JP2005223271A - Electromagnetic wave shield material and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an electromagnetic wave shield material whereby a minute metallic pattern can be formed with high accuracy without the need for an etching process and excellent adhesion of the metallic pattern to a base member can be attained, and to provide the electromagnetic wave shield material provided with the minute and highly precise metallic pattern having excellent adhesion to the base member. <P>SOLUTION: The manufacturing method of the electromagnetic wave shield material includes a step (a) of forming a region wherein a polymer having a functional group interacting with an electroless plating catalysis or its precursor is directly chemically bonded onto a transparent base member to visible light, a step (b) of providing the electroless plating catalysis or its precursor to the region, and a step (c) of applying electroless plating to the region to form a metallic pattern. The electromagnetic wave shield material is obtained by the manufacturing method above. <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.
Another object of the present invention is to provide an electromagnetic shielding material provided with a metal pattern that is fine and highly accurate and has good adhesion to a substrate.

As a result of intensive studies, the present inventors have conducted electroless plating on a region where the polymer to which the electroless plating catalyst or its precursor is applied is directly chemically bonded to the substrate in a pattern, so that The inventors have found that the object is achieved and have completed the present invention.
That is, the method for producing the electromagnetic wave shielding material of the present invention includes:
(A) 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 a substrate transparent to visible light;
(B) applying an electroless plating catalyst or a precursor thereof to the region;
(C) performing electroless plating to form a metal pattern;
In order.

Moreover, as a suitable aspect in the preparation methods of the electromagnetic wave shielding material of this invention, there exist three shown below.
That is, the preferred first aspect in the method for producing an electromagnetic wave shielding material of the present invention is:
(A1-1) 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 a substrate transparent to visible light, or the mutual Direct chemical bonding of a polymer having a functional group that loses its action to form a polymer layer;
(A1-2) applying heat, acid, or radiation to the polymer layer in a pattern to form a patterned region that interacts with the electroless plating catalyst or its precursor;
(B) applying an electroless plating catalyst or a precursor thereof to the region;
(C) performing electroless plating to form a metal pattern;
In order.

Moreover, the suitable 2nd aspect in the preparation methods of the electromagnetic wave shielding material of this invention is as follows.
(A2) After contacting a compound having a polymerizable group and a functional group that interacts with an electroless plating catalyst or a precursor thereof on a substrate transparent to visible light, the radiation is patterned. Irradiating and chemically bonding the compound directly to the substrate to form a patterned region that interacts with the electroless plating catalyst or precursor thereof;
(B) applying an electroless plating catalyst or a precursor thereof to the region;
(C) performing electroless plating to form a metal pattern;
In order.

Furthermore, a preferred third aspect in the method for producing an electromagnetic wave shielding material of the present invention is:
(A3-1) providing a photosensitive layer containing a photothermal conversion substance and a binder on a substrate transparent to visible light;
(A3-2) 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 photosensitive layer;
(A3-3) irradiating the polymer layer with a pattern of radiation, removing the photosensitive layer by ablation, and forming a patterned region that interacts with the electroless plating catalyst or its precursor;
(B) applying an electroless plating catalyst or a precursor thereof to the region;
(C) performing electroless plating to form a metal pattern;
In order.

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

  The electromagnetic wave shielding material of the present invention is formed by a polymer having a functional group that interacts with an electroless plating catalyst or a precursor thereof formed on a transparent substrate with respect to visible light, directly bonded to the substrate in a pattern. It has a metal pattern formed by applying an electroless plating catalyst or a precursor thereof to the region formed and then performing electroless plating.

As described above, according to the present invention, the electroless plating or the precursor thereof is selectively applied to the pattern-like region that interacts with the electroless plating catalyst or the precursor thereof, and then the electroless plating is performed. Therefore, it is possible to easily obtain a fine and highly accurate metal pattern as compared with the conventional electromagnetic shielding material.
In addition, the polymer formed in a pattern and the electroless plating catalyst or its precursor interact, and further, electroless plating is performed on the catalyst or its precursor. The adhesion is excellent.

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 electromagnetic shielding material can be provided with a metal pattern that is fine and highly accurate and has good adhesion to the substrate.

Hereinafter, the present invention will be described in detail.
<Method for producing electromagnetic shielding material>
First, a method for producing the electromagnetic 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 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 a substrate transparent to visible light;
(B) applying an electroless plating catalyst or a precursor thereof to the region;
(C) performing a process of performing electroless plating to form a metal pattern.
The method for producing the electromagnetic wave shielding material of the present invention will be described more specifically. First, using a polymer having a specific functional group on a substrate transparent to visible light, a region that interacts with the electroless plating catalyst or its precursor and a region that does not interact with each other are formed. Next, an electroless plating catalyst or a precursor thereof is applied to the interacting region, and then electroless plating is performed to form a metal pattern, thereby producing an electromagnetic wave shielding material.

Regarding these steps (a) to (c), preferred embodiments (1) to (3) in the method for producing an electromagnetic wave shielding material of the present invention (hereinafter, as appropriate, embodiments (1) to (3) of the present invention) Will be described in detail.
In addition, any of (a1-1) and (a1-2) processes in aspect (1), (a2) process in aspect (2), and (a3-1) to (a3-3) processes in aspect (3) Even in the method, “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 is formed on a substrate transparent to visible light (described above) (A) Step) ”.

As described above, in the aspects (1) to (3) of the present invention, since the steps (b) and (c) are the same in any aspect, they will be described later together. The steps (a1-1) and (a1-2) in (1), the step (a2) in mode (2), and the steps (a3-1) to (a3-3) in mode (3) will be described.
The “patterned region interacting with the electroless plating catalyst or its precursor” formed in the embodiments (1) to (3) of the present invention is hereinafter referred to as “interactive region” as appropriate.

<Step (a1-1) in Aspect (1) of the Present Invention>
The step (a1-1) is 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 a substrate transparent to visible light, or In this step, a polymer layer having a functional group that loses the interaction is directly chemically bonded to form a polymer layer.
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.

(Surface graft polymerization)
The polymer layer formed in the step (a1-1) 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.
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 a polymer chain having a polar conversion group is directly bonded as a graft chain to a solid surface having an active species. Alternatively, 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 describes a photograft polymerization method and a plasma irradiation graft polymerization method as surface graft polymerization methods. 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.
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.

  When forming a polymer layer in which a polymer chain having a polar conversion group is bonded to a solid surface having an active species via a trunk polymer compound, a trialkoxysilyl group is attached to the end of the trunk polymer compound chain. A reactive functional group such as a group, an isocyanate group, an amino group, a hydroxyl group, or a carboxyl group may be added, and the reactive functional group may be chemically bonded by a coupling reaction between the functional group present on the solid surface and the like. it can.

  More specifically, first, a functional group capable of undergoing a coupling reaction with a functional group present on the solid surface is imparted to the side chain of the backbone polymer, and further, a polymer chain having a polar conversion group is provided as a graft chain. In this method, an incorporated graft polymer is synthesized, and then a polymer layer is formed by a coupling reaction between the graft polymer and a functional group present on a solid surface.

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 convert the polarity of the polymer layer formed on the substrate by the surface graft polymerization described above is light energy such as an IR laser, photothermal conversion is performed to convert the light energy into heat energy. The substance is preferably contained somewhere in the polymer layer, the substrate, and the intermediate layer. Further, a photothermal conversion substance layer may be provided between the intermediate layer and the base material and added thereto.

  As the photothermal conversion material used here, any material that can absorb light such as ultraviolet rays, visible rays, infrared rays, white rays, etc. and convert it into heat can be used, for example, carbon black, carbon graphite, pigment, phthalocyanine series Examples thereof include pigment, 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.

  Further, near infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferably used, and substituted arylbenzo (thio) pyrylium salts described in US Pat. Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A Nos. 58-181051, 58-220143, 59-41363, 59-84248, Pyryllium compounds described in JP-A-59-84249, JP-A-59-146063, JP-A-59-146061, cyanine dyes described in JP-A-59-216146, and U.S. Pat. No. 4,283,475 A pentamethine thiopyrylium salt or the like, or a pyrylium compound disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used.Examples of other preferable dyes include near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993. Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.

  As pigments used, commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Applied Technology” (published by CMC, published in 1986) , “Printing Ink Technology”, published by CMC Publishing, 1984) can be used. Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  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.

〔Base material〕
[Base material surface]
The substrate used in the aspect (1) is a solid surface that is transparent to visible light and has a function of chemically bonding the terminal of a polymer chain having a polar conversion group directly or via a trunk polymer compound As long as it has.
Such a solid surface may be formed of either an inorganic layer or an organic layer as long as it has the above function. Further, in this embodiment, the polarity of the solid surface is not a problem, and may be hydrophilic or hydrophobic.
From these facts, the substrate in the present invention may be formed only from a support having such a solid surface and transparency and shape retention, and an intermediate layer or a polymerization is formed on the support. It may be provided with the above-described solid surface by providing a layer that expresses the initiating ability.
Here, the transparency of the substrate is ideally 100% with respect to visible light, but the transmittance is 80 to 98% even when an intermediate layer or a layer having a polymerization initiating ability is provided. It is preferable that it is the range of these.

[Middle layer]
As the intermediate layer capable of forming the solid surface, when the polymer layer in the embodiment (1) is formed by a photograft polymerization method, a plasma irradiation graft polymerization method, or a radiation irradiation graft polymerization method, particularly an organic layer is used. A layer having a surface is preferable, and an organic polymer layer is particularly preferable.
Such organic polymers include epoxy resins, acrylic resins, urethane resins, phenol resins, styrene resins, vinyl resins, polyester resins, polyamide resins, melamine resins, formalin resins and other synthetic resins, gelatin, casein, and cellulose. Any natural resin such as starch can be used. Among them, in the photograft polymerization method, the plasma irradiation graft polymerization method, the radiation irradiation graft polymerization method and the like, since the start of graft polymerization proceeds from the extraction of hydrogen of the organic polymer, a polymer that can easily extract hydrogen, in particular, an acrylic resin and a urethane resin. The use of styrene resin, vinyl resin, polyester resin, polyamide resin, epoxy resin, etc. is particularly preferable from the viewpoint of production suitability.

[Layer that exhibits polymerization initiation ability]
In the aspect (1), it is preferable from the viewpoint of efficiently generating active sites and improving the sensitivity of surface graft polymerization to use a layer that exhibits polymerization initiation ability by applying energy as the solid surface. .
The layer expressing the polymerization initiating ability (hereinafter, appropriately referred to as a polymerizable layer) preferably comprises a polymerizable compound and a polymerization initiator as a component that expresses the polymerization initiating ability by applying energy. .
The polymerizable layer can be formed by dissolving necessary materials in a solvent in which they can be dissolved and applying the material on a support to form a coating film, followed by heating or irradiation with light.

(A) Polymerizable compound The polymerizable compound used in the polymerizable layer has good adhesion to the support, and the end of the polymer chain having a polar conversion group is directly attached by energy application such as irradiation with actinic rays. Alternatively, there is no particular limitation as long as it can be chemically bonded via a trunk polymer compound, but among them, a hydrophobic polymer having a polymerizable group in the molecule is preferable.
Specific examples of such a hydrophobic polymer include diene homopolymers such as polybutadiene, polyisoprene, and polypentadiene, and allyl groups such as allyl (meth) acrylates and 2-allyloxyethyl methacrylate. Monomer homopolymer;
Furthermore, binary or multicomponent with styrene, (meth) acrylic acid ester, (meth) acrylonitrile, etc. containing diene monomer such as polybutadiene, polyisoprene, polypentadiene or allyl group-containing monomer as a constituent unit. Copolymer;
And linear polymers or three-dimensional polymers having a carbon-carbon double bond in the molecule such as unsaturated polyester, unsaturated polyepoxide, unsaturated polyamide, unsaturated polyacryl, and high-density polyethylene.
In this specification, when referring to both or one of “acrylic and methacrylic”, it may be expressed as “(meth) acrylic”.
The content of the polymerizable compound is preferably in the range of 0 to 100% by mass and particularly preferably in the range of 10 to 80% by mass in terms of solid content in the polymerizable layer.

(B) Polymerization initiator The polymerizable layer preferably contains a polymerization initiator for expressing the polymerization initiating ability by applying energy. The polymerization initiator used here is a known thermal polymerization initiator, photopolymerization initiator, or the like that can exhibit polymerization initiating ability by predetermined energy, for example, irradiation with actinic rays, heating, irradiation with electron beam, etc. Can be selected and used as appropriate. Among these, use of photopolymerization having a higher reaction rate (polymerization rate) than thermal polymerization is preferable from the viewpoint of production suitability, and therefore, a photopolymerization initiator is preferably used.
The photopolymerization initiator that can be used in this embodiment is active with respect to the irradiated active light, and the polymerizable compound contained in the polymerizable layer and the terminal of the polymer chain having a polar conversion group are directly or trunk-high. There is no particular limitation as long as it can be chemically bonded via a molecular compound, and for example, a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and the like can be used.

Specific examples of such a photopolymerization initiator include p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. Acetophenones such as: benzophenone (4,4′-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, ketones; benzoin, benzoin methyl ether, benzoin isopropyl Examples thereof include benzoin ethers such as ether and benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone, and the like.
The content of the polymerization initiator in the polymerizable layer is preferably in the range of 0.1 to 70% by mass and particularly preferably in the range of 1 to 40% by mass in terms of solid content.

The solvent used when applying the polymerizable compound and the polymerization initiator is not particularly limited as long as these components can be 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 in the case of forming the polymerizable layer on the support is from the standpoint of sufficient polymerization initiating ability and maintaining film properties to prevent film peeling, and is 0. 1-20 g / m < ² > is preferable and 1-15 g / m < ² > is more preferable.

As described above, the polymerizable layer-forming composition is disposed on the support by coating or the like, and the solvent is removed to form a polymerizable layer to form a polymerizable layer. Or it is preferable to harden by light irradiation. In particular, after drying by heating and pre-curing by light irradiation, the polymer compound is cured to some extent in advance, so the end of the polymer chain having a polar conversion group is directly or trunk polymer compound This is preferable because it can effectively suppress the situation where the polymerizable layer falls off after being chemically bonded via the. Here, the reason why light irradiation is used for pre-curing is the same as described in the section of the photopolymerization initiator.
The heating temperature and time may be selected under conditions that allow the coating solvent to be sufficiently dried, but from the viewpoint of production suitability, the temperature is 100 ° C. or less, the drying time is preferably within 30 minutes, and the drying temperature is 40 to 80 ° C., It is more preferable to select heating conditions within a drying time of 10 minutes.

  The light irradiation performed as desired after heat drying can be performed using a light source used for pattern formation described later, but is continued, and the polymer chain having an active site and a polarity conversion group of the polymerizable layer that is performed by applying energy. From the viewpoint of not inhibiting the formation of chemical bonds, it is preferable to irradiate with light to such an extent that even if the polymerizable compound present in the polymerizable layer is partially radically polymerized, it is not completely radically polymerized. Although it varies depending on the intensity of the light source, it is generally preferably within 30 minutes. As a standard for such pre-curing, it can be mentioned that the film remaining rate after solvent washing is 10% or more and the initiator remaining rate after pre-curing is 1% or more.

[Support]
As the support used in the electromagnetic wave shielding film material of the present invention, any support 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 resin, polyester resin, or triacetate cellulose ( TAC) film or sheet is preferably used.
In addition, if such a support has a solid surface having a function of chemically bonding the terminal of a polymer chain having a polarity converting group directly or via a trunk polymer compound, the support itself is a group. It may be used as a material.

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%.

<Step (a1-2) in Aspect (1) of the Present Invention>
In the step (a1-2), the polymer layer formed in the step (a1-1) is heated, imparted with acid, or irradiated with radiation such as light, and the polarity is changed to 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.

<Step (a2) in Embodiment (2) of the Present Invention>
In the step (a2), 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 a substrate transparent to visible light, and then radiation is applied. This is a step of forming a patterned region (interactive region) that interacts with the electroless plating catalyst or its precursor by chemically bonding the compound directly to the substrate by irradiating in a pattern.
In the aspect (2), the “compound having a polymerizable group and a functional group that interacts with the electroless plating catalyst or its precursor” is appropriately referred to as an interactive group-containing polymerizable compound.

In this way, by bringing the interactive group-containing polymerizable compound into contact with the substrate and irradiating radiation in a pattern, the polymerizable group of the interactive group-containing polymerizable compound is formed in the pattern. Since a chemical bond is formed between the base material and the base material, a strong and durable interactive region can be formed.
As a method of generating a chemical bond between the polymerizable group of such an interactive group-containing polymerizable compound and the substrate, a surface graft polymerization method can be used. By this surface graft polymerization method, a graft polymer in which the terminal of an interactive group-containing polymerizable compound chain is chemically bonded to a solid surface of a substrate having an active species directly or via a trunk polymer compound is obtained. And can be formed by the graft polymer.
The surface graft polymerization method according to aspect (2) is the same as the surface graft polymerization method described in aspect (1).

  Moreover, as a method of bringing the interactive group-containing polymerizable compound into contact with the substrate, the substrate is immersed in a liquid composition containing the interactive group-containing polymerizable compound. However, from the viewpoint of handleability and production efficiency, as described later, a layer mainly composed of the composition containing the interactive group-containing polymerizable compound is formed on the substrate surface by a coating method. It is preferable.

(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 (a2), when the radiation is irradiated in a pattern, there is no particular limitation on the radiation, and an active site is generated on the solid surface of the base material, so that the polymerizable group of the interactive group-containing polymerizable compound is present. Any one can be used as long as it can impart energy capable of binding to the solid 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 (1) 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 solid surface 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, the graft chain is further bonded to the polymerizable group of the side chain of the graft chain bonded to the substrate. By doing so, a branched graft chain structure is formed, the formation density and mobility of the graft chain are remarkably improved, and higher interaction with the electroless plating catalyst or its precursor is exhibited.

〔Base material〕
The substrate used in the embodiment (2) is transparent to visible light, and the terminal or side chain of the aforementioned interactive group-containing polymerizable compound is chemically bonded directly or via a trunk polymer compound. It has such a solid surface as possible. As such a base material, the base material described in the embodiment (1) can be used.

<Step (a3-1) in Aspect (3) of the Present Invention>
The step (a3-1) is a step of providing a photosensitive layer containing a photothermal conversion substance and a binder on a substrate transparent to visible light.

[Photosensitive layer (photosensitive layer)]
The photosensitive layer in the aspect (3) has a function of causing ablation, and in the step (a3-2), the polymer layer is formed by surface graft polymerization. From the viewpoints of efficiently generating and improving the sensitivity of surface graft polymerization, it is preferable to have a function similar to that of a layer provided on the support and exhibiting the ability to initiate polymerization.
Therefore, in this embodiment, a polymerizable compound and a polymerization initiator are added as compounds that exhibit polymerization initiating ability by applying energy to the photosensitive layer, and the photosensitive layer exhibits polymerization initiating ability. It is preferable to form it as a layer from the viewpoint of efficiently generating active sites on the surface of the photosensitive layer and improving the sensitivity.

In order to form the photosensitive layer, necessary components may be dissolved in a solvent capable of dissolving them, provided on a substrate by a method such as coating, and hardened by heating or light irradiation.
The components that can be contained in the photosensitive layer are described below.
Such a photosensitive layer needs to contain a photothermal conversion substance and a binder, which will be described later, and contains a polymerizable compound and a polymerization initiator in order to provide the same function as a layer that exhibits polymerization initiation ability. It is preferable that other additives may be contained as required.

(binder)
The binder used in the photosensitive layer is used for the purpose of enhancing the coating properties, film strength, and ablation effect, and is compatible with the photothermal conversion substance or dispersibility of the photothermal conversion substance. It is selected appropriately.
Examples of the binder include unsaturated acids such as (meth) acrylic acid and itaconic acid, alkyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, styrene, α-methylstyrene, and the like. Copolymer of alkyl methacrylate and alkyl acrylate represented by polymethyl methacrylate; Copolymer of alkyl (meth) acrylate and acrylonitrile, vinyl chloride, vinylidene chloride, styrene, etc .; Acrylonitrile and chloride Copolymer with vinyl or vinylidene chloride; modified cellulose having a carboxyl group in the side chain; polyethylene oxide; polyvinyl pyrrolidone; phenol, o-, m-, p-cresol, and / or xylenol with aldehyde, acetone, etc. Novolac resin obtained by condensation reaction; Epi Polyol of borohydrin and bisphenol A; soluble nylon; polyvinylidene chloride; chlorinated polyolefin; copolymer of vinyl chloride and vinyl acetate; polymer of vinyl acetate; copolymer of acrylonitrile and styrene; Copolymer with styrene; polyvinyl alkyl ether; polyvinyl alkyl ketone; polystyrene; polyurethane; polyethylene terephthalate isophthalate; acetyl cellulose; acetyl propoxy cellulose; acetyl butoxy cellulose; nitrocellulose; celluloid; polyvinyl butyral; Formalin resin or the like is used.
In this specification, when referring to both or one of “acrylic and methacrylic”, it may be expressed as “(meth) acrylic”.

  The content of the binder in the photosensitive layer is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and still more preferably 20 to 80% by mass in the total solid content of the photosensitive layer.

(Polymerizable compound)
As the polymerizable compound used in combination with the binder, an adhesive group-containing polymerizable compound, which will be described later, can be added by providing energy such as irradiation with actinic rays with good adhesion to the substrate. Although there will be no restriction | limiting in particular if it is a thing, Among these, the hydrophobic polymer which has a polymeric group in a molecule | numerator is preferable.
As said polymeric compound, the said binder may serve as this, The compound different from the said binder may be sufficient.
Specifically, diene homopolymers such as polybutadiene, polyisoprene, and polypentadiene, and homopolymers of allyl group-containing monomers such as allyl (meth) acrylates and 2-allyloxyethyl methacrylate relays;
Furthermore, binary or multicomponent with styrene, (meth) acrylic acid ester, (meth) acrylonitrile, etc. containing diene monomer such as polybutadiene, polyisoprene, polypentadiene or allyl group-containing monomer as a constituent unit. Copolymer;
Preferred examples include linear polymers or three-dimensional polymers having a carbon-carbon double bond in the molecule such as unsaturated polyester, unsaturated polyepoxide, unsaturated polyamide, unsaturated polyacryl, and high density polyethylene. .

  The content of the polymerizable compound in the photosensitive layer is preferably in the range of 5 to 95% by mass and particularly preferably in the range of 20 to 80% by mass in the total solid content of the photosensitive layer.

(Polymerization initiator)
As the polymerization initiator, the polymerization initiator used in the layer having the polymerization initiating ability of the previous aspect (1) can be used as it is.
The content of the polymerization initiator is preferably in the range of 0.1 to 70% by mass, particularly preferably in the range of 1 to 40% by mass in terms of solid content in the photosensitive layer.

(Photothermal conversion material)
As the photothermal conversion substance used for the photosensitive layer, any substance can be used as long as it can absorb light such as ultraviolet rays, visible rays, infrared rays, white rays, etc., and convert it into heat. Dyes, pigments and metal fine particles similar to the photothermal conversion substances described in (1) can be used.

The dye or pigment to be used is 0.01 to 50% by mass, preferably 0.1 to 10% by mass, and particularly preferably 0 in the case of a dye, from the viewpoint of sensitivity and film strength of the photosensitive layer. In the case of a pigment, it is particularly preferably used in a proportion of 3.1 to 10% by mass.
Further, the metal fine particles used are 0.01 to 50% by mass, preferably 0.1 to 30% by mass, and particularly preferably 0.1% by mass, based on the total solids of the photosensitive layer, from the viewpoint of sensitivity and film strength of the photosensitive layer. It can be used at a ratio of -10% by mass.

(Other additives)
The photosensitive layer is preferably further contained in nitrocellulose for the purpose of improving the ablation effect. Nitrocellulose is decomposed by heat generated by absorption of near-infrared laser light by a light absorber, and efficiently generates low-molecular gas to promote removal of the photosensitive layer.

[Formation of photosensitive layer]
The photosensitive layer can be provided by dissolving the above components in a suitable solvent and applying the solution on a substrate. In addition, the solvent used when apply | coating a photosensitive layer will not be restrict | limited especially if said each components, such as a photothermal conversion substance and a binder, melt | dissolve. 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.
The coating amount when the photosensitive layer is formed on the substrate is preferably 0.05 to 10 g / m ^{2 and} more preferably 0.3 to 5 g / m ² in terms of mass after drying.

The photosensitive layer is formed by applying the composition for forming the photosensitive layer on the surface of the base material by coating or the like, and forming a film by removing the solvent. At this time, heating and / or light irradiation is performed. It is preferable to harden. In particular, if the film is dried by heating and then preliminarily cured by light irradiation, the polymerizable compound is cured to some extent in advance, so in the next step (a3-2), the polymer layer is formed on the photosensitive layer. After the formation of, it is preferable because the situation where the photosensitive layer is dropped off can be effectively suppressed. Here, the reason why light irradiation is used for preliminary curing is the same as described in the section of the photopolymerization initiator in the aspect (1).
The heating temperature and time may be selected under conditions that allow the coating solvent to be sufficiently dried, but from the viewpoint of production suitability, the temperature is 100 ° C. or less, the drying time is preferably within 30 minutes, and the drying temperature is 40 to 80 ° C., It is more preferable to select heating conditions within a drying time of 10 minutes.

  Light irradiation performed as desired after heat drying can use a light source used for pattern formation described later. From the viewpoint that the light irradiation does not hinder the formation of a chemical bond between the active site of the polymerizable layer, which is carried out by applying energy, and the polymerizable group-containing polymerizable compound, the polymerization is present in the photosensitive layer. Even if the functional compound is partially radically polymerized, it is preferable that the compound is not completely radically polymerized. The light irradiation time varies depending on the intensity of the light source, but generally it is preferably within 30 minutes. As a standard for such pre-curing, it can be mentioned that the film remaining rate after solvent washing is 10% or more and the initiator remaining rate after pre-curing is 1% or more.

<Step (a3-2) in Embodiment (3) of the Present Invention>
The step (a3-2) 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 photosensitive 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 a method for forming the polymer layer in the aspect (3), a surface graft polymerization method can be used. By this surface graft polymerization method, a graft polymer in which the end of the polymer chain having an interactive group is chemically bonded to the surface of the photosensitive layer having active species directly or via a trunk polymer compound is generated. And an interactive region can be formed by the graft polymer.
The surface graft polymerization method according to aspect (3) is the same as the surface graft polymerization method described in aspect (1).

  The molecular weight of the polymer chain constituting such a polymer layer is in the range of Mw500 to 5,000,000, the preferable molecular weight is in the range of Mw1000 to 1,000,000, and more preferably in the range of Mw2000 to 1,000,000.

  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 (2).

[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 (2) 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 (a3-3) in Aspect (3) of the Present Invention>
Step (a3-3) is a step of irradiating the polymer layer with radiation to form a pattern, removing the photosensitive layer by ablation, and forming a pattern-like region that interacts with the electroless plating catalyst or its precursor. is there.

  In this step (a3-3), the irradiated radiation such as laser light causes the photosensitive layer to be ablated (melted, decomposed, volatilized, burned, etc.), thereby removing the photosensitive layer. The polymer layer provided on the layer is removed, resulting in the formation of a patterned interactive region.

[Radiation pattern irradiation]
Examples of the radiation pattern irradiation in this embodiment include a method of writing by radiation irradiation such as heating and exposure. For example, light irradiation with an infrared laser, an ultraviolet lamp, visible light, etc., electron beam irradiation such as γ rays, and thermal writing with a thermal head are 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. In addition, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also 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 order to perform direct pattern formation using digital data of a computer, a method of causing ablation 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. In particular, exposure with a solid-state high-power infrared laser such as a semiconductor laser or a YAG laser that emits infrared light having a wavelength of 700 to 1200 nm is preferable.

〔Base material〕
The substrate used in the embodiment (3) is different from the previous embodiments (1) and (2), and it is not necessary to have a specific solid surface due to the presence of the photosensitive layer, and is transparent to visible light and maintains its shape. If it has the property, it can be used without limitation. Specifically, the thing similar to what was mentioned as a support body in aspect (1) can be mentioned.

  As mentioned above, although the formation process of the interactive area | region in aspect (1)-(3) has been described, as for this interactive area | region, the terminal of a polymer has couple | bonded with the base material and the photosensitive layer, and interaction is carried out. 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.

<Step (b) in the Present Invention>
The step (b) in the present invention is a patterned region (interactive region) that interacts with the electroless plating catalyst or its precursor formed by the method of any one of the above aspects (1) to (3). ), An electroless plating catalyst or a precursor thereof.

[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.

<Step (c) in the Present Invention>
In this step, a metal pattern is formed by performing electroless plating on the substrate obtained by the step (b) 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 substrate obtained by the step (b) and provided with the electroless plating catalyst 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.

<Step (d) in the Present Invention>
In the method for producing an electromagnetic wave shielding material of the present invention, (d) a step of performing electroplating (electroplating step) can be performed after the step (c). In this step, after the electroless plating in the step (c), 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 permeability, the aperture ratio needs to be 50% or more, more preferably 60% or more, and a quadrangle is preferred 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.

<Electromagnetic wave shielding material>
The electromagnetic wave shielding material of the present invention is formed by a polymer having a functional group that interacts with an electroless plating catalyst or a precursor thereof formed on a transparent substrate with respect to visible light, directly bonded to the substrate in a pattern. It has a metal pattern formed by applying an electroless plating catalyst or a precursor thereof to the region formed and then performing electroless plating.

As described above, according to the method for producing an electromagnetic wave shielding material and the electromagnetic wave shielding material of the present invention, a region (interactive region) made of a polymer having a functional group that interacts with an electroless plating catalyst or a precursor thereof is selectively used. Electroless plating or its precursor is applied to the substrate, followed by electroless plating, so that it is easy to obtain a finer and more precise metal pattern than conventional electromagnetic shielding materials. Can do.
Thereby, the obtained electromagnetic shielding material can have both high electromagnetic shielding properties and high transparency.

In addition, since the interaction region interacts with the electroless plating catalyst or its precursor, and the electroless plating is performed on the catalyst or its precursor, the obtained metal pattern has an adhesive property with the substrate. Will be excellent. In particular, when the interactive region is formed by the method of the above-described embodiments (1) to (3), since the region is made of a graft polymer, the graft polymer and the formed metal film (electromagnetic wave shielding film) ), A hybrid state is formed at the base material interface of the metal 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.

  Furthermore, when the interactive region is made of a graft polymer, plating partially proceeds in the internal graft chain, so that 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 in 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 examining the best angle in the electromagnetic wave shielding material in the present invention, it was found that about 30 degrees is good when the mesh is orthogonal (90 degrees crossing).
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.
[Example 1]
(Preparation of base material)
Using a PET film (product name: M4100, manufactured by Toyobo Co., Ltd.) as a support, an intermediate layer coating solution having the following composition was coated on the surface using a rod 10 coating bar and dried at 100 ° C. for 1 minute. Then, an intermediate layer containing an infrared absorber having a film thickness of 1.6 μm was formed, and a base material used in Example 1 was produced.

<Intermediate layer coating solution>
・ Epoxy resin 2g
(Epicoat, Yuka-shell Co, Ltd.)
・ Infrared absorber (IR125 Wako Pure Chemicals) 0.2g
・ 9g 1-methoxy-2-propanol
・ Methyl ethyl ketone 9g

(Step (a1-1) in Embodiment (1) of the Present Invention)
The surface of the substrate was subjected to plasma treatment under the following conditions, and a polymer layer was formed by surface graft polymerization.
After treatment for 10 seconds in an argon gas atmosphere of 5.33 Pa (0.04 torr) using a Shimadzu LCVD-01 type plasma treatment apparatus, the peroxide group was introduced to the surface of the intermediate layer. By immersing the substrate A thus plasma-treated in 10 wt% α (styrene-4-sulfonyl) acetic acid sodium salt aqueous solution, bubbling argon gas for 15 minutes, and then heating to 60 ° C. for 7 hours. Surface graft polymerization was performed.
After the graft polymerization, the base material was immersed in 3000 ml of ion-exchanged water to remove a homopolymer other than the graft polymer, thereby obtaining a polymer layer.

(Step (a1-2) in Embodiment (1) 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 (b) and (c) 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]
(Preparation of base material)
Using the PET film used in Example 1 as a support, an intermediate layer coating solution having the following composition was applied to the surface using a rod bar No. 18, dried at 80 ° C. for 2 minutes, and an intermediate layer having a thickness of 6 μm was formed. Formed.
Then, a 400 W high-pressure mercury lamp (model number: UVL-400P, manufactured by Riko Kagaku Sangyo Co., Ltd.) is used for the support provided with the intermediate layer, and is irradiated with light for 10 minutes, preliminarily cured, and used in Example 2. A substrate was prepared.

<Intermediate layer coating solution>
・ Allyl methacrylate / methacrylic acid copolymer 2g
(Copolymerization molar ratio 80/20, average molecular weight 100,000)
・ Ethylene oxide modified bisphenol A diacrylate 4g
(IR125 Wako Pure Chemicals)
・ 1.6g of 1-hydroxycyclohexyl phenyl ketone
・ 16 g of 1-methoxy-2-propanol

(Step (a1-1) in Embodiment (1) of the Present Invention)
The pre-cured substrate was 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 was used under an argon atmosphere. Light irradiation 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 (a1-2) in Embodiment (1) 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 (b) and (c) 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 (a2) in the embodiment (2) of the present invention)
Acrylic acid was applied to the surface of the same substrate as in Example 2 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 (b) and (c) 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 (a2) in the embodiment (2) of the present invention)
A polymer coating solution having the following composition was applied to the same substrate as in Example 2 using rod bar # 18. The film thickness of the obtained film was 0.8 μm.

<Polymer coating solution>
・ Hydrophilic polymer (The synthesis method is shown below) 0.25g
・ Water 5g
・ Acetonitrile 3g

<Method for synthesizing the hydrophilic polymer>
18 g of polyacrylic acid (average molecular weight 25,000) was dissolved in 300 g of DMAc, 0.41 g of hydroquinone, 19.4 g of 2-methacryloyloxyethyl isocyanate and 0.25 g of dibutyltin dilaurate were added and reacted at 65 ° C. for 4 hours. . The acid value of the obtained polymer was 7.02 meq / g. The carboxyl group was neutralized with a 1N (mol / l) sodium hydroxide aqueous solution, the polymer was precipitated in addition to ethyl acetate, and washed well to obtain a hydrophilic polymer.

  The obtained film was subjected to pattern exposure for 1 minute using a 400 W high-pressure mercury lamp using a mask pattern. Thereafter, the obtained film was washed with water to form an interactive region formed by bonding a hydrophilic polymer to the exposed portion.

(Steps (b) and (c) 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 (d) 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 (a3-1) in Embodiment (3) of the Present Invention)
The same PET as in Example 1 was used as a base material, and a photopolymerizable composition having the following composition was applied onto the base material using a coating bar of No. 17 rod and dried at 80 ° C. for 2 minutes. Next, a 400 W high-pressure mercury lamp (UVL-400P, manufactured by Riken Sangyo Co., Ltd.) was used for the film on which the coating layer was formed, and UV light was irradiated for 10 minutes from above to pre-cure, thereby forming a photosensitive layer. .

<Photopolymerizable composition>
・ Allyl methacrylate / methacrylic acid copolymer 4g
(Molar ratio 80/20, molecular weight 100,000)
・ Ethylene oxide modified bisphenol A diacrylate 4g
(M210, manufactured by Toagosei Co., Ltd.)
・ 1.6g of 1-hydroxycyclohexyl phenyl ketone
・ 16 g of 1-methoxy-2-propanol
・ Carbon black (MA100, manufactured by Mitsubishi Chemical Corporation) 2g

(Step (a3-2) in aspect (3) of the present invention)
Next, an aqueous solution (30 wt%) of sodium sulfonate was applied to the surface of the photosensitive layer using a rod bar # 12, and the coated surface was laminated with a 25 μm PET film without drying. Then, UV light was irradiated from above (400 W high pressure mercury lamp irradiation time 1 minute). After light irradiation, the laminate film was removed and washed with water to obtain a polymer layer grafted with sodium sulfonate.

(Step (a3-3) in aspect (3) of the present invention)
The obtained base material having a 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 photosensitive layer that absorbed the laser beam caused ablation and was removed together with the polymer layer to form an interactive region.

(Steps (b) and (c) 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 (a1-1) in Embodiment (1) of the Present Invention)
The same substrate as in Example 2 was immersed in a t-butyl acrylate solution (30% by mass, solvent: propylene glycol monomethyl ether (MFG)), and exposed for 30 minutes using a 400 W high-pressure mercury lamp in an argon atmosphere.
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 (a1-2) in Embodiment (1) 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 400 W 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 (b) and (c) 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 an ethanol solution of silver perchlorate (5 mmol / l) and add 30 ml of sodium borohydride solution (0.4 mol / l) with vigorous stirring. The ions were slowly dropped to reduce ions, and a dispersion of Ag particles (silver particles) coated with quaternary ammonium was obtained.

[Example 8]
(Step (a2) in the embodiment (2) of the present invention)
The coating liquid which consists of the following composition was apply | coated to the same base material as Example 2 using rod bar # 18. The film thickness of the obtained film was 0.8 μm.
<Composition formation of 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>
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 1 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 dropping, 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 3 minutes using a 400 W 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 (b) and (c) of the present invention)
The obtained base material having an 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 at 50 ° C. for 20 minutes in the same electroless plating bath at 40 ° C. as in Example 1 to form a metal pattern.

[Evaluation]
(Metallic pattern shape evaluation)
Using the optical microscope (made by Nikon, OPTI PHOTO-2), the metal pattern in the electromagnetic wave shielding material obtained in Examples 1 to 8, 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 is as follows. The measurement results are shown in Table 1 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 1-8. The measurement results are shown in Table 1 below.

(Evaluation of adhesion)
The electromagnetic wave shielding materials obtained in Examples 1 to 8 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, ◯ means that when the tape peeling test was performed once on the cut grid, none of the first peeling was observed. The measurement results are shown in Table 1 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 8 was measured using Lorester EP (manufactured by Mitsubishi Chemical). The measurement results are shown in Table 1 below.

According to the results of Table 1 above, it was found that in the electromagnetic wave shielding material obtained by the example of the present invention, a thin wire having a width of 30 μm or less, which was difficult in the prior art, was formed. . In addition, it was confirmed that these thin line | wire widths can be controlled by said aspect (1)-(3) 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.
Further, the electromagnetic wave shielding materials obtained by the examples of the present invention are all excellent in electric field shielding effect and magnetic field shielding effect, and further excellent in transparency and adhesion between the substrate and the metal pattern. found.

Claims (6)

(A) 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 a substrate transparent to visible light;
(B) applying an electroless plating catalyst or a precursor thereof to the region;
(C) performing electroless plating to form a metal pattern;
The manufacturing method of the electromagnetic wave shielding material which has these. (A1-1) 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 a substrate transparent to visible light, or the mutual Direct chemical bonding of a polymer having a functional group that loses its action to form a polymer layer;
(A1-2) applying heat, acid, or radiation to the polymer layer in a pattern to form a patterned region that interacts with the electroless plating catalyst or its precursor;
(B) applying an electroless plating catalyst or a precursor thereof to the region;
(C) performing electroless plating to form a metal pattern;
The manufacturing method of the electromagnetic wave shielding material which has these. (A2) After contacting a compound having a polymerizable group and a functional group that interacts with an electroless plating catalyst or a precursor thereof on a substrate transparent to visible light, the radiation is patterned. Irradiating and chemically bonding the compound directly to the substrate to form a patterned region that interacts with the electroless plating catalyst or precursor thereof;
(B) applying an electroless plating catalyst or a precursor thereof to the region;
(C) performing electroless plating to form a metal pattern;
The manufacturing method of the electromagnetic wave shielding material which has these. (A3-1) providing a photosensitive layer containing a photothermal conversion substance and a binder on a substrate transparent to visible light;
(A3-2) 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 photosensitive layer;
(A3-3) irradiating the polymer layer with a pattern of radiation, removing the photosensitive layer by ablation, and forming a patterned region that interacts with the electroless plating catalyst or its precursor;
(B) applying an electroless plating catalyst or a precursor thereof to the region;
(C) 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 wave shielding material according to any one of claims 1 to 4, further comprising a step (d) of performing electroplating after the step (c).   Electrolessly formed in a pattern where a polymer having a functional group that interacts with the electroless plating catalyst or its precursor formed on a transparent substrate with respect to visible light is directly bonded to the substrate in a pattern. An electromagnetic wave shielding material having a metal pattern formed by electroless plating after applying a plating catalyst or a precursor thereof.