KR102418675B1 - Resin composition, prepreg, resin sheet, laminated resin sheet, laminated board, metallic foil laminated board, and printed wiring board - Google Patents

Abstract

It contains a cyanate ester compound (A) and a maleimide compound (B), and the amount of cyanate ester groups (α) of the cyanate ester compound (A) with respect to the amount of maleimide groups (β) of the maleimide compound (B) ) ratio ([α/β]) is 0.30 or more, the resin composition.

Description

Resin composition, prepreg, resin sheet, laminated resin sheet, laminated board, metal foil-clad laminated board, and printed wiring board

TECHNICAL FIELD The present invention relates to a resin composition, a prepreg, a resin sheet, a laminated resin sheet, a laminate, a metal foil-clad laminate, and a printed wiring board.

In recent years, as high-functionality and miniaturization of semiconductor packages widely used in electronic devices, communication devices, personal computers, and the like progress, high integration and high-density mounting of each component for a semiconductor package is accelerating in recent years. In connection with it, the curvature of the semiconductor plastic package which generate|occur|produces by the difference in the thermal expansion coefficient of a semiconductor element and the printed wiring board for semiconductor plastic packages has become a problem, and various countermeasures have been taken.

As one of the countermeasures, low thermal expansion of the insulating layer used for a printed wiring board is mentioned. This is the method of suppressing curvature by making the thermal expansion coefficient of a printed wiring board close to the thermal expansion coefficient of a semiconductor element, and it is introduce|transduced actively now (for example, refer patent documents 1 - 3).

As a method of suppressing the warpage of the semiconductor plastic package, in addition to lowering the thermal expansion of the printed wiring board, increasing the rigidity of the laminate (higher rigidity) and increasing the glass transition temperature of the laminate (higher Tg) are being considered ( For example, refer to Patent Documents 4 and 5).

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

However, the low thermal expansion-ization of the printed wiring board by the conventional method of patent documents 1-3 is already approaching the limit, and further low thermal expansion-ization is becoming difficult.

High-stiffness-ization of a laminated board is achieved by making a filler high in the resin composition used for a laminated board, or using inorganic fillers of high elastic modulus, such as alumina. However, there is a problem that high filling of the filler deteriorates the moldability of the laminate, and the use of an inorganic filler such as alumina deteriorates the coefficient of thermal expansion of the laminate. Therefore, the increase in rigidity of the laminate did not sufficiently achieve suppression of warpage of the semiconductor plastic package.

In addition, since the method by increasing the Tg of the laminate improves the elastic modulus at the time of reflow, it is effective in reducing the warpage of the semiconductor plastic package. However, since the method of increasing Tg causes deterioration of moisture absorption heat resistance due to increase in crosslinking density and generation of voids due to deterioration of moldability, it is a practical problem in the field of electronic materials that require very high reliability. Often times. Therefore, a method for solving these problems is desired.

Moreover, it is simultaneously calculated|required by the insulating layer of a printed wiring board that it is excellent in a high elastic modulus retention rate, high copper foil peeling strength, and plating peeling strength. However, the resin composition which provides the hardened|cured material which can satisfy|fill all these subjects has not been reported.

The present invention was made in view of the above problems, and a resin composition providing a cured product having excellent copper foil peel strength and plating peel strength, and a prepreg, a resin sheet, a laminated resin sheet, a laminated sheet, and a metal foil-clad laminate using the resin composition , and to provide a printed wiring board.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject. As a result, by using a cyanate ester compound (A) and a maleimide compound (B) in predetermined amounts, it discovered that the said malfunction could be solved, and came to complete this invention.

That is, the present invention is as follows.

[One]

containing a cyanate ester compound (A) and a maleimide compound (B);

The resin composition in which ratio ([α/β]) of the amount of cyanate ester groups (α) of the cyanate ester compound (A) to the amount of maleimide groups (β) of the maleimide compound (B) is 0.30 or more.

[2]

The resin composition as described in [1] in which the said cyanate ester compound (A) contains the compound represented by following General formula (1) and/or following General formula (2).

[Formula 1]

(In formula (1), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² is each independently selected from the group consisting of a cyanate ester group, a hydroxyl group and an allyl group as a substituent. A phenyl group, a hydrogen atom, an allyl group, a cyanate ester group, or an epoxy group which may have at least one is represented, n1 is an integer of 1 or more, and m is an integer of 1-4.)

[Formula 2]

(In formula (2), R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n2 is an integer of 1 or more.)

[3]

The cyanate ester group equivalent of a cyanate ester compound (A) is 100-220 g/eq. phosphorus, and the resin composition according to [1] or [2].

[4]

The resin composition in any one of [1]-[3] in which the said cyanate ester compound (A) contains the compound represented by the following general formula (1'').

[Formula 3]

(In formula (1''), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1 is an integer of 1 or more.)

[5]

The resin composition in any one of [1]-[4] in which the said cyanate ester compound (A) contains the compound represented by following General formula (3).

[Formula 4]

[6]

Said maleimide compound (B) is bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl- The resin composition in any one of [1]-[5] containing at least 1 sort(s) selected from the group which consists of 4-maleimidephenyl)methane and the maleimide compound represented by following formula (4).

[Formula 5]

(In the formula, R ⁴ each independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.)

[7]

The resin composition according to any one of [1] to [6], wherein the ratio ([α/β]) is 0.45 to 1.0.

[8]

The resin composition according to any one of [1] to [7], further comprising an inorganic filler (C).

[9]

The resin composition according to [8], wherein the content of the inorganic filler (C) is 25 to 700 parts by mass with respect to 100 parts by mass of the resin solid content.

[10]

The resin composition according to [8] or [9], wherein the inorganic filler (C) contains at least one selected from the group consisting of silica, boehmite, and alumina.

[11]

description and

A prepreg comprising the resin composition according to any one of [1] to [10] impregnated or applied to the base material.

[12]

A resin sheet formed by forming the resin composition according to any one of [1] to [10] in a sheet shape.

[13]

A laminated resin sheet comprising a sheet substrate and the resin composition according to any one of [1] to [10] disposed on one or both surfaces of the sheet substrate.

[14]

A laminate having one or more sheets of at least one selected from the group consisting of the prepreg according to [11], the resin sheet according to [12], and the laminated resin sheet according to [13].

[15]

At least one selected from the group consisting of the prepreg according to [11], the resin sheet according to [12], and the laminated resin sheet according to [13];

A metal foil-clad laminate comprising the prepreg, the resin sheet, and a metal foil disposed on one or both surfaces of the laminated resin sheet.

[16]

an insulating layer and a conductor layer formed on one or both surfaces of the insulating layer;

The printed wiring board in which the said insulating layer contains the resin composition in any one of [1]-[10].

According to the present invention, a resin composition for providing a cured product having excellent copper foil peel strength and plating peel strength, and a prepreg, a resin sheet, a laminated resin sheet, a laminated board, a metal foil clad laminate, and a printed wiring board using the resin composition can provide

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications are possible without departing from the gist thereof. .

[resin composition]

The resin composition of this embodiment contains a cyanate ester compound (A) and a maleimide compound (B), The said cyanate ester compound (A) with respect to the maleimide group weight ((beta)) of the maleimide compound (B) ), the ratio ([α/β]) of the amount of cyanate ester groups (α) is 0.30 or more.

[Cyanic acid ester compound (A)]

It will not specifically limit, if it is a compound which has at least 1 cyanate ester group as a cyanate ester compound (A). The cyanate ester compound (A) may or may not have reactive functional groups other than a cyanate ester group.

Although it does not specifically limit as a reactive functional group other than a cyanate ester group, For example, an allyl group, a hydroxyl group, an epoxy group, an amino group, an isocyanate group, a glycidyl group, and a phosphoric acid group are mentioned. Among these, at least 1 selected from the group which consists of an allyl group, a hydroxyl group, and an epoxy group is preferable, and an allyl group is more preferable. By having such a reactive functional group, there exists a tendency for the bending strength and bending elastic modulus of a resin composition, a glass transition temperature, and a coefficient of thermal expansion to improve more.

A cyanate ester compound (A) may be used individually by 1 type, and may use 2 or more types together. When using two or more types together, you may use together what has and does not have what has reactive functional groups other than cyanate ester, and may use together what has reactive substituents other than 2 or more types of cyanate ester groups. In that case, reactive functional groups other than a cyanate ester group may be same or different. Among these, it is preferable that the cyanate ester compound (A) contains the cyanate ester compound which has reactive functional groups other than a cyanate ester group at least. By using such a cyanate ester compound (A), there exists a tendency for the copper foil peeling strength of the hardened|cured material obtained, plating peeling strength, glass transition temperature, and elasticity modulus retention to improve more.

Although it does not specifically limit as said cyanate ester compound (A), For example, a compound represented by the following general formula (1), a compound represented by the following general formula (2) (naphthol aralkyl type cyanate ester), novolac Type cyanate ester, biphenyl aralkyl type cyanate ester, bis(3,5-dimethyl4-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-dicyana Tonaphthalene, 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, and 2,2'-bis(4-cyanatophenyl)propane; The prepolymer of these cyanate ester is mentioned. These may be used individually by 1 type, and may use 2 or more types together. Among these, the compound represented by the following general formula (1) and the compound represented by the following general formula (2) are more preferable.

Although it does not specifically limit as a compound which has reactive functional groups other than a cyanate ester group among the said cyanate ester compound (A), For example, a compound represented by the following general formula (1) is preferable, and the following general formula (1') The compound represented by is more preferable, and the compound represented by the following general formula (1'') is still more preferable. By including such a cyanate ester compound (A), there exists a tendency for the copper foil peeling strength of the hardened|cured material obtained, plating peeling strength, glass transition temperature, and elasticity modulus retention to improve more.

[Formula 6]

(In formula (1), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² is each independently selected from the group consisting of a cyanate ester group, a hydroxyl group and an allyl group as a substituent. A phenyl group, a hydrogen atom, an allyl group, a cyanate ester group, or an epoxy group which may have at least one is represented, n1 is an integer of 1 or more, and m is an integer of 1-4.)

[Formula 7]

(In formula (1'), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² is each independently selected from the group consisting of a cyanate ester group, a hydroxyl group and an allyl group as a substituent. represents a phenyl group, a hydrogen atom, an allyl group, a cyanate ester group, or an epoxy group which may have at least one, and n1 is an integer of 1 or more.)

[Formula 8]

(In formula (1''), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1 is an integer of 1 or more.)

In Formula (1), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a methyl group. In addition, R ² is each independently a phenyl group, a hydrogen atom, an allyl group, a cyanate ester group, or an epoxy group which may have at least one selected from the group consisting of a cyanate ester group, a hydroxyl group and an allyl group as a substituent. and preferably a hydrogen atom or an allyl group. Moreover, n1 is an integer of 1 or more, Preferably it is an integer of 1-10, More preferably, it is an integer of 1-5. Moreover, m is an integer of 1-4, Preferably it is an integer of 1-2.

In formulas (1') and (1''), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a methyl group. By using the compound which has the bisphenol A frame|skeleton whose R< ¹ > is a methyl group, there exists a tendency for copper foil peel, plating peeling strength, and glass transition temperature to improve more. Moreover, it exists in the tendency which flexibility and moldability also improve more by having an allyl group further. Moreover, in formulas (1') and (1''), n1 is an integer of 1 or more, Preferably it is an integer of 1-10, More preferably, it is an integer of 1-5, More preferably, it is 1.

Although it does not specifically limit as a compound represented by general formula (1''), For example, the compound represented by following formula (3) is more preferable. By including such a cyanate ester compound (A), there exists a tendency for copper foil peeling strength of hardened|cured material obtained, plating peeling strength, glass transition temperature, and elasticity modulus retention rate, flexibility, and a moldability to improve more.

[Formula 9]

In addition, although it does not specifically limit as a compound which does not have reactive functional groups other than a cyanate ester group among the said cyanate ester compound (A), For example, the compound represented by the following general formula (2) is preferable. By including such a cyanate ester compound (A), there exists a tendency for the copper foil peeling strength and plating peeling strength of the hardened|cured material obtained to improve more.

[Formula 10]

(In formula (2), R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n2 is an integer of 1 or more.)

In Formula (2), R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. Moreover, n2 is an integer of 1 or more, Preferably it is an integer of 1-10, More preferably, it is an integer of 1-5.

Although the number of cyanate ester groups in 1 molecule of cyanate ester compound (A) is not specifically limited, Preferably it is 1-50, More preferably, it is 2-12, More preferably, it is 2-6. When the number of cyanate ester groups in 1 molecule of cyanate ester compound (A) is in the said range, there exists a tendency for copper foil peeling strength, plating peeling strength, glass transition temperature, and elastic modulus retention of the hardened|cured material obtained to improve more.

Moreover, although the number of reactive functional groups other than a cyanate ester group in 1 molecule of cyanate ester compound (A) is not specifically limited, Preferably it is 1-50, More preferably, it is 2-12, More preferably, it is 2 ∼6. When the number of reactive functional groups other than the cyanate ester group in one molecule of the cyanate ester compound (A) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention rate of the obtained cured product tend to be more improved. .

Although the amount of cyanate ester groups (alpha) of a cyanate ester compound (A) is not specifically limited, Preferably it is 0.075-0.5, More preferably, it is 0.085-0.4, More preferably, it is 0.095-0.3. When the amount of cyanate ester groups (α) of the cyanate ester compound (A) is within the above range, the copper foil peeling strength, plating peeling strength, glass transition temperature, and elastic modulus retention rate of the obtained cured product tend to improve more. The amount of cyanate ester groups (α) can be obtained by dividing the content (parts by mass) of the cyanate ester compound (A) with respect to 100 parts by mass of the resin solid content by the equivalent of the cyanate ester group of the cyanate ester compound (A). In addition, in this specification, "resin solid content" refers to the component except the solvent and inorganic filler (C) in a resin composition, unless there is a rejection in particular, "resin solid content 100 parts by mass" is a resin composition It shall point out that the sum total of the component except the solvent in and an inorganic filler (C) is 100 mass parts.

Although content of a cyanate ester compound (A) is not specifically limited, To 100 mass parts of resin solid content, Preferably it is 10-65 mass parts, More preferably, it is 15-60 mass parts, More preferably, it is 15-65 mass parts. 55 parts by mass. When content of a cyanate ester compound (A) is in the said range, there exists a tendency for the copper foil peeling strength of the hardened|cured material obtained, plating peeling strength, glass transition temperature, and elasticity modulus retention to improve more.

The cyanate ester group equivalent of the cyanate ester compound (A) becomes like this. Preferably it is 100-290 g/eq. and more preferably 120 to 270 g/eq. and more preferably 150 to 220 g/eq. to be. When the cyanate ester group equivalent of a cyanate ester compound (A) exists in the said range, there exists a tendency for the copper foil peeling strength of the hardened|cured material obtained and plating peeling strength to improve more.

[Maleimide Compound (B)]

Although it will not specifically limit as a maleimide compound (B), if it is a compound which has one or more maleimide groups in a molecule|numerator, For example, N-phenylmaleimide, N-hydroxyphenyl maleimide, bis(4-maleimidephenyl)methane , 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4- Maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, a maleimide compound represented by the following formula (4), a prepolymer of these maleimide compounds, or a maleimide compound and an amine compound A prepolymer is mentioned. Among these, bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, and bis(3-ethyl-5-methyl-4-maleimidephenyl) At least one selected from the group consisting of methane and a maleimide compound represented by the following formula (4) is preferable. By including such a maleimide compound (B), there exists a tendency for the copper foil peeling strength of the hardened|cured material obtained, plating peeling strength, glass transition temperature, and elasticity modulus retention to improve more. Moreover, among those mentioned above, the maleimide compound represented by following formula (4) from a viewpoint of a high glass transition temperature (high Tg) is more preferable.

[Formula 11]

(In the formula, R ⁴ each independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.)

In Formula (4), R ⁴ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In addition, in Formula (4), n3 represents an integer of 1 or more. n3 becomes like this. Preferably it is 10 or less, More preferably, it is 7 or less.

Although the amount of maleimide groups ((beta)) of a maleimide compound (B) is not specifically limited, Preferably it is 0.175-0.6, More preferably, it is 0.185-0.5, More preferably, it is 0.195-0.4. When the amount of maleimide groups (β) of the maleimide compound (B) is in the above range, the copper foil peeling strength, plating peeling strength, glass transition temperature, and elastic modulus retention of the obtained cured product tend to improve more. The amount of maleimide groups (β) can be obtained by dividing the content (parts by mass) of the maleimide compound (B) with respect to 100 parts by mass of the resin solid content by the equivalent of the maleimide group of the maleimide compound (B).

Although content of a maleimide compound (B) is not specifically limited, To 100 mass parts of resin solid content, Preferably it is 30-80 mass parts, More preferably, it is 35-75 mass parts, More preferably, it is 40-72 mass parts. is the mass part. When content of a maleimide compound (B) is in the said range, there exists a tendency for copper foil peeling strength of the hardened|cured material obtained, plating peeling strength, glass transition temperature, and elasticity modulus retention to improve more.

The maleimide group equivalent of a maleimide compound (B) becomes like this. Preferably it is 100-350 g/eq. and more preferably 150 to 300 g/eq. to be. When the maleimide group equivalent of a maleimide compound (B) is in the said range, there exists a tendency for the copper foil peeling strength of the hardened|cured material obtained, plating peeling strength, glass transition temperature, and elasticity modulus retention to improve more.

In the resin composition of the present embodiment, the ratio ([α/β]) of the amount of cyanate ester groups (α) of the cyanate ester compound (A) to the amount of maleimide groups (β) of the maleimide compound (B) is It is 0.30 or more, Preferably it is 0.30-2.0, More preferably, it is 0.40-1.1, Especially preferably, it is 0.45-1.0. When ratio ([α/β]) is in the above range, the copper foil peeling strength, plating peeling strength, glass transition temperature, and elastic modulus retention of the obtained cured product tend to improve more.

[Inorganic Filling Material (C)]

The resin composition of this embodiment may further contain an inorganic filler (C). Although it does not specifically limit as an inorganic filler (C), For example, Silicas, such as a natural silica, a fused silica, a synthetic silica, amorphous silica, aerosil, a hollow silica; silicon compounds such as white carbon; metal oxides such as titanium white, zinc oxide, magnesium oxide, and zirconium oxide; metal nitrides such as boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride; metal sulfates such as barium sulfate; metal hydrates such as aluminum hydroxide, aluminum hydroxide heat-treated products (aluminum hydroxide is heat-treated to reduce a part of crystal water), boehmite, and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc compounds such as zinc borate and zinc stannate; Alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fiber (including fine glass powders such as E glass, T glass, D glass, S glass and Q glass.), hollow glass, spherical glass, and the like. An inorganic filler (C) may be used individually by 1 type, and may use 2 or more types together.

Among these, at least one selected from the group consisting of silica, boehmite, and alumina is preferably included. By using such an inorganic filler (C), there exists a tendency for bending strength, a bending elastic modulus, and a thermal expansion coefficient to improve more.

To [ content of an inorganic filler (C) / 100 mass parts of resin solid content], Preferably it is 25-700 mass parts, More preferably, it is 50-500 mass parts, More preferably, it is 75-300 mass parts. When content of an inorganic filler (C) exists in the said range, there exists a tendency for the copper foil peeling strength of the hardened|cured material obtained and plating peeling strength to improve more.

[Silane coupling agent and wetting and dispersing agent]

The resin composition of this embodiment may further contain a silane coupling agent and a wet dispersing agent. By including a silane coupling agent or a wet dispersing agent, the dispersibility of the said inorganic filler (C), a resin component, an inorganic filler (C), and the adhesive strength of the base material mentioned later tend to improve more.

Although it will not specifically limit if it is a silane coupling agent generally used for surface treatment of an inorganic substance as a silane coupling agent, For example, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltri aminosilane-based compounds such as methoxysilane; Epoxysilane-type compounds, such as (gamma)-glycidoxy propyl trimethoxysilane; acrylsilane-based compounds such as γ-acryloxypropyltrimethoxysilane; cationic silane compounds such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; A phenylsilane type compound etc. are mentioned. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.

Although it will not specifically limit if it is a dispersion stabilizer used for coating materials as a wetting and dispersing agent, For example, DISPER-110, 111, 118, 180, 161, BYK-W996, W9010, W903 manufactured by Bikchemy Japan Co., Ltd. etc. can be heard

[Other resins, etc.]

The resin composition of this embodiment may further contain an epoxy resin (D), an alkenyl-substituted nadiimide compound (E), and an amine-modified silicone compound (F) as needed. By including such other resin etc., copper foil peeling strength, bending strength, and a bending elastic modulus improve more and there exists a tendency for a coefficient of linear thermal expansion to fall.

[Epoxy Resin (D)]

The resin composition of this embodiment may further contain an epoxy resin (D). By further including an epoxy resin (D), there exists a tendency for the copper foil peeling strength of the hardened|cured material obtained, plating peeling strength, glass transition temperature, and elasticity modulus retention to improve more. In addition, when a cyanate ester compound (A) has an epoxy group, when using an epoxy resin (D), an epoxy resin (D) points to compounds other than the cyanate ester compound (A) which has an epoxy group make it as

The epoxy resin (D) is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, and for example, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, Phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, glycidyl Ester type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, aralkyl novolak type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, isoshi An anurate ring containing epoxy resin or these halides are mentioned. Especially, at least 1 selected from the group which consists of a naphthol aralkyl type epoxy resin, a biphenyl aralkyl type epoxy resin, and a naphthalene type epoxy resin is preferable.

To [ content of an epoxy resin (D) ] with respect to 100 mass parts of resin solid content, Preferably it is 2.5-20 mass parts, More preferably, it is 5.0-17.5 mass parts, More preferably, it is 7.5-15 mass parts. When content of an epoxy resin (D) exists in the said range, there exists a tendency for the softness|flexibility of the hardened|cured material obtained, copper foil peeling strength, chemical-resistance, and desmear resistance to improve more.

[Alkenyl-substituted nadiimide compound (E)]

An alkenyl-substituted nadiimide compound (E) will not be specifically limited if it is a compound which has one or more alkenyl-substituted nadiimide groups in a molecule|numerator. Among these, the compound represented by following formula (5) is preferable. By using such an alkenyl-substituted nadiimide compound (E), there exists a tendency for the copper foil peeling strength of the hardened|cured material obtained, plating peeling strength, glass transition temperature, and elasticity modulus retention to improve more.

[Formula 12]

(In the formula, R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁶ is an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a formula ( 6) or the group represented by (7).)

[Formula 13]

(In the formula, R ⁷ represents a methylene group, an isopropylidene group, or a substituent represented by CO, O, S, or SO ₂ .)

[Formula 14]

(In the formula, R ⁸ each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)

The alkenyl-substituted nadiimide compound (E) is preferably a compound represented by the following formulas (9) and/or (10). By using such an alkenyl-substituted nadiimide compound (E), the coefficient of thermal expansion of the hardened|cured material obtained falls more and there exists a tendency for heat resistance to improve more.

[Formula 15]

In addition, as an alkenyl-substituted nadiimide compound (E), a commercially available thing can also be used. Although it does not specifically limit as what is marketed, For example, BANI-M (Maruzen Petrochemical Co., Ltd. product, the compound represented by Formula (9)), BANI-X (Maruzen Petrochemical Co., Ltd. product, Formula ( 10) and the like. You may use these 1 type or in combination of 2 or more type.

Although content of an alkenyl-substituted nadiimide compound (E) is not specifically limited, To 100 mass parts of resin solid content, Preferably it is 20-45 mass parts, More preferably, it is 25-40 mass parts, More preferably It is 30-35 mass parts. When content of an alkenyl-substituted nadiimide compound (E) exists in the said range, there exists a tendency for the copper foil peeling strength and plating peeling strength of the hardened|cured material obtained to improve more.

[Amine-modified silicone compound (F)]

The amine-modified silicone compound (F) will not be particularly limited as long as it is a compound having one or more amino groups in the molecule. Specific examples thereof include compounds represented by the following general formula (11).

[Formula 16]

In Formula (11), R ⁸ each independently represents a hydrogen atom, a methyl group, or a phenyl group, and among these, a methyl group is preferable. R ⁹ each independently represents a single bond, an alkylene group having 1 to 8 carbon atoms, and/or an arylene group. As R ⁹ , an alkylene group having 1 to 8 carbon atoms and an arylene group may be linked to form a divalent group. Among these, R ⁹ is preferably an alkylene group having 2 to 4 carbon atoms. In Formula (11), each n ₄ independently represents an integer of 1 or more.

As an amino group equivalent of an amine-modified silicone compound (F), 130-6000 are preferable, 400-3000 are more preferable, 600-2500 are still more preferable. By using such an amine-modified silicone compound (F), the elastic modulus retention rate is favorable and the resin composition with a lower thermal expansion coefficient can be obtained.

Although content of an amine-modified silicone compound (F) is not specifically limited, To 100 mass parts of resin solid content, Preferably it is 1-40 mass parts, More preferably, it is 3-30 mass parts, More preferably, it is 5 - 20 parts by mass. When content of an amine-modified silicone compound (F) is in the said range, there exists a tendency for the elastic modulus retention rate and thermal expansion coefficient of the hardened|cured material obtained to improve more.

[curing accelerator]

The resin composition of this embodiment may further contain a hardening accelerator. Although it does not specifically limit as a hardening accelerator, For example, Organic peroxides, such as triphenylimidazole, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert- butyl- di- perphthalate, ; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine , tertiary amines such as triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; What is formed by dissolving these organometallic salts in hydroxyl-containing compounds, such as a phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; Organotin compounds, such as a dioctyl tin oxide, other alkyl tin, and an alkyl tin oxide, are mentioned. Among these, triphenylimidazole promotes the curing reaction and is particularly preferable because it tends to have excellent glass transition temperature and coefficient of thermal expansion.

[solvent]

The resin composition of this embodiment may further contain a solvent. By including a solvent, the viscosity at the time of preparation of a resin composition becomes low, while handling property improves more, there exists a tendency for the impregnability with respect to the base material mentioned later to improve more.

Although it will not specifically limit if a part or all of the resin component in a resin composition can be melt|dissolved as a solvent, For example, Ketones, such as acetone, methyl ethyl ketone, a methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; Propylene glycol monomethyl ether, its acetate, etc. are mentioned. A solvent may be used individually by 1 type, and may use 2 or more types together.

[Glass Transition Temperature (Tg)]

The glass transition temperature of the resin composition of this embodiment becomes like this. Preferably it is 270-360 degreeC, More preferably, it is 290-355 degreeC, More preferably, it is 310-350 degreeC. A glass transition temperature can be measured by the method as described in an Example.

[Elastic modulus retention rate]

The elastic modulus retention of the resin composition of this embodiment becomes like this. Preferably it is 75 to 99 %, More preferably, it is 80 to 95 %, More preferably, it is 85 to 95 %. With "elastic modulus retention", according to JIS standard C6481, the flexural modulus of 27 degreeC and 260 degreeC was measured, and the elastic modulus of the 27 degreeC bending elastic modulus (a) and 260 degreeC heat|fever bending elastic modulus (b) was obtained. It points out what computed the difference by the following formula. In addition, being excellent in elastic modulus retention points out that the difference of the bending elastic modulus in 27 degreeC and the bending elastic modulus in 260 degreeC (thermal elastic modulus) is small, for example.

Elastic modulus retention = [(b)/(a)] × 100

[Method for producing resin composition]

Although the manufacturing method of the resin composition of this embodiment is not specifically limited, For example, each component is mix|blended with a solvent one by one, and the method of fully stirring is mentioned. At this time, in order to melt|dissolve or disperse|distribute each component uniformly, well-known processes, such as stirring, mixing, and kneading|mixing process, can be implemented. The dispersibility of the inorganic filler (C) with respect to a resin composition can be improved by performing a stirring dispersion process specifically, using the stirring tank which attached the stirrer which has suitable stirring ability. The said stirring, mixing, and kneading|mixing process can be performed suitably using well-known apparatuses, such as an apparatus for the purpose of mixing, such as a ball mill and a bead mill, or a revolving or autorotation type mixing apparatus, for example.

Moreover, at the time of preparation of the resin composition of this embodiment, an organic solvent can be used as needed. The kind of organic solvent will not be specifically limited if resin in a resin composition can be melt|dissolved. The specific example is as above-mentioned.

[purpose]

The resin composition of this embodiment can be used suitably as a prepreg, a resin sheet, a laminated resin sheet, a laminated board, a metal foil clad laminated board, or a printed wiring board. Hereinafter, a prepreg, a resin sheet, a laminated resin sheet, a laminated board, a metal foil clad laminated board, or a printed wiring board is demonstrated.

[Prepreg]

The prepreg of this embodiment has a base material and the said resin composition impregnated or apply|coated to the base material. The manufacturing method of a prepreg can be implemented according to a conventional method, and is not specifically limited. For example, after impregnating or apply|coating the resin component in this embodiment to a base material, it heats for 1-30 minutes in a 100-200 degreeC dryer, or semi-hardening (B-staging), The prepreg of this embodiment can be produced.

To [ content of the resin composition (inorganic filler (C) is included. ) is preferably 30-90 mass % with respect to the total amount of a prepreg, More preferably, it is 35-85 mass %, Preferably it is 40- 80 mass %. When content of a resin composition exists in the said range, there exists a tendency for a moldability to improve more.

It does not specifically limit as a base material, According to the target use and performance, the well-known thing used for various printed wiring board materials can be selected and used suitably. Although it does not specifically limit as a specific example of the fiber which comprises a base material, For example, Glass fibers, such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, T glass; Inorganic fibers other than glass, such as quartz; Polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), copolyparaphenylene/3,4'oxydiphenylene/terephthalamide (Technora (registered trademark), manufactured by Teijin Techno Products) wholly aromatic polyamides such as; polyesters such as 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray) and Xexion (registered trademark, manufactured by KB Siren); Organic fibers, such as polyparaphenylene benzoxazole (Zylon (trademark), Toyo Spinning Co., Ltd. make), and a polyimide are mentioned. Among these, at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fiber is preferable from the viewpoint of a low coefficient of thermal expansion. These base materials may be used individually by 1 type, and may use 2 or more types together.

Although it does not specifically limit as a shape of a base material, For example, a woven fabric, a nonwoven fabric, roving, a chopped strand mat, and a surfacing mat are mentioned. Although it does not specifically limit as the weaving method of a woven fabric, For example, a plain weave, a hand-made weave, and a twill weave are known, From these well-known ones, depending on the intended use and performance, it can select and use it suitably. Moreover, the thing which carried out the opening process of these, and the glass woven fabric surface-treated with the silane coupling agent etc. are used preferably. Although the thickness and mass of a base material are not specifically limited, Usually, the thing of about 0.01-0.3 mm is used preferably. In particular, from the viewpoint 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 woven glass fabric made of glass fibers such as E glass, S glass and T glass. .

[Resin Sheet]

The resin sheet of this embodiment is formed by shape|molding the said resin composition into sheet shape. The manufacturing method of a resin sheet can be implemented according to a conventional method, and is not specifically limited. For example, in the manufacturing method of the following laminated resin sheet, after apply|coating and drying the solution which melt|dissolved the resin composition of this embodiment in the solvent on a sheet base material, the method of peeling or etching a sheet base material from a laminated resin sheet is mentioned. can In addition, 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 producing a single-layered resin sheet (resin sheet) without using a sheet substrate. you may get

[Laminated Resin Sheet]

The laminated resin sheet of this embodiment has a sheet base material and the said resin composition laminated|stacked on the single side|surface or both surfaces of this sheet base material. A laminated resin sheet is used as one means of thinning, for example, a thermosetting resin (including an inorganic filler (C)) used for a prepreg or the like is applied directly to a support such as a metal foil or a film and dried. can be manufactured by

Although it does not specifically limit as a sheet|seat base material, Well-known thing used for various printed wiring board materials can be used. For example, polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, aluminum foil, copper foil , gold leaf, and the like. Among them, an electrolytic copper foil and a PET film are preferable.

As a coating method, the method of apply|coating the solution which melt|dissolved the resin composition of this embodiment in the solvent with a bar coater, a die coater, a doctor blade, a baker applicator etc. on a sheet|seat base material is mentioned, for example.

It is preferable that the laminated resin sheet is semi-hardened (B-staged) after apply|coating the said resin composition to a sheet|seat base material. Specifically, for example, after apply|coating the said resin composition to sheet base materials, such as copper foil, it is made semi-hardened by the method of heating 1-60 minutes in a 100-200 degreeC dryer, The method of manufacturing a laminated resin sheet, etc. can be heard As for the adhesion amount of the resin composition with respect to a sheet|seat base material, the range of 1-300 micrometers in resin thickness of a laminated resin sheet is preferable.

[Laminate]

The laminated board of this embodiment has one or more at least 1 sort(s) selected from the group which consists of the said prepreg, the said resin sheet, and the said laminated resin sheet.

[Metal foil clad laminate]

The metal foil-clad laminate of the present embodiment includes at least one selected from the group consisting of the prepreg, the resin sheet, and the laminated resin sheet, and one or both surfaces of the prepreg, the resin sheet, and the laminated resin sheet. has a metal foil disposed on the That is, the metal foil-clad laminate of this embodiment is obtained by laminating|stacking and hardening at least 1 sort(s) and metal foil selected from the group which consists of the said prepreg, the said resin sheet, and the said laminated resin sheet.

The insulating layer may be the above-mentioned resin composition, single-layer prepreg, resin sheet, or laminated resin sheet, or may be formed by laminating two or more layers of the above-mentioned resin composition, prepreg, resin sheet, or laminated resin sheet.

The conductor layer can be made of metal foil such as copper or aluminum. Although the metal foil used here will not be specifically limited if it is used for a printed wiring board material, Well-known copper foils, such as a rolled copper foil and an electrolytic copper foil, are preferable. Moreover, although the thickness of a conductor layer is although it does not specifically limit, 1-70 micrometers is preferable, More preferably, it is 1.5-35 micrometers.

The molding method and the molding conditions for the metal foil-clad laminate are not particularly limited, and the general methods and conditions for the laminate for printed wiring boards and the multi-layered board are applicable. For example, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used at the time of shaping|molding of a metal foil clad laminated board. Moreover, in shaping|molding of a metal foil clad laminated board, temperature is 100-300 degreeC, a pressure is 2-100 kgf/cm<2> of surface pressure, and the range of 0.05 to 5 hours of heating time is common. Moreover, you can also perform post-curing at the temperature of 150-300 degreeC as needed. Moreover, it can also be set as a multilayer board by combining the above-mentioned prepreg and the wiring board for inner layers manufactured separately and lamination|stacking.

[Printed wiring board]

The printed wiring board of this embodiment is a printed wiring board containing an insulating layer and the conductor layer formed in the surface of the said insulating layer, The said insulating layer contains the said resin composition. The said metal foil clad laminated board can be used suitably as a printed wiring board by forming a predetermined|prescribed wiring pattern. And the said metal foil-clad laminated board has a low coefficient of thermal expansion, favorable moldability, and chemical-resistance, and can be used especially effectively as a printed wiring board for semiconductor packages which such performance is calculated|required.

The printed wiring board of this embodiment can be manufactured with the following method specifically, for example. First, the above-mentioned metal foil-clad laminated board (metal foil-clad laminated board, etc.) is prepared. The surface of the metal foil-clad laminate is etched to form an inner-layer circuit, and an inner-layer substrate is produced. The surface of the inner circuit of this inner substrate is subjected to surface treatment to increase the adhesive strength if necessary, and then the above-mentioned prepreg is superimposed on the surface of the inner circuit for the required number of sheets, and a metal foil for an outer circuit is laminated on the outside thereof. and integrally molded by heating and pressing. In this way, a multilayer laminate in which an insulating layer comprising a base material and a cured product of a thermosetting resin composition is formed between the metal foil for an inner circuit and an outer circuit is produced. Subsequently, after the multilayer laminate is subjected to a through hole or via hole drilling process, a desmear treatment is performed to remove smear, which is a residue of the resin derived from the resin component contained in the cured product layer. Thereafter, a plated metal film is formed on the wall surface of the hole to conduct an inner circuit and a metal foil for an outer circuit, and the metal foil for an outer circuit is etched to form an outer circuit, and a printed wiring board is manufactured.

For example, the above-mentioned prepreg (the base material and the above-mentioned resin composition adhering thereto), the resin composition layer (layer composed of the above-mentioned resin composition) of the metal foil clad laminate is the above-mentioned resin composition to constitute an insulating layer comprising

Moreover, when not using a metal foil-clad laminated board, you may produce the printed wiring board by forming the conductor layer used as a circuit in what consists of the said prepreg, the said laminated resin sheet, or the said resin composition. At this time, the method of electroless plating can also be used for formation of a conductor layer.

The printed wiring board of this embodiment effectively suppresses warpage of a semiconductor plastic package by maintaining the excellent elastic modulus of the above-mentioned insulating layer even under the reflow temperature at the time of semiconductor mounting, so that it can be used particularly effectively as a printed wiring board for semiconductor packages. .

Example

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. The present invention is not limited at all by the following examples.

[Synthesis Example 1: Synthesis of diallylbisphenol A-type cyanate ester compound]

700 g of diallylbisphenol A (hydroxyl group equivalent: 154.2 g/eq.) (4.54 mol in terms of OH groups) (DABPA, manufactured by Daiwa Chemical Industry Co., Ltd.) and 459.4 g (4.54 mol) of triethylamine (hydroxyl group 1) 1.0 mol per mole) was dissolved in 2100 g of dichloromethane, and this was referred to as solution 1.

474.4 g (7.72 mol) of cyanogen chloride (1.7 mol per 1 mol of hydroxyl group), 1106.9 g of dichloromethane, 735.6 g (7.26 mol) of 36% hydrochloric acid (1.6 mol per 1 mol of hydroxyl group), 4560.7 g of water , while maintaining the solution temperature at -2 to -0.5°C under stirring, the solution 1 was injected and added over 90 minutes. After completion of the dropwise addition of the solution 1, after stirring at the same temperature for 30 minutes, a solution (solution 2) in which 459.4 g (4.54 mol) of triethylamine (1.0 mol per 1 mol of hydroxyl group) was dissolved in 459.4 g of dichloromethane (Solution 2) was added to 25 The infusion was added over the course of minutes. After completion of the solution 2 injection and addition, the reaction was completed by stirring at the same temperature for 30 minutes.

After that, the reaction solution was allowed to stand to separate an organic phase and an aqueous phase. The obtained organic phase was washed with 2 L of 0.1 N hydrochloric acid, and then washed 6 times with 2000 g of water. The electrical conductivity of the wastewater at the 6th time of water washing was 20 µS/cm, and it was confirmed that the ionic compound to be removed was sufficiently removed by washing with water.

The organic phase after washing with water was concentrated under reduced pressure and finally concentrated to dryness at 90°C for 1 hour to obtain the target diallylbisphenol A cyanate ester compound (DABPA-CN, cyanate ester group equivalent: 179 g/eq.) 805 g was obtained as a light yellow liquid. The IR spectrum of the obtained DABPA-CN showed absorption of 2264 cm ^-1 (cyanic acid ester group), and absorption of hydroxyl group was not shown.

[Synthesis Example 2: Synthesis of α-naphthol aralkyl type cyanate ester compound]

In the reactor, α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g/eq., manufactured by New Nippon Chemical Co., Ltd.: naphthol aralkyl having a repeating unit number (n) of 1 to 5 is included. ) 0.47 mol (in terms of OH groups) was dissolved in 500 mL of chloroform, and 0.7 mol of triethylamine was added to this solution. While maintaining the temperature at -10°C, 300 g of a 0.93 mol cyanogen chloride solution in chloroform was added dropwise into the reactor over 1.5 hours, and after completion of the dropping, the mixture was stirred for 30 minutes. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was further added dropwise to the reactor, followed by stirring for 30 minutes to complete the reaction. After the hydrochloric acid salt of triethylamine by-produced was separated by filtration from the reaction solution, the resulting filtrate was washed with 500 mL of 0.1 N hydrochloric acid, followed by washing with 500 mL of water repeated 4 times. After drying this with sodium sulfate, it evaporated at 75 degreeC, and degassed under reduced pressure at 90 degreeC again to obtain brown solid (alpha)-naphthol aralkyl type cyanate ester resin (SNCN). As a result of analyzing the obtained α-naphthol aralkyl-type cyanate ester resin (SN495-V-CN, cyanate ester group equivalent: 261 g/eq.) by infrared absorption spectrum, cyanate ester groups in the vicinity of 2264 cm ^-1 absorption was confirmed.

[Example 1]

48.3 parts by mass of DABPA-CN obtained in Synthesis Example 1, 27 parts by mass of a novolac maleimide compound (BMI-2300, manufactured by Daiwa Chemical Industries, Ltd., maleimide group equivalent: 186 g/eq.), bismalei 14.7 parts by mass of the imide compound (BMI-80, manufactured by Daiwa Chemical Industries, Ltd., maleimide group equivalent: 285 g/eq.), an amine-modified silicone compound (X-22-161B, manufactured by Shin-Etsu Chemical Industries, Ltd.); Functional group equivalent: 1500 g/eq.) 10 parts by mass, slurry silica (SC-5050MOB, average particle diameter 1.5 µm, manufactured by Adomatex Co., Ltd.) 100 parts by mass, wetting and dispersing agent (DISPERBYK-161, Big Chemie Japan) (Co., Ltd. product) 1 mass part, Leveling agent (Bikchemi Japan Co., Ltd. product, "BYK-310") 0.05 mass part, hardening accelerator (2,4,5-triphenylimidazole, Tokyo Chemicals) Industrial Co., Ltd. product) was mixed 0.5 mass part, and the varnish was obtained. This varnish was diluted with methyl ethyl ketone, impregnated and coated on a 0.1-mm-thick T-glass woven fabric, and heat-dried at 140 degreeC for 3 minutes, and the prepreg with a resin content of 44 mass % was obtained. In addition, the amount of cyanate ester groups (α) (parts by mass/equivalent of cyanate ester groups) of the cyanate ester compound (A) is 0.270, and the amount of maleimide groups (β) of the maleimide compound (B) (parts by mass/maleimide) group equivalent) was 0.197, and the ratio ([α/β]) was 1.37.

[Example 2]

A prepreg was obtained in the same manner as in Example 1, except that the amount of DABPA-CN used was 40.3 parts by mass and the amount of BMI-2300 used was 35 parts by mass. In addition, the amount of cyanate ester groups (α) (parts by mass/equivalent of cyanate ester groups) of the cyanate ester compound (A) is 0.225, and the amount of maleimide groups (β) of the maleimide compound (B) (parts by mass/maleimide) group equivalent) was 0.240, and the ratio ([α/β]) was 0.94.

[Example 3]

A prepreg was obtained in the same manner as in Example 1, except that the amount of DABPA-CN used was 27.3 parts by mass and the amount of BMI-2300 used was 48 parts by mass. Incidentally, the amount of cyanate ester groups (α) (parts by mass/equivalent to cyanate ester group) of the cyanate compound (A) is 0.153, and the amount of maleimide groups (β) of the maleimide compound (B) (parts by mass/maleimide) group equivalent) was 0.310, and the ratio ([α/β]) was 0.49.

[Example 4]

A prepreg was obtained in the same manner as in Example 1, except that the amount of DABPA-CN used was 19.3 parts by mass and the amount of BMI-2300 used was 56 parts by mass. In addition, the amount of cyanate ester groups (α) (parts by mass/equivalent of cyanate ester groups) of the cyanate compound (A) is 0.108, and the amount of maleimide groups (β) of the maleimide compound (B) (parts by mass/maleimide) group equivalent) was 0.353, and the ratio ([α/β]) was 0.31.

[Comparative Example 1]

A prepreg was obtained in the same manner as in Example 1, except that the amount of DABPA-CN used was 14.3 parts by mass and the amount of BMI-2300 used was 61 parts by mass. In addition, the amount of cyanate ester groups (α) (parts by mass/equivalent of cyanate ester groups) of the cyanate ester compound (A) is 0.080, and the amount of maleimide groups (β) of the maleimide compound (B) (parts by mass/maleimide) group equivalent) was 0.380, and the ratio ([α/β]) was 0.21.

[Example 5]

52.7 parts by mass of SN495-V-CN obtained in Synthesis Example 2, 37.3 parts by mass of a novolak maleimide compound (BMI-2300, manufactured by Daiwa Chemical Industries, Ltd., maleimide group equivalent: 186 g/eq.); 10 parts by mass of a biphenyl aralkyl-type epoxy compound (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., functional group equivalent: 290 g/eq.), silica slurry (SC-5050MOB, average particle diameter 1.5 μm, Adomatex Co., Ltd.) ) 100 parts by mass, 1 part by mass of wetting and dispersing agent (DISPERBYK-161, manufactured by Bikchemy Japan Co., Ltd.), and 0.05 parts by mass of leveling agent (“BYK-310” manufactured by Bicchemi Japan Co., Ltd.) Bu and 0.5 mass parts of hardening accelerators (2,4,5-triphenyl imidazole, Tokyo Chemical Industry Co., Ltd. product) were mixed, and the varnish was obtained. This varnish was diluted with methyl ethyl ketone, impregnated and coated on a 0.1-mm-thick T-glass woven fabric, and heat-dried at 140 degreeC for 3 minutes, and the prepreg with a resin content of 48 mass % was obtained. The amount of cyanate ester groups (α) (parts by mass/equivalent of cyanate ester groups) of the cyanate compound (A) is 0.202, and the amount of maleimide groups (β) of the maleimide compound (B) (parts by mass/maleimide) group equivalent) was 0.201, and the ratio ([α/β]) was 1.01.

[Comparative Example 2]

A prepreg was obtained in the same manner as in Example 5, except that the amount of SN495-V-CN used was 25.3 parts by mass and the amount of BMI-2300 used was 64.7 parts by mass. In addition, the amount of cyanate ester groups (α) (parts by mass/equivalent of cyanate ester groups) of the cyanate ester compound (A) is 0.097, and the amount of maleimide groups (β) of the maleimide compound (B) (parts by mass/maleimide) group equivalent) was 0.348, and the ratio ([α/β]) was 0.28.

[Example 6]

24.9 parts by mass of SN495-V-CN obtained in Synthesis Example 2, 43.3 parts by mass of a novolak maleimide compound (BMI-2300, manufactured by Daiwa Chemical Industries, Ltd., maleimide group equivalent: 186 g/eq.); 31.8 parts by mass of bisallylnadiimide (manufactured by Maruzen Petrochemical Co., Ltd., "BANI-M"), 200 parts by mass of silica slurry (SC-5050 MOB, average particle diameter 1.5 µm, manufactured by Adomatex Co., Ltd.), wetting and dispersing agent (DISPERBYK-161, manufactured by Big Chemie Japan Co., Ltd.) 1 part by mass, leveling agent (by Big Chemie Japan Co., Ltd., "BYK-310") 0.05 parts by mass, curing accelerator (2,4,5 - 0.5 mass parts of triphenylimidazole and Tokyo Chemical Industry Co., Ltd. product) were mixed, and the varnish was obtained. This varnish was diluted with methyl ethyl ketone, impregnated and coated on a 0.1-mm-thick T-glass woven fabric, and heat-dried at 140 degreeC for 3 minutes, and the prepreg with a resin content of 48 mass % was obtained. Moreover, the amount of cyanate ester groups (α) (parts by mass/equivalent of cyanate ester groups) of the cyanate compound (A) is 0.095, and the amount of maleimide groups (β) of the maleimide compound (B) (parts by mass/maleimide) group equivalent) was 0.233, and the ratio ([α/β]) was 0.41.

[Comparative Example 3]

The amount of SN495-V-CN used was 5 parts by mass, the amount of BMI-2300 used was 49 parts by mass, and the amount of BANI-M used was 36 parts by mass, and a biphenyl aralkyl-type epoxy compound (NC-3000H, Nippon Kayakusho ( Note) A prepreg was obtained in the same manner as in Example 6 except that 10 parts by mass of the production, functional group equivalent: 290 g/eq.) was used. Incidentally, the amount of cyanate ester groups (α) (parts by mass/equivalent of cyanate ester groups) of the cyanate compound (A) is 0.019, and the amount of maleimide groups (β) of the maleimide compound (B) (parts by mass/maleimide) group equivalent) was 0.263, and the ratio ([α/β]) was 0.07.

[Example 7]

Bisphenol A-type cyanate ester compound (CA210, manufactured by Mitsubishi Gas Chemical Co., Ltd., cyanate equivalent: 139 g/eq.) 40.5 parts by mass, maleimide compound (BMI-70, maleimide group equivalent 221 g/eq, K · Ai Chemicals Co., Ltd.) 29.8 parts by mass, biphenyl aralkyl type epoxy compound (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., functional group equivalent: 290 g/eq.) 15 parts by mass, bismaleimide compound (BMI) -80, manufactured by Daiwa Chemical Industry Co., Ltd., maleimide group equivalent: 285 g/eq.) 14.7 parts by mass, 100 parts by mass of slurry silica (SC-5050MOB, average particle diameter 1.5 µm, manufactured by Adomatex Co., Ltd.) , 1 part by mass of a wetting and dispersing agent (DISPERBYK-161, manufactured by Bikchemi Japan Co., Ltd.), 0.05 parts by mass of a leveling agent (“BYK-310” manufactured by Bicchemi Japan Co., Ltd.), a curing accelerator (2, 0.5 mass parts of 4,5-triphenyl imidazole and Tokyo Chemical Industry Co., Ltd. product) were mixed, and the varnish was obtained. This varnish was diluted with methyl ethyl ketone, impregnated and coated on a 0.1-mm-thick T-glass woven fabric, and heat-dried at 140 degreeC for 3 minutes, and the prepreg with a resin content of 44 mass % was obtained. Incidentally, the amount of cyanate ester groups (α) (parts by mass/equivalent of cyanate ester groups) of the cyanate compound (A) is 0.291, and the amount of maleimide groups (β) of the maleimide compound (B) (parts by mass/maleimide) group equivalent) was 0.186, and the ratio ([α/β]) was 1.56.

[Comparative Example 4]

The amount of the bisphenol A cyanate ester compound (CA210, manufactured by Mitsubishi Gas Chemical Co., Ltd., cyanate equivalent: 139 g/eq.) was 12 parts by mass, and the maleimide compound (BMI-70, maleimide group equivalent 221 g) A prepreg was obtained in the same manner as in Example 7 except that the amount of /eq, manufactured by K-I Chemicals Co., Ltd.) was 58.3 parts by mass. In addition, the amount of cyanate ester groups (α) (parts by mass/equivalent of cyanate ester groups) of the cyanate compound (A) is 0.086, and the amount of maleimide groups (β) of the maleimide compound (B) (parts by mass/maleimide) group equivalent) was 0.315, and the ratio ([α/β]) was 0.27.

[Production of metal foil clad laminate]

4 or 8 sheets of the obtained prepreg are stacked, respectively, and 12 μm thick electrolytic copper foil (3EC-VLP, manufactured by Mitsui Metals Mining Co., Ltd.) is placed up and down, and the pressure is 30 kgf/cm 2 and the temperature is 220° C. for 120 minutes. Lamination molding was performed to obtain a metal foil-clad laminate having an insulating layer thickness of 0.4 mm and 0.8 mm. The following glass transition temperature (Tg) linear thermal expansion coefficient and copper foil peeling strength were measured using the obtained metal foil clad laminated board.

[Copper Foil Peeling Strength]

According to JIS C6481, copper foil peeling strength (kg/cm) was measured using the obtained metal foil clad laminated board (insulation layer thickness 0.8mm).

[Plating Peel Strength]

The surface copper foil of the obtained metal foil-clad laminate (insulation layer thickness 0.4 mm) was removed by etching, and an electroless copper plating process manufactured by Uemura Kogyo (Chemical name: MCD-PL, MDP-2, MAT-SP, MAB-) With 4-C, MEL-3-APEA ver.2), electroless copper plating of about 0.5 µm was performed, and drying was performed at 130°C for 1 hour. Then, electrolytic copper plating was performed so that the thickness of plating copper might be set to 18 micrometers, and it dried at 180 degreeC for 1 hour. In this way, the printed wiring board sample in which the 18-micrometer-thick conductor layer (plating copper) was formed on the 0.4-mm-thick insulating layer was produced. Using the printed wiring board sample with an insulating layer thickness of 0.4 mm produced by the said procedure, the adhesive force of plated copper was measured three times according to JIS C6481, and the average value (kg/cm) was calculated|required.

[Glass Transition Temperature (Tg)]

After cut|disconnecting the obtained metal foil clad laminated board (insulation layer thickness 0.8mm) to size 12.7x2.5mm with a dicing saw, the copper foil on the surface was removed by etching, and the sample for a measurement was obtained. Using this sample for measurement, the glass transition temperature was measured by the DMA method with a dynamic viscoelasticity analyzer (manufactured by TA Instruments) according to JIS C6481 (average value of n=3).

[Elastic modulus retention rate]

Using what removed copper foil from the obtained metal foil clad laminated board (insulation layer thickness 0.8mm) as a sample, according to the method prescribed|regulated to JIS C 6481, by autograph (Co., Ltd. Shimadzu Corporation AG-Xplus), 27 degreeC, respectively, The flexural modulus was measured at 260°C. The elastic modulus retention was calculated by the following formula from the 27 degreeC flexural modulus (a) and the 260 degreeC thermal bending elastic modulus (b) measured by the above.

Elastic modulus retention = (b)/(a) × 100

[Flexibility]

The obtained prepreg was wound around a rod of a predetermined diameter and bent at 180°, the bent portion of the prepreg was observed, and the case in which damage occurred in the prepreg was set as no breakage, and the case where breakage did not occur was evaluated.

A: No damage to the prepreg at 3 mmφ.

B: No damage to the prepreg at 5 mmφ.

C: No damage to the prepreg at 10 mmφ.

D: There is damage to the prepreg by 10 mmφ.

This application is based on the Japanese Patent Application (Patent Application 2016-92758) for which it applied to the Japan Patent Office on May 2, 2016, The content is taken in here as a reference.

Industrial Applicability

The resin composition of this invention has industrial applicability as a material of a prepreg, a resin sheet, a laminated resin sheet, a metal foil clad laminated board, and a printed wiring board.

Claims (20)

containing a cyanate ester compound (A), a maleimide compound (B), and an amine-modified silicone compound (F);
The ratio ([α/β]) of the amount of cyanate ester groups (α) of the cyanate ester compound (A) to the amount of maleimide groups (β) of the maleimide compound (B) is 0.30 to 2.0;
The resin composition in which the said cyanate ester compound (A) contains the compound represented by following General formula (1).

(In formula (1), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² is each independently selected from the group consisting of a cyanate ester group, a hydroxyl group and an allyl group as a substituent. A phenyl group, a hydrogen atom, an allyl group, a cyanate ester group, or an epoxy group which may have at least one is represented, n1 is an integer of 1 or more, and m is an integer of 1-4.) The method of claim 1,
The resin composition in which the said cyanate ester compound (A) contains the compound represented by following General formula (2).

(In formula (2), R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n2 is an integer of 1 or more.) The method of claim 1,
The cyanate ester group equivalent of the said cyanate ester compound (A) is 100-220 g/eq. phosphorus, a resin composition. The method of claim 1,
The resin composition in which the said cyanate ester compound (A) contains the compound represented by the following general formula (1'').

(In formula (1''), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1 is an integer of 1 or more.) The method of claim 1,
The resin composition in which the said cyanate ester compound (A) contains the compound represented by following General formula (3).

The method of claim 1,
Said maleimide compound (B) is bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl- A resin composition comprising at least one selected from the group consisting of 4-maleimidephenyl)methane and a maleimide compound represented by the following formula (4).

(In the formula, R ⁴ each independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.) The method of claim 1,
The resin composition, wherein the ratio ([α/β]) is 0.45 to 1.0. The method of claim 1,
The resin composition further comprising an inorganic filler (C). 9. The method of claim 8,
The resin composition whose content of the said inorganic filler (C) is 25-700 mass parts with respect to 100 mass parts of resin solid content. 9. The method of claim 8,
The resin composition in which the said inorganic filler (C) contains at least 1 type selected from the group which consists of a silica, a boehmite, and alumina. The method of claim 1,
The resin composition in which the said amine-modified silicone compound (F) contains the compound represented by following General formula (11).

(In the formula, R ⁸ each independently represents a hydrogen atom, a methyl group or a phenyl group, and R ⁹ each independently represents a single bond, an alkylene group having 1 to 8 carbon atoms, and/or an arylene group.) The method of claim 1,
The amino group equivalent of the said amine-modified silicone compound (F) is 130-6000, The resin composition. The method of claim 1,
The resin composition in which content of the said amine-modified silicone compound (F) is 1-40 mass parts with respect to 100 mass parts of resin solid content. description and
A prepreg comprising the resin composition according to any one of claims 1 to 13 impregnated or applied to the base material. A resin sheet formed by forming the resin composition according to any one of claims 1 to 13 in a sheet shape. The laminated resin sheet which has a sheet base material and the resin composition in any one of Claims 1-13 arrange|positioned on the single side|surface or both surfaces of this sheet base material. (a) a prepreg having a base material and the resin composition according to any one of claims 1 to 13 impregnated or applied to the base material;
(b) a resin sheet formed by forming the resin composition in a sheet shape; and
(c) a laminated resin sheet having a sheet substrate and the resin composition disposed on one or both surfaces of the sheet substrate;
A laminate having one or more at least one selected from the group consisting of. (a) a prepreg having a base material and the resin composition according to any one of claims 1 to 13 impregnated or applied to the base material;
(b) a resin sheet formed by forming the resin composition in a sheet shape; and
(c) a laminated resin sheet having a sheet substrate and the resin composition disposed on one or both surfaces of the sheet substrate;
A metal foil-clad laminate comprising at least one selected from the group consisting of: the prepreg, the resin sheet, and a metal foil disposed on one or both surfaces of the laminated resin sheet. an insulating layer and a conductor layer formed on one or both surfaces of the insulating layer;
The printed wiring board in which the said insulating layer contains the resin composition in any one of Claims 1-13. delete