TW202214753A - Prepreg, laminate and printed wiring board - Google Patents

Abstract

To provide a thermosetting resin composition and a prepreg having high heat resistance, low relative dielectric constants, high metal foil adhesiveness, a high glass transition temperature and low thermal expansibility, and also excellent moldability and plating uniformity, and also provide a laminate and a printed wiring board. A prepreg contains a thermosetting resin composition containing (A) a maleimide compound, (B) an epoxy resin, (C) a copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a maleic anhydride, and (D) silica treated with an amino silane coupling agent.

Description

Prepregs, Laminates and Printed Wiring Boards

The present invention relates to a prepreg, a laminate, and a printed wiring board suitable as a material for electronic equipment and the like.

In recent years, high-speed communication, high circuit density, extremely thin circuit boards, and the ratio of circuit width (L) to spacing (S) of circuit boards [L/S ] also tend to narrow. With such narrowing of L/S, it has become difficult to stably produce circuit boards with good yields. In addition, in the design of a conventional circuit board, a layer with no circuit pattern called a "skip layer" is provided in some layers in consideration of communication obstacles and the like. Electronic equipment is gradually becoming high-performance, and the number of circuit designs is gradually increasing, and the number of layers of the circuit board is gradually increasing. However, due to the provision of the aforementioned skip layer, there is a problem that the thickness of the motherboard will further increase. Among the methods for improving these problems, a more effective method is to reduce the relative permittivity of insulating materials used in circuit boards. Since it is easy to control the resistance of L/S by lowering the relative permittivity of the insulating material, it is possible to stably manufacture with L/S close to the current design, and it is possible to reduce the number of layers by reducing the number of jumping layers. Therefore, for insulating materials used in circuit boards, material properties with a relatively small relative permittivity are currently being sought.

In recent years, in motherboards of mobile phones and the like, which are being thinned and reduced in price with the increase in the density of electronic devices, materials with a low relative permittivity are also being sought in order to cope with the thinning. In addition, in the equipment of communication systems represented by servers, routers, mobile base stations, etc., they have been gradually used in higher frequency bands, and lead-free solders with high melting point have been gradually used for soldering electronic parts. Therefore, As the material of the substrate used in these, a material having a low dielectric constant, a high glass transition temperature (high Tg), and excellent reflow heat resistance is currently being sought. In addition, as the circuit density increases and the pattern width is narrowed in the motherboard used in the terminal of a multi-functional mobile phone, it is required to use a small diameter laser via to connect the layers. From the viewpoint of connection reliability, there are many examples using field plating, and the connectivity of the interface between the inner layer copper and the copper plating is very important, and therefore, the improvement of the laser beam of the substrate is being sought. Processability.

Generally, a step of partially removing resin residues (desmear treatment step) is performed after the laser processing of the substrate. Because the smear removal process is performed on the bottom surface and the wall surface of the laser through hole, when the resin component of the base material is dissolved in a large amount due to the smear removal treatment, there is a possibility that the shape of the laser through hole will be significantly deformed due to the dissolution of the resin. In addition, various problems such as unevenness of plating due to unevenness of the wall surface may occur. Therefore, it has been sought to make the following amount suitable for the resin component of the base material dissolved by the desmear treatment, that is, the desmear dissolved amount.

In order to prepare a thermosetting resin composition with a relatively small relative permittivity, the following methods have been used: a method containing an epoxy resin having a relatively small relative permittivity, a method of introducing a cyanate group, a method containing a polyphenylene ether method etc. However, by simply combining these methods, it is difficult to satisfy various requirements such as lower relative permittivity, high heat resistance, reliability, and halogen-free. For example, resin compositions containing epoxy resin (refer to Patent Document 1); resin compositions containing polyphenylene ether and bismaleimide (refer to Patent Document 2); resin compositions containing polyphenylene ether and cyanate ester have been proposed resin composition (refer to Patent Document 3); resin composition containing at least one of styrene-based thermoplastic elastomers, etc. and/or triallyl cyanurate, etc. (refer to Patent Document 4); containing polybutylene Diene resin composition (refer to Patent Document 5); obtained by preliminarily reacting polyphenylene ether-based resin with polyfunctional maleimide and/or polyfunctional cyanate resin and liquid polybutadiene resin composition (refer to Patent Document 6); containing polyphenylene ether obtained by supplying or grafting a compound having an unsaturated double bond group, and triallyl cyanurate and/or triallyl Resin composition composed of isocyanurate, etc. (see Patent Document 7); resin containing polyphenylene ether, unsaturated carboxylic acid or unsaturated acid anhydride reaction product, polyfunctional maleimide, etc. composition (refer to Patent Document 8) and the like. [Prior Art Literature] (patent literature)

Patent Document 1: Japanese Patent Laid-Open No. 58-69046 Patent Document 2: Japanese Patent Laid-Open No. 56-133355 Patent Document 3: Japanese Patent Publication No. 61-18937 Patent Document 4: Japanese Patent Laid-Open No. 61-286130 Patent Document 5: Japanese Patent Laid-Open No. 62-148512 Patent Document 6: Japanese Patent Laid-Open No. 58-164638 Patent Document 7: Japanese Patent Application Laid-Open No. 2-208355 Patent Document 8: Japanese Patent Application Laid-Open No. 6-179734

[Problems to be Solved by Invention] Although the prepregs containing the resin compositions described in Patent Documents 1 to 8 show relatively good relative permittivity, there are increasing cases in which they cannot meet the stringent demands of the market in recent years. In addition, any one of high heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties (laser workability) is often insufficient, and there are still further improvements. room. In addition, the actual situation is that the material has not been sufficiently developed from the viewpoint of being suitable for throwing properties. Therefore, the problem to be solved by the present invention is to provide a prepreg, a laminate and a printed wiring board, the prepreg has high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature and low Excellent in thermal expansion, formability and throwing properties. [Technical means to solve the problem]

The inventors of the present invention have made intensive studies in order to solve the above-mentioned problems, and as a result, they have found a prepreg that can solve the above-mentioned problems, and completed the present invention. The prepreg contains a thermosetting resin composition, and the thermosetting resin composition The compound contains: "(A) Maleimide compound"; "(B) Epoxy resin"; "(C) Copolymer resin with specific structural unit"; and, "(D) An aminosilane-based coupling agent Treated Silicon Oxide". The present invention has been accomplished based on such a technical idea.

通式(a2-1)中，R ^A4表示從羥基、羧基及磺酸基之中選出的酸性取代基，R ^A5表示碳數1～5的烷基或鹵素原子，t為1～5的整數，u為0～4的整數且滿足1≦t＋u≦5，其中，當t為2～5的整數時，複數個R ^A4可相同亦可不同，此外，當u為2～4的整數時，複數個R ^A5可相同亦可不同；

通式(a3-1)中，X ^A2表示碳數1～3的脂肪族烴基或－O－，R ^A6和R ^A7各自獨立地表示碳數1～5的烷基、鹵素原子、羥基、羧基或磺酸基，v和w各自獨立地為0～4的整數。 [3]如上述[1]或[2]所述之預浸體，其中，前述(C)成分為共聚樹脂，該共聚樹脂具有由下述通式(C-i)表示的結構單元與由下述通式(C-ii)表示的結構單元：

式(C-i)中，R ^C1為氫原子或碳數1～5的烷基，R ^C2為碳數1～5的烷基、碳數2～5的烯基、碳數6～20的芳基、羥基或(甲基)丙烯醯基，x為0～3的整數，其中，當x為2或3時，複數個R ^C2可相同亦可不同。 [4]如上述[3]所述之預浸體，其中，前述通式(C-i)中，R ^C1為氫原子且x為0。 [5]如上述[1]或[2]所述之預浸體，其中，前述(C)成分中，源自芳香族乙烯系化合物的結構單元與源自馬來酸酐的結構單元的含有比例，也就是源自芳香族乙烯系化合物的結構單元／源自馬來酸酐的結構單元，以莫耳比計，為2～9。 [6]如上述[1]或[2]所述之預浸體，其中，前述(C)成分中，源自芳香族乙烯系化合物的結構單元與源自馬來酸酐的結構單元的含有比例，也就是源自芳香族乙烯系化合物的結構單元／源自馬來酸酐的結構單元，以莫耳比計，為3～7。 [7]如上述[1]至[6]中任一項所述之預浸體，其中，前述(C)成分的重量平均分子量為4,500～18,000。 [8]如上述[1]至[7]中任一項所述之預浸體，其中，前述(C)成分的重量平均分子量為9,000～13,000。 [9]如上述[1]至[8]中任一項所述之預浸體，其中，前述(B)成分為雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、萘型環氧樹脂、蒽型環氧樹脂、聯苯型環氧樹脂、聯苯芳烷基型環氧樹脂或雙環戊二烯型環氧樹脂。 [10]如上述[1]至[9]中任一項所述之預浸體，其中，前述熱硬化性樹脂組成物進一步含有(E)硬化劑。 [11]如上述[1]至[10]中任一項所述之預浸體，其中，前述熱硬化性樹脂組成物進一步含有(F)難燃劑。 [12]一種積層板，其是含有上述[1]至[11]中任一項所述之預浸體與金屬箔而成。 [13]一種印刷線路板，其是含有上述[1]至[11]中任一項所述之預浸體或上述[12]所述之積層板而成。 [功效] The present invention relates to the following [1] to [13]. [1] A prepreg comprising a thermosetting resin composition containing: (A) a maleimide compound; (B) an epoxy resin; (C) a copolymer A resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride; and (D) silicon oxide treated with an aminosilane-based coupling agent. [2] The prepreg according to the above [1], wherein the component (A) is a maleimide compound having an N-substituted maleimide group, which has an N-substituted maleimide group. The maleimide compound of amino group is a maleimide compound having at least 2 N-substituted maleimide groups in one molecule of (a1), and (a2) is represented by the following general formula (a2-1 ) and the monoamine compound represented by (a3) are obtained by reacting the diamine compound represented by the following general formula (a3-1);

In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is an integer of 1 to 5 , u is an integer from 0 to 4 and satisfies 1≦t+u≦5, where, when t is an integer from 2 to 5, a plurality of R ^A4 can be the same or different, and when u is an integer from 2 to 4, A plurality of R ^A5 can be the same or different;

In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, and a carboxyl group. or a sulfonic acid group, v and w are each independently an integer of 0-4. [3] The prepreg according to the above [1] or [2], wherein the component (C) is a copolymer resin having a structural unit represented by the following general formula (Ci) and a The structural unit represented by the general formula (C-ii):

In formula (Ci), R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , a hydroxyl group or a (meth)acryloyl group, and x is an integer of 0 to 3, wherein when x is 2 or 3, a plurality of R ^C2 may be the same or different. [4] The prepreg according to the above [3], wherein in the general formula (Ci), R ^C1 is a hydrogen atom and x is 0. [5] The prepreg according to the above [1] or [2], wherein the content ratio of the structural unit derived from an aromatic vinyl compound to the structural unit derived from maleic anhydride in the component (C) , that is, a structural unit derived from an aromatic vinyl compound/a structural unit derived from maleic anhydride is 2 to 9 in molar ratio. [6] The prepreg according to the above [1] or [2], wherein the content ratio of the structural unit derived from an aromatic vinyl compound to the structural unit derived from maleic anhydride in the component (C) , that is, a structural unit derived from an aromatic vinyl compound/a structural unit derived from maleic anhydride is 3 to 7 in molar ratio. [7] The prepreg according to any one of the above [1] to [6], wherein the weight average molecular weight of the component (C) is 4,500 to 18,000. [8] The prepreg according to any one of the above [1] to [7], wherein the weight average molecular weight of the component (C) is 9,000 to 13,000. [9] The prepreg according to any one of the above [1] to [8], wherein the component (B) is bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac Varnish type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin or dicyclopentadiene type epoxy resin. [10] The prepreg according to any one of the above [1] to [9], wherein the thermosetting resin composition further contains (E) a curing agent. [11] The prepreg according to any one of the above [1] to [10], wherein the thermosetting resin composition further contains (F) a flame retardant. [12] A laminate comprising the prepreg according to any one of the above [1] to [11] and a metal foil. [13] A printed wiring board comprising the prepreg according to any one of the above [1] to [11] or the laminate according to the above [12]. [effect]

According to the present invention, it is possible to obtain a prepreg, a laminate and a printed wiring board which have high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion and formability and excellent leveling properties.

Hereinafter, the present invention will be described in detail. The present invention provides a prepreg containing the following thermosetting resin composition. [Thermosetting resin composition] The prepreg is made of a thermosetting resin composition containing: (A) maleimide compound; (B) epoxy resin; (C) a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride; and, (D) Silicon oxide treated with an aminosilane-based coupling agent.

通式(a2-1)中，R ^A4表示從羥基、羧基及磺酸基之中選出的酸性取代基，R ^A5表示碳數1～5的烷基或鹵素原子，t為1～5的整數，u為0～4的整數且滿足1≦t＋u≦5，其中，當t為2～5的整數時，複數個R ^A4可相同亦可不同，此外，當u為2～4的整數時，複數個R ^A5可相同亦可不同。

通式(a3-1)中，X ^A2表示碳數1～3的脂肪族烴基或－O－，R ^A6和R ^A7各自獨立地表示碳數1～5的烷基、鹵素原子、羥基、羧基或磺酸基，v和w各自獨立地為0～4的整數。 以下，關於馬來醯亞胺化合物(A)的記載，亦能夠解讀為上述具有N-取代馬來醯亞胺基之馬來醯亞胺化合物的記載。 Hereinafter, each component contained in the thermosetting resin composition will be described in detail. <(A) Maleimide Compound> (A) Component is a maleimide compound (hereinafter, sometimes referred to as a maleimide compound (A)), preferably an N-substituted maleimide compound A maleimide compound having an imino group; more preferably a maleimide compound having an N-substituted maleimide group, wherein (a1) has at least 2 N-substituted maleimide in one molecule Maleimide compound of ligimide group [hereinafter, abbreviated as maleimide compound (a1)], (a2) Monoamine compound represented by the following general formula (a2-1) [hereinafter, abbreviated as Monoamine compounds (a2)] and (a3) are obtained by reacting a diamine compound [hereinafter abbreviated as diamine compound (a3)] represented by the following general formula (a3-1).

In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is an integer of 1 to 5 , u is an integer from 0 to 4 and satisfies 1≦t+u≦5, where, when t is an integer from 2 to 5, a plurality of R ^A4 can be the same or different, and when u is an integer from 2 to 4, The plurality of R ^A5 may be the same or different.

In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, and a carboxyl group. or a sulfonic acid group, v and w are each independently an integer of 0-4. Hereinafter, the description of the maleimide compound (A) can also be interpreted as the description of the above-mentioned maleimide compound having an N-substituted maleimide group.

The weight average molecular weight (Mw) of the maleimide compound (A) is preferably from 400 to 3,500, preferably from 400 to 2,300, and preferably from 800 to 800 from the viewpoint of solubility in organic solvents and mechanical strength. 2,000 is better. In addition, in this specification, the weight average molecular weight is a value measured by a gel permeation chromatography (GPC) method (in terms of standard polystyrene) using tetrahydrofuran as an eluent, and more specifically, it is a value obtained by The value measured by the method described in the Example.

(maleimide compound (a1)) The maleimide compound (a1) is a maleimide compound having at least two N-substituted maleimide groups in one molecule. The maleimide compound (a1) includes, for example, a maleimide compound having an aliphatic hydrocarbon group between any two maleimide groups among a plurality of maleimide groups [ Hereinafter, referred to as aliphatic hydrocarbon group-containing maleimide], or a maleimide compound containing an aromatic hydrocarbon group between any two maleimide groups among a plurality of maleimide groups [Hereinafter, referred to as aromatic hydrocarbon group-containing maleimide]. Among them, from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, aromatic hydrocarbon group-containing maleia Amines are preferred. The aromatic hydrocarbon group-containing maleimide may contain an aromatic hydrocarbon group between any combination of two maleimide groups that are arbitrarily selected. From the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwability, the maleimide compound (a1) is preferably It is a maleimide compound having 2 to 5 N-substituted maleimide groups in one molecule, more preferably a maleimide compound having 2 N-substituted maleimide groups in one molecule Amine compounds. In addition, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing properties, as the maleimide compound (a1), Preferably, it is an aromatic hydrocarbon group-containing maleimide represented by any of the following general formulae (a1-1) to (a1-4), more preferably, it is represented by the following general formulae (a1-1), ( The aromatic hydrocarbon group-containing maleimide represented by a1-2) or (a1-4) is particularly preferably an aromatic hydrocarbon group-containing maleimide represented by the following general formula (a1-2).

In the above formulae (a1-1) to (a1-2), R ^A1 to R ^A3 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and X ^A1 represents an alkylene group having 1 to 5 carbon atoms, a carbon number of 2 ~5 alkylene group, -O-, -C(=O)-, -S-, -S-S-, or sulfonyl group, p, q and r are each independently an integer of 0 to 4, s is an integer from 0 to 10. Examples of the aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R ^A1 to R ^A3 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-butyl Amyl etc. From the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, the aliphatic hydrocarbon group has a carbon number of 1 to 3. Aliphatic hydrocarbon groups are preferred, and methyl and ethyl groups are preferred.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^A1 include methylene, 1,2-dimethylene, 1,3-trimethylene, 1,4-tetramethylene, 1 , 5-pentamethylene and so on. From the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, as the alkylene group, those having 1 to 3 carbon atoms are used. Alkylene is preferred, and methylene is preferred. As a C2-C5 alkylene group represented by X ^A1 , an ethylene group, a propylene group, an isopropylidene group, a butylene group, an isobutylene group, a pentylene group, an isopentylene group, etc. are mentioned, for example. Among these, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, as the alkylene group, iso-iso Propyl is preferred. Among the above options, X ^A1 is preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 2 to 5 carbon atoms. The preferred ones are as described above. p, q and r are each independently an integer of 0 to 4, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties It can be seen that any one is preferably 0 to 2, preferably 0 or 1, and more preferably 0. s is an integer of 0 to 10, and 0 to 5 are preferable, and 0 to 3 are more preferable from the viewpoint of easiness of acquisition. In particular, the aromatic hydrocarbon group-containing maleimide compound represented by the general formula (a1-3) is preferably a mixture in which s is 0 to 3.

Specific examples of the maleimide compound (a1) include N,N'-ethylidenebismaleimide, N,N'-hexamethylenebismaleimide, Bis(4-maleimidocyclohexyl)methane, 1,4-bis(maleimidomethyl)cyclohexane and other aliphatic hydrocarbon-containing maleimides; 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) phenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenyl bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) bis(4-maleimidophenyl) benzene, bis(4-maleimidophenyl) base) thioether, bis(4-maleimidophenyl)ketone, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidophenyl)cyclohexane iminomethyl)cyclohexane, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, bis[4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[ 4-(3-Maleimidophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1, 2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane Alkane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)benzene yl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy) base)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)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-maleic Imidophenoxy)biphenyl, 4,4-bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)benzene base] ketone, bis[4-(4-maleimidophenoxy)phenyl]ketone, 2,2'-bis(4-maleimidophenyl)disulfide, bis( 4-Maleimidophenyl) disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimide) phenoxy) phenyl] sulfide, bis[4-(3-maleimidophenoxy)phenyl] sulfite, bis[4-(4-maleimidophenoxy) ) phenyl] sulfene, bis[4-(3-maleimidophenoxy)phenyl] sulfite, bis[ 4-(4-maleimidophenoxy)phenyl] bis[4-(3-maleimidophenoxy)phenyl] ether, bis[4-(4-mer Leyliminophenoxy)phenyl] ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1 ,3-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimide) phenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl base]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3 -Bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3 -Maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimido) Aromatic hydrocarbon group-containing maleimide such as phenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene and polyphenylmethane maleimide. Among these, bis(4-maleimidophenyl)methane and bis(4-maleimidobenzene) are preferred from the viewpoint of high reaction rate and higher heat resistance. base) bisulfite, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) disulfide, N,N'-(1,3-phenylene) ) bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and bis(4- Maleimidophenyl)methane, N,N'-(1,3-phenylene)bismaleimide, and bis(4- maleiminophenyl)methane. The maleimide compound (a1) may be used alone or in combination of two or more.

(Monoamine compound (a2)) The monoamine compound (a2) is a monoamine compound represented by the following general formula (a2-1).

In the above general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is a group of 1 to 5 carbon atoms. Integer, u is an integer of 0 to 4 and satisfies 1≦t+u≦5, wherein, when t is an integer of 2 to 5, a plurality of R ^A4 may be the same or different, and when u is an integer of 2 to 4 , the plurality of R ^A5 may be the same or different. From the viewpoints of solubility and reactivity, as the acidic substituent represented by R ^A4 , a hydroxyl group and a carboxyl group are preferable, and when heat resistance is also considered, a hydroxyl group is preferable. t is an integer from 1 to 5, and from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing property, t is 1 to 3. is preferably an integer, preferably 1 or 2, more preferably 1. Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A5 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n-pentyl. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. As a halogen atom represented by R ^A5 , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example. u is an integer from 0 to 4, and from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, 0 to 3 An integer is preferable, an integer of 0-2 is preferable, 0 or 1 is more preferable, and 0 is especially preferable. From the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability and throwing properties, the monoamine compound (a2) is preferably the following The monoamine compound represented by the general formula (a2-2) or (a2-3) is more preferably a monoamine compound represented by the following general formula (a2-2). Among them, in the general formulae (a2-2) and (a2-3), R ^A4 , R ^A5 and u are the same as R ^A4 , R ^A5 and u in the general formula (a2-1), and the preferred examples are also the same.

As the monoamine compound (a2), for example: o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid Acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and other monoamine compounds with acidic substituents. Among these, m-aminophenol, p-aminophenol, p-aminobenzoic acid, and 3,5-dihydroxyaniline are preferred from the viewpoint of solubility and reactivity, and from the viewpoint of heat resistance, Preferred are o-aminophenol, m-aminophenol, and p-aminophenol, and in consideration of dielectric properties, low thermal expansion, and manufacturing cost, p-aminophenol is preferred. A monoamine compound (a2) may be used individually by 1 type, and may use 2 or more types together.

通式(a3-1)中，X ^A2表示碳數1～3的脂肪族烴基或－O－，R ^A6和R ^A7各自獨立地表示碳數1～5的烷基、鹵素原子、羥基、羧基或磺酸基，v和w各自獨立地為0～4的整數。 (Diamine Compound (a3)) The diamine compound (a3) is a diamine compound represented by the following general formula (a3-1).

In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, and a carboxyl group. or a sulfonic acid group, v and w are each independently an integer of 0-4.

As a C1-C3 aliphatic hydrocarbon group represented by X ^A2 , a methylene group, an ethylidene group, a propylene group, a propylene group, etc. are mentioned, for example. As X ^A2 , a methylene group is preferable. Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A6 and R ^A7 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl Base et al. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. V and w are preferably an integer of 0 to 2, preferably 0 or 1, more preferably 0.

Specific examples of the diamine compound (a3) include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, and 4,4'-diamine diphenylpropane, 2,2'-bis[4,4'-diaminodiphenyl]propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3 ,3'-Diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane Ethyl-4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3'-diphenyl ether Hydroxy-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro- 4,4'-Diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetramethylchloro-4 ,4'-diaminodiphenylmethane, 2,2',6,6'-tetrabromo-4,4'-diaminodiphenylmethane, etc. Among these, 4,4'-diaminodiphenylmethane and 3,3'-diethyl-4,4'-diaminodiphenylmethane are preferred from the viewpoint of low cost , 4,4'-diaminodiphenylmethane is more preferable from the viewpoint of solubility to a solvent.

The reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) is preferably carried out in the following manner: in the presence of an organic solvent, at a reaction temperature of 70 to 200° C. The reaction is allowed to proceed for 0.1 to 10 hours. The reaction temperature is preferably 70-160°C, more preferably 70-130°C, and particularly preferably 80-120°C. The reaction time is preferably 1 to 6 hours, more preferably 1 to 4 hours.

(Amounts of maleimide compound (a1), monoamine compound (a2), and diamine compound (a3) used) Maleimide compound (a1), monoamine compound (a2), and diamine compound (a3) ) in the reaction of ), the amount of the three used is preferably the sum of the equivalents of primary amine groups [represented as -NH ₂ group equivalents] possessed by the monoamine compound (a2) and the diamine compound (a3) and maleimide The relationship between the maleimide group equivalents of the compound (a1) satisfies the following formula. 0.1≦[Maleimide group equivalent]/[-NH ₂ group equivalent] sum]≦10 By setting [maleimide group equivalent]/[-NH ₂ group equivalent] to 0.1 or more, That is, gelation and heat resistance can not be reduced, and by setting [maleimide group equivalent]/[-NH ₂ group equivalent total] to 10 or less, the solubility in organic solvents can not be reduced. , Metal foil adhesion and heat resistance, it is better. From the same viewpoint, it is preferable to satisfy the following formula. 1≦[maleimide group equivalent]/[the sum of—NH ₂ group equivalent]≦9 More preferably, the following formula is satisfied. 2≦[Maleimide group equivalent]/[-NH ₂ group equivalent]≦8

(Organic solvents) As described above, the reaction of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3) is preferably carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not adversely affect the reaction. Examples include: alcohol-based solvents such as ethanol, propanol, butanol, methyl cellulose, butyl cellulose, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane Ketone-based solvents such as ketones; ether-based solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; including amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone Nitrogen-atom-containing solvents including sulfite-based solvents; sulfur-atom-containing solvents including sulfite-based solvents such as dimethyl sulfoxide; ester-based solvents such as ethyl acetate and γ-butyrolactone, and the like. Among them, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, and ester-based solvents are preferred, and from the viewpoint of low toxicity, cyclohexanone, propylene glycol monomethyl ether, methyl Cyclohexanone, γ-butyrolactone, and cyclohexanone, propylene glycol monomethyl ether, dimethyl ethyl ether, etc. are more preferable when considering high volatility, and when the prepreg is not easily retained as a residual solvent. Acetamide, particularly preferably dimethylacetamide. An organic solvent may be used individually by 1 type, and may use 2 or more types together. The amount of the organic solvent to be used is not particularly limited, but from the viewpoint of solubility and reaction efficiency, it is based on 100 parts by mass of the total of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) , it is preferable to make the usage-amount of an organic solvent into 25-1,000 mass parts, more preferably, it is 40-700 mass parts, and it is still more preferable to make the usage-amount of an organic solvent into 60-250 mass parts. Solubility is easily ensured by setting the usage amount of the organic solvent to 25 parts by mass with respect to 100 parts by mass in total of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3). , by setting the usage amount of the organic solvent to 1,000 parts by mass or less with respect to the total of 100 parts by mass of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3), it is easy to suppress The reaction efficiency is greatly reduced.

(reaction catalyst) The reaction of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3) can be carried out in the presence of a reaction catalyst as necessary. Examples of the reaction catalyst include amine-based catalysts such as triethylamine, pyridine, and tributylamine; imidazole-based catalysts such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. A reaction catalyst may be used individually by 1 type, and may use 2 or more types together. The usage-amount of a reaction catalyst is not specifically limited, Preferably it is 0.001-5 mass parts with respect to the sum total of 100 mass parts of the maleimide compound (a1) and the monoamine compound (a2).

<(B) Epoxy resin> The component (B) is an epoxy resin (hereinafter, sometimes referred to as an epoxy resin (B)), preferably an epoxy resin having at least two epoxy groups in one molecule. As an epoxy resin which has at least two epoxy groups in one molecule, a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, etc. are mentioned, for example. Among these, glycidyl ether type epoxy resins are preferred. Epoxy resin (B) can also be classified into various epoxy resins according to different main skeletons. Among the above types of epoxy resins, they can be further classified into bisphenol A type epoxy resin and bisphenol F type epoxy resin respectively. Resin, bisphenol S type epoxy resin and other bisphenol type epoxy resin; biphenyl aralkylphenol type epoxy resin; phenol novolac type epoxy resin, alkylphenol novolak type epoxy resin, cresol novolac type type epoxy resin, naphthol alkyl phenol copolyphenol novolak type epoxy resin, naphthol aralkyl cresol copolymer novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type ring Novolak type epoxy resin such as oxygen resin; stilbene type epoxy resin; epoxy resin containing triazine skeleton; epoxy resin containing stilbene skeleton; naphthalene type epoxy resin; Epoxy resin; biphenyl type epoxy resin; biphenyl aralkyl type epoxy resin; xylene type epoxy resin; alicyclic epoxy resin such as dicyclopentadiene type epoxy resin, etc. Among these, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing properties, bisphenol F type epoxy is preferred Resin, phenol novolak epoxy resin, cresol novolak epoxy resin, naphthalene epoxy resin, anthracene epoxy resin, biphenyl epoxy resin, biphenyl aralkyl epoxy resin, dicyclopentane From the viewpoint of low thermal expansion and high glass transition temperature, diene-type epoxy resins are more preferably cresol novolak-type epoxy resins, naphthalene-type epoxy resins, anthracene-type epoxy resins, and biphenyl-type epoxy resins Resin, a biphenyl aralkyl type epoxy resin, a phenol novolak type epoxy resin, and still more preferably a cresol novolak type epoxy resin. An epoxy resin (B) may be used individually by 1 type, and may use 2 or more types together.

The epoxy equivalent of the epoxy resin (B) is preferably 100-500 g/eq, preferably 120-400 g/eq, more preferably 140-300 g/eq, and particularly preferably 170-240 g/eq . Here, epoxy equivalent is the mass (g/eq) of resin per epoxy group, and can be measured according to the method prescribed|regulated by JIS K 7236 (2001). Specifically, it can be obtained by using an automatic titration device "GT-200 type" manufactured by Mitsubishi Chemical Analytech Co., Ltd., and after weighing 2 g of epoxy resin into a 200 mL beaker, dropwise added 90 mL of methyl ethyl ketone was dissolved with an ultrasonic cleaner, 10 mL of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide were added, and a 0.1 mol/L perchloric acid/acetic acid solution was added. to titrate. As a commercial product of epoxy resin (B), for example, a cresol novolak type epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Co., Ltd., epoxy equivalent: 205 to 215 g/ eq), naphthalene type epoxy resin "HP-4032" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 152 g/eq), biphenyl type epoxy resin "YX-4000" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g/eq), dicyclopentadiene-type epoxy resin "HP-7200H" (manufactured by DIC Co., Ltd., epoxy equivalent: 280 g/eq), and the like. In addition, the epoxy equivalent is the value described in the catalog of the manufacturing company of this product.

<(C) Specific copolymer resin> (C)component is a copolymer resin (henceforth may be referred to as a copolymer resin (C)) which has a structural unit derived from an aromatic vinyl compound, and a structural unit derived from maleic anhydride. As an aromatic vinyl compound, styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, etc. are mentioned, for example. Of these, styrene is preferred. As the component (C), a copolymer resin having a structural unit represented by the following general formula (C-i) and a structural unit represented by the following general formula (C-ii) is preferable.

式(C-i)中，R ^C1為氫原子或碳數1～5的烷基，R ^C2為碳數1～5的烷基、碳數2～5的烯基、碳數6～20的芳基、羥基或(甲基)丙烯醯基，x為0～3的整數，其中，當x為2或3時，複數個R ^C2可相同亦可不同。

In formula (Ci), R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , a hydroxyl group or a (meth)acryloyl group, and x is an integer of 0 to 3, wherein when x is 2 or 3, a plurality of R ^C2 may be the same or different.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^C1 and R ^C2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl Base et al. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ^C2 include an allyl group, a crotyl group, and the like. As the alkenyl group, an alkenyl group having 3 to 5 carbon atoms is preferable, and an alkenyl group having 3 or 4 carbon atoms is preferable. As a C6-C20 aryl group represented by R ^C2 , a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, etc. are mentioned, for example. As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is preferable. x is preferably 0 or 1, preferably 0. Among the structural units represented by the general formula (Ci), preferred are those represented by the following general formula (Ci-1) in which R ^C1 is a hydrogen atom and x is 0, that is, a structural unit derived from styrene.

In the copolymer resin (C), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride, that is, the structural unit derived from the aromatic vinyl compound/the structure derived from maleic anhydride The unit, in terms of molar ratio, is preferably 1-9, more preferably 2-9, more preferably 3-8, and particularly preferably 3-7. The same applies to the content ratio of the structural unit represented by the aforementioned general formula (C-i) to the structural unit represented by the aforementioned general formula (C-ii), that is, the molar ratio of (C-i)/(C-ii). The ground is preferably 1 to 9, more preferably 2 to 9, more preferably 3 to 8, and particularly preferably 3 to 7. When these molar ratios are 1 or more, preferably 2 or more, the effect of improving dielectric properties tends to be more sufficient, and when these molar ratios are 9 or less, compatibility tends to be good . In the copolymer resin (C), the total content of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride, and the structural unit represented by the general formula (C-i) and the general formula (C-ii) The total content of the indicated structural units is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably substantially 100% by mass. The weight average molecular weight (Mw) of the copolymer resin (C) is preferably 4,500-18,000, preferably 5,000-18,000, more preferably 6,000-17,000, more preferably 8,000-16,000, particularly preferably 8,000-15,000, and 9,000 to 13,000 is the best.

In addition, the method of lowering the dielectric constant of epoxy resin by using a copolymer resin of styrene and maleic anhydride, when applied to a material for printed wiring boards, impregnation of the base material and copper foil peeling strength will be reduced. Insufficient, so there is a tendency to generally avoid the above method. Therefore, there is a tendency to avoid the use of the above-mentioned copolymer resin (C), but the present invention has been completed by finding the fact that although the above-mentioned copolymer resin (C) is used, by containing the above-mentioned (A) component and (B) component, that is, a thermosetting resin composition with high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature and low thermal expansion, and excellent formability and throwing properties.

(Manufacturing method of copolymer resin (C)) The copolymer resin (C) can be produced by copolymerizing an aromatic vinyl compound and maleic anhydride. As mentioned above, as an aromatic vinyl compound, styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, etc. are mentioned, for example. These may be used individually by 1 type, and may use 2 or more types together. Furthermore, in addition to the aforementioned aromatic vinyl compound and maleic anhydride, various polymerizable components may be copolymerized. Examples of various polymerizable components include vinyl compounds such as ethylene, propylene, butadiene, isobutylene, and acrylonitrile; compounds having (meth)acryloyl groups such as methyl acrylate and methyl methacrylate. . In addition, substituents such as allyl group, methacryloyl group, acryl group, and hydroxyl group can be introduced into the aromatic vinyl compound by the following reaction: Friedel-Crafts reaction; or using lithium or the like Reaction of metal catalysts.

As a copolymer resin (C), a commercial item can also be used. As a commercial product, "SMA (registered trademark) 1000" (styrene/maleic anhydride=1, Mw=5,000), "SMA (registered trademark) EF30" (styrene/maleic anhydride=3, Mw=9,500), "SMA (registered trademark) EF40" (styrene/maleic anhydride=4, Mw=11,000), "SMA (registered trademark) EF60" (styrene/maleic anhydride=6, Mw=11,500) , "SMA (registered trademark) EF80" (styrene/maleic anhydride=8, Mw=14,400) [the above are manufactured by CRAY VALLEY Corporation], etc.

<(D) Silicon oxide treated with aminosilane-based coupling agent> In the thermosetting resin composition, although the inorganic filler is contained in order to reduce the thermal expansion coefficient of the insulating resin layer, in the present invention, silicon oxide treated with an aminosilane-based coupling agent among silicon oxides (hereinafter referred to as silicon oxide) is used. , sometimes referred to as silicon oxide (D) treated with an aminosilane-based coupling agent as the component (D). By incorporating the silicon oxide (D) treated with an aminosilane-based coupling agent into the thermosetting resin composition, in addition to the effect of improving the low thermal expansion, it is possible to achieve the same effect as the above-mentioned (A)- (C) Since the adhesiveness between components suppresses the peeling of silicon oxide, the effect of suppressing the deformation of the shape of the laser via hole due to the excess amount of desmear can also be obtained.

式(D-1)中，R ^D1為碳數1～3的烷基或碳數2～4的醯基，y為0～3的整數。 Specifically, as the aminosilane-based coupling agent, a silane coupling agent having a silicon group and an amino group represented by the following general formula (D-1) is preferable.

In formula (D-1), R ^D1 is an alkyl group having 1 to 3 carbon atoms or an acyl group having 2 to 4 carbon atoms, and y is an integer of 0 to 3.

As a C1-C3 alkyl group represented by R ^D1 , a methyl group, an ethyl group, a n-propyl group, and an isopropyl group are mentioned, for example. Among these, a methyl group is preferred. Examples of the acyl group having 2 to 4 carbon atoms represented by R ^D1 include an acetyl group, a propionyl group, and an acryl group. Among these, acetyl group is preferred.

The aminosilane-based coupling agent may have one amino group, two or more, and usually one or two amino groups. Examples of aminosilane-based coupling agents having one amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-amino Propyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, [3-(trimethoxysilyl)propyl]carbamic acid 2- Propargyl esters and the like, but are not particularly limited thereto. Examples of the aminosilane-based coupling agent having two amino groups include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl) Ethyl)-3-aminopropyltrimethoxysilane, 1-[3-(trimethoxysilyl)propyl]urea, 1-[3-(triethoxysilyl)propyl]urea, etc. , but are not particularly limited by these.

When silicon oxide (D) treated with an aminosilane-based coupling agent is used instead of silicon oxide treated with a specific coupling agent, the adhesiveness with the components (A) to (C) described above may be reduced. Reduces the tendency of silicon oxide to fall off easily, and lacks the effect of suppressing the shape deformation of laser vias caused by excess amount of desmear. The specific coupling agent is, for example, epoxy silane-based coupling agent, phenylsilane Coupling agent, alkylsilane-based coupling agent, alkenylsilane-based coupling agent, alkynylsilane-based coupling agent, haloalkylsilane-based coupling agent, siloxane-based coupling agent, hydrosilane-based coupling agent, silazane-based coupling agent Coupling agent, alkoxysilane-based coupling agent, chlorosilane-based coupling agent, (meth)acryloylsilane-based coupling agent, aminosilane-based coupling agent, isocyanuric acid-based silane-based coupling agent, ureidosilane-based coupling agent Coupling agent, mercaptosilane-based coupling agent, thioethersilane-based coupling agent, or isocyanatosilane-based coupling agent, etc. As long as the silicon oxide (D) treated with the aminosilane-based coupling agent is used, the silicon oxide treated with the other coupling agents described above may be used within a range not impairing the effects of the present invention. When silicon oxide treated with the other coupling agent mentioned above is used in combination, with respect to 100 parts by mass of silicon oxide (D) treated with the aminosilane-based coupling agent, the silicon oxide treated with the other coupling agent mentioned above is It is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, more preferably 15 parts by mass or less, particularly preferably 10 parts by mass or less, and most preferably 5 parts by mass or less.

Examples of the silicon oxide used in the silicon oxide (D) treated with an aminosilane-based coupling agent include: deposited silicon oxide prepared by a wet method and having a high water content; and, by a dry method to produce dry-process silica that contains almost no bound water, etc. The dry-process silicon oxide may further include pulverized silicon oxide, fumed silicon oxide, and fused silicon oxide (fused spherical silicon oxide) depending on the manufacturing method. The silicon oxide is preferably molten silicon oxide from the viewpoint of low thermal expansion and high fluidity when filled in resin. The average particle size of the silicon oxide is not particularly limited, and is preferably 0.1-10 μm, more preferably 0.1-6 μm, more preferably 0.1-3 μm, and particularly preferably 1-3 μm. When the average particle size of silicon oxide is 0.1 μm or more, the fluidity at high filling can be kept good, and when the average particle size of silicon oxide is 10 μm or less, the mixing probability of coarse particles can be reduced and suppressed Malfunctions due to coarse particles occur. Here, the average particle size refers to the particle size at a point corresponding to 50% of the volume when the cumulative particle size distribution curve is obtained from the particle size, taking the total volume of the particles as 100%, and can be obtained by using laser diffraction The particle size distribution measuring apparatus of the scattering method or the like is used for measurement. In addition, the specific surface area of the silicon oxide is preferably 4 cm ² /g or more, preferably 4-9 cm ² /g, more preferably 5-7 cm ² /g.

<(E) Curing Agent> The thermosetting resin composition may further contain a curing agent as a component (E) (hereinafter, sometimes referred to as a curing agent (E)). As the curing agent (E), for example, dicyandiamide, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropyl Chain aliphatic amines other than dicyandiamide, such as amine, tetramethylguanidine, triethanolamine; isophorone diamine, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, bis(4 -amino-3-methyldicyclohexyl)methane, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[ 5.5] Cyclic aliphatic amines such as undecane; aromatic amines such as xylylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenyl amine, and the like. Among these, dicyandiamide is preferable from the viewpoint of metal foil adhesion and low thermal expansion. The dicyandiamide is represented by H ₂ N—C(=NH)—NH—CN, and the melting point is usually 205 to 215° C., and the melting point of dicyandiamide with higher purity is 207 to 212° C. Dicyandiamide is a crystalline substance, which can be orthorhombic or lamellar. The purity of dicyandiamide is preferably above 98%, preferably above 99%, more preferably above 99.4%. Commercially available dicyandiamide can be used, and for example, commercially available products such as Nippon Carbide Co., Ltd., Tokyo Chemical Industry Co., Ltd., Kishida Chemical Co., Ltd., and Nacalai Tesque Co., Ltd. can be used.

<(F) Flame Retardant> The thermosetting resin composition of the present invention may further contain a flame retardant as the component (F) (hereinafter, sometimes referred to as a flame retardant (F)). Here, dicyandiamide and the like among the above-mentioned curing agents also have the effect of a flame retardant, but in the present invention, a substance capable of producing the function of a curing agent is classified as a curing agent, and it is not included in ( F) in the ingredients. Examples of the flame retardant include halogen-containing flame retardants containing bromine and chlorine; phosphorus-based flame retardants; nitrogen-based flame retardants such as guanidine sulfonate, melamine sulfate, melamine polyphosphate, and melamine cyanurate. ; Phosphazene flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame retardants such as antimony trioxide. Among these, phosphorus-based flame retardants are preferred. As the phosphorus-based flame retardant, there are inorganic phosphorus-based flame retardants and organic phosphorus-based flame retardants. Examples of inorganic phosphorus-based flame retardants include ammonium phosphates such as red phosphorus, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphamide; phosphoric acid; Phosphine oxide, etc. Examples of organic phosphorus-based flame retardants include aromatic phosphoric acid esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic Organic phosphorus compounds, phosphorus-containing phenol resins, etc. Among these, aromatic phosphoric acid esters and metal salts of disubstituted phosphinic acids are preferred. Here, as the metal salt, any one of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, and zinc salt is preferable, and aluminum salt is more preferable. Among the organic phosphorus-based flame retardants, aromatic phosphates are preferred.

Examples of aromatic phosphoric acid esters include triphenyl phosphate, tricresyl phosphate, tris(xylyl phosphate), cresyl diphenyl phosphate, bis(2,6-xylyl phosphate), m-cresyl phosphate, and Hydroquinone bis(diphenyl phosphate), 1,3-phenylene bis(bis(2,6-xylylene) phosphate), bisphenol A bis(diphenyl phosphate), 1,3-phenylene phenylene base bis (diphenyl phosphate), etc. As a monosubstituted phosphonic acid diester, divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl phenylphosphonate), etc. are mentioned, for example. As a disubstituted phosphinate, phenyl diphenylphosphinate, methyl diphenylphosphinate, etc. are mentioned, for example. Examples of the metal salt of disubstituted phosphinic acid include metal salts of dialkylphosphinic acid, metal salts of diallylphosphinic acid, metal salts of divinylphosphinic acid, and diarylphosphines. Acid metal salts, etc. These metal salts are as described above, preferably any of lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts. Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis(2-allylphenoxy)phosphazene and xylylphosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, honey polyphosphate White amine, etc. Examples of the cyclic organic phosphorus compound include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Among these, at least one selected from aromatic phosphoric acid esters, metal salts of disubstituted phosphinic acids, and cyclic organic phosphorus compounds is preferred, and aromatic phosphoric acid esters are more preferred.

Further, the aromatic phosphoric acid ester is preferably an aromatic phosphoric acid ester represented by the following general formula (F-1) or (F-2), and the metal salt of the disubstituted phosphinic acid is preferably the following A metal salt of a disubstituted phosphinic acid represented by the general formula (F-3).

In formulas (F-1) to (F-3), R ^F1 to R ^F5 are each independently an alkyl group with 1 to 5 carbon atoms or a halogen atom; e and F are each independently an integer of 0 to 5, g, h and i are each independently an integer of 0 to 4. R ^F6 and R ^F7 are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 14 carbon atoms; M is a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom, Zinc atom; j is an integer of 1-4.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^F1 to R ^F5 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl Base et al. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. As a halogen atom represented by R ^F1 - R ^F5 , a fluorine atom etc. are mentioned, for example. E and f are preferably an integer of 0 to 2, more preferably 2. g, h and i are preferably an integer of 0 to 2, preferably 0 or 1, more preferably 0. Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^F6 and R ^F7 include the same groups as in the case of R ^F1 to R ^F5 . As a C6-C14 aryl group represented by R ^F6 and R ^F7 , a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, etc. are mentioned, for example. The aromatic hydrocarbon group is preferably an aryl group having 6 to 10 carbon atoms. j is equal to the valence of the metal ion, that is, it varies in the range of 1 to 4 according to the type of M. M is preferably an aluminum atom. Furthermore, when M is an aluminum atom, j is 3.

(content of each ingredient) In the thermosetting resin composition, the content of the components (A) to (D) is not particularly limited, but is preferably 15 to 100 parts by mass of the total of the components (A) to (C). 65 mass parts, (B) component is 15-50 mass parts, (C) component is 10-45 mass parts, (D) component is 30-70 mass parts. High heat resistance, low relative permittivity, high glass transition temperature, and low thermal expansion can be obtained by containing 15 parts by mass or more of component (A) relative to 100 parts by mass of the total of components (A) to (C). Propensity. On the other hand, when the (A) component is 65 parts by mass or less with respect to 100 parts by mass of the total of the components (A) to (C), the flowability and moldability of the thermosetting resin composition tend to be good. When the (B) component is 15 parts by mass or more with respect to 100 parts by mass of the total of the (A) to (C) components, high heat resistance, high glass transition temperature, and low thermal expansion tend to be obtained. On the other hand, when the (B) component is 50 parts by mass or less with respect to 100 parts by mass of the total of the components (A) to (C), high heat resistance, low relative permittivity, and high glass transition temperature may occur. and the tendency for low thermal expansion. When the (C) component is 10 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), high heat resistance and low relative permittivity tend to be obtained. On the other hand, when the component (C) is 45 parts by mass or less with respect to 100 parts by mass of the total of the components (A) to (C), high heat resistance, high metal foil adhesion, and low thermal expansion can be obtained. tendency. When the (D) component is 30 parts by mass or more with respect to 100 parts by mass of the total of the (A) to (C) components, there is a tendency that excellent low thermal expansion properties can be obtained. On the other hand, when the component (D) is 70 parts by mass or less with respect to 100 parts by mass of the total of the components (A) to (C), heat resistance can be obtained and the fluidity and molding of the thermosetting resin composition can be obtained. good sex tendency.

Further, when the thermosetting resin composition of the present invention contains the component (E), the content is preferably 0.5 to 6 parts by mass relative to 100 parts by mass of the total of the components (A) to (C). When the (E) component is 0.5 parts by mass or more relative to 100 parts by mass of the total of the components (A) to (C), high metal foil adhesion and excellent low thermal expansion tend to be obtained. On the other hand, when (E) component is 6 mass parts or less with respect to the sum total of 100 mass parts of (A)-(C) components, there exists a tendency for high heat resistance to be acquired.

In addition, when the thermosetting resin composition of the present invention contains the component (F), from the viewpoint of flame retardancy, it is preferable that the amount of the component (A) to (C) in total is 100 parts by mass. The content is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass. In particular, when a phosphorus-based flame retardant is used as the component (F), from the viewpoint of flame retardancy, it is preferable that phosphorus is used in an amount of 100 parts by mass relative to the total of the components (A) to (C). The atomic content is preferably 0.1 to 3 parts by mass, preferably 0.2 to 3 parts by mass, and more preferably 0.5 to 3 parts by mass.

(other ingredients) The thermosetting resin composition of this invention can contain other components, such as an additive and an organic solvent, as needed in the range which does not impair the effect of this invention.

(additive) Examples of additives include curing accelerators, colorants, antioxidants, reducing agents, ultraviolet absorbers, optical brighteners, adhesion improvers, organic fillers, and the like. These may be used individually by 1 type, and may use 2 or more types together.

(Organic solvents) The thermosetting resin composition may contain an organic solvent from the viewpoint of being easy to handle by dilution, and from the viewpoint of easy production of a prepreg to be described later. In this specification, the thermosetting resin composition containing an organic solvent may be called resin varnish. The organic solvent is not particularly limited, and examples thereof include methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, and triethylene glycol monomethyl ether. , triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether and other alcohol solvents; acetone, methyl ethyl ether ketone-based solvents such as methyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and trimethylbenzene; including formamide, N-methylformamide, Nitrogen-containing solvents including amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; Sulfur atom-containing solvents including sulfite-based solvents; ester-based solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, and the like. Among these, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, and nitrogen-atom-containing solvents are preferred, and methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl ethyl ketone, methyl ethyl ketone, methyl Cellulose and propylene glycol monomethyl ether, methyl ethyl ketone and methyl isobutyl ketone are more preferred, and methyl ethyl ketone is particularly preferred. An organic solvent may be used individually by 1 type, and may use 2 or more types together. In the thermosetting resin composition, the content of the organic solvent may be appropriately adjusted to the extent that the thermosetting resin composition can be easily handled, and as long as the coating properties of the resin varnish are in a good range, there is no content. It is particularly limited, and the solid content concentration (the concentration of components other than the organic solvent) derived from the thermosetting resin composition is preferably 30 to 90 mass %, more preferably 40 to 80 mass %, and still more preferably 50 to 80% by mass.

[prepreg] The prepreg of the present invention contains the above-mentioned thermosetting resin composition, and its production method is not particularly limited, and can be produced by, for example, impregnating or coating a sheet-like reinforcing base material and heating or the like. It is semi-hardened (B-staged). As the sheet-like reinforcing base material of the prepreg, a conventional one used for a laminate for various electrical insulating materials can be used. Examples of the material of the sheet-like reinforcing substrate include natural fibers such as paper and cotton linters; inorganic fibers such as glass fibers and asbestos; aramid, polyimide, polyvinyl alcohol, polyester, and tetrafluoroethylene. and acrylic and other organic fibers; mixtures of these, etc. Among these, from the viewpoint of flame retardancy, glass fiber is preferable. As the glass fiber substrate, for example, a woven cloth obtained by using E glass, C glass, D glass, S glass, etc., or a glass fiber cloth obtained by bonding short fibers with an organic binder; Substrates made of mixed cellulose fibers, etc. The glass woven fabric obtained by using E glass is preferable. These sheet-like reinforcing substrates have, for example, woven fabrics, non-woven fabrics, yarn bundles, strand mats, or surface mats. In addition, the material and shape are selected according to the intended use and performance of the molded product, and one type may be used alone, or two or more types of materials and shapes may be combined as required.

As a method of impregnating or applying the thermosetting resin composition to a sheet-like reinforcing substrate, the following hot melt method or solvent method is preferable. The hot-melt method is a method of (1) temporarily coating a coated paper with good releasability from the composition, and then laminating it on a sheet without containing an organic solvent in the thermosetting resin composition. Reinforcing the substrate, or (2) directly coating the sheet-like reinforcing substrate using a die coater. On the other hand, the solvent method is a method of preparing a varnish by containing an organic solvent in a thermosetting resin composition, immersing a sheet-like reinforcing substrate in the varnish, impregnating the varnish in the sheet-like reinforcing substrate, and then Let it dry.

The thickness of the sheet-like reinforcing substrate is not particularly limited, for example, about 0.03 to 0.5 mm can be used. From the viewpoints of heat resistance, moisture resistance, and workability, a substrate surface-treated with a silane coupling agent or the like is preferred. , or a substrate subjected to mechanical fiber opening treatment. The prepreg of the present invention can be obtained by impregnating or applying the thermosetting resin composition on a substrate, and then preferably heating and drying it at a temperature of 100 to 200° C. for 1 to 30 minutes. Semi-hardened (B-staged). The obtained prepreg is used by using one sheet or by stacking 2 to 20 sheets according to needs.

[laminated board] The laminated board of this invention contains the said prepreg. It can be produced by, for example, using one sheet of the prepreg or stacking 2 to 20 sheets of the prepreg as needed, and arranging metal foil on one or both sides of the prepreg, laminating and laminating. shape. In addition, the laminated board in which the metal foil is arrange|positioned may be called a metal-clad laminated board. The metal of the metal foil is not particularly limited as long as it is a metal used for an electrical insulating material. From the viewpoint of electrical conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, Aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements is preferred, copper and aluminum are more preferred, and copper is more preferred. As the forming conditions of the laminate, conventional forming methods of laminates and multilayer boards for electrical insulating materials can be applied. 250°C, pressure 0.2 to 10 MPa, and heating time 0.1 to 5 hours for molding. In addition, the prepreg of the present invention and the printed wiring board for inner layers can be combined, laminated and molded to produce a multilayer board. The thickness of the metal foil is not particularly limited, and can be appropriately selected in accordance with the use of the printed wiring board and the like. The thickness of the metal foil is preferably 0.5 to 150 μm, preferably 1 to 100 μm, more preferably 5 to 50 μm, and particularly preferably 5 to 30 μm.

Furthermore, it is also preferable to form a plating layer by plating a metal foil. The metal of the plating layer is not particularly limited as long as it can be used for plating. The metal of the coating layer is preferably selected from the group consisting of copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and at least one of these metal elements. an alloy. The plating method is not particularly limited, and conventional methods such as electrolytic plating and electroless plating can be used.

[Printed Wiring Board] The present invention also provides a printed wiring board comprising the prepreg or the laminate. The printed wiring board of the present invention can be produced by subjecting the metal foil of the metal-clad laminate to circuit processing. Circuit processing can be carried out by the following methods, for example: after forming a resist pattern on the surface of the metal foil, remove the excess part of the metal foil by etching, peel off the resist pattern, and use a drill to form the desired pattern. After the through hole is formed and the resist pattern is formed again, the through hole is subjected to plating for conduction, and finally the resist pattern is peeled off. The above-mentioned metal-clad laminate can be further laminated on the surface of the printed wiring board obtained as described above under the same conditions as described above, and further circuit processing can be performed in the same manner as above to produce a multilayer printed wiring board. At this time, it is not necessary to form a through hole, and a via hole (via hole) may be formed, and both of these can be formed. Such multi-layering is the number of sheets required to perform. [Example]

Next, the present invention is described in more detail by the following examples, but these examples are not intended to limit the present invention in any sense. A prepreg and a copper clad laminate were produced using the thermosetting resin composition of the present invention, and the produced copper clad laminate was evaluated. The evaluation method is as follows.

[assessment method] <1. Heat resistance (reflow heat resistance)> Using the four-layer copper clad laminate obtained in each example, and setting the maximum temperature at 266°C, the four-layer copper-clad laminate was allowed to flow in a constant temperature bath environment of 260°C or higher for 30 seconds to set one cycle, and the number of cycles until the expansion of the substrate can be visually confirmed was obtained. The higher the number of cycles, the better the heat resistance.

<2. Relative permittivity (Dk)> Using a network analyzer "8722C" (manufactured by HP), the relative permittivity of a 1 GHz double-sided copper-clad laminate was measured by a three-plate structure linear line resonator method. The size of the test piece is 200 mm × 50 mm × thickness 0.8 mm, and a straight line (line length 200 mm) with a width of 1.0 mm is formed in the center of one side of a double-sided copper-clad laminate by etching, and copper remains The whole back surface is set as a cladding layer. For another double-sided copper-clad laminate, the entire one-sided surface was etched, and the back surface was set as a cladding layer. These two double-sided copper-clad laminates were superimposed so that the cladding layer was outside, and a strip line was produced. Measurements are performed at 25°C. The smaller the relative permittivity, the better.

<3. Metal foil adhesion (copper foil peel strength)> Metal foil adhesion was evaluated by copper foil peel strength. An evaluation board was produced by immersing the double-sided copper-clad laminate obtained in each example in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.) to form a copper foil with a width of 3 mm. , and used the autoclave "AG-100C" (manufactured by Shimadzu Corporation) to measure the peel strength of the copper foil. The larger the numerical value is, the more excellent the metal foil adhesiveness is.

<4. Glass transition temperature (Tg)> By immersing the double-sided copper-clad laminate obtained in each example in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.), the copper foil was removed, and an evaluation of 5 mm square was produced. The substrate was used to observe and evaluate the thermal expansion characteristics of the substrate in the plane direction (Z direction) at 30 to 260°C using a thermomechanical analysis (TMA) test apparatus "Q400EM" (manufactured by TA instruments), and the inverse inflection point of the amount of expansion was calculated. Set to glass transition temperature.

<5. Low thermal expansion> The copper foil was removed by immersing the double-sided copper-clad laminate obtained in each example in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.), Then, an evaluation substrate of 5 mm square was produced, and the thermal expansion coefficient (linear expansion coefficient) in the plane direction of the evaluation substrate was measured using a TMA test apparatus "Q400EM" (manufactured by TA instruments). Furthermore, in order to remove the influence of thermal distortion of the sample, after repeating the heating-cooling cycle twice, the thermal expansion coefficient [ppm/°C] of 30°C to 260°C in the temperature shift chart for the second time was measured and calculated. Set as an index of low thermal expansion. The smaller the numerical value, the more excellent the low thermal expansion property. In addition, in the table|surface, the thermal expansion coefficient below Tg (indicated as "<Tg") and the thermal expansion coefficient over Tg (indicated as ">Tg") are separately described. Measurement conditions ^1st Run: room temperature → 210°C (heating rate 10°C/min) ^2nd Run: 0→270°C (heating rate 10°C/min) Copper clad laminates are expected to be further thinned, and this is also expected On the other hand, the thinning of the prepreg constituting the copper-clad laminate is being studied. Since the thinned prepreg tends to warp, it is desirable that the warpage of the prepreg during heat treatment is small. In order to reduce warpage, it is effective to make the thermal expansion coefficient of the base material in the plane direction small.

<6. Throwing property (laser workability)> For the four-layer copper-clad laminates obtained in each example, a laser machine "LC-2F21B/2C" (manufactured by Hitachi Via Mechanics Co., Ltd.) was used. Laser drilling was performed by the copper direct method with a target aperture of 80 μm, Gaussian, and cyclic mode, pulse width of 15 μs×1 time, and 7 μs×4 times. For the obtained laser holed substrate, a swelling liquid "Swelling Dip Securiganth P" (manufactured by Atotech Japan Co., Ltd.) was used at 70°C for 5 minutes, and a roughening liquid "Dosing" was used at 70°C for 9 minutes. Securiganth P500J" (manufactured by Atotech Japan Co., Ltd.) was subjected to desmear treatment using a neutralizing solution "Reduction Conditioner Securiganth P500" (manufactured by Atotech Japan Co., Ltd.) at 40°C for 5 minutes. Then, the electroless plating solution "Puriganto MSK-DK" (manufactured by Atotech Japan Co., Ltd.) was used for 20 minutes at 30°C, and the plating solution "Cupracid HL" (Atotech Japan Co., Ltd.) was used at 24°C and 2 A/dm ² Co., Ltd.) for 2 hours to perform plating on the laser-processed substrate. Cross-sectional observation of the obtained laser holed substrate was carried out, and the throwing property was confirmed. As a method for evaluating the leveling property, when the difference between the thickness of the coating on the upper part of the laser hole and the thickness of the coating on the bottom of the laser hole is within 10% of the thickness of the coating on the upper part of the laser hole, the leveling property is better. , and the presence ratio (%) of pores contained in this range in 100 pores was obtained.

<7. Formability> For the four-layer copper-clad laminates obtained in each example, after removing the outer layer copper, the presence or absence of holes and scratches in a 340×500 mm plane was visually checked and used as an index of formability. The absence of holes and scratches shows good formability.

Hereinafter, each component used in an Example and a comparative example is demonstrated.

(A) component: The solution of the maleimide compound (A) produced in the following production example 1 was used. [Production Example 1] In a reaction vessel with a volume of 1 L equipped with a thermometer, a stirring device, and a moisture metering device equipped with a reflux cooling tube, 19.2 g of 4,4'-diaminodiphenylmethane, bis(4-maleimide) were added. phenyl)methane 174.0 g, p-aminophenol 6.6 g, and dimethylacetamide 330.0 g, and reacted at 100° C. for 2 hours to obtain an acidic substituent and N-substituted maleimide The dimethylacetamide solution of the maleimide compound (A) (Mw=1,370) of the base was used as the (A) component. In addition, the said weight average molecular weight (Mw) was converted from the calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is using standard polystyrene: TSK standard POLYSTYRENE (Model: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [Tosoh Co., Ltd.] is approximated by a cubic equation. The conditions of GPC are as follows. Device: (Pump: Model L-6200 [manufactured by Hitachi High-Technologies Co., Ltd.]), (Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Co., Ltd.]), (Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Co., Ltd.]) Column: TSKgel SuperHZ2000 + TSKgel SuperHZ2300 (both are manufactured by Tosoh Corporation) String size: 6.0×40 mm (protection string), 7.8×300 mm (string) Elution solution: tetrahydrofuran Sample concentration: 20 mg/5 mL Injection volume: 10 μL Flow: 0.5 mL/min Measurement temperature: 40℃

(B) Component: Cresol novolak type epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Co., Ltd.) (C-1) Component: "SMA (registered trademark) EF40" (styrene/maleic anhydride=4, Mw=11,000, manufactured by CRAY VALEY Corporation) (C-2) Component: "SMA (registered trademark) 3000" (styrene/maleic anhydride=2, Mw=7,500, manufactured by CRAY VALEY) (C-3) Component: "SMA (registered trademark) EF80" (styrene/maleic anhydride=8, Mw=14,400, manufactured by CRAY VALEY) (C-4) Component: "SMA (registered trademark) 1000" (styrene/maleic anhydride=1, Mw=5,000, manufactured by CRAY VALEY)

(D) Component: "Megasil 525 ARI" (fused silica treated with an aminosilane-based coupling agent, average particle size: 1.9 μm, specific surface area 5.8 m ² /g, manufactured by Sibelco Japan Co., Ltd.) Inorganic filler Material: "F05-30" (untreated pulverized silica, average particle size: 4.2 μm, specific surface area 5.8 m ² /g, manufactured by Fukushima Kiln Co., Ltd.)

(E) Component: Dicyandiamide (manufactured by Nippon Carbide Industrial Co., Ltd.) (F) Component: "PX-200" (aromatic phosphate ester (refer to the following structural formula), manufactured by Daihachi Chemical Industry Co., Ltd.)

[Examples 1 to 13, Comparative Example 1] As shown in Tables 1 to 4 below, each component shown above (wherein, in the case of a solution, represents the amount in terms of solid content) was prepared such that the nonvolatile content of the solution Methyl ethyl ketone was additionally added so that it might become 65-75 mass %, and the thermosetting resin composition of each Example and each comparative example was prepared. Each of the obtained thermosetting resin compositions was impregnated into a glass cloth (0.1 mm) of IPC specification #3313, and dried at 160° C. for 4 minutes to obtain a prepreg. After 8 sheets of this prepreg were stacked, 18 μm copper foil “3EC-VLP-18” (manufactured by Mitsui Metals Co., Ltd.) was stacked on both sides, and the prepreg was heated at a temperature of 190° C. and a pressure of 25 kgf/cm ² ( 2.45 MPa) heating and pressing for 90 minutes, and after making a double-sided copper-clad laminate with a thickness of 0.8 mm (8 pieces of prepreg), the copper-clad laminate was used to measure and evaluate the relative dielectric according to the aforementioned method. constant, metal foil adhesion, glass transition temperature (Tg) and low thermal expansion. On the other hand, using one sheet of the aforementioned prepreg, a 18 μm copper foil “YGP-18” (manufactured by Nippon Electron Co., Ltd.) was superimposed on both sides, and the prepreg was heated at a temperature of 190° C. and a pressure of 25 kgf/cm ² ( 2.45 MPa) heat and pressure molding for 90 minutes, and after making a double-sided copper clad laminate with a thickness of 0.1 mm (1 prepreg), the inner layer adhesion treatment (using "BF treatment liquid") is performed on both copper foil surfaces. (manufactured by Hitachi Chemical Co., Ltd.), 18 μm copper foil “YGP-18” (manufactured by Nippon Electron Co., Ltd.) was stacked on both sides of the prepreg with a thickness of 0.05 mm one at a time. , and heated and pressed for 90 minutes at a temperature of 190° C. and a pressure of 25 kgf/cm ² (2.45 MPa) to produce a four-layer copper-clad laminate. Using this four-layer copper-clad laminate, the evaluation of heat resistance, throwing property, and formability was carried out according to the aforementioned method. The results are shown in Tables 1-4.

[Table 1] unit Example 1 2 3 4 5 Element (A) Ingredient parts by mass 45 65 15 40 30 (B) Ingredient parts by mass 30 20 50 25 50 (C-1) Ingredients parts by mass 25 15 30 35 20 (C-2) Ingredient parts by mass - - - - - (C-3) Ingredients parts by mass - - - - - (C-4) Ingredients parts by mass - - - - - (D) Ingredient parts by mass 50 70 30 40 60 Inorganic filler material parts by mass - - - - - (E) Ingredient parts by mass 2 2 2 2 2 (F) Flame Retardant ^{* 1} parts by mass 2.0 2.0 2.0 2.0 2.0 evaluation result 1. Heat resistance number of cycles ≧10 ≧10 ≧10 ≧10 ≧10 2. Relative permittivity (1 GHz) - 3.8 3.8 3.9 3.8 3.8 3. Metal foil adhesion kN/m 1.1 1.1 1.2 1.1 1.2 4. Glass transition temperature °C 157 161 155 160 158 5. Thermal expansion coefficient <Tg ppm/℃ 42 34 48 43 46 >Tg ppm/℃ 211 202 217 215 208 6. Throwing property % 86 87 84 83 85 7. Formability - nothing unusual nothing unusual nothing unusual nothing unusual nothing unusual *1: Phosphorus atom equivalent

[Table 2] unit Example 6 7 8 9 10 Element (A) Ingredient parts by mass 55 45 30 60 45 (B) Ingredient parts by mass 15 45 30 20 30 (C-1) Ingredients parts by mass 30 10 40 20 25 (C-2) Ingredient parts by mass - - - - - (C-3) Ingredients parts by mass - - - - - (C-4) Ingredients parts by mass - - - - - (D) Ingredient parts by mass 50 50 50 50 50 Inorganic filler material parts by mass - - - - - (E) Ingredient parts by mass 2 2 2 0.5 5 (F) Flame Retardant ^{* 1} parts by mass 2.0 2.0 2.0 2.0 2.0 evaluation result 1. Heat resistance number of cycles ≧10 ≧10 ≧10 ≧10 ≧10 2. Relative permittivity (1 GHz) - 3.8 3.9 3.8 3.8 3.8 3. Metal foil adhesion kN/m 1.1 1.1 1.1 1.1 1.2 4. Glass transition temperature °C 160 156 155 160 158 5. Thermal expansion coefficient <Tg ppm/℃ 48 42 48 44 45 >Tg ppm/℃ 210 211 212 210 206 6. Throwing property % 83 86 85 83 85 7. Formability - nothing unusual nothing unusual nothing unusual nothing unusual nothing unusual *1: Phosphorus atom equivalent

[table 3] unit Example 11 12 13 Element (A) Ingredient parts by mass 45 45 45 (B) Ingredient parts by mass 30 30 30 (C-1) Ingredients parts by mass - - - (C-2) Ingredient parts by mass 25 - - (C-3) Ingredients parts by mass - 25 - (C-4) Ingredients parts by mass - - 25 (D) Ingredient parts by mass 50 50 50 Inorganic filler material parts by mass - - - (E) Ingredient parts by mass 2 2 2 (F) Flame Retardant ^{* 1} parts by mass 2.0 2.0 2.0 evaluation result 1. Heat resistance number of cycles ≧10 ≧10 ≧10 2. Relative permittivity (1 GHz) - 3.9 3.8 4.0 3. Metal foil adhesion kN/m 1.1 1.0 1.1 4. Glass transition temperature °C 160 161 160 5. Thermal expansion coefficient <Tg ppm/℃ 44 43 44 >Tg ppm/℃ 209 211 215 6. Throwing property % 81 82 88 7. Formability - nothing unusual nothing unusual nothing unusual *1: Phosphorus atom equivalent

[Table 4] unit Comparative example 1 Element (A) Ingredient parts by mass 40 (B) Ingredient parts by mass 30 (C-1) Ingredients parts by mass 30 (C-2) Ingredient parts by mass - (C-3) Ingredients parts by mass - (C-4) Ingredients parts by mass - (D) Ingredient parts by mass - Inorganic filler material parts by mass 50 (E) Ingredient parts by mass 2 (F) Flame Retardant ^{* 1} parts by mass 2.0 evaluation result 1. Heat resistance number of cycles ≧10 2. Relative permittivity (1 GHz) - 3.8 3. Metal foil adhesion kN/m 1.1 4. Glass transition temperature °C 156 5. Thermal expansion coefficient <Tg ppm/℃ 48 >Tg ppm/℃ 210 6. Throwing property % 57 7. Formability - nothing unusual *1: Phosphorus atom equivalent

In the embodiment, the reflow heat resistance reached more than 10 cycles above the heat resistance requirement level, and obtained low relative permittivity, high metal foil adhesion and high glass transition temperature, and exhibited low thermal expansion. In addition, since the glass cloth protruded from the wall surface and had a moderately roughened shape, it was confirmed that it had good throwing properties. In terms of formability, the embedding property of the resin was also good, and abnormalities such as scratches and holes could not be confirmed. Among these, compared with Examples 11 to 13, in Examples 1 to 10, the relative permittivity and metal foil adhesion were more favorable, and other characteristics were also stably exhibited. On the other hand, in Comparative Example 1, silicon oxide that has not been treated with an aminosilane-based coupling agent was used as the inorganic filler, but there were irregularities and glass cloths that became the wall surface of the laser hole due to an increase in the dissolving amount of desmear slag. The tendency of protruding larger hole shape, so that throwing property is greatly reduced. [Industrial Availability]

The prepreg of the present invention and the laminate comprising the prepreg have high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature and low thermal expansion, as well as formability and throwing properties. Since it is excellent, it is more suitable for use as a printed wiring board for electronic equipment.

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Claims (13)

A prepreg comprising a thermosetting resin composition containing: (A) maleimide compound; (B) epoxy resin; (C) a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride; and, (D) Silicon oxide treated with an aminosilane-based coupling agent. The prepreg according to claim 1, wherein the component (A) is a maleimide compound having an N-substituted maleimide group. The lyimide compound is a maleimide compound having (a1) at least two N-substituted maleimide groups in one molecule, and (a2) a monomolecular compound represented by the following general formula (a2-1). The amine compound and (a3) are obtained by reacting the diamine compound represented by the following general formula (a3-1);

In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is an integer of 1 to 5 , u is an integer from 0 to 4 and satisfies 1≦t+u≦5, where, when t is an integer from 2 to 5, a plurality of R ^A4 can be the same or different, and when u is an integer from 2 to 4, A plurality of R ^A5 can be the same or different;

In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, and a carboxyl group. or a sulfonic acid group, v and w are each independently an integer of 0-4. The prepreg according to claim 1 or 2, wherein the component (C) is a copolymer resin having a structural unit represented by the following general formula (Ci) and a structural unit represented by the following general formula (C-ii) ) represents the structural unit:

In formula (Ci), R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , a hydroxyl group or a (meth)acryloyl group, and x is an integer of 0 to 3, wherein when x is 2 or 3, a plurality of R ^C2 may be the same or different. The prepreg according to claim 3, wherein, in the general formula (Ci), R ^C1 is a hydrogen atom and x is 0. The prepreg according to claim 1 or 2, wherein, in the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride is that the content ratio of the structural unit derived from an aromatic The structural unit of the vinyl group compound/the structural unit derived from maleic anhydride is 2 to 9 in molar ratio. The prepreg according to claim 1 or 2, wherein, in the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride is that the content ratio of the structural unit derived from an aromatic The structural unit of the vinyl group compound/the structural unit derived from maleic anhydride is 3 to 7 in molar ratio. The prepreg according to any one of claims 1 to 6, wherein the weight average molecular weight of the component (C) is 4,500 to 18,000. The prepreg according to any one of claims 1 to 7, wherein the weight average molecular weight of the component (C) is 9,000 to 13,000. The prepreg according to any one of claims 1 to 8, wherein the component (B) is bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, Naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin or dicyclopentadiene type epoxy resin. The prepreg according to any one of claims 1 to 9, wherein the thermosetting resin composition further contains (E) a curing agent. The prepreg according to any one of claims 1 to 10, wherein the thermosetting resin composition further contains (F) a flame retardant. A laminate comprising the prepreg described in any one of claims 1 to 11 and a metal foil. A printed wiring board comprising the prepreg described in any one of claims 1 to 11 or the laminate described in claim 12.