JP6639072B2 - Resin composition for printed wiring board, prepreg, laminated board and printed wiring board - Google Patents

Description

  The present invention relates to a resin composition, a prepreg, a laminate, and a printed wiring board.

  In recent years, semiconductors widely used in electronic devices, communication devices, personal computers, etc. have been increasingly integrated, functionalized, and densely packed. Demands for characteristics and high reliability are increasing.

In recent years, there has been a strong demand for a reduction in the coefficient of thermal expansion in the surface direction of the laminate.
The reason is that there is a large difference in the coefficient of thermal expansion between the semiconductor element and the printed wiring board for the semiconductor plastic package. This is because a connection failure occurs between package printed wiring boards or between a semiconductor plastic package and a printed wiring board to be mounted.
As a method of reducing the thermal expansion coefficient in the surface direction of the laminate, there is a method of filling an inorganic filler. However, another property required for a laminate for a semiconductor plastic package is a high glass transition temperature (Tg). In order to give the laminate a high glass transition temperature, it is necessary to mix a polyfunctional resin. Polyfunctional resins have high viscosities, and it is difficult to mix many inorganic fillers. As another method, it is known that a rubber elastic organic filler is blended into a varnish containing an epoxy resin (Patent Documents 1 to 6). However, when this varnish is used, the organic filler is blended. In this case, the amount of the inorganic filler is limited and the organic filler with rubber elasticity has high flammability. Was given.
There is a method of blending a silicone resin as a method of obtaining the same effect as blending the rubber elastic component with maintaining the filling amount of the inorganic filler. However, since these resins have a low Tg and a characteristic of a low elastic modulus, However, there is a problem that the Tg and the elastic modulus are lowered depending on the addition amount.

Japanese Patent No. 3173332 JP-A-8-48001 JP 2000-158589 A JP-A-2003-246849 JP-A-2006-143973 JP 2009-035728 A

  The present invention has been made in view of the above problems, and an object of the present invention is to reduce the Tg and the elastic modulus while adding a silicone resin to a resin composition, and to reduce the thermal expansion coefficient in the plane direction. An object of the present invention is to provide a low printed wiring board material resin composition, a prepreg, a laminate, a metal-clad laminate, and a printed wiring board.

The present inventors have conducted intensive studies to solve such problems, and as a result, they have bonds (a) and (b), and the terminal is a functional group selected from R ₁ , a hydroxyl group and an alkoxy group, and the epoxy equivalent Containing a silicon-containing polymer (A), a halogen-free epoxy resin (B), a cyanate ester compound (C), a maleimide compound (D) and an inorganic filler (E), wherein the inorganic filler is 500 to 4000. The present invention has been found that the content of the resin composition (E) is 100 to 1000 parts by mass with respect to a total of 100 parts by mass of the components (B) to (D). Reached.

(1)
(Here, R ₁ is selected from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all R ₁ in the silicon-containing polymer may be the same or different. X is It represents a monovalent organic group containing an epoxy group.)

  The metal foil clad laminate according to the present invention is suitable for a material for a semiconductor plastic package that requires an excellent low thermal expansion coefficient, high heat resistance, high Tg, and high elastic modulus.

  Hereinafter, embodiments of the present invention will be described. The following embodiment is an exemplification for explaining the present invention, and the present invention is not limited to only the embodiment.

  One aspect of the present embodiment includes a silicon-containing polymer (A), a non-halogen epoxy resin (B), a cyanate ester compound (C), a maleimide compound (D), and an inorganic filler (E). The resin composition in which the content of the filler (E) in the resin composition is 100 to 1000 parts by mass based on 100 parts by mass in total of the components (B) to (D).

  Further, as another aspect of the present embodiment, a BT resin obtained by prepolymerizing a silicon-containing polymer (A), a non-halogen epoxy resin (B), a cyanate ester compound (C) and a maleimide compound (D) ( It is a resin composition containing F) and an inorganic filler (E).

  Another aspect of the present embodiment is a resin composition containing an imidazole compound in addition to the resin composition components.

  Further, in another aspect of the present embodiment, a prepreg comprising the resin composition and a base material, a laminate using the prepreg, a resin sheet using the resin composition, and a printed wiring board are also provided.

[Silicon-containing polymer (A)]
The silicon-containing polymer (A) used in the present invention has the following bonds (a) and (b), the terminal is a functional group selected from R ₁ , a hydroxyl group and an alkoxy group, and the epoxy equivalent is 500. There is no particular limitation as long as it is up to 4000, but examples of such a polymer include a branched polysiloxane.

(1)
(Here, R ₁ is selected from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all R ₁ in the silicon-containing polymer may be the same or different. X is It represents a monovalent organic group containing an epoxy group.)
R ₁ in the general formulas (a) and (b) represents a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group , An alkyl group such as 2-ethylhexyl group, an alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group and a biphenyl group; And an aralkyl group such as a phenethyl group. Among them, a methyl group or a phenyl group is preferable.
X in the general formula (b) is 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 2-glycidoxyethyl, 3-glycidoxy. A propyl group, a 4-glycidoxybutyl group, a 2- (3,4-epoxycyclohexyl) ethyl group, a 3- (3,4-epoxycyclohexyl) propyl group, among which a 3-glycidoxypropyl group is preferred. preferable.
In addition, the terminal of the silicon-containing polymer (A) needs to be any of the aforementioned R ₁ , hydroxyl group and alkoxy group from the viewpoint of storage stability of the polymer. In this case, examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Further, the epoxy equivalent of the silicon-containing polymer (A) needs to be in the range of 500 to 4000, preferably 1000 to 2500. If it is less than 500, the fluidity of the resin composition tends to decrease, and if it is more than 4000, it tends to exude on the surface of the cured product, and molding failure tends to occur.

It is preferable that the silicon-containing polymer (A) further has the following bond (c) from the viewpoint of achieving both fluidity and low warpage of the obtained resin composition.
(2)
(Here, R ₂ is selected from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all R ₂ in the silicon-containing polymer may be the same or different.)
R ₂ in the general formula (c) is a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group. Alkyl groups such as groups, alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, biphenyl group, benzyl group, phenethyl group, etc. And the like, and among them, a methyl group or a phenyl group is preferable.
The softening point of such a silicon-containing polymer (A) is preferably set to 40 ° C to 120 ° C, and more preferably set to 50 ° C to 100 ° C. If the temperature is higher than 40 ° C, the mechanical strength of the obtained cured product of the printed wiring board resin composition tends to increase, and if the temperature is lower than 120 ° C, the dispersibility of the silicon-containing polymer (A) in the resin composition improves. Tend to. As a method for adjusting the softening point of the silicon-containing polymer (A), the organic group bonded to the silicon atom, such as the molecular weight of the silicon-containing polymer (A) and the content of constituent bonding units (for example, the content ratio of (a) to (c)). It is possible to set the type of the silicon-containing polymer (A) in the resin composition for a printed wiring board, and from the viewpoint of the fluidity of the obtained resin composition for a printed wiring board. It is preferable to adjust the softening point by setting the content of the aryl group in (A) in the polymer, and the aryl group in this case includes a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group and the like. The content of the phenyl group in the monovalent organic group bonded to the silicon atom in the silicon-containing polymer (A) is preferably from 60 mol% to 99 mol%, more preferably from 70 mol% to 85 mol%. Mole% Desired silicon-containing polymer having a softening point (A) can be obtained by.
The weight average molecular weight (Mw) of the silicon-containing polymer (A) is 1000 to 30,000, preferably 2000 to 20,000, as measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. More preferably, it is 3000-10000. Also. The silicon-containing polymer (A) is preferably a random copolymer. Such a silicon-containing polymer (A) can be obtained by the production method described below, but is available as a commercial product under the trade name AY42-119 manufactured by Dow Corning Toray Silicone Co., Ltd.

The method for producing the silicon-containing polymer (A) can be produced by a known method without any particular limitation. For example, an organochlorosilane, an organoalkoxysilane, a siloxane, or a partially hydrolyzed condensate thereof which can form the units (a) to (c) by a hydrolysis and condensation reaction is used as a starting material and an organic solvent capable of dissolving the reaction product. It can be obtained by mixing all the hydrolyzable groups of the raw materials in a mixed solution with a hydrolyzable amount of water and subjecting the mixture to a hydrolytic condensation reaction. At this time, it is preferable to use organoalkoxysilane and / or siloxane as a raw material in order to reduce the amount of chlorine contained as an impurity in the resin composition for a printed wiring board. In this case, it is preferable to add an acid, a base, and an organometallic compound as a catalyst for accelerating the reaction.
Examples of the organoalkoxysilane and / or siloxane used as a raw material of the silicon-containing polymer (A) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. , Phenyltrimethoxysilane, phenyltoethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, phenylvinyldimethoxysilane, diphenyldimethoxysilane, methylphenyldiethoxysilane, methylvinyldiethoxysilane, phenylvinyldiethoxysilane Silane, diphenyldiethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane, -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (Phenyl) dimethoxysilane, 3-glycidoxypropyl (phenyl) diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) Examples include diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, and hydrolyzed condensates thereof. .

Although the content of the silicon-containing polymer (A) in the resin composition of the present embodiment is not particularly limited, the resin composition components are a silicon-containing polymer (A), a non-halogen epoxy resin (B), and a cyanate ester compound. In the system containing (C), the maleimide compound (D) and the inorganic filler (E), the amount is preferably from 1 to 200 parts by mass based on 100 parts by mass of the components (B) to (D) in total. It is more preferably from 10 to 100 parts by mass, and still more preferably from 20 to 60 parts by mass.
In a system where the resin composition contains a silicon-containing polymer (A), a non-halogen epoxy resin (B), a BT resin (F) and an inorganic filler (D), the components (B) and (F) ) Is preferably 1 to 200 parts by mass, more preferably 10 to 100 parts by mass, and still more preferably 20 to 60 parts by mass with respect to 100 parts by mass in total.
When the content of the silicon-containing polymer (A) is within the preferred range, a printed wiring board having excellent low thermal expansion, glass transition temperature, and elastic modulus can be obtained.

[Non-halogen epoxy resin (B)]
The non-halogen epoxy resin (B) in the resin composition of the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule and does not contain a halogen atom in its molecular structure.
For example, a phenol phenyl aralkyl novolak epoxy resin represented by the formula (3), a phenol biphenyl aralkyl epoxy resin represented by the formula (4), a naphthol aralkyl epoxy resin represented by the formula (5), and thermal expansion In order to lower the value, an anthraquinone epoxy resin represented by the formula (11) or a polyoxynaphthylene epoxy resin represented by the formulas (6) and (12) is used. In addition, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type Epoxy resin, biphenyl-type epoxy resin, aralkyl novolak-type epoxy resin, alicyclic epoxy resin, polyol-type epoxy resin, glycidylamine, glycidyl ester, butadiene and other double-epoxidized compounds, hydroxyl-containing silicone resins and epichlorohydrin And a phenol phenyl aralkyl novolak type epoxy represented by the formula (3) for improving flame retardancy. Phenol biphenyl aralkyl type epoxy resin represented by formula (4), naphthol aralkyl type epoxy resin represented by formula (5), anthraquinone type epoxy resin represented by formula (11), formula (6), formula The polyoxynaphthylene type epoxy resin represented by (12) is preferable.
These non-halogen epoxy resins can be used alone or in appropriate combination of two or more.

(3)
(In the formula, R ₃ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. In the formula, n ₃ represents an integer of 1 or more. The upper limit of n is usually 10, and preferably 7.)

(4)
(In the formula, R ₄ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. In the formula, n ₄ represents an integer of 1 or more. The upper limit of n ₄ is usually 10, preferably 7, preferably 7.) )

(5)
(In the formula, R ₅ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In the formula, n ₅ represents an integer of 1 or more. The upper limit of n ₅ is usually 10, preferably 7, preferably 7. )

(11)

(6)
(In the formula, R ₆ represents a hydrogen atom or a methyl group.)

(12)
(In the formula, R ₁₂ represents a hydrogen atom or a methyl group.)
Commercially available epoxy resins of the above formulas (6) and (12) can be used. Examples of the products are EXA-7311, EXA-7311-G3, EXA-7311-G4, and EXA-7311 manufactured by DIC Corporation. -G4S, EXA-7311L, HP-6000.

  Further, a phosphorus-containing epoxy resin or a brominated epoxy resin can be used in combination depending on the required application. The brominated epoxy resin is not particularly limited as long as it is a bromine atom-containing compound having two or more epoxy groups in one molecule. Specifically, a brominated bisphenol A type epoxy resin, a brominated phenol novolak type epoxy resin and the like are exemplified.

Although the content of the non-halogen epoxy resin (B) in the resin composition of the present embodiment is not particularly limited, the resin composition components are a silicon-containing polymer (A), a non-halogen epoxy resin (B), and a cyanate ester compound. In the system containing (C), the maleimide compound (D) and the inorganic filler (E), the amount is preferably 10 to 50 parts by mass with respect to 100 parts by mass in total of the components (B) to (D). More preferably, it is 10 to 40 parts by mass.
In a system where the resin composition contains a silicon-containing polymer (A), a non-halogen epoxy resin (B), a BT resin (F) and an inorganic filler (D), the components (B) and (F) ) Is preferably 10 to 50 parts by mass, more preferably 10 to 60 parts by mass, and still more preferably 20 to 40 parts by mass with respect to 100 parts by mass in total.
By setting the content of the non-halogen epoxy (B) in a preferable range, a printed wiring board having excellent low thermal expansion, glass transition temperature, and elastic modulus can be obtained.

In the resin composition of the present embodiment, the cyanate ester compound (C) is an essential component in order to impart excellent properties such as chemical resistance and adhesiveness to the cured product. Examples of the cyanate ester compound (C) include a naphthol aralkyl-type cyanate compound represented by the formula (7), a novolak-type cyanate ester represented by the formula (8), a phenolbiphenylaralkyl-type cyanate compound, Bis (3,5-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1, , 3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl) e And bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, and 2,2-bis (4-cyanatophenyl) propane. These may be used alone or in combination of two or more.
Among them, a naphthol aralkyl cyanate compound represented by the formula (7), a novolac cyanate ester and a phenol biphenyl aralkyl cyanate compound represented by the formula (8) are excellent in flame retardancy and have excellent curability. It is particularly preferable because it is high and the thermal expansion coefficient of the cured product is low.

(7)
(In the formula, each R ₇ independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable. In the formula, n ₇ represents an integer of 1 or more. The upper limit of n ₇ is usually 10, preferably 10 or more. 6)

(8)
(In the formula, R ₈ each independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
Wherein, _{n 8} is an integer of 1 or more. upper limit of n ₈ is usually 10, preferably 7.

  The method for producing these cyanate ester compounds is not particularly limited, and any of the existing methods for cyanate ester synthesis may be used. Specifically, for example, as described in JP-A-2009-35728, it is obtained by reacting a naphthol aralkyl-type phenol resin with a cyanogen halide in an inert organic solvent in the presence of a basic compound. Can be. Further, it is also possible to adopt a method of forming a salt of a similar naphthol aralkyl-type phenol resin and a basic compound in a solution containing water, and then performing a two-phase interfacial reaction with a cyanogen halide to synthesize. .

(13)
(In the formula, R ₁₃ each independently represents a hydrogen atom or a methyl group, and n ₁₃ represents an integer of 1 or more.)

  In addition, naphthol aralkyl cyanate compounds include naphthols such as α-naphthol or β-naphthol and p-xylylene glycol, α, α′-dimethoxy-p-xylene, 1,4-di (2-hydroxy- It can be selected from those obtained by condensing naphthol aralkyl resin obtained by reaction with 2-propyl) benzene or the like and cyanic acid.

  Further, the ratio (CN / Ep) of the number of cyanate groups of the cyanate ester compound (C) to the number of epoxy groups of all epoxy resins contained in the resin composition of the present embodiment is not particularly limited, but heat resistance, flame retardancy, and the like. From the viewpoint of water absorption, the content is preferably 0.2 to 2.5, more preferably 0.3 to 2.0.

Although the content of the cyanate ester compound (C) in the resin composition of the present embodiment is not particularly limited, a silicon-containing polymer (A), a non-halogen epoxy resin (B), a cyanate ester compound (C), a maleimide compound In the system containing (D) and the inorganic filler (E), it is preferably 10 to 50 parts by mass, more preferably 20 to 40 parts by mass, based on 100 parts by mass of the components (B) to (D) in total. Parts by weight.
When the total content of the cyanate ester compound (C) is within the preferred range, the degree of curing is increased, and a printed wiring board having flame retardancy, glass transition temperature, water absorption, and elastic modulus can be obtained.

[Maleimide compound (D)]
The maleimide compound (D) in the resin composition of the present embodiment is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, and bis (3,5 -Dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, represented by the formula (9) Examples thereof include a maleimide compound, a prepolymer of these maleimide compounds, or a prepolymer of a maleimide compound and an amine compound. One or more of them can be used as appropriate.
Among them, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, a compound represented by the formula ( The maleimide compound represented by 9) is preferable, and particularly, the maleimide compound exemplified by the formula (9) is preferable.

(9)
(In the formula, R ₉ each independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable. In the formula, n ₉ represents an integer of 1 or more. The upper limit of n ₉ is usually 10, preferably 10 or more. 7)

Although the content of the maleimide compound (D) in the resin composition of the present embodiment is not particularly limited, a silicon-containing polymer (A), a non-halogen epoxy resin (B), a cyanate ester compound (C), a maleimide compound (D) ) And the inorganic filler (E), the amount is preferably 10 to 50 parts by mass, more preferably 20 to 40 parts by mass, based on 100 parts by mass of the components (B) to (D) in total. It is.
By setting the content of the maleimide compound (D) within a preferable range, the degree of curing is increased, and a printed wiring board having excellent flame retardancy, glass transition temperature, water absorption, and elasticity can be obtained.

[Inorganic filler (E)]
The inorganic filler (E) in the resin composition of the present embodiment is not particularly limited as long as it is commonly used in the art. For example, silicas such as natural silica, fused silica, amorphous silica, hollow silica, etc., aluminum hydroxide, heat-treated aluminum hydroxide (heat-treated aluminum hydroxide to reduce a part of water of crystallization), aluminum nitride Metal hydrates such as boron nitride, boehmite, magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined Talc, mica, short glass fiber (glass fine powder such as E glass or D glass), hollow glass, spherical glass, titanium oxide, silicone rubber, silicone composite powder, etc., and one or more kinds are appropriately mixed. It is possible to use it.
Among them, silica, alumina, aluminum nitride, boron nitride, boehmite, aluminum hydroxide, titanium oxide, silicone rubber, silicone composite powder magnesium hydroxide, alumina, and talc are preferable from the viewpoints of thermal expansion coefficient and flame resistance. From the viewpoint of properties, a molybdenum compound or a molybdenum compound coated with an inorganic oxide is preferable.

The average particle diameter (D50) of the inorganic filler (E) is not particularly limited, but is preferably 0.2 to 5 μm in consideration of dispersibility. Furthermore, as described above, since the surface area increases as the average particle diameter of the inorganic filler becomes smaller and the viscosity of the resin composition easily increases, the effect of the present invention is easily obtained, and the upper limit of the average particle diameter is increased. It is more preferably 3 μm, and particularly preferably 1 μm.
In the present specification, the average particle diameter (D50) means the median diameter (D50), and is a value such that when the particle size distribution of the measured powder is divided into two, the larger side and the smaller side have the same amount. It is. More specifically, the particle size distribution of a powder charged in a predetermined amount into an aqueous dispersion medium is measured by a laser diffraction scattering type particle size distribution measuring device, and the volume is integrated from small particles to 50% of the total volume. The value when reached.

The content of the inorganic filler (E) in the resin composition of the present embodiment is such that the resin composition components are a silicon-containing polymer (A), a non-halogen epoxy resin (B), a cyanate ester compound (C), and a maleimide. In the system containing the compound (D) and the inorganic filler (E), it is essential that the amount is 100 to 1000 parts by mass based on 100 parts by mass of the total of the components (B) to (D). However, in a system containing the silicon-containing polymer (A), the non-halogen epoxy (B), the BT resin (F) and the inorganic filler (E), the total amount of the components (B) and (F) is 100 parts by mass. On the other hand, it is essential that the amount be 100 to 1000 parts by mass.
By setting the content of the inorganic filler (E) within the range, it is possible to obtain a printed wiring board having excellent flame retardancy, moldability, and drill workability.

In addition to the inorganic filler (E), a silane coupling agent or a wet dispersant can be used in combination to improve the dispersibility of the inorganic filler and the adhesive strength between the resin and the inorganic filler or glass cloth. is there.
The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of an inorganic substance. Specific examples include aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ Vinylsilanes such as methacryloxypropyltrimethoxysilane, cationic silanes such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, phenylsilanes, etc. One or two or more of them can be used in appropriate combination.
The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints. For example, wetting and dispersing agents such as Disperbyk-110, 111, 180, 161, BYK-W996, W9010, and W903 manufactured by Big Chemie Japan Ltd. can be used.

[BT resin (F)]
The BT resin (F) in the resin composition of the present embodiment refers to a solution of a cyanate ester compound and a maleimide compound in a solvent-free state or in an organic solvent such as methyl ethyl ketone, N-methylpyrroline, dimethylformamide, dimethylacetamide, toluene, and xylene. And heated and mixed to form a prepolymer.

The cyanate ester compound to be used is not particularly limited. For example, a naphthol aralkyl cyanate ester compound represented by the formula (7), a novolak cyanate ester represented by the formula (8), a phenol biphenyl aralkyl cyanate ester, Bis (3,5-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1, , 3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl) Ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, 2,2-bis (4-cyanatophenyl) propane, and the like, and one or more kinds are appropriately mixed. It is also possible to use it.
Among them, the naphthol aralkyl cyanate ester compound represented by the formula (7), the novolak cyanate ester represented by the formula (8), and the phenol biphenyl aralkyl cyanate ester are obtained. It is preferable from the viewpoint of curability and low coefficient of thermal expansion.
Also, the maleimide compound is not particularly limited, but N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, formula (9) And a prepolymer of these maleimide compounds, a prepolymer of a maleimide compound and an amine compound, and the like, and one or more of them can be used as appropriate.
Among them, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, a compound represented by the formula ( The maleimide compound represented by 9) is preferable, and particularly, the maleimide compound exemplified by the formula (9) is preferable.

The proportion of the maleimide compound in the BT resin (F) is not particularly limited, but is preferably in the range of 5 to 75% by mass with respect to the total amount of the BT resin (F) from the viewpoint of glass transition temperature, flame retardancy, and curability. A range of 10 to 70% by mass is particularly preferred.
The range of the molecular weight of the BT resin (F), which is a prepolymer, is not particularly limited, but is from about 100 to 100,000 in terms of number average molecular weight from the viewpoint of handling properties, glass transition temperature, and curability. Is preferred.

The content of the BT resin (F) in the resin composition of the present invention is not particularly limited, but is preferably 10 to 90 parts by mass, more preferably 100 parts by mass based on the total of components (B) and (F). Is from 20 to 80 parts by mass.
By setting the content of the BT resin (F) in a preferable range, the degree of curing is increased, and a printed wiring board excellent in flame retardancy, glass transition temperature, water absorption, and elasticity can be obtained.

The resin composition of the present embodiment may contain an imidazole compound represented by the formula (10). This imidazole compound has a function of accelerating the curing and has a function of increasing the glass transition temperature of the cured product. Examples of the substituent Ar in the formula (10) include a phenyl group, a naphthalene group, a biphenyl group, an anthracene group, and a modified hydroxyl group thereof, which may have a substituent. Of these, a phenyl group is preferable.
Further, the substituent R ₁₀ in the formula (10) is a hydrogen atom, an alkyl group or a hydroxyl-modified product is suitable aryl groups such as phenyl group which may have a substituent, further, Ar, R ₁₀ both phenyl More preferably, it is a group.
Among them, 2,4,5-triphenylimidazole in which R ₁₀ in the formula (10) is a phenyl group and Ar is a phenyl group is preferable.
(10)
(Wherein, Ar is each independently a phenyl group, a naphthalene group, a biphenyl group, an anthracene group or a modified hydroxy group thereof, and R ₁₀ is a hydrogen atom, an alkyl group or a modified hydroxy group thereof, Represents an aryl group which may have a group.)

Although the content of the imidazole compound in the resin composition of the present invention is not particularly limited, the resin composition is composed of a silicon-containing polymer (A), a non-halogen epoxy resin (B), a cyanate ester compound (C), and a maleimide compound. In the system containing (D) and the inorganic filler (E), the amount is preferably 0.01 to 10 parts by mass, more preferably 0 to 10 parts by mass, based on 100 parts by mass in total of the components (B) to (D). 0.1 to 5 parts by mass.
Further, in a system in which the resin composition component contains a silicon-containing polymer (A) represented by the formula (1), a non-halogen epoxy resin (B), a BT resin (F) and an inorganic filler (E), The amount is preferably from 0.01 to 10 parts by mass, more preferably from 0.1 to 5 parts by mass, based on 100 parts by mass of the total of components (B) and (F).
By setting the content of the imidazole compound within a preferable range, the degree of curing is increased, and a printed wiring board excellent in glass transition temperature, water absorption, and elasticity can be obtained.

  In the resin composition of the embodiment, other curing accelerators can be used in addition to the imidazole compound as long as the desired properties are not impaired. Such compounds include, for example, organic peroxides exemplified by benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate and the like; azobisnitrile The azo compound; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine Tertiary amines such as triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; monomeric phenols such as phenol, xylenol, cresol, resorcinol, catechol; lead naphthenate, lead stearate; Naphthenic acid Organic metal salts such as zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; formed by dissolving these organic metal salts in monomeric hydroxyl-containing compounds such as phenol and bisphenol. Inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyltin oxide; and other organic tin compounds such as alkyltin and alkyltin oxide.

  Further, the resin composition of the present embodiment may contain a solvent as needed. For example, when an organic solvent is used, the viscosity at the time of preparing the resin composition decreases, the handling property is improved, and the impregnation property of the glass cloth is increased. The type of the solvent may be a compound containing the formula silicon-containing polymer (A), a non-halogen epoxy resin (B), a cyanate ester compound (C), a maleimide compound (D), or a silicon-containing polymer (A) or a non-halogen epoxy resin ( There is no particular limitation as long as a part or all of the mixture of B) and the BT resin (F) can be dissolved. Specific examples thereof include, for example, ketones such as acetone, methyl ethyl ketone and methyl cellosolve, aromatic hydrocarbons such as toluene and xylene, amides such as dimethylformamide, propylene glycol methyl ether and acetates thereof. However, the present invention is not particularly limited to these. The solvents can be used alone or in combination of two or more.

  The resin composition of the present invention can be prepared according to a conventional method, and comprises a silicon-containing polymer (A), a non-halogen epoxy resin (B), a cyanate ester compound (C), a maleimide compound (D), and an inorganic filler. The material (E) and the other optional components described above, or the silicon-containing polymer (A), the non-halogen epoxy resin (B), the BT resin (F), the inorganic filler (E), and the other optional components described above are homogenized. The method for preparing the resin composition is not particularly limited as long as it is a method for obtaining a resin composition containing the same. For example, the resin composition of the present embodiment can be easily prepared by sequentially mixing a silicon-containing polymer, a non-halogen epoxy resin, a cyanate ester compound, a maleimide compound, and silica in a solvent and sufficiently stirring the mixture.

  When preparing the resin composition of the present invention, an organic solvent can be used as necessary. The type of the organic solvent is a silicon-containing polymer (A), a non-halogen epoxy resin (B), a cyanate ester compound (C), a maleimide compound (D), or a silicon-containing polymer (A), a non-halogen epoxy resin ( There is no particular limitation as long as the mixture of B) and the BT resin (F) can be dissolved. The specific example is as described above.

  At the time of preparing the resin composition, known processes (such as stirring, mixing, and kneading processes) for uniformly dissolving or dispersing each component can be performed. For example, when uniformly dispersing the inorganic filler (E), the dispersibility in the resin composition is increased by performing the stirring and dispersion treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. The above-described stirring, mixing, and kneading treatments can be appropriately performed using a known apparatus such as a mixing apparatus such as a ball mill or a bead mill, or a revolving / rotating type mixing apparatus.

  On the other hand, the prepreg of the present invention can be obtained by combining the above resin composition with a substrate, specifically, impregnating or applying the above resin composition to the substrate. The method for producing the prepreg can be performed according to a conventional method, and is not particularly limited. For example, after the resin component of the present invention is impregnated or applied to a base material, the base material is semi-cured (B-staged) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes. The prepreg of the embodiment can be manufactured. The prepreg of the present embodiment is not particularly limited, but the amount of the resin composition (including the inorganic filler) based on the total amount of the prepreg is preferably in the range of 30 to 90% by mass.

The substrate used in the present invention is not particularly limited, and known substrates used for various printed wiring board materials can be appropriately selected and used depending on the intended use and performance. . Specific examples thereof include, for example, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, and T glass, inorganic fibers other than glass such as quartz, and polyparaphenylene terephthalamide (Kevlar (A registered trademark, manufactured by DuPont), copolyparaphenylene / 3,4'oxydiphenylene terephthalamide (Technola (registered trademark), manufactured by Teijin Techno Products Ltd.), etc., 2,6-hydroxy Polyester such as naphthoic acid / parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.); organic fibers such as polyparaphenylenebenzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.); and polyimide. However, it is not particularly limited to these.
Among them, E glass, T glass, S glass, and Q glass are preferable from the viewpoint of low thermal expansion.
These substrates can be used alone or in combination of two or more.
As the shape of the base material, a woven fabric, a nonwoven fabric, a roving, a chopped strand mat, a surfing mat, and the like are known, and as a weaving method of the woven fabric, a plain weave, a Nanako weave, a twill weave, and the like are known. It can be appropriately selected and used depending on the intended use and performance, and those obtained by subjecting them to fiber opening treatment and glass woven fabric surface-treated with a silane coupling agent or the like are preferably used. The thickness and mass of the substrate are not particularly limited, but usually those having a thickness of about 0.01 to 0.3 mm are suitably used. In particular, from the viewpoints of strength and water absorption, the substrate 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 more preferably a glass woven fabric made of E glass glass fiber.

On the other hand, the metal foil-clad laminate of the present invention can be obtained by laminating at least one or more of the above-described prepregs, arranging a metal foil on one or both surfaces thereof, and performing lamination molding. Specifically, one or more of the above-described prepregs are laminated, and a metal foil such as copper or aluminum is arranged on one or both surfaces thereof as desired, and the laminate is formed by laminating as necessary. The metal foil-clad laminate of the present embodiment can be manufactured. The metal foil used here is not particularly limited as long as it is used for a printed wiring board material, but a known copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. The thickness of the metal foil is not particularly limited, but is preferably from 2 to 70 μm, and more preferably from 2 to 35 μm. The method of forming the metal foil-clad laminate and the molding conditions are also not particularly limited, and general techniques and conditions for laminated boards and multilayer boards for printed wiring boards can be applied. For example, at the time of forming a metal foil-clad laminate, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used. The temperature is 100 to 300 ° C., and the pressure is 2 to 100 kgf / surface pressure. cm ^2, the heating time in the range of 0.05 to 5 hours are common. Further, if necessary, post-curing can be performed at a temperature of 150 to 300 ° C. Moreover, it is also possible to form a multilayer board by laminating and combining the prepreg of the present embodiment and a separately manufactured inner layer wiring board.

  The metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The metal foil-clad laminate of the present invention 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 requiring such performance. be able to.

The printed wiring board in the present invention can be manufactured, for example, by the following method. First, a metal foil-clad laminate such as a copper-clad laminate of the present invention is prepared. An etching process is performed on the surface of the metal foil-clad laminate to form an inner circuit, thereby producing an inner substrate. The surface of the inner layer circuit of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, then the required number of prepregs of the present invention are stacked on the inner layer circuit surface, and a metal foil for an outer layer circuit is further provided on the outside thereof. Laminate and apply heat and pressure to form a single piece. In this way, a multilayer laminate in which an insulating layer made of a cured product of the base material and the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit is manufactured. Next, after performing a drilling process for through holes and via holes on the multilayer laminate, a desmear process is performed to remove smear, which is a resin residue derived from the resin component contained in the cured product layer. . Then, on the wall surface of this hole, a plated metal film is formed to conduct the inner layer circuit and the outer layer circuit metal foil, and then the outer layer circuit metal foil is etched to form the outer layer circuit, and the printed wiring board is manufactured. Is done.
The prepreg of the present invention (substrate and the resin composition of the present invention attached thereto) and the resin composition layer of the metal foil-clad laminate (the layer composed of the resin composition of the present invention) are the resin composition of the present invention. Will be formed.

  On the other hand, the laminated resin sheet of the present embodiment can be obtained by applying a solution obtained by dissolving the resin composition of the present embodiment described above in a solvent to a sheet substrate and drying the solution. Examples of the sheet substrate used here include, for example, a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and a release film obtained by applying a release agent to the surface of these films, Examples include organic film base materials such as polyimide films, conductive foils such as copper foils and aluminum foils, and plate-like materials such as glass plates, SUS plates, and FRP, but are not particularly limited thereto. Examples of the application method include a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied to a sheet substrate using a bar coater, a die coater, a doctor blade, a baker applicator, or the like. Further, after drying, the sheet substrate is peeled off or etched from the laminated resin sheet, whereby a single-layer sheet (resin sheet) can be obtained. Note that a solution obtained by dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-shaped cavity, dried, and formed into a sheet by using the sheet base. A single-layer sheet (resin sheet) can be obtained without the need.

  In the production of the single-layer or laminated resin sheet of the present embodiment, the drying conditions for removing the solvent are not particularly limited, but when the temperature is low, the solvent is likely to remain in the resin composition, and when the temperature is high, the resin is removed. Since the curing of the composition proceeds, the temperature is preferably 1 to 90 minutes at a temperature of 20C to 170C. In addition, the thickness of the resin layer of the single-layer or laminated resin sheet of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment and the applied thickness, and is not particularly limited. When the thickness is large, the solvent tends to remain during drying, so that the thickness is preferably 0.1 to 500 μm.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Synthesis Example 1 Synthesis of α-naphthol aralkyl cyanate compound A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was previously cooled to 0 to 5 ° C. with brine, and cyanogen chloride was added thereto. 0.47 g (0.122 mol), 9.75 g (0.0935 mol) of 35% hydrochloric acid, 76 ml of water, and 44 ml of methylene chloride were charged.
An α-naphthol aralkyl type phenol resin (SN485, OH equivalent weight) in which R ₇ in the formula (7) is all hydrogen atoms while stirring is maintained at a temperature of −5 to + 5 ° C. and a pH of 1 or less. Softening point: 86 ° C., 20 g (0.0935 mol) manufactured by Nippon Steel Chemical Co., Ltd., and a solution obtained by dissolving 14.16 g (0.14 mol) of triethylamine in 92 ml of methylene chloride were added by a dropping funnel. After dropwise addition over a period of time, 4.72 g (0.047 mol) of triethylamine was further added dropwise over 15 minutes.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 15 minutes, then, the reaction solution was separated, and the organic layer was separated. After the obtained organic layer was washed twice with 100 ml of water, methylene chloride was distilled off under reduced pressure by an evaporator, and finally concentrated and dried at 80 ° C. for 1 hour to obtain a cyanate ester of α-naphthol aralkyl resin. 23.5 g of a compound (α-naphthol aralkyl cyanate compound) was obtained.

Synthesis Example 2 Synthesis of BT Resin 1 36 parts by mass of an α-naphthol aralkyl cyanate compound (cyanate equivalent: 261 g / eq.) Synthesized by the method described in Synthesis Example 1 and all of R ₉ in the formula (9) are hydrogen 26 parts by mass of a maleimide compound (BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd.) in which n is 0 to 1 are dissolved in dimethylacetamide and reacted at 150 ° C. with stirring to obtain a BT resin 1 Was.

Synthesis Example 3 Synthesis of BT Resin 2 36 parts by mass of an α-naphthol aralkyl cyanate compound (cyanate equivalent: 261 g / eq.) Synthesized by the method described in Synthesis Example 1 and bis (3-ethyl-5-methyl- BT resin 2 was obtained by dissolving 26 parts by mass of 4-maleimidophenyl) methane (BMI-70, manufactured by Keiai Kasei Co., Ltd.) in dimethylacetamide and stirring at 150 ° C with stirring.

Example 1
30 parts by mass of a polysiloxane (AY42-119, manufactured by Dow Corning Toray Co., Ltd., epoxy equivalent: 1660 g / eq., Manufactured by Dow Corning Toray Co., Ltd.) having a softening point of 80 ° C. as a silicon-containing polymer, Synthesis Example 1 30 parts by mass of the α-naphthol aralkyl-type cyanate compound (cyanate equivalent: 261 g / eq.) Obtained in the above, a polyoxynaphthylene-type epoxy resin (HP-6000, epoxy equivalent: 250 g / eq., DIC Corporation) )), 10 parts by weight of the maleimide compound (BMI-2300) used in Synthesis Example 2, 5 parts by weight of a silane coupling agent (manufactured by Toray Dow Coating Co., Ltd.), and a wetting dispersant (disperbyk- 161, Big Chemie Japan Co., Ltd.), 1 part by mass, spherical fused silica (SC2500-SQ, average particle size) 0.5 [mu] m, were mixed 200 parts by mass of Admatechs Co., Ltd.) to obtain a varnish. This varnish was diluted with methyl ethyl ketone, impregnated and coated on a T glass woven fabric having a thickness of 0.1 mm, and dried by heating at 140 ° C. for 3 minutes to obtain a prepreg having a resin content of 50% by mass.

Example 2
Except that 30 parts by mass of a prepolymer of 2,2-bis (4-cyanatephenyl) propane (CA210, equivalent of cyanate 139, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used instead of the α-naphthol aralkyl type cyanate compound. A prepreg was obtained in the same manner as in Example 1.

Example 3
A novolak-type cyanate compound in which all of R ₈ in the formula (8) are hydrogen atoms instead of the α-naphthol aralkyl-type cyanate compound (Primaset PT-30, manufactured by Lonza Japan K.K., cyanate equivalent: 124 g / eq.) was used in the same manner as in Example 1 except that 30 parts by mass of prepreg was used.

Example 4
30 parts by mass of the silicon-containing polymer used in Example 1, 36 parts by mass of the α-naphthol aralkyl-type cyanate ester compound obtained in Synthesis Example 1, and 38 parts of polyoxynaphthylene-type epoxy resin (HP-6000) 26 parts by mass of the maleimide compound (BMI-2300) used in Synthesis Example 2, 5 parts by mass of the silane coupling agent (Z6040), 1 part by mass of the wetting and dispersing agent (disperbyk-161), 1 part by mass of spherical fused silica ( SC2500-SQ) and 200 parts by mass of 1,4,5-triphenylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) in which R ₁₀ and Ar in the formula (10) are all phenyl groups. I got a varnish. This varnish was diluted with methyl ethyl ketone, impregnated and coated on a T glass woven fabric having a thickness of 0.1 mm, and dried by heating at 140 ° C. for 3 minutes to obtain a prepreg having a resin content of 50% by mass.

Example 5
Except that 26 parts by mass of bis (3-ethyl-5-methyl-4maleimidophenyl) methane (BMI-70) used in Synthesis Example 3 was used instead of the maleimide compound (BMI-2300) used in Synthesis Example 1. A prepreg was obtained in the same manner as in Example 4.

Example 6
Instead of the polyoxynaphthylene type epoxy resin (HP-6000) used in Example 1, a phenol biphenyl aralkyl type epoxy resin (NC-3000-FH, epoxy equivalent: 320 g / eq., Manufactured by Nippon Kayaku Co., Ltd.) Was used in the same manner as in Example 4 except that 38 parts by mass of prepreg was used.

Example 7
38 masses of a naphthalene-modified epoxy resin (ESN-175V, epoxy equivalent: 255 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd.) instead of the polyoxynaphthylene type epoxy resin (HP-6000) used in Example 1 A prepreg was obtained in the same manner as in Example 4, except for using some parts.

Example 8
Instead of the polyoxynaphthylene type epoxy resin (HP-6000) used in Example 1, a phenol phenyl aralkyl novolak type epoxy resin (NC-2000-L, epoxy equivalent: 226 g / eq., Manufactured by Nippon Kayaku Co., Ltd.) A prepreg was obtained in the same manner as in Example 4 except that 38 parts by mass) was used.

Example 9
Further, a prepreg was obtained in the same manner as in Example 4 except that 0.01 parts by mass of 2-ethyl-4-methylimidazole (2E4MZ) was added.

Example 10
A prepreg was obtained in the same manner as in Example 4 except that 62 parts by mass of the BT resin obtained in Synthesis Example 2 was used without using the α-naphthol aralkyl-type cyanate compound and the maleimide compound used in Synthesis Example 2. Was.

Example 11
A prepreg was prepared in the same manner as in Example 4 except that 62 parts by mass of the BT resin obtained in Synthesis Example 3 was used without using the α-naphthol aralkyl-type cyanate compound and the bismaleimide compound used in Synthesis Example 2. Obtained.

Comparative Example 1
36 parts by mass of the α-naphthol aralkyl cyanate ester compound obtained in Synthesis Example 1, 38 parts by mass of polyoxynaphthylene type epoxy resin (HP-6000), and the maleimide compound (BMI-2300) used in Synthesis Example 2 ), 26 parts by mass of a silane coupling agent (Z6040), 1 part by mass of a wetting and dispersing agent (disperbyk-161), 200 parts by mass of spherical fused silica (SC2500-SQ), and R in the formula (10). _A varnish was obtained by mixing 1 part by mass of 2,4,5-triphenylimidazole (Wako Pure Chemical Industries, Ltd.) in which ₁₀ and Ar are all phenyl groups. This varnish was diluted with methyl ethyl ketone, impregnated and coated on a T glass woven fabric having a thickness of 0.1 mm, and dried by heating at 140 ° C. for 3 minutes to obtain a prepreg having a resin content of 50% by mass.

Comparative Example 2
Example 2 Example 3 was repeated except that 30 parts by mass of an epoxy-modified silicone resin 1 (X-22-163A, epoxy equivalent: 1000 g / eq., Manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the silicon-containing polymer used in Example 1. In the same manner as in Example 4, a prepreg was obtained.

Comparative Example 3
Example 2 Example 3 was repeated except that 30 parts by mass of an epoxy-modified silicone resin 2 (X-22-163B, epoxy equivalent: 1750 g / eq., Manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the silicon-containing polymer used in Example 1. In the same manner as in Example 4, a prepreg was obtained.

Comparative Example 4
Example 1 Except that 30 parts by mass of the epoxy-modified silicone resin 3 (X-4-1053, epoxy equivalent: 820 g / eq., Manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the silicon-containing polymer used in Example 1. In the same manner as in Example 4, a prepreg was obtained.

Comparative Example 5
In the same manner as in Example 4 except that 30 parts by mass of the epoxy-modified silicone resin 4 (KF105, epoxy equivalent: 490 g / eq., Manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the silicon-containing polymer used in Example 1. I got a prepreg.

Comparative Example 6
Example 6 Example 6 was repeated except that 30 parts by mass of an epoxy-modified silicone resin (X-22-163A, epoxy equivalent: 1000 g / eq., Manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the silicon-containing polymer used in Example 1. A prepreg was obtained in the same manner as described above.

Comparative Example 7
Example 7 Example 30 was repeated except that 30 parts by mass of an epoxy-modified silicone resin (X-22-163A, epoxy equivalent: 1000 g / eq., Manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the silicon-containing polymer used in Example 1. A prepreg was obtained in the same manner as described above.

Comparative Example 8
Example 8 Example 30 was repeated except that 30 parts by mass of an epoxy-modified silicone resin (X-22-163A, epoxy equivalent: 1000 g / eq., Manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the silicon-containing polymer used in Example 1. A prepreg was obtained in the same manner as described above.

Preparation of Metal-Foil-Clad Laminate Two prepregs obtained in Examples 1 to 11 and Comparative Examples 1 to 8 were each laminated to form an electrolytic copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) having a thickness of 12 μm. Lamination molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper-clad laminate having an insulating layer thickness of 0.2 mm.

  Tables 1 and 2 show the results of evaluation of the moldability, heat resistance, Tg, elastic modulus, and thermal expansion coefficient in the surface direction using the obtained prepreg and the copper-clad laminate.

Physical property evaluation method of prepreg and metal foil clad laminate Moldability , heat resistance, Tg, modulus of elasticity, and coefficient of thermal expansion were measured by the following methods.
Formability: After removing the copper foil of the copper-clad laminate by etching, the surface was observed to evaluate the presence or absence of voids. The sample without voids was marked with "O", the sample with voids only at the end of the Ankrat plate was marked with "△", and the sample with voids on the entire surface was marked "x".
Heat resistance: n = 5, all were solder floats at 260 ° C., no swelling for 30 minutes, and ○ were swelling.
Glass transition temperature (Tg): The entire surface of the 0.8 mm thick double-sided copper-clad laminate obtained in each of the above Examples and Comparative Examples was etched to prepare a 12 mm × 25 mm test piece, which was then transferred to a DMA device (TA Instruments). The temperature was raised at a rate of 10 ° C./min using a dynamic viscoelasticity measuring device (DMAQ400 manufactured by Mento Co., Ltd.), and the peak position of LossModulus was defined as the glass transition temperature.
Elastic modulus: Measured at room temperature using an autograph (AG5000B, manufactured by Shimadzu Corporation) according to JIS-K6911 using a test piece having a size of 10 mm x 50 mm x 0.8 mm.
Thermal expansion coefficient in the plane direction: After removing the copper foil by etching the copper-clad laminate, the temperature was raised from 40 ° C. to 340 ° C. at a rate of 10 ° C./min by a thermomechanical analyzer (manufactured by TA Instruments), and 60 ° C. The linear expansion coefficient in the plane direction at a temperature of from 120C to 120C was measured. The measurement direction was measured in the longitudinal direction (Warp) of the glass cloth of the laminate.

Moldability ○: No void ×: Whole surface void heat resistance ○: No delamination ×: With delamination Unit Tg: ° C Elasticity: GPa Thermal expansion: ppm / ° C

Moldability ○: No void ×: Whole surface void heat resistance ○: No delamination ×: With delamination Unit Tg: ° C Elasticity: GPa Thermal expansion: ppm / ° C

Claims (27)

A silicon-containing polymer (A) having bonds (a) and (b), the terminal of which is a functional group selected from R ₁ , a hydroxyl group and an alkoxy group, and an epoxy equivalent of 500 to 4000; (B) , a cyanate compound (C), a maleimide compound (D), and an inorganic filler (E), and the content of the inorganic filler (E) in the resin composition is as follows: D) 100 to 1000 parts by mass with respect to 100 parts by mass in total ;
Furthermore ing comprise an imidazole compound of the formula (10), the printed wiring board resin composition.
(1)
(Here, R ₁ is selected from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all R ₁ in the silicon-containing polymer may be all the same or different. X is It represents a monovalent organic group containing an epoxy group.)
(10)
(Wherein, Ar is each independently a phenyl group, a naphthalene group, a biphenyl group, an anthracene group or a modified hydroxy group thereof, and R ₁₀ is a hydrogen atom, an alkyl group or a modified hydroxy group thereof, Represents an aryl group which may have a group.) The resin composition for a printed wiring board according to claim 1, wherein the silicon-containing polymer (A) further has a bond (c).
(2)
(Here, R ₂ is selected from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all R ₂ in the silicon-containing polymer may be the same or different.)   3. The resin composition for a printed wiring board according to claim 1, wherein the silicon-containing polymer (A) has a softening point of 40 ° C. or more and 120 ° C. or less. 4. The silicon-containing polymer wherein R ₁ in (A) is a substituted or unsubstituted phenyl group and / or a methyl group, a printed wiring board resin composition according to any one of claims 1 to 3. The non-halogen epoxy resin (B) is a phenol phenyl aralkyl type epoxy resin represented by the formula (3), a phenol biphenyl aralkyl type epoxy resin represented by the formula (4), and a naphthol aralkyl represented by the formula (5) At least one of the group consisting of a type epoxy resin, an anthraquinone type epoxy resin represented by the formula (11) and a polyoxynaphthylene type epoxy resin represented by the formulas (6) and (12), The resin composition for a printed wiring board according to claim 1.
(3)
(In the formula, R ₃ represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more.)
(4)
(In the formula, R ₄ represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more.)
(5)
(In the formula, R ₅ represents a hydrogen atom or a methyl group, and n ₅ represents an integer of 1 or more.)
(6)
(In the formula, R ₆ represents a hydrogen atom or a methyl group.)
(11)
(12)
(In the formula, R ₁₂ represents a hydrogen atom or a methyl group.) The cyanate compound (C) comprises a naphthol aralkyl-type cyanate compound represented by the formula (7), a novolak-type cyanate compound represented by the formula (8), and a phenolbiphenylaralkyl-type cyanate compound. The resin composition for a printed wiring board according to any one of claims 1 to 5, wherein the resin composition is any one or more of a group consisting of:
(7)
(In the formula, R ₇ independently represents a hydrogen atom or a methyl group, and n ₇ represents an integer of 1 or more.)
(8)
(In the formula, R ₈ each independently represents a hydrogen atom or a methyl group, and n ₈ represents an integer of 1 or more.) The resin composition for a printed wiring board according to any one of claims 1 to 6, wherein the maleimide compound (D) is represented by the formula (9).
(9)
(In the formula, R ₉ each independently represents a hydrogen atom or a methyl group, and n ₉ represents an integer of 1 or more.)   The content of the silicon-containing polymer (A) is 1 to 200 parts by mass relative to a total of 100 parts by mass of the components (B) to (D). Resin composition for printed wiring boards.   The content of the non-halogen epoxy resin (B) is 10 to 50 parts by mass with respect to 100 parts by mass in total of the components (B) to (D). Resin composition for printed wiring boards.   The content of the cyanate ester compound (C) is 10 to 50 parts by mass with respect to 100 parts by mass in total of the components (B) to (D). Resin composition for printed wiring boards.   The print according to any one of claims 1 to 10, wherein the content of the maleimide compound (D) is 10 to 50 parts by mass with respect to 100 parts by mass in total of the components (B) to (D). Resin composition for wiring board. A silicon-containing polymer (A) having bonds (a) and (b), the terminal of which is a functional group selected from R ₁ , a hydroxyl group and an alkoxy group, and an epoxy equivalent of 500 to 4000; (B), a BT resin (F) obtained by prepolymerizing a cyanate ester compound and a maleimide compound, and an inorganic filler (E), wherein the content of the inorganic filler (E) in the resin composition is as follows: A resin composition for printed wiring boards, which is contained in an amount of 100 to 1,000 parts by mass based on 100 parts by mass in total of (B) and (F).
(1)
(Here, R ₁ is selected from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all R ₁ in the silicon-containing polymer may be all the same or different. X is It represents a monovalent organic group containing an epoxy group.) The cyanate compound used for the BT resin (F) is a naphthol aralkyl cyanate compound represented by the formula (7), a novolak type cyanate compound represented by the formula (8), and a phenol biphenyl aralkyl compound. of the group consisting of cyanate ester compound is any one or more of the printed wiring board resin composition according to claim 1 2.
(7)
(In the formula, R ₇ independently represents a hydrogen atom or a methyl group, and n ₇ represents an integer of 1 or more.)
(8)
(In the formula, R ₈ each independently represents a hydrogen atom or a methyl group, and n ₈ represents an integer of 1 or more.) The BT maleimide compound used in the resin (F) is one represented by the formula (9), according to claim 1 2 or 1 3 printed circuit board resin composition according to.
(9)
(Wherein, R ₉ independently represents a hydrogen atom or a methyl group, and n ₉ represents an integer of 1 or more.) The content of the silicon-containing polymer (A) is, relative to 100 parts by weight of the total of the non-halogen epoxy resin (B) and BT resin (F), 1 to 200 parts by weight, of claim 1 2-1 4 The resin composition for a printed wiring board according to claim 1. The content of the non-halogen epoxy resin (B), the total 100 parts by weight of the non-halogen epoxy resin (B) and BT resin (F), 10 to 50 parts by weight, of claim 1 2-1 5 The resin composition for a printed wiring board according to claim 1. The content of the BT resin (F) is, relative to 100 parts by weight of the total of the non-halogen epoxy resin (B) and BT resin (F), 10 to 90 parts by weight, any one of claims 1 2 to 1 6 The resin composition for a printed wiring board according to claim 1. The resin composition for a printed wiring board according to any one of claims 12 to 17 , further comprising an imidazole compound represented by the formula (10).
(10)
(Wherein, Ar is each independently a phenyl group, a naphthalene group, a biphenyl group, an anthracene group or a modified hydroxy group thereof, and R ₁₀ is a hydrogen atom, an alkyl group or a modified hydroxy group thereof, Represents an aryl group which may have a group.) The resin composition for a printed wiring board according to any one of claims 1 to 11, wherein the imidazole compound is 2,4,5-triphenylimidazole. The inorganic filler (E) is at least one selected from the group consisting of silica, alumina, aluminum nitride, boron nitride, boehmite, aluminum hydroxide, titanium oxide, molybdenum compound, silicone rubber, and silicone composite powder. The resin composition for a printed wiring board according to any one of claims 1 to 19 . Prepreg impregnated or coated printed circuit board resin composition according to the substrate in any one of claims 1-2 0. It said substrate E glass cloth, T glass cloth, S glass cloth, of the group consisting of Q glass cloth and organic fibers, either one or more, prepreg according to claim 2 1. Claim 2 1 or 2 2 laminate obtained by curing superimposed over one of the prepreg according to. Claim 2 1 or 2 2 prepreg and the metal foil and the metal foil-clad laminate obtained by curing by laminating described. A single-layer sheet obtained by molding the resin composition for a printed wiring board according to any one of claims 1 to 20 into a sheet. A laminated resin sheet obtained by applying and drying the resin composition for a printed wiring board according to any one of claims 1 to 20 on a surface of a sheet substrate. An insulating layer, a printed wiring board including a conductor layer formed on the surface of the insulating layer, wherein the insulating layer is a resin composition for a printed wiring board according to any one of claims 1 to 20. Including printed wiring boards.