JPH06298999A - Solution for casting cellulose and method for casting using the same - Google Patents

Abstract

PURPOSE:To obtain a solution for casting cellulose, containing a specific mixed solvent and a specific cellulose composition, capable of stably casting at a high rate, excellent in solution flowability and casting property without lowering mechanical properties of the resultant formed product and useful for producing fibers, films, etc. CONSTITUTION:The objective casting solution contains (A) a mixed solvent consisting of N-methylmorpholine-N-oxide and a solvent capable of being uniformly mixed with N-methylmorpholine-N-oxide and incapable of dissolving cellulose and (B) a cellulose composition dissolved in the mixed solvent and being a mixture composed of a component consisting of (i) a cellulose having 500-2000 degree of polymerization and (ii) a component consisting of one or more compounds selected from a group consisting of a cellulose(derivative) in the range of 350 to 900 degree of polymerization and having a degree of polymerization of <=90% of that of the component (i) and polysaccharide and having a blend weight ratio of the component (i) to the component (ii) of (95/5) to (50/50). Furthermore, the solution is preferably formed in flow having desired shape and brought into contact with a coagulating liquid and solidified.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cellulose molding solution and a molding method using the same. More specifically, it relates to a cellulose molding solution capable of molding fibers, films and the like at high speed and stably, and a cellulose molding method using this solution.

[0002]

2. Description of the Related Art Viscose method and cuprammonium method have been conventionally known as a method for producing cellulose fibers. However, it is difficult to reuse the solvent for cellulose used in this method, and if this is discarded, environmental pollution will occur. There is. In consideration of environmental safety, N-methylmorpholine-
A method of preparing a cellulose molding solution in which cellulose is dissolved in an N-oxide aqueous solution and producing a molded article such as a fiber or a film from the cellulose molding solution is disclosed in JP-B-60-
No. 28848 (or corresponding US Pat. No. 4,246,221 and US Pat. No. 4,416,698). This method is advantageous in that the solvent for cellulose can be recovered from the spinning bath and reused. Further, in JP-A-4-308220 (or corresponding US Pat. No. 5,252,284), the same cellulose molding solution as described above is extruded from a spinning nozzle having a small pore size,
A method of spinning a fine denier yarn with a low spinning draft is disclosed.

In general, a solution of cellulose in N-methylmorpholine-N-oxide has a high viscosity, and its elastic behavior as a viscoelastic body is remarkable. Since such a solution having a high viscosity is difficult to deform, it is difficult to increase the spinning draft ratio (take-off speed / the linear velocity of the solution discharged from the nozzle hole). Further, when molding is performed using a nozzle having a small hole diameter or a slit having a narrow width, when the discharge amount is increased, melt fracture (a large disturbance of the flow of the solution at the nozzle hole outlet) occurs. Therefore, the range in which stable molding can be performed is limited to a low discharge region where melt fracture does not occur, which is a factor of lowering productivity.

As a method of molding without lowering productivity, a method of lowering the viscosity of the solution can be considered. When a solution having a low viscosity is used, the occurrence of melt fracture is suppressed, so that the molding stability is improved. Further, a solution having a low viscosity is easily deformed, and the spinning draft ratio and the take-up speed can be increased.

Generally, the viscoelastic behavior of a solution of a polymer substance depends on the solution concentration, the solution temperature, the molecular weight of the dissolved polymer substance and the like. Generally, in order to reduce the viscosity of a solution of a polymer substance, a method of lowering the concentration of the polymer substance in the solution or lowering its molecular weight can be considered.

However, it is not preferable to reduce the concentration of the polymer substance in the solution, because the productivity of the molded article is lowered and the load on the solvent recovery system is increased. Further, lowering the molecular weight of the dissolved polymeric substance is not preferable because the mechanical properties such as strength and elongation of the obtained molded product become unstable and easily fluctuate.

US Pat. No. 4,983,730 discloses mixing high molecular weight cellulose acetate with low molecular weight cellulose acetate having a viscosity at least 20% lower than that of the high molecular weight cellulose acetate.
A method for obtaining a water-soluble cellulose acetate composition having excellent processability (processability) and a molded article having high tensile strength is disclosed. However, this patent does not include any mention of solutions of cellulose, especially solutions of cellulose with N-methylmorpholine-N-oxide. Moreover, cellulose acetate is a polymer substance that is soluble in a relatively large number of solvents, and its viscosity can be lowered, while the N-methylmorpholine-N-oxide solution of cellulose is
Since the viscosity is high and the elastic behavior as a viscoelastic body is remarkable, it is difficult to deform in the molding process, and thus it is difficult to increase the productivity of the molded product.

[0008]

The object of the present invention is to improve the molding processability without substantially lowering the molecular weight of cellulose, and as a result, without lowering the mechanical properties of the resulting molded article, and Another object of the present invention is to provide a cellulose molding solution that enables stable production of a molded article from a cellulose molding solution at high speed and a molding method using the same.

[0009]

The above object can be achieved by the cellulose molding solution of the present invention having the following constitution. That is, the gist of the present invention is a mixed solvent consisting of N-methylmorpholine-N-oxide and a solvent that can be uniformly mixed with N-methylmorpholine-N-oxide and that is insoluble in cellulose, And a cellulose composition dissolved in this mixed solvent, wherein the cellulose composition comprises (1) a component [I] composed of cellulose having a degree of polymerization of 500 to 2000, and (2) 35.
At least one selected from the group consisting of cellulose having a degree of polymerization of 0 to 900 and having a degree of polymerization of 90% or less of the degree of polymerization of the component [I], a cellulose derivative, and a polysaccharide. And a blending ratio of the component [I] and the component [II] in the range of 95: 5 to 50:50. Is.

The cellulose molding method of the present invention comprises forming the above-mentioned cellulose molding solution into a flow having a desired shape,
This is a cellulose molding method characterized by contacting this with a coagulating liquid to solidify it. In particular, in the above cellulose molding method, the above cellulose molding solution is discharged into the air from a spinning nozzle having at least one spinning hole, and this discharged filamentous cellulose molding solution flow is drafted. However, the method includes a cellulose molding method of bringing the coagulated fiber into contact with a coagulation liquid to coagulate the coagulated liquid, and the obtained coagulated liquid is taken out from the coagulation liquid to form a cellulose fiber, that is, a cellulose fiber spinning method.

Cellulose component [I] used in the present invention
Is 500 to 2000, preferably 1000 to 2000
It is composed of cellulose having a polymerization degree of. If the degree of polymerization is less than 500, the resulting molded article will have unsatisfactory mechanical properties such as strength and elongation.
When it exceeds 00, the moldability of the obtained cellulose molding solution becomes unsatisfactory.

The component [II] used in the present invention is
In addition to cellulose having a specific degree of polymerization, cellulose derivatives and polysaccharides can be used. The cellulose used in the component [II] has a degree of polymerization in the range of 350 to 900, and has a degree of polymerization of 90 in the component [I] cellulose.
It must be selected from those having a degree of polymerization of not more than%. In this case, if the degree of polymerization is less than 350, the resulting cellulose molding solution is markedly colored, and it is difficult to decolorize the molded product and the recovered solvent. If the degree of polymerization of this cellulose exceeds 900, the effect of improving the moldability of the resulting solution will be unsatisfactory. Further, the degree of polymerization of the cellulose for the component [II] is 9 times that of the cellulose for the component [I].
If it exceeds 0%, the effect of improving the moldability of the resulting solution becomes unsatisfactory.

The cellulose derivative used in the component [II] may be any as long as it can be dissolved in the above-mentioned specific mixed solvent used in the present invention, specifically, cellulose diacetate, cellulose triacetate, hydroxypropyl cellulose, hydroxy. Propyl methylcellulose,
Examples thereof include methyl cellulose and the like. Among these, cellulose diacetate is effective for improving the moldability of the obtained cellulose molding solution, especially for improving the spinnability.

Further, the polysaccharide used as the component [II] may be any one as long as it can be dissolved in the above-mentioned specific mixed solvent used in the present invention, and specifically, β-1,3 glucose, α-1. Among these, β-1,3 glucose is effective for improving the moldability of the resulting cellulose molding solution, especially for improving the spinnability.

In the cellulose composition used in the present invention, the blending weight ratio [I] of the component [I] and the component [II]:
[II] is 95: 5 to 50:50, and if the ratio of the component [II] is less than 5% by weight, the effect of improving the moldability of the resulting cellulose molding solution, particularly the spinnability, becomes unsatisfactory.
On the other hand, if it exceeds 50% by weight, mechanical properties such as strength and elongation of the obtained molded product become unsatisfactory.

The cellulose used in the present invention can be selected from dissolving pulp, pulp floc and the like. These pulps may contain hemicellulose, lignin and the like. Among these, it is preferable to use pulp having an α-cellulose content of 90% by weight or more.

In the present invention, the pulp used as the cellulosic material may be in the form of sheet or powder. The sheet-like material may be made into a chip-like shape with a cutting machine such as a shredder. Further, the pulp may be pulverized into particles as long as the molecular weight of cellulose is not significantly reduced.

The solution of the present invention comprises a cellulose composition and N
-Methylmorpholine-N-oxide, and a solvent that can be uniformly mixed with N-methylmorpholine-N-oxide and cannot dissolve cellulose (hereinafter referred to as non-solvent), and a mixed solvent consisting of To be done. here,
The solvent can be uniformly mixed with N-methylmorpholine-N-oxide means that the solvent and N-methylmorpholine-N-oxide are compatible with each other and form a uniform solution with each other. Alternatively, it refers to forming a uniform dispersion or emulsion.

In the present invention, N-methylmorpholine-N-oxide in a mixed solvent is used as a solvent for cellulose.
No. 91, Japanese Patent Publication No. 55-46162, and Japanese Patent Publication No. 55-
41693 (or corresponding US Pat. No. 42115)
No. 74, No. 4142913, and No. 4144080
Other tertiary amine oxides described in No.
It is possible to use together with -methylmorpholine-N-oxide. In this case, particularly preferable as the other tertiary amine oxide that can be used in combination is a cyclic mono (N-methylamine-N-oxide) compound similar to N-methylmorpholine-N-oxide, and for example, N -Methylpiperidine-N-oxide, N-methylpyrrolidone oxide and the like.

A preferred non-solvent for cellulose used in the present invention is water, but a mixed solvent of water and an alcohol such as methanol, n-propanol, isopropanol or butanol may be used. Also, any aprotic organic solvent such as toluene, xylene, dimethylsulfoxide, dimethylformamide, dimethylacetamide, etc. is used as a cellulose non-solvent unless it chemically reacts with N-methylmorpholine-N-oxide or cellulose. be able to.

Further, a stabilizer may be added to the mixed solvent. Most preferred as such a stabilizer is propyl gallate, which is disclosed in JP-B-3-29819.
Other gallic acid esters described in US Pat. No. 4,426,228 (eg corresponding US Pat. No. 4,426,228), such as methyl gallate, ethyl gallate, isopropyl gallate, etc. may be used. In addition, glycerin aldehyde, L-ascorbic acid, isoascorbic acid, triose lectductone,
Also, a compound having a compound structure in which a double bond is adjacent to a carbonyl group such as reductic acid can be used as a stabilizer. Further, ethylenediaminetetraacetic acid and the like can also be used as a stabilizer of the cellulose molding solution of the present invention. Further, as the inorganic compound, calcium pyrophosphate, calcium chloride, ammonium chloride, etc. described in US Pat. No. 4,880,469 can be used as a stabilizer of the cellulose molding solution of the present invention.

The cellulose molding solution of the present invention can be prepared either continuously or batchwise. That is, the dissolution may be continuously adjusted using a screw type extruder or the like, or the batch dissolution may be adjusted using a tank type kneader equipped with a heating means and a reduced pressure deaeration means. The melting temperature of the cellulose composition is not particularly limited, but is 90 to 120.
It is preferably carried out in the range of about ° C. If the melting temperature is too high, the degree of polymerization may be significantly lowered due to the decomposition of cellulose, and the decomposition and coloring of the solvent may be remarkable, and if it is too low, the dissolution may be difficult.

The total concentration of the cellulose composition in the cellulose molding solution of the present invention is preferably 30% by weight or less. Considering the moldability of the cellulose molding solution and the productivity of the molded product, the cellulose composition is The composition concentration is 6 to
It is preferably in the range of 25% by weight. Further, the content of N-methylmorpholine-N-oxide in the mixed solvent used for the cellulose forming solution, and the content of the solvent that is a non-solvent of cellulose and that can be mixed with N-methylmorpholine-N-oxide is: Preferred are 48 to 90% by weight and 5 to 22% by weight, respectively. When water is used as the non-solvent for cellulose, the proportion of water is set to a large value of 20 to 50% by weight in the step of adding the cellulose composition to the mixed solvent, and then the water is removed under reduced pressure heating. ,
It is preferable to adjust the proportion of water to 5 to 22% by weight.

The cellulose molding solution of the present invention is used for producing molded articles such as films and fibers. To produce a molded article from the cellulose molding solution of the present invention, this cellulose molding solution is molded into a desired shape, for example, a film shape or a fibrous shape. For this purpose, the cellulose molding solution is extruded through a film-forming slit or a spinning nozzle having at least one fiber-forming spinning hole, whereby the formed cellulose solution forming stream (film-like stream or fiber) is formed. Flow) is brought into contact with the coagulating liquid to be solidified, and the solidified product is taken out from the coagulating liquid. The cellulose molding solution of the present invention is particularly useful for spinning cellulose fibers. As the coagulating liquid, one that does not dissolve cellulose but dissolves a mixed solvent is used.

Next, a method for spinning cellulose fibers using the cellulose molding solution of the present invention will be described.
First, a mixed solvent solution of a cellulose composition prepared by a dissolver is conveyed to a spinning nozzle in a constant amount by, for example, a gear pump. The solution is once cooled and solidified, and the solidified product is crushed into an appropriate shape, then fed into a melt extruder, heated and redissolved therein, and a fixed amount is fed to a spinning nozzle via a gear pump. You may convey.

The spinning method itself is a conventionally known spinning method, that is, the cellulose molding solution is discharged into the air from a spinning nozzle having one or more spinning holes, and the formed filamentous solution flow is drafted. It is possible to employ a method of contacting the coagulation liquid with the coagulation liquid to coagulate the coagulation liquid, and to take out the solidified cellulose fiber. When the cellulose molding solution of the present invention is used, the generation of melt fracture is suppressed even when the solution is taken at a high speed of 500 m / min or more, and therefore stable spinning is possible.

In the case of the above spinning, the spinning hole of the spinning nozzle is
The diameter D is 200 μm or more, and the ratio L / D of the diameter D to the length L of the nozzle hole is preferably 10 or more, more preferably 15 or more. A spinning nozzle having such a spinning hole is used. Spinning with high draft enables stable spinning. Since the cellulose molding solution used in the present invention has a high elastic behavior as a viscoelastic body, the diameter D of the spinning hole is less than 200 μm, or the ratio L / D of the diameter D and the length L of the spinning hole is L / D. If less than 10, melt fracture may occur at the exit of the spinning hole. This phenomenon occurs remarkably when the discharge speed is high, so that it becomes impossible to increase the maximum spinning draft ratio, which makes it difficult to obtain stable and uniform fibers at high speed.

Further, in the molding method of the present invention, particularly in the spinning method, when a ceramic molding nozzle, particularly a spinning nozzle, is used, the occurrence of melt fracture is further suppressed even in the high draft region, and the speed and stability are further improved. Therefore, even a cellulose fiber having a single yarn fineness of 3 denier or less can be produced at high speed and stably.

The ceramic portion in the molding nozzle used in the present invention may be at least a portion through which the cellulose molding solution passes (spinning hole in the case of a spinning nozzle, slit in the case of a film nozzle) if the inner surface is ceramics, Therefore, the surface of the molding hole or the surface of the molding slit of the metal nozzle may be coated with ceramics, or the metal molding nozzle may be embedded with a ceramic chip having the molding hole or the molding slit. It goes without saying that the entire molding nozzle may be made of ceramics.

The ceramic used in the present invention means aluminum oxide, magnesium oxide, beryllium oxide, zirconium oxide and a mixture thereof, and zirconium oxide is particularly preferable in the present invention.

The coagulating liquid used in the molding method of the present invention, particularly in the spinning method, does not dissolve cellulose, but
There is no particular limitation as long as it dissolves the mixed solvent,
One or two selected from non-solvents of cellulose such as water and alcohols (eg, methanol, ethanol, butanol, n-propanol and isopropanol).
A mixed solvent for coagulation consisting of one or more kinds, or a mixed solvent for coagulation of the non-solvent of cellulose and N-methylmorpholine-N-oxide is preferably used. Further, other coagulating solvent for coagulation may be added with another tertiary amine oxide that can be mixed with N-methylmorpholine-N-oxide. In addition, any aprotic organic solvent that does not chemically react with N-methylmorpholine-N-oxide such as dimethylsulfoxide, dimethylformamide, dimethylacetamide or cellulose may be added to the coagulation mixed solvent. Among these, the most suitable coagulation liquid is water or water and N-methylmorpholine-N.
A mixed solvent for coagulation of oxides. Further, a pH adjusting agent such as acetic acid can be added to these coagulation liquids.

[0032]

EXAMPLES The present invention will be specifically described below with reference to examples. In these examples, the compounding ratio of the cellulose composition and the like is a weight ratio. The degree of polymerization of cellulose is B.DA.
"CELLULOSE CHEMISTRY AND TECHNOLO" of LBE, A.PEGUY, etc.
GY ”, Vlo. 24 No. 3P327-331 (1990). That is, in this measurement method, N-methylmorpholine-N-oxide hydrate, dimethyl sulfoxide, and propyl gallate were used as a solvent for cellulose in a weight ratio of 100/100, respectively.
Cellulose was dissolved in a concentration of 0.2 to 0.8 g / 100 ml using a mixture of 150/1, and the intrinsic viscosity of the cellulose solution was measured at a temperature of 34 ° C. using an Ubbelohde dilution viscometer. Then, the degree of polymerization of cellulose was determined by the following viscosity formula. [Η] = 1.99 × (DP) _v ^{0.79 In the} above formula, [η] is the intrinsic viscosity and (DP) _v is the degree of polymerization of cellulose.

(Example 1) Softwood dissolving pulp NDPT (cellulose (component [I])) made by Sanyo Kokusaku Pulp having a degree of polymerization of 1000 and KC Flock W-300 (cellulose (component (component) made by Sanyo Kokusaku Pulp) having a degree of polymerization of 400 [I
I])) and 5 mixtures (weight ratio: as shown in Table 1) with 3000 g of N-methylmorpholine-N-oxide containing about 40% by weight of water and 15 g of propyl gallate. , Kodaira Seisakusho's mixer with vacuum defoamer ACM-5 type, and while mixing this mixture under reduced pressure heating for about 2 hours, 968 g of water was dehydrated from this mixed system to obtain a uniform solution of cellulose (Samples 1 to 1). 5) was prepared. During the melting operation, the jacket temperature was kept at 100 ° C., and the pressure of the mixture system was kept at 50 Torr (66.7 hPa).

Next, each of the obtained solutions was spread on a pallet, sealed so as not to absorb moisture, and allowed to stand overnight at room temperature for solidification. The solidified product was crushed into pellets by a crusher. This pellet was supplied to a uniaxial screw extruder having a diameter of 20 mm, heated and redissolved, and then quantitatively conveyed to a spinning nozzle by a gear pump.

Each solution was discharged through a spinning nozzle having a temperature of 100 ° C. to 135 ° C. and having 10 spinning holes with a diameter D of 500 μm and L / D = 20, and passed through an air gap of 60 cm. It was wound directly by a winder. At this time, the fibers were solidified by spraying water on the winder. Maximum winding speed and spinning draft ratio (winding speed /
The ratio of the discharge linear velocities) is shown in Table 1.

[0036]

[Table 1]

Cellulose (component [II]) was added to sample 1 (comparative example), which was a single substance of cellulose (component [I]).
It can be seen that the maximum winding speed of Samples 2 to 5 in which No. 1 was mixed is increased and the spinning draft ratio is increased.

Example 2 In the same manner as in Example 1, two types of cellulose (components [I] and [II]) having different degrees of polymerization were mixed to obtain a spinning dope (samples 6 to 10).
Was evaluated for spinnability. The results are shown in Table 2. KC Flock W-as low polymerization degree cellulose (component [II])
50, W-100, W-200, W-400 (manufactured by Sanyo Kokusaku Pulp) and V-60 (manufactured by P & G Cellulose Co.) were used. Cellulose having a degree of polymerization of 1000 (component [I]) (N
10% by weight of low polymerization degree cellulose (component [II]) was mixed with 90% by weight of DPT.

[0039]

[Table 2]

The maximum winding speed was increased and the spinnability of the spinning dope was improved by mixing cellulose (component [II]) having a low degree of polymerization in all the samples.

(Example 3) In the same manner as in Example 1, two types of celluloses (component [I] and component [II]) having different polymerization degrees were mixed at the compounding ratio shown in Table 3. The spinnability of the obtained spinning dope (Samples 11 to 14) was evaluated. The results are shown in Table 3. Acetania pulp having a polymerization degree of 1950 was used as the cellulose (component [I]), and KC Flock W-300 having a polymerization degree of 400 was used as the cellulose having a low polymerization degree (component [II]).

[0042]

[Table 3]

Example 4 In the same manner as in Example 1, two kinds of celluloses (component [I] and component [II]) having different polymerization degrees were mixed. The obtained spinning dope (Samples 15 to 2)
The spinnability of 0) was evaluated. The results are shown in Table 4. As cellulose (component [I]), V-81, V-60, V
-5S (manufactured by P & G Cellulose Co.) was used to
KC Flock W-30 with a degree of polymerization of 400 relative to 0% by weight
Cellulose mixed with 10% by weight of 0 was used.

[0044]

[Table 4]

(Example 5) By the same method as in Example 1, the spinning dope (compounds 21 to 2) having the component mixture ratio shown in Table 5 was prepared.
5) was prepared, and each stock solution had a diameter D of 200 μm and L / D = 1.
5, spinning was performed using a metal nozzle having 36 spinning holes. Table 5 shows the maximum winding speed and the spinning draft ratio when the discharge linear velocity was 7.96 m / min.

[0046]

[Table 5]

(Example 6) In the same manner as in Example 1, the spinning dope (Samples 26 to 3) was prepared at the component mixing ratios shown in Table 6.
0) was prepared, solidified, pelletized, and redissolved by heating.
Further, the discharge linear velocity of the solution was set to 0.76 m / min. Other conditions were the same as in Example 1 for spinning.
Pure water was used for this coagulation bath, and the bath temperature was set to 25 ° C.
The fiber that passed through the coagulation bath was guided to the outside of the bath by a calendar roll, and further wound on a bobbin using a winder. The rotational linear velocity of the calendar roll was set to 90 m / min, and the spinning draft ratio was 118. The cellulose fiber wound on the bobbin was washed in a hot water bath at 70 ° C. and then dried. Table 6 shows the fiber physical properties of the thus produced cellulose fibers.

[0048]

[Table 6]

The mechanical properties of the yarns (Samples 27 to 30) obtained from the spinning dope prepared by blending two types of cellulose are as follows.
The physical properties were the same as those of the yarn (Sample 26) obtained from the spinning solution of the high-polymerization degree cellulose alone.

(Example 7) Using the same spinning dope (Samples 31 to 35) prepared by mixing two kinds of celluloses (component [I] and component [II]) having different degrees of polymerization in the same manner as in Example 6. I spun it. A system was used in which 90% by weight of NDPT (component [I]) having a degree of polymerization of 1000 was mixed with 10% by weight of cellulose having a low degree of polymerization (component [II]). As cellulose (component [II]), KC Flock W-5
0, W-100, W-200, W-400 (manufactured by Sanyo Kokusaku Pulp) and V-60 (manufactured by P & G Cellulose Co.) were used. Table 7 shows the physical properties of the obtained yarn.

[0051]

[Table 7]

The mechanical properties of the yarns (Samples 31 to 35) obtained from the spinning dope prepared by blending two types of cellulose are as follows.
The physical properties were the same as those of the yarn (Sample 26) obtained from the spinning solution of the high-polymerization degree cellulose alone.

Example 8 As component [I], 1000
Softwood Dissolving Pulp N from Sanyo Kokusaku Pulp having a degree of polymerization of
249.3 g of DPT (cellulose) and cellulose diacetate MBH2 manufactured by Daicel Chemical as component [II]
A mixture containing 7.7 g (weight mixing ratio 90/10) was prepared, and this was made together with 3000 g of N-methylmorpholine-N-oxide containing about 40% by weight of water and 15 g of propyl gallate, manufactured by Kodaira Seisakusho. The mixture was put into a mixer ACM-5 type equipped with a vacuum defoaming device, and 968 g of water was dehydrated from this mixed system while being mixed under reduced pressure heating for about 2 hours to obtain a uniform solution containing cellulose and cellulose diacetate (Sample 36). Was prepared. The jacket temperature was kept at 100 ° C. during the melting operation. In the same manner as in Example 1, the spinning properties of the spinning dope mixed with diacetate were evaluated, and the results are shown in Table 8.

[0054]

[Table 8]

(Example 9) In the same manner as in Example 8, except that the compounding ratio of cellulose and diacetate was changed to prepare a solution, the spinnability thereof was evaluated. As the component [I], 67
P & G Cellulose Dissolving Pulp V with a degree of polymerization of 0
276.4 g of -60 (cellulose) and cellulose diacetate MBH6 manufactured by Daicel Chemical as component [II]
A mixture containing 9.1 g (weight mixing ratio 80/20) was prepared, and this was made together with 3000 g of N-methylmorpholine-N-oxide containing about 40% by weight of water and 15 g of propyl gallate, manufactured by Kodaira Seisakusho. The mixture was put into a mixer ACM-5 type equipped with a vacuum defoaming device, and 1041 g of water was dehydrated from this mixed system while mixing under reduced pressure heating for about 2 hours.
A homogeneous solution (Sample 37) containing cellulose and cellulose diacetate was prepared. The jacket temperature was kept at 100 ° C. during the melting operation. The spinnability of the spinning dope mixed with diacetate was evaluated in the same manner as in Example 1, and the results are shown in Table 9.

[0056]

[Table 9]

(Embodiment 10) In the same manner as in Embodiment 8,
However, the spinning properties were evaluated by adjusting the solution by changing the compounding ratio of cellulose and diacetate. 1 as component [I]
Softwood dissolving pulp NDPT (cellulose (component [I])) 172.8 manufactured by Sanyo Kokusaku Pulp having a degree of polymerization of 000
172.8 g of P & G Cellulose dissolving pulp V-60 (cellulose) having a degree of polymerization of 670 g or 670
And, as the component [II], a mixture of cellulose diacetate MBH 172.8 g manufactured by Daicel Chemical Co., Ltd. or cellulose diacetate YBA 172.8 g manufactured by Daicel Chemical Co., Ltd. (weight mixing ratio 50/50) was adjusted to about 40% by weight. With 3000 g of N-methylmorpholine-N-oxide containing water and 15 g of propyl gallate,
The mixture was put into a mixer ACM-5 with a vacuum defoaming device manufactured by Kodaira Seisakusho, and 1038 g of water was dehydrated from this mixed system while mixing under reduced pressure heating for about 2 hours to obtain a uniform solution containing cellulose and cellulose diacetate ( Samples 38-40) were prepared. The jacket temperature was kept at 100 ° C. during the melting operation. The spinnability of the spinning dope mixed with diacetate was evaluated in the same manner as in Example 1, and the results are shown in Table 10.

[0058]

[Table 10]

(Example 11) A spinning dope having the composition shown in Table 11 (Samples 41 to 4) was prepared in the same manner as in Examples 9 and 10.
4) is adjusted so that each stock solution has a diameter D of 200 μm and L / D = 1.
5, spinning was performed using a metal nozzle having 36 spinning holes. Table 11 shows the maximum winding speed and the spinning draft ratio when the discharge linear velocity was 7.96 m / min.

[0060]

[Table 11]

Example 12 As the component [I], 100
249.3 g of softwood dissolving pulp NDPT (cellulose (component [I])) manufactured by Sanyo Kokusaku Pulp having a degree of polymerization of 0
And a mixture of 27.7 g of curdlan manufactured by Wako Pure Chemical Co., Ltd., which is β-1,3 glucose of a polysaccharide, as a component [II] (weight mixing ratio 90/10), and this was prepared in an amount of about 40% by weight. N-methylmorpholine-N-oxide 3 containing water
000 g and 15 g of propyl gallate were put into a mixer ACM-5 with vacuum defoaming equipment manufactured by Kodaira Seisakusho, and 968 g of water was dehydrated from this mixed system while mixing under reduced pressure heating for about 2 hours to obtain cellulose and curd. A homogeneous solution containing the orchid (Sample 45) was prepared. The jacket temperature was kept at 100 ° C. during the melting operation. The spinnability of the spinning dope prepared by mixing curdlan was evaluated in the same manner as in Example 1, and the results are shown in Table 12.

[0062]

[Table 12]

(Example 13) As component [I], 670
Dissolving pulp V- manufactured by P & G Cellulose Co. having a polymerization degree of
A mixture (weight mixing ratio 90/10) of 311.0 g of 60 (cellulose) and KC Flock W-300 (cellulose) 34.56 g manufactured by Sanyo Kokusaku Pulp having a degree of polymerization of 400 as component [II] was prepared. This was mixed with 3000 g of N-methylmorpholine-N-oxide containing about 40% by weight of water and 15 g of propyl gallate to produce a mixer ACM-5 with a vacuum defoaming device manufactured by Kodaira Seisakusho.
A uniform solution of cellulose (Samples 46 to 49) was prepared by pouring the mixture into a mold and mixing this mixture under reduced pressure heating for about 2 hours to dehydrate 1038 g of water from this mixed system. The jacket temperature was maintained at 100 ° C. during the melting operation.

The cellulose solution was spun at a spinning temperature of 130 ° C. and the spinning hole 36 had a diameter D of 300 μm and L / D = 15.
Each solution was discharged through a spinning nozzle made of ceramic (zirconium oxide) having individual pieces, passed through an air gap of 50 cm, and directly wound by a winder.
At this time, water was sprinkled on the winder to solidify the fibers (Sample 46). The maximum winding speed and the spinning draft ratio (ratio of winding speed / discharge linear speed) at a discharge linear speed of 1.18 m / min were measured. The results are shown in Table 13. For comparison, the same measurement results (Sample 47) using a metal spinning nozzle having the same shape are shown in Table 1.
3 shows. Furthermore, the cellulose component [I] and the component [I
Table 13 shows the results (Samples 48 and 49) of the same experiment performed by changing the compounding ratio with [I] to 70/30.

[0065]

[Table 13]

[0066]

The component [I] comprising the high molecular weight cellulose of the present invention, a low molecular weight cellulose, a cellulose derivative,
The specific mixed solvent solution of the cellulose composition with the component [II] consisting of a polysaccharide and / or a polysaccharide has a solution fluidity superior to that of a solution of high molecular weight cellulose alone. By using this cellulose molding solution, it is possible to produce with high productivity a cellulose molded article having mechanical properties similar to those of a molded article obtained from a solution of high molecular weight cellulose alone.

Front page continued (72) Inventor Kei Murase 20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayon Co., Ltd. Central Research Laboratory (72) Hideaki Habara 20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayon Shares Company Central Research Institute

Claims (10)

[Claims] 1. A mixed solvent comprising N-methylmorpholine-N-oxide and a solvent capable of uniformly mixing N-methylmorpholine-N-oxide and incapable of dissolving cellulose, and a mixture thereof. With a cellulose composition dissolved in a solvent, the cellulose composition,
(1) a component [I] made of cellulose having a degree of polymerization of 500 to 2000, and (2) a degree of polymerization of 350 to 900, which is 90% or less of the degree of polymerization of the component [I]. A blended weight of the component [I] and the component [II], which is a mixture of the cellulose, the cellulose derivative, and the component [II] including at least one selected from the group consisting of polysaccharides. Ratio is 95: 5 to 50:
A cellulose molding solution, which is in the range of 50. 2. The degree of polymerization of the component [I] is 1000 to 200.
The cellulose molding solution according to claim 1, which is 0. 3. The cellulose molding solution according to claim 1, wherein the cellulose derivative contained in the component [II] is cellulose diacetate. 4. The polysaccharide contained in the component [II] is β-1,
The cellulose molding solution according to claim 1 or 2, which is 3 glucose. 5. A cellulose molding method, characterized in that the cellulose molding solution according to claim 1 is formed into a flow having a desired shape and is brought into contact with a coagulating liquid to be solidified. 6. The cellulose molding solution is discharged into the air from a spinning nozzle having at least one spinning hole,
6. The filamentous cellulose molding solution flow thus discharged is brought into contact with a coagulating liquid while being drafted to be coagulated, and the coagulated fiber obtained is taken from the coagulating liquid to form a cellulose fiber. The described cellulose molding method. 7. The take-up speed is 500 m / min
The cellulose molding method according to claim 6, which is the above. 8. The spinning hole of the spinning nozzle has a diameter D of 200 μm or more, and the ratio L / D of the diameter D and the length L of the spinning hole is 10 or more. 7. The cellulose molding method according to 7. 9. The ratio L / D is 15 or more.
The described cellulose molding method. 10. The cellulose molding method according to claim 6, claim 7, claim 8, or claim 9, wherein the spinning nozzle is made of ceramics.