201245293 六、發明說明： 【發明所屬之技術領域】 本發明係關於含有纖維素及添加劑之組成物以及其製 造方法，詳言之，係有關於添加劑中均勻分散纖維素纖維 之含有纖維素纖維之纖維狀纖樹脂補強劑，及藉由該補強 劑朝熱可塑性樹脂之添加而使樹脂中之纖維素纖維均一分 散性及耐衝擊性獲得改良之樹脂組成物以及成形體。 【先前技術】 基於自然環境保護之觀點，對於有效活性目前未被利 用的資源之硏究正盛行。其中纖維素之現存量豐富，係具 有生物分解且環境負荷低的資源，具有高結晶化度、高拉 伸強度、低熱膨脹率等之作爲原料之優異特性等，故而爲 往後備受期待之材料。尤其，纖維素之分子鏈軸方向之結 晶彈性模數爲1 3 8GPa，與芳醯胺纖維及液晶聚酯之彈性 模數可相匹敵。且纖維素其線熱膨脹係數爲ΙΟ·7!^1之等 級，亦具有凌駕玻璃及金剛石之非常低的熱膨脹率。 作爲有效活用纖維素之方法之一舉例係利用作爲提高 樹脂成形體強度之補強材。以往，爲提高樹脂成形體之機 械強度，一般使用碳纖維或玻璃纖維等無機纖維作爲補強 材。然而，調配無機纖維之複合樹脂，有對模具等之成形 機內部產生磨耗之方面，燃燒時發生源自無機纖維之殘渣 故無法利用掩埋等處理予以廢棄等方面之問題。 另一方面’纖維素作爲補強材而調配於樹脂成形體之 -5- 201245293 後，由於最終亦會分解成水及二氧化碳，故不僅可消 述廢棄問題，而且基於可利用以疏伐材（thinned wo 爲代表之竹、麻、洋麻（Kenaf)等森林資源或可食 以外且成長快速且容易大量栽培之方面而備受矚目》 不過源自植物之生物分解性樹脂的聚乳酸，由於 於以往之聚丙烯樹脂、聚乙烯樹脂、聚對苯二甲酸乙 樹脂，其彈性模數雖高但有耐衝擊性差之缺點，故爲 此物性而必須並用補強材。聚乳酸其本身爲源自植物 料，故其補強材亦較好使用植物性天然纖維，基於此 ，已提案有數個關於纖維素與聚乳酸之複合樹脂之專芽 惟，爲使聚乳酸等之朝熱可塑性樹脂之分散，經 化爲奈米尺寸之纖維素由於本身具有之柔軟性及高縱 、以及起因於表面上存在之羥基所致之纖爲彼此之氫 若單獨經過乾燥狀態等則有形成強固凝集塊之問題。 爲避免此種凝集塊之發生且使纖維素分散於熱可 樹脂，已嘗試由形成爲薄片狀之微纖維化植物纖維所 者中含浸聚合性合分或樹脂溶液而製作薄片形狀之複 脂，以及探討將薄片形狀之複合樹脂細碎後進行熔融 ，接著以壓製成形等製作成形體（專利文獻1 )。 且’已報導有使聚丙烯樹脂與經疏水化之纖維素 維在水介質中，於加熱下攪拌混合，藉由脫水同時熔 練，而製造樹脂與經微細化纖維素纖維之複合樹脂之 (專利文獻2)。 另一方面，已報導於經微細化纖維素纖維中藉水 解上 〇 d ) 原料 相較 二酯 彌補 之材 觀點 ij 0 微細 橫比 鍵， 塑性 構成 合樹 混練 系纖 融混 方法 系使 -6- 201245293 聚合成分接枝聚合，獲得以熱可塑性樹脂覆蓋表面之纖維 素纖維之方法（專利文獻3 )。以同樣技術獲得之微細化 纖維素纖維由於表面經樹脂被覆，故即使透過乾燥狀態， 亦可抑制起因於纖維彼此之氫鍵所致之凝集塊形成》 [先前技術文獻] [專利文獻] 專利文獻1 :特開2009-19200號公報 專利文獻2 :特開20 1 0- 1 0625 1號公報 專利文獻3 :特開2009-67 8 1 7號公報 【發明內容】.201245293 VI. Description of the Invention: [Technical Field] The present invention relates to a composition containing cellulose and an additive, and a method for producing the same, and more particularly to a cellulose fiber containing cellulose fibers uniformly dispersed in an additive The fibrous fiber resin reinforcing agent and the resin composition and the molded body obtained by adding the reinforcing agent to the thermoplastic resin to improve the uniform dispersibility and impact resistance of the cellulose fibers in the resin. [Prior Art] Based on the viewpoint of natural environmental protection, research on resources that are currently not utilized for effective activity is prevailing. Among them, the amount of cellulose is abundant, and it is a resource which is biodegradable and has a low environmental load, and has excellent characteristics such as high crystallinity, high tensile strength, and low thermal expansion rate as raw materials, and is therefore expected in the future. material. In particular, the molecular elastic modulus of the molecular chain axis of cellulose is 138 GPa, which is comparable to the elastic modulus of linalin fibers and liquid crystal polyesters. Moreover, the linear thermal expansion coefficient of cellulose is ΙΟ·7!^1, and it also has a very low thermal expansion rate over glass and diamond. As an example of a method for effectively utilizing cellulose, a reinforcing material which is used to increase the strength of a resin molded body is used. Conventionally, in order to improve the mechanical strength of a resin molded body, inorganic fibers such as carbon fibers or glass fibers are generally used as reinforcing materials. However, the composite resin in which the inorganic fibers are blended has a problem in that the inside of the molding machine such as a mold is worn, and the residue derived from the inorganic fibers is generated during the combustion, so that it cannot be disposed of by a treatment such as burying. On the other hand, after the cellulose is used as a reinforcing material and blended in the resin molded body -5 to 201245293, it will eventually decompose into water and carbon dioxide. Therefore, not only the waste problem but also the thinned material can be used. We are attracting attention from the forest resources such as bamboo, hemp, and kenaf (Kenaf), and they are growing fast and easily cultivated in large quantities. However, polylactic acid derived from plant biodegradable resins has been used in the past. Polypropylene resin, polyethylene resin, and polyethylene terephthalate resin have high modulus of elasticity but have poor impact resistance. Therefore, it is necessary to use reinforcing materials together for physical properties. Polylactic acid itself is derived from plant material. Therefore, it is also preferred to use plant-based natural fibers for the reinforcing materials. Based on this, several specific buds of cellulose and polylactic acid have been proposed, and the polylactic acid and the like are dispersed toward the thermoplastic resin. The cellulose of nanometer size is dried by itself due to its own softness and high verticality, and the hydrogen caused by the hydroxyl groups present on the surface. There is a problem of forming a strong agglomerate. In order to avoid the occurrence of such agglomerates and to disperse the cellulose in the heat-sensitive resin, attempts have been made to impregnate the polymerizable compound into the microfibrillated plant fibers formed into flakes. In the case of a resin solution, a resin in the form of a sheet is prepared, and a composite resin having a sheet shape is finely pulverized and then melted, and then a molded body is produced by press molding or the like (Patent Document 1). In the aqueous medium, the cellulose is stirred and mixed under heating, and the composite resin of the resin and the fine cellulose fibers is produced by dehydration and simultaneous smelting (Patent Document 2). On the other hand, it has been reported In the microfibrillated cellulose fiber, the hydrolyzed upper layer d) the raw material phase is compared with the diester to make up the material view ij 0 fine transverse ratio bond, the plastic composition of the mixed tree and the fiber blending method enables the grafting polymerization of the polymer component of -6-201245293, A method of obtaining a cellulose fiber covering a surface with a thermoplastic resin (Patent Document 3). Since the surface of the microfibrillated cellulose fiber obtained by the same technique is coated with a resin, the formation of agglomerates due to hydrogen bonding of the fibers can be suppressed even in a dry state. [Prior Art Literature] [Patent Literature] Patent Literature [Patent Document 2] Japanese Laid-Open Patent Publication No. 2009-19200 (Patent Document No. JP-A-2009-2006).
[發明欲解決之課題] 以上述揭示之以往方法，有若經過薄片形狀，則需要 接枝聚合成爲必要等之煩瑣步驟，且所得材料難以應用慣 用成形方法之問題。且由於包含須要有機溶劑之步驟，另 一方面，包含在水存在下使樹脂加熱之步驟，故有聚乳酸 樹脂等水解之虞之顧慮而難以應用於樹脂等，尤其使用聚 乳酸樹脂之複合樹脂化之問題較多。 本發明係鑒於上述情況而完成者，目的係提供利用纖 維素作爲熱可塑性樹脂之補強材時會成爲問題之凝集塊發 生受到抑制，可均一分散於所調配之樹脂中，可充分發揮 作爲補強材之性能之補強劑。 尤其本發明之目的係提供於熱可塑性樹脂中作爲對聚 201245293 乳酸之補強劑，就維持樹脂本身之高彈性模數而言可展現 高的耐衝盤性，且亦可適用於有聚乳酸之如水解顧慮之樹 脂之樹脂補強劑。 再者，本發明之目的係提供不需要特別裝置或複雜製 造步驟而可藉簡便方法製造上述樹脂補強劑之樹脂補強劑 的製造方法。 而且本發明之目的係提供含有上述樹脂補強劑而贲現 機械強度之提高的樹脂組成物以及由該樹脂組成物形成之 成形體》 [用以解決課題之手段] 本發明人爲達上述目的而重覆積極檢討之結果，發現 藉由將親水性添加劑添加於經微細化之纖維素纖維之水分 散液中調製懸浮液後，去除水分，可得到經微細化之纖維 素於該添加劑中均一分散之纖維狀樹脂補強劑，且藉由將 該補強劑添加於熱可塑性樹脂而可容易獲得耐衝擊性優異 之樹脂組成物及成形體，因而完成本發明。 亦即，本發明係關於纖維狀樹脂補強劑，其係用以補 強基質樹脂之纖維狀樹脂補強劑，其特徵爲包含經微細化 之纖維素纖維（A )與親水性且HLB値（親水親油平衡） 在1 0〜20之添加劑（B )，且該經微細化之纖維素纖維（ A)係以分散於添加劑（B )中之狀態存在。 上述所謂HLB値爲10〜20意指包含以10爲下限値且 以20爲上限値之範圍。以下，說明書中，只要是HLB値 201245293 ’於使用〜表示數値範圍之表示法之下限値及上限値亦同 樣解釋。 前述經微細化之纖維素纖維（A )之利用雷射繞射. 散射式粒度分佈計以水作爲分散介質所測定之體積累計 50%內之粒徑（中値徑）較好爲0.01 # m〜40/z m。 且前述經微細化纖維素纖維（A )較好係利用自高壓 均質機、硏磨（石臼）式磨碎機及介質攪拌硏磨機所成組 群選出之任一種之濕式粉碎方法所調製。 再者前述經微細化之纖維素纖維（A )較好由源自植 物之纖維素或細菌纖維素所調製。 且前述添加劑（B )相對於前述經微細化纖維素纖維 (A)與該添加劑（B)之合計100質量份，較好含有70 質量份〜99.9質量份之量。 再者前述添加劑（B)更好具有12〜16之H LB値。 而且本發明關於製造前述纖維狀樹脂補強劑之方法， 其包含使添加劑（Β )溶解或乳化或分散於經微細化之纖 維素纖維（A )之水分散液中而調製懸浮液之步驟，及自 該懸浮液去除水分之步驟。 再者本發明有關含有前述纖維狀樹脂補強劑之樹脂組 成物。 前述樹脂組成物中，較好進而含有熱可塑性樹脂，該 熱可塑性樹脂更好爲聚乳酸。 而且本發明亦有關由前述樹脂組成物所形成之成形體 -9 - 201245293 [發明效果] 本發明之纖維狀樹脂補強劑對聚乳酸等之基I 分散容易，亦即並無須要經過使經微細化纖維素箱 於基質樹脂時以往所必須使用之有機溶劑及複雜步 且本發明之纖維狀補強劑，僅藉簡單熔融混海 與基質樹脂，即可形成纖維素纖維均一分散於基1 之組成物。 且依據本發明，上述纖維狀樹脂補強劑可簡偵 良好地製造。且不使用特殊裝置，即可以工業規模 再者，本發明之纖維狀補強劑如前述，可不侈 溶劑而製造，且可消除無機纖維所帶來之廢棄等房 而由自然環境保護或省能源之觀點而言，成爲有_ 者0 而且本發明之樹脂組成物以及由該組成物所 體中，經微細化之纖維素纖維係均一分散於基質 相較於專利文獻1至3所記載之樹脂組成物，該 維之含量低，故可顯著改善成形加工性，同時可 樹脂組成物及成形體之機械強度。 【實施方式】 本發明之纖維狀樹脂補強劑具有最大特徵在於 含有經微細化纖維素纖維之水分散液與HLB値爲 之親水性添加劑所成之懸浮液中去除水分，而成爲 t樹脂之 6維分散 驟。 丨補強劑 :樹脂中 【且效率 製造。 :用有機 丨題，故 :大改善 =之成形 脂中， 丨維素纖 幅改善 藉由自 1 0 〜20 纖維素 -10- 201245293 纖維均一分散於添加劑中之狀態。 爲此，該補強劑具有之特徵在於，即使利用以往樹脂 成形技術’亦可容易地分散於聚乳酸等之基質樹脂中且所 得之樹脂組成物中纖維素纖維爲均一分散狀態。 以下，詳細說明本發明。 [纖維狀樹脂補強劑] 本發明之纖維狀樹脂補強劑，係藉由將添加劑（B ) 溶解或乳化或分散於經微細化纖維素纖維（A)之水分散 液中而調製懸浮液，並自該懸浮液去除水分而獲得。 <經微細化纖維素纖維（A ) > 作爲本發明所使用之纖維素纖維之水分散液原料之纖 維素，可廣泛使用以往纖維素纖維製造中所使用之原料。 例如可使用木材、竹、麻、黃麻、洋麻、農作物、食物殘 渣等源自植物之纖維素、細菌纖維素、海鞘纖維素等微生 物產生或動物產生之纖維素作爲原料。該等纖維素可單獨 使用或組合兩種以上使用。 其中，較好使用源自植物之纖維素或細菌纖維素作爲 原料。 本發明中，係使用將該等纖維素原料粉碎，並經微細 化之纖維素纖維。纖維素粉碎方法並無限制，但爲微細化 至符合本發明目的之纖維徑，較好使用如高壓均質機、硏 磨（石白）式磨碎機或珠粒硏磨機等之介質攪拌硏磨機之 -11 - 201245293 可獲得強剪切力之方法。又，該等中較好使用高壓均質機 予以微細化，例如如特開2005-27089 1號公報所揭示之濕 式粉碎法，亦即將分散有纖維素之分散液自一對噴嘴以高 壓噴射出並衝撞，藉此使纖維素粉碎者，例如可藉由使用 STARBURST系統（SUGINO機器公司製之高壓粉碎裝置 )而實施。 使用前述高壓均質機使纖維素纖維微細化時，微細化 或均質化程度倚賴於高壓均質機之朝超高壓腔室壓送之壓 力'通過超高壓腔室之次數（處理次數）以及水分散液中 之纖維素濃度。 壓送壓力（處理壓力）通常爲5 01^?&〜2 5 01^?&’較好 爲 1 50MPa〜245MPa。壓送壓力未達 50MPa時，纖維素纖 維之微細化變不充分，無法獲得因微細化所期待之效果。 且，微細化處理時之水分散液中之纖維素濃度爲0.1 質量0質fi %，較好爲1質量1 0質量％。水分散液 中之纖維素濃度若未達0.1質量％，則生產性顯著降低， 高於3 0質S °/〇之濃度時粉碎效率低，無法獲得所需經微細 化纖維素纖維。 微細化處理次數，雖依據前述水分散液中之纖維素濃 度而定，但纖維素濃度爲0.1質量％〜1質量％時，處理次 數爲10次〜50次左右即可充分微細化，但於1質量％〜10 質量％，則有必要爲50次〜200次左右。且超過30質量％ 之高濃度時，需要數百次以上之處理次數，基於工業觀點 並不實際。 -12- 201245293 本發明中所用之經微細化纖維素纖維之水分散液中之 微細化評價，可使用例如雷射繞射/散射式粒度分佈測定 器。本發明中，較好使用測定纖維素纖維之水分散液之體 積粒度分佈時，體積累計50%內之粒徑（中値徑）爲0.01 从m〜40；um，最好爲0.05#m〜10；wm之纖維素纖維。粒徑 未達0.01 y m時，纖維素纖維過於微細而無法獲得添加效 果，亦即無法獲得如下含有所得纖維狀樹脂補強劑之樹脂 組成物或其成形體之機械強度之改善。又.，粒徑大於40//m 時，纖維素纖維之微細化不充分，於含有其之樹脂組成物 或其成形體之機械強度與含有未粉碎纖維素原料時之機械 強度未見到差異，無法獲得期待效果。 又，本發明所用之經微細化纖維素纖維之纖維徑並未 特別限制，但可爲0 · 0 0 1 // m至1 〇 # m，較好爲0.0 1 // m 至1 # m者。且縱橫比（L/D )亦未特別限制，但可爲 10〜100,000，較好爲 100〜10,000。 <添加劑（B ) > 作爲本發明中之添加劑（B )，若爲親水性，且H L B (親水親油平衡：Hydrophile-Lipophile-Bal ance )値爲 10〜20，而且可使前述纖維素纖維（A)均一分散者，則可 無特別限制地使用公知者。可舉例爲例如單甘油酯、乙酸 單甘油酯、乳酸單甘油酯、檸檬酸單甘油酯、琥珀酸單甘 油酯、二乙醯酒石酸單甘油酯；聚甘油酯、糖酯、山梨糖 醇酐酯、硬脂醯基乳酸鈣、卵磷脂等。 13- 201245293 本發明中，藉由調配添加劑（B )，相較於單獨使用 經微細化之纖維素纖維時，經調配之樹脂組成物或其成形 體之機械強度獲得提高。 且，本發明中，纖維素纖維及添加劑一旦構成爲纖維 狀樹脂，藉由將其調配於熱可塑性樹脂中，相較於各單獨 (不經過纖維狀樹脂補強劑之形態）調配時，可抑制所得 樹脂組成物中之經微細化纖維素纖維之凝集形成，同時該 樹脂組成物中纖維素纖維可維持微細化狀態直接分散故而 較有利》 又，作爲表示添加劑（B )之親水性或疏水性之尺度 ，係使用由親水基與親油基之平衡所得之自〇〜20之數値 表示之HLB値。HLB値若親油性高者較小，親水性高者 則較大，亦即爲意指對應於HLB値對於水之溶解性或分 散性產生變化者。至於 HLB値之算出方法，已知有 GRIFFIN法、ATLAS法、DAVIS法、川上法等，例如可 由下述GRIFFIN之式算出。 HLB = 2 0x (親水基之化學式量/全體分子量） 使用市售品作爲添加劑（B )時，可應用該商品所揭 示之目錄等中所記載之HLB値。 本發明所用之添加劑之HLB値爲10〜20，更好HLB 値爲12〜16。HLB値未達10時，纖維素纖維及添加劑在 水中之親和性低，於製造纖維狀樹脂補強劑之階段，纖維 素纖維會形成凝集塊，無法獲得如下之含有所得纖維狀樹 脂補強劑之樹脂組成物或其成形體之機械強度之提高。 -14- 201245293 又，朝纖維狀樹脂補強劑中之添加劑（B )之調配量 ，相對於經微細化之纖維素纖維（A )及添加劑（B )之合 計100質量份，爲例如50質量份-99.9質量份，較好爲 70質量份~9 9.0質量份。添加劑之調配量未達50質量份 時，含有由經微細化纖維素纖維及添加劑所成之纖維狀樹 脂補強劑之樹脂組成物中或其成形體中之纖維素纖維無法 均一分散，無法提高機械強度。 本發明之纖維狀樹脂補強劑中可使用之市售添加劑之 例舉例有如下者，但不限於該等： POEM [註冊商標]J-0021、POEM L-021、POEM J-[Problems to be Solved by the Invention] In the conventional method disclosed above, there is a troublesome step in which graft polymerization is required when the sheet shape is passed, and the obtained material is difficult to apply the conventional molding method. Further, since the step of requiring an organic solvent is included, and on the other hand, the step of heating the resin in the presence of water is involved, it is difficult to apply to a resin or the like due to hydrolysis of a polylactic acid resin or the like, and in particular, a composite resin of a polylactic acid resin is used. There are more problems with this. The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide agglomerates which are problematic when cellulose is used as a reinforcing material for a thermoplastic resin, and can be uniformly dispersed in a resin to be blended, and can be sufficiently used as a reinforcing material. The performance of the reinforcing agent. In particular, the object of the present invention is to provide a reinforcing agent for poly 201245293 lactic acid in a thermoplastic resin, which can exhibit high punching resistance in terms of maintaining a high elastic modulus of the resin itself, and can also be applied to polylactic acid. A resin reinforcing agent such as a resin that is hydrolyzed. Further, an object of the present invention is to provide a method for producing a resin reinforcing agent which can produce the above-mentioned resin reinforcing agent by a simple method without requiring a special device or a complicated manufacturing step. Further, an object of the present invention is to provide a resin composition containing the above-mentioned resin reinforcing agent and improving the mechanical strength and a molded body formed of the resin composition. [Means for Solving the Problems] The present inventors have attained the above object. As a result of repeated active review, it was found that by adding a hydrophilic additive to the aqueous dispersion of the finely divided cellulose fibers to prepare a suspension, the water was removed, and the finely divided cellulose was uniformly dispersed in the additive. The fibrous resin reinforcing agent is used, and the reinforcing agent is added to the thermoplastic resin, whereby the resin composition and the molded body excellent in impact resistance can be easily obtained. Thus, the present invention has been completed. That is, the present invention relates to a fibrous resin reinforcing agent which is a fibrous resin reinforcing agent for reinforcing a matrix resin, which comprises a micronized cellulose fiber (A) and a hydrophilic and HLB (hydrophilic parent) Oil balance) The additive (B) in the range of 10 to 20, and the finely divided cellulose fiber (A) is present in a state of being dispersed in the additive (B). The above-mentioned "HLB" of 10 to 20 means a range including 10 as the lower limit and 20 as the upper limit. Hereinafter, in the specification, the same applies to the lower limit 値 and the upper limit of the representation of HLB 値 201245293 ′ using the ～ range. The finely divided cellulose fiber (A) is subjected to laser diffraction. The particle size (medium diameter) within 50% of the volume measured by the scattering type particle size distribution meter using water as the dispersion medium is preferably 0.01 # m. ~40/zm. Further, the microfibrillated cellulose fibers (A) are preferably prepared by a wet pulverization method selected from the group consisting of a high pressure homogenizer, a honing machine, and a medium agitating honing machine. . Further, the above-mentioned finely divided cellulose fibers (A) are preferably prepared by cellulose or bacterial cellulose derived from plants. Further, the additive (B) is preferably contained in an amount of from 70 parts by mass to 99.9 parts by mass per 100 parts by mass of the total of the finely divided cellulose fibers (A) and the additive (B). Further, the aforementioned additive (B) preferably has an H LB 12 of 12 to 16. Further, the present invention relates to a method for producing the above-mentioned fibrous resin reinforcing agent, which comprises the steps of dissolving or emulsifying or dispersing an additive (Β) in an aqueous dispersion of the finely divided cellulose fibers (A) to prepare a suspension, and The step of removing moisture from the suspension. Further, the present invention relates to a resin composition containing the above-mentioned fibrous resin reinforcing agent. The resin composition preferably further contains a thermoplastic resin, and the thermoplastic resin is more preferably polylactic acid. Further, the present invention relates to a molded article formed of the above-mentioned resin composition. -9 - 201245293 [Effect of the invention] The fibrous resin reinforcing agent of the present invention is easy to disperse the base I of polylactic acid or the like, that is, it is not required to be finely pulverized. The organic solvent and the fibrous reinforcing agent of the present invention which are conventionally used in the case of the cellulose resin in the matrix resin can form the uniform dispersion of the cellulose fibers in the base 1 only by simply melting the mixed sea and the matrix resin. Things. Further, according to the present invention, the above fibrous resin reinforcing agent can be easily produced. Further, without using a special device, it can be industrially scaled. The fibrous reinforcing agent of the present invention can be produced without any solvent as described above, and can eliminate the waste caused by the inorganic fiber and be environmentally friendly or energy-saving. In view of the above, the resin composition of the present invention and the resin fiber of the present invention are uniformly dispersed in the matrix phase as compared with the resin compositions described in Patent Documents 1 to 3. Since the content of the material is low, the formability can be remarkably improved, and the mechanical strength of the resin composition and the molded body can be achieved. [Embodiment] The fibrous resin reinforcing agent of the present invention has a liquid crystal dispersion liquid containing a finely divided cellulose fiber and a hydrophilic additive such as HLB® to remove moisture, and becomes a resin of t resin. Dimensional dispersion.丨 Reinforcing agent: Resin [and efficiency manufacturing. : Using organic 丨, so: large improvement = formation of fat, 丨 素 纤 纤 纤 改善 改善 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 -10- -10- -10- -10- -10- -10- -10- -10- -10- -10- -10- -10- -10- -10- -10- -10- -10- -10- For this reason, the reinforcing agent is characterized in that it can be easily dispersed in a matrix resin such as polylactic acid by the conventional resin molding technique, and the cellulose fibers in the obtained resin composition are uniformly dispersed. Hereinafter, the present invention will be described in detail. [Fibrous Resin Reinforcer] The fibrous resin reinforcing agent of the present invention is prepared by dissolving or emulsifying or dispersing the additive (B) in an aqueous dispersion of the finely divided cellulose fibers (A), and modulating the suspension. Obtained from the suspension to remove moisture. <Micronized Cellulose Fiber (A)> As the cellulosic material of the aqueous dispersion of the cellulose fiber used in the present invention, a raw material used in the production of the conventional cellulose fiber can be widely used. For example, cellulose derived from plants such as cellulose, bamboo, hemp, jute, kenaf, crops, food residue, or the like, cellulose derived from plants, bacterial cellulose, sea squirt cellulose, or the like, can be used as a raw material. These celluloses may be used singly or in combination of two or more. Among them, cellulose derived from plants or bacterial cellulose is preferably used as a raw material. In the present invention, cellulose fibers obtained by pulverizing the cellulose raw materials and finely pulverizing are used. The cellulose pulverization method is not limited, but in order to refine the fiber diameter to the object of the present invention, it is preferred to use a medium agitating crucible such as a high pressure homogenizer, a honing (stone white) type grinder or a bead honing machine. Mill -11 - 201245293 The method of obtaining strong shear force. Further, it is preferable to use a high-pressure homogenizer for miniaturization. For example, the wet pulverization method disclosed in Japanese Laid-Open Patent Publication No. 2005-270891, that is, the dispersion in which cellulose is dispersed is ejected from a pair of nozzles at a high pressure. In addition, the cellulose pulverizer can be used, for example, by using the STARBURST system (a high-pressure pulverizing apparatus manufactured by SUGINO Machinery Co., Ltd.). When the cellulose fiber is miniaturized by using the above-mentioned high-pressure homogenizer, the degree of refinement or homogenization depends on the pressure of the high-pressure homogenizer toward the ultra-high pressure chamber, the number of passes through the ultra-high pressure chamber (the number of treatments), and the aqueous dispersion. The cellulose concentration in the medium. The pressure (pressure of treatment) is usually 5 01^?&~2 5 01^?&' is preferably 1 50 MPa to 245 MPa. When the pressure of the pressure is less than 50 MPa, the fineness of the cellulose fibers is insufficient, and the effect expected by the miniaturization cannot be obtained. Further, the cellulose concentration in the aqueous dispersion at the time of the refining treatment is 0.1 mass%, and preferably 1 mass%. If the cellulose concentration in the aqueous dispersion is less than 0.1% by mass, the productivity is remarkably lowered, and when the concentration is higher than 30% S ° / 〇, the pulverization efficiency is low, and the desired fine cellulose fibers cannot be obtained. The number of times of the micronization treatment depends on the cellulose concentration in the aqueous dispersion. However, when the cellulose concentration is 0.1% by mass to 1% by mass, the number of treatments can be sufficiently reduced from 10 to 50 times, but 1% by mass to 10% by mass, it is necessary to be about 50 times to 200 times. When the concentration is more than 30% by mass, the number of treatments of several hundred or more times is required, which is not practical from the viewpoint of industry. -12- 201245293 For the evaluation of the refinement in the aqueous dispersion of the finely divided cellulose fibers used in the present invention, for example, a laser diffraction/scattering type particle size distribution measuring instrument can be used. In the present invention, when the volume particle size distribution of the aqueous dispersion of the cellulose fibers is preferably used, the particle diameter (medium diameter) within 50% of the volume cumulative is 0.01 to m to 40; um, preferably 0.05 to m. 10; wm cellulose fiber. When the particle diameter is less than 0.01 y m, the cellulose fibers are too fine to obtain an additive effect, that is, the mechanical strength of the resin composition containing the obtained fibrous resin reinforcing agent or a molded article thereof as described below cannot be obtained. Further, when the particle diameter is more than 40/m, the cellulose fibers are not sufficiently refined, and the mechanical strength of the resin composition containing the same or the molded body thereof is not different from the mechanical strength of the unpulverized cellulose raw material. Can't get the desired results. Further, the fiber diameter of the finely divided cellulose fibers used in the present invention is not particularly limited, but may be from 0. 0 0 1 // m to 1 〇 # m, preferably from 0.0 1 // m to 1 # m . Further, the aspect ratio (L/D) is not particularly limited, but may be 10 to 100,000, preferably 100 to 10,000. <Additive (B) > As the additive (B) in the present invention, if it is hydrophilic, and HLB (Hydrophile-Lipophile-Balance) is 10 to 20, and the cellulose can be obtained If the fibers (A) are uniformly dispersed, a known one can be used without particular limitation. For example, monoglyceride, monoglyceride acetate, monoglyceride lactic acid, monoglyceride citrate, monoglyceride succinate, diglyceryl tartrate monoglyceride; polyglycerol ester, sugar ester, sorbitan ester , stearyl calcium lactate, lecithin and the like. 13-201245293 In the present invention, by blending the additive (B), the mechanical strength of the formulated resin composition or the molded body thereof is improved as compared with the case where the finely divided cellulose fibers are used alone. Further, in the present invention, when the cellulose fibers and the additives are formed into a fibrous resin, they are blended in the thermoplastic resin, and can be suppressed as compared with each of the individual (without the form of the fibrous resin reinforcing agent). The aggregation of the finely divided cellulose fibers in the obtained resin composition is formed, and at the same time, the cellulose fibers in the resin composition can be directly dispersed in a finely refined state, which is advantageous, and further, as a hydrophilic or hydrophobic property indicating the additive (B). The scale is the HLB 値 expressed by the number 〇 from the balance of the hydrophilic group and the lipophilic group. If HLB is less oleophilic and higher in hydrophilicity, it means that it corresponds to the change in solubility or dispersibility of water by HLB. As for the calculation method of HLB, the GRIFFIN method, the ATLAS method, the DAVIS method, the Kawasaki method, and the like are known, and can be calculated, for example, by the following GRIFFIN formula. HLB = 2 0x (Chemical Formula of Hydrophilic Group / Whole Molecular Weight) When a commercially available product is used as the additive (B), HLB値 described in the catalogue and the like disclosed in the product can be applied. The additive used in the present invention has an HLB 10 of 10 to 20, and more preferably an HLB 12 of 12 to 16. When the HLB is less than 10, the cellulose fibers and the additives have low affinity in water. At the stage of producing the fibrous resin reinforcing agent, the cellulose fibers form agglomerates, and the following resin containing the obtained fibrous resin reinforcing agent cannot be obtained. An increase in the mechanical strength of the composition or its molded body. -14-201245293 The amount of the additive (B) in the fibrous resin reinforcing agent is, for example, 50 parts by mass based on 100 parts by mass of the total of the finely divided cellulose fibers (A) and (B). -99.9 parts by mass, preferably 70 parts by mass to 99.0 parts by mass. When the amount of the additive is less than 50 parts by mass, the cellulose fiber containing the fibrous resin reinforcing agent formed by the fine cellulose fibers and the additive or the cellulose fibers in the molded body thereof cannot be uniformly dispersed, and the machine cannot be improved. strength. Examples of the commercially available additives which can be used in the fibrous resin reinforcing agent of the present invention are as follows, but are not limited to these: POEM [registered trademark] J-0021, POEM L-021, POEM J-
00 8 1 HV > POEM J - 0 3 8 1 V、P 〇 E M C - 7 8 1、RIK E M A L [註冊 商標]C-250、RIKEMAL B-205、RIKEMAL 0-852 (以上爲 理硏維他命（股）製）；SUNSOFT[註冊商標]Q-12S、 SUNSOFT M-12J 、 SUNSOFT Q-14S、 SUNSOFT Q-17S、 SUNSOFT Q-18S、 SUNSOFT Q-182S、 SUNSOFT A-121E、 SUNSOFT A-141E、SUNSOFT A-1 71E、SUNSOFT A-181E (以上爲太陽化學（股）製）；S-1170、S-1570、S-1670 、P- 1 5 70、P- 1 670、Μ- 1 695、0-1570、L- 1695、LWA- 1 5 70、L-10D、L-7D、M-10D、M-7D、P-8D ' S-28D、S-24D、SWA-20D、SWA-15D、SWA-10D、0-15D (以上爲 三菱化學食品（股）製）；NEWCOL 2305、NEWCOL 23 07、NEWCOL 2308、NEWCOL 2308-HE、NEWCOL 2310 、NEWCOL 23 12、NEWCOL 23 1 4、NEWCOL 23 1 8、 NEWCOL 2320、NEWCOL 2327(20)、NEWCOL 2 3 30、 -15- 20124529300 8 1 HV > POEM J - 0 3 8 1 V, P 〇EMC - 7 8 1. RIK EMAL [Registered Trademark] C-250, RIKEMAL B-205, RIKEMAL 0-852 (The above is the rationale for vitamins )))SUNSOFT[Registered Trademark]Q-12S, SUNSOFT M-12J, SUNSOFT Q-14S, SUNSOFT Q-17S, SUNSOFT Q-18S, SUNSOFT Q-182S, SUNSOFT A-121E, SUNSOFT A-141E, SUNSOFT A -1 71E, SUNSOFT A-181E (above is Sun Chemical Co., Ltd.); S-1170, S-1570, S-1670, P-1 5 70, P-1 670, Μ-1 695, 0-1570 , L-1695, LWA-1 5 70, L-10D, L-7D, M-10D, M-7D, P-8D 'S-28D, S-24D, SWA-20D, SWA-15D, SWA-10D , 0-15D (above is Mitsubishi Chemical Food Co., Ltd.); NEWCOL 2305, NEWCOL 23 07, NEWCOL 2308, NEWCOL 2308-HE, NEWCOL 2310, NEWCOL 23 12, NEWCOL 23 1 4, NEWCOL 23 1 8, NEWCOL 2320 , NEWCOL 2327(20), NEWCOL 2 3 30, -15- 201245293
NEWCOL 2344 、 NEWCOL 2360、 NEWCOL 2 3 99-S NEWCOL 23 99-S(25)、NEWCOL NT -5、NEWCOL NT-7 NEWCOL NT-9、 NEWCOL N T · 1 2 、NEWCOL NT-1 5 NEWCOL NT-20 ' NEWCOL NT-30 > NEWCOL NT-40 NEWCOL NT-50 、NEWCOL 1004 、NEWCOL 1006 NEWCOL 1 00 8 、 NEWCOL 1020 、NEWCOL 12 10 NEWCOL 1 3 0 5 、 NEWCOL 13 10 、NEWCOL 1525 NEWCOL 1 5 3 3 ' NEWCOL 1 545 、 NEWCOL 1 5 00-S NEWCOL 1 606 ' NEWCOL 1607 、NEWCOL 1807 NEWCOL 1 820、 NEWCOL 1 8 60 、 NEWCOL 3 520-C NEWCOL 2306-Y ' NEWCOL 2308-Y 、NEWCOL 23 1 4-Y NEWCOL 23 06-HY、NEWCOL 23 0 8 -LY、NEWCOL 1 008-F1、NEWCOL 1 902-Y、NEWCOL 1 3 08-FA(90)、NEWCOL 706 > NEWCOL 707、NEWCOL 708、NEWCOL 709、 NEWCOL 710、NEWCOL 711 、NEWCOL 712、NEWCOL 714 ' NEWCOL 714(80)、NEWCOL 719、NEWCOL 723、NEWCOL 2344, NEWCOL 2360, NEWCOL 2 3 99-S NEWCOL 23 99-S(25), NEWCOL NT -5, NEWCOL NT-7 NEWCOL NT-9, NEWCOL NT · 1 2 , NEWCOL NT-1 5 NEWCOL NT-20 NEWCOL NT-30 > NEWCOL NT-40 NEWCOL NT-50 , NEWCOL 1004 , NEWCOL 1006 NEWCOL 1 00 8 , NEWCOL 1020 , NEWCOL 12 10 NEWCOL 1 3 0 5 , NEWCOL 13 10 , NEWCOL 1525 NEWCOL 1 5 3 3 ' NEWCOL 1 545 , NEWCOL 1 5 00-S NEWCOL 1 606 ' NEWCOL 1607 , NEWCOL 1807 NEWCOL 1 820 , NEWCOL 1 8 60 , NEWCOL 3 520-C NEWCOL 2306-Y ' NEWCOL 2308-Y , NEWCOL 23 1 4-Y NEWCOL 23 06-HY, NEWCOL 23 0 8 -LY, NEWCOL 1 008-F1, NEWCOL 1 902-Y, NEWCOL 1 3 08-FA(90), NEWCOL 706 > NEWCOL 707, NEWCOL 708, NEWCOL 709, NEWCOL 710, NEWCOL 711 , NEWCOL 712 , NEWCOL 714 ' NEWCOL 714 (80), NEWCOL 719, NEWCOL 723,
NEWCOL NEWCOL NEWCOL NEWCOL NEWCOL NEWCOL NEWCOL NEWCOL 723(60) 、 NEWCOL 729 、 NEWCOL 73 3 、 740 ' NEWCOL 740(60) 、 NEWCOL 747 、 780(60)、NEWCOL 610、NEWCOL 610(80)、 2607 > NEWCOL 2609 、 NEWCOL 2614 、 707-F、NEWCOL 710-F、NEWCOL 714-F、 2608-F、NEWCOL 2600-FB、NEWCOL 2616-F、 36 12-FA、NEWCOL 25、NEWCOL 20-MF、 65、NEWCOL 82、NEWCOL 85、NEWCOL 80- -16- 201245293 FL、NEWCOL 3-85、NEWCOL 9 5 - F J、N E W C O L B 1 0、 NEWCOL B13、NEWCOL CMP-6、NEWCOL CMP-8、 NEWCOL CMP-1 1 、NEWCOL 3420、NEWCOL 3280、 NEWCOL LA-407、NEWCOL OD-410、NEWCOL OD-420、 NEWCOL TA-420 、 NEWCOL 560 、 NEWCOL 5 64 、 NEWCOL 5 65、NEWCOL 5 66、NEWCOL 5 68、NEWCOL 504 ' NEWCOL 506、NEWCOL 509、NEWCOL 516(以上 爲日本乳化劑（股）製）。 <纖維狀樹脂補強劑之製造方法> 前述纖維狀樹脂補強劑可藉由使前述添加劑（B )溶 解或乳化或分散於經前述微細化之纖維素纖維（A )之水 分散液中而調製懸浮液，及自該懸浮液去除水分，而製造 纖維素纖維（A)於添加劑（B)中均一分散之纖維狀樹脂 補強劑。 關於纖維狀樹脂補強劑之製造，只要可使經微細化之 纖維素纖維（A )及添加劑（B )至少於水中分別簡單共存 之狀態即可’但在去除水分之前，較好經微細化之纖維素 纖維（A )及添加劑（B )於水中均一乳化或分散而成爲懸 浮液。 朝水中乳化或分散方法並未特別限制，但例如可爲在 製造經微細化纖維素纖維（A )之步驟中，以纖維素原料 與添加劑（B )以共存狀態，同時進行前述纖維素原料之 微細化及添加劑（B)之乳化或分散處理，而調製懸浮液 -17- 201245293 除此以外，亦可例如使經微細化纖維素纖維（ 水分散液與添^卩劑（B )共存狀態，以通用之攪拌 如螺旋槳•木槳翼、均質機、分散混合機、超音波 )等調製懸浮液。 經微細化纖維素纖維（A)及添加劑（B )之水 中之濃度，以兩者合計量計，爲0.5質量％〜99質i 好爲5質fi %〜60質量％。懸浮液中之纖維素纖維< 添加劑（B )之合計量之濃度未達0.5質量％時，水 效率低，想必於實際製造時並不實際。 至於水分去除方法，舉例有慣用之濃縮及乾燥 例如加熱濃縮、減壓濃縮、熱風乾燥、真空乾燥、 燥、凍結真空乾燥）。該等處理亦可適當組合使用 去除時之溫度，在常壓時爲l〇〇°C〜200°C，較好爲 〜150 °C。與減壓、常壓無關地，在200 °C以上之溫 纖維素顯著變黃，故有損及如下所得之樹脂組成物 體外觀之虞故而不佳。 如此所得之本發明之纖維狀樹脂補強劑中所含 量爲5質量％以下，較好爲3質量％以下。又，水 測定，爲藉熱分析裝置（TG-DTA )測定時1 50t質 量、或可藉Karl Fischer等測定。纖維狀樹脂補強 含之水分fi含有多於5質量％時，纖維狀樹脂補強 配於聚乳酸中，則該聚乳酸加工成形時會因水分而 解有引起分子量降低之虞，其結果使成形體之機械 :A )之 機（例 分散機 懸浮液 [%，較 :A)及 分去除 方法（ 噴霧乾 。水分 1 1 o°c 度條件 或成形 之水分 分量之 量減少 劑中所 劑若調 經受水 強度降 -18- 201245293 低故而應避免。 <其他添加劑> 本發明之纖維狀樹脂補強劑’依據需要，亦可含有其 他添加劑。例如無機塡充劑（例如滑石、雲母、二氧化砂 、高嶺土、黏土、矽灰石、玻璃珠、玻璃片、鈦酸鉀、碳 酸鈣、磷酸鈣、硫酸錶、氧化鈦）、難燃劑（例如溴化合 物、氯化合物等之鹵系難燃劑、三聚氰胺系難燃劑、三氧 化銻、五氧化銻等之銻系難燃劑、氫氧化鋁、氫氧化鎂、 矽化合物等之無機系難燃劑、紅磷、磷酸酯類、聚磷酸銨 、磷腈等之磷系難燃劑、PTFE等氟樹脂）、熱安定劑、 光安定劑、紫外線吸收劑、抗氧化劑、衝擊改良劑、抗靜 電劑、顏料、著色劑、脫模劑、滑劑、添加劑、相溶化劑 、發泡劑、香料、抗菌抗黴劑、其他各種塡充劑、一般合 成樹脂製造時通常使用之各種添加劑亦可含於本發明之纖 維狀樹脂補強劑中。 又，亦進而含有該等 <其他添加劑 > 之纖維狀樹脂補強 劑亦爲本發明之對象。 該等添加劑之形狀爲纖維狀、粒狀、板狀、針狀、球 狀、粉末之任一者均可。該等添加劑可在相對於由經微細 化纖維素纖維（A)與添加劑（B)所成之纖維狀樹脂補強 劑1〇〇質量份，爲500質量份以內使用。 <樹脂組成物及成形體> -19- 201245293 本發明之樹脂組成物含有纖維狀樹脂補強劑及熱可塑 性樹脂，較好含有聚乳酸，該樹脂組成物之製造、成形係 使用慣用之熔融混練。 本發明之樹脂組成物中使用之聚乳酸包含聚乳酸之均 聚物或共聚物。聚乳酸爲共聚物時，共聚物之排列狀態爲 無規共聚物、交替共聚物、嵌段共聚物、接枝共聚物之任 一種均可。且，亦可爲以聚乳酸之均聚物或共聚物爲主體 之與其他樹脂之摻合聚合物。其他樹脂舉例有例如聚乳酸 以外之生物分解性樹脂、廣泛使用之熱可塑性樹脂、廣泛 使用之熱可塑性工程塑料。 至於聚乳酸並未特別限制，而可爲例如使乳交酯開環 聚合者、使乳酸之D體、L體、消旋體等直接聚縮合者， 亦可爲聚-D-乳酸、聚-L-乳酸、D-乳酸與L-乳酸之共聚物 、聚-D-乳酸與聚-L-乳酸之混合物之任一者。至於該聚-D-乳酸與聚乳酸之混合物，立體錯合型聚乳酸顯示比聚-D-乳酸或聚-L-乳酸高之耐熱性。聚乳酸之重量平均分子 量通常爲10,00 0〜5 00,000左右。且聚乳酸亦可使用.利用熱 '光、輻射線使聚乳酸利用交聯劑交聯者。 本發明之樹脂組成物中之纖維狀樹脂補強劑與熱可塑 性樹脂（聚乳酸）之調配比例，相對於纖維狀樹脂補強劑 與樹脂之合計fi 1 00質量份，纖維狀樹脂補強劑之調配量 爲例如0.1質量份~50質量份，較好爲1質量份〜30質量 份’更好爲1質量份〜20質量份。纖維狀樹脂補強劑之調 配量未達0· 1質量份時，經微細化纖維素纖維之含量低， -20- 201245293 故無法獲得樹脂之機械強度的提高。且，多於50質量份 之調配量時，纖維狀樹脂補強劑之可塑化效果變顯著，使 樹脂之機械強度降低。 樹脂組成物之製造中之熔融混練爲公知方法，例如藉 由捏合機、輥混合機、班伯理混合機、擠出機（單軸或雙 軸擠出機），獲得纖維狀樹脂補強劑與熱可塑性樹脂之樹 脂組成物。且，在熔融混練之前，亦可使用亨歇爾混合機 、超混合機、V型摻合機、高速混合機等之任一者，使纖 維狀樹脂補強劑與樹脂及其他成分（例如前述添加劑）預 先混合。又，熔融混練溫度爲50°C〜300°C，較好爲l〇〇°C 〜2 5 0°C。 使含有本發明之纖維狀樹脂補強劑之樹脂組成物成形 時，藉由使用一般射出成形、吹塑成形、真空成形、壓縮 成形等之慣用成形法，而可容易地製造各種成形體。如此 所得之成形體亦爲本發明之對象。 如上述，本發明之纖維狀樹脂補強劑處於經微細化纖 維素纖維分散於添加劑（B )中之狀態，且對成爲基質之 樹脂之分散性極爲優異。因此，於基質樹脂中調配纖維狀 樹脂補強劑之樹脂組成物及成形體，成爲經微細化纖維素 纖維均一分散之狀態，而認爲顯示樹脂組成物或成形體之 機械強度優異之特性者。 而且本發明之前述成形體由其衝擊強度顯著提高，故 可應用於汽車零件、電性電子機器框體、機械零件等。 -21 - 201245293 實施例 以下舉實施例、比較例更具體說明本發明特徵。以下 實施例所示之材料、使用量、比例、處理內容、處理順序 只要不脫離本發明主旨之範圍內均可進行適當變更。而且 ，本發明之範圍不應解釋爲由下述具體例所限定。 實施例、比較例所用之測定法記載如下。 <偏光顯微鏡觀察> 針對實施例及比較例所調製之各纖維狀樹脂補強劑及 各樹脂組成物，使用偏光顯微鏡（KIKON (股）製， ECLIPSE LV100POL)進行觀察。分別觀察各纖維狀樹脂 補強劑以在室溫下夾於玻璃板之狀態，及各樹脂組成物在 非晶狀態（於1 8 5 °C使樹脂組成物熔融，急冷至室溫）之 樹脂組成物中之纖維素纖維之分散狀態（倍率200倍）》 <雷射繞射/散射式粒度分佈測定> 纖維素之粒度測定係使用雷射繞射（MALVERN (股 )製，機器名：MASTERSIZER 2000 )。測定係在水中、 室溫、搅拌3,5 00rpm、超音波照射下進行。 <示差熱天平>NEWCOL NEWCOL NEWCOL NEWCOL NEWCOL NEWCOL NEWCOL NEWCOL 723(60) , NEWCOL 729 , NEWCOL 73 3 , 740 ' NEWCOL 740(60) , NEWCOL 747 , 780(60), NEWCOL 610, NEWCOL 610(80), 2607 > NEWCOL 2609 , NEWCOL 2614, 707-F, NEWCOL 710-F, NEWCOL 714-F, 2608-F, NEWCOL 2600-FB, NEWCOL 2616-F, 36 12-FA, NEWCOL 25, NEWCOL 20-MF, 65, NEWCOL 82, NEWCOL 85, NEWCOL 80- -16- 201245293 FL, NEWCOL 3-85, NEWCOL 9 5 - FJ, NEWCOLB 1 0, NEWCOL B13, NEWCOL CMP-6, NEWCOL CMP-8, NEWCOL CMP-1 1 , NEWCOL 3420, NEWCOL 3280, NEWCOL LA-407, NEWCOL OD-410, NEWCOL OD-420, NEWCOL TA-420, NEWCOL 560, NEWCOL 5 64, NEWCOL 5 65, NEWCOL 5 66, NEWCOL 5 68, NEWCOL 504 'NEWCOL 506, NEWCOL 509, NEWCOL 516 (above is Japanese emulsifier (share) system). <Production Method of Fibrous Resin Reinforcing Agent> The fibrous resin reinforcing agent can be obtained by dissolving or emulsifying or dispersing the additive (B) in the aqueous dispersion of the finely divided cellulose fibers (A). The suspension is prepared, and water is removed from the suspension to produce a fibrous resin reinforcing agent in which the cellulose fibers (A) are uniformly dispersed in the additive (B). The production of the fibrous resin reinforcing agent can be such that the finely divided cellulose fibers (A) and the additive (B) can be easily coexisted at least in water, but it is preferably fined before the moisture is removed. The cellulose fiber (A) and the additive (B) are uniformly emulsified or dispersed in water to form a suspension. The method of emulsifying or dispersing in the water is not particularly limited, but for example, in the step of producing the fine cellulose fibers (A), the cellulose raw material and the additive (B) may be coexisted while the cellulose raw material is simultaneously used. Further, the emulsification or dispersion treatment of the additive (B) and the preparation of the suspension -17-201245293 may be carried out, for example, in the state in which the finely divided cellulose fibers (the aqueous dispersion and the additive (B) are coexistent, The suspension is prepared by a universal stirring such as a propeller, a wooden paddle, a homogenizer, a dispersing mixer, or an ultrasonic wave. The concentration in the water of the fine cellulose fibers (A) and the additive (B) is 0.5% by mass to 99% by mass, preferably 5 parts by mass to 60% by mass. When the concentration of the cellulose fibers < additive (B) in the suspension is less than 0.5% by mass, the water efficiency is low, and it is not practical at the time of actual production. As the water removal method, there are exemplified conventional concentration and drying such as heat concentration, concentration under reduced pressure, hot air drying, vacuum drying, drying, and freeze drying under vacuum. These treatments may also be used in combination with the temperature at the time of removal, and at normal pressure, from 10 ° C to 200 ° C, preferably from 150 ° C. Regardless of the pressure reduction and the normal pressure, the temperature of the cellulose at 200 ° C or higher is significantly yellow, which is detrimental to the appearance of the resin composition obtained as follows. The content of the fibrous resin reinforcing agent of the present invention thus obtained is 5% by mass or less, preferably 3% by mass or less. Further, the water measurement was carried out by a heat analysis apparatus (TG-DTA) at a temperature of 150 tons or by Karl Fischer et al. When the content of the water-containing resin is more than 5% by mass, and the fibrous resin is reinforced in the polylactic acid, the polylactic acid is deformed by moisture to cause a decrease in molecular weight, and as a result, the molded body is formed. Machinery: A) machine (such as disperser suspension [%, compare: A) and sub-removal method (spray dry. Moisture 1 1 o ° c degree condition or formed moisture component of the amount of agent The water strength drop -18-201245293 is low and should be avoided. <Other Additives> The fibrous resin reinforcing agent of the present invention may also contain other additives as needed. For example, inorganic chelating agents (for example, talc, mica, dioxide) Sand, kaolin, clay, ash, glass beads, glass flakes, potassium titanate, calcium carbonate, calcium phosphate, sulfuric acid, titanium oxide), flame retardant (such as bromine compounds, chlorine compounds, etc.) , melamine-based flame retardant, antimony trioxide, antimony-oxide, anti-flammability agent, aluminum hydroxide, magnesium hydroxide, antimony compound, inorganic flame retardant, red phosphorus, phosphate, ammonium polyphosphatePhosphorus-based flame retardant such as phosphazene, fluororesin such as PTFE, thermal stabilizer, light stabilizer, ultraviolet absorber, antioxidant, impact modifier, antistatic agent, pigment, colorant, release agent, slippery Agents, additives, compatibilizers, foaming agents, perfumes, antibacterial and antifungal agents, various other chelating agents, and various additives generally used in the manufacture of general synthetic resins may also be contained in the fibrous resin reinforcing agent of the present invention. The fibrous resin reinforcing agent further containing the <other additives> is also the object of the present invention. The shape of the additives is any one of a fibrous form, a granular form, a plate form, a needle shape, a spherical shape, and a powder. The additive may be used in an amount of 500 parts by mass or less based on 1 part by mass of the fibrous resin reinforcing agent formed of the finely divided cellulose fiber (A) and the additive (B). Composition and molded article> -19- 201245293 The resin composition of the present invention contains a fibrous resin reinforcing agent and a thermoplastic resin, and preferably contains polylactic acid, and the resin composition is used for the production and molding. The polylactic acid used in the resin composition of the present invention comprises a homopolymer or a copolymer of polylactic acid. When the polylactic acid is a copolymer, the alignment state of the copolymer is a random copolymer, an alternating copolymer, a block copolymer. Any of the graft copolymers may be used, and may be a blended polymer with other resins mainly composed of a homopolymer or a copolymer of polylactic acid. Other resins include, for example, biodegradability other than polylactic acid. Resin, a widely used thermoplastic resin, and a widely used thermoplastic engineering plastic. The polylactic acid is not particularly limited, and may be, for example, a lactide ring-opening polymerizer, a lactic acid D body, a L body, a racemic body, or the like. The direct polycondensation may be any of poly-D-lactic acid, poly-L-lactic acid, a copolymer of D-lactic acid and L-lactic acid, or a mixture of poly-D-lactic acid and poly-L-lactic acid. As for the mixture of poly-D-lactic acid and polylactic acid, the sterically misaligned polylactic acid exhibits higher heat resistance than poly-D-lactic acid or poly-L-lactic acid. The weight average molecular weight of polylactic acid is usually about 10,00 to 5,00,000. Polylactic acid can also be used. The polylactic acid is crosslinked by a crosslinking agent by using heat and light or radiation. The blending ratio of the fibrous resin reinforcing agent to the thermoplastic resin (polylactic acid) in the resin composition of the present invention is fi 1 00 parts by mass based on the total of the fibrous resin reinforcing agent and the resin, and the blending amount of the fibrous resin reinforcing agent It is, for example, 0.1 part by mass to 50 parts by mass, preferably 1 part by mass to 30 parts by mass 'more preferably 1 part by mass to 20 parts by mass. When the amount of the fibrous resin reinforcing agent is less than 0.1 part by mass, the content of the fine cellulose fibers is low, and -20 to 201245293, the mechanical strength of the resin cannot be improved. Further, when the amount is more than 50 parts by mass, the plasticizing effect of the fibrous resin reinforcing agent becomes remarkable, and the mechanical strength of the resin is lowered. The melt kneading in the production of the resin composition is a known method, for example, by a kneader, a roll mixer, a Banbury mixer, an extruder (uniaxial or twin-screw extruder), to obtain a fibrous resin reinforcing agent and A resin composition of a thermoplastic resin. Further, before the melt-kneading, any of a Henschel mixer, an ultra-mixer, a V-type blender, a high-speed mixer, or the like may be used to form a fibrous resin reinforcing agent with a resin and other components (for example, the aforementioned additives). ) Premixed. Further, the melt kneading temperature is from 50 ° C to 300 ° C, preferably from 10 ° C to 250 ° C. When the resin composition containing the fibrous resin reinforcing agent of the present invention is molded, various molded articles can be easily produced by a conventional molding method such as general injection molding, blow molding, vacuum molding, or compression molding. The shaped body thus obtained is also the object of the present invention. As described above, the fibrous resin reinforcing agent of the present invention is in a state in which the fine cellulose fibers are dispersed in the additive (B), and is extremely excellent in dispersibility of the resin to be a matrix. Therefore, the resin composition and the molded body of the fibrous resin reinforcing agent are blended in the matrix resin, and the finely divided cellulose fibers are uniformly dispersed, and it is considered that the resin composition or the molded body is excellent in mechanical strength. Further, since the molded body of the present invention is remarkably improved in impact strength, it can be applied to automobile parts, electric electronic machine frames, mechanical parts and the like. -21 - 201245293 EXAMPLES Hereinafter, the characteristics of the present invention will be more specifically described by way of examples and comparative examples. The materials, the amounts, the ratios, the treatment contents, and the treatment procedures shown in the following examples can be appropriately changed without departing from the spirit and scope of the invention. Moreover, the scope of the invention should not be construed as being limited by the following specific examples. The measurement methods used in the examples and comparative examples are described below. <Performance of polarizing microscope> Each of the fibrous resin reinforcing agents and the respective resin compositions prepared in the examples and the comparative examples were observed using a polarizing microscope (manufactured by KIKON Co., Ltd., ECLIPSE LV100POL). Each of the fibrous resin reinforcing agents was observed to be sandwiched between the glass sheets at room temperature, and the resin composition of each of the resin compositions in an amorphous state (melting the resin composition at 185 ° C and quenching to room temperature) Dispersion state of cellulose fibers in the product (magnification 200 times) <Laser diffraction/scattering particle size distribution measurement> The particle size measurement of cellulose uses laser diffraction (MALVERN), machine name: MASTERSIZER 2000). The measurement was carried out in water, room temperature, stirring at 3,500 rpm, and ultrasonic irradiation. <Differential Thermal Balance>
使用 TG-DTA ( RIGATA (股）製，Thermo Plus，TG-8 120)，以10°C /分鐘自室溫升溫至500t，測定於150°C 之質量減少量。 -22- 201245293 <重量平均分子量> 使用凝膠滲透層析儀（TOSOH (股）製 HLC· 8220GPC，管柱：Shodex[註冊商標]KF-8 05 L + KF-8 04L) ，管柱溫度40 °C，溶劑四氫呋喃，以RI (示差折射率計 )檢測器進行檢測。 <成形體之衝擊試驗> 使用衝擊試驗機（安田精機製作所（股）製，萬能衝 擊試驗機No. 258, 2J錘），依據JIS K 7110進行凹口衝 擊試驗（邊緣方式，無凹口）。試驗片之緊固扭矩爲6N [實施例1 :由市售纖維素粉末製造纖維狀樹脂補強劑及樹 脂組成物、成形體（1 )] 將市售纖維素粉末（Celite公司製Fibra-Cell BH-100 )5質量份分散於純水495質量份中，進行微細化處理（ SUGINO 機器公司製，STARBURST 系統）（200MPa、50 次），獲得經微細化纖維素纖維水分散液。將所得纖維素 纖維水分散液量取於培養皿中，在1 1 0 °C進行5小時乾燥 ，除去水分測量殘渣量，測定濃度。其結果，水中經微細 化纖維素纖維濃度爲0 · 74質量％。於該纖維素纖維水分散 液6 76質量份（纖維素量5質量份）中，添加以十甘油單 月桂酸酯爲主成分之添加劑（理硏維他命（股）製， -23- 201245293 POEM[註冊商標]J-0021 : HLB=16.0) 45質量份，溶解後 ’於氮氣氣流下’邊搅拌邊加熱，藉此餾除水分，獲得纖 維狀樹脂補強劑（纖維素量1 0質量％)«所得纖維狀樹脂 補強劑之水分量以利用前述T G - D T A測定1 5 0。(：下之質量 減少分後，爲1 .1 9質量％ » 觀察所得纖維狀樹脂補強劑中之經微細化纖維素纖維 之分散狀態之偏光顯微鏡照片示於圖1。 對所得纖維狀樹脂補強劑，以使纖維素纖維成爲1質 量％之方式添加聚乳酸（NatureWorks公司製Ingeo[註冊 商標]3001D)，使用雙軸擠出機（東洋精機製作所（股 )製，LABO PLASTOMILL，雙軸擠出機 2 D1 5 W )，以筒 溫度1 9 0 °C進行熔融混練，獲得聚乳酸中含有1質量％纖 維素纖維之樹脂組成物。觀察所得樹脂組成物中之經微細 化纖維素纖維之分散狀態之偏光顯微鏡照片示於圖6。 接著，使用射出成形機（ThermoFisher Scientific ( 股）製，Thermo Scientific HAAKE MiniJet II )，將所得 樹脂組成物以汽缸溫度200°C熔融，朝30°C模具內射出。 保持30秒使樹脂硬化後，自模具取出成形體（長度80mm X寬度1 〇mmx厚度4mm )。 [實施例2:由市售纖維素粉末製造纖維狀樹脂補強劑及樹 脂組成物、成形體（2 )] 除了纖維狀樹脂補強劑之製造中使用之添加劑自理硏 維他命（股）至之POEM J-002 1變更爲以十甘油單油酸酯 -24- 201245293 爲主成分之添加劑（理硏維他命（股）製，POEM[註冊商 標]J-03 8 1 V; HLB = 12.0)以外’與實施例i同樣製作纖 維狀樹脂補強劑及樹脂組成物、成形體。所得纖維狀樹脂 補強劑之水分量以利用前述TG-DTA測定15〇。〇下之質量 減少分後，爲2.29質量％。 觀察所得纖維狀樹脂補強劑中之經微細化纖維素纖維 之分散狀態之偏光顯微鏡照片示於圖2，觀察含該纖維狀 樹脂補強劑之樹脂組成物中之經微細化纖維素纖維之分散 狀態之偏光顯微鏡照片示於圖7。 [實施例3 :由純化紙漿製造纖維狀樹脂補強劑及樹脂組成 物、成形體] 將純化紙漿5 0質量份分散於4 0 0質量份純水中，施 以均質機處理（ΜIC R Ο T E C NITIΟ N 製 P h y s c o t r ο n )( 1 5,000 rpm，1小時），進行粗粉碎。接著，與實施例1 同樣進行纖維素微細化處理，添加以十甘油單月桂酸酯爲 主成分之添加劑（理硏維他命（股）製，P OEM [註冊商標 ]J-002 1 ) ’藉由去除水分，獲得纖維狀樹脂補強劑，接 著製作樹脂組成物、成形體。所得纖維狀樹脂補強劑之水 分量以利用前述TG-DTA測定15(TC下之質量減少分後， 爲2.94質量％。 觀察所得纖維狀樹脂補強劑中之經微細化纖維素纖維 之分散狀態之偏光顯微鏡照片示於圖3，觀察含該纖維狀 樹脂補強劑之樹脂組成物中之經微細化纖維素纖維之分散 -25- 201245293 狀態之偏光顯微鏡照片示於圖8。 [實施例4 :由細菌纖維素製造纖維狀樹脂補強劑及樹脂組 成物、成形體] 以剪刀切斷細菌纖維素（UTAMA公司製，PT. NIRAMAS) 2,000質量份，使用家庭用混合機予以細切斷 。將由細切斷所得之水分散液（pH3左右）予以過濾，接 著以添加500質量份水而進行水洗。該操作重覆至分散液 之pH爲7止。對如此獲得之水分散液中，施以均質機處 理（MICROTEC NITION 製 Physcotron ) ( 1 5,000 rpm，1 小時），進行粗粉碎獲得細菌纖維素之水分散液。接著， 與實施例1同樣進行纖維素微細化處理，添加以十甘油單 月桂酸酯爲主成分之添加劑（理硏維他命（股）製， POEM[註冊商標]J-002 1 )，藉由去除水分，獲得纖維狀 樹脂補強劑，接著製作樹脂組成物、成形體。 觀察所得纖維狀樹脂補強劑中之經微細化纖維素纖維 之分散狀態之偏光顯微鏡照片示於圖4，觀察含該纖維狀 樹脂補強劑之樹脂組成物中之經微細化纖維素纖維之分散 狀態之偏光顯微鏡照片示於圖9。 [比較例1 :由市售纖維素粉末製造纖維狀樹脂補強劑及樹 脂組成物' 成形體（3 )] 除了纖維狀樹脂補強劑之製造中使用之添加劑自理硏 維他命（股）至之POEM[註冊商標]J-002 1變更爲以十甘 -26- 201245293 油單月桂酸酯爲主成分之添加劑（理硏維他命（股）製’ POEM[註冊商標]DL-100 ; HLB = 9.4 )以外，與實施例1 同樣製作纖維狀樹脂補強劑及樹脂組成物、成形體。所得 纖維狀樹脂補強劑之水分量以利用前述TG-DTA測定150 °C下之質量減少分後，爲1 .79質量％。 觀察所得纖維狀樹脂補強劑中之經微細化纖維素纖維 之分散狀態之偏光顯微鏡照片示於圖5，觀察含該纖維狀 樹脂補強劑之樹脂組成物中之經微細化纖維素纖維之分散 狀態之偏光顯微鏡照片示於圖1 〇。 [比較例2 :含有市售纖維素粉末之樹脂組成物、成形體之 製造] 於聚乳酸（NatureWorks公司製 Ingeo[註冊商標] 3001D) 180質量份中，添加以十甘油單月桂酸酯爲主成 分之添加劑（理硏維他命（股）製，POEM[註冊商標]J_ 0021) 18質量份、市售纖維素粉末（Celite公司製？丨1)^-Cell BH-100) 2質量份，以雙軸擠出機（東洋精機製作所 (股）製，LABO PLASTOMILL，雙軸擠出機 2D15W)， 以筒溫度1 90°C進行熔融混練，獲得聚乳酸中含有1質量 %纖維素纖維粉末之樹脂組成物。觀察所得樹脂組成物中 之市售纖維素粉末之分散狀態之偏光顯微鏡照片示於圖11 〇 接著，與實施例1同樣製作成形體。 -27- 201245293 [比較例3 :含有粗粉碎紙漿之纖維狀樹脂補強劑及樹脂組 成物、成形體之製造] 於與實施例3同樣獲得之粗粉碎紙漿之水分散液（纖 維素量3.5質量份）中，與實施例1同樣，添加以十甘油 單月桂酸酯爲主成分之添加劑（理硏維他命（股）製， POEM[註冊商標]J-002 1 )，藉由去除水分，獲得含有粗 粉碎紙漿之纖維狀樹脂補強劑，接著製作樹脂組成物、成 形體。 觀察含有所得纖維狀樹脂補強劑之樹脂組成物中之粗 粉碎紙漿之分散狀態之偏光顯微鏡照片示於圖1 2。 [比較例4 :含有粗粉碎細菌纖維素之纖維狀樹脂補強劑及 樹脂組成物、成形體之製造] 於與實施例4同樣獲得之粗粉碎細菌纖維素之水分散 液中，與實施例1同樣，添加以十甘油單月桂酸酯爲主成 分之添加劑（理硏維他命（股）製，POEM[註冊商標]J-〇〇2 1 )，藉由去除水分，獲得含有粗粉碎細菌纖維素之纖 維狀樹脂補強劑，接著製作樹脂組成物、成形體。 觀察含有所得纖維狀樹脂補強劑之樹脂組成物中之粗 粉碎細菌纖維素之分散狀態之偏光顯微鏡照片示於圖1 3。 [比較例5 :不含纖維素纖維及添加劑之樹脂組成物、成形 體之製造] 將聚乳酸（NatureWorks公司製Ingeo[註冊商標] -28- 201245293 3001D)，使用雙軸擠出機（東洋精機製作所（股）製， LABO PLASTOMILL，雙軸擠出機 2D15W)，以筒溫度 1 90t進行熔融混練，獲得樹脂組成物。接著與實施例1 同樣製作成形體。 [比較例6 :僅含添加劑之樹脂組成物、成形體之製造] 於聚乳酸（NatureWorks公司製Ingeo[註冊商標] 3 00 1D) 182質量份中，添加以十甘油單月桂酸酯爲主成 分之添加劑（理硏維他命（股）製，POEM [註冊商標]ΙΟ 021 ) 1 8 質量份 ，使 用雙軸 擠出機 （東 洋精機 製作所 （股 )製，LABO PLASTOMILL，雙軸擠出機2D15W )，以筒 溫度1 9〇°C進行熔融混練，獲得樹脂組成物。接著與實施 例1同樣製作成形體。 實施例1 ~4、比較例1 ~6所得之纖維狀樹脂補強劑中 使用之纖維素纖維及添加劑種類、由粒度測定所得之纖維 素纖維之中値徑、使用該等纖維狀樹脂補強劑等所得之樹 脂組成物之重量平均分子量、依據Π S K 7 1 1 0利用凹□衝 擊試驗所評價之成形體之凹口衝擊試驗示於表1。 -29- 201245293 【1® 樹脂組成物及成形體之評價 重量平均分子量 Mw 136,000 103,000 128,000 141,000 138,000 146,000 133,000 115,000 〇 〇Λ § 139,000 凹口衝擊強度 kJ/m2 30.9 28.7 28.7 32.1 14.5 17.4 14.5 19.0 15.9 20.2 S _ i麵 ^ 〇 11 i§ ψ i m ^ 貍藏 鐽异 •N m S | 登_ t « 1 ^ ffi ml Sm *N iS | I _ 1 HLB 16.0 12.0 16.0 1 | 16.0 寸 cK 16.0 16.0 16.0 1 16.0 f=5 腾 ilrnii P POEM J0021 POEM J0381V POEM J0021 POEM J0021 POEM DL100 POEM J0021 POEM J0021 POEM J0021 1 POEM J0021 纖維素纖維 中値徑//m 〇 VO Ο 14.0 33.7 Ο 48.9 (N 1 fS 1 1 1 種類 微細化市售纖維素 微細化市售纖維素 微細化純化紙漿 微細化細菌纖維素 微細化市售纖維素 市售纖維素粉末⑷ 粗粉碎紙漿 粗粉碎細菌纖維素 1 1 實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 比較例3 1 比較例4 比較例5 比較例6 二歡异滕赵伥枭账繫鐽_汩3|騮仔饀忒嵌炱Μ '勸洽忉-瑕湮鲤^盔繼癡賴鍵^^:^冢鎰丑一※ -30- 201245293 <結果探討> [由偏光顯微鏡之觀察] 圖1〜圖13中，白亮度高的部份表示纖維素之存在。 如圖1〜圖4所示’觀察到實施例！〜實施例4所得之 纖維狀樹脂補強劑，添加劑（H L B値：1 2〜1 6 )中之纖維 素纖維維持微細之纖維狀態，且分散性高。又，圖5所示 之比較例1所得之纖維狀樹脂補強劑中，相較於實施例， 成爲纖維素纖維凝集、均一分散性劣化之結果。 又，調配該等纖維狀樹脂補強劑之實施例1 ~實施例4 之樹脂組成物（圖6~圖9 )中，亦觀察到纖維素纖維之分 散性高。 另一方面，使用比較例1所得之纖維狀樹脂補強劑之 樹脂組成物（圖1 0 )中，相較於實施例，成爲凝集之纖維 素纖維於樹脂中分散之結果。且關於不經過纖維狀樹脂補 強劑之形態而添加市售纖維素粉末以及添加劑之樹脂組成 物··比較例2 (圖1 1 )、添加分別使用粗粉碎紙漿或粗粉 碎細菌纖維素之樹脂補強劑之樹脂組成物：比較例3 (圖 1 2 )及比較例4 (圖1 3 )，相較於實施例，成爲以非常大 粒子或纖維狀態存在，均一性差之結果。 [成形性] 含有由本發明所得之纖維狀樹脂補強劑之樹脂組成物 或成形體，可在與以往聚乳酸相同熔融溫度（雙軸擠出機 ’筒溫度1 90°C )下熔融混練，於接著進行之射出成形中 -31 - 201245293 ，亦可在與以往聚乳酸相同之汽缸溫度（200 °C )熔融， 而成爲可朝30°C之模具內射出結果。 [耐衝擊性] 如由表1所明瞭，含有由本發明所得之纖維狀樹脂補 強劑之樹脂組成物或成形體之耐衝擊性獲得顯著改善。 具體說明實施例1〜4、比較例1 ~6時，調配施以微細 化處理之市售纖維素粉末之實施例1及實施例2、調配微 細化純化紙漿之實施例3、調配微細化細菌纖維素之實施 例4，相較於比較例1〜6，衝擊強度顯著獲得改善，可見 到因添加微細化纖維素纖維所致之物性提高之結果。 尤其，對利用了使用同樣施以微細化處理之市售纖維 素粉末，但使用具有不同HLB値之添加劑之纖維狀樹脂 補強劑之樹脂組成物（成形體）之實施例1、實施例2及 比較例1進行比較時’添加劑之HLB値爲9.4之比較例1 ，相較於未添加添加劑及纖維素纖維之比較例5之樹脂組 成物，未見到衝擊強度之改善’相反地’ HLB値爲10以 上之實施例1及實施例2中，獲得衝擊強度顯著獲得改善 之結果。 【圖式簡單說明】 圖1爲觀察以實施例1製作之纖維狀樹脂補強劑中經 微細化纖維素纖維之分散狀態之偏光顯微鏡照片。 圖2爲觀察以實施例2製作之纖維狀樹脂補強劑中經 -32- 201245293 微細化纖維素纖維之分散狀態之偏光顯微鏡照片。 圖3爲觀察以實施例3製作之纖維狀樹脂補強劑中經 微細化纖維素纖維之分散狀態之偏光顯微鏡照片。 圖4爲觀察以實施例4製作之纖維狀樹脂補強劑中經 微細化纖維素纖維之分散狀態之偏光顯微鏡照片。 圖5爲觀察以比較例1製作之纖維狀樹脂補強劑中經 微細化纖維素纖維之分散狀態之偏光顯微鏡照片。 圖6爲觀察含有以實施例1製作之纖維狀樹脂補強劑 之樹脂組成物中經微細化纖維素纖維之分散狀態之偏光顯 微鏡照片。 圖7爲觀察含有以實施例2製作之纖維狀樹脂補強劑 之樹脂組成物中經微細化纖維素纖維之分散狀態之偏光顯 微鏡照片。 圖8爲觀察含有以實施例3製作之纖維狀樹脂補強劑 之樹脂組成物中經微細化纖維素纖維之分散狀態之偏光顯 微鏡照片。 圖9爲觀察含有以實施例4製作之纖維狀樹脂補強劑 之樹脂組成物中經微細化纖維素纖維之分散狀態之偏光顯 微鏡照片。 圖1 〇爲觀察含有以比較例1製作之纖維狀樹脂補強 劑之樹脂組成物中經微細化纖維素纖維之分散狀態之偏光 顯微鏡照片。 圖1 1爲觀察以比較例2製作之樹脂組成物中市售纖 維素粉末之分散狀態之偏光顯微鏡照片。 -33- 201245293 圖1 2爲觀察含有以比較例3製作之纖維狀樹脂補強 劑之樹脂組成物中經粗粉碎紙漿之分散狀態之偏光顯微鏡 照片。 圖1 3爲觀察含有以比較例4製作之纖維狀樹脂補強 劑之樹脂組成物中粗粉碎細菌纖維素之分散狀態之偏光顯 微鏡照片。 -34-Using TG-DTA (manufactured by RIGATA Co., Ltd., Thermo Plus, TG-8 120), the temperature was raised from room temperature to 500 t at 10 ° C /min, and the mass reduction amount at 150 ° C was measured. -22- 201245293 <Weight Average Molecular Weight> Using a gel permeation chromatograph (HLC·8220GPC manufactured by TOSOH Co., Ltd., column: Shodex [registered trademark] KF-8 05 L + KF-8 04L), column The temperature was 40 ° C, and the solvent was tetrahydrofuran, which was detected by a RI (differential refractometer) detector. <Effect test of molded body> Using a impact tester (manufactured by Yasuda Seiki Co., Ltd., Universal Impact Tester No. 258, 2J hammer), a notch impact test was performed in accordance with JIS K 7110 (edge method, no notch) ). The fastening torque of the test piece was 6 N. [Example 1: Production of a fibrous resin reinforcing agent and a resin composition and a molded body (1) from a commercially available cellulose powder] Commercially available cellulose powder (Fibra-Cell BH manufactured by Celite Co., Ltd.) -100) 5 parts by mass was dispersed in 495 parts by mass of pure water, and subjected to miniaturization (STARBURST system, manufactured by SUGINO CORPORATION) (200 MPa, 50 times) to obtain a finely divided cellulose fiber aqueous dispersion. The obtained cellulose fiber aqueous dispersion was weighed in a Petri dish, and dried at 110 ° C for 5 hours to remove the amount of moisture measurement residue, and the concentration was measured. As a result, the concentration of the fine cellulose fibers in the water was 0.74 mass%. In an amount of 76 parts by mass of the aqueous cellulose fiber dispersion (5 parts by mass of the cellulose), an additive containing ten glycerol monolaurate as a main component (manufactured by Lithium Vitamin Co., Ltd., -23-201245293 POEM) is added. Registered trademark] J-0021 : HLB = 16.0) 45 parts by mass, dissolved, and heated under stirring under a nitrogen gas stream to distill off water to obtain a fibrous resin reinforcing agent (cellulose content 10% by mass) « The moisture content of the obtained fibrous resin reinforcing agent was measured by the above TG-DTA. (The mass reduction of the lower part is 1.19% by mass.) The polarizing microscope photograph of the dispersed state of the fine cellulose fibers in the obtained fibrous resin reinforcing agent is shown in Fig. 1. The obtained fibrous resin is reinforced. Polylactic acid (Ingeo [registered trademark] 3001D, manufactured by NatureWorks Co., Ltd.) was added to the cellulose fiber in an amount of 1% by mass, and a biaxial extruder (Toyo Seiki Seisakusho Co., Ltd., LABO PLASTOMILL, biaxial extrusion) was used. Machine 2 D1 5 W ), melt-kneading at a cylinder temperature of 190 ° C to obtain a resin composition containing 1% by mass of cellulose fibers in polylactic acid. Observing the dispersion of fine cellulose fibers in the obtained resin composition The polarizing microscope photograph of the state is shown in Fig. 6. Next, the obtained resin composition was melted at a cylinder temperature of 200 ° C using an injection molding machine (Thermo Fisher Scientific HAAKE MiniJet II, manufactured by Thermo Fisher Scientific Co., Ltd.), and the mold was placed at 30 ° C in the mold. After the resin was cured for 30 seconds, the molded body (length 80 mm X width 1 〇 mm x thickness 4 mm) was taken out from the mold. [Example 2: Fiber made from commercially available cellulose powder. Resin reinforcing agent, resin composition, and molded body (2)] In addition to the additive used in the manufacture of the fibrous resin reinforcing agent, the self-care vitamin (share) is changed to POEM J-002 1 to ten glycerol monooleate- 24-201245293 A fibrous resin reinforcing agent and a resin composition were produced in the same manner as in Example i except for the additive of the main component (manufactured by Lithium Vitamin Co., Ltd., POEM [registered trademark] J-03 8 1 V; HLB = 12.0). The molded body was obtained by measuring the amount of water of the obtained fibrous resin reinforcing agent by 15 〇 by the TG-DTA. The mass reduction of the underarm was 2.29 mass%. The fine cellulose in the obtained fibrous resin reinforcing agent was observed. A polarizing microscope photograph showing the state of dispersion of the fibers is shown in Fig. 2. A polarizing microscope photograph showing the state of dispersion of the finely divided cellulose fibers in the resin composition containing the fibrous resin reinforcing agent is shown in Fig. 7. [Example 3: Production of fibrous resin reinforcing agent, resin composition, and molded body from purified pulp] 50 parts by mass of purified pulp was dispersed in 400 parts by mass of pure water, and subjected to homogenizer treatment (ΜIC R Ο TEC NITIΟ N P hyscotr ο n ) (1 5,000 rpm, 1 hour), and coarse pulverization was carried out. Then, in the same manner as in Example 1, cellulose finening treatment was carried out, and an additive containing dicham monolaurate as a main component was added (manufactured by vitamins) (Stock), P OEM [Registered Trademark] J-002 1) 'A fibrous resin reinforcing agent was obtained by removing moisture, and then a resin composition and a molded body were produced. The moisture content of the obtained fibrous resin reinforcing agent was measured by the TG-DTA of 15 (the mass reduction after TC was 2.94% by mass. The dispersed state of the finely divided cellulose fibers in the obtained fibrous resin reinforcing agent was observed. The polarizing microscope photograph is shown in Fig. 3, and a polarizing microscope photograph of the dispersion of the fine cellulose fibers in the resin composition containing the fibrous resin reinforcing agent in the state of -25 to 201245293 is shown in Fig. 8. [Example 4: Bacterial cellulose production of fibrous resin reinforcing agent, resin composition, and molded body] 2,000 parts by mass of bacterial cellulose (PT. NIRAMAS, manufactured by UTAMA Co., Ltd.) was cut with scissors, and finely cut with a household mixer. The obtained aqueous dispersion (about pH 3) was filtered, and then washed with 500 parts by mass of water, and the operation was repeated until the pH of the dispersion was 7. The homogenizer was applied to the thus obtained aqueous dispersion. The mixture was centrifuged (1 5,000 rpm, 1 hour), and coarsely pulverized to obtain an aqueous dispersion of bacterial cellulose. Then, cellulose was treated in the same manner as in Example 1. The refining treatment is carried out by adding an additive containing ten glycerol monolaurate as a main component (manufactured by Lithium Vitamin Co., Ltd., POEM [registered trademark] J-002 1 ), and removing the water to obtain a fibrous resin reinforcing agent, followed by obtaining a fibrous resin reinforcing agent. The resin composition and the molded body were produced. The polarizing microscope photograph of the dispersed state of the fine cellulose fibers in the obtained fibrous resin reinforcing agent is shown in Fig. 4, and the resin composition containing the fibrous resin reinforcing agent was observed. A polarizing microscope photograph of the dispersed state of the fine cellulose fibers is shown in Fig. 9. [Comparative Example 1: Production of a fibrous resin reinforcing agent and a resin composition from a commercially available cellulose powder] A molded body (3)] In addition to the fibrous resin reinforcement Additives used in the manufacture of the agent, self-care vitamins (shares) to POEM [registered trademark] J-002 1 changed to an additive containing ten gan-26-201245293 oil monolaurate (manufactured by vitamins) A fibrous resin reinforcing agent, a resin composition, and a molded body were produced in the same manner as in Example 1 except that 'POEM [registered trademark] DL-100; HLB = 9.4). The obtained fibrous resin reinforcing agent was obtained. The component was measured by the TG-DTA to determine the mass reduction at 150 ° C, which was 1.79 mass %. The polarizing microscope photograph of the dispersed state of the fine cellulose fibers in the obtained fibrous resin reinforcing agent was observed. 5. A polarizing microscope photograph showing the state of dispersion of the finely divided cellulose fibers in the resin composition containing the fibrous resin reinforcing agent is shown in Fig. 1. [Comparative Example 2: Resin composition containing commercially available cellulose powder Manufacture of a molded article] Addition of polyglycerol monolaurate as a main component to 180 parts by mass of Polylactic acid (Ingeo [registered trademark] 3001D, manufactured by NatureWorks Co., Ltd.) Trademark]J_ 0021) 18 parts by mass, commercially available cellulose powder (made by Celite)?丨1)^-Cell BH-100) 2 parts by mass, using a twin-screw extruder (made by Toyo Seiki Seisakusho Co., Ltd., LABO PLASTOMILL, 2D15W), melt-kneading at a cylinder temperature of 1 90 °C A resin composition containing 1% by mass of cellulose fiber powder in polylactic acid was obtained. A polarizing microscope photograph of the dispersed state of the commercially available cellulose powder in the obtained resin composition was observed in Fig. 11 Next, a molded body was produced in the same manner as in Example 1. -27-201245293 [Comparative Example 3: Production of a fibrous resin reinforcing agent containing a coarsely pulverized pulp, a resin composition, and a molded body] An aqueous dispersion of coarsely pulverized pulp obtained in the same manner as in Example 3 (cellulose amount: 3.5 mass) In the same manner as in the case of the first embodiment, an additive containing dicham monolaurate as a main component (manufactured by Lithium Vitamin Co., Ltd., POEM [registered trademark] J-002 1 ) was added, and the content was obtained by removing water. The fibrous resin reinforcing agent of the pulp is coarsely pulverized, and then a resin composition and a molded body are produced. A polarizing microscope photograph showing the dispersion state of the coarsely pulverized pulp in the resin composition containing the obtained fibrous resin reinforcing agent is shown in Fig. 12. [Comparative Example 4: Production of a fibrous resin reinforcing agent containing a coarsely pulverized bacterial cellulose, a resin composition, and a molded body] In the aqueous dispersion of coarsely pulverized bacterial cellulose obtained in the same manner as in Example 4, and Example 1 Similarly, an additive containing glycerol monolaurate as a main component (manufactured by Lithium Vitamin Co., Ltd., POEM [registered trademark] J-〇〇2 1 ) is added, and by removing moisture, a cellulose containing coarsely pulverized bacteria is obtained. A fibrous resin reinforcing agent is then produced into a resin composition or a molded body. A polarizing microscope photograph showing the dispersion state of the coarsely pulverized bacterial cellulose in the resin composition containing the obtained fibrous resin reinforcing agent is shown in Fig. 13. [Comparative Example 5: Production of a resin composition and a molded article containing no cellulose fibers and additives] Polylactic acid (Ingeo [registered trademark] -28-201245293 3001D, manufactured by NatureWorks Co., Ltd.), using a twin-screw extruder (Toyo Seiki) The company (manufactured by the company), LABO PLASTOMILL, twin-screw extruder 2D15W), melt-kneaded at a cylinder temperature of 1 90 t to obtain a resin composition. Then, a molded body was produced in the same manner as in Example 1. [Comparative Example 6: Production of a resin composition containing only an additive, and a molded article] In a portion of 182 parts by mass of polylactic acid (Ingeo [registered trademark] 00 1D, manufactured by NatureWorks Co., Ltd.), tetradecyl monolaurate was added as a main component. Additives (manufactured by Vitamins, POEM [registered trademark] ΙΟ 021 ) 1 8 parts by mass using a twin-screw extruder (Toyo Seiki Co., Ltd., LABO PLASTOMILL, 2D15W) The mixture was melt-kneaded at a cylinder temperature of 19 ° C to obtain a resin composition. Then, a molded body was produced in the same manner as in Example 1. The types of cellulose fibers and additives used in the fibrous resin reinforcing agents obtained in Examples 1 to 4 and Comparative Examples 1 to 6, the diameters of the cellulose fibers obtained by particle size measurement, and the use of such fibrous resin reinforcing agents The weight average molecular weight of the obtained resin composition and the notched impact test of the molded body evaluated by the concave impact test in accordance with Π SK 7 1 1 0 are shown in Table 1. -29- 201245293 [1® Evaluation of Resin Composition and Shaped Body Weight average molecular weight Mw 136,000 103,000 128,000 141,000 138,000 146,000 133,000 115,000 〇〇Λ § 139,000 Notch impact strength kJ/m2 30.9 28.7 28.7 32.1 14.5 17.4 14.5 19.0 15.9 20.2 S _ i面^ 〇11 i§ ψ im ^ 狸藏鐽异•N m S | 登_ t « 1 ^ ffi ml Sm *N iS | I _ 1 HLB 16.0 12.0 16.0 1 | 16.0 inch cK 16.0 16.0 16.0 1 16.0 f=5 腾 ilrnii P POEM J0021 POEM J0381V POEM J0021 POEM J0021 POEM DL100 POEM J0021 POEM J0021 POEM J0021 1 POEM J0021 Cellulose fiber 値 diameter / / m 〇 VO Ο 14.0 33.7 Ο 48.9 (N 1 fS 1 1 1 Commercially available cellulose fine refining Commercially available cellulose Micronized purified pulp Micronized bacterial cellulose Micronized Commercial cellulose Commercially available cellulose powder (4) Crushed pulp coarsely pulverized bacterial cellulose 1 1 Example 1 Example 2 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 1 Comparative Example 4 Comparative Example 5 Comparative Example 6 二欢异滕赵伥枭 Accounts 鐽_汩3|骝仔饀忒 embedded炱Μ '劝洽忉-瑕湮鲤^Helmets follow the crazy key ^ ^:^冢镒丑一※ -30- 201245293 <Results Discussion> [Observation by polarized light microscope] In Fig. 1 to Fig. 13, the portion with high white brightness indicates the presence of cellulose. Fig. 1 to Fig. 4 The fiber-like resin reinforcing agent obtained in Example 4 was observed, and the cellulose fibers in the additive (HLB値: 1 2 to 16) were maintained in a fine fiber state, and the dispersibility was high. The fibrous resin reinforcing agent obtained in Comparative Example 1 shown in Fig. 5 is a result of aggregation of cellulose fibers and deterioration of uniform dispersibility as compared with the examples. Further, Example 1 in which these fibrous resin reinforcing agents are blended is used. In the resin composition of Example 4 (Figs. 6 to 9), the dispersibility of the cellulose fibers was also observed to be high. On the other hand, the resin composition of the fibrous resin reinforcing agent obtained in Comparative Example 1 was used (Fig. 10) In the above, the cellulose fibers which are agglomerated are dispersed in the resin as compared with the examples, and the resin composition in which the commercially available cellulose powder and the additive are added without passing through the form of the fibrous resin reinforcing agent is compared with the comparative example. 2 (Fig. 1 1), add separately Resin composition of coarsely pulverized pulp or coarsely pulverized bacterial cellulose resin reinforcing agent: Comparative Example 3 (Fig. 12) and Comparative Example 4 (Fig. 13) were compared with the examples to be in a very large particle or fiber state. Existence, the result of poor uniformity. [Formability] The resin composition or the molded body containing the fibrous resin reinforcing agent obtained by the present invention can be melt-kneaded at the same melting temperature as that of the conventional polylactic acid (the twin-screw extruder's cylinder temperature is 1 90 ° C). Next, injection molding -31 - 201245293 can be melted at the same cylinder temperature (200 °C) as that of the conventional polylactic acid, and the result can be emitted in a mold at 30 °C. [Impact Resistance] As is apparent from Table 1, the impact resistance of the resin composition or the molded body containing the fibrous resin reinforcing agent obtained by the present invention was remarkably improved. Specifically, in Examples 1 to 4 and Comparative Examples 1 to 6, Example 1 and Example 2 of the commercially available cellulose powder subjected to the micronization treatment, Example 3 in which the finely purified pulp was prepared, and the micronized bacteria were formulated. In Example 4 of cellulose, the impact strength was remarkably improved as compared with Comparative Examples 1 to 6, and the physical properties due to the addition of the fine cellulose fibers were observed to be improved. In particular, Example 1 and Example 2 using a resin composition (molded body) using a commercially available cellulose powder which is also subjected to a micronization treatment, but using a fibrous resin reinforcing agent having an additive of different HLB(R) In Comparative Example 1, when Comparative Example 1 in which the HLB of the additive was 9.4, no improvement in impact strength was observed as compared with the resin composition of Comparative Example 5 in which the additive and the cellulose fiber were not added. In Example 1 and Example 2 of 10 or more, the results of the impact strength were remarkably improved. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a polarizing microscope photograph showing a state in which a fine cellulose fiber is dispersed in a fibrous resin reinforcing agent produced in Example 1. Fig. 2 is a polarizing microscope photograph showing the dispersion state of the microfibrillated cellulose fibers of -32-201245293 in the fibrous resin reinforcing agent produced in Example 2. Fig. 3 is a polarizing microscope photograph showing the state of dispersion of the fine cellulose fibers in the fibrous resin reinforcing agent produced in Example 3. Fig. 4 is a polarizing microscope photograph showing the state of dispersion of the fine cellulose fibers in the fibrous resin reinforcing agent produced in Example 4. Fig. 5 is a polarizing microscope photograph showing the state of dispersion of the fine cellulose fibers in the fibrous resin reinforcing agent produced in Comparative Example 1. Fig. 6 is a photograph of a polarizing microscope for observing the dispersed state of the finely divided cellulose fibers in the resin composition containing the fibrous resin reinforcing agent produced in Example 1. Fig. 7 is a photograph of a polarizing microscope for observing the dispersed state of the finely divided cellulose fibers in the resin composition containing the fibrous resin reinforcing agent produced in Example 2. Fig. 8 is a photograph of a polarizing microscope for observing the dispersed state of the finely divided cellulose fibers in the resin composition containing the fibrous resin reinforcing agent produced in Example 3. Fig. 9 is a photograph of a polarizing microscope for observing the dispersed state of the finely divided cellulose fibers in the resin composition containing the fibrous resin reinforcing agent produced in Example 4. Fig. 1 is a polarizing micrograph showing the state of dispersion of the finely divided cellulose fibers in the resin composition containing the fibrous resin reinforcing agent produced in Comparative Example 1. Fig. 11 is a polarizing microscope photograph showing the dispersion state of a commercially available cellulose powder in the resin composition prepared in Comparative Example 2. -33-201245293 Fig. 1 2 is a polarizing microscope photograph of the state in which the resin composition containing the fibrous resin reinforcing agent prepared in Comparative Example 3 was dispersed in the coarsely pulverized pulp. Fig. 13 is a photograph of a polarizing microscope for observing the dispersion state of the coarsely pulverized bacterial cellulose in the resin composition containing the fibrous resin reinforcing agent prepared in Comparative Example 4. -34-