JP2009068106A - Method for manufacturing polymer base material having metallic film, and polymer base material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a polymer base material having a metallic film excellent in adhesion property, and to provide the polymer base material. <P>SOLUTION: The method for manufacturing the polymer base material having the metallic film comprises: (1) a step of subjecting the surface of a UV curing type acrylic resin on a transparent polymer substrate to plasma treatment; and (2) a step of forming the metallic film by an electroless plating method on the UV curing type acrylic resin subjected to the plasma treatment. The polymer base material is obtained by this method. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a polymer substrate having a metal film and a polymer substrate.

  Polymer materials are inexpensive compared to metal and glass materials, have many advantages of being light and having good rigidity, excellent workability, being chemically stable and having good corrosion resistance. Therefore, recently, it is used for various uses as a material replacing metal and glass.

  In particular, by coating the surface of the polymer material with metal wiring, it is possible to add a metal function to the polymer material.

  For example, for semiconductor devices, semiconductor device mounting components, various panel display devices, IC cards, optical devices, etc., resin members having a resin base material with patterned metal fine lines formed on the surface, such as multilayer circuit boards, are used. It has been.

  In addition, a biochip used for analysis of microorganisms or the like uses a glass member having a patterned metal fine line formed on the surface thereof, but has a drawback that glass is fragile and poor in safety. Furthermore, it is difficult to incinerate glass biochips once exposed to microorganisms and the like, and there is a need for transparent plastic disposable products.

  Moreover, if a patterned metal fine line can be formed with respect to a transparent polymer material, application to various panel display parts etc. in which transparency is required can be expected.

For example, Patent Document 1 reports a method of forming a metal film on a transparent plastic substrate, but this method has failed to laminate a metal film with a polymer material with good adhesion. .
Special table 2004-519559 gazette

  An object of the present invention is to provide a method for producing a polymer substrate having a metal film and a polymer substrate.

  As a result of intensive studies to solve the above problems, the inventors of the present invention performed plasma treatment on the surface of the ultraviolet curable acrylic resin on the transparent polymer substrate, and then performed metal plating on the resin surface to thereby obtain a metal. It has been found that a polymer base material having a film laminated with good adhesion can be obtained.

  Furthermore, it has been found that by performing lithography treatment and etching treatment on the polymer substrate having the metal coating layer, the metal coating can be removed according to the lithography pattern to form fine metal lines on the polymer substrate. The polymer substrate having the metal fine line maintains the original transparency of the ultraviolet curable acrylic resin and the transparent polymer substrate, and is extremely excellent in adhesion of the metal fine line to the ultraviolet curable acrylic resin. . The present invention has been completed based on such findings and further studies.

This invention relates to the manufacturing method and polymer base material of a polymer base material which have a metal membrane | film | coat shown to the following items 1-10.
Item 1. (1) A step of plasma-treating the surface of the ultraviolet curable acrylic resin on the transparent polymer substrate, and (2) a step of forming a metal film by an electroless plating method on the surface of the ultraviolet curable acrylic resin subjected to the plasma treatment. A method for producing a polymer substrate having a metal film characterized by comprising:
Item 2. (1) Plasma treatment of the ultraviolet curable acrylic resin surface on the transparent polymer substrate,
(2) A step of forming a metal film by an electroless plating method on the surface of the ultraviolet curable acrylic resin subjected to plasma treatment,
(3) Producing a polymer substrate having a patterned metal fine line characterized by comprising a step of forming a resist pattern on a metal film by lithography and (4) a step of forming a metal pattern by etching. Method. Item 3. Item 3. The method according to Item 1 or 2, wherein the ultraviolet curable acrylic resin is obtained by ultraviolet curing a urethane acrylate, epoxy acrylate, or a mixture of urethane acrylate and epoxy acrylate.
Item 4. Item 4. The production method according to any one of Items 1 to 3, wherein the metal film is a copper film, a nickel film, a palladium film, a tin film, a tungsten film, a cobalt film, or an alloy film thereof. Item 5. Item 5. The production method according to any one of Items 1 to 4, wherein the transparent polymer substrate comprises a methacrylic resin, a polycarbonate resin, a vinyl chloride resin, a styrene resin, or a cellulose resin.
Item 6. Item 6. The manufacturing method according to any one of Items 1 to 5, wherein the plasma treatment is performed in a vacuum chamber maintained at a pressure of 760 Torr to 5 × 10 ⁻⁴ Torr and a temperature of 5 to 70 ° C.
Item 7. Item 7. The manufacturing method according to any one of Items 2 to 6, wherein the lithography process is a process using UV light or an electron beam.
Item 8. Item 8. The manufacturing method according to any one of Items 2 to 7, wherein the etching process uses a wet method or a dry method.
Item 9. A polymer substrate having a metal film on the surface of an ultraviolet curable acrylic resin on a transparent polymer substrate.
Item 10. Item 10. The polymer substrate according to Item 9, wherein the metal film is a patterned metal fine line.

  According to the present invention, a metal film can be laminated with good adhesion on the surface of an ultraviolet curable acrylic resin on a transparent polymer substrate. Furthermore, by performing lithography treatment and metal etching treatment on the transparent polymer substrate having the metal film, fine metal lines can be formed on the polymer substrate according to the lithography pattern. The transparent polymer substrate having fine metal lines maintains the original transparency of the ultraviolet curable acrylic resin and the transparent polymer substrate, and is excellent in adhesion of the fine metal lines to the resin substrate. Accordingly, the polymer substrate of the present invention is a biochip (electrophoretic electrode, flow path) used for analysis of microorganisms, semiconductor devices, semiconductor device mounting components, various panel display units requiring transparency, IC cards, and optical devices. It can be effectively used as a resin member having a resin base material having a patterned metal fine line formed on the surface thereof, such as a multilayer circuit board such as a printed wiring board used in the invention.

The manufacturing method of a polymer base material which has a metal film of this invention has the following process (1) and (2).
(1) A step of performing plasma treatment on the surface of the ultraviolet curable acrylic resin on the transparent polymer substrate, and (2) a step of forming a metal film on the surface of the ultraviolet curable acrylic resin subjected to the plasma treatment by an electroless plating method.
Hereinafter, each step will be described.

Process (1)
In the step (1) of the present invention, plasma treatment is performed on the surface of the ultraviolet curable acrylic resin laminated on the transparent polymer substrate.

  The polymer material for forming the transparent polymer substrate of the present invention is not particularly limited as long as it can be used as a transparent substrate. For example, a methacrylic resin, a polycarbonate resin, a vinyl chloride resin, a styrene resin, or a cellulose resin can be used. Among these, polycarbonate resins are preferable.

  The thickness of the transparent polymer substrate may be appropriately selected according to the required strength, transparency, etc., and is, for example, about 0.1 to 5 mm, preferably about 0.3 to 3 mm, more preferably 0.5 to It is about 1.5 mm.

  The ultraviolet curable acrylic resin of the present invention is obtained by causing radical polymerization of urethane acrylate, epoxy acrylate, a mixture of urethane acrylate and epoxy acrylate, and the like by irradiation with energy such as ultraviolet rays and curing.

  Commercially available products such as urethane acrylate, epoxy acrylate, and a mixture of urethane acrylate and epoxy acrylate, which are raw materials for the ultraviolet curable acrylic resin of the present invention, may be purchased, and may be obtained by a conventionally known method.

  Examples of the method for producing urethane acrylate include a method in which a terminal isocyanate prepolymer obtained from a polyol compound and an isocyanate compound is reacted with an acrylate having a hydroxyl group.

  Examples of the polyol compound include polyether polyols, polyester polyols, copolymers of acrylic acid esters and hydroxyethyl (meth) acrylate, and the like. Examples of the polyether polyol include polyoxytetramethylene glycol. Examples of the polyester polyol include polyadipate polyol and polycarbonate polyol. These polyol compounds can be obtained by a conventionally known method, and commercially available products may be purchased.

  Examples of the isocyanate compound include adducts of methylene bis (p-phenylene diisocyanate), hexamethylene diisocyanate / hexanetriol, hexamethylene diisocyanate, tolylene diisocyanate, tolylene diisocyanate trimethylolpropane, and 1,5-naphthylene diisocyanate. Nate, thiopropyl diisocyanate, ethylbenzene-2,4-diisocyanate, 2,4-tolylene diisocyanate dimer, hydrogenated xylylene diisocyanate, tris (4-phenyl isocyanate) neophosphate and the like. These isocyanate compounds can be obtained by a conventionally known method, and commercially available products may be purchased.

  Examples of the acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and polyethylene glycol acrylate.

  Moreover, in the ultraviolet curable acrylic resin of this invention, when using what hardened urethane acrylate with the ultraviolet-ray etc., by using together the polyfunctional monomer of the acrylate which has a hydroxyl group, the ultraviolet curable acrylic resin of this invention ( Hardness can be further imparted to the hard coat layer).

  Examples of the polyfunctional monomer of an acrylate having a hydroxyl group include trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) Examples include acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.

  Examples of the epoxy acrylate used as the raw material for the ultraviolet curable acrylic resin of the present invention include, for example, bixylenol type, bisphenol type epoxy resins or mixtures thereof, heterocyclic epoxy resins having an isocyanate skeleton, and bisphenol A type. Epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated phenol novolak type epoxy resin, glycidylamine type epoxy resin (for example, Tetraglycidyldiaminodiphenylmethane), hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac type epoxy Resins, tetraphenylolethane type epoxy resins, glycidyl phthalate resins, tetraglycidyl xylenoyl yl ethane resins, naphthalene group-containing epoxy resin, may be used an epoxy resin having a dicyclopentadiene skeleton. These epoxy acrylates may be used alone or in combination of two or more.

  On the other hand, an acrylic resin that is usually used (also used in Patent Document 1 above) is a resin comprising a methyl methacrylate (methyl methacrylate = MMA) polymer or a copolymer of methyl methacrylate and an acrylic ester (acrylate). It is.

  The ultraviolet curable acrylic resin used in the present invention and the commonly used acrylic resin such as methyl methacrylate are completely different resins in terms of chemical structure, physical properties and the like. The ultraviolet curable acrylic resin used in the present invention has more reactive points (functional groups) that are susceptible to plasma treatment than ordinary acrylic resins. Therefore, when plasma treatment is performed, the wettability (hydrophilicity) of the surface of the ultraviolet curable acrylic resin is improved, and the active points for easily depositing the plating metal are increased. In the present invention, a transparent polymer material having a metal film with good adhesion can be obtained by forming a metal film on the surface of the ultraviolet curable acrylic resin subjected to plasma treatment.

  The thickness of the ultraviolet curable acrylic resin used in the present invention may be appropriately selected according to the required strength, transparency, and the like. For example, it is usually about 0.1 to 300 μm, preferably about 0.5 to 200 μm. More preferably, it is about 1 to 100 μm.

  A transparent polymer substrate having an ultraviolet curable acrylic resin layer may be purchased commercially, or urethane acrylate, epoxy acrylate, a mixture of urethane acrylate and epoxy acrylate, etc. on the transparent polymer substrate by a known method. You may use what was obtained by apply | coating, making radical polymerization by energy irradiation, such as an ultraviolet-ray, and making it harden | cure.

  That is, in the present invention, before the step (1), there is provided a step (0) of applying the ultraviolet curable acrylic resin raw material on the transparent polymer substrate, causing radical polymerization by irradiation of energy such as ultraviolet rays, and curing. May be.

  As a method for producing a transparent polymer substrate having an ultraviolet curable acrylic resin layer, for example, a single wafer type in which an ultraviolet curable acrylic resin layer (hard coat layer) is formed for each transparent polymer substrate film (polycarbonate film, etc.) And a continuous type in which a hard coat layer is continuously formed on a long transparent polymer substrate and wound into a roll.

  When the hard coat layer is formed by a single wafer method, there are dip coating, spin coating, spraying methods and the like as coating methods. Further, in the continuous type, an improvement in productivity and a cost reduction effect by reducing the thickness of the polycarbonate film are expected. Furthermore, in the continuous type, since the hard coat layer is continuously formed, the state in which the transparent polymer substrate is in contact with the hard coat agent in a solution state is short, and the solvent in which the transparent polymer substrate is soluble as a diluting solvent for the hard coat agent Can also be used.

  In the plasma treatment in the step (1), only the ultraviolet curable acrylic resin surface on the transparent polymer substrate is selectively plasma treated.

  For the generation of plasma, for example, at least one selected from the group consisting of oxygen, nitrogen, and argon may be used, and among these, oxygen is preferably used.

The plasma treatment is usually performed in a vacuum chamber maintained at a pressure of 760 Torr (atmospheric pressure) to 5 × 10 ⁻⁴ Torr and a temperature of 5 to 70 ° C. Among these, it is preferably carried out in a vacuum chamber maintained at a pressure of 760 Torr to 0.01 Torr and a temperature of 15 to 40 ° C., more preferably a pressure of 1 Torr to 0.01 Torr and a temperature of 20 to 30 ° C.

  The plasma treatment is usually preferably performed at a generated power of about 100 to 1000 W for about 5 to 30 minutes, preferably at a generated power of about 400 to 600 W for about 10 to 20 minutes.

In addition, it is preferable to dehydrate the transparent polymer substrate having the ultraviolet curable acrylic resin layer before performing the plasma treatment. The dehydration treatment is usually performed in a vacuum dryer maintained at a pressure of about 1 × 10 ⁵ Pa to ¹ × 10 ¹ Pa and at a temperature of about 60 to 110 ° C. for about 30 to 80 hours, preferably a pressure of 1 × 10 ⁴ Pa to 1 ×. What is necessary is just to carry out about 45 to 60 hours with the vacuum dryer maintained at about 10 < ² > Pa and the temperature about 80-100 degreeC.

Step (2)
The step (2) of the present invention is a step of forming a metal film by an electroless plating method on the surface of the ultraviolet curable acrylic resin subjected to the plasma treatment in the above step (1).

  When forming a metal film by the electroless plating method, a plating catalyst such as silver, palladium, zinc or cobalt is attached on the surface of the ultraviolet curable acrylic resin, and the surface of the ultraviolet curable acrylic resin is activated with an activation liquid. It is common to activate.

  The method for depositing the plating catalyst and activating the catalyst is not particularly limited, and a known method may be employed. For example, an alkaline aqueous solution such as an aqueous potassium permanganate solution or an aqueous sodium permanganate solution is brought into contact with the surface of the ultraviolet curable acrylic resin, and then neutralized and reduced with an acidic aqueous solution such as a mixed solution of hydroxyamine sulfate and sulfuric acid, Next, the surface of the ultraviolet curable acrylic resin is dissolved in a metal compound such as silver, palladium, zinc or cobalt, or a salt or complex of these metal compounds in water, alcohol, chloroform or the like at a concentration of about 0.001 to 10% by weight. For example, a method of reducing the catalyst metal after dipping in the solution (which may contain an acid, an alkali, a complexing agent, a reducing agent, etc., if necessary) may be mentioned.

  The metal film deposited by electroless plating is not particularly limited, and examples thereof include a copper film, a nickel film, a palladium film, a tin film, a tungsten film, a cobalt film, and an alloy film thereof. Among these, a copper film, a cobalt film, a nickel film, and a nickel-tungsten film are preferable from the viewpoint of adhesion, and a nickel film is particularly preferable. Further, the cobalt coating is excellent in terms of wear resistance and antibacterial properties, the nickel-tungsten coating is excellent in wear resistance and corrosion resistance, and the nickel coating is excellent in terms of heat resistance, wear resistance, releasability, and electrical conductivity.

  As an electroless plating solution used for electroless plating, a conventionally known autocatalytic electroless plating solution may be used. For example, electroless nickel-phosphorous plating solution containing sodium hypophosphite as a reducing agent, electroless nickel-boron plating solution containing amine borane, dimethylamine borane, etc., reducing agent, ammonium hypophosphite, hypophosphorous acid Electroless copper plating solution, electroless palladium plating solution using sodium borohydride, hydrazine, formalin, etc. as a reducing agent, electroless palladium-phosphorous plating solution, reducing electroless gold plating using sodium hypophosphite, etc. Solution, electroless silver plating solution, hydrazine, electroless nickel-cobalt-phosphorous plating solution using sodium hypophosphite as a reducing agent, electroless nickel-tungsten plating solution using hypophosphorous acid etc. as reducing agent, hydrazine Electroless cobalt plating solution, electroless nickel-boron-tungsten plating solution using sodium hypophosphite as a reducing agent It can be used an electroless plating solution.

  The thickness (total thickness) of the metal film layer may be appropriately selected as necessary, but is usually about 0.05 to 5 μm, preferably about 0.05 to 3 μm, more preferably about 0.1 to 1 μm. . When the metal film layer obtained by electroless plating is used as a conductor circuit, the plating layer is preferably grown to a thickness required for the conductor circuit.

  In order to improve the adhesion between the ultraviolet curable acrylic resin surface and the metal plating layer after forming the metal plating layer on the ultraviolet curable acrylic resin surface by the electroless plating method of step (2), a metal The polymer substrate on which the film is formed is about 50 to 110 ° C., preferably about 80 to 100 ° C. using an oven or the like, about 0.1 to 10 hours, preferably about 0.1 to 5 hours, Heat treatment is preferable.

  The heat treatment is preferably performed in an inert gas atmosphere such as nitrogen or argon. Furthermore, you may pressurize the polymer base material in which the metal film was formed with the press plate etc. at the time of heat processing as needed.

  Through the above steps (1) and (2), the metal film can be laminated with good adhesion on the surface of the ultraviolet curable acrylic resin on the transparent polymer substrate.

  The polymer base material of the present invention having a metal film on the surface of the ultraviolet curable acrylic resin on the transparent polymer substrate obtained by the step (1) and the process (2) has the metal film adhered to the ultraviolet curable acrylic resin. Therefore, a metal fine line can be formed by performing the following steps (3) and (4). Hereinafter, steps (3) and (4) will be described.

Process (3)
The step (3) of the present invention is a step of applying a resist on the metal film after the steps (1) and (2) and forming a resist pattern (opening) by lithography.

  The resist pattern is formed by a method of applying a UV mask for forming a desired pattern by a UV lithography technique or a method of forming a necessary pattern on a resist by a direct drawing technique using an electron beam, a laser, or the like. be able to.

  The resist used in step (3) is not particularly limited, and either a positive resist or a negative resist can be used. Furthermore, either liquid type or dry film type resists can be used.

  In a positive resist, a resist region exposed to UV light, an electron beam or the like is decomposed and becomes soluble in a developer. In a negative resist, a resist region exposed to UV light, an electron beam or the like is cured and becomes insoluble in a developer.

  After exposing the resist to UV light, electron beam, etc., the polymer substrate is immersed in a suitable developer. By this developer, the region where the resist is exposed to UV light, electron beam or the like (in the case of a positive resist), or the region where the resist is not exposed to UV light, electron beam or the like (in the case of a negative resist) is selected selectively. And an opening is formed in the polymer substrate.

Process (4)
In step (4) of the present invention, unnecessary metal film is removed by etching the metal film using the openings formed by the resist pattern in step (3), and then resist film This is a step of forming a desired metal pattern by removing.

  The etching process may be either a wet etching process or a dry etching process.

  In the formation of the metal pattern by the wet etching process, an unnecessary nickel film can be removed by immersing in a heated nitric acid / ferric chloride mixed aqueous solution. The nitric acid concentration in the nitric acid / ferric chloride mixed aqueous solution is usually about 5 to 30%, preferably about 10 to 20%, and the ferric chloride concentration is usually about 1 to 20%, preferably 3 About 10%.

  When the metal pattern is formed by wet etching, the immersion temperature is usually about 40 to 80 ° C., preferably about 50 to 70 ° C., and the immersion time is usually about 10 seconds to 5 minutes, preferably 30 seconds to 2 It is preferable to set it to about a minute.

  Examples of the method for removing the resist film include a method of immersing the resist film in an aqueous sodium hydroxide solution. The concentration of the aqueous sodium hydroxide solution is, for example, about 1 to 20%, preferably about 5 to 10%. The immersion temperature when removing the resist film is usually about 20 to 60 ° C., preferably about 30 to 50 ° C., and the immersion time is usually about 10 seconds to 5 minutes, preferably about 30 seconds to 2 minutes. Good.

  When forming a metal pattern by dry etching, unnecessary metal film is removed by applying argon plasma to the metal film from the opening, and then unnecessary resist is removed by changing the argon plasma conditions. By doing so, a desired metal pattern is obtained. In the dry etching process, unnecessary resist may be removed by a method using sodium hydroxide or the like.

  By the above steps (1) to (4), the polymer substrate of the present invention having a patterned metal fine line can be obtained (see FIGS. 1 and 2).

  The transparent polymer base material having the metal fine line of the present invention thus obtained maintains the original transparency of the ultraviolet curable acrylic resin and the transparent polymer substrate, and is compatible with the resin base material of the metal fine line. Excellent adhesion. Accordingly, the polymer substrate of the present invention is a biochip (electrophoretic electrode, flow path) used for analysis of microorganisms, semiconductor devices, semiconductor device mounting components, various panel display units requiring transparency, IC cards, and optical devices. It can be effectively used as a resin member having a resin base material having a patterned metal fine line formed on the surface thereof, such as a multilayer circuit board such as a printed wiring board used in the invention.

Polymer substrate The polymer substrate of the present invention obtained by the above steps (1) to (2) has a metal film layer on the surface of the ultraviolet curable acrylic resin layer on the transparent polymer substrate.

  Furthermore, the polymer base material having the patterned metal fine line of the present invention obtained by the above steps (1) to (4) has a patterned metal fine line on the surface of the ultraviolet curable acrylic resin layer on the transparent polymer substrate. Have.

  The ultraviolet curable acrylic resin used in the present invention has more reactive points (functional groups) that are susceptible to plasma treatment than ordinary acrylic resins. Therefore, when plasma treatment is performed, the wettability (hydrophilicity) of the surface of the ultraviolet curable acrylic resin is improved, and the active points for easily depositing the plating metal are increased. In the present invention, a transparent polymer material having a metal film with good adhesion can be obtained by forming a metal film on the surface of the ultraviolet curable acrylic resin subjected to plasma treatment.

  The thickness of the transparent polymer substrate may be appropriately selected according to the required strength, transparency, etc., and is, for example, about 0.1 to 5 mm, preferably about 0.3 to 3 mm, more preferably 0.5 to It is about 1.5 mm.

  The thickness of the ultraviolet curable acrylic resin layer may be appropriately selected according to the required strength, transparency, and the like. For example, the thickness is about 0.1 to 300 μm, preferably about 0.5 to 200 μm, more preferably 1. It is about ~ 100 μm.

  The thickness of the metal film may be appropriately selected as necessary, but is usually about 0.05 μm to 5 μm, preferably about 0.05 μm to 3 μm, more preferably about 0.1 μm to 1 μm.

  The shape, size (width), and the like of the metal fine line can be appropriately selected according to the purpose by the lithography process and the etching process in the steps (3) and (4).

  According to the manufacturing method of the said process (1)-(4) of this invention, since a metal membrane | film | coat can be formed with sufficient adhesiveness on an ultraviolet curable acrylic resin, it is transparent with a very fine pattern-shaped metal wire. A polymer substrate is obtained. Since the metal fine line obtained by the production method of the present invention is excellent in adhesion to the polymer material, a thin metal fine line having a width of, for example, about 10 μm can be obtained.

  In addition, since the polymer base material having the patterned metal fine line of the present invention can maintain the transparency inherent in the ultraviolet curable acrylic resin and the transparent polymer substrate, the part where the patterned metal fine line is not formed. The transparency of is extremely high. Therefore, the polymer substrate of the present invention is a multilayer circuit such as a biochip (electrophoretic electrode, flow path) used for analysis of microorganisms, semiconductor devices, semiconductor device mounting components, IC cards, printed wiring boards used for optical devices, etc. In addition to being used for substrates and the like, it can also be effectively used as various panel display units that require high transparency.

  The present invention will be further clarified by the following examples, comparative examples and test examples of polymer base materials for producing a polymer base material having a metal film of the present invention. However, the present invention is not limited to these. It is not something.

Example 1 (Preparation of nickel film)
A polycarbonate substrate having a urethane acrylate layer (ultraviolet curable acrylic resin layer) (ECF100H1: manufactured by Chuchu Plastic Industry Co., Ltd., the size of the polycarbonate substrate is 55 mm × 80 mm × 1 mm (thickness)), an ultrasonic cleaner (42 KHz) Was used for 10 minutes in ethanol and in pure water. After washing, the polycarbonate substrate was dried with a vacuum dryer at a pressure of 1 × 10 ³ Pa and 90 ° C. for 48 hours.

  Next, using an oxygen plasma apparatus (manufactured by Hirano Kotone Co., Ltd. (power supply 13.56 MHz)) at a pressure of 0.2 Torr (26.66 Pa) and an output of 500 W for 10 minutes, plasma treatment of the ultraviolet curable resin surface Was done.

Next, it was immersed in a neutral degreasing agent (OPC Clean 65 aqueous solution (700 ml / L) manufactured by Okuno Pharmaceutical Co., Ltd.) at 35 ° C. for 5 minutes. After soaking, it was washed with pure water and immersed in a sulfuric acid aqueous solution (10%) for 2 minutes, and further washed with pure water using an ultrasonic cleaner UT-305H (35 KHz) for 2 minutes.

  After washing, it was immersed in a surface conditioner (Condenser FR aqueous solution (50 ml / L) manufactured by Okuno Pharmaceutical Co., Ltd.) at 40 ° C. for 5 minutes and washed with pure water. Furthermore, it was immersed in a pre-dip agent (OPC-SAL aqueous solution (50 g / L) manufactured by Okuno Pharmaceutical Co., Ltd.) for 1 minute, and a catalyst application solution (OPC-80 Catalyst M (100 ml manufactured by Okuno Pharmaceutical Co., Ltd.) (100 ml / L)), a non-hydrochloric acid additive (OPC-SAL (260 g / L) manufactured by Okuno Pharmaceutical Co., Ltd.) and an aqueous solution containing 35% hydrochloric acid at 35 ° C. for 6 minutes.

  After soaking, it was immersed in a catalyst activator (Okuno Pharmaceutical Co., Ltd. ITO accelerator aqueous solution (200 ml / L)) at 25 ° C. for 5 minutes. After immersion, rinse with pure water and immerse in electroless nickel plating solution (electroless nickel solution top Nicolon TOM-S 200ml / L aqueous solution (200ml / L) manufactured by Okuno Pharmaceutical Co., Ltd.) for 15 minutes at 65 ° C did. After electroless nickel plating, it was washed with pure water and heated and dried at 90 ° C. for 60 minutes. As a result, a nickel film having a thickness of 0.2 μm was formed.

  The obtained nickel film had good adhesion, and the nickel film was not peeled at all by a tape peeling test according to JIS D0202-1988. The results are shown in Table 1.

Example 2 (Preparation of copper film)
A polycarbonate (hereinafter PC) substrate ECF100H1 manufactured by Sumitomo Bakelite Co., Ltd. was washed with ethanol for 10 minutes with an ultrasonic cleaner (42 KHz). Next, it was cleaned for 10 minutes with an ultrasonic cleaner (42 KHz) using pure water. It vacuumed with the vacuum dryer and dried at 90 degreeC x 48 hours.

  Next, a vacuum was applied to 0.2 torr (26.66 Pa) with an oxygen plasma apparatus (power supply: 13.56 MHz) manufactured by Hirano Kotone Co., Ltd., and oxygen treatment was performed, and plasma treatment was performed for 500 W × 10 minutes.

  Next, it was immersed in a 700 ml / L aqueous solution of OPC Clean 65 manufactured by Okuno Pharmaceutical Co., Ltd. at 35 ° C. for 5 minutes. It was washed with pure water and immersed in a 10% aqueous solution of sulfuric acid for 2 minutes. Washing was performed for 2 minutes with an ultrasonic cleaner UT-305H (35 KHz) using pure water.

  After washing, it was immersed in an aqueous solution of a 50 ml / L Condizer FR manufactured by Okuno Pharmaceutical Co., Ltd. at 40 ° C. for 5 minutes. It was washed with pure water and immersed in an aqueous solution of OPC-SAL 50 g / L manufactured by Okuno Pharmaceutical Co., Ltd. for 1 minute.

  Then, it was immersed in a mixed aqueous solution of OPC-80 Catalyst M 100 ml / L manufactured by Okuno Pharmaceutical Co., Ltd., OPC-SAL 260 g / L manufactured by Okuno Pharmaceutical Co., Ltd. and 150 ml / L of 35% hydrochloric acid for 6 minutes at 35 ° C. It was immersed in an aqueous solution of ITO accelerator 200 ml / L manufactured by Okuno Pharmaceutical Co., Ltd. at 25 ° C. for 5 minutes. Washed with pure water and immersed in a mixed aqueous solution of electroless copper solution ATS Adcapper IW-A50ml / L, ATS Adcapper IW-M80ml / L and ATS Adcapper C10ml / L manufactured by Okuno Pharmaceutical Co., Ltd. at 30 ° C for 15 minutes . When washed with pure water and dried in a dryer at 90 ° C. for 60 minutes, a copper film having a thickness of 0.3 μm was formed.

Example 3 (Preparation of nickel-tungsten film)
A polycarbonate (hereinafter PC) substrate ECF100H1 manufactured by Sumitomo Bakelite Co., Ltd. was cleaned with ethanol using an ultrasonic cleaner (42 KHz) for 10 minutes. Washing was performed for 10 minutes with an ultrasonic cleaner (42 KHz) using pure water. It vacuumed with the vacuum dryer and dried at 90 degreeC x 48 hours.

  A vacuum was applied to 0.2 torr (26.66 Pa) with an oxygen plasma apparatus (power supply: 13.56 MHz) manufactured by Hirano Kotone Co., Ltd., oxygen substitution was performed, and plasma treatment was performed for 500 W × 10 minutes.

  Next, it was immersed in a 700 ml / L aqueous solution of OPC Clean 65 manufactured by Okuno Pharmaceutical Co., Ltd. at 35 ° C. for 5 minutes. It was washed with pure water and immersed in a 10% aqueous solution of sulfuric acid for 2 minutes. Ultrasonic cleaner UT-305H (35 KHz) was washed with pure water for 2 minutes.

  After washing, it was immersed in an aqueous solution of a 50 ml / L Condizer FR manufactured by Okuno Pharmaceutical Co., Ltd. at 40 ° C. for 5 minutes. It was washed with pure water and immersed in an aqueous solution of OPC-SAL 50 g / L manufactured by Okuno Pharmaceutical Co., Ltd. for 1 minute.

  Thereafter, it was immersed in a mixed aqueous solution of OPC-80 Catalyst M100 ml / L manufactured by Okuno Pharmaceutical Co., Ltd., OPC-SAL 260 g / L manufactured by Okuno Pharmaceutical Co., Ltd., and 150 ml / L of 35% hydrochloric acid for 6 minutes at 35 ° C. It was immersed in an aqueous solution of ITO accelerator 200 ml / L manufactured by Okuno Pharmaceutical Co., Ltd. at 25 ° C. for 5 minutes. It was washed with pure water and immersed in a mixed solution of electroless nickel-tungsten solution Trialloy NWP-M 96 ml / L and Trialloy NWP-R 4 ml / L manufactured by Uemura Kogyo Co., Ltd. at 65 ° C. for 15 minutes. After washing with pure water and drying with a dryer at 90 ° C. for 60 minutes, a nickel-tungsten film having a thickness of 0.3 μm was formed.

Example 4 (Preparation of nickel-cobalt film)
A polycarbonate (hereinafter PC) substrate ECF100H1 manufactured by Sumitomo Bakelite Co., Ltd. was cleaned with an ultrasonic cleaner (42 KHz) for 10 minutes using ethanol. Washing was performed for 10 minutes with an ultrasonic cleaner (42 KHz) using pure water. It vacuumed with the vacuum dryer and dried at 90 degreeC x 48 hours.

  Next, a vacuum was applied to 0.2 torr (26.66 Pa) with an oxygen plasma apparatus (power supply: 13.56 MHz) manufactured by Hirano Kotone Co., Ltd., oxygen substitution was performed, and plasma treatment was performed for 500 W × 10 minutes.

  It was immersed in a 700 ml / L aqueous solution of OPC Clean 65 manufactured by Okuno Pharmaceutical Co., Ltd. at 35 ° C. for 5 minutes. It was washed with pure water and immersed in a 10% aqueous solution of sulfuric acid for 2 minutes. Washing was performed for 2 minutes with an ultrasonic cleaner UT-305H (35 KHz) using pure water.

  After washing, it was immersed in an aqueous solution of a 50 ml / L Condizer FR manufactured by Okuno Pharmaceutical Co., Ltd. at 40 ° C. for 5 minutes. It was washed with pure water and immersed in an aqueous solution of OPC-SAL 50 g / L manufactured by Okuno Pharmaceutical Co., Ltd. for 1 minute. It was immersed in a mixed aqueous solution of OPC-80 Catalyst M 100 ml / L manufactured by Okuno Pharmaceutical Co., Ltd., OPC-SAL 260 g / L manufactured by Okuno Pharmaceutical Co., Ltd., and 150 ml / L of 35% hydrochloric acid for 6 minutes at 35 ° C. It was immersed in an aqueous solution of ITO accelerator 200 ml / L manufactured by Okuno Pharmaceutical Co., Ltd. at 25 ° C. for 5 minutes. It was washed with pure water and immersed in an electroless cobalt solution Combus-P solution manufactured by World Metal Co., Ltd. at 65 ° C. for 15 minutes. After washing with pure water and drying with a dryer at 90 ° C. for 60 minutes, a nickel-cobalt film having a thickness of 0.3 μm was formed.

Example 5 (Preparation of nickel-tungsten film)
A polycarbonate (hereinafter PC) substrate ECF100H1 manufactured by Sumitomo Bakelite Co., Ltd. was cleaned with ethanol using an ultrasonic cleaner (42 KHz) for 10 minutes. Washing was performed for 10 minutes with an ultrasonic cleaner (42 KHz) using pure water. It vacuumed with the vacuum dryer and dried at 90 degreeC x 48 hours.

  A vacuum was applied to 0.2 torr (26.66 Pa) with an oxygen plasma apparatus (power supply: 13.56 MHz) manufactured by Hirano Kotone Co., Ltd., oxygen substitution was performed, and plasma treatment was performed for 500 W × 10 minutes. It was immersed in a 700 ml / L aqueous solution of OPC Clean 65 manufactured by Okuno Pharmaceutical Co., Ltd. at 35 ° C. for 5 minutes. It was washed with pure water and immersed in a 10% aqueous solution of sulfuric acid for 2 minutes. Using pure water, the ultrasonic cleaner UT-305H (35 KHz) was washed for 2 minutes. It was immersed in an aqueous solution of Okuno Pharmaceutical Co., Ltd. Condizer FR50ml / L at 40 ° C for 5 minutes.

  After washing with pure water, it was immersed in an aqueous solution of OPC-SAL 50 g / L manufactured by Okuno Pharmaceutical Co., Ltd. for 1 minute. It was immersed in a mixed aqueous solution of OPC-80 Catalyst M100ml / L manufactured by Okuno Pharmaceutical Co., Ltd., OPC-SAL260g / L manufactured by Okuno Pharmaceutical Co., Ltd., and 150ml / L of 35% hydrochloric acid for 6 minutes at 35 ° C. It was immersed in an aqueous solution of ITO accelerator 200 ml / L manufactured by Okuno Pharmaceutical Co., Ltd. at 25 ° C. for 5 minutes. It was washed with pure water and immersed in a solution of electroless nickel-boron-tungsten solution top Nicolon PBW-S 250 ml / L manufactured by Okuno Pharmaceutical Co., Ltd. at 65 ° C. for 15 minutes. After washing with pure water and drying with a dryer at 90 ° C. for 60 minutes, a nickel-cobalt film having a thickness of 0.3 μm was formed.

Example 6 (Formation of resist pattern on nickel film)
A primer for photoresist (photoresist primer microposit manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to the substrate on which the nickel film was formed in Example 1 with a spin coater (manufactured by Kyowa Riken) (for 10 seconds). After 500rpm, 3000rpm for 20 seconds). Next, a resist (OFPR-800LB manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied with a spin coater (500 rpm for 10 seconds and then 3000 rpm for 20 seconds). The coated substrate was dried by heating at 90 ° C. for 60 minutes. The mask on which the fine pattern was arranged was allowed to stand on the resist coating surface, and was exposed for 20 seconds using an union optical exposure apparatus PER-800 (light intensity 30 mW / cm ² ). After exposure, the film was immersed in a developer (NMD-3 manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 1 minute at room temperature. Further, after washing with pure water and air drying with nitrogen, it was dried by heating at 90 ° C. for 40 minutes.

Example 7 (Wet Etching of Nickel Film)
The substrate on which the resist pattern was formed in Example 6 was immersed in a mixed aqueous solution of 15% nitric acid and 5% ferric chloride at 60 ° C. for 1 minute to dissolve and remove unnecessary nickel films. After dissolution and removal, it was washed with pure water, air-dried with nitrogen, and then heated and dried at 90 ° C. for 40 minutes.

Example 8 (Resist removal)
The substrate from which the unnecessary nickel film was removed in Example 7 was immersed in a 5% aqueous solution of sodium hydroxide at 40 ° C. for 1 minute to remove the resist. Thereafter, after washing with pure water and air drying with nitrogen, it was heated and dried at 90 ° C. for 40 minutes to obtain a polymer substrate having a patterned metal fine line. FIG. 2 shows a micrograph of the obtained polymer substrate having patterned metal fine lines.

Test example 1
The light absorbency of the transparent part (namely, the part in which the nickel pattern is not formed) from which the unnecessary nickel film was removed in Example 8 was measured. As a result, as shown in FIG. 3, the absorbance of the portion where the nickel pattern was not formed showed the same absorbance as that before the nickel film was formed.

Comparative Example 1
Acrylic substrate (SUMIPEX E ACRYLIC SHEET (methacrylic resin) manufactured by Sumitomo Chemical Co., Ltd .; thickness: 3 mm) is cleaned for 10 minutes each in ethanol and pure water using an ultrasonic cleaner (42 KHz). I did it. After washing, the polycarbonate substrate was dried with a vacuum dryer at a pressure of 1 × 10 ³ Pa and 90 ° C. for 48 hours. Next, plasma treatment was performed for 10 minutes at a pressure of 0.2 Torr (26.66 Pa) and an output of 500 W using an oxygen plasma apparatus (manufactured by Hirano Kotone Co., Ltd. (power supply 13.56 MHz)).

Next, it was immersed in a neutral degreasing agent (OPC Clean 65 aqueous solution (700 ml / L) manufactured by Okuno Pharmaceutical Co., Ltd.) at 35 ° C. for 5 minutes. After the immersion, the sample was washed with pure water, immersed in an aqueous sulfuric acid solution (10%) for 2 minutes, and further washed with pure water using an ultrasonic cleaner UT-305H (35 KHz) for 2 minutes.

  After washing, it was immersed in a surface conditioner (Condenser FR aqueous solution (50 ml / L) manufactured by Okuno Pharmaceutical Co., Ltd.) at 40 ° C. for 5 minutes and washed with pure water. Furthermore, it is immersed for 1 minute in a predip agent (OPC-SAL aqueous solution (50 g / L) manufactured by Okuno Seiyaku Kogyo Co., Ltd.), and a catalyst application solution (OPC-80 Catalyst M (100 ml / Okuno Pharmaceutical Co., Ltd.) is added. L)), a non-hydrochloric acid additive (OPC-SAL (260 g / L) manufactured by Okuno Pharmaceutical Co., Ltd.) and an aqueous solution containing 35% hydrochloric acid at 35 ° C. for 6 minutes.

  After soaking, it was immersed in a catalyst activator (Okuno Pharmaceutical Co., Ltd. ITO accelerator aqueous solution (200 ml / L)) at 25 ° C. for 5 minutes. After immersion, rinse with pure water and immerse in electroless nickel plating solution (electroless nickel solution top Nicolon TOM-S 200ml / L aqueous solution (200ml / L) manufactured by Okuno Pharmaceutical Co., Ltd.) for 15 minutes at 65 ° C did. After the electroless nickel plating, the acrylic substrate was washed with pure water. As a result, the nickel film immediately fell off and the tape peeling test could not be performed. The results are shown in Table 1.

The microscope picture of the polymer base material which has a fine pattern shape metal fine line. In the enlarged view, the bright (yellow) part is the nickel film part and the dark (brown) part is the resin part. The microscope picture of the polymer base material which has a pattern-form metal fine line. The graph which compared the light absorbency of the polymer substrate before and behind pattern formation.

Claims (10)

(1) A step of plasma-treating the surface of the ultraviolet curable acrylic resin on the transparent polymer substrate, and (2) a step of forming a metal film by an electroless plating method on the surface of the ultraviolet curable acrylic resin subjected to the plasma treatment. A method for producing a polymer substrate having a metal film characterized by comprising: (1) Plasma treatment of the ultraviolet curable acrylic resin surface on the transparent polymer substrate,
(2) A step of forming a metal film by an electroless plating method on the surface of the ultraviolet curable acrylic resin subjected to plasma treatment,
(3) Producing a polymer substrate having a patterned metal fine line characterized by comprising a step of forming a resist pattern on a metal film by lithography and (4) a step of forming a metal pattern by etching. Method. The production method according to claim 1 or 2, wherein the ultraviolet curable acrylic resin is obtained by ultraviolet curing a urethane acrylate, an epoxy acrylate, or a mixture of urethane acrylate and epoxy acrylate. The manufacturing method according to claim 1, wherein the metal film is a copper film, a nickel film, a palladium film, a tin film, a tungsten film, a cobalt film, or an alloy film thereof. The production method according to any one of claims 1 to 4, wherein the transparent polymer substrate comprises a methacrylic resin, a polycarbonate resin, a vinyl chloride resin, a styrene resin, or a cellulose resin. The manufacturing method according to claim 1, wherein the plasma treatment is performed in a vacuum chamber maintained at a pressure of 760 Torr to 5 × 10 ⁻⁴ Torr and a temperature of 5 to 70 ° C. 6. The manufacturing method according to claim 2, wherein the lithography process is a process using UV light or an electron beam. The manufacturing method according to claim 2, wherein the etching process uses a wet method or a dry method. A polymer substrate having a metal film on the surface of an ultraviolet curable acrylic resin on a transparent polymer substrate. The polymer substrate according to claim 9, wherein the metal film is a patterned metal fine line.

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