JP2006116896A - Manufacturing method of die - Google Patents
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- JP2006116896A JP2006116896A JP2004309480A JP2004309480A JP2006116896A JP 2006116896 A JP2006116896 A JP 2006116896A JP 2004309480 A JP2004309480 A JP 2004309480A JP 2004309480 A JP2004309480 A JP 2004309480A JP 2006116896 A JP2006116896 A JP 2006116896A
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Abstract
Description
本発明は、例えばＬＥＤ（発光ダイオード）に使用される反射板の表面に凹凸パターンを転写するための金型の製造方法に係わり、特に耐久性を向上させることが可能な金型の製造方法に関する。 The present invention relates to a mold manufacturing method for transferring a concavo-convex pattern onto the surface of a reflector used in, for example, an LED (light emitting diode), and more particularly to a mold manufacturing method capable of improving durability. .
例えば、ＬＥＤ（発光ダイオード）に使用される反射板の表面に凹凸パターンを転写するための金型には良好な離型性が求められる。従来、前記離型性を向上させるために金型の表面にフッ素系樹脂などの離型材を塗布していたが、前記金型を繰返し使用すると、前記離型材が剥がれたりするなどの不具合が生じ、この結果、前記離型材を塗布し直したりする必要性があることから反射板の生産性の向上を適切に図ることができず、従来よりも離型性に優れた高寿命の金型が求められた。 For example, a good mold releasability is required for a mold for transferring a concavo-convex pattern onto the surface of a reflector used in an LED (light emitting diode). Conventionally, a release material such as a fluorine-based resin has been applied to the surface of the mold in order to improve the mold release property. However, when the mold is used repeatedly, problems such as peeling of the mold release material occur. As a result, since it is necessary to re-apply the release material, it is not possible to appropriately improve the productivity of the reflector, and a long-life mold having a better release property than the conventional one can be obtained. I was asked.
下記の特許文献は、いずれもフッ素含有トリアジンジチオール誘導体に関する公知文献である。 The following patent documents are all known documents relating to fluorine-containing triazine dithiol derivatives.
下記特許文献１にはフッ素含有トリアジンジチオール誘導体を金型表面に電解重合法により成膜することが開示されている。また下記の特許文献２には、前記フッ素含有トリアジンジチオール誘導体の製造方法について詳しい説明が開示されている。また、特許文献３には前記フッ素含有トリアジンジチオール誘導体をスパッタ法や蒸着法等で被膜形成することが開示されている。
前記フッ素含有トリアジンジチオール誘導体からなる被膜を金型の凹凸パターン面に成膜すると、従来に比べて離型性に優れた金型を形成できる。本発明者らは後述する実験で前記フッ素含有トリアジンジチオール誘導体の被膜の「耐久性」を測定した。ここで「耐久性」とは、例えばアクリル系の熱硬化型樹脂等の樹脂部材の表面に凹凸パターンを金型によってプレス加工し、前記樹脂部材の表面に形成された凹凸パターンの深さ方向の長さが、前記金型に形成された凹凸パターンの深さ方向の長さの８０％を下回るまでの転写回数で評価される。 When a film made of the fluorine-containing triazine dithiol derivative is formed on the concave / convex pattern surface of the mold, it is possible to form a mold having excellent releasability as compared with the prior art. The inventors measured the “durability” of the coating film of the fluorine-containing triazine dithiol derivative in the experiment described below. Here, “durability” refers to, for example, pressing a concavo-convex pattern on the surface of a resin member such as an acrylic thermosetting resin with a mold, and the depth direction of the concavo-convex pattern formed on the surface of the resin member. The length is evaluated by the number of times of transfer until the length of the concavo-convex pattern formed on the mold is less than 80% of the length in the depth direction.
ところで前記フッ素含有トリアジンジチオール誘導体からなる被膜を電解重合法により成膜し、特に成膜時間（重合時間）を長くして前記被膜の膜厚を厚くすることで前記耐久性を向上させることが出来ることが確認された。耐久性を向上させることで、前記金型の寿命を向上させることが出来る。 By the way, a film made of the fluorine-containing triazinedithiol derivative is formed by an electropolymerization method, and in particular, the durability can be improved by increasing the film formation time (polymerization time) to increase the film thickness of the film. It was confirmed. By improving the durability, the life of the mold can be improved.
しかしながら、単に前記被膜の膜厚を厚くするだけでは、飛躍的に耐久性を向上させるには至らず、より耐久性に優れた金型が必要とされた。また前記フッ素含有トリアジンジチオール誘導体からなる被膜を特許文献３のように、スパッタ法等で形成する手法もあるが、かかる場合、前記被膜の膜厚が厚くなりすぎ、凹凸パターンのアスペクト比を所定の範囲内に収めることが困難になるため、電解重合法によるフッ素含有トリアジンジチオール誘導体の成膜において耐久性の向上を図ることが必要であった。 However, simply increasing the thickness of the coating does not lead to dramatic improvement in durability, and a mold having higher durability is required. In addition, there is a method of forming a film made of the fluorine-containing triazine dithiol derivative by a sputtering method or the like as in Patent Document 3, but in such a case, the film thickness of the film becomes too thick, and the aspect ratio of the uneven pattern is set to a predetermined value. Since it becomes difficult to fit within the range, it was necessary to improve durability in the film formation of the fluorine-containing triazine dithiol derivative by the electrolytic polymerization method.
そこで本発明は上記従来の課題を解決するためのものであり、特に、特に金型の凹凸パターン面に電解重合法によりフッ素含有トリアジンジチオール誘導体の被膜を成膜するにあたり、従来とは異なる工程で成膜することで耐久性の向上（すなわち寿命の向上）を図ることが出来る金型の製造方法を提供することを目的としている。 Therefore, the present invention is for solving the above-described conventional problems, and in particular, in forming a coating film of a fluorine-containing triazine dithiol derivative by electrolytic polymerization on an uneven pattern surface of a mold, the process is different from the conventional processes. An object of the present invention is to provide a mold manufacturing method capable of improving durability (that is, improving life) by forming a film.
本発明は、部材に凹凸パターンをプレス加工するための金型の製造方法であって、
前記金型の前記部材との対向面に、フッ素含有トリアジンジチオール誘導体を有する被膜を電解重合法により成膜した後、熱処理を行なう一連の成膜・熱処理工程を複数回行なうことを特徴とするものである。
The present invention is a method for manufacturing a mold for pressing a concavo-convex pattern on a member,
A film having a fluorine-containing triazine dithiol derivative is formed on the surface of the mold facing the member by an electrolytic polymerization method, and then a series of film formation and heat treatment steps are performed a plurality of times. It is.
上記のようにフッ素含有トリアジンジチオール誘導体を有する被膜を電解重合法により成膜した後、熱処理を行なう一連の成膜・熱処理工程を複数回行なうことで、耐久性を従来に比べて飛躍的に向上させることが出来ることが後述する実験結果によって確認された。これは、上記した一連の成膜・熱処理工程を複数回行なうことで前記フッ素含有トリアジンジチオール誘導体の配向性が向上し、前記誘導体が緻密に整然と配列し、被膜が強靭になったためであると考えられる。 Durability is dramatically improved by performing a series of film-forming and heat-treating processes multiple times after the film containing the fluorine-containing triazine dithiol derivative is formed by electrolytic polymerization as described above and then heat-treated. It was confirmed by the experimental results to be described later. This is thought to be because the orientation of the fluorine-containing triazine dithiol derivative was improved by performing the above-described series of film formation and heat treatment steps a plurality of times, and the derivative was densely and orderly arranged, and the film became tough. It is done.
なお本発明では、熱処理工程の熱処理温度を、１５０℃〜２５０℃の範囲内に制御することが好ましい。 In the present invention, it is preferable to control the heat treatment temperature in the heat treatment step within a range of 150 ° C to 250 ° C.
また本発明では、前記部材は樹脂であり、前記金型は反射板を製造するためのものであることが好ましい。 Moreover, in this invention, it is preferable that the said member is resin and the said metal mold | die is for manufacturing a reflecting plate.
本発明では、金型の凹凸パターン面に、フッ素含有トリアジンジチオール誘導体を有する被膜を電解重合法により成膜した後、熱処理を行なう一連の成膜・熱処理工程を複数回行なうことで、被膜の耐久性を従来に比べて飛躍的に向上させることが出来、前記金型の寿命を従来よりも飛躍的に延ばすことが可能になる。 In the present invention, a film having a fluorine-containing triazinedithiol derivative is formed on the concave / convex pattern surface of the mold by electrolytic polymerization, and then a series of film formation / heat treatment steps are performed multiple times, thereby improving the durability of the film. As a result, it is possible to dramatically improve the performance of the mold, and it is possible to extend the life of the mold dramatically.
図１ないし図３は、本発明における金型を用いてＬＥＤ（発光ダイオード）に使用される反射板の表面に凹凸パターンをプレス加工するための工程を示す一工程図であり、いずれも金型及び反射板を膜厚方向から切断した部分断面図、図４は図１ないし図３に示す金型をより詳細に説明するための部分断面図、図５は図４に示す金型の一部を拡大して示した部分拡大断面図、である。 FIG. 1 to FIG. 3 are process diagrams showing a process for pressing a concavo-convex pattern on the surface of a reflector used in an LED (light emitting diode) using the mold according to the present invention. FIG. 4 is a partial sectional view for explaining the mold shown in FIGS. 1 to 3 in more detail, and FIG. 5 is a part of the mold shown in FIG. It is the elements on larger scale which expanded and showed.
図１に示すように表面が平坦化された基板１上に反射板２の原料である樹脂部材３を載置する。前記樹脂部材３は、例えばアクリル系の熱硬化性樹脂、熱可塑性樹脂、またはノルボルネン、シクロペンタジエンなどのシクロ環、スピロ環等の樹脂である。 As shown in FIG. 1, a resin member 3 that is a raw material of the reflector 2 is placed on a substrate 1 having a flat surface. The resin member 3 is, for example, an acrylic thermosetting resin, a thermoplastic resin, or a resin such as norbornene or cyclopentadiene such as a cyclo ring or a spiro ring.
図１に示すように金型４の前記樹脂部材３と対向する対向面４ａには所定形状の凹凸パターンが形成されている。前記金型４の対向面４ａには、後述するようにフッ素含有トリアジンジチオール誘導体の被膜が成膜されている。前記金型４は、例えばニッケルの電鋳品であるが、材質はニッケルに限るものではない。 As shown in FIG. 1, a concave and convex pattern having a predetermined shape is formed on the opposing surface 4 a of the mold 4 facing the resin member 3. A film of a fluorine-containing triazine dithiol derivative is formed on the opposing surface 4a of the mold 4 as described later. The mold 4 is, for example, a nickel electroformed product, but the material is not limited to nickel.
図２に示すように、前記金型４の対向面４ａを前記樹脂部材３の表面３ａに押し当て、下方向へプレスすることで前記樹脂部材３の表面３ａに前記金型４の凹凸パターンを転写する。図２の状態で加熱したりあるいは紫外線を照射して前記樹脂部材３を硬化させ、図３に示すように前記金型４を上方へ向けて樹脂部材３から剥離すると表面２ａに凹凸パターンが形成された反射板２が完成する。 As shown in FIG. 2, the concavity and convexity pattern of the mold 4 is formed on the surface 3 a of the resin member 3 by pressing the facing surface 4 a of the mold 4 against the surface 3 a of the resin member 3 and pressing it downward. Transcript. When the resin member 3 is cured by heating in the state shown in FIG. 2 or by irradiating ultraviolet rays, and the mold 4 is peeled upward from the resin member 3 as shown in FIG. 3, an uneven pattern is formed on the surface 2a. The reflected reflector 2 is completed.
図４に示すように前記金型４の対向面４ａには、フッ素含有トリアジンジチオール誘導体からなる被膜５が成膜されている。前記フッ素含有トリアジンジチオール誘導体の被膜５は電解重合法によって成膜されている。前記電解重合法について以下に説明する。 As shown in FIG. 4, a coating 5 made of a fluorine-containing triazine dithiol derivative is formed on the facing surface 4 a of the mold 4. The coating film 5 of the fluorine-containing triazine dithiol derivative is formed by an electrolytic polymerization method. The electrolytic polymerization method will be described below.
図６は電解槽の構造を示す部分断面図である。図６に示すように、浴槽１０と、前記浴槽１０内に配置される陽極である金型４と、ステンレス板あるいは白金等からなる陰極１１とが設けられ、前記浴槽１０内は、フッ素含有トリアジンジチオール誘導体及び電解質を含む溶液１２で満たされる。
フッ素含有トリアジンジチオール誘導体は、下記の［化１］の化学式により表される。
FIG. 6 is a partial cross-sectional view showing the structure of the electrolytic cell. As shown in FIG. 6, the bathtub 10, the metal mold | die 4 which is an anode arrange | positioned in the said bathtub 10, and the cathode 11 which consists of a stainless steel plate or platinum, etc. are provided, The inside of the said bathtub 10 is a fluorine-containing triazine. Filled with a solution 12 containing a dithiol derivative and an electrolyte.
The fluorine-containing triazine dithiol derivative is represented by the following chemical formula [Chemical Formula 1].
ここで、Ｒ１は−Ｈ，−ＣＨ３，−Ｃ２Ｈ５，−Ｃ４Ｈ９，−Ｃ８Ｈ１７，−Ｃ６Ｈ５，−ＣＨ２ＣＨ＝ＣＨ２，−Ｃ２Ｈ４ＣＨ＝ＣＨ２，−ＣＨ２ＣＨ＝ＣＨＣＨ＝ＣＨＣＨ３，−Ｃ４Ｈ８ＣＨ＝ＣＨ２，−Ｃ６Ｈ１２ＣＨ＝ＣＨ２，−ＣＨ２Ｃ６Ｈ４ＣＨ＝ＣＨ２，−ＣＨ２Ｃ３Ｆ７，−ＣＨ２Ｃ７Ｆ１５，−Ｃ６Ｈ４Ｃ４Ｆ９，−Ｃ６Ｈ４Ｃ８Ｆ１７、Ｒ２は−ＣＨ２−，−Ｃ２Ｈ４−，−ＣＨ（Ｃ２Ｈ４）２ＣＨＯＣＯ−，−Ｃ２Ｈ４ＯＣＯ−，−Ｃ３Ｈ６−，−ＣＨ２ＣＨ＝ＣＨ−，−Ｃ６Ｈ４Ｏ−，−Ｃ６Ｈ１２−，−ＣＨ２ＣＨ（ＯＨ）ＣＨ2 −のいずれかであり、ＭはＨあるいはアルカリ金属を指し、ｎは８から１２の範囲内である。 Wherein, R 1 is -H, -CH 3, -C 2 H 5, -C 4 H 9, -C 8 H 17, -C 6 H 5, -CH 2 CH = CH 2, -C 2 H 4 CH = CH 2, -CH 2 CH = CHCH = CHCH 3, -C 4 H 8 CH = CH 2, -C 6 H 12 CH = CH 2, -CH 2 C 6 H 4 CH = CH 2, -CH 2 C 3 F 7, -CH 2 C 7 F 15, -C 6 H 4 C 4 F 9, -C 6 H 4 C 8 F 17, R 2 is -CH 2 -, - C 2 H 4 -, - CH (C 2 H 4) 2 CHOCO -, - C 2 H 4 OCO -, - C 3 H 6 -, - CH 2 CH = CH -, - C 6 H 4 O -, - C 6 H 12 -, - CH 2 CH (OH) CH 2 —, M represents H or an alkali metal, and n is in the range of 8 to 12.
例えば、Ｒ１は、−ＣＨ２ＣＨ＝ＣＨ２であり、Ｒ２は、−Ｃ２Ｈ４−であり、ＭはＨであり、ｎは８である。 For example, R 1 is —CH 2 CH═CH 2 , R 2 is —C 2 H 4 —, M is H, and n is 8.
ｎは小さいほど、パーフロロアルキルの鎖の長さが短くなるが、分子内に占めるトリアジンの占有率が大きいために前記パーフロロアルキの鎖の長さが短かすぎると重合が適切に起こらないと予測され、効果的に被膜５の耐久性を向上させることができないことがわかっている。このためｎはあまり小さい値であると好ましくなく、本発明ではｎを８〜１２の範囲内に設定した。 The smaller the n, the shorter the length of the perfluoroalkyl chain. However, since the occupation ratio of triazine in the molecule is large, the polymerization does not occur properly if the length of the perfluoroalkyl chain is too short. It is predicted that the durability of the film 5 cannot be effectively improved. For this reason, it is not preferable that n is a very small value. In the present invention, n is set within the range of 8-12.
前記フッ素含有トリアジンジチオール誘導体は、溶液１２内に１ｍｍｏｌ〜１００ｍｍｏｌ程度含有される。 The fluorine-containing triazine dithiol derivative is contained in the solution 12 in an amount of about 1 mmol to 100 mmol.
電解質は、特に限定はないがＮａ２ＣＯ３やＮａＯＨ等である。また溶剤は特に限定はないが、水やメタノール等である。電流は直流電流あるいはパルス電流を用いることができ、電流密度は、例えば０．０５ｍＡ／ｃｍ２程度である。 The electrolyte is not particularly limited, but is Na 2 CO 3 or NaOH. The solvent is not particularly limited, but is water or methanol. As the current, a direct current or a pulse current can be used, and the current density is, for example, about 0.05 mA / cm 2 .
図６に示す電解槽を用いて前記金型４の凹凸パターンが形成された対向面４ａにフッ素含有トリアジンジチオール誘導体からなる被膜５を成膜する。成膜時間は例えば１０分程度である。 A coating 5 made of a fluorine-containing triazine dithiol derivative is formed on the opposing surface 4a on which the concave / convex pattern of the mold 4 is formed using the electrolytic cell shown in FIG. The film formation time is, for example, about 10 minutes.
従来では成膜時間を延ばして前記被膜５の膜厚を厚くし、前記被膜５の耐久性を向上させる試みがなされていたが、本発明では、成膜時間を長くせず所定時間、前記被膜５を電解重合法により成膜した後、一旦、前記金型４を前記溶液１２内から取り出し前記金型４を洗浄した後、熱処理工程に移行させる。 Conventionally, attempts have been made to extend the film formation time to increase the film thickness of the coating film 5 and improve the durability of the coating film 5. After 5 is formed into a film by the electrolytic polymerization method, the mold 4 is once taken out from the solution 12 and the mold 4 is washed, and then the process proceeds to a heat treatment step.
前記熱処理工程では、１５０℃〜２５０℃の範囲内の熱処理温度で、２０分〜１時間程度の熱処理時間により前記皮膜５を熱処理する。 In the heat treatment step, the film 5 is heat treated at a heat treatment temperature within a range of 150 ° C. to 250 ° C. for a heat treatment time of about 20 minutes to 1 hour.
本発明では前記被膜５を熱処理した後、再び、前記金型４を溶液１２内に入れ、前記金型４の凹凸パターンの対向面４ａにさらに前記フッ素含有トリアジンジチオール誘導体の被膜５を電解重合法により成膜する。そして前記金型４を溶液１２内から取り出し洗浄後、上記した熱処理条件によって熱処理を施す。 In the present invention, after heat-treating the coating film 5, the mold 4 is again placed in the solution 12, and the coating film 5 of the fluorine-containing triazine dithiol derivative is further applied to the opposing surface 4 a of the concave-convex pattern of the mold 4 by an electrolytic polymerization method. The film is formed by Then, the mold 4 is taken out from the solution 12 and washed, and then heat treatment is performed under the above heat treatment conditions.
本発明では前記フッ素含有トリアジンジチオール誘導体の成膜・熱処理工程からなる一連の工程を複数回行なう点に特徴的な部分がある。 In the present invention, there is a characteristic part in that a series of steps including film formation and heat treatment steps of the fluorine-containing triazine dithiol derivative is performed a plurality of times.
図５は、前記金型４の凹凸パターンが形成された対向面４ａの部分拡大断面図であるが、図５のように、前記フッ素含有トリアジンジチオール誘導体からなる被膜５を被膜５ａ，５ｂ，５ｃと複数回、成膜し、その成膜したごとに熱処理を施す。図５では、複数回の被膜成膜をわかりやすくするため点線で各被膜間の境界を図示したが、前記点線は、このような皮膜間の境界が実際に見えることを意味するものではない。 FIG. 5 is a partially enlarged cross-sectional view of the facing surface 4a on which the concave / convex pattern of the mold 4 is formed. As shown in FIG. 5, the film 5 made of the fluorine-containing triazine dithiol derivative is coated with the films 5a, 5b, 5c. The film is formed a plurality of times, and heat treatment is performed every time the film is formed. In FIG. 5, the boundary between the films is illustrated by dotted lines in order to make it easy to understand the film formation of a plurality of times, but the dotted line does not mean that the boundary between the films is actually visible.
本発明では、以下に示す複数のサンプルを形成して各サンプルの耐久性を測定した。
図６に示す電解槽を用い、浴槽１０内に上記の［化１］のＲ１を、−ＣＨ２ＣＨ＝ＣＨ２、Ｒ２を、−Ｃ２Ｈ４−、ＭをＨ、ｎを８としたフッ素含有トリアジンジチオール誘導体（１ｍｍｏｌ）と電解質である炭酸ナトリウム（Ｎａ２ＣＯ３）との混合液（０．１ｍｏｌ）を入れた。成膜諸条件としては、前記混合液を溶剤に溶かしてフッ素含有トリアジンジチオール誘導体濃度が０．０１ｍｏｌ／Ｌとなるように調整し、電流密度を０．０５ｍＡ／ｃｍ２、成膜時間を１０分として成膜した。
In the present invention, a plurality of samples shown below were formed and the durability of each sample was measured.
Using the electrolytic cell shown in FIG. 6, R 1 of the above [Chemical Formula 1] in the bath 10 is —CH 2 CH═CH 2 , R 2 is —C 2 H 4 —, M is H, and n is 8 A mixed solution (0.1 mol) of the fluorine-containing triazine dithiol derivative (1 mmol) and sodium carbonate (Na 2 CO 3 ) as an electrolyte was added. As film formation conditions, the mixed solution was dissolved in a solvent and adjusted so that the fluorine-containing triazine dithiol derivative concentration was 0.01 mol / L, the current density was 0.05 mA / cm 2 , and the film formation time was 10 minutes. As a film formation.
（実施例１）
金型４の対向面４ａに、図８のフローに示すように、フッ素含有トリアジンジチオール誘導体の被膜５を上記の成膜諸条件で電解重合法により成膜した後（ＳＴ１）、前記金型４を前記浴槽１０内から取り出して洗浄し（ＳＴ２）、１５０℃で３０分の熱処理を施し（ＳＴ３）（以下、上記成膜諸条件によるフッ素含有トリアジンジチオール誘導体の成膜工程−洗浄工程−１５０℃で３０分の熱処理工程を「一連の実施例工程」と呼ぶ）、その後に再度、前記金型４に対し一連の実施例工程を施した。
（実施例２）
金型４の対向面４ａに前記一連の実施例工程を３回行なった。
（実施例３）
金型４の対向面４ａに前記一連の実施例工程を４回行なった。
（実施例４）
金型４の対向面４ａに前記一連の実施例工程を５回行なった。
（実施例５）
金型４の対向面４ａに前記一連の実施例工程を６回行なった。
(Example 1)
As shown in the flow of FIG. 8, a film 5 of a fluorine-containing triazine dithiol derivative is formed on the facing surface 4 a of the mold 4 by the electrolytic polymerization method under the above-described film formation conditions (ST 1), and then the mold 4. Was removed from the bath 10 and washed (ST2), and heat-treated at 150 ° C. for 30 minutes (ST3) (hereinafter referred to as film forming step of fluorine-containing triazine dithiol derivative under the above film forming conditions-cleaning step-150 ° C. The heat treatment step for 30 minutes is referred to as “a series of example steps”), and then a series of example steps were performed on the mold 4 again.
(Example 2)
The series of example steps were performed three times on the facing surface 4 a of the mold 4.
(Example 3)
The series of example steps were performed four times on the opposing surface 4 a of the mold 4.
(Example 4)
The series of example steps were performed 5 times on the opposing surface 4 a of the mold 4.
(Example 5)
The series of example steps were performed 6 times on the opposing surface 4 a of the mold 4.
（従来例１）
金型４の対向面４ａに、フッ素含有トリアジンジチオール誘導体の被膜５を上記の成膜諸条件で電解重合法により成膜した後、前記金型４を前記浴槽１０内から取り出して洗浄した（以下、上記成膜諸条件によるフッ素含有トリアジンジチオール誘導体の成膜工程−洗浄工程を「一連の従来例例工程」と呼ぶ）。なお従来例１ないし４ではいずれも熱処理は行なっていない。
（従来例２）
金型４の対向面４ａに前記一連の従来例工程を２回行なった。
（従来例３）
金型４の対向面４ａに前記一連の従来例工程を３回行なった。
（従来例４）
上記の成膜諸条件のうち、成膜時間を１０分から９０分に伸ばして、金型４の対向面４ａに、フッ素含有トリアジンジチオール誘導体の被膜５を成膜し、その後洗浄した。
(Conventional example 1)
A film 5 of a fluorine-containing triazine dithiol derivative was formed on the facing surface 4a of the mold 4 by the electrolytic polymerization method under the above-mentioned various film formation conditions, and then the mold 4 was taken out of the bath 10 and washed (hereinafter referred to as the following). The film forming step of the fluorine-containing triazine dithiol derivative under the above film forming conditions—the cleaning step is referred to as “a series of conventional example steps”). In all of the conventional examples 1 to 4, no heat treatment is performed.
(Conventional example 2)
The series of conventional steps were performed twice on the opposing surface 4a of the mold 4.
(Conventional example 3)
The series of conventional steps were performed three times on the opposing surface 4a of the mold 4.
(Conventional example 4)
Among the above film forming conditions, the film forming time was extended from 10 minutes to 90 minutes, and the coating film 5 of the fluorine-containing triazine dithiol derivative was formed on the facing surface 4a of the mold 4 and then washed.
（比較例１）
金型４の対向面４ａに前記一連の従来例工程を２回行なった後、１５０℃で３０分の熱処理を行なった。
(Comparative Example 1)
The series of conventional steps were performed twice on the facing surface 4a of the mold 4, and then heat treatment was performed at 150 ° C. for 30 minutes.
上記した実施例１〜５、従来例１〜４及び比較例１の各サンプルにおけるフッ素含有トリアジンジチオール誘導体の被膜５の膜厚をESCA（アルバックファイ社製）によって算出した。 The film thickness of the coating film 5 of the fluorine-containing triazine dithiol derivative in each sample of Examples 1 to 5, Conventional Examples 1 to 4, and Comparative Example 1 was calculated by ESCA (manufactured by ULVAC-PHI).
算出方法は、アルゴンイオンを各サンプルの被膜５に照射して、概ね１００Å／分のスピードで前記被膜５を削るとともにESCAによってＳ元素の原子強度を測定し、原子強度とスパッタ時間との関係により、各サンプルの膜厚の相対値を求めた。なお従来例１のフッ素含有トリアジンジチオール誘導体の被膜５の膜厚を１としたときの他のサンプルの膜厚を相対値として求めた。 The calculation method is to irradiate the coating film 5 of each sample with argon ions, scrape the coating film 5 at a speed of approximately 100 Å / min, measure the atomic strength of the S element by ESCA, and determine the relationship between the atomic strength and the sputtering time. The relative value of the film thickness of each sample was obtained. In addition, the film thickness of the other sample when the film thickness of the coating film 5 of the fluorine-containing triazine dithiol derivative of Conventional Example 1 was 1 was determined as a relative value.
耐久性実験では、各サンプルの金型４を用い、図１ないし図３で説明した樹脂部材３に対して凹凸パターンの転写を行ない、前記樹脂部材３の凹凸パターンの深さ方向の長さ寸法が、前記金型４の凹凸パターンの深さ方向の長さに対して８０％以上であるか否かを測定した。多数用意された各樹脂部材３に対して次々と凹凸パターンの転写を行い、上記した長さ比が８０％を下回るまでの転写回数を測定した。
その実験結果を以下の表１に示す。
In the durability experiment, the concavo-convex pattern was transferred to the resin member 3 described with reference to FIGS. 1 to 3 using the mold 4 of each sample, and the length dimension in the depth direction of the concavo-convex pattern of the resin member 3 was measured. However, it was measured whether it was 80% or more with respect to the length of the uneven | corrugated pattern of the said metal mold | die 4 in the depth direction. The concavo-convex pattern was transferred one after another to each of the prepared resin members 3, and the number of transfers until the above-mentioned length ratio fell below 80% was measured.
The experimental results are shown in Table 1 below.
表１に示すように、実施例１ないし５は、従来例１ないし４及び比較例１に比べて耐久性が飛躍的に向上したことがわかった。これにより金型４の寿命を従来よりもより効果的に伸ばすことが可能になった。 As shown in Table 1, it was found that the durability of Examples 1 to 5 was dramatically improved as compared with Conventional Examples 1 to 4 and Comparative Example 1. This makes it possible to extend the life of the mold 4 more effectively than before.
実施例１ないし５はいずれもフッ素含有トリアジンジチオール誘導体を電解重合法により成膜した後、熱処理工程を施し、この一連の成膜・熱処理工程を複数回、繰り返したものである。一方、従来例１ないし４は、いずれも熱処理工程を施さず、比較例１は熱処理を施すが、２回、フッ素含有トリアジンジチオール誘導体の被膜を成膜した後に、熱処理工程を施したものであり、実施例のように一連の成膜・熱処理工程を複数回行なうものではない。 In each of Examples 1 to 5, a fluorine-containing triazine dithiol derivative was formed into a film by electrolytic polymerization, and then a heat treatment step was performed, and this series of film formation and heat treatment steps was repeated a plurality of times. On the other hand, none of Conventional Examples 1 to 4 is subjected to a heat treatment step, and Comparative Example 1 is subjected to a heat treatment. The series of film formation / heat treatment steps are not performed a plurality of times as in the embodiments.
実施例１ないし５のように、一連の成膜・熱処理工程を施したものは、成膜のつど熱処理を施すことで、前記フッ素含有トリアジンジチオール誘導体の配向性が飛躍的に向上して、前記誘導体が緻密に整然と配列し、膜が強靭になったため、耐久性が従来例１ないし４や比較例１に比べて向上したものと考えられる。 As in Examples 1 to 5, those subjected to a series of film formation / heat treatment steps were subjected to a heat treatment for each film formation, whereby the orientation of the fluorine-containing triazine dithiol derivative was dramatically improved. It is considered that the durability was improved as compared with the conventional examples 1 to 4 and the comparative example 1 because the derivatives were arranged densely and orderly and the film became tough.
同じ回数だけフッ素含有トリアジンジチオール誘導体の成膜を行なった実施例１、従来例２及び比較例１を見ると、成膜ごとに熱処理を行なう実施例１は、全く熱処理を施さない従来例１や熱処理回数が成膜回数よりも少ない比較例１に比べて耐久性が向上していることがわかった。 Looking at Example 1, Conventional Example 2 and Comparative Example 1 in which the film formation of the fluorine-containing triazine dithiol derivative was performed the same number of times, Example 1 in which the heat treatment was performed for each film formation was as follows. It was found that the durability was improved as compared with Comparative Example 1 in which the number of heat treatments was smaller than the number of film formations.
上記の前記フッ素含有トリアジンジチオール誘導体の配向性が向上して、前記誘導体が緻密に整然と配列していると考えられるのは、表１に示す膜厚比の欄からも推測できる。すなわち、実施例１、従来例２、及び比較例１は、フッ素含有トリアジンジチオール誘導体を２回、電解重合法により成膜しているが、膜厚比は実施例１のほうが従来例２や比較例１に比べて小さくなっており、このことからも成膜のたびに熱処理を施すことで、前記誘導体が緻密に整然と配列しているものと予測できる。このように、実施例のものは、同じ成膜回数であるが成膜後、熱処理を行なう一連の工程を行なっていない（すなわち熱処理を全く行なっていないか、熱処理を行なっていても、その熱処理回数が成膜回数よりも少ない）ものに比べて膜厚比が小さくなることがわかった。 It can be estimated from the column of the film thickness ratio shown in Table 1 that the orientation of the fluorine-containing triazinedithiol derivative is improved and the derivative is considered to be densely and orderly arranged. That is, in Example 1, Conventional Example 2, and Comparative Example 1, the fluorine-containing triazine dithiol derivative was formed twice by the electrolytic polymerization method, but the film thickness ratio of Example 1 was higher than that of Conventional Example 2 and Comparative Example 1. It is smaller than Example 1, and it can be predicted from this that the derivatives are arranged in a precise and orderly manner by performing a heat treatment for each film formation. As described above, in the example, the number of film formations is the same, but a series of steps for performing heat treatment is not performed after film formation (that is, no heat treatment is performed or heat treatment is performed even if heat treatment is performed). It has been found that the film thickness ratio is smaller than that in which the number of times is smaller than the number of times of film formation.
表１に示すように、一連の成膜・熱処理工程の回数を２回よりも３回、３回よりも４回と多くしていくと耐久性が向上することがわかったが、実施例５は、実施例４に比べて耐久性が向上していない。また実施例４と実施例５とでは膜厚比はほとんど同じ結果となった。これは、一連の成膜・熱処理工程の回数を多くしすぎても、絶縁物である前記フッ素含有トリアジンジチオール誘導体の被膜の膜厚が厚くなりすぎ次に電解重合法によってフッ素含有トリアジンジチオール誘導体を成膜しようとしても適切に成膜できないためであると考えられる。 As shown in Table 1, it was found that the durability improved when the number of times of the series of film formation and heat treatment steps was increased from 3 times to 3 times to 3 times to 3 times. The durability is not improved as compared with Example 4. In addition, the film thickness ratio in Example 4 and Example 5 was almost the same. This is because the film thickness of the fluorine-containing triazinedithiol derivative, which is an insulator, becomes too thick even if the number of series of film formation / heat treatment steps is increased too much, and then the fluorine-containing triazinedithiol derivative is formed by electrolytic polymerization. This is probably because the film cannot be formed properly even if it is going to be formed.
実施例１ないし５はいずれも熱処理温度を１５０℃にした。熱処理温度は２５０℃程度まで上昇させてもよいが、あまり熱処理温度を高くしすぎても、金型４自体が酸化し腐食の問題が生じるので好ましくない。逆に熱処理温度を１５０℃よりも低くすると上記したフッ素含有トリアジンジチオール誘導体の配向性が適切に向上せず、飛躍的な耐久性の向上を期待できない。 In all of Examples 1 to 5, the heat treatment temperature was set to 150 ° C. Although the heat treatment temperature may be raised to about 250 ° C., too high a heat treatment temperature is not preferable because the mold 4 itself is oxidized and causes corrosion problems. On the other hand, if the heat treatment temperature is lower than 150 ° C., the orientation of the fluorine-containing triazine dithiol derivative is not appropriately improved, and a dramatic improvement in durability cannot be expected.
図７は、エックス線光電子分光測定（ＸＰＳ）を用いて行なった実験結果であり、実施例１と従来例３の各サンプルに対し、分析時のサンプル表面との測定プローブのなす角度（deg）と、フッ素濃度との関係を示すものである。なす角度が大きいほど、被膜の深い部分でのフッ素濃度を示している。測定では、なす角度を５，１５，４５，６５，８５（deg）で行っており、これにより皮膜の表面深さ約１０Å〜１２０Åまでのフッ素元素の濃度を検出できる。 FIG. 7 shows the results of experiments conducted using X-ray photoelectron spectroscopy (XPS). For each sample of Example 1 and Conventional Example 3, the angle (deg) formed by the measurement probe with the sample surface at the time of analysis is shown. This shows the relationship with the fluorine concentration. The larger the angle formed, the more the fluorine concentration in the deep part of the film. In the measurement, the angles formed are 5, 15, 45, 65, and 85 (deg), whereby the concentration of the fluorine element at a surface depth of about 10 to 120 mm can be detected.
図７に示すように、実施例１では、フッ素元素の濃度はなす角度が５（deg）で最大になっており、なす角度が大きくなるほど徐々にフッ素元素の濃度が低下することがわかった。これは、被膜の表面で最もフッ素元素の濃度が高まり、被膜の深さ方向へ向けて徐々にフッ素濃度が低下していくことを意味する。一方、従来例３では、なす角度の大きさに係わらず、概ねフッ素元素の濃度は一定であり、これは被膜の表面でも内部でも前記フッ素元素の濃度がほぼ一定であることを意味する。 As shown in FIG. 7, in Example 1, it was found that the concentration of the fluorine element was the maximum when the angle formed was 5 (deg), and the concentration of the fluorine element was gradually decreased as the angle formed was increased. This means that the concentration of elemental fluorine increases most on the surface of the coating, and the concentration of fluorine gradually decreases in the depth direction of the coating. On the other hand, in Conventional Example 3, regardless of the angle formed, the concentration of the fluorine element is generally constant, which means that the concentration of the fluorine element is substantially constant both on the surface and inside the coating.
図７に示す実験結果から、実施例１では、上記［化１］に示したパーフロロアルキル中のＦが被膜の表面に適切に配向し、一方チオール側は金型４の表面側に向けられており、フッ素含有トリアジンジチオール誘導体が全体的に適切に配向していることがわかった。一方、従来例３は無配向であることがわかった。 From the experimental results shown in FIG. 7, in Example 1, F in the perfluoroalkyl shown in [Chemical Formula 1] is properly oriented on the surface of the coating, while the thiol side is directed to the surface side of the mold 4. It was found that the fluorine-containing triazine dithiol derivative was properly oriented as a whole. On the other hand, it was found that Conventional Example 3 was non-oriented.
図８に示す一連の成膜・熱処理工程において、ステップ（ＳＴ０）にて、成膜のたびに上記［化１］のＲ１、Ｒ２、ｎ等が異なるフッ素含有トリアジンジチオール誘導体を用いた電解槽を準備してもよい。例えば、図８のステップ（ＳＴ０）で電解槽の溶液中におけるフッ素含有トリアジンジチオール誘導体の上記［化１］のｎが一回前の成膜工程時に使用した電解槽中におけるフッ素含有トリアジンジチオール誘導体のｎよりも大きくなるように適宜調整し、フッ素含有トリアジンジチオール誘導体の被膜中に含まれるフッ素濃度が被膜の表面に向けて図７の実施例１よりもより急激に大きくなるようにしてもよい。 In the series of film formation and heat treatment steps shown in FIG. 8, in step (ST0), electrolysis using fluorine-containing triazine dithiol derivatives in which R 1 , R 2 , n, etc. of the above [Chemical Formula 1] are different for each film formation. A tank may be prepared. For example, in step (ST0) of FIG. 8, n of the above [Chemical Formula 1] of the fluorine-containing triazine dithiol derivative in the electrolytic cell solution is the fluorine-containing triazine dithiol derivative in the electrolytic cell used in the previous film formation step. The concentration of fluorine contained in the coating of the fluorine-containing triazine dithiol derivative may be adjusted as appropriate so as to be larger than n, and the concentration of fluorine contained in the coating may be increased more rapidly than Example 1 in FIG.
また、被膜はフッ素含有トリアジンジチオール誘導体のみで構成されず他の有機成分が含まれていてもかまわない。 In addition, the coating may not be composed of only the fluorine-containing triazine dithiol derivative and may contain other organic components.
本発明は特にＬＥＤ（発光ダイオード）に内臓される反射板の表面に凹凸パターンを転写するための金型の製造方法に最適であるが、反射板の製造に使用される金型以外の金型で特に良好な離型性を必要とする金型の製造方法に本発明を適用することが出来る。 The present invention is particularly suitable for a mold manufacturing method for transferring a concavo-convex pattern onto the surface of a reflector incorporated in an LED (light emitting diode), but a mold other than the mold used for manufacturing the reflector. Therefore, the present invention can be applied to a mold manufacturing method that requires particularly good releasability.
１ 基板
２ 反射板
３ 樹脂部材
４ 金型
５ 被膜
１０ 浴槽
１１ 陰極
１２ 溶液
DESCRIPTION OF SYMBOLS 1 Substrate 2 Reflecting plate 3 Resin member 4 Mold 5 Coating 10 Bathtub 11 Cathode 12 Solution
Claims (3)
前記金型の前記部材との対向面に、フッ素含有トリアジンジチオール誘導体を有する被膜を電解重合法により成膜した後、熱処理を行なう一連の成膜・熱処理工程を複数回行なうことを特徴とする金型の製造方法。 A method of manufacturing a mold for pressing a concavo-convex pattern on a member,
A metal film characterized in that a film having a fluorine-containing triazinedithiol derivative is formed on the surface of the mold facing the member by an electrolytic polymerization method, and then a series of film formation and heat treatment steps are performed a plurality of times. Mold manufacturing method.
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| JP2004309480A JP4500928B2 (en) | 2004-10-25 | 2004-10-25 | Mold manufacturing method |
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| JP4500928B2 JP4500928B2 (en) | 2010-07-14 |
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| JP2007131919A (en) * | 2005-11-10 | 2007-05-31 | Iwate Univ | Method for producing electroforming die |
| WO2011111741A1 (en) * | 2010-03-10 | 2011-09-15 | 旭化成株式会社 | Resin mold |
| WO2011118591A1 (en) * | 2010-03-25 | 2011-09-29 | 三菱レイヨン株式会社 | Method for producing molds and method for producing products with superfine concave-convex structures on surface |
| WO2012133390A1 (en) * | 2011-03-30 | 2012-10-04 | シャープ株式会社 | Mold release treatment method, and antireflective film production method |
| KR101342441B1 (en) | 2012-01-30 | 2013-12-17 | 재영솔루텍 주식회사 | Mold for injection-molding product which displays 3-dimensional picture and method for manufacturing this mold |
| US9142663B2 (en) | 2005-05-24 | 2015-09-22 | Cree, Inc. | Silicon carbide devices having smooth channels |
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|---|---|---|---|---|
| US9142663B2 (en) | 2005-05-24 | 2015-09-22 | Cree, Inc. | Silicon carbide devices having smooth channels |
| JP2007131919A (en) * | 2005-11-10 | 2007-05-31 | Iwate Univ | Method for producing electroforming die |
| WO2011111741A1 (en) * | 2010-03-10 | 2011-09-15 | 旭化成株式会社 | Resin mold |
| CN102791452A (en) * | 2010-03-10 | 2012-11-21 | 旭化成株式会社 | Resin mold |
| US10766169B2 (en) | 2010-03-10 | 2020-09-08 | Asahi Kasei E-Materials Corporation | Resin mold |
| WO2011118591A1 (en) * | 2010-03-25 | 2011-09-29 | 三菱レイヨン株式会社 | Method for producing molds and method for producing products with superfine concave-convex structures on surface |
| CN102791454A (en) * | 2010-03-25 | 2012-11-21 | 三菱丽阳株式会社 | Method for producing molds and method for producing products with superfine concave-convex structures on surface |
| JPWO2011118591A1 (en) * | 2010-03-25 | 2013-07-04 | 三菱レイヨン株式会社 | Method for producing mold and method for producing article having fine uneven structure on surface |
| JP5549943B2 (en) * | 2010-03-25 | 2014-07-16 | 三菱レイヨン株式会社 | Method for producing mold and method for producing article having fine uneven structure on surface |
| WO2012133390A1 (en) * | 2011-03-30 | 2012-10-04 | シャープ株式会社 | Mold release treatment method, and antireflective film production method |
| KR101342441B1 (en) | 2012-01-30 | 2013-12-17 | 재영솔루텍 주식회사 | Mold for injection-molding product which displays 3-dimensional picture and method for manufacturing this mold |
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