JP2008211010A - Near-infrared ray, lamination for antielectromagnetic wave shielding, and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide near-infrared rays, a lamination for antielectromagnetic wave shielding which achieve superior shielding against near-infrared rays and electromagnetic waves and are inexpensive, and a manufacturing method therefor. <P>SOLUTION: An anti-near-infrared rays shielding layer containing a tungsten-oxide-based or phthalocyanine-based near-infrared rays absorbent is formed on one surface of a transparent base material. On the anti-near-infrared rays shielding layer, a meshed pattern of an electroless plating catalyst ink is printed, on which electroless metal plating is formed, and which is further coated with electrolytic metal plating if necessary. Then, a metal mesh layer 3 for antielectromagnetic wave shielding is formed to provide the lamination. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a near infrared / electromagnetic wave shielding laminate that can be suitably used for an optical filter mounted on a plasma display or the like, and a method for producing the same. More specifically, the present invention is an inexpensive near-infrared / electromagnetic wave shielding laminate having excellent near-infrared shielding properties, visible light transmission properties, and electromagnetic wave shielding properties, and near-infrared rays having the above properties. The present invention relates to a method for producing a near-infrared / electromagnetic wave shielding laminate capable of inexpensively producing an electromagnetic shielding laminate by a simple production process.

  The plasma display device generally includes a near-infrared / electromagnetic wave shielding laminate having a near-infrared shielding layer and an electromagnetic shielding layer for shielding near-infrared rays and electromagnetic waves generated from the device on the front glass of the light-emitting module. A filter is installed. In addition, the optical filter often includes means for imparting antireflection properties in order to improve functions other than near-infrared shielding and electromagnetic wave shielding, for example, visibility.

  Cost reduction is important for the spread of democratic plasma display televisions, and the price of optical filters is also required to be reduced. An optical filter generally includes an electromagnetic wave shielding film in which an electromagnetic wave shielding layer is laminated on a transparent film, a near infrared ray shielding film in which a near infrared ray shielding layer is laminated on a transparent film, and an antireflection layer on the transparent film. Since a plurality of various functional films including a laminated antireflection film are manufactured together, there are many manufacturing processes, low productivity, and high manufacturing costs.

  The electromagnetic shielding layer generally uses an etching mesh film formed in a lattice shape by etching a copper foil formed on a transparent film by a photolithography process. However, in the production of the etching mesh film, a copper foil layer having a mesh pattern is formed by etching the copper foil having a patterned resist resin film formed on a copper foil laminated on a transparent film. Therefore, there is a problem that the process becomes complicated, the material used is wasted, and the manufacturing cost is high. In addition, since it is difficult to manage the etching conditions, there is a problem that the manufacturing yield is low and the manufacturing cost is further increased.

  Therefore, in order to solve the above-mentioned problems relating to manufacturing cost and productivity, attempts have been made to laminate an electromagnetic wave shielding layer and a near infrared shielding layer on a single transparent film. In Japanese Patent No. 313918 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2006-243757 (Patent Document 2), a metal such as silver and a metal oxide such as tin-containing indium oxide are alternately stacked to form a film. Thus, a near infrared / electromagnetic wave shielding laminate having both near infrared shielding ability and electromagnetic shielding ability is disclosed. Japanese Patent Laid-Open No. 2002-3118433 (Patent Document 3) contains an organic absorbent that absorbs a specific wavelength of visible light and / or near infrared in a mesh made of a metal thin film formed by an etching method. A laminated body for near-infrared / electromagnetic wave shielding produced by laminating on a transparent film via an adhesive or pressure-sensitive adhesive that has both near-infrared shielding ability and electromagnetic shielding ability is disclosed.

However, in the case of the methods of Patent Documents 1 and 2, the sputtering apparatus requires a large-scale vacuum facility, so that the manufacturing cost is high, and the electromagnetic wave shielding ability and the near infrared shielding performance required for the plasma display are obtained satisfactorily. Therefore, it is necessary to laminate the electromagnetic wave shielding layer and the near-infrared shielding layer in multiple layers of 7 to 9 layers, and it is difficult to sufficiently reduce the manufacturing cost.
Further, in the case of the method of Patent Document 3, since a mesh made of a metal thin film is formed by using an etching method, the manufacturing cost of the mesh itself increases, and a sufficient cost reduction and simplification of the manufacturing process cannot be expected.

Therefore, as a method for inexpensively producing a near-infrared / electromagnetic wave shielding laminate having both a near-infrared shielding ability and an electromagnetic shielding ability by laminating a near-infrared shielding layer and an electromagnetic shielding layer on a single transparent film. A method of forming a metal mesh film on the near-infrared shielding layer formed on the surface of the transparent film by electroless plating using an inexpensive mass-productive printing method can be considered. In the case of the electroless plating treatment, in order to ensure good printability and adhesion, a receiving layer for the electroless plating catalyst ink is required as a base. If the absorbent can be contained, it can be combined without increasing the number of special steps, and a large cost reduction can be expected.
However, conventionally, organic dyes such as imoniums have been used for near-infrared absorbers. However, when these organic dyes have low acid resistance and alkali resistance, they are subjected to a process such as electroless plating. For this reason, it has been difficult to form a mesh made of a metal thin film on the near infrared shielding layer by an electroless plating process using a printing method.

JP 2006-313918 A JP 2006-243757 A JP 2002-311843 A

  Therefore, the present invention has excellent near-infrared shielding properties and visible light transmission properties, and also excellent electromagnetic shielding properties, and an inexpensive near-infrared / electromagnetic wave shielding laminate, and a near-infrared An object of the present invention is to provide a method for producing a near-infrared / electromagnetic wave shielding laminate capable of inexpensively producing an electromagnetic shielding laminate by a simple process.

  As a result of intensive investigations for solving the above problems, the present inventor has achieved excellent productivity and inexpensive printing on the near-infrared shielding layer formed on the surface of the transparent film by using a specific near-infrared absorber. It is possible to form a metal mesh film by electroless plating process using a method, and it has excellent near-infrared shielding ability, visible light transmission ability, and excellent electromagnetic shielding ability without increasing special processes. It has been found that a laminate for shielding infrared rays and electromagnetic waves can be produced at a low cost, and the present invention has been completed.

The near infrared / electromagnetic wave shielding laminate of the present invention comprises a transparent substrate, a near infrared shielding layer formed on one main surface of the transparent substrate, and an electromagnetic shielding material formed on the near infrared shielding layer. A near infrared / electromagnetic wave shielding laminate in which a metal mesh layer is laminated and integrated,
The near-infrared shielding layer contains a tungsten oxide-based and / or phthalocyanine-based near infrared absorber, and a binder resin.
The electromagnetic shielding metal mesh layer is formed by electroless plating on a mesh-like electroless plating catalyst layer formed on the near-infrared shielding layer. .
In the near infrared / electromagnetic wave shielding laminate of the present invention, it is preferable that the electromagnetic shielding metal mesh layer is formed by performing electroplating after the electroless plating. The method for producing a near-infrared / electromagnetic wave shielding laminate of the present invention comprises a tungsten oxide-based and / or phthalocyanine-based near-infrared absorber, a binder resin, and the above-mentioned near-infrared absorption on one main surface of a transparent substrate. Applying and drying a near-infrared shielding composition containing an agent and a solvent for dissolving or dispersing the binder resin to form a near-infrared shielding layer, and then electroless plating on the near-infrared shielding layer Forming a catalyst layer for electroless plating by printing a catalyst ink for mesh on the mesh, and forming a mesh electroless plating layer by electroless plating on the catalyst layer for electroless plating And a metal mesh layer forming step for shielding electromagnetic waves.
In the electromagnetic wave shielding metal mesh layer forming step of the method for producing a near-infrared / electromagnetic wave shielding laminate of the present invention, the mesh-like electroless plating layer is subjected to electrolytic plating to form a mesh-like electrolytic plating layer. It is preferable to further contain.
In the electromagnetic wave shielding metal mesh layer forming step of the method for producing a near infrared / electromagnetic wave shielding laminate of the present invention, the electroless plating catalyst ink is preferably printed using a gravure printing method.
In the method for producing a near-infrared / electromagnetic wave shielding laminate of the present invention, the electroless plating catalyst ink printing by the gravure printing method meshes the electroless plating catalyst ink in a groove on the gravure printing plate cylinder. The near-infrared shielding layer on the transparent base material is pressure-bonded to the transparent substrate for a predetermined time, whereby the electroless plating catalyst on the plate cylinder is transferred onto the near-infrared absorbing layer on the transfer sheet ( (Blanket) is preferably applied by transferring without using.
In the method for producing a near infrared / electromagnetic wave shielding laminate of the present invention, it is preferable that the predetermined pressure bonding time in the transfer of the electroless plating catalyst is 0.5 seconds to 10 seconds.

"Laminated body for near infrared and electromagnetic wave shielding"
FIG. 1 shows an embodiment (1) of the near infrared / electromagnetic wave shielding laminate of the present invention. In FIG. 1, the near-infrared electromagnetic wave shielding laminate 10 includes a transparent base material 2, a near-infrared shielding layer 4 formed on the transparent base material 2, and an electromagnetic shielding material formed on the near-infrared shielding layer 4. A metal mesh layer 3 is provided, and these layers 2, 3 and 4 are laminated in a single sheet.

  Further, in FIG. 1, the near-infrared shielding layer 4 is made of a tungsten oxide-based and / or phthalocyanine-based near-infrared absorber and a binder resin, and the electromagnetic shielding metal mesh layer 3 is shown in FIG. As schematically shown in cross section, an electroless plating layer 22 is formed on the electroless plating catalyst layer 21 formed on the near-infrared shielding layer 4, and if necessary, the electroless plating layer. An electrolytic plating layer 23 is formed on 22.

  The near-infrared absorber has high chemical resistance, in particular, has high resistance to an ink for forming a catalyst layer for electroless plating, an electroless plating bath, and an electrolytic plating bath, and is required for a plasma display. Excellent in shielding ability in the near infrared region of 850 nm to 1000 nm and transparency in the visible light region.

Examples of the tungsten oxide-based near-infrared absorber having the above-described characteristics include, for example, a general formula: W _y O _z [W represents a tungsten atom, O represents an oxygen atom, and 2.2 ≦ z / y. ≦ 2.999] and fine particles of tungsten oxide represented by the general formula: M _x W _y O _z [where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, Represents one or more atoms selected from F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, and W represents Represents a tungsten atom, O represents an oxygen atom, 0.001 ≦ x / y 1.1, 2.2 ≦ z / y ≦ 3.0] can be exemplified, and these tungsten oxide-based near infrared absorbers are commercially available. Therefore, it can be appropriately selected and used.

When using a tungsten oxide-based near-infrared absorber as the near-infrared absorber, the content in the near-infrared shielding layer 4 is not particularly limited, but to obtain good near-infrared shielding properties and visible light transmittance. is preferably 0.5 to 5 g / m ^2, more preferably 1 to 3 g / m ^2. If the content of the tungsten oxide-based near-infrared absorber is lower than 1 g / m ² , sufficient shielding ability cannot be obtained in the near-infrared region. On the other hand, if the content is higher than 3 g / m ² , visible light is obtained. The transmittance of the area is significantly reduced.
The average particle size of the tungsten oxide-based near-infrared absorber is preferably 0.01 μm to 0.1 μm from the viewpoints of near-infrared shielding, transparency, and coatability. Moreover, it is preferable that the near-infrared absorber of tungsten oxide is dispersed so that the dispersed particle diameter is 0.1 μm or less in the near-infrared shielding layer from the viewpoint of transparency.

Examples of the phthalocyanine-based near-infrared absorber having the above-described properties include those selected from compounds represented by the following general formula (I), and commercially available ones are preferably used. be able to.
In the general formula (I), eight α's each independently represent one member selected from —SR ¹ , —OR ² and —NHR ³ groups and a halogen atom, provided that at least one α represents an —NHR ³ group, and eight βs each independently represent at least one member selected from —SR ¹ , —OR ² and a halogen atom, provided that at least one β is , -SR ¹ or -OR ² group, and at least one of the 8 α and β represents a halogen atom and -OR ² group,
R ¹ , R ² and R ³ each independently represent a phenyl group having or not having a substituent, an alkyl group having 1 to 20 carbon atoms, and 7 to 20 carbon atoms. Represents a member selected from the aralkyl groups possessed,
M represents one member selected from one metal atom, one or more hydrogen atoms, one metal oxide, and a metal halide.

When using organic dyes of phthalocyanines as near-infrared absorbers, phthalocyanines often have an absorption peak at a specific wavelength in the near-infrared region. It is necessary to select the kind of class. In order to sufficiently shield the wavelength of 850 nm to 1000 nm required for the plasma display, it is preferable to use two or more kinds of phthalocyanines together.
Although there is no restriction | limiting in particular in content of the phthalocyanines contained in the near-infrared shielding layer 4, It is 0.01-2 g / m < ² > in order to obtain a favorable near-infrared shielding characteristic and visible light transmittance. Preferably, it is 0.1-1 g / m < ² >. If the content is lower than 0.01 g / m ² , sufficient shielding ability in the near infrared region may not be obtained. Conversely, if the content is higher than 2 g / m ² , the transmittance in the visible light region may be low. May decrease significantly.

  As the near-infrared absorber, the above-described tungsten oxide-based near infrared absorber and phthalocyanine-based near infrared absorber may be used in combination. The content and blending ratio in the case of using a tungsten oxide-based near infrared absorber and a phthalocyanine-based near infrared absorber in combination can be appropriately set so as to obtain a desired near-infrared shielding ability and visible light transmittance, What is necessary is just to prepare suitably according to desired performance.

  As the binder resin for the near-infrared shielding layer, a resin having high chemical resistance, in particular, a resin having a high resistance to an electroless plating catalyst layer type ink, an electroless plating bath, and an electrolytic plating bath is used. Preferably, for example, one or more of cellulose derivatives such as ethyl cellulose and propyl cellulose, polyvinyl butyral resin, acrylic resin, polyurethane resin, and rosin ester resin can be used, and two or more kinds may be mixed.

  In addition, as the binder resin, it is particularly preferable to use a resin having moderate flexibility such as a polyvinyl butyral resin. When the near-infrared shielding layer 4 has appropriate flexibility, the electroless plating catalyst ink is transferred from the body plate onto the near-infrared shielding layer 4 in gravure printing suitably used in the following production method of the present invention. At this time, the near-infrared shielding layer 4 follows the image portion (groove) of the body plate sufficiently and can enter the groove, so that the transferability is also improved.

As described above, the near-infrared shielding layer 4 preferably has a function as a receiving layer when the electroless plating catalyst ink is printed, and the electroless plating catalyst ink layer 21 printed according to a predetermined pattern. It is necessary to prevent drooling and bleeding and to improve the adhesion strength between the near-infrared shielding layer 4 and the printed electroless plating catalyst ink layer 21. Therefore, oxide fine particles (hereinafter sometimes referred to as “catalyst ink receptive oxide fine particles”) are added to enhance performance as a receiving layer when printing electroless plating catalyst ink. Is preferred. Examples of such oxide fine particles for receiving a catalyst ink include alumina (Al ₂ O ₃ ), silica (SiO ₂ ), titania (TiO ₂ ), zirconia (ZrO ₂ ), and the like. A mixture of oxide fine particles may also be used. These catalyst ink receiving oxide fine particles preferably have an average particle size of 0.01 μm to 5 μm, more preferably, catalyst ink receiving oxide fine particles having an average particle size of 0.01 μm to 0.1 μm, Dispersion in the near-infrared shielding layer 4 so that the dispersed particle diameter is 0.1 μm or less is preferable because the transparency and adhesion of the obtained near-infrared shielding layer 4 are improved.
The content of the catalyst ink-receiving oxide fine particles in the near-infrared shielding layer 4 is preferably 50% by weight or less. If it exceeds 50% by weight, the transparency of the near-infrared shielding layer 4 is lowered, which is not preferable.

  In the near-infrared shielding layer, the blending ratio of the filler (representing a near-infrared absorber or a mixture of near-infrared absorber and catalyst ink-receiving oxide fine particles) and the binder resin is 90/10 to 10 / in mass ratio. 90 is preferable, and when the ratio of the filler is higher than 90/10, the adhesion strength between the transparent base material 1 and the near-infrared shielding layer 4 is weakened, and the transmittance is lowered to increase the haze value. Sometimes. On the contrary, when the ratio of the filler is lower than 10/90, the adhesion strength is weakened and the effect as the receiving layer of the electroless plating catalyst ink is reduced. When the electroless plating catalyst layer 21 is formed, May cause dripping or bleeding.

  Moreover, it is preferable that the thickness of the near-infrared shielding layer 4 is 0.5-5 micrometers, More preferably, it is 1-3 micrometers. If the near-infrared shielding layer 4 is thinner than 0.5 μm, the effect of the electroless plating catalyst ink as a receiving layer may be insufficient, and the near-infrared shielding layer 4 has a thickness of more than 5 μm. If it is thick, cracks may occur in the electroless plating catalyst layer 21.

Examples of the transparent substrate 1 include a transparent plastic, a transparent plastic board, and glass.
As the material of the transparent plastic and the transparent plastic board, from the viewpoint of optical properties and mechanical properties, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, terephthalic acid-isophthalic acid-ethylene glycol copolymer, terephthalic acid- Polyester resins such as cyclohexanedimethanol-ethylene glycol copolymer, polyamide resins such as nylon 6, polyolefin resins such as polypropylene and polymethylpentene, acrylic resins such as polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer It is preferable to use a styrene resin such as coalescence, a cellulose resin such as triacetyl cellulose, an imide resin, or a polycarbonate resin.

The electroless plating catalyst layer 21 having the mesh pattern includes, for example, oxide fine particles supporting catalytic noble metal ultrafine particles (hereinafter, sometimes referred to as “supporting oxide fine particles”); It is formed by an ink composed of a black pigment and a polymer resin.
Examples of the noble metal ultrafine particles having a catalytic action include palladium (Pd), platinum (Pt), gold (Au) and the like, and two or more kinds of noble metals may be mixed and used.
Examples of the supporting oxide fine particles include alumina (Al ₂ O ₃ ), zinc oxide (ZnO), zirconia (ZrO ₂ ), titania (TiO ₂ ) and the like, and two or more kinds of supporting oxide fine particles. May be mixed.

The mass ratio between the noble metal ultrafine particles and the supporting oxide fine particles is preferably 0.5 / 99.5 to 5/95, more preferably 1/99 to 2/98. If the mass ratio of the precious metal ultrafine particles is lower than 0.5 / 99.5, it may not function as a catalyst for electroless plating. If it is higher than 5/95, a precious metal that is more expensive than necessary is used. This will increase the cost.
Further, by supporting the noble metal ultrafine particles on the supporting oxide fine particles, the thixotropy of the catalyst ink is increased, the printability is improved, and a good printed shape is obtained.

  Examples of the black pigment include carbon black, iron oxide, and titanium black. The content of the black pigment in the electroless plating catalyst layer is preferably 0.03 to 3.0% by mass, more preferably 0.1 to 1.0% by mass. If the content is less than 0.03% by mass, the blackness of the mesh on the back surface of the electroless plating catalyst layer may be insufficient, and when mounted on a display, good contrast may not be obtained. On the other hand, if it is higher than 30% by mass, the blackness of the mesh on the back surface of the electroless plating catalyst layer is good and good contrast can be obtained, but the printability may be insufficient.

The polymer resin contained in the electroless plating catalyst ink may be any resin that is suitable for the printing method used in the production method of the present invention and has high resistance to an alkaline electroless plating solution, such as ethyl cellulose and rosin. An ester resin, an acrylic resin, a polyvinyl butyral resin, a polyurethane resin, or the like can be used, and two or more of these may be mixed and used. Among the above polymer resins, use of ethyl cellulose is suitable for gravure printing.
In addition, the blending ratio of the oxide fine particles supporting the noble metal ultrafine particles and the polymer resin is preferably 40/60 to 80/20, more preferably 60/40 to 70 in terms of mass ratio. / 30. If the ratio of the oxide fine particles is lower than 60/40, the contained precious metal ultrafine particles are almost covered with the polymer resin, and may not function as a catalyst for electroless plating. Printability may be poor, and curing of the near-infrared shielding layer by the polymer resin and adhesion with the near-infrared shielding layer may be insufficient.

  There is no limitation on the shape of the mesh porosity of the electroless plating catalyst layer in the mesh pattern, for example, a triangle including a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a parallelogram, Other polygons including rhombuses, trapezoids, etc., hexagons, octagons, dodecagons, etc., circles, ellipses, etc., any one of these repeating patterns, or these A combination of two or more of these can also be used.

Electroless plating by an electroless plating method is performed on the electroless plating catalyst layer 21 having the mesh pattern to form an electroless metal plating layer 22. Examples of the metal constituting the electroless plating layer 22 include copper (Cu) and nickel (Ni).
If necessary, an electrolytic plating layer 23 having a desired thickness is formed on the electroless plating layer 22 by an electrolytic plating method in order to further enhance the ability to effectively shield electromagnetic waves. Examples of the metal constituting the electrolytic plating layer 23 include copper (Cu) and nickel (Ni).
The total thickness of the electroless plating layer 22 and the electrolytic plating layer 23 is preferably 30 μm or less, and more preferably 1 μm or more and 5 μm or less.
The outer surface portion of the metal mesh pattern layer for shielding electromagnetic waves is preferably a black layer in order to suppress reflection of visible light and increase contrast to improve visibility.

In this way, the electromagnetic wave shielding mesh layer in the near-infrared / electromagnetic wave shielding laminate 10 has the electroless plating layer 22 on the surface of the electroless plating catalyst layer 21 as a first conductive layer by electroless plating. The second conductive layer is formed and, if necessary, formed by electrolytic plating as an electroplating layer.
In the mesh structure constituted by the metal wire of the conductive electromagnetic wave shielding mesh layer, the interval between the metal wires is usually about 100 to 500 μm, and the metal line width is usually preferably about 10 to 80 μm, more preferably, The line spacing is about 125-500 μm and the line width is about 10-40 μm. When the distance between the metal lines is larger than 500 μm, the mesh pattern tends to be noticeable and the visibility of the display screen tends to be lowered. On the other hand, when the distance is smaller than 100 μm, the mesh pattern becomes fine and visible. The light transmittance may be reduced, and the display screen may tend to be dark.

  Further, if the metal line width exceeds about 80 μm, the mesh pattern tends to be noticeable and the visibility of the display screen tends to be reduced, and the mesh pattern with the metal line width less than about 10 μm is difficult to form. Therefore, the metal line width is usually preferably 10 μm or more and 80 μm or less. The thickness of the metal wire is preferably about 1 μm or more, but is usually preferably about 30 μm or less. If the thickness of the metal wire is less than about 1 μm, electromagnetic wave shielding may be insufficient, and if the line spacing is adjusted to make the brightness (light transmittance) the same, printing becomes difficult. It is preferable to set the metal line width to about 40 μm or less and narrow the metal line interval because the electromagnetic wave shielding ability is increased. In the case of a pattern other than a square, the line spacing is a value converted to a square, and this is obtained from the measured values of the metal line width and light transmittance.

If necessary, a functional layer 5 may be laminated on the electromagnetic wave shielding mesh layer 3 via an adhesive layer 6 as shown in FIG. In order to provide the near-infrared / electromagnetic wave shielding laminate 10 with other functions that cannot be realized from the above-described layer configuration, such as improvement of the optical properties of the shielding laminate 10, protection function, and improvement of mechanical strength. belongs to. Specific examples of the functional layer 5 include known functional layers such as an antireflection functional layer, an antiglare functional layer, a neon light shielding functional layer, an ultraviolet absorbing functional layer, and a hard coat layer for preventing scratches. Can do.
In addition, the said functional layer 5 is laminated | stacked through the adhesion layer 6 on the back surface of the said transparent base material 1, ie, the other main surface of the transparent base material 1 where the near-infrared shielding layer 4 is not laminated | stacked. It may be.

There is no restriction | limiting in particular in the adhesive which comprises the said adhesion layer 6, Although it has moderate adhesiveness, transparency, applicability | paintability from what is conventionally used as a well-known adhesive, tungsten oxide type and / or Those that react with the phthalocyanine-based near-infrared absorber and do not affect the transmission spectrum in the near-infrared and visible light regions can be appropriately selected and used.
Examples of such pressure-sensitive adhesives include acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and polyester-based pressure-sensitive adhesives, and acrylic pressure-sensitive adhesives having good light resistance are particularly preferable.

  Because the near infrared / electromagnetic wave shielding laminate having the above-described configuration uses a tungsten oxide-based and / or phthalocyanine-based near infrared absorber having excellent acid resistance and alkali resistance as a near infrared absorber. In the near-infrared shielding property and visible light transmittance, the transmittance in the near-infrared region of 850 nm to 1000 nm is 10% or less, and the total light transmittance is 40%. In addition, the electromagnetic wave shielding performance at 30 to 1000 MHz has an excellent performance of 50 dB or more, and has an excellent low price, and is mounted on a plasma display or the like. It can be suitably used as an optical filter.

"Production method of near infrared / electromagnetic wave shielding laminate"
The method of the present invention for producing the near infrared / electromagnetic wave shielding laminate of the present invention comprises, on one main surface of a transparent substrate, a tungsten oxide-based and / or phthalocyanine-based near-infrared absorber, a binder resin, Applying a near-infrared shielding composition containing the near-infrared absorber and a solvent for dissolving or dispersing the binder resin, drying the coating film, and laminating a near-infrared shielding layer, and this near-infrared ray On the shielding layer, electroless plating catalyst ink is printed in a mesh shape, and dried if necessary to form an electroless plating catalyst layer. The electroless plating catalyst layer is subjected to electroless plating. An electromagnetic shielding metal mesh layer forming step of forming a mesh-like electroless plating layer. If necessary, the mesh-like electroless plating layer is subjected to electrolytic plating to form a mesh. Forming a Interview shaped electrolytic plating layer is added.

Hereafter, the manufacturing method of the laminated body for near infrared rays and electromagnetic wave shielding is explained in full detail for every process.
Preparation of near-infrared shielding composition Tungsten oxide-based and / or phthalocyanine-based near-infrared absorber, binder resin and, if necessary, oxide fine particles, the above-mentioned near-infrared absorber, binder resin and oxide fine particles Is mixed with a solvent that dissolves or disperses to prepare a near-infrared shielding composition.
The mixing method is not particularly limited, and various conventionally known mixing methods can be appropriately employed.

There are no particular restrictions on the amount of the tungsten oxide-based near infrared absorber, binder resin, and oxide fine particles for catalyst ink in the near infrared shielding composition, and a near infrared shielding layer having desired characteristics can be obtained. May be set as appropriate.
Solvents used in the near-infrared shielding composition include aromatic solvents such as toluene and xylene, cyclized aliphatic solvents such as cyclohexanone, ketone solvents such as methyl ethyl ketone (MEK), and alcohol solvents such as isopropyl alcohol. It is possible to disperse the near-infrared absorbent and the oxide fine particles for the catalyst ink, and there is no particular limitation as long as the binder resin can be dissolved. Further, in order to facilitate the dispersion of the oxide fine particles for the catalyst ink, a phosphate ester type dispersant may be added.

Form of near-infrared shielding layer The near-infrared shielding composition is applied onto one main surface of a transparent substrate, the coating film is dried, and a near-infrared shielding layer is formed and laminated on one main surface of the transparent substrate. .

As a coating method for applying the near-infrared shielding composition on one main surface of the transparent substrate, conventionally known coating methods such as gravure printing, bar coating printing, and offset printing can be employed.
The method for drying the coating film is not particularly limited, and it is preferable to dry until the amount of the solvent remaining in the near-infrared shielding layer is 3% by mass or less, preferably 1% by mass or less. If the amount of solvent remaining in the near-infrared shielding layer exceeds 3% by mass, long-term near-infrared shielding properties may be deteriorated.

Formation of Electroless Plating Catalyst Layer An electroless plating catalyst ink is printed on the near-infrared shielding layer with a desired mesh pattern, and dried if necessary to form a meshed electroless plating catalyst layer.
The electroless plating catalyst ink includes, for example, oxide fine particles on which noble metal ultrafine particles having a catalytic action are supported, a black pigment, a polymer resin, and a solvent, as described above.

  Examples of the organic solvent for the electroless plating catalyst ink include toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), butyl acetate, cyclohexanone, butyl carbitol, butyl carbitol acetate, α-terpineol, and the like. There is no particular limitation as long as the polymer resin can be dissolved and the printing method used is appropriate.

  The viscosity of the electroless plating catalyst ink is preferably 1 to 500 Pa · s, more preferably 50 to 200 Pa · s. When the viscosity of the electroless plating catalyst ink is higher than 500 Pa · s, the electroless plating catalyst ink cannot be uniformly supplied in gravure printing suitably used in the production method of the present invention, and printing unevenness is caused. May occur. On the other hand, if the viscosity of the electroless plating catalyst ink is lower than 1 Pa · s, the thixotropy of the electroless plating catalyst ink may be insufficient, resulting in stringing and the like, and a good printed shape may not be obtained. .

  The content of the polymer resin in the electroless plating catalyst layer is preferably 1 to 15% by mass, more preferably 6 to 10% by mass. If the content of the polymer resin is more than 15% by mass, the viscosity of the electroless plating catalyst ink may become too high, and printing may be difficult. The content of the polymer resin is more than 1% by mass. If it is low, the viscosity of the electroless plating catalyst ink becomes too low, which may also be unsuitable for printing.

  As a method of printing the electroless plating catalyst ink in a mesh form on the near-infrared shielding layer, it is preferable to use a gravure printing method, and the electroless plating catalyst ink on the plate cylinder for ravia printing is used. The method for transferring the electroless plating catalyst to the near-infrared absorbing layer by pressing the near-infrared shielding layer on the transparent substrate, for example, for 0.5 to 10 seconds, that is, using a gravure direct printing method. Is preferred.

  FIG. 3 is an explanatory diagram for explaining an outline of such a gravure direct printing method. In FIG. 3, the gravure direct printing machine 30 includes a first backup roll 31, a gravure plate 32, a doctor blade 33, and a second backup rule 34. By adjusting the positions of the first and second backup rolls 31 and 34 according to the printing speed so as to obtain a fixed pressure bonding time, the gravure plate 32 can be used without using a transfer sheet (ie, a blanket). It is possible to directly transfer the electroless catalyst ink 36 onto the near-infrared shielding layer 35 on the transparent substrate to form the electroless plating catalyst layer 38.

  If the pressure-bonding time is shorter than 0.5 seconds, the absorption of the solvent into the near-infrared shielding layer is insufficient, and the viscosity of the electroless plating catalyst ink filled in the groove of the plate is not increased. Pulling or the like may occur and a good printed shape may not be obtained. If the pressure bonding time is longer than 10 seconds, the solvent is absorbed too much, the viscosity of the electroless plating catalyst ink becomes too high, and it becomes difficult to transfer the electroless plating catalyst ink onto the near-infrared shielding layer. Sometimes.

By adopting such a gravure direct printing method, the transferability and transfer rate of the electroless plating catalyst ink to the near-infrared shielding layer are improved.
In addition, by adjusting the groove depth of the gravure plate, it is possible to print a thicker ink layer compared to normal gravure printing using a blanket, and the amount of addition per unit area of the catalyst Increases, thereby facilitating metal deposition by electroless plating.
Furthermore, since the electroless plating catalyst ink is transferred without using a transfer sheet (that is, a blanket), a mesh pattern in which lattice lines constituting the mesh are continuous can be formed. Manufacturing yield is improved.

Further, according to such a gravure direct printing method, the solvent in the electroless plating catalyst ink filled in the groove of the gravure plate is bonded to the receiving layer by pressing the gravure plate and the near-infrared shielding layer for a certain period of time. The viscosity of the electroless plating catalyst ink that is absorbed in a certain near-infrared shielding layer increases rapidly, so that the electroless plating catalyst ink filled in the groove maintains the image shape of the gravure plate as it is, Transferred to the near infrared shielding layer side.
The solvent absorbed in the near infrared shielding layer once dissolves the binder resin on the surface of the near infrared shielding layer, and the dissolved binder resin layer and the printed catalyst ink layer for electroless plating are compatible at the interface. Therefore, the adhesion strength between the near-infrared shielding layer and the electroless plating catalyst layer after drying is increased. When drying after printing, it is preferably performed at 100 ° C. or lower in consideration of dry cracking of the printed electroless plating catalyst layer.

  By adopting such a gravure direct printing method, a fine pattern with a line width of about 10 to 20 μm is shielded at high speed, for example, at a high speed of about 30 m / min, while maintaining the designed image shape, and near-infrared shielding. Can be printed on the layer.

Shape of electroless metal plating layer On the mesh-like electroless plating catalyst layer, electroless plating is performed to form a mesh-like electroless plating layer.
As the electroless plating used in the method of the present invention, a conventionally known electroless plating method can be employed. For example, a catalyst layer for electroless plating in a mesh form in an electroless copper plating bath or a nickel plating bath. Deposit metal on top.

Electrolytic metal plating layer shape Electrolytic plating is performed on the mesh-like electroless metal plating layer as necessary to form an electrolytic metal plating layer, further improving the conductivity of the electromagnetic wave shielding layer and its electromagnetic shielding effect Can be increased.
As an electroplating method, a conventionally known electroless plating method can be adopted. As a metal to be deposited on the electroless plating layer, for example, copper or nickel is used, and an electrolysis metal excellent in conductivity and durability. A plating layer can be formed.

The outermost surface portion of the electromagnetic shielding metal mesh layer manufactured by the above-described method is preferably a black layer in order to suppress the reflection of visible light and increase the contrast to improve the visibility. In order to form a black layer on the outermost surface portion, a method of covering with a black metal layer or a black electrodeposition layer, a blackening method by oxidation or sulfuration treatment, or the like can be employed.
To coat with a black metal layer, for example, black nickel plating treatment or chromate plating treatment, black ternary alloy plating treatment using tin, nickel and copper, black ternary alloy plating treatment using tin, nickel and molybdenum, etc. That's fine.

  The black electrodeposition layer is a black layer provided by electrodeposition, and can be formed, for example, by electrodeposition using a black paint in which a black pigment is dispersed in an electrodeposition resin. it can. Examples of the black pigment include carbon black, and it is preferable to use a conductive black pigment. The electrodeposition resin may be an anionic resin or a cationic resin, and specifically, an acrylic resin, a polyester resin, an epoxy resin, etc., these electrodeposition resins are respectively It can be used alone or in combination of two or more. Furthermore, the metal surface can be blackened by oxidation treatment or sulfuration treatment. The oxidation treatment and sulfurization treatment for blackening can be performed by known methods, respectively.

  According to the method for producing a near-infrared / electromagnetic wave shielding laminate of the present invention, as a near-infrared absorber, a tungsten oxide-based and / or phthalocyanine-based near-infrared absorber excellent in acid resistance and alkali resistance is used. The metal mesh film can be formed with a fine pattern as designed by electroless plating using an inexpensive printing method with excellent mass productivity. A near-infrared / electromagnetic wave shielding laminate having excellent light transmittance and excellent electromagnetic shielding properties can be produced at low cost.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

(Example 1)
As a tungsten oxide-based near infrared absorber, a tungsten composite oxide (Cs _0.33 WO _x (where x = 2.2 to 2.99)) dispersion (solid content: 18.5) manufactured by Sumitomo Metal Mining Co., Ltd. Mass%) was used.
After 240 g of polyvinyl butyral was dissolved in 1800 g of methyl ethyl ketone, 1297 g of the obtained tungsten composite oxide dispersion and 552 g of cyclohexanone were added to 2111 g of toluene and mixed with a homogenizer to prepare a near-infrared shielding paint.
The obtained near-infrared shielding coating was applied to a 125 μm-thick PET film by microgravure printing, dried in air at a temperature of 120 ° C. for 2 minutes, and laminated on the PET film. A near infrared shielding PET film having a 2 μm near infrared shielding layer was obtained.

  Next, 3.5 g of palladium ultrafine particles and 171.5 g of γ-alumina fine particles are dispersed and agglomerated in alcohol, separated into solid and liquid, dried, and γ carrying the palladium ultrafine particles. -Alumina fine particles were obtained. On the other hand, 90 g of ethyl cellulose resin was dissolved in a mixed solution of 472 g of α-terpineol and 236 g of butyl carbitol acetate, and then γ-alumina fine particles supporting the above-mentioned ultrafine palladium particles and 9 g of carbon black were added thereto. Then, they were mixed and dispersed by a three roll mill to prepare a catalyst ink for electroless plating.

  The obtained electroless plating catalyst ink was printed on the near-infrared shielding layer of the above-mentioned near-infrared shielding PET film by a gravure printing method of FIG. A catalyst layer for electroless plating was formed by printing on a mesh pattern of L / pitch S = 20/280 μm, and this was dried in an air atmosphere at a temperature of 80 ° C. for 5 minutes. A near-infrared shielding PET film in which the electroless plating catalyst layer was laminated on the near-infrared shielding layer was obtained. The shape of the obtained printing mesh was very good and there was no problem in appearance.

  The near-infrared shielding PET film on which the electroless plating catalyst layer is laminated is immersed in an electroless copper plating solution, OPC-750, manufactured by Okuno Pharmaceutical Co., Ltd. for 40 minutes at 25 ° C. Copper was deposited on the electroless plating catalyst layer. Nickel / tin alloy plating was applied to the surface of the electroless copper plating layer of the resulting mesh pattern to blacken it. A laminate for shielding near infrared rays and electromagnetic waves was obtained.

The near infrared / electromagnetic wave shielding laminate of Example 1 was evaluated. The evaluation results are shown in Table 1. Evaluation items and evaluation methods are as follows.
(1) Appearance observation: The near-infrared / electromagnetic wave shielding laminate was visually observed, and a mesh-like pattern with no disconnection, bleeding, or discoloration was evaluated as “no problem”. Discoloration ”was evaluated.
(2) Line width L / pitch S: Observed with an optical microscope, the line width L and the pitch S were measured at 10 locations, and the average line width L / pitch S was calculated.
(3) Sheet resistance: Measured according to the measurement method defined in JIS K-7194 “Resistivity test method of conductive plastics by 4-probe method”.
(4) Optical characteristics: Total light transmittance, transmittance at 850 nm and 950 nm, and transmission spectrum were measured using a spectrophotometer (UV / VIS / NIR Spectrometer V-570) manufactured by JASCO Corporation.
The transmission spectrum data of the laminate for shielding near infrared rays and electromagnetic waves of Example 1 is shown in FIG.

(Example 2)
A near-infrared shielding PET film was produced in the same manner as in Example 1. However, 60 g of alumina (catalyst ink accepting oxide fine particles) powder and 7 g of a phosphoric acid ester-based dispersant were placed in 333 g of toluene, an alumina dispersion was prepared by a sand mill, and 240 g of polyvinyl butyral was dissolved in 1800 g of methyl ethyl ketone. 1297 g of the tungsten composite oxide dispersion, 552 g of the alumina dispersion, 552 g of cyclohexanone, and 1711 g of toluene were added and mixed with a homogenizer to prepare a near-infrared shielding paint.

Next, in the same manner as in Example 1, a near-infrared shielding PET film in which the electroless plating catalyst layer was laminated on the near-infrared shielding layer was produced. The shape of the obtained printing mesh was very good and there was no problem in appearance.
A near-infrared / electromagnetic wave shielding laminate was produced from the near-infrared shielding PET film having the electroless plating catalyst layer in the same manner as in Example 1. This near infrared / electromagnetic wave shielding laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 3)
In the same manner as in Example 1, a near infrared / electromagnetic wave shielding laminate was produced. However, IR-10A (manufactured by Nippon Shokubai), TX-EX-906B (manufactured by Nippon Shokubai), TX-EX-910B (manufactured by Nippon Shokubai) are used as phthalocyanine-based near infrared absorbers, and IR-10A 16. 8 g, 9 g of TX-EX-906B, and 15 g of TX-EX-910B were dissolved in 1200 g of methyl ethyl ketone to prepare a phthalocyanine solution. Further, 60 g of alumina powder (catalyst ink accepting oxide fine particles) and 7 g of a phosphoric acid ester-based dispersant were placed in 333 g of toluene, and an alumina dispersion was prepared by a sand mill.
Also, 240 g of polyvinyl butyral is dissolved in 1800 g of methyl ethyl ketone, and the phthalocyanine solution, the alumina dispersion, 552 g of cyclohexanone, and 1767.2 g of toluene are added to this solution and mixed uniformly to prepare a near infrared shielding coating. did.
Using this near infrared shielding paint, a near infrared shielding PET film was produced in the same manner as in Example 1.

Next, in the same manner as in Example 1, a near-infrared shielding PET film in which an electroless plating catalyst layer was laminated on a near-infrared shielding layer was produced. The shape of the obtained printing mesh was very good and there was no problem in appearance.
Further, in the same manner as in Example 1, a near-infrared / electromagnetic wave shielding laminate was produced from the near-infrared shielding PET film with an electroless plating catalyst layer. This near-infrared / electromagnetic wave shielding laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 4
In the same manner as in Example 1, a near infrared / electromagnetic wave shielding laminate was produced. However, on the electroless plating layer of the near infrared / electromagnetic wave shielding laminate, an electrolytic copper plating solution, Top Lucina SF, manufactured by Okuno Pharmaceutical Co., Ltd., and a condition of 3 A / dm ² for 5 minutes at a temperature of 25 ° C. Underneath was copper electroplated. Further, a nickel / tin alloy plating was applied on the copper electroplating layer to blacken the mesh surface to obtain a near infrared / electromagnetic wave shielding laminate.
This near infrared / electromagnetic wave shielding laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 5)
A near infrared / electromagnetic wave shielding laminate was prepared and evaluated in the same manner as in Example 4. However, the line width L / pitch S of the mesh pattern electroless plating catalyst layer was changed to 10/290 μm. The evaluation results are shown in Table 1.

(Example 6)
A near infrared / electromagnetic wave shielding laminate was prepared and evaluated in the same manner as in Example 14. However, the alumina powder in the electroless plating catalyst ink was changed to zirconia powder, the line width L / pitch S of the electroless plating catalyst layer in the mesh pattern was changed to 10/290 μm, and the printing speed Was changed to 20 m / min. The evaluation results are shown in Table 1.

(Comparative Example 1)
A near infrared / electromagnetic wave shielding laminate was produced and evaluated in the same manner as in Example 1. However, a diimonium dye CIR-1085 (manufactured by Nippon Carlit) was used as a near-infrared absorbing material, and 36 g of CIR-1085 was dissolved in 1200 g of methyl ethyl ketone to prepare a diimonium solution. Further, 60 g of alumina powder and 7 g of a phosphoric acid ester-based dispersant were placed in 333 g of toluene, and an alumina dispersion was prepared by a sand mill. Further, 240 g of polyvinyl butyral was dissolved in 1800 g of methyl ethyl ketone, and then the diimonium solution, the alumina dispersion, 552 g of cyclohexanone, and 1772 g of toluene were added and mixed to prepare a near-infrared shielding paint.
Using this near-infrared shielding coating, a near-infrared / electromagnetic wave shielding laminate was produced in the same manner as in Example 1. In this near-infrared / electromagnetic wave shielding laminate, the near-infrared shielding layer is discolored, resulting in appearance defects. Table 1 shows the evaluation results.

  As is clear from Table 1, the near-infrared / electromagnetic wave shielding laminates of Examples 1 to 6 have no deterioration of the near-infrared absorber and have a problem in appearance (discoloration) compared to that of the comparative example. It was confirmed that it did not occur and had excellent optical properties (low transmittance at wavelengths of 850 nm and 950 nm, that is, good shielding properties in the near infrared region).

Cross-sectional explanatory drawing of an example of the laminated body for near infrared rays and electromagnetic wave shielding of this invention. Cross-sectional explanatory drawing of the principal part of an example of the laminated body for near infrared rays and electromagnetic wave shielding of this invention. Explanatory drawing which shows the structure of the gravure direct printing-like structure used for printing of the electroless-plating catalyst ink in an example of the manufacturing method of the laminated body for near-infrared rays and electromagnetic wave shielding of this invention. The plane scoring figure which shows an example of the mesh pattern of the electromagnetic wave shielding layer of the laminated body for near-infrared electromagnetic wave shielding of this invention. The diagram which shows the transmission spectrum of an example (Example 1) of the laminated body for near-infrared rays and electromagnetic wave shielding of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Laminated body for near-infrared / electromagnetic wave shielding 2 Transparent base material 3 Electromagnetic wave shielding metal mesh layer 4 Near-infrared shielding layer 5 Functional layer 6 Adhesive layer 21 Electroless plating catalyst layer 22 Electroless plating layer 23 Electrolytic plating layer 30 Gravure direct Printer 31 First backup roll 32 Gravure plate 33 Doctor blade 34 Second backup roll 35 Transparent base material with near-infrared shielding layer 36 Electroless plating catalyst ink 37 Pressure bonding year 38 Electroless plating catalyst ink layer

Claims (7)

A near-infrared ray comprising a transparent base, a near-infrared shielding layer formed on one main surface of the transparent base, and an electromagnetic shielding metal mesh layer formed on the near-infrared shielding layer. An electromagnetic wave shielding laminate,
The near-infrared shielding layer contains a tungsten oxide-based and / or phthalocyanine-based near infrared absorber, and a binder resin.
The electromagnetic shielding metal mesh layer is formed by performing electroless plating on a mesh-like electroless plating catalyst layer formed on the near infrared shielding layer. Laminated body for electromagnetic wave shielding.   2. The near infrared / electromagnetic wave shielding laminate according to claim 1, wherein the electromagnetic shielding metal mesh layer is formed by performing electroless plating and then electrolytic plating.   Near-infrared light containing a tungsten oxide-based and / or phthalocyanine-based near-infrared absorber, a binder resin, and a solvent for dissolving or dispersing the near-infrared absorber and the binder resin on one main surface of the transparent substrate. A step of forming a near-infrared shielding layer by applying and drying the shielding composition, and then printing a catalyst ink for electroless plating on the near-infrared shielding layer in a mesh shape to form a catalyst layer for electroless plating And forming a meshed electroless plating layer by applying electroless plating on the meshed electroless plating catalyst layer, and forming an electromagnetic shielding metal mesh layer. A method for producing a laminate for shielding near infrared rays and electromagnetic waves.   The near-infrared / electromagnetic wave shielding according to claim 3, further comprising: forming a mesh-like electrolytic plating layer by performing electrolytic plating on the mesh-like electroless plating layer in the electromagnetic shielding metal mesh layer forming step. Method for manufacturing a laminated body.   The method for producing a near-infrared / electromagnetic wave shielding laminate according to claim 3, wherein in the electromagnetic shielding metal mesh layer forming step, the electroless plating catalyst ink is printed using a gravure printing method.   Printing of the electroless plating catalyst ink by the gravure printing method fills the groove on the gravure printing cylinder with the electroless plating catalyst ink in a mesh shape, and the near infrared ray on the transparent substrate The shielding layer is applied by pressure-bonding for a predetermined time, thereby transferring the electroless plating catalyst on the plate cylinder onto the near-infrared absorbing layer without using a transfer sheet (blanket). Item 6. A method for producing a laminate for shielding near infrared rays and electromagnetic waves according to Item 5.   The method for producing a near-infrared / electromagnetic wave shielding laminate according to claim 6, wherein the predetermined pressure-bonding time in the transfer of the electroless plating catalyst is 0.5 seconds to 10 seconds.