CN101869010A

CN101869010A - Method for forming image, method for manufacturing light-transmissive electromagnetic shielding material, and light-transmissive electromagnetic shielding material

Info

Publication number: CN101869010A
Application number: CN200880117109A
Authority: CN
Inventors: 船木竜也; 小坪秀史; 笹木清美; 竹之内秀章; 岩渊芳典
Original assignee: Bridgestone Corp
Current assignee: Bridgestone Corp
Priority date: 2007-11-20
Filing date: 2008-11-11
Publication date: 2010-10-20
Also published as: KR20100082793A; JP2009129969A; WO2009066584A1

Abstract

A method for easily forming a mesh-like image free of disconnection and a method for easily manufacturing a light-transmissive electromagnetic shielding material having a mesh-like conductive layer free of disconnection and an excellent electromagnetic shielding ability are provided. The image forming method comprises a step of forming a mesh-like image by forming a pattern on a base with an image-forming ink by intaglio printing using a cylinder having a mesh-like pattern of the recesses in the surface of the cylinder. The image forming method is characterized in that the areas of the bottoms of the recesses at the intersections of the mesh of the mesh-like pattern are reduced. The light-transmissive electromagnetic shielding material manufacturing method comprises a step of forming a mesh-like pretreating layer by forming a pattern on a transparent base with an electroless plating pretreating agent by intaglio printing using a cylinder having a mesh-like pattern of the recesses in the surface of the cylinder and a step of forming a mesh-like metal conductive layer on the pretreating layer by electroless plating. The manufacturing method is characterized in that the areas of the bottoms of the recesses at the intersections of the mesh of the mesh-like pattern on the cylinder are reduced.

Description

The manufacture method of image forming method, light-transmitting electromagnetic shielding material and light-transmitting electromagnetic shielding material

Technical field

The present invention relates to the manufacture method and the light-transmitting electromagnetic shielding material of image forming method and light-transmitting electromagnetic shielding material, this image forming method can advantageously utilize the formation that needs the conductive layer of employed light-transmitting electromagnetic shielding material in the window of building of electromagnetic wave shielding in the front filter of plasma display (PDP), hospital etc.

Background technology

In recent years, large scale display becomes the main flow of display, and as large screen display device, LCD and PDP popularize just gradually.Compare with LCD, PDP has advantages such as response speed is fast.Yet, among this PDP, owing to carry out the high-frequency pulse discharge at illuminating part for image shows, therefore might the unwanted electromagnetic wave of radiation, radiation becomes the infrared ray of reason of the faulty operation of infrared remote controller etc., therefore, to prevent that these from being purpose, the various PDP filters (electromagnetic wave shielding performance light inlet window material) of conductivity have been proposed to have at PDP.As the conductive layer of this electromagnetic wave shielding performance light inlet window material, known for example have: (1) contains the transparent conductive film of argent; (2) make netted metal wire or conducting fibre and conductive mesh that obtain; (3) the layer etching and processing such as Copper Foil on the transparent membrane are reticulated, and be provided with the material of peristome; (4) on transparent membrane, the conductivity ink print reticulated and material of obtaining or the like.

Yet the transparent conductive film of (1) can't obtain sufficient conductivity, and there is the shortcoming that can't obtain good light transmittance usually in the conductive mesh of (2).Owing to utilize the etching and processing of (3) and the netted conductive layer that (4) pattern printing can form expectation, therefore compare with the conductivity net, it is big that the degree of freedom of live width, spacing, shape of a mesh significantly becomes, and also can form to have that live width 200 μ m are following, fine rule and the aperture opening ratio high netted conductive layer of aperture opening ratio more than 75%.But (3) exist in and need equipment in the etching and processing and that operation is numerous and diverse, cost is high is unfavorable.On the other hand, (4) netted pattern printing especially easily and help forming above-mentioned conductive layer, as long as form conductivity print film, can obtain good light transmittance, and can prevent moore phenomenon (moire phenomenon) with the thick conductive layer of such fine rule and mesh.

The for example record to some extent in patent documentation 1 (Japan Patent the 3017988th) of the manufacture method of above-mentioned conductive layer.The conductivity ink print that the intaglio plate hectographic printing of the cylinder of this method by having used black release property excellence will contain metal dust and resin forms the pattern of specific dimensions to the surface of transparency carrier, make this pattern cured then, then only be provided with metal film coated on the surface of aforementioned pattern by plating.Promptly, pattern (conduction overlay film) to the specific dimensions that carried out the intaglio plate hectographic printing applies plating, thereby eliminates the possibility of deviation that produce, pattern line-width, broken string etc. when utilizing existing silk screen print method, pattern below the gravure processes printing live width 50 μ m.

Patent documentation 1: Japan Patent the 3017988th

Summary of the invention

The problem that invention will solve

Yet, according to the inventor's research as can be known, even if when utilizing intaglio printing as described above to form the layer of netted conductivity China ink, also might form the layer of conductivity China ink in the intersection point portion of grid well, also can't obtain sufficient conductivity even if on such layer, apply plating.

Therefore, the objective of the invention is to, the image forming method that forms the network diagramming picture that does not have broken string easily is provided.

In addition, the objective of the invention is to, the manufacture method of light-transmitting electromagnetic shielding material is provided, it can be made easily has the netted conductive layer that does not have broken string, the light-transmitting electromagnetic shielding material of excellent electromagnetic wave shielding performance.

The present invention also aims to, the manufacture method of light-transmitting electromagnetic shielding material is provided, this manufacture method can be made following light-transmitting electromagnetic shielding material easily, and it has netted conductive layer and the aperture opening ratio height that does not have broken string, thereby electromagnetic wave shielding performance, light transmission and visual excellence.

The present invention also aims in addition, above-mentioned the have netted conductive layer that does not have broken string, the light-transmitting electromagnetic shielding material of excellent electromagnetic wave shielding performance are provided.

The scheme that is used to deal with problems

The invention reside in a kind of image forming method, it comprises following operation:

By the pattern of recess that uses the surface is the intaglio printing of netted cylinder, image is formed with patterns of material print surface to substrate, forms the network diagramming picture, it is characterized in that,

The area of bottom in the intersection point part of the grid of the net-like pattern of cylinder surface, recess is reduced.

Below list the preferred version of the image forming method of the invention described above.

(1) surface configuration of protuberance before the area of the concave bottom reduction, net-like pattern is a quadrangle, and the prolongation on the summit by tetragonal angle, and the area of intersection point bottom in partly, recess is reduced.The disappearance of the image in the intersection point part of the image that obtains thus, significantly reduces or disappears.

(2) distance (L) between the summit at tetragonal angle in the above-mentioned intersection point part, relative is 30 μ m following (especially being 10～30 μ m).For making the disappearance of the image in the intersection point part of resulting image significantly reduce or disappearing effective especially.

(3) in the above-mentioned intersection point part, relative tetragonal bight has the shape of the isosceles triangle of acute angle, and the length on its base (a) is 30 μ m following (especially being 10～30 μ m).For making the disappearance of the image in the intersection point part of resulting image significantly reduce or disappearing especially effective.

(4) intaglio printing is photogravure or heliogravure hectographic printing (Gravure offset printing).Can carry out the high printing of precision.

In addition, the present invention also is a kind of manufacture method of light-transmitting electromagnetic shielding material, it is characterized in that, this manufacture method comprises:

By the pattern of recess that uses the surface is that the intaglio printing of netted cylinder is printed the operation that forms netted preprocessing layer to the surface of transparency carrier with chemical plating pretreating reagent pattern; And

On preprocessing layer, utilize chemical plating to handle and form the operation of netted metal conducting layer,

Wherein the area of bottom in the intersection point of the grid of the net-like pattern of the cylinder surface part, recess is reduced.

Below list the preferred version of manufacture method of the light-transmitting electromagnetic shielding material of the invention described above.

(1) the chemical plating pretreating reagent is the liquid that comprises composite metal oxide and/or composite metal oxide hydrate and synthetic resin.Particularly suitable in said method.

(2) the chemical plating pretreating reagent is for comprising silane coupler and the mixture of azoles (azole) based compound or the liquid of product and precious metal chemical complex.

(3) carry out also electroplating after the chemical plating.Can obtain excellent conductivity.

The preferred version of aforementioned image forming method (1)～(4) are also applicable to this manufacture method.

And then the present invention also is a kind of manufacture method of light-transmitting electromagnetic shielding material, and this manufacture method comprises following operation:

By the pattern of recess that uses the surface is the intaglio printing of netted cylinder, and the conductivity China ink pattern that will contain metal particle and resin glue prints the surface to transparency carrier, forms netted conductive layer, it is characterized in that,

(1) at the enterprising electroplating of above-mentioned netted conductive layer.

And then the present invention also is a kind of light-transmitting electromagnetic shielding material, it is characterized in that, the netted metal conducting layer that have transparency carrier, is provided with thereon, and,

The area of the intersection point part of the grid of net-like pattern is reduced.

Below list the preferred version of the light-transmitting electromagnetic shielding material of the invention described above.

(1) is provided with netted preprocessing layer between transparency carrier and the metal conducting layer.

(2) intersection point of grid part be shaped as quadrangle, and by tetragonal corner recess, the area of bottom in the intersection point part, recess is reduced.

Light-transmitting electromagnetic shielding material of the present invention and the light-transmitting electromagnetic shielding material that utilizes aforementioned manufacture method of the present invention to obtain can be advantageously used in display filter, especially the plasma display filter.

The invention effect

In the image forming method of the present invention, the pattern of the recess on the surface of the cylinder that intaglio printing is used (pattern) is netted, and the area of bottom in the intersection point part of its grid, recess is reduced.Thus, in the netted image that printing obtains,, therefore can obtain grid image clearly in the damaged basic disappearance of its intersection point parts of images.

Because the manufacture method of light-transmitting electromagnetic shielding material of the present invention is utilized above-mentioned image forming method, therefore the netted conductive layer that forms thus is in the damaged basic disappearance of its intersection point partially conductive layer, thereby the intersection point portion of netted conductive layer not have to break substantially.Therefore, the light-transmitting electromagnetic shielding material that obtains like this has excellent conductivity, and good surface appearance is provided.In addition,, therefore the live width of grid can be reduced, thereby excellent electromagnetic wave shielding performance and aperture opening ratio height, the i.e. light-transmitting electromagnetic shielding material of transparency excellence can be obtained having owing to there is not broken string.

Therefore, the light-transmitting electromagnetic shielding material that utilizes manufacture method of the present invention to obtain can be to have excellent electromagnetic wave shielding performance and aperture opening ratio height, the i.e. material of transparency excellence.

Description of drawings

Fig. 1 is the schematic cross-section of 1 example that is used to illustrate the manufacture method of light-transmitting electromagnetic shielding material of the present invention.

Fig. 2 is the figure of pattern of the recess on expression cylinder 11 surfaces.

Fig. 3 is the part enlarged drawing of pattern of the recess of Fig. 2.

Fig. 4 is the schematic cross-section of representational 1 example of the manufacture method of expression light-transmitting electromagnetic shielding material of the present invention.

Fig. 5 is the schematic cross-section of other 1 example of the manufacture method of expression light-transmitting electromagnetic shielding material of the present invention.

Fig. 6 is the schematic cross-section of other 1 example of the manufacture method of expression light-transmitting electromagnetic shielding material of the present invention.

Description of reference numerals

11 cylinders

12 pretreating reagents

14 transparency carriers

15 scrapers

16 rollers

17 protuberance surfaces

18 gaps (recess)

41,51,61 transparency carriers

42,52 pretreating reagents

63 conductivity China inks

43,53 metal conducting layers

Embodiment

Describe with reference to the manufacture method and the light-transmitting electromagnetic shielding material of accompanying drawing image forming method of the present invention, light-transmitting electromagnetic shielding material.

The schematic cross-section of representational 1 example that will be used to illustrate the manufacture method of light-transmitting electromagnetic shielding material of the present invention is shown in Fig. 1.

Fig. 1 shows following operation: utilize a kind photogravure as intaglio printing, the chemical plating pretreating reagent is printed surface to transparency carrier, form netted preprocessing layer.The cylinder 11 of the lattice that has engraving is from the teeth outwards rotated in the direction of arrows, utilize scraper 15 to give its lattice face with chemical plating pretreating reagent 12, chemical plating pretreating reagent 12 is maintained at the recess of the lattice of engraving thus.The cylinder with chemical plating pretreating reagent 12 11 that rotates contacts with the transparency carrier 14 that is transmitted by roller 16, thereby the chemical plating pretreating reagent 12 of recess that makes the grid image of engraving is transferred to the surface of transparency carrier 14, forms pretreating reagent layer (becoming preprocessing layer after the drying).

In above-mentioned operation, when using the conductivity China ink to replace the chemical plating pretreating reagent, can form conductive layer.Above-mentioned operation is not only used above-mentioned pretreating reagent, conductivity China ink, also can use image to form and be used to form image with Image forming materials such as China inks.

Pretreating reagent layer to above-mentioned formation carries out drying (also can be moist when solvent is easy to evaporate), applies chemical plating on the preprocessing layer that obtains.Can obtain the net metal conductive layer thus.And when using the conductivity China ink, form conductive layer, can apply plating etc. as required.

Among the present invention, the pattern of the recess on cylinder 11 surfaces is netted, and the area of bottom in the intersection point part of its grid, recess is reduced.Thus, the intersection point portion of the preprocessing layer that obtains by dry pretreating reagent layer does not observe broken string substantially, therefore can reduce the live width of grid.When using the cylinder that the area of the bottom of recess do not reduced, near the central authorities of intersection point portion, preprocessing layer easily produces damaged part, and the conductive layer that obtains also can produce damaged part.Thereby the light-transmitting electromagnetic shielding material that utilizes manufacture method of the present invention to obtain does not have above-mentioned damaged, therefore have good electrical conductivity, and outward appearance is also good.

The protuberance surface configuration on cylinder 11 surfaces generally is respectively polygon, the polygon of Any shape such as triangle, quadrangle, pentagon, hexagon all can, but consider that from the viewpoint that is easy to form grid quadrangle is preferred.

The pattern of the recess on preferred cylinder 11 surfaces is shown in Fig. 2.Fig. 2 is a plane graph of overlooking cylinder 11 surfaces from above, and 17 one-tenths most on protuberance surfaces is regularly arranged, utilizes their gap (recess) 18 formation grids, and the intersection point part 18 of these gaps (recess) 18 ' area reduced.The shape on protuberance surface 17 was a quadrangle before its surface area increases.Arrow is the rotation direction (being print direction) of cylinder, and as shown in Figure 2, tetragonal all angles all increase to some extent, increases to some extent at the area along 2 relative angles of the rotation direction of the cylinder vertical direction of scraping direction of scraper 15 (promptly with respect to) at least to get final product.

The part enlarged drawing of the pattern of the recess of Fig. 2 is shown in Fig. 3 (arrow is the rotation direction (being print direction) of cylinder).Here showing reduction with the recess area of intersection point part, to proceed to what degree be preferred.That is, the shape on protuberance surface 17 was a quadrangle before its surface area increases, and had the bight that is illustrated by the broken lines.The summit at the tetragonal angle of protuberance in the intersection point part of recess, relative prolongs (the recess area of intersection point part is reduced thus), and the distance between its summit (L) is preferably below the 32 μ m, more preferably below the 30 μ m, be preferably 10～30 μ m especially.Thus, making the disappearance of the image in the intersection point part of the image that obtains significantly reduce or be easy to disappears.In addition, the tetragonal bight of protuberance in the intersection point part, relative, the shape that has the isosceles triangle of acute angle as shown in Figure 3 is preferred.The length on the base of this isoceles triangle shape (a) also is preferably below the 32 μ m, more preferably below the 30 μ m, is preferably 10～30 μ m especially.The disappearance of the image in the intersection point of the image that obtains thus, the part significantly reduces or is easy to and disappears.The shape of above-mentioned isosceles triangle is isosceles triangle substantially and gets final product, for example the angle of acute angle be that two limits of isosceles equate substantially less than 90 degree, more than 20 degree, for example 10: 8～8: 10.In addition, the shape of the augmenting portion in bight can be the ellipticity that is similar to isosceles triangle.

Aforementioned intaglio printing is preferably photogravure or heliogravure hectographic printing, can carry out the high printing of precision thus.

The manufacture method of light-transmitting electromagnetic shielding material of the present invention is preferably utilized following 3 kinds of methods:

The manufacture method of light-transmitting electromagnetic shielding material (A) comprising: use the liquid comprise composite metal oxide and/or composite metal oxide hydrate and synthetic resin to carry out the pattern printing as the chemical plating pretreating reagent and form the operation of netted preprocessing layer; And

On preprocessing layer, utilize chemical plating to handle and form the operation of netted metal conducting layer.

The manufacture method of light-transmitting electromagnetic shielding material (B) comprising: the liquid that uses the mixture comprise silane coupler and azole compounds or product and precious metal chemical complex carries out the pattern printing as the chemical plating pretreating reagent and forms the operation of netted preprocessing layer; And

The manufacture method of light-transmitting electromagnetic shielding material (C) comprising: the conductivity China ink pattern that will comprise metal particle and resin glue prints the operation that forms netted conductive layer to the surface of transparency carrier.

About each method, below describe in detail.

At first, with reference to the manufacture method of the electromagnetic wave shielding performance light inlet window material of the present invention of description of drawings above-mentioned (A).

The schematic cross-section that the formation method (A) of netted metal conducting layer suitable among the present invention is described is shown in Fig. 4.At first, shown in (A1), (A2), on transparency carriers such as transparent membrane 41, the chemical plating pretreating reagent that will contain composite metal oxide and/or composite metal oxide hydrate and synthetic resin is printed as netted by method of the present invention, after the drying, on transparency carrier 41, form netted preprocessing layer 42.And, preprocessing layer 42 is carried out chemical plating, thereby on aforementioned preprocessing layer 42, forms the netted metal conducting layer 43 that constitutes by electric conducting materials such as metals.

The chemical plating pretreating reagent that contains composite metal oxide and/or composite metal oxide hydrate and synthetic resin, the intaglio printing of the intaglio plate by having used given shape is printed as previously mentioned, therefore the chemical plating pretreating reagent can be printed (area of the shape of the intersection point of general grid has the tendency that diminishes a little) by the shape of the size of design substantially.Therefore, can form the netted preprocessing layer that does not produce striped and photographic fog, has fine pattern accurately.Handle by on so netted preprocessing layer, carrying out chemical plating, can form the little fine netted metal conducting layer of live width.

As composite metal oxide that is used for aforementioned chemical plating pretreating reagent and composite metal oxide hydrate, the preferred use contained the material that is selected from least 2 kinds of metallic elements in the group of being made up of Pd, Ag, Si, Ti and Zr.More preferably, can enumerate contain Pd or Ag metallic element and, the material of Si, Ti or Zr metallic element.Such composite metal oxide and composite metal oxide hydrate have high plating precipitation ability, and then have the stability in pretreating reagent and the characteristic of excellent dispersion.

Wherein, consider from the viewpoint that afore-mentioned characteristics is excellent especially, the preferred especially composite metal oxide hydrate that uses following formula (I) expression,

M ¹ _X·M ²O ₂·n(H ₂O)…(I)

(in the formula, M ¹Expression Pd or Ag; M ²Expression Si, Ti or Zr; Work as M ¹During for Pd, x is 1, works as M ¹During for Ag, x is 2; N is 1～20 integer).

In aforementioned formula (I), M ¹Be Pd or Ag, but be preferably Pd.And M ²Be Si, Ti or Zr, but be preferably Ti.Thus, can obtain having the composite metal oxide hydrate of high plating precipitation ability.

As aforementioned composite metal oxide hydrate, can list for example PdSiO ₃, Ag ₂SiO ₃, PdTiO ₃, Ag ₂TiO ₃, PdZrO ₃And Ag ₂TiO ₃Deng hydrate.

Above-mentioned composite metal oxide hydrate can followingly obtain: general's suitable slaine separately is hydrochloride, sulfate, nitrate, halide, oxyhalide (oxyhalides) for example, the hydrates of suitable metal oxide etc. are as raw material, use the method for their heating, hydrolysis etc. is obtained.

In addition, as composite metal oxide, preferably use M ¹ _XM ²O ₂(M ¹, M ²With X and above-mentioned formula (I) synonym) expression material.

Being used for the composite metal oxide of chemical plating pretreating reagent and the average grain diameter of composite metal oxide hydrate is 0.01～10 μ m, and especially preferably using average grain diameter is the material of 0.05～3 μ m.Thus, can obtain having the repressed high dispersiveness of gathering and the composite metal oxide and the aforementioned composite metal oxide hydrate of catalytic activity.

In addition, among the present invention, the average grain diameter of composite metal oxide and composite metal oxide hydrate is: with about 1,000,000 times multiplying powers composite metal oxide and/or composite metal oxide hydrate are observed the mean value of the numerical value of being tried to achieve by the area equivalent circle diameter of at least 100 particles with electron microscope (preferred transmission type electron microscope).

With respect to 100 mass parts synthetic resin, the content of composite metal oxide and/or composite metal oxide hydrate is preferably 10～60 mass parts, is preferably 10～40 mass parts especially.When content is lower than 10 mass parts, might can't obtain sufficient plating precipitation ability, when surpassing 60 mass parts, might form because striped and the photographic fog that the gathering of these composite metal oxides causes.

The chemical plating pretreating reagent is owing to contain synthetic resin, can raising and the adaptation of transparency carrier and conductive layer, and preprocessing layer becomes and is difficult to peel off, and can form conductive layer more accurately.

As long as synthetic resin can be guaranteed the adaptation with transparency carrier and conductive layer, not special the qualification.As preferred example, can list acrylate, mylar, polyurethane resin, vinyl chloride resin and EVAc resin etc.By using them, can obtain the high adaptation with transparency carrier and conductive layer, can on preprocessing layer, form conductive layer accurately.In addition, these synthetic resin can use separately, in addition also can be mixed with two or more.

As acrylate, can use for example alkyl-acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, Hexyl 2-propenoate, homopolymers, the copolymer of alkyl methacrylates such as methyl methacrylate, EMA, butyl methacrylate, hexyl methacrylate, and particularly preferably be homopolymers, the copolymer of methyl methacrylate, EMA or butyl methacrylate etc.

As mylar, for example can list PETG, polybutylene terephthalate (PBT), PTT, poly-2,6-(ethylene naphthalate) (2,6-polyethylene naphthalate) etc.

As polyurethane resin, for example can listing, polyester is that polyurethane resin, polyethers are polyurethane resin, polycarbonate-based polyurethane resin etc.Wherein, polyester is that polyurethane resin is preferred.

As above-mentioned polyurethane resin, for example can use by polyester is that the polyester that the product of polyalcohol and polyisocyanate compound constitutes is a polyurethane resin.Polyester is that the mean molecule quantity of polyurethane resin is generally 10,000～500,000.

As polyester is polyalcohol, can list for example low-molecular-weight diol and dicarboxylic acids reaction and the condensation polyester diol that obtains, the polylactone dihydroxylic alcohols that the ring-opening polymerisation by lactone obtains, PCDL etc.In addition, as low-molecular-weight diol, can list dihydroxylic alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, trihydroxy alcohols such as trimethylolpropane, trimethylolethane, hexanetriol, glycerol, hexahydroxylic alcohols such as sorbierite (hexaol).As aforementioned dicarboxylic acids, aromatic dicarboxylic acid classes such as aliphatic dicarboxylic acid class, terephthalic acid (TPA), M-phthalic acids such as butanedioic acid, adipic acid, decanedioic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid etc. are arranged, these can use separately or use more than 2 kinds.In addition, aforementioned lactone can use 6-caprolactone etc.

And, as polyester is polyalcohol, can list for example polyethylene glycol adipate, poly adipate succinic acid ester, poly-adipic acid hexylene glycol ester, polyneopentyl glycol adipate, poly-adipic acid ethylidene butylidene ester (polyethylene butyleneadipate), poly-adipic acid butylidene six butylidene esters (polybutylenehexabutylene adipate), poly-adipic acid diethylidene ester, poly-adipic acid (poly-fourth diether) ester (poly (polytetramethylene ether) adipate), polyethylene glycol azeleate, polyethylene glycol sebacate, polytetramethylene azelaate, polydiethylene glycol sebacate, polyhexamethylene carbonic ester dihydroxylic alcohols etc., these can use separately or use more than 2 kinds.

As polyisocyanate compound, aromatic diisocyanate (for example 4 is for example arranged, 4 '-methyl diphenylene diisocyanate, 2,4-toluene di-isocyanate(TDI), 1,5-naphthalene diisocyanate, positive isocyanato-phenyl sulfonyl isocyanates, an isocyanato-phenyl sulfonyl isocyanates or to isocyanato-phenyl sulfonyl isocyanates etc.); Aliphatic diisocyanate (for example 1,6-hexamethylene diisocyanate etc.); Ester ring type vulcabond polyisocyanates such as (for example IPDI, hydrogenation xylylene diisocyanate, hydrogenated diphenyl methane diisocyanates etc.), or the addition product of these various isocyanates or polymer etc., these can use separately or use more than 2 kinds.

Polyester is the not special qualification of the usage rate of polyalcohol and polyisocyanate compound, usually can be polyalcohol at polyester: about polyisocyanate compound=1: 0.01～0.5 in the scope of (mol ratio), according to the decisions aptly such as kind of the compound that uses.

When using polyester to be polyurethane resin, the chemical plating pretreating reagent preferably also contains polyisocyanate curing agent.Can use above-mentioned polyisocyanate compound as polyisocyanate curing agent.With respect to 100 mass parts polyester is polyurethane resin, and the content of curing agent is preferably 0.1～5 mass parts, is preferably 0.1～1.0 mass parts especially.

Corvic for the independent polymer of existing known vinyl chloride, be homopolymer resin, or existing known various copolymer resins, not special the qualification.As copolymer resin, can use existing known copolymer resin, can list the copolymer resin of vinyl chloride such as vinyl chloride vinyl acetate copolymer resin, vinyl chloride-vinyl propionate ester copolymer resin and vinyl esters, the copolymer resin of vinyl chloride such as vinyl chloride-butyl acrylate copolymer resin, vinyl chloride-2-EHA copolymer resin and esters of acrylic acid, the copolymer resin of vinyl chloride such as vinyl chloride-ethylene copolymer resin, VCP resin and olefines, vinyl chloride-acrylonitrile copolymer resin etc.Especially preferably use vinyl chloride homo resin, ethylene-vinyl chloride copolymer resin, vinyl acetate-vinyl chloride copolymer resin etc.

As synthetic resin, consider that from the viewpoint that can obtain high adaptation preferred molecular end has the material of the functional group of containing reactive hydrogen.As the functional group of containing reactive hydrogen; as long as have reactive hydrogen; not special the qualification can list primary amino radical, secondary amino group, imino group, amide groups, hydrazide group, amidino groups, hydroxyl, hydroperoxy, carboxyl, formoxyl, carbamoyl, sulfonic group, sulfinic acid base, sulfenic groups, mercapto, thioformyl, pyrrole radicals, imidazole radicals, piperidyl, indazolyl, carbazyl etc.Primary amino radical, secondary amino group, imino group, amide groups, imide, hydroxyl, formoxyl, carboxyl, sulfonic group or mercapto are preferred.Primary amino radical, secondary amino group, amide groups or hydroxyl are particularly preferred.In addition, these groups can be replaced by the alkyl of halogen atom, carbon number 1～20.Wherein, hydroxyl, carbonyl and amino are preferred.

With respect to the total amount of chemical plating pretreating reagent, the content of the synthetic resin in the chemical plating pretreating reagent is preferably 40～90 quality %, is preferably 60～80 quality % especially.Thus, can form preprocessing layer with high adaptation.

In addition, the chemical plating pretreating reagent also can contain inorganic particles.By containing inorganic particles, can improve printing precision, can form the higher conductive layer of precision.As preferred inorganic particles, can list silicon dioxide, calcium carbonate, aluminium oxide, talcum, mica, sheet glass, metal whisker, ceramic whisker, calcium sulfate crystal whiskers, montmorillonite etc.These can use a kind separately, also can be mixed with two or more.

The average grain diameter of inorganic particles is preferably 0.01～5 μ m, is preferably 0.1～3 μ m especially.When the average grain diameter of inorganic particles is lower than 0.01 μ m, might printing precision be increased to the degree of expectation by adding inorganic particles, when surpassing 5 μ m, might become is easy to produce striped and photographic fog.

With respect to 100 mass parts synthetic resin, the content of the inorganic particles in the chemical plating pretreating reagent is preferably 0.01～10 mass parts, is preferably 1～5 mass parts especially.Thus, can obtain having the pretreating reagent of high printability.

In addition, the chemical plating pretreating reagent also can contain thixotropic agent.According to aforementioned thixotropic agent, can improve printing precision by the flowability of adjusting pretreating reagent, can form the higher conductive layer of precision.As thixotropic agent, as long as can use for having known material now.Can preferably use amide waxe, rilanit special, beeswax, Brazil wax, stearic amide, hydroxy stearic acid ethylene bisamides etc.

With respect to the aforementioned synthetic resin of 100 mass parts, the content of the thixotropic agent in the chemical plating pretreating reagent is preferably 0.1～10 mass parts, is preferably 1～5 mass parts especially.Thus, can obtain having the pretreating reagent of high printability.

Chemical plating pretreating reagent of the present invention also can contain black colorant.Thus, printing precision can be improved, and the antiglare effect of self-induced transparency substrate-side when seeing can be given for resulting light-transmitting electromagnetic shielding material.

As preferred black colorant, can list that carbon black, titanium are black, black iron oxide, graphite and active carbon etc.These can use a kind separately, also can be mixed with two or more.Wherein carbon black is preferred.As carbon black, can list acetylene black, channel black, furnace black etc.The average grain diameter of carbon black is preferably 0.1～1000nm, is preferably 5～500nm especially.

With respect to 100 mass parts synthetic resin, the content of the black colorant in the chemical plating pretreating reagent is preferably 0.1～10 mass parts, is preferably 1～5 mass parts especially.Thus, can form preprocessing layer accurately with antiglare effect.

When using black colorant, preferably use commercially available tusche to prepare the chemical plating pretreating reagent.As such tusche, Toyo Ink Manufacturing Co., Ltd. system SS8911, JUJO CHEMICAL CO. are arranged, LTD. system EXG-3590, the system NT-HiLamic 795R of Dainichiseika Color Chem China ink etc.For example, when using the system SS8911 of Toyo Ink Manufacturing Co., Ltd., in solvent, the carbon removal infrablack also contains vinyl chloride and acrylate etc.Therefore, as long as, can easily prepare the chemical plating pretreating reagent that contains synthetic resin and black colorant for aforementioned commercially available product.

In addition, the chemical plating pretreating reagent can contain appropriate solvent.As solvent, can enumerate water outlet, methyl alcohol, ethanol, 2-propyl alcohol, acetone, toluene, ethylene glycol, polyethylene glycol, dimethyl formamide, dimethyl sulfoxide (DMSO), diox etc.These can use a kind separately, also can be mixed with two or more.

The chemical plating pretreating reagent can further contain various additives such as extender pigment, surfactant as required.

In the method for the present invention, utilize intaglio printing,, thereby on transparency carrier, form netted preprocessing layer above-mentioned netted being printed on the transparency carrier of chemical plating pretreating reagent with specific lattice.Thus, can utilize easy method to form the preprocessing layer with fine pattern of expectation.

In order to obtain not having broken string by printing, to have the preprocessing layer of fine live width and gap (spacing), the viscosity of chemical plating pretreating reagent preferably is preferably 500～5000cps, more preferably 1000～3000cps under 25 ℃.

After the printing chemical plating pretreating reagent, preferably at 80～160 ℃, it is preferred more preferably coming drying 90～130 ℃ of following heating like this.When baking temperature was lower than 80 ℃, the evaporation rate of solvent was slow, might can't obtain sufficient film forming, and when surpassing 160 ℃, thermal decomposition might take place compound.Be preferably 5 second～5 minute the drying time when after coating, carrying out heated drying.

The thickness of preprocessing layer is generally 0.01～5 μ m, is preferably 0.1～2 μ m.Thus, can guarantee high adaptation with transparency carrier and conductive layer.

In the method for the present invention, after the operation that on transparency carrier, forms netted preprocessing layer as described above, forming the operation of netted metal conducting layer before, preprocessing layer 42 reduced to handle be preferred.By reducing processing, can make the contained chemical plating catalyst of preprocessing layer 42, be the contained metal kind reduction of composite metal oxide and composite metal oxide hydrate, and only make as the metal kind of active component and separate out equably so that ultra micro is granular.Because the metal kind of separating out of reducing like this has high catalytic activity and stable, therefore preprocessing layer 42 and the adaptation of transparency carrier and the speed of separating out that can improve chemical plating can be improved, and then the use amount of composite metal oxide and composite metal oxide hydrate can be reduced.

As long as reduction is handled for making the reduction of contained composite metal oxide of preprocessing layer and aforementioned composite metal oxide hydrate, metallized method, not special the qualification.Particularly, the preferred use: (i) liquid phase reduction of the transparency carrier that is formed with aforementioned preprocessing layer being handled with the solution that contains reducing agent; (ii) make the transparency carrier that is formed with aforementioned preprocessing layer and the contacted gas phase reduction process of reducibility gas etc.

In liquid phase reduction, contain the method that the solution of reducing agent is handled as use, can use the method for for example in containing the solution of reducing agent, flooding the transparency carrier that is formed with preprocessing layer, on the face that is formed with preprocessing layer of transparency carrier, spray the method for the solution that contains reducing agent etc.

The solution that contains reducing agent disperses or dissolves in the water equal solvent by the reducing agent that makes regulation and is prepared.As aforementioned reducing agent, not special the qualification can list sulphite, dithionite (Na such as hypophosphites, HAS, sodium sulfite such as formamide, dimethyl formamide, diethylformamide, dimethylacetylamide, DMAA, sodium borohydride, potassium borohydride, glucose, amino borane, dimethylamine borane (DMAB), trimethylamine borine (TMAB), hydrazine, diethylamine borine, formaldehyde, glyoxalic acid, imidazoles, ascorbic acid, azanol, HAS, hydroxylamine hydrochloride, hypophosphorous acid, sodium hypophosphite ₂S ₂O ₄: also claim sodium dithionite) etc.Reducing agent if use with the used chemical plating bath of subsequent handling in the contained identical material of reducing agent, the aforementioned transparency carrier after then can handling reduction is not washed and is handled and carry out chemical plating, and makes the risk of composition variation of chemical plating bath less yet.

As reducing agent, consider from the viewpoint that can obtain high reproducibility, preferably use amino borane, dimethylamine borane, sodium hypophosphite, HAS, dithionite and formalin.

The content that contains the reducing agent in the solution of reducing agent is preferably 0.01～200g/L, is preferably 0.1～100g/L especially.The concentration of reducing agent is crossed when low, and fully reducing the required time of handling might be elongated, and during the excessive concentration of reducing agent, the plating coating catalyst of separating out might come off.

In liquid phase reduction, contain the method that the solution of reducing agent is handled as use, consider from the viewpoint of the high reproducibility that can obtain contained composite metal oxide of preprocessing layer and aforementioned composite metal oxide hydrate, preferably use the method for in containing the solution of reducing agent, flooding the transparency carrier that is formed with preprocessing layer.

During the dipping transparency carrier, the temperature that contains the solution of aforementioned reducing agent is preferably 20～90 ℃, is preferably 40～80 ℃ especially.In addition, dip time was at least more than 1 minute, was preferably about 1～10 minute.

On the other hand, use gas phase reduction process to reduce when handling, as reducibility gas, as long as be the gas that hydrogen, diborane gas etc. have reproducibility, not special the qualification.Use reducing gas reduce reaction temperature when handling and reaction time according to the kind of the reducing gas that uses etc. aptly decision get final product.

Below, in the method for the present invention, on the preprocessing layer that obtains as described above, carry out chemical plating and handle, thereby enforcement forms the operation of netted metal conducting layer.Handle by carrying out chemical plating, fine metallic particles deposition forms dense continuous overlay film, can only obtain metal conducting layer on preprocessing layer selectively.

The metal of plating can use but plating is so long as have conductivity, can be metal simple-substance, alloy, conductive metal oxide etc., also can be even metal film or by through same coating and the material that the fine particulate that obtains etc. constitute.

As the plating in the chemical plating, can use aluminium, nickel, indium, chromium, gold, vanadium, tin, cadmium, silver, platinum, copper, titanium, cobalt, lead etc.Especially consider from the viewpoint of the conductive layer that can obtain high electromagnetic wave shielding performance, preferably, preferred silver, copper or the aluminium of using.With the conductive layer of these platings formation and the adaptation excellence of preprocessing layer, and suitable light transmission and the electromagnetic wave shielding performance taken into account.

Chemical plating can use chemical plating bath to carry out under normal temperature or heating according to a conventional method.Promptly, can select aptly: the dipping plating base carries out chemical plating in the plating bath that contains plating salt, chelating agent, pH conditioning agent, reducing agent etc. as basic composition being built the material of bathing and obtaining, perhaps to be divided into 2 parts more than the liquid and the mode of adding applies plating processing etc. with constituting plating bath.

If enumerate 1 example as chemical plating, then can adopt following method: when forming the conductive layer that constitutes by Cu, the method that the transparency carrier that will have preprocessing layer and an anchor coating is adjusted into 12～13.5 at pH, be preferably in 12.5～13 the following solution, 50～90 ℃ of dipping 30 second～60 minute especially, wherein aforementioned solution contains: the water-soluble mantoquita of 1～100g/L, preferred especially 5～50g/L copper sulphate etc., 0.5 reducing agents such as～10g/L, preferred especially 1～5g/L formaldehyde, complexing agents such as 20～100g/L, preferred especially 30～70g/L EDTA.

Can shake when carrying out chemical plating, rotate by the substrate of plating, also can stir near its air.

The live width of the metal conducting layer of netted (clathrate) is generally below the 20 μ m, is preferably 5～15 μ m, especially preferably has 5～12 μ m.The spacing of line is preferably below the 200 μ m.In addition, aperture opening ratio is preferably 75～95%, is preferably 80～95% especially.

The shape of the peristome that the line of conductive layer surrounded can be circle, oval, shape arbitrarily such as square (quadrangle, hexagon), and is generally squarely, is preferably square especially.

In the method for above-mentioned (A), can handle (aftermentioned) and form the coat of metal at the enterprising electroplating of netted conductive layer.In addition, also can carry out melanism and handle (aftermentioned), for example, can carry out the black plating of the oxidation processes, evanohm etc. of metal film, the coating of black or dark-coloured system China ink etc. this coat of metal.

Below, with reference to the manufacture method of the electromagnetic wave shielding performance light inlet window material of the present invention of description of drawings aforementioned (B).

With illustrating of manufacture method (B) of electromagnetic wave shielding performance light inlet window material suitable among explanation the present invention in Fig. 5.Shown in (B1), (B2), on transparency carriers such as transparent membrane 51, to contain the mixture of silane coupler and azole compounds or the chemical plating pretreating reagent of product and precious metal chemical complex, be printed as nettedly by method of the present invention, on transparency carrier 51, form netted preprocessing layer 52.Then, on preprocessing layer 52, form the netted metal conducting layer 53 that constitutes by electric conducting materials such as metals by carrying out chemical plating.

In said method, utilization has the intaglio printing on the intaglio plate surface of given shape of the present invention, the chemical plating pretreating reagent is printed to transparency carrier 51, therefore can be substantially form pretreating reagent, meet design size, fine netted metal conducting layer 53 (area of the shape of the intersection point of general grid has the tendency that diminishes a little) that live width is little substantially thereby can form by the shape of design size.In addition, by using above-mentioned chemical plating pretreating reagent, silane coupler, azole compounds and precious metal chemical complex are disperseed with atomic level in preprocessing layer, therefore can form the netted preprocessing layer that does not produce striped and photographic fog, has fine pattern accurately.Handle by on so netted preprocessing layer, carrying out chemical plating, can form the little fine netted metal conducting layer of live width.

In method of the present invention (B), the aforementioned silane coupler that is used as the chemical plating pretreating reagent preferably uses to have in a part and has the material that metal is mended the functional group of the ability of catching.Thus, can form and effectively to bring into play electronic state, the state of orientation that chemical plating catalyst is the activity of precious metal chemical complex, can obtain and the high adaptation of being plated material.

As silane coupler, can enumerate and contain the epoxy radicals silicone hydride compound.As containing the epoxy radicals silicone hydride compound, can list for example γ-glycidoxy propyl trialkoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.These can use separately, and use also capable of being combined is more than 2 kinds.Especially show with the high adaptation viewpoint of transparency carrier and conductive layer from the preprocessing layer that obtains and consider that γ-glycidoxy propyl trialkoxy silane is preferred.

Then, as the azole compounds that is used for the chemical plating pretreating reagent, can list imidazoles, oxazole, thiazole, selenazoles, pyrazoles, isoxazole, isothiazole, triazole, oxadiazole, thiadiazoles, tetrazolium, oxatriazole, thiatriazole, dibazol, indazole, benzimidazole, BTA, indazole etc.Though be not limited to these materials, consider that from the reactive excellent viewpoint of functional group such as the epoxy radicals that had with silane coupler and precious metal chemical complex imidazoles is particularly preferred.

In the chemical plating pretreating reagent, silane coupler can only mix with azole compounds, also can make their reactions in advance and the formation product.Thus, precious metal chemical complex can be carried out more high dispersive with atomic level in preprocessing layer, and can improve the light transmission of resulting preprocessing layer.

In order to make the reaction of silane coupler and azole compounds, preference mixes 0.1～10 mole silane coupler as under 80～200 ℃ with respect to 1 mole of azole compounds, reacts 5 minutes～2 hours.At this moment, solvent is not generally wanted, but can make water yet, also has organic solvents such as chloroform, diox, methyl alcohol, ethanol.Mixed noble metal compound in the product of aforementioned silane coupler that so obtains and aforementioned azole compounds, thus the chemical plating pretreating reagent can be obtained.

Then, the precious metal chemical complex that is used for the chemical plating pretreating reagent is to handle the material of separating out the catalytic effect of growth in chemical plating with showing metal selectives such as can making copper, aluminium.For example, consider the preferred compound that contains metallic atoms such as palladium, silver, platinum and gold that uses from the viewpoint that can obtain high catalytic activity.As such compound, can use the amine complex etc. of the chloride, hydroxide, oxide, sulfate, ammonium salt etc. of above-mentioned metallic atom, preferred especially palladium compound, especially preferred palladium bichloride.

With respect to azole compounds and silane coupler, the chemical plating pretreating reagent preferably contains 0.001～50 mole of %, more preferably contains 0.1～20 mole of % precious metal chemical complex.When the concentration of precious metal chemical complex is lower than 0.001 mole of %, sufficient catalytic activity can't be obtained and the conductive layer of thickness might be can't formed with expectation, when surpassing 50 moles of %, might can't obtain with the increase of addition accordingly, the catalytic effect that brings by precious metal chemical complex.

The chemical plating pretreating reagent can further contain various additives such as extender pigment, surfactant, colouring agent as required.

In order to obtain having the preprocessing layer of fine live width and gap (spacing) by printing, the viscosity of chemical plating pretreating reagent (B) is preferably 500～5000cps under 25 ℃, more preferably 1000～3000cps.

When printing chemical plating pretreating reagent, make intaglio printings such as photogravure.Print speed printing speed is preferably 5～50m/ minute.

Like this after the printing chemical plating pretreating reagent, can be preferably 80～160 ℃, more preferably 90～130 ℃ down heating come dry.When baking temperature was lower than 80 ℃, the evaporation rate of solvent was slow, might can't obtain sufficient film forming, and during above 160 ℃, thermal decomposition might take place compound.Be preferably 5 second～5 minute the drying time when after coating, carrying out heated drying.

(B) of the present invention method is identical with (A) of the present invention method, carries out chemical plating and handle on preprocessing layer.Also can handle and the formation coat of metal at the enterprising electroplating of the netted metal conducting layer that obtains.In addition, can carry out melanism to this coat of metal and handle, for example can carry out the black plating of the oxidation processes, evanohm etc. of metal film, the coating of black or dark-coloured system China ink etc.

The live width of netted metal conducting layer is generally below the 20 μ m, is preferably 5～15 μ m, especially preferably has 5～12 μ m.The spacing of line is preferably below the 200 μ m.In addition, aperture opening ratio is preferably 75～95%, is preferably 80～95% especially.

Manufacture method with reference to the electromagnetic wave shielding performance light inlet window material of the present invention of description of drawings aforementioned (C).

With illustrating of formation method (C) of light-transmitting electromagnetic shielding window material suitable among explanation the present invention in Fig. 6.Shown in (C1), the conductivity China ink that will contain conductive particle and resin glue on transparency carrier 61 is printed as netted by method of the present invention, thereby forms netted conductive layer 63.

As previously mentioned, the intaglio printing of the intaglio plate by having used given shape comes the printing conductive China ink, therefore can be substantially by the netted conductive layer (area of the shape of the intersection point of general grid has the tendency that diminishes a little) of shape printing of the size of design.Therefore, can form the netted conductive layer that does not produce striped and photographic fog, has fine pattern accurately.

As the conductive particle that is used for above-mentioned conductivity China ink, can list metal, alloys such as aluminium, nickel, indium, chromium, gold, vanadium, tin, cadmium, silver, platinum, copper, titanium, cobalt, lead; Or ITO, indium oxide, tin oxide, zinc oxide, indium oxide-tin oxide (ITO, the so-called indium tin oxide of mixing), tin oxide-antimony oxide (ATO, so-called antimony doped tin oxide), zinc oxide-aluminium oxide electroconductive oxides such as (ZAO, so-called Al-Doped ZnOs) etc.These can use a kind separately, also can be mixed with two or more.

Wherein, as aforementioned conductive particle, can preferably list silver, copper, gold, nickel, indium and tin.As long as be these conductive particles, can improve the conductivity of the netted conductive layer that obtains.

The average grain diameter of conductive particle is preferably 10nm～10 μ m, is preferably 10nm～5 μ m especially.

With respect to 100 mass parts resin glues, the content of the conductive particle in the conductivity China ink is preferably 400～1000 mass parts, is preferably 400～800 mass parts especially.Thus, can form the conductive layer of conductive particle contact excellence to each other.

As the resin glue that is used for the conductivity China ink, can list acrylate, mylar, epoxy resin, polyurethane resin, phenolic resins, maleic acid resin, melmac, Lauxite, polyimide resin, contain silicones etc.And then, preferred heat-curing resin in these resins.

In order to be adjusted to the viscosity of appropriateness, the conductivity China ink also can contain solvent.As solvent, can list alcohol such as hexanol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alchohol, pentadecanol, stearyl alcohol, ceryl alcohol, cyclohexanol, terpineol; Alkyl ethers such as ethylene glycol monobutyl ether (butyl cellosolve), ethyleneglycol monophenylether, diethylene glycol, diethylene glycol monobutyl ether (butyl carbitol), cellosolve acetate (cellosolve acetate), butyl cellosolve acetate, carbitol acetic acid esters, acetate of butyl carbitol.

The conductivity China ink also can further contain black colorant.Thus, printing precision can be improved, and the antiglare effect of self-induced transparency substrate-side when seeing can be given for resulting electromagnetic wave shielding performance light transmission window material.

As black colorant, use preferably that carbon black, titanium are black, black iron oxide, graphite and active carbon etc.These can use a kind separately, also can be mixed with two or more.Wherein carbon black is preferred.As carbon black, can list acetylene black, channel black, furnace black etc.The average grain diameter of carbon black is preferably 0.1～1000nm, is preferably 5～500nm especially.

With respect to 100 mass parts resin glues, the content of the black colorant in the conductivity China ink is preferably 0.1～10 mass parts, is preferably 1～5 mass parts especially.

The conductivity China ink can further contain existing known auxiliary agents such as dispersant, plasticizer, defoamer, curing agent such as surfactant.

Above-mentioned conductivity China ink is printed as on transparency carrier when netted, for the generation that suppresses to break, also in order to have fine live width and gap (spacing) by printing, the viscosity of conductivity China ink preferably, under 25 ℃, be preferably 100～10000cps, more preferably 500～5000cps.

The live width of netted conductive layer is generally below the 20 μ m, is preferably 5～15 μ m, especially preferably has 5～12 μ m.The spacing of line is preferably below the 200 μ m.In addition, aperture opening ratio is preferably 75～95%, is preferably 80～95% especially.In addition, aperture opening ratio is to calculate according to the quantity of the line that exists in the live width of grid and the 1 inch width to try to achieve.

For netted (metal) conductive layer that utilizes method of the present invention (comprising above-mentioned (A)～(C)) to obtain, can further carry out electroplating processes (for (C), handling or electroplating processes) and on conductive layer, form the coat of metal for chemical plating.In addition, can on this coating, form aforementioned antiglare layer, also can carry out following melanism and handle.

As being used for the material that plating is handled, need only the material that has excellent electromagnetic shielding effect for the coat of metal, not special the qualification can list for example metals such as copper, nickel, chromium, zinc, tin, silver and gold.These can use independent a kind, also can use the alloy more than 2 kinds.

The thickness of the coat of metal is preferably 0.1～10 μ m, more preferably 2～5 μ m.When aforementioned thickness is lower than 0.1 μ m, can't give sufficient electromagnetic shielding effect, on the other hand, when surpassing 10 μ m, when coating forms,, can cause the aperture opening ratio step-down of live width chap, conductive layer because plating is also expanded at Width.

As the surface resistivity in the coat of metal, be preferably 3 Ω/below the, more preferably 1 Ω/below the.When the surface resistivity of coating surpassed 3 Ω/, conductivity might be insufficient, and electromagnetic shielding effect might become insufficient.

Form after the coat of metal, can give its anti-dazzle property.When carrying out this anti-dazzleization processing, can carry out melanism to the surface of netted conductive layer and handle.For example can carry out oxidation processes, the vulcanizing treatment of conductive layer or coating, plating such as the black of evanohm etc., the coating of the China ink of black or dark-coloured system etc.

Preferably utilize the oxidation processes or the vulcanizing treatment of the metal of conductive layer or coating to carry out the melanism processing.Especially from obtaining more excellent antiglare effect, the simplicity that also has liquid waste processing and the viewpoint of environmental safety, oxidation processes is preferred.

During the oxidation processes of carrying out handling as melanism, as the melanism treatment fluid, generally can use the mixed aqueous solution etc. of mixed aqueous solution, peroxy-disulfuric acid and NaOH of mixed aqueous solution, chlorite and the NaOH of hypochlorite and NaOH, especially consider from the viewpoint of economy, preferably use the mixed aqueous solution of hypochlorite and NaOH or the mixed aqueous solution of chlorite and NaOH.

During the vulcanizing treatment of carrying out handling as aforementioned melanism, as the melanism treatment fluid, generally can use the aqueous solution of potassium sulfide, barium sulphide and ammonium sulfide etc., preferably potassium sulfide and ammonium sulfide, especially consider from the viewpoint that can use at low temperatures, preferably use ammonium sulfide.

The thickness of melanism processing layer is not special to be limited, but is generally 0.01～1 μ m, is preferably 0.01～0.5 μ m.When aforementioned thickness was lower than 0.01 μ m, the antiglare effect of light might be insufficient, and when surpassing 1 μ m, the apparent openings rate during stravismus might reduce.

In the method for the invention, as the transparency carrier of coating pretreating reagent or conductivity China ink, if transparency carrier transparent and flexible for possessing, that can stand processing afterwards, not special the qualification.Material as transparency carrier, can list for example glass, polyester (example: PETG (PET), polybutylene terephthalate (PBT)), acrylate (example: polymethyl methacrylate (PMMA)), Merlon (PC), polystyrene, primary cellulose acetate, polyvinyl alcohol, polyvinyl chloride, Vingon, polyethylene, vinyl-vinyl acetate copolymer, polyvinyl butyral resin, the metal ion crosslinked ethylene-methacrylic acid copolymer, polyurethane, glassine paper etc., in the middle of these, preferably by processed (heating, solvent, bending) deterioration that is caused is few, the material that the transparency is high, i.e. PET, PC, PMMA.In addition, sheet, film or the plate that these materials can be formed is as transparency carrier.

The thickness of transparency carrier is not special to be limited, but consider that from the viewpoint of the light transmission of keeping light-transmitting electromagnetic shielding material thin more is preferred more, usually, form during according to use, the mechanical strength of needs are set thickness aptly in the scope of 0.05～5mm.

Preferably the strip plastic film is used as transparency carrier of the present invention, in roll-to-roll mode, transmit the strip plastic film on one side continuously, on one side printing, dry preprocessing layer and carry out chemical plating processing etc. continuously, perhaps printing continuously, dry conductivity China ink, and carry out plating processing etc. as required, thereby can obtain light-transmitting electromagnetic shielding material easily.

The light-transmitting electromagnetic shielding material that obtains so also can have hard conating, anti-reflection layer, tone compensation filter layer, near infrared ray absorption layer etc. except that adhesive phase.The stacked order of these each layers determines according to purpose.In addition, in order to improve the electromagnetic wave shielding function, can in display filter, be provided for the electrode that is connected with the grounding electrode of PDP main body.

As preferred light-transmitting electromagnetic shielding material, can list following material: be provided with for example anti-reflection layer such as hard conating and low-index layer on the surface of the netted conductive layer that obtains, be provided with the material of near infrared ray absorption layer overleaf; Perhaps on the surface of netted conductive layer by means of adhesive phase or near infrared ray absorption layer directly is set, be provided with the material of anti-reflection layers such as hard conating and low-index layer overleaf.

Light-transmitting electromagnetic shielding material of the present invention can be applicable to the purposes that needs light transmission aptly, the display surface of display unit such as the LCD of the various power equipments that for example generate electromagnetic waves, PDP, CRT, or facility, the clear glass face in house, transparent panel face.Because light-transmitting electromagnetic shielding material of the present invention has high light transmittance and electromagnetic wave shielding performance, therefore can be used for the display filter of aforementioned display aptly, especially can be used for the PDP filter aptly.

Embodiment

The present invention is described by the following examples.The present invention is not limited to following embodiment.

[embodiment 1]

(1) preparation of pretreating reagent

With composite metal oxide hydrate particle (PdTiO ₃6H ₂O, average grain diameter 0.5 μ m) to be coupled to bi-component curing type polyester be in the polyurethane resin solution, be polyurethane resin wherein with respect to 100 mass parts polyester, cooperate 30 mass parts composite metal oxide hydrate particles, thereby make pretreating reagent (viscosity: 2000cps, 25 ℃).

In addition, aforementioned bi-component curing type polyester is that polyurethane resin solution uses the mass ratio with 100: 0.5 to contain mylar (Toyo-Morton, Ltd. make AD-335A, Tg:10 ℃) and alicyclic isocyanate (Toyo-Morton, Ltd. makes CAT-10L), solid component concentration be the material of 10 quality %.

2. the preparation of netted preprocessing layer

Then, aforementioned pretreating reagent is utilized photogravure on PET film (thickness 100 μ m) and after carrying out patterning,, thereby on aforementioned PET film, form netted preprocessing layer at 120 ℃, dry 5 minutes.In addition, the mesh shape of the intaglio plate of photogravure is: 1 limit of protuberance (line at interval) is the square of 254 μ m, distance between square (live width) is 20 μ m, distance (L) between the foursquare relative angle of Fig. 3 is 29 μ m, and (a) of the isosceles triangle at the foursquare relative angle of Fig. 3 is 29 μ m.The line of the netted preprocessing layer that obtains is spaced apart 254 μ m, and live width is 20 μ m, and aperture opening ratio is 85%, and thickness is 0.5 μ m.

3. the reduction of preprocessing layer is handled

The PET film that is formed with preprocessing layer that then, will obtain in above-mentioned steps is at 60 ℃ sodium hypophosphite solution (NaH ₂PO ₂Concentration: dipping is 3 minutes 30g/L), carries out the reduction of preprocessing layer and handles.

4. the preparation of metal conducting layer

To in above-mentioned steps, be formed with PET film dipping in chemical bronze plating liquid (Meltex Inc. system Melplate CU-5100) of the preprocessing layer of having passed through the reduction processing, and under 50 ℃, 20 minutes, carry out electroless copper and handle, obtain netted metal conducting layer.The live width of aforementioned metal conductive layer is 25 μ m, and line is spaced apart 254 μ m, and aperture opening ratio is 81%, and thickness is 4 μ m.

5. the melanism of metal conducting layer is handled

And then, carry out the melanism of following composition at the PET film that is formed with metal conducting layer that in abovementioned steps, obtains and handle.

The melanism treatment fluid is formed (aqueous solution)

Sodium chlorite: 10 quality %

NaOH: 4 quality %

The melanism treatment conditions

Bathe temperature: about 60 ℃

Time: 5 minutes

Handle the surface that has obtained metal conducting layer by this melanism and passed through the light-transmitting electromagnetic shielding material that melanism is handled.The carrying out on the surface of the light-transmitting electromagnetic shielding material that obtains the thickness average out to 0.5 μ m that handles of melanism.All the other sizes do not change.

[embodiment 2]

Making foursquare relative angular separation in the mesh shape of intaglio plate of photogravure, Fig. 3 is 30 μ m from (L), (a) of the isosceles triangle at the foursquare relative angle of Fig. 3 is 30 μ m, in addition, make light-transmitting electromagnetic shielding material similarly to Example 1.

The line of the netted preprocessing layer that obtains is spaced apart 254 μ m, and live width is 20 μ m, and aperture opening ratio is 85%, and thickness is 0.5 μ m.In addition, the live width of aforementioned metal conductive layer is 25 μ m, and line is spaced apart 254 μ m, and aperture opening ratio is 81%, and thickness is 4 μ m, melanism processing layer average out to 0.5 μ m.

[embodiment 3]

Making foursquare relative angular separation in the mesh shape of intaglio plate of photogravure, Fig. 3 is 31 μ m from (L), (a) of the isosceles triangle at the foursquare relative angle of Fig. 3 is 31 μ m, in addition, make light-transmitting electromagnetic shielding material similarly to Example 1.

[embodiment 4]

Making foursquare relative angular separation in the mesh shape of intaglio plate of photogravure, Fig. 3 is 32 μ m from (L), (a) of the isosceles triangle at the foursquare relative angle of Fig. 3 is 32 μ m, in addition, make light-transmitting electromagnetic shielding material similarly to Example 1.

[reference example 1]

Making foursquare relative angular separation in the mesh shape of intaglio plate of photogravure, Fig. 3 is 35 μ m from (L), (a) of the isosceles triangle at the foursquare relative angle of Fig. 3 is 35 μ m, in addition, make light-transmitting electromagnetic shielding material similarly to Example 1.

[evaluation of light-transmitting electromagnetic shielding material]

1) broken string of intersection point portion

Conductive layer surface after with microscope (model LHX-500, KEYENCE CORPORATION. system) conductive layer being formed is observed, and estimates as described below.

◎: in per 100 intersection points, the broken string of intersection point is below 3

Zero: in per 100 intersection points, the broken string of intersection point for surpass 3, below 10

△: in per 100 intersection points, the broken string of intersection point for surpass 10, below 20

*: in per 100 intersection points, the broken string of intersection point is above 20

2) sheet resistance (Ω/)

After coating forms, measure its sheet resistance according to JIS-C-2141.

3) outward appearance

After coating forms,, estimate as described below with its outward appearance of visualization.

Zero: do not observe bad order (inhomogeneous, coating is matt and be lead); △: observe a part of bad order (inhomogeneous, coating is matt and be lead)

4) electromagnetic wave shielding performance

After coating forms, utilize the KEC method to measure electromagnetic wave shielding performance, estimate as described below.

Zero: the above △ of 40dB: 20dB is above, be lower than 40dB

The results are shown in table 1.

[table 1]

	??(L)??(μm)	??(a)??(μm)	Aperture opening ratio (%)	Broken string	Printing rear surface resistance (Ω/)	Outward appearance	Shielding
	??(L)??(μm)	??(a)??(μm)	Aperture opening ratio (%)	Broken string	Printing rear surface resistance (Ω/)	Outward appearance	Shielding	Embodiment 1	??29	??29	??81	??◎	??1×10 ²	??○	??○
Embodiment 2	??30	??30	??81	??◎	??1×10 ²	??○	??○	Embodiment 1	??29	??29	??81	??◎	??1×10 ²	??○	??○
Embodiment 2	??30	??30	??81	??◎	??1×10 ²	??○	??○	Embodiment 3	??31	??31	??81	??○	??1×10 ²	??○	??○
Embodiment 4	??32	??32	??81	??○	??1×10 ²	??○	??○	Embodiment 3	??31	??31	??81	??○	??1×10 ²	??○	??○
Embodiment 4	??32	??32	??81	??○	??1×10 ²	??○	??○	Reference example 1	??35	??35	??81	??×	??3×10 ⁴	??×	??×

The light-transmitting electromagnetic shielding material that obtains in the reference example 1 is because broken string is many, so the sheet resistance height (3 * 10 after the printing ⁴Ω/), produce the plating inequality in the plating observes bad order.In addition also because sheet resistance does not reduce (2 * 10 ²Ω/), electromagnetic screen also covering property is insufficient.

The tetragonal shape of the intersection point of the grid of the light-transmitting electromagnetic shielding material that obtains among the embodiment 1～4 part is in addition utilized aforementioned microscopic examination cave in a little to the bight (the square cornicult partly of no grid goes out).

Utilizability on the industry

Utilize the image forming method that can form easily without the network diagramming picture of broken string of the present invention, can make easily the netted conductive layer with nothing broken string, the light-transmitting electromagnetic shielding material of excellent electromagnetic wave shielding performance. It is useful that the light-transmitting electromagnetic shielding material that obtains like this needs the window of the building of electromagnetic wave shielding for the front wave filter of plasma display (PDP), hospital etc.

Claims

1. image forming method, it comprises following operation:

2. image forming method according to claim 1, wherein, the surface configuration of protuberance before the reduction of the area of concave bottom, net-like pattern is a quadrangle, and the prolongation on the summit by tetragonal angle, and the area of intersection point bottom in partly, recess is reduced.

3. image forming method according to claim 2, wherein, the distance (L) between the summit at tetragonal angle in the intersection point part, relative is below the 30 μ m.

4. according to claim 2 or 3 described image forming methods, wherein, in the intersection point part, relative tetragonal bight has the shape of the isosceles triangle of acute angle, and the length on its base (a) is below the 30 μ m.

5. the manufacture method of a light-transmitting electromagnetic shielding material is characterized in that, this manufacture method comprises:

On preprocessing layer, handle the operation that forms netted metal conducting layer by chemical plating, wherein,

6. manufacture method according to claim 5, wherein, the chemical plating pretreating reagent is the liquid that comprises composite metal oxide and/or composite metal oxide hydrate and synthetic resin.

7. manufacture method according to claim 5, wherein, the chemical plating pretreating reagent is to comprise the mixture of silane coupler and azole compounds or the liquid of product and precious metal chemical complex.

8. the manufacture method of a light-transmitting electromagnetic shielding material, this manufacture method comprises following operation:

9. according to each described manufacture method of claim 5～8, wherein, the surface configuration of protuberance before the reduction of the area of concave bottom, net-like pattern is a quadrangle, and the prolongation on the summit by tetragonal angle, and the area of intersection point bottom in partly, recess is reduced.

10. according to each described manufacture method of claim 5～9, wherein, the distance (L) between the summit at tetragonal angle in the intersection point part, relative is below the 30 μ m.

11. according to each described manufacture method of claim 5～10, wherein, in the intersection point part, relative tetragonal bight has the shape of the isosceles triangle of acute angle, and the length on its base (a) is below the 30 μ m.

12. according to the manufacture method of claim 5～7 and 9～11 each described light-transmitting electromagnetic shielding materials, it is also electroplated after carrying out chemical plating.

13. a light-transmitting electromagnetic shielding material is characterized in that, the netted metal conducting layer that have transparency carrier, is provided with thereon, and,

14. light-transmitting electromagnetic shielding material according to claim 13, it is provided with netted preprocessing layer between transparency carrier and metal conducting layer.

15. according to claim 13 or 14 described light-transmitting electromagnetic shielding materials, wherein, the intersection point of grid part be shaped as quadrangle, and by tetragonal corner recess, the area of bottom in the intersection point part, recess is reduced.