JP3902140B2 - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
- Publication number
- JP3902140B2 JP3902140B2 JP2003006709A JP2003006709A JP3902140B2 JP 3902140 B2 JP3902140 B2 JP 3902140B2 JP 2003006709 A JP2003006709 A JP 2003006709A JP 2003006709 A JP2003006709 A JP 2003006709A JP 3902140 B2 JP3902140 B2 JP 3902140B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- tgic
- resin composition
- examples
- epicoat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Epoxy Resins (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、耐熱性、透明性および保存安定性に優れたエポキシ樹脂組成物に関するものであり、接着剤、塗料、注型材料、積層材料等として有用なものである。
【0002】
【従来の技術】
一般に、エポキシ樹脂は機械的強度ならびに電気的絶縁特性に優れ、また接着性、耐水性、耐熱性等が良好であることから、電気・電子機器及び部品の絶縁被覆や接着剤、LSIや発光ダイオード用封止剤、積層板、構造用複合材料、土木建築用の接着剤や防食材料、塗料等広範囲に用いられている。
上記に例示される用途に対しては、各々異なった特性が求められるが、耐熱性、耐候性および透明性を改善する手段として、トリグリシジルイソシアヌレートとトリグリシジルイソシアヌレート以外のエポキシ樹脂をベース樹脂として配合したエポキシ樹脂組成物が提案されている。
【0003】
3官能エポキシ樹脂として知られるトリグリシジルイソシアヌレート(以下、TGICという)は、化1の構造式に示されるように、トリアジン環を骨格として、1分子中に3つのエポキシ基を有するので、ベースとなるエポキシ樹脂に添加して用いられる場合には、3次元架橋剤として作用し、ベース樹脂の耐熱性、耐候性、透明性を向上させることができる。
【0004】
【化1】
【0005】
しかしながらTGICは結晶性の固体化合物であるため、有機溶媒や樹脂への溶解度が低く、TGICとエポキシ樹脂を加熱混合して液状の均一な組成物とし、更には該組成物を有機溶剤に溶かしてワニスとした場合であっても、室温で放置しておくと、TGICの結晶が一部析出してしまうという問題があった。
【0006】
このような問題点に対して、特許文献1には、有機溶剤に溶け易い化合物として、TGICとビスフェノールAまたはテトラブロモビスフェノールAとの反応生成物が提案されている。
また、特許文献2、特許文献3および特許文献4等には、従来から知られているTGICが高融点タイプと低融点タイプの立体異性体の混合物であって、この混合物から低融点タイプの異性体のみを分別したものを使用することが提案されている。
【0007】
【特許文献1】
特開平1−225641号公報(第2頁)
【0008】
【特許文献2】
特開平6−192396号公報(第2頁)
【0009】
【特許文献3】
特開平8−311162号公報(第2〜3頁)
【0010】
【特許文献4】
特開平9−183831号公報(第2頁)
【0011】
【発明が解決しようとする課題】
本発明は、TGICとTGIC以外のエポキシ樹脂を加熱混合して均一な液状のエポキシ樹脂組成物とするに当たって、該組成物を室温で放置しておいてもTGICが析出することのない保存安定性に優れたエポキシ樹脂組成物を提供することを目的とする。
【0012】
【課題を解決するための手段】
本発明者等は、上記の課題を解決するために鋭意検討を重ねた結果、トリグリシジルイソシアヌレートとモノアリルジグリシジルイソシアヌレート及び又はジアリルモノグリシジルイソシアヌレートを配合したエポキシ樹脂組成物が所期の目的を達成しうることを見い出し、本発明を完成するに至ったものである。
【0013】
【発明の実施の形態】
本発明の実施において使用されるTGICは、市販の工業薬品として容易に入手することができる。
また、モノアリルジグリシジルイソシアヌレート(以下、MA−DGICという)及びジアリルモノグリシジルイソシアヌレート(以下、DA−MGICという)は、化2の構造式で表されるものであり、公知の方法により合成することができる。
【0014】
【化2】
【0015】
本発明の実施において使用されるエポキシ樹脂としては、分子内にエポキシ基を複数個持つものならば特に限定されず、これらの具体例としては、ビスフェノールAのジグリシジルエーテル型エポキシ樹脂(エピコート815,エピコート825,エピコート827,エピコート828,エピコート834,エピコート1001,エピコート1002,エピコート1004等油化シェルエポキシ(株)製)、ビスフェノールFのジグリシジルエーテル型エポキシ樹脂(エピコート807等同)、フェノールノボラック型エポキシ樹脂(エピコート152,エピコート154等同)、脂環式エポキシ樹脂(CY−175,CY−177,CY−179等CIBA−GEIGY社製)、グリシジルエステル系エポキシ樹脂(CY−182,CY−184,CY−192等同)、グリシジルアミン型エポキシ樹脂(TGDDM,TGPAP,PGMAP等東都化成(株)製)、ポリエチレングリコールのジグリシジルエーテル型エポキシ樹脂(YD−716等同)、脂肪族ジカルボン酸のジグリシジルエーテル型エポキシ樹脂(IPU−22G等岡村製油(株)製)等が挙げられ、これらのエポキシ樹脂を、単独または二種以上を組み合わせて使用することができる。
【0016】
これらのエポキシ樹脂は、常温で液体であることが好ましいが、常温で固体のエポキシ樹脂であっても、有機溶剤や他の液体のエポキシ樹脂と併用することにより、液状のエポキシ樹脂組成物にすることができるものであれば使用可能である。
【0017】
本発明の実施において、エポキシ樹脂組成物中に配合されるTGICの割合は10〜50重量%であることが好ましい。10重量%より少ない場合及び50重量%より多い場合には、TGIC硬化物の本来の特性が得られない。
また、MA−DGIC及び又はDA−MGICの配合量は、使用するTGICに対して、0.3〜0.5の割合(重量比)であることが好ましい。TGICに対する配合割合が0.3より少ない場合には、TGICの結晶析出を抑制する効果が十分ではなく、0.5より多い場合には、徒にコスト高を招来するに過ぎない。
【0018】
本発明のエポキシ樹脂組成物は、従来公知の硬化剤を使用して硬化させることができるが、通常はフェノール性水酸基を有する化合物、酸無水物、アミン類が使用される。
フェノール性水酸基を有する化合物としては、ビスフェノール、レゾルシノール、フェノールノボラック、クレゾールノボラック等の多価フェノール類等が挙げられる。
酸無水物としては、メチルテトラ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、通常エポキシ樹脂の硬化剤として使用されるものであればよく、特に限定されるものではない。
またアミン類としてはメタフェニレンジアミン、ジ(アミノフェニル)メタン(通称ジアミノジフェニルメタン)、ジアミノジフェニルスルホン等の芳香族アミン、2−エチル−4−メチルイミダゾール等のイミダゾール類が例示される。
【0019】
また、エポキシ樹脂の硬化反応を促進させるため、硬化触媒を用いてもよい。硬化触媒として例えば、2−エチル−4−メチルイミダゾール、1−シアノエチル−2−エチル−4−メチルイミダゾール等のイミダゾール化合物、1、8−ジアザビシクロ(5、4、0)ウンデセン−7等の三級アミン化合物、トリフェニルホスフイン等の有機ホスフイン化合物などが挙げられる。
【0020】
更に、本発明のエポキシ樹脂組成物には、補強剤として例えば、フェノール樹脂、不飽和ポリエステル等の各種ポリマー、また、ジクミルパーオキシドに代表される過酸化物、2,2’−アゾビスイソブチロニトリルなどのアリル基の重合を促進する重合開始剤を添加することも可能である。
【0021】
また着色防止のため、従来ポリオレフィン等のプラスチックの酸化防止剤として用いられるラジカル補足作用を有するヒンダードフェノール類、過酸化物分解作用を有する有機スルフィド類、あるいはポリ塩化ビニル等の透明性維持に有用な可塑剤である有機亜リン酸エステル等を添加しても良い。
【0022】
【実施例】
以下、本発明を実施例および比較例によって具体的に説明するが、本発明はこれら実施例に限定されるものではない。
また、本発明の実施例および比較例で使用した原料は、以下のとおりである。
【0023】
・エポキシ樹脂:油化シェルエポキシ(株)製、商品名「エピコート828」
・TGIC:日産化学(株)製、商品名「TEPIC」
・DA−MGIC:特開平10−316665号公報記載の方法により合成した。
・MA−DGIC:特開2000−344867号公報記載の方法により合成した。
【0024】
〔実施例1〜3〕
エポキシ樹脂(エピコート828)に対し、TGIC及びMA−DGICを表1に記載した割合(重量%)でビーカー中、120℃で10分間加熱混合後、減圧脱気して均一な液状エポキシ樹脂組成物を調製した。得られた樹脂組成物を室温(約25℃)にて8時間放置した後、TGICの結晶析出の様子を目視にて確認した。
得られた試験結果は、表1に示したとおりであった。
【0025】
〔実施例4〜6〕
MA−DGICの代わりにDA−MGICを用いた以外は実施例1〜3と同様にしてエポキシ樹脂組成物を調製し、TGICの結晶析出の有無を確認した。
得られた試験結果は、表1に示したとおりであった。
【0026】
〔実施例7、8〕
MA−DGICにDA−MGICを併用した以外は実施例1〜3と同様にしてエポキシ樹脂組成物を調製し、TGICの結晶析出の有無を確認した。
得られた試験結果は、表1に示したとおりであった。
【0027】
〔比較例1〜3〕
MA−DGICまたはDA−MGICを用いない場合についても実施例1〜3と同様にして、TGICの結晶析出の有無を確認した。
得られた試験結果は、表1に示したとおりであった。
【0028】
【表1】
【0029】
表1の試験結果によれば、TGICとMA−DGIC及び又はDA−MGICを配合したエポキシ樹脂組成物において、TGICを単独で配合したものに比べて、MA−DGIC及び又はDA−MGICは、TGICの結晶析出を抑制する効果を有するものと認めらる。
【0030】
【発明の効果】
本発明のエポキシ樹脂組成物は、エポキシ樹脂にTGICと、TGICと相溶性の良いMA−DGIC及び又はDA−MGICを配合しているので、該樹脂組成物を室温で放置しておいてもTGICが析出することがなく、保存安定性に優れている。
従って本発明のエポキシ樹脂組成物は、耐熱性、透明性及び保存安定性を要求される接着剤、塗料、注型材料、積層材料等として好適なものであり、その産業上の利用効果は多大である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an epoxy resin composition excellent in heat resistance, transparency and storage stability, and is useful as an adhesive, a paint, a casting material, a laminated material and the like.
[0002]
[Prior art]
In general, epoxy resins are excellent in mechanical strength and electrical insulation properties, and have good adhesion, water resistance, heat resistance, etc., so that insulation coatings and adhesives for electrical and electronic equipment and parts, LSIs and light-emitting diodes It is used in a wide range of materials such as sealants, laminates, structural composite materials, adhesives and anticorrosive materials for civil engineering, and paints.
For the applications exemplified above, different properties are required, but as a means for improving heat resistance, weather resistance and transparency, epoxy resin other than triglycidyl isocyanurate and triglycidyl isocyanurate is used as a base resin. An epoxy resin composition formulated as is proposed.
[0003]
Triglycidyl isocyanurate (hereinafter referred to as TGIC), which is known as a trifunctional epoxy resin, has three epoxy groups in one molecule with a triazine ring as a skeleton as shown in the structural formula of Chemical Formula 1, When used by being added to the epoxy resin, it acts as a three-dimensional crosslinking agent, and can improve the heat resistance, weather resistance and transparency of the base resin.
[0004]
[Chemical 1]
[0005]
However, since TGIC is a crystalline solid compound, its solubility in organic solvents and resins is low, and TGIC and epoxy resin are heated and mixed to form a uniform liquid composition. Further, the composition is dissolved in an organic solvent. Even when the varnish is used, if it is left at room temperature, there is a problem that a part of TGIC crystals is precipitated.
[0006]
In order to solve such a problem, Patent Document 1 proposes a reaction product of TGIC and bisphenol A or tetrabromobisphenol A as a compound that is easily dissolved in an organic solvent.
In Patent Document 2, Patent Document 3, and Patent Document 4, a conventionally known TGIC is a mixture of a high melting point type and a low melting point type stereoisomer, and from this mixture, a low melting point type isomer is obtained. It has been proposed to use only a separate body.
[0007]
[Patent Document 1]
Japanese Patent Laid-Open No. 1-225641 (page 2)
[0008]
[Patent Document 2]
JP-A-6-192396 (2nd page)
[0009]
[Patent Document 3]
JP-A-8-311162 (pages 2 and 3)
[0010]
[Patent Document 4]
JP-A-9-183831 (second page)
[0011]
[Problems to be solved by the invention]
In the present invention, when TGIC and an epoxy resin other than TGIC are mixed by heating to obtain a uniform liquid epoxy resin composition, storage stability in which TGIC does not precipitate even when the composition is left at room temperature. An object of the present invention is to provide an epoxy resin composition having excellent resistance.
[0012]
[Means for Solving the Problems]
As a result of intensive studies in order to solve the above problems, the present inventors have obtained an epoxy resin composition containing triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate and / or diallyl monoglycidyl isocyanurate. It has been found that the object can be achieved, and the present invention has been completed.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The TGIC used in the practice of the present invention can be easily obtained as a commercial industrial chemical.
Monoallyl diglycidyl isocyanurate (hereinafter referred to as MA-DGIC) and diallyl monoglycidyl isocyanurate (hereinafter referred to as DA-MGIC) are represented by the structural formula of Chemical Formula 2 and synthesized by a known method. can do.
[0014]
[Chemical 2]
[0015]
The epoxy resin used in the practice of the present invention is not particularly limited as long as it has a plurality of epoxy groups in the molecule. Specific examples thereof include diglycidyl ether type epoxy resin of bisphenol A (Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1002, Epicoat 1004, etc. made by Oka Shell Epoxy Co., Ltd.), bisphenol F diglycidyl ether type epoxy resin (Epicoat 807, etc.) Resin (Epicoat 152, Epicoat 154, etc.), alicyclic epoxy resin (CY-175, CY-177, CY-179, etc. manufactured by CIBA-GEIGY), glycidyl ester epoxy resin (CY-182, CY-) 84, CY-192, etc.), glycidylamine type epoxy resin (TGDDM, TGPAP, PGMAP, etc., manufactured by Toto Kasei Co., Ltd.), polyethylene glycol diglycidyl ether type epoxy resin (YD-716, etc.), aliphatic dicarboxylic acid di Examples thereof include glycidyl ether type epoxy resins (IPU-22G, etc., manufactured by Okamura Oil Co., Ltd.), and these epoxy resins can be used alone or in combination of two or more.
[0016]
These epoxy resins are preferably liquid at room temperature, but even if they are solid at room temperature, they are used in combination with organic solvents and other liquid epoxy resins to form a liquid epoxy resin composition. Anything that can be used can be used.
[0017]
In the practice of the present invention, the proportion of TGIC blended in the epoxy resin composition is preferably 10 to 50% by weight. When it is less than 10% by weight and more than 50% by weight, the original characteristics of the TGIC cured product cannot be obtained.
Moreover, it is preferable that the compounding quantity of MA-DGIC and / or DA-MGIC is a ratio (weight ratio) of 0.3-0.5 with respect to TGIC to be used. When the blending ratio with respect to TGIC is less than 0.3, the effect of suppressing TGIC crystal precipitation is not sufficient, and when it is more than 0.5, the cost is simply increased.
[0018]
The epoxy resin composition of the present invention can be cured using a conventionally known curing agent, but usually a compound having a phenolic hydroxyl group, an acid anhydride, and an amine are used.
Examples of the compound having a phenolic hydroxyl group include polyhydric phenols such as bisphenol, resorcinol, phenol novolak, and cresol novolak.
The acid anhydride is not particularly limited as long as it is usually used as a curing agent for epoxy resins, such as methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride.
Examples of amines include aromatic amines such as metaphenylenediamine, di (aminophenyl) methane (commonly called diaminodiphenylmethane) and diaminodiphenylsulfone, and imidazoles such as 2-ethyl-4-methylimidazole.
[0019]
Moreover, in order to accelerate the curing reaction of the epoxy resin, a curing catalyst may be used. Examples of the curing catalyst include imidazole compounds such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole, and tertiary such as 1,8-diazabicyclo (5,4,0) undecene-7. Examples include amine compounds and organic phosphine compounds such as triphenylphosphine.
[0020]
Furthermore, the epoxy resin composition of the present invention includes, as a reinforcing agent, for example, various polymers such as phenol resin and unsaturated polyester, peroxides represented by dicumyl peroxide, 2,2′-azobisiso It is also possible to add a polymerization initiator such as butyronitrile that accelerates the polymerization of the allyl group.
[0021]
Also useful for maintaining transparency of hindered phenols with radical scavenging action, organic sulfides with peroxide decomposing action, or polyvinyl chloride, which are conventionally used as antioxidants for plastics such as polyolefins, to prevent coloring. An organic phosphite that is a plasticizer may be added.
[0022]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these Examples.
The raw materials used in the examples and comparative examples of the present invention are as follows.
[0023]
・ Epoxy resin: Yuka Shell Epoxy Co., Ltd., trade name “Epicoat 828”
・ TGIC: Nissan Chemical Co., Ltd., trade name “TEPIC”
DA-MGIC: synthesized by the method described in JP-A-10-316665.
MA-DGIC: synthesized by the method described in JP-A No. 2000-344867.
[0024]
[Examples 1-3]
The epoxy resin (Epicoat 828) was mixed with TGIC and MA-DGIC in the proportions (% by weight) listed in Table 1 in a beaker at 120 ° C. for 10 minutes, and then degassed under reduced pressure to obtain a uniform liquid epoxy resin composition Was prepared. The resulting resin composition was allowed to stand at room temperature (about 25 ° C.) for 8 hours, and then the state of TGIC crystal precipitation was visually confirmed.
The test results obtained were as shown in Table 1.
[0025]
[Examples 4 to 6]
Except for using DA-MGIC instead of MA-DGIC, an epoxy resin composition was prepared in the same manner as in Examples 1 to 3, and the presence or absence of TGIC crystal precipitation was confirmed.
The test results obtained were as shown in Table 1.
[0026]
[Examples 7 and 8]
An epoxy resin composition was prepared in the same manner as in Examples 1 to 3 except that DA-MGIC was used in combination with MA-DGIC, and the presence or absence of TGIC crystal precipitation was confirmed.
The test results obtained were as shown in Table 1.
[0027]
[Comparative Examples 1-3]
Also in the case where MA-DGIC or DA-MGIC was not used, the presence or absence of TGIC crystal precipitation was confirmed in the same manner as in Examples 1 to 3.
The test results obtained were as shown in Table 1.
[0028]
[Table 1]
[0029]
According to the test result of Table 1, in the epoxy resin composition which mix | blended TGIC and MA-DGIC and / or DA-MGIC, compared with what mix | blended TGIC independently, MA-DGIC and / or DA-MGIC are TGIC. It is recognized that it has the effect of suppressing the precipitation of crystals.
[0030]
【The invention's effect】
In the epoxy resin composition of the present invention, TGIC and MA-DGIC and / or DA-MGIC that are compatible with TGIC are blended in the epoxy resin. Therefore, even if the resin composition is left at room temperature, TGIC Does not precipitate and is excellent in storage stability.
Therefore, the epoxy resin composition of the present invention is suitable as an adhesive, a paint, a casting material, a laminated material, etc. that are required to have heat resistance, transparency, and storage stability. It is.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003006709A JP3902140B2 (en) | 2003-01-15 | 2003-01-15 | Epoxy resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003006709A JP3902140B2 (en) | 2003-01-15 | 2003-01-15 | Epoxy resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2004217780A JP2004217780A (en) | 2004-08-05 |
JP3902140B2 true JP3902140B2 (en) | 2007-04-04 |
Family
ID=32897009
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003006709A Expired - Fee Related JP3902140B2 (en) | 2003-01-15 | 2003-01-15 | Epoxy resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3902140B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20180132622A (en) | 2016-04-07 | 2018-12-12 | 닛산 가가쿠 가부시키가이샤 | Monoglycidyl isocyanurate compounds and methods for their preparation |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9511517B2 (en) * | 2009-07-16 | 2016-12-06 | Panasonic Intellectual Property Management Co., Ltd. | Composite optical element and process for production thereof, and imaging device and optical recording/reproduction device each equipped with the composite optical element |
JP5638812B2 (en) | 2010-02-01 | 2014-12-10 | 株式会社ダイセル | Curable epoxy resin composition |
JP6012433B2 (en) * | 2012-11-28 | 2016-10-25 | 日本化薬株式会社 | Resin composition and cured product thereof (3) |
JP5977794B2 (en) * | 2014-10-23 | 2016-08-24 | 株式会社ダイセル | Curable epoxy resin composition |
JP7322368B2 (en) * | 2018-09-14 | 2023-08-08 | 株式会社レゾナック | Curable resin composition and electronic component device |
-
2003
- 2003-01-15 JP JP2003006709A patent/JP3902140B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20180132622A (en) | 2016-04-07 | 2018-12-12 | 닛산 가가쿠 가부시키가이샤 | Monoglycidyl isocyanurate compounds and methods for their preparation |
US10676463B2 (en) | 2016-04-07 | 2020-06-09 | Nissan Chemical Corporation | Monoglycidyl isocyanurate compound and production method therefor |
Also Published As
Publication number | Publication date |
---|---|
JP2004217780A (en) | 2004-08-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102725802A (en) | Electric insulation system | |
CN102803334A (en) | Thermosettable composition containing a half ester of a cycloaliphatic diol and a thermoset product therefrom | |
KR101567971B1 (en) | Thermosetting resin composition | |
EP3255103B1 (en) | Composition containing a polymer based on epoxy compounds | |
JPS6173719A (en) | Novel epoxy resin composition | |
JP3902140B2 (en) | Epoxy resin composition | |
DE68920086T2 (en) | Thermosetting epoxy resin composition. | |
JP6650125B2 (en) | Polyester modified epoxy resin and adhesive | |
JP2003041123A (en) | Thermosetting resin composition, method for producing the same and suspensionlike mixture | |
JPH09324110A (en) | Curable epoxy resin composition and adhesive | |
JP3396562B2 (en) | Epoxy resin composition and curing agent therefor | |
JP2003049074A (en) | Thermosetting resin composition | |
JPS62201922A (en) | Epoxy resin composition | |
JP2004231787A (en) | Epoxy resin diluent, epoxy resin composition and epoxy resin cured product | |
JP6650123B2 (en) | Polyester modified epoxy resin and adhesive | |
CN101608014A (en) | A kind of composition epoxy resin that contains double-end vinyl benzene base ether third (methyl) olefin(e) acid ester activated diluting agent | |
JP6721855B2 (en) | Epoxy resin composition and adhesive | |
JP2007308601A (en) | Thermosetting epoxy resin composition | |
JP3480552B2 (en) | Epoxy resin composition | |
JP2715512B2 (en) | Epoxy resin composition and molded article obtained by curing the same | |
JP2511691B2 (en) | Epoxy resin curing agent composition and epoxy resin composition | |
JP4857598B2 (en) | Epoxy compound, method for producing the same, and epoxy resin composition | |
JP3941937B2 (en) | Epoxy resin composition | |
JP3391060B2 (en) | Reactive diluent for epoxy resin and epoxy resin composition | |
JP3391067B2 (en) | Epoxy resin composition and epoxy resin composition for laminated board |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20041215 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20061129 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20061208 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20061227 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 3902140 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100112 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110112 Year of fee payment: 4 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110112 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120112 Year of fee payment: 5 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120112 Year of fee payment: 5 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130112 Year of fee payment: 6 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130112 Year of fee payment: 6 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140112 Year of fee payment: 7 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |