200927894 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種難燃發泡材料，且特別是有關於 具有磷系耐燃劑與氮系耐燃劑之複合耐燃劑系統的難燃發 泡材料。 【先前技術】 ❹ 發泡材料具有相當廣泛的應用範圍，生活上或工業上 的各種產品皆可能使用發泡材料。例如，椅墊、椅背、頂 蓬、各種飾板、地毯、窗簾、衣料内襯、寢具、事務用品、 運動器材、音樂器材、國防軍事用品、或建材等。 在各種發泡材料中，由於聚氨酯發泡材具有優良的耐 化學性、抗溶劑性、抗磨性等，使其在工業上的應用相當 廣泛。聚氨酯發泡材可細分為軟質、半硬質、或硬質發泡 ©材。一般聚氨酯軟質發泡材主要應用於製作傢俱、床墊、 車用作墊等。聚氨酯硬質發泡材則可作為隔熱發泡材，可 應用於住宅、汽車、飛機、冰箱等。 然而，上述發泡材料多由高分子製成，容易起火燃燒 並釋放大量濃煙，往往造成逃生路線遮蔽或逃生者嗆傷， 對於公共安全影響甚鉅。隨著環保議題日漸重要及防火法 規之制定，除了要設法改善發泡材料容易起火冒煙的問題 外，還需同時考量環境之維護，避免發泡材於燃燒時發出 5 200927894 有毒氣體污染環境或傷害逃生者。 因此’業界亟需一種難燃低煙發泡材料，且難燃低煙 發泡材料之組成及其製造過程還需對環境造成最小的傷 害，並且還需維持或增強發泡材之物性。 【發明内容】 本發明提供一種難燃發泡材料，包括發泡材，磷系耐燃 劑，氮系咖劑’以及層狀無機粉體。 本發明另提供一種形成難燃發泡材料的方法，包括混合多 凡醇、層狀無機粉體、峨系耐燃劑、及氮系而寸燃劑 ，以及將二 異氰酸酯混合至上述混合物而發泡。 為讓本發明之上述和其他目的、特徵、和優點能更明 ”、員易麼下文特舉出相關實施例，並配合所附圖式，作詳 細說明如下： ❹ 【實施方式】 &仏種難燃發泡材料，包括將碟系耐燃劑與 二=燃：所組成之複合耐燃劑系統，配合層狀無機粉體 之難材中而形成本發明之難燃發泡材料。本發明 系統遇到火鋪燒時，含錢之複合_劑 體或助料〖無機粉體共同產生隔絕層，可隔絕可燃性氣 ==，達到低煙防燃的效果。本發明之難燃發 氣體二2添加含”素之添加劑’因此不會產生有毒 …人體或％境造成危害。此外’透過層狀無機 6 200927894 粉體的添加，可降低耐燃劑的使用量，還能將分子較小的 耐糾j及附住而不會浮至發泡材之表面，並增加發泡材之 物理性質。 本發明之磷/氮複合耐燃劑系統與層狀無機粉體可導 入所有相容的發泡材巾，其材質例如包括聚氨醋 、聚苯乙 烯、聚乙烯、聚氯乙烯、或前述之組合。 本發明一實施例中之磷系耐燃劑，可增加發泡材之難 ❹燃特性’其重量百分比相對於難燃發泡材料可例如為約5% 至約50% ’較佳為約5°/。至約25°/。。適合的鱗系耐燃劑例 如包括磷酸素、多聚磷酸、磷酸三聚氰胺、聚磷酸、聚磷 酸脂、紅磷膠囊化之白礦、紅碌、填酸脂、或亞碌酸脂、 diethyl N,N-bis(2-hydroxyethyl)aminoethyl phosphate、 2-(6-oxido-6H-dibenz(c,e)(l,2)oxaphosphorin-6-yl)-l,4-benz enediol 、 9,10-dihydro-9-oxo-10-itaconic acid-10-phospha_phenanthrene· 10-oid、正丁基二輕丙基氧化 磷、三羥丙基氧化磷、環辛基羥丙基氧化磷、苯基羥二羥 〇 苯基氧化碟、含經基填酸醋、多磷酸胺（ammonium polyphosphate)、多鱗酸三聚氰胺（melamine polyphosphate)、2,4,8，10-四氧 _3,9_二磷螺環[5.5]十一烷 -3.9-二氧-3,9-二三聚氰胺鹽、雙（2,6,7-三氧-1-磷-雙環 [2.2.2]辛烷-1-氧曱基)磷酸酯三聚氰胺鹽、1-氧-4羥曱基-1-磷-2,6,7_三氧雙環[2.2.2]辛烷、磷酸三甲苯（酚）酯（TCP)、 磷酸甲苯二苯酯（CDP)、磷酸三（二曱苯）酯（TXP)、磷酸二 苯異辛酯、磷酸二苯異丙苯酯、磷酸三苯酯（TPP)、磷酸三 7 200927894 (異丙苯）酯、磷酸三乙酯（TEP)、磷酸二曱苯二苯酯、磷酸 二苯異癸酯、磷酸三（丁氧基乙）酯、磷酸苯二異辛酯、磷 酸苯二乙酯、亞磷酸苯二異辛酯、亞磷酸三苯酯、亞磷酸 二甲酯、含破聚多元醇、亞鱗酸三(2,4_二叔丁基苯基）酯、 環狀磷酸酯、或前述之組合。適合的商用磷系耐燃劑例如 包括PNX(艾克索諾貝爾公司AKZO NOBEL)、200927894 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a flame-retardant foaming material, and more particularly to a flame-retardant foaming of a composite flame retardant system having a phosphorus-based flame retardant and a nitrogen-based flame retardant. material. [Prior Art] 发泡 Foaming materials have a wide range of applications, and foaming materials may be used for various products in life or industry. For example, seat cushions, seat backs, canopies, various plaques, carpets, curtains, clothing linings, bedding, office supplies, sports equipment, music equipment, defense military supplies, or building materials. Among various foaming materials, since the polyurethane foamed material has excellent chemical resistance, solvent resistance, abrasion resistance, etc., it is widely used in industry. Polyurethane foam can be subdivided into soft, semi-rigid, or rigid foam. Generally, polyurethane flexible foaming materials are mainly used for making furniture, mattresses, and cars for use as mats. Polyurethane rigid foam can be used as a thermal insulation foam for residential, automotive, aircraft, refrigerators, etc. However, the above-mentioned foaming materials are mostly made of a polymer, which is easy to ignite and emit a large amount of smoke, which often causes the escape route to be shielded or the escaped person to be bruised, which has a great impact on public safety. With the increasing importance of environmental protection issues and the development of fire prevention regulations, in addition to trying to improve the problem of foaming materials that are prone to fire and smoke, it is also necessary to consider environmental maintenance at the same time to prevent foaming materials from being emitted when burning. Injury to the escaper. Therefore, the industry needs a non-flammable low-smoke foaming material, and the composition of the flame-retardant low-smoke foaming material and its manufacturing process require minimal damage to the environment, and the physical properties of the foamed material need to be maintained or enhanced. SUMMARY OF THE INVENTION The present invention provides a flame-retardant foamed material comprising a foamed material, a phosphorus-based flame retardant, a nitrogen-based coffee agent', and a layered inorganic powder. The present invention further provides a method of forming a flame-retardant foaming material, comprising mixing a polyol, a layered inorganic powder, a lanthanide-based flame retardant, and a nitrogen-based flammable agent, and mixing the diisocyanate to the mixture to foam . The above and other objects, features, and advantages of the present invention will become more apparent from the description of the accompanying claims. The flame-retardant foaming material comprises a flame-retardant material composed of a dish-based flame retardant and a combination of a flame-retardant system and a layered inorganic powder, thereby forming a flame-retardant foaming material of the invention. When encountering fire paving, the composite of _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 2 Adding a "sugar additive" will not cause toxic ... human or % environment causes harm. In addition, the addition of layered inorganic 6 200927894 powder can reduce the amount of flame retardant used, and can also make the molecules less resistant and resistant without being floated to the surface of the foamed material, and increase the foaming material. Physical properties. The phosphorus/nitrogen composite flame retardant system and the layered inorganic powder of the present invention can be introduced into all compatible foaming materials, and the material thereof includes, for example, polyurethane, polystyrene, polyethylene, polyvinyl chloride, or a combination thereof. . The phosphorus-based flame retardant in one embodiment of the present invention can increase the hard-to-burn characteristics of the foamed material. The weight percentage thereof can be, for example, about 5% to about 50% with respect to the flame-retardant foaming material, preferably about 5°. /. Up to about 25°/. . Suitable scaly flame retardants include, for example, phosphate, polyphosphoric acid, melamine phosphate, polyphosphoric acid, polyphosphate, red phosphorus encapsulated white ore, red, acid, or linoleate, diethyl N, N -bis(2-hydroxyethyl)aminoethyl phosphate, 2-(6-oxido-6H-dibenz(c,e)(l,2)oxaphosphorin-6-yl)-l,4-benz enediol, 9,10-dihydro- 9-oxo-10-itaconic acid-10-phospha_phenanthrene· 10-oid, n-butyl dilight propyl phosphine oxide, trihydroxypropyl phosphine oxide, cyclooctyl hydroxypropyl phosphide oxide, phenyl hydroxy hydroxy hydroxybenzene Base oxide dish, containing acid-filled acid vinegar, ammonium polyphosphate, melamine polyphosphate, 2,4,8,10-tetraoxy-3,9-diphosphoryl spiro[5.5] Undecane-3.9-dioxo-3,9-dimelamine salt, bis(2,6,7-trioxo-1-phospho-bicyclo[2.2.2]octane-1-oxoyl) phosphate melamine Salt, 1-oxo-4hydroxydecyl-1-phosphono-2,6,7-trioxodicyclo[2.2.2]octane, trimethylbenzene (phenol) phosphate (TCP), toluene diphenyl phosphate (CDP) ), tris(diphenyl) phosphate (TXP), diphenyl isooctyl phosphate, diphenyl cumene phosphate Triphenyl phosphate (TPP), phosphoric acid III 7 200927894 (cumene) ester, triethyl phosphate (TEP), diphenylene diphenyl phosphate, diphenylisodecyl phosphate, tris(butyloxy) phosphate Ester, phenyl diisooctyl phosphate, phenyl diethyl phosphate, phenyl diisooctyl phosphite, triphenyl phosphite, dimethyl phosphite, containing polycondensation polyol, linoleic acid three (2, 4_ Di-tert-butylphenyl) ester, cyclic phosphate, or a combination of the foregoing. Suitable commercial phosphorus-based flame retardants include, for example, PNX (AKOX NOBEL, AKZO NOBEL),
Antiblazel045(恆橋）、DOPO(恆橋）、TEP(恆橋）、TOP(恆 橋）、TF_J12(Daihachi Chemical Industry)、〇P550(Clariant 〇 Corporation)、Frx-44-94S(nitex)、或前述之組合。在本發 明一實施例中，係使用易於加工的液態磷系耐燃劑，包括 本質即為液態之鱗系耐燃劑或經由改質後為液態之填系耐 燃劑。在本發明一實施例中，所採用的磷系耐燃劑之黏度 較佳小於10,000cps以利後續的加工與應用。應注意的是， 磷系耐燃劑除了價格普遍較貴外，還容易產生酸性物質而 對難燃發泡材造成不利的影響，例如黃變或物性下降等。 因此’磷系耐燃劑之使用需盡可能的減少以獲得物性較佳 〇 之難燃發泡材，並可減少製作成本。 本發明一實施例中之氮系耐燃劑，可增加發泡材之難 燃特性，其重量百分比相對於難燃發泡材料可例如為約 10%至約50%，較佳為約20%至約40%。適合的氮系耐燃 劑例如包括氰尿酸三聚氰胺（melamine cyanurate)、 tris(2-Hydroxyethyl)-l，3,5-triazinetrione、三聚氰胺、三聚 氰胺曱酿（melamine-formaldehyde) 、 butoxymethyl melamine、hexamethoxymethylmelamine、甲基三聚氰胺 8 200927894 (methyl melamine) 、 methoxymethyl melamine 、 methoxymethyl methylol melamine、MC-25(敦厚）、或前述 之組合。適合的商用氮系对燃劑包括Cytec industries INC. 所生產的氮系耐燃劑，例如Cymel-1158、Cymel-303、 Cymel-323、Cymel-325、Cymel-385、Cymel-300、 Cymel-301、Cymel-350、Cymel-324、Cymel-202、 Cymel-327、Cymel-370、Cymel-373、Cymel-380、Antiblazel 045 (Hengqiao), DOPO (Hengqiao), TEP (Hengqiao), TOP (Hengqiao), TF_J12 (Daihachi Chemical Industry), 〇P550 (Clariant 〇 Corporation), Frx-44-94S (nitex), or the foregoing The combination. In an embodiment of the invention, a liquid phosphorus-based flame retardant which is easy to process is used, including a scaly flame resistant agent which is intrinsically liquid or a liquid-filled flame retardant which is liquid after reforming. In an embodiment of the invention, the phosphorus-based flame retardant is preferably less than 10,000 cps for subsequent processing and application. It should be noted that, in addition to being generally more expensive, the phosphorus-based flame retardant is liable to generate an acidic substance and adversely affect the flame-retardant foam material, such as yellowing or a decrease in physical properties. Therefore, the use of the phosphorus-based flame retardant should be reduced as much as possible to obtain a flame-retardant foam having a better physical property, and the production cost can be reduced. The nitrogen-based flame retardant in one embodiment of the present invention can increase the flame retardant property of the foamed material, and the weight percentage thereof can be, for example, about 10% to about 50%, preferably about 20% to the nonflammable foaming material. About 40%. Suitable nitrogen-based flame retardants include, for example, melamine cyanurate, tris(2-Hydroxyethyl)-l, 3,5-triazinetrione, melamine, melamine-formaldehyde, butoxymethyl melamine, hexamethoxymethylmelamine, methyl melamine 8 200927894 (methyl melamine), methoxymethyl melamine, methoxymethyl methylol melamine, MC-25 (dough thick), or a combination of the foregoing. Suitable commercial nitrogen-based fuels include nitrogen-based flame retardants produced by Cytec industries INC., such as Cymel-1158, Cymel-303, Cymel-323, Cymel-325, Cymel-385, Cymel-300, Cymel-301, Cymel-350, Cymel-324, Cymel-202, Cymel-327, Cymel-370, Cymel-373, Cymel-380,
Cymel-1130、Cymel-1131、Cymel-1133、Cymel-1135、 oCymel-1130, Cymel-1131, Cymel-1133, Cymel-1135, o
Cymel-1116、Cymel-1156、CymeM 161、Cymel-1168、或 前述之組合。在本發明一實施例中，係使用易於加工的液 態氮系耐燃劑’包括本質即為液態之氮系耐燃劑或經由改 質後為液態之氮系耐燃劑。。本發明一實施例中採用碟/ 乳複合财燃劑之耐燃發泡材，與不含耐燃劑或僅含鱗系耐 燃劑之發泡材相比，在燃燒時較不會產生煙霧及有毒氣 體。在燃燒初期磷系耐燃劑會產生磷酸，而氮系耐燃$會 〇產生氨氣與氮化物。其發泡材較不易產生煙霧之機制目前 尚不清楚’不排除是因㈣酸可能會加速發泡材脫水碳 化’最後形成高溫縮和填酸脂，並與氮化物產生碳層發泡 層’隔絕可燃或助燃氣體與熱源，達到阻燃阻煙的絲。 氣系耐燃劑之添加還可中和碟系财燒劑造成的酸性物質， 可保護發泡材的物性受磷系耐燃劑影響。此外，由於务、 材成型的發泡過程是很快速的，因此曰在本發明一實^ 中’較佳採用液態的氮系财燃劑，可較均句地就他 材料混合均勾，使最後形成之難燃發泡材整體性質^ 9 200927894 句立曰加其可#度。在本發明一實施例中，所採用的氮系 财燃劑之黏錄佳切i〇,〇〇〇cps以利後續的加工與應用。 本發明貫施例中之層狀無機粉體，可增加發泡材之 難燃特性’還可減少耐燃劑的使用量並將分子較小的财燃 劑吸附住而不會浮至發泡材之表面，而因水洗發泡材時將 而才燃劑洗去’降低發泡材之難燃性質。小分子的财燃劑還 可能因被層狀無機粉體吸附而較均勻地散佈在發泡材中， ❹而使發泡材整體之難燃低煙性質更為均勻。此外，層狀無 機粉體的添加還可進一步增加發泡材的物性，例如強度、 硬度、及耐磨耗度等。層狀無機粉體之重量百分比相對於 難燃發泡材料可例如為約0 01%至約5〇% ’較佳為約0.5〇/〇 至約5% °適合的層狀無機粉體例如包括石夕蓉石類黏土 (smectite clay)、虫至石（vermicuihe)、管狀高嶺土 (halloysite)、絹雲母（sericite)、皂土（sap〇nite)、蒙脫土 (montmorillonite)、富鋁蒙脫土（beidellite)，矽鐵石 ❹（nontronite)、鋰皂土 (hectorite)、層狀雙氫氧化物（LDH)、 雲母(mica)、滑石（talc)、或前述之組合。適合的商用層狀 無機粉體例如I28E(敦厚）。亦可使用非層狀無機粉體，例 如ATH(昭和電工）。在一實施例中，較佳採用奈米級的層 狀無機粉體以增加與其他反應物的反應接觸面積。在一實 施例中’摻混有層狀無機粉體之發泡材，在燃燒時會有較 低的發煙量，煙量抑制的原因尚不清楚，不排除是因為層 狀無機粉體可與耐燃劑共同形成多層的隔絕層，因而可抑 制可燃性或助燃性氣體進入發泡材，並可隔絕熱源而達抑 200927894 制發煙的效果。在一實施例中，所用的層狀無機粉體 還帶有可釋放出水分或可降溫物質的官 面 肖b丞（例如〇h 基），可在燃燒時釋放降溫物質（例如水）來抑制發泡 燒與發煙。 、燃 以下’以本發明一實施例中的聚氨酯難燃發泡材為 例，說明本發明難燃發泡材的形成方式。此技藝人士可透 過本發明所舉實施例的形成方法’在不脫離本發明之精神 下’形成其他材質之難燃發泡材。 Ο 本發明一實施例之聚氨酯難燃發泡材的形成方式包括 將多元醇(polyol)、層狀無機粉體、磷系耐燃劑、及氮系耐 燃劑均勻混合，接著將上述混合物加入二異氰酸酯 (isocyanate)中並快速均勻混合使之發泡為聚氨酯難燃發泡 材。在一實施例中’聚氨酯難燃發泡材之形成是先將層狀 無機粉體與磷系耐燃劑及氮系耐燃劑先均勻混合，先使耐 燃劑吸附在層狀無機粉體上，接著在加入多元醇並均勻混 0合。之後，在將前述混合物加入二異氰酸酯中混合發泡。 應注意的是聚氨酯的發泡會於很短的時間内完成，因此較 佳採用液態耐燃劑來形成與多元醇及層狀無機粉體間之混 合物，可使耐燃劑較佳地分散於發泡材中。層狀無機粉體 之添加量可相對於多元醇之添加量在約〇 〇lphr至約50phr 之間，杈佳為約0.5 Phr至約5 phr之間。磷系耐燃劑之添 加量可相對於多元醇之添加量在約5咖至約卿hr之間， 較佳為約5 Phr至約35 phr之間。i系财燃劑之添加量可 相對於多元醇之添加量在約lOphr至約50_之間，較佳 200927894 為約20 phr至約40 phr之間。 本發明一實施例中，用來形成聚氨酯難燃發泡材的多 元醇包括聚丙二醇（PPG)、聚四曱基醚二醇(PTMEG)、聚 醚多元醇（polyether polyol)、聚酯多元醇（polyester polyol)、或前述之組合。 本發明一實施例中，用來形成聚氨酯難燃發泡材的二 異氰酸酯包括二異氰酸甲苯酯（TDI)、二異氰酸二苯甲烷 (MDI)、HDI、IPDI(脂肪族異酯）、H12MDI(氫化 MDI)及寡 〇 聚合二異氰酸酯、或前述之組合。 此外，本發明一實施例中，還可導入其他添加劑至聚 氨酯難燃發泡材的系統中以輔助發泡或改善發泡材的性 質。添加劑例如包括鏈擴展劑（chain extender)、發泡結構 穩定劑、氨系觸媒、金屬觸媒、發泡劑、補強添加劑、色 料、或前述之組合。適合的鍵擴展劑包括短鍵多元醇，例 如乙二醇(EG)、丁二醇(BG)、二乙二醇（diethylene glycol)、 三乙二醇（triethylene glycol) 、 1,2-丙二醇 ® (l，2-propanediol)、1，3-丙二醇（l，3_propanediol)、1,6-己二 醇（l，6-hexanediol)、或前述之組合。適合的發泡結構穩定 劑包括石夕貌(P〇lysiloxane)。適合的氨系觸媒可加速多元醇 與二異氰酸酯之間的反應，例如有TEA(員和）。適合的金 屬觸媒可加速水與二異氰酸酯之間的反應，例如有T9、 T12、或前述之組合。適合的發泡劑包括氫氟碳化合物 (HFC)、水、二氯曱烷、丙酮、或前述之組合。適合的補強 添加劑可增加強度與硬度，例如有碳酸鈣、氧化矽、或前 12 200927894 述之組合。此外，還可視實際應用狀況加入不同顏色的色 料。 以下針對本發明關於聚氨酯難燃發泡材之一些特定實 施例及比較例來作說明。 【實施例】 以下列舉之各實施例或比較實施例將以類似的配製方 法來形成各聚氨酯發泡材。首先將層狀無機粉體、磷系耐 燃劑、及氮系耐燃劑經由研磨與攪拌而形成混合均勻的有 機/無機耐燃劑系統（部分比較實施例沒有添加全部的材 料）。接著將耐燃劑系統加入多元醇中，並以攪拌轉速 500rpm預攪5分鐘。接著加入二異氰酸酯，並以攪拌轉速 3000rpm乳化攪拌5秒鐘，再將上述混合物導入模具中使 之發泡而完成各實施例與比較例之聚氨酯發泡材，其中所 採用之多元醇皆為員和公司之PAPI-27，而二異氫酸酯是 採用員和公司之XRP-3212(Index=1.0)。表一列舉各實施例 所採用之耐燃劑或層狀無機粉體之材料資訊及其供應商。 表一 商品名 外 所含材 黏度（cps) 鱗含 氮含 供應商 觀 質 量 量 峨系耐 CG1045 液 P 10000 20.5 - 恆橋 燃劑 體 鱗系耐 TEP 液 P 100 17 - 恆橋 燃劑 體 13 200927894 氮系耐 CymeI-303 F 燃劑 體 說系耐 Melamine 固 N 燃劑 體 層狀無 I28E 固 A1、 機粉體 體 Na、 Si、Cymel-1116, Cymel-1156, CymeM 161, Cymel-1168, or a combination of the foregoing. In one embodiment of the present invention, a liquid nitrogen-based flame retardant which is easy to process is used, and includes a nitrogen-based flame retardant which is liquid in nature or a nitrogen-based flame retardant which is liquid after reforming. . In one embodiment of the present invention, a flame-resistant foamed material using a dish/milk composite fuel-burning agent is less likely to generate smoke and toxic gases when burned than a foamed material containing no flame retardant or only a scaly flame retardant. . At the beginning of the combustion, the phosphorus-based flame retardant produces phosphoric acid, while the nitrogen-based flame retardant generates ammonia and nitrogen. The mechanism by which the foamed material is less prone to smoke is still unclear. 'It is not excluded that the acid may accelerate the dehydration and carbonization of the foamed material', and finally forms a high-temperature shrinkage acid-filled fat and a carbon layer foamed layer with the nitride. Isolation of combustible or combustion-supporting gas and heat source to achieve flame retardant and smoke-resistant silk. The addition of the gas-based flame retardant can also neutralize the acidic substances caused by the dish-based fuel, and protect the physical properties of the foam from the phosphorus-based flame retardant. In addition, since the foaming process of the forming of the material and the material is very fast, it is preferable to use a liquid nitrogen-based fuel in the present invention, which can be mixed with the materials evenly. The overall properties of the finally formed flame retardant foam material ^ 9 200927894 句立曰加其可#度. In an embodiment of the invention, the nitrogen-based fuel-burning agent used is well-adhered to cps for subsequent processing and application. The layered inorganic powder in the embodiment of the present invention can increase the flame retardant property of the foamed material', and can also reduce the amount of the flame retardant used and adsorb the smaller molecular weight fuel agent without floating to the foaming material. The surface, and when the foam material is washed, the flammable agent is washed away to reduce the flame retardant properties of the foamed material. The small-molecule fuel can also be more uniformly dispersed in the foamed material by being adsorbed by the layered inorganic powder, so that the flame-retardant and low-smoke properties of the foamed material as a whole are more uniform. Further, the addition of the layered inorganic powder further increases the physical properties of the foamed material such as strength, hardness, and abrasion resistance. The weight percentage of the layered inorganic powder may be, for example, from about 0.01% to about 5% by weight relative to the flame-retardant foaming material, preferably from about 0.5 〇/〇 to about 5%. Suitable layered inorganic powders include, for example, Smectite clay, vermicuihe, tubular kaolin, sericite, sap〇nite, montmorillonite, aluminum-rich montmorillonite (beidellite), nontronite, hectorite, layered double hydroxide (LDH), mica, talc, or a combination of the foregoing. Suitable commercial layered inorganic powders such as I28E (Donghou). Non-layered inorganic powders such as ATH (Showa Denko) can also be used. In one embodiment, a nano-sized layered inorganic powder is preferably employed to increase the reactive contact area with other reactants. In one embodiment, the foamed material in which the layered inorganic powder is blended has a lower amount of smoke during combustion, and the cause of the suppression of the amount of smoke is not clear, and it is not excluded because the layered inorganic powder can be used. Together with the flame retardant, a multi-layered barrier layer is formed, thereby suppressing the entry of flammable or combustion-supporting gas into the foamed material, and isolating the heat source to achieve the effect of the 200927894 smoking system. In one embodiment, the layered inorganic powder used also has a surface area (for example, 〇h base) which can release moisture or a temperature-reducing substance, and can release a cooling substance (for example, water) during combustion to suppress Foaming and smoking. The following describes the formation of the flame-retardant foamed material of the present invention by taking the polyurethane flame-retardant foamed material according to an embodiment of the present invention as an example. The skilled person can form a flame retardant foam of other materials by the method of forming the embodiment of the present invention without departing from the spirit of the invention.形成 The polyurethane flame retardant foam according to an embodiment of the present invention is formed by uniformly mixing a polyol, a layered inorganic powder, a phosphorus-based flame retardant, and a nitrogen-based flame retardant, and then adding the above mixture to the diisocyanate. (isocyanate) and quickly and evenly mixed to foam it into a polyurethane flame retardant foam. In one embodiment, the polyurethane fire-retardant foam material is formed by first uniformly mixing the layered inorganic powder with the phosphorus-based flame retardant and the nitrogen-based flame retardant, and first adsorbing the flame retardant on the layered inorganic powder, and then first adsorbing the flame retardant on the layered inorganic powder. Add the polyol and mix it evenly. Thereafter, the mixture was added to the diisocyanate to be mixed and foamed. It should be noted that the foaming of the polyurethane is completed in a short period of time. Therefore, it is preferred to use a liquid flame retardant to form a mixture with the polyol and the layered inorganic powder, so that the flame retardant is preferably dispersed in the foaming. In the material. The layered inorganic powder may be added in an amount of from about 〇lhr to about 50 phr, preferably from about 0.5 Phr to about 5 phr, relative to the amount of the polyol. The phosphorus-based flame retardant may be added in an amount of from about 5 coffee to about 2,000 hrs, preferably from about 5 Phr to about 35 phr, relative to the amount of the polyol. The amount of the i-based fuel can be added in an amount of from about 10 phr to about 50 Å, preferably from about 20 phr to about 40 phr, relative to the amount of the polyol. In one embodiment of the invention, the polyol used to form the polyurethane flame retardant foam comprises polypropylene glycol (PPG), polytetradecyl ether glycol (PTMEG), polyether polyol, polyester polyol. (polyester polyol), or a combination of the foregoing. In an embodiment of the invention, the diisocyanate used to form the polyurethane flame retardant foam comprises toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), HDI, IPDI (aliphatic isoester) H12MDI (hydrogenated MDI) and oligofluorene polymerized diisocyanate, or a combination thereof. Further, in an embodiment of the present invention, other additives may be introduced into the system of the polyurethane flame retardant foam to assist in foaming or to improve the properties of the foam. The additive includes, for example, a chain extender, a foamed structural stabilizer, an ammonia-based catalyst, a metal catalyst, a foaming agent, a reinforcing additive, a colorant, or a combination thereof. Suitable bond extenders include short bond polyols such as ethylene glycol (EG), butylene glycol (BG), diethylene glycol, triethylene glycol, 1,2-propanediol® (l, 2-propanediol), 1,3-propanediol, 1,6-hexanediol, or a combination thereof. Suitable foaming structural stabilizers include P〇lysiloxane. A suitable ammonia-based catalyst accelerates the reaction between the polyol and the diisocyanate, such as TEA. Suitable metal catalysts accelerate the reaction between water and the diisocyanate, for example, T9, T12, or a combination of the foregoing. Suitable blowing agents include hydrofluorocarbons (HFC), water, dichlorodecane, acetone, or combinations of the foregoing. Suitable reinforcing additives can increase strength and hardness, such as calcium carbonate, strontium oxide, or a combination of the previous 12 200927894. In addition, different colors of color can be added depending on the actual application. Hereinafter, some specific examples and comparative examples of the polyurethane flame retardant foam of the present invention will be described. [Examples] Each of the examples or comparative examples listed below was formed into a similar polyurethane foam by a similar formulation method. First, the layered inorganic powder, the phosphorus-based flame retardant, and the nitrogen-based flame retardant are uniformly mixed with an organic/inorganic flame resistant agent system by grinding and stirring (partial comparative examples do not add all the materials). The flame retardant system was then added to the polyol and pre-stirred for 5 minutes at a stirring speed of 500 rpm. Then, the diisocyanate was added, and the mixture was emulsified and stirred at a stirring speed of 3000 rpm for 5 seconds, and the mixture was introduced into a mold to be foamed to complete the polyurethane foaming materials of the respective examples and comparative examples, wherein the polyols used were all members. And the company's PAPI-27, and the diisohydrogenate is the XRP-3212 (Index=1.0) of the adopter and company. Table 1 lists the materials and suppliers of the flame retardant or layered inorganic powder used in each of the examples. Table 1 Product Content Viscosity (cps) Scales Nitrogen Containing Suppliers Quality 峨 CG1045 Liquid P 10000 20.5 - Hengqiao Fuel Body Scale TEP Resistant Liquid P 100 17 - Hengqiao Fuel Body 13 200927894 Nitrogen-resistant CymeI-303 F fuel body is resistant to Melamine solid N fuel body layered without I28E solid A1, machine powder body Na, Si,
❹ Ο 其中，耐燃劑（Phr)—欄之數 '"4,，，、夂知煙特性。 CAL117A難燃測試所 值是指使該種發泡材通過 耐燃劑，部分為鱗/氮複^^燃劑添加量（部分為單- 加入層狀無機粉體的添加:劑）。粉體(Phr)—攔是指所 CAU〗7A難燃測試時所需量自熄⑻一欄是指進行 任何耐燃劑或層狀無機粉體自f時間。Blank是指未添加 材無法通過CAL 117A ' 之聚氨酯發泡材，Blank發泡 之添加量，皆為相對於^燃娜試。層狀無機粉體與耐燃劑 、夕70醇之添加量。 ----- 耐燃劑系統 空 Blank 白 比 —--- TEP 種類 黏度 粉體 耐燃 發泡密 k 發煙密 (cps) (phr) 劑 度 熄 度 (phr) fKg/cm3) (S) fm2/Kg) - 66 >60 428 100 " 35 83 4〜5 463 14 200927894❹ Ο Among them, the flame retardant (Phr) - the number of columns '" 4,,,, 夂 know the characteristics of smoke. The CAL117A flame retardant test value refers to the amount of the foaming material passed through the flame retardant, and the amount of the scaly/nitrogen compound is added (partially a single-addition of the layered inorganic powder: agent). Powder (Phr) - Barrier refers to the amount of self-extinguish required for the CAU 7A flame retardant test. (8) Column refers to the time from any flame retardant or layered inorganic powder. Blank refers to the urethane foam which cannot be passed through the CAL 117A' without adding materials. The amount of Blank foam added is relative to the test. The amount of the layered inorganic powder, the flame retardant, and the 70 alcohol. ----- Flame Retardant System Blank Blank Ratio---- TEP Type Viscosity Powder Flame Resistant Foaming k-smoke (cps) (phr) Dosing Extretion (phr) fKg/cm3) (S) fm2 /Kg) - 66 >60 428 100 " 35 83 4~5 463 14 200927894
較 例 比 較 例 2 TEP/mela. P/N 10.2/40 P/N 120 35 72 4 422 比 較 例 3 CG1045 P 20.5/- P 10000 20 63 4〜5 381 比 較 例 4 CG1045/mela. P/N 10.3/33 .3 P/N 9000 25 68 3 400 比 較 例 5 CG1045/CY303 P/N 10.3/10 .8 P/N 9000 25 60 4 417 比 較 例 6 TEP/CG1045/mel a P/P/N 13.1/20 P/P/N 700 20 62 4~5 215 比 較 例 7 TEP/CG1045/CY3 03 P/P/N 13.1/6. 5 P/P/N 400 25 68 4 260 比 TEP/I28E P/粉 17.0/- p/粉 120 2 30 60 4 353 15 200927894 較 例 8 實 TEP/CG1045/mel P/P/N/ 12.7/19 P/P/N/ 1200 3 20 68 5~6 195 施 a./I28E 粉 .4 粉 例 I 貧 TEP/CG1045/CY3 P/P/N/ 12.7/6. P/P/N/ 540 3 25 68 1〜3 220 施 03/I28E 粉 3 粉 例 2 ti: mela. = melamine TEP/CG1045/CY303: 35/35/30 TEP/CG1045/meIa.; 35/35/30 TEP/CG1045/CY303/I28E: 35/35/30/3 TEP/CG1045/mela./I28E: 35/35/30/3 其中，CAL117A難燃測試方式（簡稱CA117)如下，將 ❹所得聚氨酯難燃發泡材製作成長寬高分別為304.88毫米、 76.2毫米、及12.7毫米之試片10片。測試前先將待測試 片置於溫度21°C及相對溼度小於等於55°/。下保存24小 時。另取其中5個試片於溫度為l〇〇°C的烘箱内老化24小 時。測定時，將試片垂直置於試驗櫃内，以本生燈（火焰高 度38,1毫米）於距試片底面19.05毫米處點燃試片12秒。 若測定結果滿足下述條件，則受測材料通過CAL117A試 驗。條件包括（1)10個試片燒焦成碳的平均長度小於152.44 16 200927894 毫米、（2)單一試片最大燒焦成碳的長度小於203.2毫米、 (3)10個試片有火焰燃燒之平均時間小於5秒、（4)單一試 片有火焰燃燒之最大時間小於1〇秒、以及(5)10個試片無 火焰燃燒之平均時間小於15秒。 如表二所示，可發現於聚氨酯發泡材導入碌系耐機劑 或氮系耐燃劑後’聚氨酯發泡材皆可通過CAL117A難機 測試。此外，使用碟/氮複合耐燃劑系統(例如比較例2與 4)可獲得較使用單一麟系耐燃劑（例如比較例1與3)更佳的 ®低煙效果，且還能減低磷系耐燃劑（如CG1045或TEP)之用 量’減低構系财燃劑之酸性物質對聚氨酯發泡材物性的影 響，且由於磷系耐燃劑之價格較為高昂，使用磷/氮複合耐 燃劑系統還能進一步節省成本。此外，實施例1及2於碟/ 氮複合耐燃劑系統中’還導入層狀無機粉體（例如I28E)， 可進一步降低發煙密度，並且可避免耐燃劑之小分子浮出 發泡材之表面’造成耐燃劑容易被洗去或造成使用上的問 題。其中，實施例1比之實施例2需較少的添加量即可通 ® 過CAL117A難燃測試，然而其自熄時間較長。其原因目 前尚不清楚，不排除是因為實施例2中的氮系耐燃劑 CY303是經改質的液態氮系耐燃劑，因此較固態氮系耐燃 劑m e 1 a.更容易與其他材料均勻混合，使其形成之聚氨酯發 泡材的難燃性質較為均一，而較容易自熄。 本發明實施例具有許多優點，例如透過磷/氮複合耐燃 劑系統的使用可使發泡材具有顯著地難燃低煙性質與較好 的物性，並且可大幅減少磷系耐燃劑所需之用量，可節省 17 t 200927894 【圖式簡單說明】 無。 【主要元件符號說明】 無。Comparative Example 2 TEP/mela. P/N 10.2/40 P/N 120 35 72 4 422 Comparative Example 3 CG1045 P 20.5/- P 10000 20 63 4~5 381 Comparative Example 4 CG1045/mela. P/N 10.3 /33 .3 P/N 9000 25 68 3 400 Comparative Example 5 CG1045/CY303 P/N 10.3/10 .8 P/N 9000 25 60 4 417 Comparative Example 6 TEP/CG1045/mel a P/P/N 13.1/ 20 P/P/N 700 20 62 4~5 215 Comparative Example 7 TEP/CG1045/CY3 03 P/P/N 13.1/6. 5 P/P/N 400 25 68 4 260 TEP/I28E P/Powder 17.0 /- p/Powder 120 2 30 60 4 353 15 200927894 Comparative Example 8 Real TEP/CG1045/mel P/P/N/ 12.7/19 P/P/N/ 1200 3 20 68 5~6 195 Application a./I28E Powder.4 Powder Example I Lean TEP/CG1045/CY3 P/P/N/ 12.7/6. P/P/N/ 540 3 25 68 1~3 220 Application 03/I28E Powder 3 Powder Example 2 ti: mela. Melamine TEP/CG1045/CY303: 35/35/30 TEP/CG1045/meIa.; 35/35/30 TEP/CG1045/CY303/I28E: 35/35/30/3 TEP/CG1045/mela./I28E: 35/ 35/30/3 Among them, the CAL117A flame retardant test method (CA117 for short) is as follows. The width and height of the polyurethane flame retardant foam produced by ❹ are 304.88 mm and 76.2 mil respectively. And 12.7 mm of the test piece 10. Before the test, the test piece was placed at a temperature of 21 ° C and a relative humidity of 55 ° / or less. Save for 24 hours. Five of the test pieces were aged in an oven at a temperature of 10 ° C for 24 hours. For the measurement, the test piece was placed vertically in the test cabinet, and the test piece was ignited for 12 seconds with a Bunsen burner (flame height of 38, 1 mm) at 19.05 mm from the bottom surface of the test piece. If the measurement results satisfy the following conditions, the material to be tested passes the CAL117A test. The conditions include: (1) the average length of 10 test pieces charred to carbon is less than 152.44 16 200927894 mm, (2) the maximum char length of a single test piece is less than 203.2 mm, (3) 10 test pieces have flame burning The average time is less than 5 seconds, (4) the maximum time for a single test piece to have a flame burn is less than 1 sec, and (5) the average time for no flame burning of 10 test pieces is less than 15 seconds. As shown in Table 2, it can be found that the polyurethane foam material can be tested by the CAL117A after the introduction of the polyurethane foam into the strainer or the nitrogen-based flame retardant. In addition, the use of a dish/nitrogen composite flame retardant system (such as Comparative Examples 2 and 4) results in a better low smoke effect than a single flame resistant agent (such as Comparative Examples 1 and 3), and also reduces phosphorus resistance. The amount of the agent (such as CG1045 or TEP) reduces the effect of the acidic substance of the structured fuel on the physical properties of the polyurethane foam, and because the price of the phosphorus-based flame retardant is relatively high, the use of the phosphorus/nitrogen composite flame retardant system can further cut costs. In addition, Examples 1 and 2 also introduce a layered inorganic powder (for example, I28E) in a dish/nitrogen composite flame retardant system, which can further reduce the smoke density and prevent the small molecules of the flame retardant from floating out of the surface of the foamed material. 'Causes the flame retardant to be easily washed away or causes problems in use. Among them, Example 1 requires less addition than Example 2 to pass the CAL117A flame retardant test, but its self-extinguishing time is longer. The reason for this is not clear at present, and it is not excluded that the nitrogen-based flame retardant CY303 in the second embodiment is a modified liquid nitrogen-based flame retardant, so that it is more easily mixed with other materials than the solid nitrogen-based flame retardant me 1 a. The polyurethane foam material formed by the polyurethane foam material has relatively uniform flame retardant properties and is relatively easy to self-extinguish. The embodiments of the present invention have many advantages, such as the use of a phosphorus/nitrogen composite flame retardant system, which enables the foamed material to have significantly inflammable low-smoke properties and better physical properties, and can greatly reduce the amount of phosphorus-based flame retardant required. , can save 17 t 200927894 [Simple diagram] No. [Main component symbol description] None.
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