JPS6233871A - Production of metal coated polyester fiber - 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 Application for aS> The present invention relates to a method for producing polyester fibers whose surfaces are coated with metal, and particularly relates to a method for producing polyester fibers in which a metal coating and polyester fibers have excellent adhesion properties. It is something.

Kujyorerenjutsu〉 General match F! 1. The idea of applying metal plating to fibers is
Although it is necessary to roughen the surface by etching, polyester fibers are relatively stable against acidic solutions, so etching is performed using an alkaline sludge.

However, although polyester fibers etched with this alkaline injection 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 during elongation are weak, making it a practical problem. There is.

<Object of the Invention> In view of the current situation, the present inventors have thoroughly investigated the adhesion strength and film durability between polyester fiber and gold false plating film, and as a result, have arrived at the present invention. .

<Structure of the Invention> That is, the present invention provides a method for producing polyester 4 fibers whose surfaces are coated with metal, in which the fibers undergo a reaction between a phosphorus compound and an alkaline earth metal compound represented by the following general formula %. The internally precipitated fine particles precipitated by
After uniformly dispersing the fibers, the fibers are treated with an alkaline compound water bath solution to reduce the length by at least 31 Et%, and the treated fibers are subjected to sensitization treatment and activation treatment, s)
1! This is a method for producing polyester fibers coated with elephant sails, which is characterized in that a deplating treatment is performed sequentially.

The polyester used in the present invention has terephthalic acid as its main acid component and at least one glycol, preferably at least one fullylene glycol selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol as its main glycol component. The main target is polyester.

It may also be a polyester in which a part of the terephthalic component is replaced with another difunctional carboxylic acid component, and
Alternatively, it may be a polyester in which part of the glycol component is modified with the above-mentioned glycol or other diol component other than the main component.

Examples of difunctional carbonyl relatives other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, 5- Examples include aromatic, aliphatic, and aliphatic dialphahedral carbons such as natritum, adipine, sebacin, and 1.4-cyclohexyl dicarbonate. In addition, examples of diol compounds other than the above-mentioned glycol include cyclohexane-
Aliphatic, alicyclic, such as 14-dimethator, neopentyl glycol, bisphenols, bisphenol S,
Examples include aromatic diol compounds and polyoxyalkylene glycols.

Such polyesters may be synthesized by any method. For example, in the case of polyethylene terephthalate, it is usually a direct esterification reaction between terephthalic acid and ethylene glycol, or a call ester reaction, in which a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol.
In addition, the reaction in the 131i stage in which the low-electricity combination is produced by the 6th stage, and the second stage reaction in which the reaction product of the first stage is heated under reduced pressure and reacted until it reaches a slight degree of merging. In the present invention, the above-mentioned polyester is impregnated with internal particles precipitated by a reaction between a phosphorus compound represented by the following general formula and an alkaline earth metal compound. The internal precipitation system referred to here means that the above-mentioned phosphorus compound and alkaline earth metal compound are added to the polyester reaction system without reacting in advance, and the two are reacted inside the polyester reaction system to substantially form the polyester. Insoluble means that the Am particles should be precipitated uniformly, and the ridges, which are substantially insoluble in the polyester, which have been previously externally irradiated to the desired particle size, are preferably mixed with glycol,
It is distinguished from external addition systems, which are dispersed in alcohol or wood aroma and added to the polyester reaction system.

Showing phosphorus compounds! ! In the 1j notation, l is also 1 and IL” is 1.
1'+tli is the best chance. With this 1IIlb,
A group is specifically a furkyl group, an aryl group, an aralkyl group, or +(0H2)lO), 143 (however, IL3
is a hydrogen atom, a furkyl group, an aryl group, or an aralkyl group, t is an integer of 2 or more, and k is 1 or more! ff) etc. are preferable.
Preferably, oX, which may be the same or different, is a monovalent organic group or a metal, and as a monovalent organic group, it is the same as the definition of the organic group in R',)L2 above. hand
It may be the same as or different from al and ♂, and the metal is particularly preferably an alkali metal or an alkaline earth metal.
Among them, Li, Na, Mgl/2, Cal/2, S
rl/2 and Bjl/2 are more preferred, and among them, Oa 1/2 is particularly preferred. n is 1 or O.

Such phosphorus compounds include, for example, triethyl phosphate,
Triethyl phosphate, triphenyl phosphate, triphenyl phosphate, etc., phosphorous trimethyl, triethyl diphosphate, tributyl phosphite, triphenyl phosphite, etc. Defective trinistyl, urinary chloride compounds/or dimethyl phosphate, diethyl phosphate,
Phosphate diesters such as dimethyl phosphate, phosphorous di-enyl, etc., phosphorous diesters such as dimethyl phosphate, diethyl phosphite, diptyl phosphite, diphenyl phosphite, etc. Compounds of alkali metals such as I, Na, etc. or IVrgs Oa, 5rzHa
1 selected from phosphorus compounds etc. which can be dissolved by reacting with alkaline earth metal compounds such as
One or more phosphorus compounds can be used ■ There is no particular restriction on the alkaline earth metal compound used in combination with the above phosphorus compound as long as it reacts with the above phosphorus compound to form a non-Δ salt in the polyester. Examples include alkaline earth metal oxides, chelating agents such as ethylenediaminetetraacetic acid, hydroxides, fluorates such as methylates, ethylates, glycolates, and phenolates. Preferred are organic carboxylic salts, halides, thiolate compounds, and alcoholades, which are ethylene glycol as a carrier, and organic carboxylic acid rings are particularly preferred. Among the alkaline earth metals, ca is particularly preferred. Up;
The alkaline earth metal compound may be used alone in 1fIII hQL, or two or more thereof may be used in combination.

In order to produce a polyester that contains internally precipitated particles made of the phosphorus compound and alkaline earth metal compound that are uniformly dispersed, for example, at the stage ( The above-mentioned phosphorus-resistant compounds and (b
) The above alkaline earth metal compound @ is prepared without reacting (at and (bl) in advance, and the sum of the metal base numbers of (81 and (b)) is 2.
An example of this method is to add the polyester in an amount of 0 to 3.2 times and then complete the synthesis of the polyester.

The content of the above-mentioned phosphorus compound and the alkaline earth element v toxilated compound in the polyester is 0.1 to 5 polymers.
It should be within the range of t%. If the amount is less than 0.1% by weight, the distribution of micropores on the surface of the fibers that are penetrated in a j & n manner will be irregular, and the '#a properties of the metal coating will decrease. 5](
If the content exceeds ffi%, the physical properties of the polyester fiber will be reduced.

Here, to determine the concentration of internally precipitated fine particles in polyester, the fibers made of the polyester were dissolved in 0-chlorophenol, filtered through a glass filter and centrifuged. Equinox and death) leaking minute I
# Wash repeatedly using particulate 0-chlorophenol until polyester is no longer recognized? It can be found by standing down after using the cloud.

There is no need to adopt the internal dr yarn WL MB particle method thus obtained, and the yarn material made of polyester fibers containing internally precipitated woven fine particles obtained by using ordinary polyvarnish in this way can be directly in the form of yarn φ material or @Akali compound water 8M, which was organized according to the law and made into soul knitting.
Heat the aqueous solution of an alkaline compound in a bud/
Some of it is removed by steam treatment.

Examples of the alkali compounds used here include sodium hydroxide, potassium hydroxide, tetramethyl heptammonium hydride p oxide, sodium carbonate, and potassium carbonate. Among these, sodium hydroxide and potassium hydroxide are particularly preferred.

Further, alkaline weight loss accelerators such as methyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride, etc. can be used as appropriate.

The amount reduced by this alkali treatment should be in the range of 3 beans or more based on the amount of fiber IL, and should be %.
If the weight loss rate is less than 3xm%, satisfactory surface irregularities will not be formed and sufficient effects will not be obtained.

By treating with an aqueous solution of an alkali compound, the fibers are oriented in the axial direction, and the width in the direction perpendicular to the fiber axis is in the range of 0.1 to 0.3μ at the maximum value of the frequency distribution,
fs having a size in which the length in the fiber axis direction is in the range of 0.1 to 5μ, can be formed on the entire surface of the fiber, and has micropores suitable for electroless plating treatment. Polyester fibers can be obtained.

Polyester obtained by the method of the invention.

The metal plating method in the present invention will be explained below. First, a catalyst for chemical plating is provided.

Methods for providing a catalyst include a sensitizing-7 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, sulfur, and palladium. Alternatively, noble metals may be deposited on the fiber surface as a catalyst, or the noble metal ions may be deposited on the fiber surface by first immersing the fiber in a liquid containing noble metal ions to form a layer of noble metal ions, and then reducing the fiber in a reducing agent solution to deposit the noble metal on the fiber surface. It may be precipitated and used 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.

After applying the catalyst using the method described above, chemical plating is performed.
For chemical plating, it is possible to use a known plating solution consisting of 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 steel, nickel, silver, tin, and cobalt, but copper and nickel are preferred from the viewpoint of liquid stability and adhesion between fibers and metal coating.

<Effects of the Invention> The polyester fiber produced by the method of the present invention has superior mechanical viscosity, adhesion between the fiber and metal coating, and durability compared to conventional polyester fibers.

<Examples> The present invention will be specifically described below with reference to Examples. Parts are parts by weight.

In the examples, surface resistance and durability were evaluated according to the following method using both ends of a test piece with a length of 101 and a width of 100,000,000 and a surface resistance measuring device 'Moful FIM-1000' (In-3). (manufactured by Wadenki Keikiura Seisakusho)
The surface resistance of the test piece was measured before and after stretching by 7 inches. The elongation was carried out using a tensile tester at a rate of 1 tread/tread.

durability Friction durability Friction test using hand-wave type friction fastness tester The weight before and after trial was measured and expressed as a weight ratio.

The evaluation was as follows: O1: There was no change in appearance, and O1: There was no change in appearance, such as metal spots, discoloration, or loss of gloss.

The boiling durability test piece was boiled in water at 100° C. for 10 hours, and the weight (dry weight) before and after the boiling treatment was measured and expressed as a weight ratio.

Practice 911 Comparison 1 Terephthal #dimethyl 100s, ethylene glycol 6
Methanol is produced by charging 0.06 parts of 0s1 calcium acetate monohydrate (C0,066 mol% relative to dimethyl terephthalate) into a transesterification tank and raising the temperature from 140°C to 230 t over 4 hours under a nitrogen gas atmosphere. The transesterification reaction was carried out while distilling off from the system. Subsequently, the obtained reaction product KO04 parts of trimethyl phosphate (0.554 mol % based on dimethyl terephthalate) and 0.25 parts of trimethyl phosphate (0.554 mol % based on dimethyl terephthalate)
A phosphoric acid diester prepared by reacting 1 part of calcium acetate monohydrate (l/2 times the mole relative to trimethyl phosphate) in 6.8 parts of ethylene glycol at a temperature of 120°C for 60 minutes under total overflow. Clear solution of calcium salts 7
．． A transparent mixed solution of phosphoric acid diester calcium salt and calcium acetate obtained by dissolving 0.45 parts of calcium acetate hydrate (0.9 times mole relative to trimethyl phosphate) in 45 parts at room temperature 7.9 1 part, then 0.04 part of antimony dioxide was added and transferred to a polymerization can. Next, it will be 760 waHI or 1mHI over 1 hour.
At the same time, reduce the pressure to 230℃ for 1 hour and 30 minutes.
The temperature was raised to 85°C. Polymerization was carried out for a further 3 hours at a polymerization temperature of 285° C. under reduced pressure below ltmHIi, for a total of 4 hours and 30 minutes, resulting in an intrinsic viscosity of 0.640.

The boat is made of polymer with a softening point of 259℃. After the reaction was completed, the polymer was made into chips according to a conventional method. The content of internally precipitated fine particles in this chip was 0.45%.

The chips were dried according to a conventional method, and then spun using a conventional spinneret to obtain 300 dj/24F, 'I
The yarn was obtained. Using this raw yarn, the stretching ratio is 4 according to the filling method.
．． Stretch it at 0 times and use a 75 de7' 241+1 multifilament.

From now on, the density of the raw material is 68 pieces / 2.54 cm, 446
2 / 2.54 ex 2/2 M aL d 4
The snout was elaborated.

These four proboscis were refined and preset using a conventional method, and treated with 3.5 liters of hydroxide in a water bath solution at a warm temperature.
I've made 4 & 10 pieces of fabric.

Wash with water and apply chemical plating according to the process shown below.

Wash with water 4 51 irises at 105℃ Dry 7 points of water ((z 52 at 105℃! i! Dry m Wash with water and dry (
As a result of nickel plating in this way, the metal-plated fR fiber was +1 normal polyester Ad.
(Nickel plating was applied to 1 using the method described above.)
It exhibited a very uniform and aesthetically pleasing appearance compared to Comparison 1). Also, as shown in Table 1, the nickel plating did not come off much when tested using a 4-degree tester using a 4-degree tester, and a boiling test using boiling water at 100°C. It was found that it had sufficient solidity even when crushed.

Furthermore, I also showed good surface resistance when the fiber length was restored to its original length after being elongated to 7 cm.

The results are shown in Table 1.

Example 2 Comparative Example 2 Sensitization treatment and activation treatment were carried out in the same manner as in Example 11 ratio reduction column 1. Copper plating treatment was carried out by treating sulfide 5I at 35° C. for 5 minutes in a chemical steel plating bath containing 1000 ccK of water. This in-metal treatment yielded copper-plated polyester fibers having a copper-colored, glossy, and pickled appearance. Also, the durability test (1 mK) was as shown in Table 2.

Claims (1)

[Claims] The following general formula ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are monovalent organic groups, X is a monovalent organic group or metal, n is 1 Or indicates 0. ] A polyester fiber in which 0.1 to 5% by weight of internally precipitated fine particles precipitated by the reaction between a phosphorus compound and an alkaline earth metal compound is uniformly dispersed is treated with an aqueous solution of an alkaline compound to remove at least the A method for producing metal-coated polyester fibers, which comprises sequentially subjecting the fibers to sensitization treatment, activation treatment, and electroless plating treatment after reducing the weight by 3% by weight.