TW513459B - Polyurethane foam composition derived from a reaction mixture, the preparation process thereof, and polyurethane foam articles containing the same - Google Patents

Abstract

The present invention relates to a polyurethane foam composition derived from a reaction mixture comprising: a hydrogenated polydiene diol having a number average molecular weight from 1,000 to 20,000; an aromatic polyisocyanate; a plasticiser; and a blowing agent. Preferably, the polyurethane composition further comprises a tackifying resin. The present invention further relates to a process for preparing the polyurethane foam and to articles containing the polyurethane foam.

Description

513459 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（1 ) 本發明有關聚胺甲酸酯發泡體，尤其是包含一種多元醇 與方族異戴@旨之具挽性聚胺甲酸g旨發泡體。本發明另外 有關製備聚胺甲酸酯發泡體之方法與包含聚胺甲酸酯發泡 體物件。 具有高度彈能之聚胺甲酸酯發泡體通常係由一種聚醚三 醇與一種異氰酸酯製造。該聚醚三醇類之數量平均分子量 通常自4,5〇0至6,000，平均官能度係每個分子自2 4至2 7 個羥基。使用甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、 甲苯二異氰酸酯/二苯基甲烷二異氰酸酯混合物與經改良甲 冬一異來故@旨或二本基甲fe二異氨酸S旨改造物製造處理寬 各度廣之發泡體。異氧故酿官能度通常爲2·0，在大部分 實例中每個分子不多於2.3個異氰酸酯基。於促進發泡條 件下，聚醚三醇與每個分子具有2.0至2.3個異氰酸g旨基併 用會形成該彈能發泡體。 美國專利第4,939,184號描述由陽離子型方法製備之聚異 丁烯三醇類與二醇類製造之聚胺甲酸酯發泡體。該聚異丁 烯類係與一種異氰酸酯預混合，即一種官能度爲2.0之甲 苯二異氰酸醋偏位與對位異構物混合物之異氰酸|旨。然後 添加水作爲發泡劑形成該聚胺甲酸酯發泡體。製得之發泡 體彈能低，其適用於吸收能量應用。 國際（PCT)申請案WO 97/00902描述一種製自聚二晞二 醇之高彈能聚胺甲酸酯發泡體。該發泡體之彈能係添加官 能度自每分子2.5至3.0個異氰酸酯基的芳族聚異氰酸酯確 使其適當交聯達成。與習用聚胺甲酸酯發泡體相較，該製 -4- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ^--ΊΙΙ4! (請先閲讀背面之注意事項再填寫本頁} -訂· 513459 A7 _ B7 五、發明説明（2 ) 得之聚二晞二醇發泡體顯示優良之潮濕老化性質。 美國專利第5,710,192號描述一種製自聚二晞二醇之高彈 能、高耐撕扯性聚胺甲酸酯發泡體。該發泡體之彈能係藉 由選擇適量官能度自每分子1.8至2.5個異氰酸酯基的芳族 聚異氰酸酯確使其適當交聯達成。製得之發泡體耐撕扯性 優良，而且顏色接近白色。 上述發泡體中，其問題在於兼顧處理性與孔室大小控制 與孔室分佈。所需要的是具有高度可處理性發泡體，其具 有小而均勻孔室大小及分佈，並保有適度彈能發泡體性 質。 令人驚異的是，已發現於一種製自聚二烯二醇之聚胺甲 敗酉旨發泡體添加一種增塑劑，諸如高達5 0 % w油可製得具 有高度可處理性發泡體。因此，本發明有關一種衍生自反 應混合物之聚胺曱酸酯發泡體組合物，該反應混合物包 含： 一種數量平均分子量自1，000至20,000之經氫化聚二烯 二醇； 一種芳族聚異氰酸酯； 經濟部中央標準局員工消費合作社印製 一種增塑劑；及 一種發泡劑。 該發泡體於製造期間之黏度較低，與不添加油所製得之 發泡體相較，其具有更均勻之孔室結構。 根據另一個較佳之具體實例，本發明有關一種衍生自反 應混合物之聚胺甲酸酯發泡體組合物，該反應混合物 -5- 513459 A7 B7 五、發明説明（3 ) 含： 一種數量平均分子量自1，〇〇〇至20,000之經氫化聚二烯 二醇； 一種芳族聚異氰酸醋； 一種膠黏樹脂； 一種增塑劑；及 一種發泡劑。 該增塑劑可與經氫化聚二晞二醇相容爲佳。若增塑劑可 與該經氫化聚二烯二醇相容，隨後以較佳重量比率混合此 二組份，該組份於室溫下十二小時内不會分離成兩層。 增塑劑通常由熟知本技藝者選用。該增塑劑係一種油及/ 或一種分子量自500至20,000之經氫化聚二烯單醇爲佳。 附圖簡述 圖1顯示油對於黏度之影響。 圖2顯示油對於發泡體密度之影響。 圖3顯示水含量對於如本發明發泡體密度之影響。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 根據較佳具體實例之一，本發明係包含100重量份數 (pbw)數量平均分子量自1，000至20,000(自1，000至10,000 爲佳，自3,000至6,000最佳）之聚二烯二醇，自20至55 pbw之芳族聚異氰酸酯，高達200 pbw之增塑劑（以一種烴 處理油更佳）與一種發泡劑之彈能聚胺甲酸酯發泡體爲佳。 一較佳具體實例中，該經氫化聚二烯二醇之官能度係每 個分子自1.6至2個羥基，自1.8至2個羥基爲佳，所使用 之聚異氰酸酯官能度係每個分子自2.5至3.0個異氰酸酯 -6- 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 513459 A7 B7 五、發明説明（4 基。所添加之異氰酸酯濃度使異氰酸酯基及羥基數目接 近。該NCO:OH莫耳比率自〇 9至1 2爲佳。 本發明所使用之聚二烯二醇通常係陰離子型方法製備。 熟知本技藝者已詳知陰離子聚合作用，其描述於美國專利 第 5,376,745、5,391，663、5,393,843、5,405,911 及 5,416，168 號。 ’ 該聚二烯二醇之聚合作用係由一種包含—經保護羥基之 單鋰引發劑或每個鋰位置聚合一個共軛二烯單體之二鋰引 發劑引發。基於成本優勢之考量，該共概二晞通常爲u3_ 丁二烯或異戊間二烯，但是本發明中亦可使用其他共軛二 晞。當該共軛二晞係1，3-丁二晞，且所形成聚合物會被氫 化時，通常以結構改良劑（諸如二***或i 2 _二乙氧其乙 烷）控制該陰離子聚合作用，得到所需量之丨，仁添加物。 通常於終止前添加官能化劑終止陰離子聚合作用。所使 用之官能化劑係熟知本技藝者所習知，其描述於美國專利 第5,391，637、5,393,843及5,418,296號。較佳之官能化劑 係氧化乙烯。 經濟部中央標準局員工消費合作社印製 s 11 in·— m mtmMmMm ml m·· mmmmtmi Muni in (請先閱讀背面之注意事項再填寫本頁) #1 氫化該聚二烯二醇改良其安定性爲佳，使該二醇中至少 90%碳與碳雙鍵飽和，至少95%飽和爲佳。此等聚合物與 共聚物之氫化作用可以各種已確立之方法進行，包括如美 國專利第5,039,755號描述，存在觸媒諸如raney⑧鎳、 貴金屬諸如銷、可溶性過渡金屬觸媒與鈦觸媒之下進行氫 化作用。 該經氫化聚二烯二醇提供安定彈能發泡體。該聚二婦二 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 經濟部中央標準局員工消費合作社印製 513459 A7 B7 五、發明説明（5 ) 醇每個分子中具有自1.6至2個羥基爲佳，具有自1.8至2 個羥基更佳。平均官能度係，例如1.8表示該分子約80% 爲二醇類，該分子約20%爲單醇類。因爲產物分子大部分 具有兩個羥基，該產物被視爲一種二醇。本發明聚二烯二 醇之數量平均分子量介於1，000與20,000爲佳，自1，000至 10,000更佳，自3,000至6,000最佳。以經氫化聚丁二晞二 醇爲佳，1,2 -添加物含量介於4 0 %與6 0 %者尤佳。 該二晞微結構通常於氯仿中以13C核磁共振（NMR)測 得。該聚丁二晞二醇必須具有至少40% 1，2 - 丁二烯添加 物，因爲若該聚合物包含少於40% 1，2 - 丁二烯添加物，其 於氫化之後室溫下呈蠟狀。該1,2-丁二烯添加物之含量介 於40與60%爲佳。異戊間二烯聚合物通常具有至少80% 1，4_異戊間二烯添加物，以降低玻璃化溫度（Tg)與黏度。 本發明所使用之聚二烯二醇通常具有介於約500與約 10,000間之羥基當量，介於500與5,000更佳，介於1，500 與3,000最佳。因此，就聚二烯二醇而言，適當之數量平 均分子量介於1，000與20,000，介於1,000與10,000更佳， 介於3,000與6,000最佳。 本發明之經氫化聚二烯二醇數量平均分子量爲3300，官 能度爲1.92，1，2-丁二烯含量爲54%。氫化該聚合物去除 99%以上之碳與碳雙鍵。下文中此聚合物稱爲二醇1。 所使用之聚二烯單醇類實質上係如本文所述聚二烯二醇 般製備，但是係以單鋰引發劑引發該聚合作用。該單羥基 化聚二晞聚合物之數量平均分子量通常爲500至20,000， -8- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 衣. -tr填寫太 、11 經濟部中央標準局員工消費合作社印製 513459 A7 B7 五、發明説明（6 ) 以2,000至8,000爲佳。實施例經氫化聚二晞單醇數量平均 分子量爲3850 ，官能度爲0.98 ， 1，2- 丁二烯含量爲 48%。氫化該聚合物去除99%以上之碳與碳雙鍵。下文中 此聚合物稱爲單醇1。 本文所指之數量平均分子量係以具有已知數量平均分子 量之聚丁二烯標準校準之凝膠滲透層析法（GPC)測量之數 量平均分子量。該GPC分析用之溶劑係四氫呋喃。 本發明所使用之異氰酸酯係芳族聚異氰酸酯，因爲其具 有製造發泡體所需之迅速反應性。因爲該飽和聚二烯二醇 之官能度係每個分子約2個羥基，通常使用官能度自1.8 至3.0(以.2.5至3.0爲佳）之聚異氰酸酯達成所需之交聯密 度，以形成安定、高承載容量與高彈能之發泡體。使用官 能度較低之異氰酸酯類會形成較不安定之發泡體，其承載 容量較低，且彈能較差。具有更高官能度之異氰酸酯會形 成密閉孔室含量過高之發泡體，其對於物理性質有負面影 響0 適用之芳族聚異氰酸酯實例係MONDUR® MR (Bayer)， 其係一種聚合二苯基甲烷聚異氰酸酯，異氰酸酯官能度通 常爲 2.7。亦可使用 RUBINATE® 9225 (ICI Americas)，其 係一種由2,4 -二苯基甲烷二異氰酸酯與4,4 -二苯基甲烷二 異氰酸酯混合物組成之液態異氰酸酯，官能度爲2.06 ;然 而，於此較低官能度聚異氰酸酯形成之發泡體中添加一種 油或單醇會使該發泡體崩潰，故需要調整配方。 本發明適用之油類係石油爲底質之加工油。此等油之組 -9- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ：--^--.I^衣-- (請先閱讀背面之注意事項再填寫本頁)513459 Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (1) The present invention relates to polyurethane foam, especially containing a polyhydric alcohol Urethane g purpose foam. The present invention further relates to a method for preparing a polyurethane foam and an article comprising a polyurethane foam. Highly resilient polyurethane foams are usually made from a polyether triol and an isocyanate. The number average molecular weight of the polyether triols is usually from 4,500 to 6,000, and the average functionality is from 24 to 27 hydroxyl groups per molecule. Toluene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate / diphenylmethane diisocyanate mixture, and modified metho-isocyanate @purpose or dibenzylmethyldiisocyanate S Wide and wide foam. Isopropionic functionality is usually 2.0, and in most cases no more than 2.3 isocyanate groups per molecule. Under the conditions that promote foaming, the use of polyether triol with 2.0 to 2.3 isocyanate groups per molecule will form the elastic foam. U.S. Patent No. 4,939,184 describes polyurethane foams made from polyisobutylenetriols and glycols prepared by a cationic method. The polyisobutylene is premixed with an isocyanate, that is, an isocyanate mixture of a meta- and para-isomer of toluene diisocyanate with a functionality of 2.0. Water was then added as a blowing agent to form the polyurethane foam. The resulting foam has low energy and is suitable for energy absorbing applications. International (PCT) application WO 97/00902 describes a high-elasticity polyurethane foam made from polyglycol. The elasticity of the foam is based on the addition of an aromatic polyisocyanate having an official degree of 2.5 to 3.0 isocyanate groups per molecule to ensure proper cross-linking. Compared with the conventional polyurethane foam, the paper size of this paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) ^-ΊΙΙ4! (Please read the precautions on the back before filling This page}-Order · 513459 A7 _ B7 V. Description of the invention (2) The obtained polydifluorene glycol foam exhibits excellent moisture aging properties. US Patent No. 5,710,192 describes a high level of polydifluorene glycol produced from Elastic energy, high tear-resistant polyurethane foam. The elastic energy of the foam is determined by selecting an appropriate amount of aromatic polyisocyanate having a functionality of 1.8 to 2.5 isocyanate groups per molecule to properly crosslink it. Achieved. The produced foam is excellent in tear resistance and has a color close to white. Among the above-mentioned foams, the problem lies in the balance between handleability and cell size control and cell distribution. What is needed is a highly processable hair Foam, which has small and uniform cell size and distribution, and retains the properties of a moderate elastic energy foam. Surprisingly, it has been found in a polyurethane foam made from polydiene glycol. A plasticizer, such as up to 50% W oil can be used to produce highly processable foams. Therefore, the present invention relates to a polyurethane foam composition derived from a reaction mixture, the reaction mixture comprising: a number average molecular weight from 1,000 to 20,000 hydrogenated polydiene glycol; an aromatic polyisocyanate; a plasticizer printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs; and a foaming agent. The foam has a low viscosity during manufacture, and Compared with a foam produced without adding oil, the foam has a more uniform cell structure. According to another preferred embodiment, the present invention relates to a polyurethane foam composition derived from a reaction mixture. The reaction mixture-5-513459 A7 B7 V. Description of the invention (3) Contains: A hydrogenated polydiene diol having a number average molecular weight from 1,000 to 20,000; an aromatic polyisocyanate; a gum Viscous resin; a plasticizer; and a foaming agent. The plasticizer is preferably compatible with the hydrogenated polydiene glycol. If the plasticizer is compatible with the hydrogenated polydiene glycol, then Better The two components are mixed in a weight ratio, and the components will not separate into two layers within twelve hours at room temperature. The plasticizer is usually selected by those skilled in the art. The plasticizer is an oil and / or a molecular weight of A hydrogenated polydiene monool of 500 to 20,000 is preferred. Brief description of the drawings Figure 1 shows the effect of oil on viscosity. Figure 2 shows the effect of oil on foam density. Figure 3 shows water content for foaming according to the invention The effect of body density. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). According to one of the preferred examples, the present invention contains 100 parts by weight (pbw) of the average molecular weight. Polydiene glycols from 1,000 to 20,000 (preferably from 1,000 to 10,000, most preferably from 3,000 to 6,000), aromatic polyisocyanates from 20 to 55 pbw, plasticizers up to 200 pbw (to A hydrocarbon-treated oil is more preferred) and an elastic polyurethane foam having a foaming agent is preferred. In a preferred embodiment, the functionality of the hydrogenated polydiene diol is from 1.6 to 2 hydroxyl groups per molecule, preferably from 1.8 to 2 hydroxyl groups. The functionality of the polyisocyanate used is 2.5 to 3.0 isocyanates-6- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 513459 A7 B7 5. Description of the invention (4 groups. The isocyanate concentration added makes the number of isocyanate groups and hydroxyl groups close The NCO: OH molar ratio is preferably from 09 to 12. The polydiene diol used in the present invention is usually prepared by an anionic method. Those skilled in the art have already known the anionic polymerization in detail, which is described in the US patent Nos. 5,376,745, 5,391,663, 5,393,843, 5,405,911, and 5,416,168. 'The polymerization of the polydiene diol consists of a single lithium initiator containing a protected hydroxyl group or a conjugated diene polymerized at each lithium position. Monolithic dilithium initiator. Based on cost advantages, the total difluorene is usually u3_butadiene or isoprene, but other conjugated difluorene can also be used in the present invention. When the conjugated difluorene is used When the system is 1,3-butanefluorene, and the polymer formed is hydrogenated, the anionic polymerization is usually controlled by a structural modifier (such as diethyl ether or i 2 _ diethoxy its ethane) to obtain the required amount. Functional additives are usually added before termination to terminate the anionic polymerization. The functional agents used are familiar to those skilled in the art and are described in US Patent Nos. 5,391,637, 5,393,843 and 5,418,296. Preferred The functionalizing agent is ethylene oxide. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 11 in · — m mtmMmMm ml ml · · mmmmtmi Muni in (Please read the precautions on the back before filling this page) # 1 Hydrogenated Polyethylene It is better to improve the stability of ene diol, so that at least 90% of the carbon and carbon double bonds in the diol are saturated, and at least 95% of the diol is preferably saturated. The hydrogenation of these polymers and copolymers can be carried out by various established methods This includes hydrogenation under the presence of catalysts such as raney (R) nickel, precious metals such as pins, soluble transition metal catalysts, and titanium catalysts as described in US Patent No. 5,039,755. The hydrogenated polydiene glycol It is used for stability bomb foam. The paper size of this poly two women is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 513459 A7 B7 5) Alcohol has preferably from 1.6 to 2 hydroxyl groups per molecule, and more preferably from 1.8 to 2 hydroxyl groups. The average functionality is, for example, 1.8 means that about 80% of the molecules are diols and about 20% of the molecules Monools. Because most of the product molecules have two hydroxyl groups, the product is considered a diol. The number average molecular weight of the polydiene glycol of the present invention is preferably between 1,000 and 20,000, more preferably from 1,000 to 10,000, and most preferably from 3,000 to 6,000. Hydrogenated polybutadiene glycol is preferred, and the 1,2-additive content is between 40% and 60%. This difluorene microstructure is usually measured by 13C nuclear magnetic resonance (NMR) in chloroform. The polybutadiene glycol must have at least 40% 1,2-butadiene addition, because if the polymer contains less than 40% 1,2-butadiene addition, it is waxy at room temperature after hydrogenation . The content of the 1,2-butadiene additive is preferably between 40 and 60%. Isoprene polymers typically have at least 80% 1,4-isoprene additives to reduce glass transition temperature (Tg) and viscosity. The polydiene diols used in the present invention generally have a hydroxyl equivalent weight between about 500 and about 10,000, more preferably between 500 and 5,000, and most preferably between 1,500 and 3,000. Therefore, in the case of polydiene glycols, a suitable number average molecular weight is between 1,000 and 20,000, more preferably between 1,000 and 10,000, and most preferably between 3,000 and 6,000. The hydrogenated polydiene diol of the present invention has a number average molecular weight of 3,300, a functionality of 1.92, and a 1,2-butadiene content of 54%. Hydrogenating the polymer removes more than 99% of the carbon and carbon double bonds. This polymer is hereinafter referred to as diol 1. The polydiene monools used are essentially prepared as described herein, but the polymerization is initiated by a monolithium initiator. The number average molecular weight of this monohydroxylated polydifluorene polymer is usually 500 to 20,000. -8- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling in this (Page) clothing. -Tr Fill in too, 11 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 513459 A7 B7 V. Invention description (6) Preferably 2,000 to 8,000. The hydrogenated polydifluorene monool has an average molecular weight of 3850, a functionality of 0.98, and a 1,2-butadiene content of 48%. Hydrogenating the polymer removes more than 99% of the carbon and carbon double bonds. This polymer is hereinafter referred to as Monool 1. The number average molecular weight referred to herein is a number average molecular weight measured by gel permeation chromatography (GPC) calibrated with a polybutadiene standard having a known number average molecular weight. The solvent used in this GPC analysis was tetrahydrofuran. The isocyanate-based aromatic polyisocyanate used in the present invention has the rapid reactivity required for producing a foam. Because the functionality of the saturated polydiene diol is about 2 hydroxyl groups per molecule, a polyisocyanate with a functionality from 1.8 to 3.0 (preferably .2.5 to 3.0) is usually used to achieve the desired crosslinking density to form Foam with stability, high load capacity and high elastic energy. The use of isocyanates with a lower level of energy results in less stable foams, lower load capacity, and lower elastic energy. Isocyanates with higher functionality will form foams with an excessively high content of closed cells, which have a negative impact on physical properties. 0 Examples of suitable aromatic polyisocyanates are MONDUR® MR (Bayer), which is a polymeric diphenyl Methane polyisocyanate, isocyanate functionality is usually 2.7. It is also possible to use RUBINATE® 9225 (ICI Americas), a liquid isocyanate consisting of a mixture of 2,4-diphenylmethane diisocyanate and 4,4-diphenylmethane diisocyanate with a functionality of 2.06; however, in Adding an oil or a monoalcohol to the foam of this lower-functionality polyisocyanate will cause the foam to collapse, so the formulation needs to be adjusted. The oil to which the present invention is applicable is a processing oil in which petroleum is a substrate. The group of these oils -9- This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm):-^-. I ^ 衣-(Please read the precautions on the back before filling this page)

、1T 經濟部中央標準局員工消費合作社印製 513459 A7 _________B7 五、發明説明（7 ) — 合可自石蟻類至環燒類至高級芳族類油。市售油類所包括 之黏度範圍廣泛’於1〇〇下（38。〇下自1〇至1000厘泊。 本發明所使用之油類黏度在上述範圍之石壤、環燒或石犧/ 環垸油爲佳。本發明適用之油類實例係SHELLFLEX® 3 71 (Shell Oil Company)，其係一種於 1〇〇 °F (3 8 °C)下黏度爲 80·1〇〇厘泊之石蠟/環烷加工油。 因爲该聚一晞二醇係一種烴，其與烴加工油之相容性優 良。此外’該油不會自該發泡體滲出。於該調配物中添加 油會降低黏度，因此改良處理性。圖1顯示與油 (SHELLFLEX®371 ; SHELLFLEX 係商標）掺合之聚二晞 二醇（二醇1)黏度視該摻合物中油量而改變。在任何給定 溫度下，每百份數聚二烯二醇樹脂（phr)中油之添加量高達 200重量份數時，黏度會下降1〇個係數。此等黏度下降使 知製造本發明發泡體較製造先前技藝發泡體容易，可形成 更均勻且孔室大小更小之發泡體。 圖2顯示油SHELLFLEX 3 71之濃度對於與聚異氰酸酯 (MONDUR® MR)及水摻合之聚二烯二醇發泡體密度的影 響。該油含量自0提高至200 phr，密度提高約三倍。較緻 密之發泡體孔室較小，而且孔大小分佈極爲均勻。 本發明聚胺曱酸酯發泡體之主要組份係聚二烯二醇、該 芳族聚異氰酸g旨、一種發泡劑諸如水，及一種增塑劑，以 油爲佳，及/或一種聚二烯單醇。或者，該聚胺甲酸酯發泡 體可另外包含一種膠黏樹脂。 本發明適用之膠黏樹脂分子量相當低，其主要烴聚合物 -10- 本紙張尺度適用中國國家標準（CNS ) A4規格（1_10χ 297公釐）^----：— _ 衣 訂 "" (請先閱讀背面之注意事項再填寫本頁) 513459 A7 B7 五、發明説明（8 ) 原始特性係環狀與球狀軟化點，其由ASTM標準方法E28 測量。一般而言，該樹脂之軟化點在約80 °C至約120 °C。 然而，在特定實例，例如於低溫中獲得最佳膠黏性，軟化 % 點較低之樹脂或液態樹脂較佳。 代表性膠黏樹脂係由包含60%戊間二晞、10%異戊間二 烯、5 %環戊二烯、1 5%2 -甲基_ 2 - 丁烯與約10%二聚物之 混合物陽離子聚合製得，如美國專利第3,577,398號敎示。 此種樹月旨係市售之WINGTACK® 95(Goodyear Tire & Rubber Company)，其軟化點爲95 °C。該樹脂亦可包含某 些包括苯乙烯或α -甲基苯乙烯之芳族成份，此等成份係於 該樹脂聚合作用期間導入。 適用本發明之其他促進黏合之樹脂包括經氫化松脂類、 松脂之酯類、聚萜烯類、萜烯酚樹脂類及經聚合混合烯烴 類。爲獲得良好熱氧化與顏色安定性，使用經飽和樹脂爲 佳，諸如一種經氫化二環戊二烯樹脂，諸如ESCOREZ® 5000 系列（Exxon Chemical Company)，或一種經氫化聚苯 乙晞樹脂，諸如 REGALREZ® 系列（Hercules, Inc·)。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 使用軟化點高之膠黏樹脂時，該樹脂會提高反應混合物 之軟化點，致使發泡作用無法進行。於發泡期間添加一種 油降低黏度可以改善該發泡體之處理性。適用於本發明之 代表性油類包括上述之石蠟/環烷橡膠加工油。本發明適用 之油實例係SHELLFLEX371。此油與聚二晞二醇/膠黏混 合物之相容性絕佳。因此，該油不會自該發泡體滲出，可 以調整該油濃度以製得所需黏度、發泡體密度與膠黏性 -11 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 9 45 3 1X 5 五 經濟部中央標準局員工消費合作社印製 A7 _________ B7 、發明説明（9 ) 質。 以永#| g予代替邵》聚二烯二醇亦可控制該發泡娜、 處理性。藉由調整該二醇對單醇之比率可以預定用於= 應用〈發泡體黏彈能性質。已發現單醇含量高達該二^ 醉滿合物75重量％之黏合發泡體較適宜。 早 謂經氫化聚二烯二醇/增塑劑重量比率通常至多5:1 ，至 多4·1爲佳，至多3:1更佳，至多21尤佳。該比率通常 灵少1 · 4 ，至少1 : 3爲佳，至少1 : 1 ·5更佳，至少1 · J尤 隹。 誃經氫化聚二烯二醇/膠黏樹脂之重量比率通常至多 5 : 1 ，至多4 : 1爲佳，至多3 : i更佳，至多2 : 1尤佳。該 比率通常至少1 ·· 4 ，至少} : 3爲佳，至少j : i 5更佳，至 少1 : 1尤佳。1.1T printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 513459 A7 _________B7 V. Description of the invention (7) — It can be from stone ants to ring-burning to high-grade aromatic oils. Commercially available oils include a wide range of viscosities ranging from 10 to 1000 centipoise at 100 ° C (38 ° C). Stone oil, ring-burned or stone sacrificial oils with viscosity in the above range used in the present invention / Cyclops oil is preferred. An example of an oil suitable for use in the present invention is SHELLFLEX® 3 71 (Shell Oil Company), which is a type with a viscosity of 80 · 100 centipoise at 100 ° F (38 ° C). Paraffin / naphthenic processing oil. Because the polymonomethylene glycol is a hydrocarbon, it has excellent compatibility with hydrocarbon processing oils. In addition, 'the oil will not ooze from the foam. Adding oil to the formulation will Reduces viscosity and therefore improves handleability. Figure 1 shows the viscosity of polydioxane (diol 1) blended with oil (SHELLFLEX® 371; SHELLFLEX is a trademark) depending on the amount of oil in the blend. At any given value At the temperature, when the amount of oil added per hundred parts of polydiene glycol resin (phr) is as high as 200 parts by weight, the viscosity will decrease by a factor of 10. This decrease in viscosity makes it known that the manufacturing of the foam of the present invention is more advanced than before. The technical foam is easy to form a more uniform foam with a smaller cell size. Figure 2 shows oil SHELLFLEX The effect of the concentration of 3 71 on the density of polydiene glycol foam blended with polyisocyanate (MONDUR® MR) and water. The oil content increased from 0 to 200 phr, and the density increased about three times. More dense hair The foam cell has a small pore space, and the pore size distribution is extremely uniform. The main component of the polyurethane foam of the present invention is polydiene glycol, the aromatic polyisocyanate, and a foaming agent such as Water, and a plasticizer, preferably oil, and / or a polydiene monool. Alternatively, the polyurethane foam may further include an adhesive resin. The molecular weight of the adhesive resin applicable in the present invention Quite low, its main hydrocarbon polymer-10- This paper size is applicable to Chinese National Standard (CNS) A4 specification (1_10χ 297 mm) ^ ----: — _ clothing order " " (Please read the note on the back first Please fill in this page again) 513459 A7 B7 V. Description of the invention (8) The original characteristics are ring and spherical softening points, which are measured by ASTM standard method E28. Generally speaking, the softening point of this resin is about 80 ° C to Approx. 120 ° C. However, in certain cases, for example, best adhesion is achieved at low temperatures A resin or liquid resin with a lower% softening point is preferred. Typical adhesive resins are composed of 60% pentadiene, 10% isoprene, 5% cyclopentadiene, and 1 5% 2-methyl. _ 2-Obtained by cationic polymerization of a mixture of butene and about 10% dimer, as shown in US Patent No. 3,577,398. This tree moon is commercially available WINGTACK® 95 (Goodyear Tire & Rubber Company), which The softening point is 95 ° C. The resin may also contain some aromatic components including styrene or α-methylstyrene, which are introduced during the polymerization of the resin. Other adhesion-promoting resins suitable for the present invention include hydrogenated turpentine, turpentine esters, polyterpenes, terpene phenol resins, and polymerized mixed olefins. For good thermal oxidation and color stability, it is better to use a saturated resin, such as a hydrogenated dicyclopentadiene resin, such as the ESCOREZ® 5000 series (Exxon Chemical Company), or a hydrogenated polystyrene resin, such as REGALREZ® series (Hercules, Inc.). Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). When using an adhesive resin with a high softening point, the resin will increase the softening point of the reaction mixture, making foaming impossible. Adding an oil during foaming to reduce viscosity can improve the foam's physical properties. Representative oils suitable for use in the present invention include the paraffin / naphthenic rubber processing oils described above. An example of an oil to which the present invention is applicable is SHELLFLEX371. This oil has excellent compatibility with polydioxane / adhesive blends. Therefore, the oil will not ooze from the foam, and the oil concentration can be adjusted to obtain the required viscosity, foam density and tackiness. -11-This paper size applies to China National Standard (CNS) A4 (210X297) (Mm) 9 45 3 1X 5 Five A7 _________ B7 printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the description of the invention (9). Yong # | g to replace Shao polydiene glycol can also control the foaming and handling properties. By adjusting the ratio of the diol to the monoalcohol, it can be predetermined to be used for the application of the viscoelastic properties of the foam. It has been found that a sticky foam having a monoalcohol content of up to 75% by weight of the dioxin compound is more suitable. It is said that the weight ratio of hydrogenated polydiene glycol / plasticizer is usually at most 5: 1, preferably at most 4.1, more preferably at most 3: 1, and most preferably at most 21. This ratio is usually less than 1 · 4, preferably at least 1: 3, more preferably at least 1: 1 · 5, and especially at least 1 · J.氢化 The weight ratio of hydrogenated polydiene glycol / adhesive resin is usually at most 5: 1, preferably at most 4: 1, more preferably at most 3: i, and even more preferably at most 2: 1. This ratio is usually at least 1 ·· 4, preferably at least}: 3, more preferably at least j: i 5 and even more preferably at least 1: 1.

一般而言，製備該發泡體需要觸媒與一種界面活性劑。 逋常添加界面活性劑以改良該組份之可互混性，其依序 促進孩羥基/異氰酸酯反應。此外，降低該混合物表面張 力’該表面張力影響膨脹發泡體之孔室晶核作用與安定 性’形成細微孔室結構。該界面活性劑係一種聚矽氧油爲 佳0適用之市售聚矽氧油係 TEGOSTAB-B8404 (TEGOSTAB係一種商標）。較佳聚矽氧油係DABCO® DC 5 160 。 若存 在界面 活性劑 ，其添 加量通 常係每 丨 〇〇 pbw 該 聚二烯二醇中自0.01至5重量份數（0.01-5 phr)，自0.01 至1 phr爲佳。 原則上，可使用該系統中一或多種發泡反應習知觸媒任 -12- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ：----.丨衣— (請先閲讀背面之注意事項再填寫本頁) 訂- 513459 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（1〇 ) 一者。適用之觸媒實例描述於歐洲專利申請案第0 358 282 號，其包括胺類，諸如三級胺類、羧酸鹽類及有機金屬觸 媒。 適用之三級胺實例係三伸乙基二胺、甲基嗎啉、N_ 乙基嗎4木、一乙基·乙醇-胺、N_椰子基嗎琳、1-曱基-4-二甲基胺基·乙基六氫吡啶、3_甲氧基丙基二甲胺、 N，N，N‘-二·甲基異丙基伸丙基二胺、3_二乙基胺基丙基_ 二乙胺、二甲基卞胺及二甲基環己胺。適於作爲觸媒之羧 酸鹽實例係醋酸鋼。市售胺觸媒之實例係Air Produets andGenerally speaking, the preparation of the foam requires a catalyst and a surfactant. Surfactants are often added to improve the miscibility of this component, which in turn promotes the hydroxyl / isocyanate reaction. In addition, reducing the surface tension of the mixture, 'the surface tension affects the nucleation and stability of the pore chambers of the expanded foam, and forms a fine pore chamber structure. The surfactant is a polysiloxane which is a commercially available polysiloxane which is suitable for use. TEGOSTAB-B8404 (TEGOSTAB is a trademark). The preferred silicone oil is DABCO® DC 5 160. If a surfactant is present, it is usually added in an amount of from 0.01 to 5 parts by weight (0.01-5 phr), preferably from 0.01 to 1 phr, per polypenediol. In principle, one or more foaming reaction catalysts in this system can be used. -12- This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm): ----. 丨 clothing-( (Please read the notes on the back before filling this page) Order-513459 Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of Invention (1). Examples of suitable catalysts are described in European Patent Application No. 0 358 282, which includes amines such as tertiary amines, carboxylates and organometallic catalysts. Examples of suitable tertiary amines are triethylenediamine, methylmorpholine, N_ethylmorpholine, monoethylethanol-amine, N_cocoylmorphine, 1-fluorenyl-4-dimethyl Aminoaminoethyl hexahydropyridine, 3-methoxypropyldimethylamine, N, N, N'-dimethylisopropylpropanediamine, 3-diethylaminopropyl_ Diethylamine, dimethylamidamine and dimethylcyclohexylamine. An example of a carboxylate suitable as a catalyst is steel acetate. Examples of commercially available amine catalysts are Air Produets and

Chemicals之DABCO® 33-LV及延遲作用胺觸媒DABCO DC-1。適用之有機金屬觸媒包括辛酸亞錫、油酸亞錫、醋 酸亞錫、月桂酸亞錫、辛酸鉛、環烷酸鉛、環烷酸鎳、環 烷酸姑及二氣化二丁基錫。適於作爲製造聚胺甲酸酯用觸 媒之有機金屬化合物其他實例描述於美國專利説明書第 2,846,408 號。 其中所使用之觸媒或觸媒混合物用量通常係每〗〇 〇份數 聚二晞二醇中自0.01至5.0 pbw範園内，自〇 2至2 〇 pbw 範圍内爲佳。 可使用各種發泡劑。適用之發泡劑包括_化烴類、脂族 烷類及脂環烷類以及水，此等經常稱爲化學發泡劑。因完 全氯化、氟化烷類（CFC類）會有臭氧耗盡效應之故，使用 此類發泡劑比較不好，不過在本發明範疇内亦可使用之。 至少一個氫原子未被鹵素原子取代（所謂的jjCFC類）之鹵 化烷類臭氧耗盡效應可能性較低，因此係用於物理性發泡 -13- 本紙張尺度適用中國國家標準（CNS ) M規格（210><297公釐）~~— ------ ： ·:--.--^^衣-- (請先閱讀背面之注意事項再填寫本頁) 訂 513459 經濟部中央標準局員工消費合作社印製 A7 Β7 五、發明説明（11 ) 的發泡體中之較佳經鹵化烴類。最適用之HCFC型發泡劑 係1 -氣-1，1 -二氟乙燒。更佳之發泡劑係氫氟烴類，其被 認爲零臭氧耗盡可能性。 亦已知使用水作爲一種（化學性）發泡劑。根據已知之 NCO/H2〇反應，水會與異氰酸酯基反應，因此釋放出二氧 化凌，導致發泡作用。 最後’脂族與脂環烷類已發展成C F C類之替代發泡劑。 此種燒類之實例係正戊烷、異戊烷及正己烷（脂族），及環 戊烷與環己烷（脂環族）。 已知上述發泡劑可以單獨使用或以二者以上之混合物形 式使用。所提及之發泡劑中，已發現水與環戊烷尤適於作 爲本發明目的之發泡劑。所使用之發泡劑用量係習用用 里’即在水爲發泡劑實例中，每1 〇〇份數聚二晞二醇自〇】 至5 pbw範圍内，在鹵化烴類、脂族烷類及脂環烷類實例 中，每1〇〇份數聚二烯二醇自約〇」至2〇 pbw範圍内。該 發泡劑以水爲佳。 水之添加量係每100份數聚二烯二醇中添加自〇5至3 5 重量份數（pbw)。因爲雜質會影響發泡反應，所以使用蒸餾 或去礦質水爲佳。 若情況需要，可添加阻燃劑、填料及其他添加劑。熟知 本領域者可選擇適當其他化合物添加於欲發泡組合物中。 可添加抗氧化劑與抗紫外線劑，進—步提高該發泡體之 熱安定性與光安定性。受阻酚型抗氧化劑（諸如 IRGANOX® 1G76 (Ciba Geigy))亦適於安定此等發泡體。 -14- ---：----.1-- (請先閲讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準（CNS ) A4找枚（)Chemicals' DABCO® 33-LV and delayed action amine catalyst DABCO DC-1. Suitable organometallic catalysts include stannous octoate, stannous oleate, stannous acetate, stannous laurate, lead octoate, lead naphthenate, nickel naphthenate, naphthenate and dibutyltin digas. Other examples of organometallic compounds suitable as catalysts for polyurethane production are described in U.S. Patent Specification No. 2,846,408. The amount of the catalyst or catalyst mixture used therein is usually within the range of 0.01 to 5.0 pbw in polydioxane and preferably in the range of 02 to 20 pbw per part of polydioxanediol. Various foaming agents can be used. Suitable blowing agents include hydrocarbons, aliphatic alkanes and alicyclic alkanes, and water, which are often referred to as chemical blowing agents. Because of the ozone depletion effect of fully chlorinated and fluorinated alkane (CFC), it is not good to use this type of blowing agent, but it can also be used within the scope of the present invention. Halogenated alkanes with at least one hydrogen atom not replaced by halogen atoms (so-called jjCFCs) are less likely to have an ozone depletion effect, so they are used for physical foaming. 13- This paper applies Chinese National Standards (CNS) M Specifications (210 > < 297 mm) ~~-------: ·: --.-- ^^ clothing-(Please read the notes on the back before filling this page) Order 513459 Central Ministry of Economic Affairs A7 B7 printed by the Consumer Bureau of Standards Bureau. V. Preferred halogenated hydrocarbons in the foam of the invention description (11). The most suitable HCFC type blowing agent is 1-gas-1,1-difluoroethane. Better blowing agents are hydrofluorocarbons, which are considered to have zero ozone depletion potential. It is also known to use water as a (chemical) blowing agent. According to the known NCO / H2O reaction, water reacts with isocyanate groups, and thus releases dioxide, resulting in foaming. Finally, the 'aliphatic and cycloaliphatic' have been developed as C F C alternative foaming agents. Examples of such burners are n-pentane, isopentane and n-hexane (aliphatic), and cyclopentane and cyclohexane (alicyclic). It is known that the above-mentioned foaming agents can be used alone or in the form of a mixture of two or more. Of the blowing agents mentioned, water and cyclopentane have been found to be particularly suitable as blowing agents for the purposes of the present invention. The amount of foaming agent used is conventional, that is, in the case of water as a foaming agent, the polydioxane glycol ranges from 0 to 5 pbw per 100 parts, in the range of halogenated hydrocarbons, aliphatic alkane In the examples of alicyclic and alicyclic alkanes, the polydiene glycol ranges from about 0 "to 20 pbw per 100 parts. The blowing agent is preferably water. The amount of water added is from 0.05 to 35 parts by weight (pbw) per 100 parts of polydiene glycol. Because impurities can affect the foaming reaction, it is better to use distilled or demineralized water. If necessary, flame retardants, fillers and other additives can be added. It is well known in the art that other suitable compounds may be selected for addition to the composition to be foamed. Antioxidants and anti-ultraviolet agents can be added to further improve the thermal stability and light stability of the foam. Hindered phenolic antioxidants such as IRGANOX® 1G76 (Ciba Geigy) are also suitable for stabilizing these foams. -14- ---: ----. 1-- (Please read the notes on the back before filling this page) The paper size is applicable to China National Standard (CNS) A4

- I - 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（12 ) 使用一種紫外線吸收劑（諸如TiNUVIN® 328(Ciba Geigy)) 與一種受阻胺光安定劑（諸如TINUVIN® 123(Ciba Geigy)) 之組合對於陽光所致之變質具有最佳抗力。 掺合聚異氰酸酯以外之全部組份製備該聚胺甲酸酯發泡 體爲佳。預熱（通常至約8〇 )該聚二晞二醇，若存在聚二 缔單醇，亦預熱該聚二晞單醇，以降低掺合前黏度。亦預 熱該膠黏樹脂爲佳，通常預熱至約150 °C。摻合後，迅速 添加該芳族聚異氰酸酯，並於該混合物倘入模内之前簡要 攪拌，保持該膨脹之發泡體。 因此’本發明另一方面有關一種製備聚胺甲酸酯發泡體 組合物之方法，其包括 (1)混合一種數量平均分子量自1，000至2〇 〇〇〇之經氫化 聚二晞二醇、一種增塑劑、一種發泡劑，及選擇性混合一 種膠黏樹脂、一種界面活性劑與一種觸媒，製得一種混合 物； (ii)結合芳族聚異氰酸酯與該混合物，製得一種組合 物；及 (111)使該組合物發泡，製得一種聚胺甲酸酯發泡體組合 物。 藉由加熱該發泡體至高溫（通常介於100與1 6〇。(3 ) 一段特 足時間（通常在10分鐘至96小時範圍内，自30分鐘至48 小時爲佳））對該聚胺甲酸酯發泡體進行硬化作用。不過， 該聚胺甲酸酯放熱性形成反應所產生的熱足以完成硬化作 用’故该方法係隔熱進行。 -15- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) ""' " --- ---：----·——0^-- (請先閱讀背面之注意事項再填寫本頁)-I-Printed by A7 B7, Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the Invention (12) Use a UV absorber (such as TiNUVIN® 328 (Ciba Geigy)) and a hindered amine light stabilizer (such as TINUVIN® 123 ( Ciba Geigy)) combination has the best resistance to deterioration caused by sunlight. It is preferable to blend all components other than polyisocyanate to prepare the polyurethane foam. The polydifluorene glycol is preheated (usually to about 80). If polydiol is present, the polydifluorene is also preheated to reduce the viscosity before blending. It is also good to preheat the adhesive resin, which is usually preheated to about 150 ° C. After blending, the aromatic polyisocyanate was quickly added, and the mixture was briefly stirred before being kept in the mold to maintain the expanded foam. Therefore, another aspect of the present invention relates to a method for preparing a polyurethane foam composition, which comprises (1) mixing a hydrogenated polydioxine having a number average molecular weight from 1,000 to 2000 Alcohol, a plasticizer, a foaming agent, and an admixture of an adhesive resin, a surfactant, and a catalyst to obtain a mixture; (ii) combining an aromatic polyisocyanate with the mixture to obtain a mixture A composition; and (111) foaming the composition to obtain a polyurethane foam composition. The polymer is heated by heating the foam to a high temperature (usually between 100 and 160. (3) for a sufficient time (usually in the range of 10 minutes to 96 hours, preferably from 30 minutes to 48 hours). The urethane foam performs hardening. However, the heat generated by the exothermic formation reaction of the polyurethane is sufficient to complete the hardening effect ', so this method is performed with heat insulation. -15- This paper size applies to Chinese National Standard (CNS) A4 (210X297mm) " " '" --- ---: ---- · ——0 ^-(Please read the back first (Notes for filling in this page)

、1T 513459 Α7 Β7 五、發明説明（13 ) 本發明較佳具體實例係一種彈能聚胺甲酸酯發泡體，其 包含100重量份數數量平均分子量自3,000至6,000，官能 度係每個分子自h8至2 〇個羥基之氫化聚二烯二醇，自 0.5至3.5重量份數水、一種官能度係每個分子自2 5至3 〇 個異氰酸酯基之芳族聚異氰酸酯，其濃度使異氰酸酯基與 經基數目接近相等，自20至2〇〇重量份數油，自〇 4至〇 8 重量份數胺觸媒，自〇·3至06重量份數延遲作用胺觸媒及 自0至0·06重量份數之碎界面活性劑。該發泡體之孔室大 小與孔室大小分佈優於不使用油製備之發泡體。 本發明另外較佳具體實例係一種彈能聚胺甲酸酯發泡 體，其包含100重量份數數量平均分子量自3,〇〇〇至 6,000，官能度係每個分子自1.8至2·〇個羥基之氫化聚二 烯二醇’自〇. 5至3.5重量份數水、一種官能度係每個分子 自2·5至3·0個異氰酸酯基之芳族聚異氰酸酯，其濃度使異 戴旨基與每基數目接近相等，自50至150重量份數膠黏 樹脂，自1 0至100重量份數油，自〇·4至〇·8重量份數胺 觸媒，自0.3至0.6重量份數延遲作用胺觸媒及自〇至〇〇6 重量份數之碎界面活性劑。 經濟部中央標準局員工消費合作社印製 ： :- ·I -- (請先閱讀背面之注意事項再填寫本頁) 本發明另外較佳具體實例係一種彈能聚胺甲酸醋發泡 體，其包含25至100重量份數數量平均分子量自3，〇〇〇至 6,〇〇〇，官能度係每個分子自1.8至2.0個羥基之氫化聚二 烯二醇，75至0重量份數數量平均分子量自20〇〇至4〇〇〇 之聚二烯單醇，自0· 5至3.5重量份數水、一種官能度係每 個分子自2.5至3.0個異氰酸酯基之芳族聚異氰酸酯，其濃 -16 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（14 ) ^~~ 度使異氰酸酯基與羥基數目接近相等，自5〇至15〇重量份 數膠黏樹脂，自〇至100重量份數油，自〇4至〇8重量份 數胺觸媒’自0.3至〇·6重量份數延遲作用胺觸媒及自〇至 0.06重量份數之矽界面活性劑。 另方面，本發明有關包含本發明聚胺甲酸酯發泡體之 物件。 口：列實施例並非用將本發明限制在特定具體實例中，但 疋每個實施例可支持主張可請專利發明之個別申請專利項 目。 " 實施例1 使用表1所示聚合物、異氰酸酯（M〇NDUR⑧MR)、觸媒 (DABCO® 33_LV與DBAC⑽D(M)、界面活性劑 (DABCO® DC-5160)及水之組合製備八種發泡體。樣本2_ 7亦包含一種烴加工油（SHELLFLEX⑧37”，並以此等樣本 説明本發明。樣本1係一對照實例，其不包含油。樣本8 係另一個對照實例，其包含油，但是使用一種習用聚醚多 元醇。 在代表性製備方法中，將該聚合物與油預熱至t。對 於異氰酸醋以外之所有組份進行稱重，並置於乾燥罐中， 使用具有2吋（5.1公分）矩形螺距葉輪之CAFRAMO®攪拌 器此合。然後添加異氰酸酯，並繼續檀拌約4 5秒。此時， 整體材料開始發泡，並將其倒入一紙斗。該發泡體安定並 形成表層後，於爐中以11〇 °C後烘焙該發泡體十（1 〇)分 鐘。由該圓捲狀物切下試樣，測量發泡體密度、於4〇%壓 __ -17- 本紙張尺度家標準Y&S ) M規格（BOX29?公董 — -- - m - n n m —ϋ - n ϋ n _ τ _ n n m n m (請先閲讀背面之注意事項再填寫本頁) 513459 A7 B7 五、發明説明（15 ) 縮下之硬度、彈能與滯後現象。 密度 由整體重量及大小測量密度。結果示於表2。 彈能 一直徑1 6公厘之鋼球（16 · 3克）經由内徑3 8公厘之清潔 塑料管’自咼51.6公分落下，掉到ι〇χΐ〇χ5公分之發泡 體塊上。測量反彈高度，並以1 〇〇 x(反彈高度/落下高度） 計算彈能。結果示於表2。 壓縮硬度與滯後損失 以INSTRON® Machine Model 5565測量壓縮硬度與滞後 損失。將一 10 X 10 x5公分發泡體塊置於兩個平行板間， 墨縮60%然後除去負重四個回合，記錄壓縮該發泡體4〇〇/〇 所需力量，測得該發泡體壓縮硬度。以第一回合至第四回 合之應力/高度曲線下之區域計算滯後損失。結果示於表 2 〇 ---：--:--.110^-- (請先閱讀背面之注意事項再填寫本頁) 、\呑 經濟部中央標準局員工消費合作社印製 表1發泡體配方 •18-1T 513459 Α7 B7 V. Description of the invention (13) A preferred embodiment of the present invention is a kind of elastic polyurethane foam, which contains 100 parts by weight and has an average molecular weight from 3,000 to 6,000. The functionalities are each Hydrogenated polydiene diols with molecules from h8 to 20 hydroxyl groups, from 0.5 to 3.5 parts by weight of water, an aromatic polyisocyanate having a functionality of from 25 to 30 isocyanate groups per molecule, the concentration of which is such that The number of isocyanate groups and warp groups is nearly equal, from 20 to 2000 parts by weight of oil, from 04 to 08 parts by weight of amine catalyst, from 0.3 to 06 parts by weight of delayed action amine catalyst and from 0 To 0. 06 parts by weight of crushed surfactant. The cell size and cell size distribution of this foam are better than those produced without oil. Another preferred embodiment of the present invention is an elastic polyurethane foam, which contains 100 parts by weight of a number average molecular weight from 3,000 to 6,000, and the functionality is from 1.8 to 2 · per molecule. Hydrogenated polydiene diol of each hydroxyl group from 0.5 to 3.5 parts by weight of water, an aromatic polyisocyanate having a functionality of from 2.5 to 3.0 isocyanate groups per molecule, and its concentration makes isowear The base and the number of each base are nearly equal, from 50 to 150 parts by weight of adhesive resin, from 10 to 100 parts by weight of oil, from 0.4 to 0.8 parts by weight of amine catalyst, from 0.3 to 0.6 weight Parts delay action amine catalyst and crushed surfactant from 0 to 006 parts by weight. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs::-I-(Please read the notes on the back before filling this page) Another preferred embodiment of the present invention is an elastic polyurethane foam. Contains 25 to 100 parts by weight of hydrogenated polydiene diols with an average molecular weight from 3,000 to 6,000, functionality of from 1.8 to 2.0 hydroxyl groups per molecule, 75 to 0 parts by weight Polydiene monools having an average molecular weight from 2000 to 4,000, from 0.5 to 3.5 parts by weight of water, an aromatic polyisocyanate having a functionality of from 2.5 to 3.0 isocyanate groups per molecule, which Nong-16-This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (14) ^ ~~ The degree of isocyanate groups and hydroxyl groups Numbers are nearly equal, from 50 to 150 parts by weight of adhesive resin, from 0 to 100 parts by weight of oil, from 04 to 08 parts by weight of amine catalyst 'from 0.3 to 0.6 parts by weight of retardation Amine catalyst and silicon surfactant from 0 to 0.06 parts by weight. In another aspect, the invention relates to an article comprising the polyurethane foam of the invention. Mouth: The embodiments are not intended to limit the present invention to specific specific examples, but each embodiment can support individual patent applications that claim patentable inventions. " Example 1 Eight types of hair were prepared using a combination of polymers shown in Table 1, isocyanate (MONDUR⑧MR), catalyst (DABCO® 33_LV and DBAC⑽D (M), surfactant (DABCO® DC-5160), and water. Foam. Samples 2-7 also contain a hydrocarbon processing oil (SHELLFLEX⑧37 "and illustrate the invention with these samples. Sample 1 is a comparative example that does not contain oil. Sample 8 is another comparative example that contains oil, but A conventional polyether polyol is used. In a representative preparation method, the polymer and oil are preheated to t. All components except isocyanate are weighed and placed in a dry tank using a 2 inch (5.1 cm) CAFRAMO® agitator with rectangular pitch impeller. Then add isocyanate and continue mixing for about 4 5 seconds. At this time, the whole material starts to foam and pour it into a paper bucket. The foam After the surface layer was stabilized and formed, the foam was baked in an oven at 110 ° C. for ten (10) minutes. The sample was cut out from the round roll, and the density of the foam was measured. _ -17- Y & S) M size (BOX29? Dong —--m-nnm —ϋ-n ϋ n _ τ _ nnmnm (Please read the notes on the back before filling this page) 513459 A7 B7 V. Description of the invention (15) Reduced hardness, elastic energy and hysteresis Phenomenon. Density The density is measured from the overall weight and size. The results are shown in Table 2. The elastic energy is a steel ball (16 · 3 g) with a diameter of 16 mm. It passes through a clean plastic tube with an inner diameter of 38 mm. Fall and drop onto a foam block of 5 cm. Measure the bounce height and calculate the bounce energy at 100x (bounce height / drop height). The results are shown in Table 2. The compression hardness and hysteresis loss are given in INSTRON® Machine Model 5565 measures compression hardness and hysteresis loss. A 10 X 10 x 5 cm foam block is placed between two parallel plates, the ink is shrunk by 60%, and the load is removed for four rounds. Record the compression of the foam 4 〇〇 / 〇 required strength, the compression hardness of the foam was measured. Hysteresis loss was calculated from the area under the stress / height curve of the first to fourth rounds. The results are shown in Table 2 〇 ---:-: -. 110 ^-(Please read the notes on the back before filling in this page), \ 呑 经Ministry of Consumer Cooperatives Central Bureau of Standards staff printed Table 1 foam formulation • 18-

513459 A7 B7 i、發明説明（16 ) 樣本 二醇1 (phr) 油 (phr) 水 (phr) 異氰酸酯 (phr) 胺觸媒 (phr) 延遲作用 胺觸媒 (phr) 界面活性劑 (phr) 一 1 100 0 1 23.5 0.4 0.3 0.02 2 100 11.1 1 23.5 0.4 0.3 0.02 3 100 33.3 1 23.5 0.4 0.3 0.02 4 100 100 1 23.5 0.4 0.3 0.02 5 100 200 1 22.1 0.4 0.3 0.02 6 100 200 2 37.0 0.4 0.3 0.02 7 100 200 3 51.8 0.8 0.6 0.06 8 1 … . 100 100 1 23.5 0.4 0.3 0.02 1樣本1-7使用一種氫化聚丁二烯二醇，Mn=3300，f=1.92 ;樣本8使用 一種分子量4800之聚醚三醇(ARCOL® 11-34) I ! - - ill I !- - I I (讀先閱讀背面之注意事項再填寫本頁) 表2發泡體性質 樣本 密度(g/l) 壓縮40% 之硬度(N) 彈能 (%) 滯後損失 (%) 孔室大小 分佈 發泡體孔室 結構 1 109 27.8 50 14 廣 極小 2 124 31.0 54 13 廣 _ 極小 3 135 23.5 56 16 窄 極小 4 202 20.8 50 13 極窄 _ 極小 5 339 — 32 — 極窄 極小 6 267 --- 50 極窄 小 7 163 9.6 36 8 極窄 一 小 8a … —- 15 --------— 中等 a發泡體極油，所顯示之強度差 經濟部中央標準局員工消費合作社印製 樣本1 - 5配方相同，但是油含量自樣本1 (無油）提高至樣 -19- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 513459 A7 B7 五、發明説明（17 本5 (200 phr油）。樣本Μ全都包含lphr7jc，所以其發 泡之容積大約相當，各者以約10之係數膨脹。隨著添加之 油量增加，可見到該容積、密度隨著油含量提高。可以看 到添加11 phr油（樣本2)實質上對於該發泡體性質或質感 外觀沒有影響。添加33 Phr油（樣本3)會降低孔室大小; 佈，但是僅對於密度有輕微影響。添加1〇〇至2〇〇phr油 (樣本4 #5)製得小孔t大小極均勻分佈之發泡體，但是不 會形成明顯較緻密（較重）之發泡體。此等發泡體中沒有任 何一個滲出油。 樣本5-7與圖3顯示提高水含量對於包含2〇〇 phr油發泡 體之影響。水含量較高，異氰酸酯亦較高，致使發泡情況 更明顯，因此降低該發泡體密度。一般認爲包含2〇〇 phr油 之發泡體於約4 phr水含量四可達成110 g/1密度，其與無 油樣本1之密度相當。然而，一般預料油含量高之發泡體 壓縮硬度與黏合強度低於具有相同密度之無油發泡體。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁j 樣本8係習用發泡體’其以聚醚多元醇爲基質，於其中 添加油。可看出此等習用發泡體不適於添加油。該發泡體 真有油感’並且因該油與該聚醚多元醇不相容之故而使該 油滲出。 實施例2 以表3所示，使用二醇1或二醇1 /單醇1混合物、異氨 酸酯（MONDUR® MR)、膠黏樹月旨（WINGTACK 95)、觸媒 (DABCO® 33-LV 與 DABCO® DC-1)、界面活性劑 (DABCO® DC-5160)及水之組合製備五種發泡體。兩種發 -20- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ^>U459 A7 *~__ B7_._ 五、發明説明（18 ) ~ 泡體包含一種烴加工油（SHELLFLEX 371)。 代表性製備方法中，將該二醇、單醇與油（若存在的話） 預熱至80 °C，並將該膠黏樹脂預熱至150 °C。隨後進行實 施例1之程序。 如實施例1般測量密度、彈能與壓縮硬度及滯後損失。 結果示於表4。 表3發泡體配方 樣本 二醇1 (phr) 單醇2 (phr) 油 (phr) 樹脂 (phr) 水 (phr) 異氰酸 酯 (phr) 胺觸媒 (phr) 延遲作用 胺觸媒 _ 界面活 性劑 (phr) 1 100 0 0 0 1 23.5 0.4 0.3 0.02 9 100 0 100 82 2 37.0 0.8 0.6 0.04 10 100 —0 50 100 3 51.8 0.8 0.6 0.04 」1 50 50 0 100 3 49.8 0.8 0.6 0.04 12 50 50 0 50 1.5 27.6 0.4 0.3 0.02 13 25 75 0 50 1.5 26.6 0.4 0.3 0.02 1 氫化聚丁二烯二醇，Mn=3300，f=1.92 2氫化聚丁二烯單醇，Mn=3800，f=0.98 ； :I衣-- (請先閲讀背面之注意事項再填寫本頁)513459 A7 B7 i. Description of the invention (16) Sample diol 1 (phr) oil (phr) water (phr) isocyanate (phr) amine catalyst (phr) delayed action amine catalyst (phr) surfactant (phr) a 1 100 0 1 23.5 0.4 0.3 0.02 2 100 11.1 1 23.5 0.4 0.3 0.02 3 100 33.3 1 23.5 0.4 0.3 0.02 4 100 100 1 23.5 0.4 0.3 0.02 5 100 200 1 22.1 0.4 0.3 0.02 6 100 200 2 37.0 0.4 0.3 0.02 7 100 200 3 51.8 0.8 0.6 0.06 8 1…. 100 100 1 23.5 0.4 0.3 0.02 1 Samples 1-7 use a hydrogenated polybutadiene glycol, Mn = 3300, f = 1.92; Sample 8 uses a polyether with a molecular weight of 4,800. Alcohol (ARCOL® 11-34) I!--Ill I!--II (Read the precautions on the back before filling this page) Table 2 Foam Properties Sample Density (g / l) Compression 40% Hardness ( N) Elastic energy (%) Hysteresis loss (%) Cell size distribution Foam cell structure 1 109 27.8 50 14 Wide very small 2 124 31.0 54 13 Wide_ very small 3 135 23.5 56 16 Narrow very small 4 202 20.8 50 13 pole Narrow_ very small 5 339 — 32 — very narrow very small 6 267 --- 50 extremely narrow 7 163 9.6 36 8 very narrow one small 8a… —- 15 -------- — Medium a foamed oil, showing the difference in strength. Samples 1-5 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs have the same formula, but the oil content has increased from sample 1 (no oil) to sample -19. Applicable to China National Standard (CNS) A4 specification (210X297 mm) 513459 A7 B7 V. Description of invention (17 books 5 (200 phr oil). Samples M all contain lphr7jc, so the volume of foaming is about the same. A coefficient of 10 swells. As the amount of oil added increases, it can be seen that the volume and density increase with the oil content. It can be seen that the addition of 11 phr of oil (Sample 2) has virtually no effect on the properties or texture of the foam. Adding 33 Phr oil (Sample 3) reduces the cell size; cloth, but only slightly affects density. Adding 100 to 200 phr of oil (Sample 4 # 5) produced foams with extremely uniform distribution of small pores t size, but did not form significantly denser (heavier) foams. None of these foams exuded oil. Samples 5-7 and Figure 3 show the effect of increasing water content on 200 phr oil foam. The higher water content and higher isocyanate make foaming more pronounced, thus reducing the density of the foam. It is generally believed that a foam containing 200 phr of oil can achieve a density of 110 g / 1 at about 4 phr of water content, which is comparable to the density of oil-free sample 1. However, foams with high oil content are generally expected to have lower compressive hardness and adhesive strength than oil-free foams with the same density. Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (please read the notes on the back before filling out this page. Sample 8 is a conventional foam that uses a polyether polyol as the matrix and oil is added to it. It can be seen that Conventional foams are not suitable for adding oils. The foams really feel oily, and the oil oozes out because the oil is incompatible with the polyether polyol. Example 2 As shown in Table 3, diol 1 is used Or a diol 1 / mono alcohol 1 mixture, an isocyanate (MONDUR® MR), a gluing tree (WINGTACK 95), a catalyst (DABCO® 33-LV and DABCO® DC-1), a surfactant ( DABCO® DC-5160) and water are used to prepare five kinds of foams. Two kinds of hair -20- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ^ > U459 A7 * ~ __ B7_. _ V. Description of the invention (18) ~ The foam contains a hydrocarbon processing oil (SHELLFLEX 371). In a typical preparation method, the diol, monoalcohol and oil (if present) are preheated to 80 ° C, and The adhesive resin was preheated to 150 ° C. The procedure of Example 1 was then performed. The density, elastic energy and compression were measured as in Example 1. Degree and hysteresis loss. The results are shown in Table 4. Table 3 Foam formulation samples diol 1 (phr) mono alcohol 2 (phr) oil (phr) resin (phr) water (phr) isocyanate (phr) amine catalyst ( phr) Delayed action amine catalyst_ Surfactant (phr) 1 100 0 0 0 1 23.5 0.4 0.3 0.02 9 100 0 100 82 2 37.0 0.8 0.6 0.04 10 100 —0 50 100 3 51.8 0.8 0.6 0.04 `` 1 50 50 0 100 3 49.8 0.8 0.6 0.04 12 50 50 0 50 1.5 27.6 0.4 0.3 0.02 13 25 75 0 50 1.5 26.6 0.4 0.3 0.02 1 hydrogenated polybutadiene glycol, Mn = 3300, f = 1.92 2 hydrogenated polybutadiene monool , Mn = 3800, f = 0.98;: I clothing-(Please read the precautions on the back before filling this page)

、1T 經濟部中央標準局員工消費合作社印f 表4發泡體性質 -21 - 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X：297公釐）、 1T Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Table 4 Foam Properties -21-This paper size is in accordance with China National Standard (CNS) A4 (21〇X: 297mm)

五、發明説明（19 ) 經濟部中央標準局員工消費合作社印製 樣本 密度(g/〇 壓縮40%之 硬度(N) 彈能(％) 滯後損失 (%) 發泡體孔室 結構 1 109 27.8 50 14 極小 __9 122 5.3 10 32 極小 s10 111 6.6 10 69 小 __11 … … 沒有增長 _12 ㈣· 崩潰 __13 109 0.0 0 96 極小 ---：---r---- (讀先閲讀背面之注意事項再填寫本頁) 、1Τ 樣本1係高彈能發泡體，並作爲對照用。於109 g/丨密度 下，其壓縮硬度爲2 8 N，而且具有良好彈能與低滯後損 失。然而，因爲無樹脂，其不具膠黏或黏合性質。樣本9 與10説明添加膠黏樹脂與油之效用，並調整水含量製得相 當固定密度之發泡體。結果顯示，用於壓敏性黏合劑時， 此等發泡體更易壓縮，其彈能較小而邊滞後損失大於對照 貫例1。樣本9與1〇之發泡體係極佳之壓敏性黏合劑；二 者均具有良好黏指性，而且對於紙與經油漆表面之黏合性 佳一者亦均可自基板上完整乾淨地撕下，作爲去除黏合 性發泡體。樣本1 1 - 1 3顯示使用一種不含油之聚二晞二醇 /來一烯單醇摻合物的效果。樣本〗i與i 2無法製得符合需 求之發/包m。不過，一般認爲調整預熱溫度、混合規模及 觸媒濃度可以此二種配方製得符合需求之發泡體。樣本13 係極佳、極柔軟且膠黏之發泡體。樣本13係一種常見發泡 體，其於壓縮時並未立刻回彈，當其恢復時可完全回復到 原有形狀與大小。因此，壓縮硬度爲零，滞後損失爲幾乎 爲1 0 0 /〇，因爲本試驗時間極短，該發泡體於第一次壓縮 -22-V. Description of the invention (19) Sample density (g / 〇 compression 40% hardness (N) elastic energy (%) elastic energy (%) hysteresis loss (%) foam cell structure 1 109 27.8 50 14 Minimal __9 122 5.3 10 32 Minimal s10 111 6.6 10 69 Minimal __11…… not growing _12 ㈣ · Crash __13 109 0.0 0 96 Minimal ---: --- r ---- (read first read Note on the back, please fill in this page again), 1T sample 1 series high elastic energy foam, and for comparison. At 109 g / 丨 density, its compression hardness is 2 8 N, and it has good elastic energy and low hysteresis. Loss. However, because there is no resin, it does not have tacky or cohesive properties. Samples 9 and 10 show the effect of adding tacky resin and oil, and adjusting the water content to produce a foam with a relatively constant density. The results show that In the case of sensitive adhesives, these foams are easier to compress, their elastic energy is smaller and the loss of edge hysteresis is greater than that of Comparative Example 1. Samples 9 and 10 are excellent pressure-sensitive adhesives with foaming systems; both Both have good adhesiveness, and have good adhesion to paper and painted surface Both can be completely and cleanly peeled off the substrate to remove the adhesive foam. Samples 1 1 to 1 3 show the effect of using an oil-free polydioxanediol / lylene monool blend. Samples〗 i and i 2 can not make the hair / bags that meet the requirements. However, it is generally believed that adjusting the preheating temperature, mixing scale and catalyst concentration can be used to make foams that meet the requirements. Sample 13 is excellent. Extremely soft and sticky foam. Sample 13 is a common foam that does not spring back immediately when compressed. When it recovers, it can completely return to its original shape and size. Therefore, the compression hardness is zero. , The hysteresis loss is almost 100 / 〇, because the test time is extremely short, the foam was compressed for the first time -22-

^459五、 發明説明（2〇 ) A7 B7 該發泡體僅分散落下球 後幾乎沒有恢復。在彈能試驗中， 之能量，並無回彈。 雖然已詳細描述説明本發明， ..^ ^ , 个贫月，但其並不限制本發明，而 疋包括在本發明精神與範疇内所 1 ’改變與改艮。 ---：---··--：I衣-- (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印« -23- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）^ 459 V. Description of the invention (20) A7 B7 The foam only recovered after the balls were dispersed and dropped. In the bomb test, the energy did not rebound. Although the present invention has been described in detail, .. ^ ^, a poor month, it does not limit the present invention, and includes changes and modifications within the spirit and scope of the present invention. ---: --- ··-: I clothing-- (Please read the notes on the back before filling in this page) Ordered by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs «-23- This paper size applies to Chinese national standards (CNS) A4 specification (210X297 mm)

Claims (1)

513459 第87108082號專利+請案 中文申請專利範圍修正本(91年1月）513459 Patent No. 87108082 + Petition for Amendment of Chinese Patent Application Range (January 91) 1· 一種衍生自反應混合物之聚胺甲酸酯發泡體組合物，該 反應混合物包含： 一種經氫化聚二晞二醇，其具有數量平均分子量自 1，000至20，000及每個分子自1.6至2個經基之官能度； 一種芳族聚異氰酸酯’其具有每個分子自1·8至3 〇個異 氰酸酯基之官能度； 一種增塑劑；及 一種發泡劑， 其中該增塑劑係一種油及/或一種數量平均分子量自5〇〇 至20,〇〇〇之氫化聚二缔單醇。 2·根據申請專利範圍第1項乏聚胺甲酸酯發泡體組合物，其 中該反應混合物進一步包含一種膠黏樹脂。 3·根據申請專利範圍第1或2項之聚胺甲酸酯發泡體組合 物’其中該聚二婦二醇對於增塑劑之用量在5:1至1:4範 圍内。1. A polyurethane foam composition derived from a reaction mixture, the reaction mixture comprising: a hydrogenated polydioxanediol having a number average molecular weight from 1,000 to 20,000 and each molecule Functionality from 1.6 to 2 warp groups; An aromatic polyisocyanate 'having a functionality from 1 · 8 to 30 isocyanate groups per molecule; a plasticizer; and a foaming agent, wherein the The plasticizer is an oil and / or a hydrogenated polydiethylene glycol having a number average molecular weight from 5,000 to 20,000. 2. The depleted polyurethane foam composition according to item 1 of the application, wherein the reaction mixture further comprises an adhesive resin. 3. The polyurethane foam composition according to item 1 or 2 of the scope of the patent application, wherein the amount of the polydiethylene glycol to the plasticizer is in the range of 5: 1 to 1: 4. 4·根據申請專利範圍第2項之聚胺甲酸酯發泡體組合物，其 中該聚二埽二醇對於膠黏樹脂之用量在5:1至1:4範圍 内0 5·根據申請專利範圍第1項之聚胺甲酸酯發泡體組合物， 其可由包括下列步驟之製法製得： 將經氫化聚二晞二醇與芳族聚異氰酸酯、發泡劑及增 塑劑摻合； 使該混合之聚二烯二醇、芳^聚異氰酸酯、發泡劑與 增塑劑發泡，製得該聚胺甲酸酯發泡體組合物。 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) ^1^459 A8 B8 C84. The polyurethane foam composition according to item 2 of the scope of the patent application, wherein the amount of the polydifluorene glycol to the adhesive resin is in the range of 5: 1 to 1: 4. 0 5 According to the patent application The polyurethane foam composition of the first item, which can be prepared by a manufacturing method including the following steps: blending a hydrogenated polydioxanediol with an aromatic polyisocyanate, a foaming agent, and a plasticizer; The mixed polydiene glycol, aromatic polyisocyanate, foaming agent and plasticizer are foamed to obtain the polyurethane foam composition. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ^ 1 ^ 459 A8 B8 C8 6.根據申請專利範圍第5項之聚胺甲酸酯發泡體組合物，其 中忒氫化聚二烯二醇、該發泡劑、該增塑劑與任何其他 組份係在該混合物與芳族聚異氰酸酯合併前混合。 7·根據申請專利範圍第5或6項之聚胺甲酸酯發泡體組合 物’其中該方法使用一種界面活性劑與一種觸媒。 8·根據申請專利範圍第5或6項之聚胺甲酸酯發泡體組合 物’其另外包括一種膠黏樹脂。 9· 一種聚胺甲酸酯發泡體組合物之製法，其包括 (1)混合一種數量平均分子量自1，〇〇〇至2〇,〇〇〇及每個分 子自1.6至2個羥基之官能度之經氫化聚二缔二醇、一種 增塑劑、一種發泡劑，及選擇性混合一種膠黏樹脂、一 種界面活性劑與一種觸媒，製得一混合物； (ii) 結合具有每個分子自1·8至3·〇個異氰酸酯基之官能 度之方族I異氨酸醋與該混合物，製得一種組合物；及 (iii) 使該組合物發泡，製得一種聚胺曱酸酯發泡體組合 物’其中該增塑劑係一種油及/或一種數量平均分子量自 500至20,000之氫化聚二烯單醇。 10·根據申清專利知圍第1、2或4-6項中任一項之聚胺甲酸 酯發泡體組合物，其係用於聚胺甲酸酯發泡體物件。 -2- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)6. The polyurethane foam composition according to item 5 of the application, wherein the hydrogenated polydiene glycol, the foaming agent, the plasticizer, and any other components are in the mixture and the aromatic compound. Group polyisocyanates are mixed before combining. 7. A polyurethane foam composition ' according to item 5 or 6 of the scope of the patent application, wherein the method uses a surfactant and a catalyst. 8. The polyurethane foam composition ' according to item 5 or 6 of the scope of patent application, which further includes an adhesive resin. 9. A method for producing a polyurethane foam composition, comprising (1) mixing a number average molecular weight from 1,000 to 20,000 and each molecule from 1.6 to 2 hydroxyl groups A hydrogenated polydiethylene glycol, a plasticizer, a foaming agent, and a mixture of an adhesive resin, a surfactant, and a catalyst are selectively mixed to obtain a mixture; (ii) combining And a mixture of 1 to 8 and 3.0 isocyanate functional groups of the formula I isocyanate and the mixture to prepare a composition; and (iii) foaming the composition to obtain a polyamine The gallate foam composition 'wherein the plasticizer is an oil and / or a hydrogenated polydiene monool having a number average molecular weight of 500 to 20,000. 10. The polyurethane foam composition according to any one of items 1, 2, or 4-6 of the Shenqing Patent, which is used for a polyurethane foam object. -2- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 裝Hold