JP7124410B2 - Resin film for interlayer insulating layer, laminate, printed wiring board, semiconductor device, and method for producing laminate - Google Patents
Resin film for interlayer insulating layer, laminate, printed wiring board, semiconductor device, and method for producing laminate Download PDFInfo
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- JP7124410B2 JP7124410B2 JP2018080066A JP2018080066A JP7124410B2 JP 7124410 B2 JP7124410 B2 JP 7124410B2 JP 2018080066 A JP2018080066 A JP 2018080066A JP 2018080066 A JP2018080066 A JP 2018080066A JP 7124410 B2 JP7124410 B2 JP 7124410B2
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- 150000003672 ureas Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
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- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Organic Insulating Materials (AREA)
- Insulating Bodies (AREA)
- Reinforced Plastic Materials (AREA)
Description
本発明は、層間絶縁層用樹脂フィルム、積層体、プリント配線板、半導体装置及び積層体の製造方法に関する。 The present invention relates to an interlayer insulating layer resin film, a laminate, a printed wiring board, a semiconductor device, and a method for producing a laminate.
近年、地球環境保護の観点から、はんだの鉛フリー化が進行しており、プリント配線板への部品実装時及び半導体パッケージ組み立て時におけるリフロー工程の温度が非常に高くなっている。これに伴って、プリント配線板用の積層板には、耐熱性の向上等による信頼性向上の要求が強まっている。 In recent years, from the viewpoint of global environment protection, the use of lead-free solder is progressing, and the temperature in the reflow process when mounting components on a printed wiring board and when assembling a semiconductor package has become extremely high. Along with this, laminates for printed wiring boards are increasingly required to be improved in reliability by improving heat resistance and the like.
プリント配線板用の積層板としては、エポキシ樹脂を主剤とした樹脂組成物とガラスクロスとを含むプリプレグを硬化及び一体成形化したものが一般的である。
エポキシ樹脂は、絶縁性、耐熱性、成形性、コスト等のバランスに優れるが、近年のプリント配線板の高密度実装及び高多層化構成に伴う耐熱性向上への要請に対応するには、さらなる改良が必要となっており、耐熱性に優れる材料として、ポリビスマレイミド樹脂がプリント配線板用の積層板材料に広く使用されている。
Laminates for printed wiring boards are generally produced by curing and integrally molding a prepreg containing a resin composition containing an epoxy resin as a main component and glass cloth.
Epoxy resin has an excellent balance of insulation, heat resistance, moldability, and cost. Improvement is required, and polybismaleimide resin is widely used as a laminate material for printed wiring boards as a material having excellent heat resistance.
また、近年の電子機器の小型化及び高性能化の流れに伴い、プリント配線板では配線密度の高度化及び高集積化が進展している。そのため、電子部品の実装密度を向上するために、多層プリント配線板の微細配線化の開発が進められている。これらの要求に合致する多層プリント配線板としては、ガラスクロスと樹脂とを含有する積層板又は配線板からなる層(以下、「コア層」ともいう)に、ガラスクロスを含まない層間絶縁層用樹脂フィルムを、プリプレグの代わりに絶縁層(以下、「ビルドアップ層」ともいう)として用いるビルドアップ構造の多層プリント配線板が、軽量化、小型化及び微細化に適したプリント配線板として主流になりつつある。 In addition, along with the trend toward smaller size and higher performance of electronic devices in recent years, printed wiring boards are progressing toward higher wiring density and higher integration. Therefore, in order to improve the mounting density of electronic components, development of finer wiring in multilayer printed wiring boards is underway. As a multilayer printed wiring board that meets these requirements, a layer (hereinafter also referred to as a "core layer") made of a laminate or a wiring board containing glass cloth and a resin is used for an interlayer insulating layer that does not contain glass cloth. A multi-layer printed wiring board with a build-up structure that uses a resin film as an insulating layer (hereinafter also referred to as a "build-up layer") instead of a prepreg is becoming the mainstream as a printed wiring board suitable for weight reduction, miniaturization, and miniaturization. becoming.
しかしながら、パッケージ基板は反りが発生し易く、実装工程等で問題が発生しやすいため、ビルドアップ層には高弾性率、低熱膨張係数といった反りを低減する特性が求められている。そのため、多量の無機充填材を含有する樹脂組成物が検討されている。(例えば、特許文献1参照) However, since the package substrate is likely to warp and problems are likely to occur in the mounting process, etc., the build-up layer is required to have properties such as a high elastic modulus and a low coefficient of thermal expansion to reduce warpage. Therefore, resin compositions containing a large amount of inorganic filler have been investigated. (For example, see Patent Document 1)
一方、多量の無機充填材を含有する樹脂組成物は、層間絶縁層用樹脂フィルムを取り扱う際に端部から樹脂欠けが発生する、折れ目が発生するなど、樹脂フィルムの取り扱い性が悪化するという新たな問題が発生した。樹脂フィルムの取り扱い性を向上させることを目的として、液状エポキシ樹脂を配合する方法が検討されているが、液状エポキシ樹脂は耐デスミア性が低い傾向にある。したがって、低熱膨張係数を実現しつつ、取り扱い性と耐デスミア性とを両立させることが望まれている。
さらには、多量の無機充填材を含有する樹脂組成物を使用するビルドアップ層は、コア層との間にボイドが発生し易くなる問題が確認されており、改善が望まれている。
On the other hand, a resin composition containing a large amount of inorganic fillers is said to deteriorate the handleability of the resin film, such as chipping of the resin from the edges and creases when handling the resin film for the interlayer insulation layer. A new problem has arisen. For the purpose of improving the handleability of the resin film, a method of blending a liquid epoxy resin has been studied, but the liquid epoxy resin tends to have low desmear resistance. Therefore, it is desired to achieve both ease of handling and resistance to desmear while realizing a low coefficient of thermal expansion.
Furthermore, it has been confirmed that the build-up layer using a resin composition containing a large amount of inorganic filler tends to generate voids between itself and the core layer, and improvement is desired.
本発明は、上記事情に鑑みてなされたものであり、取り扱い性及び耐デスミア性に優れ、コア層に積層した場合に、コア層との界面におけるボイドの発生を抑制することができる層間絶縁層用樹脂フィルム、該層間絶縁層用樹脂フィルムを用いた積層体、プリント配線板、半導体装置及び積層体の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an interlayer insulating layer that is excellent in handleability and desmear resistance and can suppress the generation of voids at the interface with the core layer when laminated on the core layer. It is an object of the present invention to provide a resin film for inter-layer insulation layers, a laminate using the resin film for interlayer insulating layers, a printed wiring board, a semiconductor device, and a method for producing the laminate.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、特定の組成を有する樹脂組成物を含有する層間絶縁層用樹脂フィルムが上記目的に沿うものであることを見出し、本発明に到達した。
すなわち、本発明は、下記[1]~[17]に関する。
[1](A)固形エポキシ樹脂と、
(B)1分子中に2個以上のN-置換マレイミド基を有するマレイミド化合物と、
(C)1分子中に2個以上の1級アミノ基を有するアミン化合物と、
(D)エラストマーと、
を含有する熱硬化性樹脂組成物を含有する、層間絶縁層用樹脂フィルム。
[2](D)エラストマーが、エポキシ基、アミノ基、水酸基、メタクリル基、メルカプト基、カルボキシ基及びアルコキシ基からなる群から選択される1種以上の反応性官能基を有する、上記[1]に記載の層間絶縁層用樹脂フィルム。
[3](D)エラストマーが、アクリル系エラストマーである、上記[1]又は[2]に記載の層間絶縁層用樹脂フィルム。
[4]前記熱硬化性樹脂組成物中における(D)エラストマーの含有量が、前記熱硬化性樹脂組成物中の樹脂成分の総和100質量部に対して、5~60質量部である、上記[1]~[3]のいずれかに記載の層間絶縁層用樹脂フィルム。
[5]前記熱硬化性樹脂組成物が、さらに、(E)無機充填材を含有する、上記[1]~[4]のいずれかに記載の層間絶縁層用樹脂フィルム。
[6]前記熱硬化性樹脂組成物中における(E)無機充填材の含有量が、前記熱硬化性樹脂組成物中の樹脂成分の総和100質量部に対して、20~300質量部である、上記[5]に記載の層間絶縁層用樹脂フィルム。
[7]前記熱硬化性樹脂組成物が、さらに、(F)硬化促進剤を含有する、上記[1]~[6]のいずれかに記載の層間絶縁層用樹脂フィルム。
[8](C)1分子中に2個以上の1級アミノ基を有するアミン化合物が、シロキサン骨格を含有する化合物である、上記[1]~[7]のいずれかに記載の層間絶縁層用樹脂フィルム。
[9]プリプレグ又はプリプレグを硬化してなる絶縁層に積層して用いられる、上記[1]~[8]のいずれかに記載の層間絶縁層用樹脂フィルム。
[10]前記プリプレグが、
(a)エポキシ樹脂と、
(b)1分子中に2個以上のN-置換マレイミド基を有するマレイミド化合物と、
(c)1分子中に2個以上の1級アミノ基を有するアミン化合物と、
を含有する熱硬化性樹脂組成物を含有するものである、上記[9]に記載の層間絶縁層用樹脂フィルム。
[11](c)1分子中に2個以上の1級アミノ基を有するアミン化合物が、シロキサン骨格を含有する化合物である、上記[10]に記載の層間絶縁層用樹脂フィルム。
[12]上記[1]~[11]のいずれかに記載の層間絶縁層用樹脂フィルムと、プリプレグ又はプリプレグを硬化してなる絶縁層と、を積層してなる、積層体。
[13]前記プリプレグが、
(a)エポキシ樹脂と、
(b)1分子中に2個以上のN-置換マレイミド基を有するマレイミド化合物と、
(c)1分子中に2個以上の1級アミノ基を有するアミン化合物と、
を含有する熱硬化性樹脂組成物を含有するものである、上記[12]に記載の積層体。
[14](c)1分子中に2個以上の1級アミノ基を有するアミン化合物が、シロキサン骨格を含有する化合物である、上記[13]に記載の積層体。
[15]上記[1]~[11]のいずれかに記載の層間絶縁層用樹脂フィルムを用いて形成される層間絶縁層、又は上記[12]~[14]のいずれかに記載の積層体を用いて形成される層間絶縁層を含有する、プリント配線板。
[16]上記[15]に記載のプリント配線板を含有する、半導体装置。
[17]上記[12]~[14]のいずれかに記載の積層体を製造する方法であって、前記プリプレグを硬化してなる絶縁層の片面又は両面に、上記[1]~[11]のいずれかに記載の層間絶縁層用樹脂フィルムをラミネートする、積層体の製造方法。
The present inventors have made intensive studies to achieve the above object, and as a result, have found that a resin film for an interlayer insulating layer containing a resin composition having a specific composition satisfies the above object. arrived at the invention.
That is, the present invention relates to the following [1] to [17].
[1] (A) a solid epoxy resin;
(B) a maleimide compound having two or more N-substituted maleimide groups in one molecule;
(C) an amine compound having two or more primary amino groups in one molecule;
(D) an elastomer; and
A resin film for an interlayer insulating layer, containing a thermosetting resin composition containing
[2] The above [1], wherein (D) the elastomer has one or more reactive functional groups selected from the group consisting of an epoxy group, an amino group, a hydroxyl group, a methacrylic group, a mercapto group, a carboxyl group and an alkoxy group. The resin film for interlayer insulation layers according to 1.
[3] The resin film for interlayer insulation layers according to the above [1] or [2], wherein (D) the elastomer is an acrylic elastomer.
[4] The content of (D) the elastomer in the thermosetting resin composition is 5 to 60 parts by mass with respect to the total of 100 parts by mass of the resin components in the thermosetting resin composition. The resin film for interlayer insulation layers according to any one of [1] to [3].
[5] The resin film for interlayer insulating layers according to any one of [1] to [4] above, wherein the thermosetting resin composition further contains (E) an inorganic filler.
[6] The content of (E) the inorganic filler in the thermosetting resin composition is 20 to 300 parts by mass with respect to the total 100 parts by mass of the resin components in the thermosetting resin composition. , the resin film for an interlayer insulation layer according to the above [5].
[7] The resin film for interlayer insulation layers according to any one of [1] to [6] above, wherein the thermosetting resin composition further contains (F) a curing accelerator.
[8] (C) The interlayer insulating layer according to any one of [1] to [7] above, wherein the amine compound having two or more primary amino groups in one molecule is a compound containing a siloxane skeleton. resin film for
[9] The resin film for interlayer insulating layers according to any one of the above [1] to [8], which is used by being laminated on a prepreg or an insulating layer formed by curing a prepreg.
[10] The prepreg is
(a) an epoxy resin;
(b) a maleimide compound having two or more N-substituted maleimide groups in one molecule;
(c) an amine compound having two or more primary amino groups in one molecule;
The resin film for interlayer insulating layers according to the above [9], which contains a thermosetting resin composition containing
[11] (c) The resin film for interlayer insulation layers according to the above [10], wherein the amine compound having two or more primary amino groups in one molecule is a compound containing a siloxane skeleton.
[12] A laminate obtained by laminating the interlayer insulation layer resin film according to any one of [1] to [11] above and an insulation layer formed by curing a prepreg or a prepreg.
[13] The prepreg is
(a) an epoxy resin;
(b) a maleimide compound having two or more N-substituted maleimide groups in one molecule;
(c) an amine compound having two or more primary amino groups in one molecule;
The laminate according to [12] above, which contains a thermosetting resin composition containing
[14] (c) The laminate according to [13] above, wherein the amine compound having two or more primary amino groups in one molecule is a compound containing a siloxane skeleton.
[15] An interlayer insulating layer formed using the resin film for interlayer insulating layers according to any one of [1] to [11] above, or the laminate according to any one of [12] to [14] above. A printed wiring board containing an interlayer insulating layer formed using
[16] A semiconductor device comprising the printed wiring board according to [15] above.
[17] A method for producing a laminate according to any one of [12] to [14] above, wherein the insulating layer formed by curing the prepreg is coated with the above [1] to [11] on one or both sides of the insulating layer. A method for producing a laminate, comprising laminating the resin film for an interlayer insulating layer according to any one of the above.
本発明によると、取り扱い性及び耐デスミア性に優れ、コア層に積層した場合に、コア層との界面におけるボイドの発生を抑制することができる層間絶縁層用樹脂フィルム、該層間絶縁層用樹脂フィルムを用いた積層体、プリント配線板、半導体装置及び積層体の製造方法を提供することができる。 According to the present invention, an interlayer insulation layer resin film which is excellent in handleability and desmear resistance and can suppress the generation of voids at the interface with the core layer when laminated on the core layer, and the interlayer insulation layer resin. A laminate using a film, a printed wiring board, a semiconductor device, and a method for producing a laminate can be provided.
以下、本発明の一実施形態について詳述するが、本発明は以下の実施形態に限定されるものではない。 An embodiment of the present invention will be described in detail below, but the present invention is not limited to the following embodiment.
[層間絶縁層用樹脂フィルム]
本実施形態の層間絶縁層用樹脂フィルム(以下、単に「樹脂フィルム」ともいう)は、(A)固形エポキシ樹脂と、(B)1分子中に2個以上のN-置換マレイミド基を有するマレイミド化合物と、(C)1分子中に2個以上の1級アミノ基を有するアミン化合物と、(D)エラストマーと、を含有する熱硬化性樹脂組成物を含有するものである。
なお、本実施形態の樹脂フィルムは、該樹脂フィルムの一方の表面に支持体が付いている「支持体付き樹脂フィルム」の状態であることが好ましく、更に樹脂フィルムの他方の面に保護フィルムが付いている「支持体及び保護フィルム付き樹脂フィルム」の状態であってもよい。
以下、本実施形態の樹脂フィルムに含有される熱硬化性樹脂組成物を「樹脂組成物(I)」とも称する。
[Resin film for interlayer insulating layer]
The resin film for interlayer insulating layers (hereinafter also simply referred to as "resin film") of the present embodiment comprises (A) a solid epoxy resin and (B) a maleimide having two or more N-substituted maleimide groups in one molecule. A thermosetting resin composition containing a compound, (C) an amine compound having two or more primary amino groups in one molecule, and (D) an elastomer.
The resin film of the present embodiment is preferably in the state of a "supported resin film" in which a support is attached to one surface of the resin film, and a protective film is attached to the other surface of the resin film. It may be in the state of "a resin film with a support and a protective film" attached.
Hereinafter, the thermosetting resin composition contained in the resin film of the present embodiment is also referred to as "resin composition (I)".
<(A)固形エポキシ樹脂>
本実施形態の樹脂フィルムは、(A)固形エポキシ樹脂(以下、「(A)成分」ともいう)を含有することにより耐デスミア性に優れたものとなる。
なお、本実施形態における「固形」とは常温(25℃)において流動性を示さない固体状態を呈することを意味し、「液状」とは常温(25℃)において流動性を示す液体状態を呈することを意味する。
<(A) Solid epoxy resin>
The resin film of the present embodiment becomes excellent in desmear resistance by containing (A) a solid epoxy resin (hereinafter also referred to as "component (A)").
In the present embodiment, "solid" means exhibiting a solid state that does not exhibit fluidity at room temperature (25 ° C.), and "liquid" exhibits a liquid state that exhibits fluidity at room temperature (25 ° C.). means that
(A)固形エポキシ樹脂としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、α-ナフトール/クレゾールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ビスフェノールFノボラック型エポキシ樹脂、スチルベン型エポキシ樹脂、トリアジン骨格含有エポキシ樹脂、フルオレン骨格含有エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、ビフェニル型エポキシ樹脂、キシリレン型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、脂環式エポキシ樹脂、多官能フェノール類及びアントラセン等の多環芳香族類のジグリシジルエーテル化合物、これらにリン化合物を導入したリン含有エポキシ樹脂などが挙げられる。これらの中でも、耐デスミア性、耐熱性及び難燃性の観点から、ナフタレン骨格含有型エポキシ樹脂が好ましく、α-ナフトール/クレゾールノボラック型エポキシ樹脂がより好ましい。
(A)固形エポキシ樹脂は、1種を単独で使用してもよいし、2種以上を併用してもよい。
(A) Solid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, α-naphthol/cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenolmethane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type Epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-type epoxy resins, alicyclic epoxy resins, diglycidyl ether compounds of polyfunctional phenols and polycyclic aromatics such as anthracene, and phosphorus-containing epoxies obtained by introducing phosphorus compounds into these A resin etc. are mentioned. Among these, from the viewpoint of desmear resistance, heat resistance and flame retardancy, naphthalene skeleton-containing type epoxy resins are preferred, and α-naphthol/cresol novolac type epoxy resins are more preferred.
(A) A solid epoxy resin may be used individually by 1 type, and may use 2 or more types together.
(A)固形エポキシ樹脂のエポキシ当量は、150~500g/eqが好ましく、150~400g/eqがより好ましく、200~300g/eqがさらに好ましい。
ここで、エポキシ当量は、エポキシ基あたりの樹脂の質量(g/eq)であり、JIS K 7236:2009に準拠して測定することができる。
(A) The epoxy equivalent of the solid epoxy resin is preferably 150 to 500 g/eq, more preferably 150 to 400 g/eq, even more preferably 200 to 300 g/eq.
Here, the epoxy equivalent is the mass (g/eq) of resin per epoxy group, and can be measured according to JIS K 7236:2009.
(A)固形エポキシ樹脂の含有量に特に制限はないが、耐デスミア性、成形性、電気絶縁性及び金属回路との接着強度の観点から、樹脂組成物(I)中の樹脂成分の総和100質量部に対して、1~40質量部が好ましく、3~35質量部がより好ましく、5~20質量部がさらに好ましい。
なお、本実施形態において、樹脂成分とは、(A)~(D)成分、後述する(X)成分及び任意で用いられる樹脂を意味し、後述する硬化促進剤は樹脂成分には含まないものとする。
(A) The content of the solid epoxy resin is not particularly limited. It is preferably 1 to 40 parts by mass, more preferably 3 to 35 parts by mass, and even more preferably 5 to 20 parts by mass.
In the present embodiment, the resin component means the components (A) to (D), the component (X) described later, and an optionally used resin, and the curing accelerator described later is not included in the resin component. and
<(B)1分子中に2個以上のN-置換マレイミド基を有するマレイミド化合物>
本実施形態の樹脂フィルムは、(B)1分子中に2個以上のN-置換マレイミド基を有するマレイミド化合物(以下、単に「(B)マレイミド化合物」又は「(B)成分」ともいう)を含有することにより、コア層との界面におけるボイドの発生を抑制することができる。
(B)マレイミド化合物は、1分子中に2個のN-置換マレイミド基を有するマレイミド化合物であることが好ましい。
(B)マレイミド化合物は、1種を単独で使用してもよいし、2種以上を併用してもよい。
<(B) Maleimide Compound Having Two or More N-Substituted Maleimide Groups in One Molecule>
The resin film of the present embodiment comprises (B) a maleimide compound having two or more N-substituted maleimide groups in one molecule (hereinafter also simply referred to as "(B) maleimide compound" or "(B) component"). By containing it, it is possible to suppress the generation of voids at the interface with the core layer.
(B) Maleimide compound is preferably a maleimide compound having two N-substituted maleimide groups in one molecule.
(B) A maleimide compound may be used individually by 1 type, and may use 2 or more types together.
(B)マレイミド化合物としては、複数のマレイミド基のうちの任意の2個のマレイミド基の間に芳香族炭化水素基を有さずに脂肪族炭化水素基を有するマレイミド化合物、複数のマレイミド基のうちの任意の2個のマレイミド基の間に芳香族炭化水素基を含有するマレイミド化合物(以下、「芳香族マレイミド化合物」ともいう)等が挙げられる。
これらの中でも、耐熱性、誘電特性、ガラス転移温度、熱膨張係数、成形性及びコア層との界面におけるボイドの発生を抑制する観点から、芳香族マレイミド化合物が好ましく、1分子中に2個のN-置換マレイミド基を有する芳香族マレイミド化合物がより好ましい。芳香族マレイミド化合物は、任意に選択した2つのマレイミド基の組み合わせのいずれかの間に芳香族炭化水素基を含有していればよい。
(B) As the maleimide compound, a maleimide compound having an aliphatic hydrocarbon group without an aromatic hydrocarbon group between any two maleimide groups out of a plurality of maleimide groups, A maleimide compound containing an aromatic hydrocarbon group between two arbitrary maleimide groups (hereinafter also referred to as an “aromatic maleimide compound”) and the like can be mentioned.
Among these, aromatic maleimide compounds are preferred from the viewpoint of heat resistance, dielectric properties, glass transition temperature, coefficient of thermal expansion, moldability, and suppression of void generation at the interface with the core layer. More preferred are aromatic maleimide compounds having N-substituted maleimide groups. The aromatic maleimide compound may contain an aromatic hydrocarbon group between any two arbitrarily selected combinations of maleimide groups.
1分子中に2個のN-置換マレイミド基を有する芳香族マレイミド化合物としては、下記一般式(B-1)で表される化合物が好ましい。 As the aromatic maleimide compound having two N-substituted maleimide groups in one molecule, a compound represented by the following general formula (B-1) is preferred.
(式中、RB1及びRB2は、各々独立に、炭素数1~5の脂肪族炭化水素基又はハロゲン原子を示す。XB1は、炭素数1~5のアルキレン基、炭素数2~5のアルキリデン基、-O-、-C(=O)-、-S-、-S-S-、スルホニル基、カルボニルオキシ基、単結合又は下記一般式(B1-1-1)で表される基を示す。m及びnは、各々独立に、0~4の整数である。)
(In the formula, R 1 B1 and R 2 B2 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; X B1 is an alkylene group having 1 to 5 carbon atoms; an alkylidene group, -O-, -C(=O)-, -S-, -S-S-, a sulfonyl group, a carbonyloxy group, a single bond or represented by the following general formula (B1-1-1) group, m and n are each independently an integer of 0 to 4.)
(式中、RB3及びRB4は、各々独立に、炭素数1~5の脂肪族炭化水素基又はハロゲン原子を示す。XB2は、炭素数1~5のアルキレン基、炭素数2~5のアルキリデン基、-O-、-C(=O)-、-S-、-S-S-、スルホニル基、カルボニルオキシ基又は単結合を示す。m1及びn1は、各々独立に、0~4の整数である。)
(In the formula, R B3 and R B4 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; X B2 is an alkylene group having 1 to 5 carbon atoms; an alkylidene group, -O-, -C(=O)-, -S-, -S-S-, a sulfonyl group, a carbonyloxy group or a single bond m1 and n1 are each independently 0 to 4 is an integer of
上記一般式(B-1)中、RB1及びRB2が示す炭素数1~5の脂肪族炭化水素基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基、n-ペンチル基等が挙げられる。
RB1及びRB2が示すハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
XB1が示す炭素数1~5のアルキレン基としては、メチレン基、1,2-ジメチレン基、1,3-トリメチレン基、1,4-テトラメチレン基、1,5-ペンタメチレン基等が挙げられる。これらの中でも、メチレン基が好ましい。
XB1が示す炭素数2~5のアルキリデン基としては、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。
m及びnは、各々独立に、0~4の整数であり、0~2の整数が好ましく、0又は1の整数がより好ましく、0がさらに好ましい。
In general formula (B-1) above, the aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R 1 B1 and R 2 B2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like.
Halogen atoms represented by R 2 B1 and R 2 B2 include fluorine, chlorine, bromine and iodine atoms.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X B1 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group and 1,5-pentamethylene group. be done. Among these, a methylene group is preferred.
The alkylidene group having 2 to 5 carbon atoms represented by X B1 includes ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and the like.
Each of m and n is independently an integer of 0 to 4, preferably an integer of 0 to 2, more preferably an integer of 0 or 1, and still more preferably 0.
上記一般式(B1-1-1)中、RB3及びRB4が示す炭素数1~5の脂肪族炭化水素基、ハロゲン原子としては、上記RB1及びRB2の場合と同じものが挙げられ、好ましいものも同じである。
XB2が示す炭素数1~5のアルキレン基、炭素数2~5のアルキリデン基としては、上記XB1が示す炭素数1~5のアルキレン基、炭素数2~5のアルキリデン基と同じものが挙げられ、好ましいものも同じである。
XB2としては、上記選択肢の中でも、炭素数2~5のアルキリデン基が好ましく、イソプロピリデン基がより好ましい。
m1及びn1は0~4の整数であり、入手容易性の観点から、いずれも、好ましくは0~2の整数、より好ましくは0又は1、さらに好ましくは0である。
また、前記一般式(B1-1-1)は、下記一般式(B1-1-1’)で表されることが好ましい。
In the above general formula (B1-1-1), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R 6 B3 and R 6 B4 are the same as in the case of R 6 B1 and R 6 B2 . , and the preferred ones are also the same.
The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X B2 are the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X B1 . and the preferred ones are also the same.
Among the above options, X B2 is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferably an isopropylidene group.
m1 and n1 are integers of 0 to 4, and both are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0 from the viewpoint of availability.
Further, the general formula (B1-1-1) is preferably represented by the following general formula (B1-1-1').
(式中、XB2、RB3、RB4、m1及びn1は、一般式(B1-1-1)中のものと同じであり、好ましいものも同じである。)
(Wherein, X B2 , R B3 , R B4 , m1 and n1 are the same as in general formula (B1-1-1), and preferred ones are also the same.)
(B)マレイミド化合物としては、ビス(4-マレイミドフェニル)メタン、ポリフェニルメタンマレイミド、ビス(4-マレイミドフェニル)エーテル、ビス(4-マレイミドフェニル)スルホン、3,3’-ジメチル-5,5’-ジエチル-4,4’-ジフェニルメタンビスマレイミド、4-メチル-1,3-フェニレンビスマレイミド、m-フェニレンビスマレイミド、2,2-ビス[4-(4-マレイミドフェノキシ)フェニル]プロパン等が挙げられる。これらの中でも、反応率が高く、より高耐熱性化できるという観点及びコア層との界面におけるボイドの発生を抑制する観点から、ビス(4-マレイミドフェニル)メタン、ビス(4-マレイミドフェニル)スルホン、3,3’-ジメチル-5,5’-ジエチル-4,4’-ジフェニルメタンビスマレイミド、2,2-ビス[4-(4-マレイミドフェノキシ)フェニル]プロパンが好ましく、ビス(4-マレイミドフェニル)メタン、2,2-ビス[4-(4-マレイミドフェノキシ)フェニル]プロパンがより好ましい。 (B) Maleimide compounds include bis(4-maleimidophenyl)methane, polyphenylmethane maleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3′-dimethyl-5,5 '-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, etc. mentioned. Among these, bis(4-maleimidophenyl)methane and bis(4-maleimidophenyl)sulfone are preferred from the viewpoints of high reaction rate, higher heat resistance, and suppression of void generation at the interface with the core layer. , 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and bis(4-maleimidophenyl ) methane and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane are more preferred.
(B)マレイミド化合物の含有量に特に制限はないが、耐熱性、誘電特性、ガラス転移温度、熱膨張係数、成形性及びコア層との界面におけるボイドの発生を抑制する観点から、樹脂組成物(I)中の樹脂成分の総和100質量部に対して、30~95質量部が好ましく、35~90質量部がより好ましく、40~85質量部がさらに好ましく、45~80質量部が特に好ましい。 (B) The content of the maleimide compound is not particularly limited. It is preferably 30 to 95 parts by mass, more preferably 35 to 90 parts by mass, even more preferably 40 to 85 parts by mass, and particularly preferably 45 to 80 parts by mass, relative to 100 parts by mass of the total resin components in (I). .
<(C)1分子中に2個以上の1級アミノ基を有するアミン化合物>
本実施形態の樹脂フィルムは、(C)1分子中に2個以上の1級アミノ基を有するアミン化合物(以下、単に「(C)アミン化合物」又は「(C)成分」ともいう)を含有することにより、コア層との界面におけるボイドの発生を抑制することができる。
(C)アミン化合物は、1分子中に2個の1級アミノ基を有するアミン化合物であることが好ましい。
(C)アミン化合物は、1種を単独で使用してもよいし、2種以上を併用してもよい。
<(C) Amine Compound Having Two or More Primary Amino Groups in One Molecule>
The resin film of the present embodiment contains (C) an amine compound having two or more primary amino groups in one molecule (hereinafter simply referred to as "(C) amine compound" or "(C) component"). By doing so, it is possible to suppress the generation of voids at the interface with the core layer.
(C) The amine compound is preferably an amine compound having two primary amino groups in one molecule.
(C) An amine compound may be used individually by 1 type, and may use 2 or more types together.
(C)アミン化合物としては、脂肪族アミン化合物、芳香族アミン化合物等が挙げられる。芳香族アミン化合物としては、下記一般式(C-1)で表される芳香族ジアミン化合物が好ましい。 (C) Amine compounds include aliphatic amine compounds and aromatic amine compounds. As the aromatic amine compound, an aromatic diamine compound represented by the following general formula (C-1) is preferable.
(式中、RC1及びRC2は、各々独立に、炭素数1~5のアルキル基、炭素数1~5のアルコキシ基、ハロゲン原子、水酸基、カルボキシ基又はスルホン酸基を示す。XC1は、炭素数1~5のアルキレン基、炭素数2~5のアルキリデン基、-O-、スルホニル基、-C(=O)-、フルオレニレン基、フェニレンジオキシ基又は単結合を示す。v及びwは、各々独立に、0~4の整数である。)
(In the formula, R 1 C1 and R 2 C2 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, a carboxy group or a sulfonic acid group. X C1 is , an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, —O—, a sulfonyl group, —C(═O)—, a fluorenylene group, a phenylenedioxy group, or a single bond v and w are each independently an integer from 0 to 4.)
RC1及びRC2が示す炭素数1~5のアルキル基、ハロゲン原子としては、上記一般式(B-1)中のRB1及びRB2と同じものが挙げられ、炭素数1~5のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基等が挙げられる。
XC1が示す炭素数1~5のアルキレン基及び炭素数2~5のアルキリデン基としては、上記一般式(B-1)中のXB1と同じものが挙げられる。
Examples of the alkyl group having 1 to 5 carbon atoms and the halogen atom represented by R 1 C1 and R 2 C2 include the same groups as those described for R 1 B1 and R 2 B2 in the general formula (B-1) above, and alkoxy groups having 1 to 5 carbon atoms. Examples of the group include methoxy group, ethoxy group, propoxy group and the like.
The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X 1 C1 include the same groups as X 1 B1 in the general formula (B-1).
(C)アミン化合物は、シロキサン骨格を含有する化合物であることが好ましく、1分子中に2個の1級アミノ基を有するシロキサン化合物がより好ましく、両末端に1級アミノ基を有するシロキサン化合物がさらに好ましい。
両末端に1級アミノ基を有するシロキサン化合物としては、下記一般式(C-2)で表される化合物が好ましい。
(C) The amine compound is preferably a compound containing a siloxane skeleton, more preferably a siloxane compound having two primary amino groups in one molecule, and a siloxane compound having primary amino groups at both ends. More preferred.
As the siloxane compound having primary amino groups at both ends, a compound represented by the following general formula (C-2) is preferred.
(式中、RC3、RC4、RC5及びRC6は、各々独立に、アルキル基、フェニル基又は置換フェニル基を示し、XC2及びXC3は、各々独立に、2価の有機基を示す。sは1~100の整数を示す。)
(Wherein, R C3 , R C4 , R C5 and R C6 each independently represent an alkyl group, a phenyl group or a substituted phenyl group, and X C2 and X C3 each independently represent a divalent organic group. s is an integer from 1 to 100.)
上記一般式(C-2)中、RC3、RC4、RC5及びRC6が示すアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基、n-ペンチル基等が挙げられる。該アルキル基としては、炭素数1~5のアルキル基が好ましく、炭素数1~3のアルキル基がより好ましく、メチル基がさらに好ましい。
置換フェニル基におけるフェニル基が有する置換基としては、炭素数1~5のアルキル基、炭素数2~5のアルケニル基、炭素数2~5のアルキニル基等が挙げられる。炭素数1~5のアルキル基としては、上記したものと同じものが挙げられる。炭素数2~5のアルケニル基としては、ビニル基、アリル基等が挙げられる。炭素数2~5のアルキニル基としては、エチニル基、プロパルギル基等が挙げられる。
RC3、RC4、RC5及びRC6としては、いずれも炭素数1~5のアルキル基が好ましく、メチル基がより好ましい。
sは、低熱膨張性の観点から、1~100の整数であり、相溶性及び高弾性化の観点から、5~50の整数が好ましく、10~40の整数がより好ましい。
上記一般式(C-2)中、XC2及びXC3が示す2価の有機基としては、アルキレン基、アルケニレン基、アルキニレン基、アリーレン基、-O-又はこれらが組み合わされた2価の連結基等が挙げられる。アルキレン基としては、メチレン基、1,2-ジメチレン基、1,3-トリメチレン基、1,4-テトラメチレン基、1,5-ペンタメチレン基等の炭素数1~10のアルキレン基が挙げられる。アルケニレン基としては、炭素数2~10のアルケニレン基が挙げられる。アルキニレン基としては、炭素数2~10のアルキニレン基が挙げられる。アリーレン基としては、フェニレン基、ナフチレン基等の炭素数6~20のアリーレン基が挙げられる。これらの中でも、アルキレン基が好ましく、1,3-トリメチレン基がより好ましい。
In general formula (C-2) above, examples of alkyl groups represented by R C3 , R C4 , R C5 and R C6 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
Examples of substituents of the phenyl group in the substituted phenyl group include alkyl groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, and alkynyl groups having 2 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms are the same as those described above. Examples of alkenyl groups having 2 to 5 carbon atoms include vinyl groups and allyl groups. The alkynyl group having 2 to 5 carbon atoms includes ethynyl group, propargyl group and the like.
Each of R C3 , R C4 , R C5 and R C6 is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group.
s is an integer of 1 to 100 from the viewpoint of low thermal expansion, preferably an integer of 5 to 50, more preferably an integer of 10 to 40 from the viewpoint of compatibility and high elasticity.
In general formula (C-2) above, the divalent organic group represented by X 1 C2 and X 1 C3 includes an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O—, or a combination of these divalent linkages. and the like. The alkylene group includes an alkylene group having 1 to 10 carbon atoms such as a methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, and 1,5-pentamethylene group. . The alkenylene group includes alkenylene groups having 2 to 10 carbon atoms. The alkynylene group includes an alkynylene group having 2 to 10 carbon atoms. The arylene group includes arylene groups having 6 to 20 carbon atoms such as phenylene group and naphthylene group. Among these, an alkylene group is preferred, and a 1,3-trimethylene group is more preferred.
両末端に1級アミノ基を有するシロキサン化合物のアミノ基当量は、100~6,000g/eqが好ましく、400~2,000g/eqがより好ましく、600~1,500g/eqがさらに好ましい。 The amino group equivalent weight of the siloxane compound having primary amino groups at both terminals is preferably 100 to 6,000 g/eq, more preferably 400 to 2,000 g/eq, and even more preferably 600 to 1,500 g/eq.
(C)アミン化合物は、市販品を用いることができる。(C)アミン化合物の市販品としては、例えば、両末端に1級アミノ基を有するシロキサン化合物である「PAM-E」(アミノ基当量130)、「KF-8010」(アミノ基当量430)、「X-22-161A」(アミノ基当量800)、「X-22-161B」(アミノ基当量1,500)、「KF-8012」(アミノ基当量2,200)、「KF-8008」(アミノ基当量5,700)〔以上、信越化学工業株式会社製〕、「BY16-871」(アミノ基当量130)、「BY16-853U」(アミノ基当量460)〔以上、東レダウコーニング株式会社製〕等が挙げられる。なお、アミノ基当量の単位はg/eqである。 (C) Amine compound can use a commercial item. (C) Commercially available amine compounds include, for example, "PAM-E" (amino group equivalent weight: 130), "KF-8010" (amino group equivalent weight: 430), which are siloxane compounds having primary amino groups at both ends, "X-22-161A" (amino group equivalent weight 800), "X-22-161B" (amino group equivalent weight 1,500), "KF-8012" (amino group equivalent weight 2,200), "KF-8008" ( Amino group equivalent 5,700) [manufactured by Shin-Etsu Chemical Co., Ltd.], "BY16-871" (amino group equivalent 130), "BY16-853U" (amino group equivalent 460) [manufactured by Toray Dow Corning Co., Ltd. ] etc. are mentioned. The unit of amino group equivalent is g/eq.
(C)アミン化合物の具体例としては、ジアミノベンジジン、ジアミノジフェニルメタン、ジアミノジフェニルエーテル、ジアミノジフェニルスルホン、3,3’-ジクロロ-4,4’-ジアミノビフェニル、3,3’-ジメトキシ-4,4’-ジアミノビフェニル、3,3’-ジメチル-4,4’-ジアミノビフェニル、3,3’-ジクロロ-4,4’-ジアミノビフェニル、3,3’-ジメチル-4,4’-ジアミノビフェニル-6,6’-ジスルホン酸、2,2’,5,5’-テトラクロロ-4,4’-ジアミノビフェニル、4,4’-メチレン-ビス(2-クロロアニリン)、1,3’-ビス(4-アミノフェノキシ)ベンゼン、2,2’-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、ビス[4-(4-アミノフェノキシ)フェニル]スルホン、ビス[4-(3-アミノフェノキシ)フェニル]スルホン、4,4’-ビス(4-アミノフェノキシ)ビフェニル、2,2’-ビス[4-(4-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、1,4’-ビス(4-アミノフェノキシ)ベンゼン、4,4’-ジアミノジフェニルスルフィド、2,2’-ジメチル-4,4’-ジアミノビフェニル、4,4’-ジアミノ-3,3’-ビフェニルジオール、9,9’-ビス(4-アミノフェニル)フルオレン、o-トリジンスルホン、上記した1分子中に少なくとも2個の1級アミノ基を有するシロキサン化合物等が挙げられる。 (C) Specific examples of the amine compound include diaminobenzidine, diaminodiphenylmethane, diaminodiphenylether, diaminodiphenylsulfone, 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′. -diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl-6 ,6′-disulfonic acid, 2,2′,5,5′-tetrachloro-4,4′-diaminobiphenyl, 4,4′-methylene-bis(2-chloroaniline), 1,3′-bis( 4-aminophenoxy)benzene, 2,2′-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy) phenyl]sulfone, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4'-bis(4-aminophenoxy ) benzene, 4,4′-diaminodiphenyl sulfide, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-3,3′-biphenyldiol, 9,9′-bis(4 -aminophenyl)fluorene, o-tolysine sulfone, the above-mentioned siloxane compounds having at least two primary amino groups in one molecule, and the like.
(C)アミン化合物の含有量に特に制限はないが、低反り性、寸法安定性、低熱膨張性、低弾性、耐熱性、金属回路との接着性及びコア層との界面におけるボイドの発生を抑制する観点から、樹脂組成物(I)中の樹脂成分の総和100質量部に対して、1~40質量部が好ましく、2~30質量部がより好ましく、3~25質量部がさらに好ましい。 (C) There are no particular restrictions on the content of the amine compound, but it is effective in reducing warpage, dimensional stability, low thermal expansion, low elasticity, heat resistance, adhesion to metal circuits, and formation of voids at the interface with the core layer. From the viewpoint of suppression, it is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 3 to 25 parts by mass, per 100 parts by mass of the total resin components in the resin composition (I).
<(X)変性ポリイミド>
本実施形態に用いられる樹脂組成物(I)は、(B)マレイミド化合物及び(C)アミン化合物を反応させてなる(X)変性ポリイミド(以下、「(X)成分」ともいう)を含有していてもよい。
本実施形態においては、(X)変性ポリイミドを含有することは、すなわち(B)マレイミド化合物及び(C)アミン化合物を含有することと同義である。したがって、樹脂組成物(I)が(X)変性ポリイミドを含有するとき、樹脂組成物(I)は、(B)マレイミド化合物及び/又は(C)アミン化合物を含有していなくてもよいし、(B)マレイミド化合物及び(C)アミン化合物からなる群から選択される1つ以上を含有していてもよい。
(X)変性ポリイミドは、1種を単独で使用してもよいし、2種以上を併用してもよい。
<(X) modified polyimide>
The resin composition (I) used in the present embodiment contains (X) a modified polyimide (hereinafter also referred to as "(X) component") obtained by reacting (B) a maleimide compound and (C) an amine compound. may be
In the present embodiment, containing (X) modified polyimide is synonymous with containing (B) a maleimide compound and (C) an amine compound. Therefore, when the resin composition (I) contains (X) the modified polyimide, the resin composition (I) may not contain (B) the maleimide compound and/or (C) the amine compound, It may contain one or more selected from the group consisting of (B) a maleimide compound and (C) an amine compound.
(X) Modified polyimide may be used alone or in combination of two or more.
(X)変性ポリイミドは、(B)成分と(C)成分とを反応させて得られるものであり、(B)成分由来の構造単位(B’)と、(C)成分由来の構造単位(C’)と、を含有するものである。
(B)成分と(C)成分との反応方法に特に制限はなく、反応温度は、生産性及び十分に反応を進行させる観点から、例えば、70~200℃であり、反応時間は、例えば、0.5~10時間である。
(X) Modified polyimide is obtained by reacting the component (B) and the component (C), and the structural unit (B') derived from the component (B) and the structural unit derived from the component (C) ( C′) and
There is no particular limitation on the reaction method of component (B) and component (C), the reaction temperature is, for example, 70 to 200° C. from the viewpoint of productivity and sufficient progress of the reaction, and the reaction time is, for example, 0.5 to 10 hours.
(B)成分と(C)成分との反応は、有機溶媒中で行うことが好ましい。有機溶媒としては、エタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶媒;ケトン系溶媒;エステル系溶媒;エーテル系溶媒;芳香族系溶媒;窒素原子含有溶媒;硫黄原子含有溶媒などが挙げられる。これらの中でも、溶解性、低毒性及び揮発性が高く残溶媒として残り難いという観点から、プロピレングリコールモノメチルエーテルが好ましい。 It is preferable to carry out the reaction of the component (B) and the component (C) in an organic solvent. Examples of organic solvents include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents; ester solvents; ether solvents; aromatic solvents; Contained solvent etc. are mentioned. Among these, propylene glycol monomethyl ether is preferable from the viewpoint of high solubility, low toxicity, high volatility, and less residual solvent.
(X)変性ポリイミドの含有量は、構造単位(B’)及び構造単位(C’)の含有量を、各々の原料である(B)マレイミド化合物及び(C)アミン化合物の含有量に換算して決定すればよい。
例えば、樹脂組成物(I)が、(B)成分及び(C)成分を含有せずに、(X)変性ポリイミドを含有する場合、樹脂組成物(I)中の構造単位(B’)の量から換算される原料(B)成分の含有量、並びに、樹脂組成物(I)中の構造単位(C’)の量から換算される原料(C)成分の含有量が、上記した(B)成分及び(C)成分の好適な含有量の範囲となることが好ましい。
また、例えば、樹脂組成物(I)が、(B)成分及び(C)成分と、(X)変性ポリイミドと、を含有する場合、樹脂組成物(I)中の構造単位(B’)の量から換算される原料(B)成分の含有量と、別に配合した(B)成分との合計含有量が、上記した(B)成分の好適な含有量の範囲となることが好ましく、樹脂組成物(I)中の構造単位(C’)の量から換算される原料(C)成分の含有量と、別に配合した(C)成分との合計含有量が、上記した(C)成分の好適な含有量の範囲となることが好ましい。
(X) The content of the modified polyimide is obtained by converting the content of the structural unit (B') and the structural unit (C') into the content of the raw material (B) maleimide compound and (C) amine compound. can be determined by
For example, when the resin composition (I) does not contain the components (B) and (C) and contains (X) the modified polyimide, the structural unit (B') in the resin composition (I) The content of the raw material (B) component converted from the amount and the content of the raw material (C) component converted from the amount of the structural unit (C') in the resin composition (I) are the above-mentioned (B ) component and (C) component preferably fall within suitable ranges of content.
Further, for example, when the resin composition (I) contains components (B) and (C), and (X) a modified polyimide, the structural unit (B') in the resin composition (I) It is preferable that the total content of the raw material (B) component converted from the amount and the separately blended (B) component is within the preferred content range of the (B) component described above, and the resin composition The total content of the content of the raw material (C) component converted from the amount of the structural unit (C') in the substance (I) and the separately blended component (C) is the above-described preferred component (C) content range.
樹脂組成物(I)が(X)変性ポリイミドを含有する場合、その含有量は、耐熱性、誘電特性、ガラス転移温度、熱膨張係数、成形性及びコア層との界面におけるボイドの発生を抑制する観点から、樹脂組成物(I)中の樹脂成分の総和100質量部に対して、30~80質量部が好ましく、40~70質量部がより好ましく、50~60質量部がさらに好ましい。 When the resin composition (I) contains (X) the modified polyimide, its content controls heat resistance, dielectric properties, glass transition temperature, coefficient of thermal expansion, moldability, and void generation at the interface with the core layer. 30 to 80 parts by mass, more preferably 40 to 70 parts by mass, and even more preferably 50 to 60 parts by mass based on 100 parts by mass of the total resin components in the resin composition (I).
<(D)エラストマー>
本実施形態の樹脂フィルムは、(D)エラストマー(以下、「(D)成分」ともいう)を含有することにより、取り扱い性に優れたものとなる。
(D)エラストマーは、1種を単独で使用してもよいし、2種以上を併用してもよい。
<(D) Elastomer>
The resin film of the present embodiment becomes excellent in handleability by containing (D) an elastomer (hereinafter also referred to as "(D) component").
(D) Elastomer may be used alone or in combination of two or more.
(D)エラストマーとしては、ポリエステル系エラストマー、ポリアミド系エラストマー、ポリウレタン系エラストマー、スチレン系エラストマー、アクリル系エラストマー、これらの誘導体等が挙げられる。これらの中でも、耐熱性及び絶縁信頼性の観点から、スチレン系エラストマーが好ましく、銅箔との接着性を良好に保ちながら樹脂組成物の弾性率を低減する観点からは、アクリル系エラストマーがより好ましい。 (D) Elastomers include polyester elastomers, polyamide elastomers, polyurethane elastomers, styrene elastomers, acrylic elastomers, and derivatives thereof. Among these, styrene elastomers are preferable from the viewpoint of heat resistance and insulation reliability, and acrylic elastomers are more preferable from the viewpoint of reducing the elastic modulus of the resin composition while maintaining good adhesion to the copper foil. .
(D)エラストマーは、分子末端及び分子鎖中のうち少なくとも一方に反応性官能基を有することが好ましい。反応性官能基を有することにより、他の樹脂成分との相溶性が向上し、樹脂フィルムの取り扱い性を向上させる効果がより顕著に発現すると共に、樹脂組成物の硬化時に発生する内部応力を効果的に低減することができ、結果として、基板の反りを低減することも可能となる。
反応性官能基としては、エポキシ基、アミノ基、水酸基、アクリル基、メタクリル基、メルカプト基、カルボキシ基、アルコキシ基、アミド基、イソシアナト基、ビニル基等が挙げられる。これらの中でも、低熱膨張性、金属回路との接着強度及び樹脂フィルムの取り扱い性を向上させる観点から、エポキシ基、アミノ基、水酸基、メタクリル基、メルカプト基、カルボキシ基及びアルコキシ基からなる群から選ばれる1種以上が好ましく、エポキシ基がより好ましい。
(D)エラストマーが、反応性官能基を有する場合、その官能基の含有量は、0.05~0.40eq/kgが好ましく、0.10~0.30eq/kgがより好ましく、0.15~0.25eq/kgがさらに好ましい。
(D) The elastomer preferably has a reactive functional group on at least one of the molecular terminal and the molecular chain. By having a reactive functional group, the compatibility with other resin components is improved, the effect of improving the handleability of the resin film is more pronounced, and the internal stress generated during curing of the resin composition is effectively reduced. As a result, it is also possible to reduce the warpage of the substrate.
Examples of reactive functional groups include epoxy group, amino group, hydroxyl group, acrylic group, methacrylic group, mercapto group, carboxy group, alkoxy group, amide group, isocyanato group, vinyl group and the like. Among these, it is selected from the group consisting of epoxy group, amino group, hydroxyl group, methacrylic group, mercapto group, carboxy group and alkoxy group from the viewpoint of low thermal expansion, adhesive strength with metal circuits, and improvement in handleability of resin films. is preferably one or more, more preferably an epoxy group.
(D) When the elastomer has a reactive functional group, the content of the functional group is preferably 0.05 to 0.40 eq/kg, more preferably 0.10 to 0.30 eq/kg, and 0.15 ~0.25 eq/kg is more preferred.
(スチレン系エラストマー)
スチレン系エラストマーとしては、スチレン-ブタジエン-スチレンブロックコポリマー等のスチレン-ブタジエン共重合体;スチレン-イソプレン-スチレンブロックコポリマー等のスチレン-イソプレン共重合体;スチレン-エチレン-ブチレン-スチレンブロックコポリマー、スチレン-エチレン-プロピレン-スチレンブロックコポリマーなどが挙げられる。スチレン系エラストマーの原料モノマーとしては、スチレンの他に、α-メチルスチレン、3-メチルスチレン、4-プロピルスチレン、4-シクロヘキシルスチレン等のスチレン誘導体を用いることができる。これらの中でも、スチレン-ブタジエン共重合体、スチレン-イソプレン共重合体が好ましく、これらの共重合体の二重結合部分を水素添加した水添スチレン-ブタジエン共重合樹脂、水添スチレン-イソプレン共重合樹脂等がより好ましく、水添スチレン-ブタジエン共重合樹脂がさらに好ましい。
(Styrene-based elastomer)
Styrene-based elastomers include styrene-butadiene copolymers such as styrene-butadiene-styrene block copolymers; styrene-isoprene copolymers such as styrene-isoprene-styrene block copolymers; styrene-ethylene-butylene-styrene block copolymers; Examples include ethylene-propylene-styrene block copolymers. Styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used as raw material monomers for styrene-based elastomers in addition to styrene. Among these, styrene-butadiene copolymers and styrene-isoprene copolymers are preferred, and hydrogenated styrene-butadiene copolymer resins and hydrogenated styrene-isoprene copolymers obtained by hydrogenating the double bond portions of these copolymers. A resin or the like is more preferable, and a hydrogenated styrene-butadiene copolymer resin is even more preferable.
(アクリル系エラストマー)
アクリル系エラストマーとしては、少なくともアクリル酸エステルに由来する構造単位を含む分子で形成される重合体である。アクリル系エラストマーは、分子中に異なる複数種のアクリル酸エステルに由来する構造単位を含んでいてもよく、さらに、アクリル酸エステル以外の単量体に由来する構造単位を含んでもよい。また、アクリル系エラストマーは、複数種のアクリル酸エステルに由来する構造単位からなるものであってもよい。
アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸t-ブチル、アクリル酸ペンチル、アクリル酸ヘキシル、アクリル酸シクロヘキシル、アクリル酸オクチル、アクリル酸デシル、アクリル酸ラウリル、アクリル酸ベンジル等が挙げられる。
上記アクリル酸エステル以外の単量体としては、アクリロニトリル、アクリルアミド、アクリル酸、メタクリル酸、メタクリル酸エステル、スチレン、エチレン、プロピレン、ブタジエン等のビニル系単量体が挙げられる。アクリル酸エステル以外の単量体は、1種を単独で使用してもよいし、2種以上を併用してもよい。
(acrylic elastomer)
The acrylic elastomer is a polymer formed from molecules containing at least a structural unit derived from an acrylic acid ester. The acrylic elastomer may contain structural units derived from different types of acrylic esters in the molecule, and may further contain structural units derived from monomers other than acrylic esters. Moreover, the acrylic elastomer may be composed of structural units derived from a plurality of kinds of acrylic acid esters.
Acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, and acrylic acid. octyl, decyl acrylate, lauryl acrylate, benzyl acrylate and the like.
Examples of monomers other than the above acrylic acid esters include vinyl monomers such as acrylonitrile, acrylamide, acrylic acid, methacrylic acid, methacrylic acid esters, styrene, ethylene, propylene and butadiene. Monomers other than acrylic acid esters may be used alone or in combination of two or more.
アクリル系エラストマーの重量平均分子量(Mw)に特に制限はないが、10,000~2,000,000が好ましく、50,000~1,200,000がより好ましく、100,000~900,000がさらに好ましく、500,000~900,000が特に好ましい。重量平均分子量(Mw)が10,000以上であれば、低弾性率を維持し易い傾向にあり、2,000,000以下であれば、相溶性及び流動性が良好となる傾向にある。
なお、本明細書中、重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)(東ソー株式会社製)により、標準ポリスチレンの検量線を用いて測定したものである。
The weight average molecular weight (Mw) of the acrylic elastomer is not particularly limited, but is preferably 10,000 to 2,000,000, more preferably 50,000 to 1,200,000, and more preferably 100,000 to 900,000. More preferably, 500,000 to 900,000 is particularly preferred. When the weight average molecular weight (Mw) is 10,000 or more, it tends to be easy to maintain a low elastic modulus, and when it is 2,000,000 or less, compatibility and fluidity tend to be good.
In this specification, the weight average molecular weight is measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation) using a standard polystyrene calibration curve.
(D)エラストマーの含有量に特に制限はないが、耐デスミア性及び樹脂フィルムの取り扱い性を向上させる観点から、樹脂組成物(I)中の樹脂成分の総和100質量部に対して、5~60質量部が好ましく、7~50質量部がより好ましく、8~30質量部がさらに好ましく、10~20質量部が特に好ましい。 The content of the elastomer (D) is not particularly limited, but from the viewpoint of improving the desmear resistance and the handleability of the resin film, 5 to 5 parts per 100 parts by mass of the total resin components in the resin composition (I) 60 parts by mass is preferable, 7 to 50 parts by mass is more preferable, 8 to 30 parts by mass is even more preferable, and 10 to 20 parts by mass is particularly preferable.
<(E)無機充填材>
樹脂組成物(I)は、さらに、(E)無機充填材(以下、「(E)成分」ともいう)を含有することが好ましい。
(E)無機充填材としては、シリカ、アルミナ、硫酸バリウム、タルク、マイカ、カオリン、ベーマイト、ベリリア、チタン酸バリウム、チタン酸カリウム、チタン酸ストロンチウム、チタン酸カルシウム、炭酸アルミニウム、水酸化マグネシウム、水酸化アルミニウム、ホウ酸アルミニウム、ケイ酸アルミニウム、炭酸カルシウム、ケイ酸カルシウム、ケイ酸マグネシウム、ホウ酸亜鉛、スズ酸亜鉛、酸化亜鉛、酸化チタン、炭化ケイ素、窒化ケイ素、窒化ホウ素、焼成クレー等のクレー、ガラス短繊維、ガラス粉、中空ガラスビーズなどが挙げられる。ガラスとしては、Eガラス、Tガラス、Dガラス等が挙げられる。
(E)無機充填材は、1種を単独で使用してもよいし、2種以上を併用してもよい。
<(E) Inorganic filler>
The resin composition (I) preferably further contains (E) an inorganic filler (hereinafter also referred to as "component (E)").
(E) Inorganic fillers include silica, alumina, barium sulfate, talc, mica, kaolin, boehmite, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, and water. Aluminum oxide, aluminum borate, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, zinc borate, zinc stannate, zinc oxide, titanium oxide, silicon carbide, silicon nitride, boron nitride, clay such as calcined clay , short glass fibers, glass powder, and hollow glass beads. Glass includes E glass, T glass, D glass, and the like.
(E) An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
(E)無機充填材としては、誘電特性、耐熱性及び低熱膨張性の観点から、シリカが好ましい。シリカとしては、例えば、湿式法で製造され含水率の高い沈降シリカ、乾式法で製造され結合水等をほとんど含まない乾式法シリカ等が挙げられる。乾式法シリカとしては、さらに、製造法の違いにより破砕シリカ、フュームドシリカ、溶融シリカ(溶融球状シリカ)等が挙げられる。(E)無機充填材に用いられるシリカは、低熱膨張性及び樹脂に充填した際の高流動性の観点から、溶融シリカが好ましい。 (E) As the inorganic filler, silica is preferable from the viewpoint of dielectric properties, heat resistance and low thermal expansion. Silica includes, for example, precipitated silica produced by a wet method and having a high water content, dry-process silica produced by a dry method and containing almost no bound water, and the like. Dry process silica further includes pulverized silica, fumed silica, fused silica (fused spherical silica), etc. depending on the production method. Silica used as the inorganic filler (E) is preferably fused silica from the viewpoint of low thermal expansion and high fluidity when filled in a resin.
(E)無機充填材の平均粒子径は、0.1~10μmが好ましく、0.2~5μmがより好ましく、0.3~1μmがさらに好ましい。平均粒子径が0.1μm以上であると、樹脂に高充填した際の流動性を良好に保つことができ、10μm以下であると、粗大粒子の混入確率を低減し、粗大粒子起因の不良の発生を抑えることができる。
なお、本明細書中、平均粒子径とは、粒子の全体積を100%として粒子径による累積度数分布曲線を求めたとき、体積50%に相当する点の粒子径のことであり、レーザー回折散乱法を用いた粒度分布測定装置等で測定することができる。
(E) The inorganic filler preferably has an average particle size of 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.3 to 1 μm. When the average particle diameter is 0.1 μm or more, good fluidity can be maintained when the resin is highly filled. occurrence can be suppressed.
In this specification, the average particle size is the particle size at the point corresponding to 50% volume when the cumulative frequency distribution curve by particle size is obtained with the total volume of the particles being 100%, and laser diffraction It can be measured with a particle size distribution analyzer using a scattering method.
(E)無機充填材は、シランカップリング剤、シリコーンオリゴマー等の表面処理剤で表面処理されたものであってもよい。表面処理された(E)無機充填材を用いると、(E)無機充填材と樹脂成分との接着力が向上し、(E)無機充填材の脱落が抑制され、表面粗さが低下する傾向にある。
シランカップリング剤としては、アミノシラン系カップリング剤、エポキシシラン系カップリング剤、フェニルシラン系カップリング剤、アルキルシラン系カップリング剤、アルケニルシラン系カップリング剤、シロキサン系カップリング剤等が挙げられる。
シランカップリング剤等の表面処理剤を用いる場合、その添加方式は、樹脂組成物(I)中に(E)無機充填材を配合した後、表面処理剤を添加する、いわゆるインテグラルブレンド処理方式であってもよい。
(E) The inorganic filler may be surface-treated with a surface treatment agent such as a silane coupling agent or silicone oligomer. When the surface-treated (E) inorganic filler is used, the adhesive strength between the (E) inorganic filler and the resin component is improved, the (E) inorganic filler is suppressed from falling off, and the surface roughness tends to decrease. It is in.
Silane coupling agents include aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, siloxane coupling agents, and the like. .
When using a surface treatment agent such as a silane coupling agent, the addition method is a so-called integral blend treatment method in which the surface treatment agent is added after blending the (E) inorganic filler in the resin composition (I). may be
樹脂組成物(I)が(E)無機充填材を含有する場合、その含有量に特に制限はないが、低熱膨張性及び樹脂フィルムの取り扱い性の観点から、樹脂組成物(I)中の樹脂成分の総和100質量部に対して、20~300質量部が好ましく、50~250質量部がより好ましく、80~200質量部がさらに好ましく、100~170質量部が特に好ましい。 When the resin composition (I) contains (E) an inorganic filler, the content is not particularly limited, but from the viewpoint of low thermal expansion and handleability of the resin film, the resin in the resin composition (I) It is preferably 20 to 300 parts by mass, more preferably 50 to 250 parts by mass, even more preferably 80 to 200 parts by mass, and particularly preferably 100 to 170 parts by mass based on 100 parts by mass of the total amount of the components.
<(F)硬化促進剤>
樹脂組成物(I)は、さらに、(F)硬化促進剤(以下、「(F)成分」ともいう)を含有することが好ましい。
(F)硬化促進剤としては、ナフテン酸亜鉛、ナフテン酸コバルト、オクチル酸スズ、オクチル酸コバルト、ビスアセチルアセトナートコバルト(II)、トリスアセチルアセトナートコバルト(III)等の有機金属塩;有機リン系化合物;イミダゾール化合物及びその誘導体;第2級アミン化合物、第3級アミン化合物、第4級アンモニウム塩などが挙げられる。これらの中でも、低熱膨張性の観点から、有機リン系化合物が好ましい。
(F)硬化促進剤は、1種を単独で使用してもよいし、2種以上を併用してもよい。
<(F) Curing accelerator>
The resin composition (I) preferably further contains (F) a curing accelerator (hereinafter also referred to as "component (F)").
(F) curing accelerators include organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III); compounds; imidazole compounds and derivatives thereof; secondary amine compounds, tertiary amine compounds, quaternary ammonium salts and the like. Among these, organic phosphorus compounds are preferable from the viewpoint of low thermal expansion.
(F) The curing accelerator may be used alone or in combination of two or more.
樹脂組成物(I)が(F)硬化促進剤を含有する場合、その含有量に特に制限はないが、樹脂組成物(I)中の樹脂成分の総和100質量部に対して、耐熱性、難燃性、経日安定性及び硬化性の観点から、0.1~10質量部が好ましく、0.3~5質量部がより好ましく、0.5~3質量部がさらに好ましい。 When the resin composition (I) contains (F) a curing accelerator, the content is not particularly limited. From the viewpoint of flame retardancy, aging stability and curability, it is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, even more preferably 0.5 to 3 parts by mass.
<その他の成分>
樹脂組成物(I)は、本発明の目的を阻害しない範囲で、上記各成分以外の熱硬化性樹脂(以下、「その他の熱硬化性樹脂」ともいう)、難燃剤、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤、接着性向上剤等を含有していてもよい。
その他の熱硬化性樹脂としては、上記各成分以外の、フェノール樹脂、不飽和イミド樹脂、シアネート樹脂、イソシアネート樹脂、ベンゾオキサジン樹脂、オキセタン樹脂、アミノ樹脂、不飽和ポリエステル樹脂、アリル樹脂、ジシクロペンタジエン樹脂、シリコーン樹脂、トリアジン樹脂、メラミン樹脂等が挙げられる。
難燃剤としては、臭素及び/又は塩素を含有するハロゲン系難燃剤;トリフェニルホスフェート、トリクレジルホスフェート、トリスジクロロプロピルホスフェート、リン酸エステル系化合物、赤リン等のリン系難燃剤;スルファミン酸グアニジン、硫酸メラミン、ポリリン酸メラミン、メラミンシアヌレート等の窒素系難燃剤;シクロホスファゼン、ポリホスファゼン等のホスファゼン系難燃剤などが挙げられる。
紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤等が挙げられる。
酸化防止剤としては、ヒンダードフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤等が挙げられる。
光重合開始剤としては、ベンゾフェノン類、ベンジルケタール類、チオキサントン系の光重合開始剤等が挙げられる。
蛍光増白剤としては、スチルベン誘導体の蛍光増白剤等が挙げられる。
接着性向上剤としては、尿素シラン等の尿素化合物;シラン系カップリング剤、チタネート系カップリング剤、アルミネート系カップリング剤等のカップリング剤などが挙げられる。
<Other ingredients>
The resin composition (I) is a thermosetting resin other than the above components (hereinafter also referred to as "other thermosetting resin"), a flame retardant, an ultraviolet absorber, an oxidation It may contain an inhibitor, a photoinitiator, a fluorescent whitening agent, an adhesion improver, and the like.
Other thermosetting resins other than the above components include phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, and dicyclopentadiene. resins, silicone resins, triazine resins, melamine resins, and the like.
Flame retardants include halogen flame retardants containing bromine and/or chlorine; triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric acid ester compounds, red phosphorus and other phosphorus flame retardants; guanidine sulfamate. , melamine sulfate, melamine polyphosphate, and melamine cyanurate; and phosphazene-based flame retardants such as cyclophosphazene and polyphosphazene.
Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers.
Antioxidants include hindered phenol antioxidants, hindered amine antioxidants, and the like.
Examples of photopolymerization initiators include benzophenones, benzyl ketals, thioxanthone-based photopolymerization initiators, and the like.
Examples of fluorescent brightening agents include fluorescent brightening agents of stilbene derivatives.
Examples of the adhesion improver include urea compounds such as urea silane; coupling agents such as silane coupling agents, titanate coupling agents and aluminate coupling agents;
樹脂組成物(I)は、樹脂フィルムの製造を容易にするため、各成分が有機溶媒中に溶解及び/又は分散されたワニスの状態としてもよい。
有機溶媒としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒;メチルセロソルブ等のアルコール系溶媒;テトラヒドロフラン等のエーテル系溶媒;トルエン、キシレン、メシチレン等の芳香族系溶媒などが挙げられる。有機溶媒は、1種を単独で使用してもよいし、2種以上を併用してもよい。
ワニスの固形分濃度は、40~90質量%が好ましく、50~80質量%がより好ましい。ワニスの固形分濃度が上記範囲内であると、塗工性を良好に保ち、樹脂フィルムの厚さ等を適切な範囲に調整し易くなる。
Resin composition (I) may be in the form of a varnish in which each component is dissolved and/or dispersed in an organic solvent in order to facilitate production of a resin film.
Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alcohol solvents such as methyl cellosolve; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene. . An organic solvent may be used individually by 1 type, and may use 2 or more types together.
The solid content concentration of the varnish is preferably 40-90% by mass, more preferably 50-80% by mass. When the solid content concentration of the varnish is within the above range, good coatability can be maintained, and the thickness of the resin film and the like can be easily adjusted within an appropriate range.
樹脂組成物(I)は、上記各成分を混合することにより製造することができる。混合方法としては、公知の方法を適用することができ、ニーダー、ボールミル、ビーズミル、3本ロール、ナノマイザー等の公知の混練及び分散方法を適用することができる。 The resin composition (I) can be produced by mixing the above components. As a mixing method, a known method can be applied, and a known kneading and dispersing method such as a kneader, ball mill, bead mill, triple roll, nanomizer, etc. can be applied.
<支持体>
本実施形態の樹脂フィルムは、そのいずれか一方の面に支持体が設けられたものであってもよい。
支持体としては、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィンのフィルム;ポリエチレンテレフタレート(以下、「PET」ともいう)、ポリエチレンナフタレート等のポリエステルのフィルム;ポリカーボネートフィルム、ポリイミドフィルム等の各種プラスチックフィルムなどが挙げられる。また、銅箔、アルミニウム箔等の金属箔、離型紙などを使用してもよい。支持体及び後述する保護フィルムには、マット処理、コロナ処理等の表面処理が施してあってもよい。また、支持体及び後述する保護フィルムにはシリコーン樹脂系離型剤、アルキッド樹脂系離型剤、フッ素樹脂系離型剤等による離型処理が施してあってもよい。
支持体の厚さは、例えば、10~150μmであり、25~50μmであってもよい。
<Support>
The resin film of this embodiment may have a support provided on one of its surfaces.
Examples of the support include polyolefin films such as polyethylene, polypropylene and polyvinyl chloride; polyester films such as polyethylene terephthalate (hereinafter also referred to as "PET") and polyethylene naphthalate; various plastic films such as polycarbonate films and polyimide films. is mentioned. Metal foil such as copper foil and aluminum foil, release paper, and the like may also be used. The support and the protective film described later may be subjected to surface treatment such as matte treatment and corona treatment. Further, the support and the protective film to be described later may be subjected to release treatment with a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, or the like.
The thickness of the support is, for example, 10-150 μm, and may be 25-50 μm.
<保護フィルム>
支持体上に形成された樹脂フィルムの、支持体とは反対側の面には、保護フィルムを設けてもよい。保護フィルムの厚さは、例えば、1~40μmである。保護フィルムを積層することにより、樹脂フィルムの表面へのゴミ等の付着及び傷付きを防止することができる。保護フィルムの材質は、支持体と同様のものが挙げられる。
<Protective film>
A protective film may be provided on the surface of the resin film formed on the support opposite to the support. The thickness of the protective film is, for example, 1-40 μm. By laminating the protective film, it is possible to prevent dust from adhering to the surface of the resin film and damage to the surface of the resin film. Examples of the material of the protective film include those similar to those of the support.
<樹脂フィルムの製造方法>
本実施形態の樹脂フィルムの製造方法に特に制限はなく、公知の方法を利用できる。
例えば、まず、樹脂フィルムに含有させる各成分を有機溶媒の存在下で混合することで、ワニス状の樹脂組成物(I)として、該ワニスを支持体へ塗布した後、有機溶媒を除去し、樹脂組成物(I)を半硬化(B-ステージ化)することによって、支持体付き樹脂フィルムを形成することができる。
<Method for producing resin film>
The method for producing the resin film of the present embodiment is not particularly limited, and known methods can be used.
For example, first, each component to be contained in the resin film is mixed in the presence of an organic solvent to form a varnish-like resin composition (I), and the varnish is applied to a support, then the organic solvent is removed, By semi-curing (B-staging) the resin composition (I), a resin film with a support can be formed.
ワニスを塗布する方法としては、コンマコーター、バーコーター、キスコーター、ロールコーター、グラビアコーター、ダイコーター等の公知の塗工装置を用いることができる。これらの塗工装置は、膜厚によって、適宜選択することが好ましい。
塗布後の乾燥条件は、樹脂フィルム中の揮発成分(主に有機溶媒)の含有量が、例えば、10質量%以下となる条件であり、6質量%以下となる条件が好ましい。
乾燥温度及び乾燥時間は、有機溶媒の使用量、有機溶媒の沸点等によって異なるが、例えば、30~60質量%の有機溶媒を含むワニスの場合、50~150℃で3~10分間乾燥させることにより、樹脂フィルムを好適に形成することができる。
得られる樹脂フィルムの最低溶融粘度は、800~5,000MPa・sとなるように乾燥することが好ましい。
As a method for applying the varnish, a known coating device such as a comma coater, bar coater, kiss coater, roll coater, gravure coater and die coater can be used. These coating devices are preferably selected as appropriate depending on the film thickness.
Drying conditions after coating are such that the content of volatile components (mainly organic solvents) in the resin film is, for example, 10% by mass or less, preferably 6% by mass or less.
The drying temperature and drying time vary depending on the amount of organic solvent used and the boiling point of the organic solvent. Thus, a resin film can be suitably formed.
The minimum melt viscosity of the resulting resin film is preferably 800 to 5,000 MPa·s.
本実施形態の樹脂フィルムの厚さは、求める性能に応じて適宜決定すればよいが、導体層上に配置して用いる場合、回路基板の導体層を埋め込む観点から、回路基板の導体層の厚さ以上であってもよい。具体的には、樹脂フィルムの厚さは、1~100μmが好ましく、3~50μmがより好ましく、4~40μmがさらに好ましい。 The thickness of the resin film of the present embodiment may be appropriately determined according to the required performance. may be greater than or equal to Specifically, the thickness of the resin film is preferably 1 to 100 μm, more preferably 3 to 50 μm, even more preferably 4 to 40 μm.
本実施形態の樹脂フィルムは、回路基板、ソルダーレジスト、アンダーフィル材、ダイボンディング材、半導体封止材、穴埋め樹脂、部品埋め込み樹脂等の層間絶縁層を形成するために用いられる樹脂フィルムとして好適である。これらの中でも、プリント配線板の製造において層間絶縁層を形成するために用いられることが好ましく、後述する本実施形態の積層体の製造において層間絶縁層を形成するため用いられることがより好ましい。 The resin film of the present embodiment is suitable as a resin film used for forming interlayer insulating layers such as circuit boards, solder resists, underfill materials, die bonding materials, semiconductor encapsulating materials, hole-filling resins, component-embedding resins, and the like. be. Among these, it is preferably used for forming an interlayer insulating layer in the manufacture of a printed wiring board, and more preferably used for forming an interlayer insulating layer in the manufacture of a laminate of this embodiment, which will be described later.
[積層体]
本実施形態の積層体は、本実施形態の層間絶縁層用樹脂フィルムと、プリプレグ又はプリプレグを硬化してなる絶縁層と、を積層してなる積層体である。
[Laminate]
The laminate of this embodiment is a laminate obtained by laminating the interlayer insulating layer resin film of this embodiment and an insulating layer formed by curing a prepreg or a prepreg.
<プリプレグ>
本実施形態の積層体に用いられるプリプレグは、(a)エポキシ樹脂(以下、「(a)成分」ともいう)、(b)1分子中に2個以上のN-置換マレイミド基を有するマレイミド化合物(以下、「(b)成分」ともいう)と、(c)1分子中に2個以上の1級アミノ基を有するアミン化合物(以下、「(c)成分」ともいう)と、を含有する熱硬化性樹脂組成物(以下、「樹脂組成物(II)」ともいう)を含有するプリプレグであることが好ましい。なお、本実施形態に用いられる樹脂組成物(II)は、樹脂組成物(I)と同様、(b)成分及び(c)成分を、(b)成分及び(c)成分を反応させてなる(x)変性ポリイミドとして含有する態様も好ましい。
また、樹脂組成物(II)は、上記各成分に加え、(d)エラストマー(以下、「(d)成分」ともいう)、(e)無機充填材(以下、「(e)成分」ともいう)及び(f)硬化促進剤(以下、「(f)成分」ともいう)からなる群から選択される少なくとも1種を含有していてもよい。
なお、(a)成分は上記(A)成分、(b)成分は上記(B)成分、(c)成分は上記(C)成分、(d)成分は上記(D)成分、(e)成分は上記(E)成分、(f)成分は上記(F)成分、(x)成分は上記(X)成分と、各々同じものが挙げられ、好ましい種類も同じである。また、これらは、各々について、1種を単独で使用してもよく、2種以上を併用してもよい。
<Prepreg>
The prepreg used in the laminate of the present embodiment includes (a) an epoxy resin (hereinafter also referred to as "component (a)"), and (b) a maleimide compound having two or more N-substituted maleimide groups in one molecule. (hereinafter also referred to as "(b) component") and (c) an amine compound having two or more primary amino groups in one molecule (hereinafter also referred to as "(c) component") A prepreg containing a thermosetting resin composition (hereinafter also referred to as "resin composition (II)") is preferred. The resin composition (II) used in the present embodiment is obtained by reacting the components (b) and (c) with the components (b) and (c) in the same manner as the resin composition (I). (x) A mode in which it is contained as a modified polyimide is also preferred.
In addition to the above components, the resin composition (II) includes (d) an elastomer (hereinafter also referred to as "(d) component"), (e) an inorganic filler (hereinafter also referred to as "(e) component") ) and (f) a curing accelerator (hereinafter also referred to as “component (f)”).
The component (a) is the component (A), the component (b) is the component (B), the component (c) is the component (C), the component (d) is the component (D), and the component (e). is the same as the above component (E), (f) is the same as the above component (F), and (x) is the same as the above component (X), and the preferred types are also the same. Moreover, these may be used individually by 1 type about each, and may use 2 or more types together.
本実施形態の積層体は、コア層及びビルドアップ層の両方に、1分子中に2個以上のN-置換マレイミド基を有するマレイミド化合物と1分子中に2個以上の1級アミノ基を有するアミン化合物又は変性ポリイミドを使用することで、コア層とビルドアップ層との界面におけるボイドの発生を顕著に抑制することができる。その機構は定かではないが、コア層及びビルドアップ層の両方に同一又は類似する樹脂を使用することで、コア層とビルドアップ層との親和性が向上することで濡れ性が向上し、これによってボイドの発生が抑制されたものと考えられる。
したがって、コア層とビルドアップ層との界面におけるボイドの発生を抑制する観点から、本実施形態の積層体に使用する樹脂フィルム及びプリプレグは、各々を構成する樹脂組成物の組成が近いことが好ましい。具体的には、樹脂組成物(II)が、(a)~(f)成分及び(x)成分からなる群から選択される1種以上を含有する場合、当該成分の構造は、樹脂組成物(I)が含有する(A)~(F)成分及び(X)成分のうち、対応する成分の構造と同一であるか、類似していることが好ましい。
The laminate of the present embodiment has a maleimide compound having two or more N-substituted maleimide groups per molecule and two or more primary amino groups per molecule in both the core layer and the buildup layer. By using an amine compound or modified polyimide, the generation of voids at the interface between the core layer and the buildup layer can be significantly suppressed. Although the mechanism is not clear, by using the same or similar resin for both the core layer and the buildup layer, the affinity between the core layer and the buildup layer is improved, thereby improving the wettability. It is thought that the generation of voids was suppressed by the
Therefore, from the viewpoint of suppressing the generation of voids at the interface between the core layer and the buildup layer, it is preferable that the resin film and the prepreg used in the laminate of the present embodiment have similar resin compositions. . Specifically, when the resin composition (II) contains one or more selected from the group consisting of components (a) to (f) and component (x), the structure of the component is the same as that of the resin composition Among components (A) to (F) and component (X) contained in (I), it is preferred that the structure is the same as or similar to that of the corresponding component.
樹脂組成物(II)が(a)成分を含有する場合、樹脂組成物(II)中における(a)成分の含有量は、耐デスミア性、成形性、電気絶縁性及び金属回路との接着強度の観点から、樹脂組成物(II)中の樹脂成分の総和100質量部に対して、1~85質量部が好ましく、5~70質量部がより好ましく、10~50質量部がさらに好ましく、15~30質量部が特に好ましい。 When the resin composition (II) contains the component (a), the content of the component (a) in the resin composition (II) determines desmear resistance, moldability, electrical insulation, and adhesive strength with a metal circuit. from the viewpoint of 100 parts by mass of the total resin components in the resin composition (II), preferably 1 to 85 parts by mass, more preferably 5 to 70 parts by mass, even more preferably 10 to 50 parts by mass, 15 ~30 parts by weight is particularly preferred.
樹脂組成物(II)が(b)成分を含有する場合、樹脂組成物(II)中における(b)成分の含有量は、耐熱性、誘電特性、ガラス転移温度、熱膨張係数、成形性及びビルドアップ層との界面におけるボイドの発生を抑制する観点から、樹脂組成物(II)中の樹脂成分の総和100質量部に対して、5~80質量部が好ましく、10~70質量部がより好ましく、15~60質量部がさらに好ましく、20~50質量部がよりさらに好ましく、25~40質量部が特に好ましい。 When the resin composition (II) contains the component (b), the content of the component (b) in the resin composition (II) depends on heat resistance, dielectric properties, glass transition temperature, coefficient of thermal expansion, moldability and From the viewpoint of suppressing the generation of voids at the interface with the buildup layer, it is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, with respect to 100 parts by mass of the total resin components in the resin composition (II). It is preferably 15 to 60 parts by mass, even more preferably 20 to 50 parts by mass, and particularly preferably 25 to 40 parts by mass.
樹脂組成物(II)が(c)成分を含有する場合、樹脂組成物(II)中における(c)成分の含有量は、低反り性、寸法安定性、低熱膨張性、低弾性、耐熱性、金属回路との接着性及びコア層との界面におけるボイドの発生を抑制する観点から、樹脂組成物(II)中の樹脂成分の総和100質量部に対して、1~40質量部が好ましく、2~25質量部がより好ましく、5~15質量部がさらに好ましい。 When the resin composition (II) contains the (c) component, the content of the (c) component in the resin composition (II) is low warpage, dimensional stability, low thermal expansion, low elasticity, and heat resistance. 1 to 40 parts by mass per 100 parts by mass of the total resin components in the resin composition (II) is preferable from the viewpoint of adhesion with the metal circuit and suppression of void generation at the interface with the core layer, 2 to 25 parts by mass is more preferable, and 5 to 15 parts by mass is even more preferable.
樹脂組成物(II)が(x)成分を含有する場合、樹脂組成物(II)中における(x)成分の含有量は、耐熱性、誘電特性、ガラス転移温度、熱膨張係数、成形性及びコア層との界面におけるボイドの発生を抑制する観点から、樹脂組成物(II)中の樹脂成分の総和100質量部に対して、10~80質量部が好ましく、20~60質量部がより好ましく、30~50質量部がさらに好ましい。 When the resin composition (II) contains the component (x), the content of the component (x) in the resin composition (II) depends on heat resistance, dielectric properties, glass transition temperature, coefficient of thermal expansion, moldability and From the viewpoint of suppressing the generation of voids at the interface with the core layer, it is preferably 10 to 80 parts by mass, more preferably 20 to 60 parts by mass, based on 100 parts by mass of the total resin components in the resin composition (II). , 30 to 50 parts by mass is more preferable.
樹脂組成物(II)が(d)成分を含有する場合、樹脂組成物(II)中における(d)成分の含有量は、耐デスミア性及び樹脂フィルムの取り扱い性を向上させる観点から、樹脂組成物(II)中の樹脂成分の総和100質量部に対して、5~55質量部が好ましく、10~50質量部がより好ましく、20~45質量部がさらに好ましく、30~40質量部が特に好ましい。 When the resin composition (II) contains the component (d), the content of the component (d) in the resin composition (II) is adjusted from the viewpoint of improving the desmear resistance and the handleability of the resin film. 5 to 55 parts by mass, more preferably 10 to 50 parts by mass, still more preferably 20 to 45 parts by mass, and particularly 30 to 40 parts by mass with respect to 100 parts by mass of the total resin components in the substance (II) preferable.
樹脂組成物(II)が(e)成分を含有する場合、樹脂組成物(II)中における(e)成分の含有量は、耐熱性、難燃性、経日安定性及び硬化性の観点から、樹脂組成物(II)中の樹脂成分の総和100質量部に対して、20~300質量部が好ましく、50~250質量部がより好ましく、80~200質量部がさらに好ましく、100~170質量部が特に好ましい。 When the resin composition (II) contains the component (e), the content of the component (e) in the resin composition (II) is determined from the viewpoint of heat resistance, flame retardancy, aging stability and curability. , with respect to 100 parts by mass of the total resin components in the resin composition (II), preferably 20 to 300 parts by mass, more preferably 50 to 250 parts by mass, even more preferably 80 to 200 parts by mass, 100 to 170 parts by mass Part is particularly preferred.
樹脂組成物(II)が(f)成分を含有する場合、樹脂組成物(II)中における(f)成分の含有量は、低熱膨張性、回路埋め込み性及び樹脂フィルムの取り扱い性の観点から、樹脂組成物(II)中の樹脂成分の総和100質量部に対して、0.1~10質量部が好ましく、0.3~5質量部がより好ましく、0.5~3質量部がさらに好ましい。 When the resin composition (II) contains the (f) component, the content of the (f) component in the resin composition (II) is, from the viewpoint of low thermal expansion, circuit embedding and handling of the resin film, It is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the total resin components in the resin composition (II). .
樹脂組成物(II)は、本発明の目的を阻害しない範囲で、上記各成分以外のその他の成分を含有していてもよい。その他の成分としては、樹脂組成物(I)が含有していてもよいその他の成分と同じものが挙げられる。 The resin composition (II) may contain components other than the components described above as long as the objects of the present invention are not impaired. Other components include the same as other components that may be contained in the resin composition (I).
樹脂組成物(II)は、上記各成分を混合することにより製造することができる。混合方法は、樹脂組成物(I)と同じ方法を適用することができる。 The resin composition (II) can be produced by mixing the above components. As for the mixing method, the same method as for the resin composition (I) can be applied.
(プリプレグの製造方法)
プリプレグは、例えば、樹脂組成物(II)を、基材に含浸する方法により製造することができる。具体的には、本実施形態の樹脂組成物(II)を、基材に含浸した後、例えば、加熱等により半硬化することにより、基材と半硬化した樹脂組成物(II)とを含有するプリプレグを製造することができる。
樹脂組成物(II)を基材に含浸する方法は、例えば、基材を上記ワニスに浸漬する方法、各種コーターにより塗布する方法、スプレーによる吹き付ける方法等が挙げられる。これらの中でも、含浸性の観点から、基材をワニスに浸漬する方法が好ましい。
樹脂組成物(II)を基材に含浸した後、例えば、100~200℃で1~30分間、加熱乾燥し、樹脂組成物(II)を半硬化させて、プリプレグを製造することができる。
(Prepreg manufacturing method)
A prepreg can be produced, for example, by impregnating a substrate with the resin composition (II). Specifically, after the resin composition (II) of the present embodiment is impregnated into a substrate, it is semi-cured, for example, by heating, so that the substrate and the semi-cured resin composition (II) are included. prepreg can be manufactured.
Methods for impregnating the substrate with the resin composition (II) include, for example, a method of immersing the substrate in the varnish, a method of coating with various coaters, and a method of spraying. Among these, the method of immersing the substrate in the varnish is preferable from the viewpoint of impregnation.
After the substrate is impregnated with the resin composition (II), it is dried by heating at 100 to 200° C. for 1 to 30 minutes, and the resin composition (II) is semi-cured to produce a prepreg.
プリプレグに用いられる基材としては、例えば、各種の電気絶縁材料用積層板に用いられている周知のものが使用できる。その材質としては、例えば、Eガラス、Dガラス、Sガラス、Qガラス等の無機物繊維;ポリイミド、ポリエステル、テトラフルオロエチレン等の有機繊維;炭素繊維及びこれらの混合物などが挙げられる。
これらの基材は、例えば、織布、不織布、ロービンク、チョップドストランドマット、サーフェシングマット等の形状を有する。基材の材質及び形状は、目的とする成形物の用途及び性能により選択すればよく、必要により、単独又は2種類以上の材質及び形状を組み合わせることができる。
基材は、シランカップリング剤等で表面処理したもの又は機械的に開繊処理を施したものが、耐熱性、耐湿性及び加工性の面から好適である。
基材の厚さは、例えば、約0.03~0.5mmである。
プリプレグ中における樹脂組成物(II)の含有量は、20~90質量%が好ましい。
As the substrate used for the prepreg, for example, well-known substrates used for laminates for various electrical insulating materials can be used. Materials thereof include, for example, inorganic fibers such as E glass, D glass, S glass and Q glass; organic fibers such as polyimide, polyester and tetrafluoroethylene; carbon fibers and mixtures thereof.
These substrates are in the form of, for example, woven fabrics, non-woven fabrics, roving, chopped strand mats, surfacing mats, and the like. The material and shape of the base material may be selected depending on the intended use and performance of the molded product, and if necessary, two or more types of materials and shapes can be combined.
The substrate is preferably surface-treated with a silane coupling agent or the like or mechanically fiber-opened in terms of heat resistance, moisture resistance and workability.
The thickness of the substrate is, for example, about 0.03-0.5 mm.
The content of the resin composition (II) in the prepreg is preferably 20-90% by mass.
(積層体の製造方法)
本実施形態の積層体は、上記プリプレグ又は上記プリプレグを硬化してなる絶縁層に、本実施形態の樹脂フィルムをラミネートして製造することができる。
以下、プリプレグを硬化してなる絶縁層に本実施形態の樹脂フィルムをラミネートする積層体の製造方法について説明する。
プリプレグを硬化してなる絶縁層は、例えば、上記プリプレグを単独又は2~20枚重ねて、その片面又は両面に、銅、アルミニウム等の金属箔を配置した構成で積層成形して製造することができる。積層成形の条件としては、例えば、加熱温度が100~250℃、加熱時間が0.1~5時間、圧着圧力が0.2~10MPaである。
続いて、得られた成形物を銅エッチング液に浸漬することにより両面の金属箔をエッチングして、上記プリプレグを硬化してなる絶縁層が得られる。
(Laminate manufacturing method)
The laminate of the present embodiment can be produced by laminating the resin film of the present embodiment on the prepreg or the insulating layer obtained by curing the prepreg.
A method for manufacturing a laminate in which the resin film of the present embodiment is laminated on an insulating layer formed by curing a prepreg will be described below.
The insulating layer formed by curing the prepreg can be produced, for example, by laminating and molding the prepreg alone or by stacking 2 to 20 sheets of the prepreg and placing a metal foil such as copper or aluminum on one or both sides of the prepreg. can. The conditions for lamination molding are, for example, a heating temperature of 100 to 250° C., a heating time of 0.1 to 5 hours, and a pressing pressure of 0.2 to 10 MPa.
Subsequently, the obtained molding is immersed in a copper etchant to etch the metal foils on both sides, thereby obtaining an insulating layer formed by curing the prepreg.
次に、上記で得られた絶縁層の片面又は両面に本実施形態の樹脂フィルムをラミネートする。上記ラミネートにおいて、樹脂フィルムが保護フィルムを有している場合には該保護フィルムを除去した後、樹脂フィルムを加圧及び加熱しながら絶縁層に圧着する。
本実施形態の樹脂フィルムにおいては、真空ラミネート法により減圧下で回路基板にラミネートする方法が好ましい。ラミネートにおける圧着温度(ラミネート温度)は、例えば、70~140℃であり、圧着圧力は、例えば、0.1~1.1MPaであり、空気圧20mmHg(26.7hPa)以下の減圧下でラミネートすることが好ましい。また、ラミネートの方法は、バッチ式であってもロールでの連続式であってもよい。
Next, the resin film of this embodiment is laminated on one side or both sides of the insulating layer obtained above. In the above laminate, when the resin film has a protective film, after removing the protective film, the resin film is pressure-bonded to the insulating layer while being pressed and heated.
The resin film of the present embodiment is preferably laminated on a circuit board under reduced pressure by a vacuum lamination method. The pressure bonding temperature (laminating temperature) in lamination is, for example, 70 to 140° C., the pressure bonding pressure is, for example, 0.1 to 1.1 MPa, and the lamination is performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. is preferred. Moreover, the method of lamination may be a batch type or a continuous type using rolls.
[プリント配線板]
本実施形態のプリント配線板は、本実施形態の樹脂フィルムを用いて形成される層間絶縁層、又は本実施形態の積層体を用いて形成される層間絶縁層を含有するものである。
換言すると、本実施形態のプリント配線板は、層間絶縁層を有し、該層間絶縁層のうち少なくとも一層が本実施形態の樹脂フィルムの硬化物を含むものである。
本実施形態のプリント配線板を製造するに当たっては、例えば、まず、コア層の導体層を公知のエッチング法によって配線加工を行い、コア層の片面又は両面に本実施形態の樹脂フィルムをラミネートする。次に、樹脂フィルムを熱硬化してビルドアップ層を形成し、ドリル加工、レーザー加工等によるスルーホール又はブラインドビアホールの形成と、メッキ又は導電性ペーストによる層間配線の形成を経て、プリント配線板を製造することができる。
[Printed wiring board]
The printed wiring board of the present embodiment includes an interlayer insulating layer formed using the resin film of the present embodiment or an interlayer insulating layer formed using the laminate of the present embodiment.
In other words, the printed wiring board of the present embodiment has interlayer insulating layers, and at least one layer of the interlayer insulating layers contains the cured resin film of the present embodiment.
In manufacturing the printed wiring board of the present embodiment, for example, first, the conductor layer of the core layer is subjected to wiring processing by a known etching method, and the resin film of the present embodiment is laminated on one or both sides of the core layer. Next, the resin film is thermally cured to form a buildup layer, through holes or blind via holes are formed by drilling, laser processing, etc., and interlayer wiring is formed by plating or conductive paste, and the printed wiring board is manufactured. can be manufactured.
[半導体装置]
本実施形態の半導体装置は、本実施形態のプリント配線板を含有するものである。
本実施形態の半導体装置は、本実施形態のプリント配線板の所定の位置に、公知の方法により、半導体チップ、メモリ等を搭載して製造することができる。
[Semiconductor device]
The semiconductor device of this embodiment includes the printed wiring board of this embodiment.
The semiconductor device of this embodiment can be manufactured by mounting a semiconductor chip, a memory, etc. on a predetermined position of the printed wiring board of this embodiment by a known method.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。各例で得られた樹脂フィルムは以下の方法で評価した。 EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. The resin film obtained in each example was evaluated by the following methods.
[樹脂フィルムの取り扱い性]
樹脂フィルムの取り扱い性は、以下に示す方法で評価した。
(1)カッターでの切断による評価
各例で得られた支持体及び保護フィルムを有する樹脂フィルムをカッターで切断した際の粉落ちの有無を目視で確認し、粉落ちが無いものを取り扱い性良好とした。
(2)折り曲げによる評価
各例で得られた支持体及び保護フィルムを有する樹脂フィルムの保護フィルムを剥離し、支持体から樹脂塗工面に向かって180°折り曲げ、フィルムの割れの有無を目視で確認し、割れが発生しないものを取り扱い性良好とした。
上記(1)及び(2)の評価において、どちらも良好となったものを「A」、少なくともいずれかが良好でないものを「B」とした。
[Handling of resin film]
The handleability of the resin film was evaluated by the method shown below.
(1) Evaluation by cutting with a cutter The presence or absence of powder falling when cutting the resin film having the support and protective film obtained in each example with a cutter was visually checked. and
(2) Evaluation by bending The protective film of the resin film having the support and the protective film obtained in each example was peeled off, the support was bent 180° toward the resin-coated surface, and the presence or absence of cracks in the film was visually confirmed. A sample with no cracks was judged to have good handleability.
In the evaluations of (1) and (2) above, "A" was given when both were good, and "B" was given when at least one of them was not good.
[デスミア重量減少量(耐デスミア性の評価)]
ラミネーター内において、各例で得られた支持体及び保護フィルムを有する樹脂フィルムの保護フィルムを剥離し、銅箔(電解銅箔、厚さ12μm)の光沢面上に樹脂フィルムをラミネートした。ラミネートは、30秒間減圧して圧力を0.5MPaとした後、140℃で30秒間、圧着圧力0.5MPaの条件で行った。ラミネート後、支持体を剥離して、片面銅箔付き樹脂フィルムを得た。同様の操作により、別の片面銅箔付き樹脂フィルムを作製し、2つの片面銅箔付き樹脂フィルムの樹脂面同士を合わせ、真空プレスを用いて、175℃で60分間、圧着圧力1.0MPaの条件でプレス成型を行い、両面銅箔付き樹脂板を得た。得られた両面銅箔付き樹脂板を、190℃で2時間防爆乾燥機を用いて硬化させた。続いて、塩化第二鉄で両面の銅箔をエッチングすることで、厚さ約0.2mmの樹脂板を得た。この樹脂板を4cm角に切断して、耐デスミア性の試験片とした。次いで、該試験片に表1に示す処理を順次施してデスミア処理を行った。なお、薬液はアトテック社製のものを用いた。デスミア重量減少量は、デスミア処理前乾燥重量と、デスミア処理後重量との差(処理前重量-処理後重量)を算出し、これを耐デスミア性の指標とした。
[Desmear weight loss (evaluation of desmear resistance)]
In the laminator, the protective film of the resin film having the support and the protective film obtained in each example was peeled off, and the resin film was laminated on the glossy surface of copper foil (electrolytic copper foil, thickness 12 μm). The lamination was carried out under the conditions of 0.5 MPa pressure at 140° C. for 30 seconds and 0.5 MPa compression pressure after reducing the pressure for 30 seconds. After lamination, the support was peeled off to obtain a resin film with a copper foil on one side. By the same operation, another resin film with a copper foil on one side was produced, the resin surfaces of the two resin films with a copper foil on one side were aligned, and a vacuum press was used at 175 ° C. for 60 minutes at a pressure of 1.0 MPa. Press molding was performed under the conditions to obtain a resin plate with copper foil on both sides. The obtained resin plate with copper foils on both sides was cured at 190° C. for 2 hours using an explosion-proof dryer. Subsequently, the copper foil on both sides was etched with ferric chloride to obtain a resin plate with a thickness of about 0.2 mm. This resin plate was cut into a 4 cm square to obtain a desmear resistant test piece. Next, the test pieces were subjected to desmear treatment by sequentially performing the treatments shown in Table 1. In addition, the chemical|medical solution used the thing made from Atotech. The amount of desmear weight reduction was calculated by calculating the difference between the dry weight before desmear treatment and the weight after desmear treatment (weight before treatment - weight after treatment), and this was used as an index of desmear resistance.
[ボイド数の測定]
各製造例で作製したプリプレグ(25cm角)を4枚重ね、最外層(両面)に厚さ12μmの電解銅箔を配置し、圧着圧力3.0MPa、温度240℃で60分間プレスを行った。その後、銅エッチング液に浸漬することにより両面の銅箔を除去して、銅無し積層板を得た。続いて、ラミネーター内において、各例で作製した支持体及び保護フィルムを有する樹脂フィルムの保護フィルムを剥離し、銅無し積層板の両面に樹脂フィルムをラミネートした。ラミネートは、30秒間減圧して圧力を0.5MPaとした後、140℃で30秒間、圧着圧力0.5MPaの条件で行った。その後、防爆乾燥機を用いて、190℃で2時間加熱して樹脂フィルムを硬化させ、観察基板を得た。得られた観察基板の両面を目視で観察し、ボイド数を計測した。
[Measurement of void number]
Four prepregs (25 cm square) prepared in each production example were stacked, and an electrolytic copper foil having a thickness of 12 μm was placed on the outermost layer (both sides), and pressed at a pressure of 3.0 MPa and a temperature of 240° C. for 60 minutes. Thereafter, the copper foils on both sides were removed by immersion in a copper etching solution to obtain a copper-free laminate. Subsequently, in a laminator, the protective film of the resin film having the support and the protective film prepared in each example was peeled off, and the resin films were laminated on both sides of the copper-free laminate. The lamination was carried out under the conditions of 0.5 MPa pressure at 140° C. for 30 seconds and 0.5 MPa compression pressure after reducing the pressure for 30 seconds. Thereafter, using an explosion-proof dryer, the resin film was cured by heating at 190° C. for 2 hours to obtain an observation substrate. Both surfaces of the obtained observation substrate were visually observed to measure the number of voids.
[(X)変性ポリイミドの製造]
製造例1
(変性ポリイミド(X-1))
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積2リットルの反応容器に、X-22-161A(両末端ジアミン変性シロキサン、信越化学工業株式会社製、アミノ基当量800g/eq)72gと、ビス(4-マレイミドフェニル)メタン252gと、プロピレングリコールモノメチルエーテル270.0gを入れ、110℃で3時間反応させて、変性ポリイミド(X-1)含有溶液を得た。
[(X) Production of modified polyimide]
Production example 1
(Modified polyimide (X-1))
X-22-161A (diamine-modified siloxane at both ends, manufactured by Shin-Etsu Chemical Co., Ltd., amino group Equivalent weight 800 g/eq) 72 g, bis(4-maleimidophenyl)methane 252 g, and propylene glycol monomethyl ether 270.0 g were added and reacted at 110° C. for 3 hours to obtain a modified polyimide (X-1)-containing solution. .
[層間絶縁層用樹脂フィルム及びプリプレグの製造]
実施例1~2、比較例1~3
(樹脂フィルムA~E)
表2に示す配合組成(単位:質量部。但し、溶液又は分散液の場合は固形分換算量を示す。)で各成分を混合し、希釈溶媒にメチルエチルケトンを用いて、固形分濃度65質量%のワニスA~Eを得た。
次に、該ワニスA~Eを、270mm幅のPETフィルム(帝人デュポンフィルム株式会社製、商品名:G-2)に、塗布幅250mm、乾燥後の樹脂フィルム(樹脂組成物層)の厚さが15μmになるように塗布した後、100℃で3分間乾燥した。次いで、樹脂フィルムの支持体が設けられていない面に、保護フィルムとしてポリプロピレンフィルムを貼り合わせながらロール状に巻き取り、支持体及び保護フィルムを有する樹脂フィルムA~Eを得た。
[Production of resin film for interlayer insulating layer and prepreg]
Examples 1-2, Comparative Examples 1-3
(Resin films A to E)
Each component is mixed with the formulation shown in Table 2 (unit: parts by mass. However, in the case of a solution or dispersion, the solid content conversion amount is shown.), Using methyl ethyl ketone as a dilution solvent, the solid content concentration is 65% by mass. of varnishes A to E were obtained.
Next, the varnishes A to E are applied to a 270 mm wide PET film (trade name: G-2, manufactured by Teijin DuPont Films Co., Ltd.) with a width of 250 mm and a thickness of the resin film (resin composition layer) after drying. was applied so as to have a thickness of 15 μm, and dried at 100° C. for 3 minutes. Next, a polypropylene film as a protective film was adhered to the side of the resin film not provided with the support, and wound into a roll to obtain resin films A to E each having a support and a protective film.
製造例2~4
(プリプレグI~III)
表3に示す配合組成(単位:質量部。但し、溶液又は分散液の場合は固形分換算量を示す。)で各成分を混合し、溶媒にメチルエチルケトンを用いて固形分濃度65質量%のワニスI~IIIを得た。
上記で得られたワニスI~IIIを、ガラスクロス(種類:1037クロス、厚さ:25μm)に塗工機を用いて塗布した後、130℃で3分間乾燥して、溶媒を除去させると共に、熱硬化性樹脂組成物を半硬化させて、プリプレグI~IIIを得た。なお、塗布重量の調整はスクイズロール法で行い、得られたプリプレグ中における熱硬化性樹脂組成物の含有量は、72質量%であった。
Production Examples 2-4
(Prepregs I to III)
Each component is mixed with the formulation shown in Table 3 (unit: parts by mass. However, in the case of a solution or dispersion, the solid content conversion amount is shown.), and methyl ethyl ketone is used as a solvent to create a varnish with a solid content concentration of 65% by mass. I-III were obtained.
After applying the varnishes I to III obtained above to a glass cloth (type: 1037 cloth, thickness: 25 μm) using a coater, drying at 130 ° C. for 3 minutes to remove the solvent, The thermosetting resin composition was semi-cured to obtain prepregs I to III. The coating weight was adjusted by a squeeze roll method, and the content of the thermosetting resin composition in the obtained prepreg was 72% by mass.
なお、表2及び表3に示す各成分の詳細は以下の通りである。
[(A)固形エポキシ樹脂、(a)エポキシ樹脂]
・NC-7000-L:α-ナフトール/クレゾールノボラック型エポキシ樹脂(ナフタレン骨格含有型エポキシ樹脂)(日本化薬株式会社製、エポキシ当量:234g/eq)
・NC-3000-H:ビフェニルアラルキル型エポキシ樹脂(日本化薬株式会社製、エポキシ当量:288g/eq)
[液状エポキシ樹脂]
・jER828US:液状ビスフェノールA型エポキシ樹脂(三菱ケミカル株式会社製、エポキシ当量:184~194g/eq)
[エポキシ硬化剤]
・LA3018-50P:トリアジン骨格含有クレゾールノボラック型硬化剤(DIC株式会社製)
[(B)マレイミド化合物、(b)マレイミド化合物]
・BMI-4000:2,2-ビス[4-(4-マレイミドフェノキシ)フェニル]プロパン(大和化成工業株式会社製)
[(C)アミン化合物、(c)アミン化合物]
・X-22-161A:両末端ジアミン変性シロキサン(両末端に1級アミノ基を有するシロキサン化合物)(信越化学工業株式会社製、アミノ基当量:800g/eq)
[(D)エラストマー、(d)エラストマー]
・SG-P3:エポキシ基含有アクリル系熱可撓性エラストマー(ナガセケムテックス株式会社製、重量平均分子量:850,000、エポキシ価:0.21eq/kg)
[(E)無機充填材、(e)無機充填材]
・SC-2050KC:溶融シリカ(株式会社アドマテックス製、平均粒子径:0.5μm)
・SO-C2:球状シリカ(株式会社アドマテックス製、平均粒子径:0.5μm)
[(F)硬化促進剤、(f)硬化促進剤]
・TPP-S:トリフェニルホスフィントリフェニルボラン(北興化学株式会社製)
・DMAP:4-ジメチルアミノピリジン
The details of each component shown in Tables 2 and 3 are as follows.
[(A) solid epoxy resin, (a) epoxy resin]
・ NC-7000-L: α-naphthol/cresol novolac type epoxy resin (naphthalene skeleton-containing epoxy resin) (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 234 g / eq)
・ NC-3000-H: Biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq)
[Liquid epoxy resin]
・jER828US: liquid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 184 to 194 g / eq)
[Epoxy curing agent]
・ LA3018-50P: triazine skeleton-containing cresol novolac type curing agent (manufactured by DIC Corporation)
[(B) maleimide compound, (b) maleimide compound]
・ BMI-4000: 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
[(C) amine compound, (c) amine compound]
· X-22-161A: diamine-modified siloxane at both ends (siloxane compound having primary amino groups at both ends) (manufactured by Shin-Etsu Chemical Co., Ltd., amino group equivalent: 800 g / eq)
[(D) Elastomer, (d) Elastomer]
SG-P3: Epoxy group-containing acrylic thermoplastic elastomer (manufactured by Nagase ChemteX Corporation, weight average molecular weight: 850,000, epoxy value: 0.21 eq/kg)
[(E) inorganic filler, (e) inorganic filler]
・ SC-2050KC: fused silica (manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm)
・SO-C2: Spherical silica (manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm)
[(F) curing accelerator, (f) curing accelerator]
・ TPP-S: Triphenylphosphine triphenylborane (manufactured by Hokko Chemical Co., Ltd.)
・DMAP: 4-dimethylaminopyridine
表2から、本実施形態の実施例1及び2の樹脂フィルムは、取り扱い性に優れ、耐デスミア性に優れることが分かる。一方、(A)~(D)成分の少なくとも1成分を使用しなかった比較例1~3の樹脂フィルムは、取り扱い性又は耐デスミア性に劣っていた。 From Table 2, it can be seen that the resin films of Examples 1 and 2 of the present embodiment are excellent in handleability and desmear resistance. On the other hand, the resin films of Comparative Examples 1 to 3, in which at least one of the components (A) to (D) was not used, were inferior in handleability and desmear resistance.
実施例3~6、比較例4~6
次に、上記で製造した樹脂フィルムA、B及びE並びにプリプレグI~IIIを使用して、上記[ボイド数の測定]に記載の方法に従って積層体を製造し、ボイド数の評価を行った。評価結果を表4に示す。
Examples 3-6, Comparative Examples 4-6
Next, using the resin films A, B and E produced above and the prepregs I to III, laminates were produced according to the method described in [Measurement of number of voids] above, and the number of voids was evaluated. Table 4 shows the evaluation results.
表4から、本実施形態の層間絶縁層用樹脂フィルムを使用した実施例3~6の積層体は、ボイド数が少なく、コア層との濡れ性に優れていることが分かる。一方、本実施形態の層間絶縁層用樹脂フィルムとは異なる層間絶縁層用樹脂フィルムを使用した比較例4~6の積層体は、ボイド数が多く、コア層との濡れ性に劣っていることが分かる。 From Table 4, it can be seen that the laminates of Examples 3 to 6 using the interlayer insulation layer resin film of the present embodiment have a small number of voids and excellent wettability with the core layer. On the other hand, the laminates of Comparative Examples 4 to 6 using interlayer insulating resin films different from the interlayer insulating resin film of the present embodiment had a large number of voids and poor wettability with the core layer. I understand.
Claims (17)
前記層間絶縁層用樹脂フィルムが、熱硬化性樹脂組成物を含有し、
前記層間絶縁層用樹脂フィルムが含有する熱硬化性樹脂組成物が、(A)固形エポキシ樹脂と、(B)1分子中に2個以上のN-置換マレイミド基を有するマレイミド化合物と、(C)1分子中に2個以上の1級アミノ基を有するアミン化合物と、(D)エラストマーと、を含有する熱硬化性樹脂組成物、又は、(A)固形エポキシ樹脂と、(B)1分子中に2個以上のN-置換マレイミド基を有するマレイミド化合物及び(C)1分子中に2個以上の1級アミノ基を有するアミン化合物を反応させてなる(X)変性ポリイミドと、(D)エラストマーと、を含有する熱硬化性樹脂組成物であり、
前記プリプレグが、熱硬化性樹脂組成物を含有し、
前記プリプレグが含有する熱硬化性樹脂組成物が、(a)エポキシ樹脂と、(b)1分子中に2個以上のN-置換マレイミド基を有するマレイミド化合物と、(c)1分子中に2個以上の1級アミノ基を有するアミン化合物と、を含有する熱硬化性樹脂組成物、又は、(a)エポキシ樹脂と、(b)1分子中に2個以上のN-置換マレイミド基を有するマレイミド化合物及び(c)1分子中に2個以上の1級アミノ基を有するアミン化合物を反応させてなる(x)変性ポリイミドと、を含有する熱硬化性樹脂組成物である、積層体。 A laminate obtained by laminating a resin film for an interlayer insulating layer and an insulating layer formed by curing a prepreg or a prepreg,
The interlayer insulating layer resin film contains a thermosetting resin composition,
The thermosetting resin composition contained in the interlayer insulating layer resin film comprises (A) a solid epoxy resin, (B) a maleimide compound having two or more N-substituted maleimide groups in one molecule, and (C ) A thermosetting resin composition containing an amine compound having two or more primary amino groups in one molecule, and (D) an elastomer , or (A) a solid epoxy resin, and (B) one molecule (X) a modified polyimide obtained by reacting a maleimide compound having two or more N-substituted maleimide groups therein and (C) an amine compound having two or more primary amino groups in one molecule; and (D) A thermosetting resin composition containing an elastomer,
The prepreg contains a thermosetting resin composition,
The thermosetting resin composition contained in the prepreg comprises (a) an epoxy resin, (b) a maleimide compound having two or more N-substituted maleimide groups per molecule, and (c) two A thermosetting resin composition containing an amine compound having one or more primary amino groups, or (a) an epoxy resin, and (b) having two or more N-substituted maleimide groups in one molecule A laminate, which is a thermosetting resin composition containing a maleimide compound and (c) a modified polyimide obtained by reacting an amine compound having two or more primary amino groups in one molecule (x) .
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