JP2006206862A5

JP2006206862A5 -

Info

Publication number: JP2006206862A5
Application number: JP2005142485A
Authority: JP
Filing date: 2005-05-16
Publication date: 2008-07-03
Anticipated expiration: 2025-05-16

Description

本発明者らは上記課題を解決すべく鋭意検討した結果、液状エポキシ樹脂として加水分解性塩素の含有率が０．８重量％以上のビスフェノール型液状エポキシ樹脂を用いることにより、着色防止剤を用いなくても酸無水物硬化系において加熱硬化時の着色が少ない成形硬化物が得られることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have used a coloring inhibitor by using a bisphenol-type liquid epoxy resin having a hydrolyzable chlorine content of 0.8% by weight or more as the liquid epoxy resin. The present inventors have found that a molded cured product with little coloration during heat curing can be obtained in an acid anhydride curing system, and the present invention has been completed.

即ち、本発明は、ビスフェノール型液状エポキシ樹脂（Ａ）と酸無水物硬化剤（Ｂ）とを含有する成形用エポキシ樹脂組成物であり、前記ビスフェノール型液状エポキシ樹脂（Ａ）の加水分解性塩素の含有率が０．８重量％以上であることを特徴とする成形用エポキシ樹脂組成物、及びその成形硬化物を提
供するものである。 That is, the present invention is a molding epoxy resin composition containing a bisphenol type liquid epoxy resin (A) and an acid anhydride curing agent (B), and the hydrolyzable chlorine of the bisphenol type liquid epoxy resin (A). The present invention provides a molding epoxy resin composition characterized by having a content of 0.8% by weight or more, and a molded cured product thereof.

更に本発明は、加水分解性塩素の含有率が０．８重量％以上であるビスフェノール型液状エポキシ樹脂（Ａ）と酸無水物硬化剤（Ｂ）加熱予備硬化させて脱型させた後、更に後硬化させることを特徴とする成形硬化物の製造方法をも提供するものである。 In the present invention, the bisphenol type liquid epoxy resin (A) having a hydrolyzable chlorine content of 0.8% by weight or more and the acid anhydride curing agent (B) are preliminarily heated and demolded, The present invention also provides a method for producing a molded cured product characterized by post-curing.

本発明で用いるビスフェノール型液状エポキシ樹脂（Ａ）は、加水分解性塩素の含有率が０．８重量％以上のものである。ここで、加水分解性塩素の含有率は、ＡＳＴＭＤ１７２６−９０に準じた方法で求めた値である。該含有率が０．８重量％未満のエポキシ樹脂を用いた場合は、加熱硬化時の着色抑制効果に劣るために好ましくない。又、該含有率が高くなると、必然的にエポキシ樹脂のエポキシ当量が高くなることから、得られる成形硬化物の架橋密度が低下し、機械的強度や耐熱性に悪影響を及ぼすことがあるため、該含有率の好ましい範囲としては０．９〜４．０重量％である。 The bisphenol liquid epoxy resin (A) used in the present invention has a hydrolyzable chlorine content of 0.8% by weight or more. Here, the content of hydrolyzable chlorine is a value determined by a method according to ASTM D 1726-90. When an epoxy resin having a content of less than 0.8% by weight is used, it is not preferable because it is inferior in coloring suppression effect during heat curing. In addition, since the epoxy equivalent of the epoxy resin is inevitably increased when the content is increased, the crosslinking density of the resulting molded cured product is lowered, and may adversely affect the mechanical strength and heat resistance. A preferable range of the content is 0.9 to 4.0% by weight.

前記ビスフェノール型液状エポキシ樹脂（Ａ）としては、その構造として特に限定されるものではなく、種々のものを使用することができ、例えば、ビスフェノールＡ型液状エポキシ樹脂、ビスフェノールＦ型液状エポキシ樹脂等が挙げられ、単独でも、２種以上の混合物として使用しても良い。これらの中でも、得られる硬化物の機械的物性や耐熱性に優れる点から、特にビスフェノールＡ型液状エポキシ樹脂であることが好ましい。このようなエポキシ樹脂としてはビスフェノールＡ型液状エポキシ樹脂であるＥＰＩＣＬＯＮ８５０−ＬＣ（大日本インキ化学工業株式会社製）が挙げられる。また、前記市販のエポキシ樹脂の他にも、本発明で使用するビスフェノール型液状エポキシ樹脂（Ａ）としては、市販のビスフェノール型液状エポキシ樹脂に塩素含有化合物等を添加して加水分解性塩素量を調製したものでも良い。 As the bisphenol type liquid epoxy resin (A) is not limited particularly as its structure, it can be used various ones, for example, bisphenol A type liquid epoxy resin, a bisphenol F type liquid epoxy resin These may be used alone or as a mixture of two or more. Among these, a bisphenol A liquid epoxy resin is particularly preferable from the viewpoint of excellent mechanical properties and heat resistance of the obtained cured product. Examples of such an epoxy resin include EPICLON 850-LC (Dainippon Ink Chemical Co., Ltd.), which is a bisphenol A type liquid epoxy resin. In addition to the commercially available epoxy resin, as the bisphenol type liquid epoxy resin (A) used in the present invention, a chlorine-containing compound or the like is added to a commercially available bisphenol type liquid epoxy resin to increase the amount of hydrolyzable chlorine. What was prepared may be sufficient.

また、本発明に用いるビスフェノール型液状エポキシ樹脂（Ａ）としては、本発明の効果を損なわない範囲で、種々の固形エポキシ樹脂等を併用し、加熱混合して液状化したものであっても良い。 Moreover, as a bisphenol-type liquid epoxy resin (A) used for this invention, in the range which does not impair the effect of this invention, various solid epoxy resins etc. may be used together, and may be liquefied by heating and mixing. .

本発明の成形用エポキシ樹脂組成物としては、前記ビスフェノール型液状エポキシ樹脂（Ａ）と前記酸無水物硬化剤（Ｂ）とを用いること以外、何ら制限されるものではなく、本発明の効果を損なわない範囲において、必要に応じて、硬化触媒、充填剤、紫外線吸収剤、酸化防止剤、離型剤、脱泡剤等の各種添加剤等を併用して用いても良い。着色している充填剤等を使用する際には、得られる成形硬化物は無色透明ではないが、加熱硬化時の樹脂（バインダー樹脂）由来の黄色等の着色の影響が無いため、充填剤本来の色を成形硬化物に反映させることが出来、より意匠性の高い硬化物が得られる点から、本発明の成形用エポキシ樹脂組成物を用いることが好ましいものである。 The molding epoxy resin composition of the present invention is not limited in any way other than using the bisphenol type liquid epoxy resin (A) and the acid anhydride curing agent (B), and the effects of the present invention are not limited. As long as they are not impaired, various additives such as a curing catalyst, a filler, an ultraviolet absorber, an antioxidant, a release agent, and a defoaming agent may be used in combination. When using colored fillers, etc., the resulting molded cured product is not colorless and transparent, but it is not affected by coloring such as yellow derived from the resin (binder resin) at the time of heat curing. It is preferable to use the molding epoxy resin composition of the present invention from the viewpoint that the color can be reflected in the molded cured product and a cured product with higher design can be obtained.

前記硬化触媒の配合量としては、特に限定されるものではないが、一般的に硬化条件が過酷（温度が高い、又は硬化時間が長いなど）になるほど硬化物の着色度合いが高くなることを鑑み、更に成形用エポキシ樹脂組成物の貯蔵安定性とのバランスが良好である点から、ビスフェノール型液状エポキシ樹脂（Ａ）と酸無水物硬化剤（Ｂ）との合計１００重量部に対して、硬化触媒を０．５〜５．０重量部、好ましくは１．０〜４．０重量部の範囲で配合することが好ましい。 The blending amount of the curing catalyst is not particularly limited, but in general, the degree of coloring of the cured product increases as the curing conditions become severe (temperature is high, or the curing time is long, etc.). Furthermore, from the point that the balance with the storage stability of the epoxy resin composition for molding is good, it is cured with respect to a total of 100 parts by weight of the bisphenol type liquid epoxy resin (A) and the acid anhydride curing agent (B). The catalyst is preferably blended in the range of 0.5 to 5.0 parts by weight, preferably 1.0 to 4.0 parts by weight.

本発明の成形用エポキシ樹脂組成物を得る方法としては特に限定されるものではなく、ビスフェノール型液状エポキシ樹脂（Ａ）と酸無水物硬化剤（Ｂ）とを均一に混合した後、硬化触媒やその他の添加剤等を混合し、均一になるまで攪拌する方法、予めビスフェノール型液状エポキシ樹脂（Ａ）や酸無水物硬化剤（Ｂ）の一方に硬化触媒やその他の添加剤等を混合した後、その他の成分を所定量加え、均一になるまで混合する方法等が挙げられる。また、均一攪拌に伴って発生した泡を消滅させる方法としては、例えば、減圧下で一定時間放置後、徐々に復圧させる方法等が挙げられる。 The method for obtaining the molding epoxy resin composition of the present invention is not particularly limited, and after uniformly mixing the bisphenol type liquid epoxy resin (A) and the acid anhydride curing agent (B), a curing catalyst or A method of mixing other additives and stirring until uniform, after previously mixing a curing catalyst or other additives with one of the bisphenol type liquid epoxy resin (A) or acid anhydride curing agent (B) And a method of adding a predetermined amount of other components and mixing them until uniform. Moreover, as a method of eliminating the bubbles generated with uniform stirring, for example, a method of allowing the bubbles to return gradually after being left for a certain period of time under reduced pressure can be mentioned.

特に、加水分解性塩素の含有率が０．８重量％以上であるビスフェノール型液状エポキシ樹脂（Ａ）と酸無水物硬化剤（Ｂ）との合計１００重量部に対し、アルキルハライドとトリフェニルホスフィンから成る第４級ホスホニウム塩（Ｃ）を０．５〜５．０重量部配合した成形用エポキシ樹脂組成物を、５５℃〜７５℃で３０分以上２００分以内の範囲で加熱予備硬化させて脱型させた後、更に１００℃〜１５０℃で４５分以上９０分以内の範囲で後硬化させる製造方法は、加熱硬化時の着色が抑えられると共に、得られる硬化物の耐熱性、機械的物性が優れるものである。この時予備硬化時の加熱温度が５５℃未満の場合や硬化時間が３０分未満では脱型が困難になりやすく、７５℃より高い場合や２００分を超える加熱条件では、加熱硬化時に着色しやすかったり、割れが生じたりする可能性がある。更に、脱型後の後硬化条件として、１００℃未満の場合や加熱時間が４５分未満の場合は得られる硬化物の機械的強度、耐熱性が低下しやすく、逆に１５０℃より高い場合や９０分より長くなると得られる硬化物に変色や割れなどの不具合が生じる可能性がある。又、前記ビスフェノール型液状エポキシ樹脂（Ａ）の加水分解性塩素の含有率が高くなると、必然的にエポキシ樹脂のエポキシ当量が高くなることから、得られる成形硬化物の架橋密度が低下し、脱型が困難になる可能性や、機械的強度や耐熱性に悪影響を及ぼすことがあるため、該含有率の好ましい範囲としては０．９〜４．０重量％である。
In particular, alkyl halide and triphenylphosphine with respect to a total of 100 parts by weight of bisphenol type liquid epoxy resin (A) and acid anhydride curing agent (B) having a hydrolyzable chlorine content of 0.8% by weight or more. An epoxy resin composition for molding containing 0.5 to 5.0 parts by weight of a quaternary phosphonium salt (C) consisting of is preliminarily heated at 55 ° C. to 75 ° C. for 30 minutes to 200 minutes. After demolding, the method of post-curing at 100 ° C. to 150 ° C. for 45 minutes or more and 90 minutes or less suppresses coloring during heat curing, and also provides heat resistance and mechanical properties of the resulting cured product. Is excellent. At this time, when the heating temperature at the time of pre-curing is less than 55 ° C. or when the curing time is less than 30 minutes, demolding tends to be difficult. Or cracking may occur. Furthermore, as post-curing conditions after demolding, when the temperature is less than 100 ° C. or when the heating time is less than 45 minutes, the mechanical strength and heat resistance of the obtained cured product are likely to decrease, and conversely, If it is longer than 90 minutes, the cured product obtained may have problems such as discoloration and cracking. Further, when the content of hydrolyzable chlorine in the bisphenol-type liquid epoxy resin (A) is increased, the epoxy equivalent of the epoxy resin is inevitably increased, so that the cross-linking density of the obtained molded cured product is lowered, and the depolymerization is reduced. Since the mold may be difficult, and the mechanical strength and heat resistance may be adversely affected, the preferable range of the content is 0.9 to 4.0% by weight.

Claims

A molding epoxy resin composition containing a bisphenol type liquid epoxy resin (A) and an acid anhydride curing agent (B), wherein the hydrolyzable chlorine content of the bisphenol type liquid epoxy resin (A) is 0. An epoxy resin composition for molding, characterized by being 8% by weight or more.

The epoxy resin composition for molding according to claim 1, wherein the content of hydrolyzable chlorine in the bisphenol-type liquid epoxy resin (A) is 0.9 to 4.0% by weight.

The molding epoxy resin composition according to claim 1, further comprising a quaternary phosphonium salt (C) comprising an alkyl halide and triphenylphosphine.

The content of the quaternary phosphonium salt (C) is 0.5 to 5.0 parts by weight with respect to a total of 100 parts by weight of the bisphenol type liquid epoxy resin (A) and the acid anhydride curing agent (B). The molding epoxy resin composition according to claim 3 .

A molded and cured product obtained by heat-molding and curing the molding epoxy resin composition according to any one of claims 1 to 4 .

A molding epoxy resin composition containing a bisphenol-type liquid epoxy resin (A) having a hydrolyzable chlorine content of 0.8% by weight or more and an acid anhydride curing agent (B) is preliminarily heated and removed. A method for producing a molded cured product, characterized by further post-curing after molding.

The quaternary phosphonium salt (C) comprising an alkyl halide and triphenylphosphine is added in an amount of 0.5 to 5.5 with respect to a total of 100 parts by weight of the bisphenol type liquid epoxy resin (A) and the acid anhydride curing agent (B). The epoxy resin composition for molding containing 0 part by weight was preliminarily heated at 55 ° C. to 75 ° C. for 30 minutes or longer and within 200 minutes for demolding, and further, 100 ° C. to 150 ° C. for 45 minutes or longer 90 minutes. The method for producing a molded cured product according to claim 6 , wherein post-curing is performed within a range of minutes.

The method for producing a molded cured product according to claim 6 or 7, wherein the bisphenol-type liquid epoxy resin (A) has a hydrolyzable chlorine content of 0.9 to 4.0% by weight.