201120080 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種軟質聚胺基曱酸乙醋發、泡體，在用於廣泛 =途的軟質聚胺基甲酸乙泡體中，即使長期暴露於太陽光等 ίϊΓί泡體的也不太會變色的軟f聚胺基曱酸乙泡體，特 魏胸解衣物、衛輯及紙尿布物生用品、化妝粉 撲4化妝品用、鞋子、寢具、結構積層、傢俱等。 【先前技術】 習知軟質聚祕㈣乙S旨發泡體由於綠性 於·等汽車及傢俱、胸墊及肩墊等二=等@ =製==曱苯二異氰_旨⑽)等芳香族系的聚異細旨。 ^疋’使用方香姆魏_而得_聚胺基f酸⑽發泡體 易因太陽规輕色關題。聚胺基情乙g旨發泡體變色盆 因；認為是由於紫外線而導致苯環的酿化，作為防2 t Ϊ ί i有人，使用脂肪族聚異氰酸0旨或脂環族聚異氰酸 醋代替方雜聚異氰麵的軟質聚絲情乙轉泡體。，、 例如，專利文獻1中記載之對於脂肪族 =用特剌條狀賊，翻讀2巾_之3^酸t 其中作為異氰酸酯的NCO不與芳香贿直 得到 曱酸乙酯的色調安定性。 」付到水胺基 有Λ下f題：⑴使用脂肪族或脂環族聚異 孔以及塌陷的問題，或具有獨立氣泡 問題，（2)若不添加變色防止劑，則發=斤 另外，最近有人揭示如專利文獻問通專 (卿，併用作為催化劑的錫_b劑與3級胺 4 201120080 基乙基趟以及/或是三伸乙二胺。 但是，前賴叙_在於：缺乏供給奴性 咼價的IPDI等特定的脂環族異氰酸酯。 ^ ;使用 利文獻4所示’揭示了使職脂肪顧氰S曼㈣ ^改質有機聚異氰酸敝成物而成型發泡體的^ 之醋;鹽時，成型 先前技術文獻 k其問遞。 專利文獻 專利文獻1 :日本特開昭50-64389號公報 專利文獻2 :日本特開昭52_128997號公報 專利文獻3 .日本特開平ι〇_36543號公報 專利文獻4 :日本特開2005-48038號公報 【發明内容】 [發明所欲解決的問題] 本發明的目的在於提供—種適合f知生產狀況的軟質聚胺某 曱旨發泡體，可解決習知軟質聚胺基 = 引起的變色、前述之反應性安定性低而 軋孔狀態、以及焦化之產生等問題。 [解決問題之技術手段] 本案發明人仔細研究的結果發現：本發明可解決前述問題， 具有優異的耐變色性，且具備適於f知生產狀況之成形 性的軟質聚胺基曱酸乙酯發泡體用組成物。 詳言之，本發明如以下⑴〜⑻所示。 (1)種軟質聚胺基甲酸乙醋發泡體的製造方法，使有機聚里 =巧）、多元醇⑻、催化劑(c)、發泡劑⑼、以及整泡劑⑹ 、此δ液反應發泡、硬化而得到軟質聚胺基甲酸乙酯發泡體，該 201120080 在於：該有機聚異說酸醋成分⑷使用單元醇和脂 機聚異氰的==改質有 氰酸酉旨組成合Ϊ·。酉曰所纽成的服基懷改質有機聚異 今右^載之軟f聚胺基f酸乙s旨發泡體的製造方法，兑中 法，載f軟質聚胺基曱酸乙酉旨發泡體的製造方 it夕讀⑼之標稱平均官能團數〜6 子篁為50〜20000的多元醇⑻所組成。 则干私 缴、/=)二(3)中任—者記載之軟質聚胺基甲酸乙S旨發泡體的 ϊΐί法，其中在該異她旨(A)以及該多元醇⑻中的任 者中添加受阻胺系光安定劑而加以使用。 者或兩 制、生2H〜i4)中任一者記載之軟質聚胺基曱酸乙酷發泡體的 :二其懷化劑(c)使用〗，8-二氮雜娜，‘= 其甲細成型品’使用（1)〜(5)中任一者記載之軟質聚胺 I甲酸乙泡體的製造方法得到的軟質聚胺基甲酸2= 其甲H =生用成型品’使用⑴〜(5)中任一者記載之軟質聚胺 I甲酸乙泡體的製造方法得到的軟質聚胺基甲酸 (二)-種化妝用成型品，使用⑴〜(5)中任一者 I甲酸乙轉泡體的製造方法得到的軟質聚胺基甲酸 田缺(9)種鞋用成型品，使用⑴〜(5)中任一者記載之軟曾取π其 甲酉夂泡體的製造方法得到的軟質聚胺基甲酸^;女基 [對照先前技術之功效] i /包體 根，本發明的製造方法’可得到一種軟質聚胺 跑體，其對独彳刪題之料線、膽及熱具有優異 6 201120080 f續孔構造。並且’根據本發明的製造方法，可 节、太亂酸醋而造成的作業環境惡化，且經歷長時間 利用於商社廣泛的崎巾。 ㈣締其T期待此夠 要的物i 塾衣物及鞋子等用途中，壓縮永久變形係為重 好，適I該ίίί本發鴨到的發泡體之壓縮永久變形非常良 【實施方式】 下找細地說3林發明。本發日种使用的械聚昱氰_旨 早7^醇和脂肪族系以及/或是脂環族系二里氰酸S旨所组成 的，基甲酸自旨改#有機聚異氰酸g旨組成 j 經基的醇和脂肪«以及/或是脂環族系二異2 甲酸醋改質有機聚異氰酸g旨組成物(A2) 命s j 用其他有機聚異氰酸酿。 k目應需求亦可使 2基f義域物愤關含錄化合 ==物的單元醇以及含2個以塊的ΐ = <低分子量脂肪族醇> 單元醇： 曱醇、乙醇、丙醇、異丙醇、異構丁醇、戍 細1、2-乙基己醇、以及碳原子數10〜2G的月旨肪族己^。、庚醉、 含2個以上經基的醇： 、醇 乙二醇、1，2-丙二醇、U_丙二醇、u_丁二醇 ，-丁二醇、1，5-戊二醇、新戊二醇、1>6_己二醇、’二/、 甲基1，5-戊二醇、2-甲基-2-丙基1，3-丙二醇、22 二醇、3-醇、2-乙基己二醇、2,2,4_三甲基Μ·戊二醇、1，3_丙二 醇、U0-癸二醇、十二烷1>2_二醇、2_M_丁二了甲基1，6-己一 兩穴醇、丙三醇、丁三醇、2_羥曱基冬甲基1冰丙二n?-二每、三舒基乙烧、三鮮基、季戊四醇、乙二醇 201120080 峻或是芳基轉、_ & •醇、三乙二醇 以及四 乙二醇。 内二醇單烧基趟、二乙. :脂環式醇；^ 單元醇： 環戊醇、環p 己醇、薄荷醇、甲基環己醇、三甲基環己醇、4-第三丁基環 含2個以、異冰片、以及2-羥基萘烷。 口，己二‘基 -U，3,3-四甲基·環丁二醇及1，4-環己二醇、2,4_二經基 甲燒、2,2-雙⑷經基^己芙又丙=曱==烧、雙_(4-經基環己基 戊燒、糠醇、四氫糠& ;甲郁-經基環己基> 烷。 吁又匕甲基降坎烷、以及二羥甲基-三環癸 <鬲分子多元醇> 使環氧乙烧、環氧元醇， 的起始化合物、例如水、應性氫原子 依序添加，藉_方^^： 態或 或是與其他二醇、二魏或？本身的、以及/ 麵=成聚=二=:。該 的醇t;r 經基化合物宜含有至少碳原子數^ 作為製造腺基甲酸醋改質有播命里枭於4上、& 而使用的二異氰_，只要是脂戈以=材料 可，並沒有特別限制。作為脂肪族二 的、=1酉久酉旨即 基二異氰酸酯(HDI)、離胺酸 ϋηη曰的例子’有六亞τ 另外’作為脂環族二異氛酸“厂子：;==旨 201120080 (IKDI)、虱化一苯基甲烧二異氰酸g旨(氫化、氫化二曱苯二異 氰酸醋(，化XDI)、環己烧二異氰酸醋、曱基S己烧二異氮酸脂' 以及一環己基甲烧二異氰酸g旨等二異氰酸自旨類。而且，本發明中 可使?具有料環’但異級g旨基;j；與料環直接結合的二曱苯 一異氰S«(J曰(XDI)、以及亦屬於脂肪族二異氰酸酯的四曱基二甲苯 二異氰酸酯(TMXDI)。本發明中，在考量到商業製造的情況下， 因為其生產量格而適合使用腹。在此由於腦的蒸氣壓非 t低二所以在考置到作業環境的情;兄下，宜將所使用的腺基曱酸 西曰改質有機χκ異氣酸g旨組成物中所含的游離Η〗)〗調整至1質量％ 以下。 =為製造由含醇性羥基化合物和脂肪族系以及/或是脂環族系 二異氰酸醋構成的脲基曱酸醋改質有機聚異氰酸醋組成物時所使 用的催化知彳，亦可使用已經揭示的任一驗性化合物。本發明中適 ^的催化劑為羧酸，例如碳酸、蟻酸、醋酸、丙酸及任意取代的 苯:酸之驗金;|、驗土類金屬、以及氧化驗土類金制^。根據 抑制反應性、副產物之觀點，特別是羧酸鍅以及羧酸鍅的鹽最為 合適。其他催化劑為三級胺，例如三甲胺、三乙胺、三丁^、二 甲基苯甲胺、1，4-二氮雜雙環_辛烧、！,5_二氮雜雙環_壬&、四^ :一f、四甲基丙二胺、以及雙善二甲基胺乙基醚。如酚鈉的酚 j 是適當的催化劑。亦可使用含氮的芳香族 =t物，例如吡啶、單C1〜C4_烷基吡啶、二曱基吡啶、n_二甲 基胺基•吡啶、二乙基吡啶、以及三甲基吡啶。（：1〜〇：4_^烷基-吡 咯、C1〜C4-N-烷基-吼π各啉、C1〜C4_N_烷基_吼咯咬、C1〜C4_N_ ^基♦坐、C1〜C4-N-烧基+坐、Cl〜C4-N-烧基♦坐琳、C1〜 烷基-咪唑啶、C1〜C4-N-烷基-U，3-三唑、C1〜C4_N_烷基 德，二T坐；任意烧化的°密°定、缝嗪、U，3-三氮雜苯、三氮 雜本、1，3,5-三氮雜苯；任意烷化的喹啉、異喹啉、 以 吖啶也报合適。 其田ίΪ元醇和脂肪族系以及/或是脂環族系二異氰_組成的腺 土甲义酉曰改質有機聚異氰酸酯組成物(Α1)，與由含有2個以上羥基 201120080 的醇和脂肪族系以及/或是脂環族车_ 改質有機聚異氰酸驗成物(A2)、：、= 旨構成的脲基甲酸醋 為(Α1)/(Α2) = 80/20〜30/70，而最理⑯的t率無特別限定’但宜 40/60。當(A1)的比率超過上限，為(A1)/(A2)=6_〜 當⑽的比率超過上限，貝，^能的硬度會變高。另外， 高，成形性惡化。 成有機聚異氰酸醋⑷的變 均分ΐί 醇(Γ標_官_2〜6，數目平 為單體的多元醇，除了含水。具，而言’作 油、三羥甲基丙烷、己三醇、乙二p 一一知二一丙一醇、甘 聚乙二醇及聚丙二醇作為起始劑^之外’可以 乙烯等的自由基聚合而產生^错由 *改免多兀醇、以及聚伸丁基醚多元醇。另n虱 Ι3Π曼與乙二醇、丁二醇、三經甲基丙燒、以及曰【二醇°等 醇、含石粦多元醇、以及聚_多元醇等。 该寻夕兀醇中較理想者為：標稱平均官能 〜2_的尾端含有！級以及/或是2 _基的軸多元^里曰= Ϊ ί ί ί ί疋醇、標稱平均官能團數2〜6且當量_〜2，_ 5 :或“聚i旨多元醇、以及當量·〜6，_的聚伸丁 夕’： Ξ適ΐί二2外：的，旨二醇等。該等多元醇可‘應ίί 向週田選擇，另外亦可混合2種以上使用。 、 本發明對於所使用的催化劑(c)無特別限定，本發 土 f酸乙S旨發泡體的製造_通常使用的胺㈣化劑、 有/勝基的胺及其衍生物均可使用。作為胺系催化劑， 比皿和的3級胺類，特別是三伸乙二胺最為合適，此 不者有：三f基胺基乙基乙醇胺、二f基乙基乙基乙醇胺、二/ 201120080 f胺基嗎啉、三乙胺、μ異丁基_2_甲基咪唑、曱基嗎 啉、二一乙醇月安、四甲基六亞曱基二胺、二甲基環己胺、四甲^ 一月^、二曱基胺基乙心辰嗓、四甲基乙二胺、三(二甲胺丙二 二月f、二曱基二苯乙二酮胺、二甲基胺基乙氧乙醇、二曱二 基己醇、以及曱基祕料等。另外’亦可採用—般使 甲脒基的胺及其衍生物。作_具有m基的胺及其衍生物了 使用1，8-—氮雜雙環[5，網十〜7-稀、1，5·二氮雜雙環[4,3,〇]壬稀 _5、6-二丁基絲-1，8_二氮雜雙環[5,4,〇]十一_7_稀等。 雙環錢，可示列出者有：1>8-二氮雜雙環[5,蝴十一7_稀(以^ 稱為DBUy以及1，5-二氮雜雙環[4,3,0]壬烯_5、6_二丁基胺基'心 -氮#雙環[5,4,0]十--7-稀等。此外’亦可使用弱酸的驗金屬鹽、 以及二聚物化催化劑等。作為金屬催化劑，宜使用辛酸亞錫、二 醋酸二丁H彳織二丁錫、以及其他通f在聚胺基甲酸乙醋 發泡體中使用的錫系催化劑。 本發明中，為了得到良好的反應性平衡、氣孔均勻、獨立氣 /包少、以及作為女疋的發泡體之泡沫，上述催化劑中使用Dbu與 辛酸亞錫最為合適。 作為本發明中使用的發泡劑(D) ’可使用通常在胺基曱酸乙酯 啦泡中所使用之公知的發泡劑。例如，作為物理發泡劑，可列舉 出者有.戊烧、己烧等碳氫化合物、HCFC-141b、HCFCM23、 HCFC-22、HFC-245fa、HFC-365mfc、HFC-134a 等之所謂含有代 替氟氣碳的鹵化烴等，作為化學發泡劑，可列舉出者有：水及有 機酸等。另外亦可利用氣體加載裝置在原液中混入溶解空氣、氮 氣、以及二氧化碳等而使用。該等發泡劑亦可併用2種以上而使 用’其適當的使用量為多元醇的1〜50質量％。 作為本發明中使用的整泡劑(E)，可使用L-5309、L-5366、 Y-10366、L-3151、L-5420、L-6202B(Momentive 製）、F-242T、F-303、 F-703(信越化學工業製）、SH-192、SH-193、PRX-607、SRX-280A、 SF-2914、F-122、SF-2962(Dow Coming Toray Silicone Co.，Ltd.製）、 B-8300、B-4113LF(Evonik Japan 製）、DC-5169、DC-193(Air Products 201120080 優異的耐變色性。具體而言，有_抗氧化劑、 系光女定劑(hmdered amine light stabilize^為理相 可列舉出者有：雙(1总6,6_五甲基.4«基)癸^ =而吕’ 導:面活性劑、著色劑、 ϊί：：1π^^：：ίΞίΙΙ^^-^ 器中儲存或調製完成的聚異氰容 ==鑄;:=中：=劑使 15〇 - 下等’則無此必要。根據生產效率之觀v，、l|;=; 12 201120080 明中注入後3〜8分鐘内可進行脫模，但為了減少不良率，亦可任 意設定適於生產設備之條件的脫模時間。脫模後的產品可直接使 用，亦可以一般公知的方法在壓縮或減壓下破壞氣孔，使製品的 外觀及尺寸安定化。 [實施例] 以下，更進一步敘述本發明的具體實施例，當然本發明並不 僅限定於本實施例。 〔脲基曱酸酯改質聚異氰酸酯的製造〕 <合成例1> 在具有攪拌機、溫度計、冷卻器及氮氣導入管的容量1L的反 應器中加入950g的六亞曱基二異氰酸酯(扭^ :日本聚氨酯工業公 司製)以及50g的異丙醇’在9〇。〇下進行2小時的胺基甲酸乙酯化 反應。用FT-IR分析反應產物而發現羥基消失。接著加入〇 lg的 辛酸氧錯(第1「稀有元素化學工業公司製），在贼下反應3小時。 用FT-IR及13C-NMR分析反應產物而發現胺基甲酸乙酯基消失。 接著’力〇入O.llg的JP-508(城北化學公司製），在5〇°c下進行1小 時終止反應。終止反應後的反應產物之異氰酸酯含量為4〇 46〇/〇。 ^該反應產物在。14(TC · 40Pa下進行薄膜蒸顧，得到異氰酸醋含 1為19.5%，25C下的枯度為lOOmPa.s，游離的六亞甲基二異氰 酸酯含量為0.1%，色號為20APHA的「脲基甲酸酯改質聚異氰酸 酯-1」。用FT-IR以及I3c-NMR分析「脲基曱酸酯改質聚異氰酸 酯-1」’胺基甲酸乙酯基之存在無法確認，脲基甲酸酯基之存在則 被確認。另外，確認有微量級的脲二酮基以及異三聚氰酸酯基。 <合成例2 > 除了加入95〇g的六亞曱基二異氰酸酯田即及5〇g的孓曱基 戊二醇以外^係採用與合成例丨同樣的方法，而得到「脲基曱酸 酯改質聚異氰酸酯-2」（異氰酸酯含量191%，25它下的粘度 1720mPa*s，游離六亞甲基二異氰酸酯〇，色號2从丹仪 <合成例3> 除了加入950g的六亞甲基二異氰酸酯(HDI)及5〇g的丁醇以 13 201120080 外，係採用與合成例1同樣的方法，而得到「脲基甲酸酯改質聚 異氰酸酯-3」（異氰酸酯含量19·0%，25°c下的粘度9〇mPaes，游離 六亞曱基二異氰酸酯0.1%，色號20APHA)。 <合成例4> 除了加入950g的六亞甲基二異氰酸酯(HDI)& 5〇g的 PTG-25〇(保土谷化學公司製)以外，係採用與合成例1同樣的方 法，而得到「脲基甲酸酯改質聚異氰酸酯_4」（異 ’坑下的減1770mPa.s，游離六亞甲基二異氰酸醋 0·1%，色號 20APHA)。 <異氰酸酯調製例1>201120080 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a soft polyamine phthalic acid vinegar hair, a foam body, which is used in a wide range of soft polyurethane foams, even for a long period of time. Soft f polyamine bismuth citrate exposed to sunlight, etc., which is less likely to change color, special Wei chest disguise clothing, Wei and paper diapers, cosmetics puff 4 cosmetics, shoes, bed With structure, structural layers, furniture, etc. [Prior Art] Conventional soft poly-secret (4) B-type foams due to greenness, etc., such as automobiles and furniture, chest pads and shoulder pads, etc. @=制== benzene diisocyanide_(10)) The purpose of aromatics is different. ^疋' Use Fang Xiangmu Wei _ _ polyamine-based f acid (10) foam Easy to light due to the sun rules. The polyamine-based substance is a color-changing pot of the foam; it is considered that the benzene ring is brewed due to ultraviolet rays, and as an anti- 2 t Ϊ ί, some people use aliphatic polyisocyanate or alicyclic poly Cyanic acid vinegar replaces the soft polyether Ethylene bromide of the heteropolyisocyanate. For example, in Patent Document 1, for the aliphatic group = a special strip-shaped thief, the 2 towels are read over, and the NCO which is an isocyanate does not form a tonality with ethyl citrate. . "After the addition of the amino group, there are sub-questions: (1) the use of aliphatic or alicyclic polyisotropes and collapse problems, or the problem of independent bubbles, (2) if no discoloration inhibitor is added, then = kg Recently, it has been disclosed as a patent document, and it is used as a catalyst for tin-b agent and tertiary amine 4 201120080-ethyl hydrazine and/or tri-ethylenediamine. However, the former 赖 _ lies in: lack of supply Specific alicyclic isocyanates such as IPDI, which are slavish valences. ^ ; Use of the literature shown in the literature 4 to reveal the formation of a foam of the organic fat polyisocyanate. In the case of the vinegar, the salt is formed by the prior art. The patent document 1 is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] An object of the present invention is to provide a flexible polyamine which is suitable for the production state. Body, can solve the conventional soft polyamine base = cause Problems such as discoloration, low reactivity stability, and occurrence of coking, etc. [Technical means for solving the problem] As a result of careful study by the inventors of the present invention, it has been found that the present invention can solve the aforementioned problems and has excellent discoloration resistance. Further, the composition for a soft polyamine phthalic acid ester foam which is suitable for forming the moldability in a production state is provided. In detail, the present invention is as shown in the following (1) to (8). (1) A soft polyamine group The method for producing a formic acid ethyl sulphate foam is obtained by reacting an organic condensate, a polyol (8), a catalyst (c), a foaming agent (9), and a foam stabilizer (6), and the δ liquid is foamed and hardened to obtain a soft polymer. The urethane foam, the 201120080 is: the organic polyisodide vinegar component (4) uses a unit alcohol and a fat machine polyisocyanine == modified cyanate hydrazine composition. The method of manufacturing the soft-f-poly-amino-f-acid s-shaped foam of the genus of the genus of the genus The manufacturer of the foam is composed of a polyol (8) having a nominal average functional group number of ~6 and a subunit of 50 to 20,000. In the case of the soft polyurethane, which is described in the second paragraph (3), the soft polyurethane succinate foam is described in the above, and any of the polyols (A) and the polyol (8) A hindered amine light stabilizer is added and used. The soft polyamine bismuth citrate foam described in either of the two systems and the raw materials 2H to i4): the second of its medicinal agent (c), 8-diazepine, '= its armor The fine molded product 'soft polyuretic acid 2 obtained by the method for producing soft polyamine I formic acid vesicles according to any one of (1) to (5) = its nail H = green molded product 'use (1) ~ (5) A soft polyaminocarbamic acid (II)-form cosmetic molded article obtained by the method for producing a soft polyamine I formic acid ocyanate according to any one of (1) to (5), wherein the formic acid B is used. A flexible polyurethane formic acid obtained by the method for producing a blister body (9) is a molded article for shoes, which is obtained by using any of the methods (1) to (5). Soft polyaminocarbamate; female base [controlling the efficacy of the prior art] i / inclusion root, the manufacturing method of the present invention can obtain a soft polyamine running body, which has a separate line of material and biliary The heat has an excellent 6 201120080 f continuous hole construction. Further, according to the manufacturing method of the present invention, the working environment caused by the sorrow and vinegar is deteriorated, and the kawasaki which is widely used in the company for a long time is experienced. (4) ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ Succinctly said 3 Lin invention. The mechanical polycyanide used in this invention is composed of an early alcohol and an aliphatic system and/or an alicyclic isocyanic acid. The constituents of the j-based alcohol and fat «and/or the alicyclic diiso 2 carboxylic acid vinegar modified organic polyisocyanate g (A2) sj are brewed with other organic polyisocyanates. The k-mesh should also be required to make the 2 base f sense domain angrily contain the unit alcohol of the compound == and the block containing ΐ = <low molecular weight aliphatic alcohol> unit alcohol: sterol, ethanol, propanol , isopropanol, isobutanol, quinone fine 1, 2-ethylhexanol, and a carbon atom number of 10~2G. , Geng drunk, alcohol containing more than 2 groups: alcohol, ethylene glycol, 1,2-propanediol, U_propylene glycol, u-butanediol, butanediol, 1,5-pentanediol, neopentane Glycol, 1>6-hexanediol, 'di/, methyl 1,5-pentanediol, 2-methyl-2-propyl 1,3-propanediol, 22 diol, 3-alcohol, 2- Ethylhexanediol, 2,2,4-trimethylsulfonium pentanediol, 1,3-propanediol, U0-decanediol, dodecane 1> 2-diol, 2_M_butadimethyl 1,6-hexa-and-two-alcohol, glycerol, butyl triol, 2-hydroxyindole winter methyl 1 ice-propylene di n?-di, tris-succinyl, trisyl, pentaerythritol, ethylene Alcohol 201120080 Jun or aryl, _ & • alcohol, triethylene glycol and tetraethylene glycol. Internal diol monoalkyl hydrazine, diethylene. : alicyclic alcohol; ^ unit alcohol: cyclopentanol, cyclop-hexanol, menthol, methylcyclohexanol, trimethylcyclohexanol, 4-third The butyl ring contains 2, isobornrazol, and 2-hydroxydecalin. Mouth, bis-yl-U,3,3-tetramethylcyclobutanediol and 1,4-cyclohexanediol, 2,4-di-carbyl, 2,2-bis(4)己芙和丙 = 曱 = = burning, bis (4-cyclohexyl hexyl pentylene, decyl alcohol, tetrahydro hydrazine & dimethyl thio-perylcyclohexyl) alkane And dimethylol-tricycloquinone <鬲 molecular polyol> The starting compound of epoxy bromide and epoxy diol, such as water and a hydrogen atom, are sequentially added, by means of _^^: Or with other diols, diwe or ? itself, and / face = poly = two =: The alcohol t; r via a base compound preferably contains at least a carbon number ^ as a manufacturing gland formic acid vinegar The quality of the diisocyanate used in the sequel is 4, and the diisocyanate used is not limited as long as it is a fat-based material. (HDI), an example of lysine ϋηη曰 'has six τ τ and 'as alicyclic diiso-acid acid' factory:; == 201120080 (IKDI), bismuth phenyl ketone diisocyanate g Purpose (hydrogenation, hydrogenation of diphenylbenzene diisocyanate (XDI), cyclohexane Cyanic acid vinegar, sulfhydryl succinyl diisoxamate', and monocyclohexyl succinyl diisocyanate g are equivalent to diisocyanate. Moreover, in the present invention, it is possible to have a ring of materials. g; base; diphenyl benzene monoisocyanate S « (J 曰 (XDI), and tetradecyl xylene diisocyanate (TMXDI) also belonging to the aliphatic diisocyanate. In the present invention, In the case of commercial manufacturing, it is suitable for the use of the abdomen because of its production capacity. Here, since the vapor pressure of the brain is not low, it is suitable for the working environment. Under the brother, the gland base should be used. Η 曰 曰 曰 曰 χ χ χ χ 调整 调整 调整 调整 调整 调整 调整 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = The catalyzed knowledge of the urea-based phthalic acid vinegar modified by the family of diisocyanate vinegar to modify the organic polyisocyanate composition can also use any of the compounds which have been disclosed. The catalyst is a carboxylic acid, such as carbonic acid, formic acid, acetic acid, propionic acid, and an optionally substituted benzene: acid gold test; |, soil testing The genus and the oxidized soil-based gold system are most suitable from the viewpoints of inhibition of reactivity and by-products, particularly cerium carboxylate and cerium carboxylate. Other catalysts are tertiary amines such as trimethylamine and triethylamine. Tributyl, dimethylbenzylamine, 1,4-diazabicyclo-octane, !,5-diazabicyclo-oxime &, tetra-:-f, tetramethylpropanediamine, and Shuangshan dimethylamine ethyl ether. Phenol j such as sodium phenolate is a suitable catalyst. Nitrogen-containing aromatic = t substances such as pyridine, mono C1~C4_alkylpyridine, dimercaptopyridine, N-dimethylamino]pyridine, diethylpyridine, and trimethylpyridine. (:1~〇:4_^alkyl-pyrrole, C1~C4-N-alkyl-吼π-polyline, C1~ C4_N_alkyl_吼 吼 bit, C1~C4_N_ ^ base ♦ sitting, C1~C4-N-alkyl group + sitting, Cl~C4-N-alkyl group ♦ sitting, C1~ alkyl-imidazole, C1~ C4-N-alkyl-U,3-triazole, C1~C4_N_alkylde, two T-seat; optionally sintered, sulphur, sulphide, U,3-triazabenzene, triaza 1,3,5-triazabenzene; any alkylated quinoline, isoquinoline, and acridine are also suitable. A modified organic polyisocyanate composition (Α1) composed of a glutamic acid and an aliphatic family and/or an alicyclic diisocyanine _, and an alcohol and an aliphatic group containing 2 or more hydroxyl groups 201120080 And/or an alicyclic car _ modified organic polyisocyanate test (A2), :, = ureido formic acid vinegar is (Α1) / (Α2) = 80/20~30/70 However, the t-rate of the most reasonable 16 is not particularly limited 'but 40/60. When the ratio of (A1) exceeds the upper limit, it is (A1) / (A2) = 6_~ When the ratio of (10) exceeds the upper limit, the hardness of the shell can be increased. In addition, it is high and the formability is deteriorated. The organic polyisocyanate vinegar (4) is divided into aliquots of alcohols (Γ _ _ _2 ~ 6 , the number of monomer is a single monomer, in addition to water. With, for example, 'oil, trimethylolpropane, Glycerol, Ethyldi-P-Il-Di-propanol, Glycol Polyethylene Glycol, and Polypropylene Glycol as Starting Agents can be generated by free radical polymerization of ethylene or the like. And polybutylene ether polyols. Another n虱Ι3 Πman with ethylene glycol, butanediol, trimethyl propyl ketone, and 曰 [diol diol and other alcohols, sarcophagus polyols, and poly _ Alcohol, etc. The ideal one is as follows: the nominal average functional ~2_ tail contains a ! level and / or 2 _ base axis multivariate ^ 曰 Ϊ ί ί ί ί 疋The average number of functional groups is 2 to 6 and the equivalent is _~2, _ 5 : or "polyi is the polyol, and the equivalent of ~6, _ of the condensed Ding Xi": Ξ ΐ ΐ 2 2: The above-mentioned polyols may be selected from the above, and may be used in combination of two or more kinds. The catalyst (c) to be used in the present invention is not particularly limited, and the present invention is a foam of the acid Manufacturing _ commonly used amine (tetra), amine / amine and its derivatives can be used. As an amine catalyst, the third class of amines, especially triethylene glycol diamine, the most suitable, this does not have : trif-aminoethylethanolamine, di-f-ethylethylethanolamine, bis/201120080 f-aminomorpholine, triethylamine, μ-isobutyl-2-methylimidazole, decylmorpholine, two Ethanol, tetramethylhexamethylenediamine, dimethylcyclohexylamine, tetramethylamine, January, dimethylaminoamine, tetramethylethylenediamine, tris(dimethylamine) In February and February, f, dimethyldiphenylethylenedione, dimethylaminoethoxyethanol, dinonylhexyl alcohol, and sulfhydryl-based secrets, etc. Amines and their derivatives. Used as an amine with a m group and its derivatives using 1,8-azabicyclo[5, a network of ten to 7-dilute, 1,5,diazabicyclo[4,3 ,〇]壬 _5,6-dibutyl silk-1,8_diazabicyclo[5,4,〇]11_7_稀等. Double ring money, can be listed as: 1> 8-diazabicyclo[5, 蝴蝶 eleven 7_ dilute (referred to as DBUy and 1,5-diazabicyclo[4,3,0]nonene_5 6-dibutylamino group 'heart-nitrogen #bicyclo[5,4,0]de--7-thin, etc. In addition, 'metal salt of weak acid, dimerization catalyst, etc. can also be used. As a metal catalyst, It is preferable to use stannous octoate, dibutyltin diacetate, dibutyltin, and other tin-based catalysts used in the polyurethane foam. In the present invention, in order to obtain a good balance of reactivity, Uniform pores, independent gas/small package, and foam as a foam of the privet, the most suitable use of Dbu and stannous octoate in the above catalyst. As the foaming agent (D) used in the present invention, it can be used usually in an amine. A known blowing agent used in the ethyl phthalate blisters. For example, as the physical foaming agent, a so-called content such as a hydrocarbon such as a pentylene or a hexane, or a HCFC-141b, HCFCM23, HCFC-22, HFC-245fa, HFC-365mfc, or HFC-134a may be mentioned instead. Examples of the chemical foaming agent include halogenated hydrocarbons of fluorine gas and carbon, and water and organic acids. Alternatively, a gas loading device may be used in which a dissolved air, nitrogen gas, carbon dioxide, or the like is mixed in the raw liquid. These foaming agents may be used in combination of two or more kinds, and the appropriate amount thereof is from 1 to 50% by mass based on the polyol. As the foam stabilizer (E) used in the present invention, L-5309, L-5366, Y-10366, L-3151, L-5420, L-6202B (manufactured by Momentive), F-242T, F-303 can be used. , F-703 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH-192, SH-193, PRX-607, SRX-280A, SF-2914, F-122, SF-2962 (manufactured by Dow Coming Toray Silicone Co., Ltd.) , B-8300, B-4113LF (made by Evonik Japan), DC-5169, DC-193 (Air Products 201120080) Excellent discoloration resistance. Specifically, there are _ antioxidants, hmdered amine light stabilizers. ^ For the sake of reason, there are: bis (1 total 6,6_pentamethyl.4« base) 癸^ = and Lu's guide: surfactant, colorant, ϊί::1π^^:: ίΞίΙΙ ^^-^ The polyisocyanine content stored or modulated in the device == casting;:=medium:=agent makes 15〇-lower class' is not necessary. According to the production efficiency v, l|;=; 12 201120080 Demolding can be carried out within 3 to 8 minutes after injection in the middle of the Ming Dynasty. However, in order to reduce the defect rate, the demolding time suitable for the conditions of the production equipment can be arbitrarily set. The product after demolding can be used directly or generally known. Method of destroying under compression or decompression The pores stabilize the appearance and size of the product. [Examples] Hereinafter, specific examples of the present invention will be further described. Of course, the present invention is not limited to the examples. [Manufacture of urea-based phthalate modified polyisocyanate <Synthesis Example 1> 950 g of hexamethylene diisocyanate (twist: manufactured by Nippon Polyurethane Co., Ltd.) and 50 g of isopropyl were placed in a reactor having a capacity of 1 L with a stirrer, a thermometer, a cooler, and a nitrogen gas introduction tube. The alcohol was reacted at 9 Torr for 2 hours, and the reaction product was analyzed by FT-IR to find that the hydroxyl group disappeared. Then, octyl octanoate was added (the first "rare element chemical industry company" The reaction was carried out for 3 hours under thieves. The reaction product was analyzed by FT-IR and 13C-NMR, and it was found that the urethane group disappeared. Then, the force was injected into O.llg's JP-508 (manufactured by Seongbuk Chemical Co., Ltd.). The reaction was terminated at 5 ° C for 1 hour. The isocyanate content of the reaction product after termination of the reaction was 4 〇 46 〇 / 〇. ^ The reaction product was subjected to film evaporation at 14 (TC · 40 Pa to obtain isocyanic acid vinegar 1 is 19.5%, under 25C Dry degree lOOmPa.s, free hexamethylene diisocyanate content of 0.1%, the color number 20APHA "allophanate modified polyisocyanate -1." The presence of the "ureido phthalate-modified polyisocyanate-1" urethane group was not confirmed by FT-IR and I3c-NMR, and the presence of the allophanate group was confirmed. Further, it was confirmed that there were a trace amount of a uretdione group and an isomeric cyanate group. <Synthesis Example 2 > In addition to the addition of 95 〇g of the hexamethylene diisocyanate field and 5 〇g of decyl pentane diol, the same method as in the synthesis example was used to obtain "ureido ruthenium". Acid ester modified polyisocyanate-2" (isocyanate content 191%, 25 viscosity under it 1720 mPa*s, free hexamethylene diisocyanate oxime, color No. 2 from Danyi < Synthesis Example 3) except addition of 950 g of six Methylene diisocyanate (HDI) and 5 g of butanol were used in the same manner as in Synthesis Example 1 except that the amount of the isocyanate content was 19: 0%, viscosity at 25 ° C 9 〇 mPaes, free hexamethylene diisocyanate 0.1%, color No. 20APHA). <Synthesis Example 4> In addition to 950 g of hexamethylene diisocyanate (HDI) & In the same manner as in Synthesis Example 1, except for PTG-25® (manufactured by Hodogaya Chemical Co., Ltd.), "ureourete-modified polyisocyanate_4" was obtained (subject to a reduction of 1770 mPa under the pit). s, free hexamethylene diisocyanate 0. 1%, color No. 20APHA) <isocyanate preparation example 1>
在具有餅機、溫輯、冷卻狀統導人管的容量il的反 中加入w〇g的脲基曱酸酯改質聚異氰酸酯_丨以及〇8g的 a旦在25 C下攪拌混合1小時。得到的有機聚異氰酸酯，NCO 枯度為1〇〇mPa(25°C)。以下將該異氰酸醋以 」表示。 ^異氰酸酯調製例2〜18> 氰酸同樣的方法’按照表1的捧合比，得到有機聚異 JN⑷-2」〜「Nc〇18」。 [表1] 14 201120080 調製例18 NCO-18 ! 1〇〇 48.2 調製例17 NCO-17 4 IS j 19.3 調製例16 NCO-16 1DO 50.0 調製例15 NCO-15 100 3ΰ.9 調製例Η NCO-14 100 00 d 1770 17.0 調製例13 NCO-13 σ CO d 975 17.4 調製例12 NCO-I2 R 00 d 724 17.ΰ 調製例11 NCO-11 cc o 399 18.Q 調製例10 NCO-10 〇 09 d 163 18.6 調製例9 NCO-9 〇 CiO d 121 18.8 調製例8 NCO*8 100 00 d § 19.0 調製例7 NCO-7 100 CO d 1750 19.1 調製例6 NCO-ΰ 〇 S 00 d 987 19.2 調製例5 NCO-5 cq d 742 19.2 調製例4 NCO-4 00 d 418 19.3 調製例3 NCO-3 S 〇 ec d 177 19.4 調製例2 NCO-2 g 〇 CO d 133 19.5 調製例1 NCO-1 10Q 00 d 100 19.5 有機聚異戴酸酯 脲基甲酸酯改質聚異氤酸酯-1 脲基甲酸酯改質聚異氧酸酯-2 販基甲酸酯改質聚異氪酸酯·3 : 脲基甲酸酯改質聚異氰酸酯-4 HDI IPDI Τ-80 HALS 黏度(mPa^r) NC◦含量(％) 15 201120080 (多元醇預混料的調製） 元醇’在25〇c下混合搜拌1小時 [表2] β 1」 」（調製例19〜26)。 得到多Adding the urea-based phthalate modified polyisocyanate of 〇 丨 and 〇 8g of a 〇 旦 具有 具有 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在. The obtained organic polyisocyanate had an NCO dryness of 1 〇〇mPa (25 ° C). Hereinafter, the isocyanic acid vinegar is represented by "". ^Isocyanate Preparation Examples 2 to 18> The same method as cyanic acid The organic polyiso JN(4)-2" to "Nc〇18" were obtained according to the holding ratio of Table 1. [Table 1] 14 201120080 Modification Example 18 NCO-18 ! 1〇〇48.2 Modulation Example 17 NCO-17 4 IS j 19.3 Modulation Example 16 NCO-16 1DO 50.0 Modulation Example 15 NCO-15 100 3ΰ.9 Modulation Example Η NCO- 14 100 00 d 1770 17.0 Modulation Example 13 NCO-13 σ CO d 975 17.4 Modulation Example 12 NCO-I2 R 00 d 724 17. 调制 Modulation Example 11 NCO-11 cc o 399 18.Q Modulation Example 10 NCO-10 〇09 d 163 18.6 Modification Example 9 NCO-9 〇CiO d 121 18.8 Modification Example 8 NCO*8 100 00 d § 19.0 Preparation Example 7 NCO-7 100 CO d 1750 19.1 Preparation Example 6 NCO-ΰ 〇S 00 d 987 19.2 Modulation Example 5 NCO-5 cq d 742 19.2 Preparation Example 4 NCO-4 00 d 418 19.3 Preparation Example 3 NCO-3 S 〇ec d 177 19.4 Preparation Example 2 NCO-2 g 〇CO d 133 19.5 Modulation Example 1 NCO-1 10Q 00 d 100 19.5 Organic polyisocyanurate allophanate modified polyisodecanoate-1 Ureacarboxylate modified polyisophthalate-2 Venomate modified polyisophthalate 3 : allophanate modified polyisocyanate-4 HDI IPDI Τ-80 HALS viscosity (mPa^r) NC◦ content ( ) 15201120080 (polyol premix modulation) monool 'found in 25〇c mixed for 1 hour [Table 2] β 1 "" (Preparation Example 19~26). Get more
25±2〇Ca^ J ^ Folymer Engineering Co.,LTD ;;得《軟甲,出至5〇〇—x5〇〇mmx5〇0mm尺寸的箱 示聚異氰酸醋組成;蛊多泡體。另外，表3中，励EX表 氰酸驗成物與多辑成分丨耳比’接合比表示聚異 料的=製ί，胺基甲酸乙酯發泡體。關於各原 分為ΟΗ基的數。酸誠分^NC()基的數，多元醇成 原料之種類及摻合量示二2〗3〜19以及各比較例1〜7中所使用的 [表 3] ' & ° 16 201120080 贼例7 2 ό υ ώ § < 5ύ·9 <Λ «η δ § ▼ Ο S卜 実酬19 2 ό ζ S 8 〇 κ ?! « 121 107 3.4 2 0 s ，· 実酬18 3 ό ζ S δ Ο <〇 s 2 2 〇 s 2 実施例17 6 υ ζ ώ 1 0 Ώ Oj Ό 1 106 152 3.6 d 0 s 実旄例1<5 NCO-10 m ώ S 0 56.7 in «〇 s r- ri n 0 £ 実箱例15 α υ ζ S S 〇 jn rt P 〇! H o ο s ▼ 贼例6 Μ υ ζ m § < 61.2 W1 % fl； ri <Ί o 0 s 2 比關5 NCO-18 Β·8 □ 〇 ΜΙ 100 M 8 i 3 1 3 X 次 g 実酬Μ fH υ ώ § ο 50£ 1 I l〇 110 K (Λ 2 ο s Γ< οό 贼例4 Γ|> υ ζ. ύ S < «? «η v 105 101 2 ο DO jn _例13 NCO-6 Β-5 1 100 0 54Λ X ΙΟ 114 102 »〇 2 ο s 獅例12 «η υ S 8 〇 54Α l〇 r- 102 a ，· «0 O 〇 s 実施例" ό υ ζ S § ο f» s s »n jn 〇1 2 〇 £ 〇5 例1〇 Μ υ ζ S 8 ο 58·3 <s M 2 〇 ο s 2 峨例3 ό υ ζ S S < s l〇 p 3 5 a 0 s 09 実删9 υ S S 〇 5ΐ «〇 »n 00 3 2 ο s η 実施例8 NCO-17 S § 〇 wi 5Ϊ Ό g 2 t<i < !S Os 実箱例7 1 υ ζ V) CQ ο 〇 54.1 *〇 r» 132 170 4.1 3 〇 実箱例6 ν υ ΙΟ ή S ο νί >〇 108 3 O 0 s 〇i « 実臟5 NCO-4 S S ο 51.4 » «4 PS 9 Μ o 〇 w Μ 実議 υ ζ 2 § 0 M Kl g 3 Ί (Ί n o ο s 実綱3 NCO-4 Λ ώ 1 100 〇 5,! Λ «Ο Λ g WJ rt r< d 0 s 実箱例2 υ ζ S S 0 *Λ l〇 is 3 CH ο s η •ο 実酬1 ο ζ ώ 8 〇 52Ό 1 JO Ό V d 0 s ί-Η 卜’ 贼例2 « ό υ ζ. ώ § 翟陷 诚例1 NCO-15 ώ S «陷; • • 多挪1_師料 J index 成型性 g度(kg/m3) 25%ILDCN/314cm2) 反强（％) TB ( k Pa) EB(%) TR(N/cm) S瞄永久愛形(％) 耐天氣性澍轼後的麵狀怒 抗拉強度保持辛(％) 愛黃性(ΔΥΙ) 17 201120080 <異氰酸酯成分> IPDI ·異佛爾酮二異氰酸S旨，Degussa Co., Ltd.製 T80 .曱本二異氣酸醋(商品名：c〇ronate T-80 ’日本聚氨酉旨 工業製） <多元醇成分> 多元醇A : NEF-455(聚多元醇混合物，日本聚氨酯工業製， 標稱官能團數3，OH值168) ” 多元醇B : NEF-456(聚醚多元醇與聚合物多元醇的混合物， 曰本聚氨酯工業製，標稱官能團數3，OH值157) 多元醇C : NEF-457(聚醚多元醇混合物，日本聚氨酯工業製， 標稱官能團數3.8，OH值145) ’、 夕元醇D . NEF-458(聚醚多元醇混合物，日本聚氨酯工章製， 標稱官能團數3.5，OH值362) '、 多元醇E : SannixPP-2000(聚醚多元醇，三洋化學工業製，斤 稱官能團數2，OH值56) ^ ^ <其他> CAT1 : TEDAL33(胺催化劑，東曹製） CAT2 : TOYOCATET(胺催化劑，東曹製） CAT3 : DBU(胺催化劑，San-Apro 製） CAT4 · DABCOT-9(金屬催化劑，八匕pr〇ducts製） HALS : Tinuvin765(受阻胺系光安定劑，Ciba_Geigy 製） 整泡劑1:311-192(石夕系整泡劑，1)(^〇311]^製） 整泡劑2 : SRX-280A(石夕系整泡劑，Dow c〇ming製） 水：自來水 根據本發明之軟質聚胺基曱酸乙酯發泡體的製造方法，發 體的密度根獅使㈣有卿魏_旨的麵及水等之換合^匕率 有高低，但發泡體製造時的反應性落在實用上無_問題 圍。另外，製造時及養護顧的作業環境良好，不會感覺 於HDI等有機聚異氰酸酯之令人難受的刺激臭味等。 ,、 <耐天氣性測試> ' 18 201120080 利用 Suga Test Instruments 製 Super Weather Metei^lSOW/m2， 300〜400nm，濾光器石英/#275，黑盤溫度63<t，降雨週期12 分鐘/60分鐘中)實施i8〇小時。 關於外觀，表面幾乎無變差者為〇，有若干變差者為△，嚴 重變差者為X。 關於物性保持率，抗拉強度保持率8〇%以上者為〇。 關於變黃性，係使用Minolta製色彩色差計CR_31〇測定γι 值。YI值之差(ΛΥΙ^測試結束後的YI值—測試前的Yj值為1〇 以下者為〇。 <機械物性> 關於抗拉強度，依據JISK6400-5進行測定。 抗拉強度保持率(％)=(測試結束後的抗拉強度—測試前的抗 拉強度)/測試前的抗拉強度X100 壓縮永久變形的測定方法依據JIS-6400-4以(50%壓縮，22小 時’ 70C)樣品尺寸l〇mmxi〇mmxi〇mm及n = 4加以實施。传用 以下的計算式進行計算 a25±2〇Ca^ J ^ Folymer Engineering Co.,LTD ;; obtained "soft armor, out to 5 〇〇 - x 5 〇〇 mm x 5 〇 0 mm size box shows polyisocyanate composition; 蛊 multi-foam. Further, in Table 3, the ratio of the excimer of the EX to the surface of the excipient of the EX and the ratio of the components of the cyanide showed that the bonding ratio of the polyisocyanate was a urethane foam. The number of each original is divided into thiol groups. The acidity is divided into the number of NC() groups, the type of the raw material of the polyol and the blending amount are shown in 2:3 to 19 and the [Table 3] used in each of Comparative Examples 1 to 7 ' & ° 16 201120080 Example 7 2 ό υ ώ § < 5ύ·9 <Λ «η δ § ▼ Ο S 実 19 19 2 ό ζ S 8 〇κ ?! « 121 107 3.4 2 0 s ,· 18 18 3 ό ζ S δ Ο <〇s 2 2 〇s 2 実Example 17 6 υ ζ ώ 1 0 Ώ Oj Ό 1 106 152 3.6 d 0 s 実旄 Example 1<5 NCO-10 m ώ S 0 56.7 in «〇s r - ri n 0 £ 実 box example 15 α υ ζ SS 〇jn rt P 〇! H o ο s ▼ thief example 6 Μ υ ζ m § < 61.2 W1 % fl; ri <Ί o 0 s 2 than off 5 NCO-18 Β·8 □ 〇ΜΙ 100 M 8 i 3 1 3 X times g Μ Μ fH υ ώ § ο 50£ 1 I l〇110 K (Λ 2 ο s Γ< οό thief example 4 Γ|> υ ζ. ύ S < «? «η v 105 101 2 ο DO jn _ Example 13 NCO-6 Β-5 1 100 0 54Λ X ΙΟ 114 102 »〇2 ο s lion example 12 «η υ S 8 〇54Α L〇r- 102 a ,· «0 O 〇s 実 & & & ζ § § § 2 2 2 2 2 2 2 2 2 2 2 2 s M 2 〇ο s 2 峨例3 ό υ ζ SS < sl〇p 3 5 a 0 s 09 実 9 9 υ SS 〇5ΐ «〇»n 00 3 2 ο s η 実 Example 8 NCO-17 S § 〇wi 5Ϊ Ό g 2 t<i < !S Os 実 box example 7 1 υ ζ V) CQ ο 〇 54.1 *〇r» 132 170 4.1 3 〇実 box example 6 ν υ ΙΟ ή S ο νί >〇108 3 O 0 s 〇i « 実 5 5 NCO-4 SS ο 51.4 » «4 PS 9 Μ o 〇w Μ 実 υ ζ 2 § 0 M Kl g 3 Ί (Ί no ο s 実 3 3 NCO-4 Λ ώ 1 〇 , , , , W W W W V d 0 s ί-Η 卜 ' thief example 2 « ό υ ζ. ώ § 翟 诚 诚 1 NCO-15 ώ S « 陷; • • 多多1_师 J index Formability g degree (kg/m3 ) 25% ILDCN/314cm2) Anti-Strength (%) TB (k Pa) EB(%) TR(N/cm) S-mirror permanent love shape (%) Weather-resistant facial anger tensile strength remains strong (%) Yellowishness (ΔΥΙ) 17 201120080 <Isocyanate component> IPDI ·Isophorone diisocyanate S, manufactured by Degussa Co., Ltd. T80. Hydrogen vinegar (trade name: c〇ronate T-80 'Japan Polyurethane Industrial Co., Ltd.) <Polyol Component> Polyol A: NEF-455 (Poly Polyol Mixture, Made in Japan Polyurethane Industry, Nominal Number of functional groups 3, OH value 168) ” Polyol B: NEF-456 (mixture of polyether polyol and polymer polyol, manufactured by Sigma Polyurethane Industry, nominal functional group number 3, OH value 157) Polyol C : NEF -457 (polyether polyol mixture, manufactured by Nippon Polyurethane Industry, nominal functional group number 3.8, OH value 145) ', U.S. alcohol D. NEF-458 (polyether polyol mixture, Japanese polyurethane industry, nominal functional group Number 3.5, OH value 362) ', Polyol E: Sannix PP-2000 (polyether polyol, manufactured by Sanyo Chemical Industry, kg functional group number 2, OH value 56) ^ ^ <Others> CAT1 : TEDAL33 (amine catalyst , made by Tosoh) CAT2 : TOYOCATET (amine catalyst, manufactured by Tosoh Corporation) CAT3 : DBU (amine catalyst, manufactured by San-Apro) CAT4 · DABCOT-9 (metal catalyst, manufactured by Gossip pr〇ducts) HALS : Tinuvin765 (hindered amine) Light stabilizer, Ciba_Geigy) Foaming agent 1:311-192 (Shi Xi system foaming agent, 1) (^ 〇 311] Foaming Agent 2: SRX-280A (Shishi-based foaming agent, manufactured by Dow C〇ming) Water: tap water According to the method for producing soft polyamine phthalate foam according to the present invention, the density of the hair lion (4) There is a high level of the ratio of the surface of the water and the water, etc., but the reactivity at the time of manufacture of the foam falls into practical use. In addition, the working environment at the time of manufacture and maintenance is good, and the unpleasant irritating odor of organic polyisocyanate such as HDI is not felt. , , <weather resistance test > ' 18 201120080 Super Weather Metei^lSOW/m2, 300~400nm, filter quartz/#275, black disk temperature 63<t, rain cycle 12 minutes using Suga Test Instruments In the course of 60 minutes, i8 〇 hours were implemented. Regarding the appearance, there is almost no deterioration on the surface, and there are a number of variations that are △, and those who are severely degraded are X. Regarding the physical property retention rate, the tensile strength retention rate is 8% or more. Regarding the yellowing property, the γι value was measured using a Minolta colorimeter CR_31. Difference in YI value (YI value after the end of the test) - The Yj value before the test is 1 〇 or less is 〇. <Mechanical properties> The tensile strength is measured in accordance with JIS K6400-5. (%) = (tensile strength after end of test - tensile strength before test) / tensile strength before test X100 Determination of compression set according to JIS-6400-4 (50% compression, 22 hours ' 70C The sample size l〇mmxi〇mmxi〇mm and n = 4 are implemented. The calculation is carried out using the following calculation formula a
Cs=(t〇-t1)/(t〇-t2)xl00 Cs :壓縮永久變形(〇/0) 試片原本的厚度(mm) 將試片自麗縮板取出 間隔物的厚度(mm) t〇 tl h 30分鐘後的厚度(mm) 、關於實施例中所列舉的外觀、耐天氣性、以及變黃性之纟士果 為無特別的問題。未使用(A2)的軟質聚胺基曱酸乙酯發·泡體較 例$的成形性有問題，產生沉降(發泡體的高度達到最大後會產生 下沉。表示此下沉比例的值，沉降(％)=(發泡體最大高度—I分鐘 後的高度)/發泡體最大高度><100))會發生變大等問題。另外，未使 用(A1)的軟質聚胺基甲酸乙醋發泡體(比較例句，有形成獨立氣泡 的成形性問題，產生底部隆起(成型時的發泡體底部積 ^ 泡體底部隆起的狀態)的問題。 〃只 19 201120080 【圖式簡單說明】 無。 【主要元件符號說明】 無。 20Cs=(t〇-t1)/(t〇-t2)xl00 Cs : Compression set (〇/0) Original thickness of the test piece (mm) Thickness of the spacer (mm) from the slab The thickness (mm) after 30 minutes of 〇tl h, and the appearance of the weather, the weather resistance, and the yellowing property listed in the examples are no particular problems. The soft polyamine phthalate which is not used (A2) has a problem in the formability of the foam, and sedimentation occurs. (The height of the foam reaches a maximum and sinks. The value of the sinking ratio is expressed. The settlement (%) = (the maximum height of the foam - the height after 1 minute) / the maximum height of the foam >< 100)) may become large. In addition, the flexible polyurethane foam of (A1) was not used (comparative example sentences have the problem of formability of forming closed cells, and a bottom bulge is generated (the state of the bottom of the foam at the time of molding is bulged at the bottom of the foam) The problem is only 19 201120080 [Simple description of the diagram] None. [Main component symbol description] None. 20