201207036 ^ 六、發明說明： 【日月屬4支44^·區超5^】 技術領域 本發明係有關於一種使用有源自植物之原料的生質酚 樹脂之製造方法及熱硬化性材料者。 本案係基於2010年4月20日在日本提申的日本專利特 願2010-096988號案主張優先權，且將其内容援用於此。 I：先前技術3 背景技術 近年來，為了抑制大氣中二氧化碳量的增加，使用有 源自植物之原料之生質塑膠(所謂的碳中和（carb0n neutml) 材料）已受到矚目。 可作為生質塑膠者並非只有熱塑性樹脂，針對盼樹脂 等熱硬化性樹脂亦正在研究之中。舉例而言，於專利文獻 1、2中係揭不有-種在酸性催化劑下使紛類與砂糖反應而 得之酚樹脂。又，於專利文獻3中，係揭示有一種低軟化 點的生質紛樹月曰’其係在由紛類與木材製造盼樹脂時添加 熔點100°C以下之反應性物質（笨曱醇等）而得者。 習知技術文獻 專利文獻 【專利文獻1】日本專利特開昭58_55146號公報 【專利文獻2】日本專利特開平6_248_號公報 【專利文獻3】日本專利特開2〇〇4_352978號公報 I：發明内容】 201207036 發明概要 發明欲解決之課題 然而，專利文獻1、2中所記載的生質酚樹脂係高軟化 點，成形時的流動性低，且成形加工性不足。專利文獻3 中所記載的生質酚樹脂，雖藉由添加苯曱醇而使得軟化點 降低，但會有成本變咼及源自植物之比例降低等問題產生。 又，通常酚樹脂係藉由硬化劑以硬化成硬化體，而使 用於各種用途。然而，使專利文獻卜3中所記載的生質酚 樹脂硬化而得的硬化體，係強度低且揚式模數高者，而不 一定可說是具有充分機械物性者。 本發明之目的在於提供一種生質酚樹脂之製造方法， 其可製造成形加工性優異、具有高源自植物之比例，且可 知到尚強度且低楊式模數之硬化體的生質盼樹脂。又，本 發明之目的亦在於提供一種成形加工性優異、高源自植物 之比例，且可製造高強度且低揚式模數之硬化體的熱硬化 性材料。 用以解決課題之手段 本發明具有以下之構成。 [1] 一種生質酚樹脂之製造方法，包含在酸性催化劑下 使酚類與醣類反應，該酚類含有源自植物原料之不飽和烷 基酚’且該醣類含有多於50質量％之果糖源。 [2] 如[1]所記載之生質酚樹脂之製造方法，其中源自植 物原料之不飽和烷基酚係腰果酚(cardanol)。。 [3] —種熱硬化性材料’包含以如[丨]或[2]所記載之生質 4 201207036 * . 酚樹脂之製造方法製造的生質酚樹脂及硬化劑。 發明效果 若依本發明之生質酚樹脂之製造方法，可製造成形加 工性優異、具有高源自植物之比例，並能提供高強度且低 楊式模數之硬化體的生質酚樹脂。 本發明之熱硬化性材料其成形加工性優異、具有高源 自植物之比例，且可製造高強度且低楊式模數之硬化體。 再者，於本說明書中，源自植物之比例係指所得酚樹 脂或硬化體中的源自植物之成分的比例。源自植物之成分 係藉由使用大氣中二氧化碳之光合作用而得。因此，認為 源自植物之成分在焚化時之二氧化碳產生量，可以光合作 用時的二氧化碳吸收量互相抵銷，而不會對大氣中的二氧 化碳增加造成影響（所謂的碳中和）。因此，源自植物之比例 越高，越能抑制大氣中的二氧化碳量增加，而防止地球暖 化效果會變高。 t實施方式]1 用以實施發明的形態 <生質酚樹脂之製造方法> 本發明之生質酚樹脂之製造方法係在酸性催化劑下， 使含有源自植物原料之不飽和烷基酚的酚類與醣類反應之 方法。 於此反應中，藉由酸性催化劑而從含高果糖源之醣類 生成羥甲基呋喃醛，且該羥甲基呋喃醛與酚類會因酸性催 化劑而反應，藉此形成生質酌·樹脂。 201207036 盼類中所含的源自植物原料之不飽和烷基酚類，雖可 舉例如腰果酚、腰果殼液等，但以腰果酚為佳。若源自植 物原料之不飽和烷基酚類為腰果酚，則成形加工性會變得 更高’又，所得到的硬化體之彎曲強度可變得更高，且楊 式模數可變得更低。 上述不飽和烷基酚類可使用1種，亦可組合2種以上 前述不飽和烧基紛類來使用。 又，於酚類中，除了使用源自植物原料之不飽和烷基 酚類之外，亦可因應需要包含有源自化石燃料（石油、煤 炭、天然氣等）之酚類。 源自化石燃料之酚類可舉例如：酚、曱苯酚、二甲苯 酚、丙笨酚、丁笨酚、丁基甲笨酚、苯基苯酚、茴香基酚、 曱氧酚、溴苯酚、雙酚A等。其等可使用1種，亦可組合 2種以上前述源自化石燃料之酚類來使用。 上述源自化石燃料之酚類中，以反應性高及容易獲得 的點來看’以酚、曱苯酚、二曱苯酚或雙酚A等為佳。 在酚類含有源自植物原料之不飽和烷基酚類及源自化 石燃料之酚類時，前述酚類中源自植物之原料不飽和烷基 酚類之含量以5〜100質量％為佳，且以10〜50質量％更佳。 若源自植物之原料不飽和烷基酚類之含量在5質量％以 上，則可使所得到的生質酚樹脂之源自植物之比例實質地 變高’且可使從該生質酚樹脂得到的硬化體強度更高且楊 式模數更低。又，若源自植物之原料不飽和烷基酚類之含 量在50質量％以下，則在所得之生質酚樹脂中可在成形及 6 201207036 . 加工時輕易地保持充分的硬化性。 醣類係在令醣類固狀部分全體為100質量％時，含有 大於50質量％之果糖源，且以含有55質量％以上為佳，又 以含有75質量％以上更佳。又進一步，以醣類之100質量 %為果糖源最佳。於此，果糖源係指果糖單體，或具有藉 水解等來生成果糖的部分之化合物，可舉例如：果糖、聚 果糖、低聚果糖、醣類全體之果糖源含有率多於50質量％ 之寡醣、含有多於50質量％果糖源之高果糖玉米糖漿 (high-fructose corn syrup)等0 若醣類中的果糖源含有率在50質量％以下，生質酚樹 脂之流動性會變低，成形加工性會變得不足。 為了使醣類中的果糖源含有率多於50質量％，例如， 可令醣類為含有多於50質量％果糖源之含有高果糖源之醣 類。作為含有高果糖源之醣類，以容易獲得的觀點來看， 以含有多於50質量％之果糖源的高果糖玉米糖漿為佳。 醣類除了含有高果糖源之醣類之外，在不會使醣類全 體之果糖源含有率成為50質量％以下之範圍内，亦可使單 醣類、雙醣類、三醣類、寡醣類、多醣類等醣類（以下，將 該等醣類全體之果糖源含有率在50質量％以下的糖類總稱 為「其他醣類」。）與酚類反應。作為其他醣類，具體而言， 可列舉葡萄糖、甘露糖、半乳糖、阿拉伯糖、木糖、麥芽 糖、異麥芽糖、乳糖、蔗糖、海藻糖、棉子糖、環糊精、 醣類全體之果糖源含有率在50質量％以下之寡醣、澱粉、 粗澱粉、化工澱粉、直鏈澱粉、支鏈澱粉、廢糖蜜等。上 201207036 述其他醣類可使用1種，亦可組合2種以上之醣類來使用。 當醣類包含含有高果糖源之醣類及其他醣類時，含有 高果糖源之醣類之果糖源含有率越高，越容易使醣類之果 糖源含有率多於50質量％。 在得到酚樹脂時的酚類與醣類之質量比例，在令醣類 之固狀部分為1時，酚類以1〜20倍為佳，且以2〜4倍更佳。 若酚類為醣類之2倍以上，可提高反應率而提高產率並且 可使分子量變大；若在20倍以下，可在不使生產性降低的 情況下製造。 在酚類與醣類之反應時係使用有酸性催化劑。作為酸 性催化劑，係使用無機酸類(例如硫酸、鹽酸等）、有機酸類 (例如對曱苯磺酸、草酸等）等。酸性催化劑之使用量，係在 令酚類與醣類固狀部分之合計為100質量％時，以0.1〜50 質量％為佳，且以0.2〜10質量％更佳。若酸性催化劑之使 用量在0.1質量％以上，可使其充分地反應；若在50質量 %以下則可抑制酸分解或凝膠化。 反應溫度以在20〜200°C為佳，且以在120〜160°C更 佳。若反應溫度在20°C以上，可使其充分地反應；若在200 °C以下則可抑制分解。 反應時間以0.5〜20小時為佳，且以1〜3小時更佳。若 反應時間在0.5小時以上，可以高產率得到樹脂；若為20 小時則可抑制生產性的降低。 於上述製造方法中，由於使源自植物之原料不飽和烷 基酚類，與含有多於50質量％果糖源之醣類反應，而可得 8 201207036 到源自植物之比例高的生質酚樹脂。若藉由如此的生質酚 樹脂，依據碳中和的概念，可抑制二氧化碳排出量的增加。 又，藉由上述製造方法而得之生質酚樹脂係低軟化 點、流動性高且成形加工性優異。又，若藉由該生質酚樹 脂，可使硬化而得之硬化體強度變高'揚式模數變小。 如上所述的生質酚樹脂可使用於鑄造用鑄型、成形材 料、環氧硬化劑、各種黏結劑、橡膠材添加劑等。 <熱硬化性材料> 本發明之熱硬化性材料包含有藉由上述製造方法得到 的生質酚樹脂及硬化劑。 藉由將此熱硬化性材料成形、硬化，可得到由硬化體 構成之成形物。 (硬化劑） 匕劑係使上述生質酚樹脂硬化者。 劑，舉例而言，可使用六亞曱四胺、笨甲基胺、 、偶氮曱鹼、可溶酚醛樹脂型酚樹脂。其等之 由硬化性優異的觀點來看，以六亞曱四胺為佳。 硬化.摻合量，㈣於生質轉紅合計1⑼質量 二之IT，f量份為佳’且以3〜3g質量份更佳。若硬化 異；1f量份以上，則熱硬化性材料之硬化性優 性更高。冑里&以下’射使所得朗成形物之機械物 (填料） 吏所彳于之成形物的機械物性提升，熱硬化性材料 9 201207036 亦可包含有源自植物之填料、無機填料等填料。 源自植物之填料’可舉例如：木粉、稻殼粉、綿粉、 竹粉、核桃殻粉、紙粉、竹纖維、洋麻纖維等。其等之中， 從機械物性之提升效果大及容易獲得的觀點來看，以木粉 為佳。 當源自植物之填料為粒子狀時’其平均粒徑以在 0.1〜100G，為佳。於此’平均粒徑係二轴平均展開徑。 二軸平均制㈣'肺意⑽她子，⑽微鏡及影 像解析軟體(例如KEYENCE公司製顯微鏡VH_5〇〇〇與相同 公司製軟體VH_H1A5)來測量各_長_(μηι)及短轴徑 ㈣’並求得(長軸徑+短軸徑)/2之値，平均所求得之値來 求得。 若粒子狀的源自植物之填料的平均粒徑在心爪1 上’可使熱硬化性材料之流動性更高；若在麵㈣以下 貝J 了使成形物之機械物性更高。 當源自植物之填料為纖維狀時，其平均纖維長 (U〜謂麵為佳。於此，平均纖維長係藉由爪麵心 載之偏光光源方式來測量而得之値。 =狀的源自植物之填料:平均纖維長在。 物之機械物性更高；若在__以下，納 使熱硬化性材料之流動性更高。 無機填料可舉例如二 功 > 工h 孔化矽、氧化鋁、氮化矽、碳仆 石夕。月石 '石夕酸約、碳酸 荃母、黏土、鈦白等粉體、 玻璃纖，准、碳纖維等纖維體。 10 201207036 當無機填料為粒子狀時之平均粒徑，基於與源自植物 之填料相同的理由，而以0.1〜1000" m為佳。又，當無機 填料為纖維狀時之平均纖維長，基於與源自植物之填料相 同的理由，以0.1~100mm為佳。 填料之含量，相對於生質酚樹脂之合計1〇〇質量份， 以30〜500質量份為佳，且以5〇〜3〇〇質量份更佳。若填料 之含量在30質量份以上，可使成形物之機械物性更高；若 在500質量份以下’則可使流動性更高。 (硬化催化劑） 本發明之熱硬化性材料亦可包含硬化催化劑。硬化催 化劑係可促進生質酴樹脂與硬化劑之反應者。具體而言， 可列舉氫氧化鈣（消石灰）、氧化舞、氧化鎂等。 硬化催化劑之含量’相對於生質酚樹脂之合計1〇〇質 量份’係以0.1〜20質量份為佳，且以0 5〜15質量份更佳。 若硬化催化劑之含量在0.1質量份以上，可在短時間内使 其充分硬化。然而，縱使以大於2〇質量份的方式來包含硬 化催化劑，硬化促進效果會飽和，成本會變高。 (潤滑劑） 又，本發明之熱硬化性材料亦可包含用於使流動性更 為提升之潤滑劑。作為潤滑劑，可使用例如：卡那巴蛾、 二十八酸蠟、硬脂酸鈣、硬脂酸鋁、硬脂酸辞、低分子量 聚乙烯（聚乙烯蠟）等。 (其他添加劑） 又’本發明之熱硬化性材料中亦可包含例如：碳黑等 201207036 务外線吸收劑等添 著色劑、脫模劑、偶合劑、抗氧化劑、 加劑。 (熱硬化性材料之製造方法） 熱硬化性材料可藉由混合生質酚樹脂、硬化劑及因 需要混合之填料、硬化催化劑、潤滑劑、其他添加劑口… 在進行此混合時，亦可使用混合輥等混合機。又，在尾八 時’亦可在生質酚樹脂不會硬化的範圍内加 ° y. …。又，加熱 後，亦可因應需要粉碎。 、 (作用效果） 以上所說明之上述本發明之熱硬化性材料，由於勹人 上述生質酚樹脂，故成形加工性優異、具有高源自植物= 比例，且可製造高強度且低楊式模數之硬化體。 實施例 (酚樹脂之製造） [實施例1] 將酚300_8g、腰果酚60.2g、群榮化學工業製高果糖玉 米糖漿HF95(果糖源含有率95質量％，固狀部分75質量％ 水溶液）192g(固狀部分M4g)、硫酸2.5g饋送至具有溫度 計、攪拌裝置、冷卻管之500ml的三頸燒瓶中.此時，硫 酸之添加量係設為酚及醣類之固狀部分合計量的質量 %。 接著，一邊去除升溫途中所生成的水一邊加熱至155 °C，並在保持於155。(：之狀態下攪拌丨小時後，添加懸浮於 少量水中的氫氧化4弓1.9g而中和。其後，在2〇〇。〇、ukpa 12 201207036 - 之減壓下蒸餾去除未反應之酚175g，而得到266g之酚樹脂 (F-1)。 [實施例2] 將酚300.8g、腰果酚60.2g、群榮化學工業製高果糖玉 米糖漿HF95(果糖源含有率95質量％，固狀部分75質量％ 水溶液)96g(固狀部分72g)、群榮化學工業製高果糖玉米糖 漿HF55(果糖源含有率55質量％，固狀部分75質量％水溶 液)96g(固狀部分72g)、硫酸2.5g饋送至具有溫度計、攪拌 裝置、冷卻管之500ml的三頸燒瓶中。此時，硫酸之添加 量係設為酚及腰果酚及醣類之固狀部分合計量的0.5質量 %。 接著，一邊去除升溫途中所生成的水一邊加熱至155 °C，並在保持於155°C之狀態下攪拌1小時後，添加懸浮於 少量水中的氫氧化鈣1.9g而中和。其後，在200°C、llkPa 之減壓下蒸餾去除未反應之酚164g，而得到278g之酚樹脂 (F-2)。 [實施例3] 將酚300.8g、腰果酚60.2g、群榮化學工業製高果糖玉 米糖漿HF55(果糖源含有率55質量％，固狀部分75質量％ 水溶液）192g(固狀部分144g)、硫酸2.5g饋送至具有溫度 計、攪拌裝置、冷卻管之500ml的三頸燒瓶中。此時，硫 酸之添加量係設為酚及腰果酚及醣類之固狀部分合計量的 0.5質量％。 接著，一邊去除升溫途中所生成的水一邊加熱至155 13 201207036 °C，並在保持於155°C之狀態下攪拌1小時後，添加懸浮於 少量水中的氫氧化鈣1.9g而中和。其後，在200°C、llkPa 之減壓下蒸餾去除未反應之酚155g，而得到289g之酚樹脂 (F-3)。 [實施例4] 將酚300.8g、腰果酚105.3g、群榮化學工業製高果糖 玉米糖漿HF55(果糖含有源率55質量％，固狀部分75質量 %水溶液）192g(固狀部分144g)、硫酸2.8g饋送至具有溫度 計、攪拌裝置、冷卻管之500ml的三頸燒瓶中。此時，硫 酸之添加量係設為酚及腰果酚及醣類之固狀部分合計量的 0.5 質量°/〇。 接著，一邊去除升溫途中所生成的水一邊加熱至155 °C，並在保持於155°C之狀態下攪拌1小時後，添加懸浮於 少量水中的氫氧化鈣2.1g而中和。其後，在200°C、llkPa 之減壓下蒸餾去除未反應之酚153g，而得到312g之酚樹脂 (F-4)。 [比較例1] 將酚300.8g、腰果酚60.2g、樹薯澱粉(果糖源含有率0 質量％，固狀部分88質量％)78.7g(固狀部分69.2g)、砂糖(果 糖源含有率50質量％)74.8§、硫酸2.5g饋送至具有溫度計、 攪拌裝置、冷卻管之500ml的三頸燒瓶中。此時，硫酸之 添加量係設為酚及腰果酚及醣類之固狀部分合計量的0.5 質量％。 接著，一邊去除升溫途中所生成的水一邊加熱至155 14 201207036 °C，並在保持於155°C之狀態下攪拌1小時後，添加懸浮於 少量水中的氫氧化鈣1.9g而中和。其後，在200°C、llkPa 之減壓下蒸餾去除未反應之酚131g，而得到315g之酚樹脂 (F-5)。 [比較例2] 將酚300.8g、腰果酚60.2g、樹薯澱粉（果糖源含有率0 質量％，固狀部分88質量％)128.8§(固狀部分113.3g)、砂 糖(果糖源含有率50質量％)30.6§、硫酸2.5g饋送至具有溫 度計、攪拌裝置、冷卻管之500ml的三頸燒瓶中。再者， 硫酸之添加量係設為酚及腰果酚及醣之固狀部分合計量的 0.5質量％。 接著，一邊去除升溫途中所生成的水一邊加熱至155 °C，並在保持於155°C之狀態下攪拌1小時後，添加懸浮於 少量水中的氫氧化鈣1.9g而中和。其後，在200°C、llkPa 之減壓下蒸餾去除未反應之酚122g，而得到316g之酚樹脂 (F-6)。 [比較例3] 將酚300.8g、腰果酚105.3g、樹薯澱粉（果糖源含有率 0質量％，固狀部分88質量％)128.8§(固狀部分113.3g)、砂 糖(果糖源含有率50質量％)30.6g、硫酸2.8g饋送至具有溫 度計、攪拌裝置、冷卻管之500ml的三頸燒瓶中。再者， 硫酸之添加量係設為酚及腰果酚醣類之固狀部分合計量的 0.5質量％。 接著，一邊去除升溫途中所生成的水一邊加熱至155 15 201207036 c，並在保持於155t之狀態下攪拌丨小時後，添加懸 v里水中的氫氧化的21g而中和。其後，在細。C、11吵 =壓下蒸料除未反應以U4g，術⑽g之紛樹脂& [比較例4] 將盼3m)g、5G質4%甲料溶液l56g、草酸2.1§饋 运至具有溫度計、裝置、冷卻管之獅ml的三頸燒瓶 中。再者，相對於盼的m水溶液莫耳比為G 815，草酸之 添加量則設為盼之0.7質量％。 接著’於6lkPa之減壓下加熱至95〇c，並在減壓、保 持溫度的狀態下_2小時後’減駐nkpa並去除反應 所產生的水。再於f壓下，—邊去除所生成的水_邊加熱 至180C ’並在i80°c、llkPa之減壓下蒸餾去除未反應之 酚36g及水，而得到312g之酚樹脂(F_8)。 [比較例5] 將酚270g、群榮化學工業製高果糖玉米糖漿Ηρ55(果 糖源含有_55質量％，陳部分75質量％水溶液)144g(固 狀。卩为108g)、硫酸丨9g饋送至具有溫度計、攪拌裝置、 冷卻管之5GGml的三頸驗中。再者，硫酸之添加量係設 為酚及醣之固狀部分合計量的0.5質量。/〇。 接著，一邊去除升溫途中所生成的水一邊加熱至155 °C，並在保持於155t之狀態下攪拌丨小時後，添加懸浮於 >、量水中的氫氧化鈣丨4g而中和。其後，在2〇〇。〇、llkPa 之減壓下蒸餾去除未反應之酚1〇9g，而得到2〇lg之酚樹脂 16 201207036 . (F-9)。 [比較例6] 將酚338.4g、群榮化學工業製高果糖玉米糖漿HF55(果 糖源含有率55質量％，固狀部分75質量％水溶液）144g(固 狀部分108g)、硫酸2.2g饋送至具有溫度計、攪拌裝置、 冷卻管之500ml的三頸燒瓶中。硫酸之添加量係設為酚及 醣之固狀部分合計量的0.5質量％。 接著，一邊去除升溫途中所生成的水一邊加熱至155 °C，並在保持於155°C之狀態下攪拌1小時後，添加懸浮於 少量水中的氫氧化鈣1.7g而中和。其後，在200°C、llkPa 之減壓下蒸餾去除未反應之酚162g，而得到223g之酚樹脂 (F-10)。 (評定） 針對所得到的酚樹脂，藉由以下方法來測量軟化點、 流動性、源自植物之比例、腰果酚改質率。將測量結果示 於表1。 [軟化點]遵循JIS K6910測量。 [流動性]遵循JIS K6910測量。 [源自植物之比例]源自植物之比例=100- {[(盼進料質 量）-(蒸餾去除的未反應酚質量）+ (中和鹽之質量（理論 値))]/(樹脂產量質量）} X100 [腰果酚改質率]腰果酚改質率=[(腰果酚進料質量)/(樹脂 產量質量)]xl〇〇 【表1】 17 201207036 (0 爝 ii 商采換玉米糖S 1 338.4 1 Ο g y— C^J csi 1 Ο d * · τ— CO in in to d CNJ to ^- CO CM <N4 o in 〇> r- 〇 in 匡 U η 高果糖玉米糖槳 1 ο CVJ Ο g T— O) 1— 1 ο ο 产 ΙΛ eg m u? in d s S 05 ♦>— s CO 〇6 〇 寸 餚 η 1 (〇 1〇 ο 8 ο 1 1 csi ο ο 1 1 1 <〇 CO <NJ O) σ> CO <D o 〇 CO 爝 ±i 1 300.8 105.3 5 t— 00 c^i 1 σ> LT> CM 2.8:1 r~ m d 寸 r~ T-· σ> LO CO g »— S σ> <〇 CO σ> CNJ 1 1 1 300.8 CNJ Ο <〇 5 T- m c^j 1 卜 <〇 1» in eg in d eg CM r~ CO t— CO 产 00 CO r- σ> 1 1 1 300.8 CM ο <〇 in cJ 1 r*· (Ο LO cJ <〇 CNJ in d ?； (A S 寸 r— IT- 00 CM 45.0 σ> EHaOBIMSQIEMiEliHfflEl 1 300.8 105.3 5 1— 00 csi 1 σ> LT> CM 00 OJ LO in in d CO in CNJ S g Csj 00 00 Η C0 1 300.8 S 5 IA CNJ 1 卜 cd in CNI m LO m d m in 产 O) 00 CM 〇 T— Γ0 » 00 1 300.8 CM S m cJ 1 卜 cd r- ΙΛ CNJ in in d s 00 CM CO in O) 卜 1 300.8 CS| Ο (Ο Z T- m cJ 1 卜 <6 m c\i m ΟΪ LA O in <〇 €NJ ΙΛ σ> σ> τ— m <D 〇4 CSi 睜 趙 餓 堅 bO m * m fr /-Ν bfl V-/ 窗 坳 翁 mV 豳 /-\ hfl 筢 Μ 魅 /·> b〇 N-/ 趣 握 1 /-> bO s-/ 龌 含有率（質量％) 掛 ±J H； M f^-N： 随涵 •AP· mP»' 豳魅 m 睞运 NiW 瞄贓| 齠H /-> S5 啣 s>> Φ 兵 联 蘅 3JI11 纖 i ^-N bO 窗 m 伥 ^-s bo dM m Dm BC $ ! #—\ s u /-v E E 姻 ωΚ s mi i 岫 μ 1 Ν 迴 腾 味品1 鹽s B·掛 18 201207036 使包含腰果酚之酚類與高果糖玉米糖漿（果糖源含有 率大於50質量％)反應而得之實施例1〜4之酚樹脂，其軟化 點低、流動性優異，此外，源自植物之比例高。 使用澱粉、砂糖(果糖源含有率在50質量％以下)作為 醣類而得到的比較例1〜3之酚樹脂，其軟化點高、流動性 低0 使用甲醛水溶液的一般酚樹脂即比較例4之酚樹脂， 其源自植物之比例低。 使齡與高果糖玉米糖漿（果糖源含有率大於50質量％) 反應而得之比較例5、6之酚樹脂，其源自植物之比例低， 並且权化點尚、流動性低。 (熱硬化性材料之製造） [實施例5] 將紛樹脂(F-l)lOOg、木粉98g、作為硬化劑之六亞曱 四胺20g '作為硬化助劑之氫氧化鈣7g、作為潤滑劑之硬 脂酸鋅3g、作為著色劑之碳黑1.5g混合混練，而製作成形 材料。 [實施例6〜8、比較例7〜12] 除了將酚樹脂(F-1)變更成表2所示的酚樹脂之外，與 實施例5相同地進行，而製作成形材料。 [成形加工性] 使用射出成形機（日精樹脂工業公司製ρΝχ_4〇)於170 C並以2刀鐘的成形條件將各實施例及各比較例之成形材 料射出成形，並使其硬化而得到成形物。 19 201207036 藉由以下基準評定此時的生產性、所得成形物之品 質。將評定結果示於表2。 ◎:因流動性高而易成形、且於成形物外觀亦無問題。 〇：雖可成形，但流動性稍低，射出時容易變得短射 (short shot) ° △:雖因流動性高而易成形，但由於硬化慢，而會於 成形物產生膨脹。 ▲:由於流動性低而難以成形，且由於硬化慢而會於 成形物產生膨脹。 X :射出時之樹脂黏度高，無法射出。 [彎曲強度、楊式模數及彎曲量之測量] 藉由射出成形機（曰精樹脂工業公司製PNX-40)將各實 施例及各比較例之成形材料射出成形，並使其硬化而得成 形物。使用所得成形物，依循JISK6911，於25°C測量彎曲 強度、楊式模數（彎曲彈性率）。又，於彎曲試驗中測量成形 物直到斷裂為止的彎曲變位量作為彎曲量。將測量結果示 於表2。彎曲強度越高、楊式模數越低、彎曲量越小時，機 械物性會變得越好。 再者，關於比較例7、8及11，由於無法成形，因此並 未測量彎曲強度、楊式模數及彎曲量。 【表2】 20 201207036 CSJ 1 1 1 I I 1 I I I ο τ~* 00 σ> s 卜 CO l〇 〇 CM 00 CO 9.8 I ΙΛ r— r~ 1 1 1 I I 1 I I I_100 I I X 無法成形 o 1 1 1 I I 1 I o I I ◎ Γ 94.7 I o a> 1 1 1 I I 1 Ί00 I I I ◄ 65.0 I 00 id 2.7 00 1 1 1 I I 1_100 I I I I I X 無法成形 卜 1 1 1 I _100 1 I I I I I X m HO 00 1 1 1 100 1 I I I I I < i 6.8 to CsJ 卜 1 1 1__100 I I 1 I I I I I 〇 σ> σ> 7.2 2.7 I 4¾ κ <〇 1 ο I I 1 I I I I I ◎ CM GO CO 00 o 1 I I 1 I I I I I ◎ I 34.2 | CO 1-: 〇> cvi r- 1 U. s—/ ss CM 1 Li- 鋰 m 窓 CO I U- SS i 窗 /"N I Li. 鋰 m 涵 ω 1 L- 鋰 m m (0 I \L· m 班 避 I u. s m si 00 I Ll SS m 豳 0) I L· S5 班 避 〇 r- I Ll 鋰 m 溢 /-N 长 3 S a B- 冏 ^b〇 m 3 S 趣 m im./ e ^bj HP 既 m H □ I 0. B m 埋 s 顧* « 0- S 親 m 怵 m E E «w/ 宙 if 樹脂成分 3 21 201207036 含有實施例1〜4各酴樹脂之實施例5〜8之成形材料成 形加工性優異’並且所得成形物之彎曲強度高、楊式模數 小。特別是，即便實施例5、6及7具有與使用一般酚樹脂 (比較例10)時相同程度的彎曲強度，揚式模數仍很低。 含有比較例3使用澱粉、砂糖之醣類而得之酚樹脂之 比較例9之成形材料，其成形加工性低，且所得.贊曲強度 低。 使用有比較例4之使用曱醛水溶液而得者作為酚樹脂 的比較例10之成形材料’其源自植物之比例低。又，所得 成形物之揚式模數高，且彎曲量小。 含有比較例6之使酚、殿粉與砂糖反應而得之酚樹脂 的比較例12之成形材料，所得成形物之彎曲強度低、楊式 模數高、彎曲量小。 含有比較例1之酚樹脂的比較例7之成形材料、含有 比較例2之酚樹脂的比較例8之成形材料、含有比較例5 之酚樹脂的比較例11之成形材料，由於所使用的酚樹脂之 軟化點高而流動性低，故射出成形時之樹脂黏度高，而無 法進行射出成形。 產業上之可利用性 若依據本發明之生質酚樹脂之製造方法’可製造成形 加工性優異、具有高源自植物之比例，且可提供高強度且 低楊式模數之硬化體的生質酚樹脂。本發明之熱硬化性材 料，其成形加工性優異、具有高源自植物之比例’且可製 造高強度且低楊式模數之硬化體。又’本發明之熱硬化性 22 201207036 • 材料由於具有高源自植物之比例，因此可抑制大氣中的二 氧化碳量增加，防止地球暖化效果會變高。 c圖式簡單說明3 無 【主要元件符號說明】 益 < "、 23201207036 ^ VI. Description of the Invention: [Day and Moon 4 genus 44^·region super 5^] Technical Field The present invention relates to a method for producing a phenolic resin using a plant-derived raw material and a thermosetting material . The present application claims priority on the basis of Japanese Patent Application No. 2010-096988, filed on Apr. 20, 2010, the content of which is incorporated herein. I. Prior Art 3 Background Art In recent years, in order to suppress an increase in the amount of carbon dioxide in the atmosphere, the use of a raw material having a plant-derived raw material (so-called carbon-neutral material) has been attracting attention. It can be used as a raw plastic, not only a thermoplastic resin, but also a thermosetting resin such as a resin. For example, in Patent Documents 1 and 2, there is no phenol resin which is obtained by reacting a mixture with granulated sugar under an acidic catalyst. Further, in Patent Document 3, it is disclosed that there is a low-softening point of the raw material of the tree, which is a reactive substance having a melting point of 100 ° C or less when the resin is produced from a variety of woods. ) and the winner. CITATION LIST Patent Literature [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In the case of the raw material phenol resin described in Patent Documents 1 and 2, the high softening point is low, and the fluidity at the time of molding is low, and the moldability is insufficient. The raw phenol resin described in Patent Document 3 has a softening point by adding phenylhydrin, but there are problems such as cost reduction and a decrease in the ratio of plant-derived plants. Further, in general, a phenol resin is used for various purposes by being hardened into a hardened body by a curing agent. However, the cured body obtained by curing the phenolic phenol resin described in Patent Document 3 has a low strength and a high lift modulus, and it is not necessarily a sufficient mechanical property. An object of the present invention is to provide a method for producing a raw phenol resin which is capable of producing a green resin which is excellent in moldability, has a high ratio derived from plants, and is known to have a strong strength and a low Young's modulus. Further, an object of the present invention is to provide a thermosetting material which is excellent in moldability, high in plant-derived ratio, and which can produce a high-strength and low-lift modulus hardened body. Means for Solving the Problems The present invention has the following constitution. [1] A method for producing a raw phenol resin comprising reacting a phenol with a saccharide containing an unsaturated alkyl phenol derived from a plant material under an acidic catalyst and the saccharide contains more than 50% by mass The source of fruit sugar. [2] The method for producing a phenolic resin according to [1], wherein the unsaturated alkylphenol derived from the plant material is cardanol. . [3] A thermosetting material ‘ contains a phenolic resin and a curing agent produced by the method for producing a phenol resin as described in [丨] or [2]. According to the method for producing a raw phenol resin of the present invention, a raw phenol resin which is excellent in moldability, has a high ratio derived from plants, and can provide a high-strength and low-yield hardened body can be produced. The thermosetting material of the present invention is excellent in moldability, has a high ratio of plant-derived materials, and can produce a high-strength and low-yang type modulus hardened body. Further, in the present specification, the ratio derived from plants means the ratio of the plant-derived components in the obtained phenol resin or hardened body. Plant-derived ingredients are obtained by photosynthetic use of carbon dioxide in the atmosphere. Therefore, it is considered that the amount of carbon dioxide produced by plant-derived components at the time of incineration can be offset by the amount of carbon dioxide absorbed during photosynthesis without affecting the increase of carbon dioxide in the atmosphere (so-called carbon neutralization). Therefore, the higher the proportion derived from plants, the more it can suppress the increase in the amount of carbon dioxide in the atmosphere, and the effect of preventing global warming will become higher. (Embodiment) 1 Embodiment for carrying out the invention <Method for producing a raw phenol resin> The method for producing a raw phenol resin according to the present invention is to contain an unsaturated alkylphenol derived from a plant material under an acidic catalyst. A method of reacting phenols with sugars. In this reaction, hydroxymethylfuran aldehyde is formed from a saccharide containing a high fructose source by an acidic catalyst, and the hydroxymethylfuran aldehyde and the phenol are reacted by an acidic catalyst, thereby forming a raw resin. . 201207036 The unsaturated alkylphenols derived from plant materials contained in the class are, for example, cardanol, cashew nut shell liquid, etc., but cardanol is preferred. If the unsaturated alkylphenol derived from the plant material is cardanol, the formability will become higher. Further, the bending strength of the obtained hardened body can be made higher, and the Young's modulus can become more low. The above unsaturated alkylphenols may be used singly or in combination of two or more kinds of the above-mentioned unsaturated alkyl groups. Further, in addition to the use of unsaturated alkyl phenols derived from plant materials, phenols may also contain phenols derived from fossil fuels (petroleum, coal, natural gas, etc.) as needed. The phenols derived from fossil fuels may, for example, be phenol, nonylphenol, xylenol, propofol, butanol, butyl methylphenol, phenylphenol, anisidine, nonoxyphenol, bromophenol, bisphenol A. Wait. These may be used alone or in combination of two or more kinds of phenols derived from fossil fuels. Among the above-mentioned phenols derived from fossil fuels, phenol, nonylphenol, dinonylphenol or bisphenol A is preferred from the viewpoint of high reactivity and easy availability. When the phenol contains unsaturated alkylphenols derived from plant materials and phenols derived from fossil fuels, the content of the unsaturated alkylphenols derived from plants in the phenols is preferably from 5 to 100% by mass. And more preferably 10 to 50% by mass. When the content of the plant-derived raw material unsaturated phenol is 5% by mass or more, the plant-derived ratio of the obtained phenol resin can be substantially increased, and the phenol resin can be obtained from the phenol resin. The resulting hardened body is stronger and the Young's modulus is lower. In addition, when the content of the unsaturated alkylphenols derived from the plant is 50% by mass or less, the resulting raw phenol resin can be easily formed into a sufficient curing property during molding and processing. When the total amount of the solid content of the saccharide is 100% by mass, the saccharide is preferably contained in an amount of more than 50% by mass, more preferably 55% by mass or more, more preferably 75% by mass or more. Further, it is preferred that the sugar source is 100% by mass of the sugar. Here, the fructose source refers to a fructose monomer or a compound having a moiety which produces fructose by hydrolysis or the like, and examples thereof include a fructose source content of more than 50% by mass of fructose, polyfructose, oligofructose, and saccharide. Oligosaccharide, high-fructose corn syrup containing more than 50% by mass of fructose source, etc. If the fructose source content in the saccharide is 50% by mass or less, the fluidity of the phenol resin may change. Low, the formability will become insufficient. In order to make the fructose source content in the saccharide more than 50% by mass, for example, the saccharide may be a saccharide containing a high fructose source containing more than 50% by mass of a fructose source. As the saccharide containing a high fructose source, it is preferable to use a high fructose corn syrup containing more than 50% by mass of a fructose source from the viewpoint of easy availability. In addition to the sugar containing a high fructose source, the saccharide may be such that the fructose source content of the whole saccharide is 50% by mass or less, and monosaccharides, disaccharides, trisaccharides, and oligosaccharides may be used. Sugars such as saccharides and polysaccharides (hereinafter, the saccharides in which the fructose source content of all the saccharides is 50% by mass or less are collectively referred to as "other saccharides") are reacted with phenols. Specific examples of the other sugars include fructose such as glucose, mannose, galactose, arabinose, xylose, maltose, isomaltose, lactose, sucrose, trehalose, raffinose, cyclodextrin, and sugar. Oligosaccharides, starches, crude starches, chemical starches, amylose, amylopectin, waste molasses and the like having a source content of 50% by mass or less. In 201207036, one type of other sugars may be used, and two or more types of sugars may be used in combination. When the saccharide contains a saccharide or a saccharide containing a high fructose source, the higher the fructose source content of the saccharide containing the high fructose source, the more easily the saccharide fructose content is more than 50% by mass. When the phenol resin is obtained, the mass ratio of the phenol to the saccharide is preferably from 1 to 20 times, more preferably from 2 to 4 times, when the solid portion of the saccharide is one. If the phenol is twice or more the saccharide, the reaction rate can be increased to increase the yield and the molecular weight can be increased, and if it is 20 times or less, it can be produced without lowering the productivity. An acidic catalyst is used in the reaction of phenols with sugars. As the acid catalyst, inorganic acids (e.g., sulfuric acid, hydrochloric acid, etc.), organic acids (e.g., p-toluenesulfonic acid, oxalic acid, etc.), etc. are used. When the total amount of the phenols and the saccharide-formed portion is 100% by mass, the amount of the acid catalyst is preferably from 0.1 to 50% by mass, more preferably from 0.2 to 10% by mass. When the amount of the acidic catalyst is 0.1% by mass or more, it can be sufficiently reacted; if it is 50% by mass or less, acid decomposition or gelation can be suppressed. The reaction temperature is preferably from 20 to 200 ° C, and more preferably from 120 to 160 ° C. If the reaction temperature is above 20 ° C, it can be sufficiently reacted; if it is below 200 ° C, decomposition can be inhibited. The reaction time is preferably from 0.5 to 20 hours, more preferably from 1 to 3 hours. When the reaction time is 0.5 hours or longer, the resin can be obtained in a high yield; if it is 20 hours, the decrease in productivity can be suppressed. In the above production method, since the plant-derived raw material unsaturated alkylphenols are reacted with a sugar containing more than 50% by mass of a fructose source, 8 201207036 can be obtained from the plant-derived ratio of the raw phenol. Resin. According to the concept of carbon neutralization, the increase in the amount of carbon dioxide emission can be suppressed by such a raw phenol resin. Further, the raw phenol resin obtained by the above production method has a low softening point, high fluidity, and excellent moldability. Further, when the raw phenol resin is used, the strength of the hardened body which is hardened can be increased, and the 'yang type modulus is small. The raw phenol resin as described above can be used for casting molds, molding materials, epoxy hardeners, various binders, rubber material additives, and the like. <Thermosetting material> The thermosetting material of the present invention contains the phenol resin and the curing agent obtained by the above production method. By molding and hardening the thermosetting material, a molded product composed of a hardened body can be obtained. (Hardener) The tanning agent cures the above-mentioned raw phenol resin. As the agent, for example, hexamethylenetetramine, stupid methylamine, azobenzene, or resol type phenol resin can be used. Among them, hexamethylenetetramine is preferred from the viewpoint of excellent curability. Hardening. Blending amount, (4) Total amount of raw material to red (1) mass II, IT, f parts are good' and more preferably 3 to 3 g parts by mass. If the hardening is more than 1 part, the hardenability of the thermosetting material is higher.胄里 & The following 'injection of the mechanical material (filler) of the obtained granules is improved by the mechanical properties of the molded product, and the thermosetting material 9 201207036 may also contain fillers derived from plant fillers, inorganic fillers, etc. . The plant-derived filler may, for example, be wood flour, rice husk powder, cotton powder, bamboo powder, walnut shell powder, paper powder, bamboo fiber, kenaf fiber or the like. Among them, wood powder is preferred from the viewpoint of enhancing the mechanical properties and obtaining them easily. When the filler derived from plants is in the form of particles, the average particle diameter is preferably from 0.1 to 100 G. Here, the average particle diameter is a two-axis average development diameter. Two-axis average system (four) 'pulmonary (10) her son, (10) micro-mirror and image analysis software (such as KEYENCE company microscope VH_5 〇〇〇 and the same company-made software VH_H1A5) to measure each _ long _ (μηι) and short axis diameter (four) 'And find (long axis + short axis diameter) / 2, the average to obtain the 値 to obtain. If the average particle size of the particulate plant-derived filler is on the pawl 1, the fluidity of the thermosetting material can be made higher; if it is below the surface (four), the mechanical properties of the molded article are made higher. When the plant-derived filler is fibrous, the average fiber length (U~-face is preferred. Here, the average fiber length is measured by means of a polarized light source carried by the claw face.) Plant-derived filler: The average fiber length is longer. The mechanical properties of the material are higher; if it is below __, the flowability of the thermosetting material is higher. The inorganic filler can be, for example, two-components> Alumina, tantalum nitride, carbon servant Shi Xi. Moonstone 'Ashey acid, strontium carbonate, clay, titanium white powder, glass fiber, quasi-carbon fiber, etc. 10 201207036 When the inorganic filler is a particle The average particle diameter in the case of the same is based on the same reason as the plant-derived filler, and is preferably 0.1 to 1000 " m. Further, when the inorganic filler is fibrous, the average fiber length is the same as that of the plant-derived filler. The reason for the filler is preferably 0.1 to 100 mm. The content of the filler is preferably from 30 to 500 parts by mass, and more preferably from 5 to 3 parts by mass, based on 1 part by mass of the total of the raw phenol resin. If the content of the filler is 30 parts by mass or more, the mechanical substance of the molded product can be obtained. It is higher; if it is 500 parts by mass or less, the fluidity can be made higher. (Curing catalyst) The thermosetting material of the present invention may also contain a hardening catalyst. The hardening catalyst system can promote the reaction of the raw resin and the hardener. Specific examples thereof include calcium hydroxide (slaked lime), oxidized dance, magnesium oxide, etc. The content of the curing catalyst is preferably 0.1 to 20 parts by mass based on the total mass of the raw phenol resin. Further, it is more preferably 0 to 15 parts by mass. If the content of the hardening catalyst is 0.1 part by mass or more, it can be sufficiently hardened in a short time. However, even if the curing catalyst is contained in an amount of more than 2 parts by mass, the hardening promotion is carried out. The effect is saturated and the cost is increased. (Lubricant) Further, the thermosetting material of the present invention may further contain a lubricant for improving fluidity. As the lubricant, for example, Carnauba moth may be used. 28 acid wax, calcium stearate, aluminum stearate, stearic acid, low molecular weight polyethylene (polyethylene wax), etc. (other additives) Further, the thermosetting material of the present invention may also be included For example, carbon black, etc. 201207036 Adding colorants, mold release agents, coupling agents, antioxidants, and additives, etc. (Method of manufacturing thermosetting material) Thermosetting material can be mixed with raw phenol resin, A hardener and a filler, a hardening catalyst, a lubricant, and other additive ports to be mixed... When mixing, a mixer such as a mixing roll can be used. Also, at the end of the 8th time, the raw phenol resin can also be used. In the range of hardening, it is added to the range of y. ...., and after heating, it may be pulverized as needed. (Effective effect) The above-mentioned thermosetting material of the present invention described above is formed by the above-mentioned raw phenol resin. It is excellent in workability, has a high plant-to-proportion ratio, and can produce a hardened body of high strength and low Young's modulus. Example (Production of Phenolic Resin) [Example 1] 300 g of phenol, 60.2 g of cardanol, and high fructose corn syrup HF95 (fructose source content: 95% by mass, solid portion: 75 mass% aqueous solution) 192 g (solid portion M4g) and 2.5 g of sulfuric acid were fed into a 500 ml three-necked flask equipped with a thermometer, a stirring device, and a cooling tube. At this time, the amount of sulfuric acid added was determined as the mass of the solid portion of the phenol and the saccharide. %. Next, while heating the water generated during the heating, the temperature was raised to 155 ° C and maintained at 155. (After stirring for 丨 hours, 1.9 g of hydrazine hydroxide suspended in a small amount of water was added to neutralize. Thereafter, unreacted phenol was distilled off under reduced pressure of 2 〇〇, ukpa 12 201207036 - 175 g, 266 g of phenol resin (F-1) was obtained. [Example 2] 300.8 g of phenol, 60.2 g of cardanol, and high fructose corn syrup HF95 made by Qunrong Chemical Industry (fructose source content: 95% by mass, solid state) Partially 75 mass% aqueous solution) 96 g (solid portion 72 g), Group Rong Chemical Industry High Fructose Corn Syrup HF55 (fructose source content 55 mass%, solid portion 75 mass% aqueous solution) 96 g (solid portion 72 g), sulfuric acid 2.5 g was fed to a 500 ml three-necked flask equipped with a thermometer, a stirring device, and a cooling tube. At this time, the amount of sulfuric acid added was 0.5% by mass based on the total amount of the solid portion of the phenol and the cardanol and the saccharide. While heating to 155 ° C while removing the water generated during the heating, and stirring for 1 hour while maintaining the temperature at 155 ° C, 1.9 g of calcium hydroxide suspended in a small amount of water was added to neutralize. Thereafter, at 200 164 g of unreacted phenol was distilled off under reduced pressure of ° C and ll kPa, and To 278 g of phenol resin (F-2) [Example 3] 300.8 g of phenol, 60.2 g of cardanol, and high fructose corn syrup HF55 made by Qunrong Chemical Industry (fructose source content: 55 mass%, solid portion 75 mass) 5% g (solid solution) 192 g (solid portion 144 g) and 2.5 g sulfuric acid were fed to a 500 ml three-necked flask equipped with a thermometer, a stirring device, and a cooling tube. At this time, the amount of sulfuric acid added was set to be phenol, cardanol, and saccharide. The amount of the solid portion is 0.5% by mass. Then, while removing the water generated during the heating, the mixture is heated to 155 13 201207036 ° C, and stirred for 1 hour while maintaining the temperature at 155 ° C, and then suspended in a small amount of water. After neutralizing 1.9 g of calcium hydroxide, 155 g of unreacted phenol was distilled off under reduced pressure of ll kPa at 200 ° C to obtain 289 g of phenol resin (F-3). [Example 4] Phenol 300.8 g, cardanol 105.3g, Group Rong Chemical Industry High Fructose Corn Syrup HF55 (fructose containing 555% by mass, solid portion 75 mass% aqueous solution) 192g (solid portion 144g), sulfuric acid 2.8g fed to have a thermometer, Stirring device, cooling tube in a 500 ml three-necked flask. The amount of sulfuric acid added is 0.5 mass% / 〇 of the total amount of the solid portion of phenol, cardanol and saccharide. Then, the water generated during the temperature rise is removed and heated to 155 ° C, and is maintained at 155. After stirring for 1 hour in a state of ° C, 2.1 g of calcium hydroxide suspended in a small amount of water was added to neutralize. Thereafter, 153 g of unreacted phenol was distilled off under reduced pressure of 200 ° C and ll kPa to obtain 312 g. Phenolic resin (F-4). [Comparative Example 1] 300.8 g of phenol, 60.2 g of cardanol, tapioca starch (content of fructose source 0% by mass, 88% by mass of solid portion) 78.7 g (solid portion 69.2 g), granulated sugar (fructose source content) 50% by mass) 74.8 §, 2.5 g of sulfuric acid was fed into a 500 ml three-necked flask equipped with a thermometer, a stirring device, and a cooling tube. At this time, the amount of sulfuric acid added was 0.5% by mass based on the total amount of the solid portion of phenol, cardanol and saccharide. Then, while removing the water generated during the heating, the mixture was heated to 155 14 201207036 ° C, and stirred for 1 hour while maintaining the temperature at 155 ° C, and then 1.9 g of calcium hydroxide suspended in a small amount of water was added to neutralize. Thereafter, 131 g of unreacted phenol was distilled off under reduced pressure of 200 ° C and ll kPa to obtain 315 g of a phenol resin (F-5). [Comparative Example 2] 300.8 g of phenol, 60.2 g of cardanol, tapioca starch (content of fructose source 0% by mass, 88% by mass of solid portion) 128.8 § (solid portion 113.3 g), granulated sugar (fructose source content ratio) 50% by mass) 30.6 §, 2.5 g of sulfuric acid was fed into a 500 ml three-necked flask equipped with a thermometer, a stirring device, and a cooling tube. Further, the amount of sulfuric acid added is 0.5% by mass based on the total amount of the solid portion of phenol, cardanol and sugar. Then, while heating to 155 ° C while removing the water generated during the heating, the mixture was stirred at 155 ° C for 1 hour, and then 1.9 g of calcium hydroxide suspended in a small amount of water was added to neutralize. Thereafter, 122 g of unreacted phenol was distilled off under reduced pressure of ll kPa at 200 ° C to obtain 316 g of a phenol resin (F-6). [Comparative Example 3] 300.8 g of phenol, 105.3 g of cardanol, tapioca starch (content of fructose source 0% by mass, 88% by mass of solid portion) 128.8 § (solid portion 113.3 g), granulated sugar (fructose source content ratio) 50% by mass) 30.6 g and 2.8 g of sulfuric acid were fed into a 500 ml three-necked flask equipped with a thermometer, a stirring device, and a cooling tube. Further, the amount of sulfuric acid added is 0.5% by mass based on the total amount of the solid portions of the phenol and the cardanol saccharide. Then, while removing the water generated during the heating, the mixture was heated to 155 15 201207036 c, and stirred for 155 hours while being held at 155 t, and then 21 g of hydrogen hydroxide in the suspended v water was added to neutralize. After that, it is fine. C, 11 noisy = pressed steam in addition to unreacted U4g, surgery (10) g of resin & [Comparative Example 4] will be expected 3m) g, 5G quality 4% formic solution l56g, oxalic acid 2.1 § fed to the thermometer , device, cooling tube lion ml in a three-necked flask. Further, the molar ratio of the aqueous solution to the desired m was G 815 , and the amount of the oxalic acid added was set to be 0.7% by mass. Then, it was heated to 95 ° C under a reduced pressure of 6 lkPa, and after _2 hours under reduced pressure and maintained temperature, the nkpa was reduced and the water produced by the reaction was removed. Further, under f pressure, while removing the generated water, the mixture was heated to 180 C', and 36 g of unreacted phenol and water were distilled off under a reduced pressure of i80 ° C and ll kPa to obtain 312 g of a phenol resin (F_8). [Comparative Example 5] 144 g of phenol, 5.6 g of fructose corn syrup Η55 (fructose source containing _55 mass%, and a portion of 75 mass% aqueous solution) of 144 g (solid form: 卩 is 108 g), and 9 g of barium sulfate were fed to A three-neck test with a thermometer, a stirring device, and a cooling tube of 5 GGml. Further, the amount of sulfuric acid added is 0.5 mass of the total amount of the solid portion of the phenol and the sugar. /〇. Then, while removing the water generated during the heating, the mixture was heated to 155 ° C, and stirred for 155 hours while being held at 155 t, and then 4 g of calcium hydroxide strontium suspended in > water was added and neutralized. Thereafter, at 2 〇〇.未, llkPa was distilled under reduced pressure to remove unreacted phenol 1 〇 9 g to obtain 2 〇 phenol resin 16 201207036 . (F-9). [Comparative Example 6] 144 g of a phenol, a high fructose corn syrup HF55 (a fructose source content: 55 mass%, a solid portion of a 75 mass% aqueous solution) of 144 g (solid content: 108 g) and 2.2 g of sulfuric acid were fed to A 500 ml three-necked flask equipped with a thermometer, a stirring device, and a cooling tube. The amount of sulfuric acid added was 0.5% by mass based on the total amount of the solid portion of the phenol and the sugar. Then, while heating to 155 ° C while removing the water generated during the heating, the mixture was stirred at 155 ° C for 1 hour, and then 1.7 g of calcium hydroxide suspended in a small amount of water was added to neutralize. Thereafter, 162 g of unreacted phenol was distilled off under reduced pressure of 200 ° C and ll kPa to obtain 223 g of a phenol resin (F-10). (Evaluation) With respect to the obtained phenol resin, the softening point, fluidity, plant-derived ratio, and cardanol modification rate were measured by the following methods. The measurement results are shown in Table 1. [Softening point] Measured in accordance with JIS K6910. [Liquidity] Measured in accordance with JIS K6910. [Proportion derived from plants] Proportion of plant-derived = 100- {[(feed quality) - (quality of unreacted phenol removed by distillation) + (mass of neutralized salt (theoretical 値))] / (resin production Quality)} X100 [Carrageenan upgrading rate] Cardinol modification rate = [(Cargophenol feed quality) / (resin production quality)] xl 〇〇 [Table 1] 17 201207036 (0 爝 ii trade for corn sugar S 1 338.4 1 Ο gy— C^J csi 1 Ο d * · τ— CO in in to d CNJ to ^- CO CM <N4 o in 〇> r- 〇in 匡U η high fructose corn syrup 1 ο CVJ Ο g T— O) 1— 1 ο ο ΙΛ ΙΛ eg mu? in ds S 05 ♦>- s CO 〇6 〇 肴 η 1 (〇1〇ο 8 ο 1 1 csi ο ο 1 1 1 <〇CO <NJ O) σ> CO <D o 〇CO 爝±i 1 300.8 105.3 5 t— 00 c^i 1 σ>LT> CM 2.8:1 r~ md inch r~ T-· σ> LO CO g »- S σ><〇COσ> CNJ 1 1 1 300.8 CNJ Ο <〇5 T- mc^j 1 卜<〇1» in eg in d eg CM r~ CO t- CO Production 00 CO r- σ> 1 1 1 300.8 CM ο <〇in cJ 1 r*· (Ο LO cJ <〇CNJ in d ?; (AS inch r-IT- 00 CM 45.0 σ& EHaOBIMSQIEMiEliHfflEl 1 300.8 105.3 5 1 - 00 csi 1 σ> LT> CM 00 OJ LO in in d CO in CNJ S g Csj 00 00 Η C0 1 300.8 S 5 IA CNJ 1 cd in CNI m LO mdm in Production O ) 00 CM 〇T— Γ0 » 00 1 300.8 CM S m cJ 1 cd r- ΙΛ CNJ in in ds 00 CM CO in O) 卜 1 300.8 CS| Ο (Ο Z T- m cJ 1 卜 <6 mc \im ΟΪ LA O in <〇€NJ ΙΛ σ>σ> τ— m <D 〇4 CSi 睁赵饿坚bO m * m fr /-Ν bfl V-/ window 坳翁mV 豳/-\ hfl魅 魅/·> b〇N-/ 趣 grip 1 /-> bO s-/ 龌 content rate (% by mass) hang ±JH; M f^-N: 随涵•AP· mP»' m 优运NiW 赃 赃| 龆H /-> S5 title s>> Φ 兵联蘅3JI11 fiber i ^-N bO window m 伥^-s bo dM m Dm BC $ ! #-\ su /-v EE ΚωΚ s mi i 岫μ 1 Ν 腾腾味品1 salt s B·hang 18 201207036 Example of reacting phenols containing cardanol with high fructose corn syrup (fructose source content is more than 50% by mass) a phenol resin of 1 to 4, which has a low softening point and excellent fluidity, and further, a plant-derived ratio High. The phenol resin of Comparative Examples 1 to 3 obtained by using starch or granulated sugar (the content of fructose source is 50% by mass or less) as a saccharide has a high softening point and low fluidity. 0 A general phenol resin using a formaldehyde aqueous solution is Comparative Example 4 The phenol resin, which is derived from a low proportion of plants. The phenolic resin of Comparative Examples 5 and 6 obtained by reacting the age and high fructose corn syrup (the content of fructose source is more than 50% by mass) has a low ratio of plant-derived plants, and has a low degree of weighting and low fluidity. (Production of thermosetting material) [Example 5] 7 g of resin (Fl), 98 g of wood powder, 20 g of hexamethylenetetramine as a curing agent, and 7 g of calcium hydroxide as a curing aid, as a lubricant 3 g of zinc stearate and 1.5 g of carbon black as a coloring agent were mixed and kneaded to prepare a molding material. [Examples 6 to 8 and Comparative Examples 7 to 12] A molding material was produced in the same manner as in Example 5 except that the phenol resin (F-1) was changed to the phenol resin shown in Table 2. [Forming processability] The molding materials of the respective examples and the comparative examples were injection-molded and cured at 170 C using a molding machine (manufactured by Nissei Resin Co., Ltd.) at 170 C, and cured. Things. 19 201207036 The productivity at this time and the quality of the obtained molded product were evaluated by the following criteria. The evaluation results are shown in Table 2. ◎: It is easy to form due to high fluidity and has no problem in the appearance of the molded article. 〇: Although it can be formed, the fluidity is slightly lower, and it is easy to become short shot when it is shot. △: Although it is easy to form due to high fluidity, it is swollen in the molded product due to slow curing. ▲: It is difficult to form due to low fluidity, and it will expand due to slow curing. X: The resin at the time of injection has a high viscosity and cannot be emitted. [Measurement of Bending Strength, Young Modulus, and Bending Amount] The molding materials of the respective examples and the comparative examples were injection molded and cured by an injection molding machine (PNX-40 manufactured by Seiko Seiko Co., Ltd.). Things. Using the obtained molded product, the bending strength and the Young's modulus (bending modulus) were measured at 25 ° C according to JIS K6911. Further, the amount of bending displacement of the molded article until the fracture was measured in the bending test as the amount of bending. The measurement results are shown in Table 2. The higher the bending strength, the lower the modulus of the Yang type, and the smaller the amount of bending, the better the mechanical properties become. Further, in Comparative Examples 7, 8, and 11, since the molding was impossible, the bending strength, the Young's modulus, and the amount of bending were not measured. [Table 2] 20 201207036 CSJ 1 1 1 II 1 III ο τ~* 00 σ> s 卜 CO l〇〇CM 00 CO 9.8 I ΙΛ r- r~ 1 1 1 II 1 II I_100 IIX cannot be formed o 1 1 1 II 1 I o II ◎ Γ 94.7 I o a> 1 1 1 II 1 Ί 00 III ◄ 65.0 I 00 id 2.7 00 1 1 1 II 1_100 IIIIIX Unable to form 1 1 1 I _100 1 IIIIIX m HO 00 1 1 1 100 1 IIIII < i 6.8 to CsJ 1 1 1__100 II 1 IIIII 〇σ >σ> 7.2 2.7 I 43⁄4 κ <〇1 ο II 1 IIIII ◎ CM GO CO 00 o 1 II 1 IIIII ◎ I 34.2 | CO 1-: 〇> cvi r- 1 U. s—/ ss CM 1 Li- Lithium m 窓CO I U- SS i Window/"NI Li. Lithium m ωω 1 L- Lithium mm (0 I \L· m shift Avoid I u. sm si 00 I Ll SS m 豳0) IL· S5 shift avoidance r- I Ll Lithium m overflow /-N Length 3 S a B- 冏^b〇m 3 S Interest m im./ e ^ Bj HP both m H □ I 0. B m buried s Gu* « 0- S 亲m 怵m EE «w/ 宙 if resin component 3 21 201207036 Examples 5 to 8 containing each of the enamel resins of Examples 1 to 4 The molding material is excellent in moldability and the bending of the obtained molded product High, low Young's modulus. In particular, even if Examples 5, 6 and 7 had the same degree of bending strength as when a general phenol resin (Comparative Example 10) was used, the Young mode was still low. The molding material of Comparative Example 9 containing the phenol resin obtained by using the starch of the starch and the sugar of Comparative Example 3 had low moldability and was low in strength. The molding material of Comparative Example 10 in which the aqueous solution of furfural of Comparative Example 4 was used as the phenol resin was used, and the ratio of the plant-derived material was low. Further, the obtained molded product has a high lift modulus and a small amount of warpage. The molding material of Comparative Example 12 containing the phenol resin obtained by reacting phenol, house powder and granulated sugar of Comparative Example 6 had a low bending strength, a high Young's modulus, and a small amount of bending. The molding material of Comparative Example 7 containing the phenol resin of Comparative Example 1, the molding material of Comparative Example 8 containing the phenol resin of Comparative Example 2, and the molding material of Comparative Example 11 containing the phenol resin of Comparative Example 5, the phenol used Since the softening point of the resin is high and the fluidity is low, the resin viscosity at the time of injection molding is high, and injection molding cannot be performed. INDUSTRIAL APPLICABILITY According to the method for producing a raw phenol resin of the present invention, it is possible to produce a raw material having excellent formability, high plant-derived ratio, and high-strength and low-yang modulus hardened body. Phenolic resin. The thermosetting material of the present invention is excellent in moldability, has a high ratio derived from plants, and can produce a high-strength and low-yang modulus. Further, the thermosetting property of the present invention 22 201207036 • Since the material has a high ratio of plants, it can suppress an increase in the amount of carbon dioxide in the atmosphere and prevent the global warming effect from becoming high. c Schematic description 3 None [Main component symbol description] Benefit <", 23