200817448 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於藉由機械泡沬法，而可得具更加均勻細 微腔室氣孔聚胺基甲酸乙酯發泡物之製造方法。 【先前技術】 以機械泡沬法所製造之聚胺基甲酸乙酯發泡物被使用 於影印機之滾筒、化妝用粉撲、地毯、迫緊、密封材料、 減震材料、防震材料等。根據機械泡沬法而製造聚胺基甲 酸乙酯發泡物之製造方法，已提案有例如專利文件1及專 利文件2所記載之方法。 因專利文件1之製造方法未使用泡沬穩定劑，於所得 之聚胺基甲酸乙酯發泡物中可塑劑滲出的問題較少。然而 ，所得之聚胺基甲酸乙酯發泡物其腔室氣孔的狀態係大小 不一，且因部位而有硬度上之差異。 專利文件2之製造方法因使用醇改性聚矽氧油，且以 離心方式成形，可得氣孔少之發泡物。然而因係以離心方 式成形故爲較薄者’並不適合塊狀及較厚者。 針對使用於製造聚胺基甲酸乙酯發泡物之多元醇，聚 (氧）四甲基多元醇（以下簡稱做PTMG)，有較聚（氧）丙基多 元醇（以下簡稱做PPG)可得具優異之機械性強度、耐久性 、反發彈性等物理特性之聚胺基甲酸乙酯發泡物的傾向。 然而，至今尙未確立使用以PTMG爲主之多元醇藉由 機械泡沬法製造聚胺基甲酸乙酯發泡物之技術。 -5- 200817448 (2) 專利文件1 :特開2 0 0 1 - 8 9 5 4 7號公報 專利文件2:特開平1〇-25 8437號公報 【發明內容】 ' 本發明係以提供藉由以往的機械泡沬法，可得具更加 * 均勻細微腔室氣孔聚胺基甲酸乙酯發泡物之製造方法爲目 的。 本發明係爲解決上述課題專心檢討後所發現的結果， 亦即，本發明係一種聚胺基甲酸乙酯發泡物之製造方法， 其係將有機聚異氰酸酯（A)、含PTMG之多元醇（B)、觸媒 (C)以及泡沬穩定劑（D)分散混合後聚胺基甲酸乙酯發泡物 形成性組成物，進而於惰性氣體存在下藉由機械攪拌使其 混合分散後，再使其發泡硬化而成，其特徵在於該PTMG 含有量，係於聚胺基甲酸乙酯發泡物中佔50〜80質量％， 且該泡沬穩定劑（D)，係具末端烷基與平均數目分子量爲 1，000〜2,000的聚醚部之矽含有量爲5〜20質量％之二甲 基聚矽氧烷-聚醚塊共聚物。 另外，本發明係聚胺基甲酸乙酯發泡物之製造方法， 其中有機聚異氰酸酯（A)，係使二苯基甲烷二異氰酸酯（a) 與PTMG(b)反應而得之異氰酸酯基末端預聚合物，且，多 元醇（B)係含有PTMG(b)爲70〜90質量％者。 根據本發明，可得較以往的機械泡沬法，具更加均勻 細微腔室氣孔聚胺基甲酸乙酯發泡物。 於本發明中所使用之有機聚異氰酸酯（A)，可舉出二 -6- 200817448 (3) 苯基甲烷二異氰酸酯（以下簡稱做MDI)、聚苯基具亞甲基 聚異氰酸酯（以下簡稱做MDI系多核縮合體）、甲苯二異氰 酸酯、二甲苯二異氰酸酯、四甲基二甲苯二異氰酸酯、異 佛爾酮二異氰酸酯、六亞甲基二異氰酸酯、萘二異氰酸酯 、加氫二苯基甲烷二異氰酸酯、加氫二甲苯二異氰酸酯等 ，或這些具異氰酸酯基之化合物之異氰酸酯基的一部分於 胺基甲酸乙酯、二縮脲、脲基甲酯、碳二亞胺、亞胺、惡 唑烷酮、胺、醯亞胺、異氰酸酯、二酮等改性後者。可將 這些物質因應需要單獨或倂用二種以上而使用。 針對MDI、MDI系多核縮合體加以詳述。 MDI係以4,4’-二苯基甲烷二異氰酸酯（以下簡稱4,4’-MDI)，2,4’-二苯基甲烷二異氰酸酯（以下簡稱2,4’-MDI)， 2,2’-二苯基甲烷二異氰酸酯（以下簡稱2,2’-MDI)此三種異 構物任意比例之混合物（依不同狀況而爲何單品）之形式存 在。 MDI系多核體混合物係於一分子中異氰酸酯基所鍵結 有3個以上的苯環，以不同縮合度之化合物的形式而存在 。一般並不供應以MDI系多核體混合物單獨之形式，係 以與MDI之混合物（MDI與MDI系多核體混合物之混合物 ，簡稱爲「聚合MDI」）的形式而供給。 原本聚合MDI係將藉由苯胺與福馬林之縮合反應而 得之縮合混合物（聚胺），藉由光氣反應而使胺基轉化爲異 氰酸酯基所得者，生成物爲MDI與縮合度相異之MDI系 多核體混合物之混合物。MDI與聚合MDI的組成係依據 200817448 (4) 變動縮合時原料組成比及反應條件，或以蒸餾除去一部分 MDI而可加以改變。 MDI與聚合MDI的含有量及MDI的異構物之構成比 係可以凝膠滲透層析儀及氣體層析儀所得之各波形之面積 百分率爲基準再以檢量線換算而求得。 ’於本發明中，考量製造發泡物時之作業環境、發泡物 之成形性、所得聚胺基甲酸乙酯發泡物之物性等時，以含 有4,4’-MDI之含量爲50質量％以上之MDI、4,4’-MDI之 含量爲50〜100質量％以上之MDI之聚合MDI，以及使用 其所製造之異氰酸酯基末端胺基甲酸乙酯預聚合物爲佳， 而考量實際成形時之混合比及發熱狀況等時，前述之異氰 酸酯基末端胺基甲酸乙酯預聚合物爲更佳。 該異氰酸酯基末端胺基甲酸乙酯預聚合物，係可於有 機聚異氰酸酯（特別以前述之MDI爲佳），與後述之高分子 多元醇及異氰酸酯基過剩之條件下使其反應而得。反應溫 度以50〜lOOt：爲佳。有機聚異氰酸酯與高分子多元醇之 混合比大約爲等量，而考量異氰酸酯基末端胺基甲酸乙酯 預聚合物之黏度等時，異氰酸酯之含量以5〜35質量％爲 佳，8〜15質量％特佳。於製造該異氰酸酯基末端胺基甲 酸乙酯預聚合物時，有機聚異氰酸酯與高分子多元醇之混 合比，以有機聚異氰酸酯/高分子多元醇= 20/8 0〜50/50( 質量比）爲佳。爲確保於聚胺基甲酸乙酯發泡物中PTMG 之含量，於製造該異氰酸酯基末端胺基甲酸乙酯預聚合物 時，高分子多元醇以PTMG爲佳。 -8 - (5) (5) [數學式1] PTMG回收率（％ )= 200817448 於本發明中所使用之多元醇（B)係含PTMG之 多元醇與鏈延長劑所組成。此處之高分子多元醇係 數目分子量爲500以上之多元醇，鏈延長劑係指平 分子量未達500之多元醇。 根據本發明所得之聚胺基甲酸乙酯發泡物，其 甲酸乙酯發泡物中之PTMG僅含有50〜80質量％之 於此處之「PTMG含量」之測定方法，例如可 基甲酸乙酯發泡物以Kolisch分解再回收PTMG， 式所示，以相對於分解前聚胺基甲酸乙酯發泡物之 回收量之比而求得。200817448 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a method for producing a more uniform fine-cell pore-porous polyurethane foam by a mechanical foaming method. [Prior Art] Polyurethane foam produced by the mechanical foaming method is used for a roller of a photocopier, a cosmetic puff, a carpet, a pressing, a sealing material, a shock absorbing material, a shockproof material, and the like. A method for producing a polyurethane foam according to the mechanical foaming method has been proposed, for example, in Patent Document 1 and Patent Document 2. Since the foaming stabilizer is not used in the production method of Patent Document 1, there is less problem that the plasticizer oozes out in the obtained polyurethane foam. However, the obtained polyurethane foam has a state in which the pores of the chamber are different in size and have a difference in hardness due to the site. The production method of Patent Document 2 is obtained by using an alcohol-modified polysiloxane oil and being formed by centrifugation, whereby a foam having a small number of pores can be obtained. However, it is a thinner because it is formed by centrifugation. It is not suitable for bulk and thicker. For polyols used in the manufacture of polyurethane foams, poly(oxy)tetramethyl polyol (hereinafter referred to as PTMG) has a poly(oxy)propyl polyol (hereinafter referred to as PPG). There is a tendency to obtain a polyurethane foam having excellent physical properties such as mechanical strength, durability, and resilience. However, a technique for producing a polyurethane foam by a mechanical foaming method using a PTMG-based polyol has not been established so far. -5- 200817448 (2) Patent Document 1: Japanese Patent Laid-Open Publication No. Hei 2 0 0 1 - 8 9 5 4 7 Patent Document 2: Japanese Laid-Open Patent Publication No. Hei No. Hei. In the conventional mechanical foaming method, it is possible to obtain a method for producing a more uniform and uniform chamber pore polyurethane foam. The present invention is a result of intensive review after solving the above problems, that is, the present invention is a method for producing a polyurethane foam, which is an organic polyisocyanate (A), a PTMG-containing polyol. (B), the catalyst (C) and the foam stabilizer (D) are dispersed and mixed, and the polyurethane foam forming composition is further mixed and dispersed by mechanical stirring in the presence of an inert gas. Further, it is foamed and hardened, and is characterized in that the PTMG content is 50 to 80% by mass in the polyurethane foam, and the foam stabilizer (D) is a terminal alkane. The dimethylpolysiloxane-polyether block copolymer having a ruthenium content of from 5 to 20% by mass in the polyether portion having an average number of molecular weights of 1,000 to 2,000. Further, the present invention is a method for producing a polyurethane foam, wherein the organic polyisocyanate (A) is obtained by reacting diphenylmethane diisocyanate (a) with PTMG (b) to obtain an isocyanate group terminal. The polymer and the polyol (B) contain PTMG (b) in an amount of 70 to 90% by mass. According to the present invention, it is possible to obtain a more uniform fine-chamber ventilated polyurethane foam in the conventional mechanical foaming method. The organic polyisocyanate (A) used in the present invention may be exemplified by di-6-200817448 (3) phenylmethane diisocyanate (hereinafter referred to as MDI) and polyphenyl group with methylene polyisocyanate (hereinafter referred to as MDI polynuclear condensate), toluene diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate a portion of the isocyanate group of the compound having an isocyanate group, or a portion of the isocyanate group of the compound having an isocyanate group, in the group of ethyl urethane, biuret, ureidomethyl ester, carbodiimide, imine, oxazolidinone, The latter is modified by an amine, a quinone imine, an isocyanate, a diketone or the like. These materials can be used alone or in combination of two or more depending on the need. The MDI and MDI multinuclear condensates are described in detail. MDI is 4,4'-diphenylmethane diisocyanate (hereinafter referred to as 4,4'-MDI), 2,4'-diphenylmethane diisocyanate (hereinafter referred to as 2,4'-MDI), 2,2 '-Diphenylmethane diisocyanate (hereinafter referred to as 2,2'-MDI) is present in the form of a mixture of these three isomers in any ratio (why depending on the condition). The MDI-based multinuclear mixture is one molecule in which isocyanate groups are bonded with three or more benzene rings, and are present in the form of compounds having different degrees of condensation. It is generally not supplied in the form of a MDI-based multinuclear mixture alone, and is a mixture with MDI (a mixture of MDI and MDI-based multinuclear mixtures, abbreviated as "polymeric MDI"). The original polymeric MDI is a condensation mixture (polyamine) obtained by condensation reaction of aniline with formalin, and the amine group is converted into an isocyanate group by phosgene reaction, and the product is MDI and the degree of condensation is different. MDI is a mixture of multinuclear mixtures. The composition of MDI and polymeric MDI can be changed according to 200817448 (4) by changing the raw material composition ratio and reaction conditions during condensation, or by removing a part of MDI by distillation. The ratio of the content of MDI to the content of the polymerized MDI and the isomer of the MDI can be obtained by converting the area percentage of each waveform obtained by the gel permeation chromatograph and the gas chromatograph to the basis of the calibration curve. In the present invention, when the working environment at the time of producing the foam, the formability of the foam, the physical properties of the obtained polyurethane foam, and the like, the content of the 4,4'-MDI is 50. A polymerized MDI of MDI having a mass % or more of MDI and a 4,4'-MDI content of 50 to 100% by mass or more, and an isocyanate-terminated ethyl urethane prepolymer prepared using the same, preferably considering actual The above-mentioned isocyanate group-terminated ethyl urethane prepolymer is more preferable in the case of the mixing ratio at the time of molding and the heat generation condition. The isocyanate-terminated ethyl urethane prepolymer can be obtained by reacting an organic polyisocyanate (especially the above MDI) with an excess of a polymer polyol and an isocyanate group to be described later. The reaction temperature is preferably 50 to 100 t:. The mixing ratio of the organic polyisocyanate to the high molecular polyol is about the same amount, and when the viscosity of the isocyanate-terminated ethyl urethane prepolymer is considered, the content of the isocyanate is preferably 5 to 35 mass%, and the mass is 8 to 15 mass. % is particularly good. When the isocyanate-terminated ethyl urethane prepolymer is produced, the mixing ratio of the organic polyisocyanate to the polymer polyol is as follows: organic polyisocyanate/polymer polyol = 20/8 0 to 50/50 (mass ratio) It is better. In order to secure the content of PTMG in the polyurethane foam, the polymer polyol is preferably PTMG in the production of the isocyanate-terminated ethyl urethane prepolymer. -8 - (5) (5) [Math. 1] PTMG recovery (%) = 200817448 The polyol (B) used in the present invention is composed of a PTMG-containing polyol and a chain extender. Here, the polymer polyol is a polyol having a number of molecular weights of 500 or more, and the chain extender means a polyol having a molecular weight of less than 500. According to the polyurethane foam obtained by the present invention, the PTMG in the ethyl formate foam contains only 50 to 80% by mass of the "PTMG content" method, for example, the ethyl benzoate. The ester foam was decomposed by Kolisch to recover PTMG, as shown by the formula, in terms of the ratio of the recovered amount of the polyurethane foam before decomposition.
心/Zd分解後被回收之P7MG質量 分解前軟質聚胺基甲酸乙酯發泡物質量X 高分子多元醇可舉出聚醚多元醇、聚酯多元醇 酸酯多元醇、疏水性多元醇等。高分子多元醇之平 分子量以1，〇〇〇〜1 0,000爲佳，1，500〜5,000特佳。 目分子量過大時，發泡物之硬度易過低。平均數目 過小時，易損及發泡物之彈性。 聚醚多元醇可舉出例如將丙二醇、乙二醇、甘 甲基醇丙烷、己烷三醇等用作原材料之氧化亞烷進 聚合而得者，及將低分子環狀醚進行開環聚合而得 聚酯多元醇以使用藉由將二甲酸與三醇等進行 得之縮合系聚酯多元醇、將二醇及三醇做爲基底藉The quality of the soft polyurethane foam before the mass decomposition of P7MG recovered after the decomposition of the heart/Zd X. The polymer polyol may, for example, be a polyether polyol, a polyester polyol ester polyol, a hydrophobic polyol, or the like. . The molecular weight of the high molecular polyol is preferably from 1, 〇〇〇 to 1,000,000, and particularly preferably from 1,500 to 5,000. When the molecular weight of the mesh is too large, the hardness of the foam is liable to be too low. The average number is too small, the elasticity of the foam and the foam. The polyether polyol may, for example, be obtained by polymerizing oxyalkylene as a raw material such as propylene glycol, ethylene glycol, glycolol or hexane triol, and ring-opening polymerization of a low molecular cyclic ether. The polyester polyol is obtained by condensing a polyester polyol obtained by dicarboxylic acid with a triol or the like, and using a diol and a triol as a base.
高分子 指平均 均數目 聚胺基 量。 將聚胺 如下述 PTMG 、聚碳 均數目 平均數 分子量 行附加 者。 縮合而 由進行 -9 - 200817448 (6) 內酯開環聚合而得之內酯系聚酯多元醇、及於聚醚多元醇 之末端，以內酯使酯改性後之酯改性多元醇等爲佳。 聚碳酸酯多元醇可舉出將丁烷二醇及己烷二醇等低分 子多元醇，與碳酸丙烯酯及碳酸二甲酯等低分子碳酸酯， 進行酯交換反應而得者等。 疏水性多元醇可使用異戊二烯多元醇、聚丁二烯多元 醇、加氫聚丁二烯多元醇等。 可將這些高分子多元醇以一種或組合二種以上而使用 。於多元醇（B)中之高分子多元醇，以含有PtmG爲70〜 90質量％爲佳，進而與PTMG倂用之多元醇，以末端經 EO處理之PPG爲佳。 鏈延長劑可舉出例如乙二醇、丙二醇、1，4-丁烷二醇 、三甲基醇丙烷、四甲基醚二醇、聚乙二醇等。可將這些 鏈延長劑單獨或倂用二種以上而使用。於本發明中以H 丁烷二醇爲佳。其原因係1,4 - 丁烷二醇具一級羥基而有良 好的反應性，且於常溫下爲液狀有利於作業性，而因其具 適度之分子量故可得聚優異機械性強度之發泡物。 於本發明中所使用之觸媒（C)爲例如三乙基胺、二甲 基環己基安等單胺類，四甲基乙基二胺、四甲基丙基二胺 、四甲基己基二胺等二胺類，五甲基二次乙基三胺、五甲 基二次丙基三胺、四甲基胍等三胺類，三乙基二胺、二甲 基振嗪、甲基乙基振嗪、甲基嗎啉、二甲基胺乙基嗎啉、 二甲基咪唑等環狀胺類，二甲基胺乙醇、二甲基胺乙氧基 乙醇、三甲基胺乙基乙醇胺、甲基羥基乙基振嗪、羥基乙 -10- 200817448 (7) 基嗎啉等醇胺類’雙（二甲基胺乙基）醚、乙二醇雙（二甲基 )胺丙基醚等醚胺類，辛酸亞錫、醋酸丁二錫、月桂酸丁 二錫、二丁基錫硫醇鹽、二丁基錫硫碳酸酯鹽、二丁基錫 蘋果酸酯鹽、二辛基錫硫醇鹽、二辛基錫硫碳酸酯鹽、丙 酸苯汞、辛烯酸鹽等有機金屬化合物等周知之觸媒，可將 這些鏈延長劑單獨或倂用二種以上而使用。 於本發明中所使用之泡沬穩定劑（D)，係二甲基聚矽 氧烷-聚醚多元醇塊共聚物，矽含有量爲5〜20質量％， 具末端烷基與平均數目分子量爲1,000〜2,000的聚醚部。 泡沬穩定劑（D)若不符合上述條件中的任一個，即無 法充分形成細微的腔室氣孔，而無法獲得均勻的發泡物。 矽含有量係以灰化法而測定，具體而言係以下述順序 而加以測定。 測定矽含有量方法： 1 ·將樣品置於坩鍋中正確量秤。 2·加熱坩鍋使內容物燃燒。 3 ·量秤坩鍋中殘餘物質（灰分）。 4·以下述式計算出矽含有量。 [數學式2] 矽含有量（％ 末端烷基之定性則以NMR進行測定。於本發明中 NMR測定之條件如下所述。 -11 - 200817448 (8) 機種：Varian 製之 Unity500(FT-NMR) 測定時週波數：500 MHz 泡沫穩定劑（D)聚醚部之平均數目分子量，係將泡沬 穩定劑以Kolisch分解，再對其回收物測定GPC而求得。 本發明亦可因應需要而使用其他周知之添加劑。添加 劑可舉出例如防止氧化劑、紫外線吸收劑、耐火劑、著色 劑、導電劑、絕緣劑、發光劑、抗菌劑、芳香劑等。 使用這些原料而製造本發明之聚胺基甲酸乙酯發泡物 時，將分別保存或預先調製完成而置於各容器中之有機聚 異氰酸酯、多元醇、觸媒、泡沬穩定劑以及因應需要之添 加劑，於混入惰性氣體同時投入同一個攪拌器中，使其均 勻混合，再將該混合物注入舖有框型或底紙之輸送帶上， 接著可舉出加熱使其硬化，或將該混合液注入規定之模型 中加熱使其硬化等方法。以該方法所得之發泡物，具均勻 細微的腔室氣孔及適當硬度。 此時之異氰酸酯指數（異氰酸酯基/活性氫基xl 00)範圍 係以50〜150爲佳，60〜120特佳。指數過低時，發泡物表 面容易產生黏著感。指數過高時，會出現無法發泡、及凹 陷而無法得到柔軟的發泡物。 進行如上所述步驟後所得之聚胺基甲酸乙酯發泡物， 會成爲具密度爲0.3〜0.9 g/cm3之均勻細微腔室氣孔之發泡 物。 根據本發明所得之聚胺基甲酸乙酯發泡物，可適用於 電子照相裝置之碳粉運送滾筒、影印機之滾筒、帶電滾筒 -12- 200817448Polymer refers to the average number of polyamine groups. Polyamines such as the following PTMG, polycarbon number average molecular weight are added. a lactone-based polyester polyol obtained by ring-opening polymerization of a lactone at -9 - 200817448 (6), and an ester-modified polyol obtained by modifying a lactone with a lactone-based polyester polyol at the end of the polyether polyol It is better. Examples of the polycarbonate polyol include a low molecular weight polyol such as butanediol or hexanediol, and a low molecular weight carbonate such as propylene carbonate or dimethyl carbonate, which is obtained by transesterification. As the hydrophobic polyol, an isoprene polyol, a polybutadiene polyol, a hydrogenated polybutadiene polyol, or the like can be used. These polymer polyols may be used alone or in combination of two or more. The polymer polyol in the polyol (B) is preferably a PPG having a PtmG ratio of 70 to 90% by mass, and further a phenol treated with PTMG, preferably an EO-treated PPG. The chain extender may, for example, be ethylene glycol, propylene glycol, 1,4-butanediol, trimethylolpropane, tetramethyl ether glycol or polyethylene glycol. These chain extenders can be used singly or in combination of two or more. In the present invention, H-butanediol is preferred. The reason is that 1,4 - butanediol has a first hydroxyl group and has good reactivity, and it is liquid at normal temperature, which is advantageous for workability, and because of its moderate molecular weight, it can obtain excellent mechanical strength. Foam. The catalyst (C) used in the present invention is, for example, a monoamine such as triethylamine or dimethylcyclohexylamine, tetramethylethyldiamine, tetramethylpropyldiamine or tetramethylhexyl. Diamines such as diamines, triamines such as pentamethyldiethyltriamine, pentamethyldipropyltriamine, tetramethylhydrazine, triethyldiamine, dimethylpiperazine, methyl a cyclic amine such as ethylpyrazine, methylmorpholine, dimethylamine ethylmorpholine or dimethylimidazole, dimethylamine ethanol, dimethylamine ethoxyethanol, trimethylamine ethyl Ethanolamine, methylhydroxyethylpyrazine, hydroxyethyl-10-200817448 (7) Alcoholamines such as morpholine, 'bis(dimethylaminoethyl)ether, ethylene glycol bis(dimethyl)aminepropyl Ether amines such as ether, stannous octoate, dibutyltin acetate, dibutyltin laurate, dibutyltin thiolate, dibutyltin thiocarbonate, dibutyltin malate, dioctyltin thiolate, A well-known catalyst such as an octyl tin thiocarbonate salt, an organometallic compound such as phenylmercuric propionate or an octenoate can be used alone or in combination of two or more. The foam stabilizer (D) used in the present invention is a dimethyl polyoxyalkylene-polyether polyol block copolymer having a cerium content of 5 to 20% by mass, a terminal alkyl group and an average number molecular weight. It is a polyether part of 1,000 to 2,000. If the foam stabilizer (D) does not satisfy any of the above conditions, it is impossible to sufficiently form fine chamber pores, and a uniform foam cannot be obtained. The oxime content is measured by the ashing method, specifically, in the following order. To determine the amount of barium: 1 • Place the sample in the crucible and weigh the scale. 2. Heat the crucible to burn the contents. 3 · Residual material (ash) in the crucible. 4. Calculate the cerium content by the following formula. [Math 2] 矽 content (% of the terminal alkyl group is determined by NMR. The conditions for NMR measurement in the present invention are as follows. -11 - 200817448 (8) Model: Unity500 (FT-NMR) manufactured by Varian The number of cycles in the measurement: 500 MHz The average number of molecular weights of the polyether portion of the foam stabilizer (D) is obtained by decomposing the foam stabilizer in Kolisch and measuring the GPC of the recovered product. The present invention can also be obtained according to the need. Other known additives are used. Examples of the additive include an oxidizing agent, an ultraviolet absorber, a fire retardant, a colorant, a conductive agent, an insulating agent, a luminescent agent, an antibacterial agent, an aromatic agent, etc. The use of these raw materials to produce the polyamine of the present invention In the case of the ethyl urethane foam, the organic polyisocyanate, the polyol, the catalyst, the foam stabilizer, and the additive as needed in each container, which are separately stored or prepared in advance, are simultaneously mixed with the inert gas. In a stirrer, mix it evenly, and then inject the mixture into a conveyor belt with frame or bottom paper, then heat it to harden it, or note the mixture A method of heating and hardening in a prescribed mold, etc. The foam obtained by the method has uniform and fine chamber pores and appropriate hardness. The isocyanate index (isocyanate group / active hydrogen group xl 00) is in this range 50 to 150 is preferred, 60 to 120 is particularly good. When the index is too low, the surface of the foam is likely to have a sticky feeling. When the index is too high, there is a foam which cannot be foamed and dented and cannot be obtained softly. The polyurethane foam obtained after the step becomes a foam of uniform fine chamber pores having a density of 0.3 to 0.9 g/cm 3. The polyurethane obtained according to the present invention is obtained. Foaming material, applicable to toner conveying roller of electrophotographic device, roller of photocopying machine, charging roller-12-200817448
枕頭及床墊等寢具，化妝用粉撲 、減震材料、免震材料、防震材 、顯像滾筒等各種滾筒， 、迫緊、密封材料、地毯 料、隔音材料等各種領域 【實施方式】 實施例 以下以實施例將本發明更詳細地說明，但本發明並未 限定於這些實施例。於實施例以及比較例中，若無特別聲 明時，比率係質量比，「％」係「質量％」。 〔泡沬穩定劑之解析〕 針對泡沬穩定劑，將其矽含有量、末端基種類、聚醚 部之平均數目分子量之測定後結果示於表1。 表1 泡沬穩定劑名稱 F-341 X20-1749 F-374 B-8471 SZ-1136 矽含有量(％) 8 25 11 10 9 末端基 _ 甲基 甲基 羥基 甲基 甲基 聚醚部之平均數目分子· 1630 1680 1640 960 2200 於表1中’ @含有量：以前述之灰化法測定。 末端基··以NMR確認。 聚釀部之平均數目分子量··以Kolisch分解後將其回 -13- 200817448 (10) 收物以GPC-IR而測定。 所使用之泡沬穩定劑 F-341 :信越化學工業製之聚矽氧系泡沬穩定劑 X2 0- 1 749 :信越化學工業製之聚矽氧系泡沫穩定劑 F-3 74 :信越化學工業製之聚矽氧系泡沬穩定劑 ' B-847 1 : Goldschmidt製之聚矽氧系泡沬穩定劑 SZ-1 136 : Nippon Uni car製之聚矽氧系泡沬穩定劑 〔合成異氰酸酯基末端胺基甲酸乙酯預聚合物〕 合成例 於具備攪拌機、冷卻管、氮氣導入管以及溫度計之容 量爲1L之反應器中，加入376g之 MDI-1，與624g之 PTG-2000，攪拌同時使其於80°C下反應4小時，可得異氰 酸酯基末端胺基甲酸乙酯預聚合物NCO-l°NCO-l中異氰 酸酯含量爲10.0%。 於合成例中， MD1-1 :係含1 % MDI異構物混合體之二苯基甲烷二 異氰酸酯（MDI) PTG-2000 ：公稱平均官能基數=2，平均數目分子量 = 2,000之PTMG，保土谷化學工業製 ※MDI異構物混合體：4,4，-MDI之外的異構物（2,2’_ MDI以及2,4’-MDI)之混合物 〔調製多元醇預混合物〕 -14- 200817448 (11) 混合例1〜8 於容量爲2L之反應器中，加入如表2所示之各種物質 ，調製多元醇預混合物〇Η_1〜8。 表2 混合例 1 2 3 4 5 6 7 8 PTMG系高分子多 元醇(g)PTG-2000 非PTMG系高分子多 元醇(g)GL-3000 850 100 950 鏈延長劑(g) 1,4-BD 50 50 觸媒(g) DOTDL 0.08 0.08 泡沬穩定劑(g) F-341 10 50 5 10 X20-1749 10 F-374 10 B-8471 10 SZ-1136 10 多元醇預混合物名稱 OH-1 OH-2 OH-3 OH-4 OH-5 OH-6 OH-7 OH-8 於混合例1〜8及表2中， -15- 200817448 (12) PTG-2000 ：公稱平均官能基數=2，平均數目分子量 =2,000之？丁]\40，保土谷化學工業製 GL-3000:公稱平均官能基數=3，平均數目分子量= 3，000，羥乙烯基含量二11%之末端羥乙烯經處理後之聚（ 氧）丙基多元醇（PPG)，三洋化成工業製 • 1，4-BD ·· 1，4-丁 烷二醇 DOTDL:二辛基錫二月桂酯鹽 〔製造聚胺基甲酸乙酯發泡物〕 實施例1 將以表3所示比例混合後液溫爲40 °C之多元醇預混合 物OH-1，與液溫爲40°C之異氰酸酯基末端胺基甲酸乙酯 預聚合物NCO-1混合，將攪拌1分鐘使乾燥空氣混入後之 混合液，流注於金屬模具中（lOcmxlOcmxlOcm，無蓋）， 接著，將注入混合液後之金屬模具調整爲120 °C，置於熱 風烘箱中3 〇分鐘，使發泡胺基甲酸乙酯原料硬化。將硬化 後之聚胺基甲酸乙酯發泡物自金屬模具取下，完成聚胺基 甲酸乙酯發泡物之製造。 實施例2〜3、比較例1〜5 以表3所示之混合比，除將〇 Η -1變更爲〇 Η - 2〜8之外 ，其餘均以與實施例1相同之順序，製造聚胺基甲酸乙酯 發泡物。 -16- (13) (13)200817448 表3 實施例 比較例 1 2 3 1 2 3 4 5 多元醇預混合物 OH-1 OH-2 OH-3 OH-4 OH-5 OH-6 OH-7 OH-8 異氰酸酯指數 105 105 PTMG回收率(％该1 74 72 74 74 74 74 74 30 PTMG回收率(％该2 70 75 80 68 75 70 80 35 密度(g/cm3) 0.43 0.40 0.48 0.76 0.90 0.71 0.92 0.78 JIS-A硬度 45 43 48 64 72 60 74 65 腔室氣孔狀態 腔室氣孔平均個數比※3 1.00 1.05 0.91 0.42 0.18 0.51 0.14 0.39 腔室氣孔徑平均値(//m) 88 110 70 60 45 72 43 59 ※1 :加入後之理論値 ※2 :實測値 ※3 :以實施例1爲1.00時每單位面積之腔室氣孔個數比 〔評價聚胺基甲酸乙酯發泡物〕 發泡物之評價項目及測定方法如下所述。 PTMG回收率：以Kolisch分解將聚胺基甲酸乙酯發 泡物分解後，回收PTMG以相對於分解前聚胺基甲酸乙酯 發泡物，PTMG回收量之比而計算出。 密度、硬度：以JIS K 6401爲準而求得。 腔室氣孔平均個數比：測定存在於任意選擇的3個剖 面中之腔室氣孔個數，以實施例1爲1時之相對比而表示。 腔室氣孔徑平均値：測定存在於任意選擇的3個剖面 中之腔室氣孔直徑，將其平均値做爲腔室氣孔徑。 自表3可知，根據本發明所得之聚胺基甲酸乙酯發泡 -17- 200817448 (14) 物，係具均勻細微腔室氣孔，且低密度者。反之，於比較 例中，氣泡形成不順利，且密度變大，變爲無法充分形成 氣泡。 -18-Bedding such as pillows and mattresses, various types of rollers such as puffs, shock absorbing materials, shock-absorbing materials, shock-proof materials, developing rollers, etc., pressing, sealing materials, carpet materials, sound-insulating materials, etc. [Embodiment] Implementation EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to these examples. In the examples and comparative examples, the ratio is the mass ratio, and "%" is "% by mass" unless there is no special statement. [Analysis of the foam stabilizer] The results of the measurement of the oxime content, the terminal group type, and the average number molecular weight of the polyether portion of the foam stabilizer are shown in Table 1. Table 1 Bubble Stabilizer Name F-341 X20-1749 F-374 B-8471 SZ-1136 Antimony Content (%) 8 25 11 10 9 Average of Terminal Group_Methylmethylhydroxymethylmethyl Polyether Number of molecules · 1630 1680 1640 960 2200 In Table 1 ' @Content: determined by the aforementioned ashing method. The terminal group was confirmed by NMR. The average number of molecular weights of the brewing section was determined by GPC-IR after decomposition by Kolisch and returning it to -13-200817448 (10). Foam Stabilizer F-341 used: Polyoxo-based foam stabilizer Stabilizer manufactured by Shin-Etsu Chemical Co., Ltd. X2 0- 1 749: Polyoxo-based foam stabilizer F-3 74 manufactured by Shin-Etsu Chemical Co., Ltd.: Shin-Etsu Chemical Industry Polyoxygenated foam stabilizer Stabilizer' B-847 1 : Polyxanthene foam stabilizer SZ-1 136 by Goldschmidt : Polyoxygenated foam stabilizer for Nippon Uni car [synthetic isocyanate end Ethyl urethane prepolymer] In a reactor having a capacity of 1 L equipped with a stirrer, a cooling tube, a nitrogen gas introduction tube, and a thermometer, 376 g of MDI-1 was added, and 624 g of PTG-2000 was stirred and allowed to stand. After reacting at 80 ° C for 4 hours, the isocyanate-terminated ethyl urethane prepolymer NCO-l ° NCO-1 had an isocyanate content of 10.0%. In the synthesis example, MD1-1: diphenylmethane diisocyanate (MDI) containing a mixture of 1% MDI isomer PTG-2000: nominal average number of functional groups = 2, average number of molecular weight = 2,000 PTMG, Baotu Valley Chemical Industry ※MDI isomer mixture: a mixture of isomers other than 4,4,-MDI (2,2'_ MDI and 2,4'-MDI) [Preparation of polyol premix] -14- 200817448 (11) Mixing Examples 1 to 8 In a reactor having a capacity of 2 L, various substances as shown in Table 2 were added to prepare polyol premixes 〇Η_1 to 8. Table 2 Mixed Example 1 2 3 4 5 6 7 8 PTMG-based polymer polyol (g) PTG-2000 Non-PTMG-based polymer polyol (g) GL-3000 850 100 950 Chain extender (g) 1,4- BD 50 50 Catalyst (g) DOTDL 0.08 0.08 Bubble Stabilizer (g) F-341 10 50 5 10 X20-1749 10 F-374 10 B-8471 10 SZ-1136 10 Polyol Premix Name OH-1 OH -2 OH-3 OH-4 OH-5 OH-6 OH-7 OH-8 in mixing examples 1 to 8 and Table 2, -15-200817448 (12) PTG-2000: nominal average functional group number = 2, average Number of molecular weight = 2,000? D]]40, GT-3000, manufactured by Baotu Valley Chemical Industry Co., Ltd.: nominal average functional group number = 3, average number of molecular weight = 3,000, hydroxyvinyl group content of 11% of terminal hydroxyethylene treated poly(oxy)propyl group Polyol (PPG), manufactured by Sanyo Chemical Co., Ltd. • 1,4-BD ·· 1,4-butanediol DOTDL: dioctyltin dilaurate (manufacture of polyurethane foam) Example 1 Mix the polyol premix OH-1 at a liquid temperature of 40 °C in the ratio shown in Table 3, and mix it with the isocyanate-terminated ethyl urethane prepolymer NCO-1 at a liquid temperature of 40 °C. After stirring for 1 minute, the dry air was mixed into the mixture, and the mixture was poured into a metal mold (10 cm×10 cm×10 cm, without a cover). Then, the metal mold after the injection of the mixture was adjusted to 120 ° C, and placed in a hot air oven for 3 minutes. The foaming urethane raw material is hardened. The hardened polyurethane foam was removed from the metal mold to complete the production of the polyurethane foam. Examples 2 to 3 and Comparative Examples 1 to 5 In the mixing ratios shown in Table 3, except that 〇Η -1 was changed to 〇Η - 2 to 8, the same procedure was carried out in the same manner as in Example 1. A urethane foam. -16- (13) (13) 200817448 Table 3 Example Comparative Example 1 2 3 1 2 3 4 5 Polyol Premix OH-1 OH-2 OH-3 OH-4 OH-5 OH-6 OH-7 OH -8 isocyanate index 105 105 PTMG recovery rate (% of the 1 74 72 74 74 74 74 74 30 PTMG recovery rate (% of the 2 70 75 80 68 75 70 80 35 density (g / cm3) 0.43 0.40 0.48 0.76 0.90 0.71 0.92 0.78 JIS-A hardness 45 43 48 64 72 60 74 65 Chamber stomatal state chamber stomatal average number ratio *3 1.00 1.05 0.91 0.42 0.18 0.51 0.14 0.39 Chamber air permeability average 値 (//m) 88 110 70 60 45 72 43 59 *1 : Theory after joining 値 *2 : Actual measurement 値 *3 : Number of pores per unit area in the case of Example 1 at 1.00 [Evaluation of polyurethane foam] Foam The evaluation items and measurement methods are as follows: PTMG recovery rate: After decomposing the polyurethane foam by Kolisch decomposition, PTMG is recovered to recover PTMG relative to the pre-decomposition polyurethane foam. The ratio is calculated according to JIS K 6401. The average number of chamber pores: the measurement exists in any of the 3 selected The number of chamber vents in the face is expressed as the relative ratio when the embodiment 1 is 1. The chamber pore diameter average 値: the diameter of the chamber pores existing in any of the selected three sections is measured, and the average 値 is made. It is the pore diameter of the chamber. It can be seen from Table 3 that the polyurethane urethane foam -17-200817448 (14) obtained according to the present invention has uniform fine chamber pores and low density. In the example, the bubble formation is not smooth, and the density becomes large, and the bubble cannot be sufficiently formed.