TW202012481A - Resin composition, prepreg, metal foil-clad laminated plate, resin sheet, and printed-wiring board - Google Patents

Abstract

Provided are: a resin composition that is capable of achieving a high peel strength and a low melt viscosity while maintaining a low dielectric constant (Dk) and a low dielectric tangent (Df); and a prepreg, a metal foil-clad laminated plate, a resin sheet, and a printed-wiring board. This resin composition comprises: (A) a compound having two or more aromatic ring structures per molecule and a group represented by -Si(OR01)m(R02)3-m; (B) at least one type selected from resins having an aromatic ring structure and elastomers having an aromatic ring structure; and (C) a filler, wherein R01 and R0 2 each independently represent a hydrocarbon group, and m is an integer of 1-3.

Description

Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board

The present invention relates to a resin composition, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board.

In recent years, the high integration and miniaturization of semiconductors used in electronic equipment, communication equipment, personal computers, etc. have accelerated. Along with this, various characteristics required for the laminated board for semiconductor packages used in printed wiring boards (for example, metal-clad laminated boards, etc.) have become more stringent. The required characteristics include, for example, low dielectric constant, low dielectric loss factor, low thermal expansion, and heat resistance. Among them, if it is an insulator material with a large dielectric constant and a dielectric loss factor, the electrical signal will be attenuated and the reliability is impaired, so a material with a small dielectric constant and a dielectric loss factor is required.

In order to obtain printed wiring boards that improve these various characteristics, some people have discussed the use of materials that are used as materials for printed wiring boards. For example, Patent Documents 1 and 2 disclose vinyl compounds having low dielectric constants and dielectric loss factors.

(式中，X表示含有聚苯醚結構之n價有機基，R¹ 各自獨立地表示無取代或經取代之碳原子數1～10之烷基、或者無取代或經取代之碳原子數6～10之芳基，R² 各自獨立地表示無取代或經取代之碳原子數1～10之烷基、或者無取代或經取代之碳原子數6～10之芳基，A¹ 表示單鍵或含雜原子之2價連結基，A² 表示不含雜原子之無取代或經取代之碳原子數1～20之2價烴基，m為1～3之數，n為1～10之數。) [先前技術文獻] [專利文獻]On the other hand, Patent Document 3 discloses an organosilicon compound (silane coupling agent) that provides a hardened product that can exhibit good dielectric properties such as copper foil adhesion, dielectric constant, and dielectric loss factor. The characteristic is an organosilicon compound represented by the average structural formula (i). [Chemical 1]

(In the formula, X represents an n-valent organic group containing a polyphenylene ether structure, and R ¹ each independently represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted carbon atom having 6 carbon atoms. ～10 aryl groups, R ² each independently represents an unsubstituted or substituted C 1-10 alkyl group, or an unsubstituted or substituted C 6-10 aryl group, A ¹ represents a single bond Or a divalent linking group containing a heteroatom, A ² represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms without a heteroatom, m is a number of 1 to 3, and n is a number of 1 to 10 .) [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-59644 [Patent Document 2] Japanese Patent Laid-Open No. 2006-83364 [Patent Document 3] Japanese Patent Application Publication No. 2018-16709

[Problems to be solved by the invention]

As mentioned above, there have been various discussions on materials used for electronic materials such as printed wiring boards. However, with the development of technology in recent years, more novel materials are needed. In particular, there is a need for materials that can maintain a low dielectric constant (Dk) and a low dielectric loss factor (Df) while achieving high peel strength and excellent manufacturability, that is, low melt viscosity. The present invention aims to solve this problem, and aims to provide a resin composition capable of maintaining low dielectric constant (Dk) and low dielectric loss factor (Df) while achieving high peel strength and low melt viscosity, and prepreg Body, metal-clad laminate, resin sheet and printed wiring board. [Means to solve the problem]

(X) 式(X)中，X表示包含聚苯醚結構之n價之有機基，R¹ 及R² 各自獨立地表示碳原子數1～10之烷基或碳原子數6～10之芳基，A¹ 表示單鍵或含有雜原子之2價之連結基，A² 表示單鍵或2價之連結基，m係1～3之整數，n係1～10之數。 >5>如>1>記載之樹脂組成物，其中，該化合物(A)包含式(Y)表示之化合物； 式(Y) [化3]

(Y) 式(Y)中，A² 係單鍵或2價之連結基，R¹ 及R² 各自獨立地表示碳原子數1～10之烷基或碳原子數6～10之芳基，m係1～3之整數，n係1～10之數。 >6>如>1>～>5>中任一項記載之樹脂組成物，其中，該化合物(A)之重量平均分子量為1000以上。 >7>如>1>～>6>中任一項記載之樹脂組成物，其中，該具有芳香環結構之彈性體包含苯乙烯系彈性體。 >8>如>1>～>7>中任一項記載之樹脂組成物，其中，該具有芳香環結構之樹脂包含聚苯醚化合物。 >9>如>8>記載之樹脂組成物，其中，該聚苯醚化合物包含下式(1)表示之聚苯醚化合物； [化4]

式(1)中，X表示芳香族基，-(Y-О)n₂ -表示聚苯醚結構，R¹ 、R² 、及R³ 各自獨立地表示氫原子、烷基、烯基或炔基，n₁ 表示1～6之整數，n₂ 表示1～100之整數，n₃ 表示1～4之整數。 >10>如>8>或>9>記載之樹脂組成物，其中，該聚苯醚化合物之數量平均分子量為1000以上且7000以下。 >11>如>1>～>10>中任一項記載之樹脂組成物，更含有馬來醯亞胺化合物。 >12>如>11>記載之樹脂組成物，其中，該馬來醯亞胺化合物包含選自由式(2M)表示之化合物、式(3M)表示之化合物、及式(4M)表示之化合物構成之群組中之至少1種； [化5]

式(2M)中，R⁴ 各自獨立地表示氫原子或甲基，n₄ 表示1以上之整數； [化6]

式(3M)中，R⁵ 各自獨立地表示氫原子、碳原子數1～8之烷基或苯基，n₅ 表示1以上且10以下之整數； [化7]

式(4M)中，R⁶ 各自獨立地表示氫原子、甲基或乙基，R⁷ 各自獨立地表示氫原子或甲基。 >13>如>12>記載之樹脂組成物，其中，該馬來醯亞胺化合物包含式(3M)表示之化合物。 >14>如>1>～>13>中任一項記載之樹脂組成物，更含有氰酸酯化合物。 >15>如>1>～>14>中任一項記載之樹脂組成物，更含有阻燃劑。 >16>如>1>～>15>中任一項記載之樹脂組成物，其中，該化合物(A)之含量，相對於樹脂成分100質量份為1～10質量份。 >17>如>1>～>16>中任一項記載之樹脂組成物，其中，該具有芳香環結構之樹脂及具有芳香環結構之彈性體之合計含量，相對於樹脂成分100質量份為1～50質量份。 >18>如>1>～>17>中任一項記載之樹脂組成物，其中，該填充材(C)之含量相對於樹脂成分100質量份為50～300質量份。 >19>一種預浸體，係由基材、及如>1>～>18>中任一項記載之樹脂組成物形成。 >20>一種覆金屬箔疊層板，包含至少一片之如>19>記載之預浸體、及配置於該預浸體之單面或兩面之金屬箔。 >21>一種樹脂片，包含支持體、及配置於該支持體之表面之由如>1>～>18>中任一項記載之樹脂組成物形成之層。 >22>一種印刷配線板，包含絕緣層、及配置於該絕緣層之表面之導體層； 該絕緣層包含由如>1>～>18>中任一項記載之樹脂組成物形成之層及由如>19>記載之預浸體形成之層之至少一種。 [發明之效果]Based on the above-mentioned problems, the present inventors conducted an investigation and found that in a resin composition containing a resin or an elastomer and a filler, a compound having an aromatic ring structure is used as the resin or elastomer, and further blended in one molecule has 2 More than one compound (A) with aromatic ring structure can solve the above problems. Specifically, the above problems are solved by the following means>1>, preferably using>2>to>22>.>1>A resin composition containing: a compound (A) having more than two aromatic ring structures in one molecule and a group represented by -Si(OR ⁰¹ ) _m (R ⁰² ) _3-m ; component (B ) Is at least one of a resin having an aromatic ring structure and an elastomer having an aromatic ring structure; and a filler (C); the R ⁰¹ and R ⁰² are each independently a hydrocarbon group, and m is an integer of 1 to 3. >2> The resin composition according to >1>, wherein the compound (A) has a repeating unit containing an aromatic ring structure. >3> The resin composition according to >2>, wherein the repeating unit containing an aromatic ring structure of the compound (A) is polyphenylene ether. >4> The resin composition according to >1>, wherein the compound (A) includes a compound represented by formula (X); formula (X) [Chem 2]

(X) In formula (X), X represents an n-valent organic group containing a polyphenylene ether structure, and R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms. group, A ¹ represents a single bond or a divalent heteroatom-containing linking group of atoms, A ² represents a single bond or a divalent linking group of, m an integer of 1 to 3, the system, n the number of lines 1 to 10. >5> The resin composition as described in >1>, wherein the compound (A) includes a compound represented by formula (Y); formula (Y)

(Y) In formula (Y), A ² is a single bond or a divalent linking group, and R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, m is an integer from 1 to 3, and n is a number from 1 to 10. >6> The resin composition according to any one of >1>to>5>, wherein the weight average molecular weight of the compound (A) is 1,000 or more. >7> The resin composition according to any one of >1>to>6>, wherein the elastomer having an aromatic ring structure includes a styrene-based elastomer. >8> The resin composition according to any one of >1>to>7>, wherein the resin having an aromatic ring structure contains a polyphenylene ether compound. >9> The resin composition according to >8>, wherein the polyphenylene ether compound includes a polyphenylene ether compound represented by the following formula (1);

In formula (1), X represents an aromatic group, -(Y-О)n ₂ -represents a polyphenylene ether structure, and R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkyne Base, n ₁ represents an integer of 1 to 6, n ₂ represents an integer of 1 to 100, and n ₃ represents an integer of 1 to 4. >10> The resin composition according to >8> or >9>, wherein the number average molecular weight of the polyphenylene ether compound is 1,000 or more and 7,000 or less. >11> The resin composition described in any one of >1>to>10> further contains a maleimide compound. >12> The resin composition according to >11>, wherein the maleimide compound includes a compound selected from the group consisting of a compound represented by formula (2M), a compound represented by formula (3M), and a compound represented by formula (4M) At least one of the group; [Chem 5]

In formula (2M), R ⁴ each independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more; [Chem 6]

In formula (3M), R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n ₅ represents an integer of 1 or more and 10 or less;

In formula (4M), R ⁶ each independently represents a hydrogen atom, a methyl group or an ethyl group, and R ⁷ each independently represents a hydrogen atom or a methyl group. >13> The resin composition according to >12>, wherein the maleimide compound includes a compound represented by formula (3M). >14> The resin composition described in any one of >1>to>13> further contains a cyanate compound. >15> The resin composition described in any one of >1>to>14> further contains a flame retardant. >16> The resin composition according to any one of >1>to>15>, wherein the content of the compound (A) is 1 to 10 parts by mass relative to 100 parts by mass of the resin component. >17> The resin composition according to any one of >1>to>16>, wherein the total content of the resin having an aromatic ring structure and the elastomer having an aromatic ring structure is 100 parts by mass with respect to the resin component 1-50 parts by mass. >18> The resin composition according to any one of >1>to>17>, wherein the content of the filler (C) is 50 to 300 parts by mass relative to 100 parts by mass of the resin component. >19> A prepreg formed from a base material and the resin composition described in any one of >1> to >18>. >20> A metal foil-clad laminate, comprising at least one prepreg as described in >19>, and metal foil disposed on one or both sides of the prepreg. >21> A resin sheet comprising a support and a layer formed of the resin composition described in any one of >1> to >18> disposed on the surface of the support. >22> A printed wiring board including an insulating layer and a conductor layer disposed on the surface of the insulating layer; the insulating layer includes a layer formed of the resin composition described in any one of >1>to>18> and At least one of the layers formed by the prepreg described in >19>. [Effect of invention]

According to the present invention, a resin composition capable of maintaining a low dielectric constant (Dk) and a low dielectric loss factor (Df) while achieving high peel strength and low melt viscosity, as well as a prepreg and metal-clad laminate , Resin sheet and printed wiring board.

The content of the present invention will be described in detail below. In addition, in this specification, "~" is used with the meaning including the numerical value described before and after it as a lower limit and an upper limit.

The resin composition of this embodiment includes: a compound (A) having two or more aromatic ring structures in one molecule and a group represented by -Si(OR ⁰¹ ) _m (R ⁰² ) _3-m (hereinafter sometimes referred to as "Compound (A)"); at least one component (B) of a resin having an aromatic ring structure and an elastomer having an aromatic ring structure; and a filler (C); the R ⁰¹ and R ⁰² are independent of each other Ground is a hydrocarbon group, m is an integer of 1-3. With such a configuration, it is possible to maintain a low dielectric constant (Dk) and a low dielectric loss factor (Df) while achieving high peel strength. In addition, since a low melt viscosity can be achieved, a resin composition excellent in manufacturability can be obtained. The reason is presumably as follows. That is, the group represented by -Si(OR ⁰¹ ) _m (R ⁰² ) _{3-m in the} compound (A) will be bonded to the filler (C). In addition, the two or more aromatic ring structures of the compound (A) will interact with the resin having the aromatic ring structure and/or the elastomer having the aromatic ring structure in a π-π system. It is considered that due to these effects, the connection between the resin and/or elastomer and the filler (C) is strengthened, whereby the peel strength can be improved. Moreover, it is considered that the aromatic ring structure of the compound (A) and the resin having the aromatic ring structure and/or the elastomer having the aromatic ring structure are effectively compatible, so the dispersibility of the filler (C) in the resin composition is improved And the melt viscosity decreases. In addition, when the resin composition is made into a state of varnish, it is possible to effectively suppress aggregation of components and the like. In addition, when the resin composition is formed into a layer, layer separation in the layer can be less likely to occur. That is, a resin composition excellent in manufacturability can be produced. The present invention will be described in detail below.

> A compound having two or more aromatic ring structures and a group represented by -Si(OR ⁰¹ ) _m (R ⁰² ) _{3-m in} one molecule (A)> The resin composition of this embodiment contains one molecule having A compound having two or more aromatic ring structures and a group represented by -Si(OR ⁰¹ ) _m (R ⁰² ) _3-m (compound (A)). Compound (A), the group represented by -Si(OR ⁰¹ ) _m (R ⁰² ) _3-m is bonded to the filler (C), and the aromatic ring structure of the compound (A) and the resin having the aromatic ring structure and/ Or elastomers with aromatic ring structure are mutually compatible. That is, the compound (A) functions like a silane coupling agent. As a result, a low dielectric constant (Dk) and a low dielectric loss factor (Df) can be maintained while achieving high peel strength and low melt viscosity. The compound (A) preferably contains a repeating unit containing an aromatic ring structure, the aforementioned repeating unit containing an aromatic ring structure is more preferably polyphenylene ether, and the compound (A) more preferably contains polyphenylene ether. Since the compound (A) includes a repeating unit containing an aromatic ring structure, the compatibility with the resin having an aromatic ring structure and the elastomer having an aromatic ring structure is further improved. In particular, when the resin having an aromatic ring structure contains a polyphenylene ether compound, the compound (A) preferably contains polyphenylene ether.

-Si(OR ⁰¹ ) _m (R ⁰² ) In the group represented by _3-m , R ⁰¹ and R ⁰² are each independently a hydrocarbon group, and m is an integer of 1 to 3. R ⁰¹ and R ⁰² are each independently preferably an alkyl group or an aryl group, and in formula (X) described later, R ¹ and R ^{2 are} more preferably in the same range. m is preferably 2 to 3, more preferably 3. Compound (A) may contain only one group represented by -Si(OR ⁰¹ ) _m (R ⁰² ) _3-m in one molecule, or may have 2 or more, preferably 1 to 10, more preferably 1 to Five, and more preferably one or two. Compound (A) may contain only one kind of group represented by -Si(OR ⁰¹ ) _m (R ⁰² ) _3-m in one molecule, or may contain two or more kinds.

(X) 式(X)中，X表示含有聚苯醚結構之n價之有機基，R¹ 及R² 各自獨立地表示碳原子數1～10之烷基、或碳原子數6～10之芳基，A¹ 表示單鍵或含有雜原子之2價之連結基，A² 表示單鍵或2價之連結基，m係1～3之整數，n係1～10之數。The compound (A) preferably includes a compound represented by the formula (X). Formula (X) [Chem 8]

(X) In formula (X), X represents an n-valent organic group containing a polyphenylene ether structure, and R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms, or 6 to 10 carbon atoms. Aryl group, A ¹ represents a single bond or a divalent linking group containing a heteroatom, A ² represents a single bond or a divalent linking group, m is an integer of 1 to 3, and n is a number of 1 to 10.

In formula (X), X represents an n-valent organic group containing a polyphenylene ether structure, which may also have a linear structure, a branched structure, or a cross-linked structure. The present invention is preferably a linear chain structure. The above X is not particularly limited as long as it contains an n-valent organic group having a polyphenylene ether structure, but in view of improving the metal foil adhesion and low dielectric properties, the present invention is especially the following formula (X1) The base represented by ~(X3) is ideal.

式(X1)～(X3)中，R³ 及R⁴ 各自獨立係碳原子數1～12之烷基、碳原子數1～12之烷氧基、或鹵素原子。a及b各自獨立地係1～100之數。Z表示以式(XX)表示之連結基。[化9]

In formulas (X1) to (X3), R ³ and R ⁴ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. a and b are independently 1 to 100. Z represents a linking group represented by formula (XX).

[化10]

In formula (XX), and R ⁴ in the formula (X1) ~ (X3) R ⁴ represents the same as the meaning, L represents a linking group selected from the following formulas.

[Chem 11]

R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ⁶ each independently represents an alkyl group having 1 to 12 carbon atoms, k represents an integer of 1 to 12, j represents 1 to 1,000 number.

In the formulae (X1) to (X3), the alkyl groups having 1 to 12 carbon atoms as R ³ and R ^{4 may} be any of straight chain, branched, and cyclic. Specific examples of R ³ and R ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, n-hexyl, and n Linear or branched alkyl groups such as heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl , Cyclooctyl and other cyclic alkyl groups. These groups may also be substituted with substituents. In the formulae (X1) to (X3), the alkoxy groups having 1 to 12 carbon atoms as R ³ and R ^{4 may} be linear, branched, or cyclic. Specific examples of R ³ and R ⁴ include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, second butoxy, third butoxy, n-pentyl Straight-chain or branched alkoxy, cyclopentyloxy such as oxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, etc. Group, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy and other cyclic alkoxy groups. These groups may also be substituted with substituents. In formulas (X1) to (X3), some or all of the hydrogen atoms of R ³ and R ⁴ may also be replaced by halogen atoms such as F, Cl, Br, hydrogenthio, cyano, etc. For example, 3-chloropropyl, 3,3,3-trifluoropropyl, 3-hydrothiopropyl, 2-cyanoethyl and the like can be exemplified. In the formulae (X1) to (X3), examples of the halogen atoms for R ³ and R ⁴ include F, Cl, and Br. Among these, from the viewpoint of the ease of manufacture in terms of R ³ , it is preferably methyl or methoxy, and more preferably methyl. In addition, R ^{4 is} preferably a hydrogen atom, a methyl group, or a methoxy group, and more preferably a hydrogen atom.

In formulas (X1) to (X3), a and b are each independently a number of 1 to 100, considering the viewpoint of metal foil adhesion and dielectric properties of compound (A), it is preferably 3 to 50, more preferably 5 ~20. By setting a and b to 1 or more, the metal foil adhesion tends to be more improved and the dielectric characteristics tend to be better. In addition, by setting a and b to 100 or less, the compatibility of the resin component of the compound (A) tends to be more improved.

In formula (X), R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms. In formula (X), R ¹ and R ^{2 may have} any one of linear, branched, and cyclic alkyl groups having 1 to 10 carbon atoms. Specific examples include methyl group and ethyl group. Linear, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and other straight-chain or Cyclic alkyl groups such as branched alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. In the formula (X), specific examples of the aryl group having 6 to 10 carbon atoms for R ¹ and R ² include phenyl, α-naphthyl, and β-naphthyl. In formula (X), part or all of the hydrogen atoms of R ¹ and R ² may also be substituted with halogen atoms such as F, Cl, Br, cyano group, etc. For specific examples of such groups, 3 can be exemplified -Chloropropyl, 3,3,3-trifluoropropyl, 2-cyanoethyl, tolyl, xylyl, etc.

In formula (X), from the viewpoint of R ¹ , considering the hydrolyzability, it is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, and even more preferably a methyl group. In formula (X), R ^{2 is} preferably a linear alkyl group, more preferably a methyl group, an ethyl group, and even more preferably a methyl group.

In formula (X), m is an integer of 1 to 3, and the viewpoint of reactivity is preferably 2 to 3, more preferably 3. In formula (X), n is a number of 1 to 10, preferably 1 to 5, more preferably 1 to 2. n is the average number. By setting n to 1 or more, the reactivity can be further improved, and by setting n to 10 or less, the storage stability is improved and the resin composition can hardly crack when cured.

In formula (X), A ¹ represents a single bond or a divalent linking group containing a heteroatom. In the formula (X), specific examples of the divalent linking group containing a hetero atom represented by A ¹ include an ether bond (-O-), a thioether bond (-S-), and an amine bond (-NH -), sulfonamide bond (-S(=O) ₂ -), phosphine bond (-P(=O)OH-), carbonyl bond (-C(=O)-), thiocarbonyl bond (-C (=S)-), ester bond (-C(=O)O-), thioester bond (-C(=O)S-), thioester bond (-C(=S)O-), di Thioester bond (-C(=S)S-), carbonate bond (-OC(=O)O-), thiocarbonate bond (-OC(=S)O-), amide bond (- C(=O)NH-), thioamide bond (-C(=S)NH-), urethane bond (-OC(=O)NH-), thiocarbamate bond (-SC (=O)NH-), thiocarbamate bond (-OC(=S)NH-), dithiocarbamate bond (-SC(=S)NH-), urea bond (-NHC (=O)NH-), thiourea bond (-NHC(=S)NH-), etc. Among these, to A ^1, the ether bond should be (-O-), or a carbamate bond (-OC (= O) NH-) .

In formula (X), A ² represents a single bond or a divalent linking group. On the other hand, the divalent linking group represented by A ² is preferably a linking group containing no hetero atom. In formula (X), the divalent linking group represented by A ² is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, and examples include methylene, ethylidene, trimethylene, propylidene, and isopropylidene. Group, tetramethylene, isobutylene, pentamethylene pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, Twelve methylene, thirteen methylene, fourteen methylene, fifteen methylene, sixteen methylene, seventeen methylene, eighteen methylene, nineteen methylene, twenty methylene Methyl groups such as alkylene groups; cyclic alkylene groups such as cyclopentyl groups, cyclohexyl groups; aryl groups such as phenyl groups, α-, β-naphthyl groups, etc. Among these, trimethylene and octamethylene are preferred, and trimethylene is more preferred.

In formula (X), with respect to the -A ¹ -A ² -group, a trimethylene group having a urethane bond (-OC(=O)NH-) represented by formula (12), formula (13) The represented trimethylene having an ether bond (-O-) is ideal.

[化12]

Therefore, as for the compound (A), the average structural formula is preferably represented by formula (1A) or formula (2A). By using these compounds, better metal foil adhesion and dielectric properties can be exhibited.

[Chem 13]

In the formula (1A) and ^{(2A), R 1, R} 2, A 1, A 2 and m in the formula ^{(X) R 1, R 2} , A 1, A 2 , and m the same meaning, R ³ Each independently represents a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, or a halogenation having 1 to 12 carbon atoms Alkoxy, R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, or carbon In the halogenated alkoxy group having 1 to 12 atoms, a and b are each independently a number of 1 to 100, c is a number of 0 or more and less than 2, and Z represents a linking group represented by formula (3) described later.

(Y) 式(Y)中，A² 係單鍵或2價之連結基，R¹ 及R² 各自獨立地表示碳原子數1～10之烷基、或碳原子數6～10之芳基，m係1～3之整數，n係1～10之數。 式(Y)中，A² 、R¹ 、R² 、m、n之理想的範圍與式(X)中之該等之範圍為相同。In this embodiment, the compound (A) more preferably includes the compound represented by the formula (Y). Formula (Y) [Chem. 14]

(Y) In formula (Y), A ² is a single bond or a divalent linking group, and R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. , M is an integer from 1 to 3, and n is a number from 1 to 10. In formula (Y), the ideal ranges of A ² , R ¹ , R ² , m, and n are the same as those in formula (X).

The weight average molecular weight of the compound (A) is not particularly limited, but it is preferably 1,000 or more, and more preferably 4,000 or more. The upper limit of the weight average molecular weight is, for example, 20,000 or less, and more preferably 10,000 or less. In addition, the weight-average molecular weight in this embodiment is the polystyrene conversion value which the gel permeation chromatography (GPC) has. In addition, the details of the compound (A) can be referred to the description of Japanese Patent Laid-Open No. 2018-016709, and these contents are incorporated in this specification.

The lower limit of the content of the compound (A) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more relative to 100 parts by mass of the resin component in the resin composition. The upper limit of the content of the compound (A) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition. In addition, the lower limit of the content of the compound (A) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit of the content of the compound (A) in the resin composition is preferably 10% by mass or less, or 8% by mass or less. The resin composition in this embodiment may contain only one kind of compound (A) or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

>>Other silane coupling agent>> The resin composition of this embodiment may contain a silane coupling agent other than the above-mentioned compound (A), or may not. When a silane coupling agent other than the compound (A) is contained, the surface treatment of fillers generally used for electronic materials can be preferably used, and the type is not particularly limited. Specific examples include aminosilane-based γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-propylene oxide. Epoxy silanes such as oxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyl -Tris(β-methoxyethoxy)silane and other vinyl silane series, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc. Cationic silane series, phenyl silane series, etc. When the resin composition of this embodiment contains a silane coupling agent other than the compound (A), its content may be about 1 to 5 parts by mass relative to 100 parts by mass of the resin component in the resin composition. In addition, the resin composition of this embodiment may be configured to substantially not contain a silane coupling agent other than the compound (A). The term "substantially free" means 10 mass% or less of the content of the compound (A), preferably 5 mass% or less, and more preferably 1 mass% or less.

>(B) Resin with aromatic ring structure and elastomer with aromatic ring structure> The resin composition of this embodiment contains at least one kind of resin having an aromatic ring structure and an elastomer having an aromatic ring structure, and preferably contains both a resin having an aromatic ring structure and an elastomer having an aromatic ring structure. In the resin composition of this embodiment, the total of the resin having an aromatic ring structure and the elastomer having an aromatic ring structure should preferably account for more than 10% by mass of the resin component, more preferably more than 20% by mass, and more preferably more than 30% by mass. . In terms of the upper limit, it should preferably account for 90% by mass or less of the resin component, more preferably 60% by mass or less, or 50% by mass or less.

In addition, the content of the resin component in the resin composition (referring to a resin having an aromatic ring structure, an elastomer having an aromatic ring structure, and other resin components) is preferably 10% by mass or more of the resin composition in total , More preferably 25% by mass or more, and more preferably 40% by mass or more. In addition, the upper limit of the content of the resin component is preferably 80% by mass or less of the resin composition, more preferably 70% by mass or less, and still more preferably 60% by mass or less. Hereinafter, a resin having an aromatic ring structure, an elastomer having an aromatic ring structure, and other resin components will be described in detail.

化合物，至少含有聚苯醚化合物較佳，至少含有利用含有碳-碳不飽和雙鍵(馬來醯亞胺除外)之取代基進行末端改性而成之改性聚苯醚化合物又更佳。>>Resin with aromatic ring structure>> Resin with aromatic ring structure is a resin containing more than one aromatic ring structure in one molecule, preferably contains more than two in one molecule, more preferably contains more than two A polymer containing a repeating unit of an aromatic ring structure (for example, a compound having a weight average molecular weight of 1,000 or more). Examples of resins having an aromatic ring structure include polyphenylene ether compounds, phenol resins, and benzoxanthenes.

The compound preferably contains at least a polyphenylene ether compound, and at least contains a modified polyphenylene ether compound obtained by terminal modification using a substituent containing a carbon-carbon unsaturated double bond (excluding maleimide).

>>>Polyphenylene ether compound>>> The polyphenylene ether compound is not particularly limited as long as it has a polyphenylene ether structure, and known compounds can be used. For example, a compound having a phenylene ether skeleton represented by the following formula (X1) can be exemplified.

(式(X1)中，R²⁴ 、R²⁵ 、R²⁶ 、及R²⁷ 可為相同或不同，表示碳原子數6以下之烷基、芳基、鹵素、或氫。)[化15]

(In formula (X1), R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ may be the same or different, and represent an alkyl group, an aryl group, a halogen, or hydrogen having 6 or less carbon atoms.)

(式(X2)中，R²⁸ 、R²⁹ 、R³⁰ 、R³⁴ 、R³⁵ 可為相同亦可為不同，係碳原子數6以下之烷基或苯基。R³¹ 、R³² 、R³³ 可為相同亦可為不同，係氫原子、碳原子數6以下之烷基或苯基。) [化17]

(式(X3)中，R³⁶ 、R³⁷ 、R³⁸ 、R³⁹ 、R⁴⁰ 、R⁴¹ 、R⁴² 、R⁴³ 可為相同亦可為不同，係氫原子、碳原子數6以下之烷基或苯基。-A-係碳原子數20以下之直鏈、分支或環狀之2價的烴。)The polyphenylene ether compound may further contain a repeating unit represented by formula (X2) and/or a repeating unit represented by formula (X3). [Chem 16]

(In formula (X2), R ²⁸ , R ²⁹ , R ³⁰ , R ³⁴ , and R ³⁵ may be the same or different, and are an alkyl group or a phenyl group having 6 or less carbon atoms. R ³¹ , R ³² , and R ³³ It may be the same or different, and it is a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group.) [Chem. 17]

(In formula (X3), R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , and R ⁴³ may be the same or different, and are hydrogen atoms, alkyl groups having 6 or less carbon atoms Or phenyl. -A- is a linear, branched or cyclic divalent hydrocarbon with 20 or less carbon atoms.)

The polyphenylene ether compound can also be a modified polyphenylene ether which is functionalized by part or all of the terminal by functionalization using ethylenic unsaturated groups, epoxy groups, amine groups, hydrogen sulfide groups, carboxyl groups, and silicon groups. Compound. It is especially suitable for modified polyphenylene ether compound which is functionalized by ethylenic unsaturated group. By using such modified polyphenylene ether compound. It can make Df smaller and improve the peel strength. These can be used alone or in combination of two or more.

The method for producing the modified polyphenylene ether compound is not particularly limited as long as the effect of the present invention can be obtained. For example, by functionalizing with ethylenically unsaturated groups (specifically, vinylbenzyl, etc.), by dissolving the difunctional phenylene ether oligomer and vinylbenzyl chloride in a solvent, and After adding and reacting the base with heating and stirring, the resin is solidified to produce. Those functionalized with carboxyl groups, for example, by functionalizing polyphenylene ether compounds with unsaturated carboxylic acids or unsaturated carboxylic acids in the presence or absence of free radical initiators The derivatives are melt-kneaded and reacted to produce them. Alternatively, the polyphenylene ether compound and the unsaturated carboxylic acid or the functional derivative of the unsaturated carboxylic acid are dissolved in an organic solvent in the presence or absence of a radical initiator, and allowed to react in a solution, thereby To manufacture.

The modified polyphenylene ether compound is preferably contained in a modified polyphenylene ether compound having ethylenic unsaturated groups at both ends (hereinafter sometimes also referred to as "modified polyphenylene ether compound (g)"). Examples of the ethylenically unsaturated group include vinyl groups, allyl groups, acrylic groups, methacrylic groups, propenyl groups, butenyl groups, hexenyl groups, and octenyl groups. Cyclic alkenyl groups such as hexenyl, alkenyl groups such as vinylbenzyl and vinylnaphthyl are preferably vinylbenzyl. The two ethylenically unsaturated groups at both ends may be the same functional group or different functional groups. By using such modified polyphenylene ether compound, Df can be made smaller and the peel strength can be improved.

Examples of the modified polyphenylene ether compound (g) include compounds represented by formula (1).

式(1)中，X表示芳香族基，-(Y-О)n₂ -表示聚苯醚結構，R¹ 、R² 、及R³ 各自獨立地表示氫原子、烷基、烯基或炔基，n₁ 表示1～6之整數，n₂ 表示1～100之整數，n₃ 表示1～4之整數。[Chemical 18]

In formula (1), X represents an aromatic group, -(Y-О)n ₂ -represents a polyphenylene ether structure, and R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkyne Base, n ₁ represents an integer of 1 to 6, n ₂ represents an integer of 1 to 100, and n ₃ represents an integer of 1 to 4.

此處，-(O-X-O)-宜以式(3)及/或式(4)表示。 [化20]

(式(3)中，R⁴ 、R⁵ 、R⁶ 、R¹⁰ 、R¹¹ 可為相同亦可為不同，係碳原子數6以下之烷基或苯基。R⁷ 、R⁸ 、R⁹ 可為相同亦可為不同，係氫原子、碳原子數6以下之烷基或苯基。) [化21]

(式(4)中，R¹² 、R¹³ 、R¹⁴ 、R¹⁵ 、R¹⁶ 、R¹⁷ 、R¹⁸ 、R¹⁹ 可為相同亦可為不同，係氫原子、碳原子數6以下之烷基或苯基。-A-係碳原子數20以下之直鏈、分支或環狀之2價之烴基。)The modified polyphenylene ether compound (g) in this embodiment is preferably represented by formula (2). [Chem 19]

Here, -(OXO)- is preferably expressed by formula (3) and/or formula (4). [化20]

(In formula (3), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , and R ¹¹ may be the same or different, and are an alkyl group or a phenyl group having 6 or less carbon atoms. R ⁷ , R ⁸ , and R ⁹ It may be the same or different, and it is a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group.) [Chem. 21]

(In formula (4), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different, and are a hydrogen atom or an alkyl group having 6 or less carbon atoms Or phenyl. -A- is a linear, branched or cyclic divalent hydrocarbon group with 20 or less carbon atoms.)

(式(5)中，R²² 、R²³ 可為相同亦可為不同，係碳原子數6以下之烷基或苯基。R²⁰ 、R²¹ 可為相同亦可為不同，係氫原子、碳原子數6以下之烷基或苯基。) 式(2)中，a、b中至少任一者不為0，係表示0～100之整數。a及/或b為2以上之整數時，2以上之-(Y-O)a-及/或2以上之-(Y-O)b-各自獨立地可為1種結構配置而成者，亦可為2種以上之結構呈嵌段或無規配置。Also, -(YO)- should be expressed by formula (5). [化22]

(In formula (5), R ²² and R ²³ may be the same or different, and are an alkyl group or a phenyl group having 6 or less carbon atoms. R ²⁰ and R ²¹ may be the same or different, and are hydrogen atoms, An alkyl group or a phenyl group having 6 or less carbon atoms.) In formula (2), at least one of a and b is not 0, and represents an integer of 0 to 100. When a and/or b is an integer of 2 or more, 2 or more -(YO)a- and/or 2 or more -(YO)b- can be independently configured for one structure, or 2 More than one kind of structure is in block or random configuration.

Examples of -A- in formula (4) include methylene, ethylene, 1-methylethylene, 1,1-propylene, and 1,4-phenylenebis(1 -Methylethylene), 1,3-phenylenebis(1-methylethylene), cyclohexylene, phenylmethylene, naphthylmethylene, 1-phenylethylene, etc. The 2-valent organic group is not limited to these.

Among the above modified polyphenylene ether compounds (g), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ²⁰ , and R ²¹ are alkyl groups having 3 or less carbon atoms, and R ⁷ , R ⁸ , and R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²² and R ^{23 are} preferably hydrogen atoms or polyalkylene ether compounds with an alkyl group of 3 or less carbon atoms, In particular, it is preferably represented by formula (3) or formula (4)-(OXO)-system formula (9), formula (10), and/or formula (11), and-(YO)-represented by formula (5) Formula (12) or formula (13). When a and/or b is an integer of 2 or more, two or more -(YO)a- and/or two or more -(YO)b- are each independently formula (12) and/or formula (13) There are more than two structures, or it can be a block or random structure of formula (12) and formula (13).

[化24]

(式(10)中，R⁴⁴ 、R⁴⁵ 、R⁴⁶ 、R⁴⁷ 可為相同亦可為不同，係氫原子或甲基。-B-係碳原子數20以下之直鏈、分支或環狀之2價之烴基。) -B-可列舉與式(4)中之-A-之具體例相同者作為具體例。 [化25]

(式(11)中，-B-係碳原子數20以下之直鏈、分支或環狀之2價之烴基。) -B-可列舉與式(4)中之-A-之具體例相同者作為具體例。 [化26]

[化27]

[化23]

[化24]

(In formula (10), R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , and R ⁴⁷ may be the same or different, and are a hydrogen atom or a methyl group. -B- is a linear, branched, or cyclic carbon number of 20 or less A divalent hydrocarbon group.) -B- The specific example of -A- in the formula (4) can be cited as a specific example. [化25]

(In formula (11), -B- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.) -B- can be the same as the specific example of -A- in formula (4) As a specific example. [化26]

[化27]

The preparation method (manufacturing method) of the modified polyphenylene ether compound (g) represented by the formula (2) of this embodiment is not particularly limited. For example, it can be produced by the following steps: combining the 2-functional phenol compound and 1 The step of oxidatively coupling the functional phenol compound to obtain a 2-functional phenylene ether oligomer (oxidative coupling step), and the terminal phenolic hydroxyl group of the obtained 2-functional phenylene ether oligomer to vinylbenzyl Step of etherification (vinylbenzyl etherification step). In addition, as such a modified polyphenylene ether compound, for example, Mitsubishi Gas Chemical Co., Ltd. (OPE-2St1200, etc.) can be used.

In the oxidative coupling step, for example, the 2-functional phenylene ether oligomer can be obtained by dissolving the 2-functional phenol compound, the 1-functional phenol compound, and the catalyst in a solvent, and blowing oxygen under heating and stirring Thing. The bifunctional phenol compound is not particularly limited, and examples thereof include selected from 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenyl)-4, 4'-diol, 4,4'-methylene bis(2,6-dimethylphenol), 4,4'-dihydroxyphenylmethane, and 4,4'-dihydroxy-2,2' -At least one of the groups consisting of diphenylpropane. The monofunctional phenol compound is not particularly limited, and examples thereof include 2,6-dimethylphenol and/or 2,3,6-trimethylphenol. The catalyst is not particularly limited, and examples thereof include copper salts (eg, CuCl, CuBr, CuI, CuCl ₂ , CuBr ₂ etc.), amines (eg, di-n-butylamine, n-butyldimethylamine, N,N'-di-tert-butylethylenediamine, pyridine, N,N,N',N'-tetramethylethylenediamine, piperidine, imidazole, etc.). The solvent is not particularly limited, and examples thereof include at least one selected from the group consisting of toluene, methanol, methyl ethyl ketone, and xylene.

Vinyl benzyl etherification step, for example, by dissolving the 2-functional phenylene ether oligomer obtained by the oxidative coupling step and vinyl benzyl chloride in a solvent, and adding a base under heating and stirring to react , The resin is solidified and manufactured. The vinyl benzyl chloride is not particularly limited, and examples thereof include at least one selected from the group consisting of o-vinyl benzyl chloride, m-vinyl benzyl chloride, and p-vinyl benzyl chloride. The alkali is not particularly limited, and examples thereof include at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide. In the vinyl benzyl etherification step, in order to neutralize the base remaining after the reaction, an acid may also be used. The acid is not particularly limited, and may be selected from hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and nitric acid, for example. At least one of the group. The solvent is not particularly limited, and examples thereof include selected from toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethyl acetamide, methane chloride, and At least one of the groups consisting of chloroform. The method of solidifying the resin includes, for example, a method of evaporating the solvent and drying and solidifying it, a method of mixing the reaction solution with a poor solvent and reprecipitating it.

In addition to the above, the polyphenylene ether compound used in this embodiment may be an unmodified polyphenylene ether compound having a hydroxyl group at the end. For the unmodified polyphenylene ether compound, for example, the descriptions in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2017-119739 can be adopted, and these contents are incorporated into this specification.

The polyphenylene ether compound (preferably a modified polyphenylene ether compound) preferably has a number average molecular weight of 500 or more and 3000 or less in terms of polystyrene converted by the GPC method. When the number average molecular weight is 500 or more, when the resin composition of this embodiment is formed into a coating film shape, there is a tendency to further suppress the viscosity. When the number average molecular weight is 3000 or less, the solubility of the solvent tends to be further improved. In addition, the weight average molecular weight of the polyphenylene ether compound in terms of polystyrene by GPC is preferably 800 or more and 10,000 or less, and more preferably 800 or more and 5000 or less. By setting it to the above lower limit, the dielectric constant and dielectric loss factor tend to become lower. By setting it to the above upper limit, the solubility, low viscosity, and moldability of the solvent are more improved The tendency. In addition, the equivalent of carbon-carbon unsaturated double bond at the end of the modified polyphenylene ether compound is preferably 400-5000 g per carbon-carbon unsaturated double bond, and more preferably 400 g-2500 g. By setting it to the above lower limit or more, the dielectric constant and the dielectric loss factor tend to become lower. By setting it to the above upper limit or less, the solubility, low viscosity, and moldability of the solvent tend to be more improved.

The lower limit of the content of the polyphenylene ether compound, when contained, is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and more preferably 10 parts by mass relative to 100 parts by mass of the resin component in the resin composition. More than 15 parts by mass, more preferably 15 parts by mass or more, and more preferably 20 parts by mass or more. The upper limit of the content of the polyphenylene ether compound, when contained, is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and more preferably 40 parts by mass relative to 100 parts by mass of the resin component in the resin composition. Below mass parts. In particular, when the content of the modified polyphenylene ether compound is within the above range, there is a tendency for the low dielectric loss factor and the reactivity to be further improved. The resin composition in this embodiment may contain only one kind of polyphenylene ether compound, or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

>>>Phenol resin>>> The phenol resin is not particularly limited as long as it is a phenol compound or resin having two or more phenolic hydroxyl groups in one molecule. Examples of phenol resins include bisphenol A phenol resin, bisphenol E phenol resin, bisphenol F phenol resin, bisphenol S phenol resin, phenol phenol resin, bisphenol A phenol resin, epoxypropyl ester. Phenol resin, aralkyl phenol resin, biphenyl aralkyl phenol resin, cresol phenol resin, polyfunctional phenol resin, naphthol phenol resin, naphthol phenol resin, polyfunctional naphthol phenol resin, anthracene phenol Resin, naphthalene skeleton modified phenolic phenol resin, phenol aralkyl phenol resin, naphthol aralkyl phenol resin, dicyclopentadiene phenol resin, biphenyl phenol resin, alicyclic phenol resin, multicomponent Alcohol-type phenol resin, phosphorus-containing phenol resin, hydroxyl-containing polysiloxane resin, etc. Among these, from the viewpoint of further improving the flame resistance, it is preferably selected from the group consisting of biphenyl aralkyl phenol resin, naphthol aralkyl phenol resin, phosphorus-containing phenol resin, and hydroxyl-containing polysiloxane resin At least one of the group.

As long as the effect of the present invention is not impaired, a phenol resin is preferably contained. When contained, it is preferably 0.1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition. The resin composition in this embodiment may contain only one kind of phenol resin, or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range. In addition, the resin composition in the present embodiment may be a structure substantially free of phenol resin. The term "substantially free" means that the content of the phenol resin is less than 0.1 part by mass with respect to 100 parts by mass of the resin component in the resin composition.

化合物>>> 就苯并㗁

化合物而言，只要係1分子中具有2個以上之二氫苯并㗁

環之化合物即可，並無特別限定。 就苯并㗁

化合物而言，例如可列舉雙酚A型苯并㗁

BA-BXZ(小西化學(股)製品)、雙酚F型苯并㗁

BF-BXZ(小西化學(股)製品)、雙酚S型苯并㗁

BS-BXZ(小西化學(股)製品)等。>>>Benzo

Compound >>> Benzene

As far as the compound is concerned, as long as it has 2 or more dihydrobenzobenzenes in 1 molecule

The compound of the ring is sufficient, and is not particularly limited. Just benzo

As for the compound, for example, bisphenol A type benzo㗁 can be mentioned

BA-BXZ (Xiaoxi Chemical Co., Ltd. product), bisphenol F-type benzo㗁

BF-BXZ (Xiaoxi Chemical Co., Ltd. product), bisphenol S type benzo㗁

BS-BXZ (Xiaoxi Chemical Co., Ltd. products), etc.

化合物。於含有之情況下，相對於樹脂組成物中之樹脂成分100質量份，宜為0.1質量份以上，且宜為50質量份以下。 本實施形態中之樹脂組成物可僅含有1種苯并㗁

化合物，亦可含有2種以上。含有2種以上時，合計量宜為上述範圍。 又，本實施形態中之樹脂組成物，亦可設為實質不含苯并㗁

化合物之構成。所謂實質不含，係指苯并㗁

化合物之含量相對於樹脂組成物中之樹脂成分100質量份，未達0.1質量份。As long as the effect of the present invention is not compromised, it is preferable to contain benzo

Compound. In the case of content, it is preferably 0.1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition. The resin composition in this embodiment may contain only one kind of benzoxanthene

The compound may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range. In addition, the resin composition in this embodiment may be substantially free of benzoxanthene

The composition of the compound. Substantially free, means benzo㗁

The content of the compound is less than 0.1 part by mass with respect to 100 parts by mass of the resin component in the resin composition.

In addition to the above, as a preferred example, a resin having an aromatic ring structure which is another resin component described later is also exemplified. In the resin composition in this embodiment, the content of the resin having an aromatic ring structure is preferably 1 part by mass or more, more preferably 5 parts by mass, and more preferably 10 parts by mass or more relative to 100 parts by mass of the resin component. . In terms of the upper limit, it may be 100 parts by mass relative to 100 parts by mass of the resin component, preferably 90 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 50 parts by mass or less. It is 45 parts by mass or less, and may be 40 parts by mass or less. The resin composition in this embodiment may contain only one kind of resin having an aromatic ring structure, or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

>>Elastomer with aromatic ring structure>> An elastomer with an aromatic ring structure is an elastomer with more than one aromatic ring structure in one molecule, preferably containing more than two in one molecule, and more preferably a repeat containing more than two aromatic ring-containing structures Unit elastomers (eg compounds with a weight average molecular weight of 1000 or more). The elastomer having an aromatic ring structure is preferably a styrene elastomer. For the styrene-based elastomer, it is preferably selected from the group consisting of styrene-butadiene-styrene elastomer (SBS), styrene-isoprene-styrene elastomer (SIS), and polystyrene-poly( Ethylene-propylene) elastomer (SEP), polystyrene-poly(ethylene-propylene)-polystyrene elastomer (SEPS), polystyrene-poly(ethylene-butylene)-polystyrene elastomer (SEBS) At least one of the group consisting of polystyrene-poly(ethylene/ethylene-propylene)-polystyrene elastomer (SEEPS).

In the styrene-based elastomer, the proportion of repeating units derived from styrene is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. By setting it as such a range, solvent solubility and low dielectric characteristics can be improved.

In the resin composition of this embodiment, the content of the elastomer having an aromatic ring structure is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 8 parts by mass or more relative to 100 parts by mass of the resin component. In addition, the upper limit is preferably 60 parts by mass or less, and more preferably 40 parts by mass or less with respect to 100 parts by mass of the resin component. The resin composition in this embodiment may contain only one kind of elastomer having an aromatic ring structure, or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

>Other resin components> In addition to the above, the resin composition in this embodiment may contain other resin components. As for other resin components, there can be exemplified elastomers other than maleimide compounds, cyanate ester compounds, epoxy resins, oxetane resins, elastomers having an aromatic ring structure, active ester compounds and At least one or more of the group consisting of compounds having a polymerizable unsaturated group preferably contains at least a maleimide compound and a cyanate compound.

式(2M)中，R⁴ 各自獨立地表示氫原子或甲基，n₄ 表示1以上之整數。n₄ 宜為1～10之整數，更宜為1～5之整數，又更宜為1～3之整數，又更宜為1或2。 [化29]

式(3M)中，R⁵ 各自獨立地表示氫原子、碳原子數1～8之烷基或苯基，n₅ 表示1以上10以下之整數。 R⁵ 宜為氫原子、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、苯基，更宜為氫原子及甲基之其中一者，又更宜為氫原子。 n₅ 宜為1以上5以下之整數，更宜為1～3之整數，又更宜為1或2。 [化30]

式(4M)中，R⁶ 各自獨立地表示氫原子、甲基或乙基，R⁷ 各自獨立地表示氫原子或甲基。>>Maleimide compound>> The maleimide compound is not particularly limited as long as it is a compound having two or more maleimide groups in the molecule. An example of the maleimide compound includes maleimide compounds represented by formula (2M) to formula (4M). When these maleimide compounds are used in printed wiring board materials (for example, laminates, metal-clad laminates), etc., excellent heat resistance can be imparted while improving peel strength, low water absorption, Resistance to degumming and flammability. [Chem 28]

In formula (2M), R ⁴ each independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more. n _{4 is} preferably an integer of 1-10, more preferably an integer of 1-5, still more preferably an integer of 1-3, and still more preferably 1 or 2. [Chem 29]

In formula (3M), R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n ₅ represents an integer of 1 or more and 10 or less. R ^{5 is} preferably a hydrogen atom, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, phenyl, more preferably one of a hydrogen atom and a methyl group , And more preferably hydrogen atom. n _{5 is} preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 to 3, and still more preferably 1 or 2. [化30]

In formula (4M), R ⁶ each independently represents a hydrogen atom, a methyl group or an ethyl group, and R ⁷ each independently represents a hydrogen atom or a methyl group.

The maleimide compound represented by the aforementioned formula (2M) to formula (4M) is more preferably a maleimide compound represented by formula (3M). The maleimide compound can be prepared by a known method, and a commercially available product can also be used. Examples of commercially available products include "MIR-3000" manufactured by Nippon Kayaku Co., Ltd.

In addition, the maleimide compounds other than the above include, for example, 4,4-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide Imine, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-di Phenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl ) Hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenyl bismaleimide, 1,3-bis(3-maleimidephenoxy ) Benzene, 1,3-bis(4-maleimidephenoxy)benzene, polyphenylmethane maleimide, and prepolymers of these, such as maleimide and amine Prepolymer etc.

The lower limit of the content of the maleimide compound, when contained, is preferably 1 part by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the resin component in the resin composition. 15 parts by mass or more. When the content of the maleimide compound is 1 part by mass or more, the flame resistance tends to be improved. In addition, the upper limit of the content of the maleimide compound, when contained, is preferably 70 parts by mass or less, more preferably 50 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition. It is more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less. When the content of the maleimide compound is 70 parts by mass or less, the peel strength and low water absorption tend to improve. The resin composition in this embodiment may contain only one kind of maleimide compound, or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

>>cyanate compounds>> The cyanate compound is not particularly limited as long as it has a cyanate structure. Examples of the cyanate compound include phenol novolac type cyanate compounds, naphthol aralkyl type cyanate compounds (naphthol aralkyl type cyanate compounds), and naphthalene ether cyanate compounds. , Biphenyl aralkyl type cyanate compound, xylene resin type cyanate compound, triphenol methane type cyanate compound, adamantane skeleton type cyanate compound, bisphenol M type cyanate compound, bisphenol At least one of the group consisting of the A-type cyanate compound and the diallyl bisphenol A-type cyanate compound. Among these, from the viewpoint of further improving the low water absorption, it is preferably selected from the group consisting of phenol novolac type cyanate compounds, naphthol aralkyl type cyanate compounds, naphthalene ether type cyanate compounds, and xylene resin type cyanide At least one of the group consisting of an acid ester compound, a bisphenol M type cyanate compound, a bisphenol A type cyanate compound, and a diallyl bisphenol A type cyanate compound, preferably naphthol Aralkyl cyanate compound. These cyanate ester compounds can be prepared by a known method, and commercially available products can also be used. In addition, cyanate compounds having a naphthol aralkyl skeleton, a naphthalene ether skeleton, a xylene skeleton, a triphenol methane skeleton, or an adamantane skeleton have a functional group equivalent number larger than that of unreacted cyanate esters There are fewer bases, so there is a tendency for the water absorption to decrease further. In addition, mainly because it has an aromatic skeleton or an adamantane skeleton, it tends to further improve the adhesion of plating.

As long as the effect of the present invention is not impaired, a cyanate compound is preferably contained. In the case of content, the lower limit of the content is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and more preferably 20 parts by mass or more with respect to 100 parts by mass of the resin component in the resin composition. The content of the cyanate compound is 1 part by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, thereby having heat resistance, flame resistance, chemical resistance, low dielectric constant, and low dielectric loss factor 1. Tendency to improve insulation. The upper limit of the content of the cyanate compound, when contained, is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and more preferably 70 parts by mass relative to 100 parts by mass of the resin component in the resin composition Below mass parts, it is more preferably below 60 mass parts, and still more preferably below 50 mass parts. The resin composition in this embodiment may contain only one kind of cyanate compound, or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

>>Epoxy resin>> The epoxy resin is not particularly limited as long as it is a compound or resin having two or more epoxy groups in one molecule. Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, and bisphenol A novolac epoxy resin. Epoxy resin, epoxypropyl ester epoxy resin, aralkyl novolac epoxy resin, biphenyl aralkyl epoxy resin, naphthalene ether epoxy resin, cresol novolac epoxy resin, multifunctional Phenol epoxy resin, naphthalene epoxy resin, anthracene epoxy resin, naphthalene skeleton modified phenolic epoxy resin, phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentane Diene-type epoxy resin, biphenyl-type epoxy resin, alicyclic epoxy resin, polyol-type epoxy resin, phosphorus-containing epoxy resin, epoxypropylamine, epoxypropyl ester, butadiene Epoxidized compounds such as double bonds, compounds obtained by reaction of hydroxyl-containing polysiloxane resins with epichlorohydrin, etc. Among these, in view of further improvement in flame retardancy and heat resistance, biphenyl aralkyl type epoxy resin, naphthalene ether type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, More preferably, it is a biphenyl aralkyl type epoxy resin.

The epoxy resin should preferably be contained within the range that does not impair the effects of the present invention. From the viewpoint of formability and adhesion, when contained, it is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and more preferably 2 parts by mass relative to 100 parts by mass of the resin component in the resin composition. the above. When the content of the epoxy resin is 0.1 parts by mass or more, the peel strength and toughness of the metal foil tend to improve. The upper limit of the epoxy resin content, when contained, is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 20 parts by mass with respect to 100 parts by mass of the resin component in the resin composition. Less than 10 parts by mass, more preferably less than 10 parts by mass, and more preferably less than 8 parts by mass. When the content of the epoxy resin is 50 parts by mass or less, the electrical characteristics tend to improve. The resin composition in this embodiment may contain only one kind of epoxy resin or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range. In addition, the resin composition in the present embodiment may be a structure that does not substantially contain epoxy resin. The term "substantially free" means that the content of epoxy resin is less than 0.1 part by mass with respect to 100 parts by mass of the resin component in the resin composition.

>>Oxetane Resin>> The oxetane resin is not particularly limited as long as it is a compound having two or more oxetane groups. Examples of oxetane resins include oxetane and alkyl oxetane (e.g. 2-methyloxetane, 2,2-dimethyloxetane , 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-bis( Trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl oxetane, OXT -101 (East Asian synthetic products), OXT-121 (East Asian synthetic products), etc.

As long as the effect of the present invention is not impaired, an oxetane resin is preferably contained. When it is contained, it is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more with respect to 100 parts by mass of the resin component in the resin composition. When the content of the oxetane resin is 0.1 parts by mass or more, there is a tendency for the metal foil peel strength and toughness to improve. The upper limit of the content of oxetane resin, when contained, is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of the resin component in the resin composition It is 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 8 parts by mass or less. When the content of the oxetane resin is 50 parts by mass or less, the electrical characteristics tend to improve. The resin composition in this embodiment may contain only one kind of oxetane resin or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range. In addition, the resin composition in the present embodiment may be a structure that does not substantially contain an oxetane resin. The term "substantially free" means that the content of the oxetane resin is less than 0.1 parts by mass with respect to 100 parts by mass of the resin component in the resin composition.

>>Elastomers other than elastomers with aromatic ring structure>> Examples of elastomers other than those having an aromatic ring structure include polyester-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, and polyacrylic-based elastomers. , Polysiloxane-based elastomers, polyimide-based elastomers, etc. that do not contain aromatic rings. As long as the effect of the present invention is not impaired, elastomers other than those having an aromatic ring structure are preferably contained. When it is contained, it is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more with respect to 100 parts by mass of the resin component in the resin composition. The upper limit of the content of the elastomer other than the elastomer having an aromatic ring structure, when contained, is preferably 50 parts by mass or less, more preferably 30 parts by mass relative to 100 parts by mass of the resin component in the resin composition Below, it is more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 8 parts by mass or less. The resin composition in this embodiment may contain only one kind of elastomer other than the elastomer having an aromatic ring structure, or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range. In addition, the resin composition in the present embodiment may be configured to include substantially no elastomer other than the elastomer having an aromatic ring structure. The term "substantially free" means that the content of the elastomer other than the elastomer having an aromatic ring structure is less than 0.1 parts by mass with respect to 100 parts by mass of the resin component in the resin composition.

二硫醇構成之群組中之1種以上。又，活性酯化合物，考量更進一步提升與環氧樹脂間之互容性之觀點，宜為在1分子中具有至少2個以上之羧酸且含有脂肪族鏈之化合物，考量使耐熱性更進一步改善之觀點，宜為具有芳香環之化合物。就更具體的活性酯化合物而言，可列舉日本特開2004-277460號公報記載之活性酯化合物。>>Active ester compound>> The active ester compound is not particularly limited, and examples thereof include compounds having two or more active ester groups in one molecule. The active ester compound may also be a linear or branched or cyclic compound. Among these, the viewpoint of further improving heat resistance is preferably an active ester compound obtained by reacting a carboxylic acid compound and/or thiocarboxylic acid compound, a hydroxyl compound and/or a thiol compound, and more An active ester compound obtained by reacting a carboxylic acid compound with one or more compounds selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is preferred, and a carboxylic acid compound and Aromatic compounds obtained by reacting phenolic hydroxyl aromatic compounds with two or more active ester groups in one molecule are particularly suitable for compounds having at least two carboxylic acids in one molecule and with Aromatic compounds having two or more active ester groups in one molecule are obtained by reacting phenolic hydroxyl aromatic compounds. Examples of the above carboxylic acid compounds include those selected from the group consisting of benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, terephthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. One or more of the group, and among these, considering the viewpoint of further improving the heat resistance, it is preferably selected from the group consisting of succinic acid, maleic acid, itaconic acid, terephthalic acid, isophthalic acid, and p-benzene One or more types of dicarboxylic acid is more preferably one or more types selected from the group consisting of isophthalic acid and terephthalic acid. The thiocarboxylic acid compound may be one or more selected from the group consisting of thioacetic acid and thiobenzoic acid. Examples of the phenol compound or naphthol compound are selected from hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein (phenolphthalin), methylated bisphenol A, Methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene , 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, pyrogallol ( benzenetriols), dicyclopentadienyl diphenol, and phenol novolac, one or more of them, considering the viewpoint of further improving heat resistance and solvent solubility, it is preferably bisphenol A, bisphenol F, bisphenol Phenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadienyldiene Phenol, phenol novolac, more preferably selected from catechol, 1,5-catechol, 1,6-catechol, 2,6-catechol, dihydroxybenzophenone, triol One or more of the group consisting of hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadienyl diphenol, and phenol novolac, and is more preferably selected from 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene One or more types selected from the group consisting of bisphenol and phenol novolac, especially preferably selected from dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl di One or more of the group consisting of phenol and phenol novolac (preferably one or more selected from the group consisting of dicyclopentadienyl diphenol and phenol novolac, more preferably dicyclopentadienyl diphenol phenol). The thiol compound mentioned above may be selected from phenyl dithiol and tri

More than one species in the group consisting of dithiols. In addition, the active ester compound is considered to further enhance the compatibility with the epoxy resin, and it is preferably a compound having at least two or more carboxylic acids in one molecule and containing an aliphatic chain, considering further heat resistance The improvement point is preferably a compound having an aromatic ring. As a more specific active ester compound, the active ester compound described in Japanese Patent Laid-Open No. 2004-277460 can be cited.

The active ester compound may be a commercially available product or may be prepared by a known method. Examples of commercially available products include compounds containing a dicyclopentadienyl diphenol structure (for example, EXB9451, EXB9460, EXB9460S, HPC-8000-65T (both are DIC products), etc.), and phenol novolac Acrylic compounds (such as DC808 (Mitsubishi Chemical Co., Ltd. products)), and phenol novolac benzoyl compounds (such as YLH1026, YLH1030, YLH1048 (all are Mitsubishi Chemical Co., Ltd. products)), considering the preservation stability of varnish, more To further improve the low thermal expansion rate when curing the resin composition (hardened material), EXB9460S is preferable.

The active ester compound can be prepared by a known method, for example, it can be obtained by a condensation reaction of a carboxylic acid compound and a hydroxy compound. Specific examples include (a) a carboxylic acid compound or a halide thereof, (b) a hydroxy compound, and (c) an aromatic monohydroxy compound, with respect to (a) a carboxyl group or a halogenated acyl group of 1 mole. , (B) the phenolic hydroxyl group is 0.05 to 0.75 moles, (c) is 0.25 to 0.95 moles of the reaction method.

As long as the effect of the present invention is not impaired, the active ester compound is preferably contained. When it is contained, it is preferably 1 part by mass or more and preferably 90 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition. The resin composition in this embodiment may contain only one kind of active ester compound, or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range. In addition, the resin composition in this embodiment may be configured to substantially not contain an active ester compound. The term "substantially free" means that the content of the active ester compound is less than 1 part by mass with respect to 100 parts by mass of the resin component in the resin composition.

>(C) Filling material> In order to improve the low dielectric constant, low dielectric loss factor, flame resistance, and low thermal expansion, the resin composition of this embodiment preferably contains a filler (C). As for the filler (C) used in the present embodiment, a well-known one can be used as appropriate, and its type is not particularly limited, and it can be ideally used by general users in the industry to which it belongs. Specific examples include natural silica, fused silica, synthetic silica, amorphous silica, silica aerogel (aerosil), hollow silica and other silicas, white carbon, Titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat treatment products (heat treatment of aluminum hydroxide And remove part of the crystal water), metal hydrates such as boehmite, magnesium hydroxide, molybdenum compounds such as molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, Calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fiber (including E glass, T Inorganic fillers such as glass, D glass, S glass, Q glass and other glass fine powders), insulating glass, spherical glass, etc. In addition, rubbers such as styrene type, butadiene type, acrylic type and the like Organic fillers such as powder, core shell rubber powder, polysiloxane resin powder, polysiloxane rubber powder, polysiloxane composite powder, etc. Among these, one or more selected from the group consisting of silicon dioxide, aluminum hydroxide, boehmite, magnesium oxide, and magnesium hydroxide is desirable. By using these fillers, the thermal expansion characteristics, dimensional stability, flame retardancy and other characteristics of the resin composition will be improved.

The content of the filler (C) in the resin composition of this embodiment can be appropriately set according to the desired characteristics, and is not particularly limited. It is preferably 50 parts by mass or more relative to 100 parts by mass of the resin component in the resin composition. , More preferably 75 parts by mass or more. Also, it is preferably 1600 parts by mass or less, more preferably 1200 parts by mass or less, and more preferably 1000 parts by mass or less, and even more preferably 750 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition. It is preferably 500 parts by mass or less, and more preferably 300 parts by mass or less. The resin composition in this embodiment may contain only one kind of filler (C) or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

>Flame retardant> The resin composition of this embodiment may contain a flame retardant. As the flame retardant, well-known ones can be used, and examples thereof include brominated epoxy resins, brominated polycarbonates, brominated polystyrenes, brominated styrenes, brominated phthalimides, and tetrabromobis Phenol A, pentabromobenzyl (meth)acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, halogenated polystyrene, Halogen flame retardants such as halogenated paraffin, red phosphorus, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tris(xylyl) phosphate, trialkyl phosphate, dioxane phosphate Base ester, ginseng (chloroethyl) phosphate, phosphazene, phosphazene, 1,3-benzyl bis(xylylene phosphate), 10-(2,5-dihydroxyphenyl)-10H -9-oxa-10-phosphaphenanthrene-10-oxide and other phosphorus-based flame retardants, aluminum hydroxide, magnesium hydroxide, some boehmite (Boehmite), boehmite (Boehmite), zinc borate, three Inorganic flame retardants such as antimony oxide, polysiloxane-based flame retardants such as polysiloxane rubber, polysiloxane resin. These flame retardants may be used alone or in combination of two or more. Among these, 1,3-phenylene bis (xylylene phosphate) does not impair the low dielectric properties and is therefore ideal.

The content of the flame retardant, when contained, is preferably 0.1 to 20% by mass of the resin composition. One type of flame retardant may be used, or two or more types may be used in combination. When two or more types are used, the total amount is within the above range.

>Dispersant> The resin composition of this embodiment may contain a dispersant. As for the dispersant, it can be preferably used for those who are generally used for coatings, and the type is not particularly limited. In this embodiment, a urethane-based dispersant is exemplified. In addition, the dispersant is preferably a copolymer-based wetting and dispersing agent. Specific examples thereof include Disperbyk-110, 111, 161, 180, 2009, 2152, 2155, BYK-W996, BYK-W9010, BYK-W903, BYK-W940, etc.

When the content of the dispersant is contained, the lower limit is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and 0.3 parts by mass or more relative to 100 parts by mass of the resin component in the resin composition. . In addition, the upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition. One type of dispersant may be used, or two or more types may be used in combination. When two or more types are used, the total amount is within the above range.

啉、三乙醇胺、三乙二胺、四甲基丁二胺、N-甲基哌啶等3級胺類；苯酚、二甲苯酚、甲酚、間苯二酚、兒茶酚等苯酚類；環烷酸鉛、硬脂酸鉛、環烷酸鋅、辛酸鋅、辛酸錳、油酸錫、馬來酸二丁基錫、環烷酸錳、環烷酸鈷、乙醯丙酮鐵等有機金屬鹽；將這些有機金屬鹽溶解於苯酚、雙酚等含有羥基之化合物而得者；氯化錫、氯化鋅、氯化鋁等無機金屬鹽；氧化二辛基錫、其他烷基錫、氧化烷基錫等有機錫化合物等。 理想的硬化促進劑為咪唑類及有機金屬鹽，更宜為組合咪唑類及有機金屬鹽之兩者來使用。>Curing accelerator> The resin composition of this embodiment may further contain a curing accelerator. The hardening accelerator is not particularly limited, and examples thereof include imidazoles such as triphenylimidazole; benzoyl peroxide, lauryl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, and diperbenzol Organic peroxides such as di(third butyl) dicarboxylate; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N- Dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methyl

Class 3 amines such as porphyrin, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol and catechol; Organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, manganese octoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetone; It is obtained by dissolving these organometallic salts in compounds containing hydroxyl groups such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, aluminum chloride; dioctyl tin oxide, other alkyl tin, alkyl oxide Organic tin compounds such as tin. The ideal hardening accelerators are imidazoles and organic metal salts, and it is more preferable to use both imidazoles and organic metal salts in combination.

The content of the hardening accelerator is, when contained, the lower limit value is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass with respect to 100 parts by mass of the resin component in the resin composition. More than. In addition, the upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less with respect to 100 parts by mass of the resin component in the resin composition. One type of hardening accelerator may be used alone, or two or more types may be used in combination. When two or more types are used, the total amount is within the above range.

>Solvent> The resin composition of this embodiment may also contain a solvent, preferably an organic solvent. In this case, the resin composition of the present embodiment is such that at least a part of the above-mentioned various resin components are dissolved in the solvent, preferably all of them are dissolved in the solvent, or in a mutually compatible form (solution or varnish). As far as the solvent is concerned, as long as it can dissolve at least a part of the above-mentioned various resin components, it is desirable to dissolve all of them, or a polar organic solvent or a non-polar organic solvent that is compatible with each other, and is not particularly limited, as far as the polar organic solvent is concerned , For example, ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), celluloids (such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters ( For example, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (such as dimethyl Oxyacetamide, dimethylformamide, etc.), for the non-polar organic solvent, for example, aromatic hydrocarbons (for example, toluene, xylene, etc.) may be mentioned. One type of solvent may be used alone, or two or more types may be used in combination. When two or more types are used, the total amount is within the above range.

>Other ingredients> The resin composition of the present embodiment may contain various polymer compounds such as thermoplastic resins and oligomers, and various additives in addition to the above-mentioned components. Examples of additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, tackifiers, flow regulators, lubricants, defoamers, Leveling agent, gloss agent, polymerization inhibitor, etc. These additives may be used alone or in combination of two or more.

>Use> The resin composition of this embodiment is used as a cured product. Specifically, the resin composition of the present embodiment can be preferably used as a material for a low dielectric constant material and/or a low dielectric loss factor material for an insulating layer of a printed wiring board and a semiconductor package. The resin composition of this embodiment can be preferably used as a material constituting a prepreg, a metal-clad laminate using a prepreg, a resin sheet, and a printed wiring board. The resin composition of the present embodiment uses a layered material (including film-like, sheet-like, etc.) as an insulating layer, prepreg, resin sheet, etc. of a printed wiring board, when the layered material is made The thickness is preferably 5 μm or more, more preferably 10 μm or more. The upper limit is preferably 200 μm or less, and more preferably 180 μm or less. In addition, the thickness of the layered material is, for example, the thickness of the glass cloth when the resin composition of the present embodiment is impregnated with glass cloth or the like. The material formed from the resin composition of this embodiment can be used for exposure and development to form a pattern, and can also be used for applications that are not subjected to exposure and development. In particular, it is suitable for use without exposure development.

>>Prepreg>> The prepreg system of this embodiment is formed of a base material (prepreg base material) and the resin composition of this embodiment. The prepreg of this embodiment, for example, after using the resin composition of this embodiment on a substrate (for example, impregnation or coating), by heating (for example, a method of drying at 120 to 220°C for 2 to 15 minutes, etc.) Obtain it by semi-hardening. At this time, the amount of the resin composition attached to the substrate, that is, the amount of the resin composition relative to the total amount of the semi-hardened prepreg (including the filler (C)) is preferably in the range of 20 to 99% by mass .

The base material is not particularly limited as long as it is used for various printed wiring board materials. Examples of the material of the substrate include glass fiber (for example, E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, and spherical glass) Etc.), inorganic fibers other than glass (such as quartz, etc.), organic fibers (such as polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the substrate is not particularly limited, and examples thereof include woven fabric, non-woven fabric, roving, cut strand felt, and surface felt. These substrates may be used alone or in combination of two or more. Among these substrates, the viewpoint of dimensional stability is preferably a woven fabric subjected to super open fiber treatment and filling treatment, and the viewpoint of strength and water absorption is considered. The substrate is preferably a thickness of 200 μm or less and a mass of 250 g/m The glass woven fabric of ² or less is preferably a glass woven fabric surface-treated with a silane coupling agent such as epoxy silane treatment or amino silane treatment in consideration of moisture absorption and heat resistance. In view of electrical characteristics, a low-dielectric glass cloth composed of glass fibers exhibiting low dielectric constant and low dielectric loss factor such as L-glass, NE-glass, and Q-glass is more suitable.

>>Metal foil-clad laminate>> The metal foil-clad laminate of this embodiment includes at least one layer formed of the prepreg of this embodiment, and is disposed on one side of the layer formed of the prepreg or Metal foil on both sides. The metal foil-clad laminate of the present embodiment includes, for example, a method of arranging at least one prepreg of the present embodiment (preferably overlapping two or more sheets) and arranging metal foil on one or both sides to form a laminate. More specifically, it can be produced by arranging metal foils such as copper and aluminum on one or both sides of a prepreg and laminating them. The number of prepregs is preferably 1-10, more preferably 2-10, and even more preferably 2-7. The metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples thereof include copper foil such as rolled copper foil and electrolytic copper foil. The thickness of the metal foil (preferably copper foil) is not particularly limited, and may be about 1.5 to 70 μm. Examples of the forming method include methods commonly used when forming laminated and multilayer boards for printed wiring boards, and more specific examples include the use of multi-layer laminators, multi-layer vacuum presses, continuous forming machines, and high-pressure machines. In a kettle forming machine, etc., a method of lamination forming is carried out under the conditions of a temperature of about 180 to 350° C., a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100 kg/cm ² . In addition, by combining the prepreg of this embodiment and a wiring board for an inner layer that is separately prepared and performing lamination molding, a multilayer board can also be produced. For the manufacturing method of the multilayer board, for example, a copper foil of about 35 μm is arranged on both sides of one prepreg of the present embodiment, and after lamination is formed by the above-mentioned forming method, an inner layer circuit is formed, and the circuit is blackened After processing, an inner layer circuit board is formed. After that, the inner layer circuit board and the prepreg of this embodiment are alternately arranged one by one, and a copper foil is further arranged on the outermost layer. Under the above conditions, it is preferable to apply vacuum Multilayer board can be produced by lamination forming under. The metal-foil-clad laminate of this embodiment can be preferably used as a printed wiring board.

>>Printed wiring board>> The printed wiring board of this embodiment is a printed wiring board including an insulating layer and a conductor layer disposed on the surface of the insulating layer, the insulating layer includes at least a layer formed of the resin composition of this embodiment and a prepreg of this embodiment One of the layers formed by the body. Such a printed wiring board can be manufactured according to a normal method, and the manufacturing method is not particularly limited. In the following, an example of a method of manufacturing a printed wiring board is presented. First, the metal foil-clad laminate such as the metal foil-clad laminate described above is prepared. Then, an etching process is applied to the surface of the metal foil-clad laminate to form an inner-layer circuit to produce an inner-layer substrate. On the surface of the inner layer circuit of the inner substrate, if necessary, surface treatment for improving the bonding strength is performed, and then the required number of prepregs are superimposed on the surface of the inner layer circuit, and an outer layer circuit is laminated on the outside The metal foil used is heated and pressed and integrally formed. In this way, it is possible to manufacture a multi-layer laminated board in which an insulating layer composed of a base material and a hardened resin composition is formed between the metal foil for the inner layer circuit and the outer layer circuit. Then, a through hole or a via hole is applied to the multilayer laminated board, and then a plating is formed on the wall surface of the hole to conduct the metal foil for the inner layer circuit and the outer layer circuit. A metallized film is applied to further etch the metal foil for the outer layer circuit to form the outer layer circuit, thereby manufacturing a printed wiring board.

The printed wiring board obtained in the above manufacturing example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes the resin composition of the present embodiment described above. That is, the above-mentioned prepreg of the present embodiment (for example, a substrate and a prepreg formed of the resin composition of the present embodiment impregnated or coated on the substrate), and the above-mentioned metal foil-clad laminate The layer formed by the resin composition is the insulating layer of this embodiment.

>>Resin sheet>> The resin sheet of this embodiment includes a support, and a layer formed of the resin composition of this embodiment disposed on the surface of the support. The resin sheet can be used as a build-up film or dry film solder mask. The manufacturing method of the resin sheet is not particularly limited, and for example, a resin obtained by applying (coating) a solution obtained by dissolving the resin composition of the present embodiment in a solvent to a support and drying the resin Film method.

Examples of the support used here include polyethylene films, polypropylene films, polycarbonate films, polyethylene terephthalate films, ethylene tetrafluoroethylene copolymer films, and the surfaces of these films. Organic film substrates such as release films coated with release agents, polyimide films, conductive foils such as copper foil and aluminum foil, glass plates, SUS (Steel Use Stainless) plates, FRP (Fiber-Reinforced Plastics) There is no particular limitation on plate-like materials.

As for the coating method (coating method), for example, a solution obtained by dissolving the resin composition of this embodiment in a solvent can be applied to a support using a coating rod, die coater, doctor blade, BAKER-type applicator, etc. The physical method. Furthermore, by drying or peeling or etching the resin sheet obtained by laminating the support from the support and the resin composition, a single-layer sheet can also be produced. In addition, a solution obtained by dissolving the resin composition of the present embodiment described above in a solvent is supplied into a mold having a sheet-shaped cavity and dried to form a sheet, which can also be obtained without using a support Single layer.

In addition, in the preparation of the single-layer sheet or the resin sheet of this embodiment, the drying conditions when removing the solvent are not particularly limited. It is considered that if the temperature is low, the solvent composition is likely to remain in the resin composition, and if the temperature is high, the resin composition will Hardening is carried out, so it is preferably 1 to 90 minutes at a temperature of 20°C to 200°C. In addition, in the single-layer sheet or the resin sheet, the resin composition can be used in an uncured state obtained by simply drying the solvent, or can be used in a semi-cured (B-staged) state as needed. In addition, the thickness of the resin layer in the single-layer sheet or the resin sheet of this embodiment can be adjusted by the concentration and the coating thickness of the solution of the resin composition of this embodiment, and is not particularly limited, considering the coating thickness in general When it becomes thicker, the solvent tends to remain during drying, so it is preferably 0.1 to 500 μm. [Example]

The following examples illustrate the present invention more specifically. The materials, usage amounts, ratios, processing contents, processing order, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

>Synthesis Example 1 Synthesis of naphthol aralkyl cyanate compound (SNCN)> 300 g of 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) (OH group converted to 1.28 mol) and 194.6 g (1.92 mol) of triethylamine (1.5 mol relative to 1 mol of hydroxyl group) was dissolved in 1800 g of dichloromethane, and this was made into a solution 1. 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol relative to 1 mol of hydroxyl group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol relative to 1 mol of hydroxyl group), and water 1205.9 g was kept at a liquid temperature of -2 to -0.5°C under stirring, and solution 1 was injected over 30 minutes. After the injection of solution 1 is completed, after stirring at the same temperature for 30 minutes, it takes 10 minutes to inject a solution prepared by dissolving 65 g (0.64 mol) of triethylamine (0.5 mol relative to 1 mol of hydroxyl group) in 65 g of dichloromethane (solution 2 ). After the solution 2 was injected, the solution was stirred at the same temperature for 30 minutes to complete the reaction. Thereafter, the reaction solution was allowed to stand to separate the organic phase from the aqueous phase. The obtained organic phase was washed with 1300 g of water 5 times. The conductivity of the wastewater after the fifth washing was 5 μS/cm, and it was confirmed that the removal of the ionic compounds was sufficiently removed by washing with water. The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated at 90° C. for 1 hour and dried and solidified to obtain 331 g of a target naphthol aralkyl cyanate compound (SNCN) (orange sticky substance). The weight average molecular weight of the obtained SNCN was 600. In addition, the IR spectrum of SNCN showed absorption of 2250 cm ^-1 (cyanate group), and did not show absorption of hydroxyl groups.

>Synthesis Example 2 Synthesis of modified polyphenylene ether compound>>>Synthesis of 2-functional phenylene ether oligomer>> Add to 12L vertical reactor equipped with stirring device, thermometer, air inlet pipe, and baffle CuBr ₂ 9.36g (42.1mmol), N,N'-di-tert-butylethylenediamine 1.81g (10.5mmol), n-butyldimethylamine 67.77g (671.0mmol), toluene 2,600g, at a reaction temperature of 40 Stirring at ℃ will make 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenol)-4,4'-diol 129.32g (0.48mol) in advance 、878.4g (7.2mol) of 2,6-dimethylphenol, 1.22g (7.2mmol) of N,N'-di-tert-butylethylenediamine, 26.35g (260.9mmol) of n-butyldimethylamine dissolved in A mixed solution of 2,300 g of methanol was mixed with nitrogen and air and adjusted to an oxygen concentration of 8% by volume. The mixed gas was bubbled at a flow rate of 5.2 L/min, and it was added dropwise for 230 minutes. Stir. After the dropwise addition, 1,500 g of water in which 48.06 g (126.4 mmol) of tetrasodium ethylenediaminetetraacetic acid was dissolved was added to terminate the reaction. The aqueous layer and the organic layer were separated, and the organic layer was first washed with 1N aqueous hydrochloric acid solution and then washed with pure water. The obtained solution was concentrated to 50% by mass using an evaporator to obtain 1981 g of a toluene solution of a bifunctional diphenylene ether oligomer (resin "A"). The number average molecular weight of the resin "A" in terms of polystyrene converted by the GPC method is 1975, the weight average molecular weight in terms of polystyrene converted by the GPC method is 3514, and the hydroxyl equivalent is 990.

>>Synthesis of modified polyphenylene ether compounds>> In a reactor equipped with a stirring device, a thermometer, and a reflux tube, 833.4 g of a toluene solution of resin "A", vinyl benzyl chloride (SEIMI CHEMICAL Co., Ltd., "CMS-P") 76.7 g, and methylene chloride were added 1,600 g, 6.2 g of benzyldimethylamine, 199.5 g of pure water, and 83.6 g of a 30.5 mass% NaOH aqueous solution were stirred at a reaction temperature of 40°C. After stirring for 24 hours, the organic layer was washed with 1N aqueous hydrochloric acid solution and then with pure water. The obtained solution was concentrated with an evaporator, added dropwise to methanol to solidify, the solid was recovered by filtration, and vacuum dried to obtain 450.1 g of a modified polyphenylene ether compound. The modified polyphenylene ether compound has a polystyrene equivalent number average molecular weight of 2250 by GPC, a polystyrene equivalent weight average molecular weight of 3920 by GPC, and a vinyl equivalent of 1189 g/vinyl.

>Manufacturing evaluation> The state after the varnish and copper-clad laminates obtained in Examples and Comparative Examples described below were prepared was evaluated visually as follows. A: When it is a varnish, no aggregation of components is considered, and after the copper-clad laminate is made, phase separation does not occur. B: When it is a varnish, it is considered that some components are aggregated, but a copper-clad laminate can be produced, and after the copper-clad laminate is produced, phase separation does not occur. C: The separation of the components is seen and the varnish cannot be adjusted, or the varnish can be adjusted, but it is considered that there are agglomeration of many components.

>Electrical characteristics (Dk and Df)> The 0.8-mm-thick copper-clad laminates obtained in the examples and comparative examples described below were etched, and the dielectric constant (Dk) and the dielectric constant (Dk) of 10 GHz were measured using a cavity resonator for a test piece from which copper foil was removed. Dielectric loss factor (Df). The perturbation method cavity resonator used Agilent Technologies (stock) product, Agilent8722ES.

>Peel strength> For the 0.8-mm-thick copper-clad laminate obtained in the examples and comparative examples described below, an Autograph device (AG-IS manufactured by Shimadzu Corporation) was used in accordance with JIS C6481 at a temperature of 25°C and the number of tests was 5 The bending strength is measured, and the average value of the maximum value is the measured value. The unit system is expressed in kN/m.

>Minimum melt viscosity> Using 1 g of the mixed resin powder obtained in Examples and Comparative Examples described later as a sample, the lowest melt viscosity was measured with a rheometer. Here, using a disposable disk with a disk diameter of 25 mm, the minimum melting of the mixed resin powder is measured from 40° C. to 200° C. under the conditions of a heating rate of 2° C./min, a frequency of 10.0 rad/sec, and a deformation of 0.1%. Viscosity. The unit is expressed in poise. The rheometer is used by TA Instruments, ARES-G2.

>Example 1> 15 parts by mass of biphenyl aralkyl type polymaleimide compound ("MIR-3000", manufactured by Nippon Kayaku Co., Ltd.), 35 parts by mass of SNCN obtained in Synthesis Example 1, styrene-isoprene-benzene 10 parts by mass of ethylene elastomer ("SEPTON2104", manufactured by Kuraray Co., Ltd.), 20 parts by mass of phosphorus flame retardant ("PX200", manufactured by Da Ba Chemical Industry Co., Ltd.), and the modified polyphenylene ether obtained in Synthesis Example 2 above 20 parts by mass of compound, 2.5 parts by mass of PPE coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., X-12-1288), 100 parts by mass of spherical silica (SC2500SQ, manufactured by Admatechs, average particle size 0.5 μm) Ester-based dispersant (BYK161, manufactured by BYK) 1 part by mass, manganese octoate ("Oct-Mn", manufactured by Nippon Chemical Industry Co., Ltd., hardening accelerator) 0.05 part by mass, and TPIZ (2,4,5-tribenzene (Bamidazole, hardening accelerator) 0.3 parts by mass was dissolved in methyl ethyl ketone and mixed to obtain a varnish. In addition, each blending amount mentioned above shows the solid content. Based on the obtained varnish, the manufacturability was evaluated. The results are shown in Table 1 together with the manufacturability of the copper-clad laminate.

In addition, methyl ethyl ketone was distilled off from the obtained varnish, thereby obtaining mixed resin powder. Fill the mixed resin powder into a mold with a length of 40mm×80mm and a depth of 0.8mm, and arrange 12μm copper foil (3EC-M3-VLP, made by Mitsui Metals and Mining Co., Ltd.) on both sides at a pressure of 40kg/cm ² and a temperature of 210℃ Vacuum pressing was carried out for 120 minutes to obtain a hardened product with a length of 40 mm×80 mm and a thickness of 0.8 mm. Using the obtained cured product, the electrical characteristics (Dk and Df) and peel strength were measured. In addition, the lowest melt viscosity was measured using a mixed resin powder. These results are shown in Table 1.

>Example 2> In Example 1, the same procedure as in Example 1 was performed except that the blending amount of the PPE-based coupling agent was changed to 5 parts by mass. The results are shown in Table 1.

>Comparative example 1> In Example 1, the PPE-based coupling agent was not blended, except that it was carried out in the same manner as in Example 1. It can be seen that the filler material is agglomerated, and a uniform varnish cannot be prepared. Therefore, no follow-up evaluation was conducted. The results are shown in Table 1.

>Comparative example 2> In Example 1, the PPE-based coupling agent was changed to an equivalent amount of an epoxy-based coupling agent (manufactured by Shin-Etsu Silicone, KBM403, 3-glycidoxypropyltrimethoxysilane, 2.5 parts by mass), Other than that, the same composition is made. Various evaluations and measurements were performed in the same manner as in Example 1. The results are shown in Table 1.

>Comparative Example 3> In Example 2, the PPE-based coupling agent was changed to an equivalent amount of epoxy-based coupling agent (manufactured by Shin-Etsu Silicone, KBM403, 3-glycidoxypropyltrimethoxysilane silane, 5 parts by mass) , Except for that, made the same composition. Various evaluations and measurements were performed in the same manner as in Example 2. The results are shown in Table 1.

>Comparative Example 4> In Example 1, the modified polyphenylene ether compound and the styrene-isoprene-styrene elastomer obtained in Synthesis Example 2 above were not blended. Instead, nitrile rubber (N220S, manufactured by JSR Corporation) was blended. 10 parts by mass, except for the same composition. It can be seen that the components are separated and a uniform varnish cannot be prepared. Therefore, no follow-up evaluation was conducted. The results are shown in Table 1.

[Table 1]

From the above results, it is clear that the resin composition of this embodiment can maintain a low dielectric constant (Dk) and a low dielectric loss factor (Df) while achieving high peel strength and low melt viscosity (Examples 1 and 2). In addition, the manufacturability is also excellent. In contrast to this, in the case where the compound (A) is not blended, there is a possibility that the varnish cannot be manufactured, or even if it can be manufactured, the dielectric loss factor (Df) becomes higher, the peel strength becomes smaller, and the minimum melt viscosity becomes higher. Situation (Comparative Examples 1 to 3). Furthermore, even if the compound (A) is blended, varnish cannot be produced when neither the resin having an aromatic ring structure nor the elastomer having an aromatic ring structure is blended.

Claims (22)

A resin composition containing: Compound (A), which has more than two aromatic ring structures in one molecule and a group represented by -Si(OR ⁰¹ ) _m (R ⁰² ) _3-m ; component (B), At least one of a resin having an aromatic ring structure and an elastomer having an aromatic ring structure; and a filler (C); R ⁰¹ and R ⁰² are each independently a hydrocarbon group, and m is an integer of 1 to 3. The resin composition as claimed in item 1 of the patent application, wherein the compound (A) has a repeating unit containing an aromatic ring structure. A resin composition as claimed in item 2 of the patent application, wherein the repeating unit containing an aromatic ring structure of the compound (A) is polyphenylene ether. A resin composition as claimed in item 1 of the patent scope, wherein the compound (A) includes a compound represented by formula (X); formula (X)

(X) In formula (X), X represents an n-valent organic group containing a polyphenylene ether structure, and R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms. group, A ¹ represents a single bond or a divalent heteroatom-containing linking group of atoms, A ² represents a single bond or a divalent linking group of, m an integer of 1 to 3, the system, n the number of lines 1 to 10. A resin composition as claimed in item 1 of the patent application, wherein the compound (A) includes a compound represented by formula (Y); formula (Y)

(Y) In formula (Y), A ² is a single bond or a divalent linking group, and R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, m is an integer from 1 to 3, and n is a number from 1 to 10. The resin composition according to any one of claims 1 to 5, wherein the weight average molecular weight of the compound (A) is 1,000 or more. The resin composition according to any one of claims 1 to 5, wherein the elastomer having an aromatic ring structure includes a styrene-based elastomer. The resin composition according to any one of items 1 to 5 of the patent application range, wherein the resin having an aromatic ring structure contains a polyphenylene ether compound. For example, in the resin composition of claim 8, the polyphenylene ether compound includes the polyphenylene ether compound represented by the following formula (1);

In formula (1), X represents an aromatic group, -(Y-О)n ₂ -represents a polyphenylene ether structure, and R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkyne Base, n ₁ represents an integer of 1 to 6, n ₂ represents an integer of 1 to 100, and n ₃ represents an integer of 1 to 4. For example, in the resin composition of claim 8, the polyphenylene ether compound has a number average molecular weight of 1,000 or more and 7,000 or less. The resin composition according to any one of items 1 to 5 of the patent application range further contains a maleimide compound. A resin composition as claimed in item 11 of the patent application, wherein the maleimide compound comprises a compound selected from the group consisting of a compound represented by formula (2M), a compound represented by formula (3M), and a compound represented by formula (4M) At least one of the group;

In formula (2M), R ⁴ each independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more;

In formula (3M), R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n ₅ represents an integer of 1 or more and 10 or less;

In formula (4M), R ⁶ each independently represents a hydrogen atom, a methyl group or an ethyl group, and R ⁷ each independently represents a hydrogen atom or a methyl group. A resin composition as claimed in item 12 of the patent application, wherein the maleimide compound includes a compound represented by formula (3M). The resin composition according to any one of items 1 to 5 of the patent application scope further contains a cyanate compound. The resin composition according to any one of items 1 to 5 of the patent application range further contains a flame retardant. The resin composition according to any one of items 1 to 5 of the patent application range, wherein the content of the compound (A) is 1 to 10 parts by mass relative to 100 parts by mass of the resin component. The resin composition according to any one of items 1 to 5 of the patent application range, wherein the total content of the resin having an aromatic ring structure and the elastomer having an aromatic ring structure is 1 to 50 parts by mass relative to 100 parts by mass of the resin component Quality parts. The resin composition according to any one of claims 1 to 5, wherein the content of the filler (C) is 50 to 300 parts by mass relative to 100 parts by mass of the resin component. A prepreg is formed of a base material and a resin composition as described in any one of patent application items 1 to 18. A metal foil-clad laminated board comprising at least one piece of prepreg as claimed in item 19 of the patent application, and metal foil arranged on one or both sides of the prepreg. A resin sheet comprising a support, and a layer formed of the resin composition according to any one of claims 1 to 18 disposed on the surface of the support. A printed wiring board includes an insulating layer and a conductor layer disposed on the surface of the insulating layer; The insulating layer includes a layer formed of the resin composition as described in any one of patent application items 1 to 18.