TW201012864A - Resin particle - Google Patents

Abstract

Resin particles composed of a cyclic olden resin and having excellent heat resistance and transparency. The resin particles are suitable for use as a light-diffusing agent, a powder coating material, a toner material, an ink, a spacer For a liquid crystal display and the like), a filler, a blocking-preventing agent, a lubricant component, a powder for forming a three-dimensional object, and the like. The resin particles are characterized by having a weight average molecular weight as determined by gel permeahon chromatography of 30,000-200,000, by being composed of a specific cyclic olefin resin, and by having a volume average particle diameter of 1-200 μm.

Description

201012864 六、發明說明： 【發明所屬之技術領域】 本發明係關於樹脂粒子。更詳言之，係關於與其他材 料之密著性或接著性良好，爲高透明，進而爲高耐熱性之 由特定之環狀烯烴系樹脂所構成，且作爲光擴散劑、粉體 塗料、色劑用材料、油墨、隔離材（例如液晶顯示器使用 )、塡充材、抗結塊劑、潤滑劑成分、立體物造形用粉末 . 等有用之樹脂粒子。 【先前技術】 由各種樹脂所構成之粒子已使用作爲光擴散劑、粉體 塗料、色劑用材料、油墨、隔離材（例如液晶顯示器使用 )、塡充材、抗結塊劑、潤滑劑成分、立體物造形用粉末 等。尤其是藉由粉末燒結層合造形法之立體物造形就縮短 成形物開發期間以及節省費用方面而言，近年來以聚醯胺 ❹ 樹脂粒子作爲中心之立體物造形用粉末之需求持續擴大。 粉末燒結層合造形法係由以下步驟所構成，爲製造標 的造形物之技術，例如專利文獻1中揭示之技術。 (1) 先製備作爲標的之造形物之一定間隔之剖面形 狀之數據（第1號〜第η號之剖面之數據）之步驟； (2) 對平鋪成前述一定間隔之厚度之樹脂·金屬粉 末掃描照射雷射，成爲對應於前述第1編號之剖面數據之 剖面形狀，使樹脂或金屬熔接之步驟 (3) 於熔接之樹脂或金屬上再度鋪上一定間隔之厚 -5- 201012864 度之樹脂•金屬粉末，且掃描照射雷射成對應於前述第2 編號之剖面數據之剖面形狀，熔接層合前述樹脂.金屬之 步驟； (4)重複步驟（1)〜（3)，進行樹脂•金靥熔接層 合直至第η編號之剖面形狀爲止之步驟。 另外，作爲粉末燒結層合造形法以外之使用遠紅外線 雷射之加工法，亦以大肆探討使用遠紅外線雷射之雕刻、 切削、標記等。該等雷射加工法係利用削減雷射照射部份 @ 並使表面形狀產生變化，藉由雷射照射使被照射物展色或 退色之性質進行標示。 另一方面，環狀烯烴系樹脂由於玻璃轉移溫度、光線 透過率高，且折射率之各向異性小，因此相較於過去之光 學薄膜具有顯示低雙折射性等之特點。又由前述環狀烯烴 系樹脂在耐熱性、透明性、光學特性之均衡上均比聚醯胺 樹脂優異，而作爲透明熱可塑性樹脂受到矚目（參照例如 專利文獻2〜6 ) 。 _ 另外，利用前述特徵，已檢討環狀烯烴系樹脂在例如 光碟、光學鏡片、光纖、透明塑膠基板、低介電材料等之 電子•光學材料、光半導體封裝等之封裝材料等領域中之 應用。 具有該等優異性質之環狀烯烴系樹脂亦可期望作爲粒 子之特性，尤其是若應用粉末燒結層合造形，可期待獲得 利用以往之光硬化反應之光造形法難以製造之高耐熱、高 透明且高強度之造形物。 -6 - 201012864 然而，粉末燒結層合造形法係藉由對樹脂粉末照射雷 射（詳言之爲遠紅外線雷射）並使發熱而使前述樹脂粉末 熔接。然而，環狀烯烴系由於爲非晶性，因此如前述之透 明性優異之另一方面，溫度上升時之熔接黏度下降之程度 比尼龍等結晶材料小。據此，環狀烯烴系樹脂亦被指出爲 雷射加工性不良，不利於粉末燒結層合造形等（參考專利 文獻7 )。 〇 [先前技術文獻] [專利文獻] [專利文獻l]WO 1 997/029 1 48號說明書 [專利文獻2]特開平1 - 1 3 2625號公報 [專利文獻3]特開昭63-218726號公報 [專利文獻4]特開平2-133413號公報 [專利文獻5]特開昭61-12081 6號公報 [專利文獻6]特開昭61-115912號公報 Ο [專利文獻7]w〇 1 996/006 8 8 1號說明書 【發明內容】 [發明欲解決之課題] 本發明之課題係提供一種耐熱性及透明性優異，適合 使用作爲光擴散劑、粉體塗料、色劑用材料、油墨、隔離 材（例如液晶顯示器使用）、塡充材、抗結塊劑、潤滑劑 成分、立體物造形用粉末等之由環狀烯烴系樹脂所構成之 樹脂粒子。又，本說明書中，前述所謂透明性係指樹脂粒 201012864 子之透明性及使樹脂粒子熱熔接後之透明性兩者。 又本發明之目的亦提供一種遠紅外線之吸收能力優異 ，且對於使用於利用遠紅外線雷射之粉末燒結層合造形、 彫刻、切削、標記等適用之樹脂粒子。 [解決課題之手段] 本發明者等對解決前述問題積極進行硏究之結果，發 現由特定之環狀烯烴系樹脂或含有該樹脂之樹脂組成物所 @ 組成，且體積平均粒徑在一定範圍內之樹脂粒子可滿足前 述之要求，而完成本發明。 亦即本發明之要旨如下。 一種樹脂粒子，其特徵爲以凝膠滲透層析儀測定之重 量平均分子量爲30,000〜200,000，且由具有以下述通式（ 1)表式之重複單位之環狀烯烴系樹脂所構成，體積平均 粒徑爲1〜200μιη :201012864 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to resin particles. More specifically, it is composed of a specific cyclic olefin-based resin which is excellent in adhesion to other materials and has high adhesion and high heat resistance, and is used as a light diffusing agent or a powder coating material. Useful resin particles such as materials for toners, inks, separators (for example, for liquid crystal displays), enamel fillers, anti-caking agents, lubricant components, and powders for three-dimensional shape forming. [Prior Art] Particles composed of various resins have been used as light diffusing agents, powder coating materials, materials for toners, inks, separators (for example, for liquid crystal displays), enamel fillers, anti-caking agents, and lubricant components. , a three-dimensional shape forming powder, and the like. In particular, the demand for the three-dimensional shape of the powder-sintered lamination method is shortened. In the development of the molded article and the cost saving, the demand for the three-dimensional shape-forming powder centered on the polyamide resin particles in recent years has continued to expand. The powder sintered laminate forming method is composed of the following steps, and is a technique for producing a target shaped object, for example, the technique disclosed in Patent Document 1. (1) A step of preparing data (a data of a section of No. 1 to No. n) of a cross-sectional shape at a certain interval as a target shape; (2) a resin/metal which is laid to a thickness of the aforementioned interval The powder scanning irradiates the laser to have a cross-sectional shape corresponding to the cross-sectional data of the first number, and the step (3) of welding the resin or the metal is further spread on the resin or metal to be welded to a thickness of -5 to 201012864 degrees. Resin/metal powder, and scanning the laser beam into a cross-sectional shape corresponding to the cross-sectional data of the aforementioned No. 2, and fusing the resin to the metal; (4) repeating steps (1) to (3) for resin The step of laminating the gold crucible to the cross-sectional shape of the n-th number. In addition, as a processing method using a far-infrared laser other than the powder sintering layer forming method, engraving, cutting, marking, and the like using a far-infrared laser are also discussed. These laser processing methods use the reduction of the laser-irradiated portion @ and change the shape of the surface to indicate the nature of the illuminated object to be discolored or discolored by laser irradiation. On the other hand, the cyclic olefin resin has a high glass transition temperature and a high light transmittance, and has a small anisotropy of refractive index, and thus has a characteristic of exhibiting low birefringence and the like compared with the conventional optical film. Further, the above-mentioned cyclic olefin-based resin is superior to the polyamine resin in the balance of heat resistance, transparency, and optical properties, and is attracting attention as a transparent thermoplastic resin (see, for example, Patent Documents 2 to 6). _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . The cyclic olefin-based resin having such excellent properties can also be expected as a property of particles, and in particular, when a powder sintered laminate is used, it is expected to obtain high heat resistance and high transparency which are difficult to manufacture by a photoforming method using a conventional photocuring reaction. And high-strength shapes. -6 - 201012864 However, the powder sintered laminate forming method fuses the above-mentioned resin powder by irradiating a resin powder with a laser (in detail, a far-infrared laser) and generating heat. However, since the cyclic olefin is amorphous, the above-mentioned transparency is excellent, and the degree of fusion viscosity at the time of temperature rise is smaller than that of a crystalline material such as nylon. Accordingly, the cyclic olefin resin is also pointed out to be poor in laser workability, which is disadvantageous for powder sintered laminate formation and the like (refer to Patent Document 7).先前 [Prior Art Document] [Patent Document] [Patent Document 1] WO 1 997/029 1 48 [Patent Document 2] Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. No. Hei No. 63-218726 [Patent Document 5] Japanese Laid-Open Patent Publication No. JP-A No. 61-115912 (Patent Document No. JP-A-61-115912) [Patent Document 7] w〇1 996 [0061] [Invention of the Invention] [Problems to be Solved by the Invention] The object of the present invention is to provide an excellent heat resistance and transparency, and it is suitably used as a light diffusing agent, a powder coating material, a toner material, an ink, A resin particle composed of a cyclic olefin resin such as a separator (for example, used in a liquid crystal display), an enamel filler, an anti-caking agent, a lubricant component, or a powder for three-dimensional shape forming. In the present specification, the term "transparency" refers to both the transparency of the resin particles 201012864 and the transparency after heat-welding the resin particles. Further, it is an object of the present invention to provide a resin particle which is excellent in absorption ability of far-infrared rays and which is suitable for use in powder sintering lamination, engraving, cutting, marking, etc., which is used for laser beam using far-infrared laser light. [Means for Solving the Problem] The inventors of the present invention have found that the specific cyclic olefin resin or the resin composition containing the resin is composed of a specific cyclic olefin resin or a resin composition containing the resin, and the volume average particle diameter is within a certain range. The resin particles therein can satisfy the foregoing requirements, and the present invention has been completed. That is, the gist of the present invention is as follows. A resin particle characterized by having a weight average molecular weight of 30,000 to 200,000 as measured by a gel permeation chromatography, and consisting of a cyclic olefin resin having a repeating unit of the following formula (1), and an average volume Particle size is 1~200μιη:

-8- 201012864 [X表示以式：-CH = CH-表示之基或以式：-(：Η2(：Η2-表 示之基’a及b獨立地表示0或1，且c及d獨立地表示 〇~2之整數， R4、R5、R6、R7、R8及R9各自獨立地表示下述（i) 〜（v )之任一種： (i)氫原子 (ii )鹵素原子 〇 ( iii)經取代或非取代之碳數1〜40之烴基 (iv) 具有包含氧原子、硫原子、氮原子或矽原子之 連結基之經取代或非取代之碳數1~40之烴基 (v) 極性基 R1Q、R11、R12及R13各自獨立爲前述（i)〜（v)之 任一種，或爲下述（vi)〜（vii)之任一種； (vi) R1()與R11’或R12與R13鍵結形成單環或多環 之烴環或雜環，與前述鍵結無關之R1Q〜R13各自獨立爲前 〇 述U)〜（v)之任一種 (vii) R1()或R11與R12或R13彼此鍵結形成單環或多 環之烴環或雜環，與前述鍵結無關之R1G〜R13各自獨立爲 前述（i)〜（v)之任一種]。 前述環狀烯烴系樹脂使用烏伯羅德氏（Ubbelohde ) 型黏度計測定之對數黏度較佳爲0.30〜〇.95dL/g。 作爲本發明之樹脂粒子較佳者爲前述環狀烯徑系樹脂 之玻璃轉移溫度爲115 ~2 00 °C，且體積平均粒徑爲 10~80μπι之樹脂粒子。 201012864 前述環狀烯烴系樹脂中’較佳爲芳香族性之不飽和鍵 以外之碳-碳雙鍵部份中95 %以上被氫化。 又本發明之樹脂粒子亦可爲由前述環狀烯烴系樹脂與 具有以下述式（4)表示之構造單位之苯乙烯系聚合物之 樹脂組成物所構成，且體積平均粒徑爲之樹脂粒 子： [化2]-8- 201012864 [X represents a base represented by the formula: -CH = CH- or by the formula: -(:Η2(:Η2- indicates that the bases 'a and b independently represent 0 or 1, and c and d independently An integer representing 〇~2, R4, R5, R6, R7, R8 and R9 each independently represent any one of the following (i) to (v): (i) a hydrogen atom (ii) a halogen atom 〇 (iii) Substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms (iv) substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms (v) having a linking group of an oxygen atom, a sulfur atom, a nitrogen atom or a ruthenium atom R1Q, R11, R12 and R13 are each independently any one of the above (i) to (v), or any one of the following (vi) to (vii); (vi) R1() and R11' or R12 and R13 The bond is formed into a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring, and R1Q to R13 irrelevant to the aforementioned bonding are each independently of any of U) to (v) (vii) R1 () or R11 and R12 or And R.sup.1 and R. Ubbelohde type viscometer The logarithmic viscosity is preferably from 0.30 to 95.95 dL/g. The resin particles of the present invention preferably have a glass transition temperature of from 115 to 200 ° C and a volume average particle diameter of from 10 to 00 ° C. In the cyclic olefin resin, 95% or more of the carbon-carbon double bond portion other than the aromatic unsaturated bond is preferably hydrogenated. Further, the resin particles of the present invention may be The cyclic olefin-based resin and a resin composition having a styrene polymer having a structural unit represented by the following formula (4), and a volume average particle diameter of the resin particles: [Chemical 2]

參 ⑷ [前述式中，R表示碳數1〜4之烷基、羥基或羧基，n 表示0~5之整數，η爲2以上時，複數存在之R可相同或 〇 相異]。 本發明之樹脂粒子較佳進而含有遠紅外線吸收劑，且 與構成樹脂粒子之前述環狀烯烴系樹脂或樹脂組成物之重 量比成爲環狀烯烴系樹脂（樹脂組成物）：遠紅外線吸收 劑=99.99: 0.01 ~7 0: 30之量。該等樹脂粒子由於良好地 吸收遠紅外線，因此可適當使用於利用遠紅外線之粉末燒 結層合造形法等中。 前述遠紅外線吸收劑之例舉例爲矽酸鹽礦物或磷酸酯 -10- 201012864 本發明之樹脂粒子較佳進而含有抗氧化劑。 本發明之樹脂粒子可使用於粉末燒結層合造形方法中 [發明效果] 依據本發明，提供一種耐熱性、透明性優異之樹脂粒 〇 子，該樹脂粒子適用於光擴散劑、粉體塗料、色劑用材料 、油墨、隔離材（例如液晶顯示器用）、塡充材、抗結塊 劑、潤滑劑成分、立體物造形用粉末等各種粒子之用途中 〇 【實施方式】 以下對本發明加以詳細說明。 本發明之樹脂粒子之特徵爲以凝膠滲透層析儀測定之 © 重量平均分子量爲30,000〜200,000，且由具有以下述通式 (1)表式之重複單位之環狀烯烴系樹脂所構成，體積平 均粒徑爲1〜200μιη。且，如後所述般，本發明之樹脂粒子 亦可爲由含有前述環狀烯烴系樹脂與特定之苯乙烯系聚合 物之樹脂組成物所構成之樹脂粒子。 -11 - 201012864 [化3]Reference (4) [In the above formula, R represents an alkyl group having a carbon number of 1 to 4, a hydroxyl group or a carboxyl group, and n represents an integer of 0 to 5, and when η is 2 or more, R in the plural may be the same or different in 〇). The resin particles of the present invention preferably further contain a far-infrared ray absorbing agent, and the weight ratio of the cyclic olefin-based resin or the resin composition constituting the resin particles is a cyclic olefin-based resin (resin composition): far-infrared ray absorbing agent = 99.99: 0.01 ~ 7 0: 30 amount. Since the resin particles absorb the far infrared rays well, they can be suitably used in a powder sintering lamination forming method using far infrared rays or the like. Examples of the far-infrared ray absorbing agent are citrate minerals or phosphate esters. -10-201012864 The resin particles of the present invention preferably further contain an antioxidant. The resin particles of the present invention can be used in a method of forming a powder sintered laminate. [Effect of the Invention] According to the present invention, there is provided a resin pellet which is excellent in heat resistance and transparency, and which is suitable for a light diffusing agent, a powder coating material, Use of various particles such as a toner material, an ink, a separator (for example, for liquid crystal display), an enamel filler, an anti-caking agent, a lubricant component, and a three-dimensional shape forming powder. [Embodiment] Hereinafter, the present invention will be described in detail. Description. The resin particles of the present invention are characterized in that the weight average molecular weight is 30,000 to 200,000 as measured by a gel permeation chromatography, and is composed of a cyclic olefin resin having a repeating unit of the following formula (1). The volume average particle diameter is from 1 to 200 μm. Further, as described later, the resin particles of the present invention may be resin particles composed of a resin composition containing the above cyclic olefin resin and a specific styrene polymer. -11 - 201012864 [Chem. 3]

上式中，X表示以式：-CH = CH-表示之基或以式：-CH2CH2-表示之基，a及b獨立地表示0或1，且c及d獨 立地表示0〜2之整數， R4、R5、R6、R7、R8及R9各自獨立地表示下述（i) ~(v)之任一種： (i)氫原子 (Π )鹵素原子 (iii) 經取代或非取代之碳數1〜40之烴基 (iv) 具有包含氧原子、硫原子、氮原子或矽原子之 連結基之經取代或非取代之碳數1〜40之烴基 (v )極性基 R10、R11、R12及R13各自獨立爲前述（i) ~(v)之 任一種，或爲下述（vi) ~(vii)之任一種； (vi) R1q與R11，或R12與R13鍵結形成單環或多環 之烴環或雜環，與前述鍵結無關之R1G〜R13各自獨立爲前 述（i)〜（v)之任一種 -12- 201012864 (Vii) R1G或與Rl2或Rl3彼此鍵結形成單環或多 環之烴環或雜環，與前述鍵結無關之R1()~Ri3各自獨立爲 前述（i)〜（v)之任一種。 以下就構成本發明之樹脂粒子之環狀烯烴系樹脂及其 製造方法加以說明。 [環狀烯烴系樹脂] G 構成本發明之樹脂粒子之環狀烯烴系樹脂以凝膠滲透 層析儀（GPC )測定換算成聚苯乙烯之重量平均分子量 [\1评]爲 30,00〇〜200,00〇，較佳爲 32,000〜1 80,000，最佳爲 35，000~ 160,000。Mw未達30,000時，於將樹脂粒子加熱 並熱熔接獲得之成型體強度變得不足。又超過200,000時 ，將樹脂粒子加熱並熱熔接獲得之成型體之透明性變得不 足，且熔接強度亦變得不足。 且，前述環狀烯烴系樹脂之分子量分布[Mw/Μη]較佳 〇 爲1.1〜10.0，更佳爲1.3〜8_0，最佳爲1.5〜6.0。 構成本發明之樹脂粒子之環狀烯烴系樹脂使用烏伯羅 德氏（Ubbelohde )型黏度計測定之對數黏度通常爲 0.30~0.95 dL/g，較佳爲 0.32〜0.90dL/g，最佳爲 0.35〜 0.80dL/g。對數黏度小於〇.3〇dL/g時，會有使樹脂粒子加 熱並熱熔接獲得之成型體強度變得不足之情況。又超過 0.95dL/g時，會有使樹脂粒子加熱並熱熔接獲得之成型體 之透明性變得不足之傾向’且亦會有熔接強度變得不足之 傾向。 -13- 201012864 另外，構成本發明之樹脂粒子之環狀烯烴系樹脂之玻 璃轉移溫度[Tg]通常爲115~200 °c，較佳爲120~180°C。In the above formula, X represents a group represented by the formula: -CH = CH- or a group represented by the formula: -CH2CH2-, a and b independently represent 0 or 1, and c and d independently represent an integer of 0 to 2 R4, R5, R6, R7, R8 and R9 each independently represent any of the following (i) to (v): (i) a hydrogen atom (Π) a halogen atom (iii) a substituted or unsubstituted carbon number a hydrocarbon group of 1 to 40 (iv) a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms (v) having a linking group of an oxygen atom, a sulfur atom, a nitrogen atom or a ruthenium atom, and a polar group R10, R11, R12 and R13 Each of them is independently one of the above (i) to (v), or any one of the following (vi) to (vii); (vi) R1q and R11, or R12 and R13 are bonded to form a single or multiple ring a hydrocarbon ring or a heterocyclic ring, and R1G to R13, which are independent of the foregoing bonding, are each independently one of the above (i) to (v) -12- 201012864 (Vii) R1G or bonded to Rl2 or Rl3 to form a single ring or more The hydrocarbon ring or heterocyclic ring of the ring, R1() to Ri3 which are not related to the aforementioned bonding, are each independently of any of the above (i) to (v). Hereinafter, the cyclic olefin resin constituting the resin particles of the present invention and a method for producing the same will be described. [Cyclic olefin resin] G The cyclic olefin resin constituting the resin particles of the present invention is measured by a gel permeation chromatography (GPC), and the weight average molecular weight in terms of polystyrene is [30]. ~200,00 〇, preferably 32,000 to 1 80,000, and most preferably 35,000 to 160,000. When the Mw is less than 30,000, the strength of the molded body obtained by heating and thermally welding the resin particles becomes insufficient. When the amount is more than 200,000, the transparency of the molded body obtained by heating and thermally welding the resin particles is insufficient, and the weld strength is also insufficient. Further, the molecular weight distribution [Mw/Μη] of the cyclic olefin-based resin is preferably from 1.1 to 10.0, more preferably from 1.3 to 8_0, most preferably from 1.5 to 6.0. The cyclic olefin resin constituting the resin particles of the present invention has a logarithmic viscosity of 0.30 to 0.95 dL/g, preferably 0.32 to 0.90 dL/g, preferably 0.35, as measured by an Ubbelohde type viscometer. ~ 0.80dL/g. When the logarithmic viscosity is less than 〇.3〇dL/g, the strength of the molded body obtained by heating and thermally welding the resin particles may be insufficient. When the amount is more than 0.95 dL/g, the transparency of the molded body obtained by heating and thermally welding the resin particles tends to be insufficient, and the weld strength tends to be insufficient. In addition, the glass transition temperature [Tg] of the cyclic olefin resin constituting the resin particles of the present invention is usually 115 to 200 ° C, preferably 120 to 180 ° C.

Tg未達1 1 5 °C時，在高溫條件下使用時樹脂粒子有變形之 情況。另一方面，當Tg超過200 °C時，樹脂粒子變得難 以成形加工，又由於必須提高成形加工時之加熱溫度，故 而有因熱造成樹脂劣化之可能性。 構成本發明之樹脂粒子之環狀烯烴系樹脂爲具有以如 前述之前述通式（1)表示之重複單位之聚合物。前述環 _ 狀烯烴系樹脂亦可依據需要具有其他重複單位。又，前述 環狀烯烴系樹脂可僅具有一種相當於上式（1)之重複單 位，亦可具有構造不同，但同時相當於上式（1)之複數 種重複單位。 具有以前述通式（1)表示之重複單位之環狀烯烴系 樹脂係使以下述通式（3)表示之單體（以下亦稱爲「單 體（1)」）及依據需要之其他單體經開環（共）聚合獲 得。再者，藉由該開環（共）聚合獲得之環狀烯烴系樹脂 @ 之以通式（1)表示之重複單位中，X爲以式：-CH = CH-表 示之基。後述藉由進行氫化，獲得X爲以式：-CH2-CH2-表示之基之環狀烯烴系樹脂（氫化物）。 -14- 201012864 [化4]When the Tg is less than 1 15 °C, the resin particles are deformed when used under high temperature conditions. On the other hand, when the Tg exceeds 200 °C, the resin particles are difficult to be formed, and since the heating temperature at the time of molding processing must be increased, there is a possibility that the resin is deteriorated by heat. The cyclic olefin-based resin constituting the resin particles of the present invention is a polymer having a repeating unit represented by the above formula (1). The above cyclic olefin-based resin may have other repeating units as needed. Further, the cyclic olefin-based resin may have only one type of repeating unit corresponding to the above formula (1), or may have a different structure, but at the same time correspond to a plurality of repeating units of the above formula (1). The cyclic olefin resin having a repeating unit represented by the above formula (1) is a monomer represented by the following formula (3) (hereinafter also referred to as "monomer (1)") and other orders as needed The body is obtained by ring opening (co)polymerization. Further, in the repeating unit represented by the formula (1), the cyclic olefin resin obtained by the ring-opening (co)polymerization is represented by the formula: -CH = CH-. The hydrogenation is carried out to obtain a cyclic olefin resin (hydride) having a group represented by the formula: -CH2-CH2-. -14- 201012864 [Chem. 4]

❹ 式（3)中，a及b獨立地表示0或1，c及d獨立地 表示0〜2之整數。R4、R5、R6、R7、R8及R9各自獨立地 表示以上式（1)之說明所述之（1)〜（v)之任一者， R10、R11、Ri2及R13各自獨立爲以上式（1)之說明所述 之前述（i) ~(v)之任一者，或（vi)〜（vii)之任一者 至於前述（ii)之鹵素原子舉例爲例如氟原子、氯原 ®子及溴原子。 前述（iii)之經取代或非取代之碳數1〜40之烴基可 舉例爲例如甲基、乙基、丙基等烷基； 環戊基、環己基等環烷基； 乙烯基、烯丙基、丙烯基等烯基； 甲基、乙基、丙基等碳數1~10之烷基之至少一個氫 被甲基、乙基、丙基等烷基，環戊基、環己基等環烷基， 乙烯基、烯丙基、丙烯基等烯基等取代之基； 苯基、萘基、聯苯基等芳基； -15- 201012864 以甲基、乙基、丙基等烷基取代之苯基、萘基、聯苯 基等經烷基取代之芳基；等。 又，前述經取代或非取代之烴基可直接鍵結於環構造 上，或者亦可透過如前述（iv)所示之連結基鍵結。 至於前述連結基舉例爲例如羰基（-CO_)、氧羰基（-o(co)-)、碳氧基（-COO-)、碾基（-so2-)、醚鍵（-〇-)、硫醚 鍵（-S-)、亞胺基（-NH·)、醯胺鍵（-NHCO-、-CONH-)及矽 氧烷鍵（-〇SI(R)-(式中，R爲甲基、乙基等烷基））等 φ 。前述連結基亦可包含複數個該等之基。 前述（v)之極性基舉例爲例如羥基、碳數1〜10之烷 氧基、羰氧基、烷氧羰基、芳氧羰基、氰基、醯胺基、醯 亞胺基、三有機矽氧烷基、三有機矽烷基、胺基、醯基、 烷氧基矽烷基、磺醯基及羧基等。 更具體而言，前述烷氧基舉例爲甲氧基、乙氧基等； 羰氧基舉例爲乙醯氧基、丙醯氧基等烷基羰氧基，以 及苯甲醯基氧基等芳基羰氧基； @ 烷氧基羰基舉例爲甲氧羰基、乙氧羰基等； 芳氧基羰基舉例爲苯氧羰基、萘氧羰基、蕗氧基羰基 、聯苯基氧羰基等； 三有機矽氧烷基舉例爲三甲基矽氧烷基、三乙基矽氧 烷基等； 三有機矽烷基舉例爲三甲基矽烷基、三乙基矽烷基等 > 胺基舉例爲一級胺基； -16- 201012864 醯基舉例爲乙醯基、丙醯基、苯甲醯基等； 烷氧基矽烷基舉例爲三甲氧基矽烷基、三乙氧基矽烷 基等。 如前述（Vi )所示，上式（1 )中，Rie與R11或R12 與R13亦可鍵結形成單環或多環之烴環或或雜環。又如前 述（vii)所示，R1G或R11與R12或R13亦可彼此鍵結形成 單環或多環之烴環或雜環。 ❻ 至於該環狀構造可例舉例如以下式表示者。 下式中之R表示碳數2〇以下之直鏈狀、分支狀或環 狀烷基’或芳基。前述烷基或或芳基具體而言舉例爲甲基 、乙基、丙基、異丙基、環己基、苯基、萘基、聯苯基等In the formula (3), a and b independently represent 0 or 1, and c and d independently represent an integer of 0 to 2. R4, R5, R6, R7, R8 and R9 each independently represent any one of (1) to (v) described in the above formula (1), and R10, R11, Ri2 and R13 are each independently of the above formula ( 1) The above-mentioned (i) to (v), or any one of (vi) to (vii) to the halogen atom of the above (ii) is exemplified by, for example, a fluorine atom or a chlorinogen And bromine atoms. The substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms of the above (iii) may, for example, be an alkyl group such as a methyl group, an ethyl group or a propyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a vinyl group or an allylic group; An alkenyl group such as a propylene group; an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group or a propyl group; an alkyl group such as a methyl group, an ethyl group or a propyl group; a cyclopentyl group or a cyclohexyl group; a substituted group such as an alkyl group, a vinyl group, an allyl group or a propenyl group; an aryl group such as a phenyl group, a naphthyl group or a biphenyl group; -15- 201012864 substituted with an alkyl group such as a methyl group, an ethyl group or a propyl group; An alkyl group-substituted aryl group such as a phenyl group, a naphthyl group or a biphenyl group; Further, the above substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure or may be bonded through a linking group as shown in the above (iv). As the aforementioned linking group, for example, a carbonyl group (-CO_), an oxycarbonyl group (-o(co)-), a carboxy group (-COO-), a ground group (-so2-), an ether bond (-〇-), sulfur Ether bond (-S-), imine group (-NH.), guanamine bond (-NHCO-, -CONH-) and oxime bond (-〇SI(R)-(wherein R is methyl , ethyl, etc., alkyl)), etc. φ. The aforementioned linking group may also comprise a plurality of such groups. The polar group of the above (v) is exemplified by, for example, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a decylamino group, a quinone imine group, and a triorganophosphonium group. An alkyl group, a triorganoalkylene group, an amine group, a decyl group, an alkoxyalkyl group, a sulfonyl group, a carboxyl group or the like. More specifically, the alkoxy group is exemplified by a methoxy group, an ethoxy group or the like; and the carbonyloxy group is exemplified by an alkylcarbonyloxy group such as an ethoxycarbonyl group or a propyloxy group, and an aromatic group such as a benzyl group. Alkoxycarbonyl; @ alkoxycarbonyl is exemplified by methoxycarbonyl, ethoxycarbonyl, etc.; aryloxycarbonyl is exemplified by phenoxycarbonyl, naphthyloxycarbonyl, decyloxycarbonyl, biphenyloxycarbonyl, etc.; The oxyalkyl group is exemplified by trimethylphosphonyloxy group, triethylphosphonium oxyalkyl group, etc.; triorganoalkylene alkyl group is exemplified by trimethyldecylalkyl group, triethyldecylalkyl group, etc. > The amine group is exemplified by a primary amino group; -16- 201012864 The mercapto group is exemplified by an ethyl fluorenyl group, a propyl fluorenyl group, a benzhydryl group or the like; and an alkoxy fluorenyl group is exemplified by a trimethoxydecyl group, a triethoxydecyl group or the like. As shown in the above (Vi), in the above formula (1), Rie and R11 or R12 and R13 may be bonded to form a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring. Further, as shown in the above (vii), R1G or R11 and R12 or R13 may be bonded to each other to form a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring. ❻ The ring structure is exemplified by the following formula. R in the following formula represents a linear, branched or cyclic alkyl group or aryl group having a carbon number of 2 Å or less. The above alkyl or aryl group is specifically exemplified by methyl, ethyl, propyl, isopropyl, cyclohexyl, phenyl, naphthyl, biphenyl, and the like.

[化5][Chemical 5]

[化6][Chemical 6]

-17- 201012864 [化7]-17- 201012864 [化7]

[化8][化8]

-18- 201012864 [化u]-18- 201012864 [化u]

R ❻ 單體（η之具體例舉例爲以下之化合物： 雙環[2.2.1]庚-2-烯、三環[4.3.0.12.5]-3-癸烯、三環 [5 · 2.1 · 0 2.6 ]-癸-3，8 -二嫌、三環[4.4.0 · 12.5 ] · 3 - Ί--碳嫌 四環[4.4.0.12 5.17.1。]_3_十二碳烯、五環 [6·5·1·1 . 〇 7 · 〇9·13 ] _4·十五碳稀、五環 [7.4.0.12 5.19 12·〇8.ΐ3]_3_十五碳烯、5_甲基雙環[2 21]庚-2-烯、5-乙基雙環[2,2.1]庚-2-烯、5-甲氧羰基雙環[2.2.Π 庚-2-烯、-5-甲基-5_甲氧羰基雙環[2·2丨卜庚.〉烯、5_亞 乙基雙環[2.2.1]庚_2_烯、5_氰基雙環[2 2 u庚·2_烯、8_亞 乙基四環[HO.lU.y.io]」·十二碳烯、8_甲氧羰基四環 [4·4·0·125·171()]-3-十二碳烯、8_甲氧羰基_8·甲基四環 [4·4·0·125·171()]-3·十二碳烯、8_乙氧羰基四環 [4·4·0·12 5_17 1β]-3-十二碳烯、8_正丙氧羰基四環 [4·4·0·125，171<)]-3-十二碳烯' 8_異丙氧羰基四環 [4·4·0_125_171()]-3·十二碳烯、8_正丁氧羰基四環 -19- 201012864 [44〇12517.1(>]-3-十二碳烯、8-苯氧羰基四環 [44()12.517.1°]-3-十二碳烯、8-(1-萘氧基）羰基四環 [44〇12'17.1〇]-3-十二碳烯、8-(2-萘氧基）羰基四環 U , η ,2.510]-3-十二碳烯、8_ ( 4-苯基苯氧基）幾基四 [4.4.0.1 · 1 1 η P.5 l7lG]-3-十二碳嫌、8-甲基-8-乙氧鑛基四環 環[4.4,0.1 · u , η P 5 十二碳烯、8_甲基-8-正丙氧鑛基四環 [4.4.0.1 · 1R ❻ monomer (specific examples of η are exemplified by the following compounds: bicyclo [2.2.1] hept-2-ene, tricyclo[4.3.0.12.5]-3-decene, tricyclo[5 · 2.1 · 0 2.6 ]-癸-3,8-two suspects, three rings [4.4.0 · 12.5 ] · 3 - Ί--carbon suspected four rings [4.4.0.12 5.17.1.]_3_dodecene, pentacyclic [ 6·5·1·1 . 〇7 · 〇9·13 ] _4·15 carbon rare, pentacyclic [7.4.0.12 5.19 12·〇8.ΐ3]_3_pentadecene, 5-methylbicyclo[ 2 21]hept-2-ene, 5-ethylbicyclo[2,2.1]hept-2-ene, 5-methoxycarbonylbicyclo[2.2.Πhept-2-ene,-5-methyl-5-A Oxycarbonyl double bicyclo[2·2丨bhg.> alkene, 5-ethylidene bicyclo[2.2.1]hept-2-ene, 5-cyanobicyclo[2 2 uhept-2-ene, 8_A Tetracyclic ring [HO.lU.y.io]", dodecene, 8-methoxycarbonyl tetracyclo[4·4·0·125·171()]-3-dodecene, 8_A Oxycarbonyl-3-8-methyltetracyclo[4·4·0·125·171()]-3·dodecene, 8-ethoxycarbonyltetracyclo[4·4·0·12 5_17 1β]-3 - dodecene, 8-n-propoxycarbonyltetracyclo[4·4·0·125,171<)]-3-dodecene-8-isopropoxycarbonyltetracyclo[4·4·0_125_171 ( )]-3·dodecene, 8_n-butoxycarbonyltetracyclic-19- 201012864 [ 44〇12517.1(>]-3-dodecene, 8-phenoxycarbonyltetracyclo[44()12.517.1°]-3-dodecene, 8-(1-naphthyloxy)carbonyltetra Ring [44〇12'17.1〇]-3-dodecene, 8-(2-naphthyloxy)carbonyltetracyclic U, η, 2.510]-3-dodecene, 8-(4-phenylbenzene) Oxy) alkyltetraki [4.4.0.1 · 1 1 η P.5 l7lG]-3-dodecan, 8-methyl-8-ethoxylated tetracyclic ring [4.4, 0.1 · u , η P 5 dodecene, 8-methyl-8-n-propoxy-based tetracyclic [4.4.0.1 · 1

Η 4 0 125_1710卜3_十二碳嫌、8_甲基_8_異丙氧鑛基四環 [44〇 l2.5l7.1〇]-3-十二碳烯、8-甲基_8_正丁氧羰基四環 [4 4 0 I2.5 171〇]_3_十二碳烯、8·甲基·8·苯氧羰基四環 [4 4 0.12 Μ7 1〇]_3_十二碳烯、8_甲基I ( 1_萘氧基）羰 基四環[4.4.0·125·17丨〇]-3-十一碳稀、8*甲基_8_(2-萘氧 基）羰基四瓌[4.4,〇.125.171〇]-3-十二碳烯、8-甲基-8-( 4-苯基苯氧基）羰基四環[4·4.Ο.12·5·17.10]-3-十二碳烯、五 環[8.4.0.1 2.5_ 1 9.12·〇 13]-3-十 /、碳嫌、七環Η 4 0 125_1710 Bu 3_12 carbon suspect, 8_methyl_8_isopropoxy ore tetracyclo[44〇l2.5l7.1〇]-3-dodecene, 8-methyl_8 _ n-Butoxycarbonyltetracyclo[4 4 0 I2.5 171〇]_3_dodecene, 8·methyl·8·phenoxycarbonyltetracyclo[4 4 0.12 Μ7 1〇]_3_dodecene , 8-methyl I ( 1 -naphthyloxy)carbonyltetracyclo[4.4.0·125·17丨〇]-3-undene carbon, 8*methyl-8-(2-naphthyloxy)carbonyltetra瓌[4.4,〇.125.171〇]-3-dodecene, 8-methyl-8-(4-phenylphenoxy)carbonyltetracyclo[4·4.Ο.12·5·17.10]- 3-dodecene, pentacyclic [8.4.0.1 2.5_ 1 9.12·〇13]-3-10/, carbon suspected, seven rings

[8.7.0.13 6.1丨° ΐ7·112·15·〇2 7·〇η ΐ6]_4-二十碳烯、七環 [8 · 8 · 0 · 1 4 7.111 1 * · 1 13 ·1 6 · 0 3 8. 〇12 17 ] - 5 -二十一碳烯、5 -亞乙 基雙環[2.2.1]庚-2-烯、8·亞乙基四環[4.4.0.1 2 5.1 7丨0]-3-十二碳嫌、5_苯基雙環[2.2.1]庚-2-稀、5-苯基-5-甲基雙環 [2.2.1] 庚.2-烯、8-苯基四環[4_4.〇.12.5.；(7.1〇]_3_十二碳矣 、5-正丁基雙環[2.2.1]庚-2-嫌、5-正己基雙環[2.2.1]庚 烯、5-環己基雙環[221]庚_2_烯、5_(2•環己烯基）雙 [2.2.1] 庚-2-稀、5_正辛基雙環[2 2 lm_2·嫌、5-正癸基 環[2.2.1]庚-2,、5_異丙基雙環[2 2丨浪小嫌、5_ (丄 基）雙環[2.2.1]庚_2-嫌、5-(2-萘基）雙環[221]庚_2 •20- 201012864 5- ( 4-聯苯基 5_三甲氧基矽烷 、5- ( 2_萘基）_5_甲基雙環[2.2丨]庚·2稀 -5-甲基雙環[2 2 )雙環[2.2.1]庚-2-嫌、5- ( 4 -聯苯基） 庚-2-烯、5·胺基甲基雙環[2.2·1]庚_2_烯 基雙環烯、5-三乙氧基矽烷基雙環[2 2丨]庚 2-烯、5-三正丙氧基矽烷基雙環[2 2丨]庚_2烯、5二正 氧基矽烷基雙環[2.2.1]庚-2-烯、5_氯甲基雙環[2 2」]庚[8.7.0.13 6.1丨°ΐ7·112·15·〇2 7·〇ηΐ6]_4-Eicocarbene, seven-ring [8 · 8 · 0 · 1 4 7.111 1 * · 1 13 ·1 6 · 0 3 8. 〇12 17 ] - 5 - hexacarbene, 5-ethylenebicyclo[2.2.1]hept-2-ene, 8·ethylenetetracyclo[4.4.0.1 2 5.1 7丨0] -3-12 carbon, 5_phenyl bicyclo [2.2.1] hept-2-dilute, 5-phenyl-5-methyl bicyclo [2.2.1] g. 2-ene, 8-phenyl four Ring [4_4.〇.12.5.; (7.1〇]_3_dodecafluorene, 5-n-butylbicyclo[2.2.1]hept-2-pyrene, 5-n-hexylbicyclo[2.2.1]heptene, 5-cyclohexylbicyclo[221]hept-2-ene, 5-(2•cyclohexenyl)bis[2.2.1]hept-2-pyrene, 5_n-octylbicyclo[2 2 lm_2·s, 5-癸 癸 环 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Naphthyl)bicyclo[221]hept_2 •20- 201012864 5-(4-biphenyl-5-trimethoxydecane, 5-(2-naphthyl)-5-methylbicyclo[2.2丨]heptan-2 -5-Methylbicyclo[2 2 ]bicyclo[2.2.1]hept-2-y, 5-(4-diphenyl)hept-2-ene,5-aminomethylbicyclo[2.2·1]g _2-alkenyl bicycloalkenene, 5-triethoxydecylbicyclo[2 2丨]heptane 2- , 5-tri-n-propoxydecylbicyclo[2 2丨]hept-2-ene, 5 di-n-decyloxycycloalkyl [2.2.1]hept-2-ene, 5-chloromethylbicyclo[2 2" Geng

2-烯、5-羥基甲基雙環烯、5_環己烯基雙環 [2.2.1]庚-2-烯、5-氟雙環[2.2.1]庚_2_烯、5_氟甲基雙環 [2.2_1]庚-2-烯、5-三氟甲基雙環[2·2丨]庚5 9 -無 雙環[2.2.1]庚-2-烯、5,6-二氟雙環[2·2 1；1庚_2烯、5,5•雙 (二氟甲基）雙環[2.2.1]庚-2-烯、5，6·雙（三氟甲基）雙 環[2.2.1]庚-2-烯、5-甲基-5-三氟甲基雙環[221]庚_2·烯 、5,5,6-二氟雙環[2.2.1]庚-2-烯、5,5,66_四氟雙環[2 2 庚-2-烯、8-氟四環[4.4.0· 十二碳烯、8氟甲 基四環[4.4.0.12.5·17.10]-3-十二碳烯、8_三氟甲基四環 [4.4.0.I25·".”]」-十二碳烯、8,8_二氣四環 [4.4·0_125·17 1()]-3-十二碳嫌、螺[弗·9,8’·三環 [4.3_0_125][3]癸烯]等。 單體（1)可單獨使用或組合兩種以上使用。 前述通式（1)中，a及b各自獨立爲〇或丨，但較佳 爲a=l，b = 0。另外，c及d各自獨立地表示〇〜2之整數， 但較佳爲〇〜1，更佳爲c = 0且d = 〇或d=l。a〜d爲該等數 値之單體，係在製造單體之原料取得性及經濟性上優異， 且可生產性佳地製造單體。 -21 - 201012864 前述通式（1 )中，R4〜R9各自獨立爲（i) ~(v)之 任一種，較佳爲氫原子或碳數之烴基，更佳爲氫原 子或碳數1~4之烴基，最佳爲氫原子。R4〜R9爲前述基之 單體由於可以高產率製造而較佳。 又，R1G~R13各自獨立爲前述（i)〜（v)之任一種， 或爲前述（vi)〜（vii)之任一種，但以R1()及R11或R12 及R13之任一者均爲氫原子，或R1G或R11與R12或R13鍵 結形成環構造爲佳。R1()~R13爲前述構造之單體係因製造 @ 容易，且自該單體獲得之環狀烯烴系樹脂因其玻璃轉移溫 度[Tg]高，且機械強度亦優異之故而較佳。 該等較佳之單體可舉例如下述者。雙環[2.2.1]庚-2-烯 、三環[4·3.0·125]-3-癸烯、三環[5.2.1.02 6]·癸-3,8-二烯 、四環[4.4.0.12 5.17 10]-3-十二碳烯、5-甲基-5·甲氧羰基 雙環[2.2.1]庚-2-烯、5-亞乙基雙環[2.2.1]庚-2-烯、8-亞乙 基四環[4.4.0·125·1710]-3-癸烯、8-甲氧基_8_甲基四環 [4.4.0.12 5 ΐ7.ι〇]_3_癸烯、5_苯基雙環[2 21]庚 2_烯。 參 該等中，最佳者爲雙環[2.2.1]庚-2·烯、三環 [5.2.1.〇26]_癸_3,8-二烯、5-甲基_5-甲氧羰基雙環[2.2.1] 庚-2-烯及8-甲氧羰基-8-甲基四環[4.4.0.ίο] ·3·癸烯 〇 (共聚合性單體） 前述環狀烯烴系樹脂亦可爲使除前述通式（3)表示 之單體（單體（1))以外之共聚合性單體共聚合而成。 -22- 201012864 共聚合性單體可舉例爲碳數4〜20之環烯烴，較佳爲碳數 4〜12之環烯烴。其具體例列舉爲環丁烯、環戊烯、環庚烯 、環辛烯。 該等共聚合性單體可單獨使用一種或兩種以上倂用。 單體（1 )/共聚合性單體之較佳使用比例以重量比表 示爲 100/0〜5 0/50，更佳爲 100/0〜60/40。以使用比例 100/0〜5 0/5 0使單體（1 )與共聚合性單體開環（共）聚合 Φ 時所得之開環（共）聚合物中之單體（1)/共聚合性單體 之比例以重量比表示爲 100/0〜50/50，以使用比例 1 0 0/0〜6 0/4 0進行開環（共）聚合時，單體（1) /共聚合 性單體之比例以重量比表示爲100/0〜60/40。 (開環聚合觸媒） 前述環狀烯烴系樹脂之製造所用之開環（共）聚合用 之觸媒較佳使用烯烴複分解及複分解聚合反應（Olefin ❹ Metathesis and Metathesis Polymerization) ( K. J. IVIN, J. C. MOL，學院出版社1 997 )中所述之觸媒。 該等觸媒可舉例如由（a)選自由W、Mo、Re、V及 Ti之化合物所構成之群組之至少一種化合物，與（b)選 自 Li、Na、K、Mg、Ca、Zn、Cd、Hg、B ' Al、Si、Sη、 Pb等之化合物，且具有至少一種該元素-碳鍵或該元素 -氫鍵者之至少一種之組合所構成之複分解聚合觸媒。該 觸媒爲了提高觸媒活性，亦可爲添加有後述之添加劑（c )者。 -23- 201012864 添加劑的（C)成分之較佳代表例舉例爲醇類、醛類 、酮類、胺類等，另舉例爲特開平1 -2405 1 7號公報所示 之化合物。添加之目的爲調整該等觸媒之活性，或調整觸 媒對溶劑之溶解性。 又，前述複分解聚合觸媒以外之其他觸媒舉例爲（d )由未使用輔助觸媒之週期表第4族〜8族過渡金屬-碳烯 錯合物或金屬環丁烷錯合物等所構成之複分解觸媒。 複分解觸媒（d)之代表例舉例爲 W( = N-2,6-C6H3iPr2)( = CHtBu)(OtBu)2、 Mo(=N-2,6-C6H3iPr2)( = CHtBu)(OtBu)2、2-ene, 5-hydroxymethylbicycloalkenene, 5-cyclohexenylbicyclo[2.2.1]hept-2-ene, 5-fluorobicyclo[2.2.1]hept-2-ene, 5-fluoromethyl Bicyclo[2.2_1]hept-2-ene, 5-trifluoromethylbicyclo[2·2丨]hepton-5 9-nobicyclo[2.2.1]hept-2-ene, 5,6-difluorobicyclo[2 · 2 1; 1 hept-2-ene, 5,5•bis(difluoromethyl)bicyclo[2.2.1]hept-2-ene, 5,6·bis(trifluoromethyl)bicyclo[2.2.1] Hept-2-ene, 5-methyl-5-trifluoromethylbicyclo[221]hept-2-ene, 5,5,6-difluorobicyclo[2.2.1]hept-2-ene, 5,5 , 66_tetrafluorobicyclo[2 2 hept-2-ene, 8-fluorotetracyclo[4.4.0·dodecene, 8-fluoromethyltetracyclo[4.4.0.12.5·17.10]-3-12 Carbene, 8-trifluoromethyltetracyclo[4.4.0.I25·"."]-dodecene, 8,8-digastetracycline [4.4·0_125·17 1()]-3 - 12 carbon suspected, snail [Fo, 9,8', tricyclo[4.3_0_125][3] decene] and so on. The monomer (1) may be used singly or in combination of two or more. In the above formula (1), a and b are each independently ruthenium or osmium, but a = l and b = 0 are preferable. Further, c and d each independently represent an integer of 〇~2, but preferably 〇~1, more preferably c=0 and d=〇 or d=l. Each of a to d is a monomer which is excellent in material availability and economy in the production of a monomer, and is excellent in productivity. In the above formula (1), R4 to R9 are each independently (i) to (v), preferably a hydrogen atom or a hydrocarbon group having a carbon number, more preferably a hydrogen atom or a carbon number of 1~. The hydrocarbon group of 4 is preferably a hydrogen atom. The monomer in which R4 to R9 are the above groups is preferable because it can be produced in a high yield. Further, each of R1G to R13 is independently any one of the above (i) to (v), or any one of the above (vi) to (vii), but any of R1() and R11 or R12 and R13. It is preferably a hydrogen atom, or a structure in which R1G or R11 is bonded to R12 or R13 to form a ring. R1() to R13 are a single system of the above-mentioned structure, and it is easy to manufacture, and the cyclic olefin-based resin obtained from the monomer is preferable because its glass transition temperature [Tg] is high and mechanical strength is also excellent. The preferred monomers may be, for example, those described below. Bicyclo[2.2.1]hept-2-ene, tricyclo[4.3.0.125]-3-decene, tricyclo[5.2.1.02 6]·癸-3,8-diene, tetracyclo[4.4. 0.12 5.17 10]-3-dodecene, 5-methyl-5.methoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-ethylenebicyclo[2.2.1]hept-2-ene , 8-ethylenetetracyclo[4.4.0·125·1710]-3-decene, 8-methoxy-8-methyltetracyclo[4.4.0.12 5 ΐ7.ι〇]_3_pinene, 5-Phenylbicyclo[2 21]hept-2-ene. Among the above, the best one is bicyclo [2.2.1] hept-2-ene, tricyclo[5.2.1.〇26]_癸_3,8-diene, 5-methyl-5-methoxy Carbonylbicyclo[2.2.1]hept-2-ene and 8-methoxycarbonyl-8-methyltetracyclo[4.4.0.ίο] ·3·decene oxime (copolymerizable monomer) The above cyclic olefin system The resin may be obtained by copolymerizing a copolymerizable monomer other than the monomer (monomer (1)) represented by the above formula (3). -22- 201012864 The copolymerizable monomer may, for example, be a cycloolefin having 4 to 20 carbon atoms, preferably a cycloolefin having 4 to 12 carbon atoms. Specific examples thereof include cyclobutene, cyclopentene, cycloheptene, and cyclooctene. These copolymerizable monomers may be used alone or in combination of two or more. The preferred ratio of use of the monomer (1) / copolymerizable monomer is represented by a weight ratio of 100/0 to 5 0/50, more preferably 100/0 to 60/40. Monomer (1)/common in a ring-opening (co)polymer obtained by ring-opening (co)polymerization of monomer (1) with a copolymerizable monomer in a ratio of 100/0 to 5 0/5 0 The ratio of the polymerizable monomer is represented by a weight ratio of 100/0 to 50/50, and the monomer (1) / copolymerization is carried out by ring-opening (co)polymerization using a ratio of 1 0 0/0 to 6 0/40. The ratio of the monomer is expressed by weight ratio of 100/0 to 60/40. (Open-loop polymerization catalyst) The catalyst for ring-opening (co)polymerization used for the production of the above-mentioned cyclic olefin resin is preferably Olefin ❹ Metathesis and Metathesis Polymerization (KJ IVIN, JC MOL). , the catalyst described in the College Press 1 997). The catalyst may be, for example, at least one compound selected from the group consisting of (a) a compound selected from the group consisting of W, Mo, Re, V, and Ti, and (b) selected from the group consisting of Li, Na, K, Mg, and Ca. a metathesis polymerization catalyst comprising a compound of Zn, Cd, Hg, B'Al, Si, S?, Pb or the like and having at least one combination of at least one of the element-carbon bond or the element-hydrogen bond. In order to increase the activity of the catalyst, the catalyst may be added with the additive (c) described later. -23- 201012864 A preferred representative example of the component (C) of the additive is exemplified by an alcohol, an aldehyde, a ketone, an amine, etc., and a compound represented by JP-A No. 1 - 2405 1 7 is also exemplified. The purpose of the addition is to adjust the activity of the catalysts or to adjust the solubility of the catalyst to the solvent. Further, other catalysts other than the metathesis polymerization catalyst are exemplified by (d) a transition metal-carbene complex or a metal cyclobutane complex which is a group 4 to 8 of the periodic table which does not use an auxiliary catalyst. The metathesis catalyst that constitutes. A representative example of the double decomposition catalyst (d) is W( = N-2,6-C6H3iPr2)(=CHtBu)(OtBu)2, Mo(=N-2,6-C6H3iPr2)(=CHtBu)(OtBu)2 ,

Ru( = CHCH = CPh2)(PPh3)2Cl2、 Ru(= CΗPh)(P C6Η! j)2C12 等 (聚合反應用溶劑） 開環聚合反應中使用之聚合反應用溶劑（後述之分子 量調節劑之溶劑、單體（1)及/或複分解觸媒之溶劑）可 舉例爲例如苯、己烷、庚烷、辛烷、壬烷、癸烷等烷類； 環己烷、環庚烷、環辛烷、十氫萘、原冰片烷等環烷 類； 苯、甲苯、二甲苯、乙基苯、枯烯等芳香族烴； 氯丁烷、溴己烷、二氯甲烷、二氯乙烷、六亞甲基二 溴、氯苯、氯仿、四氯乙烯等鹵化烷、鹵化芳基化合物； 乙酸乙酯、乙酸正丁酯、乙酸異丁酯、丙酸甲酯、二 甲氧基乙烷等飽和羧酸酯類； -24- 201012864 二丁基醚、四氫呋喃、二甲氧基乙烷等醚類等。該等 可單獨使用一種，或混合兩種以上使用。該等中以芳香族 烴較佳。 聚合反應用溶劑之使用量通常係使「溶劑：單體（1 )(重量比）」成爲1: 1〜10: 1之量，較佳爲1: 1〜5: 1之量。又，後述（1)〜（4)之（共）聚合物之製造時’ 亦可使用與前述相同之聚合反應用溶劑。 (分子量調節劑） 所得開環（共）聚合物之分子量調節可藉由聚合溫度 、觸媒種類、溶劑種類予以進行，但本發明中可藉由使分 子量調節劑共存於聚合反應系統中而調節。 此處，適用之分子量調節劑可舉例爲例如乙烯、丙烯 、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯等α-烯烴類及苯乙烯。該等中，以1-丁烯、1-己基 ❹最佳。 該等分子量調節劑可單獨使用一種或混合兩種以上使 用。 分子量調節劑之使用量相對於供給於開環聚合反應中 之全部單體1莫耳，通常爲0.005〜0.6莫耳，較佳爲 0.02〜0_5莫耳。再者，後述之（1) 、（2)及（4)之（ 共）聚合物之製造時亦可使用與前述相同之分子量調節劑 -25- 201012864 (聚合反應） 聚合反應可在常壓〜1 MPa之壓力下進行，反應溫度通 常爲40〜140 °C，反應時間通常爲0.5〜5小時。 獲得開環（共）聚合物可在開環聚合步驟中使單體（ 1)與共聚合性單體經開環共聚合而成，但另外，亦可在 聚丁二烯、聚異戊間二烯等共軛二烯化合物、苯乙烯-丁 二烯共聚物、乙烯-非共軛二烯共聚物、聚原冰片烯等之 主鏈上含有兩個以上之碳-碳雙鍵之不飽和烴系聚合物之 _ 存在下，使單體（1)經開環聚合而成，亦可使該等成爲 開環（共）聚合物之構造單位導入。 <氫化物> 如前述般獲得之開環（共）聚合物可直接使用，但使 該等進一步氫化獲得之氫化物可使用作爲耐熱性大的樹脂 粒子原料。 所謂的氫化物爲前述通式（1)中之X自以-CH = CH- φ 表示之烯烴性不飽和基轉換成以-CH2-CH2-表示之基之開 環（共）聚合物。單體（1)具有芳香族性取代基時，該 芳香族性之不飽和鍵可殘存，亦可依據需要而經氫化。 (氫化觸媒） 前述氫化反應中所用之氫化觸媒可使用一般之烯烴性 化合物之氫化反應中使用者。該氫化觸媒可使用習知之不 均質系觸媒及均質系觸媒之任一種。 -26- 201012864 至於不均質系觸媒可舉例爲將鈀、鉑、鎳、鍺、釕等 貴金屬觸媒物質支撐於碳、氧化矽、氧化鋁、氧化鈦等支 撐物上而成之固體觸媒。 另外，均質系觸媒可舉例爲環烷酸鎳/三乙基鋁、雙 (乙醯基丙酮酸）鎳（II) /三乙基鋁、辛酸鈷/正丁基鋰 、二茂鈦二氯化物/二乙基鋁單氯化物、乙酸铑、氯參（ 三苯基膦）铑、二氯參（三苯基膦）釕、氯氫羰基參（三 Φ 苯基膦）釕、二氯羰基參（三苯基膦）釕、（乙醯氧基） 羰基（氫化）雙（三苯基膦）釕、（4-戊基苯甲醯氧基） 羰基（氫化）雙（三苯基膦）釕等。 觸媒之型態可爲粉末狀亦可爲粒狀。另外，該等氫化 觸媒可單獨使用一種，亦可組合兩種以上使用。 該等氫化觸媒須適當調整其使用量，但較佳使「開環 (共）聚合物：氫化觸媒（重量比）」成爲1: 1χ1〇·6〜1 :2之比例使用。 © 又’氫化之比例通常爲前述開環（共）聚合物中之以 前述通式（1 )表示之重複單位全體中，95莫耳％以上， 較佳97莫耳％以上，更佳99莫耳％以上，係期望使X爲 以-CH2-CH2-表示之基之比例。亦即，以前述開環（共） 聚合物中，除芳香族性不飽和鍵以外之碳-碳雙鍵部份之 95%以上被氫化者較佳。若氫化之比例愈高，則愈可抑制 所得氫化物中因熱造成之著色或劣化，因此由抗氧化性之 觀點而言較佳。 氫化反應可例如藉由將氫化觸媒添加於開環（共）聚 -27- 201012864 合物之溶液（溶劑爲製造開環（共）聚合物所使用之聚合 反應用溶劑）中，且通常在40〜250 °C ，通常在常壓 〜30MPa，較佳在2〜20MPa，更佳在3〜18MPa下，通常使 氫作用〇.5~5小時而進行。 <純化> 前述開環（共）聚合物或其氫化物之合成反應後，可 藉由純化獲得高純度之環狀烯烴系樹脂。純化可使用過去 _ 習知之方法。至於前述方法舉例爲例如以甲苯或四氫呋喃 等良溶劑稀釋所得反應物溶液後，將甲醇、水或該等之混 合溶液等之弱溶劑添加於稀釋溶液中使聚合物適度的凝聚 ，經萃取處理之方法。 萃取處理時作爲反應溶劑使用之溶劑以及爲稀釋而添 加之溶劑合計之良溶劑重量與聚合物重量之比（良溶劑/ 聚合物）通常爲0.5/1〜6/1，較佳爲0.7/1 ~4/1。 又，萃取所使用之甲醇、水或該等之混合溶液等弱溶 @ 劑之使用量（重量）與前述良溶劑重量之比（弱溶劑/前 述良溶劑）通常成爲0.3〜5，較佳爲0.5〜3之量。 萃取溫度通常爲40〜120°C，較佳爲50~100°C。 如前述般經萃取後，使溶液冷卻分離成輕重層，且以 離心分離機去除輕層。重複該等萃取操作1〜10次後，使 重層液濃縮並以蒸發器、雙軸擠出機等脫溶裝置脫溶。脫 溶時之溫度爲150〜3 50 t，較佳爲200~3 50。(：，真空度爲 0.1 〜50mmHg，較佳爲 1〜40mmHg。 -28- 201012864 又，脫溶前亦可經稀釋進行循環過濾。過濾之際可單 獨使用一種孔徑爲0.1〜ΙΟΟμιη之濾劑，亦可階段性地設置 複數種孔徑不同之過濾器。又，亦可藉由使脫溶後之熔接 聚合物過濾而純化。此時聚合物過濾器之孔徑較佳爲 0 · 1 〜1 00 μιη 〇 [其他（共）聚合物] 〇 又，具有源自以前述通式（3)表示之單體之構造單 體之其他（共）聚合物舉例爲以下者。 (1) 藉由使構成本發明之樹脂粒子之環狀烯烴系樹 脂（開環（共）聚合物或開環（共）聚合氫化物）經氟瑞 德—克雷夫（Friedel-Crafts )反應環化後，經氫化獲得之 開環（共）聚合氫化物； (2) 以前述通式（3)表示之環狀烯烴係單體之加成 (共）聚合物； ® (3)以前述通式（3)表示之環狀烯烴系單體與乙烯 或單取代之乙烯之加成共聚物； (4)選自由以前述通式（3)表示之環狀烯烴系單體 、乙烯系環狀烴系單體及環戊二烯系單體所組成群組之至 少一種單體之加成型（共）聚合物或其氫化物 前述（3)之加成共聚物中’單取代之乙烯可舉例爲 例如丙烯、丁烯等，較佳爲碳數2〜12,更佳爲碳數2〜8 之α烯烴系化合物。 使用前述（1) ~(4)之其他（共）聚合物時亦可藉 -29- 201012864 由後述之樹脂粒子之製造方法獲得樹脂粒子，但就耐熱性 、機械強度、加工性、透明性及生產性等之均衡而言，以 前述環狀烯烴系樹脂（開環（共）聚合物或其氫化物）最 佳。 [含有環狀烯烴系樹脂與苯乙烯系聚合物之樹脂組成物] 本發明之樹脂粒子亦可爲由含有前述環狀烯烴系樹脂 及具有以下式（4)表示之構造單位之苯乙烯系聚合物之 ❹ 樹脂組成物所構成之樹脂粒子。由含有具有下式（4)之 構造單位之苯乙烯系聚合物之樹脂組成物，可獲得熔融時 之流動性特別優異之樹脂粒子。 [化 14]Ru(=CHCH=CPh2)(PPh3)2Cl2, Ru(=CΗPh)(P C6Η! j)2C12, etc. (solvent for polymerization) Solvent for polymerization reaction used in ring-opening polymerization reaction (solvent of molecular weight modifier described later) The solvent of the monomer (1) and/or the metathesis catalyst may, for example, be an alkane such as benzene, hexane, heptane, octane, decane or decane; cyclohexane, cycloheptane, cyclooctane , naphthenes such as decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, dichloromethane, dichloroethane, and hexa Halogenated alkane such as methyl dibromide, chlorobenzene, chloroform or tetrachloroethylene; halogenated aryl compound; saturated carboxylic acid such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate or dimethoxyethane Acid esters; -24- 201012864 Ethers such as dibutyl ether, tetrahydrofuran, dimethoxyethane, etc. These may be used alone or in combination of two or more. Among these, aromatic hydrocarbons are preferred. The solvent for the polymerization reaction is usually used in an amount such that the "solvent: monomer (1) (weight ratio)" is from 1:1 to 10:1, preferably from 1:1 to 5:1. Further, in the production of the (co)polymer (1) to (4) described later, the same solvent for the polymerization reaction as described above may be used. (Molecular weight modifier) The molecular weight adjustment of the obtained ring-opened (co)polymer can be carried out by polymerization temperature, catalyst type, solvent type, but can be adjusted in the present invention by allowing a molecular weight regulator to coexist in a polymerization reaction system. . Here, suitable molecular weight modifiers are exemplified by, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-decene. Such as α-olefins and styrene. Among these, 1-butene and 1-hexyl fluorene are preferred. These molecular weight modifiers may be used alone or in combination of two or more. The molecular weight modifier is used in an amount of usually 0.005 to 0.6 mol, preferably 0.02 to 0_5 mol, based on 1 mol of all monomers supplied to the ring-opening polymerization. Further, in the production of the (co)polymer of (1), (2), and (4), the same molecular weight modifier as described above may be used -25-201012864 (polymerization). The polymerization reaction may be at normal pressure~ The reaction is carried out at a pressure of 1 MPa, and the reaction temperature is usually 40 to 140 ° C, and the reaction time is usually 0.5 to 5 hours. Obtaining a ring-opening (co)polymer can form a ring-opening copolymerization of a monomer (1) and a copolymerizable monomer in a ring-opening polymerization step, but in addition, it can also be in a polybutadiene or a polyisoprene. The conjugated diene compound such as a diene, a styrene-butadiene copolymer, an ethylene-non-conjugated diene copolymer, a polynorbornene or the like contains two or more carbon-carbon double bonds in the main chain. In the presence of the hydrocarbon-based polymer, the monomer (1) may be subjected to ring-opening polymerization, or the structural unit which is a ring-opening (co)polymer may be introduced. <Hydride> The ring-opened (co)polymer obtained as described above can be used as it is, but the hydride obtained by further hydrogenation can be used as a raw material of a resin particle having high heat resistance. The hydride is an open-cell (co)polymer in which X in the above formula (1) is converted from an olefinic unsaturated group represented by -CH = CH-φ to a group represented by -CH2-CH2-. When the monomer (1) has an aromatic substituent, the aromatic unsaturated bond may remain or may be hydrogenated as needed. (Hydrogenation Catalyst) The hydrogenation catalyst used in the above hydrogenation reaction can be used in a hydrogenation reaction of a general olefinic compound. As the hydrogenation catalyst, any of a conventional heterogeneous catalyst and a homogeneous catalyst can be used. -26- 201012864 The heterogeneous catalyst can be exemplified by a solid catalyst obtained by supporting a noble metal catalyst such as palladium, platinum, nickel, rhodium or ruthenium on a support such as carbon, ruthenium oxide, aluminum oxide or titanium oxide. . Further, the homogeneous catalyst may be exemplified by nickel naphthenate/triethylaluminum, bis(ethylmercaptopyruvate) nickel(II)/triethylaluminum, cobalt octoate/n-butyllithium, and titanocene dichloride. Compound/diethylaluminum monochloride, barium acetate, chloroform (triphenylphosphine) ruthenium, dichlorostilbene (triphenylphosphine) ruthenium, chlorohydrocarbonyl ruthenium (tri-p-phenylphosphine) ruthenium, dichlorocarbonyl Reference (triphenylphosphine) ruthenium, (ethoxycarbonyl) carbonyl (hydrogenated) bis(triphenylphosphine) ruthenium, (4-pentylbenzylideneoxy) carbonyl (hydrogenated) bis(triphenylphosphine) Hey. The type of the catalyst can be either powder or granular. Further, these hydrogenation catalysts may be used alone or in combination of two or more. The hydrogenation catalyst should be appropriately adjusted in its amount. However, it is preferred to use a "ring-opening (co)polymer: hydrogenation catalyst (weight ratio)" in a ratio of 1:1χ1〇·6~1:2. The ratio of the 'hydrogenation' is usually 95% by mole or more, preferably 97% by mole or more, more preferably 99%, of the total of the repeating units represented by the above formula (1) in the above-mentioned ring-opening (co)polymer. Above the ear %, it is desirable to make X a ratio of a group represented by -CH2-CH2-. That is, in the above-mentioned ring-opening (co)polymer, 95% or more of the carbon-carbon double bond portion other than the aromatic unsaturated bond is preferably hydrogenated. When the ratio of hydrogenation is higher, the coloring or deterioration due to heat in the obtained hydride is suppressed, and therefore, it is preferable from the viewpoint of oxidation resistance. The hydrogenation reaction can be carried out, for example, by adding a hydrogenation catalyst to a solution of a ring-opened (co)poly-27-201012864 compound (solvent is a solvent for polymerization for use in producing a ring-opening (co)polymer), and usually 40 to 250 ° C, usually at a normal pressure of ~ 30 MPa, preferably at 2 to 20 MPa, more preferably at a temperature of 3 to 18 MPa, usually carried out by hydrogen for 5 to 5 hours. <Purification> After the synthesis reaction of the above-mentioned ring-opened (co)polymer or its hydride, a highly pure cyclic olefin-based resin can be obtained by purification. Purification can be done using the methods of the past _. In the above method, for example, after diluting the obtained reactant solution with a good solvent such as toluene or tetrahydrofuran, a weak solvent such as methanol, water or a mixed solution thereof is added to the diluted solution to appropriately agglomerate the polymer, and the mixture is subjected to extraction treatment. method. The ratio of the weight of the good solvent to the weight of the polymer (good solvent/polymer) of the solvent used as the reaction solvent in the extraction treatment and the solvent added for the dilution is usually 0.5/1 to 6/1, preferably 0.7/1. ~4/1. Further, the ratio of the amount (weight) of the weakly soluble agent such as methanol, water or a mixed solution used for the extraction to the weight of the good solvent (weak solvent/previous solvent) is usually 0.3 to 5, preferably 0.5 to 3 amount. The extraction temperature is usually 40 to 120 ° C, preferably 50 to 100 ° C. After extraction as described above, the solution was cooled to separate into a light and heavy layer, and the light layer was removed by a centrifugal separator. After repeating the extraction operations 1 to 10 times, the supernatant liquid is concentrated and desolvated by a desolvation device such as an evaporator or a twin-screw extruder. The temperature at the time of desolvation is 150 to 3 50 t, preferably 200 to 3 50. (:, the degree of vacuum is 0.1 to 50 mmHg, preferably 1 to 40 mmHg. -28- 201012864 Further, it may be diluted and subjected to circulation filtration before desolvation. When filtering, a filter having a pore diameter of 0.1 to ΙΟΟμηη may be used alone. Further, a plurality of filters having different pore diameters may be disposed in stages, or may be purified by filtering the melted polymer after desolvation. The pore size of the polymer filter is preferably 0 · 1 to 1 00 μm. 〇 [Other (co)polymer] Further, another (co)polymer having a structural monomer derived from the monomer represented by the above formula (3) is exemplified as follows: (1) By constituting the composition The cyclic olefin-based resin (open-loop (co)polymer or ring-opening (co)polymerized hydride) of the resin particles of the invention is obtained by hydrogenation after Friedel-Crafts reaction cyclization a ring-opening (co)polymerization hydride; (2) an addition (co)polymer of a cyclic olefin monomer represented by the above formula (3); (3) a ring represented by the above formula (3) An addition copolymer of an olefin-based monomer with ethylene or a mono-substituted ethylene; (4) selected from Addition (co)polymer of at least one monomer of the group consisting of a cyclic olefin monomer, a vinyl cyclic hydrocarbon monomer, and a cyclopentadiene monomer represented by the formula (3) or In the addition copolymer of the above (3), the mono-substituted ethylene may, for example, be propylene, butylene or the like, and is preferably an α-olefin compound having a carbon number of 2 to 12, more preferably 2 to 8 carbon atoms. When the other (co)polymers of the above (1) to (4) are used, the resin particles can be obtained by the method for producing resin particles described later by -29-201012864, but the heat resistance, mechanical strength, workability, transparency, and The cyclic olefin resin (ring-opening (co)polymer or its hydride) is optimal in terms of balance of productivity, etc. [Resin composition containing a cyclic olefin resin and a styrene polymer] The resin particles of the invention may be resin particles composed of a ruthenium resin composition containing the above-mentioned cyclic olefin resin and a styrene polymer having a structural unit represented by the following formula (4). The structural composition of the styrene polymer resin composition The resin particles which are particularly excellent in fluidity at the time of melting can be obtained.

式（4)中，R表示碳數1~4之烷基、羥基或羧基，η 表示0〜5之整數，η爲2以上時，複數存在之R可相同或 相異。 就樹脂粒子之熔融時的流動性、與環狀烯烴系樹脂之 相溶性之觀點而言，R較佳爲甲基或羥基，η較佳爲0或 -30- 201012864 具有以前述式（4)表示之構造單位之聚合物可 爲聚苯乙烯、苯乙烯/羥基苯乙烯共聚物、苯乙嫌/ α· 苯乙烯共聚物、苯乙烯/烯烴共聚物、苯乙嫌/ 丁二嫌 物' 苯乙烯/ 丁二烯共聚物之氫化物。 前述聚合物中，聚苯乙烯、苯乙烯/嫌烴系共聚 苯乙烯/ 丁二烯共聚物之氫化物由於對環狀烯烴系樹 〇 相溶性良好，且可改善樹脂粒子之流動性或強度而較 聚苯乙烯較佳爲以凝膠滲透層析儀測定之重量平 子量爲1 000~300〇〇，較佳爲1 500-1 50000者。重量 分子量在前述範圍之聚苯乙烯就對環狀烯烴系樹脂之 性良好且可改善樹脂粒子之流動性方面而言較佳。該 苯乙烯之製造方法爲習知，該聚苯乙烯亦爲市售。市 之例可舉例爲 SX100(YASUHARA CHEMICAL (股） ，Mw ： 2500 ) 、RESITE S94 (三洋化成工業（股） Φ ，Mw : 4000 ) 、HIMER ST95 (三洋化成工業（股） ，Mw : 5000 )。 前述苯乙烯/ 丁二烯共聚物之氫化物之全部構造 1 00重量％中，源自苯乙烯之構造單位之比例通常爲 重量％，較佳爲10〜65重量％。源自苯乙烯之構造單 前述範圍內時，就對環狀烯烴系樹脂之相溶性良好且 樹脂粒子之強度方面而言較佳。苯乙烯/ 丁二烯共聚 氫化物之氫化率作爲源自丁二烯之烯烴性二聚物之氫 通常在70°/。以上’較佳在80%以上。氫化率在該範圍 舉例 甲基 共聚 物及 脂之 圭。 均分 平均 相溶 等聚 售品 製造 製造 製造 單位 5~70 位在 提升 物之 化率 內時 -31 - 201012864 ’由於樹脂粒子之耐熱性變良好而較佳。該等共聚合氫化 物亦可依據其構造而稱爲苯乙烯/乙烯/丁烯共聚物等。 該等苯乙烯/ 丁二烯共聚物之氫化物較佳爲以凝膠滲 透層析儀測定換算成聚苯乙烯之重量平均分子量爲 1 0,000~300,000’較佳爲20,000〜250,000者。由含有重量 平均分子量在前述範圍之苯乙烯/ 丁二烯共聚物之氫化物 之樹脂組成物’可獲得強度優異之樹脂粒子故而較佳。該 等苯乙烯/ 丁二烯共聚物之氫化物之製造方法爲習知，該 _ 氫化物亦爲市售。市售品之例可舉例爲苯乙烯/乙烯•丁 烯比率爲30/70重量％之TAFUTACK H1041(旭化成（股 )製造，Mw: 70,000 )、苯乙烯/乙烯.丁烯比率爲48/52 重量％之JSR (股）製造之DAINARON 8900)。 構成本發明之樹脂粒子之樹脂組成物中，環狀烯烴系 樹脂與苯乙烯系聚合物之重量比通常爲環狀烯烴系樹脂/ 苯乙烯系聚合物=99/1~50/50，較佳爲95/5~70/30。環狀烯 烴系樹脂與苯乙烯系聚合物之重量比滿足前述比率時，一 @ 方面可維持源自環狀烯烴系樹脂之優異耐熱性及透明性， 一方面可改善樹脂粒子之流動性或強度而較佳。 又，構成本發明之樹脂粒子之樹脂組成物在不損及本 發明效果之下，可包含相對於1〇〇重量％之樹脂成分較佳 爲0~60重量％之例如特開平9-221577號公報、特開平10- 2 8773 2號公報中所述之特定烴系樹脂或習知之熱可塑性樹 脂、熱可塑性彈性體、橡膠質聚合物、有機粒子等作爲除 前述環狀烯烴系樹脂及苯乙烯系聚合物以外之樹脂成分。 -32- 201012864 又’樹脂組成物可以習知之方法，將環狀烯烴系樹脂 與苯乙烯系聚合物，及視情況之前述烴系樹脂等混合製造 。例如藉由使用雙軸擠出機將該等混練，獲得顆粒狀之樹 脂組成物。又，亦可將環狀烯烴系樹脂與苯乙烯系樹脂， 及視情況之前述烴系樹脂等溶解於適當之溶劑中均勻混合 後’以與環狀烯烴系樹脂之脫溶方法相同之方法獲得經脫 溶之粒狀樹脂組成物。 φ 由該等樹脂組成物所構成之本發明樹脂粒子熔接時之 流動性特別優異，具體而言在荷重10kg，於溫度260°c測 定之熔接流動速率（MFR)通常爲10〜250g/min，較佳爲 20〜200g/min 〇 &lt;遠紅外線吸收劑&gt; 本發明之樹脂粒子就遠紅外線之吸收能力之觀點而言 較佳含有遠紅外線吸收劑。 G 遠紅外線吸收劑只要是在遠紅外線之波長領域（ 4~10 00μιη)中顯示吸收者即不限定其種類。遠紅外線吸收 劑之例可舉例爲有機染料、有機顔料、無機染料、無機顏 料、其他有機物或無機物。另外，該等遠紅外線吸收劑在 不損及本發明效果之範圍內可經著色，亦可爲無色。較佳 依據本發明樹脂粒子之使用目的，適當選擇遠紅外線吸收 劑之顏色或吸收特性。 前述無機物之例可舉例爲無機微粒子，前述有機物之 例可舉例爲含有磷原子之化合物。 -33- 201012864 無機微粒子多爲熱安定，且在不損及環狀烯烴系樹脂 及樹脂組成物（以下稱爲「環狀烯烴系樹脂等」）之玻璃 轉移溫度等耐熱特性之下，可進一步使其粒徑•形狀等多 樣化，以滿足各種目的故而較佳。無機微粒子之具體例可 舉例爲碳酸鈣、碳酸緦等碳酸鹽類；矽酸鹽白土、雲母、 高嶺土礦物、雲母黏土礦物、蒙脫石（Smectite)、蛇紋 石礦物、滑石、綠泥石、姪石（Vermiculite )等黏土礦物 •矽酸鹽礦物。 _ 該等中以矽酸鹽礦物較佳，最佳爲雲母。無機微粒子 之形狀並無特別限制，亦可爲球形、針狀、其他無定型。 無機微粒子之粒徑之一次體積平均粒徑通常爲0.1〜3 0 μιη ，較佳爲 〇·3~28μιη，最佳爲 0.5〜25μιη。平均粒徑大於 3 Ομιη時，會損及環狀烯烴系樹脂等具有之透明性。· 前述含有磷原子之化合物可舉例爲磷酸、磷酸酯、聚 磷酸、亞磷酸、亞磷酸酯類、膦酸酯類。該等中，磷酸酯 類、亞磷酸酯類、膦酸酯之腐蝕性低，對環狀烯烴系樹脂 參 等之相溶性優異而較佳，最佳爲磷酸酯類。 磷酸酯類、亞磷酸酯類、膦酸酯較佳分別具有（¥〇_ )3Ρ、（Υ0-)3Ρ = 0、Υ(Υ〇-)2Ρ構造（其中，同—分子內存在 之複數個Υ可相同或相異，Υ爲甲基及乙基等烷基（該烷 基亦可具有取代基）、苯基及聯苯基等芳基（該芳基亦可 具有取代基）等）。 該等之具體例舉例爲三苯基亞磷酸酯、苯基膦酸二苯 酯、苯基膦酸二甲酯、三甲基磷酸酯、三乙基磷酸酯、三 -34- 201012864 丁基磷酸酯、三苯基磷酸鹽、三甲酚磷酸酯、三二甲苯磷 酸酯、縮水甘油基苯基磷酸酯、二甲苯基二苯基磷酸酯、 甲酚基雙（二-2,6 -二甲苯基）磷酸酯、二-2 -乙基己基碟 酸酯、間苯二甲酚雙（二-2,6-二甲苯基）磷酸鹽、雙酚A 雙（二苯基）磷酸酯、雙酚A雙（二甲酚基）磷酸鹽、 4，4’-二酚雙（二苯基）磷酸酯。 該等中，甲酚二苯基磷酸酯、二甲苯基二苯基磷酸酯 φ 、甲酚雙（二-2,6-二甲苯基）磷酸酯、間苯二甲酚雙（ 二-2,6-二甲苯基）磷酸酯、雙酚A雙（二苯基）磷酸酯' 雙酚A雙（二甲酚基）磷酸酯、4,4’-二酚雙（二苯基）磷 酸酯，因低揮發性而較佳。另外，由於間苯二甲酚雙（ 二-2,6-二甲苯基）磷酸酯及4,4，-二酚雙（二苯基）磷酸 酯爲固態，適合乾式摻合製程而最佳。 無機化合物、磷酸酯類、亞磷酸酯類及膦酸醋類可依 據耐熱性或透明性等要求之品質水準做選擇°又名·個可單 Θ 獨使用或組合複數種使用。另外亦可複合地使用無機化合 物與磷酸酯類、亞磷酸酯類及膦酸酯類。 該等遠紅外線吸收劑之添加量相對於構成樹脂粒子之 環狀烯烴系樹脂或樹脂組成物之重量，係成爲環狀烯烴系 樹脂（樹脂組成物）：遠紅外線吸收劑=99·99 : 0·0 1〜70 : 30之量，較佳爲99.95 : 0.05~75 : 25之量’最佳爲99.9 :0.1〜80 : 20之量。遠紅外線吸收劑之添加量超過前述範 圍時，會損及環狀烯烴系樹脂等本身具有之透明性或耐熱 性。另外少於前述範圍時，無法提高遠紅外線能量之利用 -35- 201012864 效率。 添加遠紅外線吸收劑之環狀烯烴系樹脂或樹脂組成物 具有優異之遠紅外線吸收能力，加工成100 μιη厚度之薄膜 時，在波數94 5(:1^1中之吸光度超過0.36，更佳爲超過 0.4。吸光度爲0.36以下時，由於紅外線之吸收性低，因 此提供於使用紅外線加工本發明之樹脂粒子時，會產生熱 效率下降等之問題。 又將添加遠紅外線吸收劑之環狀烯烴系樹脂等加工成 Λ ΙΟΟμηι厚度之薄膜之全光透光率通常爲85%以上，較佳爲 8 8%以上，最佳爲90%以上，又濁度通常爲10%以下，較 佳爲9%以下，最佳爲8%以下。全光透光率未達85%或濁 度超過10%時，以粉末燒結層合造形法等加工本發明之樹 脂粒子獲得之成型體中，其內部之辨識性會下降。 &lt;添加劑&gt; 構成本發明之樹脂粒子之環狀烯烴系樹脂或樹脂組成 _ 物在不損及本發明之效果之範圍內可依據需要添加抗氧化 劑、熱安定劑、光安定劑、紫外線吸收劑、紅外線吸收劑 、抗靜電劑、分散劑、加工性提升劑、氯擷取劑、難燃劑 、結晶化核劑、抗結塊劑、防霧劑、脫模劑、染料、顏料 、螢光增白劑、有機或無機塡充材、中和劑、滑劑、分解 劑、金屬惰性化劑、抗污染材、抗菌劑或其他樹脂、熱可 塑性彈性體等習知之添加劑。該等添加劑可單獨使用一種 亦可倂用複數種。添加劑之添加量通常相對於100質量份 -36- 201012864 之環狀烯烴系樹脂等爲ι〇質量份以下。 前述抗氧化劑舉例爲2,6-二第三丁基-4-甲基酚、 2,2’-二氧基·3,3’-二第三丁基-5,5’-二甲基二苯基甲烷、肆 [亞甲基-3- (3,5-二第三丁基-4-羥基苯基）丙酸酯]甲烷、 1，1，3-參（2-甲基-4-羥基-5-第三丁基苯基）丁烷、l，3,5-三甲基-2，4,6-參（3，5-二第三丁基-4-羥基苄基）苯、硬脂 基-(3,5-二第三丁基-4-羥基苯基）丙酸酯、2,2，-二氧 φ 基-3,3’-二第三丁基-5，5’-二乙基苯基甲烷、3，9-雙[1,1-二 甲基-2-( yS-(3-第三丁基-4·羥基-5-甲基苯基）丙醯氧基 )乙基]、2,4,8，10-四氧雜螺[5,5]十一烷、參（2,4-二第三 丁基苯基）亞磷酸酯、環狀新戊烷四基雙（2,4-二第三丁 基苯基）亞磷酸酯、環狀新戊烷四基雙（2,6-二第三丁基-4-甲基苯基）亞磷酸酯、2,2-亞甲基雙（4,6-二第三丁基 苯基）辛基亞磷酸酯等。 又抗氧化劑之市售商品可舉例爲以下者。汽巴•曰本 e 股份有限公司製造之 Irganox 1010、 Irganox 1035、 Irganox 1 076、Irganox 1 3 30、Irganox 245、Irgafos 168、 Irgafos 38，ADEKA股份有限公司製造之 ADEKASTAB AO-50 、 ADEKASTAB AO-60 、 ADEKASTAB AO-3 3 0 、 ADEKASTAB 21 12。 前述紫外線吸收劑舉例爲例如2,4-二羥基二苯甲酮、 2-羥基-4-甲氧基二苯甲酮、2- (2H-苯并***-2-基）-4,6-雙（1-甲基-1-苯基乙基）酚、2-(2H-苯并***-2-基）-4,6-二第三丁基酚、2-苯并***-2-基4,6-二第三丁基酚、 -37- 201012864 2,2’-亞甲基雙[4-(1,1，3,3-四甲基丁基）-6-[(211-苯并三 唑-2·基）酚]]等。 [樹脂粒子] 本發明之樹脂粒子之體積平均粒徑爲1〜200μιη，較佳 爲10~80μιη。體積平均粒徑大於該200μιη時，以粉末燒結 層合造形法造型時剖面一層份（薄片）之厚度變厚，造成 缺乏立體造型物之精細性。另一方面，體積平均粒徑小於 ^ Ιμιη時，薄片數變得太多而造成缺乏生產性。再者，本說 明書中所謂的體積平均粒徑，與粒子之形狀無關，均係使 用日機裝（股）製造之MICROTACK ΜΤ3 300測定之體積 平均粒徑。 本發明之樹脂粒子形狀並無特別限制，可爲球形亦可 爲不定型。 又，所得樹脂粒子之粒度分佈比期望之分布更廣之情 況下，亦可藉由習知之分級機分級。分級方式可爲濕式亦 _ 可爲乾式。分級機具體而言可使用空氣分離機等慣性分級 機，鼓風機、微分離機等乾式離心分級機，離心沉降機、 液體鼓風機等濕式離心分級機，篩網分級機等。 本發明之樹脂粒子爲由前述環狀烯烴系樹脂，或含有 環狀烯烴系樹脂與前述苯乙烯系聚合物之樹脂組成物所構 成之粒子。使樹脂或樹脂組成物成爲粒子之方法可採用習 知之各種方法，例如可藉由乳化法或機械粉碎法使環狀烯 烴系樹脂等成爲樹脂粒子。以下針對該二方法加以說明。 -38- 201012864 &lt;乳化法&gt; 以乳化法製造本發明之樹脂粒子時，作爲其製造方法 ，舉例有具有下列步驟特徵之製造方法：將環狀烯烴系樹 脂或樹脂組成物溶解於有機溶劑中之步驟1，使步驟1中 獲得之溶劑A在水中或含有界面活性劑之水溶液B中乳化 之步驟2，回收分散於步驟2中獲得之乳化液中之環狀烯 φ 烴系樹脂等粒子並乾燥之步驟3。以下針對該等各步驟加 以說明。 (步驟1 ) 步驟1中使用之有機溶劑只要可使前述環狀烯烴系樹 脂或樹脂組成物溶解則無特別限制，例如爲石油醚、戊烷 、己烷、庚烷、辛烷、壬烷、癸烷等烴類； 環戊烷、環己烷、甲基環己烷、環丁烷、環辛烷、十 © 氫萘烷、原冰片烷等環狀烴類； 苯、甲苯、二甲苯、乙基苯、枯烯、氯苯等芳香族烴 類； 二氯甲烷、二氯乙烷、氯丁烷、氯仿、四氯乙烯等鹵 化烴類； 乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、丙 酸甲酯等酯類； 二丁基醚、四氫呋喃、二甲氧基乙烷、二噁烷等醚類 -39- 201012864 Ν,Ν-二甲基甲醯胺、Ν,Ν-二甲基乙醯胺、N-甲基毗咯 啶酮等醯胺類。 該等可單獨使用或混合兩種以上使用。該等中，就環 狀烯烴系樹脂等之溶解性之觀點而言較佳使用芳香族烴類 〇 步驟1可例如以下列之任一者實施。 (1) 將下述（a)〜（d)之任一種溶解於前述有機溶 劑中。 參 (a )環狀烯烴系樹脂等顆粒 (b) 除了由本說明書說明之樹脂粒子之製造方法製 造之樹脂粒子以外之環狀烯烴系樹脂等之粉末 (c) 回收利用環狀烯烴系樹脂或樹脂組成物製之薄 膜或射出成形物時，該薄膜及射出成形物或其粉碎物等 (d) 環狀烯烴系樹脂顆粒與苯乙烯系聚合物等之異 種樹脂顆粒之混合物 (2) 於前述有機溶劑中合成環狀烯烴系樹脂，且依 @ 據需要氫化。亦即，環狀烯烴系樹脂之合成中使用之有機 溶劑直接作爲前述有機溶劑使用。 (3) 使於前述有機溶劑中合成環狀烯烴系樹脂，且 依據需要使該樹脂氫化獲得之反應溶液，進行萃取純化或 吸附處理等純化並去除殘留之單體或觸媒。 環狀烯烴系樹脂等之有機溶劑溶液（以下亦簡稱爲溶 液A)中之環狀烯烴系樹脂之濃度通常爲5〜40質量％，較 佳爲7〜35質量％，最佳爲10〜30質量％。濃度小於5質量 -40- 201012864 %時，環狀烯烴系樹脂等之粒子之生產性有變低之虞。另 外，超過40質量％時，會造成溶液A於後述之水中或含 有界面活性劑之水溶液B中之分散性下降，產生無法獲得 期望粒徑之樹脂粒子等之問題。 驟 步 步驟2中，藉由使步驟1中獲得之溶液A乳化於水中 〇 或含有界面活性劑之水溶液B中，使環狀烯烴系樹脂等分 散於水中或水溶液B中，成爲粒子形狀。 前述乳化時之攪拌•分散手段舉例爲過去習知之攪拌 裝置，但並不特別限定於此。該等裝置之具體例可舉例爲 螺旋槳式攪拌機、鋸齒狀之摻合混練機、密閉式滾筒混練 機、滾筒/定子式混練機、靜態混練機、直列式螺旋槳/渦 流式混練機、直列式轉子/定子式混練機、膠質混合機、 高壓均質機等。 〇 攪拌機之轉速等攪拌條件由於依據設備或樹脂粒子之 生產量及其他條件而變，因此無法槪括的決定，但可藉由 一般攪拌條件（例如，10〜3 000Orpm )進行。 對攪拌時間同樣無法槪括決定，但通常爲5 ~3 00分鐘 ，較佳爲10〜180分鐘，更佳爲15〜120分鐘。攪拌時間比 5分鐘短時，環狀烯烴系樹脂等之分散不充分，會有無法 獲得期望粒徑之樹脂粒子之狀況。又攪拌時間比300分鐘 長時，會有樹脂粒子之生產性下降之傾向。 使溶液A於水中或水溶液B中乳化時之溫度通常爲 -41 - 201012864 0~100t，較佳爲5〜80°C，最佳爲l〇~6(TC »乳化時之溫 度超過100°C時，樹脂粒子會有容易在乳化有溶液A之乳 化液中凝聚之傾向。另一方面於溫度未達時會有樹脂 粒子之製造費用變高之傾向。 步驟2中溶液A與水或溶液B之質量比（使用量比） 通常爲[溶液 A]/[水或水溶液 B] = l/100〜5/1，較佳爲 1/5 0〜4Π，最佳爲1/3 0〜3/1。溶液A與水或水溶液B之質 量比小於1/100時會有樹脂粒子之生產性下降之傾向。另 φ 一方面，當大於5/1時，樹脂粒子容易在乳化液中凝聚， 會有無法獲得具有期望粒徑之樹脂粒子之情況。 使溶液A分散之介質係使用水或水溶液B，但較佳爲 水溶液B。藉由存在界面活性劑，使樹脂粒子在步驟2中 獲得之乳化液中之安定性提高。 前述界面活性劑可使用習知之脂肪酸鈉、脂肪酸鉀、 烷基苯磺酸鈉、烷基硫酸酯鈉、烷基醚硫酸酯鈉、α -烯 烴磺酸鈉、烷基磺酸鈉等陰離子界面活性劑； @ 烷基三甲基銨鹽、二烷基二甲基銨鹽等陽離子界面活 性劑； 烷基胺基脂肪酸鈉、烷基甜菜鹼、烷基胺氧化物等兩 性界面活性劑； 蔗糖脂肪酸酯、山梨糖酐脂肪酸酯、聚氧伸乙基山梨 糖酐脂肪酸酯、聚氧伸乙基烷酯、脂肪酸烷醇醯胺、聚氧 伸乙基烷基醚、聚氧伸乙基烷基苯基醚、聚氧伸丙基烷基 醚、聚氧伸丙基脂肪酸酯等非離子系界面活性劑；但並不 -42- 201012864 限於該等。 該等中非離子性界面活性劑就與環狀烯烴系樹脂等之 相溶性高、於樹脂粒子中微量殘留時對樹脂粒子之影響小 的方面而言較佳。界面活性劑最佳者爲聚氧伸乙基烷基醚 、聚氧伸乙基烷酯、聚氧伸丙基烷基醚、聚氧伸丙基烷酯 等聚氧伸乙基或聚氧伸丙基之衍生物。In the formula (4), R represents an alkyl group having 1 to 4 carbon atoms, a hydroxyl group or a carboxyl group, η represents an integer of 0 to 5, and when η is 2 or more, R in the plural may be the same or different. From the viewpoint of fluidity at the time of melting of the resin particles and compatibility with the cyclic olefin resin, R is preferably a methyl group or a hydroxyl group, and η is preferably 0 or -30 to 201012864 having the above formula (4) The polymer represented by the structural unit may be polystyrene, styrene/hydroxystyrene copolymer, styrene/α·styrene copolymer, styrene/olefin copolymer, styrene/butyl susceptibility benzene A hydride of an ethylene/butadiene copolymer. Among the above polymers, the hydride of the polystyrene, styrene/hydrocarbon-based copolystyrene/butadiene copolymer has good compatibility with the cyclic olefin-based tree stalk, and can improve the fluidity or strength of the resin particles. The polystyrene is preferably a weight of 1 000 to 300 Å, preferably 1,500 to 50,000, as measured by a gel permeation chromatograph. The polystyrene having a molecular weight in the above range is preferable in that it is excellent in the properties of the cyclic olefin resin and can improve the fluidity of the resin particles. The method for producing styrene is conventionally known, and the polystyrene is also commercially available. Examples of the city can be SX100 (YASUHARA CHEMICAL, Mw: 2500), RESITE S94 (Sanyo Chemical Industry Co., Ltd. Φ, Mw: 4000), HIMER ST95 (Sanyo Chemical Industry Co., Ltd., Mw: 5000). The ratio of the structural unit derived from styrene in the total structure of the hydride of the styrene/butadiene copolymer is 100% by weight, preferably 10 to 65% by weight. When the structure of the styrene is within the above range, the compatibility with the cyclic olefin resin is good and the strength of the resin particles is preferable. Styrene/Butadiene Copolymer The hydrogenation rate of the hydride is usually 70 ° / as the hydrogen derived from the butadiene-derived olefin dimer. The above is preferably more than 80%. The hydrogenation rate in this range is exemplified by methyl copolymers and fats. It is preferable that the average heat-dissipating ratio of the resin particles is good, and the average heat-dissipating ratio of the resin particles is from 5 to 70 in the production rate of the lifter -31 - 201012864. These copolymerized hydrides may also be referred to as styrene/ethylene/butene copolymers and the like depending on their structures. The hydride of the styrene/butadiene copolymer is preferably a gel permeation chromatograph having a weight average molecular weight of from 1,000,000 to 300,000', preferably from 20,000 to 250,000. It is preferred to obtain a resin particle having excellent strength by a resin composition 1,4-containing a hydride of a styrene/butadiene copolymer having a weight average molecular weight within the above range. A method of producing a hydride of the styrene/butadiene copolymer is conventionally known, and the hydride is also commercially available. Examples of the commercially available product are TAFUTACK H1041 (manufactured by Asahi Kasei Co., Ltd., Mw: 70,000) having a styrene/ethylene/butene ratio of 30/70% by weight, and a styrene/ethylene.butene ratio of 48/52 by weight. % of JSR (shares) manufactured by DAINARON 8900). In the resin composition of the resin particles of the present invention, the weight ratio of the cyclic olefin resin to the styrene polymer is usually a cyclic olefin resin/styrene polymer = 99/1 to 50/50, preferably It is 95/5~70/30. When the weight ratio of the cyclic olefin resin to the styrene polymer satisfies the above ratio, the excellent heat resistance and transparency derived from the cyclic olefin resin can be maintained, and the fluidity or strength of the resin particles can be improved. Better. Further, the resin composition constituting the resin particles of the present invention may contain, as long as the effect of the present invention is not contained, preferably from 0 to 60% by weight based on 1% by weight of the resin component, for example, JP-A-9-221577 A specific hydrocarbon resin, a conventional thermoplastic resin, a thermoplastic elastomer, a rubbery polymer, an organic particle, or the like described in the above-mentioned publication, Japanese Laid-Open Patent Publication No. Hei. It is a resin component other than the polymer. Further, the resin composition can be produced by mixing a cyclic olefin resin with a styrene polymer and, if appropriate, the above hydrocarbon resin. For example, the mixture is kneaded by using a twin-screw extruder to obtain a granulated resin composition. In addition, the cyclic olefin resin and the styrene resin and, if appropriate, the hydrocarbon resin may be dissolved in a suitable solvent and uniformly mixed, and then obtained by the same method as the method for desolving the cyclic olefin resin. A desolvated granular resin composition. φ The resin particles of the present invention comprising the resin composition are particularly excellent in fluidity when welded, and specifically, the load flow rate (MFR) measured at a temperature of 260 ° C is usually 10 to 250 g/min at a load of 10 kg. It is preferably 20 to 200 g/min. &lt; Far infrared ray absorbing agent&gt; The resin particles of the present invention preferably contain a far infrared ray absorbing agent from the viewpoint of the absorption ability of far infrared rays. G The far-infrared ray absorbing agent is not limited to a type as long as it exhibits absorption in the wavelength range of the far-infrared rays (4 to 100 μm). Examples of the far-infrared ray absorbing agent are exemplified by organic dyes, organic pigments, inorganic dyes, inorganic pigments, other organic substances or inorganic substances. Further, the far-infrared ray absorbing agents may be colored or may be colorless within a range not impairing the effects of the present invention. Preferably, the color or absorption characteristics of the far-infrared absorbing agent are appropriately selected in accordance with the purpose of use of the resin particles of the present invention. Examples of the inorganic substance may be exemplified by inorganic fine particles, and examples of the organic substance may be exemplified by a compound containing a phosphorus atom. -33- 201012864 Inorganic fine particles are mostly heat-stable, and further resistant to heat resistance such as glass transition temperature of a cyclic olefin resin and a resin composition (hereinafter referred to as "cyclic olefin resin") It is preferable to diversify its particle size, shape, and the like to satisfy various purposes. Specific examples of the inorganic fine particles may be exemplified by carbonates such as calcium carbonate and barium carbonate; silicate clay, mica, kaolin mineral, mica clay mineral, smectite, serpentine mineral, talc, chlorite, strontium Clay minerals such as Vermiculite • Tellurite minerals. _ These are preferably citrate minerals, most preferably mica. The shape of the inorganic fine particles is not particularly limited, and may be spherical, needle-like, or other amorphous. The primary volume average particle diameter of the particle diameter of the inorganic fine particles is usually from 0.1 to 30 μm, preferably from 3 to 28 μm, and most preferably from 0.5 to 25 μm. When the average particle diameter is more than 3 Ομιη, the transparency of the cyclic olefin resin or the like is impaired. The compound containing a phosphorus atom may, for example, be phosphoric acid, a phosphate, a polyphosphoric acid, a phosphorous acid, a phosphite or a phosphonate. Among these, phosphates, phosphites, and phosphonates are low in corrosiveness, and are excellent in compatibility with a cyclic olefin resin component, and are preferably phosphate esters. The phosphates, phosphites, and phosphonates preferably have (¥〇_)3Ρ, (Υ0-)3Ρ = 0, and Υ(Υ〇-)2Ρ structures (wherein, the same number of molecules exist in the same molecule) The oxime may be the same or different, and the oxime may be an alkyl group such as a methyl group or an ethyl group (the alkyl group may have a substituent), an aryl group such as a phenyl group or a biphenyl group (the aryl group may have a substituent), and the like. Specific examples of such are triphenyl phosphite, diphenyl phenylphosphonate, dimethyl phenylphosphonate, trimethyl phosphate, triethyl phosphate, tri-34-201012864 butyl phosphate Ester, triphenyl phosphate, tricresol phosphate, trixyl phosphate, glycidyl phenyl phosphate, xylyl diphenyl phosphate, cresol bis (di-2,6-dimethylphenyl) Phosphate, di-2-ethylhexyl discate, meta-xylylene bis(di-2,6-dimethylphenyl)phosphate, bisphenol A bis(diphenyl)phosphate, bisphenol A Bis(xylenol) phosphate, 4,4'-diphenol bis(diphenyl) phosphate. Among these, cresol diphenyl phosphate, xylyl diphenyl phosphate φ, cresol bis(di-2,6-dimethylphenyl) phosphate, meta-xylenol bis (two-2, 6-dimethylphenyl)phosphate, bisphenol A bis(diphenyl)phosphate 'bisphenol A bis(xylenol) phosphate, 4,4'-diphenol bis(diphenyl)phosphate, It is preferred because of low volatility. Further, since meta-xylylene bis(di-2,6-dimethylphenyl)phosphate and 4,4,-diphenol bis(diphenyl)phosphate are solid, it is most suitable for a dry blending process. Inorganic compounds, phosphates, phosphites, and phosphonic acid vines can be selected according to the quality standards required for heat resistance or transparency. Also known as singly, singly or in combination. Further, inorganic compounds and phosphates, phosphites and phosphonates may be used in combination. The amount of the far-infrared ray absorbing agent added is a cyclic olefin-based resin (resin composition) with respect to the weight of the cyclic olefin-based resin or resin composition constituting the resin particles: Far-infrared ray absorbing agent = 99·99 : 0 · 0 1~70 : 30 amount, preferably 99.95 : 0.05~75 : 25 amount 'best 99.9: 0.1~80: 20 amount. When the amount of the far-infrared ray-absorbing agent added exceeds the above range, the transparency or heat resistance of the cyclic olefin-based resin or the like itself is impaired. In addition, when it is less than the above range, the utilization of far-infrared energy cannot be improved -35-201012864. The cyclic olefin resin or resin composition to which the far-infrared ray absorbing agent is added has excellent far-infrared absorbing ability, and when processed into a film having a thickness of 100 μm, the absorbance at a wave number of 94 5 (:1^1 is more than 0.36, more preferably When the absorbance is more than 0.4, the absorbance of the infrared ray is low, and therefore, when the resin particles of the present invention are processed by infrared rays, there is a problem that the thermal efficiency is lowered, etc. The cyclic olefin system to which the far-infrared ray absorbing agent is added is added. The total light transmittance of the film processed into a thickness of Λμηι is usually 85% or more, preferably 8 8% or more, more preferably 90% or more, and the turbidity is usually 10% or less, preferably 9%. In the following, it is preferably 8% or less. When the total light transmittance is less than 85% or the turbidity exceeds 10%, the internal identification of the molded body obtained by processing the resin particles of the present invention by a powder sintering lamination method or the like is performed. <The additive> The cyclic olefin resin or the resin composition constituting the resin particles of the present invention may be added with an antioxidant or a heat stabilizer as needed within a range not impairing the effects of the present invention. Light stabilizer, ultraviolet absorber, infrared absorber, antistatic agent, dispersant, processability enhancer, chlorine extractant, flame retardant, crystallization nucleating agent, anti-caking agent, anti-fogging agent, mold release agent , dyes, pigments, fluorescent whitening agents, organic or inorganic cerium materials, neutralizers, lubricants, decomposers, metal inerting agents, anti-contaminants, antibacterial or other resins, thermoplastic elastomers, etc. The additive may be used singly or in a plurality of kinds. The amount of the additive is usually 10,000 parts by mass or less based on 100 parts by mass of the cyclic olefin resin of -36 to 201012864. , 6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, hydrazine Methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,1,3-parade (2-methyl-4-hydroxy-5-third Butylphenyl)butane, 1,3,5-trimethyl-2,4,6-glucosin (3,5-di-t-butyl-4-hydroxybenzyl)benzene, stearyl-(3 ,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2 - Dioxo-yl-3,3'-di-t-butyl-5,5'-diethylphenylmethane, 3,9-bis[1,1-dimethyl-2-(yS-(3) -Tertibutyl-4.hydroxy-5-methylphenyl)propoxycarbonyl)ethyl], 2,4,8,10-tetraoxaspiro[5,5]undecane, ginseng (2 , 4-di-tert-butylphenyl)phosphite, cyclic neopentyltetrakis(2,4-di-t-butylphenyl)phosphite, cyclic neopentane tetrakis , 6-di-t-butyl-4-methylphenyl)phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, and the like. Further, commercially available products of antioxidants can be exemplified by the following. Irganox 1010, Irganox 1035, Irganox 1 076, Irganox 1 3 30, Irganox 245, Irgafos 168, Irgafos 38 manufactured by Ciba 曰本e Co., Ltd., ADEKASTAB AO-50, ADEKASTAB AO-60, manufactured by ADEKA Co., Ltd. , ADEKASTAB AO-3 3 0 , ADEKASTAB 21 12. The aforementioned ultraviolet absorber is exemplified by, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-(2H-benzotriazol-2-yl)-4,6. - bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-t-butylphenol, 2-benzotriazole- 2-based 4,6-di-t-butylphenol, -37- 201012864 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-[( 211-benzotriazol-2yl)phenol]]. [Resin Particles] The resin particles of the present invention have a volume average particle diameter of from 1 to 200 μm, preferably from 10 to 80 μm. When the volume average particle diameter is larger than the 200 μm, the thickness of one layer (sheet) of the cross section becomes thick when molded by the powder sintering lamination method, resulting in a lack of fineness of the three-dimensional shape. On the other hand, when the volume average particle diameter is less than ^ Ιμιη, the number of sheets becomes too large to cause lack of productivity. Further, the volume average particle diameter referred to in the present specification is the volume average particle diameter measured by MICROTACK ΜΤ 3 300 manufactured by Nikkiso Co., Ltd. regardless of the shape of the particles. The shape of the resin particles of the present invention is not particularly limited, and may be spherical or amorphous. Further, in the case where the particle size distribution of the obtained resin particles is wider than the desired distribution, it can be classified by a conventional classifier. The classification method can be wet or _ dry. Specifically, the classifier may be an inertial classifier such as an air separator, a dry centrifugal classifier such as a blower or a micro separator, a wet centrifugal classifier such as a centrifugal sediment machine or a liquid blower, or a sieve classifier. The resin particles of the present invention are particles composed of the above cyclic olefin resin or a resin composition containing a cyclic olefin resin and the styrene polymer. The method of forming the resin or the resin composition into particles can be carried out by various methods. For example, a cyclic olefin resin or the like can be used as the resin particles by an emulsification method or a mechanical pulverization method. The two methods will be described below. -38-201012864 &lt;Emulsification method&gt; When the resin particles of the present invention are produced by an emulsification method, a production method having the following steps is exemplified as a method for producing the same: a cyclic olefin resin or a resin composition is dissolved in an organic solvent In step 1, the solvent A obtained in the step 1 is emulsified in water or the aqueous solution B containing the surfactant B, and the particles such as the cyclic olefin hydrocarbon resin dispersed in the emulsion obtained in the step 2 are recovered. And dry step 3. These steps are explained below. (Step 1) The organic solvent to be used in the step 1 is not particularly limited as long as it can dissolve the cyclic olefin resin or the resin composition, and is, for example, petroleum ether, pentane, hexane, heptane, octane or decane. Hydrocarbons such as decane; cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, cyclobutane, cyclooctane, decahydronaphthalene, and norbornane; benzene, toluene, xylene, Aromatic hydrocarbons such as ethylbenzene, cumene, chlorobenzene; halogenated hydrocarbons such as dichloromethane, dichloroethane, chlorobutane, chloroform, tetrachloroethylene; methyl acetate, ethyl acetate, n-butyl acetate An ester such as isobutyl acetate or methyl propionate; an ether such as dibutyl ether, tetrahydrofuran, dimethoxyethane or dioxane-39- 201012864 Ν, Ν-dimethylformamide, hydrazine , guanamine such as hydrazine-dimethylacetamide or N-methylpyrrolidone. These may be used alone or in combination of two or more. Among these, aromatic hydrocarbons are preferably used from the viewpoint of solubility of a cyclic olefin resin or the like. Step 1 can be carried out, for example, by any of the following. (1) Any one of the following (a) to (d) is dissolved in the above organic solvent. (a) a powder such as a cyclic olefin resin other than the resin particles produced by the method for producing a resin particle described in the present specification, (c) recycling of a cyclic olefin resin or resin In the case of a film or an injection molded product of the composition, the film, the injection molded product or the pulverized product thereof, and the like (d) a mixture of the cyclic olefin resin particles and the dissimilar resin particles of the styrene polymer (2) are organic A cyclic olefin resin is synthesized in a solvent and hydrogenated as needed. In other words, the organic solvent used in the synthesis of the cyclic olefin resin is used as the organic solvent as it is. (3) A reaction solution obtained by synthesizing a cyclic olefin resin in the organic solvent and hydrogenating the resin as needed, and purifying and removing the residual monomer or catalyst by extraction purification or adsorption treatment. The concentration of the cyclic olefin resin in the organic solvent solution (hereinafter also referred to simply as the solution A) such as a cyclic olefin resin is usually 5 to 40% by mass, preferably 7 to 35% by mass, most preferably 10 to 30% by weight. quality%. When the concentration is less than 5 mass -40 to 201012864%, the productivity of particles such as a cyclic olefin resin is lowered. On the other hand, when it exceeds 40% by mass, the dispersibility of the solution A in the water or the aqueous solution B containing the surfactant described later is lowered, and there is a problem that resin particles having a desired particle diameter cannot be obtained. In the step 2, the solution A obtained in the step 1 is emulsified in the aqueous solution 〇 or the aqueous solution B containing the surfactant, and the cyclic olefin resin or the like is dispersed in the water or the aqueous solution B to have a particle shape. The stirring/dispersing means at the time of the emulsification is exemplified by a conventional stirring device, but is not particularly limited thereto. Specific examples of such devices may be, for example, a propeller type agitator, a serrated mixing and kneading machine, a closed drum kneading machine, a drum/stator type kneading machine, a static kneading machine, an in-line propeller/vortex type kneading machine, an in-line rotor. / Stator type kneading machine, colloidal mixer, high pressure homogenizer, etc.搅拌 The stirring conditions such as the rotation speed of the mixer vary depending on the production amount of the equipment or resin particles and other conditions, so the determination cannot be made, but it can be carried out by general stirring conditions (for example, 10 to 3,000 rpm). The stirring time is also not determined, but it is usually 5 to 300 minutes, preferably 10 to 180 minutes, more preferably 15 to 120 minutes. When the stirring time is shorter than 5 minutes, the dispersion of the cyclic olefin resin or the like is insufficient, and the resin particles having a desired particle diameter cannot be obtained. When the stirring time is longer than 300 minutes, the productivity of the resin particles tends to decrease. When the solution A is emulsified in water or in aqueous solution B, the temperature is usually -41 - 201012864 0~100t, preferably 5~80 °C, and most preferably l〇~6 (TC » emulsification temperature exceeds 100 ° C At this time, the resin particles tend to aggregate in the emulsion in which the solution A is emulsified. On the other hand, when the temperature is not reached, the production cost of the resin particles tends to increase. In the second step, the solution A and the water or the solution B The mass ratio (usage ratio) is usually [solution A] / [water or aqueous solution B] = l/100~5/1, preferably 1/5 0~4 Π, preferably 1/3 0~3/ 1. When the mass ratio of the solution A to water or the aqueous solution B is less than 1/100, the productivity of the resin particles tends to decrease. On the other hand, when it is more than 5/1, the resin particles are easily aggregated in the emulsion. There is a case where the resin particles having a desired particle diameter cannot be obtained. The medium in which the solution A is dispersed is water or an aqueous solution B, but is preferably aqueous solution B. The emulsification of the resin particles in the step 2 is carried out by the presence of a surfactant. The stability in the liquid is improved. The above surfactants can use conventional sodium fatty acid, potassium fatty acid, alkylbenzene Anionic surfactants such as sodium, sodium alkyl sulfate, sodium alkyl ether sulfate, sodium α-olefin sulfonate, sodium alkyl sulfonate; @ alkyltrimethylammonium salt, dialkyldimethylammonium salt a cationic surfactant such as a salt; an amphoteric surfactant such as an alkylamino fatty acid sodium, an alkylbetaine or an alkylamine oxide; a sucrose fatty acid ester, a sorbitan fatty acid ester, and a polyoxyethyl sorbitan Fatty acid esters, polyoxyalkylene esters, fatty acid alkanolamines, polyoxyalkylene ethers, polyoxyalkylene ethers, polyoxyalkylidene ethers, polyoxyalkylenes a nonionic surfactant such as a propyl fatty acid ester; however, it is not limited to these. The intermediate nonionic surfactant is compatible with a cyclic olefin resin or the like and is in a resin particle. It is preferable in terms of small residual effect on the resin particles. The best surfactant is polyoxyethylene ethyl ether, polyoxyalkylene ester, polyoxypropyl propyl ether, poly A derivative of polyoxyalkylene or polyoxypropylidene propyl such as propyl propyl acrylate.

更具體而言可舉例爲花王（股）製造之EMULGEN系 〇 列、LEODOL系列、EMUNOL系列，LION (股）製造之 LEOKUS 系列、LEOKOL 系列、LI ΟΝ Ο L 系列、LIΟ F A C T 系列、LIONON系列等。該等可單獨使用亦可複數種倂用 〇 前述界面活性劑之HLB値（親水性一親脂性平衡） 由於依據所用環狀烯烴系樹脂等之種類或有機溶劑之種類 適當的選擇而無法槪括的決定，但通常爲6〜20，較佳爲 7〜19.5 ，最佳爲7.5〜19。 © 前述界面活性劑於水溶液B中之濃度通常爲0.1〜20 質量％，較佳爲0.2~18質量％，最佳爲0.3〜15質量％。濃 度小於0.1質量％時樹脂粒子於步驟2中所得之乳化液中 之安定性不足。另一方面當濃度超過20質量％時，會有所 得樹脂粒子之粒徑小於必要以上，同時樹脂粒子中殘留之 界面活性劑量增加之傾向。 (步驟3 ) 以過濾器或網目等回收分散於前述步驟2中所得之乳 -43- 201012864 化物中之樹脂粒子並經乾燥，可獲得體積平均粒徑爲 1〜200μιη之樹脂粒子。 又，進行該回收之前’較佳將與步驟1所用之有機溶 劑及水二者相溶且不溶解環狀烯烴系樹脂等之溶劑C，與 步驟2中所得之乳化物混合。 藉由使用溶劑C，可使幾乎維持球形狀之樹脂粒子固 化，進而可萃取去除用以使環狀烯烴系樹脂等溶解所使用 之有機溶劑或界面活性劑而較佳。 前述所謂的「不溶解環狀烯烴系樹脂等」具體而言爲 溶解於25 °C之100克溶劑C中之環狀烯烴系樹脂等爲一 克以下。 滿足該等條件之溶劑C較佳爲甲醇、乙醇、丙醇、異 丙醇、正丁醇、第二丁醇、異丁醇等醇類，且最佳爲甲醇 、乙醇、丙醇、異丙醇。 溶劑C之使用量相對於100質量份之前述乳化液通常 爲30〜2000質量％，較佳爲50〜1000質量％。 又溶劑C與乳化液之混合較佳以攪拌機藉攪拌進行， 此時之攪拌條件通常爲轉數 1〇〜30,000rPm，攪拌溫度 〇〜6〇°C，攪拌時間5-120分鐘。 又，以過濾器或網目等回收分散於步驟2中所得之乳 化液中之樹脂粒子前，或者混合前述溶劑C與前述乳化液 之前，亦可加入對用以溶解環狀烯烴系樹脂等所用之有機 溶劑濃縮之步驟。藉由加入濃縮步驟，使乾燥時自樹脂粒 子中揮發之有機溶劑之量變少，可獲得更接近真球形狀之 -44 - 201012864 樹脂粒子。 回收前述樹脂粒子之過濾器或網目之孔徑係依據所需 樹脂粒子之粒徑選擇。藉由真空或熱風乾燥機等使回收之 樹脂粒子乾燥可成爲形狀安定之樹脂粒子。 乾燥溫度通常爲20〜160 °C，較佳爲30〜140 °C，更佳 爲40〜120°C。乾燥溫度未達20°C時會有乾燥時間變長使 生產性下降之傾向。另外，乾燥溫度超過160 °C時，會有 ❹樹脂粒子彼此熔接而無法獲得期望粒徑之樹脂粒子之問題 〇 如此般獲得之樹脂粒子中之殘留溶劑量通常未達1質 量％，較佳未達0.5質量％，更佳未達0.2質量％。殘留溶 劑在該範圍內之樹脂粒子長期儲存時之結塊性低。 另外，如前述之環狀烯烴系樹脂及樹脂組成物中可添 加遠紅外線吸收劑或各種添加劑。該等添加劑之添加例如 可在步驟1開始之前進行，又，於步驟1中使環狀烯烴系 ❹ 樹脂等溶解於有機溶劑中時，亦可將添加劑與環狀烯烴系 樹脂等同時添加於有機溶劑中並溶解。 又在添加中，爲了使環狀烯烴系樹脂等與添加劑充分 混合，可混合環狀烯烴系樹脂等之有機溶劑溶液與添加劑 之溶液或分散液，並使用習知之脫溶裝置脫溶。經過該操 作之混合物供給於前述步驟1中。 &lt;機械性粉碎法&gt; 機械性粉碎法係製造前述環狀烯烴系樹脂或樹脂組成 -45- 201012864 物，且藉由使該樹脂等經機械性粉碎，獲得樹脂粒子。 機械性粉碎可凍結粉碎，亦可在常溫下粉碎。實施機 械性粉碎之裝置列舉習知之各種裝置，舉例爲例如班柏里 硏磨機、噴射硏磨機、球磨機、螺旋硏磨機、切割硏磨機 、針磨機、二軸粉碎硏磨機。機械性粉碎時會產生樹脂之 摩擦熱，會有因溫度上升造成熔接而無法獲得期望粒徑之 粉末之狀況。據此，使用液態氮等使裝置及樹脂等一起冷 卻，使樹脂等脆化而破碎較佳。 _ 於環狀烯烴系樹脂等中添加包含前述遠紅外線吸收劑 之各種添加劑時，一般係在進行粉碎之前進行添加劑之添 加。添加時，可採用混合前述之溶液且採用脫溶之方法， 亦可採用使用擠出機等之混練方法。 再者，一般之機械粉碎法比乳化法更難以獲得球形粒 子。樹脂粒子之形狀不爲球形時，由於供給薄片一層份之 樹脂粒子時樹脂粒子之滑動性不良而不佳情況，因此使環 狀烯烴系樹脂等成爲樹脂粒子之方法，有以乳化法較佳之 @ 情況。另一方面，生產性由於以機械性粉碎法較佳’因此 依據要求之品質與製造成本適當的選擇樹脂粒子之製造方 法。 &lt;其他製法&gt; 本發明之樹脂粒子可採用前述方法以外之以下習知之 方法製造。 •使環狀烯烴系樹脂或樹脂組成物之顆粒與環狀稀煙 -46- 201012864 系樹脂等非相容性之異種高分子材料混練，將前述顆粒分 散於前述異種高分子材料中之後，將前述異種高分子材料 溶解於僅不溶解前述環狀烯烴系樹脂等之溶劑中，且回收 本發明之樹脂粒子之方法。該等技術揭示於特開2007-217651號公報中。 •使環狀烯烴系樹脂等之有機溶劑溶液經噴霧乾燥之 方法。該等技術揭示於特表2000-504642號公報中。 &lt;樹脂粒子之改質&gt; 於粉末燒結層合造形法等中使用以例如前述方法製造 之本發明之樹脂粒子時，因雷射造成樹脂粒子之熔接性· 溶接性不足時，係在樹脂粒子之表面上塗佈或接枝聚合異 種樹脂進行表面修飾，亦可使樹脂粒子成爲蕊•殼構造。 該等情況下，爲了不損及本發明之樹脂粒子原先具有之透 明性，因此以使用與前述樹脂粒子之折射率接近之材料或 ©修飾劑較佳。 另外，以粉末燒結層合造形法獲得之造形物中存在氣 泡等，且造成透明性不足時，亦可將與樹脂粒子之折射率 接近之熱或光硬化性樹脂含浸於前述造形物中，隨後進行 硬化處理等後處理。藉由進行該後處理，使造形物中之氣 泡消失，成爲透明性足夠者。 [實施例] 以下以實施例爲基準更具體說明本發明，但本發明並 -47- 201012864 不受該等實施例之限制。 &lt;分析方法&gt; GPC:使用凝膠滲透層析裝置（TOSOH (股）製造之 HLC-8220GPC，管柱；依序串聯 TOSOH製造之 GUARD COLUMN Hxl-H、TSK gel G7000HXL、TSK gel GMHX 兩 根、TSK gel G2000HXL，溶劑：四氫呋喃，流速： lmL/min，樣品濃度0.7~0.8wt%，樣品注入量：70μί ’測 _ 定溫度：40°C，檢出器：RI(40°C )，標準物質：TOSOH (股）製造之TSK標準聚苯乙烯），測定重量平均分子量 (Mw)及分子量分布（Mw/Mn)。又，前述Μη爲數平均 分子量。 NMR :使用超導核磁共振吸收裝置（NMR，Bruker公 司製造，商品名：AVANCE5 00 )，於氘化氯仿中測定1H-NMR，並計算出共聚合組成比及氫化率。 對數黏度7?:使用烏伯羅德氏型黏度計，於氯仿中， @ 試料濃度〇.5g/dL，於溫度30°C進行測定。More specifically, it can be exemplified by EMULGEN series, LEODOL series, EMUNOL series manufactured by Kao (share), LEOKUS series manufactured by LION (series), LEOKOL series, LI ΟΝ Ο L series, LI Ο F A C T series, LIONON series, and the like. These may be used singly or in combination with HLB(Hydrophilic-lipophilic balance) of the above-mentioned surfactant, and may not be selected depending on the type of the cyclic olefin resin to be used or the type of the organic solvent. The decision is usually 6 to 20, preferably 7 to 19.5, and most preferably 7.5 to 19. The concentration of the surfactant in the aqueous solution B is usually 0.1 to 20% by mass, preferably 0.2 to 18% by mass, most preferably 0.3 to 15% by mass. When the concentration is less than 0.1% by mass, the stability of the resin particles in the emulsion obtained in the step 2 is insufficient. On the other hand, when the concentration exceeds 20% by mass, the particle diameter of the resin particles is less than necessary, and the amount of surfactant remaining in the resin particles tends to increase. (Step 3) The resin particles dispersed in the milk-43-201012864 obtained in the above step 2 are recovered by a filter or a mesh or the like and dried to obtain a resin particle having a volume average particle diameter of 1 to 200 μm. Further, before the recovery, the solvent C which is compatible with both the organic solvent and the water used in the step 1 and which does not dissolve the cyclic olefin resin or the like is mixed with the emulsion obtained in the step 2. By using the solvent C, it is preferable to cure the resin particles having almost the spherical shape, and to extract and remove the organic solvent or the surfactant used for dissolving the cyclic olefin resin or the like. Specifically, the above-mentioned "insoluble cyclic olefin-based resin or the like" is preferably one or less gram of the cyclic olefin-based resin or the like dissolved in 100 g of the solvent C at 25 °C. The solvent C satisfying the above conditions is preferably an alcohol such as methanol, ethanol, propanol, isopropanol, n-butanol, second butanol or isobutanol, and is preferably methanol, ethanol, propanol or isopropanol. alcohol. The amount of the solvent C used is usually 30 to 2000% by mass, preferably 50 to 1000% by mass based on 100 parts by mass of the emulsion. Further, the mixing of the solvent C and the emulsion is preferably carried out by stirring with a stirrer. The stirring condition is usually a number of revolutions of 1 〇 to 30,000 rpm, a stirring temperature of 〇 6 6 ° C, and a stirring time of 5 to 120 minutes. Further, before the resin particles dispersed in the emulsion obtained in the step 2 are collected by a filter or a mesh, or before the solvent C and the emulsion are mixed, a solvent for dissolving the cyclic olefin resin or the like may be added. The step of concentrating the organic solvent. By adding a concentration step, the amount of the organic solvent volatilized from the resin particles during drying is reduced, and -44 - 201012864 resin particles closer to the true spherical shape can be obtained. The pore size of the filter or mesh for recovering the aforementioned resin particles is selected depending on the particle diameter of the desired resin particles. The recovered resin particles are dried by a vacuum or a hot air dryer to obtain a resin pellet having a stable shape. The drying temperature is usually from 20 to 160 ° C, preferably from 30 to 140 ° C, more preferably from 40 to 120 ° C. When the drying temperature is less than 20 °C, the drying time becomes long and the productivity is lowered. In addition, when the drying temperature exceeds 160 ° C, there is a problem that the resin particles are welded to each other and the resin particles having a desired particle diameter cannot be obtained. The amount of the residual solvent in the resin particles thus obtained is usually less than 1% by mass, preferably not Up to 0.5% by mass, more preferably less than 0.2% by mass. The residual solvent has a low caking property when the resin particles in this range are stored for a long period of time. Further, a far-infrared ray absorbing agent or various additives may be added to the above-mentioned cyclic olefin-based resin and resin composition. The addition of the additives may be carried out, for example, before the start of the step 1, and when the cyclic olefin-based resin or the like is dissolved in the organic solvent in the step 1, the additive and the cyclic olefin resin may be simultaneously added to the organic compound. Dissolved in the solvent. In addition, in order to sufficiently mix the cyclic olefin resin or the like with the additive, a solution or dispersion of an organic solvent solution such as a cyclic olefin resin and an additive may be mixed and desolvated by a conventional desolvation device. The mixture subjected to this operation is supplied to the aforementioned step 1. &lt;Mechanical Pulverization Method&gt; The mechanical pulverization method produces the above-mentioned cyclic olefin resin or resin composition -45-201012864, and the resin particles are mechanically pulverized to obtain resin particles. Mechanical pulverization can freeze and pulverize, and can also be pulverized at normal temperature. The apparatus for carrying out mechanical pulverization enumerates various conventional devices, such as, for example, a Banbury honing machine, a jet honing machine, a ball mill, a screw honing machine, a cutting honing machine, a pin mill, and a two-axis pulverizing honing machine. In the case of mechanical pulverization, the frictional heat of the resin is generated, and there is a case where the powder of the desired particle size cannot be obtained due to the temperature rise. According to this, it is preferable to use a liquid nitrogen or the like to cool the device together with a resin or the like, and to embrittle the resin or the like to be broken. When various additives containing the above-mentioned far infrared ray absorbing agent are added to a cyclic olefin resin or the like, the addition of the additive is generally performed before pulverization. When the addition is carried out, a method of mixing the above-mentioned solution and desolvation may be employed, or a kneading method using an extruder or the like may be employed. Further, the general mechanical pulverization method is more difficult to obtain spherical particles than the emulsification method. When the shape of the resin particles is not spherical, the slidability of the resin particles is poor when the resin particles of one layer of the sheet are supplied. Therefore, the method of forming the cyclic olefin resin or the like into the resin particles is preferably by the emulsification method. Happening. On the other hand, productivity is preferable because of the mechanical pulverization method. Therefore, a method of producing resin particles is appropriately selected in accordance with the required quality and manufacturing cost. &lt;Other Preparation Methods&gt; The resin particles of the present invention can be produced by the following conventional methods other than the above methods. • The particles of the cyclic olefin resin or the resin composition are kneaded with an incompatible polymer material such as a ring-shaped thin tobacco-46-201012864 resin, and the particles are dispersed in the heterogeneous polymer material. The heterogeneous polymer material is dissolved in a solvent which does not dissolve the cyclic olefin resin or the like, and the resin particles of the present invention are recovered. These techniques are disclosed in Japanese Laid-Open Patent Publication No. 2007-217651. • A method in which an organic solvent solution such as a cyclic olefin resin is spray-dried. These techniques are disclosed in Japanese Patent Publication No. 2000-504642. &lt;Modification of Resin Particles&gt; When the resin particles of the present invention produced by the above method are used in the powder sintering laminate forming method or the like, when the resin particles are insufficient in fusion and the solubility due to laser, the resin is insufficient. The surface of the particles is coated or graft-polymerized with a heterogeneous resin for surface modification, and the resin particles may be made into a core/shell structure. In these cases, in order not to impair the transparency originally possessed by the resin particles of the present invention, it is preferred to use a material or a modifier which is close to the refractive index of the resin particles. In addition, when bubbles or the like are present in the formed product obtained by the powder sintering layer forming method, and the transparency is insufficient, the heat or photocurable resin which is close to the refractive index of the resin particles may be impregnated into the above-mentioned shape, and then Post-treatment such as hardening treatment. By performing this post-treatment, the bubbles in the form are eliminated, and transparency is sufficient. [Examples] Hereinafter, the present invention will be more specifically described on the basis of examples, but the present invention is not limited by the examples. &lt;Analytical method&gt; GPC: using a gel permeation chromatography apparatus (HLC-8220GPC manufactured by TOSOH Co., Ltd., column; GUARD COLUMN Hxl-H, TSK gel G7000HXL, TSK gel GMHX manufactured by serially connected TOSOH) , TSK gel G2000HXL, solvent: tetrahydrofuran, flow rate: lmL / min, sample concentration 0.7 ~ 0.8wt%, sample injection amount: 70μί 'measurement _ constant temperature: 40 ° C, detector: RI (40 ° C), standard Substance: TSK standard polystyrene manufactured by TOSOH (stock), weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were measured. Further, the above Μη is a number average molecular weight. NMR: 1H-NMR was measured in deuterated chloroform using a superconducting nuclear magnetic resonance absorption apparatus (NMR, manufactured by Bruker, trade name: AVANCE 5 00), and a copolymerization composition ratio and a hydrogenation ratio were calculated. Logarithmic viscosity 7?: Determined at a temperature of 30 ° C using an Ubbeld-type viscometer in chloroform, @sample concentration 〇.5g/dL.

Tg:不差掃描熱量計（SII Nanotechnology公司製造 ，商品名：DSC6220 )，依據日本工業規格K7121求得外 插之玻璃轉移溫度。 體積平均粒徑：使用日機裝（股）製造之 MICROTRACK mt3300 測定。 掃描型電子顯微鏡：使用日本電子（股）製造之JSM 6360LA 型。 -48- 201012864 MFR :使用TECHNO · JAPAN (股）製造之半自動化 融熔指數計L251’以JIS K7210B法爲準’測定荷重10Kg ，溫度26(TC下之融熔流動率（MFR)。 [合成例1] 於經氮氣置換之反應容器中饋入1〇〇克作爲單體之下 述式（la)表示之 8-甲氧羰基-8-甲基四環 φ [4.4.0.125.l7Q]-3 -十二碳烯、7.2克作爲分子量調節劑之 1-己烯，以及200克之甲苯，且加熱至80 °C。 於其中添加0.21毫升含三乙基鋁（0.6莫耳/升）之甲 苯溶液，及0.86毫升之甲醇改質之WC16甲苯溶液（ 0.025莫耳/升），且藉由在80°C下反應一小時獲得開環聚 合物。 接著，於所得開環聚合物溶液中添加0.04克之氫化 觸媒氯羰基參（三苯基膦）釕（RuHC1(CO)[P(C6H5)3]3) ❿ ，使氫氣壓力成爲9〜lOMPa，並於160~165°c之溫度反應 3小時。 反應結束後，藉由使所得產物於大量甲醇中沉澱獲得 氫化物[玻璃轉移溫度（Tg ) =163°C，重量平均分子量（ Mw) = 6·7χ104，分子量分布（Mw/Mn) =5.0，對數黏度 0.45dL/g，MFR=13g/10min，產量 90 克（產率 90%)]。 以NMR測定求得之氫化物之氫化率爲99.0%以上。爾後 ，所得開環聚合氫化物稱爲環狀烯烴系樹脂1A。 -49- 201012864 [化 15]Tg: an inferior scanning calorimeter (manufactured by SII Nanotechnology Co., Ltd., trade name: DSC6220), and an external glass transition temperature was obtained in accordance with Japanese Industrial Standard K7121. Volume average particle size: determined by using MICROTRACK mt3300 manufactured by Nikkiso Co., Ltd. Scanning Electron Microscope: JSM 6360LA type manufactured by JEOL Ltd. -48- 201012864 MFR : The semi-automatic melt index meter L251' manufactured by TECHNO · JAPAN Co., Ltd. is based on JIS K7210B method. 'Measure the load 10Kg, temperature 26 (melt flow rate (TCF) under TC. [Synthesis Example 1] 8-methoxycarbonyl-8-methyltetracyclic φ [4.4.0.125.l7Q] represented by the following formula (la) which is fed in a nitrogen-substituted reaction vessel with 1 gram of a monomer as a monomer. 3-dodecene, 7.2 g of 1-hexene as a molecular weight regulator, and 200 g of toluene, and heated to 80 ° C. 0.21 ml of toluene containing triethylaluminum (0.6 mol/liter) was added thereto. The solution, and 0.86 ml of methanol-modified WC16 toluene solution (0.025 mol/L), and a ring-opening polymer was obtained by reacting at 80 ° C for one hour. Next, 0.04 was added to the obtained ring-opening polymer solution. Hydrogenation catalyst chlorocarbonyl ginseng (triphenylphosphine) ruthenium (RuHC1(CO)[P(C6H5)3]3) ❿ , making hydrogen pressure 9~lOMPa, and reacting at 160~165°c for 3 hours After the end of the reaction, a hydride was obtained by precipitating the obtained product in a large amount of methanol [glass transition temperature (Tg) = 163 ° C, weight average fraction The amount (Mw) = 6·7χ104, molecular weight distribution (Mw/Mn) = 5.0, logarithmic viscosity 0.45dL/g, MFR=13g/10min, yield 90g (yield 90%)]. Hydrogenation determined by NMR measurement The hydrogenation ratio of the material is 99.0% or more. Thereafter, the obtained ring-opening polymerization hydride is referred to as a cyclic olefin resin 1A. -49- 201012864 [Chem. 15]

[合成例2] 將144克以前述式（la)表示之單體，6克以下述式 (2a)表示之單體，14.4克作爲分子量調節劑之1-己烯及 參[Synthesis Example 2] 144 g of the monomer represented by the above formula (la), 6 g of the monomer represented by the following formula (2a), and 14.4 g of 1-hexene as a molecular weight modifier and ginseng

225克甲苯饋入經氮氣置換之反應容器中，且加熱至80°C 〇 於其中添加0.34毫升含三乙基鋁（0.6莫耳/升）之甲 苯溶液’及1.37毫升之甲醇改質之 WC16甲苯溶液（ 0.025莫耳/升），藉由在80°C下反應一小時獲得開環聚合 物。 接著，於所得開環聚合物溶液中添加0.06克之氫化 觸媒氯羰基參（三苯基膦）釕（ruhci(co)[p(c6h5)3]3 ) ® ，且使氫氣壓力成爲9~10MPa，在160〜165°C之溫度反應 3小時。 反應結束後，藉由使所得產物於大量甲醇中沉澱獲得 氫化物[玻璃轉移溫度（Tg ) =154 t，重量平均分子量（225 g of toluene was fed into a nitrogen-substituted reaction vessel and heated to 80 ° C. 0.34 ml of a toluene solution containing triethylaluminum (0.6 mol/liter) was added thereto and 1.37 ml of methanol-modified WC16 was added thereto. A toluene solution (0.025 mol/liter) was obtained by reacting at 80 ° C for one hour to obtain a ring-opening polymer. Next, 0.06 g of a hydrogenation catalyst chlorocarbonyl ginseng (triphenylphosphine) ruthenium (ruhci(co)[p(c6h5)3]3) ® was added to the obtained ring-opening polymer solution, and the hydrogen pressure was 9 to 10 MPa. The reaction was carried out at a temperature of 160 to 165 ° C for 3 hours. After completion of the reaction, a hydride was obtained by precipitating the obtained product in a large amount of methanol [glass transition temperature (Tg) = 154 t, weight average molecular weight (

Mw) = 7.4xl〇4，分子量分布（Mw/Mn ) =4.2，對數黏度 0.55dL/g，產量90克（產率90% )]。以NMR測定求得之 氫化物之氫化率爲99.0%以上。共聚合組成比爲[源自（la )之構造]/[源自（2a)之構造]= 95.8/4 ·2(重量比）。爾 -50- 201012864 後，所得開環聚合氫化物稱爲環狀烯烴系樹脂2A。 [化 16]Mw) = 7.4xl〇4, molecular weight distribution (Mw/Mn) = 4.2, logarithmic viscosity 0.55dL/g, yield 90g (yield 90%)]. The hydrogenation ratio of the hydride obtained by NMR measurement was 99.0% or more. The copolymerization composition ratio is [structure derived from (la)] / [structure derived from (2a)] = 95.8 / 4 · 2 (weight ratio). After the -50-201012864, the obtained ring-opening polymerization hydride is referred to as a cyclic olefin resin 2A. [Chemistry 16]

(2a) ® [合成例3] 將113.2克以前述式（la)表示之單體，1.5克以前 述式（2a)表示之單體，35.3克以下述式（3a)表示之單 體’ 20.5克作爲分子量調節劑之1-己烯及225克甲苯饋入 經氮氣置換之反應容器中，且加熱至8 0 °C。 於其中添加0.34毫升含三乙基鋁（0.6莫耳/升）之甲 苯溶液，及1.39毫升之甲醇改質之 WC16甲苯溶液（ 0.025莫耳/升），且藉由在80°C反應一小時獲得開環聚合 ❹ 物。 接著，於所得開環聚合物溶液中添加〇.〇6克之氫化 觸媒（4-戊基苯甲醯氧基）羰基（氫化）雙（三苯基膦） 釘{RuH(OCO-Ar-CH2CH2CH2CH2CH3)(CO)[P(C6H5)3]2 (式 中Ar表示對伸苯基）}，升溫至9(TC後，使氫氣壓力成爲 9~ 10MPa，接著升溫至160〜165 °C反應3小時。 反應結束後，藉由使所得產物於大量甲醇中沉澱獲得 氫化物[玻璃轉移溫度（Tg ) =141°C，重量平均分子量（ Mw) =4.4χ104，分子量分布（Mw/Mn) =5_1，對數黏度 -51 - 201012864 0.41 dL/g ’產量90克（產率90% )]。以NMR測定求得之 氫化物之氫化率爲99.0%以上。共聚合組成比爲[源自（la )之構造]/[源自（2a)之構造]/[源自（3a)之構造 ]=75.3/1.1 /23.6 (重量比）。爾後，所得開環聚合氫化物 稱爲環狀烯烴系樹脂3A。 [化 17](2a) ® [Synthesis Example 3] 113.2 g of the monomer represented by the above formula (la), 1.5 g of the monomer represented by the above formula (2a), and 35.3 g of the monomer represented by the following formula (3a) 20.5 The 1-hexene as a molecular weight regulator and 225 g of toluene were fed into a nitrogen-substituted reaction vessel and heated to 80 °C. 0.34 ml of a toluene solution containing triethylaluminum (0.6 mol/liter), and 1.39 ml of a methanol-modified WC16 toluene solution (0.025 mol/liter) were added thereto, and reacted at 80 ° C for one hour. A ring-opening polymeric oxime is obtained. Next, 6 g of a hydrogenation catalyst (4-pentyl benzhydryloxy)carbonyl (hydrogenated) bis(triphenylphosphine) nail {RuH(OCO-Ar-CH2CH2CH2CH2CH3) was added to the obtained ring-opening polymer solution. (CO)[P(C6H5)3]2 (wherein Ar represents a para-phenylene group)}, and the temperature is raised to 9 (after TC, the hydrogen pressure is 9 to 10 MPa, and then the temperature is raised to 160 to 165 ° C for 3 hours) After completion of the reaction, a hydride was obtained by precipitating the obtained product in a large amount of methanol [glass transition temperature (Tg) = 141 ° C, weight average molecular weight (Mw) = 4.4 χ 104, molecular weight distribution (Mw / Mn) = 5_1, Logarithmic viscosity -51 - 201012864 0.41 dL/g 'yield 90 g (yield 90%)]. The hydrogenation ratio of the hydride obtained by NMR measurement was 99.0% or more. The copolymerization composition ratio was [from (la) Structure] / [Structure derived from (2a)] / [Structure derived from (3a)] = 75.3 / 1.1 / 23.6 (weight ratio). Thereafter, the obtained ring-opening polymerization hydride is referred to as cyclic olefin resin 3A. [化17]

[合成例4] 除將1-己烯之使用量變成1.8克以外，餘與合成例1 相同，獲得開環聚合氫化物。玻璃轉移溫度（Tg) =168 °C ，重量平均分子量（Mw) =22xl04，分子量分布（Mw/Mn )=5.0，對數黏度1.00dL/g，產量90克（產率90%)]。 以NMR測定求得之氫化物之氫化率爲99.0%以上。爾後 ，所得開環聚合氫化物稱爲環狀烯烴系樹脂4A。 [合成例5] 除將卜己烯之使用量變成12克以外，餘與合成例1 相同，獲得開環聚合氫化物。玻璃轉移溫度（Tg )= 1 60 °C ，重量平均分子量（Mw) =2·8χ104，分子量分布（Mw/Mn )=5.0，對數黏度〇.29dL/g，產量90克（產率90%)]。 -52- 201012864 以NMR測定求得之氫化物之氫化率爲99.0%以上。爾後 ，所得開環聚合氫化物稱爲環狀烯烴系樹脂5A。 [合成例6] 將133.5克以前述式（la)表示之單體，16.5克以前 述式（2a)表示之單體，15.4克作爲分子量調節劑之1-己 烯及22 5克甲苯饋入經氮氣置換之反應容器中，且加熱至 ©80。。。 於其中添加0.34毫升含三乙基鋁（0.6莫耳/升）之甲 苯溶液，及1.37毫升之甲醇改質之 WC16甲苯溶液（ 0.025莫耳/升），且藉由在80 °C反應一小時獲得開環聚合 物。 接著，於所得開環聚合物溶液中添加0.06克之氫化 觸媒氯羰基參（三苯基膦）釕（RuHC1(CO)[P(C6H5)3]3) ，且使氫氣壓力成爲9〜lOMPa，在160〜165°C之溫度反應 © 3小時。 反應結束後，藉由使所得產物於大量甲醇中沉澱獲得 氫化物[玻璃轉移溫度（Tg ) =126°C，重量平均分子量（ Mw) =5·0χ104，分子量分布（Mw/Mn) =4.2，對數黏度 0.43dL/g，產量90克（產率90% )]。以NMR測定求得之 氫化物之氫化率爲99.0%以上。共聚合組成比爲[源自（la )之構造]/[源自（2a)之構造]= 89/11 (重量比）。爾後 ，所得開環聚合氫化物稱爲環狀烯烴系樹脂6A。 -53- 201012864 [合成例7] 將113.2克以前述式（la)表示之單體，i.5克以前 述式（2a)表示之單體，35.3克以前述式（3a)表示之單 體，17.0克作爲分子量調節劑之卜己烯及225克甲苯饋入 經氮氣置換之反應容器中，且加熱至80 °c ° 於其中添加0.34毫升含三乙基鋁（〇.6莫耳/升）之甲 苯溶液，及1_39毫升之甲醇改質之WCU甲苯溶液（ 0.025莫耳/升），且藉由在80 °C反應一小時獲得開環聚合 麵 物。 接著，於所得開環聚合物溶液中添加〇.〇6克之氫化 觸媒（4-戊基苯甲醯氧基）羰基（氫化）雙（三苯基膦） 釕{RuH(OCO-Ar-CH2CH2CH2CH2CH3)(CO)[P(C6H5)3]2 (式 中Ar表示對伸苯基）}，升溫至90°C後，使氫氣壓力成爲 9~10MPa，接著升溫至16 0~165°C反應3小時。 反應結束後，藉由使所得產物於大量甲醇中沉澱獲得 氫化物[玻璃轉移溫度（Tg) =144 °C，重量平均分子量（ _[Synthesis Example 4] A ring-opening polymerization hydride was obtained in the same manner as in Synthesis Example 1, except that the amount of 1-hexene used was changed to 1.8 g. Glass transition temperature (Tg) = 168 ° C, weight average molecular weight (Mw) = 22 x 10 4 , molecular weight distribution (Mw / Mn) = 5.0, logarithmic viscosity 1.00 dL / g, yield 90 g (yield 90%)]. The hydrogenation ratio of the hydride obtained by NMR measurement was 99.0% or more. Thereafter, the obtained ring-opening polymerization hydride is referred to as a cyclic olefin resin 4A. [Synthesis Example 5] A ring-opening polymerization hydride was obtained in the same manner as in Synthesis Example 1, except that the amount of use of the hexene was changed to 12 g. Glass transition temperature (Tg) = 1 60 °C, weight average molecular weight (Mw) = 2. 8 χ 104, molecular weight distribution (Mw / Mn) = 5.0, logarithmic viscosity 〇. 29dL / g, yield 90 grams (yield 90%) ]. -52-201012864 The hydrogenation ratio of the hydride obtained by NMR measurement was 99.0% or more. Thereafter, the obtained ring-opening polymerization hydride is referred to as a cyclic olefin resin 5A. [Synthesis Example 6] 133.5 g of the monomer represented by the above formula (la), 16.5 g of the monomer represented by the above formula (2a), and 15.4 g of 1-hexene as a molecular weight modifier and 22 5 g of toluene were fed. The reaction vessel was replaced with nitrogen and heated to 80. . . 0.34 ml of a toluene solution containing triethylaluminum (0.6 mol/liter) and 1.37 ml of a methanol-modified WC16 toluene solution (0.025 mol/liter) were added thereto, and reacted at 80 ° C for one hour. A ring-opening polymer is obtained. Next, 0.06 g of a hydrogenation catalyst chlorocarbonyl ginseng (triphenylphosphine) ruthenium (RuHC1(CO)[P(C6H5)3]3) was added to the obtained ring-opening polymer solution, and the hydrogen pressure was changed to 9 to 10 MPa. The reaction was carried out at a temperature of 160 to 165 ° C for 3 hours. After completion of the reaction, a hydride was obtained by precipitating the obtained product in a large amount of methanol [glass transition temperature (Tg) = 126 ° C, weight average molecular weight (Mw) = 5.0 χ 104, molecular weight distribution (Mw / Mn) = 4.2, The logarithmic viscosity was 0.43 dL/g, and the yield was 90 g (yield 90%)]. The hydrogenation ratio of the hydride obtained by NMR measurement was 99.0% or more. The copolymerization composition ratio is [structure derived from (la)] / [structure derived from (2a)] = 89/11 (weight ratio). Thereafter, the obtained ring-opening polymerization hydride is referred to as a cyclic olefin resin 6A. -53-201012864 [Synthesis Example 7] 113.2 g of the monomer represented by the above formula (la), i. 5 g of the monomer represented by the above formula (2a), and 35.3 g of the monomer represented by the above formula (3a) 17.0 g of p-hexene as a molecular weight regulator and 225 g of toluene were fed into a nitrogen-substituted reaction vessel, and heated to 80 ° C °, and 0.34 ml of triethylaluminum-containing (〇.6 mol/liter) was added thereto. A toluene solution, and 1 - 39 ml of a methanol-modified WCU toluene solution (0.025 m/l), and a ring-opening polymeric facestock was obtained by reacting at 80 ° C for one hour. Next, 6 g of a hydrogenation catalyst (4-pentyl benzhydryloxy)carbonyl (hydrogenated) bis(triphenylphosphine) ruthenium {RuH(OCO-Ar-CH2CH2CH2CH2CH3) was added to the obtained ring-opening polymer solution. (CO)[P(C6H5)3]2 (wherein Ar represents a para-phenylene group)}, after raising the temperature to 90 ° C, the hydrogen pressure is 9 to 10 MPa, and then the temperature is raised to 16 0 to 165 ° C. hour. After completion of the reaction, a hydride was obtained by precipitating the obtained product in a large amount of methanol [glass transition temperature (Tg) = 144 ° C, weight average molecular weight ( _

Mw) =5·3χ104，分子量分布（Mw/Mn) =4.8，對數黏度 0.51dL/g，MFR = 25 克/ lOmin，產量 90 克（產率 90%)]。 以N M R測定求得之氫化物之氫化率爲9 9 · 0 %以上。共聚 合組成比爲[源自（la)之構造]/[源自（2a)之構造]/[源 自（3a )之構造]= 75.3/1.4/23.3 (重量比）。爾後，所得 開環聚合氫化物稱爲環狀烯烴系樹脂7A。 [實施例1] -54- 201012864 使49克合成例1中所得之環狀烯烴系樹脂1A溶解於 148克甲苯中，調製溶液。另一方面，將2.0克花王（股 )製造之非離子界面活性劑EMULGEN 130Κ (聚氧伸乙基 月桂基醚 HLB = 18.1)溶解於188克離子交換水中，調製 水溶液。 將界面活性劑之水溶液注入500毫升容器中，且在 PRIMIX (股）製造之 TK均質機MARKII中，一邊於 H 2000〜25 00 rpm之轉數下攪拌，一邊將環狀烯烴系樹脂1 A 之甲苯溶液倒入界面活性劑之水溶液中。 隨後，在2 5 °C繼續攪拌1小時。 將該乳化液注入1420克甲醇中，使用三一馬達（螺 旋翼），在25°C以2 00rpm攪拌10分鐘。以不鏽鋼製之 5 00網目金屬網回收析出之樹脂，且於100 °C之真空乾燥 機中乾燥12小時。樹脂粒子之回收率爲95%，體積平均 粒徑爲36μιη。以掃描電子顯微鏡觀察回收之樹脂粒子之 〇形狀後，大致上爲球狀。 [實施例2] 除使EMULGEN 13 0Κ之使用量成爲1_〇克以外，餘與 實施例1相同，以回收率98%獲得樹脂粒子。樹脂粒子之 體積平均粒徑爲67μιη，且形狀大致上爲球形。 [實施例3] 除使用合成例2中獲得之環狀烯烴系樹脂2Α以外， -55- 201012864 餘與實施例1相同’以回收率96%獲得樹脂粒子。樹脂粒 子之體積平均粒徑爲5 0μιη ’且形狀大致上爲球形。 [實施例4] 除使用合成例3中獲得之環狀烯烴系樹脂3Α以外， 餘與實施例1相同，以回收率9 5 %獲得樹脂粒子。樹脂粒 子之體積平均粒徑爲78 μπι，且形狀大致上爲球形。 [實施例5] 除使用合成例3中獲得之環狀烯烴系樹脂3Α，使 EMULGEN 130Κ之使用量成爲20.0克以外，餘與實施例1 相同’以回收率95 %獲得樹脂粒子。樹脂粒子之體積平均 粒徑爲18μιη，且形狀大致上爲球形。 [實施例6] 如實施例2般製備樹脂粒子。將所得樹脂粒子置於濕 φ 式振動過篩機上，通過63μιη孔徑之篩網，回收被捕集留 在53μιη孔徑之篩網上之粒子並經真空乾燥。回收率爲 2 5%。 [實施例7] 除使2〇克合成例I中所得之環狀烯烴系樹脂ΙΑ溶解 於180克之甲苯中，且將EMULGEN 130Κ之使用量變成 1 ·〇克以外，餘與實施例1相同，以回收率95%獲得樹脂 -56- 201012864 粒子。樹脂粒子之體積平均粒徑爲15μιη，且形狀大致上 爲球形。 [實施例8] 以雙軸擠出機使將0.3重量份之抗氧化劑肆[亞甲基-3-(3,5-二第三丁基-4-羥基苯基）丙酸酯]甲烷添加於100 重量份之合成例1中獲得之環狀烯烴系樹脂1Α而成者作 〇 成顆粒後，使用鎚式硏磨機（Hummer Mill )進行機械凍 結粉碎後，獲得體積平均粒徑49μιη之樹脂粒子，回收率 爲 90%。 [實施例9] 以雙軸擠出機使將0.3重量份之抗氧化劑肆[亞甲基-3-(3,5-二第三丁基-4-羥基苯基）丙酸酯]甲烷添加於100 重量份之合成例2中獲得之環狀烯烴系樹脂2A而成者作 ® 成顆粒後，使用鎚式硏磨機（Hummer Mill )進行機械凍 結粉碎後，獲得體積平均粒徑60μΓη之樹脂粒子，回收率 爲 90%。 [實施例10] 以雙軸擠出機使將0.3重量份之抗氧化劑肆[亞甲基· 3-(3,5-二第三丁基-4-羥基苯基）丙酸酯]甲烷添加於100 重量份之合成例·3中獲得之環狀烯烴系樹脂3A而成者作 成顆粒後，使用鎚式硏磨機（Hummer Mill)進行機械凍 -57- 201012864 結粉碎後，獲得體積平均粒徑60 μιη之樹脂粒子，回收率 爲 9 0%。 [實施例11] 以雙軸擠出機使將0.3重量份之抗氧化劑肆[亞甲基-3-(3,5-二第三丁基-4-羥基苯基）丙酸酯]甲烷添加於1〇〇 重量份之合成例6中獲得之環狀烯烴系樹脂6A而成者成 爲顆粒後，使用鎚式硏磨機（Hummer Mill )進行機械凍 參 結粉碎後，獲得體積平均粒徑46μιη之樹脂粒子’回收率 爲 92%。 [實施例12] 使用雙軸擠出機（TEM-37BS ’東芝機械製造）混練 9.5公斤之將0.3重量份之抗氧化劑肆[亞甲基-3- ( 3,5-二 第三丁基-4-羥基苯基）丙酸酯]甲烷添加於1〇〇重量份之 合成例1中獲得之環狀烯烴系樹脂1Α而成者’與0.5公 春 斤之苯乙烯/乙烯•丁烯比率爲3 0/70重量％之苯乙烯系熱 可塑性彈性體（旭化成（股）製造，TAFT A CK Η1041 ) ’ 獲得顆粒狀之熱可塑性樹脂組成物。汽缸溫度爲280 °C ’ 軸轉速爲10 〇r pm，擠出速度爲10〜2 Okg/hr。所得顆粒外 観爲透明，其MFR爲21克/ lOmin。 使用鎚式硏磨機對所得顆粒進行機械凍結粉碎後’獲 得體積平均粒徑50μπι之樹脂粒子’回收率爲90%° -58- 201012864 [實施例13] 除使用9公斤之將0.3重量份之抗氧化劑肆[亞甲基-3-(3,5-二第三丁基-4-羥基苯基）丙酸酯]甲烷添加於100 重量份之合成例1中獲得之環狀烯烴系樹脂1A而成者， 與1.0公斤之苯乙烯/乙烯•丁烯比率爲30/70重量％之苯 乙烯系熱可塑性彈性體（旭化成（股）製造，TAFTACK Η 1 04 1 )以外，餘與實施例1 2相同獲得顆粒。所得顆粒之 φ MFR 爲 28 克 /1 Omin。 使用鎚式硏磨機對所得顆粒進行機械凍結粉碎後，獲 得體積平均粒徑52μιη之樹脂粒子，回收率爲90%。 [實施例14] 除使用9.5公斤之將0.3重量份之抗氧化劑肆[亞甲 基-3-(3,5-二第三丁基-4-羥基苯基）丙酸酯]甲烷添加於 1〇〇重量份之合成例7中獲得之環狀烯烴系樹脂7Α而成 © 者，與0.5公斤之苯乙烯/乙烯•丁烯比率爲3 0/70重量％ 之苯乙烯系熱可塑性彈性體（旭化成（股）製造， TAFTACK H1041 )以外，餘與實施例12相同獲得顆粒。 所得顆粒之MFR爲41克/ lOmin。 使用鎚式硏磨機對所得顆粒進行機械凍結粉碎後，獲 得體積平均粒徑51μιη之樹脂粒子，回收率爲92%。 [實施例15] 除使用8.5公斤之將0.3重量份之抗氧化劑肆[亞甲 -59- 201012864 基- 3-( 3，5-二第三丁基-4-羥基苯基）丙酸酯]甲烷添加於 100重量份之合成例7中獲得之環狀烯烴系樹脂7A而成 者，與1.5公斤之苯乙烯/乙烯•丁烯比率爲3 0/70重量％ 之苯乙烯系熱可塑性彈性體（旭化成（股）製造， TAFTACK H1041 )以外，餘與實施例12相同獲得顆粒。 所得顆粒之MFR爲63克/ lOmin。 使用鎚式硏磨機對所得顆粒進行機械凍結粉碎後，獲 得體積平均粒徑50μπι之樹脂粒子，回收率爲90%。 [實施例16] 除使用9公斤之將0.3重量份之抗氧化劑肆[亞甲基-3-(3,5-二第三丁基-4-羥基苯基）丙酸酯]甲烷添加於1〇〇 重量份之合成例7中獲得之環狀烯烴系樹脂7Α而成者， 與1.0公斤之苯乙烯/乙烯•丁烯比率爲48/52重量％之苯 乙烯系熱可塑性彈性體（JSR (股）製造，Dynaron 8900 )以外，餘與實施例12相同獲得顆粒。所得顆粒之MFR _ 爲 5 2 克 /1 Omin。 使用鎚式硏磨機對所得顆粒進行機械凍結粉碎後，獲 得體積平均粒徑50μπι之樹脂粒子，回收率爲91%。 [實施例17] 除使用8公斤之將〇·3重量份之抗氧化劑肆[亞甲基-3-(3,5-二第三丁基-4-羥基苯基）丙酸酯]甲烷添加於100 重量份之合成例1中獲得之環狀烯烴系樹脂1Α而成者， -60- 201012864 與2公斤之苯乙烯系樹脂（YASUHARA化學（股）製造 ，SX100)以外，餘與實施例12相同獲得顆粒。所得顆粒 之 MFR 爲 1 00 克 /1 Omin。 使用鎚式硏磨機對所得顆粒進行機械凍結粉碎後，獲 得體積平均粒徑50μιη之樹脂粒子，回收率爲89%。 [實施例18] φ 除使用8.5公斤之將0.3重量份之抗氧化劑肆[亞甲 基-3-(3,5-二第三丁基-4-羥基苯基）丙酸酯]甲烷添加於 1 〇〇重量份之合成例7中獲得之環狀烯烴系樹脂7A而成 者，與1.5公斤之苯乙烯系樹脂（YASUHARA化學（股） 製造，SX100)以外，餘與實施例12相同獲得顆粒。所得 顆粒之MFR爲140克/lOrnin。 使用鎚式硏磨機對所得顆粒進行機械凍結粉碎後，獲 得體積平均粒徑48 μιη之樹脂粒子，回收率爲89%。 ❹ [比較例1] 除使用合成例4獲得之環狀烯烴系樹脂4Α以外，餘 與實施例1相同，以回收率96%獲得樹脂粒子。樹脂粒子 之體積平均粒徑爲99 μιη，且形狀大致上爲球形。 [比較例2] 除使用合成例5獲得之環狀烯烴系樹脂5Α以外，餘 與實施例1相同’以回收率96%獲得樹脂粒子。樹脂粒子 -61 - 201012864 之體積平均粒徑爲20μιη，且形狀大致上爲球形。 [比較例3] 如實施例2般製備樹脂粒子。將所得樹脂粒子置於濕 式振動過篩機上，回收被捕集留在2ΟΟμιη孔徑之篩網上之 樹脂粒子。所回收之樹脂粒子體積平均粒徑爲220μϊη，回 收率爲5%。 ❹ &lt;評價&gt; 將1克實施例與比較例獲得之樹脂粒子加入3.5毫升 之樣品瓶中，在設定在比環狀烯烴系樹脂之玻璃轉移溫度 高5 0°C之溫度之烘箱中加熱熔接。進行所得熔接物之透明 性及熔接強度之評價。結果彙整列於下表1及2。 關於表1及2之透明性，〇表示熔接物之外觀呈現透 明，X表示儘管透明但含有較大的氣泡使透明性不足。 又關於熔接強度，〇表示對熔接物施加l〇Kg之荷重 參 亦不會破損，X表示破損。又，所謂熔接物意指在前述烘 箱中使粉末加熱熔接獲得之塊狀者，l〇Kg之荷重係自該 樣品之上部施加。 -62- 201012864 【i 比較例3 &lt; 67000 0.45 乳化 捕集超過 200μιη 之 粒子 220 球形 X X 比較例2 &lt; 28000 0.29 § 乳化 m 球形 〇 X 丨比較例1 &lt; 寸 220000 p 00 v〇 乳化 m 〇\ OS 球形 X X 實施例10 44000 0.41 寸 粉碎 m § 不定型 〇 〇 實施例9 74000 0.55 粉碎 m § 不定型 〇 〇 實施例8 &lt; 67000 0.45 m 粉碎 « 不定型 〇 〇 1 實施例7 &lt; 67000 0.45 m so 乳化 m 球形 〇 〇 實施例6 &lt; 67000 0.45 ΓΛ 1—&lt; 乳化 通過 63μιη,以 53μηι 捕 集 m 球形 〇 〇 實施例5 &lt; 44000 0.41 乳化 躲 00 球形 〇 〇 實施例4 &lt; m 44000 0.41 —ή 2 乳化 m 00 球形 〇 〇 實施例3 &lt; (N 74000 0.55 乳化 摧 球形 〇 〇 ! 實施例2 &lt; 67000 0.45 cn »—! 乳化 摧 νο 球形 〇 〇 實施例1 &lt; 67000 0.45 乳化 摧 v〇 球形 〇 〇 樹脂 Mw 粒子製法 分級 體積平均粒 徑_)* 形狀 透明性 熔接強度 w^ls 蜃i薦 il' -63- 201012864 rrs 參考値2 &lt; 卜 53000 0.51 摧 CS 1 1 1 1 1 1 參考値1 &lt; 67000 0.45 ΓΟ τ·*Η m 1 1 1 1 1 1 實施例18 &lt; 卜 53000 0.51 等 SX100 15% 〇 粉碎i 凝 不定型 〇 〇 實施例π &lt; 67000 0.45 ΓΟ VO SX100 20% o 1—H 粉碎 m 不定型 〇 〇 實施例16 &lt; 〇 53000 0.51 DR8900 10% cs in 粉碎 紫 不定型 〇 〇 實施例15 &lt; 卜 53000 0.51 H1041 15% cn vo 粉碎 壊 不定型 〇 〇 實施例14 &lt; 卜 53000 0.51 H1041 5% ψ·^ 粉碎 壊 ί〇 不定型 〇 〇 實施例13 &lt; 67000 0.45 ro H1041 10% 00 (N 粉碎 壊 不定型 〇 〇 實施例12 &lt; 67000 0.45 m H1041 5% 粉碎 课 不定型1 〇 〇 實施例11 &lt; ο 50000 0.43 (S 摧 1 粉碎 m 不定型 〇 〇 樹脂 Mw 添加劑 MFR 粒子製法 分級 體積平均粒徑 (m) 形狀 透明性 熔接強度 ^ ^ ^ ^ -1# Μ^ιϋι1κφωΗ^ ^ Ί -64- 201012864 由前述實施例及比較例之評價結果，可知由本發明之 特定環狀烯烴系樹脂或樹脂組成物所構成之樹脂粒子，由 於透明性及熔接強度優異故而適於粉末燒結層合造形。且 ，可知由樹脂組成物（含有特定之環狀烯烴系樹脂及苯乙 烯系聚合物），可獲得比由同樣之環狀烯烴系樹脂所構成 之樹脂粒子之融熔時流動性（MFR )更優異之樹脂粒子。 再者，本發明之樹脂粒子由於具有高的耐熱性因此在粉末 〇燒結層合造形以外之各種用途中亦有用。 [試驗例] 接著，顯示於環狀烯烴系樹脂中添加遠紅外線吸收劑 時之效果之試驗例。 [試驗例1] 計量47.5 2克合成例1中獲得之環狀烯烴系樹脂1A、 〇 0.14克汽巴•日本（股）製遙之Irganox 1010、及0.4 8克 作爲遠紅外線吸收劑之商品名：Laserfrair 800 ( Merck股 份有限公司製造，分級爲體積平均粒徑15 μιη以下之雲母 )，且以密閉型混練機在2 8 0 °C混練2 5分鐘獲得樹脂組成 物（1 )。 樹脂組成物（1 )之外觀爲透明，玻璃轉移溫度爲1 63 。(：。又，將該組成物沖壓成型爲l〇0Mm厚度所得之薄膜在 波數94 5 cm·1之吸光度爲0.49，全光透過率爲91.7 %’濁 度爲4.1%。 -65- 201012864 [試驗例2] 計量46.56克合成例1中獲得之環狀烯烴系樹脂1A、 0.14克汽巴•日本（股）製造之Irganox 1010、及1_44克 作爲遠紅外線吸收劑之商品名：Laserfrair800，且以密閉 型混練機在280 °C混練25分鐘獲得樹脂組成物（2) ° 樹脂組成物（2)之外觀爲透明’玻璃轉移溫度爲163 °C。將該組成物沖壓成型爲ιοομιη厚度所得之薄膜在波數 0 945CHT1之吸光度爲0.85，全光透過率爲91%，濁度爲 5.2%。 [試驗例3] 計量45.6克合成例1中獲得之環狀烯烴系樹脂1 A、 0.14克汽巴•曰本（股）製造之Irganox 1010、及2.4克 作爲遠紅外線吸收劑之商品名：Laserfrair 800，且以密閉 型混練機在280°C混練25分鐘獲得樹脂組成物（3) 。 〇 樹脂組成物（3)之外觀爲透明，玻璃轉移溫度爲163 °C。將該組成物沖壓成型爲ΙΟΟμηι厚度所得之薄膜在波數 945cnT1之吸光度爲1.05，全光透過率爲 91%，濁度爲 5.7%。 [試驗例4] 除使用以合成例2獲得之環狀烯烴系樹脂2A以外， 餘與試驗例1相同，製備樹脂組成物（4)。 -66- 201012864 樹脂組成物（4)之外觀爲透明，玻璃轉移溫度爲154 t。將該組成物沖壓成型爲100 μπι厚度所得之薄膜在波數 945cm·1之吸光度爲0.54，全光透過率爲92.5¾，濁度爲 2.3%。 [試驗例5] 除使用以合成例2獲得之環狀烯烴系樹脂2A以外， © 餘與試驗例2相同，製備樹脂組成物（5)。 樹脂組成物（5)之外觀爲透明，玻璃轉移溫度爲154 °C。將該組成物沖壓成型爲ΙΟΟμπι厚度所得之薄膜在波數 945 cnT1之吸光度爲0.97，全光透過率爲92.3%，濁度爲 2.8%。 [試驗例6] 除使用以合成例2獲得之環狀烯烴系樹脂2A以外， © 餘與試驗例3相同，製備樹脂組成物（6)。 樹脂組成物（6)之外觀爲透明，玻璃轉移溫度爲154 °C。將該組成物沖壓成型爲ΙΟΟμπι厚度所得之薄膜在波數 94 5cm·1之吸光度爲1.13，全光透過率爲92%，濁度爲 3 · 4 % » [試驗例7] 計量46.56克合成例1中獲得之環狀烯烴系樹脂ία、 0.14克汽巴•日本（股）製造之Irganox 1010、及1.44克 -67- 201012864 作爲遠紅外線吸收劑之八大化學工業（股）製造之ρχ-200 (磷酸酯化合物），且以密閉型混練機在280 °C混練 25分鐘獲得樹脂組成物（7)。 樹脂組成物（7)之外觀爲透明，玻璃轉移溫度爲153 °C。將該組成物沖壓成型爲ΙΟΟμηι厚度所得之薄膜在波數 945(:1^1之吸光度爲0.76，全光透過率爲93%，濁度爲2% [試驗例8] 計量45.6克合成例1中獲得之環狀烯烴系樹脂1A、 0.14克汽巴•日本（股）製造之Irganox 1010、及2.4克 作爲遠紅外線吸收劑之八大化學工業（股）製造之PX-200，且以密閉型混練機在280°C混練25分鐘獲得樹脂組 成物（8 )。 樹脂組成物（8)之外觀爲透明，玻璃轉移溫度爲144 °C。將該組成物沖壓成型爲ΙΟΟμιη厚度所得之薄膜在波數 @ 945 cnT1之吸光度爲0.98，全光透過率爲93%，濁度爲2% [試驗例9] 計量46.56克合成例1中獲得之環狀烯烴系樹脂1 A、 0.14克汽巴•日本（股）製造之lrganox 10 10、及1.44克 作爲遠紅外線吸收劑之以下式（lb)表示之4,4’-二酚雙 (二苯基）磷酸酯，且以密閉型混練機在28(TC混練25分 -68- 201012864 鐘獲得樹脂組成物（9 )。 樹脂組成物（9)之外觀爲透明，玻璃轉移溫度爲154 t。將該組成物沖壓成型爲1〇〇 μπι厚度所得之薄膜在波數 WScnT1之吸光度爲0.88，全光透過率爲93%，濁度舄2%Mw) = 5 · 3 χ 104, molecular weight distribution (Mw / Mn) = 4.8, logarithmic viscosity 0.51 dL / g, MFR = 25 g / lOmin, yield 90 g (yield 90%)]. The hydrogenation ratio of the hydride obtained by the measurement of N M R was 9 9 · 0 % or more. The copolymer composition ratio is [structure derived from (la)] / [structure derived from (2a)] / [structure derived from (3a)] = 75.3/1.4/23.3 (weight ratio). Thereafter, the obtained ring-opening polymerization hydride is referred to as a cyclic olefin resin 7A. [Example 1] -54-201012864 49 g of the cyclic olefin-based resin 1A obtained in Synthesis Example 1 was dissolved in 148 g of toluene to prepare a solution. On the other hand, 2.0 g of a nonionic surfactant EMULGEN 130 (polyoxyethylene ethyl lauryl ether HLB = 18.1) manufactured by Kao Co., Ltd. was dissolved in 188 g of ion-exchanged water to prepare an aqueous solution. The aqueous solution of the surfactant was poured into a 500 ml container, and the cyclic olefin resin 1 A was stirred while stirring at a number of revolutions of H 2000 to 25 rpm in a TK homogenizer MARK II manufactured by PRIMIX. The toluene solution is poured into an aqueous solution of the surfactant. Subsequently, stirring was continued at 25 ° C for 1 hour. The emulsion was poured into 1420 g of methanol, and stirred at 200 ° C for 10 minutes at 200 ° C using a Trin motor (spiral). The precipitated resin was recovered by a stainless steel mesh of 500 mesh and dried in a vacuum dryer at 100 ° C for 12 hours. The recovery ratio of the resin particles was 95%, and the volume average particle diameter was 36 μm. When the shape of the recovered resin particles was observed by a scanning electron microscope, it was substantially spherical. [Example 2] Resin particles were obtained at a recovery rate of 98% in the same manner as in Example 1 except that the amount of use of EMULGEN 130 was changed to 1 gram. The resin particles had a volume average particle diameter of 67 μm and a substantially spherical shape. [Example 3] Except that the cyclic olefin resin obtained in Synthesis Example 2 was used, -55-201012864 was the same as in Example 1 and resin particles were obtained at a recovery rate of 96%. The resin particles have a volume average particle diameter of 50 μm and have a substantially spherical shape. [Example 4] A resin particle was obtained at a recovery rate of 95%, except that the cyclic olefin resin obtained in Synthesis Example 3 was used. The resin particles have a volume average particle diameter of 78 μm and are substantially spherical in shape. [Example 5] Resin particles were obtained at a recovery ratio of 95% except that the cyclic olefin resin obtained in Synthesis Example 3 was used, and the amount of EMULGEN 130 was used in an amount of 20.0 g, the same as in Example 1. The resin particles have a volume average particle diameter of 18 μm and a substantially spherical shape. [Example 6] Resin particles were prepared as in Example 2. The obtained resin particles were placed on a wet φ type vibration sifting machine, passed through a 63 μm pore size sieve, and the particles trapped on a sieve having a pore size of 53 μm were collected and vacuum dried. The recovery rate is 25%. [Example 7] The same procedure as in Example 1 was carried out except that the cyclic olefin resin ruthenium obtained in Synthesis Example I was dissolved in 180 g of toluene, and the amount of EMULGEN 130 使用 was changed to 1 gram. Resin-56-201012864 particles were obtained at a recovery rate of 95%. The resin particles had a volume average particle diameter of 15 μm and a substantially spherical shape. [Example 8] 0.3 parts by weight of an antioxidant 肆[Methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane was added in a twin-screw extruder 100 parts by weight of the cyclic olefin resin obtained in Synthesis Example 1 was used as a granule, and then subjected to mechanical freeze-pulverization using a hammer honing machine (Hummer Mill) to obtain a resin having a volume average particle diameter of 49 μm. The particle has a recovery of 90%. [Example 9] 0.3 parts by weight of an antioxidant 肆[Methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane was added in a twin-screw extruder After 100 parts by weight of the cyclic olefin resin 2A obtained in Synthesis Example 2 was used as a pellet, it was mechanically freeze-pulverized using a hammer honing machine (Hummer Mill) to obtain a resin having a volume average particle diameter of 60 μ? The particle has a recovery of 90%. [Example 10] 0.3 parts by weight of an antioxidant 肆[Methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane was added in a twin-screw extruder After 100 parts by weight of the cyclic olefin-based resin 3A obtained in Synthesis Example 3, granules were prepared, and then subjected to mechanical blasting using a hammer honing machine (Hummer Mill) to obtain a volume average granule after pulverization by mechanical jelly-57-201012864 Resin particles having a diameter of 60 μm have a recovery of 90%. [Example 11] 0.3 parts by weight of an antioxidant 肆 [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane was added in a twin-screw extruder The obtained cyclic olefin resin 6A obtained in Synthesis Example 6 was granulated, and then subjected to mechanical freeze kiln pulverization using a hammer honing machine (Hummer Mill) to obtain a volume average particle diameter of 46 μm. The resin particle 'recovery rate was 92%. [Example 12] A 9.5 kg portion of 0.3 kg parts of an antioxidant 肆 [methylene-3-(3,5-di-tert-butyl-) was kneaded using a twin-screw extruder (TEM-37BS 'Toshiba Machine Manufacturing Co., Ltd.). 4-hydroxyphenyl)propionate] methane was added to 1 part by weight of the cyclic olefin resin obtained in Synthesis Example 1 and the ratio of styrene/ethylene/butene of 0.5 kg was 30 0/70% by weight of a styrene-based thermoplastic elastomer (manufactured by Asahi Kasei Co., Ltd., TAFT A CK Η1041) 'A pelletized thermoplastic resin composition was obtained. The cylinder temperature is 280 °C. The shaft speed is 10 〇r pm and the extrusion speed is 10~2 Okg/hr. The resulting granules were transparent and had an MFR of 21 g / lOmin. After mechanically freeze-pulverizing the obtained pellets using a hammer honing machine, 'recovery of resin particles having a volume average particle diameter of 50 μm' was 90%-58-201012864 [Example 13] 0.3 parts by weight except for using 9 kg Antioxidant 肆[Methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane was added to 100 parts by weight of the cyclic olefin-based resin 1A obtained in Synthesis Example 1. The styrene-based thermoplastic elastomer (manufactured by Asahi Kasei Co., Ltd., TAFTACK Η 1 04 1 ) having a ratio of 1.0 kg of a styrene/ethylene/butene ratio of 1.0 kg (TAFTACK Η 1 04 1 ) 2 The same particles were obtained. The obtained pellet had a φ MFR of 28 g / 1 Omin. After the obtained pellets were mechanically freeze-pulverized by a hammer honing machine, resin particles having a volume average particle diameter of 52 μm were obtained, and the recovery was 90%. [Example 14] In addition to using 9.5 kg, 0.3 part by weight of an antioxidant 肆[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane was added to 1 A styrene-based thermoplastic elastomer having a ratio of a styrene/ethylene/butene ratio of 0.5 kg to 30/70% by weight, based on the weight of the cyclic olefin resin obtained in Synthesis Example 7 A pellet was obtained in the same manner as in Example 12 except that Asahi Kasei Co., Ltd. was manufactured, TAFTACK H1041. The MFR of the obtained granules was 41 g / lOmin. After the obtained pellets were mechanically freeze-pulverized by a hammer honing machine, resin particles having a volume average particle diameter of 51 μm were obtained, and the recovery was 92%. [Example 15] In addition to the use of 8.5 kg, 0.3 parts by weight of an antioxidant 亚 [methylene-59-201012864 bis-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] Methane was added to 100 parts by weight of the cyclic olefin-based resin 7A obtained in Synthesis Example 7, and a styrene-based thermoplastic elastomer having a ratio of styrene/ethylene/butene of 1.5 kg of 30/70% by weight. The pellets were obtained in the same manner as in Example 12 except for the production of Asahi Kasei Co., Ltd., TAFTACK H1041. The MFR of the obtained granules was 63 g / lOmin. After the obtained pellets were mechanically freeze-pulverized by a hammer honing machine, resin particles having a volume average particle diameter of 50 μm were obtained, and the recovery was 90%. [Example 16] In addition to using 9 kg, 0.3 part by weight of an antioxidant 肆[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane was added to 1 A styrene-based thermoplastic elastomer (JSR (with a ratio of 1.0 kg of a styrene/ethylene/butene ratio of 1.0 kg) obtained by synthesizing a cyclic olefin resin obtained in Synthesis Example 7. The pellets were obtained in the same manner as in Example 12 except that Dynaron 8900 was produced. The MFR _ of the obtained granules was 5 2 g / 1 Omin. After the obtained pellets were mechanically freeze-pulverized by a hammer honing machine, resin particles having a volume average particle diameter of 50 μm were obtained, and the recovery was 91%. [Example 17] In addition to using 8 kg of 〇·3 parts by weight of antioxidant 肆[Methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane was added In addition to 100 parts by weight of the cyclic olefin resin obtained in Synthesis Example 1, -60-201012864 and 2 kg of styrene resin (manufactured by YASUHARA Chemical Co., Ltd., SX100), and Example 12 The same particles were obtained. The MFR of the obtained granules was 1 00 g / 1 Omin. After the obtained pellets were mechanically freeze-pulverized by a hammer honing machine, resin particles having a volume average particle diameter of 50 μm were obtained, and the recovery was 89%. [Example 18] φ In addition to using 8.5 kg, 0.3 part by weight of an antioxidant 肆[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane was added to In the same manner as in Example 12, except that the cyclic olefin resin 7A obtained in Synthesis Example 7 was obtained in an amount of 1 part by weight, the same as in Example 12 except that 1.5 kg of a styrene resin (manufactured by YASUHARA Chemical Co., Ltd., SX100) was obtained. . The MFR of the obtained granules was 140 g/l Ornin. After mechanically freeze-pulverizing the obtained pellets using a hammer honing machine, resin particles having a volume average particle diameter of 48 μη were obtained, and the recovery was 89%. [Comparative Example 1] A resin particle was obtained at a recovery rate of 96%, except that the cyclic olefin resin obtained in Synthesis Example 4 was used. The resin particles have a volume average particle diameter of 99 μm and a substantially spherical shape. [Comparative Example 2] The same procedure as in Example 1 was carried out except that the cyclic olefin resin obtained in Synthesis Example 5 was used, except that the resin particles were obtained at a recovery rate of 96%. The resin particles -61 - 201012864 have a volume average particle diameter of 20 μm and a substantially spherical shape. [Comparative Example 3] Resin particles were prepared as in Example 2. The obtained resin particles were placed on a wet vibrating screen to recover resin particles trapped on a sieve having a pore size of 2 μm. The recovered resin particles had a volume average particle diameter of 220 μϊη and a recovery of 5%. ❹ &lt;Evaluation&gt; 1 g of the resin particles obtained in the examples and the comparative examples were placed in a 3.5 ml sample bottle, and heated in an oven set at a temperature higher than the glass transition temperature of the cyclic olefin resin by 50 ° C. Welding. The transparency of the obtained weld and the evaluation of the weld strength were evaluated. The results are summarized in Tables 1 and 2 below. Regarding the transparency of Tables 1 and 2, 〇 indicates that the appearance of the weld was transparent, and X indicates that although it was transparent, it contained a large bubble to make the transparency insufficient. Further, regarding the welding strength, 〇 indicates that the load of 1 〇 Kg applied to the welded material is not damaged, and X indicates breakage. Further, the term "welding material" means a block obtained by heat-welding a powder in the above-mentioned oven, and a load of 10 Kg is applied from the upper portion of the sample. -62- 201012864 [i Comparative Example 3 &lt; 67000 0.45 Emulsified capture of particles of more than 200 μη 220 Sphere Comparative Example 2 &lt; 28000 0.29 § Emulsification m Spherical 〇X 丨 Comparative Example 1 &lt; 220,000 p 00 v 〇 Emulsification m 〇\OS Sphere XX Example 10 44000 0.41 inch pulverization m § Unshaped 〇〇 Example 9 74000 0.55 pulverization m § Unshaped 〇〇 Example 8 &lt; 67000 0.45 m pulverization «Indefinite 〇〇 1 Example 7 &lt; 67000 0.45 m so emulsified m spherical 〇〇 Example 6 &lt; 67000 0.45 ΓΛ 1 - &lt; Emulsification through 63 μηη, capturing 53 μηι m 〇〇 〇〇 Example 5 &lt; 44000 0.41 emulsified hiding 00 spherical 〇〇 Example 4 &lt m 44000 0.41 - ή 2 emulsified m 00 spherical 〇〇 Example 3 &lt; (N 74000 0.55 emulsified spheroidal 〇〇! Example 2 &lt; 67000 0.45 cn » -! Emulsification destroying ο spherical 〇〇 Example 1 &lt; 67000 0.45 emulsified to destroy v 〇 spherical enamel resin Mw particle method classification volume average particle size _) * shape transparency welding strength w ^ ls 荐i recommended il' -63- 201012864 rrs Reference 値2 &lt; Bu 53000 0.51 Destroy CS 1 1 1 1 1 1 Reference 値 1 &lt; 67000 0.45 ΓΟ τ·*Η m 1 1 1 1 1 1 Example 18 &lt; 53000 0.51 etc. SX100 15% 〇 〇 i Condensation type 〇〇Example π &lt; 67000 0.45 ΓΟ VO SX100 20% o 1—H pulverization m amorphous 〇〇 Example 16 &lt; 〇 53000 0.51 DR8900 10% cs in pulverized purple indeterminate 〇〇 Example 15 &lt;; 53000 0.51 H1041 15% cn vo smashing 壊 amorphous 〇〇 Example 14 &lt; 53000 0.51 H1041 5% ψ·^ 碎 壊 〇 〇 〇 〇〇 〇〇 〇〇 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 N 壊 壊 壊 壊 〇〇 Example 12 &lt; 67000 0.45 m H1041 5% Crushing class indeterminate 1 〇〇 Example 11 &lt; ο 50000 0.43 (S 1 1 pulverization m Unshaped 〇〇 resin Mw additive MFR particle grading Volume average particle diameter (m) Shape transparency weld strength ^ ^ ^ ^ -1# Μ ^ιϋι1κφωΗ ^ ^ Ί -64- 201012864 From the evaluation results of the foregoing examples and comparative examples, it is understood that the specific cyclic olefin resin of the present invention Or resin The resin constituting the particles into the composition, is excellent in the welding strength and transparency and therefore is suitable powder sintered laminated Zaoxing. In addition, it is understood that the resin composition (containing a specific cyclic olefin resin and a styrene polymer) can be obtained more than the fluidity (MFR) during melting of the resin particles composed of the same cyclic olefin resin. Excellent resin particles. Further, since the resin particles of the present invention have high heat resistance, they are also useful in various applications other than powder mash sintering. [Test Example] Next, a test example of the effect of adding a far-infrared ray absorbing agent to a cyclic olefin-based resin is shown. [Test Example 1] 47.5 2 g of the cyclic olefin-based resin 1A obtained in Synthesis Example 1, 〇 0.14 g of Ciba, Japan's Iriganox 1010, and 0.48 g of the product name of the far-infrared absorbing agent were measured. : Laserfrair 800 (mica manufactured by Merck Co., Ltd., classified into a mica having a volume average particle diameter of 15 μm or less), and kneaded at 280 ° C for 25 minutes in a closed kneader to obtain a resin composition (1). The appearance of the resin composition (1) was transparent, and the glass transition temperature was 1 63 . (: Further, the film obtained by press-forming the composition into a thickness of 10 mm thick has an absorbance of 0.49 at a wavenumber of 94 5 cm·1, a total light transmittance of 91.7%, and a turbidity of 4.1%. -65- 201012864 [Test Example 2] 46.56 g of the cyclic olefin-based resin 1A obtained in Synthesis Example 1, 0.14 g of Irganox 1010 manufactured by Ciba (Japan), and 1 - 44 g were used as the far-infrared absorbing agent trade name: Laserfrair 800, and The resin composition (2) was obtained by kneading at 280 ° C for 25 minutes in a closed type kneader. The appearance of the resin composition (2) was transparent, and the glass transition temperature was 163 ° C. The composition was press-formed to a thickness of ιοομιη. The film had an absorbance of 0.85 at a wavenumber of 0 945 CHT1, a total light transmittance of 91%, and a haze of 5.2%. [Test Example 3] 45.6 g of the cyclic olefin-based resin 1 A, 0.14 g of steam obtained in Synthesis Example 1 was measured. Irganox 1010 manufactured by Ba Sakamoto Co., Ltd. and 2.4 g were used as the far-infrared absorbing agent under the trade name: Laserfrair 800, and the resin composition (3) was obtained by kneading at 280 ° C for 25 minutes in a closed type kneader. The appearance of the composition (3) is transparent, glass The transfer temperature was 163 ° C. The film obtained by press-forming the composition into a thickness of ΙΟΟμηι had an absorbance of 1.05 at a wavenumber of 945cnT1, a total light transmittance of 91%, and a haze of 5.7%. [Test Example 4] The resin composition (4) was prepared in the same manner as in Test Example 1 except for the cyclic olefin-based resin 2A obtained in Synthesis Example 2. -66-201012864 The resin composition (4) was transparent in appearance and had a glass transition temperature of 154 t. The composition obtained by press-forming the composition into a thickness of 100 μm had an absorbance of 0.54 at a wavenumber of 945 cm·1, a total light transmittance of 92.53⁄4, and a haze of 2.3%. [Experiment 5] Except that the synthesis example 2 was used. The resin composition (5) was prepared in the same manner as in Test Example 2 except for the cyclic olefin resin 2A. The appearance of the resin composition (5) was transparent, and the glass transition temperature was 154 ° C. The composition was formed by press molding. The film obtained by the thickness of ΙΟΟμπι had an absorbance of 0.97 at a wave number of 945 cnT1, a total light transmittance of 92.3%, and a haze of 2.8%. [Test Example 6] Except that the cyclic olefin resin 2A obtained in Synthesis Example 2 was used. , © The same as Test Example 3, preparation The fat composition (6). The appearance of the resin composition (6) was transparent, and the glass transition temperature was 154 ° C. The film obtained by press-forming the composition into a thickness of ΙΟΟμπι had an absorbance at a wave number of 94 5 cm·1 of 1.13. The total light transmittance was 92%, and the turbidity was 3 · 4 % » [Test Example 7] 46.56 g of the cyclic olefin resin obtained in Synthesis Example 1, ία, 0.14 g of Ciba, Japan, Irganox 1010 And 1.44 g-67-201012864 ρχ-200 (phosphate compound) manufactured by the eight major chemical industries (shares) as a far-infrared absorbing agent, and kneaded at 280 °C for 25 minutes in a closed type kneader to obtain a resin composition (7) ). The appearance of the resin composition (7) was transparent, and the glass transition temperature was 153 °C. The film obtained by press-forming the composition into a thickness of ΙΟΟμηι was at a wave number of 945 (the absorbance of the lens was 0.76, the total light transmittance was 93%, and the turbidity was 2% [Test Example 8] Measurement 45.6 g Synthesis Example 1 The obtained cyclic olefin resin 1A, 0.14 g of Irganox 1010 manufactured by Ciba Japan Co., Ltd., and 2.4 g of PX-200 manufactured by the eight major chemical industries (shares) as far-infrared absorbing agents, and sealed in a closed type The resin composition (8) was obtained by kneading at 280 ° C for 25 minutes. The appearance of the resin composition (8) was transparent, and the glass transition temperature was 144 ° C. The composition was press-formed into a film having a thickness of ΙΟΟμηη in wave number. @945 cnT1 has an absorbance of 0.98, a total light transmittance of 93%, and a haze of 2%. [Test Example 9] 46.56 g of the cyclic olefin resin 1 A obtained in Synthesis Example 1, 0.14 g Ciba·Japan ( Lrganox 10 10, and 1.44 g of 4,4'-diphenol bis(diphenyl)phosphate represented by the following formula (lb) as a far infrared ray absorbing agent, and a closed type kneading machine at 28 (TC) The resin composition (9) was obtained by mixing 25 minutes-68-201012864. Resin composition (9) Appearance transparent, glass transition temperature was 154 t. The composition was press-molded film thickness 1〇〇 μπι obtained from the absorbance at the wave number WScnT1 0.88, 93% total light transmittance, haze shoe 2%

[化 18][Chem. 18]

(lb) [試驗例10] 計量45.6克合成例1中獲得之環狀烯烴系樹脂1A、 0.14克汽巴•曰本（股）製造之Irganox 1010、及2·4克 作爲遠紅外線吸收劑之以前述式（lb)表示之4，4’·二酚 雙（二苯基）磷酸酯，且以密閉型混練機在280 °C混練25 分鐘獲得樹脂組成物（1 〇 )。 樹脂組成物（10)之外觀爲透明，玻璃轉移溫度爲 145°C。將該組成物沖壓成型爲1〇〇μηι厚度所得之薄膜在 波數94 5(^-1之吸光度爲1.16，全光透過率爲93%，濁度 爲2%。 [比較試驗例1] -69- 201012864 除未使用遠紅外線吸收劑以外，餘與試驗例1相同， 獲得樹脂組成物（11 )。樹脂組成物（11 )之外觀爲透明 ，玻璃轉移溫度爲163°c。將該組成物沖壓成型爲ΙΟΟμπι 厚度所得之薄膜在波數945(:1^1之吸光度爲0.36，全光透 過率爲93%，濁度爲2.3%。 [比較試驗例2] 除未使用遠紅外線吸收劑以外，餘與試驗例4相同， φ 獲得樹脂組成物（12)。樹脂組成物（12)之外觀爲透明 ，玻璃轉移溫度爲153°C。將該組成物沖壓成型爲ΙΟΟμιη 厚度所得之薄膜在波數945CHT1之吸光度爲0.36,全光透 過率爲9 3 %，濁度爲2.0 %。 [比較試驗例3] 計量32克合成例1中獲得之環狀烯烴系樹脂1A、 0.14克汽巴•曰本（股）製造之Irganox 1010、及16克 Θ 作爲遠紅外線吸收劑之商品名：Laserfrair 800，且以密閉 型混練機在280°C混練25分鐘獲得樹脂組成物（13)。 樹脂組成物（13)之外觀爲不透明，對該組成物實施 沖壓成形後，由於強度不足而無法獲得評價用薄膜。 [比較試驗例4] 計量32克合成例1中獲得之環狀烯烴系樹脂1A、 〇·14克汽巴•日本（股）製造之Irganox 1010、及16克 -70- 201012864 作爲遠紅外線吸收劑之八大化學工業（股）製造之PX-200，且以密閉型混練機在28 0 °C混練25分鐘獲得樹脂組 成物（14 )。 樹脂組成物（1 4 )之外觀爲透明，但玻璃轉移溫度低 至80°C，該組成物爲無法發揮環狀烯烴系樹脂之特徵之耐 熱性者。 Θ [產業上之可能利用性] 本發明之樹脂粒子耐熱性及透明性優異，適用作爲光 擴散劑、粉體塗料、色劑用材料、油墨、隔離材（例如液 晶顯示器使用）、塡充材、抗結塊劑、潤滑劑成分、立體 物造形用粉末等。 又本發明之樹脂粒子含有遠紅外線吸收劑時，該樹脂 粒子之遠紅外線吸收能力優異，特別適用於使用遠紅外線 雷射之粉末燒結層合造形、彫刻、切削、標記等。 ❹ -71 -(lb) [Test Example 10] 45.6 g of the cyclic olefin resin 1A obtained in Synthesis Example 1, 0.14 g of Irganox 1010 manufactured by Ciba Barbine, and 2.4 g were measured as far infrared ray absorbing agents. The 4,4'-diphenol bis(diphenyl)phosphate represented by the above formula (lb) was kneaded at 280 ° C for 25 minutes in a sealed kneader to obtain a resin composition (1 〇). The appearance of the resin composition (10) was transparent, and the glass transition temperature was 145 °C. The film obtained by press-forming the composition into a thickness of 1 〇〇μηι had an absorbance of 1.16 at a wave number of 94 5 (^-1, a total light transmittance of 93%, and a haze of 2%. [Comparative Test Example 1] - 69-201012864 A resin composition (11) was obtained in the same manner as in Test Example 1 except that the far-infrared absorbing agent was not used. The appearance of the resin composition (11) was transparent, and the glass transition temperature was 163 ° C. The film obtained by press forming into a thickness of ΙΟΟμπι was at a wave number of 945 (: 1^1, the absorbance was 0.36, the total light transmittance was 93%, and the haze was 2.3%. [Comparative Test Example 2] Except that the far infrared ray absorbing agent was not used. In the same manner as in Test Example 4, φ obtained the resin composition (12). The appearance of the resin composition (12) was transparent, and the glass transition temperature was 153 ° C. The film was formed by press-forming the composition into a thickness of ΙΟΟμηη The absorbance of the number 945 CHCT1 was 0.36, the total light transmittance was 93%, and the haze was 2.0%. [Comparative Test Example 3] 32 g of the cyclic olefin resin 1A obtained in Synthesis Example 1 and 0.14 g of Ciba·曰 were measured. Irganox 1010 and 16 gram manufactured by the company as far infrared rays The product name of the collector: Laserfrair 800, and the resin composition (13) was obtained by kneading at 280 ° C for 25 minutes in a closed kneader. The appearance of the resin composition (13) was opaque, and after the composition was subjected to press forming, The film for evaluation was not obtained due to insufficient strength. [Comparative Test Example 4] 32 g of the cyclic olefin-based resin 1A obtained in Synthesis Example 1 and I·14 g of Ciba and Japan's Irganox 1010 and 16 were measured.克-70- 201012864 PX-200 manufactured by the eight major chemical industries (shares) of the far-infrared absorbing agent, and the resin composition (14) is obtained by kneading at a temperature of 28 ° C for 25 minutes in a closed type kneader. Resin composition (1) 4) The appearance is transparent, but the glass transition temperature is as low as 80 ° C. The composition is a heat resistant property which does not exhibit the characteristics of the cyclic olefin resin. Θ [Industrial Applicability] The resin particles of the present invention are heat resistant Excellent in properties and transparency, suitable for use as a light diffusing agent, powder coating, toner material, ink, separator (for liquid crystal display), enamel filler, anti-caking agent, lubricant component, three-dimensional shape powder Further, when the resin particles of the present invention contain a far-infrared ray absorbing agent, the resin particles are excellent in far-infrared absorbing ability, and are particularly suitable for powder sintering lamination, engraving, cutting, marking, etc. using a far-infrared laser. 71 -

Claims (1)

201012864 七、申請專利範固： 1. 一種樹脂粒子，其特徵爲： 以凝膠滲透層析儀測定之重量平均分子量爲 30,000〜200,000 ， 由具有以下述通式（1)表示之重複單位之環狀烯烴 系樹脂所構成， 體積平均粒徑爲1〜200μιη ;201012864 VII. Patent application: 1. A resin particle characterized by having a weight average molecular weight of 30,000 to 200,000 as measured by a gel permeation chromatography, and having a ring having a repeating unit represented by the following general formula (1) The olefin-based resin is composed of a volume average particle diameter of 1 to 200 μm; [X表示以式：-CH = CH-表示之基或以式：-CH2CH2-表 示之基，a及b獨立地表示0或1，c及d獨立地表示0〜2 之整數， R4、R5、R6' R7、R8及R9各自獨立地表示下述（i) ~(v)之任一者： (i)氫原子； (ii )鹵素原子； -72- 201012864 (iii )經取代或非取代之碳數1〜40之烴基； (iv)具有包含氧原子、硫原子、氮原子或矽原子之 連結基之經取代或非取代之碳數1〜4 0之烴基； (v )極性基； R1D、R11、R12及R13各自獨立爲前述（i)〜（V)之 任一者，或爲下述（vi)〜（vii)之任一者； (vi) 與R11，或以2與Ri3鍵結形成單環或多環 β 之烴環或雜環，與前述鍵結無關之R1G〜R13各自獨立爲前 述（i)〜（v)之任一者； (Vii) R1()或R11與Rl2或R13彼此鍵結形成單環或多 環之烴環或雜環，與前述鍵結無關之R1()〜R13各自獨立爲 前述（i)〜（v)之任一者]。 2·如申請專利範圍第1項之樹脂粒子，其中前述環 狀烯烴系樹脂使用烏伯羅德氏（Ubbelohde )型黏度計測 定之對數黏度爲0.30〜0.95dL/g。 ® 3.如申請專利範圍第1或2項之樹脂粒子，其中前 述環狀烯徑系樹脂之玻璃轉移溫度爲115〜200°C，體積平 均粒徑爲10〜80μιη。 4. 如申請專利範圍第1至3項中任一項之樹脂粒子 ，其中前述環狀烯烴系樹脂中，除芳香族性之不飽和鍵以 外之碳-碳雙鍵部份中之95 %以上被氫化。 5. 如申請專利範圍第1至4項中任一項之樹脂粒子 ，其進而含有遠紅外線吸收劑，且其含量係與前述環狀烯 烴系樹脂之重量比成爲環狀烯烴系樹脂：遠紅外線吸收劑 -73- 201012864 = 99.99 ： 0.01 〜70 : 30 之量 ° 6. 如申請專利範圍第5項之樹脂粒子’其中前述遠 紅外線吸收劑爲矽酸鹽礦物或磷酸酯類。 7. —種樹脂粒子，其特徵爲由含有申請專利範圍第1 項之環狀烯烴系樹脂與具有以下述式（4)表示之構造單 位之苯乙烯系聚合物之樹脂組成物所構成， 且體積平均粒徑爲1〜200μιη，[X represents a group represented by the formula: -CH = CH- or a group represented by the formula: -CH2CH2-, a and b independently represent 0 or 1, and c and d independently represent an integer of 0 to 2, R4, R5 R6' R7, R8 and R9 each independently represent any of the following (i) to (v): (i) a hydrogen atom; (ii) a halogen atom; -72- 201012864 (iii) substituted or unsubstituted a hydrocarbon group having 1 to 40 carbon atoms; (iv) a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms having a linking group of an oxygen atom, a sulfur atom, a nitrogen atom or a ruthenium atom; (v) a polar group; R1D, R11, R12 and R13 are each independently any of the above (i) to (V), or any of the following (vi) to (vii); (vi) with R11, or with 2 and Ri3 The bond forms a hydrocarbon ring or a heterocyclic ring of a monocyclic or polycyclic β, and R1G to R13 which are not related to the aforementioned bonding are each independently of any of the above (i) to (v); (Vii) R1() or R11 and Rl2 or R13 are bonded to each other to form a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring, and R1() to R13 which are independent of the above-mentioned bonding are each independently of any of the above (i) to (v). 2. The resin particles according to claim 1, wherein the cyclic olefin resin has a logarithmic viscosity of 0.30 to 0.95 dL/g as measured by an Ubbelohde type viscometer. The resin particles according to claim 1 or 2, wherein the cyclic olefin resin has a glass transition temperature of 115 to 200 ° C and a volume average particle diameter of 10 to 80 μm. 4. The resin particles according to any one of claims 1 to 3, wherein the cyclic olefin resin has 95% or more of the carbon-carbon double bond portion other than the aromatic unsaturated bond. It is hydrogenated. 5. The resin particles according to any one of claims 1 to 4, further comprising a far-infrared ray absorbing agent, wherein the weight ratio of the content to the cyclic olefin-based resin is a cyclic olefin resin: far infrared ray Absorbent-73-201012864 = 99.99: 0.01 to 70: 30. 6. The resin particles of claim 5, wherein the far-infrared absorbing agent is a phthalate mineral or a phosphate. 7. A resin particle comprising a cyclic olefin resin according to the first aspect of the patent application and a resin composition having a styrene polymer having a structural unit represented by the following formula (4), and The volume average particle size is 1~200μιη, [化2][Chemical 2] [R表示碳數卜4之烷基、羥基或羧基，η表示0〜5之 ® 整數，ri爲2以上時，複數個存在之R可相同或相異]。 8. 如申請專利範圍第7項之樹脂粒子，其進而含有 遠紅外線吸收劑，且其含量係與前述樹脂組成物之重量比 成爲樹脂組成物：遠紅外線吸收劑=99.99 : 0.01~70 ·· 30 之量。 9. 如申請專利範圍第8項之樹脂粒子，其中前述遠 紅外線吸收劑爲矽酸鹽礦物或磷酸酯類。 10. 如申請專利範圍第1至9項中任一項之樹脂粒子 -74- 201012864 ，其進而含有抗氧化劑。 π. —種粉末燒結層合造形方法，其特徵爲使用申請 專利範圍第1至1 〇項中任一項之樹脂粒子。[R represents an alkyl group, a hydroxyl group or a carboxyl group of carbon number 4, η represents an integer of 0 to 5, and when ri is 2 or more, plural R may be the same or different]. 8. The resin particle of claim 7 further comprising a far infrared ray absorbing agent, and the content ratio of the resin composition to the resin composition is a resin composition: far infrared ray absorbing agent = 99.99 : 0.01 to 70 · 30 amount. 9. The resin particle of claim 8, wherein the far infrared absorbing agent is a silicate mineral or a phosphate. 10. The resin particle-74-201012864 of any one of claims 1 to 9, which further contains an antioxidant. π. A method of forming a powder sintered laminate, which is characterized by using the resin particles of any one of claims 1 to 1. -75- 201012864 四 指定代表圖： (一） 、本案指定代表圖為：無 (二） 、本代表圖之元件代表符號簡單說明：無 201012864 五、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無-75- 201012864 Four designated representatives: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: No 201012864 V. If there is a chemical formula in this case, please reveal the best display invention. Chemical formula of the feature: none -4--4-