JPS58217689A - Preparation of metal matrix mold for duplicating plate body having recessed and protruded information - Google Patents

Abstract

PURPOSE:To obtain the titled metal matrix mold, by a method wherein the nucleus of an activating metal is formed on the sensitized and activated surface of resin and electroless plating of Ni and Co is applied to the treated surface of resin to form a conductive film for electroless plating. CONSTITUTION:The nucleus of an activating metal is formed on the sensitized and activated surface of resin and Ni or Co is subsequently applied to the activated surface at an almost room temp. by electroless plating to form a conductive film for electroless plating. Ni electrolytic plating is further applied to obtain a metal body. This metal body is separated at the interface with the activated surface to form a negative matrix mold with a recessed and protruded information pattern.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a metal master mold for replicating a plate-like object having unevenness information such as a needle tip grinder for a video disk, an optical disk memory, or a grooved capacitive video disk stylus. It is related to the manufacturing method.

Reproductions of these uneven information patterns can be made using almost the same techniques as those used for making general phonograph records. In other words, the method used to make phonograph records is to cut sound grooves into the nitrocellulose lacquer surface using a vibrating cutting needle, and then coat this surface with a nickel coating that will serve as a matrix from which many pressure molds will be manufactured. be coated.

In the case of duplicating an uneven information pattern as described above, an uneven information pattern is formed on a glass master by photolithography, transferred onto a soluble resin or an ultraviolet curable resin surface, and then transferred to the resin surface. A suitable method is to form a nickel coating that serves as a matrix for manufacturing a large number of pressure molds.

In the above-mentioned method, the conductive base layer d is usually formed by suitably activating the surface and then forming a thin layer of silver by chemical reduction as a pretreatment before applying the nickel coating. Nickel is then electroplated onto the base layer to form a nickel layer of appropriate thickness, and the structure is then separated at the interface between the silver layer and the lacquer base layer. This method typically
In order to harden the surface of the silver layer, nickel and/or
Alternatively, deposit chromium or etch away the silver layer to expose a hard nickel surface. Therefore, this surface does not completely faithfully reproduce the original resin surface, resulting in a drawback that the original recording is slightly deteriorated. Therefore, in order to eliminate the above-mentioned drawbacks, a method can be considered in which the conductive base layer is formed by vapor deposition of a metal such as nickel. This method is suitable when the unevenness of the pattern is small, but in general cases with deep grooves, deep bits, or high protrusions, there is less metal film adhesion on the sides of the grooves, focuses, and protrusions, and the metal film is less likely to adhere during electroplating. There are drawbacks such as wire breakage and inaccurate side profile.

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned drawbacks of the prior art and to provide a method for manufacturing a metal master mold for replicating a plate-shaped body having uneven information, which can accurately transfer an original information pattern.

In order to achieve the above object, the present invention first sensitizes and activates the surface of a nickel coating serving as a matrix to form activated metal nuclei on the surface, and then The key point is to form a conductive film for electrolytic plating by electroless plating nickel or metal at room temperature, and then perform nickel electrolytic plating.

First, the basics of the present invention will be comprehensively explained. The above-mentioned drawbacks of the prior art are overcome by electroless plating of nickel or cobalt at about room temperature to provide a conductive base layer for electrolytic plating. The method described in Japanese Patent Publication No. 49-47615 by R.CA Company can be adopted. This is limited to the case where the adherend is a synthetic resin positive photoresist material that is easily attacked by alkaline IJ media, but if the conditions are specified, the adherend can be treated as a negative photoresist. We have found that this method is applicable to both curable resins and soluble resins such as acetyl cellulose, ethyl cellulose, methyl cellulose, flobil cellulose, and methyl cellulose. As the chemical plating method at approximately room temperature, not only the immersion method but also the spray method described in Japanese Patent Application Laid-Open No. 50-94901 by Nippon Columbia Co., Ltd. was applicable.

A problem when forming a conductive base layer for electrolytic plating by electroless plating of nickel or conorct at about room temperature is high plating stress. For example, C
When trying to form a conductive base layer to a thickness of 0.4 to 0.8 μm by electroless nickel plating, as in the example described in Japanese Patent Publication No. 56-26482 by BS Sony Corporation, it becomes impossible to form a conductive base layer, especially in flat areas. Cracks and peeling occur in the deposited metal film during electrolytic plating or during subsequent electrolytic plating. However, electroless plating of nickel or cobalt can be applied by stopping at the stage before a completely mirror-like metal surface is obtained and the film becomes opaque. found.

That is, the drawing shows that a groove with a depth of 5 μm and a width of 2 μm is formed with a 10 μm pinch from a position of a radius of 3 cm to a position of a radius of 8.5 cm on the surface of an ultraviolet curable resin on an acrylic substrate carrier with a diameter of 3 cm. This figure shows an example of the dependence of the resistance between the inner and outer circumferences on the electroless plating time when a nickel film is attached by electroless plating to a substrate onto which a negative image of a spirally carved pattern has been transferred. In resistance region 6, where a metal mirror surface was obtained and became opaque, cracks and peeling occurred in the deposited metal film on the flat part during electroless plating or during electrolytic plating in the next step. A wire break occurred during plating. Therefore, the preferred resistance value in this case was in the range of 20Ω to 1Ω, but this value changes depending on the shape of the uneven information pattern to be transferred. In other words, even if the shape of the uneven information pattern changes, the one thing that can be said in common is that it is preferable to stop electroless plating before a completely metallic mirror surface is obtained and it becomes opaque. It is.

Even with the conductive base layer in such a state, a good transfer surface can be obtained after the subsequent electrolytic plating is performed.

Examples of the present invention will be described below.

[Example 1] A pattern in which grooves of 5 μm in depth and 2 μm in width were carved in a spiral pattern at a pitch of 10 μm from a position with a radius of 3 cm to a position of 14 cm was formed on a glass master disk using an ultraviolet curable resin manufactured by Dainippon Ink & Chemicals. It was transferred onto an acrylic substrate carrier using HDS-i. This was immersed in a 60% HNO3 solution to perform a hydrophilic treatment, and then immersed in a tin chloride sensitizing solution and a palladium chloride activation solution. Next, electroless plating solution for room temperature nickel/porous wood type (bath temperature 60℃)
A conductive base layer for electrolytic plating was obtained by immersing it in water for 4 minutes.

The composition of this room temperature electroless plating bath is as follows.

Nl50.6H208,3g/1 NaP2O7,H2017g/1 (CH3)2NHBH30,5g/1 pH (adjusted with ammonia) 10.3 The conductive base layer obtained above has a translucent and completely metallic mirror surface. Many. The resistance between the inner and outer circumferences was approximately 30Ωf. next,
Electrolytic nickel plating was performed using sulfamic acid nickel solution to deposit 0.25 mm of nickel. Bath temperature is 30℃,
prH is 4.0 initial current density is 0.03 ampere/dm
It is.

When the nickel surface was separated from the resin surface and the groove shape was observed, it was found that grooves that accurately corresponded to the groove shape of the glass master disk were obtained.

・[Example 2] From an optical disc video record master in which information bits and guide grooves were formed on a glass substrate from a radius of 3 cm to a position of 14 cm, ultraviolet curable resin H8D-1 manufactured by Dainippon Ink and Chemicals was used. , an information pattern was transferred onto a glass substrate carrier.

This was subjected to hydrophilization treatment, sensitization treatment, and activation treatment in the same manner as in Example 1. Next, it was immersed in a room temperature nickel phosphorus type electroless plating solution (bath temperature 30° C.) for 6 minutes to form a conductive base layer for electrolytic plating. The composition of this room temperature electroless plating bath is as follows.

NIC12・6H207, 1g/l NaH2PO2, H2O3, 3g/1 Na4P207・110H2O17/lN H40H(
58wt, liquid solution) 3.5 CC/l The conductive base layer obtained above was semitransparent and did not have a perfect metal mirror surface. The resistance between the inner and outer circumferences was approximately 800Ω. Next, in the same manner as in Example 1, electrolytic nickel plating was performed, the nickel surface was separated from the resin surface, and the information pattern shape was observed. It was found that an information pattern that accurately corresponded to the information pattern shape on the glass master was obtained. Ta.

[Example 5] A solution of acetyl cellulose, ethyl cellulose, methyl cellulose, flobyl cellulose, and butyl cellulose was applied to an optical disk memory master disk in which information pits and guide grooves were formed on a glass substrate from a radius of 4 cm to a position of 14 cm. After each solvent was dried, the information pattern was transferred onto a glass substrate carrier using ultraviolet curable resin E-15 manufactured by Dainichiseika Chemical Co., Ltd. as an adhesive. This was subjected to hydrophilization treatment, sensitization treatment, and activation treatment in the same manner as in Example 1. Next, electroless cobalt plating solution for room temperature (Jiri 3
0° C.) for 5 minutes to form a conductive base layer for electrolytic plating. The composition of this room temperature electroless plating bath is as follows.

Na4P2.0. , 10H2012g/1CO8O4
・7H209, 1g/l NHOH (58wt, chili liquid) 1.3 CC/
1(CH,,)2NHBH, 0.3 g/l The conductive base layer obtained above was semitransparent and did not have a perfect metallic mirror surface. The resistance between the inner and outer circumferences was approximately 60Ω. next,
As in Example 1, electrolytic plating was performed, the cobalt surface was separated from the resin surface, and the information pattern shape was observed.
An information pattern that accurately corresponds to the information pattern shape of the glass master disk was obtained.

[Example 4] Electroless nickel plating on the same adherend as in Example 1 was investigated using a spray method. Liquid temperature is 30℃, application time is 6
The composition of the liquid is as follows.

Nickel liquid: N1Cl ・6I] 2050 g
/1 NHCl 50 g/1 Reducing liquid: Na B H41 g / 13 NaO
H4g/1 p)I 12 The conductive base layer obtained above was semitransparent and did not have a perfect metallic mirror surface. The resistance between the inner and outer circumferences was about 40Ω. Next, electrolytic nickel plating was performed in the same manner as in Example 1, and the results were as good as in Example 1.

[Comparative example]

When the same study as in Example 1 was conducted and the immersion time in the electroless nickel plating solution was set to 8 minutes, cracks and peeling occurred in the plated film on the flat part during the subsequent nickel plating.

Furthermore, when the immersion time in the electroless nickel plating solution was increased to 15 minutes, cracks and peeling had occurred in the nickel film on the flat portions at this point. These conductive base layers for electrolytic plating had a perfect metal mirror surface.

As described above, according to the present invention, it is possible to stably obtain a metal master mold for replicating a plate-like object having unevenness information with an accurate transfer pattern, and to obtain an extremely good metal mold for the next process. Can you provide the mother mold?

[Brief explanation of the drawing]

The drawing is a chart showing the dependence of the resistance value between the inner and outer circumferences of the disk on the electroless nickel plating time when the present invention is implemented. Representative Patent Attorney Junnosuke Nakamura, Chisel 1 #≦, 2' Furume Yarrow Imai (cold) Continued from page 1 0 Author Hirokai Miwa 292 Yoshida-cho, Totsuka-ku, Yokohama City Hitachi Co., Ltd. Inside the Production Technology Research Institute

Claims (1)

[Scope of Claims] (1) For reproduction of an uneven information pattern formed by transferring an uneven information pattern formed on the surface of a hard plate-like object such as glass to the surface of an ultraviolet curable resin or a soluble resin. A method for manufacturing a metal matrix, in which the resin surface is sensitized and activated to form activated metal nuclei on the surface, and then nickel or cobalt is electrolessly plated on the activated surface at about room temperature. A conductive film for electrolytic plating is obtained, and further nickel electroplating is performed to obtain a metal body, and the metal body is separated at the interface with the activated surface to form the uneven information. A method for producing a metal matrix for replicating a plate-like object having uneven information, characterized by forming a negative matrix of a pattern. (2. In the method for manufacturing a metal matrix for replicating a plate-like object having unevenness information as set forth in claim 1, the electroless plating is stopped at a stage before a perfect metal mirror surface is obtained. (b) In the method for manufacturing a metal matrix for replicating a plate-like body having unevenness information as set forth in claim 1, A method for manufacturing a metal master mold for replicating a plate-like object having uneven information, characterized in that the curable resin is an organic material having a carbon-carbon double bond. (4) Claim 1. 1. A method for producing a metal matrix for replicating a plate-like body having unevenness information, characterized in that the soluble resin is a cellulose-based polymer substance. (5) In the method for manufacturing a metal matrix for replicating a plate-like body having unevenness information according to claim 1, the soluble resin is at least one of acetyl cellulose, ethyl cellulose, methyl cellulose, propyl cellulose, and butyl cellulose. 1. A method for manufacturing a metal matrix for replicating a plate-like object having unevenness information, characterized in that it is made of a single resin.