JP2010219368A - Method of manufacturing base material for forming electromagnetic shielding layer and light-transmissive electromagnetic shielding material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a base material for forming an electromagnetic shielding layer having an anchor coat layer, which is formed using a composition having an superior pot life, and which has superior abrasion resistance, blocking resistance, adhesion to a printing ink and printing precision for the printing ink. <P>SOLUTION: The base material for forming the electromagnetic shielding layer is manufactured by including a step of forming the anchor coat layer 202 by coating and curing a composition containing a synthetic resin having a group containing an active hydrogen, polyisocyanate having at least two isocyanate groups and an organic metal catalyst on a transparent base material 201, wherein the content of the organic metal catalyst is 0.5-1.0 mass% to the total solid part of the composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  INDUSTRIAL APPLICABILITY The present invention is suitably used for a light-transmitting electromagnetic wave shielding material useful as a front sheet filter of a plasma display panel (PDP) or a sticking sheet that can be used for a window of a building requiring an electromagnetic wave shield such as a hospital. The present invention relates to a method for producing a substrate for forming an electromagnetic wave shielding layer.

  In recent years, with the spread of OA equipment, communication equipment, etc., there is a concern about the influence on the human body caused by electromagnetic waves generated from these equipment. In addition, electromagnetic waves from a mobile phone or the like may cause malfunction of precision equipment, and electromagnetic waves are regarded as a problem.

  Therefore, a light-transmitting electromagnetic wave shielding material having an electromagnetic wave shielding property and a light transmitting property has been developed and put into practical use as a front filter for a PDP of an OA device. Such a light-transmitting electromagnetic wave shielding material is also used as a window material for installation of precision equipment such as hospitals and laboratories in order to protect precision equipment from electromagnetic waves.

  In this light-transmitting electromagnetic wave shielding material, it is necessary to satisfy both the light transmitting property and the electromagnetic wave shielding property. For that purpose, for example, (1) a material having an electromagnetic wave shielding layer made of a conductive mesh in which a metal wire or a conductive fiber is made into a net is provided on one surface of a transparent substrate. The Electromagnetic waves are shielded by the conductive mesh portion, and light transmission is ensured by the opening.

  In addition, various types of light transmissive electromagnetic wave shielding materials have been proposed as filters for electronic displays. For example, (2) a transparent substrate provided with a transparent conductive thin film containing metallic silver, (3) a layer of copper foil or the like on the transparent substrate is etched into a net shape, and an opening is provided, (4) a transparent substrate In general, a conductive ink containing conductive powder printed on a mesh is known.

  In such an electromagnetic wave shielding layer, in order to achieve both excellent light transmittance and electromagnetic wave shielding properties, it is necessary to use a mesh-like transparent electromagnetic wave shielding layer, to make the line width extremely thin and to make a very fine pattern. . However, with the conventional light-transmitting electromagnetic wave shielding material described above, it has been difficult to achieve both light transmission and electromagnetic wave shielding sufficiently. That is, the light-transmitting electromagnetic wave shielding material (1) has a limitation in thinning, and it is difficult to obtain a fine mesh pattern, and there is a problem that the arrangement of fibers such as misalignment and bending is disturbed. In the case of the light-transmitting electromagnetic wave shielding material (2), there are problems such as insufficient electromagnetic wave shielding properties and strong reflection gloss specific to metals. The light-transmitting electromagnetic wave shielding material (3) has problems such as a long manufacturing process and high cost. Further, in the light transmissive electromagnetic wave shielding material of (4), it is difficult to obtain sufficient electromagnetic wave shielding properties. If the pattern is thickened to increase the electromagnetic shielding properties and the amount of conductive powder is increased, There are problems such as a decrease in permeability.

  However, the production of the light-transmitting electromagnetic wave shielding material (4) is performed by using an intaglio offset printing method on a transparent substrate using, for example, a conductive ink containing a conductive powder such as metal powder or carbon powder and a resin. This is performed using a method for forming a print pattern. Therefore, the light-transmitting electromagnetic wave shielding material (4) has an advantage that it can be produced by a simple method and at a low cost without requiring an etching process.

  Therefore, as an improvement of the technique of (4), in Patent Documents 1 and 2, in order to further improve the electromagnetic wave shielding property after forming a printing pattern on a transparent substrate with a conductive ink using an intaglio offset printing method. A method of selectively forming a metal layer on the printed pattern by electroless plating or electrolytic plating is disclosed.

  Further, in Patent Document 3, pattern printing is performed with a paste containing a carrier produced by supporting the noble metal ultrafine particle catalyst on particles having a surface charge opposite to that of the noble metal ultrafine particle catalyst on a transparent substrate. A method for producing a light-transmitting electromagnetic wave shielding material is disclosed in which electroless plating is performed on a printed noble metal ultrafine particle catalyst to form a conductive metal layer only on a pattern printing portion.

Japanese Patent No. 3017987 Japanese Patent No. 3532146 Japanese Patent No. 336383

  However, in the light-transmitting electromagnetic wave shielding material according to Patent Documents 1 to 3 described above, the printing ink such as conductive ink or catalyst ink printed on the transparent substrate is distorted or spreads, so that the printing ink can be accurately used. It was difficult to print, and it was difficult to form a mesh-like electromagnetic shielding layer having a fine pattern.

  Therefore, the present applicant forms an anchor coat layer in advance using a composition containing a synthetic resin having a specific glass transition temperature and a number average molecular weight on a transparent substrate, and a specific electroless layer is formed on the anchor coat layer. It has been found that dripping and spreading of the catalyst ink after printing can be suppressed by the method of printing the catalyst ink for plating, and a patent application has been filed earlier (Japanese Patent Application No. 2008-290572).

  However, the above-described anchor coat layer has low scratch resistance and blocking resistance, and there is a problem in that the surface of the anchor coat layer is scratched or transparency and adhesion are deteriorated in a subsequent process. In order to solve such problems, it is considered effective to crosslink the synthetic resin using a polyisocyanate compound and a curing catalyst. According to the means, an anchor coat layer having excellent hardness and flexibility can be formed. However, in an anchor coat layer in which a synthetic resin is cross-linked using a curing catalyst, not only the adhesion and printing accuracy of a printing ink such as a catalyst ink are lowered, but the composition is cured early and becomes unsuitable for printing ( In some cases, the problem of reduction in pot life may occur.

  Accordingly, an object of the present invention is to form an electromagnetic wave shield having an anchor coat layer which is formed using a composition excellent in pot life and has excellent scratch resistance, blocking resistance, adhesion to printing ink, and printing ink printing accuracy. It aims at providing the manufacturing method of the base material for layer formation.

The method for producing a substrate for forming an electromagnetic wave shielding layer according to the present invention for solving the above-described problems includes a synthetic resin having a group containing active hydrogen on a transparent substrate, a polyisocyanate having at least two isocyanate groups, and Applying a composition containing an organometallic catalyst and curing to form an anchor coat layer,
Content of the said organometallic catalyst is 0.5-1.0 mass% with respect to the total solid of the said composition, It is characterized by the above-mentioned.

  In the method of the present invention, an anchor coat excellent in hardness and flexibility is obtained by using a composition comprising a synthetic resin having a group containing active hydrogen, a polyisocyanate having at least two isocyanate groups, and an organometallic catalyst. A layer can be obtained. In particular, by using a predetermined amount of an organometallic catalyst as a curing catalyst, an anchor coat having excellent scratch resistance, blocking resistance, adhesion to printing ink, and printing ink printing accuracy without reducing the pot life of the composition. A layer can be formed.

  Therefore, on the anchor coat layer formed by the method of the present invention, it is possible to form a patterned electromagnetic wave shielding layer with excellent dimensional accuracy, and thereby, light transmission properties excellent in electromagnetic wave shielding properties and light transmission properties. An electromagnetic shielding material can be provided. Furthermore, since the anchor coat layer is excellent in scratch resistance and blocking resistance, the transparency of the light-transmitting electromagnetic wave shielding material can be improved.

It is explanatory drawing which shows an example of the process of forming an anchor coat layer. It is explanatory drawing which shows an example of the manufacturing method of the light-transmitting electromagnetic wave shielding material of this invention.

  The method for producing a substrate for forming an electromagnetic wave shielding layer of the present invention comprises a composition comprising a synthetic resin having a group containing active hydrogen, a polyisocyanate having at least two isocyanate groups, and an organometallic catalyst on a transparent substrate. Is applied and cured to form an anchor coat layer.

  In the method of the present invention, in particular, the content of the organometallic catalyst is 0.5 to 1.0% by mass, more preferably 0.5 to 0.7% by mass, based on the total solid content of the composition. It is characterized by that. By using the organometallic catalyst in such an amount, the synthetic resin can be appropriately cross-linked, scratch resistance, blocking resistance, adhesion to printing ink (especially electroless plating pretreatment agent), and It becomes possible to form an anchor coat layer having excellent printing accuracy of printing ink. Furthermore, the composition has a sufficiently long pot life and excellent long-term reliability.

  In addition, solid content of a composition means what remove | excluded the component which evaporates when forming an anchor coat layer, such as an organic solvent, for example, a synthetic resin, polyisocyanate, an organometallic catalyst, etc. are mentioned.

  As these organometallic catalysts, it is possible to form an anchor coat layer excellent in scratch resistance and blocking resistance by using these catalysts in which an organotin catalyst and an organotitanium catalyst are preferably used.

  Examples of organic titanium catalysts include tetrabutyl titanate, tetrapropyl titanate, diisopropoxy titanium bis (acetylacetonate), diisopropoxy bis (ethyl acetoacetate) titanium, 1,3-propanedioxytitanium bis (ethyl acetoacetate), di Examples thereof include titanium compounds such as oxytitanium bis-titanium ethyl acetoacetate and titanium tetraacetylacetonate.

  Examples of organotin catalysts include dialkyltin dicarboxylate, tetrabutyltin, tin tetrachloride, monobutyltin trichloride, dibutyltin dichloride, monobutyltin oxide, dibutyltin oxide, tetraoctyltin, dioctyltin dichloride, dioctyltin oxide, tetramethyltin, And tin compounds such as stannous octylate.

  The organometallic catalyst mentioned above may be used individually by 1 type, and can also use 2 or more types together.

  Of these, dialkyltin dicarboxylate is particularly preferably used as the organometallic catalyst. Specifically, the dialkyltin dicarboxylate is represented by the following formula (1):

(In the formula, R ¹ may be the same or different and each represents an alkyl group having 1 to 10, particularly 3 to 10 carbon atoms, and R ² may be the same or different. Each of which represents an alkyl group having 10 to 20 carbon atoms, particularly 10 to 15 carbon atoms). By using such a dialkyl tin dicarboxylate, it becomes possible to form an anchor coat layer capable of printing a printing ink (particularly, an electroless plating pretreatment agent) with excellent accuracy.

  Preferred examples of the dialkyltin dicarboxylate represented by the formula (1) include dimethyltin dilaurate, diethyltin dilaurate, dibutyltin dilaurate, and dioctyltin dilaurate. Of these, dibutyltin dilaurate is particularly preferable.

  The composition used in the method of the present invention includes a synthetic resin having a group containing active hydrogen. Examples of the group containing active hydrogen include a hydroxyl group, a primary amino group, a secondary amino group, and a carboxyl group, and a hydroxyl group is preferable.

  The equivalent (eg, hydroxyl value) of the group containing active hydrogen is preferably in the range of 0.5 to 10 mgKOH / g, particularly 0.5 to 5 mgKOH / g, based on the resin (1 g). Thereby, a synthetic resin can be bridge | crosslinked moderately in an anchor coat layer.

  Specifically as a synthetic resin, a polyester resin, a polyurethane resin, an acrylic resin, a vinyl acetate resin, and a cellulose resin can be mentioned preferably. These may be used alone or in combination of two or more. Other resins may be used in small amounts (about 20% by mass or less). Of these, polyester resins are particularly preferable.

  Examples of the polyester resin include unsaturated polyester resins obtained by a condensation reaction of a polyhydric alcohol and a dibasic acid. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, pentane glycol, hexanediol, neopentyl glycol, hydrogenated bisphenol A, bisphenol A, and glycerin. It is done. Examples of the dibasic acid include maleic anhydride, fumaric acid, adipic acid, phthalic anhydride, terephthalic acid, and isophthalic acid.

  The number average molecular weight Mn of the polyester resin is preferably in the range of 10,000 to 40,000, preferably 10,000 to 35,000, particularly preferably 10,000 to 30,000. By using such a polyester resin, it is possible to form an anchor coat layer excellent in printing accuracy of printing ink.

  The composition used in the method of the present invention comprises a polyisocyanate having at least two isocyanate groups. Examples of the polyisocyanate include aromatic diisocyanates such as tolylene diisocyanate (TDI), isophorone diisocyanate, xylylene diisocyanate, diphenylmethane-4,4-diisocyanate, polymethylene polyphenyl isocyanate (crude MDI); dicyclopentanyl diisocyanate. , Hexamethylene diisocyanate, 2,4,4′-trimethylhexamethylene diisocyanate, and 2,2 ′, 4-trimethylhexamethylene diisocyanate. Polyisocyanates such as trifunctional or higher functional isocyanate compounds such as a TDI adduct of trimethylolpropane can also be used. Of these, aromatic polyisocyanates, particularly polymethylene polyphenyl isocyanate, are preferred.

  The molecular weight of the polyisocyanate, particularly polymethylene polyphenyl isocyanate, is preferably 500 or less, particularly 200 to 400.

  The concentration of the isocyanate group is preferably 1 to 10% by mass, particularly 1 to 5% by mass, based on the total solid content of the composition. If the isocyanate group concentration exceeds 10% by mass, a composition having a sufficient pot life may not be obtained. If the isocyanate group concentration is less than 1% by mass, the synthetic resin cannot be sufficiently crosslinked and the anchor coat layer is flexible. May be reduced. Therefore, it is preferable to use polyisocyanate so as to obtain such a concentration of isocyanate groups.

  The composition preferably further comprises silicone oil. By using silicone oil, it is possible to form an anchor coat layer excellent in printing accuracy of printing ink.

  The content of the silicone oil is preferably 0.001 to 1.0 part by mass, particularly 0.005 to 0.5 part by mass with respect to 100 parts by mass of the synthetic resin.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, amino-modified silicone oil, and epoxy-modified silicone oil. Of these, dimethyl silicone oil is preferable.

  The dimethyl silicone oil is generally a dimethylpolysiloxane having a terminal and side chain of a methyl group, and the methylphenyl silicone oil is a part of the methyl group of the side group of the dimethylpolysiloxane having a terminal and side chain of a methyl group. The methyl hydrogen silicone oil is a hydrogenated polysiloxane in which a part of the methyl group of the side group of the dimethylpolysiloxane having a terminal side chain and a methyl group is replaced with hydrogen. Generally, it is a linear silicone oil.

  Alkyl-modified silicone oils, amino-modified silicone oils, and epoxy-modified silicone oils are generally modified polysiloxanes in which the terminal or side chain of the polysiloxane is replaced with an organic group (polyether group, alkyl group, or epoxy group). It is.

  The composition preferably further contains an organic solvent. Moreover, you may add a filler, surfactant, etc. to the said composition suitably.

  Examples of the organic solvent include toluene, ethyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropanol, xylene, n-butyl acetate, cellosolve, cellosolve acetate, n-butanol, isobutanol, and And cyclohexanone. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The content of the organic solvent is preferably 500 to 2000 parts by mass, particularly 500 to 1500 parts by mass with respect to 100 parts by mass of the synthetic resin. By using the organic solvent in such an amount, a composition having a sufficiently long pot life can be obtained.

  The anchor coat layer is formed by applying and curing a composition containing a synthetic resin, polyisocyanate, organometallic catalyst, and, if necessary, silicone oil on a transparent substrate. In the method of the present invention, the step of forming the anchor coat layer is performed by applying the composition onto the long transparent base material while the long transparent base material is running, and then curing the composition. It is preferable to carry out by winding a scale-like transparent substrate. In order to run the long transparent substrate in this manner, it is particularly preferable to use a roll-to-roll method as shown in FIG.

  The roll-to-roll method is performed as follows. The transparent base material 101 is pulled out from the roll 100A around which the long transparent base material 101 is wound, and the anchor coat layer forming composition is applied onto the transparent base material by the coating device 110 while the transparent base material 101 is running. After the process, the anchor coat layer 102 is formed by curing. In order to cure the applied composition, it is preferably performed by a curing device 111 that performs heating or the like. Thereafter, the long transparent substrate 101 having the anchor coat layer 102 is again wound into a roll to obtain a roll 100B.

  The anchor coat layer can be mass-produced efficiently by using the above-described means. When the formed anchor coat layer is wound up in a roll shape, scratches and blocking are particularly likely to occur. However, since the anchor coat layer of the present invention is excellent in scratch resistance, blocking resistance, etc., the occurrence of scratches and blocking can be suppressed to a high level.

  As a method for applying the composition, any of existing coating methods such as gravure coating, micro gravure coating, die coating, lip coating, roll reverse coating, wire bar coating, and kiss coating can be employed.

  In order to cure the applied composition, it is possible even at room temperature, in which case it is left for 1 to 5 days (especially 2 to 4 days). However, the composition coated on the transparent substrate is preferably heated to 80 to 140 ° C., particularly 90 to 120 ° C., and cured. The heating time at this time is preferably about 0.5 to 5 minutes, particularly about 0.5 to 3 minutes. Thereby, a synthetic resin can be bridge | crosslinked moderately and the anchor coat layer excellent in various characteristics can be formed.

  The thickness of the anchor coat layer is preferably 0.1 to 1 μm, particularly preferably 0.1 to 0.5 μm. The anchor coat layer having such a thickness is excellent in flexibility, scratch resistance, and blocking resistance.

  As described above, the anchor coat layer formed by the method of the present invention is excellent in adhesion to printing ink and printing accuracy of printing ink. Therefore, on the anchor coat layer, it is possible to form a patterned electromagnetic shielding layer having a uniform line width and thickness and excellent dimensional accuracy (that is, there is almost no difference from the design dimension). . A transparent substrate having such an anchor coat layer is used as a substrate for forming an electromagnetic wave shield layer. Moreover, the base material for electromagnetic wave shield layer formation in which the electromagnetic wave shield layer was formed on the anchor coat layer is used as a light transmissive electromagnetic wave shield material.

  In order to form the electromagnetic wave shielding layer on the anchor coat layer, since the anchor coat layer has excellent adhesion and printing accuracy to various inks such as printing ink, a conventionally known method using printing ink is used. Can be used. In particular, in the present invention, the electromagnetic wave shielding layer is formed by electroless plating after printing an electroless plating pretreatment agent in a predetermined pattern on the anchor coat layer formed by the above-described method. preferable.

That is, in the present invention, as shown in FIG.
The step of forming the anchor coat layer 202 on the transparent substrate 201 by the method described above (arrow A),
A process of forming a patterned pretreatment layer 203 by printing an electroless plating pretreatment agent on the anchor coat layer 202 in a mesh form (arrow B), and a pattern by electroless plating on the pretreatment layer 203 A step of forming the electromagnetic shielding layer 204 in the shape (arrow C),
It is particularly preferable to form an electromagnetic wave shielding layer on the anchor coat layer by a method having

  The anchor coat layer has excellent adhesion to the electroless plating pretreatment agent (printing ink), the line width and thickness are uniform on the anchor coat layer, and excellent dimensional accuracy (ie, design dimensions) A pattern-like pretreatment layer can be formed. Therefore, according to the above-described method, it is possible to easily form a patterned electromagnetic shielding layer with high accuracy and to provide a light-transmitting electromagnetic shielding material that is excellent in light transmission and electromagnetic shielding properties. it can.

  In the step of forming the patterned pretreatment layer, as the electroless plating pretreatment agent, an electroless plating pretreatment agent (A) containing a composite metal oxide and / or a composite metal oxide hydrate and a binder resin. Is particularly preferred. Such a pretreatment agent (A) has excellent adhesion to the anchor coat layer. In the pretreatment agent (A), the composite metal oxide and the composite metal oxide hydrate are excellent in stability and dispersibility, and they adhere uniformly during printing, so that the pretreatment agent (A) is almost as designed. It becomes possible to print on the anchor coat layer in the shape of dimensions.

  As the composite metal oxide and the composite metal oxide hydrate, those containing at least two metal elements selected from the group consisting of Pd, Ag, Si, Ti, and Zr are preferably used. More preferably, one containing a metal element of Pd or Ag and a metal element of Si, Ti or Zr is mentioned. Such composite metal oxides and composite metal oxide hydrates have high plating metal deposition ability, and further have excellent stability and dispersibility in the pretreatment agent (A).

  Especially, since the said characteristic is especially excellent, following formula (2)

(In the formula, M ¹ represents Pd or Ag, M ² represents Si, Ti, or Zr. When M ¹ is Pd, x is 1, and when M ¹ is Ag, x is 2. And n is an integer of 1 to 20). It is particularly preferable to use a composite metal oxide hydrate.

In the formula (I), M ¹ is Pd or Ag, but is preferably Pd. M ² is Si, Ti or Zr, but is preferably Ti. Thereby, the composite metal oxide hydrate having a high plating precipitation ability is obtained.

The specifically as a composite metal oxide _{hydrate, PdSiO 3, Ag 2 SiO 3} , PdTiO 3, hydrates of such Ag ₂ TiO _3, PdZrO ₃ and Ag ₂ TiO ₃ and the like.

  The above-mentioned mixed metal oxide hydrates are obtained by heating each corresponding metal salt, such as hydrochloride, sulfate, nitrate, halide, oxyhalide, hydrate of the corresponding metal oxide, and the like. And obtained by using a hydrolysis method or the like.

Further, as the composite metal oxide, (for M ^1, M ² and X, the equation (2) as _{^{synonymous) M 1 X · M 2 O}} 3 as represented by is preferably used.

  The average particle size of the composite metal oxide and the composite metal oxide hydrate is preferably 0.01 to 10 μm, particularly 0.05 to 3 μm. Thereby, it can be set as the composite metal oxide which has the high dispersibility and catalyst activity in which aggregation was suppressed, and the said composite metal oxide hydrate.

  In the present invention, the average particle diameter of the composite metal oxide and the composite metal oxide hydrate is obtained by observing the cross section of the pretreatment layer with an electron microscope (preferably a transmission electron microscope) at a magnification of about 1,000,000 times. Then, the projected area equivalent circle diameter of at least 100 composite metal oxides and the composite metal oxide hydrate is obtained and the number average value thereof is obtained.

  The content of the composite metal oxide and the composite metal oxide hydrate is preferably 10 to 100 parts by mass, more preferably 10 to 70 parts by mass with respect to 100 parts by mass of the binder resin. If the content is less than 10 parts by mass, sufficient plating deposition ability may not be obtained, and if it exceeds 100 parts by mass, streaks and fogging based on aggregation of these composite metal oxides may be formed.

  The electroless plating pretreatment agent (A) includes a binder resin. Thereby, adhesiveness with the anchor coat layer and electromagnetic wave shield layer of a pretreatment layer can be improved, it becomes difficult to peel a pretreatment layer, and it becomes possible to form an electromagnetic wave shield layer more accurately.

  The binder resin is not particularly limited as long as it can secure adhesion with the anchor coat layer and the electromagnetic wave shielding layer. Preferred examples of the binder resin include acrylic resins, polyester resins, polyurethane resins, vinyl chloride resins, and ethylene vinyl acetate copolymer resins. In particular, a polyurethane resin and a polyester resin are preferable. According to these, high adhesiveness with an anchor coat layer and an electromagnetic wave shield layer is obtained, and an electromagnetic wave shield layer can be accurately formed on a pretreatment layer. These binder resins may be used alone or in combination of two or more.

  In addition, as a polyester resin as binder resin, the thing similar to what was mentioned above as a synthetic resin used for an anchor coat layer is mentioned.

  The content of the binder resin is preferably 10 to 100% by mass, particularly 10 to 30% by mass, based on the total amount of the electroless plating pretreatment agent (A). Thereby, a pretreatment layer having high adhesion can be formed.

  The electroless plating pretreatment agent (A) preferably further contains a curing agent such as a polyisocyanate compound.

  The electroless plating pretreatment agent (A) may further contain inorganic fine particles. By containing the inorganic fine particles, it is possible to improve printing accuracy and to form an electromagnetic wave shielding layer with higher accuracy. Preferred examples of the inorganic fine particles include silica, calcium carbonate, alumina, talc, mica, glass flake, metal whisker, ceramic whisker, calcium sulfate whisker, and smectite. These may be used individually by 1 type, and may mix and use 2 or more types.

  The average particle size of the inorganic fine particles is preferably 0.01 to 5 μm, particularly preferably 0.1 to 3 μm. If the average particle size of the inorganic fine particles is less than 0.01 μm, the addition of the inorganic fine particles may not provide the desired improvement in printing accuracy, and if it exceeds 5 μm, streaks and fog may be likely to occur. is there.

  The content of the inorganic fine particles in the electroless plating pretreatment agent (A) is preferably 10 to 100 parts by mass, particularly preferably 10 to 30 parts by mass with respect to 100 parts by mass of the binder resin. Thereby, it can be set as the pretreatment agent with high printing appropriateness.

  Moreover, the electroless plating pretreatment agent (A) may further contain a thixotropic agent. According to the thixotropic agent, it is possible to improve the printing accuracy by adjusting the fluidity of the pretreatment agent, and it is possible to form an electromagnetic shielding layer with higher accuracy. As the thixotropic agent, any conventionally known thixotropic agent can be used. Preferably, amide wax, hydrogenated castor oil, beeswax, carnauba wax, stearamide, hydroxystearic acid ethylene bisamide and the like can be used.

  The content of the thixotropic agent in the electroless plating pretreatment agent (A) is preferably 0.1 to 20 parts by mass, particularly 1 to 15 parts by mass with respect to 100 parts by mass of the binder resin. Thereby, it can be set as the pretreatment agent with high printing appropriateness.

  The electroless plating pretreatment agent (A) of the present invention may further contain a black colorant. Thereby, with the improvement of a printing precision, the glare-proof effect at the time of seeing from the transparent base material side can be provided in the light transmissive electromagnetic wave shielding material obtained.

  Preferred examples of the black colorant include carbon black, titanium black, black iron oxide, graphite, and activated carbon. These may be used individually by 1 type and may be used in mixture of 2 or more types. Of these, carbon black is preferable. Examples of carbon black include acetylene black, channel black, and furnace black. The average particle size of carbon black is preferably 0.1 to 1,000 nm, particularly preferably 5 to 500 nm.

  The content of the black colorant in the electroless plating pretreatment agent (A) is preferably 0.1 to 10 parts by mass, particularly 1 to 5 parts by mass with respect to 100 parts by mass of the binder resin. This makes it possible to accurately form a pretreatment layer having an antiglare effect.

  When using a black colorant, it is preferable to prepare the electroless plating pretreatment agent (A) using a commercially available black ink. Examples of such black ink include SS8911 manufactured by Toyo Ink Manufacturing Co., Ltd., EXG-3590 manufactured by Jujo Chemical Co., Ltd., and NT Hiramic 795R Black manufactured by Dainichi Seika Kogyo Co., Ltd. For example, in the case of SS8911 manufactured by Toyo Ink Manufacturing Co., Ltd., the solvent contains vinyl chloride and acrylic resin in addition to carbon black. Therefore, if it is an above-mentioned commercial item, preparation of the electroless-plating pre-processing agent containing binder resin and a black coloring agent can be performed easily.

  Moreover, it is preferable that the electroless-plating pretreatment agent (A) contains an organic solvent. Specific examples of the organic solvent include toluene, ethyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropanol, xylene, n-butyl acetate, cellosolve, cellosolve acetate, n-butanol, isoform. Examples include butanol and cyclohexanone. These may be used individually by 1 type, and 2 or more types may be mixed and used for them. These organic solvents can ensure excellent adhesion between the anchor coat layer and the transparent substrate even if the organic solvent contained in the printed electroless plating pretreatment agent is absorbed by the anchor coat layer. it can.

  The electroless plating pretreatment agent (A) may further contain various additives such as extender pigments and surfactants as necessary.

  The viscosity of the electroless plating pretreatment agent (A) is preferably 500 to 5000 cps, more preferably 1000 to 25 ° C. in order to obtain a pretreatment layer having a fine line width and a gap (pitch) by printing. It is good to set it as 3000 cps.

  In the method of the present invention, an electroless plating pretreatment agent (B) containing a mixture or reaction product of a silane coupling agent and an azole compound and a noble metal compound is also preferably used. As with the electroless plating pretreatment agent (A), the electroless plating pretreatment agent (B) is almost designed by pattern printing on the anchor coat layer. It can be formed with street dimensions.

  As the silane coupling agent used for the electroless plating pretreatment agent (B), it is preferable to use a silane coupling agent having a functional group having a metal-capturing ability in one molecule. Thereby, it becomes possible to set it as the electronic state and orientation which express the activity of the noble metal compound which is an electroless-plating catalyst effectively, and high adhesiveness with a to-be-plated material is obtained.

  Preferred examples of the silane coupling agent include epoxy group-containing silane compounds. Examples of the epoxy group-containing silane compound include γ-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyltriethoxysilane. , 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. These may be used alone or in combination of two or more. In particular, γ-glycidoxypropyltrialkoxysilane is preferred because the pretreatment layer obtained exhibits high adhesion to the anchor coat layer and the electromagnetic wave shielding layer.

  Next, as an azole compound used for the electroless plating pretreatment agent (B), imidazole, oxazole, thiazole, selenazole, pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole, Examples include thiatriazole, benzazole, indazole, benzimidazole, benzotriazole, and indazole. Although not limited to these, imidazole is particularly preferable because it is excellent in reactivity with a functional group such as an epoxy group of the silane coupling agent and a noble metal compound.

  In the electroless plating pretreatment agent (B), the silane coupling agent and the azole compound may be simply mixed, but they may be reacted in advance to form a reaction product. Thereby, while being able to disperse | distribute a noble metal compound more highly in a pretreatment layer, the light transmittance of the pretreatment layer obtained can be improved.

  In order to react the silane coupling agent with the azole compound, for example, 0.1 to 10 mol of the silane coupling agent is mixed with 1 mol of the azole compound at 80 to 200 ° C. for 5 minutes to 2 minutes. It is preferable to react for a time. At that time, a solvent is not particularly required, but an organic solvent such as chloroform, dioxanemethanol, ethanol or the like may be used in addition to water. An electroless plating pretreatment agent can be obtained by mixing a noble metal compound with the reaction product of the silane coupling agent and the azole compound thus obtained.

  Next, the noble metal compound used for the electroless plating pretreatment agent (B) exhibits a catalytic effect capable of selectively depositing and growing a metal such as copper or aluminum in the electroless plating treatment. Specifically, it is preferable to use a compound containing a metal atom such as palladium, silver, platinum, and gold because high catalytic activity is obtained. Examples of the compound include chlorides, hydroxides, oxides, sulfates, ammonium salts, and the like of the metal atom, and palladium compounds, particularly palladium chloride is preferable.

  The electroless plating pretreatment agent (B) preferably contains 0.001 to 50 mol%, more preferably 0.1 to 20 mol% of a noble metal compound with respect to the azole compound and the silane coupling agent. If the concentration of the noble metal compound is less than 0.001 mol%, sufficient catalytic activity may not be obtained and an electromagnetic wave shielding layer having a desired thickness may not be formed. If the concentration exceeds 50 mol%, the noble metal commensurate with the increase in the amount added. There is a possibility that the catalytic effect of the compound cannot be obtained.

  Moreover, it is preferable that the electroless-plating pretreatment agent (B) contains an organic solvent. As an organic solvent, the same thing as the electroless-plating pretreatment agent (A) mentioned above is used. The electroless plating pretreatment agent (A) may further contain various additives such as extender pigments, surfactants, and colorants as necessary.

  The viscosity of the electroless plating pretreatment agent (B) is preferably 500 to 5000 cps, more preferably 1000 to 25 ° C in order to obtain a pretreatment layer having a fine line width and a gap (pitch) by printing. It is good to set it as 3000 cps.

  In the method of the present invention, the above-described electroless plating pretreatment agent (A) or (B), in particular, the electroless plating pretreatment agent (A) is printed in a pattern on the anchor coat layer, thereby fixing the anchor coat layer. A patterned pretreatment layer is formed thereon. Thereby, a pretreatment layer having a desired fine pattern can be formed by a simple method.

  In order to print the electroless plating pretreatment agent (A) or (B) on the anchor coat layer, a printing method such as gravure printing, flexographic printing, gravure offset printing, screen printing, inkjet printing, electrostatic printing or the like is used. it can. In particular, gravure printing and gravure offset printing are suitable for thinning. When using gravure printing, the printing speed is preferably 5 to 50 m / min.

  After printing the electroless plating pretreatment agent (A) or (B) in this way, it is preferably dried by heating at 80 to 160 ° C., more preferably 90 to 130 ° C. If the drying temperature is less than 80 ° C., the evaporation rate of the solvent is slow, and there is a possibility that sufficient film formability may not be obtained. The drying time for heat drying after coating is preferably 5 seconds to 5 minutes.

  The pattern shape of the pretreatment layer may be appropriately determined so as to obtain a desired electromagnetic wave shielding layer, but is preferably a stripe shape and a mesh shape (including a lattice shape), particularly a mesh shape.

  The shape of the mesh pattern in the pretreatment layer is not particularly limited, and examples thereof include a lattice shape in which square openings are formed, and a punching metal shape in which circular, hexagonal, triangular, or elliptical openings are formed. It is done. Further, the openings are not limited to those regularly arranged, and may be a random pattern.

  The line width of the mesh-shaped pretreatment layer is generally 25 μm or less, preferably 5 to 20 μm, particularly 5 to 15 μm. The line pitch is preferably 300 μm or less. Further, the aperture ratio is preferably 75 to 95%, particularly 80 to 95%. The aperture ratio refers to the ratio of the opening portion in the projected area of the pretreatment layer.

  The shape of the opening surrounded by the line of the pretreatment layer can be an arbitrary shape such as a circle, an ellipse, or a square (quadrangle, hexagon), but is generally a square, and particularly preferably a square. .

  The pretreatment layer has a thickness of 0.01 to 5 μm, preferably 0.1 to 2 μm. Thereby, high adhesiveness with an anchor coat layer and an electromagnetic wave shield layer is securable.

  When the step of forming the patterned pretreatment layer using the electroless plating pretreatment agent (A) is performed, the pretreatment layer is formed after the step and before the step of forming the patterned electromagnetic wave shielding layer. It is preferable to carry out a reduction treatment step. Reduction treatment reduces the metal species contained in the composite metal oxide and composite metal oxide hydrate that are electroless plating catalysts contained in the pretreatment layer, and only the metal species that are active components are in the form of ultrafine particles. Can be deposited uniformly. The metal species thus reduced and deposited have high catalytic activity and are stable, so that the adhesion between the pretreatment layer and the anchor coat layer and the deposition rate of electroless plating are improved. It becomes possible to reduce the usage-amount of a thing and a composite metal oxide hydrate.

  The reduction treatment is not particularly limited as long as it is a method capable of reducing and metallizing the composite metal oxide and the composite metal oxide hydrate contained in the pretreatment layer. Specifically, (i) a liquid phase reduction method in which a transparent substrate on which a pretreatment layer is formed is treated with a solution containing a reducing agent, (ii) a transparent substrate on which a pretreatment layer is formed, A gas phase reduction method in which a reducing gas is contacted is preferably used.

  As a method of processing using a solution containing a reducing agent in a liquid phase reduction method, specifically, a method of immersing a transparent substrate on which a pretreatment layer is formed in a solution containing a reducing agent, A method of spraying a solution containing a reducing agent on the surface on which the treatment layer is formed is used.

The solution containing a reducing agent is prepared by dispersing or dissolving a predetermined reducing agent in a solvent such as water. The reducing agent is not particularly limited, but formamide, dimethylformamide, diethylformamide, dimethylacetamide, dimethylacrylamide, sodium borohydride, potassium borohydride, glucose, aminoborane, dimethylamineborane (DMAB), trimethylamineborane (TMAB) Hydrazine, diethylamine borane, formaldehyde, glyoxylic acid, imidazole, ascorbic acid, hydroxylamine, hydroxylamine sulfate, hydroxylamine hydrochloride, hypophosphite, sodium hypophosphite and other hypophosphites, hydroxylamine sulfate, sulfite Examples thereof include sulfites such as sodium, hydrosulfite (Na ₂ S ₂ O ₄ : also referred to as sodium dithionite), and the like. If the reducing agent is the same as the reducing agent contained in the electroless plating bath used in the post-process, electroless plating can be performed without washing the transparent substrate after the reduction treatment with water. There is little risk of changing the composition of the electroplating bath.

  As the reducing agent, aminoborane, dimethylamine borane, sodium hypophosphite, hydroxylamine sulfate, hydrosulfite, and formalin are preferably used because high reducibility can be obtained.

  The content of the reducing agent in the solution containing the reducing agent is preferably 0.01 to 200 g / L, particularly preferably 0.1 to 100 g / L. If the concentration of the reducing agent is too low, it may take a long time to sufficiently perform the reduction treatment, and if the concentration of the reducing agent is too high, the deposited plating catalyst may fall off.

  As a method of processing using a solution containing a reducing agent in the liquid phase reduction method, since the high reducibility of the composite metal oxide and composite metal oxide hydrate contained in the pretreatment layer is obtained, the pretreatment layer is It is preferable to use a method of immersing the formed transparent substrate in a solution containing a reducing agent.

  When the transparent substrate is immersed, the temperature of the solution containing the reducing agent is preferably 20 to 90 ° C, particularly 50 to 80 ° C. Further, the immersion time may be at least 1 minute or more, preferably about 1 to 10 minutes.

  On the other hand, when the reduction treatment is performed using the gas phase reduction method, the reducing gas is not particularly limited as long as it is a reducing gas such as hydrogen gas or diborane gas. What is necessary is just to determine suitably the reaction temperature and reaction time at the time of the reduction process using reducing gas according to the kind etc. of reducing gas to be used.

  Next, a step of forming a patterned electromagnetic wave shielding layer by electroless plating treatment is performed on the pretreatment layer formed as described above. By performing the electroless plating treatment, fine metal particles are deposited and formed as a dense and substantially continuous film, and an electromagnetic wave shielding layer can be selectively obtained only on the pretreatment layer.

  The plating metal can be used as long as it is conductive and can be plated, and may be a single metal, an alloy, a conductive metal oxide, etc. It may be made of fine fine particles.

  As a plating metal in electroless plating, aluminum, nickel, indium, chromium, gold, vanadium, tin, cadmium, silver, platinum, copper, titanium, cobalt, lead, or the like can be used. In particular, silver, copper, or aluminum is preferably used because a conductive layer with high electromagnetic shielding properties can be obtained. The electromagnetic wave shielding layer formed using these plated metals is excellent in adhesion to the pretreatment layer, and is suitable for achieving both light transmittance and electromagnetic wave shielding properties.

  Electroless plating can be performed at room temperature or under heating according to a conventional method using an electroless plating bath. That is, the plating substrate is immersed in a bath containing a plating solution containing a plating metal salt, a chelating agent, a pH adjuster, a reducing agent, etc. as a basic composition, or a component plating solution is added separately from two or more solutions What is necessary is just to select suitably, such as performing a plating process by a system.

  As an example of electroless plating, when an electromagnetic shielding layer made of Cu is formed, a water-soluble copper salt such as copper sulfate 1 to 100 g / L, particularly 5 to 50 g / L, a reducing agent such as formaldehyde 0.5 to 0.5 10 g / L, especially 1 to 5 g / L, a solution containing 20 to 100 g / L, particularly 30 to 70 g / L of a complexing agent such as EDTA, and adjusted to pH 12 to 13.5, particularly 12.5 to 13 A method of immersing a transparent substrate having a pretreatment layer and an anchor coat layer at 50 to 90 ° C. for 30 seconds to 60 minutes can be employed.

  When performing electroless plating, the substrate to be plated may be rocked and rotated, or the vicinity thereof may be agitated with air.

  The pattern shape of the electromagnetic wave shielding layer is preferably a stripe shape and a mesh shape (including a lattice shape), particularly a mesh shape. The electromagnetic wave shielding layer having these patterns can ensure conductivity by the pattern forming portion and can ensure light transmission by the opening.

  The shape of the mesh pattern in the electromagnetic wave shielding layer is not particularly limited, and examples thereof include a lattice shape in which square openings are formed, and a punching metal shape in which circular, hexagonal, triangular or elliptical openings are formed. It is done. Further, the openings are not limited to those regularly arranged, and may be a random pattern.

  The line width of the mesh-shaped electromagnetic wave shielding layer is generally 25 μm or less, preferably 5 to 20 μm, particularly 5 to 15 μm. The line pitch is preferably 300 μm or less. Further, the aperture ratio is preferably 75 to 95%, particularly 80 to 95%. In addition, an aperture ratio means the ratio for which the opening part accounts in the projection area of an electromagnetic wave shield layer.

  The shape of the opening surrounded by the line of the electromagnetic wave shielding layer can be any shape such as a circle, an ellipse, and a square (quadrangle, hexagon), but is generally a square, and particularly preferably a square. .

  In the method of the present invention, a metal plating layer may be formed on the electromagnetic wave shielding layer by performing an electroplating treatment after the step of forming the patterned electromagnetic wave shielding layer.

  The material used for the electroplating treatment is not particularly limited as long as the metal plating layer has an excellent electromagnetic wave shielding effect, but for example, copper, nickel, chromium, zinc, tin, silver, gold, etc. A metal is mentioned. These may be used individually by 1 type and may be used as 2 or more types of alloys.

  0.1-10 micrometers is preferable and, as for the thickness of a metal plating layer, 2-5 micrometers is more preferable. When the thickness is less than 0.1 μm, a sufficient electromagnetic shielding effect may not be imparted. On the other hand, when the thickness exceeds 10 μm, the electroplating layer spreads in the width direction, so that the line width increases and the electromagnetic shielding layer May have a low aperture ratio.

  The surface resistivity of the metal plating layer is preferably 3Ω / □ or less, and more preferably 1Ω / □ or less. If the surface resistivity of the metal plating layer exceeds 3Ω / □, the conductivity may be insufficient and the electromagnetic shielding effect may be insufficient.

  Further, the meshed electromagnetic wave shielding layer or the metal plating layer may be subjected to blackening treatment, for example, oxidation treatment of a metal film, black plating of a chromium alloy, application of black or dark color ink, or the like. be able to.

  In the method of the present invention, as described above, the step of forming the anchor coat layer, the step of forming the pretreatment layer, the step of forming the electromagnetic wave shielding layer, and the step of forming the metal plating layer as necessary, and black Each process such as a process for performing the chemical conversion treatment is performed. On the other hand, when the roll which wound up the elongate transparent base material in which the anchor coat layer was formed was produced like the form shown by FIG. 1, the anchor coat layer was formed from the said roll in the post process. It is preferable to carry out while running on a long transparent substrate. The long transparent substrate on which the anchor coat layer is formed is cut into a shape such as a rectangular shape according to the application in a subsequent step. The time for cutting the long transparent substrate in this way is not particularly limited, but it is particularly preferable to carry out after performing all subsequent steps.

The light-transmitting electromagnetic wave shielding material obtained by the method of the present invention described above includes a transparent base material, an anchor coat layer formed on the transparent base material, and a pattern-shaped pretreatment formed on the anchor coat layer. A layer and a patterned electromagnetic shielding layer formed on the patterned pretreatment layer,
The anchor coat layer comprises a cured layer of a composition comprising a synthetic resin having a group containing active hydrogen, a polyisocyanate having at least two isocyanate groups, and an organometallic catalyst;
Content of the said organometallic catalyst is 0.5-1.0 mass% with respect to the total solid of the said composition, It is characterized by the above-mentioned.

  Such a light-transmitting electromagnetic wave shielding material of the present invention prints the electroless plating pretreatment agent with high accuracy without causing dripping or repellency by the anchor coat layer formed on the transparent substrate. be able to. This makes it possible to easily form a mesh-shaped pretreatment layer with uniform line width and thickness and excellent dimensional accuracy (that is, there is almost no difference from the design dimension). A shape with excellent dimensional accuracy can be obtained. Therefore, the light transmissive electromagnetic wave shielding material obtained by the method of the present invention is excellent in electromagnetic wave shielding properties and light transmissive properties.

  The light-transmitting electromagnetic wave shielding material of the present invention is used for applications requiring electromagnetic wave shielding and light transmission, for example, display surfaces of display devices such as LCDs, PDPs, and CRTs of various electric devices that generate electromagnetic waves, or facilities and houses. It is suitably applied to the transparent glass surface and the transparent panel surface. In addition, it can be applied to panel switches such as touch panels and light transmission switches, noise countermeasure components, heating elements, electrodes for organic electroluminescence, electrodes for backlights, and the like. Especially, since it has high light transmittance and electromagnetic wave shielding property, it is preferably used as a light transmissive electromagnetic wave shielding material suitably used for the display filter of the display device described above.

  When using the light-transmitting electromagnetic wave shielding material of the present invention as a display filter, the light-transmitting electromagnetic wave shielding material is not particularly limited, but is bonded to a transparent substrate such as a glass plate via an adhesive layer or the like. Used. In such a display filter, the opening of the conductive pattern layer having a predetermined pattern, particularly a mesh pattern, is filled with an adhesive layer.

  Moreover, the light-transmitting electromagnetic wave shielding material may further have an antireflection layer, a color tone correction filter layer, a near infrared cut layer, and the like in addition to the transparent base material, the anchor coat layer, and the electromagnetic wave shielding layer. The order of stacking these layers is determined according to the purpose. Further, the light transmissive electromagnetic wave shielding material may be provided with an electrode for connecting to the ground electrode of the PDP main body in order to enhance the electromagnetic wave shielding function.

  Hereinafter, the present invention will be described with reference to examples. The present invention is not limited by the following examples.

Example 1
1. Preparation of anchor coat layer forming composition 100 parts by mass of unsaturated polyester resin (number average molecular weight 30,000, hydroxyl number 2.0) as resin component, polymethylene polyphenyl polyisocyanate (isocyanate group content 4) 0.5 mass%) 5 parts by mass, 500 parts by mass of cyclohexanone and 500 parts by mass of methyl ethyl ketone as a solvent, and silicone oil (dimethylpolysiloxane KF-96-200CS manufactured by Shin-Etsu Chemical Co., Ltd.) as a smoothing agent were mixed. Dibutyltin dilaurate was added to the obtained mixture in an amount of 0.5% by mass based on the total amount of the mixture, and mixed well to prepare an anchor coat layer forming composition.

2. Preparation of Anchor Coat Layer The composition for forming an anchor coat layer was applied on a PET film (thickness 100 μm, S grade, manufactured by Teijin) with a micro gravure coating machine, and the inside of a drying furnace having an average temperature of 100 ° C. An anchor coat layer was formed by passing for 60 seconds.

3. Preparation of Pretreatment Layer Composite Metal Oxide Hydrate Particles (PdTiO ₃ .6H ₂ O, Average Particle Diameter 0.5 μm) are added to a two-component curable polyester urethane resin solution with respect to 100 parts by mass of polyester urethane resin. A pretreatment agent was prepared by blending 30 parts by mass of the composite metal oxide hydrate particles. The two-component curable polyester urethane resin solution is a mass ratio of polyester resin (AD-335A manufactured by Toyo Morton Co., Ltd., Tg: 10 ° C.) and alicyclic isocyanate (CAT-10L manufactured by Toyo Morton Co., Ltd.). 100: 0.5 and a solid concentration of 10% by mass was used.

  The pretreatment agent was printed in a mesh shape on the anchor coat layer by gravure printing, and then dried at 120 ° C. for 5 minutes to form a mesh-like pretreatment layer on the anchor coat layer. As the gravure printing plate, a mold having a groove with a line width of 30 μm, a line depth of 0.5 μm, and a line interval of 165 μm was used.

4). Next, the PET film on which the pretreatment layer has been formed as described above is immersed in a sodium hypophosphite solution (NaH ₂ PO ₂ concentration: 30 g / L) at 60 ° C. for 3 minutes. The pretreatment layer was reduced.

5). Production of Electromagnetic Shielding Layer The PET film on which the pretreatment layer reduced as described above is formed is immersed in an electroless copper plating solution (Melplate CU-5100 manufactured by Meltex Co., Ltd.) at 50 ° C. for 20 minutes. Electroless copper plating treatment was performed to produce a mesh-like electromagnetic wave shielding layer, and a light-transmitting electromagnetic wave shielding material was obtained. The metal conductive layer had a line width of 30 μm, a line interval of 165 μm, an aperture ratio of 67%, and a thickness of 3 μm.

(Example 2)
In the preparation of the anchor coat layer forming composition of Example 1, a light-transmitting electromagnetic wave shield was obtained in the same manner as in Example 1 except that the addition amount of dibutyltin dilaurate was changed from 0.5% by mass to 1.0% by mass. A material was prepared.

Example 3
In the preparation of the anchor coat layer forming composition of Example 1, light was used in the same manner as in Example 1 except that 1.0% by mass of diisopropoxybis (ethylacetoacetate) titanium was used instead of dibutyltin dilaurate. A transmissive electromagnetic shielding material was produced.

(Reference Example 1)
A light-transmitting electromagnetic wave shielding material was produced in the same manner as in Example 1 except that dibutyltin dilaurate was not used in the preparation of the anchor coat layer forming composition of Example 1.

(Reference Example 2)
In the preparation of the anchor coat layer forming composition of Example 1, dibutyltin dilaurate was not used, and the time for the PET film coated with the anchor coat layer forming composition to pass through the drying furnace was changed to 180 ° C. Produced a light-transmitting electromagnetic wave shielding material in the same manner as in Example 1.

(Reference Example 3)
In the preparation of the anchor coat layer forming composition of Example 1, a light-transmitting electromagnetic wave shield was obtained in the same manner as in Example 1 except that the addition amount of dibutyltin dilaurate was changed from 0.5% by mass to 5.0% by mass. A material was prepared.

(Reference Example 4)
In the preparation of the anchor coat layer-forming composition of Example 1, light was used in the same manner as in Example 1 except that 4.0% by mass of diisopropoxybis (ethylacetoacetate) titanium was used instead of dibutyltin dilaurate. A transmissive electromagnetic shielding material was produced.

(Reference Example 5)
In the preparation of the anchor coat layer forming composition of Example 1, a light-transmitting electromagnetic wave shield was obtained in the same manner as in Example 1 except that the addition amount of dibutyltin dilaurate was changed from 0.5% by mass to 0.005% by mass. A material was prepared.

(Evaluation)
The following evaluation was performed about each anchor coat layer produced above. The results are shown in Table 1.

1. Thickness The thickness of the anchor coat layer was measured using a thin film measuring device (F20 Filmetrics Co., Ltd.). The thickness was measured at three locations, and the average value of the measured values was taken.

2. Scratch resistance In order to evaluate the scratch resistance of the anchor coat layer, a steel wool test was performed according to the following procedure. Using # 0000 steel wool, a load of 100 g / cm ² was applied, and the anchor coat layer was rubbed 10 times at a stroke of 50 MM and a speed of 10 MM / SEC, and then the presence or absence of scratches was visually evaluated. In Table 1, the case where no scratch was generated was indicated as “◯”, and the case where a scratch was generated was indicated as “X”.

3. Blocking resistance Five anchor coat layers cut to 5 cm × 5 cm were stacked, and then sandwiched between two glass plates (thickness 25 mm). The obtained laminate was placed on a 10 kg weight in a constant temperature bath at 50 ° C. and left for 8 hours and left in an atmosphere at 25 ° C. for 1 hour, and then the anchor coat layer disposed on the uppermost layer was placed at 1 cm / second. It pulled up with the hand at speed, and observed the degree of resistance to the hand and ease of peeling at that time. In Table 1, when the anchor coat layer was peeled off, “○” indicates that there was no resistance to the hand and it was easy to peel off, and “△” indicates that there was a slight resistance to the hand. The case where there was a sense of resistance or was not peeled off at all was designated as “x”.

4). Printing characteristics The line width and pitch of the mesh-shaped pretreatment layer formed on the anchor coat layer were measured. The printing accuracy decreases as the difference is larger than the line width (30 μm) and the line interval (165 μm) of the groove of the gravure printing plate as the design dimension.

5). Adhesiveness A cellophane tape (CT24 manufactured by Nichiban Co., Ltd.) was adhered to the mesh-shaped pretreatment layer prepared on the anchor coat layer, and then peeled off. The peeling state was confirmed visually. In Table 1, a case where no peeling of the mesh-shaped pretreatment layer was observed was indicated as “◯”, and a case where the mesh-shaped pretreatment layer was peeled as a whole was indicated as “x”.

6). Pot life The composition for forming an anchor coat layer was sealed and allowed to stand at room temperature for 24 hours, and the viscosity of the composition before and after being left was measured. When the rate of change in viscosity was within 15%, “◯” was given, and when the viscosity was over 15%, “X” was given.

6). Number average molecular weight Mn
The number average molecular weight Mn of the polyester resin used for forming the anchor coat layer was measured under the following conditions.

Apparatus: manufactured by Tosoh Corporation, high performance liquid chromatography “HLC-8120GPC”,
Column: manufactured by Tosoh Corporation, “Super H2000 + H4000”, 6 mm D. , 15cm,
Eluent: THF, g
Flow rate: 0.500 ml / min,
Detector: RI,
Column bath temperature: 40 ° C
Polystyrene standard.

  From the results shown in Table 1, it can be seen that the anchor coat layers formed in Examples 1 to 3 are excellent in scratch resistance, blocking resistance, adhesion to printing ink, and printing accuracy of printing ink. Therefore, a pretreatment layer and an electromagnetic wave shielding layer having a uniform line width and thickness and excellent dimensional accuracy can be formed on such an anchor coat layer.

100A: a roll obtained by winding a long transparent substrate,
100B: a roll obtained by winding a long transparent substrate on which an anchor coat layer is formed,
110: Coating device,
111: Curing device,
101, 201: transparent substrate,
102, 202: anchor coat layer,
203: Patterned pretreatment layer,
204: Patterned electromagnetic wave shielding layer,
Arrow a: traveling direction of the transparent substrate.

Claims (15)

A process of forming an anchor coat layer by applying and curing a composition containing a synthetic resin having a group containing active hydrogen, a polyisocyanate having at least two isocyanate groups, and an organometallic catalyst on a transparent substrate. Have
The manufacturing method of the base material for electromagnetic wave shield layer formation whose content of the said organometallic catalyst is 0.5-1.0 mass% with respect to the total solid of the said composition.   The method for producing a substrate for forming an electromagnetic wave shield layer according to claim 1, wherein the organometallic catalyst is an organotin catalyst and / or an organotitanium catalyst. The organometallic catalyst is represented by the following formula (1):

(Wherein R ¹ may be the same or different, each represents an alkyl group having 1 to 10 carbon atoms, and R ² may be the same or different, The method for producing a base material for forming an electromagnetic wave shield layer according to claim 1 or 2, wherein the dialkyltin dicarboxylate is represented by the following formula: an alkyl group having 10 to 20 carbon atoms.   In the step of forming the anchor coat layer, a long transparent substrate is used as the transparent substrate, and the composition is formed on the long transparent substrate while the long transparent substrate is running. The manufacturing method of the base material for electromagnetic wave shield layer formation of any one of Claims 1-3 performed by winding up the said elongate transparent base material after apply | coating and hardening.   The manufacturing method of the base material for electromagnetic wave shield layer formation of any one of Claims 1-4 which perform the said hardening by heating at 80-140 degreeC for 0.5 to 5 minutes. Forming an anchor coat layer by the method according to any one of claims 1 to 5,
A process of forming a pattern-shaped pretreatment layer by printing an electroless plating pretreatment agent on the anchor coat layer in a pattern, and a pattern-shaped electromagnetic wave shielding layer on the pretreatment layer by electroless plating Forming a process,
The manufacturing method of the light-transmitting electromagnetic wave shielding material which has this.   The method for producing a light-transmitting electromagnetic wave shielding material according to claim 6, wherein the electroless plating pretreatment agent includes a composite metal oxide and / or a composite metal oxide hydrate and a binder resin. The composite metal oxide hydrate is represented by the following formula (2):

(In the formula, M ¹ represents Pd or Ag, M ² represents Si, Ti or Zr. When M ¹ is Pd, x is 1, and when M ¹ is Ag, x is 2 and n is an integer of 1 to 20, and the method for producing a light-transmitting electromagnetic wave shielding material according to claim 7.   The method for producing a light-transmitting electromagnetic wave shielding material according to claim 7 or 8, further comprising a step of reducing the pretreatment layer before the step of forming the mesh-shaped metal electromagnetic wave shielding layer.   The method for producing a light-transmitting electromagnetic wave shielding material according to any one of claims 6 to 9, wherein a plating metal in the electroless plating is silver, copper, or aluminum. A transparent substrate, an anchor coat layer formed on the transparent substrate, a patterned pretreatment layer formed on the anchor coat layer, and a pattern formed on the patterned pretreatment layer Having an electromagnetic shielding layer of
The anchor coat layer comprises a cured layer of a composition comprising a synthetic resin having a group containing active hydrogen, a polyisocyanate having at least two isocyanate groups, and an organometallic catalyst;
The light transmissive electromagnetic wave shielding material whose content of the said organometallic catalyst is 0.5-1.0 mass% with respect to the total solid of the said composition.   The light-transmitting electromagnetic wave shielding material according to claim 11, wherein the organometallic catalyst is an organotin catalyst and / or an organotitanium catalyst. The organometallic catalyst is represented by the following formula (1):

(Wherein R ¹ represents the same or different alkyl group having 1 to 10 carbon atoms, and R ² represents the same or different carbon group. The light-transmitting electromagnetic wave shielding material according to claim 11 or 12, which is a dialkyltin dicarboxylate represented by an alkyl group having 10 to 20 atoms.   The light-transmitting electromagnetic wave shielding material according to claim 11, wherein the patterned pretreatment layer includes a composite metal oxide and / or a composite metal oxide hydrate and a binder resin. The composite metal oxide hydrate is represented by the following formula (2):

(In the formula, M ¹ represents Pd or Ag, M ² represents Si, Ti or Zr. When M ¹ is Pd, x is 1, and when M ¹ is Ag, x is The light-transmitting electromagnetic wave shielding material according to claim 14, wherein n is an integer of 1 to 20.

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