JP2005228879A - Method of fabricating electromagnetic wave shielding material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of fabricating an electromagnetic wave shielding material which can form a fine metal pattern with high accuracy without carrying out an etching process, and which can achieve good adhesion between the metal pattern and a substrate. <P>SOLUTION: The method of fabricating the electromagnetic wave shielding material comprises the following processes which are carried out in this order: a process (a) of forming a polymerization initiating layer containing a polymer having a polymerization initiating group on the substrate transparent to visible lights; a process (b) of forming, on the polymerization initiating layer, a region wherein polymers having a functional group interacting with an electroless plating catalyst or its precursor are directly chemical-bonded into a pattern; a process (c) of applying the electroless plating catalyst or its precursor to the region; and a process (d) of carrying out electroless plating to form the metal pattern. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing an electromagnetic shielding material and an electromagnetic shielding material, and particularly to a shielding member for electromagnetic waves generated from the front surface of a display such as a CRT, PDP (plasma display), liquid crystal, and EL.

  In recent years, as the use of various electric facilities and electronic application facilities has increased, electromagnetic noise interference (EMI) has been increasing. Noise is roughly divided into conduction noise and radiation noise. As a countermeasure against conduction noise, there is a method using a noise filter or the like. On the other hand, as countermeasures against radiation noise, it is necessary to insulate the space electromagnetically, so the housing is made of a metal body or a high conductor, a metal plate is inserted between the circuit board and the cable, A method such as wrapping with metal foil is taken. However, display devices such as CRT (CRT) displays and color display plasma displays emit electromagnetic waves from the screen, and in these display devices, the time that the user is in front of the screen of the display device becomes relatively long. Because it is easy, it is necessary to sufficiently shield the electromagnetic wave radiated from the screen without degrading the image quality. However, in the above method, the electromagnetic wave generated from the front surface of the display such as a CRT or PDP is opaque. Because it was, it was not suitable.

  Therefore, in recent years, a method for forming a thin film conductive layer by vapor-depositing a metal or a metal oxide on a transparent substrate has been proposed as a method for achieving both electromagnetic shielding properties and transparency (see, for example, Patent Document 1). .) However, in this method, when the film thickness is such that transparency can be achieved (several hundreds to 2,000 mm), the surface resistance of the conductive layer becomes too large, so that the shielding effect of 30 dB or more required at 30 MHz to 1 GHz is achieved. On the other hand, it was insufficient at 20 dB or less.

  In addition, an electromagnetic shielding material in which a highly conductive fiber is embedded in a transparent substrate has been proposed (see, for example, Patent Document 2). This electromagnetic wave shielding material has an electromagnetic wave shielding effect of 30 MHz to 1 GHz of 40 to 50 dB, but the fiber diameter necessary for regularly arranging the conductive fibers so as not to leak electromagnetic waves is too thick as 35 μm, and the fibers can be seen. The required visible light transmittance of 60% or more is insufficient to 55% or less, and is not suitable for display applications.

  Further, a conductive layer formed on the plastic film is provided with a photosensitive layer that is exposed by irradiation with active electromagnetic waves. The photosensitive layer is imagewise exposed and developed to form a resist image. The metal is etched to form a conductive metal geometric pattern, and finally the resist is stripped to form a conductive metal geometric pattern, which has been proposed to be used as an electromagnetic shielding film ( For example, see Patent Document 3.) In this method, a thin line pattern of about 30 μm can be formed by using a so-called over-etching method in which the line width after etching becomes narrower than the line width of the formed etching resist pattern. However, since most of the area other than the metal geometric pattern portion is removed by the etching process, there is a lot of waste and the cost of processing the copper waste liquid generated by the etching process is low. There is a limit to conversion. Further, since the pattern is formed by the etching process, there is a disadvantage that the intersection of the pattern is thick and the accuracy is low. This defect causes moiré, and there is a demand for a reduction in thickness at the intersection of patterns, that is, an improvement in accuracy.

In addition, a shielding material is proposed in which an electroless plating catalyst is provided on a transparent substrate in a pattern by a printing method, and a copper mesh pattern is formed thereon by an electroless plating method (for example, Patent Document 4). reference.). Since this method does not require an etching process, the copper waste liquid is not discharged, and the thickness of the intersection of the metal pattern is small. However, because the printing method is used, the accuracy of the metal pattern is limited, and the line Since the width is around 30 μm, there is a problem that the visible light transmittance is insufficient at 55% or less. In addition, there is a problem that the adhesion between the substrate and the metal pattern is poor.
JP-A-5-323101 JP-A-5-327274 Japanese Patent Laid-Open No. 10-41682 Japanese Patent Laid-Open No. 5-288989

An object of the present invention is to solve the conventional technical problems and achieve the following objects.
That is, an object of the present invention is to provide a method for producing an electromagnetic wave shielding material, which can form a fine metal pattern with high accuracy without performing an etching process and has good adhesion to the substrate of the metal pattern. It is to provide.

As a result of intensive studies, the present inventors have formed a specific polymerization initiation layer on a transparent substrate, and a polymer having a functional group that interacts with the electroless plating catalyst or its precursor on the layer is patterned. The present inventors have found that the above object can be achieved by forming a region chemically bonded directly to the substrate and performing electroless plating on the region, thereby completing the present invention.
That is, the method for producing the electromagnetic wave shielding material of the present invention includes:
(A) forming a polymerization initiating layer containing a polymer having a polymerization initiating group on a substrate transparent to visible light;
(B) forming a region in which a polymer having a functional group that interacts with an electroless plating catalyst or a precursor thereof is directly chemically bonded in a pattern on the polymerization initiation layer;
(C) applying an electroless plating catalyst or a precursor thereof to the region;
(D) performing electroless plating to form a metal pattern;
It is characterized by having.

  In the method for producing an electromagnetic wave shielding material of the present invention, it is more preferable to have a step of (e) electroplating after the step (d). Thus, there is an advantage that an electromagnetic wave shielding film having a desired film thickness can be formed by performing electroplating after electroless plating.

  Step (b) in the present invention, that is, interaction with an electroless plating catalyst or a precursor thereof on a polymerization initiation layer containing a polymer having a polymerization initiation group (hereinafter sometimes referred to as a specific polymerization initiation layer). Examples of the step of forming a region in which a polymer having a functional group to be directly chemically bonded in a pattern form includes the following modes (b1) to (b3).

(B1) (b1-1) A functional group that changes into a structure that interacts with an electroless plating catalyst or a precursor thereof by heat, acid, or radiation on the specific polymerization initiation layer, or the interaction. A step of directly bonding a polymer having a functional group to be lost to form a polymer layer; and (b1-2) applying heat, acid, or radiation to the polymer layer in a pattern, thereby forming an electroless plating catalyst. Or a step of forming a pattern-like region that interacts with a precursor thereof.

(B2) A compound having a multi-layered group and a functional group that interacts with the electroless plating catalyst or its precursor is brought into contact with the specific polymerization initiating layer, and then irradiated with radiation in a pattern. A mode in which a pattern-like region interacting with an electroless plating catalyst or a precursor thereof is formed by directly chemically bonding to the polymerization initiation layer.

(B3) (b3-1) a step of directly polymerizing a polymer having a functional group that interacts with the electroless plating catalyst or a precursor thereof on the specific polymerization initiation layer to form a polymer layer; 2) irradiating the polymer layer with radiation in a pattern, removing the specific polymerization initiating layer by ablation, and forming a patterned region that interacts with the electroless plating catalyst or its precursor. Aspect.

Although the effect | action in this invention is not clear, it estimates as follows.
In the present invention, since the polymerization initiating group present in the specific polymerization initiating layer is pendant to the polymer chain, the region having the polymer having a functional group that interacts with the electroless plating catalyst or its precursor is directly chemically bonded in a pattern. When the specific polymerization initiating layer is immersed in the monomer solution, or when the monomer solution is applied onto the layer, the initiator component does not dissolve into the monomer solution, and the surface of the specific polymerization initiating layer is stably formed. It is presumed that the polymerization reaction starts from the existing active species. On the other hand, a photopolymerization initiating layer generally known in the surface grafting technique is present in which a low molecular weight initiator component is dispersed in a crosslinked binder. In such a photopolymerization initiating layer, Since the immobilization ability (stabilization ability) of the initiator is low, it dissolves into the monomer solution, and not only the graft polymerization from the surface but also the polymerization reaction with the eluted initiator component starts in the monomer solution. As a result, a homopolymer that is not directly bonded to the surface of the substrate is by-produced.
As described above, in the present invention, radicals are generated and polymerized only on the surface of the specific polymerization initiating layer as a result of extremely little dissolution of the initiator component. It is estimated that the by-product of the homopolymer that has not been removed is suppressed, and the electromagnetic shielding film formed by plating will not be peeled off due to wear or the like, and the adhesion between the substrate and the electromagnetic shielding film will be improved. Is done.

  In the present invention, the region formed of the polymer having a functional group interacting with the electroless plating catalyst or its precursor formed in the step (b) (including the above-described aspects (b1) to (b3)), In order to selectively apply electroless plating or its precursor, and then perform electroless plating, compared to conventional pattern formation methods by etching using a resist pattern, a finer and more precise metal pattern is used. It is assumed that it can be easily obtained. Further, there is an advantage that there is no etching waste liquid.

According to the method for producing an electromagnetic wave shielding material of the present invention, a fine metal pattern can be formed with high accuracy without performing an etching step, and adhesion to the metal pattern substrate is also improved.
In addition, the obtained electromagnetic shielding material can be provided with a metal pattern that is fine and highly accurate and has good adhesion to the substrate.

Hereinafter, a method for producing the electromagnetic wave shielding material of the present invention will be described.
The method for producing the electromagnetic wave shielding material of the present invention is as follows:
(A) forming a polymerization initiating layer containing a polymer having a polymerization initiating group on a substrate transparent to visible light;
(B) forming a region in which a polymer having a functional group that interacts with an electroless plating catalyst or a precursor thereof is directly chemically bonded in a pattern on the polymerization initiation layer;
(C) applying an electroless plating catalyst or a precursor thereof to the region;
(D) performing electroless plating to form a metal pattern;
In order.
The method for producing the electromagnetic wave shielding material of the present invention will be described more specifically. First, a region that interacts with the electroless plating catalyst or its precursor and a region that does not interact are formed on the specific polymerization initiation layer provided on the transparent substrate, and then the region that interacts Then, after applying an electroless plating catalyst or a precursor thereof, electroless plating is performed to form a metal pattern, thereby producing an electromagnetic wave shielding material. In the present invention, a region where a polymer that interacts with the electroless plating catalyst or its precursor is appropriately referred to as an “interactive region”.
Hereafter, each process in this invention is demonstrated sequentially.

<< (a) Polymerization start layer formation process >>
(A) In the polymerization initiation layer forming step, a polymerization initiation layer containing a polymer having a polymerization initiation group is formed on a substrate transparent to visible light.

First, a polymer having a polymerization initiating group used in this step (hereinafter, a specific polymerization initiating polymer as appropriate) will be described.
This specific polymerization initiating polymer is essential to have a polymerization initiating group in the polymer structure, and is preferably obtained by polymerizing a monomer having a polymerization initiating group.

(Monomer having a polymerization initiating group)
The monomer having a polymerization initiating group constituting the specific polymerization initiating polymer is preferably composed of a monomer having a radical, anionic, or cationic polymerizable group capable of being polymerized with a pendant structure having the following polymerization initiating ability. That is, this monomer has a structure in which a polymerizable group and a polymerization initiating group are both present in the molecule.
The structure having the ability to initiate polymerization includes (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) Examples thereof include ketoxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) active ester compounds, (j) compounds having a carbon halogen bond, and (k) pyridinium compounds. Specific examples of the above (a) to (k) are given below, but the present invention is not limited to these.

(A) Aromatic ketones In the present invention, (a) aromatic ketones preferable as a structure having a polymerization initiating ability include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. Fouassier, J. et al. F. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in Rabek (1993), p77-117. For example, the following compounds are mentioned.

Among these, particularly preferred examples of (a) aromatic ketones are listed below.
The α-thiobenzophenone compound described in JP-B-47-6416 and the benzoin ether compound described in JP-B-47-3981 include, for example, the following compounds.

  Examples of the α-substituted benzoin compound described in JP-B-47-22326 include the following compounds.

  Examples thereof include benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, and the following compounds, for example.

  Examples of the benzoin ethers described in JP-B-60-26403 and JP-A-62-81345 include the following compounds.

  The α-aminobenzophenones described in JP-B-1-34242, US Pat. No. 4,318,791, and European Patent 0284561A1, for example, the following compounds may be mentioned.

P-Di (dimethylaminobenzoyl) benzene described in JP-A-2-211452, for example, the following compounds may be mentioned.

  Examples of the thio-substituted aromatic ketone described in JP-A-61-194062 include the following compounds.

  Examples of the acylphosphine sulfide described in JP-B-2-9597 include the following compounds.

  Examples of the acylphosphine described in JP-B-2-9596 include the following compounds.

  Further, thioxanthones described in JP-B-63-61950, coumarins described in JP-B-59-42864, and the like can also be mentioned.

(B) Onium Salt Compound In the present invention, examples of the preferable (b) onium salt compound as a structure having polymerization initiating ability include compounds represented by the following general formulas (1) to (3).

In general formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a carbon atom having 12 or less carbon atoms. An aryloxy group is mentioned. (Z ² ) ⁻ represents a counter ion selected from the group consisting of halogen ion, perchlorate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonate ion, preferably perchloric acid Ions, hexafluorophosphate ions, and aryl sulfonate ions.

In General Formula (2), Ar ³ represents an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. (Z ³ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

In general formula (3), R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. (Z ⁴ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

  Specific examples of the (b) onium salt compound that can be suitably used in the present invention include paragraph numbers [0030] to [0033] of JP-A No. 2001-133969 and paragraph numbers of JP-A No. 2001-305734. Examples include [0048] to [0052] and those described in paragraph numbers [0015] to [0046] of JP-A-2001-343742.

(C) Organic peroxide In the present invention, the organic peroxide (c) preferable as a structure having a polymerization initiating ability includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl peroxylaurate, tertiary carbonate, 3,3′4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3′4,4 ′ -Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) ) Benzophenone, 3,3'4,4'-tetra- ( - isopropyl) benzophenone, carbonyl di (t-butylperoxy) and carbonyl di (t-hexyl peroxy dihydrogen diphthalate), and the like.

(D) Thio compound In the present invention, the (d) thio compound which is preferable as a structure having a polymerization initiating ability includes a compound having a structure represented by the following general formula (4).

In the general formula (4), R ²⁶ represents an alkyl group, an aryl group or a substituted aryl group, and R ²⁷ represents a hydrogen atom or an alkyl group. R ²⁶ and R ²⁷ represent a group of nonmetallic atoms necessary to form a 5-membered to 7-membered ring which may be bonded to each other and contain a hetero atom selected from oxygen, sulfur and nitrogen atoms.
Specific examples of the thio compound represented by the general formula (4) include the following compounds.

(E) Hexaarylbiimidazole compound In the present invention, preferred (e) hexaarylbiimidazole compounds as a structure having a polymerization initiating ability include lophine dimers described in JP-B Nos. 45-37377 and 44-86516. For example, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5, 5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

(F) Ketooxime ester compound In the present invention, (f) a ketoxime ester compound which is preferable as a structure having a polymerization initiating ability includes 3-benzoyloxyiminobutane-2-one and 3-acetoxyiminobutane-2-one. ON, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1 -One, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

(G) Borate Compound In the present invention, examples of the (g) borate compound that is preferable as a structure having a polymerization initiating ability include compounds represented by the following general formula (5).

In general formula (5), R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be the same or different from each other, and each is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Represents an alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, and R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are bonded to form a cyclic structure. May be. However, at least one of R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ is a substituted or unsubstituted alkyl group. (Z ⁵ ) ⁺ represents an alkali metal cation or a quaternary ammonium cation.

In the general formula (5), the alkyl group represented by R ^{28 to} R ³¹ includes linear, branched, and cyclic groups, and those having 1 to 18 carbon atoms are preferable. Specifically, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are included. In addition, examples of the substituted alkyl group include the above alkyl groups, halogen atoms (eg, —Cl, —Br, etc.), cyano groups, nitro groups, aryl groups (preferably phenyl groups), hydroxy groups, —COOR. ³² (wherein R ³² represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group), —OCOR ³³ or —OR ³⁴ (wherein R ³³ and R ³⁴ represent 1 to 1 carbon atoms) 14 alkyl groups or aryl groups), and those having the following formula as substituents.

In the formula, R ³⁵ and R ³⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group.

  Specific examples of the compound represented by the general formula (5) are described in US Pat. Nos. 3,567,453 and 4,343,891, European Patents 109,772 and 109,773. And the compounds shown below.

(H) Azinium compound In the present invention, preferable as a structure having a polymerization initiating ability, (h) As the azinium salt compound, JP-A Nos. 63-138345, 63-142345 and 63-142346 are disclosed. And compounds having an N—O bond described in JP-A-63-143537 and JP-B-46-42363.

(I) Active ester compound In the present invention, a structure having a polymerization initiating ability is preferred. (I) As an active ester compound, an imide sulfonate compound described in JP-B-62-2623, JP-B-63-14340, JP Examples thereof include active sulfonates described in JP-A-59-174831.

(J) Compound having carbon halogen bond In the present invention, (j) a compound having a carbon halogen bond, which is preferable as a structure having a polymerization initiating ability, includes compounds described in the following general formulas (6) and (7). be able to.

In the general formula (6), X ² represents a halogen atom, and Y ¹ represents —C (X ² ) ₃ , —NH ₂ , —NHR ³⁸ , —NR ³⁸ , —OR ³⁸ . Here, ^R38 represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R ³⁷ represents -C (X ²⁾ _3, alkyl group, substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

In general formula (7), R ³⁹ represents an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group, or a cyano group. . X ³ represents a halogen atom. n represents an integer of 1 to 3.

  Specific examples of the compounds represented by the general formulas (6) and (7) include the following compounds.

(K) Pyridium compounds In the present invention, examples of the (k) pyridium compounds that are preferable as a structure having a polymerization initiating ability include compounds represented by the following general formula (8).

In general formula (8), preferably, R ⁵ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, or a substituted alkynyl group, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom, a halogen atom or a monovalent organic residue, at least one of which is represented by the following general formula (9 ). R ⁵ and R ⁶ , R ⁵ and R ¹⁰ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ may be bonded to each other to form a ring. Furthermore, X represents a counter anion. m represents an integer of 1 to 4.

In general formula (9), R ¹² and R ¹³ are each independently a hydrogen atom, halogen atom, alkyl group, substituted alkyl group, aryl group, substituted aryl group, alkenyl group, substituted alkenyl group, alkynyl group or substituted alkynyl group. R ¹¹ represents a hydrogen atom, alkyl group, substituted alkyl group, aryl group, substituted aryl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group Represents an amino group or a substituted amino group. R ¹² and R ¹³ , R ¹¹ and R ¹² , and R ¹¹ and R ¹³ may be bonded to each other to form a ring. L represents a divalent linking group containing a hetero atom.

  Among these structures having polymerization initiating ability, aromatic ketones and triazines having the following structure are preferably pendant to the polymerizable group. Moreover, as a preferable aromatic ketone, commercial items, such as Irgacure 184, can also be used.

  Moreover, as for the structure which has such a polymerization initiating ability, only 1 type may be pendant to the polymeric group, and 2 or more types may be pendant.

  Examples of the polymerizable group pendant with such a structure having a polymerization initiating ability include a polymerizable group capable of undergoing radical, anionic, and cationic polymerization such as an acryl group, a methacryl group, an acrylamide group, a methacrylamide group, and a vinyl group. Among these, an acrylic group and a methacryl group are particularly preferable from the viewpoint of ease of synthesis.

  Specific examples of the monomer having a polymerization initiating group in the present invention include monomers having the following structures.

  The specific polymerization initiating polymer in the present invention can be synthesized by polymerizing these monomers. In addition, any polymerization method can be used for the synthesis, but it is preferable to use a radical polymerization reaction from the viewpoint of simplicity of the polymerization reaction. In this case, the radical generator for causing radical polymerization reaction is preferably a compound that generates a radical by heat.

The weight average molecular weight of the specific polymerization initiating polymer in the present invention is preferably 10,000 to 10,000,000, more preferably 10,000 to 5,000,000, and further preferably 100,000 to 1,000,000. When the weight average molecular weight of the specific polymerization initiating polymer in the present invention is less than 10,000, the polymerization initiating layer may be easily dissolved in the monomer solution.
In addition, the preferable range of this weight average molecular weight is the case where the specific polymerization initiating polymer in the present invention is a copolymer with a monomer having a crosslinkable group or other third copolymerization component (monomer) described later. Is the same.

  Further, the specific polymerization initiating polymer in the present invention is preferably a polymer having a crosslinkable group in addition to the above-mentioned polymerization initiating group. Thus, because the specific polymerization initiating polymer has a crosslinkable group, the specific polymerization initiating polymer has the polymerization initiating group bonded to the polymer chain, and the polymer chain is immobilized by a cross-linking reaction. It is possible to form a specific polymerization initiation layer that is strong and in which elution of the initiator component is effectively suppressed.

  In the present invention, a graft polymer is generated on the surface of such a polymerization initiating layer as described later. By providing the specific polymerization initiating layer as described above, a compound having a polymerizable group is contained. When the solution is contacted or applied, it is possible to prevent the initiator component (component having a polymerization initiating ability) in the polymerization initiation layer from eluting into the solution. In addition, when forming a specific polymerization initiating layer, by using a specific polymerization initiating polymer having a crosslinkable group, it is possible to use not only a normal radical crosslinking reaction but also a condensation reaction or addition reaction between polar groups. Therefore, a stronger cross-linked structure can be obtained. As a result, it is possible to more efficiently prevent the initiator component in the polymerization initiation layer from eluting, and by suppressing the by-production of a homopolymer not directly bonded to the surface of the polymerization initiation layer, the polymerization initiation layer A directly bonded graft polymer is preferentially produced on the surface.

Hereinafter, the specific polymerization initiating polymer having a crosslinkable group will be described.
The specific polymerization initiating polymer having a crosslinkable group can be obtained by copolymerizing the above-described monomer having a polymerization initiating group and a monomer having a crosslinkable group.

(Monomer having a crosslinkable group)
As the monomer having a crosslinkable group constituting the specific polymerization initiating polymer in the present invention, for example, a conventionally known crosslinkable group (structure used for the crosslink reaction as described in Shinji Yamashita “Crosslinker Handbook”). It is preferably a monomer comprising a radical, anion, or cationic polymerizable group having a pendant functional group). That is, this monomer has a structure in which a polymerizable group and a crosslinkable group are both present in the molecule.

Among these conventionally known crosslinkable groups, a carboxylic acid group (—COOH), a hydroxyl group (—OH), an amino group (—NH ₂ ), and an isocyanate group (—NCO) are pendant to the polymerizable group. preferable.
Moreover, as for such a crosslinkable group, only 1 type may be pendant by the polymeric group, and 2 or more types may be pendant.

  Examples of the polymerizable group pendant with these crosslinkable groups include polymerizable groups capable of polymerizing radicals, anions, and cationic groups such as acrylic groups, methacrylic groups, acrylamide groups, methacrylamide groups, and vinyl groups. Among these, an acrylic group and a methacryl group are particularly preferable from the viewpoint of ease of synthesis.

  Specific examples of the monomer having a crosslinkable group in the present invention include monomers having the following structures.

  In the specific polymerization initiating polymer in the present invention, the copolymerization molar ratio of the copolymerization component (A) having a polymerization initiating group and the copolymerization component (B) having a crosslinkable group is (A) 1-40. It is preferable that the mol% and (B) is 20 to 70 mol%. From the viewpoint of the film properties of the polymerization initiation layer after the graft polymerization reaction or the crosslinking reaction, it is more preferable that (A) is 5 to 30 mol% and (B) is 30 to 60 mol%.

[Other copolymerization components (monomers)]
For the specific polymerization initiating polymer in the present invention, a third copolymerization component (monomer) as shown below is used in order to adjust the film forming property, hydrophilicity / hydrophobicity, solvent solubility, polymerization initiating property, etc. Also good.
As the third copolymer component, any compound can be used as long as it is a radical, anion, or cationic polymerizable compound. In view of polymerizability and the like, an acrylic or methacrylic monomer in which an alkyl group having 1 to 20 carbon atoms is pendant is preferable. At this time, the alkyl group is preferably an alkyl group having tertiary hydrogen in order to generate more active species by UV exposure. The alkyl group may be substituted with any substituent, but from the viewpoint of preventing the polymerization initiation layer from dissolving into the monomer solution, the alkyl group may be substituted with a substituent having a quaternary ammonium salt structure. preferable.

  A specific polymerization initiating polymer having a preferred structure can be synthesized by appropriately copolymerizing these monomers. In addition, any polymerization method can be used to synthesize the copolymer, but from the viewpoint of simplicity of the polymerization reaction, it is preferable to use a radical polymerization reaction. In this case, the radical generator for causing radical polymerization reaction is preferably a compound that generates a radical by heat.

  Further, the specific polymerization initiating polymer having this preferable structure is not limited to being synthesized by copolymerization as described above. For example, a polymer having a polymerization initiating group in the side chain is synthesized, and then You may synthesize | combine by introduce | transducing an appropriate amount of crosslinkable groups in a polymer. Alternatively, a specific polymerization initiating polymer may be synthesized by polymerizing one monomer unit having both a polymerization initiating group and a crosslinkable group.

  In consideration of the availability of the monomer, etc., the specific polymerization initiating polymer having a preferable structure is a mode in which a polymerization initiating group and a crosslinkable group are copolymerized and synthesized in different monomer units. It is preferable that

[Polymerization initiation layer formed by immobilizing a specific polymerization initiation polymer by a crosslinking reaction]
In the polymerization initiation layer forming step, as a method for fixing the specific polymerization initiating polymer by a crosslinking reaction, there are a method using a self-condensation reaction of the specific polymerization initiating polymer and a method using a crosslinking agent in combination, and a crosslinking agent is used. Is preferred. As a method of using the self-condensation reaction of the specific polymerization initiating polymer, for example, when the crosslinkable group is -NCO, the property that the self-condensation reaction proceeds by applying heat is used. As this self-condensation reaction proceeds, a crosslinked structure can be formed.

Moreover, as a crosslinking agent used for the method of using a crosslinking agent together, a conventionally well-known thing as described in Shinji Yamashita "crosslinking agent handbook" can be used.
Preferred combinations of the crosslinkable group and the crosslinker in the specific polymerization initiating polymer include (crosslinkable group, crosslinker) = (— COOH, polyvalent amine), (—COOH, polyvalent aziridine), (—COOH, Polyvalent isocyanate), (—COOH, polyvalent epoxy), (—NH ₂ , polyvalent isocyanate), (—NH ₂ , aldehydes), (—NCO, polyvalent amine), (—NCO, polyvalent isocyanate) , (—NCO, polyhydric alcohol), (—NCO, polyhydric epoxy), (—OH, polyhydric alcohol), (—OH, polyhalogenated compound), (—OH, polyhydric amine), (− OH, acid anhydride). Among these, (functional group, cross-linking agent) = (— OH, polyvalent isocyanate) is a more preferable combination in that a urethane bond is generated after the cross-linking and a high-strength cross-linking can be formed.
Specific examples of the crosslinking agent in the present invention include the structures shown below.

  Such a crosslinking agent is added to the coating solution containing the above-mentioned specific polymerization initiating polymer when the polymerization initiating layer is formed. Thereafter, the crosslinking reaction proceeds by the heat during the drying of the coating film, and a strong crosslinked structure can be formed. More specifically, the following ex1. Or the dehydration reaction indicated by ex2. The cross-linking reaction proceeds by the addition reaction represented by the above, and a cross-linked structure is formed. The temperature conditions in these reactions are preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 80 ° C. or higher and 200 ° C. or lower.

  The amount of the crosslinking agent added in the coating solution varies depending on the amount of the crosslinkable group introduced into the specific polymerization initiating polymer, but is usually 0.01 to 50 with respect to the number of moles of the crosslinkable group. It is preferably an equivalent, more preferably 0.01 to 10 equivalent, and still more preferably 0.5 to 3 equivalent. When the addition amount of the crosslinking agent is less than this upper limit value, the degree of crosslinking becomes low and the polymerization initiating layer is easily dissolved in the monomer solution. Further, when the amount of the crosslinking agent added is larger than the upper limit value, the unreacted crosslinking agent component may remain in the polymerization initiation layer and may elute into the monomer solution, thereby adversely affecting the polymerization reaction.

[Deposition of polymerization initiation layer]
In this step, the above-mentioned specific polymerization initiating polymer is dissolved in a suitable solvent, a coating solution is prepared, the coating solution is placed on the substrate by coating, the solvent is removed, and the crosslinking reaction proceeds. The film is formed by
In addition, when a specific polymerization initiating polymer synthesized only from a monomer having a polymerization initiating group is used when forming the polymerization initiating layer, it is not necessary for the crosslinking reaction to proceed. After the preparation, the coating solution may be disposed on the substrate by coating or the like, and the solvent may be removed (dried).

(solvent)
The solvent used when applying the polymerization initiation layer is not particularly limited as long as the above-mentioned specific polymerization initiation polymer is dissolved. From the viewpoint of easy drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
Specifically, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, methanol, Ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, - such as methoxypropyl acetate.
These solvents can be used alone or in combination. The concentration of the solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount of the polymerization initiation layer is a weight after drying is preferably 0.1 to 20 g / m ^2, further, 0.1 to 15 g / m ² is preferred. Application amount 0. can not express a sufficient polymerization initiation ability is less than lg / m ^2, becomes insufficient graft polymerization, there is a concern that desired rigid graft structure can not be obtained, the film property when the coating amount exceeds 20 g / m ² is Neither is preferable because it tends to decrease and film peeling tends to occur.

〔Base material〕
As the base material used for the electromagnetic wave shielding film material of the present invention, any base material can be used as long as it has shape retention and is transparent to visible light.
Specifically, for example, colorless and transparent glass, various kinds of transparent plastic substrates, various kinds of transparent plastic films, and the like can be used as the transparent support.
Furthermore, as the transparent plastic substrate and the transparent plastic film, specifically, most general-purpose resin materials can be used, and in particular, (meth) acrylic resins, polyester resins, or triacetyl cellulose. It is preferable to use a film or sheet of (TAC).

The size and thickness of the transparent support vary depending on the intended use. For example, the thickness of the transparent support may be a thin film having appropriate flexibility when applied to a small display, and preferably 0.03 mm to 0.5 mm. In addition, when applied to a large display of several tens of inches or more, a firm flexible film or a rigid support is preferable, and a thickness of 0.3 to 10.0 mm is preferable. This is because when applied to a large display, it is necessary to mechanically install the display using an accessory jig or the like.
In any case, the transparency of the support is ideally 100% with respect to visible light, but it is preferable to select one having a transmittance of 80 to 98%.
As described above, the specific polymerization initiation layer is formed on the substrate by the polymerization initiation layer forming step of the present invention.

<< (b) Pattern formation process >>
In this step, a region (interactive region) is formed on the specific polymerization initiation layer, in which a polymer having a functional group that interacts with the electroless plating catalyst or its precursor is chemically bonded directly in a pattern.
As an aspect which forms an interactive area | region, the aspect of (b1)-(b3) mentioned above is mentioned. Hereinafter, the aspects (b1) to (b3) will be described in detail.

<Aspect (b1)>
Aspect (b1) is (b1-1) a functional group that changes to a structure that interacts with an electroless plating catalyst or a precursor thereof by heat, acid, or radiation on the specific polymerization initiation layer, or A step of directly chemically bonding a polymer having a functional group that loses interaction to form a polymer layer; and (b1-2) applying heat, acid, or radiation to the polymer layer in a pattern. Forming a patterned region that interacts with the electroplating catalyst or its precursor.
Hereinafter, as appropriate, “a functional group that changes to a structure that interacts with an electroless plating catalyst or a precursor thereof by heat, acid, or radiation, or a functional group that loses the interaction” is referred to as a polar conversion group. Called.

<Step (b1-1) in Aspect (b1)>
(Surface graft polymerization)
The polymer layer formed in the step (b1-1) is produced by applying a means generally called surface graft polymerization. Graft polymerization is a method of synthesizing a graft (grafting) polymer by giving an active species on a polymer compound chain, thereby further polymerizing another monomer that initiates the polymerization. When a molecular compound forms a solid surface, it is called surface graft polymerization. In the present invention, this solid surface serves as the specific polymerization initiation layer. Moreover, as means for providing active species, means such as irradiation with a width ray such as UV light can be cited, whereby energy is imparted and active species are generated.
Here, the polymer layer obtained from the surface graft polymerization in the present invention may be composed of a graft polymer in which the terminal of the polymer chain having a polar conversion group is directly bonded as a graft chain to the surface of the specific polymerization initiation layer. Further, it may be composed of a graft polymer in which a polymer chain having a polarity converting group is bonded via a trunk polymer compound.

As the surface graft polymerization method for realizing this embodiment, any known method described in literatures can be used. For example, New Polymer Experimental Science 10, edited by Polymer Society, 1994, published by Kyoritsu Shuppan Co., Ltd., p135, Japanese Patent Laid-Open Nos. 63-92658, 10-296895, and 11-119413. The photo-graft polymerization method and the plasma irradiation graft polymerization method described in 1) are described. In addition, the adsorption technique manual, NTS Co., Ltd., supervised by Takeuchi, 1999.2, p203, p695 describes radiation-induced graft polymerization methods such as γ rays and electron beams. Of these, photograft polymerization is preferred.
As a specific method of the photograft polymerization method, the methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413 can be used.

Next, the polarity conversion group used in this embodiment will be described. The polarity conversion group in this aspect includes (A) a type whose polarity is changed by heat or acid, and (B) a type whose polarity is changed by radiation (light).
In the present invention, the “structure interacting with an electroless plating catalyst or a precursor thereof” is not particularly limited as long as it is a functional group to which an electroless plating catalyst or a precursor thereof described later can be attached. Includes a hydrophilic group.

[(A) Functional group whose polarity is changed by heat or acid]
First, (A) the functional group whose polarity is changed by heat or acid will be described.
(A) The functional group whose polarity is changed by heat or acid includes two functional groups that change from hydrophobic to hydrophilic by heat or acid, and one that changes from hydrophilic to hydrophobic by heat or acid. There are types.

((A-1) Functional group that changes from hydrophobic to hydrophilic by heat or acid)
(A-1) Examples of the functional group that changes from hydrophobic to hydrophilic by heat or acid include known functional groups described in the literature.
Below, the example of the compound which has (A-1) the functional group which changes from hydrophobicity to hydrophilicity with a heat | fever or an acid, and this functional group is given.
For example, alkylsulfonic acid esters, disulfones, sulfonimides described in JP-A-10-282672, alkoxyalkyl esters described in EP0652483 and WO92 / 9934, H.P. Ito et al., Macromolecules, vol. 21, pp. Examples thereof include t-butyl ester described in 1477, carboxylic acid ester protected with an acid-decomposable group described in literature such as silyl ester and vinyl ester.

Also, Masahiro Tsunooka, “Surface” vol. 133 (1995), p. 374, an iminosulfonate group described by Masahiro Tsunooka, Polymer preprints, Japan vol. 46 (1997), p. Examples thereof include β-ketone sulfonate esters described in 2045, nitrobenzyl sulfonate compounds disclosed in Aoyama Yamaoka and JP-A 63-257750, but are not limited to these functional groups.
Also suitable are functional groups described in JP-A No. 2001-117223. Among these publications, a secondary alkyl sulfonate group represented by the general formula (1), a tertiary carboxylic acid ester group, and an alkoxyalkyl ester group represented by the general formula (2) are particularly preferable. Among them, the secondary alkylsulfonic acid ester group represented by the general formula (1) is most preferable. Specific examples of particularly preferred functional groups are shown below.

((A-2) Functional group that changes from hydrophilic to hydrophobic by heat or acid)
In the present invention, (A-2) As the functional group that changes from hydrophilic to hydrophobic by heat or acid, a known functional group can be exemplified.
Examples of (A-2) functional groups that change from hydrophilic to hydrophobic by heat or acid and examples of compounds having the functional groups are given below.
Examples thereof include polymers containing onium bases, particularly polymers containing ammonium salts described in JP-A-10-296895 and US Pat. No. 6,190,830. More specific examples include (meth) acryloloxyalkyltrimethylammonium.
Also suitable are functional groups described in JP-A No. 2001-117223. Among these publications, the carboxylic acid group and the carboxylic acid group represented by the general formula (3) are particularly preferable, but are not particularly limited to these examples. Specific examples of particularly preferred functional groups are shown below.

  The polymer having a polar conversion group in the present invention may be a homopolymer of one kind of monomer having the functional group as described above, or may be a copolymer of two or more kinds. Moreover, as long as the effect of this invention is not impaired, the copolymer with another monomer may be sufficient.

  (A-1) Specific examples of monomers having a functional group that changes from hydrophobic to hydrophilic by heat or acid are shown below.

  (A-2) Specific examples of monomers having a functional group that changes from hydrophilic to hydrophobic by heat or acid are shown below.

[Photothermal conversion material]
If the energy applied to the polymer layer formed on the specific polymerization initiating layer by the surface graft polymerization described above is light energy such as an IR laser, the light energy is converted into heat energy. It is preferable that the photothermal conversion substance is contained somewhere in the polymer layer, the specific polymerization initiation layer, and the substrate. Moreover, a photothermal conversion substance layer may be provided between the specific polymerization initiating layer and the base material and added thereto.

  The photothermal conversion material used here can be any material that can absorb ultraviolet light, visible light, infrared light, white light, etc. and convert it into heat. For example, carbon black, carbon graphite, pigment, phthalocyanine Examples thereof include pigments, iron powder, graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, and chromium sulfide. Particularly preferred are dyes, pigments or metal fine particles having a maximum absorption wavelength from 760 nm to 1200 nm, which is the exposure wavelength of an infrared laser used for energy application.

  As the dye used, commercially available dyes and known dyes described in the literature (for example, “Dye Handbook” edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, and metal thiolate complexes. Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., naphthoquinone dyes, JP-A-58-112792, etc. And cyanine dyes described in British Patent 434,875.

  As the metal fine particles used, fine particles composed of Au, Ag, Pt, Cu, Ni, Zn, Pd, Cr, Fe, Pb, etc., and fine particles composed of oxides or sulfides of those metals are used. Specific examples include iron powder, graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, and chromium sulfide.

From the viewpoint of sensitivity and film strength of the photothermal conversion substance-containing layer, these dyes or pigments are 0.01 to 50% by mass, preferably 0.1 to 10% by mass of the total solids of the photothermal conversion substance-containing layer. In the case, it is particularly preferably 0.5 to 10% by mass, and in the case of a pigment, particularly preferably 3.1 to 10% by mass.
In addition, the metal fine particles are 0.01 to 50% by mass, preferably 0.1 to 30% by mass, particularly preferably the total solid content of the photothermal conversion material-containing layer, from the viewpoint of sensitivity and film strength of the photothermal conversion material-containing layer. It can be used at a ratio of 0.1 to 10% by mass.

[Acid generator]
In order to give an acid for polarity conversion to the polymer layer formed on the substrate by the surface graft polymerization described above, an acid generator is contained in any of the polymer layer, the substrate, and the intermediate layer. It is preferable to keep it. Further, an acid generating material layer may be provided between the intermediate layer and the base material and added thereto.

  The acid generator is a compound that generates an acid by heat or light. Generally, it is a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, or a photochromic agent. Further, compounds that generate acid by known light used in microresist and the like, and mixtures thereof can be used, and these can be appropriately selected and used.

  For example, S.M. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al. , Polymer, 21, 423 (1980), ammonium salts described in JP-A-3-140140, etc., phosphonium salts described in US Pat. No. 4,069,055, etc. Iodonium salts described in JP-A-2-150848, JP-A-2-296514, and the like; V. Crivello et al. , Polymer J. et al. 17, 73 (1985), U.S. Pat. No. 3,902,114, European Patent 233,567, U.S. 297,443, U.S. 297,442, U.S. Pat. 933,377, 4,491,628, 5,041,358, 4,760,013, 4,734,444, 2, No. 833,827, German Patent No. 2,904,626, No. 3,604,580, No. 3,604,581, etc.,

J. et al. V. Crivello et al. Selenonium salts described in C., Macromolecules, 10 (6), 1307 (1977) and the like. S. Wen et al. , Teh, Proc. Conf. Rad. Curing ASIA, p478, Tokyo, Oct (1988) and other onium salts such as arsonium salts, organic halogen compounds described in JP-A-63-298339, and organic compounds described in JP-A-2-161445, etc. Metal / organic halides; Hayase et al. , J .; Polymer Sci. , 25, 753 (1987), Japanese Patent Application Laid-Open No. 60-198538, Japanese Patent Application Laid-Open No. 53-133022, etc., photo acid generator having an o-nitrobenzyl type protecting group, Japanese Patent Application Laid-Open No. 64-18143. JP-A-2-165756, JP-A-3-140109, and the like, compounds such as iminosulfonates, which are photodecomposed to generate sulfonic acid, described in JP-A-61-166544, etc. The disulfone compound can be mentioned.

  From the viewpoint of sensitivity and film strength of the acid generating material-containing layer, these acid generating materials are 0.01 to 50% by mass, preferably 0.1 to 30% by mass of the total solid content of the acid generating material-containing layer. Can be used.

[(B) Functional group whose polarity changes with light]
Among the functional groups whose polarity changes, there are those that change their polarity by light irradiation of 700 nm or less. Such a functional group whose polarity is changed by (B) light (polarity-converting group sensitive to light of 700 nm or less) is directly irradiated with light of a predetermined wavelength, regardless of long-wavelength exposure such as infrared rays or heat, It is characterized in that the polarity changes with high sensitivity by the occurrence of decomposition, ring opening or dimerization reaction. Hereinafter, the functional group whose polarity changes by light irradiation of 700 nm or less will be described.
(B) As for the functional group whose polarity changes by light, (B-1) a functional group that changes from hydrophobic to hydrophilic by light, and (B-2) a functional group that changes from hydrophilic to hydrophobic by light. There are two types.

((B-1) Functional group that changes from hydrophobic to hydrophilic by light)
(B-1) Examples of functional groups that change from hydrophobic to hydrophilic by light include general formulas (1) to (4) and (7) to (9) described in JP-A-2003-222972. The functional group represented by can be used.

((B-2) Functional group that changes from hydrophilic to hydrophobic by light)
(B-2) Examples of the functional group that changes from hydrophilic to hydrophobic by light include a bispyridinioethylene group.

<Step (b1-2) in Aspect (b1)>
In the (b1-2) step, the polymer layer formed in the (b1-1) step is subjected to heating, application of acid, or irradiation of radiation such as light, and the polarity is changed into a pattern. This is a step of forming a region (interactive region) that interacts with the electroplating catalyst or its precursor.

As a method of changing the polarity into a pattern, for example, writing by irradiation with radiation such as heating or exposure can be used. For example, light irradiation with an infrared laser, an ultraviolet lamp, visible light, or the like, electron beam irradiation such as γ rays, thermal writing with a thermal head, or the like is possible. Examples of these light sources include mercury lamps, metal halide lamps, xenon lamps, chemical lamps, and carbon arc lamps. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
Specific examples generally used include direct writing with a thermal recording head, scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
In addition, as one mode of light irradiation, if the polymer layer contains a photothermal conversion substance, the polarity can be changed into a pattern by heating by scanning exposure such as laser light in the infrared region.

  On the other hand, in the case of a polymer layer obtained by using a polarity converting group that is sensitive to light of 700 nm or less, as a means for converting the polarity into a pattern, the polarity converting group is decomposed, ring-opened or dimerized, and the affinity is determined. Any means of light irradiation can be used as long as the aqueous property can be changed. For example, light irradiation with an ultraviolet lamp, visible light, or the like can be used. Examples of these light sources include mercury lamps, metal halide lamps, xenon lamps, chemical lamps, and carbon arc lamps.

In order to perform direct pattern formation using digital data from a computer, a method of changing polarity by laser exposure is preferable. Lasers include gas lasers such as carbon dioxide lasers, nitrogen lasers, Ar lasers, He / Ne lasers, He / Cd lasers, Kr lasers, solid state lasers such as liquid (pigment) lasers, ruby lasers, Nd / YAG lasers, GaAs / Semiconductor lasers such as GaAlAs and InGaAs lasers, KrF lasers, XeCl lasers, XeF lasers, and excimer lasers such as Ar ₂ can be used.

<Aspect (b2)>
In the embodiment (b2), a compound having a polymerizable group and a functional group that interacts with an electroless plating catalyst or a precursor thereof is brought into contact with the specific polymerization initiation layer, and then radiation is irradiated in a pattern. In this step, the compound is directly chemically bonded to the substrate to form a patterned region (interactive region) that interacts with the electroless plating catalyst or its precursor.
In the following description, “a compound having a polymerizable group and a functional group that interacts with an electroless plating catalyst or a precursor thereof” is appropriately referred to as an interactive group-containing polymerizable compound.

As described above, the interactive group-containing polymerizable compound is brought into contact with the specific polymerization initiating layer and irradiated with radiation in a pattern, thereby polymerizing the interactive group-containing polymerizable compound in the pattern. Since the functional group and the specific polymerization initiating layer generate chemical bonds, a strong and durable interactive region can be formed.
As a method of generating a chemical bond between the polymerizable group of the interactive group-containing polymerizable compound and the specific polymerization initiating layer, a surface graft polymerization method can be used. By this surface graft polymerization method, a graft polymer in which the end of an interactive group-containing polymerizable compound chain is chemically bonded directly or via a trunk polymer compound to the surface of a specific polymerization initiating layer having active species And can be formed by the graft polymer.
The surface graft polymerization method according to aspect (b2) is the same as the surface graft polymerization method described in aspect (b1).

  In addition, as a method of bringing the interactive group-containing polymerizable compound into contact with the specific polymerization initiating layer, a substrate having the specific polymerization initiating layer is used as a liquid composition containing the interactive group-containing polymerizable compound. However, from the viewpoint of handling and production efficiency, as described later, a layer containing the composition containing the interactive group-containing polymerizable compound as a main component is specifically polymerized. It is preferably formed on the surface of the start layer by a coating method.

(Interactive group-containing polymerizable compound)
The interactive group-containing polymerizable compound used in the embodiment is a polymer obtained by polymerizing a monomer having an interactive group, which will be described later, and a homopolymer or copolymer obtained using at least one selected from the monomers having the interactive group. This refers to a polymer into which an ethylene addition polymerizable unsaturated group (polymerizable group) such as a vinyl group, an allyl group, or a (meth) acryl group is introduced, and this polymer has a polymerizable group at least at the terminal or side chain. In particular, those having a polymerizable group at the terminal are preferable, and those having a polymerizable group at the terminal and side chain are more preferable.

Such an interactive group-containing polymerizable compound can be synthesized as follows.
Synthesis methods include (I) a method of copolymerizing a monomer having an interactive group and a monomer having a polymerizable group, and (II) a monomer having an interactive group and a monomer having a double bond precursor. A method of introducing a double bond by copolymerization and then treating with a base or the like, (III) introducing a double bond by reacting a polymer having an interactive group with a monomer having a polymerizable group (polymerizable group Method). A preferred synthesis method is a method of (II) copolymerizing a monomer having an interactive group and a monomer having a double bond precursor from the viewpoint of synthesis suitability, and then introducing a double bond by treatment with a base or the like. (III) A method of introducing a polymerizable group by reacting a polymer having an interactive group with a monomer having a polymerizable group.

  Monomers used for the synthesis of the interactive group-containing polymerizable compound include (meth) acrylic acid or alkali metal salts and amine salts thereof, itaconic acid or alkali metal salts and amine salts thereof, 2-hydroxyethyl (meth) Acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or its hydrohalide, 3-vinylpropionic acid or its alkali metal salt and amine salt, vinylsulfonic acid Or alkali metal salts and amine salts thereof, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxypolyoxyethylene Carboxyl group, sulfonic acid group, phosphoric acid group, amino group, hydroxyl group, amide group, phosphine group, imidazole group, pyridine group, ether group, etc. such as recall mono (meth) acrylate and N-vinylpyrrolidone (the following structure) And a monomer having a functional group (a salt thereof when a salt structure can be formed).

Examples of the allyl group-containing monomer copolymerized with the monomer having an interactive group include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.
Examples of the monomer having a double bond precursor include 2- (3-chloro-1-oxopropoxy) ethyl methacrylate, and compounds (i-1 to i-60) described in JP-A No. 2003-335814. Among these, the following compound (i-1) is particularly preferable.

  Furthermore, a polymerizable group used for introducing an unsaturated group by utilizing a reaction with a functional group such as a carboxyl group, an amino group or a salt thereof, a hydroxyl group and an epoxy group in a polymer having an interactive group. Examples of the monomer include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.

Next, (III) a method of copolymerizing a monomer having an interactive group and a monomer having a double bond precursor and then introducing a double bond by treatment with a base or the like will be described in detail.
Regarding this synthesis method, the method described in JP-A No. 2003-335814 can be used.

(Base used for elimination reaction)
Preferred examples of the base used when introducing a double bond by treatment with a base include alkali metal hydrides, hydroxides or carbonates, organic amine compounds, and metal alkoxide compounds.

  Preferred examples of alkali metal hydrides, hydroxides or carbonates include sodium hydride, calcium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, carbonate Examples include potassium hydrogen and sodium hydrogen carbonate.

  Preferable examples of the organic amine compound include trimethylamine, triethylamine, diethylmethylamine, tributylamine, triisobutylamine, trihexylamine, trioctylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N- Methyldicyclohexylamine, N-ethyldicyclohexylamine, pyrrolidine, 1-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 1-methylpiperidine, 2,2,6,6-tetramethylpiperidine, piperazine, 1,4-dimethyl Piperazine, quinuclidine, 1,4-diazabicyclo [2,2,2] -octane, hexamethylenetetramine, morpholine, 4-methylmorpholine, pyridine, picoline, 4-dimethylaminopyridine, Cytidine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), N, N'-dicyclohexylcarbodiimide (DCC), diisopropylethylamine, Schiff base, and the like.

  Preferable examples of the metal alkoxide compound include sodium methoxide, sodium ethoxide, potassium t-butoxide and the like.

These bases may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The amount of the base used may be equal to or less than the equivalent of the double bond precursor in the compound, or may be equal to or more than the equivalent.
The temperature condition in the elimination reaction may be any of room temperature, cooling, and overheating. As preferable temperature conditions, it is the range of -20-100 degreeC.

Macromonomer can also be used as an example of an interactive group containing polymeric compound. The method for producing the macromonomer used in this embodiment is described in, for example, Chapter 2 of “Macromonomer Chemistry and Industry” (Editor, Yuya Yamashita) published on September 20, 1999 by the IP Publishing Office. Various production methods have been proposed in “Synthesis”. Particularly useful macromonomers used in this embodiment include macromonomers derived from carboxyl group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylstyrenesulfonic acid, And sulfonic acid macromonomer derived from a monomer of the salt thereof, (meth) acrylamide, N-vinylacetamide, N-vinylformamide, amide macromonomer derived from N-vinylcarboxylic acid amide monomer, hydroxyethyl methacrylate Macromonomer derived from hydroxyl group-containing monomers such as cocoon, hydroxyethyl acrylate, glycerol monomethacrylate, methoxyethyl acrylate, methoxy polyethylene glycol acrylate, polyethylene glycol Acrylate macromonomers derived from alkoxy group or ethylene oxide group-containing monomers such as. A monomer having a polyethylene glycol chain or a polypropylene glycol chain can also be usefully used as the macromonomer used in this embodiment.
Among these macromonomers, a useful molecular weight is in the range of 250 to 100,000, and a particularly preferable range is 400 to 30,000.

The solvent used in the composition containing such an interactive group-containing polymerizable compound is not particularly limited as long as the macromonomer or monomer as a main component can be dissolved, but water, a water-soluble solvent, etc. Aqueous solvents are preferred, and mixtures thereof and those obtained by further adding a surfactant to the solvent are preferred.
The water-soluble solvent refers to a solvent that is miscible with water in an arbitrary ratio, and examples of such a water-soluble solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, and glycerin, acids such as acetic acid, Examples thereof include ketone solvents such as acetone, amide solvents such as formamide, and the like.

The surfactant that can be added to the solvent as needed may be any that dissolves in the solvent. Examples of such surfactants include an anionic surfactant such as sodium n-dodecylbenzenesulfonate. Agents, cationic surfactants such as n-dodecyltrimethylammonium chloride, polyoxyethylene nonylphenol ether (commercially available products include, for example, Emulgen 910, manufactured by Kao Corporation), polyoxyethylene sorbitan monolaurate (commercially available) Examples of the product include a trade name “Tween 20” and the like, and nonionic surfactants such as polyoxyethylene lauryl ether.
In the case where the composition is brought into contact in a liquid state, it can be arbitrarily performed. However, when the coating layer is formed by a coating method, the coating amount is sufficient to interact with the plating catalyst or its precursor, and from the viewpoint of obtaining a uniform coating film is preferably 0.1 to 10 g / m ² in terms of solid content, in particular 0.5 to 5 g / m ² is preferred.

[Radiation pattern irradiation]
In the step (b2), when the radiation is irradiated in a pattern, there is no particular limitation on the radiation, and an active site is generated on the surface of the polymerization initiation layer, so that the polymerizable property of the interactive group-containing polymerizable compound is increased. Any group can be used as long as it can provide energy capable of bonding the group and the polymerization initiation layer surface, but from the viewpoint of cost and simplicity of the apparatus, a method of irradiating actinic rays is preferable.
When irradiating actinic light, both scanning exposure based on digital data and pattern exposure using a lith film can be used.
Further, as the pattern writing method, the various writing methods previously mentioned in the aspect (b1) can be preferably applied to this aspect as well.

  In this way, the reactive group-containing polymerizable compound is polymerized with respect to the active sites generated on the surface of the polymerization initiating layer by irradiation with radiation, and a graft chain having high mobility is formed. Further, as a preferred embodiment, by using an interactive group-containing polymerizable compound having a polymerizable group at the terminal and side chain, a graft chain is further added to the polymerizable group of the side chain of the graft chain bonded to the polymerization initiation layer. By bonding, a graft chain structure having a branch is formed, the formation density and mobility of the graft chain are dramatically improved, and higher interaction with the electroless plating catalyst or its precursor is expressed. .

<< Aspect (b3) >>
Aspect (b3) includes (b3-1) a step of directly polymerizing a polymer having a functional group that interacts with the electroless plating catalyst or a precursor thereof on the specific polymerization initiation layer to form a polymer layer; (B3-2) irradiating the polymer layer with a pattern of radiation, removing the specific polymerization initiating layer by ablation, and forming a patterned region that interacts with the electroless plating catalyst or its precursor; ,including.
In this embodiment, it is necessary that the specific polymerization initiation layer contains a photothermal conversion substance. As a result, the irradiated radiation such as laser light is absorbed by the photothermal conversion substance in the specific polymerization start layer and converted into heat, so that the specific polymerization start layer is ablated (melting, decomposition, volatilization, combustion, etc. As a result of the removal of the specific polymerization initiating layer, the overlying polymer layer is also removed, and as a result, a pattern-like interactive region is selectively formed on the substrate surface. Is.

<Step (b3-1) in Aspect (b3)>
Step (b3-1) is a step of forming a polymer layer by directly chemically bonding a polymer having a functional group that interacts with the electroless plating catalyst or its precursor on the specific polymerization initiation layer.
Hereinafter, the “functional group that interacts with the electroless plating catalyst or its precursor” is appropriately referred to as an interactive group.

(Formation of polymer layer)
As the method for forming the polymer layer in the step (b3-1), a surface graft polymerization method can be used. By this surface graft polymerization method, a graft polymer is produced in which the end of the polymer chain having an interactive group is chemically bonded directly or via a trunk polymer compound to the surface of the polymerization initiation layer having active species. And the graft polymer can form an interactive region.
The surface graft polymerization method according to aspect (b3) is the same as the surface graft polymerization method described in aspect (b1).

(Photothermal conversion material)
When the mode (b3) is applied, the photothermal conversion substance added to the specific polymerization initiation layer is a substance that can absorb light such as ultraviolet rays, visible rays, infrared rays, white rays, etc. and convert it into heat. All can be used. More specifically, the same dyes, pigments, and metal fine particles as the photothermal conversion substance described in the embodiment (b1) can be used.
From the viewpoint of sensitivity and film strength of the photothermal conversion substance-containing layer (specific polymerization initiation layer), the dye or pigment used in this embodiment preferably has a total solid content of 0.01 to 50% by mass, 0.1-10 mass% is more preferable. When the dye is used, it is particularly preferably 0.5 to 10% by mass, and when the pigment is used, it is particularly preferably 3.1 to 10% by mass. The metal fine particles used are 0.01 to 50% by mass, preferably 0.1 to 30% by weight based on the total solid content of the photosensitive layer, from the viewpoint of sensitivity and film strength of the photothermal conversion substance-containing layer (specific polymerization initiation layer). It can be used at a ratio of mass%, particularly preferably 0.1 to 10 mass%.

(Other additives)
In this embodiment, it is preferable to further contain nitrocellulose in the polymerization initiation layer for the purpose of improving the ablation effect of the specific polymerization initiation layer. Nitrocellulose promotes the removal of the polymerization initiating layer by decomposing near infrared laser light by the heat generated by the absorption of the light absorber and efficiently generating a low molecular gas.

  The polymer having an interactive group in this embodiment is synthesized by surface graft polymerization of the interactive group-containing polymerizable compound used in the above embodiment (b2).

[Interactive group-containing polymerizable compound]
As the interactive group-containing polymerizable compound suitably used in this embodiment, the same compound as the interactive group-containing polymerizable compound used in the embodiment (b2) can be used.
Moreover, the same thing can be used for the solvent, additive, etc. which are used for the composition containing an interactive group containing polymeric compound.

<Step (b3-2) in Aspect (b3) of the Present Invention>
Step (b3-2) is a step of forming a patterned region that interacts with the electroless plating catalyst or its precursor by irradiating the polymer layer with radiation in a pattern, removing the photosensitive layer by ablation. is there.

In this (a3-2) step, the radiation of the irradiated laser beam or the like causes the specific polymerization start layer to be ablated, and the specific polymerization start layer is thereby removed. The polymer layer formed thereon is also removed, and as a result, a patterned region (interactive region) that interacts with the electroless plating catalyst or its precursor is formed. This also exposes the substrate that does not interact with the electroless plating catalyst or its precursor.
For the radiation pattern irradiation in this step, the same aspect as the above aspect (b2) can be preferably applied.

  As mentioned above, although the formation process of the interactive area | region in aspect (b1)-(b3) has been described, the terminal of a polymer has couple | bonded with the base material and the photosensitive layer, and this interaction area | region has interaction. It has the characteristic that the part which expresses a sex group is formed of the graft polymer which can maintain high mobility. For this reason, the outstanding interaction property of an interaction area | region and an electroless-plating catalyst or its precursor is expressed.

<(C) Step of imparting an electroless plating catalyst or a precursor thereof to the interactive region>
Step (c) in the present invention is a step of applying an electroless plating catalyst or a precursor thereof onto the interactive region.

[Electroless plating catalyst]
The electroless plating catalyst used in this step is mainly a zero-valent metal, and examples thereof include Pd, Ag, Cu, Ni, Al, Fe, and Co. In the present invention, Pd and Ag are particularly preferable because of their good handleability and high catalytic ability. As a method for fixing the zero-valent metal to the interactive region, for example, a method in which a metal colloid whose charge is adjusted so as to interact with the interactive group of the interactive region is applied to the interactive region is used. It is done. In general, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be adjusted by the surfactant or the protective agent used here, and the metal colloid whose charge is adjusted in this way interacts with the interactive group of the interactive region. Thus, the metal colloid (electroless plating catalyst) can be selectively adsorbed on the interactive region.

[Electroless plating catalyst precursor]
The electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. Mainly, metal ions of zero-valent metal used in the electroless plating catalyst are used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The electroless plating catalyst precursor metal ion is applied to the interactive region in the step (b), and before being immersed in the electroless plating bath, it is changed to a zero-valent metal by a separate reduction reaction. A catalyst may be used, or the electroless plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

Actually, the metal ion which is the electroless plating precursor is applied to the pattern region in the form of a metal salt. The metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) n, MCn, M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions, and Ag ions and Pd ions are preferable in terms of catalytic ability.

  As a method for imparting a metal colloid that is an electroless plating catalyst or a metal salt that is an electroless plating precursor to an interactive region, the metal colloid is dispersed in an appropriate dispersion medium, or the metal salt is an appropriate solvent. If a solution containing the metal ions dissolved and dissociated is prepared, and the solution is applied to a substrate having an interactive region, or a substrate having an interactive region is immersed in the solution. Good. Contacting a solution containing a metal ion to adsorb the metal ion to the interacting group in the interacting region using an ion-ion interaction or a dipole-ion interaction, or The interactive region can be impregnated with metal ions. From the viewpoint of sufficiently performing such adsorption or impregnation, the metal ion concentration or the metal salt concentration in the solution to be contacted is preferably in the range of 0.01 to 50% by mass, preferably 0.1 to 30%. More preferably, it is in the range of mass%. Further, the contact time is preferably about 1 minute to 24 hours, more preferably about 5 minutes to 1 hour.

<(D) Step of performing electroless plating to form a metal pattern>
In this step, a metal pattern is formed by performing electroless plating on the substrate obtained by the step (c) and having the electroless plating catalyst or precursor thereof applied to the interactive region. . That is, by performing electroless plating in this step, a high-density metal film (electromagnetic wave shielding film) according to the pattern of the interactive region is formed, and becomes a metal pattern. The formed metal pattern has excellent electromagnetic shielding properties.

[Electroless plating]
Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
In the electroless plating in this step, for example, the base material obtained in the step (c) to which the electroless plating catalyst is applied in the interactive region is washed with water to remove an excess electroless plating catalyst (metal). After removing, it is immersed in an electroless plating bath. As the electroless plating bath to be used, a generally known electroless plating bath can be used.
In the case where the substrate provided with the electroless plating catalyst precursor in the interactive region is immersed in the electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the interactive region, The substrate is washed with water to remove excess precursors (such as metal salts) and then immersed in an electroless plating bath. In this case, reduction of the precursor and subsequent electroless plating are performed in the electroless plating bath. As the electroless plating bath used here, a generally known electroless plating bath can be used as described above.

The composition of a general electroless plating bath is as follows: 1. metal ions for plating, 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included. In addition to these, the plating bath may contain known additives such as a plating bath stabilizer.
As the types of metals used in the electroless plating bath, copper, tin, lead, nickel, gold, palladium, and rhodium are known, and among these, copper and gold are particularly preferable from the viewpoint of conductivity.
In addition, there are optimum reducing agents and additives according to the above metals. For example, a copper electroless plating bath contains Cu (SO ₄ ) ₂ as a copper salt, HCOH as a reducing agent, and a chelating agent such as EDTA or Rochelle salt as a copper ion stabilizer as an additive. The plating bath used for electroless plating of CoNiP includes cobalt sulfate and nickel sulfate as metal salts, sodium hypophosphite as a reducing agent, sodium malonate, sodium malate and sodium succinate as complexing agents. It is included. Further, the electroless plating bath of palladium contains (Pd (NH ₃ ) ₄ ) Cl ₂ as metal ions, NH ₃ and H ₂ NNH ₂ as reducing agents, and EDTA as a stabilizer. These plating baths may contain components other than the above components.

  The film thickness of the electromagnetic shielding film (metal pattern) formed in this way can be controlled by the concentration of the metal salt or metal ion in the plating bath, the immersion time in the plating bath, the temperature of the plating bath, or the like. From the viewpoint of electromagnetic shielding properties, it is preferably 0.5 μm or more, and more preferably 3 μm or more. Further, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.

<(E) Electroplating process>
In the method for producing an electromagnetic wave shielding material of the present invention, (e) a step of performing electroplating (electroplating step) can be performed after the step (d). In this step, after the electroless plating in the step (d), electroplating can be performed using the electromagnetic wave shielding film formed in this step as an electrode. Thereby, an electromagnetic wave shielding film (metal pattern) having an arbitrary thickness can be easily formed on the electromagnetic wave shielding film having excellent adhesion to the substrate. By adding this step, the metal pattern can be formed to a thickness according to the purpose, which is useful for improving the electromagnetic shielding properties.

As the electroplating method in the present invention, a conventionally known method can be used. In addition, as a metal used for the electroplating of this process, copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. are mentioned. From the viewpoint of conductivity, copper, gold, and silver are preferable. More preferred.
The film thickness of the electromagnetic shielding film obtained by electroplating varies depending on the required electromagnetic shielding properties, and can be controlled by adjusting the concentration of metal contained in the plating bath, the immersion time, or the current density. can do. In addition, the film thickness when used for a general electromagnetic shielding material or the like is preferably 0.3 μm or more, and more preferably 3 μm or more, from the viewpoint of electromagnetic shielding properties.

<Metal pattern>
In the present invention, the geometrical figure of the metal pattern (geometrical figure of the interactive region) is a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square such as a square, a rectangle, a rhombus, a parallelogram, a trapezoid, (Positive) hexagons, (Positive) octagons, (Positive) dodecagons, (Positive) n-gons such as dodecagons, circles, ellipses, stars, etc. It can be used alone or in combination of two or more. From the viewpoint of electromagnetic shielding properties, the triangle is the most effective, but from the viewpoint of visible light transmission, the aperture ratio increases as the n number of (positive) n-gons increases with the same line width. From the viewpoint of visible light transmittance, the aperture ratio needs to be 50% or more, more preferably 60% or more, and a quadrangle is preferable as a form that achieves both electromagnetic wave shielding properties and visible light transmittance. The aperture ratio is a percentage of the ratio of the area obtained by subtracting the area of the conductive metal in the geometric figure drawn with the conductive metal from the effective area with respect to the effective area of the electromagnetic wave shielding material. When the area of the display screen is the effective area of the electromagnetic wave shielding material, the screen is visible.

  Further, the electromagnetic wave shielding property of the electromagnetic wave shielding material is required to have both an electric field shielding effect and a magnetic field shielding effect of 50 dB or less. Generally, it is known that when the surface resistance of the metal pattern (electromagnetic wave shielding film) surface of the electromagnetic wave shielding material is 1Ω / □ or less, both the electric field shielding effect and the magnetic field shielding effect are 50 dB or less. It is preferable to adjust the film thickness of the metal pattern and the metal pattern shape (geometrical figure) to make the surface resistance value 1Ω / □ or less.

As described above, according to the method for producing an electromagnetic wave shielding material of the present invention, the adhesion between the base material and the electromagnetic wave shielding film is excellent due to the presence of the specific polymerization initiation layer. In particular, since an interactive region made of a graft polymer is formed on the specific polymerization initiation layer as described above, a metal is formed between the graft polymer and the formed metal film (electromagnetic wave shielding film). A hybrid state is formed at the base material interface of the film, and better adhesion can be exhibited.
Thereby, even if it is a case where the obtained electromagnetic wave shielding material is deformed and used, a metal pattern does not peel and it can maintain high electromagnetic wave shielding property.

  In addition, in order to selectively apply electroless plating or a precursor thereof to the interactive region and then perform electroless plating, it is finer than the conventional pattern formation method by etching using a resist pattern. Thus, a highly accurate metal pattern can be easily obtained. Thereby, the obtained electromagnetic shielding material can have both high electromagnetic shielding properties and high transparency.

  Furthermore, since the interactive region is made of a graft polymer, plating partially proceeds in the internal graft chain, and metal particles having a small particle size are deposited there. Since the metal particles having a small particle diameter are black, the electromagnetic shielding material is blackened. As a result, when applied as an electromagnetic shielding material for a display, the contrast of the screen can be increased.

<Usage of electromagnetic shielding material>
The electromagnetic wave shielding material obtained by the production method of the present invention is used, for example, by attaching it to the front surface of the display. Examples of the display include a CRT, a PDP, an EL panel, and a liquid crystal panel.
Moire occurs on the screen depending on the installation method. Moire becomes inconspicuous when conductive metal lines (metal patterns) intersect the scanning lines at a certain angle or more. As a result of investigating the best angle in the electromagnetic wave shielding material produced in the present invention, it was found that about 30 degrees is good when an orthogonal mesh (90 degrees crossing) is used.
In addition, the electromagnetic shielding material preferably has a solid conductive layer, for example, formed on the periphery of one side or both sides so as to remove electricity from an arbitrary place. In particular, in the present invention, a method in which a solid conductive layer is formed on the periphery of the electromagnetic wave shielding material, which is used as a static elimination terminal portion, and is connected to a ground or the like for simple static elimination is a more preferable aspect. is there.
Furthermore, a layer having an infrared shielding property, a layer having an antireflection treatment, a layer having an antiglare treatment, and a layer having high surface hardness and abrasion resistance can be formed on any surface of the electromagnetic wave shielding material. . These are merely examples, and can be used in other forms.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
[Synthesis Example 1]
(Synthesis of specific polymerization initiating polymer A)
30 g of propylene glycol monomethyl ether (MFG) was added to a 300 ml three-necked flask and heated to 75 degrees. There, 8.1 g of [2- (acryloyloxy) ethyl] (4-benzoylbenzyl) dimethylammonium bromide, 9.9 g of 2-hydroxyethyl methacrylate, 13.5 g of isopropyl methacrylate, and dimethyl-2,2′-azobis A solution of (2-methylpropionate) 0.43 g and MFG 30 g was added dropwise over 2.5 hours. Thereafter, the reaction temperature was raised to 80 ° C., and the reaction was further continued for 2 hours to obtain the following specific polymerization initiation polymer A.

[Synthesis Example 2]
(Synthesis of specific polymerization initiating polymer B)
30 g of propylene glycol monomethyl ether (MFG) was added to a 300 ml three-necked flask and heated to 75 degrees. There, 5.1 g of 4-methacryloyloxy-benzophenone, 9.9 g of 2-hydroxyethyl methacrylate, 9.8 g of isopropyl methacrylate, 3.97 g of [2- (methacryloyloxy) ethyl] trimethylammonium bromide, A solution of 0.43 g of dimethyl-2,2′-azobis (2-methylpropionate) and 30 g of propylene glycol monomethyl ether (MFG) was added dropwise over 2.5 hours. Thereafter, the reaction temperature was raised to 80 ° C. and the reaction was further continued for 2 hours to obtain the following specific polymerization initiation polymer B.

[Synthesis Example 3]
(Synthesis of specific polymerization initiation polymer C)
30 g of propylene glycol monomethyl ether (MFG) was added to a 300 ml three-necked flask and heated to 75 degrees. There, 8.1 g of [2- (acryloyloxy) ethyl] (4-benzoylbenzyl) dimethylammonium bromide, 9.9 g of 2-aminoethyl methacrylate, 13.5 g of isopropyl methacrylate, and dimethyl-2,2′-azobis A solution of 0.43 g (2-methylpropionate) and 30 g of propylene glycol monomethyl ether (MFG) was added dropwise over 2.5 hours. Thereafter, the reaction temperature was raised to 80 ° C., the reaction was further continued for 2 hours, and the reaction was further continued for 2 hours to obtain the following specific polymerization initiating polymer C.

[Example 1]
(Step (a) of the present invention)
A PET film (product name: M4100, manufactured by Toyobo Co., Ltd.) is used as a base material, and a polymerization initiation layer coating solution 1 having the following composition is applied to the surface using a rod bar No. 9 and dried at 110 ° C. for 10 minutes and crosslinked. I let you. The film thickness of the obtained specific polymerization initiation layer was 1.5 μm.

<Polymerization initiation layer coating solution 1>
-0.1 g of the above specific polymerization initiating polymer A
・ TDI (Tolylene-2,4-diisocyanate) 0.04g
・ Infrared absorber (IR125 Wako Pure Chemicals) 0.02g
・ Methyl ethyl ketone (MEK) 1.9g

(Step (b1-1) in Embodiment (b1) of the Present Invention)
The base material on which the specific polymerization initiating layer is formed is immersed in 10 wt% α (styrene-4-sulfonyl) acetic acid sodium salt aqueous solution, and irradiated with light for 5 minutes using a 1.5 kW high pressure mercury lamp in an argon atmosphere. did. After the light irradiation, the substrate was thoroughly washed with water to form a polymer layer in which α (styrene-4-sulfonyl) acetic acid Na salt was graft polymerized.

(Step (b1-2) in the embodiment (b1) of the present invention)
The obtained polymer layer was pattern-exposed with an infrared laser (beam diameter 20 μm) that emits infrared light having a wavelength of 830 nm to form an interactive region.

(Steps (c) and (d) of the present invention)
Next, the base material having the interactive region was immersed in an aqueous solution of 0.1% by mass of palladium nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) for 1 hour, and then washed with distilled water.
Then, it was immersed in an electroless plating bath at 40 ° C. having the following composition for 20 minutes to form a metal pattern.

<Electroless plating bath components>
・ OPC Kappa-H T1 (Okuno Pharmaceutical Co., Ltd.) 6mL
・ OPC Kappa-H T2 (Okuno Pharmaceutical Co., Ltd.) 1.2mL
・ OPC Kappa-H T3 (Okuno Pharmaceutical Co., Ltd.) 10mL
・ Water 83mL

[Example 2]
(Step (a) of the present invention)
Using a PET film (product name: M4100, manufactured by Toyobo Co., Ltd.) as a base material, a polymerization initiation layer coating solution 2 having the following composition is applied to the surface using a rod bar No. 9, and dried at 110 ° C. for 10 minutes and crosslinked. I let you. The film thickness of the obtained specific polymerization initiation layer was 1.1 μm.

<Polymerization initiation layer coating solution 2>
-0.1 g of the above specific polymerization initiating polymer A
・ TDI (Tolylene-2,4-diisocyanate) 0.04g
・ Methyl ethyl ketone (MEK) 1.7g

(Step (b1-1) in Embodiment (b1) of the Present Invention)
The base material on which the specific polymerization initiating layer is formed is immersed in an aqueous solution containing acrylic acid (10 wt%) and sodium periodate (NaIO ₄ , 0.01 wt%), and the above 400 W high-pressure mercury lamp in an argon atmosphere. And irradiated with light for 30 minutes. After light irradiation, the obtained base material was thoroughly washed with ion-exchanged water to obtain a base material grafted with acrylic acid.

  Next, an aqueous solution comprising 1 liter of water, 40 g of N-ethyl-N ′ (3-dimethylaminopropyl) carbodiimide hydrochloride and 6 g of N-hydroxysuccinimide was prepared, and acrylic acid was grafted thereon. The material was immersed for 1 hour for ester conversion. Thereafter, 6 g of 2-nitrobenzylphenol was further added and reacted to obtain a polymer layer composed of a graft polymer having a photodegradable functional group (polar conversion group).

(Step (b1-2) in the embodiment (b1) of the present invention)
The obtained polymer layer was exposed imagewise with a laser emitting blue light having a wavelength of 400 nm (beam diameter 20 μm) to form an interactive region.

(Steps (c) and (d) of the present invention)
The base material having the interactive region was immersed in an aqueous solution of 0.1% by mass of palladium nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) for 1 hour, and then washed with distilled water.
Thereafter, electroless plating was performed in the same electroless plating bath at 40 ° C. as in Example 1 for 20 minutes to form a metal pattern.

[Example 3]
(Step (a) of the present invention)
A PET film (product name: M4100, manufactured by Toyobo Co., Ltd.) is used as a base material, and a polymerization initiation layer coating solution 3 having the following composition is applied to the surface using a rod bar No. 9, and dried and crosslinked at 110 ° C. for 10 minutes. I let you. The film thickness of the obtained specific polymerization initiation layer was 1.1 μm.

<Polymerization initiation layer coating solution 3>
・ 0.1 g of the specific polymerization initiation polymer B
・ TDI (Tolylene-2,4-diisocyanate) 0.04g
・ Methyl ethyl ketone (MEK) 1.9g

(Step of embodiment (b2) of the present invention)
Acrylic acid was applied to the base material on which the specific polymerization initiation layer was formed using rod bar # 6, and the coated surface was laminated with a PET film having a thickness of 25 μm.
Furthermore, the mask pattern which vapor-deposited chromium was piled up on it, and UV light was irradiated from the top (400W high pressure mercury lamp: UVL-400P, Riken Kagaku Sangyo Co., Ltd. product, irradiation time 30 seconds). After light irradiation, the mask and the laminate film were removed and washed with water to form an interactive region in which polyacrylic acid was grafted in a pattern.

(Steps (c) and (d) of the present invention)
Next, the base material having the interactive region was immersed in an aqueous solution of 0.1% by mass of palladium nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) for 1 hour, and then washed with distilled water. Then, it was immersed in a 0.2 M (mol / l) NaBH ₄ aqueous solution for 20 minutes and reduced to zerovalent palladium.
Thereafter, electroless plating was performed for 20 minutes in the same electroless plating bath at 40 ° C. as in Example 1 to form a metal pattern.

[Example 4]
(Step (a) of the present invention)
A PET film (product name: M4100, manufactured by Toyobo Co., Ltd.) is used as a base material, and a polymerization initiation layer coating solution 4 having the following composition is applied to the surface using a rod bar No. 9 and dried at 110 ° C. for 10 minutes and crosslinked. I let you. The film thickness of the obtained specific polymerization initiation layer was 0.8 μm.

<Polymerization initiation layer coating solution 4>
-0.1 g of the above specific polymerization initiating polymer A
・ TDI (Tolylene-2,4-diisocyanate) 0.04g
・ Methyl ethyl ketone (MEK) 1.9g

(Step of embodiment (b2) of the present invention)
A polymer coating solution having the following composition was applied to the base material on which the specific polymerization initiating layer was formed using rod bar # 18. The film thickness of the obtained film was 0.8 μm.

<Composition formation of polymer coating solution>
・ Polymerizable group-containing polymer (synthesis method is shown below) 0.25 g
・ Cyclohexyl ketone 8.0g

<Method for synthesizing the polymerizable group-containing polymer>
(Synthesis of monomer A)
In a 500 ml three-necked flask, 58.6 g of 2-hydroxyethyl methacrylate was added, 250 ml of acetone was added and stirred. After adding 39.2 g of pyridine and 0.1 g of p-methoxyphenol, the mixture was cooled in an ice bath containing ice water. After the temperature of the mixture became 5 ° C. or lower, 114.9 g of 2-bromoisobutanoic acid bromide was added dropwise using a dropping funnel over 3 hours. After completion of dropping, the ice bath was removed and the mixture was further stirred for 3 hours. The reaction mixture was poured into 750 ml of water and stirred for 1 hour. The aqueous mixture was extracted three times with 500 ml of ethyl acetate using a separatory funnel. The organic layer was washed successively with 500 ml of 1M (mol / l) hydrochloric acid, 500 ml of saturated aqueous sodium hydrogen carbonate solution and 500 ml of saturated brine. 100 g of magnesium sulfate was put into the organic layer, dehydrated and dried, and then filtered. The solvent was distilled off under reduced pressure to obtain 120.3 g of monomer A.

Next, 40 g of N, N-dimethylacetamide was placed in a 1000 ml three-necked flask and heated to 70 ° C. under a nitrogen stream. A solution of monomer A 12.58 g, methacrylic acid 27.52 g, V-601 (manufactured by Wako Pure Chemical Industries) 0.921 g in N, N-dimethylacetamide 40 g was added dropwise over 2.5 hours. After completion of dropping, the mixture was heated to 90 ° C. and further stirred for 2 hours. After cooling the reaction solution to room temperature, it was poured into 3.5 L of water to precipitate a polymer compound. The precipitated polymer compound was collected by filtration, washed with water and dried to obtain 30.5 g of a polymer compound. As a result of measuring the mass average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 124,000.
In a 200 ml three-necked flask, 26.0 g of the polymer compound obtained and 0.1 g of p-methoxyphenol were added, dissolved in 60 g of N, N-dimethylacetamide and 60 g of acetone, and cooled in an ice bath containing ice water. After the temperature of the mixture became 5 ° C. or lower, 60.4 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was added dropwise over 1 hour using a dropping funnel. After completion of the dropwise addition, the ice bath was removed and the mixture was further stirred for 8 hours. The reaction solution was poured into 2 L of water in which 17 ml of concentrated hydrochloric acid was dissolved to precipitate a polymerizable group-containing polymer. The precipitated polymerizable group-containing polymer was collected by filtration, washed with water, and dried to obtain 15.6 g.

  The obtained film was subjected to pattern exposure for 1 minute using a 1.5 kW high-pressure mercury lamp using a mask pattern. Thereafter, the obtained film was immersed in a saturated aqueous sodium bicarbonate solution for 5 minutes, and the unexposed area was developed to form an interactive region.

(Steps (c) and (d) of the present invention)
The base material having the interactive region was immersed in an aqueous solution containing 0.1% by mass of silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) for 1 hour, and then washed with distilled water.
Thereafter, electroless plating was performed in the same electroless plating bath at 40 ° C. as in Example 1 for 20 minutes to form a metal pattern.

[Example 5]
(Step (e) of the present invention)
The metal pattern (electromagnetic wave shielding film) formed in Example 4 was further electroplated at room temperature for 15 minutes.
<Composition of electroplating bath>
・ Copper sulfate 38g
・ 95 g of sulfuric acid
・ Hydrochloric acid 1mL
・ Kappa-Gream PCM (Meltex Co., Ltd.) 3mL
・ Water 500g

[Example 6]
(Step (a) of the present invention)
A PET film (product name: M4100, manufactured by Toyobo Co., Ltd.) is used as a base material, and a polymerization initiation layer coating solution 5 having the following composition is applied to the surface using a rod bar No. 9, and dried and crosslinked at 110 ° C. for 10 minutes. I let you. The film thickness of the obtained specific polymerization initiation layer was 1.5 μm.

<Polymerization initiation layer coating solution 5>
-0.1 g of the above specific polymerization initiating polymer C
・ TDI (Tolylene-2,4-diisocyanate) 0.04g
・ Carbon black (MA100, manufactured by Mitsubishi Chemical Corporation) 0.02g
・ Methyl ethyl ketone (MEK) 1.9g

(Step (b3-1) in Embodiment (b3) of the Present Invention)
An aqueous solution of sodium sulfonate (30% by mass) was applied to the base material on which the specific polymerization initiating layer was formed using a rod bar # 12, and the coated surface was laminated with a 25 μm PET film without drying. Then, a pattern UV light was irradiated for 1 minute using a 1.5 kW high-pressure mercury lamp from above. After light irradiation, the laminate film was removed and washed with water to obtain a polymer layer grafted with sodium sulfonate.

(Step (b3-2) in Embodiment (b3) of the Present Invention)
The obtained polymer layer was exposed imagewise with an infrared laser (beam diameter 20 μm) emitting infrared light having a wavelength of 830 nm. By this laser exposure, the specific polymerization initiating layer that absorbed the laser beam ablated, and was removed together with the polymer layer to form an interactive region.

(Steps (c) and (d) of the present invention)
The base material having the interactive region was immersed in an aqueous solution containing 0.1% by mass of silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) for 1 hour, and then washed with distilled water.
Thereafter, electroless plating was performed in the same electroless plating bath at 40 ° C. as in Example 1 for 20 minutes to form a metal pattern.

[Example 7]
(Step (b1-1) in Embodiment (b1) of the Present Invention)
A base material having a specific polymerization initiating layer produced in the same manner as in Example 2 was immersed in a t-butyl acrylate solution (30% by mass, solvent: propylene glycol monomethyl ether (MFG)) and 1.5 kW under an argon atmosphere. Exposure was performed for 15 minutes using a high-pressure mercury lamp.
The substrate obtained after light irradiation was thoroughly washed with propylene glycol monomethyl ether (MFG) to obtain a polymer layer obtained by grafting poly-t-butyl acrylate onto the substrate.

(Step (b1-2) in the embodiment (b1) of the present invention)
Next, a solution having the following composition was applied on the polymer layer. The film thickness of the obtained film was 0.5 μm.
・ Triphenylsulfonium triflate 0.05g
・ Methyl ethyl ketone (MEK) 1g

  Next, the obtained film was subjected to pattern exposure for 1 minute using a 1.5 kW high-pressure mercury lamp using a mask pattern, followed by post-heating at 90 ° C. for 2 minutes. Thereafter, the obtained film was washed with methyl ethyl ketone (MEK) to form an interaction region formed by converting the functional group of the exposed portion into a hydrophilic group.

(Steps (c) and (d) of the present invention)
The base material having the interaction region formed was immersed in a liquid in which Ag particles having positive charges prepared by the following method were dispersed, and then washed with distilled water.
Thereafter, electroless plating was performed in the same electroless plating bath at 40 ° C. as in Example 1 for 20 minutes to form a metal pattern.

<Method of synthesizing Ag particles having positive charge>
Add 3 g of bis (1,1-trimethylammoniumdecanoylaminoethyl) disulfide to 50 ml of ethanol solution of silver perchlorate (5 mM) and slowly drop 30 ml of sodium borohydride solution (0.4M) with vigorous stirring. Ions were reduced to obtain a dispersion of Ag particles (silver particles) coated with quaternary ammonium.

[Evaluation]
(Metallic pattern shape evaluation)
Using the optical microscope (Nikon, OPTI PHOTO-2), the metal pattern in the electromagnetic wave shielding material obtained in Examples 1 to 7, the pattern shape of the opening, the metal pattern width, the width between the metal patterns, and the intersection We measured fatness. The evaluation index of “weight of intersection” is as follows. The measurement results are shown in Table 2 below.
○: No intersection weight x: Thickness intersection

(Measurement of visible light transmittance)
Using the spectrophotometer (made by Varian), the average value of the transmittance | permeability in 400-800 nm was calculated | required for the electromagnetic wave shielding material obtained in Examples 1-7. The measurement results are shown in Table 2 below.

(Evaluation of adhesion)
The electromagnetic wave shielding materials obtained in Examples 1 to 7 were evaluated for film adhesion (adhesion between the substrate and the metal pattern) by a cross-cut tape method in accordance with JIS 5400. In addition, in the following evaluation index, O means that when the tape peeling test was repeated twice on the cut grid, none of the first peeling was observed. The measurement results are shown in Table 2 below.
○: No peeling ×: There was peeling

(Evaluation of surface resistance)
The surface resistance of the surface on which the metal pattern was formed in the electromagnetic wave shielding materials obtained in Examples 1 to 7 was measured using Lorester EP (manufactured by Mitsubishi Chemical). The measurement results are shown in Table 2 below.

According to the results in Table 2 above, it was found that in the electromagnetic wave shielding materials obtained by the examples of the present invention, thin wires having a width of 30 μm or less, which were difficult in the prior art, were formed. . In addition, it was confirmed that these thin line | wire widths are controllable with said aspect (b1)-(b3) of this invention, and exposure conditions. For example, when the interactive region is formed by ablation, the thin line width is about 28 μm, and it has been confirmed that a practically sufficient thin line width can be obtained. Furthermore, when the interactive region was formed by UV exposure using a mask, the fine line width was about 10 to 15 μm, and a very fine metal pattern could be obtained. Thus, according to the present invention, a desired thin line width can be obtained depending on the purpose. Also, no pattern intersections were found.
In addition, the electromagnetic shielding materials obtained by the examples of the present invention all have a low surface resistance value, excellent electric field shielding effect and magnetic field shielding effect, and further transparency and adhesion between the substrate and the metal pattern. Was also found to be excellent.

Claims (2)

(A) forming a polymerization initiating layer containing a polymer having a polymerization initiating group on a substrate transparent to visible light;
(B) forming a region in which a polymer having a functional group that interacts with an electroless plating catalyst or a precursor thereof is directly chemically bonded in a pattern on the polymerization initiation layer;
(C) applying an electroless plating catalyst or a precursor thereof to the region;
(D) performing electroless plating to form a metal pattern;
The manufacturing method of the electromagnetic wave shielding material which has these.   The method for producing an electromagnetic shielding material according to claim 1, further comprising (e) a step of performing electroplating after the step (d).