JP5079369B2 - Frequency selective shielding type electromagnetic shielding laminate - Google Patents

Description

  The present invention relates to a frequency selective shielding type electromagnetic wave shield laminate that selectively shields only electromagnetic waves in a predetermined frequency band and transmits electromagnetic waves of other frequencies. More specifically, it can be attached to a building window or used for a transparent partition in a room in order to prevent electromagnetic waves from entering the outdoors or prevent indoor electromagnetic waves from leaking. In addition, the present invention relates to a frequency selective shielding type electromagnetic wave shield laminate that can be thinned and has a wide-band resonance frequency.

In recent years, electromagnetic waves generated from various electronic devices have adversely affected the human body, and malfunctions of surrounding electronic devices have become a problem. Furthermore, with the spread of wireless LAN, communication data has moved outside buildings. There is a need to prevent leakage and interception.
For this reason, the countermeasure of the frequency selective shielding type electromagnetic wave shield which selectively shields only the electromagnetic wave of a predetermined frequency and permeate | transmits the electromagnetic wave of other frequencies is increasingly regarded as important.

Specifically, in order to prevent unnecessarily leaking communication data by wireless LAN for business use outside the building, or in the case of a complex building where multiple companies are mixed, outside the partition wall. It is necessary to shield the transmission of radio waves from wireless LANs using frequencies in the 2.4 GHz band and the 5.2 GHz band.
In addition, radio waves for mobile phone (0.8 GHz band, 1.5 GHz band, 2.0 GHz band) and digital terrestrial television broadcasting (470-770 MHz) used for business communication with outside are for business communication or It is important for obtaining information in an emergency and needs to be transmitted without being shielded.
Therefore, there is a need for a frequency selective shielding type electromagnetic shielding material having a function of selectively shielding only electromagnetic waves in a predetermined frequency band and transmitting electromagnetic waves of other frequencies.

  Conventionally, a frequency selective shielding type electromagnetic shielding material and an electromagnetic shielding laminate that selectively shields only electromagnetic waves of a predetermined frequency intended to be shielded and transmits electromagnetic waves of other frequencies are made of a conductor. A device in which FSS elements (FSS: Frequency Selective Surface) are repeatedly arranged is known (see Patent Documents 1 to 7).

The following configuration is known as a method of using a frequency-selective electromagnetic wave shielding (shield) material using an FSS element and an electromagnetic wave shielding (shield) laminate.
(1) A transparent base material having an FSS element formed on the surface is pasted on one side of a window glass or the like (Patent Documents 1, 2, 3, 6).
(2) A plurality of base material layers on the surface of which FSS elements are formed are provided at regular intervals (Patent Documents 4 and 5).
(3) A resistor layer is provided as an electromagnetic wave absorbing layer on one surface of the dielectric, and an FSS element is formed as a reflective layer on the other surface (Patent Document 7).

In the prior art, the frequency selective shielding with the single FSS element of (1) above is a basic and simple configuration, but from the characteristic of having a sharp resonant frequency only for a specific frequency, trial and error. However, it was necessary to adjust the figure shape and dimensions of the fine line pattern.
In addition, the configuration in which the base material layer on which the FSS element of (2) is formed is provided at a predetermined interval to provide a plurality of numbers has an effect that the shielding level is higher than that using one FSS element, It was not intended to reduce the thickness of the electromagnetic shielding body (for example, Patent Document 4).

  Further, in the case where a resistor layer is provided as an electromagnetic wave absorbing layer on one side of the dielectric material of the above (3) and an FSS element is formed as a reflective layer on the other surface, the thickness of the dielectric is ¼ of the wavelength λ (here The wavelength λ represents a wavelength at a frequency intended to be shielded in the dielectric. This is a so-called λ / 4 type shield. The surface reflected wave reflected on the surface of the resistor layer and the internal reflected wave reflected by the FSS element with only the electromagnetic wave having a specific frequency are absorbed by the opposite phase and the same amplitude. For this reason, in order to selectively shield against a specific frequency, it is necessary to adjust the dielectric constant and thickness of the dielectric, but when applied to existing window glass, the dielectric of the specified window glass is required. The thickness of the window glass was changed according to the rate, and it was difficult to put it into practical use for general purposes.

On the other hand, the following three types of FSS element manufacturing methods are known.
(A) An etching method in which a metal foil is bonded to one side of a transparent substrate, or a metal thin film is deposited on the transparent substrate, and then a pattern of an FSS element is formed by a photolithographic method (Patent Documents 1, 3, and 5).
(B) A printing method in which a metal paste is printed on a transparent substrate to form an FSS element pattern (Patent Documents 4 and 6).
(C) A metal wire method in which a pattern of an FSS element is formed on a transparent substrate with a metal wire or a metal piece (Patent Document 2).

  In the method of manufacturing the fine line pattern of the FSS element, the etching method (a) leaves only a small part that becomes a fine line part by etching, and it is a resource to dissolve and remove most of the other most of the metal. It is a problem from the viewpoint of saving. Furthermore, there is a problem that the manufacturing cost increases because the cost for the waste liquid treatment of the etching treatment liquid increases. In addition, when a metal thin film is deposited, there is a problem that it cannot be easily manufactured because a huge equipment cost is required.

  In addition, in the method for producing a fine line pattern of an FSS element by the printing method (b), the line width of the fine line pattern is 100 μm or more (Patent Document 2) or 0.1 to 1.2 mm (Patent Document 5). Therefore, there is a problem that the figure of the fine line pattern is visible and gives a psychological discomfort to the viewer.

In addition, the metal wire method (c) has a problem that it is technically difficult to efficiently arrange extremely thin metal wires that cannot be visually observed in a thin wire pattern.
US Pat. No. 4,656,487 Japanese Patent Laid-Open No. 08-330783 Japanese Patent Laid-Open No. 10-1206090 Japanese Patent Laid-Open No. 11-068374 Japanese Patent Laid-Open No. 11-195890 JP 2000-068675 A JP 2000-323920 A

  An electromagnetic wave shield laminate in which a transparent base material having an FSS element formed on the surface of (1) is bonded to one side of a window glass or the like, and a base material having an FSS element formed on the surface of (2) In an electromagnetic wave shield laminated body in which a plurality of layers are separated at regular intervals, the half-value width of the shielding level with respect to the set value of the resonance frequency is usually narrow, resulting in a sharp peak of the resonance frequency and a very narrow tolerance. It has become. Therefore, there is a problem that the shielding effect is remarkably deteriorated even if it slightly deviates from the set value of the resonance frequency.

Further, as a conventional technique, it is known that a plurality of base layers having FSS elements formed on the surface as described in (2) above are provided at a constant interval, but the thickness is reduced as in the present invention. In order to obtain a frequency selective shielding type electromagnetic shielding material having a wide-band resonance frequency, the thickness is approximately λ / 60 to λ / 8 (where λ is a predetermined frequency for shielding electromagnetic waves in the intermediate base material layer). The transparent base material made of a dielectric is laminated on both end surfaces of the intermediate base material layer made of a transparent solid dielectric via an adhesive layer, and is arranged on one surface of the transparent base material. There is no known one in which the base material layers are arranged at regular intervals so that the fine line patterns of the provided FSS elements substantially overlap.

  For example, Patent Document 4 discloses a frequency-selective structure in which a base material layer having an FSS element formed on a surface is interposed with a substance having a predetermined dielectric constant (specifically, an air layer), and a plurality of numbers are provided at a predetermined interval. An electromagnetic wave shielding body, in which a base material layer having FSS elements formed on a surface thereof is arranged at a constant interval that is an odd multiple of approximately λ / 4, where λ is the wavelength of the electromagnetic wave to be electromagnetically shielded. Further, in the second and third embodiments of Patent Document 4, a sheet in which an FSS element is arranged on a winding roll is attached, and the stopping position of the winding roll is arbitrary, so that the patent Document 4 is not intended to overlap the patterns of the FSS elements on a sheet in which two FSS elements are arranged at a predetermined interval.

  Further, in Patent Document 5, a method for producing a fine line pattern of an FSS element by etching is used, and a plurality of regularly arranged on a plurality of planes parallel to each other so as not to overlap when viewed from a direction perpendicular to the plane. A frequency-selective electromagnetic wave shield laminate using an FSS element pattern is disclosed. In the case of three-dimensional arrangement, there is a description that a part of the FSS element pattern may overlap when viewed from the direction perpendicular to the plane, but basically, adjacent FSS element patterns do not overlap. It is arranged.

Also, the figure shape, line width, and dimensions of the fine line pattern of the FSS element that affects the resonance frequency (in the case of an open figure, the figure length is ½ of the wavelength λ, and in the case of an annular figure, Since the peripheral length is set equal to the wavelength λ) and the pattern interval is set by trial and error, a lot of complicated work is required until the figure shape and arrangement of the fine line pattern are finally determined.
In particular, in order to be able to shield against a plurality of resonance frequencies, it is necessary to arrange a plurality of types of FSS elements, and there is a problem that adjustment of the graphic arrangement of each FSS element becomes complicated.

  In Patent Document 6, as described in paragraph 0019, the line width of the conductive bipolar element (FSS element) is generally 0.1 to 10 mm, preferably 0.1 to 5 mm, more preferably. It is said that it is 0.1-1 mm. It is described that when the line width is less than 0.1 mm, the shielding power becomes weak, and when it exceeds 10 mm, there is no problem in shielding properties, but transparency is a problem. It was difficult to improve the visibility to 1 mm (100 μm) or less.

  Moreover, in the manufacturing method of the fine line pattern of the FSS element by the printing method of the above (b), the line width of the fine line pattern is set to 100 μm or more (Patent Document 2) or 0.1 to 1.2 mm (Patent Document 5). Therefore, there is a problem that the figure of the fine line pattern is visible and gives a psychological discomfort to the viewer.

  In order to solve the above problems, in the electromagnetic wave shield laminate of the frequency selective shield type, even if some tolerances are included in the shape dimensions of the FSS element pattern, the arrangement interval, the thickness of the dielectric, etc. An electromagnetic wave shielding effect at a predetermined resonance frequency can be obtained, and the visibility is excellent so as not to give psychological discomfort to the viewer, and the thickness can be reduced and the resonance frequency is wide. There has been a need for an electromagnetic shielding laminate.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the frequency selective shielding type electromagnetic wave shield laminated body which is excellent in visibility, can make thickness thin, and has a broadband resonance frequency.

To solve the above problems, the present invention provides an electromagnetic wave shielding laminate of the frequency selective shielded to shield electromagnetic waves of a predetermined frequency band, has a see-through property, different two or more layers of transparent dielectric constant A transparent substrate of a resin film made of a dielectric is laminated on both end faces of an intermediate substrate layer made of a solid dielectric via an adhesive layer, and one surface of the transparent substrate is for electromagnetic wave shielding, respectively. A thin line pattern made of FSS elements is provided , and the thickness of the intermediate base layer is approximately λ / 60 to λ / 8 adjusted using a laminate of resin sheets (where λ is the intermediate base layer) 2 represents a wavelength at a predetermined frequency at which the electromagnetic wave is to be shielded), and the two thin line patterns arranged on both sides of the intermediate base layer are metal layers composed of developed silver layers generated by a photographic method. And one side of the transparent substrate As viewed from a direction perpendicular against the arrangement interval of the two fine line patterns Ri is Na is disposed substantially overlapping position, the line width of the fine line pattern composed of the metal layer is 15～80Myuemu, and a thickness 0 providing an electromagnetic wave shielding laminate according to claim .05~15μm der Rukoto.

The present invention also provides an electromagnetic wave shielding laminate of the frequency selective shielded to shield electromagnetic waves of a predetermined frequency band, has a see-through property, two or more layers of transparent solid dielectrics having different dielectric constants A transparent base material of a resin film made of a dielectric is laminated on both end faces of the intermediate base material layer via an adhesive layer, and a thin wire made of an FSS element for shielding electromagnetic waves is formed on one surface of the transparent base material. The intermediate base material layer has a thickness of about λ / 60 to λ / 8, which is adjusted by using a laminate of resin sheets (where λ is to shield electromagnetic waves in the intermediate base material layer) The two fine line patterns arranged on both sides of the intermediate base material layer are metal layers generated by printing a conductive paste containing a black pigment. And one of the transparent substrates When viewed from a direction perpendicular to the plane, the arrangement interval of the two fine line patterns Ri is Na is disposed substantially overlapping position, the line width of the fine line pattern composed of the metal layer is 15～80Myuemu, and thickness There is provided an electromagnetic wave shielding laminate according to claim 0.05~15μm der Rukoto.

  In the electromagnetic wave shield laminate of the present invention, when the figure shape of the fine line pattern of the FSS element is an open figure, the length between both ends of the figure is ½ of the wavelength λ. It is preferable to make the entire circumference of the figure equal to the wavelength λ.

  Further, at least one surface of the transparent base material is a logo mark and / or alignment mark of a specific trade name, trademark, model number, etc., and two fine lines arranged on both sides of the intermediate base material layer One or more types selected from the group of figures, characters, symbols, codes, etc. that can be used to adjust the overlapping positions of patterns are arranged at regular intervals in the vertical and horizontal directions depending on the size that can be seen. It is preferable to be made.

  In addition, it is preferable that the fine line pattern is formed by arranging FSS elements having one or more types of shapes so as to be shielded against one or more resonance frequencies.

  According to the electromagnetic wave shielding laminate of the frequency selective shielding type of the present invention, the both side surfaces of the intermediate base material layer made of a transparent solid dielectric are formed on both side surfaces as viewed from the direction perpendicular to the plane of the intermediate base material layer. Since the fine line patterns made of FSS are arranged so that the intervals are substantially overlapped, the half-value width of the shielding level is wide and the peak becomes dull compared to the case where the FSS elements are arranged only on one side. That is, since it has a broadband resonance frequency, the range of allowable error of the line width and pattern dimension of the FSS element pattern that affects the resonance frequency is widened, and it becomes easy to determine the pattern shape and the arrangement interval.

  Further, according to the present invention, since the resonance frequency is widened, an intermediate base made of a transparent solid dielectric so that the frequency to be shielded comes to the upper limit side of the allowable resonance frequency band. The thickness of the material layer, and hence the electromagnetic wave shield laminate, can be adjusted to be thin. That is, a thin electromagnetic wave shield laminate can be obtained.

Moreover, according to the electromagnetic wave shield laminate of the frequency selective shielding type of the present invention, the line width of the metal layer of the fine line pattern is 15 to 80 μm and the thickness is 0.05 to 15 μm. And can prevent psychological discomfort for the viewer.
In particular, when a developed silver layer formed by a photographic method is used for a fine line pattern made of a conductive metal of an FSS element, the fine line width can be reduced to 30 μm or less, and has better visibility (not visible). It can be set as an electromagnetic wave shield laminated body.

  The present invention will be described below with reference to the drawings based on the best mode.

FIG. 1 is a schematic enlarged sectional view showing a reference example of a frequency selective shielding electromagnetic wave laminate, and FIG. 2 is a schematic enlarged sectional view showing an example of a frequency selective shielding electromagnetic shield laminate of the present invention. It is a drawing. FIG. 1 shows that transparent substrates 5 and 6 in which fine line patterns 3, 3 and 4 and 4 made of FSS elements are formed on both end faces of a transparent intermediate substrate layer 2 made of a single layer are adhesive layers 7 and 8. It is a schematic sectional drawing of the electromagnetic wave shield laminated body 1 laminated | stacked through.

  FIG. 2 shows a transparent base material 15, 16 in which fine line patterns 13, 13 and 14, 14 made of FSS elements are formed on both end surfaces of a transparent intermediate base material layer 11, 12 consisting of two layers, and an adhesive layer 17, 1 is a schematic cross-sectional view of an electromagnetic wave shield laminate 10 laminated via 18. The intermediate base material layers 11 and 12 are laminated via the pressure-sensitive adhesive layer 19.

FIGS. 3A and 3B are conceptual diagrams showing a difference in bandwidth at the resonance frequency P between the prior art and the present invention.
4A to 4K are partially enlarged front views showing examples of the shape of the fine line pattern of the FSS element pattern.

FIG. 3 is a diagram conceptually showing the effect of the present invention, and FIG. 3 (a) is a diagram showing the shielding level α at the resonance frequency P when a thin line pattern made of one FSS element according to the prior art is used. The bandwidth w ₁ of the allowable frequency is shown. FIG. 3B shows the bandwidth w ₂ of the allowable frequency at the shielding level α at the resonance frequency P when using a thin line pattern composed of two FSS elements that overlap with each other at a constant interval according to the present invention. .
Figure 3 (a) and Comparing FIG. 3 (b), compared with the allowed bandwidth w ₁ of the prior art by blocking level alpha, towards the bandwidth w ₂ of the allowable frequency of a shielding level alpha according to the present invention Is broadband. Therefore, according to the electromagnetic wave shield laminate according to the present invention, a constant shielding level α can be maintained even if the maximum resonance frequency in the produced electromagnetic wave shield laminate is slightly deviated from the target resonance frequency.

In a conventional frequency selective shielding type electromagnetic wave shield laminate, the half-value width of the shielding level with respect to the set value of the resonance frequency is usually narrow, and as a result, the resonance frequency has a sharp peak and the tolerance is very narrow. Therefore, there is a problem that the shielding effect is remarkably deteriorated even if it slightly deviates from the set value of the resonance frequency.
In particular, when a plurality of types of FSS elements are arranged so as to be shielded against a plurality of resonance frequencies, there is a problem that adjustment of the graphic arrangement of each FSS element becomes complicated.
However, by using the present invention, it is possible to further simplify the adjustment of the graphic arrangement of the shielding FSS elements for a plurality of frequencies.

The frequency selective shielding type electromagnetic wave shielding laminate 1 shown in FIG. 1 has fine line patterns 3, 3 and 4, 4 made of FSS elements on both end faces of an intermediate base material layer 2 made of a single layer of transparent solid dielectric. The formed transparent base materials 5 and 6 are laminated via the pressure-sensitive adhesive layers 7 and 8, and shield electromagnetic waves having a predetermined frequency.
In FIG. 1, assuming that electromagnetic waves are incident from the left direction, electromagnetic waves of other frequencies that are not shielded by the thin line patterns 3 and 3 are transmitted in the right direction. Further, a part of the electromagnetic wave having a predetermined frequency that is transmitted without being shielded by the fine line patterns 3 and 3 is again shielded by the fine line patterns 4 and 4 provided on the other surface of the transparent substrate 6.
The thin line patterns 3, 3 and 4, 4 are thin line patterns made of a conductive metal layer. The two thin line patterns 3 are viewed from a direction perpendicular to one surface of the transparent substrates 5, 6. , 3 and 4 and 4 are arranged at positions where the arrangement intervals substantially overlap.

As a method of concretely using the frequency selective shielding type electromagnetic wave shielding laminate 1 shown in FIG. 1, a thin line pattern made of FSS elements is formed on both end faces of an intermediate base material layer 2 made of one transparent solid dielectric. A pressure-sensitive adhesive layer is provided on one surface of a frequency selective shielding type electromagnetic wave shield laminate 1 in which transparent base materials 5 and 6 on which 3, 3 and 4 and 4 are formed are laminated via pressure-sensitive adhesive layers 7 and 8, respectively. It may be attached to the window glass of a building.
Further, in the indoor transparent partition, fine line patterns 3, 3 and 4 and 4 made of FSS elements are formed on both end faces of the intermediate base material layer 2 made of a single layer of transparent solid dielectric that becomes a partition member. Further, the transparent base materials 5 and 6 may be laminated via the pressure-sensitive adhesive layers 7 and 8 to form the frequency selective shielding type electromagnetic wave shielding laminate 1 of the present invention.

  In addition, a logo mark and / or an alignment mark such as a specific trade name, trademark, or model number is provided on the surface on which the thin line patterns 3, 3 and 4, 4 made of the FSS element of the transparent substrate are not disposed. One or more selected from the group of figures, characters, symbols, codes, etc., which can be used to adjust the overlapping position of the two thin line patterns, are fixed in the vertical and horizontal directions depending on the size that can be seen Therefore, it becomes easy to adjust and arrange the two thin line patterns at positions where the arrangement intervals substantially overlap.

  Graphics, characters, symbols, symbols, and other graphics that can be used to adjust the overlapping position of two thin line patterns can be printed with ink and paint using known printing methods, inkjet printers, laser printers, etc. It may be used and imprinted. Moreover, you may affix the small piece which printed such a figure on the surface of the transparent resin film using an adhesive in the vertical and horizontal directions of the single side | surface of the transparent base materials 5 and 6, respectively with a fixed space | interval.

  Compared to the case where electromagnetic waves of a predetermined frequency are shielded by only one thin line pattern 3, 3 formed on the transparent substrate 5, the two thin line patterns 3, 3, 4, 4 separate the thickness of the intermediate substrate layer. If the electromagnetic waves having a predetermined frequency are shielded by being arranged so as to substantially overlap each other, the half-value width of the shielding level is wider than the set value of the resonance frequency, and the peak becomes dull. That is, since it has a wideband resonance frequency, the tolerance range of the line width and pattern dimension of the FSS element pattern that affects the resonance frequency is widened, so that the pattern shape and the arrangement interval can be easily determined.

A frequency selective shielding type electromagnetic wave shielding laminate 10 shown in FIG. 2 is a transparent material comprising intermediate base material layers 11 and 12 made of two transparent solid dielectric materials having different dielectric constants laminated via an adhesive layer 19. Transparent base materials 15 and 16 on which fine line patterns 13 and 13 made of FSS elements and fine line patterns 14 and 14 are formed are laminated on both end faces of the intermediate base material layer with adhesive layers 17 and 18 interposed therebetween.
As a method of concretely utilizing this embodiment, for example, the transparent intermediate base material layer 12 is a window glass, and the dielectric constant is different from that of the window glass for adjusting the thickness on one side of the window glass. A transparent base material 15 in which a transparent intermediate base material layer 11 is laminated via an adhesive layer 19, and fine line patterns 13, 13 and 14, 14 of two FSS elements are formed on both end faces of these intermediate base material layers. And 16 are laminated via the pressure-sensitive adhesive layers 17 and 18, and the electromagnetic wave shielding laminate 10 of a frequency selective shielding type can be formed.

  1 and 2 show a case where a pressure-sensitive adhesive layer is provided on the surface side on which the metal layer of the transparent base material is formed and laminated on the intermediate base material layer. You may provide an adhesive layer in the surface side in which the layer is not formed, and you may laminate | stack on an intermediate | middle base material layer.

  The fine line patterns 3, 4, 13, and 14 of the FSS element shown in FIG. 1 and FIG. 2 are produced from a developed silver layer produced by printing a conductive paste on the surface of a transparent substrate or by a photographic process. It can be formed using the method of generation.

(Transparent substrate)
The transparent substrates 5, 6, 15, and 16 made of a dielectric material used in the present invention are preferably transparent in the visible region and generally have a total light transmittance of 90% or more. Specifically, transparent glass, a resin sheet, a resin film, or the like can be used. Especially, the resin film which has flexibility is preferable as a material of a transparent base material, since it is excellent in handleability. Specific examples of resin films used for transparent substrates include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins, epoxy resins, fluororesins, silicone resins, polycarbonate resins, and diacetate resins. , Triacetate resin, polyarylate resin, polyvinyl chloride, polysulfone resin, polyether sulfone resin, polyimide resin, polyamide resin, polyolefin resin, cyclic polyolefin resin, etc. A multi-layer composite film may be mentioned.

(Transparent intermediate base material layer)
The intermediate base layers 2, 11, and 12 made of a transparent solid dielectric are inserted to maintain the distance between the two fine line patterns laminated on both sides of the intermediate base layer, and are shown above. The material used for the transparent substrate can be selected and used. Among them, it is preferable to use a transparent glass, a single layer or a laminate of a resin sheet, and to have a required thickness.

(FSS element)
On one surface of the transparent base materials 5, 6 and 15, 16, fine line patterns 3, 4, 13 and 14 made of electromagnetic wave shielding FSS elements for shielding electromagnetic waves of a predetermined frequency are regularly arranged at regular intervals. It is arranged.
In general, a fine line pattern composed of an FSS element for shielding electromagnetic waves of a predetermined frequency resonates with electromagnetic waves of a predetermined frequency and consumes part of the energy as heat to attenuate the electromagnetic waves of the resonance frequency. The part is re-emitted to the incident side of the electromagnetic wave and the opposite side, and apparently reflects from the thin line pattern, and a slight part is transmitted.
In FIG. 1 and FIG. 2, if electromagnetic waves are incident from the left direction, the fine line patterns 3, 3 and 13, 13 composed of FSS elements for shielding electromagnetic waves basically shield electromagnetic waves having a resonating frequency. Thus, electromagnetic waves other than the resonance frequency are transmitted in the right direction without being shielded.

On the transparent substrates 6 and 16, fine line patterns 4, 4, 14, and 14 for shielding electromagnetic waves having a predetermined frequency are regularly arranged at regular intervals. Similar to the fine line patterns 3 and 3, the fine line patterns 4 and 4 are elements that resonate with an electromagnetic wave having a predetermined frequency and consume part of the energy as heat, and attenuate the electromagnetic wave with the resonant frequency. A part of the electromagnetic wave is re-emitted to the incident side of the electromagnetic wave and the opposite side, and apparently reflects the fine line patterns 4 and 4, and a slight part is transmitted.
The thin line patterns 4, 4 and 14, 14 basically shield electromagnetic waves having a resonating frequency, and electromagnetic waves other than the resonant frequency are transmitted without being shielded.

  As in the present invention, a transparent base material made of a transparent dielectric is laminated on both surfaces of an intermediate base material layer made of a transparent solid dielectric via an adhesive layer, and is arranged on one surface of the transparent base material. When the base material layers are arranged at regular intervals so that the fine line patterns of the provided FSS elements substantially overlap, the shielding effect of electromagnetic waves is enhanced. Furthermore, although the reason is not clear, a phenomenon that the resonance frequency is widened was observed.

  By utilizing this phenomenon, it is possible to obtain an electromagnetic wave shielding effect at a predetermined resonance frequency even if a certain tolerance is included in the geometric dimensions, arrangement interval, dielectric thickness, etc. of the FSS element pattern.

More specifically, for example, in the case of a transparent partition in which the intermediate base material layer is made of a single layer of a transparent solid dielectric and the electromagnetic wave shield laminate is installed indoors, a synthetic solid dielectric is used. The transparent base film in which the fine line pattern of the FSS element is formed on both surfaces of the resin plate can be bonded and laminated using an adhesive.
In this case, the wavelength λ at the frequency of the electromagnetic wave intended to be shielded in the intermediate base material layer is determined from the intrinsic dielectric constant of the synthetic resin plate as the dielectric in the air as calculated by the following formula (1). It is known that the wavelength is shortened compared to

  λ = λ (a) / √ε (1)

  Here, λ is the wavelength [mm] in the dielectric (intermediate base material layer), λ (a) is the wavelength in air [mm], and ε is the relative dielectric constant [−] of the dielectric. is there.

For this reason, as the intermediate base material layer has a higher relative dielectric constant, the wavelength λ at the frequency of the electromagnetic wave intended to be shielded in the intermediate base material layer becomes shorter, and as a result, the thickness of the intermediate base material layer can be reduced. For example, when a general acrylic resin is used as a dielectric material as a transparent synthetic resin, the relative dielectric constant of the acrylic resin is 4.0. Therefore, the wavelength λ of the intermediate base material layer is the wavelength λ ( It becomes 1/2 of a).
That is, when an acrylic resin is used as the intermediate base material layer made of a solid dielectric, the thickness of the intermediate base material layer is generally set to 1 as compared with the case where the wiring pattern of the FSS element is isolated via the air layer. / 2 can be made thinner.

In addition, according to the present invention, the thickness of the intermediate base material layer made of a transparent solid dielectric can be adjusted so that the frequency to be shielded comes to the upper limit side of the allowable resonance frequency band. That is, in the present invention, in addition to the reduction of the thickness due to the effect of the relative dielectric constant of the intermediate base material layer, further utilizing the fact that the resonance frequency is widened, the intermediate base material layer made of a solid dielectric is used. The thickness can be reduced, and as a result, the thickness of the electromagnetic wave shield laminate can be reduced.
In the present invention, the thickness of the intermediate base material layer made of a solid dielectric is approximately λ / 60 to λ / 8 (where λ represents a wavelength at a predetermined frequency for shielding electromagnetic waves in the intermediate base material layer). It can be. If the thickness of the intermediate base material layer is less than about λ / 60, the effect of widening the resonance frequency is small, and if it is thicker than about λ / 5, the weight becomes heavy, resulting in inconvenience in handling during installation work. There is an inconvenience.

  In addition, as the graphic size of the FSS element pattern, when the wavelength at the frequency to be selectively shielded in the intermediate base material layer made of a solid dielectric is λ, the figure shape of the fine line pattern of the FSS element is an open figure. The length between both ends of the figure is ½ of the wavelength λ, and in the case of an annular figure, the entire circumference of the figure is made equal to the wavelength λ.

  By the way, in the case of the electromagnetic wave shielding laminate of the frequency selective shielding type of the present invention, a fine line pattern made of an FSS element is used from the viewpoint of transparency. The shape, size, arrangement interval, and the like of the FSS elements used for the fine line pattern are set to optimum values according to the frequency to be shielded.

Further, the fine line patterns 3, 3, and 4, 4 shown in FIG. 1, and the fine line patterns 13, 13, 14, and 14 shown in FIG. 2 are fine line patterns made of a conductive metal layer, When viewed from a direction perpendicular to one surface of 6, 15, 16, the two thin line patterns 3, 3, 4, 4, 13, 13, 14, 14 are arranged at positions where the arrangement intervals substantially overlap. Has been.
Compared to the case where electromagnetic waves of a predetermined frequency are shielded only by the fine line patterns 3, 3 and 13, 13, two fine line patterns 4, 4 and 14, 14 are arranged opposite to the position substantially overlapping with the fine line pattern. The arrangement is such that the half-value width of the shielding level is wider than the set value of the resonance frequency and the peak becomes dull, that is, since it has a broadband resonance frequency, the line width and pattern dimension of the FSS element pattern that affect the resonance frequency. Since the allowable error range becomes wider, the pattern shape and the arrangement interval can be easily determined.

  In the frequency selective shielding type electromagnetic wave shielding laminate of the present invention, the metal layer of the fine line pattern comprising the FSS element is a metal layer produced by printing a conductive paste, a metal produced from a developed silver layer produced by a photographic process. It is preferably any of the layers.

  In particular, when performing high-level electromagnetic shielding, in order to further increase the conductivity of the fine line pattern made of the metal layer of the FSS element, a developed silver layer of the fine line pattern made of the target FSS element is produced by a photographic method, and It is preferable to carry out by a method of forming a metal plating layer on this developed silver layer.

For the electromagnetic wave shield laminate of the frequency selective shielding type of the present invention, a fine line pattern of an FSS element pattern having a shape example as shown in FIG. 4 is used.
The shape of the electromagnetic wave shielding laminate according to the present invention is not particularly limited, but has transparency, on both end surfaces of an intermediate base material layer made of one or more transparent solid dielectrics having different dielectric constants, A transparent base material made of a dielectric is laminated via an adhesive layer, and a thin line pattern made of an FSS element for shielding electromagnetic waves is disposed on one surface of the transparent base material, and the intermediate base material The thickness of the layer is approximately λ / 60 to λ / 8 (where λ represents the wavelength at a predetermined frequency at which the electromagnetic wave in the intermediate base material layer is to be shielded), and is disposed on both sides of the intermediate base material layer. two thin lines pattern is a metal layer, as viewed from a direction perpendicular to the one surface of the transparent substrate, the intended arrangement interval of the two fine line patterns, which are disposed substantially overlapping position is there.

The line width of the fine line pattern made of the metal layer forming the FSS element is preferably 15 to 80 μm, and more preferably 15 to 50 μm. When the line width is set to a fine line of 15 μm or less, an original for screen printing for forming a fine line pattern of a metal layer by printing using a conductive paste, or for forming a fine line pattern of a metal layer by a photographic method This is not preferable because the manufacturing cost of the exposure mask is significantly increased. On the contrary, if the line width is increased to 80 μm or more, the conductivity is increased, but the transparency is lowered, which is not preferable.
Moreover, although the thickness of the thin line pattern of a metal layer can be changed arbitrarily according to the desired characteristic, Preferably it is the range of 0.05-15 micrometers, More preferably, it is the range of 0.05-10 micrometers. If the thickness of the fine line pattern of the metal layer is thin, the electromagnetic shielding performance is too low, and if the thickness of the fine line pattern is thick, the cost increases.

  Among the FSS elements shown in FIG. 4, a more preferable shape is an open figure formed by a combination of line segments having ends as shown in FIGS. 4B and 4C, and FIGS. 4F and 4G. A closed figure (circular figure) having no end as shown in FIG. 4B, and in addition, a combination of an open figure and a closed figure as shown in FIG. 4D, as shown in FIG. There are two types of closed graphic combinations. The dimension of the FSS element is about ¼ of the wavelength of the electromagnetic wave to be shielded by the length from the center of the line segment in the case of an open figure composed of a combination of line segments having ends. Further, in the case of a closed figure (annular figure) that does not have an end, the length of the periphery is set to be the same as the wavelength of the electromagnetic wave to be shielded.

The FSS element shown in FIG. 4A is a set of four squares (square loop type) whose outline is formed by fine lines of a metal layer.
The FSS element shown in FIG. 4B has an inverted Y-shape (tripol type) formed by a thin metal layer. According to the element of this shape, each of the three sides functions as a dipole antenna, and an electromagnetic wave shield can be provided against any inclination of radio waves.
The FSS element shown in FIG. 4C has a cross shape (cross dipole type) formed of thin metal layers. Thereby, an electromagnetic wave shield can be provided in both the horizontal direction and the vertical direction.
The FSS element shown in FIG. 4 (d) is formed by forming a triangular outline and a Y-shape inside the thin-line metal layer. The triangular element and the inverted Y-shaped element emit electromagnetic waves having different wavelengths. Can be shielded.

The FSS element shown in FIG. 4 (e) has a double square outline formed by thin metal layer lines.
The FSS element shown in FIG. 4 (f) has an inverted Y-shaped contour formed in an annular shape by a thin metal layer.
In the FSS element shown in FIG. 4G, a cross-shaped contour is formed in an annular shape by a thin line of a metal layer.
The FSS element shown in FIG. 4 (h) is formed by forming a cross-shaped outline and an X-shaped outline in an annular shape by thin lines of a metal layer.

The FSS element shown in FIG. 4 (i) is formed by forming an H-shaped outline by a thin wire of a metal layer, and alternately arranging a vertical H-shape and a horizontal H-shape.
The FSS element shown in FIG. 4 (j) has a triangular outline formed by fine lines of a metal layer. In the horizontal direction, triangles in the normal position and triangles in the reverse position are alternately arranged, and in the vertical direction. Are the same in the forward and reverse positions, arranged in rows. Thereby, the installation density of a FSS element can be made high and the electromagnetic wave shielding effect can be improved.
The FSS element shown in FIG. 4 (k) is formed by forming a V-shaped outline by a thin line of a metal layer and alternately arranging a V-shape at a normal position and a V-shape at a reverse position.

  In addition, although illustration is omitted, a circular ring type, a Jerusalem cross type, or a fractal shape that is self-similar to a desired basic shape may be exemplified as FSS element shapes that can be applied to the present invention. it can. It is also possible to configure an electromagnetic wave shield laminate that can selectively shield electromagnetic waves having two or more types of frequencies by using a combination of two or more different types of FSS elements having different shapes and dimensions. .

  In the present invention, as a method for producing a conductive metal layer which is a fine line pattern of an FSS element, a method for producing by printing a conductive paste, a method for producing from a developed silver layer produced by a photographic method, and a photographic method. A method of generating from the generated developed silver layer and a metal plating layer laminated thereon can be used. In addition, a method for producing a fine line pattern by a conductive metal layer by each method is described below. The method of electroless plating will be described in order.

(Generation of metal layer by printing)
Since the conductive paste used in the present invention is a fine line pattern of an FSS element made of a conductive metal layer, a conductive paste in which metal powder is mixed with a resin component serving as a binder is usually used. As said metal powder, metal powders, such as copper, silver, nickel, aluminum, are used, However, It is preferable to use the fine powder of copper or silver from the point of electroconductivity and a price.

  Carbon black is used in the conductive paste to remove the metallic luster caused by the metal powder contained in the fine line pattern of the printed FSS element and suppress reflection of external light, and to improve the visibility when attached to the window glass. It is preferable to mix a black pigment such as. The black pigment is preferably contained at 0.1 to 10% by weight in the conductive paste.

Since the line width of the fine line pattern of the FSS element to be printed is about 15 to 80 mm, the metal powder used for the conductive paste does not have to be special ultrafine particles, and the particle diameter of the metal powder is 0.1 to What is necessary is just 5 micrometers.
The thickness of the printed electrode frame is not particularly limited, but is about 0.05 to 15 μm.

As a resin component used for the conductive paste, a thermoplastic resin such as a polyester resin, a (meth) acrylic resin, a polyethylene resin, a polystyrene resin, or a polyamide resin is preferably used. Moreover, thermosetting types, such as an epoxy resin, an amino resin, a polyimide resin, (meth) acrylic resin, may be sufficient.
In the conductive paste, the metal powder and the black pigment are mixed into these resin components, and then the viscosity is adjusted by adding an organic solvent such as alcohol or ether.

A fine line pattern of the FSS element is printed on one side of the transparent base materials 5 and 6 in FIG. 1 and the transparent base materials 15 and 16 in FIG. 2 using a conductive paste, and the solvent is removed by drying to cure the fine line pattern. .
The method for applying the conductive paste to form the fine line pattern of the FSS element is not particularly limited, but printing by screen printing is preferred for simplicity.

(Generation of metal layer from developed silver layer by photographic method)
In the exposure development method based on the photographic method for forming a developed silver layer, (a) developed silver appears in an exposed portion that is not covered with an exposure mask, that is, developed in a shape opposite to the exposure mask. A so-called negative exposure and development method in which silver appears; and (b) a so-called positive type in which developed silver appears in a portion that is covered with an exposure mask and is not exposed, that is, developed silver appears in the same shape as the exposure mask. There are two exposure development methods.

  In the present invention, any of the above-described two photographic production methods (a) negative exposure / development method and (b) positive exposure / development method can be applied.

(Photo production method)
Hereinafter, a method for producing a developed silver mesh pattern by a positive exposure / development method (DTR method) will be described. In the case of the DTR method, it is preferable that a physical development nucleus layer is provided in advance on the transparent substrate surface. As the physical development nuclei, fine particles (having a particle size of about 1 to several tens of nm) made of heavy metals or sulfides thereof are used. Examples thereof include colloids such as gold and silver, metal sulfides obtained by mixing water-soluble salts such as palladium and zinc and sulfides, and the like. The fine particle layer of these physical development nuclei can be provided on the transparent substrate by a vacuum deposition method, a cathode sputtering method, a coating method or the like. From the viewpoint of production efficiency, a coating method is preferably used. The content of physical development nuclei in the physical development nuclei layer is suitably about 0.1 to 10 mg per square meter in solid content.

  The transparent base materials 5 and 6 in FIG. 1 and the transparent base materials 15 and 16 in FIG. 2 can be provided with an adhesive layer of a polymer latex layer such as vinylidene chloride or polyurethane, and between the adhesive layer and the physical development nucleus layer. An intermediate layer made of a hydrophilic binder such as gelatin can be provided therebetween.

  The physical development nucleus layer preferably contains a hydrophilic binder. The amount of the hydrophilic binder is preferably about 10 to 300% by mass with respect to the physical development nucleus. As the hydrophilic binder, gelatin, gum arabic, cellulose, albumin, casein, sodium alginate, various starches, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, a copolymer of acrylamide and vinyl imidazole, and the like can be used. The physical development nucleus layer may also contain a hydrophilic binder crosslinking agent.

  The physical development nucleus layer and the intermediate layer can be applied by an application method such as dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, spray coating, and the like. In the present invention, the physical development nucleus layer is preferably provided as a continuous and uniform layer by the above-described coating method.

  The supply of silver halide for precipitating metallic silver on the physical development nucleus layer is performed by a method in which the physical development nucleus layer and the silver halide emulsion layer are integrally provided in this order on the substrate, or another paper or plastic resin film. There is a method of supplying a soluble silver complex salt from a silver halide emulsion layer provided on a substrate such as the above. From the viewpoint of cost and production efficiency, the former physical development nucleus layer and the silver halide emulsion layer are preferably provided integrally.

The silver halide emulsion can be produced according to a general method for producing a silver halide emulsion of a silver halide photographic light-sensitive material. The silver halide emulsion is usually prepared by mixing and ripening an aqueous silver nitrate solution, an aqueous halogen solution of sodium chloride or sodium bromide in the presence of gelatin.
The silver halide composition of the silver halide emulsion layer preferably contains 80 mol% or more of silver chloride, and more preferably 90 mol% or more is silver chloride. The conductivity of the physically developed silver formed by increasing the silver chloride content is improved.

    The silver halide emulsion layer is sensitive to various light sources. In the present invention, when the pattern of the FSS element is formed by physically developed silver, as a method for exposing the silver halide emulsion layer, a method of exposing the FSS element pattern transmission original and the silver halide emulsion layer in close contact, or various lasers There is a method of scanning exposure using light. The former contact exposure is possible even if the silver halide has relatively low photosensitivity, but in the case of scanning exposure using laser light, relatively high photosensitivity is required. Therefore, when the latter exposure method is used, the silver halide may be subjected to chemical sensitization or spectral sensitization with a sensitizing dye in order to increase the sensitivity of the silver halide.

  Chemical sensitization includes metal sensitization using a gold compound or silver compound, sulfur sensitization using a sulfur compound, or a combination thereof. Gold-sulfur sensitization using a gold compound and a sulfur compound in combination is preferable. In the above-described method of exposing with laser light, a laser beam having an oscillation wavelength of 450 nm or less, for example, a blue semiconductor laser (also referred to as a violet laser diode) having an oscillation wavelength of 400 to 430 nm is used. It can be handled even under a yellow fluorescent lamp.

  Any position on the substrate on which the physical development nucleus layer is provided, for example, an adhesive layer, an intermediate layer, a physical development nucleus layer or a silver halide emulsion layer, a protective layer, or a backing layer provided with a support interposed therebetween. A dye or pigment for preventing irradiation may be contained.

  When developing silver using a photosensitive material in which a silver halide emulsion layer is applied directly on the physical development nucleus layer or via an intermediate layer, the transparent original of the FSS element pattern and the photosensitive material are adhered to each other. After exposure or scanning exposure of the above-mentioned photosensitive material to a digital image of an FSS element pattern with various laser light output machines, the silver is processed in an alkaline solution in the presence of a soluble silver complex salt forming agent and a reducing agent. Complex salt diffusion transfer development (DTR development) occurs, the silver halide in the unexposed area is dissolved to form a silver complex salt, which is reduced on the physical development nuclei to deposit metal silver to obtain a physically developed silver thin film having an FSS element pattern. be able to. The exposed portion is chemically developed in the silver halide emulsion layer to become blackened silver. After development, the silver halide emulsion layer and the intermediate layer, or the protective layer provided as necessary, are washed away with water, and the physically developed silver thin film of the FSS element pattern is exposed on the surface.

  After DTR development, the silver halide emulsion layer or the like provided on the physical development nucleus layer may be removed by washing with water or transferring and peeling to a release paper or the like. There are two methods for removing the water washing: a method of removing hot water using a scrubbing roller or the like while jetting it with a nozzle or the like, and a method of removing hot water by jetting with a nozzle or the like.

  On the other hand, when supplying a soluble silver complex salt from a silver halide emulsion layer provided on a substrate different from the substrate on which the physical development nucleus layer was coated, the silver halide emulsion layer was exposed in the same manner as described above. After that, the substrate coated with the physical development nucleus layer and another photosensitive material coated with the silver halide emulsion layer are superposed and adhered in an alkaline solution in the presence of a soluble silver complex salt forming agent and a reducing agent. Then, after taking out from the alkaline solution, after several tens of seconds to several minutes have passed, the both are removed to obtain a physically developed silver thin film having an FSS element pattern deposited on the physical development nuclei.

  Next, a soluble silver complex salt forming agent, a reducing agent, and an alkali solution necessary for silver complex diffusion transfer development will be described. The soluble silver complex forming agent is a compound that dissolves silver halide to form a soluble silver complex salt, and the reducing agent is a compound that reduces this soluble silver complex salt to precipitate metallic silver on physical development nuclei. These actions are performed in an alkaline solution.

  Examples of the soluble silver complex forming agent used in the present invention include sodium thiosulfate, thiosulfate such as ammonium thiosulfate, thiocyanate such as sodium thiocyanate and ammonium thiocyanate, alkanolamine, sodium sulfite, and potassium bisulfite. Sulfites such as T. H. Examples include the compounds described in 474-475 (1977) of James The Theory of the Photographic Process 4th edition.

  As the reducing agent, a developing agent known in the field of photographic development can be used. For example, hydroquinone, catechol, pyrogallol, methylhydroquinone, polyhydroxybenzenes such as chlorohydroquinone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl- Examples include 3-pyrazolidones such as 4-hydroxymethyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine, and the like.

  The above-described soluble silver complex salt forming agent and reducing agent may be applied to the substrate together with the physical development nucleus layer, added to the silver halide emulsion layer, or contained in an alkaline solution. Further, it may be contained in a plurality of positions, but it is preferably contained in at least the alkaline liquid.

  The content of the soluble silver complex salt forming agent in the alkaline solution is suitably used in the range of 0.1 to 5 mol per liter of the developer, and the reducing agent is 0.05 to 1 per liter of the developer. It is suitable to use in the molar range.

  The pH of the alkaline solution is preferably 10 or more, and more preferably in the range of 11-14. Application of the alkaline solution for silver complex diffusion transfer development may be an immersion method or a coating method. The immersion method is, for example, a method in which a substrate provided with a physical development nucleus layer and a silver halide emulsion layer is transported while being immersed in an alkaline liquid stored in a large amount in a tank. About 40 to 120 ml of alkali solution per square meter is applied on the silver halide emulsion layer.

In order to ensure transparency (not visually observed), the FSS element is constituted by a fine line pattern made of a metal layer. The line width of the metal layer of the fine line pattern made of the FSS element is preferably 15 to 80 μm, and more preferably 15 to 40 μm. The thickness of the metal layer of the fine line pattern can be arbitrarily changed according to desired characteristics, but is preferably in the range of 0.05 to 12 μm, more preferably in the range of 0.05 to 3 μm.
As described above, in the frequency selective shielding type electromagnetic wave shielding laminate of the present invention, when the line width of the fine line pattern made of the FSS element is reduced to 15 μm or less, the transparency (not visually observed) increases, but the conductivity ( In addition, when the line width is increased to 80 μm or more, the transparency is reduced but the conductivity is increased. In addition, if the line width is a fine line of 15 μm or less, the manufacturing cost of an exposure mask for forming a fine line pattern of the metal layer by a photographic method is remarkably increased.

The developed silver layer by physical development of an arbitrary fine line pattern formed on the transparent substrate according to the present invention has a very thin film thickness but is highly conductive, so it can be thinned and is of a frequency selective shielding type. The transparency of the electromagnetic wave shield laminate can be increased.
In addition, the developed silver layer itself by this physical development, the metal silver particles forming the developed silver layer obtained after the development process is very small, and the amount of the hydrophilic binder present in the developed silver layer is extremely small, Since the developed silver layer is formed in the state where the developed silver layer is close to the close-packed state and has electric conductivity, it can be plated with a metal such as copper or nickel. If necessary, a metal plating layer can be laminated on the developed silver layer.

(Metal plating layer)
The plating method used when laminating a metal plating layer on the developed silver layer, which is a metal layer of a fine line pattern made of FSS elements, is an electroless plating method. The developed silver layer, which is the basic part of the fine line pattern composed of FSS elements, is electrically conductive. However, the FSS element patterns composed of the developed silver layer are individually arranged independently, and the adjacent FSS element patterns are electrically connected to each other. Is electrically insulated. Therefore, a large number of FSS element patterns cannot be electroplated simultaneously and the electroless plating method must be applied.

  In the present invention, the metal plating method can be performed by a known method. For example, the electroless plating method is conventionally known, such as copper, nickel, silver, gold, tin, solder, or a multilayer or composite system of copper / nickel. These methods can be used, and for these, reference can be made to documents such as “Basics and Applications of Electroless Plating; Nikkan Kogyo Shimbun, May 30, 1994, First Edition”.

Copper (Cu) and / or nickel (Ni) is preferable as the metal used for plating because it is easy to plate and the plating layer has excellent conductivity, can be plated into a thick film, and is low in cost. . The metal plating layer is preferably formed by laminating a plurality of layers of the same kind of metal or different kinds of metals by performing plating a plurality of times. For example, when a first plating layer is laminated on a developed silver layer and a second plating layer is further laminated thereon, one plating layer is an electroless nickel plating layer, and the other plating layer is an electroless copper. A combination that is a plating layer is preferred.
The type of plating tank used for plating may be either a vertical type or a horizontal type, but the length is determined so as to ensure a predetermined plating residence time.

(Blackening treatment)
You may form the blackening layer for reducing a reflectance by performing the blackening process on the surface of the said metal plating layer. The blackening layer may be a dark layer that hardly reflects light, and may be not only black but also, for example, blackish brown or blackish green. The formation of the blackened layer is preferable because the fine metal wires are less noticeable and, for example, when the electromagnetic wave shielding laminate is attached to a window glass or the like, the other side can be easily seen through the transparent substrate.
The blackening layer may be formed by an ink treatment by applying black ink, a blackening plating treatment by plating a metal such as ruthenium, nickel, or tin that has a black surface, or a chemical conversion treatment (oxidation treatment, etc.) of a fine metal wire. it can. Among these, in the chemical conversion treatment, a thin film of metal oxide is formed on the surface of the metal layer, and thus black color is exhibited.

(Exposure equipment)
As the exposure apparatus for exposing the silver halide emulsion layer, there are a single wafer processing type exposure apparatus using a single wafer type exposure mask (photomask) and a continuous exposure apparatus capable of forming a continuous pattern. A single wafer processing type exposure apparatus uses a single wafer type exposure mask (photomask) on which a predetermined mask pattern is formed, feeds the substrate to the exposure apparatus intermittently, and evacuates the inside of the apparatus for exposure. After the mask and the substrate are brought into close contact with each other and no gap is formed, exposure is performed with, for example, ultraviolet rays. In a single wafer processing type exposure apparatus, since vacuum evacuation, exposure, and release to the atmosphere are intermittently performed, continuous production cannot be performed, and the processing speed becomes slow.

On the other hand, when a continuous exposure apparatus capable of continuously exposing the substrate is used, there is an advantage that the processing speed is higher than that of the single wafer processing type exposure apparatus and continuous production is possible.
As an example of a continuous exposure apparatus, a cylindrical drum made of a material that transmits light used for exposure in a photographic method, an exposure mask film on which a pattern corresponding to an FSS element provided on the outer peripheral wall of the cylindrical drum is formed, An exposure light source disposed inside the cylindrical drum and exposing a substrate wound around the cylindrical drum by light emitted from the light source inside the cylindrical drum.

(Adhesive layer)
The electromagnetic wave shielding laminate of the present invention is a transparent substrate in which fine line patterns of FSS elements are formed on both end surfaces of an intermediate base material layer made of a transparent solid dielectric, such as a window material using a glass plate or a transparent plastic plate. The material is laminated through an adhesive layer.
In addition, the electromagnetic wave shielding laminate of the present invention in which a transparent base material on which a fine line pattern of an FSS element is formed is laminated on both end faces of an intermediate base material layer made of a transparent solid dielectric via an adhesive layer, You may affix on a window glass using an adhesive layer.
The pressure-sensitive adhesive layer used is preferably transparent. Specifically, the total light transmittance of the pressure-sensitive adhesive layer is preferably 70% or more, and more preferably 80% or more.

As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, for example, any of rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives and the like may be used, and among them, acrylic pressure-sensitive adhesives are particularly preferable. Thereby, it is excellent in transparency and the weather resistance of an adhesive layer can be maintained favorable.
Examples of such an acrylic pressure-sensitive adhesive component include a low-Tg main monomer that provides tackiness, a high-Tg comonomer that provides adhesion and cohesion, and a functional group for improving crosslinking and adhesion. Those composed of a group-containing monomer (monoethylenically unsaturated monomer) and the like are used.

Examples of the main monomer include alkyl acrylates such as ethyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, benzyl acrylate, butyl methacrylate, and methacrylic acid. Examples thereof include methacrylic acid alkyl esters such as 2-ethylhexyl, cyclohexyl methacrylate and benzyl methacrylate, and these can be used alone or in combination of two or more.
Examples of the comonomer include vinyl group-containing compounds such as methyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, vinyl propionate, vinyl ether, styrene, acrylonitrile, and methacrylonitrile.
Examples of functional group-containing monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta ) Acrylate, 4-hydroxybutyl (meth) acrylate, N-methylolacrylamide, hydroxyl group-containing monomers such as allyl alcohol, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) ) Tertiary amino group-containing monomers such as acrylate, amide group-containing monomers such as acrylamide and methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide N- ethoxymethyl (meth) acrylamide, N-t-butyl acrylamide, N- substituted amide group-containing monomers such as N- octyl acrylamide, an epoxy group-containing monomers such as glycidyl methacrylate.

By using such a material, it is excellent in adhesiveness, cohesiveness, and durability, and arbitrary quality and characteristics according to the application can be obtained by selecting the kind and combination of monomers.
The weight average molecular weight of the pressure-sensitive adhesive component is preferably 300,000 to 3,000,000, more preferably 500,000 to 2,000,000. If the molecular weight of the pressure-sensitive adhesive component is too small, the pressure-sensitive adhesive strength and cohesive strength of the pressure-sensitive adhesive will be poor, and sufficient blister resistance will not be obtained. If the molecular weight is too large, the pressure-sensitive adhesive will become hard and the pressure-sensitive adhesive will be insufficient. Workability of sticking deteriorates.

Moreover, it is preferable that the glass transition point (Tg) of an adhesive component is -20 degrees C or less. When the glass transition point exceeds −20 ° C., the pressure-sensitive adhesive becomes hard depending on the use temperature, and the adhesiveness may not be maintained.
As the above-mentioned pressure-sensitive adhesive, either a crosslinked type or a non-crosslinked type can be used. In the case of the crosslinking type, examples include methods using various crosslinking agents such as epoxy compounds, isocyanate compounds, metal chelate compounds, metal alkoxides, metal salts, amine compounds, hydrazine compounds, aldehyde compounds, and the like. The functional group is appropriately selected.
The curable component contained in the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include those having thermosetting properties such as epoxy resins, phenolic resins, melamine resins, and polyester resins, or those having radiation curable properties described later. Particularly preferred are those having radiation curability. As a result, the curable component can be cured at room temperature or low temperature in a very short time, and the handleability is excellent.

The term “radiation curable” as used herein means, for example, that molecular chain growth or crosslinking reaction is induced by irradiation with ultraviolet rays, laser beams, α rays, β rays, γ rays, X rays, or electron beams, and the curable components are cured. Means nature.
Such a radiation curable component is not particularly limited, but for example, a component having an acrylic monomer or oligomer is preferable. Thereby, an adhesive layer having excellent weather resistance can be formed.
Examples of such radiation curable acrylic monomers and / or oligomers include hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane acrylate, epoxy acrylate, polyester acrylate, and the like. These may be used alone or in combination.

Further, the acrylic monomer or oligomer preferably includes a reactive monomer or oligomer having an acryloyl group, and more preferably has two or more acryloyl groups. By including two or more acryloyl groups, the network structure is sufficiently formed, the cohesiveness of the pressure-sensitive adhesive is further improved, and a good pressure-sensitive adhesive layer is obtained.
0.05-50 weight part is preferable with respect to 100 weight part of said adhesive components, and, as for content of curable components, such as the said radiation-curable component, 0.1-20 weight part is more preferable. If the amount of the curable component is too small, the effect of suppressing foaming and swelling due to the generated gas may not be sufficiently obtained due to the cohesive force of the pressure-sensitive adhesive. On the other hand, when there is too much quantity of a sclerosing | hardenable component, there exists a possibility that an adhesive layer may become hard too much and adhesive force may fall.
When the curable component is blended with the pressure-sensitive adhesive component, those having good compatibility with the pressure-sensitive adhesive component are preferable. In addition, the curable component can be used as a copolymer with the main polymer of the pressure-sensitive adhesive component.
When the radiation curable component is cured by ultraviolet irradiation or the like, the pressure-sensitive adhesive layer is preferably light-transmitting, for example, substantially transparent or semi-transparent (colorless or colored), and thus the pressure-sensitive adhesive layer The agent layer can be easily cured.
The pressure-sensitive adhesive layer in the present invention may be formed with what is usually called an adhesive.

  From the viewpoint of transparency, colorlessness, and handleability, the thickness of the pressure-sensitive adhesive layer is preferably about 1 to 100 μm. When the pressure-sensitive adhesive layer is formed of an adhesive, the thickness of the pressure-sensitive adhesive layer is made thinner within the above range. Specifically, about 1 to 20 μm is preferable. When forming with an adhesive, the thickness of an adhesive layer is made thick in the said range. Specifically, about 5-60 micrometers is preferable.

  According to the present invention, it can be easily attached to a window of a building or used for a transparent partition in a room, which cannot be dealt with by the prior art, has excellent visibility and is thicker than a conventional λ / 4 type electromagnetic wave shield. Therefore, it is possible to provide a frequency selective shielding type electromagnetic wave shield laminate having a wide-band resonance frequency, which greatly facilitates and improves the environment of wireless communication.

It is a partial expanded sectional view which shows schematic structure of the electromagnetic wave shield laminated body of the frequency selective shielding type which concerns on a reference example . Is an enlarged partial sectional view showing an outline substantially arrangement of the electromagnetic wave shielding laminate of the frequency selective shielding type according to the present invention. (A) is a conceptual diagram showing the bandwidth w ₁ at the shielding level α at the resonance frequency P in the prior art. (B) is a conceptual diagram showing the bandwidth w ₂ at the shielding level α at the resonance frequency P in the present invention. (A)-(k) is a partial enlarged front view which shows the example of the pattern of a FSS element, respectively.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,10 ... Frequency selective shielding type electromagnetic wave shield laminated body, 2, 11, 12 ... Transparent intermediate base material layer, 3, 4, 13, 14 ... FSS element thin wire pattern metal layer, 5, 6, 15, 16 ... transparent substrate, 7, 8, 17, 18, 19 ... adhesive layer.

Claims (5)

A wave shielding laminate of the frequency selective shielded to shield electromagnetic waves of a predetermined frequency band, has a see-through property, both ends of the intermediate base layer made of different two or more layers of transparent solid dielectric permittivity A transparent substrate of a resin film made of a dielectric material is laminated on the surface via an adhesive layer, and a thin line pattern made of an FSS element for shielding electromagnetic waves is disposed on one surface of the transparent substrate. The thickness of the intermediate base material layer is approximately λ / 60 to λ / 8 adjusted using a laminate of resin sheets (where λ is a predetermined frequency to shield electromagnetic waves in the intermediate base material layer) The two fine line patterns arranged on both sides of the intermediate base material layer are metal layers composed of developed silver layers produced by a photographic method, and are one of the transparent base materials. Viewed from the direction perpendicular to the surface, 2 Arrangement interval of the fine line pattern Ri is Na is disposed substantially overlapping position, the line width of the fine line pattern composed of the metal layer becomes 15～80Myuemu, and the characteristics of the 0.05~15μm der Rukoto thickness Electromagnetic wave shield laminate. A wave shielding laminate of the frequency selective shielded to shield electromagnetic waves of a predetermined frequency band, has a see-through property, both ends of the intermediate base layer made of different two or more layers of transparent solid dielectric permittivity A transparent substrate of a resin film made of a dielectric material is laminated on the surface via an adhesive layer, and a thin line pattern made of an FSS element for shielding electromagnetic waves is disposed on one surface of the transparent substrate. The thickness of the intermediate base material layer is approximately λ / 60 to λ / 8 adjusted using a laminate of resin sheets (where λ is a predetermined frequency to shield electromagnetic waves in the intermediate base material layer) The two fine line patterns arranged on both sides of the intermediate base material layer are metal layers generated by printing a conductive paste containing a black pigment, and are transparent. Perpendicular to one side of the substrate Viewed from the direction, the arrangement interval of the two fine line patterns Ri is Na is disposed substantially overlapping position, the line width of the fine line pattern composed of the metal layer is 15～80Myuemu, and the thickness 0.05~15μm electromagnetic wave shielding laminate according to claim der Rukoto.   When the figure shape of the fine line pattern of the FSS element is an open figure, the length between both ends of the figure is ½ of the wavelength λ, and in the case of an annular figure, the entire circumference of the figure is the wavelength λ. The electromagnetic wave shielding laminate according to claim 1, wherein the electromagnetic wave shielding laminate is equal.   On at least one surface of the transparent base material, logo marks and / or alignment marks such as specific trade names, trademarks, and model numbers, which are two thin line patterns arranged on both sides of the intermediate base material layer One or more types selected from the group of figures, characters, symbols, codes, etc. that can be used to adjust the overlapping position are arranged at regular intervals in the vertical and horizontal directions depending on the size that can be seen. The electromagnetic wave shielding laminate according to any one of claims 1 to 3, wherein The thin line pattern, as can be shielded from one or more resonant frequencies, to any one of claims 1 to 4, characterized in that FSS element consisting of one or more kinds of shapes are arrayed The electromagnetic wave shielding laminate according to the description.

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