JP3870944B2 - Thermoplastic cellulose acetate propionate composition and fibers comprising the same - Google Patents

Description

  The present invention relates to thermoplastic cellulose acetate propionate compositions and fibers obtained by melt spinning them.

  Cellulose derivatives such as cellulose, cellulose ester, and cellulose ether are attracting great attention as biomass materials that are produced most in the world and as biodegradable materials in the environment. Representative examples of cellulose esters currently used commercially include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, etc., and are used in a wide range of fields such as plastics, filters and paints. Yes.

  Regarding the use of cellulose as a fiber, it has long been practiced to spin and use short fibers such as cotton and hemp produced in nature. In order to obtain a filament material instead of short fibers, cellulose is dissolved in a special solvent system such as carbon disulfide as in rayon, and is produced by wet spinning, or cellulose is derivatized as in cellulose acetate. Then, after dissolving in an organic solvent such as methylene chloride or acetone, there is only a method for producing yarn by a dry spinning method in which spinning is performed while evaporating the solvent.

  However, these wet spinning methods or dry spinning methods not only have a problem of low productivity due to slow spinning speed, but also organic solvents such as carbon disulfide, acetone, and methylene chloride used have an adverse effect on the environment. Therefore, when considering harmony with the environment, it cannot be said that it is a good method for yarn production.

  As a method using the melt spinning method, a fiber for hollow fiber is manufactured by blending cellulose acetate with a water-soluble plasticizer such as polyethylene glycol and performing melt spinning (see Patent Document 1). . However, when a large amount of polyethylene glycol having an average molecular weight of 200 to 1000 is used, melt spinning is difficult unless a low spinning draft is used from the viewpoint of the yarn breaking rate during spinning. Further, the use of a large amount of plasticizer has a problem that the plasticizer volatilizes violently during melt spinning.

  The cellulose ester resin has several problems in obtaining a molded product by melt processing by thermoplastic molding like a general-purpose synthetic resin. For example, the melting point of the cellulose acetate resin is around 280 ° C., which is higher than the decomposition point, and a plasticizer must be mixed in order to lower the melting point to a temperature suitable for melt processing.

  Therefore, as a plasticizer for cellulose esters used for extrusion and injection molding, phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate, and ethyl phthalyl ethyl glycolate are trimellitic acid esters. Some trimethyl trimellitates, triethyl trimellitates and the like are known. The fatty acid cellulose ester-based composition containing the plasticizer is easy to process due to a decrease in softening temperature, such as sheets, films, pulp, bars, stamps, decorations, eyeglass frames, tool patterns, food utensils patterns, toys. Widely used in miscellaneous goods.

  However, in the cellulose fatty acid ester composition using these plasticizers, for example, when continuous molding is performed for a long time such as melt spinning, there is a problem that the volatilization of the plasticizer is severe. Specific adverse effects caused by this include deterioration of the working environment and a decrease in texture when the fabric is made by volatilizing the plasticizer from the obtained yarn and adhering to the surface. In addition, compounds represented by phthalate esters may be environmental hormones, and the volatilization of the plasticizer causes serious problems.

  As described above, the combination of cellulose acetate and an existing plasticizer cannot sufficiently satisfy the melt-spinnable fluidity and the thermoplastic effect obtained.

  In addition, since cellulose esters are made from natural products such as linter and pulp, they contain many impurities that cause coloring during heating. In order to remove the color-causing substances, various treatments such as bleaching, high-temperature heating, and filtration are performed at the time of refining the linter, pulp, or manufacturing the cellulose ester. However, it is technically and economically limited to solve the coloring only by the purity and quality of the constituent raw materials. In order to solve this problem, it is known to add a phosphite to the cellulose ester as a heat stabilizer (see, for example, Patent Documents 2 to 5).

However, the combination of cellulose ester, existing plasticizer and phosphite ester does not provide a sufficient anti-coloring effect under molding conditions that provide melt spinning fluidity.
JP 51-70316 A (second page) JP-A-10-306175 (2nd page) JP-A-57-78431 (2nd page) JP 54-157159 A (2nd page) Japanese Patent Laid-Open No. 55-13765 (2nd page)

  The object of the present invention is to overcome the above-mentioned problems and to make a cellulose acetate propionate, which is a biomass material, and a thermoplastic cellulose acetate comprising a component having a low environmental load mainly composed of a biodegradable polyether compound. It is an object of the present invention to provide a propionate composition and thermoplastic cellulose acetate propionate fibers which are excellent in melt spinnability composed of them and excellent in not only high elongation properties but also fineness uniformity.

An object of the present invention described above is a heat characterized by comprising at least 80 to 95% by weight of cellulose acetate propionate and 5 to 20% by weight of a polyether compound represented by the following general formula (1). It can be solved by a plastic cellulose acetate propionate composition.
R1-O-[(CH2) nO] m-R2 (1)
(However, R1 and R2 represent the same or different groups selected from the group consisting of H, an alkyl group, and an acyl group. N is an integer of 2 to 5, m is an integer of 3 to 30)

  According to the present invention, a thermoplastic cellulose acetate propionate composition comprising a component having a low environmental impact, which is mainly composed of cellulose acetate propionate, which is a biomass-based material to which a plasticizer is added, is obtained. It becomes possible to provide excellent fibers. The composition and fiber obtained are suitable for fields utilizing biodegradability, that is, agricultural materials, forestry materials, marine products, civil engineering materials, sanitary materials, daily necessities, clothing fibers, industrial fibers, non-woven fabrics, etc. Can be used.

  The cellulose acetate propionate in the present invention refers to one in which at least a part of the hydroxyl group of cellulose is substituted with an acetyl group and a propionyl group. Specific examples of the acylating agent include acid chlorides, acid anhydrides, carboxylic acid compounds, and carboxylic acid compound derivatives, but are not particularly limited. The method for producing the cellulose ester used in the present invention may be carried out by a conventionally known method and is not particularly limited. Cellulose acetate substituted with only acetyl groups is insufficient in its own thermoplasticity, so a large amount of plasticizer needs to be added in order to have good thermal fluidity. By acylating cellulose with a propionyl group, the productivity is good because cellulose is more reactive than acylating with a long chain acyl group rather than a butyryl group at the time of producing a cellulose ester.

  The substitution degree of cellulose ester (DSac + DSpr) is preferably 1.6 to 3.0 per glucose unit. If the degree of substitution is 1.6 or more, thermoplastic molding is possible by adding a polyether compound.

In view of compatibility with the polyether compound and strength of the resulting fiber, the substitution degree of the acetyl group (DSac) and the substitution degree of the propionyl group (DSpr) preferably satisfy the following formulas.
(I) 1.6 ≦ DSac + DSpr ≦ 3.0
(II) 0.1 ≦ DSac ≦ 0.9
(III) 1.5 ≦ DSpr ≦ 2.9
The content of cellulose acetate propionate in the thermoplastic cellulose acetate propionate composition is 80 to 95% by weight. By setting the content to 95% by weight or less, the thermoplastic effect by adding the polyether compound is increased, and the melt moldability is improved. By setting the content to 80% by weight or more, the strength, which is a characteristic of cellulose ester, is increased, and a molded product having excellent mechanical properties can be obtained.

In the present invention, the polyether compound represented by the general formula (1) is used as a plasticizer.
R1-O-[(CH2) nO] m-R2 (1)
(However, R1 and R2 represent the same or different groups selected from the group consisting of H, an alkyl group, and an acyl group. N is an integer of 2 to 5, m is an integer of 3 to 30)
This is because the polyether compound represented by the general formula (1) is excellent in compatibility with cellulose acetate propionate, so that not only the thermoplastic effect is remarkably exhibited, but also the heat resistance of the polyether compound itself is good. This is because the color tone of the added polymer is also improved. Furthermore, the polyether compound represented by the general formula (1) has a characteristic of good biodegradability because it is not substituted with an aromatic group such as a phenyl group, an alkylphenyl group, and an arylphenyl group, which have low biodegradability. is doing.

  Specific polyether compounds include polyethylene glycol, polypropylene glycol, polyoxyethylene dimethyl ether, polyoxyethylene monostearate, polyoxyethylene monooleate, polyoxyethylene dilaurate, polyoxyethylene distearate, polyoxyethylene diolate However, it is not limited to this.

  Among these, polyethylene glycol and polyoxyethylene dilaurate are preferable.

  The polyether compound having a molecular weight of 200 to 1000 is preferable because volatilization of the polyether compound is suppressed and compatibility with cellulose acetate propionate is improved. 300-800 is more preferable.

  The compounding quantity of a polyether compound is 5 to 20 weight%. When the blending amount is 20% by weight or less, the mechanical properties are improved, and the volatilization of the polyether compound during heating can be suppressed. In addition, the strength is increased from the viewpoint of melt spinnability, and the spinning breakage rate is reduced. On the other hand, when the blending amount is 5% by weight or more, the molding temperature can be lowered from the viewpoint of thermal fluidity, and the color tone of the polymer obtained by suppressing the thermal decomposition of the composition is improved.

  A phosphite coloration inhibitor can be added to the composition of the present invention. When a phosphite coloration inhibitor is added to the composition of the present invention containing at least cellulose acetate propionate and a polyether compound, the coloration prevention effect is very remarkable even when the molding temperature is high. The color tone of the polymer is improved. The specific phosphite coloration inhibitor is not particularly limited, but the phosphite coloration inhibitor represented by the following general formulas (2), (3), and (4) includes at least cellulose acetate propionate and a polyether compound. High anti-coloring effect on the composition is preferable.

(Where R1, R2, R3, R4, R5, R6, R′1, R′2, R′3... R′n, R′n + 1 are hydrogen or alkyl having 4 to 23 carbon atoms, aryl, A group selected from the group consisting of alkoxyalkyl, aryloxyalkyl, alkoxyaryl, arylalkyl, alkylaryl, polyaryloxyalkyl, polyalkoxyalkyl and polyalkoxyaryl groups, provided that they are represented by the general formulas (2) (3) In the same formula (4), not all are hydrogen.X in the phosphite colorant represented by the general formula (3) is an aliphatic having an aliphatic chain and an aromatic nucleus in the side chain. A group selected from the group consisting of a chain, an aliphatic chain having an aromatic nucleus in the chain, and a chain including two or more non-continuous oxygen atoms in the chain, and k and q are integers of 1 or more, p represents an integer of 3 or more.
The numbers of k and q in these phosphite colorants are preferably 1 to 10. When the number of k and q is 1 or more, volatility during heating is reduced, and when it is 10 or less, compatibility with cellulose acetate propionate is improved, which is preferable. The value of p is preferably 3-10. By making it 3 or more, the volatility at the time of a heating becomes small, and since compatibility with a cellulose acetate propionate improves by making it 10 or less, it is preferable.

  As a specific example of the phosphite coloration inhibitor represented by the following general formula (2), those represented by the following formulas (5) to (8) are preferable.

  Moreover, what is represented by following formula (9) (10) (11) as a specific example of the phosphite type | system | group coloring inhibitor represented by following General formula (3) is preferable.

  The blending amount of the phosphite coloration inhibitor is preferably 0.005 to 0.5% by weight. A blending amount of 0.005% by weight or more is preferable because coloring of the composition during heating can be suppressed. More preferably, it is 0.01 weight% or more, More preferably, it is 0.05 weight% or more. On the other hand, when the blending amount is 0.5% by weight or less, deterioration due to cutting the molecular chain of cellulose acetate propionate and lowering the polymerization degree is preferably suppressed. More preferably, it is 0.2 weight% or less, More preferably, it is 0.1 weight% or less.

  The thermoplastic cellulose acetate propionate composition of the present invention has a heating loss rate at 220 ° C. of 5% by weight or less. Here, the weight loss rate by heating means the weight loss rate at 220 ° C. when the temperature of the sample is increased from room temperature at a rate of temperature increase of 10 ° C./min under nitrogen. A heating loss ratio of 5% by weight or less means that no smoke is generated during the molding process due to a large amount of low molecular plasticizer. For example, smoke does not occur during melt spinning, and fibers having good physical properties with good spinning properties can be obtained. The heating loss rate at 220 ° C. is preferably 3% by weight or less. Thus, the thermoplastic cellulose acetate propionate composition of the present invention having a low weight loss rate is suitable for melt spinning.

The thermoplastic cellulose acetate propionate composition of the present invention has a melt viscosity of 20 to 200 Pa · sec at 220 ° C. and 1000 sec ⁻¹ . By setting the melt viscosity at 220 ° C. and 1000 sec ⁻¹ to 20 Pa · sec or more, when subjected to melt spinning, the solidification after spinning proceeds sufficiently, and even if converged, the fibers do not stick together. Further, in this case, a sufficient pressure on the back surface of the die can be obtained, so that the distribution property is good and the uniformity of the fineness is ensured. On the other hand, when the melt viscosity is set to 200 Pa · sec or less, the spinning yarn has good spinning properties, sufficient orientation is obtained, and the fiber has excellent mechanical properties. In addition, troubles due to an abnormal increase in piping pressure do not occur. From the viewpoint of good fluidity, the melt viscosity at 220 ° C. and 1000 sec ⁻¹ is preferably 50 to 190 Pa · sec, and most preferably 80 to 180 Pa · sec.

  It is preferable that b value which shows the yellowness of the thermoplastic cellulose acetate propionate composition of this invention is -2-8. When the b value of the composition is −2 or more, the bluish color after molding is not strong, and when the b value of the composition is 8 or less, the yellowness of the molded product is not strong and the molded product has a dye. And colorability when colored with a pigment is favorable. The b value is more preferably 0 or more and 5 or less. In the present invention, one or two kinds of epoxy compounds, weak organic acids, phosphates, thiophosphates, and the like are used as stabilizers for preventing thermal deterioration and preventing coloration, as long as required performance is not impaired. You may mix and add above. In addition, other additives such as organic acid biodegradation accelerators, lubricants, antistatic agents, dyes, pigments, lubricants, matting agents and the like can be used.

  In mixing the cellulose acetate propionate and the plasticizer used in the present invention, a casting method using a known co-solvent may be used, or a commonly used known method such as an extruder, kneader, roll mill, or Banbury mixer. A mixer may be used without any particular limitation. In the case of mixing, the cellulose acetate propionate particles may be finely pulverized in advance to 50 mesh or more by a pulverizer in order to facilitate mixing. Moreover, a plasticizer may be added at the time of cellulose acetate propionate synthesis to obtain cellulose acetate propionate containing a plasticizer simultaneously with the production of cellulose acetate propionate.

  When mixing the phosphite colorant used in the present invention, the phosphite colorant may be mixed with the plasticizer and added before mixing the cellulose acetate propionate and the plasticizer. In addition, the phosphite-based anti-coloring agent may be directly mixed with cellulose acetate propionate and added. Further, a cast method using a known cosolvent may be used for a cellulose acetate propionate composition containing a premixed plasticizer and a phosphite-based anti-coloring agent, an extruder, a kneader, a roll mill, a Banbury mixer, etc. The commonly used known mixer may be used without particular limitation.

  The composition of the present invention has good heat fluidity and can be made into a fiber by a melt spinning method.

  The strength of the fiber comprising the thermoplastic cellulose acetate propionate composition of the present invention is preferably 0.5 to 2 cN / dtex. By setting the strength to 0.5 cN / dtex or more, it is preferable because it is easy to pass through higher processing steps such as weaving and knitting, and the strength of the final product is not insufficient. Further, it is preferable that it is 2 cN / dtex or less because elongation does not decrease, fuzz is suppressed, and yarn breakage is small. From the viewpoint of good strength characteristics, the strength is preferably 0.7 cN / dtex or more, and most preferably 1.0 cN / dtex or more.

  The elongation of the fiber comprising the thermoplastic cellulose acetate propionate composition of the present invention is preferably 2 to 50%. By setting the elongation to 2% or more, yarn breakage does not occur frequently in higher processing steps such as weaving and knitting. Further, if it is 50% or less, it is preferable that the stress is low, so that it does not deform, and a dyeing defect of the final product does not occur due to wetting marks at the time of weaving. The good elongation is more preferably 5 to 45%, and most preferably 10 to 40%.

  Moreover, it is preferable that U% of the fiber which consists of the thermoplastic cellulose acetate propionate composition of this invention is 3% or less. When U% is 3% or less, a fiber having excellent uniformity in fineness can be obtained. Good U% is preferably 2% or less, and most preferably 1% or less.

  Moreover, it is preferable that the color tone (b value) which shows the yellowness of the fiber which consists of a thermoplastic cellulose acetate propionate composition of this invention is -1-7. When it is −1 or more, the bluishness of the fiber is not strong, and when it is 7 or less, the yellowishness is not strong, and the color developability at the time of dyeing becomes good. The b value is more preferably 0 or more and 4 or less.

  In the melt spinning method used in the present invention, the above-described composition can be heated and melted in a known melt spinning machine, then extruded from a die, spun, and stretched and wound up as necessary. At this time, the spinning temperature is preferably 190 ° C to 250 ° C, more preferably 200 ° C to 240 ° C. It is preferable to set the spinning temperature to 190 ° C. or higher because the melt viscosity is lowered and the melt spinnability is improved. Moreover, since it is suppressed to 250 degrees C or less, thermal decomposition of a composition is suppressed, it is preferable.

  Further, in order to minimize the mixing of bubbles, the mixture is preferably pelletized using an extruder before being supplied to the melt spinning machine, or the extruder is preferably connected to the melt spinning machine by piping. In addition, the pelletized thermoplastic cellulose acetate propionate composition for melt molding should be dried to a water content of 0.1% by weight or less prior to melt spinning in order to prevent hydrolysis and generation of bubbles during melting. Is preferred.

  The fiber comprising the cellulose acetate propionate composition of the present invention has excellent mechanical properties and fineness uniformity, is excellent in biodegradability, and has excellent thermal fluidity when producing the fiber. The yarn cutting rate at the time of spinning is extremely low and the productivity is excellent. The obtained long fiber may be used as a fiber structure such as a woven fabric or a knitted fabric, or a nonwoven fabric by a melt blow method or a spun bond method.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

  In addition, the substitution degree of cellulose acetate propionate, melt viscosity, heating loss rate, strong elongation, and U% were evaluated by the following methods.

(1) Degree of substitution of cellulose acetate propionate 0.9 g of dried cellulose acetate propionate was weighed, 35 ml of acetone and 15 ml of dimethyl sulfoxide were added and dissolved, and then 50 ml of acetone was further added. While stirring, 30 ml of 0.5N sodium hydroxide aqueous solution was added and saponified for 2 hours. After adding 50 ml of hot water and washing the side of the flask, it was titrated with 0.5N sulfuric acid using phenolphthalein as an indicator. Separately, a blank test was performed in the same manner as the sample. The supernatant of the solution after titration was diluted 100 times, and the composition of the organic acid was measured using an ion chromatograph. From the measurement result and the acid composition analysis result by ion chromatography, the substitution degree was calculated by the following formula.

TA = (B−A) × F / (1000 × W)
DSac = (162.14 × TA) /
[[1- (Mwac− (16.00 + 1.01)) × TA] + [1- (Mwpr− (16.00 + 1.01)) × TA] × (Pr / Ac)]]
DSpr = DSac × (Pr / Ac)
TA: Total organic acid amount (ml)
A: Sample titration (ml)
B: Blank test titration (ml)
F: titer of sulfuric acid W: sample weight (g)
DSac: Degree of substitution of acetyl group DSpr: Degree of substitution of propionyl group Mwac: Molecular weight of acetic acid Mwpr: Molecular weight of propionic acid Pr / Ac: Molar ratio of acetic acid (Ac) to propionic acid (Pr) 162.14: Repeated cellulose Unit molecular weight 16.00: atomic weight of oxygen 1.01: atomic weight of hydrogen.

(2) Melt Viscosity Using a capillary rheometer manufactured by Toyo Seiki Co., Ltd. (Trademark: Capillograph 1B, L = 10 mm, D = 1.0 mm using a die), the viscosity is measured at a measurement temperature of 220 ° C. and a shear rate of 1000 sec ^−1. The melt viscosity was used.

(3) Heat loss rate When using TG-DTA2000S manufactured by Mac Science Co., Ltd. and heating the sample from room temperature to 400 ° C. at a rate of temperature increase of 10 ° C./min under nitrogen, the weight of the sample 10 mg at 220 ° C. The change was the heating loss rate.

(4) Color tone (composition)
10 g of the pellets of the composition cut to 5 mm square were put in a special container, L, a, and b values were measured with an SM color computer manufactured by Suga Test Instruments Co., Ltd., and the b value representing yellowishness was used as the color tone.

(5) High elongation Using Tensilon UCT-100 manufactured by Orientec Co., Ltd., a tensile test was conducted under the conditions of a sample length of 20 cm and a tensile speed of 20 mm / min, and the stress at the point showing the maximum load was determined as the fiber strength (cN / Dtex). Further, the elongation at break was defined as the elongation (%) of the fiber.

(6) U%
Measurement was performed for 1 minute at a yarn feeding speed of 25 m / min using a Worcester tester 4-CX manufactured by Zerbegger Worcester, and the obtained value was defined as U%.

(7) Texture A 27-gauge circular knitting was prepared using the obtained fiber, and the texture was evaluated by a sensory test. A thing with sufficient dry feeling was marked with ◯, a thing without dry feeling was marked with △, and a thing with remarkable sliminess was marked with x. In addition, (circle) is preferable and (triangle | delta) is an acceptable range, but x has a problem.

(8) Spinning property Under conditions where melt spinning is performed, the polyether compound was not volatilized and the spun yarn had good thinning deformability was evaluated as ◯. On the other hand, those that were difficult to produce due to volatilization of the polyether compound or poor spun yarn deformability were evaluated as x. In addition, although the yarn can be produced but the volatilization of the polyether compound is recognized, the symbol Δ is given.

(9) Color tone (fiber)
The obtained fiber was wound around a plate, L, a, and b values were measured with an SM color computer manufactured by Suga Test Instruments Co., Ltd., and the b value representing yellowishness was used as the color tone. The amount of fiber wound on the plate is measured using, for example, a fiber having a fineness of 110 dtex and 180 m of fibers wound on a plate having a width of 6 cm to a length of 4 cm, and the average thickness of the yarn on the plate is about 2 mm. went. Further, the incident angle of light of the color computer was 45 degrees.

Synthesis example 1
Acetic acid (20 g) and propionic acid (90 g) were added to cellulose (Nippon Paper Industries Co., Ltd. dissolving pulp) and mixed at 55 ° C. for 30 minutes. After the mixture was cooled to room temperature, acylation was carried out by adding 10 g of acetic anhydride, 140 g of propionic anhydride and 1.2 g of sulfuric acid cooled in an ice bath. In acylation, when it exceeded 40 degreeC, it cooled with the water bath. After stirring for 150 minutes, a mixed solution of 30 g of acetic acid and 10 g of water was added over 20 minutes as a reaction terminator to hydrolyze excess anhydride. Thereafter, 100 g of acetic acid and 30 g of water were added and stirred at 60 ° C. for 1 hour. After completion of the reaction, an aqueous solution containing 2 g of sodium carbonate was added and the precipitated cellulose acetate propionate was filtered off, washed with water, and dried at 60 ° C. for 4 hours. The substitution degree of the obtained cellulose acetate propionate was acetyl group 0.2 and propionyl group 2.4.

Example 1
92% by weight of cellulose acetate propionate obtained in Synthesis Example 1 and 8% by weight of polyethylene glycol (molecular weight 600) as a plasticizer were mixed at 220 ° C. in a kneader to obtain a mixed polymer. This was cut to about 5 mm square to obtain pellets of a thermoplastic cellulose ester composition. The pellets were dried in a hot air dryer heated to 80 ° C. for 10 hours, and then the melt viscosity at 220 ° C. and 1000 sec ⁻¹ was measured. The melt viscosity was 163.5 Pa · sec. Further, the heating loss rate was 0.9%, and the color tone (b value) was 4.2.

  The obtained pellets were melted at a melting temperature of 220 ° C. and a pack temperature of 220 ° C. with a single-screw extruder melt spinning machine, and spun from a die having 36 holes of 0.20 mmφ−0.30 mmL. The spun yarn had good thinning deformability, and no dirt adhered to the die. Further, no smoke was observed from the spun yarn. The spun yarn was cooled by a chimney wind at 25 ° C., taken up by a godet roller at a speed of 600 m / min, and wound with a winder. No spun yarn breakage was observed. The spinnability of the composition was very good.

  The obtained fiber had a strength of 1.3 cN / dtex and an elongation of 23%, and was excellent in mechanical properties. Moreover, U% was 1.1%, and the uniformity of the fineness in the fiber longitudinal direction was excellent. The color tone (b value) was 4.9, and a slight yellowish color was observed, but it was a level with no problem.

  A knitted fabric was prepared using the obtained fibers and the texture was evaluated. As a result, no slime was found, and the desired texture was soft and dry.

Example 2
Pellets were prepared in the same manner as in Example 1 except that 90% by weight of cellulose acetate propionate (Synthesis Example 1) and 10% by weight of polyoxyethylene dilaurate (molecular weight 600) were used as a plasticizer. Melt viscosity, loss on heating The rate and color tone were measured. The melt viscosity was 125.3 Pa · sec, the heat loss rate was 1.0%, and the color tone (b value) was 4.0.

  The obtained pellets were spun in the same manner as in Example 1. As a result, the spun yarn had good thinning deformability, and no dirt adhered to the die. Further, no fuming from the spun yarn was observed, and no spun yarn breakage was observed. The spinnability of the composition was very good.

  The obtained fiber had a strength of 1.2 cN / dtex and an elongation of 26%, and was excellent in mechanical properties. Moreover, U% was 1.2%, and the uniformity of fineness was excellent. The color tone (b value) was 4.2, and a slight yellowish color was observed, but it was a level with no problem.

  A knitted fabric was prepared using the obtained fibers and the texture was evaluated. As a result, no slime was found, and the desired texture was soft and dry.

Example 3
Pellets were prepared in the same manner as in Example 1 except that 85% by weight of cellulose acetate propionate (Synthesis Example 1) and 15% by weight of polyoxyethylene monooleate (molecular weight 800) were used as a plasticizer. Melt viscosity, heating The weight loss rate and color tone were measured. The melt viscosity was 98.5 Pa · sec, the heat loss rate was 2.1%, and the b value was 3.5.

  The obtained pellets were spun in the same manner as in Example 1. As a result, the spun yarn had good thinning deformability, and no dirt adhered to the die. Smoke from the spun yarn was slightly recognized, but spun yarn breakage was not observed. The spinning property of this composition was good.

  The obtained fiber had a strength of 1.0 cN / dtex and an elongation of 28%, and was excellent in mechanical properties. Moreover, U% was 1.0%, and the uniformity of fineness was excellent. The color tone (b value) was 4.1, and a slight yellowish color was observed, but it was a level with no problem.

  When the knitted fabric was created using the obtained fiber and the texture was evaluated, it had a soft texture although a slight slime was observed.

Synthesis example 2
Cellulose acetate propionate was obtained by reacting in the same manner as in Synthesis Example 1 except that 5 g of acetic anhydride and 120 g of propionic anhydride were used. The substitution degree of the obtained cellulose acetate propionate was acetyl group 0.1 and propionyl group 2.4. Cellulose acetate propionate was obtained by the above method.

Example 4
Pellets were prepared in the same manner as in Example 1 except that 92% by weight of cellulose acetate propionate (Synthesis Example 2) and 8% by weight of polyoxyethylenediolate (molecular weight 600) were used as a plasticizer, melt viscosity, heating The weight loss rate and color tone were measured. The melt viscosity was 110.7 Pa · sec, the heat loss rate was 1.8%, and the color tone (b value) was 4.5.

  The obtained pellets were spun in the same manner as in Example 1. As a result, the spun yarn had good thinning deformability, and no dirt adhered to the die. Smoke from the spun yarn was slightly recognized, but spun yarn breakage was not observed. The spinning property of this composition was good.

  The obtained fiber had a strength of 1.1 cN / dtex and an elongation of 22%, and was excellent in mechanical properties. Moreover, U% was 1.3%, and the uniformity of fineness was excellent. The color tone (b value) was 5.1 and a slight yellowish color was observed, but it was a level with no problem.

  A knitted fabric was prepared using the obtained fibers, and the texture was evaluated. As a result, no slime was found, and the desired texture was soft and dry.

Example 5
Cellulose acetate propionate (Synthesis Example 1) 92% by weight, polyethylene glycol (molecular weight 600) as a plasticizer 7.9% by weight, and phosphite-based anti-coloring agent bis (2.6-di-t-butyl-4- Pellets were prepared in the same manner as in Example 1 except that 0.1% by weight of methylphenyl) pentaerythritol diphosphite (the following formula (6)) was used, and the melt viscosity, heating loss rate, and color tone were measured. The melt viscosity was 168.2 Pa · sec, the heat loss rate was 0.9%, and the color tone (b value) was 4.0.

  When the obtained pellets were spun in the same manner as in Example 1, no fuming from the spun yarn was observed, and no spun yarn breakage was observed. The spinnability of the composition was very good.

  The obtained fiber had a strength of 1.4 cN / dtex and an elongation of 23%, and was excellent in mechanical properties. Moreover, U% was 1.1%, and the uniformity of fineness was excellent. The color tone (b value) was 2.2, which was very good.

  A knitted fabric was prepared using the obtained fibers and the texture was evaluated. As a result, no slime was found and the texture was soft and dry.

Example 6
Cellulose acetate propionate (Synthesis example 1) 90% by weight, polyoxyethylene dilaurate (molecular weight 600) 9.92% by weight as a plasticizer, bis (2,4-di-t-butylphenyl) as a phosphite-based anti-coloring agent ) Pellets were prepared in the same manner as in Example 1 except that 0.08% by weight of pentaerythritol diphosphite (the following formula (7)) was used, and the melt viscosity, the heat loss rate and the color tone were measured. The melt viscosity was 130.1 Pa · sec, the heat loss rate was 1.1%, and the color tone (b value) was 3.5.

  When the obtained pellets were spun in the same manner as in Example 1, no fuming from the spun yarn was observed, and no spun yarn breakage was observed. The spinnability of the composition was very good.

  The obtained fiber had a strength of 1.3 cN / dtex and an elongation of 27%, and was excellent in mechanical properties. Moreover, U% was 1.2%, and the uniformity of fineness was excellent. The color tone (b value) was 2.1, which was very good.

  A knitted fabric was prepared using the obtained fibers and the texture was evaluated. As a result, no slime was found and the texture was soft and dry.

Example 7
Cellulose acetate propionate (Synthesis example 1) 92% by weight, 7.4% by weight of polyethylene glycol (molecular weight 600) as a plasticizer, and bis (2,4-di-t-butylphenyl) penta as a phosphite-based anti-coloring agent Pellets were prepared in the same manner as in Example 1 except that 0.6% by weight of erythritol diphosphite (the following formula (6)) was used, and the melt viscosity, the heat loss rate and the color tone were measured. The melt viscosity was 158.3 Pa · sec, the heat loss rate was 1.2%, and the color tone (b value) was 4.2.

  When the obtained pellets were spun in the same manner as in Example 1, no fuming from the spun yarn was observed, and no spun yarn breakage was observed. The spinnability of the composition was very good.

  The obtained fiber had a strength of 0.6 cN / dtex and an elongation of 18%. Although the mechanical properties were slightly inferior, there was no problem. U% was 2.9%. The color tone (b value) was 2.3, which was very good.

  A knitted fabric was prepared using the obtained fibers and the texture was evaluated. As a result, no slime was found and the texture was soft and dry.

Synthesis example 3
50 g of cellulose (dissolved pulp manufactured by Nippon Paper Industries Co., Ltd.) is immersed in 500 ml of deionized water and left for 10 minutes. This is filtered through a glass filter, drained, dispersed in 700 ml of acetic acid, shaken occasionally and left for 10 minutes. Subsequently, the same operation is repeated again with fresh acetic acid.

  To the flask, 900 g of acetic acid and 0.9 g of concentrated sulfuric acid were taken and stirred. To this was added 180 g of acetic anhydride, and the mixture was stirred for 60 minutes while cooling with a water bath so that the temperature did not exceed 40 ° C. After completion of the reaction, an aqueous solution containing 2 g of sodium carbonate was added and the precipitated cellulose ester was filtered off, washed with water, and dried at 60 ° C. for 4 hours. The obtained cellulose acetate was 85.3 g, and the substitution degree of cellulose acetate was 2.9.

Comparative Example 1
Except using the cellulose acetate synthesize | combined in the synthesis example 3, it carried out similarly to Example 1, the pellet was created, and melt viscosity, the heat loss rate, and the color tone were measured. The heating loss rate was as low as 1.3%, but the melt viscosity was a remarkably high value of 251.2 Pa · sec. Further, the color tone (b value) was 8.2, which was very yellowish.

  When spinning was attempted using the obtained pellets in the same manner as in Example 1, no smoke was generated from the spun yarn, and the base was not soiled. However, the melt viscosity was too high, the fluidity was poor and the spun yarn was not thinned and could not be taken up. This composition had a very poor yarn forming property.

Comparative Example 2
Pellets were prepared in the same manner as in Comparative Example 1 except that polyoxyethylenediolate (molecular weight 600) was used as the plasticizer, and the melt viscosity, the heat loss rate and the color tone were measured. Although the heat loss rate was as low as 1.4%, the melt viscosity was a remarkably high value of 243.9 Pa · sec. Further, the color tone (b value) was 8.5, which was very yellowish.

  When spinning was attempted using the obtained pellets in the same manner as in Example 1, no smoke was generated from the spun yarn, and the base was not soiled. However, the melt viscosity was too high, the fluidity was poor and the spun yarn was not thinned and could not be taken up. This composition had a very poor yarn forming property.

Comparative Example 3
Pellets were prepared in the same manner as in Example 1 except that 98% by weight of cellulose acetate propionate (Synthesis Example 1) and 2% by weight of polyethylene glycol (molecular weight 600) were used as a plasticizer. And the color tone was measured. The heating loss rate was as low as 0.8%, but the melt viscosity was a remarkably high value of 261.2 Pa · sec. Further, the color tone (b value) was 8.1, which was very yellowish.

  When spinning was attempted using the obtained pellets in the same manner as in Example 1, no smoke was generated from the spun yarn, and the base was not soiled. However, the melt viscosity was too high, the fluidity was poor and the spun yarn was not thinned and could not be taken up. This composition had a very poor yarn forming property.

Comparative Example 4
Pellets were prepared in the same manner as in Example 1 except that 70% by weight of cellulose acetate propionate synthesized in Synthesis Example 1 and 30% by weight of polyethylene glycol (molecular weight 600) as a plasticizer were used. The weight loss rate and color tone were measured. The melt viscosity was 17.8 Pa · sec. The heating weight loss rate was a high value of 18.4%. The color tone (b value) was 4.1.

  Spinning was attempted in the same manner as in Example 1 using the obtained pellets, but the fluidity was very high. Further, since the yarn breakage occurred frequently at the spinning speed of 500 m / min and could not be taken up, spinning was performed at a spinning temperature as low as 300 m / min. From the spun yarn, intense smoke due to the volatilization of the plasticizer was observed, and the running yarn was not stable. This composition was poor in yarn production from the viewpoint of smoke generation and frequent yarn breakage.

  The obtained fiber had a low strength of 0.3 cN / dtex and an elongation of 27%. U% was 3.8%, which was inferior in uniformity of fineness. In addition, although the color tone (b value) was 4.9, which was slightly yellowish, it was a level with no problem.

  When the knitted fabric was created using the obtained fibers and the texture was evaluated, it was very strong and could not be used as a fabric.

Synthesis example 4
50 g of cellulose (dissolved pulp manufactured by Nippon Paper Industries Co., Ltd.) is immersed in 500 ml of deionized water and left for 10 minutes. This is filtered through a glass filter, drained, dispersed in 700 ml of acetic acid, shaken occasionally and left for 10 minutes. Subsequently, the same operation is repeated again with fresh acetic acid.

  To the flask, 900 g of acetic acid and 0.9 g of concentrated sulfuric acid were taken and stirred. To this was added 180 g of acetic anhydride, and the mixture was stirred for 60 minutes while cooling with a water bath so that the temperature did not exceed 40 ° C. After completion of the reaction, an aqueous acetic acid solution was slowly added, followed by stirring overnight at room temperature. Thereafter, an aqueous solution containing 2 g of sodium carbonate was added and the precipitated cellulose ester was filtered off, washed with water, and dried at 60 ° C. for 4 hours. The obtained cellulose acetate was 80.1 g, and the degree of substitution of cellulose acetate was 2.5.

Comparative Example 5
Pellets were prepared in the same manner as in Example 1 except that 70% by weight of cellulose acetate synthesized in Synthesis Example 4 and 30% by weight of caprolactone oligomer (molecular weight 550) as a plasticizer were used. The color tone was measured. The melt viscosity was as high as 203.0 Pa · sec, and the heat loss rate was as high as 19.0%. The color tone (b value) was as high as 8.2.

  When spinning was attempted using the obtained pellets in the same manner as in Example 1, no smoke was generated from the spun yarn, and the base was not soiled. However, the melt viscosity was high, the fluidity was poor, and the spun yarn was not thinned and could not be taken up. This composition had a very poor yarn forming property.

  The composition and fiber obtained are suitable for fields utilizing biodegradability, that is, agricultural materials, forestry materials, marine products, civil engineering materials, sanitary materials, daily necessities, clothing fibers, industrial fibers, non-woven fabrics, etc. Can be used.

Claims (6)

Thermoplastic cellulose acetate propionate composition comprising at least 80 to 95% by weight of cellulose acetate propionate and 5 to 20% by weight of a polyether compound represented by the following general formula (1) .
R1-O-[(CH2) nO] m-R2 (1)
(However, R1 and R2 represent the same or different groups selected from the group consisting of H, an alkyl group, and an acyl group. N is an integer of 2 to 5, m is an integer of 3 to 30)   The thermoplastic cellulose acetate propionate composition according to claim 1, wherein the polyether compound has a molecular weight of 200 to 1,000. The acetyl group substitution degree (DSac) and propionyl group substitution degree (DSpr) of cellulose acetate propionate satisfy the following formulas (I) to (III): A thermoplastic cellulose acetate propionate composition.
(I) 1.6 ≦ DSac + DSpr ≦ 3.0
(II) 0.1 ≦ DSac ≦ 0.9
(III) 1.5 ≦ DSpr ≦ 2.9 The thermoplastic cellulose acetate according to any one of claims 1 to 3, wherein the heat loss rate at 220 ° C is 5 wt% or less, and the melt viscosity at 220 ° C and 1000 sec ^-1 is 20 to 200 Pa · sec. Propionate composition.   The thermoplastic cellulose acetate propionate composition according to any one of claims 1 to 4, further comprising 0.005 to 0.5% by weight of a phosphite coloration inhibitor.   It consists of the thermoplastic cellulose acetate propionate composition as described in any one of Claims 1-5, intensity | strength 0.5-2cN / dtex, elongation 2-50%, U% being 3% or less. Characteristic cellulose acetate propionate fiber.