JP2000226720A - Cellulose yarn having controlled fibrillation and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cellulose yarn having high dry and wet strengths and Young's modulus and greatly improved fibrillation resistance characteristics, which has not been sufficiently solved in known conventional method, by a production method friendly to the global environment. SOLUTION: A cellulose spinning dope dissolved in a mixed solvent of tertiary amine oxide/water is subjected to dry-wet spinning using a low-temperature solidifying bath having a specific ratio of methanol/water to give a cellulose filament having 30-48% crystallization degree of cellulose, >=1.8 g/dtex wet strength and, in fibrillation evaluation in a wet state, <=50 μm average fibril length and <=15% rate of occurrence of fibril having >=100 μm length.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a high wet strength.
Despite this, cells with highly suppressed fibrillation properties
It relates to loin fiber and its production method, for example, clothing
Suitable for food, living and industrial materials
The present invention relates to a cellulose fiber that can be used. 2. Description of the Related Art Pulp is produced by using caustic soda and carbon disulfide.
Regenerate xanthosed viscose stock solution containing sulfuric acid etc.
Viscose rayon fiber that is introduced into the bath and solidified and regenerated
Is produced in large quantities worldwide as regenerated cellulose fiber
However, with the recent rise of the global environmental protection movement,
Vigorous development of sphere-friendly cellulose fiber
Recently, N-methylmorpholine-N-oxide (hereinafter NMMO)
Abbreviated. ) As the undiluted solvent and water as the solidifying solvent
Solvent-based cellulose (Lyocell) fiber from Coatles (UK)
And Lenzing (Austria) have succeeded in developing
Tons / year of cut staples are produced. [0003] This resource is manufactured in an environmentally friendly manner.
Yossel staple is a conventional viscose rayon fiber
Cellulose has a higher degree of crystallinity,
Although it has the major feature of high
Which one-dimensional products such as two-dimensional products and ropes
Fine fibrils are formed during
It has the disadvantage of being easy to manufacture, especially for knitted fabrics.
Dry and wet during the process of knitting and fabric processing
When rubbed in a state, it fibrillates and becomes fluff,
In the field of long-filament filaments, which are easily linked to product defects
This is fatal, and despite the high demand,
Lyocell long fibers are not currently in production
It is. An attempt to suppress fibrillation of lyocell fiber
Is being done energetically and many suggestions have been made.
You. For example, spinning lyocell staples and spinning
After making the yarn into a knitted fabric, the enzyme treatment is applied to increase the cellulose.
Remove the oriented and highly crystallized fiber surface layer,
Monoaldehydes such as phosphorus, dia such as glyoxal
Cellulose by polyamines such as aldehyde and melamine
Introducing cross-linking and the like into loin has been performed.
In particular, enzymatic treatment is considered to be effective.
Enzyme treatment is a long-term treatment,
Cost increases due to the need for agent costs, personnel costs, process management costs, etc.
Leads to. [0005] Long fiber filaments are used for knitting and woven fabrics.
In the process, friction is more severe than staple of spun yarn
Is easy to fibrillate, and the generated fibrils
Process troubles such as fluffing and thread breakage occur frequently
And the processability is poor, and the obtained knitted fabric
The quality is also inadequate. The ease of fibrillation of lyocell fiber has been improved.
In order to improve, the cellulose spinning solution is solidified (usually
In the present invention, solidification and regeneration are called solidification and regeneration.
These phenomena, including essentially distinct gelation phenomena
It is regarded as a solidification phenomenon, which is a superordinate concept of, and is called solidification. )
Proposal of technology to suppress fibrillation in the solidification process
Have been. For example, Japanese Patent Application Laid-Open No. Hei 8-505120 and Japanese Patent Application Laid-Open
-508555 discloses that the solidification bath has a larger molecular weight than NMMO.
For example, added polyethylene glycol or surfactant
The fibril can be prepared by adding a surfactant to the stock solution.
It is possible to obtain lyocell fiber with suppressed
As shown, the fiber fibers obtained by these methods are
The effect of suppressing ibrillability is not suitable for long fiber filaments.
Is still not enough considering the use of
When trying to produce it operationally, NMMO is recovered from the solidification bath,
When reused, decomposition products and decomposition of polyethylene glycol
Post-reacted by-products and surfactants accumulate in the solidification bath,
It is difficult to solidify under certain conditions. In addition, Japanese Patent Application Laid-Open No. 9-505118 discloses an air jet below a spinning nozzle.
Methanol, ethanol, propano
Gas of aliphatic alcohol such as
It has been proposed that However, the fibrillation inhibitory effect
The fruits are inadequate and alcohol
Dissolves and is difficult to maintain under certain conditions. Further
Viscose Chemistry held in Stockholm in 1994
Weigel.P et al. Used isopropanol for solidification bath at seminar
Reports that fibrillation is suppressed when
However, according to the experiments of the present inventors, the lyosome
Fiber also cannot suppress fibrillation in the post-process
It was not enough. Furthermore, in German Publication No. 19600572A1,
By including ethanol in the post-treatment bath and washing bath
And the fibrillation of lyocell fiber is suppressed.
Disclosed, but required as long fiber filaments
It did not have high fibrillation resistance. An object of the present invention is to provide disulfur
Eco-friendly manufacturing method that does not use carbonized
Strength and Young's modulus are high, and
The fibrillation resistance that has not been solved
It is to provide an improved cellulose fiber. Means for Solving the Problems [0009] The present inventors have set forth the above object.
All process steps from spinning dope to winding
As a result of thorough examination of the matter,
Only when the solidification bath composition and solidification bath temperature are adopted,
Finding that the resistance to fibrillation is significantly improved
The present invention has been completed. [0010] That is, the present invention relates to the crystallinity of cellulose.
30 to 48%, wet strength of 1.8 g / dtex or more, and
Fibrillation in wet condition using an int shaker
In the evaluation, the average fibril length was 50 μm or less
The occurrence rate of fibrils of 100 μm or more is 15% or less.
Cellulose fiber characterized by the following:
Spinning of cellulose dissolved in mine oxide / water mixed solvent
When spinning a stock solution by wet or dry-wet method
The use of a solidification bath that satisfies the following conditions
This is a method for producing a cellulose fiber. Solidification bath composition: methanol (A) / water (B) (A) / (B) = 95/5 to 10/90 (volume ratio) Solidification bath temperature: −6 ° C. to 25 ° C. Morphology Crystallization of the cellulose fiber of the present invention
The degree is 30-48%. Here, the degree of crystallinity is expressed by the rotating anti-
X-ray using X-ray diffractometer RU-300 (DO201 type, manufactured by Rigaku Corporation)
This is a value obtained by a diffraction method. Crystallinity less than 30%
Then, the strength and Young's modulus are insufficient. 48% crystallinity
If it exceeds, it is easy to fibrillate. Crystallinity 33-46%
Is more preferable, and more preferably 35 to 45%. In the present invention, the cellulose constituting the fiber is
The degree of polymerization of the polymer is not particularly limited, but should be 100 to 2000.
Is desirable. The polymerization degree of cellulose referred to in the present invention is JIS P-
Measured using Oken viscometer according to 8101-1994
It is an average degree of polymerization. High strength when the degree of polymerization is less than 100
Fibers may not be obtained. Also, the degree of polymerization exceeds 2000
Results in insufficient solubility in tertiary amine oxides
And the spinnability may be poor. Therefore, the degree of polymerization is 200
~ 1500 is more preferable, and 300 ~ 1200 is more preferable.
New The cellulose fiber of the present invention has a wet strength of 1.8.
g / dtex or more. Here, wet strength refers to JIS-L1013.
Measured using Shimadzu Autograph A-500
Value. If the wet strength is less than 1.8g / dtex,
Fluff and thread breakage easily occur in the process. Therefore, the wet strength
More preferably, it is 2.2 g / dtex or more. High strength
I've never done that, but generally it should be stronger
The higher the fibrillability, the higher the wet strength is 3 g / d
It is preferable not to exceed tex. Further, the cellulose fiber of the present invention is preferably
Of fibrillation in wet condition using a shaker
In, the average fibril length is 50μm or less, and the length 100
Extremely low fibrillation rate of 15% or less
This fiber satisfies excellent fibrillation resistance. Average fibril length exceeding 50μm or 100μm length
Cellulose with an incidence of fibrils above 15%
Fibers are subject to long fibrils when rubbed in wet conditions.
Liable to occur, leading to fluff and breakage. Also made of pills
This is not preferred because defects in the product are likely to occur. The determination of the fibrillation property in a wet state is required.
The method is as follows. Cut to 5mm, oil
A single fiber sample from which the agent has been removed is covered with a lid containing 5 ml of water.
In addition to a glass bottle with a capacity of 20m1, the glass bottle was manufactured by Toyo Seiki
Shosha Co., Ltd. Paint Shaker A-30 Type Set to 30
After vigorous shaking for a minute, remove the monofilament with forceps
Single fiber sample fibrillated by shaking
Of microfibrils suspended in the residue after desorption from the membrane
Laser distribution particle size distribution analyzer manufactured by Shima Ritsu Seisakusho Co., Ltd.
Measured using SALD-1000, 50% average fibril length (single
Of fibrils with a fibril length of 100 μm or more
Determine the birth rate (%). The measurement was performed n = 12 times, and the average value was
A parameter that shows the fibrillation resistance of wet samples in the wet state.
Meter. The cellulose fiber of the present invention can be used in a dry state.
Shows excellent fibrillation resistance.For example, TM type yarn inclusion test
The number of fibrils in the test is 80 or more,
Fibrils are less likely to occur when rubbed, and
Difficult to become a point. The number of fibrils generated in a dry state is
Use a TM-type yarn inclusion tester manufactured by Kagaku Seiki Co., Ltd.
The sample is twisted at a rate of 1000 times / m.
10 samples with 100g / dtex load applied
At the same time, check for fibril occurrence every 10 times.
And the number of frictions until fibrils are observed
Is measured. Repeat n = 10 times and average the value
The number of occurrences. When the number of fibrils is less than 80,
Fluff is generated in post-processing processes such as the weaving and dyeing processes.
When using the product, defects such as pills are likely to occur. Fi
More preferably, the number of occurrences of brill is 90 or more,
In particular, it is preferably 100 times or more. The cellulose fiber of the present invention has high strength.
However, the reason why it is difficult to fibrillate is unknown, but will be described later.
By adopting specific fiberization conditions, cellulose weight
One factor is that the crystallization of coalescence is controlled at a low level.
It is estimated that there is. The cellulose fiber of the present invention is very good
Combines excellent fibrillation resistance and practical high wet strength
Therefore, it is useful as a material
The number of synthetic fibers is 10-200 and the yarn fineness is 20-400dtex.
When used as a fiber filament,
Can be Conventionally, lyocell fiber commercially available is
Staples based on spun yarn
Products, even if the fibers are fibrillated,
If it were, it was a type that was inconspicuous as a drawback. Of the present invention.
Lulose fiber has a lower number of twists than spun yarn, and
Easy to fibrillate when subjected to friction or shear force, and
Long-filament filaments in which formed fibrils are noticeable as a defect
It is difficult to fibrillate even when used as a paint. H
The number of constituent fibers as filament yarn is 20 to 100, yarn
More preferably, the fineness is 30 to 300 dtex. Next, the method for producing the cellulose fiber of the present invention will be described.
explain about. Cellulose fiber of the present invention, tertiary amine oxide / water
A stock solution of cellulose dissolved in a mixed solvent is wet-spun.
Rui or dry-wet spinning, satisfy the following conditions
It can be produced by using a solidification bath. Solidification bath composition: methanol (A) / water (B) (A) / (B) = 95/5 to 10/90 (volume ratio) Solidification bath temperature: −6 ° C. to 25 ° C. Spinning used in the present invention The stock solution is a tertiary amine.
The tertiary amine
As the oxide, for example, N-methylmorpholine-N-
Oxide (NMMO), dimethanolamine-N-oxide, etc.
Can be used, of which NMMO is most preferred
used. NMMO is an oxidizing solvent.
Explosion hazard, usually monohydrate (water based on weight)
(13% fraction) or more
It is. However, if the water in NMMO is more than 23.5%
Cellulose just before spinning-
The water contained in the NMMO spinning solution is 1 to 25 per 100 g of NMMO.
It is preferable to adjust to g. Temperature of spinning dope during spinning
Is not particularly limited, but from the viewpoint of solution coloring property and safety.
The temperature is preferably from 80 to 160 ° C.
Temperature is 82-168 ° C due to the relationship with the temperature of the spinning dope.
It is preferable to set. Next, a solidification bath which is a feature of the production method of the present invention.
Will be described. In the present invention,
The solidifying solvent that solidifies the cellulose is methanol
Mainly a mixed system of (A) and water (B), methanol (A) and water (B)
Should be 95/5 to 10/90. Of the solidifying solvent
The composition is alcohol other than methanol or water.
If the amount of methanol used exceeds 95% or water
%, A high wet state intended in the present invention is obtained.
It is possible to obtain cellulose fibers having fibrillation resistance.
Can not. The reason for this is unknown, but methanol or water
When used alone, the solidification ability is too high.
Class formed with a single solvent by using a mixed system of
At least part of the cement is destroyed,
Presumed to be From this viewpoint, the volume ratio of methanol (A) / water (B) is 90/10
~ 30/70, more preferably 90/10 ~ 50/50, especially 90
It is preferably from / 10 to 60/40. In the production method of the present invention, the solidified solution
In addition to the media (A) and (B), NM which is a stock solution
Since MO (C) is brought into the solidification bath, the composition of the solidification bath is strict.
Tightly, it becomes a mixed three-component system, but with fibril resistance
In order to stably produce fibers with excellent
Meta in the solidification bath due to the effect of the stock solution solvent
Change in composition ratio and solidification of mixed system of knoll (A) and water (B)
Add methanol and water to the bath to avoid
Perform solidification while controlling to be constant
Is preferred. In that case, add [Methanol (A) + water
(B)] can be adjusted so that more than 95%
preferable. On the other hand, if the solidification bath contains a large amount of NMMO (C),
Insufficient solidification ability makes normal spinning impossible
Or it becomes difficult to lower the temperature of the solidification bath. Next, the temperature of the solidification bath is from -6 ° C to 25 ° C.
You. If the temperature is lower than -10 ° C, the solidified yarn freezes and spins normally.
It is difficult to do. When the solidification bath temperature exceeds 15 ℃
Gelling properties are low and high strength fibers cannot be obtained.
No. Therefore, the solidification bath temperature is preferably between -6 ° C and 13 ° C.
It is more preferable that the temperature is −5 ° C. to 10 ° C. As described above, the solidification bath is supplied with methanol (A) and
Water and water (B), and the solidification bath temperature can be lowered.
This is the point of the present invention. The specified solidification bath conditions
The use of a cell with excellent fibrillation resistance
Lurose fiber can be obtained. The method for producing the cellulose fiber of the present invention is described above.
By setting the solidification bath to specific conditions as in
High fibrillation resistance in wet conditions
The point is to obtain cellulose fibers.
There is no particular limitation on the external manufacturing conditions, and known manufacturing techniques may be applied.
Can be used. For example, as the cellulose used in the present invention, dissolved pulp,
Pulp blocks are used, and these pulp
Cellulose, lignin and the like may be contained. these
Among them, α-cellulose content of 90% or more is particularly preferable.
Pulp. This pulp is in the form of sheet, powder,
Various shapes such as a fibrous shape are used. Also now
Used primarily in the production of viscose rayon
Not only high-quality softwood pulp
From hardwood pulp and fast-growing bamboo
Rups can also be used. The degree of polymerization of cellulose DP (one glucose ring
If it is too large, the viscosity of the solution will increase.
It is difficult to achieve uniform dissolution, and if it is too small, the viscosity decreases.
However, the yarn physical properties are reduced. To prepare a homogeneous solution
The polymerization degree of cellulose is preferably from 200 to 1500. The cellulose pulp is, for example, provided with a stirring blade.
Knead with tertiary amine oxide containing water in a container
To obtain a precursor before melting, and kneading and stirring the mixture to raise the temperature.
Dehydration under reduced pressure is performed to remove excess water to obtain a spinning stock solution.
Dehydration can be performed using a cylindrical concentrator or thin film evaporator.
Wear. Tertiary amine during kneading for precursor preparation
Oxide / water mixing ratio depends on tertiary amine oxide species
Depending on the type, it is preferably 40/60 to 70/30% by weight.
NMMO in spinning stock solution after dehydration of excess water under reduced pressure
The water / water weight ratio is preferably 94.5 / 5.5 to 82/18. [0030] The cellulose concentration of the spinning dope is preferably 5 to 25%.
Tertiary amine oxide
Cellulose concentration should be too high due to the high viscosity of
I can't do that. In addition, this spinning stock solution is removed by oxidative decomposition.
It is easy to cause a decrease in the polymerization degree and coloration of cellulose.
Prevention of oxidation of n-probilic acid and ascorbic acid
0.05 to 5% by weight of cellulose, especially 0.2 to 1% by weight
% Is preferably added. Furthermore, to improve spinnability, the interface of sodium lauryl sulfate etc.
No activator, no titanium oxide, etc. for gloss adjustment and friction suppression
Machine fine particles, pigment for spreading, etc. are added to the spinning dope
Is also good. When adding a surfactant, the addition amount is 0.1
-10% by weight is preferred, and 0.2-1% by weight is more preferred. The spinning stock solution is passed through a spinning nozzle to a solidifying bath and wet.
Spun or dry-wet spinning. Special limitations on spinning nozzles
There is no, but it is a conventional xanthosed viscose stock solution
High viscosity and high discharge pressure, the spinning
Pickles are preferably used. It also promotes the development of the liquid crystal structure.
Therefore, it is sometimes preferable to increase the nozzle land length.
is there. As the shape of the spinning nozzle, for example, a projection type or a flat tie
Various types such as loops and cones can be used. Also spinning nose
Although the hole diameter is not particularly limited, for example, the hole diameter D is 60 μm or less.
Above, those with a hole length L (unit mm) of L / D of 8 or more are stable.
It is preferably used because it can be spun with high draft.
You. In the spinning method, a solidifying bath is brought into contact with a spinning nozzle.
Even in wet spinning, there is a gas layer (d) between the spinning nozzle and the solidification bath.
Wet spinning with an air gap is also possible,
The fiber of the invention is mainly composed of long fiber filaments.
From this point of view, dry-wet spinning capable of high-speed spinning is advantageously suitable.
Used. The length of the gas layer is appropriately selected between 1 mm and 50 cm.
You. The spinning solution discharged from the spinning nozzle passes through the gas layer,
As described above, it is introduced into a specific solidification bath,
Be transformed into The solidified yarn is subsequently introduced into the extraction bath,
The tertiary amine oxide remaining in the yarn is extracted and removed,
Apply oils as needed, dry, roll up on bobbin
You. Thus, the method of the present invention is obtained.
Cellulose fiber has a crystallinity of 30 to 48% and a wet strength of 1.
Controlled at 8g / dtex or more and wet
Remarkable fibrillation resistance in conventional state
Lyocell fiber has not been able to enter
Opened the way to long fiber filament products
It is. Hereinafter, the present invention will be described specifically with reference to examples.
However, the present invention is not limited to these examples.
Absent. In addition, each measured value in the example was determined by the following method.
It is a measurement that has been carried out. Yarn fineness (dtex); denier computer
(SEARCH SEIGYO EM.CO, LTD) Strength, elongation, Young's modulus measurement; JIS-L1013, Autograph Island
Tsu A-500 Degree of polymerization of cellulose DP; viscosity of cellulose as described above; viscometer (HB
(T type). Crystallinity of the fiber; fibrillability of the fiber as described above; spinning stability as described above; conditions under which the fineness of the drawn yarn is 2.2 dtex
When it is taken out very stably for 20 minutes when spun at
"◎", Stable spinning without fiber breakage, but slight hair
“○” when feathers occur, slight fiber breakage or many
"△" when the fluff comes out, when it cannot be picked up
Is indicated by "x". Bath draft ratio (DR); take-off speed in solidification bath (VL: M / min)
And the ratio of the spinning solution discharge rate (g / min). Example 1 A small dry-wet spinning apparatus was previously placed in a melting tank (internal volume 10 L).
Opened pulp (Western pulp, degree of polymerization DP = 621, kana
A, ALICELL) 500 g, heat to 80 ° C and leave for 1 hour
Was. Separately, N-methylmorpholine heated to 90 ° C
-N-oxide hydrate solution (NMMO aqueous solution) in 4500 g
N-Propyl gallate (GnP) as a stabilizer for pulp
0.25% by weight and sodium lauryl sulfate as a surfactant
Lithium (SLS) is added at a rate of 0.25% by weight, and dissolved by stirring.
The prepared solution was prepared. Next, the solution was added to the solution in the dissolution tank.
Sprinkle evenly on the heated pulp, cover the melting tank
Replace with nitrogen and let stand for 30 minutes to fully swell the pulp.
And stir for 1 hour with a stirrer installed in the dissolution tank to completely remove the pulp.
Dissolved. Then raise the temperature of the melting tank to 100 ° C and stir
And leave it for 4 hours to remove bubbles sufficiently to prepare the spinning solution.
It was adjusted. The obtained spinning dope is NMMO with a cellulose concentration of 10%.
Solution, and using this, the following
Fiberization was performed under spinning conditions. Spinning conditions Spinning temperature: 124 ° C. Spinning nozzle hole diameter-number of holes: 120 μm-40 holes Spinning nozzle discharge rate: lg / min Air gap (AG) length: 50 mm Solidification bath conditions Solidification bath composition ratio; methanol (A) ) / Water (B) = 95/5 vol% The solidification bath composition ratio is constant after adding methanol and water
It controlled so that it might become. Solidification bath temperature: 2 ° C Winding conditions Yarn speed in solidification bath: 16M / min Drying temperature: 90 ° C Bath draft ratio: 16 Cellulose fiber obtained under the above spinning conditions
Has a fineness of 1.7 dtex, a crystallinity of 43%, and a wet strength of 2.9 g / dte
x, wet elongation is 13.5%, wet Young's modulus is 20.1g / dtex,
Painted 150 times in the dry state evaluation of TM type yarn inclusion tester
Average fibrils in wet conditions using a shaker
The incidence of fibrils with a length of 22.1 μm and a length of 100 μm or more
The fiber had good fibrillation resistance of 3.2% or less.
(Refer to Table 2.)
Rayon, copper ammonia method rayon, organic solvent cellulo
Staples, spun yarns and filaments
The brillability was evaluated, and as shown in Table 4,
Compared with the cellulose fiber of the present invention, the fibrillation resistance
It can be seen that it has been greatly improved. The spinning conditions and spinning test results in the examples are summarized below.
It is shown in Table 1 and its physical properties, crystallinity and fibril resistance are shown in Table 2.
The results of evaluation of chemical properties are shown. [Table 1] [Table 2] [Table 3] [Table 4] Examples 2 to 5 The solidification bath composition and the solidification bath temperature were changed as shown in Table 1.
Except that, fiberization and evaluation were performed in the same manner as in Example 1.
Was. The spinning conditions and spin test results are shown in Table 1 and Table 2.
The results of measurement of the yarn physical properties, crystallinity, and fibrillation properties are shown in FIG. Example 6 Cellulose concentration, spinning temperature, solidification bath take-off speed, bath draft
Ratio, solidification bath composition, and solidification bath temperature were changed as shown in Table 1.
Fiberization and evaluation in the same manner as in Example 1 except that
went. Table 1 shows the overall spinning conditions and the results of the spinning test.
The evaluation results of the properties, crystallinity and fibrillation properties were shown. Example 7 Cellulose concentration, discharge rate, spinning temperature, take-off speed in a solidifying bath,
The bath draft ratio, solidification bath composition, and solidification bath temperature are shown in Table 1.
Fiberization in the same manner as in Example 1 except that
And evaluation. Table 1 shows the overall spinning conditions and the results of the spinning test.
The evaluation results of the properties, crystallinity and fibrillation properties were shown. Example 8 Contains 1028 g of pulp (degree of polymerization DP = 621) and 40% by weight of water
6000 g of N-methylmorpholine-N-oxide
Then, reduce the pressure while heating and stirring at about 100 ° C to steam about 1080 g of water.
Then, a solution having a cellulose concentration of 20% by weight was prepared. this
The solution was spun at a spinning temperature of 138 ° C with a diameter of 200 μm and an L / D of 17.
The thread nozzle hole is extruded from a spinneret having 36 pieces,
After passing through a 50 mm air layer with
Nord / water = 90 / 10vol%, solidified at a solidification bath temperature of -4 ° C, and yarn
The article has taken over. 0.434 g of discharge per spinning nozzle hole
/ M, a take-off speed of 5 OOM / min yielded 1.7 dtex yarn. Table 1 shows the spinning conditions and spinning test results.
The results of evaluation of crystallinity and fibrillation properties are shown. Example 9 Using pulp having a polymerization degree DP of 300, spinning temperature and solidification bath take-off speed
Degree, bath draft ratio and solidification bath temperature were changed as shown in Table 1.
Except that the fiberization and evaluation was performed in the same manner as in Example 1.
went. Table 1 shows the spinning conditions and spinning test results.
The results of evaluation of crystallinity and fibrillation properties are shown. Example 10 Alaska pulp (Alaska-pulp co. Ltd.) having a degree of polymerization of 1050 was used.
The cellulose concentration and solidification bath temperature were varied as shown in Table 1.
Fiberization and evaluation in the same manner as in Example 1 except for the changes
Was done. Table 1 shows the spinning conditions and spinning test results.
The results of evaluation of physical properties, crystallinity, and fibrillation properties are shown. Comparative Example 1 The spinning dope used in Example 1 was subjected to dry-wet spinning.
In the gas layer from the yarn nozzle outlet to the solidification bath,
Spraying a stream of methanol gas to change the solidification bath composition to water alone
And the same as in Example 1 except that the solidification bath temperature was set to 8 ° C.
And evaluated for fiberization (Table 3). Cellulose fibers obtained under the above spinning conditions are
Average in evaluation of fibrillation in wet condition using a shaker
Fibril length is 82 μm, fibrils with a length of 100 μm or more
The incidence was as bad as 28%. Comparative Example 2 The solidification bath composition was set to 100% isopropanol, and the solidification bath temperature was set to
Except that the temperature is 30 ° C., fiberization and the same as in Example 1
Evaluation was performed (Table 3). The cellulose fibers obtained under the above spinning conditions are
In the evaluation of fibrillation in a wet state using a shaker,
The average fibril length is 119μm and the fibril length is 100μm or more.
The incidence of le was as low as 60%. Comparative Example 3 The solidification bath composition was 100% polyethylene glycol (molecular weight 500).
And the same as in Example 1 except that the solidification bath temperature was set to 30 ° C.
And evaluated for fiberization (Table 3). The cellulose fibers obtained under the above spinning conditions are
In the evaluation of fibrillation in a wet state using a shaker,
Fibrils with an average fibril length of 69 μm and a length of 100 μm or more
The incidence was as bad as 17%. Comparative Example 4 The solidification bath composition was set to 100% water.
The wet yarn just before the dryer is treated with ethanol, and dried for 90 minutes.
Except that the fiberization was carried out in the same manner as in Example 1.
And evaluation (Table 3). The cellulose fibers obtained under the above spinning conditions are
In the evaluation of fibrillation in a wet state using a shaker,
Fibrils with an average fibril length of 76 μm and a length of 100 μm or more
The incidence was poor at 36%. Comparative Example 5 The solidification bath composition was set to 100% water, and the solidification bath temperature was set to 2 ° C.
Fiberization and evaluation were performed in the same manner as in Example 1 except for and.
At this time, water was continuously corrected and added to the solidification bath, and the N
The effect of MMO was minimized. The cellulose fibers obtained under the above spinning conditions have a crystallinity of 34.
%, Wet strength 2.3g / dtex.
Fibrils are generated 30 times in the dry state, paint
In the evaluation of fibrillation in a wet state using a shaker,
Average fibril length is 105 μm, fibrils with a length of 100 μm or more
The incidence of le was 88.5%. Table 3 shows the spinning conditions and spinning test results.
The results of evaluation of crystallinity and fibrillation properties are shown. Comparative Examples 6, 7, 8 The solidification bath composition and the solidification bath temperature were changed as shown in Table 3.
Fiberization and evaluation were performed in the same manner as in Example 1 except that
Was. Table 3 shows the overall spinning conditions and the results of the spinning test.
The evaluation results of the properties, crystallinity and fibrillation properties were shown. Comparative Example 9 The procedure of Example 1 was repeated except that the solidification bath temperature was changed to 30 ° C.
Fiberization and evaluation were performed. The spinning conditions and spinning test results are shown in Table 3, and Table 4 shows the yarn
The results of evaluation of crystallinity and fibrillation properties are shown. Comparative Example 10 Solidification bath composition and solidification bath temperature were set to the conditions shown in Table 3.
Except for the above, fiberization and evaluation were performed in the same manner as in Example 1.
Table 3 shows the spinning conditions and spinning test results.
The results of evaluation of crystallinity and fibrillation properties are shown. Reference Examples 1 to 6 The following cellulose fibers had the same physical properties and resistance as in the examples.
The fibrillation property was evaluated. (Refer to Table 4.) Reference Example 1: Viscose rayon (Kuraray, 75d / 35f) Reference Example 2: Copper ammonia method rayon (Asahi Kasei, 75d / 50f) Reference Example 3: Company A organic solvent-based cellulose fiber (staple raw material)
Cotton, 2.4 dtex) Reference Example 4: Company B organic solvent-based cellulose fiber (30-count spun yarn,
1.l8dtex) Reference Example 5: Company C organic solvent-based cellulose fiber (long fiber, 1.68dte
x) The cellulose fiber of the present invention has excellent wettability.
Extremely good fibrillation resistance while maintaining strength
Has the traditional Lyocell fiber can enter
Suitable for the field of long fiber filament woven and knitted fabrics
can do.

Continuation of front page    (72) Inventor Satoshi Maeda             1621 Sazu, Kurashiki City, Okayama Prefecture Kura Corporation             Inside (72) Inventor Shoji Akiyama             2045, Sakurazu, Kurashiki City, Okayama Prefecture 1             In Kuraray F term (reference) 4L035 BB04 BB06 BB11 BB14 BB15                       BB16 BB22 EE08 EE20 FF01                       HH10

Claims (1)

Claims: 1. In the evaluation of fibrillability in a wet state using a paint shaker, wherein the crystallinity of cellulose is 30 to 48%, the wet strength is 1.8 g / dtex or more, and A cellulose fiber having an average fibril length of 50 µm or less and a fibril generation rate of 100 µm or more of 15% or less. 1. The cellulose fiber according to claim 1, wherein the number of constituent fibers is 10 to 200, and the yarn fineness is 20 to 200.
Multifilament which is 400dtex. 3. A cellulose fiber characterized by using a solidification bath satisfying the following conditions when spinning a stock solution of cellulose dissolved in a tertiary amine oxide / water mixed solvent by a wet or dry-wet method. Manufacturing method. Solidification bath composition: methanol (A) / water (B) (A) / (B) = 95/5 to 10/90 (volume ratio) Solidification bath temperature: −6 ° C. to 25 ° C. 4. Methanol (A) ) / Water (B) composition ratio (A) /
4. The method for producing a cellulose fiber according to claim 3, wherein (B) = 90/10 to 60/40 (volume ratio).