JP2009190305A - Manufacturing method of electroformed mold - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To uniformly form a plated coating formed into an uneven surface without deforming or swelling a transfer layer having an uneven surface even in an electrodeless plating process. <P>SOLUTION: In a manufacturing method of an electroformed mold, the transfer surface of a transfer material having the transfer surface formed of an ultraviolet curable resin composition is brought into contact with the uneven pattern of a matrix mold with the predetermined uneven pattern formed thereon; an uneven surface corresponding to the uneven pattern is formed on the transfer material by ultraviolet-curing the transfer surface; then electrodeless plating and electroforming are executed to a surface of the transfer material having the uneven surface. In the manufacturing method of the electroformed mold, the transfer material has a double-layer structure of a transfer layer having the transfer surface and a base material layer; and the base material is formed of a resin material having a glass transition temperature of 120°C or above, ultraviolet permeability at a wavelength of 365 nm not smaller than 30%, and a volume swelling ratio not larger than 3% when immersed in hydrochloric acid. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an electroforming mold such as a nickel mold used for forming recording surfaces of various optical information recording media.

  In order to mold the information surface of an optical information recording medium such as a DVD, a mold-making technique by nickel (Ni) electroforming has been conventionally used. Tens of thousands to hundreds of thousands of optical information recording media such as DVDs can be duplicated from one stamper produced by this electroforming technique. That is, in order to produce a stamper, generally, a glass master having a fine uneven surface corresponding to an information pattern of an optical information recording medium formed on the surface of a substrate such as a glass material is used as a master, and a conductive film is used as the master. Is formed, and electroforming with a metal such as nickel is performed to manufacture a stamper (electroforming mold) for an optical information recording medium.

  Various methods for producing the stamper have been proposed. For example, Japanese Patent Application Laid-Open No. 54-40239 (Patent Document 1), Japanese Patent Application Laid-Open No. 59-173288 (Patent Document 2) and Japanese Patent Application Laid-Open No. 8-287529. (Patent document 3) etc. are mentioned.

  Japanese Patent Laid-Open No. 2007-291339 (Patent Document 4) previously proposed by the applicant of the present application includes a technique using a transfer material made of synthetic resin. In other words, this technology presses a photocurable transfer material against a stamper, cures by light irradiation in this state, and removes the stamper from the cured photocurable transfer material, whereby a fine concavo-convex pattern is transferred to the photocurable transfer material. It is formed on the material.

  However, in order to perform electroforming as a post process, the surface of the concavo-convex pattern of the photocurable transfer material is subjected to a pretreatment of electroless plating, and the transfer material swells during the plating process, resulting in a fine There is a problem in that a distorted uneven pattern is distorted and a desired electroformed mold cannot be obtained.

JP 54-40239 A JP 59-173288 A JP-A-8-287529 JP 2007-291339 A

  The present invention has been made in view of the above circumstances, and an electroforming mold having the same concavo-convex pattern as that formed on the master mold without deformation of the concavo-convex surface applied to the transfer material during the electroless plating process. An object of the present invention is to provide a method for producing an electroforming mold capable of reliably and accurately obtaining the above.

  As a result of intensive studies to solve the above problems, the inventors of the present invention formed a concavo-convex surface corresponding to a desired concavo-convex pattern on the transfer surface of a transfer material made of an ultraviolet curable resin composition, and no surface was formed on the surface. When electroforming through an electroplating film to produce an electroforming mold, the resin transfer material used has a two-layer structure of a transfer layer having a transfer surface and a base material layer, and When the base material layer is formed of a resin material having a glass transition temperature of 120 ° C. or higher, an ultraviolet transmittance at a wavelength of 365 nm of 30% or higher, and a volume swelling rate of 3% or less when immersed in concentrated hydrochloric acid, Even during the electroless plating process, the transfer layer with the uneven surface will not be deformed or swell, and the plating film formed on the uneven surface can be uniformly formed, and highly accurate electroformed molds can be manufactured reliably To find out Which has led to the completion of the method of production.

  That is, the present invention brings the transfer surface of a transfer material having a transfer surface made of an ultraviolet curable resin composition into contact with the concavo-convex pattern of a base mold on which a predetermined concavo-convex pattern is formed, Curing to form a concavo-convex surface corresponding to the concavo-convex pattern on the transfer material, then performing electroless plating and electroforming on the surface of the transfer material having the concavo-convex surface, and removing the transfer material, In the method of manufacturing an electroforming mold for obtaining an electroformed mold having the same unevenness as a predetermined uneven pattern, the transfer material has a two-layer structure of a transfer layer having the transfer surface and a base material layer, and the base material The layer is formed of a resin material having a glass transition temperature of 120 ° C. or more, an ultraviolet transmittance of 30% or more at a wavelength of 365 nm, and a volume swelling ratio of 3% or less when immersed in concentrated hydrochloric acid. Electroforming mold Production method, in particular, the resin of the base layer is to provide a method of manufacturing a electroforming die which polysulfone is selected.

  According to the manufacturing method of the present invention, the transfer layer having the uneven surface is not deformed or swells even during the electroless plating process, and the plating film formed on the uneven surface can be uniformly formed. A precision electroformed mold can be reliably manufactured.

Hereinafter, the production method of the present invention will be described in more detail.
The present invention finally forms an electroforming mold using a transfer layer made of an ultraviolet curable resin composition. That is, a transfer material provided with a base material layer and an ultraviolet curable transfer layer is pressed and brought into close contact with the mother mold to transfer the fine shape of the mother mold, and the fine shape is formed on the transfer layer by ultraviolet irradiation. Is.

  As the mother mold, those formed of a metal such as nickel or glass can be used. A predetermined concavo-convex pattern corresponding to the purpose of use of the electroforming mold is formed on the master mold, and the concavo-convex pattern is transferred to the transfer layer.

  As shown in FIG. 1A, the transfer material includes a transfer layer 10 and a base material layer 11 having the transfer surface, and the base material layer 11 has a glass transition temperature of 120 ° C. or higher and a wavelength of 365 nm. It is characterized by being formed of a resin material having an ultraviolet transmittance of 30% or more and a volume swelling ratio of 3% or less when immersed in concentrated hydrochloric acid.

  As the material of the base material layer, it is preferable to use a resin material having a high ultraviolet transmittance and sufficient stiffness. Moreover, since electroless plating is performed as described later, it is required to have plating resistance so as not to be hydrolyzed in the plating bath.

  As the material of the base material layer, it is preferable that the bending stress evaluated by the measuring method shown in FIG. 4 is 15 gf / 25 mm or more.

  In the base material layer, the glass transition temperature (Tg) is an index of the thermoplasticity and temperature dependency of the resin, and the Tg is 120 ° C. or higher for obtaining the desired effect of the present invention. C. or higher, more preferably 160.degree. C. or higher.

  Further, it is necessary that the ultraviolet transmittance at a wavelength of 365 nm is 30% or more. This is based on the fact that the transfer layer laminated on the base material layer is UV-cured by being irradiated with UV light from the base material layer side in a state where the transfer surface of the transfer material is in contact with the concave-convex pattern of the matrix mold. This is because the material layer needs to have a predetermined permeability. A higher ultraviolet transmittance at a wavelength of 365 nm is preferable, and the lower limit is preferably 30% or more.

  Furthermore, it is necessary to select a resin base material having a volume swelling rate of 3% or less when immersed in concentrated hydrochloric acid so that the transfer material is not deformed during the electroless plating process.

  The material of the base material layer having the above physical properties is not particularly limited as long as it is a material having the above physical properties, and specific examples include polysulfone (PSF), polyethersulfone (PES) and the like. In particular, it is preferable to use polysulfone.

  The transfer layer 10 constituting the transfer material 1 is formed of an ultraviolet curable resin composition, and it is preferable that the cured product of the resin composition is relatively strong and has alkali resistance.

  As the ultraviolet curable resin composition for the transfer layer, a composition containing a reactive diluent having a photopolymerizable functional group and a polymer can be used. The composition described in 2007-291339 can be used. Specifically, the following composition components can be employed.

  As the reactive diluent having the photopolymerizable functional group, for example, as (meth) acrylic monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) Acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl polyethoxy (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, phenyloxyethyl ( (Meth) acrylate, tricyclodecane mono (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acryloylmorpholine, N-vinylcaprolactam o-phenylphenyloxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol dipropoxy di (meth) acrylate, hydroxypivalate neopentyl glycol di (Meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, glycerin diacrylate, glycerin acrylate methacrylate, glycerin dimethacrylate, trimethylol Propane diacrylate, trimethylolpropane acrylate methacrylate, trimethylolpropane dimethacrylate, trimethylolpropane (Meth) acrylate monomers such as li (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, ditrimethylolpropane tetra (meth) acrylate Polyol compounds (eg, ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1; , 3-propanediol, trimethylolpropane, diethylene glycol, dipropylene glycol, polypropylene glycol, 1,4-dimethylolcyclohexane, bisphenol A polyethoxydiol, polyteto Polyols such as lamethylene glycol, the above polyols and polybasic acids such as succinic acid, maleic acid, itaconic acid, adipic acid, hydrogenated dimer acid, phthalic acid, isophthalic acid, terephthalic acid, and the acid anhydrides thereof Polyester polyols which are reactants of the above, polycaprolactone polyols which are reactants of the polyols and ε-caprolactone, reaction of the polyols with ε-caprolactone of the polybasic acids or acid anhydrides thereof Products, polycarbonate polyols, polymer polyols, etc.) and organic polyisocyanates (for example, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentanyl diisocyanate, hexamethylene dii) Socyanate, 2,4,4′-trimethylhexamethylene diisocyanate, 2,2 ′, 4-trimethylhexamethylene diisocyanate, etc.) and a hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl) (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, cyclohexane-1,4-dimethylol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, Bisphenol type epoxy resin such as polyurethane (meth) acrylate, bisphenol A type epoxy resin, bisphenol F type epoxy resin and (meth) acrylic, which are reaction products of glycerin di (meth) acrylate, etc. It can be mentioned a reactant (meth) acrylate oligomers such as bisphenol type epoxy (meth) acrylate. These compounds having a photopolymerizable functional group can be used alone or in combination of two or more.

  Examples of the polymer include acrylic resin, polyvinyl acetate, vinyl acetate / (meth) acrylate copolymer, ethylene / vinyl acetate copolymer, polystyrene and its copolymer, polyvinyl chloride and its copolymer, butadiene / acrylonitrile. Copolymer, acrylonitrile / butadiene / styrene copolymer, methacrylate / acrylonitrile / butadiene / styrene copolymer, 2-chlorobutadiene-1,3-polymer, chlorinated rubber, styrene / butadiene / styrene copolymer, styrene / Examples include isoprene / styrene block copolymer, epoxy resin, polyamide, polyester, polyurethane, cellulose ester, cellulose ether, polycarbonate, and polyvinyl acetal. From, it is preferable to use an acrylic resin.

  In addition, the above composition can contain a phosphorus atom-containing compound as a lubricant, and various hydrocarbon resins and ultraviolet absorbers, anti-aging agents, dyes, for the purpose of improving processability such as processability and bonding, A processing aid or the like can be appropriately added as necessary.

  The transfer layer 10 is formed of an ultraviolet curable resin composition. After transferring the concave / convex pattern of the master mold, the transfer layer 10 is irradiated with ultraviolet rays under predetermined conditions. In the transfer layer 10, an ultraviolet curable resin composition is applied to one end surface of the base material layer 11, and after the transfer, this is irradiated with ultraviolet light from the base material layer side to obtain a cured product of the resin composition. Specifically, as shown in FIG. 3, the ultraviolet curable resin composition applied to the end surface of the base material layer 11 is shown in the figure by pressing the transfer material 1 against the surface of the master mold 50 on which the concave / convex pattern is formed. In this state, as shown by the arrow in the figure, the resin composition is cured by irradiating with ultraviolet rays from the base material layer side. In addition, the formation method of a ultraviolet curable resin composition can employ | adopt the aspect formed into a film form by film forming methods, such as solvent coating, a calendar | calender, a roll, T-die extrusion, and inflation. In this case, the thickness of the film to be formed is appropriately selected, but is preferably in the range of 5 to 100 μm.

  In addition, the resin composition can be formed on the surface of the base material layer using various laminating apparatuses by a wet lamination method or the like.

  The ultraviolet curing of the ultraviolet curable resin composition can be performed by a conventional method.

  A release sheet can be provided on the surface of the transfer layer made of the resin composition. Specifically, as shown in FIG. 2, by sticking the release sheet 20 to the outer surface of the transfer material so as to be peelable, the adhesiveness is maintained before use, and contamination such as dust adhesion In addition, the handling property is improved during use. In this case, examples of the release sheet include polyethylene terephthalate (PET), polyethylene (PE), and polypropylene (PP) as main materials, and particularly preferably PET.

  Next, as shown in FIG. 1B, the transfer material is separated from the master mold 50, and then the transfer surface is cast into a concavo-convex pattern shape as shown in FIG. 1C. An electroless plating film 12 is formed on a transfer layer having a concavo-convex surface corresponding to the concavo-convex pattern of the transfer material 1 composed of the layer 10 and the base material layer 11. The electroless plating film is thinly formed on the surface of the resin transfer layer on which the uneven surface is formed, as indicated by reference numeral 12 in FIG.

  Regarding the formation method of the electroless plating film, known plating baths, that is, reducing agents such as water-soluble metal salts, hypophosphorous acid or salts thereof, stabilizers, accelerators, lubricants, and complexing agents such as ammonium sulfate. Can be used. Electroless plating usually includes nickel plating, cobalt plating, copper plating, etc. In the present invention, nickel plating should be used from the viewpoint of adhesion with various types of electroforming molds. Is preferred. In addition, the composition of the plating bath called a prevailing bath or a low temperature bath can be normally used for an electroless nickel plating bath, It is preferable to make the pH into the range of 4.0-6.0.

  As a method of performing electroless plating using the above plating bath, a normal method can be adopted, and after treatment with an aqueous stannous chloride solution, a sensitizing-activating treatment in which treatment is performed with an aqueous palladium chloride solution. After forming metal palladium nuclei on the uneven surface of the transfer layer by a known pretreatment method such as, electroless plating on the uneven surface to which the metal palladium nuclei are attached is immersed in the electroless plating bath. In this case, the plating concentration, the plating temperature, and the plating time are appropriately selected according to the desired plating film thickness. In addition, a commercial item can be used as an electroless plating bath such as a pretreatment for forming the metal palladium nucleus and an electroless nickel plating bath.

  Next, as shown in FIG. 1 (D), after an electroless plating film is formed on the uneven surface of the transfer material 1, the surface of the plating film is further subjected to electroforming.

  A known working method can be adopted for electroforming. Like the electroless plating film, it is preferable to employ nickel electroforming using nickel as the metal. The nickel electroforming bath is generally selected from nickel chloride baths, watt baths, nickel borofluoride baths, nickel sulfamate baths, etc., but from the viewpoint of reducing electrodeposition stress and electrodeposition efficiency, sulfamic acid can be used. It is preferred to use a nickel bath. In this case, the bath composition is in the range of nickel sulfamate 300-450 g / l, nickel chloride 0-30 g / l and boric acid 30-45 g / l, and the working conditions are usually pH 3.5-4.5, The temperature is 40-60 ° C.

  A desired electroformed mold 30 can be manufactured by a removal method such as dissolution or peeling of the transfer material 1 (see FIG. 1E). When the transfer material 1 is peeled from the electroforming mold 30, the plating film 12 formed by electroless plating is integrated with the electroformed layer laminated by electroforming to form an electroforming mold.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.

[Examples 1 and 2, Comparative Examples 1 to 4]
The transfer layer which consists of an ultraviolet curable resin composition shown in following Table 1 common to all the Examples and comparative examples was formed in the base material layer of the Example shown in following Table 3, and a comparative example. That is, the ultraviolet curable resin composition was applied to the film by a wet lamination method.

Synthesis of Polymer 1 2-hydroxyethyl methacrylate “12.1 parts by mass”, methyl methacrylate “74.6 parts by mass”, butyl methacrylate “13.2 parts by mass”, AIBN “5 parts by mass”, toluene “50 parts by mass” And 50 parts by mass of ethyl acetate were added, the monomer solution was heated, and polymer synthesis was performed until the weight average molecular weight reached 110,000.

  Next, as shown in FIG. 1, the uneven surface of the master mold is brought into contact with the transfer surface of the transfer material having a transfer surface made of a resin composition, and the transfer surface is UV-cured so that the transfer material has an uneven surface. Formed.

  Next, as shown in FIG. 1, electroless plating and electroforming were performed on the surface of the transfer material having an uneven surface.

  As shown in the following table, a series of plating processes centered on a plating solution (“Nickel Pomer HCR” manufactured by Nippon Chemical Industry Co., Ltd.) were performed.

※上記の商品名は全て日本化学産業社製

* The above product names are all manufactured by Nippon Chemical Industry Co., Ltd.

  The plating conditions include electroless nickel plating at a plating bath, 89 to 94 ° C., pH 4.6 (constant), nickel concentration 5.0 to 6.0 g / l, and a predetermined thin film electroless nickel plating film. Got. Next, nickel electroforming of about 300 μm was performed using the following nickel sulfamate plating bath.

(Nickel sulfamate plating bath)
Nickel sulfamate 300g / L
Nickel chloride 30g / L
Boric acid 30g / L
pH 4.0
Temperature 50 ℃

  Thereafter, the transfer material was immersed in acetone for 1 hour, and then the transfer material was removed by ultrasonic cleaning to obtain a nickel electroforming mold.

※各実施例の基材の詳細については下記の表３のとおりである。

* Details of the base material of each example are as shown in Table 3 below.

(1) UV transmittance (%)
When the 365 nm transmittance was 30% or more, it was generally evaluated as good.

(2) Glass transition temperature Tg (° C)
The base material was cut into a length of 20 mm and a width of 4 mm (thickness 25 μm) to prepare a sample. Using a TMA (Thermal Mechanical Analysis) apparatus SS6100 (manufactured by SII Nanotechnology Co., Ltd.), the sample temperature was 30 to 120 ° C., the heating rate was 5 ° C./min, and the tensile tension was 4.9 ×. The measurement was performed at 10 ⁵ Pa.

(3) Acid resistance (swelling rate)
When immersed in 37% hydrochloric acid for 1 hour, the appearance was visually evaluated as “◯” if there was a phenomenon of cloudiness or solubility, and “X” otherwise.

(4) Simple bending stress (gf / 25mm)
As shown in FIG. 4, a base film having a predetermined size of 30 mm in width and 80 mm in length is used, and a product name “HEIDON” load measuring device (manufactured by Shinto Kagaku Co., Ltd.) is used. The repulsive force when the film sample was narrowed at a moving speed of 5 mm / s as in the direction was measured.

(5) Transfer layer curability Quantification of curing level of UV cured layer of transfer layer before immersion of plating solution (evaluation method)
After transferring the concavo-convex pattern of the master mold, the transfer layer was cured by irradiation with 5000 mJ / cm ² from the substrate side, and the master mold was peeled off.
(Evaluation criteria)
When the tack of the UV cured layer was reduced and the peelability was good, “◯” was indicated. Otherwise, “X” was assigned.

(6) Stability of plating solution (evaluation method)
Electroless plating and electroforming were performed, and the stability of the plating solution of the base material layer of the transfer material was visually evaluated.
(Evaluation criteria)
In the electroless plating process, discoloration and deformation due to dissolution and swelling of the base material layer by the plating solution were evaluated. If it was good, it was “◯”, otherwise it was “x”.

It is the schematic explaining process (A)-(E) of the manufacturing method which concerns on one Example of this invention. It is a fragmentary sectional view which shows the transcription | transfer material (2 layer structure) used for the manufacturing method which concerns on one Example of this invention. It is the schematic which shows a mode that the ultraviolet-ray was irradiated in the state which pressed the transfer material to the mother mold, and the transfer layer which has an uneven | corrugated pattern was formed. It is explanatory drawing for measuring the bending stress of base resin which comprises a transfer material.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transfer material 10 Transfer layer 11 Base material layer 12 Plating film 20 Release sheet 30 Electroformed layer (electroformed mold)
50 Master mold D Distance (span)

Claims (2)

  The transfer surface of a transfer material having a transfer surface made of an ultraviolet curable resin composition is brought into contact with the uneven pattern of the master mold on which a predetermined uneven pattern is formed, and the transfer surface is UV-cured to form a transfer material. By forming an uneven surface corresponding to the uneven pattern, and then performing electroless plating and electroforming on the surface of the transfer material having the uneven surface, and removing the transfer material, the same as the predetermined uneven pattern In the method for manufacturing an electroforming mold for obtaining an electroforming mold having irregularities, the transfer material has a two-layer structure of a transfer layer having a transfer surface and a base material layer, and the base material layer has a glass transition temperature. Is formed of a resin material having an ultraviolet transmittance of 120% or more at a wavelength of 365 nm of 30% or more and a volume swelling ratio of 3% or less when immersed in concentrated hydrochloric acid. .   2. The method for producing an electroforming mold according to claim 1, wherein the resin of the base material layer is polysulfone.

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