CN100414039C - Dyeing method of fine-denier polypropylene fiber blended with rare earth-containing material modified polyolefin and polypropylene - Google Patents

Abstract

The present invention discloses to a dyeing method for a fine denier polypropylene fiber blended with modified polyolefine comprising a rare earth material and polypropylene of a red group, a yellow group, a blue group and an original color group which are suitable for fine denier dyed polypropylene fiber dispersion dye are sieved out by comparing the lifting property, the light fastness, the friction fastness and the washing fastness of dispersion dye. Steps of dye pretreatment, dye, dye aftertreatment, etc., are orderly carried out in the dye process. In the dye pretreatment, the fine denier polypropylene fiber is treated by detergent and sodium carbonate; in the dye, the fine denier polypropylene fiber is added with acetic acid and dyed by using dispersion dye and raising temperature; and in the dye aftertreatment, a loose colour is washed off. The fine denier polypropylene fiber is dyed by one kind of selected dispersion dye or a mixture of several kinds of selected dispersion dye. The dye uptake of dye is largely improved, and color freshness, uniformity and color fastness are good after dyed.

Description

Dyeing method of fine-denier polypropylene fiber blended with rare earth-containing material modified polyolefin and polypropylene

technical field

The invention relates to a dyeing method of fine-denier polypropylene fibers, in particular to a dyeing method of fine-denier polypropylene fibers prepared by in-situ polymerization modified polyolefin and polypropylene blended resins containing rare earth materials.

Background technique

Due to the rich source of raw materials, simple manufacture and low price, polypropylene fiber has developed rapidly and has many excellent properties, and has been widely used in industry and daily life. Due to the successful development of fine-denier polypropylene fiber, it has been found that fine-denier polypropylene fiber has a unique hydrophobic and moisture-conducting effect, and the underwear made of it is smooth and comfortable to wear. However, due to the non-polar structure of polypropylene fiber, there is no polar group in the molecule that can be combined with any dye molecule, and the crystallinity of polypropylene fiber is very high, the structure is compact, and the interior lacks the necessary pores for dye diffusion, hydrophobicity. It is very significant, so the dye molecules can only diffuse or penetrate into the amorphous region of the fiber molecules, but cannot enter the crystal region. Therefore, currently commonly used dyes cannot dye polypropylene fibers (including disperse dyes). As a clothing textile material, the dyeing of polypropylene fiber is an urgent problem to be solved in the further development of polypropylene fiber.

People focus on how to solve the dyeing problem of polypropylene fiber, in the dyeing of unmodified polypropylene fiber, block copolymerization and graft copolymerization modified polypropylene fiber, low molecular compound (metal compound) modified polypropylene fiber and high polymer A lot of research work has been done on blending modified polypropylene fibers. Among them, polymer blending modification should be an effective way to improve the dyeability of polypropylene fibers. Patent CN1339623A discloses the preparation of a special resin for dyeing fine-denier polypropylene fibers, 77-98% (by weight) of polypropylene materials that can be spun into fine-denier fibers, 2-20% (by weight) of Polyolefin materials and 0-3% (by weight) of polyolefin derivatives are subjected to binary or ternary melt blending modification at a temperature of 200-280°C, and the finished product can be spun and can be used for common disperse dyes Dyeable fine denier polypropylene. However, due to the low polarity of the added polyolefin materials and polyolefin derivatives, the affinity with disperse dyes is weak, so the soaping fastness in actual dyeing is not ideal, especially when dyeing medium and dark colors.

Disperse dyes are a kind of dyes with relatively small molecules and no water-soluble groups in the structure. They have complete chromatography and are widely used in dyeing synthetic fibers such as polyester and acetate fibers. Patent CA1264443A is based on obtaining the best dyeing effect, selecting disperse dyes with good aggregation, good fastness (friction resistance, water resistance, sun resistance, etc.) and high K/S value, and combining these disperse dyes, Allow it to work at its maximum concentration before dye rubbing occurs. This patent is said to allow reliable dyeing of polypropylene fibers at atmospheric pressure, and the dyed fibers exhibit good fastness. However, due to changes in the internal structure of polypropylene fibers and the interaction mechanism with disperse dyes after blending and modification, some changes will also occur in the disperse dyes mentioned in the red, yellow and blue primary color families mentioned in the patent claims .

Using surface-modified rare earth materials to participate in the polymerization of polyolefins through in-situ hybridization, and then blending with polypropylene to prepare blended resins for fine-denier dyeable polypropylene fibers is a kind of fine-denier dyeable polypropylene fibers with great industrial prospects. It can not only realize the uniform dispersion of inorganic nanoparticles in the polymer, but also maintain the nanometer characteristics of the particles. For this new type of fine denier dyeable polypropylene, there is no satisfactory dyeing method at present, and it needs to be re-screened according to the aggregation, fastness (friction resistance, water resistance, sun resistance, etc.) and K/S value of the dye. Disperse dyes, analysis and research on dyeing methods, in order to realize the industrial production of this fine-denier dyeable polypropylene fiber.

Contents of the invention

The technical problem to be solved in the present invention is to disclose a dyeing method of fine-denier polypropylene blended with rare earth-containing material-modified polyolefin and polypropylene, so as to meet the needs of industrial production.

The so-called rare earth-containing material-modified polyolefin and polypropylene blended fine-denier polypropylene fiber is a resin obtained by blending rare-earth-containing material-modified polyolefin and polypropylene. After melt spinning and stretching, the obtained single Fibers with a silk fineness of 0.9-2dtex, wherein the weight content of the modified polyolefin containing rare earth materials is 2-8%, the weight content of polypropylene is 92-98%, and in the modified polyolefin containing rare earth materials, the weight content of rare earth materials 7.5-12.5%, the weight content of modified polyolefin is 87.5-92.5%;

The preparation method of said rare earth-containing material modified polyolefin comprises the following steps:

At 70-75°C, add Na ₂ S ₂ O ₃ to the aqueous solution containing dispersant, then add the mixture of surface-modified nano-rare earth particles, initiator and modified olefin monomer, and react at 70-80°C for 50-70 Minutes, heat up to 81-85°C for 80-100 minutes, continue to heat up to 86-90°C for 80-100 minutes, finally raise the temperature to 91-96°C, harden the particles for 100-140 minutes, obtain mature hybrid particles, wash , drying to obtain rare earth-containing material-modified polyolefin;

Then it is mixed with polypropylene, melt-blended, and extruded to obtain a special fiber-forming resin for fine-denier fibers blended with modified polymeric polyolefin and polypropylene containing rare earth materials. After melt-spinning and stretching, the obtained fibers are monofilament The fineness is 0.9～2dtex;

Based on the total weight of the rare earth material-modified polyolefin and polypropylene blended fine-denier polypropylene fiber, the weight of the rare earth material-modified polyolefin is 2-8%, and the weight of the polypropylene is 92-98%;

Said dispersant is selected from one of polyvinyl alcohol, polyacrylic acid, polymethacrylate or maleic anhydride-styrene copolymer, and in the aqueous solution containing dispersant, the content of dispersant is 0.01～0.04 g/ ml;

The amount of Na ₂ S ₂ O ₃ added is 0.0005-0.001 g/ml aqueous solution;

The amount of the surface-modified nano-rare earth particles is 0.03-0.05 g/ml aqueous solution;

The addition amount of initiator is 0.002～0.006 g/ml aqueous solution;

The addition amount of the modified olefin monomer is 0.3-0.5 g/ml aqueous solution;

The initiator is selected from one of dibenzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), potassium persulfate (K ₂ S ₂ O ₈ ) or peroxycarbonate;

Said modified polyolefin is prepared according to the basic method of (in-situ) suspension polymerization, such as the method disclosed in the document "Blends of Polypropylene and Modified Polystyrene for Dyeable Fibers" such as Huang Xin, which is a polyolefin containing a benzene ring structure unit. Alkenes, the general structural formula is:

In the formula, preferred R is selected from one of H or _CH3 ; m=1, 2, 3 or 4, n=180-720;

Said surface-modified nano-rare earth particles can be prepared by the method disclosed in "Research on the Surface Modification of _CeO Nanoparticles with Stearic Acid" by Xi Baoxin et al. ;

The rare earth is selected from cerium oxide, yttrium oxide or uranium oxide; the average particle size of the nano rare earth particles is 50-100 nanometers;

The dyeing method of said rare earth-containing material polyolefin and polypropylene blended fine denier dyeable polypropylene fiber of the present invention comprises the following steps:

(1) Put said rare earth-containing material-modified polyolefin and polypropylene blended fine-denier polypropylene fiber in the dyeing bath, add water according to the weight ratio of 1:15-30, and then add the blended fine-denier dyeable Use 1.0-3.0% polypropylene weight to remove oil and detergent, 0.5-3.0% soda ash, heat up to 70-85°C, and keep warm for 20-40min;

(2) Add disperse dyes and acetic acid, heat up to 50-60°C at a rate of 2-4°C/min, and then run for 10-20min;

The amount of disperse dye added is determined according to the color matching requirements. Based on the weight of the blended fine-denier dyeable polypropylene, the preferred amount is greater than 0 to 5%, and the amount of acetic acid added is 0.5-2.0% of the weight of the blended fine-denier dyeable polypropylene;

(3) Raise the temperature to 90-120°C at a rate of 1-2°C/min. When dyeing light-medium colors, the temperature is 90-100°C. When dyeing medium-dark colors, the temperature is 100-120°C, and run for 30-60 minutes;

(4) Drop water at a rate of 2-4°C/min to 80-90°C, and wash with clean water;

Further, after dyeing, the fine-denier polypropylene fiber should be treated to remove floating color. For the light-medium-color sample, add water at a bath ratio of 1:15-30, add a soaping agent blended with a fine-denier dyeable polypropylene fiber weight of 0-1.0%, and heat up to Run at 50-70°C for 20-40 minutes, wash with water; for medium-dark samples, add water at a bath ratio of 1:15-30, add soaping agent blended with 1.0-3.0% of the weight of fine-denier dyeable polypropylene, and heat up to 60- Run at 90°C for 20-40 minutes, wash with water;

The terms "light-medium color" and "medium-dark color" are clearly defined in the document "Dyeing Standard Depth Color Card" by Chen Guanlong.

Said soaping agent is selected from polyacrylic acid sodium salt or modified phosphoric acid ester, can adopt commercially available product, as the soap flake of Beijing Jieershuang High-tech Co., Ltd., Shandong Shilong Chemical Co., Ltd. and Ciba;

Said degreasing detergent is selected from fatty alcohol polyoxyethylene ether, polyoxyethylene phenol ether or alkylphenol polyoxyethylene ether, commercially available products can be used, such as Beijing Jieershuang High-Tech Co., Ltd. and Shandong Shilong The brand name of Chemical Co., Ltd. is the product of special oil degreasing agent LD-22;

By adopting the above method, the dyeing rate of disperse dyes can be greatly improved, and the color brightness, uniformity and color fastness of the dyed fibers are good.

The present invention requires that commercially available disperse dyes are screened according to the aggregation, fastness (friction resistance, water resistance, sun resistance, etc.) and K/S value of the dyes to find out the red, yellow and blue primary color families of the disperse dyes . By adopting one or more mixtures of disperse dyes and the dyeing process of the present invention, not only the dyeing rate of disperse dyes can be greatly improved, but also the color brightness, uniformity and color fastness after dyeing are better.

Detailed ways

Example 1

Preparation of fine-denier dyeable polypropylene blended with rare earth-containing materials modified polyolefin and polypropylene

Add 100 ml of absolute ethanol, 10 g of Y ₂ O ₃ nano powder and 8% C15 titanate coupling agent relative to the mass of Y ₂ O ₃ nano powder into a 250 ml three-necked flask. Then Y ₂ O ₃ nanoparticles dried at 100 °C for 2 h were gradually added into the flask, ultrasonically oscillated at 25 °C while stirring for 30 min. After shaking, heat and reflux at a constant temperature in a water bath at 80°C for 4 hours.

After ultrasonically dispersing the mixed suspension _of 6 grams of the surface-modified _Y2O3 nanoparticles together with 0.7 grams of dibenzoyl peroxide (BPO) and 80 grams of modified olefin monomers, add 4 grams of dispersant polyethylene Alcohol (PVA) and 0.2 g of Na ₂ S ₂ O ₃ in 250 ml of deionized water, react at 75°C for 1 hour, raise the temperature to 80°C for 1.5 hours, raise the temperature to 90°C for 1.5 hours, raise the temperature to 95°C, and harden the particles for 2 hours .

The general structural formula of the modified polyolefin is as formula 1, wherein, R is H, m=1, n=360.

Finally, the prepared hybrid modified polyolefin additive and polypropylene were melt-blended in a twin-screw extruder at 220° C. in a mass ratio of 6:94, and pelletized.

After melt spinning at 250°C, stretching 3 times at 80°C at a spinning speed of 1000 m/min, a fiber with a single filament fineness of 1dtex can be obtained.

Example 2

Raw material: the fiber of Example 1

The fiber samples were dyed light red by the following method.

The whole dyeing process includes steps such as pre-dyeing treatment, dyeing, and post-dyeing treatment in sequence. In the pre-dyeing process, after adding water to the prepared fine-denier polypropylene fiber at a bath ratio of 1:20, add special oil-removing yarn agent LD-22, the addition amount is 3.0% of the weight of the fine-denier polypropylene fiber, 3.0% of soda ash, and the temperature is raised to 85 ℃, keep warm for 40min. After adding water to the fiber after the pre-dyeing treatment with a bath ratio of 1:20, add 0.1% Disperse Red E-4B (Disperse Red 60) of the fine denier polypropylene weight, and the acetic acid addition is 0.7% of the fine denier polypropylene weight. Raise the temperature at 3°C/min to 50°C and run for 15 minutes. Then heat up to a certain temperature at 1.5°C/min, and the temperature for dyeing light and medium colors is 100°C. After running for 40 minutes, lower the temperature at 3°C/min to 90°C, then turn on the water, and wash with water twice. After dyeing, fine-denier polypropylene fiber should be dyed to remove floating color. For light-medium-color samples, add water at a liquor ratio of 1:30, heat up to 60°C and run for 30 minutes, then wash with water twice, and finally dry the dyed fiber. The method specified in Xu Muqing's "Printing and Dyeing Test" document, GB/T 3920-1997, GB/T3921.1-5-1997, GB/T 3922-1995 and GB/T 8424.1-3-2001 was used for detection. as follows:

Example 3

Using the same method as in Example 1, the fine denier dyeable polypropylene fiber blended with cerium oxide modified polyolefin and polypropylene was prepared. The weight ratio of cerium oxide modified polyolefin to polypropylene was 6:94, and the single filament fineness was 2dtex. The following method dyes the fiber sample blue.

The whole dyeing process includes steps such as pre-dyeing treatment, dyeing, and post-dyeing treatment in sequence. In the pre-dyeing process, add water to the prepared fine-denier polypropylene fiber at a bath ratio of 1:20, add 2.0% special oil-removing agent LD-22, add 1.5% soda ash, heat up to 75°C, and keep warm for 30 minutes. After adding water to the pre-dyeing fiber at a liquor ratio of 1:20, add 1% of Terasil Navy Blue GRL-C (Disperse Blue 79), and 1.0% of acetic acid. Raise the temperature at 3°C/min to 50°C and run for 15 minutes. Then heat up to a certain temperature at 1.5°C/min, and the temperature for dyeing light and medium colors is 100°C. After running for 60 minutes, lower the temperature at 3°C/min to 90°C, then turn on the water and wash it twice with clean water. After dyeing, the fine-denier polypropylene fiber needs to be dyed to remove floating color, add water at a bath ratio of 1:30, add 0.5% soap flakes, heat up to 60°C and run for 30 minutes, then wash with water for 3 times, and finally dry the dyed fiber. The method specified in Xu Muqing's "Printing and Dyeing Test" document, GB/T3920-1997, GB/T 3921.1-5-1997, GB/T 3922-1995 and GB/T 8424.1-3-2001 was used for detection. The results are as follows:

Example 4

Raw material: the fiber of embodiment 1, single filament fineness is 2dtex, with following method the fiber sample is dyed red.

The whole dyeing process includes steps such as pre-dyeing treatment, dyeing, and post-dyeing treatment in sequence. In the pre-dyeing process, add water to the prepared fine-denier polypropylene fiber at a bath ratio of 1:20, add 1.0% special oil-removing agent LD-22, add 1.0% soda ash, heat up to 75°C, and keep warm for 30 minutes. Add 2.5% of Disperse Red E-4B (Disperse Red 60) and 2.0% of acetic acid to the pre-dyeing fiber after adding water at a bath ratio of 1:20. Raise the temperature at 3°C/min to 50°C and run for 15 minutes. Then heat up to a certain temperature at 1.5°C/min, and the temperature for dyeing light and medium colors is 100°C. After running for 60 minutes, lower the temperature at 3°C/min to 90°C, then turn on the water and wash it twice with clean water. After dyeing, fine-denier polypropylene fiber should be dyed to remove floating color. For light-medium-color samples, add water at a bath ratio of 1:30, add 1.5% soap flakes, heat up to 60°C and run for 30 minutes, then wash with water for 4 times, and finally dry it. Dyed fiber. The method specified in Xu Muqing's "Printing and Dyeing Test" document, GB/T 3920-1997, GB/T 3921.1-5-1997, GB/T 3922-1995 and GB/T 8424.1-3-2001 is used for detection, and the results are as follows :

Example 5

Raw material: the fiber of embodiment 3, monofilament fineness is 2dtex, with following method the fiber sample is dyed yellow.

The whole dyeing process includes steps such as pre-dyeing treatment, dyeing, and post-dyeing treatment in sequence. In the pre-dyeing process, add water to the prepared fine-denier polypropylene fiber at a bath ratio of 1:20, add 1.0% special oil-removing agent LD-22, add 0.5% soda ash, heat up to 75°C, and keep warm for 30 minutes. After adding water to the pre-dyeing treated fiber at a bath ratio of 1:20, add 4.5% of Disperse Golden E-3RL (Disperse Yellow 23), 0.5% of Disperse Red E-4B (Disperse Red 60), and 2.0% of acetic acid. Raise the temperature at 3°C/min to 50°C and run for 15 minutes. Then the temperature was raised to 120°C at 1.5°C/min. After running for 60 minutes, lower the temperature at 3°C/min to 90°C, then turn on the water and wash it twice with clean water. After dyeing, the fine-denier polypropylene fiber needs to be dyed to remove floating color. For light-medium-color samples, add water at a bath ratio of 1:30, add soap flakes 3.0%, heat up to 70°C and run for 30 minutes, then wash with water for 5 times, and finally dry it. Dyed fiber. The method specified in Xu Muqing's "Printing and Dyeing Test" document, GB/T 3920-1997, GB/T 3921.1-5-1997, GB/T 3922-1995 and GB/T8424.1-3-2001 was used for detection. as follows:

Claims (7)

1. a kind of dyeing method that contains rare earth material modified polyolefin and polypropylene blending fine denier polypropylene fiber, is characterized in that, comprises the steps: (1) Put rare earth-containing material-modified polyolefin and polypropylene blended fine-denier polypropylene fiber in the dyeing bath, add water according to the weight ratio of the bath ratio of 1:15-30, add the blended fine-denier polypropylene fiber weight 1.0-3.0 % oil-removing detergent, 0.5-3.0% soda ash, heat up to 70-85°C, keep warm for 20-40min; (2) Add disperse dyes and acetic acid, heat up to 50-60°C at a rate of 2-4°C/min, and then run for 10-20min; The amount of disperse dye added is determined according to the color matching requirements, and the amount of acetic acid added is 0.5-2.0% of the weight of the blended fine-denier polypropylene fiber; (3) Heat up to 90-120°C at a rate of 1-2°C/min, and run for 30-60min; (4) Drop water at a rate of 2-4°C/min to 80-90°C, and wash with clean water. The general structural formula of said modified polyolefin is: Formula 1 In the formula, preferably R is selected from one of H or CH ₃ ; m=1, 2, 3 or 4, n=180-720. 2. The method according to claim 1, characterized in that, the amount of disperse dyes is greater than 0 to 5% based on the weight of the blended fine denier polypropylene fiber. 3. The method according to claim 1, wherein the temperature is 90-100°C when the step (3) dyes a light-medium color. 4. The method according to claim 1, characterized in that, when step (3) is dyed in a dark color, the temperature is 100-120°C. 5. The method according to claim 1, characterized in that, after dyeing, the fine denier polypropylene fiber is processed to remove floating color. 6. The method according to any one of claims 1 to 5, characterized in that said rare earth-containing material-modified polyolefin and polypropylene blended fine-denier polypropylene fiber is the modified polyolefin containing rare-earth material and The resin obtained by blending polypropylene is melt-spun and stretched to obtain a fiber with a single filament fineness of 0.9-2dtex, wherein the weight content of the modified polyolefin containing rare earth materials is 2-8%, and the weight of polypropylene The content is 92-98%. In the modified polyolefin containing the rare earth material, the weight content of the rare earth material is 7.5-12.5%, and the weight content of the modified polyolefin is 87.5-92.5%. 7. The method according to claim 6, wherein said rare earth is selected from cerium oxide, yttrium oxide or uranium oxide.