TW201807063A - Resin composition and method for producing same, prepreg, resin sheet, laminate, metal foil-clad laminate and printed wiring board - Google Patents

Abstract

The present invention provides a resin composition containing a reaction product (P) obtained by reacting an amino-modified silicone (A), a maleimide compound (B), and one or more compounds selected from the group consisting of carboxylic acids (C) and carboxylic acid anhydrides (D).

Description

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

The present invention relates to a resin composition and a manufacturing method thereof, a prepreg, a resin sheet, a laminated board, a metal foil-clad laminated board, and a printed circuit board.

In recent years, with the advancement of high-performance and miniaturization of semiconductor packages widely used in electronic equipment, communication equipment, personal computers, and the like, the high integration and high-density mounting of various components used in semiconductor packages has been accelerating in recent years. Among them, the warpage of the semiconductor plastic package caused by the difference in thermal expansion coefficient between the semiconductor element and the printed circuit board for the semiconductor plastic package becomes a problem, and various countermeasures have been proposed.

One of the countermeasures is to reduce the thermal expansion of the insulating layer used in the printed wiring board. This is a method of suppressing warpage by making the thermal expansion coefficient of a printed circuit board close to the thermal expansion coefficient of a semiconductor element, and has been actively adopted (for example, refer to Patent Documents 1 to 3).

As a method for suppressing the warpage of semiconductor plastic packages, in addition to the low thermal expansion of printed circuit boards, there have also been discussions to increase the rigidity (high rigidity) of the laminated board and increase the glass transition temperature (higher Tg) of the laminated board. (See, for example, Patent Documents 4 and 5). [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. 2013-216884 Patent Document 2: Japanese Patent Application Publication No. 3173332 Patent Document 3: Japanese Patent Application Publication No. 2009-035728 Patent Document 4: Japanese Patent Application Publication No. 2013-001807 Patent Document 5: Japanese Patent Laid-Open No. 2011-178992

(Problems to be Solved by the Invention) However, even if a printed wiring board using a thermosetting resin composition is described in Patent Documents 1 to 5, it is still difficult to take into consideration the peeling strength of a laminated board in which metal foils are laminated, or for example The alkali cleaning solution has chemical resistance (residue removal resistance) and other characteristics, and as a result, the problem of warping of the semiconductor plastic package remains.

Here, in order to reduce the above-mentioned difference in thermal expansion rate and to solve the above-mentioned problem of warpage, the resin composition may be formed by reacting, for example, an amine-modified polysiloxane as a low elastic component with a thermosetting component. Amine modified polymer. However, polymers modified with amine groups generally have the property that the polymers further polymerize with each other or with other resin components. Therefore, during storage or molding of the resin composition and the prepreg, excellent storage stability may not be obtained due to further polymerization reaction of the polymer modified with the amine group.

An object of the present invention is to provide a resin composition containing an amine-modified polymer but having excellent storage stability in order to solve the above-mentioned problems.

That is, the present invention is as follows. [1] A resin composition comprising a reaction product (P), the reaction product (P) being an amino-modified polysiloxane (A), a maleimide compound (B), and a carboxylic acid (C) It is obtained by reacting at least one of 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 resin composition according to [1] or [2], wherein the reaction product (P) is obtained by reacting at least the carboxylic acid anhydride (D), and the carboxylic acid anhydride (D) is selected from the group consisting of Malay One or more of the group consisting of acid anhydride, phthalic anhydride, succinic anhydride, and acetic anhydride. [4] The resin composition according to any one of [1] to [3], wherein the reaction product (P) is obtained by reacting at least the carboxylic acid (C), and the carboxylic acid (C) is selected from One or two or more of 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 containing a thermosetting component (E). [6] The resin composition according to [5], wherein the thermosetting component (E) contains a material selected from the group consisting of a maleimide compound (B), an epoxy resin (F), and a cyanate ester compound (G ), And one or two or more of the group consisting of aldiyl-substituted nadiimide (H). [7] The resin composition according to any one of [1] to [6], wherein the amine-modified polysiloxane (A) in the reaction product (P) contains one represented by the following general formula (1) Compound In the formula (1), a plurality of R _a each independently represent a hydrogen atom, a methyl group, or a phenyl group, a plurality of R _b each independently represent a single bond, an alkylene group, or an aryl group, and n represents an integer of 1 or more. [8] The resin composition according to any one of [1] to [7], wherein the amine group equivalent of the amine-modified polysiloxane (A) in the reaction product (P) is 130 or more and 6000 or less . [9] The resin composition according to any one of [1] to [8], wherein the maleimide compound (B) contains a compound selected from bis (4-maleimidephenyl) methane , 2,2-bispyridine 4- (4-maleimidoiminophenoxy) -phenylpyridinepropane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane One or two or more of the group consisting of polycyclobutane oxide-bis (4-maleimide iminobenzoate), and a compound represented by the following general formula (2); In the formula (2), a plurality of R ₅ each independently represent 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 containing a filler (J). [11] The resin composition according to [10], wherein the filler (J) contains one or two or more members selected from the group consisting of silicon dioxide, aluminum oxide, and aluminum nitride. [12] The resin composition according to [10] or [11], wherein the resin composition contains 50 parts by mass based on 100 parts by mass of the total amount of the reaction product (P) and the thermosetting component (E). The filler (J) is at least 300 parts by mass. [13] A prepreg comprising: a substrate; and the resin composition according to any one of [1] to [12] impregnated or coated on the substrate. [14] The prepreg according to [13], wherein the substrate is one or two selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers the above. [15] A resin sheet comprising: a support; and the resin composition according to any one of [1] to [12] arranged on a surface of the support. [16] The resin sheet according to [15], wherein the support is a resin sheet or a metal foil. [17] A laminated board having one or two selected from the group consisting of a prepreg such as [13] or [14] and a resin sheet such as [15] or [16] the above. [18] A metal foil-clad laminate having one selected from the group consisting of a prepreg such as [13] or [14], and a resin sheet such as [15] or [16], or More than two kinds; and metal foil. [19] A printed circuit board having: an insulating layer containing the resin composition according to any one of [1] to [12]; and a conductor layer formed on a surface of the insulating layer. [20] A method for producing a resin composition, comprising: a first reaction step of reacting an amine-modified polysiloxane (A) with a maleimide compound (B) to obtain a primary polymer; and a second reaction A step of reacting the primary polymer and the carboxylic acid (C) with at least one of the carboxylic acid anhydride (D).

Hereinafter, this embodiment (hereinafter referred to as "this embodiment") will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist thereof.

[Resin composition] The resin composition of this embodiment includes at least one of amine-modified polysiloxane (A), maleimide compound (B), and carboxylic acid (C) and carboxylic anhydride (D). The reaction product (P) (prepolymer) obtained by one reaction. Here, the reaction product (P) is one of the aforementioned amine-modified polymers.

The resin composition of this embodiment has excellent storage stability. The reason is speculated as follows (but the reason is not limited to this). A conventional resin composition containing an amine-modified polysiloxane and a thermosetting component, because the reactive amine of the amine-modified polysiloxane used as a raw material in the amine-modified polymer contained in the resin composition A large amount of residues remain in the structure of the prepolymer. This amine group will further react with the thermosetting component, resulting in the resin composition (containing varnish) and the shaped body (for example, prepreg) obtained from the resin composition. And its formed body) cannot obtain excellent storage stability. For example, when the resin composition is stored at normal temperature, the residual amine group and the thermosetting component further react with each other, which results in an increase in the viscosity and molecular weight of the resin composition, and it is impossible to obtain excellent storage stability. In addition, in the case of varnish, gelation is caused, and in the case of prepreg, the moldability is not good due to the increase in the viscosity of the prepreg, and excellent storage stability cannot be obtained. On the other hand, the resin composition of this embodiment contains an amine group and a carboxylic acid (C) remaining in the reaction between the amine group-modified polysiloxane (A) and the maleimide compound (B) and / Or the reaction product (P) obtained by reacting the carboxylic acid anhydride (D) can make the resin composition and the molded body obtained from the resin composition obtain excellent storage stability.

The amine value of a resin composition is an amine value with respect to the total amount of a primary amine and a secondary amine. The amine value is not particularly limited, but is preferably 2.0 mgKOH / g or less, more preferably 1.0 mgKOH / g or less, and even more preferably 0.5 mgKOH / g or less. When the amine value is 2.0 mgKOH / g or less, there is a tendency that the increase in viscosity of the resin composition, increase in molecular weight, gelation of varnish, and increase in viscosity of the prepreg tend to be suppressed. In addition, the smaller the amine value, the more the viscosity of the resin composition and the increase in molecular weight can be suppressed. The lower limit of the amine value is preferably 0 mgKOH / g. The amine value can be measured in accordance with the method in accordance with JIS K 7237: 1995.

[Reaction product (P)] The reaction product (P) of this embodiment is an amino-modified polysiloxane (A), a maleimide compound (B), a carboxylic acid (C), and a carboxylic acid anhydride (D ).

The reaction product (P) may be used singly or in combination of two or more kinds.

The weight average molecular weight (Mw) of the reaction product (P) is not particularly limited, but is preferably 5,000 or more and 20,000 or less, and more preferably 10,000 or more and 15,000 or less. When the weight average molecular weight is from 5000 or more, the thermal expansion coefficient of the prepreg tends to decrease. When the weight average molecular weight is 20,000 or less, it can suppress the increase in viscosity of the resin composition, increase in molecular weight, gelation of varnish, and prepreg. Increasing tendency of body viscosity. In order to obtain a reaction product (P) having a weight average molecular weight of 5,000 to 20,000, the reaction conditions such as temperature may be controlled. The weight average molecular weight is measured by a gel permeation chromatography (GPC) method, and is calculated | required by the standard polystyrene calibration curve in the form of 値. Specifically, it can measure by the method as described in the Example mentioned later.

The content of the reaction product (P) in the resin composition of this embodiment is not particularly limited. When combined with the thermosetting component (E), it is relative to the reaction product (P) and the thermosetting component in the resin composition. The total amount of (E) (100% by mass; the solid content of the solvent and solvent components and filler (J) is not included), preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass 70% by mass or more, 20% by mass or more and 60% by mass or less. When the content of the reaction product (P) is within the above range, it can be used as a printed circuit board with excellent moldability, low thermal expansion coefficient, thermoelastic modulus, slag resistance, and chemical resistance when filled with a filler. tendency.

<Amine-modified polysiloxane (A)> The amine-modified polysiloxane (A) used in this embodiment is not particularly limited as long as it is a polysiloxane having one or more amine groups in the molecule. It is preferable to contain a compound represented by the following general formula (1). [Chemical 3] In the formula (1), a plurality of R _a each independently represent a hydrogen atom, a methyl group, or a phenyl group, with a methyl group being preferred. The plurality of R _b each independently represent a single bond, an alkylene group or an aryl group, with alkylene groups being preferred. The carbon number of the alkylene group is preferably 1 to 4 in its main chain. The specific alkylene group is not particularly limited, and it is more preferably methylene, ethylene, trimethylene, or tetramethylene, and trimethylene is more preferable. In Formula (1), n represents an integer of 1 or more.

The amine-modified polysiloxane (A) may be used singly or in combination of two or more kinds.

The amine group equivalent of the amine-modified polysiloxane (A) is not particularly limited, but is preferably 130 or more and 6000 or less, more preferably 500 or more and 3000 or less, and even more preferably 600 or more and 2500 or less. When the amine group equivalent of the amine-modified polysiloxane (A) is within the above range, a printed circuit board with better peeling strength of metal foil and resistance to slag removal can be obtained. The amine group equivalent can be measured in accordance with the method in accordance with JIS K 7237: 1995.

In the resin composition of this embodiment, the content of the amine-modified polysiloxane (A) is not particularly limited, and it is relative to the total amount (100% by mass) of the reaction product (P) in the resin composition; The solvent component and the solid content of the filler (J) are preferably 5.0% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 50% by mass or less, and more preferably 15% by mass or more and 45% by mass or less. . In addition, when the content of the amine-modified polysiloxane (A) is combined with the reaction product (P) and the thermosetting component (E), the amine-modified polysiloxane used in the production of the reaction product (P) is used. The total amount of oxygen (A) and the amine-modified polysiloxane (A) contained as the thermosetting component (E) is relative to the reaction product (P) and the thermosetting component (E) in the resin composition. ) (100% by mass; solid content excluding solvents and solvent components), preferably 1.0% by mass or more and 70% by mass or less, more preferably 3.0% by mass or more and 40% by mass or less It is 5.0 mass% or more and 20 mass% or less. In addition, when the content of the amine-modified polysiloxane (A) is within the above range, a printed circuit board having more excellent metal foil peeling strength and resistance to slag removal can be obtained. In addition, the content of the amine-modified polysiloxane (A) referred to herein includes, in addition to the production of the reaction product (P), the use of the amine-modified polysiloxane (A), as well as a thermosetting component described later ( E) Amine-modified polysiloxane (A).

<Maleimide compound (B)> The maleimide compound (B) used in this embodiment is not limited as long as it is a compound having one or more maleimide groups in one molecule. . Specific examples thereof include, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, 2,2-bisamidine4- ( 4-maleimide phenoxy) -phenylamidine propane, bis (3,5-dimethyl-4-maleimide phenyl) methane, bis (3-ethyl-5-methyl -4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, polycyclobutane oxide-bis (4-maleimide Amine benzoate), maleimide compounds represented by the following general formula (2), prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. One of them may be used or two or more of them may be appropriately mixed and used.

Among them, the maleimide compound (B) preferably contains a compound selected from the group consisting of bis (4-maleimidephenyl) methane and 2,2-bisamidine 4- (4-maleimideimidephenoxy). ) -Phenylphosphonium propane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, polycyclobutane oxide-bis (4-maleimide iminobenzoic acid) Esters), and one or two or more of the group consisting of maleimide compounds represented by the following general formula (2), and preferably contains 2,2-bisfluorene 4- (4-maleimide benzene Oxy) -phenylphosphonium propane is more preferred.

[Chemical 4] In the formula (2), a plurality of R ₅ each independently represent a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.

In the formula (2), a plurality of R ₅ each independently represent a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferred.

In formula (2), n ₁ represents an integer of 1 or more. The upper limit 値 of n ₁ is preferably 10, and more preferably 7.

The maleimidine compound (B) may be used alone or in combination of two or more.

In the reaction product (P) of this embodiment, the content ratio of the maleimidine imine compound (B) to the amine-modified polysiloxane (A) is not particularly limited, and it is preferably 1.0 or more and 3.0 or less on a mass basis. , More preferably 1.0 or more and 2.5 or less, and even more preferably 1.0 or more and 2.0 or less. When the content is within the above range, the reaction product (P) tends to be more excellent in manufacturability.

The content of the maleimidine imine compound (B) in the resin composition of this embodiment is not particularly limited, and it does not include a solvent or a solvent with respect to the total amount (100% by mass) of the reaction product (P) in the resin composition. In terms of the solid content of the components and filler (J)), it is preferably 10% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 80% by mass or less, and more preferably 45% by mass or more and 75% by mass or less. . In addition, when the content of the maleimide imine compound (B) is a combination of the reaction product (P) and the thermosetting component (E), the maleimide imine compound is used in the production of the reaction product (P). The total amount of (B) and the maleimide compound (B) contained as the thermosetting component (E) is relative to the total amount of the reaction product (P) and the thermosetting component (E) (100). % By mass; in terms of solid content of the solvent, solvent component and filler (J)), preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less It is 30% by mass or more and 70% by mass or less. When the content of the maleimide compound (B) is within the above range, there is a tendency that a printed circuit board having more excellent moldability, thermoelastic modulus, scum resistance, and chemical resistance can be obtained. In addition, the content of the maleimide imine compound (B) referred to herein includes the maleimide compound (B) used as the reaction product (P), as well as the thermosetting component (E) described later. Maleimide compound (B).

<Carboxylic acid (C), carboxylic anhydride (D)> The carboxylic acid (C) used in this embodiment is not particularly limited, and is preferably selected from the group consisting of maleic acid, phthalic acid, succinic acid, acetic acid, and propionic acid One or two or more of the groups are preferable, and one or two or more of them are more preferably selected from the group consisting of maleic acid, phthalic acid, succinic acid, and acetic acid, and are selected from the group consisting of maleic acid, One or more of phthalic acid and succinic acid are more preferred. In addition, the carboxylic acid anhydride (D) used in this embodiment is not particularly limited, but is preferably selected from one or two or more selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, acetic anhydride, and propionic anhydride. Preferably, one or two or more selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, and acetic anhydride, and more preferably selected from maleic anhydride, phthalic anhydride, and One or more of succinic anhydride.

The carboxylic acid (C) and the carboxylic acid anhydride (D) are preferably the monocarboxylic acid and the monocarboxylic acid anhydride, or the dicarboxylic acid and the dicarboxylic acid anhydride, respectively, and the dicarboxylic acid and the dicarboxylic acid anhydride are more preferable. good. The carboxylic acids (C) and carboxylic anhydrides (D) are dicarboxylic acids and dicarboxylic anhydrides, respectively. Compared with monocarboxylic acids and monocarboxylic anhydrides, the resin composition has better storage stability, and, There is a tendency to suppress a decrease in insulation reliability when the printed circuit board is manufactured. The reason is not particularly limited, and it is presumed that if a dicarboxylic acid or a dicarboxylic anhydride is used, the amino group and the diamine of the amino-modified polysiloxane (A) are compared with the monocarboxylic acid and the monocarboxylic acid anhydride. When a carboxyl group of a carboxylic acid or a dicarboxylic anhydride reacts with a carboxyl group that has reacted with a carboxyl group, it is difficult to remain in the resin composition as a free carboxylic acid.

The carboxylic acid (C) and the carboxylic anhydride (D) may be used singly or in combination of two or more kinds. The carboxylic acid (C) and the carboxylic anhydride (D) may be used alone or in combination.

Moreover, in this embodiment, it is preferable to use only a carboxylic acid anhydride (D) rather than using only a carboxylic acid (C). Thereby, the reactivity with amine-modified polysiloxane (A) is more excellent, and storage stability tends to be more excellent.

In the reaction product (P) of this embodiment, the content ratio of the carboxylic acid (C) and the carboxylic anhydride (D) to the amine-modified polysiloxane (A) is not particularly limited, and it is preferably 0.01 or more on a mass basis 0.4 or less, more preferably 0.01 or more and 0.2 or less, and even more preferably 0.02 or more and 0.1 or less. The content tends to be more excellent than the storage stability of the reaction product (P) within the above range.

In the resin composition of this embodiment, the content of the carboxylic acid (C) and the carboxylic anhydride (D) is not particularly limited, and it is relative to the total amount of the reaction product (P) (100% by mass; it does not include solvents, solvent components, and filler The solid content of the material (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, and more preferably 1.0 mass% or more and 5.0 mass% or less. When the content of the carboxylic acid (C) and the carboxylic anhydride (D) is a combination of the reaction product (P) and the thermosetting component (E), the content of the reaction product (P) and the thermosetting component (E) The total amount (100% by mass; the solid content of the solvent / solvent component and the filler (J) is not included) is preferably 0.05% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 5.0% by mass or less. , More preferably 0.2 mass% or more and 2.0 mass% or less. When the content of the carboxylic acid (C) and the carboxylic anhydride (D) is within the above range, there is a tendency that a printed circuit board having more excellent moldability, thermoelastic modulus, scum resistance, and chemical resistance can 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 in this embodiment is not particularly limited as long as it is a component that hardens due to heat. The thermosetting component (E) is not particularly limited, and examples thereof include the above-mentioned amine-modified polysiloxane (A) and maleimide compound (B), and further include epoxy resin (F) and cyanate described later. Compound (G), and nadiimide (H) substituted with alkenyl. That is, the amine-modified polysiloxane (A) and maleimide compound (B) used as the thermosetting component (E) can be used in combination with the above-mentioned amine-modified polysiloxane (A), It is the same as maleimide compound (B). Among them, the thermosetting component (E) preferably contains a material selected from the group consisting of a maleimide compound (B), an epoxy resin (F), a cyanate compound (G), and an alkenyl-substituted nadic acid. One or more of the group consisting of amines (H) is preferred, and the maleimide compound (B) is more preferred.

The content of the thermosetting component (E) in the resin composition of this embodiment is not particularly limited. When the reaction product (P) and the thermosetting component (E) are combined, the reaction product (P) and the thermosetting The total amount of the sexual component (E) (100% by mass; in terms of solid content of the solvent, solvent component and filler (J)), preferably 20% by mass or more and 85% by mass or less, more preferably 30% by mass It is more than 85% by mass and more preferably more than 40% by mass and less than 80% by mass. When the content of the thermosetting component (E) is within the above range, the printed circuit board tends to be excellent in formability, thermoelastic modulus, scum resistance, and chemical resistance even when the filler is filled.

<Epoxy resin (F)> When the resin composition of this embodiment contains an epoxy resin (F), there exists a tendency for adhesiveness, moisture absorption heat resistance, flexibility, etc. to be more excellent. The epoxy resin (F) is not particularly limited as long as it is a compound having two or more epoxy groups in one 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 novolac epoxy resin, biphenyl Epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, xylenol novolac epoxy resin, polyfunctional phenol epoxy resin, naphthalene epoxy resin, naphthalene skeleton modified phenolic Varnish type epoxy resin, napthyl ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin, 4-functional phenol type epoxy resin, tripropylene oxide Isocyanurate, propylene oxide epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac epoxy resin, biphenol novolac epoxy resin, phenol aralkyl novolac Epoxy resin, naphthol aralkyl novolac epoxy resin, aralkyl novolac epoxy resin, biphenylaralkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentyl Diene-type epoxy resin, polyol-type epoxy resin, phosphorus-containing epoxy resin, epoxypropylamine 2. Compounds obtained by epoxidizing double bonds such as butadiene, compounds obtained by reacting hydroxyl-containing polysiloxane resins with epichlorohydrin, and the halides thereof.

Among them, the epoxy resin (F) is selected from the group consisting of a biphenylaralkyl epoxy resin, a naphthyl ether epoxy resin, a polyfunctional phenol epoxy resin, and a naphthalene epoxy resin. One or more of the groups are preferred. By containing such an epoxy resin (F), the flame retardance and heat resistance of the obtained hardened | cured material tend to improve more.

The epoxy resin (F) may be used alone or in combination of two or more.

The content of the epoxy resin (F) in the resin composition of this embodiment is not particularly limited, and it does not include a solvent or a solvent with respect to the total amount (100% by mass) of the reaction product (P) and the thermosetting component (E). The solid content of the components and filler (J)) is preferably 1.0% by mass or more and 20% by mass or less, more preferably 1.0% by mass or more and 15% by mass or less, and more preferably 2.0% by mass or more and 10% by mass or less. . When the content of the epoxy resin (F) is in the above range, the adhesiveness and flexibility tend to be more excellent.

<Cyanate Compound (G)> The cyanate compound (G) used in this embodiment is not particularly limited. For example, a naphthol aralkyl cyanate represented by the following general formula (3), and the following general formula (4) ), Novolac cyanate, biphenylaralkyl cyanate, bis (3,3-dimethyl-4-cyanoxyphenyl) methane, bis (4-cyanoxyphenyl) Methane, 1,3-dicyanooxybenzene, 1,4-dicyanooxybenzene, 1,3,5-tricyanooxybenzene, 1,3-dicyanoxynaphthalene, 1,4-dicyanocyanine Oxynaphthalene, 1,6-dicyanoxynaphthalene, 1,8-dicyanoxynaphthalene, 2,6-dicyanoxynaphthalene, 2,7-dicyanoxynaphthalene, 1,3,6- Tricyanoxynaphthalene, 4,4'-dicyanooxybiphenyl, bis (4-cyanoxyphenyl) ether, bis (4-cyanoxyphenyl) sulfide, bis (4-cyanoxyoxy) Phenyl) fluorene, and 2,2-bis (4-cyanooxyphenyl) propane.

Among them, the naphthol aralkyl type cyanate compound represented by the following general formula (3), the novolac type cyanate ester represented by the following general formula (4), and biphenylaralkyl type cyanate ester because of flame retardancy It has excellent properties, high hardenability, and low thermal expansion coefficient of the hardened material, and is particularly preferably selected from the naphthol aralkyl cyanate compound represented by the following general formula (3) and the following general formula (4) One or two or more of the group consisting of novolac-type cyanate are more preferable.

[Chemical 5] In the formula (3), a plurality of R ₆ each independently represent a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more.

In the formula (3), a plurality of R ₆ each independently represent a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferred.

In formula (3), n ₂ represents an integer of 1 or more. The upper limit 値 of n ₂ is preferably 10, and more preferably 6.

[Chemical 6] In formula (4), a plurality of R ₇ each independently represent a hydrogen atom or a methyl group, a plurality of R ₈ each independently represent a hydrogen atom or an alkyl or alkenyl group having 1 to 4 carbon atoms, and n ₃ represents 1 or more Integer.

In the formula (4), a plurality of R ₇ each independently represent a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferred.

In the formula (4), a plurality of R ₈ each independently represent a hydrogen atom or an alkyl or alkenyl group having 1 to 4 carbon atoms.

In formula (4), n ₃ represents an integer of 1 or more. The upper limit 値 of n ₃ is preferably 10, and more preferably 7.

The manufacturing method of these cyanate ester compounds is not specifically limited, It can manufacture according to the various existing methods with respect to 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) and a cyanogen halide in a passive organic solvent in the presence of a basic compound. Alternatively, a method in which a salt made from the same naphthol aralkyl phenol resin and a basic compound is formed in a solution containing water, and then a two-phase interface reaction with a cyanogen halide is performed and synthesized.

[Chemical 7] In the formula (5), a plurality of R ₆ each independently represent a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more.

In the formula (5), a plurality of R ₆ each independently represent a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferred.

In formula (5), n ₄ represents an integer of 1 or more. The upper limit 値 of n ₄ is preferably 10, and more preferably 6.

The naphthol aralkyl cyanate compound can be selected from naphthols such as α-naphthol or β-naphthol, p-xylylene glycol, α, α'-dimethoxy-p-xylene, 1, The naphthol aralkyl resin obtained by the reaction of 4-bis (2-hydroxy-2-propyl) benzene and the like is selected from those obtained by condensing with cyanic acid.

The cyanate ester compound (G) may be used alone or in combination of two or more.

The content of the cyanate ester compound (G) in the resin composition of this embodiment is not particularly limited, and it is not included in the solvent relative to the total amount of the reaction product (P) and the thermosetting component (E) (100% by mass; In terms of the solid content of the solvent component and the filler (J)), it 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, and more preferably 0.1 mass% or more and 1.0 mass% or less. the following. When the content of the cyanate ester compound (G) is within the above range, there is a tendency that a printed circuit board having more excellent moldability, thermoelastic modulus, scum resistance, and chemical resistance can be obtained.

＜ Aldiyl-substituted nadicarium imine (H) ＞ The aldiyl-substituted nadicarium imine (F) used in this embodiment, as long as there is more than one alkenyl-substituted sodium in the molecule There is no particular limitation on the compound of dikeminimine. Specific examples thereof include compounds represented by the following general formula (6).

[Chemical 8]

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

[Chemical 9]

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

[Chemical 10]

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

In addition, a commercially available product may be used as the aldiyl substituted nadicarium imine (F) represented by the formula (6). Commercial products are not particularly limited, for example, a compound represented by the following formula (9) (BANI-M (Maruzen Petrochemical Co., Ltd.)) and a compound represented by the following formula (10) (BANI-X (Maruzen Petrochemical Co., Ltd.) ) System)) and so on.

The aldiyl-substituted nadicarium imine (H) may be used singly or in combination of two or more kinds.

[Chemical 11]

[Chemical 12]

In the resin composition according to this embodiment, the content of the aldiyl-substituted nadicarium imine (H) is not particularly limited, and it is relative to the total amount of the reaction product (P) and the thermosetting component (E) (100% by mass). ; In terms of solid content of solvent, solvent component and filler (J)), preferably 5.0% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass More than 40% by mass. When the content of the aldiyl-substituted nadicarium imine (H) is within the above range, it is possible to obtain a printed circuit board with better moldability, thermoelastic modulus, slag resistance, and chemical resistance. tendency.

The epoxy resin (F), the cyanate ester compound (G), and the aldiyl substituted nadicarium imine (H) can also be used as raw materials for the reaction product (P).

The thermosetting component (E) may be used alone or in combination of two or more.

In addition, in the resin composition of the present embodiment, other resins may be added in addition to the reaction product (P) and the thermosetting component (E) as long as the desired characteristics are not impaired. The type of the other resin is not particularly limited as long as it has insulation properties, and examples thereof include thermoplastic resins. By appropriately using a thermoplastic resin. Properties such as metal adhesion and stress relaxation can be imparted.

[Filling Material (J)] The resin composition of the present embodiment should preferably further contain a filler (J). The filler (J) is not particularly limited as long as it has insulation properties, such as: natural silicon dioxide, fused silicon dioxide, amorphous silicon dioxide, hollow silicon dioxide, and other silicon dioxide; alumina, Aluminum nitride, boron nitride, boehmite, molybdenum oxide, titanium oxide, zinc borate, zinc stannate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, short glass fibers (E glass, D Glass powders such as glass), inorganic fillers such as hollow glass and spherical glass, organic fillers such as silicone rubber, and polysiloxane composite powder. One of them may be used or two or more of them may be appropriately mixed and used.

Among them, the filler (J) should contain silicon dioxide in view of low thermal expansion, and should preferably contain one selected from the group consisting of alumina and aluminum nitride in view of high thermal conductivity, or Two or more are preferred.

In the resin composition of this embodiment, the content of the filler (J) is not particularly limited. When the reaction product (P) is combined with the thermosetting component (E), the content of the filler (J) is higher than that of the reaction product (P) and the thermosetting component. The total amount of (E) (100 parts by mass; the total amount of the reaction product (P) when the reaction product (P) is used without the solvent, the solvent component, and the solid content of the filler (J)) ( 100 parts by mass; in terms of the solid content of the solvent, solvent component and filler (J)), if the content of the filler (J) is 50 parts by mass or more and 300 parts by mass or less, low thermal expansion and high thermal conductivity are considered The viewpoint of such characteristics is more preferable, among which 100 mass parts to 300 mass parts is more preferable, and 100 mass parts to 250 mass parts is more preferable.

[Silane coupling agent, wetting and dispersing agent] In the resin composition of this embodiment, in order to improve the dispersibility of the particles of the filler, the adhesion strength of the resin and the particles, and the glass cloth, a silane coupling agent and / or wetting may be used in combination. Dispersant. The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for the surface treatment of inorganic substances. Specific examples, for example: amine silane based on γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane; γ-glycidyloxy Silyl epoxy systems such as propyltrimethoxysilane; acrylate silane systems such as γ-propenyloxypropyltrimethoxysilane; N-β- (N-vinylbenzylaminoethyl) -γ-amine Cationic silane-based silane coupling agents such as propyltrimethoxysilane hydrochloride; phenylaryl silane-based silane coupling agents such as styrylsilane can be used alone or in a suitable combination of two or more. The wetting and dispersing agent is not particularly limited as long as it is a dispersing stabilizer used for coating applications. Specific examples include, for example, wetting and dispersing agents such as BYPER Chemical Corporation's product names DISPER-BYK110, 111, 118, 180, 161, BYK-W996, W9010, and W903.

[Hardening Accelerator] In the resin composition of this embodiment, a hardening accelerator may be used in combination as long as the desired characteristics are not impaired. The hardening accelerator is not particularly limited. For example, exemplified organic compounds such as benzamidine peroxide, lauryl peroxide, acetamidine peroxide, benzamidine p-chloroperoxide, and di-tert-butyl phthalate. Oxides; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylaniline ethanol , Tri-n-butylamine, pyridine, quinoline, N-methyl Tertiary amines such as phosphine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol ; Organometallic salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron ethylacetonate; etc. Organometallic salts dissolved in hydroxy-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; dioctyl tin oxide, other alkyl tin, and alkyl tin oxide And other organotin compounds, and triphenylimidazole (TPIZ).

[Organic solvent] The resin composition of this embodiment may contain a solvent as needed. For example, if an organic solvent is used, the viscosity of the resin composition during preparation is reduced, the operability is improved, and the impregnation property to the glass cloth can be improved. The type of the solvent is not particularly limited as long as it is a part or all of the resin in the resin composition. Specific examples thereof are not particularly limited, for example: ketones such as acetone, methyl ethyl ketone, methylcythreon; aromatic hydrocarbons such as toluene and xylene; fluorenamines such as dimethylformamide; propylene glycol monomethyl ether and its ethyl Acid ester. The solvent may be used singly or in combination of two or more kinds.

[Other components] In the resin composition of this embodiment, other thermosetting resins, thermoplastic resins, oligomers, elastomers, and other polymer compounds may be used in combination within a range that does not impair desired characteristics; other flame retardants Sexual compounds; additives, etc. They are not limited as long as they are general users. Examples of flame retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, Ring compound. In terms of additives, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, light sensitizers, dyes, pigments, tackifiers, lubricants, defoamers, surface modifiers, A glossing agent, a polymerization inhibitor, and the like are appropriately used in combination as necessary.

[Manufacturing method of resin composition] The manufacturing method of the resin composition of this embodiment can be modified with an amino group-modified polysiloxane (A), a maleimide compound (B), and a carboxylic acid (C) and The reaction product (P) obtained by reacting at least one of the carboxylic acid anhydride (D) is directly used as a resin composition. The obtained reaction product (P) can be mixed with the thermosetting component (B) to obtain a resin composition. Moreover, other arbitrary components may be mixed as needed.

The method for producing the resin composition of this embodiment is not particularly limited. In an ideal state, the method has a method of reacting an amine-modified polysiloxane (A) with a maleimide compound (B) to obtain a primary polymer. A first reaction step (hereinafter simply referred to as "first reaction step"), and a second reaction step (hereinafter also referred to as "first reaction step") in which at least one of a primary polymer and a carboxylic acid (C) and a carboxylic anhydride (D) is reacted; If it is simply referred to as "the second reaction step"), it is preferable to obtain a more excellent storage stability of the reaction product (P).

The reaction temperature in the first reaction step is not particularly limited as long as it is a temperature at which the reaction between the amine-modified polysiloxane (A) and the maleimide compound (B) proceeds. Good, 100 ℃ ~ 150 ℃ is better.

Supply the viscosity of the primary polymer obtained in the first reaction step in the second reaction step. Considering the viewpoint of obtaining better storage stability of the reaction product (P), it is preferably 100 ~ 500mPa · s, 150mPa · s ~ 400mPa・ S is better. The method for measuring the viscosity of the primary polymer is not particularly limited, and it can be measured using a general viscometer. For example, a cone-plate viscometer (eg, an ICI viscometer) can be used for the measurement.

The reaction temperature in the second reaction step is not particularly limited, but is preferably 50 ° C to 200 ° C, and more preferably 100 ° C to 150 ° C. The reaction time is not particularly limited, but is preferably 0.5 hours to 5 hours, and more preferably 1.5 hours to 3.5 hours.

Of course, in the manufacturing method of the resin composition of this embodiment, amine-modified polysiloxane (A), maleimide compound (B), and carboxylic acid (C) and carboxylic anhydride (D) may be used. At least one of them reacts at the same time. That is, the first reaction step and the second reaction step may be performed simultaneously.

In the first and second steps, at least one of an amine-modified polysiloxane (A), a maleimide compound (B), a carboxylic acid (C), and a carboxylic anhydride (D), and a primary polymerization In order to improve their operability, it is better to dilute with solvents. The type of the solvent is not particularly limited, for example, ketones such as acetone, methyl ethyl ketone, and methyl cyperidine; aromatic hydrocarbons such as toluene and xylene; amines such as dimethylformamide; propylene glycol monomethyl ether and ethyl acetate thereof Acid ester. The solvent may be used singly or in combination of two or more kinds.

When manufacturing a resin composition, a well-known process (stirring, mixing, kneading process, etc.) may be performed in order to dissolve or disperse each component uniformly. When the filler (J) and the like are uniformly dispersed, the dispersibility of the resin composition can be improved by performing a stirring dispersion treatment using a stirring tank equipped with a stirrer having an appropriate stirring ability. The above-mentioned stirring, mixing, and kneading processes can be appropriately performed using, for example, a device for mixing purposes such as a ball mill and a bead mill, or a known device such as a revolving or self-converting mixing device.

[Prepreg] The prepreg according to this embodiment includes a substrate and a resin composition of this embodiment impregnated or coated on the substrate. The manufacturing method of the prepreg can be carried out according to a conventional method, and there is no particular limitation. For example, after impregnating or coating the above-mentioned resin composition on a substrate, the resin composition is semi-hardened (B-staged) by heating in a dryer at 100 to 200 ° C for 1 to 30 minutes to obtain a prepreg. method. In this embodiment, the content of the resin composition (including fillers and additive components) with respect to the total amount (100% by mass) of the prepreg is not particularly limited, and a range of 30% by mass to 90% by mass is preferred. .

The base material used for the prepreg of this embodiment is not particularly limited, and it can be appropriately selected and used from known products used in various printed circuit board materials according to the purpose and performance. Specific examples thereof are not particularly limited, and examples thereof include glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; inorganic fibers other than glass such as quartz; Phenyl p-xylylenediamine (Kevlar (registered trademark), manufactured by DuPont), copolymerized p-xylene, 3,4'oxydiphenylene, p-xylylenediamine (Technora (registered trademark) And Teijin technoproducts, etc.) Fully aromatic polyamines, 2,6-hydroxynaphthoic acid and p-hydroxybenzoic acid (Vectran (registered trademark), Kuraray Corporation) and other polyesters Benzobenzobis Organic fibers such as poly (p-phenylene-2,6-benzobisoxazole) (Zylon (registered trademark), manufactured by Toyobo Corporation), polyimide, and the like.

Among these, from the viewpoint of considering low thermal expansion, 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 preferred. .

The shape of the substrate is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, cut strand felts, and surface felts. The weaving method of the weaving cloth is not particularly limited. For example, plain weaving, basket weave, and twill weave are known, and can be appropriately selected from these known products according to the purpose and performance. Further, it is preferable to use a glass woven fabric which has been subjected to a fiber-opening treatment and a surface treatment such as a silane coupling agent. The thickness and quality of the substrate are not particularly limited, and generally about 0.01 to 0.3 mm is suitable. In particular, from the viewpoint of strength and water absorption, the substrate is preferably a glass woven fabric with a thickness of 200 μm or less and a mass of 250 g / m ² or less. A glass woven fabric composed of glass fibers such as E glass, S glass, and T glass. More ideal.

The laminated plate according to this embodiment can be obtained by, for example, laminating a plurality of prepregs and curing them. The metal foil-clad laminate according to the present embodiment can be obtained by, for example, laminating and curing the above-mentioned prepreg with a metal foil.

Specifically, the metal foil-clad laminate according to this embodiment can be obtained, for example, by laminating at least one or more of the above-mentioned prepregs, arranging metal foils on one or both sides, and forming the laminates. More specifically, one or two or more of the above-mentioned prepregs are stacked, and metal foils such as copper and aluminum are arranged on one or both sides of the prepreg as required, and laminated as necessary to obtain a coating. Metal foil laminate. The metal foil used here is not particularly limited as long as it is a user in a printed circuit board material, and a known copper foil such as a rolled copper foil or an electrolytic copper foil is preferred. The thickness of the metal foil is not particularly limited, but is preferably 1.0 μm to 70 μm, and more preferably 1.5 μm to 35 μm. The forming method and forming conditions of the metal foil-clad laminated board are also not particularly limited, and methods and conditions of general laminated boards and multilayer boards for printed circuit boards can be used. For example, when forming a metal-clad laminate, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, and the like can be used. When forming a metal foil-clad laminate, generally, the temperature is in the range of 100 to 300 ° C., the pressure is 2.0 to 100 kgf / cm ² , and the heating time is in the range of 0.05 to 5 hours. Furthermore, if necessary, post-curing may be performed at a temperature of 150 to 300 ° C. Furthermore, the above-mentioned prepreg and a separately prepared wiring board for an inner layer may be combined and laminated to form a multilayer board.

The metal foil-clad laminate of this embodiment can be suitably used as a printed circuit board by using a predetermined wiring pattern. In addition, the metal foil-clad laminate of this embodiment has low thermal expansion coefficient, good formability, metal foil peel strength, and chemical resistance (especially resistance to slag removal), and can be effectively used as a semiconductor package requiring such performance. With printed circuit board.

In addition, in this embodiment, in addition to the form of the prepreg, a landfill sheet in the form in which the resin composition is applied to a metal foil or a film may be adopted.

[Resin sheet] The resin sheet according to this embodiment includes a support and a resin composition according to this embodiment which is arranged on the surface of the support. A resin sheet obtained by coating the above resin composition on one or both sides of a support. Here, the resin sheet can be produced by applying a thermosetting resin (including a filler) used in a prepreg or the like directly on a support such as a metal foil, a film, and the like by using one of the methods of thinning, and drying it. .

The support used in the production of the resin sheet in this embodiment is not particularly limited, and known products used for various printed circuit board materials can be used, and resin sheets or metal foils are preferred. Resin sheet and metal foil, such as: polyimide film, polyimide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film Resin sheets such as polypropylene (PP) film and polyethylene (PE) film, and metal foils such as aluminum foil, copper foil, and gold foil. Among them, electrolytic copper foil and PET film are preferred.

The resin sheet of this embodiment is preferably one in which the above-mentioned resin composition is applied to a support and then semi-hardened (B-staged). The manufacturing method of the resin sheet of this embodiment is preferably a method of generally manufacturing a composite of a B-stage resin and a support. Specifically, for example, a method of manufacturing a resin sheet by coating the resin composition on a support such as a copper foil, and then heating it in a dryer at 100 to 200 ° C for 1 to 60 minutes, and then semi-hardening it. . The adhesion amount of the resin composition to the support is preferably in a range of 1.0 μm to 300 μm based on the resin thickness of the resin sheet.

The resin sheet of this embodiment can be used as a build-up material for a printed circuit board.

The laminated board according to this embodiment can be obtained by, for example, laminating one or more of the above resin sheets and curing them.

The metal foil-clad laminate according to this embodiment can be obtained by, for example, laminating and curing the above-mentioned resin sheet and metal foil.

Specifically, the metal foil-clad laminate according to this embodiment can be obtained by, for example, using the above-mentioned resin sheet, arranging metal foils on one or both sides thereof, and laminating them. More specifically, for example, one of the aforementioned resin sheets or the support is peeled off if necessary, and a plurality of sheets are overlapped, and metal foils such as copper and aluminum are arranged on one or both sides, and then laminated as necessary To manufacture metal foil-clad laminates. The metal foil used here is not particularly limited as long as it is a user in a printed circuit board material, and a known copper foil such as a rolled copper foil or an electrolytic copper foil is preferred. The forming method and forming conditions of the metal foil-clad laminate are not particularly limited, and methods and conditions for general laminates and multilayer boards for printed circuit boards can be used. For example, multi-stage presses, multi-stage vacuum presses, continuous forming machines, and autoclave forming machines can be used when forming metal-clad laminates. When forming a metal foil-clad laminate, generally, the temperature is in the range of 100 to 300 ° C., the pressure is 2.0 to 100 kgf / cm ² , and the heating time is in the range of 0.05 to 5 hours. Furthermore, if necessary, it may be post-cured at a temperature of 150 to 300 ° C.

The laminated board of the present embodiment may be a laminated board having a large number of resin sheets and / or prepregs, or a metal foil-clad laminated board including a resin sheet and / or a prepreg and a metal foil. These laminated plates can be obtained by laminating and curing a resin sheet, a prepreg, and a metal foil.

In the present embodiment, when a conductor layer to be a circuit is formed and a printed circuit board is manufactured, if the form of a metal foil-clad laminate is not adopted, an electroless plating method may be used.

[Printed Circuit Board] The printed circuit board of this embodiment includes an insulating layer containing the resin composition of this embodiment, and a conductor layer formed on a surface of the insulating layer.

The printed circuit board of this embodiment can be produced by, for example, forming a metal foil on an insulating layer and forming a conductive layer to be a circuit by electroless plating. The conductor layer is generally composed of copper and aluminum. The insulating layer for a printed circuit board on which a conductor layer has been formed is suitable for a printed circuit board by forming a predetermined wiring pattern. The printed circuit board of this embodiment contains the above-mentioned resin composition through the insulating layer, and maintains an excellent elastic modulus even at the reflow temperature during semiconductor mounting, thereby effectively suppressing the warpage of the semiconductor plastic package, and the metal foil Since it has excellent peel strength and resistance to dross removal, it is particularly effective as a printed circuit board for semiconductor packages.

The printed circuit board of this embodiment can be specifically manufactured by the following method, for example. First, the above-mentioned metal-clad laminate (copper-clad laminate, 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 layer circuit of the inner layer substrate is subjected to surface treatment for improving the adhesive strength as needed. Secondly, the above-mentioned prepreg is superposed on the inner circuit surface with the required number of sheets. The outer layer is laminated with metal for the outer layer circuit. The foil is heated and pressurized and formed into one piece. In this way, a base material and an insulating layer composed of a hardened material of a thermosetting resin composition are formed between the inner layer circuit and the metal foil for the outer layer circuit, and a multi-layer laminate is produced. Next, the multilayer laminated board is subjected to opening processing for through-holes and vias, and in order to remove residues from the resin of the resin component contained in the hardened layer, a slag removal treatment is performed. Thereafter, a plated metal film is formed on the wall surface of the hole to allow the inner layer circuit and the outer layer metal foil to communicate with each other, and then the metal foil for the outer layer circuit is etched to form an outer layer circuit to manufacture a printed circuit board.

In the printed circuit board of this embodiment, for example, the prepreg (the substrate and the resin composition attached to the substrate), the resin sheet (the support and the resin composition attached to the support), and a metal foil The resin composition layer (layer composed of the resin composition) of the laminated board constitutes an insulating layer containing the resin composition. [Example]

Hereinafter, the present invention will be specifically described according to examples and comparative examples, but the present invention is not limited by these examples.

[Weight-average molecular weight] The weight-average molecular weight of the reaction product is determined by using the resin composition obtained in the following examples and comparative examples as a sample, and according to a gel permeation chromatography (GPC) method, using a standard polystyrene calibration curve. , Calculate the conversion 値. Specifically, the relationship between the dissolution time from the column and the molecular weight was first determined, and the dissolution time was replaced with the molecular weight according to this relationship. The graph representing the "dissolution time versus molecular weight" used at this time is called the "calibration curve" (or calibration curve). "Relationship between dissolution time and molecular weight" varies according to each type of polymer. In principle, it is necessary to use a standard polymer with the same structure as the measurement object and a narrow molecular weight distribution with a known molecular weight. However, in reality, there are almost all difficulties, so a commercially available standard polymer is actually used. Here, polystyrene is used as the standard polymer. The molecular weight obtained in this way is called the standard conversion molecular weight. Accordingly, the weight average molecular weight (Mw) can be calculated from the following formula. [Number 1] In the formula, N is the number of polymer molecules, M is the molecular weight, and C is the sample concentration. The sample concentration C is proportional to the unit number of the monomer, so C = M × N.

[Synthesis Example 1] Synthesis of α-naphthol aralkyl cyanate resin The reactor having a thermometer, a stirrer, a dropping funnel, and a reflux cooler was previously cooled to 0 to 5 ° C with brine, and added to the reactor. 7.47 g (0.122 mol) of cyanogen chloride, 9.75 g (0.0935 mol) of 35% hydrochloric acid, 76 mL of water, and 44 mL of dichloromethane.

The temperature in this reactor is maintained at -5 ~ + 5 ℃, pH was maintained at 1 or less, using a dropping funnel with stirring consuming dropped for 1 hour in the formula (5) R ₆ are both hydrogen atom of the naphthol α- Aralkyl-type phenol resin (SN485, OH group equivalent: 214g / eq. Softening point: 86 ° C, manufactured by Nippon Steel Chemical Co., Ltd.) 20g (0.0935mol), and triethylamine 14.16g (0.14mol) are dissolved After 92 ml of dichloromethane was obtained as a solution, 4.72 g (0.047 mol) of triethylamine was added dropwise over 15 minutes after the dropwise addition was completed. [Chemical 13] n ₄ represents an integer of 1 or more.

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

[Example 1] Under conditions of heating and refluxing at a temperature of 130 ° C, 25 parts by mass of a maleimide imine compound (maleimide imide equivalent 285 g / eq, trade name "BMI-80" manufactured by KI Kasei Corporation) was used. Dissolved in a solution of 40 parts by mass of propylene glycol monomethyl ether (manufactured by KHneochem) to make a diamine-modified polysiloxane (X-22-161B, amine equivalent 1500 g / eq, a product made by Shin-Etsu Chemical Industry Co. The name "X-22-161B") was dissolved in 15 parts by mass to prepare a primary polymer. After that, the stirring was continued under the condition of a heating and reflux temperature of 130 ° C. When the viscosity of the polymer was increased to 200 to 300 mPa · s at one time measured by an ICI viscometer (cone-plate viscometer, manufactured by Towa Industrial Co., Ltd.), the A solution prepared by dissolving 1.0 part by mass of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 22.5 parts by mass of propylene glycol monoethyl ether acetate (manufactured by The Dow Chemical Co., Ltd.) was added to the polymer, and the solution was maintained at a reflux temperature of 130 ° C. After several hours of reaction, a resin composition containing a reaction product was obtained. A part of the obtained resin composition was used as a sample, and the weight average molecular weight of the reaction product was measured. Further, a part of this resin composition was stored at 25 ° C 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] 1.0 part by mass of maleic anhydride was replaced by 1.0 part by mass of acetic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and a reaction product containing a weight average molecular weight of 13,200 was obtained in the same manner as in Example 1. Resin composition. A part of the obtained resin composition was used as a sample, and the weight average molecular weight of the reaction product was measured. Further, a part of this resin composition was stored at 25 ° C 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] 1.0 part by mass of maleic anhydride was replaced with 1.0 part by mass of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and a weight average molecular weight of 12,500 was obtained in the same manner as in Example 1. The resin composition of the reaction product. A part of the obtained resin composition was used as a sample, and the weight average molecular weight of the reaction product was measured. A part of this resin composition was stored at 25 ° C 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] A reaction product containing a weight average molecular weight of 12,000 was obtained in the same manner as in Example 1 except that 1.0 part by mass of maleic anhydride was replaced with 1.0 part by mass of maleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). Resin composition. A part of the obtained resin composition was used as a sample, and the weight average molecular weight of the reaction product was measured. Further, a part of this resin composition was stored at 25 ° C 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] A resin composition containing a reaction product having a weight average molecular weight of 11710 was obtained in the same manner as in Example 1 except that 1.0 part by mass of maleic anhydride was replaced with 0.5 part by mass of maleic anhydride. A part of the obtained resin composition was used as a sample, and the weight average molecular weight of the reaction product was measured. Further, a part of this resin composition was stored at 25 ° C 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] A resin composition containing a reaction product having a weight average molecular weight of 13,900 was obtained in the same manner as in Example 1 except that 1.0 part by mass of maleic anhydride and 22.5 parts by mass of propylene glycol monoethyl ether acetate were not used. . A part of the obtained resin composition was used as a sample, and the weight average molecular weight of the reaction product was measured. Further, a part of this resin composition was stored at 25 ° C 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] A resin composition containing a reaction product having a weight average molecular weight of 14,100 was obtained in the same manner as in Example 1 except that 1.0 part by mass of maleic anhydride was not used. A part of the obtained resin composition was used as a sample, and the weight average molecular weight of the reaction product was measured. Further, a part of this resin composition was stored at 25 ° C for 7 days, and the weight-average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Table 1]

In Table 1, "increase rate" refers to the ratio (%) of the weight average molecular weight of the resin composition after storage for 7 days to the weight average molecular weight of the resin composition before storage. The "weight-average molecular weight" of the resin composition before storage does not refer to the osmium measured at the time of obtaining each resin composition, but the osmium measured at the date of obtaining each resin composition. Therefore, the initial storage stability can be compared with 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 and a maleimide compound (maleimide imide equivalent 186 g / eq, trade name "BMI-2300" manufactured by Daiwa Chemical Industry Co., Ltd.) 30 parts by mass, 4.5 parts by mass of biphenol novolac epoxy resin (trade name "NC-3000FH" manufactured by Nippon Kayaku Co., Ltd.), bisdiallyl nadic acid imine (alkenyl equivalent 286 g / eq, Maruzen 25 parts by mass of the trade name "BANI-M" manufactured by Petrochemical Corporation, 0.5 part by mass of the cyanate of the α-naphthol aralkyl phenol resin obtained in the above Synthesis Example 1, and slurry silicon dioxide (manufactured by Admatechs) (Trade name "SC-2050MB") 200 parts by mass, epoxy silane coupling agent (trade name "Z6040" manufactured by Toray Dow Corning Corporation) 5 parts by mass, and triphenylimidazole (Tokyo Chemical Industry Co., Ltd.) as a hardening accelerator (Manufactured by the company) 0.5 parts by mass were mixed to obtain a resin composition.

[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 replaced with 40.0 parts by mass of the resin composition obtained in Comparative Example 2.

[Amine value] The amine value was measured for each resin composition obtained in Example 6 and Comparative Example 3. Specifically, in accordance with JIS K 7237: 1995, the amine value is measured in terms of the total amount of the primary amine and secondary amine of the resin composition. The results are shown in Table 2.

[Preparation of prepreg] Each resin composition obtained in Example 6 and Comparative Example 3 was diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on T glass cloth (T2118), and heated and dried at 150 ° C for 3 minutes to adjust the content (% by mass) of the resin composition so that the thickness of the insulating layer when the following laminated board was made was 100 μm. A prepreg was obtained.

[Varnish gel time] A part of each varnish obtained when the prepreg was prepared was used as a sample, and the gel time (seconds) at 170 ° C was measured. A part of this varnish was stored at 25 ° C for 7 days, and the gel time (seconds) after storage was measured in the same manner as described above. The results are shown in Table 2.

[Prepreg Viscosity] The resin component was obtained from the prepreg produced according to the above method, and a dynamic viscoelasticity measuring device (trade name "AR2000" manufactured by TA Instrument Corporation) was used to measure an angular velocity of 1 rad / s and a geometric gap of 120 ° C at 1 mm The viscosity of the measurement conditions (mPa · s). The prepreg was stored at 25 ° C. for 7 days. The resin component was obtained from the prepreg after storage, and the shear viscosity (mPa · s) was measured in the same manner as described above. The results are shown in Table 2.

[Table 2]

[Laminate board] On top of the obtained prepreg, a 12 μm-thick electrolytic copper foil (trade name “3EC-III” manufactured by Mitsui Metals Mining Co., Ltd.) was placed, and the pressure was 30 kgf / cm ² at a temperature of 220 ° C. for 120 The laminate was formed for one minute to obtain a copper-clad laminate having an insulating layer thickness of 100 μm (formed before storage). Further, the obtained prepreg was stored at 25 ° C for 7 days, and one piece of the prepreg after the storage was used, and laminated in accordance with the same method as above to obtain a copper-clad laminate having an insulation layer thickness of 100 μm. (Formed after storage).

[Coefficient of Thermal Expansion] After each copper-clad laminate obtained (formed before storage and formed after storage) was removed from the copper foil by full etching, the temperature was increased from 40 ° C at 10 ° C per minute using a thermomechanical analysis device (manufactured by TA Instruments). At 340 ° C, the linear expansion coefficient in the plane direction of 60 ° C to 120 ° C was measured, and the obtained 値 was used as the evaluation coefficient of thermal expansion coefficient (ppm / degC). The measurement direction is a measurement of the longitudinal direction (Warp) of the glass cloth of the laminate. The results are shown in Table 3.

[table 3]

This application is based on 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 May 2017-000666), and their contents are incorporated herein by reference. [Industrial availability]

The resin composition of the present invention and the printed circuit board obtained from the resin composition are suitable for use in various electronic devices such as personal computers and components of communication equipment.

no

Claims (20)

A resin composition comprising a reaction product (P), the reaction product (P) is an amino-modified polysiloxane (A), a maleimide compound (B), and a carboxylic acid (C) and a carboxylic anhydride It is obtained by reacting at least one of (D). For example, the resin composition of the first patent application range, wherein the resin composition has an amine value of 2.0 mgKOH / g or less. For example, the resin composition of claim 1 or 2, wherein the reaction product (P) is obtained by reacting at least the carboxylic acid anhydride (D), and the carboxylic acid anhydride (D) is selected from the group consisting of maleic anhydride, One or more of phthalic anhydride, succinic anhydride, and acetic anhydride. For example, the resin composition of claim 1 or 2, wherein the reaction product (P) is obtained by reacting at least the carboxylic acid (C), and the carboxylic acid (C) is selected from the group consisting of maleic acid, One or two or more of the group consisting of phthalic acid, succinic acid, and acetic acid. For example, the resin composition in the scope of claims 1 or 2 further includes a thermosetting component (E). For example, the resin composition of claim 5 in which the thermosetting component (E) contains a material selected from the group consisting of a maleimide compound (B), an epoxy resin (F), and a cyanate compound (G ), And one or two or more of the group consisting of aldiyl-substituted nadiimide (H). For example, the resin composition of claim 1 or 2, wherein the amine-modified polysiloxane (A) in the reaction product (P) includes a compound represented by the following general formula (1); (1) In the formula (1), a plurality of R _a each independently represent a hydrogen atom, a methyl group or a phenyl group, a plurality of R _b each independently represent a single bond, an alkylene group or an aryl group, and n represents an integer of 1 or more . For example, the resin composition of claim 1 or 2, wherein the amine group equivalent of the amine-modified polysiloxane (A) in the reaction product (P) is 130 or more and 6000 or less. For example, the resin composition of claim 1 or 2, wherein the maleimide compound (B) contains a compound selected from bis (4-maleimidephenyl) methane, 2,2-bis ｛4- (4-maleimideiminophenoxy) -phenylammonium propane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, polycyclobutane oxidation One or two or more of the group consisting of bis (4-maleimide benzoate) and a compound represented by the following general formula (2); (2) In the formula (2), a plurality of R ₅ each independently represent a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more. For example, the resin composition in the scope of patent application No. 1 or 2 further contains a filler (J). For example, the resin composition of claim 10, wherein the filler (J) contains one or two or more members selected from the group consisting of silicon dioxide, aluminum oxide, and aluminum nitride. For example, the resin composition of the scope of application for patent No. 10, wherein the resin composition contains 50 parts by mass or more and 300 parts by mass relative to 100 parts by mass of the total amount of the reaction product (P) and the thermosetting component (E). The filler (J) is below. A prepreg comprising: a substrate; and a resin composition impregnated or coated on the substrate according to any one of claims 1 to 12 of the scope of patent application. For example, the prepreg of item 13 of the patent application scope, wherein the substrate is one or two selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers. the above. A resin sheet comprising: a support; and a resin composition as set forth in any one of claims 1 to 12 of the scope of patent application arranged on the surface of the support. For example, the resin sheet of the scope of application for patent No. 15 wherein the support is a resin sheet or a metal foil. A laminated board having one or two or more members selected from the group consisting of a prepreg such as the scope of patent application 13 or 14 and a resin sheet such as the scope of patent application 15 or 16 . A metal foil-clad laminate having one or two selected from the group consisting of a prepreg such as the scope of patent application 13 or 14 and a resin sheet such as the scope of patent application 15 or 16 More than one species; and metal foil. A printed circuit board includes: an insulating layer containing the resin composition as described in any one of claims 1 to 12 of the scope of patent application; and a conductor layer formed on the surface of the insulating layer. A method for manufacturing a resin composition, comprising: a first reaction step for reacting an amine-modified polysiloxane (A) with a maleimide compound (B) to obtain a primary polymer; and a second reaction step for The primary polymer and the carboxylic acid (C) react with at least one of the carboxylic acid anhydride (D).