1295699 九、發明說明： 【發明所屬之技術領域】 於汽車或建築物内裝材 本發明、例如係有關一種使用 料等的纖維薄片。 【先前技術】 以往、係提供作為此種纖維薄片之：經以針軋（n e e “ e punching)纏合纖維編網薄片的針織不織布或針織毛氈、及 經以合成樹脂接著纖維編網的樹脂不織布或樹脂毛童:、 維編織物等（例如、參照專利文獻1、2 )。 [專利文獻1] 曰本專利特開平11 一 61616號公報 [專利文獻2] 曰本專利特開平8— 39596號公報 【發明内容】 [發明所欲解決之技術問題] 對於此種纖維薄片便要求具有防音性或隔熱性。為了 f有防音性或隔熱性則以提高該纖維薄片内的空隙率為 佳、。、但一旦提高該纖維薄片内的空隙率則纖維薄片的剛性 便減低、搬運時易變形、並且成形時成形形狀變得不安定。 再者、只單純提高該纖維薄片内的空隙率、對於低周波至 高周波的廣範圍周波數的吸音性則無法保證。 [解決問題之技術方案] 广本如明係為用以解決上述習知問題之方案、係提供一 _ $ ^ 維薄片係於纖維中混合熱膨脹性顆粒r 315986 5 1295699 2薄片化之同k、一邊限定其厚度一邊加熱使該熱膨脹性 顆粒體熱膨脹 ▲該纖維係財空纖維或混合有巾线維為佳、並且於 遠纖維中以混合有溶點18{rc以下的低溶點纖維為更佳。 成幵戴、·隹薄片k、該纖維以藉由合成樹脂黏合劑接著 〜錢％脹性顆粒體、係以於具有低軟化點熱塑性樹脂 缚喊中封人低彿點溶劑的微膠囊、或係以於具有低軟化點1295699 IX. Description of the Invention: [Technical Field of the Invention] The present invention is, for example, a fiber sheet relating to a use material or the like. [Prior Art] Conventionally, as such a fiber sheet, a knitted non-woven fabric or a knitted felt which is entangled (nee punched) with a fiber-entangled sheet, and a resin-nonwoven fabric which is subjected to a synthetic resin and a fiber-woven web Or a resin woven fabric, a woven fabric, and the like (for example, refer to Patent Documents 1 and 2). [Patent Document 1] Japanese Patent Laid-Open No. Hei 11-61616 [Patent Document 2] Japanese Patent Laid-Open No. Hei 8-39596 SUMMARY OF THE INVENTION [Technical Problem to be Solved by the Invention] Such a fiber sheet is required to have soundproofness or heat insulation. In order to have soundproofness or heat insulation, it is preferable to increase the void ratio in the fiber sheet. However, when the void ratio in the fiber sheet is increased, the rigidity of the fiber sheet is reduced, the shape is easily deformed during transportation, and the formed shape is unstable during molding. Further, only the void ratio in the fiber sheet is simply increased. The sound absorption of a wide range of cycle numbers from low frequency to high frequency is not guaranteed. [Technical Solution to Problem] 广本如明 is a solution to solve the above-mentioned conventional problems. Providing a _ $ ^ dimension sheet in the fiber and mixing the heat-expandable particles r 315986 5 1295699 2 flaking the same k, while limiting the thickness thereof while heating to thermally expand the heat-expandable granule ▲ the fiber is a hollow fiber or a mixed towel The line dimension is preferred, and the low-melting point fiber having a melting point of 18{rc or less is preferably blended in the far fiber. The 幵 幵 、 隹 隹 隹 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Expandable granules, which are used to encapsulate microcapsules with a low softening point thermoplastic resin in a low-point solvent, or to have a low softening point
熱塑性樹脂珠粒中含浸㈣點溶劑的發泡性珠粒、或係以 熱膨脹性無機顆粒體為佳。 一r' 本發明再提供一種成形物、該成形物係以既定形狀將 上述纖維薄片成形。 ’ 作用The thermoplastic resin beads are preferably impregnated with a (four) point solvent, or a thermally expandable inorganic granule. Further, the present invention further provides a molded article obtained by molding the above-mentioned fiber sheet in a predetermined shape. Function
將該纖維薄片-邊限制厚度-邊加熱至含有該熱至 ，性顆粒體之膨脹溫度以上時、該熱膨脹性顆粒體因熱 2:因如上之所述限定該纖維薄片的厚度、藉由該顆 體_壓縮周圍的纖維、纖維部分的密度變高剛性增 強。但作為纖維薄片全體之空隙率不變、因： 化。 J…、 【實施方式】 以下詳細說明本發明 [纖維] 例如；聚酯纖維、聚醯 聚氯乙烯纖維、聚偏氯 作為本發明中所使用的纖維、 胺纖維、尿烷纖維、丙烯酸纖維、 315986 6 1295699 乙烯纖維、乙酸醋纖維等合成纖維、洋毛、馬诲毛、羊絨、 轮毛、羊轮毛、路馬絨、安哥拉山羊毛、蠢絲、稻草纖維、 ，維、紙漿、椰子纖維、麻纖維、竹纖維、洋麻纖維 寺的天然纖維、人造纖維(人造絲、人造短纖）、高濕模量 黏膠纖維（P〇lyn0sic)、銅錢人造纖維（Cupr〇)、乙酸西旨、 三乙酸酉旨纖維等的纖維素系人造纖維、玻璃纖維、碳纖维、 陶究纖維、石棉纖維等的無機纖維、卩及將使用此等纖維 的纖維製品之碎布予以開鬆所得之再生纖料。此等纖維 可單獨或二種以上組合使用。 中空纖維係最理想之纖維。 該中空鐵維係由；聚對苯二甲酸乙二醇酯（ρ Ε Τ )、聚 對苯二甲酸丁二醇酯（ΡΒΤ)、聚六亞甲基苯二甲酯、聚二 卜4-二Τ基環己烷對苯二甲醋等的聚醋、耐倫6、耐倫66、 :倫Ί倫1G等的聚醯胺、聚乙稀、聚丙烯等的聚稀 ，丙稀S文尿烧、聚氯乙烯、聚偏氯乙稀、乙酸醋等的 熱塑性樹脂所組成。此等中空纖維可單獨或二種以上组合 使用。 。…該中空纖維〜藉由熔融紡絲法以⑴以“^^^仙^^、 或藉由優先溶出除去復合紡絲二種聚合物所得之纖維一方 成分等的周知方法而製造。 該中工纖維、具有1個或2個以上的截面圓形、橢圖 形等=狀的中空管部、中空率係5%至7〇%、較佳為1〇% 至50%。並且中空率的比率係相對於纖維截面積的中空管 部截面積。 315986 7 1295699 並且中空纖維的纖度範圍係ldtex至5〇dtex、較佳為 2dtex 至 30 。 混合上述中空纖維和其他纖維使用時、上 以混合30質量％以上為佳。 義、，隹 如使用上述中空纖維時、纖維薄片的剛性藉由中空管 效果而增強。 再者、於本發明中、亦可使用融點係J 8〇。〇以下的低 融點纖維。作為該低融點纖維、例如；聚乙烯、聚丙烯、 乙烯一乙酸乙烯酯共聚物、乙烯一丙烯酸乙酯共聚物等的 聚烯烴系纖維、聚氣乙烯纖維、聚尿烷纖維、聚酯纖維、 聚酯共聚物纖維、聚醯胺纖維、聚醯胺共聚物纖維等。此 荨低融點纖維可早獨或二種以上組合使用。 該低融點纖維的纖度範圍係0eldtex S6〇dtex。 上述低rglfe點纖維通常於上述纖維中以1至50質量％混 合0 [熱膨脹性顆粒體] 使用於本發明的熱膨脹性顆粒體、例如由具有低軟化 點的熱塑性樹脂和低沸點溶劑所組成。作為具有低軟化點 的熱塑性樹脂、可例舉如··丙烯酸甲酯、丙烯酸乙酯、丙 焊酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸異丁 酯、丙烯酸第三丁酯、丙烯酸一2—乙基己酯、丙烯酸環己 醋、丙烯酸四氫糠酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、 甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁 醋、甲基丙烯酸異丁酯、甲基丙烯酸一2~乙基己酯、甲基 315986 8 1295699 丙烯酸環己酯、曱基丙烯酸四氫糠酯、甲基丙烯酸硬脂酯、 甲基丙烯酸月桂酯等的脂肪族或環式丙烯酸酯及/或甲基 丙烯酸酯、曱基乙烯（基）醚、乙基乙烯（基）醚、正丙基乙 烯（基）醚、正丁基乙烯（基）醚、異丁基乙烯（基）醚等的乙 烯（基）醚系、苯乙烯、α -曱基苯乙烯等苯乙烯類、丙烯腈、 曱基丙烯腈等的腈系單體、乙酸乙烯酯、丙酸乙烯酯等的 脂肪族乙烯、氣乙烯、二氣乙烯、氟乙烯、二氟乙烯等的 鹵素含有單體、乙烯、丙烯等的烯烴系、異戊二烯、氣丁 一烯、丁二烯等的二烯系、丙烯酸、甲基丙烯酸、衣康酸、 馬來酸、巴豆酸、阿托酸、擰康酸等的α、Ρ—不飽和羧酸、 曱基丙烯酸2 —烴乙酯、丙烯酸2 —烴乙酯、曱基丙烯酸2 —烴丙酯、丙稀酸2 —烴丙酯、烯丙醇等含氫氧基之單體、 丙烯^&胺、甲基丙烯醯胺、二丙g同丙烯醯胺等醯胺類、曱 基丙烯酸二甲胺基乙酯、丙烯酸二曱胺基乙酯、曱基丙稀 酸二甲胺基丙酯、丙烯酸二甲胺基丙酯等含胺基之單體、 丙稀酸縮水甘油醋、甲基丙烯酸縮水甘油酯、縮水甘油稀 丙醚等含環氧基含之單體、以及其他乙烯吡咯酮、乙烯吼 啶、乙烯咔唑等的水溶性單體、以及以二乙烯基苯、二丙 細酸一甘酵酉曰專的多元丙細酸醋或甲基丙稀酸g旨、酿酸二 烯丙酯、縮水甘油烯丙醚等的交聯劑將γ_ (甲基丙烯醯氧 基）丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、對三曱氧 基矽烷苯乙烯、對三乙氧基矽烷苯乙烯、對三甲氧基矽烷 一 α-甲基苯乙嫦、對三乙氧基石夕烧一α -甲基苯乙烯、γ-(丙 烯醯氧基）丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、Ν — 9 315986 1295699 β(Ν-乙烯基节基胺基乙基—γ-胺基丙基）三甲氧基矽烷. 鹽酸鹽等含水解性矽烷基單體等的—種或二種以上的^合 物或上述聚合物交聯的聚合物、低軟化點聚醯胺、低軟化 點聚醋等的具有丨8(TC以下軟化點較佳的熱塑性樹脂、作 為低沸點溶劑之例如：正己烷、環己烷、正戊烷、異戊烷、 正丁烧、異丁烧、正庚烧、正辛烧、異辛烧、汽油、二乙 謎、丙酮、苯等濟點15(TC以下之有機溶劑。熱膨服性顆 粒體係由上述熱塑性樹脂顆粒體中含浸上述低沸點溶劑之 發泡性粒及上述低軟化點熱紐樹㈣殼中充填上述低沸 點溶劑之微膠㈣所組成。該顆㈣的直徑通常係〇.5至 作為使用於本發明的熱膨脹性顆粒體、還有經石、波 來鐵、矽膠球等熱膨脹性無機顆粒體。 [纖維薄片] p 本1月的、截維薄片、係藉由針軋纏合纖維編網薄片或 的方法、或於纖維編網薄片或墊子中含浸或混合合成 私n σ翁接著、或藉㈣軋纏合纖維纖網薄片或塾子 的河提下含浸合成樹脂黏合劑來接著的以 維的方法等製造。 1m 〜脹性顆粒體、通常於纖維薄片化或墊子化之 ^ 仁於缚片或墊子中含浸或混合合成樹脂 T 、亦可混合於該合成樹脂黏合劑中。混合比率可 n/ k $係相對於纖維而添加該顆粒體〇· 1至50質量 315986 10 1295699 入,上述薄片化的纖維中含浸合成樹脂、通常於液體狀 :成樹脂或合成樹脂溶液中浸潰該薄片化纖維、或藉由喷 =刮塗、輥塗、流塗等對該薄片化纖維塗敷液體狀合成 知f脂或合成樹脂溶液。 對於為即已含次或混合了合成樹脂的薄片化纖維中的 二篁、係於合成樹脂含浸或混合後、將薄片化纖維 、<争輥或壓榨盤絞擰。此時、纖維化薄片雖減少厚度、 =於該纖維化薄片中含有中空纖維時、則剛性較高、 彈性地復原、可保持一定程度的厚度。特別於該 、、隹化薄#巾含有低n纖維時、以使該纖維薄片化、加 熱熔融低融點纖維、並藉由該熔融物接著纖維為佳。如此 :來、。該纖維薄片其強度和剛性更加提高、合成樹脂含浸 k的操作性提高、並且絞擰後的厚度制亦趨顯著。 如j之所述、於本發明的纖維十含有中空纖維時、薄 1化的薄片成為高剛性、並能使薄片化纖維的合成樹脂黏 黏合劑的含量 絲的薄片化纖維的合成樹脂 於該薄片化纖維中含浸或混合合成樹脂溶液後、將該 ，片化纖維乾燥。於該薄片化纖維中含有的合成樹脂黏合 別係熱固性樹脂時、如使該樹脂呈β狀態則可長期保存、 且可在低溫短時間成形。 [合成樹脂黏合劑] .作為^述纖維的黏合劑所使甩的合成樹脂、例如可使 用，聚乙烯、聚丙烯、乙烯—丙稀共聚物、乙稀〜乙酸乙 315986 11 1295699 . 曰共t物、聚氣乙細、聚偏氣乙稀、聚苯乙稀、聚乙酸 乙烯酯、氟樹脂、熱塑性丙烯酸樹脂、熱塑性聚酯、熱塑 性聚醯胺、熱塑性尿烷樹脂、丙烯睛—丁二烯共聚物、苯 乙烯一 丁二烯共聚物、丙烯睛一丁二烯一笨乙烯共聚物、 乙烯一丙烯共聚物、乙烯-丙烯三共聚物、乙烯—乙酸乙烯 共聚物等熱塑性合成樹脂、尿烷樹脂、蜜胺樹脂、熱固型 丙烯酸樹脂、尿素樹脂、酚樹脂、環氧樹脂、熱固型聚酯 等之熱固性合成樹脂、也可使用生成該合成樹脂的尿燒樹 脂預聚物、％氧樹脂預聚物、蜜胺樹脂預聚物、尿素樹脂 預聚物、酚樹脂預聚物、酞酸二烯丙酯（DAP)預聚物、丙二 酸募聚物、多元異氰酸鹽、甲基丙烯酸酯單體、酞酸二烯 丙醋（MP)單體等預聚物、寡聚物、單體等合成樹脂預聚 物。上述合成樹脂亦可單獨或二種以上併用、通常以 乳液、乳膠、水溶液、有機溶劑等使用。 作為本發明所使用的合成樹脂黏合劑、最 脂。以謂細說财關本發明所使㈣㈣樹脂。 酚糸樹脂係藉由將酚系化合物和醛及/或醛給 合而知。為賦予水溶性、亦可對 ^ 及/或硫絲化。 ^對_讀脂進行魏基化 本發明的酚系樹脂、作為初 合物液）含浸於薄片基材。該初期縮终=水=初=縮 使用··甲醇、乙醇、正丙醇、h ‘勿，夜依所^、亦可 筮一 > 卜 · 一丙醇、正丁醇、里丁醇、 弟一丁醇、弟三丁醇、正戊醇、里 一 丁％、 酉子、2-乙基丁醇、正庚醇、正 — 予甲基戊 、三甲基壬醇、環己醇、 315986 12 1295699 苄醇、糠醇、四氫糠醇、松香醇、雙丙酮醇等醇類；丙酮、 甲基丙酮、甲基乙基酮、甲基正丙酮、甲基正丁酮、甲基 異丁酮、二乙酮、二正丙酮、二異丁酮、丙酮基丙酮、二 甲醚、裱己酮、甲基環己酮、乙醯苯、樟腦等酮類；乙二 醇一乙—醇、二乙二醇、丙二醇、三甲二醇、聚乙二醇 等二醇類；乙二醇單甲醚、乙二醇單乙醚、乙二醇異丙醚、 二乙二醇單甲醚、三乙二醇單甲醚等二醇醚；乙二醇二乙 酸s曰、二乙二醇單乙醚乙酸酯等上述二醇類的酯類或其衍 生物，1 ’ 4二噁烷等醚類、二乙基溶纖劑、二乙基卡必醇、 乙基乳酸酯、異丙基乳酸酯、二乙二醇二乙酸酯、二甲基 甲醯胺等水溶性有機溶劑。 [酚系化合物] 作為使用於上述盼糸樹脂中的盼系化合物、可為單元 齡亦了為多盼或單元驗和多紛的混合物、但只使用單元 酚時、於硬化時以及硬化後因容易釋放出曱醛、因而以使 用多酚或單元酚和多酚的混合物為佳。 [單元紛] 作為上述單元酚、可例舉：酚；或鄰曱酚、間甲酚、 對甲酚、乙基酚、異丙基酚、二曱酚、3，5一二曱酚、丁基 酚、第二丁基酚、壬基酚等烷基酚、鄰默酚、間氟酚、對 氟酚、鄰氣酚、間氯酚、對氣酚、鄰溴酚、間溴酚、對溴 酚、鄰碘酚、間碘酚、對碘酚、鄰胺基酚、間胺基酚、對 胺基酚、鄰硝基酚、間硝基酚、對硝基酚、2, 4—二硝基酚、 2，4，6-二硝基酚等單元酚取代物；奈酚等多環式單元酚 315986 13 1295699 等、而此等單元酚可以單獨或二種以上混合使用。 [多盼] 作為上述多酚、可例舉：間苯二酚、烷基間苯二酚、 焦掊酚、兒茶酚、烷基兒茶酚、氫醌、烷基氫醌、均笨三 酜、雙酚、三羥基萘等。此等多酚可以單獨或二種以上混 合使用。多酚中較佳之物為間苯二酚或烷基間苯二酚、特 佺之物為與醛之反應速度較間苯二酚為快速的烷基間笨二 盼0 作為上述烷基間笨二酚、可例舉：5__曱基間苯二酚、 間苯二酚、2， 2，5-二丙基間苯 5-乙基間苯二酚、5—丙基間苯二酚、5-正丁基間苯二酚、4, 5-一甲基間苯二酚、2，5-二甲基間苯二酚、4，5一二乙基 二基間苯二酚、4，5-二丙基間苯二酚、 盼、4-甲基一5 -乙基間苯二盼、2 —甲基 5 - -5-乙基間苯二酚、2—曱基一5一丙基間苯二酚 T基間苯二酚、2，4，5-三乙基間苯二酚等。 愛沙尼亞（Estonia)國出產的油頁岩藉由乾餾所得之 ^酉分混合物因價廉，且除了 5_甲基間苯二齡之外並含有多 量反應性較高的各種垸基間苯二汾、因此為本發明 多酚原料。 本發明中、上述酚系化合物與醛及/或醛給予體（醛類） 雖經縮合、而所謂上祕給傾係指—經分解時生成給予 醛的化合物或其混合物。此類醛可例舉如：甲醛、乙醛、 丙醛、氯醛、糠醛、乙二醛、正丁醛、己醛、丙烯醛、苯 μ '巴㈣、丙祕、苯乙搭、鄰甲苯酸、水揚盤等、 315986 14 1295699 作為醛給予體、可例舉如：對曱醛、三噁烷、六亞曱基四 胺、四曱醛等。 如上所述、為改良水溶性酚系樹脂的安定性、最好將 上述酚系樹脂予以磺曱基化及/或硫曱基化。 [續曱基化劑] 作為能使用於改良水溶性酚系樹脂的安定性的磺曱基 化劑、可例舉如：藉由亞硫酸、重亞硫酸或偏亞硫酸與鹼 金屬或二曱胺及苄基三甲鏔等四級胺或四級銨反應所得之 水溶性亞硫酸鹽、或藉由此等水溶性亞硫酸鹽與越之反應 所得之醛附加物。 丙醛、氣醛、糠醛、乙When the fiber sheet is heated to a temperature exceeding the expansion temperature of the granules, the heat-expandable granules are heated by the heat 2: as defined above, the thickness of the fiber sheet is defined by The density of the fibers and the fiber portion around the body _ compression becomes high and the rigidity is enhanced. However, the void ratio of the entire fiber sheet is unchanged. J. [Embodiment] Hereinafter, the present invention [fiber], for example, polyester fiber, polyfluorene polyvinyl chloride fiber, and polyvinylidene chloride are used as fibers, amine fibers, urethane fibers, acrylic fibers, and the like, which are used in the present invention. 315986 6 1295699 Synthetic fibers such as vinyl fiber, acetate acetate, etc., hair, horsehair, cashmere, hair, sheep hair, road horse, Angora wool, stupid silk, straw fiber, wei, pulp, coconut fiber , hemp fiber, bamboo fiber, natural fiber of kenaf fiber temple, rayon (rayon, staple fiber), high-moisture modulus viscose fiber (P〇lyn0sic), copper coin rayon (Cupr〇), acetic acid And a cellulose-based rayon fiber such as a triacetate fiber, a glass fiber, a carbon fiber, a ceramic fiber, an asbestos fiber, or the like, and a crepe obtained by opening a rag of a fiber product using the fiber. Fiber. These fibers may be used alone or in combination of two or more. Hollow fiber is the most desirable fiber. The hollow iron is made of: polyethylene terephthalate (ρ Ε Τ ), polybutylene terephthalate (ΡΒΤ), polyhexamethylene phthalate, polydibu-4- Polydimethyl phthalate such as dimercaptocyclohexane-p-xylylene vinegar, ruthenium 6, ruthenium 66, polyglycol, polypropylene, polypropylene, etc. It is composed of a thermoplastic resin such as urinary burning, polyvinyl chloride, polyvinylidene chloride or acetic acid vinegar. These hollow fibers may be used singly or in combination of two or more. . The hollow fiber is produced by a melt spinning method by a well-known method of (1) "(1), or by preferentially eluting and removing a fiber component obtained by conjugated two kinds of polymers. The fiber has a hollow tube portion having one or two or more circular cross-sections, an elliptical shape, or the like, and has a hollow ratio of 5% to 7% by weight, preferably 1% to 50%, and a ratio of hollow ratio. The cross-sectional area of the hollow tube portion relative to the cross-sectional area of the fiber. 315986 7 1295699 and the fineness of the hollow fiber ranges from ldtex to 5〇dtex, preferably from 2dtex to 30. Mixing the above hollow fiber and other fibers when used, mixing 30% by mass or more is preferable. For example, when the hollow fiber is used, the rigidity of the fiber sheet is enhanced by the effect of the hollow tube. Further, in the present invention, the melting point system J 8〇 can also be used. The following low-melting fiber, as the low-melting fiber, for example, a polyolefin fiber such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer or ethylene ethyl acrylate copolymer, polystyrene fiber, and poly Urethane fiber, polyester fiber, poly Copolymer fiber, polyamide fiber, polyamide copolymer fiber, etc. This low melting fiber can be used alone or in combination of two or more. The fineness of the low melting fiber is 0eldtex S6〇dtex. The point fiber is usually mixed with 1 to 50% by mass in the above fibers. [The heat-expandable granules] are used for the heat-expandable granules of the present invention, for example, a thermoplastic resin having a low softening point and a solvent having a low boiling point. The softening point thermoplastic resin may, for example, be methyl acrylate, ethyl acrylate, n-propyl propylene acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tributyl acrylate or acrylic acid. 2-ethylhexyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate , isobutyl methacrylate, 2-ethylhexyl methacrylate, methyl 315986 8 1295699 cyclohexyl acrylate, tetrahydrofurfuryl methacrylate, stearyl methacrylate, methacryl Aliphatic or cyclic acrylates and/or methacrylates such as lauryl ester, decyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl ethylene a vinyl (yl) ether such as ether or isobutylethylene (meth) ether, a styrene such as styrene or α-mercapto styrene, a nitrile monomer such as acrylonitrile or decyl acrylonitrile, or vinyl acetate. A halogen such as an ester or a vinyl propionate such as an aliphatic ethylene, a gas ethylene, a diethylene glycol, a vinyl fluoride or a difluoroethylene contains a monomer, an olefin such as ethylene or propylene, isoprene or a butylene. Alkenes, acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, atropic acid, tococanic acid, etc., α, Ρ-unsaturated carboxylic acid, methacrylic acid 2-hydrocarbon Ethyl ester, 2-hydrocarbon ethyl acrylate, 2-hydrocarbyl acrylate, 2-hydroxypropyl acrylate, hydroxyl-containing monomer such as allyl alcohol, propylene, amine, methacryl Amine, dipropyl g and decylamine such as acrylamide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, sulfhydryl An amine group-containing monomer such as dimethylaminopropyl dimethyl ester or dimethylaminopropyl acrylate, glycidyl acrylate, glycidyl methacrylate, glycidyl dimethyl ether, etc. Monomer, and other water-soluble monomers such as vinylpyrrolidone, vinyl acridine, vinyl carbazole, etc., and polyacrylic acid vinegar or methyl propyl monochloride, divinyl benzoic acid A cross-linking agent such as a dilute acid, a diallyl acrylate, or a glycidyl allyl ether, etc., may be γ-(methacryloxy)propyltrimethoxydecane, vinyltriethoxydecane, or the like.曱 methoxy decane styrene, p-triethoxydecane styrene, p-trimethoxydecane-α-methyl phenethyl hydrazine, p-triethoxy zephyr-a-methyl styrene, γ-(acrylic hydrazine Oxy) propyl trimethoxy decane, vinyl trimethoxy decane, hydrazine — 9 315986 1295699 β (Ν-vinyl benzyl aminoethyl γ-aminopropyl) trimethoxy decane. a polymer or a combination of two or more kinds of hydrolyzable decyl-based monomers or a polymer crosslinked with the above polymer, low softening point Polyamide, low softening point, polyester, etc. having 丨8 (a thermoplastic resin having a softening point below TC, and a low boiling point solvent such as n-hexane, cyclohexane, n-pentane, isopentane, and n-butylene , Isobutan, Zhenggeng, Zhengxin, Yixin, gasoline, Erji, acetone, benzene, etc. 15 (TC below the organic solvent. The heat-expandable particle system is composed of the above-mentioned thermoplastic resin particles, which are impregnated with the above-mentioned low-boiling solvent, and the low-softening point of the heat-sensitive (4) shell, which is filled with the above-mentioned low-boiling solvent (4). The diameter of the (four) is usually 〇.5 to the heat-expandable granules used in the present invention, and also heat-expandable inorganic granules such as feldspar, wave iron, and silica gel. [Fiber flakes] p January, cut-off sheets, by means of needle-rolling entangled fibers, or by impregnation or mixing in fiber-woven sheets or mats, or by lending (4) Rolling a synthetic resin adhesive impregnated with a sheet of entangled fiber web or a raft, followed by a dimensional method or the like. The 1 m-expanded granules are usually impregnated or mixed with a synthetic resin T in a fiber sheet or a mat, or may be mixed in the synthetic resin binder. The mixing ratio n/k $ is added to the fiber relative to the fiber 〇·1 to 50 mass 315986 10 1295699, and the above-mentioned exfoliated fiber is impregnated with a synthetic resin, usually in a liquid state: into a resin or a synthetic resin solution. The exfoliated fiber is crushed, or the exfoliated fiber is coated with a liquid to synthesize a f-fat or a synthetic resin solution by spray coating, roll coating, flow coating or the like. For the diterpenes in the exfoliated fibers which are already contained or mixed with the synthetic resin, after being impregnated or mixed with the synthetic resin, the flaked fibers, <striking rolls or press plates are twisted. In this case, when the fiber sheet is reduced in thickness, and the hollow fiber is contained in the fiber sheet, the rigidity is high and the elasticity is restored, and the thickness can be maintained to a certain extent. In particular, when the niobium thin film contains a low n fiber, the fiber is flaked, the low melting fiber is heated and melted, and the fiber is preferably followed by the fiber. So: Come. The fiber sheet is improved in strength and rigidity, the handleability of the synthetic resin impregnated k is improved, and the thickness after twisting is also remarkable. When the fiber of the present invention contains a hollow fiber as described in JP, the thinned sheet is made of a synthetic resin having a high rigidity and capable of forming a sheet of the synthetic resin adhesive of the exfoliated fiber. After impregnating or mixing the synthetic resin solution into the exfoliated fibers, the sheet fibers are dried. When the synthetic resin contained in the exfoliated fiber is bonded to the thermosetting resin, the resin can be stored for a long period of time in a β state, and can be molded at a low temperature for a short period of time. [Synthetic Resin Adhesive] As a synthetic resin which is used as a binder of the fiber, for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-acetic acid B 315986 11 1295699 can be used. , polystyrene, polyethylene, styrene, polyvinyl acetate, fluororesin, thermoplastic acrylic resin, thermoplastic polyester, thermoplastic polyamide, thermoplastic urethane resin, acrylonitrile butadiene Copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-propylene copolymer, ethylene-propylene tri-copolymer, ethylene-vinyl acetate copolymer, thermoplastic synthetic resin, urethane A thermosetting synthetic resin such as a resin, a melamine resin, a thermosetting acrylic resin, a urea resin, a phenol resin, an epoxy resin, or a thermosetting polyester, or a urethane resin prepolymer which produces the synthetic resin, % oxygen Resin prepolymer, melamine resin prepolymer, urea resin prepolymer, phenol resin prepolymer, diallyl citrate (DAP) prepolymer, malonic acid condensate, polyisocyanate, Methacrylate Monomer prepolymers, diallyl phthalate vinegar (MP) monomers, oligomers, monomers and other synthetic resin prepolymer. The above synthetic resins may be used singly or in combination of two or more kinds, usually in the form of an emulsion, a latex, an aqueous solution, an organic solvent or the like. The synthetic resin binder used in the present invention is the most lipid. According to the invention, (4) (4) Resin is used. The phenolphthalein resin is known by combining a phenolic compound with an aldehyde and/or an aldehyde. To impart water solubility, it is also possible to sinter the ^ and/or sulfur. ^Wetting of the _reading grease The phenolic resin of the present invention, as a preliminary liquid, is impregnated into the sheet substrate. The initial shrinkage = water = initial = shrinkage use · methanol, ethanol, n-propanol, h 'do not, night according to ^, can also be one > b · propanol, n-butanol, butitol, Di-butanol, tricbutanol, n-pentanol, ri-butyl, scorpion, 2-ethylbutanol, n-heptanol, n-methylpentamidine, trimethylnonanol, cyclohexanol, 315986 12 1295699 Alcohols such as benzyl alcohol, decyl alcohol, tetrahydrofurfuryl alcohol, rosin alcohol, diacetone alcohol; acetone, methyl acetone, methyl ethyl ketone, methyl n-propanone, methyl n-butanone, methyl isobutyl ketone , ketones such as diethyl ketone, di-n-acetone, diisobutyl ketone, acetonyl acetone, dimethyl ether, hexanone, methylcyclohexanone, ethyl benzene, camphor; ethylene glycol monoethyl alcohol, two Glycols such as ethylene glycol, propylene glycol, trimethyl glycol, polyethylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, triethylene glycol a glycol ether such as an alcohol monomethyl ether; an ester or a derivative thereof of the above glycol such as ethylene glycol diacetic acid s?, diethylene glycol monoethyl ether acetate; an ether such as 1 '4 dioxane; Ethyl cellosolve, two Carbitol, ethyl lactate, isopropyl lactate, diethylene glycol diacetate, dimethylformamide and the like water-soluble organic solvent. [Phenol-based compound] As a compound which is used in the above-mentioned antimony resin, it can be a mixture of a unity or a unit test, but only when a unit phenol is used, at the time of hardening, and after hardening. It is easy to release furfural, and thus it is preferred to use a polyphenol or a mixture of a monophenol and a polyphenol. [Units] As the above unit phenol, exemplified by: phenol; or o-nonylphenol, m-cresol, p-cresol, ethyl phenol, isopropyl phenol, dinonol, 3,5-dioxanol, butyl Alkylphenols such as phenol, tert-butylphenol, nonylphenol, o-merol, m-fluorophenol, p-fluorophenol, o-phenol, m-chlorophenol, para-phenol, o-bromophenol, m-bromophenol, Bromophenol, o-iodophenol, m-iodophenol, p-iodophenol, o-aminophenol, m-aminophenol, p-aminophenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, 2, 4-2 a unit phenol substitute such as nitrophenol or 2,4,6-dinitrophenol; a polycyclic unit phenol such as naphthol 315986 13 1295699, and the like, and these unit phenols may be used alone or in combination of two or more. [Multiple expectations] As the above polyphenol, resorcinol, alkyl resorcinol, pyrogallol, catechol, alkyl catechol, hydroquinone, alkyl hydroquinone, and stupid are exemplified. Bismuth, bisphenol, trihydroxynaphthalene, etc. These polyphenols may be used singly or in combination of two or more. Preferably, the polyphenol is resorcinol or alkyl resorcinol, and the special product is a reaction rate with an aldehyde which is faster than that of resorcinol. The diphenol may, for example, be 5__mercaptoresorcin, resorcinol, 2,2,5-dipropylisophenyl 5-ethylresorcinol, 5-propyl resorcinol, 5-n-butyl resorcinol, 4, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 4,5-diethyldiyl resorcinol, 4, 5-dipropyl resorcinol, hop, 4-methyl-5-ethylisophthalic acid, 2-methyl-5--5-ethyl resorcinol, 2-mercapto-5-propanoid Resorcinol T-based resorcinol, 2,4,5-triethyl resorcinol, and the like. The oil shale produced in Estonia is produced by dry distillation because of its low cost, and it contains a large amount of highly reactive various fluorenyl meta-benzoquinones in addition to 5-methylm-phenylene. Therefore, it is a polyphenol raw material of the present invention. In the present invention, the phenolic compound and the aldehyde and/or aldehyde donor (aldehyde) are condensed, and the compound is added to the aldehyde to form a compound or a mixture thereof. Such aldehydes may, for example, be: formaldehyde, acetaldehyde, propionaldehyde, chloral, furfural, glyoxal, n-butyraldehyde, hexanal, acrolein, benzene, phenanthrene, acetophenone, phenylethylidene, o-toluene Acid, water platter, etc., 315986 14 1295699 As the aldehyde donor, for example, it may be exemplified by furfural, trioxane, hexamethylenetetramine or tetradecanal. As described above, in order to improve the stability of the water-soluble phenol-based resin, it is preferred to subject the phenol-based resin to sulfonation and/or thiolation. [Continuation of the thiolating agent] The sulfonylating agent which can be used for improving the stability of the water-soluble phenol-based resin may, for example, be a sulfuric acid, a heavy sulfurous acid or a meta-sulfuric acid and an alkali metal or a diterpene. a water-soluble sulfite obtained by reacting a quaternary amine or a quaternary ammonium such as an amine or benzyltrimethylhydrazine, or an aldehyde addition obtained by reacting the water-soluble sulfite with the water. Propionaldehyde, gas aldehyde, furfural, B
該搭附加物、係曱搭、乙酸 二醛、正丁醛、己醛、丙烯醛、苯甲醛、巴豆醛、丙烯醛、 笨乙醛、鄰甲苯醛、水楊醛等醛與上述水溶性亞硫酸鹽之 附加反應所得物、例如曱醛與亞硫酸鹽反應所成之醛附加 物、係經甲烧磺酸鹽。 [硫甲基化劑]The aldehyde, the aldehyde, the acetic acid dialdehyde, the n-butyraldehyde, the hexanal, the acrolein, the benzaldehyde, the crotonaldehyde, the acrolein, the acetaldehyde, the o-tolualdehyde, the salicylaldehyde, etc. An additional reaction product of a sulfate, for example, an aldehyde addition product obtained by reacting furfural with a sulfite, is a mesylate sulfonate. [thiomethylating agent]
作為能使用於改良水溶性㈣樹脂的安定性的硫甲^ 化劑、可例舉如··次硫酸甲㈣（雕白粉、i i t)、二: 硫酸苯甲軸等的脂肪族、芳香族㈣驗金屬次硫酸鹽 ==酸氫鈉、亞硫酸絲輪金屬、驗土類金屬的互 ::二：*連—亞硫酸鹽）類、羥基甲烷亞磺酸鹽等的葬 基烧煙亞續酸鹽等。 · 在製造上述酚系樹脂時、 硫酸、（正）磷酸、（正）蝴酸、 因應必要、可將例如：鹽酸、 草酸、甲酸、乙酸、丁酸（丙 315986 1295699 基甲酸）、苯磺酸、苯酚磺酸、對—甲基苯磺酸、萘1一碏 酸、奈-β-磺酸等無機或有機酸、草酸二甲酯等有機酸酯 類、順丁稀二酸酐、_等酸酐、氯化銨、硫酸錢、石肖曰酸 敍、草酸銨、乙酸銨、磷酸銨、硫氰酸銨、亞胺基碏酸銨 等銨鹽、氯乙酸或該納鹽、α，α，_二氯醇等有機“物、 三乙醇胺鹽酸鹽、鹽酸苯胺等胺類的鹽酸鹽、水楊酸尿素 加成物、硬脂酸尿素加成物'庚酸尿素加成物等的尿素加 f物、Ν—三甲基牛磺酸、氯化鋅、氯化鐵等酸性物質、氨、 月:類、氫氧化納、氫氧化鉀、氫氧化鋇、氫氧化舞等驗金 屬或驗土類金相氫氧化物、錢㈣土類金屬的氧化 =石反酉夂鈉、亞硫酸納、乙酸納、碟酸納等驗性金屬的弱 酉文鹽類等鹼性物質作為觸媒或pH調整劑混合。 [酚系樹脂的製造] 上述=樹脂（初期縮合物）可依-般方法製造、具體 此藉由⑷單凡紛及/或多紛與駿類縮合之方法、 n員縮合之初期縮合物及/或多酚與醛類縮人 合物、和單元齡及/或多I缩合之方法、(C;單： 合與(=縮合之初期縮合物、和單㈣及7或多酴縮 之(:):r:r 二合圳 ^ , , σ物之縮合方法、（〇單元酚與醛類縮人 之初期縮合物及/或多紛與_ 、二 酚與多酚與醛類裣人夕、* 仞肩雒σ物、和早兀 於本發明中縮合物之縮合方法等而製造。 縮合物。上述盼笨I糸樹脂、格烧基間笨二盼共 土日1本一酚共縮合物係、該共縮合物（初 315986 16 1295699 * =物）的水溶性良好、且與只由賴成之縮合物比 二溫條件下能長期保存之優點。並且使該水溶 液μ於缚片基材、予前處理使所得纖維薄片安定性良 、:二且該Λ維胃片即使長期保存也不喪失成形性。再者、 „ 扪夂應性較南、捕集遊離醛而反應、 :::靡：的遊祕量亦有漸為減少等優點。上述 ::::合物之最佳製造方法、係首先使 合物、接著於I系樹脂初期縮合物^ 冰、元土間苯—酝、如有必要添加醛並使其反應之方法。 例如、上述⑷單元紛及/或多齡與_之縮合中 常祕1莫耳單元_添加U至3莫耳㈣類、對於1 Ϊ耳讀則添加0.1至0·8莫耳的酸類、以及因應必要之 :谷成分、再以液溫55至lorc之條件下加熱反應 8至2(M，。此時的駿類在反應開始時可全部加入 分批或連續滴入。 將上述盼系樹脂初期縮合物予以石黃甲基化及/或硫甲 基化時、於該初期縮合物中、於任意階段下添加續甲基化 劑=/或硫甲基化劑、再將I系化合物及/或初期縮合物予 以磺甲基化及/或硫甲基化。 、，磺甲基化劑及/或硫甲基化劑之添加、可於縮合反應 前、反應中、反應後之任一階段中進行。 磺甲基化劑及/或硫甲基化劑之總添加i、對於J莫 酚系化合物、通常係0.001至15莫耳。在〇 〇〇1莫耳以 下時之酚系樹脂的親水性不足、h5莫耳以上時之酚 315986 17 1295699 脂的耐水性變差。為良好地保持所製造之初期縮合物的硬 化性、及硬化後樹脂的物性等性能、以〇 〇1至〇 8莫耳的 程度為最佳。 ·、 為將上述i系樹脂初期縮合物予以石黃甲基化及/或硫 甲基化而添加之磺甲基化劑及/或硫甲基化劑、經愈該初期 縮合物的經甲基及/或該初期縮合物的芳香族反應、於該初 期縮合物中導入磺甲基及/或硫甲基。 士此H石戸、甲基化及/或硫甲基㈣旨㈣ j縮合物的水溶性、於酸性（PH1G)至驗性的廣範圍中為安 疋、即使於酸性、中性以及驗性的各個範圍中亦能硬化。 2別㈣性時、-旦使其硬化、殘存的經甲基減少、硬化 物經分解不會有發生甲醛的可能性。 、天再者於本發明中、作為上述紛系樹脂、如有必要亦可 :力::尿素、硫脲、蜜胺、硫代蜜胺、二氛胺、胍、胍胺、 s'苯基M胺、2,6二胺基-1，3二胺的胺系單體及/ 或樹脂皁體所成之初期縮合體並與紛系化合物及/ 或初期Ιί§合物共縮合。 喃人H於本發明的讀系樹脂的初期縮合物（包含初期共 = 村再添加混㈣及/祕料體、或烧醇化 —虱酮讨生物等硬化劑。 作為上㈣及/絲給ϋ與❹ 初期共縮合物）祕及/或酸給予體所使用i 。枚物、烷化三氮酮 / ^ ^ ^ 醛及/或醛”〜…猎由尿素系化合物與胺類與 予肢之反應所得。作為使用於製造烧醇化三氮 315986 1295699 物的上述尿料、化合物、可例舉如：尿素、硫服、 ^水素等烧基尿素、甲基硫尿等的烧基硫脲、苯基尿素、 素、i化苯基尿素，輕烧基尿素等單獨或二種以 氣σ物纟中特佳之尿素化合物係尿素或硫脲。又、 乍=類、可例舉如：甲胺、乙胺、丙胺、異丙胺、丁胺、 女:脂肪族月安、节（基）胺、糠（基）胺、乙醇胺、乙二胺、 =二胺、六亞f基四胺等胺類之外另有氨、此等作為單獨 4種以上的混合物使用。使用於製造烧醇化三氮酉同衍生 勿的私及/或酸給予體與使用於製造酉分系樹脂初期縮合物 的醛及/或醛給予體係同樣之物。 於上述烧基化二偶氮衍生物的合成中、通常對於1莫 耳尿素化合物胺類及/或氨以U至1.2莫耳、駿及/或路 ，予體1.5 1 4· G莫耳的比例使其反應。上述反應時、此 等的：加順序係任意、但作為最佳之反應方法、係首先於 反應益中投入所需量的醛及/或醛給 啊以下的溫度-邊徐徐加人所需量的胺減保^ 加所需量的尿素化合物、然後於8〇至9(rc的條件下加熱 櫈拌2至3小時使其反應之方法。作為酸及/祕給予體、 通常係使用37%甲膝水、但為提高反應生成物的濃度、盆 令一部分亦可換成多聚甲搭。又、如使用六亞甲基四胺（耽 胺酸）能得到較高固形分的反應生成物。尿素系化合物與胺 類及/或氨和醛及/或醛給予體的反應通常以水溶液進行、 仁以使用甲酵、乙醇、異丙醇、正丁醇、乙二醇、二甘醇 等醇颂的單獨或二種以上的混合物亦可取代之部分或全部 315986 19 1295699 二能添加使用丙鋼、甲基乙基_等酮類等之溶水 性有機洛劑之單獨或二 ，奋水 加量、於酸及/十“ 上的此合物。上述硬化劑的添 ； 或略給予體時、相對1 00暂旦八ώΑ 4»々 酚系樹脂的初期縮人物Ρ #从 〇貝里刀的本發明的 分、於烧Α化…α (、縮合物）係10至100質量 flt6A ' 土二虱酮衍生物時、相對100質量分的酚车抖 知的初期縮合物(初期共縮合物)係10至5。。質：:心 現人於：::：所使用的合成樹脂黏合劑中、亦可再添加、 酸二亞― Λ 卜 虱軋化鎂、虱氧化鋁、氧化鎂、氧化鈦、 ^匕鐵、減鋅、氧化紹、二氧 :岩)、石膏、滑石、黏土 (泥土 )、石：:；二 膨潤土（皂土）、白# _ m 矽馱鈣、 古靜黑、鐵粉、崎、玻璃粉、石粉、 填材、天然橡膠或= 塵)=、氧化錯:等的無機 丁生物本乙烯—丁二烯橡膠、丙烯 I膠里Λ、橡膠、^丁二婦橡膠、乙烯—丙烯橡膠、異戊 —烤—異丁烯橡膠等的合成橡膠、聚乙稀醇、 :去·、、，n版粉衍生物、骨膠、明膠、血粉、甲基纖 p/…，甲基纖維素、經乙基纖維素、聚丙烯酸鹽、聚丙 =她寻水溶性高分子或天崎膠；碳酸.滑石、石膏、 A ’：、木叔胡桃粉、椰殼粉、小麥粉、米粉等的填材、 界面活性劑；硬脂酸r • Q正十八k )、棕櫚酸（十六酸）等高級 月曰方:彳不櫚知、硬脂醇等高級醇、硬脂酸丁酯、單硬脂 天然“合成蠟類；石蠟類、石蠟油、矽酮油、矽酮樹 315986 20 1295699 . 脂、敦樹脂、聚乙烯酉卜潤滑脂等脫模劑、偶說二甲臨胺、 =亞 '基五亞甲基四胺、p，p，_氧雙(苯磺醯哄)、偶氮雙 ’ 2’-(2—曱基丙睛）等有機發泡劑、碳酸氫鋼、碳酸 虱鉀、碳酸氫銨等無機發泡劑、石夕膠球、珍珠岩、玻璃球、 玻璃、中空陶瓷等的中空顆粒體、發泡聚乙烯、發泡 聚苯乙烯、發泡聚丙烯等的塑膠發泡體或發泡顆粒;顏料、 染料、抗氧化劑、抗靜電劑、結晶促進劑、難燃劑、防火 劑、防水（Waterrepellent)劑、撥油劑、防蟲劑、防腐劑、 蠟類、潤滑劑、抗老化劑、紫外線吸收劑（uv吸收劑）、辦 f劑(―_、可塑劑⑽p)、助增塑劑（鄰苯二曱酸二環己酉旨曰) 等邠苯一甲酸酯系可塑劑或其他的磷酸甲苯 Phosphate)等可塑劑等。 yl 本發明的纖維薄片、一邊限制厚度一邊以含有該熱膨 =顆粒體的熱膨脹溫度以上加熱、使該熱膨脹性顆粒體 ^脹。，本發明的纖維薄片以平板狀或規定形狀成形、但 =;成ϋΐ $以熱壓成形為適用、該熱膨脹性顆粒體的加 '.、、膨脹係於上述熱麼成形時、一邊限制厚度一邊進行。本 發明的，維薄片藉由熱壓形成平板狀後、亦可藉由熱壓成 訥^見疋形狀、並且於含有低融點纖維或熱塑性樹脂黏接 劑時=經加熱使低融點纖維或熱塑性樹脂黏合劑軟化後、 ” y藉由冷磨成形規定形狀。本發明的纖維薄片亦可數声 =疊使用。並且亦可使該纖維薄片和表皮材、内襯材、^ 的其他元件層積。本發明的纖維薄片係適用作為例如 八的天花板材料、儀表板隔音材料、引擎罩隔音材、引 315986 21 1295699 ，部隔音材料、汽缸前蓋隔音材料、緩衝材料、鋪墊、 ΐίΐ、車門修邊等的内裝材料的基材、或積層於積材的 子 、或吸音材、隔熱材、建築材料等。 —以下、以實施例詳細說明本發明。但本發明並不只限 疋於以下所示之實施例。 [實施例1 ] 用由聚賴維（纖度黯ex、纖維長度：54龍_ 貝里％所成纖維的薄片狀的編網、並藉由針軋（needie P隱hing)法製造薄片化纖維（單位面積重量、厚 度15咖）。纟95 f量分的祕初期縮合物（45%質量固形 分）中已添加混合作為熱膨脹性顆粒體的聚偏氯乙稀薄殼 中充填異戊院的5質量分微膠囊的含浸液、以達到作為固 形分50質量％含有量的程度含浸於該纖維薄片中、狹後於 乾燥室内一邊吸引一邊以i〇(rc的溫度乾燥3分鐘並予前 硬化製得纖維薄片。最後以2〇〇。〇的溫度熱壓制成形予前 硬化㈣該纖維薄片60秒鐘、並一邊限定厚度一邊使該微 膠囊恥脹而製得8mm厚的成形物。 [比較例1] 除了 κ鈀例1中的熱膨脹性顆粒體之外，其他與上述 相同之壓製成形製得8mm厚的成形物。 ” 對上述實施例1及比較例i的成形物進行彎曲測試和 吸音率及抗通氣測試。彎曲測試係依照JIS —K6911的仄17 之彎曲強度進行、測試條件為寬度：25_、支點間距離： 100mm並且吸曰率係依照j I s _ a 145 [依管内法的建築材 315986 22 1295699 料垂直入射吸音率測定法]。通氣抵抗係依照Fraz i 1型通 氣度測試機（Frazi 1 — type Air permeabi 1 i ty)、並使用加 藤技研（Katotech)股份有限公司製的通氣性測試機（KE s —F 8 — API )、測定單位面積的通氣量為4cc/s · cm2時的 通氣抵抗。測試結果如表1所示。 表1 成形物 彎曲試驗 吸音率（％) 通氣抵抗 KPa · s/m (MPa) 500Hz 1 000 Hz 2000 Hz 4000 Hz 實施例1 0. 38 30 58 79 88 0-346 比較例1 0. 32 18 29 60 78 0. 072 [實施例2] 對由50質量％的聚酯中空纖維（纖度：5dtex、中空 率：20%、纖維長度：56mm)、和35質量％的聚酯纖雄（纖 度：7dtex、纖維長度：60mm)、和15質量％的低融點纖維 (纖度· 2· 5dtex、融點· 120 C、纖維長度：65_)所成混 合纖維的編網薄片以18 0 °C的溫度加熱5分鐘、再使該聚 酉旨低融點纖維溶融並藉由該溶融物相互接著纖維、由此製 得薄片化纖維（單位面積重量40Og/m2、厚度20mm)。再將 於9 0質量分的盼_烧基間苯二盼一曱酸初期縮合物水溶 液（50%質量固形分）中已添加混合2質量分的氮系難燃 劑、2質量分的氟系防水·防油劑、及6質量分的熱膨脹 性顆粒體（膠囊型、松本彳政球粒（Matsumotoiiiircospher) F -100 :松本油脂製藥股份有限公司製、薄殼軟化溫度135 315986 23 1295699 . 至140 C )的含〉叉液、以達到作為固形分3〇質量％含有量 的程度含浸於該薄片化纖維中、然後於乾燥室内一邊吸引、 一邊以100°C的溫度乾燥3分鐘並予前硬化製得纖維薄 — 片。最後以200 C的溫度熱壓制成形予前硬化後的該纖維 溥片6 0秒鉍、並一邊限定厚度一邊使該顆粒體膨脹而製得·， 15mm厚的成形物。 1 [實施例3] " 使用由45質量％的聚酯中空纖維（纖度：7dtex、中空 率：30%、纖維長度：75mm)、和30質量％的聚醯胺纖維（纖每 度：12dtex、纖維長度：75mm)、和10質量％的洋麻纖維（纖 度：20至25dtex、纖維長度：5〇_)、和15質量％的聚酯 低融點纖維（纖度·· 12dtex、融點：11(TC、纖維長度ι5_) 所成混合纖維的薄片狀編網、並藉由針軋（needle 、 punching)法製造薄片化纖維（單位面積重量4〇〇g/m2、厚 - 度18mm)。再將實施例2所用的含浸液、以達到作為固形 分50質量％含有量的程度含浸於該薄片化纖維中、然後於 乾燥室内一邊吸引一邊以l〇(TC的溫度乾燥4分鐘並予前 馨 硬化製得纖維薄片。最後和實施例2同樣的方法熱壓成形 該予前硬化後的該纖維薄片、並一邊限定厚度一邊使該顆 粒體膨脹、由此製得15mm厚的成形物。 .The thioformate which can be used for improving the stability of the water-soluble (tetra) resin may, for example, be an aliphatic or aromatic (tetra) such as methyl sulfonate (four) (carved white powder, iit) or two: benzoyl sulfate. Examination of metal sulphite == sodium hydrogen hydride, sulphite wire metal, soil for soil testing:: two: * _ sulfite), hydroxymethane sulfinate, etc. Acid salt, etc. · In the production of the above phenolic resin, sulfuric acid, (n-)phosphoric acid, (n-)flavic acid, if necessary, for example: hydrochloric acid, oxalic acid, formic acid, acetic acid, butyric acid (C-315986 1295699 carboxylic acid), benzenesulfonic acid , organic acids such as phenolsulfonic acid, p-toluenesulfonic acid, naphthalene monodecanoic acid, naphthalene-β-sulfonic acid, organic acid esters such as dimethyl oxalate, cis-succinic anhydride, and the like Ammonium salt such as ammonium chloride, sulfuric acid, sulphuric acid, ammonium oxalate, ammonium acetate, ammonium phosphate, ammonium thiocyanate, ammonium imide amide, chloroacetic acid or the sodium salt, α, α, _ Urea addition of an organic substance such as dichlorohydrin, a hydrochloride of an amine such as triethanolamine hydrochloride or aniline hydrochloride, a urea salicylic acid adduct, a urea stearate urea adduct, a heptanoic acid urea adduct, or the like f, Ν-trimethyl taurine, zinc chloride, ferric chloride and other acidic substances, ammonia, month: sodium hydroxide, potassium hydroxide, barium hydroxide, hydroxide dance, etc. Oxidation of metallographic hydroxides, money (4) soil metals = stone antimony sodium, sodium sulfite, sodium acetate, sodium silicate, etc. An alkaline substance such as a weak salt is mixed as a catalyst or a pH adjuster. [Production of phenolic resin] The above = resin (initial condensate) can be produced by a general method, and specifically by (4) Or a method of condensation with a genus, an initial condensate of n-member condensation, and/or a polyphenol and an aldehyde condensate, and a method of condensing unit age and/or multiple I, (C; single: = initial condensate of condensation, and single (four) and 7 or more collapsed (:): r:r dimerization, sigma condensation method, (initial condensate of phenolic phenol and aldehydes) / or a variety of _, diphenols and polyphenols and aldehydes, 仞 仞 仞 、 、 、 和 和 和 、 、 、 、 、 、 、 、 、 、 、 、 缩合 缩合 缩合 缩合 缩合 缩合 缩合 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The resin and the lattice base are both stupid and hope to have a phenolic co-condensate system, and the co-condensate (initial 315986 16 1295699 * = material) has good water solubility, and is more temperate than the condensate only The advantage of being able to be preserved for a long period of time under conditions, and the aqueous solution is allowed to be applied to the substrate of the substrate, and the obtained fiber sheet is well-stabilized, and the obtained fiber sheet is stable even if In the period of preservation, the formability is not lost. In addition, „ 扪夂 性 较 、 、 、 、 、 捕 捕 捕 捕 捕 捕 捕 捕 :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: The preferred method of production is a method of first reacting a compound, followed by an initial condensate of the I-based resin, ice, and benzene, and if necessary, adding an aldehyde and reacting it. For example, the above (4) unit and/or In the condensation of multi-aged and _, the 1st molar unit is added to the U to 3 molar (4) class, and for the 1 Ϊ ear reading, 0.1 to 0.8 mol of acid is added, and the necessary: grain component, and liquid The reaction is heated at a temperature of 55 to lrc to a temperature of 8 to 2 (M. At this time, the precursor can be added to the batch or continuously at the beginning of the reaction. The initial condensate of the above-mentioned desired resin is subjected to pyronylation and/or In the case of thiomethylation, a methylating agent =/or a thiomethylating agent is added to the initial condensate at any stage, and the I-based compound and/or the initial condensate are sulfomethylated and/or Or thiomethylation. The addition of the sulfomethylating agent and/or the thiomethylating agent can be carried out in any stage before, during or after the condensation reaction. The total addition i of the sulfomethylating agent and/or the thiomethylating agent is usually 0.001 to 15 moles for the J phenol compound. When the hydrophilicity of the phenolic resin is less than 〇〇1, the phenolic 315986 17 1295699 of the phenol is deteriorated in water resistance. In order to satisfactorily maintain the properties such as the hardenability of the initial condensate produced and the physical properties of the resin after curing, it is preferably from 〇1 to 莫8 mol. a sulfomethylating agent and/or a thiomethylating agent which is added to the initial condensate of the i-based resin by pyromethylation and/or thiomethylation, and a methyl group of the initial condensate Or an aromatic reaction of the initial condensate, and introduction of a sulfomethyl group and/or a thiomethyl group in the initial condensate.士此H, 甲基, methylation and / or thiomethyl (4) (4) j condensate water solubility, a wide range of acid (PH1G) to the test for ampoules, even acidic, neutral and experimental It can also be hardened in every range. 2 (4) When it is used, it will harden and the residual methyl group will decrease, and the hardened material will not decompose. In the present invention, as the above-mentioned variegated resin, if necessary, it is also possible: force: urea, thiourea, melamine, thiomelamine, diamine, guanidine, guanamine, s' phenyl An initial condensate of an amine-based monomer and/or a resin soap of M amine or 2,6-diamino-1,3 diamine, and co-condensation with a compound and/or an initial compound. The initial condensate of the read-system resin of the present invention (including the initial total = village re-mixed (four) and / secret material, or smoldering - ketone ketones and other hardeners. As the upper (four) and / silk to give ϋ And ❹ initial co-condensate) and / or acid donor used i. The above-mentioned urine material is obtained by reacting a urea-based compound with an amine and a pre-limb. The above-mentioned urine material is used as a product for producing an alcohol-soluble trinitrogen 315986 1295699. And the compound may, for example, be urea, sulfur, hydrous urea, methyl thiourea, etc., thiourea, phenyl urea, phenyl, phenyl urea, lightly burned urea, etc. alone or The urea compound or urea thiourea, which is particularly good in the gas sputum, can be exemplified by methylamine, ethylamine, propylamine, isopropylamine, butylamine, female: aliphatic genomic, Other than amines such as alkylamine, anthraceneamine, ethanolamine, ethylenediamine, =diamine, and hexa-f-tetraamine, ammonia is used, and these are used as a mixture of four or more kinds alone. The same is made of the aldehyde and/or aldehyde donor system used to produce the initial condensate of the oxime resin. The above-described alkylated diazo derivative is produced. In the synthesis, usually for 1 mole urea compound amines and / or ammonia with U to 1.2 m, Jun and / or road, The ratio of 1.5 1 4 · G mole is reacted. The above reaction time, the like: the order of addition is arbitrary, but as the optimum reaction method, the required amount of aldehyde and/or the first amount is added to the reaction benefit. The aldehyde is given to the following temperature - the amount of amine reduction is added slowly. The required amount of urea compound is added, and then the mixture is heated for 2 to 3 hours at 8 Torr to 9 (rc) to react. As an acid and/or secret donor, 37% of knee water is usually used, but in order to increase the concentration of the reaction product, a part of the pot may be replaced with polymethylate. Also, if hexamethylenetetramine is used ( The proline acid can obtain a reaction product of a higher solid content. The reaction of the urea compound with the amine and/or the ammonia and the aldehyde and/or the aldehyde donor is usually carried out in an aqueous solution, and the bene, ethanol, and isopropyl ester are used. Alcohol, n-butanol, ethylene glycol, diethylene glycol, etc., alone or in combination of two or more, may be substituted for part or all of 315986 19 1295699. Two ketones such as propylene steel, methyl ethyl ketone, etc. may be added. Separate or two of the water-soluble organic granules, the amount of water, the acid and / ten" The compound of the present invention is added to the above-mentioned hardening agent; or when it is slightly given to the body, the initial shrinkage of the phenolic resin is relatively small. When α (, condensate) is a 10- to 100-mass flt6A 'm-dioxanone derivative, the initial condensate (initial co-condensate) which is pulverized with respect to 100 parts by mass is 10 to 5. The heart is now in:::: The synthetic resin binder used can be added, acid di- Λ Λ 虱 虱 rolling magnesium, lanthanum aluminum oxide, magnesium oxide, titanium oxide, lanthanum iron, zinc reduction, Oxidation, dioxane: rock), gypsum, talc, clay (soil), stone::; two bentonite (saponin), white # _ m 矽驮 calcium, ancient static black, iron powder, saki, glass powder, stone powder , filler, natural rubber or = dust) =, oxidation error: inorganic inorganic bio-butadiene rubber, propylene I rubber, rubber, rubber, ethylene-propylene rubber, isoprene - Bake-synthetic rubber such as isobutylene rubber, polyethylene glycol, : go,,, n version of powder derivatives, bone glue, gelatin, blood powder, methyl fiber p /... , methyl cellulose, ethyl cellulose, polyacrylate, polypropylene = her water-soluble polymer or Tianqi gum; carbonic acid, talc, gypsum, A ':, wood uncle walnut powder, coconut shell powder, wheat flour , rice flour and other fillers, surfactants; stearic acid r • Q is 18 k), palmitic acid (hexadecanoic acid) and other high-grade menstruation: high-grade alcohol, stearic alcohol, etc. Butyl acrylate, mono-hard fat natural "synthetic wax; paraffin, paraffin oil, decyl ketone oil, ketone ketone tree 315986 20 1295699. Release agent such as grease, Dun resin, polyethylene bismuth grease, etc. Organic foaming agents such as lining amine, =y'-pentamethylenetetramine, p,p,_oxybis(benzenesulfonate), azobis' 2'-(2-mercaptopropene), carbonic acid Inorganic foaming agent such as hydrogen steel, cesium carbonate, ammonium hydrogencarbonate, hollow granules such as Shixi rubber balls, perlite, glass spheres, glass, hollow ceramics, foamed polyethylene, expanded polystyrene, foaming Plastic foam or foamed granules such as polypropylene; pigments, dyes, antioxidants, antistatic agents, crystallization accelerators, flame retardants, fire retardants, waterproof Waterrepellent), oil repellent, insect repellent, preservative, wax, lubricant, anti-aging agent, UV absorber (uv absorber), agent f (-_, plasticizer (10) p), plasticizer (Phenylphthalic acid dicyclohexanide) A plasticizer such as a phthalic acid ester-based plasticizer or other toluene Phosphate. Yl The fiber sheet of the present invention is heated at a temperature higher than the thermal expansion temperature containing the heat-expanding granule while limiting the thickness, and the heat-expandable granule is swollen. The fiber sheet of the present invention is formed into a flat shape or a predetermined shape, but is formed by hot press forming, and the heat-expandable particle body is added, and the expansion is limited to the thickness of the heat-forming body. Do it on one side. In the present invention, after the sheet is formed into a flat plate by hot pressing, it can also be formed into a shape by hot pressing, and when it contains a low melting point fiber or a thermoplastic resin adhesive = heating to make the low melting point fiber After the thermoplastic resin binder is softened, "y" is formed into a predetermined shape by cold grinding. The fiber sheet of the present invention can also be used in several sounds/folding, and the fiber sheet and the skin material, the inner lining material, and other components of the material can also be used. The fiber sheet of the present invention is suitable for use as, for example, eight ceiling materials, instrument panel sound insulation materials, hood noise insulation materials, 315986 21 1295699, partial sound insulation material, cylinder front cover sound insulation material, cushioning material, bedding, ΐίΐ, door The base material of the interior material such as trimming, or the sub-layer of the built-in material, or the sound absorbing material, the heat insulating material, the building material, etc. - The present invention will be described in detail below by way of examples. However, the invention is not limited to The examples shown below are as follows. [Example 1] A flaky braided web made of poly ray (fibrous 黯ex, fiber length: 54 dragon _Berry%), and needle-punched (needie P hidden) Hing) manufacturing Flaky fiber (weight per unit area, thickness 15 coffee). The initial condensate (45% mass solids) of 纟95 f is added to the polyvinylidene chloride shell as a heat-expandable granule filled with isoprene The impregnation liquid of the micro-capsules of the 5 parts by mass of the hospital is impregnated into the fiber sheet to the extent that it is 50% by mass of the solid content, and is then sucked while being sucked in the drying chamber for 3 minutes. The fiber sheet was obtained by pre-hardening. Finally, the fiber sheet was pre-cured at a temperature of 2 Torr. The fiber sheet was pre-cured (4) for 60 seconds, and the microcapsules were swelled while limiting the thickness to obtain a molded article having a thickness of 8 mm. [Comparative Example 1] A molded article having a thickness of 8 mm was produced by press molding in the same manner as described above except for the heat-expandable granules in Example 1 of κ Palladium. ” Bending test of the molded articles of the above Example 1 and Comparative Example i And the sound absorption rate and anti-ventilation test. The bending test is carried out according to the bending strength of 仄17 of JIS-K6911, the test condition is width: 25_, the distance between the fulcrums: 100 mm and the suction rate is according to j I s _ a 145 [in the tube Building materials 315986 22 1295699 Material vertical incident sound absorption rate measurement method. Ventilation resistance according to Frazi i 1 type air permeability tester (Frazi 1 - type Air permeabi 1 ty), and using Katotech (Katotech) Co., Ltd. The ventilation tester (KE s - F 8 - API ) measures the ventilation resistance per unit area of ventilation at 4 cc / s · cm 2 . The test results are shown in Table 1. Table 1 The bending test of the molded product bending test rate (%) Ventilation resistance KPa · s/m (MPa) 500 Hz 1 000 Hz 2000 Hz 4000 Hz Example 1 0. 38 30 58 79 88 0-346 Comparative Example 1 0. 32 18 29 60 78 0. 072 [Example 2] 50% by mass of polyester hollow fiber (denier: 5dtex, hollow ratio: 20%, fiber length: 56mm), and 35% by mass of polyester fiber (denier: 7dtex, fiber length: 60mm), and 15 mass % of the low-melting fiber (denier · 2.5dtex, melting point · 120 C, fiber length: 65_), the meshed sheet of the mixed fiber is heated at a temperature of 18 ° C for 5 minutes, and the polythene is low. Melting fibers are melted and the fibers are bonded to each other by the melt, thereby producing a thinned fiber (Unit weight: 40Og/m2, thickness 20mm). Further, a nitrogen-based flame retardant of 2 mass% and a fluorine-based system of 2 mass% may be added to an aqueous solution of an initial condensate (50% by mass) of 90% by mass of benzophenone benzoic acid. Waterproof and oil repellent, and 6 parts by mass of heat-expandable granules (Capsule type, Matsumoto iii granules F-100: manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd., thin shell softening temperature 135 315986 23 1295699 . to 140 The acyl-containing liquid of C) is impregnated into the exfoliated fiber to such an extent that the solid content is 3% by mass of the solid content, and then dried at a temperature of 100 ° C for 3 minutes while being sucked in the drying chamber and pre-hardened. Made of thin fiber - sheet. Finally, the fiber sheet which had been previously hardened was thermoformed at a temperature of 200 C for 60 seconds, and the pellet was expanded while defining the thickness to obtain a molded product having a thickness of 15 mm. 1 [Example 3] " Use of 45% by mass of polyester hollow fiber (denier: 7dtex, hollow ratio: 30%, fiber length: 75 mm), and 30% by mass of polyamide fiber (fiber per degree: 12 dtex , fiber length: 75 mm), and 10% by mass of kenaf fiber (denier: 20 to 25 dtex, fiber length: 5 〇 _), and 15% by mass of polyester low melting point fiber (denier · · 12 dtex, melting point: 11 (TC, fiber length ι5_) A sheet-like woven fabric of a mixed fiber was produced, and a flaky fiber (weight per unit area: 4 〇〇g/m 2 , thickness - 18 mm) was produced by a needle punching method. Further, the impregnation liquid used in Example 2 was impregnated into the exfoliated fiber to such an extent that the solid content was 50% by mass of the solid content, and then the inside of the drying chamber was suctioned while drying at a temperature of TC for 4 minutes. The fiber sheet was obtained by singly hardening. Finally, the pre-hardened fiber sheet was hot-pressed in the same manner as in Example 2, and the granules were expanded while limiting the thickness to thereby obtain a molded article having a thickness of 15 mm.
[比較例2 ] 依照火焰法、以200°C的溫度熱壓60秒鐘成形作為結 合材的含有20質量％甲階酚醛樹脂型酚樹脂初期縮合物 的一般玻璃棉（單位面積重量6〇〇g/m2、厚度5〇mm)而製得 315986 24 1295699 15mm厚的成形物。 α對上述貝知例2、3及比較例2的成形物進行彎曲測試 ^作II f i s率及通氣抵抗測試驗。該測試結果如表2所 示。 表2 成形物 彎曲測 試驗 (MPa) 操作性* 吸音率（％) 通氣抵抗 kPa·s/m 500Hz 1000Hz 2000Hz 4000 Hz 實施例2 實施例3 比較例2 0. 62 0. 58 0. 12 〇 〇 X 40 43 21 63 65 35 84 87 66 95 97 80 0. 396 0.493 0. 488 *操作性 〇：於成形操作時、纖維不飛散、操作性係良好。 X ·於成形刼作時、來自玻璃之粉塵飛散、該粉塵（玻璃） 易刺手使操作性極差、且對人體有不良影響。 根據表1的結果、確定實施例1的試料和比較例1的 試料相比於周波數的廣範圍中吸音率大且彎曲強度良好。 此係試料纖維因熱膨脹性顆粒體的膨脹而收縮、由此可認 為隨著通氣抵抗值變大所入射的音波能量就減少。這些也 可由通氣抵抗值來確定。 根據表2的結果、確定實施例2、實施例3的試料和 比較例2的试料相比彎曲測試、吸音率均大幅度的提高。 並且貫把例2、貫施例3和比較例2的通氣抵抗值之差距 雖不大、但也得到吸音率提高的預期結果。 25 315986 1295699 · [實施例4 ] 使用由55質量％的聚酯中空纖維（纖度·· 4dtex、中空 率M5%、纖維長度：55關）、和35質量％的維尼論纖維（纖 度、· 7· 5dtex、纖維長度：6〇_)、和1〇質量％的人造纖維 (纖度· 6dtex、纖維長度·· 55mm)所成混合纖維的薄片狀編 網、亚藉由針軋（needle punching)法製造薄片化纖維（單 位面積重1 600g/m2、厚度15_)。再將於9〇質量分的磺 甲基化酚一烷基間苯二酚一曱醛初期縮合物水溶液（45% 質量固形分）中已添加混合5質量分的含氮/燐之難燃劑、工 質量分的矽膠系防水劑、及4質量分的熱膨脹性顆粒體（微 膠囊型微球粒F-85)的含浸液、以達到作為固形分6〇質量 %含有量的程度含浸於該薄片化纖維中、然後於乾燥室内 一邊吸引一邊以1〇〇。〇的溫度乾燥4分鐘並予前硬化製得 纖維薄片。予前硬化後、於該纖維薄片的一面積層作為表 皮材的已塗敷熱熔融黏接劑（聚醯胺樹脂、融點：16〇艽、 粒度：200網眼全通）的聚酯纖維的不織布（藉由網枝法 (Spunbond)製造、單位面積重量3〇g/m2、厚度i5_)、最 後以2 0 0 C的溫度熱壓成形6 〇秒鐘、並一邊限定厚度一邊 使該熱膨脹顆粒體膨脹而製得成形物。該成形物係具有良 好難燃性、防水性、剛性且吸音性之物。 [實施例5] 使用由85質量％的聚酯中空纖維（纖度：7dtex、中空 率：20%、纖維長度：75mm)、和15質量％的難燃聚醋纖 維（識度：4dtex、纖維長度：55mm)所成混合纖維的薄片狀 315986 26 1295699 . 、、為、”罔、並藉由針軋（needle punching)法製造薄片化纖維 (單位面積重量：4〇〇g/m2、厚度：Kmm)。再將於95質量 分的硫甲基化酚一烷基間苯二酚一曱醛初期縮合物水溶液 (50%固形分）中已添加混合5質量分的熱膨脹性顆粒體 (i放勝囊型、松本微球粒（MatSum〇t〇mirc〇Spher)F—1QQ) 的含π液、以達到作為固形分50質量％含有量的程度含浸 於該薄片化纖維中、然後於乾燥室内一邊吸引一邊以110 C的溫度乾燥3分鐘並予前硬化製得纖維薄片。最後以2 i 〇 C的狐度熱壓40秒鐘成形予前硬化後的該纖維薄片、並一 邊限定厚度一邊使該顆粒體膨脹而製得1〇_厚的成形物。 除了實施例5中的熱膨脹性顆粒體以外，其他則相同 而製得10mm厚的成形物。 使用上述貝把例5及比較例3所得的試料、依照ρ μ v S S -302的水平賴法依序進行燃燒測試。其結果如表3 所示。 表3 成形物 燃燒測f 實施例5 不燃_ 比較例3 遲燃~ 根據表3、確定實施例c； α ^ ^ π 1 只他1幻b和比較例3相比具有良好燃 燒性。由此可認為因藉由埶膨胳 阳…恥脹顆粒體的膨脹效果填滿試 料纖維的空隙而使燃燒時試料内的空氣量減少。 [實施例6 ] 使用作為膨脹性顆粒體 (Matsumotomircospher)F -之取代實施例2之松本微球粒 1 〇〇之聚甲基丙烯酸酯珠粒 315986 27 1295699 (粒徑200至300 // m)中含浸正戊烷的發泡性珠粒、其他和 實施例2同樣的方法製得15_厚的成形物。該成形物的彎 曲測試結果係〇· 59MPa、作業性〇、吸音率（％)如表4所示。 表4 500Hz 1000Hz 2000Hz 4000Hz 38 60 81 93 [發明之功效] 而厂：：：明的纖維薄片中、藉由熱膨脹性顆粒體的膨脹 m#、因不使重量增A便能使纖維部 度、因此其彎曲強度大、且從彻闽、士 s丄 々门山 ^ , 低周波至向周波的廣範圍周 能呈現實現難燃化的預二片及其成形物、以及 物作為汽車哎建筚物的石立 再者、该纖維薄片或成形 域㈣的吸音材料或隔熱材料極其有用。 315986 28[Comparative Example 2] A general glass wool (unit weight: 6 重量) containing 20% by mass of a resol phenol resin initial condensate as a binder, was formed by a flame method at a temperature of 200 ° C for 60 seconds. g/m2, thickness 5 〇 mm) to obtain 315986 24 1295699 15 mm thick molded product. α was subjected to a bending test on the molded articles of the above-mentioned Examples 2, 3 and Comparative Example 2 for the II f i s rate and the ventilation resistance test. The test results are shown in Table 2. Table 2 Bending test of molded product (MPa) Operational property* Sound absorption rate (%) Ventilation resistance kPa·s/m 500 Hz 1000 Hz 2000 Hz 4000 Hz Example 2 Example 3 Comparative Example 2 0. 62 0. 58 0. 12 〇〇 X 40 43 21 63 65 35 84 87 66 95 97 80 0. 396 0.493 0. 488 *Operability 〇: During the forming operation, the fibers do not scatter and the handling properties are good. X · When forming, the dust from the glass flies, and the dust (glass) is easy to handle, which makes the handling property extremely poor and has an adverse effect on the human body. According to the results of Table 1, it was confirmed that the sample of Example 1 and the sample of Comparative Example 1 had a large sound absorption rate and a good bending strength as compared with a wide range of the number of cycles. The fiber of this type is shrunk by the expansion of the heat-expandable granules, and it is considered that the incident sound energy is reduced as the venting resistance value becomes larger. These can also be determined by the ventilation resistance value. According to the results of Table 2, it was confirmed that the samples of Example 2, Example 3, and the sample of Comparative Example 2 were significantly improved in bending test and sound absorption rate. Further, the difference in the ventilation resistance values of Example 2, Example 3, and Comparative Example 2 was not large, but the expected result of the improvement in the sound absorption rate was also obtained. 25 315986 1295699 [Example 4] The use of 55 mass% of polyester hollow fiber (denier · 4 dtex, hollow ratio M 5%, fiber length: 55 off), and 35 mass % of Pooh fiber (denier, · 7) · 5dtex, fiber length: 6〇_), and 1% by mass of rayon (fineness · 6dtex, fiber length · 55mm), the flaking of the mixed fiber, the needle punching method A thinned fiber (having a weight per unit area of 1 600 g/m 2 and a thickness of 15 mm) was produced. Further, 5 parts by mass of a nitrogen/niobium-containing flame retardant may be added to a 9 〇 mass fraction of a sulfomethylated phenol monoalkyl resorcinol-furfural initial condensate aqueous solution (45% by mass solids). The impregnation liquid of the silicone-based water-repellent agent of the mass fraction and the heat-expandable granules (microcapsule-type microspheres F-85) of 4 mass parts are impregnated to the extent of the content of the solid content of 6% by mass. In the flaky fibers, one side is then attracted to the inside of the drying chamber. The temperature of the crucible was dried for 4 minutes and pre-hardened to obtain a fiber sheet. a polyester fiber coated with a hot-melt adhesive (polyamide resin, melting point: 16 〇艽, particle size: 200 mesh all-pass) as a skin material after pre-hardening Non-woven fabric (manufactured by Spunbond, weight per unit area: 3 〇g/m2, thickness i5_), and finally hot-pressed at a temperature of 200 ° C for 6 〇 seconds, and the thickness of the thermal expansion granule is defined while limiting the thickness. The body is expanded to obtain a shaped body. The molded article has a property of being excellent in flame retardancy, water repellency, rigidity, and sound absorbing property. [Example 5] A flame retardant polyester fiber of 85% by mass of polyester hollow fiber (denier: 7 dtex, hollow ratio: 20%, fiber length: 75 mm), and 15% by mass (discussion: 4 dtex, fiber length) was used. : 55mm) The flaky fiber of the mixed fiber is 315986 26 1295699 . . . , and the flaky fiber is produced by the needle punching method (weight per unit area: 4〇〇g/m2, thickness: Kmm) Then, 5 parts by mass of heat-expandable granules (i will be added) will be added to 95 parts by mass of thiomethylated phenol monoalkyl resorcinol-furfural initial condensate aqueous solution (50% solids). The π-containing liquid of the capsule type, Matsumoto microsphere (MatSum〇t〇mirc〇Spher) F-1QQ) is impregnated into the exfoliated fiber to the extent of 50% by mass of the solid content, and then is dried in the drying chamber. The fiber sheet was dried at a temperature of 110 C for 3 minutes and pre-cured to obtain a fiber sheet. Finally, the fiber sheet was pre-hardened by hot pressing for 2 seconds at a temperature of 2 μC, and the thickness was limited while limiting the thickness. The granules were expanded to obtain a 1 〇 thick workpiece. Except in Example 5 A molded article having a thickness of 10 mm was prepared in the same manner as the heat-expandable granules. The samples obtained in the above Examples 5 and 3 were subjected to a burning test in accordance with the horizontal ruthenium of ρ μ v SS -302. The results are shown in Table 3. Table 3 Compressed burning test f Example 5 Non-combustible _ Comparative Example 3 Chiral igniting ~ According to Table 3, Example c was determined; α ^ ^ π 1 only 1 phantom b compared with Comparative Example 3 It is considered to have good flammability. Therefore, it is considered that the amount of air in the sample during combustion is reduced by filling the gap of the sample fiber by the expansion effect of the swellable granules. [Example 6] Use as expansion property The foaming property of the immersion of n-pentane in the granules of the granules of the granules of the granules of the granules of the granules of the granules of the granules of the granules of the granules of the granules of the granules of the granules of the granules The beads and the other molded articles were obtained in the same manner as in Example 2. The bending test results of the molded articles were MPa·59 MPa, workability 〇, and sound absorption rate (%) as shown in Table 4. Table 4 500 Hz 1000Hz 2000Hz 4000Hz 38 60 81 93 [Effect of invention] And factory::: Ming In the fiber sheet, by the expansion m# of the heat-expandable granules, the fiber portion can be obtained without increasing the weight, so that the bending strength is large, and from the 闽 闽, 士 丄々 山 ^ ^ , low cycle To the wide range of the circumference of the cycle, it is possible to present a pre-two piece which is difficult to ignite and a molded object thereof, and as a stone stand for the automobile building, the sound absorbing material or the heat insulating material of the fiber sheet or the forming field (4) is extremely it works. 315986 28