JPS6116846A - Electromagnetic shielding molded shape - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a molded product with excellent electromagnetic shielding properties. Specifically, the present invention relates to an electromagnetic shielding molded product made by integrating a fabric made of metal-coated fibers having a specific structure and a thermoplastic resin.

<Prior Art> Conventionally, metallized sheet materials have been known as electromagnetic shielding molded products. For example r O, 01~100O
In a reflective material for V-p-waves and high-frequency radiation within the GH2 (7) range, the reflective material is applied to a sheet-type fiber material of synthetic polymer or natural fiber, after activation, by a currentless wet process. By chemical deposition, 0.02-2.5μ, I
o) Application of metal with full metal layer thickness [, and metallization 1. ``The above-mentioned reflective material characterized by using a sheet-type fiber material'' (Japanese Unexamined Patent Application Publication No. 55-66106) has been proposed, and ``The reflective material is further coated with PVC.

"Applying a protective coating of rubber or polyurethane lacquer" and "this latter lamination increases the reflective power of the sheet-type material by 1. (the same publication, page 5, upper left column, line 20 to line 3, upper right column of the same page).

or "metalized sheet-type fibrous material arranged in several layers, with an insulating interlayer or surface lining or covering of unmetallized fabric, film or lacquer arranged between the individual metalized layers""Radiation shielding material"
(Japanese Unexamined Patent Publication No. 55-74200) is disclosed.

1. However, repeated bending stress is applied to the molded product made of metallized sheet material and resin.

In applications where abrasion stress etc. are applied, metallized 1-
1. When the molded product is integrated, the sheet material and the resin layer may peel off or the electromagnetic shielding properties may deteriorate.
Hand strength is reduced.

<Object of the Invention> The present invention has been made to solve these problems. That is, the present invention provides an electromagnetic shielding molding material that has improved bonding strength between the metallized sheet material and the resin layer and has improved electromagnetic shielding durability.

<Structure of the Invention> That is, the present invention consists of "(1) A metal-coated hollow polyester fiber containing a modified polyester copolymerized with an organic sulfonic acid compound represented by the following general formula (1) and having micropores on at least the surface. Electromagnetic shielding molded product X-Mu-Y (1) SO, Z formed by integrating a fabric and a thermoplastic resin.

The organic sulfonic acid compound here is represented by the following general formula +11.

X - A - Y (1) 0sZ A is an aromatic group or an aliphatic hydrocarbon group, and an aromatic group is more preferable. , x, and y are ester-forming functional groups, and specific examples include (1. R3 is a lower alkyl group or a phenyl group, a and C are an integer of 1 or more, and b is an integer of 2 or more). be able to. Y may be the same as or different from X. Among such organic sulfonic acid compounds, sodium (or potassium) 3,5-di(carbomethoxy)benzenesulfonate is particularly preferred.
, sodium (or potassium) 1,8-di(carbomethoxy)naphthalene-3-sulfonate, sodium (or potassium) 12,5-bis(hydroxyethoxy)benzenesulfonate, and the like.

In order to produce a modified polyester copolymerized with such an organic sulfonic acid compound, the organic sulfonic acid compound is added at any stage before the synthesis of the polyester described above is completed, preferably at any stage before the first stage reaction is completed. An acid compound may be added. The amount of the organic sulfonic acid compound to be used at this time is in the range of 2 to 16 molti based on the bifunctional carboxylic acid component (excluding the organic sulfonic acid component) mainly consisting of terephthalic acid that constitutes the modified polyester. preferable. The amount of the modified polyester to be blended with respect to the unmodified polyester is preferably 5 to 100 parts by weight of the modified polyester per 100 parts by weight of the unmodified polyester.

The micropore-forming agent is selected from the group consisting of phosphorus compounds or sulfonic acid compounds represented by the following general formula (11) or (11).

Cloud 2' where the range is a metal, particularly preferably an alkali metal, an alkaline earth metal, Mnl/2, Col/2 or Znl/, especially Ll + Na l K r Cat/
21Mg1/2 is particularly preferred 1. stomach. m is 0 or 1.

R is a monovalent organic group, specifically an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or +-fo■IF〒R'' (where R1/ is a hydrogen atom, an alkyl group, or a phenyl group, (t is an integer of 2 or more, p is an integer of 1 or more), etc. 2' is l and -R'111 (R"' is a monovalent organic group). R″′ and R may be the same and have a difference of 4) J%. A specific example of R″′ is R
is the same as

Preferred specific examples of such phosphorus compounds include monomethyl disodium phosphate, dimethyl monosodium phosphate, monophenyl dipotassium phosphate, monomethyl heptanomagnesium phosphate, monomethyl manganese phosphate, and polyoxyethylene (5 moles of KO added) lauryl ether. Potassium phosphate salt (805 mol addition means 5 mol ethylene oxide addition, hereinafter the same meaning), polyoxyethylene (5 mol EO addition), lauryl ether phosphate magnesium salt, polyoxyethylene (5 mol EO addition) ) Methyl ether phosphate sodium salt, monoethyl dipotassium phosphite, diphenyl monosodium phosphite, polyoxyethylene (E
050 mole addition) methyl ether phosphite disodium, phenylphosphonate monomethyl heptanosodium,
Examples include monomethyl heptanopotassium nonylbenzenephosphonate and monomethyl heptanosodium phenylphosphinate.

The sulfonic acid compound is represented by the general formula, where crab and is a metal, and crab is particularly an alkali metal, alkaline earth metal T Mnl/21Cot/2 or Znl/2
I-(, especially Li) is preferred.

Particularly preferred are Na, K, Cat/2, and Mgl/2. Especially preferred are alkali metals or alkaline earth metals, especially Ll + Na e C
Particularly preferred is at/2 + Mg1/2. and the range may be the same or different. n is 1 or 2. R
' is a hydrogen atom or an ester-forming functional group, and the ester-forming functional group is -COOR'' (However, RI
I/l is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group) or -CO(-0(C) (where t is 2
or more, p is an integer of 1 or more) Go is preferable.

Preferred specific examples of such sulfonic acid compounds include 3-
Sodium carbomethoxybenzenesulfonate-5
-Sodium carboxylate, sodium 3-carbomethoxybenzenesulfonate-potassium 5-carboxylate.

Potassium 3-carbomethoxybenzenesulfonate-5
- Potassium carboxylate, Sodium 3-hydroxyethoxycarbonyl benzenesulfonate - Sodium 5-carboxylate, Sodium 3-carboxybenzenesulfonate - Sodium 5-carboxylate, Sodium 3-hydroxyethoxycarbonyl benzenesulfonate -5-
Carboxylic acid Mgl/2, benzenesulfonic acid Na-
Sodium 3,5-dicarboxylate.

Benzenesulfonic acid Na-L5-dicarboxylic acid Mgl
/We meet by giving second place.

The blending amount of the above phosphorus compound or sulfonic acid compound is 0.3 to 0.3 to the acid component constituting the polyester to be added.
A range of 15 moles is appropriate, and a range of 0.5 to 5 moles is preferred.

When spinning polyester fibers blended with such a micropore-forming agent, a spinneret capable of producing the desired hollow fibers is used.

For example, in order to obtain a hollow fiber having a circular outer shape and a hollow part shape, a spinneret having a partially closed circular slit or a horseshoe-shaped opening can be used as the spinneret. The polyester fibers containing the micropore-forming agent obtained as described above are treated with an aqueous solution of an alkaline compound to dissolve and remove at least a portion of the micropore-forming agent, thereby performing an electroless plating treatment. Polyester fibers with micropores suitable for use can be obtained.

The metal plating method according to the present invention will be explained below.

First, a catalyst for chemical plating is provided.

There are two methods: a catalyst-imparting method, a sensitizing-activating method, and a catalyst-accelerator method. In the former method, a relatively strong reducing agent such as stannous chloride, monophosphorous acid, or hydrazine chloride is first adsorbed onto the fiber surface, and then the fiber is immersed in a catalyst solution containing noble metal ions such as gold, silver, or palladium. Alternatively, the fiber may be first immersed in a solution containing noble metal ions to adsorb the noble metal ions, and then reduced in a reducing agent solution. Alternatively, noble metals may be precipitated on the fiber surface and combined with the catalyst.

The latter method involves immersing the fibers in a tin-palladium mixed catalyst solution. After that, the catalyst is activated with an acid such as hydrochloric acid or sulfuric acid to precipitate palladium on the surface of the fiber.

After applying a catalyst using the method described above, chemical plating is performed, but metal salts are generally used for chemical plating.

It is possible to use a known chemical plating solution containing components such as a reducing agent and a pH adjuster.

Application to the fibers of the present invention 1 - Metals that can be plated include copper, nickel, silver, tin, cobalt, etc., but copper and nickel have the advantage of stability of liquid, adhesion between fiber and metal coating, etc. This is preferable from this point of view.

Fabrics include woven and knitted fabrics, non-woven fabrics, and net-like bodies.

A scrim or the like can be used. The molded product may have any shape as long as the metal-coated hollow polyester fibers are uniformly distributed and the bonds between the fibers are maintained.

The thermoplastic resin material may be any material as long as it is compatible with the molded product and has flexibility. For example polyester, polyamide or polyethylene.

Examples include polyolefin-based materials such as polypropylene, and vinyl-based materials such as polyvinyl chloride and polyacrylate. Conventionally known methods may be used to integrate the fabric made of metal-coated hollow polyester fibers and the thermoplastic resin. For example, coating or spraying a thermoplastic resin solution onto a fabric made of metal-coated hollow polyester fibers.1. After that, there are methods such as heat treatment to remove the solvent, bonding a thermoplastic resin film to the fabric with an adhesive, and coating the fabric with a thermoplastic resin melt.Polyester When using a resin that has a high affinity with the fabric, the fabric and the thermoplastic resin thin film may be laminated and then heat-pressure treated to fuse them.

<Effects of the Invention> As described in detail above, the present invention as constructed has the following effects.

(1) Improved peel strength between a fabric made of metal-coated hollow polyester fibers and a thermoplastic resin.

(2) The improvement in peel strength is particularly remarkable when bending stress or abrasion stress is applied to the molded product.

(3) Since the inner space of the hollow part of the metal-coated hollow polyester fiber is also coated with metal, there is no elongation stress.

Electromagnetic shielding performance does not deteriorate even when the molded body is deformed due to bending stress, abrasion stress, etc. applied to the molded body.

EXAMPLES Hereinafter, the method for manufacturing an electromagnetic shielding molded product of the present invention will be explained with reference to Examples. In the examples, parts or parts mean parts by weight.

Example 1. Comparative Example 1 was placed in a glass flask equipped with a rectification tower, and transesterification was carried out according to a conventional method. After the theoretical amount of methanol was distilled out, the reaction product was placed in a polycondensation flask equipped with a rectification tower, and transesterification was carried out as a stabilizer. Add 0.112 parts of trimethyl phosphate and 0.079 parts of antimony trioxide as a polycondensation catalyst,
The mixture was reacted for 20 minutes at a temperature of 280° C. under normal pressure, for 15 minutes under reduced pressure of 30 ml and 11 g, and then for 800 minutes under high vacuum. The final internal pressure was 0.38 mHg, and the resulting modified polymer had an intrinsic viscosity of 0.600 (solvent: orthofururphenol, 25°C) and a softening point of 258°C. After the reaction was completed, the modified polymer was made into chips according to a conventional method.

After drying this chip according to a conventional method, a spinneret and a circular slit with a width of 0,005 m+ and a diameter of 0.6 wa closed at two places (having an arc-shaped opening) were prepared. The yarn was spun according to a conventional method, and the ratio of outer diameter to inner diameter was 2:
A hollow fiber of No. 1 (hollowness ratio: 25 cm) was made. This yarn is 3
00 do/24 fil, and this yarn was drawn according to a conventional method at a draw ratio of 4.0 times to give 75 da/24 fil.
A 24fil multifilament was obtained. This fiber was subjected to alkali weight loss treatment (98°C).

The specimens were treated in a bath with an alkaline concentration of 20 f/l for 30 minutes, resulting in a weight loss of 15 inches. After washing with water, chemical plating was applied according to the steps shown below.

After washing with water, drying at 105°C for 5 dollars ↓ After washing with water, drying at 105°C for 5 minutes ↓ Washing and drying (10m+ at 105°C) As a result of nickel plating using this method, the resulting metal-plated fiber is similar to ordinary polyester. Ia, fa
Compared to the one plated with nickel using the above-mentioned method (Comparative Example 1), it exhibited a very uniform and aesthetically pleasing appearance. And friction test using Gakushinho friction fastness tester, 10
As shown in Table 1, even in a boiling test in 0°C boiling water, there was little shedding of the nickel plating layer, and it was recognized that the product had excellent robustness sufficient for practical use.

The thus obtained fibers were nickel-plated on the surface, and 1 hollow fiber with a fineness of 250 denier was used as the warp and weft, 95 pieces/inch in the warp direction and 1 piece in the weft direction.
A plain weave fabric was woven at a weave density of 0.5 strands/inch.The fabric was mixed with 100 parts by weight of epoxy acrylate resin (Neopol 8250T (■, manufactured by Nihon Yubika ■) and 0.5 parts by weight of cobalt naphthenate as a curing accelerator. Add and stir (2 parts by weight)
After curing, 1.0 parts by weight of methyl ethyl ketone peroxide was added as a curing agent and stirred. The plain woven fabric was impregnated with the obtained resin composition, drawn into a mold in the form of a sheet, and left in a hot air dryer at 100° C. for 3 hours to harden to obtain a molded product with a thickness of 1 mm. The electromagnetic shielding properties of the obtained samples were measured. Using the fabric according to the present invention 1. In this case, a shielding effect of 60 to 70 dB for electric field waves and 40 to 50 dB for magnetic field waves was obtained in the frequency band of 100 to 1000 MH.

Nickel plating is applied to a normal polyester fabric (comparative example 12, same structure as the inventive product).1. When we measured the electromagnetic shielding performance of a molded product made in the same way, the electric field wave was 40~
50 dB, and the magnetic field wave had a shielding effect of 30 to 40 dB.

When the center of the molded product was bent at 90°, the shielding performance for both electric field waves and magnetic field waves did not change in the product of the present invention, but the shielding performance for both electric field waves and magnetic field waves did not change with the product using ordinary polyester fabric.
dB or less, the magnetic field wave was OdB, and there was almost no shielding performance.

The electromagnetic shielding properties in the examples were measured using a shielding effect evaluator (TR-17301) and a spectrum analyzer (TR-4172) manufactured by Takeda Riken.

As described above, when the fabric according to the present invention is used, the adhesion of the plating film is good, and even after the molded product is bent, the metal film does not break and the shielding performance does not deteriorate. Ta.

Claims (1)

[Claims] (1) A fabric made of metal-coated hollow polyester fibers containing a modified polyester copolymerized with an organic sulfonic acid compound represented by the following general formula (I) and having at least micropores on the surface and a thermoplastic resin are integrated. Electromagnetic shielding molded product made of ▲Mathematical formulas, chemical formulas, tables, etc.▼...(I) [Here, A is an aromatic group or aliphatic hydrocarbon group, X and Y are ester-forming functional groups, and Z is an ester-forming functional group. It is a metal or a hydrogen atom. ]