JPWO2019003823A1 - Active ester compound and curable composition - Google Patents
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Abstract
硬化物において高温条件下での弾性率が低い活性エステル化合物、これを含有する硬化性組成物、その硬化物、半導体封止材料及びプリント配線基板を提供することを目的とする。具体的には、ジヒドロキシベンゼン化合物（ａ１）と芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）とのエステル化物であって、前記ジヒドロキシベンゼン化合物（ａ１）が１，２−ジヒドロキシベンゼン化合物又は１，３−ジヒドロキシベンゼン化合物である活性エステル化合物、これを含有する硬化性組成物、その硬化物、半導体封止材料及びプリント配線基板を提供する。An object of the present invention is to provide an active ester compound having a low elastic modulus under a high temperature condition in a cured product, a curable composition containing the same, a cured product thereof, a semiconductor encapsulating material and a printed wiring board. Specifically, it is an esterified product of a dihydroxybenzene compound (a1) and an aromatic monocarboxylic acid or an acid halide thereof (a2), wherein the dihydroxybenzene compound (a1) is a 1,2-dihydroxybenzene compound or 1 , An active ester compound which is a 3-dihydroxybenzene compound, a curable composition containing the same, a cured product thereof, a semiconductor encapsulating material and a printed wiring board.
Description
本発明は高温条件下での弾性率が低い活性エステル化合物、これを含有する硬化性組成物、その硬化物、半導体封止材料及びプリント配線基板に関する。 The present invention relates to an active ester compound having a low elastic modulus under high temperature conditions, a curable composition containing the same, a cured product thereof, a semiconductor encapsulating material and a printed wiring board.
半導体や多層プリント基板等に用いられる絶縁材料の技術分野では、各種電子部材の薄型化や小型化に伴い、これらの市場動向に合わせた新たな樹脂材料の開発が求められている。半導体封止材料に求められる性能としては、リフロー性向上の為に高温条件下での弾性率低いことが求められる。この他、硬化物における耐熱性や耐吸湿性は勿論のこと、信号の高速化及び高周波数化対策として、硬化物における誘電率及び誘電正接値が低いこと、高温条件下での信頼性としてガラス転移温度（Ｔｇ）等の物性変化がないこと、薄型化に伴う反りや歪み対策として硬化収縮率や線膨張係数が低いこと等も重要である。 In the technical field of insulating materials used for semiconductors, multilayer printed circuit boards, and the like, with the thinning and miniaturization of various electronic members, development of new resin materials that meet these market trends is required. As a performance required for a semiconductor encapsulating material, a low elastic modulus under high temperature conditions is required for improving reflowability. In addition to the heat resistance and moisture absorption resistance of the cured product, the low dielectric constant and dielectric loss tangent value of the cured product as a measure for speeding up the signal and increasing the frequency, and glass for reliability under high temperature conditions It is also important that there is no change in physical properties such as the transition temperature (Tg), and that the curing shrinkage rate and the linear expansion coefficient are low as a measure against warpage and distortion that accompany thinning.
硬化物における耐熱性や誘電特性等に優れる樹脂材料として、ジ（１−ナフチル）イソフタレートをエポキシ樹脂の硬化剤として用いる技術が知られている（下記特許文献１参照）。特許文献１に記載されたエポキシ樹脂組成物は、ジ（α−ナフチル）イソフタレートをエポキシ樹脂硬化剤として用いることにより、フェノールノボラック樹脂のような従来型のエポキシ樹脂硬化剤を用いた場合と比較して硬化物における誘電率や誘電正接の値は確かに低いものの、硬化物における高温条件下での弾性率が近年要求されるレベルを満足するものでは無かった。また、溶融粘度が高いことから、半導体封止材料等溶融粘度が低いことが求められる用途においては使用に制限があった。 A technique using di (1-naphthyl) isophthalate as a curing agent for an epoxy resin is known as a resin material having excellent heat resistance and dielectric properties in a cured product (see Patent Document 1 below). The epoxy resin composition described in Patent Document 1 uses di (α-naphthyl) isophthalate as an epoxy resin curing agent to compare with the case of using a conventional epoxy resin curing agent such as phenol novolac resin. Although the values of the dielectric constant and dielectric loss tangent of the cured product are certainly low, the elastic modulus of the cured product under high temperature conditions did not satisfy the level required in recent years. Further, since the melt viscosity is high, there is a limitation in use in applications such as semiconductor encapsulation materials where low melt viscosity is required.
従って、本発明が解決しようとする課題は、高温条件下での弾性率が低い活性エステル化合物、これを含有する硬化性組成物、その硬化物、半導体封止材料及びプリント配線基板を提供することにある。 Therefore, the problem to be solved by the present invention is to provide an active ester compound having a low elastic modulus under high temperature conditions, a curable composition containing the same, a cured product thereof, a semiconductor encapsulating material and a printed wiring board. It is in.
本発明者らは前記課題を解決すべく鋭意検討した結果、１，２−ジヒドロキシベンゼン化合物又は１，３−ジヒドロキシベンゼン化合物と芳香族モノカルボン酸又はその酸ハロゲン化物とのジエステル化物である活性エステル化合物は、硬化物における高温条件下での弾性率が低い上、溶融粘度も低いことを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that an active ester which is a diester of a 1,2-dihydroxybenzene compound or a 1,3-dihydroxybenzene compound and an aromatic monocarboxylic acid or an acid halide thereof. The compound was found to have a low elastic modulus in a cured product under high temperature conditions and a low melt viscosity, and completed the present invention.
即ち、本発明は、ジヒドロキシベンゼン化合物（ａ１）と芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）とのエステル化物であって、前記ジヒドロキシベンゼン化合物（ａ１）が１，２−ジヒドロキシベンゼン化合物又は１，３−ジヒドロキシベンゼン化合物である活性エステル化合物に関する。 That is, the present invention is an esterified product of a dihydroxybenzene compound (a1) and an aromatic monocarboxylic acid or an acid halide thereof (a2), wherein the dihydroxybenzene compound (a1) is a 1,2-dihydroxybenzene compound or It relates to active ester compounds which are 1,3-dihydroxybenzene compounds.
本発明は更に、前記活性エステル化合物と、硬化剤とを含有する硬化性組成物に関する。 The present invention further relates to a curable composition containing the active ester compound and a curing agent.
本発明は更に、前記硬化性組成物の硬化物に関する。 The present invention further relates to a cured product of the curable composition.
本発明は更に、前記硬化性組成物を用いてなる半導体封止材料に関する。 The present invention further relates to a semiconductor encapsulating material using the curable composition.
本発明は更に、前記硬化性組成物を用いてなるプリント配線基板に関する。 The present invention further relates to a printed wiring board using the curable composition.
本発明によれば、硬化物において高温条件下での弾性率が低い活性エステル化合物、これを含有する硬化性組成物、その硬化物、半導体封止材料及びプリント配線基板を提供することができる。 According to the present invention, it is possible to provide an active ester compound having a low elastic modulus in a cured product under high temperature conditions, a curable composition containing the same, a cured product thereof, a semiconductor encapsulating material, and a printed wiring board.
以下、本発明を詳細に説明する。
本発明の活性エステル化合物は、ジヒドロキシベンゼン化合物（ａ１）と芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）とのエステル化物であって、前記ジヒドロキシベンゼン化合物（ａ１）が１，２−ジヒドロキシベンゼン化合物又は１，３−ジヒドロキシベンゼン化合物であることを特徴とする。Hereinafter, the present invention will be described in detail.
The active ester compound of the present invention is an esterified product of a dihydroxybenzene compound (a1) and an aromatic monocarboxylic acid or an acid halide thereof (a2), wherein the dihydroxybenzene compound (a1) is 1,2-dihydroxybenzene. It is a compound or a 1,3-dihydroxybenzene compound.
前記ジヒドロキシベンゼン化合物（ａ１）は、１，２−ジヒドロキシベンゼン、１，３−ジヒドロキシベンゼン、及びこれらの芳香環上に一つ乃至複数の置換基を有するジヒドロキシベンゼン化合物が挙げられる。前記置換基は、例えば、脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基等が挙げられる。前記脂肪族炭化水素基は直鎖型及び分岐型のいずれでもよく、構造中に不飽和結合を有していてもよい。具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、へキシル基等のアルキル基；シクロへキシル基等のシクロアルキル基；ビニル基、アリル基、プロパギル基等の不飽和結合含有基等が挙げられる。前記アルコキシ基は、メトキシ基、エトキシ基、プロピルオキシ基、ブトキシ基等が挙げられる。前記ハロゲン原子は、フッ素原子、塩素原子、臭素原子等が挙げられる。前記アリール基は、フェニル基、ナフチル基、アントリル基、及びこれらの芳香核上に前記脂肪族炭化水素基やアルコキシ基、ハロゲン原子等が置換した構造部位等が挙げられる。前記アラルキル基は、ベンジル基、フェニルエチル基、ナフチルメチル基、ナフチルエチル基、及びこれらの芳香核上に前記アルキル基やアルコキシ基、ハロゲン原子等が置換した構造部位等が挙げられる。前記ジヒドロキシベンゼン化合物（ａ１）は一種類を単独で用いても良いし、２種類以上を併用しても良い。 Examples of the dihydroxybenzene compound (a1) include 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, and dihydroxybenzene compounds having one or more substituents on their aromatic rings. Examples of the substituent include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group and an aralkyl group. The aliphatic hydrocarbon group may be linear or branched, and may have an unsaturated bond in its structure. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group; cycloalkyl groups such as cyclohexyl group; unsaturated groups such as vinyl group, allyl group, and propargyl group. Examples include a bond-containing group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural part in which the aliphatic hydrocarbon group, the alkoxy group, a halogen atom or the like is substituted on the aromatic nucleus thereof. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a structural site in which the alkyl group, the alkoxy group, a halogen atom or the like is substituted on the aromatic nucleus thereof. The dihydroxybenzene compound (a1) may be used alone or in combination of two or more.
前記芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）は、ベンゼンカルボン酸、ナフタレンカルボン酸、これらの芳香核上に脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基等の置換基を一つ乃至複数有する化合物、及びこれらの酸ハロゲン化物等が挙げられる。これらは一種類を単独で用いても良いし、２種類以上を併用しても良い。中でも、硬化物における高温条件下での弾性率が低く、また、硬化性等にも優れる活性エステル化合物となることから、ベンゼンカルボン酸又はそのハロゲン化物が好ましい。したがって、本発明の活性エステル化合物のより好ましい構造としては、下記構造式（１−１）又は（１−２）で表されるものが挙げられる The aromatic monocarboxylic acid or its acid halide (a2) is a benzenecarboxylic acid, a naphthalenecarboxylic acid, or a substituent such as an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group on the aromatic nucleus thereof. Examples thereof include compounds having one or more groups and acid halides thereof. These may be used alone or in combination of two or more. Among them, benzenecarboxylic acid or its halide is preferable because it is an active ester compound that has a low elastic modulus in a cured product under high temperature conditions and is excellent in curability and the like. Therefore, more preferable structures of the active ester compound of the present invention include those represented by the following structural formula (1-1) or (1-2).
前記ジヒドロキシベンゼン化合物（ａ１）と芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）との反応は、例えば、アルカリ触媒の存在下、４０〜６５℃程度の温度条件下で加熱撹拌する方法により行うことができる。反応は必要に応じて有機溶媒中で行っても良い。また、反応終了後は所望に応じて、水洗や再沈殿等により反応生成物を精製しても良い。 The reaction between the dihydroxybenzene compound (a1) and the aromatic monocarboxylic acid or its acid halide (a2) is carried out, for example, by heating and stirring under the temperature condition of about 40 to 65 ° C. in the presence of an alkali catalyst. be able to. The reaction may be carried out in an organic solvent if necessary. Further, after the completion of the reaction, the reaction product may be purified by washing with water or reprecipitation, if desired.
前記アルカリ触媒は、例えば、水酸化ナトリウム、水酸化カリウム、トリエチルアミン、ピリジン等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。また、３．０〜３０％程度の水溶液として用いても良い。中でも、触媒能の高い水酸化ナトリウム又は水酸化カリウムが好ましい。 Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. These may be used alone or in combination of two or more. Further, it may be used as an aqueous solution of about 3.0 to 30%. Among them, sodium hydroxide or potassium hydroxide having high catalytic ability is preferable.
前記有機溶媒は、例えば、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溶媒、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル溶媒、セロソルブ、ブチルカルビトール等のカルビトール溶媒、トルエン、キシレン等の芳香族炭化水素溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上の混合溶媒としても良い。 The organic solvent is, for example, a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetate ester solvent such as carbitol acetate, cellosolve, butyl carbitol. And the like, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. These may be used alone or as a mixed solvent of two or more kinds.
前記ジヒドロキシベンゼン化合物（ａ１）と芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）との反応割合は、目的の活性エステル化合物を高収率で得られることから、前記ジヒドロキシベンゼン化合物（ａ１）が有する水酸基の合計１モルに対し、前記芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）が０．９５〜１．０５モルとなる割合であることが好ましい。 The reaction ratio between the dihydroxybenzene compound (a1) and the aromatic monocarboxylic acid or its acid halide (a2) is such that the target active ester compound can be obtained in a high yield. The ratio of the aromatic monocarboxylic acid or its acid halide (a2) to 0.95 to 1.05 mol is preferable with respect to the total 1 mol of the hydroxyl groups.
前記活性エステル化合物の溶融粘度は、ＡＳＴＭ Ｄ４２８７に準拠し、ＩＣＩ粘度計にて測定した１５０℃における値が０．０１〜５０ｄＰａ・ｓの範囲であることが好ましく、０．０１〜５ｄＰａ・ｓの範囲であることがより好ましく、０．０１〜０．１ｄＰａ・ｓの範囲であることが特に好ましい。 The melt viscosity of the active ester compound is based on ASTM D4287, and the value at 150 ° C. measured by an ICI viscometer is preferably in the range of 0.01 to 50 dPa · s, and in the range of 0.01 to 5 dPa · s. The range is more preferable, and the range of 0.01 to 0.1 dPa · s is particularly preferable.
本発明の硬化性組成物は、前記本発明の活性エステル化合物と併せて、その他の活性エステル化合物を含有しても良い。前記その他の活性エステル化合物としては、分子構造中にフェノール性水酸基を一つ有する化合物と芳香族ポリカルボン酸又はその酸ハロゲン化物とのエステル化物、ポリヒドロキナフタレンと芳香族モノカルボン酸又はその酸ハロゲン化物とのエステル化物、分子構造中にフェノール性水酸基を一つ有する化合物、芳香族ポリカルボン酸又はその酸ハロゲン化物及び分子構造中にフェノール性水酸基を２つ以上有する化合物のエステル化物、芳香族ポリカルボン酸又はその酸ハロゲン化物、分子構造中にフェノール性水酸基を２つ以上有する化合物及び芳香族モノカルボン酸又はその酸ハロゲン化物のエステル化物等が挙げられる。 The curable composition of the present invention may contain other active ester compounds in addition to the active ester compound of the present invention. Examples of the other active ester compound include an ester compound of a compound having one phenolic hydroxyl group in the molecular structure with an aromatic polycarboxylic acid or an acid halide thereof, polyhydroquinaphthalene and an aromatic monocarboxylic acid or an acid halogen thereof. Ester compound, a compound having one phenolic hydroxyl group in the molecular structure, an aromatic polycarboxylic acid or an acid halide thereof and an esterified compound of a compound having two or more phenolic hydroxyl groups in the molecular structure, an aromatic poly Examples thereof include carboxylic acids or acid halides thereof, compounds having two or more phenolic hydroxyl groups in the molecular structure, and aromatic monocarboxylic acids or esterified products of acid halides thereof.
前記その他の活性エステル化合物を用いる場合、本発明が奏する効果が十分に発揮されることから、本発明の活性エステル化合物とその他の活性エステル化合物との合計に対する本発明の活性エステル化合物の割合が８０質量％以上であることが好ましく、９０質量％以上であることがより好ましい。また、本発明の活性エステル化合物とその他の活性エステル化合物との配合物の溶融粘度が０．０１〜５０ｄＰａ・ｓの範囲であることが好ましく、０．０１〜５ｄＰａ・ｓの範囲であることがより好ましく、０．０１〜０．１ｄＰａ・ｓの範囲であることが特に好ましい。配合物の溶融粘度はＡＳＴＭ Ｄ４２８７に準拠し、ＩＣＩ粘度計にて測定した１５０℃における値である。 When the other active ester compound is used, the effect of the present invention is sufficiently exerted, and therefore the ratio of the active ester compound of the present invention to the total of the active ester compound of the present invention and the other active ester compound is 80. It is preferably at least mass%, more preferably at least 90 mass%. Further, the melt viscosity of the blend of the active ester compound of the present invention and the other active ester compound is preferably in the range of 0.01 to 50 dPa · s, and more preferably in the range of 0.01 to 5 dPa · s. More preferably, it is particularly preferably in the range of 0.01 to 0.1 dPa · s. The melt viscosity of the blend is a value at 150 ° C. measured by an ICI viscometer according to ASTM D4287.
本発明の硬化性組成物は、前述の活性エステル化合物と硬化剤とを含有する。前記硬化剤は前記活性エステル化合物と反応し得る化合物であれば良く、特に限定なく様々な化合物が利用できる。硬化剤の一例としては、例えば、エポキシ樹脂が挙げられる。 The curable composition of the present invention contains the above-mentioned active ester compound and a curing agent. The curing agent may be any compound that can react with the active ester compound, and various compounds can be used without particular limitation. An example of the curing agent is an epoxy resin.
前記エポキシ樹脂は、例えば、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、ナフトールノボラック型エポキシ樹脂、ビスフェノールノボラック型エポキシ樹脂、ビフェノールノボラック型エポキシ樹脂、ビスフェノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、テトラフェノールエタン型エポキシ樹脂、ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂等が挙げられる。 The epoxy resin is, for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol novolac type epoxy resin, biphenol novolac type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, triphenol methane. Type epoxy resin, tetraphenolethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin and the like.
本発明の硬化性組成物において、前記活性エステル化合物と硬化剤との配合割合は特に限定なく、所望の硬化物性能等に応じて適宜調整することができる。硬化剤としてエポキシ樹脂を用いる場合の配合の一例としては、硬化性組成物中のエポキシ基の合計１モルに対して、前記活性エステル化合物中の官能基の合計が０．７〜１．５モルとなる割合であることが好ましい。 In the curable composition of the present invention, the mixing ratio of the active ester compound and the curing agent is not particularly limited, and can be appropriately adjusted according to the desired performance of the cured product. As an example of the composition when an epoxy resin is used as a curing agent, the total of the functional groups in the active ester compound is 0.7 to 1.5 mol with respect to the total of 1 mol of the epoxy groups in the curable composition. The following ratio is preferable.
本発明の硬化性組成物は、更にその他の樹脂成分を含有しても良い。その他の樹脂成分は、例えば、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、イミダゾ−ル、ＢＦ３−アミン錯体、グアニジン誘導体等のアミン化合物；ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂等のアミド化合物；無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等の酸無水物；シアン酸エステル樹脂；ビスマレイミド樹脂；ベンゾオキサジン樹脂；スチレン−無水マレイン酸樹脂；ジアリルビスフェノールやトリアリルイソシアヌレートに代表されるアリル基含有樹脂；ポリリン酸エステルやリン酸エステル−カーボネート共重合体等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。これらその他の樹脂成分の配合割合は特に限定なく、所望の硬化物性能等に応じて適宜調整することができる。The curable composition of the present invention may further contain other resin components. Other resin components include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complex, guanidine derivative; dicyandiamide, dimer of linolenic acid, and the like. Amide compounds such as polyamide resins synthesized with ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride Acids, acid anhydrides such as methylhexahydrophthalic anhydride, cyanate ester resins, bismaleimide resins, benzoxazine resins, styrene-maleic anhydride resins, diallyl bisphenols and triaries Allyl group-containing resin represented by isocyanurate; polyphosphoric acid ester or phosphoric acid ester - carbonate copolymer, and the like. These may be used alone or in combination of two or more. The mixing ratio of these other resin components is not particularly limited, and can be appropriately adjusted according to the desired performance of the cured product and the like.
本発明の硬化性組成物は必要に応じて硬化促進剤、難燃剤、無機質充填材、シランカップリング剤、離型剤、顔料、乳化剤等の各種添加剤を含有しても良い。 The curable composition of the present invention may contain various additives such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment and an emulsifier, if necessary.
前記硬化促進剤は、例えば、リン系化合物、第３級アミン、イミダゾール化合物、ピリジン化合物、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。中でも、硬化性、耐熱性、電気特性、耐湿信頼性等に優れる点から、リン系化合物ではトリフェニルホスフィン、第３級アミンでは１，８−ジアザビシクロ−［５．４．０］−ウンデセン（ＤＢＵ）、イミダゾール化合物では２−エチル−４−メチルイミダゾール、ピリジン化合物では４−ジメチルアミノピリジンが好ましい。 Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, Lewis acids, amine complex salts and the like. Of these, triphenylphosphine is a phosphorus compound and 1,8-diazabicyclo- [5.4.0] -undecene (DBU) is a tertiary amine because of its excellent curability, heat resistance, electrical characteristics, and moisture resistance reliability. ), 2-ethyl-4-methylimidazole is preferable for the imidazole compound, and 4-dimethylaminopyridine is preferable for the pyridine compound.
前記難燃剤は、例えば、赤リン、リン酸一アンモニウム、リン酸二アンモニウム、リン酸三アンモニウム、ポリリン酸アンモニウム等のリン酸アンモニウム、リン酸アミド等の無機リン化合物；リン酸エステル化合物、ホスホン酸化合物、ホスフィン酸化合物、ホスフィンオキシド化合物、ホスホラン化合物、有機系含窒素リン化合物、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド、１０−（２，５―ジヒドロオキシフェニル）―１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド、１０―（２，７−ジヒドロオキシナフチル）−１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド等の環状有機リン化合物、及びそれをエポキシ樹脂やフェノール樹脂等の化合物と反応させた誘導体等の有機リン化合物；トリアジン化合物、シアヌル酸化合物、イソシアヌル酸化合物、フェノチアジン等の窒素系難燃剤；シリコーンオイル、シリコーンゴム、シリコーン樹脂等のシリコーン系難燃剤；金属水酸化物、金属酸化物、金属炭酸塩化合物、金属粉、ホウ素化合物、低融点ガラス等の無機難燃剤等が挙げられる。これら難燃剤を用いる場合は、硬化性組成物中０．１〜２０質量％の範囲であることが好ましい。 Examples of the flame retardant include red phosphorous, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, inorganic phosphorus compounds such as phosphoric acid amides; phosphate ester compounds and phosphonic acids. Compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl ) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organic phosphorus Compounds and compounds such as epoxy resins and phenolic resins Organic phosphorus compounds such as reacted derivatives; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazines; silicone-based flame retardants such as silicone oils, silicone rubbers and silicone resins; metal hydroxides, metals Inorganic flame retardants such as oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass are included. When using these flame retardants, it is preferably in the range of 0.1 to 20 mass% in the curable composition.
前記無機質充填材は、例えば、本発明の硬化性組成物を半導体封止材料用途に用いる場合などに配合される。前記無機質充填材は、例えば、溶融シリカ、結晶シリカ、アルミナ、窒化珪素、水酸化アルミ等が挙げられる。中でも、無機質充填材をより多く配合することが可能となることから、前記溶融シリカが好ましい。前記溶融シリカは破砕状、球状のいずれでも使用可能であるが、溶融シリカの配合量を高め、且つ、硬化性組成物の溶融粘度の上昇を抑制するためには、球状のものを主に用いることが好ましい。更に、球状シリカの配合量を高めるためには、球状シリカの粒度分布を適当に調整することが好ましい。その充填率は硬化性組成物１００質量部中、０．５〜９５質量部の範囲で配合することが好ましい。 The inorganic filler is blended, for example, when the curable composition of the present invention is used for semiconductor encapsulation material. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among them, the fused silica is preferable because it is possible to add a larger amount of the inorganic filler. The fused silica may be used in the crushed form or in the spherical form, but in order to increase the blending amount of the fused silica and suppress the increase in the melt viscosity of the curable composition, the spherical form is mainly used. It is preferable. Further, in order to increase the compounding amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably 0.5 to 95 parts by mass in 100 parts by mass of the curable composition.
この他、本発明の硬化性組成物を導電ペーストなどの用途に使用する場合は、銀粉や銅粉等の導電性充填剤を用いることができる。 In addition, when the curable composition of the present invention is used for applications such as a conductive paste, a conductive filler such as silver powder or copper powder can be used.
以上詳述した通り、本発明の活性エステル化合物及びこれを含有する硬化性組成物は、硬化物における高温条件下での弾性率が低い特徴を有する。この他、汎用有機溶剤への溶解性や、耐熱性、耐吸水性、低硬化収縮性、誘電特性にも優れ、また、溶融粘度が低い等、樹脂材料に求められる他の一般的な要求性能も十分に高いものである。このため、プリント配線基板や半導体封止材料、レジスト材料等の電子材料用途の他、塗料や接着剤、成型品等の用途にも広く利用することができる。 As described above in detail, the active ester compound of the present invention and the curable composition containing the same are characterized in that the cured product has a low elastic modulus under high temperature conditions. In addition, other general required performance required for resin materials such as solubility in general-purpose organic solvents, heat resistance, water absorption resistance, low curing shrinkage, excellent dielectric properties, low melt viscosity, etc. Is also high enough. Therefore, it can be widely used not only for electronic materials such as printed wiring boards, semiconductor encapsulation materials, resist materials and the like, but also for applications such as paints, adhesives and molded products.
本発明の硬化性組成物をプリント配線基板用途やビルドアップ接着フィルム用途に用いる場合、一般には有機溶剤を配合して希釈して用いることが好ましい。前記有機溶剤は、メチルエチルケトン、アセトン、ジメチルホルムアミド、メチルイソブチルケトン、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、エチルジグリコールアセテート、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。有機溶剤の種類や配合量は硬化性組成物の使用環境に応じて適宜調整できるが、例えば、プリント配線板用途では、メチルエチルケトン、アセトン、ジメチルホルムアミド等の沸点が１６０℃以下の極性溶剤であることが好ましく、不揮発分が４０〜８０質量％となる割合で使用することが好ましい。ビルドアップ接着フィルム用途では、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン溶剤、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル溶剤、セロソルブ、ブチルカルビトール等のカルビトール溶剤、トルエン、キシレン等の芳香族炭化水素溶剤、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等を用いることが好ましく、不揮発分が３０〜６０質量％となる割合で使用することが好ましい。 When the curable composition of the present invention is used for printed wiring board applications and build-up adhesive film applications, it is generally preferable to use an organic solvent after diluting it. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The type and blending amount of the organic solvent can be appropriately adjusted according to the environment in which the curable composition is used. For example, in printed wiring board applications, methyl ethyl ketone, acetone, dimethylformamide, etc. must be a polar solvent with a boiling point of 160 ° C. or less. Is preferable, and it is preferable to use it in a ratio such that the nonvolatile content is 40 to 80% by mass. For build-up adhesive film applications, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, acetic acid ester solvents such as cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, carbitol such as cellosolve, butyl carbitol, etc. It is preferable to use a solvent, an aromatic hydrocarbon solvent such as toluene or xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone or the like, and it is preferable to use a nonvolatile content of 30 to 60% by mass.
また、本発明の硬化性組成物を用いてプリント配線基板を製造する方法は、例えば、硬化性組成物を補強基材に含浸し硬化させてプリプレグを得、これと銅箔とを重ねて加熱圧着させる方法が挙げられる。前記補強基材は、紙、ガラス布、ガラス不織布、アラミド紙、アラミド布、ガラスマット、ガラスロービング布などが挙げられる。硬化性組成物の含浸量は特に限定されないが、通常、プリプレグ中の樹脂分が２０〜６０質量％となるように調製することが好ましい。 Further, the method for producing a printed wiring board using the curable composition of the present invention is, for example, impregnating a curable composition into a reinforcing base material and curing it to obtain a prepreg. A method of pressure bonding may be mentioned. Examples of the reinforcing substrate include paper, glass cloth, glass non-woven cloth, aramid paper, aramid cloth, glass mat, and glass roving cloth. The impregnated amount of the curable composition is not particularly limited, but it is usually preferable to prepare it so that the resin content in the prepreg is 20 to 60% by mass.
本発明の硬化性組成物を半導体封止材料用途に用いる場合、一般には無機質充填材を配合することが好ましい。半導体封止材料は、例えば、押出機、ニーダー、ロール等を用いて配合物を混合して調製することができる。得られた半導体封止材料を用いて半導体パッケージを成型する方法は、例えば、該半導体封止材料を注型或いはトランスファー成形機、射出成型機などを用いて成形し、更に５０〜２００℃の温度条件下で２〜１０時間加熱する方法が挙げられ、このような方法により、成形物である半導体装置を得ることが出来る。 When the curable composition of the present invention is used for semiconductor encapsulation materials, it is generally preferable to add an inorganic filler. The semiconductor encapsulating material can be prepared by mixing the compound using an extruder, a kneader, a roll, or the like. The method of molding a semiconductor package using the obtained semiconductor encapsulating material is, for example, molding the semiconductor encapsulating material using a casting or transfer molding machine, an injection molding machine or the like, and further, at a temperature of 50 to 200 ° C. There is a method of heating for 2 to 10 hours under the conditions, and a semiconductor device which is a molded product can be obtained by such a method.
次に本発明を実施例、比較例により具体的に説明する。実施例中の「部」及び「％」の記載は、特に断わりのない限り質量基準である。 Next, the present invention will be specifically described with reference to Examples and Comparative Examples. Descriptions of "part" and "%" in Examples are based on mass unless otherwise specified.
◆溶融粘度測定法
本願実施例において活性エステル化合物の溶融粘度は、ＡＳＴＭ Ｄ４２８７に準拠し、１５０℃における溶融粘度をＩＣＩ粘度計にて測定した。◆ Melt Viscosity Measurement Method In the examples of the present application, the melt viscosity of the active ester compound was measured according to ASTM D4287, and the melt viscosity at 150 ° C. was measured with an ICI viscometer.
実施例１ 活性エステル化合物（１）の製造
温度計、滴下ロート、冷却管、分留管、攪拌器を取り付けたフラスコにレゾルシン１１０ｇとメチルイソブチルケトン１０００ｇを仕込み、系内を減圧窒素置換しながら溶解させた。次いで、塩化ベンゾイル２１８ｇを仕込み、系内を減圧窒素置換しながら溶解させた。テトラブチルアンモニウムブロマイド０．５ｇを加え、窒素ガスパージを施しながら、系内を６０℃以下に制御して、２０％水酸化ナトリウム水溶液４２０ｇを３時間かけて滴下した。滴下終了後、そのまま１時間撹拌を続けて反応させた。反応終了後、反応混合物を静置して分液し、水層を取り除いた。残った有機層に水を加えて約１５分間攪拌混合した後、混合物を静置して分液し、水層を取り除いた。水層のｐＨが７になるまでこの操作を繰り返した後、デカンタ脱水で水分とトルエンを除去し、活性エステル化合物（１）を得た。活性エステル化合物（１）の溶融粘度は０．０２ｄＰａ・ｓであった。Example 1 Production of Active Ester Compound (1) 110 g of resorcin and 1000 g of methyl isobutyl ketone were charged into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, and the system was dissolved under reduced pressure with nitrogen. Let Next, 218 g of benzoyl chloride was charged, and the system was dissolved while substituting nitrogen under reduced pressure. While adding 0.5 g of tetrabutylammonium bromide and purging with nitrogen gas, the inside of the system was controlled at 60 ° C. or lower and 420 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropping, stirring was continued for 1 hour to carry out the reaction. After completion of the reaction, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and the mixture was stirred and mixed for about 15 minutes, and then the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer reached 7, water and toluene were removed by decanter dehydration to obtain an active ester compound (1). The melt viscosity of the active ester compound (1) was 0.02 dPa · s.
実施例２ 活性エステル化合物（２）の製造
温度計、滴下ロート、冷却管、分留管、攪拌器を取り付けたフラスコにカテコール１１０ｇとメチルイソブチルケトン１０００ｇを仕込み、系内を減圧窒素置換しながら溶解させた。次いで、塩化ベンゾイル２１８ｇを仕込み、系内を減圧窒素置換しながら溶解させた。テトラブチルアンモニウムブロマイド０．５ｇを加え、窒素ガスパージを施しながら、系内を６０℃以下に制御して、２０％水酸化ナトリウム水溶液４２０ｇを３時間かけて滴下した。滴下終了後、そのまま１時間撹拌を続けて反応させた。反応終了後、反応混合物を静置して分液し、水層を取り除いた。残った有機層に水を加えて約１５分間攪拌混合した後、混合物を静置して分液し、水層を取り除いた。水層のｐＨが７になるまでこの操作を繰り返した後、デカンタ脱水で水分とトルエンを除去し、活性エステル化合物（２）を得た。活性エステル化合物（２）の溶融粘度は０．０２ｄＰａ・ｓであった。Example 2 Production of Active Ester Compound (2) 110 g of catechol and 1000 g of methyl isobutyl ketone were charged into a flask equipped with a thermometer, a dropping funnel, a cooling pipe, a fractionating pipe, and a stirrer, and the system was dissolved under reduced pressure with nitrogen. Let Next, 218 g of benzoyl chloride was charged, and the system was dissolved while substituting nitrogen under reduced pressure. While adding 0.5 g of tetrabutylammonium bromide and purging with nitrogen gas, the inside of the system was controlled at 60 ° C. or lower and 420 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropping, stirring was continued for 1 hour to carry out the reaction. After completion of the reaction, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and the mixture was stirred and mixed for about 15 minutes, and then the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer reached 7, water and toluene were removed by decanter dehydration to obtain an active ester compound (2). The melt viscosity of the active ester compound (2) was 0.02 dPa · s.
実施例３ 活性エステル化合物（３）の製造
温度計、滴下ロート、冷却管、分留管、攪拌器を取り付けたフラスコにターシャリーブチルカテコール１６６ｇとメチルイソブチルケトン１１００ｇを仕込み、系内を減圧窒素置換しながら溶解させた。次いで、塩化ベンゾイル２１８ｇを仕込み、系内を減圧窒素置換しながら溶解させた。テトラブチルアンモニウムブロマイド０．６ｇを加え、窒素ガスパージを施しながら、系内を６０℃以下に制御して、２０％水酸化ナトリウム水溶液４２０ｇを３時間かけて滴下した。滴下終了後、そのまま１時間撹拌を続けて反応させた。反応終了後、反応混合物を静置して分液し、水層を取り除いた。残った有機層に水を加えて約１５分間攪拌混合した後、混合物を静置して分液し、水層を取り除いた。水層のｐＨが７になるまでこの操作を繰り返した後、デカンタ脱水で水分とトルエンを除去し、活性エステル化合物（３）を得た。活性エステル化合物（３）の溶融粘度は０．０２ｄＰａ・ｓであった。Example 3 Production of Active Ester Compound (3) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer was charged with 166 g of tertiary butyl catechol and 1100 g of methyl isobutyl ketone, and the system was replaced with nitrogen under reduced pressure. While dissolving. Next, 218 g of benzoyl chloride was charged, and the system was dissolved while substituting nitrogen under reduced pressure. Tetrabutylammonium bromide (0.6 g) was added, and the inside of the system was controlled at 60 ° C or lower while purging with nitrogen gas, and 20% aqueous sodium hydroxide solution (420 g) was added dropwise over 3 hours. After completion of the dropping, stirring was continued for 1 hour to carry out the reaction. After completion of the reaction, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and the mixture was stirred and mixed for about 15 minutes, and then the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer reached 7, water and toluene were removed by decanter dehydration to obtain an active ester compound (3). The melt viscosity of the active ester compound (3) was 0.02 dPa · s.
比較製造例１ 活性エステル化合物（１’）の製造
温度計、滴下ロート、冷却管、分留管、攪拌器を取り付けたフラスコにイソフタル酸クロリド２０２ｇとトルエン１２５０ｇを仕込み、系内を減圧窒素置換しながら溶解させた。次いで、１−ナフトール２８８ｇを仕込み、系内を減圧窒素置換しながら溶解させた。テトラブチルアンモニウムブロマイド０．６ｇを加え、窒素ガスパージを施しながら、系内を６０℃以下に制御して、２０％水酸化ナトリウム水溶液４２０ｇを３時間かけて滴下した。滴下終了後、そのまま１時間撹拌を続けて反応させた。反応終了後、反応混合物を静置して分液し、水層を取り除いた。残った有機層に水を加えて約１５分間攪拌混合した後、混合物を静置して分液し、水層を取り除いた。水層のｐＨが７になるまでこの操作を繰り返した後、デカンタ脱水で水分とトルエンを除去し、活性エステル化合物（１’）を得た。活性エステル化合物（１’）の溶融粘度は０．６５ｄＰａ・ｓであった。Comparative Production Example 1 Production of Active Ester Compound (1 ′) 202 g of isophthalic chloride and 1250 g of toluene were charged into a flask equipped with a thermometer, a dropping funnel, a cooling pipe, a fractionating pipe, and a stirrer, and the system was replaced with nitrogen under reduced pressure. While dissolving. Next, 288 g of 1-naphthol was charged, and the system was dissolved while substituting nitrogen under reduced pressure. Tetrabutylammonium bromide (0.6 g) was added, and the inside of the system was controlled at 60 ° C or lower while purging with nitrogen gas, and 20% aqueous sodium hydroxide solution (420 g) was added dropwise over 3 hours. After completion of the dropping, stirring was continued for 1 hour to carry out the reaction. After completion of the reaction, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and the mixture was stirred and mixed for about 15 minutes, and then the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer reached 7, water and toluene were removed by decanter dehydration to obtain an active ester compound (1 ′). The melt viscosity of the active ester compound (1 ′) was 0.65 dPa · s.
実施例４〜６及び比較例１
下記表１に示す割合で各成分を配合し、硬化性組成物を製造した。硬化性組成物を型枠へ流し込み、プレス機を用いて１７５℃の温度で１０分間成型した。型枠から成型物を取り出し、１７５℃の温度で５時間硬化させて硬化物を得た。硬化物について下記要領で評価試験を行った。結果を表１に示す。Examples 4 to 6 and Comparative Example 1
A curable composition was produced by mixing the components in the proportions shown in Table 1 below. The curable composition was poured into a mold and molded using a press machine at a temperature of 175 ° C. for 10 minutes. The molded product was taken out of the mold and cured at 175 ° C. for 5 hours to obtain a cured product. The cured product was evaluated by the following procedure. The results are shown in Table 1.
高温条件下での貯蔵弾性率の測定
前記硬化物から５ｍｍ×５４ｍｍ×２．４ｍｍサイズの試験片を切り出した。試験片について、粘弾性測定装置（レオメトリック社製「固体粘弾性測定装置ＲＳＡＩＩ」）を用い、レクタンギュラーテンション法、周波数１Ｈｚ、昇温温度３℃／分の条件で、２６０℃における貯蔵弾性率を測定した。Measurement of storage elastic modulus under high temperature condition A test piece of 5 mm × 54 mm × 2.4 mm size was cut out from the cured product. For the test piece, using a viscoelasticity measuring device (“solid viscoelasticity measuring device RSAII” manufactured by Rheometric Co., Ltd.), the storage elastic modulus at 260 ° C. was measured under the conditions of rectangular tension method, frequency 1 Hz, temperature rising temperature 3 ° C./min. It was measured.
高温条件下での曲げ弾性率及び曲げ歪の測定
前記硬化物から２５ｍｍ×７０ｍｍ×２．４ｍｍサイズの試験片を切り出した。試験片について、万能材料試験機（インストロン社製「５５８２型」）を用い、試験速度１．０ｍｍ/分、試験温度２６０℃の条件で、曲げ弾性率及び曲げ歪を測定した。Measurement of flexural modulus and flexural strain under high temperature conditions Test pieces of 25 mm x 70 mm x 2.4 mm size were cut out from the cured product. The flexural modulus and the flexural strain of the test piece were measured using a universal material testing machine (“5582 type” manufactured by Instron Co., Ltd.) under the conditions of a test speed of 1.0 mm / min and a test temperature of 260 ° C.
エポキシ樹脂（＊１）：クレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製「Ｎ−６５５−ＥＸＰ−Ｓ」、エポキシ当量２０２ｇ/当量） Epoxy resin (* 1): Cresol novolac type epoxy resin ("N-655 EXP-S" manufactured by DIC Corporation, epoxy equivalent 202 g / equivalent)
Claims (6)
で表される分子構造を有する請求項１記載の活性エステル化合物。The following structural formula (1-1) or (1-2)
The active ester compound according to claim 1, which has a molecular structure represented by:
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