JPH06501994A - fiber processing - 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] fiber processing Background technology Regenerated cellulose fibers by spinning a solution of cellulose into a suitable solvent Various proposals have been made for manufacturing. An example of such a process is the UK patent It is described in Specification No. 2043525, the contents of which are referred to herein. It will be done. In such a solvent spinning process, the solvent for cellulose is For example, tertiary amine N-oxyto, which is N-methylmorpholine N-oxyto. Cellulose is dissolved in a suitable solvent. The solution is then spun through a suitable die. The filament is then washed in water to remove the solvent. be done. The fibers are washed during the processing process, sometimes both before and after washing, if necessary. It is recommended that the film be stretched. The fibers are then typically processed in a known manner prior to being utilized. Finished.

The present invention specifically seeks to reduce the tendency of fibers to fibrillate. The present invention relates to the treatment of solvent-spun cellulose fibers. Fibrillation refers to the formation of fibers in the longitudinal direction. separation and the formation of a fluff-like structure. Actual to reduce fibrillation The process is necessary only to reduce fibrillation itself; In order to have a minimal effect on the subsequent dyeability of the fiber, and to have a slight effect on the strength and elongation of the fiber. It is necessary to provide the maximum possible effect. Fibrillation decreases, but Unfortunately, various processes are being studied to reduce the strength and elongation of fibers. Strong elongation of fibers Various other processes that do not reduce the dyeability but have an adverse effect on the dyeability of the fibers being researched.

The present invention not only reduces the fibrillation tendency but also clearly reduces the strength and elongation. Visibly inhibits fibrillation of fibers without any obvious adverse effect on color. The need for a process to obtain treated fibers that develops a clearly reduced tendency It is a challenge. Maintaining a balance between all the required properties of fibers is extremely difficult. Because the tendency to fibrillation is low, but very Producing fibers with low strength, very low elongation, or very low dyeability. This is because it is not enough. It is also so rigid that it cannot be handled. It is unsatisfactory to produce fibers that are so brittle that they cannot be otherwise processed.

Disclosure of invention A book on producing regenerated cellulose fibers with a reduced tendency to fibrillation In the method according to the invention, undried regenerated cellulose fibers are treated with a plurality of cationic ions. It is characterized in that it is treated with an aqueous solution or dispersion of a polymer having a polymerization site. dry Regenerated cellulose that has not been dried (more specifically, rice has never been dried) Fibers are fibers that have been prepared for drying but have never been dried. This is regenerated cellulose fiber that has been washed after regeneration. Fibers that have not been dried should be dried. have different physical properties than the fibers that are being dried and rewetted, e.g. develops high water swelling properties.

The regenerated cellulose fiber according to the present invention has a plurality of cationic ionization sites. The fibers are characterized in that they have a coating consisting of lima. This coating may optionally further include an emulsifying polymer.

The regenerated cellulose fiber according to the present invention is prepared by a method including the following steps. Preferably, the fiber is a synthetic fiber.

(1) Dissolve cellulose in a water-compatible solvent to form a dope (4) Dry The obtained wet fibers in an untreated state are treated with an aqueous solution or dispersion of a polymer according to the method of the present invention. It may be treated with a mixture of liquids, emulsions. This mixture is further Glyoxal may further be included as a crosslinking agent. Additionally this mixture Contains a catalyst to strengthen the cross-linking of glyoxal with a weight of 0.3 to 0.6 % range, more preferably 0.4 to 0.5% by weight fiber or to remove the solvent. during or after passing through water and treatment with polyelectrolytes. , and may be treated with a variety of conventional finishes.

When emulsifying polymers are used, polymers can be used for simultaneous processing of cellulosic fiber materials. The child electrolyte and emulsifying polymer may be mixed together or the cellulosic material may It may be treated first with a polyelectrolyte and then with an emulsifying polymer.

A preferred class of polyelectrolytes has constituent units of the following formula on a dedicated backbone of carbon atoms: viscosity average of 20.000 to 10.000.000 molecular weight).

In the above formula, A is an alkali of C1 to C3 in which different carbon atoms are bonded to two nitrogen atoms. It is a kylene group. Such polymers contain di- or polyamines as nitrogen group-containing monomers. It may be prepared by reacting with a polymer. A is C, alkylene group At some times, the constituent units are imidacillin units. Particularly preferred of this class The polyelectrolyte appears to be poly(vinylimidapurine) within the lines described earlier. It is sold under the trademark Primafloc C7. Apart from this Polyelectrolytes based on polyacrylamide or water-soluble amides are used for It's okay to stay.

Particularly preferred classes of polyelectrolytes include cationic ionization in polyelectrolytes. At least some of the moieties are azetidinium cations. Departments like this The reaction of the secondary amine group with ebihalohydrin, such as epichlorohydrin, can be formed by Polymers containing secondary amine groups are, for example, adipine The two primary amine groups of the acid diacid, for example diethylenetriamine, and the can be prepared by condensation with a compound containing at least one secondary amine group . Such condensation results in a polyamide containing secondary amine groups. Multiple classes of this class One suitable polymer having thionic ionization sites is under the trade name rHercose. tt 125 J is Hercules Powder Corporation? It is commercially available. Other suitable polymers are under the trade name rListrian SRJ5. It is commercially available from the Tephenson Group.

Polymers combined with azetidinium cations as dyeing aids for cotton, For more information on the use of Hercosett 125, see the Journal of the Society of Dyers and Colorists Magazine No. 105 Volume (1989) pp. 391-398 and Vol. 106 (1990) 307-31 5, by S. M. Burkinshaw et al. This way The use of dyeing aids is not known to have a significant effect on the strength properties of cotton fibers. However, such use may affect the properties of the fibers, particularly their tendency towards fibrillation. There is no indication that there will be any impact. In fact, cotton fibers are fibrillated. It does not have a tendency. This means that cotton fiber is a complex material based on cellulose I structure. While solvent-spun regenerated cellulose fibers have a cellulose structure, It is related to the fact that it has a relatively simple form.

In addition, these polymers are more likely to be used on undried recycled cotton fibers than on cotton fibers just before dyeing. There is no suggestion that it is of value when applied to cellulose fibers.

A wide variety of polymers may be used as emulsifying polymers of choice in the method of the invention. The basic requirement is simply that the polymers are emulsifiable in water. That is true. Applicable polymers include polyacrylate, polyvinyl acetate Copolymers of vinyl acetate and polyolefin (especially polyethylene) is included.

Polyethylene emulsion is trademarked as Bradsyn P, E, J. From the former ckson & Welch, the trademark flberlene P, E, J. From Harrison Chemicals, with the trademark rMykon SFJ. Commercially available products from Warwick Chemicals can be used. Polyvinyl acetate is manufactured under the trademark rcatatacVBJ.1. C, I Commercially available products can be used. In the case of polyethylene emulsion , the polymer preferably has a melting point of about 100-105°C and a molecular weight of about 5000 or less. , having an acid value of not more than 20 and a carbonyl content not greater than 1% by weight of >C-0. should.

Emulsifiers are often needed to emulsify polymers, and Nitrogen-free nonionic emulsifiers such as xyalkylyphenols) may also be used. stomach.

Aqueous polymer emulsions can be cationic, nonionic, or nonionic. However, nonionic polymer emulsions are more preferred.

The pH of the emulsion is preferably between 4 and 7, especially between 5 and 6. stomach. Emulsions should be rather dilute, generally less than 1% by weight of solids. It would be good if it was included at a fairly low level. Under favorable conditions, release is rapid and complete. Yes, the initially cloudy solution becomes completely clear after the fibers are soaked in the treatment solution. Therefore, the completion of the process can be easily observed.

A temperature in the range of 20°C to 60°C, for example 25°C to 30°C, is the processing temperature. It is preferable.

The concentration of polyelectrolyte and optional emulsifying polymer in the treatment solution is regarding the amount of solids desired and the type of equipment that will be used for processing. selected in succession. The concentration of the polymer solid component in the treatment solution is, for example, 1 to 25 g#. preferably 5 to 20 g/I! , most preferably 10-15 It is good if it is g/z.

It is also advantageous to include a crosslinking agent such as glyoxal in the treatment bath. When used, cross-linked The agent is 2~log/l! , more preferably at a concentration of 4 to 8 g#). It is preferable that The processing bus may also include, for example, the trademark rcondensol. A crosslinking catalyst commercially available from BASF as FBJ may be included.

The amount of polyelectrolyte attached to the fiber is 0.0% by weight relative to the fiber weight. It is preferably 5% to 1.0%, more preferably 0.1% to 0.5%. When using The amount of emulsifying polymer released onto the fibers is from 0.1 to 4.0% by weight, more preferably It is preferably 0.75% to 2.0%.

The term ``release'' refers to emulsions or suspensions (when the emulsion or suspension is broken). fibers or emulsions that are seeded in emulsions etc. It is used to indicate that particles of the dispersed phase migrate through the fibers. complete release provides automatic control over the amount of polymer deposited Although generally advantageous in batch operations where must be complete (i.e. the supply of particles of the dispersed phase must be released). It is not intended to indicate that

After the discharge has taken place, excess liquid is removed from the treated fibers, e.g. by centrifugation or mangling. It is removed from the treated fibers by dewatering operations such as manipulating. Then regenerated cellulose The fibers are preferably dried at a temperature of about 80-100'C.

When the process of the present invention is carried out in a batch operation, the fibers are one piece containing the treatment liquid. Or simply seeded in multiple treatment tanks. The bath ratio of fibers in the bath is critical in the present invention. There are no boundary conditions. The bath ratio is conveniently from 5:1 to 100:l, for example 30:1. Seem.

Alternatively, the process may be performed continuously on continuous fibers. Continuous processing , although the pad may be made from multiple baths of normal pack washers This is best done using a mangle. In either case, during the impregnation step or Later, sufficient release of the polymer onto the fibers to reduce the tendency to fibrillate. After the treated product has been subjected to rinsing, treatment with other agents or drying, This is the basic thing that must be done before undergoing further processing steps. Release is done The amount of time the fibers are processed depends on both the polymer mixture and the nature of the fibers being processed. However, it should usually not exceed 15 minutes. The exact time and conditions will depend on experimentation. can be easily determined.

When the regenerated cellulose fiber is a solvent spun fiber, the solvent is a tertiary amine N-oxide. Preferably, N-methylmorpholine N-oxyto is more preferable.

Brief description of the drawing Embodiments of the invention, shown by way of example only, will now be described with reference to the accompanying drawings.

Figure 1 is a graph of fibrillation index (F, 1.) versus concentration. .

FIG. 2 is a graph of strength elongation versus treatment bath concentration.

The method described in this specification is described in British Patent Specification No. 1340859. It is recognized that there is some similarity to the process used in the It describes the process of treating wool to give it. Gives wool anti-shrink properties The wool treatment process imparts fibrillation resistance to the regenerated cellulose fibers and drying to make it possible to maintain proper strength and elongation and dyeability of the cellulose fibers. We do not know why it is suitable for processing untreated regenerated cellulose fibers. It has not been done. In addition, there are a large number of processes existing for the processing of fibers. or with regenerated cellulose fibers such as solvent-spun regenerated cellulose. It is impractical to predict the effects of processing protein fibers such as wool by comparison; In other words, it is impossible.

Example 1~12゜ From multiple cellulose strands or cellulose solutions to perform a series of tests. N-methylmorpholine N-oxide was extruded into a water bath to remove the solvent. passed through. The fibers thus produced are then produced in a large number of different chemical compositions. (Bus 1 to 12) to apply the normal spinning finish. The finished product is then passed through a finishing bath.

Details of the processing bus contents associated with the basic elements of the invention are given below.

The cellulose fibers treated in different treatment baths are then processed by conventional spinning techniques. The yarn samples obtained are then subjected to a process that simulates large-scale dyeing. stained on a small scale by

Details of fiber dyeing are as follows.

2g of fiber is placed in a stainless steel cylinder with a height of about 25an and a diameter of 4ao. placed inside. The cylinder has a capacity of approximately 250 d, and is used for each process step. Then, 50-g of the solution is added to 2 g of fiber.

The first step is to scouring the fibers to remove the spinning lubricant.

A normal scouring solution of anionic detergent and Na1COz is added to the fibers at 94°C. , the threaded cap is fitted, and the lidded cylinder is then cycled approximately 60 times per minute. The material is then dumped end to end for 45 minutes.

The scouring solution is then removed and the fibers are washed in water and bleached at 95°C for 1 hour. . The lid was placed on the cylinder again and rolled at a rate of 60 times per minute.

The bleaching solution used includes:

7, 5cc/litre 82oz (35% concentration), 1g/litre of NaOH1 1 g/itre peroxide stabilizer and heavy metal ion sequestrant (rContivan (Available from CHT Products Limlted as SNT J) .

After bleaching, the fibers are washed and treated with 4% Procion Navy) IER150 reaction. Chemical dye (Procin is Imperial Chemical Industry ies Pie trademark). Staining is done with 80g/1itre of Na. 9 in a covered cylinder with an aqueous solution containing Cl and 20 g/itre of NazCOi. Performed at 0°C. Again the cylinder is rolled from end to end at a rate of 60 times per minute. .

After dyeing, the fibers are washed and dried. The amount of fibrillation in the fiber, the dyeing of the fiber, It is evaluated for fiber strength, fiber elongation and water swelling.

Measure fibrillation and fix scale to allow changes in fibrillation to be determined In order to It will be done. A standard length of fiber is then taken and the fibrils along the standard length are The number of thin fluff-like protrusions extending from the main body of the fiber is counted. each fib The length of the rill is measured and the fibril multiplied by the average length of each fibril. An arbitrary number that is the product of the number of brills is determined for each fiber. Second series The fiber with the highest value among the fibers is identified as the most fibrillated fiber. The fibrillation index is 10. Fibers that are not fibrillated at all Fibers are defined as fibers with a fibrillation index of O, and are based on an arbitrary number measured with a microscope. The remaining fibers are then divided evenly between 1 and 10. Seen as a guideline , the fibrils on the fiber with fibrillation index l are just visible to the eye. degree.

The measured fibers are used to establish an optical scale. other fibers To determine the fibrillation index for fibers, 5 to 10 fibers were The sample is compared visually under a microscope with a set of graded a-fibers. Visual The number determined for the fibrillation index for a given treated fiber is are averaged to give a Visual comparison and averaging are much more than measurements It is recognized that skilled textile technicians are consistent in these evaluations of textiles. It has been found that it grows.

Strength (centinewtons per tex) and elongation (%) are measured using conventional equipment. determined. Again, the measurements are made on multiple fibers (usually 10) and the arithmetic average The average is calculated.

Stainability is determined by visual comparison.

not treated according to the present invention, i.e. between the water bath and the spinning finish as described above. Untreated solvent-spun cellulose typically develops the following properties:

Fibrillation index; 3 Strength: 40-42CN/leX Elongation: 13-15% Dyeability: Good c) All dyeability tests described below are simple visual comparisons with untreated fibers) In a first series of tests to determine the effectiveness of using the treatment of the invention , Precision Process (Textile) Lim1ted? The commercial product rPolymer GJ from et al., containing glyoxal and crosslinker catalyst The mixture is used in one processing bath. Polymer G has a concentration of 0.1% by weight of poly(vinylimidapurine) and a solution of nonionic polyester at a concentration of 0.1% by weight. It is believed to be an aqueous solution consisting of an emulsion of tyrene.

A series of processing baths were prepared as shown in Table 1 below, and Polymer in the processing solution was The concentrations shown here of G and glyoxal are given in g/itre. place Ribas also uses a crosslinker catalyst for glyoxal at a level of 25% of the glyoxal concentration. Contained in Typically, rCondensolFBJ (BASF AG (trade name) is used as a catalyst, which consists of magnesium chloride and fluorobore It is believed to be a formulation of zinc.

Table 1 Polymer G glyoxal fibrillated layer degree concentration index Kusu The information shown in Table 1 is illustrated in FIG.

Approximately 20g/itre of Polymer G and 4g/itre of glyoxer The fibrillation index is improved at a level greater than or equal to the concentration of can be seen.

In other series of baths, Polymer G is used alone with different concentrations of treatment agents. It is used as The results of these tests are shown in Table 2.

Bus 10 10 2.2 〃11　20　1.5 '12 30 1.1 These results are also graphed in FIG.

Polymer G with strength and elongation test of 10g/1itre, 2g/1itr fibers treated with glyoxal of e and 0.5 g/litre of catalyst, 20g/itre of Pa1yrner G, 4g/itre of glyoxer and Ig/itre of catalyst treated fibers and 30g/itre of P olymer G, 6g/1itre of glyoxal and 1.2g/1 Itre catalyst treated fibers. The results of these tests are shown in Table 3. be done.

Untreated 0 40-4213-15 Bus 10 10 39.7 14.7 ”II 20 38.2 14.3 〃12　30　41.4　15.7 Fibers treated only with Polymer G at a concentration of 25g/litre were 40.2CN/l It has a strength of ex and an elongation of 16.4%.

The strength and elongation values are shown in FIG. It has been revealed that it has brought about a slight change.

Visually, which Polymer G, glyoxal and catalyst combinations were treated? There is no difference in the color of treated fibers after dyeing compared to untreated fibers.

A water swellability test was performed as a measure of the comfort of the fibers during use.

Cotton, which is usually considered a comfort fiber, has a water swellability of 50%.

The results for the comparative example and the fibers treated according to the invention are shown in Table 4.

Table 4 Water swelling property% Untreated fiber 65 20g/1itre Polymer G 6340g/1itre Paly +ner G 61.7 cotton 50 Therefore, the present invention reduces fibrillation while improving dyeability, strength, elongation or clearly provides a treatment that does not significantly affect water swelling properties. It is clear. Fibrillation causes pilling in the fabric, giving it undesirable fuzz. and undesirable visual effects on fabrics made from highly fibrillated fibers. will be given.

Items present in combination in fibers treated according to preferred embodiments of the invention The properties may be considered almost mutually exclusive.

For example, adding materials to the fibers that bind them in a way to reduce fibrillation. It was thought that this would affect dyeability and elongation, but this is not true. The method of invention is not found to be true. These properties are retained only in fibers It can also be applied to slivers, threads and fabrics. of the present invention Treatments can be applied to all of these and are resistant to scouring, bleaching and dyeing treatments. You can get it.

Other suitable formulations can be included in the processing bath.

(1) Polyethylene emulsion (Bra dsyn P, E,) and polymer electrolyte with a solid content of 0.1% based on the weight of the fiber. Solution (1?oh+n and Haas Ljmited quotient’11.rPr imafloc C7J)] 75g of solid components and polymer electrolyte per tre (Primafloc C7) 1. The solid component of Og Treated at 40'C.

Example I3 Cellulose fibers are prepared as described in Example 1.

The treatment bath was made of polyamide shrimp commercially available by Hercules Inc. 12. of the trademark rHercosett 125 J in water of chlorohydrin resin. 100g/itre solution as a 5% aqueous solution. The pH of the bus is about 7.3~ Best results are obtained when controlled at 7.9. The result in this pH range The results are shown below in comparison with comparative examples.

Comparative example Hercosett treatment Fibrillation index 3.8 1.3 Strength CN/tex 42.3 41.2 Elongation % 14.9 14.5 Water swelling property % 5656 Examples 14 and 15 Cellulose fibers are prepared as described in Example 1. The processing bus used is as follows It is as follows.

Bus 14 30g/1itre Polymer VG6g/1itre Gri Oxal 4 g/1itre Con5ensol FB bus t5 30g/l Boria VG “Polymer vG (trademark)” is a product of Precision Process (Texti le) Available from Limlted. This is poly(vinyl imidasyl) It is believed to be a 0.1% by weight aqueous solution of

The results are shown below.

Bus 14 Bus 15 Fibrillation index 1.1 1.3 Strength CN/tex 39.2 43.6 Elongation % 14.8 14.4 International Search Report Qf〒1. ,Q01Vn117F.

Claims (1)

[Claims] 1. Producing regenerated cellulose fibers with a reduced tendency to fibrillation In this method, undried regenerated cellulose fibers are injected with multiple cationic ions. A regeneration cell characterized in that it is treated with an aqueous solution or dispersion of a polymer having a polymerization site. A method for producing lullose fiber. 2. The polymer has a dedicated main chain consisting of a plurality of carbon atoms, and the main chain has a structure of the following formula. The method according to claim 1, characterized in that a forming unit is attached: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The above A is a C2 to C3 alkyl group in which different carbon atoms are bonded to two nitrogen atoms. It is a ren group. 3. At least some of the cationic ionization sites of the polymer are acetidinium cations. 2. The method according to claim 1, wherein the method is on. 4. The polymer comprises two primary amine groups and at least one secondary amine group. condensation of the compound with a diacid followed by reaction with an epihalohydrin 4. A method according to claim 3, characterized in that the method is prepared by: 5. The fibers are treated such that 0.1-0.5% by weight of polymer is deposited on the fibers. The method according to any one of claims 1 to 4, characterized in that . 6. The undried fibers are further treated with an aqueous emulsion of an emulsifying polymer. The method according to any one of claims 1 to 5, characterized in that: 7. The aqueous emulsion of the emulsifying polymer is a nonionic polymer emulsion. 7. The method according to claim 6, characterized in that: 8. Claim 7, wherein the emulsifying polymer is polyethylene. How to put it on. 9. Claim 6: The emulsion contains 1% or less by weight of the emulsifying polymer. The method described in any one of paragraphs 8 through 8. 10. Claims characterized in that the pH of the emulsion is in the range of 4 to 7. The method described in any one of Boxes 6 to 9. 11. The undried fiber has a plurality of cationic ionization sites. From claim 6, characterized in that it is treated with a mixture of lima and an emulsifying polymer. The method described in any one of items up to item 10. 12. The undried fiber has a plurality of cationic ionization sites. Claim 6 characterized in that the treatment is performed sequentially with lima and an emulsifying polymer. The method described in any one of paragraphs 1 to 10. 13. 0.75 to 2.0% by weight of the emulsifying polymer is deposited on the fibers. , any one of claims 6 to 12, characterized in that the fibers are treated. The method described in. 14. An aqueous solution or dispersion of a polymer having multiple cationic ionization sites is Any one of claims 1 to 13, characterized in that it contains oxal. The method described in. 15. The aqueous solution or dispersion may contain 2 to 10 g of glyoxal per liter. 15. The method according to claim 14, characterized in that: 16. The undried regenerated cellulose fibers are processed by a method comprising the following steps: 15. The method according to claim 14, characterized in that the solvent-spun fibers are prepared: (1) dissolving cellulose in a water-compatible solvent to form a dope; (2) extruding the dope to form a plurality of extruded filaments; Beauty (3) extruded filaments to remove solvent and form regenerated cellulose fibers; The process of passing mento into water. 17. Claim characterized in that the water-compatible solvent is a tertiary amine N-oxide. The method according to item 16. 18. Claim characterized in that the solvent is N-methylmorpholine N-oxide. The method described in item 17. 19. Responsible for coatings made of polymers with multiple cationic ionization sites. A regenerated cellulose fiber characterized by having 20. The polymer has a dedicated main chain consisting of a plurality of carbon atoms, and the main chain has the following formula: 20. Fiber according to claim 19, characterized in that it is provided with structural units: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The above A is a C2-C3 alkylene group in which different carbon atoms are bonded to two nitrogen atoms. It is a group. 21. At least some of the cationic ionization sites of the polymer are acetidinium carbon atoms. 20. The fiber according to claim 19, which is thione. 22. the polymer comprises two primary amino groups and at least one secondary amino group The compound is subjected to condensation with a diacid followed by reaction with an epihalohydrin. 22. The fiber according to claim 21, characterized in that it is prepared by: 23. The weight of polymer in the coating is between 0.1 and 0 based on the weight of the fiber. ．． Any one of claims 19 to 22, characterized in that the amount is 5% by weight. The fibers mentioned. 24. The coating may additionally comprise a water-emulsifiable polymer. The fiber according to any one of claims 19 to 23, characterized in that: 25. At least a part of the emulsifying polymer is polyethylene. The fiber according to claim 24. 26. The weight of emulsifying polymer in the coating is 0 based on the weight of the fibers. ．． Claim 24 or 25, characterized in that the content is 75 to 2.0% by weight. fiber.