JP2007502904A - Polyphosphonate flame retardant curing agent for polyexic resin - Google Patents
Polyphosphonate flame retardant curing agent for polyexic resin Download PDFInfo
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- 0 *c(cc1)ccc1OP(*)(Oc1ccc(*)cc1)=N Chemical compound *c(cc1)ccc1OP(*)(Oc1ccc(*)cc1)=N 0.000 description 1
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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
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- 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
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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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
- C08G59/621—Phenols
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
【課題】エポキシ樹脂用の新しい難燃硬化剤を提供する。
【解決手段】エポキシ樹脂の有効硬化剤として式：
【化１】
但しＹはアリーレン基であり、ｎは約２〜約３０である、
で示されるエポキシ反応性ポリホスホネートを用いる。
A novel flame retardant for epoxy resin is provided.
An effective curing agent for epoxy resins is represented by the formula:
[Chemical 1]
Where Y is an arylene group and n is about 2 to about 30.
An epoxy-reactive polyphosphonate represented by
Description
本発明はエポキシ樹脂組成物に関する。 The present invention relates to an epoxy resin composition.
本発明は特許文献１及び特許文献２に記載されているタイプのポリホスホネートの新規用途に関する。特許文献３にはポリ（ｍ−フェニレンシクロヘキシルホスホネート）により難燃性を改良したポリエステルフィラメントが記載されているが、本発明は後記するようにエポキシ樹脂組成物に関するものである。ここで「ポリホスホネート」なる用語は、オリゴマー状物質と高分子物質の両者を包含するものとして用いる。 The present invention relates to novel uses of polyphosphonates of the type described in US Pat. Patent Document 3 describes a polyester filament whose flame retardancy is improved by poly (m-phenylenecyclohexylphosphonate). The present invention relates to an epoxy resin composition as described later. Here, the term “polyphosphonate” is used to encompass both oligomeric and polymeric materials.
非特許文献１には、エポキシ化合物とホスホネートとの次式の反応が記載されている。 Non-Patent Document 1 describes a reaction of the following formula between an epoxy compound and a phosphonate.
この反応は残存するエポキシをほとんど又は全くもたない重合体状線状ホスホネートを製造することを目的としている。 This reaction is aimed at producing polymeric linear phosphonates with little or no residual epoxy.
本発明は、たとえば電子分野用の印刷回路板に用いうるエポキシ樹脂組成物を提供する。 The present invention provides an epoxy resin composition that can be used, for example, in a printed circuit board for the electronic field.
本発明は特許文献４に記載されているタイプのエポキシ樹脂組成物（そこでは本発明のエポキシ樹脂組成物で用いると同様のタイプのポリホスホネート難燃剤を含有するエポキシ樹脂をメチルイミダゾール硬化剤の存在下に硬化している）を越える新しい態様を対象としている。 The present invention relates to an epoxy resin composition of the type described in Patent Document 4 (wherein an epoxy resin containing a polyphosphonate flame retardant of the same type used in the epoxy resin composition of the present invention is present in the presence of a methylimidazole curing agent). It is intended for a new embodiment that goes beyond).
本発明はエポキシ樹脂及びその有効な硬化剤としてのエポキシ−反応性ポリホスホネートからなることを特徴とするエポキシ樹脂組成物である。 The present invention is an epoxy resin composition comprising an epoxy resin and an epoxy-reactive polyphosphonate as its effective curing agent.
本発明の組成物は第１の基本成分としてエポキシ樹脂を含有する。この成分は組成物の合計重量の約５０〜約９０％の量で存在する。この成分は、ビスフェノールＡ型エポキシ樹脂又は（たとえばビスフェノールＦエポキシ、フェノールノボラックエポキシ、クレゾールノボラックエポキシ及び／又はビスフェノールＡノボラックエポキシ等の）印刷回路板や他の電子基材の製造に有用なハロゲン不含エポキシ樹脂でありうる。所望によりこれら樹脂の相溶性混合物も用いうる。 The composition of the present invention contains an epoxy resin as the first basic component. This component is present in an amount of about 50 to about 90% of the total weight of the composition. This component is free of halogens useful in the manufacture of bisphenol A type epoxy resins or printed circuit boards (such as bisphenol F epoxy, phenol novolac epoxy, cresol novolac epoxy and / or bisphenol A novolac epoxy) and other electronic substrates. It can be an epoxy resin. If desired, compatible mixtures of these resins may also be used.
本発明組成物の他方の基本成分であるポリホスホネート難燃硬化剤は、一般に、組成物の合計重量の約５〜約５０％、たとえば約１０〜約３５％存在する。本発明のエポキシ樹脂では、特許文献４に記載の発明とは異なり、このポリホスホネートがエポキシ樹脂に対する有効な硬化剤として作用する。
この硬化剤は式：
The polyphosphonate flame retardant, the other basic component of the composition of the present invention, is generally present from about 5 to about 50%, such as from about 10 to about 35%, of the total weight of the composition. In the epoxy resin of the present invention, unlike the invention described in Patent Document 4, this polyphosphonate acts as an effective curing agent for the epoxy resin.
This curing agent has the formula:
但しＹはアリーレン基であり、ｎは約２〜約３０である、で示されるポリホスホンートである。所望により、混合アリーレンジオールと混合アルキルホスホネートを混合生成物の製造に用いうる。 Y is an arylene group, and n is a polyphosphonate represented by the formula: If desired, mixed arylene diols and mixed alkyl phosphonates can be used in the preparation of the mixed product.
このオリゴマー状ないしポリマー状物質はＯＨ末端基を含むか又は含まないタイプのオリゴマーないしポリマーでありうる。ＯＨ末端基を含む個別ポリホスホネート種はモノヒドロキシ置換体又はヒドロキシ置換体でありうる。ヒドロキシ末端基を含む組成物中のポリホスホネート種の濃度はこの末端基を本来持ちうる末端（鎖端）の合計数基準で、約２０〜約１００％、たとえば約５０〜約１００％でありうる。ＯＨ末端基数はアリーレン／ホスホネートの比によって又は第３級ホスフェート等の末端封止剤の使用によって制御しうる。 This oligomeric or polymeric material can be an oligomer or polymer of the type with or without OH end groups. Individual polyphosphonate species containing OH end groups can be monohydroxy substituted or hydroxy substituted. The concentration of the polyphosphonate species in the composition containing hydroxy end groups can be from about 20 to about 100%, such as from about 50 to about 100%, based on the total number of ends (chain ends) that can naturally have this end group. . The number of OH end groups may be controlled by the arylene / phosphonate ratio or by the use of an end capping agent such as a tertiary phosphate.
前者の場合、過剰のアリーレン含有ジオールを、たとえばポリホスホネートをつくる際に、ホスホネート反応剤と用いると、最終生成物中のヒドロキシル含量はより高くなる。好ましいＲ基はメチルだが、低級（Ｃ６以下）のアルキルも用いうる。 In the former case, when an excess of arylene-containing diol is used with a phosphonate reactant, for example in making a polyphosphonate, the hydroxyl content in the final product is higher. The preferred R group is methyl, but lower (C6 or lower) alkyl can also be used.
「アリーレン」なる用語は２価フェノールの適宜のラジカルを意味する。２価フェノールは非隣接位に２個のヒドロキシル基をもちうる。その例としては、レゾルシノール、ヒドロキノン及びビスフェノール、たとえば、ビスフェノールＡビスフェノールＦ及び４，４’−ビスフェノール、フェノールフタレン、４，４’−チオジフェノール又は４，４’−スルホニルジフェノールがある。３個以上のヒドロキシル基をもつ、ノボラック又はフロログルシノール（ｐｈｌｏｒｏｇｌｕｃｉｎｏｌ）等の、多価フェノールを少量用いて分子量を増加させうる。アリーレン基の例としては１，３−フェニレン、１，４−フェニレン又はビスフェノールジラジカル単位等があるが、１，３−フェニレンが好ましい。 The term “arylene” refers to the appropriate radical of a dihydric phenol. A dihydric phenol can have two hydroxyl groups in non-adjacent positions. Examples thereof are resorcinol, hydroquinone and bisphenols, such as bisphenol A bisphenol F and 4,4'-bisphenol, phenolphthalene, 4,4'-thiodiphenol or 4,4'-sulfonyldiphenol. A small amount of a polyhydric phenol such as novolak or phloroglucinol having 3 or more hydroxyl groups can be used to increase the molecular weight. Examples of arylene groups include 1,3-phenylene, 1,4-phenylene or bisphenol diradical units, with 1,3-phenylene being preferred.
本発明のエポキシ樹脂組成物用ポリホスホネート硬化剤は次のいくつかのルートで製造しうる；（１）ＲＰＯＣｌ２とＨＯ−アリール−ＯＨ又はその塩との反応（但しＲは低級アルキル、好ましくはメチル）、（２）ジフェニルアルキルホスホネート、好ましくはメチルホスホネートとＨＯ−アリーレン−ＯＨとのエステル交換条件下の反応、（３）−ＯＰ（ＯＲ’）−Ｏ−アリーレン−の反復単位をもつホスファイトオリゴマーとアルブゾフ転移触媒との反応（但しＲ’は低級アルキル、好ましくはメチル）、（４）−ＯＰ（Ｏ−Ｐｈ）−Ｏ−アリーレンの反復単位をもつホスファイトオリゴマーとトリメチルホスファイト及びアルブゾフ触媒との又はジメチルホスホネートと、所望によりアルブゾフ触媒との反応。 The polyphosphonate curing agent for an epoxy resin composition of the present invention can be produced by the following several routes: (1) Reaction of RPOCl 2 with HO-aryl-OH or a salt thereof, wherein R is a lower alkyl, preferably Methyl), (2) diphenylalkylphosphonate, preferably a reaction under transesterification conditions of methylphosphonate with HO-arylene-OH, (3) a phosphite having a repeating unit of -OP (OR ')-O-arylene- Reaction of oligomer with Arbuzov transfer catalyst (where R 'is lower alkyl, preferably methyl), (4) Phosphite oligomers having repeating units of -OP (O-Ph) -O-arylene, trimethylphosphite and Arbuzov catalyst Or with dimethylphosphonate and optionally an Arbuzov catalyst.
ＯＨ末端基がアリーレンに結合している場合、それは反応媒体中でのＨＯ−アリーレン−ＯＨの制御されたモル過剰をもたせることで製造しうる。このタイプのオリゴマーの末端基は主に−アリーレン−ＯＨ型であることが好ましい。 If the OH end group is attached to arylene, it can be prepared by having a controlled molar excess of HO-arylene-OH in the reaction medium. The end groups of this type of oligomer are preferably mainly of the -arylene-OH type.
本発明のエポキシ樹脂組成物は、補助的難燃添加剤や、補助的硬化触媒、繊維及び／又は布状強化剤、鉱物質充填剤、たとえばＡｌ（ＯＨ）３、Ｍｇ（ＯＨ）２又はシリカ、制型剤、着色剤等の適宜の添加剤を含有しうる。
次に本発明を実施例で例証する。
The epoxy resin composition of the present invention comprises an auxiliary flame retardant additive, an auxiliary curing catalyst, a fiber and / or cloth reinforcing agent, a mineral filler such as Al (OH) 3 , Mg (OH) 2 or silica. Further, it may contain appropriate additives such as an antimolding agent and a coloring agent.
The invention will now be illustrated by the examples.
前記のポリホスホネート硬化剤（ポリ（ｍ−フェニレンメチルホスホネート）（２９．１ｇ）を７０．１ｇのビスフェノールＡ型エポキシ（エポキシ当量：１８０）と混合してマスターバッチをつくった。このマスターバッチから１０ｇのサンプルを取り出して、窒素パージした１７９℃オーブンに入れた。９０分後にサンプルを取り出して室温に冷却した。Ｇ１ ９３４−１ メーターを用いてバーコル（Ｂａｒｋｏｌ）硬度を測定した。サンプルは硬度２８〜２９で均一に硬化されていた。このサンプルをアセトン中に１２時間浸漬した。膨潤や溶解は認められなかった。 A masterbatch was prepared by mixing the polyphosphonate curing agent (poly (m-phenylenemethylphosphonate) (29.1 g) with 70.1 g of bisphenol A type epoxy (epoxy equivalent: 180) from this masterbatch. The sample was removed and placed in a nitrogen-purged oven at 179 ° C. After 90 minutes, the sample was removed and cooled to room temperature, and the Barcol hardness was measured using a G1 934-1 meter. The sample was uniformly cured at 29. This sample was immersed in acetone for 12 hours, and no swelling or dissolution was observed.
〔比較例１〕
ビスフェノールＡ型エポキシ（エポキシ当量：１８０）のサンプル１０ｇを窒素パージした１７９℃のオーブンに１００分間入れた。サンプルは硬化もゲル化もしなかった。それは室温で粘性液体でありアセトンに完全溶解した。
〔比較例２〕
式：
[Comparative Example 1]
A 10 g sample of bisphenol A type epoxy (epoxy equivalent: 180) was placed in an oven at 179 ° C. purged with nitrogen for 100 minutes. The sample did not cure or gel. It was a viscous liquid at room temperature and was completely dissolved in acetone.
[Comparative Example 2]
formula:
（但し、ＢｕはＣ４Ｈ８）の脂肪族ホスホネートオリゴマーをビスフェノールＡジエポキシ樹脂（エポキシ当量：１８０）と混合して７０重量％のエポキシ樹脂含有混合物をつくった。この混合物は１５０℃のオーブン中で１時間半加熱した。硬化は起こらなかった。生成物は室温で粘性の液体だった。 An aliphatic phosphonate oligomer (Bu is C 4 H 8 ) was mixed with a bisphenol A diepoxy resin (epoxy equivalent: 180) to form a 70 wt% epoxy resin-containing mixture. This mixture was heated in an oven at 150 ° C. for 1.5 hours. Curing did not occur. The product was a viscous liquid at room temperature.
〔比較例２〕
ジメチルメチルホスホネート、Ｐ２Ｏ５及びエチレンオキシド（アクゾノベル社製商品名ＦＹＲＯＬＨＰ）の反応生成物（ヒドロキシ数１２５ｍｇ ＫＯＨ／ｇ）であるポリホスホネートをビスフェノールＡジエポキシ樹脂（エポキシ当量：１８０）と混合してエポキシ樹脂７０％とポリホスホネート３０％の混合物をつくった。この混合物を１５０℃のオーブン中で１時間半加熱した。硬化は起こらなかった。
[Comparative Example 2]
Polyphosphonate which is a reaction product (hydroxy number 125 mg KOH / g) of dimethylmethylphosphonate, P 2 O 5 and ethylene oxide (trade name FYROLHP manufactured by Akzo Nobel) is mixed with bisphenol A diepoxy resin (epoxy equivalent: 180) to form an epoxy. A mixture of 70% resin and 30% polyphosphonate was made. This mixture was heated in an oven at 150 ° C. for 1.5 hours. Curing did not occur.
３０％重量のジフェニルメチルホスホネートとビスフェノールＡジエポキシ樹脂（エポキシ当量：１８０）の混合物を１５０℃で１．５時間加熱した。反応生成物は室温で粘性の液体だった。これをＰ３１ＮＭＲで分析した。モノ挿入した生成物２０％と未反応ＤＰＭＰ５６％）とジ挿入した生成物２１％を含有していた。１３Ｃ ＮＭＲとＦＴＩＲスペクトルではかなりの量の未反応エポキシ基の存在を示した。これはエポキシ組成物中に生成物が含まれていることを示している。 A mixture of 30% by weight diphenylmethylphosphonate and bisphenol A diepoxy resin (epoxy equivalent: 180) was heated at 150 ° C. for 1.5 hours. The reaction product was a viscous liquid at room temperature. This was analyzed by P 31 NMR. 20% mono-inserted product and 56% unreacted DPMP) and 21% di-inserted product. 13 C NMR and FTIR spectra indicated the presence of significant amounts of unreacted epoxy groups. This indicates that the product is contained in the epoxy composition.
実施例１で用いたポリホスホネートの３０重量％とビスフェノールＡジエポキシ樹脂（エポキシ当量：１８０）の混合物を１３７℃で１．５時間加熱した。反応混合物は室温で固体だが、クロロホルム又はアセトンには完全溶解した。Ｐ３１ＮＭＲで分析した。約５２％のリンが未反応で残り、残りのリンがエポキシ樹脂と反応した。 A mixture of 30% by weight of the polyphosphonate used in Example 1 and bisphenol A diepoxy resin (epoxy equivalent: 180) was heated at 137 ° C. for 1.5 hours. The reaction mixture was solid at room temperature but was completely dissolved in chloroform or acetone. Analysis by P 31 NMR. About 52% of phosphorus remained unreacted, and the remaining phosphorus reacted with the epoxy resin.
実施例３のエポキシ挿入生成物を１５０℃のオーブン中で１．５時間加熱し、次いで１８０℃で１時間加熱した。生成物の硬化エポキシ組成物は（Ｇ１ ９３４−１ メーターを用いて測定すると）３２のバーコル硬度を示した。 The epoxy insertion product of Example 3 was heated in an oven at 150 ° C. for 1.5 hours and then at 180 ° C. for 1 hour. The cured epoxy composition of the product exhibited a Barcol hardness of 32 (measured using a G1 934-1 meter).
実施例３のエポキシ挿入生成物をアセトンに溶かし、ＡＴＨと混合してＡＴＨ６２％とエポキシ樹脂組成物３６％の混合物をつくった。アセトンを減圧下に蒸発させた。得られたペースト状物を十分に混合し１５０℃で１時間硬化しさらに３０分かけて温度を１６０℃に上げた。生成した硬化エポキシ組成物は５２のバーコル硬度を示した。 The epoxy insertion product of Example 3 was dissolved in acetone and mixed with ATH to make a mixture of 62% ATH and 36% epoxy resin composition. Acetone was evaporated under reduced pressure. The obtained paste was thoroughly mixed and cured at 150 ° C. for 1 hour, and the temperature was further raised to 160 ° C. over 30 minutes. The resulting cured epoxy composition exhibited a Barcol hardness of 52.
実施例３のエポキシ挿入生成物をアセトンに溶かし、１０００ｐｐｍのメチルイミダゾール及び１０００ｐｐｍのトリフェニルホスフィンと混合した。アセトンを減圧下に蒸発させた。同サンプルを１３８℃で１時間硬化させた。生成した硬化エポキシ組成物は２５のバーコル硬度を示した。 The epoxy insertion product of Example 3 was dissolved in acetone and mixed with 1000 ppm methylimidazole and 1000 ppm triphenylphosphine. Acetone was evaporated under reduced pressure. The sample was cured at 138 ° C. for 1 hour. The resulting cured epoxy composition exhibited a Barcol hardness of 25.
Claims (6)
で示される請求項１〜５のいずれか１項の組成物。 The epoxy-reactive polyphosphonate has the formula:
The composition of any one of Claims 1-5 shown by these.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47265403P | 2003-05-22 | 2003-05-22 | |
| PCT/US2004/016459 WO2004113411A1 (en) | 2003-05-22 | 2004-05-19 | Polyphosphonate flame retardant curing agent for epoxy resin |
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| Publication Number | Publication Date |
|---|---|
| JP2007502904A true JP2007502904A (en) | 2007-02-15 |
| JP2007502904A5 JP2007502904A5 (en) | 2007-07-12 |
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| JP2006533410A Pending JP2007502904A (en) | 2003-05-22 | 2004-05-19 | Polyphosphonate flame retardant curing agent for polyexic resin |
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| Country | Link |
|---|---|
| EP (1) | EP1625171A1 (en) |
| JP (1) | JP2007502904A (en) |
| KR (1) | KR20060019547A (en) |
| CN (1) | CN1795223A (en) |
| CA (1) | CA2525856A1 (en) |
| WO (1) | WO2004113411A1 (en) |
Cited By (5)
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| JP2010530017A (en) * | 2007-06-14 | 2010-09-02 | ビーエーエスエフ ソシエタス・ヨーロピア | Flame retardant composition |
| JP4782789B2 (en) * | 2004-08-31 | 2011-09-28 | スプレスタ エルエルシー | Process for preparing oligomeric / polymeric derivatives of alkylphosphonic acid diaryl esters and alkylphosphonic acid arylene derivatives |
| JP2012507599A (en) * | 2008-10-29 | 2012-03-29 | アイシーエル−アイピー アメリカ インコーポレイテッド | Phosphorus-containing flame-retardant epoxy resin composition, prepreg and laminate thereof |
| WO2012165665A1 (en) * | 2011-06-03 | 2012-12-06 | Arisawa Mfg. Co., Ltd. | Fire-retardant resin composition, metal-clad base laminate for flexible printed circuit board utilizing said composition, cover lay, adhesive sheet for flexible printed circuit board and flexible printed circuit board |
| US10167377B2 (en) | 2013-01-22 | 2019-01-01 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
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| US20110132646A1 (en) * | 2009-06-12 | 2011-06-09 | Icl-Ip America Inc. | Flame retardant epoxy resin composition, prepreg and laminate thereof |
| WO2012088435A2 (en) | 2010-12-22 | 2012-06-28 | Frx Polymers, Inc. | Hyperbranched oligomeric phosphonates and compositions including the same |
| TWI475052B (en) * | 2011-12-22 | 2015-03-01 | Frx Polymers Inc | Oligomeric phosphonates and compositions including the same |
| KR101469270B1 (en) * | 2011-12-30 | 2014-12-08 | 제일모직주식회사 | Polyphosphonate copolymer, method for preparing thereof and flame retardant thermoplastic resin composition comprising the same |
| CN105802127B (en) * | 2014-12-29 | 2018-05-04 | 广东生益科技股份有限公司 | A kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits |
| CN105801814B (en) * | 2014-12-29 | 2018-05-04 | 广东生益科技股份有限公司 | A kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits |
| CN105330824A (en) * | 2015-12-09 | 2016-02-17 | 西安元创化工科技股份有限公司 | Flame retardant curing agent for epoxy resin and preparation method of flame retardant curing agent |
| TWI620785B (en) * | 2016-08-10 | 2018-04-11 | Taiwan Union Technology Corporation | Resin composition, and prepreg, metal-clad laminate and printed circuit board prepared using the same |
| TWI620763B (en) * | 2017-04-27 | 2018-04-11 | Taiwan Union Technology Corporation | Resin composition, and prepreg, metal-clad laminate and printed circuit board prepared using the same |
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| CN107778456A (en) * | 2017-11-22 | 2018-03-09 | 吉林省高性能复合材料制造业创新中心有限公司 | Middle temperature curing epoxy low resin and preparation method thereof and the application in large-tow carbon fiber epoxy composite power transmission shaft |
| CN107903383A (en) * | 2017-11-22 | 2018-04-13 | 吉林省高性能复合材料制造业创新中心有限公司 | Middle temperature curing epoxy low resin and preparation method thereof and the application in size tow carbon fiber epoxy composite transmission shaft |
| CN109705530B (en) * | 2018-12-29 | 2021-06-04 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg, laminate and high-frequency circuit board containing the same |
| CN112480373A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Flame-retardant epoxy resin composition and preparation method and application thereof |
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- 2004-05-19 CN CNA2004800140798A patent/CN1795223A/en active Pending
- 2004-05-19 JP JP2006533410A patent/JP2007502904A/en active Pending
- 2004-05-19 KR KR1020057022045A patent/KR20060019547A/en not_active Application Discontinuation
- 2004-05-19 EP EP04776110A patent/EP1625171A1/en not_active Withdrawn
- 2004-05-19 WO PCT/US2004/016459 patent/WO2004113411A1/en active Application Filing
- 2004-05-19 CA CA002525856A patent/CA2525856A1/en not_active Abandoned
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| JPH1180178A (en) * | 1997-09-12 | 1999-03-26 | Hitachi Chem Co Ltd | Oligomer terminated with phosphorus-containing phenol and its production |
| JP2001019746A (en) * | 1999-07-09 | 2001-01-23 | Asahi Denka Kogyo Kk | Flame retardant epoxy resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4782789B2 (en) * | 2004-08-31 | 2011-09-28 | スプレスタ エルエルシー | Process for preparing oligomeric / polymeric derivatives of alkylphosphonic acid diaryl esters and alkylphosphonic acid arylene derivatives |
| JP2010530017A (en) * | 2007-06-14 | 2010-09-02 | ビーエーエスエフ ソシエタス・ヨーロピア | Flame retardant composition |
| JP2012507599A (en) * | 2008-10-29 | 2012-03-29 | アイシーエル−アイピー アメリカ インコーポレイテッド | Phosphorus-containing flame-retardant epoxy resin composition, prepreg and laminate thereof |
| WO2012165665A1 (en) * | 2011-06-03 | 2012-12-06 | Arisawa Mfg. Co., Ltd. | Fire-retardant resin composition, metal-clad base laminate for flexible printed circuit board utilizing said composition, cover lay, adhesive sheet for flexible printed circuit board and flexible printed circuit board |
| US10167377B2 (en) | 2013-01-22 | 2019-01-01 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2525856A1 (en) | 2004-12-29 |
| KR20060019547A (en) | 2006-03-03 |
| EP1625171A1 (en) | 2006-02-15 |
| WO2004113411A1 (en) | 2004-12-29 |
| CN1795223A (en) | 2006-06-28 |
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