JP6399337B2 - Insulating resin composition for printed circuit board and product using the same - Google Patents
Insulating resin composition for printed circuit board and product using the same Download PDFInfo
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- JP6399337B2 JP6399337B2 JP2014129440A JP2014129440A JP6399337B2 JP 6399337 B2 JP6399337 B2 JP 6399337B2 JP 2014129440 A JP2014129440 A JP 2014129440A JP 2014129440 A JP2014129440 A JP 2014129440A JP 6399337 B2 JP6399337 B2 JP 6399337B2
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0271—Arrangements for reducing stress or warp in rigid printed circuit boards, e.g. caused by loads, vibrations or differences in thermal expansion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/06—Thermal details
- H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important
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Description
本発明は、プリント回路基板用絶縁樹脂組成物およびこれを用いた製品に関する。 The present invention relates to an insulating resin composition for a printed circuit board and a product using the same.
電子機器の発展に伴い、プリント回路基板の低重量化、薄板化および小型化が日々進行中である。このような傾向に応えるために、プリント回路の配線がさらに複雑化および高密度化しつつある。このように基板に対して要求される電気的、熱的および機械的特性は、より重要な要素として作用している。プリント回路基板は、主に、回路配線の機能を果たす銅と、層間絶縁の機能を果たす高分子からなる。絶縁層を構成する高分子は、銅と比較すると、熱膨張係数、ガラス転移温度および厚さ均一性など、様々な特性が要求され、特に、絶縁層の厚さを薄く作製する必要がある。 With the development of electronic devices, printed circuit boards are becoming lighter, thinner, and smaller every day. In order to respond to such a tendency, the wiring of the printed circuit is becoming more complicated and dense. Thus, the electrical, thermal and mechanical properties required for the substrate are acting as more important factors. The printed circuit board is mainly composed of copper that functions as circuit wiring and a polymer that functions as interlayer insulation. The polymer constituting the insulating layer is required to have various characteristics such as a thermal expansion coefficient, a glass transition temperature, and a thickness uniformity as compared with copper. In particular, it is necessary to make the insulating layer thin.
近年、電子製品の軽薄短小化に伴い、プリント回路基板やエポキシモールディングコンパウンド（ＥＭＣ）などの電子素材も薄層化および多層化しつつあり、これに用いられる材料に対しても、耐熱性および熱膨張係数特性の改善が要求されている。また、電子製品における情報処理の高速化および大容量化が進むにつれて、これに用いられる部品や材料などに対しても高速応答特性が要求されている。 In recent years, electronic materials such as printed circuit boards and epoxy molding compounds (EMC) are becoming thinner and multi-layered as electronic products become lighter, thinner, and more heat resistant and thermally expandable. Improvement of coefficient characteristics is required. In addition, as information processing in electronic products increases in speed and capacity, high-speed response characteristics are required for components and materials used therefor.
そのため、従来、基板材料などに用いられていたエポキシ樹脂の他に、高速応答特性を満たすために、シアネートエステルなどが添加剤として用いられている。 Therefore, in addition to the epoxy resin conventionally used as a substrate material, cyanate ester or the like is used as an additive in order to satisfy high-speed response characteristics.
基板材料の特性上、銅箔との接着を維持し、且つ基板製造工程に適用するために、所定量以上のエポキシを用いることが必須である。しかし、エポキシが硬化反応を起こして生じる第二級アルコールなどによる誘電定数の上昇やエポキシ分子自体の高い誘電率によって、実際、基板材料において誘電定数を大幅に低減することは困難である。 Due to the characteristics of the substrate material, it is essential to use a predetermined amount or more of epoxy in order to maintain adhesion with the copper foil and to apply to the substrate manufacturing process. However, it is actually difficult to significantly reduce the dielectric constant in the substrate material due to the increase in dielectric constant caused by secondary alcohol generated by the epoxy curing reaction and the high dielectric constant of the epoxy molecule itself.
従来、基板材料の耐熱性を確保するために芳香族分子をベースとするエポキシ分子が用いられている。従来用いられているエポキシ分子は、芳香族分子の特性上、分子レベルで所定方向に配向しようとする性質があるため、他の分子の分極に影響を与える範囲内で分子の密集が起こる。そのため、かかる密集によって基板材料の自由体積（ｆｒｅｅ ｖｏｌｕｍｅ）が減少して、誘電定数を所定レベル以下に低減することが困難になった。 Conventionally, epoxy molecules based on aromatic molecules have been used to ensure the heat resistance of the substrate material. Conventionally used epoxy molecules have the property of being oriented in a predetermined direction at the molecular level due to the characteristics of aromatic molecules, and therefore, molecular crowding occurs within a range that affects the polarization of other molecules. For this reason, the density has reduced the free volume of the substrate material, making it difficult to reduce the dielectric constant below a predetermined level.
一方、特許文献１には、エポキシ樹脂および硬化剤を含む難燃性エポキシ樹脂組成物について開示されているが、通常のエポキシ樹脂を適用することで誘電定数を所定数値以下に低減するには限界があった。 On the other hand, Patent Document 1 discloses a flame retardant epoxy resin composition containing an epoxy resin and a curing agent, but it is a limit to reduce the dielectric constant to a predetermined value or less by applying a normal epoxy resin. was there.
本発明者らは、鋭意研究を重ねた結果、スピロビフルオレン（Ｓｐｉｒｏ ｂｉｆｌｕｏｒｅｎｅ）構造のエポキシ樹脂を含む絶縁樹脂組成物によりこれらの問題を解決できることを見出し、本発明を完成するに至った。したがって、本発明の第１目的は、耐熱性および熱膨張係数の特性を同様に維持するか向上させ、且つ誘電率（Ｄｋ）および誘電損（Ｄｆ）の特性を向上させたプリント回路基板用絶縁樹脂組成物を提供することにある。 As a result of intensive studies, the present inventors have found that these problems can be solved by an insulating resin composition containing an epoxy resin having a spiro bifluorene structure, and have completed the present invention. Therefore, the first object of the present invention is to maintain or improve the characteristics of heat resistance and thermal expansion coefficient in the same manner, and to improve the dielectric constant (Dk) and dielectric loss (Df) characteristics. The object is to provide a resin composition.
本発明の第２目的は、前記樹脂組成物を用いて製造されたプリプレグを提供することにある。 The second object of the present invention is to provide a prepreg produced using the resin composition.
本発明の第３目的は、前記プリプレグを適用して製造された銅張積層板上にビルドアップ層を積層して製造されたプリント回路基板を提供することにある。 The third object of the present invention is to provide a printed circuit board manufactured by stacking a buildup layer on a copper clad laminate manufactured by applying the prepreg.
本発明の一実施例によるプリント回路基板用絶縁樹脂組成物は、下記式で表されるスピロビフルオレン（Ｓｐｉｒｏ ｂｉｆｌｕｏｒｅｎｅ）構造のエポキシ樹脂と、硬化剤と、を含むことができる。 An insulating resin composition for a printed circuit board according to an embodiment of the present invention may include an epoxy resin having a Spiro bifluorene structure represented by the following formula, and a curing agent.
前記プリント回路基板用絶縁樹脂組成物において、前記スピロビフルオレン構造のエポキシ樹脂は、前記分子中心の炭素原子（Ｃ）が１０９．５゜の結合角を有しており、ＳＰ３の混成軌道であることができる。 In the insulating resin composition for a printed circuit board, the spirobifluorene structure epoxy resin has a bond angle of 109.5 ° in the carbon atom (C) of the molecular center, and is in a hybrid orbital of SP 3. Can be.
前記プリント回路基板用絶縁樹脂組成物において、前記スピロビフルオレン構造のエポキシ樹脂は、フルオレンの二つのベンゼン環が同一平面上に位置し、それぞれのフルオレンが互いに直交していることができる。 In the insulating resin composition for a printed circuit board, in the spirobifluorene structure epoxy resin, two benzene rings of fluorene may be located on the same plane, and the respective fluorenes may be orthogonal to each other.
前記プリント回路基板用絶縁樹脂組成物において、スピロビフルオレン構造のエポキシ樹脂を４０〜８０質量％含み、硬化剤を２０〜６０質量％含むことができる。 The insulating resin composition for a printed circuit board may include 40-80% by mass of an epoxy resin having a spirobifluorene structure and 20-60% by mass of a curing agent.
前記プリント回路基板用絶縁樹脂組成物において、前記硬化剤は、アミン系硬化剤、酸無水物系硬化剤、ポリアミン硬化剤、ポリスルフィド硬化剤、フェノールノボラック型硬化剤、ビスフェノールＡ型硬化剤およびジシアンジアミド硬化剤からなる群から選択される一つ以上のものであることができる。 In the insulating resin composition for a printed circuit board, the curing agent is an amine curing agent, an acid anhydride curing agent, a polyamine curing agent, a polysulfide curing agent, a phenol novolac curing agent, a bisphenol A curing agent, and a dicyandiamide curing. It can be one or more selected from the group consisting of agents.
前記プリント回路基板用絶縁樹脂組成物において、前記絶縁樹脂組成物１００質量部に対して、１〜６６質量部のシアネートエステル樹脂をさらに含むことができる。 The insulating resin composition for a printed circuit board may further include 1 to 66 parts by mass of a cyanate ester resin with respect to 100 parts by mass of the insulating resin composition.
前記プリント回路基板用絶縁樹脂組成物において、前記絶縁樹脂組成物１００質量部に対して、１〜６６質量部のビスマレイミド樹脂をさらに含むことができる。 The insulating resin composition for a printed circuit board may further include 1 to 66 parts by mass of a bismaleimide resin with respect to 100 parts by mass of the insulating resin composition.
前記プリント回路基板用絶縁樹脂組成物において、前記絶縁樹脂組成物１００質量部に対して、１〜６００質量部の無機充填剤をさらに含むことができる。 The insulating resin composition for a printed circuit board may further include 1 to 600 parts by mass of an inorganic filler with respect to 100 parts by mass of the insulating resin composition.
前記プリント回路基板用絶縁樹脂組成物において、前記無機充填剤は、シリカ（ＳｉＯ２）、アルミナ（Ａｌ２Ｏ３）、硫酸バリウム（ＢａＳＯ４）、水酸化アルミニウム（Ａｌ（ＯＨ） ３ ）、水酸化マグネシウム（Ｍｇ（ＯＨ）２）、炭酸カルシウム（ＣａＣＯ３）、炭酸マグネシウム（ＭｇＣＯ３）、酸化マグネシウム（ＭｇＯ）、窒化ホウ素（ＢＮ）、炭化ケイ素（ＳｉＣ）、ホウ酸アルミニウム（ＡｌＢＯ３）、チタン酸バリウム（ＢａＴｉＯ３）およびジルコン酸カルシウム（ＣａＺｒＯ３）から選択される一つ以上のものであることができる。 In the insulating resin composition for a printed circuit board, the inorganic filler includes silica (SiO 2 ), alumina (Al 2 O 3 ), barium sulfate (BaSO 4 ), aluminum hydroxide (Al (OH) 3 ) , water Magnesium oxide (Mg (OH) 2 ), calcium carbonate (CaCO 3 ), magnesium carbonate (MgCO 3 ), magnesium oxide (MgO), boron nitride (BN), silicon carbide (SiC), aluminum borate (AlBO 3 ), It may be one or more selected from barium titanate (BaTiO 3 ) and calcium zirconate (CaZrO 3 ).
本発明の一実施例によるプリプレグは、前記樹脂組成物を含むワニス（ｖａｒｎｉｓｈ）に無機繊維または有機繊維を含浸および乾燥してなることができる。 The prepreg according to an embodiment of the present invention may be formed by impregnating and drying a varnish containing the resin composition with an inorganic fiber or an organic fiber.
前記プリプレグにおいて、前記無機繊維または有機繊維は、ガラス繊維、炭素繊維、ポリパラフェニレンベンゾビスオキサゾール繊維、サーモトロピック（ｔｈｅｒｍｏｔｒｏｐｉｃ）液晶高分子繊維、リオトロピック液晶高分子繊維、アラミド繊維、ポリピリドビスイミダゾール繊維、ポリベンゾチアゾール繊維、およびポリアリレート繊維から選択される一つ以上のものであることができる。 In the prepreg, the inorganic fiber or the organic fiber may be glass fiber, carbon fiber, polyparaphenylene benzobisoxazole fiber, thermotropic liquid crystal polymer fiber, lyotropic liquid crystal polymer fiber, aramid fiber, polypyridobisimidazole. It can be one or more selected from fibers, polybenzothiazole fibers, and polyarylate fibers.
本発明の一実施例によるプリント回路基板は、前記プリプレグの片面または両面に銅箔を貼り付けて得た銅張積層板（ＣＣＬ）上にビルドアップ層を積層してなることができる。 The printed circuit board according to an embodiment of the present invention may be formed by laminating a buildup layer on a copper clad laminate (CCL) obtained by attaching a copper foil to one or both sides of the prepreg.
本発明の一実施例によるプリント回路基板用絶縁樹脂組成物は、スピロビフルオレン構造のエポキシ樹脂を含むことで自由体積が大きくなり、誘電率および誘電損の物性特性を向上させることができる。 The insulating resin composition for a printed circuit board according to an embodiment of the present invention includes a spirobifluorene structure epoxy resin, thereby increasing the free volume and improving the physical properties of dielectric constant and dielectric loss.
また、前記スピロビフルオレン構造のエポキシ樹脂により、従来技術と同様であるかより向上した耐熱性および熱膨張係数の特性を有するプリント回路基板用絶縁樹脂組成物を提供することができる。 In addition, the insulating resin composition for a printed circuit board having the same heat resistance and thermal expansion coefficient characteristics as those of the prior art can be provided by the spirobifluorene structure epoxy resin.
また、前記樹脂組成物に、無機充填剤、シアネートエステル樹脂、またはビスマレイミド樹脂を添加することで、耐熱性および熱膨張係数の特性をより向上させることができる。 Moreover, the characteristic of heat resistance and a thermal expansion coefficient can be improved more by adding an inorganic filler, cyanate ester resin, or a bismaleimide resin to the said resin composition.
本発明の一実施例によるプリント回路基板用絶縁樹脂組成物を用いて製造された絶縁フィルムまたはプリプレグをプリント回路基板に適用して、耐熱性、熱膨張係数、誘電率および誘電損の特性が向上した製品を得ることができる。 An insulating film or prepreg manufactured using an insulating resin composition for a printed circuit board according to an embodiment of the present invention is applied to a printed circuit board to improve heat resistance, thermal expansion coefficient, dielectric constant, and dielectric loss characteristics. Product can be obtained.
本発明の目的、特定の長所および新規の特徴は、添付図面に係る以下の詳細な説明および好ましい実施例によってさらに明らかになるであろう。本明細書において、各図面の構成要素に参照番号を付け加えるに際し、同一の構成要素に限っては、たとえ異なる図面に示されても、できるだけ同一の番号を付けるようにしていることに留意しなければならない。また、「一面」、「他面」、「第１」、「第２」などの用語は、一つの構成要素を他の構成要素から区別するために用いられるものであり、構成要素が前記用語によって限定されるものではない。以下、本発明を説明するにあたり、本発明の要旨を不明瞭にする可能性がある係る公知技術についての詳細な説明は省略する。 Objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description and preferred embodiments with reference to the accompanying drawings. In this specification, it should be noted that when adding reference numerals to the components of each drawing, the same components are given the same number as much as possible even if they are shown in different drawings. I must. The terms “one side”, “other side”, “first”, “second” and the like are used to distinguish one component from another component, and the component is the term It is not limited by. Hereinafter, in describing the present invention, detailed descriptions of known techniques that may obscure the subject matter of the present invention are omitted.
以下、添付図面を参照して、本発明の好ましい実施例を詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
［スピロビフルオレン（Ｓｐｉｒｏ ｂｉｆｌｕｏｒｅｎｅ）構造のエポキシ樹脂］
本発明の一実施例によるプリント回路基板用絶縁樹脂組成物は、下記式で表されるスピロビフルオレン構造のエポキシ樹脂を含むことができる。
[Epoxy resin having a spiro bifluorene structure]
The insulating resin composition for a printed circuit board according to an embodiment of the present invention may include an epoxy resin having a spirobifluorene structure represented by the following formula.
前記エポキシ樹脂は、分子中心の炭素原子（Ｃ）を中心として上／下に二つのフルオレン（ｆｌｕｏｒｅｎｅ）基が９０゜をなして三次元構造を形成することができる。前記エポキシ樹脂は、三次元上でいずれのエポキシ樹脂の化学的構造よりも分子間の距離が遠くなり、立体障害によって分子間の密集が低下し、特に、上／下に９０゜で曲がった構造によってそれぞれのフルオレンのベンゼン環が一致する法線ベクトル（ｎｏｒｍａｌ ｖｅｃｔｏｒ）を有することができる。したがって、三次元上で一枚ずつ（ｓｈｅｅｔ ｂｙ ｓｈｅｅｔ）配列されることを防止することができ、これにより、前記エポキシ樹脂を含む樹脂組成物自体の誘電率および誘電損を低減することができる。 The epoxy resin can form a three-dimensional structure by forming two fluorene groups at 90 ° above / below the carbon atom (C) at the center of the molecule. The epoxy resin has a larger intermolecular distance than the chemical structure of any epoxy resin in three dimensions, and the intermolecular density decreases due to steric hindrance, and in particular, a structure bent at 90 ° up / down. Can have a normal vector in which the benzene rings of the respective fluorenes coincide with each other. Therefore, it is possible to prevent the sheets from being arranged one by one in three dimensions, and thereby the dielectric constant and dielectric loss of the resin composition containing the epoxy resin can be reduced.
また、前記エポキシ樹脂の分子構造上の特徴により自由体積が大きくなり、これにより誘電率低減の効果を奏することができる。 In addition, the free volume is increased due to the molecular structure characteristics of the epoxy resin, and the effect of reducing the dielectric constant can be obtained.
前記エポキシ樹脂は、分子中心の炭素原子（Ｃ）が１０９．５゜の結合角を有しており、ＳＰ３の混成軌道であることができる。これにより、前記炭素原子は、各結合原子間の距離が最も遠くなることができる。また、前記エポキシ樹脂は、フルオレンの二つのベンゼン環が同一平面上に位置し、それぞれのフルオレンが互いに直交していることができる。 The epoxy resin has a bond angle of 109.5 ° at the carbon atom (C) at the molecular center, and can be a hybrid orbit of SP 3 . As a result, the carbon atom can have the longest distance between each bonding atom. In the epoxy resin, two benzene rings of fluorene may be located on the same plane, and the respective fluorenes may be orthogonal to each other.
前記式で表されるエポキシ樹脂は、二つのベンゼン環が同一平面上に位置することで、二つのベンゼン環は、炭素−炭素結合を軸として回転することができず、同一平面上に固定した構造を有することができる。そのため、各分子間のパッキング（ｐａｃｋｉｎｇ）が困難となり、分子間の距離が遠くなりうる。通常、芳香族分子は、互いにパッキングして低いエネルギー状態を維持しようとする特性を示すが、かかる特性によって誘電率が高くなりうる。しかし、本発明の一実施例によるスピロビフルオレン構造のエポキシ樹脂は、三次元上で分子間の距離が遠くなると、自由体積が高くなって誘電率が相対的に低くなり、基板材料への適用が有利になりうる。 In the epoxy resin represented by the above formula, the two benzene rings are positioned on the same plane, and the two benzene rings cannot be rotated around the carbon-carbon bond and are fixed on the same plane. Can have a structure. Therefore, packing between molecules becomes difficult, and the distance between molecules can be increased. Aromatic molecules typically exhibit properties that attempt to pack each other and maintain a low energy state, but such properties can increase the dielectric constant. However, an epoxy resin having a spirobifluorene structure according to an embodiment of the present invention has a high free volume and a relatively low dielectric constant when the distance between molecules increases in three dimensions. Can be advantageous.
本発明の一実施例によるプリント回路基板用樹脂組成物において、前記スピロビフルオレン構造のエポキシ樹脂の使用量は特に制限されず、４０〜８０質量％含んでもよい。前記エポキシ樹脂が４０質量％未満の場合には、樹脂組成物の誘電率および誘電損の低減効果が現れないことがあり、８０質量％を超える場合には、未硬化のエポキシ樹脂が樹脂組成物内に存在して、耐熱性が減少し、熱膨張係数が増加することがある。 In the resin composition for a printed circuit board according to one embodiment of the present invention, the amount of the epoxy resin having the spirobifluorene structure is not particularly limited, and may be 40 to 80% by mass. When the epoxy resin is less than 40% by mass, the effect of reducing the dielectric constant and dielectric loss of the resin composition may not appear. When it exceeds 80% by mass, an uncured epoxy resin is used as the resin composition. The heat resistance may decrease and the thermal expansion coefficient may increase.
前記エポキシ樹脂は、末端部に２〜４個のエポキシ基を含むことができ、フルオレンの３，６位に４個のグリシジルエステル（ｇｌｙｃｉｄｙｌ ｅｔｈｅｒ）官能基を含むことができる。 The epoxy resin may include 2 to 4 epoxy groups at a terminal portion, and may include 4 glycidyl ester functional groups at the 3rd and 6th positions of fluorene.
［硬化剤］
本発明の一実施例によるプリント回路基板用絶縁樹脂組成物は、例えば、図１に示したように、スピロビフルオレン構造のエポキシ樹脂と、硬化剤と、を含むことができる。前記硬化剤としては、通常、エポキシ樹脂に含まれたエポキシ基と反応可能な硬化剤を含むことができ、特にこれに限定されるものではない。
[Curing agent]
The insulating resin composition for a printed circuit board according to an embodiment of the present invention may include, for example, an epoxy resin having a spirobifluorene structure and a curing agent as illustrated in FIG. As the curing agent, a curing agent capable of reacting with an epoxy group contained in an epoxy resin can be included, and the curing agent is not particularly limited thereto.
前記硬化剤の使用量は、特に制限されず、２０〜６０質量％含んでもよい。前記硬化剤が２０質量％未満の場合には、硬化反応が十分に行われず、樹脂組成物の耐熱性が減少し、熱膨張係数が増加することがあり、６０質量％を超える場合には、前記スピロビフルオレン構造のエポキシ樹脂の誘電率および誘電損の低減効果が現れないこともある。 The usage-amount of the said hardening | curing agent is not restrict | limited in particular, You may contain 20-60 mass%. When the curing agent is less than 20% by mass, the curing reaction is not sufficiently performed, the heat resistance of the resin composition is decreased, and the thermal expansion coefficient may be increased. The effect of reducing the dielectric constant and dielectric loss of the epoxy resin having the spirobifluorene structure may not appear.
前記硬化剤は、特に制限されず、アミン系硬化剤、酸無水物系硬化剤、ポリアミン硬化剤、ポリスルフィド硬化剤、フェノールノボラック型硬化剤、ビスフェノールＡ型硬化剤、ジシアンジアミド硬化剤などが挙げられ、硬化剤を１種または２種以上組み合わせて用いてもよい。 The curing agent is not particularly limited, and examples thereof include amine curing agents, acid anhydride curing agents, polyamine curing agents, polysulfide curing agents, phenol novolac curing agents, bisphenol A curing agents, dicyandiamide curing agents, and the like. You may use a hardening | curing agent 1 type or in combination of 2 or more types.
本発明の一実施例による前記樹脂組成物は、硬化促進剤を選択的に含有させることで効率よく硬化させることができる。前記硬化促進剤は、特に制限されず、金属系硬化促進剤、イミダゾール系硬化促進剤、アミン系硬化促進剤などが挙げられ、これらを１種または２種以上組み合わせて用いてもよい。 The resin composition according to an embodiment of the present invention can be efficiently cured by selectively containing a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include metal-based curing accelerators, imidazole-based curing accelerators, and amine-based curing accelerators. These may be used alone or in combination of two or more.
前記金属系硬化促進剤としては、特に制限されず、コバルト、銅、亜鉛、鉄、ニッケル、マンガン、スズなどの金属の有機金属錯体または有機金属塩が挙げられる。有機金属錯体の具体例としては、コバルト（ＩＩ）アセチルアセトナート、コバルト（ＩＩＩ）アセチルアセトナートなどの有機コバルト錯体、銅（ＩＩ）アセチルアセトナートなどの有機銅錯体、亜鉛（ＩＩ）アセチルアセトナートなどの有機亜鉛錯体、鉄（ＩＩＩ）アセチルアセトナートなどの有機鉄錯体、ニッケル（ＩＩ）アセチルアセトナートなどの有機ニッケル錯体、マンガン（ＩＩ）アセチルアセトナートなどの有機マンガン錯体などが挙げられる。有機金属塩としては、オクチル酸亜鉛、オクチル酸スズ、ナフテン酸亜鉛、ナフテン酸コバルト、ステアリン酸スズ、ステアリン酸亜鉛などが挙げられる。金属系硬化促進剤としては、硬化性、溶剤溶解性の面において、コバルト（ＩＩ）アセチルアセトナート、コバルト（ＩＩＩ）アセチルアセトナート、亜鉛（ＩＩ）アセチルアセトナート、ナフテン酸亜鉛、鉄（ＩＩＩ）アセチルアセトナートが好ましく、特に、コバルト（ＩＩ）アセチルアセトナート、ナフテン酸亜鉛が最も好ましい。金属系硬化促進剤を１種または２種以上組み合わせて用いてもよい。 The metal curing accelerator is not particularly limited, and examples thereof include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. As the metal-based curing accelerator, in terms of curability and solvent solubility, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate, iron (III) Acetylacetonate is preferred, and cobalt (II) acetylacetonate and zinc naphthenate are most preferred. You may use a metal type hardening accelerator 1 type or in combination of 2 or more types.
前記イミダゾール系硬化促進剤としては、特に制限されず、２−メチルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、１，２−ジメチルイミダゾール、２−エチル−４−メチルイミダゾール、１，２−ジメチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、１−シアノエチル−２−メチルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾリウムトリメリテート、１−シアノエチル−２−フェニルイミダゾリウムトリメリテート、２，４−ジアミノ−６−［２´−メチルイミダゾリル−（１´）］−エチル−ｓ−トリアジン、２，４−ジアミノ−６−［２´−ウンデシルイミダゾリル−（１´）］−エチル−ｓ‐トリアジン、２，４−ジアミノ−６−［２´−エチル−４´−メチルイミダゾリル−（１´）］−エチル−ｓ−トリアジン、２，４−ジアミノ−６−［２´−メチルイミダゾリル−（１´）］−エチル−ｓ−トリアジンイソシアヌル酸付加物、２−フェニルイミダゾールイソシアヌル酸付加物、２−フェニル−４、５−ジヒドロキシメチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２，３−ジヒドロキシ−１Ｈ−ピロロ［１，２−ａ］ベンゾイミダゾール、１−ドデシル−２−メチル−３−ベンジルイミダゾリウムクロリド、２−メチルイミダゾリン、２−フェニルイミダゾリンなどのイミダゾール化合物およびイミダゾール化合物とエポキシ樹脂の添加物が挙げられる。イミダゾール硬化促進剤を１種または２種以上組み合わせて用いてもよい。 The imidazole curing accelerator is not particularly limited, and 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2 -Dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-shear Ethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'- Undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2, 4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydroxy-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecy -2-methyl-3-benzyl-imidazolium chloride, 2-methyl-imidazoline, 2-phenyl-imidazoline imidazole compounds such as and imidazole compounds and additives epoxy resins. One or two or more imidazole curing accelerators may be used in combination.
前記アミン系硬化促進剤としては、特に制限されず、トリエチルアミン、トリブチルアミンなどのトリアルキルアミン、４−ジメチルアミノピリジン、ベンジルジメチルアミン、２，４，６−トリス（ジメチルアミノメチル）フェノール、１，８−ジアザビシクロ（５，４，０）−ウンデセンなどのアミン化合物などが挙げられる。アミン系硬化促進剤を１種または２種以上組み合わせて用いてもよい。 The amine curing accelerator is not particularly limited, and is a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1, And amine compounds such as 8-diazabicyclo (5,4,0) -undecene. You may use 1 type, or 2 or more types of amine type hardening accelerators in combination.
［シアネートエステル樹脂］
本発明の一実施例によるプリント回路基板用絶縁樹脂組成物は、耐熱性向上のために、シアネートエステル樹脂をさらに含んでもよい。
[Cyanate ester resin]
The insulating resin composition for a printed circuit board according to an embodiment of the present invention may further include a cyanate ester resin for improving heat resistance.
前記シアネートエステル樹脂の使用量は、特に制限されず、前記樹脂組成物１００質量部に対して１〜６６質量部を含んでもよい。前記シアネートエステル樹脂の使用量が１質量部未満の場合には、前記樹脂組成物の耐熱性が低下して基板材料としての使用が困難になる恐れがあり、６６質量部を超える場合には、樹脂組成物内のスピロビフルオレン構造のエポキシ樹脂添加量が相対的に減少して、誘電率および誘電損の低減効果が低下する恐れがある。 The amount of the cyanate ester resin used is not particularly limited, and may include 1 to 66 parts by mass with respect to 100 parts by mass of the resin composition. When the amount of the cyanate ester resin used is less than 1 part by mass, the heat resistance of the resin composition may be reduced, making it difficult to use as a substrate material. When the amount exceeds 66 parts by mass, The addition amount of the spirobifluorene structure epoxy resin in the resin composition may be relatively reduced, and the effect of reducing the dielectric constant and the dielectric loss may be reduced.
前記シアネートエステル樹脂は、ビスフェノールＡ型、クレゾールノボラック型およびフェノールノボラック型シアネートエステルから選択される一つ以上のものであってもよく、特にこれに限定されるものではない。 The cyanate ester resin may be one or more selected from bisphenol A type, cresol novolac type and phenol novolac type cyanate ester, and is not particularly limited thereto.
［ビスマレイミド樹脂］
本発明の一実施例によるプリント回路基板用絶縁樹脂組成物は、耐熱性向上のために、ビスマレイミドをさらに含んでもよい。
[Bismaleimide resin]
The insulating resin composition for a printed circuit board according to an embodiment of the present invention may further include bismaleimide for improving heat resistance.
前記ビスマレイミド樹脂の使用量は、特に制限されず、前記樹脂組成物１００質量部に対して１〜６６質量部を含んでもよい。前記ビスマレイミド樹脂の使用量が１質量部未満の場合には、前記樹脂組成物の耐熱性が低下して、基板材料としての使用が困難になる恐れがあり、６６質量部を超える場合には、樹脂組成物内のスピロビフルオレン構造のエポキシ樹脂添加量が相対的に減少して、誘電率および誘電損の低減効果が低下する恐れがある。 The amount of the bismaleimide resin used is not particularly limited and may include 1 to 66 parts by mass with respect to 100 parts by mass of the resin composition. When the amount of the bismaleimide resin used is less than 1 part by mass, the heat resistance of the resin composition may be reduced, making it difficult to use as a substrate material. In addition, the amount of the spirobifluorene structure epoxy resin in the resin composition may be relatively reduced, and the dielectric constant and dielectric loss reduction effects may be reduced.
前記ビスマレイミドは、当業界に公知の物質を適用することができる。 As the bismaleimide, a substance known in the art can be applied.
［無機充填剤］
本発明の一実施例によるプリント回路基板用絶縁樹脂組成物は、熱膨張係数の向上のために、無機充填剤をさらに含んでもよい。
[Inorganic filler]
The insulating resin composition for a printed circuit board according to an embodiment of the present invention may further include an inorganic filler for improving the thermal expansion coefficient.
前記無機充填剤の使用量は、特に制限されず、前記樹脂組成物１００質量部に対して１〜６００質量部を含んでもよい。前記無機充填剤の使用量が１質量部未満の場合には、前記樹脂組成物の熱膨張係数が高くなり、耐熱性が低下して、基板材料としての使用が困難になる恐れがあり、６００質量部を超える場合には、金属層との剥離強度が低下して、基板工程への適用が困難になる恐れがある。 The amount of the inorganic filler used is not particularly limited and may include 1 to 600 parts by mass with respect to 100 parts by mass of the resin composition. When the amount of the inorganic filler used is less than 1 part by mass, the thermal expansion coefficient of the resin composition is increased, the heat resistance is lowered, and the use as a substrate material may be difficult. 600 When it exceeds the mass part, the peel strength from the metal layer is lowered, and it may be difficult to apply to the substrate process.
前記無機充填剤は、シリカ（ＳｉＯ２）、アルミナ（Ａｌ２Ｏ３）、硫酸バリウム（ＢａＳＯ４）、水酸化アルミニウム（Ａｌ（ＯＨ） ３ ）、水酸化マグネシウム（Ｍｇ（ＯＨ）２）、炭酸カルシウム（ＣａＣＯ３）、炭酸マグネシウム（ＭｇＣＯ３）、酸化マグネシウム（ＭｇＯ）、窒化ホウ素（ＢＮ）、炭化ケイ素（ＳｉＣ）、ホウ酸アルミニウム（ＡｌＢＯ３）、チタン酸バリウム（ＢａＴｉＯ３）およびジルコン酸カルシウム（ＣａＺｒＯ３）から選択される一つ以上のものであってもよく、特にこれに限定されるものではない。 The inorganic filler includes silica (SiO 2 ), alumina (Al 2 O 3 ), barium sulfate (BaSO 4 ), aluminum hydroxide (Al (OH) 3 ) , magnesium hydroxide (Mg (OH) 2 ), carbonic acid Calcium (CaCO 3 ), magnesium carbonate (MgCO 3 ), magnesium oxide (MgO), boron nitride (BN), silicon carbide (SiC), aluminum borate (AlBO 3 ), barium titanate (BaTiO 3 ) and calcium zirconate It may be one or more selected from (CaZrO 3 ), and is not particularly limited thereto.
本発明の一実施例による絶縁樹脂組成物は、本技術分野において公知のいずれの一般的な方法で半固状のフィルムからなることができる。例えば、ロールコータ（ｒｏｌｌ ｃｏａｔｅｒ）、カーテンコータ（ｃｕｒｔａｉｎ ｃｏａｔｅｒ）、またはコンマコータ（ｃｏｍｍａ ｃｏａｔｅｒ）などを用いてフィルム状に製造して乾燥した後、これを基板上に適用して、ビルドアップ方式により多層プリント回路基板を製造する際に、絶縁フィルムまたはプリプレグとして用いられることができる。かかる絶縁フィルムまたはプリプレグは、耐熱性、熱膨張係数、誘電率および誘電損の特性を向上させることができる。 The insulating resin composition according to one embodiment of the present invention can be formed of a semi-solid film by any general method known in the art. For example, a roll coater, a curtain coater, a comma coater, or a comma coater is used to produce a film and then dry it. In manufacturing a printed circuit board, it can be used as an insulating film or prepreg. Such an insulating film or prepreg can improve the properties of heat resistance, thermal expansion coefficient, dielectric constant and dielectric loss.
このように、本発明の一実施例による絶縁樹脂組成物を含むワニスに無機繊維または有機繊維などの基材に含浸してから硬化させてプリプレグを製造し、これの片面または両面に銅箔を貼り付けて銅張積層板を製造することができる。 Thus, a varnish containing an insulating resin composition according to an embodiment of the present invention is impregnated into a base material such as inorganic fiber or organic fiber and then cured to produce a prepreg, and copper foil is provided on one or both sides of the prepreg. A copper clad laminate can be manufactured by pasting.
また、前記樹脂組成物からなる絶縁フィルムは、多層プリント回路基板の製造の際に内層として用いられる銅張積層板上に積層して、多層プリント回路基板の製造の際に用いることができる。 The insulating film made of the resin composition can be laminated on a copper clad laminate used as an inner layer in the production of a multilayer printed circuit board and used in the production of a multilayer printed circuit board.
例えば、前記樹脂組成物からなる絶縁フィルムをパターン加工した内層回路基板上に積層してから約８０〜１１０℃の温度で約３０分間硬化させ、デスミア（ｄｅｓｍｅａｒ）工程を行った後、回路層を無電解めっきおよび電気めっき工程により形成して、多層プリント回路基板を製造することができる。 For example, after laminating an insulating film made of the resin composition on a patterned inner layer circuit board, it is cured at a temperature of about 80 to 110 ° C. for about 30 minutes, and after performing a desmear process, A multilayer printed circuit board can be manufactured by forming by an electroless plating and electroplating process.
前記無機繊維または有機繊維は、ガラス繊維、炭素繊維、ポリパラフェニレンベンゾビスオキサゾール繊維、サーモトロピック（ｔｈｅｒｍｏｔｒｏｐｉｃ）液晶高分子繊維、リオトロピック液晶高分子繊維、アラミド繊維、ポリピリドビスイミダゾール繊維、ポリベンゾチアゾール繊維、およびポリアリレート繊維から選択される一つ以上のものであってもよく、特にこれに限定されるものではない。 The inorganic fiber or organic fiber includes glass fiber, carbon fiber, polyparaphenylenebenzobisoxazole fiber, thermotropic liquid crystal polymer fiber, lyotropic liquid crystal polymer fiber, aramid fiber, polypyridobisimidazole fiber, polybenzo It may be one or more selected from thiazole fiber and polyarylate fiber, and is not particularly limited thereto.
以下、実施例および比較例により、本発明をより具体的に説明するが、下記例に本発明の範疇が限定されない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, the category of this invention is not limited to the following example.
［スピロビフルオレン構造のエポキシの製造］
［製造例１］
５００ｍｌのフラスコ反応器に３，３´，６，６´−テトラヒドロキシ−９，９´−スピロビ［９Ｈ−フルオレン］１９ｇ、エピクロロヒドリン９２．５ｇをＩＰＡ６０ｇおよび蒸留水３０ｇに添加して溶解した。次に、攪拌装置を用いて反応器を攪拌して約６５℃まで昇温させた後、約６５℃で約３０分間さらに攪拌した。２０質量％の水酸化ナトリウム水溶液１８０ｇを約３０分間一滴ずつ滴下（ｄｒｏｐｗｉｓｅ）して反応器に添加した。添加後、温度を維持して約１時間さらに反応させた。反応器を常温（２５℃）に冷却した後、有機層のみを抽出してＭｇＳＯ４を加えて残りの水分を除去した。次に、減圧蒸留装置を用いて溶媒を除去し、真空下で約１２時間さらに乾燥して、スピロビフルオレン構造のエポキシを製造した。
[Production of spirobifluorene structure epoxy]
[Production Example 1]
In a 500 ml flask reactor, 19 g of 3,3 ′, 6,6′-tetrahydroxy-9,9′-spirobi [9H-fluorene] and 92.5 g of epichlorohydrin are added to 60 g of IPA and 30 g of distilled water and dissolved. did. Next, the reactor was stirred using a stirrer and heated to about 65 ° C., and then further stirred at about 65 ° C. for about 30 minutes. 180 g of a 20% by weight aqueous sodium hydroxide solution was added dropwise to the reactor drop by drop for about 30 minutes. After the addition, the reaction was further continued for about 1 hour while maintaining the temperature. After the reactor was cooled to room temperature (25 ° C.), only the organic layer was extracted and MgSO 4 was added to remove the remaining water. Next, the solvent was removed using a vacuum distillation apparatus, and further dried for about 12 hours under vacuum to produce an epoxy having a spirobifluorene structure.
（実施例１）
５００ｍｌのフラスコに溶剤であるＭＥＫ８０ｇを加え、前記製造例１で製造されたスピロビフルオレン（Ｓｐｉｒｏ ｂｉｆｌｕｏｒｅｎｅ）構造のエポキシ３５ｇ、フェノール性硬化剤（コーロン社製、ＫＰＨ−Ｆ３１００）１５ｇ、硬化触媒としてイミダゾール（Ａｌｄｒｉｃｈ社製、２−Ｐｈｅｎｙｌ ｉｍｉｄａｚｏｌｅ）０．５ｇを加えて１時間攪拌した後、球状シリカ（アドマテックス社製、５００ｎｍ）１１７ｇをさらに加えて１時間以上さらに攪拌し、ワニスを製造した。
Example 1
MEK 80 g as a solvent is added to a 500 ml flask, 35 g of an epoxy having a spiro bifluorene structure produced in Production Example 1 above, 15 g of a phenolic curing agent (KPH-F3100, manufactured by Kolon Co., Ltd.), and imidazole as a curing catalyst After adding 0.5 g (manufactured by Aldrich, 2-Phenyl imidazole) and stirring for 1 hour, 117 g of spherical silica (manufactured by Admatechs, 500 nm) was further added and further stirred for 1 hour or more to produce a varnish.
前記ワニスをガラス繊維（日東紡社製、Ｅ２１１６）に均一に含浸した。混合溶液が含浸したガラス繊維は、２００℃の加熱帯（ｈｅａｔｉｎｇ ｚｏｎｅ）を通過して半硬化してプリプレグ（Ｐｒｅｐｒｅｇ）を得た。この際、プリプレグの全体重量に対する高分子の重量は５６質量％である。製造されたプリプレグの上下両面に厚さ１２μｍの銅箔を貼り付けて圧力２．３ＭＰａ、温度２２０℃で約１８０分間加圧して、銅張積層板（ＣＣＬ）を製造した。 The varnish was uniformly impregnated into glass fiber (Nittobo, E2116). The glass fiber impregnated with the mixed solution passed through a heating zone at 200 ° C. and was semi-cured to obtain a prepreg. At this time, the weight of the polymer with respect to the total weight of the prepreg is 56% by mass. A copper foil having a thickness of 12 μm was attached to both the upper and lower surfaces of the manufactured prepreg and pressed at a pressure of 2.3 MPa and a temperature of 220 ° C. for about 180 minutes to manufacture a copper clad laminate (CCL).
（実施例２）
５００ｍｌのフラスコに溶剤であるＭＥＫ８０ｇを加え、前記製造例１で製造されたスピロビフルオレン（Ｓｐｉｒｏ ｂｉｆｌｕｏｒｅｎｅ）構造のエポキシ３５ｇ、フェノール性硬化剤（コーロン社製、ＫＰＨ−Ｆ３１００）１５ｇ、ビスマレイミド（大和化成社製、ＢＭＩ−２３００）２５ｇ、シアネートエステル（Ｌｏｎｚａ社製、ＰＴ−３０）２５ｇ、硬化触媒としてイミダゾール（Ａｌｄｒｉｃｈ社製、２−Ｐｈｅｎｙｌ ｉｍｉｄａｚｏｌｅ）０．５ｇを加えて１時間攪拌した後、球状シリカ（アドマテックス社製、５００ｎｍ）２３３ｇをさらに加えて１時間以上さらに攪拌し、ワニスを製造した。
(Example 2)
MEK 80 g as a solvent was added to a 500 ml flask, and 35 g of spiro bifluorene-structured epoxy produced in Production Example 1 above, 15 g of phenolic curing agent (KPH-F3100, manufactured by Kolon Co., Ltd.), bismaleimide (Daiwa) After adding 25 g of Kasei Co., BMI-2300), 25 g of cyanate ester (Lonza, PT-30) and 0.5 g of imidazole (Aldrich, 2-phenyl imidazole) as a curing catalyst, the mixture was stirred for 1 hour, and then spherical. Further, 233 g of silica (manufactured by Admatechs, 500 nm) was further added and further stirred for 1 hour or more to produce a varnish.
前記製造されたワニスを実施例１のような条件下で銅張積層板を製造した。 A copper clad laminate was produced from the produced varnish under the conditions as in Example 1.
（比較例１）
５００ｍｌのフラスコに溶剤であるＭＥＫ８０ｇを加えてエポキシ（日本化薬社製、ＮＣ−３０００Ｈ）３５ｇ、フェノール性硬化剤（コーロン社製、ＫＰＨ−Ｆ３１００）１５ｇ、硬化触媒としてイミダゾール（Ａｌｄｒｉｃh社製、２−Ｐｈｅｎｙｌ ｉｍｉｄａｚｏｌｅ）０．５ｇを加えて１時間攪拌した後、球状シリカ（アドマテックス社製、５００ｎｍ）１１７ｇをさらに加えて１時間以上さらに攪拌し、ワニスを製造した。
(Comparative Example 1)
MEK80g which is a solvent is added to a 500 ml flask, 35 g of epoxy (Nippon Kayaku Co., Ltd., NC-3000H), 15 g of phenolic curing agent (Kohlon, KPH-F3100), imidazole (manufactured by Aldrich, 2 -Phenyl imidazole) 0.5 g was added and stirred for 1 hour, and then 117 g of spherical silica (manufactured by Admatechs, 500 nm) was further added and further stirred for 1 hour or more to produce a varnish.
前記ワニスをガラス繊維（日東紡社製、Ｅ２１１６）に均一に含浸した。混合溶液が含浸したガラス繊維は、２００℃の加熱帯（ｈｅａｔｉｎｇ ｚｏｎｅ）を通過して半硬化させてプリプレグ（Ｐｒｅｐｒｅｇ）を得た。この際、プリプレグの全体重量に対する高分子の重量は５６質量％である。製造されたプリプレグの上下両面に厚さ１２μｍの銅箔を貼り付けて圧力２．３ＭＰａ、温度２２０℃で約１８０分間加圧して銅張積層板（ＣＣＬ）を製造した。 The varnish was uniformly impregnated into glass fiber (Nittobo, E2116). The glass fiber impregnated with the mixed solution was passed through a 200 ° C. heating zone and semi-cured to obtain a prepreg. At this time, the weight of the polymer with respect to the total weight of the prepreg is 56% by mass. A copper foil having a thickness of 12 μm was attached to both the upper and lower surfaces of the manufactured prepreg and pressed at a pressure of 2.3 MPa and a temperature of 220 ° C. for about 180 minutes to manufacture a copper clad laminate (CCL).
（比較例２）
５００ｍｌのフラスコに溶剤であるＭＥＫ８０ｇを加え、エポキシ（ｋｕｋｄｏｅｐｏｘｙ社製、ＹＤ−１２８）３５ｇ、フェノール性硬化剤（コーロン社製、ＫＰＨ−Ｆ３１００）１５ｇ、ビスマレイミド（大和化成社製、ＢＭＩ−２３００）２５ｇ、シアネートエステル（Ｌｏｎｚａ社製、ＰＴ−３０）２５ｇ、硬化触媒としてイミダゾール（Ａｌｄｒｉｃｈ社製、２−Ｐｈｅｎｙｌ ｉｍｉｄａｚｏｌｅ）０．５ｇを加えて１時間攪拌した後、球状シリカ（アドマテックス社製、５００ｎｍ）２３３ｇをさらに加えて１時間以上さらに攪拌し、ワニスを製造した。
(Comparative Example 2)
MEK80g which is a solvent is added to a 500 ml flask, 35 g of epoxy (manufactured by kukudopexy, YD-128), 15 g of phenolic curing agent (manufactured by Kolon, KPH-F3100), bismaleimide (manufactured by Daiwa Kasei Co., Ltd., BMI-2300) 25 g, 25 g of cyanate ester (manufactured by Lonza, PT-30), 0.5 g of imidazole (manufactured by Aldrich, 2-phenyl imidazole) as a curing catalyst was added and stirred for 1 hour, and then spherical silica (manufactured by Admatechs, 500 nm). ) 233 g was further added and further stirred for 1 hour or more to produce a varnish.
前記製造されたワニスを比較例１のような条件下で銅張積層板を製造した。 A copper clad laminate was produced from the produced varnish under the conditions as in Comparative Example 1.
（銅張積層板の特性評価）
実施例と比較例によって製造された銅張積層板の銅箔を硝酸溶液を用いて完全にエッチングして除去した後、３５×５ｍｍサイズのサンプルを作製し、動的力学分析装置（ＤＭＡ：Ｄｙｎａｍｉｃ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｚｅｒ、ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ ＤＭＡ Ｑ８００）を用いて空気（ａｉｒ）雰囲気下で温度を３℃／ｍｉｎに昇温してサンプルのガラス転移温度（Ｔｇ）を測定した。
(Characteristic evaluation of copper clad laminate)
After removing the copper foil of the copper clad laminate manufactured according to the example and the comparative example by completely etching with a nitric acid solution, a sample of 35 × 5 mm size was prepared, and a dynamic mechanical analyzer (DMA: Dynamic) The glass transition temperature (Tg) of the sample was measured by raising the temperature to 3 ° C./min in an air atmosphere using a Mechanical Analyzer, TA Instruments DMA Q800.
また、同じ銅張積層板で３０×４ｍｍのサンプルを作製し、熱膨張係数（ＣＴＥ、Ｃｏｅｆｆｉｃｉｅｎｔ ｏｆ Ｔｈｅｒｍａｌ Ｅｘｐａｎｓｉｏｎ）を熱分析装置（ＴＭＡ:Ｔｈｅｒｍｏｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｚｅｒ、ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ ＴＭＡ Ｑ４００）を用いて窒素雰囲気で温度を１０℃／ｍｉｎに昇温して測定した。 In addition, a 30 × 4 mm sample was prepared with the same copper-clad laminate, and a coefficient of thermal expansion (CTE, Coefficient of Thermal Expansion) was measured using a thermal analyzer (TMA: Thermomechanical Analyzer, TA Instruments TMA Q400) in a nitrogen atmosphere. Was measured by raising the temperature to 10 ° C./min.
全面エッチングされた銅張積層板に圧延銅箔を貼り付けてＮｅｔｗｏｒｋ ａｎａｌｙｚｅｒ（ＰＮＡ Ｓｅｒｉｅｓ Ｎｅｔｗｏｒｋ Ａｎａｌｙｚｅｒ、Ａｇｉｌｅｎｔ社製、Ｅ８３６４Ｂ）を用いて１ＧＨｚの領域で誘電率（Ｄｋ）および誘電損（Ｄｆ）を測定した。 Rolled copper foil is applied to a copper-clad laminate that has been etched on the entire surface, and dielectric constant (Dk) and dielectric loss (Df) are measured in the 1 GHz region using a network analyzer (PNA Series Network Analyzer, manufactured by Agilent, E8364B). did.
前記表１は、本発明の実施例および比較例による組成物の含量を記録したデータである。 Table 1 is data recording the content of the compositions according to the examples and comparative examples of the present invention.
前記表２から分かるように、スピロビフルオレン構造のエポキシを含む実施例１および実施例２のサンプルの物性は、通常のエポキシを含んで製造した比較例１および比較例２のサンプルより相対的に熱膨張係数およびガラス転移温度が向上したことが分かる。 As can be seen from Table 2, the physical properties of the samples of Example 1 and Example 2 containing an epoxy having a spirobifluorene structure are relatively larger than those of the samples of Comparative Examples 1 and 2 produced by containing an ordinary epoxy. It can be seen that the coefficient of thermal expansion and the glass transition temperature have improved.
特に、実施例１および実施例２の誘電損および誘電率は、比較例１および比較例２の誘電損および誘電率よりはるかに低いことが分かる。これにより、スピロビフルオレン構造のエポキシ樹脂を含む樹脂組成物は自由体積が大きくなるため、誘電損および誘電率の向上に優れた効果を奏することが分かる。 In particular, it can be seen that the dielectric loss and dielectric constant of Example 1 and Example 2 are much lower than those of Comparative Example 1 and Comparative Example 2. Accordingly, it can be seen that the resin composition containing the epoxy resin having the spirobifluorene structure has a large free volume, and thus has an excellent effect in improving the dielectric loss and the dielectric constant.
本発明の一実施例によるプリント回路基板用絶縁樹脂組成物は、スピロビフルオレン構造のエポキシ樹脂を含むことで自由体積が大きくなり、誘電率および誘電損の物性特性を向上させることができる。 The insulating resin composition for a printed circuit board according to an embodiment of the present invention includes a spirobifluorene structure epoxy resin, thereby increasing the free volume and improving the physical properties of dielectric constant and dielectric loss.
また、前記スピロビフルオレン構造のエポキシ樹脂により、従来技術と同様であるかより向上した耐熱性および熱膨張係数の特性を有するプリント回路基板用絶縁樹脂組成物を提供することができる。 In addition, the insulating resin composition for a printed circuit board having the same heat resistance and thermal expansion coefficient characteristics as those of the prior art can be provided by the spirobifluorene structure epoxy resin.
また、前記樹脂組成物に、無機充填剤、シアネートエステル樹脂、またはビスマレイミド樹脂を添加することで、耐熱性および熱膨張係数の特性をより向上させることができる。 Moreover, the characteristic of heat resistance and a thermal expansion coefficient can be improved more by adding an inorganic filler, cyanate ester resin, or a bismaleimide resin to the said resin composition.
本発明の一実施例によるプリント回路基板用絶縁樹脂組成物を用いて製造された絶縁フィルムまたはプリプレグをプリント回路基板に適用して、耐熱性、熱膨張係数、誘電率および誘電損の特性が向上した製品を得ることができる。 An insulating film or prepreg manufactured using an insulating resin composition for a printed circuit board according to an embodiment of the present invention is applied to a printed circuit board to improve heat resistance, thermal expansion coefficient, dielectric constant, and dielectric loss characteristics. Product can be obtained.
以上、本発明を具体的な実施例に基づいて詳細に説明したが、これは本発明を具体的に説明するためのものであり、本発明はこれに限定されず、該当分野における通常の知識を有する者であれば、本発明の技術的思想内にての変形や改良が可能であることは明白であろう。 As described above, the present invention has been described in detail based on the specific embodiments. However, the present invention is only for explaining the present invention, and the present invention is not limited thereto. It will be apparent to those skilled in the art that modifications and improvements within the technical idea of the present invention are possible.
本発明の単純な変形乃至変更はいずれも本発明の領域に属するものであり、本発明の具体的な保護範囲は添付の特許請求の範囲により明確になるであろう。 All simple variations and modifications of the present invention belong to the scope of the present invention, and the specific scope of protection of the present invention will be apparent from the appended claims.
本発明は、プリント回路基板用絶縁樹脂組成物およびこれを用いた製品に適用可能である。 The present invention is applicable to an insulating resin composition for printed circuit boards and products using the same.
Claims (12)
硬化剤と、を含む、プリント回路基板用絶縁樹脂組成物。
An insulating resin composition for printed circuit boards, comprising a curing agent.
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| US11427707B2 (en) * | 2017-09-29 | 2022-08-30 | Nippon Steel Chemical & Material Co., Ltd. | Curable epoxy resin composition and fiber-reinforced composite material using same |
| JP7209470B2 (en) * | 2018-03-13 | 2023-01-20 | 帝人株式会社 | Prepregs and carbon fiber reinforced composites |
| US11718580B2 (en) * | 2019-05-08 | 2023-08-08 | Meta Platforms Technologies, Llc | Fluorene derivatized monomers and polymers for volume Bragg gratings |
| US11780819B2 (en) | 2019-11-27 | 2023-10-10 | Meta Platforms Technologies, Llc | Aromatic substituted alkane-core monomers and polymers thereof for volume Bragg gratings |
| US11879024B1 (en) | 2020-07-14 | 2024-01-23 | Meta Platforms Technologies, Llc | Soft mold formulations for surface relief grating fabrication with imprinting lithography |
| CN115093686A (en) * | 2022-07-20 | 2022-09-23 | 亚洲泰格集团有限公司 | Liquid crystal polymer film and preparation method thereof |
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2013
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| JP2015117358A (en) | 2015-06-25 |
| KR101987310B1 (en) | 2019-06-10 |
| KR20150069895A (en) | 2015-06-24 |
| TW201525053A (en) | 2015-07-01 |
| TWI624506B (en) | 2018-05-21 |
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