JPH09302584A - Method for preventing fibrillation of solvent-spun cellulose fibers - Google Patents

Abstract

(57) Abstract: [PROBLEMS] To provide a method for preventing fibrillation, which is capable of treating a solvent-spun cellulosic fiber at any manufacturing step of a fiber product and does not adversely affect dyeability. SOLUTION: The solvent-spun cellulose fiber is treated with a water-soluble epoxy compound having two or more epoxy groups in one molecule, a method for preventing fibrillation of a solvent-spun cellulose fiber, and a fibrillation resistance treated in this way. Excellent solvent-spun cellulose fiber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing fibrillation of solvent-spun cellulose fibers and a solvent-spun cellulose fiber having improved fibril resistance.

[0002]

2. Description of the Related Art Solvent-spun cellulose fibers have excellent physical properties because they have a highly oriented fiber structure, but on the other hand, due to their high orientation, mechanical forces such as friction are applied especially in a wet state. And has the property of being easily fibrillated. Utilizing this fibrillation, clothing products having a fancy texture have been marketed. For example, a product in which only fine fibrils remain has been produced by extremely generating fibrils in a dyeing and arranging process of woven fabrics and knitting, and then removing large fluff using a cellulolytic enzyme cellulase. However, such fibrillation often becomes fluff, which makes it unattractive and causes pilling. Further, recently, the needs have been diversified, and there has been an increasing demand for products that have no fibrils and have a clear and flexible feel.

In order to meet such recent needs, many methods for preventing fibrillation of solvent-spun cellulose fibers have been investigated. JP-A-5-11797
No. 0 discloses a technique of treating cellulose fibers with a chemical having 2 to 6 functional groups that react with cellulose. Specific chemical agents include polyfunctional triazine compounds, vinyl sulfones, and reactive dyes having a plurality of triazine-based reactive groups, but it is also clear that the former was developed as a dye-proofing agent. As described above, it markedly inhibits the dyeability after treatment,
In the latter case, the prevention of fibrillation can be achieved to some extent if the color is dark, but the effect is insufficient as the color becomes lighter, and reactive dyes having a plurality of reactive groups are generally of low temperature type. It is classified, uneven,
Due to the problem of wrinkles, the dyeing method is usually avoided in dyeing with cloth. That is, the processing method for preventing fibrillation is the shape of the material to be dyed (for example, sliver, yarn, woven fabric, knitting).
Must be conscious of this, and the processing steps are greatly limited when manufacturing textile products for clothing.

ITB Dyeing / Printing
/ Finishing Vol.40, No.2, P.5-
8, JP-A-6-146168, JP-A-6-322
In Japanese Patent Laid-Open No. 666 and Japanese Patent Laid-Open No. 7-70930,
N-methylol amine crosslinking agent (glyoxal,
Urea, melamine resin) is disclosed. Also in this method, since the dyeing property after treatment is significantly impaired, it is essential to carry out after dyeing, and there are drawbacks that not only the post-dyeing cannot be dealt with in the process, but also the fibrillation that occurs during the pre-dyeing cannot be prevented. Further, when such resin processing is performed, it is unavoidable that the texture of the fibers is coarse and hard. Japanese Unexamined Patent Publication No. 8-013363 discloses that
Although a method for preventing fibrillation using a cationizing agent is disclosed, the introduced quaternary ammonium salt significantly increases the affinity for anionic dyes (ordinary cellulosic fiber dyes) and improves the initial dyeing property. It has a drawback that it causes uneven dyeing due to high cost.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for preventing fibrillation, which is capable of treating solvent-spun cellulosic fibers at any manufacturing step of a fiber product. Ie sliver, thread,
A technology that can be applied to top dyeing machines, cheese dyeing machines, cassette dyeing machines, anti-dying machines, or pad processing during the organizing process, regardless of the form of woven fabric or knitting, and has no adverse effect on post-dyeing. To provide.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a method for preventing fibrillation of solvent-spun cellulose fibers by treating solvent-spun cellulose fibers with a water-soluble epoxy compound having two or more epoxy groups in one molecule. The present invention relates to a solvent-spun cellulosic fiber which is excellent in fibril resistance and has been treated.

In one embodiment of the treatment method of the present invention, a water-soluble epoxy compound is added to a dyeing bath together with an alkaline agent, whereby the fiber is subjected to a fibrillation preventing treatment simultaneously with dyeing in the dyeing step. In another aspect,
The fiber is subjected to a fibril prevention treatment with a water-soluble epoxy compound before or after dyeing.

Garment fiber manufacturing processes are extremely diverse. For the sale of solvent-spun cellulose fibers with improved fibril resistance, pretreatment with raw cotton such as sliver is required. This pretreatment is also essential when producing a blended yarn with other fibers. In addition, knitted yarn, which will be a product if knitted, requires processing with raw cotton or knitted yarn. In this case, if it is a small lot, it is advantageous to process the yarn with a cassette dyeing machine or a cheese dyeing machine. The same applies to the case of a small amount of patterned fabric (including interwoven with other fiber yarn, including jacquard) and patterned knit (including interwoven with other fiber yarn).
Further, in the case of a large amount of the same lot of fabrics, continuous treatment by post-processing (before dyeing, after dyeing) with a piece of fabric is often advantageous. The present invention can be applied to any of the above cases. That is, it can be processed with a top dyeing machine, a cheese dyeing machine, and a cassette dyeing machine before and after dyeing, and a fabric can be processed by padding before and after dyeing.

In the present invention, a water-soluble epoxy compound which reacts with the active hydrogen of the fiber is used because the treatment is carried out in a usual processing step. The fibrillation-preventing effect of the present invention is considered to be due to the formation of crosslinks between the molecules of the cellulose fiber by the water-soluble epoxy compound. The water-soluble epoxy compound used in the present invention has two or more epoxy groups in one molecule in order to form a crosslink, and a functional group not present in the cellulose structure in order not to adversely affect the dyeability. The feature is that it is not introduced into cellulose. For example, the presence of amines, imides, etc. affects the dyeability, and epoxy compounds containing these functional groups are not preferred in the present invention.

Preferred epoxy compounds which can be used in the present invention are represented by the general formula (I)

Embedded image It has a chemical structure exemplified by

Of these, a particularly preferred epoxy compound is
Diglycidyl ether and R _{-O- (CH 2 CH 2 O)} n -
O-, where n = 1-5.

Another preferred epoxy compound is

Embedded image It has a chemical structure exemplified by

Of these, particularly preferred epoxy compounds are
Glycerol polyglycidyl ether and diglycerol polyglycidyl ether.

However, the water-soluble epoxy compound that can be used in the present invention is not limited to those exemplified above. The molecular weight of the epoxy compound is not particularly limited, but the number of cross-links with the active hydrogen of cellulose reacts at a molar ratio, and therefore relatively small ones are economically preferable because the same effect can be expressed even if the amount used is small. . That is, epoxy equivalent (WPE: weight per epoxy equival
The smaller the ent), the more preferable. In general, the higher the molecular weight, the higher the melting point and the gelation at room temperature, making it difficult to use. For example, in the case of polyethylene glycol diglycidyl ether, the number of chains of ethylene glycol is 1
It is preferably about 20.

Crosslinking of cellulose fibers with the water-soluble epoxy compound of the present invention can be carried out without problems by various known methods. In the case of batch processing using a dyeing machine, the reaction may be performed in the presence of an alkaline agent such as sodium hydroxide. There is no significant difference in dyeability after crosslinking treatment from that of untreated one, and there is no problem at all. Moreover, the dye used for the cellulose fiber is usually a reactive dye, and the dyeing conditions and the crosslinking conditions with the epoxy compound are the same, and the dyeing and the fibrillation preventing treatment can be carried out simultaneously in the same bath. Although its kinetic mechanism is not well understood, good dyeing property and fibril resistance can be achieved by one-bath treatment, which is extremely advantageous for labor saving of the process.

When the crosslinking treatment of the present invention is carried out before or after dyeing, the batch treatment may be carried out in the presence of an alkaline agent in the same manner as described above. The weight of the general alkaline agent used is 1/10 to 1/2 of the amount of the water-soluble epoxy compound used in the case of sodium hydroxide. It is possible and more advantageous to add the alkaline agent in a divided manner in order to uniformly cause a crosslinking reaction between the cellulose molecules. When the fibril-proofing treatment is continuously carried out by processing the cloth, the padding treatment can be carried out by an ordinary known method. For example, the epoxy compound and the acidic catalyst may be added to water or an isopropyl alcohol aqueous medium for padding, followed by drying and heat treatment. As an acidic catalyst used with a stabilizer such as zinc oxide,
Examples thereof include magnesium borofluoride, zinc borofluoride, and aluminum sulfate.

The amount of the epoxy compound required to completely prevent the fibrillation of the cellulose fiber is determined by the molecular weight thereof and the yarn, the woven fabric, or the yarn composed of the cellulose fiber.
Although this cannot be generally stated depending on the properties of the knitted product, the epoxy compound is used in an amount of 0.08 mol or more, preferably 0.08 to 0.8 mol, in consideration of the epoxy equivalent per 100 g of the cellulose fiber. For example, "Denacol EX-850" (ethylene polyethylene glycol diglycidyl ether, n
= 2, WPE = 121) (Epoxy compound manufactured by Nagase & Co., Ltd.), when the knitted yarn-shaped solvent-spun cellulose fiber "TENCEL" (manufactured by Courtesle) is treated,
Denacol EX-850 may be used at 10% owf or more.

The solvent-spun cellulose fibers to be subjected to the fibril treatment in the present invention are solvents capable of dissolving cellulose such as wood pulp and cotton, for example, N-methylmorpholine-N-oxide, dimethyl sulfoxide, N. -A fiber produced by spinning a solution dissolved in methylpiperidine-N-oxide, dimethylacetamide or the like by a dry or wet spinning method. One that is currently in practical use is "TENCEL" (trade name), which is developed and marketed by Courtalls Ltd. in the UK. This is a cellulose fiber obtained by wet-preventing pulp from a spinning dope prepared by dissolving it in N-methylmorpholine-N-oxide. This solvent-spun cellulose fiber is a cellulose fiber produced by conventional chemical regeneration,
For example, unlike viscose rayon, cuprammonium rayon, and polynosic fiber, it is highly crystalline and highly oriented.

The fibrillation preventing method of the present invention can be applied to cellulosic fibers other than solvent-spun cellulose fibers. However, in the case of the conventional regenerated cellulose fiber, fibrillation is not so remarkable, and in general, such treatment is not always required at present. Further, the cellulose fibers to be treated in the present invention not only mean fibers in a yarn state but also include woven fabrics, knitted fabrics, textile processed products such as sliver, and intermediate products.

Hereinafter, the present invention will be described in more detail with reference to examples. Example 1 Solvent-spun cellulose fiber "TENCEL" (manufactured by Courtes Co.) using a spinning raw material (2.4 dTex, 60 to 90 mm cut) by a conventional spinning (card, top) process,
Created a sliver top ball. Twenty-four top balls (7 kg per top ball) were filled in a top dyeing machine and scoured by a conventional method using a nonionic surfactant and an aqueous NaOH solution. After the reconstitution, water was added so that the bath ratio became 1:15, and the epoxy compound "Denacol EX-810" was added to this.
(Ethylene glycol diglycidyl ether, n = 1,
WPE = 112) (made by Nagase & Co., Ltd.) 40% owf
And the fibrillation preventing treatment was started. After 10 minutes (water temperature) after adding the epoxy compound, 5% owf of sodium hydroxide was slowly added additionally over 10 minutes. After that, the temperature is raised at a heating rate of 1 ° C./min to 80 ° C.
After reaching the temperature of 60 minutes, the solution was maintained for 60 minutes, and the fibril prevention treatment was completed by carrying out liquid modification, soaping and neutralization. After drying and combing the sliver, a knitting yarn of 2/50 (bottom twist; Z700, top twist; S360) was manufactured by a conventional spinning process. Is it because the ethylene glycol group is introduced in the spinning?
It had an appropriate moisturizing property and was extremely good. The produced yarn is made into cheese, and the cheese dyeing machine uses the reactive dye "Civbacron Scarlet 2G-" as a dye.
E "(manufactured by Ciba-Geigy Co.) 3% owf was used for dyeing by a conventional method to produce a 12-gauge (double take-up) textured weft knitted sweater.

Example 2 Using the same tencel spinning raw material as in Example 1, by a conventional spinning process, 2/50 (bottom twist; Z700, top twist; S36)
0) A knitted yarn was produced. Manufactured cheese-like thread 1
00 kg (1 kg / cheese) was scoured by a cheese dyeing machine in a conventional manner. After washing with water, the epoxy compound "Denacol EX-851" (ethylene polyethylene glycol diglycidyl ether, n = 2, WPE = 1 with a bath ratio of 1:10)
54) (manufactured by Nagase & Co., Ltd.) was added to 40% owf to start the fibrillation preventing treatment. Sodium hydroxide 2% owf was added at room temperature. While increasing the temperature at 1 ° C./min, 2% owf of sodium hydroxide was added at 50 ° C., and 2% owf was further added at 80 ° C., and the mixture was treated at 80 ° C. for 60 minutes. After the liquid was reconstituted, it was dyed in the same manner as in Example 1 to produce a flat knit sweater.

Example 3 2/50 obtained by spinning and refining in the same manner as in Example 2.
The knitted yarn was dyed with a cheese dyeing machine and subjected to fibril prevention treatment in the same bath. 100 kg of the above knitting yarn was put into a cheese dyeing machine, and then water was added so that the bath ratio was 1:10, and a leveling agent (“Texport DL-91”; manufactured by Nika Chemical Industry Co., Ltd.) 1 g / L, a reactive dye. "Procio
n Navy H-EXL ”(manufactured by ICI) 3% owf,
Epoxy compound “Denacol EX-851” 40% ow
f, anhydrous sodium sulfate 40 g / L, soda ash 15 g
/ L in that order. The temperature was raised to 95 ° C. at 1 ° C./min, the temperature was treated for 35 minutes, the temperature was gradually cooled to 60 ° C., 4% owf of sodium hydroxide was added, and the treatment was continued for 20 minutes. A sweater was obtained in the same manner as in Example 2 after liquid modification, soaping and neutralization.

Example 4 Tencel spun yarn (product name: USA-1, 30
/ 1, Shin Inner and Outer Cotton Co., Ltd., twill structure; 3/1, density: inch-to-inch diaper 33.0 / 4 = 1 per draw
32 pieces, the number of plunges; 88 pieces of 100% tencel fabric were obtained. It was exposed to air and dried in the usual way. 100 parts by weight of water, epoxy compound "Denacol EX-821" (ethylene polyethylene glycol diglycidyl ether,
n = 4, WPE = 195) A padding bath containing 25 parts by weight, 1.6 parts by weight of aluminum sulfate and 0.2 parts by weight of zinc oxide was prepared, and 2 dips and 2 nip (squeezing ratio 80%).
Then, it was pre-dried at 80 ° C. and heat-treated at 150 ° C. for 4 minutes. The fabric is then placed in a jet dyeing machine, soaped and then the reactive dye Drimarene Navy X-GN.
(Manufactured by Sand Co.) was dyed with 3% owf by a conventional method (all-in method) at 90 ° C. for 60 minutes and finished by a usual method to obtain a product.

Example 5 A product dyed and treated with an epoxy compound was obtained in exactly the same manner as in Example 4 except that the order of dyeing and padding was changed and the padding treatment was carried out after dyeing.

Comparative Example 1 A dyed weft-knitted sweater was produced in the same manner as in Example 2 except that the anti-fibrillation treatment was not performed.

Comparative Example 2 A dyed woven fabric was obtained in the same manner as in Example 4 except that the padding (anti-fibrillation) treatment was not performed.

Results of fibrillation test The products obtained in Examples 1-5 and Comparative Examples 1-2 were subjected to a fibrillation test and the following results were obtained. [Evaluation 1] The practical washing test of JIS L-0217 103 method was repeated 10 times and dried by a tumbler dryer, and the state of fibril generation on the surface of the fabric was observed. Example 1: No change from before washing (no generation of fibrils) 2: 〃 3: 〃 4: 〃 5: 〃 Comparative example 1: Whitening phenomenon due to fibrillation appeared, and it was also pill-like 2: 〃

[Evaluation 2] Gakushin-type friction test A wet friction test was conducted using a fastness tester to evaluate the surface condition of the knitted fabric and the woven fabric after the test. Dyeability evaluation results All the products treated in Examples 1 to 5 were dyed well without trouble such as uneven dyeing, and there was almost no significant difference in dyeability (color) from the corresponding Comparative Example. It was

[0029]

INDUSTRIAL APPLICABILITY The method of the present invention can completely suppress the generation of fibrils in solvent-spun cellulose fibers, does not adversely affect the dyeability, and can be adopted at any position in the general dyeing and organizing process. .

Claims (6)

[Claims] 1. A method for preventing fibrillation of a solvent-spun cellulose fiber, which comprises treating a solvent-spun cellulose fiber with a water-soluble epoxy compound having two or more epoxy groups in one molecule. 2. A water-soluble epoxy compound has the general formula (I): The method for preventing fibrillation of solvent-spun cellulose fibers according to claim 1, which is a mixture of one or two or more selected from the compounds represented by: 3. The temperature is increased while immersing the solvent-spun cellulose fiber in an alkaline aqueous solution of a water-soluble epoxy compound, or the aqueous solution of an aqueous epoxy compound containing an acidic catalyst is adhered to the solvent-spun cellulose fiber, dried and then acidified. The method for preventing fibrillation of solvent-spun cellulose fibers according to claim 1, wherein heating is performed at a temperature at which the catalyst is activated or higher. 4. The solvent according to claim 1, wherein the water-soluble epoxy compound according to claim 1 or 2 is added to a dyeing bath of cellulose containing an alkaline agent, and the epoxy compound treatment is performed simultaneously with dyeing. A method for preventing fibrillation of spun cellulose fibers. 5. The cellulose fiber before or after dyeing is treated with a water-soluble epoxy compound.
A method for preventing fibrillation of a solvent-spun cellulose fiber according to any one of 1. 6. A solvent-spun cellulose fiber excellent in fibrillation resistance, which is treated by the method according to any one of claims 1 to 5.