TW202146576A - Resin composition, cured product of resin composition, resin sheet, printed wiring board, and semiconductor device containing (A) a polycarbonate resin and (B) a maleimide compound - Google Patents

Abstract

A subject of this invention is to provide a resin composition which may obtain a cured product having excellent adhesion and chemical resistance; a cured product of the resin composition; a resin sheet containing the resin composition; a printed wiring board including an insulating layer formed by the cured product of the resin composition, and a semiconductor device. Means for solving this subject is to provide a resin composition of the present invention, which contains (A) a polycarbonate resin and (B) a maleimide compound, wherein the maleimide compound contains a hydrocarbon chain of at least any one of an alkyl group having more than 5 carbon atoms and an alkylene group having more than 5 carbon atoms.

Description

Resin composition, cured product of resin composition, resin sheet, printed wiring board, and semiconductor device

The present invention relates to a resin composition. Furthermore, it is about the hardened|cured material of this resin composition, and the resin sheet obtained by using this resin composition, a printed wiring board, and a semiconductor device.

As a manufacturing technique of the printed wiring board for semiconductor devices, the manufacturing method of the build-up system by overlapping an insulating layer and a conductor layer alternately is known. In addition, the wiring system formed on the insulating layer is further miniaturized.

Patent Document 1 discloses, for example, a resin composition containing a maleimide compound as an insulating material used for a printed wiring board of such an insulating layer. In addition, in the applicant's unpublished patent application (application number: Japanese Patent Application No. 2019-061616; publication number: JP 2020-158705 A), a resin containing a maleimide compound is also described composition. Moreover, patent document 2 discloses a resin composition containing a polycarbonate resin as an insulating material of a printed wiring board. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2019-044128 [Patent Document 2] Japanese Patent Laid-Open No. 2019-035056

[The problem to be solved by the invention]

However, in recent years, as the frequency of the signal in the circuit board of the semiconductor device increases, the insulating layer is required to have excellent dielectric properties. Here, since a cured product of a resin composition containing a maleimide compound is generally excellent in dielectric properties, the use of a maleimide compound in the resin composition has been studied.

However, as a result of research by the present inventors, it was found that "the hardened material of the resin composition containing the maleimide compound has a dense bond between the hardened material and the conductor (for example, copper foil) provided on the hardened material as a base. The adhesion (hereinafter also referred to as "substrate adhesion") may be poor, and further, the adhesion of the plating provided on the hardened material (hereinafter also referred to as "plating adhesion") may also be There is a bad situation." In addition, the base adhesion and plating adhesion are sometimes referred to as "adhesion".

In addition, as a result of research by the present inventors, it was found that "the cured product of the resin composition containing the maleimide compound may have poor chemical resistance". When the chemical resistance of the cured product is poor, when the surface of the insulating layer for plating or the like is exposed to a chemical solution (for example, an alkaline solution), the surface is excessively roughened, and as a result, particularly high The skin effect in frequency applications may become larger.

The subject of the present invention is to provide a resin composition which can obtain a cured product excellent in adhesion and chemical resistance; a cured product of the resin composition; a resin sheet comprising the resin composition; A printed wiring board and a semiconductor device of an insulating layer formed of the cured product. [Means of Solving Problems]

As a result of intensive research, the present inventors found that "By using (A) a polycarbonate resin and (B) a maleimide compound in combination, the maleimide compound contains 5 or more carbon atoms. At least one hydrocarbon chain among the alkyl group and the alkylene group having 5 or more carbon atoms can solve the above-mentioned problems", thus completing the present invention.

一般式(B1)中，M表示可具有取代基的包含碳原子數為5以上的伸烷基的2價的脂肪族烴基，L表示單鍵或2價的連結基。 [8]. 如[1]~[7]中任一項之樹脂組成物，其中，(B)成分為馬來醯亞胺化合物，該馬來醯亞胺化合物包含碳原子數為5以上50以下的烷基及碳原子數為5以上50以下的伸烷基中之至少任1種的烴鏈。 [9]. 如[1]~[8]中任一項之樹脂組成物，其中，將樹脂組成物中的不揮發成分設為100質量%時，(B)成分的含有量為0.1質量%以上且60質量%以下。 [10]. 如[1]~[9]中任一項之樹脂組成物，其中，進而包含(C)無機填充材。 [11]. 如[10]之樹脂組成物，其中，將樹脂組成物中的不揮發成分設為100質量%時，(C)成分的含有量為30質量%以上。 [12]. 如[1]~[11]中任一項之樹脂組成物，其中，進而包含(D)自由基聚合性化合物。 [13]. 如[12]之樹脂組成物，其中，(D)成分係分子中包含選自乙烯基、烯丙基、丙烯醯基、甲基丙烯醯基、反丁烯二醯基、順丁烯二醯基、乙烯基苯基、苯乙烯基及桂皮醯基中之至少1種來作為自由基聚合性不飽和基。 [14]. 如[12]或[13]之樹脂組成物，其中，(D)成分係分子中具有2個以上的自由基聚合性不飽和基。 [15]. 如[1]~[14]中任一項之樹脂組成物，其中，以測量頻率5.8GHz及測量溫度23℃的條件下，藉由空腔共振擾動法(cavity resonance perturbation method)來測量以200℃進行熱處理90分鐘後所得到的硬化物的介電率為3.2以下。 [16]. 如[1]~[15]中任一項之樹脂組成物，其中，以測量頻率5.8GHz及測量溫度23℃的條件下，藉由空腔共振擾動法來測量以200℃進行熱處理90分鐘後所得到的硬化物的介電正切為0.0040以下。 [17]. 如[1]~[16]中任一項之樹脂組成物，其中，將以180℃進行熱處理30分鐘後所得到的硬化物在80℃的粗化液中浸漬20分鐘後，利用非接觸型表面粗糙度計來測量該硬化物時的算術平均表面粗糙度為260nm以下。 [18]. 如[1]~[17]中任一項之樹脂組成物，其為絕緣層形成用。 [19]. 如[1]~[18]中任一項之樹脂組成物，其為用來形成導體層的絕緣層形成用。 [20]. 一種如[1]~[19]中任一項之樹脂組成物之硬化物。 [21]. 一種樹脂薄片，包含支撐體與設置於該支撐體上的樹脂組成物層，其中，該樹脂組成物層包含如[1]~[19]中任一項之樹脂組成物。 [22]. 一種印刷配線板，包含藉由如[1]~[19]中任一項之樹脂組成物之硬化物或[20]之硬化物所形成的絕緣層。 [23]. 一種半導體裝置，包含如[22]之印刷配線板。 [發明的效果]That is, the present invention includes the following contents. [1]. A resin composition comprising (A) a polycarbonate resin and (B) a maleimide compound, wherein the maleimide compound comprises an alkyl group having 5 or more carbon atoms and a carbon A hydrocarbon chain of at least any one of alkylene groups having 5 or more atoms. [2]. The resin composition according to [1], wherein the component (A) is any one or more of an aliphatic skeleton-containing polycarbonate resin and an aromatic skeleton-containing polycarbonate resin. [3]. The resin composition according to [2], wherein the component (A) contains an aromatic skeleton-containing polycarbonate resin. [4]. The resin composition according to any one of [1] to [3], wherein the number average molecular weight or viscosity average molecular weight of the (A) component is 1,000 or more and 300,000 or less. [5]. The resin composition according to any one of [1] to [4], wherein the content of the component (A) is 1 mass % when the nonvolatile content in the resin composition is 100 mass % more than 40 mass % or less. [6]. The resin composition according to any one of [1] to [5], wherein the value of A/B representing the mass ratio of the (A) component to the (B) component is 0.01 or more and 1.5 or less. [7]. The resin composition according to any one of [1] to [6], wherein the (B) component is represented by the following general formula (B1),

In general formula (B1), M represents an optionally substituted divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms, and L represents a single bond or a divalent linking group. [8]. The resin composition according to any one of [1] to [7], wherein the component (B) is a maleimide compound, and the maleimide compound contains 5 or more and 50 carbon atoms. A hydrocarbon chain of at least one of the following alkyl groups and alkylene groups having 5 to 50 carbon atoms. [9]. The resin composition according to any one of [1] to [8], wherein the content of the component (B) is 0.1 mass % when the non-volatile matter in the resin composition is 100 mass % more than 60 mass % or less. [10]. The resin composition according to any one of [1] to [9], further comprising (C) an inorganic filler. [11]. The resin composition according to [10], wherein the content of the component (C) is 30% by mass or more when the nonvolatile content in the resin composition is 100% by mass. [12]. The resin composition according to any one of [1] to [11], further comprising (D) a radically polymerizable compound. [13]. The resin composition according to [12], wherein the (D) component-based molecule contains a group selected from the group consisting of vinyl, allyl, acryl, methacryloyl, fumarate, cis At least one of a butenediyl group, a vinylphenyl group, a styryl group, and a cinnamonyl group is used as the radically polymerizable unsaturated group. [14]. The resin composition according to [12] or [13], wherein the component (D) has two or more radically polymerizable unsaturated groups in the molecule. [15]. The resin composition according to any one of [1] to [14], wherein, under the conditions of a measurement frequency of 5.8GHz and a measurement temperature of 23°C, by cavity resonance perturbation method The dielectric constant of the cured product obtained after heat treatment at 200° C. for 90 minutes was measured to be 3.2 or less. [16]. The resin composition according to any one of [1] to [15], wherein, under the conditions of a measurement frequency of 5.8 GHz and a measurement temperature of 23° C., the cavity resonance perturbation method is used to measure at 200° C. The dielectric tangent of the cured product obtained after the heat treatment for 90 minutes was 0.0040 or less. [17]. The resin composition according to any one of [1] to [16], wherein the cured product obtained by heat treatment at 180° C. for 30 minutes is immersed in a roughening liquid at 80° C. for 20 minutes, The arithmetic mean surface roughness of the cured product when measured with a non-contact surface roughness meter was 260 nm or less. [18]. The resin composition according to any one of [1] to [17], which is used for forming an insulating layer. [19]. The resin composition according to any one of [1] to [18], which is for forming an insulating layer for forming a conductor layer. [20]. A hardened product of the resin composition according to any one of [1] to [19]. [21]. A resin sheet comprising a support and a resin composition layer disposed on the support, wherein the resin composition layer comprises the resin composition according to any one of [1] to [19]. [22]. A printed wiring board comprising an insulating layer formed by the cured product of the resin composition according to any one of [1] to [19] or the cured product of [20]. [23]. A semiconductor device comprising the printed wiring board of [22]. [Effect of invention]

According to the present invention, there can be provided a resin composition which can obtain a cured product excellent in adhesion and chemical resistance; a cured product of the resin composition; a resin sheet comprising the resin composition; A printed wiring board of an insulating layer formed of a cured product, and a semiconductor device.

[The best form of implementing the invention]

Hereinafter, the resin composition, the cured product of the resin composition, the resin sheet, the printed wiring board, and the semiconductor device of the present invention will be described in detail.

[resin composition] The resin composition of the present invention is a resin composition comprising (A) a polycarbonate resin and (B) a maleimide compound, wherein the maleimide compound includes an alkyl group having 5 or more carbon atoms and a hydrocarbon chain of at least one of alkylene groups having 5 or more carbon atoms. This resin composition can obtain a cured product excellent in adhesion and chemical resistance. Using such a resin composition can provide a cured product of the resin composition; a resin sheet including a resin composition layer of the resin composition; a printed wiring board provided with an insulating layer formed using the resin composition, and semiconductor devices.

In addition to (A) component and (B) component, the resin composition may contain (C) inorganic filler, (D) radical polymerizable compound, (E) hardening accelerator, and (G) optional of additives. Hereinafter, each component contained in the resin composition of this invention is demonstrated in detail.

<(A) Polycarbonate resin> The resin composition contains (A) polycarbonate resin. When the resin composition contains the component (A), the chemical resistance of the cured product of the resin composition can be improved. In addition, since the cured product has excellent chemical resistance, when the surface of the insulating layer, which is intended for plating, etc., is exposed to a chemical solution (for example, an alkaline solution), excessive roughening of the surface can be suppressed (low level can be achieved). roughening), as a result, the skin effect can be suppressed especially in high frequency applications. One of the reasons why such an effect can be exhibited is that the (A) component does not contain or contains a small amount of atoms or atomic groups that are easily invaded by chemicals (especially oxidizing agents in alkaline solutions) in the molecule. Moreover, by containing (A) component, the adhesiveness between the hardened|cured material of a resin composition and the conductor layer (particularly plating) provided on the surface of this hardened|cured material can be improved. As one of the reasons why the component (A) exhibits such an effect, it is considered that the component (A) has a carbonate group having excellent rigidity in the molecule, which improves the overall toughness of the cured product of the resin composition, and thus improves the Because of the physical adhesion strength. Moreover, since the physical adhesiveness of a hardened|cured material can be improved, it can become difficult to generate|occur|produce peeling of a conductor layer accompanying a breakage. Therefore, the adhesiveness between the hardened|cured material of the resin composition of this invention and the conductor with low roughness (for example, the copper foil of the surface whose arithmetic mean roughness Ra is 50 micrometers or less) is also excellent. In addition, when the resin composition does not contain epoxy resin, in general, the cured product of the resin composition tends not to be excellent in adhesiveness, but in the present invention, it is possible to form excellent adhesiveness. The advantages of hardened material.

The component (A) is not particularly limited as long as it has a carbonate group in the molecule, and examples thereof include aliphatic skeleton-containing polycarbonate resins, aromatic skeleton-containing polycarbonate resins, and the like. Furthermore, a polycarbonate resin containing an aromatic skeleton and an aliphatic skeleton can also be used, which is classified as an aromatic skeleton-containing polycarbonate resin. (A) Component system may be used individually by 1 type, and may be used in combination of 2 or more types. Here, the carbonate group refers to a group represented by "-O-C(=O)-".

The component (A) can generally be produced by reacting a polyhydroxy compound with a carbonate-based precursor, and has a structural unit derived from the polyhydroxy compound. The polyhydroxy compound and the carbonate-based precursor system may each be used alone or in combination of two or more. Moreover, (A) component can be manufactured by making the copolymer which copolymerized the polyhydroxy compound of 2 or more types, and a carbonate group precursor react. The structural unit means a structure in which one or more hydrogen atoms are removed from a compound.

As a carbonate-based precursor, carbonate, phosgene, etc. are mentioned, for example.

As a polyhydroxy compound, the polyhydroxy compound containing an aliphatic skeleton, the polyhydroxy compound containing an aromatic skeleton, etc. are mentioned. Here, the aliphatic skeleton-containing polyhydroxy compound refers to a polyhydroxy compound that does not contain an aromatic ring in the molecule, and the aromatic skeleton-containing polyhydroxy compound refers to a polyhydroxy compound that contains an aromatic ring in the molecule. Moreover, the polycarbonate resin obtained using the polyhydroxy compound containing an aliphatic skeleton is called an aliphatic skeleton-containing polycarbonate resin, and the polycarbonate resin obtained using the polyhydroxy compound containing an aromatic skeleton is called a polycarbonate resin containing an aliphatic skeleton. Polycarbonate resin containing aromatic skeleton.

As the aromatic skeleton-containing polyhydroxy compound, an aromatic skeleton-containing dihydroxy compound is preferred from the viewpoint of enhancing the effect expected by the present invention. Examples of the aromatic skeleton-containing dihydroxy compound include bisphenol, naphthalenediol, and the like, and bisphenol is preferred from the viewpoint of enhancing the effect expected by the present invention. That is, as the polycarbonate resin containing an aromatic skeleton, a carbonate resin having a bisphenol structural unit is preferable. Here, bisphenol is a general term for compounds having two hydroxyphenyl groups.

Examples of bisphenols constituting the bisphenol structural unit include bisphenol A, bisphenol B, bisphenol C, bisphenol E, bisphenol F, bisphenol Z, and the like. Bisphenol A and bisphenol C are preferable from the viewpoint of being particularly good in adhesion and embedment.

A commercial item can be used as a polycarbonate resin system containing an aromatic skeleton. As a commercial item, "FPC2136", "FPC0220", "PCZ200", "FPC0330", "PCZ300", "PCZ400" by Mitsubishi Gas Chemical Co., Ltd., etc. are mentioned, for example.

As the aliphatic skeleton-containing polyhydroxy compound, an aliphatic skeleton-containing dihydroxy compound is preferable from the viewpoint of enhancing the effect expected by the present invention. As a dihydroxy compound containing an aliphatic skeleton, a diol compound etc. are mentioned, for example. That is, as the polycarbonate resin containing an aliphatic skeleton, a carbonate resin having a diol structural unit is preferable. As a diol compound which comprises a diol structural unit, 6-hexamethylenediol etc. are mentioned, for example.

A commercial item can be used as an aliphatic skeleton-containing polycarbonate resin system. As a commercial item, "T5652", "G3452", "G4672" etc. made by Asahi Kasei Corporation are mentioned, for example.

As the component (A), any one or more of an aliphatic skeleton-containing polycarbonate resin and an aromatic skeleton-containing polycarbonate resin are preferred from the viewpoint of enhancing the effect expected by the present invention, and Any one or more of a carbonate resin having a diol structural unit and a polycarbonate resin having a bisphenol structural unit is also preferable. From the viewpoint of further enhancing the expected effect of the present invention, it is more preferable that the component (A) contains a polycarbonate resin containing an aromatic skeleton.

The number average molecular weight (Mn) of the component (A) is preferably 1,000 or more, more preferably 1,500 or more, and more preferably 2,000 or more, from the viewpoint of improving the effect expected by the present invention. In addition, the upper limit is not particularly limited, but from the viewpoint of reducing the melt viscosity of the resin composition, it is preferably 300,000 or less, and can be 200,000 or less, 100,000 or less, 50,000 or less, or 35,000 or less. The number average molecular weight system can be measured according to the description of the following <Method for Measuring Number Average Molecular Weight of Polycarbonate Resin>.

<Measuring Method of Number Average Molecular Weight of Polycarbonate Resin> First, 100 mg of the polycarbonate resin to be measured and 5 g of a dispersant (“N-methylpyrrolidone” manufactured by Kanto Chemical Co., Ltd.) were weighed into a vial, and ultrasonically dispersed for 20 minutes. Next, filtration was performed using a membrane filter (“ADVANTEC” manufactured by Toyo Filter Paper Co., Ltd., 0.5 μm pore size (cut)). In addition, the number average molecular weight in terms of polystyrene was measured about the obtained filtrate using a gel permeation chromatography measuring apparatus (“Shodex GPC-101” manufactured by Shoko Scientific Co., Ltd.). According to this measurement method, the number average molecular weight of the polycarbonate resin described in the column of Examples described later was measured.

The viscosity average molecular weight (Mv) of the component (A) is preferably 1,000 or more, more preferably 1,500 or more, and more preferably 2,000 or more, from the viewpoint of improving the effect expected by the present invention. In addition, the upper limit is not particularly limited, but from the viewpoint of reducing the melt viscosity of the resin composition, it is preferably 300,000 or less, and can be 200,000 or less, 100,000 or less, 50,000 or less, or 30,000 or less. As a method for measuring and calculating the viscosity average molecular weight, for example, the method described in Japanese Patent No. 6343680 can be used.

The content of the component (A) is preferably determined according to the content of the component (B), and from the viewpoint of enhancing the expected effect of the present invention, the content of the component (B) is preferably smaller than that of the component (B). good. The lower limit of the value of A/B representing the mass ratio of (A) component to (B) component in the resin composition can be 0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, or 0.05 or more. Moreover, the upper limit of the value of A/B can be 1.5 or less, 1.3 or less, 1.1 or less, 1.0 or less, less than 1.0, or 0.9 or less. From the viewpoint of enhancing the expected effect of the present invention, the upper limit of the value of A/B is preferably less than 1.0. In addition, as the number of carbon atoms in the hydrocarbon chain that the component (B) has in the molecule increases, the content of the component (A) tends to be increased. In this case, the value of A/B is, for example, 0.5 or more and less than 1.0, preferably 0.6 or more and less than 1.0.

In addition, when the non-volatile matter of the resin composition is 100% by mass, the content of the (A) component depends on the content of the components other than the (A) component and the (B) component, but the expectation of the present invention is exhibited. From the viewpoint of the effect, it can be 0.1 mass % or more, 1 mass % or more, 2 mass % or more, or 3 mass % or more. From the viewpoint of improving the effect expected by the present invention, the lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more. When the resin composition does not contain components other than (A) component and (B) component, the upper limit can be set to 50 mass % or less, 45 mass % or less, and 40 mass % or less. From the viewpoint of improving the effect expected by the present invention, it is preferably 40% by mass or less, more preferably 35% by mass or less, and more preferably 30% by mass or less.

<(B) Maleimide compound> The resin composition contains a maleimide compound (hereinafter also referred to as "aliphatic structure-containing maleimide compound") as the component (B), the maleimide compound containing 5 or more carbon atoms A hydrocarbon chain of at least one of the alkyl group and the alkylene group having 5 or more carbon atoms. (B) Component system may be used individually by 1 type, and may be used in combination of 2 or more types. The component (B) is preferably a maleimide compound containing a hydrocarbon chain of at least one of an alkyl group having 5 to 50 carbon atoms and an alkylene group having 5 to 50 carbon atoms or less. .

When the resin composition contains the component (B), the adhesiveness between the cured product of the resin composition and the conductor layer provided on the surface of the cured product can be improved. As one of the reasons why the component (B) exhibits such an effect, it is considered that the component (B) has at least any one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms in the molecule. One type of hydrocarbon chain can improve the chemical adhesion strength of the conductor provided on the surface of the cured product. In addition, since the chemical adhesion of the cured product can be improved, and the synergistic effect of the improvement of the physical adhesion of the component (A) is added, the peeling of the conductor layer accompanying the breakage can be reduced. more difficult to produce. Furthermore, since the maleimide compound has a maleimide group having reactivity in the molecule, as will be described later, it is considered that the (A) component contained in the resin composition is surrounded and formed at the time of the crosslinking reaction. The cross-linked structure improves the adhesion of the cured product. On the other hand, although the (B) component has a hydrocarbon chain in the molecule and generally tends to have poor chemical resistance (for example, resistance to alkaline solutions or resistance to oxidation by radicals), the resin composition has Since the component (A) which is excellent in chemical resistance is contained together with the component (B), deterioration of the chemical resistance of the cured product can be suppressed. Furthermore, the cured product of the resin composition containing the maleimide compound generally exhibits a tendency to become brittle, but since the resin composition of the present invention contains the component (B) together, it is generally Since the component (A) has excellent flexibility, it can compensate for the embrittlement of the cured product caused by the inclusion of the component (B), and as a result, it is considered that it contributes to the improvement of the relationship between the cured product and the conductor layer provided on the surface of the cured product. the tightness between.

(B) The maleimide compound containing an aliphatic structure containing at least one maleimide group represented by the following formula in the molecule. In the structure represented by the following formula, one of the three bonds of the nitrogen atom, which is not bonded to other atoms, represents a single bond.

From the viewpoint of obtaining a cured product having excellent dielectric properties, the number of maleimide groups per molecule in the component (B) is 1 or more, preferably 2 or more, and more preferably 3 In the above, the upper limit is not limited, but may be 10 or less, 6 or less, 4 or less, or 3 or less.

The aliphatic structure-containing maleimide compound has an alkyl group having 5 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 or more, preferably 50 or less, and more preferably 45 or less, more preferably 40 or less. The alkyl group may be linear, branched, or cyclic, and among them, linear is preferred. As such an alkyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. are mentioned, for example. The alkyl group having 5 or more carbon atoms may be a substituent of the alkylene group having 5 or more carbon atoms. The alkyl group having 5 or more carbon atoms may be a part of an alkenyl group or a part of an alkapolyenyl group (the number of double bonds is preferably 2).

The carbon number system of the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, more preferably 50 or less, still more preferably 45 or less, more preferably 40 or less. The alkylene group may be linear, branched, or cyclic. Among them, a straight chain is preferred. Here, the term "cyclic alkylene group" refers to a concept including a case where it is formed only by a cyclic alkylene group and a case where both a linear alkylene group and a cyclic alkylene group are included. Examples of such an alkylene group include pentylene, hexylene, heptyl, octyl, nononyl, decyl, undecyl, dodecyl, and tridecyl. base, pentadecylidene, hexatriacontylene, group with octylene-cyclohexylene structure, group with octylene-cyclohexylene-octylene structure, propylidene -The base of cyclohexylene-octylene structure, etc. The alkylene group having 5 or more carbon atoms may be a part of an alkenylene group or a part of an alkapolyenylene group (the number of double bonds is preferably 2).

From the viewpoint of enhancing the expected effect of the present invention, the maleimide compound containing an aliphatic structure contains both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms. More preferably, it is further more preferable to contain both an alkyl group having 5 or more and 50 or less carbon atoms and an alkylene group having 5 or more and 50 or less carbon atoms.

The alkyl group with 5 or more carbon atoms and the alkylene group with 5 or more carbon atoms may be chain-like, but at least a part of the carbon atoms may be bonded to each other to form a ring, and the ring structure system also includes a spiro ring or a condensed ring . As a ring formed by mutual bonding, a cyclohexane ring etc. are mentioned, for example.

The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms may not have a substituent, but may have a substituent. Examples of the substituent include a halogen atom, -OH, -OC _1-10 alkyl group, -N(C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _6-10 aryl group, -NH ₂ , -CN, -C(O)OC _1-10 alkyl, -COOH, -C(O)H, -NO _2, etc. Here, a term such as "C _xy " (x and y are positive integers and satisfy x<y) means that the number of carbon atoms of the organic group described immediately after the term is x to y. For example, expressions such as "C _1-10 alkyl" mean an alkyl group having 1 to 10 carbon atoms. These substituents can be bonded to each other to form a ring, and the ring structure also includes a spiro ring or a condensed ring. Here, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms. The above-mentioned substituent system may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As the secondary substituent, unless otherwise specified, the same ones as those described above can be used.

In the maleimide compound containing aliphatic structure, the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms are directly bonded to the nitrogen atom of the maleimide group. good.

The number of maleimide groups per molecule in the maleimide compound containing aliphatic structure may be 1, but preferably 2 or more, preferably 10 or less, and more preferably 6 Hereinafter, three or less are particularly preferred. By setting the maleimide compound containing an aliphatic structure to have two or more maleimide groups per molecule, the effect of the present invention can be remarkably obtained.

一般式(B1)中，M表示可具有取代基的包含碳原子數為5以上的伸烷基的2價的脂肪族烴基，L表示單鍵或2價的連結基。The maleimide compound containing an aliphatic structure is preferably a maleimide compound represented by the following general formula (B1).

In general formula (B1), M represents an optionally substituted divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms, and L represents a single bond or a divalent linking group.

M represents an optionally substituted divalent aliphatic hydrocarbon group including an alkylene group having 5 or more carbon atoms. M preferably represents an optionally substituted alkylene group, alkenylene group or alkanepolyalkenylene group having 5 or more carbon atoms (more preferably, the number of double bonds is 2). The alkylene group of M is the same as the above-mentioned alkylene group having 5 or more carbon atoms. As the substituent of M, for example, a halogen atom, -OH, -OC _1-10 alkyl group, -N(C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _6-10 aryl group, - NH ₂ , -CN, -C(O)OC _1-10 alkyl, -COOH, -C(O)H, -NO ₂ and the like. Here, a term such as "C _xy " (x and y are positive integers and satisfy x<y) means that the number of carbon atoms of the organic group described immediately after the term is x to y. For example, expressions such as "C _1-10 alkyl" mean an alkyl group having 1 to 10 carbon atoms. These substituents can be bonded to each other to form a ring, and the ring structure also includes a spiro ring or a condensed ring. The above-mentioned substituent system may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As the secondary substituent, unless otherwise specified, the same ones as those described above can be used. The substituent of M is preferably an alkyl group having 5 or more carbon atoms. Here, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkylene group having 5 or more carbon atoms.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylidene group, -C(=O)-, -C(=O)-O-, -NR ⁰ -(R ⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms), an oxygen atom, a sulfur atom, C(=O)NR ⁰ -, a divalent group derived from phthalimide, a group derived from pyromellitic acid A divalent group of diimide, a group formed by a combination of two or more of these divalent groups, and the like. Alkylene group, alkenylene group, alkynylene group, arylidene group, divalent group derived from phthalimide, divalent group derived from pyromellitic acid diimide, and two or more types The group formed by the combination of the divalent groups may have an alkyl group having 5 or more carbon atoms as a substituent.

The divalent group derived from phthalimide means a divalent group derived from phthalimide, and is specifically a group represented by the following general formula. In the formula, "*" represents a bond bond.

The divalent group derived from pyromellitic acid diimide refers to a divalent group derived from pyromellitic acid diimide, and is specifically a group represented by the following general formula. In the formula, "*" represents a bond bond.

The alkylene system as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, and is further preferably an alkylene group having 1 to 45 carbon atoms, and an alkylene group having 1 to 45 carbon atoms is preferable. Alkylene groups of ~40 are particularly preferred. The alkylene group may be linear, branched, or cyclic. Examples of such an alkylene group include methyl ethylidene, cyclohexylene, pentylene, hexylene, heptylene, octylene, nononyl, decylene, undecylene, Dodecylene extension, tridecyl extension, pentadecyl extension, trihexadecyl extension, base with extension octyl-cyclohexylene structure, with extension octyl-cyclohexylene- extension octyl structure the base, the base having the structure of propylidene-cyclohexylene-octylidene, etc.

The alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 20 carbon atoms, and is also preferably an alkenylene group having 2 to 15 carbon atoms. Alkenyl groups of ~10 are particularly preferred. The alkenylene group may be linear, branched, or cyclic. As such an alkenylene group, a methyl vinylidene group, a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, etc. are mentioned, for example.

As the alkynylene group of the divalent linking group in L, an alkynylene group having 2 to 20 carbon atoms is preferable, and an alkynylene group having 2 to 15 carbon atoms is also preferable, and an alkynylene group having 2 to 15 carbon atoms is preferable. Alkynylene groups of ~10 are particularly preferred. The alkynylene group may be linear, branched, or cyclic. As such an alkynylene group, a methylethynylene group, a cyclohexylene group, a pentynylene group, a hexylene group, a heptynylene group, a cyclooctynyl group, etc. are mentioned, for example.

The aryl-extended group as the divalent linking group in L is preferably an aryl-extended group having 6 to 24 carbon atoms, and is also preferably an aryl-extended group having 6 to 18 carbon atoms. The aryl extended group of ~14 is more preferable, and the aryl extended group of 6 to 10 carbon atoms is even more preferable. As the arylidene group, for example, a phenylene group, a naphthylene group, an anthracylene group, etc. are mentioned.

The alkylene group, the alkenylene group, the alkynylene group, and the arylidene group as the divalent linking group in L may have a substituent. The substituent is the same as that of M in the general formula (B1), and is preferably an alkyl group having 5 or more carbon atoms.

As a group formed by a combination of two or more divalent groups in L, for example, a group formed by a combination of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom may be mentioned. A valent group; a divalent group formed by a combination of a divalent group derived from phthalimide, an oxygen atom, an arylidene group and an alkylene group; a divalent group derived from an alkylene group and a diamide derived from pyromellitic acid A divalent group formed by a combination of a divalent group of an imine, and the like. A group formed by a combination of two or more divalent groups can form a ring such as a condensed ring by the combination of each group. In addition, in the group formed by a combination of two or more divalent groups, the number of repeating units may be 1 to 10 repeating units.

Among them, as L in the general formula (B1), an oxygen atom, an optionally substituted aryl group having 6 to 24 carbon atoms, an optionally substituted alkylene group having 1 to 50 carbon atoms, a carbon An alkyl group having 5 or more atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, or a combination of two or more of these groups. The formed divalent group is preferable. Among them, L is also preferably an alkylene group; a structure having an alkylene group-a divalent group derived from phthalimide-oxygen atom-a divalent group derived from phthalimide The 2-valent group; has an alkylene group - a 2-valent group derived from phthalimide - an oxygen atom - an aryl group - an alkylene group - an aryl group - an oxygen atom - derived from phthalimide A divalent group having a structure of a divalent group of an amine; a divalent group having a structure derived from an alkylene group-diimide pyromellitic acid.

一般式(B2)中，M¹ 係分別獨立表示可具有取代基的包含碳原子數為5以上的伸烷基的2價的脂肪族烴基，A係分別獨立表示可具有取代基的碳原子數為5以上的伸烷基或可具有取代基的具有芳香環的2價的基。T係表示1~10的整數。The maleimide compound containing an aliphatic structure is preferably a maleimide compound represented by the following general formula (B2).

In the general formula (B2), each of M ¹ independently represents an optionally substituted divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms, and A represents each independently an optionally substituted carbon number. It is an alkylene group having 5 or more or a divalent group having an aromatic ring which may have a substituent. T represents an integer from 1 to 10.

Each of M ¹ independently represents a divalent aliphatic hydrocarbon group including an alkylene group having 5 or more carbon atoms which may have a substituent. M ¹ preferably each independently represents an optionally substituted alkylene group, alkenylene group, or alkane polyalkenylene group having 5 or more carbon atoms (more preferably, the number of double bonds is 2). Still more preferable M ¹ is the same as M in the general formula (B1).

A group each independently represents a C5 or more alkylene group which may have a substituent or a divalent group which has an aromatic ring which may have a substituent. The alkylene system in A may be any one of chain, branched, and cyclic, and among them, a cyclic (that is, a cyclic alkylene having 5 or more carbon atoms that may have a substituent) base) is preferred. The carbon number system of the alkylene group is preferably 6 or more, more preferably 8 or more, more preferably 50 or less, still more preferably 45 or less, more preferably 40 or less. Such an alkylene group includes, for example, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a propylidene-cyclohexylene-octylene group The base of the base construction, etc.

Examples of the aromatic ring in the divalent group having an aromatic ring represented by A include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, an aromatic ring, and an aromatic ring. A group of heterocycles, etc., preferably a benzene ring, a phthalimide ring, and a pyromellitic acid diimide ring. That is, as a divalent group having an aromatic ring, an optionally substituted divalent group having a benzene ring, an optionally substituted divalent group having a phthalimide ring, an optionally substituted divalent group, The divalent group having a pyromellitic acid diimide ring of the group is preferable. As the divalent group having an aromatic ring, for example, a group formed by a combination of a divalent group derived from phthalimide and an oxygen atom; a group derived from a divalent phthalimide The group formed by the combination of the alkylene group, the oxygen atom, the aryl group and the alkylene group; the group formed by the combination of the alkylene group and the divalent group derived from pyromellitic acid diimide; derived from pyromellitic acid A divalent group of diimide; a group formed by a combination of a divalent group derived from phthalimide and an alkylene group, and the like. The arylidene group and the alkylene group mentioned above are the same as the arylidene group and the alkylene group in the divalent linking group represented by L in the general formula (B1).

The alkylene group and the divalent group having an aromatic ring represented by A may have a substituent. The substituents are the same as those represented by the substituents of M in the general formula (B1).

Specific examples of the group represented by A include the following groups. In the formula, "*" represents a bond bond.

一般式(B2-1)中，M² 及M³ 係分別獨立表示可具有取代基的包含碳原子數為5以上的伸烷基的2價的脂肪族烴基，R³⁰ 係分別獨立表示氧原子、伸芳基、伸烷基、或由該等基的2種以上的組合所形成的2價的基。t1係表示1~10的整數。

一般式(B2-2)中，M⁴ 、M⁶ 及M⁷ 係分別獨立表示可具有取代基的包含碳原子數為5以上的伸烷基的2價的脂肪族烴基，M⁵ 係分別獨立表示可具有取代基的具有芳香環的2價的基，R³¹ 及R³² 係分別獨立表示碳原子數為5以上的烷基。t2係表示0~10的整數，u1及u2係分別獨立表示0~4的整數。The maleimide compound represented by the general formula (B2) is preferably a maleimide compound represented by the following general formula (B2-1) and a maleimide compound represented by the following general formula (B2-2) Any of the maleimide compounds.

In the general formula (B2-1), M ² and M ³ each independently represent an optionally substituted divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms, and R ³⁰ each independently represents an oxygen atom , an arylidene group, an alkylene group, or a divalent group formed by a combination of two or more of these groups. t1 represents an integer from 1 to 10.

In the general formula (B2-2), M ⁴ , M ⁶ and M ⁷ each independently represent a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent, and M ⁵ is each independently represents an optionally substituted divalent group having an aromatic ring, and R ³¹ and R ³² each independently represent an alkyl group having 5 or more carbon atoms. t2 represents an integer from 0 to 10, and u1 and u2 each independently represent an integer from 0 to 4.

M ² and M ³ each independently represent a divalent aliphatic hydrocarbon group including an alkylene group having 5 or more carbon atoms which may have a substituent. Preferably, M ² and M ³ each independently represent an optionally substituted alkylene group, alkenylene group, or alkane polyalkenylene group having 5 or more carbon atoms (more preferably, the number of double bonds is 2). Further preferred M ² and M ³ are the same as the alkylene groups having 5 or more carbon atoms represented by M in the general formula (B1), and trihexadecane is more preferred.

R ³⁰ each independently represents an oxygen atom, an aryl group, an alkyl group, or a group formed by a combination of two or more divalent groups of these. The arylidene group and the alkylene group are the same as the arylidene group and the alkylene group in the divalent linking group represented by L in the general formula (B1). R ³⁰ is preferably a group formed by a combination of two or more divalent groups or an oxygen atom.

As ^{a group formed by a combination of two or more divalent groups in R 30} , an oxygen atom, an aryl group, and a combination of an alkyl group can be mentioned. The following groups are mentioned as a specific example of the group which consists of a combination of 2 or more types of divalent groups. In the formula, "*" represents a bond bond.

M ⁴ , M ⁶ and M ⁷ each independently represent a divalent aliphatic hydrocarbon group including an alkylene group having 5 or more carbon atoms which may have a substituent. M ⁴ , M ⁶ and M ⁷ preferably each independently represent an alkylene group, an alkenylene group or an alkane polyalkenylene group having a carbon number of 5 or more which may have a substituent (more preferably, the number of double bonds is 2). ). M ⁴ , M ⁶ and M ⁷ are the same as an alkylene group having 5 or more carbon atoms which may have a substituent represented by M in the general formula (B1). Radix, nonyl, and decyl are preferred, and octyl is further preferred.

M ⁵ represents each independently a divalent group having an aromatic ring which may have a substituent. M ⁵ is the same as the divalent group having an aromatic ring which may have a substituent represented by A in the general formula (B2), preferably: an alkylene group and 2 derived from pyromellitic acid diimide A group formed by a combination of valent groups; a group formed by a combination of a divalent group derived from phthalimide and an alkylene group, and preferably a group formed by a combination of an alkylene group and a pyromellitic acid dicarboxylic acid A group formed by a combination of divalent groups of imide.

As a specific example of the group represented by M<^5> , the following group is mentioned, for example. In the formula, "*" represents a bond bond.

R ³¹ and R ³² each independently represent an alkyl group having 5 or more carbon atoms. R ³¹ and R ³² are the same as the above-mentioned alkyl groups having 5 or more carbon atoms, preferably hexyl, heptyl, octyl, nonyl, and decyl, and more preferably hexyl and octyl.

u1 and u2 each independently represent an integer of 1 to 15, preferably an integer of 1 to 10.

Specific examples of the aliphatic structure-containing maleimide compound include the following compounds (b1), (b2), (b3), (b4), (b5) and (b6). However, the maleimide compound containing an aliphatic structure is not limited to these specific examples. In formulas (b1), (b2), (b3), (b5) and (b6), n9, n10, n11, n12 and n13 each represent an integer of 1 to 10.

Specific examples of the aliphatic structure-containing maleimide compound include "BMI-1500" (compound of formula (b1), compound of formula (b5)) and "BMI-1700" manufactured by Designer Molecules Co., Ltd. (compound of formula (b2), compound of formula (b6)), "BMI-3000J" (compound of formula (b3)), "BMI-689" (compound of formula (b4)), and the like. From the viewpoint of enhancing the expected effect of the present invention, "BMI-3000J" is preferably used as the maleimide compound containing an aliphatic structure.

The maleimide group equivalent of the component (B) is preferably 50 g/eq. to 2000 g/eq., more preferably 100 g/eq. to 1000 g, from the viewpoint of remarkably obtaining the effect expected by the present invention. /eq., more preferably 150g/eq.~500g/eq.. The maleimide group equivalent refers to the mass of the maleimide compound containing 1 equivalent of the maleimide group.

When the non-volatile content of the resin composition is 100% by mass, the content of the component (B) depends on the content of the components other than the component (A) and (B), but can be 0.01 mass or more and 0.02 Over mass, over 0.03 mass, over 0.04 mass, or over 0.05 mass. From the viewpoint of exhibiting the effects expected by the present invention, the lower limit can be made 0.1 mass % or more, 1 mass % or more, 2 mass % or more, or 3 mass % or more. The lower limit is preferably 15% by mass or more, more preferably 17% by mass or more, more preferably 20% by mass, from the viewpoint of improving the effect expected by the present invention or obtaining a cured product having excellent dielectric properties. above. The content of the component (B) is preferably larger than the content of the component (A). When the resin composition does not contain components other than (A) component and (B) component, the upper limit can be made 60 mass % or less, 55 mass % or less, and 50 mass % or less. From the viewpoint of improving the effect expected by the present invention, it is preferably 45% by mass or less, more preferably 40% by mass or less, and more preferably 35% by mass or less.

<(C) Inorganic fillers> In addition to the above-mentioned components, the resin composition may further contain an inorganic filler as the component (C) as an optional component. From the viewpoint of obtaining a cured product having excellent dielectric properties, obtaining a cured product having excellent mechanical strength, or obtaining a cured product having a low expansion ratio, the resin composition contains the component (C) as better. Since the component (C) and the curable resin component are different components, in general, the compatibility with the resin component tends to be poor, but in the cured product (crosslinked structure) of the resin composition of the present invention , (C) component has the advantage of being uniformly coated. This is considered to be because the compatibility with the component (C) tends to be excellent in the same way as the adhesiveness of the component (A) and the component (B) contained in the resin composition of the present invention is excellent. the reason.

As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and gibbsite , aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanate Bismuth, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among them, silica is particularly suitable. As silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. are mentioned, for example. Moreover, spherical silica is preferable as a silica system. (C) Inorganic filler system may be used individually by 1 type, and may be used in combination of 2 or more types.

As a commercial item of the component (C), "UFP-30" manufactured by Denka Corporation; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Corporation; "YC100C" manufactured by Admatechs "YA050C", "YA050C-MJE", "YA010C"; "Shirufiru NSS-3N", "Shirufiru NSS-4N", "Shirufiru NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4 manufactured by Admatechs Corporation" ", "SO-C2", "SO-C1", etc.

The specific surface area of the component (C) is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly ^{preferably 3 m 2} /g or more. The upper limit is not particularly limited, but is preferably not more than 60 m ² /g, ^{not more than 50 m 2} /g, or not more than 40 m ² /g. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas on the sample surface using a BET automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mounttech) and calculating by the BET multipoint method.

From the viewpoint of remarkably obtaining the effect expected by the present invention, the average particle diameter of the component (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5 μm or less. , and preferably 2 μm or less, more preferably 1 μm or less.

The average particle diameter of the component (C) can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is produced on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median diameter is measured as the average particle size. For the measurement sample, one that weighs 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and disperses it by ultrasonic for 10 minutes can be used. Using a laser diffraction particle size distribution measuring device for the measurement sample, and setting the wavelength of the light source to be blue and red, the volume-based particle size distribution of the component (C) is measured by a flow cell method. From the obtained particle size distribution, the average particle size was calculated as the median particle size. As a laser diffraction particle size distribution measuring device, "LA-960" manufactured by HORIBA, Ltd., etc. is mentioned, for example.

From the viewpoint of improving moisture resistance and dispersibility, it is preferable that the component (C) is treated with a surface treating agent. Examples of surface treatment agents include vinylsilane-based coupling agents, (meth)acrylic-based coupling agents, fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, and mercaptosilane-based coupling agents. , Silane-based coupling agents, alkoxysilanes, organic silazane compounds, titanate-based coupling agents, etc. Among them, vinylsilane-based coupling agents, (meth)acrylic-based coupling agents, and aminosilane-based coupling agents are preferred from the viewpoint of remarkably obtaining the effects of the present invention. Moreover, a surface treatment agent system may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types.

As a commercial item of the surface treatment agent, "KBM1003" (vinyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM503" (3-methacryloyloxypropyl triacetate) manufactured by Shin-Etsu Chemical Co., Ltd. Ethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidyloxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by the company, "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type manufactured by Shin-Etsu Chemical Co., Ltd.) Silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

From the viewpoint of improving the dispersibility of the inorganic filler, it is preferable to control the degree of surface treatment by the surface treatment agent within a specified range. Specifically, 100 parts by mass of the inorganic filler is preferably subjected to surface treatment by 0.2 to 5 parts by mass of a surface treatment agent, preferably 0.2 to 3 parts by mass, and preferably 0.2 to 3 parts by mass. The surface treatment is preferably carried out by 0.3 to 2 parts by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of the inorganic filler ^{is preferably 0.02 mg/m 2} or more, more preferably 0.1 mg/m ² or more, and 0.2 mg /m ² or more is more preferable. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the form of flakes, it ^{is preferably 1 mg/m 2} or less, more preferably 0.8 mg/m ² or less, and 0.5 mg/m 2 or less. m ² or less is more preferable.

The carbon content per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with a surface-treating agent, and ultrasonic cleaning was performed at 25° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer system, "EMIA-320V" manufactured by Horiba, Ltd., etc. can be used.

From the viewpoint of obtaining a cured product having excellent dielectric properties, when the nonvolatile content in the resin composition is 100% by mass, the content of the component (C) is preferably 30% by mass or more, and more preferably 35% by mass. mass % or more, more preferably 40 mass % or more or 45 mass % or more. The upper limit is determined according to the content of other components, and can be, for example, 90 mass % or less, 80 mass % or less, or 70 mass % or less.

<(D) Radically polymerizable compound> The resin composition system may contain (D) a radically polymerizable compound as an optional component. However, those corresponding to the (B) component are excluded from the (D) component. By containing (D)component in a resin composition, the reaction of (B)component and (D)component is induced, and hardening of (B)component can be accelerated|stimulated. (D) Component system may be used individually by 1 type, and may be used in combination of 2 or more types.

As (D)component, the compound (namely, the compound which has a radically polymerizable unsaturated group in a molecule|numerator) which has the function of generating a radical by heat or light and hardening (B)component can be used. Examples of such compounds include vinylphenyl-based radically polymerizable compounds containing vinylphenyl groups, (meth)acrylic-based radically polymerizable compounds, allyl-based radically polymerizable compounds, and butylated A diene-based radically polymerizable compound.

Generally, (D)component has a radically polymerizable unsaturated group. As a radically polymerizable unsaturated group, the group which has an ethylenic double bond which shows hardenability by irradiation with an active energy ray is mentioned, for example. Examples of such groups include vinyl, allyl, acryl, and methacryloyl, fumaric, maleic, vinylphenyl, styryl, and Among the cinnamyl groups, those having an ethylenic double bond at the terminal of the radically polymerizable unsaturated group are preferred.

The component (D) usually has one or more radically polymerizable unsaturated groups, and preferably has two or more radically polymerizable unsaturated groups. The upper limit of the number of radically polymerizable unsaturated groups is not particularly limited, and may be 10 or less.

When having plural radically polymerizable unsaturated groups, the component (D) is preferably a radically polymerizable compound having a linking group (main skeleton) between plural radically polymerizable unsaturated groups, wherein the linking The group has a bonding bond, and the bonding bond has the same number as the number of the radically polymerizable unsaturated groups. From the viewpoint of obtaining a cured product having excellent chemical resistance or obtaining a cured product having excellent dielectric properties, it is preferable that the above-mentioned linking group has one or more cyclic structures, and one Or a plurality of aromatic ring structures (eg, polyphenylene ether structure, biphenyl structure) are also preferred. From the viewpoint of obtaining a cured product excellent in adhesiveness, it is also preferable that the above-mentioned linking group includes an alicyclic structure. From the viewpoint of improving chemical adhesion, the above-mentioned linking group may contain one or more polar groups (eg -O-, -C(=O)-, -C(=O)-O-) is better. From the viewpoint of improving physical adhesion, the linking group may contain a hydrocarbon group. In this case, the number of carbon atoms in the hydrocarbon group is not particularly limited, and a hydrocarbon group having 2 or more carbon atoms is preferred. , from the viewpoint of improving chemical resistance, a hydrocarbon group having 4 or less carbon atoms is preferable.

(*表示鍵結鍵)。The vinylphenyl-based radically polymerizable compound is a radically polymerizable compound having a vinylphenyl group. The vinyl phenyl group means a group having the structure shown below.

(* indicates a bond key).

From the viewpoint of obtaining a cured product having excellent dielectric properties, the vinylphenyl-based radically polymerizable compound preferably has two or more vinylphenyl groups per molecule.

From the viewpoint of obtaining a cured product having excellent dielectric properties, the vinylphenyl-based radically polymerizable compound preferably has a structure containing a cyclic group. The structure containing a cyclic group contains a cyclic group. As the cyclic group system, a divalent cyclic group is preferable. The cyclic group may be any of an alicyclic cyclic group and an aromatic group. In addition, the cyclic group-containing structural system may have plural divalent cyclic groups.

From the viewpoint of improving the expected effect of the present invention, the divalent cyclic group is preferably 3-membered or more, more preferably 4-membered or more, more preferably 5-membered or more, more preferably 20-membered ring Hereinafter, 15-membered or less-membered ring is also preferred, and 10-membered or less-membered ring is more preferred. Moreover, as a divalent cyclic group, a monocyclic structure may be sufficient as it, and a polycyclic structure may be sufficient as it.

The ring in the divalent cyclic group may constitute the skeleton of the ring by a hetero atom in addition to the carbon atom. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example, Oxygen atom is preferable. In the aforementioned ring, one hetero atom may be present, or two or more hetero atoms may be present.

(2價的基(xii)、(xiii)中，R⁵¹ 、R⁵² 、R⁵⁵ 、R⁵⁶ 、R⁵⁷ 、R⁶¹ 、及R⁶² 係分別獨立表示鹵素原子、碳原子數為6以下的烷基、或苯基，R⁵³ 、R⁵⁴ 、R⁵⁸ 、R⁵⁹ 、及R⁶⁰ 係分別獨立表示氫原子、鹵素原子、碳原子數為6以下的烷基、或苯基)。As a specific example of the structure containing a cyclic group, the following divalent group (xii) or (xiii) is mentioned.

(In the divalent groups (xii) and (xiii), R ⁵¹ , R ⁵² , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁶¹ , and R ⁶² each independently represent a halogen atom and an alkane having 6 or less carbon atoms group, or phenyl group, R ⁵³ , R ⁵⁴ , R ⁵⁸ , R ⁵⁹ , and R ⁶⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group).

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Examples of the alkyl group having 6 or less carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like, and a methyl group is preferred. R ⁵¹ , R ⁵² , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁶¹ , and R ⁶² preferably represent a methyl group. R ⁵³ , R ⁵⁴ , R ⁵⁸ , R ⁵⁹ , and R ⁶⁰ are preferably hydrogen atoms or methyl groups.

(式(D-a)中，R⁷¹ 、R⁷² 、R⁷⁵ 、R⁷⁶ 、R⁷⁷ 、R⁸¹ 、R⁸² 、R⁸⁵ 及R⁸⁶ 係分別獨立表示鹵素原子、碳原子數為6以下的烷基、或苯基，R⁷³ 、R⁷⁴ 、R⁷⁸ 、R⁷⁹ 、R⁸⁰ 、R⁸³ 及R⁸⁴ 係分別獨立表示氫原子、鹵素原子、碳原子數為6以下的烷基、或苯基。d1及d2表示0~300的整數。但不包括d1及d2之一方為0之情形)。Moreover, the structure containing a cyclic group may contain a combination of plural divalent cyclic groups. As a specific example when a divalent cyclic group is combined, the divalent cyclic group represented by the following formula (Da) is mentioned.

(In formula (Da), R ⁷¹ , R ⁷² , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms, or phenyl, R ⁷³ , R ⁷⁴ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. d1 and d2 represents an integer from 0 to 300. However, the case where one of d1 and d2 is 0 is not included).

R ⁷¹ , R ⁷² , R ⁸⁵ and R ⁸⁶ are the same as ^{R 51} in formula (xii). R ⁷³ , R ⁷⁴ , R ⁸³ and R ⁸⁴ are the same as ^{R 53} in formula (xii). R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸¹ , and R ⁸² are the same as ^{R 55} in formula (xiii). R ⁷⁸ , R ⁷⁹ , and R ⁸⁰ are the same as ^{R 58} in formula (xiii).

d1 and d2 represent integers from 0 to 300. However, the case where one of d1 and d2 is 0 is not included. As d1 and d2, an integer representing 1-100 is preferable, an integer representing 1-50 is more preferable, and an integer representing 1-10 is more preferable. d1 and d2 may be the same or different.

The divalent cyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, and an oxygen group. group, etc., preferably an alkyl group.

The vinylphenyl group may be directly bonded to a divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include alkylene, alkenylene, aryl, heteroaryl, -C(=O)O-, -O-, -NHC(=O)-, -NC (=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc., may also be a base formed by a combination of these plural numbers. As the alkylene system, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is also preferable, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having a carbon number of 1 to 5 is preferable. The alkylene group having 1 to 4 atoms is more preferable. The alkylene system may be any of straight chain, branched and cyclic. As such an alkylene group, for example, a methylene group, an ethylidene group, a propylidene group, a butylidene group, a pentylene group, a hexylene group, a 1,1-dimethylethylidene group, etc. are mentioned, and a methylene group is represented by a methylene group. , ethylidene and 1,1-dimethyl ethylidene are preferred. As the alkenylene group, an alkenylene group with 2 to 10 carbon atoms is preferable, an alkenylene group with a carbon number of 2 to 6 is preferable, and an alkenylene group with 2 to 5 carbon atoms is more preferable. . As the aryl extended group and the extended heteroaryl group, an extended aryl group or a extended heteroaryl group with a carbon number of 6 to 20 is preferable, and an extended aryl group or a extended heteroaryl group with a carbon number of 6 to 10 is also preferable. . As the divalent linking group, an alkylene group is preferable, and among them, a methylene group is preferable.

(式(D1)中，R⁹¹ 及R⁹² 係分別獨立表示2價的連結基。環B1表示2價的環狀基)。The vinylphenyl-based radically polymerizable compound is preferably represented by the following formula (D1).

(In formula (D1), R ⁹¹ and R ⁹² each independently represent a divalent linking group. Ring B1 represents a divalent cyclic group).

R ⁹¹ and R ⁹² each independently represent a divalent linking group. The divalent linking group is the same as the above-mentioned divalent linking group.

Ring B1 represents a divalent cyclic group. The ring B1 is the same as the above-mentioned divalent cyclic group.

Ring B1 may have a substituent. As a substituent, it is the same as that which the above-mentioned divalent cyclic group may have.

(上述式中，q1係與式(D-a)中的d1相同，q2係與式(D-a)中的d2相同)。The following are specific examples showing vinylphenyl-based radically polymerizable compounds, but the present invention is not limited to these.

(In the above formula, q1 is the same as d1 in formula (Da), and q2 is the same as d2 in formula (Da)).

As the vinylphenyl-based radically polymerizable compound, a commercial item can be used, and examples thereof include "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd. and the like. The vinylphenyl-based radically polymerizable compound may be used alone or in combination of two or more.

The number average molecular weight of the vinylphenyl-based radically polymerizable compound is preferably 3,000 or less, more preferably 2,500 or less, more preferably 2,000 or less and 1,500 or less, from the viewpoint of exhibiting the effects expected by the present invention. The lower limit is preferably 100 or more, more preferably 300 or more, more preferably 500 or more, or 1000 or more. The number average molecular weight is the number average molecular weight in terms of polystyrene measured using gel permeation chromatography (GPC).

The (meth)acrylic radical polymerizable compound is a compound containing an acryl group, a methacryl group, and a combination of these. As a (meth)acrylic-type radically polymerizable compound, it is preferable to have 2 or more (meth)acryloyl groups per molecule from a viewpoint of improving the effect anticipated by this invention. The term "(meth)acryloyl" is meant to include acryl and methacryloyl groups and combinations of these.

From the viewpoint of enhancing the effect expected by the present invention, the (meth)acrylic radical polymerizable compound preferably has a structure containing a cyclic group. The structure containing a cyclic group contains a cyclic group. As the cyclic group system, a divalent cyclic group is preferable. The cyclic group may be any of an alicyclic cyclic group and an aromatic group. Among them, it is preferable to contain an alicyclic cyclic group from the viewpoint of enhancing the effect expected by the present invention.

From the viewpoint of improving the expected effect of the present invention, the divalent cyclic base is preferably 3-membered or more, more preferably 4-membered or more, more preferably 5-membered or more, more preferably 20-membered. ring or less, preferably 15-membered ring or less, more preferably 10-membered ring or less. Moreover, as a divalent cyclic group, a monocyclic structure may be sufficient as it, and a polycyclic structure may be sufficient as it.

The ring in the divalent cyclic group may constitute the skeleton of the ring by a hetero atom in addition to the carbon atom. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example, Oxygen atom is preferable. In the aforementioned ring, one hetero atom may be present, or two or more hetero atoms may be present.

Specific examples of the structure containing a cyclic group include the following divalent groups (i) to (xi). Among them, (x) or (xi) is preferable as a bivalent cyclic group.

The divalent cyclic group may have a substituent. Examples of such a substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a silyl group, an acyl group, an aryloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, A mercapto group, an oxy group, etc., preferably an alkyl group.

The (meth)acryloyl group may be directly bonded to a divalent cyclic group, or may be bonded via a bivalent linking group. Examples of the divalent linking group include alkylene, alkenylene, aryl, heteroaryl, -C(=O)O-, -O-, -NHC(=O)-, -NC (=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc., may also be a base formed by a combination of these plural numbers. As the alkylene system, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is also preferable, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having a carbon number of 1 to 5 is preferable. The alkylene group having 1 to 4 atoms is more preferable. The alkylene system may be any of straight chain, branched and cyclic. As such an alkylene group, for example, a methylene group, an ethylidene group, a propylidene group, a butylidene group, a pentylene group, a hexylene group, a 1,1-dimethylethylidene group, etc. are mentioned, and a methylene group is represented by a methylene group. , ethylidene and 1,1-dimethyl ethylidene are preferred. As the alkenylene group, an alkenylene group with 2 to 10 carbon atoms is preferable, an alkenylene group with a carbon number of 2 to 6 is preferable, and an alkenylene group with 2 to 5 carbon atoms is more preferable. . As the aryl extended group and the extended heteroaryl group, an extended aryl group or a extended heteroaryl group with a carbon number of 6 to 20 is preferable, and an extended aryl group or a extended heteroaryl group with a carbon number of 6 to 10 is also preferable. . The divalent linking group is preferably an alkylene group, and among them, a methylene group and a 1,1-dimethylethylidene group are preferable.

(式(D2)中，R¹⁰¹ 及R¹⁰⁴ 係分別獨立表示丙烯醯基或甲基丙烯醯基，R¹⁰² 及R¹⁰³ 係分別獨立表示2價的連結基。環B2表示2價的環狀)。The (meth)acrylic radical polymerizable compound is preferably represented by the following formula (D2).

(In formula (D2), R ¹⁰¹ and R ¹⁰⁴ each independently represent an acryl group or a methacryloyl group, and R ¹⁰² and R ¹⁰³ each independently represent a divalent linking group. Ring B2 represents a divalent cyclic ring) .

R ¹⁰¹ and R ¹⁰⁴ each independently represent an acryl group or a methacryl group, preferably an acryl group.

R ¹⁰² and R ¹⁰³ each independently represent a divalent linking group. The divalent linking group is the same as the divalent linking group to which the (meth)acryloyl group can be bonded.

Ring B2 represents a divalent cyclic group. Ring B2 is the same as the above-mentioned divalent cyclic group. Ring B2 may have a substituent. As a substituent, it is the same as that which the above-mentioned divalent cyclic group may have.

Although the following are mentioned as a specific example of a (meth)acrylic-type radically polymerizable compound, this invention is not limited to these.

As the (meth)acrylic radical polymerizable compound, commercially available products can be used, and examples include "A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "DCP-A" manufactured by Kyōeisha Chemical Co., Ltd., and Nippon Kayaku Co., Ltd. "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA" manufactured by the company, "NK EsterDCP" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc.

From the viewpoint of exhibiting the effects expected by the present invention, the (meth)acryloyl equivalent of the (meth)acrylic radically polymerizable compound is preferably 30 g/eq. to 400 g/eq., and more preferably It is 50g/eq.~300g/eq., more preferably 75g/eq.~200g/eq.. The (meth)acryloyl equivalent means the mass of the (meth)acrylic radical polymerizable compound containing 1 equivalent of the (meth)acryloyl group.

The allyl-based radically polymerizable compound refers to a compound having at least one allyl group in the molecule. The allyl-based radically polymerizable compound preferably has one or more allyl groups per molecule, and more preferably has two or more allyl groups. The lower limit is not particularly limited, but preferably 10 or less, and preferably 5 or less.

Furthermore, from the viewpoint of enhancing the effects expected by the present invention, in addition to allyl groups, allyl-based radically polymerizable compounds have benzoxazine rings, phenol rings, isocyanuric acid rings, Any of an epoxy group and a carboxylic acid derivative having a cyclic structure is preferable.

The allyl-based radically polymerizable compound having a benzoxazine ring is preferably bonded to either a nitrogen atom or a benzene ring of the benzoxazine ring, and is more preferably bonded to a nitrogen atom

Examples of the allyl-based radically polymerizable compound having a phenol ring include allyl-containing cresol resins, allyl-containing novolak-type phenol resins, allyl-containing cresol phenol resins, and the like.

It is preferable that the allyl-based radically polymerizable compound having an isocyanuric acid structure is directly bonded to an allyl group by a nitrogen atom of the isocyanuric acid structure. Examples of the allyl-based radically polymerizable compound having an isocyanuric structure include allyl isocyanurate, diallyl isocyanurate, and isocyanurate triene. propyl ester, etc.

It is preferable that the allyl radical polymerizable compound which has an epoxy group contains 2 or more epoxy groups in 1 molecule. In addition, the allyl-based radically polymerizable compound having an epoxy group preferably has an aromatic structure, and when two or more types of allyl-based radically polymerizable compounds having an epoxy group are used, at least It is also preferable that one type has an aromatic structure. The so-called aromatic structure system is generally defined as an aromatic chemical structure, and also includes polycyclic aromatic and aromatic heterocycles. The allyl-based radically polymerizable compound having an epoxy group preferably has a bisphenol structure, and examples of the bisphenol structure include bisphenol A type, bisphenol F type, bisphenol AF type, and the like.

The allyl-based radically polymerizable compound containing a carboxylic acid derivative having a cyclic structure is preferably an allyl carboxylate having a cyclic structure. The cyclic structure system may be any of a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic ring structure. In addition, the cyclic group may constitute the skeleton of the ring by a hetero atom in addition to the carbon atom. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example, A nitrogen atom is preferable. In the aforementioned ring, one hetero atom may be present, or two or more hetero atoms may be present.

As a carboxylic acid which has a cyclic structure, isocyanuric acid (isocyanuric acid), diphenic acid (diphenic acid), phthalic acid, cyclohexanedicarboxylic acid, etc. are mentioned, for example. Examples of the allyl-based radically polymerizable compound containing a carboxylic acid derivative having a cyclic structure include allyl isocyanurate, diallyl isocyanurate, isocyanurate Acid triallyl ester, diphenic acid diallyl, allyl diphenic acid, ortho-diallyl phthalate, meta-diallyl Phthalates, para-diallyl phthalates, allyl cyclohexanedicarboxylate, diallyl cyclohexanedicarboxylate, etc.

As the allyl radically polymerizable compound, a commercial item can be used. As commercially available products, "MEH-8000H" and "MEH-8005" (allyl-based radically polymerizable compounds having a phenol ring) manufactured by Meiwa Chemical Co., Ltd.; "RE-810NM" manufactured by Nippon Kayaku Co., Ltd. ( Allyl-based radically polymerizable compound having an epoxy group); "ALP-d" (allyl-based radically polymerizable compound having a benzoxazine ring) manufactured by Shikoku Chemical Industry Co., Ltd.; Shikoku Chemical Industry Co., Ltd. "L-DAIC" (allyl radical polymerizable compound with isocyanuric acid ring) manufactured by the company; "TAIC" (allyl radical polymerizable compound with isocyanuric acid ring) manufactured by Nippon Kasei Corporation chemical compound (triallyl isocyanate)); "MDAC" (allyl-based radically polymerizable compound having a cyclohexanedicarboxylic acid derivative) manufactured by Osaka Soda Corporation; "DAD" manufactured by Nisshoku Techno Fine Chemical Co., Ltd. ( Diallyl biphthalate); "DAISO DAP (registered trademark) Monomer" (ortho-diallyl phthalate) manufactured by Osaka Soda Corporation, and the like.

From the viewpoint of exhibiting the effect expected by the present invention, the allyl equivalent of the allyl radically polymerizable compound is preferably 20 g/eq. to 1000 g/eq., and more preferably 50 g/eq. to 50 g/eq. 500g/eq., more preferably 100g/eq.~300g/eq.. The allyl equivalent means the mass of the allyl radically polymerizable compound containing 1 equivalent of allyl groups.

The term "butadiene-based radically polymerizable compound" refers to a compound having at least one butadiene skeleton in the molecule. The polybutadiene structural system may be contained in the main chain or in the side chain. Also, polybutadiene structures can be partially hydrogenated. The butadiene-based radically polymerizable compound is selected from the group consisting of hydrogenated polybutadiene skeleton-containing resin, hydroxyl group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxyl group-containing butadiene resin, One or more of the group consisting of acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin, and urethane group-containing butadiene resin Resin is also preferred.

Specific examples of the butadiene-based radically polymerizable compound include "JP-100" manufactured by Nippon Soda Co., Ltd., "Ricon100", "Ricon150", "Ricon130MA8", "Ricon130MA13", "Ricon130MA13", "Ricon100", "Ricon150", "Ricon130MA8", "Ricon130MA20", "Ricon131MA5", "Ricon131MA10", "Ricon131MA17", "Ricon131MA20", "Ricon184MA6", etc.

From the viewpoint of promoting the reaction of the (B) component, the content of the (D) component is preferably 0.1% by mass or more, and more preferably 100% by mass of the nonvolatile content in the resin composition. 0.2 mass % or more, more preferably 1 mass % or more or 2 mass %, preferably 30 mass % or less, still more preferably 20 mass % or less, more preferably 10 mass % or less.

<(E) Hardening accelerator> In addition to the above-mentioned components, the resin composition system may contain (E) a hardening accelerator as an optional component. By using the hardening accelerator (E), hardening can be accelerated when the resin composition is hardened.

(E) As a hardening accelerator, a phosphorus type hardening accelerator, an amine type hardening accelerator, an imidazole type hardening accelerator, a guanidine type hardening accelerator, a metal type hardening accelerator, and a peroxide type hardening accelerator are mentioned, for example. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferred, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are also preferred. Preferably, an amine-based hardening accelerator is particularly preferred. (E) Hardening accelerator type may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-paraffin (Dimethylaminomethyl)phenol, 1,8-diazabis(5,4,0)-undecene. Among them, 4-dimethylaminopyridine and 1,8-diazabis(5,4,0)-undecene are preferred.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4- Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitic acid salt, 1-cyanoethyl-2-phenylimidazole trimellitic acid salt, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ten Monoalkylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')] -Ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-Phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3- Dihydro-1H-pyrro[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazole imidazole compounds such as linoline; and adducts of imidazole compounds and epoxy resins. Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

As an imidazole type hardening accelerator system, a commercial item can be used, for example, "P200-H50" by Mitsubishi Chemical Corporation is mentioned.

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dicyandiamide Methylguanidine, Diphenylguanidine, Trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl- 1,5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide , 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide. Among them, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

As the metal-based hardening accelerator, for example, metal organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin are exemplified. Specific examples of the organometallic complex include organocobalt complexes such as cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, and the like, and organocopper complexes such as copper (II) acetylacetonate. compounds, organozinc complexes such as zinc (II) acetylacetonate, organoiron complexes such as iron (III) acetylacetonate, organonickel complexes such as nickel (II) acetylacetonate, etc. Organic manganese complexes such as manganese (II) acetonate. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of peroxide-based curing accelerators include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, and tert-butyl cumyl peroxide. Benzene, di-tert-butyl peroxide, dicumyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide.

As a peroxide type hardening accelerator system, a commercial item can be used, for example, "Percumyl (registered trademark) D" manufactured by NOF Corporation is mentioned.

When the (E) hardening accelerator is used, the amount of the (E) hardening accelerator in the resin composition with respect to 100% by mass of the nonvolatile matter in the resin composition from the viewpoint of exhibiting the effects expected by the present invention is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, particularly preferably 0.05% by mass or more, more preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass the following.

<(F) Other additives> In addition to the above-mentioned components, the resin composition system may further contain other additive components as optional components. As such an additive component, resin additives, such as a thickener, an antifoamer, a leveling agent, and an adhesiveness imparting agent, etc. are mentioned, for example. These additive components may be used alone or in combination of two or more. Those skilled in the art can appropriately set the respective contents. Moreover, as an additive component, an epoxy resin, a thermosetting resin, and a maleimide compound which does not belong to (B) component can be mentioned, and the content of these components can be contained so that the desired content of the present invention is not excessively impaired. Make appropriate settings within the range of the amount of the effect.

<Physical properties and applications of resin composition> The resin composition of this invention contains (A) component and (B) component. Thereby, a cured product excellent in adhesion and chemical resistance can be obtained. Generally speaking, the adhesiveness of a resin composition not containing an epoxy resin tends to be inferior to that of a resin composition containing an epoxy resin, but according to the present invention, a resin composition having sufficiently excellent adhesiveness can be provided. hardened material. Moreover, the resin composition system of this invention can provide the hardened|cured material which is excellent in dielectric property as mentioned later. Therefore, the resin composition of the present invention can be suitably used for generating high-frequency signals in printed wiring boards, circuit boards, and semiconductor devices including the cured product.

Regarding the resin composition of the present invention, the cured product obtained by heat-treating the resin composition at 180° C. for 30 minutes is excellent in chemical resistance. For example, the arithmetic mean surface roughness of the cured product when the cured product is immersed in an alkaline solution at 80° C. for 20 minutes is measured with a non-contact surface roughness meter. 270 nm or less, preferably 260 nm or less. In this way, when the resin composition of the present invention is cured, since it is excellent in chemical resistance, a cured product with low roughness can be provided. Thereby, even when the above-mentioned cured product is used as an insulating layer in a printed wiring board or a circuit board for generating high-frequency signals, the skin effect can be suppressed. Therefore, the resin composition of the present invention, printed wiring boards, circuit boards, and semiconductor devices using the cured product can be suitably used for generating high-frequency signals.

Regarding the resin composition of the present invention, the cured product obtained by heat-treating the resin composition at 200° C. for 90 minutes has excellent dielectric properties. For example, the dielectric constant of the above-mentioned cured product when measured by the cavity resonance perturbation method under the conditions of a measurement frequency of 5.8 GHz and a measurement temperature of 23°C is 3.2 or less as verified in the examples described later, preferably Less than 3.2. For example, the dielectric tangent of the cured product when measured by the cavity resonance perturbation method under the conditions of a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. is, as verified in the examples to be described later, for example, less than 0.0044. Preferably it is 0.0040 or less, more preferably 0.0039 or less, and more preferably 0.0038 or less.

The resin composition of the present invention can provide an insulating layer formed of a cured product having excellent adhesion and chemical resistance. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating purposes. Specifically, it can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a conductor layer) on the insulating layer. rewiring layer).

In the multilayer printed wiring board described later, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (a resin composition for forming an insulating layer of a multilayer printed wiring board), A resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for forming an interlayer insulating layer of a printed wiring board).

In particular, the resin composition of the present invention can be suitably used for forming a high-frequency circuit by taking advantage of the advantages of obtaining a cured product with excellent dielectric properties and a cured product with low roughness capable of suppressing the skin effect. Resin composition for insulating layers of substrates (resin compositions for forming insulating layers of high-frequency circuit boards). Among them, this resin composition can be used more suitably as a resin composition for forming an interlayer insulating layer of a high-frequency circuit board (a resin composition for forming an interlayer insulating layer of a high-frequency circuit board). Here, the "high-frequency circuit board" means a circuit board that can operate even under an electric signal of a high-frequency band. In addition, "high frequency band" means the frequency band of 1 GHz or more normally, and the said resin composition is effective even in the frequency band of 28 GHz - 80 GHz, for example.

In addition, the resin composition system of the present invention can also be suitably used as a rewiring-forming layer for forming an insulating layer for a rewiring layer when a semiconductor chip package is produced through, for example, the following steps (1) to (6). A resin composition (resin composition for rewiring formation layer formation), and a resin composition for sealing a semiconductor wafer (resin composition for sealing a semiconductor wafer). When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the sealing layer. (1) The step of laminating and temporarily fixing the film on the substrate; (2) the step of temporarily fixing the semiconductor wafer on the temporary fixing film; (3) the step of forming a sealing layer on the semiconductor wafer; (4) the step of peeling the base material and the temporary fixing film from the semiconductor wafer; (5) a step of forming a rewiring formation layer as an insulating layer on the surface of the base material of the semiconductor wafer and the surface from which the temporary fixing film is peeled off; and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

<Preparation method of resin composition> The preparation method of the resin composition of this invention is not specifically limited, For example, the preparation component is mixed with a solvent etc. as needed, and the method of dispersing using a rotary mixer etc. is mentioned, for example.

[hardened product of resin composition] <Physical properties and uses of hardened resin composition> The cured product obtained by heat-treating the resin composition of the present invention is generally excellent in chemical resistance. For example, the arithmetic mean surface roughness of the cured product obtained by heat-treating the resin composition of the present invention is immersed in an alkaline solution of 80° C. for 20 minutes, and the arithmetic mean surface roughness of the cured product when measured with a non-contact surface roughness meter can be, for example, is 270 nm or less. The preferable range and the like of the value of the arithmetic mean surface roughness are the same as those described for the resin composition. In this way, the cured product of the resin composition of the present invention is generally excellent in chemical resistance, and thus can have a low roughness. This makes it possible to suppress the skin effect even in a printed wiring board or a circuit board for generating high-frequency signals using the cured product as an insulating layer. Therefore, printed wiring boards, circuit boards, and semiconductor devices using the cured product of the resin composition of the present invention can be suitably used for generating high-frequency signals.

The cured product obtained by heat-treating the resin composition of the present invention is generally excellent in dielectric properties. For example, the hardened product obtained by heat-treating the resin composition of the present invention can have a dielectric constant of 3.2 or less when measured by the cavity resonance perturbation method under the conditions of a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. The preferable range and the like of the value of the dielectric constant are the same as those described for the resin composition. Moreover, when the said hardened|cured material is measured under the conditions of a measurement frequency of 5.8 GHz and a measurement temperature of 23 degreeC by the cavity resonance perturbation method, for example, the dielectric tangent may be less than 0.0044, for example. The preferable range and the like of the value of the dielectric tangent are the same as those described for the resin composition.

The cured product of the resin composition of the present invention can generally obtain an insulating layer formed of a cured product excellent in adhesion and chemical resistance. Therefore, the cured product of the resin composition of the present invention can be suitably used as a resin composition for insulating purposes. Specifically, the cured product of the resin composition of the present invention can be suitably used as an insulating layer for forming a conductor layer (including a rewiring layer) on the insulating layer.

Moreover, in the multilayer printed wiring board mentioned later, the hardened|cured material system of the resin composition of this invention can be used suitably as an insulating layer of a multilayer printed wiring board.

[resin sheet] The resin sheet of the present invention includes a support body, and a resin composition layer formed of the resin composition of the present invention provided on the support body.

The thickness of the resin composition layer is preferably from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product excellent in insulation even when the cured product of the resin composition is a thin film. 50 μm or less, preferably 45 μm or less, and more preferably 42 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and it is usually 5 μm or more.

As the support, for example, a film, a metal foil, or a release paper made of a plastic material is mentioned, and a film or a metal foil made of a plastic material is preferable.

When a film formed of a plastic material is used as a support, the plastic material may, for example, include polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate (hereinafter referred to as "PET"). Polyester such as "PEN"), polycarbonate (hereinafter abbreviated as "PC"), acrylic acid such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polymer Ester sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using a metal foil as a support body, a copper foil, an aluminum foil, etc. are mentioned as a metal foil, for example, a copper foil is preferable. As the copper foil system, a foil made of a simple metal of copper can be used, or a foil made of an alloy of copper and other metals (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used .

A matte treatment, corona treatment and antistatic treatment may be applied to the surface where the support body and the resin composition layer are joined.

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface joined to the resin composition layer can be used. As a mold release agent used for the mold release layer of the support with a mold release layer, for example, one selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a polysiloxane resin can be mentioned. 1 or more release agents. As a support system with a release layer, commercially available products can be used, for example, "SK-1", "AL- 5", "AL-7", "Lumirror T60" manufactured by Toray Corporation, "PUREX" manufactured by Teijin Corporation, "Unipeel" manufactured by Unitika Corporation, etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and further preferably in the range of 10 μm to 60 μm. Furthermore, when a support with a mold release layer is used, the thickness of the entire support with a mold release layer is preferably within the above range.

In one embodiment, the resin sheet system may further include other layers as needed. As said other layer, the protective film based on a support body etc. are provided on the surface (that is, the surface on the opposite side to the support body) of the resin composition layer which is not joined to a support body, for example. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion and scratches of dust and the like to the surface of the resin composition layer can be suppressed.

The resin sheet can be produced by, for example, the following method: preparing a resin varnish in which the resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and drying it to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol Acetates such as alcohol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide (DMAc) and amide-based solvents such as N-methylpyrrolidone and the like. An organic solvent system may be used individually by 1 type, and may be used in combination of 2 or more types.

Drying can be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent in the resin composition layer is 10 mass % or less, preferably 5 mass % or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing an organic solvent of 30 to 60 mass % is used, it is dried at 50° C. to 150° C. for 3 minutes to 10 minutes, and A resin composition layer can be formed.

The resin sheet system can be wound up in a roll shape and stored. When the resin sheet has a protective film, it can be used later by peeling off the protective film.

[Printed Wiring Board] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

A printed wiring board can be manufactured by, for example, using the above-mentioned resin sheet and a method including the steps of the following (I) and (II). (1) Laminating the resin sheet on the inner substrate in a manner that the resin composition layer of the resin sheet is bonded to the inner substrate; (II) A step of thermosetting the resin composition layer to form an insulating layer.

The "inner layer substrate" used in the step (I) refers to a member that becomes a substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting substrates, etc. type polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one or both surfaces of the substrate is sometimes referred to as an "inner layer circuit substrate". Moreover, when manufacturing a printed wiring board, the intermediate product which further needs to form an insulating layer and/or a conductor layer is also included in the so-called "inner-layer board|substrate" of this invention. When the printed wiring board is a component-embedded circuit board, the component-embedded inner-layer substrate can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermally pressure-bonding the resin sheet on the inner layer substrate from the support side. As a member for thermocompression-bonding the resin sheet on the inner-layer substrate (hereinafter also referred to as a "heat compression member"), a heated metal plate (SUS mirror plate, etc.), a metal roll (SUS roll), etc. are mentioned, for example. Furthermore, it is preferable that the thermocompression bonding member is not directly pressed against the resin sheet, but is pressed so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate through an elastic material such as heat-resistant rubber.

The lamination of the inner layer substrate and the resin sheet can be carried out by a vacuum lamination method. In the vacuum lamination method, the heating pressure bonding temperature is preferably 60°C to 160°C, and preferably 80°C to 140°C, and the heating pressure bonding pressure is preferably 0.098MPa to 1.77MPa, and preferably 0.29 In the range of MPa to 1.47 MPa, the heating and pressing time is preferably 20 seconds to 400 seconds, and more preferably 30 seconds to 300 seconds. The lamination system is preferably carried out under a reduced pressure condition of a pressure of 26.7 hPa or less.

The lamination system can be performed by a commercially available vacuum laminating machine. As a commercially available vacuum laminating machine, the vacuum pressurization type|mold lamination machine by Meiki Seisakusho Co., Ltd., the vacuum lamination machine by Nikko-Materials Co., Ltd., a batch type vacuum pressurization lamination machine, etc. are mentioned, for example.

After lamination, the laminated resin sheet can be smoothed under normal pressure (atmospheric pressure), for example, by pressing the thermocompression bonding member from the support side. The pressing conditions of the smoothing treatment can be set to the same conditions as the heat and pressure bonding conditions of the above-mentioned laminate. The smoothing process can be performed by a commercially available laminator. Furthermore, the lamination and smoothing can be continuously performed using the above-mentioned commercially available vacuum laminating machine.

The support system can be removed between step (I) and step (II), and can also be removed after step (II).

In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions of the resin composition layer are not particularly limited, and the conditions generally employed when forming an insulating layer of a printed wiring board can be used.

For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition, etc. The curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and more preferably 170°C to 170°C. 210°C. The hardening time can be preferably set to 5 minutes to 120 minutes, more preferably can be set to 10 minutes to 100 minutes, and more preferably can be set to 15 minutes to 100 minutes.

Before thermally curing the resin composition layer, the resin composition layer may be pre-heated at a temperature lower than the curing temperature. For example, before thermosetting the resin composition layer, the resin composition layer may be heated at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 115°C or less, and preferably 70°C or more and 110°C or less). Preliminary heating is performed for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, (III) the step of opening a hole to the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming the conductor layer may be further implemented. The steps (III) to (V) for the manufacture of the printed wiring board can be carried out according to various methods known to those skilled in the art. Furthermore, when the support is removed after step (II), the removal of the support may be between step (II) and step (III), between step (III) and step (IV), or step (IV) and step (V) to implement. In addition, the formation of the insulating layer and the conductor layer in the steps (II) to (V) can be repeated as necessary to form a multilayer wiring board.

The step (III) is a step of opening holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) can be implemented using, for example, drilling, laser, plasma, etc., depending on the composition of the resin composition used in the formation of the insulating layer, and the like. The size or shape of the hole may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Generally speaking, smear removal is also performed in this step (IV). The procedures and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions generally used when forming an insulating layer of a printed wiring board can be adopted. For example, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid can be sequentially performed to roughen the insulating layer.

The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include an alkaline solution, a surfactant solution, and the like, and an alkaline solution is preferred, and a sodium hydroxide solution and a potassium hydroxide solution are used as the alkaline solution. better. As a commercially available swelling liquid, "Swelling Dip Securiganth P", "Swelling Dip Securiganth SBU", "Swelling Dip Securiganth P" by Atotech Japan, etc. are mentioned, for example. The swelling treatment by the swelling liquid is not particularly limited, and for example, it can be performed by immersing the insulating layer in the swelling liquid at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

The roughening liquid system used for roughening treatment usually contains an oxidizing agent. Although it does not specifically limit as a roughening liquid, For example, the alkaline permanganic acid solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment by an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 minutes to 30 minutes. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. The pH of the roughening liquid is preferably 11 or more. As a commercially available roughening liquid, the alkaline permanganic acid solution, such as "Concentrate Compact P", "Concentrate Compact CP", "Dosing solution Securiganth P" by Atotech Japan company, is mentioned, for example.

Moreover, an acidic aqueous solution is preferable as a neutralization liquid system used for a roughening process, and "Reduction solution Securiganth P" by Atotech Japan is mentioned as a commercial item, for example. The treatment by the neutralization solution can be performed by immersing the treated surface roughened by the oxidizing agent in the neutralization solution at 30° C. to 80° C. for 1 minute to 30 minutes. From a viewpoint of workability etc., the method of immersing the object roughened by an oxidizing agent in the neutralization liquid of 35 degreeC - 70 degreeC for 5 minutes - 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and more preferably 200 nm or less. The lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises at least one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium Metal. The conductor layer can be a simple metal layer or an alloy layer. As the alloy layer, for example, a layer formed of an alloy of two or more metals selected from the above-mentioned group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy) can be mentioned. Among them, from the viewpoints of versatility, cost, easiness of patterning, etc. of conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel, Alloy layers of chromium alloys, copper-nickel alloys, copper-titanium alloys are preferred, and elemental metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloys are preferred. It is still more preferable, and the elemental metal layer of copper is more preferable.

The conductor layer system may be a single-layer structure, or may be a multi-layer structure obtained by laminating two or more simple metal layers or alloy layers formed of different kinds of metals or alloys. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a simple metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer can be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern, from the viewpoint of simplicity of manufacture , preferably formed by a semi-additive method. An example in which the conductor layer is formed by the semi-additive method is shown below.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer is formed in accordance with a desired wiring pattern. After the metal layer is formed by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, by removing the unnecessary plating seed layer by etching or the like, a conductor layer having a desired wiring pattern can be formed.

[semiconductor device] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electrical products (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, airplanes, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The term "conduction site" refers to "a site where electrical signals are transmitted in a printed wiring board", and this site may be either a surface or a site that is embedded. In addition, the semiconductor wafer is not particularly limited as long as it is an electric circuit element using a semiconductor as a material.

There is no particular limitation on the mounting method of the semiconductor chip when manufacturing the semiconductor device, as long as the semiconductor chip can function effectively. Mounting method of bump build-up layer (BBUL), mounting method by anisotropic conductive film (ACF), mounting method by non-conductive film (NCF), etc. Here, the term "mounting method by means of a bumpless build-up layer (BBUL) layer" refers to "mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board, and the semiconductor chip is connected to the wiring on the printed wiring board." . [Example]

Hereinafter, the present invention will be specifically described by showing examples. However, the present invention is not limited to the following examples. In the following description, the "parts" and "%" indicating amounts represent the meanings of "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the operation demonstrated below was performed in the environment of normal temperature and normal pressure unless otherwise specified.

[Example 1] <Preparation of Resin Varnish A> 25 parts of maleimide compound b1 (“BMI-3000J” manufactured by Designer Molecules Co., Ltd.) as component (B), and polycarbonate resin a1 (“FPC2136” manufactured by Mitsubishi Gas Chemical Co., Ltd.) as component (A); Molecular weight: 20895) 20 parts were dissolved in 20 parts of methyl ethyl ketone (MEK) and 15 parts of toluene by heating and stirring, thereby obtaining a solution.

The resulting solution was cooled to room temperature. Then, a radically polymerizable compound d1 ("OPE-2St" (oligo-phenylene ether styrene resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added as the component (D) to the solution; number average molecular weight: 1200, non-volatile 9 parts of a toluene solution with a component of 65% by mass), an inorganic filler c as the component (C) (Spherical silica “SO-SO-2” manufactured by Admatechs Co., Ltd. surface-treated with an amine-based silane coupling agent “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd. C2" (average particle size: 0.5 μm, specific surface area: 5.8 m ² /g)) 50 parts, and 0.1 part of a hardening accelerator (“Perhexyl (registered trademark) D” manufactured by NOF Corporation) as component (E) Mixed, and further dispersed uniformly by a high-speed rotary mixer. Thereby, a dispersion liquid was obtained. Thereby, the resin varnish (nonvolatile content content: 73%) containing the resin composition of (A)-(E) component was prepared. Hereinafter, the resin varnish prepared in this way is also collectively referred to as "resin varnish A".

<Preparation of resin sheet B> As a support, a PET film (“Lumirror R80” manufactured by Toray Co., Ltd.; thickness 38 μm, softening point 130) in which one main surface was released with an alkyd resin-based mold release agent (“AL-5” manufactured by LINTEC Corporation) was prepared. °C, hereinafter sometimes referred to as "release PET").

Using a die coater, the resin varnish A was uniformly coated on the release-treated surface of the release PET so that the thickness of the resin composition layer after drying was 40 μm, and dried at 90° C. for 3 minutes. Thereby, a resin sheet including a support body and a resin composition layer containing a resin composition provided on the support body is obtained. Next, the rough surface of a polypropylene film (“Arufun MA-411” manufactured by Oji f-tex Co., Ltd., thickness 15 μm) as a protective film was laminated on the surface of the resin composition layer that was not bonded to the mold release PET, and the It is bonded to the resin composition layer. Thereby, the resin sheet which consists of a mold release PET (support body), a resin composition layer, and a protective film in this order (Hereinafter, the resin sheet produced in this way is also collectively referred to as "resin sheet B") is obtained.

<Evaluation of cured product of resin composition> Using the resin composition layer of the resin sheet B, the cured product of the resin composition was evaluated in terms of dielectric properties, substrate adhesion, roughness after chemical treatment, and plating adhesion according to the evaluation method described later. evaluate.

[Example 2] In Example 1, 20 parts of polycarbonate resin a1 ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd.; number average molecular weight: 20895) as component (A) was changed to polycarbonate resin a2 ( "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd.; number average molecular weight: 18911) 20 parts. Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[Example 3] In Example 1, 20 parts of polycarbonate resin a1 (“FPC2136” manufactured by Mitsubishi Gas Chemical Co., Ltd.; number average molecular weight: 20895) as component (A) was changed to polycarbonate resin a3 ( "PCZ200" manufactured by Mitsubishi Gas Chemical Co., Ltd.; viscosity average molecular weight: 21500) 20 parts. Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[Example 4] In Example 1, 25 parts of maleimide compound b1 (“BMI-3000J” manufactured by Designer Molecules Co., Ltd.) as component (B) was changed to maleimide compound b2 (Designer Molecules) as component (B). 25 copies of "BMI-1700" manufactured by Molecules. Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[Example 5] In Example 1, 25 parts of maleimide compound b1 (“BMI-3000J” manufactured by Designer Molecules Co., Ltd.) as component (B) was changed to maleimide compound b3 (Designer Molecules) as component (B) 25 copies of "BMI-1500" made by Molecules. Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[Example 6] In Example 1, 25 parts of maleimide compound b1 (“BMI-3000J” manufactured by Designer Molecules Co., Ltd.) as component (B) was changed to maleimide compound b3 (Designer Molecules) as component (B) 25 copies of "BMI-689" manufactured by Molecules. Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[Example 7] In Example 1, 9 parts of radical polymerizable compound d1 ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd.; number average molecular weight: 1200, 65 mass % nonvolatile content in toluene solution) as component (D) was changed 6 parts of radically polymerizable compound d2 (NK Ester "DCP" (tricyclodecane dimethanol dimethacrylate) by Shin-Nakamura Chemical Industry Co., Ltd.; molecular weight: 332) as the component (D) was prepared. Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[Example 8] In Example 1, 9 parts of radical polymerizable compound d1 ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd.; number average molecular weight: 1200, 65 mass % nonvolatile content in toluene solution) as component (D) was changed The radical polymerizable compound d3 (diallyl diphenyl dicarboxylate "DAD" (2,2'-diphenyl dicarboxylate diallyl ester (2,2'-biphenyl dicarboxylate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd. , 2'-biphenyldicarboxylic acid diallyl ester); molecular weight: 322) 6 parts. Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[Example 9] In Example 1, 9 parts of radical polymerizable compound d1 ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd.; number average molecular weight: 1200, 65 mass % nonvolatile content in toluene solution) as component (D) was changed 6 parts of radically polymerizable compound d4 (NK Ester "A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; molecular weight: 326) as the component (D) was prepared. Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[Comparative Example 1] In Example 1, 25 parts of the maleimide compound b1 (“BMI-3000J” manufactured by Designer Molecules Co., Ltd.) as the component (B) was not used. In Example 1, the radical polymerization of the component (D) was carried out. The mass parts of the volatile compound d1 ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd.; number average molecular weight: 1200, toluene solution of 65 mass % nonvolatile content) was changed from 9 parts to 48 parts. Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[Comparative Example 2] In Example 1, 25 parts of the maleimide compound b1 (“BMI-3000J” manufactured by Designer Molecules Co., Ltd.) as the component (B) was not used. In Example 1, the radical polymerization of the component (D) was carried out. 9 parts of chemical compound d1 ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd.; number average molecular weight: 1200, toluene solution of 65% by mass of non-volatile content) was changed to 9 parts of radically polymerizable compound d4 (NK manufactured by Shin-Nakamura Chemical Industry Co., Ltd. Ester "A-DOG"; molecular weight: 326) 31 parts. Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[Comparative Example 3] In Example 1, instead of using 20 parts of polycarbonate resin a1 ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd.; number average molecular weight: 20895) as the component (A), the thermoplastic resin as the component (A') was used ("YX6954BH30" by Mitsubishi Chemical Co., Ltd.; 1:1 solution of MEK with 30 mass % of non-volatile content and cyclohexanone, weight average molecular weight of non-volatile content: 35000) 66 parts. Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[Comparative Example 4] In Example 1, instead of using 25 parts of the maleimide compound b1 (“BMI-3000J” manufactured by Designer Molecules Co., Ltd.) as the component (B), the maleimide compound as the component (B') was used. ("BMI-70" (Bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane) manufactured by KI Chemical Co., Ltd.); maleimide compound not included in (B) component ) 25 servings. Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[Comparative Example 5] In Example 1, instead of using 25 parts of the maleimide compound b1 (“BMI-3000J” manufactured by Designer Molecules Co., Ltd.) as the component (B), the maleimide compound as the component (B') was used. ("BMI-70" (Bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane) manufactured by KI Chemical Co., Ltd.); maleimide compound not included in (B) component ) 25 servings. In addition, in Example 1, 9 parts of radically polymerizable compound d1 ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd.; number average molecular weight: 1200, 65 mass % nonvolatile content in toluene solution) as the component (D) was added , was changed to 6 parts of radically polymerizable compound d4 (NK Ester "A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; molecular weight: 326). Resin varnish A containing a resin composition was prepared in the same manner as in Example 1 except for the above matters. Moreover, using the resin varnish A, the resin sheet B was obtained in the same manner as in Example 1; similarly to Example 1, the resin composition layer of the resin sheet B was provided for evaluation.

[assessment method] Using the resin composition layer of the resin sheet B obtained in the above-mentioned Examples and Comparative Examples, from the viewpoints of dielectric properties, substrate adhesion, roughness after chemical treatment, and plating adhesion, The cured product of the resin composition layer was evaluated by the following method.

<<Evaluation of Dielectric Properties>> The evaluation of the dielectric properties was performed by measuring the values of the dielectric constant and the dielectric tangent by the following procedure, and by comprehensively evaluating the measured values. The measurement results and evaluation results are shown in Tables 1 and 2.

<Preparation of hardened product C for evaluation> The protective film was peeled off from the resin sheets B prepared in the examples and comparative examples, and the resin composition layer was thermally cured by heating at 200° C. for 90 minutes. material film. The cured product film was cut out with a width of 2 mm and a length of 80 mm to obtain a cured product C for evaluation.

＜Measurement＞ For each cured product C for evaluation, "HP8362B" manufactured by Agilent Technologies was used, and the values of the dielectric constant and the dielectric tangent were measured by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Three test pieces were measured, and the average value was calculated.

＜Assessment＞ The calculated average values of dielectric constant and dielectric tangent were evaluated according to the following criteria. "○": When the average value of the dielectric constant is 3.2 or less and the average value of the dielectric tangent is 0.0040 or less, the dielectric properties are evaluated to be excellent. "X": When one or both of the average value of the dielectric constant and the average value of the dielectric tangent did not satisfy the above criteria, the dielectric properties were evaluated as poor.

<<Assessment of Substrate Adhesion>> Evaluation of substrate adhesion was carried out by measuring copper foil peel strength according to the following procedure. The measurement results and evaluation results are shown in Tables 1 and 2.

<Preparation of Evaluation Board D> (1) Base treatment of copper foil By dipping the glossy surface of "3EC-III" (electrolytic copper foil, 35μm) manufactured by Mitsui Metal Mining Co., Ltd. in MEC MECetchBOND "CZ-8201" manufactured by MEC Corporation, the Ra value of the copper surface becomes 0.5μm. Roughening treatment was performed, and then, rust preventive treatment (CL8300) was applied. This copper foil is called CZ copper foil. Furthermore, it heat-processed for 30 minutes in the oven of 130 degreeC. Thereby, the CZ copper foil whose surface is low roughness is obtained.

(2) Lamination of resin composition layers, lamination of copper foils, and formation of insulating layers The protective film was peeled off from each resin sheet B produced in the Example and the comparative example, and the resin composition layer was exposed. Using a batch type vacuum pressure laminating machine ("MVLP-500" manufactured by Meiki Co., Ltd.), the exposed resin composition layer and the glass cloth base epoxy resin double-sided copper clad laminate (copper The thickness of the foil is 18 μm, the thickness of the substrate is 0.4 mm, and “R1515A” manufactured by Panasonic Co., Ltd.) was bonded, and the resin sheet B with the protective film peeled off was laminated on both sides of the laminate. The lamination treatment was performed by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then performing pressure bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds. The support is peeled off from the laminated resin sheet B. Under the same conditions as above, the treated surface of the CZ copper foil was laminated on each resin composition layer. Moreover, the resin composition layer was hardened under hardening conditions of 190 degreeC and 90 minutes, and the insulating layer was formed. In the same manner, the evaluation board D in which the CZ copper foil was layered in two areas was produced.

<Measurement of copper foil peel strength> The produced evaluation substrate D was cut into small pieces of 150×30 mm. Using a dicing knife, cut a 10 mm wide and 100 mm long portion in the copper foil portion of the small piece, peel off one end of the copper foil, grasp it with a clipper attached to a tensile tester described later, and measure at room temperature ( In normal temperature), the load [kgf/cm] when peeling off 35mm in the vertical direction at a speed of 50mm/min. The measurement system used a tensile testing machine (Autocom universal testing machine "AC-50C-SL" manufactured by TSE Corporation). The measurement was performed according to the Japanese Industrial Standard JIS C6481. The load value obtained as a result of this measurement is also referred to as copper foil peel strength.

＜Assessment＞ The value of the copper foil peel strength obtained as a result of the measurement was evaluated according to the following criteria. "○": When the value of the copper foil peeling strength satisfies 0.50 kgf/cm or more, the base adhesion is evaluated to be excellent. "X": When the value of the copper foil peeling strength did not satisfy the above-mentioned standard (when it was less than 0.50 kgf/cm), the base adhesion was evaluated as poor.

<<Evaluation of chemical resistance and evaluation of plating adhesion>> The evaluation of the plating adhesion was carried out by measuring the plating peeling strength according to the following procedure. The evaluation of the roughness after the chemical solution treatment was performed by measuring the arithmetic mean roughness in the middle of preparing the evaluation substrate for evaluation of the plating adhesion. The measurement results and evaluation results are shown in Tables 1 and 2.

<Preparation of Evaluation Board E> (1) Base treatment of laminates The glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, "R5715ES" manufactured by Matsushita Electric Co., Ltd.) on which the inner layer circuit was formed was immersed in MEC (Co., Ltd.). ) made "CZ8100" to roughen the copper surface. Thereby, the laminated board whose copper surface was roughened was obtained.

(2) Lamination of resin composition layers The protective film was peeled off from the resin sheet B produced in the Examples and Comparative Examples to expose the resin composition layer. Using a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Co., Ltd.), the resin sheet B from which the protective film was peeled off was laminated to the exposed resin composition layer. Both sides of the laminate. The lamination treatment was performed by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then performing pressure bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Formation of insulating layer The support is peeled off from the laminated resin sheet B. In addition, the resin composition layer was cured under the curing conditions of 100° C. for 30 minutes and then 180° C. for 30 minutes. Thereby, the laminated board in which the insulating layer was formed in both surfaces was obtained.

(4) Measurement of the arithmetic mean roughness (Ra) of the insulating layer after roughening treatment and roughening treatment The laminate was immersed in a swelling solution "Swelling Dip Securiganth P" (containing diethylene glycol) manufactured by Atotech Japan at 60°C. monobutyl ether) for 5 minutes. Next, the laminate was immersed in a roughening solution "Concentrate Compact P" (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution, pH: 11) manufactured by Atotech Japan at 80° C. for 20 minutes. Finally, the laminate was immersed in a neutralizing solution "Reduction solution Securiganth P" manufactured by Atotech Japan at 40°C for 5 minutes. In this manner, roughening treatment is given to the insulating layers exposed on both surfaces of the laminate. With respect to the insulating layer to which the roughening treatment has been given, the chemical resistance is evaluated in the manner described later.

(5) Formation of conductor layer by semi-additive process (SAP) In order to form a circuit on the surface of the insulating layer to which the roughening treatment has been applied, the laminate is immersed in a solution for electroless plating _{containing PdCl 2 ,} Next, it is immersed in an electroless copper plating solution. After that, annealing treatment was performed by heating at 150° C. for 30 minutes. Furthermore, after forming the etching resist, pattern formation by etching is performed. Next, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30±5 μm. Next, annealing treatment was performed at 180° C. for 60 minutes. In the same manner, the evaluation substrate E was produced. For this evaluation substrate E, the plating adhesion was evaluated in the following manner.

<Evaluation of drug resistance> The chemical resistance was evaluated by measuring the arithmetic mean roughness (Ra) of the insulating layer after the roughening treatment in the above (4), and evaluating the arithmetic mean roughness (Ra) value obtained from the measurement results. evaluate. The measurement results and evaluation results are shown in Tables 1 and 2.

<Measurement of Arithmetic Average Roughness (Ra)> Using a non-contact surface roughness meter (“WYKO NT3300” manufactured by Veeco Instruments), the arithmetic mean roughness (Ra) was obtained from the value obtained in the measurement range of 121 μm × 92 μm by the VSI mode and the 50x lens. Value [nm]. In addition, the measurement was performed by obtaining the average value of 10 points.

＜Assessment＞ The average value of the arithmetic mean roughness (Ra) obtained as a result of the measurement was evaluated according to the following criteria. "○": When the average value of the arithmetic mean roughness (Ra) is less than 300 nm, it is evaluated that the roughness after the chemical solution treatment is sufficiently low and the chemical resistance is excellent. "X": When the average value of the arithmetic mean roughness (Ra) was 300 nm or more, the roughness after the chemical solution treatment was evaluated to be high and the chemical resistance was poor.

<Measurement of plating peel strength (peel strength)> The conductor layer of the evaluation substrate E was cut with a width of 10 mm and a length of 100 mm, and one end of the conductor layer was peeled off, grasped with a clipper, measured at room temperature, and peeled off in the vertical direction at a speed of 50 mm/min. Load at 35mm [kgf/cm]. The measurement system used a tensile tester (Auto COM universal testing machine "AC-50C-SL" manufactured by TSE Corporation) in the same manner as the measurement of the copper foil peeling strength. The measurement was performed according to the Japanese Industrial Standard JIS C6481. The value of the load obtained as a result of this measurement is also referred to as plating peel strength (peel strength).

＜Assessment＞ The value of the plating peel strength obtained as a result of the measurement was evaluated according to the following criteria. "○": When the value of the plating peel strength satisfies 0.35 kgf/cm or more, the plating adhesion is evaluated to be excellent. "X": When the value of the plating peel strength did not satisfy the above-mentioned standard (when it was less than 0.35 kgf/cm), the plating adhesion was evaluated as poor.

[result] The results of the above-mentioned Examples and Comparative Examples are shown in Tables 1 and 2 below. In the following Table 1 and Table 2, the amount of each component represents the amount in terms of non-volatile components. In addition, "A/resin component" shown in Table 1 and Table 2 represents the content of (A) component when the resin component in the resin composition is 100% by mass; "A/B" represents ( The value of the mass ratio of A) component to (B) component; "C/non-volatile matter" shows the content of (A) component when the non-volatile matter in the resin composition is 100% by mass. In addition, the so-called resin component refers to all components after deducting the (C) component and (A') component from the non-volatile components in the resin composition.

＜Seminar＞ As can be seen from Table 1 and Table 2, it can be seen from the comparison between the examples and the comparative examples that the examples can provide a resin composition, and the resin composition can be obtained without damaging the resultant obtained by using the maleimide compound. The resulting excellent dielectric properties, adhesion and chemical resistance are excellent cured products. In addition, it was found that the cured product of the resin composition according to the embodiment; the resin sheet including the resin composition; the printed wiring board including the insulating layer formed by the cured product of the resin composition, and the semiconductor can also be provided device. In addition, the cured resin composition according to the examples can realize low roughness due to its excellent chemical resistance, and also has excellent dielectric properties, so it is suitable for operation even under high-frequency electrical signals. circuit boards and semiconductor devices.

Furthermore, in Examples 1 to 9, even if the components (C) to (E) are not contained, although the degree is different, it was confirmed that the results were the same as those of the above-mentioned Examples. Furthermore, in Examples 1 to 9, even if one or both of (A') component and (B') component are contained in an amount within a range that does not inhibit the desired effect of the present invention, although the degree is different, However, it was confirmed that the results were the same as those of the above-mentioned examples.

Claims (23)

A resin composition comprising (A) a polycarbonate resin and (B) a maleimide compound, wherein the maleimide compound comprises an alkyl group having 5 or more carbon atoms and an alkyl group having 5 carbon atoms A hydrocarbon chain of at least one of the above alkylene groups. The resin composition according to claim 1, wherein the component (A) is any one or more of an aliphatic skeleton-containing polycarbonate resin and an aromatic skeleton-containing polycarbonate resin. The resin composition according to claim 2, wherein the component (A) contains an aromatic skeleton-containing polycarbonate resin. The resin composition according to claim 1, wherein the number average molecular weight or viscosity average molecular weight of the component (A) is 1,000 or more and 300,000 or less. The resin composition according to claim 1, wherein the content of the component (A) is 1 mass % or more and 40 mass % or less when the nonvolatile matter in the resin composition is 100 mass %. The resin composition according to claim 1, wherein the value of A/B representing the mass ratio of the (A) component to the (B) component is 0.01 or more and 1.5 or less. The resin composition of claim 1, wherein the component (B) is represented by the following general formula (B1),

In general formula (B1), M represents an optionally substituted divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms, and L represents a single bond or a divalent linking group. The resin composition according to claim 1, wherein the component (B) is a maleimide compound, and the maleimide compound contains an alkyl group having 5 to 50 carbon atoms and an alkyl group having 5 to 50 carbon atoms. A hydrocarbon chain of at least any one of the following alkylene groups. The resin composition according to claim 1, wherein the content of the component (B) is 0.1 mass % or more and 60 mass % or less when the non-volatile matter in the resin composition is 100 mass %. The resin composition according to claim 1, further comprising (C) an inorganic filler. The resin composition of Claim 10 whose content of (C)component is 30 mass % or more when the non-volatile matter in the resin composition is 100 mass %. The resin composition according to claim 1, further comprising (D) a radically polymerizable compound. The resin composition according to claim 12, wherein the component (D) contains a molecule selected from the group consisting of vinyl, allyl, acryl, methacryloyl, fumaric, and maleic At least one of a group, a vinylphenyl group, a styryl group, and a cinnamyl group is used as a radically polymerizable unsaturated group. The resin composition according to claim 12, wherein the component (D) has two or more radically polymerizable unsaturated groups in the molecule. The resin composition of claim 1, wherein the dielectric of the cured product obtained by heat treatment at 200°C for 90 minutes is measured by cavity resonance perturbation method under the conditions of a measurement frequency of 5.8 GHz and a measurement temperature of 23°C The rate is below 3.2. The resin composition of claim 1, wherein the dielectric of the cured product obtained by heat treatment at 200°C for 90 minutes is measured by cavity resonance perturbation method under the conditions of a measurement frequency of 5.8 GHz and a measurement temperature of 23°C The tangent is below 0.0040. The resin composition according to claim 1, wherein the cured product obtained by heat treatment at 180° C. for 30 minutes is immersed in a roughening liquid at 80° C. for 20 minutes, and then the cured product is measured with a non-contact surface roughness meter The arithmetic mean surface roughness of the material is 260 nm or less. The resin composition according to claim 1, which is for forming an insulating layer. The resin composition according to claim 1, which is for forming an insulating layer for forming a conductor layer. A hardened product of the resin composition according to any one of claims 1 to 19. A resin sheet, comprising a support body and a resin composition layer disposed on the support body, wherein the resin composition layer comprises the resin composition according to any one of claims 1 to 19. A printed wiring board comprising an insulating layer formed by the cured product of the resin composition according to any one of Claims 1 to 19 or the cured product of Claim 20. A semiconductor device comprising the printed wiring board of claim 22.