JP2682809B2 - Flexible sheet containing amorphous metal - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amorphous metal-containing flexible sheet. More specifically, the present invention relates to an amorphous metal-containing flexible sheet containing an amorphous metal powder and a conductive material additive different from that, and having excellent electromagnetic field wave shielding properties. .

[0002]

2. Description of the Related Art In recent years, with the recent progress of electronic devices, the cases where these devices are densely used or used as advanced power products are increasing. When using such electronic devices, it is necessary to protect them from the adverse effects of static electricity and electromagnetic field waves and prevent troubles such as breakdowns and malfunctions.

Conventionally, in order to solve the above-mentioned problems, means for accommodating and sealing the device body in a conductive housing or accommodating the device in a conductive storage case have been adopted. The conductive case is a rigid container molded of conductive plastic obtained by mixing a conductive material with a molding material such as plastic, or the conductive case is coated with conductive paint on the surface of the non-conductive case. It was manufactured by a method such as coating.

However, when a large number of electronic devices are distributed and used in a factory or an office, these devices are individually used to prevent electromagnetic field waves from diverging to the outside and to prevent electromagnetic waves from the outside. It is necessary to prevent the entry of field waves. For this reason, it is desirable to cover each device with a flexible cover sheet or film structure having antistatic properties and electromagnetic wave shielding properties.

It has been attempted to utilize a metal plate or a metal foil as a sheet material for the above-mentioned use.
Due to its rigidity, it could only be used for specific applications and shapes.

[0006]

In view of the above problems,
INDUSTRIAL APPLICABILITY The present invention has high antistatic properties and electromagnetic field wave shielding properties, is flexible, can be easily processed into a desired shape, and can be easily adapted to the shape and usage condition of the equipment to be used. It is intended to provide a flexible sheet containing an amorphous metal.

[0007]

The amorphous metal-containing flexible sheet of the present invention comprises a base fabric made of a fibrous material, and a flexible polymer resin formed on at least one surface of the base fabric as a base material. And at least one resin layer, wherein at least one layer of the resin layer is dispersed in the flexible polymer resin matrix, and the amorphous metal powder and the non-metal conductive material powder are provided. And at least one conductive material additive selected from a conductive organic material and a body. At least one of the above resin layers
The layer may further include a non-amorphous metal powder that is different from the amorphous metal powder.

The amorphous metal-containing flexible sheet having at least one amorphous metal-containing resin layer of the present invention is contained in various electromagnetic wave shielding articles as a part of its constituent components. Such an electromagnetic wave shielding article of the present invention includes a film structure, a wall material, a covering material, a floor material, a floor sheet material, and other articles having various shapes and sizes.

[0009]

The flexible polymer resin used in the amorphous metal-containing flexible sheet of the present invention can be selected from natural rubber, synthetic rubber and flexible synthetic resin, preferably polyvinyl chloride (PVC), polyurethane, Ethylene-vinyl acetate copolymer, isotactic polypropylene, polyethylene, polyacrylonitrile, polyester and polyamide, fluorine-containing resin, silicone resin, styrene-butadiene rubber (SBR), chlorosulfonated polyethylene rubber, polyurethane rubber, butyl rubber, fluorine-containing It can be selected from rubber, silicone rubber and isoprene rubber. The most preferred synthetic resin is PVC, which is a plasticizer, filler, colorant, stabilizer and / or
Alternatively, it may contain other modifiers. The base material may be a porous body or a non-porous solid body.

In the amorphous metal-containing resin layer, the amorphous metal powder particles dispersed in the flexible base material may be any of spherical particles, granular particles, flake-shaped particles, fibrous particles, and the like. There is no particular limitation on the size of the width and the length, but a size of about 0.1 to 5 mm is generally preferable. The content of the amorphous metal powder in the base material is not particularly limited as long as the object of the present invention is achieved, but it is generally preferably 1 to 70% by weight, and 3 to
It is more preferably 50% by weight.

The amorphous metal used in the present invention is
Generally, iron is the main component, and boron, silicon, carbon,
It is preferable to be selected from an amorphous alloy obtained by adding at least one selected from nickel, cobalt, molybdenum, and the like. For example, Allied's product name METGLAS No. 2602SC (Fe: 81%,
B: 13.5%, Si: 3.5%, C: 2% amorphous alloy), No. 2605 S-2 (Fe: 78%,
B: 13%, Si: 9% amorphous alloy), No. 2
605-CO (87 parts of Fe, 14 parts of B, Si: 1)
Part, Co: 18 parts amorphous alloy), No. 2826
-MB (Fe: 40%, Ni: 38%, Mo: 4%,
B: 18% amorphous alloy).

Further, in addition to the alloys containing iron as a main component,
An alloy system containing cobalt as a main component (for example, Co₉₀Zr
_Ten, Co₇₈Si_TenB₁₂, Co₅₆Cr₂₆C₁₈, Co₄₄Mo
₃₆C ₂₀, Co₃₄Cr₂₈Mo₂₀C₁₈), Nickel as main component
Alloy system (for example, Ni₉₀Zr_Ten, Ni₇₈Si
_TenB₁₂, Ni₃₄Cr_{twenty four}Mo_{twenty four}C₁₈), And other gold
Alloys based on metals (eg, Pd₈₀Si₂₀, Cu₈₀
Zr₂₀, Nb₅₀Ni₅₀, Ti ₅₀Cu₅₀) Etc. are also available
You. Amorphous alloys have a thickness of 1-100 μm, generally
It is manufactured as a ribbon-shaped thin film of 5 to 50 μm.

The above-mentioned amorphous metal powder particles impart good electromagnetic field wave shielding property, particularly magnetic field wave shielding property, to the amorphous metal-containing flexible sheet of the present invention.

The amorphous metal powder particles used in the present invention may have a plating layer made of a conductive metal formed on at least a part of the outer peripheral surface thereof. Such a conductive metal plating layer further improves the electromagnetic field wave shielding property of the amorphous metal-containing flexible sheet of the present invention,
In particular, it is effective to enhance the electric field wave shielding effect.

The conductive metal used for forming the plated layer can be selected from, for example, copper, nickel, cobalt, iron, aluminum, gold, silver, tin, zinc, and alloys of two or more of these.

In the amorphous metal-containing flexible sheet of the present invention, the amorphous metal-containing resin layer has, in addition to the amorphous metal powder particles dispersed in the flexible polymer resin base material, at least 1 different from that.
A conductive material additive of some kind.

The conductive material additive useful in the present invention is selected from non-metallic conductive material powders and conductive organic materials,
If necessary, non-amorphous metal powder particles may be further included.

The non-amorphous metal powder particles have good conductivity and electromagnetic field wave shielding effect, especially electromagnetic wave shielding effect, and for example, copper, nickel, cobalt, iron, aluminum, gold, silver, tin, zinc. , And compounds containing at least one of these, and alloys such as stainless steel, brass, bronze, nickel silver, etc., which are spherical, granular, flaky, and fibrous. Any of them may be used, and the content rate in the base material is preferably set so that the total content rate of the additives in the base material is within the range of 1 to 70%.

The non-metal conductive material powder used in the present invention can be selected from carbon black, graphite, carbon fiber and the like, and the size and content thereof are the same as those of the non-amorphous metal powder. Can be set.

The conductive organic material used in the present invention can be selected, for example, from a conductive plasticizer or a conductive polymer material.

The electrically conductive plasticizer is, for example, a polycarboxylic acid ester compound of mono- and poly-alkylene glycol monoalkyl ether, and has, for example, the following general formulas (I), (II) and (III):

Embedded image(However, in the above formula, X has a substituent having 2 to 8 carbon atoms,
Aliphatic, alicyclic and aromatic polybasic acids with and without
Represents a member selected from the residues, Y is epoxidized
Cyclohexa with and without substituents
Represents a member selected from ring groups, and Z is a member of 2 to 22 carbon atoms.
Aliphatic, alicyclic and aromatic polybasic carboxylic acid residues
A member selected from₁, A_Two, A_Three, A_FourAnd
And A_FiveAre independently of each other an alkyle having 2 to 4 carbon atoms.
R represents a member selected from the group₁, R_Two, R_Three, R
_FourAnd R_FiveAre independently of each other having 1 to 15 carbon atoms
Represents a member selected from straight and branched chain alkyl groups.
I, but A₁And R₁, A_TwoAnd R_TwoAnd A_ThreeAnd R_Threeof
The total number of carbon atoms N is 5 to 17, and m₁, M_Two, M
_ThreeAnd m_FourAre each independently of the other an integer from 1 to 7
And n₁Represents an integer of 1 to 5, and n_TwoIs 1, young
Represents an integer of 3 to 6, and m_FiveIs an integer from 1 to 7
I, n_TwoIs 3 to 6, n_TwoCOO (A_FiveO)
m_FiveR_FiveM in the base_FiveAnd R_FiveAre different from each other
It may well be the same. ) A group of compounds
You can choose from one.

The mono- and poly-alkylene glycol monoalkyl ethers used in the production of the above conductive ester compounds are addition compounds of propanol and 1 to 7 mol of ethylene oxide, 1 to 4 propylene oxide or 1 to 3 mol of butylene oxide. : Butanol, ethylene oxide 1-6 mol, propylene oxide 1-4
Addition compound with 1 to 3 mol or butylene oxide:
Addition compound of hexanol and ethylene oxide 1-5 mol, propylene oxide 1-3 mol or butylene oxide 1-2 mol: heptanol and ethylene oxide 1-
Addition compound of 5 mol, 1 to 3 mol of propylene oxide or 1 to 2 mol of butylene oxide: Octanol and 1 to 4 mol of ethylene oxide, addition compound of 1 to 3 mol of propylene oxide or 1 to 2 mol of butylene oxide: nonanol and ethylene oxide Addition compound of 1 to 4 moles, propylene oxide 1 to 2 moles or butylene oxide 1 to 2 moles: Addition compound of decanol and ethylene oxide 1 to 3 moles, propylene oxide 1 to 2 moles or butylene oxide 1 mole: dodecanol and ethylene oxide Addition compound of 1 to 2 mol, 1 mol of propylene oxide or 1 mol of butylene oxide: addition compound of tridecanol and ethylene oxide 1 to 2 mol, 1 mol of propylene oxide or 1 mol of butylene oxide: tetradecanol and ethylene Kishido 1 mole of propylene oxide to 1 mole and the addition compounds: and and addition compounds of pentadecanol with ethylene oxide 1 mole may be exemplified.

Examples of the dicarboxylic acid used for producing the conductive ester compound of the above formula (I) include adipic acid, azelaic acid, sebacic acid, succinic acid, brassic acid, tetrahydrophthalic acid and phthalic acid. .

The carboxylic acid used in the production of the conductive ester compounds of the above formulas (II) and (III) is a monocarboxylic acid, a trivalent or higher polyvalent carboxylic acid, or a divalent epoxycyclohexane ring. It is a carboxylic acid. These carboxylic acids may have a substituent containing a heteroalkyl such as a lower alkyl group such as a methyl group or an ethyl group, a hydroxyl group, oxygen, silicon, or a halogen.

As the monocarboxylic acid, an aliphatic monocarboxylic acid having 2 to 22 carbon atoms can be used. Further, the polybasic acid is an aliphatic, alicyclic or aromatic polybasic acid composed of a carboxylic acid residue having 3 to 8 carbon atoms, and specifically, citric acid, aconitic acid, butanetricarboxylic acid,
Aliphatic polycarboxylic acids such as butanetetracarboxylic acid, alicyclic carboxylic acids such as epoxyhexahydrophthalic acid, aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid, and acid anhydrides of these carboxylic acids The thing etc. can be used. These carboxylic acids may be used alone or as a mixture of two or more.

In the present invention, when the above-mentioned conductive plasticizer is mixed in the base material of the resin layer, the conductive plasticizer has the same chemical and physical characteristics as those of general plasticizers. Therefore, the amount of the other plasticizer added can be appropriately reduced according to the amount of the conductive plasticizer added.

As the conductive organic material, a conductive polymer material such as π-electron conjugated polymer material such as polyacetylene or polyphenylene, a metal coordination polymer material such as metal phthalocyanine, tetrathiofulvalene and tetracyanoxy A charge transfer complex polymer material composed of an electron donor and an electron acceptor such as a dimethane complex, or a quaternary ammonium salt-type polymer material, a chlorosulfonic acid-type polymer material, or the like can also be used. .

The content of the conductive organic material is not particularly limited, but it is preferable to set the content of the additive substance in the base material within the range of 1 to 70% by weight.

To mix and knead the flexible polymer resin base material, the amorphous metal powder and the different additives, a conventional method such as roll kneading, mixer mixing, kneader kneading or the like may be used.

The amorphous metal-containing flexible sheet of the present invention may have both an amorphous metal-containing resin layer and a resin layer containing no amorphous metal.

The resin layer containing no amorphous metal is
Non-amorphous metal powder, non-metal conductive material powder,
It may be a conductive layer containing a conductive organic material and / or a semi-conductive layer, or may be an insulating layer not containing them.

The base cloth used for the amorphous metal-containing flexible sheet of the present invention is made of a fiber material. The fibers used for the base fabric include natural fibers such as cotton and hemp, inorganic fibers such as glass fibers, carbon fibers and metal fibers, recycled fibers such as viscose rayon, and cupra such as semi-synthetic fibers. For example, cellulose di- and triacetate fibers and the like, and synthetic fibers such as nylon 6, nylon 66, polyester (polyethylene terephthalate), aromatic polyamide, aromatic polyester, acrylic polymer, polyvinyl chloride, vinylon, and polyolefin fibers. It can be selected from among, and particularly high strength fiber (15 to 50 g /
d) and / or high heat resistant fibers and the like can also be used.

The fibers in the base fabric are short fiber spun yarn, long fiber yarn,
It may be in any shape such as a split yarn or a tape yarn, and the base fabric may be any of a woven fabric, a knitted fabric, a non-woven fabric, a paper-like product, and a composite sheet of two or more of these. . Generally, the fibers used in the amorphous metal-containing flexible sheet of the present invention are preferably polyester fibers, and the fibers are preferably in the form of long fibers (filaments). The fibrous base fabric is useful for maintaining the mechanical strength of the obtained amorphous metal-containing flexible sheet at a high level.

The woven fabrics useful in the present invention include twill weaves, plain weaves, leno weaves, warp weaves, special knitted woven fabrics and other woven fabrics having a general structure.

In the amorphous metal-containing flexible sheet of the present invention, at least one resin layer containing an amorphous metal is formed on one side or both sides of the base cloth. This amorphous metal-containing resin layer has a flexible polymer resin as a base material, in which a mixture of amorphous metal powder particles and a conductive material additive different from that is dispersed. Is. The amorphous metal-containing resin layer may be directly adhered to the base cloth, or may be adhered via another intermediate layer containing no amorphous metal. The amorphous metal-containing flexible sheet of the present invention may have an upper surface resin layer containing no amorphous metal.

In order to form a resin layer containing or not containing an amorphous metal on the base cloth, a calendering method, laminating method, topping method, coating method, impregnation method or other coating method can be used.

The amorphous metal-containing flexible sheet of the present invention has an excellent protective effect for electronic equipment.

The effect of protecting the electronic equipment is that the electromagnetic field wave energy is absorbed or reflected by the electromagnetic field wave shielding means so that the electronic equipment is not affected by the electromagnetic field wave energy. Say. The degree of electromagnetic field wave energy attenuation by the electromagnetic field wave shield means is expressed in a unit decibel (dB), and as the electromagnetic field wave shield material has a larger value, the attenuation effect is larger, which is preferable. Generally, the electromagnetic wave shielding effect is preferably 10 dB or more, and 30 dB
More preferably, it is more preferably 60 dB or more, further preferably 90 dB or more.

The amorphous metal-containing flexible sheet of the present invention has the following properties in terms of the conventional electromagnetic field wave shielding material such as a rigid plastic molding, a metal material, and a metal foil.
Dimensional shape, mechanical strength, flexibility, and the convenience of use are eliminated, and it can be processed into any size, thickness, and shape, and has sufficient mechanical strength and flexibility. However, it can withstand the harsh conditions of use as a tent or covering sheet. Furthermore, the amorphous metal-containing flexible sheet of the present invention exhibits sufficient flexibility and flexibility even if it has a considerable thickness, is easy to bond and sew, and has excellent appearance and touch.

Further, the amorphous metal-containing flexible sheet of the present invention can be easily attached to other materials, has good conformability to any size and shape, and can be easily and easily operated to shield electromagnetic wave waves. It is possible to obtain various products having

[0041]

EXAMPLES The present invention will be further described below with reference to examples. Examples 1 to 7 and Comparative Examples 1 to 3 The following polyester spun yarn plain woven fabric was used as the base fabric in each of the Examples and Comparative Examples. The above cloth was scoured and dried by a conventional method.

A resin composition liquid for forming a resin layer was prepared with the composition shown in Table 1.

The base cloth is dipped in the resin composition liquid, squeezed, and
It was pre-dried at 0 ° C, gelled and fixed at 180 ° C, cooled and wound.

The thickness of the obtained flexible sheet is about 0.65 mm, and its tensile strength is 165 kg / 3 in the longitudinal direction.
cm, the weft direction was 132 kg / 3 cm, and the electromagnetic wave shielding effect was as shown in Table 1.

The electromagnetic field wave shield effect was measured by a near field electromagnetic wave shield material evaluator (TR-1730 manufactured by Takeda Riken.
1) and a spectrum analyzer (TR-4172) were used together, and a magnetic field wave and a plane wave were performed [all 1
Shown as an average value from 00MHz to 600MHz]

[0046]

[Table 1]

[0047] In each of Examples 8-14 Example 8-14, respectively, Examples 1
The same operation was performed for each of Nos. 7 and 7. However, the spun yarn plain woven fabric has the following composition: And immerse it in a colorless resin liquid containing no amorphous metal powder, squeeze it, and pre-dry it at a temperature of 150 ° C.
At this temperature, gelation was fixed, cooling and winding were performed, whereby a pretreated cloth having a resin adhesion amount of about 120 g / m ² was prepared. An amorphous metal-containing resin layer was formed on the pretreatment cloth having the resin layer containing no amorphous metal, as in Examples 1 to 7, to prepare an amorphous metal-containing flexible sheet. The amorphous metal-containing flexible sheet had a thickness of about 0.75 mm.

Each of the amorphous metal-containing flexible sheets exhibited the same electromagnetic wave shielding effect as the corresponding amorphous metal-containing flexible sheets of Examples 1 to 7.

In each of the amorphous metal-containing flexible sheets of Examples 8 to 14, since the resin layer containing no amorphous metal is formed between the base cloth and the amorphous metal-containing resin layer, the base cloth, The amorphous metal-containing resin layer was firmly bound by the resin layer containing no amorphous metal, and the amorphous metal-containing flexible sheet had excellent durability as a whole.

On one side of each of the above-mentioned amorphous metal-containing flexible sheets, a KFC sheet having a thickness of 50 μm (a trademark of a three-layer structure film of vinylidene fluoride polymer resin layer / acrylic polymer resin layer / vinyl chloride polymer resin layer, Kureha Chemical Co., Ltd.) was heat-bonded so that the surface of the vinyl chloride polymer tree layer was adhered.

Then, the amorphous metal-containing resin layer of the amorphous metal-containing flexible sheet and the KFC sheet were extremely firmly adhered to each other.

In this way, the vinylidene fluoride polymer resin layer forming the outermost surface layer of the amorphous metal-containing flexible sheet formed a surface having extremely high antifouling property.

That is, the flexible laminated sheet thus obtained exhibited excellent electromagnetic wave shielding properties, antifouling properties and durability.

[0054]

Industrial Applicability The amorphous metal-containing flexible sheet of the present invention is at least selected from amorphous metal powder particles, non-metal conductive material powder particles and conductive organic material, which are laminated on a base cloth made of a fiber material. A coating layer containing a kind of conductive material additive shows good electromagnetic field wave shielding property, and further, by using different kinds of non-amorphous metal powder particles together, the electric field wave shielding property can be further improved. And has mechanical strength sufficient for practical use.

Further, in the case where an existing electronic device is shielded by an electromagnetic field wave, it is preferable to store this device in a separately prepared electromagnetic field wave shielding case before use.
In this case, the amorphous metal-containing flexible sheet of the present invention can be easily attached to any shape and size of such a case to improve its shielding property.

As described above, the amorphous metal-containing flexible sheet of the present invention is used as a sheet for shielding from the influence of electromagnetic field waves of electronic equipment and the like, a film structure material, a wall (equipment) material, a cover, a floor material, It can be used in a wide variety of applications such as floor sheets.

Claims (7)

(57) [Claims] 1. A base fabric made of a fibrous material, and at least one resin layer formed on at least one surface of the base fabric and having a flexible polymer resin as a base material. At least one of the resin layers is at least one selected from amorphous metal powder particles dispersed in the flexible polymer resin matrix, non-metal conductive material powder particles, and conductive organic materials. An amorphous metal-containing flexible sheet, comprising: 2. The amorphous metal-containing flexible sheet according to claim 1, wherein the amorphous metal powder particles have a conductive metal plating layer formed on at least a part of the outer peripheral surface thereof. 3. The amorphous metal-containing flexible sheet according to claim 1, wherein at least one of the resin layers further includes a non-amorphous metal powdery substance different from the amorphous metal powdery substance. 4. The non-amorphous metal powder is copper,
Nickel, cobalt, iron, aluminum, gold, silver, tin,
The amorphous metal-containing flexible sheet according to claim 3, which is selected from zinc, a compound containing at least one of these, and an alloy powder. 5. The amorphous metal-containing flexible sheet according to claim 1, wherein the non-metal conductive material powder is selected from carbon black, graphite, and carbon fiber. 6. The amorphous metal-containing flexible sheet according to claim 1, wherein the conductive organic material is selected from a conductive plasticizer and a conductive polymer material. 7. An electromagnetic wave shielding article comprising at least one amorphous metal-containing flexible sheet according to any one of claims 1 to 6.