TW202323438A - Resin composition, prepreg, laminate, resin film, printed wiring board, and semiconductor package - Google Patents

Abstract

The present invention relates to: a resin composition comprising (A) a heat-curable resin, (B) a poly(phenylene ether)-based resin, (C) an alkoxysilane compound having a primary amino group, and (D) an inorganic filler; and a prepreg, a laminate, a resin film, a printed wiring board, and a semiconductor package each obtained using the resin composition.

Description

Resin composition, prepreg, laminate, resin film, printed wiring board, and semiconductor package

This embodiment relates to a resin composition, a prepreg, a laminate, a resin film, a printed wiring board, and a semiconductor package.

The speed and capacity of signals used by mobile communication devices represented by mobile phones, base station devices, network infrastructure devices such as servers and routers, and electronic devices such as large computers are increasing year by year. With this progress, the dielectric characteristics [hereinafter sometimes referred to as "high-frequency characteristics"], also That is, low relative permittivity and low dielectric loss tangent. In recent years, in addition to the above-mentioned electronic equipment, in the field of ITS (Intelligent Transport Systems, Intelligent Transport System) related to automobiles and traffic systems, and in the field of indoor short-distance communication, the development of novel systems for processing high-frequency wireless signals Practical or practical plans are also in progress. Therefore, it is expected that the need for substrate materials excellent in high-frequency characteristics will also increase in the future for printed wiring boards used in these fields.

The problem to be solved in Patent Document 1 is to provide a curable resin composition as a resin composition that can be applied to the insulating layer of a printed wiring board, and the relative permittivity and The dielectric loss tangent is low and the heat resistance is also excellent, and a curable resin composition is disclosed, which is characterized by containing a naphthol novolak type epoxy resin and a polyphenylene ether resin. [Prior Art Literature] (patent documents)

Patent Document 1: Japanese Patent Laid-Open No. 2013-185080

[Problem to be solved by the invention] However, when polyphenylene ether is mixed with thermosetting resin like the technique of patent document 1, sufficient copper foil peeling strength may not be acquired. In order to respond to the increasing demand for high-frequency characteristics in the future, a technology that can obtain excellent copper foil peel strength even when polyphenylene ether is compounded is expected. In addition, the fluidity of the polyphenylene ether itself and the mass concentration of the thermosetting resin in the resin composition decrease due to the preparation of the polyphenylene ether, and the resin composition may flow excessively during lamination pressurization. Formability deteriorated. To solve this problem, it is more effective to improve the curability of the resin composition. The curability of the resin composition can be improved, for example, by using a hardening accelerator. However, since the hardening accelerator may lower the dielectric properties, it is preferable to keep the amount of the hardening accelerator low.

In view of such current situation, the problem to be solved by this embodiment is to provide a resin composition, a prepreg using the resin composition, a laminate, a resin film, a printed wiring board, and a semiconductor package. Excellent copper foil peel strength and hardenability. [Technical means to solve the problem]

As a result of intensive studies by the present inventors in order to solve the above-mentioned problem to be solved, it was found that the above-mentioned problem to be solved can be solved by the present embodiment described below. In other words, this embodiment relates to the following [1] to [14]. [1] A resin composition comprising: (A) thermosetting resin; (B) polyphenylene ether resin; (C) alkoxysilane compounds having primary amino groups; and (D) Inorganic filler material. [2] The resin composition according to the above [1], wherein the (A) thermosetting resin is selected from the group consisting of epoxy resins, cyanate resins, and maleimide resins. more than 1 species. [3] The resin composition according to the above [1] or [2], wherein the (A) thermosetting resin is a maleimide resin. [4] The resin composition according to any one of [1] to [3] above, wherein the (B) polyphenylene ether-based resin has a functional group containing an ethylenically unsaturated bond. [5] The resin composition according to the above [4], wherein the functional group containing an ethylenically unsaturated bond is a (meth)acryl group. [6] The resin composition according to any one of the above [1] to [5], wherein the (C) alkoxysilane compound having a primary amino group has a trialkoxysilyl group. [7] The resin composition according to any one of the above [1] to [6], wherein the (C) has a primary amino group with respect to the total solid content (100% by mass) of the resin composition The content of the alkoxysilane compound is 0.1 to 10% by mass. [8] The resin composition according to any one of [1] to [7] above, wherein the (D) inorganic filler is silicon oxide. [9] The resin composition according to any one of [1] to [8] above, further comprising: (E) a styrene-based elastomer. [10] A prepreg comprising the resin composition according to any one of [1] to [9] above or a semi-cured product of the resin composition. [11] A laminate comprising a cured product of the prepreg according to the above [10]. [12] A resin film comprising the resin composition according to any one of [1] to [9] above or a semi-cured product of the resin composition. [13] A printed wiring board having a cured product of the resin composition according to any one of the above [1] to [9]. [14] A semiconductor package comprising the printed wiring board described in [13] above. [effect]

According to this embodiment, there can be provided a resin composition having excellent copper foil peel strength and curability, and a prepreg, laminate, resin film, printed wiring board, and semiconductor package using the resin composition.

In this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as a minimum value and a maximum value, respectively. For example, a notation such as a numerical range "X~Y" (X and Y are real numbers) means a numerical range between X and Y. In addition, in this specification, description of "X or more" means X and the numerical value exceeding X. In addition, in this specification, description of "below Y" means Y and the numerical value below Y. The lower limit and upper limit of the numerical range described in this specification can be arbitrarily combined with the lower limit or upper limit of another numerical range, respectively. In the numerical range described in this specification, the lower limit value or the upper limit value of the numerical range can be replaced with the value disclosed in an Example.

Each component and material illustrated in this specification may be used individually by 1 type, and may use 2 or more types together, unless otherwise indicated. In this specification, when a plurality of substances corresponding to each component exist in the resin composition, the content of each component in the resin composition means the content of the plurality of substances present in the resin composition unless otherwise specified. total amount.

In the present specification, "solid content" means components other than solvents, and includes liquid, syrupy and waxy ones at room temperature. Here, in this specification, room temperature means 25°C.

In this specification, "(meth)acryl" means "acryl" and its corresponding "methacryl".

In the present specification, the weight average molecular weight (Mw) means a value measured in terms of polystyrene by gel permeation chromatography (GPC; Gas Permeation Chromatography). Specifically, in the present specification, the weight average molecular weight (Mw) can be measured by the method described in the examples.

The mechanism of action described in this specification is only speculation, and is not intended to limit the mechanism for producing the effects of this embodiment.

Embodiments in which the items described in this specification are combined arbitrarily are also included in this embodiment.

[Resin composition] The resin composition of this embodiment contains: (A) thermosetting resin; (B) polyphenylene ether resin; (C) alkoxysilane compounds having primary amino groups; and (D) Inorganic filler material. In addition, in this specification, the said component may abbreviate and call it (A) component, (B) component, (C) component, (D) component etc., respectively, and may employ the same abbreviation form about other components.

The reason why the resin composition of the present embodiment is excellent in copper foil peel strength and curability is presumed to be as follows. The resin composition of this embodiment contains: (A) thermosetting resin, and (B) polyphenylene ether resin. The (B) polyphenylene ether-based resin tends to have weaker intermolecular forces with other components due to the lower probability of presence of polar groups than the (A) thermosetting resin. Therefore, it is considered that the resin composition is easily broken when stress for peeling copper foil is added to the resin composition (B) polyphenylene ether-based resin. On the other hand, we speculate that the resin composition of this embodiment can solve the above-mentioned problems by containing (C) an alkoxysilane compound having a primary amino group. (C) The alkoxysilane compound having a primary amino group has: a primary amino group excellent in reactivity and affinity with an organic component; and an alkoxysilyl group excellent in reactivity and affinity with an inorganic component Excellent affinity. Therefore, we speculate that: the resin composition of this embodiment contains (C) an alkoxysilane compound with a primary amino group, and the main reason is that the interfacial adhesion between the organic component and the inorganic component has been strengthened, and it is not easy to produce resin. The interface between the phase and the (D) inorganic filler material is broken, while the copper foil peel strength has increased. In addition, we think that the reaction between the above-mentioned (C) alkoxysilane compound having a primary amino group and the organic component, and the strengthening of the interfacial adhesion between the organic component and the inorganic component appear in the hardening reaction, and this The curability of the resin composition of the embodiment is improved. Each component which can be contained in this embodiment is demonstrated in order below.

＜(A) Thermosetting resin＞ The resin composition of this embodiment contains: (A) thermosetting resin. (A) Thermosetting resin may be used individually by 1 type, and may use 2 or more types together.

(A) Thermosetting resins include, for example, epoxy resins, phenol resins, maleimide resins, cyanate resins, isocyanate resins, benzoxazine resins, and oxetane resins. Resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, etc. (A) Thermosetting resin From the viewpoint of heat resistance, among these, one or more selected from the group consisting of epoxy resins, cyanate resins, and maleimide resins is preferable. , preferably maleimide resins, from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins At least one selected from the group is more preferable.

Furthermore, in the following description, sometimes "from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins One or more selected from the group" is called "maleimide-based resin". In addition, in the following description, a maleimide resin having one or more N-substituted maleimide groups may be referred to as "maleimide resin (AX)" or "(AX) component ". In addition, derivatives of maleimide resins having one or more N-substituted maleimide groups are sometimes referred to as "maleimide resin derivatives (AY)" or "(AY) component ".

(maleimide resin (AX)) The maleimide resin (AX) is not particularly limited as long as it is a maleimide resin having one or more N-substituted maleimide groups. From the viewpoint of conductor adhesion and heat resistance, the maleimide resin (AX) is preferably an aromatic maleimide resin having two or more N-substituted maleimide groups. An aromatic maleimide resin having two N-substituted maleimide groups is preferable. In addition, in this specification, "aromatic maleimide resin" means the compound which has the N-substituted maleimide group directly bonded to an aromatic ring. In addition, in this specification, "aromatic bismaleimide resin" means the compound which has two N-substituted maleimide groups directly bonded to an aromatic ring. In addition, in this specification, "aromatic polymaleimide resin" means the compound which has 3 or more N-substituted maleimide groups directly bonded to an aromatic ring. In addition, in this specification, "aliphatic maleimide resin" means the compound which has the N-substituted maleimide group directly bonded to aliphatic hydrocarbon.

The maleimide resin (AX) is preferably a maleimide resin represented by the following general formula (A1-1) [hereinafter referred to as maleimide resin (A1)].

式(A1-1)中，X ^a11為2價有機基。

In formula (A1-1), X ^a11 is a divalent organic group.

In the above general formula (A1-1), X ^a11 is a divalent organic group. In the above-mentioned general formula (A1-1), the divalent organic group represented by X ^a11 includes, for example: a divalent organic group represented by the following general formula (A1-2), a 2-valent organic group represented by the following general formula (A1-3) A valent organic group, a divalent organic group represented by the following general formula (A1-4), a divalent organic group represented by the following general formula (A1-5), a divalent organic group represented by the following general formula (A1-6) Base etc.

式(A1-2)中，R ^a11為碳數1～5的脂肪族烴基或鹵素原子；n ^a11為0～4的整數；＊表示鍵結部位。

In formula (A1-2), R ^a11 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; n ^a11 is an integer of 0 to 4; * represents a bonding site.

In the above-mentioned general formula (A1-2), the aliphatic hydrocarbon group having 1 to 5 carbons represented by R ^a11 can be exemplified: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, three Alkyl groups with 1 to 5 carbons such as butyl and n-pentyl; alkenyls with 2 to 5 carbons, alkynyls with 2 to 5 carbons, etc. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. The aliphatic hydrocarbon group having 1-5 carbons is preferably an aliphatic hydrocarbon group having 1-3 carbons, preferably an alkyl group having 1-3 carbons, and more preferably a methyl group. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom and the like. In the above-mentioned general formula (A1-2), n ^a11 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and more preferably 0 from the viewpoint of ease of acquisition. When n ^a11 is an integer of 2 or more, plural R ^a11 may be the same as or different from each other.

式(A1-3)中，R ^a12及R ^a13分別獨立地為碳數1～5的脂肪族烴基或鹵素原子；X ^a12為碳數1～5的伸烷基、碳數2～5的亞烷基、醚基、硫醚基、磺醯基、羰氧基、羰基(keto group)、單鍵、或下述通式(A1-3-1)表示的2價基；n ^a12及n ^a13分別獨立地為0～4的整數；＊表示鍵結部位。

In formula (A1-3), R ^a12 and R ^a13 are independently an aliphatic hydrocarbon group or a halogen atom with 1 to 5 carbons; X ^a12 is an alkylene group with 1 to 5 carbons, an alkylene group with 2 to 5 carbons; Alkyl group, ether group, thioether group, sulfonyl group, carbonyloxy group, carbonyl (keto group), single bond, or a divalent group represented by the following general formula (A1-3-1); n ^a12 and n ^a13 are each independently an integer of 0 to 4; * represents a bonding site.

In the above general formula (A1-3), the aliphatic hydrocarbon groups with 1 to 5 carbons represented by R ^a12 and R ^a13 include, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Alkyl groups with 1 to 5 carbons such as tertiary butyl, n-pentyl, etc.; alkenyls with 2 to 5 carbons, alkynyls with 2 to 5 carbons, etc. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. The aliphatic hydrocarbon group having 1 to 5 carbons is preferably an aliphatic hydrocarbon group having 1 to 3 carbons, more preferably an alkyl group having 1 to 3 carbons, more preferably methyl or ethyl. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom and the like.

In the above general formula (A1-3), the alkylene group having 1 to 5 carbons represented by X ^a12 includes, for example, methylene, 1,2-dimethylene, 1,3-trimethylene, 1, 4-tetramethylene, 1,5-pentamethylene, etc. The alkylene group having 1 to 5 carbons is preferably an alkylene group having 1 to 3 carbons, more preferably an alkylene group having 1 or 2 carbons, and more preferably methylene.

In the above general formula (A1-3), the alkylene group having 2 to 5 carbon atoms represented by X ^a12 includes, for example, ethylene, propylene, isopropylidene, butylene, isobutylene, pentylene group, isopentylene, etc. Among these, an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and isopropylidene is more preferable.

In the above general formula (A1-3), n ^a12 and n ^a13 are each independently an integer of 0-4. When n ^a12 or n ^a13 is an integer of 2 or more, the plurality of R ^a12 or the plurality of R ^a13 may be the same as or different from each other.

In the general formula (A1-3), the divalent group represented by the general formula (A1-3-1) represented by X ^a12 is as follows.

式(A1-3-1)中，R ^a14及R ^a15分別獨立地為碳數1～5的脂肪族烴基或鹵素原子；X ^a13為碳數1～5的伸烷基、碳數2～5的亞烷基、醚基、硫醚基、磺醯基、羰氧基、羰基、或單鍵；n ^a14及n ^a15分別獨立地為0～4的整數；＊表示鍵結部位。

In the formula (A1-3-1), R ^a14 and R ^a15 are independently an aliphatic hydrocarbon group or a halogen atom with 1 to 5 carbons; X ^a13 is an alkylene group with 1 to 5 carbons, The alkylene group, ether group, thioether group, sulfonyl group, carbonyloxy group, carbonyl group, or single bond; n ^a14 and n ^a15 are each independently an integer of 0 to 4; * represents a bonding site.

In the above general formula (A1-3-1), the aliphatic hydrocarbon groups having 1 to 5 carbons represented by R ^a14 and R ^a15 include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, Alkyl groups with 1 to 5 carbons such as isobutyl, tertiary butyl, and n-pentyl; alkenyls with 2 to 5 carbons, alkynyls with 2 to 5 carbons, etc. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. The aliphatic hydrocarbon group having 1-5 carbons is preferably an aliphatic hydrocarbon group having 1-3 carbons, preferably an alkyl group having 1-3 carbons, and more preferably a methyl group. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom and the like.

In the above general formula (A1-3-1), the alkylene group having 1 to 5 carbons represented by X ^a13 includes, for example, methylene, 1,2-dimethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,5-pentamethylene, etc. The alkylene group having 1 to 5 carbons is preferably an alkylene group having 1 to 3 carbons, more preferably an alkylene group having 1 or 2 carbons, and more preferably methylene.

In the above general formula (A1-3-1), the alkylene group having 2 to 5 carbons represented by X ^a13 includes, for example, ethylene, propylene, isopropylidene, butylene, isobutylene, Pentylene, isopentylene, etc. Among these, an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and isopropylidene is more preferable.

In the above general formula (A1-3-1), among the above options, X ^a13 is preferably an alkylene group with 2 to 5 carbons, preferably an alkylene group with 2 to 4 carbons, and more preferably an isopropylidene group. good.

In the above general formula (A1-3-1), n ^a14 and n ^a15 are each independently an integer of 0 to 4, and from the viewpoint of ease of acquisition, an integer of 0 to 2 is preferred, and 0 or 1 Better, 0 is better. When n ^a14 or n ^a15 is an integer of 2 or more, plural R ^a14 or plural R ^a15 may be the same as or different from each other.

In the above general formula (A1-3), among the above options, X ^a12 is an alkylene group with 1 to 5 carbons, an alkylene group with 2 to 5 carbons, or 2 represented by the above general formula (A1-3-1). The valence group is preferred, preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group.

式(A1-4)中，n ^a16為0～10的整數；＊表示鍵結部位。

In the formula (A1-4), n ^a16 is an integer of 0 to 10; * represents a bonding site.

In the general formula (A1-4), n ^a16 is preferably an integer of 0-5, more preferably an integer of 0-4, and more preferably an integer of 0-3, from the viewpoint of ease of acquisition.

式(A1-5)中，n ^a17為0～5的數；＊表示鍵結部位。

In the formula (A1-5), n ^a17 is a number from 0 to 5; * represents a bonding site.

式(A1-6)中，R ^a16及R ^a17分別獨立地為氫原子或碳數1～5的脂肪族烴基；n ^a18為1～8的整數；＊表示鍵結部位。

In formula (A1-6), R ^a16 and R ^a17 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbons; n ^a18 is an integer of 1 to 8; * represents a bonding site.

In the above general formula (A1-6), the aliphatic hydrocarbon groups with 1 to 5 carbons represented by R ^a16 and R ^a17 include, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Alkyl groups with 1 to 5 carbons such as tertiary butyl, n-pentyl, etc.; alkenyls with 2 to 5 carbons, alkynyls with 2 to 5 carbons, etc. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. In the above general formula (A1-6), n ^a18 is an integer of 1-8, preferably an integer of 1-5, preferably an integer of 1-3, and more preferably 1. When n ^a18 is an integer of 2 or more, plural R ^a16 or plural R ^a17 may be the same or different from each other.

As maleimide resin (A1), aromatic bismaleimide resin, aromatic polymaleimide resin, aliphatic maleimide resin etc. are mentioned, for example. Specific examples of maleimide resin (A1) can be, for example: N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N' -(1,3-phenylene)bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[ 1,3-(4-Methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimide Aminophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenyl Methyl methane bismaleimide, bis (4-maleimide phenyl) ether, bis (4-maleimide phenyl) sulfide, bis (4-maleimide phenyl) sulfur ether, bis(4-maleimidephenyl) ketone, bis(4-maleimidecyclohexyl)methane, 1,4-bis(4-maleimidephenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy ) benzene, 1,3-bis(3-maleimidephenoxy)benzene, bis[4-(3-maleimidephenoxy)phenyl]methane, bis[4-(4- Maleimidephenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidephenoxy)phenyl]ethane, 1,1-bis[4-(4 -Maleimidephenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidephenoxy)phenyl]ethane, 1,2-bis[4- (4-maleimidephenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidephenoxy)phenyl]propane, 2,2-bis[4 -(4-maleimidephenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidephenoxy)phenyl]butane, 2,2-bis[ 4-(4-maleimidephenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidephenoxy)phenyl]-1,1,1, 3,3,3-Hexafluoropropane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-maleimidephenoxy)biphenyl, 4,4-bis(4-maleimidephenoxy)biphenyl, bis[4-(3-maleimide Iminophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy)phenyl]ketone, bis(4-maleimidophenyl)disulfide, bis[ 4-(3-maleimidephenoxy)phenyl]sulfide, bis[4-(4-maleimidephenoxy)phenyl]sulfide, bis[4-(3-maleimide Acrylimidephenoxy)phenyl]sulfide, bis[4-(4-maleimidephenoxy)phenyl]sulfide, bis[4-(3-maleimidephenoxy) base) phenyl] phenyl], bis [4-(4-maleimidephenoxy) phenyl] phenyl, bis [4- (3-maleimide phenoxy) phenyl] ether, bis [4-(4-maleimidephenoxy)phenyl]ether, 1,4-bis[4-(4-maleimidephenoxy)-α,α-dimethylbenzyl base]benzene, 1,3-bis[4-(4-maleimidephenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimide Maleimidephenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidephenoxy)-α,α-dimethyl Benzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1, 3-bis[4-(4-maleimidephenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3 -maleimidephenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidephenoxy base)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethane maleimide, biphenylaralkyl type maleimide, etc. Among them, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane is preferable.

(maleimide resin derivative (AY)) The maleimide resin derivative (AY) is an aminomaleimide resin having a structural unit derived from the above-mentioned maleimide resin (AX) and a structural unit derived from a diamine compound [hereinafter referred to as It is preferably called "aminomaleimide resin (A2)" or "component (A2)"].

[Aminomaleimide resin (A2)] Amino maleimide resin (A2) has a structural unit derived from maleimide resin (AX) and a diamine compound [hereinafter sometimes referred to as "diamine compound (a)" or "(a ) component "] structural unit.

"Structural Units Derived from Maleimide Resin (AX)" Structural units derived from maleimide resin (AX) include, for example, at least one N-substituted maleimide group among N-substituted maleimide groups possessed by maleimide resin (AX). A structural unit in which an imine group and an amine group of a diamine compound undergo Michael addition reaction. The structural unit derived from the maleimide resin (AX) contained in the aminomaleimide resin (A2) may be one type alone, or two or more types.

In the aminomaleimide resin (A2), the content of the structural unit derived from the maleimide resin (AX) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 30 to 93% by mass , more preferably 60-90% by mass. When the content of the structural unit derived from the maleimide resin (AX) in the aminomaleimide resin (A2) is within the above range, the dielectric properties and film handling properties tend to be better.

"Structural unit derived from diamine compound (a)" Structural units derived from the diamine compound (a) include, for example: one or both of the amine groups of the diamine compound (a) and the N- Structural unit obtained by substituted maleimide group by Myco addition reaction. In the aminomaleimide resin (A2), the structural unit derived from the diamine compound (a) may be one type alone or two or more types.

The amine group that the diamine compound (a) has is preferably a primary amine group. As a structural unit derived from the diamine compound (a) which has two primary amino groups, the group represented by following general formula (a-1), the group represented by following general formula (a-2), etc. are mentioned, for example.

式(a-1)、(a-2)中，X ^a21為2價有機基，＊表示鍵結部位。

In formulas (a-1) and (a-2), X ^a21 is a divalent organic group, and * represents a bonding site.

In the above-mentioned general formula (a-1) and the above-mentioned general formula (a-2), X ^a21 is a divalent organic group and corresponds to a divalent group obtained by removing two primary amino groups from the diamine compound (a). .

In the above-mentioned general formula (a-1) and the above-mentioned general formula (a-2), X ^a21 is preferably a divalent group represented by the following general formula (a-3).

式(a-3)中，R ^a21及R ^a22分別獨立地為碳數1～5的脂肪族烴基、碳數1～5的烷氧基、羥基、或鹵素原子；X ^a22為碳數1～5的伸烷基、碳數2～5的亞烷基、醚基、硫醚基、磺醯基、羰氧基、羰基、伸茀基、單鍵、或下述通式(a-3-1)或下述通式(a-3-2)表示的2價基；n ^a21及n ^a22分別獨立地為0～4的整數；＊表示鍵結部位。

In formula (a-3), R ^a21 and R ^a22 are independently an aliphatic hydrocarbon group with 1 to 5 carbons, an alkoxy group with 1 to 5 carbons, a hydroxyl group, or a halogen atom; X ^a22 is an aliphatic hydrocarbon group with 1 to 5 carbons; 5 alkylene groups, alkylene groups with 2 to 5 carbons, ether groups, thioether groups, sulfonyl groups, carbonyloxy groups, carbonyl groups, terpenyl groups, single bonds, or the following general formula (a-3- 1) or a divalent group represented by the following general formula (a-3-2); n ^a21 and n ^a22 are each independently an integer of 0 to 4; * represents a bonding site.

式(a-3-1)中，R ^a23及R ^a24分別獨立地為碳數1～5的脂肪族烴基或鹵素原子；X ^a23為碳數1～5的伸烷基、碳數2～5的亞烷基、間苯二異丙基、對苯二異丙基、醚基、硫醚基、磺醯基、羰氧基、羰基、或單鍵；n ^a23及n ^a24分別獨立地為0～4的整數；＊表示鍵結部位。

In formula (a-3-1), R ^a23 and R ^a24 are independently an aliphatic hydrocarbon group or a halogen atom with 1 to 5 carbons; X ^a23 is an alkylene group with 1 to 5 carbons, The alkylene group, m-phenylene diisopropyl group, p-phenylene diisopropyl group, ether group, thioether group, sulfonyl group, carbonyloxy group, carbonyl group, or single bond; n ^a23 and n ^a24 are independently 0 An integer of ~4; * represents a bonding site.

式(a-3-2)中，R ^a25為碳數1～5的脂肪族烴基或鹵素原子；X ^a24及X ^a25分別獨立地為碳數1～5的伸烷基、碳數2～5的亞烷基、醚基、硫醚基、磺醯基、羰氧基、羰基、或單鍵；n ^a25為0～4的整數；＊表示鍵結部位。

In the formula (a-3-2), R ^a25 is an aliphatic hydrocarbon group or a halogen atom with 1 to 5 carbons; X ^a24 and X ^a25 are independently an alkylene group with 1 to 5 carbons, and an alkylene group with 2 to 5 carbons. The alkylene group, ether group, thioether group, sulfonyl group, carbonyloxy group, carbonyl group, or single bond; n ^a25 is an integer from 0 to 4; * represents the bonding site.

In the above general formula (a-3), the above general formula (a-3-1) and the above general formula (a-3-2), the carbon numbers represented by R ^a21 , R ^a22 , R ^a23 , R ^a24 and R ^a25 The aliphatic hydrocarbon group of 1 to 5 can be, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl and other alkyl groups with 1 to 5 carbons ; alkenyl having 2 to 5 carbons, alkynyl having 2 to 5 carbons, etc. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. The aliphatic hydrocarbon group having 1 to 5 carbons is preferably an aliphatic hydrocarbon group having 1 to 3 carbons, more preferably an alkyl group having 1 to 3 carbons, more preferably methyl or ethyl. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom and the like.

The number of carbons represented by X ^a22 in the above general formula (a-3), X ^a23 in the above general formula (a-3-1), and X ^a24 and X ^a25 in the above general formula (a-3-2) Examples of alkylene groups of 1 to 5 include: methylene, 1,2-dimethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,5-pentamethylene, etc. . The alkylene group having 1 to 5 carbons is preferably an alkylene group having 1 to 3 carbons, more preferably an alkylene group having 1 or 2 carbons, and more preferably methylene.

The number of carbons represented by X ^a22 in the above general formula (a-3), X ^a23 in the above general formula (a-3-1), and X ^a24 and X ^a25 in the above general formula (a-3-2) Examples of the 2-5 alkylene group include ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, and isopentylene. The alkylene group having 2 to 5 carbons is preferably an alkylene group having 2 to 4 carbons, more preferably an alkylene group having 2 or 3 carbons, and more preferably isopropylidene.

In the above general formula (a-3), n ^a21 and n ^a22 are each independently an integer of 0 to 4, from the viewpoint of ease of acquisition, an integer of 0 to 3 is preferred, and an integer of 0 to 2 is preferred. Preferably, 0 or 2 is more preferred. When n ^a21 or n ^a22 is an integer of 2 or more, plural R ^a21 or plural R ^a22 may be the same or different from each other.

In the above general formula (a-3-1), n ^a23 and n ^a24 are each independently an integer of 0 to 4, from the viewpoint of ease of acquisition, an integer of 0 to 2 is preferred, and 0 or 1 Better, 0 is better. When n ^a23 or n ^a24 is an integer of 2 or more, plural R ^a23 or plural R ^a24 may be the same or different from each other.

In the above general formula (a-3-2), n ^a25 is an integer of 0 to 4, preferably an integer of 0 to 2 from the viewpoint of ease of acquisition, preferably 0 or 1, and more preferably 0 . When n ^a25 is an integer of 2 or more, plural R ^a25 may be the same or different from each other.

In addition, in the above-mentioned general formula (a-1) and the above-mentioned general formula (a-2), X ^a21 may be a divalent group containing a structural unit represented by the following general formula (a-4), or may be the following general formula: Divalent group represented by formula (a-5).

式(a-4)中，R ^a26及R ^a27分別獨立地為碳數1～5的脂肪族烴基、苯基或經取代的苯基；＊表示鍵結部位。

In formula (a-4), R ^a26 and R ^a27 are each independently an aliphatic hydrocarbon group having 1 to 5 carbons, a phenyl group or a substituted phenyl group; * represents a bonding site.

式(a-5)中，R ^a26及R ^a27與上述通式(a-4)中的R ^a26及R ^a27相同，R ^a28及R ^a29分別獨立地為碳數1～5的脂肪族烴基、苯基或經取代的苯基；X ^a26及X ^a27分別獨立地為2價有機基；n ^a26為2～100的整數；＊表示鍵結部位。

In formula (a-5), R ^a26 and R ^a27 are the same as R ^a26 and R ^a27 in the above general formula (a-4), and R ^a28 and R ^a29 are independently aliphatic hydrocarbon groups with 1 to 5 carbon atoms, Phenyl or substituted phenyl; X ^a26 and X ^a27 are each independently a divalent organic group; n ^a26 is an integer of 2 to 100; * represents a bonding site.

In the above general formulas (a-4) and (a-5), the aliphatic hydrocarbon groups having 1 to 5 carbons represented by R ^a26 to R ^a29 include, for example, methyl, ethyl, n-propyl, isopropyl, Alkyl groups with 1 to 5 carbons such as n-butyl, isobutyl, tertiary butyl and n-pentyl; alkenyls with 2 to 5 carbons, alkynyls with 2 to 5 carbons, etc. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. The aliphatic hydrocarbon group having 1 to 5 carbons is preferably an aliphatic hydrocarbon group having 1 to 3 carbons, preferably an alkyl group having 1 to 3 carbons, and more preferably a methyl group. The substituents that the phenyl groups in the substituted phenyl groups represented by R ^a26 to R ^a29 include, for example, the above-mentioned aliphatic hydrocarbon groups having 1 to 5 carbon atoms.

The divalent organic groups represented by X ^a26 and X ^a27 include, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylylene group, —O—, or a divalent linking group formed by combining them. The above-mentioned alkylene group includes, for example, an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylidene group, and a propylidene group. The above-mentioned alkenylene group may, for example, be an alkenylene group having 2 to 10 carbon atoms. The above-mentioned alkynylene group may, for example, be an alkynylene group having 2 to 10 carbon atoms. Examples of the above-mentioned arylylene group include arylylene groups having 6 to 20 carbon atoms such as phenylene and naphthylene. Among them, X ^a26 and X ^a27 are preferably alkylene or aryl, more preferably alkylene.

n ^a26 is an integer of 2-100, preferably an integer of 2-50, more preferably an integer of 3-40, more preferably an integer of 5-30. When n ⁿ²⁶ is an integer of 2 or more, plural R ^a26 or plural R ^a27 may be the same or different from each other.

In the aminomaleimide resin (A2), the content of the structural unit derived from the diamine compound (a) is not particularly limited, preferably 5-95% by mass, preferably 7-70% by mass, and preferably 10% by mass. ~40% by mass is more preferred. When the content of the structural unit derived from the diamine compound (a) in the aminomaleimide resin (A2) is within the above range, the dielectric properties, heat resistance, flame retardancy and glass transition temperature are better Propensity

Examples of diamine compounds (a) include: 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'- Diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diamine 4,4'-diaminodiphenylketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3 ,3'-Dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis [4-(4-aminophenoxy)phenyl]propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1 ,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis[1-[4-(4-aminophenoxy) Oxy)phenyl]-1-methylethyl]benzene, 1,4-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 4 ,4'-[1,3-Phenylbis(1-methylethylene)]bisaniline, 4,4'-[1,4-Phenylbis(1-methylethylene)] Dianiline, 3,3'-[1,3-phenylenebis(1-methylethylene)]bisaniline, bis[4-(4-aminophenoxy)phenyl]pyridine, bis[ Aromatic diamine compounds such as 4-(3-aminophenoxy)phenyl]pyridine and 9,9-bis(4-aminophenyl)oxene; silicon oxide compounds with two primary amino groups, etc. In addition, in this specification, an "aromatic diamine compound" means a compound which has two amine groups directly bonded to an aromatic ring.

From the viewpoint of excellent solubility in organic solvents, reactivity, heat resistance, dielectric properties, and low water absorption, among these, the diamine compound (a) is 4,4'-diaminodiphenyl methyl methane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2 -bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, and 4,4 '-[1,4-Phenylbis(1-methylethylene)]bisaniline is preferred, and 3,3'-diethyl-4,4'-diaminodiphenylmethane is preferred . Also, from the viewpoint of low thermal expansion, a silicone compound having two primary amine groups is preferable.

The silicon oxide compound having two primary amino groups is preferably a silicon oxide compound having primary amino groups at both ends. The primary amine equivalent of the silicone compound having two primary amine groups is not particularly limited, preferably 300-2,000 g/mol, more preferably 400-1,500 g/mol, more preferably 500-1,000 g/mol.

In the aminomaleimide resin (A2), the total equivalent (Ta2) of the groups derived from the _-NH2 group of the diamine compound (a) and the N-substitution of the maleimide resin (AX) The equivalent ratio of the total equivalents (Ta1) of the maleimide groups, that is, the equivalent ratio Ta2/Ta1 is not particularly limited, and from the viewpoint of dielectric properties, heat resistance, flame retardancy, and glass transition temperature, it is 0.05 to 10 is preferable, 1-8 is more preferable, and 3-7 is more preferable. In addition, the group derived from _-NH2 group of the said diamine compound (a) is assumed to also include _-NH2 itself. In addition, the group derived from the N-substituted maleimide group of the said maleimide resin (AX) is assumed to also include the N-substituted maleimide group itself.

The weight average molecular weight (Mw) of the aminomaleimide resin (A2) is not particularly limited, but it is preferably 400-10,000, more preferably 1,000-5,000, and 1,500- 4,000 is better, and 2,000-3,000 is especially good.

(Method for producing aminomaleimide resin (A2)) Amino maleimide resin (A2) can be manufactured by making maleimide resin (AX) and diamine compound (a) react in an organic solvent, for example. By reacting the maleimide resin (AX) with the diamine compound (a), it is possible to obtain a product obtained by the Myco addition reaction between the maleimide resin (AX) and the diamine compound (a). Aminomaleimide resin (A2).

When making maleimide resin (AX) and diamine compound (a) react, a reaction catalyst can be used as needed. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. These can be used individually by 1 type or in combination of 2 or more types. The blending amount of the reaction catalyst is not particularly limited, and from the viewpoint of the reaction rate and the uniformity of the reaction, it is 0.01 to 100 parts by mass relative to the total amount of the maleimide resin (AX) and the diamine compound (a). 5 parts by mass is preferable, more preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass.

From the standpoint of workability such as reaction speed and inhibition of product gelation during the reaction, the reaction temperature of the Myco addition reaction is preferably 50 to 160°C, more preferably 60 to 150°C, and 70 to 140°C. better. The reaction time of the Myco addition reaction is preferably from 0.5 to 10 hours, more preferably from 1 to 8 hours, and more preferably from 2 to 6 hours, from the viewpoint of productivity and sufficient progress of the reaction. However, these reaction conditions can be appropriately adjusted in accordance with the types of raw materials used, etc., and are not particularly limited.

((A) content of thermosetting resin) In the resin composition of this embodiment, the content of (A) thermosetting resin is not particularly limited, but it is 20 to 95% by mass relative to the total amount of resin components (100% by mass) in the resin composition of this embodiment. Preferably, it is 50-90 mass %, More preferably, it is 70-85 mass %. When content of (A) thermosetting resin is more than the said lower limit, it exists in the tendency for heat resistance, moldability, processability, and conductor adhesiveness to become more favorable easily. Moreover, it exists in the tendency for a dielectric characteristic to become more favorable easily that content of (A) thermosetting resin is below the said upper limit.

Here, in this specification, a "resin component" means a resin and a compound that forms a resin by a curing reaction. For example, in the resin composition of this embodiment, (A) thermosetting resin and (B) polyphenylene ether resin correspond to resin components. When the resin composition of the present embodiment contains, as an optional component, a resin or a compound that forms a resin by a curing reaction in addition to the above components, these optional components are also included in the resin component. The optional components corresponding to the resin components include, for example, (E) styrene-based elastomers, (F) hardening accelerators and the like which will be described later. On the other hand, (C) an alkoxysilane compound having a primary amino group and (D) an inorganic filler are not included in the resin component.

In the resin composition of the present embodiment, the total content of the resin components is not particularly limited, and from the viewpoint of low thermal expansion, heat resistance, flame retardancy, and conductor adhesion, the solid content of the resin composition of the present embodiment The total amount of components (100% by mass) is preferably from 30 to 95% by mass, more preferably from 50 to 90% by mass, more preferably from 70 to 80% by mass.

(A) In the thermosetting resin, the content of the above-mentioned maleimide-based resin is not particularly limited, but it is preferably 80 to 100% by mass relative to the total amount (100% by mass) of the (A) thermosetting resin, It is preferably 90 to 100% by mass, more preferably 95 to 100% by mass. There exists a tendency for heat resistance, moldability, processability, and conductor adhesiveness to become more favorable that content of maleimide resin is more than the said lower limit. Moreover, it exists in the tendency for a dielectric characteristic to become more favorable easily that content of a maleimide-type resin is below the said upper limit.

＜(B) Polyphenylene ether resin＞ (B) The polyphenylene ether-based resin is not particularly limited as long as it has a polyphenylene ether chain. (B) The polyphenylene ether-based resin may be used alone or in combination of two or more.

(B) The polyphenylene ether-based resin has a phenylene ether bond, and preferably has a structural unit represented by the following general formula (B-1).

式(B-1)中，R ^b1表示碳數1～5的脂肪族烴基或鹵素原子；n ^b1表示0～4的整數。

In formula (B-1), R ^b1 represents an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms; n ^b1 represents an integer of 0 to 4.

In the above-mentioned general formula (B-1), the aliphatic hydrocarbon group having 1 to 5 carbons represented by R ^b1 can be exemplified: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tris Grade butyl, n-pentyl, etc. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group with 1 to 3 carbons, more preferably an alkyl group with 1 to 3 carbons, and more preferably a methyl group. n ^b1 represents an integer of 0 to 4, preferably 1 or 2, more preferably 2. Furthermore, when n ^b1 is 1 or 2, R ^b1 is preferably substituted at the ortho position on the benzene ring (provided that the substitution position of the oxygen atom is taken as the basis). In addition, when n ^b1 is an integer of 2 or more, plural R ^b1 may be the same as or different from each other. The structural unit represented by the above general formula (B-1) is preferably a structural unit represented by the following general formula (B-1').

From the viewpoint of heat resistance, the (B) polyphenylene ether-based resin preferably has a functional group containing an ethylenically unsaturated bond [hereinafter, it may be referred to as a "group containing an ethylenically unsaturated bond"]. In addition, in this specification, an "ethylenically unsaturated bond" means a carbon-carbon double bond which can undergo an addition reaction, and is a double bond not including an aromatic ring.

Examples of groups containing ethylenically unsaturated bonds include vinyl, allyl, 1-methallyl, isopropenyl, 2-butenyl, 3-butenyl, styryl, maleyl An imino group, a group represented by the following general formula (B-2), and the like. Among these, a group represented by the following general formula (B-2) is preferable from the viewpoint of dielectric properties.

式(B-2)中，R ^b2表示氫原子或碳數1～20的烷基。

In formula (B-2), R ^b2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

The alkyl group having 1 to 20 carbons represented by R ^b2 may be any of straight-chain alkyl, branched-chain or cyclic alkyl, preferably straight-chain alkyl. The carbon number of the above-mentioned alkyl group is preferably 1-10, more preferably 1-5, more preferably 1-3, and particularly preferably 1. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, pentadecyl, hexadecyl, heptadecyl, etc. Among them, methyl is preferred. From the viewpoint of dielectric properties, the group represented by the above general formula (B-2) is preferably a (meth)acryl group, more preferably a methacryl group.

(B) The number of ethylenically unsaturated bond-containing groups in one molecule of the polyphenylene ether resin is not particularly limited, but is preferably 1 to 5, more preferably 2 to 3, and more preferably 2. There exists a tendency for heat resistance to become more favorable easily that the number of the groups containing an ethylenically unsaturated bond is more than the said lower limit. On the other hand, when the number of ethylenically unsaturated bond-containing groups is not more than the above-mentioned upper limit, moldability tends to be more favorable.

(B) The polyphenylene ether-based resin preferably has an ethylenically unsaturated bond-containing group at the terminal, and more preferably has an ethylenically unsaturated bond-containing group at both terminals. (B) The polyphenylene ether-based resin may have an ethylenically unsaturated bond-containing group other than the terminal, but it is preferable to have an ethylenically unsaturated bond-containing group only at the terminal.

The (B) polyphenylene ether-based resin is preferably a compound represented by the following general formula (B-3) from the viewpoint of dielectric properties.

式(B-3)中，R ^b1及n ^b1是如同上述通式(B-1)中所說明；R ^b3及R ^b4分別獨立地表示碳數1～5的脂肪族烴基或鹵素原子；n ^b2及n ^b3分別獨立地表示0～4的整數；n ^b4及n ^b5分別獨立地表示0～20的整數，且n ^b4與n ^b5的合計為1～30的整數；X ^b1表示碳數1～5的伸烷基、碳數2～5的亞烷基、醚基、硫醚基、磺醯基、羰氧基、羰基、或單鍵；Y ^b1及Y ^b2分別獨立地表示上述含乙烯性不飽和鍵的基。

In the formula (B-3), R ^b1 and n ^b1 are as explained in the above-mentioned general formula (B-1); R ^b3 and R ^b4 independently represent an aliphatic hydrocarbon group or a halogen atom with 1 to 5 carbon atoms; n ^b2 and n ^b3 each independently represent an integer of 0 to 4; n ^b4 and n ^b5 each independently represent an integer of 0 to 20, and the total of n ^b4 and n ^b5 is an integer of 1 to 30; X ^b1 represents a carbon number of 1 ~5 alkylene groups, alkylene groups with 2 to 5 carbons, ether groups, thioether groups, sulfonyl groups, carbonyloxy groups, carbonyl groups, or single bonds; Y ^b1 and Y ^b2 independently represent the above-mentioned ethylene-containing base of sexually unsaturated bonds.

The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^b3 and R ^b4 in the above general formula (B-3) is the same as that for the carbon number 1 represented by R ^b1 in the above general formula (B-1). The description of the aliphatic hydrocarbon group to 5 is the same. n ^b2 and n ^b3 represent an integer of 0-4, preferably an integer of 0-3, more preferably 2 or 3. When n ^b2 or n ^b3 is an integer of 2 or more, plural R ^b3 or plural R ^b4 may be the same as or different from each other. n ^b4 and n ^b5 represent an integer of 0 to 20, preferably an integer of 1 to 20, more preferably an integer of 2 to 15, and more preferably an integer of 3 to 10. When n ^b4 or n ^b5 is an integer of 2 or more, the plurality of R ^b1 may be the same or different from each other. The total of n ^b4 and n ^b5 is an integer of 1-30, preferably an integer of 2-25, more preferably an integer of 5-20, more preferably an integer of 7-15.

In the above general formula (B-3), the alkylene group having 1 to 5 carbons represented by X ^b1 includes, for example, methylene, 1,2-dimethylene, 1,3-trimethylene, 1, 4-tetramethylene, 1,5-pentamethylene, etc. The alkylene group having 2 to 5 carbon atoms represented by X ^b1 includes, for example, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, and an isopentylene group. From the viewpoint of dielectric properties, among the groups represented by X ^b1 , an isopropylidene group is preferable. Desirable aspects of the ethylenically unsaturated bond-containing groups represented by Y ^b1 and Y ^b2 are as described above. From the viewpoint of dielectric properties, the compound represented by the above general formula (B-3) is preferably a compound represented by the following general formula (B-4).

式(B-4)中，n ^b4及n ^b5是如同上述通式(B-3)中所說明；R ^b5及R ^b6分別獨立地表示氫原子或甲基；X ^b2表示亞甲基或亞異丙基。

In the formula (B-4), n ^b4 and n ^b5 are as explained in the above-mentioned general formula (B-3); R ^b5 and R ^b6 independently represent a hydrogen atom or a methyl group; X ^b2 represents a methylene or a methylene Isopropyl.

[(B) Weight average molecular weight (Mw) of polyphenylene ether resin] (B) The weight average molecular weight (Mw) of the polyphenylene ether resin is not particularly limited, but is preferably 500-7,000, more preferably 800-5,000, more preferably 1,000-3,000, and particularly preferably 1,200-2,500. When the weight average molecular weight (Mw) of (B) polyphenylene ether resin is more than the said lower limit, it exists in the tendency which has the excellent dielectric characteristic of polyphenylene ether and is excellent in the hardened|cured material of heat resistance easily. Moreover, when the weight average molecular weight (Mw) of (B) polyphenylene ether resin is below the said upper limit, it exists in the tendency for moldability to become more favorable easily.

(B) The synthesis method of the polyphenylene ether resin can be applied to the conventional synthesis method and modification method of polyphenylene ether, and is not particularly limited.

((B) content of polyphenylene ether resin) In the resin composition of this embodiment, the content of (B) polyphenylene ether-based resin is not particularly limited, and it is 1 to 30% by mass relative to the total amount of resin components (100% by mass) in the resin composition of this embodiment. % is preferable, more preferably 4 to 20 mass %, more preferably 7 to 15 mass %. It exists in the tendency for a dielectric characteristic to become more favorable easily that content of (B) polyphenylene ether resin is more than the said lower limit. Moreover, when content of (B) polyphenylene ether resin is below the said upper limit, heat resistance, moldability, and processability tend to become more favorable easily.

＜(C) Alkoxysilane compound having a primary amino group＞ (C) The alkoxysilane compound which has a primary amino group will not be specifically limited if it is a compound which has a primary amino group and an alkoxysilyl group. (C) The alkoxysilane compound which has a primary amino group may be used individually by 1 type, and may use 2 or more types together.

(C) Alkoxysilane compounds with primary amino groups include, for example, compounds with monoalkoxysilyl groups, dialkoxysilyl groups, and trialkoxysilyl groups. Oxysilyl compounds are preferred. The number of carbon atoms of the alkyl group constituting the alkoxy group contained in the alkoxysilyl group is preferably 1-10, more preferably 1-5, and more preferably 1 or 2. The alkyl group constituting the alkoxy group contained in the alkoxysilyl group may be linear or branched.

(C) The number of the primary amino group which the alkoxysilane compound which has a primary amino group has is not specifically limited, Preferably it is 1-3, Preferably it is 1 or 2, More preferably, it is 1.

(C) The alkoxysilane compound having a primary amino group is preferably a compound represented by the following general formula (C-1).

式(C-1)中，R ^c1分別獨立地為碳數1～10的烷基，R ^c2為具有一級胺基的碳數1～10的烴基。

In formula (C-1), R ^c1 is each independently an alkyl group having 1 to 10 carbons, and R ^c2 is a hydrocarbon group having 1 to 10 carbons having a primary amino group.

In the above-mentioned general formula (C-1), the alkyl group having 1 to 10 carbons represented by R ^c1 includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl base, dodecyl, etc. The alkyl group having 1 to 10 carbon atoms may be either linear or branched. Among these, methyl, ethyl, and propyl are preferable, and methyl and ethyl are more preferable.

In the above general formula (C-1), the carbon number of the hydrocarbon group with 1 to 10 carbons represented by R ^c2 having a primary amino group [hereinafter sometimes referred to as "a hydrocarbon group with a primary amino group"] preferably has a carbon number of 1 to 8 , preferably 2-7, more preferably 3-6. The hydrocarbon group which has a primary amino group may have a substituent other than a primary amino group, and may not have a substituent. When the hydrocarbon group having a primary amine group has a substituent in addition to the primary amine group, the primary amine group may be bonded to the substituent. When the hydrocarbon group having a primary amino group has a substituent, the above carbon number is assumed to also include the carbon number of the substituent.

Hydrocarbon groups having a primary amino group include, for example: an alkyl group having 1 to 10 carbons having a primary amine group, an alkenyl group having 1 to 10 carbons having a primary amine group, and an alkyne group having 1 to 10 carbons having a primary amine group Base etc. Among these, an alkyl group having 1 to 10 carbon atoms having a primary amino group is preferable. Furthermore, the so-called "having a primary amine group" here is not only the case where the primary amine group is directly bonded to the carbon atoms used to form the above-mentioned alkyl, alkenyl, and alkynyl groups, but also includes the carbon atoms used to form the above-mentioned alkyl groups. The case where the carbon atoms of a radical, alkenyl, or alkynyl group are substituted by a substituent other than a primary amino group, and a part of the substituent contains a primary amino group. In addition, below, the substituent which contains a primary amino group may be called "the primary amino group containing group."

The alkyl group used to constitute the above-mentioned C1-C10 alkyl group having a primary amino group can be, for example: methyl, ethyl, propyl, butyl, substituted by a primary amino group or a group containing a primary amino group, Pentyl, hexyl, heptyl, octyl, decyl, dodecyl, etc. Among these, methyl, ethyl, and propyl groups substituted by primary amino groups or groups containing primary amino groups are preferred, and propyl groups substituted by primary amino groups or groups containing primary amino groups are more preferred. The propyl group substituted by the primary amino group can be, for example, 3-aminopropyl group.

The group containing a primary amino group is preferably, for example, a substituted amino group having a primary amino group. The substituted amine group having a primary amine group includes, for example, an amine group substituted with a hydrocarbon group having a primary amine group. The hydrocarbon group having a primary amine group is preferably an alkyl group having 1 to 5 carbons having a primary amine group, more preferably an alkyl group having 2 to 4 carbons having a primary amine group. The substituted amine group substituted with a hydrocarbon group having a primary amine group is preferably 2-aminoethylamine group. The alkyl group having 1 to 10 carbons having a substituted amino group substituted with a hydrocarbon group having a primary amino group is preferably 3-(2-aminoethylamino)propyl.

(C) Alkoxysilane compounds with primary amino groups include, for example: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethylamine base) propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, N-(trimethoxysilylpropyl)melamine, N-(triethoxysilane propyl) melamine, etc. Among these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-( 2-Aminoethylamino)propyltriethoxysilane is preferred, 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyltriethoxy Silane is preferred.

((C) Content of alkoxysilane compound having primary amino group) In the resin composition of the present embodiment, the content of (C) the alkoxysilane compound having a primary amino group is not particularly limited, and it is 0.05% with respect to the total solid content (100% by mass) of the resin composition of the present embodiment. It is preferably from 0.1 to 5% by mass, more preferably from 0.3 to 2% by mass, and particularly preferably from 0.5 to 1% by mass. In addition, in the resin composition of the present embodiment, the content of (C) the alkoxysilane compound having a primary amino group is not particularly limited, but it is preferably 0.1 to 15 parts by mass relative to 100 parts by mass of the inorganic filler (D). , preferably 0.3-10 parts by mass, more preferably 0.6-5 parts by mass, particularly preferably 0.8-2 parts by mass. (C) There exists a tendency for copper foil peeling strength and curability to become more favorable that content of the alkoxysilane compound which has a primary amino group is more than the said lower limit. Moreover, when content of the alkoxysilane compound which has (C) a primary amino group is below the said upper limit, it exists in the tendency for a dielectric characteristic to become more favorable easily. In addition, in the resin composition of this embodiment, (C)component may exist in the form which reacted with another component. In this case, in the resin composition of this embodiment, content of (C)component is set as the quantity which also includes the reacted (C)component. In other words, the total amount of (C)component compounded in the resin composition of this embodiment is regarded as content of (C)component in the resin composition of this embodiment.

＜(D) Inorganic filler＞ The resin composition of this embodiment tends to obtain more excellent low thermal expansion property, heat resistance, and flame retardance by containing (D) an inorganic filler. (D) The inorganic filler may be used alone or in combination of two or more.

(D) Inorganic filler materials can be, for example: silicon oxide, aluminum oxide, titanium oxide, mica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide , aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, etc. From the viewpoint of low thermal expansion, heat resistance, and flame retardancy, among these, silicon oxide, aluminum oxide, mica, and talc are preferable, and silicon oxide and aluminum oxide are more preferable. Examples of silicon oxide include the following: deposited silicon oxide, which is produced by a wet process and has a high water content; and dry process silicon oxide, which is produced by a dry process and hardly contains bound water. Furthermore, depending on the manufacturing method, dry silicon oxide can be, for example, pulverized silicon oxide, fumed silicon oxide, fused silicon oxide, etc.

(D) The average particle size of the inorganic filler is not particularly limited, but from the viewpoint of the dispersibility and fine line linearity of the (D) inorganic filler, it is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, and 0.2 to 1 μm is more preferable, and 0.3 to 0.8 μm is particularly preferable. In addition, in this specification, (D) the average particle diameter of an inorganic filler is the particle|grains corresponding to the point of 50% of a volume when the cumulative frequency distribution curve obtained from particle diameter is calculated|required assuming that the total volume of a particle is 100%. path. (D) The average particle diameter of an inorganic filler can be measured using the particle size distribution measuring apparatus etc. which used the laser diffraction scattering method, for example. (D) The shape of the inorganic filler can be, for example, spherical, pulverized, etc., preferably spherical.

((D) content of inorganic filler) In the resin composition of the present embodiment, the content of (D) the inorganic filler is not particularly limited, but it is preferably 20 to 90 mass %, preferably 40 to 80 mass %, based on the total solid content (100 mass %) of the resin composition. The mass % is preferable, 50-75 mass % is more preferable, and 55-70 mass % is especially preferable. It exists in the tendency for low thermal expansion property, heat resistance, and flame retardance to become more favorable easily that content of (D) inorganic filler is more than the said lower limit. Moreover, there exists a tendency for moldability and conductor adhesiveness to become more favorable easily that content of (D) inorganic filler is below the said upper limit.

＜(E) Styrene-based elastomer＞ It is preferable that the resin composition of this embodiment further contains: (E) a styrene-type elastomer. The resin composition of this embodiment tends to obtain more excellent dielectric characteristics easily by containing (E) a styrene-type elastomer. In addition, the term "elastomer" here means a polymer having a glass transition temperature of 25° C. or lower as measured by differential scanning calorimetry in accordance with JIS K 6240:2011. (E) The styrene-type elastomer can be used individually by 1 type, or in combination of 2 or more types.

(E) The styrene-based elastomer preferably has a structural unit derived from a styrene-based compound represented by the following general formula (E-1).

式(E-1)中，R ^e1為氫原子或碳數1～5的烷基，R ^e2為碳數1～5的烷基；n ^e1為0～5的整數。

In formula (E-1), R ^e1 is a hydrogen atom or an alkyl group having 1 to 5 carbons, R ^e2 is an alkyl group having 1 to 5 carbons, and n ^e1 is an integer of 0 to 5.

In the above-mentioned general formula (E-1), the alkyl groups having 1 to 5 carbon atoms represented by R ^e1 and R ^e2 include, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , Tertiary butyl, n-pentyl, etc. The alkyl group having 1 to 5 carbon atoms may be either linear or branched. Among them, an alkyl group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is more preferable. In the above general formula (E-1), n ^e1 is an integer of 0-5, preferably an integer of 0-2, more preferably 0 or 1, more preferably 0.

(E) The styrene-based elastomer may contain structural units other than those derived from styrene-based compounds. (E) Structural units other than the structural units derived from styrene compounds possessed by styrene-based elastomers include, for example, structural units derived from butadiene, structural units derived from isoprene, A structural unit of an acid, a structural unit derived from maleic anhydride, and the like. The above-mentioned butadiene-derived structural unit and the above-mentioned isoprene-derived structural unit may be subjected to hydrogenation. When subjected to hydrogenation, the structural unit derived from butadiene becomes a structural unit in which ethylene units and butene units are mixed, and the structural unit derived from isoprene becomes a structure in which ethylene units and propylene units are mixed unit.

(E) Styrene-based elastomers include, for example: hydrogenated products of styrene-butadiene-styrene block copolymers, hydrogenated products of styrene-isoprene-styrene block copolymers, styrene- Maleic anhydride copolymer, etc. The hydrogenated product of styrene-butadiene-styrene block copolymer can be for example: make the carbon-carbon double bond in the butadiene block carry out complete hydrogenation and form SEBS; And make the butadiene block SBBS obtained by partially hydrogenating the carbon-carbon double bond at the 1,2-bonding site. Furthermore, the so-called complete hydrogenation in SEBS means that the hydrogenation rate of the overall carbon-carbon double bond is usually above 90%, may be above 95%, may be above 99%, or may be 100%. In addition, the partial hydrogenation rate in SBBS is, for example, 60 to 85% with respect to the entire carbon-carbon double bond. The hydrogenated product of the styrene-isoprene-styrene block copolymer is obtained as SEPS by partially hydrogenating polyisoprene. From the viewpoint of dielectric properties, conductor adhesion, heat resistance, glass transition temperature, and low thermal expansion, among these, SEBS and SEPS are preferable, and SEBS is more preferable.

In the above-mentioned SEBS, the content of structural units derived from styrene [hereinafter sometimes referred to as "styrene content"] is not particularly limited, but is preferably 5 to 60% by mass, more preferably 7 to 40% by mass, and preferably 7 to 40% by mass. 10 to 20% by mass is more preferable.

The melt flow rate (MFR) of SEBS is not particularly limited. Under the measurement conditions of 230°C and a load of 2.16 kgf (21.2 N), it is preferably 0.1-20 g/10 min, preferably 1-10 g/10 min. 3-7 g/10 min is better.

Examples of commercially available SEBS products include: Tuftec (registered trademark) H series and M series manufactured by Asahi Kasei Co., Ltd.; SEPTON (registered trademark) series manufactured by Kuraray Co., Ltd.; KRATON (registered trademark) manufactured by Kraton Polymers Japan Co., Ltd. Trademark) G POLYMER series, etc.

(E) The weight average molecular weight (Mw) of the styrene-based elastomer is not particularly limited, but is preferably 10,000-500,000, more preferably 20,000-350,000, more preferably 40,000-200,000, and particularly preferably 60,000-90,000.

((E) content of styrene-based elastomer) When the resin composition of the present embodiment contains the (E) styrene-based elastomer, the content of the (E) styrene-based elastomer is not particularly limited, and is relative to the total amount of the resin component in the resin composition of the present embodiment ( 100% by mass), preferably 1 to 30% by mass, more preferably 4 to 20% by mass, more preferably 7 to 15% by mass. It exists in the tendency for a dielectric characteristic and flexibility to become more favorable easily that content of (E) a styrene-type elastomer is more than the said lower limit. Moreover, it exists in the tendency for heat resistance and a flame retardance to become more favorable easily that content of (E) a styrene-type elastomer is below the said upper limit.

＜(F) Hardening Accelerator＞ From the viewpoint of accelerating the curing reaction of the resin composition, it is preferable that the resin composition of the present embodiment further contains: (F) a curing accelerator. (F) The hardening accelerator may be used alone or in combination of two or more.

(F) Hardening accelerators include, for example, amine-based hardening accelerators, imidazole-based hardening accelerators, phosphorus-based hardening accelerators, organic metal salts, acid catalysts, organic peroxides, and the like. In addition, in the present embodiment, the imidazole-based hardening accelerator is not classified as an amine-based hardening accelerator. Examples of the amine-based hardening accelerator include amine compounds having primary to tertiary amines such as triethylamine, pyridine, tributylamine, and dicyandiamide; quaternary ammonium compounds, and the like. Examples of imidazole-based hardening accelerators include imidazole compounds such as methylimidazole, phenylimidazole, and 2-undecylimidazole; addition reactions between hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole The isocyanate groups such as substances cover imidazole and so on. Examples of the phosphorus-based hardening accelerator include triphenylphosphine and other tertiary phosphines; p-benzoquinone tri-n-butylphosphine addition reactants and other quaternary phosphonium compounds; and the like. Examples of organic metal salts include carboxylates such as manganese, cobalt, and zinc. The acidic catalyst may, for example, be p-toluenesulfonic acid or the like. Examples of organic peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-bis(tertiary butylperoxy)hexyne-3, 2,5 -Dimethyl-2,5-bis(tertiary butylperoxy)hexane, tertiary butylperoxyisopropyl monocarbonate, α,α'-bis(tertiary butylperoxy ) diisopropylbenzene, etc. From the viewpoint of dielectric properties, heat resistance, adhesion to conductors, and elastic modulus, among these, amine-based hardening accelerators, imidazole-based hardening accelerators, and phosphorus-based hardening accelerators are preferable. Dicyandiamide, imidazole-based hardening accelerators, and quaternary phosphonium compounds are preferred, and these are more preferably used in combination.

When the resin composition of the present embodiment contains (F) a hardening accelerator, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of (A) thermosetting resin, More preferably, it is 1-3 mass parts. There exists a tendency for sufficient hardening acceleration effect to be acquired easily that content of (F) hardening accelerator is more than the said lower limit. Moreover, when content of (F) hardening accelerator is below the said upper limit, it exists in the tendency for storage stability to become more favorable easily.

＜Other ingredients＞ The resin composition of this embodiment may further contain one or more optional components selected from the group consisting of: resin materials other than the above-mentioned components, flame retardants, antioxidants, and heat stabilizers as needed. , antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, organic solvents, and additives other than these. The above arbitrary components may be used alone or in combination of two or more. In the resin composition of this embodiment, the content of the said arbitrary component is not specifically limited, What is necessary is just to use as needed within the range which does not inhibit the effect of this embodiment. In addition, the resin composition of this embodiment may not contain the above-mentioned arbitrary components according to desired performance.

＜Manufacturing method of resin composition＞ The resin composition of this embodiment can be manufactured by mixing each said component. When mixing the components, the components can be dissolved or dispersed while being stirred. In addition, conditions such as the order of mixing the raw materials, mixing temperature, and mixing time are not particularly limited, and may be set arbitrarily according to the types of raw materials and the like.

＜Gelation time＞ The gelation time at 180°C of the resin composition of this embodiment is not particularly limited, but is preferably 150-350 seconds, more preferably 200-300 seconds, and more preferably 220-270 seconds. When the gelation time is more than the above lower limit, it tends to be easy to suppress excessive flow when the resin composition of the present embodiment is laminated and pressurized in the form of a resin film or a prepreg. Moreover, there exists a tendency for storage stability and embedding property to become more favorable easily that a gelation time is below the said upper limit. In addition, the gelation time can be measured by the method described in an Example.

[Prepreg] The prepreg of the present embodiment contains the resin composition of the present embodiment or a semi-cured product of the aforementioned resin composition. In other words, the prepreg of this embodiment is formed using the resin composition of this embodiment. The prepreg of the present embodiment preferably contains: a B-staged resin composition obtained by B-staged the resin composition of the present embodiment; and a sheet-shaped fibrous base material. The prepreg of the present embodiment can be produced, for example, by impregnating or applying the resin composition of the present embodiment to a sheet-shaped fibrous base material, and then B-staging it. In addition, in this specification, B-staged means the state which made it into the B-stage defined in JISK6900:1994, and is also called semi-cured.

As the sheet-shaped fibrous base material contained in the prepreg of this embodiment, for example, conventional sheet-shaped fiber base materials used in various laminates for electrical insulating materials can be used. The material of the flake-shaped fiber substrate can be, for example, inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; mixtures thereof, and the like. Such sheet-like fibrous substrates have, for example, shapes of woven fabrics, nonwoven fabrics, rovings, cut mats, surface mats, and the like. The thickness of the flaky fibrous base material is not particularly limited, but is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, and more preferably 0.03 to 0.1 mm from the viewpoint of mechanical strength and thinning of the prepreg. From the viewpoints of impregnation properties of the resin composition, heat resistance after being made into a laminate, moisture absorption resistance, and processability, the sheet-shaped fiber base material may be a base material that has been surface-treated with a coupling agent or the like. It may be a substrate subjected to mechanical fiber opening treatment.

The prepreg of the present embodiment can be produced, for example, by impregnating or applying the resin composition of the present embodiment to a sheet-shaped fibrous base material, followed by drying if necessary. As a method of impregnating or applying the resin composition of this embodiment to a sheet-shaped fibrous base material, for example, a hot-melt method, a solvent method, or the like can be employed.

The hot-melt method is a method of impregnating or coating a sheet-shaped fibrous base material with a resin composition not containing an organic solvent. One aspect of the hot-melt method is, for example, a method in which the resin composition of this embodiment that does not contain an organic solvent is once coated on a coated paper with good releasability, and then the coated resin composition is laminated on a Sheet-like fibrous substrate. Another aspect of the hot-melt method includes, for example, a method of directly applying the resin composition of this embodiment that does not contain an organic solvent to a sheet-shaped fiber base material using a die coater or the like.

The solvent method is a method of impregnating or applying a resin composition containing an organic solvent to a sheet-shaped fibrous substrate. Specifically, for example, a method of immersing a sheet-shaped fibrous base material in the resin composition of the present embodiment containing an organic solvent, followed by drying. By drying, the organic solvent in the resin composition can be removed and the resin composition can be B-staged. The drying temperature is not particularly limited, but it is preferably 50 to 200°C, more preferably 100 to 190°C, more preferably 150 to 180°C from the viewpoint of productivity and moderately B-staged the resin composition of the present embodiment. °C is better. The drying time is not particularly limited, but it is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and 3 to 10 minutes from the viewpoint of productivity and appropriately B-staged the resin composition of the present embodiment. Minutes are better.

The solid content concentration derived from the resin composition in the prepreg of the present embodiment is not particularly limited, but it is preferably 20 to 90% by mass from the viewpoint of making it easier to obtain better moldability after making a laminate. It is preferably 25 to 80% by mass, more preferably 30 to 75% by mass.

The thickness of the prepreg of this embodiment is not particularly limited, but from the viewpoint of formability and high-density wiring, it is preferably 0.01-0.5 mm, more preferably 0.02-0.3 mm, and more preferably 0.03-0.1 mm.

[resin film] The resin film of the present embodiment contains the resin composition of the present embodiment or a semi-cured product of the aforementioned resin composition. In other words, the resin film of this embodiment is formed using the resin composition of this embodiment. The resin film of the present embodiment is preferably formed by making the B-staged resin composition obtained by B-staged the resin composition of the present embodiment into a film form. The resin film of the present embodiment can be produced by, for example, applying the resin composition of the present embodiment containing an organic solvent, that is, a resin varnish to a support, followed by heating and drying.

Examples of the support include plastic film, metal foil, release paper and the like. Plastic films include, for example, polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate [hereinafter sometimes referred to as "PET"] and polyethylene naphthalate; Film; polycarbonate film, polyimide film, etc. Among these, a polyethylene terephthalate film is preferable from the viewpoint of economic efficiency and handleability. As metal foil, copper foil, aluminum foil, etc. are mentioned, for example. When using copper foil as a support body, it is also possible to form a circuit by making copper foil a conductor layer as it is. In this case, rolled copper foil, electrolytic copper foil, etc. can be used for copper foil. When using a thinner copper foil, it is possible to use a copper foil with a carrier from the viewpoint of improving workability. The support can be subjected to surface treatments such as matting treatment and corona treatment. In addition, the support body may be subjected to a release treatment with a silicone resin-based release agent, an alkyd resin-based release agent, a fluororesin-based release agent, or the like. The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 20 to 100 μm, and more preferably 25 to 50 μm from the viewpoint of handling and economical efficiency.

The coating device used to coat the resin varnish can use, for example, the following coating devices known to those skilled in the art of the present invention: a notched wheel (comma) coater, a bar coater, an anastomosis Kiss coater, roll coater, gravure coater, die coater, etc. These coating devices may be appropriately selected according to the thickness of the film to be formed. The drying conditions after coating the resin varnish are not particularly limited as long as they are appropriately determined according to the content, boiling point, and the like of the organic solvent. For example: in the case of a resin varnish containing about 40 to 60% by mass of an aromatic hydrocarbon-based solvent, the drying temperature is not particularly limited, but from the viewpoint of productivity and a moderate B-stage of the resin composition of this embodiment. Look, 50-200°C is better, 100-190°C is better, and 150-180°C is better. In addition, in the case of the above-mentioned resin varnish, the drying time is not particularly limited, but it is preferably 1 to 30 minutes, and 2 to 30 minutes from the viewpoint of productivity and the moderate B-stage of the resin composition of the present embodiment. 15 minutes is better, more preferably 3 to 10 minutes.

The thickness of the resin film of this embodiment can be appropriately determined according to the application of the resin film. From the viewpoint of formability and high-density wiring, it is preferably 5-150 μm, more preferably 10-100 μm, and 15 μm. ~60 μm is better.

The resin film of this embodiment may have a protective film on the surface opposite to the surface on which the support is provided from the viewpoint of preventing adhesion and damage of foreign matter and the like. The protective film is peeled off before laminating the resin film of this embodiment on a circuit board or the like.

The resin film of this embodiment is preferably used to form an insulating layer when producing a printed wiring board. For example, when manufacturing a printed wiring board, the resin film of this embodiment is a layer that functions as a layer that is laminated on a circuit board to melt and flow to fill the circuit board. In addition, for example, when the circuit board has a through hole, a through hole, etc., the resin film of this embodiment functions to flow through the hole and fill the hole.

[laminate] The laminated board of this embodiment has the cured product of the prepreg of this embodiment. In other words, the laminate of this embodiment is formed using the prepreg of this embodiment. It is preferable that the laminated board of this embodiment has the hardened|cured material of the prepreg of this embodiment, and metal foil. Furthermore, laminates with metal foils are also sometimes referred to as metal-clad laminates.

The metal of the metal foil is not particularly limited, and examples thereof include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium; alloys containing one or more of these metal elements, and the alloy can be For example: copper-based alloys, aluminum-based alloys, iron-based alloys, etc. Copper-based alloys include, for example, copper-nickel alloys and the like. Examples of iron-based alloys include iron-nickel alloys and the like. Among these, copper, nickel, aluminum, and an iron-nickel alloy are preferable, copper and aluminum are more preferable, and copper is more preferable from the viewpoint of conductivity and availability. The thickness of the metal foil is not particularly limited, but is preferably 1-200 μm, more preferably 2-100 μm, more preferably 3-50 μm.

The laminated board of the present embodiment can be produced, for example, by arranging metal foil on one or both sides of the prepreg of the present embodiment, followed by heat-press molding. Usually, the laminated board of this embodiment can be obtained by hardening the prepreg in a semi-hardened state by this heat press molding. In heat and pressure molding, only one prepreg can be used, and two or more prepreg bulk layers can also be used. In addition, the prepreg and the metal foil may also include a substrate subjected to inner layer circuit processing for heat and pressure molding. For heating and press molding, for example, multistage pressurization, multistage vacuum pressurization, continuous molding, autoclave molding machines, and the like can be used. The heating temperature for heating and press molding is not particularly limited, but is preferably 100 to 300°C, more preferably 150 to 280°C, and more preferably 200 to 250°C. The heating and pressing time of the heating and pressing molding is not particularly limited, but is preferably 10 to 300 minutes, more preferably 30 to 200 minutes, and more preferably 80 to 150 minutes. The pressure of heating and press molding is not particularly limited, but is preferably 1.5-5 MPa, more preferably 1.7-3 MPa, more preferably 1.8-2.5 MPa. However, these conditions can be appropriately adjusted according to the type of raw materials to be used, etc., and are not particularly limited.

[Printed Circuit Board] The printed wiring board of this embodiment has the hardened|cured material of the resin composition of this embodiment. The printed wiring board of the present embodiment is formed using, for example, one or more selected from the group consisting of the prepreg of the present embodiment, the resin film of the present embodiment, and the laminate of the present embodiment. . The printed wiring board includes at least: the cured product of the prepreg of the present embodiment, the cured product of the resin film of the present embodiment, or the laminated board of the present embodiment; and a conductor circuit layer. In addition, the printed wiring board of this embodiment is preferably a multilayer printed wiring board. Hereinafter, the method of manufacturing the printed wiring board of this embodiment using the resin film of this embodiment is demonstrated.

When a printed wiring board is manufactured using the resin film of this embodiment, first, the resin film of this embodiment is laminated|stacked on one surface or both surfaces of a circuit board. Specifically, for example, after arranging the resin film of the present embodiment on the circuit board, the resin film of the present embodiment can be laminated on the circuit board by using a vacuum laminator to apply pressure and heat while laminating the circuit board. . The circuit substrates used in printed circuit boards can be, for example, glass epoxy, metal substrates, polyester substrates, polyimide substrates, BT (bismaleimide-triazine) resin substrates, thermosetting poly A circuit board or the like with a patterned conductor layer formed on one or both sides of a phenylene ether substrate or the like. From the viewpoint of adhesiveness, the surface of the conductor layer of the circuit board may be roughened in advance by blackening treatment or the like.

Then, after the support body of the resin film is peeled off as needed, the resin film is heated and hardened, and an insulating layer is formed. The heating temperature during heat hardening is not particularly limited, but is preferably 100 to 300°C, more preferably 120 to 280°C, and more preferably 150 to 250°C. The heating time during heat hardening is not particularly limited, but is preferably 2 to 300 minutes, more preferably 5 to 200 minutes, and more preferably 10 to 150 minutes.

After the insulating layer is formed by the above method, openings can be made as required. Opening holes refers to the following steps: opening holes in the circuit substrate and the formed insulating layer by methods such as drills, lasers, plasmas, and combinations thereof to form through holes, through holes, and the like. As the laser used for opening holes, carbon dioxide laser, YAG (yttrium aluminum garnet) laser, UV (ultraviolet) laser, excimer laser, etc. can be used, for example.

Then, the surface of the insulating layer can be roughened by an oxidizing agent. In addition, when through holes, through holes, etc. are formed in the insulating layer and the circuit substrate, the so-called "smear" generated during the formation can be removed by conventional oxidizing agents. Roughening treatment and smear removal can be carried out simultaneously. Through the roughening treatment, uneven anchor portions (anchor) can be formed on the surface of the insulating layer, and the anchor portions are used to improve the adhesion strength with the conductor layer.

Then, a conductor layer is formed on the surface of the roughened insulating layer. The conductor layer can be formed, for example, by plating. As a plating method, an electroless plating method, an electrolytic plating method, etc. are mentioned, for example. Examples of metals for plating include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, and chromium; alloys containing at least one of these metal elements; and the like. Among these, copper and nickel are preferable, and copper is more preferable.

The method of patterning the conductor layer to form a circuit can utilize, for example, the following known methods: subtractive method, full additive method, semi-additive method (SAP: SemiAdditive Process), modified semi-additive method (m-SAP: modified Semi Additive Process), etc.

[Semiconductor Package] The semiconductor package of this embodiment has the printed wiring board of this embodiment. In other words, the semiconductor package of the present embodiment is formed using the printed wiring board of the present embodiment, preferably the multilayer printed wiring board of the present embodiment. The semiconductor package of the present embodiment can be manufactured, for example, by mounting a semiconductor chip, a memory, and the like on the printed wiring board of the present embodiment by a known method. [Example]

Examples are given below to describe this embodiment concretely. However, this embodiment is not limited by the following examples.

In addition, in each example, weight average molecular weight (Mw) was measured by the following method. Conversion from a calibration curve obtained by gel permeation chromatography (GPC) using standard polystyrene. The calibration curve is made using standard polystyrene: TSKstandard POLYSTYRENE (Type: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [TOSOH Co., Ltd. Company system, product name], approximated by a cubic formula. The measurement conditions of GPC are as follows. device: Pump: Model L-6200 [manufactured by Hitachi High-Technologies Co., Ltd.] Detector: Type L-3300 RI [manufactured by Hitachi High-Technologies Co., Ltd.] Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Co., Ltd.] Column: Guard column: TSK Guardcolumn HHR-L + Column: TSKgel G4000HHR + TSKgel G2000HHR (both manufactured by TOSOH Co., Ltd., trade name) String size: 6.0×40 mm (protection string), 7.8×300 mm (pipe string) Eluent: Tetrahydrofuran Sample concentration: 30 mg/5 mL Injection volume: 20 μL Flow rate: 1.00 mL/min Measuring temperature: 40°C

[Production Example 1: Production of Aminomaleimide Resin] Put 2,2-bis[4-(4-maleimidobenzene) into a reaction vessel with a volume of 5 L capable of heating and cooling, equipped with a thermometer, a stirring device, and a moisture meter with a reflux cooling tube. 100 parts by mass of oxy)phenyl]propane, 5.6 parts by mass of silicon oxide compound with primary amino groups at both ends (primary amino group equivalent 750 g/mol), 3,3'-diethyl-4,4'-di 7.9 parts by mass of aminodiphenylmethane and 171 parts by mass of propylene glycol monomethyl ether were reacted for 2 hours while refluxing. This was concentrated at reflux temperature for 3 hours to produce a solution of an aminomaleimide resin having a solid content concentration of 65% by mass. The resulting aminomaleimide resin had a weight average molecular weight (Mw) of about 2,700.

[Examples 1-3, Comparative Examples 1-4] (manufacture of resin composition) According to the formulation composition described in Table 1, prepare each component described in Table 1, and stir and mix together with toluene and methyl isobutyl ketone at room temperature (25°C) to produce a solid content concentration of 55-65 % by mass of the resin composition. In addition, in Table 1, the unit of the compounding quantity of each component is a mass part, and when it is a solution, it means the mass part of solid content conversion. In addition, the compounding quantity of (C)component and the component for comparison in Table 1 was the quantity which made the addition amount of (C)component and the component for comparison in each example the same mol number.

(Manufacture of prepregs and double-sided copper-clad laminates) The resin composition obtained above was coated on glass cloth (E glass, manufactured by Nitto Industries Co., Ltd.) with a thickness of 0.08 mm, and then heated and dried at 150° C. for 5 minutes to prepare a solid content derived from the resin composition. 47% by mass of prepreg. A low-profile copper foil with a thickness of 18 μm (manufactured by CIRCUIT FOIL, trade name "BF-ANP18", Rz of the M surface: 1.5 μm) was placed on the prepreg so that the M surface was in contact with the prepreg The upper and lower sides, and under the conditions of temperature 230°C, pressure 3.0 MPa, and time 90 minutes, heat and press forming to manufacture double-sided copper-clad laminates (thickness: 0.10 mm).

[assessment method] Each evaluation was performed by the following method using the resin composition and double-sided copper-clad laminate obtained in each example. The results are shown in Table 1.

(Measurement of Copper Foil Peel Strength) The copper foil of the double-sided copper-clad laminated board obtained in each example was processed into the linear shape of 5 mm width by etching, and it was set as the test piece. The formed straight line-shaped copper foil was mounted on a tabletop tester (manufactured by Shimadzu Corporation, trade name "EZ-TEST"), and tested at room temperature (25°C) at 90°C in accordance with JIS C6481:1996.ﾟ direction peeling, to measure the peeling strength of copper foil. In addition, the stretching speed at the time of peeling copper foil was set to 50 mm/min.

(Measurement of gelation time) The resin composition obtained in each example was coated on a PET film (manufactured by Teijin Co., Ltd., trade name: G2-38) with a thickness of 38 μm, and then heated and dried at 170°C for 5 minutes to prepare a B-stage resin film . This resin film was peeled off from the PET film, and pulverized to produce resin powder in a B-stage state. 0.1 g of the obtained resin powder was used as a measurement sample, and the time until the resin hardened (gelation time) was measured on a 180 degreeC hot plate. For the measurement, a gelation tester "GT-D-JIS" manufactured by Nisshin Scientific Co., Ltd. was used.

(Determination of Relative Permittivity and Dielectric Loss Tangent) The outer layer copper foil of the double-sided copper-clad laminate obtained in each example was removed by immersion in a copper etching solution (10 mass % solution of ammonium persulfate, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and cut into 90 mm and a width of 70 mm, set it as a test piece. Using this test piece, the relative permittivity and dielectric loss tangent under the conditions of a frequency of 10 GHz and a measurement temperature of 25° C. were measured by the SPDR (Split post dielectric resonators) method. The measuring device used was Network Analyzer "E5071C" manufactured by Keysight Technologies, the relative permittivity measuring jig used "SPDR-10GHz" manufactured by QWED, and the measurement program used material measurement software "85071E" manufactured by Keysight Technologies.

[Table 1]

In addition, the abbreviation etc. of each material in Table 1 are as follows. [(A) component: thermosetting resin] ・Maleimide-based resin: Aminomaleimide resin obtained in Production Example 1

[(B) component: polyphenylene ether resin] ・Polyphenylene ether-based resin: polyphenylene ether having methacryl groups at both ends (a compound contained in the above general formula (B-4), weight average molecular weight (Mw) 1,700)

・3-胺基丙基三乙氧基矽烷 [Component (C): Alkoxysilane compound having a primary amino group] ・3-(2-aminoethylamino)propyltriethoxysilane・N-(triethoxysilylpropyl) Melamine: a compound represented by the following formula (C-2)

・3-Aminopropyltriethoxysilane

式(C’-1)中，R表示2價鍵結基。 ・三聚氰胺 [Components for comparison] ・3-anilinopropyltriethoxysilane・Benzotriazolyl-containing silane coupling agent: a compound represented by the following general formula (C'-1), manufactured by Shin-Etsu Chemical Co., Ltd. , product name "X-12-1214A"

In formula (C'-1), R represents a divalent bonding group.・Melamine

[(D) component: inorganic filler] ・Silicon oxide: Spherical fused silica with an average particle size of 0.5 μm

[Component (E): Styrene-based elastomer] ・SEBS: Maleic anhydride-modified hydrogenated styrene-based elastomer (SEBS), acid value 10 mgCH ₃ ONa/g, styrene content 30%, MFR 5.0 g/ 10min (Measurement conditions of MFR: according to ISO1133, measured at 230°C, with a load of 2.16 kg)

[(F) ingredient: hardening accelerator] ・Tri-n-butylphosphine addition reaction product of p-benzoquinone ・2-Undecylimidazole ・Dicyandiamide

From the results shown in Table 1, it can be seen that the resin compositions of Comparative Examples 1 to 4 did not contain (C) an alkoxysilane compound having a primary amino group, while the copper foils of the resin compositions of Examples 1 to 3 in this embodiment The peel strength was more excellent than the resin composition of Comparative Examples 1-4. In addition, it can be seen from the results of the gelation time that the resin composition of Comparative Example 1 did not contain (C) an alkoxysilane compound having a primary amino group and components for comparison, while the resins of Examples 1 to 3 of this embodiment The curability of the composition is better than that of the resin composition of Comparative Example 1. [industrial availability]

The resin composition of this embodiment is excellent in copper foil peel strength and curability, so prepregs, laminates, printed circuit boards, semiconductor packages, etc. obtained using the resin composition are suitable for electronic devices that process high-frequency signals. Part use.

Domestic deposit information (please note in order of depositor, date, and number) none Overseas storage information (please note in order of storage country, institution, date, and number) none

Claims (14)

A resin composition comprising: (A) thermosetting resin; (B) polyphenylene ether resin; (C) alkoxysilane compounds having primary amino groups; and (D) Inorganic filler material. The resin composition according to claim 1, wherein the (A) thermosetting resin is at least one selected from the group consisting of epoxy resins, cyanate resins, and maleimide resins . The resin composition according to claim 1 or 2, wherein the (A) thermosetting resin is a maleimide resin. The resin composition according to claim 1 or 2, wherein the (B) polyphenylene ether-based resin has a functional group containing an ethylenically unsaturated bond. The resin composition according to claim 4, wherein the functional group containing an ethylenically unsaturated bond is a (meth)acryl group. The resin composition according to claim 1 or 2, wherein the (C) alkoxysilane compound having a primary amino group has a trialkoxysilyl group. The resin composition according to claim 1 or 2, wherein the content of the (C) alkoxysilane compound having a primary amino group is 0.1 with respect to the total solid content (100% by mass) of the resin composition. ~10% by mass. The resin composition according to claim 1 or 2, wherein the (D) inorganic filler is silicon oxide. The resin composition according to claim 1 or 2, further comprising: (E) a styrene-based elastomer. A prepreg comprising the resin composition according to claim 1 or 2 or a semi-cured product of the resin composition. A laminate comprising the hardened prepreg according to claim 10. A resin film comprising the resin composition according to claim 1 or 2 or a semi-cured product of the resin composition. A printed wiring board having a cured product of the resin composition according to claim 1 or 2. A semiconductor package having the printed wiring board described in Claim 13.