JPH0222333A - Amorphous metal-containing flexible sheet - Google Patents

Abstract

PURPOSE:To obtain a sheet of an optional shape having at least one layer containing a matrix of a flexible polymer resin and an amorphous metal powdery or granular substance dispersed therein with excellent electromagnetic field wave shielding properties. CONSTITUTION:A flexible sheet having at least one layer containing a matrix consisting of a flexible polymer resin and an amorphous metal powdery or granular substance dispersed therein. An amorphous metal powdery or granular substance having an electrically conductive metal plating layer in at least part of an outer peripheral surface thereof is used as the above-mentioned amorphous metal powdery or granular substance. A nonamorphous metal powdery or granular substance, nonmetal electrically conductive material powdery or granular substance and electrically conductive organic material are further blended as an electrically conductive material additive. A resin layer is formed on at least one surface of a fiber base fabric.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an amorphous metal-containing flexible sheet. More specifically, the present invention relates to a flexible sheet containing amorphous metal powder and having excellent electromagnetic shielding properties.

[Prior art and problems to be solved by the invention] In recent years, with the rapid progress of electronic devices, cases are increasing where these devices are used closely together or used as high power products. .

When using such electronic devices, it is necessary to protect them from the negative effects of static electricity and electromagnetic waves to prevent troubles such as breakdowns and malfunctions.

Conventionally, in order to solve the above-mentioned problems, measures have been adopted, such as housing the device body in a conductive housing and sealing it, or housing the device in a conductive storage case. A conductive case is a rigid container made of conductive plastic obtained by mixing a conductive substance with a molding material such as plastic, or a conductive case is a rigid container made of conductive plastic that is obtained by mixing a conductive substance with a molding material such as plastic, or a conductive case is a non-conductive case with conductive paint applied to the surface. It was manufactured using methods such as coating.

However, when a large number of electronic devices are distributed and used in a factory or office, these devices must be individually controlled to prevent electromagnetic field waves from dispersing to the outside, and to prevent electromagnetic field waves from emitting from the outside. It is necessary to prevent intrusion. For this reason, it is desirable to cover each device with a flexible cover sheet or membrane structure that has antistatic properties and electromagnetic shielding properties.

Attempts have been made to use metal plates or metal foils as sheet materials for the above purposes, but their rigidity has limited their use to specific applications and shapes.

In view of the above problems, the product should have high anti-static properties and electromagnetic shielding properties, be flexible, be easily processed into the desired shape, and be easily adapted to the shape and usage conditions of the equipment to be used. There was a strong desire to develop a flexible sheet that could

[Means to solve the problem]

The amorphous metal-containing flexible sheet of the present invention is
It has at least one resin layer including a base material made of a flexible polymer resin and amorphous metal powder dispersed therein.

Another amorphous metal-containing flexible sheet of the present invention includes a base material made of a flexible polymer resin, amorphous metal powder dispersed therein, and at least one conductive material additive of a different type. It has at least one resin layer including.

Another flexible sheet of the present invention also contains an amorphous metal, and has a structure including a base fabric made of a fiber material, and a flexible polymer resin formed on at least one surface of the base fabric. and at least one resin layer serving as a base material, wherein at least one layer of the resin layer includes amorphous metal powder dispersed in the flexible polymer resin base material. It is something to do.

In another flexible sheet according to the present invention, the at least one resin layer includes an amorphous metal powder dispersed in the flexible polymer resin matrix and at least one species different from the amorphous metal powder. It may also contain a conductive material additive.

That is, in such a flexible sheet of the present invention, the at least one resin layer includes a base material made of a flexible polymer resin and amorphous metal powder dispersed therein, or amorphous metal powder. conductive material and a dissimilar conductive material additive.

The flexible sheet of the present invention having at least one amorphous metal-containing resin layer is included as a component in various electromagnetic shielding products. Such an electromagnetic wave shielding article of the present invention includes a film-like structure,
It includes wall materials, covering materials, floor materials, floor sheet materials, and other articles of various shapes and sizes.

The flexible polymer resin 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,
It can be selected from polyurethane rubber, butyl rubber, fluorine-containing rubber, silicone rubber, isoprene rubber, etc. The most preferred synthetic resin is PVC, which may contain plasticizers, fillers, colorants, stabilizers and/or 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 spherical, granular, flaky, fibrous, etc., and the size may vary depending on the size. There is no limitation, but generally O,1~
Something around 5 dragons is preferable. The content of amorphous metal powder in the base material is not particularly limited as long as the purpose of the present invention is achieved, but it is generally preferably 1 to 70% by weight, and 3 to 50% by weight. It is more preferable that there be.

The amorphous metal used in the present invention is generally selected from amorphous alloys obtained by adding one or more selected from boron, silicon, carbon, nickel, cobalt, molybdenum, etc. to iron as a main component. It is preferable that For example, Allied's product name METGLM
SN [12602SC (Fe: 81%, B:
13.5%, Si: 3.5%, C: 2% amorphous alloy), m2605 S-2 (Fe: 78%, B
:13%, Si:9% amorphous alloy), 11h
2605-Co (Fe: 87 parts, B: 14 parts, 5il
1 part, CO: 18 parts amorphous alloy), Na28
26-MB (Fe: 40%, Ni: 38%, Mo: 4%
, B: 18% amorphous alloy), etc. can be used.

In addition to the above-mentioned alloys containing iron as the main component, alloys containing cobalt as the main component (for example, C0qoZ7o+C07
8SjlOB+21 C05hCrzhC+e+ C0
44M0ti+Cz.

Coff4CrzJozoC+ a), alloy system whose main component is nickel (e.g. Ni*oZr+o+ N1ta
Si+oB+z.

NizaCrtaWIOtaClm), and other metal-based alloy systems (e.g. PdB (ISi2o
, Cu5oZrzo+NtlSONjSO+ Ti5
oCuso) etc. can also be used.

The amorphous metal powder as described above provides the flexible sheet of the present invention with good electromagnetic field wave shielding properties, particularly magnetic field wave shielding properties.

The amorphous metal powder used in the present invention may have a plating layer made of a conductive metal formed on at least a portion of its outer peripheral surface. Such a conductive metal plating layer is effective in further improving the electromagnetic shielding properties of the flexible sheet of the present invention, and particularly in enhancing the electromagnetic shielding effect.

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

In the flexible sheet of the present invention, the amorphous metal-containing resin layer contains at least one conductive material additive of a different type in addition to the amorphous metal powder dispersed in the flexible polymer resin matrix. May contain.

Conductive material additives useful in the present invention can be selected from non-amorphous metal powders, non-metallic conductive material powders, and conductive organic materials.

Non-amorphous metal powder has good conductivity and electromagnetic shielding effect, especially electric field wave shielding effect, such as copper, nickel, cobalt, iron, aluminum, gold,
Silver, tin, zinc, and compounds containing at least one of these, and alloys such as stainless steel, brass,
It can be selected from bronze, nickel silver, etc., and these may be any of spherical bodies, granular bodies, flaky bodies, and fibrous bodies, and the size thereof is about 0.1 to 5 haze. Preferably, the content in the base material is set so that the total content 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, etc., and its size and content can be set similarly to those of the non-amorphous metal powder. I can do it.

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

The conductive plasticizer is, for example, a polycarboxylic acid ester compound of 7-N and poly-alkylene gellicol monoalkyl ether, and includes, for example, the following maximum (1).
, (II) and (■): Z (Coo(
AsO)IRs) nZ (DI) (wherein, in the above formula, Y represents a member selected from epoxidized cyclohexane rings with and without substituents; Z represents an aliphatic, alicyclic and aromatic group having 2 to 22 carbon atoms; represents a member selected from polybasic carboxylic acid residues; A+, Az, A!, A4 and A each independently represent a member selected from alkylene groups having 2 to 4 carbon atoms; R+, RzR3,R
4 and R2 each independently represent a member selected from straight chain and branched chain alkyl groups having 1 to 15 carbon atoms, provided that A, R1, A2, R2, and A, R3 each have a carbon atom number N of The total is 5 to 17, m,, m2,
m3 and m4 each independently represent an integer of 1 to 7, n represents an integer of 1 to 5, n2 represents 1 or an integer of 3 to 6, and l represents an integer of 1 to 7. When n2 is 3 to 6, n2 C00(AsO)
IRs base! and R5 may be different from each other or may be the same. ) can be selected from a group of compounds represented by

The mono- and poly-alkylene glycol monoalkyl ethers used in the production of the above-mentioned conductive ester compound include propatool and 1 to 7 moles of ethylene oxide, 1 to 4 moles of propylene oxide, or 1 to 4 moles of butylene oxide.
Addition compound with 3 moles: Addition compound between butanol and 1 to 6 moles of ethylene oxide, 1 to 4 moles of propylene oxide, or 1 to 3 moles of butylene oxide: Addition compound of hexanol with 1 to 5 moles of ethylene oxide, 1 mole of propylene oxide
-3 mol or addition compound with 1-2 mol of butylene oxide: heptanol with 1-5 mol of ethylene oxide, 1-3 mol of propylene oxide or 1-2 mol of butylene oxide
Addition compound with octanol and 1 to 4 mol of ethylene oxide, 1 to 3 mol of propylene oxide or 1 to 2 mol of butylene oxide: Addition compound of nonanol with 1 to 4 mol of ethylene oxide, 1 to 2 mol of propylene oxide
mol or addition compound with 1 to 2 mol of butylene oxideAddition compound of nidodecanol with 1 to 3 mol of ethylene oxide, 1 to 2 mol of propylene oxide or 1 mol of butylene oxideNidodecanol with 1 to 2 mol of ethylene oxide, 1 mol of propylene oxide or butylene Addition compound of nitridecanol with 1 mole of oxide; Addition compound of nitridecanol with 1 to 2 moles of ethylene oxide, 1 mole of propylene oxide, or 1 mole of butylene oxide; Addition compound of tetradecanol with 1 mole of ethylene oxide, 1 mole of propylene oxide; Examples include addition compounds of pentadecanol and 1 mole of ethylene oxide.

Further, dicarboxylic acids used in the production of the conductive ester compound of formula (1) include adipic acid, azelaic acid, sebacic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, phthalic acid, and the like.

In addition, the carboxylic acids used in the production of the conductive ester compounds of the above formulas (n) and (1) are monocarboxylic acids, polyvalent carboxylic acids of trivalent or higher valence, or divalent carboxylic acids having an epoxycyclohexane ring. be. These carboxylic acids may have a substituent containing a lower alkyl group such as a methyl group or an ethyl group, a hydroxyl group, or a heteroatom such as oxygen, silicon, or halogen.

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

In the present invention, when the conductive plasticizer as described above is mixed into the base material of the resin layer, the conductive plasticizer has chemical and physical properties similar to those of the fishing plasticizer. Therefore, depending on the amount of this conductive plasticizer added, the amount of other plasticizers added can be reduced as appropriate.

Conductive organic materials include conductive polymer materials such as π-electron conjugated polymer materials such as polyacetylene and polyphenylene, metal coordination polymer materials such as metal phthalocyanine, and tetrathiofulvalene and tetracyanoxydimethane complexes. It is also possible to use a charge transfer complex polymer material consisting of an electron donor and an electron acceptor such as the above, a quaternary ammonium salt type polymer material, a chlorsulfonic acid type polymer material, or the like.

The content of the conductive organic material is not particularly limited, but it is preferably set within a range such that the total content of additive substances in the base material is 1 to 70% by weight.

A flexible polymer resin base material, an amorphous metal powder,
Conventional methods are used to mix and knead different additives if necessary.
For example, roll kneading, mixer mixing, kneader mixing, etc. may be used.

The flexible sheet of the present invention may have both an amorphous metal-containing resin layer and, in addition, a resin layer that does not contain an amorphous metal.

The resin layer that does not contain an amorphous metal may be a conductive layer containing a non-amorphous metal powder, a non-metallic conductive material powder, and/or a conductive organic material, or may be semiconductive, Alternatively, an insulating layer that does not contain these may be used.

The base fabric used in the flexible sheet of the present invention is composed of a fibrous material. The fibers used for the base fabric include natural fibers such as cotton and linen, inorganic fibers such as glass fibers, carbon fibers and metal fibers, recycled fibers such as viscose rayon and cupro, semi-synthetic fibers, such as cellulose di- and triacetate fibers, as well as synthetic fibers such as nylon 6, nylon 66, polyester (polyethylene terephthalate)
, aromatic polyamides, aromatic polyesters, acrylic polymers, polyvinyl chloride, vinylon, and polyolefin fibers, especially high-strength fibers (
15 to 50 g/d) and/or highly heat resistant fibers can also be used.

The fibers in the base fabric may be in any form such as short fiber spun yarn, long fiber yarn, split yarn, tape yarn, etc., and the base fabric may be woven, knitted, nonwoven, paper-like, and Any composite sheet of two or more of these may be used. Generally, the fibers used in the sheet of the present invention are preferably polyester fibers, and these fibers are preferably in the form of long fibers (filaments). The fibrous base fabric is useful for maintaining high mechanical strength of the resulting sheet.

Further, useful woven fabrics include twill weave, plain weave, leno weave, leno weave, special knitted fabric, and other common textures.

In the flexible sheet of the present invention, at least one layer containing an amorphous metal is formed on one or both sides of the base fabric.
A layer of resin is formed. This amorphous metal-containing resin layer has a flexible polymer resin as a base material, and contains amorphous metal powder or amorphous metal powder and a conductive material additive of a different type. The mixture is dispersed. This amorphous metal-containing resin layer may be directly bonded to the base fabric, or may be bonded via another intermediate layer that does not contain an amorphous metal. Moreover, the flexible sheet of the present invention is
It may have an upper surface resin layer that does not contain an amorphous metal.

To form a resin layer containing or not containing an amorphous metal on a base fabric, a calendering method, a laminating method,
Topping methods, coating methods, impregnation methods and other covering methods can be used.

The flexible sheet of the present invention has an excellent protective effect on electronic equipment.

The protective effect of electronic equipment refers to the effect of absorbing or reflecting electromagnetic energy by an electromagnetic shielding means to prevent the influence of electromagnetic energy from reaching the electronic equipment. The degree of electromagnetic field energy attenuation by this electromagnetic field wave shielding means is expressed in units of decibels (dB), and the larger this value is, the greater the attenuation effect is, which is preferable for the electromagnetic field wave shielding material. Generally speaking, the electromagnetic field wave shielding effect is
It is preferably 10 dB or more, more preferably 30 dB or more, even more preferably 60 dB or more, and even more preferably 90 dB or more.

The flexible sheet of the present invention has advantages over conventional electromagnetic shielding materials, such as rigid plastic moldings, metal materials, and metal foils, in terms of performance, size, shape, mechanical strength, flexibility, and convenience of use. A product that eliminates the defects, can be processed into any size, thickness, and shape, has sufficient mechanical strength and flexibility, and can withstand harsh usage conditions as a tent material or covering sheet material. It is. Furthermore, the flexible sheet of the present invention exhibits sufficient flexibility and flexibility even when it is considerably thick, is easy to adhere and sew, and has an excellent appearance and feel.

In addition, the 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 simply operated to produce various products with electromagnetic shielding properties. Obtainable.

〔Example〕

The present invention will be further explained below with reference to Examples.

1-15 and 1-2 In each of the Examples and Comparative Examples, the following polyester spun yarn plain woven fabric was used as the base fabric.

10 S/I
The above fabric was scoured and dried in a conventional manner.

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

The base fabric was immersed in the resin composition liquid, squeezed, pre-dried at 150°C, gelled and fixed at 180°C, cooled and rolled up.

The thickness of the obtained flexible sheet was approximately 0.65 mm, and its tensile strength was 165 kg/3 cm in the radial direction.
It was 132 kg/3 ctrr in the latitudinal direction, and its electromagnetic shielding effect was as shown in Table 1.

The electromagnetic field wave shielding effect was measured for magnetic field waves and plane waves using Takeda Riken's Proximity Shoryu Magnetic Wave Shield Material Evaluator (TR-17301) and Spectrum Analyzer (TR-4172) [both at 100MIIz]
Shown as an average value at ~600 MHz] Actual f Using the same resin composition as in Example 1, except that the solvent was removed, the resin composition was calendered to a thickness of 0.3 MHz.
An extremely flexible film of Tsuru was produced. The magnetic field wave shielding effect of this film was approximately 52 dB, and the electric field wave shielding effect was 60 dB. When this film was applied as a lining to the entire inside of a television box, it was easily applied and showed good electromagnetic shielding properties.

11th Earthwork A flexible film with a thickness of 0.3 am was prepared by the procedure described in Example 16 from the same resin composition as in Example 6 except that the solvent was removed. This film has a magnetic field wave shielding effect of approximately 60 dB and a
It showed an electric field shielding effect of 0 dB.

Actual Situation ■Earthwork Using the same composition as in Example 5, but excluding the solvent, the thickness was 0.0 mm as described in Example 16.
A flexible film of 3 am was prepared.

This film has a magnetic field wave shielding property of approximately 74 dB and approximately 66 dB.
Demonstrated dB electric field shielding properties.

Using the same composition as in Example 3, except for the solvent, a thickness of 0 was prepared as described in Example 16.
．． A 3M flexible film was created.

This film exhibited a magnetic field wave shielding effect of about 72 dB and an electric field wave shielding effect of about 68 dB.

Ura Seed ■1 Work A flexible film having a thickness of 0.3 fin was prepared in the same manner as in Example 16 using the same composition as in Example 4 except that the solvent was removed.

This film has a magnetic field wave shielding property of approximately 72 dB,
It showed an electric field shielding property of about 67 dB.

Implementation ■ In each of Examples 21 to 35, Example 1
The same operation as this was performed corresponding to each of 15 to 15.

However, the spun yarn hand-woven fabric has the following composition: PVC resin.
100 parts O, P, 70 parts CdBa-based stabilizer 3 parts Toluene (solvent) 130 parts, immersed in a colorless resin liquid containing no amorphous metal powder, squeezed and pre-dried at a temperature of 150 ° C. ,180℃
The fabric was gelatinized and fixed at a temperature of about 120 g/m, cooled, and rolled up, thereby producing a pretreated fabric with a resin coverage of about 120 g/m. An amorphous metal-containing resin layer was formed on this pretreated cloth having a resin layer not containing an amorphous metal in the same manner as described in Examples 1 to 15 to prepare a flexible sheet. This sheet had a thickness of approximately 0.75 mm.

Each flexible sheet corresponds to Example 1~
It showed the same electromagnetic shielding effect as No. 15 flexible sheet.

The flexible sheets of Examples 21 to 35 each had
Since a resin layer that does not contain an amorphous metal is formed between the base fabric and the amorphous metal-containing resin layer,
The base fabric and the amorphous metal-containing resin layer were firmly bound by this amorphous metal-free resin layer, and the flexible sheet had excellent durability as a whole.

On one side of each of the above flexible sheets, a 50n thick KFC sheet (trademark for a three-layer structure film of vinylidene fluoride polymer resin layer/acrylic polymer resin N/vinyl chloride polymer resin layer, manufactured by Kureha Chemical Co., Ltd.) was placed on one side of each of the above flexible sheets. The vinyl chloride polymer tree layer surfaces were bonded together by heating and pasting.

Then, the amorphous metal-containing resin layer of the 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 flexible sheet formed a surface with extremely high stain resistance.

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

In each of Examples 36 to 40, the same operations as in the corresponding Examples 16 to 20 were performed. However, on one side of the obtained flexible sheet, PVC with a thickness of 0.1 +
A film was attached, and the same KFC film as described in Examples 21 to 35 was similarly attached to the other side.

The obtained flexible sheet exhibited excellent electromagnetic shielding properties, stain resistance, and durability as in Examples 16 to 20, and the surface of the attached PvC film layer was completely resistant to other articles. It showed excellent adhesion.

〔Effect of the invention〕

The flexible sheet of the present invention has good electromagnetic shielding properties due to the coating layer containing amorphous metal powder, and further improves the electromagnetic shielding properties by using different types of conductive additives together. can be done.

Furthermore, when shielding existing electronic equipment from electromagnetic waves, it is preferable to use the equipment by storing it in a separately prepared electromagnetic shielding case. In this case, the flexible sheet of the present invention can be used in any of such cases. It can be easily attached to objects with such shapes and dimensions to improve their shielding properties. In such a case, the flexible sheet of the present invention may or may not contain a fiber material base fabric.

As described above, the flexible sheet of the present invention can be used as a sheet for shielding electronic equipment from the influence of electromagnetic waves, such as membrane structure materials, wall (covering) materials, coverings, flooring materials, floor sheets, etc. It can be used in a wide range of applications.

Claims (1)

[Scope of Claims] 1. An amorphous metal-containing flexible sheet having at least one resin layer including a base material made of a flexible polymer resin and amorphous metal powder particles dispersed therein. 2. The sheet according to claim 1, wherein the amorphous metal powder has a conductive metal plating layer formed on at least a portion of its outer peripheral surface. 3. At least one resin layer comprising a base material made of a flexible polymer resin, amorphous metal powder dispersed therein, and at least one conductive material additive of a different type. An amorphous metal-containing flexible sheet with 4. The sheet according to claim 3, wherein the conductive material additive is selected from non-amorphous metal powder, non-metallic conductive material powder, and conductive organic material. 5. A base fabric made of a fiber 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 An amorphous metal-containing flexible sheet, wherein one layer includes amorphous metal powder particles dispersed in the flexible polymer resin matrix. 6. The sheet according to claim 5, wherein the amorphous metal powder has a conductive metal plating layer formed on at least a portion of its outer peripheral surface. 7. A base fabric made of a fiber 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, the resin layer at least one layer of the flexible polymer resin matrix comprises amorphous metal powder dispersed in the flexible polymer resin matrix and at least one conductive material additive different from the amorphous metal powder, Flexible sheet containing amorphous metal. 8. The sheet according to claim 7, wherein the conductive material additive is selected from non-amorphous metal powder, non-metallic conductive material powder, and conductive organic material. 9. An electromagnetic shielding article comprising at least one amorphous metal-containing flexible sheet according to any one of claims 1 to 8.