JP2007116137A - Light-transmitting electromagnetic wave shielding film, film for display panels, optical filter for display panels, plasma display panel, and manufacturing method of light-transmitting electromagnetic wave shielding film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light-transmitting electromagnetic wave shielding film that is excellent in chemical resistance such as salt water resistance, moreover heat resistance, heat-humidity resistance, durability and discoloration resistance and has high electromagnetic wave shielding properties and high light transmittance with low light scattering, and provide a film for display panels using the same, an optical filter for display panels and a plasma display panel. <P>SOLUTION: There are provided: a light transmitting electromagnetic wave shielding film provided with a printing pattern having silver as a main component and an anticorrosive (preferably thiol and a disulfide compound) on a transparent substrate; a film for display panels using the same; an optical filter for display panels; and a plasma display panel. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to electromagnetic waves generated from the front surface of a display such as a CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electroluminescence), FED (field emission display), microwave oven, electronic device, printed wiring board, etc. The present invention relates to a light-transmitting electromagnetic wave shielding film having a light-transmitting property, a display panel film using the same, an optical filter for display panel, a plasma display panel, and a method for producing a light-transmitting electromagnetic wave shielding film.

  2. Description of the Related Art In recent years, with the increase in use of various electric facilities and electronic application facilities, electromagnetic interference (Electro-Magnetic Interference: EMI) has increased rapidly. The EMI has been found to cause malfunction and failure of electronic and electrical equipment. For this reason, electronic and electrical equipment is required to keep the intensity of electromagnetic wave emission within the standard or regulation.

  Although it is necessary to shield the electromagnetic wave in order to take measures against the EMI, it is obvious that a property that does not allow the metal electromagnetic wave to penetrate may be used. For example, a method of making the casing a metal body or a high conductor, a method of inserting a metal plate between the circuit board and the circuit board, a method of covering the cable with a metal foil, and the like are adopted. However, in CRT, PDP, etc., since the operator needs to recognize characters displayed on the screen, transparency in the display is required. For this reason, in any of the above methods, the front surface of the display often becomes opaque, which is inappropriate as an electromagnetic wave shielding method.

Particularly, since PDP generates a large amount of electromagnetic waves as compared with CRT or the like, stronger electromagnetic shielding ability is required. The electromagnetic wave shielding ability can be simply expressed by a surface resistance value. For example, in a translucent electromagnetic shielding material for CRT, the surface resistance value is required to be about 300 Ω / sq or less, whereas in a translucent electromagnetic shielding material for PDP, it is 2.5 Ω / sq or less. In consumer plasma televisions using PDPs, there is a high need for 1.5 Ω / sq or less, and a very high conductivity of 0.1 Ω / sq or less is more desirable.
Further, the required level for transparency is about 70% or more (total visible light transmittance) for CRT and 80% or more for PDP, and further higher transparency is desired.

  In order to solve the above problems, as shown below, various materials and methods have been proposed so far that achieve both electromagnetic shielding properties and light transmittance using a metal mesh having openings, A typical example is an etching mesh using a photolithography method. An etching mesh using a conventional photolithography method can be finely processed, and therefore has an advantage that a mesh with a high aperture ratio (high transmittance) can be created and strong electromagnetic wave emission can be shielded. On the other hand, the manufacturing process is complicated and has a problem of high cost, and improvement is demanded.

As a method for producing a metal mesh at a low cost, a method for obtaining a metal mesh by printing a paste or ink containing metal particles in a lattice pattern has been proposed.
For example, Patent Document 1 discloses a method of manufacturing an electromagnetic wave shielding material by printing a conductive fine particle dispersion such as silver by an ink jet method, followed by overheating and baking.
Patent Document 2 discloses a method for producing an electromagnetic wave shielding film by printing a paste having a silver compound and then heating to promote reduction / decomposition into a metal and promoting fusion between metals. It is disclosed.

JP 2003-318593 A JP 2004-111988

The metal mesh obtained by using the conventional printing method as described above can be manufactured with a smaller number of steps and can reduce the manufacturing cost as compared with the manufacturing process of the etching mesh using photolithography. On the other hand, it had the following problems.
That is, the chemical resistance of the metal part required for the electromagnetic shielding material used for the display is not sufficient, and improvement has been desired.
Further, in addition to the chemical resistance of the metal part as described above, there is a problem that a part that transmits light that is not the metal part (light transmissive part) is discolored, and improvement has been desired.
As a result of investigations by the present inventors, it was found that the metal phase of the metal mesh portion is not a complete continuous phase but tends to be an agglomerated phase of metal fine particles having a large surface area in order to print a fine particle dispersion of a metal or metal compound. It was. That is, it was considered that the surface area of the metal part tends to be larger than when the metal foil is etched, which is disadvantageous from the viewpoint of chemical resistance of the metal part.
Furthermore, when the metal mesh obtained by using the conventional printing method is made of silver and has high conductivity, gloss and reflection peculiar to metal silver are seen, and there is a problem as an electromagnetic shielding application for electronic displays. there were. For this reason, a black material having a small reflection and having no problem as described above has been demanded.

  The present invention has been made in view of such circumstances, and an object of the present invention is excellent in chemical resistance such as salt water resistance, heat resistance, moist heat resistance, durability, hardly discolored over time, and high. Translucent electromagnetic wave shielding film having electromagnetic wave shielding properties, low light scattering, high light transmittance, and reduced metal reflection, film for display panel using the same, optical filter for display panel, and plasma display In providing panels.

As a result of intensive studies, the present inventors have recognized that it is effective to suppress metal corrosion for improving chemical resistance and durability, and have completed the present invention.
That is, the present invention is as follows.

(1)
A light-transmitting electromagnetic wave shielding film comprising a transparent substrate and a printing pattern mainly composed of silver and at least one rust inhibitor. However, the printing pattern mainly composed of silver refers to a printing pattern that is composed of a conductive metal part and a light-transmitting part, and the mass% of silver with respect to the metal constituting the pattern is 60% or more.
(2)
The light-transmitting electromagnetic wave shielding film according to (1), wherein the printed pattern is a pattern in which the silver mass% is 85% or more.
(3)
The translucent electromagnetic wave shielding film according to (1) or (2), wherein the printing pattern containing silver as a main component contains silver and a noble metal other than silver.
(4)
The translucent electromagnetic wave shielding film according to any one of (1) to (3), wherein the printed pattern containing silver as a main component contains silver and palladium, or silver and gold.
(5)
The translucent electromagnetic wave shielding film according to any one of (1) to (4), wherein the rust inhibitor is a 5-membered azole compound having an NH structure.
(6)
The translucent electromagnetic wave shielding film according to any one of (1) to (4), wherein the rust inhibitor is an organic mercapto compound.
(7)
The translucent electromagnetic wave shielding film according to any one of (1) to (4), wherein the rust inhibitor is a combination of a 5-membered azole compound having an NH structure and an organic mercapto compound.
(8)
The translucent electromagnetic wave shielding film according to (6) or (7), wherein the organic mercapto compound is represented by the following general formula (2).
General formula (2)
Z-SM
[In General Formula (2), Z is an alkyl group, an aromatic group, or a heterocyclic group, and is a hydroxyl group, —SO ₃ M ² group, or —COOM ² group (where M ² is a hydrogen atom or an alkali metal atom) Or an ammonium group), a group substituted by at least one group selected from the group consisting of an amino group and an ammonio group, or a substituent having at least one selected from this group. M represents a hydrogen atom, an alkali metal atom, or an amidino group (which may form a hydrohalide salt or a sulfonate salt). ]
(9)
The translucency according to (6) or (7), wherein the organic mercapto compound is one or more organic mercapto compounds selected from the following general formulas (1) and (3) to (5): Electromagnetic shielding film.
General formula (1)

[In the general formula (1), -D = and -E = each independently -CH = group, -C ^(R 0) = represents a group or -N = group,, ^{R 0} represents a substituent. L ¹ , L ² and L ³ each independently represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring through any of a carbon atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Provided that at least one of ^{L 1,} L 2, ^{L 3} and ^{R 0} is representative of the -SM group (M represents an alkali metal atom, a hydrogen atom or an ammonium group).
General formula (3), general formula (4)

[In General Formulas (3) and (4), R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group. However, R ₂₁ and R ₂₂ are not simultaneously a hydrogen atom, and the alkyl group may have a substituent. R ₂₃ and R ₂₄ each represent a hydrogen atom or an alkyl group, and R ₂₅ represents a hydroxyl group (or a salt thereof), an amino group, an alkyl group, or a phenyl group. R ₂₆ and R ₂₇ each represent a hydrogen atom, an alkyl group, an acyl group, or —COOM ₂₂ . However, R ₂₆ and R ₂₇ are not simultaneously hydrogen atoms. M ₂₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. M ₂₂ represents a hydrogen atom, an alkyl group, an alkali metal atom, an aryl group or an aralkyl group. m represents 0, 1 or 2. n represents 2. ]
General formula (5)

[In the general formula (5), X ₄₀ represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxyl group or a sulfo group, and M ₄₁ and Ma are a hydrogen atom, an alkali metal atom or ammonium, respectively. Represents a group. ]
(10)
The translucent electromagnetic wave shielding film according to (9), wherein the organic mercapto compound is represented by the general formula (1).
(11)
Translucent electromagnetic waves according to any one of and having an amount of 0.001g / m ² ~0.04g / m ² with respect to the printed pattern the rust inhibitor (1) - (10) Shield film.
(12)
Functional transparency with one or more functions selected from infrared shielding properties, hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, UV protection properties, gas barrier properties, and display panel damage prevention properties The translucent electromagnetic wave shielding film according to any one of (1) to (11), further comprising a layer.
(13)
(1) The film for display panels using the translucent electromagnetic wave shielding film in any one of (12).
(14)
An optical filter for a plasma display panel, wherein the display panel film according to (13) is used.
(15)
A plasma display panel comprising the film for display panel according to (13) or the optical filter for plasma display panel according to (14).
(16)
On the transparent substrate, fine particles mainly composed of silver having a silver mass% of 60% or more with respect to the metal are printed to form a conductive metal portion and a light transmissive portion, and then the conductive metal portion and A method for producing a light-transmitting electromagnetic wave shielding film, wherein the light-transmitting portion is treated with at least one rust inhibitor.
(17)
On the transparent substrate, fine particles mainly composed of silver having a silver mass% of 60% or more with respect to the metal are printed to form a conductive metal portion and a light transmissive portion, and then the conductive metal portion and A method for producing a light-transmitting electromagnetic wave shielding film, wherein the light-transmitting part is treated with a liquid containing Pd ions and then treated with at least one rust preventive agent.

  According to the present invention, it is excellent in chemical resistance such as salt water resistance, heat resistance, moist heat resistance, durability, hardly discolored over time, high electromagnetic shielding properties, small light scattering and high light transmission. The translucent electromagnetic wave shielding film which has a rate, the film for display panels using the same, the optical filter for display panels, and the plasma display panel can be provided.

  The present invention is described in further detail below. In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

[Transparent substrate]
Examples of the transparent substrate used in the present invention include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, and EVA; polyvinyl chloride, Vinyl resins such as polyvinylidene chloride; polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC) A transparent plastic substrate such as can be used.
In the present invention, the transparent plastic substrate is preferably a polyethylene terephthalate film from the viewpoint of transparency, heat resistance, ease of handling, and cost. The thickness of the transparent plastic substrate is preferably 5 to 200 μm from the viewpoints of handleability and visible light transmittance. More preferably, it is 10-130 micrometers, More preferably, it is 40-80 micrometers.

Since the electromagnetic shielding film for a display panel requires transparency, it is desirable that the substrate has high transparency. In this case, the total visible light transmittance of the transparent plastic substrate is preferably 70 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100%. Moreover, in this invention, what was colored to such an extent that the objective of this invention is not disturbed as said transparent plastic base material can also be used.
The transparent plastic substrate in the present invention can be used as a single layer, but it can also be used as a multilayer film in which two or more layers are combined.

  In the present invention, a glass plate can also be used as the transparent substrate. Although the kind of glass plate is not specifically limited, When using as a use of the electromagnetic wave shielding film for a display, it is preferable to use the tempered glass which provided the reinforced layer on the surface. There is a high possibility that tempered glass can prevent damage compared to glass that has not been tempered. Furthermore, the tempered glass obtained by the air cooling method is preferable from the viewpoint of safety because even if it is broken, the crushed pieces are small and the end face is not sharp.

[Print pattern]
Next, the printing pattern mainly containing silver in the present invention will be described.
The printed pattern includes a conductive metal portion and a light transmissive portion.
As a printing method, a known printing method such as gravure printing, offset printing, letterpress printing, screen printing, flexographic printing, inkjet printing, or the like can be used.
A surface treatment may be performed on the transparent substrate, or an anchor coat layer may be provided. Effective surface treatment methods include primer coating, plasma treatment, corona discharge treatment, and the like. The critical surface tension of the transparent substrate after the treatment is preferably 3.5 × 10 ⁻⁴ N / cm or more by these treatments, and more preferably 4.0 × 10 ⁻⁴ N / cm or more.

The paste or ink used for printing preferably contains a metal or a metal compound for obtaining a conductive pattern by printing, and further contains a solvent, a binder, a dispersant, and the like for dispersing them.
Examples of the metal include fine particles such as silver, copper, nickel, palladium, gold, platinum, and tin. In the present invention, the printing pattern is mainly composed of silver, and silver alone or two or more kinds containing silver are included. You may mix and use the said metal. However, the printing pattern containing silver as a main component refers to a printing pattern in which the mass% of silver with respect to the metal constituting the pattern is 60% or more, and 85% or more is a viewpoint of conductivity and durability. To preferred. In this invention, when using 2 or more types of metals, it is also preferable to coat | cover with one metal. Examples of the metal include nickel, zinc, tin, cobalt, chrome, and the like, as well as noble metals such as gold, platinum, and palladium. Precious metals are more preferable, and silver and palladium or silver and gold are further contained. preferable.
The coating method includes (1) a method of preparing alloy fine particles of palladium or gold and printing them when preparing metal fine particles contained in paste or ink used for printing, or (2) printing of silver fine particles. Later, there is a method in which silver is coated with palladium or gold by treatment with a liquid containing palladium (II) ions such as Na ₂ PdCl ₄ or a chloroauric acid aqueous solution. Among these, the method (2) is particularly preferable from the viewpoint of enhancing durability such as particularly excellent salt water resistance.
In the present invention, a metal compound can also be used. The metal compound is a metal oxide or an organometallic compound, and a compound that can easily reduce or decompose by applying energy from the outside and can impart conductivity is preferable. As the metal oxide, gold oxide, silver oxide, or the like can be used. In particular, silver oxide is preferable because it has self-reducing properties. As the organometallic compound, silver acetate, silver citrate and the like having a relatively small molecular weight are preferable. In the case where the paste contains a metal, for example, it is preferably made from a nano-order size (5 to 60 nm) metal, a dispersant, and a solvent. In addition, when the paste contains a metal oxide, it is preferably made from a nano-order size metal oxide, a reducing agent necessary for the reduction of the metal oxide, and a solvent. It is preferable to prepare from an organometallic compound having a low temperature and a solvent. Above all, when a paste using a combination of nano-order size metal oxide and organometallic compound is used, not only can fine lines be printed, but also external energy can be applied by appropriately selecting the structure of the reducing agent and organometallic compound. When imparting electrical conductivity, it is possible to promote reductive decomposition from metal oxide to metal under conditions that do not damage the flexible film, and to promote fusion between metals. Further, the resistance value can be further reduced. In addition, when a metal oxide can be reduced without adding a reducing agent, for example, when it can be self-reduced by heating, it is not particularly necessary to add a reducing agent. As the solvent, which will be described later in detail, it can be appropriately used depending on the printing method and paste viscosity adjusting method to be used, and a high boiling point solvent such as carbitol and propylene glycol can be used. The viscosity of the paste can be appropriately set according to the printing method and the solvent to be used, but is preferably 5 mPa · s or more and 20000 mPa · s or less.

  Examples of the binder contained in the paste and ink used in the present invention include the following resins such as polyester resin, polyvinyl butyral resin, ethyl cellulose resin, (meth) acrylic resin, polyethylene resin, polystyrene resin, polyamide resin and the like. Any of thermosetting resins such as plastic resin; polyester-melamine resin, melamine resin, epoxy-melamine resin, phenol resin, epoxy resin, amino resin, polyimide resin, and (meth) acrylic resin can be used. Two or more kinds of these resins may be copolymerized as required, or two or more kinds may be blended and used.

  Specific examples of usable solvents include hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, seryl alcohol, cyclohexanol, terpineol and other alcohols; ethylene glycol monobutyl ether (Butyl cellosolve), ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monobutyl ether (butyl carbitol), cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate and other alkyl ethers. It may be selected as appropriate in consideration.

  When higher alcohol is used as the solvent, the drying and fluidity of the ink may decrease, so butyl carbitol, butyl cellosolve, ethyl carbitol, butyl cellosolve acetate, butyl carbitol acetate, etc. have better drying properties than these May be used in combination. The amount of the solvent used is determined by the viscosity of the ink or paste, but is usually 100 to 500 parts by weight, preferably 100 to 300 parts by weight with respect to 100 parts by weight of the binder in consideration of the amount of the metal powder added. It is good to be.

Metal, as a binder, and a solvent component ratio (mass ratio), with respect to for example, metal 1, a binder ¹⁰ -5 to 10 ^2, solvent 10 ^5, preferably to a metal 1, a binder ¹⁰ -3 to 10, solvent 10 to 10 is ^three.
The conductive metal part after printing is preferably fired at a high temperature. Thereby, the organic component is removed and the metal fine particles adhere to each other, and the surface resistance value is lowered. The firing temperature is, for example, 50 to 1000 ° C., preferably 70 to 600 ° C., and the firing time is, for example, 3 to 600 minutes, preferably 10 to 300 minutes.

  Since the translucent electromagnetic wave shielding film in the present invention has a conductive metal part, good conductivity can be obtained. For this reason, the surface resistance value of the translucent electromagnetic wave shielding film of the present invention is preferably 10Ω / sq or less, more preferably 2.5Ω / sq or less, and 1.5Ω / sq or less. Is more preferable, and most preferably 0.1Ω / sq or less.

In the conductive metal portion of the present invention, the conductive metal is a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, or the like, (positive) hexagon, (positive) It is preferably arranged so as to constitute a geometric figure combining octagons and the like, and more preferably a mesh shape composed of these geometric figures.
In the present invention, it is most preferable to have a grid-like mesh form composed of squares.

  The line width of the conductive metal portion is preferably 20 μm or less, and the line interval is preferably 100 μm or more. The conductive metal portion may have a portion whose line width is wider than 20 μm for the purpose of ground connection or the like. Further, from the viewpoint of making the image inconspicuous, the line width of the conductive metal portion is more preferably less than 15 μm.

  The thickness of the conductive metal portion is preferable for the display panel because the viewing angle of the display is increased as the thickness is reduced. It is preferably 1 μm or more and 20 μm or less, more preferably 1 μm or more and 13 μm or less, further preferably 2 to 10 μm, and most preferably 3 to 7 μm. Moreover, it is preferable that a conductive metal part is pattern shape. The conductive metal portion may be a single layer or a multilayer structure of two or more layers.

  The conductive metal portion in the present invention has an aperture ratio of preferably 85% or more, more preferably 90% or more, and most preferably 95% or more from the viewpoint of visible light transmittance. Further, the “aperture ratio” is a ratio of a portion having no fine line forming the mesh to the whole. For example, the aperture ratio of a square lattice mesh having a line width of 10 μm and a pitch of 200 μm is approximately 90%. In addition, although there is no restriction | limiting of an upper limit in particular regarding the aperture ratio of the electroconductive metal part in this invention, As said aperture ratio, it is preferable that it is 98% or less from the relationship between a surface resistance value and a line | wire width value.

[anti-rust]
Next, the rust inhibitor used in the present invention will be described.
As the rust preventive agent used in the present invention, a 5-membered azole compound or an organic mercapto compound having an N—H structure is preferable. The N—H structure means a nitrogen-hydrogen bond contained in azoles, and the hydrogen is dissociable.

  Preferred examples of the 5-membered azole compound having an NH structure include tetrazoles, triazoles, imidazoles, thiadiazoles, benzimidazoles, and tetraazaindenes.

These rings may have a substituent, and the substituent is represented by Ln-Rm.
L represents a single bond, a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, or a linking group combining these.
L is preferably a single bond, an alkylene group having 1 to 10 carbon atoms (for example, each group of methylene, ethylene, propylene, butylene, isopropylene, 2-hydroxypropylene, hexylene, and octylene), and an alkenylene group having 2 to 10 carbon atoms. (For example, each group of vinylene, propenylene, and butenylene), an aralkylene group having 7 to 12 carbon atoms (for example, phenethylene group), an arylene group having 6 to 12 carbon atoms (for example, phenylene, 2-chlorophenylene, 3-methoxyphenylene, naphthylene) Each group), a divalent group of a heterocyclic group having 1 to 10 carbon atoms (for example, pyridyl, thienyl, furyl, triazolyl, imidazolyl groups), a single bond, and a group arbitrarily combining these groups It _{may, -CO -, - sO 2 -} , - NR 202 -, - O- or -S- and also any combination But good. Here, R ₂₀₂ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, butyl, or hexyl groups), an aralkyl group having 7 to 10 carbon atoms (for example, benzyl phase, phenethyl group), 6 carbon atoms. To 10 aryl groups (for example, phenyl and 4-methylphenymethylphenyl groups). A single bond is particularly preferable.

  R represents a nitro group, a halogen atom (eg, chlorine atom, bromine atom), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, propyl, t-butyl, cyanoethyl groups), aryl Groups (eg phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl, naphthyl groups), alkenyl groups (eg allyl groups), aralkyl groups (eg benzyl, 4-methylbenzyl, Phenethyl groups), sulfonyl groups (eg methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl groups), carbamoyl groups (eg unsubstituted carbamoyl, methylcarbamoyl, phenylcarbamoyl groups), sulfamoyl groups (eg unsubstituted) Sulfamoyl, methylsulfamoyl Phenylsulfamoyl groups), carbonamide groups (eg acetamido and benzamide groups), sulfonamido groups (eg methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide groups), acyloxy groups (eg acetyl) Oxy, benzoyloxy groups), sulfonyloxy groups (for example, methanesulfonyloxy), ureido groups (for example, unsubstituted ureido, methylureido, ethylureido, phenylureido groups), acyl groups (for example, acetyl, benzoyl groups) ), Oxycarbonyl groups (for example, methoxycarbonyl, phenoxycarbonyl groups), oxycarbonylamino groups (for example, methoxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarbonylamino groups), Etc. In Dorokishiru group may be substituted.

  n and m each represent an integer of 0 and 1 to 3. When n and m each represent 2 or 3, each L and R may be the same or different.

  Specific examples of preferable nitrogen-containing organic heterocyclic compounds include the following. That is, examples include imidazole, benzimidazole, benzoindazole, benzotriazole, and the like, and these may have a substituent such as an alkyl group, a carboxyl group, and a sulfo group.

As the rust inhibitor used in the present invention, an organic mercapto compound is preferably used.
Examples of the organic mercapto compound include alkyl mercapto compounds, aryl mercapto compounds, and heterocyclic mercapto compounds.

Preferably, it is an organic mercapto compound represented by the following general formula (2).
General formula (2)
Z-SM
[In General Formula (2), Z is an alkyl group, an aromatic group, or a heterocyclic group, and is a hydroxyl group, —SO ₃ M ² group, or —COOM ² group (where M ² is a hydrogen atom or an alkali metal atom) Or an ammonium group), at least one group selected from the group consisting of an amino group and an ammonio group, or a group substituted by a substituent having at least one selected from this group. M represents a hydrogen atom, an alkali metal atom, or an amidino group (which may form a hydrohalide salt or a sulfonate salt). ]

In addition, organic mercapto compounds represented by the following general formulas (1) and (3) to (5) are also preferable, and compounds of the general formula (1) are particularly preferable.
General formula (1)

[In the general formula (1), -D = and -E = each independently -CH = group, -C ^(R 0) = represents a group or -N = group,, ^{R 0} represents a substituent. L ¹ , L ² and L ³ each independently represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring through any of a carbon atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Provided that at least one of ^{L 1,} L 2, ^{L 3} and ^{R 0} is representative of the -SM group (M represents an alkali metal atom, a hydrogen atom or an ammonium group). When one of -D = and -E = is -N = group, -D = represents -CH = group or -C (R ⁰ ) = group, and -E = represents -N = group. To express. ]

General formula (3), general formula (4)

[In General Formulas (3) and (4), R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group. However, R ₂₁ and R ₂₂ are not simultaneously a hydrogen atom, and the alkyl group may have a substituent. R ₂₃ and R ₂₄ each represent a hydrogen atom or an alkyl group, and R ₂₅ represents a hydroxyl group, an amino group, an alkyl group or a phenyl group. R ₂₆ and R ₂₇ each represent a hydrogen atom, an alkyl group, an acyl group, or —COOM ₂₂ . However, R ₂₆ and R ₂₇ are not simultaneously hydrogen atoms. M ₂₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. M ₂₂ represents a hydrogen atom, an alkyl group, an alkali metal atom, an aryl group or an aralkyl group. m represents 0, 1 or 2. n represents 2. ]

General formula (5)

[In the general formula (5), X ₄₀ represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxyl group or a sulfo group, and M ₄₁ and Ma are a hydrogen atom, an alkali metal atom or ammonium, respectively. Represents a group. ]

  The compound represented by the general formula (2) will be described.

  In the general formula (2), the alkyl group represented by Z is preferably one having 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 2 to 20 carbon atoms, the above-mentioned You may have a substituent other than a substituent. The aromatic group represented by Z is preferably a monocyclic or condensed ring having 6 to 32 carbon atoms, and may have a substituent in addition to the above-described substituents. The heterocyclic group represented by Z is preferably a monocyclic or condensed ring having 1 to 32 carbon atoms, and has 1 to 6 heteroatoms independently selected from nitrogen, oxygen and sulfur in one ring. It is a 5- or 6-membered ring and may have a substituent in addition to the above. However, when the heterocyclic group is tetrazole, it does not have a substituted or unsubstituted naphthyl group as a substituent. Among the compounds represented by the general formula (2), a compound in which Z is a heterocyclic group having two or more nitrogen atoms is preferable.

  A preferable compound represented by the general formula (2) is represented by the following formula (2-a).

In the general formula, Z is necessary for forming an unsaturated 5-membered heterocycle having a nitrogen atom or a 6-membered heterocycle (pyrrole ring, imidazole ring, pyrazole ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc.). A compound having at least one —SM group or thione group, and from a hydroxyl group, a —COOM group, a —SO ₃ M group, a substituted or unsubstituted amino group, a substituted or unsubstituted ammonio group Having at least one substituent selected from the group consisting of In the formula, R ¹¹ and R ¹² are each independently a hydrogen atom, —SM group, halogen atom, alkyl group (including those having a substituent), alkoxy group (including those having a substituent), a hydroxyl group, -COOM group, -SO 3 _M group, (including those having a substituent) alkenyl group (including those having a substituent) amino group, (including those having a substituent) carbamoyl group, a phenyl group (substituted Including a group having a group), and R ¹¹ and R ¹² may form a ring. The ring that can be formed is a 5-membered ring or a 6-membered ring, preferably a nitrogen-containing heterocycle. M is synonymous with M defined in the general formula (2). Z is preferably a group that forms a heterocyclic compound containing two or more nitrogen atoms, and may have a substituent other than the -SM group or thione group, and the substituent includes a halogen atom, Lower alkyl groups (including those having substituents, preferably those having 5 or less carbon atoms such as methyl and ethyl groups), lower alkoxy groups (including those having substituents; carbons such as methoxy, ethoxy and butoxy) And a lower alkenyl group (including those having a substituent. Preferred are those having 5 or less carbon atoms), a carbamoyl group, a phenyl group, and the like. Furthermore, the compounds represented by the following formulas A to F in the general formula (2-a) are particularly preferable.

In the formula, R ²¹ , R ²² , R ²³ , and R ²⁴ are each independently a hydrogen atom, —SM group, halogen atom, lower alkyl group (including those having a substituent. Carbon number such as methyl group, ethyl group, etc. 5 or less are preferred), a lower alkoxy group (including those having a substituent, preferably those having 5 or less carbon atoms), a hydroxy group, —COOM ² , —SO ₃ M ⁵ group, a lower alkenyl group ( Including those having a substituent, preferably those having 5 or less carbon atoms), an amino group, a carbamoyl group, and a phenyl group, at least one of which is an -SM group. M, M ² and M ⁵ each represent a hydrogen atom, an alkali metal atom or an ammonium group. In particular, hydroxy groups as substituents other than _{^{-SM, -COOM 2, -SO 3 M}} 5 group, it preferably has a water-soluble group such as an amino group.

The amino group represented by R ²¹ , R ²² , R ²³ , R ²⁴ represents a substituted or unsubstituted amino group, and a preferred substituent is a lower alkyl group. The ammonium group represented by M, M ² and M ⁵ is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

  Although the specific example of a compound represented by General formula (2) below is shown, it is not limited to these.

  The compounds represented by the general formulas (1) and (3) to (5) will be described.

The compound represented by the general formula (1) will be described in detail. In the general formula (1), -D = and -E = each independently -CH = group, -C ^(R 0) = represents a group or -N = group, wherein the ^{R 0} is a substituent. L ^{1, L 2,} L ³ each independently represent a hydrogen atom, he represents a halogen atom or a carbon atom, a nitrogen atom, an oxygen atom, an optional substituent attached to the ring either sulfur or phosphorus atom, L ¹ ~L ³ may be the same or different. However, at least one of L ¹ , L ² , L ³ and R ¹ represents a —SM group (M is an alkali metal atom, a hydrogen atom, or an ammonium group). When one of -D = and -E = is -N = group, -D = represents -CH = group or -C (R ⁰ ) = group, and -E = represents -N = group. To express. ]

Specific examples of the optional substituent represented by L ¹ , L ² , and L ³ and the substituent represented by R ⁰ include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), Alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic group containing quaternized nitrogen atom (for example, pyridinio group), acyl Group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, Hydroxy group, alkoxy group (ethyleneoxy group or propyleneoxy group unit Aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group , Hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino Group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, ( (Alkyl, aryl or heterocyclic) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, And a group containing a phosphoric acid amide or phosphoric acid ester structure. These substituents may be further substituted with these substituents.

More preferably, the arbitrary substituents represented by L ¹ , L ² and L ³ and the substituent represented by R ⁰ are a substituent having ⁰ to 15 carbon atoms, such as a chlorine atom, an alkyl group, an aryl group, a complex A cyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, a cyano group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group, an (alkyl, aryl or heterocyclic ring) amino group, a hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocyclic) thio Group, a sulfo group or a salt thereof, and a sulfamoyl group, and more preferably an alkyl group, an aryl group, a complex Group, alkoxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, alkoxy group, aryloxy group, acyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group, hydroxyamino group, N-substituted saturated or unsaturated A saturated nitrogen-containing heterocyclic group, acylamino group, sulfonamido group, ureido group, thioureido group, sulfamoylamino group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, sulfo group or a salt thereof; Most preferred are amino group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylthio group, arylthio group, mercapto group, carboxy group or salt thereof, sulfo group or salt thereof. In the general formula (1), L ¹ , L ² , L ³ and R ⁰ may be bonded to each other to form a condensed ring in which a hydrocarbon ring, a hetero ring, or an aromatic ring is condensed.

In General Formula (1), at least one of L ¹ , L ² , L ³ , and R ¹ represents a —SM group (M is an alkali metal atom, a hydrogen atom, or an ammonium group). Here specifically the alkali metal atom is Na, K, Li, Mg, Ca, etc., it -S ^- present as a counter cation. M is preferably a hydrogen atom, an ammonium group, Na ⁺ , or K ⁺ , and particularly preferably a hydrogen atom. Among the compounds represented by the general formula (1), compounds represented by the following general formula (1-A) and general formula (1-B) are preferable.

Next, the general formula (1-A) will be described in detail. R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring by a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, which is represented by the general formula (1) And L ¹ , L ² , and L ³ have the same meanings, and preferred ranges thereof are also the same. However, R ¹ and R ³ do not represent a hydroxy group. R ^{1 to} R ⁴ may be the same or different, but at least one of them is a —SM group. M represents a hydrogen atom, an alkali metal atom, or an ammonium group. R ¹ and R ² may be bonded to each other to form a condensed ring in which a hydrocarbon ring, a hetero ring, or an aromatic ring is condensed.

In general formula (1-A), at least one of R ^{1 to} R ⁴ is an —SM group, and more preferably at least two of R ^{1 to} R ⁴ are —SM groups. When at least two of R ^{1 to} R ⁴ are —SM groups, preferably R ⁴ and R ¹ , or R ⁴ and R ³ are —SM groups.

  In the present invention, among the compounds represented by the general formula (1-A), compounds represented by the following general formulas (1-A-1) to (1-A-3) are particularly preferable.

In the general formula (1-A-1), R ¹⁰ represents a mercapto group, a hydrogen atom, or an arbitrary substituent, and X represents a water-soluble group or a substituent substituted with a water-soluble group. In the general formula (1-A-2), Y ¹ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ²⁰ represents a hydrogen atom or an arbitrary substituent. In General Formula (1-A-3), Y ² represents a water-soluble group or a substituent substituted with a water-soluble group, and R ³⁰ represents a hydrogen atom or an arbitrary substituent. However, R ¹⁰ and Y ¹ do not represent a hydroxy group.

Next, the compounds represented by the general formulas (1-A-1) to (1-A-3) will be described in detail.
In General Formula (1-A-1), R ¹⁰ represents a mercapto group, a hydrogen atom, or an arbitrary substituent. Here, the arbitrary substituents are the same as those described for R ^{1 to} R ^{4 in} the general formula (1-A). R ¹⁰ is preferably a mercapto group, a hydrogen atom, or a group selected from the following substituents having 0 to 15 carbon atoms. That is, amino group, alkyl group, aryl group, alkoxy group, aryloxy group, acylamino group, sulfonamido group, alkylthio group, arylthio group, alkylamino group, arylamino group and the like can be mentioned. In general formula (1-A-1), X represents a water-soluble group or a substituent substituted with a water-soluble group. Here, the water-soluble group is a sulfonic acid group or a carboxylic acid group and a salt thereof, a salt such as an ammonio group, or a group containing a dissociable group that can be partially or completely dissociated by an alkaline developer. Specifically, sulfo group (or salt thereof), carboxy group (or salt thereof), hydroxy group, mercapto group, amino group, ammonio group, sulfonamido group, acylsulfamoyl group, sulfonylsulfamoyl group, active methine Represents a group or a substituent containing these groups. In the present invention, the active methine group means a methyl group substituted with two electron-withdrawing groups, specifically, dicyanomethyl, α-cyano-α-ethoxycarbonylmethyl, α-acetyl-α-ethoxy. Examples include groups such as carbonylmethyl. The substituent represented by X in the general formula (1-A-1) is the above-described water-soluble group or a substituent substituted with the above-mentioned water-soluble group, and the substituent has 0 carbon atoms. ˜15 substituents, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkyl, aryl or heterocyclic) amino group, an acylamino group, a sulfonamide group, Examples include ureido group, thioureido group, imide group, sulfamoylamino group, (alkyl, aryl or heterocyclic) thio group, (alkyl, aryl) sulfonyl group, sulfamoyl group, amino group and the like. 10 alkyl groups (especially methyl groups substituted with amino groups), aryl groups, aryloxy groups, amino groups, (alkyl, aryl, or Ring) amino group, an (alkyl, aryl or heterocyclic) group such as thio group.

  Among the compounds represented by the general formula (1-A-1), a compound represented by the following general formula (1-A-1-a) is more preferable.

Wherein ^{R 11} has the same meaning as ^{R 10} in formula (1-A-1), and the preferred range is also the same. R ¹² and R ¹³ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. However, at least one of R ¹² and R ¹³ has at least one water-soluble group. Here, the water-soluble group is a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonio group, a sulfonamide group, an acylsulfamoyl group, or a sulfonylsulfamoyl group. Represents a group, an active methine group, or a substituent containing these groups, and preferred examples include a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, an amino group, and the like. R ¹² and R ¹³ are preferably an alkyl group or an aryl group, and when R ¹² and R ¹³ are an alkyl group, the alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, As the substituent, a water-soluble group, particularly a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, or an amino group is preferable. When R ¹² and R ¹³ are an aryl group, the aryl group is preferably a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and the substituent is a water-soluble group, particularly a sulfo group (or a salt thereof). , A carboxy group (or a salt thereof), a hydroxy group, or an amino group is preferable. When R ¹² and R ¹³ represent an alkyl group or an aryl group, they may be bonded to each other to form a cyclic structure. A saturated heterocyclic ring may be formed by a cyclic structure.

In General Formula (1-A-2), Y ¹ represents a water-soluble group or a substituent substituted with a water-soluble group, and has the same meaning as X in General Formula (1-A-1). In the general formula (1-A-2), the water-soluble group represented by Y ¹ or the substituent substituted with the water-soluble group is more preferably an active methine group or the following group substituted with a water-soluble group, That is, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl group, and an aryl group. Y ¹ is more preferably an active methine group or an amino group (alkyl, aryl, or heterocyclic) substituted with a water-soluble group, wherein the water-soluble group includes a hydroxy group, a carboxy group or a salt thereof, sulfo A group or a salt thereof is particularly preferred. Y ¹ is particularly preferably an (alkyl, aryl, or heterocyclic) amino group substituted with a hydroxy group, a carboxy group (or a salt thereof), or a sulfo group (or a salt thereof), and —N (R ⁰¹ ) It is represented by (R ⁰² ) group. R ⁰¹ and R ⁰² are groups having the same meanings as R ¹² and R ^{13 in the} general formula (1-A), respectively, and preferred ranges thereof are also the same.

In the general formula (1-A-2), R ²⁰ represents a hydrogen atom or an arbitrary substituent, and here, the arbitrary substituent is the one described for R ^{1 to} R ^{4 in} the general formula (1-A). The same thing is mentioned. R ²⁰ is preferably a hydrogen atom or a group selected from the following substituents having 0 to 15 carbon atoms. That is, a hydroxy group, an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, a hydroxylamino group and the like can be mentioned. R ²⁰ is most preferably a hydrogen atom.

In General Formula (1-A-3), Y ² represents a water-soluble group or a substituent substituted with a water-soluble group, and R ³⁰ represents a hydrogen atom or an arbitrary substituent. Y ² and R ³⁰ in formula (1-A-3) are the same groups as Y ¹ in formula (1-A-2) and R ^{20 in} formula (1-A-2), respectively. The range is also the same.

Next, the general formula (1-B) will be described in detail. ^R 5 to R ⁷ in the formula (1-B) has the same meaning as ^R 1 to R ⁴ of formula (1-A) independently, the preferred range thereof is also the same. Of the compounds represented by the general formula (1-B), the compound represented by the general formula (1-B-1) is particularly preferable.
Formula (1-B-1)

In the general formula (1-B-1), R ⁵⁰ has the same meaning as R ^{5 to} R ^{7 in the} general formula (1-B), and more preferably the general formulas (1-A-1) to (1-A- 3) a water-soluble group having the same meaning as X, Y ¹ , and Y ² or a group substituted with a water-soluble group. Furthermore, among the compounds of general formula (1-B-1), the compound represented by general formula (1-B-1-a) is most preferable.
General formula (1-B-1-a)

In the general formula (1-B-1-a), R ⁵¹ and R ⁵² are groups having the same meanings as R ¹² and R ^{13 in the} general formula (1-A-1-a), and preferred ranges thereof are also the same. .

  Specific examples of the compound represented by the general formula (1) are shown below, but the compound represented by the general formula (1) that can be used in the present invention is not limited to these.

In the general formulas (3) and (4), the alkyl group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ preferably has 1 to 3 carbon atoms, such as a methyl group or an ethyl group. The alkyl group represented by R ₂₆ and R ₂₇ preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. The acyl group preferably has 18 or less carbon atoms, and examples thereof include an acetyl group and a benzoyl group. The alkyl group represented by M ₂₂ preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and the aryl group includes a phenyl group, a naphthyl group, and the like as an aralkyl group. Preferably has 15 or less carbon atoms, and examples thereof include a benzyl group and a phenethyl group.

  Various synthetic methods are known for the compound represented by the general formula (3) or (4). For example, a Strecker amino acid synthesis method known as an amino acid synthesis method may be used. Is performed by alternately adding alkali and acetic anhydride in an aqueous solution.

  Next, although the specific example of a compound represented by General formula (3) or (4) is shown, this invention is not limited only to these.

The lower alkyl group represented by X _{40 in} the general formula (5) is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an isopropyl group. Although the example of a specific compound represented by General formula (5) is shown, it is not limited to these.

These rust inhibitors can be used alone or in combination.
The rust preventive agent used in the present invention can be included by treating the electromagnetic wave shielding film with a bath containing a rust preventive agent. For example, after forming an aqueous solution, a conductive metal portion is formed in the aqueous solution. It is applied to the conductive metal part by immersing a transparent substrate. The rust prevention treatment is preferably performed on the conductive metal part after the firing treatment. The rust inhibitor aqueous solution used at this time contains the rust inhibitor compound in a concentration of 10 ⁻⁶ to 10 ⁻¹ mol, preferably 10 ⁻⁵ to 10 ⁻² mol, in 1 liter. preferable. In addition, the pH of the aqueous solution is preferably adjusted to 2 to 12 (more preferably adjusted to 5 to 10) from the viewpoint of dissolving the rust preventive agent, and the pH adjustment may be performed using a normal alkali such as sodium hydroxide or sulfuric acid, In addition to the acid, phosphoric acid or a salt thereof, carbonate, acetic acid or a salt thereof, boric acid or a salt thereof, or the like can be used as a buffer. The temperature of the aqueous solution is 0 to 100 ⁰ set in C range are, 10 to 80 ⁰ C is preferable from the viewpoint of dissolving the rust inhibitor.
It is presumed that the rust preventive agent is adsorbed on the fine mesh wire, and it is considered that the rust preventive / stabilizing effect is exhibited in this state.
Further, in the present invention, rust inhibitor, the effect of discoloration resistance, it is preferably provided in the range of 0.001g / m ² ~0.04g / m ² with respect to the viewpoint of a metal pattern such as economy. More preferably from ^{0.003g / m 2 ~0.03g / m 2} , more preferably from ^{0.01g / m 2 ~0.02g / m 2} .
The content of the rust inhibitor can be adjusted by the concentration, pH, temperature, and immersion time of the rust inhibitor aqueous solution. The content of the rust inhibitor can be quantified by an extraction method such as liquid chromatography or NMR after extracting the rust inhibitor from the sample of the present invention. When extracting the rust inhibitor, select an appropriate one from methods such as extracting the metal pattern by oxidizing and dissolving it with nitric acid or EDTA / Fe (III) complex, or extracting with an alkaline aqueous solution. can do.

[Functional membrane]
The translucent electromagnetic wave shielding film of the present invention may be provided with a functional transparent layer having a desired function, if necessary. For example, display panel applications include infrared-shielding layers composed of infrared-absorbing compounds and metals; hard-coating layers that are not easily scratched; antireflection with antireflection properties adjusted for refractive index and film thickness Non-glare layer or anti-glare layer having antiglare properties such as a glare prevention function; a layer for preventing static electricity; an antifouling layer having a function for easily removing dirt such as fingerprints; a layer for cutting ultraviolet rays; a gas barrier A layer having a property; for example, a display panel breakage preventing layer having a function of preventing glass scattering when glass is broken can be provided. These functional layers may be provided on the conductive metal part, or may be provided on the opposite side of the conductive metal part via a transparent substrate.

  Some of the functional transparent layers will be further described.

The layer having infrared shielding properties, for example, the near infrared absorbing layer is a layer containing a near infrared absorbing dye such as a metal complex compound, or a silver sputtered layer. Here, the silver sputter layer can cut light of 1000 nm or more from near infrared rays, far infrared rays to electromagnetic waves by alternately laminating dielectric layers and metal layers on the substrate by sputtering or the like. The dielectric layer includes a transparent metal oxide such as indium oxide or zinc oxide as a dielectric. The metal contained in the metal layer is generally silver or a silver-palladium alloy. The sputtered silver layer generally has a structure in which about 3, 5, 7 or 11 layers are laminated, starting from the dielectric layer.
In the PDP, the phosphor that emits blue light has a characteristic of emitting red light in addition to blue, but has a problem that a portion to be displayed in blue is displayed in a purplish color. . The layer having a color tone adjusting function that absorbs visible light in the specific wavelength range is a layer that corrects the colored light as a countermeasure, and contains a dye that absorbs light in the vicinity of 595 nm.

  As a method of forming an antireflection layer imparted with antireflection properties, metal oxides, fluorides, silicides, borides, carbides, nitrides, sulfides are used in order to suppress reflection of external light and suppress a decrease in contrast. A method of laminating an inorganic substance such as a single layer or multiple layers by a vacuum deposition method, a sputtering method, an ion plating method, or an ion beam assist method, or a single layer or a resin having a different refractive index such as an acrylic resin or a fluororesin There is a method of laminating on a functional layer in multiple layers. Moreover, the film which gave the antireflection process can also be affixed on a film | membrane.

  As a method for forming the non-glare layer or the anti-glare layer, a method of forming a fine powder such as silica, melamine, or acrylic into an ink and coating the surface can be used. At this time, the ink can be cured by thermal curing or photocuring. In addition, a film that has been subjected to non-glare treatment or anti-glare treatment can be attached to the film.

The translucent electromagnetic wave shielding film of the present invention is particularly useful as a display panel film because it has good electromagnetic wave shielding properties and translucency. The film for a display panel comprising the translucent electromagnetic wave shielding film of the present invention can be used as an optical filter for a plasma display panel, for example, by providing the functional transparent layer. These members can be applied to the front surface of displays such as CRT, PDP, liquid crystal, and EL, microwave ovens, electronic devices, printed wiring boards, and the like, and are particularly useful for PDPs.
The PDP of the present invention has high electromagnetic shielding ability, high contrast and high brightness, and can be produced at low cost.

  Hereinafter, the present invention will be described more specifically with reference to examples of the present invention. In addition, the material, usage-amount, ratio, processing content, processing procedure, etc. which are shown in the following Examples can be changed suitably unless it deviates from the meaning of this invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
A transparent polyethylene naphthalate (PEN) film having a thickness of 100 μm provided with a gelatin undercoat layer was used as a transparent plastic substrate, and the following silver paste was printed thereon by screen printing.
Subsequently, it heat-processed at 150 degreeC for 60 minutes. The obtained mesh pattern was a silver lattice mesh having a line width of 20 μm and a pitch of 300 μm.
Furthermore, the antirust process was performed in the aqueous solution containing the compound (0.1 mol / L) used for this invention of Table 1. The rust prevention treatment was performed by immersing in the above aqueous solution for 3 minutes.
After the rust prevention treatment, the sample was washed with water and dried to obtain a sample of the present invention.
(Create silver paste)
In accordance with a method for preparing Carey-Lea's silver sol (see M. Carey Lea, Brit. J. Photog., Vol. 24, p. 297 (1877) and Vol. 27, p. 279 (1880)) After the silver fine particles were prepared, a chloroauric acid solution was added to prepare silver gold fine particles containing silver as a main component, and ultrafiltration was performed to remove by-product salts. As a result of observation with an electron microscope, the particle size of the obtained fine particles was approximately 10 nm.
The particles were mixed with a solvent containing isopropyl alcohol and a binder to prepare a paste.
The mass% of silver with respect to the metal constituting this printed pattern was 96%.

(Comparative Example 1)
A sample was prepared in the same manner as in Example 1 except that the rust prevention treatment was not performed.

<Evaluation method>
(Surface resistance)
The surface resistivity was measured with a low resistivity meter Loresta manufactured by Mitsubishi Chemical.
The sample described in Table 1 below was 0.6Ω / □.
(Chemical resistance (salt water resistance))
The said sample was immersed for 1 hour using the physiological saline, and after drying, the discoloration condition of the metal part of an immersion part was evaluated visually. Those in which discoloration was observed were marked with ×, and those in which discoloration was not recognized were marked with ○.
(Heat-resistant)
A heat resistance test was conducted at 100 ° C. for 1 week, and the increase in surface resistance (conductivity decrease) after the test was evaluated as x when the resistance was 1Ω / □ or more, and ○ when the resistance was less than 1Ω / □.

As can be seen from Table 1, it was found that the sample of the present invention shown in Example 1 was excellent in chemical resistance such as salt water resistance and durability such as heat resistance. It was also confirmed that the surface low efficiency was sufficiently low and the electromagnetic wave shielding ability was provided.
Surprisingly, an improvement effect was recognized in terms of pencil hardness (surface hardness) and tape peelability (adhesion).
[Example 2]
A silver paste was prepared without using the chloroauric acid used in the preparation of the silver paste of Example 1, and the silver paste was printed in the same manner as in Example 1. Samples of the present invention Examples 2-A to 2-D containing a rust preventive agent in the same manner as in Example 1 except that the heat treatment was followed by treatment with an aqueous Na ₂ PdCl ₄ .2H ₂ 0 solution (0.01 M). It was created. Moreover, the comparative sample 2 which does not use a rust preventive agent was created. _{Further, Na 2 PdCl 4 · 2H 2} 0 process to prepare a comparative sample 3 not treated rust inhibitor.
<Evaluation method>
(Discoloration resistance of light transmissive part)
A time-lapse test was conducted at 100 ° C. for one week, and after that, the decrease in transmittance at 410 nm was 8% or more, x was 4-8%, and Δ was 4% or less.

As can be seen from the above results, among the samples treated with the Na ₂ PdCl ₄ .2H ₂ 0 aqueous solution, those not treated with the rust preventive agent have a problem that the light-transmitting portion, not the metal portion, is significantly discolored over time. There has occurred. On the other hand, it was surprisingly found that the sample of the present invention in which the anticorrosion treatment was applied to the metal had a small decrease in transmittance (discoloration) in the light transmissive portion instead of the metal portion. Further, among the present invention, compounds 21 and 32 which are compounds of the general formula (1) exhibited particularly excellent effects.
In addition, since the sample of this example was treated with palladium, the printed pattern was black, and the sample not treated with palladium had a silver reflection color, but its reflection was significantly reduced. It had been. For this reason, it turned out that it can utilize suitably as a translucent electromagnetic wave shielding film for a display.

Claims (17)

  A light-transmitting electromagnetic wave shielding film comprising a transparent substrate and a printing pattern mainly composed of silver and at least one rust inhibitor. However, the printing pattern containing silver as a main component refers to a printing pattern composed of a conductive metal portion and a light-transmitting portion, and the mass% of silver with respect to the metal constituting the pattern is 60% or more.   The translucent electromagnetic wave shielding film according to claim 1, wherein the printed pattern is a pattern in which the mass% of silver is 85% or more.   The translucent electromagnetic wave shielding film according to claim 1 or 2, wherein the printing pattern containing silver as a main component contains silver and a noble metal other than silver.   The translucent electromagnetic wave shielding film according to claim 1, wherein the printing pattern containing silver as a main component contains silver and palladium, or silver and gold.   The translucent electromagnetic wave shielding film according to claim 1, wherein the rust inhibitor is a 5-membered azole compound having an N—H structure.   The translucent electromagnetic wave shielding film according to claim 1, wherein the rust inhibitor is an organic mercapto compound.   The translucent electromagnetic wave shielding film according to claim 1, wherein the rust preventive is a combination of a 5-membered ring azole compound having an N—H structure and an organic mercapto compound. The translucent electromagnetic wave shielding film according to claim 6 or 7, wherein the organic mercapto compound is represented by the following general formula (2).
General formula (2)
Z-SM
[In General Formula (2), Z is an alkyl group, an aromatic group, or a heterocyclic group, and is a hydroxyl group, —SO ₃ M ² group, or —COOM ² group (where M ² is a hydrogen atom or an alkali metal atom) Or an ammonium group), a group substituted by at least one group selected from the group consisting of an amino group and an ammonio group, or a substituent having at least one selected from this group. M represents a hydrogen atom, an alkali metal atom, or an amidino group (which may form a hydrohalide salt or a sulfonate salt). ] The translucent electromagnetic wave shield according to claim 6 or 7, wherein the organic mercapto compound is one or more organic mercapto compounds selected from the following general formulas (1) and (3) to (5). film.
General formula (1)

[In the general formula (1), -D = and -E = each independently -CH = group, -C ^(R 0) = represents a group or -N = group,, ^{R 0} represents a substituent. L ¹ , L ² and L ³ each independently represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring through any of a carbon atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Provided that at least one of ^{L 1,} L 2, ^{L 3} and ^{R 0} is representative of the -SM group (M represents an alkali metal atom, a hydrogen atom or an ammonium group).
General formula (3), general formula (4)

[In General Formulas (3) and (4), R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group. However, R ₂₁ and R ₂₂ are not simultaneously a hydrogen atom, and the alkyl group may have a substituent. R ₂₃ and R ₂₄ each represent a hydrogen atom or an alkyl group, and R ₂₅ represents a hydroxyl group (or a salt thereof), an amino group, an alkyl group, or a phenyl group. R ₂₆ and R ₂₇ each represent a hydrogen atom, an alkyl group, an acyl group, or —COOM ₂₂ . However, R ₂₆ and R ₂₇ are not simultaneously hydrogen atoms. M ₂₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. M ₂₂ represents a hydrogen atom, an alkyl group, an alkali metal atom, an aryl group or an aralkyl group. m represents 0, 1 or 2. n represents 2. ]
General formula (5)

[In the general formula (5), X ₄₀ represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxyl group or a sulfo group, and M ₄₁ and Ma are a hydrogen atom, an alkali metal atom or ammonium, respectively. Represents a group. ]   The translucent electromagnetic wave shielding film according to claim 9, wherein the organic mercapto compound is represented by the general formula (1). Light-transmitting electromagnetic wave-shielding film according to claim 1, characterized in that it comprises the corrosion inhibitor in an amount of 0.001g / m ² ~0.04g / m ² with respect to the printed pattern .   Functional transparency with one or more functions selected from infrared shielding properties, hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, UV protection properties, gas barrier properties, and display panel damage prevention properties The translucent electromagnetic wave shielding film according to claim 1, further comprising a layer.   A translucent electromagnetic wave shielding film according to claim 1 is used.   An optical filter for a plasma display panel, wherein the display panel film according to claim 13 is used.   A plasma display panel comprising the film for display panel according to claim 13 or the optical filter for plasma display panel according to claim 14.   On the transparent substrate, fine particles mainly composed of silver having a silver mass% of 60% or more with respect to the metal are printed to form a conductive metal portion and a light transmissive portion, and then the conductive metal portion and A method for producing a light-transmitting electromagnetic wave shielding film, wherein the light-transmitting portion is treated with at least one rust inhibitor.   On the transparent substrate, fine particles mainly composed of silver having a silver mass% of 60% or more with respect to the metal are printed to form a conductive metal portion and a light transmissive portion, and then the conductive metal portion and A method for producing a light-transmitting electromagnetic wave shielding film, wherein the light-transmitting part is treated with a liquid containing Pd ions and then treated with at least one rust preventive agent.