 to 7.

The method for producing the cyanate ester compound (B) is not particularly limited, and a known method can be used as a method for synthesizing the cyanate ester compound. The known method is not particularly limited, but for example, a method of reacting a phenol resin and cyanogen halide in the presence of a basic compound in an inert organic solvent, a salt of the phenol resin and the basic compound, and water. Examples thereof include a method in which the mixture is formed in the contained solution, and then the obtained salt and cyanogenated cyanide are subjected to a two-phase interfacial reaction.

The phenol resin used as the raw material of these cyanate ester compounds (B) is not particularly limited, and for example, a naphthol aralkyl type phenol resin represented by the following formula (4), a novolak type phenol resin, and a biphenyl aralkyl type phenol resin can be used. Can be mentioned.

(In the formula, R ₉ independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 to 50.)

In the formula (4), R ₉ independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. Further, in the formula (4), n ₄ represents an integer of 1 to 50, preferably 1 to 10, and more preferably 1 to 6.

The naphthol aralkyl type phenol resin represented by the formula (4) can be obtained by condensing the naphthol aralkyl resin and cyanic acid. Here, the naphthol aralkyl type phenol resin is not particularly limited, and for example, naphthols such as α-naphthol and β-naphthol, p-xylene glycol, α, α'-dimethoxy-p-xylene, and 1 , 4-Di (2-Hydroxy-2-propyl) Benzene and other benzenes are obtained by reaction with benzenes. The naphthol aralkyl type cyanate ester can be selected from those obtained by condensing the naphthol aralkyl resin obtained as described above with cyanic acid.

Here, the content of the cyanate ester compound (B) is preferably 1 to 90 parts by mass, preferably 10 to 80 parts by mass, and more preferably 20 to 20 parts by mass with respect to 100 parts by mass of the resin solid content. It is 70 parts by mass, more preferably 30 to 60 parts by mass. When the content of the cyanate ester compound is within the above range, the copper foil peel strength and the plating peel strength of the obtained cured product tend to be further improved.

[Filler (C)]
The resin composition of the present embodiment may further contain a filler (C). The filler (C) is not particularly limited, and examples thereof include an inorganic filler and an organic filler. As the filler (C), one type may be used alone, or two or more types may be used in combination.

The inorganic filler is not particularly limited, but for example, silicas such as natural silica, molten silica, synthetic silica, amorphous silica, aerodil and hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, magnesium oxide, etc. Metal oxides such as zirconium oxide; metal nitrides such as boron nitride, coagulated boron nitride, silicon nitride and aluminum nitride; metal sulfates such as barium sulfate; aluminum hydroxide and aluminum hydroxide heat-treated products (heating aluminum hydroxide) Treated and partially reduced crystalline water), metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdenum; zinc compounds such as zinc borate and zinc tintate; alumina , Clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20 , Glass short fibers (including fine glass powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, spherical glass, and the like.

The organic filler is not particularly limited, and examples thereof include rubber powders such as styrene type powder, butadiene type powder, and acrylic type powder; core shell type rubber powder; silicone resin powder; silicone rubber powder; and silicone composite powder. Be done.

Among these, it is preferable to contain at least one selected from the group consisting of silica, alumina, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride, preferably alumina and boron nitride. It is more preferable to contain at least one selected from the group consisting of aggregated boron nitride, silicon nitride, and aluminum nitride. By using such a filler (C), the thermal conductivity of the obtained cured product tends to be further improved, and the copper foil peel strength and the plating peel strength tend to be further improved.

Here, the content of the filler (C) is preferably 50 to 1600 parts by mass, more preferably 50 to 1000 parts by mass, and further preferably 50 to 500 parts by mass with respect to 100 parts by mass of the resin solid content. It is a mass part. When the content of the filler (C) is within the above range, the thermal conductivity of the obtained cured product tends to be further improved.

[Silane coupling agent and wet dispersant]
The resin composition of the present embodiment may further contain a silane coupling agent and a wet dispersant.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances, but for example, γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ. Aminosilane compounds such as −aminopropyltrimethoxysilane; epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; acrylicsilane compounds such as γ-acryloxypropyltrimethoxysilane; N-β- (N-) Examples thereof include thionic silane compounds such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; and phenylsilane compounds. The silane coupling agent may be used alone or in combination of two or more.

The wet dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints, but for example, DISPERBYK-110, 111, 118, 180, 161 and BYK-W996 manufactured by Big Chemie Japan Co., Ltd. , W9010, W903 and the like.

[Other ingredients]
The resin composition of the present embodiment may contain other components in addition to the above components, if necessary. The other components are not particularly limited, but are, for example, other epoxy resins other than the epoxy resin represented by the general formula (1), maleimide compounds, phenol resins, oxetane resins, benzoxazine compounds, and polymerizable unsaturated compounds. One or more selected from the group consisting of compounds having a group can be mentioned.

[Other epoxy resins]
As the other epoxy resin, any compound other than the epoxy resin represented by the above formula (1) and having two or more epoxy groups in one molecule can be used, and generally known ones can be used. The type is not particularly limited. Specific examples thereof include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, and cresol novolac. Type epoxy resin, xylene novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional Phenol type epoxy resin, tetrafunctional phenol type epoxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, phenol aralkyl novolac type epoxy resin, Double naphthol aralkylnovolac type epoxy resin, aralkylnovolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, butadiene, etc. Examples thereof include a compound having an epoxy bond, a compound obtained by reacting a hydroxyl group-containing silicone resin with epichlorohydrin, and a halide thereof. These epoxy resins may be used alone or in combination of two or more.

Among these, it is preferable that the epoxy resin is at least one selected from the group consisting of biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, polyfunctional phenol type epoxy resin, and naphthalene type epoxy resin.

[Maleimide compound]
The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule, and for example, 1,3-bis (3-maleimidephenoxy) benzene and 1,3-bis (4-). Maleimide phenoxy) benzene, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 2,2-bis (4- (4-maleimide phenoxy) -phenyl) propane, 3,3-dimethyl-5, 5-diethyl-4,4-diphenylmethanebismaleimide, 4,4-diphenylether bismaleimide, 4,4-diphenylsulphon bismaleimide, 4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylene bismaleimide, m -Phenylene bismaleimide, N-hydroxyphenylmaleimide, N-phenylmaleimide, bis (3,5-diethyl-4-maleimidephenyl) methane, bis (3,5-dimethyl-4-maleimidephenyl) methane, bis (3-) Ethyl-5-methyl-4-maleimidephenyl) methane, bis (4-maleimidephenyl) methane, phenylmethanemaleimide, novolac-type maleimide compound, biphenylaralkyl-type maleimide and prepolymers of these maleimide compounds, or maleimide compounds and amine compounds Prepolymers can be mentioned.

Among these, bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, novolak. Type maleimide compounds and biphenyl aralkyl type bismaleimide are preferred.

[Phenol resin]
As the phenol resin, generally known phenol resins can be used as long as they have two or more hydroxy groups in one molecule, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, and aralkyl novolac type. Phenolic resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol resin , Novolac aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, hydroxyl group-containing silicone resin, etc., but are particularly limited. It's not a thing. These phenol resins can be used alone or in combination of two or more.

[Oxetane resin]
As the oxetane resin, generally known ones can be used, and the type thereof is not particularly limited. Specific examples thereof include alkyl oxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3'. -Di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (trade name manufactured by Toa Synthetic), OXT-121 (manufactured by Toa Synthetic) Product name) and the like. These oxetane resins can be used alone or in combination of two or more.

[Benzooxazine compound]
As the benzoxazine compound, a generally known compound can be used as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A type benzoxazine BA-BXZ (trade name manufactured by Konishi Chemicals), bisphenol F type benzoxazine BF-BXZ (trade name manufactured by Konishi Chemicals), and bisphenol S type benzoxazine BS-BXZ (trade name manufactured by Konishi Chemicals). First name) and so on. These benzoxazine compounds can be used alone or in admixture of two or more.

[Compounds with polymerizable unsaturated groups]
As the compound having a polymerizable unsaturated group, generally known compounds can be used, and the type thereof is not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polypropylene glycol di (. (Meta) of monovalent or polyhydric alcohols such as trimethylolpropane di (meth) acrylate, trimethylol propanedi (meth) acrylate, trimethylol propanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Acrylates: Epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate and bisphenol F type epoxy (meth) acrylate; benzocyclobutene resin; (bis) maleimide resin and the like. These compounds having unsaturated groups can be used alone or in admixture of two or more.

[Curing accelerator]
The resin composition of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, but for example, imidazoles such as triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate and the like. Organic peroxides; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-dimethylpyridine, 2-N-ethylanilino Tertiary amines such as ethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenol, xylenol, cresol, resorcin, catechol Phenols such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, organic metal salts such as acetylacetone iron; these organic metal salts Those dissolved in hydroxyl group-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyl tin oxide and other organic tin compounds such as alkyl tin and alkyl tin oxide. .. Among these, triphenylimidazole is particularly preferable because it promotes the curing reaction and tends to have excellent glass transition temperature and coefficient of thermal expansion.

〔solvent〕
The resin composition of the present embodiment may further contain a solvent. By containing the solvent, the viscosity at the time of preparing the resin composition is lowered, the handleability is further improved, and the impregnation property into the base material described later tends to be further improved.

The solvent is not particularly limited as long as it can dissolve a part or all of the resin components in the resin composition, but for example, ketones such as acetone, methyl ethyl ketone and methyl cell solve; aromatics such as toluene and xylene. Group hydrocarbons; amides such as dimethylformamide; propylene glycol monomethyl ether and acetates thereof and the like. As the solvent, one type may be used alone, or two or more types may be used in combination.

[Manufacturing method of resin composition]
The method for producing the resin composition of the present embodiment is not particularly limited, and examples thereof include a method in which each component is sequentially mixed with a solvent and sufficiently stirred. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading can be performed. Specifically, the dispersibility of the filler (C) in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirring machine having an appropriate stirring ability. The above-mentioned stirring, mixing, and kneading treatment can be appropriately performed using, for example, an apparatus for mixing such as a ball mill or a bead mill, or a known apparatus such as a revolving or rotating type mixing apparatus.

Further, when preparing the resin composition of the present embodiment, an organic solvent can be used if necessary. The type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition. Specific examples thereof are as described above.

[Use]
The resin composition of the present embodiment can be suitably used as a prepreg, a metal foil-clad laminate, a laminate resin sheet, a resin sheet, or a printed wiring board. Hereinafter, the prepreg, the metal foil-clad laminate, the laminate resin sheet, the resin sheet, or the printed wiring board will be described.

[Prepreg]
The prepreg of the present embodiment has a base material and the above-mentioned resin composition impregnated or coated on the base material. The method for producing the prepreg can be carried out according to a conventional method, and is not particularly limited. For example, after impregnating or coating the base material with the resin component of the present embodiment, it is semi-cured (B stage) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes. The prepreg of the present embodiment can be produced.

The content of the resin composition (including the filler (C)) is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, still more preferably 40, based on the total amount of the prepreg. ~ 80% by mass. When the content of the resin composition is within the above range, the moldability tends to be further improved.

The base material is not particularly limited, and known materials used for various printed wiring board materials can be appropriately selected and used depending on the intended use and performance. Specific examples of the fibers constituting the base material are not particularly limited, but for example, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; quartz and the like. Inorganic fibers other than glass; polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technora (registered trademark), Teijin Techno Products ( Total aromatic polyamides such as (manufactured by Co., Ltd.); polyesters such as 2,6-hydroxynaphthoic acid / parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Klaray Co., Ltd.), Zexion (registered trademark, manufactured by KB Salen) Examples thereof include organic fibers such as polyparaphenylene benzoxazole (Zylon (registered trademark), manufactured by Toyo Spinning Co., Ltd.) and polyimide. Among these, at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers is preferable from the viewpoint of low coefficient of thermal expansion. These base materials may be used alone or in combination of two or more.

The shape of the base material is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surfaced mats. The weaving method of the woven fabric is not particularly limited, but for example, plain weave, Nanako weave, twill weave and the like are known, and can be appropriately selected from these known ones according to the intended use and performance. .. Further, a glass woven fabric obtained by opening the fibers or surface-treating with a silane coupling agent or the like is preferably used. The thickness and mass of the base material are not particularly limited, but usually those having a thickness of about 0.01 to 0.3 mm are preferably used. In particular, from the viewpoint of strength and water absorption, the base material is preferably a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g / m ² or less, and a glass woven fabric made of glass fibers of E glass, S glass, and T glass is preferable. More preferred.

[Laminated resin sheet]
The laminated resin sheet of the present embodiment has a support and the resin composition arranged on the support. The laminated resin sheet is used as one means for thinning leaves, and can be produced, for example, by directly coating and drying the resin composition on a support such as a metal leaf or a film.

The support is not particularly limited, but known materials used for various printed wiring board materials can be used. For example, polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polycarbonate film, ethylene tetrafluoroethylene copolymer film, and Organic film base materials such as release films coated with a release agent on the surface of these films, conductor foils such as aluminum foil, copper foil and gold foil, glass plates, SUS plates, plate-like inorganic materials such as FPR. Film is mentioned. Among them, electrolytic copper foil and PET film are preferable.

Examples of the coating method include a method in which a solution of the resin composition of the present embodiment dissolved in a solvent is coated on a support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like.

The laminated resin sheet is preferably one in which the above resin composition is applied to a support and then semi-cured (B-staged). Specifically, for example, the resin composition is applied to a support such as a copper foil and then semi-cured by a method of heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes to obtain a laminated resin sheet. Examples include the manufacturing method. The amount of the resin composition adhered to the support is preferably in the range of 1 to 300 μm in terms of the resin thickness of the laminated resin sheet.

[Resin sheet]
The resin sheet of this embodiment contains a resin composition. The resin sheet is formed by molding a resin composition into a sheet shape. The method for producing the resin sheet can be carried out according to a conventional method, and is not particularly limited. For example, it can be obtained by peeling or etching the support from the laminated resin sheet. A solution prepared by dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-like cavity and dried to form a sheet, so that a sheet base material is not used. A resin sheet (single layer resin sheet) can also be obtained.

[Metal leaf-clad laminate]
The metal foil-clad laminate of the present embodiment has the above-mentioned prepreg in which at least one or more sheets are laminated, and metal foil arranged on one side or both sides of the prepreg. That is, the metal foil-clad laminate of the present embodiment is obtained by laminating and curing the prepreg and the metal foil.

The conductor layer can be a metal foil such as copper or aluminum. The metal foil used here is not particularly limited as long as it is used as a material for a printed wiring board, but a known copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. The thickness of the conductor layer is not particularly limited, but is preferably 1 to 70 μm, more preferably 1.5 to 35 μm.

The molding method of the metal foil-clad laminate and the molding conditions thereof are not particularly limited, and general methods and conditions of the laminated plate for printed wiring boards and the multilayer plate can be applied. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when forming a metal foil-clad laminate. Further, in molding a metal leaf-clad laminate, the temperature is generally in the range of 100 to 350 ° C., the pressure is generally in the range of ^{2 to} 100 kgf / cm ² , and the heating time is in the range of 0.05 to 5 hours. Further, if necessary, post-curing can be performed at a temperature of 150 to 350 ° C. Further, it is also possible to form a multilayer plate by laminating and molding the above-mentioned prepreg in combination with a wiring plate for an inner layer prepared separately.

[Printed circuit board]
The printed wiring board of the present embodiment includes an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition. The metal foil-clad laminate can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The metal leaf-clad laminate has a low coefficient of thermal expansion, good moldability and chemical resistance, and is particularly effectively used as a printed wiring board for a semiconductor package in which such performance is required. Can be done.

Specifically, the printed wiring board of the present embodiment can be manufactured by, for example, the following method. First, the above-mentioned metal foil-clad laminate (copper-clad laminate, etc.) is prepared. An inner layer circuit is formed by etching the surface of a metal foil-clad laminate to prepare an inner layer substrate. The inner layer circuit surface of this inner layer substrate is subjected to surface treatment to increase the adhesive strength as necessary, then the required number of the above-mentioned prepregs are laminated on the inner layer circuit surface, and the metal foil for the outer layer circuit is laminated on the outer side thereof. Then, heat and pressurize to integrally mold. In this way, a multi-layer laminated board in which an insulating layer made of a base material and a cured product of a thermosetting resin composition is formed between an inner layer circuit and a metal foil for an outer layer circuit is manufactured. Next, after drilling holes for through holes and via holes in this multilayer laminated plate, desmear treatment is performed to remove smear, which is a resin residue derived from the resin component contained in the cured product layer. .. After that, a plated metal film that conducts the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of this hole, and the metal foil for the outer layer circuit is further etched to form the outer layer circuit, and the printed wiring board is manufactured. Will be done.

The printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes the resin composition of the present embodiment described above. That is, the above-mentioned prepreg (the base material and the above-mentioned resin composition attached thereto) and the resin composition layer of the metal leaf-clad laminate (the layer composed of the above-mentioned resin composition) include the above-mentioned resin composition. It will form an insulating layer.

When the metal foil-clad laminate is not used, a conductor layer to be a circuit may be formed on the prepreg, the laminate resin sheet, or the resin composition to produce a printed wiring board. At this time, an electroless plating method can also be used to form the conductor layer.

In the printed wiring board of the present embodiment, since the above-mentioned insulating layer has excellent characteristics of copper foil peel strength, plating peel strength, bending strength, water absorption rate, dielectric constant, thermal expansion coefficient, and thermal weight reduction rate, it is a semiconductor. It can be particularly effectively used as a printed wiring board for a package.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

[Synthesis Example 1] Synthesis of 1-naphthol aralkyl type cyanate ester resin (SNCN) In a reactor, α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd.) 300 g (1.28 mol in terms of OH group) and 194.6 g (1.92 mol) of triethylamine (1.5 mol with respect to 1 mol of hydroxy group) were dissolved in 1800 g of dichloromethane, which was used as Solution 1.

125.9 g (2.05 mol) of cyanogen chloride (1.6 mol with respect to 1 mol of hydroxy group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol with respect to 1 mol of hydroxy group), Solution 1 was poured over 30 minutes while maintaining a liquid temperature of -2 to -0.5 ° C. with stirring 1205.9 g of water. After pouring 1 solution, the mixture was stirred at the same temperature for 30 minutes, and then a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of hydroxy group) was dissolved in 65 g of dichloromethane was added for 10 minutes. I poured it over. After 2 pouring of the solution was completed, the reaction was completed by stirring at the same temperature for 30 minutes.

After that, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water, and the electric conductivity of the wastewater in the 5th washing was 5 μS / cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.

The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90 ° C. for 1 hour to obtain 331 g of the target naphthol aralkyl type cyanate ester compound (SNCN) (orange viscous substance). The mass average molecular weight Mw of the obtained SNCN was 600. Infrared absorption spectrum of SNCN showed absorption of 2250 cm ^-1 (cyanic acid ester group) and no absorption of hydroxy group.

[Example 1]
50 parts by mass of SNCN obtained in Synthesis Example 1, 50 parts by mass of epoxy resin (manufactured by Dainippon Ink Co., Ltd., EPICLON EXA-4816, epoxy equivalent 408 g / eq.) Satisfying formula (1), molten silica (SC2050MB, ( A varnish was obtained by mixing 100 parts by mass of Admatex Co., Ltd. (average particle size 5 μm) and 0.10 parts by mass of zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd.).

[Example 2]
Implemented except that 50 parts by mass of an epoxy resin (manufactured by Dainippon Ink Co., Ltd., EPICLON EXA-4850-150, epoxy equivalent 435 g / eq.) Satisfying the formula (1) was used instead of EPICLON EXA-4816. A varnish was obtained by the same operation as in Example 1.

[Comparative Example 1]
Instead of the epoxy resin represented by the above formula (1), 50 parts by mass of a biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC3000FH, epoxy equivalent 320 g / eq.) Is used, and zinc octylate (Nippon Kayaku). A varnish was obtained by the same operation as in Example 1 except that the amount used by Sangyo Co., Ltd. was 0.12 parts by mass.

[Manufacturing method of copper-clad laminate]
The varnish obtained as described above is impregnated and coated on an E glass cloth having a thickness of 0.1 mm, and used at 150 ° C. using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.). The mixture was dried by heating for 1 minute to obtain a prepreg having a resin composition of 50% by mass. Two or eight of these prepregs are stacked, and 12 μm thick electrolytic copper foil (3EC-M3-VLP, manufactured by Mitsui Metal Mining Co., Ltd.) is placed on both sides, and vacuum is applied at a pressure of 30 kg / cm ² and a temperature of 220 ° C. for 150 minutes. Pressing was performed to obtain a copper-clad laminate having an insulating layer thickness of 0.2 mm and 0.8 mm. The following evaluation was performed using the obtained copper-clad laminate. The results are shown in Table 1.

[Copper foil peel strength]
A method for testing a copper-clad laminate for a printed wiring board of JIS C6481 using a test piece (30 mm × 150 mm × thickness 0.8 mm) of a copper-clad laminate having an insulating layer thickness of 0.8 mm obtained as described above. (Refer to 5.7 Peeling strength.) The peeling strength of the copper foil was measured three times, and the average value of the lower limit values was taken as the measured value.

The copper foil on the surface layer of the copper-clad laminate having an insulating layer thickness of 0.8 mm obtained above was removed by etching, and the obtained insulating layer was placed in an alkaline aqueous solution (1N-sodium hydroxide aqueous solution) at 40 ° C. 5 Soaked for minutes (desmear treatment). After washing the insulating layer taken out from the alkaline aqueous solution with water, an electroless copper plating process manufactured by Uemura Kogyo Co., Ltd. (names of chemicals used: MCD-PL, MDP-2, MAT-SP, MAB-4-C, MEL-3-APEA) In ver. 2), electroless copper plating of about 0.5 μm was applied to the insulating layer, and the insulating layer was dried at 130 ° C. for 1 hour. Subsequently, electrolytic copper plating was applied so that the thickness of the plated copper was 20 μm, and drying was performed at 180 ° C. for 1 hour. In this way, a test piece of a printed wiring board in which a conductor layer (plated copper) having a thickness of 20 μm was formed on an insulating layer having a thickness of 0.1 mm was prepared and used for evaluation of an electroless plating peel (with desmear treatment). .. Further, a test piece of a printed wiring board on which a conductor layer was formed was prepared by a step of removing the treatment with an alkaline aqueous solution from the above step, and used for evaluation of an electroless plating peel (without desmear treatment).

[Plating peel strength]
Using the test piece obtained as described above, the plating peel strength (adhesive strength) was measured three times according to JIS C6481, and the average value was calculated. The test piece that swelled due to drying after electrolytic copper plating was evaluated using the non-swelled part. The results are shown in Table 1.

[Water absorption rate]
Using a test piece of a copper-clad laminate with an insulating layer thickness of 0.8 mm obtained as described above, a pressure cooker tester (manufactured by Hirayama Seisakusho, PC-3 type) was used in accordance with JIS C 6481. The water absorption rate after treatment at 121 ° C. and 2 atm for 5 hours was measured.

The resin composition of the present embodiment has industrial applicability as a material for a prepreg, a resin sheet, a metal foil-clad laminate, or a printed wiring board.

Claims (12)

Epoxy resin (A) represented by the following formula (1) and
Containing cyanate ester compound (B) and
Among the group consisting of the naphthol aralkyl type cyanate ester compound represented by the following formula (2) and the biphenyl aralkyl type cyanate ester compound represented by the following formula (3), the cyanate ester compound (B) is represented by the following formula (2). Containing any one or more,
Resin composition.
(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R _{3 to} R ₆ each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. , X are independently ethyleneoxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group. , Or an alkylene group having 2 to 15 carbon atoms, where n is n> 0).
(In the equation, R ₇ independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of ₁ to 50.)
(In the formula, R ₈ independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 to 50.) The epoxy equivalent of the epoxy resin (A) is 250 to 850 g / eq. Is,
The resin composition according to claim 1. The epoxy equivalent of the epoxy resin (A) is 350 to 550 g / eq. Is,
The resin composition according to claim 1 or 2. The content of the epoxy resin (A) is 1 to 90 parts by mass with respect to 100 parts by mass of the resin solid content.
The resin composition according to any one of claims 1 to 3. Further, it contains a filler (C),
The resin composition according to any one of claims 1 to 4. Further, any one of the group consisting of an epoxy resin other than the epoxy resin represented by the general formula (1), a maleimide compound, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. Contains more than seeds,
The resin composition according to any one of claims 1 to 5. The content of the filler (C) is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content.
The resin composition according to claim 5 or 6. With the base material
The resin composition according to any one of claims 1 to 7, which is impregnated or coated on the base material.
Prepreg. The prepreg according to claim 8, wherein at least one or more sheets are laminated.
The prepreg has metal foils arranged on one or both sides of the prepreg.
Metal leaf-clad laminate. With the support
The resin composition according to any one of claims 1 to 7 , which is arranged on the surface of the support.
Laminated resin sheet. A resin sheet containing the resin composition according to any one of claims 1 to 7. Insulation layer and
It has a conductor layer formed on the surface of the insulating layer and
The insulating layer contains the resin composition according to any one of claims 1 to 7.
Printed wiring board.