CN103820992A - Preparation method for silver golden regenerated cellulose fiber/silver golden regenerated cellulose fiber fabric - Google Patents

Abstract

The invention discloses a preparation method for a silver golden regenerated cellulose fiber/silver golden regenerated cellulose fiber fabric. According to the preparation method, regenerated cellulose fiber and/or regenerated cellulose fiber fabric is taken as a raw material and soluble silver salts are adopted to obtain the golden regenerated cellulose fiber/golden regenerated cellulose fiber fabric, under the action of lewis acid catalysts and by adopting a catalytic nano chemical plating technology. The silver golden regenerated cellulose fiber/silver golden regenerated cellulose fiber fabric has the functions of antibiosis, deodorization, static electricity resistance and anti-electromagnetic radiation, and can be applied to the fields of military, medical treatment, public health, home furnishing and clothing. The regenerated cellulose fiber, adopted as the raw material by the invention, is cotton pulp regenerated cellulose fiber, wood pulp regenerated cellulose fiber, bamboo pulp regenerated cellulose fiber, or sodium alginate regenerated cellulose fiber; the regenerated cellulose fiber fabric, adopted as the raw material by the invention, is pure fabrics or blended fabrics of the regenerated cellulose fibers, or the blended fabrics of the regenerated cellulose fibers and other chemical fibers.

Description

A kind of preparation method of silver golden regenerated cellulose fiber/regenerated cellulose fiber fabric

technical field

The invention relates to a dyeing and finishing method of regenerated cellulose fibers/regenerated cellulose fiber fabrics, in particular to a preparation method of silver golden regenerated cellulose fibers/regenerated cellulose fiber fabrics.

Background technique

Silver is the metal with the lowest resistivity among all metals, so it has high conductivity and can resist 5000 volts of static electricity. No static comfort, so the silver fiber can conduct static electricity very quickly and efficiently, which can protect the human body from electromagnetic waves, especially for pregnant women, protect the fetus in the abdomen from electromagnetic waves, and ensure long-term work near electromagnetic sources such as computers The health of personnel plays an important role in health care. The mechanism of metal silver sterilization is to block the physiological process of bacteria. Under wet conditions, silver ions can coagulate the proteins inside and outside the bacterial cell membrane, thereby blocking the respiration and reproduction process of bacterial cells. The antibacterial ability of silver ions is amazing, and a few milligrams of silver in parts per billion can purify 1 kilogram of water. Common antibiotics can eliminate six different pathogens, while silver-containing antibiotics can eliminate more than 650 pathogens. This characteristic of silver material has been widely used in medicine as early as more than two thousand years ago. Because of the excellent antibacterial function of silver, silver fiber has the function of anti-mildew and deodorization.

The American Society for Testing and Materials ASTMD4935-99 standard is used to test, the silver fiber electromagnetic radiation attenuation rate is ≥99.9%, the shielding broadband is 500KHZ-6GHZ, and it is highly effective in antibacterial and antistatic. In the fields of clothing (electromagnetic radiation shielding clothing for pregnant women, antistatic clothing, military uniforms, etc.), decorative fabrics (performance clothing, curtains, car interiors, ship interiors, curtains), etc., its functional fibers and textiles have an important market value.

Silver fiber manufacturing methods include pure silver drawing method and textile fiber silver deposition method. Pure silver fiber is not only expensive, but also does not have textile fiber properties such as sweat absorption, breathability, and softness, so its application is limited. The textile fiber silver deposition method is generally to obtain silver-coated fibers by electroless plating or vacuum sublimation deposition on the surface of chemical fiber (such as nylon, polyester, etc.) substrates. The fiber is moderate in price and high in strength, but chemical fibers do not have sweat-absorbing and breathable properties. , poor performance. In particular, no matter it is pure silver wire drawing method or textile fiber silver deposition method, the silver fibers obtained are all silver gray or silver gray to black transition color, and gold-like golden fibers cannot be obtained.

For example, the earliest silver-plated fiber brand in the world is X-Static of Nobel Fiber Technologies-nologies in the United States. It initially used electroless plating technology, that is, a layer of pure silver was plated on the surface of nylon fibers. Japan's TOYOSHIMA&Co., Ltd (Toyoshima Textile Co., Ltd.) developed a silver-plated polyester fiber (silver-plated polyester) with the trade name μ-func in 1999. In 2001, Mitsubishi Materials Corporation also developed silver-plated polyester fiber-AGposs fiber.

Chinese patent application 200410024079.8 discloses a method for preparing silver-plated fiber fabrics. It uses chemical fiber fabrics or polyester non-woven fabrics as a substrate, and uses ion plating to plate silver or stainless steel under the protection of nitrogen or argon. The electroplating plastic process continuously plated nickel, copper or silver on the surface of the substrate, and finally electroplated a layer of silver to produce a non-clothing silver-plated fiber fabric with shielding properties.

The paper "Preparation and Properties of Silver-plated Conductive Fiber" published by Jiao Hongjuan introduced the method of electroless silver-plated polyester staple fiber.

In the above-mentioned prior art, its silver-plated fibers are all based on synthetic fibers such as polyester or nylon, and the final products are all silver-gray, and silvery golden fibers cannot be obtained, and regenerated cellulose fibers/regenerated cellulose cannot be used. Silver-plated fibers were prepared from fiber fabrics.

And the golden-yellow fiber in the prior art generally adopts pure gold drawing or obtains by adding golden color pigment in chemical fiber. There are obvious defects in these two types of golden yellow fibers. On the one hand, the former is expensive. For example, in 2011, Nylstar Corporation of the United States developed a 24K Nylgold gold fiber, which is said to have skin care, beauty, and anti-aging effects, but the price per gram exceeds 90. US dollars; the latter has no shielding and antibacterial effects, and due to the introduction of chrome yellow and medium chrome yellow chemical pigments containing toxic elements chromium, the fastness of the combination between fibers and pigments cannot be compared with "plating", it is difficult to avoid There is a certain degree of pollution, which is not suitable for home textile products. On the other hand, the golden-yellow fiber prepared by the pure gold drawing method does not have the sweat-absorbing, breathable, and comfortable wearing properties of natural cotton fibers, so it is difficult to be used for taking; Fiber, because chemical fiber is used as the base material, the waste after use is difficult to degrade in nature, which is not conducive to environmental protection.

Contents of the invention

The object of the present invention is to provide a kind of regenerated cellulose fiber/regenerated cellulose fiber fabric as substrate, utilize soluble soluble silver salt or silver complex, under the action of catalyst, prepare the product by catalytic nano chemical plating process Silvery golden regenerated cellulose fiber/regenerated cellulose fiber fabric with high added value and good decorative effect.

The technical solution adopted by the present invention to achieve the above object is: a preparation method of silver golden regenerated cellulose fiber/regenerated cellulose fiber fabric, which is characterized in that it comprises the following steps in sequence:

(1) Put the degreased and cleaned regenerated cellulose fibers and/or regenerated cellulose fiber fabrics in the finishing processing equipment at a bath ratio of 1:4-100, and the bath liquid is guaranteed to be circulated effectively. Soluble silver salt or silver complex, the addition ratio is 1:0.01-0.10 according to the weight percentage of regenerated cellulose and/or regenerated cellulose fiber fabric and silver, and react at a constant temperature of 10-75°C for 20-100min;

(2) Add a composite stabilizer containing five components of ethylenediamine, tetraacetic acid sodium salt, benzotriazole, thiosemicarbazide, and ammonia water, and react at 10-90°C for 30-90min; among them,

Among the above composite stabilizers, the weight-number ratio of the five components of ethylenediamine, sodium tetraacetate, benzotriazole, thiosemicarbazide and ammonia water is 1:0.2:0.1:0.3:1-5;

The weight percentage of regenerated cellulose fiber and/or regenerated cellulose fiber fabric and above-mentioned composite stabilizer is 1: 0.01-0.10;

(3) According to the weight percentage of regenerated cellulose fiber and/or regenerated cellulose fiber fabric and Lewis acid catalyst is 1:0.0001-0.05, add their solution and circulate for 15-40min;

Then according to the weight percentage of regenerated cellulose fibers and/or regenerated cellulose fiber fabrics and glucose or sodium hypophosphite is 1:0.02-0.20, add their solutions dropwise, and react at a constant temperature of 35-65°C for 20-70min;

(4) The treated regenerated cellulose fibers and/or regenerated cellulose fiber fabrics are sequentially washed with surfactants, passivated, rinsed with clean water, dehydrated and dried.

Preferably, the above-mentioned soluble silver salt is silver nitrate and silver acetate, and the soluble silver complex is silver iminodisulfonic acid complex.

More preferably, the above-mentioned regenerated cellulose fibers are cotton pulp regenerated cellulose fibers, wood pulp regenerated cellulose fibers, bamboo pulp regenerated cellulose fibers or sodium alginate regenerated cellulose fibers.

More preferably, the above-mentioned Lewis acid catalyst is palladium dichloride, ammonium hexachloroplatinate, palladium chloride, nickel dichloride.

More preferably, the above-mentioned regenerated cellulose fiber fabric is pure regenerated cellulose fiber fabric or a blended fabric of regenerated cellulose fiber and chemical fiber.

More preferably, the silver golden regenerated cellulose fiber/regenerated cellulose fiber fabric prepared according to the above preparation method is characterized in that the antibacterial rate is ≥ 90%, and the electromagnetic radiation attenuation rate is ≥ 91%.

More preferably, the silver golden regenerated cellulose fiber prepared according to the above preparation method can be used for pure spinning or blended with other fibers in any proportion.

The technical effect directly brought by the above technical scheme is that the regenerated cellulose fiber/regenerated cellulose fiber fabric is used as a raw material, and the soluble silver salt or silver complex is used to prepare the product through a catalytic nano-electroless plating process under the action of a catalyst. Silver and golden regenerated cellulose fiber/regenerated cellulose fiber fabric with high added value and good decorative effect has the following features and advantages:

1. Use relatively cheap soluble silver salts or silver complexes as raw materials to obtain a product with the same gold color as the product directly prepared by the pure gold wire drawing method in the prior art, which has high added value and good decorative effect.

2. The sweat-absorbing, breathable, soft, anti-allergic, easy to clean, not easy to fluff, pilling and other excellent wearing characteristics of regenerated cellulose fiber are well preserved, and the waste after use can be naturally degraded.

3. Due to the use of catalytic nano chemical plating process for "silver plating", it has good antibacterial, self-cleaning, conductive, antistatic, shielding electromagnetic radiation and other functions, and the color durability is good.

4. The silver golden regenerated cellulose fiber prepared by the method of the present invention can be purely spun or blended with other fibers in any proportion. The silver gold natural regenerated fiber textile made by weaving has the characteristics of good moisture absorption, moisture absorption, sweat absorption and air permeability, and good wearing comfort.

Description of drawings

Fig. 1 is the X-ray diffraction pattern of silver golden regenerated cellulose fiber/regenerated cellulose fiber fabric; among them: (a) X-ray diffraction pattern of ordinary regenerated cellulose fiber without silver; (b) golden silver-plated regenerated Cellulose fiber/regenerated cellulose fiber fabric X-ray diffraction pattern;

Figure 2-1 to Figure 2-6 are electron micrographs of silvery golden regenerated cellulose fibers.

Detailed ways

Example 1

(1) Put 100Kg of degreased and cleaned viscose fiber into the spray-type finishing processing equipment according to the bath ratio of 1:4, add 1.6Kg of silver nitrate into the batching kettle, prepare a solution and enter the circulation system, React at 35°C for 100 min.

(2) Following step (1), mix the five components of ethylenediamine, tetraacetic acid sodium salt, benzotriazole, thiosemicarbazide, and ammonia water in a ratio of 1:0.2:0.1:0.3:1 in parts by weight Form a compound stabilizer, weigh 1Kg to prepare a solution, enter the circulation system, and react at 40°C for 30 minutes.

(3) Following step (2), weigh 0.01Kg of palladium dichloride to prepare a solution and enter the circulation system for 30 minutes;

Then weigh 2Kg of glucose to prepare a solution, drop it into the circulation system, and react at a constant temperature of 45°C for 70min.

(4) Following step (3), the treated regenerated fibers or their fabrics are first washed with nonionic surfactants, then passivated with cationic surfactants, and finally rinsed with clean water, dehydrated, and dried to obtain silver. Gold viscose or its fabric.

The silvery golden viscose fiber or its fabric is golden in color, has a bacteriostasis rate greater than 90%, and an electromagnetic radiation attenuation rate of ≥91%.

Example 2

(1) 100Kg of degreased and cleaned wood pulp regenerated fiber fabric (modal fiber) is placed in the spray-type finishing processing equipment at a bath ratio of 1:4, and 0.065Kg of silver acetate is added to the batching tank to prepare After forming a solution, it enters the circulation system and reacts at 75°C for 60 minutes.

(2) Following step (1), mix the five components of ethylenediamine, tetraacetic acid sodium salt, benzotriazole, thiosemicarbazide, and ammonia water in a ratio of 1:0.2:0.1:0.3:3 in parts by weight Form a compound stabilizer, weigh 1.3Kg to prepare a solution, enter the circulation system, and react at 75°C for 40 minutes.

(3) Following step (2), weigh 0.05Kg of ammonium hexachloroplatinate to prepare a solution and enter the circulation system for 40 minutes;

Then weigh 20Kg of sodium hypophosphite to prepare a solution, drop it into the circulation system, and react at a constant temperature of 65°C for 45min.

(4) Following step (3), the treated regenerated fibers or their fabrics are first washed with nonionic surfactants, then passivated with cationic surfactants, and finally rinsed with clean water, dehydrated, and dried to obtain silver. Gold modal fabric.

The silver gold modal fabric silver gold viscose fiber or the color of the fabric is golden yellow, the antibacterial rate is greater than 99%, and the electromagnetic radiation attenuation rate is more than or equal to 98%.

Example 3

(1) Put 100Kg of degreased and cleaned bamboo pulp regenerated fiber (Tencel) in the overflow finishing processing equipment at a liquor ratio of 1:100, and add 0.11Kg of iminodisulfonic acid into the batching tank Acid-complexed silver concentrate (silver content 27%), prepared into a solution, enters the circulation system, and reacts at 45°C for 60 minutes.

(2) Following step (1), mix the five components of ethylenediamine, tetraacetic acid sodium salt, benzotriazole, thiosemicarbazide, and ammonia water in a ratio of 1:0.2:0.1:0.3:4 in parts by weight Form a compound stabilizer, weigh 5Kg to prepare a solution, enter the circulation system, and react at 45°C for 50min.

(3) Following step (2), weigh 2Kg of nickel dichloride to prepare a solution and enter the circulation system for 40 minutes;

Then weigh 20Kg of glucose to prepare a solution, drop it into the circulation system, and react at a constant temperature of 50°C for 20min.

(4) Following step (3), the treated regenerated fibers or their fabrics are first washed with nonionic surfactants, then passivated with cationic surfactants, and finally rinsed with clean water, dehydrated, and dried to obtain silver. Gold tencel fibers.

The color of the silvery golden tencel fiber is golden yellow, the antibacterial rate is greater than 97%, and the electromagnetic radiation attenuation rate is ≥96%.

Example 4

(1) Put 100Kg of degreased and cleaned calcium alginate regenerated cellulose fibers in the overflow finishing processing equipment at a bath ratio of 1:50, and add 15.75Kg of silver nitrate into the batching tank to prepare a solution Then enter the circulation system and react at 10°C for 85min.

(2) Following step (1), mix the five components of ethylenediamine, tetraacetic acid sodium salt, benzotriazole, thiosemicarbazide, and ammonia water in a ratio of 1:0.2:0.1:0.3:5 in parts by weight Form a compound stabilizer, weigh 10Kg to prepare a solution, enter the circulation system, and react at 20°C for 90 minutes.

(3) Following step (2), weigh 0.03Kg of palladium chloride to prepare a solution and enter the circulation system for 25 minutes;

Then weigh 13.8Kg of sodium hypophosphite to prepare a solution, drop it into the circulation system, and react at a constant temperature of 35°C for 65min.

(4) Following step (3), the treated regenerated fibers or their fabrics are first washed with nonionic surfactants, then passivated with cationic surfactants, and finally rinsed with clean water, dehydrated, and dried to obtain silver. Gold calcium alginate fibers.

The silvery golden calcium alginate fiber is golden yellow in color, has a bacteriostasis rate greater than 99.9%, and an electromagnetic radiation attenuation rate of ≥99.9%.

Example 5

(1) Put 100Kg of the cleaned 30/70% polyester-viscose blended fabric into the spray-type finishing processing equipment according to the bath ratio of 1:20, add 3.15Kg of silver nitrate into the batching tank, prepare it into a solution, and enter Circulation system, react at 25°C for 75min.

(2) Following step (1), mix the five components of ethylenediamine, tetraacetic acid sodium salt, benzotriazole, thiosemicarbazide, and ammonia water in a ratio of 1:0.2:0.1:0.3:2 in parts by weight Form a compound stabilizer, weigh 2.1Kg to prepare a solution, enter the circulation system, and react at 35°C for 90 minutes.

(3) Following step (2), weigh 0.02Kg of palladium dichloride to prepare a solution and enter the circulation system for 35 minutes;

Then weigh 5.2Kg of glucose to prepare a solution, drop it into the circulation system, and react at a constant temperature of 45°C for 60min.

(4) Following step (3), the treated regenerated fibers or their fabrics are first washed with nonionic surfactants, then passivated with cationic surfactants, and finally rinsed with clean water, dehydrated, and dried to obtain silver. Gold viscose or its fabric.

The silver gold 30/70 polyester viscose blended fabric has a bacteriostasis rate of more than 95%, and an electromagnetic radiation attenuation rate of ≥99%.

Example 6

(1) Put 100Kg of cleaned seaweed fiber cloth in the overflow finishing processing equipment according to the bath ratio of 1:50, add 4.7Kg of silver nitrate into the batching kettle, prepare a solution and enter the circulation system, React at 55°C for 65 minutes.

(2) Following step (1), mix the five components of ethylenediamine, tetraacetic acid sodium salt, benzotriazole, thiosemicarbazide, and ammonia water in a ratio of 1:0.2:0.1:0.3:3.5 in parts by weight Form a compound stabilizer, weigh 4.25Kg to prepare a solution, enter the circulation system, and react at 55°C for 30 minutes.

(3) Following step (2), weigh 0.055Kg of palladium dichloride to prepare a solution and enter the circulation system for 15 minutes;

Then weigh 7.6Kg of glucose to prepare a solution, drop it into the circulation system, and react at a constant temperature of 55°C for 20min.

(4) Following step (3), the treated regenerated fibers or their fabrics are first washed with nonionic surfactants, then passivated with cationic surfactants, and finally rinsed with clean water, dehydrated, and dried to obtain silver. Gold kelp cloth.

The color of the silver golden seaweed fiber cloth is golden yellow, the antibacterial rate is greater than 99%, and the electromagnetic radiation attenuation rate is ≥99%.

Fig. 1 is the X-ray diffraction pattern of silver golden regenerated cellulose fiber/regenerated cellulose fiber fabric; among them: (a) X-ray diffraction pattern of ordinary regenerated cellulose fiber without silver; (b) golden silver-plated regenerated Cellulose fiber/regenerated cellulose fiber fabric X-ray diffraction pattern;

As shown in Figure 1, the diffraction peaks at 38.2 °, 44.4 °, 64.7 ° and 77.3 ° are corresponding to the face-centered cubic (fcc) elemental silver (111), (200), (220) and (311) four Diffraction peaks of a crystal plane. Proof that the silver on the silver gold regenerated cellulose fiber/regenerated cellulose fiber fabric is nano silver.

Figure 2-1 to Figure 2-6 are electron micrographs of silvery golden regenerated cellulose fibers. Wherein, Fig. 2-1 to Fig. 2-6 are the electron micrographs of the silver golden regenerated cellulose fiber prepared in embodiment 1-6 respectively, the magnification of Fig. 2-2 is 100,000 times, and the others are 50,000 times times.

As shown in Figure 2-1 to Figure 2-6, the products obtained in the above-mentioned Examples 1-6, under the electron microscope, it can be seen that silver exists in the state of nanoparticles in the fibers, and the particle size is 10-20nm.

Claims (7)

1. a preparation method of silver gold regenerated cellulose fiber/regenerated cellulose fiber fabric, is characterized in that, comprises the following steps successively: (1) Put the degreased and cleaned regenerated cellulose fibers and/or regenerated cellulose fiber fabrics in the finishing processing equipment at a bath ratio of 1:4-100, and the bath liquid is guaranteed to be circulated effectively. Soluble silver salt or silver complex, the addition ratio is 1:0.01-0.10 according to the weight percentage of regenerated cellulose and/or regenerated cellulose fiber fabric and silver, and react at a constant temperature of 10-75°C for 20-100min; (2) Add a composite stabilizer containing five components of ethylenediamine, tetraacetic acid sodium salt, benzotriazole, thiosemicarbazide, and ammonia water, and react at 10-90°C for 30-90min; among them, Among the above composite stabilizers, the weight-number ratio of the five components of ethylenediamine, sodium tetraacetate, benzotriazole, thiosemicarbazide and ammonia water is 1:0.2:0.1:0.3:1-5; The weight percentage of regenerated cellulose fiber and/or regenerated cellulose fiber fabric and above-mentioned composite stabilizer is 1: 0.01-0.10; (3) According to the weight percentage of regenerated cellulose fiber and/or regenerated cellulose fiber fabric and Lewis acid catalyst is 1:0.0001-0.05, add their solution and circulate for 15-40min; Then according to the weight percentage of regenerated cellulose fibers and/or regenerated cellulose fiber fabrics and glucose or sodium hypophosphite is 1:0.02-0.20, add their solutions dropwise, and react at a constant temperature of 35-65°C for 20-70min; (4) The treated regenerated cellulose fibers and/or regenerated cellulose fiber fabrics are sequentially washed with surfactants, passivated, rinsed with clean water, dehydrated and dried. 2. the preparation method of silver gold regenerated cellulose fiber/regenerated cellulose fiber fabric according to claim 1 is characterized in that, described soluble silver salt is silver nitrate, silver acetate, and described soluble silver complex is Silver iminodisulfonic acid complex. 3. the preparation method of silver gold regenerated cellulose fiber/regenerated cellulose fiber fabric according to claim 1, is characterized in that, described regenerated cellulose fiber is cotton pulp regenerated cellulose fiber, wood pulp regenerated fiber Vegan fiber, bamboo pulp regenerated cellulose fiber or sodium alginate regenerated cellulose fiber. 4. the preparation method of silver gold regenerated cellulose fiber/regenerated cellulose fiber fabric according to claim 1, is characterized in that, described Lewis acid catalyst is palladium dichloride, ammonium hexachloroplatinate, palladium chloride , Nickel dichloride. 5. the preparation method of silvery golden cotton fiber/cotton fiber fabric according to claim 1 is characterized in that, described regenerated cellulose fiber fabric is the pure fabric of regenerated cellulose fiber or regenerated cellulose fiber and chemical fiber Blended fabrics. 6. The silver golden regenerated cellulose fiber/regenerated cellulose fiber fabric prepared by the preparation method according to claim 1 is characterized in that the antibacterial rate is ≥ 90%, and the electromagnetic radiation attenuation rate is ≥ 91%. 7. The silver golden regenerated cellulose fiber prepared by the preparation method according to claim 1 is characterized in that it can be used for pure spinning or blended with other fibers in any proportion.

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