JP2019059958A - Resin composition for printed wiring board, prepreg, laminate sheet, and printed wiring board - Google Patents

Abstract

To provide a printed wiring board material resin composition of which reductions of Tg and elasticity are suppressed even though a silicone resin is added to the resin composition, and low in thermal expansion coefficient in a surface direction, a prepreg, a laminate sheet, a metal-clad laminate sheet and a printed wiring board.SOLUTION: There is provided a resin composition for printed wiring board containing a silicon-containing polymer (A) having bonds (a) and (b), a terminal which is a functional group selected from R1, a hydroxyl group and an alkoxyl group, and epoxy equivalent of 500 to 4000, a non-halogen epoxy resin (B), a cyanic acid ester compound (C), a maleimide compound (D), and an inorganic filler (E), with content of the inorganic filler (E) in the resin composition of 100 to 1000 pts.mass based on 100 pts.mass of total of components (B) to (D).SELECTED DRAWING: None

Description

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

  In recent years, semiconductors that are widely used in electronic devices, communication devices, personal computers, etc. are increasingly accelerating to become highly integrated, highly functional, and high density packaging, and for semiconductor plastic package laminates more than before. The demand for characteristics and high reliability is increasing.

In recent years, reduction of the thermal expansion coefficient in the surface direction of the laminate has been strongly demanded.
The reason is that the difference between the thermal expansion coefficient of the semiconductor element and the printed wiring board for the semiconductor plastic package is large, and when a thermal shock is applied, the semiconductor plastic package is warped due to the thermal expansion difference, and the semiconductor element and the semiconductor plastic This is because connection defects occur between the printed wiring boards for package and between the printed wiring boards mounted with the semiconductor plastic package.
As a method of reducing the coefficient of thermal expansion in the surface direction of the laminate, there is a method of filling with an inorganic filler. However, other characteristics required for laminates for semiconductor plastic packages are high glass transition temperature (Tg), and in order to make the laminate have high glass transition temperature, it is necessary to blend a multifunctional resin, The polyfunctional resin has a high viscosity and it is difficult to mix many inorganic fillers. Moreover, as another method, it is known to mix an organic filler having rubber elasticity into a varnish containing an epoxy resin (patent documents 1 to 6), but when this varnish is used, an organic filler is mixed. In such a case, the filler content of the inorganic filler is limited, and the organic filler having rubber elasticity has high flammability, so a brominated flame retardant may be used to make the laminate flame-retardant, which causes an impact on the environment. Have given.
As a method of maintaining the filling amount of the inorganic filler and obtaining the same effect as blending the rubber elastic component, there is a method of blending a silicone resin, but these resins are characterized by low Tg and low modulus of elasticity. Depending on the addition amount, there is a problem that Tg is lowered and elastic modulus is lowered.

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

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

  As a result of intensive studies to solve such problems, the present inventors have bonds (a) and (b), and the terminal is a functional group selected from R1, a hydroxyl group and an alkoxy group, and the epoxy equivalent is An inorganic filler (A) containing 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) It is found that the resin composition in which the content in the resin composition of E) is 100 to 1000 parts by mass with respect to a total of 100 parts by mass of the components (B) to (D) can solve the above problems, and reaches the present invention did.

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

  The metal foil-clad laminate according to the present invention is suitable as a material for a semiconductor plastic package which is required to have an excellent coefficient of thermal expansion, high heat resistance, high Tg, and high elastic modulus.

  Hereinafter, embodiments of the present invention will be described. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

  One aspect of this embodiment contains 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), and the inorganic The content of the filler (E) in the resin composition is 100 to 1000 parts by mass with respect to a total of 100 parts by mass of the components (B) to (D).

  Moreover, as another aspect of the present embodiment, a BT resin formed 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).

  Moreover, in addition to the said resin composition component, it is a resin composition containing an imidazole compound as another aspect of this embodiment.

  Furthermore, 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), and the terminal is a functional group selected from R ₁ , a hydroxyl group and an alkoxy group, and has an epoxy equivalent of 500 There is no particular limitation as long as it is ~ 4000, and as such a polymer, for example, branched polysiloxane and the like can be mentioned.

(1)
(Here, R ₁ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and all R ₁ in the silicon-containing polymer may be the same or different. X is Indicates a monovalent organic group containing an epoxy group.)
As R ₁ in the general formulas (a) and (b), 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 And alkyl groups such as 2-ethylhexyl group, alkenyl groups such as vinyl, allyl, butenyl, pentenyl and hexenyl groups, aryl groups such as phenyl, tolyl, xylyl, naphthyl and biphenyl, and benzyl And aralkyl groups such as phenethyl group etc., among which methyl group or phenyl group is preferable. Moreover, as X in the above general formula (b), 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxy Propyl group, 4-glycidoxybutyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, etc. are mentioned, among which 3-glycidoxypropyl group is preferable. Further, 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. Examples of the alkoxy group in this case include a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Furthermore, the epoxy equivalent of the silicon-containing polymer (A) needs to be in the range of 500 to 4,000, and preferably 1,000 to 2,500. If it is less than 500, the flowability of the resin composition tends to decrease, and if it is more than 4000, it tends to exude onto the surface of the cured product, and tends to cause molding defects.

The silicon-containing polymer (A) is further preferable from the viewpoint of coexistence of the flowability and the low warping property of the resin composition obtained to have the following bond (c).
(2)
(Here, R ₂ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and all R ₂ in the silicon-containing polymer may be the same or different.) Above As R ₂ in the general formula (c), methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group And alkyl groups such as vinyl, allyl, butenyl, pentenyl and hexenyl, phenyl, tolyl, xylyl, naphthyl, aryl such as biphenyl and the like, benzyl and phenethyl. Aralkyl groups and the like can be mentioned, with preference given to methyl and phenyl.
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. When the temperature is higher than 40 ° C., the mechanical strength of the cured product of the resin composition for printed wiring board tends to increase, and when the temperature is lower than 120 ° C., the dispersibility of the silicon-containing polymer (A) in the resin composition is improved. Tend to As a method of adjusting the softening point of the silicon-containing polymer (A), the molecular weight of the silicon-containing polymer (A), the structural bonding unit (for example, the content ratio of (a) to (c), etc., an organic group bonded to a silicon atom) It is possible to set the type of the metal, but in particular from the viewpoint of the dispersibility of the silicon-containing polymer (A) in the resin composition for printed wiring board and the fluidity of the resin composition for printed wiring board obtained It is preferable to adjust the softening point by setting the content of the aryl group in the polymer (A), and in this case, the aryl group includes phenyl group, tolyl group, xylyl group, naphthyl group, biphenyl group, etc. The content of the phenyl group in the monovalent organic group bonded to the silicon atom in the silicon-containing polymer (A) is 60 mol% to 99 mol%, preferably 70 mol% to 85. Set at 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 measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve, and is 1000 to 30,000, preferably 2,000 to 20,000, 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 shown below, but as a commercial product, it can be obtained as Toray Dow Corning Silicone Co., Ltd. under the trade name AY 42-119.

The method for producing the silicon-containing polymer (A) can be produced by a known method without particular limitation. For example, organochlorosilanes, organoalkoxysilanes, siloxanes, or partial hydrolytic condensates thereof that can form the above (a) to (c) units by hydrolysis and condensation reactions as a raw material and an organic solvent capable of dissolving the reaction product It can be obtained by mixing all hydrolyzable groups of the raw material in a mixed solution with a hydrolysable amount of water and subjecting it to hydrolytic condensation reaction. At this time, in order to reduce the amount of chlorine contained as an impurity in the resin composition for printed wiring boards, it is preferable to use organoalkoxysilane and / or siloxane as a raw material. In this case, it is preferable to add an acid, a base or an organic metal compound as a catalyst for promoting the reaction.
As organoalkoxysilanes and / or siloxanes which are raw materials of the silicon-containing polymer (A), methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Phenyltrimethoxysilane, phenyltoethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, phenylvinyldimethoxysilane, diphenyldimethoxysilane, methylphenyldiethoxysilane, methylvinyldiethoxysilane, phenylvinyldiethoxy 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) Diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, and their hydrolysis condensates, etc. .

The content of the silicon-containing polymer (A) in the resin composition of the present embodiment is not particularly limited. However, the resin composition components may be silicon-containing polymer (A), non-halogen epoxy resin (B), cyanate ester compound In a system containing (C), a maleimide compound (D) and an inorganic filler (E), it is preferably 1 to 200 parts by mass with respect to 100 parts by mass in total of the components (B) to (D), More preferably, it is 10-100 mass parts, More preferably, it is 20-60 mass parts.
Further, in a system in which the resin composition component 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) It is preferable that it is 1-200 mass parts with respect to a total of 100 mass parts of (a), More preferably, it is 10-100 mass parts, More preferably, it is 20-60 mass parts.
By setting the content of the silicon-containing polymer (A) in a preferable range, a printed wiring board excellent in 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 the molecular structure.
For example, phenol phenyl aralkyl novolac epoxy resin represented by formula (3), phenol biphenyl aralkyl epoxy resin represented by formula (4), naphthol aralkyl epoxy resin represented by formula (5), and thermal expansion In order to lower the ratio, an anthraquinone epoxy resin represented by the formula (11) or a polyoxynaphtalene epoxy resin represented by the formula (6) or the formula (12) is used. In addition, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type Epoxy resin, biphenyl type epoxy resin, aralkyl novolac type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, compound obtained by epoxidizing double bond such as glycidyl amine, glycidyl ester, butadiene, hydroxyl group-containing silicone resin and epichlorohydrin And the like. Among these compounds, phenolphenylaralkyl novolac type epoxy represented by the formula (3) to improve the flame retardancy, among Fat, 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 It is preferable that it is a polyoxynaphthylene type epoxy resin represented by (12).
These non-halogen epoxy resins can be used alone or in combination of two or more.

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

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

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

(11)

(6)
(Wherein, R ₆ represents a hydrogen atom or a methyl group)

(12)
(Wherein, R ₁₂ represents a hydrogen atom or a methyl group)
The epoxy resin of said Formula (6) and Formula (12) can use a commercial item, As a product example, the product made by DIC Corporation, EXA-7311, EXA-7311-G3, EXA-7311-G4, EXA-7311 -G4S, EXA-7311L, HP-6000.

  Furthermore, a phosphorus-containing epoxy resin and a brominated epoxy resin can also 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, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin and the like are exemplified.

The content of the non-halogen epoxy resin (B) in the resin composition of the present embodiment is not particularly limited, but the resin composition components include the silicon-containing polymer (A), the non-halogen epoxy resin (B) and the cyanate ester compound In a system containing (C), a maleimide compound (D) and an inorganic filler (E), it 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 10-40 mass parts.
Further, in a system in which the resin composition component 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) It is preferable that it is 10-50 mass parts with respect to a total of 100 mass parts of (a), More preferably, it is 10-60 mass parts, More preferably, it is 20-40 mass parts.
By setting the content of the non-halogen epoxy (B) in a preferable range, a printed wiring board excellent in 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 the cured product with excellent properties such as chemical resistance and adhesiveness. As the cyanate ester compound (C), for example, naphthol aralkyl type cyanate ester compound represented by the formula (7), novolak type cyanate ester represented by the formula (8), phenol biphenyl aralkyl type cyanate ester compound, Bis (3,5-dimethyl 4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene 1,3-dicyanato naphthalene, 1,4-dicyanato naphthalene, 1,6-dicyanato naphthalene, 1,8-dicyanato naphthalene, 2,6-dicyanato naphthalene, 2,7-dicyanato naphthalene, , 3, 6-tricyanatonaphthalene, 4, 4'-dicyanatobiphenyl, bis (4-cyanatophenyl) ether And bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, 2,2-bis (4-cyanatophenyl) propane, and the like. These may be used alone or in combination of two or more.
Among them, naphthol aralkyl type cyanate ester compound represented by the formula (7), novolak type cyanate ester represented by the formula (8), and phenol biphenyl aralkyl type cyanate ester compound are excellent in flame retardancy, and the curability is excellent. It is particularly preferable because it is high and the thermal expansion coefficient of the cured product is low.

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

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

  The preparation method of these cyanate ester compounds is not particularly limited, and may be prepared by any method existing as cyanate ester synthesis. Specifically, for example, as described in JP-A-2009-35728, it is obtained by reacting a naphthol aralkyl type phenol resin and a halogenated cyanogen in an inert organic solvent in the presence of a basic compound. Can. Alternatively, a salt of a similar naphthol aralkyl type phenol resin and a basic compound may be formed in a solution containing water and then subjected to a two-phase interfacial reaction with cyanogen halide for synthesis. .

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

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

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

The content of the cyanate ester compound (C) in the resin composition of the present embodiment is not particularly limited, but the silicon-containing polymer (A), non-halogen epoxy resin (B), cyanate ester compound (C), 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 with respect to 100 parts by mass in total of the components (B) to (D). It is a mass part.
By setting the total content of the cyanate ester compound (C) in a preferable range, the degree of curing increases, and a printed wiring board having flame retardancy, glass transition temperature, water absorption coefficient, 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-phenyl maleimide, N-hydroxyphenyl maleimide, 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, represented by the formula (9) A maleimide compound, a prepolymer of these maleimide compounds, or a prepolymer of a maleimide compound and an amine compound may, for example, be mentioned. It is also possible to use one or two or more appropriately mixed.
Among them, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, The maleimide compound represented by 9) is preferable, and the maleimide compound exemplified by the formula (9) is particularly preferable.

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

The content of the maleimide compound (D) in the resin composition of the present embodiment is not particularly limited, but the silicon-containing polymer (A), non-halogen epoxy resin (B), cyanate ester compound (C), maleimide compound (D) And the inorganic filler (E) 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). It is.
By making content of a maleimide compound (D) into a preferable range, a hardening degree goes up and the printed wiring board excellent in the outstanding flame retardance, the glass transition temperature, the water absorption, and the elasticity modulus 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 generally used in the art. For example, natural silica, fused silica, amorphous silica, silicas such as hollow silica, aluminum hydroxide, aluminum hydroxide heat-treated product (a product obtained by heat-treating aluminum hydroxide to reduce part of water of crystallization), aluminum nitride Metal hydrates such as boron nitride, boehmite and 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 fibers (fine glass powders such as E glass and D glass), hollow glass, spherical glass, titanium oxide, silicone rubber, silicone composite powder, etc. may be mentioned, and one or more kinds may be mixed as appropriate 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 viewpoint of thermal expansion and flame resistance. A molybdenum compound or a molybdenum compound coated with an inorganic oxide is preferable from the viewpoint of the properties.

The average particle size (D50) of the inorganic filler (E) is not particularly limited, but in consideration of dispersibility, the average particle size (D50) is preferably 0.2 to 5 μm. Furthermore, as described above, the smaller the average particle size of the inorganic filler, the larger the surface area thereof, and the viscosity increase of the resin composition tends to occur. Thus, the effect of the present invention can be easily obtained. More preferably, it is 3 μm, particularly preferably 1 μm.
In the present specification, the average particle diameter (D50) means the median diameter (D50), and the value obtained when the measured particle size distribution of the powder is divided into two, with the larger and smaller sides being equal. It is. More specifically, the particle size distribution of a predetermined amount of powder introduced into the aqueous dispersion medium is measured by a laser diffraction / scattering type particle size distribution measuring apparatus, and volume integration is performed from small particles to 50% of the total volume. It means the value when reached.

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

In addition to the inorganic filler (E), in order to improve the dispersibility of the inorganic filler and the adhesive strength of the resin and the inorganic filler or glass cloth, it is also possible to use a silane coupling agent or a wetting dispersant in combination. is there.
It will not specifically limit, if it is a silane coupling agent generally used for the surface treatment of an inorganic substance as these silane coupling agents. Specific examples thereof include aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, and γ Vinylsilanes such as -methacryloxypropyltrimethoxysilane, cationic silanes such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, phenylsilanes and the like; It is also possible to use one kind or two or more kinds in combination as appropriate.
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, W903 manufactured by Big Chemie Japan Co., Ltd. may be mentioned.

[BT resin (F)]
The BT resin (F) in the resin composition of the present embodiment is a cyanate ester compound and a maleimide compound dissolved in no solvent or in an organic solvent such as methyl ethyl ketone, N methyl pyrodrine, dimethyl formamide, dimethyl acetamide, toluene and xylene. The mixture was heated and mixed, and prepolymerized.

The cyanate ester compound to be used is not particularly limited. For example, naphthol aralkyl type cyanate ester compound represented by the formula (7), novolak type cyanate ester represented by the formula (8), phenol biphenyl aralkyl type 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-dicyanato naphthalene, 1,4-dicyanato naphthalene, 1,6-dicyanato naphthalene, 1,8-dicyanato naphthalene, 2,6-dicyanato naphthalene, 2,7-dicyanato naphthalene, , 3,6-Tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl) Ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, 2, 2- bis (4-cyanatophenyl) propane, etc. are mentioned, and 1 type or 2 types or more are mixed suitably It is also possible to use it.
Among them, naphthol aralkyl type cyanate ester compound represented by the formula (7), novolak type cyanate ester represented by the formula (8) and phenol biphenyl aralkyl type cyanate ester are flame retardant of the printed wiring board obtained. It is preferable from the viewpoint of curability and low thermal expansion coefficient.
Also, the maleimide compound is not particularly limited, but N-phenyl maleimide, N-hydroxyphenyl maleimide, 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) The maleimide compound represented by these, the prepolymer of these maleimide compounds, or the prepolymer of a maleimide compound and an amine compound etc. are mentioned, It is also possible to use 1 type, or 2 or more types, mixing suitably.
Among them, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, The maleimide compound represented by 9) is preferable, and the maleimide compound exemplified by the formula (9) is particularly 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. The range of 10 to 70% by mass is particularly preferable.
Further, the range of the molecular weight of the prepolymer, BT resin (F), is not particularly limited, but from the viewpoint of handling property, glass transition temperature and curability, it is in the range of about 100 to 100,000 in number average molecular weight Is preferred.

Although content of BT resin (F) in the resin composition of this invention is not specifically limited, It is preferable that it is 10-90 mass parts with respect to a total of 100 mass parts of component (B) and (F), and more preferable. Is 20 to 80 parts by mass.
By making content of BT resin (F) into a preferable range, a hardening degree goes up and the printed wiring board excellent in a flame retardance, a glass transition temperature, a water absorption, and an elasticity modulus can be obtained.

The resin composition of this embodiment may contain the imidazole compound represented by Formula (10). The imidazole compound has an action of promoting curing and has an action of raising the glass transition temperature of the cured product. Examples of the substituent Ar in the formula (10) include a phenyl group which may have a substituent, a naphthalene group, a biphenyl group, an anthracene group or a hydroxyl group modified product thereof and the like, among which a phenyl group is preferable.
Further, the substituent R ₁₀ in the formula (10) is preferably a hydrogen atom, an alkyl group or its hydroxyl group-modified product, or an aryl group such as a phenyl group which may have a substituent, and both Ar and R ₁₀ are 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 which may have a substituent, a naphthalene group, a biphenyl group, an anthracene group or a hydroxyl-modified product thereof, R ₁₀ is a hydrogen atom, an alkyl group or a hydroxyl-modified polymer thereof, a substitution Represents an aryl group which may have a group)

The content of the imidazole compound in the resin composition of the present invention is not particularly limited. However, the resin composition components include silicon-containing polymer (A), non-halogen epoxy resin (B), cyanate ester compound (C), maleimide compound In the system containing (D) and the inorganic filler (E), it is preferably 0.01 to 10 parts by mass, more preferably 0 based on 100 parts by mass in total of the components (B) to (D). .1 to 5 parts by mass.
In a system in which the resin composition component contains the silicon-containing polymer (A) represented by the formula (1), the non-halogen epoxy resin (B), the BT resin (F) and the inorganic filler (E), It is preferable that it is 0.01-10 mass parts with respect to a total of 100 mass parts of components (B) and (F), More preferably, it is 0.1-5 mass parts.
By making content of an imidazole compound into a preferable range, a hardening degree goes up and the printed wiring board excellent in a glass transition temperature, a water absorption, and an elasticity modulus can be obtained.

  Moreover, in the resin composition of embodiment, in addition to the said imidazole compound, it is also possible to use together other hardening accelerators in the range which does not impair the desired characteristics. 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; azobisnitriles The corresponding azo compounds; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyl toluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine , Tertiary amines such as triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine, etc .; 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, iron acetylacetonate; these organic metal salts are dissolved in a monomer hydroxyl group-containing compound such as phenol or bisphenol Inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; and organic tin compounds such as dioctyl tin oxide and other alkyl tins and alkyl tin oxides.

  Furthermore, the resin composition of the present embodiment may contain a solvent, if necessary. For example, when an organic solvent is used, the viscosity at the time of preparation of the resin composition is lowered, the handling property is improved, and the impregnation property to the glass cloth is enhanced. The type of the solvent is represented by the formula silicon-containing polymer (A), non-halogen epoxy resin (B), cyanate ester compound (C), maleimide compound (D), or silicon-containing polymer (A), non-halogen epoxy resin ( B) It will not be limited especially if it can dissolve a part or all of the mixture of BT resin (F). Specific examples thereof include 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 acetate thereof and the like. There is no particular limitation on these. The solvents may be used alone or in combination of two or more.

  The resin composition in the present invention can be prepared according to a conventional method, and the silicon-containing polymer (A), non-halogen epoxy resin (B), cyanate ester compound (C), maleimide compound (D) and inorganic filler Material (E) and other optional components mentioned above, or silicon-containing polymer (A), non-halogen epoxy resin (B), BT resin (F) and inorganic filler (E) and other optional components mentioned above uniformly The preparation method is not particularly limited as long as it is a method by which the resin composition contained in is obtained. For example, the resin composition of this embodiment can be easily prepared by sequentially blending a silicon-containing polymer, a non-halogen epoxy resin, a cyanate ester compound, a maleimide compound, and silica into a solvent and sufficiently stirring.

  At the time of preparation of the resin composition of the present invention, an organic solvent can be used as needed. The type of organic solvent is silicon-containing polymer (A), non-halogen epoxy resin (B), cyanate ester compound (C), maleimide compound (D), or silicon-containing polymer (A), non-halogen epoxy resin ( It will not be limited especially if B) and the mixture of BT resin (F) can be dissolved. The specific example is as described above.

  In addition, at the time of preparation of a resin composition, the well-known process (stirring, mixing, kneading process, etc.) for dissolving or disperse | distributing each component uniformly can be performed. For example, when uniformly dispersing the inorganic filler (E), the dispersibility with respect to the resin composition is enhanced by performing the stirring and dispersing treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. The above-mentioned stirring, mixing, and kneading processing can be appropriately performed using, for example, a device intended for mixing such as a ball mill and a bead mill, or a known device such as a mixing device of revolution and rotation type.

  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 a substrate. The preparation method of a prepreg can be performed according to a conventional method, and is not particularly limited. For example, after impregnating or applying the resin component of the present invention to a substrate, the substrate is semi-cured (B-staging) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes. The prepreg of the embodiment can be produced. In addition, although the prepreg of this embodiment is not specifically limited, It is preferable that the quantity of the resin composition (an inorganic filler is included) with respect to the total amount of a prepreg is the range of 30-90 mass%.

The substrate used in the present invention is not particularly limited, and known materials used for various printed wiring board materials can be appropriately selected and used according to the intended application 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, polyparaphenylene terephthalamide (Kevlar Totally aromatic polyamide such as (registered trademark), manufactured by DuPont Co., Ltd., copolyparaphenylene, 3,4 'oxydiphenylene terephthalamide (manufactured by TENORA®, manufactured by Teijin Techno Products Co., Ltd.) Polyesters such as naphthoic acid and parahydroxybenzoic acid (Bectran (registered trademark), Kuraray Co., Ltd.), etc., polyparaphenylene benzoxazole (Zylon (registered trademark)
Organic fiber such as Toyobo Co., Ltd., polyimide, etc., but it is not particularly limited thereto.
Among these, E glass, T glass, S glass, and Q glass are preferable from the viewpoint of low thermal expansion.
These substrates can be used singly or in combination of two or more.
As the shape of the base material, woven fabrics, non-woven fabrics, rovings, chopped strand mats, surfacing mats, etc. are known as weaves of woven fabrics such as plain weave, inner weave, twill weave etc. It can be appropriately selected and used according to the intended use and performance, and those obtained by opening the fibers and glass woven fabrics surface-treated with a silane coupling agent are suitably used. The thickness and mass of the substrate are not particularly limited, but usually, those having about 0.01 to 0.3 mm are suitably used. In particular, from the viewpoint of strength and water absorption, a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g / m ² or less is preferable, and a glass woven fabric made of E glass fiber is more preferable.

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 metal foils on one side or both sides, and laminating and forming them. Specifically, one or more of the above-described prepregs are stacked, and if desired, a metal foil such as copper or aluminum is disposed on one side or both sides, and this is laminated and formed as necessary. The metal foil-clad laminate of this embodiment can be produced. 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. Moreover, the thickness of metal foil is although it does not specifically limit, 2-70 micrometers is preferable, More preferably, it is 2-35 micrometers. It does not specifically limit also about the shaping | molding method of metal foil tension laminate sheet, and its shaping condition, The method and conditions of a general laminated board for printed wiring boards and a multilayer board are applicable. For example, when forming a metal foil-clad laminate, a multi-stage press, multi-stage vacuum press, continuous forming machine, autoclave forming machine, etc. can be used, and the temperature is 100 to 300 ° C., and the pressure is a surface pressure of 2 to 100 kgf / cm ^2, the heating time in the range of 0.05 to 5 hours are common. Furthermore, if necessary, post curing can be performed at a temperature of 150 to 300 ° C. Moreover, it is also possible to make it a multilayer board by carrying out lamination molding of the prepreg of this embodiment, and the wiring board for inner layers produced separately, combining.

  The metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board by forming a predetermined wiring pattern. And, the metal foil-clad laminate of the present invention has a low coefficient of thermal expansion, good formability and chemical resistance, and is particularly effectively used as a printed wiring board for a semiconductor package for which such performance is required. 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 the copper-clad laminate of the present invention, is prepared. The surface of the metal foil-clad laminate is subjected to etching treatment to form an inner layer circuit, thereby producing an inner layer substrate. If necessary, the inner layer circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength, and then the required number of prepregs of the present invention is stacked on the inner layer circuit surface, and metal foil for the outer layer circuit is further provided outside thereof. The layers are laminated, heated and pressurized to be integrally molded. In this manner, a multilayer laminate is produced in which an insulating layer made of a cured product of a base material and a thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after the multi-layer laminate is subjected to drilling for through holes and via holes, desmearing is performed to remove smear which is a residue of resin derived from the resin component contained in the cured product layer. . After that, a plated metal film is formed on the wall surface of the hole to electrically connect the inner layer circuit and the metal foil for the outer layer circuit, and the metal foil for the outer layer circuit is etched to form the outer layer circuit. Be done.
The prepreg (base and the resin composition of the present invention attached thereto) of the present invention, the resin composition layer of the metal foil-clad laminate (layer of the resin composition of the present invention) To form an insulating layer.

  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 above present embodiment in a solvent on a sheet substrate and drying. The sheet substrate used here is, 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. An organic film substrate such as a polyimide film, a conductor foil such as copper foil or aluminum foil, a glass plate, a SUS plate, a plate such as FRP, etc. may be mentioned, but it is not particularly limited thereto. Examples of the application method include a method of applying a solution obtained by dissolving the resin composition of the present embodiment in a solvent on a sheet substrate with a bar coater, a die coater, a doctor blade, a baker applicator, or the like. Moreover, it can also be set as a single layer sheet (resin sheet) by peeling or etching a sheet | seat base material from a lamination | stacking resin sheet after drying. A solution obtained 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, thereby using a sheet substrate. It is also possible to obtain a single layer sheet (resin sheet).

  In the preparation of the single layer or laminated resin sheet of the present embodiment, the drying conditions for removing the solvent are not particularly limited, but if the temperature is low, the solvent tends to remain in the resin composition, and if the temperature is high, the resin is C. to 170.degree. C. for 1 to 90 minutes is preferable because curing of the composition proceeds. 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 application thickness, and is not particularly limited. The thickness is preferably 0.1 to 500 μm because the solvent tends to remain at the time of drying when the thickness is increased.

  EXAMPLES The present invention will be described in detail by way of Examples and Comparative Examples, but the present invention is not limited by these Examples.

Synthesis Example 1 Synthesis of α-naphthol Aralkyl Type Cyanate Compound A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was cooled beforehand to 0 to 5 ° C. with brine, .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 (SN 485, equivalent of OH group) in which all R 7 in the formula (7) are hydrogen atoms under stirring while keeping the temperature in the reactor at −5 to + 5 ° C. and the pH at 1 or less. Softening point: 86 ° C, manufactured by Nippon Steel Chemical Co., Ltd., 20 g (0.0935 mol), and 14.16 g (0.14 mol) of triethylamine dissolved in 92 ml of methylene chloride for 1 hour with a dropping funnel The reaction solution was added dropwise over a period of 15 minutes after the completion of dropwise addition, after which 4.72 g (0.047 mol) of triethylamine was further added dropwise over 15 minutes.
After completion of the dropwise addition, the reaction solution was separated after stirring for 15 minutes at the same temperature, and the organic layer was separated. The obtained organic layer is washed twice with 100 ml of water, and then methylene chloride is distilled off under reduced pressure with an evaporator, and finally concentrated to dryness 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 type cyanate ester compound) was obtained.

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

Synthesis Example 3 Synthesis of BT Resin 2 36 parts by mass of α-naphtholaralkyl type cyanate ester compound (cyanate equivalent: 261 g / eq.) Synthesized by the method described in Synthesis Example 1 and bis (3-ethyl-5-methyl- 26 parts by mass of 4 maleimidophenyl) methane (BMI-70, manufactured by Kaiai Kasei Co., Ltd.) was dissolved in dimethylacetamide and reacted with stirring at 150 ° C. to obtain BT resin 2.

Example 1
30 parts by mass of polysiloxane having a softening point of 80 ° C. (AY 42-119, manufactured by Toray Dow Corning, epoxy equivalent 1660 g / eq., Manufactured by Toray Dow Corning) as a silicon-containing polymer, Synthesis Example 1 30 parts by weight of the α-naphthol aralkyl type cyanate ester compound (cyanate equivalent: 261 g / eq.) Obtained in the above, polyoxynaphthylene type epoxy resin (HP-6000, epoxy equivalent: 250 g / eq., DIC (strain ), 10 parts by mass of the maleimide compound (BMI-2300) used in Synthesis Example 2, 5 parts by mass of a silane coupling agent (manufactured by Toray Dow Coatings Co., Ltd.), and a wetting and dispersing agent (disperbyk-). 161, 1 part by mass of Big Chemie Japan Co., Ltd., 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. The varnish was diluted with methyl ethyl ketone, impregnated and applied to a 0.1 mm thick T glass woven fabric, and dried by heating at 140 ° C. for 3 minutes to obtain a prepreg having a resin content of 50% by mass.

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

Example 3
Novolak-type cyanate ester compound (primaset PT-30, manufactured by Lonza Japan Co., Ltd., cyanate equivalent weight: 124 g / eq) in which all R 8 in the formula (8) are hydrogen atoms instead of α-naphthol aralkyl type cyanate ester compound A prepreg was obtained in the same manner as in Example 1 except that 30 parts by mass of.) 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, 38 parts of polyoxynaphthylene type epoxy resin (HP-6000) Parts by mass, 26 parts by mass of maleimide compound (BMI-2300) used in Synthesis Example 2, 5 parts by mass of silane coupling agent (Z 6040), 1 part by mass of wetting dispersant (disperbyk-161), spherical fused silica ( 200 parts by mass of SC2500-SQ), 1 part by mass of 2,4,5-triphenylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) in which R10 and Ar in the formula (10) are all phenyl groups and mixed with varnish I got The varnish was diluted with methyl ethyl ketone, impregnated and applied to a 0.1 mm thick T glass woven fabric, 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 using 26 parts by mass of bis (3-ethyl-5-methyl-4maleimidophenyl) methane (BMI-70) used in Synthesis Example 3 instead of the maleimide compound (BMI-2300) used in Synthesis Example 1 In the same manner as in Example 4, a prepreg was obtained.

Example 6
Phenol biphenylaralkyl epoxy resin (NC-3000-FH, epoxy equivalent: 320 g / eq., Manufactured by Nippon Kayaku Co., Ltd.) instead of the polyoxynaphthylene epoxy resin (HP-6000) used in Example 1 A prepreg was obtained in the same manner as in Example 4 except that 38 parts by mass of B was used.

Example 7
38 mass of 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 that part was used.

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

Example 9
Furthermore, 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 the α-naphthol aralkyl type cyanate ester compound and the maleimide compound used in Synthesis Example 2 were not used, and 62 parts by mass of the BT resin obtained in Synthesis Example 2 was added. The

Example 11
A prepreg was prepared in the same manner as in Example 4, except that the α-naphthol aralkyl type cyanate ester compound and the bismaleimide compound used in Synthesis Example 2 were not used, and 62 parts by mass of the BT resin obtained in Synthesis Example 3 was added. Obtained.

Comparative Example 1
36 parts by mass of α-naphthol aralkyl type cyanate ester compound obtained in Synthesis Example 1, 38 parts by mass of polyoxynaphthylene type epoxy resin (HP-6000), and maleimide compound used in Synthesis Example 2 (BMI-2300 26 parts by weight, 5 parts by weight of silane coupling agent (Z6040), 1 part by weight of wetting dispersant (disperbyk-161), 200 parts by weight of spherical fused silica (SC2500-SQ), R10 in formula (10) And 1 part by mass of 2,4,5-triphenylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) in which all Ars are phenyl groups to obtain a varnish. The varnish was diluted with methyl ethyl ketone, impregnated and applied to a 0.1 mm thick T glass woven fabric, 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 except that 30 parts by mass of epoxy-modified silicone resin 1 (X-22-163A, epoxy equivalent weight: 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 in 4.

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

Comparative example 4
Example except using 30 parts by mass of epoxy-modified silicone resin 3 (X-41-1053, epoxy equivalent: 820 g / eq., Manufactured by Shin-Etsu Chemical Co., Ltd.) instead of the silicon-containing polymer used in Example 1 A prepreg was obtained in the same manner as in 4.

Comparative example 5
Example 4 was repeated except that 30 parts by mass of epoxy-modified silicone resin 4 (KF 105, epoxy equivalent: 490 g / eq., Shin-Etsu Chemical Co., Ltd.) was used instead of the silicon-containing polymer used in Example 1. The prepreg was obtained.

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

Comparative example 7
Example 7 except that 30 parts by mass of epoxy-modified silicone resin (X-22-163A, epoxy equivalent weight: 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 in.

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

Preparation of metal foil-clad laminates The prepregs obtained in Examples 1 to 11 and Comparative Examples 1 to 8 are stacked two each to form an electrolytic copper foil (3EC-III, manufactured by Mitsui Metal Mining Co., Ltd.) with a thickness of 12 μm. The laminate was placed at the top and bottom and laminated for 120 minutes at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. 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 formability, heat resistance, Tg, elastic modulus, and thermal expansion coefficient in the plane direction using the obtained prepreg and copper-clad laminate.

Physical Property Evaluation Method of Prepreg and Metal Foil-Clad Laminate Moldability , heat resistance, Tg, elastic modulus 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. Those with no void were rated ○, those with a void only at the end of the ancrat plate were rated △, and those with an overall void were rated ×.
Heat resistance: n = 5, and all were solder floats at 260 ° C., 30 minutes without swelling at 30 minutes, and those with swelling at ×.
Glass transition temperature (Tg): A 0.8 mm thick double-sided copper-clad laminate obtained in the above Examples and Comparative Examples is etched over the entire surface to prepare a 12 mm × 25 mm test piece, and a DMA device (TA instrument) The temperature was raised at 10 ° C./min using a dynamic viscoelasticity measuring device DMAQ400 manufactured by Mento Co., Ltd., and the peak position of LossModulus was regarded as the glass transition temperature.
Elastic modulus: Measured at normal temperature using an autograph (manufactured by Shimadzu Corporation, AG 5000 B) according to JIS-K 6911 using a test piece of 10 mm × 50 mm × 0.8 mm in size.
Thermal expansion coefficient in the plane direction: After removing the copper foil by etching the copper-clad laminate, the temperature is raised from 40 ° C. to 340 ° C. at 10 ° C./min using a thermomechanical analyzer (manufactured by TA Instruments), The coefficient of linear expansion in the plane direction at 120 ° C. to 120 ° C. was measured. The measurement direction was measured in the longitudinal direction (Warp) of the glass cloth of the laminate.

Moldability ○: no void ×: overall void heat resistance ○: no delamination ×: delamination in units Tg: ° C modulus of elasticity: GPa coefficient of thermal expansion: ppm / ° C

Moldability ○: no void ×: overall void heat resistance ○: no delamination ×: delamination in units Tg: ° C modulus of elasticity: GPa coefficient of thermal expansion: ppm / ° C

Claims (28)

Silicon-containing polymer (A) having bonds (a) and (b), an end being a functional group selected from R ₁ , a hydroxyl group and an alkoxy group, and having an epoxy equivalent of 500 to 4000 (A), non-halogen epoxy resin (B) The cyanate ester compound (C), the maleimide compound (D) and the inorganic filler (E) are contained, and the content of the inorganic filler (E) in the resin composition is the components (B) to (D) The resin composition for printed wiring boards contained 100-1000 mass parts with respect to a total of 100 mass parts.
(1)
(Here, R ₁ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and all R ₁ in the silicon-containing polymer may be the same or different. X is Indicates a monovalent organic group containing an epoxy group.) The resin composition for printed wiring boards according to claim 1, wherein the silicon-containing polymer (A) further has a bond (c).
(2)
(Here, R ₂ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and all R ₂ in the silicon-containing polymer may be the same or different.)   The resin composition for printed wiring boards according to claim 1 or 2 whose softening point of said silicon content polymer (A) is 40 ° C or more and 120 ° C or less. The resin composition for printed wiring boards according to any one of claims 1 to 3, wherein R ₁ in the silicon-containing polymer (A) is a substituted or unsubstituted phenyl group and / or a methyl group. The non-halogen epoxy resin (B) is a phenolphenylaralkyl epoxy resin represented by the formula (3), a phenolbiphenylaralkyl epoxy resin represented by the formula (4), a naphthol aralkyl represented by the formula (5) Type epoxy resin, anthraquinone type epoxy resin represented by formula (11), and polyoxynaphthylene type epoxy resin represented by formulas (6) and (12), any one or more of them being The resin composition for printed wiring boards as described in any one of Claims 1-4.
(3)
(Wherein, R ₃ represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more).
(4)
(Wherein, R ₄ represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more).
(5)
(Wherein, R ₅ represents a hydrogen atom or a methyl group, and n ₅ represents an integer of 1 or more).
(6)
(Wherein, R ₆ represents a hydrogen atom or a methyl group)
(11)
(12)
(Wherein, R ₁₂ represents a hydrogen atom or a methyl group) The naphthol aralkyl type cyanate ester compound represented by the formula (7), the novolak type cyanate ester compound represented by the formula (8), and the phenol biphenyl aralkyl type cyanate ester compound represented by the formula (8) The resin composition for printed wiring boards according to any one of claims 1 to 5, which is any one or more of the group consisting of
(7)
(Wherein, each R ₇ independently represents a hydrogen atom or a methyl group, and n ₇ represents an integer of 1 or more).
(8)
(Wherein each R ₈ independently represents a hydrogen atom or a methyl group, and n ₈ represents an integer of 1 or more). The resin composition for printed wiring boards as described in any one of Claims 1-6 whose said maleimide compound (D) is represented by Formula (9).
(9)
(Wherein, each 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 said silicon-containing polymer (A) is 1-200 mass parts as described in any one of Claims 1-7 with respect to a total of 100 mass parts of component (B)-(D). Resin composition for printed wiring boards.   The content of the said non-halogen epoxy resin (B) is 10-50 mass parts with respect to a total of 100 mass parts of component (B)-(D), It is described in any one of Claims 1-8. Resin composition for printed wiring boards.   The content of the said cyanate ester compound (C) is 10-50 mass parts with respect to a total of 100 mass parts of component (B)-(D), It is described in any one of Claims 1-9. 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 a total of 100 parts by mass of the components (B) to (D). Resin composition for wiring board.   The content of the said inorganic filler (E) is 100-1000 mass parts with respect to a total of 100 mass parts of component (B)-(D), It is described in any one of Claims 1-11. Resin composition for printed wiring boards.   The silicon-containing polymer (A), non-halogen epoxy resin (B), BT resin (F) prepared by prepolymerizing cyanate ester compound and maleimide compound, and inorganic filler (E), the inorganic filler The resin composition for printed wiring boards whose content in the resin composition of (E) is contained 100-1000 mass parts with respect to a total of 100 mass parts of component (B) and (F).   A naphthol aralkyl type cyanate ester compound represented by the formula (7), a novolak type cyanate ester compound represented by the formula (8) and a phenol biphenyl aralkyl type represented by the formula (7): The resin composition for printed wiring boards according to claim 13, which is any one or more of a group consisting of cyanate ester compounds.   The resin composition for printed wiring boards of Claim 13 or 14 whose maleimide compound used for said BT resin (F) is represented by Formula (9).   The content of the silicon-containing polymer (A) is 1 to 200 parts by mass with respect to a total of 100 parts by mass of the non-halogen epoxy resin (B) and the BT resin (F). The resin composition for printed wiring boards as described in one term.   The content of the said non-halogen epoxy resin (B) is 10-50 mass parts with respect to a total of 100 mass parts of non-halogen epoxy resin (B) and BT resin (F). The resin composition for printed wiring boards as described in one term.   The content of the said BT resin (F) is 10-90 mass parts with respect to a total of 100 mass parts of a non-halogen epoxy resin (B) and BT resin (F), Any one of Claims 13-17 The resin composition for printed wiring boards as described in-. The resin composition for printed wiring boards according to any one of claims 1 to 18, further comprising an imidazole compound represented by formula (10).
(10)
(Wherein, Ar is each independently a phenyl group which may have a substituent, a naphthalene group, a biphenyl group, an anthracene group or a hydroxyl group modified product thereof, R 10 is a hydrogen atom, an alkyl group or a hydroxyl group modified product thereof, a substituent group Represents an aryl group which may have   The resin composition for a printed wiring board according to claim 20, 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 compounds, silicone rubber, and silicone composite powder. The resin composition for printed wiring boards as described in any one of Claims 1-20.   A prepreg having the substrate impregnated or coated with the resin composition for a printed wiring board according to any one of claims 1 to 21.   The prepreg according to claim 22, wherein the substrate is any one or more of the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth and organic fibers.   A laminated board obtained by laminating one or more prepregs according to claim 22 or 23 and curing.   A metal foil-clad laminate obtained by laminating and curing the prepreg according to claim 22 or 23 and a metal foil.   A single layer sheet formed by forming the resin composition for a printed wiring board according to any one of claims 1 to 21 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 21 on the surface of a sheet substrate.   A printed wiring board comprising an insulating layer and 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 21. Printed wiring board including.