WO2006068175A1 - 導体層パターン付き基材の製造法、導体層パターン付き基材及びそれを用いた電磁波遮蔽部材 - Google Patents
導体層パターン付き基材の製造法、導体層パターン付き基材及びそれを用いた電磁波遮蔽部材 Download PDFInfo
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- WO2006068175A1 WO2006068175A1 PCT/JP2005/023483 JP2005023483W WO2006068175A1 WO 2006068175 A1 WO2006068175 A1 WO 2006068175A1 JP 2005023483 W JP2005023483 W JP 2005023483W WO 2006068175 A1 WO2006068175 A1 WO 2006068175A1
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- conductor layer
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- base material
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0001—Rooms or chambers
- H05K9/0003—Shielded walls, floors, ceilings, e.g. wallpaper, wall panel, electro-conductive plaster, concrete, cement, mortar
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- the present invention relates to a method for producing a substrate with a conductor layer pattern, a substrate with a conductor layer pattern, and an electromagnetic wave shielding member using the same, and is particularly patterned so as to have excellent conductivity and light transmittance.
- the present invention relates to a method for producing a substrate with a conductor layer pattern and a conductive substrate for adhesion, a substrate with a conductor layer pattern, a conductive substrate for adhesion, and an electromagnetic wave shielding member using the same.
- electromagnetic shielding member is required to be extremely thin, and light transmittance (transparency) and electromagnetic shielding properties contrary to this can be achieved with good tolerance. There is a demand for electromagnetic shielding members.
- a thin film conductive layer is formed by vapor-depositing a metal or metal oxide on a transparent substrate (see Patent Document 1 and Patent Document 2), Electromagnetic shielding material (see Patent Document 3 and Patent Document 4) embedded with a transparent conductive base material itself or a conductive fiber mesh with a conductive property attached, transparent conductive resin containing metal powder, etc. Electromagnetic wave shielding material printed directly on the substrate (see Patent Document 5 and Patent Document 6), electroless plating catalyst paint pattern printed on a flat substrate, and conductive layer formed by electroless plating (patent Reference 7 and Patent Reference 8), metal layer bonded on substrate An electromagnetic wave shielding layer is formed by etching the material into a mesh by the photolithographic method (see Patent Document 9).
- the method of forming a conductive layer by vapor-depositing a metal or metal oxide on a transparent substrate has a film thickness that can achieve transparency (several hundred A to 2,000 A). Since the surface resistance of the conductive layer becomes too large, the electromagnetic wave shielding property was insufficient.
- An electromagnetic wave shielding material composed of a metal mesh-attached fiber mesh or an electromagnetic wave shielding material in which a fiber mesh with conductivity is embedded in a transparent base material has a sufficiently large electromagnetic wave shielding effect!
- the fiber diameter necessary to arrange conductive fibers regularly is too large, so that the fibers can be seen (hereinafter referred to as “Visibility”). It was not suitable for display applications.
- Visibility the fiber diameter necessary to arrange conductive fibers regularly is too large, so that the fibers can be seen. It was not suitable for display applications.
- an electromagnetic wave shielding material in which a conductive fiber mesh is embedded in a transparent substrate unintentional distortion occurs between the fiber mesh and the resin board during thermal lamination in the manufacturing process, and the fluoroscopic image. Problems such as warping and cracking of the cling layer during thermal lamination, resulting in reduced electromagnetic shielding performance.
- the thickness of the fibers to which conductivity is imparted is limited to about 50 m, so that the transparency is improved and the overall thickness of the electromagnetic wave shielding sheet is reduced compared to the case where the fine diameter is difficult. There was a problem that it was difficult to do.
- Patent Document 7 a transparent resin layer is formed on a transparent substrate such as polycarbonate having a thickness of about 2 mm, and a copper mesh pattern is formed on the transparent resin layer by an electroless plating method to shield it.
- a method for producing a member it is necessary to roughen the surface of the transparent substrate in order to ensure adhesion with electroless adhesion.
- a highly toxic oxidizing agent such as chromic acid or permanganic acid must be used as a roughening means. This method is difficult to achieve a satisfactory roughening with a non-ABS fat. It becomes.
- the electromagnetic wave shielding property and transparency can be achieved by this method, it is difficult to reduce the thickness of the transparent substrate, which is not suitable as a thin film method (for example, film formation). Furthermore, if the transparent substrate is thick, it cannot be brought into close contact with the display, and this force increases the leakage of electromagnetic waves. Ma On the other hand, in terms of manufacturing, the shielding material cannot be made into a scroll or the like, which makes it bulky or suitable for automation, which increases manufacturing costs!
- Electromagnetic wave shielding members used for applications requiring transparency have a problem of poor appearance.
- electroless plating has a problem of increasing costs.
- the size of the electromagnetic wave shielding material depends on the size of the fitting line, when producing an electromagnetic wave shielding sheet having a large dimensional force of about 2 m in width, the electromagnetic wave shielding sheet 2 to the plating line 2 to It is necessary to connect the three sheets. Therefore, there is a concern that the joint force may be leaked and the shielding cannot be performed sufficiently.
- an electromagnetic wave shielding member manufactured by using a photolithographic method as described in Patent Document 9 can impart excellent electromagnetic wave shielding properties and transparency.
- a manufacturing method since it is necessary to apply a photolithographic method including an etching step for each electromagnetic wave shielding member, the number of steps increases as a whole, and there remains a problem in cost.
- a metal electrolyte is electrodeposited on an electrodeposition substrate capable of metal electrodeposition in a mesh shape, and an electromagnetic wave shielding plate is produced by adhesive transfer onto the electromagnetic wave shielding substrate via an adhesive.
- This method is described (see Patent Document 10).
- a mesh pattern is formed on an electrically conductive substrate such as a metal plate with an insulating film that inhibits electrodeposition.
- electrodeposition that enables metal electrodeposition in a mesh shape is possible. It is produced so that the part is exposed.
- the electrodeposition is on the groove.
- a photoresist is used as the insulating film, the durability of the insulating film is inferior, and the electromagnetic wave shielding plate can be repeatedly used only several times to several tens of times.
- Patent Document 10 describes a method in which a convex conductive mesh layer is formed on an insulating layer support to obtain the above-mentioned electrodeposition substrate.
- the conductive mesh is actually used.
- Metal is also electrodeposited on the sides of the metal, which becomes resistance to adhesion transfer of the mesh electrodeposited metal layer. Even if it cannot be peeled off, the mesh pattern will be broken and the electromagnetic shielding properties will be reduced. The inventors have confirmed that a failure will occur. It was.
- Patent Document 1 JP-A-1-278800
- Patent Document 2 JP-A-5-323101
- Patent Document 3 Japanese Patent Laid-Open No. 5-327274
- Patent Document 4 JP-A-5-269912
- Patent Document 5 Japanese Patent Laid-Open No. 62-57297
- Patent Document 6 JP-A-2-52499
- Patent Document 7 JP-A-5-283889
- Patent Document 8 Japanese Patent Laid-Open No. 11 170420
- Patent Document 9 JP-A-10-41682
- Patent Document 10 Japanese Patent Laid-Open No. 11 26980
- Patent Document 11 JP-A-10-29370
- Patent Document 12 JP 2000-294981 A
- Non-Patent Document 1 “Practical Medication for On-Site Engineers” edited by Japan Plating Association (published by Sakai Shoten in 1986)
- the transfer method described in Patent Document 10 is intended to solve the cost problem. I can expect.
- the electrodeposition substrate is formed on a conductive substrate such as a metal plate with a mesh pattern made of an insulating film that inhibits electrodeposition. As a result, the electrodeposited portion that can be electrodeposited in a mesh shape is exposed. It is made to make it.
- this electrodeposition substrate When this electrodeposition substrate is used, it can be used repeatedly several times to several tens of times. There is a problem that it cannot be used repeatedly several hundred times to several thousand times and cannot be mass-produced. This is because the insulating film forming the mesh pattern on the electrodeposited substrate is subjected to peeling stress by adhesion transfer, and the insulating film is peeled off from the conductive base material after a few repeated uses.
- Patent Document 10 describes a method using an electrodeposited substrate in which a convex conductive mesh layer is formed on an insulating layer support. According to this method, actually, the side surface of a conductive mesh is used. When the metal is electrodeposited, this causes resistance to the adhesion transfer of the mesh electrodeposited metal layer, and when it cannot be peeled off or even if it can be peeled off, the mesh pattern will be broken and the electromagnetic shielding properties will be reduced. A bad thing happens. Furthermore, in order to increase the production efficiency, if the current density during metal electrodeposition is increased, the insulating layer support is caused to generate heat by the convex conductive mesh layer formed on the insulating layer support. The present inventors have confirmed that problems such as thermal melting or ignition occur, and in particular, the above problem becomes more prominent as the current value applied in a large area increases.
- a baffle plate or the like is installed in the plating bath, and the current density of the mesh part and the outer peripheral part is adjusted to be uniform, so that the outer peripheral part and the mesh part have a uniform thickness.
- the current density generated in the conductive substrate is reduced as compared with the case where there is no baffle plate, so that the production speed is significantly reduced.
- the present invention relates to a method for producing a substrate with a conductor layer pattern pattern that is patterned so as to have excellent electrical conductivity and light transmittance, and a substrate with a conductor layer pattern produced by the method.
- a material and an electromagnetic wave shielding member using the same are provided.
- the present invention provides a method in which the electrodeposition substrate can withstand repeated use and is excellent in mass productivity in the transfer method.
- the purpose is to provide an efficient blackening process with less powder fall-off on the finished metal.
- the present invention also provides a method in which the metal electrodeposited and deposited in the transfer method can be easily peeled off from the electrodeposition substrate during the transfer.
- the present invention includes a step of forming a metal layer by plating on a conductive substrate having a pattern of convex portions having an upper surface and a concave portion having a geometrical shape drawn by the pattern, and the conductive layer. It is a manufacturing method of the base material with a conductor layer pattern including the process of transcribe
- the present invention provides a conductive pattern having a convex pattern having a top surface and a convex pattern in which the side surface of the convex part has an inclination angle of 30 ° or more and a geometrical figure-shaped concave portion drawn thereby.
- a method for producing a substrate with a conductor layer pattern comprising a step of forming a metal layer on a substrate by plating and a step of transferring the metal layer formed on the upper surface of the convex portion of the conductive substrate to another substrate. .
- the present invention provides a region A having a pattern of convex portions having an upper surface and a concave portion having a geometrical shape drawn by the pattern, and the area ratio of the concave portions is 50% or more and 97% or less of the whole.
- the area ratio of the recesses in the region A is larger than the area ratio of the recesses in the region B.
- the present invention is also a method of using the conductive substrate in which the area ratio of the recesses in the region B is less than 0% or less than 97% in the manufacturing method.
- the present invention provides a method for producing a substrate with a conductor layer pattern, wherein in the step of transferring the metal layer formed on the upper surface of the convex portion of the conductive substrate to another substrate, the conductive layer Of the metal layers formed on the base material, only the metal layer formed on the upper surface of the convex portion of the conductive base material is selectively transferred to another base material.
- the present invention provides the above-described method for producing a substrate with a conductor layer pattern, wherein the conductive substrate is a conductive group having a surface roughness of convex portions of 2 or less in terms of a ten-point average roughness Rz. This is a method of using wood.
- the present invention provides the above-mentioned method for producing a substrate with a conductor layer pattern, wherein the conductive substrate has a concave surface roughness of 3 or more in terms of a ten-point average roughness Rz of 3 or more. It is a method of using.
- the present invention b has a pattern of a convex part having an upper surface and a concave part having a geometrical shape drawn by the pattern, and the concave part is formed so as to be a thin film at least near the upper surface end of the convex part.
- the present invention provides the method for producing a substrate with a conductor layer pattern, wherein the surface of the metal layer formed before or after the transfer of the metal deposited on the upper surface of the convex portion of the conductive substrate is further provided. It is a method including the process of blackening.
- the present invention provides a step of forming a metal layer by fitting on a conductive substrate having a pattern of convex portions having an upper surface and a geometrically shaped concave portion drawn thereby, the conductive substrate
- the process of transferring the metal layer formed on the upper surface of the convex part to another substrate, and depositing a black alloy metal containing group VIII elements on the surface of the metal layer formed before or after transferring the formed metal layer It is a manufacturing method of the base material with a conductor layer pattern including the process of making it blacken.
- the present invention provides a region A having a pattern of convex portions having an upper surface and a concave portion having a geometrical figure drawn by the pattern, and the area ratio of the concave portions is 50% or more and 97% or less of the whole.
- a region B which has a convex pattern having an upper surface and a concave portion having a geometrical shape drawn by the convex pattern arranged on the outer side thereof, and the area ratio of the concave portion is 40% or more and less than 97% of the whole.
- the area ratio of the recesses in the region A is larger than the area ratio of the recesses in the region B.
- the insulating layer is such that the recesses in the two regions become a thin film at least near the end of the upper surface of the protrusions. It is an electroconductive base material coat
- the present invention also includes a step of forming a geometric pattern-shaped pattern on the surface of the conductive base material using a photocurable or thermosetting resin, and etching the conductive base material.
- This is a method for producing a conductive substrate for plating, which comprises a step of removing the cured resin of the photocurable resin or thermosetting resin.
- the base material with a conductor layer pattern can be obtained by transferring a metal layer formed in a pattern to a base material.
- the transfer can be easily and reliably performed.
- the base material can be a transparent base material.
- the convex pattern of the conductive base material can have a long life, and for repeated use, it can be several thousand to tens of thousands of times. It is fully compatible with mass production levels. Furthermore, the plating solution is not contaminated by contact with the conductive substrate.
- the metal pattern can be produced and peeled continuously. This further improves production efficiency.
- the total length of the conductive base material used can be lengthened, so that plating, blackening treatment, transfer, removal of residual metal by etching, etc. Since it can be performed in one process, the production efficiency is very high.
- the metal can be blackened. Thereby, the transparency without reflecting the color of the metal is improved.
- the metal remaining on the conductive substrate can be etched, removed by an adhesive film, etc. in one continuous process.
- the production efficiency becomes very high, and the remaining metal can be easily removed by transfer removal using an adhesive film. This improves the efficiency of recycling the conductive substrate.
- a transparent substrate is bonded to the surface having the conductor layer pattern of the substrate with the conductor layer pattern.
- the conductor layer pattern can be protected by coating with transparent resin.
- an adhesive layer is formed in advance on the conductor layer transfer surface of another base material, there is also an effect of preventing foreign matter from adhering to the adhesive layer.
- the transparent substrate can be bonded by pressing the transparent substrate directly or through another adhesive to the adhesive layer. In this case, since the conductor layer pattern is embedded in the adhesive layer with an appropriate pressure, it is possible to improve transparency and adhesion to the transparent substrate.
- the transparent base material with the conductor layer pattern is used to shield the electromagnetic wave having both high light transmittance (particularly, the conductor layer pattern has a small line width and high definition) and good conductivity (high shielding property).
- the body can be easily obtained. For this reason, when used as an electromagnetic wave shield for a display such as a PDP, a clear image can be comfortably viewed under almost the same conditions as in a normal state without increasing the brightness.
- the electromagnetic wave shielding body is excellent in electromagnetic wave shielding properties, it is necessary to generate a display or other electromagnetic wave, or to open a window or housing that crawls inside a measuring device, measuring device, manufacturing device, etc. that should be protected from the electromagnetic wave. The effect is great if it is used on the body, especially in parts such as windows and display surfaces where transparency is required.
- the production method of the electromagnetic wave shielding body according to the present invention is excellent in production efficiency as in the production of the conductor layer pattern.
- the smoothness of the metal layer formed on the upper surface can be improved.
- the surface roughness of the concave portion a specific size, selective transfer can be reliably performed, the surface roughness of the upper surface of the convex portion is reduced, and the surface roughness of the concave portion is increased. Ensures more selective transfer
- an insulating layer in the concave portion of the conductive base material, it is possible to selectively form a metal layer on the upper surface of the convex portion. Furthermore, when the thickness of the insulating layer is 1Z2 or less of the height of the convex pattern, the insulating layer hardly comes into contact with the adhesive when transferring the formed metal layer, so conventional strength is also a problem. The life of the convex pattern that has been formed can be extended, and with respect to repeated use, it can sufficiently handle a mass production level of several hundred to several thousand times. In addition, when an insulating layer is formed by electrodeposition coating, an insulating layer having high adhesion to metal and plating solution resistance can be obtained, and a film can be formed uniformly. wear.
- the side surface of the convex portion of the conductive substrate has a specific taper angle, in particular, the metal layer formed on the upper surface of the convex portion is selectively transferred, and the other unnecessary metal portion. Transfer of (a metal appearing in a recess) (when the metal is copper, it is simply “copper pretend”) can be effectively suppressed.
- the present invention by using a specific conductive substrate, a metal layer formed in a pattern on the conductive substrate is transferred to another substrate to produce a substrate with a conductor layer pattern. Therefore, the substrate with a conductor layer pattern that has been obtained with good production efficiency has high light transmittance (especially, the metal pattern has a small line width and high definition) and good conductivity (high shielding). Since it can be combined, it is useful as an electromagnetic wave shielding member.
- the region B is formed outside the region A, and the area ratio of the recesses is made smaller in the region B than in the region A, whereby the frame of the substrate with the conductor layer pattern obtained is obtained. Pinholes, cracks, etc. during transfer and subsequent use can be reliably eliminated in the part, so that when using the metal layer formed in region B as a grounding part, It is possible to suppress an increase in connection resistance with the body.
- the geometric figure formed in the region B can be various.
- the surface of another substrate onto which the conductor layer pattern is transferred has adhesiveness, the transfer can be easily and reliably performed. Further, it is possible to impart near-infrared shielding to a substrate with a conductor layer pattern by imparting near-infrared shielding to this other substrate.
- the present invention by forming the insulating layer in the concave portion of the conductive base material, it is possible to selectively form the metal layer only on the upper surface of the convex portion. For repeated use It is possible to cope with mass production levels of hundreds to thousands of times.
- the conductor layer of the substrate with the conductor layer pattern is electrically connected and the effect of grounding is achieved. Make fruits more efficient. Further, in the present invention, when at least a portion corresponding to the region A is blackened among the conductor layers of the base material with the conductor layer pattern, the transparency without reflecting the color of the conductor layer (metal) is improved.
- the conductive substrate is formed by etching after forming the pattern with a resist.
- a method of forming a pattern on the material can be taken.
- an insulating layer is formed before removing the resist, and then the resist is removed. This makes it possible to expose the convex portion efficiently and accurately.
- the insulating layer is formed on the entire surface of the conductive support after removing the resist, and then only the insulating layer on the upper surface of the convex portion is removed, a high level of processing accuracy is required.
- such a step can be omitted, so that a conductive substrate for plating can be produced efficiently.
- the insulation layer is excessively peeled off during polishing, and as a result, there will be no variation in line thickness or line width of the conductor layer pattern! A conductive base material for plating can be produced.
- an insulating layer in the concave portion of the conductive base material, it is possible to selectively form a metal layer only on the upper surface of the convex portion. Furthermore, if the thickness of the insulating layer is 1Z2 or less of the height of the convex pattern, the insulating layer will hardly come into contact with the adhesive when transferring the deposited metal, so conventional strength is also a problem. The life of the convex pattern that has been formed can be extended, and with respect to repeated use, it can sufficiently cope with a mass production level of several hundred to several thousand times. In addition, when an insulating layer is formed by electrodeposition coating, an insulating layer having high adhesion to metal and plating solution resistance can be obtained, and a film can be formed uniformly.
- a substrate with a conductor layer pattern can be produced with high productivity.
- the conductive base material has an insulating layer in the concave portion, unnecessary metal plating does not occur, and during the transfer, the formed metal layer is smoothly peeled off, and the transfer process is performed efficiently.
- the surface of the metal layer selectively formed on the upper surface of the convex portion of the conductive base material can be uniformly blackened regardless of whether it is a fine line portion or a wide width portion without falling off.
- the conductor layer pattern suppresses the reflection of light emitted from the plasma display screen and external light, and the transparency and image contrast are improved.
- a group VIII element especially black nickel plating containing nickel as a component, and if an insulating layer is formed in the recess of the conductive substrate, the insulation is formed.
- a black film can be formed on the surface of the metal conductor without invading the layer and without powder falling.
- FIG. 1 is a perspective view showing an example of a conductive base material on which a geometrical figure of a concave portion with respect to a convex portion is formed.
- FIG. 2-a is a perspective view of an example of a conductive substrate including region A and region B.
- FIG. 2-b is a perspective view of another example of a conductive substrate including region A and region B.
- Fig. 3-a is a cross-sectional view of an example of a conductive base material in which a geometric figure of a concave portion with respect to a convex portion is formed.
- Fig. 3-b is a cross-sectional view of an example of a conductive base material in which a geometric pattern of a concave portion with respect to a convex portion is formed.
- Fig. 3-c is a cross-sectional view of an example of a conductive base material in which a geometric pattern of a concave portion with respect to a convex portion is formed.
- Fig. 3-d is a cross-sectional view of an example of a conductive base material in which a geometrical figure of a concave portion with respect to a convex portion is formed.
- Fig. 3-e is a cross-sectional view of an example of a conductive base material in which a geometrical figure of a concave portion with respect to a convex portion is formed.
- FIG. 4 is a part of a plan view of an example of a conductive substrate including region A and region B.
- FIG. 5 is a part of a plan view of an example of a conductive substrate including region A and region B.
- FIG. 6 is a part of a plan view of an example of a conductive substrate including region A and region B.
- FIG. 7 is a part of a plan view of an example of a conductive substrate including region A and region B.
- FIG. 8 is a part of a plan view of an example of a conductive substrate including region A and region B.
- FIG. 9 a is a part of a sectional view showing an example of a conductive substrate for plating according to the present invention.
- FIG. 9-b is a part of a cross-sectional view showing an example of a conductive substrate for plating according to the present invention.
- FIG. 9-c is a part of a sectional view showing an example of the conductive substrate for plating according to the present invention.
- FIG. 10 is a cross-sectional view sequentially showing the steps of producing a conductive substrate for adhesion according to the present invention.
- FIG. 11-a is a cross-sectional view showing a resist pattern and an insulating film formed on the upper surface of the convex portion.
- Fig. 11-b is a cross-sectional view showing the formation of the resist pattern and insulating film on the top surface of the protrusion.
- Fig. 11-c is a cross-sectional view showing the formation of the resist pattern and insulating film on the top surface of the protrusion.
- Fig. 11-d is a cross-sectional view showing the formation of the resist pattern and insulating film on the top surface of the protrusion.
- FIG. 11-e is a cross-sectional view showing the resist pattern on the top surface of the convex portion and the formation state of the insulating film.
- Fig. 12-a is the pattern of the convex part with the top surface and the geometrical shape drawn by it.
- Fig. 12-b shows the pattern of the convex part having the upper surface and the geometrical shape drawn by the pattern.
- FIG. 2 is a cross-sectional view of a conductive base material having an insulating layer formed on the surface of the conductive base material having a figure-shaped recess.
- FIG. 13 is a cross-sectional view showing an example of a conductive substrate for plating according to the present invention.
- FIG. 14 shows a conductive base material having a pattern of convex portions having an upper surface and a geometric figure-shaped concave portion drawn thereby, in a state where the concave portions are filled with an insulating layer. That is, it is a cross-sectional view of a plating transfer plate.
- FIG. 15 is a cross-sectional view of a conductive substrate having a pattern of convex portions having an upper surface and a geometrically shaped concave portion drawn thereby, with an insulating layer formed in the concave portion.
- FIG. 16 is a cross-sectional view of a conductive substrate having a pattern of convex portions having an upper surface and a geometric-shaped concave portion drawn thereby, with an insulating layer formed in the concave portion.
- FIG. 17-a is a cross-sectional view of a state where plating is deposited on a conductive substrate.
- Fig. 17-b is a cross-sectional view showing a state where plating is deposited on a conductive substrate.
- Fig. 17-c is a cross-sectional view of a state where plating is deposited on a conductive substrate.
- Fig. 17-d is a cross-sectional view showing a state where plating is deposited on a conductive substrate.
- FIG. 17-e is a cross-sectional view showing a state where plating is deposited on a conductive substrate.
- FIG. 18 is a cross-sectional view showing a state in which a transparent base material coated with an adhesive is laminated on a metal surface deposited on the upper surface of the convex portion of the conductive base material.
- FIG. 19a is a cross-sectional view of a conductive layer patterned base material and a conductive base material in which metal remains.
- FIG. 19b is a cross-sectional view of the base material with a conductor layer pattern and the conductive base material in which the metal remains.
- FIG. 20 is a cross-sectional view of a base material with a conductor layer pattern in which the conductor pattern is blackened and has a metal pattern force.
- FIG. 21 is a cross-sectional view of a base material with a conductor layer pattern in which the conductor layer pattern is blackened and also has a metal pattern force.
- Fig. 22 shows the pattern of the conductor layer with the metal pattern force with the conductor layer pattern blackened.
- FIG. 23 is a cross-sectional view showing an example of a method for producing a substrate with a conductor layer pattern.
- FIG. 24 is a conceptual cross-sectional view of an apparatus for continuously producing a substrate with a conductor layer pattern using a rotating body.
- FIG. 25 is a conceptual cross-sectional view of an apparatus for continuously producing a substrate with a conductor layer pattern using a hoop-like conductive substrate for plating.
- FIG. 26 is a conceptual cross-sectional view of another example of an apparatus for continuously producing a substrate with a conductor layer pattern using a hoop-like conductive substrate for plating.
- FIG. 27 is a chart showing characteristics of Example a.
- FIG. 28 is a chart showing characteristics of Example b.
- FIG. 29 is a chart showing characteristics of Example c.
- FIG. 30 is a chart showing characteristics of Example d.
- FIG. 31 is a chart showing characteristics of Example e.
- FIG. 32 is a first chart showing characteristics of Example f.
- FIG. 33 is a second chart showing the characteristics of Example f.
- Insulating layer Photo-curable resin layer
- Base material with conductor layer pattern 110 Hoop-like conductive substrate
- the present inventors made conductive patterns by forming and transferring a metal layer by plating using a pattern of convex portions having an upper surface and a conductive substrate having concave portions having a geometrical shape drawn thereby as a plate. It was discovered that a conductor layer pattern patterned to have excellent light transmittance can be produced with high productivity.
- the method for producing a conductive substrate for plating according to the present invention is further characterized by excellent dimensional accuracy even for a fine pattern as a patterning plate for repeated plating, peeling and use. A conductive base material excellent in durability that can be used can be easily produced.
- a force that uses a conductive substrate in which a concave portion having a geometric figure shape is formed with respect to a convex portion forms a metal layer on the surface by electrical contact.
- the conductive substrate has sufficient conductivity for that purpose, and the conductive base material has sufficient conductivity for electrodeposition coating of the insulating film.
- the conductive base material is sufficient for anodizing the surface. It has conductivity.
- the conductive base material is particularly preferably a metal.
- the conductive base material is such that the metal layer formed thereon is easily peeled off so that the metal layer formed by plating on the surface can be transferred to the adhesive support. Is preferred.
- Materials for such conductive substrates include stainless steel, chrome-plated pig iron, chrome-plated steel, titanium, titanium-lined materials, nickel and other plating releasability! Is particularly preferred!
- Examples of the shape of the conductive base material on which the convex portions are formed include a sheet shape, a plate shape, a tool shape, and a hoop shape.
- a sheet or plate attached to a rotating body (roll) may be used.
- a hoop shape it is conceivable that a roll is installed at two power points inside the hoop and a hoop-shaped conductive substrate is passed through the roll. Since metal foil can be continuously produced in both roll and hoop forms, it is preferable because production efficiency is higher than sheet and plate forms.
- the convex portion of the conductive substrate corresponds to the conductor layer pattern in the substrate with the conductor layer pattern, and the conductor layer pattern is an electromagnetic wave shield when the electromagnetic wave shielding material is finally produced. It corresponds to the layer.
- the geometrical figure of the concave part with respect to this convex part includes triangles such as regular triangles, isosceles triangles, right triangles, squares, rectangles, rhombuses, parallelogram Quadrangle such as shape, trapezoid, (positive) hexagon, (positive) octagon, (positive) dodecagon, (positive) decagon, etc. (positive) n-gon (n is an integer of 3 or more), circle,
- the pattern is a combination of ellipses, stars, etc. These units can be repeated alone or in combination of two or more.
- the triangle is the most effective. From the point of view of visible light transmission, if the line width is the same (positive), the n number of the n-gon is larger, and the aperture ratio of the conductor layer pattern is larger. Go up. From the viewpoint of visible light transmission, the aperture ratio is required to be 50% or more, and the aperture ratio of the conductor layer pattern is more preferably 60% or more.
- the aperture ratio of the conductor layer pattern is the effective area force with respect to the effective area of the electromagnetic wave shielding material (for example, the area of the range in which the geometric figure is drawn, such as the area that functions effectively for electromagnetic wave shielding). This is the percentage of the ratio of the area covered by the area covered by.
- the peripheral portion of the conductor layer pattern may be a ground portion, and a ground portion may be provided around the outside of the conductor layer pattern.
- the part corresponding to the grounding part is designated as area B, and the inside thereof is designated as area A.
- the region A of the conductive substrate corresponds to a portion corresponding to the conductor layer pattern, and the area ratio (%) of the recesses in the region A corresponds to the opening ratio.
- the region B is a portion corresponding to the same or different conductor layer pattern as the conductor layer pattern corresponding to the region A, and may be a flat portion having the same height as the upper surface of the convex portion 3.
- the ground portion corresponds to a layer for grounding the electricity collected by the electromagnetic wave shielding layer when the base material with the conductor layer pattern is finally used as an electromagnetic wave shielding material.
- the geometric figure of the concave part with respect to the convex part in the area B the geometric figure of the concave part as a planar shape drawn by the convex part
- the same one as in the area A can be adopted.
- a concave portion having the above geometric figure shape is formed on a conductive base material having a smooth surface.
- the most convenient method is to carry out a caroé.
- FIG. 1 is a perspective view showing an example of a conductive substrate on which a concave geometrical figure with respect to a convex part is formed. Illustrated in FIG. 1 is a square as the geometrical figure of the concave part 2, and the convex part 3 is formed in a lattice shape on the conductive substrate 1 so that the geometrical figure of the concave part 2 becomes a square. .
- FIG. 2 shows an example of a conductive base material in which a geometrical figure of a concave portion with respect to a convex portion is formed.
- FIG. Figure 2-a shows the entire region B without specifically showing region B (reference 4).
- Figure 2-b conceptually shows how region B has a specific grid pattern. Illustrated in FIG. 2 is a square as the geometrical figure of the concave part 2, and the convex part 3 is formed in a lattice shape on the conductive substrate 1 so that the geometrical figure of the concave part 2 becomes a square. .
- region B reference numeral 4
- FIG. 2-b there is a region B outside the geometrical figure formed by the surface, the concave portion 2 and the convex portion 3, and in FIG. 2-b, formed by the convex portion 3 and embodied in the concave portion 2.
- a concave portion 5 having a geometric shape with a shape different from the geometric shape is formed by the convex portion 6.
- Fig. 3 shows a part of the A-A section of Fig. 1 or Fig. 2-a, and shows five types of Fig. 3-a to Fig. 3-e.
- the cross-sectional view corresponding to Fig. 1 is Fig. 3-a
- Fig. 3-b to Fig. 3-e are variants of Fig. 3-a.
- the cross-sectional shapes of the concave portion 2 and the convex portion 3 are determined as appropriate, and the side surface 7 of the convex portion 3 includes a vertical surface (in the case of Fig. 3-a), a slope (in the case of Fig. 3-b and Fig. 3-c), a curved surface ( It is optional such as Figure 3-d) and stepped slope (Figure 3-e).
- the convex portion 3 has an upper surface 8, and the bottom surface 9 of the concave portion 2 has various shapes.
- the height of the convex portion 3 formed on the conductive substrate is defined as the height from the most depressed partial force of the concave portion 2 to the upper surface 4 of the convex portion 3.
- the height of the convex portion 3 is preferably l / z m to: LOO / z m. If the height of the convex portion 3 is low, when the metal layer formed on the upper surface 8 of the convex portion 3 is transferred to the transparent substrate, the pressure-sensitive adhesive appears on the metal or the concave portion 2 that appears in the concave portion 2 of the conductive substrate.
- the metal appearing in the recess 2 or the insulating layer formed in the recess 2 may be attached to the transparent substrate at the same time, so the height of the protrusion 3 is 5 ⁇ m. More preferably, the above is true. Further, if the height of the convex portion is increased, the aspect ratio becomes large, so that the processing becomes difficult and the processing cost increases. Therefore, the height of the convex portion is more preferably 50 m or less. Further, the width of the upper surface 8 of the convex portion 3 and the interval thereof are set such that the width (line width) of the upper surface 8 of the convex portion 3 is 1 111 to 40 111 so that the aperture ratio of the conductor layer pattern is 50% or more.
- the center spacing (line pitch) force of the upper surface of the part is preferably ⁇ m to 1000 ⁇ m.
- the width of the upper surface 8 (line width) of the convex portion 3 is 1 111-to improve the non-visibility, transparency, and electromagnetic shielding properties of the substrate with the conductive layer pattern. 20 111, center distance (line pitch) force between convex portions S 250 ⁇ m to 500 ⁇ m is more preferable.
- the center interval (line pitch) of the upper surface of the convex portion is a figure with a complicated pattern. If it cannot be easily determined because it is a combination of multiple figures, the area is converted to a square area based on the pattern repeat unit and defined as the length of one side.
- the height of the convex portion 6 formed on the conductive substrate is defined as the height of the concave portion 5 where the concave portion is most depressed to the upper surface of the convex portion 6.
- the height of the convex portion 6 is preferably LOO / zm. If the height of the convex portion 6 is low, the adhesive is transferred to the metal or concave portion 5 that appears in the concave portion 5 of the conductive substrate when the metal layer formed on the upper surface of the convex portion 6 is transferred to another base material.
- the height of the convex portion 6 is 5 m or more because the insulating layer formed in the concave portion 5 may be attached to the transparent substrate at the same time because it easily comes into contact with the formed insulating layer. . Further, when the height of the convex portion is increased, the aspect ratio increases, so that the processing becomes difficult and the processing cost becomes high.
- the height of the convex portion is more preferably 50 m or less.
- a indicates the inclination angle (taper angle) of the side surface of the convex portion. This taper angle is measured with respect to the top surface.
- the side surface of the convex portion having a taper angle of 30 ° or more is preferably 5 ⁇ m or more in depth from the upper surface, particularly preferably 7 ⁇ m or more.
- the taper angle is preferably 45 degrees or more in order to surely reduce copper swing.
- the shape of the metal layer formed by plating is continuous on the top surface of the convex portion. It is preferably formed of a film and formed of a discontinuous film in the recess.
- the metal layer on which the adhesive is formed on the upper surface of the convex part when transferred to another substrate is also formed on the top surface of the projections in order to peel off from the conductive substrate. It is difficult to selectively transfer only the metal layer.
- the metal appearing in the recess is a discontinuous film, the metal appearing in the recess or the side is transferred to the metal layer formed on the upper surface of the protrusion when transferring to another substrate. Since it does not follow and peel, the metal layer formed on the upper surface of the convex portion can be selectively transferred to another substrate.
- the surface roughness of the upper surface of the convex portion in the conductive substrate is low, and conversely the surface roughness in the concave portion.
- the coarseness is that the metal appearing in the recesses becomes granular and tends to be discontinuously deposited, so that only the metal layer formed on the upper surface of the protrusions by another substrate is selectively transferred. Preferred above.
- the surface roughness of the top surface of the convex part is preferably 10 ⁇ m or less (measured according to the ten-point average roughness Rz CFIS B 0601—1994), and the Rz is 1 or less. More preferably, it is 0 ⁇ m or less. Further, the surface roughness in the recess is preferably such that Rz exceeds 2.0 m, more preferably Rz is 3.0 m or more.
- the width of the upper surface of the convex portion and the interval between the convex portions are such that the width of the upper surface of the convex portion is l / zm to 40 ⁇ m and the central interval of the convex portion is 100 ⁇ m so that the aperture ratio of the conductor layer pattern is 60% or more. It is preferable that it is m-1000 micrometers.
- Conductor layer By optimizing the pattern shape of the substrate with no turn, the line width, line pitch, and line thickness of the substrate with the conductor layer pattern can be transferred from the substrate, or the transfer of metal in unnecessary parts can be suppressed. In order to optimize the thickness of the projection and easily produce it, the width of the upper surface of the convex portion is particularly preferably in the range of 1 to 20 m.
- Examples of the method for forming the convex portion on the conductive substrate include the following methods.
- a portion of the conductive base material where the concave portion should be formed (the portion corresponding to the opening of the conductive layer pattern of the base material with the conductive layer pattern) is directly irradiated with laser light to form a concave portion, and the conductive layer A method of forming a convex portion corresponding to the pattern,
- the material of the conductive substrate is hard, it is preferable to use the method (1) (laser processing method) or (2) (etching method) for direct processing. When using a material with excellent solid workability, it can be processed by the above method (3) (engraving method). At this time, further, hard plating such as chromium is applied to the surface to increase the strength. You can. [0063]
- the region B will be mainly described with reference to FIGS. 4 to 8 show a part of a plan view of the conductive substrate including region A and region B.
- the planar shape 10 of the concave portion is black
- the upper surface 11 of the convex portion is white
- the region A shows only a lattice pattern with a bias angle of 45 °.
- the geometric figure formed in region B is selected as appropriate.
- the top surface at the end of region A is continuous with the top surface of region B (Fig. 4)
- part of the line at the end of region A is region B.
- the geometrical figure formed in region B is round (Fig. 6)
- the geometrical figure force formed in region B is S stripe shape (Fig. 5). 7), if the geometric figure formed in region B is a large rectangle ( Figure 8), etc.
- the width of the convex portion formed in the region B is too thin, the width of the formed conductor layer is reduced, the ground area is reduced, the connection resistance is increased, and the electromagnetic shielding property is reduced. There is. Conversely, if the width of the convex portion formed in region B is too large, the width of the formed conductor layer becomes large, and the ground area transferred to another substrate becomes large, so that the connection resistance is stable. However, cracks and pinholes are likely to occur in the transferred conductor layer.
- the metal layer formed on the upper surface of the conductive base material is transferred to another base material, if the metal layer is cracked, the transfer is performed (when the conductive base material is peeled off). It is considered that the metal layer cannot follow the deformation of another base material (or, in some cases, the deformation of the adhesive layer laminated on another base material). If the metal layer formed on the upper surface of the recess is selectively transferred by increasing the thickness or by disposing an insulating layer in the recess so that the metal is not plated in the recess, It is considered that cracking can be prevented in order to relieve the stress generated in the transfer of the geometric figure corresponding to the concave figure.
- the width of the upper surface of the convex portion (line width) in region B is p and the center interval (line pitch) of the upper surface of the convex portion is q, the smaller p is, the larger q is, the metal during transfer Layer cracking is reduced. If p is small, the pinhole at the outer peripheral edge for grounding reduces the force q. If the p is small, the peeling stress of the adhesive due to the opening is not sufficiently relaxed. ) q is at least 3 times the width of the top surface of the convex part (line width) p in region B (q ⁇ 3p), in other words, the width of the concave part is at least twice the width of the front of the convex part. I like it.
- the spacing q between the top surfaces of the protrusions is less than 10 times the line width (q ⁇ That is, it is preferable that the width of the concave portion is not more than 9 times the width of the front surface of the convex portion.
- the area ratio of the recesses in the region A is preferably 50% to 97% or less, and the area ratio of the region B is preferably 40% to less than 97%.
- the area ratio of the recesses in region A is 70% to More preferably, it is 95%.
- the area ratio of the recesses in area B is more preferably 45% to 70% in order to ensure both crack resistance and pinhole resistance.
- the intersection of the convex portions tends to be rounded at a right angle. If the corner is a right angle, it is easy to start the cracking of the metal, but if the corner is rounded or the opening is round or curved, the stress applied to the metal plating line during transfer Since it can be made more uniform, it becomes a crack.
- etching methods when a printing method is used, various methods can be used as a printing method for forming a resist pattern. For example, screen printing, letterpress printing, letterpress offset printing, letterpress reverse printing, intaglio printing, letterpress offset printing Inkjet printing, flexographic printing, and the like can be used.
- a dry film resist or the like is laminated, a mask is attached, and after exposure and development, an etching process can be performed. After applying a liquid resist, the solvent is dried or dried. A similar process can be performed after the temporary curing. If the photocurable resin can be patterned by irradiating active energy rays through a mask, the mode is not limited.
- the method of laminating a dry film resist and exposing through a mask is preferable from the viewpoint of productivity.
- direct processing a method in which a dry film resist is bonded or a liquid resist is applied and then directly exposed with a laser or the like without using a mask is preferable.
- the polishing method may be a well-known! / Or any other method, but can be performed by puffing, general mechanical polishing using a puffol, polishing paper, belt sander, or the like. If the polishing puff is rough, the line width of the convex part after polishing may become extremely thick. Therefore, it is preferable to use an extremely fine polishing puff of # 1500 or more.
- FIG. 9 shows a cross section of the conductive base material in a state where an insulating layer is formed in the concave portion of the conductive base material having the convex pattern having the upper surface and the concave portion of the geometrical shape drawn by the upper surface in the region A. A part of the figure is shown.
- a conductive substrate having the cross-sectional shape shown in FIG. 3D is used.
- the insulating layer 12 is formed by a pattern of convex portions 3 having an upper surface 8 and a concave portion 2 of the geometrical shape drawn thereby.
- the insulating layer 12 is formed so as to be flush with the upper surface 8 from the end of the upper surface 8 of the protrusion 3. In this way, it is particularly preferable that the insulating layer 12 protrudes above the upper surface 8 when the conductive substrate is leveled.
- the insulating layer 12 may be formed so that the bottom portion of the concave portion 2 is thicker than the side portion 7. Further, as shown in FIG. The thickness of the insulating layer 12 may gradually decrease near the edge of the insulating layer 12, and the thickness of the insulating layer 12 may be zero in the same plane direction as the upper surface 8. This can be obtained by forming the insulating layer shown in FIGS. 9a and 9-b and then processing it by the polishing method as described above.
- the thickness of the insulating layer on the side surface 7 of the convex portion is preferably 10 m or less. At the end of the upper surface 8, the thickness is 0 ⁇ m in the same plane direction as the upper surface 8. Especially preferred to be! /.
- the insulating height of the convex portion 3 is defined as the height from the most depressed portion when the concave portion 2 is covered with the insulating layer 12 to the upper surface 8 of the convex portion 3 (this is the force defined in the region A) Define area B in the same way). At this time, it is preferable to form the insulating layer 12 so that the insulating height of the convex portion 3 is 1Z2 or more of the height of the convex portion 3 of the conductive substrate. The thinner the insulating layer 12, the lower the possibility that the insulating layer 12 will come into contact with another substrate (or the adhesive or adhesive layered on the surface thereof).
- the insulating layer 12 is formed so that the height of the convex portion is 3Z4 or more. If the insulation height of the protrusion is smaller than 1Z2 which is the height of the protrusion, the base material (or the adhesive or adhesive layered on the surface) separates from the insulating layer due to deformation of the adhesive during transfer. Since it becomes easy to contact, the lifetime of a convex part pattern becomes short.
- an insulating material having good adhesion to the conductive substrate 1 can be used. The insulating layer 12 easily peels from the conductive substrate 1 due to repeated peeling stress.
- the insulating height of the convex part 3 is preferably 10 m or more lower than the height of the convex part 3.
- the thickness is preferably 1 ⁇ m or more.
- the insulating layer 12 Since the formation of the insulating layer 12 is easier to form when it is uniform, it is preferably 1 to 10 ⁇ m as a whole, preferably a thin film insulating layer.
- FIG. 11 is a cross-sectional view showing an example of a process showing a method for producing a conductive substrate for plating.
- FIG. 11 shows an example using a conductive substrate having the cross-sectional shape shown in FIG. 3d.
- a photocurable resin layer 7 is formed on the surface of the conductive substrate 1 (FIG. 11a).
- Photolithographic method 13 is used to pattern the photocurable resin layer 13 ( Figure 11-b). By etching the conductive substrate using the patterned photocurable resin layer 13 as an etching resist, the etched conductive substrate shown in FIG. 11 is obtained (FIG. 11- c ). At that time, the photocurable resin layer 13 as an etching resist is left without being peeled off.
- an insulating layer 8 is formed in the recess 2 of the conductive substrate 1 (FIG. 11d).
- the photocurable resin layer 13 as an etching resist remains on the upper surface 8 of the convex portion of the conductive base material, no insulating layer is formed.
- the etching resist can be selectively peeled off, and the insulating layer 12 can be selectively formed in a portion other than the upper surface 8 of the convex portion of the conductive substrate, that is, in the concave portion (FIG. 11e).
- the surface of the photocurable resin layer 13 as a resist can be lightly polished in order to remove dirt on the surface.
- the force varies depending on the type of the conductive base material, so it cannot be generally stated, but it is preferable to polish with a weak force.
- polishing it is possible to perform treatment with a chemical solution using a degreasing treatment agent or the like. In this case, it is possible to appropriately select a chemical solution such as V in which the insulating layer is not broken.
- the width of the upper surface of the convex pattern after etching becomes narrower than the width of the etching resist pattern.
- Etching is preferred (see Figure 11-c).
- the width of the etching resist pattern is preferably 20 m or more from the viewpoint of facilitating the formation of a good pattern or a good pattern. If you try to form a pattern with a narrower width than this, the etching resist pattern will blur. It is also a force that easily causes disconnection or the like. For safety in this respect, the width of the etching resist pattern may be 30 m or more.
- the width of the etching resist pattern is too large, the degree of over-etching becomes too large, so it is preferable that the width is 100 ⁇ m or less, particularly 50 ⁇ m or less. If the width of the etching resist pattern exceeds 100 ⁇ m, it tends to be difficult to make the width of the upper surface of the convex portion of the conductive substrate after overetching 40 m or less.
- the line width by etching can be adjusted by the width of the original resist and the etching time.
- etching liquids depending on the conductive metal material, and since etching liquids are commercially available for the respective metals, they can be used.
- conductive metal strength S stainless steel it is common to use salty ferric iron, and in the case of titanium, a hydrofluoric acid-based etching solution is often used.
- FIGS. 12-a to 12-c are enlarged cross-sectional views of the upper surface portion of the convex portion 3 after the insulating layer 8 is formed and before the etching resist pattern 13 is peeled off.
- Fig. 12-a is an example of the case where the over-etching method is not applied!
- the insulating layer 12 is deposited on the side surface of the resist pattern 13 above the upper surface of the convex portion 3 of the conductive substrate. Resulting in. In this case, the etching resist 13 may be removed.
- contact between the insulating layer 12 and the adhesive of the transfer substrate tends to occur, and the insulating layer 12 tends to be partially broken. If the degree is too small or the insulating layer 12 is formed too thick, as shown in FIG.
- the over-etched width z is obtained by the following equation (1).
- Equation 2 [Equation 2] w ⁇ z ⁇ , 2) w is preferably a force that is the same size as z, smaller than that, as shown in Figure 12-c.
- the photocurable resin layer 13 as an etching resist was peeled off, and then the insulating layer 12 was removed.
- the insulating layer 12 is formed not only on the concave portion 2 but also on the upper surface 8 of the convex portion, as shown in FIG. Only the insulating layer 12 formed on the upper surface 8 of the convex portion by processing may be removed.
- a force that requires a certain amount of accuracy is required. According to the above method, the step of selectively removing the insulating layer 12 is not necessary. The number of processes is reduced, and the fabrication becomes easy.
- the photo-curable resin layer 13 using a photolithographic method has been described as an etching resist.
- the upper surface of the convex portion is finally plated with a hard metal such as nickel or chrome in the above process.
- the insulating material for the insulating layer used in the present invention a material having high chemical resistance and high adhesion to a metal is preferably used. In the process of electroplating or electroless plating, it is immersed in the pretreatment solution or plating solution, so that the strong material is more resistant to both acid resistance and alkali resistance. Is preferred.
- resins for example, thermosetting resins are preferred, such as bamboo resin, epoxy resin, urea resin, errin resin, melamine resin. , Phenolic resin (including alkylphenolic resin), formalin resin, metal oxide, metal chloride, oxime, etc., which are self-curing (even if a curing catalyst is used) Good).
- thermosetting resin can be used as a thermosetting resin.
- a resin having a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an unsaturated hydrocarbon group, and an epoxy group, a hydroxyl group, an amino group, an amide group, a carboxyl group, and a thiol group.
- a curing agent having a functional group or a curing agent such as a metal chloride, isocyanate, acid anhydride, metal oxide, peroxide, etc., which has a functional group reactive with the above resin. There is something to be done.
- additives such as general-purpose catalysts can also be used.
- Specific examples include curable acrylic resin compositions, unsaturated polyester resin compositions, diallyl phthalate resins, epoxy resin compositions, polyurethane resin compositions, and the like.
- Examples of the method for forming the insulating layer include brush coating, spray coating, and after dubbing, removing the grease with a squeegee blade and drying it.
- the electrodeposition coating is preferred because of the uniformity of the film, the ease of formation, and the environmental load.
- Electrodeposition paints can be used in any known cationic type or eron type. Here, an example of electrodeposition paints that can be used is shown.
- a resin paste having a basic amino group is prepared, and this is neutralized with an acid and water-solubilized (water-dispersed). Paint is included.
- the cationic electrodeposition coating is applied using the conductive substrate (object to be coated) as a cathode.
- the resin having a basic amino group includes, for example, bisphenol type epoxy resin, epoxy group (or glycidyl group) -containing acrylic resin, glycidyl ether of alkylene glycol, epoxidized polybutadiene, and epoxidized product of novolac phenol resin.
- An epoxy group (oxysilane ring) of an epoxy group-containing resin with an amine compound added, or an unsaturated compound having a basic amino group for example, dimethylaminoethyl methacrylate, N-biphenyl).
- amine compound is a basic amine compound, which is an aliphatic, cycloaliphatic or araliphatic primary or secondary amine, alkanolamine, tertiary amine.
- amine compounds such as quaternary ammonia salts. Typical examples of these amine compounds having a basic amino group include the following. (1)
- Primary amines such as methylamine, ethylamine, n- or iso-propylamine, monoethanolamine, n- or iso-propanolamine; (2) jetylamine, diethanolamine, di-n- or iso-propanolamine Secondary amines such as amine, N-methylethanolamine, N-ethylethanolamine; (3) ethylenediamine, diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine , Polyamines such as dimethylaminoethylamine and dimethylaminopropylamine. Of these, alkanolamines having a hydroxyl group are preferred.
- the primary amino group may be blocked by reacting with a ketone in advance, and then reacted with an epoxy group with the remaining active hydrogen.
- basic compounds such as ammonia, guanidine, hydroxylamine, hydrazine, and hydroxyethyl hydrazine can be used in the same manner.
- the basic group formed using these compounds can be converted to a cationic group by protonation with an acid, particularly preferably a water-soluble organic carboxylic acid such as formic acid, acetic acid or lactic acid.
- tertiary grades such as triethylamine, triethanolamine, ⁇ , ⁇ -dimethylethanolamine, ⁇ -methyljetanolamine, ⁇ , ⁇ -jetylethanolamine, ⁇ -ethylethylethanolamine, etc.
- Amines can also be used, which can be pre-protonated with acid and quaternized with epoxy groups.
- sulfides such as dimethylsulfide, diphenylsulfide, tetramethylenesulfide, and thiodiethanol, which react with epoxy groups to form cationic groups, boric acid, carbonic acid, and organic monocarboxylic acids.
- This salt may be reacted with an epoxy group to form a tertiary sulfo-um salt.
- triethyl phosphine, phenol dimethyl A quaternary phosphonium salt can also be obtained by reacting a salt of a phosphine such as phosphine, diphenylmethylphosphine, triphenylphosphine and the like with an acid as described above with an epoxy group to form a quaternary phosphonium salt. Phosphine salts can also be used.
- Examples of the acid that is a neutralizing agent for neutralizing the coconut resin having a basic amino group and making it water-soluble (water-dispersed) include acetic acid, hydroxylacetic acid, propionic acid, butyric acid, lactic acid, glycine, etc. Inorganic acids such as organic acids, sulfuric acid, hydrochloric acid and phosphoric acid can be used.
- the amount of neutralizing agent used is suitably in the range of about 0.1 to 0.4 neutralizing equivalent to the base number of the resin (about 20 to 200).
- a crosslinking agent can be mix
- a crosslinking agent a blocked polyisocyanate compound is well known, but when the coating film is heated (about 140 ° C or higher), the blocking agent is dissociated to regenerate the isocyanate group, Crosslinking reaction is carried out with respect to the isocyanate groups such as hydroxyl groups in the cationic resin as described above and reactive groups, and the cationic electrodeposition paints include pigments (colored pigments, extender pigments, antifouling pigments, etc. face).
- the blending amount of the material is preferably 40 parts by weight or less per 100 parts by weight of the resin solid content), hydrophilic solvent, water, additives and the like can be blended as necessary.
- the cationic electrodeposition paint is preferably diluted with deionized water or the like so that its solid content concentration is about 5 to 40% by weight, and the pH is adjusted within the range of 5.5 to 8.0.
- Cationic electrodeposition paints using cationic electrodeposition paints prepared in this way can usually be carried out with the substrate to be coated as a cathode under conditions of a bath temperature of 15 to 35 ° C and a load voltage of 100 to 400V. it can.
- a baking temperature of the coating film is generally suitable in the range of 100 to 200 ° C.
- the ion-on electrodeposition paint is based on a resin having a carboxyl group and is preferably an anodic deposition electrodeposition paint that is neutralized and water-solubilized (water-dispersed) with a basic compound. It is coated with the conductive substrate (object) as the anode.
- maley coconut oil resin obtained by adding maleic anhydride to dry oil (such as linseed oil, dehydrated castor oil, tung oil), polybutadiene (1, 2-type, 1, 4-type, etc.) Maleated polybutadiene with maleic anhydride attached to it, epoxy resin with unsaturated fatty acid ester with maleic anhydride added, and high molecular weight polyhydric alcohol (molecule It can be obtained by adding polybasic acid (trimellitic anhydride, maleated fatty acid, maleated oil, etc.) to an amount of about 1000 or more, including a partial ester of epoxy resin and styrene alcohol alcohol copolymer).
- Reaction product of polymerizable unsaturated monomer and unsaturated fatty acid containing carboxyl group-containing polyester resin including fatty acid-modified one
- carboxyl group-containing acrylic resin including glycidyl group or hydroxyl group
- a resin or a copolymer formed by adding maleic anhydride or the like to a polymer or copolymer formed by using carboxylic acid, and a carboxyl group content strength For example, a resin or a copolymer formed by adding maleic anhydride or the like to a polymer or copolymer formed by using carboxylic acid, and a carboxyl group content strength.
- an acid value in the range of about 30 to 200 is suitable. is doing.
- Examples of the basic compound that is a neutralizing agent for neutralizing these carboxyl group-containing resins and making them water-soluble (dispersed) include alkanolamines such as monoethanolamine, diethanolamine, and dimethylaminoethanol. Further, alkylamines such as jetylamine and triethylamine, and inorganic alkalis such as potassium hydroxide and sodium hydroxide can be used.
- the amount of these neutralizing agents used is suitably in the range of about 0.1 to 1.0 times equivalent (preferably 0.4 to 0.8 times equivalent) of the theoretical neutralization equivalent to the acid value of the resin.
- a cross-linking agent can be blended in the ion-on electrodeposition paint.
- the cross-linking agent low molecular weight melamine greaves such as hexakis methoxymethyl melamine, butoxylated methyl melamine, and ethoxylated methyl melamine can be used as necessary.
- pigments colored pigments, extender pigments, anti-fouling pigments, etc.
- the amount of pigment is preferably 40 parts by weight or less per 100 parts by weight of the solid content of the resin), hydrophilic Solvents, water, additives, etc. can be blended as necessary.
- the on-electrode coating can be carried out according to a conventional method.
- the coating can be carried out with the object to be coated as an anode under conditions of a bath temperature of 15 to 35 ° C. and a load voltage of 100 to 350 V.
- the electrode-on electrodeposition coating can be cured by heating in the range of 100 to 200 ° C, preferably 140 to 200 ° C. If so, dry at room temperature.
- durability is not limited to ceramics or the like. Machine materials can also be used.
- Inorganic materials include alkali metal, organopolymetal, organoalkoxymetal, alkoxymetal, modified acetylethylacetonate metal, and other metal oxide polymers and inorganic fillers when wet coating is used.
- the applied paint can be applied by spray, dispenser, datebing, roll, spin coat, etc. with a solvent such as alcohol or water.
- An insulating layer can also be formed by a liquid layer deposition method (LPD method) using a metal fluoride complex.
- a coating method it can be produced by using a PVD method such as vapor deposition, sputtering, ion plating, a CVD method such as plasma CVD or thermal CVD, or a thermal spraying method.
- the insulating material may be used alone, but it is preferable to form a film of two or more layers by combining the above methods.
- An insulating film formed by a single wet coating method such as sol-gel has a large difference in expansion coefficient from the underlying metal, so cracks are likely to occur. Therefore, it is preferable to form one layer or two or more layers of metals, oxides, nitrides, carbides, etc. as an intermediate layer so as to alleviate the difference in expansion coefficient by dry coating. If the layer coated on the outermost surface has an insulating property, the lower layer does not necessarily have an insulating property.
- film types formed by dry coating include Al, Au, Co, Cr, Cu, Ge, In, Mo, Nb, Ni, Pb, Pd, Pt, Ru, Si, Sn, Ta, Ti, W, In addition to pure metals such as Y, Zn, Zr and their alloys, Al O, BaTiO, Cr O, Fe O, InO,
- Metals such as O, indium tin oxide (ITO), and antimontin oxide (ATO)
- a carbide such as TiC can be used. These metals and metal compounds can also be used in combination.
- the conductive substrate is an iron-based material, nitrides and carbides are particularly preferred because of their good adhesion to the conductive substrate.
- an insulating layer may be formed by stacking dry coating layers, or wet coating on the dry coating.
- a film may be formed by
- a high-strength and high-hardness film as an insulating layer
- at least the surface of the carbon thin film similar to diamond or the so-called diamond-like carbon (hereinafter referred to as DLC thin film) is insulated. It is preferable to form it with what has property.
- the insulating layer may be formed entirely by the above-mentioned insulating DLC thin film, but it improves the adhesion of the DLC thin film to a conductive substrate such as a metal plate, thereby improving the durability of the insulating layer.
- the above S or SiC thin film has excellent adhesion to a metal such as stainless steel, and also forms SiC at the interface with the insulating DLC thin film to be laminated on it. Has the effect of improving the performance.
- S, SiC and DLC thin films can be formed by the dry coating method described above.
- a well-known method can be employ
- the plating method an electric plating method, an electroless plating method, or other plating methods can be applied.
- Electric plating will be further described.
- a copper sulfate bath, a copper borofluoride bath, a copper pyrophosphate bath, or a copper cyanide bath can be used as an electrolytic bath for plating.
- a stress relaxation agent also having an effect as a brightening agent
- electro nickel plating a Watt bath, a sulfamic acid bath, or the like can be used.
- additives such as saccharin, paratoluenesulfonamide, sodium benzenesulfonate, sodium naphthalenetrisulfonate, and commercially available additives which are their preparations are used as necessary. Additives may be added.
- alloy plating using cyan gold potassium or pure gold plating using citrate ammonium bath or potassium citrate bath is used.
- alloy plating binary alloys of gold copper, gold silver, gold cobalt, and ternary alloys of gold copper silver are used.
- other known methods can be used for other metals. For example, see pages 87 to 504 of Non-Patent Document 1 for the electrical plating method. can do.
- electroless plating examples include copper plating, nickel plating, and other methods, such as tin plating, gold plating, silver plating, cobalt plating, iron plating, and chromium plating.
- a reducing agent is added to the plating solution, and electrons generated by the oxidation reaction are used for metal deposition reaction. It consists of salt, complexing agent, reducing agent, pH adjuster, pH buffer, stabilizer and so on.
- copper sulfate is preferably used as the metal salt, formalin as the reducing agent, and Rossel salt or ethylenediamine tetraacetic acid (EDTA) as the complexing agent.
- the pH is mainly adjusted with sodium hydroxide, but potassium hydroxide and lithium hydroxide can also be used.
- Carbonates and phosphates are used as buffers, and stabilizers are used.
- Cyanides preferentially complexed with monovalent copper, thiourea, bibilidyl, 0-phenantorin, neocuproin, etc. are used.
- nickel sulfate is preferably used as the metal salt
- sodium hypophosphite, hydrazine, borohydride compounds, etc. are preferably used as the reducing agent.
- sodium hypophosphite is used, phosphorus is contained in the plating film, and corrosion resistance and wear resistance are excellent.
- the buffering agent a monocarboxylic acid or an alkali metal salt thereof is often used.
- Complexing agents that form stable soluble complexes with nickel ions in the plating solution are used, and acetic acid, lactic acid, tartaric acid, malic acid, citrate, glycine, alanine, EDTA, etc. are used. For example, sulfur compounds and lead ions are added.
- Non-Patent Document 1 pages 505 to 545 of Non-Patent Document 1 can be referred to. Furthermore, in order to obtain the reducing action of the reducing agent, it is necessary to activate the catalyst on the metal surface.
- the substrate is a metal such as iron, steel, or nickel
- the metal has catalytic activity, so it can be deposited just by immersing it in an electroless plating solution.
- copper, silver, their alloys, and stainless steel are the base materials.
- a method of immersing the covering object in an acidic hydrochloric acid solution of palladium chloride and depositing palladium on the surface by ion substitution is used.
- the electroless plating that can be used in the present invention is, for example, the convex pattern of the convex portion having the upper surface described above and the convex portion of the conductive base material having the concave portion of the geometrical drawing shape drawn thereby.
- a copper catalyst is applied by adhering a palladium catalyst if necessary and then immersing it in an electroless copper plating solution at a temperature of about 60 to 90 ° C.
- the substrate need not necessarily be conductive.
- the base material needs to be conductive, and is deposited on the base material in preparation for electroless plating.
- the substrate needs to be conductive.
- the material of the conductive base material is Ni
- the conductive base material having the convex pattern having the upper surface and the geometrical figure-shaped concave portion drawn thereby is anodized.
- copper is deposited by dipping in an electroless copper plating solution.
- conductive materials such as silver, copper, gold, aluminum, tandasten, nickel, iron, and chromium are used.
- Volume resistivity at 20 ° C (specific resistance) It is desirable to contain at least one type of metal with a Q Zcm or less.
- the metal constituting it is grounded as an electric current, so that the higher the conductivity, the better the electromagnetic wave shielding property.
- These metals include silver (1.62 ⁇ Q Zcm), copper (1.72 ⁇ Q Zcm), gold (2.4 ⁇ Q Zcm), aluminum (2.75 ⁇ Q Zcm), tungsten (5 .5 ⁇ Q Zcm), nickel (7.24 ⁇ ) , Iron (9. ⁇ ⁇ 0 ⁇ 11), chromium (17 ⁇ / cm, all values at 20 ° C), etc., but are not limited thereto.
- the volume resistivity is more preferably 10 Q Zcm, more preferably 5 Q Zcm.
- copper is most preferably used.
- These metals may be used alone or may be an alloy with another metal or a metal oxide to give further functionality.
- the thickness of the metal layer (plating thickness) formed by plating on the upper surface of the convex portion of the conductive base material having the insulating layer in the concave portion described above exhibits sufficient conductivity (in this case, the electromagnetic wave shielding property is sufficient).
- the thickness is not less than / zm.
- the thickness of the formed metal is 20 m or less. In order to shorten the plating time and increase the production efficiency, The thickness of is more preferably 10 ⁇ m or less.
- FIGS. 14 to 16 A method for forming a plastic substrate with a conductive layer pattern will be described with reference to FIGS. 14 to 16, taking as an example the case where convex portions 3 having a trapezoidal cross section are formed on a conductive substrate.
- FIG. 14 is a cross-sectional view of a state in which a metal layer is formed on the conductive substrate 1.
- the metal layer formed on the conductive substrate 1 is composed of a metal layer 14 formed on the upper surface of the convex portion, a metal 15 appearing on the bottom surface of the concave portion 2, and a side surface of the convex portion, depending on where the metal layer is formed.
- metal 16 that appeared in For metals appearing on the conductive substrate 1, depending on the conditions such as the composition of the plating bath, the type of additive, the surface shape of the conductive substrate, the height of the projections, and the current density, metals 14, 15, 16, It is possible to change the thickness and shape of each. For example, when the current density is high, the embedding of the surface having a large surface roughness is poor and the particles are deposited in a granular form.In addition, when the height of the convex portion is high, the metal film thickness appearing in the concave portion is thin. Become. In any case, as long as only the metal 14 can be selectively transferred to the transparent substrate under the above-described conditions, there is no limitation on the above-mentioned conditions.
- the plating thickness is preferably 0.5 m or more in order to exhibit sufficient electromagnetic shielding properties. Furthermore, if the plating thickness is too thick, the metal 15 appearing on the bottom surface of the recess 2 and the metal 16 appearing on the side surface also grow, so the metal 15 and 16 are also transferred at the same time and formed on the top surface of the projection. Since it may be difficult to selectively transfer only the deposited metal layer 14 (selective transferability), the thickness of the metal layer 14 formed on the upper surface of the convex portion should be 20 m or less. It is preferable to do. Furthermore, in order to shorten the plating time and increase the production efficiency, the thickness of the plating is more preferably 10 m or less.
- FIG. 15 is a cross-sectional view showing a state in which a transparent substrate 18 coated with an adhesive 17 is laminated on the surface of the metal layer 14 formed on the upper surface of the convex portion of the conductive substrate 1 as shown in FIG.
- FIG. Fig. 16 shows that the transparent substrate 18 coated with the adhesive 17 is peeled off, and only the metal layer 14 formed on the upper surface 8 of the convex portion of the conductive substrate 1 is removed, and the adhesive 17 is applied to the transparent substrate 18.
- FIG. 6 is a cross-sectional view showing a base material 19 with a conductor layer pattern produced by transfer through and a conductive base material 1 in which metals 15 and 16 remain on the bottom and side surfaces of a recess 2.
- an adhesive including an adhesive
- an adhesive is applied.
- the adhesive 17 is applied to any part of the conductive base material 1 as long as only the metal 14 is transferred.
- the metal 17 and 16 may be transferred to the transparent substrate simultaneously with the metal 14, so that the adhesive 17 is applied to the upper surface 8 of the convex portion. It is preferable to contact only the formed metal layer 14. Also, if the adhesive is too thin, adhesion to the metal 14 may be reduced and transfer failure may occur, and if the adhesive is too thick, the manufacturing cost of the adhesive will increase. Since the amount of deformation of the adhesive increases when laminating, it is easy to come into contact with the metals 15 and 16, so the thickness of the adhesive is preferably smaller than the height of the convex part. Since the chance of coming into contact with the metal 15 is reduced, the height is more preferably half or less of the height of the convex portion. The thickness of the adhesive is preferably 1 to 50 m, and preferably 5 to 30 / zm.
- the conductive base material 1 metal, the metal 15, 16 and, in some cases, a part of the metal 14 are repeatedly plated.
- the metal layer 14 formed on the upper surface 8 of the convex portion 3 in a favorable state during the subsequent transfer.
- a method of etching the remaining metal is preferable.
- the etching solution is preferably a solution that dissolves the remaining metal and does not corrode the conductive substrate 1.
- the metal that appears in the plating is copper
- ferric chloride solution, copper chloride solution, sulfuric acid / hydrogen peroxide solution, ammonium persulfate solution, etc. are preferably used as the etching solution.
- the etching solution is a force that can be used when the conductive substrate 1 is titanium.
- ferric chloride solution or copper chloride solution is used, stainless steel is corroded, so it cannot be used.
- Etching solution is used without corroding stainless steel such as ammonium persulfate.
- the etching solution is appropriately selected depending on the remaining metal and the material of the conductive substrate 1.
- Other methods for removing the metal remaining on the conductive substrate include a method of removing the residual metal by transferring it to an adhesive film.
- the thickness of the adhesive of the adhesive film that removes the residual metal is such that the thickness of the adhesive layer is equal to or greater than the height of the convex portion in order to facilitate contact with the metal remaining in the concave portion. More preferably, it has a thickness that is at least twice the height of the preferred protrusion. After the transfer, the metal can be removed from the conductive substrate 1 and then staking can be performed again.
- FIG. 17 An example of a method for producing a plastic substrate with a conductive layer pattern is explained with reference to Fig. 17, taking as an example the case where convex part 3 (see Fig. 3-b) with a trapezoidal cross-section is formed on a conductive substrate. To do.
- FIG. 17-a shows the pattern of the convex portion 3 having the upper surface 8 and the thin film insulating layer 12 formed on the entire surface having the convex portion of the conductive substrate 1 having the geometrical shape-shaped concave portion drawn thereby. It is sectional drawing which shows the state which carried out.
- the thin film insulating layer 12 can be formed by electrodeposition coating as described above.
- the upper surface 8 of the convex portion 3 is polished until the upper surface 8 of the convex portion 3 is exposed.
- Figure 17-b shows a cross-sectional view of this state.
- the metal 14 is attached to the adhesive layer 21 and peeled off from the conductive substrate 1, that is, transferred to another substrate 20 to obtain a substrate 22 with a conductor layer pattern.
- a cross-sectional view of this state is shown in FIG.
- the thickness of the metal layer (plating thickness) formed by plating on the upper surface of the convex portion of the conductive base material having the insulating layer in the concave portion described above should exhibit sufficient conductivity (at this time, In order for the base material with a conductor layer pattern to exhibit sufficient electromagnetic shielding properties, a pinhole is formed in the conductor layer, which is preferably 0.5 m or more in the region B. In order to reduce the possibility that the electromagnetic wave shielding property will be reduced at this time, the thickness is more preferably 3 m or more.
- the thickness of the metal layer to be formed is preferably 20 m or less. In addition, in order to shorten the plating time and increase the production efficiency, More preferably, the plating thickness is 10 m or less.
- Examples of the other base material include glass, a plate such as a plastic, a plastic film, and a plastic sheet.
- glass such as soda glass, non-alkali glass, and tempered glass can be used.
- Plastics include polystyrene resin, acrylic resin, polymethylmethacrylate resin, polycarbonate resin, polyvinyl chloride resin, polysalt vinylidene resin, polyethylene resin, polypropylene resin, polyamide resin, Polyamideimide resin, polyetherimide resin, polyetheretherketone resin, polyarylate resin, polyacetal resin, polybutylene terephthalate resin, polyethylene terephthalate resin, etc., thermoplastic polyester resin, cellulose acetate resin, Thermoplastic resins such as fluorine resins, polysulfone resins, polyether sulfonate resins, polymethylpentene resins, polyurethane resins, diallyl phthalate resins and the like can be mentioned.
- plastics polystyrene resin, acrylic resin, polymethyl methacrylate resin, polycarbonate resin, and polyvinyl chloride resin that are excellent in transparency are suitably used.
- Another base material thickness is 0.5mn! ⁇ 5mm is also preferred for display protection and strength, handling and sexuality.
- Another substrate in the present invention is preferably a plastic film.
- This plastic film includes polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefins such as polyethylene, polypropylene, polystyrene, and EVA, and burres such as polyvinyl chloride and polyvinyl chloride vinylidene.
- a film made of plastic such as polysulfone, polyether nosale phone, polycarbonate, polyamide, polyimide, acrylic resin, etc., having a total visible light transmittance of 70% or more is preferable. These can be used as a single layer, but may be used as a multilayer film combining two or more layers.
- plastic films a polyethylene terephthalate film or a polycarbonate film is particularly preferable from the viewpoints of transparency, heat resistance, ease of handling, and cost.
- the thickness of the plastic film is not particularly limited, but a thickness of 1 mm or less is preferable. If it is too thick, the visible light transmittance tends to decrease. In view of the fact that if the film is too thin, the handleability deteriorates, and the thickness of the plastic film is more preferably 50 to 200 / ⁇ ⁇ , more preferably 5 to 500 ⁇ m.
- These substrates such as plastic films are preferably transparent (that is, transparent substrates) in order to be used as an electromagnetic wave shielding film for preventing leakage of electromagnetic waves from the front surface of the display.
- the surface of the other substrate on which the conductor layer pattern is transferred needs to have adhesiveness when transferred.
- the substrate itself may have the necessary adhesiveness, but it is preferable to laminate an adhesive layer on the transfer surface.
- the adhesive layer is preferably one that has adhesiveness at the time of transfer or one that exhibits adhesiveness under heating or pressure.
- the material having adhesiveness it is most preferable to use a resin having a glass transition temperature of 0 ° C. or less, which is preferable to a resin having a glass transition temperature of 20 ° C. or less.
- thermoplastic resin, thermosetting resin, resin cured by irradiation with an activated energy line, and the like can be used.
- thermoplastic resin, thermosetting resin, active energy ray It is preferable that the glass transition point of the resin cured by irradiation of 80 ° C or less.
- the weight average molecular weight of the thermoplastic resin, the thermosetting resin, and the resin cured by irradiation with active energy rays is 5 It is preferable to use 00 or more. If the molecular weight is less than 500, the cohesive strength of the resin is too low, which may reduce the adhesion to the metal.
- thermoplastic rosin examples include the following.
- natural rubber polyisoprene, poly 1,2-butadiene, polyisobutene, polybutene, poly 2 heptilo, 1,3 butadiene, poly 2 tert-butyl-1,3 butadiene, poly-1,3-butadiene)
- Polyethers such as polyoxyethylene, polyoxypropylene, polyvinylino ethinoreateoret, polyvinylinolehexenoleatenore, polyvinylinolebutinoleate, polybutylacetate, polybulupropionate, etc.
- Polyesters Polyurethane, Ethylcellulose, Polyvinyl chloride, Polyacrylonitrile, Polymethallyl-tolyl, Polysulfone, Polysulfide, Phenoxy resin, Polyethyl acrylate, Polybutyl acrylate, Poly 2-ethylhexyl acrylate, Poly tert-butyl Luata Relay , Poly-3-ethoxypropyl acrylate), polyoxycarbonyltetramethacrylate, polymethylacrylate, polyisopropylmethacrylate, polydodecylmethacrylate, polytetradecylmethacrylate, polyn-propylmethacrylate, poly-3 , 3, 5 Trimethylcyclohexyl metatalylate, Polyethyl metatalylate, Poly 1-Traw 2-Methylpropyl metatalylate, Poly 1,1-jetylpropyl metatalylate, Polymethyl metatalylate Poly (meth) acrylic acid esters such as
- acrylic resin, epoxy resin, polyester resin, urethane resin, etc. are used as base polymers, and each is provided with radically polymerizable or cationically polymerizable functional groups.
- the material made can be illustrated.
- radically polymerizable functional groups there are carbon-carbon double bonds such as acryl group (attalyloyl group), methacryl group (methacryloyl group), bur group, allyl group, etc., and highly reactive acrylic group (attalyloyl group). ) Is preferably used.
- an epoxy group (glycidyl ether group or glycidylamine group) is typical, and a highly reactive alicyclic epoxy group is preferably used.
- Specific materials include acrylic urethane, epoxy (meth) acrylate, epoxy-modified poly Examples include butadiene, epoxy-modified polyester, polybutadiene (meth) acrylate, and acrylic-modified polyester.
- active energy rays ultraviolet rays, electron beams and the like are used.
- Photoinitiators include benzophenone, anthraquinone, benzoin, snorephonium salt, diazo-um salt, and oum. Known materials such as salt and haum-um salt can be used. Moreover, you may blend general purpose thermoplastic resin other than said material.
- thermosetting resins include natural rubber, isoprene rubber, chloroprene rubber, polyisobutylene, butyl rubber, halogenated butyl, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyisobutene, carboxy rubber, neoprene, and polybutadiene.
- thermosetting resin those using a curing agent include a resin having a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an unsaturated hydrocarbon group, an epoxy group, and a hydroxyl group.
- a curing agent having a functional group such as a group, amino group, amide group, carboxyl group or thiol group, or a curing agent such as a metal chloride, isocyanate, acid anhydride, metal oxide or peroxide.
- an additive such as a general-purpose catalyst can be used. Specifically, curable acrylic resin composition, unsaturated polyester resin composition, diallyl phthalate resin, epoxy resin composition, polyurethane resin composition and the like are exemplified.
- thermosetting resins or resins cured with active energy rays examples include acrylic acid or methacrylic acid adducts.
- urethane acrylate, epoxy acrylate, and polyether acrylate are excellent from the viewpoint of adhesion.
- epoxy acrylate 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether are used.
- a crosslinking agent for those having adhesiveness! / Scratching or exhibiting adhesiveness (hereinafter referred to as "adhesive"), a crosslinking agent, a curing agent, a dilution agent are used as necessary.
- Additives such as additives, plasticizers, antioxidants, fillers, colorants, UV absorbers and tackifiers may be added.
- the thickness of the pressure-sensitive adhesive layer is more preferably 3 / zm or more in order to ensure transfer reliability during mass production, which is preferably 1 ⁇ m or more.
- the adhesive layer is thick, the manufacturing cost of the adhesive layer increases, and the amount of deformation of the adhesive layer increases when laminated. The thickness is more preferably 10 m or less because it reduces the chance of contact between the thin-film insulating layer and the adhesive layer, which are preferred below.
- the line width of the conductor layer pattern of the substrate with the conductor layer pattern that is finally obtained is 40 m.
- the line spacing is preferably in the range of 100 m or more.
- the line width is more preferably 25 ⁇ m or less from the viewpoint of non-visibility of the conductor layer pattern (geometrical figure), and the line interval is more preferably 120 m or more from the viewpoint of visible light transmittance. If the line width is too small and thin, the surface resistance becomes too large and the shielding effect is poor, so 1 ⁇ m or more is preferable.
- the larger the line spacing the better the aperture ratio and the visible light transmittance.
- the aperture ratio needs to be 50% or more, more preferably 60% or more. If the line spacing becomes too large, the electromagnetic wave shielding property is deteriorated. Therefore, the line spacing is preferably 1000 m (lmm) or less.
- the line interval is complicated by a combination of geometric figures, etc., the area is converted into a square area based on the repetition unit, and the length of one side is used as the line interval.
- the aperture ratio of the portion that performs the electromagnetic wave shielding function is required to be 50% or more from the viewpoint of visible light transmittance. A certain force of 60% or more is more preferable. If the aperture ratio is too large, the line width becomes too small, so the aperture ratio is preferably 97% or less. From the viewpoint of line spacing, the line spacing is preferably 1000 m (lmm) or less. If the line spacing becomes too large, the electromagnetic shielding properties tend to decrease. When the line spacing is complicated by a combination of geometric figures, etc., the area is converted to a square area based on the repetition unit, and the length of one side is taken as the line spacing. From the viewpoint of visible light transmittance, the line spacing is preferably 100 m or more, more preferably 120 / z m or more. The larger the line spacing, the better the aperture ratio and the visible light transmittance.
- the thickness of the conductor layer pattern line is preferably 100 ⁇ m or less
- the thinner the thickness the wider the viewing angle of the display and the better the electromagnetic shielding material.
- the thickness of the conductor layer pattern line in the portion that assumes the grounding function is preferably 0.5 m or more, and more preferably 1 m or more, in order to ensure sufficient electric resistance. Furthermore, if the difference between the line thickness of the conductor layer pattern at the part that is responsible for the electromagnetic wave shielding function is large, a step is formed during transfer, and the boundary part is not transferred or folds are likely to occur. For this reason, the difference between the conductor layer pattern line thickness of the part that performs the electromagnetic shielding function is preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less.
- the aperture ratio of the conductor layer pattern can be increased, thereby making it possible to improve the translucency.
- a metal such as copper, silver or nickel
- the conductivity is particularly excellent.
- the base material with a conductor layer pattern in the present invention can be used as a translucent electromagnetic wave shielding member.
- an antireflection layer, a near infrared shielding layer, or the like may be further laminated.
- the base material itself that transfers the metal layer formed on the conductive base material 1 may also serve as a functional layer such as an antireflection layer or a near infrared shielding layer.
- the cover film used when coating the resin layer pattern layer with a resin may also serve as a functional layer such as an antireflection layer or a near infrared shielding layer.
- the conductive layer pattern in the present invention is blackened to ensure visibility including antireflection. It is preferable that it has been subjected to a soot treatment.
- the front surface of the electromagnetic wave shielding member is preferably black because it satisfies the requirements such as high contrast and a black screen when the display is turned off! /
- the blackening treatment various methods such as plating, oxidation treatment, and printing can be used for the metal layer.
- various methods such as plating, oxidation treatment, and printing can be used for the metal layer.
- the surface of the metal layer is oxidized and blackened by chemical conversion treatment, a fine black powder is generated in the conductor layer pattern line portion, the transmitted light intensity of the electromagnetic wave shielding member is lowered, and color unevenness occurs.
- a black material such as carbon black is mixed with a screen or the like
- it is difficult to blacken only the metal layer and the translucency of the electromagnetic wave shielding member is also impaired. Therefore, the insulating film formed on the concave portion of the conductive base material is not affected, and the metal layer and other portions are not blackened by the plating process.
- Black nickel plating that can treat only the surface of the metal layer without generating powder is most effective.
- Black nickel plating is a plating method for forming a black alloy film containing nickel sulfate as a main component by electrodeposition. it can.
- sulfur-nickel has a suitable black color and also has good adhesion to the underlying metal.
- silver, mercury, copper, lead, etc. can be used.
- a blackening treatment layer (black layer) with good adhesion should be formed only on the metal layer that does not fall off even when using an alloy plating such as tin and nickel, tin and cobalt, or black chromium plating. Is possible.
- the process of forming these blackening treatment layers can be performed before or after forming the metal layer on the upper surface of the convex portion of the conductive base material, and before transferring to another base material. It can also be done after the transfer.
- FIGS. 18 to 20 are cross-sectional views of a base material with a conductor layer pattern which also has a metal pattern force in which the conductor layer pattern is blackened.
- Fig. 18 shows the conductor layer pattern obtained by transferring the metal layer 14 formed on the convex portion from the conductive substrate to the substrate 18 via the adhesive 17, and then blackening the metal surface. It is sectional drawing of the base material with a conductor layer pattern which has. A conductor layer pattern in which a black layer 23 is formed on the side surface and the upper surface of the metal 14 is attached to a transparent substrate 18 as a substrate via an adhesive 17. Also, FIGS.
- FIG. 2 is a cross-sectional view of a base material with a conductor layer pattern obtained by blackening and then transferring the blackened metal (conductor layer pattern) to the base material 18 through an adhesive 17.
- the black layer 24 is attached to the transparent base material 18 as a base material via the adhesive 17.
- the metal 14 side is also blackened, but in Fig. 19b the metal side is blackened.
- the above electromagnetic shielding member is generally used so that the surface on which the black layer is provided faces the viewer side of the display.
- a plating solution containing nickel sulfate 60-: LOOgZL, nickel sulfate 30-50 g / L, zinc sulfate 20-40 gZL, sodium thiocyanate 10-20 gZL can be used.
- Temperature: 45 ⁇ 55 ° C Current density 0.5 ⁇ 3. OAZdm 2 conditions, stainless steel or nickel anode, circulation pump and air agitation for agitation.
- a black nickel plating layer suitable for a display panel can be formed.
- the pretreatment for black nickel plating it is more preferable to perform appropriate alkaline degreasing and acid cleaning in order to improve the adhesion to the metal layer as the base.
- plating is performed at a concentration exceeding the concentration range of each component, it becomes difficult to obtain a good black color as soon as the clinging liquid decomposes.
- plating is performed at a temperature exceeding 55 ° C, the clinging solution is easily decomposed.
- the product becomes rough and easy to fall off, which also shortens the life of the liquid. Less than 45 ° C 1.
- the optimum temperature range when performing black nickel plating in a short time using the plating solution with the above concentration composition is 45-55 ° C.
- the current density can be less than 0.5 AZdm 2 within the temperature range, but long plating is required to obtain the desired black color. 3.
- a black coating is formed that decomposes the adhesive solution and easily breaks down.
- the plating solution life will be shortened, so it is usually desirable to use a nickel anode.
- the thickness of the black treatment layer plating of 0.5 m or less does not result in complete blackness, and rainbow-like color unevenness tends to occur on the surface.
- the thickness of the blackening treatment layer is preferably 0.5 / ⁇ ⁇ to 3. O / z m.
- a fender treatment can be further performed.
- a chromate treatment, benzotriazole, or the like can be used as a known means.
- a commercially available antifungal agent can also be used.
- the blackened layer is formed again by the same method after transferring the conductive layer pattern with the blackened layer to another substrate, it is desirable to carry out the same antifouling treatment.
- the substrate with a conductor layer pattern according to the present invention is used as an electromagnetic wave shielding member, it can be used as it is by being attached to the display screen through another adhesive as appropriate or not. It may be applied to other substrates by applying to other substrates. Other substrates need to be transparent to be used to block the electromagnetic waves that are the front power of the display.
- FIG. 20 shows a cross-sectional view of an electromagnetic wave shielding member obtained by pasting a base material with a conductor layer pattern onto another base material.
- a conductor layer pattern made of a metal 14 is embedded in an adhesive layer 21 laminated on a base material (another base material) 20, and the adhesive layer 21 and the metal 14 are connected to another base material 2.
- the conductor layer pattern of the substrate with the conductor layer pattern having the conductor layer pattern made of the metal 14 bonded to the substrate (another substrate) 20 via the adhesive 21 exists. It can be produced by a method of pressure-bonding to another base material 25 with an appropriate pressure. In this case, the metal 14 is embedded in the adhesive layer 21 by applying an appropriate pressure while the adhesive layer 21 has sufficient fluidity or sufficient fluidity. In this electromagnetic wave shielding body, the adhesive layer 21 and the other base material 25 are in direct contact with each other, and good adhesion can be obtained.
- the base material (another base material) 20 is the base material (other base material) 25, which has transparency, and has a high transparency by using a material that has excellent strength and smoothness on its surface. It is possible to obtain an electromagnetic shield.
- Fig. 21 shows a cross-sectional view of an electromagnetic wave shielding member in which the base material with a conductor layer pattern is covered with a protective resin.
- a conductor layer pattern made of metal 14 is attached to an adhesive layer 21 laminated on a base material (another base material) 20, and this is covered with a transparent protective resin 26.
- FIG. 22 is a cross-sectional view of an electromagnetic wave shielding body according to another aspect. This electromagnetic wave shield is shown in Fig. 21.
- the electromagnetic shielding member is bonded to another substrate 28 via an adhesive 27 on the surface opposite to the surface on which the conductor layer pattern of the substrate (another substrate) 20 is provided.
- FIG. 23 further shows a cross-sectional view of an electromagnetic wave shielding member according to another embodiment.
- a conductor layer pattern made of metal 14 is bonded to a base material (another base material) 20 through an adhesive layer 21, and the conductive layer pattern is covered with an adhesive or an adhesive 29 made of a transparent resin. Furthermore, a protective film 30 is laminated thereon.
- Another substrate 28 such as a glass plate is attached to the other surface of the substrate 20 via an adhesive layer 27.
- the surface on which the conductor layer pattern of the substrate with the conductor layer pattern having the conductor layer pattern adhered to the substrate (another substrate) 20 via the adhesive 21 is disposed on the transparent resin.
- a protective film 30 is further laminated, and then an adhesive is applied to the other side (the surface on which nothing is laminated) of the base material 20 of the obtained laminate to form an adhesive layer 27. It can be produced by forming it and pressing it against another substrate 28 for adhesion.
- a resin that is cured with active energy rays can be used. It is preferable to use a resin that hardens with active energy rays because it hardens instantaneously or in a short time, and thus the productivity increases.
- a rotating body can be used as the conductive base material used in the present invention, and further details thereof will be described.
- the rotating body (roll) is preferably made of metal.
- a drum electrode or the like used in the drum-type electrolytic deposition method as the rotating body.
- the material that forms the surface of the drum electrode has relatively low adhesion to stainless steel, chromium-plated pig iron, chromium-plated steel, titanium, and titanium-lined materials. , Prefer to use the material.
- a rotating body as the conductive base material, it is possible to obtain a base material with a conductor layer pattern as a roll, and in this case, productivity is greatly increased.
- FIG. Fig. 24 shows an apparatus for continuously depositing metal by electric plating while continuously rotating the drum electrode when a drum electrode is used as the conductive base material. It is sectional drawing (partial front view) which shows a concept. That is, the electrolytic solution 101 in the electrolytic bath 100 is supplied to the space between the anode 102 and the rotating body 103 such as the drum electrode by the pipe 104 and the pump 105.
- a convex portion and a concave portion having a geometric diagram shape drawn thereby are formed on the surface of the rotating body 103.
- the surface of the rotating body 103 is subjected to etching cleaning (not shown) before being immersed in the electrolytic solution 101.
- the upper end of the anode 102 may be installed with a draining roll to prevent the electrolyte circulating at high speed from being ejected upward. Returns from outside the anode 102 to the lower electrolyte bath and is circulated by the pump.
- a hoop-shaped conductive substrate can be produced by forming a convex portion on the surface of a strip-shaped conductive substrate and then joining the end portions.
- the material that forms the surface of the conductive base material has relatively high adhesion to stainless steel, chromium-plated pig iron, chromium-plated steel, titanium, titanium-lined materials, etc. It is preferable to use a small wrinkle material.
- the blackening process, anti-bacterial treatment, transfer process, etc. can be processed in one continuous process, so the productivity of the substrate with a conductive pattern is high.
- a substrate with a conductive pattern can be continuously produced to obtain a product as a scroll.
- the thickness of the hoop-like conductive substrate may be determined as appropriate, but is 100 to 1000 m. Preferably there is.
- FIG. 25 is a conceptual diagram of an apparatus for continuously peeling a conductor layer pattern by electroplating when a hoop-like conductive substrate is used as the conductive substrate.
- the hoop-like conductive substrate 110 is transferred to the pretreatment tank 129, the plating tank 130, the water washing tank 131, the blackening treatment tank 132, the water washing tank 133, and the fender treatment tank 134 using the transport rolls 111 to 128.
- the water tank 1 35 will be installed so that it can orbit around.
- the conductive substrate 110 is degreased, acid-treated, etched, etc. to remove the metal remaining on the conductive substrate. Thereafter, metal is deposited on the conductive substrate 110 in a plating bath (electrolytic bath) 130.
- the water washing tank 131, the blackening treatment tank 132, the water washing tank 133, the antifouling treatment tank 134, and the water washing tank 135 are sequentially passed, and the surface of the metal deposited on the conductive substrate 110 is blackened. Further anti-bacterial treatment is performed. Although only one tank is shown after each treatment process, a plurality of tanks may be used as necessary, or some pretreatment tank may be provided before each treatment process.
- the plastic film substrate 136 with the adhesive layer laminated is transferred between the conductive substrate 110 and the pressure roll 137 on the transport roll 128 so that the metal deposited on the upper surface of the convex portion of the conductive substrate 110 is transferred.
- the metal can be transferred to the plastic film substrate 136 and the substrate 138 with a conductive layer pattern can be continuously produced.
- the obtained base material 138 with a conductive layer pattern can be wound into a roll.
- the pressure-bonding roll 137 can be heated.
- the plastic film substrate 136 may be preheated through a preheating tank before passing through the pressure-bonding roll.
- release PET or the like may be inserted as needed to remove the transferred film.
- the hoop-like conductive base material repeats the above process. In this way, it is possible to continuously produce a substrate with a conductor layer pattern with high productivity.
- FIG. Fig. 26 shows another example in which a conductive layer material is continuously peeled while being deposited by electrical contact when a hoop-like conductive substrate is used as the conductive substrate. It is a conceptual diagram of the apparatus shown.
- the hoop-like conductive substrate 110 is installed through the transport rolls 111 to 116, 140 to 143, 127 and 128.
- a pretreatment tank 129 for example, an etching tank for removing residual metal in the conductive base 110 after transfer
- the metal is deposited on the conductive substrate in two plating baths (electrolytic baths) 130 and 150.
- a blackening treatment tank 151 may be installed to blacken the surface of the deposited metal.
- a fender treatment tank or the like may be provided (not shown). These baths may be a single plating bath (electrolytic bath) 130, a blackening treatment bath 150, and a fender treatment bath 151.
- the metal deposited on the upper surface of the convex portion of the conductive substrate 110 is transferred to the plastic film substrate 136 using the plastic film substrate 136 and the pressure roll 137 on which the adhesive layer is stacked, and the conductive layer pattern is transferred.
- the point that the base material 138 with a lead is continuously manufactured is the same as in FIG.
- an antireflection layer, a near infrared shielding layer, or the like may be further laminated.
- the base material itself that transfers the metal deposited on the conductive base material 1 may also serve as a functional layer such as an antireflection layer or a near infrared shielding layer.
- the cover film used when coating the resin layer pattern layer with a resin may also serve as a functional layer such as an antireflection layer or a near infrared shielding layer.
- the present invention is not limited to the plating method as described above, and it is also possible to produce a single wafer.
- the drum When performed on a single wafer, the drum is easy to handle during the production of the conductive substrate for plating, and the insulation layer peels off only once after the same conductive substrate for plating is used repeatedly. It is difficult to extract or replace only a specific part if it is a substrate in the shape of a hoop or a hoop, but if it is a sheet, it is possible to extract or replace only the conductive substrate for plating in which a defect has occurred. is there. Thus, by making it by a single wafer, it is easy to cope when a defect occurs in the conductive substrate for plating.
- the thickness of the sheet-like conductive substrate may be determined as appropriate, but the thickness is preferably 20 m or more in consideration of providing sufficient strength that is not affected by the stirring of the liquid in the plating tank. If it is too thick, the weight increases and it is difficult to handle.
- fixing the insulating layer to the conductive base means that the resin corresponding to the insulating layer is hardened. This process is generally called a curing or baking process.
- Inert gas refers to V and gas that do not react with the resin component that forms the thin-film insulation layer.
- an inert gas refers to a gas that is not reactive with neon or argon, but in the present invention, a gas that is not reactive with a thin film insulating layer, such as nitrogen, is not limited thereto. Etc. Nitrogen is also preferred for points such as availability, price and consideration for the environment.
- An electrodeposition paint will be described as an example.
- pre-curing or pre-drying in which water or solvent adhering to the surface is dried at a low temperature after the electrodeposition coating is applied to the conductive substrate.
- the resin is not completely cured, and the atmosphere at this time does not have to be an inert gas atmosphere.
- the resin is reacted at a high temperature for the purpose of completely curing the resin.
- UV-curing electrodeposition paints UV rays are irradiated instead of baking at high temperatures. At this time, the electrodeposition paint reacts with reactive functional groups in the resin so that it is highly reactive and easily causes side reactions.
- a typical example is the oxidation reaction by reaction with oxygen in the air, and the resin tends to deteriorate due to the acid-acid reaction, especially when it is attempted to cure the resin completely for a long time at a high temperature. It is in. It is important to cure or bake in an inert gas atmosphere in order to prevent such side reactions.
- the concentration of these inert gases may vary slightly depending on the ratio between the size of the curing furnace and the area of the insulating layer to be cured.
- the volume ratio of the inert gas is preferably 90% or more with respect to the entire atmosphere. It is more preferably 95% or more, more preferably 98% or more, and even more preferably 99% or more.
- the line width, pitch, and aperture ratio were measured based on micrographs.
- the thickness of the line and the thickness of the copper foil were measured by partially cutting the obtained base material with a conductor layer pattern, casting it with a resin, and observing the cross section under a microscope.
- the visible light transmittance was determined by measuring the transmittance of 400 to 700 nm using a double beam spectrophotometer (200-10 type, manufactured by Hitachi, Ltd.), and calculating the average value. The presence or absence of pattern abnormality was confirmed with the naked eye using a magnifier.
- Electromagnetic shielding uses the Advantest method, Measurement was performed at a frequency of 300 MHz.
- the durability of the conductive substrate was confirmed by observing the conductive substrate directly with a magnifier after repeated fitting and peeling.
- the average transmittance of 850 to 1 lOOnm was determined by measuring the transmittance of 850 to LlOOnm using a double beam spectrophotometer (200-10, manufactured by Hitachi, Ltd.).
- a resist film (Photec H-Y920, manufactured by Hitachi Chemical Co., Ltd.) was bonded to a 10 cm square stainless steel (SUS304) plate.
- the bonding conditions were a roll temperature of 105 ° C, a pressure of 0.5 MPa, and a line speed of lmZmin.
- the negative film formed in a lattice shape with the line width of the light transmitting portion of 30 m, the line pitch of 300 ⁇ m, and the bias angle force of 5 ° was left on the stainless steel plate bonded with the resist film. .
- ultraviolet irradiation device ultraviolet rays were irradiated at 120 miZcm 2 from above the negative film under a vacuum of 600 mmHg or less. further.
- electrolytic copper plating with a stainless steel plate (a conductive substrate having a convex pattern having an upper surface and a geometrical figure-shaped concave portion drawn thereby) having a lattice pattern as a cathode.
- Electrolytic copper plating bath (copper sulfate (pentahydrate) 80gZL, sulfuric acid 180g ZL, Cubelite VF1 (supplied by Ebara Eugene Co., Ltd., additive) 20mlZL aqueous solution, 25 ° C) A stainless steel plate was immersed, and phosphorous copper was immersed in the electrolytic copper plating bath as an anode.
- a primer HP-1; manufactured by Hitachi Chemical Co., Ltd.
- PTT polyethylene terephthalate
- A-4100 manufactured by Toyobo Co., Ltd.
- an acrylic polymer HTR-280, manufactured by Nagase Chemtech was sequentially applied to a thickness of 10 m to prepare an adhesive film.
- the pressure-sensitive adhesive surface of this pressure-sensitive adhesive film was bonded to the surface of the stainless steel plate with copper plating using a roll laminator.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0. IMP a, and a line speed of lmZmin.
- the copper layer formed on the upper surface of the convex portion of the SUS plate was buried by about 0.5 m in the adhesive layer of the adhesive film.
- the adhesive film bonded to the stainless steel plate is peeled off, the copper deposited on the upper surface of the convex portion of the stainless steel plate is a continuous film, so it is transferred to the adhesive film, whereas it is deposited on the concave portion and the side portion.
- the copper was a granular and discontinuous film, it remained on the stainless steel plate without following the copper deposited on the upper surface of the convex portion, and was not transferred to the adhesive film. In this way, a metal pattern having a line width of 20 m, a line pitch of 300 ⁇ m, and a conductor thickness of 5 ⁇ m was selectively transferred onto the adhesive film.
- the adhesive film onto which the metal pattern obtained above was transferred was immersed in an aqueous solution obtained by diluting alkaline degreasing solution Degree A (Odec Co., Ltd.) 5 times at room temperature for 3 minutes. Next, after washing with water, it was immersed in a 10% nitric acid aqueous solution at room temperature for 2 minutes. Further, after washing with water, the substrate was immersed in a 4-fold diluted aqueous solution of blackening solution copar (Odec Co., Ltd.), and the metal pattern was blackened to produce a substrate with a conductor layer pattern of the present invention.
- the stainless steel plate on which the convex pattern was formed was immersed in lOOgZ liters of ammonium persulfate solution heated to 40 ° C to form the convex pattern. Copper remaining in the concave portion and the side portion of the formed stainless steel plate was dissolved.
- a grid pattern (line width 10 / ⁇ ⁇ , pitch) was formed on the SUS plate in the same manner as in Example 1 except that the etching was performed until the line width of the convex portion formed on the SUS plate was 10 ⁇ m.
- a stainless steel plate etched in a lattice pattern (a conductive substrate having a convex pattern having an upper surface and a geometric pattern-shaped concave portion drawn thereby) is used as a cathode for electrolytic copper plating.
- Electrolytic bath (copper sulfate (pentahydrate) 150gZL, sulfuric acid 150gZL, Kaparaside HL (manufactured by Atotech Japan Co., Ltd., additive) 50ml ZL in water, 30 ° C) Immerse in the bath. Voltage was applied to both poles, the current density was lOAZdm 2 , and the metal deposited on the top surface of the protrusions reached the thickness of 3 ⁇ m. The force with which copper was deposited as a continuous film on the upper surface of the convex part of the stainless steel plate.
- Granular copper with a particle size of about 1 ⁇ m was deposited in a continuous manner on the concave part and side part.
- a primer HP-1; manufactured by Hitachi Chemical Co., Ltd.
- a 100 m thick polyethersulfone film Silicon FS-1300, manufactured by Sumitomo Beta Light Co., Ltd.
- the adhesive surface of the adhesive film and the copper-plated surface of the stainless steel plate were bonded together using a roll laminator.
- Lamination conditions are: roll temperature 150 ° C, pressure 0.1M Pa and line speed were set to 0.5 mZmin. Since lamination was performed at a temperature exceeding the Tg of the adhesive, tackiness was developed on the adhesive surface.
- the blackened copper layer formed on the upper surface of the convex portion of the SUS plate was buried in the adhesive layer of the adhesive film by about 1 ⁇ m.
- the adhesive film bonded to the stainless steel plate was peeled off, the copper deposited on the upper surface of the convex portion of the stainless steel plate was a continuous film, and thus transferred to the adhesive film.
- the copper deposited on the concave portions and the side portions is a granular and non-continuous film, it remains on the SUS plate without following the copper deposited on the upper surface of the convex portions and transferred to the adhesive film. There was no. In this way, a metal pattern having a line width of 10 ⁇ m, a line pitch of 300 ⁇ m, and a conductor thickness of 3 ⁇ m and further blackened is selectively transferred onto the adhesive film, and the conductor of the present invention. A substrate with a layer pattern was produced.
- a UV curable resin hyaloid 7983AA3 manufactured by Hitachi Chemical Co., Ltd.
- PET film A-4100, manufactured by Toyobo Co., Ltd., 75 m
- UV curable resin to form a conductive layer pattern. It was embedded in a curable type rosin.
- the UV curable resin was cured by irradiating UV light of UZcm 2 using an ultraviolet lamp, and then the PET film (A-4100, manufactured by Toyobo Co., Ltd., 75 m) was peeled off.
- the copper remaining on the concave portions and the side portions of the stainless steel plate on which the convex pattern was formed was dissolved in the same manner as in Example al.
- Byron UR-1350 adheresive, manufactured by Toyobo Co., Ltd.
- SUS304 foil Takeuchi Metal Foil Powder Co., Ltd., thickness 100 m
- PET film A-4100, manufactured by Toyobo Co., Ltd.
- the adhesive film produced by applying the dry coating thickness to 20 m was pasted with a press.
- the pressing conditions were a hot press at 130 ° C, a pressure of 4 MPa, and pressing for 30 minutes. The sample was taken out after cooling to 25 ° C with pressure applied.
- the SUS foil with PET film obtained above was etched under the same conditions as in Example al until the width of the convex portion was 15 / zm, and a lattice pattern (line width 15 / zm pitch 300 / zm
- the height of the convex part is 20 m
- the cross-sectional shape of the convex part is a curved surface (similar to Fig. 3-d).
- electrolysis using a SUS foil with a PET film on which a lattice-like pattern is formed (a conductive base material having a notch of a convex part having an upper surface and a concave part of a geometrical figure drawn by the same) as a cathode.
- an electrolytic bath for copper plating copper sulfate (pentahydrate) 180gZL, sulfuric acid 10 OgZL, Kaparaside HL (manufactured by Atotech Japan Co., Ltd.), 70mlZL aqueous solution, 30 ° C), and use phosphorous copper as an anode
- a voltage was applied to both electrodes, the current density was set to 30 AZdm 2 , and plating was performed until the thickness of the metal deposited on the top surface of the protrusion became 1 ⁇ m.
- the SUS foil with PET film on which copper plating was deposited was immersed in an aqueous solution obtained by diluting alkaline degreasing solution Degrease A (Odec Co., Ltd.) 5 times at room temperature for 3 minutes.
- a 10% nitric acid aqueous solution was immersed in a 10% nitric acid aqueous solution at room temperature for 10 seconds.
- blackening solution copal Odec Co., Ltd.
- Resin composition 1 was applied to the easy-adhesion surface of a 100 ⁇ m thick PET film (A-4100, manufactured by Toyobo Co., Ltd.) so that the dry coating thickness was .
- a composition comprising 100 parts by weight of AS-406 (acrylic polymer, manufactured by Katsushi Yushi Co., Ltd.) and 2 parts by weight of Tetrad X (manufactured by Mitsubishi Gas Chemical Co., Ltd., curing agent).
- This adhesive film and the above-mentioned SUS foil with PET film on which a blackened copper plating is laminated are combined with the former adhesive surface and the latter blackened copper plating surface. As expected, they were bonded in the same manner as in Example 1. At this time, the black copper-treated copper layer formed on the upper surface of the convex portion of the SUS foil was buried in the adhesive layer of the adhesive film by about 0.5 m.
- the copper deposited on the upper surface of the convex part of the SUS foil with PET film is a continuous film, so that it is transferred to the adhesive film, whereas the copper and Since the copper deposited on the part is a granular and discontinuous film, the upper surface of the convex part It remained on the SUS plate without following the copper deposited on it and was not transferred to the adhesive film.
- a blackened metal pattern with a line width of 15 ⁇ m, a line pitch of 300 m, and a thickness of 1 m was selectively transferred onto the adhesive film.
- the dissolution and removal of the copper remaining on the concave portions and side portions of the SUS foil with PET film on which the convex pattern was formed was performed in the same manner as in Example al.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film obtained above (the surface on which the copper plating was transferred) was applied to a glass sheet having a thickness of 2 mm and laminated.
- Lamination conditions were a temperature of 25 ° C, a pressure of 0.5 MPa, and a line speed of 0.5 mZmin.
- the 1 m thick conductor layer pattern was embedded in the adhesive, and a highly transparent electromagnetic shielding body was obtained.
- a Ni foil with PET film was prepared in the same manner as Example a3 except that electrolytic Ni foil (Fukuda Metal Co., Ltd., thickness 35 ⁇ m) was used instead of SUS304 foil.
- a lattice pattern (line width 15 / ⁇ ⁇ , pitch 300 / ⁇ ⁇ , convex height 20 / ⁇ ⁇ , convex sectional shape is curved (similar to Fig. 3-d)) was formed.
- an acid film was formed on the Ni surface with Ni anodic acid. The anodic oxidation was performed in a 10% aqueous solution of sodium hydroxide and sodium hydroxide for 30 seconds using a Ni foil as the anode and a SUS plate as the cathode, with a voltage of IV applied to both electrodes.
- Ni foil with PET film etched in a lattice pattern was used as the cathode for electrolytic copper plating Soaked in an electrolytic bath (copper sulfate (pentahydrate) 180gZL, sulfuric acid 100gZL, power Noracid HL (manufactured by Atotech Japan Co., Ltd., 70ml ZL aqueous solution, 30 ° C)) Immerse in an electrolytic bath. Voltage was applied to both poles, and the current density was set to 30 AZdm 2 until the thickness of the metal deposited on the upper surface of the protrusion reached 10 ⁇ m.
- Copper was deposited as a continuous film on the upper surface of the convex part of the Ni foil with PET film. On the side, granular copper having a particle size of about 0.8 m was discontinuously deposited.
- the thickness of the PET film (Mylar D, manufactured by Teijin DuPont Films Co., Ltd.) with a thickness of 100 ⁇ m on the surface of the resin composition a2 containing the following infrared absorber is 20 ⁇ m after drying.
- An adhesive film was prepared by applying to the above.
- BR-80 Mitsubishi Rayon Co., Ltd., PMMA
- IRG-022 Nippon Kayaku Co., Ltd., Dimo-um salt-based infrared absorber
- MEK Methyl ethyl ketone
- the resin composition a3 was applied to the release-treated surface of release PET (S-32, manufactured by Teijin DuPont Co., Ltd.) so that the dry application thickness was 8 m.
- An adhesive film having a near-infrared shielding property was prepared by laminating a film coated with the resin composition a3 on the surface coated with the resin composition a2 of an adhesive film containing a near-infrared absorber.
- HTR-860- P3 (Nagase Chemtech Co., Ltd., acrylic polymer) 100 parts by weight and Coupnate L (Nihon Polyurethane Co., Ltd., isocyanate compound) 3 parts by weight of toluene 100 parts by weight of ethyl acetate 300 parts by weight Part of a mixed solvent.
- the copper deposited on the concave portions and the side portions is a granular and discontinuous film, it remains on the Ni foil that does not follow the copper deposited on the upper surface of the convex portions and is transferred to the adhesive film. Hana was strong.
- the obtained adhesive film with a conductor layer pattern was subjected to blackening. Processed. Further, after the blackening treatment, the surface on which the conductor layer pattern of the substrate with the conductor layer pattern is present is coated with an ultraviolet curable resin (Hitaroid 7851, manufactured by Hitachi Chemical Co., Ltd.), and a polycarbonate film ( After laminating Macro Hall DE, Bayer Co., Ltd. (75 m), UZcm 2 ultraviolet rays were irradiated using an ultraviolet lamp, and the conductor layer pattern was coated with resin. Next, an adhesive layer was formed on the surface of the film obtained above opposite to the surface on which the conductor layer pattern was formed, and was bonded to a 3 mm thick PMMA plate (Comoglass) to obtain an electromagnetic wave shielding member.
- an ultraviolet curable resin Haitaroid 7851, manufactured by Hitachi Chemical Co., Ltd.
- Example a3 SUS foil with PET film treated with copper plating and black wrinkle in the same manner as Example a3 (line width 15 m, pitch 300 m, convex height 20 m, convex sectional shape is curved surface ( Fig. 3d)) was formed. Furthermore, the following resin composition a4 was applied to the surface of a 100 m thick polyethersulfone film (Sumilite FS-1300, manufactured by Sumitomo Bakelite Co., Ltd.) so that the thickness after drying was 13 m. An adhesive film was obtained. Drying conditions were 90 ° C for 5 minutes.
- the obtained adhesive film and a stainless steel foil with a PET film having a blackened metal pattern on the convex part obtained in Example a3 were bonded with a laminator.
- Lamination conditions were a roll temperature of 120 ° C, a pressure of 3 MPa, and a line speed of lmZmin.
- the blackened metal existing on the upper surface of the convex part of the stainless steel plate is selectively transferred to the adhesive surface, and the line width is 15 m, the line pitch is 300 m, and the conductor thickness is 1 ⁇ m.
- a conductor layer pattern was formed on the adhesive film.
- the transferred stainless steel plate is the same as in Example al, and the copper remaining on the surface is removed.
- the adhesive film having the conductor layer pattern obtained above was treated at 150 ° C for 60 minutes to cure the adhesive, thereby obtaining a substrate with a conductor layer pattern.
- PET After coating the surface of the base material with the conductor layer pattern obtained above with the UV curable resin hyaloid 7983AA3 (manufactured by Hitachi Chemical Co., Ltd.) in the same manner as in Example al, PET
- the surface of the film (A-4100, manufactured by Toyobo Co., Ltd., 75 / zm) that has not been subjected to easy adhesion treatment is laminated with UV curable resin to embed the conductor layer pattern in UV curable resin.
- the PET film (A-4100, manufactured by Toyobo Co., Ltd., 75 / zm) was peeled off.
- the dissolution of the copper remaining on the concave portions and the side portions of the stainless steel plate on which the convex pattern was formed was performed in the same manner as in Example al.
- S-32 manufactured by Teijin DuPont Co., Ltd.
- Resist film (Photec LF-1515, manufactured by Hitachi Chemical Co., Ltd.) The film was bonded to a 10 cm copper plate (thickness 2 mm). The bonding conditions were a roll temperature of 105 ° C, a pressure of 0.5 MPa, and a line speed of lmZmin. Next, a negative film formed in a lattice shape with a line width of the light transmitting portion of 30 m, a line pitch of 200 ⁇ m, and a bias angle of 30 ° was left on a copper plate bonded with a resist film.
- ultraviolet rays were irradiated from the top of the negative film at 120 mjZcm 2 under a vacuum of 60 OmmHg or less. further.
- a resist film having a line width of 30 ⁇ m, a line pitch of 200 ⁇ m, and a bias angle of 30 ° was formed on a copper plate.
- the copper plate was etched using a salty ferric aqueous solution heated to 40 ° C. Etching was performed until the line width of the copper plate reached 25 m.
- the resist film formed on the copper plate is peeled off to form a lattice pattern (line width 25 / ⁇ ⁇ , line pitch 200 / ⁇ ⁇ , convex
- the height of the part is 11 / ⁇ ⁇
- the cross-sectional shape of the convex part is a curved surface ( Figure 3-—same as d).
- a chromium layer was formed by sputtering on the surface of the copper plate on which the lattice pattern was formed so as to have a thickness of 0.3 ⁇ m.
- the copper plating applied thereon is easily peeled off.
- Electrolytic copper plating was performed using the copper plate sputtered with chromium as a cathode. In the electrolytic copper plating bath (copper sulfate (pentahydrate) 100g / L, sulfuric acid 180gZL, Topchina H-380 (Okuno Pharmaceutical Co., Ltd., additive) 2.
- the copper plate on which the chromium layer plated with copper was formed was immersed in the black solution 1 and treated at 80 ° C. for 1 minute to blacken the copper. Transfer the blackened copper to the same adhesive film as in Example a 1 except that the thickness of the adhesive layer was 5 m, line width 25 ⁇ m, line pitch 200 ⁇ m, conductor thickness 3 ⁇ m A substrate with a conductor layer no turn was prepared. Further, the copper plate on which the chromium layer after transfer was formed was the same as in Example al, and the copper remaining on the surface was removed.
- the substrate with a conductor layer pattern obtained above and a glass plate having a thickness of 2 mm were heated so that the surface on which the conductor layer pattern of the substrate was formed was in contact with the glass plate. 30 ° C, pressure 2. Laminated with OMPa and bonded together. The conductor layer pattern was embedded in the pressure-sensitive adhesive, and a highly transparent and electromagnetic shielding member was obtained.
- a grid pattern (line width 20 / ⁇ ⁇ , pitch 300 / ⁇ ⁇ , convex height 15 / ⁇ ⁇ , convex section) on a stainless steel roll with a diameter of 150 mm in the same manner as in Example al.
- the shape was a curved surface (similar to Fig. 3-d).
- the current density of 40AZdm 2 were plated to the metal thickness to be deposited on the upper surface of the protrusion by applying a voltage to the both electrodes becomes 5 mu m thick.
- the upper surface of the convex portion of the stainless steel roll was the force of copper deposition as a continuous film. In the concave portion, granular copper with a particle diameter of about 3 ⁇ m precipitated discontinuously.
- Example al The pressure-sensitive adhesive film used in Example al was produced in a roll shape, and the adhesive surface of copper and the pressure-sensitive adhesive film deposited on the upper surface of the convex portion of the stainless steel roll was bonded together under the same lamination conditions as in Example al. . At this time, the copper layer formed on the upper surface of the convex portion of the stainless steel roll was buried by about 0.5 m in the adhesive layer of the adhesive film.
- the copper deposited on the upper surface of the convex portion of the stainless steel roll is a continuous film, so it is transferred to the adhesive film, whereas the copper deposited in the concave portion is Since it is a granular and discontinuous film, it remained on the SUS plate without following the copper deposited on the upper surface of the convex part, and was not transferred to the adhesive film.
- a conductor layer pattern having a line width of 20 m, a line pitch of 300 ⁇ m, and a conductor thickness of 5 ⁇ m was selectively transferred onto the adhesive film.
- the adhesive film on which the metal pattern obtained above was transferred was blackened in the same manner as in Example al to produce a substrate with a conductor layer pattern of the present invention.
- the surface of the substrate with the conductor layer pattern obtained, on which the conductor layer pattern is formed is coated with a UV curable resin (ALONIX UV-3701, manufactured by Toagosei Co., Ltd.) with a thickness of 15 m, and a PET film (Mylar 1D, made by Teijin DuPont Films, Ltd., 75 m), and then irradiated with lj / cm 2 ultraviolet rays using an ultraviolet lamp.
- a UV curable resin ALONIX UV-3701, manufactured by Toagosei Co., Ltd.
- PET film Mylar 1D, made by Teijin DuPont Films, Ltd., 75 m
- Example a8 Rolled SUS304 foil (thickness 100 ⁇ m), PET film (A-4100, manufactured by Toyobo Co., Ltd.) and Byron UR-1350 (adhesive, manufactured by Toyobo Co., Ltd.) with a dry coating thickness of 20
- a roll-like adhesive film prepared by coating so as to be m was pasted with a roll laminator to produce a SUS foil with a roll-like PET film.
- Lamination conditions were a roll temperature of 120 ° C, a preheat of 120 ° C for 30 seconds, a pressure of 3 MPa, and a line speed of 0.5 mZmin.
- the SUS foil with PET film was etched in the same manner as in Example a3 except that the roll was continuously transferred from roll to roll in the same manner as in Example a7, and a lattice-like pattern (line) was formed on the SUS foil.
- the width was 15 / ⁇ ⁇
- the pitch was 300 / ⁇ ⁇
- the height of the convex portion was 20 / ⁇ ⁇
- the cross-sectional shape of the convex portion was a curved surface (same as in Fig. 3-d).
- the surface roughness Rz of the top surface of the convex portion formed on the SUS foil was 0.4 m, whereas the surface roughness Rz of the concave portion was 5.
- paper was passed through an apparatus as shown in FIG. 26 using the SUS foil having a lattice pattern formed on the roll obtained above. The joints were bonded with Mylar tape to form a hoop-like conductive substrate.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film with a conductor layer pattern obtained above (the surface on which the copper plating was transferred) was applied to a glass sheet having a thickness of 2 mm and laminated.
- Lamination conditions were a temperature of 25 ° C, a pressure of 0.5 MPa, and a line speed of 0.5 m / min.
- the 1 m thick conductor layer pattern was embedded in the adhesive, and a highly transparent electromagnetic shielding body was obtained.
- a dry film photoresist (HY-920 (manufactured by Hitachi Chemical Co., Ltd., thickness 20 / zm)) was bonded to a stainless steel (SUS304) plate at a roll temperature of 100 ° C, a linear pressure of 0.3 MPa, and a line speed of lmZmin.
- a negative pattern with a line width of 30 m and a line pitch of 300 m is placed on a stainless steel plate with a resist film attached, and the upper force of the negative pattern is also irradiated with UV under the condition of lOOmj / cm 2.
- Development was performed with a 1% aqueous sodium carbonate solution to form a resist film having a groove with a width of 30 m on a SUS plate, and then heat-cured at 150 ° C. for 1 hour.
- an electrolytic bath for electrolytic copper plating using the SUS plate on which the resist is formed as a cathode [copper sulfate (pentahydrate) 100gZL, sulfuric acid 180gZL, Top Lucina H-380 (Okuno Pharmaceutical Co., Ltd., (Additives) (What is this?) 2.
- a voltage was applied to both electrodes to set the current density to 3 A / dm 2 and plating was performed with a thickness of 20 m so that the resist groove was completely filled.
- a metal plated in a non-turn pattern is adhesive when transferred to an adhesive film, for example. Since the layer is in contact with the insulator that forms the pattern, a peel stress is applied to the insulator every time the adhesive film to which the metal pattern is transferred is peeled off. Furthermore, since the insulator is formed in a pattern, the contact area of the insulator with SUS is very small, so the process of plating ⁇ transfer in a pattern is repeated several to several hundred times. However, at the mass production level of several thousand to several tens of thousands of times, the insulation is peeled off from the conductive substrate! /, And the pattern life is short.
- the resin used to form the pattern and the adhesive used to peel the conductor layer from the conductive substrate Organic strength such as film peeling residue
- the plating solution is contaminated, so the life of the plating solution is shortened and plating deposition failure is likely to occur.
- Example 9 (hereinafter, also referred to as “Example bl”. The same applies to Example 15) will be described. (Manufacture of conductive substrate having notched convex part with upper surface and concave part of geometric figure drawn by it)
- a resist film (Photech H-Y920, manufactured by Hitachi Chemical Co., Ltd.) was bonded to a 10 cm square stainless steel (SUS304, finished 3Z4H, thickness 100 m, manufactured by Nisshin Steel Co., Ltd.).
- the shelling conditions were as follows: roll temperature 105 ° C, pressure 0.5 MPa, line speed lm Zmin.
- a negative film formed in a lattice pattern with a line width of 30 ⁇ m, a line pitch of 300 ⁇ m, and a bias angle force of S45 ° is allowed to stand on a stainless steel plate to which a resist film is bonded. did.
- ultraviolet rays were irradiated at 120 mjZcm 2 from above the negative film under a vacuum of 600 mmHg or less. further. 1
- a resist mask having a line width of 30 m, a line pitch of 300 ⁇ m, and a bias angle of 45 ° was formed on the SUS plate.
- the SUS plate was etched using a ferric chloride aqueous solution (45 ° Be ', manufactured by Tsurumi Soda Co., Ltd.) heated to 40 ° C. Etching was performed until the line width of the SUS plate reached 20 / zm.
- the resist film formed on the SUS plate is peeled off to form a lattice pattern (line width, that is, the width of the upper surface of the convex portion is 20 m, the pitch is 300 m).
- line width that is, the width of the upper surface of the convex portion is 20 m, the pitch is 300 m.
- m height of convex part 15; ⁇ ⁇ , cross-sectional shape of convex part forms a curved surface (similar to Fig. 3-d)), convex part of convex part with upper surface and geometric figure shape drawn by it
- a conductive base material having a recess was prepared.
- the above conductive base material is used as a cathode, and the anode is used as a titanium plate.
- a cationic electrodeposition paint (Insuleed 3020, manufactured by Nippon Paint Co., Ltd.), it is etched into a lattice pattern under the condition of 15 V for 10 seconds.
- a stainless steel plate was electrodeposited. After washing with water and drying at 100 ° C for 10 minutes, baking was performed at 190 ° C for 25 minutes. The coating thickness of the electrodeposition paint was 2.
- the electrodeposited stainless steel plate is polished on the top surface of the convex part using polishing powder (alumina solution B0. 05 ⁇ m, manufactured by Refinetech) and polishing cloth (made by CONSUMABLES Buehler GMBH).
- the SUS surface was exposed, and a conductive substrate having an insulating film was produced.
- the thickness of the electrodeposition coating on the top edge of the convex part of this conductive substrate is 2.5 m (however, measured in the plane direction of the top surface), and the thickness of the electrodeposition coating in the concave part is 2. It was 5 m.
- This conductive substrate was covered with an insulating film except for the upper surface of the convex portion.
- Electrolytic copper plating bath (copper sulfate (pentahydrate) 80gZL, sulfuric acid 180gZL, Cubelite VF1 (supplied by Sakakibara Eulite Co., Ltd., additive) 20mlZL aqueous solution, 25 ° C) etched into a lattice pattern
- the stainless steel plate was immersed, and immersed in the electrolytic copper plating bath using phosphorous copper as an anode.
- a current density of 25AZdm 2 the thickness of the metal deposited on the upper surface of the convex portion of the conductive substrate was plated to a 5 mu m.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film and the copper-coated surface of the conductive substrate were bonded together using a roll laminator.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0.1 IMPa, and a line speed of lmZmin.
- copper deposited on the upper surface of the convex portion of the conductive substrate was transferred to the adhesive film. From this, a substrate with a conductor layer pattern consisting of a metal pattern having a line width of 28 ⁇ m, a line pitch of 300 ⁇ m, and a conductor thickness of 5 ⁇ m was obtained.
- the portion where the insulating film was peeled off was strong.
- the substrate with the conductor layer obtained above was immersed in an aqueous solution obtained by diluting alkaline degreasing solution Degrease A (Odec Co., Ltd.) 5 times at room temperature for 3 minutes, then washed with water, and then 10% nitric acid solution Immerse it in a solution at room temperature for 2 minutes, and after washing with water, immerse it in a 4-fold diluted aqueous solution of black candy treatment liquid COPAL (Odek Co., Ltd.) to obtain a conductor layer pattern that has been blackened. A substrate was obtained.
- Degrease A Odec Co., Ltd.
- UV curable resin hyaloid 7983AA3 manufactured by Hitachi Chemical Co., Ltd.
- a polycarbonate film Micro Hall DE, Bayer Co., Ltd., 75 ⁇ m
- UV curable resin was cured to obtain a substrate with a conductor layer pattern having a protective film.
- a grid pattern (line width 7 / ⁇ ⁇ , pitch) was formed on the SUS plate in the same manner as in Example bl except that the line width of the protrusions formed on the SUS plate was etched to 7 ⁇ m. 300 m, the height of the convex part 30 m, the cross-sectional shape of the convex part forms a curved surface (similar to Fig. 3-d)), the convex part of the convex part with the upper surface and the geometric figure shape drawn by it A conductive substrate having a recess was obtained.
- the above conductive base material is used under the condition of 10 V 60 seconds in an on-type electrodeposition paint (AMG-5EZ5W, manufactured by Shimizu Co., Ltd.) using the above conductive base material as the anode and the cathode as the titanium plate.
- the material was electrodeposited. After washing with water and drying at 100 ° C for 10 minutes, it was baked at 180 ° C for 30 minutes. The coating thickness of the electrodeposition paint was 2.6 m.
- the electrodeposited conductive base material is polished with polishing powder (TypeO. 1R, manufactured by Baikalox) and polishing cloth (made by CONSUMABLES Buehler G MBH) to expose the SUS surface.
- polishing powder TypeO. 1R, manufactured by Baikalox
- polishing cloth made by CONSUMABLES Buehler G MBH
- the thickness of the electrodeposition coating film in the recesses of this conductive substrate was 2.6 m. However, the thickness of the electrodeposition coating at the edge of the upper surface of the convex portion was 0 (measured in the plane direction of the upper surface).
- This conductive base material was covered with an insulating film except for the upper surface of the convex portion.
- This conductive base material was covered with an insulating film except for the upper surface of the convex portion.
- the sample was immersed in an aqueous solution (30 ° C), and immersed in an electrolytic copper plating bath using phosphorous copper as an anode. Voltage was applied to both poles, the current density was lOAZdm 2 , and the metal deposited on the top surface of the protrusions was stuck to 3 ⁇ m.
- composition of bl was applied to a 125 m thick PET film (A-4100, manufactured by Toyobo Co., Ltd.) so that the dry coating thickness was 5 m, and an adhesive film was prepared.
- A-4100 manufactured by Toyobo Co., Ltd.
- Nylon UR— 1350 (Toyobo Co., Ltd., polyester resin) 100 parts by weight Coronate L (Nihon Polyurethane Co., Ltd., isocyanate compound) 3 parts by weight [0175] (Transfer blackening treatment)
- the adhesive surface of the adhesive film obtained above and the surface of the conductive substrate that had been subjected to copper plating and blackening treatment were bonded together using a roll laminator.
- Lamination conditions were a roll temperature of 100 ° C, a pressure of 0.1 lMPa, and a line speed of 0.3 mZmin. Since lamination was performed at a temperature exceeding the glass transition point (Tg) of the adhesive, tackiness was exhibited on the adhesive surface.
- Tg glass transition point
- UV curing type resin hyaloid 7983AA3 manufactured by Hitachi Chemical Co., Ltd.
- PET film A-4100, manufactured by Toyobo Co., Ltd., 75 m
- UV curable resin to form the conductor layer pattern in UV curable resin. Buried in.
- the PET film (A-4100, manufactured by Toyobo Co., Ltd., 75 m) was peeled off to form a protective film.
- the base material with a conductor layer pattern was obtained.
- Example bl Except for etching using stainless steel (SUS304 finish H, Takeuchi Metal Foil Powder Co., Ltd., thickness 100 m) until the line width of the protrusions reaches 15 m, the same conditions as in Example bl were applied. Form a pattern (line width 15 m, pitch 300 m, convex height 20 m, convex cross-section is curved (similar to Fig. 3-d)). And a conductive substrate having recesses in the shape of the geometrical drawing drawn thereby.
- stainless steel SUS304 finish H, Takeuchi Metal Foil Powder Co., Ltd., thickness 100 m
- the cathode as the titanium plate, and etching into a lattice pattern in a cationic electrodeposition paint (UC-2000, manufactured by Shimizu Corporation) under the conditions of 30 V 60 seconds.
- the coated stainless steel plate was electrodeposited. After washing with water and drying at 100 ° C. for 10 minutes, it was cured under irradiation conditions of 3jZcm 2.
- the coating thickness of the electrodeposition paint was 3.9 m.
- the electrodeposited stainless steel plate was polished with # 4000 abrasive paper, and the thickness of the electrodeposition coating film in the recess of this conductive substrate was 3.9 m.
- the thickness of the electrodeposition coating film at the end of the upper surface of the convex portion was 0.5 m (measured in the plane direction of the upper surface).
- This conductive substrate was covered with an insulating film except for the upper surface of the convex portion.
- a cathode copper sulfate (pentahydrate) 180 gZL, sulfuric acid 100 gZL, Kavalaside HL (manufactured by Atotech Japan Co., Ltd., additive) 70 ml ZL aqueous solution, 30 ° C.
- composition of rosin composition b2 Composition of rosin composition b2
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film obtained above was bonded to the conductive base material using a copper laminator and a blackened surface using a roll laminator.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0.1 MPa, and a line speed of lmZmin.
- copper (blackened) deposited on the upper surface of the convex portion of the conductive substrate was transferred to the adhesive surface of the pressure-sensitive adhesive film.
- a metal pattern having a line width of 17 m, a line pitch of 300 m, and a conductor thickness of 1 ⁇ m and further blackened is selectively transferred onto the adhesive film, and the conductor layer of the present invention is thus transferred.
- a substrate with a pattern was manufactured.
- the pressure-sensitive adhesive surface (surface having a conductor layer pattern) of the substrate with a conductor layer pattern obtained above was laminated on and bonded to glass having a thickness of 2 mm.
- Lamination conditions are temperature 25. C, pressure 0.5 MPa, line speed 0.5 mZmin.
- the conductor layer pattern with a thickness of 1 ⁇ m was embedded in the adhesive, and a highly transparent electromagnetic shielding body was obtained.
- IRG— 022 (Nippon Yakuyaku Co., Ltd., Dimo-um salt-based infrared absorber) 3.3 parts by weight
- IR—12 (Nippon Shokubai Co., Ltd., phthalocyanine-based infrared absorber) 1.5 parts by weight
- the resin composition 4 was applied to the release-treated surface of the release PET film (S-32, manufactured by Teijin DuPont Co., Ltd.) so that the dry coating thickness was 8 m.
- An adhesive film having a near-infrared shielding property was prepared by laminating a film coated with the resin composition 4 on the surface of the adhesive film containing the near-infrared absorber coated with the resin.
- composition of rosin composition b4 Composition of rosin composition b4
- a substrate with a conductor layer pattern was used in the same manner as Example bl except that the adhesive film having the near infrared shielding property obtained above was used as the adhesive film (except that the release PET film was peeled off). And the base material with a conductor layer pattern by which the conductor layer pattern was blackened was manufactured.
- the surface of the base material with the conductor layer pattern obtained by blackening the conductor layer pattern obtained above is coated with an ultraviolet curable resin (Hitaroid 7851, manufactured by Hitachi Chemical Co., Ltd.), and After laminating polycarbonate film (Macro Hall DE, manufactured by Bayer Co., Ltd., 75 m), UZcm 2 ultraviolet rays were irradiated with an ultraviolet lamp to coat the conductor layer pattern with resin. Then, of the film obtained above An adhesive layer was formed on the surface opposite to the surface on which the conductor layer pattern was formed, and was bonded to a 3 mm thick PMMA plate (Comoglass) to obtain an electromagnetic wave shielding member.
- an ultraviolet curable resin Haroid 7851, manufactured by Hitachi Chemical Co., Ltd.
- Micro Hall DE manufactured by Bayer Co., Ltd. 75 m
- UZcm 2 ultraviolet rays were irradiated with an ultraviolet lamp to coat the conductor layer pattern with resin.
- An adhesive layer was formed on the surface opposite to the
- the (copper plating black spot treatment) process and the (transfer black spot treatment) process were performed. As in Example b2, the test was repeated 100 times. As a result, no peeling of the insulating film where there was no change in the transferability of copper plating was observed.
- a substrate with a conductor layer pattern was produced in the same manner as in Example b2, except that in Example b2 (Preparation of adhesive film), the dry coating thickness of the resin composition bl was 10 / zm.
- the substrate with the conductor layer pattern was immersed in the following black wrinkle treatment solution heated to 80 ° C for 3 minutes to blacken the conductor layer and the surface of the conductor layer was blackened.
- the base material with a conductor layer pattern which has a pattern was manufactured.
- An electromagnetic wave shielding member was obtained in the same manner as in Example b4 (Preparation of electromagnetic wave shielding body), using the base material with a conductive layer pattern having a conductive layer pattern whose surface was blackened.
- Stainless steel with a diameter of 150 mm and a width of 200 mm for the continuous production of rolls, tows and rolls By applying the same method as in Example b 1 to the surface of the loess roll, a lattice pattern (line width, ie, the width of the upper surface of the convex portion 20 ⁇ m, the pitch 300 ⁇ m, the height of the convex portion 15 m, the cross-sectional shape of the convex part was a curved surface (similar to Fig. 3-d).
- the above-mentioned stainless steel roll is used as a cathode
- the anode is used as a titanium plate
- it is etched into a lattice pattern in a cationic electrodeposition paint (Insuleed 3020, manufactured by Nippon Paint Co., Ltd.) under the condition of 15 V for 10 seconds.
- Electrodeposition coating was applied to a stainless steel roll. After washing with water and drying at 100 ° C for 10 minutes, it was baked at 190 ° C for 25 minutes. The coating thickness of the electrodeposition paint was 2.
- the surface of the stainless steel roll coated with the above electrodeposition was polished by applying the same method as in Example bl to expose the upper surface of the convex portion.
- electrolytic copper plating was performed with the apparatus configuration shown in FIG.
- the anode 102 was an insoluble titanium electrode coated with iridium oxide, and the stainless steel roll 103 was used as a drum electrode for the cathode.
- the adhesive film of copper and the adhesive film (107) deposited on the upper surface of the convex portion of the stainless steel tool was laminated under the same laminating conditions as in Example b 1, and the adhesive film was bonded to the stainless steel roll as shown in FIG. Bonding was performed continuously between 103 and the pressure roll 108.
- the adhesive film to which the conductor layer pattern (copper layer) was transferred was wound around a roll.
- a conductor layer pattern with a line width of 28 ⁇ m, a line pitch of 300 ⁇ m, and a conductor thickness of 5 m was transferred onto the adhesive film.
- Blocking at the time of scraping is performed by winding release PET (S 32, manufactured by Teijin Dubon Co., Ltd.) while laminating it on the surface of the substrate with the conductor layer pattern (109) onto which the conductor layer pattern is transferred. Prevented.
- the adhesive film was continuously rolled with a so-called roll “toe” roll in which the roll force was also pushed out and the conductor layer pattern was wound around the roll after transfer. Even after 50 m of the adhesive film to which the copper plating had been transferred, the copper plating on the stainless steel roll and the insulating film peeling point where the transferability did not change were observed.
- the surface of the obtained substrate with the conductor layer pattern on which the conductor layer pattern is formed is coated with a UV curable resin (Alonics UV-3701, manufactured by Toagosei Co., Ltd.) with a thickness of 15 m, and a PET film ( After laminating with Mylar D, manufactured by Teijin DuPont Films, Ltd., 75 m), a protective film was formed by irradiating UZcm 2 ultraviolet rays using an ultraviolet lamp.
- a UV curable resin Alonics UV-3701, manufactured by Toagosei Co., Ltd.
- PET film After laminating with Mylar D, manufactured by Teijin DuPont Films, Ltd., 75 m), a protective film was formed by irradiating UZcm 2 ultraviolet rays using an ultraviolet lamp.
- Rolled SUS304 foil (Nisshin Steel Co., Ltd., finish 3Z4H, width 200mm, thickness 100 / zm), PET film (A-4100, manufactured by Toyobo), Byron UR-1350 (adhesive, Toyo A roll-like adhesive film produced by applying Spinning Co., Ltd.) to a dry coating thickness of 20 ⁇ m was bonded with a roll laminator to produce a rolled SUS foil with a PET film.
- Lamination conditions were a roll temperature of 120 ° C, a preheat of 120 ° C for 30 seconds, a pressure of 3 MPa, and a line speed of 0.5 mZmin.
- the SUS foil with PET film is etched under the same conditions as in Example b3 except that the roll-to-roll is performed, and the SUS foil has a lattice pattern (line width, that is, the upper surface of the convex portion).
- the width was 15 / ⁇ ⁇
- the pitch was 30 O ⁇ m
- the height of the protrusion was 20 m
- the cross-sectional shape of the protrusion was a curved surface (similar to FIG. 3D).
- the etched SUS foil with PET film was cut to a length of lm, and then the above SUS foil with PET film was used as the anode, and the cathode was used as the titanium plate.
- Cationic electrodeposition paint (UC-2000, Co., Ltd.) (Shimizu) was electrodeposited on a stainless steel plate etched in a lattice pattern under the condition of 30V 60 seconds. After drying 100 ° C10 minutes after washing with water and cured at irradiation conditions 3jZcm 2. The coating thickness of the electrodeposition paint was 3.9 m. In addition, the electrodeposition coating The stainless steel plate was polished with # 4000 polishing paper to expose the conductive substrate only on the upper surface of the convex portion. In the same manner, 10 SUS foils with PET film were electrodeposited and polished.
- the PET film surface of the SUS foil with the 10 PET films prepared above was formed without any gaps.
- a SUS foil with a PET film having a lattice pattern of 10 m in length was obtained.
- a SUS foil with a PET film having the above-described lattice pattern was passed through an apparatus as shown in FIG. The joint was bonded using a commercially available gum tape to form a hoop-like conductive support.
- one electrolytic bath for electrolytic copper plating ((copper sulfate (pentahydrate) 180gZL, sulfuric acid 100gZL, Kaparaside HL (Atotech)) using the rolled lattice pattern obtained above as a cathode. Japan Co., Ltd., additive) 70mlZL aqueous solution, 30 ° C) (Fig. 26-130), current density is 30AZdm 2 with phosphorous copper as anode and the thickness of the metal deposited on the upper surface of the convex part is: After washing with water, the same blackening treatment as in Example bl was performed in the blackening treatment layer (Fig. 26-150; in this example, a black soot treatment tank).
- Example b3 plastic substrate, Fig. 26 — Conductor layer pattern that has been blackened using roll 137 to 136), line width of 17 ⁇ m, line pitch of 300 m, thickness of 1 m.
- the substrate was continuously transferred onto the adhesive film to obtain a substrate 138 with a conductor layer pattern, and when the substrate 138 with a conductor layer pattern was rolled up, it was separated from the surface of the conductor layer pattern.
- Type PET (S-32, manufactured by Teijin DuPont Co., Ltd.) was laminated so that the process of copper plating, black wrinkle treatment and transfer could be performed in one line. Even after the substrate 33 with the conductor layer pattern was wound up by 50 m, the insulation film peeled off where there was no change in the transferability of the copper plating was observed.
- the etching tank 129 is omitted in this example.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film with a conductor layer pattern obtained above (the surface to which the copper plating was transferred) was applied to a glass sheet having a thickness of 2 mm and laminated.
- Lamination conditions were a temperature of 25 ° C, a pressure of 0.5 MPa, and a line speed of 0.5 m / min.
- the 1 m thick conductor layer pattern is embedded in the adhesive, and a highly transparent electromagnetic wave shield Obtained.
- a dry film photoresist (HY-920 (manufactured by Hitachi Chemical Co., Ltd., thickness 20 / zm)) was bonded to a stainless steel (SUS304) plate at a roll temperature of 100 ° C, a linear pressure of 0.3 MPa, and a line speed of lmZmin.
- a negative pattern with a line width of 30 m and a line pitch of 300 m is placed on a stainless steel plate with a resist film attached, and the upper force of the negative pattern is also irradiated with UV under the condition of lOOmj / cm 2.
- Development was performed with a 1% aqueous sodium carbonate solution to form a resist film having a groove with a width of 30 m on a SUS plate, and then heat-cured at 150 ° C. for 1 hour.
- an electrolytic bath for electrolytic copper plating using the SUS plate on which the resist is formed as a cathode [copper sulfate (pentahydrate) 100 gZL, sulfuric acid 180 gZL, Top Lucina H-380 (Okuno Pharmaceutical Co., Ltd., Additive) 2. Dipped in 5 ml ZL aqueous solution, 30 ° C], and immersed in the same electrolytic bath with phosphorous copper as anode. As 3AZdm 2 current density by applying a voltage to both electrodes, grooves of the resist is plated to completely fill.
- Example bl was used as an adhesive film.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film was bonded to the surface of the SUS plate that had been subjected to copper plating using a roll laminator.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0.1 lMPa, and a line speed of lmZmin.
- the adhesive film bonded to the conductive substrate was peeled off, the copper deposited in the resist grooves of the SUS plate was transferred to the adhesive film.
- Example bl was performed in the same manner as Example bl except that the electrodeposition condition was 150 V for 10 seconds.
- the thickness of the electrodeposition paint was 25 / zm.
- the concave portion of the convex portion pattern is formed as shown in FIG. The shape was completely filled with an insulating layer.
- copper plating was performed in the same manner as in Example bl, and the copper plating was transferred onto the adhesive film. If the process of (copper plating and blackening process) and the process of (transfer blackening process) are repeated 7 times, a part of the insulating film is peeled off. Copper was deposited at the locations where the peeled off. As a result of transferring the copper plating to the adhesive film, the copper plating at the part where the insulating film peeled off was not transferred.
- Conductive substrate having the aperture ratio, visible light transmittance, presence / absence of pattern abnormality, visibility, electromagnetic wave shielding (300 MHz), and pattern of the conductor layer pattern obtained in the above examples or comparative examples Fig. 28 shows the results of evaluating the durability of the conductive substrate after repeated peeling and peeling 30 times.
- Example 16 (hereinafter, also referred to as “Example cl”, the same applies to Example 23) will be described.
- a resist film (Photec H-Y920, manufactured by Hitachi Chemical Co., Ltd.) was bonded to a 10 cm stainless steel (SUS304) plate.
- the bonding conditions were a roll temperature of 105 ° C, a pressure of 0.5 MPa, and a line speed of lmZmin.
- the negative film formed in a lattice shape with the line width of the light transmitting portion of 30 m, the line pitch of 300 ⁇ m, and the bias angle force of 5 ° was left on the stainless steel plate bonded with the resist film. .
- ultraviolet rays were irradiated at 120 miZcm 2 from above the negative film under a vacuum of 600 mmHg or less. further.
- a resist film having a line width of 30 ⁇ m, a line pitch of 300 ⁇ m, and a bias angle of 45 ° was formed on the SUS plate.
- the SUS plate was etched using a salty ferric aqueous solution heated to 40 ° C. Etching was performed until the line width of the SUS plate reached 20 m.
- the resist film formed on the SUS plate was peeled off to form a lattice pattern (line width 20 ⁇ m, pitch 300 ⁇ m, convex height 15 ⁇ m in length, taper angle 60 °
- the cross-sectional shape of the convex part was a curved surface (similar to Fig. 3-d).
- the surface roughness Rz of the upper surface of the convex portion was 0.3 m, whereas the surface roughness Rz of the concave portion was 4.2 m.
- a stainless steel plate (a conductive base material having a convex pattern having an upper surface and a concave part having a geometrical shape drawn by the stainless steel plate) on which a lattice pattern is formed is used as a cathode.
- Electrolytic copper plating bath (copper sulfate (pentahydrate) 80gZL, sulfuric acid 180g ZL, Cubelite VF1 (supplied by Ebara Eugene Co., Ltd., additive) 20mlZL aqueous solution, 25 ° C) A stainless steel plate was immersed, and phosphorous copper was immersed in the electrolytic copper plating bath as an anode.
- the current density was 25AZdm 2 and the metal deposited on the top surface of the convex part of the stainless steel plate was stuck to 5 m.
- the line width was 30 / zm. Copper was deposited as a continuous film on the upper surface of the convex part of the stainless steel plate, but a small amount of particulate copper was also deposited on the concave part and the side part.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film was bonded to the surface of the stainless steel plate with copper plating using a roll laminator.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0. IMP a, and a line speed of lmZmin.
- the copper layer on the upper surface of the convex portion of the SUS plate was partially buried in the adhesive layer of the adhesive film.
- the adhesive film bonded to the stainless steel plate was peeled off, the copper deposited on the upper surface of the convex portion of the stainless steel plate was a continuous film, and thus transferred to the adhesive film.
- a metal pattern having a line width of 20 ⁇ m, a line pitch of 300 m, and a conductor thickness of 5 ⁇ m was selectively transferred onto the adhesive film.
- the adhesive film onto which the metal pattern obtained above was transferred was immersed in an aqueous solution obtained by diluting alkaline degreasing solution Degree A (Odec Co., Ltd.) 5 times at room temperature for 3 minutes. Next, after washing with water, it was immersed in a 10% nitric acid aqueous solution at room temperature for 2 minutes. Further, after washing with water, the substrate was immersed in a 4-fold diluted aqueous solution of blackening solution copar (Odec Co., Ltd.), and the metal pattern was blackened to produce a substrate with a conductor layer pattern of the present invention.
- the surface of the substrate with the conductor layer pattern obtained above, on which the conductor layer pattern is present, is coated with UV-cured rosin hyaloid 7983AA3 (manufactured by Hitachi Chemical Co., Ltd.), and then a polycarbonate film. (Macro Hall DE, Bayer Co., Ltd., 75 m) is laminated and the conductor layer pattern is buried in UV curable resin, and then an ultraviolet lamp is used. The UV curable resin was cured by irradiating UZcm 2 ultraviolet rays.
- the stainless steel plate on which the convex pattern was formed was dipped in lOOgZ liters of ammonium persulfate solution heated to 40 ° C after copper was transferred to the adhesive film. A small amount of copper remaining in the concave and side portions of the formed stainless steel plate was dissolved.
- a lattice pattern (the cross-sectional shape of the convex part is a curved surface (similar to Fig. 3-d)) was formed on the SUS plate.
- Electrolytic bath copper sulfate (pentahydrate) 150gZL, sulfuric acid 150gZL, Kaparaside HL (manufactured by Atotech Japan Co., Ltd., additive) 50ml ZL in water, 30 ° C) Immerse in the bath.
- the SUS plate on which the copper plating was deposited was immersed for 3 minutes in a black wrinkle treatment solution having the following composition heated to 80 ° C, and the copper plating deposited on the stainless steel plate was blackened. It was processed.
- Dried primer HP-1; Hitachi Chemical Co., Ltd.
- 100 / zm thick polyethersulfone film Silicon FS-1300, manufactured by Sumitomo Beta Light Co., Ltd.
- an adhesive film was prepared by coating sequentially.
- the adhesive surface of the adhesive film and the copper-plated surface of the stainless steel plate were bonded together using a roll laminator.
- Lamination conditions were a roll temperature of 150 ° C., a pressure of 0.1 MPa, and a line speed of 0.5 mZmin. Since lamination was performed at a temperature exceeding the Tg of the adhesive, tackiness was developed on the adhesive surface.
- the blackened copper layer on the upper surface of the convex portion of the SUS plate was partially embedded in the adhesive layer of the adhesive film.
- the adhesive film bonded to the stainless steel plate was peeled off, the copper deposited on the upper surface of the convex portion of the stainless steel plate was a continuous film, and thus transferred to the adhesive film.
- a small amount of copper deposited on the concave and side portions is a granular and discontinuous film, so it remains on the SUS plate without following the copper deposited on the upper surface of the convex portion and transferred to the adhesive film. It was very powerful. In this way, the metal pattern having a line width of 16 ⁇ m, a line pitch of 300 ⁇ m, and a conductor thickness of 3 ⁇ m, and further blackened, is selectively transferred onto the adhesive film, and the conductor layer of the present invention. A patterned substrate was produced.
- a UV curable resin hyaloid 7983AA3 (manufactured by Hitachi Chemical Co., Ltd.) is copied in the same manner as in Example cl.
- PET film A-4100, manufactured by Toyobo Co., Ltd., 75 m
- UV curable resin to form a conductive layer pattern. It was embedded in a curable type rosin.
- the UV curable resin was cured by irradiating UV light of UZcm 2 using an ultraviolet lamp, and then the PET film (A-4100, manufactured by Toyobo Co., Ltd., 75 m) was peeled off. A small amount of copper remaining on the concave portions and side portions of the stainless steel plate on which the convex portion pattern was formed was dissolved in the same manner as in Example cl.
- Byron UR-1350 adheresive, manufactured by Toyobo Co., Ltd.
- SUS304 foil Takeuchi Metal Foil Powder Co., Ltd., thickness 100 m
- PET film A-4100, manufactured by Toyobo Co., Ltd.
- the adhesive film produced by applying the dry coating thickness to 20 m was pasted with a press. press The conditions were a hot press at 130 ° C, a pressure of 4 MPa, and a press for 30 minutes. The sample was taken out after cooling to 25 ° C with pressure applied.
- Example cl Using the SUS foil with PET film obtained above in the same manner as in Example cl, a no-turn pattern (line width 15 m, pitch 300 m, convex height 15 m, taper angle 70) was applied to the SUS foil. ° The cross-sectional shape of the convex part was curved (similar to Fig. 3-d)).
- electrolysis using a SUS foil with a PET film on which a lattice-like pattern is formed (a conductive base material having a notch of a convex part having an upper surface and a concave part of a geometrical figure drawn by the same) as a cathode.
- an electrolytic bath for copper plating copper sulfate (pentahydrate) 180gZL, sulfuric acid 10 OgZL, Kaparaside HL (manufactured by Atotech Japan Co., Ltd.), 70mlZL aqueous solution, 30 ° C), and use phosphorous copper as an anode And immersed in the same electrolytic bath.
- the current density was set to 30 AZdm 2 and plating was performed until the thickness of the metal deposited on the top surface of the convex portion reached 1 ⁇ m. Natsu.
- Copper was deposited as a continuous film on the upper surface of the convex part of the SUS foil with PET film, but a small amount of particulate copper was also deposited on the concave part and the side part.
- the SUS foil with PET film on which copper plating was deposited was immersed in an aqueous solution in which alkaline degreasing solution Degrease A (Odec Co., Ltd.) was diluted 5 times at room temperature for 3 minutes.
- alkaline degreasing solution Degrease A Odec Co., Ltd.
- it was immersed in a 10% nitric acid aqueous solution at room temperature for 10 seconds.
- blackening solution copal Odec Co., Ltd.
- Resin composition 1 was applied to the easy-adhesion surface of a 100 ⁇ m thick PET film (A-4100, manufactured by Toyobo Co., Ltd.) so that the dry coating thickness was 20 m. Produced.
- AS-406 Analic polymer, manufactured by Yukisha Co., Ltd.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film obtained above (the surface to which the copper plating was transferred) was applied to a glass sheet having a thickness of 2 mm and laminated and bonded.
- Lamination conditions were a temperature of 25 ° C, a pressure of 0.5 MPa, and a line speed of 0.5 mZmin.
- the 1 m thick conductor layer pattern was embedded in the adhesive, and a highly transparent electromagnetic shielding body was obtained.
- a grid pattern (line width) was applied to the Ni foil in the same manner as in Example c3 except that electrolytic Ni foil (Fukuda Metal Co., Ltd., 35 ⁇ m thick) was used instead of SUS foil 304. 15 / ⁇ ⁇ , pitch 300 m, height of convex part 20 m, taper angle 60 °
- the cross-sectional shape of the convex part was a curved surface (similar to Fig. 3-d).
- an acid film was formed on the Ni surface with Ni anodic acid. The anodic oxidation was performed in a 10% aqueous solution of sodium hydroxide and sodium hydroxide for 30 seconds using a Ni foil as the anode and a SUS plate as the cathode, with a voltage of IV applied to both electrodes.
- Electrolysis bath for plating (copper sulfate (pentahydrate) 180gZL, sulfuric acid lOOgZ L, Kaparaside HL (manufactured by Atotech Japan Co., Ltd., additive) immersed in an aqueous solution of 70 ml ZL, 30 ° C), and immersed in the same electrolytic bath with phosphorous copper as an anode.
- the current density was 30AZdm 2
- the metal deposited on the top surface of the convex part was 10 m thick, the plated metal also deposited on both sides, so the line width was 35 / zm
- Copper was deposited as a continuous film on the upper surface of the convex part of the Ni foil with PET film, but a small amount of particulate copper was also deposited on the concave part and the side part.
- the thickness of the PET film (Mylar D, manufactured by Teijin DuPont Films Co., Ltd.) with a thickness of 100 ⁇ m on the surface of the resin composition 2 containing the following infrared absorber is 20 ⁇ m after drying.
- An adhesive film was prepared by coating the film.
- IRG-022 (Nippon Kayaku Co., Ltd., dimo-um salt infrared absorber) 3.3 parts by weight Tolene 60 parts by weight
- the resin composition c3 was applied to the release-treated surface of release PET (S-32, manufactured by Teijin DuPont Co., Ltd.) so that the dry application thickness was 8 m.
- An adhesive film having a near infrared shielding property was prepared by laminating a film coated with the resin composition 3 on the surface coated with the resin composition c2 of an adhesive film containing a near infrared absorber.
- the obtained adhesive film with a conductor layer pattern was blackened in the same manner as in Example cl. Further, after the blackening treatment, the surface on which the conductor layer pattern of the substrate with the conductor layer pattern is present is coated with an ultraviolet curable resin (Hitaroid 7851, manufactured by Hitachi Chemical Co., Ltd.), and a polycarbonate film ( After laminating Macro Hall DE, Bayer Co., Ltd. (75 m), UZcm 2 ultraviolet rays were irradiated using an ultraviolet lamp, and the conductor layer pattern was coated with resin. Next, an adhesive layer was formed on the surface of the film obtained above opposite to the surface on which the conductor layer pattern was formed, and was bonded to a 3 mm thick PMMA plate (Comoglass) to obtain an electromagnetic wave shielding member.
- Example c3 SUS foil with PET film treated with copper plating and black wrinkle treatment in the same manner as Example c3 (line width 15 ⁇ m, pitch 300 ⁇ m, convex height 20 ⁇ m, taper angle 60 ° convex
- the cross-sectional shape of the part formed a curved surface (similar to Fig. 3-d).
- the metal thickness reached l / z m, the plated metal deposited on both sides, resulting in a line width of 17 m.
- the following resin composition c4 was applied to the surface of a polyether sulfone film (Sumilite FS-1300, manufactured by Sumitomo Bakelite Co., Ltd.) having a thickness of 100 / zm so that the thickness after drying was 13 m.
- An adhesive film was obtained. Drying conditions were 90 ° C for 5 minutes.
- the blackened metal present on the upper surface of the convex portion of the stainless steel plate is selectively transferred to the adhesive surface, and the line width is 17 m, line pitch is 300 m, and conductor thickness is 1 ⁇ m.
- a conductor layer pattern was formed on the adhesive film.
- the transferred stainless steel plate was the same as in Example cl, and a small amount of copper remaining on the surface was removed.
- the adhesive film having the conductor layer pattern obtained above was treated at 150 ° C for 60 minutes to cure the adhesive, to obtain a substrate with a conductor layer pattern.
- UV-cured mortar hyaloid 7983AA3 manufactured by Hitachi Chemical Co., Ltd.
- the surface of the film (A-4100, manufactured by Toyobo Co., Ltd., 75 / zm) that has not been subjected to easy adhesion treatment is laminated with UV curable resin to embed the conductor layer pattern in UV curable resin. It was.
- the PET film (A-4100, manufactured by Toyobo Co., Ltd., 75 / zm) was peeled off.
- the dissolution of a small amount of copper remaining on the concave portions and side portions of the stainless steel plate on which the convex portion pattern was formed was performed in the same manner as in Example cl.
- a resist film (Photec LF-1515, manufactured by Hitachi Chemical Co., Ltd.) was bonded to a 10 cm-thick copper plate (thickness 2 mm).
- the bonding conditions were a roll temperature of 105 ° C., a pressure of 0.5 MPa, and a line speed of lmZmin.
- a negative film formed in a lattice shape with a line width of 30 m for the light transmitting portion, a line pitch of 200 ⁇ m, and a bias angle of 30 ° Then, it was allowed to stand on a copper plate to which a resist film was bonded.
- ultraviolet rays were irradiated from the top of the negative film at 120 mjZcm 2 under a vacuum of 6 OOmmHg or less. Further, by developing with a 1% aqueous sodium carbonate solution, a resist film having a line width of 30 ⁇ m, a line pitch of 200 ⁇ m, and a bias angle of 30 ° was formed on the copper plate. Further, the copper plate was etched using a salty ferric aqueous solution heated to 40 ° C. Etching was performed until the line width of the copper plate reached 25 m.
- the resist film formed on the copper plate is peeled off to form a lattice pattern (line width 25 / ⁇ ⁇ , line pitch 200 / ⁇ ⁇ , convex
- the height of the part was 11 / ⁇ ⁇
- the cross-sectional shape of the convex part was a curved surface (similar to Fig. 3-d).
- a chromium layer was formed by sputtering on the surface of the copper plate on which the lattice pattern was formed so as to have a thickness of 0.3 m.
- the copper plating applied thereon is easily peeled off.
- Electrolytic copper plating was performed using the copper plate sputtered with chromium as a cathode. In an electrolytic copper plating bath (copper sulfate (pentahydrate) 100g / L, sulfuric acid 180gZL, Topchina H-380 (Okuno Pharmaceutical Co., Ltd., additive) 2.
- a copper plate sputtered with chromium was immersed in the same electrolytic copper plating bath with phosphorous copper as an anode. Voltage was applied to both electrodes, and the current density was 25 AZdm 2 until the thickness of the copper deposited on the upper surface of the convex portion of the copper plate sputtered with chromium was 3 ⁇ m. Copper was deposited as a continuous film on the upper surface of the convex portion of the copper plate sputtered with chromium, but granular copper having a particle size of about 1 m was discontinuously deposited on the concave portion and side portions. Further, the copper plate on which copper plating was formed was immersed in a black bath treatment solution 1 and treated at 80 ° C. for 1 minute to blacken the copper plating.
- the above-obtained substrate with a conductor layer pattern and a glass plate having a thickness of 2 mm were laminated so that the surface of the substrate with the conductor layer pattern formed thereon was in contact with the glass plate (30 ° C, 2. OMPa) and pasted together.
- the conductor layer pattern was embedded in the adhesive, and a highly transparent electromagnetic wave shielding member was obtained.
- a stainless steel roll with a diameter of 150 mm was applied to a grid pattern (line width 20 m, pitch 300 m, convex height 15 m, taper in the same manner as in Example cl.
- the cross-sectional shape of the convex part with a 60 ° angle formed a curved surface (similar to Fig. 3-d).
- electrolytic bath for electrolytic copper plating using the processed stainless steel roll as the cathode copper sulfate (pentahydrate) 80gZL, sulfuric acid 180gZL, Cubelite VF1 (supplied by Ebara New Light Co., Ltd.), 20ml ZL aqueous solution, 25 ° C) and immersed in the same electrolytic bath with phosphorous copper as an anode.
- the current density was 40 AZdm 2 and voltage was applied to both poles until the thickness of the metal deposited on the upper surface of the convex portion reached 5 m, the plated metal deposited on both sides, so the line width was 30 m. It became. Copper was deposited as a continuous film on the upper surface of the convex portion of the stainless steel roll, but granular copper having a particle size of about 3 ⁇ m was deposited discontinuously on the concave portion and side portions.
- Example cl The pressure-sensitive adhesive film used in Example cl was produced in a roll shape, and the adhesive surface of copper and the pressure-sensitive adhesive film deposited on the upper surface of the convex portion of the stainless steel roll was bonded together under the same lamination conditions as in Example cl. . At this time, the copper layer formed on the upper surface of the convex portion of the stainless steel roll was partially buried in the adhesive layer of the adhesive film. Next, when the adhesive film bonded to the stainless steel roll is peeled off, the copper deposited on the upper surface of the convex part of the stainless steel roll is a continuous film, so it is transferred to the adhesive film, but is deposited on the concave part and the side part.
- the deposited copper was a discontinuous film in a small amount, it remained on the SUS plate without following the copper deposited on the upper surface of the convex portion.
- a conductor layer pattern having a line width of 30 ⁇ m, a line pitch of 300 ⁇ m, and a conductor thickness of 5 ⁇ m was selectively transferred onto the adhesive film.
- the adhesive film (substrate with the conductor layer pattern) to which the conductor layer pattern was transferred was released from the release PET (S-32, Teijin DuPont). The product was wound up in a roll shape while laminating (made by Co., Ltd.).
- Example c4 After the transfer, in the same line as in Example c4, a small amount of copper remaining on the concave portion and the side portion of the stainless steel roll was removed by etching, and then the stainless steel roll was subjected to copper plating again. In this way, the three steps of copper plating, transfer to adhesive, and etching of residual copper were continuously performed with a roll 'toe' roll.
- the adhesive film to which the metal pattern obtained above was transferred was blackened in the same manner as in Example cl to produce a substrate with a conductor layer pattern of the present invention.
- the surface of the substrate with the conductor layer pattern obtained, on which the conductor layer pattern is formed is coated with a UV curable resin (Alonics UV-3701, manufactured by Toagosei Co., Ltd.) with a thickness of 15 m, and a PET film (Mylar 1D, made by Teijin DuPont Films, Ltd., 75 m), and then irradiated with UZcm 2 ultraviolet rays using an ultraviolet lamp.
- a UV curable resin Alonics UV-3701, manufactured by Toagosei Co., Ltd.
- PET film Mylar 1D, made by Teijin DuPont Films, Ltd., 75 m
- Rolled SUS304 foil (thickness 100 ⁇ m) and PET film (A-4100, manufactured by Toyobo Co., Ltd.), Neuron UR-1350 (adhesive, manufactured by Toyobo Co., Ltd.) is applied to a dry coating thickness of 20 ⁇ m.
- the roll-shaped adhesive film produced by coating in this manner was bonded with a roll laminator to produce a rolled SUS foil with a PET film.
- Lamination conditions were a roll temperature of 120 ° C, a preheat of 120 ° C for 30 seconds, a pressure of 3 MPa, and a line speed of 0.5 m / min.
- the SUS foil with PET film is etched in the same manner as in Example c7 except that the roll-to-roll process is performed, and a lattice pattern (line width 15 m, pitch 300 m, protrusions) is formed on the SUS foil.
- the length of 20m, taper angle 60 °, and the cross-sectional shape of the convex part was a long curved surface (similar to Fig. 3-d).
- paper was passed through an apparatus as shown in FIG.
- the joints were bonded with Mylar tape to form a hoop-like conductive substrate.
- the etching tank (129 in Fig. 26) is passed through the SUS foil (hoop-like conductive base material) with PET film obtained above, washed appropriately, and then the hoop-like conductivity is obtained.
- Electrolytic bath for electrolytic copper plating with the base material as the cathode ((copper sulfate (pentahydrate) 180gZL, sulfuric acid lOOgZL , Cupracid HL (Atotech Japan Co., additives) aqueous 70MlZL, at 30 ° C) (130 in FIG.
- the current density phosphorous-containing copper as the anode as 30AZdm 2 convex hoop conductive substrate
- the metal width deposited on both sides resulted in a line width of 17 m.
- Copper was deposited as a continuous film on the upper surface of the convex part of the SUS foil with PET film, but a slight amount of granular copper having a particle size of about 0.3 m was deposited on the concave part and the side part.
- the black smoke treatment similar to that of Example cl was performed in the black smoke treatment tank (150 in FIG. 26), passed through the fouling treatment tank (151 in FIG. 26), and continuously transferred. After the transfer, the copper remaining in the recesses and side portions of the SUS foil was removed in an etching tank (129 in FIG. 26) (lOOgZl aqueous ammonium persulfate solution, liquid temperature 40 ° C.).
- the conductor layer was continuously transferred to the roll-shaped adhesive film (136 in FIG. 26) used in Example c3, the line width was 17 ⁇ m, the line pitch was 300 ⁇ m, the thickness was At 1 m, an adhesive film with a conductor layer pattern was obtained in which the conductor layer pattern (138 in FIG. 26) subjected to blackening treatment was selectively transferred onto the adhesive film. Since the copper deposited on the top surface of the convex part of the SUS foil with PET film is a continuous film, it is transferred to the adhesive film, whereas the copper deposited on the concave part and the side part is granular and discontinuous.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film with a conductor layer pattern obtained above (the surface to which the copper plating was transferred) was applied to a glass sheet having a thickness of 2 mm and laminated.
- Lamination conditions were a temperature of 25 ° C, a pressure of 0.5 MPa, and a line speed of 0.5 m / min.
- the 1 m thick conductor layer pattern was embedded in the adhesive, and a highly transparent electromagnetic shielding body was obtained.
- the depth from the top surface of the portion of the convex side surface where the taper angle) has the angle indicated in each example is a vertical distance. There was at least half of the height of the protrusion.
- a metal plated in a non-turn pattern is adhesive when transferred to an adhesive film, for example. Since the layer is in contact with the insulator that forms the pattern, a peel stress is applied to the insulator every time the adhesive film to which the metal pattern is transferred is peeled off. Furthermore, since the insulator is formed in a pattern, the contact area of the insulator with SUS is very small, so the process of plating ⁇ transfer in a pattern is repeated several to several hundred times. However, at the mass production level of several thousand to several tens of thousands of times, the insulation is peeled off from the conductive substrate! /, And the pattern life is short.
- the resin used to form the pattern and the adhesive used to peel the conductor layer from the conductive substrate Organic strength such as film peeling residue
- the plating solution is contaminated, so the life of the plating solution is shortened and plating deposition failure is likely to occur.
- Example 24 (hereinafter, also referred to as “Example dl”. The same applies to Example 30) will be described. (Negative film specifications 1)
- the size of the pattern drawing part is 300mm square, and the line width of the light transmission part is 100 ⁇ m, the line pitch is 300 ⁇ m, and the bias angle is 45 ° on the four sides (corresponding to the area B) 30 mm inside from the outermost periphery of the pattern drawing part.
- a grid pattern is formed (in the regular square, the line is arranged at an angle of 45 degrees with respect to the side of the regular square), and light is applied to the entire inner surface (corresponding to the area A).
- a grid pattern with a line width of 30 m at the transmission part, a line pitch of 300 m, and a bias angle of 45 ° was formed. Each inner line is connected to the outer line at the inner and outer boundary.
- This negative film pattern corresponds to the pattern shown in Figure 3-d.
- Resist film (Photech H—Y920, manufactured by Hitachi Chemical Co., Ltd.) was bonded to both sides of 300 mm square stainless steel (SUS304, finished 3Z4H, thickness 100 / ⁇ ⁇ , manufactured by Nisshin Steel Co., Ltd.).
- the bonding conditions were a roll temperature of 105 ° C, a pressure of 0.5 MPa, and a line speed of lmZmin.
- the negative film specification 1 was allowed to stand on one surface of the stainless steel plate to which the resist film was bonded.
- the resist pattern line width formed on the outside of the SUS plate was 100 ⁇ m
- the line pitch was 300 m
- the bias angle was 45 °
- the resist pattern was formed on the inside.
- a resist pattern having a line width of 30 m, a line pitch of 300 ⁇ m, and a bias angle of 45 ° was formed. Note that the opposite surface of the surface on which the pattern is formed is exposed to the whole surface, so that it is not developed and a resist film is formed on the entire surface.
- the SUS plate was etched using a salty ferric aqueous solution (45 ° Be ', manufactured by Tsurumi Soda Co., Ltd.) heated to 40 ° C. Etching was performed until the width (line width) of the upper surface of the convex portion in region A reached 20 / zm. The surface opposite to the surface on which the pattern was formed was not etched because a resist film was formed on the entire surface.
- a salty ferric aqueous solution 45 ° Be ', manufactured by Tsurumi Soda Co., Ltd.
- the resist film (including the resist film on the back surface) formed on the SUS plate is peeled off using a 5% by weight sodium hydroxide / sodium salt solution, and a convex pattern having an upper surface is drawn.
- a conductive base material having a recess having a geometrical figure shape was obtained.
- This conductive base material has a width of the upper surface of the convex portion (line width) of 20 m, an interval of the upper surface of the convex portion (line pitch) of 300 / ⁇ ⁇ , and a height of the convex portion of 15 m.
- the width of the upper surface of the convex part is 90 / ⁇ ⁇
- the distance between the upper surfaces of the convex part is 300 m
- the height of the convex part is 15 m. This was the same as in FIG.
- the cross-sectional shape of the recesses in the regions A and B was a curved surface (similar to Fig. 3-d).
- the anode as a titanium plate, and applying a voltage for 10 seconds at 15 V in a cationic electrodeposition paint (Insuleed 3020, Nippon Paint Co., Ltd.)
- a cationic electrodeposition paint Insuleed 3020, Nippon Paint Co., Ltd.
- the coating thickness of the electrodeposition paint was 2.5 m.
- the upper surface of the convex part of the electrodeposited stainless steel plate is polished with polishing powder (alumina solution BO. 0,5 m, manufactured by Refinetech Co., Ltd.) and polishing cloth (manufactured by CONSUMABLES Buehler GMBH).
- polishing powder alumina solution BO. 0,5 m, manufactured by Refinetech Co., Ltd.
- polishing cloth manufactured by CONSUMABLES Buehler GMBH.
- a conductive base material having an insulating film was produced by exposing the top surface of the surface.
- the thickness of the electrodeposition coating film in the concave portion of this conductive substrate was 2.5 m.
- the electrodeposition coating film at the edge of the upper surface of the convex portion was flush with the upper surface.
- the concave portions were covered with a thin film insulating film in both the regions A and B.
- a thin film insulating layer was formed on the entire surface opposite to the surface on which the convex and concave portions exist.
- Electrolytic copper plating bath (copper sulfate (pentahydrate) 80gZL, sulfuric acid 180gZL, Cubelite VF1 (supplied by Ebara Eugene, Inc., 20ml ZL aqueous solution, 25 ° C), conductive base with insulating film
- the material was immersed and immersed in the electrolytic copper plating bath using phosphorous copper as an anode.
- a voltage was applied to both electrodes, and the current density was set to lOAZdm 2 until the thickness of the metal deposited on the upper surface of the convex portion in the region A of the conductive substrate reached 5 / zm.
- the thickness of the metal (grounding part) deposited on the upper surface of the convex part in region B was 4 m, and there were almost no pinholes.
- the entire surface was covered with a thin film insulating layer, so that the copper plating did not precipitate.
- a primer HP-1; manufactured by Hitachi Chemical Co., Ltd. 1 m thick on the surface of a 100 m thick polyethylene terephthalate (PET) film (A-4100, manufactured by Toyobo Co., Ltd.) as an adhesive layer Acrylic polymer (HTR-280, manufactured by Nagase ChemteX Corporation) was sequentially applied to a thickness of 10 ⁇ m to prepare an adhesive film.
- PET polyethylene terephthalate
- A-4100 manufactured by Toyobo Co., Ltd.
- Acrylic polymer HTR-280, manufactured by Nagase ChemteX Corporation
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film and the surface on which the conductive layer pattern of the conductive substrate was present were bonded together using a roll laminator.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0.1 lMPa, and a line speed of lmZmin.
- the adhesive film was peeled off, the copper deposited on the upper surface of the convex portion of the conductive substrate was transferred to the adhesive film, and the transfer residue was also strong.
- the copper plating pattern transferred to the adhesive film has a partial force corresponding to area A, S line width of 28 ⁇ m, line pitch of 300 ⁇ m, conductor thickness of 5 ⁇ m, and a part corresponding to area B (grounding part)
- the line width was 97 ⁇ m
- the line pitch was 300 ⁇ m
- the conductor thickness was 4 ⁇ m.
- the substrate with the conductor layer obtained above is immersed in an aqueous solution obtained by diluting alkaline degreasing solution Degrease A (Odec Co., Ltd.) 5 times at room temperature for 3 minutes, then washed with water, 10% by weight glass Immerse in an acid aqueous solution at room temperature for 2 minutes, and after washing with water, immerse it in a 4-fold diluted aqueous solution of blackening solution Copal (Odek Co., Ltd.) to make the conductor layer pattern blackened.
- a substrate with an adhesive was obtained.
- UV curable resin hyaloid 7983AA3 (Hitachi Chemical Co., Ltd.)
- a polycarbonate film (Macro Hall DE, Bayer, 75 ⁇ m) is laminated on it, and UV light of UZcm 2 is applied using an ultraviolet lamp. Irradiation was performed to harden the UV curable resin to obtain a substrate with a conductor layer pattern having a protective film having a thickness of 20 m.
- a grid pattern with a light transmission part line width of 70 ⁇ m, a line pitch of 350 ⁇ m, and a bias angle of 45 ° is formed on four sides 30 mm inside from the outermost periphery of the pattern drawing part Furthermore, a lattice pattern with a line width of 30 m, a line pitch of 300 m, and a bias angle of 45 ° was formed on the entire inner surface. The inner and outer lines have different line pitch, so there are some unconnected areas .
- This negative film pattern corresponds to the pattern shown in FIG.
- the negative film produced in the negative film specification 2 was used in the same manner as in Example dl, except that etching was performed until the width (line width) of the upper surface of the convex portion in region A reached 7 ⁇ m.
- a conductive base material having a pattern of parts and a concave part of the geometrical figure drawn by the pattern was obtained.
- This conductive substrate has a width (line width) 7 / ⁇ ⁇ at the top surface of the convex portion in region A, a distance of 300 m between the top surfaces of the convex portion, and a height of 19 m at the convex portion.
- the surface opposite to the surface on which the pattern was formed was not etched because the resist film was formed on the entire surface, and the resist was removed after the etching as described above.
- the shape of the pattern is as shown in FIG. 5.
- the convex part of region A and the convex part of region B are continuous, and there are also parts.
- the cross-sectional shape of the recesses in region A and region B was a curved surface (similar to Fig. 3-d).
- Electrodeposition coating was performed on the entire surface of the stainless steel plate etched into a lattice pattern of the conductive base material (including the back side that was etched!). After washing with water and drying at 100 ° C for 10 minutes, baking was performed at 180 ° C for 30 minutes. The coating thickness of the electrodeposition paint was 2.6 m.
- the upper surface of the convex part of the electrodeposited conductive substrate is polished with polishing powder (TypeO. 1R, manufactured by Baikalox) and polishing cloth (manufactured by CONSUMABLES Buehler GMBH), and the upper surface (SUS surface) was exposed to produce a conductive substrate having an insulating film.
- the thickness of the electrodeposition coating in the recess of this conductive substrate is 2.6 m.
- the thickness of the electrodeposition coating near the top edge of the force projection was 0.2 m.
- the electrodeposition coating film at the edge of the upper surface of the convex portion was flush with the upper surface.
- the concave portions were covered with a thin film insulating film in both the region A and the region B.
- Neuron UR— 1350 (Toyobo Co., Ltd., polyester resin) 100 parts by weight Coronate L (Nihon Polyurethane Co., Ltd., isocyanate compound) 3 parts by weight [0247] (Transfer)
- the adhesive surface of the adhesive film obtained above and the surface of the conductive substrate on which the blackened copper plating was present were bonded using a roll laminator.
- Lamination conditions were a roll temperature of 100 ° C, a pressure of 0.1 MPa, and a line speed of 0.3 mZmin. Since it was laminated at a temperature exceeding the glass transition point (Tg) of the adhesive, tackiness appeared on the adhesive surface.
- Tg glass transition point
- Conductive substrate pattern A pattern formed by transferring the copper plating deposited on the top of the convex part of area A to the adhesive film is 11 ⁇ m in line width, 300 ⁇ m in line pitch, 3 ⁇ m in conductor thickness.
- the pattern formed by transferring the copper plating (grounding part) deposited on the upper surface of the convex part in area B to the adhesive film is a line width of 63 ⁇ m, a line pitch of 350 ⁇ m, and a conductor thickness of 2. It was 8 ⁇ m. After the transfer to the adhesive film, the transferred line was observed with a microscope. As a result, the cracks on the entire surface were ineffective. In this way, the blackened metal pattern is bonded to the adhesive film. It was transcribe
- the PET film (A-4100, manufactured by Toyobo Co., Ltd., 75 ⁇ m) was peeled off, A substrate with a conductor layer pattern having a protective film having a thickness of 20 ⁇ m was obtained.
- the size of the pattern drawing part is 300 mm square, and the stripe pattern with a line width of 250 ⁇ m and a line pitch of 750 ⁇ m on the four sides, 30 mm inside from the outermost periphery of the pattern drawing part. It was formed perpendicular to the drawing part.
- a grid pattern with a line width of 20 ⁇ m, a line pitch of 250 ⁇ m, and a bias angle of 30 ° was formed on the entire inner surface. Because the outer line is striped, there are some areas that are not connected to the inner line and the outer line.
- This negative film pattern corresponds to FIG.
- the width of the convex part in area A (line width) S Conducted under the same conditions as in Example dl, except that etching was performed until 15 m, to obtain a conductive substrate having a convex pattern having a top surface and a geometrical figure-shaped concave portion drawn thereby. It was.
- the width of the upper surface of the convex portion (line width) of the conductive substrate region A (line width) is 15 m
- the spacing between the upper surfaces of the convex portion (line pitch) is 250 m
- the height of the convex portion is 13 m.
- the width of the convex pattern (line width) is 245 ⁇ m, and the distance between the top surfaces of the convex parts (line pitch) H)
- the height of the convex part was 750 ⁇ m and the height was 13 ⁇ m.
- the planar shape of the pattern in region A and the pattern in region B was the same as that shown in FIG.
- the cross-sectional shape of the recesses in region A and region B was curved (similar to Fig. 3-d).
- the lattice pattern The entire surface of the etched stainless steel plate (etched, including the back side) was electrodeposited. After washing with water and drying at 100 ° C. for 10 minutes, it was cured under irradiation conditions of 3jZcm 2 .
- the coating thickness of the electrodeposition paint was 3.
- the upper surface of the convex portion of the electroconductive substrate coated with electrodeposition was polished with # 4000 abrasive paper to expose the upper surface of the convex portion. At this time, the thickness of the electrodeposition coating film at the edge of the upper surface of the convex portion of the conductive substrate was 0.5 ⁇ m.
- an electrolytic bath for electrolytic copper plating using a conductive substrate having an insulating film as a cathode copper sulfate (pentahydrate) 180 gZL, sulfuric acid 100 gZL, Kavalaside HL (manufactured by Atotech Japan Co., Ltd., additive) 70 ml ZL aqueous solution, 30 ° C.
- Voltage was applied to both electrodes, and the current density was 25 AZdm 2 until the thickness of the copper deposited on the upper surface of the convex part in region A of the conductive substrate reached 6 m.
- the thickness of the metal (grounding part) deposited on the upper surface of the convex part in area B was 3.5 m, and there was almost no pinhole.
- copper plating did not deposit on the surface opposite to the surface on which the pattern was formed because the entire surface was covered with a thin film insulating layer.
- the copper plating deposited on the upper surface of the convex portion of the conductive base material was subjected to blackening treatment under the same conditions as in Example dl.
- the following resin composition 2 was applied to the easy attachment surface of a 100 / zm thick PET film (A-4100, manufactured by Toyobo Co., Ltd.) so that the dry coating thickness was 15 m. Was made.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film obtained above and the surface of the conductive substrate on which the blackened copper was present were bonded using a roll laminator.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0.1 MPa, and a line speed of lmZmin.
- the pressure-sensitive adhesive film was peeled off from the conductive substrate, the copper deposited on the upper surface of the convex portion of the conductive substrate (the one that was blackened) was transferred to the adhesive surface of the pressure-sensitive adhesive film, and the transfer residue There was not.
- the pattern formed by transferring the copper plating deposited on the upper surface of the convex part of area A of the conductive substrate onto the adhesive film is 25 ⁇ m in line width, 250 ⁇ m in line pitch, and 6 ⁇ m in conductor thickness.
- the striped pattern formed by transferring the copper plating deposited on the upper surface of the convex part in area B to the adhesive film has a line width of 255 ⁇ m, a line pitch of 750 ⁇ m, and a conductor thickness of 3. It was 5 ⁇ m.
- the transferred line was observed with a microscope. As a result, the line was completely broken on the entire surface. In this way, the metal pattern subjected to the blackening treatment was transferred onto the adhesive film to obtain a substrate with a conductor layer pattern of the present invention.
- the pressure-sensitive adhesive surface (surface having a conductor layer pattern) of the substrate with a conductor layer pattern obtained above was laminated on and bonded to glass having a thickness of 2 mm. Bonding was performed only on the entire surface of region A, and the entire surface of region B was protruded from the glass.
- the lamination conditions when bonded to glass were a temperature of 25 ° C, a pressure of 0.5 MPa, and a line speed of 0.5 m / min. By roll lamination, the 6 m thick conductor layer pattern was embedded in the adhesive, and a highly transparent electromagnetic shielding material was obtained.
- BR-80 Mitsubishi Rayon Co., PMMA 100 parts by weight IRG— 022 (Nippon Yakuyaku Co., Ltd., Dimo-um salt-based infrared absorber) 3.3 parts by weight IR—12 (Nippon Shokubai Co., Ltd., phthalocyanine-based infrared absorber) 1.5 parts by weight Tolenene 60 Parts by weight
- the resin composition d4 was applied to the release treated surface of the release PET film (S-32, manufactured by Teijin DuPont Co., Ltd.) so that the dry coating thickness was 8 m and dried.
- a film coated with the resin composition d4 was bonded to the surface of the adhesive film containing the near-infrared absorber coated with a resin to produce a pressure-sensitive adhesive film having a near-infrared shielding property.
- a substrate with a conductor layer pattern was used in the same manner as in Example dl except that the adhesive film having the near-infrared shielding property obtained above (but used after peeling the release PET film) was used as the adhesive film. And the base material with a conductor layer pattern by which the conductor layer pattern was blackened was manufactured.
- the surface of the substrate with the conductor layer pattern of the substrate with the conductor layer pattern obtained by the blackening of the conductor layer pattern obtained above was irradiated with UV curable resin (Hitaloy 7851, Hitachi Chemical) After coating with polycarbonate film (Macro Hall DE, Bayer Co., Ltd., 75 ⁇ m), it was irradiated with lj / cm 2 ultraviolet rays using an ultraviolet lamp, and the conductor layer The pattern was coated with greaves. Next, an adhesive layer is formed on the surface of the film obtained above opposite to the surface on which the conductor layer pattern is formed, and is attached to a 3 mm thick PMMA plate (Comoglass) to attach the electromagnetic wave shielding member. Obtained.
- UV curable resin Hydrophilic acid
- a substrate with a conductor layer pattern was produced in the same manner as in Example d2 except that in Example d2 (Preparation of adhesive film), the dry coating thickness of the resin composition dl was 10 / zm.
- the substrate with the conductor layer pattern was immersed in the following black wrinkle treatment solution heated to 80 ° C for 3 minutes to blacken the conductor layer and the surface of the conductor layer was blackened.
- the base material with a conductor layer pattern which has a pattern was manufactured.
- An electromagnetic wave shielding member was obtained in the same manner as in (Production of electromagnetic wave shielding body) of Example d4 using the base material with a conductive layer pattern having a conductive layer pattern whose surface was blackened.
- a grid pattern with a line width of 100 ⁇ m, a line pitch of 300 ⁇ m, and a noise angle of 45 ° is formed on four sides 30 mm inside from the outermost periphery of the pattern drawing area. Further, a lattice pattern having a light transmission portion line width of 30 ⁇ m, a line pitch of 300 ⁇ m, and a bias angle of 45 ° was formed on the entire inner surface. The inner line and the outer line are all connected.
- This negative film pattern corresponds to the pattern shown in Figure 6.
- Example dl Similar to Example dl, except that the size of the SUS plate was 470 mm X 200 mm, a conductive substrate having a convex pattern having an upper surface and a geometrical figure-shaped concave portion drawn thereby. A material was prepared. In area A of this conductive substrate, the width of the upper surface of the convex part (line width) 20 / zm The distance between the upper surfaces of the convex part (line pitch) is 300 m, and the height of the convex part is 15.
- Width (line width) 90 ⁇ m, spacing between top surfaces of protrusions (line pitch) 300 ⁇ m, height of protrusions 15 / zm, and the planar shape of the pattern of protrusions and recesses in region A and region B is Fig 6 It was the same. Further, in the region A and the region B, the cross-sectional shape of the concave portion was a curved surface (similar to FIG. 3D). Note that the surface opposite to the surface on which the pattern was formed was not etched because the resist film was formed on the entire surface, and the resist was removed after the etching as described above.
- Example dl production of a conductive substrate having an insulating film
- a commercially available adhesive film was bonded to the opposite side of the surface on which the pattern was formed, and then electrodeposition coating was performed.
- electrodeposition coating, baking, and polishing of the upper surface of the convex portion were performed to obtain a conductive base material in which the concave portion was covered with an insulating film in both the region A and the region B.
- a substrate with a conductive layer pattern was continuously produced using an apparatus as shown in FIG. That is, as the rotating body 103, the conductive base material in which the recesses are covered with an insulating film in both the area A and the area B prepared above is wound on the surface of an iron rotating body (roll) having a diameter of 150 mm and a width of 200 mm. A drum electrode in which seams were bonded with tape was used. When the conductive substrate is wound around the rotating body, the adhesive bonded to the opposite side of the surface on which the pattern is formed is used to ensure electrical connection between the rotating body and the conductive substrate. The film was peeled off and wound so that the SUS surface and the rotating body surface were in contact.
- electrolytic copper was attached to the rotating body 103 with the apparatus configuration shown in FIG.
- anode 102 an insoluble electrode made of titanium coated with iridium oxide was used.
- the cathode is the drum electrode.
- electrolytic bath 100 for electrolytic copper plating copper sulfate (pentahydrate) 80gZL, sulfuric acid 180gZL, Cubelite VF1 (supplied by Ebara Eugene Co., Ltd., additive) 20mlZL aqueous solution 25 ° C charge solution 101 It is accommodated and sent between the anode 102 and the rotating body 103 by the pump 105 through the pipe 104 and filled. About half of the rotating body 103 is immersed in this electrolytic solution.
- a voltage was applied to both electrodes so that the current density was 40 AZdm 2, and the metal deposited on the upper surface of the convex portion of the region A of the conductive base material was stuck to a thickness of 5 ⁇ m. At this time.
- the above stainless steel roll was rotated at a speed of lmZ.
- Example 1 The adhesive film produced in dl was rolled up in a roll shape to obtain a roll-shaped adhesive film.
- the pressure-sensitive adhesive film 107 is unwound from the roll-shaped pressure-sensitive adhesive film, and the surface of the pressure-sensitive adhesive layer is deposited on the metal (copper) 106 deposited on the upper surface of the convex portion of the rotating body.
- More Example Under the same laminating conditions as in dl, by continuously bonding and peeling, the metal 106 was transferred to the adhesive layer of the adhesive film, and a substrate with a conductor layer pattern 109 was continuously produced. . The obtained base material 109 with a conductor layer pattern was wound into a roll.
- the conductor layer pattern formed by transferring the copper plating deposited on the upper surface of the convex part formed on the inner side to the adhesive film corresponds to the area A of the conductive substrate.
- the line width is 28 ⁇ m
- the line pitch is 300 ⁇ m
- the conductor thickness is 5 / zm.
- the area corresponding to the region B (ground part) is the line width of 97 m
- the conductor thickness is 4 m. Met.
- the substrate with the conductor layer pattern wound up in a roll was cut, sampled at three force points at equal intervals in the width direction, and the conductor layer pattern was observed with a microscope.
- the base material with the conductor layer pattern obtained above was rolled up while peeling the release PET, and continuously blackened.
- the substrate with a conductor layer pattern in which the conductor layer pattern was blackened was wound into a roll through a 4-fold diluted aqueous solution tank.
- the release layer (S-32, manufactured by Teijin DuPont Co., Ltd.) is laminated on the surface of the adhesive film to which the conductor layer pattern has been transferred. Prevented.
- the adhesive film was continuously rolled out by a so-called roll-to-roll, in which the roller was also unwound and the conductor layer pattern was wound around the roll after transfer.
- the copper plating on the stainless steel roll and its transferability remained unchanged. Furthermore, almost no pinholes were generated in the portion where the copper plating deposited on the pattern formed on the outside was transferred.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film with the conductor layer pattern obtained above (the surface on which the copper plating was transferred) was applied to a glass sheet having a thickness of 2 mm and laminated.
- Lamination conditions are temperature The temperature was 25 ° C, the pressure was 0.5 MPa, and the line speed was 0.5 m / min.
- the 1 m thick conductor layer pattern was embedded in the adhesive, and a highly transparent electromagnetic shielding body was obtained.
- Rolled SUS304 foil (made by Nisshin Steel Co., Ltd., finish 3Z4H, width 350mm, thickness 100 / ⁇ ⁇ ), PET film ( ⁇ -4100, manufactured by Toyobo Co., Ltd.) 1350 [Adhesive, manufactured by Toyobo Co., Ltd.] is applied to a dry adhesive thickness of 20 ⁇ m.
- SUS foil was produced as a conductive substrate (unprocessed). Lamination conditions were a roll temperature of 120 ° C, a preheat of 120 ° C for 30 seconds, a pressure of 3 MPa, and a line speed of 0.5 mZmin.
- a resist film (Phototech H-Y920, manufactured by Hitachi Chemical Co., Ltd.) is continuously bonded to one surface of the raw roll-shaped conductive substrate with a roll laminator, and wound into a roll. It was. Shell occupying conditions were a roll temperature of 105 ° C, a pressure of 0.5 MPa, and a line speed of lm / min. Further, using the negative film used in Example d2, set a pair on the resist film formed on the conductive substrate so that the distance between the pattern including the set of areas A and B is 10 mm. The pattern consisting of area A and area B was exposed 30 times intermittently. Exposure was performed only to the pattern forming section each time.
- Ultraviolet rays were irradiated with 120 mJ Zcm 2 of ultraviolet rays from above the negative film under a vacuum of lOOmmHg or less.
- the conductive substrate exposed to the above pattern is set in a developing machine having a roll unwinding part and a scooping part, and the film is flowed at a line speed of 2 mZmin, developed, washed, dried, and then wound into a roll. I took it.
- the development was performed by showering, the length of the developing tank was 2 m, and the developer was a 1% by weight aqueous sodium carbonate solution.
- the conductive base material having the resist pattern obtained above is set in an etching apparatus having a roll unwinding part and a scooping part, and is flowed at a line speed of 1.5 mZmin. After etching, washing with water, and drying, Rolled up into a roll. Etching is done with shower ring, The length of the etching tank was 4 m, and the etching solution was a salty ferric aqueous solution (45 ° Be ′, manufactured by Tsurumi Soda Co., Ltd.) heated to 40 ° C. In this way, a conductive base material was prepared in which a set of region A and region B force patterns were arranged at regular intervals.
- the upper surfaces of the convex portions of the regions B and A had a part that was not continuous, and the shape of the opening was the same as that shown in FIG.
- the size of the pattern consisting of a pair of area A and area B is 300 mm square, and area B is set on four sides, 30 mm inside from the outermost periphery of the pattern drawing area. Thirty patterns, each consisting of a pair of region A and region B, were produced at an interval of 10 mm.
- a cationic electrodeposition paint (UC-2000, manufactured by Shimizu Corporation) with the conductive substrate having the pattern consisting of the above-mentioned pair of regions A and B as the anode and the cathode as the titanium plate.
- a voltage was applied for 60 seconds to electrodeposit the SUS foil surface of the conductive substrate.
- the electrodeposition paint was irradiated with ultraviolet rays under an irradiation condition of 3jZcm 2 to be cured.
- the coating thickness of the electrodeposition paint was 3.9 m.
- the electrodeposition-coated stainless steel plate was polished with # 4000 polishing paper, and only the upper surface of the convex portion was exposed, and a conductive base material in which the concave portion was covered with an insulating film was produced.
- the above operation was performed on the other 29 conductive substrates having a pattern composed of the above-described pair of regions A and B.
- Each of the 30 conductive substrates whose recesses were covered with an insulating film was cut to 300 mm square, each of which was cut off unnecessary portions.
- a substrate with a conductor layer pattern was prepared using the apparatus shown in FIG. This apparatus will be described using.
- the hoop-like conductive substrate 110 obtained above is pre-treated tank 129, electrolytic bath 130, water washing tank 131, blackening treatment tank 132, water washing tank 133, anti-bacterial treatment by rolls 111-128. It is configured to circulate through the tank 134 and the rinsing tank 135.
- the pretreatment tank 129 contains a 5% sulfuric acid aqueous solution
- the electrolytic bath 130 contains copper sulfate (pentahydrate) 180 gZL, sulfuric acid lOOgZL, and Kaparaside HL (manufactured by Atotech Japan Co., Ltd., additive) 70 mlZL. It contains an electrolyte whose temperature is adjusted to 30 ° C.
- the black soot treatment tank 132 contains a 4-fold diluted solution of Copal (Odek Co., Ltd.).
- 0.5% benzotriazole aqueous solution is stored in the fender tank 134.
- the electrolytic bath 130 is configured such that the hoop-like conductive substrate 110 is used as a cathode, phosphorous copper is used as an anode, and the current density is 30 AZdm 2 .
- the metal layer deposited on the upper surface of the convex portion in region A was attached to a thickness of 3 m, and a conductor layer pattern was formed on the conductive substrate.
- the conductive layer pattern on the conductive substrate was subjected to blackening treatment in the blackening treatment layer 132 in the same manner as in Example dl using copal liquid (manufactured by Odec Co., Ltd.). After washing with water in the rinsing tank 132, it was rust-treated in the rust-proofing tank 134, further washed with water in the rinsing tank 135, and then rolled into Example d3 using the adhesive film 136 used in Example d3. Under the same conditions, using the crimping roll 137, the conductor layer pattern was continuously transferred onto the adhesive film 136 to obtain the substrate 138 with the conductor layer pattern continuously. It was wound up into a roll.
- the pattern formed by transferring the copper plating deposited on the upper surface of the convex part in area A to the adhesive film has a line width of 11 ⁇ m, a line pitch of 300 ⁇ m, and a conductor thickness of 3 ⁇ m.
- the pattern formed by transferring the copper plating deposited on the top of the protrusions onto the adhesive film had a line width of 63 ⁇ m, a line pitch of 350 ⁇ m, and a conductor thickness of 2.8 ⁇ m.
- the transferred line was observed with a microscope. As a result, the line was completely broken on the entire surface.
- the substrate 138 with the conductor layer pattern was wound up in a roll shape, lamination was performed so that the release PET (S-32, manufactured by Teijin DuPont) was in contact with the surface of the conductor layer pattern. Even after the substrate with the conductor layer pattern is wound up to 50 meters, the peeling of the insulating film formed in the recess of the conductive substrate where the transferability of the copper plating deposited on the conductive substrate remains unchanged is also observed. It was n’t. Furthermore, there were almost no pinholes with no cracks in the line of the portion corresponding to region B (grounding portion) of the obtained substrate with a conductor layer pattern.
- a protective film was continuously formed with a so-called roll-to-roll by irradiating UV light of / cm 2 to obtain a substrate with a conductor layer pattern having a protective tank.
- a dry film photoresist (HY-920 (manufactured by Hitachi Chemical Co., Ltd., thickness 20 / zm)) was bonded to a stainless steel (SUS304) plate at a roll temperature of 100 ° C, a linear pressure of 0.3 MPa, and a line speed of lmZmin.
- a negative pattern with an optically opaque frame (corresponding to the grounding part) with a line width of 30 m and a line pitch of 300 m at the outer periphery and a resist film on the stainless steel plate
- the negative pattern was applied with UV light under the conditions of lOOmjZcm 2.
- the resist film was developed with 1% sodium carbonate aqueous solution to form a 30 / zm wide groove on the SUS plate. Heat cure at 1 ° C for 1 hour I let you.
- an electrolytic bath for electrolytic copper plating using the SUS plate formed with the above resist as a cathode [copper sulfate (pentahydrate) 100gZL, sulfuric acid 180gZL, Top Lucina H-380 (Okuno Pharmaceutical Co., Ltd., Additive) 2. Dipped in 5 ml ZL aqueous solution, 30 ° C], and immersed in the same electrolytic bath with phosphorous copper as anode. As 3AZdm 2 current density by applying a voltage to both electrodes, grooves of the line portion formed in the resist is plated to completely fill.
- Example dl was used as an adhesive film.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film was bonded to the surface of the SUS plate that had been subjected to copper plating using a roll laminator.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0.1 lMPa, and a line speed of lmZmin.
- the adhesive film bonded to the conductive substrate was peeled off, the copper deposited in the resist groove of the SUS plate was transferred to the adhesive film, but the copper (grounding part) formed on the frame portion was Some parts remained on the conductive substrate without being transferred.
- the copper skin film was cracked.
- Example dl a conductor layer pattern obtained by attaching the entire surface of the portion corresponding to the region B of the conductive base material to the light opaque portion without patterning the portion corresponding to the region B in the negative film Except for the formation of the grounding part of the base material with an adhesive, all of the pinholes were generated in the copper of the grounding part as a result of producing a substrate with a conductive layer pattern that had been blackened in the same manner as Example dl. In addition, it was confirmed that cracks occurred over the entire surface of the grounding portion.
- Figure 30 shows the results of evaluating the durability of the conductive substrate after repeating the 30th peeling and peeling.
- Example 31 (hereinafter, also referred to as “Example el”. The same applies to Example 35) will be described. (Manufacture of conductive substrate having notched convex part with upper surface and concave part of geometric figure drawn by it)
- Resist film (Photech H—Y920, 20 ⁇ m thick, manufactured by Hitachi Chemical Co., Ltd.) on both sides of 1 Ocm square stainless steel (SUS304, finished 3Z4H, thickness 100 / ⁇ ⁇ , manufactured by Nisshin Steel Co., Ltd.) Pasted together.
- the shelling conditions were as follows: roll temperature 105 ° C, pressure 0.5 MPa, line speed lmZmin. Next, the line width of the light transmitting part is 40 m, the line pitch is 300 ⁇ m, and the bias angle is 45 ° (in the regular square, the line is arranged at an angle of 45 degrees with respect to the side of the regular square.
- the negative film formed in a lattice shape was allowed to stand on one surface of a stainless steel plate to which a resist film was bonded.
- ultraviolet rays were irradiated at 120 miZcm 2 from above and below the stainless steel plate on which the negative film was placed under a vacuum of 600 mmHg or less. further.
- a resist mask having a line width of 40 m, a line pitch of 300 m, and a bias angle of 45 ° was formed on the SUS plate. Note that the surface opposite to the surface on which the pattern is formed is exposed to the whole surface, so that it is not developed and a resist film is formed on the entire surface.
- the SUS plate was etched using a salty ferric aqueous solution (45 ° Be ', manufactured by Tsurumi Soda Co., Ltd.) heated to 40 ° C. Etching is carried out until the line width of the SUS plate (the width of the upper surface of the convex portion) reaches about 7 m, on the conductive substrate having the convex portion pattern having the upper surface and the concave portion of the geometrical drawing shape drawn thereby.
- a conductive base material for intermediate (intermediate product) was prepared in which a resist mask remained. When the surface of the resist mask was observed with a microscope, the width of the line (the width of the upper surface of the convex portion) was 5 to 8 / ⁇ ⁇ . The surface opposite to the surface on which the pattern was formed was not etched because a resist film was formed on the entire surface.
- the anode as a stainless steel (SUS 304) plate, and in a cationic electrodeposition paint (Insuleed3020, manufactured by Nippon Paint Co., Ltd.) under the condition of 15V10 seconds
- electrodeposition was applied to a stainless steel plate etched into a lattice pattern. After washing with water and drying at 100 ° C for 10 minutes, the resist mask was peeled off with a 2% aqueous sodium hydroxide solution, and then the electrodeposition coating film was baked at 230 ° C for 40 minutes in a nitrogen stream. The oxygen concentration in the furnace is 1% Met.
- the coating thickness of the electrodeposition paint was 2.
- the conductive base material for plating in which the recesses thus obtained were covered with an insulating film had an insulating film selectively formed in the recesses as shown in FIG. 11-e.
- Electrolytic copper plating was performed using the conductive substrate for plating with the adhesive film attached as a cathode.
- Electrolytic copper plating bath (copper sulfate (pentahydrate) 230gZL, sulfuric acid 55gZL, cube light # 1AHH (Sugawara Eugilite, additive) 4mlZL aqueous solution, 25 ° C)
- the porous substrate was immersed in the cathode and the phosphorous copper was immersed in the anode.
- Voltage was applied to both electrodes, and the current density was set to 5AZdm 2 until the thickness of the metal deposited on the upper surface of the convex part of the conductive base material for plating reached 5 ⁇ m.
- a primer HP-1; manufactured by Hitachi Chemical Co., Ltd. 1 m thick on the surface of a 100 m thick polyethylene terephthalate (PET) film (A-4100, manufactured by Toyobo Co., Ltd.) as an adhesive layer Acrylic polymer (HTR-280, manufactured by Nagase Chemtech) was sequentially applied to a thickness of 10 m to prepare an adhesive film for transfer.
- PET polyethylene terephthalate
- A-4100 manufactured by Toyobo Co., Ltd.
- Acrylic polymer HTR-280, manufactured by Nagase Chemtech
- the surface of the pressure-sensitive adhesive layer of the transfer pressure-sensitive adhesive film and the surface subjected to copper plating of the conductive substrate for adhesion were bonded together using a roll laminator.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0.1 MPa, and a line speed of lmZmin. Subsequently, when the adhesive film bonded to the plating transfer plate was peeled off, the copper deposited on the upper surface of the convex portion of the adhesive conductive substrate was transferred to the adhesive film.
- a substrate with a conductor layer pattern having a line width of 11 to 18 / ⁇ ⁇ , a line pitch of 300 ⁇ m, and a conductor thickness of 5 ⁇ m and having a grid-like metal pattern force was obtained.
- the insulating film was peeled off, and the part where the insulation film was peeled was strong.
- UV Coated curable resin hyaloid 7983AA3 manufactured by Hitachi Chemical Co., Ltd.
- polycarbonate film laminated with polycarbonate film (macro hole DE, Bayer Co., Ltd., 75 ⁇ m).
- Conductor layer pattern in UV curable resin was coated with a conductor layer pattern having a protective film by irradiating UV light of UZc m 2 with an ultraviolet lamp to cure the UV curable resin.
- the process of one transfer of copper plating was repeated 250 times in the same manner as described above, and as a result, the insulating film was peeled off with no change in the transfer performance of copper plating. Was also not observed. Further, the visible light transmittance of the obtained base material with a conductor layer pattern (with a protective film) was 80% or more.
- the SUS plate was etched using a ferric chloride aqueous solution (45 ° Be ′, manufactured by Tsurumi Soda Co., Ltd.) heated to 40 ° C. Etching is performed until the width (line width) of the upper surface of the convex portion formed on the SUS plate reaches 30 m, and the conductive substrate having the convex portion pattern having the upper surface and the geometrical figure-shaped concave portion drawn thereby.
- a ferric chloride aqueous solution 45 ° Be ′, manufactured by Tsurumi Soda Co., Ltd.
- a conductive base material for adhesion (intermediate) in which the resist mask remained on the material was produced.
- the width of the line was 29 to 32 ⁇ m as observed with a microscope over the resist mask.
- Electroconductive coating (intermediate) was electrodeposited. After washing with water and drying at 100 ° C for 10 minutes, the resist mask was peeled off with a 2% aqueous sodium hydroxide solution, and then the electrodeposition coating film was baked under a nitrogen stream at 180 ° C for 30 minutes. The oxygen concentration in the furnace was 0.5%. The coating thickness of the electrodeposition paint was 3. l / z m.
- the conductive substrate for plating in which the recesses thus obtained were covered with an insulating film was such that the insulating film was selectively formed in the recesses as shown in FIG. 11-e.
- an adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the uneven pattern of the conductive substrate for plating obtained above was not formed.
- Electrolytic bath for electrolytic copper plating (copper sulfate (pentahydrate) 250gZL, sulfuric acid 70gZL, Cubright AR) using the conductive substrate for plating with this adhesive film as the cathode and phosphorous copper as the anode (Supplied by EBARA Eugeneite Co., Ltd., 4mlZL in water, 25 ° C), voltage is applied to both electrodes, the current density is 2 OAZdm 2 , and deposits on the top of the convex part of the conductive substrate for plating Until the thickness of the finished metal reached 3 ⁇ m.
- Example el the same adhesive film for transfer as obtained in Example el was bonded using a roll laminator so that the adhesive layer strength was in contact with the copper-plated surface of the conductive substrate for bonding.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0.1 MPa, and a line speed of 1 mZmin.
- the adhesive substrate film for plating was peeled off, the copper deposited on the upper surface of the convex portion of the conductive substrate for plating was transferred to the surface of the adhesive layer.
- UV curable resin hyaloid 7983AA3 manufactured by Hitachi Chemical Co., Ltd.
- PET film A-4100, manufactured by Toyobo Co., Ltd., 75 m
- UV curable resin was laminated with UV curable resin to form a conductor layer pattern. It was embedded in UV-cured cocoon.
- the PET film (A-4100, manufactured by Toyobo Co., Ltd., 75 m) was peeled off to form a protective film. A base material with a conductor layer pattern was obtained.
- the process of one transfer with copper was repeated 250 times in the same manner as above, and as a result, the peeled part of the insulating film with no change in the transfer property of copper plating was observed. The power was not. Further, the visible light transmittance of the obtained base material with a conductor layer pattern (with a protective film) was 80% or more.
- a resist film (Phototech H—Y920, 20 / zm thickness, manufactured by Hitachi Chemical Co., Ltd.) is wrapped around a stainless steel roll with a diameter of 150 mm and a width of 200 mm, and is applied with pressure using a hand roll at room temperature. Combined. Next, a negative film formed in a lattice shape with a line width of 35 m, a line pitch of 275 ⁇ m, and a bias angle of 45 ° was also wrapped around the resist film's upper force, under a parallel exposure machine. It was exposed while turning by hand.
- a resist mask having a line width of 60 ⁇ m and a line pitch of 275 ⁇ m was formed on the surface of the stainless steel roll by developing with a 1% sodium carbonate aqueous solution. Because the part of the negative film wrapped around the curved surface was exposed with a parallel exposure machine, the resist mask line width was thicker than the negative film line width. Furthermore, the stainless steel roll was etched using a salted ferric iron solution heated to 40 ° C., and a lattice pattern (line width, ie, the width of the upper surface of the convex portion 20) was formed on the surface of the stainless steel roll. ⁇ 27 111, pitch 275 m, convex height 30 m). At this stage, the resist mask still remains on the upper surface of the convex portion.
- the above-mentioned stainless steel roll is used as the cathode, the anode as the stainless steel (SUS304) plate, and in a cationic electrodeposition paint (Insuleed3020, manufactured by Nippon Paint Co., Ltd.) in a grid pattern at 15V10 seconds.
- Electrodeposition coating was performed on an etched stainless steel roll. After washing with water and drying at 100 ° C for 10 minutes, the resist mask was peeled off with a 2% aqueous sodium hydroxide solution. Baking was performed under an argon atmosphere at 230 ° C. for 40 minutes. The oxygen concentration at that time was 2%.
- the coating thickness of the electrodeposition paint was 2.
- Electroplated copper was attached to the rotating body 103 with the apparatus configuration shown in FIG.
- As the anode 102 an insoluble electrode made of titanium coated with platinum was used.
- the stainless steel tool was used as the drum electrode for the cathode.
- electrolytic bath 100 for electrolytic copper plating copper sulfate (pentahydrate) 70gZ L, sulfuric acid 180gZL, Kabaraside HL (manufactured by Atotech Japan Co., Ltd.) 20mlZ L of aqueous solution 25 ° C electrolyte 101 It is accommodated and sent between the anode 102 and the rotating body 103 by the pump 105 through the pipe 104 and filled. About half of the rotating body 103 is immersed in this electrolytic solution.
- Example el A voltage was applied to both electrodes so that the current density was 7 AZdm 2, and plating was performed until the thickness of the metal deposited on the upper surface of the convex portion in the region A of the conductive substrate became 2 m. At this time.
- the above-mentioned stainless steel roll was rotated at a speed of lmZ.
- the pressure-sensitive adhesive film produced in Example el was rolled up in a roll shape to obtain a roll-shaped pressure-sensitive adhesive film.
- the pressure-sensitive adhesive film 107 is unwound from the roll-shaped pressure-sensitive adhesive film, and the surface of the pressure-sensitive adhesive layer is applied to the metal (copper) 106 deposited on the upper surface of the convex portion of the rotating body (stainless steel roll) by the pressure-bonding roll 108 and the el.
- the metal 106 was transferred to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film, and the substrate 109 with a conductor layer pattern was continuously produced.
- the substrate 109 with the conductor layer pattern was wound up in a roll (not shown).
- the conductor layer pattern had a line width of 22 to 31 m, a line pitch of 275 ⁇ m, and a conductor thickness of 2 ⁇ m. Even after 50 m of the adhesive film to which the copper plating had been transferred, the copper plating on the stainless steel roll and the insulating film peeling site where there was no change in the transferability were observed.
- a portion of the obtained base material with a conductor layer pattern is cut off, and a UV curable resin (Alonics UV-3701, manufactured by Toagosei Co., Ltd.) is applied to the surface on which the conductor layer pattern is formed (Yoshimi Seiki Co., Ltd.).
- a UV curable resin Alonics UV-3701, manufactured by Toagosei Co., Ltd.
- PEBA made by company
- PE T film Mylar D, manufactured by Teijin DuPont Film Co., Ltd., 75 m
- a protective film was formed.
- the resulting substrate with a conductor layer pattern (with a protective film) has a visible light transmittance of 80% or more.
- Rolled SUS304 foil (Nisshin Steel Co., Ltd., finished 3Z4H, width 200mm, thickness 100 / zm), PET film (A-4100, manufactured by Toyobo), Byron UR-1350 (adhesive, Toyobo) Roll-type adhesive film made by applying (Co., Ltd.) to a dry coating thickness of 20 ⁇ m is pasted together using a roll laminator to produce a rolled SUS foil with PET film (unprocessed) did.
- Lamination conditions were a roll temperature of 120 ° C, a preheat of 120 ° C for 30 seconds, a pressure of 3 MPa, and a line speed of 0.5 mZmin.
- This process was repeated 10 times to expose 10 patterns on SUS304 foil. This is developed through a developing machine using 1% sodium carbonate, and the line width is 40 ⁇ m on the SUS foil. Then, a SUS304 foil with a PET film in which resist masks having a line pitch of 400 ⁇ m were arranged at regular intervals was formed. Next, this SUS foil with PET film is passed through an etching line, and a lattice-like pattern (line width, that is, the width of the upper surface of the convex portion is 9 to 14 ⁇ m, the pitch is 400 ⁇ m, the height of the convex portion is 20 A conductive base material with ⁇ m) arranged at regular intervals was produced.
- line width that is, the width of the upper surface of the convex portion is 9 to 14 ⁇ m, the pitch is 400 ⁇ m, the height of the convex portion is 20 A conductive base material with ⁇ m
- the etched SUS foil with PET film was cut into patterns, and each SUS foil with PET film was made into a cathode, and the anode was made into a stainless steel (SUS304) plate.
- 5EZ5W manufactured by Shimizu Co., Ltd.
- electrodeposition was applied to a stainless steel plate etched in a lattice pattern under the condition of 20V 60 seconds. After washing with water and drying at 100 ° C for 15 minutes, the resist mask is peeled off with 2% sodium hydroxide, and the electrodeposition coating film is baked at 200 ° C for 30 minutes in a nitrogen atmosphere. A conductive base material for plating with a PET film covered with a coating was obtained. The oxygen concentration at that time was 0.5%.
- the coating thickness of the electrodeposition paint was: In the same manner, a total of 10 conductive substrates for stencil attachment with PET film in which the recesses were covered with an insulating layer were manufactured.
- the PET film with the 10 recesses prepared above covered with an insulating layer is attached on the adhesive surface of an adhesive film (SGA, manufactured by Hitachi Chemical Co., Ltd.) with a width of 200 mm and a length of 10 m.
- the PET film surface of the conductive substrate for bonding is bonded without gaps, and the 10m long recess is covered with an insulating layer.
- the long conductive substrate for plating was passed through an apparatus as shown in FIG. 25 to obtain a hoop-like conductive substrate.
- the joint was bonded from the back side of the joint using a commercially available gum tape, and the front side was bonded with a copper tape (CHO-FOIL, 50 mm width, manufactured by Taiyo Wire Mesh Co., Ltd.).
- a substrate with a conductor layer pattern was produced according to Example d7 using the apparatus shown in FIG.
- the obtained conductor layer pattern of the substrate with the conductor layer pattern has a line width of 11 to 16 m and a line width of 11 to 16 m.
- the pitch was 400 m and the thickness was 1 m.
- the surface of the obtained substrate with the conductor layer pattern on which the conductor layer pattern was formed was applied to the UV curable resin (Aronix UV-3701, Toagosei Co., Ltd.). Co., Ltd.) is coated with a thickness of 15 m, laminated with PET film (Mylar D, Teijin DuPont Films Co., Ltd., 75 m), and then irradiated with UZcm 2 ultraviolet rays using an ultraviolet lamp.
- a protective film was continuously formed by roll-to-roll to obtain a substrate with a conductor layer pattern having a protective tank.
- the substrate with a conductor layer pattern (with a protective film) having this protective tank had a visible light transmittance of 80% or more.
- a resist film (Photech H—Y920, 20 ⁇ m thickness, manufactured by Hitachi Chemical Co., Ltd.) was bonded to a 10 cm square stainless steel (SUS304, finished 3Z4H, thickness 100 m, manufactured by Nisshin Steel Co., Ltd.) plate.
- the bonding conditions were a roll temperature of 105 ° C, a pressure of 0.5 MPa, and a line speed of lmZmin.
- a negative film formed in a lattice pattern with a line width of 40 m, a line pitch of 300 ⁇ m, and a bias angle force of 5 ° was allowed to stand on a stainless steel plate bonded with a resist film. .
- ultraviolet rays were irradiated at 120 miZcm 2 from above the negative film under a vacuum of 600 mm Hg or less. further.
- a resist mask having a line width of 40 m, a line pitch of 300 ⁇ m, and a bias angle of 45 ° was formed on the SUS plate.
- 40 ° C The SUS plate was etched using an aqueous ferric chloride solution (45 ° Be ', manufactured by Tsurumi Soda Co., Ltd.). Etching was performed until the line width of the SUS plate reached 7 m.
- the resist mask formed on the SUS plate is peeled off, and the pattern on the lattice pattern (line width, that is, the width of the upper surface of the convex portion is 5 to 8). / ⁇ ⁇ , pitch 300 m, convex height 15 m) was formed, and a conductive substrate having a convex pattern having an upper surface and a concave portion having a geometric shape drawn thereby was produced.
- the anode as a stainless steel (SUS304) plate, and in the force thio-based electrodeposition paint (Insuleed 3020, manufactured by Nippon Paint Co., Ltd.), the above conductive group
- the material was electrodeposited. After washing with water and drying at 110 ° C for 10 minutes, it was baked under a nitrogen stream at 230 ° C for 40 minutes. The oxygen concentration in the furnace was 0.1%.
- the coating thickness of the electrodeposition paint was 2.6 m. Furthermore, the electrodeposited conductive base material is polished with an abrasive powder (TypeO. 1R, manufactured by Baikalox) and a polishing cloth (Microcloth, manufactured by BUEHLER) to expose the SUS surface, A conductive substrate having an insulating film was produced.
- the thickness of the electrodeposition coating film in the concave portion of the electroconductive substrate for adhesion was 2.6 m.
- the thickness of the electrodeposition coating film at the edge of the upper surface of the convex portion was 0.2 m (measured in the plane direction of the upper surface).
- the line width after polishing that is, the width of the upper surface of the convex portion was 5 to 15 m. In this conductive base material for plating, the concave portion was covered with an insulating film.
- an electroplating bath for electrolytic copper plating (copper sulfate (pentahydrate) 250gZL, sulfuric acid 50gZL, Cubelite # 1A (supplied by Ebara Eugleite Co., Ltd., additive) ) It was immersed in a 4 ml / L aqueous solution (25 ° C), and immersed in the same electrolytic bath using phosphorous copper as an anode.
- 7AZdm 2 current density by applying a voltage to both electrodes, the thickness of the metal deposited on the protrusion upper surface was plated to a 5 mu m.
- the pressure-sensitive adhesive surface of the same pressure-sensitive adhesive film as prepared in Example el and the surface of the conductive substrate for plating that had been subjected to copper plating were bonded using a roll laminator.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0.1 lMPa, and a line speed of lmZmin. Then When the pressure-sensitive adhesive film adhered to the sticky transfer plate was peeled off, the copper deposited on the upper surface of the convex portion of the sticky transfer plate was transferred to the pressure-sensitive adhesive surface.
- a metal pattern having a line width (width of the upper surface of the protrusion) of 11 to 30 ⁇ m, a line pitch of 300 ⁇ m, and a conductor thickness of 5 ⁇ m was transferred onto the adhesive film.
- the plating transfer plate prepared by polishing had a variation in line width, and some lines were wobbled.
- the conductor layer pattern thus obtained also had a line width variation.
- the obtained substrate with the conductor layer pattern had a visible light transmittance of 80% or more.
- Conductive base material for adhesion in which a resist mask remains on a conductive base material having a pattern of convex portions having an upper surface and a geometrical figure-shaped concave portion drawn thereby in the same manner as in Example el ) was produced.
- the obtained conductive substrate had a line width of 14 to 19 m, a line pitch of 350 ⁇ m, and a height of the convex part of 20 ⁇ m.
- the anode as a stainless steel (SUS 304) plate, in a cationic electrodeposition paint (Insuleed 3020, Nippon Paint Co., Ltd.) The material was electrodeposited. After washing with water and drying at 110 ° C.
- the resist mask was peeled off with a 2% aqueous sodium hydroxide solution. Next, it was baked under a nitrogen stream at 230 ° C for 40 minutes. The thickness of the electrodeposition paint was 20 ⁇ m. Since the resist mask width was 40 ⁇ m, the electrodeposition paint was electrodeposited beyond the width of the resist mask in the calculation. The resin flowed and flattened during baking. Almost no protrusion was found above the upper surface of the convex pattern. In this conductive base material for plating, the concave portion was covered with an insulating film. As shown in FIG. 10, the obtained plate for plating transfer had a shape in which the concave portions of the convex pattern were completely filled with the insulating layer.
- an electrolytic bath for electrolytic copper plating using the above plate for plate transfer as a cathode (copper sulfate (pentahydrate) 250gZL, 50gZL sulfuric acid, Cubelite AR (manufactured by Ebara Eugene Corporation, additive) ) It was immersed in an aqueous solution of 4 ml ZL, 30 ° C), and immersed in the same electrolytic bath with phosphorous copper as an anode. Voltage was applied to both poles to obtain a current density of 25AZdm 2 until the thickness of the metal deposited on the upper surface of the protrusion reached 5 ⁇ m.
- the line width and pitch were measured based on micrographs.
- the line thickness was measured by cutting a portion of the obtained conductor layer pattern, casting it with resin, and observing the cross section under a microscope.
- the copper pattern transferred to the adhesive film was observed with a magnifying glass, and the case where there was no transfer failure was judged good and the case where a transfer failure occurred was judged as bad.
- the presence / absence of transfer failure before peeling of the electrodeposition paint was described.
- the presence or absence of pattern abnormality was confirmed with the naked eye using a magnifier.
- the durability of the plating transfer plate was confirmed by directly observing the plating transfer plate after repeated fitting and peeling with a magnifier.
- Example 36 (hereinafter, also referred to as “Example fl”. The same applies to Example 42) will be described. (Manufacture of conductive substrate having notched convex part with upper surface and concave part of geometric figure drawn by it)
- a resist film (Photech H-Y920, manufactured by Hitachi Chemical Co., Ltd.) was bonded to a 10 cm square stainless steel (SUS304, finished 3Z4H, thickness 100 m, manufactured by Nisshin Steel Co., Ltd.).
- the shelling conditions were as follows: roll temperature 105 ° C, pressure 0.5 MPa, line speed lm Zmin. Next, the line width of the light transmission part is 30 ⁇ m, the line pitch is 300 ⁇ m, A negative film formed in a lattice shape with a bias angle force of S45 ° was allowed to stand on a stainless steel plate to which a resist film was bonded.
- ultraviolet rays were irradiated at 120 mjZcm 2 from above the negative film under a vacuum of 600 mmHg or less. further.
- a resist mask with a line width of 30 m, a line pitch of 300 ⁇ m, and a bias angle of 45 ° was formed on the SUS plate.
- the SUS plate was etched using a ferric chloride aqueous solution (45 ° Be ', manufactured by Tsurumi Soda Co., Ltd.) heated to 40 ° C. Etching was performed until the line width of the SUS plate reached 20 / zm.
- the resist film formed on the SUS plate is peeled off to form a lattice-like pattern (line width, that is, the width of the upper surface of the convex portion 20 m, line pitch).
- line width that is, the width of the upper surface of the convex portion 20 m, line pitch.
- the distance between the top surfaces of the protrusions is 300 m
- the height of the protrusions is 15 m
- the cross-sectional shape of the protrusions is a curved surface (similar to Fig. 3-d).
- a conductive base material having a concave portion having a geometric diagram shape to be drawn was produced.
- the above conductive base material is used as a cathode, and the anode is used as a titanium plate.
- a cationic electrodeposition paint (Insuleed 3020, manufactured by Nippon Paint Co., Ltd.), it is etched into a lattice pattern under the condition of 15 V for 10 seconds.
- a stainless steel plate was electrodeposited. After washing with water and drying at 100 ° C for 10 minutes, baking was performed at 190 ° C for 25 minutes. The coating thickness of the electrodeposition paint was 2.
- the electrodeposited stainless steel plate is polished with polishing powder (alumina solution B0. 05 ⁇ m, manufactured by Refinetech Co., Ltd.) and polishing cloth (CONSUMABLES manufactured by BUEHLER).
- the thickness of the electrodeposition coating film on the upper surface edge of the convex portion of this conductive substrate was 2.5 111, and the thickness of the electrodeposition coating film on the concave portion was 2.
- This conductive substrate was covered with an insulating film except for the upper surface of the convex portion.
- Electrolytic copper plating bath (copper sulfate (pentahydrate) 80gZL, sulfuric acid 180gZL, Cubelite VF1 (supplied by Sakakibara Eulite Co., Ltd., additive) 20mlZL aqueous solution, 25 ° C) etched into a lattice pattern
- the stainless steel plate was immersed, and immersed in the electrolytic copper plating bath using phosphorous copper as an anode. Both poles A voltage was applied to the substrate, and the current density was set to 25 AZdm 2 until the thickness of the metal deposited on the upper surface of the convex portion of the conductive substrate reached 5 ⁇ m.
- the conductive layer pattern on the conductive substrate obtained above was treated in the order of alkaline degreasing, water washing, pickling and water washing, then nickel sulfate 75gZL, nickel sulfate 45gZL, zinc sulfate 38gZL, sodium thiocyanate Use a dip solution containing 15 g ZL 50. C, 2.
- the thickness of the blackening treatment layer under the conditions of 5AZdm 2 makes a black nickel Me with so as to 0. 6 m.
- the plate was washed with pure water, immersed in a 20 mL ZL aqueous solution of water-soluble antifungal agent Evafin G800 (manufactured by Ebara Eugleite Co., Ltd.) at 40 ° C for 30 seconds, and then dried at 50 ° C. Unevenness of color of the black treatment layer and powder falling off did not occur.
- Evafin G800 manufactured by Ebara Eugleite Co., Ltd.
- a primer HP-1; manufactured by Hitachi Chemical Co., Ltd. 1 m thick on the surface of a 100 m thick polyethylene terephthalate (PET) film (A-4100, manufactured by Toyobo Co., Ltd.) as an adhesive layer Acrylic polymer (HTR-280, manufactured by Nagase ChemteX Corporation) was sequentially applied to a thickness of 10 ⁇ m to prepare an adhesive film.
- PET polyethylene terephthalate
- A-4100 manufactured by Toyobo Co., Ltd.
- Acrylic polymer HTR-280, manufactured by Nagase ChemteX Corporation
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film and the copper-plated surface of the conductive substrate were bonded together using a roll laminator.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0. IMP a, and a line speed of lmZmin.
- copper deposited on the upper surface of the convex portion of the conductive substrate was transferred to the adhesive film. From this, a substrate with a conductor layer pattern consisting of a metal pattern having a line width of 28 ⁇ m, a line pitch of 300 ⁇ m, and a conductor thickness of 5 ⁇ m was obtained.
- the portion where the insulating film was peeled off was strong.
- UV curable resin hyaloid 7983AA3 manufactured by Hitachi Chemical Co., Ltd. Laminated with polycarbonate film (Macro Hall DE, Bayer Co., Ltd., 75 ⁇ m) and the conductor layer pattern was buried in UV curable resin. Thereafter, the UV curable resin was cured by irradiating UZcm 2 ultraviolet rays using an ultraviolet lamp to obtain a substrate with a conductor layer pattern having a protective film.
- a grid pattern (line width 7 m, pitch 300 m) was formed on the SUS plate in the same manner as in Example fl except that etching was performed until the line width of the convex portion formed on the SUS plate was 7 ⁇ m.
- the height of the convex part is 30 m, and the cross-sectional shape of the convex part is a curved surface (similar to Fig. 3-d)), and the convex part of the convex part having the upper surface and the concave part of the geometric figure drawn by it are formed.
- a conductive base material was obtained.
- the above conductive base material is used under the condition of 10 V 60 seconds in an on-type electrodeposition paint (AMG-5EZ5W, manufactured by Shimizu Co., Ltd.) using the above conductive base material as the anode and the cathode as the titanium plate.
- the material was electrodeposited. After washing with water and drying at 100 ° C for 10 minutes, baking was performed at 180 ° C for 30 minutes. The coating thickness of the electrodeposition paint was 2.6 m.
- the electrodeposited conductive base material is polished with polishing powder (TypeO. 1R, manufactured by Baikalox) and polishing cloth (CONSUMABLES, manufactured by BUEHLER) to expose the SUS surface, A conductive substrate having an insulating film was produced.
- the thickness of the electrodeposition coating film on the upper surface edge of the convex portion of this conductive substrate was 0.2 ⁇ , and the thickness of the electrodeposition coating film on the concave portion was 2.
- This conductive base material was covered with an insulating film except for the upper surface of the convex portion.
- This conductive base material was covered with an insulating film except for the upper surface of the convex portion.
- the sample was immersed in an aqueous solution (30 ° C), and immersed in an electrolytic copper plating bath using phosphorous copper as an anode. Voltage was applied to both poles, the current density was lOAZdm 2 , and the metal deposited on the top surface of the protrusions was stuck to 3 ⁇ m.
- the conductive layer pattern on the conductive substrate obtained above was treated in the order of alkaline degreasing, water washing, pickling and water washing, then nickel sulfate 62gZL, nickel sulfate ammonium 40gZL, zinc sulfate 23gZL, sodium thiocyanate Use a dip solution containing 20 g ZL 50. C, 2.
- the thickness of the blackening treatment layer under the conditions of 5AZdm 2 makes a black nickel Me with so as to 0. 6 m.
- the plate was washed with pure water, immersed in a 20 mL ZL aqueous solution of water-soluble antifungal agent Evafin G800 (manufactured by Ebara Eugleite Co., Ltd.) at 40 ° C for 30 seconds, and then dried at 50 ° C. Unevenness of color of the black treatment layer and powder falling off did not occur.
- Evafin G800 manufactured by Ebara Eugleite Co., Ltd.
- Nylon UR— 1350 (made by Toyobo Co., Ltd., polyester resin) 100 parts by weight Coronate L (made by Nippon Polyurethane Co., Ltd., isocyanate compound) 3 parts by weight
- the adhesive surface of the adhesive film obtained above and the surface of the conductive substrate that had been subjected to copper plating and blackening treatment were bonded together using a roll laminator.
- Lamination conditions were a roll temperature of 100 ° C, a pressure of 0.1 lMPa, and a line speed of 0.3 mZmin. Since lamination was performed at a temperature exceeding the glass transition point (Tg) of the adhesive, tackiness was exhibited on the adhesive surface.
- Tg glass transition point
- UV curing type resin hyaloid 7983AA3 manufactured by Hitachi Chemical Co., Ltd.
- PET film A-4100, manufactured by Toyobo Co., Ltd., 75 m
- UV curable resin to UV cure the conductor layer pattern. It was buried in the mold.
- the PET film (A-4100, manufactured by Toyobo Co., Ltd., 75 m) is peeled off to form a protective film.
- the cathode as the titanium plate, and etching into a lattice pattern in a cationic electrodeposition paint (UC-2000, manufactured by Shimizu Corporation) under the conditions of 30 V 60 seconds.
- the coated stainless steel plate was electrodeposited. After washing with water and drying at 100 ° C. for 10 minutes, it was cured under irradiation conditions of 3jZcm 2.
- the coating thickness of the electrodeposition paint was 3.9 m.
- the electrodeposited stainless steel plate was polished with # 4000 abrasive paper, and the thickness of the electrodeposition coating on the top of the convex part of this conductive substrate was 0.5 m.
- the film thickness was 3.9 m o
- This conductive substrate was covered with an insulating film except for the upper surface of the convex portion.
- an electrolytic bath for electrolytic copper plating using a conductive substrate having an insulating film as a cathode copper sulfate (pentahydrate) 180 gZL, sulfuric acid 100 gZL, Kavalaside HL (manufactured by Atotech Japan Co., Ltd., additive) 70 ml ZL aqueous solution, 30 ° C.) and immersed in the same electrolytic bath using phosphorous copper as an anode. Voltage was applied to both electrodes, the current density was set to 30 AZdm 2 , and the metal deposited on the top surface of the protrusion was stuck to 1 ⁇ m. [0314] (Blackening treatment-Anti-bacterial treatment)
- the conductive layer pattern on the conductive substrate obtained above was treated in the order of alkaline degreasing, water washing, pickling and water washing, and then nickel sulfate 100gZL, nickel sulfate ammonium 30gZL, zinc sulfate 15g / L, thiocyan Use a moisturizing solution containing 10 g / L of sodium acid 50. C, 2.
- the thickness of the blackening treatment layer under the conditions of 5AZdm 2 makes a black nickel Me with so as to 0. 6 m.
- the plate was washed with pure water, immersed in a 20 mL ZL aqueous solution of water-soluble antifungal agent Evafin G800 (manufactured by Ebara Eugleite Co., Ltd.) at 40 ° C for 30 seconds, and then dried at 50 ° C. Unevenness of color of the black treatment layer and powder falling off did not occur.
- Evafin G800 manufactured by Ebara Eugleite Co., Ltd.
- the following resin composition 2 was applied to the easy attachment surface of a 100 / zm thick PET film (A-4100, manufactured by Toyobo Co., Ltd.) so that the dry coating thickness was 15 m. Was made.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film obtained above was bonded to the conductive base material using a copper laminator and a blackened surface using a roll laminator.
- Lamination conditions were a roll temperature of 25 ° C, a pressure of 0.1 MPa, and a line speed of lmZmin.
- copper (blackened) deposited on the upper surface of the convex portion of the conductive substrate was transferred to the adhesive surface of the pressure-sensitive adhesive film.
- a metal pattern having a line width of 17 m, a line pitch of 300 m, and a conductor thickness of 1 ⁇ m and further blackened is selectively transferred onto the adhesive film, and the conductor layer of the present invention is thus transferred.
- a substrate with a pattern was manufactured.
- the pressure-sensitive adhesive surface (surface having a conductor layer pattern) of the substrate with a conductor layer pattern obtained above was laminated on and bonded to glass having a thickness of 2 mm.
- Lamination conditions were a temperature of 25 ° C, a pressure of 0.5 MPa, and a line speed of 0.5 mZmin. Thick by roll lamination
- the 1 m conductor layer pattern was embedded in the adhesive, and a highly transparent electromagnetic wave shield was obtained.
- Example f2 Preparation of adhesive film, except that the dry coating thickness of the resin composition 1 was 10 m, a substrate with a conductor layer pattern was produced in the same manner as in Example f2. It was.
- the conductive layer of the base material with the conductive layer pattern is subjected to blackening treatment under the same conditions as the blackening treatment in Example f2 and the surface is blackened on the surface.
- the material was manufactured. Color unevenness of the black treatment layer and powder omission did not occur.
- An electromagnetic wave shielding member was obtained in the same manner as in Example f 3 (Preparation of electromagnetic wave shielding body), using the substrate with a conductive layer pattern having a conductive layer pattern whose surface was blackened.
- the surface of the conductor layer was oxidized by immersing the substrate with the conductor layer pattern in the following blackening treatment solution heated to 80 ° C for 3 minutes.
- the same base material with a conductor layer pattern was produced except that a base material having a conductor layer pattern that had been blackened was manufactured.
- Example 41 Using the base material having the conductor layer pattern with the black surface treated as obtained above, a base material with a conductor layer pattern having a protective film was obtained in the same manner as in Example fl. As a result, black powder powder is generated in the vicinity of the conductor layer pattern. As a result, the dropped light intensity as an electromagnetic wave shielding plate is reduced to about 10% as L * as shown in FIG. Color irregularities appear on the appearance. As a result, the electromagnetic wave shielding performance was evaluated by the Advantest method. As a result, it was 48 dB, and the electromagnetic wave shielding performance was not significantly reduced.
- Example 41 Example 41
- Example 1 blackening treatment Ichigo
- the substrate with the conductor layer pattern was immersed in Meltex Co., Ltd. Ebonol C special aqueous solution heated to 80 ° C for 3 minutes, so that the surface of the conductor layer was A similar base material with a conductor layer pattern was produced except that a base material having a conductor layer pattern oxidized and blackened was manufactured.
- a base material having a conductor layer pattern whose surface was blackened a base material with a conductor layer pattern having a protective film was obtained in the same manner as in Example fl.
- black powder powder is generated in the vicinity of the conductor layer pattern.
- the dropped light intensity as an electromagnetic wave shielding plate is impaired by about 10% as shown in FIG. Color unevenness occurred.
- it was 47 dB it was 47 dB, and the electromagnetic wave shielding property was not significantly lowered.
- the surface of the conductor layer was oxidized by immersing the substrate with the conductor layer pattern in an aqueous solution of Copper Black No. 65, Isolate Institute of Science Ltd. at room temperature for 1 minute.
- the same base material with a conductor layer pattern was produced except that a base material having a conductor layer pattern that had been blackened was manufactured.
- a base material with a conductor layer pattern having a protective film was obtained in the same manner as in Example fl.
- Example f6 black powder powdered off in the vicinity of the conductor layer pattern, and as a result, the transmitted light intensity as an electromagnetic wave shielding plate was reduced by about 10% to L * as shown in FIG. In addition, uneven color occurred in the appearance of the conductor layer.
- the electromagnetic wave shielding property by the Advantest method it was 46 dB, and the electromagnetic wave shielding property was not deteriorated.
- Embodiment 1 of the present invention is a method in which a metal is formed by plating on a conductive substrate having a pattern of convex portions having an upper surface and a concave portion having a geometric diagram shape drawn thereby. It is a manufacturing method of the base material with a conductor layer pattern characterized by including the process of forming a layer, and the process of transferring the metal layer formed in the upper surface of the convex part of the said conductive base material to another base material.
- Embodiment 2 of the present invention is a method for producing a base material with a conductor layer pattern according to Embodiment 1 in which a conductive base material having an inclination angle of a side surface of a convex portion having an upper surface of 30 ° or more is used. .
- the conductive substrate is arranged on the outside of the region A in which the area ratio of the recesses is 50% or more and 97% or less of the entire recess, and the area ratio of the recesses is the entire area ratio.
- Production of a substrate with a conductor layer pattern according to Embodiment 1 or 2, which has region B that is 0% or less than 97%, and the area ratio of the recesses in region A is larger than the area ratio of the recesses in region B Is the method.
- Embodiment 4 of the present invention is a method for manufacturing a substrate with a conductor layer pattern of Embodiment 3 in which the area ratio of the recesses in region B is 40% or more and less than 97% of the whole.
- the upper surface of the convex portion of region A and the upper surface of the convex portion of region B are continuous at least at one force point. It is a manufacturing method.
- Embodiment 6 of the present invention in the step of transferring the metal deposited on the upper surface of the convex portion of the conductive base material to another base material, the conductive material out of the metal precipitated on the conductive base material. It is a manufacturing method of the base material with any one conductor layer pattern of Embodiment 1-5 which selectively transcribe
- the surface roughness of the convex portion has a ten-point average roughness Rz of 2 or less.
- the conductive base material according to any one of the embodiments 1 to 6 is used. This is a method for manufacturing a substrate.
- Embodiment 8 of the present invention is a method for producing a substrate with a conductor layer pattern according to Embodiment 6 or 7, wherein a conductive substrate having a concave surface roughness of 3 or more in terms of 10-point average roughness Rz is used. It is.
- Embodiment 9 of the present invention is any one of Embodiments 1 to 8, wherein the conductive base material is such that a recess is covered with an insulating layer so as to be a thin film at least in the vicinity of the upper surface end of the protrusion. This is a method for producing a substrate with a conductor layer pattern.
- Embodiment 10 of the present invention is a method for manufacturing a substrate with a conductor layer pattern of Embodiment 9, wherein the thickness of the insulating layer is 1Z2 or less of the height of the convex portion.
- Embodiment 11 of the present invention is the method for producing a substrate with a conductor layer pattern according to Embodiment 9 or 10, wherein the conductive substrate has a recess coated with a thin film insulating layer.
- Embodiment 12 of the present invention is the production of a substrate with a conductor layer pattern according to Embodiment 11, wherein the thickness of the thin film insulating layer at the end of the upper surface of the convex portion of the conductive substrate is lO / zm or less. Is the method.
- Embodiment 13 of the present invention is a method for producing a substrate with a conductor layer pattern according to Embodiment 11 or 12, wherein the thin film insulating layer covering the recesses of the conductive substrate is formed by electrodeposition coating. is there.
- Embodiment 14 of the present invention further includes a step of blackening the surface of the metal deposited before or after transfer of the formed metal layer.
- the fifteenth embodiment of the present invention is performed after the manufacturing method of any one of the first to thirteenth embodiments is performed.
- Embodiment 16 of the present invention is the production of a substrate with a conductor layer pattern according to Embodiment 14 or 15, wherein the blackening treatment is performed by depositing a black alloy metal containing a Group VIII element on the surface of the formed metal layer. Is the method.
- Embodiment 17 of the present invention is such that the black wrinkle treatment is black nickel plating, nickel sulfate 60 to: LOOgZL, nickel sulfate ammonium 30 to 50g ZL, zinc sulfate 20 to 40g 17 is a process for producing a substrate with a conductor layer pattern according to Embodiment 16, using a plating solution containing ZL and sodium thiocyanide in an amount of 10 to 20 g ZL.
- Embodiment 18 of the present invention is a method for producing a substrate with a conductor layer pattern according to any one of Embodiments 14 to 17, wherein the thickness of the blackened layer is 0.5 ⁇ m to 3 ⁇ m It is.
- Embodiment 19 of the present invention is Embodiments 14 to 18 in which the blackened layer has no powder fallout in portions other than the conductive layer pattern that adheres well to the metal deposited on the conductive substrate.
- Embodiment 20 of the present invention is Embodiment 14 having an antifouling treatment step after the blackening treatment.
- Embodiment 21 of the present invention is any one of Embodiments 1 to 20, in which another substrate has adhesiveness.
- Embodiment 22 of the present invention is the method for producing a substrate with a conductor layer pattern of Embodiment 21, wherein another substrate has an adhesive layer or a pressure-sensitive adhesive layer on the surface.
- Embodiment 23 of the present invention any one of Embodiments 1 to 22, wherein the other substrate has an average transmittance of 900% or less in the near infrared region of LlOOnm of 15% or less 1
- This is a method for producing a substrate with two conductor layer patterns.
- the height of the convex pattern of the conductive substrate is: L m to 10
- Embodiment 1 in which 0 m, width is 1 ⁇ m to 40 ⁇ m, and the distance between the upper surfaces of the convex portions is 100 ⁇ m to 1000 ⁇ m. Manufacturing method of substrate with one conductor layer pattern It is.
- the metal thickness on the upper surface of the convex portion of the conductive substrate is 0.1-20 / A method for producing a substrate with a single conductor layer pattern according to any one of Embodiments 1 to 24, in which metal is deposited so as to be ⁇ ⁇ .
- Embodiment 26 of the present invention includes at least one metal having a volume resistivity of 20 ⁇ / cm or less at a metal force of 20 ° C used for plating. It is a manufacturing method of a base material with two conductor layer patterns.
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Manufacturing Of Electric Cables (AREA)
- Laminated Bodies (AREA)
Abstract
Description
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006549027A JPWO2006068175A1 (ja) | 2004-12-24 | 2005-12-21 | 導体層パターン付き基材の製造法、導体層パターン付き基材及びそれを用いた電磁波遮蔽部材 |
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004-373287 | 2004-12-24 | ||
| JP2004373287 | 2004-12-24 | ||
| JP2005131620 | 2005-04-28 | ||
| JP2005-131620 | 2005-04-28 | ||
| JP2005153860 | 2005-05-26 | ||
| JP2005-153860 | 2005-05-26 | ||
| JP2005279805 | 2005-09-27 | ||
| JP2005-279805 | 2005-09-27 | ||
| JP2005284084 | 2005-09-29 | ||
| JP2005-284084 | 2005-09-29 | ||
| JP2005290053 | 2005-10-03 | ||
| JP2005-290053 | 2005-10-03 |
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| WO2006068175A1 true WO2006068175A1 (ja) | 2006-06-29 |
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| PCT/JP2005/023483 Ceased WO2006068175A1 (ja) | 2004-12-24 | 2005-12-21 | 導体層パターン付き基材の製造法、導体層パターン付き基材及びそれを用いた電磁波遮蔽部材 |
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| Country | Link |
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| JP (1) | JPWO2006068175A1 (ja) |
| TW (1) | TW200641918A (ja) |
| WO (1) | WO2006068175A1 (ja) |
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| JP2009167523A (ja) * | 2007-12-18 | 2009-07-30 | Hitachi Chem Co Ltd | めっき用導電性基材、その製造方法及びそれを用いた導体層パターン若しくは導体層パターン付き基材の製造方法、導体層パターン付き基材および透光性電磁波遮蔽部材 |
| JP2009176761A (ja) * | 2006-12-27 | 2009-08-06 | Hitachi Chem Co Ltd | めっき用導電性基材、その製造方法及びそれを用いた導体層パターン付き基材の製造方法、導体層パターン付き基材、透光性電磁波遮蔽部材 |
| JP2010007095A (ja) * | 2008-06-24 | 2010-01-14 | Hitachi Chem Co Ltd | めっき方法 |
| JP2010007127A (ja) * | 2008-06-26 | 2010-01-14 | Hitachi Chem Co Ltd | めっき用導電性基材、その製造方法及びそれを用いた導体層パターン若しくは導体層パターン付き基材の製造方法。 |
| JP2010182640A (ja) * | 2009-02-09 | 2010-08-19 | Toda Kogyo Corp | 透明導電性基板、色素増感型太陽電池用透明導電性基板及び透明導電性基板の製造方法 |
| JP2012140793A (ja) * | 2010-12-28 | 2012-07-26 | Aquaintech Corp | 地下構造物用蓋体 |
| CN103313516A (zh) * | 2012-03-16 | 2013-09-18 | 张有谅 | 导电图样薄膜基材及制造方法 |
| US8673428B2 (en) | 2006-12-27 | 2014-03-18 | Hitachi Chemical Company, Ltd. | Engraved plate and substrate with conductor layer pattern using the same |
| JP2015045220A (ja) * | 2014-10-01 | 2015-03-12 | アクアインテック株式会社 | 地下構造物用蓋体 |
| CN107006137A (zh) * | 2014-09-03 | 2017-08-01 | 大陆配件公司 | 用于移动设备的rf屏蔽 |
| JP2019052354A (ja) * | 2017-09-15 | 2019-04-04 | トヨタ自動車株式会社 | インテークマニホールドの製造方法 |
| JP2020009705A (ja) * | 2018-07-12 | 2020-01-16 | 三菱製紙株式会社 | 導電性材料の製造方法 |
| JP2020015191A (ja) * | 2018-07-24 | 2020-01-30 | 三菱製紙株式会社 | 金属調パターン転写物の製造方法 |
| CN113809509A (zh) * | 2020-06-11 | 2021-12-17 | 华为技术有限公司 | 一种天线成型方法、盖板组件及终端设备 |
| JPWO2022158357A1 (ja) * | 2021-01-21 | 2022-07-28 | ||
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| TWI872836B (zh) * | 2023-11-30 | 2025-02-11 | 凱新全球科技股份有限公司 | 保護膠及製造無縫顯示單元的方法 |
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| KR20170036820A (ko) * | 2012-07-24 | 2017-04-03 | 미쯔비시 레이온 가부시끼가이샤 | 도전체, 도전성 조성물, 및 적층체 |
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| JP2974665B1 (ja) * | 1998-08-28 | 1999-11-10 | 日本写真印刷株式会社 | 透光性電磁波シールド材とその製造方法 |
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| JP2009176761A (ja) * | 2006-12-27 | 2009-08-06 | Hitachi Chem Co Ltd | めっき用導電性基材、その製造方法及びそれを用いた導体層パターン付き基材の製造方法、導体層パターン付き基材、透光性電磁波遮蔽部材 |
| JP2013239722A (ja) * | 2006-12-27 | 2013-11-28 | Hitachi Chemical Co Ltd | めっき用導電性基材、その製造方法及びそれを用いた導体層パターン付き基材の製造方法、導体層パターン付き基材、透光性電磁波遮蔽部材 |
| US8673428B2 (en) | 2006-12-27 | 2014-03-18 | Hitachi Chemical Company, Ltd. | Engraved plate and substrate with conductor layer pattern using the same |
| JP2009167523A (ja) * | 2007-12-18 | 2009-07-30 | Hitachi Chem Co Ltd | めっき用導電性基材、その製造方法及びそれを用いた導体層パターン若しくは導体層パターン付き基材の製造方法、導体層パターン付き基材および透光性電磁波遮蔽部材 |
| JP2010007095A (ja) * | 2008-06-24 | 2010-01-14 | Hitachi Chem Co Ltd | めっき方法 |
| JP2010007127A (ja) * | 2008-06-26 | 2010-01-14 | Hitachi Chem Co Ltd | めっき用導電性基材、その製造方法及びそれを用いた導体層パターン若しくは導体層パターン付き基材の製造方法。 |
| JP2010182640A (ja) * | 2009-02-09 | 2010-08-19 | Toda Kogyo Corp | 透明導電性基板、色素増感型太陽電池用透明導電性基板及び透明導電性基板の製造方法 |
| JP2012140793A (ja) * | 2010-12-28 | 2012-07-26 | Aquaintech Corp | 地下構造物用蓋体 |
| CN103313516A (zh) * | 2012-03-16 | 2013-09-18 | 张有谅 | 导电图样薄膜基材及制造方法 |
| JP2017531325A (ja) * | 2014-09-03 | 2017-10-19 | コンチネンタル・アクセサリー・コーポレーション | モバイルデバイスのためのrf遮蔽 |
| KR102248202B1 (ko) * | 2014-09-03 | 2021-05-04 | 콘티넨탈 액세서리 코퍼레이션 | 모바일 디바이스들을 위한 rf 차폐 |
| KR20170093103A (ko) * | 2014-09-03 | 2017-08-14 | 콘티넨탈 액세서리 코퍼레이션 | 모바일 디바이스들을 위한 rf 차폐 |
| CN107006137A (zh) * | 2014-09-03 | 2017-08-01 | 大陆配件公司 | 用于移动设备的rf屏蔽 |
| JP2015045220A (ja) * | 2014-10-01 | 2015-03-12 | アクアインテック株式会社 | 地下構造物用蓋体 |
| JP2019052354A (ja) * | 2017-09-15 | 2019-04-04 | トヨタ自動車株式会社 | インテークマニホールドの製造方法 |
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| JPWO2006068175A1 (ja) | 2008-06-12 |
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