TW201224033A - Solvent-free benzoxazine based thermosetting resin composition - Google Patents

Solvent-free benzoxazine based thermosetting resin composition Download PDF

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TW201224033A
TW201224033A TW100126665A TW100126665A TW201224033A TW 201224033 A TW201224033 A TW 201224033A TW 100126665 A TW100126665 A TW 100126665A TW 100126665 A TW100126665 A TW 100126665A TW 201224033 A TW201224033 A TW 201224033A
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group
solvent
resin composition
thermosetting resin
substituted
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TW100126665A
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Chinese (zh)
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Frank Tran
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Huntsman Adv Mat Americas Inc
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers

Abstract

The present disclosure relates to a solvent-free thermosetting resin composition including a benzoxazine component, a liquid epoxy compound and a toughening agent comprising a phenol-terminated polyurethane, polyurea or polyurea-urethane. The solvent-free thermosetting resin composition, upon curing, provides a cured product exhibiting improved thermal and physical properties, and is therefore useful in high temperature applications in various industries, such as in the aerospace, automotive and rail industries.

Description

201224033 六、發明說明： 【發明所屬之技術領域】 本發明係關於以苯并〇惡„并兔 ^ 不开〜'开為主之不含溶劑的熱固性樹脂 組合物及其在多種應用中之用途，諸如，製造預浸片、壓 層板、模造材料及黏著劑。 本申請案主張2〇10年7月28曰申請的美國專利申請號第 61/368,3 1 1號之優先權，其以引用方式併人本文。) 【先前技術】 複合物件-般由兩主要構件組成：連續樹脂基質及強化 纖維。該等複合物件通常要求在特定環境中（例如，在航 太及汽車工業）執行，且其等熱及物理限制及特點至關重 要。 酚醛樹脂係爲人所熟知應用於製造複合物件，係由於其 展現極佳之火、煙霧及毒性（FST)性質，在長期暴露於高 溫後保持熱及機械性質’及極佳電及化學耐性。然而，亦 知由於其高黏度、低固化速率及高空隙含量，而相當難以 拉擠。在過去也用到改性環氧樹脂及氰基丙烯酸酯，但是 其等在高於150 °C之運作溫度時易於迅速降解。含石夕化合 物具有極佳高溫性質’然而，其等缺少對於許多應用所必 需之雨摺痕抗剪強度。 近來，已採用苯并噁哨化合物及其組合物經由浸潰及灌 輸過程製造預浸、壓層板、及結構複合物（參見，例 如，美國專利第4,607,091號；美國專利第5,200,452號及 美國專利第6,207,786號）。此類化合物展現改善的處理及 157587.doc 201224033 固化性質’諸如低黏度、固化期間無揮發物釋放、趨近零 之收縮、高玻璃轉移溫度、極佳之化學/電耐性及阻燃性 質。然而’其等係典型潛在物質，且因此需要更高溫度來 膠化及完全固化。另外，其等亦易於在固化後變為固有腌 性。 已開發出多種苯并噁畊爲主之韌化組合物以改善其等撓 性。例如，WO 2010/031826 及 WO 2007/075743 揭示含有 苯并噁畊化合物及酚（較佳雙酚A)封端預聚物韌化劑之固 化組合物；EP 163903S揭示含有苯并噁啡及丙烯腈-丁二 烯共聚物韌化劑之固化組合物；w〇 2〇〇9/〇75746教示包含 苯并噁喷及含有至少3個苯并。惡，環及至少一個脂肪族、 雜脂肪族、芳脂肪族、雜芳脂肪族、芳香族或雜芳族軟片 段之苯并t井巨單體減劑；w〇2_/G75744教示苯并设 味爲主及用於苯并㈣基質樹脂成分之以非苯并嗯啡爲^ 之勃化添加劑之應用；及_ 2〇〇7/〇648〇1揭示一種电人 物，其含有苯并^井及兩加成動化劑之結合物：第一種加 成動化劑係自含經基化合物、含異氛酸§旨基化合物及紛類 :σ物製備，1’第一種加成韌化劑係自第一加成物及含 環氧化合物及第二酚類化合物製備。 餐於此技術狀態’本發明目沾 目的之一為提供一種經改善的 以苯并噁喑爲主之熱固性樹 一 、、且σ物，其—旦固化， 在高溫長時間熱及物理地執行， 便得其可用於多種工業中 之高溫應用’諸如在航太、汽車及鋼轨工業。 ^ 【發明内容】 157587.doc 201224033 本發明提供一種不含溶劑之熱固性樹脂組合物，其包括 (a) 含有雙官能基苯并噁畊及單官能基苯并噁畊之苯并 噁嗜成分； (b) 液體環氧化合物；及 (c) 含有式（III)之酚終端聚胺基甲酸酯、聚脲或聚脲_胺 基甲酸酯的韌化劑 0201224033 VI. OBJECTS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a solvent-free thermosetting resin composition based on benzoindole and the like, and its use in various applications. For example, the manufacture of prepreg sheets, laminates, molding materials, and adhesives. The present application claims priority to U.S. Patent Application Serial No. 61/368,311, filed on Jan. 28, 2008. Citation is by reference.) [Prior Art] Composite articles are generally composed of two main components: a continuous resin matrix and reinforced fibers. These composites are usually required to be executed in a specific environment (for example, in aerospace and automotive industries). And its isothermal and physical limitations and characteristics are essential. Phenolic resins are well known for their use in the manufacture of composite articles due to their excellent fire, smoke and toxicity (FST) properties, after prolonged exposure to high temperatures. Maintains thermal and mechanical properties' and excellent electrical and chemical resistance. However, it is also known to be difficult to pull due to its high viscosity, low cure rate and high void content. Modified epoxy has also been used in the past. Lipids and cyanoacrylates, but they are prone to rapid degradation at operating temperatures above 150 ° C. Containing Shi Xi compounds have excellent high temperature properties' However, they lack the rain crease shear required for many applications. Intensity. Recently, benzoxanthate compounds and compositions thereof have been used to make prepreg, laminate, and structural composites by impregnation and infusion processes (see, for example, U.S. Patent No. 4,607,091; U.S. Patent No. 5,200,452 and U.S. Patent No. 6,207,786). Such compounds exhibit improved handling and 157587.doc 201224033 Curing properties such as low viscosity, no volatile release during curing, shrinkage towards zero, high glass transition temperature, excellent chemical/electricity Resistance and flame retardant properties. However, 'it is a typical latent substance, and therefore requires higher temperature for gelation and complete curing. In addition, it is also easy to become inherently cured after curing. A variety of benzoxime has been developed. Toughing-based toughening compositions to improve their flexibility. For example, WO 2010/031826 and WO 2007/075743 disclose the inclusion of benzoin-fermenting compounds and phenols ( a cured composition of a bisphenol A) capped prepolymer toughening agent; EP 163903S discloses a cured composition comprising a benzoxanine and an acrylonitrile-butadiene copolymer toughening agent; w〇2〇〇9/ 〇75746 teaches benzoxene containing at least 3 benzo, oxime, ring and at least one aliphatic, heteroaliphatic, araliphatic, heteroaromatic aliphatic, aromatic or heteroaromatic soft segment Well giant monomer reducer; w〇2_/G75744 teaches the application of benzoate-based styrene and benzo (4) matrix resin component with non-benzophenone as the saponification additive; and _ 2〇〇7 /〇648〇1 discloses an electric character comprising a combination of a benzoxene well and a two addition catalyzing agent: the first addition catalyzing agent is a compound containing a thiol compound and a acetyl-containing compound And a variety of: σ preparation, 1 'the first addition toughening agent is prepared from the first adduct and the epoxy-containing compound and the second phenolic compound. One of the purposes of the present invention is to provide an improved thermosetting tree based on benzoxanthine, and σ, which is solidified, thermally and physically executed at high temperatures for a long time. It can be used in high temperature applications in a variety of industries, such as in the aerospace, automotive and rail industries. [Invention] 157587.doc 201224033 The present invention provides a solvent-free thermosetting resin composition comprising (a) a benzoxanthophilic component containing a difunctional benzoxamic acid and a monofunctional benzoin; (b) liquid epoxy compounds; and (c) toughening agents containing phenolic terminal polyurethanes of the formula (III), polyureas or polyureas-urethanes 0

〇 II R〇 X 一· C —-Y—R2 —- (〇H)m wm J η (III) 其中m為1或2，η為2至6，RG為移除終端異氰酸酯基、胺基 或羥基基團後之彈性預聚物之n_價基，此彈性預聚物可溶 於或分散於環氧樹脂，X及γ彼此獨立為或_NR3_，至少 一個X或Y為-NR3- ’ R2為分別移除酚類羥基或胺基或胺基 與酚類經基二者後之多元酚或胺基酚之⑺+丨―價基，及…為 氫、CVC6燒基或盼。 以上組分，當結合及固化時，意外地產生一種固化產 物’其展現改善的熱及物理性質’諸如高玻璃轉移溫度、 撓性心性’ 0而適用於運作溫度可自周圍溫度至175t 或更1¾溫度範圍内之應用。 【實施方式】 如果本文出現術語「包括」及其衍生體並非旨在排除其 它任意額外組分，步驟或程序的存在，無論本文所揭示是 否相同。！ 了避免任何疑惑，本文申請之所有組合物藉由 I57587.doc 201224033 使用術語「包括」可包含任意額外添加劑、輔劑或化合 物，除非有相反陳述。相反地，若本文存在術語「基本上 由…組成」’則係自該範圍中排除任意後續载述、任意其 他成分、步驟或程序，但非必要操作者除外；且純用術 語「由…組成」’則排除未特別描述或列出之任专纟且分、 步驟或程序。術語「或」，除非相反表示，否則意指所列 各別組分以及其任意組合。 本文採用冠詞「一」意指一個或一個以上（例，至少一 個)本文之語法對象，來説「一環氧基」意指一個環 氧基或一個以上之環氧基。 片語「在-實施例中」「依據一實施例」等一般意指該 片語後所跟隨之特定特徵、結構或特點均包含在至少本發 明之一實施例中，且可包含在本發明之—個以上實施例 中。重要地，此類片語未必意指同一實施例。 本發明實質上係有關一種不含溶劑之熱固性樹脂組合 物’其包括：⑴含有雙官能基苯并心井及單官能基苯并嗯 畊之苯并噁畊成分；（2)液體環氧化合物；及（3)含有上式 则之盼終端聚胺基曱酸自旨 '聚腺或聚腺·胺基曱酸醋的動 化劑。如本文所用’ Γ不含溶劑」意指無溶劑或水存在於 熱固性樹脂組合物中，但微量作爲雜質存在於任意熱固性 樹脂成分者除外。相對於熱固性樹脂組合物之總重，較佳 任何此等雜質係少於2重量％，更佳少於〇5重量％及尤佳 :於0.01重量％。意外地發現該不含溶劑之熱固性樹脂組 口物，一旦固化，將產生展現極佳熱與物理性質平衡之固 157587.doc -6 - 201224033 化產物，包括’例如高玻璃轉移溫度（Tg)、在周圍溫度及 溫度高於約177°C (350°F)之高摺痕抗剪強度、良好繞性及 低可燃性。為避免疑慮，應了解本文所採用之「周圍溫 度」意指工作環境周圍之溫度（例如’使用組合物時之地 區、建築物或室内的溫度）’排除由直接施加熱於組合物 上以促進熱固性樹脂組合物固化所引起的任何溫度變化。 此周圍溫度係一般介於l〇°C至30°c。 依據一實施例，此不含溶劑之熱固性樹脂組合物包括每 100重量份不含溶劑之熱固性樹脂組合物為約〇 5_90重量 份，較佳約10-80重量份，且更佳約20-70重量份之包括雙 官能基苯并°惡畊及單官能基苯并噁畊之苯并。惡P井成分。 在一實施例中，雙官能基苯并噁畊可為由式⑴表示之化 合物：〇II R〇X··C—-Y—R 2 —( 〇H)m wm J η (III) wherein m is 1 or 2, η is 2 to 6, and RG is a terminal isocyanate group, an amine group or The n-valent group of the elastic prepolymer after the hydroxyl group, the elastic prepolymer is soluble or dispersed in the epoxy resin, and X and γ are independently of each other or _NR3_, and at least one X or Y is -NR3-' R2 is a (7)+丨-valent group of a polyhydric phenol or an aminophenol which is respectively removed from a phenolic hydroxyl group or an amine group or an amine group and a phenolic group, and is hydrogen, CVC6 or a desired group. The above components, when combined and cured, unexpectedly produce a cured product that exhibits improved thermal and physical properties such as high glass transition temperature, flexible core '0 and is suitable for operating temperatures from ambient temperature to 175t or more. Applications in the 13⁄4 temperature range. [Embodiment] If the term "comprising" and its derivatives are not intended to exclude any additional additional components, the existence of steps or procedures, whether or not disclosed herein. ! To avoid any doubt, all of the compositions claimed herein may contain any additional additives, adjuvants or compounds by the use of the term "comprising" by I57587.doc 201224033, unless stated to the contrary. Conversely, if the term "consisting essentially of" is used herein, any subsequent description, any other component, step or procedure is excluded from the scope, except for non-essential operators; and the term "consisting of" is used purely. ''Excludes any specifics, steps, or procedures not specifically described or listed. The term "or", unless indicated to the contrary, refers to the individual components listed and any combination thereof. The article "a" is used herein to mean one or more (eg, at least one of) grammatical objects herein, and "monooxy" means an epoxy or more than one epoxy. The phrase "in an embodiment", "in accordance with an embodiment", and the like generally mean that a particular feature, structure, or characteristic that is followed by the phrase is included in at least one embodiment of the invention and may be included in the present invention. One or more of the above embodiments. Importantly, such phrases are not necessarily referring to the same embodiment. The present invention relates substantially to a solvent-free thermosetting resin composition comprising: (1) a benzoaceline containing a difunctional benzoxin well and a monofunctional benzoin; (2) a liquid epoxy compound And (3) a kinetic agent containing the above formula for the terminal polyamine decanoic acid from the purpose of 'poly-gland or poly-glycolamine citrate. As used herein, "Γ without solvent" means that no solvent or water is present in the thermosetting resin composition, except that trace amounts are present as impurities in any thermosetting resin component. Preferably, any such impurities are less than 2% by weight, more preferably less than 5% by weight and more preferably 0.01% by weight, based on the total weight of the thermosetting resin composition. It has been unexpectedly discovered that the solvent-free thermosetting resin composition, once cured, will produce a solid product of 157587.doc -6 - 201224033 which exhibits excellent thermal and physical properties, including, for example, a high glass transition temperature (Tg), High crease shear strength, good winding and low flammability at ambient temperatures and temperatures above about 177 ° C (350 ° F). For the avoidance of doubt, it should be understood that the term "ambient temperature" as used herein means the temperature around the working environment (eg 'area, building or indoor temperature when using the composition'' is excluded by direct application of heat to the composition to promote Any temperature change caused by curing of the thermosetting resin composition. This ambient temperature is generally between 10 ° C and 30 ° C. According to an embodiment, the solvent-free thermosetting resin composition comprises about 5 to 90 parts by weight, preferably about 10 to 80 parts by weight, and more preferably about 20 to 70 parts per 100 parts by weight of the solvent-free thermosetting resin composition. The parts by weight include difunctional benzoxanthene and monofunctional benzophenone. The composition of the evil P well. In one embodiment, the difunctional benzoxanthene may be a compound represented by the formula (1):

其中1^為直接鍵、經取代或未經取代之CrC^o伸烧基、經 取代或未經取代之C6_C2〇伸芳基、經取代或未經取代之c2_ C2〇伸雜芳基或C=0，且Rb為氫、經取代或未經取代之Ci_ Go烷基、經取代或未經取代之Ca-Cso烯基、經取代或未經 取代之C6-C2q芳基、經取代或未經取代之c2-c2〇雜芳基、 157587.doc 201224033 =取代或未經取代C4_C2g碳環基、經取代或未經取代之c” 2。雜環基、扣.c】。㈣基。aRb基上之合適取代基可 0括胺基、C1-C4烷基及烯丙基。 在又-實施例中，Ra為經取代^3伸燒基且^為經取 代或未經取代之<：6芳基。 在另一實施例中 示之化合物： 該單官能基苯并噁畊可為由式（11)表Wherein 1 is a direct bond, a substituted or unsubstituted CrC^o extended alkyl group, a substituted or unsubstituted C6_C2 fluorene extended aryl group, a substituted or unsubstituted c2_C2 fluorene heteroaryl group or C =0, and Rb is hydrogen, substituted or unsubstituted Ci_Go alkyl, substituted or unsubstituted Ca-Csoalkenyl, substituted or unsubstituted C6-C2q aryl, substituted or not Substituted c2-c2 anthracene aryl, 157587.doc 201224033 = substituted or unsubstituted C4_C2g carbocyclic group, substituted or unsubstituted c" 2. heterocyclic group, deuterium.c]. (d) group. aRb Suitable substituents on the group may include an amine group, a C1-C4 alkyl group, and an allyl group. In still another embodiment, Ra is a substituted alkyl group and is substituted or unsubstituted. : 6 aryl. Compound shown in another embodiment: the monofunctional benzoic argon can be obtained from the formula (11)

c (Π) 其中R為氣、經取代或未經取代之滅基、經取代或 未經取代之C2_C2q婦基、經取代或未經取代之C6_C2。芳 ^ i取代或未經取代之C2-C2〇雜芳基、經取代或未經取 ^之C^C：2。碳環基、經取代或未經取代雜環基、 或Κ,ο%烷基。Rc基上之合適取代基可包括胺基、 燒基及烯丙基。 在一實施例中，RC為經取代或未經取代之q_C2〇芳基， 較佳為經取代或未經取代之c6芳基。 式⑴之雙官能基苯并噁畊與式（11)之單官能基苯并噁畊 之相對量可在自80:20至20:80(重量：重量）範圍内，較佳約 6〇.4〇_4〇:6〇(重量：重量），且更佳約55:45-45:55(重量：重 157587.docc (Π) wherein R is a gas, substituted or unsubstituted thiol, substituted or unsubstituted C2_C2q phenyl group, substituted or unsubstituted C6_C2. A substituted or unsubstituted C2-C2 anthracene aryl group, substituted or unsubstituted C^C:2. Carbocyclyl, substituted or unsubstituted heterocyclic, or oxime, ο% alkyl. Suitable substituents on the Rc group may include amine groups, alkyl groups, and allyl groups. In one embodiment, RC is a substituted or unsubstituted q_C2 fluorenyl group, preferably a substituted or unsubstituted c6 aryl group. The relative amount of the difunctional benzoxylene of formula (1) and the monofunctional benzoxylene of formula (11) may range from 80:20 to 20:80 (weight:weight), preferably about 6 〇. 4〇_4〇: 6〇 (weight: weight), and more preferably about 55:45-45:55 (weight: weight 157587.doc

S -8 - 201224033 量）’且甚至更佳約50:50(重量：重量）。 雙S此基及單官能基苯并。惡p井係購自多處，包括 Huntsman Advanced Materials Americas LLC ' GeorgiaS -8 - 201224033 重量)' and even better about 50:50 (weight: weight). Double S this base and monofunctional benzo. The pp well is purchased from several locations, including Huntsman Advanced Materials Americas LLC ' Georgia

Pacific Resins公司及Shikoku Chemicals公司。該苯并噁畊 亦可藉由使單紛類化合物（例如，苯酚或經取代笨酚）或二 紛類化合物（例如雙酚A、雙酚F、雙酚S、酚酞、硫代二 酚、雙環戊二烯或萘），與醛（例如，甲醛）及一級胺反應而 獲得。此一級胺可為芳香族單胺或二胺、脂族胺、環脂族 胺、雜環狀單胺、例如苯胺、鄰苯二胺 '間苯二胺及對苯 一胺、聯苯胺、4,4'-二胺基二苯基曱烷、環己胺、丁胺、 甲胺、己胺、烯丙基胺、糠胺乙二胺及丙二胺。該等一級 胺可在其等各自碳部分’經C,-C8烷基或烯丙基取代。較 佳之-級胺係通式RdNH2，#中〜為稀丙基、未經取代或 經取代苯基、未經取代或經取代Ci_C8烷基或未經取代或Pacific Resins and Shikoku Chemicals. The benzoic acid can also be obtained by using a single compound (for example, phenol or substituted phenol) or a compound such as bisphenol A, bisphenol F, bisphenol S, phenolphthalein, thiodiphenol, Dicyclopentadiene or naphthalene) is obtained by reacting with an aldehyde (for example, formaldehyde) and a primary amine. The primary amine may be an aromatic monoamine or diamine, an aliphatic amine, a cycloaliphatic amine, a heterocyclic monoamine such as aniline, o-phenylenediamine 'm-phenylenediamine and p-phenyleneamine, benzidine, 4 4'-Diaminodiphenylnonane, cyclohexylamine, butylamine, methylamine, hexylamine, allylamine, guanamine ethylenediamine and propylenediamine. The primary amines may be substituted at their respective carbon moieties by C, -C8 alkyl or allyl. Preferably, the -amine is of the formula RdNH2, #~ is a propyl, unsubstituted or substituted phenyl, unsubstituted or substituted Ci_C8 alkyl or unsubstituted or

Rd基上之合適取代基包括胺基、Cl_Suitable substituents on the Rd base include an amine group, Cl_

發明之苯并噁哨·的方法。 經取代〇3_08環燒基。 C4烧基及稀丙基。在一些 代基。較佳Rd為苯基。The method of inventing the benzoin and whistle. Substituted 〇3_08 cycloalkyl. C4 alkyl and dilute propyl. In some generations. Preferably Rd is a phenyl group.

施例，該液體環氧化合物包括含有平均至 至少兩個環氧基之 157587.doc 201224033 環氧化合物。在又另一實施例中，該液體環氧化合物包括 含有平均不超過1()個環氧基之環氧化合物，較佳不超過4 個％氧基’且更佳不超過2.5個環氧基。 -實施例中，該液體環氧化合物包含具有環氧當量相當 低例如少於約500,且較好少於约2〇〇之環氧化合物。在其 他實施例中’該液體環氧化合物之環氧當量在約％至約 500之範圍，較好約1〇〇至約2〇〇之範圍，且更好約us至約 150之範圍。名同」環氧當量重量」表示具有】克當量環氧 基之化合物重量克數。 依據一實施例，該液體環氧化合物為非縮水甘油基環氧 化合物。此類環氧化合物結構上可為直鏈、支鏈或環狀。 例如，可包括一種或多種環氧化合物，其中其環氧基形成 部分脂環族或雜環系環系統。其他包括含至少一個環氧基 %己基直接或間接與含至少一個矽原子之基鍵結之含環氧 基化合物。實例揭示於美國專利案第5,639,413號，其以引 用之方式併入本文中。又其他係包括含有一個或多個環己 烯氧化基之環氧化合物及含有一個或多個環戊烯氧化基之 環氧化合物。 特別適且之非缩水甘油基環氧化合物包括下列雙官能基 非缩水甘油基環氧化合物，其中環氧基構成脂環族及雜環 系環系統之一部分：雙（2,3-環氧環戊基）醚、1,2-雙（2,3-環 氧裱戍氧基）乙烷、3,4_環氧環己基羧酸3,4_環氧環已基-曱 S曰、3’4-%氧基曱基環己烷羧酸3,4_環氧基甲基-環己 基曱S曰、—（3,4-環氧環己基曱基）己二酸酯、二（3,4_環氧 157587.doc 201224033 基-6-曱基環己基甲基）己二酸酯、伸乙基雙（3,4_環氧基環 已基甲酸酯）、乙二醇二（3,4-環氧基環己基曱基）醚、二氧 化乙烯基環己烯、二環氧化二環戊二烯或2_(3,4_環氧基環 己基-5,5-螺-3,4-環氧基）環己烧_丨，3二噁烧，及2,2'_雙_ (3,4-環氧基-環己基）-丙烷。 南度較佳之雙g能基非缩水甘油基環氧化合物包括環脂 族雙官能基環氧樹脂，諸如，3'，4，-環氧基環己烷羧酸3,4-環氧基環己基-曱酯及2,2，-雙-(3,4-環氧基-環己基丙烷， 以前者最佳。 該不含溶劑之熱固性樹脂組合物亦包含每1〇〇重量份之 不含溶劑之熱固性樹脂組合物為約01_40重量份，較佳約 0.5-20重量份之動化劑。 在一實施例中，該韌化劑包括式（ΠΙ)之酚終端聚胺基曱 酸酯、聚脲、或聚脲-胺基曱酸酯： ΟBy way of example, the liquid epoxy compound comprises 157587.doc 201224033 epoxy compound containing an average of at least two epoxy groups. In still another embodiment, the liquid epoxy compound comprises an epoxy compound containing an average of no more than 1 (1) epoxy groups, preferably no more than 4% by weight 'and more preferably no more than 2.5 epoxy groups. . In an embodiment, the liquid epoxy compound comprises an epoxy compound having a relatively low epoxy equivalent weight, such as less than about 500, and preferably less than about 2 Torr. In other embodiments, the epoxy equivalent of the liquid epoxy compound is in the range of from about % to about 500, preferably from about 1 Torr to about 2 Torr, and more preferably from about us to about 150. The same "epoxy equivalent weight" means the weight of the compound having a gram equivalent of the epoxy group. According to an embodiment, the liquid epoxy compound is a non-glycidyl epoxy compound. Such epoxy compounds may be linear, branched or cyclic in structure. For example, one or more epoxy compounds may be included in which the epoxy group forms a partial alicyclic or heterocyclic ring system. Others include an epoxy group-containing compound having at least one epoxy group having a hexyl group bonded directly or indirectly to a group containing at least one ruthenium atom. An example is disclosed in U.S. Patent No. 5,639,413, incorporated herein by reference. Still other examples include epoxy compounds containing one or more cyclohexene oxide groups and epoxy compounds containing one or more cyclopentene oxide groups. Particularly suitable non-glycidyl epoxy compounds include the following bifunctional non-glycidyl epoxy compounds wherein the epoxy group forms part of an alicyclic and heterocyclic ring system: bis (2,3-epoxy ring) Pentyl)ether, 1,2-bis(2,3-epoxydecyloxy)ethane, 3,4-epoxycyclohexylcarboxylic acid 3,4-epoxycyclohexyl-曱S曰, 3 '4-% oxodecylcyclohexanecarboxylic acid 3,4-epoxymethyl-cyclohexyl fluorene S曰, —(3,4-epoxycyclohexyldecyl) adipate, di(3) , 4_epoxy 157587.doc 201224033 -6-fluorenylcyclohexylmethyl) adipate, ethyl bis(3,4-epoxycyclodecyl), ethylene glycol ( 3,4-epoxycyclohexyldecyl)ether, vinylcyclohexene oxide, dicyclopentadienyl dicyclopentene or 2-(3,4-epoxycyclohexyl-5,5-spiro-3 , 4-epoxy)cyclohexanyl hydrazine, 3 dioxin, and 2,2'-bis-(3,4-epoxy-cyclohexyl)-propane. The preferred double g-energy non-glycidyl epoxy compound of the south includes a cycloaliphatic difunctional epoxy resin such as a 3,4-epoxy ring of 3',4,-epoxycyclohexanecarboxylic acid. Hexyl-nonyl ester and 2,2,-bis-(3,4-epoxy-cyclohexylpropane, the former is the best. The solvent-free thermosetting resin composition also contains no part by weight per part. The solvent thermosetting resin composition is about 01 to 40 parts by weight, preferably about 0.5 to 20 parts by weight, of the kinetic agent. In one embodiment, the toughening agent comprises a phenolic terminal polyamino phthalate of the formula (ΠΙ), Polyurea, or polyurea-amino phthalate: Ο

II R0--X—C ——Y—R2 一 (0H)m (III) 其中m為1或2，η為2至6，RQ為移除終端異氰酸酯基、胺基 或經基後之彈性預聚物之n-價基，此彈性預聚物可溶於或 分散於環氧樹脂，X及Υ彼此獨立為_〇_或_NR3_，至少一個 X或Y為-NR3- ’ R2為分別移除酚性羥基或胺基或胺基與酚 性經基一者後之多元驗或胺基齡之m+l_價基，及R3為氫、 q-c：6烷基或酚。術語「彈性預聚物基rG」意指以預聚物 I57587.doc •11- 201224033 之η-異氰酸酯基、η-胺基、或n-羥基終端之基，當此等基 團被封住後得到式（III)之紛終端之聚胺基曱酸酯、聚脲、 或聚脲-胺基曱酸酯’其當與笨并噁畊及液體環氧化合物 組合後’固化後’產生彈性體相或彈性體相之混合物。美 國專利第5,278,257號’第4欄第20行至第16攔第20行提出 了式（III)韌化劑之詳細描述，其揭示以引用的方式併入本 文中。較佳地，式（III)之韌化劑為酚終端之聚胺基曱酸 酯’更佳地為二烯丙基雙酚Α終端之聚胺基曱酸酯。此韌 化劑之實施例為Flexibilizer dY 965(購自Huntsman Advanced Materials Americas LLC，依據美國專利第 5,278,257號之實例16製備）。 視情況’該不含溶劑之熱固性樹脂組合物亦可包括觸 媒、阻燃劑、及填充料或添加劑。 該等觸媒實例包括（但不限於）酸類（諸如硫代二丙酸、乙 酸、丙酸、草酸、己二酸、癸二酸、苯甲酸、硫酸、對曱 苯磺酸、及磷酸）及酚類（諸如鄰甲酚、鄰-、間-或對-二羥 基苯、2,4,6-三硝基苯紛、2,6-二-第三丁基對-甲酚-經基 苯、2,2’-二經基聯苯盼、雙紛a、雙酚F、雙酚S、4,4-硫 代二苯酚、苯酚-酚醛、鄰曱酚-酚醛、對曱酚_酚醛、第三 丁基苯酚-酚醛 '四苯酚乙烷酚醛，具有二環戊二烯結構 之甲酚-酚醛、二烯丙基雙酚A、及二胺基二苯酚砜）。該 熱固性樹脂基質可包括每1 〇 〇重量份之不含溶劑之熱固性 樹脂組合物為約0.001 -15重量份之觸媒。 阻燃劑之實施例包括（但不限於）鱗系阻燃劑，諸如II R0--X—C—Y—R 2 —(0H)m (III) wherein m is 1 or 2 and η is 2 to 6, and RQ is an elastic pre-removal of the terminal isocyanate group, amine group or base group. The n-valent group of the polymer, the elastic prepolymer is soluble or dispersed in the epoxy resin, X and Υ are independently _〇_ or _NR3_, and at least one X or Y is -NR3- 'R2 is shifted separately In addition to the phenolic hydroxyl or amine or amine group and the phenolic vial, the qualifier or the amine group m+l_valent group, and R3 is hydrogen, qc:6 alkyl or phenol. The term "elastic prepolymer base rG" means an η-isocyanate group, an η-amino group, or an n-hydroxyl terminal group of the prepolymer I57587.doc •11-201224033, after such groups are blocked Obtaining a polyamino phthalate, polyurea, or polyurea-amino phthalate ester of the formula (III), which is combined with a stupid and sloping liquid epoxy compound to form an elastomer after curing. a mixture of phases or elastomer phases. A detailed description of the toughening agent of formula (III) is set forth in U.S. Patent No. 5,278,257, at col. 4, line 20 to line 16, line 20, the disclosure of which is incorporated herein by reference. Preferably, the toughening agent of formula (III) is a phenolic terminal polyamine phthalate', more preferably a diallyl bisphenol quinone terminated polyamine phthalate. An example of such a toughening agent is Flexibilizer dY 965 (available from Huntsman Advanced Materials Americas LLC, according to Example 16 of U.S. Patent No. 5,278,257). The solvent-free thermosetting resin composition may also include a catalyst, a flame retardant, and a filler or an additive, as the case may be. Examples of such catalysts include, but are not limited to, acids such as thiodipropionic acid, acetic acid, propionic acid, oxalic acid, adipic acid, sebacic acid, benzoic acid, sulfuric acid, p-toluenesulfonic acid, and phosphoric acid, and Phenols (such as o-cresol, o-, m- or p-dihydroxybenzene, 2,4,6-trinitrobenzene, 2,6-di-t-butyl-p-cresol-perylene) , 2,2'-di-biphenyl, bisphenol A, bisphenol S, 4,4-thiodiphenol, phenol-phenolic, o-nonylphenol-phenolic, p-nonylphenol-phenolic, Third butyl phenol-phenolic 'tetraphenol ethane phenol, cresol-phenolic having dicyclopentadiene structure, diallyl bisphenol A, and diaminodiphenol sulfone). The thermosetting resin matrix may comprise from about 0.001 to 15 parts by weight of the catalyst per part by weight of the solvent-free thermosetting resin composition. Examples of flame retardants include, but are not limited to, scaly flame retardants, such as

157587.doc 32 S 201224033 DOPO(9，10-二氫_9_氧雜-磷雜菲_〗〇_氧化物）；Fyroflex® PMP阻燃劑（在其鏈端經羥基改性之反應性有機磷添加 劑）；CN2645A(購自 Great Lakes Chemical Corp，基於氧化 磷且含酚類官能度之物質）；Ex〇m阻燃劑（購自claHant); 溴化聚苯醚；及二茂鐵。該不含溶劑之熱固性樹脂組合物 可包含每100重量份之不含溶劑之熱固性樹脂組合物為约 〇_〇〇1-50重量份之阻燃劑。 填充料或添加劑之實例包括（但不限於）安定劑、流動控 制《I石夕烧偶合劑、多麟酸錢、增塑劑、含無機及有機填 之化合物、微空心球、顏料、染料、增黏劑、橡膠、稀釋 劑、脫模劑、及霧化金屬粉末，該不含溶劑之熱固性樹脂 組合物可包含每100重量份之不含溶劑之熱固性樹脂組合 物為約0.001-15重量份之填充料或添加劑。 本發月之不3 ;谷劑之熱固性樹脂組合物可藉由採用常用 設備（例如，攪拌容器、攪拌棒、球磨機、樣品混合器、 靜態混合器或肋條混合器)將各種成分以任意添加順序混 合在-起的熟知方式製備。在一實施例中，提供一種製備 該不含溶劑之熱固性樹脂組合物之方法，該方法包括以下 v驟將約0.5-90重量份苯并噁畊成分與約〇卜3〇重量份 液體環氧化合物及約〇· i _4〇重量份之包含式（m)之齡終端 之聚胺基甲酸酯、聚脲、或聚脲胺基甲酸酯之韌化劑混 合—起’所有重量份均係基於⑽重量份之不含溶劑之熱 固性樹脂組合物。在另—實施例中，提供—種製備不含溶 劑之熱固性樹脂組合物之方法，該方法包括以下步驟：將 157587.doc 13 201224033 約20-70重量份苯并"惡p井成分與約0.5-20重量份液體環氧化 合物及約0.5-20重量份包括式（III)之酚終端聚胺基曱酸 酯、聚脲、或聚脲-胺基甲酸酯之勃化劑及約〇 〇〇1_15重量 份酴觸媒混合在一起，所有重量份均係基於1 〇〇重量份不 含溶劑之熱固性樹脂組合物。該方法的時間及溫度並非關 鍵’但一般可將該等成分在約1 〇 至約6 〇 °c之溫度範圍 内，較佳約2(TC至約6(TC，且更佳約25。(：至4(TC下混合足 夠長時間，直至獲得完全均勻性。 在另一態樣申，本發明提供一種製備樹脂塗覆基板之方 法。該等方法步驟包括使基板與本發明之不含溶劑之熱固 性樹脂組合物接觸。本發明之組合物可藉由熟習此項技術 者已知之任思方法與基板接觸。此等接觸方法之實例包括 (但不僅限於）浸塗、喷塗、模塗、報塗、樹脂灌注方法， 及使物件與含有不含溶劑之熱固性樹脂組合物之浴液接 觸。該基板可為（例如）塑料、玻璃、合金、金屬、陶瓷、 木材、水泥、混凝土、橡膠或強化纖維物質。 依據另一實施例，該不含溶劑之熱固性樹脂組合物，混 〇後，可與任意合適基板接觸且依據工業實施之製程固化 以形成固化產&。如本文所用「固化」表示法係表示上述 不含溶劑之熱固性樹脂組合物轉變成不可溶及不熔交聯產 物，且同時成形以獲得成型物件（諸如模塑、衝壓件或層 壓製件)或獲冑二維結構(諸如塗層、瓷漆或黏合體)。典型 固化：法包括採用加熱、輻射或能源組合使周圍溫度固化 升至高溫固化。該不含溶劑之熱固性樹脂組合物可藉一步 157587.doc157587.doc 32 S 201224033 DOPO(9,10-Dihydro_9_oxa-phosphonium _]〇_oxide); Fyroflex® PMP flame retardant (reactive organic modified by hydroxyl group at its chain end) Phosphorus additive); CN2645A (available from Great Lakes Chemical Corp. based on phosphorus oxide and containing phenolic functionality); Ex〇m flame retardant (available from claHant); brominated polyphenylene ether; and ferrocene. The solvent-free thermosetting resin composition may comprise from about 1 to about 50 parts by weight of the flame retardant per 100 parts by weight of the solvent-free thermosetting resin composition. Examples of fillers or additives include, but are not limited to, stabilizers, flow control, "I Shi Xia coupling agent, polylinic acid, plasticizers, inorganic and organic filler-containing compounds, micro hollow spheres, pigments, dyes, a tackifier, a rubber, a diluent, a mold release agent, and an atomized metal powder, the solvent-free thermosetting resin composition may comprise from about 0.001 to 15 parts by weight per 100 parts by weight of the solvent-free thermosetting resin composition. Filler or additive. This month's not more than 3; the thermosetting resin composition of the cereal can be added in any order by using conventional equipment (for example, a stirring vessel, a stirring rod, a ball mill, a sample mixer, a static mixer or a rib mixer) Mixing is prepared in a well known manner. In one embodiment, a method of preparing the solvent-free thermosetting resin composition is provided, the method comprising the following steps: about 0.5-90 parts by weight of a benzoic acid component and about 3 parts by weight of a liquid epoxy The compound and the toughening agent comprising a polyurethane of a terminal of the formula (m), a polyurea, or a polyurea urethane at a weight of about 〇·i _4 parts by weight - from 'all parts by weight It is based on (10) parts by weight of a solvent-free thermosetting resin composition. In another embodiment, a method of preparing a solvent-free thermosetting resin composition is provided, the method comprising the steps of: 157587.doc 13 201224033 about 20-70 parts by weight of a benzo" 0.5-20 parts by weight of a liquid epoxy compound and about 0.5-20 parts by weight of a phenolic terminal polyamino phthalate, polyurea, or polyurea-urethane-containing hydrazide comprising the formula (III) and about hydrazine 〇〇1_15 parts by weight of the ruthenium catalyst are mixed together, and all parts by weight are based on 1 part by weight of the solvent-free thermosetting resin composition. The time and temperature of the process are not critical 'but generally the components may be in the range of from about 1 Torr to about 6 〇 ° C, preferably from about 2 (TC to about 6 (TC, and more preferably about 25.) : to 4 (TC mixed for a sufficient time until full uniformity is obtained. In another aspect, the present invention provides a method of preparing a resin coated substrate. The method steps include dissolving the substrate and the solvent of the present invention. The thermosetting resin composition is contacted. The composition of the present invention can be contacted with the substrate by any of the methods known to those skilled in the art. Examples of such contacting methods include, but are not limited to, dip coating, spray coating, die coating, Coating, resin infusion, and contacting the article with a bath containing a solvent-free thermosetting resin composition. The substrate can be, for example, plastic, glass, alloy, metal, ceramic, wood, cement, concrete, rubber, or The reinforced fibrous material. According to another embodiment, the solvent-free thermosetting resin composition, after mixing, can be contacted with any suitable substrate and cured according to an industrially practiced process to form a cured product & As used herein, the term "curing" means that the above solvent-free thermosetting resin composition is converted into an insoluble and non-meltable crosslinked product, and simultaneously shaped to obtain a molded article (such as a molded, stamped or laminated member) or obtained.胄 two-dimensional structure (such as coating, enamel or adhesive). Typical curing: the method includes heating, radiation or energy combination to cure the ambient temperature to high temperature curing. The solvent-free thermosetting resin composition can take a step 157587. Doc

S .14· 201224033 或多步固化(諸如通常在電層壓板及複合物 一固化)。或，該不含溶劑之熱固性樹脂=可的 在始固化循環後採用不同溫度或能源進行後固化。 因此，本發明亦提供-種固化產物，係藉由將任何適宜 基板與不含溶狀熱祕樹社合物關且㈣熱、輕射 及能源組合固化該不含溶劑之熱固性樹脂組合物的方法而 獲得。在-實施例中，該樹脂塗覆基板可藉由施加敎於該 不含溶劑之熱固性樹脂組合物進行熱固化，溫度為約赃 至約23〇。(：，較佳自165。〇至約2阶，_間為約】分鐘至約 300分鐘，較佳自45分鐘至約15〇分鐘。視情況，該固化產 物之模製品可在約12〇t至約25G°C溫度真空條件下持續約 3〇分鐘至約12小時之時間進一步進行後固化。此較好地產 生均勻、無空隙、及完全固化產品。 此外本發明之不含溶劑之熱固性樹脂組合物可用於將 個或更多個基板結合在一起之方法中，該方法係在足以 固化该不含溶劑之熱固性樹脂組合物的條件下使一或多個 待釔合之相似表層或不同基板與該不含溶劑之熱固性樹脂 組口物接觸。此等條件為熟習此項技術者操作之目前已知 方法中採用者且可包括施加壓力及/或熱。 在一替代實施例中，藉由固化本發明之不含溶劑之熱固 性樹脂組合物’可由工業中已熟知技術（例如，擠壓成 型、灌潰、模壓、囊封或塗覆）獲得易燃複合物件。因 此’本發明之不含溶劑之熱固性樹脂組合物可用於製造阻 燃複合物件之方法中，諸如鑄件、預浸片、黏合薄片、層 157587.doc •15· 201224033 板及金屬箔包覆層板。如本文所用，「阻燃」意指符合 94標準。 该阻燃複合物件之性質可藉由添加強化纖維使之適用於 某種應用。該等強化纖维之實施包括玻璃、石英、碳、氧 化鋁、陶瓷、金屬、芳族聚醯胺、天然纖維（例如亞麻、 黃麻、劍麻、***）、紙、丙烯酸及聚乙烯纖維及其等混 合物。該等強化纖維可為任意多種模式，例如，由平行連 續纖維或單方向不連續纖維（短纖維）形成的股線或粗紡； 布（諸如紡織品或墊，編織物，單向、雙向、隨機、偽各 向同性或二維分散似墊物質）；異質晶格或網狀物質；及 三維物質（諸如三軸織物）。 因此，在另一態樣中，係提供製造阻燃複合物件之方 法，其包括步驟⑴提供一層或一束強化纖維；（⑴提供不 含溶劑之熱固性樹脂組合物；iu)將強化纖維與不含溶劑 之熱固性樹脂組合物接觸以塗覆及/或浸潰該強化纖維； 及（iv)在溫度至少約8〇〇c，較佳至少約15〇它，且更佳至少 ”勺19 5 C下固化s亥經塗覆及/或浸潰之強化纖維。 可用濕式法或是熱熔法進行塗覆及/或浸潰。在濕式法 中，將該不含溶劑之熱固性樹脂組合物先溶解在溶劑中以 降低黏度，隨後，進行強化纖維之塗覆及/或浸潰且使用 烘箱或類似物蒸發掉溶劑。在熱熔法中，塗覆及/或浸潰 可藉由直接用已加熱至減小黏度的不含溶劑之熱固性樹脂 組合物塗覆及/或浸潰該等強化纖維而進行，或者，可先 在離型紙或其類似物上製得不含溶劑之熱固性樹脂組合物 157587.docS.14·201224033 or multi-step curing (such as usually in an electrical laminate and composite curing). Alternatively, the solvent-free thermosetting resin = can be post-cured using a different temperature or energy source after the initial curing cycle. Accordingly, the present invention also provides a cured product by curing any solvent-free thermosetting resin composition by combining any suitable substrate with a solvent-free heat-clearing compound and (iv) heat, light, and energy. Obtained by the method. In the embodiment, the resin-coated substrate may be thermally cured by applying the solvent-free thermosetting resin composition at a temperature of from about 赃 to about 23 Å. (: preferably from 165. 〇 to about 2 steps, _ between about 约 minutes to about 300 minutes, preferably from 45 minutes to about 15 minutes. Depending on the case, the molded product of the cured product may be about 12 inches. Further post-curing is carried out at a temperature of from about 25 G ° C under vacuum for about 3 minutes to about 12 hours. This preferably produces a uniform, void-free, and fully cured product. Further, the solvent-free thermosetting of the present invention. The resin composition can be used in a method of bonding one or more substrates together in a manner sufficient to cure the solvent-free thermosetting resin composition to make one or more similar skin layers or different to be kneaded The substrate is contacted with the solvent-free thermosetting resin set. These conditions are employed in currently known methods of operation by those skilled in the art and may include application of pressure and/or heat. In an alternate embodiment, The flammable composite member can be obtained from the solvent-free thermosetting resin composition of the present invention by techniques well known in the art (for example, extrusion molding, potting, molding, encapsulation or coating). Thus, the present invention The solvent-free thermosetting resin composition can be used in a method of manufacturing a flame-retardant composite article such as a casting, a prepreg, an adhesive sheet, a layer 157587.doc • 15·201224033, and a foil clad laminate. As used herein, "Flame retardant" means conforming to the standard of 94. The properties of the flame retardant composite can be adapted to an application by adding reinforcing fibers. The implementation of the reinforcing fibers includes glass, quartz, carbon, alumina, ceramics, Metal, aromatic polyamide, natural fiber (such as linen, jute, sisal, hemp), paper, acrylic and polyethylene fibers, and the like. These reinforcing fibers can be in any of a variety of modes, for example, by parallel continuous Strands or rovings formed of fibers or unidirectional discontinuous fibers (staple fibers); cloth (such as textiles or mats, woven fabrics, unidirectional, bidirectional, random, pseudo-isotropic or two-dimensionally dispersed mat-like materials); heterogeneous crystals a mesh or a mesh material; and a three-dimensional material (such as a triaxial fabric). Therefore, in another aspect, a method of manufacturing a flame retardant composite article is provided, which comprises the step (1) providing a Or a bundle of reinforcing fibers; ((1) providing a solvent-free thermosetting resin composition; iu) contacting the reinforcing fibers with a solvent-free thermosetting resin composition to coat and/or impregnate the reinforcing fibers; and (iv) The temperature is at least about 8 〇〇 c, preferably at least about 15 Å, and more preferably at least "sprayed at 19 5 C to cure the s-coated and/or impregnated reinforcing fibers. Wet or hot melt method can be used. Coating and/or impregnation. In the wet process, the solvent-free thermosetting resin composition is first dissolved in a solvent to lower the viscosity, followed by coating and/or impregnation of the reinforcing fibers and using an oven. Or the like evaporates the solvent. In the hot melt process, the coating and/or impregnation can be applied and/or impregnated directly by the solvent-free thermosetting resin composition that has been heated to a reduced viscosity. The fiber is carried out, or the solvent-free thermosetting resin composition can be first prepared on a release paper or the like. 157587.doc

S -16· 201224033 之塗膜’且將該膜置於該等強化纖維之一側或兩側且施加 熱及壓力以達成組合物之塗覆及/或浸潰。該熱熔法由於 無殘留溶劑故較佳。 依據另一態樣，提供一種在RTM系統中製造阻燃複合物 件之方法。該方法包括以下步驟：a)將含強化纖維之纖維 預製品導入模具中；b)將不含溶劑之熱固性樹脂組合物注 入模具中；c)使該熱固性樹脂組合物浸潰該纖維預製品； 及d)在至少約8〇。(：（較佳至少約150°C，且更佳至少約 195°C )之溫度下加熱該樹脂浸潰預製品一段時間，以製得 至少部分固化之固體物件；及e)視情況使部分固化之固體 物件在約120。(：至約250eC之溫度下進行後固化操作。 在一替代實施例中，本發明提供一種用於在VaRTM系統 中形成阻燃複合物件的方法。該方法包括以下步驟：a)將 含強化纖維之纖維預製品導入模具中；b)將不含溶劑之熱 固性樹脂組合物注入模具中；c)減小模具内部壓力；幻維 持模具處於大約該減壓；幻使該熱固性樹脂組合物浸潰該 纖維預製品；及f)在至少約8〇t (較佳至少約l5〇〇c，且更 佳至〉、約195 C )之溫度下加熱該樹脂浸潰預製品一段時 間，以製得至少部分固化之固體製品；及g)視情況使部分 固化之固體製品進行約l2〇〇c至約25〇°c溫度的後固化操 作。 ’、 除RTM及VaRTM系統以外，該不含溶劑之熱固性樹脂組 °物可用於其他方法或系統中以製造含有熱壓預浸片、片 狀模製化合物、模壓、鑄造、拉擠成型及纖維纏繞之阻燃 I57587.doc •17- 201224033 複合物件。 在另-態樣中，該不含溶劑之熱固性樹脂組合物，固化 後，提供具有極佳均衡性質的固化產品。依照本發明之均 衡固化產品之性質包括至少兩者：大於約15〇。〇之玻璃轉 移溫度（Tg)，較佳大於170它，且更佳大於2〇〇。〇;當在約 195。(：-2()5。(：之溫度下固化2小時且隨後在環境溫度下測試 夺之至父3500 psi之摺痕抗剪強度，較佳至少約4000 psi ; 當在約1 95。(： -205°C之溫度下固化2小時且隨後在測 試時之至少700 psi之摺痕抗剪強度，較佳至少約9⑼psi，· 及，依據UL94分級至少¥1，較佳v〇之阻燃性。 本發明之固化產物及阻燃複合物件可用於多種應用中， 例士 S航太應用’其中其等可用來作爲飛機主要結構材 料(主翼、尾翼、托樑等）’二級結構材料(襟翼、副翼、通 風罩查級罩、内裝飾等），火箭發動機殼，人造衛星之 L構材料、及其類似物。此外，#等可用來作爲結構材料 用於移動物體（諸如汽車1、鐵道車）、驅動轴、燃料電 池、板彈簧、風渦輪葉片、高壓容器、制動輪、造紙親' 土木工程及建築材料(屋頂材料、電纜、強化桿、加固材 料）及其類似物》 本發明將藉由參考以下實例進—步闡述，其意欲舉例本 發明。 157587.docS-16·201224033 Coating film' and placing the film on one or both sides of the reinforcing fibers and applying heat and pressure to achieve coating and/or impregnation of the composition. This hot melt method is preferred because it has no residual solvent. According to another aspect, a method of making a flame retardant composite article in an RTM system is provided. The method comprises the steps of: a) introducing a fiber preform containing a reinforcing fiber into a mold; b) injecting a solvent-free thermosetting resin composition into a mold; c) causing the thermosetting resin composition to impregnate the fiber preform; And d) at least about 8 inches. Heating the resin to impregnate the preform for a period of time at a temperature of (: preferably at least about 150 ° C, and more preferably at least about 195 ° C) to produce an at least partially cured solid article; and e) as appropriate The solidified solid article is at about 120. (: Post-cure operation to a temperature of about 250 eC. In an alternate embodiment, the present invention provides a method for forming a flame-retardant composite in a VaRTM system. The method comprises the steps of: a) containing reinforcing fibers The fiber preform is introduced into the mold; b) the solvent-free thermosetting resin composition is injected into the mold; c) the internal pressure of the mold is reduced; the mold is maintained at about the reduced pressure; and the thermosetting resin composition is impregnated. a fiber preform; and f) heating the resin to impregnate the preform for a period of time at a temperature of at least about 8 Torr (preferably at least about 15 〇〇c, and more preferably to about 195 C) to produce at least The partially cured solid article; and g) the partially cured solid article is subjected to a post-cure operation at a temperature of from about 12 ° C to about 25 ° C, as appropriate. 'In addition to the RTM and VaRTM systems, the solvent-free thermosetting resin group can be used in other methods or systems for the manufacture of hot-pressed prepregs, sheet molding compounds, molding, casting, pultrusion and fiber. Wound-fired I57587.doc •17- 201224033 Composite object. In another aspect, the solvent-free thermosetting resin composition, after curing, provides a cured product having excellent balance properties. The properties of the equilibrium cured product in accordance with the present invention include at least two: greater than about 15 Torr. The glass transition temperature (Tg) is preferably greater than 170, and more preferably greater than 2 Å. Hey; when at about 195. (:-2()5. (: cured at a temperature for 2 hours and then tested at ambient temperature to obtain a crease shear strength of 3500 psi to the parent, preferably at least about 4,000 psi; when at about 1 95. : a crease shear strength of at least 700 psi at a temperature of -205 ° C for 2 hours and then at least about 9 psi, preferably at least about 9 (9) psi, and, according to UL94, at least $1, preferably v. The cured product and the flame-retardant composite of the present invention can be used in a variety of applications, such as the application of the second-class structural material (the main structural material (main wing, empennage, joist, etc.) of the aircraft] Flaps, ailerons, hoods, grading covers, interior trims, etc.), rocket engine casings, L-shaped materials for satellites, and the like. In addition, # etc. can be used as structural materials for moving objects (such as automobiles). 1. Railway cars, drive shafts, fuel cells, leaf springs, wind turbine blades, high pressure vessels, brake wheels, papermaking, civil engineering and building materials (roof materials, cables, reinforcing bars, reinforcement materials) and their analogues. The present invention will by reference to the following examples - Step forth, for example of the present invention which is intended 157587.doc.

S •18- 201224033 實例 實例1。攪拌下，在周圍溫度組合下列成分： 成分 實例1 實例2 比較例3 比較例4 液體環氧化合物 13.5 12.3 13.5 13.5 單官能基苯并噁畊 41.1 37 41.1 41.1 雙官能基苯并噁畊 22.2 20.1 22.2 22.2 烯丙基雙紛A-終端 聚胺基曱酸酯 11.4 15 *Jeffol® AD 500 多元醇 11.4 *Jeffol® AD 800 多元醇 11.4 四酚基乙烷酚醛 4.9 觸變填料 1 0.9 1 1 矽烷偶合劑 0.8 0.7 0.8 0.8 霧化金屬 10 9.1 10 10 總量 100 100 100 100 *Jeffol® AD 500及 800 多元醇購；自 Huntsman International LLC。 各實施例接著經歷約195°C -205°C之溫度以形成具有以 下熱及物理性質之固化產物。 157587.doc 19- 201224033 性質 實例1 實例2 比較例3 比較例4 起始溫度(°c) 240 220 211 234 最大溫度(°c) 250 236 230 237 加熱(J/g) 247 236 234 207 Tg DSC (°C) 215 170 144 135 摺痕抗剪強度(psi) (在200°C固化2小時，在 25°C測試） 4199 4193 1726 1244 摺痕抗剪強度(psi) (在200°C固化2小時， 在177°C測試） 980 952 417 349 摺痕抗剪強度(psi) (在200°C固化100小時， 在25°C測試） 1734 1526 摺痕抗剪強度(psi) (在200°C固化500小時， 在25°C測試） 1526 1482 摺痕抗剪強度(psi) (在200°C固化1000小時， 在25 °C測試） 1953 1337 以上揭示旨在説明，而非限制，且附屬申請專利範圍意 欲涵蓋所有落於本發明實際範圍内之該等修改、改良及其 它實施例。因此，就法律上最大程度允許下，本發明之範 圍由以下申請專利範圍及其等等效物之最廣可允許闡述範 圍所決定，且不由前述詳細描述所約束及限定。S •18- 201224033 Example Example 1. The following ingredients were combined at ambient temperature with stirring: Ingredient Example 1 Example 2 Comparative Example 3 Comparative Example 4 Liquid Epoxy Compound 13.5 12.3 13.5 13.5 Monofunctional Benzoindole 41.1 37 41.1 41.1 Bifunctional Benzoindigo 22.2 20.1 22.2 22.2 Allyl double A-terminal polyamino phthalate 11.4 15 *Jeffol® AD 500 Polyol 11.4 *Jeffol® AD 800 Polyol 11.4 Tetraphenol ethane phenolic 4.9 Thixotropic filler 1 0.9 1 1 Decane coupling agent 0.8 0.7 0.8 0.8 Atomized metal 10 9.1 10 10 Total 100 100 100 100 *Jeffol® AD 500 and 800 polyols purchased; from Huntsman International LLC. Each of the examples is then subjected to a temperature of from about 195 ° C to about 205 ° C to form a cured product having the following thermal and physical properties. 157587.doc 19- 201224033 Property Example 1 Example 2 Comparative Example 3 Comparative Example 4 Starting temperature (°c) 240 220 211 234 Maximum temperature (°c) 250 236 230 237 Heating (J/g) 247 236 234 207 Tg DSC (°C) 215 170 144 135 Crease Shear Strength (psi) (2 hours at 200 °C, tested at 25 °C) 4199 4193 1726 1244 Crease Strength (psi) (Cure at 200 °C 2 Hour, tested at 177 ° C) 980 952 417 349 Crease Shear Strength (psi) (100 hours at 200 ° C, tested at 25 ° C) 1734 1526 Crease Shear Strength (psi) (at 200 ° C Curing for 500 hours, tested at 25 ° C) 1526 1482 Crease Shear Strength (psi) (1000 hours at 200 ° C, tested at 25 ° C) 1953 1337 The above disclosure is intended to be illustrative, not limiting, and ancillary applications The scope of the patent is intended to cover all such modifications, modifications and The scope of the invention is to be determined by the scope of the appended claims and the claims

157587.doc -20- S157587.doc -20- S

Claims (1)

201224033 七、申請專利範圍： 1 · 一種不含溶劑之熱固性樹脂組合物，其包括： (a)包括雙官能苯并噁畊及單官能苯并噁畊之苯并邊_ 成分； ， （b)液體環氧化合物；及 * 包含式（HI)之酚終端聚胺基曱酸酯、聚脲或聚腺-胺 基曱酸酯之韌化劑： 〇 II R〇--X —C —Y—R2 ——(〇H)m ^ η (III) 其中m為1或2，η為2至6，R〇為移除終端異氰酸酯基、胺 基或羥基後之彈性預聚物之η-價基，該彈性預聚物可溶 於或分散於環氧樹脂，X及γ彼此獨立地為_〇_或氺尺3_， 至少一個X或Υ為_NR3_，R2為分別移除酚性羥基或胺基 或胺基與酚性羥基二者後之多元酚或胺基酚之m+1•價 基’及R3為氫、Cl-c6烷基或酚。 2.如請求項1之不含溶劑之熱固性樹脂組合物，其中該雙 官能苯并噁畊為式（I)之化合物：201224033 VII. Patent application scope: 1 · A solvent-free thermosetting resin composition, comprising: (a) a benzophenone _ component comprising a bifunctional benzoindol and a monofunctional benzoin; and (b) Liquid epoxy compound; and * Toughening agent comprising phenolic terminal polyamine phthalate, polyurea or poly-glycosyl phthalate of formula (HI): 〇II R〇--X-C-Y- R2 ——(〇H)m ^ η (III) wherein m is 1 or 2, η is 2 to 6, and R is the η-valent group of the elastic prepolymer after removal of the terminal isocyanate group, amine group or hydroxyl group The elastic prepolymer is soluble or dispersible in the epoxy resin, and X and γ are independently _〇_ or 氺3_, at least one X or Υ is _NR3_, and R2 is a phenolic hydroxyl group or an amine removed, respectively. The m+1• valency group and R3 of the polyhydric phenol or aminophenol after the base or the amine group and the phenolic hydroxyl group are hydrogen, Cl-c6 alkyl or phenol. 2. The solvent-free thermosetting resin composition of claim 1, wherein the difunctional benzoin is a compound of the formula (I): 157587.doc (I) 201224033 其中尺3為直接鍵、經取代或未經取代之Ci_c^伸烷基、 經取代或未經取代之c6_c20伸芳基、經取代或未2代 之CrC：2。伸雜芳基或〇〇且Rb為氫、經取代或未經取代 之烷基、經取代或未經取代之q-Cm烯基、經取代 或未經取代之C0_C2Q芳基、經取代或未經取代之c2_C2〇雜 芳基、經取代或未經取代之碳環基、經取代或未 經取代之（VCm雜環基、或C3-C1Q環烷基。 3_ 2請求項2之不含溶劑之熱固性樹脂組合物，其中該單 官能苯并噁畊為以式（Π)表示之化合物：157587.doc (I) 201224033 wherein the ruler 3 is a direct bond, a substituted or unsubstituted Ci_c alkyl group, a substituted or unsubstituted c6_c20 extended aryl group, a substituted or non-2nd generation CrC:2. Heteroaryl or hydrazine and Rb is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted q-Cm alkenyl, substituted or unsubstituted C0_C2Q aryl, substituted or not Substituted c2_C2 doped aryl, substituted or unsubstituted carbocyclic group, substituted or unsubstituted (VCm heterocyclic group, or C3-C1Q cycloalkyl group. a thermosetting resin composition, wherein the monofunctional benzoin is a compound represented by the formula (Π): 〃、中^為氫、經取代或未經取代之烷基、經取千 =未經取代之c2_c一基、經取代或未經取代之 ^經取代或未經取代之CVC2。雜芳基、經取代或未海 /之^20碳„、經取代或未經取代U2_C20雜与 基、或C3-C1G環烷基。 4. 5. 如！求項1之不含溶劑之熱固性樹脂組合物 體環氧化合物為非縮水甘油基環氧化合物。 其中該液 =求項4之不含溶劑之熱固性樹脂組合物，其中該非 &水甘油基環氧化合物係選自雙（2,3•環氧基環戊基㈣、 157587.doc 201224033 i，2·雙（2,3-環氧基環戊氧基）乙烷、3,4_環氧基環己烷羧 酸3,4-環氧基環己基曱酯、3,4_環氧基_6_曱基環己烷羧 酸3,4-環氧基_6_曱基_環己基甲酯、二（3,4_環氧環己基曱 基）己二酸酯、二（3,4-環氧基-6-甲基環己基甲基）己二酸 西曰伸乙基雙（3,4-環氧基環己炫緩酸醋）、乙二醇二（3，4_ J哀氧基環己基曱基）醚、二氧化乙烯基環己烯、二環氧化 -¾戊二烯或2-(3,4-環氡基環己基-5,5-螺-3，4-環氧基）環 己烷-1，3-二噁烷及2,2，_雙_(3,4_環氧基_環己基）_丙烷。 6.如請求項1之不含溶劑之熱固性樹脂組合物，其中該韌 化知彳包括一稀丙基雙紛A終端聚胺基甲酸g旨。 7·如請求項1之不含溶劑之熱固性樹脂組合物，其進一步 包括酚觸媒。 8. —種製備不含溶劑之熱固性樹脂組合物之方法，其包括 將約0.5-90重量份之含雙官能苯并噁畊及單官能苯并噁 畊之苯并噁畊成分，及約0.1-30重量份之液體環氧化合 物，及約0.1-40重量份之包含式（111)之酚終端聚胺基曱 酸酯、聚脲或聚脲-胺基曱酸酯之韌化劑混合在一起， mm 0 R。 M 2 R X —-C ——Y—R2 ——(〇H)m 」η (III) 其中m為1或2, 11為2至6, R〇為移除終端異氰酸酯基、胺 基或羥基後之彈性預聚物之n_價基，該彈性預聚物可溶 於或分散於環氧樹脂，χ及γ彼此獨立地為·〇_或_nr3_， 157587.doc 201224033 至少一個X或Y為_NR3_，R2為分別移除酚性羥基或胺基 或胺基與酚性羥基二者後之多元酚或胺基酚之m+1-價 基’及R3為氫、（^-(^烷基或酚，其中所有重量份係基於 1 〇 0重:g份之不含溶劑之熱固性樹脂組合物。 9. 如請求項8之方法，其進一步包括另外混合每100重量份 不含溶劑之熱固性樹脂組合物約〇.〇〇 1 -15重量份之酚觸 媒於組合物中。 10. 一種形成樹脂塗覆基板之方法’其包括使基板與如請求 項1之不含溶劑之熱固性樹脂組合物接觸。 11. 如請求項10之方法，其中該基板為塑料、玻璃、合金、 金屬、陶瓷、木材、水泥、混凝土、橡膠或強化纖維材 料。 12· 一種形成固化產物之方法，其包括使基板與如請求項i 之不含溶劑之熱固性樹脂組合物接觸，且藉由施加熱及/ 或輪射能於樹脂塗覆基板上而固化該樹脂塗覆基板。 13. —種藉由如請求項i 2之方法獲得的固化產物。 14. —種製造阻燃複合物件之方法，其包括以下步驟：⑴提 供一層或一束強化纖維；（Π)提供如請求項i之不含溶劑 之熱固性樹脂組合物；（iii)使該等強化纖維與該不含溶 劑之熱固性樹脂組合物接觸以塗覆及/或浸潰該等強化纖 維；及（W)在約1951-205。(：之溫度下固化該經塗覆及/或 浸潰之強化纖維。 —種阻燃複合物件，其係根據如請求項14之方法製得。 16.-種不含溶劑之熱固性樹脂組合物，其包括⑷包括雙官 157587.doc * 4 - 3 201224033 能苯并噁畊及單官能苯并噁畊之笨并噁畊成分；（b)液體 環氧化合物；及（C)包含式（III)之酚終端聚胺基甲酸酯、 聚脲或聚脲-胺基甲酸酯之韌化劑： Ο R0 II X ——C —Y——R2 —-(〇H)m (III) 其中m為1或2，η為2至6，RG為移除終端異氰酸酯基、胺 基或羥基後之彈性預聚物之n_價基，該彈性預聚物可溶 於或分散於環氧樹脂，X及γ彼此獨立地為_〇_或_>^3-， 至夕' 個X或Y為-NR3-，R2為分別移除紛性經基或胺基 或胺基與紛性羥基二者後之多元酚或胺基酚之m+1-價 基’及R3為氫、烷基或酚，其中藉由固化該不含溶 劑之熱固性樹脂組合物所形成之所得固化產物包含至少 兩個或更多個下述均衡性質：大於約l7〇〇c之玻璃轉移 溫度（Tg);當在約i95«>c_2〇5°c之溫度下固化2小時且隨 後在環境溫度下測試時，至少35〇〇 psi，較佳至少約 4〇OOpsi之摺痕抗剪強度；當在195U〇rc下固化2小時 且隨後在177°C下測試時，至少700 psi，較佳至少約9〇〇 psi之摺痕抗剪強度；及依據uL94分級，至少vi，較佳 V0之阻燃性。 157587.doc 201224033 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 〇 II R0--X -C -Y-R2 -(OH)m η (III) 157587.doc〃, 中中 is hydrogen, substituted or unsubstituted alkyl, substituted by unsubstituted c2_c-based, substituted or unsubstituted, substituted or unsubstituted CVC2. Heteroaryl, substituted or unsubstituted / 20 carbon „, substituted or unsubstituted U 2 —C20 hetero and phenyl, or C 3 -C 1 G cycloalkyl. 4. 5. The solvent-free thermosetting of claim 1 The resin composition object epoxy compound is a non-glycidyl epoxy compound, wherein the liquid is the solvent-free thermosetting resin composition of claim 4, wherein the non-glycidyl epoxy compound is selected from the group consisting of double (2, 3) • Epoxycyclopentyl (IV), 157587.doc 201224033 i,2·bis(2,3-epoxycyclopentyloxy)ethane, 3,4-epoxycyclohexanecarboxylic acid 3,4- Epoxycyclohexyl decyl ester, 3,4-epoxy-6-nonylcyclohexanecarboxylic acid 3,4-epoxy-6-mercapto-cyclohexylmethyl ester, bis(3,4-ring Oxycyclohexyl decyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, bismuth, ethyl bis(3,4-epoxycyclohexyl) Acidic vinegar), ethylene glycol bis(3,4_J sethoxycyclohexyl decyl) ether, vinyl cyclohexene dioxide, dicyclooxy-3⁄4 pentadiene or 2-(3,4-cycloindole Cyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,3-dioxane and 2,2,_bis-(3,4-epoxy-cyclohexyl) 6. The propane. The solvent-free thermosetting resin composition of claim 1, wherein the toughening sensitization comprises a dipropyl propyl group A terminal polyglycolic acid g. 7. If the claim 1 is not a solvent-containing thermosetting resin composition further comprising a phenol catalyst. 8. A method for preparing a solvent-free thermosetting resin composition, comprising comprising about 0.5 to 90 parts by weight of a bifunctional benzoate and a single a functional benzoin-dominated benzoxanthene component, and about 0.1-30 parts by weight of a liquid epoxy compound, and about 0.1-40 parts by weight of a phenolic terminal polyaminophthalate, polyurea comprising the formula (111) Or polyurea-amino phthalate toughening agents are mixed together, mm 0 R. M 2 RX —-C ——Y—R 2 ——(〇H)m η (III) where m is 1 or 2 , 11 is 2 to 6, R is the n-valent group of the elastic prepolymer after removing the terminal isocyanate group, amine group or hydroxyl group, the elastic prepolymer is soluble or dispersed in the epoxy resin, χ and γ Independently from each other, 〇_ or _nr3_, 157587.doc 201224033 At least one X or Y is _NR3_, and R2 is a phenolic hydroxyl or amine group or an amine group and a phenolic group, respectively. The m+1-valency group and R3 of the polyphenol or aminophenol after the hydroxyl group are hydrogen, (^-(^alkyl or phenol, wherein all parts by weight are based on 1 〇 0 weight: g parts are not included A solvent thermosetting resin composition. 9. The method of claim 8, further comprising additionally mixing, per 100 parts by weight of the solvent-free thermosetting resin composition, about 1 to 15 parts by weight of the phenolic catalyst to the composition. in. A method of forming a resin-coated substrate, which comprises contacting a substrate with a solvent-free thermosetting resin composition as claimed in claim 1. 11. The method of claim 10, wherein the substrate is plastic, glass, alloy, metal, ceramic, wood, cement, concrete, rubber or reinforced fiber material. 12. A method of forming a cured product, comprising: contacting a substrate with a solvent-free thermosetting resin composition as claimed in claim i, and curing the resin by applying heat and/or sputtering energy to the resin-coated substrate The substrate is coated. 13. A cured product obtained by the method of claim i2. 14. A method of making a flame-retardant composite article comprising the steps of: (1) providing a layer or bundle of reinforcing fibers; (Π) providing a solvent-free thermosetting resin composition as claimed in claim i; (iii) enabling such The reinforcing fibers are contacted with the solvent-free thermosetting resin composition to coat and/or impregnate the reinforcing fibers; and (W) is at about 1951-205. (The cured fiber coated and/or impregnated at a temperature of: a flame retardant composite according to the method of claim 14. 16. A solvent-free thermosetting resin composition , which includes (4) including Shuangguan 157587.doc * 4 - 3 201224033 capable of benzoic argon and monofunctional benzoic phlegm and stupid and arable ingredients; (b) liquid epoxy compounds; and (C) inclusion formula (III) a toughening agent for phenolic terminal polyurethanes, polyureas or polyurea-urethanes: Ο R0 II X ——C—Y——R 2 —(〇H)m (III) m is 1 or 2, and η is 2 to 6, and RG is an n-valent group of an elastic prepolymer obtained by removing a terminal isocyanate group, an amine group or a hydroxyl group, and the elastic prepolymer is soluble or dispersed in an epoxy resin. X and γ are independently of each other _〇_ or _>^3-, 至夕' X or Y is -NR3-, and R2 is a separate removal of a divalent radical or an amine group or an amine group and a divalent hydroxyl group. The m+1-valency group and R3 of the polyphenol or aminophenol after the two are hydrogen, an alkyl group or a phenol, wherein the obtained cured product formed by curing the solvent-free thermosetting resin composition contains at least two Or More of the following equilibrium properties: a glass transition temperature (Tg) greater than about 1 〇〇c; when cured at a temperature of about i95 «>c_2 〇 5 ° C for 2 hours and then tested at ambient temperature, at least A crease shear strength of 35 psi, preferably at least about 4,000 psi; at least 700 psi, preferably at least about 9 psi when cured at 195 U 〇rc for 2 hours and then tested at 177 °C. The crease shear strength; and according to uL94 classification, at least vi, preferably V0 flame retardancy. 157587.doc 201224033 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) A brief description of the symbol of the figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 〇II R0--X -C -Y-R2 -(OH)m η (III) 157587.doc
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109071918A (en) * 2016-04-28 2018-12-21 Jxtg能源株式会社 Solidified resin composition and its solidfied material

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201205574D0 (en) 2012-03-29 2012-05-16 Cytec Tech Corp Benzoxazines and compositions containing the same
US9777155B2 (en) 2012-06-27 2017-10-03 Toray Industries, Inc. Benzoxazine resin composition, prepreg, and fiber-reinforced composite material
US9427943B2 (en) * 2013-03-15 2016-08-30 Henkel IP & Holding GmbH Prepreg curing process for preparing composites having superior surface finish and high fiber consolidation
JP6570854B2 (en) * 2014-03-26 2019-09-04 三洋化成工業株式会社 Resin composition for fiber reinforced composite material, resin composition impregnated reinforced fiber for fiber reinforced composite material, and fiber reinforced composite material
US9708440B2 (en) 2015-06-18 2017-07-18 Novoset, Llc High temperature three dimensional printing compositions
EP3325533B1 (en) 2015-07-23 2023-09-13 Huntsman Advanced Materials Americas LLC Curable benzoxazine compositions
CN110885419B (en) * 2019-10-18 2022-08-26 淮北绿洲新材料有限责任公司 Ultrahigh-frequency low-dielectric-property carboxylated graphene reinforced poly (benzoxazine-urethane) nano composite resin and preparation method thereof
CA3154312A1 (en) * 2019-10-31 2021-05-06 Huntsman Advanced Materials Americas Llc Phthalonitrile resins, methods of making same and compositions thereof
CN111825875B (en) * 2020-07-25 2023-01-20 周有松 Toughened benzoxazine foamed plate and preparation method thereof
CN116987378B (en) * 2023-09-27 2023-12-22 常州宏巨电子科技有限公司 Super-temperature-resistant benzoxazine-polyurethane foam material as well as preparation method and application thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5278257A (en) * 1987-08-26 1994-01-11 Ciba-Geigy Corporation Phenol-terminated polyurethane or polyurea(urethane) with epoxy resin
US6207786B1 (en) * 1998-11-10 2001-03-27 Edison Polymer Innovation Corporation Ternary systems of benzoxazine, epoxy, and phenolic resins
US7452585B1 (en) * 2000-07-21 2008-11-18 Henkel Corporation Monolithic structures, methods of manufacture and composite structures
US6743852B2 (en) * 2001-11-13 2004-06-01 Henkel Corporation Benzoxazines, thermosetting resins comprised thereof, and methods for use thereof
DK2115069T3 (en) * 2007-02-08 2021-03-29 Huntsman Adv Mat Licensing Switzerland Gmbh HEAT-CURING COMPOSITION
ES2736175T3 (en) * 2007-12-06 2019-12-26 Henkel Ag & Co Kgaa Curable benzoxazine macromonomers, their preparation and cured products thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109071918A (en) * 2016-04-28 2018-12-21 Jxtg能源株式会社 Solidified resin composition and its solidfied material
CN109071918B (en) * 2016-04-28 2022-04-15 Jxtg能源株式会社 Composition for curing resin and cured product thereof
TWI762483B (en) * 2016-04-28 2022-05-01 日商Ｊｘｔｇ能源股份有限公司 Composition for curing resin and cured product thereof

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