JP2012186222A - Molding electromagnetic wave shield sheet and electromagnetic wave shield molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding electromagnetic wave shield sheet which is light-weight and superior in processability and which can maintain the electromagnetic wave shielding performance superior even after processing.SOLUTION: The molding electromagnetic wave shield sheet comprises at least a resin layer (A), a metal layer (B) and a conductive polymer layer (C) containing a conductive polymer having conductivity of 0.05 S/cm or more, includes the metal layer (B) on at least one surface of the resin layer (A) and also includes the conductive polymer layer (C) on at least one surface of a laminate having the resin layer (A) and the metal layer (B).

Description

The present invention relates to an electromagnetic wave shielding sheet for molding and an electromagnetic wave shield molding.

In recent years, various troubles due to electromagnetic waves have been regarded as problems, such as electromagnetic waves emitted from electronic devices and the like affecting other electronic devices and causing malfunctions. Therefore, there is an increasing demand for shielding electromagnetic waves emitted from electronic devices and the like.

Conventionally, it is well known that metal has electromagnetic wave shielding performance, and a metal plate is used as an electromagnetic wave shielding member. An electromagnetic wave shielding member made of a metal plate is an electromagnetic wave shielding member excellent in electromagnetic wave shielding performance.
However, the electromagnetic wave shielding member made of a metal plate is inferior in handleability because of its heavy weight, and in addition, it has been difficult to cope with the recent weight reduction of electronic devices. Moreover, since the metal plate is inferior in workability (moldability) as compared with the resin film, there is a problem that the degree of freedom in design as an electromagnetic wave shielding member is low.

In addition, an electromagnetic wave shielding member in which a conductive polymer electrolytically polymerized by polymerization in a thermoplastic polymer film is dispersed, a composite film in which a polymer film is laminated on at least one surface of a gas-liquid interface polymerized conductive polymer film, An electromagnetic wave shield molded product formed by integrally molding a plastic polymer or a thermosetting polymer has also been proposed (see, for example, Patent Documents 1 and 2).
Since these electromagnetic wave shielding members are made of a polymer, they are lightweight and have excellent workability (moldability). However, the electromagnetic wave shielding performance of the conductive polymer is lower than that of metal, and with such an electromagnetic wave shielding member, sufficient electromagnetic wave shielding performance could not be obtained.

Patent Document 3 discloses a transparent substrate film, a coating layer formed in a pattern containing conductive polymer fine particles and a binder on the surface of the substrate, and an electroless plating method on the coating layer. The binder is present in an amount of 0.1 to 10 parts by mass with respect to 1 part by mass of the conductive polymer fine particles, and the thickness of the coating layer is 20 to 500 nm. A transparent electromagnetic wave shielding film having a metal plating film thickness of 100 to 3000 nm is disclosed.
Since this electromagnetic wave shielding film includes a metal plating film, the conductive polymer fine particles of 0.01 S / cm or less have excellent electromagnetic wave shielding performance compared to the case where the conductive polymer bears the electromagnetic wave shielding performance. The coating layer containing conductive polymer fine particles itself does not have electromagnetic wave shielding ability because the coating layer is formed using, and when this electromagnetic shielding film is processed, the metal plating film may be disconnected. In some cases, cracks may occur. In this case, there is a problem that the electromagnetic wave shielding performance of the molded product is remarkably deteriorated.

JP-A-60-228544 JP-A-11-97886 JP 2009-16696 A

The object of the present invention is to provide an electromagnetic shielding sheet for molding that is lightweight, excellent in workability, and capable of maintaining excellent electromagnetic shielding performance even after processing, and is lightweight and excellent in handleability. An object of the present invention is to provide an electromagnetic wave shielding molded product that can take any shape while maintaining excellent electromagnetic wave shielding performance.

As a result of intensive studies to solve the above problems, the present inventors have found that an electromagnetic wave shielding sheet in which a conductive polymer layer is formed on at least one surface of a laminate including a metal layer on at least one surface of a resin layer is lightweight and processed. The electromagnetic wave shielding sheet for molding according to the present invention was completed by finding that the electromagnetic wave shielding performance was excellent even after processing.
In addition, an electromagnetic wave shield molded body made of a member having a conductive polymer layer on at least one side of a laminate having a metal layer on at least one side of the resin layer is lightweight, excellent in handleability, and having a more complicated shape. Even if it exists, it discovered that it had the outstanding electromagnetic wave shielding performance, and completed the electromagnetic wave shielding molded object of this invention.

That is, the electromagnetic wave shielding sheet for molding of the present invention comprises at least a resin layer (A), a metal layer (B), and a conductive polymer layer (C) containing a conductive polymer having a conductivity of 0.05 S / cm or more. )
A metal layer (B) is provided on at least one side of the resin layer (A), and
The conductive polymer layer (C) is provided on at least one surface of a laminate having the resin layer (A) and the metal layer (B).

In the electromagnetic wave shielding sheet for molding, the metal layer (B) is preferably made of a conductive metal or metal oxide, or a magnetic material.
Moreover, it is preferable that the said metal layer (B) is a layer formed by vapor deposition, and thickness is 0.01-10.0 micrometers.

In the electromagnetic wave shielding sheet for molding, the conductive polymer is preferably composed of a composite of poly (3,4-disubstituted thiophene) and polyanion.

In the electromagnetic wave shielding sheet for molding, the conductive polymer layer (C) preferably contains a binder, and at least one of the binders is an acrylic resin.
Moreover, the said conductive polymer layer (C) contains a conductive polymer and a conductive improvement agent, and the compounding quantity of the said conductive improvement agent is 10 to 10 weight part of solid content of the said conductive polymer. A layer formed using a conductive polymer composition of 1500 parts by weight is preferable.

The electromagnetic wave shield molding of the present invention comprises at least a resin layer (A), a metal layer (B), and a conductive polymer layer (C) containing a conductive polymer having a conductivity of 0.05 S / cm or more. ,
A metal layer (B) is provided on at least one side of the resin layer (A), and
The conductive polymer layer (C) is provided on at least one surface of a laminate having the resin layer (A) and the metal layer (B).

The electromagnetic shielding molded body is preferably formed by molding the electromagnetic shielding sheet for molding according to the present invention, and is a molding obtained by molding a laminated sheet comprising at least a resin layer (A) and a metal layer (B). It is also preferable that the conductive polymer layer (C) is formed on the surface of the body.
Moreover, the said electromagnetic wave shield molded object has a preferable thing used as an electromagnetic wave shield of an electronic device.

Since the electromagnetic wave shielding sheet for molding of the present invention has the above-described configuration, it is lightweight, excellent in workability, and can maintain excellent electromagnetic wave shielding performance even after processing, so as an electromagnetic wave shielding sheet for molding Very good.
Here, the point which can maintain the excellent electromagnetic wave shielding performance after processing will be described in a little more detail.
When using the laminated body which formed the metal layer on the single side | surface or both surfaces of the resin film as an electromagnetic wave shield sheet, it is possible to ensure sufficient electromagnetic wave shielding performance resulting from having the metal layer.
However, if this electromagnetic shielding sheet is molded (processed) and attempted to be used, the metal layer of the electromagnetic shielding sheet is broken (cracked) at the time of molding (processing). Shielding may not be possible, and electromagnetic wave shielding performance may be significantly reduced.
On the other hand, the electromagnetic wave shielding sheet for molding of the present invention further comprises a conductive polymer layer on one side or both sides of the laminate, and this conductive polymer layer is superior in workability compared to a metal layer, Even if the metal layer is processed under conditions such as disconnection, the conductive polymer layer is not damaged, so even if the metal layer is disconnected, the electromagnetic wave shielding performance of the portion can be supplemented by the conductive polymer layer, As a result, the electromagnetic wave shielding sheet for molding of the present invention can maintain excellent electromagnetic wave shielding performance even after processing.

Moreover, since the electromagnetic wave shielding molded body of the present invention has the above-described configuration, it is lightweight, excellent in handleability, and can take any shape while maintaining excellent electromagnetic wave shielding performance.

It is sectional drawing which shows an example of the shield sheet of this invention typically. It is sectional drawing which shows typically another example of the shield sheet of this invention. (A) is a perspective view which shows typically an example of the electromagnetic wave shield molding of this invention, (b) is sectional drawing which shows typically the AA line cross section of (a). It is a perspective view which shows typically another example of the electromagnetic wave shield molding of this invention. It is a perspective view which shows typically another example of the electromagnetic wave shield molding of this invention.

First, the electromagnetic wave shielding sheet for molding of the present invention will be described with reference to the drawings.
The electromagnetic wave shielding sheet for molding of the present invention (hereinafter also simply referred to as a shielding sheet) contains at least a resin layer (A), a metal layer (B), and a conductive polymer having a conductivity of 0.05 S / cm or more. A conductive polymer layer (C)
A metal layer (B) is provided on at least one side of the resin layer (A), and
The conductive polymer layer (C) is provided on at least one surface of a laminate having the resin layer (A) and the metal layer (B).

1 and 2 are cross-sectional views schematically showing examples of the shield sheet of the present invention.
As shown in FIG. 1, the shield sheet 10 has a laminated body 13 in which a metal layer 12 is formed on one surface of a resin layer 11, and is electrically conductive on the surface of the resin layer 11 opposite to the side where the metal layer 12 is formed. The conductive polymer layer 14 is formed.

Further, the layer configuration of the shield sheet is not necessarily provided with the layer configuration shown in FIG. 1, and may have a layer configuration like the shield sheet 20 shown in FIG. 2, for example.
The shield sheet 20 is a laminate 23 in which a metal layer 22 is formed on one surface of a resin layer 21, and a conductive polymer layer 24 is further formed on the surface of the resin layer 21 on which the metal layer 22 is formed. It is.

Moreover, although the layer structure of the said shield sheet is not shown in figure, you may provide the following structures, for example.
That is, the metal layer may be formed on both sides of the resin layer to form a laminate, and the conductive polymer layer may be formed on both sides or one side of the laminate.
When the metal layers are formed on both surfaces of the resin layer (when the shield sheet includes two metal layers), the electromagnetic shielding performance of the shield sheet is further improved.

Further, another layer may be formed between the resin layer, the metal layer, and the conductive polymer layer, or on the outermost layer of the shield sheet.
Specifically, for example, a primer layer for improving the adhesion of each layer, a printed layer for imparting a lot number or a pattern to the shield sheet, and the like may be formed.

Further, the metal layer may be a solid layer formed on the entire surface of the resin layer, or may be a pattern layer formed only on a desired part of the one surface of the resin layer.
Similarly, the conductive polymer layer may be a solid layer formed on the entire surface of the resin layer or the metal layer, or only on a desired part of the surface of the resin layer or the metal layer. It may be a formed pattern layer.

Next, the structural member of the shield sheet of this invention is demonstrated.
(Resin layer (A))
The resin layer is a layer that becomes a base layer of the shield sheet.
The material of the resin layer is not particularly limited. For example, polyethylene terephthalate such as amorphous polyethylene terephthalate (A-PET), crystalline polyethylene terephthalate (C-PET), polyimide, polyethersulfone, polyetheretherketone, Polycarbonate, polyethylene, polypropylene, polyamide, acrylamide, cellulose propionate, polyvinyl chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, acrylonitrile butadiene styrene resin, acrylonitrile styrene copolymer resin, acrylic resin, polyamide, polyacetal, modified polyphenylene Ether, polybutylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone Acrylate polymer, polyimide, polyamide-imide, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ionomer copolymers, other acrylic resins, acrylonitrile butadiene styrene.
Among these, thermoplastic resins such as A-PET, C-PET, polypropylene, polystyrene, polyvinyl acetate, polycarbonate, modified polyphenylene ether, and amorphous polyarylate are preferable because of excellent molding processability. A-PET Is more preferable.

(Metal layer (B))
The metal layer is a layer mainly responsible for the function of shielding electromagnetic waves in the shield sheet.
Examples of the material of the metal layer include conductive metals and metal oxides, and magnetic materials. These may be used alone or in combination of two or more. In the present invention, the magnetic substance means a ferromagnetic substance.

Examples of the metal include conductive metals such as aluminum, copper, magnesium, calcium, zinc, silver, cadmium, and gold.
Of these, aluminum, copper, silver, and gold are preferable. The reason is that it has a high electromagnetic shielding effect because of its relatively high conductivity.

The metal oxide, _{e.g., TiO 2, ZnO, StTiO 3} , ITO, FTO, ATO, GZO , and the like.
Of these, ITO is preferred. The reason is that it has a high electromagnetic shielding effect because of its relatively high conductivity.

Examples of the magnetic material include iron oxide, chromium oxide, cobalt, and ferrite.

Although the thickness of the said metal layer is not specifically limited, 0.01-10 micrometers is preferable.
If it is less than 0.01 μm, it is difficult to develop a sufficient electromagnetic wave shield, and if it exceeds 10 μm, there may be a problem that molding processability is deteriorated and disadvantageous in terms of weight reduction.

The metal layer can be formed using, for example, vapor deposition such as PVD or CVD, sputtering, electroless plating, ion plating, or the like. For example, depending on the thickness of the metal layer, a relatively thick metal layer may be formed by performing electroplating after forming a thin metal layer by the above-described method.

(Conductive polymer layer (C))
The said conductive polymer layer is a layer which bears the function which supplements the shielding property of the electromagnetic waves by the said metal layer in the said shield sheet, and is a layer containing a conductive polymer.
Examples of the conductive polymer include polyphenylacetylene, poly (p-phenylene), poly (m-phenylene), polythiophene, polypyrrole, polyaniline, polyazobenzene, polyacetylene, polyacene, polyphenanthrene, polyphenylene vinylene, polynaphthalene, poly (vinylene). Sulfide), derivatives thereof, and complexes of these with dopants such as polyanions.
Among these, polythiophene (derivative) is preferable, and a complex of poly (3,4-disubstituted thiophene) and polyanion is more preferable. This is because it is extremely excellent in chemical stability in addition to conductivity and transparency. Furthermore, when a conductive polymer layer is formed using a conductive polymer composition containing a complex of poly (3,4-disubstituted thiophene) and a polyanion, a thin film can be formed at a low temperature in a short time. Therefore, it will be extremely excellent in productivity.

The complex of the poly (3,4-disubstituted thiophene) and the polyanion includes poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) and the polyanion. A composite is particularly preferred.
As the poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene), the following formula (I):

A polythiophene in a cationic form consisting of repeating structural units represented by Here, R ¹ and R ² each independently represent a hydrogen atom or a C _1-4 alkyl group, or a C _1-4 alkylene group which may be substituted together.
Examples of the C _1-4 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.
Examples of the optionally substituted C _1-4 alkylene group formed by combining R ¹ and R ² include a methylene group, a 1,2-ethylene group, and a 1,3-propylene group. 1,4-butylene group, 1-methyl-1,2-ethylene group, 1-ethyl-1,2-ethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene Groups and the like. Preferred are a methylene group, 1,2-ethylene group, and 1,3-propylene group, and a 1,2-ethylene group is particularly preferred. As the polythiophene having an alkylene group, poly (3,4-ethylenedioxythiophene) is particularly preferable.

The poly anion forms a complex by forming an ion pair with the polythiophene (derivative), and the polythiophene (derivative) can be stably dispersed in water.
Examples of the poly anion include carboxylic acid polymers (for example, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), sulfonic acid polymers (for example, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyisoprene sulfonic acid, etc.), and the like. Can be mentioned. These carboxylic acid polymers and sulfonic acid polymers are also copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as aromatic vinyl compounds such as acrylates, styrene, vinyl naphthalene, etc. It may be. Among these, polystyrene sulfonic acid is particularly preferable.

The polystyrene sulfonic acid preferably has a weight average molecular weight of more than 20000 and 500,000 or less. More preferably, it is 40000-200000. If polystyrene sulfonic acid having a molecular weight outside this range is used, the dispersion stability of the polythiophene-based conductive polymer in water may decrease. The weight average molecular weight of the polymer is a value measured by gel permeation chromatography (GPC). For the measurement, an ultrahydrogel 500 column manufactured by Waters was used.

The conductivity of the conductive polymer is 0.05 S / cm or more. This is because practical electromagnetic shielding performance cannot be ensured when the conductivity is less than 0.05 S / cm.
A preferable lower limit of the conductivity is 0.10 S / cm. When the conductivity is less than 0.10 S / cm, sufficient electromagnetic wave shielding performance may not be maintained when formed into a coating film. A more preferred lower limit is 0.20 S / cm.

A conductive polymer having a conductivity of 0.10 (S / cm) or more can be easily produced by appropriately selecting the polymerization conditions and molecular weight. For example, by increasing the molecular weight, the conductive polymer has a high conductivity as described above. A conductive polymer exhibiting properties can be obtained. In addition, when the conductive polymer is a complex composed of poly (3,4-disubstituted thiophene) and a polyanion, the conductive polymer exhibits high conductivity by optimizing the pH exhibited by the polymerization system during production. A polymer can be obtained. Moreover, you may use a commercial item for the conductive polymer which shows such high electroconductivity.
In addition, after forming the conductive layer which consists of the said conductive polymer on a base material, the electrical conductivity of the conductive polymer said by this invention measures the film thickness and surface resistivity which the conductive layer shows, and shows to a following formula Calculate based on
Conductivity (S / cm) = 1 / {Surface resistivity (Ω / □) × film thickness (cm)}

The content of the conductive polymer in the conductive polymer layer is preferably 5.0~0.001mg / ^{m 2,} and more preferably 1.0~0.01mg / ^{m 2.} If it is less than 0.001 mg / m ² , the shielding property of the electromagnetic wave may be insufficient. On the other hand, if it exceeds 5.0 mg / m ² , a crack occurs in the conductive polymer layer when the electromagnetic wave shielding sheet is molded. It becomes easy and the problem that the shielding effect of an electromagnetic wave shield molding becomes low may arise.

The conductive polymer layer may contain other components in addition to the conductive polymer. That is, the conductive polymer layer is a layer formed using a conductive polymer composition containing the conductive polymer.
In addition to the conductive polymer, the conductive polymer composition may contain a water-soluble antioxidant, a binder, a crosslinking agent, a surfactant, a leveling agent, a conductivity improver, a solvent, and the like.

(Water-soluble antioxidant)
The said water-soluble antioxidant is a compound for improving the heat resistance and heat-and-moisture resistance of an electroconductive polymer layer, or suppressing the resistance increase by air exposure.
In addition, when a water-soluble antioxidant is blended, the water-soluble antioxidant can be uniformly present in the conductive polymer layer, so that an increase in resistance due to air exposure can be effectively suppressed. In addition, since a fat-soluble antioxidant cannot exist uniformly in a thin film, it cannot suppress the resistance increase by air exposure.
Furthermore, when a water-soluble antioxidant is blended, even if the amount used is relatively large (unless an excessive amount is added), the conductive polymer layer does not fog and can ensure high transparency. . On the other hand, when a fat-soluble antioxidant is used, the conductive polymer layer is clouded, which causes a decrease in transparency.

It does not specifically limit as said water-soluble antioxidant, A reducing or non-reducing water-soluble antioxidant is mentioned. Examples of the water-soluble antioxidant having reducibility include L-ascorbic acid, sodium L-ascorbate, potassium L-ascorbate, D (-)-isoascorbic acid (erythorbic acid), sodium erythorbate, erythorbic acid Compounds having a lactone ring substituted with two hydroxyl groups such as potassium; monosaccharides or disaccharides (excluding sucrose) such as maltose, lactose, cellobiose, xylose, arabinose, glucose, fructose, galactose, mannose; , Flavonoids such as rutin, myricetin, quercetin, kaempferol, sanmerin (registered trademark) Y-AF; two phenolic hydroxyl groups such as curcumin, rosmarinic acid, chlorogenic acid, hydroquinone, 3,4,5-trihydroxybenzoic acid more than Compounds; cysteine, glutathione, a compound having a pentaerythritol tetrakis (3-mercapto butyrate) thiol groups, such as and the like. Non-reducing water-soluble antioxidants include, for example, oxidative degradation such as phenylimidazolesulfonic acid, phenyltriazolesulfonic acid, 2-hydroxypyrimidine, phenyl salicylate, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate. The compound which absorbs the ultraviolet-ray which causes this is mentioned. These may be used alone or in combination of two or more.

Among these, at least one compound selected from the group consisting of a compound having a lactone ring substituted with two hydroxyl groups and a compound having two or more phenolic hydroxyl groups is preferable. ) -Isoascorbic acid or Sanmerin Y-AF is more preferred.

The content of the water-soluble antioxidant is preferably 0.01 to 5000 parts by weight, more preferably 0.05 to 2500 parts by weight, more preferably 0.1 to 100 parts by weight based on 100 parts by weight of the solid content of the conductive polymer. Part by weight is particularly preferred.
If the content is less than 0.01 parts by weight, the heat resistance and heat-and-moisture resistance of the conductive polymer layer may not be improved, or the increase in resistance due to air exposure may not be sufficiently suppressed. When it exceeds, it may become the cause of the fall of the electroconductivity of an electroconductive polymer layer, and electromagnetic wave shielding performance.

(binder)
The binder is used for the purpose of improving the adhesion between the conductive polymer layer and the resin layer or the metal layer, and the strength of the conductive polymer layer itself.
Examples of the binder include homopolymers such as epoxy resin, polyester, acrylic resin (polyacrylate, polymethacrylate), polyurethane, polyvinyl acetate, polyvinylidene chloride, polyamide, polyimide; styrene, vinylidene chloride, vinyl chloride, alkyl Copolymers obtained by copolymerizing monomers such as acrylate and alkyl methacrylate; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And the like, and the like. These binders may be used independently and may use 2 or more types together.

The binder preferably contains at least an acrylic resin.
This is because the acrylic resin has high toughness, and therefore, when blended in the conductive polymer layer, it can impart extensibility to the conductive polymer layer. The conductive polymer layer to which extensibility is imparted does not lower the electromagnetic shielding effect even when the conductive polymer layer is stretched by about 150%. Therefore, when an electromagnetic shielding molded body is molded using the above electromagnetic shielding sheet, even if the bent portion is stretched and the metal layer is disconnected, the conductive polymer layer is stretched to compensate the metallic layer, and the electromagnetic shielding molded body It is possible to prevent the electromagnetic wave shielding effect from decreasing.

Examples of the acrylic resin include (meth) acrylic resins and vinyl ester resins. As these acrylic resins, for example, a polymer containing a polymerizable monomer having an acidic group such as a carboxyl group, an acid anhydride group, a sulfonic acid group, or a phosphoric acid group as a constituent monomer may be used. Examples thereof include a single or copolymer of a polymerizable monomer having an acid group, a copolymer of a polymerizable monomer having a acid group and a copolymerizable monomer, and the like.

The (meth) acrylic resin may contain a (meth) acrylic monomer as a main constituent monomer (for example, 50 mol% or more). It is sufficient that at least one of the monomers has an acid group. As the (meth) acrylic resin, for example, a (meth) acrylic monomer having an acid group [(meth) acrylic acid, sulfoalkyl (meth) acrylate, sulfonic acid group-containing (meth) acrylamide, etc.) alone Or a copolymer, the (meth) acrylic monomer optionally having an acid group and another polymerizable monomer having an acid group [other polymerizable carboxylic acid, polymerizable polyvalent carboxylic acid or Anhydride, vinyl aromatic sulfonic acid and the like] and / or the copolymerizable monomer [for example, (meth) acrylic acid alkyl ester, glycidyl (meth) acrylate, (meth) acrylonitrile, aromatic vinyl monomer, etc.] Copolymer, other polymer monomer having an acid group and (meth) acrylic copolymerizable monomer [for example, (meth) acrylic acid alkyl ester, hydroxyalkyl (meta Acrylate, glycidyl (meth) acrylate, and copolymers of (meth) acrylonitrile, etc.].

Among these (meth) acrylic resins, polymers containing at least (meth) acrylic acid, for example, (meth) acrylic acid- (meth) acrylic acid ester polymers (acrylic acid-methyl methacrylate copolymer, etc.) , (Meth) acrylic acid- (meth) acrylic acid ester-styrene copolymers (acrylic acid-methyl methacrylate-styrene copolymers, etc.) are preferred.

Examples of the vinyl ester resin include a polymerizable monomer having the acid group (for example, (meth) acrylic acid, vinyl sulfonic acid, etc.), the vinyl ester monomer, and other copolymerization as necessary. And copolymers with monomers (such as α-olefins).

Although content of a binder is not specifically limited, 1-170 weight part is preferable with respect to 100 weight part of solid content of an electroconductive polymer in conversion of solid content, and 5-5000 weight part is more preferable.
If the content is less than 1 part by weight, it may be difficult to uniformly form the film thickness of the conductive polymer layer of the electromagnetic wave shielding sheet. On the other hand, if the content exceeds 170000 parts by weight, the electromagnetic wave shield of the conductive polymer layer may be difficult. It may cause a decrease in the effect.

(Crosslinking agent)
The crosslinking agent is used for the purpose of further improving the strength of the conductive thin film.
The crosslinking agent may be used in combination with a binder for the purpose of crosslinking the binder, or a self-crosslinking film of the crosslinking agent may be formed without using the binder. As a catalyst for crosslinking, an acidic group of a dopant may be used, or an organic acid or an inorganic acid may be newly added. Moreover, you may add a heat sensitive acid generator, a radiation sensitive acid generator, an electromagnetic wave sensitive acid generator, etc.

Examples of the crosslinking agent include melamine-based, polycarbodiimide-based, polyoxazoline-based, polyepoxy-based, and polyisocyanate-based crosslinking agents. These crosslinking agents may be used independently and may use 2 or more types together.

Although content of the said crosslinking agent is not specifically limited, 1-100,000 weight part is preferable with respect to 100 weight part of solid content of a conductive polymer in conversion of solid content, and 10-1000 weight part is more preferable.
If the content is less than 1 part by weight, the strength of the conductive polymer layer may be insufficient. On the other hand, if it exceeds 100,000 parts by weight, the electromagnetic wave shielding effect of the conductive polymer layer may be reduced. is there.

(Surfactant)
The surfactant is not particularly limited as long as it can improve leveling properties and obtain a uniform coating film.
Examples of the surfactant include polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic group-containing polydimethylsiloxane, Siloxane compounds such as perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane; fluorine-containing organic compounds such as perfluoroalkylcarboxylic acid and perfluoroalkylpolyoxyethyleneethanol; polyoxyethylene Polyether compounds such as alkyl phenyl ethers, propylene oxide polymers, ethylene oxide polymers; coconut oil fatty acid polymers Carboxylic acids such as citrate salts and gum rosins; Castor oil sulfates, phosphate esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonate esters, phosphate esters, succinate esters, and other ester compounds; alkyl aryl sulfonate amines Examples thereof include salts, sulfonate compounds such as dioctyl sodium sulfosuccinate; phosphate compounds such as sodium lauryl phosphate; amide compounds such as coconut oil fatty acid ethanolamide; and acrylic copolymers. Among these, siloxane compounds and fluorine-containing compounds are preferable from the viewpoint of leveling properties, and polyether-modified polydimethylsiloxane is particularly preferable.

Although content of the said surfactant is not specifically limited, 0.01-23000 weight part is preferable with respect to 100 weight part of solid content of a conductive polymer in conversion of solid content, and 0.1-5000 weight part is more. preferable.
If the content is less than 0.01 parts by weight, it may be difficult to form a uniform film thickness of the conductive polymer layer of the electromagnetic wave shielding sheet. On the other hand, if the content exceeds 23000 parts by weight, the conductive polymer layer It may cause a decrease in the electromagnetic shielding effect.

(Leveling agent)
Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic group-containing polydimethylsiloxane, Siloxane compounds such as fluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane; fluorine-containing organic compounds such as perfluoroalkylcarboxylic acid and perfluoroalkylpolyoxyethyleneethanol; polyoxyethylenealkyl Polyether compounds such as phenyl ether, propylene oxide polymer, ethylene oxide polymer; coconut oil fatty acid polymer Carboxylic acids such as citrate salts and gum rosins; Castor oil sulfates, phosphate esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonate esters, phosphate esters, succinate esters, and other ester compounds; alkyl aryl sulfonate amines Examples thereof include salts, sulfonate compounds such as dioctyl sodium sulfosuccinate; phosphate compounds such as sodium lauryl phosphate; amide compounds such as coconut oil fatty acid ethanolamide; and acrylic copolymers. These leveling agents may be used independently and may use 2 or more types together.

Although content of the said leveling agent is not specifically limited, 0.01-23000 weight part is preferable with respect to 100 weight part of solid content of a conductive polymer in conversion of solid content, and 0.1-5000 weight part is more preferable. .
If the content is less than 0.01 parts by weight, it may be difficult to form a uniform film thickness of the conductive polymer layer of the electromagnetic wave shielding sheet. On the other hand, if the content exceeds 230000 parts by weight, the conductive polymer layer It may cause a decrease in the electromagnetic shielding effect.

(Conductivity improver)
The conductivity improver is used by blending with the conductive polymer composition. Moreover, the electromagnetic wave shielding performance of a conductive polymer layer can be improved by mix | blending the said electroconductivity improver.
Examples of the conductivity improver include (a) a compound having a boiling point of 60 ° C. or higher and having at least one ketone group in the molecule, and (b) a boiling point of 100 ° C. or higher and having at least one ether group in the molecule. Compound, (c) a compound having a boiling point of 100 ° C. or more and having at least one sulfinyl group in the molecule, (d) a compound having a boiling point of 100 ° C. or more and having at least one amide group in the molecule, (e) a boiling point of 50 A compound having at least one carboxyl group in the molecule at or above ° C, (f) a compound having a boiling point of 100 ° C or more and having two or more hydroxyl groups in the molecule, and (g) 1 in the molecule having a boiling point of 100 ° C or more. And compounds having two lactam groups.

Examples of the compound (a) having a boiling point of 60 ° C. or more and having at least one ketone group in the molecule include isophorone, propylene carbonate, γ-butyrolactone, β-butyllactone, 1,3-dimethyl-2-imidazolide. Non etc. are mentioned.
Examples of the compound (b) having a boiling point of 100 ° C. or higher and having at least one ether group in the molecule include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, 2-phenoxyethanol, dioxane, morpholine, and 4-acryloylmorpholine. , N-methylmorpholine N-oxide, 4-ethylmorpholine, oxetane, THF, THP and the like.
Examples of the compound (c) having a boiling point of 100 ° C. or higher and having at least one sulfinyl group in the molecule include dimethyl sulfoxide.
Examples of the compound (d) having a boiling point of 100 ° C. or higher and having at least one amide group in the molecule include N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide, acetamide, and N-ethyl. Examples include acetamide, N-phenyl-N-propylacetamide, and benzamide.
Examples of the compound (e) having a boiling point of 50 ° C. or higher and having at least one carboxyl group in the molecule include acrylic acid, methacrylic acid, methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, Octanoic acid, decanoic acid, dodecanoic acid, benzoic acid, p-toluic acid, p-toluic acid, p-chlorobenzoic acid, p-nitrobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, isophthalic acid, Examples include oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid and the like.
Examples of the compound (f) having a boiling point of 100 ° C. or higher and having two or more hydroxyl groups in the molecule include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, β-thiodiglycol, triethylene glycol, triethylene glycol, Propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerin, erythritol, glycerin, Examples include inmitol, lactitol, maltitol, mannitol, sorbitol, xylitol, and sucrose.
Examples of the compound (g) having a boiling point of 100 ° C. or higher and having at least one lactam group in the molecule include N-methylpyrrolidone, β-lactam, γ-lactam, δ-lactam, ε-caprolactam, laurolactam and the like. Is mentioned.
When the boiling point of the conductivity improver is equal to or higher than a specific temperature, the conductivity improver gradually volatilizes by heating during formation of the conductive layer. In the process, the orientation of the conductive polymer is changed to electromagnetic waves. It is considered that the orientation is controlled to be advantageous for the shielding performance, and as a result, the electromagnetic shielding performance is improved. On the other hand, if the boiling point of the conductivity improver is less than a specific temperature, the conductivity improver rapidly evaporates, so the orientation of the conductive polymer is not sufficiently controlled and the electromagnetic shielding performance is not improved. It is considered a thing.
The said electrical conductivity improver may be used independently and may use 2 or more types together.

Although content of the said electroconductivity improver is not specifically limited, In a conductive polymer composition, 5-2000 weight part is preferable with respect to 100 weight part of solid content of a conductive polymer, and 10-1500 weight part is more. preferable.
When the content of the conductivity improver is less than 5 parts by weight, the electromagnetic shielding performance may not be sufficiently improved. On the other hand, when the content exceeds 2000 parts by weight, the conductive polymer layer is formed. There are cases where the conductive component of the conductive polymer composition becomes dilute and sufficient electromagnetic wave shielding performance cannot be imparted when the conductive polymer layer is formed.

The conductive polymer composition for forming the conductive polymer layer may contain a solvent. It is preferable that the solvent does not remain in the conductive polymer layer.
In addition, although what completely dissolves all the components of the composition for conductive coating is referred to as “solvent”, and what disperses insoluble components is referred to as “dispersion medium”. Is also described as “solvent”.
(solvent)
Examples of the solvent include alcohols such as water, methanol, ethanol, 2-propanol, and 1-propanol; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; ethylene glycol monomethyl ether and diethylene glycol monomethyl. Glycol ethers such as ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; Glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; Propylene glycol, dipropylene glycol, tripropylene glycol, etc. Propylene rubber Coles: propylene glycol such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether Ethers: propylene glycol ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; tetrahydrofuran; acetone; acetonitrile and the like It is. These may be used alone or in combination of two or more.

Among these, water or a mixture of water and an organic solvent is preferable.
When using water as said solvent, 20-500000 weight part is preferable with respect to 100 weight part of solid content of a conductive polymer, and, as for content of water, 200-10000 weight part is more preferable.
When the water content exceeds 500,000 parts by weight, the conductive component in the conductive polymer composition for forming the conductive polymer layer becomes diluted, and sufficient electromagnetic wave shielding performance can be imparted when the conductive polymer layer is formed. This is because it may disappear.

Moreover, when using the mixture of water and an organic solvent, as an organic solvent, methanol, ethanol, or 2-propanol is preferable.
In this case, the content of the organic solvent is not particularly limited, and is preferably 20 to 770000 parts by weight and more preferably 200 to 20000 parts by weight with respect to 100 parts by weight of the solid content of the conductive polymer. Moreover, when using water and an organic solvent together, the ratio of both (ratio of water and organic solvent) is preferably 100: 0 to 5:95, and more preferably 100: 0 to 30:70.

As described above, the shield sheet may include a primer layer and a printing layer.
Examples of the primer layer include homopolymers such as polyester, acrylic resin (polyacrylate, polymethacrylate), polyurethane, polyvinyl acetate, polyvinylidene chloride, polyamide, polyimide; styrene, vinylidene chloride, vinyl chloride, alkyl acrylate, A copolymer obtained by copolymerizing monomers such as alkyl methacrylate; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. The thing which consists of an alkoxysilane compound etc. is mentioned. These may be used alone or in combination of two or more.
The printing layer may be formed using a conventionally known printing ink.

Although the thickness of the said shield sheet which consists of such a structure is not specifically limited, 0.01-10 mm is preferable.
The reason is that when the thickness of the shield sheet is less than 0.01 mm, it is difficult to maintain the shape of the molded body because the strength of the molded body after molding the shield sheet is insufficient. This is because if the thickness exceeds 10 mm, it may be difficult to mold into various shapes.

Moreover, the electromagnetic wave shielding performance measured by the KEC method of the shield sheet is preferably 20 dB or more, and more preferably 30 dB or more in the frequency range of 1 to 100 MHz.
If it is within this range, the electromagnetic wave shield molded body obtained by molding the shield sheet can sufficiently shield electromagnetic waves emitted from various electronic devices.

Next, the manufacturing method of the said shield sheet is demonstrated.
(1) As the resin layer, a resin film made of the above-described material is used as a starting material.
In addition, as a method for obtaining the resin film, the resin film may be produced by using a conventionally known film-like molding method such as extrusion molding or calendar molding, or a commercially available product may be used.

(2) A metal layer is formed on one side or both sides of the resin film. The method for forming the metal layer is as described above.
In addition, what is necessary is just to form a metal layer through a mask, for example, when forming a patterned metal layer as said metal layer.

(3) Next, the conductive polymer layer is formed on one side or both sides of the resin film (laminate) on which the metal layer is formed.
The said conductive polymer layer can be formed by apply | coating the said conductive polymer composition, and performing a drying process as needed after that, for example.

Here, as a method of applying the conductive coating composition, a known application method can be used. Examples of the application method include spin coating, gravure coating, bar coating, dip coating, curtain coating, die coating, and spray coating. Furthermore, printing methods such as screen printing, spray printing, ink jet printing, relief printing, intaglio printing, and lithographic printing can also be applied. What is necessary is just to select suitably from these methods according to the objective.

Moreover, when drying the apply | coated composition for electroconductive coating, the method is not specifically limited, For example, what is necessary is just to perform using drying machines, such as a ventilation dryer, a hot air dryer, an infrared dryer. Further, when a dryer having a heating means (hot air dryer, infrared dryer, etc.) is used, drying and heating can be performed simultaneously. Further, in addition to these dryers, a heating / pressurizing roll having a heating / pressurizing function, a press machine, or the like may be used.
Also, the drying conditions are not particularly limited, but conditions of 25 to 200 ° C. for about 10 seconds to 2 hours are preferable, and conditions of 50 to 150 ° C. for about 20 seconds to 15 minutes are more preferable.

The shield sheet can be manufactured through such steps.
Moreover, what is necessary is just to form each layer suitably in a suitable process, when manufacturing a shield sheet provided with a primer layer, an adhesive bond layer, and a printing layer.

Next, the electromagnetic wave shielding molded product of the present invention will be described with reference to the drawings.
The electromagnetic wave shield molding of the present invention comprises at least a resin layer (A), a metal layer (B), and a conductive polymer layer (C) containing a conductive polymer having a conductivity of 0.05 S / cm or more. ,
A metal layer (B) is provided on at least one side of the resin layer (A), and
The conductive polymer layer (C) is provided on at least one surface of a laminate having the resin layer (A) and the metal layer (B).

Fig.3 (a) is a perspective view which shows typically an example of the electromagnetic wave shield molding of this invention, (b) is sectional drawing which shows typically the AA line cross section of (a).
As shown in FIGS. 3 (a) and 3 (b), the electromagnetic wave shield molded body 100 has a shape that is formed so that the sheet-like object 110 includes a quadrangular prism-like convex portion 110a at the center portion. The convex part 110a is configured to accommodate an electromagnetic wave shielding device (device that emits electromagnetic waves) such as a hard disk.
And the sheet-like object 110 forms the laminated body 113 by forming the metal layer 112 on one surface of the resin layer 111, and the conductive polymer layer 114 on the surface of the resin layer 111 opposite to the side on which the metal layer 112 is formed. Has a layer structure.
That is, the sheet-like object 110 has the same layer configuration as the shield sheet 10 shown in FIG.

The layer configuration of the electromagnetic wave shield molded body of the present invention is not limited to the layer configuration shown in FIG. 3, and a metal layer is formed on one side of the resin layer as in the above-described shield sheet of the present invention. Layer structure in which a conductive polymer layer is further formed on the surface of the resin layer on which the metal layer is formed (see FIG. 2), and a metal layer is formed on both surfaces of the resin layer to form a laminate. The layer structure in which a conductive polymer layer is formed on both surfaces or one surface of the laminate may be used.
Furthermore, similarly to the shield sheet of the present invention, a layer configuration including an adhesive layer, a primer layer, and a printing layer may be used.

Moreover, since the specific example of each layer which comprises the said electromagnetic wave shield molded object is the same as the specific example of each layer which comprises the shield sheet of this invention already demonstrated, the description is abbreviate | omitted here.

The shape of the electromagnetic wave shield molded body is not limited to the shape shown in FIG. 3 and may be, for example, the shape shown in FIGS.
4 and 5 are perspective views schematically showing another example of the electromagnetic wave shield molded body of the present invention.
As shown in FIG. 4, the electromagnetic wave shield molded body 200 includes a convex portion 210 a having a shape obtained by cutting off a part of a spherical surface at the central portion of the seal-like object 210.
As shown in FIG. 5, the electromagnetic wave shield molded body 300 includes a columnar convex portion 310 a at the center of the seal-like object 310.
Also in the electromagnetic shielding molded body having such a shape, the electromagnetic wave shielding device is accommodated in the convex portion.

That is, the shape of the electromagnetic wave shielding molded body may be any shape as long as the electromagnetic wave shielding device is accommodated and covered.

Next, the manufacturing method of the electromagnetic wave shield molding of this invention is demonstrated.
The electromagnetic wave shield molded body can be manufactured, for example, by molding the shield sheet of the present invention.
When the shield sheet of the present invention is molded and manufactured, a roll-to-roll process can be applied as a method for manufacturing an electromagnetic wave shield molded body, and thus the productivity is excellent.
Examples of the method for molding the shield sheet include vacuum molding, press molding, compressed air molding, blow molding, and the like.

In addition, the electromagnetic wave shield molded body is formed, for example, by molding a laminated body (corresponding to the laminated body of the shield sheet) in which a metal layer is formed on one side or both sides of a resin film by the above-described vacuum molding or the like. You may manufacture by forming a conductive polymer layer.
As a method for forming the conductive polymer layer, for example, a method similar to the method for forming the conductive polymer layer in the above-described method for producing a shield sheet of the present invention can be used.

As already described, one of the excellent effects of the electromagnetic wave shield molded body of the present invention is the inconvenience caused when a conventional shield sheet consisting only of a resin layer and a metal layer is molded, that is, the metal layer in the molding process. It is possible to avoid the inconvenience that a part of the wire breaks (cracks occur) and the electromagnetic wave shielding performance deteriorates.
Therefore, when a conductive polymer layer is formed later on the molded laminate, there is an advantage that the conductive polymer layer only needs to be formed only at the disconnected portion of the metal layer.
In addition, the disconnection location of a metal layer can be specified by observing the metal surface with a microscope, for example.

Further, the electromagnetic wave shield molded body is, for example, a method of forming a metal layer and a method of forming a conductive polymer layer in the above-described method for producing a shield sheet of the present invention after molding only a resin film by vacuum molding or the like. The metal layer and the conductive polymer layer may be formed by the same method or the like.

Further, the electromagnetic wave shielding molded body preferably has an electromagnetic wave shielding performance measured by the KEC method of 20 dB or more, and more preferably 30 dB or more in a frequency range of 1 to 100 MHz.

In addition, when the electromagnetic shielding molded body is manufactured using the shielding sheet of the present invention, the electromagnetic shielding performance measured by the KEC method is maintained at 80% or more of the shielding sheet before molding in the frequency range of 1 to 100 MHz. Preferably it is.
If 80% or more is maintained, it is possible to deal with various shapes of electromagnetic shielding molded bodies, and the electromagnetic shielding molded bodies can be easily designed.

Such an electromagnetic wave shield molded body of the present invention includes a personal computer, a mobile phone, a digital camera, a game machine, a medical device, an electric vehicle (including a hybrid vehicle), an automobile, and other precision devices on which a semiconductor such as an LSI is mounted. It can be particularly suitably used as a member for shielding electromagnetic waves of electronic components mounted on electronic devices.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to a following example. Hereinafter, “part” or “%” means “part by weight” or “% by weight”, respectively, unless otherwise specified.

(Preparation of conductive polymer composition A)
An aqueous dispersion of a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (HC Starck Co., Ltd .: CleviosPH500, solid content 1.0%, conductivity = 0.23 S / cm) 100 parts, 20 parts acrylic resin aqueous dispersion (Nippon Pure Chemicals Co., Ltd .: Jurimer AT-613, solid content 23.5%) as binder, 4.6 parts dimethyl sulfoxide (Kanto Chemical Co., Ltd.) as conductivity improver ), 2.0 parts surfactant (100% solids), 2.0 parts leveling agent (100% solids), 10 parts water, and 10 parts ethanol and stirred for 1 hour did. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition A.

(Preparation of conductive polymer composition B)
An aqueous dispersion of a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (HC Starck Co., Ltd .: CleviosPH500, solid content 1.0%, conductivity = 0.23 S / cm) In 100 parts, 10 parts of an acrylic resin water dispersion (manufactured by Nippon Pure Chemicals Co., Ltd .: Jurimer AT-613, solid content 23.5%) and 3.3 parts of an epoxy resin (manufactured by Nagase ChemteX Corporation: Denacol) EX-861, solid content 100%), 4.6 parts dimethyl sulfoxide (manufactured by Kanto Chemical Co., Inc.) as a conductivity improver, 2.0 parts surfactant (solid content 100%), 2.0 parts leveling Agent (100% solids), 10 parts water, and 10 parts ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition B.

(Preparation of conductive polymer composition C)
Instead of 3.3 parts of epoxy resin (manufactured by Nagase ChemteX Corporation: Denacol EX-861, solid content 100%), 10 parts of polyester resin aqueous dispersion (manufactured by Nagase ChemteX Corporation: Gabsen ES-210, solid content) A conductive polymer composition C was obtained in the same manner as the conductive polymer composition B except that 25.0%) was used.

Example 1
A shield sheet having the layer structure shown in FIG. 1 was produced by the following method.
Vacuum deposition machine (SVC-700, manufactured by Sanyu Electronics Co., Ltd.) on one side of an A-PET (amorphous polyethylene terephthalate) film (Mitsubishi Chemical Corporation: Novaclear SH046, thickness: 0.40 mm, corresponding to 11 in FIG. 1) -2 TURBO-TM) was used to deposit Al (equivalent to the metal layer 12 in FIG. 1, the thickness was 0.2 μm), and an Al deposited film was obtained. Next, the conductive polymer composition A was placed on the surface opposite to the Al deposition surface with the wire bar No. 22 (wet film thickness 50 μm) was applied by a bar coating method and dried at 70 ° C. for 15 minutes to form a conductive polymer layer, thereby producing a shield sheet having the layer structure shown in FIG.

(Example 2)
A shield sheet having the layer structure shown in FIG. 1 was produced by the following method.
On one side of A-PET film (thickness: 0.40 mm, manufactured by Mitsubishi Chemical Co., Ltd .: Novaclear SH046, thickness: 0.40 mm), a vacuum vapor deposition machine (SVC-700-2 TURBO-TM, manufactured by Sanyu Electronics Co., Ltd.) Cu was vapor-deposited (corresponding to the metal layer 12 in FIG. 1 and the thickness was 0.2 μm) to obtain a Cu vapor-deposited film. Next, the conductive polymer composition A was placed on the surface opposite to the Cu deposition surface with the wire bar No. 22 (wet film thickness 50 μm) was applied by a bar coating method and dried at 70 ° C. for 15 minutes to form a conductive polymer layer, thereby producing a shield sheet having the layer structure of FIG.

(Example 3)
A shield sheet was produced in the same manner as in Example 1 except that the conductive polymer composition B was used in place of the conductive polymer composition A.

Example 4
A shield sheet was produced in the same manner as in Example 1 except that the conductive polymer composition C was used in place of the conductive polymer composition A.

(Example 5)
A shield sheet having the layer structure shown in FIG. 2 was produced by the following method.
A shield sheet was prepared in the same manner as in Example 1 except that the conductive polymer composition A was not applied to the surface opposite to the Al deposited surface, and the conductive polymer composition A was applied to the Al deposited surface.

(Comparative Example 1)
The Al vapor deposition film produced in Example 1 was used as a shield sheet.

(Comparative Example 2)
The Cu vapor deposition film produced in Example 2 was used as a shield sheet.

(Comparative Example 3)
A Cu plate having a thickness of 0.5 mm was used as a shield sheet.

(Comparative Example 4)
An Al plate having a thickness of 0.5 mm was used as a shield sheet.

(Evaluation)
Each shield sheet manufactured in Examples 1 to 5 and Comparative Examples 1 to 4 was cut into 10 cm × 10 cm to obtain a shield sheet for evaluation.

(Weight measurement)
The weight of each evaluation shield sheet was measured with a balance (manufactured by METLER TLLENDO). The results are shown in Table 1.

The shield sheet for evaluation was molded under any of the following molding conditions 1-1 to 2-2 to obtain an electromagnetic wave shield molded body, which was used as the shield molded body for evaluation. The electromagnetic shielding performance and processability of each evaluation shield molding were evaluated.

(Molding condition 1-1)
Molded by a method generally referred to as “vacuum molding” through the following steps (1) to (4).
(1) The evaluation shield sheet is uniformly heated with a heater at 400 ° C. for 60 seconds to be softened.
(2) Next, the softened evaluation shield sheet is separated from the heater, and the softened evaluation shield sheet is pressed against the mold. Here, as the mold, a mold having a height of 1 cm and capable of forming a convex part having a size of 5 cm × 5 cm at the bottom (in FIG. 3A, h = 1 cm, W ₁ , W ₂ = 5 cm) was used. .
(3) Thereafter, the vacuum pump is operated to suck the air in the gap between the softened evaluation sample and the mold, and the softened evaluation shield sheet and the mold are brought into close contact with each other.
(4) After cooling to room temperature, it removes from a metal mold | die, and obtains the electromagnetic wave shield molded object which has a convex part with a height of 1 cm and a size of 5 cm × 5 cm at the bottom.

(Molding condition 1-2)
Molding was performed except that a mold having a height of 10 cm and a convex part having a bottom size of 5 cm × 5 cm (in FIG. 3A, h = 10 cm, W ₁ , W ₂ = 5 cm) was used. Vacuum molding is performed under the same conditions as in Condition 1-1, and an electromagnetic wave shield molded body having a height of 10 cm and a bottom portion having a size of 5 cm × 5 cm at the center is obtained.

(Molding conditions 2-1)
Molded by a method generally called “press molding” through the following steps.
The evaluation shield sheet is positioned between the convex mold and the concave mold, and pressure is applied to the evaluation sample for 10 seconds with a force of 20,000 N at room temperature. Thereafter, the electromagnetic wave shield molding is obtained by releasing the force and removing it from the mold.
Here, as the convex mold and the concave mold, a mold having a height of 1 cm and a convex part having a bottom size of 5 cm × 5 cm (in FIG. 3A, h = 1 cm, W ₁ , W ₂ = 5 cm) can be formed. used.

(Molding condition 2-2)
Except for using a convex shape and a concave shape that can form a convex portion having a height of 10 cm and a bottom size of 5 cm × 5 cm (in FIG. 3A, h = 10 cm, W ₁ , W ₂ = 5 cm). Then, press molding is performed under the same conditions as the molding condition 2-1, and an electromagnetic wave shield molded body having a height of 10 cm and a bottom portion having a size of 5 cm × 5 cm at the center is obtained.

(Evaluation of electromagnetic shielding performance)
The electromagnetic wave shielding performance of each evaluation shield sheet is previously measured in the frequency region of 1 to 100 MHz by the KEC method.
Next, the evaluation shield sheets of Examples 1 to 5 and Comparative Examples 1 and 2 were molded under the molding condition 1-1, and the evaluation shield sheets of Comparative Examples 3 and 4 were molded according to the molding condition 2- 1 to produce an evaluation shield molding, and for each of the evaluation shield moldings, the electromagnetic shielding performance is measured in the frequency region of 1 to 100 MHz by the KEC method.
The electromagnetic shielding performance of each evaluation shield sheet and each evaluation shield molding was evaluated according to the following criteria. The results are shown in Table 1.
(Evaluation criteria for electromagnetic shielding performance)
A: There is an electromagnetic wave shielding effect of 30 dB or more.
Δ: There is an electromagnetic wave shielding effect of 10 or more and less than 30 dB.
X: Electromagnetic wave shielding effect of less than 10 dB.

Furthermore, the ratio (shield performance maintenance rate (%)) of the electromagnetic shielding performance of each evaluation shield molding to the electromagnetic shielding performance before molding (evaluation shield sheet) was calculated. The results are shown in Table 1.

(Processability evaluation)
About the shielding sheet for evaluation of Examples 1-5 and Comparative Examples 1 and 2, it shape | molds on the said molding conditions 1-2, About the shielding sheet for evaluation of Comparative Examples 3 and 4, it shape | molds on the said molding conditions 2-2. Then, a shield molded body for evaluation was produced, each shield molded body for evaluation was visually observed, and the workability was evaluated according to the following criteria. The results are shown in Table 1.
(Processing evaluation criteria)
○: No crack in the appearance of the molded body ×: There is a crack in the appearance of the molded body

(Example 6)
The shield sheet produced in Comparative Example 1 was molded under molding conditions 1-1, and a molded body a (see FIG. 3) having a height of 1 cm and a bottom portion having a size of 5 cm × 5 cm at the center was prepared. Then, the electroconductive polymer composition A was applied to the molded body a at a lifting speed of 1 mm / sec using a dip coater (manufactured by Asumi Giken Co., Ltd., M series) to prepare an electromagnetic wave shield molded body A.

(Evaluation)
The following evaluation was performed using each of the molded body a and the electromagnetic wave shield molded body A produced in Example 6 as an evaluation sample.

(Weight measurement)
The weight of each evaluation sample was measured with a balance (manufactured by METTTLER TLLENDO). The results are shown in Table 2.

(Evaluation of electromagnetic shielding performance)
The electromagnetic shielding performance of each of the molded product a and the electromagnetic shielding molded product A produced in Example 6 was measured in the frequency range of 1 to 100 MHz by the KEC method.
And each electromagnetic wave shielding performance of the molded object a and the electromagnetic wave shield molded object A was evaluated on the following reference | standard. The results are shown in Table 2.
(Evaluation criteria for electromagnetic shielding performance)
A: There is an electromagnetic wave shielding effect of 30 dB or more.
Δ: There is an electromagnetic wave shielding effect of 10 or more and less than 30 dB.
X: Electromagnetic wave shielding effect of less than 10 dB.

表１の結果から、実施例１〜５の成型用シールドシートは、比較例１、２のシールドシートに比べて成型後の電磁波シールド性能の維持率が高く、成型体が実用上充分な電磁波シールド性能を有していることが明らかとなった。また、比較例３、４のシールドシートに比べて、軽量で、かつ、成型性に優れることも明らかとなった。
また、表２の結果から、樹脂層上に金属層が形成された積層体を成型した後、得られた成型体に導電性ポリマー層を形成した場合も、電磁波シールド性能に優れた電磁波シールド成型体となることが明らかとなった。

From the results of Table 1, the shielding sheets for molding of Examples 1 to 5 have a higher retention rate of the electromagnetic shielding performance after molding than the shielding sheets of Comparative Examples 1 and 2, and the electromagnetic shielding with a molded body that is practically sufficient. It became clear that it had performance. Moreover, it became clear that it was lightweight and excellent in a moldability compared with the shield sheet of Comparative Examples 3 and 4.
In addition, from the results of Table 2, after molding a laminated body in which a metal layer is formed on a resin layer, an electromagnetic wave shielding molding excellent in electromagnetic wave shielding performance even when a conductive polymer layer is formed on the obtained molded body. It became clear that it became a body.

The present invention is mounted on electronic devices, in particular, personal computers, mobile phones, digital cameras, game machines, medical devices, automobiles, electric vehicles (including hybrid vehicles), and other precision devices on which semiconductors such as LSIs are mounted. It is suitably used for shielding electromagnetic waves emitted by electrical components.

10, 20 Shield sheet 11, 21 Resin layer 12, 22 Metal layer 13, 23 Laminated body 14, 24 Conductive polymer layer 100, 200, 300 Electromagnetic wave shield molding

Claims (10)

At least a resin layer (A), a metal layer (B), and a conductive polymer layer (C) containing a conductive polymer having a conductivity of 0.05 S / cm or more,
A metal layer (B) is provided on at least one surface of the resin layer (A), and
An electromagnetic wave shielding sheet for molding comprising the conductive polymer layer (C) on at least one surface of a laminate having the resin layer (A) and the metal layer (B). The electromagnetic wave shielding sheet for molding according to claim 1, wherein the metal layer (B) is made of a conductive metal, metal oxide, or magnetic material. The electromagnetic wave shielding sheet for molding according to claim 1 or 2, wherein the metal layer (B) is a layer formed by vapor deposition and has a thickness of 0.01 to 10.0 µm. The electromagnetic wave shielding sheet for molding according to any one of claims 1 to 3, wherein the conductive polymer is composed of a composite of poly (3,4-disubstituted thiophene) and a polyanion. The electromagnetic wave shielding sheet for molding according to any one of claims 1 to 4, wherein the conductive layer (C) contains a binder, and at least one of the binders is an acrylic resin. The conductive layer (C) contains a conductive polymer and a conductivity improver, and the compounding amount of the conductivity improver is 10 to 1500 parts by weight with respect to 100 parts by weight of the solid content of the conductive polymer. The electromagnetic wave shielding sheet for molding according to any one of claims 1 to 5, wherein the electromagnetic wave shielding sheet is a layer formed using a conductive polymer composition. At least a resin layer (A), a metal layer (B), and a conductive polymer layer (C) containing a conductive polymer having a conductivity of 0.05 S / cm or more,
A metal layer (B) is provided on at least one surface of the resin layer (A), and
An electromagnetic wave shield molded article comprising the conductive polymer layer (C) on at least one surface of a laminate having the resin layer (A) and the metal layer (B). The electromagnetic wave shielding molded product according to claim 7, wherein the electromagnetic wave shielding sheet for molding according to claim 1 is molded. The electromagnetic wave shield molded article according to claim 7, wherein a conductive polymer layer (C) is formed on the surface of a molded article obtained by molding a laminated sheet comprising at least a resin layer (A) and a metal layer (B). . The electromagnetic wave shield molded article according to any one of claims 7 to 9, which is used as an electromagnetic wave shield for electronic equipment.

Images