TW202136415A - Thermosetting resin composition, prepreg, laminate, printed wiring board and semiconductor package - Google Patents

Abstract

The present invention relates to: a thermosetting resin composition which contains (a) a compound that has at least one N-substituted maleimide group, (b) a compound that has at least two unsaturated aliphatic hydrocarbon groups, and (c) a benzoxazine compound; a prepreg which uses this thermosetting resin composition; a laminate; a printed wiring board; and a semiconductor package.

Description

Thermosetting resin composition, prepreg, build-up board, printed wiring board, and semiconductor package

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

In recent years, along with the trend of miniaturization and higher performance of electronic equipment, the development of higher line density and higher integration of printed circuit boards has also begun. Along with this, for copper clad laminates and interlayer insulating materials for printed wiring boards, there is a demand for improved reliability due to improvements in copper foil adhesion, heat resistance (high glass transition temperature), and low thermal expansion. Also gradually improved. Since the crosslinked structure peculiar to the cured product of the thermosetting resin can express high heat resistance and dimensional stability, the thermosetting resin is widely used in technical fields such as electronic parts. As thermosetting resins with high heat resistance, maleimide resins are known, but maleimide resins have low curability. Therefore, various studies have been conducted to improve this point.

Patent Document 1 discloses a thermosetting resin composition containing a compound having a maleimide group and a compound having an allyl or methacrylic group with a specific structure, and the thermosetting resin composition The material can be molded at a relatively low temperature, and further, it can be made into a thermosetting resin composition having excellent heat resistance, water absorption characteristics, mechanical strength, and thermal decomposition characteristics after curing. [Prior Technical Literature] (Patent Document)

Patent Document 1: International Publication No. 2017/170844.

[The problem to be solved by the invention] However, according to research conducted by the present inventors, it has been found that the insulating layer formed of the thermosetting resin composition of Patent Document 1 has poor adhesion to copper foil (hereinafter, also referred to as "copper foil adhesion").

In view of the above-mentioned current situation, the problem to be solved by this embodiment is to provide a thermosetting resin composition, a prepreg, a laminate, a printed wiring board, and a semiconductor package using the thermosetting resin composition, the thermosetting resin composition The flexible resin composition has good heat resistance and excellent copper foil adhesion.

通式(c-1)中，R^c1 和R^c2 各自獨立地為碳數1～10的烴基；X^c1 為碳數1～5的伸烷基、碳數2～5的亞烷基、－O－、磺醯基、羰氧基、－C(＝O)－或單鍵；n^c1 和n^c2 各自獨立地為0～4的整數。 [6] 如上述[1]～[5]中任一項所述之熱硬化性樹脂組成物，其中，相對於前述(a)成分100質量份，前述(b)成分的含量為5～85質量份。 [7] 如上述[1]～[6]中任一項所述之熱硬化性樹脂組成物，其中，相對於前述(a)成分100質量份，前述(c)成分的含量為1～30質量份。 [8] 如上述[1]～[7]中任一項所述之熱硬化性樹脂組成物，其中，前述(b)成分與前述(c)成分的含量比也就是(b)成分/(c)成分，以質量比計為1～15。 [9] 如上述[1]～[8]中任一項所述之熱硬化性樹脂組成物，其中，進一步含有環氧樹脂作為(d)熱硬化性樹脂。 [10] 如上述[1]～[9]中任一項所述之熱硬化性樹脂組成物，其中，進一步含有(e)無機填充材料。 [11] 一種預浸體，其是含有上述[1]～[10]中任一項所述之熱硬化性樹脂組成物而成。 [12] 一種積層板，其是含有上述[11]所述之預浸體而成。 [13] 一種印刷線路板，其是含有上述[12]所述之積層板而成。 [14] 一種半導體封裝體，其是將半導體元件裝配於上述[13]所述之印刷線路板上而成。 [發明的效果][Technical Means for Solving the Problem] In order to solve the above-mentioned problems, the inventors have repeatedly studied and found that the above-mentioned problems can be solved by the following technologies [1] to [14], and thus completed the present embodiment. [1] A thermosetting resin composition comprising: (a) a compound having at least one N-substituted maleimide group; (b) a compound having at least two unsaturated aliphatic hydrocarbon groups; and, (c) Benzoxazine compounds. [2] The thermosetting resin composition according to the above [1], wherein the component (a) contains a reactant, and the reactant is (a1) having at least two N-substituted maleimide groups The compound of (a2) is formed by reacting with (a2) a silicon oxide compound having at least two primary amine groups. [3] The thermosetting resin composition according to [1] or [2] above, wherein the component (b) is a compound having at least 3 unsaturated aliphatic hydrocarbon groups. [4] The thermosetting resin composition according to any one of [1] to [3] above, wherein the unsaturated aliphatic hydrocarbon group contained in the component (b) is selected from allyl groups and 1- One or more of the group consisting of acrylic groups. [5] The thermosetting resin composition according to any one of [1] to [4] above, wherein the component (c) is a compound represented by the following general formula (c-1):

In the general formula (c-1), R ^c1 and R ^c2 are each independently a hydrocarbon group having 1 to 10 ^{carbons; X c1} is an alkylene group having 1 to 5 carbons, an alkylene group having 2 to 5 carbons,- O-, sulfonyl group, carbonyloxy group, -C(=O)- or a single bond; n ^c1 and n ^c2 are each independently an integer of 0-4. [6] The thermosetting resin composition according to any one of [1] to [5] above, wherein the content of the component (b) is 5 to 85 with respect to 100 parts by mass of the component (a) Mass parts. [7] The thermosetting resin composition according to any one of [1] to [6] above, wherein the content of the component (c) is 1 to 30 relative to 100 parts by mass of the component (a) Mass parts. [8] The thermosetting resin composition according to any one of the above [1] to [7], wherein the content ratio of the (b) component to the (c) component is the (b) component/( c) Ingredients, 1-15 by mass ratio. [9] The thermosetting resin composition according to any one of [1] to [8] above, which further contains an epoxy resin as (d) the thermosetting resin. [10] The thermosetting resin composition according to any one of [1] to [9] above, which further contains (e) an inorganic filler. [11] A prepreg comprising the thermosetting resin composition according to any one of [1] to [10] above. [12] A laminated board comprising the prepreg described in [11] above. [13] A printed wiring board comprising the laminated board described in [12] above. [14] A semiconductor package formed by mounting a semiconductor element on the printed wiring board described in [13] above. [Effects of the invention]

According to this embodiment, it is possible to provide a thermosetting resin composition, a prepreg, a laminate, a printed wiring board, and a semiconductor package using the thermosetting resin composition, the thermosetting resin composition having good heat resistance It has excellent properties and copper foil adhesion.

In this manual, the numerical range indicated by "～" means the range that includes the numerical values before and after "～" as the minimum and maximum values, respectively. Regarding the numerical range described in this specification, the upper limit or lower limit of the numerical range can be replaced with the numerical values shown in the examples. In addition, the lower limit value and the upper limit value of the numerical range can be arbitrarily combined into the lower limit value or the upper limit value of other numerical ranges, respectively. Unless otherwise specified, each component and material exemplified in this specification may be used alone or in combination of two or more. In this specification, the content of each component in the thermosetting resin composition, when there are multiple substances corresponding to each component in the thermosetting resin composition, unless otherwise specified, it means that it is present in the thermosetting resin composition. The total content of the plurality of substances in the resin composition. The aspect which combined the description in this specification arbitrarily is also included in this embodiment. The mechanism of action described in this specification is an estimation, and is not a mechanism for limiting the effect exerted by the thermosetting resin composition of this embodiment. The aspect which combined the description in this specification arbitrarily is also included in this embodiment.

In addition, in this specification, the "resin component" refers to (a) component, (b) component, (c) component, (d) component used as needed, and other arbitrarily usable resins. The resin component is not Contains (e) inorganic fillers, hardening accelerators, additives, etc. In addition, in this specification, the term "solid content" refers to a non-volatile content that does not include volatile components such as organic solvents, and means a component that does not volatilize and remains when the thermosetting resin composition is dried. The solid content includes Those that are liquid, syrupy or waxy at room temperature.

[Thermosetting resin composition] The thermosetting resin composition of this embodiment is the following thermosetting resin composition, which includes: (a) A compound having at least one N-substituted maleimino group [hereinafter, sometimes referred to as (a) component]; (b) A compound having at least two unsaturated aliphatic hydrocarbon groups [hereinafter, sometimes referred to as (b) component]; and, (c) A benzoxazine compound [Hereinafter, it may be referred to as (c) component]. The thermosetting resin composition of the present embodiment has the property that it can be thermoset by heating the above-mentioned components to react. Hereinafter, each component contained in the thermosetting resin composition of this embodiment is described in detail.

<(a) Compounds with at least 1 N-substituted maleimide group> The thermosetting resin composition of this embodiment has a tendency to obtain particularly excellent heat resistance and low thermal expansion by containing the component (a). (a) A component may be used individually by 1 type, and may use 2 or more types together.

As component (a), from the viewpoint of heat resistance and low thermal expansion, (a1) a compound having at least two N-substituted maleimino groups [hereinafter, sometimes referred to as component (a1) ]. In addition, as the component (a), from the viewpoints of heat resistance, low thermal expansion, and copper foil adhesion, a reaction product of the component (a1) and a compound having at least two primary amine groups is preferred, and more preferred is ( a1) The reactant [hereinafter, sometimes referred to as modified maleimide resin (A )].

<(a1) Compounds with at least 2 N-substituted maleimido groups> As the (a1) component, a compound represented by the following general formula (a1-1) is preferred.

式(a1-1)中，X^a1 是由下述通式(a1-2)、(a1-3)、(a1-4)或(a1-5)表示的基團。

In the formula (a1-1), X ^a1 is a group represented by the following general formula (a1-2), (a1-3), (a1-4) or (a1-5).

式(a1-2)中，R^a1 是碳數1～5的脂肪族烴基或鹵素原子。p1是0～4的整數。＊表示鍵結部位。

In the formula (a1-2), ^Ra1 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p1 is an integer of 0-4. ＊Indicating the bonding site.

式(a1-3)中，R^a2 各自獨立地為碳數1～5的脂肪族烴基或鹵素原子。X^a2 為碳數1～5的伸烷基、碳數2～5的亞烷基、－O－、硫醚基、磺醯基、羰氧基、－C(＝O)－、單鍵或由下述(a1-3’)表示的基。q1各自獨立地為0～4的整數。＊表示鍵結部位。

In formula (a1-3), R ^{a2 is} each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X ^a2 is an alkylene group having 1 to 5 carbons, an alkylene group having 2 to 5 carbons, -O-, thioether group, sulfonyl group, carbonyloxy group, -C(=O)-, single bond or The group represented by the following (a1-3'). q1 is an integer of 0-4 each independently. ＊Indicating the bonding site.

式(a1-3’)中，R^a3 各自獨立地為碳數1～5的脂肪族烴基或鹵素原子。X^a3 為碳數1～5的伸烷基、碳數2～5的亞烷基、－O－、硫醚基、磺醯基、羰氧基、－C(＝O)－或單鍵。r1各自獨立地為0～4的整數。＊表示鍵結部位。

In the formula (a1-3 '), R ^a3 are each independently an aliphatic hydrocarbon group having a carbon number of 1 to 5 or a halogen atom. X ^a3 is an alkylene group having 1 to 5 carbon atoms, an alkylene group having 2 to 5 carbon atoms, -O-, thioether group, sulfonyl group, carbonyloxy group, -C(=O)- or a single bond. r1 is each independently an integer of 0-4. ＊Indicating the bonding site.

式(a1-4)中，n1表示1～10的整數。＊表示鍵結部位。

In formula (a1-4), n1 represents an integer of 1-10. ＊Indicating the bonding site.

式(a1-5)中，R^a4 各自獨立地為氫原子或碳數1～5的脂肪族烴基。u1各自獨立地為1～8的整數。＊表示鍵結部位。

In formula (a1-5), R ^{a4 is} each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u1 is an integer of 1-8 each independently. ＊Indicating the bonding site.

In the above general formula (a1-2) ^{, examples of the aliphatic hydrocarbon group represented by Ra1} include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, N-pentyl and so on. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. p1 is an integer of 0-4, and it is preferably an integer of 0-2, more preferably 0 from the viewpoint of ease of purchase. When p1 is an integer of 2 or more, a plurality of ^Ra1 may be the same or different from each other.

In the case of the general formula (a1-3), examples of the aliphatic hydrocarbon group represented by R ^a2 1 to 5 carbon atoms, a halogen atom, in the illustrated embodiment include the same as those of R ^a1. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably an ethyl group. Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^a2 include methylenyl group, 1,2-ethylene group, 1,3-propylene group, 1,4-butylene group, and 1,5 -Pentyl and others. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is preferred, and a methylenyl group is more preferred. Examples of the alkylene group having 2 to 5 carbon atoms represented by X ^a2 include ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, and isopentylene. Among these, isopropylidene is preferred. q1 is each independently an integer of 0-4, and from the viewpoint of ease of purchase, an integer of 0-2 is preferable, and 0 or 2 is more preferable.

In the formula (a1-3 '), as the carbon number of R ^a3 represents an aliphatic hydrocarbon group having 1 to 5 halogen atoms, the same as those of the case include the R ^a2. Examples of the alkylene having 1 to 5 carbons and the alkylene having 2 to 5 carbons represented by X ^a3 include alkylenes having 1 to 5 carbons represented by ^{X a2 in the general formula (a1-3).} The same group and the alkylene group having 2 to 5 carbon atoms. As X ^a3 , among the above options, an alkylene group having 2 to 5 carbon atoms is preferred, and an isopropylidene group is more preferred. r1 is an integer of 0-4, and from the viewpoint of ease of purchase, an integer of 0-2 is preferable, and 0 is more preferable. As the component (a1) used as a raw material of the modified maleimide resin (A), it is preferable to have a group represented by the above general formula (a1-3) as the above general formula (a1-1) Among the compounds of X ^a1 , among these, X ^{a2 is more} preferably a compound having a group represented by the above general formula (a1-3').

In the above general formula (a1-4), n1 is an integer of 1-10, and from the viewpoint of ease of purchase, it is preferably an integer of 1-5, and more preferably an integer of 1-3. In the general formula (A1-5), as the carbon number of the aliphatic hydrocarbon group represented by R ^a4 1 to 5, a halogen atom, in the general formula include the same as R ^a1 to (a1-2) are those, preferred The same is true. u1 is an integer of 1-8, preferably an integer of 1-3, more preferably 1. The component (a1) that can be used without reacting with the component (a2) is preferably a compound having a group represented by the general formula (a1-4) as X ^a1 of the general formula (a1-1) .

As the (a1) component, for example, N,N'-ethylenebismaleimide, N,N'-hexylbismaleimide, N,N'-(1,3-ethyleneimide Phenyl) bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4- Methyl phenylene)) bismaleimide, N,N'-(1,4-phenylene) bismaleimide, bis(4-maleiminophenyl) methane, bismaleimide (3-Methyl-4-maleiminophenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane Amine, bis(4-maleimidphenyl) ether, bis(4-maleimidphenyl) sulfide, bis(4-maleimidphenyl)sulfide, bis(4-maleimidphenyl) Leximinophenyl) ketone, bis(4-maleimidinylcyclohexyl)methane, 1,4-bis(4-maleimidinyl)cyclohexane, 1,4-bis(maleimidine) Leximinomethyl) cyclohexane, 1,4-bis(maleimidine methyl)benzene, 1,3-bis(4-maleimidine phenoxy)benzene, 1,3- Bis(3-maleiminophenoxy)benzene, bis[4-(3-maleiminophenoxy)phenyl]methane, bis[4-(4-maleiminophenoxy) Yl)phenyl]methane, 1,1-bis[4-(3-maleiminophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleiminobenzene) Oxy)phenyl]ethane, 1,2-bis[4-(3-maleiminophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimines Aminophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleiminophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimide) Iminophenoxy)phenyl]propane, 2,2-bis[4-(3-maleiminophenoxy)phenyl]butane, 2,2-bis[4-(4-male Aminophenoxy)phenyl]butane, 2,2-bis[4-(3-maleiminophenoxy)phenyl]-1,1,1,3,3,3-hexa Fluoropropane, 2,2-bis[4-(4-maleimidphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4'-bis( 3-maleimine phenoxy) biphenyl, 4,4'-bis(4-maleimine phenoxy) biphenyl, bis[4-(3-maleimine phenoxy) ) Phenyl] ketone, bis[4-(4-maleiminophenoxy)phenyl]ketone, 2,2-bis(4-maleiminophenyl)phenyl]disulfide, Bis[4-(3-maleimidephenoxy)phenyl]sulfide, bis[4-(4-maleimidephenoxy)phenyl]sulfide, bis[4-(3 -Maleimide phenoxy) phenyl] sulfide, bis[4-(4-maleimide phenoxy) phenyl] sulfide, bis[4-(3-maleimide) Phenoxy) phenyl] chrysene, bis[4-(4-maleimidin phenoxy) phenyl] chrysene, bis[4-(3-maleimid phenoxy) phenyl] ether , Bis[4-(4-maleimide phenoxy) phenyl] ether, 1,4-bis[4-(4- Maleimide phenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimide phenoxy)-α,α-dimethyl Benzyl]benzene, 1,4-bis[4-(3-maleiminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-( 3-maleiminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleiminophenoxy)-3,5- Dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleiminophenoxy)-3,5-dimethyl-α,α- Dimethylbenzyl]benzene, 1,4-bis[4-(3-maleiminophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene , 1,3-Bis[4-(3-maleiminophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethane maleic acid Amine (for example, manufactured by Daiwa Chemical Co., Ltd., trade name: BMI-2300, etc.) and the like. (a1) A component may be used individually by 1 type, and may use 2 or more types together.

Among these, bis(4-bismaleiminophenyl)methane and bis(4-maleimide) are preferred from the viewpoint of high reaction rate and possible higher heat resistance. Phenyl) sulfide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 2,2-bis[4-(4- Maleimidephenoxy)phenyl]propane, more preferably 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane.

((a2) Silicone compounds with at least 2 primary amine groups) As the component (a2) used to produce the modified maleimide resin (A) and react with the component (a1), a silicone compound having a primary amine group at at least one molecular terminal is preferred, and more preferably Siloxy compounds with primary amine groups on both ends of the molecule. In addition, the component (a2) may be a silicone compound having a primary amine group on the side chain, or a silicone compound having a primary amine group on the side chain and at least one molecular terminal. Among these, silicon oxide compounds having primary amine groups on both ends of the molecule are preferred. As such a silica compound, an amino modified silica compound represented by the following general formula (a2-1) is preferably used.

通式(a2-1)中，R^a21 各自獨立地表示烷基、苯基或經取代之苯基。R^a22 和R^a23 各自獨立地表示有機基。n表示2～50的整數。

In the general formula (a2-1), R ^a21 each independently represents an alkyl group, a phenyl group, or a substituted phenyl group. R ^a22 and R ^a23 each independently represent an organic group. n represents an integer of 2-50.

In the above general formula (a2-1), ^{the alkyl group represented by R a21} is preferably an alkyl group having 1 to 5 carbons, more preferably an alkyl group having 1 to 3 carbons, and still more preferably a carbon number of 1. Or 2 alkyl groups. Examples of the alkyl group represented by ^Ra21 include methyl, ethyl, propyl, butyl, and pentyl. Among these, methyl is preferred. Examples of the substituent in the substituted phenyl group represented by R ^a21 include an alkyl group, an alkenyl group, and an alkynyl group. Among these, an alkyl group is preferred. As an alkyl group, the same thing as the above-mentioned alkyl group is mentioned preferably. Among ^{the groups represented by Ra21} , from the viewpoint of solubility with other resins, a phenyl group or a methyl group is preferable, and a methyl group is more preferable. As the organic group represented by R ^a22 or R ^a23 , for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, or a linking group formed by a combination of these, etc. may be mentioned. Among these, substituted or unsubstituted alkylene groups, substituted or unsubstituted arylalkylene groups are preferred, and substituted or unsubstituted alkylene groups are more preferred. As the ^{alkylene group represented by R a22} or R ^a23 , for example, a methylene group, an ethylene group, a propylene group, etc. are mentioned, and a propylene group is preferable. Moreover, as a substituent of this alkylene group, a C6-C10 aryl group etc. are mentioned, for example. Examples of the arylene group represented by R ^a22 or R ^a23 include phenylene, naphthylene, and the like. In addition, examples of the substituent of the arylene group include an alkyl group having 1 to 5 carbon atoms.

(a2) The functional group equivalent of the component is not particularly limited, but is preferably 400 to 6000 g/eq, from the viewpoint of low thermal expansion, more preferably 400 to 5000 g/eq, and still more preferably 450 to 3500 g/eq , Particularly preferably 500～1500g/eq, most preferably 600～1500g/eq. In addition, the functional group equivalent of (a2) component means a primary amine group equivalent. (a2) A component may be used individually by 1 type, and may use 2 or more types together.

As the (a2) component, a commercially available product can be used. Examples of commercially available products include those having primary amine groups on both ends, such as "KF-8010" (functional group equivalent of 430 g/eq) and "X-22-161A" (functional group equivalent of 800 g/eq ), "X-22-161B" (functional group equivalent is 1500g/eq), "KF-8012" (functional group equivalent is 2200g/eq), "KF-8008" (functional group equivalent is 5700g/eq), " X-22-9409" (functional group equivalent is 700g/eq), "X-22-1660B-3" (functional group equivalent is 2200g/eq, the above is made by Shin-Etsu Chemical Co., Ltd.), "BY16-853U" (Functional group equivalent is 460g/eq), "BY16-853" (functional group equivalent is 650g/eq), "BY16-853B" (functional group equivalent is 2200g/eq, the above is manufactured by Toray Dow Corning Co., Ltd.); Those with a primary amine group on the side chain are "KF-868" (functional group equivalent of 8800g/eq), "KF-865" (functional group equivalent of 5000g/eq), "KF-864" (functional group Equivalent is 3800g/eq), "KF-880" (functional group equivalent is 1800g/eq), "KF-8004" (functional group equivalent is 1500g/eq, the above is made by Shin-Etsu Chemical Co., Ltd.), "XF42- "C5379" (trade name, manufactured by Momentive Performance Materials Japan Co., Ltd., functional group equivalent 740 g/eq) and the like. Among the commercially available products, from the viewpoint of low water absorption, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, BY16-853B, XF42-C5379 is preferably X-22-161A, X-22-161B, KF-8012, XF42-C5379 from the viewpoint of low thermal expansion.

(Azomethine modified silicone) Furthermore, as the component (a2), from the viewpoints of improvement in adhesion to copper foil and low thermal expansion, it is preferable to use those having an azomethine group, and more preferably those having an aromatic azomethine group, It is further preferable to use azomethine obtained by reacting with a dialdehyde compound to modify siloxane [hereinafter, sometimes referred to as azomethine modified siloxane (a2')]. Here, the aromatic azomethine group means a azomethine group (-N=CH-) bonded with at least one aromatic group (preferably an aromatic hydrocarbon group). As said dialdehyde compound, aliphatic dialdehyde compound, aromatic dialdehyde compound, etc. are mentioned, for example. Among these, aromatic dialdehyde compounds are preferred. The aromatic dialdehyde compound has an aromatic hydrocarbon group, and as long as it has an aromatic hydrocarbon group, it may also have an aliphatic hydrocarbon group. For example, when the structure has an aromatic hydrocarbon group-aliphatic hydrocarbon group-aromatic hydrocarbon group in the molecule, it is also included in the aromatic aldehyde compound.

As the aromatic dialdehyde compound, for example, terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde, 2,2'-bipyridine-4,4'-dialdehyde, etc. may be mentioned. Among these, terephthalaldehyde can be selected from the viewpoint of enabling further low thermal expansion, high reactivity, excellent solubility in organic solvents, and easy commercial purchase. The method for producing azomethine-modified silicone (a2') is not particularly limited. For example, the amine-modified silicone compound represented by the general formula (a2-1) can be combined with the dialdehyde compound. It is produced by performing dehydration condensation reaction in an organic solvent. Here, the usage amount of the amino-modified silica compound represented by the general formula (a2-1) and the dialdehyde compound is preferably, for example, the amino-modified siloxane compound represented by the general formula (a2-1) The number of primary amine groups of the silica compound [the usage amount of the amine modified silica compound/the equivalent of the primary amine group of the amine modified silica compound] is the number of the aldehyde groups of the dialdehyde compound [the usage amount of the dialdehyde compound/the dialdehyde compound The equivalent of aldehyde groups] is 1.1 times or more, more preferably 1.5 to 5 times, and still more preferably 2 to 4 times. By setting it to 1.1 times or more, the reaction can proceed sufficiently, and the obtained azomethine-modified siloxane (a2') will have primary amine groups on both ends of the molecule.

(Production method of modified maleimide resin (A)) The production method of the modified maleimide resin (A) is not particularly limited. For example, the primary amino group of the component (a2) can be paired with the carbon-carbon of the maleimide group of the component (a1). The double bond undergoes an addition reaction, thereby producing a modified maleimide resin (A). By manufacturing the modified imine resin (A) as component (a), the molecular weight of the resin in the thermosetting resin composition can be easily controlled, and excellent low thermal expansion and elastic modulus can be obtained. Propensity. The production of the modified imine resin (A) is preferably carried out while heating and keeping the temperature in an organic solvent. The reaction temperature is preferably 70 to 200°C, more preferably 80 to 150°C, and still more preferably 100 to 130°C. The reaction time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours.

In the production of the modified imine resin (A), a reaction catalyst can be used as needed. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazole and phenylimidazole; phosphorus-based catalysts such as triphenylphosphine. A reaction catalyst may be used individually by 1 type, and may use 2 or more types together.

In the production of modified maleimide resin (A), the number of maleimide groups of (a1) component [(a1) usage amount of component (g)/(a1) maleimide group of component The functional group equivalent (g/eq)] of (a2) component is preferably the number of primary amine groups [(a2) component usage (g)/(a2) component’s primary amine functional group equivalent (g/eq) )] is 0.1 to 10 times, more preferably 1 to 9 times, still more preferably 1.1 to 9 times, particularly preferably 2 to 8 times. If it is 0.1 times or more, especially 2 times or more, gelation will be suppressed and heat resistance tends to become good. If it is 10 times or less, solubility and heat resistance to organic solvents will tend to become good. .

In the production of the modified maleimide resin (A), it is preferably carried out in the presence of an organic solvent. The organic solvent is not particularly limited, and examples thereof include alcoholic solvents such as ethanol, propanol, butanol, methyl cellophane, butyl cellophane, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; dimethylformamide and dimethylacetamide Solvents containing nitrogen atoms such as amines and N-methylpyrrolidone; solvents containing sulfur atoms such as dimethyl sulfide, etc. An organic solvent may be used individually by 1 type, and may use 2 or more types together. Among them, from the viewpoint of solubility, cyclohexanone, propylene glycol monomethyl ether, and methyl cellophane are preferred, and from the viewpoint of low toxicity, cyclohexanone and propylene glycol monomethyl ether are more preferred. The methyl ether is more preferably propylene glycol monomethyl ether from the viewpoint of high volatility and less likely to remain residual solvent during the production of the prepreg.

The content of component (a) in the thermosetting resin composition of this embodiment is not particularly limited. From the viewpoints of heat resistance, low thermal expansion, and copper foil adhesion, it is relative to the thermosetting resin composition 100 parts by mass of the resin component is preferably 30 to 99 parts by mass, more preferably 40 to 95 parts by mass, still more preferably 50 to 90 parts by mass, particularly preferably 55 to 80 parts by mass.

<(b) Compounds with at least 2 unsaturated aliphatic hydrocarbon groups> The thermosetting resin composition of the present embodiment, by containing the component (b), has a tendency to obtain particularly excellent heat resistance and desmear resistance. (b) A component may be used individually by 1 type, and may use 2 or more types together.

The component (b) is a compound having at least two unsaturated aliphatic hydrocarbon groups from the viewpoint of heat resistance and scumming resistance, preferably a compound having at least three unsaturated aliphatic hydrocarbon groups. In addition, the unsaturated aliphatic hydrocarbon group contained in the component (b) is not particularly limited, but an unsaturated aliphatic hydrocarbon group capable of undergoing a radical reaction is preferred, and examples thereof include vinyl, isopropenyl, and 1-propylene Group, allyl group, 1-methylallyl group, 3-butenyl group, etc. Among them, from the viewpoint of resistance to scumming, an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms is preferred, an unsaturated aliphatic hydrocarbon group having 2 to 5 carbon atoms is more preferred, and an unsaturated aliphatic hydrocarbon group having 2 to 5 carbon atoms is more preferred. One or more selected from the group consisting of allyl and 1-propenyl. Furthermore, in this embodiment, groups such as maleimide groups and (meth)acrylic acid groups, which partially have unsaturated aliphatic hydrocarbon groups, cannot be said to be non-functional when the whole group is observed. The saturated aliphatic hydrocarbon group is not included in the "unsaturated aliphatic hydrocarbon group" in the component (b).

Examples of the component (b) include: (b1) a compound having an aromatic hydrocarbon group [hereinafter, sometimes referred to as compound (b1)], and (b2) a compound having a heterocyclic group [hereinafter, sometimes referred to as compound ( b2)] etc.

As an aromatic hydrocarbon group which the said compound (b1) has, a benzene residue, a naphthalene residue, a biphenyl residue, etc. are mentioned, for example. Among these, the residue of benzene and the residue of biphenyl are preferable. In addition, the residue referred to here means a group in which at least one of the hydrogen atoms contained in the aromatic ring is substituted with a group other than a hydrogen atom. In addition, the aromatic hydrocarbon group may have a substituent such as a hydroxyl group and an alkoxy group.

As specific examples of the compound (b1), the following compounds can be cited.

上述通式中，R^b1 ～R^b3 各自獨立地為有機基。m^b1 各自獨立地為0或1。n^b1 及n^b2 皆表示被中括號所包圍的部位的重複單元數，並且各自獨立地為1～100。

上述通式中，R^b4 ～R^b7 各自獨立地為有機基。m^b2 及m^b3 各自獨立地為0或1。n^b3 ～n^b6 皆表示被中括號所包圍的部位的重複單元數，並且各自獨立地為1～100。

上述通式中，R^b8 及R^b9 各自獨立地為有機基。n^b7 ～n^b10 皆表示被小括號所包圍的部位的重複單元數，並且各自獨立地為1～100。

In the above general formula, R ^b1 to R ^b3 are each independently an organic group. m ^b1 is 0 or 1 each independently. ^Both n b1 and n ^b2 represent the number of repeating units in the part enclosed by square brackets, and each independently is 1-100.

In the above general formula, R ^b4 to R ^b7 are each independently an organic group. m ^b2 and m ^b3 are each independently 0 or 1. n ^b3 to n ^b6 all represent the number of repeating units in the part enclosed by square brackets, and each independently is 1-100.

In the above general formula, R ^b8 and R ^b9 are each independently an organic group. n ^b7 to n ^b10 all represent the number of repeating units in the part surrounded by parentheses, and each independently is 1-100.

In the aforementioned general formula ^{, examples of the organic groups represented by R b 1} to R ^b9 include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and undecyl. , Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and other alkyl groups with 2 to 20 carbons; phenyl, biphenyl, naphthyl, etc. Aryl groups with 6 to 18 ring carbon atoms; aralkyl groups with 6 to 18 ring carbon atoms such as benzyl groups; 5 to 18 carbon atoms such as adamantyl, cyclohexyl, and cyclopentadienyl groups Alicyclic hydrocarbon group and so on. Among ^these, R ^{b 1,} the organic group R ^b4 and R ^b6 represents -O- or -S- may be via bonding. The organic groups represented by R ^{b 1} to R ^b9 are preferably the bulky organic groups in the above options, and more preferably are alkyl groups with 4 to 20 carbons, aryl groups with 6 to 18 ring carbons, An aralkyl group having 6 to 18 ring carbon atoms, an alicyclic hydrocarbon group having 5 to 18 carbon atoms, more preferably an alkyl group having 4 to 20 carbon atoms, an aralkyl group having 6 to 18 ring carbon atoms, and 5-18 alicyclic hydrocarbon group. Furthermore, when there are a plurality of R ^{b 1} in one molecule, the plurality of R ^{b 1} may be the same or different, or the same and different may be mixed. ^{The same is true} for R ^b2 to R b9 as described above for R ^{b 1} . m ^b1 to m ^b3 may each independently be any one of 0 and 1. As n ^b1 to n ^b10 , it is preferable that it is 1-100 each independently, and it is more preferable that it is 3-30.

上述通式中，R^b10 是碳數2～18的脂肪族烴基，其可包含選自由醚基及羥基所組成之群組中的至少1種。As a specific example of the said compound (b2), the following compounds can be mentioned, for example.

In the above general formula, R ^b10 is an aliphatic hydrocarbon group having 2 to 18 carbon atoms, which may include at least one selected from the group consisting of an ether group and a hydroxyl group.

通式中，p^b1 表示甲烯基的重複單元數，並且為2～18的整數。p^b2 表示氧伸乙基的重複單元數，並且為0或1。＊表示鍵結部位As the aforementioned R ^b10 , for example, a group represented by any one of the following general formulas (i) to (iii) is preferable.

In the general formula, p ^b1 represents the number of repeating units of the methylene group, and is an integer of 2-18. p ^b2 represents the number of repeating units of oxyethylene group, and is 0 or 1. ＊Indicating bonding part

The aforementioned p ^{b1 is} preferably an integer of 2-10, more preferably an integer of 3-8, and still more preferably an integer of 3-5. The aforementioned p ^{b2 is} preferably 1.

The content of the (b) component in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoint of low thermal expansion and desmear resistance, the carbon in the (b) component is preferred. The ratio of the number of carbon double bonds to the number of maleimino groups of the component (a) [number of carbon-carbon double bonds/number of maleimino groups] is adjusted so as to be 0.01 to 0.3.

The content of component (b) in the thermosetting resin composition of this embodiment is not particularly limited. From the viewpoints of heat resistance, scumming resistance, low thermal expansion, and copper foil adhesion, it is relative to heat 100 parts by mass of the resin component of the curable resin composition is preferably 2 to 80 parts by mass, more preferably 5 to 60 parts by mass, still more preferably 7 to 40 parts by mass, particularly preferably 10 to 30 parts by mass. In addition, the content of component (b) in the thermosetting resin composition of the present embodiment is not particularly limited. From the viewpoints of heat resistance, desmear resistance, low thermal expansion, and copper foil adhesion, it is relatively Based on 100 parts by mass of (a) component, it is preferably 5 to 85 parts by mass, more preferably 7 to 60 parts by mass, still more preferably 10 to 45 parts by mass, and particularly preferably 15 to 35 parts by mass.

〈(C) benzoxazine compound〉 The thermosetting resin composition of this embodiment contains (c) a benzoxazine compound. In addition, the benzoxazine compound in this embodiment means a compound having at least one benzoxazine ring in the molecule. The benzoxazine ring here conceptually includes a hydrogen atom to be bonded substituted with a substituent. The thermosetting resin composition of this embodiment can have good heat resistance and can obtain excellent copper foil adhesion by containing (c) a benzoxazine compound. Although the reason is not clear, it is presumed to be due to the following reasons: the benzoxazine compound acts as a hardening agent for the component (a) to increase the degree of hardening of the component (a), and the benzoxazine compound is derived from Heteroatoms promote electrostatic interaction with copper, etc. (c) A component may be used individually by 1 type, and may use 2 or more types together.

(c) The number of benzoxazine rings that the component has in one molecule may be 1 or more, and more preferably 2 or more. As the component (c), conventional benzoxazine compounds can be used, and examples thereof include Pd-type benzoxazine compounds, Fa-type benzoxazine compounds, ALP-d-type benzoxazine compounds, and T-ala Type benzoxazine compounds and so on.

Examples of the component (c) include a compound represented by the following general formula (c-1), a compound represented by the following general formula (c-2), and a compound represented by the following general formula (c-3) Wait.

通式(c-1)中，R^c1 和R^c2 各自獨立地為碳數1～10的烴基。X^c1 是碳數1～5的伸烷基、碳數2～5的亞烷基、－O－、磺醯基、羰氧基、－C(＝O)－或單鍵。n^c1 和n^c2 各自獨立地為0～4的整數。

In the general formula (c-1), R ^c1 and R ^c2 are each independently a hydrocarbon group having 1 to 10 carbon atoms. X ^c1 is an alkylene group having 1 to 5 carbon atoms, an alkylene group having 2 to 5 carbon atoms, -O-, a sulfonyl group, a carbonyloxy group, -C(=O)-, or a single bond. n ^c1 and n ^c2 are each independently an integer of 0-4.

通式(c-2)中，R^c3 各自獨立地為碳數1～10的烴基。R^c4 各自獨立地為碳數1～10的烴基或氫原子。X^c2 是碳數1～5的伸烷基、碳數2～5的亞烷基、－O－、磺醯基、羰氧基、－C(＝O)－或單鍵。n^c3 為0～3的整數。

In the general formula (c-2), R ^{c3 is} each independently a hydrocarbon group having 1 to 10 carbons. R ^{c4 is} each independently a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. X ^c2 is an alkylene group having 1 to 5 carbon atoms, an alkylene group having 2 to 5 carbon atoms, -O-, a sulfonyl group, a carbonyloxy group, -C(=O)-, or a single bond. n ^c3 is an integer of 0-3.

通式(c-3)中，R^c5 為碳數1～10的烴基。R^c6 為碳數1～10的烴基或氫原子。n^c4 為0～4的整數。

In the general formula (c-3), R ^c5 is a hydrocarbon group having 1 to 10 carbons. R ^c6 is a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. n ^c4 is an integer of 0-4.

In the above general formula (c-1) ^{, examples of the hydrocarbon groups having 1 to 10 carbons represented by R c1} and R ^c2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. Aliphatic hydrocarbon groups such as phenyl group, tertiary butyl group, n-pentyl group, n-octyl group, n-decyl group, etc.; aromatic hydrocarbon group such as phenyl group, etc. In the above general formula (c-1), n ^c1 and n ^c2 are each independently an integer of 0-4, and from the viewpoint of ease of purchase, an integer of 0-2 is preferable, and 0 is more preferable. When n ^c1 and n ^c2 are integers of 2 or more, plural n ^c1 and n ^c2 may be the same as or different from each other. In the above general formula (c-1) ^{, examples of the alkylene group having 1 to 5 carbon atoms represented by X c1} include, for example, a methylenyl group, 1,2-ethylene group, 1,3-propylene group, and 1 ,4-butylene, 1,5-pentylene, etc. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is preferred, and a methylenyl group is more preferred. In the above general formula (c-1), examples of the alkylene group having 2 to 5 carbon atoms represented by ^{X c1 include ethylene, propylene, isopropylene, butylene, isobutylene,} Pentylene, isopentylene, etc. Among these, isopropylidene is preferred.

In the above general formula (c-2) ^{, examples of the hydrocarbon group having 1 to 10 carbons represented by R c3} include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tri Aliphatic hydrocarbon groups such as butyl, n-pentyl, n-octyl, and n-decyl groups; aromatic hydrocarbon groups such as phenyl groups. In the above general formula (c-2), n ^c3 is an integer of 0 to 3. From the viewpoint of ease of purchase, an integer of 0 to 2 is preferable, and 0 is more preferable. In the above general formula (c-2), the alkylene group having 1 to 5 carbon atoms and the alkylene group having 2 to 5 carbon atoms represented by ^{X c2 include those of X c1 in the general formula (c-1).} The alkylene group having 1 to 5 carbon atoms and the alkylene group having 2 to 5 carbon atoms are the same. In the above general formula (c-2) ^{, examples of the hydrocarbon group having 1 to 10 carbons represented by R c4} include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tri Alkyl groups such as butyl and n-pentyl; aromatic hydrocarbon groups such as phenyl and naphthyl. Among these, an aromatic hydrocarbon group is preferred, and a phenyl group is more preferred.

In the above general formula (c-3) ^{, examples of the hydrocarbon group having 1 to 10 carbons represented by R c5} include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tri Aliphatic hydrocarbon groups such as butyl, n-pentyl, n-octyl, and n-decyl groups; aromatic hydrocarbon groups such as phenyl groups. In the above general formula (c-3), n ^c4 is an integer of 0-4, and from the viewpoint of ease of purchase, an integer of 0-2 is preferable, and 0 is more preferable. When n ^c4 is an integer of 2 or more, a plurality of R ^c5 may be the same or different from each other. In the above general formula (c-3), examples of the hydrocarbon group having 1 to 10 carbons represented by ^{R c6} include the same ones as those of the hydrocarbon group having 1 to 10 carbons represented by ^{R c4 in the general formula (c-2).}

Among the compounds represented by any of the above general formulas (c-1) to (c-3), from the viewpoint of low thermal expansion and heat resistance, it is preferably represented by the above general formula (c-1) The compound represented by the above general formula (c-2) is more preferably the compound represented by the above general formula (c-1). In addition, the compound represented by the above general formula (c-1) is preferably a compound represented by the following formula (c-4), and the compound represented by the above general formula (c-2) is preferably The compound represented by the formula (c-5).

The content of component (c) in the thermosetting resin composition of this embodiment is not particularly limited. From the viewpoints of heat resistance, low thermal expansion, moldability, and copper foil adhesion, it is relative to thermosetting resin 100 parts by mass of the resin component of the composition is preferably 0.2 to 20 parts by mass, more preferably 1 to 15 parts by mass, still more preferably 1 to 10 parts by mass, particularly preferably 1 to 8 parts by mass. In addition, the content of component (c) in the thermosetting resin composition of the present embodiment is not particularly limited. From the viewpoints of heat resistance, low thermal expansion, moldability, and copper foil adhesion, it is relative to (a ) 100 parts by mass of the component, preferably 1-30 parts by mass, more preferably 1-20 parts by mass, still more preferably 1-15 parts by mass, particularly preferably 1-10 parts by mass.

The content ratio of the aforementioned (b) component to the aforementioned (c) component in the thermosetting resin composition of the present embodiment [(b) component/(c) component] is not particularly limited, and is in terms of heat resistance and low thermal expansion. From the viewpoints of formability and copper foil adhesion, in terms of mass ratio, it is preferably 1-15, more preferably 1-10, and still more preferably 1-8.

〈(D) Thermosetting resin〉 The thermosetting resin composition of the present embodiment may further contain (d) thermosetting resin [hereinafter, sometimes referred to as (d) component]. By containing the component (d), the thermosetting resin composition of the present embodiment can further improve the adhesion to metal foils such as copper foil. In addition, the definition of (d) thermosetting resin in this embodiment shall be what does not contain (a)-(c) component. (d) A component may be used individually by 1 type, and may use 2 or more types together.

Examples of the component (d) include epoxy resins, phenol resins (excluding the above-mentioned (b) component), unsaturated amide resins (excluding the above-mentioned (a) component), and cyanate resins. , Isocyanate resin, oxetane (oxetane) resin, amine resin, unsaturated polyester resin, allyl resin (not including the above (b) component), dicyclopentadiene resin, silicone resin, trinitrogen The heterophenyl resin, melamine resin, etc. are preferably at least one selected from the group consisting of these resins. Among these, epoxy resin is preferable from the viewpoint of formability and electrical insulation, and from the viewpoint of improving the adhesiveness of copper foil.

As the epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, novolac type epoxy resin containing naphthalene skeleton, stilbene type epoxy resin, epoxy resin containing triazabenzene skeleton, Epoxy resins containing stilbene skeleton, triphenylmethane type epoxy resins, biphenyl type epoxy resins, xylene type epoxy resins, biphenylarane type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type Epoxy resins, alicyclic epoxy resins, polycyclic aromatic diglycidyl ether compounds such as polyfunctional phenols and anthracene, and phosphorus-containing epoxy resins obtained by introducing phosphorus compounds into these epoxy resins Resin etc. Among them, from the viewpoint of formability, more preferred are novolac type epoxy resins containing naphthalene skeletons, biphenylarane type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins. The resin, naphthalene-type epoxy resin, and dicyclopentadiene-type epoxy resin are more preferably biphenylarane-type epoxy resin.

When the thermosetting resin composition of this embodiment contains (d) thermosetting resin, its content is not particularly limited. From the viewpoints of heat resistance, low thermal expansion, and copper foil adhesion, it is relative to thermosetting resin. 100 parts by mass of the resin component of the resin composition is preferably 1-20 parts by mass, more preferably 2-15 parts by mass, and still more preferably 4-12 parts by mass.

〈(E)Inorganic fillers〉 The thermosetting resin composition of this embodiment may further contain (e) an inorganic filler [hereinafter, it may be referred to as (e) component]. By containing the component (e), the thermosetting resin composition of the present embodiment has more excellent low thermal expansion and desmear resistance. (e) A component may be used individually by 1 type, and may use 2 or more types together.

As the (e) component, for example, silicon dioxide, aluminum oxide, titanium oxide, mica, beryllium earth, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, hydrogen Alumina, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, quartz powder, short glass fiber, glass fine powder ) And insulating glass, etc., preferably at least one selected from the group consisting of these. As glass, E-type glass, T-type glass, D-type glass, etc. are mentioned preferably. Among them, from the viewpoint of dielectric properties, heat resistance, and low thermal expansion, silicon dioxide is preferred. As the silica, for example, precipitated silica with a high moisture content produced by a wet method, and dry silica produced by a dry method that hardly contain bound water, etc. can be cited. As dry-process silica, it can be classified into broken silica, fumed silica, molten spherical silica, etc. due to the difference in its manufacturing method. Among these, from the viewpoint of low thermal expansion and fluidity when filled in a resin, molten spherical silica is preferred.

The component (e) may be surface-treated with a coupling agent. The method of surface treatment by coupling agent can be dry or wet surface treatment of the inorganic filler material before blending, or integral blending treatment. After the surface-treated inorganic filler is blended into other components to form a composition, a silane coupling agent is added to the composition. Examples of coupling agents include silane coupling agents, titanate coupling agents, and silicone oligomers. Among them, the silane coupling agent is preferred, and the aminosilane coupling agent is more preferred.

(e) The average particle diameter of the component is not particularly limited, but is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm, and still more preferably 0.1 to 1 μm. Here, the so-called average particle diameter in this embodiment refers to the particle diameter at the point corresponding to 50% of the volume when the total volume of particles is set to 100% to obtain the cumulative particle size distribution curve based on the particle diameter. The particle size can be measured by a particle size distribution measuring device using a laser diffraction scattering method or the like.

When the thermosetting resin composition of this embodiment contains (e) an inorganic filler, its content is not particularly limited. From the viewpoints of heat resistance, low thermal expansion, and copper foil adhesion, it is relative to thermosetting resin 100 parts by mass of the resin component of the composition is preferably 10 to 500 parts by mass, more preferably 50 to 400 parts by mass, still more preferably 100 to 300 parts by mass, particularly preferably 150 to 300 parts by mass.

〈Other ingredients〉 The thermosetting resin composition of this embodiment may contain, for example, thermoplastic resins, hardening accelerators, organic fillers, flame retardants, ultraviolet absorbers, and peroxides within a range that does not impair the purpose of this embodiment. , Antioxidants, photopolymerization initiators, fluorescent whitening agents, and adhesion promoters consisting of one or more types. In addition, these other components may be used individually by 1 type, respectively, and may use 2 or more types together.

Examples of thermoplastic resins include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamide resin, and polyamide resin. Amide resin, xylene resin, polyphenylene sulfide resin, polyether imide resin, polydietherketone resin, silicone resin, tetrafluoroethylene resin, etc.

Examples of hardening accelerators include imidazole compounds and their derivatives; organic phosphorus compounds such as phosphines and phosphonium salts, adducts of tertiary phosphines and quinones; secondary amines, tertiary amines, and Grade ammonium salt and so on.

Examples of organic fillers include resin fillers composed of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc.; and those with a core shell structure. Resin filler, etc.

Examples of flame retardants include aromatic phosphate compounds, azo compounds, phosphonates, metal salts of phosphonic acid compounds, red phosphorus, 9,10-dihydro-9-oxa-10-phosphine Phosphorus-based flame retardants such as phenanthrene-10-oxide and its derivatives; nitrogen-based flame retardants such as guanidine sulfonate, melamine sulfate, melamine polyphosphate, and melamine cyanurate; containing bromine and chlorine Halogen-containing flame retardants; antimony trioxide and other inorganic flame retardants.

As an ultraviolet absorber, a benzotriazole type ultraviolet absorber is mentioned, for example. The peroxide is preferably one that can promote the reaction of component (a) and component (b), and examples include organic peroxides such as α,α'-bis(tertbutylperoxy)dicumylbenzene Wait. Examples of antioxidants include hindered phenol-based antioxidants, hindered amine-based antioxidants, and the like. Examples of the photopolymerization initiator include photopolymerization of benzophenones, benzyl ketal, 9-oxysulfur [口+山][口+星] system (thioxanthone), etc. Starter. As a fluorescent whitening agent, the fluorescent whitening agent of a stilbene derivative etc. are mentioned, for example. Examples of the adhesion enhancing agent include urea compounds such as urea silane, the aforementioned coupling agent, and the like.

(Varnish) The thermosetting resin composition of the present embodiment may be in a varnish state, and is formed by dissolving or dispersing each component in an organic solvent for use in the production of a prepreg or the like. That is, the varnish is also included in the thermosetting resin composition of this embodiment. Examples of organic solvents used in varnishes include alcoholic solvents such as methanol, ethanol, propanol, butanol, methyl cellulose, butyl cellulose, and propylene glycol monomethyl ether; acetone, methyl ethyl Ketone solvents such as methyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; toluene, xylene, homo Aromatic solvents such as trimethylbenzene; solvents containing nitrogen atoms such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; solvents containing sulfur atoms such as dimethylsulfoxide, etc. . An organic solvent may be used individually by 1 type, and may use 2 or more types together. Among them, from the viewpoint of solubility, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellulose, and propylene glycol monomethyl ether are preferred, and they are less toxic. From a viewpoint, methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable. The solid content concentration of the varnish is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. If the solid content concentration of the varnish is within the above range, good coating properties can be maintained, and a prepreg with an appropriate amount of adhesion of the thermosetting resin composition can be obtained.

[Prepreg] The prepreg of this embodiment contains the thermosetting resin composition of this embodiment. Specifically, it contains a B-staged thermosetting resin composition. The prepreg of the present embodiment can be manufactured by impregnating the thermosetting resin composition of the present embodiment in a fiber base material and semi-curing (B-staged) by heating or the like. As the above-mentioned fibrous base material, conventional fibrous base materials used for various laminated sheets for electrical insulating materials can be used. Examples of the material include: E-glass, S-glass, low-dielectric glass, Q-type glass and other inorganic fibers; low-dielectric glass polyimide, polyester, tetrafluoroethylene and other organic fibers ; And, such mixtures, etc. In particular, from the viewpoint of obtaining a substrate having excellent dielectric properties, low-dielectric glass fibers and Q-type glass fibers are preferred.

The fibrous substrates may, for example, have the shape of woven fabric, non-woven fabric, roving, chopped strand mat, or surfacing mat. The material and shape of the fibrous base material can be appropriately selected based on the intended use and performance of the molded article, and according to needs, it may be a fibrous base material composed of one material and one shape, or two A fibrous substrate composed of more than one material, or a fibrous substrate having two or more shapes. The thickness of the fibrous base material can be, for example, a thickness of about 0.03 to 0.5 mm. These fiber substrates are suitable for those made by surface treatment with silane coupling agent, or those made by mechanical opening treatment from the perspective of heat resistance, moisture resistance, and processability.

For the prepreg of this embodiment, for example, the adhesion amount of the thermosetting resin composition to the fiber substrate (the content of the thermosetting resin composition that does not contain an organic solvent in the obtained prepreg) is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, still more preferably 40 to 70% by mass. The prepreg of this embodiment can be obtained by the following method: After impregnating the thermosetting resin composition in the fiber base material, it is generally heated and dried at a temperature of 100 to 200°C for 1 to 30 minutes for semi-curing. (Phase B).

[Laminates] The laminated sheet of this embodiment is a laminated sheet containing the prepreg of this embodiment. The laminated sheet of this embodiment can be obtained by forming the prepreg bulk layer of this embodiment. Specifically, it can be manufactured by, for example, preparing one sheet of the prepreg of this embodiment or stacking 2-20 sheets of this prepreg, and arranging copper on one or both sides of the prepreg. The structure made of metal foils such as aluminum, aluminum, etc., is laminated and formed. With this manufacturing method, it is possible to obtain a laminated board having an insulating layer formed using the prepreg of this embodiment, and metal foils arranged on one or both sides of the insulating layer. The metal foil is not particularly limited as long as it can be used as an electrical insulating material. Furthermore, a laminated board having a structure in which a metal foil is arranged on one or both sides of the laminated board is particularly called a metal-clad laminated board. As the forming conditions when manufacturing the laminated board, for example, the method of the laminated board for electrical insulating materials and the multilayer board can be applied. Examples of the molding device include multi-stage pressurization, multi-stage vacuum pressurization, continuous molding, and hot press molding machines. As molding conditions, molding can be performed using, for example, a temperature range of 100 to 250°C, a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours. In addition, the prepreg of the present embodiment and the wiring board for the inner layer can be combined to be laminated and molded to produce a laminated board.

[Printed Circuit Board] The printed wiring board of this embodiment is a printed wiring board containing the laminated board of this embodiment. The printed wiring board of this embodiment can be manufactured by performing circuit processing on the metal-clad laminated board of this embodiment, for example. Examples of circuit processing methods include: subtractive process, fully-additive process, semi-additive process, or simulated semi-additive process (mSAP, modified semi-additive process). additive process) and other known methods. In addition, a plurality of circuit-processed laminated boards can be laminated via the prepreg of this embodiment and subjected to hot press processing, thereby enabling multi-layering at once. After that, the multilayer printed wiring board can also be manufactured through the following steps: forming through holes or blind holes by drilling or laser processing; and forming interlayer lines by plating or conductive paste.

[Semiconductor Package] The semiconductor package of this embodiment is formed by mounting a semiconductor on the printed wiring board of this embodiment. The semiconductor package of this embodiment can be manufactured by, for example, the following method: semiconductor elements such as semiconductor chips, memory, etc. are mounted on specific positions of the printed wiring board of this embodiment, and the semiconductor package is sealed by sealing resin or the like. The components are sealed. [Example]

Then, the following embodiments are used to describe this embodiment in further detail, but these embodiments are not intended to limit the embodiment. In addition, the copper clad laminated board obtained in each example was measured and evaluated by the following method.

(1) Glass transition temperature The copper clad laminate was immersed in a copper etching solution to remove the copper foil, and an evaluation substrate with a width of 4 mm × a length of 30 mm × a thickness of 0.4 mm was prepared, and then a dynamic viscoelasticity measuring device (manufactured by UBM Co., Ltd., trade name DVE) -V4) to determine the glass transition temperature. After mounting the evaluation board made by the above operation on the detector, it is measured under the measuring conditions of temperature rise rate of 5°C/min, frequency of 10Hz, and measurement temperature range of 40 to 360°C, and the loss elastic modulus becomes the largest The temperature is set as the glass transition temperature. The higher the glass transition temperature, the better the heat resistance. In addition, in Table 1, the case where the loss elastic modulus exceeds 360°C is described as ">360".

(2) Soldering heat resistance An evaluation board cut into a 25mm square copper clad laminate was produced, and the evaluation board was floated in a solder bath at 288°C for a maximum of 90 minutes, and the appearance of the evaluation board was visually observed. Measure the time until swelling occurs. In Table 1, those who have not been confirmed to swell even after they have floated for 90 minutes are described as "A".

(3) Thermal expansion coefficient The copper foil is removed by immersing the copper-clad laminate in a copper etching solution, and a 5mm×5mm square evaluation substrate is made, and then a TMA test device (manufactured by TA Instrument Corporation, trade name TMAQ400EM) is used to perform heat by compression. Mechanical analysis. After mounting the evaluation board in the above device, the temperature is raised to 260°C at a temperature increase rate of 10°C/min, and the temperature is lowered to 10°C at a temperature decrease rate of 10°C/min, and then the temperature is raised again at a temperature rise rate of 10°C/min. To 320°C. The coefficient of thermal expansion was measured based on the two temperature increases during the first temperature increase and the second temperature increase. The average coefficient of thermal expansion from 30°C to 100°C in the second measurement was calculated, and this numerical value was used as the value of the coefficient of thermal expansion.

(4) Desmear resistance (measurement of weight loss after desmear treatment) The copper foil is removed by immersing the copper-clad laminate in a copper etching solution, and an evaluation substrate of 40mm×40mm is made, and then the The evaluation substrate was immersed in a swelling liquid, namely "Swelling Dip Securiganth P" (aqueous solution of glycol ethers and sodium hydroxide, manufactured by Atotech Japan Co., Ltd.) at 60°C for 10 minutes, and then immersed in roughness at 80°C. The chemical solution is "Concentrate Compact P" (KMnO ₄ is 60g/L and NaOH is 40g/L aqueous solution, manufactured by Atotech Japan Co., Ltd.) for 20 minutes, and finally immersed in the neutralization solution, which is "Reduction Solution" at 40°C. Securiganth P" (aqueous solution of sulfuric acid, manufactured by Atotech Japan Co., Ltd.) for 5 minutes, and then dried at 80°C for 10 minutes, thereby performing a desmear treatment. The value of the weight loss (g/m ² ) after the desmear treatment with respect to the dry weight before the desmear treatment was calculated, and this value was used as an index of desmear resistance. The smaller the weight reduction of scum removal, the better the resistance to scum removal.

(5) Peel strength between layers The copper foil was removed by immersing the copper-clad laminate in a copper etching solution, and an evaluation substrate with a width of 10 mm × a length of 100 mm × a thickness of 0.4 mm was prepared. At the interface between the insulating layer and the laminated insulating layer, one end of the insulating layer on the outermost surface of the evaluation substrate was peeled, and the peeled part was clamped with a jig. The tensile tester was used to measure the peeling in the vertical direction. Peel strength between layers. Furthermore, the stretching speed was about 50 mm/min, and the measurement temperature was room temperature.

(6) Peel strength of copper foil The copper-clad laminate was immersed in a copper etching solution to prepare an evaluation substrate formed with an outer layer copper foil with a width of 3 mm. One end of the evaluation substrate was peeled off at the interface between the outer copper layer and the insulating layer, the peeled portion was clamped with a jig, and the copper foil peeling strength when peeled in the vertical direction was measured using a tensile tester. Furthermore, the stretching speed was about 50 mm/min, and the measurement temperature was room temperature.

[Synthesis example 1: Synthesis of modified maleimide resin (A)] (1. Synthesis of azomethine modified silicone [(a2’) component]) In a reaction vessel with a volume of 2 liters, pour 592 parts by mass of both terminal amine modified silica compound "XF42-C5379" (trade name, manufactured by Momentive Performance Materials Japan, functional group equivalent 740g/eq), 33 mass parts Parts of terephthalaldehyde and 939 parts by mass of propylene glycol monomethyl ether were reacted at 115°C for 2 hours. The reaction vessel was equipped with a thermometer, a stirring device, and a moisture meter with a reflux cooling tube. After that, the temperature is raised to 125°C and dehydration is carried out by concentration under normal pressure to obtain a solution containing azomethine-modified siloxane. (2. Synthesis of modified maleimide resin (A)) In a reaction vessel with a volume of 2 liters, pour 119 parts by mass (in terms of solid content) of the above-mentioned solution containing azomethine-modified siloxane, and 161 parts by mass of 2,2-bis[4(4-马Leximine phenoxy) phenyl] propane (component (a1)) and 376 parts by mass of propylene glycol monomethyl ether were reacted at 120°C for 4 hours to obtain a modified maleimide-containing resin ( A) [Hereinafter referred to as a solution of modified maleimide resin (a-1)], the reaction vessel is equipped with a thermometer, a stirring device, and a moisture meter with a reflux cooling tube.

[Examples 1 to 5, Comparative Examples 1 to 2] Use methyl ethyl ketone as the diluting solvent, and mix the ingredients with the formulation described in Table 1 and stir for 6 hours to prepare the solid content concentration (that is, the content of the thermosetting resin composition that does not contain organic solvent) 65 mass% varnish. Then, the obtained varnish was impregnated and applied to an E-type glass fiber cloth with a thickness of 0.1 mm, and dried by heating at 110°C for 3 minutes to obtain a thermosetting resin composition with a content of 47 to 48% by mass Of prepreg. Stack 4 pieces of this prepreg, and arrange 12μm electrolytic copper foil on top and bottom. After heating to 240°C under conditions of pressure 3.0MPa and temperature rising rate of 4.0°C/min, hold for 85 minutes and release the pressure, then cool for 30 minutes. In this way, a copper clad laminate is obtained. Using the obtained copper-clad laminated board, the above-mentioned measurement and evaluation were carried out. The results are shown in Table 1.

Each component described in Table 1 is shown below. [(a) Component: a compound having at least one N-substituted maleimide group] Modified maleimide resin (a-1): Modified maleimide resin (a-1) synthesized in Synthesis Example 1.

[Component (b): Compound having at least two unsaturated aliphatic hydrocarbon groups] Allylized phenol resin: "LVA01" manufactured by Qunrong Chemical Industry Co., Ltd., a compound represented by the following formula (b-8).

[Component (c): benzoxazine compound] 3,3'-(Menyl-1,4-diphenylene) bis(3,4-dihydro-2H-1,3-benzoxazine): Pd-type benzoxazine, from the above formula The compound represented by (c-4).

[Component (d): Thermosetting resin] Biphenylarane epoxy resin: manufactured by Nippon Kayaku Co., Ltd., trade name "NC-3000-H".

[Component (e): Inorganic filler] Molten spherical silica: average particle size 0.5μm.

[Table 1] Example Comparative example 1 2 3 4 5 1 2 Blending composition (a) Ingredients Modified maleimide resin (a-1) Mass parts 75.0 70.0 70.0 70.0 70.0 75.0 70.0 (b) Ingredients Allyl phenol resin Mass parts 15.0 15.0 20.0 17.5 20.0 20.0 20.0 (c) Ingredients 3,3'-(Menyl-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine) Mass parts 5.0 5.0 5.0 2.5 2.5 0.0 0.0 (d) Ingredients Biphenyl Arane Type Epoxy Resin Mass parts 5.0 10.0 5.0 10.0 7.5 5.0 10.0 (e) Ingredients Molten spherical silica Mass parts 230 230 230 230 230 230 230 Evaluation results (1) Glass transition temperature °C 359 355 ＞360 ＞360 ＞360 ＞360 ＞360 (2) Soldering heat resistance - A A A A A A A (3) Thermal expansion coefficient ppm/℃ 7.6 7.8 8.0 8.0 7.8 7.6 7.7 (4) Desmear resistance (weight reduction after desmear treatment) g/m ² 3.08 1.74 1.85 1.81 1.87 3.39 2.18 (5) Peel strength between layers kN/m 0.65 0.59 0.62 0.59 0.57 0.38 0.33 (6) Peel strength of copper foil kN/m 0.60 0.47 0.54 0.48 0.48 0.43 0.32

As can be seen from Table 1, compared with Comparative Example 1 which does not contain component (c), Example 1 using the thermosetting resin composition of this embodiment has the same degree of glass transition temperature, soldering heat resistance, and thermal expansion coefficient, and Improved resistance to slag removal, interlayer peeling strength, and copper foil glass strength. In addition, it can be seen that the examples 2 to 5 using the thermosetting resin composition of this embodiment have the same degree of glass transition temperature, soldering heat resistance, and coefficient of thermal expansion as compared with Comparative Example 2 which does not contain the component (c), and Improved resistance to slag removal, interlayer peeling strength, and copper foil glass strength. From the foregoing, it can be seen that the thermosetting resin of the present embodiment has good heat resistance and excellent copper foil adhesion.

According to the thermosetting resin composition of the present embodiment, a laminated board having good heat resistance and excellent copper foil adhesion can be obtained, and therefore, a high-density and high-multilayer printed wiring board can be manufactured. Therefore, the thermosetting resin composition of the present embodiment is suitable for use in printed circuit boards of electronic equipment, which can be used in computers, information equipment terminals, etc., which process a large amount of data at high speed. In particular, it can be used in printed circuit boards of tablet personal computers and notebook personal computers that have a high demand for thinning.

without

without

Domestic deposit information (please note in the order of deposit institution, date and number) without Foreign hosting information (please note in the order of hosting country, institution, date, and number) without

Claims (14)

A thermosetting resin composition containing: (a) Compounds having at least one N-substituted maleimino group; (b) Compounds having at least 2 unsaturated aliphatic hydrocarbon groups; and, (c) Benzoxazine compounds. The thermosetting resin composition according to claim 1, wherein the aforementioned component (a) is a reactant, and the reactant is (a1) a compound having at least two N-substituted maleimide groups, and (a2) A silicon oxide compound having at least two primary amine groups is reacted. The thermosetting resin composition according to claim 1 or 2, wherein the component (b) is a compound having at least 3 unsaturated aliphatic hydrocarbon groups. The thermosetting resin composition according to any one of claims 1 to 3, wherein the unsaturated aliphatic hydrocarbon group contained in the component (b) is selected from the group consisting of allyl group and 1-propenyl group One or more in the group. The thermosetting resin composition according to any one of claims 1 to 4, wherein the component (c) is a compound represented by the following general formula (c-1):

In the general formula (c-1), R ^c1 and R ^c2 are each independently a hydrocarbon group having 1 to 10 ^{carbons; X c1} is an alkylene group having 1 to 5 carbons, an alkylene group having 2 to 5 carbons,- O-, sulfonyl group, carbonyloxy group, -C(=O)- or a single bond; n ^c1 and n ^c2 are each independently an integer of 0-4. The thermosetting resin composition according to any one of claims 1 to 5, wherein the content of the component (b) is 5 to 85 parts by mass relative to 100 parts by mass of the component (a). The thermosetting resin composition according to any one of claims 1 to 6, wherein the content of the component (c) is 1 to 30 parts by mass relative to 100 parts by mass of the component (a). The thermosetting resin composition according to any one of claims 1 to 7, wherein the content ratio of the aforementioned component (b) to the aforementioned component (c) is (b) component/(c) component, by mass The ratio is 1-15. The thermosetting resin composition according to any one of claims 1 to 8, which further contains an epoxy resin as (d) thermosetting resin. The thermosetting resin composition according to any one of claims 1 to 9, which further contains (e) an inorganic filler. A prepreg containing the thermosetting resin composition according to any one of claims 1 to 10. A laminated board comprising the prepreg described in claim 11. A printed circuit board comprising the laminated board described in claim 12. A semiconductor package which is formed by assembling semiconductor elements on the printed circuit board described in claim 13.