201226428 六、發明說明： 【發明所屬之技術領域】 修ίίϊί、關於可用於廣泛用途的軟f聚氨酯發泡體，即使暴 i棉、紙以生色’尤其係關於適用於i 泡體 、治触„ 、 月墊、胸墊寺衣料品的軟質聚氨酯發 【先前技術】 & =往’軟質聚氨g旨發泡體由於柔軟性與彈力 在其輛3,,途，胸墊、脸等衣*用途等， 然而，使:芳i:ii:c(TDi)?芳香族系聚異氰酸酉旨。 方法，化，作為防止這焱黃ί的 來代替料料料—旨或蹄麵異氰酸酯 術，專糊化劑的技201226428 VI. Description of the invention: [Technical field of invention] 修ίίί, about soft f-polyurethane foam that can be used for a wide range of applications, even if it is violent, the paper is colored, especially for the application of i-bubble, touch „ , 月 mat, chest pad temple clothing item soft polyurethane hair [prior art] & = to 'soft polyurethane powder foam due to softness and elasticity in its 3,, way, chest pad, face, etc. *Use, etc., however, to: fang i:ii:c(TDi)? Aromatic polyisocyanate. Method, as a substitute for the material, or hoof isocyanate Technique
Si獻3中揭示了軟質聚氨醋發泡體的製s法°，’ 使用異佛爾酮二異氰酸醋(IPDI)作為二$玫在於， :或轉造聚魏發 產生粗大泡孔不=:呈J二與發泡的不平衡等而 -用會產生錄。⑶被局限 然而，如專敝獻4所述，可列舉岐物旨肪婦氰酸轉 3 201226428 成的脲基曱酸g旨·有機聚異氰酸g旨組合 :使用欠缺反應性的脂肪族異氰酸酯 '缺而， 機械物性沒有充分示出。 了於成型卜生、硬化性、 專利文獻1 專利文獻2 專利文獻3 專利文獻4 曰本特開昭50-64389號公報 曰本特開昭52-128997號公報 曰本特開平10-36543號公報 曰本特開2005-48038號公報 【發明内容】 (發明的效果） = ΪΪ造方上，，慎有均勻且美觀的泡孔結構 另外，在胸塾等用途中，壓縮永久變形為重要的物 本發明中壓縮永久變形是非常良好的，適用於墊 (發明要解決的問題） ' ' 本發_目的是解決屬於以往聚偏旨發泡體缺點 等導致_色、上述提案的因反舰不平衡導致料u =產生焦燒等問題，提供適合於目前生產狀況的軟質聚氨酿發 的軟質聚氨i旨發泡體，該軟質聚氨g旨發泡體具有迄止= 題的對於紫外線、叫和熱的優異的耐變色性。此外為 明的製紗法’可以不使作業環境惡化地_發泡體 的軟質聚氨酯發泡體，可期待在商業上用於廣泛的用途/ 泡體 (用於解決問題的方案） 為了提供解決了上述課題，提供具有優異的耐變色性且呈 適於現有生產狀況的成型性的軟質聚氨酯發泡體用組合 了深入研究，結果完成了本發明。 退4丁 即，本發明如以下的第⑴〜(13)項所述。 (1)一種軟質聚氨酯發泡體，其係使有機聚異氰酸酯 _ 醇(B)、催化劑(C)、發泡劑(D)、穩泡劑(E)的混合液反應發泡2 4 201226428 化而得到， 武Η心2彳聚異氰酸®旨成分(A)是* -元醇與脂肪族系及/ 系一異氰酸s旨構成的腺基甲酸s旨變性有機聚異氰1酸醋組 二〆々）、和由含有2個以上羥基的醇與脂肪族系及/或脂環族系二 乂 夂醋構成的脲基曱酸醋·變性有機聚異驗酯、组合物(A2)的混 δ物，異氰酸酯成分的平均官能基數為28〜43。 ?如亡述(υ之軟質聚氨醋發泡體，其中，異氰酸醋成分㈧ ί燃二與脂f族系及/或脂環族系二異氰酸醋構成的脲基甲酸 幾聚異氰_旨組合斷A1)、和由含有2個以上祕的醇斑 脂環族系二異氰酸酷構成_基曱義變性有機聚 广且ΐ物(A2)、和由脂月方族系及/或脂;裒族系二異氰酸酯構 能基數S3組合離3)舰合物，錄酸赋分⑷的平均官 中六之軟質聚氨醋發泡體，其+，在異氰酸醋成分⑷ 成分的平均官能基數為3.〇〜4.0。 ^ j (4)如上述(2)之軟質聚氨醋發泡體，其中，在異 =加有脂肪族及/或脂環族系二異氮酸 體㈣ 刀 成分的平均官能基數取〇〜3.7。 早MA4)異认S曰 夕述⑴〜(4)中任一項之軟質聚氨醋發泡體，盆中，所述Si Xian 3 reveals the method of making soft polyurethane foam, 'using isophorone diisocyanate (IPDI) as the second one, or turning into poly-fat to produce coarse cells Not =: In the case of J II and the imbalance of foaming, etc. - will be recorded. (3) Limitation However, as described in the special offer 4, it can be exemplified by the combination of the sulphate and the sulphate sulphate 3 201226428. The isocyanate is absent and the mechanical properties are not sufficiently shown. Patent document 1 Patent Document 2 Patent Document 3 Patent Document 4 曰本特开昭-50-64389 曰本特开昭 52-128997 曰本本开平平#-36543号曰本特开开开开开开开开开开开下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下In the present invention, the compression set is very good, and is suitable for the mat (the problem to be solved by the invention) ' ' The present invention is intended to solve the problem that the conventional proposal has the disadvantages of the foam, etc. The balance causes the material u to cause problems such as scorching, and provides a soft polyurethane foam which is suitable for the soft state of the current production condition, and the soft polyurethane foam has a UV-resistant foam Excellent resistance to discoloration, called heat. In addition, it is a flexible urethane foam which can be used for a wide range of applications/bubbles (solutions for solving problems) in order to provide a solution. In view of the above-mentioned problems, it has been intensively studied to provide a combination of a flexible polyurethane foam having excellent discoloration resistance and moldability suitable for the conventional production conditions, and as a result, the present invention has been completed. The present invention is as described in the following items (1) to (13). (1) A flexible polyurethane foam which is obtained by reacting a mixture of an organic polyisocyanate-alcohol (B), a catalyst (C), a foaming agent (D), and a foam stabilizer (E) 2 2012 201228 And, the Wuyixin 2彳 polyisocyanate® component (A) is an adenosine and an aliphatic isocyanate. A vinegar group of bismuth), and a ureido vinegar vinegar composed of an alcohol having two or more hydroxyl groups and an aliphatic and/or alicyclic diterpene vinegar, a denatured organic polyisoester, a composition (A2) The mixed δ, the isocyanate component has an average number of functional groups of 28 to 43. Such as the death of the soft polyurethane foam, which is composed of isocyanic acid (8) Isocyanide combination A1), and consisting of two or more secret oleophosic ring diisocyanate _ 曱 曱 变性 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机And/or fat; steroidal diisocyanate structure energy base S3 combination from 3) hull compound, recording acid distribution (4) of the average official six soft polyurethane foam, its +, in isocyanic acid vinegar The average functional group number of the component (4) is 3. 〇 to 4.0. ^ j (4) The flexible polyurethane foam according to the above (2), wherein the average functional group number of the knife component of the aliphatic and/or alicyclic diisocyanate (IV) is different 3.7. Early MA4) a soft polyurethane foam according to any one of (1) to (4), in the pot, said
多兀SMB)由標稱平均官能基數 约、T 6〇〜20，_的多_(Β)構成。 數里千如子i為 (6)如上述(1)〜(5)中任一項之軟質聚氨酯發泡體，豆 及多元醇(Β)的任何-者或兩者中添加受阻胺系 τ里^ϋ_〜(7)中任一項之軟f聚氨®旨發泡體，1二在所 ΐ)亞多元醇⑼的任何一者或兩者中添加三(二丙二 201226428 中任賴物侧造如上叫⑻ 衣卿細品，其_吐述⑴，中任- 聚氨酯發泡體 (11)一種術生用成型品，其使用如上 聚氨醋發泡體。 w w中任一 項之軟質 項之軟質 ==化胳用成型品，其使用如上述⑴〜⑻中任- 項之軟質 項之軟質聚 聚氨酯發泡體 (13)—種鞋用成型品，其使用如上 氨醋發泡體。 任- 【實施方式】 [實施發明之形態] 以下更存細說明本發明。本發明中取 使用由一元醇與脂肪族系及/ 為承/'氰齩酯(A) 酸醋變財機料_敝合^旨構成的脲基甲 醇與脂肪族系及/哎^:产> & 由3有2個以上羥基的 機聚異異嫌構錢憎賴性有 出下脲基曱酸醋組合物的含醇性羥基的化合物，可列舉 低分子量脂肪族醇：Polyterpenoid SMB) consists of a number of nominal average functional groups, T 6 〇 20 20, and _ _ (Β). (6) A soft polyurethane foam according to any one of the above (1) to (5), a hindered amine system τ added to any or both of beans and polyols (Β) In any one or both of the sub-polyols (9) of the above-mentioned ϋ_~(7), the addition of three (2, 2, 2, 2, 2, 2, 2, 2, 2, The side of the object is as follows (8) Yiqing fine product, which is described as (1), and the middle-polyurethane foam (11) is a molded article for use in the manufacture of the polyurethane foam as described above. The soft material of the soft item == a molded article for stagnation, which uses the soft polyurethane foam (13) of the soft item according to any one of the above (1) to (8) - a molded article for shoes, which is foamed with the above-mentioned ammonia vinegar [Embodiment] [Embodiment of the Invention] The present invention will be described in more detail below. In the present invention, the use of a monohydric alcohol and an aliphatic system and/or a cyano oxime ester (A) vinegar is used for profit.机 敝 脲 脲 脲 脲 U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U Sour vinegar composition Hydroxyl compounds include low molecular weight aliphatic alcohol:
埽丙醇乙^己^醇、山異丙醇、異構丁醇、戊醇、己醇和庚醇、 丙二醇、丨3 ^ L、&原子數1Q〜20的簡鱗、乙二醇、H 戊4、i戊!二丁謂、以丁二醇、μ-丁二醇、i 厶曱基-2-丙基4 3_而Γ己一醇、2,5_己二醇、3-曱基-1，5·戊二醇、 癸二醇、1>2•十 拉「醇、2,2,4·二甲基-16-己二醇、1，1〇、 甲基丙烧、季戌喊Γ 知、三μ基乙院、三瘦 •、乙一醇單烧基_或_烯丙基醚、丙二醇單垸義 6 201226428 醚、二乙二醇'三乙二醇以及四乙。 脂環醇： 醇m、i if、曱基環已醇、三曱基環己醇、4·叔丁基環己 環己烷二醇、M_環己产_酿基十虱奈裱己烷二酵、υ- 1 4-雔-辦甲其_ ί Ι 士二羥基-1，1，3,3-四曱基-環丁烷、 己二二Λ衣烧、又”基環己基)_曱统、2,2_雙(4-經基環 雙·^曱^降、水J’4_雙(4_經基環己基)戊烧、糠醇、四氫糠醇、 克气T基降冰片燒和二輕曱基-三環癸烧。 高分子多元醇： 醇。：聚Γ多元醇、聚碳酸酯多元醇、聚醋多元 使用公知的具有1〜6她基的《多元醇， 或表氯醇之_環氧丄氧::烯;：氫:喃、氧化苯乙烯 =醇^^的具有反；性氣軒===:次: it還可以使用硫二甘醇自身的縮合產物及/或與其 成分的縮合產物作為聚硫趟。該產物根據辅助 峰)的黏度、與多元醇⑻的相以 匕基的化5物祕為至少含有韻子數HQ崎化合物。 语视H作為製造脲基f酸酯變性有卿魏酸驗合物的起妒 二異氰酸醋’只要是脂肪族系或脂環族系的二ί‘ 2 有特別限制。作為脂肪族二異氰酸酯的例子，有六i :基編旨(HDI)、離胺酸二異氰酸酯謂、亞丁基二異 二麵，’3£7'，_1、’4_二，氰酸§旨、八亞甲基二異氰酸醋等二異氰酸 西ϋητ^ 作為脂環族二異氛酸醋的例子，有異佛爾酮二里气 J醋(腿)、氫化二苯基甲烷二異氛酸醋(氫化刚)、氫化苯二 :一異氰酸酉旨(氫化XDI)、環己炫二異氰酸酉旨、甲基環己烧二異 、一^己基甲烷二異氰酸酯等二異氰酸酯類。另外，具有劣 9壤但異氰酸醋基不直接缘结於芳香環的苯二甲基二異氛酸酯 201226428 Γ基苯二甲基二異氮酸醋(tmxdi)也可以作為屬於脂肪 物質在本發明中使用。在本發日种，在# 宜使用脳。在此處，由於腹的蒸氣壓非常低了因此 境時，較佳為，進行調整以使得所使用的脲基曱酸 ^，有機聚異氰酸酯組合物中所含有的遊離聰為i質量。/。以 巧在製造由含醇性經基的化合物與脂肪族系及/或脂環 旨構成觸基曱酸㈣性有機聚異驗合物時使用 鹽過土金屬鹽和氧化驗土金屬鹽。尤其，從ϋ性 二二物的觀點來看’羧酸錯鹽、紐氧錯鹽是最適合的'作 卞月女丨，4-—氮雜雙環辛烷、15-二氮雜雙環壬烯、四甲美丁二脸 =曱基丙二胺和雙·Ν_二甲基氨基乙基_。苯_之類“ 吼ϊ納是適合的催化劑。含氮的芳香族化合物例如 =早C1〜C4-烧基*定、二曱基咖定、队二甲基氨基-吡。定、二 乙基吡义和二曱基吡啶也可以使用。〇〜(：4_1^烷基-吡 C1 〜C4-N-烷基-吡咯啉、 吡唑、Cl〜C4-N-烧基-咪唑、C1〜C4_N_烷基_σ米唾木 基ΐ唾Λ：α〜⑽縣]，2,3·三唾、α〜⑽销 ^及、，·里任思烷基化的嘧啶、噠畊、HI三哄、丨又伞三 二畊以及經任意烷基化的喹啉、異喹啉、喹喔啉和吖啶也是^宜 另一方面，作為異氰脲酸酯化反應，可列舉出在显 化催化劑的存在下將聚異氰酸酯變性(三聚體化)的方法、。作為這= 變性方法，例如，可以使用日本專利第33714_ 太: 2002-241458號公報中記載的方法。 日本特開 作為異氰服酸醋化催化劑，例如可以使用脂肪 鹽、苯_甲等酉分鹽、2,4,6_三(二曱基氨基曱基)苯酉分、2,4_雙㈡甲 8 201226428 ^氨基曱基)苯酚、2,6-二叔丁基_4_二曱基氨基三曱基矽烷苯酚、 士^胺、N，N’，N，，-三(二曱基氨基丙基)六氫_s_三哄、二氮雜雙環十 一碳烯等胺系化合物。其中，脂肪族羧酸的錫鹽、鉀鹽、鈉鹽、 、鋅鹽'絲鹽較佳，醋酸、丙酸、十一酸、癸酸、辛酸、肉 豆蔻酸的鹽是最適合的。作為市售產品，還可以使用2_羥丙基三曱 基録.鋅酸鹽(DABCO TMR ’ Air Products (股）製造）、辛酸鉀 (DABCOK-15 ’ Air Products (股)製造）。 如上所述得到的聚異氰脲酸酯具有異氰脲酸酯基，還具有 反應時副生成的腺基曱酸醋基。 所巧異氰酸脲醋中的服基曱酸醋基與異氮腺酸酿基的莫耳 t可以錯由射調整異氰腺酸g旨化反應時間縣適當調整。 此外也了以將預先脲基甲酸醋化了的聚異氰酸g旨進一步里 氰服酸S旨絲調整麟情絲/異細_旨基的莫耳比。 平的多元醇⑻是標稱平均官能基數為2〜6、數量 J泡體的?爾棒聚§旨多元醇 酉曰 J含有;二，二乙二醇、二丙二醇、;油作: 己一醉乙—月女、山梨醇等，此外有以聚乙二二二 „成聚合環氧乙烧⑽）、環氧 ： 的聚合物多元醇、基!:合丙細腈、乙烯基而得到 含有分散的脲的變性氰酸s旨的反應而得到的 醇、丁二醇、甘為來酉曰多几醇，可以使用己二酸與乙二 含磷多元醇、聚酯醚多元醇等。-醇、來丁一烯多元醇、 60〜為2〜6、數量平均分子量 等的變性聚_多元醇1 』轉基的》多元醇或此 〜2，_的縮合= 3數^〜6、數量平均分子量為 口承酉曰夕讀，數量平均分子量200〜6，_的 201226428 承四亞曱基_多元醇，當量2⑽〜2，_的聚碳咖二醇等。這 兀醇根據騎轉即可，另外還可以將兩_上混合使用。— ^對本發明中使用的催化劑(c)沒有特別限制’在本發明中，通 令用於製缺IU旨發泡體的齡催化劑、金屬催化劑、具有牌基 =及其衍巧均可使t作為胺系催化劑，比較溫和的叔胺類， 尤=乙二胺是適宜的’此外，可列舉出三曱基氨基乙基乙醇胺、 -曱基乙基乙基乙醇胺、二甲基氨基贼、三乙胺、丨_異丁 I基咪唑、曱基味啉、乙基味啉、二乙醇胺、四甲基六亞曱基二 ，、二甲基-己胺、四甲基丙二胺、三曱基氨基乙基轉、四甲 二^一胺二二(二甲基氨基丙基)六氫-P-三胺、二曱基苄胺、二曱 =氨基乙氧基乙醇、一曱基氨基己醇、曱基經基D瓜哄等。另外， 2可^使肋往仙的具有絲的驗其衍生物。料該具有脉 二的胺及其射物，較佳為使m，8_4雜雙環(5,4，G)十一碳_7_ 二Ϊ雜雙環(4,3,0)壬參5,6_二丁基氨基-1，8-。氮雜雙環 (，，）十一碳-7-烯等。作為二氮雜雙環烷烴類，可列舉出丨8_二 雜雙環(5,4,〇)十-碳_7_烯(以下亦簡稱為DBU)、以二氮雜錐^ 另外，逦可以使用弱酸的鹼金屬鹽、三聚化催化劑等。作 ，化劑，較佳為使用辛酸亞錫、二乙酸二丁基錫、二月桂酸丄丁 土錫、其他通常用於聚氨酯發泡體的比較溫和的錫系催化劑。 在上述催化劑中，在本發明中，為了獲得反應性平衡良好、 =的均勻性良好、閉孔性低、作為穩定的發泡體的發泡體 適&至少使用DBU和辛酸亞錫。 作為本發明中使用的發泡劑(D)，可以使用通常用於聚氨酯發 知的♦泡劑。例如，作為物理發泡劑，可列舉出戊；)：完、己 烷等烴化合物，包括HCFC-141b、HCFC-123、HCFC-n、 ^145ίν™Μ65Π^、脏-13知等所謂的氣利昂替代品的4 、Α导，作為化學發泡劑，可列舉出水、有機酸等。另外，還可 =巧氣體填充裝置，使空氣、氮氣、碳酸氣鮮混人溶解在 攻中來使用。這些發泡劑可以將兩種以上組合使用，其用量適宜 10 201226428 為多元醇的1〜50質量％。 作為本發明中使用的穩泡劑(E)，可以使用L-5309、L-5366、 L-5420、L6202B(Momentive公司製造）、F-242T、F-303、F-703(信 越化學工業公司製造）、SH-192、SH-193、PRX-607、SRX-280A、 SF-2914、F-122、SF-2962(Dow Corning Corporation製造）、B-8300、 B-4113LF(Evonik公司製造）、DC-5169、DC-193(Air Products (股) 製造)等用於軟質、硬質或HR用聚氨酯發泡體的穩泡劑。 本發明中’另外，根據需要還可以使用以往公知的其他添加 劑。例如’藉由配混抗氧化劑或紫外線吸收劑，可以進一步提高 作為本發明的特徵的優異的耐變色性。具體而言，有酚系抗氧化 劑、磷系抗氧化劑等抗氧化劑、苯並三唑系、二苯曱酮系紫外線 吸收劑等。 、’ 尤其’作為填系抗氧化劑，從抑制變色的效果大的理由考慮， 較佳為 COLOR STABILIZER CS-22(M〇mentiVe公司製造）。心 另外’除此以外，還可以添加公知的阻燃劑、介面活性劑、 =焦燒劑、著色劑、導電劑、絕緣劑、發光劑、抗菌劑、芳香劑 尤其作為防焦燒劑，從抑制焦燒的效果大的理由考慮，可列 舉出JPE-10、JPE-13R(城北化學公司製造）。 為了使用這些原料物f製造本發明的軟質聚㈣旨發泡體，不 制的麟，可喊接使祕有錄質聚躺發泡體的 ίϊϊί。;將預先在各自容器中保管或製備的聚異氰 tir多70醇成分、催化劑、發泡劑和其他添加劑投入到-、、曰^攪拌混合以達到均f，同時引發反應。接著，將 :ίίί ΐ框、鋪設有底_傳送帶上，進行反應、發泡和 藉由用異―旨成分、多元醇成分的雙組分系， 咬勢備的脰卜’將預先在各自的容器中保管 乳體的πw认到—似合頭巾，混合至均f，在規定 11 201226428 的模=中鑄型，再加熱魏的方法也是可行的。 此日可的異氰酸自旨指數(異氰酸旨基/ ^150 ^ #,J^^6〇.12〇0,r,s 〇 表面產生黏腻感。另外，指數過高時 合 陷而無法得到柔軟發泡體。 《柯泡，有k會塌 if相3模if ’為了使此時硬化均勻且獲得充分的發泡㈣， ，的^框調節在30〜8叱的範圍内，但在’二= 4,這疋不需要的。從生產效率的方^ 體成盃日寸 =^^生/_件__。品ΐ ^ 的料壓軸在越下破壞泡 實施例 施例^彳^步描述本發_具體實闕’本發财僅限於本實 [脲基曱酸酯變性聚異氰酸酯的製備丄] 合成例1 fe又有攪拌機、溫度計、冷凝H和氮氣導人管的容量：匕的 反。應器中，加入950g六亞甲基二異氰酸酯(HDI)、5〇g異丙醇，在 9〇C下進行2小時氨基甲酸醋化反應。藉由印瓜分析反應產物的 ，果’羥基消失。接著’加入〇.4辛酸氧錘，在9(rc下反應3小時。 藉由FT-IR和13C-NMR分析反應產物的結果，氨基甲酸酯基消失。 接著，添加O.llg JP-508(城北化學製造），在5〇t下進行丨小時終止 反應。終止反應後的反應產物的異氰酸酯含量為4〇46%。將該反 應產物在140°C · 40Pa下進行薄膜蒸餾，得到異氰酸酯含量為 19.5%、25 C的黏度為lOOmPa · s、遊離六亞曱基二異氰酸酯含量 為0.1%、色數20APHA的“腺基甲酸酯變性聚異氰酸酯_丨，，。藉由 FT-IR、13C-NMR分析“脲基曱酸酯變性聚異氰酸n”的結果，没 有發現氨基甲酸酯基的存在，確認脲基甲酸酯基的存在。另外， 發現了微量程度的脲二酮基和異氰脲酸酯基。 12 201226428 - [脲基曱_變性聚異氰酸酷的製備2] 合成例2 人除了添^795(^六亞曱基二異氰酸酯(11〇1)、5吆丁醇以外，用 與合成例1同樣的方法，得到“脲基曱酸酯變性聚異氰酸酯_2，，(異氰 酸醋含1為19.0%、25。(：的黏度為9〇11^.5、遊離六&曱基二里氰 酸醋含量為0.1%、色數20APHA)。 [脲基甲酸酷變性聚異氰酸醋的製備3] 合成例3 除了添加950g六亞曱基二異氰酸酯(HDI)、5〇g 3_甲基戊二醇 以外’用與合成例丨同樣的方法’得到“脲基曱酸酯變性聚異氰酸 S旨-3”(異氰酸醋含量為191%、坑的黏度為172〇偷· s、遊離六 亞甲基二異氰酸酯含量為〇.1〇/〇、色數20APHA)。 [脲基甲酸酯變性聚異氰酸酯的製備4] 合成例4 除了添加95〇g六亞甲基二異氰酸酯(HDI)、50g PTG-250(保土 威化學公司製造)以外’用與合成例1同樣的方法，得到“腺基曱酸 酯變性聚異氰酸酯-4”(異氰酸酯含量為17.0%、^艽的黏度為 1770mPa · s、遊離六亞曱基二異氰酸酯含量為〇1%、色數 20APHA) ° [脂肪族系異氰酸酯變性三聚體的製備] (聚異氰酸酯合成例1 :異氰酸酯1(含異氰脲酸酯基的異氰酸 酯)） . 在設有溫度計、攪拌機和氮氣導入管的1000ml的帶蓋的玻璃 制四頸燒瓶内’加入997g六亞甲基二異氰酸酯、2g 1,3-丁二醇，氮 氣吹掃後，邊攪拌邊升溫至5〇°C，添加lg苯酚、〇.2g催化劑(異 酸鉀）’在50°C下反應1.5小時。接著，立即在65°C下進行反應，在 達到目標NCO含量的時刻’加入〇」g作為終止劑的填酸，進行y、 時終止反應。接著’在130¾、0.04kPa的條件下進行薄膜蒸餾，除 去遊離HDI。 ~ • 這樣得到的異氰酸酯“含異氰脲酸酯基的異氰酸酯-Γ是淡黃 13 201226428 色液體，NC0含量為23.2%，黏度為118〇(mPa，25°C下）。 使用以下的原料製備軟質聚氨酯發泡體。各原料的標稱平均 I能對於異氰酸酯成分而言*NC0基的數量，對於多元醇成 分而言是OH基的數量。在各實施例丨〜^和各比較例丨.〜22中使用的 原料的種類和用量在表1〜4中總結示出。 表1〜4中的各數值對於異氰酸酯成分而言表示質量％，對於其 他成分而言表示質量份數。 <多元醇成分> 多元醇A : NEF-455(聚醚多元醇’曰本聚氨酯工業製造，標稱 S 月&基數3 ’ OH值=150KOHmg/g) 多元醇B : NEF-456(聚醚多元醇，日本聚氨酯工業製造，標稱 s 月b基數3，OH值=l48KOHing/g) 多元醇C : SANNIXPP-1000(聚醚多元醇，三洋化學工業公司 製造’標稱官能基數2，OH值=112KOHmg/@ <催化劑> CAT1 · TOYOCATET(胺催化劑，東曹製造） CAT2 : DBU(胺催化劑，SAN-APROLTD·製造） CAD : DABCOT_9(金屬催化劑，Air Products (股)製造） <其他> 添加劑1 : Color stabilizer CS-22(填系抗氧化劑，Momentive公 司製造） HALS : TINUVIN765(受阻胺系光安定劑，BASF製造） 穩泡劑1 : SH-192(石夕系穩泡劑，Dow Coming Corporation製造) 水：自來水 14 201226428Propyl alcohol, isopropyl alcohol, isopropanol, pentanol, hexanol and heptanol, propylene glycol, hydrazine 3 ^ L, & atomic number 1Q~20, simple scale, ethylene glycol, H戊四, i 戊! Dibutyl, with butanediol, μ-butanediol, i-mercapto-2-propyl 4 3_ and hexamethylene alcohol, 2,5-hexanediol, 3-曱Base-1,5·pentanediol, decanediol, 1>2•Tra “alcohol, 2,2,4·dimethyl-16-hexanediol, 1,1 〇, methyl propyl ketone, season戌 Γ Γ, 知, 三μ基乙院, 三瘦•, ethyl alcohol monoalkyl _ or _ allyl ether, propylene glycol monoterpene 6 201226428 ether, diethylene glycol 'triethylene glycol and tetraethyl. Cyclic alcohol: alcohol m, i if, mercaptocyclohexanol, tridecylcyclohexanol, 4 · tert-butylcyclohexyl cyclohexane diol, M_cyclohexyl _ brewing base 虱 虱 裱 二Yeast, υ- 1 4-雔-办甲其_ ί Ι 二 dihydroxy-1,1,3,3-tetradecyl-cyclobutane, hexamethylene benzoate, and "cyclohexyl" 曱System, 2,2_double (4-trans-base ring double ^^^^^, water J'4_bis(4_ylylcyclohexyl)pentane, decyl alcohol, tetrahydrofurfuryl alcohol, gram gas T-based borneol And two light sulfhydryl-tricyclic terpines. Alcohol.: Polyfluorene polyol, polycarbonate polyol, and polyacetate. The well-known "polyol, which has 1~6 her group, or epichlorohydrin, epoxidized oxime:: ene; hydrogen: butyl, The styrene oxide = alcohol ^ ^ has the opposite; the gas qi ===: times: it can also use the condensation product of thiodiglycol itself and / or the condensation product with its constituents as polysulfonium. The viscosity and the phase of the polyol (8) are thiol-based. The substance is at least a rhyme-numbered HQ-salt compound. As a result of the production of the urea-based f-ester, the fluorinated diisocyanate vine having a fatty acid or alicyclic system is particularly limited as long as it is an aliphatic or alicyclic system. As an example of the aliphatic diisocyanate, there are six i: base code (HDI), lysine diisocyanate, butylene diiso, and '3 £7', _1, '4 _, cyanate § , octamethyl diisocyanate vinegar, etc., as the alicyclic diisole vinegar, as an example of alicyclic diiso-acid vinegar, there are isophorone Erli J vinegar (leg), hydrogenated diphenylmethane Anisotropic acid vinegar (hydrogenated hydride), hydrogenated benzene: one isocyanate (hydrogenated XDI), cyclohexyl diisocyanate, methylcyclohexanyl diiso, monohexyl methane diisocyanate, etc. Isocyanates. In addition, benzene dimethyl diisocyanate 201226428 decyl benzene dimethyl diisocyanate (tmxdi) which has inferior 9 soil but isocyanate vinegar does not directly bind to the aromatic ring can also be used as a fatty substance. Used in the present invention. On this day of the day, it is advisable to use 脳. Here, since the vapor pressure of the abdomen is extremely low, it is preferable to adjust so that the urea-based bismuth acid used in the organic polyisocyanate composition has a mass of i. /. The salt-over-metallized metal salt and the oxidized soil-measured metal salt are used in the manufacture of a tetrahydro-organic polyisomeric complex of a compound having an alcoholic group and an aliphatic and/or alicyclic ring. In particular, from the point of view of the bismuth two-two substance, 'carboxylic acid mis-salt, neo-oxo-salt salt is the most suitable' as a virgin, 4-azabicyclooctane, 15-diazabicyclononene , 甲甲美丁二脸=mercaptopropane diamine and bis-indole dimethylaminoethyl _. Benzene or the like "Cannes are suitable catalysts. Nitrogen-containing aromatic compounds such as = early C1~C4-alkyl*, dimercapto, dimethylamino-pyridyl. Pyridyl and dimercaptopyridine can also be used. 〇~(:4_1^alkyl-pyridyl C1 ～C4-N-alkyl-pyrroline, pyrazole, Cl~C4-N-alkyl-imidazole, C1~C4_N _Alkyl _ σ 唾 唾 ΐ Λ Λ α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α α丨 伞 伞 伞 伞 伞 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 喹 喹 喹 喹 喹 喹 喹 喹 喹 喹 喹 喹 喹 喹 喹A method of denaturation (trimerization) of a polyisocyanate in the presence of the polyisocyanate is used. As the method of denaturation, for example, the method described in Japanese Patent No. 33714_Tai: 2002-241458 can be used. As the acidification catalyst, for example, a fatty salt, a bismuth salt such as benzoyl, a 2,4,6-tris(didecylaminofluorenyl)benzoquinone, 2,4-bis(di)methyl 8 201226428 ^aminoguanidine can be used. Phenol, 2,6-di tert-Butyl-4-didecylaminotridecylnonanephenol, s-amine, N,N',N,,-tris(didecylaminopropyl)hexahydro-s-triazine, diazabicyclo An amine compound such as undecene. Among them, a tin salt, a potassium salt, a sodium salt, and a zinc salt of an aliphatic carboxylic acid are preferred, and acetic acid, propionic acid, undecanoic acid, citric acid, octanoic acid, and nutmeg. Acidic salts are most suitable. As a commercially available product, 2-hydroxypropyltridecylamine, zincate (DABCO TMR 'Air Products), potassium octoate (DABCOK-15 ' Air Products) can also be used. (manufactured by the company). The polyisocyanurate obtained as described above has an isocyanurate group and also has a glyphosate-based phthalic acid group formed by reaction. The oleic acid of citrate and azeotropic acid can be adjusted by the time adjustment of the isocyanate g. The polyisocyanate which has been pre-formulated with urea. g. Further, the cyanoic acid S is used to adjust the molar ratio of the lyrics/isofines. The flat polyol (8) is a nominal average functional group of 2 to 6, and the number J bubble is aggregated. § Polyol 酉曰J contains; diethylene glycol, dipropylene glycol, oil for: digestive B - moon female, sorbitol, etc., in addition to polyethylene 2 222 polymerized epoxy (10)), an epoxy: polymer polyol, a base: a propionitrile or a vinyl group, and an alcohol, butanediol, and gansate obtained by reacting a modified cyanic acid containing a dispersed urea As the alcohol, adipic acid and ethylene phosphorus-containing polyol, polyester ether polyol, and the like can be used. - alcohol, butylene polyol, 60~2~6, number average molecular weight, etc., denatured poly-polyol 1 "transfer" polyol or condensation of this ~ 2, _ = 3 number ^ ~ 6, The number average molecular weight is 口 酉曰 ,, the number average molecular weight is 200~6, _ 201226428 承四亚曱基_polyol, equivalent 2 (10)~2, _ polycarbocene diol and the like. This sterol can be used according to the ride, and it is also possible to mix the two _. — ^ There is no particular limitation on the catalyst (c) used in the present invention. In the present invention, the age-based catalyst, the metal catalyst, the card base, and the derivative thereof, which are used for making the IU-based foam, can be used as t. Amine-based catalysts, relatively mild tertiary amines, especially = ethylenediamine is suitable 'in addition, tridecylaminoethylethanolamine, -mercaptoethylethylethanolamine, dimethylamino thief, triethyl Amine, hydrazine-isobutyl I-imidazole, decyl sulphate, ethyl sulphate, diethanolamine, tetramethylhexamethylenediamine, dimethyl-hexylamine, tetramethylpropanediamine, triterpene Aminoethyltrans, tetramethyldiamine-di(dimethylaminopropyl)hexahydro-P-triamine, dinonylbenzylamine, dioxime=aminoethoxyethanol, monodecylaminohexanol , 曱 经 based on the base D melon and so on. In addition, 2 can make the ribs to the fairy's silky test of its derivatives. The amine having a vein and its emitter are preferably m, 8_4 heterobicyclo(5,4,G) undecene_7_dioxabicyclo(4,3,0) quinone 5,6_ Dibutylamino-1,8-. Azabicyclo (,,) undec-7-ene. Examples of the diazabicycloalkane include 丨8_diheterobicyclo(5,4,fluorene)deca-carbon-7-ene (hereinafter also referred to as DBU) and diaza cones. A weak acid alkali metal salt, a trimerization catalyst, and the like. As the catalyst, it is preferred to use stannous octoate, dibutyltin diacetate, butyltin dilaurate, and other relatively mild tin-based catalysts which are generally used for polyurethane foams. Among the above-mentioned catalysts, in the present invention, in order to obtain a good balance of reactivity, a good uniformity of =, a low closed cell property, and a foam which is a stable foam, at least DBU and stannous octoate are used. As the foaming agent (D) used in the present invention, a foaming agent which is generally used for the polymerization of polyurethane can be used. For example, as the physical foaming agent, pentane;): a hydrocarbon compound such as hexane or hexane, including HCFC-141b, HCFC-123, HCFC-n, ^145ίνTMΜ65Π^, dirty-13, etc. As a chemical foaming agent, water, an organic acid, etc. are mentioned. In addition, it can also be used in a gas filling device to dissolve air, nitrogen, and carbonic acid in the attack. These foaming agents may be used in combination of two or more kinds, and the amount thereof is suitably 10 201226428, which is 1 to 50% by mass of the polyol. As the foam stabilizer (E) used in the present invention, L-5309, L-5366, L-5420, L6202B (manufactured by Momentive Co., Ltd.), F-242T, F-303, and F-703 (Shin-Etsu Chemical Industry Co., Ltd.) can be used. Manufactured, SH-192, SH-193, PRX-607, SRX-280A, SF-2914, F-122, SF-2962 (manufactured by Dow Corning Corporation), B-8300, B-4113LF (manufactured by Evonik), A foam stabilizer for soft, hard or HR polyurethane foams, such as DC-5169 and DC-193 (manufactured by Air Products). In the present invention, in addition, other conventionally known additives may be used as needed. For example, by blending an antioxidant or an ultraviolet absorber, it is possible to further improve the excellent discoloration resistance which is a feature of the present invention. Specifically, there are an antioxidant such as a phenol antioxidant or a phosphorus antioxidant, a benzotriazole-based or a benzophenone-based ultraviolet absorber. In particular, as a filling antioxidant, COLOR STABILIZER CS-22 (manufactured by M〇mentiVe Co., Ltd.) is preferable because of the reason that the effect of suppressing discoloration is large. In addition to the above, a known flame retardant, a surfactant, a scorch, a colorant, a conductive agent, an insulating agent, a luminescent agent, an antibacterial agent, an aromatic agent, and the like may be added as a scorch prevention agent. The reason why the effect of suppressing the scorch is large is JPE-10 and JPE-13R (manufactured by Seongbuk Chemical Co., Ltd.). In order to produce the soft poly(4-) foam of the present invention by using these raw materials f, it is possible to scream the secret of the recording and grading foam. The polyisocyanur tir poly 70 alcohol component, catalyst, foaming agent and other additives previously stored or prepared in respective containers are put into -, and stirred to achieve the same f, and the reaction is initiated. Next, the : ίίί ΐ frame, laid on the bottom _ conveyor belt, reaction, foaming and by using a two-component system of different ingredients, polyol components, The πw of the milk stored in the container is recognized as a headscarf, and mixed to the average f. In the mold of the specified 11 201226428, the method of heating the Wei is also feasible. This is an isocyanate self-property index (isocyanate base / ^150 ^ #, J ^ ^ 6 〇.12 〇 0, r, s 〇 surface of the sticky feeling. In addition, the index is too high However, it is impossible to obtain a soft foam. "Ke bubble, there will be a collapse of the if phase 3 mode if 'In order to make the hardening at this time uniform and obtain sufficient foaming (4), the frame adjustment is in the range of 30 to 8 inches, But in 'two = 4, this is not needed. From the production efficiency of the body ^ cup into the day = ^ ^ raw / _ pieces __. The pressure axis of the product ^ under the destruction of the bubble embodiment example ^彳^step description of the hair _ specific implementation 本 本 阙 本 本 本 本 本 本 本 本 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 脲 合成 fe 合成 fe fe fe fe fe fe fe fe fe fe fe fe In the reactor, 950 g of hexamethylene diisocyanate (HDI) and 5 μg of isopropanol were added, and the carbamate reaction was carried out for 2 hours at 9 ° C. The reaction product was analyzed by Yingua. The fruit hydroxy group disappeared. Then, the 〇.4 octanoic acid oximeter was added and reacted at 9 (rc for 3 hours. The urethane group disappeared as a result of analyzing the reaction product by FT-IR and 13C-NMR. Next, O.llg JP-508 (manufactured by Seiki Chemical Co., Ltd.) was used to terminate the reaction at 5 Torr, and the isocyanate content of the reaction product after termination of the reaction was 4 〇 46%. The reaction product was at 140 ° C · 40 Pa. Thin film distillation was carried out to obtain "glycosylation-denatured polyisocyanate" having an isocyanate content of 19.5%, a viscosity of 25 C of 100 mPa·s, a free hexamethylene diisocyanate content of 0.1%, and a color number of 20 APHA. As a result of analyzing "ureido phthalate-denatured polyisocyanate n" by FT-IR and 13C-NMR, the presence of a urethane group was not observed, and the presence of an allophanate group was confirmed. A slight degree of uretdione and isocyanurate groups. 12 201226428 - [Urea-based oxime _ denatured polyisocyanate cool preparation 2] Synthesis Example 2 In addition to adding 795 (^ hexamethylene diisocyanate) In the same manner as in Synthesis Example 1, except that 11 〇 1) and 5 butyl butanol, "ureido phthalate-denatured polyisocyanate 2 was obtained, (isocyanate containing 1 was 19.0%, 25 (:: The viscosity is 9〇11^.5, the free six & thioglycolic acid vinegar content is 0.1%, the color number is 20APHA). Preparation of denatured polyisocyanuric acid vinegar 3] Synthesis Example 3 A urea was obtained in the same manner as in the synthesis example except that 950 g of hexamethylene diisocyanate (HDI) and 5 〇g 3 -methylpentanediol were added. The phthalate-denatured polyisocyanate S is -3" (the isocyanic acid content is 191%, the viscosity of the pit is 172 〇 stealing s, and the free hexamethylene diisocyanate content is 〇.1 〇 / 〇, Color number 20APHA). [Preparation 4 of allophanate-denatured polyisocyanate] Synthesis Example 4 In addition to 95 gram of hexamethylene diisocyanate (HDI) and 50 g of PTG-250 (manufactured by Hodgkin Chemical Co., Ltd.) In the same manner as in Synthesis Example 1, "glycosyl decanoate-denatured polyisocyanate-4" was obtained (the isocyanate content was 17.0%, the viscosity of the oxime was 1770 mPa·s, and the free hexamethylene diisocyanate content was 〇1%. , color number 20APHA) ° [Preparation of aliphatic isocyanate denatured trimer] (Polyisocyanate synthesis example 1: Isocyanate 1 (isocyanurate-containing isocyanate)). With thermometer, stirrer and nitrogen inlet tube Adding 997g of hexamethylene diisocyanate to a 1000ml glass four-necked flask with a lid After 2 g of 1,3-butanediol was purged with nitrogen, the mixture was heated to 5 ° C under stirring, and lgphenol and ruthenium (2 g of a catalyst (potassium acid hydride) were added to react at 50 ° C for 1.5 hours. Next, the reaction was immediately carried out at 65 ° C, and acid was added as a terminator at the time when the target NCO content was reached, and the reaction was terminated by y. Then, thin film distillation was carried out under conditions of 1303⁄4 and 0.04 kPa to remove free HDI. ~ ? The isocyanate thus obtained "isocyanurate-containing isocyanate-oxime is light yellow 13 201226428 color liquid, NC0 content is 23.2%, viscosity is 118 〇 (mPa, 25 ° C). Preparation using the following raw materials Soft polyurethane foam. The nominal average I of each raw material can be the number of *NC0 groups for the isocyanate component and the number of OH groups for the polyol component. In each of the examples, ^~^ and each comparative example. The types and amounts of the raw materials used in ～22 are summarized in Tables 1 to 4. The numerical values in Tables 1 to 4 represent the mass% for the isocyanate component and the mass fraction for the other components. Alcohol component > Polyol A : NEF-455 (polyether polyol 'Mulberry polyurethane industrial manufacturing, nominal S month & base 3 ' OH value = 150 KOHmg / g) Polyol B : NEF-456 (polyether multi-component Alcohol, manufactured by Japan Polyurethane Industry, nominal s monthly b base 3, OH value = l48KOHing / g) Polyol C : SANNIXPP-1000 (polyether polyol, manufactured by Sanyo Chemical Industry Co., Ltd. 'Nominal functional group number 2, OH value = 112KOHmg/@ <catalyst> CAT1 · TOYOCATET (amine catalyst, Cao Manufacturing) CAT2: DBU (Amine Catalyst, manufactured by SAN-APROLTD) CAD: DABCOT_9 (Metal Catalyst, manufactured by Air Products) <Other> Additive 1: Color stabilizer CS-22 (filling antioxidant, Momentive Manufactured by the company) HALS: TINUVIN765 (hindered amine light stabilizer, manufactured by BASF) Foam stabilizer 1: SH-192 (Shihsian foam stabilizer, manufactured by Dow Coming Corporation) Water: tap water 14 201226428
【II 製備例 12 NCO-12 8 ^ 1750 〇\ ι~Η ν〇 製備例 11 NCO-11 Ο 〇 〇〇 (N 00 〇 卜 00 On 1 19.2 寸· 製備例 10 NCO-10 Ο Ο m 卜 〇 742 19.2 CN — 製備例9 NCO-9 Ο 〇 m 卜 〇 724 17.6 rn 一 製備例8 NCO-8 〇 o ^ 〇 ε； 19.0 νο ΓΛ 製備例7 NCO-7 Ο 〇 420 1________ 19.3 VO cn 製備例6 NCO-6 ο ο 10^0 ο 418 '19.3 〇 ΓΛ 製備例5 NCO-5 ο ο in m 〇 421 1 18.2 CO 製備例4 NCO-4 ο ο 00 CS 〇 m Ό 18.6 00 CN 製備例3 NCO-3 Ο Ο 00 〇〇 CN 〇 I-< 19.4 00 CN 製備例2 NCO-2 Ο ο ΟΝ — 〇 m m 19.5 v〇 CN 製備例1 NCO-1 100 1 0.8 Ο ι—Η 19.5 寸 CN 1 — cs m 寸 》~η 1 1 1 1 1 no am iHQ 〇){□ i)tu vet >d «π ven 镏智怒遛盔 isS^ 吨邮略邮邮 想遝遛遛遛镏 ¢- ¢- ¢- δ-兹砩砩硪蝴邮 杯辑骧辑筚+ 黏度(mPa，25°C) NC0含量(％) 官能基數 201226428 製備例 25 NCO-25 Ο Ο Ο 5 (N CN 〇 ο On 20.0 ΟΊ 製備例 24 NCO-24 ο ο 〇 cn (N un 〇 〇〇 oo 21.3 rS 製備例 23 NCO-23 ο ο ο 对 cn m 〇 485 20.5 cn 製備例 22 NCO-22 〇 〇 〇 οο 们 m CN 〇 m VO m 19.2 寸 cn 製備例 21 NCO-21 Ο ο ο ό m cn 〇 1 381 20.1 m 製備例 20 NCO-20 ο ο ο Ό ^ * 〇 379 19.4 i〇 ΟΊ 製備例 19 NCO-19 Ο Ο Ο 们 〇 1 399 19.7 in cn 製備例 18 NCO-18 Ο ο ο 寸 — ο i-H o 18.9 l〇 rn 製備例： 17 NCO-17 ο ο ο 〇〇 CN CN ο 286 20.2 製備例 16 NCO-16 Ο Ο Ο Ό <Ν (Ν 〇 269 19.4 製備例 15 NCO-15 Ο Ο Ο 00 卜 — CN 〇 215 20.2 ο CO- 製備例 14 NCO-14 Ο ο Ο 〇〇 0〇 *-Η 1->Η ON 19.8 oo CN 製備例 13 NCO-13 Ξ 2 1100 23.2 〇 ro V ^ ^ t "Τ 〇)(□ am jjtn a)cq 〇jo >cn ten ten ten >en 怒窗谱涊链 ^ ^ ^ mu do uni iim am ^ ^ >q νςπ >en >d >d 祐怒韶龆涊辑 ®— ¢- ¢- φ— ΐιΐ^ f ^ _ 邮 黏度(mPa，25°C) NCO含量(％) 官能基數 201226428 製備例 35 NCO-35 Ο Ο 〇 00 <N (N 〇 <Ν 25.4 1—M 製備例 34 NCO-34 Ο Ο 〇 00 ΓΛ (N 〇 Os ί-Η 25.4 00 cn 製備例i 33 NCO-33 Ο 〇 〇 〇〇 cn Ό (N 〇 οο »-H 25.2 卜 ΓΟ 製備例 32 NCO-32 m 〇 〇〇 ^ 〇 ! 235 21.2 v〇 ΓΠ 製備例 31 NCO-31 v〇 tn Ο 245 22.4 Ό cn 製備例 30 NCO-30 Ο Ο Ο <» Ό ΓΠ ^ s 22.4 口 製備例 2?__ NCO-29 Ο Ο Ο 00 VO ΓΛ *-η ^ 21.5 (N CO 製備例 28 NCO-28 〇 〇 〇 0〇 Γ-- CS — 6 S 22.0 〇 cn 製備例 27 NCO-27 ο ο 〇 οο C^· (Ν ^ 〇 宕 F·^ 22.5 O cn 製備例 26 NC026 Ο ο ο 卜 — （Ν 〇 VO 25.6 ON (N '―' (Ν m Tj- τ—· • III· i)〇i um ajoi am im «π »e3 «3 >en 怒键盔涊韶 ^ ^ ±i±i±llii^PQd ijtn inn akd im 4^! ~ «I «π *ea es «a §怒磁盔窗辑 ^ ®- ®- φ- . ®- ^ 奪？§ + 黏度(mPa，25°C) NCO含量(％) 官能基數 201226428 【寸< 製備例 45 NCO-45 100 <N 36.9 0 01 製備例 44 NCO-44 〇 (N 50.0 o <N 製備例 43 NCO-43 Ο Ο Ο 〇 寸― cn 〇 cn (N 28.8 00 cn 製備例 42 NCO-42 导沄 -^ S VO o 27.0 r- cn 製備例 41 NCO-41 沄？ - s S m cn i—H 27.1 l> c<i 製備例 40 NCO-40 ο ο ο 〇 °〇 (N ' (N 〇 s i-H 25.9 CN CO 製備例 39 NCO-39 Ο Ο Ο 〇 m CS — <Ν 〇 00 On 25.2 CN 製備例 38 NCO-38 0 0 0 0 5 t-H 1-H f—^ in T-H 22.7 〇 cn 製備例 37 NCO-37 ο ο ο o °〇 f·^· i-H y—i 2 r*H 22.9 〇 cn 製備例 36 NC036 ^ S d OS 25.8 〇\ CN T ^ 'T V iKQ i)tn Dd Λ)σΐ i)ID tCI >C3 »CI tCI td 键键韶韶键 ^ fc!S^ yes uni no ajoi Dm ^ 祝）et 阳 >d >en vex =龆龆怒怒辑 ¢- ¢- 6- ¢-$蝴硪砩砩邮 g辑_ _留♦ 黏度(mPa，25°C) NC0含量(％) 官能基數 201226428 (夕元醇預混物的製備） “Β_1，Ϊΐ表,5中記載的各原料，混合_半，得到多元醇預混物 衫-5’’ 〇 表5 ____ ----- 製備例46 製 --'一， 1 製備例4?! 製備例49 製備例50 多70醇及ι B-1 B-4 ——---- --- Β·5 多元•醇(A) 多元醇(B) _.多元雙、 ^~~~ CAT2 CAT^ 100 ---— 0.6 0.8 0.15 1〇〇 --------- 90 -_10 —— 100 100 0.6 0.8 0.6 0.8 0.6 0.8 0.15 0.6 0.8 Λ 1 « "—— HALS ” 1 添加劍1 __*-- ---—__ ·> 穩泡®|丨1 3 3 J η 水 3.6 L—^__ 3.6 D 3,6 (軟質聚氨酯發泡體的製造） 使用有機聚異氰酸酯(異氰酸醋成分)“NCO-1〜NCO-45”和上述 多元醇預混物“Β1〜Β5”，如下所述製備軟質聚氨酯發泡體。即，按 表6〜9所示的比例，將各聚異氰酸酯組合物和多元醇預混物調溫至 溫度25±2°C，用Polymer Engineering公司製造的低壓發泡機攪拌之 後，排出到500mmx500mmx500mm尺寸的箱中，得到軟質聚气萨 發泡體。另外，表6〜9中，指數表示異氰酸酯成分與多元醇預 的莫耳比，配混比表示異氰酸酯成分與多元醇預混物的質量份數。 關於官能基數的測定’用GPC進行測定。測定儀器、測定條件 在以下示出。 〃 測定儀器：HLC-8220(GPC，東曹製造） 測定條件：管柱 TSKgel G3000H)a xTSKgel (32()()01¾ xG1000HXL(3 根）[II Preparation Example 12 NCO-12 8 ^ 1750 〇\ ι~Η ν〇 Preparation Example 11 NCO-11 Ο 〇〇〇 (N 00 〇 00 On 1 19.2 inch · Preparation Example 10 NCO-10 Ο Ο m 〇 742 19.2 CN - Preparation 9 NCO-9 Ο 〇m 〇 724 17.6 rn a preparation example 8 NCO-8 〇o ^ 〇 ε; 19.0 νο 制备 Preparation Example 7 NCO-7 Ο 〇 420 1________ 19.3 VO cn Preparation Example 6 NCO-6 ο ο 10^0 ο 418 '19.3 制备 Preparation Example 5 NCO-5 ο ο in m 〇 421 1 18.2 CO Preparation Example 4 NCO-4 ο ο 00 CS 〇m Ό 18.6 00 CN Preparation Example 3 NCO- 3 Ο Ο 00 〇〇CN 〇I-< 19.4 00 CN Preparation 2 NCO-2 Ο ο ΟΝ — 〇mm 19.5 v〇CN Preparation Example 1 NCO-1 100 1 0.8 Ο ι—Η 19.5 inch CN 1 — cs m inch》~η 1 1 1 1 1 no am iHQ 〇){□ i)tu vet >d «π ven 镏智怒遛Helmet isS^ ton postal postal postal 遝遛遛遛镏¢- ¢- ¢ - δ- 砩砩硪 砩砩硪 邮 邮 邮 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 ( ( ( ( ( ( ( Example 24 NCO-24 ο ο 〇cn (N un 〇〇〇oo 21.3 rS Preparation Example 23 NCO-23 ο ο ο vs cn m 〇 485 20.5 cn Preparation Example 22 NCO-22 〇〇〇οο m m 〇m VO m 19.2 inch cn Preparation Example 21 NCO-21 Ο ο ο ό m cn 〇1 381 20.1 m Preparation Example 20 NCO-20 ο ο ο Ό ^ * 〇 379 19.4 i〇ΟΊ Preparation Example 19 NCO-19 Ο Ο Ο 〇 1 399 19.7 in cn Preparation 18 NCO-18 Ο ο ο 寸 — ο iH o 18.9 l〇rn Preparation: 17 NCO-17 ο ο ο 〇〇CN CN ο 286 20.2 Preparation 16 NCO-16 Ο Ο Ο Ό <Ν (Ν 〇 269 19.4 Preparation 15 NCO-15 Ο Ο Ο 00卜—CN 〇215 20.2 ο CO- Preparation Example 14 NCO-14 Ο ο Ο 〇〇0〇*-Η 1->Η ON 19.8 oo CN Preparation 13 NCO-13 Ξ 2 1100 23.2 〇ro V ^ ^ t "Τ 〇)(□ am jjtn a)cq 〇jo >cn ten ten ten >en 怒窗谱涊 chain ^ ^ ^ mu do uni iim am ^ ^ >q νςπ >en >d > d 韶龆涊 韶龆涊 ® — - ¢ - ¢ - φ - ΐιΐ^ f ^ _ zip viscosity (mPa, 25 ° C) NCO content (%) Functional Group 201226428 Preparation 35 NCO-35 Ο Ο 〇 00 < N (N 〇 < Ν 25.4 1 - M Preparation Example 34 NCO-34 Ο Ο 〇00 ΓΛ (N 〇Os ί-Η 25.4 00 cn Preparation i 33 NCO-33 Ο 〇〇〇〇cn Ό (N 〇οο »-H 25.2 ΓΟ Preparation Example 32 NCO-32 m 〇〇〇^ 〇 235 21.2 v〇ΓΠ Preparation 31 NCO-31 v〇tn Ο 245 22.4 Ό cn Preparation Example 30 NCO-30 Ο Ο Ο <» Ό ΓΠ ^ s 22.4 Preparation Example 2?__ NCO-29 Ο Ο Ο 00 VO ΓΛ *-η ^ 21.5 (N CO Preparation Example 28 NCO-28 〇〇〇0〇Γ--CS-6S 22.0 〇cn Preparation Example 27 NCO-27 ο ο 〇οο C^· (Ν ^ 〇宕F ·^ 22.5 O cn Preparation 26 NC026 Ο ο ο 卜 — (Ν 〇 VO 25.6 ON (N '―' (Ν m Tj- τ—· • III· i)〇i um ajoi am im «π »e3 «3 >en anger key helmet 涊韶 ^ ^ ±i±i±llii^PQd ijtn inn akd im 4^! ~ «I «π *ea es «a § anger magnetic helmet window series ^ ®- ®- φ- . - ^ Capture? § + viscosity (mPa, 25 ° C) NCO content (%) Functional Group Number 201226428 [Inch < Preparation Example 45 NCO-45 100 < N 36.9 0 01 Preparation Example 44 NCO-44 〇 (N 50.0 o < N Preparation Example 43 NCO-43 Ο Ο Ο 〇 inch - cn 〇cn (N 28.8 00 cn Preparation 42 NCO-42 Guide -^ S VO o 27.0 r- cn Preparation 41 NCO-41 沄? - s S m cn i —H 27.1 l>c<i Preparation Example 40 NCO-40 ο ο ο 〇°〇(N ' (N 〇s iH 25.9 CN CO Preparation 39 NCO-39 Ο Ο Ο CSm CS — <Ν 〇00 On 25.2 CN Preparation 38 NCO-38 0 0 0 0 5 tH 1-H f—^ in TH 22.7 〇cn Preparation 37 NCO-37 ο ο ο o °〇f·^· iH y—i 2 r*H 22.9 〇cn Preparation 36 NC036 ^ S d OS 25.8 〇\ CN T ^ 'TV iKQ i)tn Dd Λ)σΐ i)ID tCI >C3 »CI tCI td key 韶韶 key ^ fc!S^ yes uni no Ajoi Dm ^ b) et yang > d > en vex = 龆龆 怒 ¢ ¢ - ¢ - 6- ¢ - $ 硪砩砩 硪砩砩 g _ _ _ ♦ ♦ viscosity (mPa, 25 ° C) NC0 content (%) Functional group number 201226428 (Preparation of oxime alcohol premix) "Β_1, Ϊΐ表, each raw material described in 5, mixed _ half, get more Pre-alcohol premix shirt-5'' 〇 Table 5 ____ ----- Preparation Example 46 - '1, 1 Preparation 4?! Preparation 49 Preparation Example 50 Poly 70 alcohol and ι B-1 B- 4 ———————— --- Β·5 Multi-alcohol (A) Polyol (B) _.Multiple, ^~~~ CAT2 CAT^ 100 ---— 0.6 0.8 0.15 1〇〇--- ------ 90 -_10 —— 100 100 0.6 0.8 0.6 0.8 0.6 0.8 0.15 0.6 0.8 Λ 1 « "—— HALS ” 1 Add Sword 1 __*-- ---___ ·> Stable Bubble® |丨1 3 3 J η Water 3.6 L—^__ 3.6 D 3,6 (Manufacture of flexible polyurethane foam) Using organic polyisocyanate (isocyanate component) “NCO-1~NCO-45” and the above plural The alcohol premix "Β1 to Β5" was prepared as described below to prepare a flexible polyurethane foam. That is, each of the polyisocyanate composition and the polyol premix was adjusted to a temperature of 25 ± 2 ° C in a ratio shown in Tables 6 to 9, and stirred with a low pressure foaming machine manufactured by Polymer Engineering, and then discharged to 500 mm x 500 mm x 500 mm. In the size of the box, a soft polygas foam is obtained. Further, in Tables 6 to 9, the index indicates the molar ratio of the isocyanate component to the polyol, and the compounding ratio indicates the parts by mass of the isocyanate component and the polyol premix. The measurement of the number of functional groups was measured by GPC. The measuring instrument and the measurement conditions are shown below. 〃 Measuring instrument: HLC-8220 (GPC, manufactured by Tosoh) Measuring conditions: column TSKgel G3000H)a xTSKgel (32()() 013⁄4 xG1000HXL (3 pieces)
THF流速：l.OOOml/min 檢測器：RI 19 201226428 測定溫度：40°C(管柱烘箱，注射，檢測器） 校準曲線：聚苯乙烯 官能基數的計算方法：NCO含量/4.2/ΙΟΟΟχ數量平均分子量 20 2 2 1X20 r*-l9<u—I 428 I NCO-ii I «/> ώ § Δ 55.2 Π5 寸 § 2 3 <〇 〇〇〇 S Ξ 實施例 ll NCO-IO »r> ώ § 〇 49.2 62 m 2 § = 〇〇〇 S 2 實施例 10 NC0-9 κη ώ § 〇 49.2 70 §； 2 S vq 〇〇Ο S 二 實施例 9 NC0-8 in ώ § Ο 47.7 60 寸 \〇 〇〇ο ΙΛ — 00 r4 實施例 8 NC0-5 ώ § 〇 48.2 58 \〇 § s 5 寸. 〇〇〇 5 ^ 實施例 7 NC0-4 «/*> ώ § 〇 48.9 73 cn ^ ^ >n 〇〇〇 卜 Ό 〇〇 “ 實施例 6 NCO-3 Β-5 § 〇 49.2 70 s 2 S >〇 〇ο〇 比較例 6 NCO-2 ώ § 〇 49.5 43 对 s S S X ο ο S3 實施例 5 NCO-7 m § 〇 47.1 65 m E ?： ' — —H 对 寸· ο ο ο S3 2 實施例 4 NC0-6 ώ § 〇 47.3 62 寸 fN un 1— I—« 〇〇〇 s s 實施例 3 NC0-6 Β-3 § 〇 48.2 83 v〇 S § 5 ο ο ο 實施例 2 NC0-6 Β-2 § 〇 44.3 72 ir» S ξ 5 Ό O ο ο ο in (N 〇〇 iri 實施例 I NC0-5 ώ § 〇 5 00 »-H «-Η 〇〇〇 \〇 ΓΛ 〇〇 v〇 比較例5 NCO-45 ώ § 塌陷 1 i i 比較例4 NCO-44 ώ § 塌陷 1 1 t 比較例3 NC0-I3 ώ § 塌陷 i i 比較例2 NCO-12 ώ g < η s v〇 — 寸 s S 5 cn o 〇ο〇 m 〇〇 OO 比較例 I NC0-1 ώ § △ 48.2 32 in 9 § S d X〇〇 s S 有機聚異氰酸酯 多元醇預混物 指數 成型性 密度(kg/m3) 25%ILD(N/3l4cm2) 落球回彈率(％) TB(kPa) EB(%) TR(N/cm) 壓縮永久變形(％) 10分鐘後的表面硬化性 焦燒 外觀 件柄1 雎 ^ g < i遂 li 11 QSOS:s-SKf^H^^^^^¥w^qTi^^^^r,u^^-fi-r,u^frvs^4,it^^^l,PQ3,PQI饫荩,00寸9^-8口鳍迻^酰回铪飨客乎6<〜9<^ 201226428 比較例9 NCO-25 B-5 § Δ 50.6 108 〇\ s g 3 1—H CO 〇 〇〇〇 S 2 實施例21 NCO-24 B-5 r—< o 42.3 72 13.5 CN Ό 〇 O CN Z; 1—H >-H cn o 〇〇〇 實施例20 NCO-23 B-5 〇 43.5 85 寸 卜 — 二I 2 夺 in o 〇〇〇 — — 00 實施例19 NCO-22 j B-5 o ^ s »/*) § 5 °° CO 00 o 〇〇〇 2 S 實施例18 NCO-21 i B-5 另 〇 43.3 79 ^ s $ o 〇〇〇 實施例17 NCO-20 ； B-5 i 闵 o 45.2 84 v〇 g ® ， — ΓΠ o 〇〇〇 實施例16 NCO-19 B-5 1 呂 i-Η 〇 44.3 81 m r- o 〇〇〇 寸 q OO 實施例15 NCO-18 1 B-5 S r-H 〇 44.1 78 OO s笃^ Τ—( τ-Η ΓΠ yn o 〇〇〇 00 — 實施例14 NCO-Π | B-5 120 〇 42.8 69 as 93 174 3.5 00 o 〇〇〇 實施例13 NCO-16 B-5 o 43.5 74 o VO o 〇〇〇 v〇 ' OO 〇i 實施例12 NCO-15 | B-5 o 42.3 73 等§ ：Q o 〇〇〇 2 S 比較例8 NCO-14 B-5 o (N r—> 〇 , 1 42.5 84 〇\ ?! 2 ^ o X ο ο <N ^ 〇0 CS 有機聚異氰酸酯 It 指數 1 成型性 密度(kg/m3) 25%ILD(N/314cm2) 落球回彈率(％) TB(kPa) EB(%) TR(N/cm) 壓縮永久變形(％) 10分鐘後的表面硬化性 焦燒 外觀 耐候性試驗後之TB保持率 耐候性試驗後之ΛΥ1值 201226428 比較例11 NCO-35 B-5 37.4 52 s 5 S 〇〇 o X X〇 S 2 實施例29 NCO-34 B-5 1-H 〇 36.4 56 CN ^ 5 S o 〇〇〇 a ^ 實施例28 NCO-33 B-5 〇 36.8 59 i—Η s S ^ d 〇〇〇 s ^ 實施例27 NCO-32 B-5 〇 39.5 86 | od s S 5 o 〇〇〇 實施例26 NCO-31 B-5 〇 39.2 82 | ss ^ " 〇〇〇 s s 實施例25 NCO-30 B-5 〇 38.4 65 s $ ^ o 〇〇〇 實施例24 NCO-29 B-5 〇 39.2 — —6 7 一 I Ό s § 2 o 〇〇〇 實施例23 NCO-28 B-5 ί-Η 〇 38.8 72 I cn 72 114 2.1 o 〇〇〇 S3 實施例22 NCO-27 B-5 宕 〇 39.3 75 in s S 2 00 o 〇〇〇 叫 CO 00 CS 比較例10 NCO-26 B-5 宕 塌陷 1 1 1 1 1 1 1 有機聚異氰酸酯 多元醇預混物 指數 成型性 密度(kg/m3) 25%ILD(N/314cm2) 落球回彈率(％) TB(kPa) EB(°/〇) TR(N/cm) 壓縮永久變形(％) 10分鐘後的表面硬化性 焦燒 外觀 t： s g <1 5 ί % i ^ ή±Κ 箬i 201226428 比較例13 NCO-43 Β-5 120 塌陷 1 1 1 1 1 1 1 實施例35 NCO-42 Β-5 〇 35.2 48 寸 S ^ 〇〇〇 實施例34 NCO-41 j Β-5 1—Μ 〇 35.5 52 13.5 73 113.3 3.1 vq 〇 〇〇〇 <N ^ 〇〇 — 實施例33 NCO-40 Β-5 〇艺S 12.5 85 126.5 3.5 o 〇〇〇 —〇〇 〇〇 “ 實施例32 NCO-39 Β-5 1-Η 〇 35.6 61 14.5 s 2 ^ o 〇〇〇 實施例31 NCO-38 Β-5 120 〇 39.2 78 S 2 ^ vn o 〇〇〇 00 — 實施例30 ί NCO-37 Β-5 1—Η 〇 38.9 81 12.5 ^ 2 ^ \〇 o 〇〇〇 寸 9 〇〇 — 比較例12 NCO-36 Β-5 120 塌陷 1 1 1 1 1 1 有機聚異氰酸酯 * 指數 成型性 密度(kg/m3) 25%ILD(N/314cm2) 落球回彈率(％) TB(kPa) EB(%) TR(N/cm) 壓縮永久變形(％) 10分鐘後的表面硬化性 焦燒 外觀 耐候性試驗後之TB保持率 耐候性試驗後之ΛΥ1值 201226428 麵表6〜9 ’發泡體的密度根據所使用的有機聚異氰酸醋的種 Ϊ卢ίί:，比率而見到了高低差別，而發泡體製造時的反應 ，處於在使用上不特別構成問題的範圍内。另外造時和硬化 作業環境是良好的，沒有感覺到來自_等有&聚異氮酸醋 的々人不快的刺激氣味等。 <成型性評價方法> 由下式求出的值為5%以下則評價為0 : /回^ (%)={(上升時間時的發泡體高度)_(從上升時間起2分鐘 之後的高度卜(上升時間時的發泡體高度)χ1〇〇 <岔度· 25%ILD(N/314cm2)的測定方法〉 密度依據JISK7222測定，25%ILD依據JIS-K6400-2測定。 <壓縮永久變形的測定方法> 依據JISK6400-4測定。 <10分鐘後的表面硬化性試驗方法> 、從發泡開始起經過10分鐘的時刻，確認在發泡體表面是否無 黏腻，有黏腻的場合評價為x。在表面無黏腻，用手按壓時不殘留 手跡則評價為〇。 <焦燒的評價方法> 將發泡體按50cmx50cmx50cm的尺寸發泡，第二天切割發泡 如果中心部無變色則評價為〇。 關於外觀耐候性和頁變性的試驗，用sUga 丁6贫ins^mentsTHF flow rate: 1.00 ml/min Detector: RI 19 201226428 Measurement temperature: 40 ° C (column oven, injection, detector) Calibration curve: calculation method of polystyrene functional number: NCO content / 4.2 / ΙΟΟΟχ number average Molecular weight 20 2 2 1X20 r*-l9<u-I 428 I NCO-ii I «/> ώ § Δ 55.2 Π5 inch § 2 3 <〇〇〇〇S Ξ Example ll NCO-IO »r> ώ § 9.249.2 62 m 2 § = 〇〇〇S 2 Example 10 NC0-9 κη ώ § 〇 49.2 70 §; 2 S vq 〇〇Ο S II Example 9 NC0-8 in ώ § Ο 47.7 60 inches 〇 〇〇ο ΙΛ — 00 r4 Example 8 NC0-5 ώ § 8.2 48.2 58 \〇§ s 5 inches. 〇〇〇 5 ^ Example 7 NC0-4 «/*> ώ § 〇48.9 73 cn ^ ^ > ; n 〇〇〇 Ό 〇〇 "Example 6 NCO-3 Β-5 § 〇 49.2 70 s 2 S > 〇〇 ο 〇 Comparative Example 6 NCO-2 ώ § 9.5 49.5 43 s SSX ο ο S3 implementation Example 5 NCO-7 m § 〇47.1 65 m E ?: '--H pairs inch · ο ο ο S3 2 Example 4 NC0-6 ώ § 〇 47.3 62 inch fN un 1—I—« 〇〇〇ss implementation Example 3 NC0-6 Β-3 § 〇48. 2 83 v〇S § 5 ο ο ο Example 2 NC0-6 Β-2 § 〇44.3 72 ir» S ξ 5 Ό O ο ο ο in (N 〇〇iri Example I NC0-5 ώ § 〇 5 00 »-H «-Η 〇〇〇\〇ΓΛ 〇〇v〇Comparative Example 5 NCO-45 ώ § Collapse 1 ii Comparative Example 4 NCO-44 ώ § Collapse 1 1 t Comparative Example 3 NC0-I3 ώ § Collapse ii Comparison Example 2 NCO-12 ώ g < η sv〇 - s s S 5 cn o 〇ο〇m 〇〇OO Comparative Example I NC0-1 ώ § △ 48.2 32 in 9 § S d X〇〇s S Organic polyisocyanate Polyol premix index Formability density (kg/m3) 25% ILD (N/3l4cm2) Falling ball rebound rate (%) TB(kPa) EB(%) TR(N/cm) Compression set (%) 10 After the minute, the surface-hardening scorch appearance handle 1 雎^ g < i遂li 11 QSOS: s-SKf^H^^^^^¥w^qTi^^^^r, u^^-fi-r , u^frvs^4,it^^^l, PQ3, PQI饫荩, 00 inch 9^-8 mouth fins 酰 铪飨 铪飨 铪飨 铪飨 & & & 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 ^ ^ ^ ^ N N N N N N N N N N 5 § Δ 50.6 108 〇\ sg 3 1—H CO 〇〇〇〇S 2 Example 21 NCO-24 B-5 r—< o 42.3 72 13.5 CN Ό 〇O CN Z; 1—H >-H Cn o 〇〇〇Example 20 N CO-23 B-5 〇43.5 85 inch - two I 2 in in o 〇〇〇 - 00 Example 19 NCO-22 j B-5 o ^ s »/*) § 5 ° ° CO 00 o 〇〇 〇 2 S Example 18 NCO-21 i B-5 〇 43.3 79 ^ s $ o 〇〇〇 Example 17 NCO-20 ; B-5 i 闵 o 45.2 84 v〇g ® , — ΓΠ o 〇〇〇 Example 16 NCO-19 B-5 1 吕 i-Η 〇44.3 81 m r- o qq OO Example 15 NCO-18 1 B-5 S rH 〇44.1 78 OO s笃^ Τ—( τ -Η yn yn o 〇〇〇 00 - Example 14 NCO-Π | B-5 120 〇 42.8 69 as 93 174 3.5 00 o 〇〇〇 Example 13 NCO-16 B-5 o 43.5 74 o VO o 〇〇 〇v〇' OO 〇i Example 12 NCO-15 | B-5 o 42.3 73 et al. §: Q o 〇〇〇 2 S Comparative Example 8 NCO-14 B-5 o (N r—> 〇, 1 42.5 84 〇 \ ?! 2 ^ o X ο ο <N ^ 〇0 CS Organic Polyisocyanate It Index 1 Moldability Density (kg/m3) 25% ILD (N/314cm2) Falling Ball Rebound Rate (%) TB (kPa EB(%) TR(N/cm) Compression set (%) Surface hardening after 10 minutes of appearance. TB retention rate after weather resistance test ΛΥ1 value after weather resistance test 201226428 Comparative Example 11 NCO-35 B-5 37.4 52 s 5 S 〇〇o XX〇S 2 Example 29 NCO-34 B-5 1-H 〇36.4 56 CN ^ 5 S o 〇〇〇a ^ Example 28 NCO-33 B-5 〇36.8 59 i-Η s S ^ d 〇〇〇s ^ Example 27 NCO-32 B-5 〇39.5 86 | od s S 5 o 〇〇〇Example 26 NCO-31 B- 5 〇39.2 82 | ss ^ " 〇〇〇ss Example 25 NCO-30 B-5 〇38.4 65 s $ ^ o 〇〇〇Example 24 NCO-29 B-5 〇39.2 — —6 7 I I Ό s § 2 o 〇〇〇Example 23 NCO-28 B-5 ί-Η 〇38.8 72 I cn 72 114 2.1 o 〇〇〇S3 Example 22 NCO-27 B-5 宕〇39.3 75 in s S 2 00 o COCot CO 00 CS Comparative Example 10 NCO-26 B-5 宕 Collapse 1 1 1 1 1 1 1 Organic polyisocyanate polyol premix index Formability density (kg/m3) 25% ILD (N/314cm2 Falling ball rebound rate (%) TB (kPa) EB (° / 〇) TR (N / cm) Compression set (%) Surface hardenable scorch appearance after 10 minutes t: sg <1 5 ί % i ^ ή±Κ 箬i 201226428 Comparative Example 13 NCO-43 Β-5 120 Collapse 1 1 1 1 1 1 1 Example 35 NCO-42 Β-5 〇35 .2 48 inch S ^ 〇〇〇 Example 34 NCO-41 j Β-5 1—Μ 〇35.5 52 13.5 73 113.3 3.1 vq 〇〇〇〇<N ^ 〇〇—Example 33 NCO-40 Β-5 〇艺S 12.5 85 126.5 3.5 o 〇〇〇—〇〇〇〇 “Example 32 NCO-39 Β-5 1-Η 〇35.6 61 14.5 s 2 ^ o 〇〇〇 Example 31 NCO-38 Β-5 120 〇39.2 78 S 2 ^ vn o 〇〇〇00 — Example 30 ί NCO-37 Β-5 1—Η 〇38.9 81 12.5 ^ 2 ^ \〇o 9 9 〇〇—Comparative Example 12 NCO-36 Β-5 120 Collapse 1 1 1 1 1 1 Organic polyisocyanate* Index Formability density (kg/m3) 25% ILD (N/314cm2) Falling ball rebound rate (%) TB(kPa) EB(%) TR(N /cm) Compression set (%) Surface hardening after 10 minutes of appearance. TB retention rate after weather resistance test ΛΥ1 value after weather resistance test 201226428 Table 6~9 'The density of the foam according to the used The type of organic polyisocyanuric acid vinegar Lu: The ratio is high and the difference is seen, and the reaction at the time of foam production is in a range that does not pose a problem in use. In addition, the working time and hardening work environment were good, and there was no feeling of unpleasant irritating odor from the & and other polyamino vinegars. <Formability evaluation method> When the value obtained by the following formula is 5% or less, the evaluation is 0: /back ^ (%) = {(foam height at the time of rise) _ (2 minutes from the rise time) Subsequent heights (foam height at the time of rise) χ1〇〇<Measurement method of 25% ILD (N/314cm2)> The density is measured in accordance with JIS K7222, and 25% ILD is measured in accordance with JIS-K6400-2. <Measurement method of compression set>>Measured according to JIS K6400-4. <Test method for surface hardenability after 10 minutes>, at the time of 10 minutes from the start of foaming, it was confirmed whether there was no stickiness on the surface of the foam. It is greasy, and it is evaluated as x when it is sticky. It is not sticky on the surface, and it is evaluated as 〇 without leaving handwriting when pressed by hand. <Evaluation method of scorching> Foaming is foamed at a size of 50 cm x 50 cm x 50 cm, Two-day cutting foaming is evaluated as 〇 if there is no discoloration in the center. Regarding the appearance weathering and variability test, sUga ding 6 lean ins^ments
Co” Ltd.製造的Super Weather Meter(180W/m2，300〜400nm，濾光 器石英/#275，黑板溫度63。〇進行300小時試驗。 “ 關於外觀，基本上幾乎無表面劣化評價為〇,有劣化則評價為 X C關於耐候性，拉伸強度保持率為80%以上則評價為〇。 黃變性使用MINOLTA公司製造的色彩色差計CR_31〇測定γι 值。YI值之差(ΔΥΙ)為10以下則評價為〇。 貫施例中列舉的材料在外觀、耐候性、黃變性上獲得了沒有 特別問題的結果。 ^ 25 201226428 【圖式簡單說明】 〇 【主要元件符號說明】 無0Super Weather Meter manufactured by Co" Ltd. (180 W/m2, 300 to 400 nm, filter quartz/#275, blackboard temperature 63. 300 300 hours test. "About the appearance, almost no surface deterioration was evaluated as 〇, When the deterioration was evaluated, XC was evaluated as weather resistance, and when the tensile strength retention rate was 80% or more, it was evaluated as 〇. The yellow variability was measured using a color difference meter CR_31 制造 manufactured by MINOLTA Co., Ltd. The difference in YI value (ΔΥΙ) was 10 or less. The evaluation is 〇. The materials listed in the examples have no special problems in appearance, weather resistance, and yellowing. ^ 25 201226428 [Simple description of the diagram] 〇 [Main component symbol description] No 0