200923008 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用有彈性體之橡皮擦及其製造方 法’詳細而言’係關於一種不需依存石化資源、能夠回收、 對環境負擔少且因應循環型社會之橡皮擦及其製造方法。 【先前技術】 截至目前’產業、經濟是隨著石油、石碳等之石化資 源的利用而發展，而建構出大量生產、大量消費、大量廢 棄的社會系統’現在多生活的基礎都是依存著預料會 枯竭的石化資源。 現在的社會系統雖能創造出經濟的富裕與便利，和另 ::面超過自然淨化能力的廢棄物和二氧化碳的排出、地 球>皿暖化、有害物質等的環境問題也愈來愈嚴重。 v. 為了解決這些問題，正大力地謀求把目前為止這種將 源而來的商品大量生產、大量消 1、廢棄之單向 二 =改變’#變為抑制廢棄物的產生'將有限的資 ===型社會。面對此循環性社會的形成，曰 本統合 (biomass)· g 」且双力在產業競爭力的再建構上。 生質，意即自然的恩惠所帶來的可持續再 源。燃燒生質雖會排出二氧化碳，但 ：機貧 會吸收、固定大氣中的_ 、光《作用 氣化碳，此為其特徵所在。此…不曰广：二 —Μ)」，把石化資源而來的能量或製α以生曹：°η· 至-人表σ口 U生質的方式置 200923008 換使得二氧化碳的排放量可以大幅削減，因此，其技術以 及製品的開發正強力地被尋求當中。 近年’在高分子材料上，出現許多考慮到循環型社會 的形成的提案。 例如，天然橡膠和生物分解性塑膠所構成之橡膠製造 用組成物（在實施例中使用加硫劑、加硫促進劑）（專利文獻 1)，生物分解性材料和環氧化聚異戊二烯、如必要更進一 步混合交聯劑所得之生物分解性材料組成物（專利文獻2)， 在天然橡膠中添加生物分解性樹脂和填充劑之生物分解性 橡膠組成物（專利文獻3)，由結晶性聚乳酸和選自天然橡 勝、聚異戊二財之橡勝成分所構成之聚乳酸系樹脂組成 物（專利讀4)，聚乳酸所構成之連續相中有天然橡膠等 所構成之分散相均—微分散之高分子摻合材料（專利文獻 〃 一不面，橡皮擦可大致分為由氣乙烯樹脂所構成之 皮擦、由苯乙稀系熱可塑性彈性體或稀烴系熱可 = :所構成之非氯乙烯橡皮擦、以及天然橡膠橡皮 的市場2I乙稀橡皮擦、非氯乙烯橡皮擦佔了超過九成 劑都是源自==擦之高分子材料或是可塑劑、軟化 會違反上、+.，貧源的材料，繼續利用此等橡皮擦 會堤反上4之循環型社會形成的主旨。 造之天然橡皮擦係從天然橡膠或由植物油所製 ”（硫化油膏：—)等之活用生質且因應循環 200923008 型 社會形成的主旨之物（專利文獻6,非專利文獻υ。 曰本專利文獻1 :特開平10-274494號公報 曰本專利文獻2 :特開2000-95898號公報 曰本專利文獻3 :特開2000-319446號公報 曰本專利文獻4 :特開2003-183488號公報 曰本專利文獻5 :特開20044433^號公報 曰本專利文獻6 :特開2〇〇〇_43492號公報（參見實施例200923008 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to an eraser using an elastomer and a method for manufacturing the same, 'detailed' relates to a kind of petrochemical resource that does not need to be stored, can be recycled, and has less environmental burden And in response to the eraser of the recycling society and its manufacturing methods. [Prior Art] Up to now, 'industry and economy have developed with the utilization of petrochemical resources such as petroleum and stone carbon, and have constructed a large-scale production, mass consumption, and a large number of abandoned social systems. Petrochemical resources expected to be depleted. Although the current social system can create economic affluence and convenience, and environmental problems such as the discharge of waste and carbon dioxide that exceeds the natural purification capacity, the earth, the warmth of the dish, and harmful substances, are becoming more and more serious. v. In order to solve these problems, we are vigorously seeking to make the production of such products from the mass production, mass elimination, and one-way disposal of the two-changed '# become waste suppression. ===type society. Faced with the formation of this circular society, this is the integration of biomass and g and the dual construction of industrial competitiveness. Biomass, meaning a sustainable source of natural bounty. Although burning biomass will emit carbon dioxide, but the machine will absorb and fix the _ and light in the atmosphere, which is characterized by its role in gasification. This is not enough: 2 - Μ)", the energy or system of the petrochemical resources to the production of Cao: ° η · to - people σ mouth U biogeneity set 200923008 change so that carbon dioxide emissions can be significantly Reduction, therefore, the development of its technology and products is being strongly sought. In recent years, there have been many proposals for the formation of a recycling society in polymer materials. For example, a rubber manufacturing composition composed of natural rubber and biodegradable plastic (a sulfurizing agent and a vulcanization accelerator are used in the examples) (Patent Document 1), a biodegradable material, and an epoxidized polyisoprene. Further, if necessary, a biodegradable material composition obtained by mixing a crosslinking agent is further added (Patent Document 2), and a biodegradable rubber composition containing a biodegradable resin and a filler is added to the natural rubber (Patent Document 3). A polylactic acid-based resin composition composed of a natural polyether and a rubber component selected from the group consisting of natural rubber and polyisoprene (patent read 4), and a dispersion composed of natural rubber such as polylactic acid Coherent-microdispersed polymer blending materials (patent literature 〃 不 , , , 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮 橡皮= : The non-vinyl chloride eraser and the natural rubber rubber market 2I Ethylene Eraser, non-vinyl chloride eraser accounted for more than 90% of the agent is derived from == rubbing polymer material or plasticizer Softening will violate the materials of the upper, +, and poor sources, and continue to use these erasers to counter the four-cycle society. The natural eraser is made of natural rubber or vegetable oil. In the case of the use of the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus Japanese Laid-Open Patent Publication No. JP-A No. 2000-319446 (Patent Document No. JP-A-2003-183488). JP-A-2-43492 (see the example)
非專利文獻1· 「橡膠工業便覽」（新版）日本橡膠協會 編表25.2 ’ 817頁’昭和48年η θ 15日社團法人橡膠協 會發行。 【發明内容】 然而，關於上述習知技術，因為沒有實施加硫或交聯 之橡膠其抗拉強度或彈性不夠，有些情況下用途會受限 制，例如作為橡皮擦用材料時無法展現橡膠彈性而不適 當。另一方面，也有因為實施加硫或交聯之橡膠其抗拉強 度或彈性過大而用途受限之情況，例如作為橡皮擦用材料 ，變硬且失去橡膠彈性因此不適t。再者，@ ^要加硫或 交聯步驟使得製程不僅複雜，對於加硫劑的硫或加硫促進 劑、助劑之氧化辞等之加硫藥劑的安全性也有报大的問 題0 另一方面’天然橡膠橡皮擦如同上述雖然適合循環型 杜會形成之要求，但例如跟氯乙烯橡皮擦相比其消字性能 車乂差、而且因包含加硫步驟所以比起氣乙烯橡皮擦或非氯 200923008 乙烯橡皮擦其製造步驟更為複雜，此外，如上所述也有硫 或加硫促進劑等加硫藥劑的安全性問題。再者，因製造步 驟内.產生之端材的再利用會有困難而不經濟，且在生產性 上也存有問題。 本發明人等為了解決上述習知技術之問題點，提供了 一種橡皮擦’其係含有於微生物所生產之聚（3_羥基丁酸酯 -共-3-羥基己酸酯（以下記為ΡίίΒΗ))所構成之基質中有交 聯天然橡膠粒子分散成島狀所得之彈性體而成者（專利申請 2007-29048 8、平成19年11月8日申請）。 ,，、、:而，含有上述PHBH而成之橡皮擦，雖能夠回收、 對環境負擔少且因應循環型社會，並且安全性優異，但和 氯乙烯橡皮擦相比，有消字能力並不一定足夠之問題。 本發明人等有鑑於實際情況’為解決上述問題而努力 研究的結果’發現本發明所使用之彈性體其與氣乙稀樹脂 之相办性優異’藉由含有該兩者，可提高彈性體所構成之 橡皮擦的消字性能，而完成本發明。 古’、即’本發明之請求項1内容為-種橡皮擦，其係含 ^^生物所生產之聚（3·經基丁㈣·共·3·經基己酸酿（以 二為ΡΗΒΗ))所構成之基質中有交聯天然橡膠粒子分散 成島狀所得之彈性體、以及氣乙稀樹脂而成。 刀散 本發明之凊求項2内宏五4 ε phrh 各 巧合為如5月求項1之橡皮擦，其中， ΗΒΗ之重複單位的組 己酸Wx上、2 ^ (3_线丁㈣）/聚（3·趣基 上 99/1 以下（mol/mol)。 本發明之請求項3内 令為如凊求項1或2之橡皮擦， 200923008 其中’彈性體係藉由將PHBH、天然橡 之熔融溫 橡膠交聯劑於 又从上且橡膠父聯劑之交聪、迫 混練，來使得續哪，皿度以上加以 便仔該PHBH所構成之基f令分 粒子而成者。 欣有該交聯橡膠 本發明之請求項4之内容為如請求項 之橡皮擦，JL中，踩至3中任一項 八 彈性體為天然橡膠50 〇〇 PHBH50〜1會旦。/ 0〜99重量％、 更里八、及橡膠交聯劑相對於 量份為0.1〜5啻旦八, 天然橡膠100重 «仏所構成之彈性體橡皮擦植成物。 發明之請求項5内容為如請求項 一步含有軟化劑。 橡皮擦，其進 本發明之請求項6内容為如請求項 軟化劑係來自生質。 、之橡皮擦，其中， 本發明之請求項7之内容為如請 其中，軟化劑儀撰唄次6之橡皮擦， 本發明β β $ 目於動植物油之可塑劑。 項㈠容為如請求 橡皮擦，其中，赴& ^^ 項5至7中任一項之 敕化劑相對於天然橡膠蛊 重量份為〜P_之合汁100 本發明之請求項9内容為如 橡皮擦，其進-步含有填充劑。項4至8中任一項之 本發明之請求項J 〇内容 < 填充劑係來自生質。 ‘，、、租永項9之橡皮擦，其中， 本發明之請求項丨丨内容 ▲主 豆中，埴右才丨〆 ' 為如δ月永項9或10之橡皮擦， 其中填充劑係選自貝殼粉末、 本發明之技4 粉末。 …12内容為如請求項9至η中任一項 200923008 橡皮其中，填充劑相對於天然橡膠與ΡΗΒη之合計 10〇重量份為10〜1000重量份。 本發月之1求項13内容為如請求項丨至12中任—項 橡皮其中，氯乙烯樹脂為氣乙烯樹脂} 00重量份、 Hhowo重4份所構成之氯乙烯樹脂橡皮擦組成物。 本發明之請求項14内容為-種橡皮擦之製造方法，其 、徵在於係、將彈性體橡皮擦組成物所構成之橡皮擦、氣 乙烯樹脂橡皮擦紙成物所構成之橡皮擦加以熔融混練、成 形。 止本發月之。月求項15内容為如請求項14之橡皮擦之製 方法其中彈性體橡皮擦組成物係由天然橡膠5〇〜99 重里％ PHBH50〜1 ^量％、及橡谬交聯劑相對於天然橡勝 100重份為〇.1〜5重量份所構成。Non-Patent Document 1· "Rubber Industry Fact Sheet" (new edition) Japan Rubber Association Schedule 25.2 ‘817 </ s> Showa 48 η θ 15th Corporate Rubber Rubber Association issued. SUMMARY OF THE INVENTION However, with regard to the above-mentioned prior art, since the rubber which is not subjected to vulcanization or cross-linking is insufficient in tensile strength or elasticity, the use may be limited in some cases, for example, the rubber elasticity may not be exhibited as a material for an eraser. Not appropriate. On the other hand, there are cases where the rubber which is subjected to vulcanization or cross-linking has a tensile strength or elasticity which is too large and its use is limited. For example, as a material for an eraser, it hardens and loses rubber elasticity and is therefore unsuitable. Furthermore, @^ has to add sulfur or cross-linking steps to make the process not only complicated, but also the safety of the sulfur-adding agent such as the sulfur or vulcanization accelerator of the vulcanizing agent or the oxidizing agent of the auxiliary agent. In terms of the above-mentioned 'natural rubber eraser, although it is suitable for the formation of the circulating type Duhui, it is worse than the vinyl chloride eraser because of its poor performance, and because it contains a vulcanization step, it is more than an ethylene eraser or a non-e. Chlorine 200923008 The ethylene eraser is more complicated in its manufacturing process. In addition, as mentioned above, there are also safety problems of sulfur-added chemicals such as sulfur or a vulcanization accelerator. Furthermore, the reuse of the end material produced in the manufacturing step is difficult and uneconomical, and there is also a problem in productivity. In order to solve the problems of the above-mentioned prior art, the present inventors have provided an eraser which is a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate produced by a microorganism (hereinafter referred to as ΡίίΒΗ). (a) The above-mentioned matrix is composed of an elastomer obtained by dispersing the crosslinked natural rubber particles into an island shape (patent application No. 2007-290488, filed on November 8, 1999). ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, There must be enough problems. The inventors of the present invention have found that the elastomer used in the present invention is excellent in coherence with the ethylene-epoxy resin in view of the actual situation, and the elastomer used in the present invention is improved by the inclusion of both. The eraser performance of the constructed eraser completes the present invention. The ancient ', that is, the content of the claim 1 of the present invention is an eraser, which is composed of a poly(3·pyridinium (tetra)·co-3·perylene hexanoic acid produced by the ^^ organism. )) The matrix is composed of an elastomer obtained by dispersing crosslinked natural rubber particles in an island shape and a vinyl ether resin. Knife Dispersion The intent of the invention 2 Inner Macro 5 4 ε phrh Each coincidence is an eraser such as the May 1 item, in which the group of repeating units of hexanoic acid Wx, 2 ^ (3_ line (4)) /聚(3. The following is based on 99/1 (mol/mol). The claim 3 of the present invention is an eraser as claimed in item 1 or 2, 200923008 wherein 'elastic system by PHBH, natural oak The molten warm rubber cross-linking agent is used in the cross-over and rubber-parent agent to make the cross-training and forced mixing, so that the continuation of the above-mentioned degree can be added to the base of the PHBH to make the particles. The crosslinked rubber The content of the claim 4 of the present invention is the eraser as claimed in the JL, and the one of the eight elastomers which are stepped to 3 is a natural rubber 50 〇〇PHBH50~1 meeting denier. / 0~99 weight %, more ali, and the rubber cross-linking agent is 0.1~5 啻8, and the natural rubber 100 仏 仏 弹性 弹性 弹性 弹性 弹性 弹性 。 。 。 。 。 。 。 。 。 。 。 。 。 弹性 弹性 弹性 弹性 弹性 弹性 弹性 弹性 弹性 弹性 弹性One step contains a softener. The eraser, which is in the scope of claim 6 of the present invention, is as claimed in the softener from the raw material. The content of the claim 7 of the present invention is as follows, the softener is written as the eraser of the sixth, and the ββ$ of the present invention is a plasticizer for the animal and vegetable oil. The item (1) is as requested, such as an eraser. The content of the deuteration agent according to any one of items 5 to 7 with respect to the natural rubber crucible is -P_100. The content of claim 9 of the present invention is as an eraser, and the step-by-step contains Filler. The claim J of the present invention according to any one of items 4 to 8 is the content of the filler from the raw material. The eraser of the renting item 9, wherein the request of the present invention is 丨丨Content ▲ In the main bean, 埴右才丨〆' is an eraser such as δ月永永9 or 10, wherein the filler is selected from the group consisting of shell powder, the powder of the invention 4 ... 12 contents as in claim 9 Any one of η 200923008 rubber wherein the filler is 10 to 1000 parts by weight based on 10 parts by weight of the total of the natural rubber and the ΡΗΒη. The content of the item 13 of the present month is as claimed in the item 丨 to 12 In the rubber, the vinyl chloride resin is 00 parts by weight of the ethylene resin, and the chlorine consisting of 4 parts of the Hhowo The olefin resin eraser composition. The content of claim 14 of the present invention is a method for manufacturing an eraser, which is characterized in that an eraser composed of an elastomer eraser composition and a vinyl rubber eraser paper product are used. The eraser is melted and kneaded and formed. The present invention is the method of the eraser of claim 14, wherein the elastomer eraser composition is made of natural rubber 5〇~99% The PHBH 50 〜1 ^ % by weight, and the rubber crosslinking agent are composed of 〜. 1 to 5 parts by weight relative to 100 parts by weight of the natural rubber.
寂本&明之明求項16内容為如請求項或15之橡皮 τ之衣k方法’其令’ t乙烯樹脂橡皮擦組成物係由氯乙 稀樹脂刚重量份、可塑劑6〇〜18〇重量份所構成。 如請求項14至1 6中任一項 彈性體橡皮擦組成物所構成 乙稀樹脂橡皮擦組成物所構 本發明之請求項17内容為 之橡皮擦之製造方法，其中， 之橡皮擦為30〜90重量％、氣 成之橡皮擦為70〜1〇重量％。 本發明令所用之彈性體不需依存石化資源’用作為原 枓之材料係來自生質之天然橡膠及來自生質之生物分解性 聚酉旨系之塑料PHBH，因此，即使廢棄亦不會使空氣中 的二氧化碳增加，纟自然環境下會受到分解，為環境適應 200923008 型之彈性體。 因此’本發明之彈性體與氣 、虱乙烯樹脂所構成之橡皮擦 與以在之乳乙稀橡皮擦相比，可试w J减輕對環境造成之負荷。 且在廢棄階段’將彈性體以堆脃 ^ L ^ v *肥4手段使之預先生物分 解，藉此可將氯乙烯樹脂分離、回收。 又，本發明所使用之彈性砰 f體因為是熱可塑性彈性體， 故成形時所產生之端材可易於掂 勿、僱缞，因此，可謀求降低成 本同時適合資源循環型社會。 本’X月所使用之彈性體’因天然橡膠肖ρΗΒΗ的混練 和天然橡膠的交聯是同時進行1以步驟被簡略化，生產 I·生於疋提间。此外’因於天然、橡膠之交聯不使用硫、氧化 鋅等之加硫劑或加硫促進劑，所以安全性也提高。 再者，以往之天然橡膠橡皮擦必須要有混練步驟以外 其他的交聯步w ’相對於此，本發明所使用之彈性體因交 聯與混練同時進行，故步驟簡化而生產性提高。 又，以往之天然橡膠橡皮擦係使用硫、氧化辞等加硫 劑或加硫促進劑，相對於此，本發明之橡皮擦因未使用此 種藥劑故安全性亦高。 再者而且本發明之橡皮擦與以往之天然橡膠橡皮擦或 非氯乙烯橡皮擦相比，消字能力高。 【實施方式】 本發明之橡皮擦特徵在於：係含有於PHBH所構成之 基貝中有父聯天然橡膠粒子分散成島狀所得之彈性體、以 及氣乙稀樹脂而成。 11 200923008 本發明之橡皮擦雖可將彈性體與氣乙烯樹脂和軟化 劑、填充材、可塑劑、著色劑、香料等添加物一起加以熔 融混練並成形，但由可有效提高消字性能之觀點來看較 佳係將彈性體橡皮擦組成物所構成之橡皮擦與氯乙烯樹脂 橡皮擦組成物所構成之橡皮擦加以混合進行熔融混練。因 此，以下，沿循此較佳之方法進行說明。 本發明中所用之彈性體係於PHBH所構成之基質（海） 中有父聯天然橡膠粒子分散成島狀之海島構造所構成者。The content of the book is as follows: the request item or the rubber τ of the 15th method. The method of the vinyl eraser composition is from the weight of the vinyl chloride resin, the plasticizer 6〇~18 It consists of 〇 by weight. The method for manufacturing an eraser according to claim 17 of the present invention, wherein the eraser composition of any one of claims 14 to 16 is composed of an elastomer eraser composition, wherein the eraser is 30 ~90% by weight, the air-cured eraser is 70~1% by weight. The elastomer used in the present invention does not need to be dependent on the petrochemical resources. The material used as the original material is the natural rubber derived from the raw material of the raw material and the plastic PHBH derived from the biodegradable polyglycolate of the raw material. Therefore, even if it is discarded, it will not be The increase of carbon dioxide in the air will be decomposed in the natural environment, adapting to the environment of the 200923008 elastomer. Therefore, the eraser composed of the elastomer of the present invention and the gas and the vinyl resin can reduce the load on the environment as compared with the eraser eraser. Further, in the discarding stage, the elastomer is preliminarily decomposed by means of a stack of L ^ v * fertilizer 4, whereby the vinyl chloride resin can be separated and recovered. Further, since the elastic body used in the present invention is a thermoplastic elastomer, the end material produced during molding can be easily handled and employed, and therefore, it is possible to reduce the cost and suit the resource recycling society. The elastomer used in the 'X month' was mixed with the natural rubber by the mixing of the natural rubber and the natural rubber. The steps were simplified in the first step, and the production was carried out in the kitchen. In addition, since the sulfurization agent such as sulfur or zinc oxide or the sulfurization accelerator is not used for the crosslinking of natural rubber, the safety is also improved. Further, in the conventional natural rubber eraser, it is necessary to have other crosslinking steps other than the kneading step. In contrast, since the elastomer used in the present invention is simultaneously subjected to crosslinking and kneading, the steps are simplified and the productivity is improved. Further, in the conventional natural rubber eraser, a sulfur-adding agent such as sulfur or an oxidizing agent or a vulcanization accelerator is used. On the other hand, the eraser of the present invention has high safety because it is not used. Further, the eraser of the present invention has a high erasing ability as compared with the conventional natural rubber eraser or non-vinyl chloride eraser. [Embodiment] The eraser of the present invention is characterized in that it is composed of an elastomer obtained by dispersing a parent rubber natural rubber particle in an island shape and a gas-thin resin in a base made of PHBH. 11 200923008 The eraser of the present invention can melt and knead and form an elastomer together with a gas-vinyl resin and a softener, a filler, a plasticizer, a colorant, a fragrance, etc., but the viewpoint of effectively improving the character of the word can be improved. In view of the above, an eraser composed of an elastomer eraser composition and an eraser composed of a vinyl chloride resin eraser composition are preferably mixed and melt-kneaded. Therefore, the following description will be made along the preferred method. The elastic system used in the present invention is composed of a sea-island structure in which a parent-linked natural rubber particle is dispersed into an island shape in a matrix (sea) composed of PHBH.
本發明中所用之天然橡膠，隨乳膠到固態橡膠之加工 的方法不同分成席特膠（seat rubber)、佩爾膠（pale以邛勻、 布朗膠（br〇Wn craPe)、布蘭凱特膠（blanket Crape)、布落克 膠（bolck rubber)、庫拉姆膠（crumb rubber)等種類，雖有各 種的品質等級’但本發明對此並無限制，f可利用，也無 產地限制。此外，如環氧化天然橡膠般之天然橡膠衍生物 也可利用。I亥等可單獨使用’視情況也可組合2種以上來 使用。 本發明中彈性體中所用之pHBH，如日本專利特開 2007-77232號公報所記載，微生物所生產，且重複單位之 組成比由柔軟性與強度平衡之觀點來看，聚（3_經基丁酸醋）〆 聚（3-經基己酸醋）為80/2〇以±、99/1以下（_/叫較佳。 酬Η藉由改變重複單位之組成比，可使融點、結晶化度 變化，且亦可能使揚格模量、《熱性等物性變化，並且可 使之具有聚丙烯至聚乙烯之範圍的物性。 天然橡膠與ΡΗΒΗ之組成比率可視目的之彈性體組成 12 200923008 物的用it或物I生來適當決$，例如作為橡皮擦之基材來 說，天然橡膠為50〜卯重量％、pHBH為”〜丨重量％之範 圍較佳，更佳為天然橡膠70〜95重量％、阳冊為3〇〜5重 量％。PHBH若未滿！重量％，則有時彈性體組成物之流動 性差且成形性有問題βΡΗΒΗ^超過5()重量％，則有彈性 體組成物變硬而橡㈣性未充分展現，且無法發揮充分消 字性能之傾向。 以本發明所用之橡膠交聯劑而言，可適宜使用有機過 氧化物具體而吕，例如有過氧化二異丙苯(例如日本油脂 公司製帕格米_ D)、2,5_二甲基_2,5_二_第三τ基過氧化己 烷（例如曰本油脂公司製帕赫奇沙25β)、二-第三丁基過氧 化二異丙笨（例如日本油脂公司製帕布其爾ρ)、2,5_二甲基 -2,5 一帛二丁基過氧化己炔_3(例如日本油脂公司製帕赫 奇辛25Β)等。此外，也可使用其他有機加硫劑。具體而言， Ν，Ν間-苯伸一馬來醯亞胺（例如大内新興化學公司製巴爾 諾克ΡΜ)、對-苯醌二肟（例如大内新興化學公司製巴爾諾 克GM)烷基酚甲醛樹脂（例如大内田岡化學公司製塔奇羅 爾）等該等可單獨使用，視情況也可組合2種以上來 使用。 橡膠又聯劑相對於天然橡膠丨00重量份係使用〇 _ id O 重量份。橡膠交聯劑未滿θ ΐ重量份則交聯會不充分、天 然橡膠無法成為粒子而得不到想要的構造。另一方面，超 過5·〇重量份則交聯粒子的反彈性會過大，有產生成形性 問題的傾向。 13 200923008 如上㈣PHBH、天然橡膠及橡膠交聯劑所構成之彈 性體橡皮擦組成物亦可進一步視需要適當地任意添加軟化 劑、填充劑、有機、無機顏料，染料等芸ώ '巴何、香料、安 定劑、抗氧化劑、紫外線吸收劑、光劣化防止劑、防徽劑 等其他添加物。 以軟化劑而言’可以使用礦物油 '動植物油或源自礦 物油、動植物油之可塑劑。以破物油而言，具體而言例如 有石蠟系加工處理油、環烷系加工處理油、芳香族系加工 處理油等。以動植物油而言，具體上例如有菜籽油、藥麻 I油、棉實油、亞麻仁油、大豆油、胡麻油、玉米油、紅 论油、棕櫊油、椰子油、落花生油、木蠟、松香、松焦油、 松油等。以源自動植物油之可塑劑而t，例如有甘：脂肪 酸酯等’具體上例如有甘油二丙酮單月桂酸酯、甘油三醋 酸酯、甘油二醋酸酯等。該等可單獨使用，視情況也可組 合2種以上來使用。w可提供更具環境適應型《彈性體组 成物的觀點而t，使用可再生資源之源自生f之動植物油 或源自動植物油之可塑劑是較佳的。 軟化劑的配合量，一般相對於天然橡膠與phbh的曰 合：⑽重量份而言可以添…〇〇重量份。添加ι〇〜二 重讀較佳。軟化劑的配合量若未滿1重量份則軟化劑之 =量不足’另一方面’超㉟200重量份則有參出⑽ed) 之虞。 —填充劑可舉出：重質碳酸辦、輕質碳酸詞、二氧化石夕、 矽凍土、氧化鎂、氧化鈦、滑石、雲母、石英粉末、蒙脫 14 200923008 石、扇貝、牡蠣、蛤等貝殼粉末'蛋殼粉末、有機中空粒 子、無機中空粒子等。此等可單獨使用，視情況也可組合 2種以上來使用。以可提供更具環境適應型之彈性體組成 物的觀點而言，使用大量產生成為廢棄物之來自生質之扇 貝、牡蠣等貝類粉末或蛋殼粉末較佳。 填充劑之配合量，通常相對於天然橡膠與之混 合物100重量份為10〜;1000重量份。較佳為5〇〜5〇〇重量 份。未满10重量份，則填充劑之添加效果不足，另一方 面，若超過1000重量份，則有組成物變硬而橡膠彈性未 充分展現’且無法發揮充分消字性能之傾向 如上所述’彈性體橡皮擦組成物可藉由在PHBH之熔 融溫度以上且橡膠交聯劑之交聯溫度以上混練而獲得。混 練較佳係在高剪切下進行，而此種混練機可舉出雙軸混練 擦製機、班伯里混合機、加壓捏合機、混合觀等。該等之 中以使用雙轴混練擠製機較佳。 PHBH之熔融溫度以上係指高於ρηβη之熔融溫度 10〜5 0 C之溫度為佳，又，橡膠交聯劑之交聯溫度以上係 指高於橡膠交聯劑之交聯溫度5〜20。(：之溫度為佳。 上述彈性體橡皮擦組成物可藉由加壓成形、射出成形、 擠壓成形等而成形，並裁切成既定之尺寸而得到橡皮擦。 另一方面，本發明中所用之氣乙烯樹脂並無特別限制， 係使用習知的氯乙烯樹脂’糊狀樹脂、原樹脂皆可。於氯 乙烯樹脂可添加可塑劑’進一步視情況可適當地任意添加 安定劑、著色料、香料等添加物。 15 200923008 就可塑劑而言，例如有苯二甲酸二辛基酯（D〇p)、苯 一曱酸一壬基酯（DNP)、苯二曱酸二異壬基酯（DiNp)、笨 一甲酸二異癸基酯（DIDp)、苯二甲酸二十三烷基酯 (DTDP)、苯二曱酸二十—烷基酯（DUp)等之苯二甲酸酯系 可塑劑；偏苯三甲酸二異辛基酯（TI〇TM)等之偏苯三甲酸 酯系可塑劑；聚I系可塑劑等，料可單獨使用，視情況 也可組合2種以上來使用。 可塑劑相對於氯乙烯樹脂1〇〇重量份添加6〇〜18〇重 量^、較佳為100〜160重量份。可塑劑的配合量若未滿1〇〇 重里份則組成物會變硬而無法充分發揮消字能力、另一方 面，超過160重量份則可塑劑會移動而有滲出之虞。 糊狀樹脂的情況，將糊狀樹脂與可塑劑、進一步視情 況和其他添加物所構成之橡皮擦組成物加以混練、脫泡後 將之流入既定深度的成形用金屬模具中，以既定的時間加 熱後々郃，然後從金屬模具中取出再以既定的尺寸裁切得 到橡皮擦。 f 另一方面，原樹脂的情況，原樹脂與可塑劑、視情況 和其他添加物所構成之橡皮擦組成物以射出成形機、擠製 成形機等使之成形，然後再以既定的尺寸裁切得到橡皮 擦。 "上述方式所得之彈性體橡皮擦組成物所構成之橡皮擦 與氯乙烯樹脂橡皮擦組成物所構成之橡皮擦以期望的比例 篁取，然後以加熱過的捏合機混練，冷卻後加以粉碎得到 小粒’再以射出成形、擠製成形等方式使之成形，然後再 16 200923008 以既疋的尺寸裁切得到本發明之高消字性能橡皮擦 彈性體橡皮擦組成物所構成之橡皮擦與氣乙焙4 t 皮擦組成物所構成之橡皮擦《混合比例並無特別曰橡 重點擺在資源回收或對環境負擔的減輕的 J以The natural rubber used in the present invention is divided into a seat rubber, a Pel (Pale), a brown rubber (br〇Wn craPe), and a Brancaite rubber according to the method of processing the latex to the solid rubber. Blanket Crape), bolck rubber, and crumb rubber have various quality grades, but the present invention is not limited thereto, and f is available and has no production restrictions. A natural rubber derivative such as an epoxidized natural rubber may be used. IHai or the like may be used singly or in combination of two or more kinds. The pHBH used in the elastomer of the present invention, such as Japanese Patent Laid-Open Publication No. 2007 Japanese Patent Publication No. 77-23232, which is produced by microorganisms, and the composition ratio of the repeating unit is from the viewpoint of balance between flexibility and strength, and poly(3-hydroxybutyric acid vinegar) ruthenium (3-aminohexanoic acid vinegar) is 80/2〇 is ±, 99/1 or less (_/ is better. Reward can change the melting point, crystallization degree by changing the composition ratio of the repeating unit, and can also make the Yangge modulus, "heat" Physical properties change, and can be made from polypropylene to polyethylene The physical properties of the range. The composition ratio of natural rubber to enamel can be determined by the purpose of the elastomer composition 12 200923008 The substance is made with it or the substance I, for example, as the substrate of the eraser, the natural rubber is 50~卯% by weight. The pHBH is preferably in the range of “~% by weight, more preferably 70 to 95% by weight of the natural rubber, and 3 to 55% by weight of the solar book. If the PHBH is less than % by weight, the elastomer composition may be When the fluidity is inferior and the formability is more than 5 (% by weight), the elastomer composition becomes hard and the rubber (tetra) property is not sufficiently exhibited, and the sufficient hyphenation performance is not exhibited. The rubber cross-linking used in the present invention As the agent, an organic peroxide can be suitably used, for example, dicumyl peroxide (for example, Pagmi _D manufactured by Nippon Oil Co., Ltd.), 2,5-dimethyl-2,5_2 The third τ-based peroxane (for example, Pachchsha 25β manufactured by Sakamoto Oil Co., Ltd.), di-t-butylperoxy-diisopropyl bromide (for example, Pabcil ρ manufactured by Nippon Oil Co., Ltd.), 2, 5 _Dimethyl-2,5-di-dibutylperoxyhexyne_3 (for example, Pach, manufactured by Nippon Oil & Fats Co., Ltd.) In addition, other organic sulfurizing agents can also be used. Specifically, hydrazine, hydrazine-benzene-extension-maleimide (for example, Barnock® manufactured by Okinawa Chemical Co., Ltd.), p-Benzene Alkyl phenol formaldehyde resin (for example, Barnock GM manufactured by Ouchi Shinko Chemical Co., Ltd.) can be used alone or in combination of two or more kinds as the case may be. The rubber jointing agent is used in an amount of 〇 _ _ O by weight relative to 00 parts by weight of the natural rubber ruthenium. If the rubber crosslinking agent is less than θ ΐ by weight, the crosslinking will be insufficient, and the natural rubber cannot be a particle and cannot be obtained. The desired construction. On the other hand, when the amount exceeds 5 parts by weight, the repulsive property of the crosslinked particles is excessively large, which tends to cause moldability problems. 13 200923008 (4) The elastomeric eraser composition composed of PHBH, natural rubber and rubber cross-linking agent may be further optionally added with softeners, fillers, organic and inorganic pigments, dyes, etc. as appropriate. Other additives such as stabilizers, antioxidants, ultraviolet absorbers, photodegradation inhibitors, and anti-indicators. In the case of softeners, mineral oils, animal and vegetable oils or plasticizers derived from mineral oils and animal and vegetable oils can be used. Specific examples of the fracture oil include paraffin-based processing oil, naphthenic processing oil, and aromatic processing oil. In terms of animal and vegetable oils, for example, rapeseed oil, medicinal oil I, cotton oil, linseed oil, soybean oil, sesame oil, corn oil, red oil, palm oil, coconut oil, groundnut oil, wood Wax, rosin, pine tar, pine oil, etc. The plasticizer of the source of the vegetable oil may be, for example, a glycerol: a fatty acid ester or the like. Specifically, for example, glycerol diacetone monolaurate, glycerin triacetate, glycerin diacetate or the like may be mentioned. These may be used alone or in combination of two or more kinds as appropriate. w can provide a more environmentally compatible "elastomer composition", and it is preferred to use a renewable resource derived from the vegetable oil of the raw material or the vegetable oil of the original automatic vegetable oil. The blending amount of the softener is generally relative to the blend of natural rubber and phbh: (10) parts by weight may be added. Add ι〇~2 Rereading is better. If the amount of the softener is less than 1 part by weight, the amount of the softener is insufficient. On the other hand, the excess of 35,200 parts by weight is as shown in (10) ed). - Fillers include: heavy carbonate, light carbonate, sulphur dioxide, sorghum, magnesium oxide, titanium oxide, talc, mica, quartz powder, montmorillon 14 200923008 stone, scallop, oyster, cockroach, etc. Shell powder 'egg shell powder, organic hollow particles, inorganic hollow particles, and the like. These may be used alone or in combination of two or more kinds as appropriate. From the viewpoint of providing a more environmentally-adapted elastomer composition, it is preferred to use a large amount of shellfish powder or eggshell powder derived from raw scallops, oysters or the like which is waste. The compounding amount of the filler is usually 10 to 1000 parts by weight based on 100 parts by weight of the mixture of the natural rubber. It is preferably 5 Å to 5 Å by weight. When the amount is less than 10 parts by weight, the effect of adding the filler is insufficient. On the other hand, when it exceeds 1000 parts by weight, the composition becomes hard and the rubber elasticity is not sufficiently exhibited, and the tendency to exhibit sufficient hyphenation performance is as described above. The elastomeric eraser composition can be obtained by kneading above the melting temperature of PHBH and above the crosslinking temperature of the rubber crosslinking agent. The kneading is preferably carried out under high shear, and the kneading machine can be exemplified by a two-axis kneading machine, a Banbury mixer, a pressure kneader, a mixing machine, and the like. It is preferable to use a two-axis kneading extruder in the above. The melting temperature of PHBH means that the temperature is higher than the melting temperature of ρηβη by 10 to 50 ° C, and the crosslinking temperature of the rubber crosslinking agent is higher than the crosslinking temperature of the rubber crosslinking agent of 5 to 20. (The temperature is preferably: The above-described elastomer eraser composition can be formed by press molding, injection molding, extrusion molding, or the like, and cut into a predetermined size to obtain an eraser. On the other hand, in the present invention The vinyl resin to be used is not particularly limited, and a conventional vinyl chloride resin, a paste resin or a raw resin, may be used. A plasticizer may be added to the vinyl chloride resin. Further, a stabilizer or a coloring agent may be appropriately added as the case may be. Additives such as spices. 15 200923008 For plasticizers, for example, dioctyl phthalate (D〇p), monodecyl benzoate (DNP), diisononyl phthalate (DiNp), diisodecyl benzoate (DIDp), tridecyl phthalate (DTDP), phthalic acid hexadecanoate (DUp), etc. a plasticizer; a trimellitate-based plasticizer such as diisooctyl trimellitate (TI〇TM); a poly-I-based plasticizer; the material may be used alone or in combination of two or more kinds as appropriate. The plasticizer is added in an amount of 6 〇 to 18 〇 by weight relative to 1 part by weight of the vinyl chloride resin. It is 100 to 160 parts by weight. If the amount of the plasticizer is less than 1 part by weight, the composition becomes hard and the ability to erase the characters is not sufficiently exerted. On the other hand, if more than 160 parts by weight, the plasticizer moves and exudes. In the case of a paste resin, the paste resin and the plasticizer, and optionally the eraser composition composed of other additives, are kneaded, defoamed, and then flowed into a molding die of a predetermined depth to After a predetermined period of time, the crucible is heated, and then taken out from the metal mold and then cut to obtain an eraser in a predetermined size. f On the other hand, in the case of the original resin, the original resin and the plasticizer, as the case may be, and other additives The rubbing composition is formed by injection molding, extrusion molding, etc., and then cut to obtain an eraser in a predetermined size. "Eraser and vinyl chloride resin composed of the elastomer eraser composition obtained in the above manner The eraser composed of the eraser composition is drawn in a desired ratio, and then kneaded by a heated kneader, cooled and pulverized to obtain small particles, which are then ejected. Forming, squeezing, etc., forming it, and then cutting it in the size of the 疋 16 16 200923008 to obtain the eraser and air bake bake of the high erase performance eraser elastomer eraser composition of the present invention. The eraser composed of the rubbing composition "The mixing ratio is not particularly ambiguous. The focus of the rubber is on the recovery of resources or the reduction of the environmental burden.
性體橡皮擦的比例要高，另-方面，重點擺在：字：：: 情況下，後者氯乙烯樹脂橡皮擦的比例要高較好，氯乙烯 樹脂橡皮擦如果較少則作為本發明目的之消字能力的提升 效果就會變小。因此，相對於彈性體橡皮擦3〇〜重量％ 而言氯乙烯樹脂橡皮擦為7〇〜1〇重量％ ;彈性體橡皮擦 30〜80重量％而言氯乙烯樹脂橡皮擦為7〇〜2〇重量％較佳。 氯乙烯樹脂橡皮擦即使超過7〇重量％其消字性能大致相 同’但對環境的負擔有變大的傾向。 實施例 以下，根據實施例、參考例、以及比較例對本發明做 更詳細之說明，但本發明的範圍並無限制。 以下之貫施例、參考例、以及比較例中所用之材料示 於表1。 17 200923008 表1 商品名 物質名 製造公司 RSS#1 天然橡膠 印尼產 PHBH 生物分解性塑膠 聚(3-羥基丁酸酯-共-3-羥基己酸酯） (熔融溫度：120°〇 鐘化股份公司 力克馬爾PL-004 軟化劑 甘油二丙酮單月桂酸酯 理研維他命股份公司 SS#80 填充劑 重質碳酸鈣 曰東粉化工業股份公司 優尼卡 填充劑 輕質碳酸鈣 米庄石灰工業股份公司 帕黑奇薩C-40 橡膠交聯劑 1，1 -二(第三丁基過氧化)環己烷40%稀釋品 (交聯溫度·· 120~150°C) 日本油脂股份公司 阿迪卡斯塔布LA-32 紫外線吸收劑 苯并三峻系 ADEKA股份公司 ZESTP-21 氯乙烯樹脂 新第一鹽股份公司 DOP 可塑劑 苯二甲酸二辛酯 股份公司傑正 NS#400 填充劑 重質碳酸鈣 曰東粉化工業股份公司 ES-A 安定劑 硬脂酸鈣 鉛市化學工業股份公司 ES-Z 安定劑 硬脂酸辞 鉛市化學工業股份公司 參考例1 :彈性體橡皮擦的製造 表2所示之材料中，將天然橡膠、軟化劑、填充劑、 紫外線吸收劑預先以加壓捏合機混練，再用輥添加橡膠交 聯劑得到橡膠混練物。所得之混練物裁切為5mm見方左右 之小粒狀。然後，使用特克若貝爾公司製雙軸擠製機 KZW-15TW-60(同方向完全嚆合型，螺桿半徑 15mm， 18 200923008 L/D=60)，將橡膠混練物小粒和生物分解性塑膠小粒以表2 所示之配合比例分別用定量供給器供給、螺桿旋轉數在 400rpm、滾筒（cylinder)溫度設定在110〜155°C以上來混練， 然後裁切成3mm見方之小粒狀。 將所得之組成物小粒以單軸擠製機（滾筒溫度為 100~120°C，氣缸頭溫度130〇C)擠製成形為方條狀，裁切後 製作成橡皮擦（尺寸12x18x43mm)。 測定評價所得之橡皮擦的硬度與消字性能（消字率）。 結果示於表2。 硬度依循「JIS S 6050塑膠橡皮擦」，用c型硬度計（高 分子計量儀器製C型硬度計）測定。 此外’消字率用以下的方法測定。 (1) 將試料切成5mm的板狀，和試驗紙的接觸部分作 成半徑6mm的圓弧以此作為試驗片 (2) 將試驗片相對於著色紙呈垂直，且相對於著色線成 直角的方式來接觸’試驗片上放置站碼（缺碼和秤盤的質量 和為0.5kg)，j^ 150 士⑺咖/分鐘的速度在著色部上往返摩 PDA65 sakura 公司製）？ 分別測定著色部以及摩 (3)以》辰度 §十（densitometer 著色紙的非著色部分濃度當作0， 除部的濃度。 (4)消字率用下式算出。The proportion of sexual eraser should be high. On the other hand, the focus is on: Word::: In the case, the proportion of the vinyl chloride resin eraser is higher, and if the vinyl chloride resin eraser is less, it is the purpose of the present invention. The effect of improving the ability to erase words will be reduced. Therefore, the vinyl chloride resin eraser is 7〇~1〇% by weight relative to the elastomer eraser 3〇~wt%; the vinyl eraser eraser is 7〇~2 for the elastomer eraser 30~80% by weight 〇% by weight is preferred. Even if the vinyl chloride resin eraser exceeds 7% by weight, its erase performance is substantially the same, but the burden on the environment tends to increase. EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, reference examples, and comparative examples, but the scope of the invention is not limited. The materials used in the following examples, reference examples, and comparative examples are shown in Table 1. 17 200923008 Table 1 Trade name substance name manufacturing company RSS#1 Natural rubber Indonesian PHBH Biodegradable plastic poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (Melting temperature: 120°〇钟化股份Company Lectra PL-004 Softener Glycerol Diacetone Monolaurate Riken Vitamin Co., Ltd. SS#80 Filler Heavy Calcium Carbonate Jidong Powder Chemical Industry Co., Ltd. Unica Filler Light Calcium Carbonate Mizhuang Lime Industry Co., Ltd. Pahechisa C-40 rubber crosslinker 1,1 - di (t-butyl peroxy) cyclohexane 40% dilution (crosslinking temperature · · 120 ~ 150 ° C) Japan Oil and Fats Corporation Adikas Tabu LA-32 UV absorber benzotricarb ADEKA AG ZESTP-21 vinyl chloride resin new first salt company DOP plasticizer dioctyl phthalate company Jiezheng NS#400 filler heavy calcium carbonate Jidong Powder Chemical Industry Co., Ltd. ES-A Stabilizer Calcium Stearate Lead Chemical Industry Co., Ltd. ES-Z Stabilizer Stearic Acid Lead Lead Chemical Industry Co., Ltd. Reference Example 1: Manufacturing of Elastomer Eraser Table 2 Among the materials shown, The natural rubber, the softener, the filler, and the ultraviolet absorber are previously kneaded by a pressure kneader, and a rubber cross-linking agent is added by a roller to obtain a rubber kneaded product, and the obtained kneaded material is cut into small particles of about 5 mm square. Then, The rubber kneaded material pellets and biodegradable plastic pellets were obtained by using the twin-axis extruder KZW-15TW-60 (the same direction, the screw radius 15mm, 18 200923008 L/D=60). The mixing ratios shown in Table 2 were respectively supplied by a dose supplier, the number of screw rotations was 400 rpm, and the cylinder temperature was set to 110 to 155 ° C or more, and then kneaded, and then cut into small pieces of 3 mm square. The pellets are extruded into a square strip shape by a single-axis extruder (roller temperature of 100-120 ° C, cylinder head temperature 130 ° C), and then cut into an eraser (size 12×18×43 mm). The hardness and erasing performance of the rubbing (characterized rate). The results are shown in Table 2. The hardness was measured by "JIS S 6050 plastic eraser" and measured by a type C hardness tester (C type hardness tester made of polymer measuring instrument). Word elimination rate The sample was measured by the following method: (1) The sample was cut into a plate shape of 5 mm, and an arc of a radius of 6 mm was formed with the contact portion of the test paper as a test piece (2) The test piece was perpendicular to the colored paper, and was opposed to The coloring line is in a right angle to contact the 'stationary film on the station code (the missing code and the quality of the weighing pan is 0.5kg), j^150 士(7) coffee / minute speed in the coloring department to the PDA65 sakura company) The coloring portion and the friction (3) were measured as "the degree of non-coloring portion of the densitometer colored paper as 0, and the concentration of the division portion. (4) The word elimination rate was calculated by the following formula.
’肖予率（％) = (1_(摩除部的濃度十著色部濃度））xlOO 19 200923008 表2 參考例1 天然橡膠 RSS#1 100 生物分解性塑膠 PHBH 45 軟化劑 力克馬爾PL-004 70 填充劑 SS#80 200 優尼卡 10 橡膠交聯劑 帕黑奇薩C-40 2 紫外線吸收劑 阿迪卡斯塔布LA-32 1 天然橡膠：生物分解性塑膠比 69 ： 31 特性 硬度(C型） 84 消字率(％) 94.4 參考例2 :氯乙烯樹脂橡皮擦的製造 如表3所示，將氯乙烯樹脂、可塑劑、填充劑、安定 劑混合攪拌得到糊狀微粒子。將所得之糊狀微粒子真空脫 泡後，再流入保溫成 130 °C之成型用金屬模具 (100 xl 00 XI 0mm)，加熱26分鐘後冷卻，然後從金屬模具 中取出，裁切後製作成氯乙烯樹脂橡皮擦（尺寸 1 0X 1 8><43mm) ° 以與參考例1相同之方式來測定評價所得之橡皮擦的 硬度與消字率。結果以表3所示。 表3 參考例3 氯乙烯樹脂 ZEST P-21 100 可塑劑 DOP 160 填充劑 NS#400 100 安定劑 ES-A 0.5 ES-Z 0.5 特性 硬度(C型） 60 消字率(％) 97.7 20 200923008 ' 實施例1〜6 將參考例1所得之彈性體橡皮擦與參考例2所得之氯 乙烯樹脂橡皮擦以表4所示之混合比例（重量基準）加以混 合，以保溫成120〇C之加壓捏合機混練5分鐘。將所得之 組成物冷卻後粉碎得到小粒，再用單軸擠製機以既定的形 狀擠製成形’裁切後製作成橡皮擦（尺寸12xl8x43nim)。 以與參考例1相同之方式來測定評價所得之橡皮擦的 硬度與消字率。結果示於表4。 表4 實施例1 實施例2 實施例3 實施例4 實施例5 實施你J 6 參考例1之彈性體橡皮擦 (重量 90 80 70 50 30 10 參考例2之彈性體橡皮擦 ____ (重: 1%) Γ 10 20 30 50 70 90 特性 硬度(C型） 82 78 75 70 65 62 消字率(％) 95.1 95.7 96.1 96.9 97.7 97.7 (產業利用性） 如上所述’本發明之橡皮擦，因係使用生物分解性之 PHBH與天然橡膠作為主成分，故可不需依存石化資源、 即使丟棄’大氣中之二氧化碳增加也少、對環境負擔小且 因應循環型社會’ I同時藉由併用氯乙烯樹脂，可提供消 子此力優良之橡皮擦。此外，本發明之橡皮擦在丟棄階段 日守，於堆肥等階段會預先將彈性體生物分解，藉此可將氯 乙烯樹脂加以分離、回收。 21 200923008 【圖式簡單說明】 無 【主要元件符號說明】'Xiao Yu rate (%) = (1_(concentration of the smear part of the ten coloring part concentration)) xlOO 19 200923008 Table 2 Reference example 1 Natural rubber RSS #1 100 Biodegradable plastic PHBH 45 Softener LYKOL PL-004 70 Filler SS#80 200 Unica 10 Rubber Crosslinker Pahecsa C-40 2 UV Absorber Adikastabu LA-32 1 Natural Rubber: Biodegradable Plastic Ratio 69 : 31 Characteristic Hardness (Type C 84. The erasing rate (%) 94.4 Reference Example 2: Production of a vinyl chloride resin eraser As shown in Table 3, a vinyl chloride resin, a plasticizer, a filler, and a stabilizer were mixed and stirred to obtain paste-like fine particles. The obtained paste-like fine particles were vacuum-deaerated, and then poured into a molding die (100 x l 00 XI 0 mm) kept at 130 ° C, heated for 26 minutes, cooled, and then taken out from the metal mold, and cut into chlorine. Vinyl Eraser (size 1 0X 1 8 < 43 mm) ° The hardness and the erasing rate of the obtained eraser were measured in the same manner as in Reference Example 1. The results are shown in Table 3. Table 3 Reference Example 3 Vinyl chloride resin ZEST P-21 100 Plasticizer DOP 160 Filler NS#400 100 Stabilizer ES-A 0.5 ES-Z 0.5 Characteristic hardness (Type C) 60 Word elimination rate (%) 97.7 20 200923008 ' Examples 1 to 6 The elastomer eraser obtained in Reference Example 1 and the vinyl chloride resin eraser obtained in Reference Example 2 were mixed at a mixing ratio (weight basis) shown in Table 4 to maintain a pressure of 120 ° C. Kneading machine for 5 minutes. The resulting composition was cooled and pulverized to obtain granules, which were then extruded into a shape by a uniaxial extruder to form an eraser (size 12xl8x43nim). The hardness and the erasing rate of the eraser obtained by the evaluation were measured in the same manner as in Reference Example 1. The results are shown in Table 4. Table 4 Example 1 Example 2 Example 3 Example 4 Example 5 Implementation of your J 6 Reference Example 1 Elastomer Eraser (Weight 90 80 70 50 30 10 Reference Example 2 Elastomer Eraser ____ (Heavy: 1%) Γ 10 20 30 50 70 90 Characteristic hardness (Type C) 82 78 75 70 65 62 Word elimination rate (%) 95.1 95.7 96.1 96.9 97.7 97.7 (Industrial use) As described above, the eraser of the present invention, The biodegradable PHBH and natural rubber are used as the main components, so that it is not necessary to rely on petrochemical resources, even if it is discarded, the increase in carbon dioxide in the atmosphere is small, the environmental burden is small, and the recycling society is adopted. In addition, the eraser of the present invention is cleaned at the discarding stage, and the elastomer is biodegraded in advance in the composting stage, whereby the vinyl chloride resin can be separated and recovered. 200923008 [Simple description of the diagram] No [Main component symbol description]