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JP5903495B2 - Manufacturing method of patterning roll for continuous plating - Google Patents

Manufacturing method of patterning roll for continuous plating Download PDF

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JP5903495B2
JP5903495B2 JP2014543384A JP2014543384A JP5903495B2 JP 5903495 B2 JP5903495 B2 JP 5903495B2 JP 2014543384 A JP2014543384 A JP 2014543384A JP 2014543384 A JP2014543384 A JP 2014543384A JP 5903495 B2 JP5903495 B2 JP 5903495B2
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resist pattern
continuous plating
pattern portion
patterning roll
photoresist
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JPWO2014125972A1 (en
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重田 龍男
龍男 重田
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Think Laboratory Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/50Controlling or regulating the coating processes
    • C23C2/54Controlling or regulating the coating processes of the mixing or stirring the bath
    • C23C2/544Controlling or regulating the coating processes of the mixing or stirring the bath using moving mixing devices separate from the substrate, e.g. an impeller of blade
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/04Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04Coating on selected surface areas, e.g. using masks
    • C23C16/042Coating on selected surface areas, e.g. using masks using masks
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00Coating not provided for in groups C23C2/00 - C23C24/00
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/02Local etching
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • C25D7/0614Strips or foils
    • C25D7/0657Conducting rolls
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Electroplating Methods And Accessories (AREA)
  • ing And Chemical Polishing (AREA)
  • Chemical Vapour Deposition (AREA)
  • Printing Plates And Materials Therefor (AREA)

Description

本発明は、DLC(ダイヤモンドライクカーボン)によって絶縁層のパターニングを施した連続メッキ用パターニングロール及びその製造方法に関する。   The present invention relates to a patterning roll for continuous plating in which an insulating layer is patterned by DLC (diamond-like carbon) and a method for manufacturing the same.

連続メッキ用ロールは、連続メッキ装置に用いられるもので、例えば、リールに巻き付けた鋼板等の帯状のワークを連続的に巻き取りながらメッキ浴中を通すことで、連続的にメッキを行うものである。連続メッキ用ロールの例としては、例えば、特許文献1や特許文献2に開示されたシンクロール等のロールがある。   The roll for continuous plating is used for a continuous plating apparatus. For example, the roll is continuously plated by passing a strip-shaped workpiece such as a steel sheet wound around a reel through a plating bath while continuously winding it. is there. As an example of the roll for continuous plating, there exist rolls, such as a sink roll disclosed by patent document 1 or patent document 2, for example.

上述したようなパターニングロールを製作する場合、基材に感光材を塗布して露光・現像・バーニングしてエッチングすると、いわゆるサイドエッチングと呼ばれるオーバーエッチングが発生する問題があった。そして、パターニングが微細になる程、サイドエッチングの問題がより一層顕在化する。さらに、パターニングが微細になる程、絶縁層の密着性の問題が生じる。   When the patterning roll as described above is manufactured, there is a problem in that over-etching called so-called side etching occurs when a photosensitive material is applied to a base material and exposed, developed, burned, and etched. As the patterning becomes finer, the problem of side etching becomes more obvious. Furthermore, the finer the patterning, the more problems arise with the adhesion of the insulating layer.

特開2006−283044号公報JP 2006-283044 A 特開2001−89836号公報JP 2001-89836 A 特開2009−093170号公報JP 2009-093170 A

本発明は、上記した従来技術の問題点に鑑みなされたもので、サイドエッチングの問題を解消し、絶縁層の密着性に優れた連続メッキ用パターニングロール及びその製造方法を提供することを目的とする。   The present invention has been made in view of the above-described problems of the prior art, and has an object to provide a patterning roll for continuous plating and a method for manufacturing the same, which solves the problem of side etching and has excellent adhesion of an insulating layer. To do.

上記課題を解決するため、連続メッキ用パターニングロールは、メッキ可能な円筒状金属基材の表面にフォトレジストを塗布し、露光・現像せしめてレジストパターン部と非レジストパターン部を形成し、前記非レジストパターン部の前記円筒状金属基材をエッチングせしめてエッチング凹部を形成し、前記エッチング凹部及びレジストパターン部の表面にDLC被覆膜を形成し、前記レジストパターン部上に形成されたDLC被覆膜を前記レジストパターン部ごと剥離せしめ、前記エッチング凹部内に前記DLC被覆膜が残存してなることを特徴とする。 To solve the above problems, patterned roll the continuous plating, a photoresist is applied to the surface of the plating can be cylindrically-shaped metallic substrate, the resist pattern portion and the non-resist pattern portion formed allowed exposure and development, the The cylindrical metal substrate of the non-resist pattern portion is etched to form an etching recess, a DLC coating film is formed on the surface of the etching recess and the resist pattern portion, and the DLC coating formed on the resist pattern portion is formed. The covering film is peeled off together with the resist pattern portion, and the DLC coating film remains in the etching recess.

このようにして、レジストパターン部上に形成されたDLC被覆膜を前記レジストパターン部ごと剥離せしめるため、サイドエッチングの問題が解消される利点がある。また、前記円筒状金属基材のエッチング凹部にDLC被覆膜を残存させることで、残存したDLC被覆膜が絶縁膜となる。そして、エッチング凹部にDLC被覆膜を残存させるため、密着性に優れるという利点がある。   Thus, since the DLC coating film formed on the resist pattern portion is peeled off together with the resist pattern portion, there is an advantage that the problem of side etching is solved. Further, by leaving the DLC coating film in the etching recesses of the cylindrical metal substrate, the remaining DLC coating film becomes an insulating film. And since a DLC coating film remains in an etching recessed part, there exists an advantage that it is excellent in adhesiveness.

前記フォトレジストが塗布される金属基材が、ニッケル、タングステン、クロム、チタン、金、銀、白金、ステンレス鋼、鉄、銅、アルミニウムからなる群から選ばれた少なくとも一種の材料から構成されるのが好適である。   The metal substrate to which the photoresist is applied is made of at least one material selected from the group consisting of nickel, tungsten, chromium, titanium, gold, silver, platinum, stainless steel, iron, copper, and aluminum. Is preferred.

前記エッチング凹部のエッチング深さが、1μm〜10μmであるのが好適である。   It is preferable that the etching depth of the etching recess is 1 μm to 10 μm.

前記被覆したDLC被覆膜の厚さが、1μm〜10μmであるのが好適である。   The thickness of the coated DLC coating film is preferably 1 μm to 10 μm.

また、前記円筒状金属基材が、ゴム又はクッション性を有する樹脂からなるクッション層を備えるようにしてもよい。前記クッション層としては、シリコンゴム等の合成ゴムやポリウレタン、ポリスチレン等の弾力性のある合成樹脂を使用することができる。このクッション層の厚さはクッション性即ち弾力性を付与できる厚さであればよく、特別の限定はないが、例えば、1cm〜5cm程度の厚さがあれば充分である。ゴム又はクッション性を有する樹脂からなるクッション層を備えた円筒状金属基材の例として、例えば特許文献3に記載されたグラビア版のように、ゴム又はクッション性を有する樹脂からなるクッション層を備えたロールを採用することができる。   Moreover, you may make it the said cylindrical metal base material equip with the cushion layer which consists of resin which has rubber | gum or cushioning properties. As the cushion layer, a synthetic rubber such as silicone rubber, or a synthetic resin having elasticity such as polyurethane or polystyrene can be used. The thickness of the cushion layer is not particularly limited as long as it can provide cushioning properties, that is, elasticity. For example, a thickness of about 1 cm to 5 cm is sufficient. As an example of a cylindrical metal substrate provided with a cushion layer made of rubber or a resin having cushioning properties, a cushion layer made of a resin having rubber or cushioning properties is provided, for example, a gravure plate described in Patent Document 3. Rolls can be employed.

前記フォトレジストとしては、ポジ型フォトレジスト又はネガ型フォトレジストのいずれも適用可能であるが、ネガ型フォトレジストであるのが好適である。   As the photoresist, either a positive photoresist or a negative photoresist can be applied, but a negative photoresist is preferable.

連続メッキ転写物は、連続メッキ用パターニングロールによって製造されてなることを特徴とする。 The continuous plating transfer product is manufactured by a patterning roll for continuous plating.

連続メッキ用パターニングロールによってメッキされる金属としては、公知のメッキ可能な金属であればいずれも適用可能である。例えば、ニッケル、タングステン、クロム、チタン、金、銀、白金、鉄、銅、亜鉛からなる群から選ばれた少なくとも一種の材料などが挙げられる。 As the metal plated by the patterning roll for continuous plating, any known metal that can be plated can be applied. Examples thereof include at least one material selected from the group consisting of nickel, tungsten, chromium, titanium, gold, silver, platinum, iron, copper, and zinc.

本発明の連続メッキ用パターニングロールの製造方法は、メッキ可能な円筒状金属基材の表面にフォトレジストを塗布し、露光・現像せしめてレジストパターン部と非レジストパターン部を形成する工程と、前記非レジストパターン部の前記円筒状金属基材をエッチングせしめてエッチング凹部を形成する工程と、前記エッチング凹部及びレジストパターン部の表面にDLC被覆膜を形成する工程と、前記レジストパターン部上に形成されたDLC被覆膜を前記レジストパターン部ごと剥離せしめ、前記エッチング凹部内に前記DLC被覆膜を残存させる工程と、を含むことを特徴とする。   The method for producing a patterning roll for continuous plating according to the present invention comprises a step of applying a photoresist to the surface of a cylindrical metal substrate that can be plated, exposing and developing to form a resist pattern portion and a non-resist pattern portion, Etching the cylindrical metal substrate of the non-resist pattern portion to form an etching recess, forming a DLC coating film on the etching recess and the surface of the resist pattern portion, and forming on the resist pattern portion Peeling the entire DLC coating film together with the resist pattern portion to leave the DLC coating film in the etching recess.

前記フォトレジストが塗布される金属基材が、ニッケル、タングステン、クロム、チタン、金、銀、白金、ステンレス鋼、鉄、銅、アルミニウムからなる群から選ばれた少なくとも一種の材料から構成されるのが好適である。   The metal substrate to which the photoresist is applied is made of at least one material selected from the group consisting of nickel, tungsten, chromium, titanium, gold, silver, platinum, stainless steel, iron, copper, and aluminum. Is preferred.

前記エッチング凹部のエッチング深さが、1μm〜10μmであるのが好適である。   It is preferable that the etching depth of the etching recess is 1 μm to 10 μm.

前記DLC被覆膜の厚さが、1μm〜10μmであるのが好適である。   The thickness of the DLC coating film is preferably 1 μm to 10 μm.

前記フォトレジストが塗布される金属基材が、ゴム又はクッション性を有する樹脂からなるクッション層を備えるのが好ましい。   It is preferable that the metal base material to which the photoresist is applied includes a cushion layer made of rubber or a resin having cushioning properties.

前記フォトレジストとしては、ポジ型フォトレジスト又はネガ型フォトレジストのいずれも適用可能であるが、ネガ型フォトレジストであるのが好適である。   As the photoresist, either a positive photoresist or a negative photoresist can be applied, but a negative photoresist is preferable.

本発明によれば、サイドエッチングの問題を解消し、絶縁層の密着性に優れた連続メッキ用パターニングロール及びその製造方法を提供することができるという著大な効果を有する。   ADVANTAGE OF THE INVENTION According to this invention, it has the remarkable effect that the problem of side etching can be eliminated and the patterning roll for continuous plating excellent in the adhesiveness of the insulating layer and its manufacturing method can be provided.

本発明の連続メッキ用パターニングロールの製造方法の各工程における態様の一例を模式的に示す説明図であり、(a)は円筒状金属基材の表面にフォトレジストを塗布した状態の要部断面図、(b)は露光・現像せしめてレジストパターン部と非レジストパターン部を形成した状態の要部断面図、(c)は非レジストパターン部の円筒状金属基材をエッチングせしめてエッチング凹部を形成した状態の要部断面図、(d)はエッチング凹部及びレジストパターン部の表面にDLC被覆膜を形成した状態の要部断面図、(e)はレジストパターン部上に形成されたDLC被覆膜をレジストパターン部ごと剥離せしめ、エッチング凹部内にDLC被覆膜を残存せしめた状態の要部断面図である。It is explanatory drawing which shows typically an example of the aspect in each process of the manufacturing method of the patterning roll for continuous plating of this invention, (a) is principal part cross section of the state which apply | coated the photoresist on the surface of the cylindrical metal base material (B) is a cross-sectional view of the main part in a state where a resist pattern portion and a non-resist pattern portion are formed by exposure and development, and (c) is an etching recess by etching a cylindrical metal substrate of the non-resist pattern portion. FIG. 4D is a cross-sectional view of the main part in the formed state, FIG. 4D is a cross-sectional view of the main part in a state where the DLC coating film is formed on the surfaces of the etching concave portion and the resist pattern portion, and FIG. It is principal part sectional drawing of the state which peeled off the coating film with the resist pattern part, and left the DLC coating film in the etching recessed part. 図1に示した連続メッキ用パターニングロールの製造方法の工程順を示すフローチャートである。It is a flowchart which shows the process order of the manufacturing method of the patterning roll for continuous plating shown in FIG. 連続メッキ転写物の製造手順を示す模式的説明図であり、(a)は連続メッキ用パターニングロール上に形成されたパターンメッキ層をプリント用基材上に転写する状態、(b)はプリント用基材上にパターンメッキ層を転写して連続メッキ転写物を製造した状態をそれぞれ示す。It is typical explanatory drawing which shows the manufacture procedure of a continuous plating transcription | transfer material, (a) is the state which transcribe | transfers the pattern plating layer formed on the patterning roll for continuous plating on the base material for printing, (b) is for printing The state which transferred the pattern plating layer on the base material and manufactured the continuous plating transcription | transfer material is each shown.

以下に本発明の実施の形態を説明するが、これら実施の形態は例示的に示されるもので、本発明の技術思想から逸脱しない限り種々の変形が可能なことはいうまでもない。   Embodiments of the present invention will be described below, but these embodiments are exemplarily shown, and it goes without saying that various modifications can be made without departing from the technical idea of the present invention.

図1において、符号10は連続メッキ用パターニングロールを示す。符号12はメッキ可能な円筒状金属基材を示し、ニッケル、タングステン、クロム、チタン、金、銀、白金、ステンレス鋼、鉄、銅、アルミニウムからなる群から選ばれた少なくとも一種の材料からからなるものを用いることができる。また、ゴム又はクッション性を有する樹脂からなるクッション層を備えるようにしてもよい。該クッション層は、ゴム又はクッション性を有する樹脂からなり、1mm〜10cm程度の均一な厚さで表面の平滑度が高いシート状のものを、継ぎ目に隙間が開かないように円筒状金属基材12の裏面に強固に接着するようにすればよい。   In FIG. 1, the code | symbol 10 shows the patterning roll for continuous plating. Reference numeral 12 denotes a cylindrical metal base material that can be plated, and is made of at least one material selected from the group consisting of nickel, tungsten, chromium, titanium, gold, silver, platinum, stainless steel, iron, copper, and aluminum. Things can be used. Moreover, you may make it provide the cushion layer which consists of resin which has rubber | gum or cushioning properties. The cushion layer is made of rubber or a resin having a cushioning property, and a cylindrical metal base material having a uniform thickness of about 1 mm to 10 cm and having a high surface smoothness so that a gap is not opened at the seam. What is necessary is just to make it adhere | attach to the back surface of 12 firmly.

まず、円筒状金属基材12の表面にフォトレジスト14を塗布する(図1(a)及び図2のステップ100)。露光・現像せしめてレジストパターン部16と非レジストパターン部18を形成する(図1(b)及び図2のステップ102)。フォトレジストはネガ型及びポジ型のいずれでも使用可能であるが、ネガ型フォトレジストを用いるのが好ましい。   First, a photoresist 14 is applied to the surface of the cylindrical metal substrate 12 (step 100 in FIG. 1A and FIG. 2). The resist pattern portion 16 and the non-resist pattern portion 18 are formed by exposure and development (step 102 in FIG. 1B and FIG. 2). The photoresist can be either a negative type or a positive type, but it is preferable to use a negative type photoresist.

次に、非レジストパターン部18の円筒状金属基材12をエッチングせしめてエッチング凹部20を形成する(図1(c)及び図2のステップ104)。   Next, the cylindrical metal substrate 12 of the non-resist pattern portion 18 is etched to form an etching recess 20 (FIG. 1C and step 104 in FIG. 2).

そして、エッチング凹部20及びレジストパターン部16の表面にDLC被覆膜22を形成する(図1(d)及び図2のステップ106)。前記DLC被覆膜はCVD(Chemical Vapor Deposition)法やスパッタ法によって形成すればよい。   Then, a DLC coating film 22 is formed on the surfaces of the etching recess 20 and the resist pattern portion 16 (step 106 in FIG. 1D and FIG. 2). The DLC coating film may be formed by a CVD (Chemical Vapor Deposition) method or a sputtering method.

次いで、前記レジストパターン部16上に形成されたDLC被覆膜22を前記レジストパターン部16ごと剥離せしめ、前記エッチング凹部20内に前記DLC被覆膜22を残存させる(図1(e)及び図2のステップ108)。このようにして、連続メッキ用パターニングロール10が完成する。連続メッキ用パターニングロール10は、前記エッチング凹部20内に残存した前記DLC被覆膜22が絶縁層となっている。   Next, the DLC coating film 22 formed on the resist pattern portion 16 is peeled off together with the resist pattern portion 16 to leave the DLC coating film 22 in the etching recess 20 (FIG. 1E and FIG. Step 108 of 2). In this way, the continuous plating patterning roll 10 is completed. In the patterning roll 10 for continuous plating, the DLC coating film 22 remaining in the etching recess 20 is an insulating layer.

次に、連続メッキ用パターニングロール10を用いた連続メッキ転写物の製造手順を図3に示す。   Next, FIG. 3 shows a procedure for producing a continuous plating transfer product using the patterning roll 10 for continuous plating.

図3(a)において、連続メッキ用パターニングロール10は、メッキ槽(図示省略)を通って前記DLC被覆膜22の残存していない円筒状金属基材12上に連続的にメッキ層24が形成されている。   In FIG. 3A, the continuous plating patterning roll 10 has a plating layer 24 continuously formed on a cylindrical metal substrate 12 where the DLC coating film 22 does not remain through a plating tank (not shown). Is formed.

そして、図3(a)によく示される如く、圧着転写ローラー26に掛装されてなるプリント用基材28にメッキ層24が連続的に転写され、図3(b)に示される連続メッキ転写物30となる。なお、プリント用基材としては、合成樹脂などのフィルムが挙げられる。このように、本発明の連続メッキ用パターニングロールは、微細にパターニングされたメッキ層を合成樹脂などのフィルムに転写することができるので、プリント回路基板等の製造に好適に用いることができる。   Then, as well shown in FIG. 3A, the plating layer 24 is continuously transferred to the printing substrate 28 that is hung on the pressure transfer roller 26, and the continuous plating transfer shown in FIG. It becomes the thing 30. In addition, as a base material for printing, films, such as a synthetic resin, are mentioned. Thus, the patterning roll for continuous plating of the present invention can transfer a finely patterned plating layer to a film such as a synthetic resin, and therefore can be suitably used for manufacturing a printed circuit board or the like.

以下に実施例をあげて本発明をさらに具体的に説明するが、これらの実施例は例示的に示されるもので限定的に解釈されるべきでないことはいうまでもない。   The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

(実施例1)
円周600mm、面長1100mmの版母材(アルミ中空ロール)を準備し、ブーメランライン(株式会社シンク・ラボラトリー製全自動レーザーグラビア製版ロール製造装置)を用いて下記する銅メッキ層の形成までを行った。まず、版母材(アルミ中空ロール)を銅メッキ槽に装着し、中空ロールをメッキ液に全没させて20A/dm2、6.0Vで80μmの銅メッキ層を形成した。メッキ表面はブツやピットの発生がなく、均一な銅メッキ層を得た。この銅メッキ層の表面を4ヘッド型研磨機(株式会社シンク・ラボラトリー製研磨機)を用いて研磨して当該銅メッキ層の表面を均一な研磨面とした。上記形成した銅メッキ層を基材としてその表面にフォトレジスト(サーマルレジスト:TSER−NS(株式会社シンク・ラボラトリー製))を塗布(ファウンテンコーター)、乾燥した。得られたフォトレジストの膜厚は膜厚計(FILLMETRICS社製F20、松下テクノトレーデイング社販売)で計ったところ、7μmであった。ついで、画像をレーザー露光し現像した。上記レーザー露光は、Laser Stream FXを用い露光条件300mJ/cm2で所定のパターン露光を行った。また、上記現像は、TLD現像液(株式会社シンク・ラボラトリー製現像液)を用い、現像液希釈比率(原液1:水7)で、24℃90秒間行い、所定のレジストパターン部と非レジストパターン部を形成した。
(Example 1)
Prepare a plate base material (aluminum hollow roll) with a circumference of 600 mm and a surface length of 1100 mm, and use the boomerang line (a fully automatic laser gravure plate making apparatus manufactured by Sink Laboratories, Inc.) to form the copper plating layer described below. went. First, a plate base material (aluminum hollow roll) was mounted on a copper plating tank, and the hollow roll was completely immersed in a plating solution to form a copper plating layer of 80 μm at 20 A / dm 2 and 6.0 V. The plating surface was free of bumps and pits, and a uniform copper plating layer was obtained. The surface of the copper plating layer was polished using a 4-head type polishing machine (Sink Laboratory Co., Ltd. polishing machine) to make the surface of the copper plating layer a uniform polishing surface. Using the formed copper plating layer as a base material, a photoresist (thermal resist: TSER-NS (manufactured by Sink Laboratories)) was applied to the surface (fountain coater) and dried. The film thickness of the obtained photoresist was 7 μm as measured by a film thickness meter (F20 manufactured by FILLMETRICS, sold by Matsushita Techno Trading). The image was then developed with laser exposure. In the laser exposure, a laser stream FX was used and a predetermined pattern exposure was performed under an exposure condition of 300 mJ / cm 2 . The above development is performed using a TLD developer (Developer manufactured by Sink Laboratories, Inc.) at a developer dilution ratio (stock solution 1: water 7) at 24 ° C. for 90 seconds, and a predetermined resist pattern portion and a non-resist pattern. Part was formed.

次に、非レジストパターン部の銅メッキ層に対して、塩化第二銅腐食液を60秒間スプレーエッチングし、エッチング深さが5μmのエッチング凹部を形成した。   Next, a cupric chloride corrosive solution was spray-etched for 60 seconds on the copper plating layer of the non-resist pattern portion to form an etching recess having an etching depth of 5 μm.

該銅メッキ層及びレジストパターン部の表面にDLC被覆膜をCVD法で形成した。雰囲気アルゴン/水素ガス雰囲気、原料ガスにヘキサメチルジシロキサン、成膜温度80−120℃、成膜時間60分で膜厚0.1μmの中間層を成膜した。次に、原料ガスにトルエン、成膜温度80−120℃、成膜時間180分で膜厚5μmのDLC被覆膜を成膜した。   A DLC coating film was formed on the surfaces of the copper plating layer and the resist pattern portion by a CVD method. An intermediate layer having a film thickness of 0.1 μm was formed in an argon / hydrogen gas atmosphere, hexamethyldisiloxane as a source gas, a film formation temperature of 80 to 120 ° C., and a film formation time of 60 minutes. Next, a DLC coating film having a film thickness of 5 μm was formed on the source gas using toluene, a film formation temperature of 80 to 120 ° C., and a film formation time of 180 minutes.

次いで、該中空ロールを水酸化ナトリウム水溶液中で超音波処理を30分行った。そして、該レジストパターン部上に形成されたDLC被覆膜を該レジストパターン部ごと剥離せしめ、エッチング凹部内に前記DLC被覆膜を残存させた。このようにして、連続メッキ用パターニングロールを得た。   Next, the hollow roll was sonicated in an aqueous sodium hydroxide solution for 30 minutes. Then, the DLC coating film formed on the resist pattern portion was peeled off together with the resist pattern portion, and the DLC coating film was left in the etching recess. In this way, a patterning roll for continuous plating was obtained.

この連続メッキ用パターニングロールの表面を光学顕微鏡で観察したところ、高精細な連続メッキ用パターニングロールが観察された。   When the surface of this continuous plating patterning roll was observed with an optical microscope, a high-definition continuous plating patterning roll was observed.

(実施例2)
レジストパターン形成の表面の基材をステンレス鋼とし、腐食液を硝酸・過酸化水素水とした以外は実施例1と同様にして、連続メッキ用パターニングロールを得た。得られた連続メッキ用パターニングロールを電子顕微鏡で観察したところ、高精細なDLCパターンが絶縁層として観察された。
(Example 2)
A patterning roll for continuous plating was obtained in the same manner as in Example 1 except that the base material on the resist pattern formation surface was stainless steel and the corrosive liquid was nitric acid / hydrogen peroxide solution. When the obtained patterning roll for continuous plating was observed with an electron microscope, a high-definition DLC pattern was observed as an insulating layer.

(実施例3)
レジストパターン形成の表面の基材をチタンとし、腐食液をフッ酸水溶液とした以外は実施例1と同様にして、連続メッキ用パターニングロールを得た。得られた連続メッキ用パターニングロールを電子顕微鏡で観察したところ、高精細なDLCパターンが絶縁層として観察された。
(Example 3)
A patterning roll for continuous plating was obtained in the same manner as in Example 1 except that the substrate on the surface of resist pattern formation was titanium and the corrosive solution was an aqueous hydrofluoric acid solution. When the obtained patterning roll for continuous plating was observed with an electron microscope, a high-definition DLC pattern was observed as an insulating layer.

(実施例4)
基材として、シリコンゴム上に板厚0.4mmのニッケルスリーブを嵌着せしめたロールを使用し、腐食液を硝酸・過酸化水素水とした以外は実施例1〜3と同様にして連続メッキ用パターニングロールを作製した。得られた連続メッキ用パターニングロールを電子顕微鏡で観察したところ、高精細なDLCパターンが絶縁層として観察された。
Example 4
Continuous plating was carried out in the same manner as in Examples 1 to 3 except that a roll in which a nickel sleeve having a thickness of 0.4 mm was fitted on silicon rubber was used as a base material, and the corrosive liquid was nitric acid / hydrogen peroxide. A patterning roll was prepared. When the obtained patterning roll for continuous plating was observed with an electron microscope, a high-definition DLC pattern was observed as an insulating layer.

10:連続メッキ用パターニングロール、12:円筒状金属基材、14:フォトレジスト、16:レジストパターン部、18:非レジストパターン部、20:エッチング凹部、22:DLC被覆膜、24:メッキ層、26:圧着転写ローラー、28:プリント用基材、30:連続メッキ転写物。 10: patterning roll for continuous plating, 12: cylindrical metal substrate, 14: photoresist, 16: resist pattern portion, 18: non-resist pattern portion, 20: etching recess, 22: DLC coating film, 24: plating layer , 26: pressure transfer roller, 28: printing substrate, 30: continuous plating transfer.

Claims (6)

メッキ可能な円筒状金属基材の表面にフォトレジストを塗布し、露光・現像せしめてレジストパターン部と非レジストパターン部を形成する工程と、前記非レジストパターン部の前記円筒状金属基材をエッチングせしめてエッチング凹部を形成する工程と、前記エッチング凹部及びレジストパターン部の表面にDLC被覆膜を形成する工程と、前記レジストパターン部上に形成されたDLC被覆膜を前記レジストパターン部ごと剥離せしめ、前記エッチング凹部内に前記DLC被覆膜を残存させる工程と、を含むことを特徴とする連続メッキ用パターニングロールの製造方法。   Applying a photoresist to the surface of a cylindrical metal substrate that can be plated, exposing and developing to form a resist pattern portion and a non-resist pattern portion, and etching the cylindrical metal substrate in the non-resist pattern portion A step of forming an etching recess, a step of forming a DLC coating film on the surface of the etching recess and the resist pattern portion, and a peeling of the DLC coating film formed on the resist pattern portion together with the resist pattern portion. And a step of allowing the DLC coating film to remain in the etching recess, and a method for producing a patterning roll for continuous plating. 前記フォトレジストが塗布される金属基材が、ニッケル、タングステン、クロム、チタン、金、銀、白金、ステンレス鋼、鉄、銅、アルミニウムからなる群から選ばれた少なくとも一種の材料から構成されることを特徴とする請求項記載の連続メッキ用パターニングロールの製造方法。 The metal substrate to which the photoresist is applied is composed of at least one material selected from the group consisting of nickel, tungsten, chromium, titanium, gold, silver, platinum, stainless steel, iron, copper, and aluminum. method for producing a continuous plating patterning roll according to claim 1, wherein. 前記エッチング凹部のエッチング深さが、1μm〜10μmであることを特徴とする請求項又は項記載の連続メッキ用パターニングロールの製造方法。 The method for producing a patterning roll for continuous plating according to claim 1 or 2, wherein the etching depth of the etching recess is 1 µm to 10 µm. 前記DLC被覆膜の厚さが、1μm〜10μmであることを特徴とする請求項1〜3いずれか1項記載の連続メッキ用パターニングロールの製造方法。 The thickness of the said DLC coating film is 1 micrometer-10 micrometers, The manufacturing method of the patterning roll for continuous plating of any one of Claims 1-3 characterized by the above-mentioned. 前記フォトレジストが塗布される金属基材が、ゴム又はクッション性を有する樹脂からなるクッション層を備えることを特徴とする請求項1〜4いずれか1項記載の連続メッキ用パターニングロールの製造方法。 The method for producing a patterning roll for continuous plating according to any one of claims 1 to 4, wherein the metal substrate to which the photoresist is applied includes a cushion layer made of rubber or a resin having cushioning properties. 前記フォトレジストが、ネガ型フォトレジストであることを特徴とする請求項1〜5いずれか1項記載の連続メッキ用パターニングロールの製造方法。 The method for producing a patterning roll for continuous plating according to any one of claims 1 to 5 , wherein the photoresist is a negative photoresist.
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