CN1469943A - Fiber and its production - Google Patents
Fiber and its production Download PDFInfo
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- CN1469943A CN1469943A CNA018173632A CN01817363A CN1469943A CN 1469943 A CN1469943 A CN 1469943A CN A018173632 A CNA018173632 A CN A018173632A CN 01817363 A CN01817363 A CN 01817363A CN 1469943 A CN1469943 A CN 1469943A
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- lyocell fibers
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
Abstract
A method for the manufacture of lyocell fibre includes the steps of: (i) forming a solution of cellulose in an aqueous tertiary amine N-oxide solvent at a temperature above ambient temperature, the solution having from a trace (as herein defined) to 30 percent by weight of particles of a thermoplastic polymer having a glass transition temperature below the temperature at which the solution is formed, based on the weight of cellulose dispersed therein; ii) extruding the solution by way of a die into an aqueous coagulating bath, thereby forming lyocell fibre; iii) washing the fibre to remove residual amine N-oxide therefrom, and drying the fibre; and (iv) crimping the fibre so as to induce from 2.5 to 8 crimps/cm in the fibre. In the method according to the invention, the thermoplastic polymer is preferably dispersed throughout the lyocell in domains, and the maximum dimension of substantially all of the domains is preferably no more than 50 nanometres (nm). The invention provides lyocell fibre having a trace to 30 percent by weight of low melting thermoplastic polymer and 2.5 to 8 crimps per centimetre.
Description
Technical field
The present invention relates to a kind of Lyocell fibers and manufacture method thereof of modification." fiber " described in the present invention comprises the yarn bundle of continuous filament yarn yarn, cutting short-forming fiber, also comprises the staple fibre that is formed by such yarn bundle.
Background technology
Lyocell fibers is by making cellulose dissolution in N-tertiary amine oxide such as oxidation N-methylmorpholine that suitable solvent for example mixes with water.US-A-4416698 has described a kind of appropriate preparation method.The solution of cellulose in amine oxide solvent is solid-state in room temperature, extrudes from spinnerets under 95-125 ℃ of temperature, by one section air duct, enter the coagulating bath of water or amine oxide dilute aqueous solution, amine oxide solvent leaches and enters in the coagulating bath, forms cellulose fibre.
JP-A-8-170224 has disclosed a kind of sea-island type bicomponent fiber that can dispersion dyeing, wherein continuous " sea " component is a spun cellulosic polymer in the organic solvent system, " island " component comprises can be by the polymer of disperse dyeing, be of a size of 0.01-3m, account for the 2-45% of fibre weight.
GB-A-2121069 has disclosed a kind of viscose for preparing supatex fabric, it contains mineral filler barium sulfate, talcum powder, muscovite or their mixture, content is the 15-60% of total weight of fiber, preferred 40-50%, if desired, also contain hydrophobic polymer or oligomer, for example polyethylene, polypropylene, polystyrene, polyacrylate, polyester, polytetrafluoroethylene (PTFE) or wax, content is the 1-60% of total weight of fiber, preferred 25-50%.GB-A-2008126 has disclosed and has used the delustering agent of polystyrene as viscose.
WO-A-98/46814 Lyocell fibers, it contains the elongated phase farmland of polyester, polyamide or olefin copolymer, and the aspect ratio on described phase farmland is at least 1.5, and is arranged in substantially parallel with fiber axis.The long 70-1000nm in described phase farmland, diameter is 30-400nm.But, find in industrial production, be difficult to phase farmland size Control in these limited ranges.Aspect this, also enlighten out, fiber need not make with lubricator just can carry out combing.On the contrary, the Lyocell fibers that does not contain the eutectic thermoplastic polymer just needs lubricant to carry out combing, and the conventional steps that applies lubricant is in preparation process, moistening fiber before drying.
Lyocell fibers is natural to be unconvoluted.But especially staple fibre is to need to curl.According to the content that EP-A-0797696 discloses, just can in Lyocell fibers, produce by the extruding wet fiber curling, or curling by means of the effect of dry saturated steam by stuffer box, as described in EP-A-0703997.Experience shows, such dry saturated steam processing, though little to fibre damage, can not under the situation of not damaging conventional Lyocell fibers, form be higher than about 2.3 curling/centimetre.Described herein term " conventional Lyocell fibers " refers to not contain the Lyocell fibers of eutectic thermoplastic polymer.Only can buy at present conventional Lyocell fibers.
Find that also high speed combing Lyocell fibers can produce such problem, the rolling that for example forms too much flying chip and fiber is overlapping.High productivity manufacturing staple fibre yarn is especially made supatex fabric and is just required the high speed combing.
The content of invention
An object of the present invention is to reduce or overcome substantially these defectives.
According to the present invention, a kind of method of making Lyocell fibers is provided, it comprises the steps:
(1) is being higher than the temperature of room temperature, the solution of preparation cellulose in moisture N-tertiary amine oxide solvent, this solution contains from trace (as defined herein) to 30 weight %, preferred 0.001-30 weight %, more preferably 0.01-20 weight %, the thermoplastic polymer particles of 0.1-10 weight % most preferably, the glass transition temperature of this thermoplastic polymer are lower than the temperature that forms solution, and this percentage is a benchmark with the cellulosic weight that is scattered in the solution;
(2) with mould solution is clamp-oned in the moisture coagulating bath, formed Lyocell fibers thus;
(3) washing the fibre removes residual N-amine oxide, and dried fibres;
(4) crimped fibre, making the interior 2.5-8 of formation of fiber curls/centimetre.
Term " trace " is enough to demonstrate the amount of the thermoplastic polymer of change color when referring to the disperse dyeing of fiber that contains thermoplastic polymer.
Glass transition temperature Tg represents that polymer becomes the temperature province of elasticity or sticky polymers from the state-transition that firmly, more or less is brittle glass, when described elasticity or viscosity attitude, the motion of the part of strand (being commonly referred to segment) is not subjected to interactional obstruction (the Principles of PolymerChemistry of adjacent molecule chain, Paul J Flory, Comell University publishing house, the 15th printing, 1992, ISBN0-8014-0134-8, the 56th page).
In a preferred implementation of the inventive method, the fusing point of described thermoplastic polymer is higher than 50 ℃, is preferably 50-150 ℃, more preferably 80-130 ℃, is recorded by the differential thermal analysis method.
Preferred-20 ℃-130 ℃ of the glass transition temperature Tg of polymer, more preferably 30-130 ℃.
Thermoplastic polymer is preferably selected from polyester, polyamide and olefin polymer.
Thermoplastic polymer preferably is scattered in the whole Lyocell fibers with phase farmland form, and the full-size on all phase farmlands preferably is not more than 50nm basically.
Fiber preferably curls, make intrastitial crispation number be 3.5-8 to curl/centimetre.
Described solution can contain delustering agent, for example is scattered in titanium dioxide granule wherein.Thus, formed fiber just contains the 0.1-5 weight % that is scattered in wherein, preferred 0.1-2 weight %, and more preferably the titanium dioxide granule of 0.2-1 weight % is a benchmark with the cellulose.
In a preferred implementation of method of the present invention, before curling, fiber is applied soft finishing agent (lubricant).
The preferred 0.01-2 weight of the content of the soft finishing agent that is applied %, more preferably 0.1-0.5 weight %, most preferably 0.15-0.4 weight % is a benchmark with the fibre weight.Find at least these scopes under the zone in, obtainable crimpness directly changes with the amount of the soft finishing agent that is applied.
Curl and to be formed in the fiber by the described method of EP-A-0703997.The fiber number of formed fiber is preferably the 0.5-5 dtex, more preferably the 1-3.5 dtex.
Method of the present invention can also comprise the step that fiber is cut into the staple fibre of 3-100mm length, more preferably 20-75mm.
In a preferred implementation of the inventive method, after fiber wash and before the drying, apply chemical substance with 2-6 and functional group of fibrin reaction, they are before the drying or between dry period, through reaction bonded to fiber.
According to the present invention, the another kind of method of making Lyocell fibers also is provided, it comprises the steps:
(1) make the solution of cellulose in moisture N-tertiary amine oxide solvent, this solution contains the eutectic thermoplastic polymer particles to 30 weight % from trace (as defined herein), and this percentage is a benchmark with the cellulosic weight that is scattered in the solution;
(2) with mould solution is clamp-oned in the moisture coagulating bath, formed Lyocell fibers thus;
(3) washing the fibre removes residual N-amine oxide, and dried fibres;
(4) crimped fibre, making the interior 2.5-8 of formation of fiber curls/centimetre.
According to the present invention, a kind of Lyocell fibers also is provided, it contain be scattered in wherein from trace (as defined herein) to 30 weight %, preferred 0.001-30 weight %, more preferably 0.01-10 weight %, most preferably the eutectic thermoplastic polymer particles of 0.1-10 weight % is a benchmark with cellulosic weight, and have 2.5-8 curl/centimetre.
The eutectic thermoplastic polymer is preferably selected from polyester, polyamide and olefin polymer.
Be surprised to find that fiber of being made by the inventive method and fiber of the present invention can be significantly to carry out gratifying combing at a high speed, in some cases, even can adopt the twice of the employed gratifying speed of conventional Lyocell fibers.In the manufacture process of supatex fabric, combing speed is a very important speed limiting factor.Supatex fabric often uses delustering fibre, can not harm method of the present invention as the existence of the titanium dioxide of delustering agent, or the performance of fiber of the present invention, comprises the performance of its high speed combing.
Lyocell fibers of the present invention can be that length is preferably 3-100mm, more preferably the staple fibre form of 20-75mm.
The soft finishing agent that Lyocell fibers of the present invention applied is preferably 0.01-2 weight %, more preferably 0.1-0.5 weight %, and most preferably 0.15-0.4 weight % is a benchmark with the fibre weight.
According to the present invention, a kind of Lyocell fibers also is provided, it comprises the phase farmland of eutectic thermoplastic polymer, described polymer is selected from polyester, polyamide and olefin polymer, it is characterized in that described fiber contains 0.1-30 weight %, preferred 0.5-10 weight %, 1-5 weight % eutectic thermoplastic polymer most preferably, with the cellulose is benchmark, and when its feature also was with the electron microscope observation that amplifies 9000 times, all basically phase farmlands all be can't see.The full-size on all basically phase farmlands all is not more than 50nm.At higher multiple, when for example amplifying 55000 times, the phase farmland also can be seen.
Fiber of the present invention can by cellulose moisture N-tertiary amine oxide (" amine oxide ") for example the solution in the N-oxidation N-methylmorpholine make, described solution contains suitable molten state eutectic thermoplastic polymer.This solution is extruded from spinnerets, through one section air duct, enters moisture coagulating bath.Extrusion temperature is generally 90-125 ℃.Then, with fiber wash and the drying extruded like this.
The eutectic thermoplastic polymer usually should be fully compatible with cellulose solution, can not be gathered into independent phase in cellulose solution during polymer melt, but in the amine oxide that it preferably is insoluble in the coagulating bath to be diluted or in the water.Should select such polymer, it substantially all is retained in the fiber in extruding (spinning), washing and dry run.The preferred low melting point polymer of one class is a polyester, the polyester of especially preferred carboxyl-functional.
We find, exist carboxylic acid functional can increase the compatibility of it and cellulose solution usually in the low melting point polymer, and cellulose is mixed more fully with low melting point polymer.Use for great majority, the acid number of polymer is preferably from least 10 to up to for example 50 or 100 or even 150.We believe that also the branched polymers structure is favourable.
Such example with desired low-melting polyester is by aromatic dicarboxilic acid, with optional and aliphatic dicarboxylic acid, form with the mixture of one or more aliphatic glycols, described aromatic dicarboxilic acid is selected from M-phthalic acid, terephthalic acid (TPA) and O-phthalic acid or anhydride, described aliphatic dicarboxylic acid is for example adipic acid, succinic acid or decanedioic acid, described aliphatic glycol is for example neopentyl glycol, ethylene glycol, propylene glycol, propane-1,3-glycol, butane-1,4-glycol, butanediol or diethylene glycol.Branching can be introduced by trifunctional chemistry material, for example trihemellitic acid or acid anhydride or trimethylolpropane, glycerine or pentaerythrite.By adopting the chemical substance of suitable excessive carboxylic-acid functional, just can obtain desired acid number.Such polyester is for example sold with trade mark " Alftalat ", " Uralac " or " Grilesta ", is used for the thermosetting powder coating.
Other eutectic thermoplastic polymer comprises polyamide, the polyamide that forms by aliphatic acid dimer and aliphatic diamine for example, or the copolyamide of selling with trade mark " Griltex ", or olefin copolymer for example ethylene or ethylene/butylene/butyl acrylate copolymer, preferably contain a small amount of acrylic comonomers, to provide preferred acid number.Another eutectic thermoplastic polymer is a for example polyvinyl alcohol of olefin polymer.
The concentration of cellulose in extrusion solution (being also referred to as spinning solution) is generally 10-20 weight %, preferably is at least 13 weight % or 15 weight % to 17 weight % or 18 weight %.Spinning solution preferably contains water, and content is 5-15 weight % usually, and remaining 65-83 weight % is amine oxide normally.Normally 95-125 ℃ of extrusion temperature.
Low melting point polymer can join in the cellulose solution in any stage in its preparation process.Polymer can be for example and the cellulose paste premixed, and slurry mixes with amine oxide and water then, forms spinning solution.Described polymer also can preferably join in the preformed cellulose solution with molten state.In another kind of mode, low melting point polymer and preformed cellulose solution premixed with higher proportion for example form 10-50 weight % mixture.Then, this premix joins low melting point polymer in the cellulose solution with desired amount as masterbatch.In another mode, polymer is joined in the amine oxide solvent, formed mixture is used for dissolving cellulos.
The cellulose solution that contains low melting point polymer can adopt the conventional same spinning plate that adopts of preparation Lyocell fibers to extrude the formation fiber under same temperature.
The phase farmland that it is believed that low melting point polymer is as being scattered in equably in the whole fiber mutually separately.
Low melting point polymer is from trace to 30 weight % at intrastitial content, is benchmark with the cellulose.The existence on the phase farmland of low melting point polymer produces not same-action according to the concentration of low melting point polymer and the type of used low melting point polymer.More particularly, if only require to curl effect (as described below), content can be preferably up to 15 weight %, preferred 0.01-5 weight %, and if require weaving effect (as described below), content is 1-20 weight % preferably, preferably 5-15 weight %.
The little phase farmland of desired thermoplastic polymer can be obtained by multiple mode.For example, described polymer can synthesize granule.In addition, bulky grain can for example be pulverized by grinding or preferably making spinning solution stand high shear.
We are surprised to find that, and are opposite with conventional Lyocell fibers, the described method of EP-A-0703997 can in fiber of the present invention, form up to about 8 curl/centimetre.In addition, we are surprised to find that also the content of soft finishing agent is more much bigger to the influence of conventional Lyocell fibers than them to the influence of fiber of the present invention on curl typing and variation of temperature and the fiber.We find that also crimped fibre of the present invention has higher curling density and lower crimp amplitude, and in curly course, it is compared with conventional Lyocell fibers, is not easy to through being mechanically damaged.
We are surprised to find that also fiber of the present invention is compared with conventional Lyocell fibers, and are much dry easily.This just can save the useful energy.
In order to reduce fibrillation trend, known Lyocell can with multifunctional chemical substance reaction.See for example EP0538977, EP0665904 and EP0755467.Their content is in conjunction with being referred to this.Such reaction can or carried out on the dry fiber of crossing on the dry fiber of crossing never in advance.Same reaction also can be carried out on fiber of the present invention.
We find that the fiber that is higher than 6 weight % low melting point thermoplastic polyesters that contains of the present invention is compared with conventional fibre, not too is easy to and so multifunctional chemical substance reaction.This can offset by adopting the stronger for example higher chemical substance concentration of condition.
We are surprised to find that, by the spun yarn of fiber of the present invention can be favourable raising weaving effect, comprise higher intensity and extensibility, the irregularity quantity and the white star content of thin knot (thick and) is also less, lacks than the burr by the spun yarn of conventional fibre.If the fiber that compares is never to react under the dry state of crossing, described difference is especially obvious.
The yarn and the fabric of the Lyocell fibers that can curl than routine by the spun yarn of crimped fibre of the present invention with by its fabric of making are more fluffy.This means that the fabric with qualified porosity can be made the littler yarn of promptly special number by thinner yarn.More even by the fabric that these spun yarns are made, drapability is better.
Fiber of the present invention can be continuous long filament or staple fibre.
Fiber of the present invention can be made into woven fabric, knitted fabric or supatex fabric (for example water thorn, acupuncture or melt bonded) fabric.Such fabric can carry out conventional processed, for example carries out the resin impregnation of anti-crape arrangement and handles.We find this fabric of such resin impregnation behind repeated washing, can show the outward appearance that the resin impregnation fabric than conventional Lyocell fibers more cleans.We find, if the fiber that contains polyester of the present invention in the hot causticization of about temperature more than 50 ℃, should be very careful because NaOH can hydrolysis of ester bonds with.
Fiber of the present invention can be with cellulosic conventional dyeing, for example direct dyes and chemically-reactive dyes.The water imbibition of fiber of the present invention is lower than conventional fibre usually.It is wetting to this means that fiber is not easy, and in some applications, this can improve the uniformity of dyeing.
A kind of arrangement of known Lycoell fabrics is handled and is for example comprised and cause fibrillation in advance by thick moistening processing, and for example enzyme is handled and fiber separation is carried out in dyeing by carrying out with cellulase.We find preferably to use the little cellulase of aggressivity of the fabric that forms than conventional fibre to handle by the fibroplastic fabric of the present invention.We find that also the fabric put in order by this mode is bigger than the water imbibition of the fabrics in general of being put in order by this mode, and show better wicking properties, also are like this even form the water imbibition of fiber of fabric less.
Low melting point polymer is hydrophobic polymer normally, therefore dyes with disperse dyes easily.But we find, use the fiber of the present invention of disperse dyeing intersection to dye when washing.Therefore, not recommended usually with the fiber of the present invention of disperse dyeing.
Curling in the Lyocell fibers can be estimated in the following manner., and place under the enough tension force stretching curling from about 200 spies' of the intrafascicular taking-up of shredded dried bean curd sample.10cm makes a mark at interval on sample, removes tension force.Then, the crispation number between the calculating mark.Stretching length has just provided curling density or has curled ratio with the ratio of not carrying out stretching length.
With embodiment the present invention is described below, wherein umber, percentage and ratio all are meant weight.
Embodiment 1
At about 70 ℃, the saturated polyester resin of carboxyl-functional is mixed in the ploughshare blender with 77/23 N-oxidation N-methylmorpholine (NMMO)/water, and the type of described mylar is the type that is used for powder coating, and acid number is about 40,95-130 ℃ of fusion, and has branched structure.After about 2 minutes, add the wood fragments slurry, continue again to mix after 10 minutes, wood pulp is 92.8: 7.2 with the ratio of resin.
Described mixture is passed through Buss 5.5m
2Film extruder (trade mark) device HS0055 removes excess water, forms spinning solution thus.In this film extruder, mixture is heated under the vacuum of 200mmHg by 130 ℃ water leg.But, can use 80-150 ℃ temperature, and can use higher or lower vacuum.Through during the film extruder, mixture about 2-2.5mm thick layer in stand high shear and reach about 10 minutes, about 5 meter per seconds of blade velocity.Spinning solution contains 13.5% cellulose, 1.1% polyester, and 75.4%NMMO, other are water.
Spinning solution is extruded from spinnerets at 105 ℃, enters moisture coagulating bath by air duct, forms fibre bundle in a usual manner.Then, fiber carries out drying with pencil, and curls in the described mode of EP-A-0703997.The dry fiber of crossing is 1.7 dtexs, contains have an appointment 8.1% polyester and 8% moisture content on the cellulose.The diameter of the fiber that forms is about 10 * 10
-6M.The section of the fiber that forms as shown in Figure 1, it is to adopt the transmission electron microscope that amplifies 9000 times to take.Big black crack is that the preparation sample produces, and does not represent to exist cellulose other materials in addition.When amplifying 9000 times, can see vestige (it is believed that resolution ratio), but all in fact polyester phase farmlands be can't see all corresponding to about 50nm on intrastitial polyester phase farmland.Optics enlarged photograph shown in Figure 1 does not demonstrate other vestiges on any polyester phase farmland.
Adopt transmission electron microscope amplify 55000 times of shootings same fiber section as shown in Figure 2, the longitudinal profile of same multiplication factor is as shown in Figure 3.
In these figure, polyester phase farmland is shown as white area.Can see polyester farmland mutually from Fig. 2 and 3, compare that full-size is about 20nm with the ratio of figure bottom.
Fiber has 2.6 and curls/centimetre, curling density is 1.3.By contrast, the conventional Lyocell fibers that curls under the similarity condition has 2.3 and curls/centimetre, curling density is 1.23.
Fiber is cut into the 38mm staple fibre, and RING SPINNING becomes 20 spies' yarn.The result who obtains is as shown in the table, wherein:
Tester is conventional Lyocell fibers;
C.V.% is the coefficient of variation of thickness of yarn, represents with percentage;
The C.V.% of irregularity index=reality is divided by limit C.V.%, limit C.V.%=100/ √ n wherein, and wherein n is the fibre number (the special number of yarn is divided by the special number of fiber) in section, the irregularity index is the desirable yarn of 1 expression.
Details content (40%)=on 1 kilometer yarn, the thickness of yarn is less than the quantity at the position of 40% nominal thickness, by 3 tests of Uster tester.
Slubbing content (+50%)=on the yarn of 1 milimeter number, thickness of yarn is greater than the quantity at the position of 50% nominal thickness, by 3 tests of Uster tester.
White star content (+200%)=on the yarn of 1 milimeter number, thickness of yarn is greater than the quantity at the position of 200% nominal thickness, by 3 tests of Uster tester.
The quantity of all fibres of burr=stretch out from yam surface and the indirect measurement of cumulative length are by 3 tests of Uster tester.
| Yarn | Intensity cN/tex | Percentage elongation % | Evening ratio C.V.% | The irregularity index | Details content (40 %) | Slubbing content (+50 %) | White star content (+200 %) | Burr |
| Tester | 25 | 7.3 | 13.3 | 1.44 | 87 | 10 | 15 | 5.85 |
| Embodiment 1 | 27 | 8.5 | 12.3 | 1.34 | 41 | 7 | 7 | 5.52 |
Embodiment 2
Repeat embodiment 1, except changing the condition and the fiber softening finish content of crimping machine.Conventional fibre can curl as described in EP-A-0703997, adopts stuffer box pressure to be about 8psig (55kPa), and steam pressure is about 20psig (138kPa).Higher pressure can cause inhomogeneously curling, tow damages and stuffer box stops up.Opposite with conventional Lyocell fibers, fiber of the present invention can bear stronger curling condition (higher stuffer box pressure, higher steam pressure and the nip pressure of Geng Gao), and so stronger condition then can be damaged conventional Lyocell fibers inevitably.These stronger conditions can produce the crispation number on more every centimetre.The known combing lubricant that is applied on the conventional Lyocell fibers does not have a significant impact the parameter of curling.WO-A-98/46814 enlightens out the Lyocell that contains polyester can not add combing under the lubricant situation.The adding that is surprised to find that soft finishing agent or lubricant has very big advantageous effect to the curling parameter of fiber of the present invention.Fig. 4 demonstrates and increases the benefit of lubricant content to obtainable maximum crimpness.As can be seen, the soft finish agent content that applies is increased to 0.35% from 0.17%, maximum crispation number can be brought up to 5/centimetre from 3.5/centimetre.This figure also demonstrates maximum stuffer box pressure also can be the twice of conventional Lyocell fibers.In addition, it is directly relevant with the raising of soft finish agent content that this figure demonstrates the raising of maximum crimpness.Lower pressure make fiber produce the crispation number same with conventional crimped fibre/centimetre, but density descends because crimp amplitude reduces to curl.
Embodiment 3
Repeat embodiment 1, except fiber under the dry state of crossing never with 1,3,5-triacryl six hydrogen-1,3,5-six hydrogen, three azines (TAHT), as described in EP-A-0755467, its applied amount on fiber is 0.7 weight %, as antigen fibrillation finishing agent.In following table, tester refers to the fiber made with the conventional Lyocell fibers that contains 0.7%TAHT.Following result obtains on by the spun yarn of the fiber of handling.
| Yarn | Crispation number/10cm | Intensity cN/te x | Percentage elongation % | The irregularity index | Details content (30 %) | Details content (40 %) | Slubbing content (+50 %) | White star content (+20 0%) | Burr |
| Tester | 24 | 24 | 7.9 | 1.48 | 1049 | 72 | 62 | 48 | 6.37 |
| Embodiment 3 | 24 | 25 | 8.2 | 1.32 | 595 | 29 | 23 | 31 | 5.30 |
| Embodiment 3 | 30 | 26 | 8.5 | 1.32 | 590 | 25 | 12 | 19 | 5.05 |
| Embodiment 3 | 40 | 26 | 8.8 | 1.27 | 443 | 14 | 13 | 13 | 5.09 |
The single jersey of the dyeing that the spun yarn of being handled by the present invention of fiber is made does not have the vestige of fibrillation after through 40 ℃ 10 home washings/circulation of rolling.
Embodiment 4
Use usual manner, spin the Lyocell fibers of 1.7 dtexs at the solution of moisture NMMO with cellulose, this solution contains the saturated polyester resin of the 4% thermoplasticity carboxyl-functional that disperses, that uses in type and the powder-type coating is the same, acid number is about 40, and fusing point has branched structure in 95-130 ℃ of scope, with 0.5% titanium dioxide as delustering agent, the both is benchmark with the cellulose.Washing the fibre, and apply 0.25% soft finishing agent, with the fibre weight benchmark.Then, fiber carries out drying, and extruding in the presence of dry saturated steam in stuffer box, and purpose is fiber to be produced curl.The condition of fiber crimp is as shown in the table, and as shown in Figure 5.
| Stuffer box pressure (psig) | Relative stuffer box pressure | Average crimpness (crispation number/10 centimetre) |
| 8 | 1 | 25 |
| 20 | 2.5 | 35 |
| 26 | 3.3 | 40 |
Then, fiber is cut into the staple fibre that length is 38mm.
Fiber combing on Thibeau CA11 carding machine, its wide 2.5m, and two doffing rollers are housed.The target Unit Weight of carded web is 30gsm.Be fiber of the present invention that obtains and the result who contrasts fiber below.
Maximum combing speed m/min
The fiber of embodiment 4,2.5 curl/centimetres about 140
The fiber of embodiment 4,3.5 curl/centimetre 200-220
The fiber of embodiment 4,4.0 curl/centimetre 250-270
Conventional Lyocell fibers, 2.3 curl/centimetres 100
Viscose about 150
Polyester 200+
Polypropylene about 250
Because the unstability of curly course can not obtain higher curling in conventional Lyocell fibers.On the contrary, fiber of the present invention can carry out stable curling under the pressure higher than conventional fibre, and what produce under setting pressure curls than conventional fibre height.
Claims (51)
1. method of making Lyocell fibers, it comprises the steps:
(1) is being higher than the temperature of room temperature, the solution of preparation cellulose in moisture N-tertiary amine oxide solvent, this solution contains the thermoplastic polymer particles to 30 weight % from trace (as defined herein), the glass transition temperature of this thermoplastic polymer is lower than the temperature that forms solution, and this percentage is a benchmark with the cellulosic weight that is scattered in the solution;
(2) with mould described solution is clamp-oned in the moisture coagulating bath, formed Lyocell fibers thus;
(3) washing the fibre removes residual N-amine oxide, and dried fibres;
(4) crimped fibre, making the interior 2.5-8 of formation of fiber curls/centimetre.
2. the method for claim 1 is characterized in that described cellulose solution contains 0.001-30 weight % thermoplastic polymer particles.
3. method as claimed in claim 2 is characterized in that described cellulose solution contains 0.01-20 weight % thermoplastic polymer particles.
4. method as claimed in claim 2 is characterized in that described cellulose solution contains 0.1-10 weight % thermoplastic polymer particles.
5. as each described method among the claim 1-4, it is characterized in that the fusing point of described eutectic thermoplastic polymer is higher than 50 ℃.
6. method as claimed in claim 5, the fusing point that it is characterized in that described thermoplastic polymer is 50-150 ℃.
7. method as claimed in claim 6, the fusing point that it is characterized in that described thermoplastic polymer is 80-130 ℃.
8. as each described method among the claim 1-7, it is characterized in that the glass transition temperature of described thermoplastic polymer is-20 ℃-130 ℃.
9. method as claimed in claim 8, the glass transition temperature that it is characterized in that described thermoplastic polymer is 30-130 ℃.
10. as each described method among the claim 1-9, it is characterized in that described thermoplastic polymer is selected from polyester, polyamide and olefin polymer.
11. as each described method among the claim 1-10, it is characterized in that described thermoplastic polymer is scattered in the whole Lyocell fibers with phase farmland form, the full-size on all phase farmlands all is not more than 50nm substantially.
12., it is characterized in that describedly before washed fiber is curling, applying soft finishing agent as each described method among the claim 1-11.
13. method as claimed in claim 12, the applied amount that it is characterized in that described soft finishing agent is 0.01-2 weight %, is benchmark with the fibre weight.
14. method as claimed in claim 13, the applied amount that it is characterized in that described soft finishing agent is 0.1-0.5 weight %, is benchmark with the fibre weight.
15. method as claimed in claim 14, the applied amount that it is characterized in that described soft finishing agent is 0.15-0.4 weight %, is benchmark with the fibre weight.
16., it is characterized in that described fiber is curled as each described method among the claim 1-15, so that making fiber form 3.5-8 curls/centimetre.
17., it is characterized in that described solution comprises delustering agent, so that make fiber contain delustering agent as each described method among the claim 1-16.
18. method as claimed in claim 17 is characterized in that being dispersed with in the described solution titanium dioxide granule as delustering agent, thus, just is dispersed with 0.1-5 weight % titanium dioxide granule in the fiber of formation, is benchmark with the cellulose.
19. method as claimed in claim 18 is characterized in that being dispersed with titanium dioxide granule in the described solution, thus, just is dispersed with 0.1-2 weight % titanium dioxide granule in the fiber of formation, is benchmark with the cellulose.
20. method as claimed in claim 18 is characterized in that being dispersed with titanium dioxide granule in the described solution, thus, just is dispersed with 0.2-1 weight % titanium dioxide granule in the fiber of formation, is benchmark with the cellulose.
21., it is characterized in that described method also comprises the step that fiber is cut into the staple fibre of long 3-100mm as each described method among the claim 1-20.
22. method as claimed in claim 21 is characterized in that described fiber is cut into the staple fibre of long 20-75mm.
23. the method according to any one of the preceding claims, the fiber number that it is characterized in that formed fiber is the 0.5-5 dtex.
24. method as claimed in claim 23, the fiber number that it is characterized in that formed fiber is the 1-3.5 dtex.
25. as each described method among the claim 1-24, it is characterized in that described fiber is applied with the chemical substance with 2-6 and functional group of responding property of cellulose after washing and before the drying, this material is reacted on the fiber before drying or in the dry run.
26. a method, it will become the carded web fabric by the fiber process that each described method among the claim 21-25 is made.
27. method as claimed in claim 26, it is characterized in that the described fiber of being made by each described method among the claim 21-25 is processed to the carded web that weight is 30gsm, this method be included on ThibeauCA 11 carding machines with 150-275 rice/minute the one-tenth net spee, or on the identical machine of function, to act on identical speed carded fiber.
28. a Lyocell fibers, its inside are dispersed with the eutectic thermoplastic polymer particles to 30 weight % from trace (as described herein), are benchmark with the cellulose, and have 2.5-8 curl/centimetre.
29. Lyocell fibers as claimed in claim 28 is characterized in that its inside is dispersed with 0.001-30 weight % eutectic thermoplastic polymer particles.
30. Lyocell fibers as claimed in claim 29 is characterized in that its inside is dispersed with 0.01-20 weight % eutectic thermoplastic polymer particles.
31. Lyocell fibers as claimed in claim 30 is characterized in that its inside is dispersed with 0.1-10 weight % eutectic thermoplastic polymer particles.
32., it is characterized in that described eutectic thermoplastic polymer is selected from polyester, polyamide and olefin polymer as each described Lyocell fibers among the claim 28-31.
33. as each described Lyocell fibers among the claim 28-32, it is characterized in that having a kind of chemical substance on the described fiber, this chemical substance has the functional group of 2-6 and responding property of cellulose, this chemical substance is applied on the not dry fiber of crossing, and is reacting on fiber before the drying or between dry period.
34. as each described Lyocell fibers among the claim 28-33, it is characterized in that described thermoplastic polymer is scattered in the whole Lyocell fibers with phase farmland form, the full-size on all phase farmlands all is not more than 50nm substantially.
35., it is characterized in that its inside is dispersed with 0.1-5 weight % titanium dioxide granule, be benchmark with the cellulose as each described Lyocell fibers among the claim 28-34.
36. Lyocell fibers as claimed in claim 35 is characterized in that its inside is dispersed with 0.1-2 weight % titanium dioxide granule, is benchmark with the cellulose.
37. Lyocell fibers as claimed in claim 36 is characterized in that its inside is dispersed with 0.2-1 weight % titanium dioxide granule, is benchmark with the cellulose.
38. as each described Lyocell fibers among the claim 28-37, the fiber number that it is characterized in that it is the 0.5-5 dtex.
39. Lyocell fibers as claimed in claim 38, the fiber number that it is characterized in that it is the 1-3.5 dtex.
40., it is characterized in that it is the staple fibre of long 3-100mm as each described Lyocell fibers among the claim 28-39.
41. Lyocell fibers as claimed in claim 40 is characterized in that it is the staple fibre of long 20-75mm.
42., it is characterized in that being applied with above it 0.01-2 weight % soft finishing agent, be benchmark with the fibre weight as each described Lyocell fibers among the claim 28-41.
43. Lyocell fibers as claimed in claim 42 is characterized in that being applied with above it 0.1-0.5 weight % soft finishing agent, is benchmark with the fibre weight.
44. Lyocell fibers as claimed in claim 43 is characterized in that being applied with above it 0.15-0.4 weight % soft finishing agent, is benchmark with the fibre weight.
45. Lyocell fibers, it comprises the farmland mutually of the eutectic thermoplastic polymer that is selected from polyester, polyamide and olefin polymer, described fiber contains 0.1-30 weight % eutectic thermoplastic polymer, with the cellulose is benchmark, during with the electron microscope observation that amplifies 9000 times, all basically phase farmlands all be can't see.
46. Lyocell fibers, it comprises the farmland mutually of the eutectic thermoplastic polymer that is selected from polyester, polyamide and olefin polymer, described fiber contains 0.1-30 weight % eutectic thermoplastic polymer, is benchmark with the cellulose, and the full-size on all phase farmlands all is not more than 50nm basically.
47., it is characterized in that described fiber contains 0.5-10 weight % eutectic thermoplastic polymer as claim 45 or 46 described Lyocell fibers.
48. Lyocell fibers as claimed in claim 47 is characterized in that described fiber contains 1-5 weight % eutectic thermoplastic polymer.
49. a method for preparing Lyocell fibers, described fiber are substantially as described in this paper and the embodiment.
50. a Lyocell fibers, it is substantially as described in this paper and the embodiment.
51. a method for preparing Lyocell fibers, it comprises the steps:
(1) solution of preparation cellulose in moisture N-tertiary amine oxide solvent, this solution contains the eutectic thermoplastic polymer particles to 30 weight % from trace (as defined herein), is benchmark with the cellulosic weight that is scattered in the solution;
(2) with mould described solution is clamp-oned in the moisture coagulating bath, formed Lyocell fibers thus;
(3) washing the fibre removes residual N-amine oxide, and dried fibres;
(4) crimped fibre, so that making the interior 2.5-8 of formation of fiber curls/centimetre.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0025080A GB2368342A (en) | 2000-10-12 | 2000-10-12 | Lyocell fibre and its production |
| GB0025080.3 | 2000-10-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1469943A true CN1469943A (en) | 2004-01-21 |
| CN1214136C CN1214136C (en) | 2005-08-10 |
Family
ID=9901190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018173632A Expired - Fee Related CN1214136C (en) | 2000-10-12 | 2001-10-12 | Fiber and its production |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1327013B1 (en) |
| KR (1) | KR100808724B1 (en) |
| CN (1) | CN1214136C (en) |
| AU (1) | AU2001294030A1 (en) |
| DE (1) | DE60125964T2 (en) |
| GB (1) | GB2368342A (en) |
| WO (1) | WO2002031236A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102317515A (en) * | 2007-08-31 | 2012-01-11 | 可隆工业株式会社 | Preparation method for lyocell filament fibers, lyocell filament fibers, tire cord, and preparation method for tire cord |
| CN101743347B (en) * | 2007-07-11 | 2014-12-17 | 连津格股份公司 | Fibrefill fibre having improved opening characteristics, production and use thereof |
| CN107109707A (en) * | 2014-12-31 | 2017-08-29 | 可隆工业株式会社 | Lyocell material for cigarette filter and preparation method thereof |
| CN111630214A (en) * | 2018-01-15 | 2020-09-04 | 兰精股份公司 | Molded body comprising elastic fibers bound to cellulose and method for producing same |
| TWI828955B (en) * | 2020-03-30 | 2024-01-11 | 日商日東紡績股份有限公司 | Straight glass yarn bundles, and long glass fiber reinforced thermoplastic resin particles |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1936017B1 (en) * | 2006-12-22 | 2013-08-21 | Reifenhäuser GmbH & Co. KG Maschinenfabrik | Method and device for manufacturing a spunbonding fabric made of cellulose filaments |
| KR200457862Y1 (en) * | 2009-09-10 | 2012-01-05 | 세원셀론텍(주) | A apparatus of picking cartilage |
| KR101627768B1 (en) * | 2009-12-23 | 2016-06-08 | 코오롱인더스트리 주식회사 | Process for preparing lyocell filament fiber, lyocell filament fiber, and tire cord |
| KR101455002B1 (en) * | 2013-06-28 | 2014-11-03 | 코오롱인더스트리 주식회사 | Lyocell Material Cigarette Filter and Method for the Same |
| WO2016003145A1 (en) * | 2014-06-30 | 2016-01-07 | 코오롱인더스트리 주식회사 | Modified cross-section lyocell material for tobacco filter, and preparation method therefor |
| KR102211219B1 (en) | 2014-06-30 | 2021-02-03 | 코오롱인더스트리 주식회사 | Lyocell Material with Noncircle Cross Section for Cigarette Filter And Manufacturing Method of the same |
| WO2016052998A1 (en) * | 2014-09-30 | 2016-04-07 | 코오롱인더스트리 주식회사 | Lyocell crimped fiber |
| CN105200670B (en) * | 2015-08-17 | 2017-08-01 | 赖明荣 | A kind of low temperature resistant non-woven fabrics |
| EP3467174A1 (en) * | 2017-10-06 | 2019-04-10 | Lenzing Aktiengesellschaft | Knitted continuous filament lyocell fabrics |
| TWI814782B (en) * | 2018-03-06 | 2023-09-11 | 奧地利商蘭仁股份有限公司 | Solvent-spun cellulosic fibre |
| US11359309B2 (en) | 2018-12-21 | 2022-06-14 | Target Brands, Inc. | Ring spun yarn and method |
| TW202041732A (en) * | 2019-04-10 | 2020-11-16 | 奧地利商蘭仁股份有限公司 | Lyocell fiber tow, its manufacture and use |
| CN115559007B (en) * | 2022-09-23 | 2024-04-12 | 当阳市鸿阳新材料科技有限公司 | Extinction lyocell fiber and production method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2008126A (en) * | 1977-10-13 | 1979-05-31 | Courtaulds Ltd | Regenerated cellulose filaments |
| AT384628B (en) * | 1982-05-17 | 1987-12-10 | Chemiefaser Lenzing Ag | CELLULOSE FIBERS, ESPECIALLY FOR THE PRODUCTION OF FLEECES AND METHOD FOR PRODUCING THE FIBERS |
| TR28495A (en) * | 1993-05-24 | 1996-09-02 | Courtaulds Fibres Holdings Ltd | Production of cellulose fiber, cured from the strainer, curled. |
| GB9407496D0 (en) * | 1994-04-15 | 1994-06-08 | Courtaulds Fibres Holdings Ltd | Fibre treatment |
| JPH08170224A (en) * | 1994-12-20 | 1996-07-02 | Kuraray Co Ltd | Organic solvent-based cellulosic fiber soluble in disperse dye and its production |
| JPH09302520A (en) * | 1996-05-14 | 1997-11-25 | Kuraray Co Ltd | Production of readily fibrillating fiber |
| GB2324064A (en) * | 1997-04-11 | 1998-10-14 | Courtaulds Fibres | Modified lyocell fibre and method of its formation |
-
2000
- 2000-10-12 GB GB0025080A patent/GB2368342A/en not_active Withdrawn
-
2001
- 2001-10-12 DE DE60125964T patent/DE60125964T2/en not_active Expired - Fee Related
- 2001-10-12 AU AU2001294030A patent/AU2001294030A1/en not_active Abandoned
- 2001-10-12 EP EP01986728A patent/EP1327013B1/en not_active Expired - Lifetime
- 2001-10-12 KR KR1020037004647A patent/KR100808724B1/en not_active IP Right Cessation
- 2001-10-12 WO PCT/GB2001/004562 patent/WO2002031236A1/en active IP Right Grant
- 2001-10-12 CN CNB018173632A patent/CN1214136C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101743347B (en) * | 2007-07-11 | 2014-12-17 | 连津格股份公司 | Fibrefill fibre having improved opening characteristics, production and use thereof |
| CN102317515A (en) * | 2007-08-31 | 2012-01-11 | 可隆工业株式会社 | Preparation method for lyocell filament fibers, lyocell filament fibers, tire cord, and preparation method for tire cord |
| CN102317515B (en) * | 2007-08-31 | 2015-06-10 | 可隆工业株式会社 | Preparation method for lyocell filament fibers, lyocell filament fibers, tire cord, and preparation method for tire cord |
| CN107109707A (en) * | 2014-12-31 | 2017-08-29 | 可隆工业株式会社 | Lyocell material for cigarette filter and preparation method thereof |
| CN107109707B (en) * | 2014-12-31 | 2020-04-07 | 可隆工业株式会社 | Lyocell material for cigarette filter tip and preparation method thereof |
| CN111630214A (en) * | 2018-01-15 | 2020-09-04 | 兰精股份公司 | Molded body comprising elastic fibers bound to cellulose and method for producing same |
| TWI828955B (en) * | 2020-03-30 | 2024-01-11 | 日商日東紡績股份有限公司 | Straight glass yarn bundles, and long glass fiber reinforced thermoplastic resin particles |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1327013B1 (en) | 2007-01-10 |
| GB0025080D0 (en) | 2000-11-29 |
| GB2368342A (en) | 2002-05-01 |
| KR100808724B1 (en) | 2008-02-29 |
| AU2001294030A1 (en) | 2002-04-22 |
| CN1214136C (en) | 2005-08-10 |
| DE60125964D1 (en) | 2007-02-22 |
| KR20030061374A (en) | 2003-07-18 |
| WO2002031236A1 (en) | 2002-04-18 |
| EP1327013A1 (en) | 2003-07-16 |
| DE60125964T2 (en) | 2007-10-18 |
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Owner name: LENZING FIBERS LTD. Free format text: FORMER OWNER: TENCEL LIMITED Effective date: 20110517 Owner name: LENZING AKTIENGESELLSCHAFT Free format text: FORMER OWNER: LENZING FIBERS LTD. Effective date: 20110517 |
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Effective date of registration: 20110517 Address after: Austria Jinge Patentee after: LENZING AG Address before: British Nottingham Patentee before: Lion True Fiber Co.,Ltd. Effective date of registration: 20110517 Address after: British Nottingham Patentee after: Lion True Fiber Co.,Ltd. Address before: English Derby Patentee before: Tencel Ltd. |
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