JP2000054261A - Treatment of cellulose fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the fibrillation by treating a lyocell cellulose fiber with a specific compound. SOLUTION: A lyocell cellulose fiber in a state after spinning and before drying or before dyeing or simultaneously with the dyeing is treated with at least one kind of compound represented by the formula [A is phenyl or the phenyl substituted with hydroxy, carboxy or the like, a (substituted) naphthyl or the like; R2 is a halogen; R2 is a halogen; a (substituted) phenyl, a (substituted) naphthyl or the like; R3 is H or a 1-4C alkyl] in an amount of 0.1-15 wt.%, preferably 1-10 wt.%, more preferably 2-6 wt.% based on the fiber weight in a treating bath or a dye bath containing an alkaline medium such as sodium carbonate or sodium hydroxide and reducing the tendency to form microfibers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a method for reducing the tendency to form microfibrils in lyocellulose fibers.

[0002] "Lyocell" means a fiber obtained by dissolving cellulose in an organic solvent, a combination of an organic solvent and an inorganic salt, or an aqueous salt solution and then spinning from that solution.

[0003] However, the utility of flat products, such as textile materials, made from such fibers is severely limited as a result of their pronounced tendency to microfibrillation in the wet state. "Microfibrillation" refers to the formation of wet fibers in the longitudinal direction such that the fibrils separate along the surface of the fiber when subjected to mechanical forces, giving the fiber a hairy or fluffy appearance. It should be understood to mean destruction. Furthermore, fabrics made from such fibers result in a significant loss of color strength after several launderings.

[0004] Therefore, there is a need for a method of reducing or completely preventing microfiber formation in lyocell fibers.

Surprisingly, it has been found that the process of the present invention substantially reduces the tendency of treated lyocell fibers to form fibrils.

[0006] Accordingly, the present invention is a method for treating lyocellulose fiber, wherein the lyocellulose fiber is treated by the formula (1):

[0007]

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Wherein A is unsubstituted phenyl or phenyl substituted by hydroxy, carboxy, -NH-CO-CBr = CH ₂ or -NH-CO-CHBr-CH ₂ Br, or unsubstituted naphthyl or hydroxy, carboxy, _{sulfo, -SO 2 -CH = CH 2,} -S
O ₂ —CH ₂ CH ₂ —OSO ₃ H, —NH—CO—CBr =
Is CH ₂ or naphthyl which is substituted by _{-NH-CO-CHBr-CH 2} Br, R 1 is halogen, R ₂ is halogen, unsubstituted groups phenyl, or hydroxy, carboxy, -NH-CO- CBr = CH ₂
Or phenyl substituted by _{-NH-CO-CHBr-CH 2} Br, unsubstituted naphthyl or hydroxy, carboxy, _{sulfo, -SO 2 -CH = CH 2,} -S
O ₂ —CH ₂ CH ₂ —OSO ₃ H, —NH—CO—CBr =
Naphthyl substituted by CH ₂ or _{-NH-CO-CHBr-CH 2} Br, and R ₃ is hydrogen, unsubstituted C ₁ -C ₄ alkyl or hydroxyalkyl or C ₁ -C ₄ alkyl substituted by a sulfo With the proviso that R ₁ and R ₂
Is halogen, and A and R ₃ are as defined above, or A and R ₂ are phenyl or naphthyl, and —SO ₂ —CH ＝ CH ₂ , —SO ₂ —CH ₂ CH _{2
-OSO 3 H, -NH-CO-} CBr = CH 2 and -NH
Is selected from -CO-CHBr-CH ₂ group consisting of Br, a method of processing at least one same or different at least two must contain a substituent), a compound represented by.

As C ₁ -C ₄ alkyl, R ₃ is methyl, ethyl, propyl, isopropyl, n-butyl, se
c-butyl, isobutyl or tert-butyl.

As halogen, the radicals R ₁ and R ₂ are each, independently of the others, fluoro, in particular chloro.

Compounds of formula (1) of particular interest for the process of the present invention are those wherein R ₂ is halogen.

Compounds of formula (1) of particular interest for the process of the invention are those wherein R ₁ and R ₂ are chloro.

Compounds of formula (1) of particular interest in the process of the present invention are those wherein R ₁ and R ₂ are chloro and -NR ₃ is-
_{NH -, - N (CH 2} CH 2 OH) -, - N (CH 2 SO 3
H) - or -N (CH ₂ CH ₃₎ - and is, and A is represented by the following formula:

[0014]

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Are those which are any of the groups

Compounds of particular interest for the process according to the invention are those of the formulas (100) to (107):

[0017]

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Is a compound of the formula:

Particularly important compounds for the process according to the invention are compounds of the formulas (103), (106) and (107).

The compounds of the formulas (106) and (107)
New and the invention is also related to it.

The preparation of the compounds of the formula (1) used in the process according to the invention can be carried out in a manner known per se, for example of the formula (20):

[0022]

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The trichlorotriazine of the formula (21):

[0024]

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(Wherein R ₃ and A are as defined in formula (1)) with an equimolar amount of a compound of formula (1), and then isolating the obtained target compound of formula (1). You.

The preparation of the novel compounds of the formulas (106) and (107) involves the conversion of the trichlorotriazine of the formula (20) to the compound of the formula (30) or (31)

[0027]

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The reaction is carried out in a similar manner by reacting with an amine of the formula

An advantageous embodiment of the method according to the invention comprises treating the lyocellulose fiber with the compound used according to the invention in an alkaline medium.

The alkaline medium is preferably formed by an alkali metal carbonate and / or an alkali metal hydroxide, such as sodium carbonate, sodium hydroxide or potassium hydroxide.

The treatment is carried out either on undyed fibers or on the fibers to be dyed before, during or immediately after the dyeing step.

If the compounds used in the present invention are applied to undyed fibers, they may be treated baths or freshly spun yet not dried fibers (which are
For example, EP-A-0538977, page 4, or US-
A-5580354, as described in column 4, the so-called "never-dried fiber".
d) is applied immediately after the spinning operation.

If the compounds used according to the invention are applied in the course of a dyeing process, their application is conveniently effected before or during the actual dyeing operation.

In this case, the compound used in the present invention is
It can be applied in a separate treatment bath or under suitable dyeing conditions together with the dyes preferably used in the dyeing bath.

If the compound used in the present invention is applied to fibers from another treatment bath, it may be between 15 and 14
0 ° C., preferably 40-100 ° C., 10-120
Minutes, preferably for a period of 30 to 90 minutes. A further advantageous embodiment of the invention is that the fibers are wetted with an aqueous solution of the compound used according to the invention, and then they are dried for 5 to 60, preferably 10 to 30 seconds, 90 to 90 seconds.
Subject to steam at a temperature of 130 ° C. The fibers can be wetted by dipping or spraying in a bath.

The lyocellulose fiber can be in the form of a fiber, in the form of a yarn, or in the form of a flat product such as a woven, knitted or web. But it can be processed.

The compound used in the present invention is usually 0.1 to 15% by weight, especially 1 to 15% by weight, based on the weight of the fiber.
A quantity of 10% by weight, more particularly 2 to 6% by weight, is used in the treatment or dyeing bath.

The present invention relates to the use of the compounds of formula (1) for reducing the formation of microfibrils in lyocellulose. The tendency of the untreated and treated fibers to form microfibers is indicated by the improved Martindale rub test (Martindale a
brasion test, in which a wet specimen of the fabric was evaluated by being worn down at a defined load until holes were formed. The number of abrasion cycles required for the holes formed provides resistance to wet attrition and is a measure of fibril formation.

The following examples serve as an illustration of the present invention. Unless indicated otherwise, temperatures are in degrees Celsius, parts are parts by weight, and percentages are by weight. Parts by weight relate to parts by volume and kilograms to liters.

[0040]

Example 1 In a laboratory reaction vessel, 18.5 g of cyanuric chloride in a mixture of 100 parts of ice and 100 parts of water containing 0.1 g of a commercially available surfactant aid were stirred vigorously.
Then, 13.7 g of neutral solution of 4-aminobenzoic acid was added and the temperature was maintained at 0 ° C. and the pH at 6.0. When the amine was no longer detectable by HPLC, the reaction product was precipitated by salting out and isolated by filtration. After drying at 30 ° C., the formula (103):

[0041]

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The compound was obtained.

Examples 2 to 8: Proceed as described in Example 1, but substituting 13.7 g of 4-aminobenzoic acid with the formula (5
Using the equimolar amounts of the compounds of (0) to (55) or (30) or (31), the formulas (100) to (10) shown in Table 1 were used.
2) and the compounds of (104) to (107) were obtained.

[0044]

[Table 1]

Table 2 shows the HPLC data of some compounds of the present invention.

[0046]

[Table 2]

Measurement conditions: Column: Hewlett Packard Hypersil ODS 5 UM; 250 × 4 mm Flow rate: 1.2 ml / min; Solvent A: 2 g / l of TBAB (tetrabutylammmoniumbromide)
Solvent B: 40.0% water containing 2 g / l of TBAB; furnace temperature: 40.0 ° C .; injection volume: 10.0 μl; water / acetonitrile (60/4)
1% solution of sample in 0)

[0048]

[Table 3]

Example 9: 50 ml of water and sodium sulfate 2
A solution consisting of 15 ml of a 0% aqueous solution was introduced into a laboratory dyeing machine and heated to 50 ° C. A 10 g piece of lyocell fabric was immersed in this solution, and the temperature was raised to 90 ° C. at a rate of 2 ° C./min. Upon heating, 0.6 g of the compound of formula (114) in 27.5 ml of water was added at 70 ° C. Lyocell fabric 60 at 90 ° C
Minutes. Next, the treatment liquid is cooled to 70 ° C.
7.5 ml of aqueous sodium carbonate solution are added and the mixture is
C. for another 45 minutes. The bath was then removed and the treated lyocell fabric was rinsed with water, boiled for 5 minutes in a fresh bath containing only water, cold rinsed again and dried. In the Martindale rub test, the dried lyocell fabric has about 60 times the number of rub test cycles compared to the untreated lyocell fabric.
% & Many times endured.

In this way of application, the lyocell fabric can be dyed simultaneously with the addition of one or more reactive dyes immediately after the addition of the compound of the formula (107).

Proceeding as described in Example 9, but replacing the compound of formula (107) with formulas (101), (1
Using the same amount of the compound of (03), (104), (105) or (106), a lyocell fabric having a high Martindale rub test value was likewise obtained.

Example 10 A solution consisting of 50 ml of water and 15 ml of a 20% aqueous solution of sodium sulphate was introduced into a laboratory dyeing machine and heated to 60.degree. A 10 g piece of lyocell fabric was immersed in this liquid, and dissolved in 25.5 ml of water after 3 minutes.
0.6 g of the compound of 6) was added. After another 15 minutes, 20%
7.5 ml of aqueous sodium carbonate solution was added to this solution. The solution was then maintained at 60 ° C. for 30 minutes. Then, 2 ml of a 3% aqueous sodium hydroxide solution was added, and the mixture was further heated at 60 ° C. for 10 minutes.
And the lyocell fabric was finished as described in Example 9. The finished lyocell fabric can then be dyed in a customary manner, for example with a reactive dye. In the Martindale rub test, the dried lyocell fabric withstood about 60% more number of rub test cycles compared to the untreated lyocell fabric.

Proceeding as described in Example 10, but replacing the compound of formula (106) with formulas (101), (1
Using the same amount of the compound of (03), (104), (105) or (107), a lyocell fabric having a high Martindale rub test value was likewise obtained.

Example 11: A lyocell fabric was prepared according to the formula (10)
7):

[0055]

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Compound 42 g / l, calcined sodium carbonate 3
The lyocell fabric so treated, dyed with an aqueous liquor containing 0 g / l and 1 g / l of a commercially available humectant (liquid absorption: 70%), is dried without drying in a saturated steam at a temperature of 102 ° C. for 8 minutes. Processed directly. The lyocell fabric is then rinsed with water,
Boil for 5 minutes in a fresh bath containing only water, rinse again cold and dry. In the Martindale rub test, the dried lyocell fabric withstood about 1.5 times the number of rub test cycles compared to the untreated lyocell fabric.

Claims (10)

[Claims] 1. A method of treating lyocellulose fiber, comprising the steps of: treating lyocellulose fiber with the formula (1): Wherein A is an unsubstituted phenyl or hydroxy, carboxy,
-NH-CO-CBr = CH ₂ or -NH-CO-
Phenyl substituted by CHBr—CH ₂ Br, or unsubstituted naphthyl or hydroxy, carboxy, sulfo, —SO ₂ —CH ＝ CH ₂ , —SO ₂ —CH ₂ CH ₂ —O
_{SO 3 H, -NH-CO-} CBr = CH 2 or -NH
-CO-CHBr-CH ₂ naphthyl substituted by Br, R ₁ is halogen, R ₂ is halogen, unsubstituted groups phenyl or hydroxy,
Carboxy, -NH-CO-CBr = CH 2 or -
NH-CO-CHBr-CH phenyl substituted by ₂ Br, or unsubstituted naphthyl or hydroxy, carboxy, _{sulfo, -SO 2 -CH = CH 2,} -SO 2 -C
H ₂ CH ₂ -OSO ₃ H, naphthyl substituted by -NH-CO-CBr = CH ₂ or _{-NH-CO-CHBr-CH 2} Br, and R ₃ is hydrogen, unsubstituted C ₁
-C ₄ alkyl or C ₁ -C ₄ alkyl substituted with hydroxy or sulfo, provided that R ₁ and R ₂ are halogen and A and R ₃ are as defined above, or A and R ₂ is a phenyl or naphthyl, and _{-SO 2 -CH = CH 2, -SO} 2 -CH 2 CH 2 -OS
_{O 3 H, -NH-CO-} CBr = CH 2 and -NH-CO
It is selected from the group consisting of -CHBr-CH ₂ Br, wherein the treatment with at least one same or different at least two must contain a substituent), a compound represented by. 2. A lyocellulose fiber, R ₁
And R ₂ is chloro, -N-R ₃ is -NH -, - N
_{(CH 2 CH 2 OH) -} , - N (CH 2 SO 3 H) - or -
N (CH ₂ CH ₃ ) —, and A is of the following formula: The method of claim 1, comprising treating with at least one compound of formula (1) that is any of the groups: 3. A lyocell cellulose fiber having the formula (100) to (107): 3. The method according to claim 2, comprising treating with at least one compound of the formula: 4. Formula (1) based on fiber weight
2. The method according to claim 1, comprising using 0.1 to 15% by weight of a compound of formula (I). 5. The formula (10) based on the weight of the fiber
4. The method according to claim 3, comprising using 0.1 to 15% by weight of one of the compounds of 0) to (108). 6. applying the compound of formula (1) to the freshly spun fiber which has not been dried yet.
The method of claim 1. 7. The method of claim 1, comprising applying the compound of formula (1) to the fiber before or during the dyeing step. 8. A compound of the formula (106) or (107): A compound represented by the formula: 9. The expression (106) or (10) according to claim 8,
A method for producing the compound of 7), comprising the step of formula (20): With a trichlorotriazine of formula (30) or (31): A method characterized by reacting with the compound of the above. 10. Use of a compound according to claim 1 for reducing microfibril formation in lyocellulose fibers.