1248861 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關各種射出成形裝置及用於該裝置之例如 針狀物、成形模具、豎澆道、多支管、加熱筒、螺桿、噴 嘴等的構件，特別是有關具有與成形用樹脂之剝離性或成 形用樹脂之流動性優的保護膜的射出成形裝置及用於該裝 置的構件及表面處理方法。 【先前技術】 在將熔融樹脂射出到模槽內之噴嘴本體的內側配置針 狀物，被壓送來的熔融樹脂會通過形成在噴嘴本體和針狀 物之間的狹窄間隙，並從噴嘴本體的前端部射出到模槽內 。並於保壓後稍微移動針狀物而密射澆口，然後自射出成 形裝置取出樹脂成形品的構造。 再者，有關成形用模具例如可舉以下所述的日本特許 文獻1的例子。 [特許文獻1] 日本特開平第1-234214號公報 L發明內容】 (發明欲解決的課題） 可是，前述針狀物和噴嘴本體是用普通鋼材製成的， ^與成形用樹脂的剝離性不佳。因此利用該針狀物密封澆口 時’易在成形品的澆口密封部產生氣泡狀的突出部、毛邊 -5- (2) 1248861 、剝落等。而且與成形用樹脂之剝離性不良的緣故，當成 形結束時，會在針狀物的周面和噴嘴本體的內面附著樹脂 ，其次於射出成形之際，’該附著的樹脂會燒焦變色，且該 燒焦渣滓會從針狀物和噴嘴本體剝落而擠壓流入模槽內， 混入到成形品中。如此一來成品價値降低，成形不良非常 明顯時，具生產良率下降等缺點。 而在成形模具表面上的成形用樹脂之流動性不一定很 良好，使用分子量比較小的樹脂，因此成形品的機械性強 度不足。甚至雖然樹脂的流動良好但欲需要提高成形溫度 (加熱器溫度），因此有耗電量激增等缺點。 本發明之目的在於提供一種解決此種習知技術的缺點 ，且成形性良好，而且耐用壽命長的射出成形裝置及用於 該裝置的各種構件及表面處理方法。 裝部 形 I 成的 出面 射之 在接 以相 係脂 段樹 手用 1 形 第成 的 的 } 明材 段發基 手本之 的，路 題的流 課目脂 決此樹 解成成 以達形 用爲與 C 中 分或全部是利用由含有氟的金鋼石狀的碳（以下稱含氟 DLC)所組成的保護膜所覆爲其特徵。 本發明的第2手段乃於前述第1手段中，在前述基材 和保護膜之間，形成以周期表4a族（Ti、Zr、Hf) 、4b 族（Si、Ge、Sn、Pb) 、5壮族（^、>^、丁&) 、6a 族（1248861 (1) Field of the Invention The present invention relates to various injection molding apparatuses and, for example, needles, forming dies, vertical runners, manifolds, heating cylinders, screws, nozzles for the apparatus. In particular, the member is an injection molding apparatus which has a protective film which is excellent in fluidity with a resin for molding or a resin for molding, and a member and a surface treatment method for the same. [Prior Art] A needle is disposed inside a nozzle body that ejects molten resin into a cavity, and the molten resin that is pumped is passed through a narrow gap formed between the nozzle body and the needle, and from the nozzle body The front end portion is injected into the cavity. After the pressure is held, the needle is slightly moved to cover the gate, and then the structure of the resin molded article is taken out by the molding device. In addition, examples of the molding die include the following Japanese Patent Literature 1. [Patent Document 1] Japanese Laid-Open Patent Publication No. 1-342214. SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) However, the needle and the nozzle body are made of ordinary steel materials, and the peeling property with the molding resin is Not good. Therefore, when the gate is sealed by the needle, it is easy to produce a bubble-like projection, a burr -5 - (2) 1248861, peeling, or the like in the gate sealing portion of the molded article. Further, when the peeling property with the molding resin is poor, when the molding is completed, the resin adheres to the circumferential surface of the needle and the inner surface of the nozzle body, and secondly, when the injection molding is performed, the attached resin may be burnt and discolored. And the char residue is peeled off from the needle and the nozzle body, squeezed into the cavity, and mixed into the molded article. As a result, the price of the finished product is reduced, and when the forming defect is very conspicuous, the production yield is lowered. On the other hand, the flowability of the molding resin on the surface of the molding die is not necessarily good, and a resin having a relatively small molecular weight is used, so that the mechanical strength of the molded article is insufficient. Even though the flow of the resin is good, it is necessary to increase the forming temperature (heater temperature), so that there is a disadvantage that the power consumption is sharply increased. SUMMARY OF THE INVENTION An object of the present invention is to provide an injection molding apparatus which solves the disadvantages of the prior art, has good formability, and has a long durability and a variety of members and surface treatment methods for the apparatus. The shape of the part I is shot in the same way as the one of the first section of the tree. The flow of the course is used to solve the problem. A part or all of C is characterized by a protective film composed of a diamond-containing carbon containing fluorine (hereinafter referred to as fluorine-containing DLC). According to a second aspect of the present invention, in the first aspect, the group 4a (Ti, Zr, Hf) and the group 4b (Si, Ge, Sn, Pb) are formed between the substrate and the protective film. 5 Zhuang (^, > ^, Ding &), 6a (
Cr、Mo、W)中之至少一種元素爲主成份的基底層爲其特 徵。 -6 - (3) 1248861 本發明的第3手段乃屬於用於射出成形裝置的構件， 與成形用樹脂彳目接之面的一部分或全部是利用由含有氟的 金鋼石狀的碳所組成的保護膜而覆蓋爲其特徵。 本發明的第4手段乃於前述第3手段中，前述構件是 指成形模具爲其特徵。 本發明的第5手段乃於前述第3手段中，前述構件是 指針狀物、豎繞道、多支管、加熱筒、螺桿、噴嘴中之至 少一個構件爲其特徵。 本發明的第6手段乃於前述第3至第5手段中，在前 述構件的基材和保護膜之間，形成以周期表4 a族、4 b族 、5a族、6a族中之至少一種元素爲主成份的基底層爲其 特徵。 本發明的第7手段乃於前述第6手段中，前述基底層 的主成份元素是從Cr、W、Ti、Si的群中所選出的至少一 種元素爲其特徵。 本發明的第8手段乃於前述第6或第7手段中，在前 述基底層和保護膜之間，形成構成基底層之元素和構成保 護膜之元素的混合區域層爲其特徵。 本發明的第9手段乃於前述第6手段中，在前述基底 層和保護膜之間，形成由金鋼石狀的碳所組成的中間膜爲 其特徵。 本發明之第1〇手段乃於前述第9手段中，在前述基 底層和前述中間膜之間，形成構成基底層之元素和構成中 間膜之元素的混合區域層爲其特徵。 1248861 (4) 本發明的第Π手段，係將以周期表4a族、4b族、 5a族、6a族中之至少一種元素爲主成份的基底層用標靶 、和由碳所組成‘的保護膜用標靶、和面對前述基底層用標 靶及保護膜用標靶而配置的射出成形裝置用構件的基材配 置在不活性氣體中；並對前述基底層用標靶施加預定的濺 鍍電力並施行濺鍍而在基材上形成基底層；且該基底層之 膜厚成爲預定的厚度時，一邊慢慢針對基底層用標靶慢慢 下降濺鑛電力一邊針對保護膜用標靶慢慢提高濺鍍電力； 且一旦針對保護膜用標靶的濺鍍電力達到預定的値，即停 止針對基底層用標靶的濺鍍電力供給，並將含氟氣體混合 於不活性氣體中，施行所定時間的濺鍍，而在基底層上形 成由含有氟的金鋼石狀的碳所組成的保護膜，藉此在基底 層和保護膜之間形成構成基底層之元素和構成保護膜之元 素的混合區域爲其特徵。 本發明的第12手段，係將以周期表4a族、4b族、 5a族、6a族中之至少一種元素爲主成份的基底層用標靶 、和由碳所組成的中間膜·保護膜用標靶、和面對前述基 底層用標靶及中間膜·保護膜用標靶而配置的射出成形裝 置用構件的基材配置在不活性氣體中；並對前述基底層用 標靶施加預定的濺鍍電力並施行濺鍍而在基材上形成基底 層；且該基底層之膜厚成爲預定的厚度時，一邊慢慢針對 基底層用標靶慢慢下降濺鍍電力一邊針對中間膜·保護膜 用標靶慢慢提高濺鍍電力；且一旦針對中間膜·保護膜用 標靶的濺鍍電力達到預定的値，即停止針對基底層用標靶 -8- 1248861 (5) 的濺鍍電力供給，並施行所定時間的濺鍍，而在基底層上 形成由金鋼石狀碳所組成的中間膜，藉此在基底層和中間 膜之間形成構成基底層之元素和構成中間膜之元素的混合 區域；其次，於前述不活性氣體中混合含氟氣體並施行所 定時間的濺鍍，而在前述中間膜之上形成由含有氟的金 鋼石狀的碳所組成的保護膜爲其特徵。 本發明的第13手段乃於前述第11手段或第12手段 中，前述基底層的主成份元素爲由Cr、W、Ti、Si之群中 所選出的至少一種元素爲其特徵。 再者，本發明中的「主成份」是以構成的元素含有率 超過5 0重量％爲佳，也包括1 〇 〇重量％的情形。 【實施方式】 以下與圖面一同說明本發明的實施形態。第1圖係欲 說明有關第1實施形態之射出成形裝置的射出部的圖。 圖中之1係爲將例如AB S樹脂等的熔融樹脂2供給 到多支管3的豎澆道，4係爲安裝在多支管3之前端部的 複數個噴嘴本體（第1圖只描繪一個噴嘴本體4) ，5係 爲可移動配置在噴嘴本體4內並以樹脂密封澆口的針狀物 ’ 6係爲將針狀物5保持在噴嘴本體4之中心位置的針狀 物導套，7係爲內內有欲驅動針狀物5之活塞的圓筒，8 係爲成形模具，由固定側模具8a和可動側模具8b所構成 〇 由豎澆道1所供給的熔融樹脂2是經由多支管3分流 -9- 1248861 (6) 到各模具8的方向，且通過噴嘴本體4和針狀物5之間的 狹窄間隙，從噴嘴本體4之前端部射出到成形模具8 (模 槽）內，且保壓後藉由針狀物5密封澆口而得到樹脂成形 品。該射出成形裝置中，豎澆道1、多支管3、噴嘴本體 4，針狀物5、針狀物導套6、成形模具8等構件就會與成 形用的熔融樹脂2接觸。 第2圖係欲說明使用有關第2實施形態之螺桿的射出 成形裝置的射出部的圖。 圖中之11係爲加熱筒，12係爲捲裝在加熱筒11之 外側的帶式加熱器，1 3係爲配置在加熱筒1 1內並於旋轉 的同時在軸向移動的螺桿，1 4係爲設在螺桿1 3之前端部 側並可在螺桿1 3之軸向移動的鎖緊環，1 5係爲設置在螺 桿1 3之前端部的鎖緊頭，1 6係爲設置在加熱筒1 1之前 端部的加熱筒頭，1 7係爲安裝在加熱筒頭1 6的開式噴嘴 〇 從加料斗（圖未示）投入至加熱筒1 1之後端部1 8的 樹脂顆粒會一邊藉由螺桿1 3的旋轉將加熱筒1 1內移動到 前端側一邊利用來自加熱筒1 1 (帶式加熱器1 2 )的熱氣 而可塑化、混合。而充分熔融的樹脂會藉由向著螺桿13 之軸向的瞬間移動，通過螺桿1 3和鎖緊環1 4的間隙、鎖 緊頭1 5和加熱筒頭1 6的間隙，而從開式噴嘴1 7射出到 模具（圖未示）內。該射出成形裝置中，加熱筒11、螺 桿1 3、鎖緊環14、鎖緊頭1 5、開式噴嘴1 7等的構件就 會與熔融樹脂接觸。 -10- (7) 1248861 第3圖係欲說明有關第3實施形態的射出成形裝置 成形部的圖。圖中之2 1係爲安裝固定側模具22的固定 板，23係爲透過模具安裝板24而安裝可動側模具25 可動模板。可動模板23是利用鎖模裝置（圖未示）在 後（圖中爲左右）驅動，且取得可動側模具2 5密固在 定側模具22的鎖模位置和自可動側模具25離開固定側 具22的開模位置。 將可動側模具25密固在固定側模具22的狀態，並 由兩模具22、25形成模槽26，模槽26是透過澆口、 流道及豎澆道27而與樹脂注入口 28連通，且樹脂注入 28會壓住噴嘴29。自噴嘴29射出的熔融樹脂30會通 豎澆道27而塡充在模槽26內，且保壓、冷卻。然後打 模具，且前進移動推頂銷3 1，藉此將成形品自可動側 具25內突出並取出。在該成形部中，固定側模具22、 動側模具2 5或配合需要的型芯（圖未示），噴嘴2 9等 件會與熔融樹脂3 0接觸。 第4圖係欲說明有關第4實施形態的射出成形裝置 成形部的圖。圖中之32係爲由形成在在內面的鎳材形 對應數位影音光碟（DVD )之記錄資訊的微細凹凸面的 模，3 3係爲固定側模具，3 4係爲可動側模具，3 5係爲 模外周夾具。組合該些成形模具並閉合，藉此形成令成 品（本實施形態的情形是DVD用基板）成形的模槽3 6 模槽3 6會與安裝在固定側模具3 3的澆口構件3 7 及可上下動作的安裝在可動側模具3 4的澆口切斷構件 之 模 的 刖 固 模 藉 橫 □ 過 開 模 可 構 之 成 壓 壓 形 以 -11 - 38 (8) 1248861 所形成的橫流道3 9和豎澆道40連通。熔融狀態的聚碳酸 酯等的成形用樹脂會經由豎澆道40及橫流道3 9而射出塡 充到模槽3 6。 該樹脂冷卻、固化後，澆口切斷構件3 8會移動到上 方，並利用成形的成形品中央部的澆口切割部而加以切斷 ，然後移動可動側模具3 4而打開模具’取出轉印著壓模 32之微細凹凸面的DVD用基板。再者，圖中43係爲第 1 〇圖所詳述的保護膜，44係爲第1 1圖所詳述的中間膜。 前述實施形態所述的豎澆道1、多支管3、噴嘴本體 4、針狀物5、針狀物導套6、成形模具8、加熱筒1 1、螺 桿1 3、鎖緊環14、鎖緊頭1 5、開式噴嘴1 7、固定側模具 22、可動側模具25、型芯（圖未示）、噴嘴29、固定側 模具33、可動側模具34、壓模外周夾具35等射出成形裝 置的構件是適當選擇例如HPM1，2，17,31，38，50，PSL、 SUS420，440、SLD、HAP、SKD11， 6 1、STAVAX 、 NAK55，80，101等鋼材作爲基材。 於本發明中，於前述射出成形裝置之構件的至少一個 ，利用本發明形成保護膜。再者，不必在與前述基材之成 形用樹脂接觸的所有面形成保護膜，可形成一部分。 第5圖係表示在該基材之至少與成形用樹脂接觸的位 置形成保護膜狀態的部分放大斷面圖。如同圖所示，在基 材41上透過基底層42而形成保護膜43。基材41是由前 述的SKD等鋼材所組成，在其上形成以周期表4a族（Ti 、Zr、Hf) 、4b 族 （Si、Ge、Sn、Pb ) 、5a 族 （V、 -12- (9) 1248861The underlayer of at least one of Cr, Mo, and W) as a main component is a feature thereof. -6 - (3) 1248861 The third means of the present invention belongs to a member for an injection molding apparatus, and a part or all of the surface which is in contact with the molding resin is composed of carbon-containing carbon containing fluorine. The protective film is covered by its characteristics. According to a fourth aspect of the present invention, in the third aspect, the member means a molding die. According to a fifth aspect of the present invention, in the third aspect, the member is characterized by at least one of a pointer, a vertical bypass, a manifold, a heating cylinder, a screw, and a nozzle. According to a sixth aspect of the present invention, in the third to fifth aspect, at least one of Group 4a, Group 4b, Group 5a, and Group 6a of the periodic table is formed between the base material of the member and the protective film. The base layer of the element as the main component is characterized by it. According to a seventh aspect of the invention, in the sixth aspect, the main component element of the underlayer is characterized by at least one element selected from the group consisting of Cr, W, Ti, and Si. According to a sixth aspect of the present invention, in the sixth or seventh aspect, the mixed region layer constituting the element of the underlayer and the element constituting the protective film is formed between the underlayer and the protective film. According to a ninth aspect of the invention, in the sixth aspect, an intermediate film composed of diamond-like carbon is formed between the underlayer and the protective film. According to a ninth aspect of the invention, in the ninth aspect, a mixed region layer constituting an element of the underlayer and an element constituting the intermediate film is formed between the underlayer and the intermediate film. 1248861 (4) The third method of the present invention is to protect the basal layer mainly composed of at least one of the elements of Groups 4a, 4b, 5a, and 6a of the periodic table, and the composition of carbon. a substrate target, and a substrate of the member for injection molding device disposed to face the target for the base layer and the target for the protective film are disposed in an inert gas; and a predetermined splash is applied to the target for the base layer. When the thickness of the underlayer is a predetermined thickness, the substrate is layered with a power source and a sputtering thickness is applied to the substrate. Slowly increasing the sputtering power; and once the sputtering power for the protective film target reaches a predetermined enthalpy, the sputtering power supply to the substrate for the base layer is stopped, and the fluorine-containing gas is mixed in the inert gas, Sputtering for a predetermined period of time is performed, and a protective film composed of carbon-containing carbon-like carbon is formed on the base layer, whereby an element constituting the base layer and a protective film are formed between the base layer and the protective film. Mixed area of elements Its characteristics. According to a twelfth aspect of the present invention, a base layer target having at least one element selected from Groups 4a, 4b, 5a, and 6a of the periodic table and an intermediate film/protective film composed of carbon are used. The target substrate and the substrate of the member for injection molding device disposed to face the target for the base layer and the target for the interlayer film and the protective film are disposed in an inert gas; and the target for the base layer is applied to the target Sputtering electric power and performing sputtering to form a base layer on a substrate; and when the thickness of the underlying layer is a predetermined thickness, the interlayer film is gradually lowered while the sputtering power is gradually lowered for the underlying layer target. The film is gradually increased in sputtering power by the target; and once the sputtering power for the intermediate film/protective film target reaches a predetermined enthalpy, the sputtering power for the substrate -8-122481 (5) is stopped. Supplying and performing sputtering for a predetermined time, and forming an intermediate film composed of diamond-like carbon on the base layer, thereby forming an element constituting the base layer and an element constituting the intermediate film between the base layer and the intermediate film Mixed area; secondly, Mixing the inert gas and the fluorine-containing gas sputtering predetermined time implementation of plating, the protective film is formed of gold steel stone-like carbon containing fluorine is composed of the intermediate film over its characteristics. According to a thirteenth aspect of the present invention, in the first or fourth aspect, the main component element of the underlayer is characterized by at least one element selected from the group consisting of Cr, W, Ti, and Si. Further, the "main component" in the present invention is preferably such that the element content of the composition exceeds 50% by weight, and also includes 1% by weight. [Embodiment] Hereinafter, embodiments of the present invention will be described together with the drawings. Fig. 1 is a view for explaining an injection portion of the injection molding apparatus according to the first embodiment. In the figure, 1 is a vertical runner that supplies molten resin 2 such as AB S resin to the manifold 3, and 4 is a plurality of nozzle bodies installed at the front end of the manifold 3 (the first figure depicts only one nozzle) The body 4), 5 is a needle guide sleeve 6 which is movably disposed in the nozzle body 4 and sealed with a resin, and is a needle guide sleeve for holding the needle 5 at the center of the nozzle body 4, 7 It is a cylinder having a piston for driving the needle 5 therein, and 8 is a molding die, and is composed of a fixed side mold 8a and a movable side mold 8b. The molten resin 2 supplied from the vertical runner 1 is passed through The branch pipe 3 is diverted-9- 1248861 (6) to the direction of each of the molds 8, and is ejected from the front end portion of the nozzle body 4 into the forming mold 8 (cavity) through a narrow gap between the nozzle body 4 and the needle 5. After the pressure is maintained, the gate is sealed by the needle 5 to obtain a resin molded article. In the injection molding apparatus, members such as the vertical runner 1, the manifold 3, the nozzle body 4, the needle 5, the needle guide 6, and the molding die 8 are brought into contact with the molten resin 2 for forming. Fig. 2 is a view for explaining an injection portion of an injection molding apparatus using a screw according to a second embodiment. In the figure, 11 is a heating cylinder, 12 is a belt heater packaged on the outer side of the heating cylinder 11, and 13 is a screw disposed in the heating cylinder 1 1 and moving in the axial direction while rotating, 1 4 is a locking ring provided on the end side of the screw 13 and movable in the axial direction of the screw 13, and 15 is a locking head provided at the front end of the screw 13, and 16 is disposed at The heating head of the front end of the heating cylinder 1 1 is a resin pellet which is attached to the open nozzle of the heating cylinder head 16 and is fed from the hopper (not shown) to the end portion 18 after the heating cylinder 1 1 . While the inside of the heating cylinder 1 1 is moved to the front end side by the rotation of the screw 13, the hot gas from the heating cylinder 1 1 (belt heater 1 2) can be plasticized and mixed. The fully molten resin is moved from the axial direction of the screw 13, through the gap between the screw 13 and the lock ring 14, the gap between the lock head 15 and the heating head 16 from the open nozzle. 1 7 is shot into the mold (not shown). In the injection molding apparatus, members such as the heating cylinder 11, the screw 13, the lock ring 14, the lock head 15, and the open nozzle 17 are brought into contact with the molten resin. -10- (7) 1248861 Fig. 3 is a view for explaining a molding portion of the injection molding apparatus according to the third embodiment. In the figure, 2 1 is a fixing plate to which the fixed side mold 22 is attached, and 23 is a movable template which is attached to the movable side mold 25 through the mold mounting plate 24. The movable die plate 23 is driven by a mold clamping device (not shown) in the rear (left and right in the drawing), and the movable side mold 25 is fixed to the mold clamping position of the fixed side mold 22 and the movable side mold 25 is separated from the fixed side. With a mold opening position of 22. The movable side mold 25 is fixed in the state of the fixed side mold 22, and the mold grooves 26 are formed by the two molds 22 and 25. The mold groove 26 is communicated with the resin injection port 28 through the gate, the flow path and the vertical runner 27. And the resin injection 28 will press the nozzle 29. The molten resin 30 emitted from the nozzle 29 is filled in the cavity 26 through the vertical runner 27, and is kept pressurized and cooled. Then, the mold is punched, and the ejector pin 3 1 is moved forward to thereby project and take out the molded article from the movable side member 25. In the molded portion, the fixed side mold 22, the movable side mold 25, or a core (not shown) required for the fitting, and the nozzles 29 and the like are brought into contact with the molten resin 30. Fig. 4 is a view for explaining a molding portion of an injection molding apparatus according to a fourth embodiment. In the figure, 32 is a mold having a fine uneven surface on which a nickel-shaped corresponding digital audio-visual disc (DVD) formed on the inner surface is formed, and 3 3 is a fixed side mold, and 34 is a movable side mold, 3 The 5 series is a mold outer peripheral jig. Combining the molding dies and closing them, thereby forming a cavity for molding the finished product (the substrate for DVD in the present embodiment), the molding groove 36, and the gate member 37 of the fixed side mold 3 3 and The tamping mold of the mold of the gate cutting member which can be moved up and down in the movable side mold 34 can be formed into a cross flow passage formed by -11 - 38 (8) 1248861 by a cross-opening mold. 3 9 is connected to the down sprue 40. The molding resin such as polycarbonate in a molten state is discharged to the cavity 36 via the down sprue 40 and the cross flow path 39. After the resin is cooled and solidified, the gate cutting member 38 is moved upward, and is cut by the gate cutting portion at the center portion of the formed molded article, and then the movable side mold 34 is moved to open the mold 'take-out A substrate for a DVD on which a fine uneven surface of the stamper 32 is printed. Further, in the figure, 43 is a protective film detailed in Fig. 1 and 44 is an intermediate film detailed in Fig. 11. The vertical runner 1, the manifold 3, the nozzle body 4, the needle 5, the needle guide 6, the forming die 8, the heating cylinder 1, the screw 13, the locking ring 14, and the lock according to the foregoing embodiment The tight head 15 , the open nozzle 17 , the fixed side mold 22 , the movable side mold 25 , the core (not shown), the nozzle 29 , the fixed side mold 33 , the movable side mold 34 , the stamper outer peripheral jig 35 , etc. are injection molded. The members of the apparatus are suitably selected as a substrate such as HPM1, 2, 17, 31, 38, 50, PSL, SUS420, 440, SLD, HAP, SKD11, 61, STAVAX, NAK55, 80, 101. In the present invention, at least one of the members of the injection molding apparatus is used to form a protective film by the present invention. Further, it is not necessary to form a protective film on all the faces in contact with the forming resin of the above-mentioned base material, and a part thereof can be formed. Fig. 5 is a partially enlarged cross-sectional view showing a state in which a protective film is formed at a position where at least the substrate is in contact with the molding resin. As shown in the figure, a protective film 43 is formed on the substrate 41 through the base layer 42. The base material 41 is composed of the above-described steel material such as SKD, and is formed thereon with Group 4a (Ti, Zr, Hf), Group 4b (Si, Ge, Sn, Pb) and Group 5a (V, -12-) of the periodic table. (9) 1248861
Nb、Ta) 、6a族 （Cr、Mo、W)中之至少一種元素， 其中尤以從Cr、W、ΤΙ、Si群中選出的至少一種元素爲 主成份的基底層42，且在該基底層42之上形成由含氟 DLC所組成的保護膜43。 第5圖中，基底層42爲一層，但配合需要可爲兩層 以上的複數層，在例如由鋼材（Fe )形成的基材上形成由 Cr製成的第一基底層，且在其上形成由W製成的第二基 底層，並更可在其上形成由含氟DLC製成的保護膜。 相對於保護膜中的碳之氟的比例（F / C )爲0.2 5以 上的話，相對於成形用樹脂的剝離性及成形用樹脂的流動 性很良好，並隨著該比例（F / C )增加，剝離性、流動 性就會提高。但比例（F / C )增加的同時，保護膜之硬 度會有下降的傾向，比例（F I C )以0.3〜0 · 9的範圍爲佳 〇 該比例（FIC )可根據後述之濺鑛時的CF4、C2F8等 之含氟氣體的濃度所控制。而爲了使保護膜獲得 性也可 含氫，此時可使用cf4、c2f8等的含氟氣體和ch4、c2h8 等的碳氫化合物系氣體的混合氣體，且根據該混合比例可 控制保護膜中的氫含有率，隨著氫之含有量增多，而提高 保護膜的 性，但其比例（H/C )以0.05〜0.4的範圍爲 佳。 在基底層42、保護膜43及後述的中間膜之成膜很適 合使用濺鍍和離子噴鍍等之物理式蒸鍍法（PVD )或化學 式蒸鍍法（C V D )。 -13- (10) 1248861 第6圖係爲連續形成基底層42和保護膜4 3之濺鍍 置的槪略構成圖。 如同圖所示，在處理室51之中央部設有工作台52 且在工作台52上安裝複數個支撐台53。第7圖係表示 支撐台5 3上的構件6 5之支撐狀態的放大立體圖。如同 所示，在支撐台53之中央部直立設置支柱66，且在支 66的頭部固定頂板67，並在該頂頂板67的周圍吊掛複 個例如由針狀物5 (參考第1圖）等所組成之射出成形 置的構件6 5。第7圖中是表示像針狀物5之較細長的 件65吊掛在頂板67的例子，但構件65比較大的時候 也可將構件各個安裝在支撐台53上。工作台52和支撐 53是藉由馬達及其動力傳達機構（圖未均示）在預定 方向定速旋轉，該支撐台53所支撐的構件65也是隨著 撐台5 3的旋轉而轉動。 沿著工作台52的外周而搭載著板狀的基底層用標 54和保護膜用標靶55之濺鍍蒸發源56是略爲等間隔 各別設置。本實施形態的情形由於基底層42之厚度比 護膜43還薄，所以基底層用標靶54配置一個、保護膜 標靶55配置三個。基底層爲兩層的時候，例如第一基 層用標靶配置一個、第二基底層用標靶配置一個、保護 用標靶5 5配置兩個即可。基底層用標靶5 4是由從Cr、 、Ti、Si群中選出的至少一種金屬板所組成的，且保護 用標靶5 5是由石墨板所組成。 並在處理室51內設置氣體配管62，且處理室51 裝 在 圖 柱 數 裝 構 ， 台 的 支 靶 的 保 用 底 膜 W 膜 內 -14- (11) 1248861 的真空度保持在1(^〜ltr1 Pa的範圍，放電用不活性氣體 是氬（Ar )氣，但可用含氟氣體的四氟化甲烷（CF4 )、 六氟化乙烷（C2F6 )等。於濺鍍蒸發源56利用如後述的 定時自濺鍍電源（圖未示）施加濺鍍電力。經由施加該濺 鍍電力，會一邊整個形成氬之電漿64 —邊連續成膜出基 底層42和保護膜43。 第8圖係欲說明針對標靶54、55的濺鍍電力之施加 狀態圖。如同圖所示，最先在基底層用標靶54施加5 00W 的電壓（實線），且保護膜用標靶55這方爲off ( 0W) 狀態（虛線）。經由施加該濺鍍電力產生電漿，且氬離子 會衝撞基底層用標靶54而彈跳標靶材料，該濺鑛的粒子 會堆積到構件65的基材41而形成基底層42。構件65會 自行一邊旋轉一邊幾次通過基底層用標靶54之前，就會 整體沒有斑點的形成基底層42。基底層42大約堆積到預 定的厚度，即將濺鍍電力保持在一定的程度。 然後一邊針對基底層用標靶54慢慢下降濺鍍電力一 邊針對保護膜用標靶5 5慢慢上升濺鍍電力，針對保護膜 用標靶55的電力達到1 000W的時候，針對基底層用標靶 54的電力爲0W，然後以該狀態維持一定時間的方式進行 控制。 因氬離子衝撞而彈跳的碳粒子會堆積在基底層42之 上而形成DLC膜，但此時在碳粒子堆積時，在氣體中混 合著含氟氣體，氟也會一起捲入，形成由含氟DLC所組 成的保護膜43。此時構件65也會自行一邊旋轉一邊幾次 -15- 1248861 (12) 通過各保護膜用標靶5 5之前，就會整體沒有斑點的形成 保護膜43。 由基底層42的形成換切到保護膜43的形成之際，如 前所述，施行一邊慢慢下降針對基底層用標靶54的濺鍍 電力一邊上升針對保護膜用標靶5 5的濺鍍電力的操作。 藉此連續變化基底層42和保護膜43的組成而有濃度增減 率，且結果基底層42之基材4 1側之構成該基材的金屬含 有率約爲1 00%，而隨著完成保護膜43側金屬含有率會慢 慢減少，而含氟DLC的含有率會增加，在基底層42和保 護膜4 3的中間部分，金屬成份和含氟D L C的含有率約爲 一半一半，保護膜43側和金屬成份的含有率更少，在保 護膜43的表面附近，含氟DLC的含有率大約爲100%。 因而，不能很明確的確認基底層4 2和保護膜4 3的邊界（ 因此第5圖中基底層42和保護膜43的邊界部附近以點線 表示）。 基底層42的膜厚爲Ο.ίμηι〜2μπι，最好爲Ο.ίμιη〜Ιμιη ，保護膜43的膜厚爲Ο.ίμιη〜5μηι，最好爲 〇.5μιη〜3μιη 一旦剩下很薄的膜厚就很難發揮良好的剝離性、流動性， 一方面，太厚的話，保護膜43自身易從基材4 1側剝離， 其機能受損，所此推薦上述範圍的膜厚。 例如有孔和凹部、凸部等之構件65的情形下，在該 構件和標靶54、55之間使用配置著格子狀的平行光管電 極的平行光管濺鍍法的話，就能選擇性附著上相對於構件 65之孔和凹部、凸部之面而垂直之成份的濺鍍粒子很理 -16- (13) 1248861 想。 第9圖係欲說明適於形成前述基底層42、保護膜43 及後述·之中間膜的非平衡磁控濺鍍法原理的圖。 如圖所示，在與基底層用標靶5 4及保護膜用標靶5 5 之略中央部面對面的位置配置形成弱磁場的內側磁極56 ，且在與標靶54、55之外周部面對面的位置配置形成強 磁場的外側磁極5 7，並形成非平衡的磁場。 並一邊形成電漿64 —邊藉著強力的外側磁極5 7產生 的磁力線58的部分達到構件65附近。沿著該磁力線58 而於濺鍍時產生的等離子（例如氬離子）和電子，比平常 濺鍍更多達到構件65的表面，因此能夠形成很密且平面 平滑的基底層42、保護膜43、中間膜。 第1 0圖係表示在有關本發明之變形例的基材上形成 保護膜狀能的部分放大斷面圖。如同圖所示，在由SKD 等鋼材所製成的基材4 1上，形成以Cr爲主成份的基底層 42，且在其上形成由以碳及氫爲主成份的DLC所製成的 中間膜44。 此時，由於一邊慢慢下降針對基底層用標靶的濺鍍電 力一邊慢慢上升針對欲形成DLC膜的石墨板（中間膜· 保護膜用標靶）的濺鍍電力，故在基底層42和中間膜44 的邊界部會形成具有Cr和DLC之濃度增減率的混合區域 層45。而從中間膜44的形成中途供給含氟氣體，並在中 間膜44之上形成由含氟DLC製成的保護膜43。 本實施形態中的膜厚係基底層42約爲O.bm ’混合 -17- (14) 1248861 區域層4 5約爲〇 · 2 μ m，中間膜4 4約爲Ο . 7 μ m， 約爲0·5μιη。就算不形成中間膜44並將由含氟 成的保護膜43直接形成在基底層42之上’或j 43之下設置中間膜44 ’中間膜44這方比保護 的時候，膜整體還是會有彎曲的傾向。 因此如本實施形態，在基底層42和保護膜 置中間膜44，且將中間膜44的膜厚做的比保| 膜厚還厚的話，中間膜44就有補強保護膜43 d 形成耐久性強的膜。 第4圖所示的射出成形裝置之情形，在與固 3 3之模槽3 6面對面的表面流入成形用樹脂並相 故，如第1 0圖所示，需要在表面形成保護膜43 一方面，可動側模具3 4的表面是用壓模3 2 與成形用樹脂接觸，取而代之的是與壓模3 2接 。因此可動側模具3 4的表面乃如第1 1圖所示 41之上形成基底層42、混合區域層45、中間膜 設保護膜4 3。在基材4 1的表面設置由D L C所組 膜44，藉此利用優異的耐磨耗性和低摩擦性， 因與壓模3 2的滑接引起可動側模具3 4的磨耗。 成形用樹脂接觸的壓模32之表面也可適當形成 保護膜43。 在可動側模具3 4的外表面也能設置由含氟 的保護膜43 ’但中間膜44這方的機械強度比| 強的緣故，可動側模具3 4的外表面以中間膜4 4 保護膜43 DLC所製 :在保護膜 莫43還薄 4 3之間設 I膜43的 f效果，且 定側模具 丨接合的緣 〇 覆蓋，不 觸的構造 ，於基材 44，而不 成的中間 就能防止 此時在與 含氟DLC DLC製成 呆護膜43 追方爲佳 -18- (15) 1248861 第12圖和第13圖係表不利用第1圖之成形裝置並由 AB S樹脂所組成的卡匣盒之澆口密封部狀態的放大平面圖 。而第12圖係如第5圖所示在由SKD製成的基材41上 形成由W製成的基底層42，且使用在其上形成整個由含 氟DLC所組成的保護膜43的針狀物5 (參考第1圖）， 並密封澆口者，第1 3圖係使用由S KD所製成，且在表面 不形成保護膜4 3的習知針狀物並密封澆口者的放大平面 圖。 使用習知針狀物的時候，與樹脂之剝離性不良的緣故 ，如第1 3圖所示，會在成形品之遮蔽澆口部形成氣泡狀 的突出部，或是產生毛邊，因此澆口部的凹凸很顯眼，外 觀上不佳。 對此，若使用形成由含氟DLC製成的保護膜43的針 狀物，與樹脂之剝離性佳的緣故，如第12圖所示，在成 形品的遮蔽澆口部幾乎找不到氣泡狀的突出部，且大體上 很平整的澆口部，第1 3圖所示的習知者，外觀上非常差 〇 射出成形裝置之構件中尤其是針狀物，與噴嘴本體之 間的間隙很窄，壓送熔融樹脂之際要施加相當的高壓，樹 脂溫度也很高，很容易附著成形結束時所殘留下的樹脂， 而且與針狀物導套6 (參考第1圖）滑接的緣故，在針狀 物表面形成含有氟的金鋼石狀的碳的保護膜43，對於與 前述針狀物導套6的滑動特性會變得很良好，所以很有效 -19- (16) 1248861 第1 4圖和第1 5圖係欲說明剝離性之試驗方法的圖。 如第1 4圖所示。在由鏡面加工之S U S材料（Η Ρ Μ 3 8 )所 製成的試驗片7 1之表面形成各式各樣的D L C膜7 2，且將 各種樹脂粉末塡充至內徑3 m m的鋁管7 3內。並且以鋁管 73之下端開口部與前述DLC膜72接觸的方式直立在前述 試驗片7 1之上，並利用加熱板加熱到2 5 0 °C，並將鋁管 7 3接合在試驗片7 1上。 其次，如第1 4圖所示，以鋁管73爲水平的方式將試 驗片71設置在基台74上，且使推拉計75的壓制部76以 2 5 mm/m in的一定速度下降，使剪斷方向的應力施加在鋁 管73。然後以鋁管73自試驗片71剝離時的推壓強度作 爲剝離強度進行評估。各試驗的試料數量爲五個。 第1 6圖和第1 7圖係表示其剝離強度試驗結果的圖， 分別爲第1 6圖係表示使用塡充在前述鋁管73的樹脂爲 AB S樹脂，第1 7係表示使用聚苯乙烯樹脂的情形。而各 圖中，X爲沒有任何構件形成在試驗片7 1上，而是在 SU S的鏡面上直接利用樹脂接合鋁管73，Y是在試驗片 71上形成DLC膜，Z是在試驗片71上形成本發明的含氟 DLC膜的試驗結果。 由該些圖即可明白，形成本發明之含氟DLC膜的（Z )’與其他構件（X，Y )相比，剝離強度低，亦即針對 樹脂的剝離性良好，且剝離強度的誤差，與其他構件（X ，Y )相比較少。 -20- (17) 1248861 第1 8圖係爲用於模具內之樹脂的流動性試驗 側模具的平面圖。如同圖所示，在試驗用可動側辛 的表面，如斜線所示，形成螺旋溝82，螺旋溝82 爲0.5mm、寬度爲l〇mm。在螺旋溝82的中途隔著 置合計12根的彈射銷83、84。 一方面’不在試驗用固定側模具形成螺旋溝 對前述可動側模具8 1之螺旋溝8 2的表面很平坦。 定側模具的中心部，在與前述彈射銷8 3對應的位 樹脂注入孔，樹脂會自該注入孔供給到螺旋溝82。 接合該試驗用的可動側模具和固定側模具並予 且以成形溫度320°C 、射出速度200mm/s、射 2 OOMpa的條件，試驗出自樹脂注入孔83注入聚碳 R 1 7 0 0 )之際，樹脂是否會自螺旋溝8 2的中央部順 溝8 2流出至各處，其結果於第1 9圖示之。 於第1 9圖中，橫軸是以在模具內流出樹脂的 爲流動量而表現，且縱軸是表示次（個）數。圖中 棒圖形是表示可動側模具及固定側模具也一起鏡面 SUS材料（HPM38) ’黑棒圖形是表示在可動側模 定側模具也一起鏡面加工的S U S材料（Η P Μ 3 8 ) 成本發明之含氟DLC保護膜。再者，在各模具進朽 射注過程，顯示2 5次射注過程的次數分佈。 由該圖即可明白，在模具表面形成含氟DLC 的本發明構件，就連螺旋溝82之深度〇.5mm之極 形下，在模具內的樹脂流動性極爲良好，而且能充 之可動 莫具81 的深度 間隔配 82，面 在該固 置設置 鎖模， 出壓力 酸酯（ 著螺旋 長度作 的反白 加工的 具及固 之上形 F 25次 保護膜 淺的情 分對應 -21 - (18) l248861 形成薄壁。 構成射出成形裝置的構件中尤其是成形模具，成形用 樹脂流動性良好，且與成形用樹脂的脫模性良好，具有如 &下所記載的特長。 〇可使用分子量高的成形用樹脂，可提高成形品的機 械性質； 〇可降低成形溫度，達到削減加熱用電力； 〇成形模具不需要脫模錐度’或者錐形角度可以很小 〇彈射銷數量減少； 〇接觸（成形週期時間）縮短； 〇可形成薄壁； 〇可形成複雜的形狀； 〇成形模具的耐蝕性提高； 〇成形條件的限度出現餘裕，成形週期具穩定性； 〇成形模具不易損傷，模具處理性變佳； 〇習知之成形模具爲了保持與成形用樹脂的脫模性， 不得降低模具的面粗度，但提高模具的面粗度就能鏡面加 工模具表面； 〇噴射形成品時，並未施加不當的力，故具有彎曲等 之變形少等等的特長。 成形樹脂材料於氯乙烯樹脂的情形下產生氯氣，難燃 性樹脂的情形下產生氯、溴等鹵化物、磷化物，AB S樹脂 的情形下產生加硫劑，聚甲醛樹脂的情形下產生蟻酸、福 -22- (19) 1248861 馬林，低發泡樹脂的情形下產生氨、一氧化碳等腐蝕性氣 體的可能性很高。 可是，由本發明之含氟DLC製成的保護膜耐蝕性優 的緣故，能夠阻止成形裝置之構件受到前述腐蝕性氣體的 侵飩，能延長成形裝置的耐用壽命，且能經常維持穩定的 成形週期。 (發明效果） 本發明係爲如前所述的構成，與樹脂接合的面是由含 氟DLC製成的保護膜所覆蓋，藉此與樹脂的剝離性良好 ，且在成形品的表面不會產生氣泡狀的突出部、毛邊、剝 落等以及樹脂燒焦。而且樹脂流動良好，因此成形性獲得 改善，可形成薄壁、精密成形。 而由含氟DLC所製成的保護膜耐蝕性優，構件不會 因成形時等產生的腐蝕性氣體所侵鈾，成形裝置的耐用壽 命延長，且能經常維持穩定的成形週期。 更且只要在基材和保護膜之間設置基底層、中間膜， 基材和保護膜的接合性即變得很優良，如前所述的保護膜 效果就能長期間有效的發揮。 更還在基底層和保護膜之間形成構成基底層之元素和 構成保護膜之元素的混合區域，一旦在基底層和保護膜之 間不存在明確的界面，基底層和保護膜就能連續性地一體 化，結果基材和保護膜的接合性變得更強，且具有保護膜 效果可長期間有效發揮等之特長。 -23- (20) 1248861 【圖式簡單說明】 第1圖係欲說明有關本發明之第1實施形態的射出成 形裝置之射出部的圖。 第2圖係欲說明有關本發明之第2實施形態的射出成 形裝置之射出部的圖。 第3圖係欲說明有關本發明之第3實施形態的射出成 形裝置之成形部的圖。 第4圖係欲說明有關本發明之第4實施形態的射出成 形裝置之成形部的圖。 第5圖係表示在本發明的基材上形成保護膜狀態的部 分放大斷面圖。 弟r 6圖係爲潑鑛裝置的槪略構成圖。 第7圖係表示在支撐台上的構件之支撐狀態的放大立 體圖。 第8圖係欲說明針對標靶的濺鍍電力施加狀態的圖。 第9圖係欲說明非平衡磁控濺鍍法原理的圖。 第10圖係表示在有關本發明之變形例的基材上形成 保護膜狀態的部分放大斷面圖。 第1 1圖係表示第4圖所示的可動側模具之表面狀態 的部分放大斷面圖。 第1 2圖係表示使用有關本發明之實施形態的針狀物 情形之澆口密封部狀態的放大平面圖。 第1 3圖係表示使用習知針狀物情形之澆口密封部狀 -24- (21) 1248861 態的放大平面圖。 第1 4圖係欲說明剝離性試驗方法的圖。 第1 5圖係欲說明剝離性試驗方法的圖。 第1 6圖係表示使用AB S樹脂情形之剝離性試驗結果 的特性圖。 第1 7圖係表示使用聚苯乙烯樹脂情形之剝離性試驗 結果的特性圖。 第1 8圖係用於試驗模具內之樹脂流動性的試驗用可 動側模具的平面圖。 第1 9圖係表不流動性試驗結果的特性圖。 【主要元件對照表】 1:豎澆道、2:熔融樹脂、3:多支管、4:噴嘴本體、 5 :針狀物、6 :針狀物導套、7 :圓筒、8 :成形模具、 8 a:固定側模具、8b:可動側模具、1 1 :加熱筒、 12:帶式加熱器、13:螺桿、14:鎖緊環、15:鎖緊頭、 16:加熱筒頭、17:開式噴嘴、21:固定模板、 22:固定側模具、23:可動模板、24:模具安裝板、 25:可動側模具、26:模槽、27:豎澆道、28:樹脂注入口、 29:噴嘴、30:熔融樹脂、31:推頂銷、32:壓模、 33:固定側模具、34:可動側模具、35:壓模外周夾具、 3 6 :模槽、3 7 :澆口構件、3 8 :澆口切斷構件、3 9 :橫流道、 40:豎澆道、41:基材、42:基底層、43:保護膜、44:中間膜 、45:混合區域層、51:處理室、52:工作台、53:支撐台、 -25- (22) 1248861 54:基底層用標靶、55:保護膜用標靶、56:內側磁極、 57:外側磁極.、58:磁力線、62:氣體配管、64:電漿、 6 5 :構成零件、6 6 :支柱、6 7 :頂板。 -26-At least one of Nb, Ta), Group 6a (Cr, Mo, W), wherein at least one element selected from the group consisting of Cr, W, ΤΙ, and Si is a base layer 42 having a main component, and is on the substrate A protective film 43 composed of fluorine-containing DLC is formed on the layer 42. In Fig. 5, the base layer 42 is a single layer, but a plurality of layers of two or more layers may be required for the formation, and a first base layer made of Cr is formed on a substrate formed of, for example, a steel material (Fe), and is formed thereon. A second substrate layer made of W is formed, and a protective film made of fluorine-containing DLC is further formed thereon. When the ratio (F / C) of fluorine to carbon in the protective film is 0.2 5 or more, the releasability with respect to the molding resin and the fluidity of the molding resin are excellent, and along with the ratio (F / C) Increase, peeling, and liquidity will increase. However, when the ratio (F / C) increases, the hardness of the protective film tends to decrease, and the ratio (FIC) is preferably in the range of 0.3 to 0.9 · 9. The ratio (FIC ) can be CF4 according to the sputtering method described later. The concentration of the fluorine-containing gas such as C2F8 is controlled. In order to obtain the protective film, hydrogen may be contained. In this case, a mixed gas of a fluorine-containing gas such as cf4 or c2f8 and a hydrocarbon-based gas such as ch4 or c2h8 may be used, and the protective film may be controlled according to the mixing ratio. The hydrogen content rate increases the properties of the protective film as the content of hydrogen increases, but the ratio (H/C) is preferably in the range of 0.05 to 0.4. The film formation of the underlayer 42 and the protective film 43 and an intermediate film to be described later is suitably carried out by physical vapor deposition (PVD) or chemical vapor deposition (C V D ) such as sputtering or ion plating. -13- (10) 1248861 Fig. 6 is a schematic view showing the sputtering of the underlying layer 42 and the protective film 43. As shown in the figure, a table 52 is provided at a central portion of the processing chamber 51, and a plurality of support tables 53 are mounted on the table 52. Fig. 7 is an enlarged perspective view showing the supporting state of the member 65 on the support table 53. As shown, a pillar 66 is erected at a central portion of the support table 53, and a top plate 67 is fixed to the head of the branch 66, and a plurality of needles 5 are suspended around the top plate 67 (refer to Fig. 1). And a component 65 that is formed by injection molding. Fig. 7 shows an example in which the elongated member 65 of the needle 5 is hung on the top plate 67. However, when the member 65 is relatively large, the members can be attached to the support table 53. The table 52 and the support 53 are rotated at a constant speed in a predetermined direction by a motor and a power transmission mechanism thereof (not shown), and the member 65 supported by the support table 53 is also rotated in accordance with the rotation of the support 53. The sputter evaporation source 56 on which the plate-shaped base layer flag 54 and the protective film target 55 are mounted along the outer circumference of the table 52 are provided at equal intervals. In the case of the present embodiment, since the thickness of the underlying layer 42 is thinner than the protective film 43, the underlying layer is disposed one by one target 54 and the protective film target 55 is disposed in three. When the base layer is two layers, for example, the first base layer is disposed by the target, the second base layer is disposed by the target, and the protective target is disposed at two. The target layer target 5 4 is composed of at least one metal plate selected from the group consisting of Cr, Ti, and Si, and the protective target 5 5 is composed of a graphite plate. A gas pipe 62 is disposed in the processing chamber 51, and the processing chamber 51 is installed in the number of columns of the column, and the vacuum degree of the film 14-(11) 1248861 in the film of the support base of the table is maintained at 1 (^ In the range of ~ltr1 Pa, the inert gas for discharge is argon (Ar) gas, but a fluorine-containing gas such as tetrafluoromethane (CF4) or hexafluoride (C2F6) can be used. The sputtering power is applied from a sputtering power source (not shown) to be described later. By applying the sputtering power, the underlying layer 42 and the protective film 43 are continuously formed while forming the argon plasma 64. The application state diagram of the sputtering power for the targets 54 and 55 is described. As shown in the figure, a voltage of 500 W (solid line) is first applied to the substrate layer target 54, and the target film 55 is used for the protective film. The square is off (0W) state (dashed line). The plasma is generated by applying the sputtering power, and the argon ions collide with the base layer target 54 to bounce the target material, and the splashed particles are deposited on the base of the member 65. The base layer 42 is formed by the material 41. The member 65 passes through the base layer several times while rotating oneself. Before the target 54, the base layer 42 is formed without spots as a whole. The base layer 42 is deposited to a predetermined thickness, that is, the sputtering power is maintained to a certain extent. Then, the sputtering is slowly lowered by the target 54 for the base layer. When the electric power of the protective film target 55 reaches 1 000 W, the electric power of the target 55 for the protective film is 0 W, and the power is maintained at this state. The time is controlled. The carbon particles bounced by the argon ion collision will accumulate on the base layer 42 to form a DLC film. However, at the time of carbon particle deposition, the fluorine gas is mixed in the gas, and the fluorine is also mixed. Involved, a protective film 43 composed of fluorine-containing DLC is formed. At this time, the member 65 is also rotated a few times by itself - 15 - 1248861 (12), before passing through the target 5 5 for each protective film, there is no spot as a whole. When the formation of the protective layer 43 is changed from the formation of the underlayer 42 to the formation of the protective film 43 as described above, the protective film is raised while gradually lowering the sputtering power for the underlying layer target 54. The operation of the sputtering power of the target 55. Thereby, the composition of the underlying layer 42 and the protective film 43 is continuously changed to have a concentration increase and decrease rate, and as a result, the metal constituting the substrate on the substrate 41 side of the underlayer 42 contains The rate is about 100%, and the metal content rate on the side of the protective film 43 is gradually decreased, and the content of the fluorine-containing DLC is increased. In the middle portion of the base layer 42 and the protective film 43, the metal component and the content The content of fluorine DLC is about half of that, and the content of the protective film 43 side and the metal component is less. The content of fluorine-containing DLC is about 100% in the vicinity of the surface of the protective film 43. Therefore, the boundary between the base layer 42 and the protective film 43 cannot be clearly confirmed (so that the vicinity of the boundary portion between the base layer 42 and the protective film 43 in Fig. 5 is indicated by a dotted line). The film thickness of the base layer 42 is Ο.ίμηι~2μπι, preferably Ο.ίμιη~Ιμιη, and the film thickness of the protective film 43 is Ο.ίμιη~5μηι, preferably 〇.5μιη~3μιη once the thin film is left When it is thick, it is difficult to exhibit good peelability and fluidity. On the other hand, if it is too thick, the protective film 43 itself is easily peeled off from the side of the substrate 41, and its function is impaired, and the film thickness in the above range is recommended. For example, in the case of a member 65 having a hole, a concave portion, a convex portion, or the like, a parallel light pipe sputtering method in which a lattice-like collimator electrode is disposed between the member and the targets 54 and 55 can be selectively used. It is reasonable to attach a sputtered particle which is perpendicular to the surface of the hole and the concave portion and the convex portion of the member 65. 16-(13) 1248861 Fig. 9 is a view for explaining the principle of the unbalanced magnetron sputtering method suitable for forming the underlying layer 42, the protective film 43, and the intermediate film described later. As shown in the figure, the inner magnetic pole 56 which forms a weak magnetic field is disposed at a position facing the central portion of the base layer target 5 4 and the protective film target 5 5, and is face-to-face with the outer periphery of the targets 54, 55. The position is configured to form an outer magnetic pole 57 of a strong magnetic field and form an unbalanced magnetic field. The portion of the magnetic field line 58 generated by the strong outer magnetic pole 5 7 is formed near the member 65 while forming the plasma 64. The plasma (for example, argon ions) and electrons generated at the time of sputtering along the magnetic lines of force 58 reach the surface of the member 65 more than usual, so that a dense and smooth base layer 42 and a protective film 43 can be formed. Intermediate film. Fig. 10 is a partially enlarged cross-sectional view showing the ability of forming a protective film on a substrate according to a modification of the present invention. As shown in the figure, on the substrate 41 made of steel such as SKD, a base layer 42 mainly composed of Cr is formed, and a DLC mainly composed of carbon and hydrogen is formed thereon. Intermediate film 44. At this time, the sputtering power for the graphite plate (the intermediate film/protective film target) on which the DLC film is to be formed is gradually increased while gradually lowering the sputtering power for the underlying layer target, so that the underlying layer 42 is At the boundary portion with the intermediate film 44, a mixed region layer 45 having a concentration increase and decrease rate of Cr and DLC is formed. On the other hand, a fluorine-containing gas is supplied from the middle of the formation of the intermediate film 44, and a protective film 43 made of fluorine-containing DLC is formed on the intermediate film 44. The film thickness base layer 42 in the present embodiment is approximately O.bm 'mixed -17-(14) 1248861. The region layer 4 5 is approximately 〇· 2 μ m, and the intermediate film 4 4 is approximately Ο. 7 μ m, approximately It is 0·5μιη. Even if the intermediate film 44 is not formed and the protective film 43 made of fluorine is directly formed on the base layer 42 or the intermediate film 44 is disposed under the j 43 as the intermediate film 44, the film is generally bent. Propensity. Therefore, according to the present embodiment, when the intermediate layer 44 is placed on the base layer 42 and the protective film, and the film thickness of the intermediate film 44 is made thicker than the film thickness, the intermediate film 44 has the durability of the reinforcing protective film 43d. Strong film. In the case of the injection molding apparatus shown in Fig. 4, the molding resin flows into the surface facing the cavity 33 of the solid 3 3 and is inferior. As shown in Fig. 10, it is necessary to form the protective film 43 on the surface. The surface of the movable side mold 34 is brought into contact with the molding resin by the stamper 3 2, and replaced with the stamper 32. Therefore, the surface of the movable side mold 34 is formed with the base layer 42, the mixed region layer 45, and the intermediate film provided with the protective film 43 as shown in Fig. 11. A film 44 composed of DLC is provided on the surface of the substrate 41, whereby the wear resistance and the low friction property are utilized, and the movable side mold 34 is worn by the sliding contact with the stamper 32. The protective film 43 can also be formed as appropriate on the surface of the stamper 32 which is in contact with the molding resin. The outer surface of the movable side mold 34 can also be provided with a fluorine-containing protective film 43', but the mechanical strength ratio of the intermediate film 44 is stronger, and the outer surface of the movable side mold 34 is protected by the intermediate film 44. 43 DLC: The f-effect of the I film 43 is set between the protective film Mo43 and the thin film 4, and the edge of the fixed side mold 丨 is covered, and the non-touching structure is in the middle of the substrate 44. It can prevent the formation of the protective film 43 with the fluorine-containing DLC DLC at this time. It is better to use the -18- (15) 1248861. Figure 12 and Figure 13 do not use the forming device of Figure 1 and are made of AB S resin. An enlarged plan view of the state of the gate seal of the assembled cassette. On the other hand, in Fig. 12, a base layer 42 made of W is formed on the substrate 41 made of SKD as shown in Fig. 5, and a needle on which the entire protective film 43 composed of fluorine-containing DLC is formed is used. 5 (refer to Fig. 1), and sealing the gate, the 13th figure uses a conventional needle made of S KD and does not form a protective film 43 on the surface and seals the gate Zoom in on the floor plan. When the conventional needle is used, the peeling property with the resin is poor, and as shown in Fig. 3, a bubble-like protruding portion is formed in the shielding gate portion of the molded article, or a burr is generated, so that the gate is formed. The bumps in the section are conspicuous and the appearance is not good. On the other hand, when a needle formed of the protective film 43 made of fluorine-containing DLC is used, the peeling property with the resin is good, as shown in Fig. 12, almost no bubbles are found in the shielding gate portion of the molded article. a generally protruding portion, and a substantially flat gate portion, the conventional one shown in Fig. 3 is very poor in appearance, and the member of the injection molding device, particularly the needle, and the gap between the nozzle body and the nozzle body It is very narrow, and when the molten resin is pressed, a high pressure is applied, and the resin temperature is also high. It is easy to attach the resin remaining at the end of the forming, and is slidably attached to the needle guide 6 (refer to Fig. 1). For this reason, the protective film 43 of the diamond-containing carbon containing fluorine is formed on the surface of the needle, and the sliding property with the needle guide sleeve 6 is excellent, so it is effective -19-(16) 1248861 Fig. 14 and Fig. 15 are diagrams for explaining the test method of the peelability. As shown in Figure 14. A variety of DLC films 72 were formed on the surface of the test piece 71 made of mirror-finished SUS material (Η Μ 8 3 8 ), and various resin powders were filled into an aluminum tube having an inner diameter of 3 mm. 7 3 inside. And the opening portion of the lower end of the aluminum tube 73 is erected on the test piece 7 1 in contact with the DLC film 72, and heated to 250 ° C by a heating plate, and the aluminum tube 7 3 is joined to the test piece 7 1 on. Next, as shown in Fig. 14, the test piece 71 is placed on the base 74 so that the aluminum tube 73 is horizontal, and the pressed portion 76 of the push-pull gauge 75 is lowered at a constant speed of 25 mm/m in The stress in the shearing direction is applied to the aluminum tube 73. Then, the pressing strength at the time of peeling off from the test piece 71 by the aluminum tube 73 was evaluated as the peeling strength. The number of samples for each test was five. Fig. 16 and Fig. 17 show the results of the peel strength test. Fig. 16 shows that the resin used in the aluminum tube 73 is AB S resin, and the seventh system indicates the use of polyphenylene. The case of vinyl. In each of the figures, X is formed without any member on the test piece 71, but the aluminum tube 73 is directly joined by a resin on the mirror surface of the SU S, Y is a DLC film formed on the test piece 71, and Z is a test piece. The test results of the fluorine-containing DLC film of the present invention were formed on 71. As is apparent from these figures, the (Z)' forming the fluorine-containing DLC film of the present invention has a lower peel strength than the other members (X, Y), that is, the peeling property against the resin is good, and the peel strength error , compared with other components (X, Y). -20- (17) 1248861 Figure 18 is a plan view of the side mold for the fluidity test of the resin used in the mold. As shown in the figure, on the surface of the movable side of the test, as shown by the oblique line, a spiral groove 82 is formed, and the spiral groove 82 is 0.5 mm and the width is l〇mm. In the middle of the spiral groove 82, 12 projecting pins 83 and 84 are placed in total. On the other hand, the spiral groove is not formed in the test side mold, and the surface of the spiral groove 8 2 of the movable side mold 8 1 is flat. The center portion of the fixed side mold is supplied to the spiral groove 82 from the injection hole in the position resin injection hole corresponding to the above-described ejection pin 8.3. The movable side mold and the fixed side mold for the test were joined, and a polycarbon R 1 7 0 0 was injected from the resin injection hole 83 under the conditions of a molding temperature of 320 ° C, an injection speed of 200 mm/s, and a shot of 2 OOMpa. Then, whether or not the resin flows out from the center portion of the spiral groove 8 2 to the groove 8 2 is obtained, and the result is shown in Fig. 19. In Fig. 19, the horizontal axis represents the flow amount of the resin flowing out of the mold, and the vertical axis represents the number of times. In the figure, the bar graph indicates that the movable side mold and the fixed side mold are also mirrored together with the SUS material (HPM38). The black rod pattern indicates that the movable side mold side mold is also mirror-finished with the SUS material (Η P Μ 3 8 ). Fluorine-containing DLC protective film. Furthermore, in each of the molds, the number of times of the injection process is shown. As can be understood from the figure, the member of the present invention in which the fluorine-containing DLC is formed on the surface of the mold, even under the pole shape of the spiral groove 82 having a depth of 〇5 mm, the resin flowability in the mold is extremely good, and the charge can be filled. With 81 depth spacing with 82, the surface is set in the fixed mode, the pressure acid ester (the spiral length of the reverse white processing and the solid upper F 25 times protective film shallow corresponding to the score - 21 - (18) L248861 Thin wall is formed. Among the members constituting the injection molding apparatus, a molding die is particularly preferable, and the molding resin has good fluidity and good mold release property with the molding resin, and has the characteristics as described in & The use of a molding resin having a high molecular weight can improve the mechanical properties of the molded article; 〇 can lower the forming temperature and reduce the power for heating; the 〇 forming mold does not require a demolding taper' or the taper angle can be small; 〇 contact (forming cycle time) is shortened; 〇 can form thin walls; 〇 can form complex shapes; 耐 forming molds have improved corrosion resistance; 〇 forming conditions have margins The forming cycle is stable; the forming die is not easily damaged, and the mold handling property is improved. The conventional forming die must not reduce the surface roughness of the mold in order to maintain the mold release property with the molding resin, but increase the surface roughness of the mold. The surface of the mold can be mirror-finished; when the squirting product is formed, no undue force is applied, so that the deformation is small such as bending, etc. The molding resin material generates chlorine gas in the case of vinyl chloride resin, and the case of flame retardant resin Under the conditions of chlorine, bromine and other halides, phosphides, AB S resin in the case of sulfurizing agents, in the case of polyacetal resin, the production of formic acid, Fu-22- (19) 1248861 Marlin, low foaming resin There is a high possibility that a corrosive gas such as ammonia or carbon monoxide is generated. However, the protective film made of the fluorine-containing DLC of the present invention is excellent in corrosion resistance, and can prevent the member of the forming device from being invaded by the corrosive gas, and can be prolonged. The durable life of the molding apparatus can be maintained at a constant molding cycle. (Effect of the Invention) The present invention is a configuration as described above, and a surface joined to a resin Covered with a protective film made of fluorine-containing DLC, the peeling property with the resin is good, and no bubble-like projections, burrs, peeling, and the like are generated on the surface of the molded article, and the resin is burnt. Therefore, the formability is improved, and thin-walled and precision-formed can be formed. The protective film made of fluorine-containing DLC is excellent in corrosion resistance, and the member does not invade uranium by corrosive gas generated during molding, and the durable life of the forming device It is extended and can maintain a stable molding cycle. Further, as long as a base layer and an intermediate film are provided between the substrate and the protective film, the bondability between the substrate and the protective film becomes excellent, and the protective film as described above The effect can be effectively exerted for a long period of time. Further, a mixed region of an element constituting the base layer and an element constituting the protective film is formed between the base layer and the protective film, and if there is no clear interface between the base layer and the protective film, The base layer and the protective film can be continuously integrated, and as a result, the bondability between the base material and the protective film becomes stronger, and the protective film effect can be effectively exhibited for a long period of time. -23- (20) 1248861 [Brief Description of the Drawings] Fig. 1 is a view for explaining an injection portion of an injection molding apparatus according to a first embodiment of the present invention. Fig. 2 is a view for explaining an injection portion of an injection molding apparatus according to a second embodiment of the present invention. Fig. 3 is a view for explaining a molding portion of an injection molding apparatus according to a third embodiment of the present invention. Fig. 4 is a view for explaining a molded portion of an injection molding apparatus according to a fourth embodiment of the present invention. Fig. 5 is a partially enlarged sectional view showing a state in which a protective film is formed on a substrate of the present invention. The brother r 6 is a schematic diagram of the mining device. Fig. 7 is an enlarged perspective view showing the supported state of the member on the support table. Fig. 8 is a view for explaining a state of application of a sputtering power to a target. Figure 9 is a diagram for explaining the principle of the unbalanced magnetron sputtering method. Fig. 10 is a partially enlarged cross-sectional view showing a state in which a protective film is formed on a substrate according to a modification of the present invention. Fig. 1 is a partially enlarged cross-sectional view showing the surface state of the movable side mold shown in Fig. 4. Fig. 2 is an enlarged plan view showing the state of the gate sealing portion in the case of using the needle according to the embodiment of the present invention. Fig. 13 is an enlarged plan view showing the state of the gate seal portion in the case of the conventional needle-like-24-(21) 1248861. Figure 14 is a diagram for explaining the peelability test method. Figure 15 is a diagram for explaining the peelability test method. Fig. 16 is a characteristic diagram showing the results of the peeling test in the case of using AB S resin. Fig. 17 is a characteristic diagram showing the results of the peeling test in the case of using a polystyrene resin. Fig. 18 is a plan view of a movable side mold for testing the flowability of the resin in the mold. Figure 19 is a characteristic diagram showing the results of the no-flow test. [Main component comparison table] 1: vertical runner, 2: molten resin, 3: manifold, 4: nozzle body, 5: needle, 6: needle guide, 7: cylinder, 8: forming die , 8 a: fixed side mold, 8b: movable side mold, 1 1 : heating cylinder, 12: belt heater, 13: screw, 14: locking ring, 15: locking head, 16: heating head, 17 : open nozzle, 21: fixed template, 22: fixed side mold, 23: movable template, 24: mold mounting plate, 25: movable side mold, 26: mold groove, 27: vertical runner, 28: resin injection port, 29: nozzle, 30: molten resin, 31: push pin, 32: stamper, 33: fixed side mold, 34: movable side mold, 35: stamper peripheral clamp, 3 6 : mold groove, 3 7 : gate Member, 3 8 : gate cut member, 39: cross flow passage, 40: vertical runner, 41: base material, 42: base layer, 43: protective film, 44: intermediate film, 45: mixed region layer, 51 : processing chamber, 52: table, 53: support table, -25- (22) 1248861 54: target for base layer, 55: target for protective film, 56: inner magnetic pole, 57: outer magnetic pole., 58: Magnetic field line, 62: gas piping, 64: plasma, 6 5: component parts, 6 6 : pillar, 6 7 :roof. -26-