TWI730075B - 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 its manufacturing method, prepreg, resin sheet, laminated board, metal foil-clad laminated board and printed circuit board

The present invention relates to a resin composition and its manufacturing method, a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, 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, etc., the high integration and high-density mounting of various parts for semiconductor packages has also been accelerating in recent years. Among them, the warpage of the semiconductor plastic package caused by the difference in the 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 can be the low thermal expansion of the insulating layer used in the printed circuit board. This is a method of suppressing warpage by making the thermal expansion coefficient of the printed circuit board close to the thermal expansion coefficient of the semiconductor element, and it has been actively adopted now (for example, refer to Patent Documents 1 to 3).

As a method to suppress the warpage of semiconductor plastic packages, in addition to lower thermal expansion of printed circuit boards, there are also discussions to increase the rigidity of the laminate (high rigidity) and increase the glass transition temperature of the laminate (high Tg) (For example, refer to Patent Documents 4 and 5). [Prior Technical Documents] [Patent Documents]

Patent Document 1: Japanese Patent Application Publication No. 2013-216884 Patent Document 2: Japanese Patent 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 Publication No. 2011-178992

(Problems to be Solved by the Invention) However, even with printed circuit boards using thermosetting resin compositions described in Patent Documents 1 to 5, it is still difficult to balance the peeling strength of metal foil-laminated laminates, or for example Other characteristics such as chemical resistance (resistance to scum removal) of the alkaline cleaning solution, as a result, still have the problem of warping of the semiconductor plastic package.

Here, in order to reduce the above-mentioned difference in thermal expansion coefficient and solve the above-mentioned problem of warpage, the resin composition may be made by reacting a low-elasticity component such as amino-modified polysiloxane with a thermosetting component. Amino-modified polymer. However, polymers modified with amine groups generally have the property of further polymerizing the polymers with each other or with other resin components. Therefore, sometimes during the storage or molding of the resin composition or prepreg, the polymer modified by the amine group may undergo further polymerization reaction, resulting in failure to obtain excellent storage stability.

The object of the present invention is to solve the above-mentioned problems and provide a resin composition containing a polymer modified with an amine group but having excellent storage stability.

式(1)中，多數個R_a 各自獨立地表示氫原子、甲基或苯基，多數個R_b 各自獨立地表示單鍵、伸烷基或芳基，n表示1以上之整數。 [8]如[1]至[7]中任一項之樹脂組成物，其中，該反應產物(P)中之該胺基改性聚矽氧(A)之胺基當量為130以上6000以下。 [9]如[1]至[8]中任一項之樹脂組成物，其中，該馬來醯亞胺化合物(B)含有選自於由雙(4-馬來醯亞胺苯基)甲烷、2,2-雙｛4-(4-馬來醯亞胺苯氧基)-苯基｝丙烷、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷、聚環丁烷氧化物-雙(4-馬來醯亞胺苯甲酸酯)、及下列通式(2)表示之化合物構成之群組中之一種或二種以上； [化2]

式(2)中，多數個R₅ 各自獨立地表示氫原子或甲基，n₁ 表示1以上之整數。 [10]如[1]至[9]中任一項之樹脂組成物，更含有填充材(J)。 [11]如[10]之樹脂組成物，其中，該填充材(J)含有選自於由二氧化矽、氧化鋁、及氮化鋁構成之群組中之一種或二種以上。 [12]如[10]或[11]之樹脂組成物，其中，該樹脂組成物中，相對於該反應產物(P)及熱硬化性成分(E)之合計量100質量份，含有50質量份以上300質量份以下之該填充材(J)。 [13]一種預浸體，具有：基材；及含浸或塗佈於該基材之如[1]至[12]中任一項之樹脂組成物。 [14]如[13]之預浸體，其中，該基材選自於由E玻璃布、T玻璃布、S玻璃布、Q玻璃布、及有機纖維構成之群組中之一種或二種以上。 [15]一種樹脂片，具有：支持體；及配置在該支持體之表面之如[1]至[12]中任一項之樹脂組成物。 [16]如[15]之樹脂片，其中，該支持體為樹脂片或金屬箔。 [17]一種疊層板，具有多數個選自於由如[13]或[14]之預浸體、及如[15]或[16]之樹脂片構成之群組中之一種或二種以上。 [18]一種覆金屬箔疊層板，具有：選自於由如[13]或[14]之預浸體、及如[15]或[16]之樹脂片構成之群組中之一種或二種以上；及金屬箔。 [19]一種印刷電路板，具有： 含有如[1]至[12]中任一項之樹脂組成物之絕緣層；及 形成在該絕緣層之表面之導體層。 [20]一種樹脂組成物之製造方法，具有： 第一反應步驟，使胺基改性聚矽氧(A)與馬來醯亞胺化合物(B)反應而獲得一次聚合物；及 第二反應步驟，使該一次聚合物和羧酸(C)與羧酸酐(D)中之至少一者反應。That is, the present invention is as follows. [1] A resin composition comprising a reaction product (P), the reaction product (P) being modified with an amino group polysiloxane (A), a maleimide compound (B), and a carboxylic acid (C) It is obtained by reacting at least one of and carboxylic anhydride (D). [2] The resin composition according to [1], wherein the amine value of the resin composition is 2.0 mgKOH/g or less. [3] The resin composition of [1] or [2], wherein the reaction product (P) is obtained by reacting at least the carboxylic anhydride (D), and the carboxylic anhydride (D) is selected from One or two 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 more than two in 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 maleimide compound (B), an epoxy resin (F), and a cyanate ester compound (G ), and one or more of the group consisting of nadiimide (H) substituted with alkenyl groups. [7] The resin composition according to any one of [1] to [6], wherein the amino-modified polysiloxane (A) in the reaction product (P) comprises the following general formula (1) Compound; [化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 represents an integer of 1 or more. [8] The resin composition according to any one of [1] to [7], wherein the amino group equivalent of the amino-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 selected from bis(4-maleiminophenyl) methane , 2,2-bis{4-(4-maleiminophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleiminophenyl)methane , Polycyclobutane oxide-bis(4-maleimidin benzoate), and one or more of the group consisting of compounds represented by the following general formula (2); [化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 containing a filler (J). [11] The resin composition of [10], wherein the filler (J) contains one or two or more 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 relative to 100 parts by mass of the total amount of the reaction product (P) and the thermosetting component (E) Part or more and 300 parts by mass or less of the filler (J). [13] A prepreg having: a substrate; and the resin composition of any one of [1] to [12] impregnated or coated on the substrate. [14] The prepreg of [13], wherein the substrate is selected from one or two of the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fiber the above. [15] A resin sheet comprising: a support; and the resin composition of any one of [1] to [12] arranged on the surface of the support. [16] The resin sheet of [15], wherein the support is a resin sheet or metal foil. [17] A laminated board having a plurality of 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 Two or more; and metal foil. [19] A printed circuit board having: an insulating layer containing the resin composition of any one of [1] to [12]; and a conductor layer formed on the surface of the insulating layer. [20] A method for producing a resin composition, comprising: a first reaction step of reacting the amino-modified polysiloxane (A) with a maleimide compound (B) to obtain a primary polymer; and a second reaction In the step, the primary polymer is reacted with at least one of the carboxylic acid (C) and the carboxylic anhydride (D).

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

[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 above-mentioned amine-modified polymers.

The resin composition of this embodiment has excellent storage stability. The reason is presumed as follows (but the reason is not limited to this). The conventional resin composition containing amino-modified silicone and thermosetting components, because the resin composition contains the reactive amine of the amino-modified polymer as the raw material of the amino-modified silicone A large amount of the base remains in the structure of the prepolymer. This amine group will further react with the thermosetting component, resulting in the resin composition (including varnish) and the molded body obtained from the resin composition (for example: prepreg) And its molded body) cannot obtain excellent storage stability. For example, when the resin composition is stored at room temperature, further reaction between the remaining amine groups and the thermosetting component will cause the viscosity and molecular weight of the resin composition to increase, resulting in failure to obtain excellent storage stability. In addition, in the case of varnishes, gelation may occur, and in the case of prepregs, due to the increase in viscosity of the prepregs, the moldability is not good, and excellent storage stability cannot be obtained. On the other hand, the resin composition of this embodiment contains the amine group remaining in the reaction between the amino group-modified polysiloxane (A) and the maleimide compound (B), the carboxylic acid (C) and/ Or the reaction product (P) obtained by reacting the carboxylic anhydride (D) can provide the resin composition and the molded body obtained from the resin composition with excellent storage stability.

The amine value of the resin composition is the amine value in terms of the total amount of the primary amine and the 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 to suppress the increase in the viscosity of the resin composition, the increase in molecular weight, the gelation of varnish, and the increase in viscosity of the prepreg. In addition, the smaller the amine value, the more it is possible to suppress the increase in viscosity and molecular weight of the resin composition. The lower limit value of the amine value is preferably 0 mgKOH/g. The amine value can be measured in accordance with the method of JIS K 7237:1995.

[Reaction product (P)] The reaction product (P) of this embodiment is a combination of amine-modified polysiloxane (A), maleimide compound (B), carboxylic acid (C) and carboxylic anhydride (D) ) Is obtained by reacting at least one of them.

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

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. The weight average molecular weight is above 5000, and the thermal expansion rate of the prepreg tends to decrease. By the weight average molecular weight below 20,000, it can inhibit the viscosity increase of the resin composition, the increase of the molecular weight, the gelation of the varnish, and the prepreg. The tendency of body viscosity to rise. In order to obtain the reaction product (P) with a weight average molecular weight of 5000 or more and 20000 or less, it is sufficient to control the reaction conditions such as temperature. The weight average molecular weight is measured by the gel permeation chromatography (GPC) method, and is obtained as a value converted using a standard polystyrene calibration curve. Specifically, it can be measured in accordance with the method described in the examples described later.

In the resin composition of the present embodiment, the content of the reaction product (P) is not particularly limited, and when combined with the thermosetting component (E), it is relative to the reaction product (P) and thermosetting component in the resin composition The total amount of (E) (100% by mass; does not contain solvents, solvent components, and the solid content of the filler (J)), preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass 70% by mass or less, 20% by mass or more and 60% by mass or less. When the content of the reaction product (P) is within the above-mentioned range, there is a printed circuit board with excellent formability, low thermal expansion coefficient, thermoelastic modulus, scumming resistance, and chemical resistance even when it is filled as a filler. tendency.

式(1)中，多數個R_a 各自獨立地表示氫原子、甲基或苯基，其中甲基為較佳。多數個R_b 各自獨立地表示單鍵、伸烷基或芳基，其中伸烷基為較佳。伸烷基之碳數在其主鏈宜為1~4較佳。具體的伸烷基不特別限定，為亞甲基、伸乙基、三亞甲基、或四亞甲基更佳，三亞甲基又更佳。式(1)中，n表示1以上之整數。<Amino-modified polysiloxane (A)> The amine-modified polysiloxane (A) used in this embodiment is not particularly limited as long as it has one or more amine groups in the molecule. It is preferable to contain the compound represented by the following general formula (1). [化3]

(1) In the formula, a plurality of R _a each independently represent a hydrogen atom, a methyl group or a phenyl group, wherein the methyl group is preferred. A plurality of R _b each independently represents a single bond, an alkylene group or an aryl group, of which an alkylene group is preferred. The carbon number of the alkylene 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 more preferably trimethylene. In formula (1), n represents an integer of 1 or more.

The amino-modified silicone (A) may be used alone or in combination of two or more.

The amine group equivalent of the amino-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 more preferably 600 or more and 2500 or less. When the amine equivalent of the amine modified polysiloxane (A) is within the above range, a printed circuit board with better metal foil peeling strength and scum removal resistance can be obtained. The amine equivalent can be measured in accordance with the method of JIS K 7237:1995.

In the resin composition of this embodiment, the content of the amino-modified polysiloxane (A) is not particularly limited, and is relative to the total amount of the reaction product (P) in the resin composition (100% by mass; not including the solvent. In terms of the solid content of the solvent component and filler (J)), it is 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, the content of the amino-modified silicone (A) is determined by the amino-modified silicone used in the production of the reaction product (P) when the reaction product (P) is combined with the thermosetting component (E) The total amount of oxygen (A) and the amino-modified polysiloxane (A) contained as the thermosetting component (E) is relative to the reaction product (P) and thermosetting component (E) in the resin composition The total amount of) (100% by mass; in terms of 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, more preferably It is 5.0% by mass or more and 20% by mass or less. In addition, when the content of the amino-modified polysiloxane (A) is within the above-mentioned range, a printed circuit board with more excellent metal foil peeling strength and scumming resistance can be obtained. In addition, the content of the amino-modified silicone (A) referred to here includes not only the use of the amino-modified silicone (A) in the production of the reaction product (P), but also includes the following thermosetting component ( E) Amino modified polysiloxane (A).

<Maleimine compound (B)> The maleimine compound (B) used in this embodiment is not particularly limited as long as it has one or more maleimine groups in one molecule. . Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleiminophenyl)methane, 2,2-bis{4-( 4-maleiminophenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleiminophenyl)methane, bis(3-ethyl-5-methyl) -4-maleimidphenyl)methane, bis(3,5-diethyl-4-maleimidphenyl)methane, polycyclobutane oxide-bis(4-maleimidyl) Amino benzoate), maleimide compounds represented by the following general formula (2), prepolymers of these maleimine compounds, and prepolymers of maleimine compounds and amine compounds. One of them can be used or two or more of them can be appropriately mixed and used.

Among them, the maleimide compound (B) preferably contains selected from the group consisting of bis(4-maleiminophenyl)methane, 2,2-bis{4-(4-maleiminophenoxy) )-Phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidinyl) methane, polycyclobutane oxide-bis(4-maleimidin benzoic acid Ester), and one or more of the group consisting of maleimine compounds represented by the following general formula (2), preferably containing 2,2-bis{4-(4-maleimine benzene Oxy)-phenyl}propane is more preferred.

式(2)中，多數個R₅ 各自獨立地表示氫原子或甲基，n₁ 表示1以上之整數。[化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 the formula (2), a plurality of R ₅ each independently represents 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 of n ₁ is preferably 10, more preferably 7.

The maleimide compound (B) may be used singly or in combination of two or more kinds.

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

In the resin composition of this embodiment, the content of the maleimide compound (B) is not particularly limited, and is relative to the total amount (100% by mass) of the reaction product (P) in the resin composition; no solvent or solvent is included. In terms of the solid content of ingredients and fillers (J)), 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, the content of the maleimide compound (B) is the maleimide compound used in the production of the reaction product (P) when the reaction product (P) is combined with the thermosetting component (E) (B) and the total amount of 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 Mass%; in terms of solid content that does not contain solvents, solvent components, and fillers (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, more preferably 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-mentioned range, there is a tendency to obtain a printed circuit board with better moldability, thermoelastic modulus, scumming resistance, and chemical resistance. In addition, the content of the maleimide compound (B) referred to here includes not only the maleimide compound (B) used in the reaction product (P), but also includes the content of the thermosetting component (E) described later Maleimide compound (B).

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

Carboxylic acid (C) and carboxylic acid anhydride (D) are preferably monocarboxylic acid and monocarboxylic acid anhydride, or dicarboxylic acid and dicarboxylic acid anhydride, and more preferably dicarboxylic acid and dicarboxylic acid anhydride. good. Carboxylic acid (C) and carboxylic acid anhydride (D) are dicarboxylic acid and dicarboxylic acid anhydride, respectively. Compared with monocarboxylic acid and monocarboxylic acid anhydride, the resin composition has better storage stability. In addition, There is a tendency to suppress the decrease in insulation reliability when it is made into a printed circuit board. The reason is not particularly limited. It is presumed that if dicarboxylic acid or dicarboxylic acid anhydride is used, compared with monocarboxylic acid and monocarboxylic anhydride, the amine group and dicarboxylic acid of amine modified polysiloxane (A) When the carboxyl group of the carboxylic acid or dicarboxylic acid anhydride reacts, the carboxyl group paired with the reacted carboxyl group is not likely 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 two or more of them may be used in combination. In addition, the carboxylic acid (C) and the carboxylic anhydride (D) may be used alone or in combination.

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

In the reaction product (P) of this embodiment, the content ratio of the carboxylic acid (C) and the carboxylic anhydride (D) to the amino-modified polysiloxane (A) is not particularly limited, but is preferably 0.01 or more based on the mass. 0.4 or less, more preferably 0.01 or more and 0.2 or less, more preferably 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 this embodiment, the content of carboxylic acid (C) and carboxylic anhydride (D) is not particularly limited, and relative to the total amount of reaction product (P) (100% by mass; it does not contain solvents, solvent components, and fillers). In terms of the solid content of the material (J)), it is preferably 0.5% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and more preferably 1.0% by mass or more and 5.0% by mass or less. In addition, the content of carboxylic acid (C) and carboxylic anhydride (D), when the reaction product (P) and the thermosetting component (E) are combined, are relative to the ratio of the reaction product (P) and the thermosetting component (E) The total amount (100% by mass; in terms of the amount of solid content not containing solvents, solvent components, and fillers (J)) is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5.0% by mass or less , More preferably 0.2% by mass or more and 2.0% by mass or less. When the content of carboxylic acid (C) and carboxylic anhydride (D) is within the above range, there is a tendency to obtain a printed circuit board with better moldability, thermoelastic modulus, scumming resistance, and chemical resistance.

[Thermosetting component (E)] The resin composition of this embodiment preferably further contains the thermosetting component (E).

The thermosetting component (E) used in this embodiment is not particularly limited as long as it is a component that is hardened by heat. The thermosetting component (E) is not particularly limited. For example, the above-mentioned amino-modified polysiloxane (A), maleimide compound (B), and epoxy resin (F), cyanate ester described below, Compound (G), and nadiimide (H) substituted with alkenyl. That is, the amine-modified polysiloxane (A) and the maleimide compound (B) used as the thermosetting component (E) can be used with the above-mentioned amine-modified polysiloxane (A), It is the same as the maleimide compound (B). Among them, the thermosetting component (E) preferably contains selected from the maleimide compound (B), epoxy resin (F), cyanate ester compound (G), and nadic acid substituted with alkenyl groups. One or two or more of the group consisting of the amine (H) is preferable, and the maleimide compound (B) is more preferable.

In the resin composition of this embodiment, the content of the thermosetting component (E) is not particularly limited. When the reaction product (P) and the thermosetting component (E) are combined, the content of the reaction product (P) and the thermosetting The total amount of the sexual component (E) (100% by mass; as far as the solid content of the solvent, solvent component and filler (J) is not included), it is preferably 20% by mass or more and 85% by mass or less, more preferably 30 Mass% or more and 85% by mass or less, more preferably 40% by mass or more and 80% by mass or less. When the content of the thermosetting component (E) is within the above-mentioned range, it tends to become a printed circuit board with excellent formability, thermoelastic modulus, scumming resistance, and chemical resistance even when the filler is filled.

<Epoxy resin (F)> By containing the epoxy resin (F), the resin composition of the present embodiment tends to be more excellent in adhesiveness, moisture absorption and heat resistance, flexibility, etc. 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: bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A novolac epoxy resin, biphenyl Type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, xylene novolak type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified phenolic resin Varnish type epoxy resin, naphthyl ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, triglycidyl Based isocyanurate, glycidyl epoxy resin, cycloaliphatic epoxy resin, dicyclopentadiene novolac epoxy resin, biphenol novolac epoxy resin, phenol aralkyl novolac Type epoxy resin, naphthol aralkyl novolak type epoxy resin, aralkyl novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentane Diene epoxy resins, polyol epoxy resins, phosphorus-containing epoxy resins, glycidylamine, compounds obtained by epoxidizing butadiene and other double bonds, hydroxyl-containing silicone resins and table Compounds obtained by the reaction of chlorohydrins and these halides.

Among them, the epoxy resin (F) is selected from the group consisting of biphenyl aralkyl type epoxy resin, naphthyl ether type epoxy resin, multifunctional phenol type epoxy resin, and naphthalene type epoxy resin. More than one kind in the group is preferred. By containing such epoxy resin (F), the flame retardancy and heat resistance of the cured product obtained tend to be more improved.

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

In the resin composition of this embodiment, the content of the epoxy resin (F) is not particularly limited, and is relative to the total amount (100% by mass) of the reaction product (P) and the thermosetting component (E); no solvent or solvent is included. In terms of the solid content of ingredients and fillers (J)), 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 within the above range, the adhesiveness and flexibility tend to be more excellent.

<Cyanate ester compound (G)> The cyanate ester compound (G) used in this embodiment is not particularly limited. For example, the naphthol aralkyl type cyanate ester represented by the following general formula (3), the following general formula (4) ) Means novolac type cyanate ester, biphenyl aralkyl type cyanate ester, bis(3,3-dimethyl-4-cyanooxyphenyl)methane, bis(4-cyanooxyphenyl) Methane, 1,3-dicyanooxybenzene, 1,4-dicyanooxybenzene, 1,3,5-tricyanooxybenzene, 1,3-dicyanooxynaphthalene, 1,4-dicyanooxybenzene Oxynaphthalene, 1,6-dicyanooxynaphthalene, 1,8-dicyanooxynaphthalene, 2,6-dicyanooxynaphthalene, 2,7-dicyanooxynaphthalene, 1,3,6- Tricyanooxynaphthalene, 4,4'-dicyanooxybiphenyl, bis(4-cyanooxyphenyl) ether, bis(4-cyanooxyphenyl)sulfide, bis(4-cyanooxy) Phenyl) sulfide, and 2,2-bis(4-cyanooxyphenyl)propane.

Among them, the naphthol aralkyl type cyanate compound represented by the following general formula (3), the novolak type cyanate ester represented by the following general formula (4), and the biphenyl aralkyl type cyanate ester are because they are flame retardant Excellent properties, high curability, and low thermal expansion coefficient of the cured product, it is particularly desirable, selected from the naphthol aralkyl type 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 esters is more desirable.

式(3)中，多數個R₆ 各自獨立地表示氫原子或甲基，n₂ 表示1以上之整數。[化5]

In the formula (3), a plurality of R ₆ each independently represents 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 represents 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 value of n ₂ is preferably 10, more preferably 6.

式(4)中，多數個R₇ 各自獨立地表示氫原子或甲基，多數個R₈ 各自獨立地表示氫原子或碳數為1~4之烷基或烯基，n₃ 表示1以上之整數。[化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 represents one or more Integer.

In the formula (4), a plurality of R ₇ each independently represents a hydrogen atom or a methyl group, and preferably represents a hydrogen atom.

In formula (4), a plurality of R ₈ each independently represents 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 of n ₃ is preferably 10, more preferably 7.

The production method of these cyanate ester compounds is not particularly limited, and can be produced in accordance with various existing methods for the cyanate ester synthesis method. For specific examples, it can be obtained by reacting the naphthol aralkyl type phenol resin represented by the following general formula (5) with a cyanogen halide in a passive organic solvent in the presence of a basic compound. In addition, a method of forming a salt made of the same naphthol aralkyl phenol resin and a basic compound in a solution containing water, and then performing a two-phase interfacial reaction with cyanogen halide to synthesize.

式(5)中，多數個R₆ 各自獨立地表示氫原子或甲基，n₄ 表示1以上之整數。[化7]

In formula (5), a plurality of R ₆ each independently represents 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 represents 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 of n ₄ is preferably 10, more preferably 6.

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

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

In the resin composition of this embodiment, the content of the cyanate ester compound (G) is not particularly limited, and is relative to the total amount of the reaction product (P) and the thermosetting component (E) (100% by mass; no solvent is included) In terms of the solid content of the solvent component and 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% the following. When the content of the cyanate ester compound (G) is within the above-mentioned range, there is a tendency to obtain a printed circuit board with better moldability, thermoelastic modulus, desmear resistance, and chemical resistance.

<Alkenyl-substituted Nadicimines (H)> The alkenyl-substituted nadicimines (F) used in this embodiment, as long as there are more than one alkenyl substituted sodium in the molecule The compound of the diketimine group is sufficient, and there is no particular limitation. Specific examples thereof include compounds represented by the following general formula (6).

[化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 represents an alkylene group, a phenylene group, a biphenylene group, and a C1-C6 alkylene group. Naphthyl, or a group represented by the following general formula (7) or (8).

[化9]

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

[化10]

In the formula (8), a plurality of R ₄ each independently represents 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 can also be used for the alkenyl substituted nadicimines (F) represented by the formula (6). Commercial products are not particularly limited. For example, the compound represented by the following formula (9) (BANI-M (Maruzen Petrochemical Co., Ltd.)), the compound represented by the following formula (10) (BANI-X (Maruzen Petrochemical Co., Ltd.) )System)) etc.

The alkenyl substituted nadicimines (H) may be used singly or in combination of two or more.

[化11]

[化12]

In the resin composition of this embodiment, the content of the alkenyl-substituted nadicimine (H) is not particularly limited, and is relative to the total amount (100% by mass) of the reaction product (P) and the thermosetting component (E) ; As far as the solid content of the solvent, solvent component and filler (J) is not included), it is 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, and more preferably 20 More than 40% by mass. By having the content of alkenyl substituted nadicimine (H) within the above range, it is possible to obtain a printed circuit board with better formability, thermoelastic modulus, scum resistance, and chemical resistance. tendency.

The above-mentioned epoxy resin (F), cyanate ester compound (G), and alkenyl substituted nadicimines (H) can also be used as raw materials for the reaction product (P).

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

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) within a range that does not impair the expected characteristics. The type of the other resin is not particularly limited as long as it has insulating properties, for example, a thermoplastic resin. By appropriately combining thermoplastic resins. It can impart characteristics such as metal adhesion and stress relaxation.

[Filling material (J)] The resin composition of this embodiment preferably further contains a filler (J). The filler (J) is not particularly limited as long as it has insulating properties, such as natural silica, fused silica, amorphous silica, hollow silica and other silicas; 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 fiber (E glass, D Fine glass powders such as glass), inorganic fillers such as insulating glass and spherical glass, and organic fillers such as silicone rubber and polysilicon composite powder. One of these can be used, or two or more of them can be appropriately mixed and used.

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

In the resin composition of the present embodiment, the content of the filler (J) is not particularly limited. When the reaction product (P) and the thermosetting component (E) are combined, it is relative to the reaction product (P) and the thermosetting component The total amount of (E) (100 parts by mass; in terms of the amount of solid content that does not contain solvents, solvent components, and fillers (J)) or the total amount of reaction products (P) when only the reaction product (P) is used ( 100 parts by mass; as far as the solid content of the filler (J) is not solvent, solvent components, etc.), if the content of filler (J) is 50 parts by mass or more and 300 parts by mass or less, low thermal expansion and high thermal conductivity should be considered The viewpoint of such characteristics is more desirable. Among them, 100 parts by mass or more and 300 parts by mass or less are more preferable, and 100 parts by mass or more and 250 parts by mass or less are more preferable.

[Silane coupling agent, wetting and dispersing agent] In the resin composition of this embodiment, in order to improve the dispersibility of the filler particles, the adhesive strength of the resin and the particles, and the glass cloth, a silane coupling agent and/or wetting can also be used in combination. Dispersant. As long as the silane coupling agents are generally used in the surface treatment of inorganic substances, there are no special restrictions. Specific examples, such as: γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane and other aminosilane series; γ-glycidoxy Silane oxide series such as propyl propyl trimethoxysilane; Acrylic silane series such as γ-acryloxy propyl trimethoxysilane; N-β-(N-vinylbenzylaminoethyl)-γ-amine Cationic silane coupling agents such as propyl trimethoxysilane hydrochloride; phenyl aryl silane coupling agents such as styryl silane can be used singly or in combination of two or more. In addition, as for the wetting and dispersing agent, as long as it is a dispersion stabilizer used in coating applications, there are no special restrictions. Specific examples include, for example, wetting and dispersing agents such as DISPER-BYK110, 111, 118, 180, 161, BYK-W996, W9010, and W903 manufactured by BYK Chemie Japan.

啉、三乙醇胺、三乙二胺、四甲基丁烷二胺、N-甲基哌啶等三級胺類；苯酚、二甲酚、甲酚、間苯二酚、兒茶酚等苯酚類；環烷酸鉛、硬脂酸鉛、環烷酸鋅、辛酸鋅、油酸錫、蘋果酸二丁基錫、環烷酸錳、環烷酸鈷、乙醯基丙酮鐵等有機金屬鹽；此等有機金屬鹽溶解在苯酚、雙酚等含羥基之化合物而成者；氯化錫、氯化鋅、氯化鋁等無機金屬鹽；二辛基氧化錫、其他之烷基錫、烷基氧化錫等有機錫化合物、及三苯基咪唑(TPIZ)。[Curing accelerator] In the resin composition of the present embodiment, a curing accelerator may be used in combination within a range that does not impair the expected characteristics. The hardening accelerator is not particularly limited, and examples include organic peroxides such as benzyl peroxide, laurel peroxide, acetyl peroxide, p-chlorobenzyl peroxide, di-tert-butyl diperoxyphthalate, etc. Oxides; azo compounds such as azobisnitriles; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol , Tri-n-butylamine, pyridine, quinoline, N-methyl

Tertiary amines such as morpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, catechol, etc. ; Lead naphthenate, lead stearate, zinc naphthenate, zinc octanoate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone and other organic metal salts; these Organic metal salt is dissolved in phenol, bisphenol and other hydroxyl-containing compounds; tin chloride, zinc chloride, aluminum chloride and other inorganic metal salts; dioctyl tin oxide, other alkyl tin, alkyl tin oxide Other organotin compounds, and triphenylimidazole (TPIZ).

[Organic Solvent] The resin composition of this embodiment may contain a solvent if necessary. For example, if an organic solvent is used, the viscosity during the preparation of the resin composition will decrease, the workability will be improved, and the impregnation of the glass cloth can be improved. The type of solvent is not particularly limited as long as part or all of the resin in the resin composition is soluble. The specific examples are not particularly limited, for example: ketones such as acetone, methyl ethyl ketone, and methyl serotonin; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and its ethyl esters Acid ester. One type of solvent can be used, or two or more types can be used in combination.

環之化合物。就添加劑而言，可將紫外線吸收劑、抗氧化劑、光聚合起始劑、螢光增白劑、光增感劑、染料、顏料、增黏劑、潤滑劑、消泡劑、表面調整劑、光澤劑、聚合抑制劑等因應需要而適當組合使用。[Other components] In the resin composition of this embodiment, various polymer compounds such as other thermosetting resins, thermoplastic resins and their oligomers, elastomers, etc. can also be used in combination within the range that does not impair the expected characteristics; other flame retardant Sexual compounds; additives, etc. As long as they are general users, there are no special restrictions. For example: flame retardant compounds can include nitrogen-containing compounds such as melamine, benzoguanamine, etc.,

Ring compound. As for additives, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, tackifiers, lubricants, defoamers, surface regulators, Brighteners, polymerization inhibitors, etc. are appropriately combined and used according to needs.

[Method for producing resin composition] The method for producing a resin composition of this embodiment can be modified by amino group-modified polysiloxane (A), maleimide compound (B), and carboxylic acid (C) and The reaction product (P) obtained by reacting at least one of the carboxylic anhydrides (D) is directly used as the resin composition. In addition, the obtained reaction product (P) and the thermosetting component (B) can be mixed to obtain a resin composition. Furthermore, other optional ingredients can be mixed as needed.

The method for producing the resin composition of this embodiment is not particularly limited. In an ideal form, it has the ability to react the amino-modified polysiloxane (A) with the maleimide compound (B) to obtain a primary polymer. The first reaction step (hereinafter also simply referred to as the "first reaction step"), and the second reaction step (hereinafter also referred to as the "first reaction step") and the second reaction step of reacting the primary polymer and at least one of the carboxylic acid (C) and the carboxylic anhydride (D) Simply referred to as the "second reaction step"), it is desirable to obtain better storage stability of the reaction product (P).

The reaction temperature in the first reaction step may be the temperature at which the reaction of the amino-modified polysiloxane (A) and the maleimide compound (B) will proceed, and it is not particularly limited. It is 50°C to 200°C. Good, 100℃~150℃ is even better.

Supplying the viscosity of the primary polymer obtained in the first reaction step in the second reaction step, considering the point of view of obtaining better storage stability of the reaction product (P), it is preferably 100~500mPa·s, 150mPa·s~400mPa・S is better. In addition, the method for measuring the viscosity of the primary polymer is not particularly limited, and it can be measured with a general viscometer. For example, a cone-plate viscometer (for example: ICI viscometer) can be used for measurement.

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

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

In the first step and the second step, at least one of the amine-modified polysiloxane (A), maleimide compound (B), carboxylic acid (C), and carboxylic anhydride (D), and a polymerization In order to improve their operability, it is better to dilute with a solvent. The type of solvent is not particularly limited, for example: ketones such as acetone, methyl ethyl ketone, methyl serotonin; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and its ethyl esters Acid ester. One type of solvent can be used, or two or more types can be used in combination.

In the production of the resin composition, a known treatment (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component may also be performed. When the filler (J) and other fillers are uniformly dispersed, the dispersibility of the resin composition can be improved by using a stirring tank equipped with a stirrer with appropriate stirring ability to perform the stirring and dispersing treatment. The above-mentioned stirring, mixing, and kneading treatments can be suitably carried out using a known device such as a ball mill or a bead mill for mixing, or a revolving or self-transforming mixing device.

[Prepreg] The prepreg of this embodiment has a substrate and the resin composition of this embodiment impregnated or coated on the substrate. The manufacturing method of the prepreg can be carried out in accordance with common methods without special restrictions. For example: after impregnating or coating the above resin composition on the substrate, it is heated in a dryer at 100 to 200°C for 1 to 30 minutes to semi-cured (B-staged) to obtain the prepreg method. Also, in this embodiment, the content of the resin composition (including fillers and additive components) relative to the total amount of the prepreg (100% by mass) is not particularly limited, but a range of 30% by mass to 90% by mass is preferable .

唑(poly(p-phenylene-2,6-benzobisoxazole)(Zylon(註冊商標)、東洋紡(股)公司製)、聚醯亞胺等有機纖維。The base material used in 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 intended use and performance. The specific examples are not particularly limited, and examples 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-terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copolymerized paraphenylene, 3,4'oxydiphenylene, and p-xylylenedimethamide (Technora (registered trademark) , Teijin Technoproducts Co., Ltd.) and other wholly aromatic polyamides, 2,6-hydroxynaphthoic acid and p-hydroxybenzoic acid (Vectran (registered trademark), Kuraray Co., Ltd.) and other polyesters, polymer Benzobis

Organic fibers such as poly(p-phenylene-2,6-benzobisoxazole) (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.), and polyimide.

Among them, considering the viewpoint of low thermal expansion, it is preferable to select one or more kinds selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fiber. .

The shape of the substrate is not particularly limited, such as woven fabric, non-woven fabric, roving, strand mat, and surface mat. The weaving method of the weaving cloth is not particularly limited. For example, plain weave, basket weave, and twill weave are known, and can be appropriately selected from these known products according to the intended use and performance. In addition, it is suitable to use glass woven fabrics that have been subjected to fiber opening treatment and surface-treated with a silane coupling agent. The thickness and quality of the substrate are not particularly limited, and it is usually suitable to use about 0.01~0.3mm. In particular, considering the strength and water absorption, the substrate should preferably be a ^{glass woven fabric with a thickness of 200μm or less and a mass of 250g/m 2} or less. It is preferably a glass woven fabric composed of glass fibers such as E glass, S glass, and T glass. More ideal.

The laminated board of this embodiment can be obtained, for example, by stacking a plurality of sheets of the above-mentioned prepreg and curing them. In addition, the metal foil-clad laminate of this embodiment can be obtained, for example, by laminating the above-mentioned prepreg and metal foil and hardening.

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 foils on one or both sides of the prepreg, and laminating and molding them. More specifically, by stacking one or more of the above-mentioned prepregs, arranging metal foils such as copper and aluminum on one or both sides as necessary, and laminating and forming them as necessary to obtain a coating Metal foil laminated board. The metal foil used here is not particularly limited as long as it is used in printed circuit board materials, and it is preferably a known copper foil such as rolled copper foil and electrolytic copper foil. Furthermore, the thickness of the metal foil is not particularly limited, but 1.0 μm or more and 70 μm or less is preferable, and more preferably 1.5 μm or more and 35 μm or less. The forming method and forming conditions of the metal foil-clad laminate are also not particularly limited, and the methods and conditions of general laminates and multilayer boards for printed circuit boards can be used. For example, a multi-stage pressing machine, a multi-stage vacuum pressing machine, a continuous forming machine, an autoclave forming machine, etc. can be used when forming a metal foil-clad laminate. In addition, when forming a metal foil-clad laminate, generally, the temperature is 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 can be post-cured at a temperature of 150~300℃. In addition, the above-mentioned prepreg and a separately produced wiring board for the 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-clad laminate of this embodiment has low thermal expansion, good formability, metal foil peeling strength, and chemical resistance (especially resistance to scumming), and can be effectively used as a semiconductor package that requires such performance. Use printed circuit boards.

In addition, in this embodiment, in addition to the form of the above-mentioned prepreg, the form of a landfill sheet in which the above-mentioned resin composition is coated on a metal foil or a thin film may also be adopted.

[Resin Sheet] The resin sheet of this embodiment has a support and the resin composition of this embodiment arranged on the surface of the support. It is a resin sheet obtained by coating the above-mentioned resin composition on one or both sides of a support. Here, the resin sheet can be manufactured by directly coating the thermosetting resin (including filler) used in prepregs, etc., on a support such as metal foil, film, etc., and drying it. .

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

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

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

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

In addition, the metal foil-clad laminate of this embodiment can be obtained, for example, by laminating the above-mentioned resin sheet and metal foil and hardening.

Specifically, the metal foil-clad laminate of the present embodiment can be obtained by using the above-mentioned resin sheet, and arranging and laminating metal foils on one or both sides of the resin sheet. More specifically, for example, one or more of the aforementioned resin sheets are peeled off the support as needed, and then a plurality of sheets are stacked, and metal foils such as copper and aluminum are placed on one or both sides of the resin sheet, and then laminated and formed as needed. , To manufacture metal-clad laminates. The metal foil used here is not particularly limited as long as it is used in printed circuit board materials, and it is preferably a known copper foil such as rolled copper foil and electrolytic copper foil. The forming method and forming conditions of the metal foil-clad laminate are not particularly limited, and the methods and conditions of general laminates and multilayer boards for printed circuit boards can be used. For example: Multi-stage presses, multi-stage vacuum presses, continuous forming machines, autoclave forming machines, etc. can be used when forming metal-clad laminates. In addition, when forming a metal foil-clad laminate, generally, the temperature is 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 can be performed at a temperature of 150 to 300°C.

The laminated board of this embodiment may be a laminated board having a large number of resin sheets and/or prepregs, or a metal foil-clad laminated board having resin sheets and/or prepregs, and metal foil. These laminated boards can be obtained by stacking and hardening resin sheets, prepregs, and metal foils.

In this embodiment, when a conductor layer that becomes a circuit is formed and a printed circuit board is produced, if the form of a metal foil-clad laminate is not adopted, the method of electroless plating can also 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 the surface of the insulating layer.

The printed circuit board of this embodiment can be produced by forming a metal foil on an insulating layer, and forming a conductor layer that becomes a circuit by electroless plating, for example. The conductor layer is generally composed of copper and aluminum. The insulating layer for a printed circuit board with a conductor layer formed is suitable for use on a printed circuit board by forming a predetermined wiring pattern. The printed circuit board of this embodiment contains the above-mentioned resin composition in 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 It has excellent peel strength and scumming resistance, so it is particularly effective as a printed circuit board for semiconductor packages.

Specifically, the printed circuit board of this embodiment can be 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 circuit of the inner substrate is subjected to surface treatment to increase the adhesion strength as needed. Secondly, the required number of the above-mentioned prepregs are superimposed on the surface of the inner circuit, and the metal for the outer circuit is laminated on the outer side. The foil is heated and pressurized and integrally formed. In this way, a base material and an insulating layer composed of a cured product of a thermosetting resin composition are formed between the metal foil for the inner layer circuit and the outer layer circuit, and a multi-layer laminated board is produced. Secondly, after drilling through holes and via holes on the multilayer laminate, in order to remove the resin residue from the resin component contained in the hardened layer, a desmear treatment is performed. After that, a plated metal film is formed on the wall surface of the hole to connect the metal foil for the inner layer circuit and the outer layer circuit, and then the metal foil for the outer layer circuit is etched to form the outer layer circuit to manufacture a printed circuit board.

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

Hereinafter, the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited by these examples.

式中，N表示聚合物分子之數目，M表示分子量，C表示試樣濃度。試樣濃度C和單體之單位數成比例，故C＝M×N。[Weight average molecular weight] The weight average molecular weight of the reaction product is measured by the gel permeation chromatography (GPC) method using the resin composition obtained in the following examples and comparative examples as a sample, and using a standard polystyrene calibration curve , Calculate the conversion value. Specifically, the relationship between the elution time from the column and the molecular weight is first obtained, and the elution time is replaced with the molecular weight based on this relationship. The graph representing the "relationship between dissolution time and molecular weight" used at this time is called "calibration curve" (or calibration curve). "The relationship between dissolution time and molecular weight" varies with each type of polymer. In principle, a standard polymer with the same structure and a known molecular weight with a narrow molecular weight distribution must be used as the measurement object. But in reality, there are almost all difficulties, so the actual system is to use commercially available standard polymers. Here, polystyrene is used as the standard polymer. The molecular weight obtained in this way is called the standard converted molecular weight. Accordingly, the weight average molecular weight (Mw) can be calculated from the following formula. [Number 1]

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

[Synthesis example 1] Synthesis of α-naphthol aralkyl cyanate ester resin The reactor equipped with thermometer, stirrer, dropping funnel and reflux cooler was cooled to 0~5℃ with brine in advance, and added to it 7.47g (0.122mol) of cyanogen chloride, 9.75g (0.0935mol) of 35% hydrochloric acid, 76mL of water, and 44mL of dichloromethane.

n₄ 表示1以上之整數。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 phenol resin (SN485, OH group equivalent: 214g/eq. Softening point: 86°C, manufactured by Nippon Steel Chemical Co., Ltd.) 20g (0.0935mol), and 14.16g (0.14mol) of triethylamine are dissolved in After the solution of 92 ml of dichloromethane was added, 4.72 g (0.047 mol) of triethylamine was added dropwise for 15 minutes. [化13]

n ₄ represents an integer of 1 or more.

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

[Example 1] 25 parts by mass of a maleimide compound (maleimide equivalent 285 g/eq, trade name "BMI-80" manufactured by KI Kasei Co., Ltd.) under the conditions of heating and reflux temperature of 130°C Dissolved in a solution of 40 parts by mass of propylene glycol monomethyl ether (manufactured by KHneochem) to make diamine-modified polysiloxane (X-22-161B, amine equivalent 1500g/eq, a product manufactured by Shin-Etsu Chemical Co., Ltd.) Name "X-22-161B") 15 parts by mass were dissolved to prepare a primary polymer. After that, continue to stir under the condition of heating and reflux temperature of 130℃. When the viscosity of the primary polymer increases to 200~300mPa·s measured by ICI viscometer (cone-plate viscometer, manufactured by Towa Industry Co., Ltd.), Add 1.0 part by mass of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) to the polymer and dissolve it in 22.5 parts by mass of propylene glycol monoethyl ether acetate (manufactured by Dow Chemical Co., Ltd.), and maintain it at a reflux temperature of 130°C. After reacting for several hours, a resin composition containing the reaction product is 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. Furthermore, 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.), except that the same method as in Example 1 was followed to obtain a reaction product containing a weight average molecular weight of 13,200 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. Furthermore, 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.), except that the same method as in Example 1 was followed to obtain a product containing a weight average molecular weight of 12,500 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] 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.), except that the same method as in Example 1 was followed to obtain a reaction product containing a weight average molecular weight of 12,000 The 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. Furthermore, 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 with 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. Furthermore, 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] Without using 1.0 part by mass of maleic anhydride and 22.5 parts by mass of propylene glycol monoethyl ether acetate, the same method as in Example 1 was followed to obtain a resin composition containing a reaction product with a weight average molecular weight of 13,900 . A part of the obtained resin composition was used as a sample, and the weight average molecular weight of the reaction product was measured. Furthermore, 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 with 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. Furthermore, 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. In addition, the "weight average molecular weight" of the resin composition before storage does not refer to the value measured immediately after obtaining each resin composition, but the value measured on the day when each resin composition was obtained. Therefore, the initial storage stability can be compared with the results of the "weight average molecular weight" in Table 1.

[Example 6] 41.0 parts by mass of the resin composition obtained in Example 1, maleimide compound (maleimide group equivalent 186 g/eq, trade name "BMI-2300" manufactured by Daiwa Chemical Industry Co., Ltd.) 30 parts by mass, biphenol novolac type epoxy resin (trade name "NC-3000FH" manufactured by Nippon Kayaku Co., Ltd.) 4.5 parts by mass, bis-diallyl nadic imide (alkenyl equivalent 286 g/eq, Maruzen 25 parts by mass of the trade name "BANI-M" manufactured by Petrochemical Corporation, 0.5 parts by mass of the cyanate ester of α-naphthol aralkyl phenol resin obtained in Synthesis Example 1 above, and slurry silica (manufactured by Admatechs) Product name "SC-2050MB") 200 parts by mass, epoxy silane coupling agent (product name "Z6040" manufactured by Toray Dow Corning Corporation) 5 parts by mass, and triphenylimidazole (Tokyo Chemical Industry Co., Ltd.) as a hardening accelerator Made 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] For each resin composition obtained in Example 6 and Comparative Example 3, the amine value was measured. 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] The resin compositions obtained in Example 6 and Comparative Example 3 were diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on T glass cloth (T2118), heated and dried at 150°C for 3 minutes, and adjusted the content (mass%) of the resin composition so that the thickness of the insulating layer when the following laminated board is made is 100μm, Obtain a prepreg.

[Varnish gel time] A part of each varnish obtained when the above-mentioned prepreg was produced was used as a sample, and the gel time (sec) at 170°C was measured. In addition, 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] Obtain the resin composition from the prepreg prepared according to the above method, and use a dynamic viscoelasticity measuring device (trade name "AR2000" manufactured by TA Instrument) to measure the angular velocity of 1rad/s and the geometric gap of 1mm at 120°C The viscosity of the measurement conditions (mPa·s). In addition, the above-mentioned prepreg was stored at 25°C for 7 days, and the resin component was obtained from the stored prepreg, and the shear viscosity (mPa·s) was measured in the same manner as described above. The results are shown in Table 2.

[Table 2]

[Laminated board] A 12μm-thick electrolytic copper foil (trade name "3EC-III" manufactured by Mitsui Mining & Mining Co., Ltd.) is placed on and under one piece of the obtained prepreg. The pressure is 30kgf/cm ² and the temperature is 220°C for 120°C. It takes minutes to laminate and form to obtain a copper-clad laminate with an insulating layer thickness of 100μm (formed before storage). In addition, the obtained prepreg was stored at 25°C for 7 days, and one sheet of the stored prepreg was used for lamination forming in the same manner as above to obtain a copper-clad laminate with an insulating layer thickness of 100μm (Forming after preservation).

[Thermal expansion rate] The obtained copper-clad laminates (formed before storage and formed after storage) were completely etched to remove the copper foil, and then heated from 40°C at 10°C per minute using a thermomechanical analysis device (manufactured by TA INSTRUMENT) At 340°C, the coefficient of linear expansion in the plane direction from 60°C to 120°C was measured, and the obtained value was used as the evaluation value of the thermal expansion coefficient (ppm/degC). The measuring direction is to measure the longitudinal direction (Warp) of the glass cloth of the laminated board. The results are shown in Table 3.

[table 3]

This application is based on the Japanese patent application filed with the Japan Patent Office on April 5, 2016 (Japanese Patent Application No. 2016-076144) and the Japanese patent application filed with the Japan Patent Office on January 5, 2017 (Japan Patent Office). May 2017-000666), and use their content as a reference here. [Industrial Utilization]

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

Claims (20)

A resin composition comprising a reaction product (P), the reaction product (P) is a primary polymer obtained by reacting an amine-modified polysiloxane (A) with a maleimide compound (B), and a carboxylic acid It is obtained by reacting at least one of (C) and carboxylic anhydride (D). For example, the resin composition of item 1 in the scope of patent application, wherein the amine value of the resin composition is 2.0 mgKOH/g or less. For example, the resin composition of item 1 or 2 of the scope of patent application, wherein the reaction product (P) is obtained by at least reacting the carboxylic anhydride (D), and the carboxylic anhydride (D) is selected from maleic anhydride, One or two or more of the group consisting of phthalic anhydride, succinic anhydride, and acetic anhydride. For example, the resin composition of item 1 or 2 of the scope of patent application, wherein the reaction product (P) is obtained by reacting at least the carboxylic acid (C), and the carboxylic acid (C) is selected from maleic acid, One or two or more of the group consisting of phthalic acid, succinic acid, and acetic acid. For example, the resin composition of item 1 or 2 of the scope of patent application further contains thermosetting component (E). For example, the resin composition of item 5 of the scope of patent application, wherein the thermosetting component (E) contains selected from maleimide compound (B), epoxy resin (F), cyanate ester compound (G ), and one or more of the group consisting of nadiimide (H) substituted with alkenyl groups. For example, the resin composition of item 1 or 2 of the scope of patent application, wherein the amino-modified polysiloxane (A) in the reaction product (P) comprises a compound represented by the following general 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 represents an integer of 1 or more. For example, the resin composition of item 1 or 2 in the scope of patent application, wherein the amino group equivalent of the amino-modified polysiloxane (A) in the reaction product (P) is 130 or more and 6000 or less. For example, the resin composition of item 1 or 2 in the scope of the patent application, wherein the maleimide compound (B) contains selected from the group consisting of bis(4-maleiminophenyl) methane, 2,2-bis {4-(4-Maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, polycyclobutane oxidation One or two or more of the group consisting of bis(4-maleimidin benzoate) and the compound represented by the following general formula (2); [化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. For example, the resin composition of item 1 or 2 of the scope of patent application further contains filler (J). For example, the resin composition of item 10 of the scope of patent application, wherein the filler (J) contains one or two or more selected from the group consisting of silicon dioxide, aluminum oxide, and aluminum nitride. For example, the resin composition of item 10 of the scope of patent application, 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 thermosetting component (E) The following filler (J). A prepreg has: a substrate; and a resin composition such as any one of items 1 to 12 in the scope of patent application impregnated or coated on the substrate. Such as the prepreg of item 13 of the scope of patent application, wherein the substrate is selected from one or two of the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers the above. A resin sheet has: a support; and a resin composition such as any one of items 1 to 12 of the scope of patent application arranged on the surface of the support. For example, the resin sheet of item 15 in the scope of patent application, wherein the support is a resin sheet or metal foil. A laminated board having a plurality of one or more selected from the group consisting of the prepreg of the 13th or 14th patent application and the resin sheet of the 15th or 16th patent application . A metal foil-clad laminate having: one or two selected from the group consisting of a prepreg as in the scope of patent application 13 or 14 and a resin sheet as in the scope of patent application 15 or 16 More than species; and metal foil. A printed circuit board has: an insulating layer containing the resin composition of any one of items 1 to 12 in the scope of the patent application; and a conductor layer formed on the surface of the insulating layer. A method for producing a resin composition includes: 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 step of reacting The primary polymer reacts with at least one of the carboxylic acid (C) and the carboxylic anhydride (D).