JPS6099071A - Metal coated polyester fiber and its production - 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 polyester fibers whose surfaces are coated with metal and a method for producing the same, and particularly to polyester fibers and fibers in which the metal coating and polyester fibers have excellent adhesion properties. It is something.

Conventional technology Generally, when applying metal plating to synthetic fibers, it is necessary to roughen the surface by etching, but polyester fibers are relatively stable against acidic solutions, so they cannot be coated with alkaline solutions. Perform etching process. However, although polyester fibers etched with this alkaline solution can be metal-plated to some extent, the adhesion between the metal-plated film and the base material and the durability of the film when stretched are weak, which poses practical problems. .

Purpose of the Invention In view of the current situation, the present inventors have conducted intensive studies to improve the adhesion between polyester fibers and metal plating coatings and the durability of the coatings, and as a result they have arrived at the present invention.

Structure of the Invention That is, the present invention provides a polyester fiber whose surface is coated with a metal, wherein the fiber contains a modified polyester copolymerized with an organic sulfonic acid compound represented by the following general formula (11), and at least the surface of the fiber is coated with a metal. A metal-coated polyester fiber characterized by being a hollow fiber having micropores.

Contains a modified polyester copolymerized with an organic sulfonic acid compound represented by the following general formula +11, and has the following general formula (1
) and a sulfonic acid compound represented by the following general formula (1).Hollow polyester fibers containing a pore-forming agent selected from the group consisting of a phosphorus compound represented by A method for producing metal-coated polyester fiber, which comprises sequentially performing treatment, activation treatment, and electroless plating treatment.

Here, the organic sulfonic acid compound has the following general formula % Formula % A is an aromatic group or an aliphatic hydrocarbon group, but an aromatic group is more preferable. X and Y are ester-forming functional groups, and specific examples include -0(CH,)-Etan H→H, -C (Cru?Hb
be 11 (where bird is a lower alkyl group or phenyl group, a and C are an integer of 1 or more, and b is an integer of 2 or more), and the like. Y may be the same as or different from X. Particularly preferred examples of such organic sulfonic acid compounds include sodium (or potassium) 3,5-di(carbomethoxy)benzenesulfonate, sodium (or potassium) 1,S-di(carbomethoxy)naphthalene-3-sulfonate; ), sodium (or potassium) 2,5-bis(hydroxyethoxy)benzenesulfonate, and the like.

In order to produce a modified polyester obtained by copolymerizing such an organic sulfonic acid compound, it is preferable that 1- (preferably 1- The organic sulfonic acid compound may be added at this stage.The amount of the organic sulfonic acid compound used at this time is the same as the difunctional carboxylic acid component (excluding the organic sulfonic acid component) mainly composed of terephthalic acid that constitutes the modified polyester. The amount of the modified polyvarnish and chill in the unmodified polyester is preferably 5 to 100 parts by weight per 100 parts by weight of the unmodified polyester. The ratio is preferred.

The micropore forming agent is selected from the group consisting of phosphorus compounds or sulfonic acid compounds represented by the following general formula (1) or (11).

2' In the formula, M is a metal, particularly preferably an alkali metal, an alkaline earth metal, Mnl/2, Col/2 or Znl/2, especially LL+ Na, K, Cal/2
+ I especially like Mgl/2! Ft-i. m is 0 or l. R is a monovalent organic group, specifically a furkyl group, an aryl group, a furkylaryl group, an arylalkyl group, or ←0→3-R'' (However, R' is a hydrogen atom.

p alkyl group or phenyl group, t is an integer of 2 or more, p is 1
or larger integer), etc. are preferable. 2′ is.”

-R"', -Ml. (R"' is a -valent organic group) R"' and R may be the same or different and may be at a temperature of .degree.

The specific example of R″′ is the same as R.

Preferred specific examples of such phosphorus compounds include monomethyl disodium phosphate, dimethyl monosodium phosphate, monophenyl dipotassium phosphate, monomethyl 7/magnesium phosphate, monomethyl manganese phosphate, polyoxyethylene (Eo 5 mole addition) lauryl Ether phosphate potassium salt (1 (1, l=, 5 mol EO addition means 15 mol ethylene oxide addition, hereinafter the same meaning), polyoxyethylene (, 5 mol EO addition) lauryl ether phosphate magnesium salt , polyoxyethylene (EO50 mole addition) methyl ether phosphate sodium salt, monoethyl dipotassium phosphite, diphenyl monosodium phosphite, polyoxyethylene (EO50 mole addition) methyl ether phosphite disodium salt, phenylphosphonate monomethyl 7 Examples include sodium, monomethyl monopotassium nonylbenzenephosphonate, monomethyl heptanosodium phenylphosphinate, etc. The sulfonic acid compound is represented by the following general formula.

In the formula, M and M are metals, and M is particularly alkali metal, alkaline earth gold FL Mnl/2°Col
/2 or Znl/2 is preferred L-<, especially Li.

Particularly preferred are Na + K + Ca +/2 + Mg +/2.1. Li, M, and °C are particularly preferably alkali metals or alkaline earth metals, especially Li + Na
Particularly preferred are IlC, Cal/2, and Mgl/2, and M and M may be the same or different. n is l
Or 2. R' is a hydrogen atom or an ester-forming functional group, and the ester-forming functional group is IOOR""
(However, R″″ is a hydrogen atom, an alkyl group having carbons a1 to 4, or a phenyl group) or i0-(-cJ←H0) pH (
However, t is preferably an integer of 2 or more, p is an integer of 1 or more, etc.

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

Sodium 3-carbomethoxybenzenesulfonate-5-potassium carboxylate, Potassium 3-carbomethoxybenzenesulfonate-5-carboxylate, 3
-Hydroxyethoxycarbonyl penze/sodium sulfonate-sodium 5-carboxylate, sodium 3-carboxybenzenesulfonate-sodium 5-carboxylate, 3-hydroxyethoxycarbonyl benzenesulfonic acid N*-5-carboxylic acid Mgl/ 2,
Benzene sulfone 1lNa-3,5-dicarboxylic acid N
a, Na-benzenesulfonic acid, Mg172-3,5-dicarboxylic acid, and the like.

The blending amount of the above 313 phosphorus compound or sulfonic acid compound is 0.00% relative to the acid component constituting the polyester to be added.
A range of 3 to 15 moles is suitable, and a range of 0.5 to 5 moles is preferred. When spinning polyester fibers containing such a micropore-forming agent, use a spinneret that can obtain the desired hollow fibers. As a normal spinneret, one having a horseshoe-shaped opening in which a circular slit is partially closed can be used. The polyester fiber containing the micropore-forming agent obtained as described above is treated with an aqueous solution of an alkaline compound [7] Then, at least a part of the micropore-forming agent is dissolved and removed, thereby performing electroless plating treatment. It is possible to obtain polyester fibers having micropores suitable for.

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 hypophosphorous 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, and palladium. It is also possible to precipitate a noble metal on the fiber surface and coat it with a catalyst.Alternatively, the fiber surface is first immersed in a solution containing noble metal ions to adsorb the noble metal ions, and then reduced in a reducing agent solution. It is also possible to precipitate a noble metal as a catalyst.

The latter method is a method of providing a catalyst, which is typified by immersing fibers in a tin-palladium mixed catalyst solution and then activating the fibers with an acid such as hydrochloric acid or sulfuric acid to precipitate palladium on the surface of the fibers.

Catalyst application by the method described above 1. After that, chemical plating is performed. For chemical plating, it is possible to use a known chemical plating solution that generally includes components such as a metal salt, a reducing agent, and a pH adjuster.

Plated metals that can be applied to the fibers of the present invention include:
Examples include copper, nickel, silver, tin, cobalt, etc., and copper and nickel are preferred from the viewpoint of liquid stability and adhesion between fibers and metal coating.

The metal-plated polyester fiber according to the present invention has superior mechanical properties compared to conventional fibers.

The resulting polyester fiber has the adhesion of the fiber to the metal coating and the durability of the metal coating.

Hereinafter, the present invention will be specifically explained with reference to Examples. Parts are parts by weight.

Example 1. Comparative Example 1 was placed in a glass flask equipped with a rectification column, 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 column, and the mixture was sealed with a stabilizer. Adding 0.112 parts of nitrimethyl phosphate and 0.079 parts of 7thimony dioxide as a polycondensation catalyst,
After reacting at a temperature of 280° C. for 20 minutes under normal pressure and 15 minutes under a reduced pressure of 30 waH9, the reaction was carried out for 80 minutes under high vacuum. The final internal pressure was 0.38 ■■ g, and the intrinsic viscosity of the obtained modified polymer was 0.600 (solvent: orthochlorophenol, 25°C) Softening point +! The temperature was 258°C. After the reaction was completed, the modified polymer was made into chips according to a conventional method. The chips were dried according to a conventional method and used as a spinneret with a width of 0.
．． A circular slit with a diameter of 0.611111 mm and a diameter of 0.611111 closed at two places (with an arc-shaped opening) was used and spun according to a conventional method, so that the ratio of the outer diameter to the inner diameter was 2:
1 of hollow fibers ($25% hollow) were made. This yarn is 3
00 De/24 fll, and using this raw yarn, the yarn was stretched 1-17 sDθ/ at a stretching ratio of 4.0 times according to a conventional method.
24 fil of multifilament was obtained. This fiber was subjected to alkali weight loss treatment (98°C).

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

Minato Minato familiar”)! ” After heather washing, dry 5I at 105℃ ↓ After washing with water, dry 5B at 105℃ ↓ Wash and dry (1o order at 105℃) As a result of nickel plating using this method, the gold M-plated fibers obtained are usually Polyester fibers plated with nickel using the method described above (compared to Comparative Example 1 showed a very uniform and aesthetically pleasing appearance.Friction tests using a Gakushin type friction durability tester were carried out at 100%. As shown in Table 1, even in a boiling test in boiling water at °C, it was found that the nickel plating layer did not come off much, and it was found to have excellent robustness sufficient to withstand practical use.

Furthermore, even after the yarn was stretched to about 7 inches and then restored to its original yarn length, it exhibited good surface resistance [7]. The results are shown in Table 1.

Example 2. Comparative Example 2 After carrying out sensitization treatment and activation treatment in the same manner as in Example 1, 10 f of copper sulfate, 5 t of antamine chloride, 3 f of Ptsiel salt, and 5 t of hydrosulfide were added to 1000 c of water.
Copper plating treatment was performed at 35° C. for 5 minutes in a chemical copper plating solution dissolved in c. Through the hard plating treatment, copper-plated polyester fibers having an excellent copper-colored, glossy appearance were obtained. Moreover, the durability test results were also as shown in Table 2.

Claims (1)

[Claims] +ti A polyester fiber whose surface is coated with a metal, the fiber containing a modified polyester copolymerized with an organic sulfonic acid compound represented by the following general formula +11, and having micropores at least on the surface. Metal-coated polyester fiber characterized by being a hollow fiber (2) Contains a modified polyester copolymerized with an organic sulfonic acid compound represented by the following general formula (iris), containing a phosphorus compound represented by the following general formula +11 and T-methane. Lower i--A hollow polyester fiber selected from the group consisting of sulfuric acid paste compound (also known as a kind of micropore-forming agent) is treated with an alkaline solution 1- After that, it becomes sensitive. A method for producing metal-coated polyester fiber, which comprises sequentially applying a coating treatment, an activation treatment, and an electroless plating treatment.
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