JP7804887B2 - Epoxy resin curing agent and epoxy resin composition - Google Patents
Epoxy resin curing agent and epoxy resin compositionInfo
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- JP7804887B2 JP7804887B2 JP2022127976A JP2022127976A JP7804887B2 JP 7804887 B2 JP7804887 B2 JP 7804887B2 JP 2022127976 A JP2022127976 A JP 2022127976A JP 2022127976 A JP2022127976 A JP 2022127976A JP 7804887 B2 JP7804887 B2 JP 7804887B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4035—Hydrazines; Hydrazides
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/625—Hydroxyacids
- C08G59/626—Lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/625—Hydroxyacids
- C08G59/628—Phenolcarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2190/00—Compositions for sealing or packing joints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
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Description
本発明は、エポキシ樹脂用硬化剤およびエポキシ樹脂組成物に関する。 The present invention relates to a curing agent for epoxy resins and an epoxy resin composition.
ジヒドラジド化合物はエポキシ樹脂の硬化剤として使用した場合、透明性の高い硬化物が得られる特徴があり、透明性が必要な電子デバイスなどのエポキシ樹脂封止材や接着剤の硬化剤として有用である。しかしながら、ジヒドラジド化合物を使用したエポキシ樹脂組成物は硬化性、特に低温での硬化性が不十分であるという問題がある。 When used as a curing agent for epoxy resins, dihydrazide compounds are characterized by the ability to produce highly transparent cured products, making them useful as curing agents for epoxy resin encapsulants and adhesives for electronic devices that require transparency. However, epoxy resin compositions that use dihydrazide compounds have the problem of insufficient curing properties, particularly at low temperatures.
特許文献１には、ジヒドラジド化合物と二塩基酸を組合せて使用することで、エポキシ樹脂組成物の硬化性を改善する技術が開示されている。しかしながら、特許文献１のエポキシ樹脂組成物の硬化性は必ずしも十分なものとはいえず、更なる硬化性の改善が求められている。 Patent Document 1 discloses a technique for improving the curability of an epoxy resin composition by using a combination of a dihydrazide compound and a dibasic acid. However, the curability of the epoxy resin composition in Patent Document 1 is not necessarily sufficient, and further improvements in curability are desired.
本発明の課題は、硬化性に優れるエポキシ樹脂組成物をもたらす、ジヒドラジド化合物を含むエポキシ樹脂用硬化剤を提供することである。 The objective of the present invention is to provide an epoxy resin curing agent containing a dihydrazide compound that results in an epoxy resin composition with excellent curing properties.
本発明者らは、上記課題を解決すべく鋭意検討した結果、ジヒドラジド化合物と、特定の構造を有するカルボン酸化合物とを組み合わせることによって、エポキシ樹脂組成物の硬化性を向上できることを見出し、本発明を完成するに至った。すなわち、本発明は以下の態様を含むものである。 As a result of extensive research aimed at solving the above problems, the inventors discovered that the curing properties of epoxy resin compositions can be improved by combining a dihydrazide compound with a carboxylic acid compound having a specific structure, leading to the completion of the present invention. Specifically, the present invention encompasses the following aspects:
〔１〕
（Ａ）ジヒドラジド化合物と、
（Ｂ）芳香族カルボン酸又は脂肪族カルボン酸と、
を含む、硬化剤組成物であって、
前記芳香族カルボン酸が、１個のカルボキシ基と０～２個のヒドロキシ基とを有する芳香環を１個又は２個含み、
前記脂肪族カルボン酸が、１個のカルボキシ基と１個のヒドロキシ基とを含む、直鎖又は分岐鎖の飽和脂肪族カルボン酸である、
硬化剤組成物。
〔２〕（Ｂ）成分として前記芳香族カルボン酸を含み、前記芳香族カルボン酸が、３００℃以下の融点を有する、前記〔１〕に記載の硬化剤組成物。
〔３〕前記芳香族カルボン酸が、ベンゼン環又はナフタレン環構造を有する、前記〔２〕に記載の硬化剤組成物。
〔４〕前記芳香族カルボン酸が、サリチル酸、メチレンジサリチル酸、２－ヒドロキシ－１－ナフトエ酸、３－メチルサリチル酸、２，５－ジヒドロキシ安息香酸、３－フェニルサリチル酸、安息香酸及びこれらの組み合わせからなる群から選択される、前記〔３〕に記載の硬化剤組成物。
〔５〕（Ｂ）成分として前記脂肪族カルボン酸を含み、前記脂肪族カルボン酸の炭素数が、２個又は３個である、前記〔１〕に記載の硬化剤組成物。
〔６〕前記脂肪族カルボン酸が、乳酸である、前記〔５〕に記載の硬化剤組成物。
〔７〕前記ジヒドラジド化合物が、２５０℃以下の融点を有する、前記〔１〕～〔６〕に記載の硬化剤組成物。
〔８〕前記〔１〕～〔７〕のいずれか１項に記載の硬化剤組成物と、（Ｃ）エポキシ樹脂とを含有する、エポキシ樹脂組成物。
〔９〕前記〔８〕に記載のエポキシ樹脂組成物を含むエポキシ樹脂材料であって、接着剤、接合剤、導電材、磁性材、熱伝導材、絶縁材、封止材、コーティング材、制振・防振材、防音材、充填材及び塗料からなる群から選択される、エポキシ樹脂材料。
〔１０〕接着剤又は封止材である、前記〔９〕に記載のエポキシ樹脂材料。
〔１１〕前記〔８〕に記載のエポキシ樹脂組成物を硬化させてなる、硬化物。
〔１２〕前記〔１１〕に記載の硬化物を含む、電子デバイス。
[1]
(A) a dihydrazide compound;
(B) an aromatic carboxylic acid or an aliphatic carboxylic acid;
A hardener composition comprising:
the aromatic carboxylic acid contains one or two aromatic rings having one carboxy group and zero to two hydroxy groups;
The aliphatic carboxylic acid is a linear or branched saturated aliphatic carboxylic acid containing one carboxy group and one hydroxy group.
Hardener composition.
[2] The curing agent composition according to [1], which contains the aromatic carboxylic acid as component (B), and the aromatic carboxylic acid has a melting point of 300°C or less.
[3] The curing agent composition according to [2] above, wherein the aromatic carboxylic acid has a benzene ring or a naphthalene ring structure.
[4] The curing agent composition according to [3] above, wherein the aromatic carboxylic acid is selected from the group consisting of salicylic acid, methylenedisalicylic acid, 2-hydroxy-1-naphthoic acid, 3-methylsalicylic acid, 2,5-dihydroxybenzoic acid, 3-phenylsalicylic acid, benzoic acid, and combinations thereof.
[5] The curing agent composition according to [1], which contains the aliphatic carboxylic acid as component (B), and the aliphatic carboxylic acid has 2 or 3 carbon atoms.
[6] The curing agent composition according to [5], wherein the aliphatic carboxylic acid is lactic acid.
[7] The curing agent composition according to any one of [1] to [6], wherein the dihydrazide compound has a melting point of 250°C or less.
[8] An epoxy resin composition comprising the curing agent composition according to any one of [1] to [7] above and (C) an epoxy resin.
[9] An epoxy resin material comprising the epoxy resin composition according to [8] above, wherein the epoxy resin material is selected from the group consisting of adhesives, bonding agents, conductive materials, magnetic materials, thermally conductive materials, insulating materials, sealing materials, coating materials, vibration damping/anti-vibration materials, soundproofing materials, fillers, and paints.
[10] The epoxy resin material according to [9] above, which is an adhesive or a sealant.
[11] A cured product obtained by curing the epoxy resin composition described in [8] above.
[12] An electronic device comprising the cured product according to [11] above.
本発明により、硬化性に優れるエポキシ樹脂組成物をもたらす、ジヒドラジド化合物を含むエポキシ樹脂用硬化剤を提供することができる。 The present invention provides an epoxy resin curing agent containing a dihydrazide compound that results in an epoxy resin composition with excellent curing properties.
本発明は、（Ａ）ジヒドラジド化合物と、（Ｂ）芳香族カルボン酸又は脂肪族カルボン酸と、を含む、硬化剤組成物であって、前記芳香族カルボン酸が、１個のカルボキシ基と０～２個のヒドロキシ基とを有する芳香環を１個又は２個含み、前記脂肪族カルボン酸が、１個のカルボキシ基と１個のヒドロキシ基とを含む、直鎖又は分岐鎖の飽和脂肪族カルボン酸である、硬化剤組成物に関する。 The present invention relates to a curing agent composition comprising (A) a dihydrazide compound and (B) an aromatic carboxylic acid or an aliphatic carboxylic acid, wherein the aromatic carboxylic acid contains one or two aromatic rings each having one carboxy group and zero to two hydroxy groups, and the aliphatic carboxylic acid is a linear or branched saturated aliphatic carboxylic acid containing one carboxy group and one hydroxy group.
本発明では、硬化剤としてジヒドラジド化合物を使用することによって、透明性の高い硬化物を得ることができる。ジヒドラジド化合物は、特に限定されないが、エポキシ樹脂組成物の硬化性の観点から、融点が２５０℃以下のものが好ましく、硬化物の透明性の観点からは、１８５℃以下のものがより好ましく、１７０℃以下のものがさらにより好ましい。ジヒドラジド化合物の融点の下限値は特に制限されず、例えば、６０℃、８０℃、又は１００℃であってもよい。 In the present invention, by using a dihydrazide compound as a curing agent, a highly transparent cured product can be obtained. The dihydrazide compound is not particularly limited, but from the viewpoint of the curability of the epoxy resin composition, one with a melting point of 250°C or less is preferred. From the viewpoint of the transparency of the cured product, one with a melting point of 185°C or less is more preferred, and one with a melting point of 170°C or less is even more preferred. The lower limit of the melting point of the dihydrazide compound is not particularly limited, and may be, for example, 60°C, 80°C, or 100°C.
ジヒドラジド化合物は粒子状のものが好ましい。粒子状のジヒドラジド化合物の粒子径は、エポキシ樹脂への溶解性や反応性を高める観点からメジアン径が１００μｍ以下のものが好ましく、エポキシ樹脂組成物の粘性を下げる、あるいはエポキシ樹脂への分散性を高めるためにはメジアン径が０．１μｍ以上のものが好ましく、１～５０μｍであることがより好ましく、１～２０μｍであることが更により好ましい。粒子径がこの範囲外にあるもの、あるいは粒子同士が密着して凝集物を形成している場合は、エポキシ樹脂と混合する過程で３本ロールミルやプラネタリーミキサーなどで粒子を潰して、あるいは分散させて、メジアン径を上記範囲内とすることが好ましい。メジアン径は、レーザー回折散乱式粒度分布測定（ＪＩＳ Ｚ ８８２５）により粒度分布を体積基準で作成したときの該粒度分布から求めることができる。レーザー回折散乱式粒径分布測定装置としては、堀場製作所社製「ＬＡ－５００」、島津製作所社製「ＳＡＬＤ－２２００」等を使用することができる 。 The dihydrazide compound is preferably in particulate form. The particle size of the particulate dihydrazide compound preferably has a median diameter of 100 μm or less to enhance solubility and reactivity in the epoxy resin. To reduce the viscosity of the epoxy resin composition or enhance dispersibility in the epoxy resin, the median diameter is preferably 0.1 μm or more, more preferably 1 to 50 μm, and even more preferably 1 to 20 μm. If the particle size is outside this range or if the particles adhere to each other to form aggregates, it is preferable to crush or disperse the particles using a three-roll mill or planetary mixer during mixing with the epoxy resin to bring the median diameter within the above range. The median diameter can be determined from the particle size distribution obtained by laser diffraction/scattering particle size distribution measurement (JIS Z 8825) on a volume basis. Examples of laser diffraction/scattering particle size distribution measuring devices that can be used include the LA-500 manufactured by Horiba Ltd. and the SALD-2200 manufactured by Shimadzu Corporation.
好ましいジヒドラジド化合物としては、例えば、１，３－ビス（ヒドラジノカルボノエチル）－５－イソプロピルヒダントイン、７，１１－オクタデカジエン－１,１８－ジカルボヒドラジド、アジピン酸ジヒドラジド、ドデカン二酸ジヒドラジド、イソフタル酸ジヒドラジド等を挙げることができる。ジヒドラジド化合物は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Preferred dihydrazide compounds include, for example, 1,3-bis(hydrazinocarbonoethyl)-5-isopropylhydantoin, 7,11-octadecadiene-1,18-dicarbohydrazide, adipic acid dihydrazide, dodecanedioic acid dihydrazide, and isophthalic acid dihydrazide. Dihydrazide compounds may be used alone or in combination of two or more.
硬化剤組成物を１００質量％とした場合、ジヒドラジド化合物は、好ましくは８０～９９質量％、より好ましくは８５～９８．５質量％、更に好ましくは９０～９８質量％の量で、硬化剤組成物に含まれる。ジヒドラジド化合物の量が上記範囲内であれば、エポキシ樹脂と混合してエポキシ樹脂組成物とした場合に、組成物のポットライフが良好であり、また硬化反応が均一となる傾向となるので好ましい。 When the curing agent composition is taken as 100% by mass, the dihydrazide compound is preferably contained in the curing agent composition in an amount of 80 to 99% by mass, more preferably 85 to 98.5% by mass, and even more preferably 90 to 98% by mass. If the amount of the dihydrazide compound is within the above range, when it is mixed with an epoxy resin to form an epoxy resin composition, the composition will have a good pot life and the curing reaction will tend to be uniform, which is preferable.
本発明の硬化剤組成物は、特定の構造を有する芳香族カルボン酸又は脂肪族カルボン酸を含む。芳香族カルボン酸又は脂肪族カルボン酸は、ジヒドラジド化合物によるエポキシ樹脂組成物の硬化を促進する機能を有する。 The curing agent composition of the present invention contains an aromatic carboxylic acid or an aliphatic carboxylic acid having a specific structure. The aromatic carboxylic acid or the aliphatic carboxylic acid functions to promote the curing of the epoxy resin composition with the dihydrazide compound.
芳香族カルボン酸は、１個のカルボキシ基と０～２個のヒドロキシ基とを有する芳香環を１個又は２個含む。カルボキシ基、ヒドロキシ基及び芳香環の数が上記範囲内であれば、ジヒドラジド化合物の反応をより促進することが可能である。芳香族カルボン酸は、エポキシ樹脂組成物の硬化性の観点から、融点が３００℃以下であることが好ましく、硬化物の透明性の観点から、２５０℃以下であることがより好ましく、２２０℃以下であることがさらにより好ましい。芳香族カルボン酸の融点の下限値には特に制限はないが、例えば、８０℃以上、１００℃以上、または１２０℃以上であってもよい。 The aromatic carboxylic acid contains one or two aromatic rings each having one carboxy group and zero to two hydroxy groups. If the number of carboxy groups, hydroxy groups, and aromatic rings is within the above range, the reaction of the dihydrazide compound can be further accelerated. From the viewpoint of the curability of the epoxy resin composition, the aromatic carboxylic acid preferably has a melting point of 300°C or less. From the viewpoint of the transparency of the cured product, the melting point is more preferably 250°C or less, and even more preferably 220°C or less. There is no particular restriction on the lower limit of the melting point of the aromatic carboxylic acid, but it may be, for example, 80°C or more, 100°C or more, or 120°C or more.
芳香族カルボン酸としては、例えば、ベンゼン環を有する化合物の他、ビフェニルやベンゾフェノンのような複数のベンゼン環が結合している芳香族多環化合物、ナフタレン環、アントラセン、フェナントレンのような縮合環化合物、ピリジン、フラン、インドールのように炭素の他、窒素、酸素などの複数の元素で環構造が構成される複素芳香族化合物等が挙げられる。エポキシ樹脂への溶解性の観点から、一分子中の環数が３以下のものが好ましい。好ましい芳香族カルボン酸としては、例えば、サリチル酸、メチレンジサリチル酸、２－ヒドロキシ－１－ナフトエ酸、３－メチルサリチル酸、２，５－ジヒドロキシ安息香酸、３－フェニルサリチル酸、安息香酸等を挙げることができる。芳香族カルボン酸は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Aromatic carboxylic acids include, for example, compounds having a benzene ring; aromatic polycyclic compounds having multiple benzene rings bonded together, such as biphenyl and benzophenone; condensed ring compounds such as naphthalene, anthracene, and phenanthrene; and heteroaromatic compounds having a ring structure composed of multiple elements, such as carbon, nitrogen, and oxygen, such as pyridine, furan, and indole. From the perspective of solubility in epoxy resins, compounds having three or fewer rings per molecule are preferred. Preferred examples of aromatic carboxylic acids include salicylic acid, methylenedisalicylic acid, 2-hydroxy-1-naphthoic acid, 3-methylsalicylic acid, 2,5-dihydroxybenzoic acid, 3-phenylsalicylic acid, and benzoic acid. Aromatic carboxylic acids may be used alone or in combination.
脂肪族カルボン酸は、１個のカルボキシ基と１個のヒドロキシ基とを含む、直鎖又は分岐鎖の飽和脂肪族カルボン酸である。脂肪族カルボン酸の炭素数は、エポキシ樹脂への溶解性の観点から、２個又は３個であることが好ましい。本明細書において、脂肪族カルボン酸の炭素数とは、化合物全体に含まれる炭素のうち、カルボキシ基を構成する炭素を除いた残りの炭素の数をいう。 Aliphatic carboxylic acids are linear or branched saturated aliphatic carboxylic acids containing one carboxy group and one hydroxy group. From the viewpoint of solubility in epoxy resins, the number of carbon atoms in the aliphatic carboxylic acid is preferably two or three. In this specification, the number of carbon atoms in the aliphatic carboxylic acid refers to the number of carbon atoms remaining in the entire compound, excluding the carbon atoms constituting the carboxy group.
好ましい脂肪族カルボン酸としては、例えば、乳酸を挙げることができる。 A preferred aliphatic carboxylic acid is, for example, lactic acid.
硬化剤組成物を１００質量％とした場合、芳香族カルボン酸又は脂肪族カルボン酸は、好ましくは１～２０質量％、より好ましくは１．５～１５質量％、更に好ましくは２～１０質量％の量で、硬化剤組成物に含まれる。芳香族カルボン酸又は脂肪族カルボン酸の量が上記範囲内であれば、ジヒドラジド化合物によるエポキシ樹脂の硬化を十分に促進できる。 When the curing agent composition is taken as 100% by mass, the aromatic carboxylic acid or aliphatic carboxylic acid is preferably contained in the curing agent composition in an amount of 1 to 20% by mass, more preferably 1.5 to 15% by mass, and even more preferably 2 to 10% by mass. If the amount of aromatic carboxylic acid or aliphatic carboxylic acid is within the above range, curing of the epoxy resin by the dihydrazide compound can be sufficiently promoted.
本発明における芳香族カルボン酸や脂肪族カルボン酸は、エポキシ樹脂組成物の硬化促進の観点から、アミノ基、ホルミル基、カルボニル基、チオール基、スルホン酸基、ハロゲン等の、カルボキシ基及びヒドロキシ基以外の官能基を含まないことが好ましい。 From the viewpoint of accelerating the curing of the epoxy resin composition, the aromatic carboxylic acid and aliphatic carboxylic acid used in the present invention preferably do not contain functional groups other than carboxyl groups and hydroxyl groups, such as amino groups, formyl groups, carbonyl groups, thiol groups, sulfonic acid groups, or halogens.
硬化剤組成物は、本発明の効果を損なわない範囲で、任意に、水分やジヒドラジド化合物合成時の未反応物等を含んでもよい。 The curing agent composition may optionally contain moisture, unreacted materials from the synthesis of the dihydrazide compound, etc., as long as the effects of the present invention are not impaired.
硬化剤組成物の製造方法に特に制限は無く、ジヒドラジド化合物と、芳香族カルボン酸又は脂肪族カルボン酸と、任意に他の成分とを混合することによって得ることができる。 There are no particular restrictions on the method for producing the curing agent composition, and it can be obtained by mixing a dihydrazide compound with an aromatic carboxylic acid or an aliphatic carboxylic acid, and optionally other components.
本発明はまた、硬化剤組成物と、（Ｃ）エポキシ樹脂とを含有する、エポキシ樹脂組成物に関する。 The present invention also relates to an epoxy resin composition containing the curing agent composition and (C) an epoxy resin.
エポキシ樹脂組成物に含有されるエポキシ樹脂としては、従来公知のエポキシ樹脂を特に制限なく使用できる。エポキシ樹脂は、用途や硬化物の所望の性質に応じて適宜選択でき、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。エポキシ樹脂は液状であっても、固形状であってもよい。また液状樹脂と固形状樹脂の混合物を用いてもよい。ここで、「液状」および「固形状」とは、常温（２５℃）でのエポキシ樹脂の状態を指す。 The epoxy resin contained in the epoxy resin composition can be any conventionally known epoxy resin, without any particular restrictions. The epoxy resin can be selected appropriately depending on the application and the desired properties of the cured product. One type may be used alone, or two or more types may be used in combination. The epoxy resin may be liquid or solid. A mixture of liquid and solid resins may also be used. Here, "liquid" and "solid" refer to the state of the epoxy resin at room temperature (25°C).
液状エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＦ型エポキシ樹脂、ナフタレン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、エステル骨格を有する脂環式エポキシ樹脂、及びブタジエン構造を有するエポキシ樹脂が好ましい。液状エポキシ樹脂の具体例としては、ＤＩＣ社製の「ＨＰ４０３２」、「ＨＰ４０３２Ｄ」、「ＨＰ４０３２ＳＳ」（ナフタレン型エポキシ樹脂）、三菱化学社製の「８２８ＵＳ」、「ｊＥＲ８２８ＥＬ」（ビスフェノールＡ型エポキシ樹脂）、「ｊＥＲ８０７」（ビスフェノールＦ型エポキシ樹脂）、「ｊＥＲ１５２」（フェノールノボラック型エポキシ樹脂）、「ＹＬ７７６０」（ビスフェノールＡＦ型エポキシ樹脂）、新日鉄住金化学社製の「ＺＸ１０５９」（ビスフェノールＡ型エポキシ樹脂とビスフェノールＦ型エポキシ樹脂の混合品）、ナガセケムテックス社製の「ＥＸ－７２１」（グリシジルエステル型エポキシ樹脂）、ダイセル社製の「セロキサイド２０２１Ｐ」（エステル骨格を有する脂環式エポキシ樹脂）、「ＰＢ－３６００」（ブタジエン構造を有するエポキシ樹脂）が挙げられる。 Preferred liquid epoxy resins are bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins with an ester skeleton, and epoxy resins with a butadiene structure. Specific examples of liquid epoxy resins include DIC's "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy resins); Mitsubishi Chemical's "828US," "jER828EL" (bisphenol A-type epoxy resin), "jER807" (bisphenol F-type epoxy resin), "jER152" (phenol novolac-type epoxy resin), and "YL7760" (bisphenol AF-type epoxy resin); Nippon Steel & Sumikin Chemical's "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin); Nagase ChemteX's "EX-721" (glycidyl ester-type epoxy resin); and Daicel's "Celloxide 2021P" (alicyclic epoxy resin with an ester skeleton) and "PB-3600" (epoxy resin with a butadiene structure).
固体状エポキシ樹脂としては、ナフタレン型４官能エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノール型エポキシ樹脂、ナフトール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、アントラセン型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂が好ましい。固体状エポキシ樹脂の具体例としては、ＤＩＣ社製の「ＨＰ４０３２Ｈ」（ナフタレン型エポキシ樹脂）、「ＨＰ－４７００」、「ＨＰ－４７１０」（ナフタレン型４官能エポキシ樹脂）、「Ｎ－６９０」（クレゾールノボラック型エポキシ樹脂）、「Ｎ－６９５」（クレゾールノボラック型エポキシ樹脂）、「ＨＰ－７２００」（ジシクロペンタジエン型エポキシ樹脂）、「ＨＰ－７２００ＨＨ」、「ＥＸＡ７３１１」、「ＥＸＡ７３１１－Ｇ３」、「ＥＸＡ７３１１－Ｇ４」、「ＥＸＡ７３１１－Ｇ４Ｓ」、「ＨＰ６０００」（ナフチレンエーテル型エポキシ樹脂）、日本化薬社製の「ＥＰＰＮ－５０２Ｈ」（トリスフェノール型エポキシ樹脂）、「ＮＣ７０００Ｌ」（ナフトールノボラック型エポキシ樹脂）、「ＮＣ３０００Ｈ」、「ＮＣ３０００」、「ＮＣ３０００Ｌ」、「ＮＣ３１００」（ビフェニル型エポキシ樹脂）、新日鉄住金化学社製の「ＥＳＮ４７５Ｖ」（ナフトール型エポキシ樹脂）、「ＥＳＮ４８５」（ナフトールノボラック型エポキシ樹脂）、三菱化学社製の「ＹＸ４０００Ｈ」、「ＹＬ６１２１」（ビフェニル型エポキシ樹脂）、「ＹＸ４０００ＨＫ」（ビキシレノール型エポキシ樹脂）、「ＹＸ８８００」（アントラセン型エポキシ樹脂）、大阪ガスケミカル社製の「ＰＧ－１００」、「ＣＧ－５００」、三菱化学社製の「ＹＬ７８００」（フルオレン型エポキシ樹脂）、三菱化学社製の「ｊＥＲ１０１０」（固体状ビスフェノールＡ型エポキシ樹脂）、「ｊＥＲ１０３１Ｓ」（テトラフェニルエタン型エポキシ樹脂）等が挙げられる。 Preferred solid epoxy resins include naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, and tetraphenylethane-type epoxy resins. Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", and "HP6000" (naphthylene ether type epoxy resin), manufactured by DIC Corporation; and "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), and "NC3000H" manufactured by Nippon Kayaku Co., Ltd. "," "NC3000," "NC3000L," and "NC3100" (biphenyl-type epoxy resins), Nippon Steel & Sumikin Chemical Co., Ltd.'s "ESN475V" (naphthol-type epoxy resin) and "ESN485" (naphthol novolac-type epoxy resin), Mitsubishi Chemical Corporation's "YX4000H," "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), and "YX8800" (anthracene-type epoxy resin), Osaka Gas Chemicals Co., Ltd.'s "PG-100" and "CG-500," Mitsubishi Chemical Corporation's "YL7800" (fluorene-type epoxy resin), Mitsubishi Chemical Corporation's "jER1010" (solid bisphenol A-type epoxy resin), and "jER1031S" (tetraphenylethane-type epoxy resin), etc.
エポキシ樹脂は、硬化剤組成物との均一混合のしやすさや接着性の観点から、使用するエポキシ樹脂全体の少なくとも１０質量％以上が液状であるのが好ましく、少なくとも３０質量％以上が液状であるのがより好ましく、少なくとも５０質量％以上が液状であるのがさらに好ましく、少なくとも８０質量％以上が液状であるのが特に好ましい。 From the viewpoints of ease of uniform mixing with the curing agent composition and adhesive properties, it is preferable that at least 10% by mass of the total epoxy resin used be liquid, more preferably at least 30% by mass or more, even more preferably at least 50% by mass or more, and particularly preferably at least 80% by mass or more.
エポキシ樹脂のエポキシ当量は、例えば、５０～１０００ｇ／ｅｑ、好ましくは１００～５００ｇ／ｅｑ、より好ましくは１５０～３００ｇ／ｅｑである。ここで、エポキシ当量とは、１当量のエポキシ基あたりのエポキシ樹脂の質量であり、ＪＩＳ Ｋ７２３６（２００９）に準拠して測定することができる。 The epoxy equivalent of the epoxy resin is, for example, 50 to 1,000 g/eq, preferably 100 to 500 g/eq, and more preferably 150 to 300 g/eq. Here, the epoxy equivalent is the mass of epoxy resin per equivalent of epoxy groups, and can be measured in accordance with JIS K7236 (2009).
エポキシ樹脂組成物中のエポキシ樹脂の含有量は特に制限されないが、５０～９５質量％であるのが好ましく、６０～９０質量％であるのがより好ましく、６５～８５質量％であるのが更に好ましい。 The content of epoxy resin in the epoxy resin composition is not particularly limited, but is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and even more preferably 65 to 85% by mass.
エポキシ樹脂と硬化剤組成物は、（Ｃ）エポキシ樹脂のエポキシ当量１に対し、（Ａ）ジヒドラジド化合物と（Ｂ）芳香族カルボン酸又は脂肪族カルボン酸との合計の当量が、好ましくは０．８～１．２、より好ましくは０．９～１．１となる量で配合する。配合量が上記範囲内であれば、エポキシ樹脂の未反応物の残留を抑制することができる。 The epoxy resin and curing agent composition are blended in such an amount that the total equivalent of the (A) dihydrazide compound and (B) aromatic carboxylic acid or aliphatic carboxylic acid is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, per 1 epoxy equivalent of the (C) epoxy resin. If the blending amount is within the above range, it is possible to prevent the residue of unreacted epoxy resin.
エポキシ樹脂組成物は、さらに、（Ａ）成分以外の硬化剤、（Ｂ）成分以外の硬化促進剤、熱硬化性樹脂、熱可塑性樹脂、無機充填材、有機充填材、増粘剤、消泡剤、レベリング剤、密着性付与剤、着色剤、有機溶剤および水からなる群から選択される１以上を含有することができる。 The epoxy resin composition may further contain one or more components selected from the group consisting of a curing agent other than component (A), a curing accelerator other than component (B), a thermosetting resin, a thermoplastic resin, an inorganic filler, an organic filler, a thickener, an antifoaming agent, a leveling agent, an adhesion promoter, a colorant, an organic solvent, and water.
硬化剤としては、本発明の（Ａ）成分以外のエポキシ樹脂硬化剤を意味し、潜在性硬化剤であることが好ましく、例えば、ウレア化合物、アミン系化合物、チオール化合物、酸無水物化合物、グアニジン化合物、ヒドラジド化合物、フェノール化合物、ナフトール化合物、活性エステル化合物、ベンゾオキサジン化合物、シアネートエステル化合物、及びカルボジイミド化合物などが挙げられる。 The curing agent refers to an epoxy resin curing agent other than component (A) of the present invention, and is preferably a latent curing agent, such as a urea compound, an amine compound, a thiol compound, an acid anhydride compound, a guanidine compound, a hydrazide compound, a phenol compound, a naphthol compound, an active ester compound, a benzoxazine compound, a cyanate ester compound, or a carbodiimide compound.
ウレア化合物は、ウレア基を有するものでエポキシ樹脂と反応し得る化合物であれば特に制限はないが、好ましくは芳香族ジメチルウレア又は脂肪族ジメチルウレアが挙げられる。好ましい芳香族ジメチルウレアとしては、例えば、Ｎ，Ｎ－ジメチル－Ｎ’－フェニルウレア、Ｎ，Ｎ－ジメチル－Ｎ’－（３，４－ジクロロフェニル）ウレア、４，４’－メチレンビス（フェニルジメチルウレア）、トルエンビスジメチルウレア等を挙げることができる。好ましい脂肪族ジメチルウレアとしては、ジメチルアミノカルボキシルアミノメチルトリメチルシクロヘキシルジメチルウレア等を挙げることができる。 The urea compound is not particularly limited as long as it has a urea group and can react with an epoxy resin, but aromatic dimethylurea or aliphatic dimethylurea is preferred. Preferred aromatic dimethylureas include N,N-dimethyl-N'-phenylurea, N,N-dimethyl-N'-(3,4-dichlorophenyl)urea, 4,4'-methylenebis(phenyldimethylurea), and toluenebisdimethylurea. Preferred aliphatic dimethylureas include dimethylaminocarboxylaminomethyltrimethylcyclohexyldimethylurea.
アミン系化合物は、イミダゾール化合物、イミダゾールと酸性化合物の塩、アミン化合物、アミン化合物と酸性化合物の塩、及びアミンアダクト化合物からなる群から選ばれる少なくとも一つであることが好ましい。 The amine compound is preferably at least one selected from the group consisting of imidazole compounds, salts of imidazole and acidic compounds, amine compounds, salts of amine compounds and acidic compounds, and amine adduct compounds.
エポキシ樹脂組成物の調製は、特別の困難はなく、従来公知の方法に準じて行うことができる。例えば、硬化剤組成物の各成分、エポキシ樹脂、及び任意に他の成分を混合して、エポキシ樹脂組成物を調製することができる。混合手段には、従来公知の混合手段を特に制限なく使用することができる。例えば、市販の公転自転撹拌機を用いて撹拌してもよい。 Preparing the epoxy resin composition is not particularly difficult and can be carried out in accordance with conventionally known methods. For example, the epoxy resin composition can be prepared by mixing the components of the curing agent composition, the epoxy resin, and optionally other components. Any conventionally known mixing method can be used without any particular restrictions. For example, stirring can be carried out using a commercially available planetary stirrer.
本発明の硬化剤組成物を使用することで、硬化性に優れるエポキシ樹脂組成物を得ることができる。エポキシ樹脂組成物の硬化性は、例えば、ホットプレート式ゲル化試験機（ＧＴ－Ｄ:日新化学社製）を用い、特定の温度（例えば、１００～１５０℃の間の温度）に加熱したホットプレート上に約０．５ｇの樹脂組成物を直径２５ｍｍの範囲内となるように乗せ、先端幅約５ｍｍのスパチュラで混ぜながら１秒間に１回転となるように攪拌し、ホットプレート上面から３０ｍｍの高さにスパチュラで持ち上げて糸を引かなくなるまでの時間（ゲルタイム）により評価することができる。ゲルタイムが短いほど硬化性が高く、特に１００℃でのゲルタイムが短いほど、低温硬化性に優れている。 By using the curing agent composition of the present invention, an epoxy resin composition with excellent curing properties can be obtained. The curing properties of an epoxy resin composition can be evaluated, for example, using a hot plate gelation tester (GT-D: manufactured by Nissin Chemical Co., Ltd.) by placing approximately 0.5 g of the resin composition on a hot plate heated to a specific temperature (e.g., between 100 and 150°C) so that the resin composition is within a diameter of 25 mm, stirring with a spatula with a tip width of approximately 5 mm at one rotation per second, lifting the spatula to a height of 30 mm above the top surface of the hot plate, and measuring the time it takes for the composition to no longer form strings (gel time). The shorter the gel time, the higher the curing properties. The shorter the gel time, especially at 100°C, the better the low-temperature curing properties.
エポキシ樹脂組成物は、例えば、建築、土木、自動車、船舶、宇宙航空、産業機械、ロボット、通信、電気電子、半導体、ディスプレイ等の各分野におけるエポキシ樹脂材料等として用いることができる。より具体的には、接着剤、接合剤、導電材、磁性材、熱伝導材、絶縁材、封止材、コーティング材、制振・防振材、防音材、充填材及び塗料、等として用いることができる。 The epoxy resin composition can be used as an epoxy resin material in various fields, such as architecture, civil engineering, automobiles, ships, aerospace, industrial machinery, robots, communications, electrical and electronics, semiconductors, and displays. More specifically, it can be used as an adhesive, bonding agent, conductive material, magnetic material, thermally conductive material, insulating material, sealing material, coating material, vibration damping/anti-vibration material, soundproofing material, filler, paint, etc.
本発明は、また、エポキシ樹脂組成物を含む接着剤に関する。ここで接着剤は、好ましくは、電子部品の接着剤の分野で使用できる接着剤である。上記接着剤は、本発明のエポキシ樹脂組成物以外に、任意にＡ成分及びＢ成分以外のエポキシ樹脂用硬化剤、硬化促進剤、難燃剤、保存安定性向上剤、充填剤、希釈剤、溶剤、顔料、可撓性付与剤、カップリング剤、酸化防止剤、沈降防止剤、分散剤等の各種添加剤を含んでいてもよい。 The present invention also relates to an adhesive containing an epoxy resin composition. The adhesive is preferably one that can be used in the field of adhesives for electronic components. In addition to the epoxy resin composition of the present invention, the adhesive may optionally contain various additives such as epoxy resin curing agents other than Components A and B, curing accelerators, flame retardants, storage stability improvers, fillers, diluents, solvents, pigments, flexibility-imparting agents, coupling agents, antioxidants, anti-settling agents, and dispersants.
本発明は、また、エポキシ樹脂組成物を含む封止材に関する。ここで封止材とは、フリップチップ実装時のアンダーフィル剤、チップオンボード用封止剤などの封止用材料である。上記封止材は、本発明のエポキシ樹脂組成物以外に、任意にＡ成分及びＢ成分以外のエポキシ樹脂用硬化剤、硬化促進剤、難燃剤、保存安定性向上剤、充填剤、希釈剤、溶剤、顔料、可撓性付与剤、カップリング剤、酸化防止剤、沈降防止剤、分散剤等の各種添加剤を含んでいてもよい。 The present invention also relates to an encapsulant containing an epoxy resin composition. Here, the encapsulant refers to an encapsulating material such as an underfill agent for flip-chip mounting or a chip-on-board encapsulant. In addition to the epoxy resin composition of the present invention, the encapsulant may optionally contain various additives such as epoxy resin curing agents other than Components A and B, curing accelerators, flame retardants, storage stability improvers, fillers, diluents, solvents, pigments, flexibility-imparting agents, coupling agents, antioxidants, anti-settling agents, and dispersants.
本発明は、また、上記のエポキシ樹脂組成物を硬化させて得られる硬化物及び当該硬化物を含有する電子デバイスに関する。電子デバイスとしては、例えば、ＬＥＤ、半導体、レーザー、太陽電池、有機ＥＬデバイス等が挙げられる。 The present invention also relates to a cured product obtained by curing the above-mentioned epoxy resin composition, and an electronic device containing the cured product. Examples of electronic devices include LEDs, semiconductors, lasers, solar cells, and organic EL devices.
エポキシ樹脂組成物の硬化は、特別の困難はなく、従来公知の方法に準じて行うことができる。例えば、得られたエポキシ樹脂組成物を加熱することで硬化することができる。加熱は、例えば、６０～１５０℃、好ましくは７０～１３０℃、より好ましくは８０～１２０℃の温度で、例えば１～１２０分、好ましくは３～１００分、より好ましくは５～８０分の時間行うことが適当である。 Curing the epoxy resin composition is not particularly difficult and can be carried out using conventional methods. For example, the resulting epoxy resin composition can be cured by heating it. Heating is typically carried out at a temperature of 60 to 150°C, preferably 70 to 130°C, and more preferably 80 to 120°C, for a period of time of 1 to 120 minutes, preferably 3 to 100 minutes, and more preferably 5 to 80 minutes.
本発明のエポキシ樹脂組成物の硬化物は、高い透明性を有する。硬化物の透明性は、例えば、特定の硬化条件で得られた硬化物について、φ８０ｍｍ積分球（型名ＳＲＳ－９９－０１０、反射率９９％）を装着したファイバ式分光光度計（ＭＣＰＤ－７７００、形式３１１Ｃ、大塚電子社製、外部光源ユニット：ハロゲンランプＭＣ－２５６４（２４Ｖ、１５０Ｗ仕様））を使用し、硬化物の光透過率スペクトルを測定し、得られた光透過率スペクトルから、硬化物の４００ｎｍの全光線透過率を算出することで評価することができる。全光線透過率が高いほど、透明性に優れている。 The cured product of the epoxy resin composition of the present invention has high transparency. The transparency of a cured product can be evaluated, for example, by measuring the light transmittance spectrum of a cured product obtained under specific curing conditions using a fiber spectrophotometer (MCPD-7700, Model 311C, manufactured by Otsuka Electronics Co., Ltd., external light source unit: halogen lamp MC-2564 (24V, 150W specification)) equipped with an 80mm φ integrating sphere (model SRS-99-010, reflectance 99%), and then calculating the total light transmittance at 400nm of the cured product from the obtained light transmittance spectrum. The higher the total light transmittance, the better the transparency.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 The present invention will be explained in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples.
［エポキシ樹脂組成物の調製］
エポキシ樹脂（ｊＥＲ８２８ＥＬ、三菱化学社製、エポキシ当量１９０）１００質量部に、ジヒドラジド化合物と、本発明の芳香族カルボン酸（実施例１～７、９～１２）、本発明の脂肪族カルボン酸（実施例８）又は比較物質（比較例２～９）とを、表１～３に示される組成となるように添加し、公転自転撹拌機（株式会社シンキー製ＡＲＥ－２５０「あわとり錬太郎」）で２分間撹拌して樹脂組成物を得た。比較例１及び１０～１３については、エポキシ樹脂にジヒドラジド化合物のみを添加して攪拌した。使用したジヒドラジド化合物は、以下のとおりである。
[Preparation of Epoxy Resin Composition]
To 100 parts by mass of an epoxy resin (jER828EL, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 190), a dihydrazide compound and an aromatic carboxylic acid of the present invention (Examples 1 to 7, 9 to 12), an aliphatic carboxylic acid of the present invention (Example 8), or a comparative substance (Comparative Examples 2 to 9) were added so as to obtain the composition shown in Tables 1 to 3, and the mixture was stirred for 2 minutes using a revolving centrifugal mixer (ARE-250 "Awatori Rentaro" manufactured by Thinky Corporation) to obtain a resin composition. In Comparative Examples 1 and 10 to 13, only the dihydrazide compound was added to the epoxy resin and stirred. The dihydrazide compounds used were as follows:
ＶＤＨ－Ｊ：１，３－ビス（ヒドラジノカルボノエチル）－５－イソプロピルヒダントイン（味の素ファインテクノ社製、メジアン径２μｍ）
ＵＤＨ－Ｊ：７，１１－オクタデカジエン－１,１８－ジカルボヒドラジド（味の素ファインテクノ社製、メジアン径２μｍ）
ＡＤＨ：アジピン酸ジヒドラジド（日本ファインケム社製、メジアン径１３μｍ）
Ｎ－１２：ドデカン二酸ジヒドラジド（日本ファインケム社製、メジアン径９μｍ）
ＩＤＨ：イソフタル酸ジヒドラジド（日本ファインケム社製）
VDH-J: 1,3-bis(hydrazinocarbonoethyl)-5-isopropylhydantoin (manufactured by Ajinomoto Fine-Techno Co., Inc., median diameter 2 μm)
UDH-J: 7,11-octadecadiene-1,18-dicarbohydrazide (manufactured by Ajinomoto Fine-Techno Co., Ltd., median diameter 2 μm)
ADH: adipic acid dihydrazide (manufactured by Nippon Finechem Co., Ltd., median diameter 13 μm)
N-12: Dodecanedioic acid dihydrazide (manufactured by Nippon Finechem Co., Ltd., median diameter 9 μm)
IDH: Isophthalic dihydrazide (manufactured by Japan Finechem Co., Ltd.)
［ゲルタイムの測定］
ホットプレート式ゲル化試験機（ＧＴ－Ｄ：日新化学社製）を用い、ジヒドラジド化合物としてＶＤＨ－Ｊを含む組成物については１００℃、ＶＤＨ－Ｊ以外を含む組成物については１３０℃、１４０℃又は１５０℃に加熱したホットプレート上に約０．５ｇの樹脂組成物を直径２５ｍｍの範囲内となるように乗せ、先端幅約５ｍｍのスパチュラで混ぜながら１秒間に１回転となるように攪拌し、ホットプレート上面から３０ｍｍの高さにスパチュラで持ち上げて糸を引かなくなるまでの時間をゲルタイムとした。結果を表１～３に示す。
[Gel time measurement]
A hot plate gelation tester (GT-D, manufactured by Nissin Chemical Co., Ltd.) was used. Approximately 0.5 g of the resin composition was placed on a hot plate heated to 100°C for compositions containing VDH-J as a dihydrazide compound, or to 130°C, 140°C, or 150°C for compositions containing compounds other than VDH-J, so that the diameter of the composition was within 25 mm. The composition was stirred with a spatula having a tip width of approximately 5 mm, rotating once per second, and the gel time was determined by lifting the spatula to a height of 30 mm from the top of the hot plate until the composition no longer formed strings. The results are shown in Tables 1 to 3.
［硬化物の透明性の測定］
各エポキシ樹脂組成物を直径３ｃｍの底面が平滑な缶の容器に気泡が入らないように２ｍｌ投入し、容器の底面全面が樹脂配合物で満たされるようにスパチュラを用いて樹脂配合物を広げ、熱風循環式オーブンで、ジヒドラジド化合物としてＶＤＨ－Ｊを含む組成物については１００℃、ＶＤＨ－Ｊ以外を含む組成物については１３０℃、１４０℃又は１５０℃で３０分加熱し、硬化したものについて、硬化物に傷がつかないように缶の容器からはがして硬化物を得た。φ８０ｍｍ積分球（型名ＳＲＳ－９９－０１０、反射率９９％）を装着したファイバ式分光光度計（ＭＣＰＤ－７７００、形式３１１Ｃ、大塚電子社製、外部光源ユニット：ハロゲンランプＭＣ－２５６４（２４Ｖ、１５０Ｗ仕様））を使用して、硬化物の光透過率スペクトルを測定した。得られた光透過率スペクトルから、硬化物の４００ｎｍの全光線透過率を算出した。結果を表１～３に示す。
[Measurement of Transparency of Cured Product]
2 ml of each epoxy resin composition was poured into a 3 cm diameter, smooth-bottomed canister, taking care to avoid air bubbles. The resin formulation was spread using a spatula so that the entire bottom of the canister was filled with the resin formulation. The composition was then heated in a hot-air circulating oven for 30 minutes at 100°C for compositions containing VDH-J as a dihydrazide compound, or at 130°C, 140°C, or 150°C for compositions containing compounds other than VDH-J. The cured product was then peeled from the canister without scratching it to obtain a cured product. The light transmittance spectra of the cured products were measured using a fiber-optic spectrophotometer (MCPD-7700, Model 311C, Otsuka Electronics Co., Ltd., external light source unit: halogen lamp MC-2564 (24 V, 150 W specification)) equipped with an 80 mm φ integrating sphere (model SRS-99-010, reflectance 99%). The total light transmittance at 400 nm of the cured product was calculated from the obtained light transmittance spectra. The results are shown in Tables 1 to 3.
ジヒドラジド化合物としてＶＤＨ－Ｊを含む実施例１～８と比較例１～９とを比較すると、本発明のカルボン酸化合物を含む実施例１～８では、本発明のカルボン酸化合物及び比較物質を含まない比較例１や、同程度の量の比較物質を含む比較例２～９よりも、ゲルタイムが短かった。また、ＶＤＨ－Ｊ以外のジヒドラジド化合物を含む実施例９～１２と比較例１０～１３についても、同じジヒドラジド化合物を含むもの同士で比較すると、本発明のカルボン酸化合物を含む実施例９～１２では、本発明のカルボン酸化合物及び比較物質を含まない比較例１０～１３よりも、ゲルタイムが短かった。 When Examples 1 to 8, which contain VDH-J as the dihydrazide compound, are compared with Comparative Examples 1 to 9, Examples 1 to 8, which contain the carboxylic acid compound of the present invention, had a shorter gel time than Comparative Example 1, which does not contain the carboxylic acid compound of the present invention or a comparative substance, and Comparative Examples 2 to 9, which contain similar amounts of a comparative substance. Furthermore, when Examples 9 to 12 and Comparative Examples 10 to 13, which contain dihydrazide compounds other than VDH-J, are compared with each other, Examples 9 to 12, which contain the carboxylic acid compound of the present invention, had a shorter gel time than Comparative Examples 10 to 13, which do not contain the carboxylic acid compound of the present invention or a comparative substance.
硬化物の透明性の測定において、比較例１～１３ではいずれも硬化性が不十分なため、測定のための硬化物が得られなかったのに対し、実施例１～１２ではいずれも硬化物が得られた。硬化物が得られた実施例１～１２について、透過率を求めたところ、使用したジヒドラジド化合物の融点が低いものほど透明性が高い傾向が見られ、特にＶＤＨ－Ｊを含む組成物からは透明性の高い硬化物が得られた。 When measuring the transparency of the cured products, Comparative Examples 1 to 13 all showed insufficient curing, making it impossible to obtain cured products suitable for measurement, whereas Examples 1 to 12 all produced cured products. When the transmittance was measured for Examples 1 to 12, in which cured products were obtained, it was found that the lower the melting point of the dihydrazide compound used, the higher the transparency tended to be, and compositions containing VDH-J in particular produced cured products with high transparency.
本発明の硬化剤組成物を使用したエポキシ樹脂組成物は、接着剤や封止材に好適に用いることができ、その硬化物は、電子デバイスとして使用することができる。 Epoxy resin compositions using the curing agent composition of the present invention can be suitably used as adhesives and sealants, and the cured products can be used in electronic devices.
Claims (8)
（Ｂ）脂肪族カルボン酸と、
を含む、硬化剤組成物、及び
（Ｃ）エポキシ樹脂、
を含有するエポキシ樹脂組成物であって、
前記脂肪族カルボン酸が、１個のカルボキシ基と１個のヒドロキシ基とを含む、直鎖又は分岐鎖の飽和脂肪族カルボン酸であり、
前記エポキシ樹脂組成物における前記エポキシ樹脂の含有量が、５０～９５質量％であり、
前記エポキシ樹脂の少なくとも１０質量％以上が２５℃で液状である、
エポキシ樹脂組成物。 (A) a dihydrazide compound;
(B) an aliphatic carboxylic acid;
and (C) an epoxy resin ;
An epoxy resin composition comprising:
the aliphatic carboxylic acid is a linear or branched saturated aliphatic carboxylic acid containing one carboxy group and one hydroxy group;
the content of the epoxy resin in the epoxy resin composition is 50 to 95% by mass,
At least 10% by mass of the epoxy resin is liquid at 25°C.
Epoxy resin composition.
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| CN202310953513.3A CN117586479A (en) | 2022-08-10 | 2023-07-31 | Curing agent for epoxy resin and epoxy resin composition |
| TW112129338A TW202411288A (en) | 2022-08-10 | 2023-08-04 | Hardener for epoxy resin and epoxy resin composition |
| KR1020230103645A KR20240021722A (en) | 2022-08-10 | 2023-08-08 | Curing agent for epoxy resin and epoxy resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060573A (en) | 2003-08-15 | 2005-03-10 | Ajinomoto Co Inc | Hardenable resin composition |
| JP2009149727A (en) | 2007-12-19 | 2009-07-09 | Nippon Steel Chem Co Ltd | Film adhesive, semiconductor package using the same, and manufacturing method thereof |
| CN111057503A (en) | 2019-12-23 | 2020-04-24 | 烟台信友新材料有限公司 | Non-yellowing, non-shrinkage and high-toughness low-temperature curing adhesive and preparation method thereof |
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| JPH0657741B2 (en) | 1986-09-25 | 1994-08-03 | 味の素株式会社 | One-part epoxy resin composition |
| JP2778182B2 (en) * | 1990-02-16 | 1998-07-23 | 東亞合成株式会社 | Epoxy powder coating composition |
| JPH0931165A (en) * | 1995-07-24 | 1997-02-04 | Otsuka Chem Co Ltd | Water-based resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005060573A (en) | 2003-08-15 | 2005-03-10 | Ajinomoto Co Inc | Hardenable resin composition |
| JP2009149727A (en) | 2007-12-19 | 2009-07-09 | Nippon Steel Chem Co Ltd | Film adhesive, semiconductor package using the same, and manufacturing method thereof |
| CN111057503A (en) | 2019-12-23 | 2020-04-24 | 烟台信友新材料有限公司 | Non-yellowing, non-shrinkage and high-toughness low-temperature curing adhesive and preparation method thereof |
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