KR102376567B1 - Resin composition and its manufacturing method, prepreg, resin sheet, laminated board, metal foil-clad laminated board, and printed wiring board - Google Patents

Abstract

This invention is obtained by making an amino-modified silicone (A), a maleimide compound (B), and 1 type(s) or 2 or more types chosen from the group which consists of carboxylic acid (C) and carboxylic acid anhydride (D) react A resin composition containing a reaction product (P) is provided.

Description

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

The present invention relates to a resin composition and a method for manufacturing the same, a prepreg, a 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 semiconductor packages has been further accelerated in recent years. Especially, 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 a 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 laminated board (higher rigidity) and increasing the glass transition temperature of the laminated sheet (higher Tg) are being considered (e.g. For example, refer to Patent Documents 4 and 5).

Japanese Patent Laid-Open No. 2013-216884 Japanese Patent Publication 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, even if it is a printed wiring board using the thermosetting resin composition described in Patent Documents 1 to 5, the peel strength of a laminated sheet laminated with metal foil, for example, chemical resistance to a strong alkaline cleaning liquid (desmear resistance), etc. The problem that warpage occurs in the semiconductor plastic package as a result remains because it is difficult to achieve compatibility.

Here, in order to reduce the difference in the coefficient of thermal expansion and solve the problem of warpage, as a low elastic component in the resin composition, for example, amino-modified silicone produced by reacting an amino-modified silicone and a thermosetting component Polymers may be incorporated. However, the amino-modified polymer generally has a property of further polymerization-reacting with each other or with other resin components. For this reason, it originates in the amino-modified polymer causing a polymerization reaction further during storage or molding of a resin composition or a prepreg, and excellent storage stability may not be obtained.

Then, this invention was made|formed in order to solve the subject mentioned above, and an object of this invention is to provide the resin composition which has the outstanding storage stability, containing the amino-modified polymer.

That is, the present invention is as follows.

[One]

an amino-modified silicone (A);

A maleimide compound (B), and

A resin composition comprising a reaction product (P) obtained by reacting at least any of carboxylic acid (C) or carboxylic acid anhydride (D).

[2]

The resin composition according to [1], wherein the resin composition has an amine value of 2.0 mgKOH/g or less.

[3]

The reaction product (P) is obtained by reacting at least the carboxylic acid anhydride (D),

The resin composition according to [1] or [2], wherein the carboxylic acid anhydride (D) is one or more selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, and acetic anhydride.

[4]

The reaction product (P) is obtained by at least reacting the carboxylic acid (C),

The resin composition according to any one of [1] to [3], wherein the carboxylic acid (C) is one or more selected from the group consisting of maleic acid, phthalic acid, succinic acid, and acetic acid.

[5]

The resin composition according to any one of [1] to [4], further comprising a thermosetting component (E).

[6]

The said thermosetting component (E) is 1 type or 2 types selected from the group which consists of a maleimide compound (B), an epoxy resin (F), a cyanate ester compound (G), and an alkenyl-substituted nadiimide (H). The resin composition according to [5], containing the above.

[7]

The resin composition according to any one of [1] to [6], wherein the amino-modified silicone (A) in the reaction product (P) contains a compound represented by the following general formula (1).

[Formula 1]

(in formula (1), a plurality of R _a each independently represents a hydrogen atom, a methyl group or a phenyl group, a plurality of R _b each independently represents a single bond, an alkylene group or an aryl group, and n is an integer of 1 or more (represents 整數)

[8]

The resin composition according to any one of [1] to [7], wherein the amino group equivalent of the amino-modified silicone (A) in the reaction product (P) is 130 or more and 6000 or less.

[9]

Said maleimide compound (B) is bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl- containing one or two or more selected from the group consisting of 4-maleimidephenyl)methane, polytetramethyleneoxide-bis(4-maleimidebenzoate), and a compound represented by the following general formula (2), [ The resin composition according to any one of 1] to [8].

[Formula 2]

(in formula (2), a plurality of R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more)

[10]

The resin composition according to any one of [1] to [9], further comprising a filler (J).

[11]

The resin composition according to [10], wherein the filler (J) contains one or more selected from the group consisting of silica, alumina, and aluminum nitride.

[12]

The resin composition contains 50 parts by mass or more and 300 parts by mass or less of the filler (J) with respect to 100 parts by mass of the total amount of the reaction product (P) and the thermosetting component (E), [10] or [11] The resin composition described in.

[13]

A prepreg comprising a substrate and the resin composition according to any one of [1] to [12] impregnated or applied to the substrate.

[14]

The prepreg according to [13], wherein the substrate is one or more selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth and organic fibers.

[15]

A resin sheet comprising a support and the resin composition according to any one of [1] to [12] disposed on the surface of the support.

[16]

The resin sheet according to [15], wherein the support is a resin sheet or metal foil.

[17]

A laminate comprising a plurality of one or two or more types selected from the group consisting of the prepreg according to [13] or [14] and the resin sheet according to [15] or [16].

[18]

A metal foil-clad laminate comprising one or two or more selected from the group consisting of the prepreg according to [13] or [14] and the resin sheet according to [15] or [16], and a metal foil.

[19]

A printed wiring board comprising an insulating layer containing the resin composition according to any one of [1] to [12], and a conductor layer formed on the surface of the insulating layer.

[20]

A first reaction step of reacting an amino-modified silicone (A) with a maleimide compound (B) to obtain a primary polymer;

The manufacturing method of the resin composition which has a 2nd reaction process of making the said primary polymer react at least either of a carboxylic acid (C) or a carboxylic acid anhydride (D).

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. The following present embodiment is an illustration for explaining the present invention, and is not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist.

[resin composition]

The resin composition of the present embodiment is a reaction product (P) obtained by reacting an amino-modified silicone (A), a maleimide compound (B), and at least any one of a carboxylic acid (C) or a carboxylic acid anhydride (D) (prepolymer). Here, the reaction product (P) is one type of the above-mentioned amino-modified polymer.

The resin composition of this embodiment has the outstanding storage stability. This factor is estimated as follows (however, a factor is not limited to this). In the conventional resin composition containing an amino-modified silicone and a thermosetting component, in the amino-modified polymer contained in the resin composition, a relatively large amount of amino groups that are reactive groups of the amino-modified silicone of the raw material remain in the structure of the prepolymer, and the amino groups Due to further reaction with the heat-curable component, excellent storage stability is not obtained in the resin composition (including varnish) and the molded article obtained from the resin composition (for example, the prepreg and the molded article) . For example, when the resin composition is stored at room temperature, the reaction between the remaining amino group and the thermosetting component further proceeds, so that the resin composition is excellent in storage due to an increase in viscosity and increase in molecular weight. stability cannot be obtained. Moreover, in the case of a varnish, gelatinization is raise|generated, and in the case of a prepreg, moldability worsens by the raise of a prepreg viscosity, and the outstanding storage stability cannot be obtained. On the other hand, in the resin composition of this embodiment, the amino group which remained by reaction of an amino-modified silicone (A) and a maleimide compound (B) reacts with carboxylic acid (C) and/or carboxylic acid anhydride (D) By containing one reaction product (P), the storage stability excellent in the said resin composition and the molded object obtained from this resin composition is acquired.

The amine titer of the resin composition is the amine titer as the total amount of the primary amine and the secondary amine. Although the amine titer is not specifically limited, Preferably it is 2.0 mgKOH/g or less, More preferably, it is 1.0 mgKOH/g or less, More preferably, it is 0.5 mgKOH/g or less. When an amine value is 2.0 mgKOH/g or less, there exists a tendency which can suppress the increase of the viscosity of a resin composition, the increase of molecular weight, gelatinization of a varnish, and a raise of a prepreg viscosity. Moreover, there exists a tendency which can suppress the increase of the viscosity of a resin composition, the increase of molecular weight, etc., so that an amine titer is small. The lower limit of the amine titer is preferably 0 mgKOH/g. An amine titer is measured by the method based on JISK7237:1995.

[reaction product (P)]

The reaction product (P) of this embodiment is obtained by making an amino-modified silicone (A), a maleimide compound (B), and at least any one of carboxylic acid (C) or carboxylic acid anhydride (D) react.

A reaction product (P) may be used individually by 1 type, and may mix and use 2 or more types.

Although the weight average molecular weight (Mw) of a reaction product (P) is not specifically limited, Preferably it is 5000 or more and 20000 or less, More preferably, it is 10000 or more and 15000 or less. When the weight average molecular weight is 5000 or more, the thermal expansion coefficient of the prepreg tends to decrease, and when the weight average molecular weight is 20000 or less, the increase in the viscosity of the resin composition, increase in molecular weight, gelation of the varnish, increase in the viscosity of the prepreg tend to be restrained. What is necessary is just to control reaction conditions, such as temperature, in order to obtain the reaction product (P) whose weight average molecular weights are 5000 or more and 20000 or less. A weight average molecular weight can be measured by the gel permeation chromatography (GPC) method, and can be calculated|required as the value converted using the standard polystyrene analytical curve. Specifically, it is measured by the method described in Examples to be described later.

In the resin composition of the present embodiment, the content of the reaction product (P) is not particularly limited, but when combined with the thermosetting component (E), the reaction product (P) and the thermosetting component (E) in the resin composition with respect to the total amount of (100 mass %; solvent/solvent components, as solid content not containing filler (J)), preferably 10 mass % or more and 80 mass % or less, more preferably 15 mass % or more and 70 mass % % or less, and are 20 mass% or more and 60 mass% or less. When content of a reaction product (P) is in the said range, also at the time of filler filling, it is excellent in a moldability, and there exists a tendency to become a printed wiring board excellent in low thermal expansion coefficient, thermal elasticity modulus, desmear resistance, and chemical-resistance.

<Amino-modified silicone (A)>

The amino-modified silicone (A) used in the present embodiment is not particularly limited as long as it is a silicone having one or more amino groups in the molecule, but it is preferable to contain a compound represented by the following general formula (1).

[Formula 3]

In Formula (1), some R<a> represents _a hydrogen atom, a methyl group, or a phenyl group each independently, and a methyl group is especially preferable. A plurality of R _b each independently represents a single bond, an alkylene group, or an aryl group, and among these, an alkylene group is preferable. It is preferable that carbon number of an alkylene group is 1-4 in the principal chain. Although a specific alkylene group is not specifically limited, It is more preferable that it is a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group, It is still more preferable that it is a trimethylene group. In formula (1), n represents an integer of 1 or more.

An amino-modified silicone (A) may be used individually by 1 type, and may be used in mixture of 2 or more type.

Although the amino group equivalent of an amino-modified silicone (A) is not specifically limited, Preferably it is 130 or more and 6000 or less, More preferably, it is 500 or more and 3000 or less, More preferably, it is 600 or more and 2500 or less. When the amino group equivalent of an amino-modified silicone (A) exists in the said range, the printed wiring board excellent in metal foil peeling strength and desmear resistance can be obtained. An amino group equivalent is measured by the method based on JISK7237:1995.

In the resin composition of this embodiment, the content of the amino-modified silicone (A) is not particularly limited, but the total amount of the reaction product (P) in the resin composition (100% by mass; solvent/solvent component, filler (J) is not contained. As the amount of solid content not present), preferably 5.0 mass% or more and 70 mass% or less, more preferably 10 mass% or more and 50 mass% or less, and still more preferably 15 mass% or more and 45 mass% or less. In addition, content of amino-modified silicone (A) is amino-modified silicone (A) and thermosetting component used for preparation of reaction product (P), when combining reaction product (P) and thermosetting component (E). As the total amount of the amino-modified silicone (A) contained as (E), the total amount of the reaction product (P) and the thermosetting component (E) in the resin composition (100% by mass; the solvent/solvent component is not contained as a solid amount ), preferably 1.0 mass% or more and 70 mass% or less, more preferably 3.0 mass% or more and 40 mass% or less, and still more preferably 5.0 mass% or more and 20 mass% or less. Moreover, when content of an amino-modified silicone (A) exists in the said range, the printed wiring board excellent in metal foil peeling strength and desmear resistance can be obtained. In addition to the amino-modified silicone (A) used for preparation of the reaction product (P), the amino-modified silicone (A) as a thermosetting component (E) described later is also included in the content of the amino-modified silicone (A) here. do.

<Maleimide compound (B)>

The maleimide compound (B) used for this embodiment will not be specifically limited if it is a compound which has one or more maleimide groups in a molecule|numerator. Specific examples thereof include, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, 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, polytetramethyleneoxide-bis(4-maleimidebenzoate), a maleimide compound represented by the following general formula (2), a prepolymer of these maleimide compounds, and a prepolymer of a maleimide compound and an amine compound polymers. These can also be used 1 type or in mixture of 2 or more types suitably.

Among them, the maleimide compound (B) is bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, and bis(3-ethyl-5- One or two or more selected from the group consisting of methyl-4-maleimidephenyl)methane, polytetramethyleneoxide-bis(4-maleimidebenzoate), and a maleimide compound represented by the following general formula (2) It is preferable to contain, and it is more preferable to contain 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane.

[Formula 4]

In Formula (2), a plurality of R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.

In Formula (2), it is preferable that some R< ₅ > represents a hydrogen atom or a methyl group each independently, and especially represents a hydrogen atom.

In formula (2), n ₁ represents an integer of 1 or more. _The upper limit of n1 becomes like this. Preferably it is 10, More preferably, it is 7.

A maleimide compound (B) may be used individually by 1 type, and may mix and use 2 or more types.

In the reaction product (P) of this embodiment, the content ratio of the maleimide compound (B) to the amino-modified silicone (A) is not particularly limited, but on a mass basis, preferably 1.0 or more and 3.0 or less, more preferably Preferably it is 1.0 or more and 2.5 or less, More preferably, it is 1.0 or more and 2.0 or less. When the content ratio is within the above range, the productivity of the reaction product (P) tends to be more excellent.

In the resin composition of this embodiment, the content of the maleimide compound (B) is not particularly limited, but the total amount of the reaction product (P) in the resin composition (100% by mass; solvent/solvent component, filler (J) is not contained As the amount of solid content not present), preferably 10 mass % or more and 90 mass % or less, more preferably 30 mass % or more and 80 mass % or less, and still more preferably 45 mass % or more and 75 mass % or less. Moreover, when content of a maleimide compound (B) combines a reaction product (P) and a thermosetting component (E), the maleimide compound (B) and thermosetting component used for preparation of a reaction product (P) As the total amount of the maleimide compound (B) contained as (E), the total amount of the reaction product (P) and the thermosetting component (E) (100% by mass; the solvent/solvent component, the filler (J) does not contain the solid content ), Preferably it is 10 mass % or more and 90 mass % or less, More preferably, it is 20 mass % or more and 80 mass % or less, More preferably, it is 30 mass % or more and 70 mass % or less. When content of a maleimide compound (B) exists in the said range, there exists a tendency for the printed wiring board more excellent in moldability, thermal elastic modulus, desmear resistance, and chemical-resistance to be obtained. In addition, the maleimide compound (B) as a thermosetting component (E) mentioned later is also contained in content of the maleimide compound (B) here in addition to the maleimide compound (B) used for the reaction product (P).

<Carboxylic acid (C), Carboxylic anhydride (D)>

Although the carboxylic acid (C) used in this embodiment is not specifically limited, It is preferable that it is 1 type or 2 or more types selected from the group which consists of maleic acid, phthalic acid, succinic acid, acetic acid, and propionic acid, Maleic acid, phthalic acid, succinic acid and more preferably 1 type or 2 or more types selected from the group consisting of acetic acid, and still more preferably 1 type or 2 or more types selected from the group consisting of maleic acid, phthalic acid and succinic acid. Moreover, although the carboxylic anhydride (D) used for this embodiment is not specifically limited, It is preferable that it is 1 type, or 2 or more types selected from the group which consists of maleic anhydride, phthalic anhydride, succinic anhydride, acetic anhydride, and propionic anhydride. and more preferably one or two or more selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride and acetic anhydride, and one or two selected from the group consisting of maleic anhydride, phthalic anhydride and succinic anhydride More preferably, it is more than a species.

Carboxylic acid (C) and carboxylic acid anhydride (D) are monovalent|monohydric carboxylic acid and monovalent|monohydric carboxylic acid anhydride, or divalent carboxylic acid, and bivalent carboxylic acid anhydride, respectively among those mentioned above. It is preferable that it is, and it is more preferable that they are a divalent carboxylic acid and a divalent carboxylic acid anhydride. Carboxylic acid (C) and carboxylic acid anhydride (D) are divalent carboxylic acid and divalent carboxylic acid anhydride, respectively, compared with the case of monovalent carboxylic acid and monovalent carboxylic acid anhydride. , the storage stability of the resin composition is more excellent, and there exists a tendency which can suppress the fall of insulation reliability when it is set as a printed wiring board. Although this factor is not particularly limited, when a divalent carboxylic acid or a divalent carboxylic acid anhydride is used, compared with the case of using a monovalent carboxylic acid and a monovalent carboxylic acid anhydride, the amino-modified silicone (A ), when the carboxyl group of the divalent carboxylic acid or divalent carboxylic acid anhydride reacts with the amino group of .

Carboxylic acid (C) and carboxylic acid anhydride (D) may be used individually by 1 type, respectively, and may mix and use 2 or more types. Moreover, carboxylic acid (C) and carboxylic acid anhydride (D) may be used independently, respectively, and may use them together.

Moreover, in this embodiment, compared with using only carboxylic acid (C), it is preferable to use only carboxylic acid anhydride (D). Thereby, when the reactivity with an amino-modified silicone (A) is more excellent, there exists a tendency for storage stability to be more excellent.

In the reaction product (P) of the present embodiment, the content ratio of the carboxylic acid (C) and the carboxylic acid anhydride (D) to the amino-modified silicone (A) is not particularly limited, but on a mass basis, preferably They are 0.01 or more and 0.4 or less, More preferably, they are 0.01 or more and 0.2 or less, More preferably, they are 0.02 or more and 0.1 or less. When the content ratio is within the above range, the storage stability of the reaction product (P) tends to be more excellent.

In the resin composition of the present embodiment, the content of the carboxylic acid (C) and the carboxylic acid anhydride (D) is not particularly limited, but the total amount of the reaction product (P) (100% by mass; solvent/solvent component, filler ( J) is preferably 0.5 mass % or more and 20 mass % or less, more preferably 0.5 mass % or more and 10 mass % or less, further preferably 1.0 mass % or more and 5.0 mass % or more % or less. Moreover, when content of carboxylic acid (C) and carboxylic acid anhydride (D) combines reaction product (P) and thermosetting component (E), reaction product (P) and thermosetting component (E) with respect to the total amount of (100 mass %; solvent/solvent components, as solid content not containing filler (J)), preferably 0.05 mass % or more and 10 mass % or less, more preferably 0.1 mass % or more and 5.0 mass % % or less, and more preferably 0.2 mass% or more and 2.0 mass% or less. When content of a carboxylic acid (C) and a carboxylic acid anhydride (D) is in the said range, there exists a tendency for the printed wiring board more excellent in a moldability, the modulus of thermal elasticity, desmear resistance, and chemical-resistance to be obtained.

[thermosetting component (E)]

It is preferable that the resin composition of this embodiment further contains a thermosetting component (E).

The thermosetting component (E) used for this embodiment will not be specifically limited if it is a component hardened|cured by heat. Although it does not specifically limit as a thermosetting component (E), For example, in addition to the amino-modified silicone (A) and a maleimide compound (B) mentioned above, the epoxy resin (F) mentioned later, a cyanate ester compound (G) and alkenyl-substituted nadiimide (H). That is, the amino-modified silicone (A) and maleimide compound (B) used as the thermosetting component (E) may be the same as those of the above-described amino-modified silicone (A) and maleimide compound (B). . Among them, the thermosetting component (E) is one selected from the group consisting of a maleimide compound (B), an epoxy resin (F), a cyanate ester compound (G), and an alkenyl-substituted nadiimide (H), or It is preferable to contain 2 or more types, and it is more preferable to contain a maleimide compound (B).

In the resin composition of this embodiment, although content of a thermosetting component (E) is not specifically limited, When combining a reaction product (P) and a thermosetting component (E), a reaction product (P) and a thermosetting component With respect to the total amount of (E) (100 mass %; solvent/solvent components, as solid content not containing filler (J)), Preferably it is 20 mass % or more and 85 mass % or less, More preferably, it is 30 mass %. It is 85 mass % or more, More preferably, it is 40 mass % or more and 80 mass % or less. When content of a thermosetting component (E) is in the said range, also at the time of filler filling, it is excellent in a moldability, and there exists a tendency to become a printed wiring board excellent in thermal elastic modulus, desmear resistance, and chemical-resistance.

<Epoxy resin (F)>

When the resin composition of this embodiment contains an epoxy resin (F), there exists a tendency which is more excellent in adhesiveness, moisture absorption heat resistance, flexibility, etc. An epoxy resin (F) will not be specifically limited if it is a compound which has two or more epoxy groups in 1 molecule. Specific examples thereof include, for example, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A novolak epoxy resin, biphenyl epoxy resin, phenol furnace Volak type epoxy resin, cresol novolak type epoxy resin, xylene novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, naphthylene ether type epoxy resin, phenol are Alkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, triglycidyl cyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac Type epoxy resin, biphenyl novolak type epoxy resin, phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type epoxy resin, aralkyl novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin Epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, phosphorus containing epoxy resin, compound obtained by epoxidizing double bonds such as glycidylamine and butadiene, hydroxyl group containing silicone resin and epichlorhydrin compounds obtained by the above method, and halides thereof.

Among these, it is preferable that an epoxy resin (F) is 1 or more types chosen from the group which consists of a biphenyl aralkyl type epoxy resin, a naphthylene ether type epoxy resin, a polyfunctional phenol type epoxy resin, and a naphthalene type epoxy resin. By containing such an epoxy resin (F), there exists a tendency for the flame retardance and heat resistance of the hardened|cured material obtained to improve more.

An epoxy resin (F) may be used individually by 1 type, and may mix and use 2 or more types.

In the resin composition of the present embodiment, the content of the epoxy resin (F) is not particularly limited, but the total amount of the reaction product (P) and the thermosetting component (E) (100 mass%; solvent/solvent component, filler (J)) is preferably 1.0 mass% or more and 20 mass% or less, more preferably 1.0 mass% or more and 15 mass% or less, still more preferably 2.0 mass% or more and 10 mass% or less am. When content of an epoxy resin (F) exists in the said range, there exists a tendency which is more excellent in adhesiveness and flexibility.

<Cyanic acid ester compound (G)>

Although it does not specifically limit as cyanate ester compound (G) used for this embodiment, For example, a naphthol aralkyl type cyanate ester represented by the following general formula (3), and a novolak type represented by the following general formula (4) Cyanate ester, biphenyl aralkyl cyanate ester, bis(3,3-dimethyl-4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1, 4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-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.

Among these, the naphthol aralkyl-type cyanate ester compound represented by the following general formula (3), the novolac-type cyanate ester and the biphenyl aralkyl-type cyanate ester represented by the following general formula (4) are excellent in flame retardancy and have excellent curability. It is high, and it is preferable from the viewpoint of a low coefficient of thermal expansion of the cured product. The 1 type(s) or 2 or more types chosen are more preferable.

[Formula 5]

In Formula (3), some R< ₆ > represents a hydrogen atom or a methyl group, respectively independently, and n< ₂ > represents 1 or more integer.

In Formula (3), it is preferable that some R< ₆ > represents a hydrogen atom or a methyl group each independently, and, especially, represents a hydrogen atom.

In formula (3), n ₂ represents an integer of 1 or more. _The upper limit of n2 becomes like this. Preferably it is 10, More preferably, it is 6.

[Formula 6]

In formula (4), a plurality of R ₇ each independently represents a hydrogen atom or a methyl group, a plurality of R ₈ each independently represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 4 carbon atoms, and n ₃ is , represents an integer of 1 or more.

In Formula (4), some R< ₇ > represents a hydrogen atom or a methyl group each independently, and it is preferable to represent a hydrogen atom especially.

In Formula (4), some R< ₈ > represents a hydrogen atom, a C1-C4 alkyl group, or an alkenyl group each independently.

In formula (4), n ₃ represents an integer of 1 or more. The upper limit of n ₃ becomes like this. Preferably it is 10, More preferably, it is 7.

The manufacturing method of these cyanate ester compounds is not specifically limited, You may manufacture by any existing method as a cyanate ester synthesis method. Specifically, it can be obtained by reacting a naphthol aralkyl type phenol resin represented by the following general formula (5) with a cyan halide in an inert organic solvent in the presence of a basic compound. Moreover, the same naphthol aralkyl type phenol resin and the salt by a basic compound are formed in the solution containing water, and the method of performing a two-phase interface reaction with cyanogen halide after that, and synthesizing can also be taken.

[Formula 7]

In Formula (5), some R< ₆ > represents a hydrogen atom or a methyl group, respectively independently, and n< ₄ > represents 1 or more integer.

In Formula (5), some R< ₆ > represents a hydrogen atom or a methyl group each independently, and a hydrogen atom is especially preferable.

In formula (5), n ₄ represents an integer of 1 or more. The upper limit of n ₄ becomes like this. Preferably it is 10, More preferably, it is 6.

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

A cyanate ester compound (G) may be used individually by 1 type, and may mix and use 2 or more types.

In the resin composition of the present embodiment, the content of the cyanate ester compound (G) is not particularly limited, but the total amount of the reaction product (P) and the thermosetting component (E) (100% by mass; solvent/solvent component, filler ( J) is preferably 0.005 mass% or more and 5.0 mass% or less, more preferably 0.005 mass% or more and 3.0 mass% or less, still more preferably 0.1 mass% or more and 1.0 mass% or more % or less. When content of a cyanate ester compound (G) exists in the said range, there exists a tendency for the printed wiring board more excellent in moldability, thermal elastic modulus, desmear resistance, and chemical-resistance to be obtained.

<Alkenyl-substituted nadiimide (H)>

The alkenyl-substituted nadiimide (F) used for this embodiment will not be specifically limited if it is a compound which has one or more alkenyl-substituted nadiimide groups in a molecule|numerator. As the specific example, the compound represented by the following general formula (6) is mentioned, for example.

[Formula 8]

In formula (6), a plurality of R ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₂ is an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, or a naphthylene group. , or a group represented by the following general formula (7) or (8).

[Formula 9]

In Formula (7), R ₃ represents a substituent represented by a methylene group, an isopropylidene group, CO, O, S, or SO ₂ .

[Formula 10]

In Formula (8), some R< ₄ > represents a C1-C4 alkylene group or a C5-C8 cycloalkylene group each independently.

Moreover, a commercially available thing can also be used for the alkenyl-substituted nadiimide (F) represented by Formula (6). Although it does not specifically limit as what is marketed, For example, the compound represented by the following formula (9) (BANI-M (Maruzen Petrochemical Co., Ltd. product)), the compound represented by the following formula (10) (BANI-X) (Maruzen Petrochemical Co., Ltd. product)) etc. are mentioned.

Alkenyl-substituted nadiimide (H) may be used individually by 1 type, and may be used in mixture of 2 or more type.

[Formula 11]

[Formula 12]

The resin composition of this embodiment WHEREIN: Although content of alkenyl-substituted nadiimide (H) is not specifically limited, The total amount of reaction product (P) and thermosetting component (E) (100 mass %; solvent/solvent component, filler) (J) is preferably 5.0 mass% or more and 90 mass% or less, more preferably 10 mass% or more and 60 mass% or less, still more preferably 20 mass% or more and 40 mass% or less. When content of an alkenyl-substituted nadiimide (H) is in the said range, there exists a tendency for the printed wiring board more excellent in moldability, thermal elasticity modulus, desmear resistance, and chemical-resistance to be obtained.

You may use the above-mentioned epoxy resin (F), a cyanate ester compound (G), and an alkenyl-substituted nadiimide (H) as a raw material of a reaction product (P).

A thermosetting component (E) may be used individually by 1 type, and may mix and use 2 or more types.

Moreover, in the resin composition of this embodiment, in addition to the reaction product (P) and the thermosetting component (E), it is also possible to add other resin in the range which a desired characteristic is not impaired. Although it will not specifically limit if it has insulation about the kind of said other resin, For example, a thermoplastic resin is mentioned. By appropriately using a thermoplastic resin together, properties such as metal adhesion and stress relaxation properties can be imparted.

[Filling material (J)]

It is preferable that the resin composition of this embodiment further contains a filler (J). The filler (J) is not particularly limited as long as it has insulating properties, and for example, silicas such as natural silica, fused silica, amorphous silica, and hollow silica; alumina, aluminum nitride, boron nitride, boehmite, molybdenum oxide, Inorganic materials such as titanium oxide, zinc borate, zinc stannate, 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 and spherical glass Organic fillers, such as a filler, a silicone rubber, and silicone composite powder, are mentioned. These can be used 1 type or in mixture of 2 or more types suitably.

Among these, it is preferable that the filler (J) contains 1 type(s) or 2 or more types selected from the group which consists of silica from a viewpoint of low thermal expansion, alumina from a viewpoint of high thermal conductivity, and aluminum nitride.

Although content of the filler (J) in the resin composition of this embodiment is not specifically limited, When combining a reaction product (P) and a thermosetting component (E), the reaction product (P) and thermosetting component ( The total amount of the reaction product (P) in the case of using only the total amount of E) (100 parts by mass; as a solid content not containing the solvent/solvent component and the filler (J)) or the total amount of the reaction product (P) (100 parts by mass) ; The solvent/solvent component and the filler (J) are not contained in the solid content), containing 50 parts by mass or more and 300 parts by mass or less of the filler (J) from the viewpoint of characteristics such as low thermal expansion and high thermal conduction. Especially, it is more preferable that they are 100 mass parts or more and 300 mass parts or less, and it is still more preferable that they are 100 mass parts or more and 250 mass parts or less.

[Silane coupling agent, wetting and dispersing agent]

In the resin composition of this embodiment, in order to improve the dispersibility of the microparticles|fine-particles of a filler, and adhesive strength between resin and microparticles|fine-particles or a glass cloth, a silane coupling agent and/or a wetting and dispersing agent can also be used together. As these silane coupling agents, if it is a silane coupling agent generally used for surface treatment of an inorganic substance, it will not specifically limit. Specific examples include, for example, aminosilane systems such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane; γ-glycidoxypropyltrimethoxy Epoxy silanes such as silane; Acrylic silanes such as γ-acryloxypropyltrimethoxysilane; Cationic silanes such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride ; Phenylaryl silane-based silane coupling agents, such as styryl silane, are mentioned, It is also possible to use 1 type or in combination of 2 or more type suitably. Moreover, as a wetting and dispersing agent, if it is a dispersion stabilizer used for coating materials, it will not specifically limit. As a specific example, wetting and dispersing agents, such as DISPER-BYK 110, 111, 118, 180, 161, BYK-W996, W9010, W903, are mentioned by the brand name of Bikchemi Japan Co., Ltd. product, for example.

[curing accelerator]

In the resin composition of this embodiment, it is also possible to use a hardening accelerator together in the range in which an expected characteristic is not impaired. Although it does not specifically limit as a hardening accelerator, For example, Organic peroxides exemplified by benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate, etc.; azobis Azo compounds such as nitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N- tertiary amines such as methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; lead naphthenate; Organometallic salts such as lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; These organometallic salts are dissolved in a hydroxyl group-containing compound such as phenol and bisphenol and inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyl tin oxide and other organic tin compounds such as alkyl tin and alkyl tin oxide; and triphenylimidazole (TPIZ).

[organic solvent]

The resin composition of this embodiment may contain the solvent as needed. For example, when an organic solvent is used, the viscosity at the time of preparation of a resin composition becomes low, while handling property improves, the impregnation property to a glass cloth can be improved. The kind of solvent will not be specifically limited if a part or all of resin in a resin composition can be melt|dissolved. Although it does not specifically limit as the specific example, For example, Ketones, such as acetone, methyl ethyl ketone, methyl cellosolve; Aromatic hydrocarbons, such as toluene and xylene; Amides, such as dimethylformamide; Propylene glycol monomethyl ethers and their acetates. A solvent can be used 1 type or in combination of 2 or more type.

[Other ingredients]

In the resin composition of this embodiment, within the range in which the desired properties are not impaired, various high molecular compounds such as other thermosetting resins, thermoplastic resins and their oligomers and elastomers; other flame retardant compounds; combined use of additives, etc. is also possible These will not be specifically limited as long as they are generally used. For example, as a flame retardant compound, nitrogen-containing compounds, such as a melamine and benzoguanamine, and an oxazine ring containing compound are mentioned. As additives, ultraviolet absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, brighteners, polymerization inhibitors, etc. are used in appropriate combination as desired. It is also possible to

[Method for Producing Resin Composition]

The reaction product obtained by the manufacturing method of the resin composition of this embodiment by making an amino-modified silicone (A), a maleimide compound (B), and at least any one of carboxylic acid (C) or carboxylic anhydride (D) react (P) can be obtained as a resin composition as it is. Moreover, a resin composition can be obtained by mixing the obtained reaction product (P) and a thermosetting component (B). Moreover, you may mix other arbitrary components as needed.

Although the manufacturing method of the resin composition of this embodiment is not specifically limited, As a preferable aspect, the 1st reaction process (hereinafter simply " Also referred to as a first reaction step”) and a second reaction step in which the primary polymer and at least any of carboxylic acid (C) or carboxylic acid anhydride (D) are reacted (hereinafter also referred to simply as “second reaction step”) It is preferable from the viewpoint of obtaining more excellent storage stability of the reaction product (P).

Although it will not specifically limit if the reaction temperature in a 1st reaction process is the temperature which reaction of an amino-modified silicone (A) and a maleimide compound (B) advance, It is preferable that it is 50 degreeC - 200 degreeC, and it is 100 degreeC - 150 It is more preferable that it is °C.

The viscosity of the primary polymer obtained by the first reaction step to be subjected to the second reaction step is preferably 100 to 500 mPa·s from the viewpoint of obtaining more excellent storage stability of the reaction product (P), and 150 mPa It is more preferable that they are *s - 400 mPa*s. In addition, the measuring method of the viscosity of a primary polymer is not specifically limited, It can measure using a general viscometer. For example, it can measure using a cone plate type viscometer (eg, ICI viscometer).

Although the reaction temperature in a 2nd reaction process is not specifically limited, It is preferable that it is 50 degreeC - 200 degreeC, and it is more preferable that it is 100 degreeC - 150 degreeC. Although reaction time is not specifically limited, Preferably they are 0.5 hour - 5 hours, More preferably, they are 1.5 hours - 3.5 hours.

Naturally, even if the manufacturing method of the resin composition of this embodiment makes an amino-modified silicone (A), a maleimide compound (B), and at least any one of carboxylic acid (C) or carboxylic acid anhydride (D) react simultaneously, do. That is, you may implement a 1st reaction process and a 2nd reaction process simultaneously.

In the first step and the second step, at least any of the amino-modified silicone (A), the maleimide compound (B), the carboxylic acid (C) or the carboxylic acid anhydride (D), and the primary polymer are these It is preferable to dilute in a solvent in order to improve handling property. The kind of solvent is not particularly limited, For example, ketones such as acetone, methyl ethyl ketone, methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and its acetate. A solvent can be used 1 type or in combination of 2 or more type.

At the time of manufacture of the resin composition, a well-known process (stirring, mixing, kneading process, etc.) for dissolving or dispersing each component uniformly can be performed. Uniform dispersion of fillers, such as a filler (J), WHEREIN: The dispersibility with respect to a resin composition increases by performing a stirring dispersion process using the stirring tank which attached the stirrer which has suitable stirring ability. The above stirring, mixing, and kneading treatment can be appropriately carried out using, for example, an apparatus for the purpose of mixing such as a ball mill or a bead mill, or a known apparatus such as a revolving or autorotating mixing apparatus. .

[Prepreg]

The prepreg of this embodiment has a base material and the resin composition of this embodiment 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 said resin composition to a base material, the method of obtaining a prepreg is mentioned by heating in a 100-200 degreeC dryer for 1-30 minutes, or making it semi-hardened (B-staging). In addition, in this embodiment, although content of the said resin composition with respect to the total amount (100 mass %) of a prepreg (it contains a filler, an additive component) is not specifically limited, 30 mass % or more and 90 mass % or less range It is preferable to be

It does not specifically limit as a base material used for the prepreg of this embodiment, The well-known thing used for various printed wiring board materials can be selected suitably according to the intended use and performance, and can be used. Although it does not specifically limit as the specific example, For example, Glass fibers, such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, T glass; Inorganic fiber other than glass, such as quartz; Polypara phenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), copolyparaphenylene, 3,4'oxydiphenylene, terephthalamide (Technora (registered trademark), manufactured by Teijin Techno Products), etc. wholly aromatic polyamide; polyester such as 2,6-hydroxynaphthoic acid/parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kurare); polyparaphenylenebenzoxazole (Zylon (registered trademark); Organic fibers, such as Toyo Spinning Co., Ltd. product) and polyimide, are mentioned.

Among these, from the viewpoint of low thermal expansibility, one or two or more selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth and organic fibers are preferable.

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. .

The laminated board of this embodiment can be obtained by overlapping and hardening a plurality of the prepregs mentioned above, for example. Moreover, the metal foil clad laminated board of this embodiment can be obtained by laminating|stacking and hardening the prepreg and metal foil mentioned above, for example.

Specifically, the metal foil-clad laminate of the present embodiment can be obtained by, for example, stacking at least one or more of the above-mentioned prepregs, arranging metal foil on one side or both sides thereof, and laminating molding. More specifically, one or more of the above-mentioned prepregs are superimposed on top of each other, and a metal foil such as copper or aluminum is disposed on one or both sides as desired. A metal foil-clad laminate can be manufactured. 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 metal foil is not specifically limited, 1.0 micrometer or more and 70 micrometers or less are preferable, More preferably, they are 1.5 micrometers or more and 35 micrometers or less. The forming method of the metal foil-clad laminate and the forming conditions thereof are not particularly limited, and the methods and conditions for general printed wiring board laminates and multilayer boards 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 2.0-100 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 is also possible to set it as a multilayer board by combining and laminating|stacking the above-mentioned prepreg and the wiring board for inner layers manufactured separately.

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 this embodiment has a low coefficient of thermal expansion, good formability, metal foil peel strength and chemical resistance (especially desmear resistance), and can be particularly effectively used as a printed wiring board for semiconductor packages requiring such performance. can

Moreover, in this embodiment, other than the form of the prepreg mentioned above, it can also be set as the form of the embedding sheet of the form which apply|coated the above-mentioned resin composition to metal foil or a film.

[resin sheet]

The resin sheet of this embodiment has a support body and the resin composition of this embodiment arrange|positioned on the surface of this support body. It is the resin sheet which apply|coated the above-mentioned resin composition to the single side|surface or both surfaces of the support body. Here, the resin sheet is used as one means of thinning, and for example, a thermosetting resin (including a filler) used for a prepreg is directly applied to a support such as a metal foil or a film and dried, can be manufactured.

Although the support body used in manufacturing the resin sheet of this embodiment is not specifically limited, The well-known thing used for various printed wiring board materials can be used, It is preferable that they are a resin sheet or metal foil. Examples of the resin sheet and metal foil include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene ( PE) resin sheets, such as films, and metal foils, such as aluminum foil, copper foil, and gold foil, are mentioned. Among them, an electrolytic copper foil and a PET film are preferable.

After apply|coating the resin composition mentioned above to a support body, as for the resin sheet of this embodiment, it is preferable that it semi-hardened (B-staging). As for the manufacturing method of the resin sheet of this embodiment, the method of manufacturing the composite_body|complex of generally B-stage resin and a support body is preferable. Specifically, for example, after applying the resin composition to a support such as copper foil, semi-cured by a method of heating for 1 to 60 minutes in a dryer at 100 to 200° C., a method of manufacturing a resin sheet, etc. can be heard As for the adhesion amount of the resin composition with respect to a support body, the range of 1.0 micrometer or more and 300 micrometers or less is preferable with the resin thickness of a resin sheet.

The resin sheet of this embodiment can be used as a buildup material of a printed wiring board.

The laminated board of this embodiment can be obtained by overlapping and hardening|curing 1 or more sheets of the above-mentioned resin sheet, for example.

Moreover, the metal foil clad laminated board of this embodiment can be obtained by laminating|stacking and hardening the above-mentioned resin sheet and metal foil, for example.

The metal foil-clad laminated board of this embodiment can be obtained by laminating|stacking and forming metal foil on the single side|surface or both surfaces specifically, using the resin sheet mentioned above, for example. More specifically, for example, one resin sheet or a plurality of sheets of which the support has been peeled as desired are superimposed, and a metal foil such as copper or aluminum is disposed on one or both surfaces thereof, and this A metal foil-clad laminated board can be manufactured by lamination|stacking as needed. 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. The forming method of the metal foil-clad laminate and the forming conditions thereof are not particularly limited, and the methods and conditions for general printed wiring board laminates and multilayer boards 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, at the time of shaping|molding of a metal foil clad laminated board, the temperature is 100-300 degreeC, the pressure is 2.0-100 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.

The laminated board provided with two or more resin sheets and/or prepregs may be sufficient as the laminated board of this embodiment, and the metal foil clad laminated board provided with a resin sheet and/or a prepreg, and metal foil may be sufficient as it. These laminated boards are obtained by overlapping and hardening a resin sheet, a prepreg, and metal foil.

In this embodiment, when forming the conductor layer used as a circuit and producing a printed wiring board, when not taking the form of a metal foil clad laminated board, the method of electroless plating can also be used.

[printed wiring board]

The printed wiring board of this embodiment is equipped with the insulating layer containing the resin composition of this embodiment, and the conductor layer formed in the surface of the insulating layer.

The printed wiring board of this embodiment forms the conductor layer used as a circuit by metal foil or electroless plating in an insulating layer, for example, and is produced. The conductor layer is generally composed of copper or aluminum. The insulating layer for printed wiring boards with a conductor layer can be used suitably for a printed wiring board by forming a predetermined wiring pattern. And the printed wiring board of this embodiment suppresses the curvature of a semiconductor plastic package effectively by maintaining the outstanding elastic modulus also under the reflow temperature at the time of semiconductor mounting by an insulating layer containing the above-mentioned resin composition, and metal foil peeling strength and desmear resistance Since it is excellent in property, it can use especially effectively as a printed wiring board for semiconductor packages.

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 (copper-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 adhesive strength if necessary, and then the above-mentioned prepreg is superimposed on the surface of the inner circuit by a 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, the multilayer laminated board in which the insulating layer which consists of a base material and the hardened|cured material of a thermosetting resin composition was formed between the metal foil for inner-layer circuits and outer-layer circuits is manufactured. Next, after perforating for through-holes or via-holes to this multilayer laminated board, in order to remove the smear which is a residue of resin derived from the resin component contained in the hardened|cured material layer, a desmear process is performed. 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.

In the printed wiring board of this embodiment, for example, the above-mentioned prepreg (the base material and the above-mentioned resin composition affixed thereto), the above-mentioned resin sheet (the support body and the above-mentioned above-mentioned resin composition affixed thereto) Resin composition) and the resin composition layer (layer which consists of the above-mentioned resin composition) of a metal foil clad laminated board constitute the insulating layer containing the above-mentioned resin composition.

Example

Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples.

[Weight Average Molecular Weight]

The weight average molecular weight of the reaction product was measured by gel permeation chromatography (GPC) using the resin compositions obtained in the following Examples and Comparative Examples as samples, and was calculated as a value converted using a standard polystyrene calibration curve. Specifically, the relationship between the elution time from the column and the molecular weight is determined in advance, and the elution time is substituted for the molecular weight based on this. A graph showing the "relationship between dissolution time and molecular weight" used at this time is called a "calibration curve" (or calibration curve). Since the "relationship between elution time and molecular weight" differs for each type of polymer, in principle, it is necessary to use a standard polymer having the same structure as the measurement target and a known molecular weight distribution with a narrow molecular weight distribution. However, in practice, since it is difficult in most cases, a commercially available standard polymer is actually used. Here, polystyrene is used as a standard polymer. The molecular weight obtained in this way is called standard conversion molecular weight. From this, a weight average molecular weight (Mw) is computed from a following formula.

[Equation 1]

In the formula, N represents the number of polymer molecules, M represents molecular weight, and C represents sample concentration. Since the sample concentration C is proportional to the number of monomer units, C = M x N.

[Synthesis Example 1] Synthesis of α-naphthol aralkyl type cyanate ester resin

A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser is previously cooled to 0-5°C with brine, and there, 7.47 g (0.122 mol) of cyanogen chloride, 9.75 g (0.0935 mol) of 35% hydrochloric acid, and 76 ml of water and 44 ml of methylene chloride were injected.

α-naphthol aralkyl type phenol resin (SN485, OH group in which all R ₆ in Formula (5) represents a hydrogen atom under stirring while maintaining the temperature in this reactor at -5 to +5° C. and pH of 1 or less Equivalent: 214 g/eq. Softening point: 86° C., manufactured by Shin-Nitetsu Chemical Co., Ltd.) 20 g (0.0935 mol) and a solution obtained by dissolving 14.16 g (0.14 mol) of triethylamine in 92 ml of methylene chloride with a dropping funnel It was dripped over 1 hour, and triethylamine 4.72g (0.047mol) was further dripped after completion|finish of dripping over 15 minutes.

[Formula 13]

n ₄ represents an integer of 1 or more.

After completion of the dropwise addition, after stirring at the same temperature for 15 minutes, the reaction liquid was separated and the organic layer was separated. The obtained organic layer was washed twice with 100 ml of water, then methylene chloride was distilled off under reduced pressure with an evaporator, and finally concentrated to dryness at 80°C for 1 hour, and cyanate ester of α-naphthol aralkyl phenol resin 23.5 g of a product (α-naphthol aralkyl type cyanate ester resin) was obtained.

[Example 1]

25 parts by mass of a maleimide compound (maleimide group equivalent 285 g/eq, trade name "BMI-80" manufactured by K-I Chemicals Co., Ltd.) 40 parts by mass of propylene glycol monomethyl ether (manufactured by KH Neochem) at a heating and reflux temperature of 130°C In a solution dissolved under the conditions of was prepared. Then, stirring is continued under the conditions of 130 degreeC of heating reflux temperature, and when the viscosity of a primary polymer increases to 200-300 mPa*s with an ICI viscometer (cone plate type viscometer, Towa Kogyo Co., Ltd. make), the primary polymer To this was added a solution obtained by dissolving 1.0 parts by mass of maleic anhydride (manufactured by Tokyo Chemical Company) in 22.5 parts by mass of propylene glycol monoethyl ether acetate (manufactured by Dow Chemical Corporation), followed by reaction for several hours under the condition of a heating and reflux temperature of 130°C. Thus, a resin composition containing a reaction product was obtained. Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. Moreover, a part of the resin composition was preserve|saved on 25 degreeC conditions for 7 days, and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Example 2]

The resin composition containing the reaction product whose weight average molecular weight is 13200 was obtained by the method similar to Example 1 except having changed 1.0 mass part of maleic anhydride into 1.0 mass part of acetic anhydride (made by Tokyo Chemical Industry Co., Ltd.). Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. Moreover, a part of the resin composition was preserve|saved on 25 degreeC conditions for 7 days, and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Example 3]

A resin composition containing a reaction product having a weight average molecular weight of 12500 was obtained in the same manner as in Example 1 except that 1.0 parts by mass of maleic anhydride was changed to 1.0 parts by mass of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. Moreover, a part of the resin composition was preserve|saved on 25 degreeC conditions for 7 days, and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Example 4]

The resin composition containing the reaction product whose weight average molecular weight is 12000 was obtained by the method similar to Example 1 except having changed 1.0 mass part of maleic anhydride into 1.0 mass parts of maleic acid (made by Tokyo Chemical Industry Co., Ltd.). Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. Moreover, a part of the resin composition was preserve|saved on 25 degreeC conditions for 7 days, and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Example 5]

The resin composition containing the reaction product whose weight average molecular weight is 11710 was obtained by the method similar to Example 1 except having changed 1.0 mass part of maleic anhydride into 0.5 mass parts of maleic anhydride. Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. Moreover, a part of the resin composition was preserve|saved on 25 degreeC conditions for 7 days, and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Comparative Example 1]

The resin composition containing the reaction product whose weight average molecular weight is 13900 was obtained by the method similar to Example 1 except not having used 1.0 mass part of maleic anhydride and 22.5 mass parts of propylene glycol monoethyl ether acetate. Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. Moreover, a part of the resin composition was preserve|saved on 25 degreeC conditions for 7 days, and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Comparative Example 2]

The resin composition containing the reaction product whose weight average molecular weight is 14100 was obtained by the method similar to Example 1 except having not used 1.0 mass part of maleic anhydride. Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. Moreover, a part of the resin composition was preserve|saved on 25 degreeC conditions for 7 days, and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

In Table 1, "increase rate" is the ratio (%) of the weight average molecular weight of the resin composition after 7-day storage with respect to the weight average molecular weight of the resin composition before storage. In addition, the "weight average molecular weight" of the resin composition before storage was not the value obtained by measuring immediately after obtaining each resin composition, but the value obtained by measuring on the day when each resin composition was obtained. Therefore, about the storage stability of an initial stage, it can compare from the result of "weight average molecular weight" in Table 1.

[Example 6]

41.0 parts by mass of the resin composition obtained in Example 1, 30 parts by mass of a maleimide compound (maleimide group equivalent: 186 g/eq, trade name "BMI-2300" manufactured by Owa Chemical Industry Co., Ltd.), and a biphenyl novolac-type epoxy resin (Brand name "NC-3000FH" manufactured by Nippon Kayaku Co., Ltd.) 4.5 parts by mass, and 25 parts by mass of bisdialylnadiimide (alkenyl group equivalent: 286 g/eq, trade name "BANI-M" manufactured by Maruzen Petrochemical Corporation); 0.5 parts by mass of the cyanate ester of the α-naphthol aralkyl type phenol resin obtained in Synthesis Example 1, 200 parts by mass of slurry silica (trade name "SC-2050MB" manufactured by Adomatex Co., Ltd.), and an epoxysilane coupling agent ( 5 mass parts of Toray Dow Coatings brand name "Z6040") and 0.5 mass parts of triphenylimidazole (Tokyo Chemical Industry Co., Ltd. make) of a hardening accelerator were mixed, and the resin composition was obtained.

[Comparative Example 3]

A resin composition was obtained in the same manner as in Example 6 except that 41.0 parts by mass of the resin composition obtained in Example 1 was changed to 40.0 parts by mass of the resin composition obtained in Comparative Example 2.

[Aminga]

About each resin composition obtained in Example 6 and Comparative Example 3, the amine value was measured. Specifically, based on JISK7237:1995, the amine value was measured as the total amount of the primary amine and secondary amine of a resin composition. The results are shown in Table 2.

[Production of prepreg]

The varnish was obtained by diluting each resin composition obtained in Example 6 and Comparative Example 3 with methyl ethyl ketone. This varnish is impregnated with T glass cloth (T2118), dried by heating at 150 ° C. for 3 minutes, and the thickness of the insulating layer is 100 µm when the following laminate is obtained. The content (mass%) of the resin composition is adjusted, got a prepreg.

[Varnish Gel Time]

The gel time (seconds) in 170 degreeC was measured as a sample for a part of each varnish obtained at the time of manufacture of the above-mentioned prepreg. Moreover, a part of the varnish was preserve|saved on 25 degreeC conditions for 7 days, and the gel time (sec) after storage was measured similarly to the above. The results are shown in Table 2.

[Prepreg Viscosity]

A resin component was obtained from the prepreg manufactured by the method described above, and using a dynamic viscoelasticity measuring apparatus (trade name "AR2000" manufactured by TAA Instruments), the angular velocity was 1 rad/s and the geometrical gap was 1 mm. The viscosity (mPa·s) under the measurement conditions of 120°C was measured. Moreover, the prepreg mentioned above was stored on 25 degreeC conditions for 7 days, the resin content was acquired from the prepreg after storage, and the shear viscosity (mPa*s) was measured similarly to the above. The results are shown in Table 2.

[Laminate]

Electrolytic copper foil with a thickness of 12 µm (trade name "3EC-III" manufactured by Mitsui Metals Mining Co., Ltd.) is placed above and below the obtained prepreg sheet, and lamination molding is performed at a pressure of 30 kgf/cm 2 and a temperature of 220° C. for 120 minutes. Thus, a copper-clad laminate (molding before storage) having an insulating layer thickness of 100 µm was obtained. In addition, the obtained prepreg was stored for 7 days under the conditions of 25°C, laminated molding was performed in the same manner as above using one prepreg after storage, and a copper clad laminate with an insulating layer thickness of 100 µm (after storage) molding) was obtained.

[Coefficient of Thermal Expansion]

After removing the copper foil by performing full etching of each obtained copper-clad laminate (molding before storage and molding after storage), using a thermomechanical analyzer (manufactured by TA Instruments), the temperature was raised from 40°C to 340°C at 10°C per minute, , the coefficient of linear expansion in the plane direction from 60°C to 120°C was measured, and the obtained value was made into the evaluation value of the coefficient of thermal expansion (ppm/degC). As for the measurement direction, the longitudinal direction (Warp) of the glass cloth of the laminate was measured. The results are shown in Table 3.

This application is a Japanese Patent Application filed with the Japan Patent Office on April 5, 2016 (Japanese Patent Application No. 2016-076144), and a Japanese Patent Application filed with the Japan Patent Office on January 5, 2017 (Japanese Patent Application 2017) -000666), the contents of which are incorporated herein by reference.

Industrial Applicability

The resin composition of the present invention and a printed wiring board obtained from the resin composition can be suitably used as members of various electronic devices and communication devices including personal computers.

Claims (20)

A primary polymer obtained by reacting an amino-modified silicone (A) with a maleimide compound (B);
A resin composition comprising a reaction product (P) obtained by reacting at least any of carboxylic acid (C) or carboxylic acid anhydride (D), comprising:
The amine value of the resin composition is 2.0 mgKOH/g or less, the resin composition. delete The method of claim 1,
The reaction product (P) is obtained by reacting at least the carboxylic acid anhydride (D),
The said carboxylic acid anhydride (D) is 1 type(s) or 2 or more types chosen from the group which consists of maleic anhydride, phthalic anhydride, succinic anhydride, and acetic anhydride, The resin composition. The method of claim 1,
The reaction product (P) is obtained by reacting at least the carboxylic acid (C),
The said carboxylic acid (C) is 1 type(s) or 2 or more types selected from the group which consists of maleic acid, phthalic acid, succinic acid, and acetic acid, The resin composition. The method of claim 1,
The resin composition which further contains a thermosetting component (E). 6. The method of claim 5,
The said thermosetting component (E) is 1 type or 2 types selected from the group which consists of a maleimide compound (B), an epoxy resin (F), a cyanate ester compound (G), and an alkenyl-substituted nadiimide (H). The resin composition containing the above. The method of claim 1,
The resin composition wherein the amino-modified silicone (A) in the reaction product (P) contains a compound represented by the following general formula (1).
[Formula 1]

(in formula (1), a plurality of R _a each independently represents a hydrogen atom, a methyl group or a phenyl group, a plurality of R _b each independently represents a single bond, an alkylene group or an aryl group, and n is an integer of 1 or more represents) The method of claim 1,
The amino group equivalent of the said amino-modified silicone (A) in the said reaction product (P) is 130 or more and 6000 or less, The resin composition. The method of claim 1,
The maleimide compound (B) is bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl- A resin containing one or two or more selected from the group consisting of 4-maleimidephenyl)methane, polytetramethyleneoxide-bis(4-maleimidebenzoate), and a compound represented by the following general formula (2) composition.
[Formula 2]

(in formula (2), a plurality of R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more) The method of claim 1,
The resin composition which further contains a filler (J). 11. The method of claim 10,
The said filler (J) contains the 1 type(s) or 2 or more types chosen from the group which consists of silica, an alumina, and aluminum nitride, The resin composition. 11. The method of claim 10,
The said resin composition contains 50 mass parts or more and 300 mass parts or less of the said filler (J) with respect to 100 mass parts of total amounts of the said reaction product (P) and a thermosetting component (E). A prepreg comprising a substrate and the resin composition according to any one of claims 1 to 13 impregnated or applied to the substrate. 14. The method of claim 13,
A prepreg, wherein the base material is one or more selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth and organic fiber. The resin sheet which has a support body and the resin composition in any one of Claims 1, 3-12 arrange|positioned on the surface of this support body. 16. The method of claim 15,
The support is a resin sheet or metal foil, a resin sheet. A prepreg having the resin composition according to any one of claims 1 and 3 to 12 impregnated or applied to the substrate, the prepreg, and the support, and claim 1 disposed on the surface of the support; The laminated board provided with 1 type(s) or 2 or more types chosen from the group which consists of a resin sheet which has the resin composition in any one of Claims 3-12 in multiple numbers. A prepreg having the resin composition according to any one of claims 1 and 3 to 12 impregnated or applied to the substrate, the prepreg, and the support, and claim 1 disposed on the surface of the support; The metal foil-clad laminated board provided with 1 type(s) or 2 or more types chosen from the group which consists of a resin sheet which has the resin composition in any one of Claims 3-12, and metal foil. A printed wiring board provided with the insulating layer containing the resin composition in any one of Claims 1-12, and the conductor layer formed in the surface of this insulating layer. A first reaction step of reacting an amino-modified silicone (A) with a maleimide compound (B) to obtain a primary polymer;
A method for producing a resin composition comprising a second reaction step of reacting the primary polymer with at least any one of carboxylic acid (C) or carboxylic acid anhydride (D),
The amine value of the said resin composition is 2.0 mgKOH/g or less, The manufacturing method of the resin composition.