KR101788632B1 - The thermoplastic cellulose derivative and thereby made fiber - Google Patents

Abstract

The present invention relates to a thermoplastic cellulose derivative composition and a fiber produced therefrom, and is capable of melt spinning without using an organic solvent which is toxic to the environment and human body, thereby providing a cellulose fiber having improved strength and biodegradability have. In addition, it is possible to provide a cellulose fiber having improved dyeability by allowing high-speed spinning to increase productivity, capable of spinning three spindles, and preventing a water-soluble plasticizer from being eluted during the dyeing process.

Description

TECHNICAL FIELD The present invention relates to a thermoplastic cellulose derivative composition,

TECHNICAL FIELD The present invention relates to a thermoplastic cellulose derivative composition and a fiber produced thereby. More particularly, the present invention relates to an eco-friendly cellulose derivative composition and fiber capable of melt-spinning without dissolving in an organic solvent and being biodegradable.

Polymer synthetic resins have been extensively used for a variety of purposes because of their excellent mechanical properties, chemical resistance and durability. However, such synthetic resins have a disadvantage in that harmful substances are released when they are incinerated because they are not decomposed by themselves in nature.

Recently, environmental pollution problem has become a big social problem, and biodegradable resins that can be completely decomposed in nature have been actively studied and are attracting interest worldwide.

Although biodegradable resins such as polybutylene succinate, polyethylene succinate and polylactic acid are excellent in biodegradability, they are not economical due to their high cost, or have a low melting point, In the manufacture of products such as textile products, it is difficult to develop a product group that needs to maintain thermal stability.

Recently, products such as polylactic acid (PLA) or starch have been spotlighted in recent biomass-based products, which are supplied from nature. However, they can not be dyed at high temperature for fiberization and are susceptible to hydrolysis, It has various disadvantages such as hardening and brittle property when the tenter work is carried out, and it is difficult to carry out spinning at 4000mpm in the spinning apparatus which emits the conventional polyester.

Cellulosic materials are the most massively biodegradable resource recycling biomass materials on the planet. The use of cellulose as a fiber has been conventionally carried out by spinning short fibers such as cotton and hemp produced in the natural environment. In order to obtain a filament material other than short fibers, cellulose is dissolved in a specific solvent to effect wet spinning, cellulose is derivatized such as cellulose acetate, dissolved in an organic solvent such as methylene chloride or acetone, A dry spinning process has been carried out in which the spinning is carried out while evaporating.

However, these wet spinning or dry spinning fibers have a problem of low productivity due to a slow spinning speed, and also have problems in that organic solvents such as carbon disulfide, acetone, and methylene chloride used in the production of fibers have a bad influence on the environment and human body . Therefore, in order to obtain an environmentally friendly fiber comprising cellulose as a raw material, it is necessary to use a melt spinning method without using an organic solvent.

As a thermoplastic cellulose composition capable of melt spinning and fibers made of the same, a cellulose composition in which a large amount of a water-soluble plasticizer such as polyethylene glycol is added to cellulose acetate, and a fiber comprising the cellulose composition are known. However, since the content of the plasticizer in the composition is high, the spin rate during spinning is high, and melt spinning is difficult unless the spinning draft is low.

It is impossible to spin at a high speed of about 4,000 mpm even at a spinning speed, resulting in a decrease in productivity. In addition, since it is not stiff, flexible and easily damaged when a fabric is made into a fabric, There was a difficult problem.

Also, since a high content of a water-soluble plasticizer is contained in the composition, a water-soluble plasticizer produced from a textile product after being dyed in the dyeing process may be eluted and cause a problem of dyes. There is a problem that it can be discharged.

Japanese Patent Application Laid-Open No. 2003-0058950 (published July 2003)

Disclosure of the Invention The present invention has been conceived to solve the above-mentioned problems, and it is an object of the present invention to provide a process for producing a polymerizable composition capable of melt spinning without using an organic solvent toxic to the environment and human body, To provide a thermoplastic cellulose derivative composition and a fiber produced therewith.

 Also, it is an object of the present invention to provide a thermoplastic cellulose derivative composition capable of spinning three fibers, dissolving a water-soluble plasticizer in the dyeing process to prevent the occurrence of a dyestuff and improving dyeability, and a fiber produced by the method.

In order to solve the above-described problems,

A first resin comprising a cellulose ester, a water-soluble plasticizer and polylactic acid (PLA); And a second resin prepared by esterifying and polycondensing a mixture of an acid component comprising an aromatic polycarboxylic acid, an aliphatic polycarboxylic acid and a sulfonic acid metal salt, and a diol component having 2 to 14 carbon atoms, and a thermoplastic cellulose derivative composition .

According to a preferred embodiment of the present invention, the composition may have a mixing weight ratio of the first resin and the second resin of 2: 8 to 4: 6.

According to another preferred embodiment of the present invention, the first resin may comprise 70 to 90% by weight of a cellulose ester, 5 to 20% by weight of a water-soluble plasticizer and 5 to 20% by weight of polylactic acid (PLA).

According to another preferred embodiment of the present invention, the weight ratio of the water-soluble plasticizer and the polylactic acid (PLA) may be 4: 6 to 9: 1.

According to another preferred embodiment of the present invention, the mixing ratio of the first resin and the second resin is 2: 8 to 4: 6, the weight ratio of the water-soluble plasticizer and the polylactic acid (PLA) To 9: 1.

According to another preferred embodiment of the present invention, tetrakis methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane and tris (2, Di-t-butylphenyl) phosphate, and 0.1 to 0.5 parts by weight of at least one antioxidant selected from the group consisting of 4-di-t-butylphenyl) phosphate.

According to another preferred embodiment of the present invention, the cellulose ester is selected from the group consisting of cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate caproate, cellulose acetate caprylate, cellulose acetate laurethate, cellulose Acetate palmitate, cellulose acetate stearate, and cellulose acetate oleate.

According to another preferred embodiment of the present invention, the degree of substitution of the cellulose ester may be 2.2 to 2.6.

According to another preferred embodiment of the present invention, the water-soluble plasticizer may be at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polycaprolactone, polyglycolic acid and polybutyl adipate.

According to another preferred embodiment of the present invention, the acid component may comprise 70 to 89 mol% of an aromatic polycarboxylic acid, 10 to 30 mol% of an aliphatic polycarboxylic acid and 0.1 to 3.0 mol% of a sulfonic acid metal salt have.

According to another preferred embodiment of the present invention, the acid component and the diol component may be mixed and polymerized at a weight ratio of 1.0: 1.0 to 1.4.

The present invention also relates to a biodegradable polyester prepared by esterifying and polycondensing a mixture of an acid component containing an aromatic polycarboxylic acid, an aliphatic polycarboxylic acid and a sulfonic acid metal salt, and a diol component having 2 to 14 carbon atoms, Ester and polylactic acid (PLA). ≪ Desc / Clms Page number 2 >

According to a preferred embodiment of the present invention, the fibers may comprise 1 to 10% by weight of polylactic acid (PLA) and 50 to 80% by weight of biodegradable polyester.

According to another preferred embodiment of the present invention, the acid component comprises 70 to 89 mol% of an aromatic polycarboxylic acid, 10 to 30 mol% of an aliphatic polycarboxylic acid and 0.1 to 3.0 mol% of a sulfonic acid metal salt .

According to another preferred embodiment of the present invention, the acid component and the diol component may be mixed and polymerized at a weight ratio of 1.0: 1.0 to 1.4.

According to another preferred embodiment of the present invention, the thermoplastic cellulose derivative fiber may have a strength of 2.5 g / de or more and an elongation of 30% or more.

According to another preferred embodiment of the present invention, the thermoplastic cellulose derivative fiber may have a fineness of 100 De or less.

The thermoplastic cellulose derivative composition of the present invention is capable of melt spinning without using an environmentally and toxic organic solvent, thereby providing a cellulose fiber having improved strength and biodegradability.

In addition, it is possible to increase productivity by enabling high-speed spinning, and it is possible to spin three spindles, to dissolve a water-soluble plasticizer during the dyeing process to prevent occurrence of a dyed yarn, And the like can be practically used.

Hereinafter, the present invention will be described in more detail.

As described above, the conventional thermoplastic cellulose derivative composition and the fibers produced therefrom have a problem of not being able to spin at high speed, resulting in a low productivity, and a lack of strength and stiffness when fabricated. In addition, since a high content of water-soluble plasticizer is contained in the composition, a water-soluble plasticizer prepared from a textile product after being dyed in a dyeing process may be eluted and cause a problem of dyes, and a water-soluble plasticizer may be discharged There was a problem.

 Accordingly, in the present invention, a first resin comprising a cellulose ester, a water-soluble plasticizer and polylactic acid (PLA); And a second resin prepared by esterifying and polycondensing a mixture of an acid component comprising an aromatic polycarboxylic acid, an aliphatic polycarboxylic acid and a sulfonic acid metal salt, and a diol component having 2 to 14 carbon atoms, and a thermoplastic cellulose derivative composition To solve the above-mentioned problem. As a result, high-speed spinning is possible, which can increase productivity, improve the strength and biodegradability of cellulosic fibers, and prevent the water-soluble plasticizer from being eluted during the dyeing process to generate dyes.

 The cellulose ester of the present invention is a cellulose derivative in which a part or all of the hydroxyl groups of cellulose are substituted by an ester bond, weakening strong hydrogen bonds of the cellulose hydroxyl groups and allowing the plasticizer to mix well therebetween. By effectively mixing the plasticizer, strong hydrogen bonding due to cellulose hydroxyl groups can be prevented and melt spinning can be enabled.

The cellulose ester is preferably selected from the group consisting of cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate caprate, cellulose acetate caprylate, cellulose acetate laurethate, cellulose acetate palmitate, cellulose acetate stearate Or cellulose acetate oleate, and the like.

The cellulose ester of the present invention may have an average degree of polymerization of 30,000 to 50,000 and a degree of substitution of 2.2 to 2.6. The substitution degree of the cellulose ester means the degree of substitution of the hydroxyl group of the cellulose by the ester bond. When the degree of substitution of the cellulose ester is less than 2.2, the fluidity may be lowered and the strength may be lowered at the time of wetting. There may be a problem of degradation.

 The water-soluble plasticizer contained in the first resin of the present invention is not particularly limited as long as it can be mixed with a cellulose derivative to inhibit strong hydrogen bonding due to cellulose hydroxyl groups and to be capable of melt spinning, , And more preferably, a low molecular weight of 1000 or less can be used so that plasticization can be promoted.

 The water-soluble plasticizer may be in the form of polyethylene glycol, polypropylene glycol, poly (ethylene-propylene) glycol, polycaprolactone, polyglycolic acid or polybutyl adipate.

The first resin may include 70 to 90 wt% of a cellulose ester, 5 to 20 wt% of a water-soluble plasticizer, and 5 to 20 wt% of polylactic acid (PLA). By including polylactic acid (PLA) as a plasticizer in an amount of 5 to 20% by weight, the cellulose ester can be effectively plasticized even when the water-soluble plasticizer is not contained in an excessive amount, and an excessive amount of the water-soluble plasticizer is not used. And can be eluted during the dyeing process or using the fiber to reduce the side effects of slipping. Further, by optimally adjusting the content ratio of the water-soluble plasticizer and polylactic acid (PLA), the strength of the fiber can be remarkably improved, and the three denier yarns of 100 Da or less can be radiated and the dyeability can be improved. (PLA) having an average molecular weight of 1,000 to 20,000 may be included, and when an excessive amount of polylactic acid (PLA) is added, plasticization rate is poor and compounding workability is poor, There is a problem that the spinning workability due to yarn thread trimming is poor.

The weight ratio of the water soluble plasticizer and polylactic acid (PLA) may be 4: 6 to 9: 1. When the weight ratio of the water-soluble plasticizer and polylactic acid (PLA) is out of the range, the plasticization rate may be lowered and the compounding operation may be problematic.

 The first resin of the present invention may further comprise an antioxidant, which serves to prevent thermal degradation in the process of thermolabeling the cellulose ester and of radiating the plasticized cellulose ester.

Such antioxidants are preferably selected from the group consisting of tetrakis- methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane and tris (2,4- Or mixed form, and may include 0.1 to 0.5 parts by weight based on 100 parts by weight of the first resin. When the amount of the antioxidant is less than 0.1 part by weight, the ability of the thermal decomposition prevention is insufficient, and the cellulose ester may be thermally decomposed in the thermoplastic or radial process. If the amount is more than 0.5 part by weight,

The first resin may preferably have an intrinsic viscosity of 0.95 to 1.42, a melt specific gravity (MD) of 1.01 to 1.18 g / cc, and a melt flow index (MI) of 50 to 80 g / 10 min.

 The present invention relates to a biodegradable polyol produced by esterification and polycondensation of an acid component comprising an aromatic polycarboxylic acid, an aliphatic polycarboxylic acid and a sulfonic acid metal salt and a diol component having 2 to 14 carbon atoms, And a second resin which is an ester. The composition of the present invention is capable of high-speed melt spinning by mixing the first resin with the second resin, which is the biodegradable polyester, and the thermoplastic cellulose derivative fiber thus produced can have improved strength and biodegradability.

When conventional polyester other than the modified polyester according to the present invention is mixed, it is possible to improve the strength of the cellulose fiber. However, since it is impossible to spin at high speed, the productivity may be decreased and the biodegradability may be rapidly deteriorated.

The acid component used in the biodegradable polyester polymerization which is the second resin may comprise 70 to 89 mol% of aromatic polycarboxylic acid, 10 to 30 mol% of aliphatic polycarboxylic acid and 0.1 to 3.0 mol% of sulfonic acid metal salt have.

The aromatic polycarboxylic acid in the acid component may more preferably be a single compound or a mixture of terephthalic acid, isophthalic acid, dimethyl terephthalate or dimethyl isophthalate . The amount of the aromatic acid to be used may be used as the remaining amount excluding the content of the aliphatic acid and the sulfonic acid metal salt in the total weight of the acid components. When the amount of the aromatic acid used is less than 70 mol%, the resultant biodegradable polyester There may be a problem of poor radioactivity for application to a fiber product group, and when it is more than 89 mol%, it may be difficult to decompose and compost the biodegradable polyester obtained.

The aliphatic polycarboxylic acid in the acid component is more preferably selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, The organic acid may be selected from the group consisting of suberic acid, citric acid, pimeric acid, azelaic acid, sebasic acid, nonanoic acid, decanoic acid, Dodecanoic acid or hexanoadecanoic acid may be used alone or in combination.

The aliphatic acid is most preferably an oxalic acid, succinic acid, adipic acid, sebacic acid or the like which is an even number of carbon atoms and can be used by mixing one or more of these aliphatic acids because these aliphatic acids have excellent physical properties when reacted with divalent glycol It is because. When the amount of the aliphatic acid used is less than 10 mol%, it may be disadvantageous in that it does not have biodegradability. On the contrary, when the amount of the aliphatic acid is more than 30 mol% There is a problem that the mechanical properties are very poor at the time of molding.

In addition, the sulfonic acid metal salt in the acid component may improve the biodegradability by using an alkali metal or an alkaline earth metal. The sulfonic acid metal salt is preferably used in an amount of 0.1 to 3 mol%. When the sulfonic acid metal salt is used in an amount of less than 0.1 mol%, there may be a problem that the biodegradability of the obtained biodegradable polyester is lowered, and when it exceeds 3.0 mol%, moldability may be deteriorated.

The diol component used in the biodegradable polyester polymerization may be any one of ethylene glycol, propylene glycol, trimethyl glycol, tetramethylene glycol, pentamethyl glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, Aliphatic divalent glycols such as decamethylene glycol, undecamethylene glycol, dodecamethylene glycol, tridecamethylene glycol, and tetradecamethylene glycol, especially those having 2 to 6 carbon atoms and even-numbered ethylene glycol, tetramethylene glycol, hexamethylene glycol Etc. are excellent in improvement of physical properties.

The biodegradable polyester of the present invention can be prepared by mixing the polyvalent carboxylic acid component and the diol component having 2 to 14 carbon atoms at a weight ratio of 1: 1.0 to 1.4 in the esterification step and the polycondensation step.

The esterification step is a step of preparing an acid component and a diol component with a composition according to the biodegradable polyester use and then producing an oligomer at 200 to 260 ° C for 210 to 330 minutes at 40 to 80 rpm. In the esterification step, the reaction is carried out at a temperature of 260 ° C or less, which is less likely to produce by-products and can prevent thermal decomposition of the raw material.

In the polycondensation process, the oligomer produced by the ester process is polycondensed at 240 to 285 DEG C for 180 to 210 minutes at 40 to 100 rpm to produce a polyester. In general, the aliphatic polyester polymer is carried out at a low temperature of 200 to 270 ° C. In the case of the present invention, the catalyst and the heat stabilizer are selected by reacting at a higher temperature of 240 to 285 ° C. in order to prepare the aromatic copolymer polyester polymer It is important.

In the polymerization process, a titanium catalyst or an antimony catalyst may be used as the polymerization catalyst.

It is preferable that tetrabutyl isopropoxide or tetrabutyl titanate is used as the titanium catalyst, and antimony trioxide is preferably used as the antimony catalyst will be.

The polymerization catalyst may be a titanium catalyst or an antimony catalyst alone, but it is preferable to use a mixture of two catalysts. When the titanium catalyst and the antimony catalyst are mixed, the titanium catalyst and the antimony catalyst are mixed with 25 : 75 to 50: 50.

The composition of the present invention can increase the productivity by allowing high-speed melt spinning by mixing an appropriate amount of a second resin, which is a biodegradable polyester, with a first resin including a cellulose ester and a plasticizer, and the thermoplastic cellulose derivative fiber thus produced has high strength And biodegradability can be improved.

The preferred mixing weight ratio of the first resin and the second resin may be from 2: 8 to 4: 6. If the range is out of the range, strand formation during compounding is not smooth, yarn incidence is high during the spinning process, There is a problem that the improvement is deteriorated.

Most preferably, the weight ratio of the first resin to the second resin is from 2: 8 to 4: 6 and the weight ratio of the water-soluble plasticizer of the first resin to the polylactic acid (PLA) is from 7: 3 to 9: 1 have. In this case, high-speed spinning of 4000mpm or more is possible, productivity can be increased, yarn dyes are not generated, dyes are excellent, and three-fineness of 80 denier or less can be emitted. The fiber thus prepared can satisfy the strength of not less than 3.5 g / de and elongation of not less than 35%.

The present invention also relates to a biodegradable polyester prepared by esterifying and polycondensing a mixture of an acid component containing an aromatic polycarboxylic acid, an aliphatic polycarboxylic acid and a sulfonic acid metal salt, and a diol component having 2 to 14 carbon atoms, Ester and polylactic acid (PLA). ≪ Desc / Clms Page number 2 >

 The cellulose ester is a cellulose ester in which a part or all of the hydroxyl groups of the cellulose are substituted with an ester bond, more preferably cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate caproate, cellulose acetate caprylate , Cellulose acetate laurethate, cellulose acetate palmitate, cellulose acetate stearate or cellulose acetate oleate, or the like.

The cellulose ester of the present invention may have an average degree of polymerization of 30,000 to 50,000 and a degree of substitution of 2.2 to 2.6. If the degree of substitution is less than 2.2, the fluidity may be lowered and the strength may be lowered at the time of wetting. If the degree of substitution is more than 2.6, the biodegradability may be deteriorated.

The acid component used in the biodegradable polyester polymerization may comprise 70 to 89 mol% of an aromatic polycarboxylic acid, 10 to 30 mol% of an aliphatic polycarboxylic acid, and 0.1 to 3.0 mol% of a sulfonic acid.

The aromatic polycarboxylic acid in the acid component may more preferably be a single compound or a mixture of terephthalic acid, isophthalic acid, dimethyl terephthalate or dimethyl isophthalate . The amount of the aromatic acid to be used may be used as the remaining amount excluding the content of the aliphatic acid and the sulfonic acid metal salt in the total weight of the acid components. When the amount of the aromatic acid used is less than 70 mol%, the resultant biodegradable polyester There may be a problem of poor radioactivity for application to a fiber product group, and when it is more than 89 mol%, it may be difficult to decompose and compost the biodegradable polyester obtained.

The aliphatic polycarboxylic acid in the acid component is more preferably selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, The organic acid may be selected from the group consisting of suberic acid, citric acid, pimeric acid, azelaic acid, sebasic acid, nonanoic acid, decanoic acid, Dodecanoic acid or hexanoadecanoic acid may be used alone or in combination.

The aliphatic acid is most preferably an oxalic acid, succinic acid, adipic acid, sebacic acid or the like which is an even number of carbon atoms and can be used by mixing one or more of these aliphatic acids because these aliphatic acids have excellent physical properties when reacted with divalent glycol It is because. When the amount of the aliphatic acid used is less than 10 mol%, it may be disadvantageous in that it does not have biodegradability. On the contrary, when the amount of the aliphatic acid is more than 30 mol% There is a problem that the mechanical properties are very poor at the time of molding.

In addition, the sulfonic acid metal salt in the acid component may improve the biodegradability by using an alkali metal or an alkaline earth metal. The sulfonic acid metal salt is preferably used in an amount of 0.1 to 3 mol%. If the sulfonic acid metal salt is used in an amount of less than 0.1 mol%, the biodegradability of the obtained biodegradable polyester may be deteriorated. If the amount is more than 3.0 mol%, the moldability may be deteriorated.

The diol component used in the biodegradable polyester polymerization may be any one of ethylene glycol, propylene glycol, trimethyl glycol, tetramethylene glycol, pentamethyl glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, Aliphatic divalent glycols such as decamethylene glycol, undecamethylene glycol, dodecamethylene glycol, tridecamethylene glycol, and tetradecamethylene glycol, especially those having 2 to 6 carbon atoms and even-numbered ethylene glycol, tetramethylene glycol, hexamethylene glycol Etc. are excellent in improvement of physical properties.

The biodegradable polyester of the present invention can be prepared by mixing the polyvalent carboxylic acid component and the diol component having 2 to 14 carbon atoms at a ratio of 1.0: 1.0 to 1.4: 1 by weight, followed by an esterification step and a polycondensation step.

The fiber of the present invention may contain 1 to 10% by weight of polylactic acid (PLA) and 50 to 80% by weight of biodegradable polyester. When the biodegradable polyester is contained in an amount of less than 50% by weight, there is a problem that high-speed spinning is not possible or the physical properties of the yarn are weak, and when the content is more than 80% by weight, the biodegradability may be low. When the content of polylactic acid (PLA) is less than 1% by weight, unreacted materials of the water-soluble plasticizer are eluted to cause slipping on the surface of the yarn. When the content exceeds 10% by weight, .

 Such fibers of the present invention include a first resin comprising a cellulose ester, a water soluble plasticizer and polylactic acid (PLA); And a second resin which is a biodegradable polyester prepared by esterifying and polycondensing a mixture of an acid component containing an aromatic polycarboxylic acid, an aliphatic polycarboxylic acid and a sulfonic acid metal salt and a diol component having 2 to 14 carbon atoms, : 8 to 4: 6, and the water-soluble plasticizer and polylactic acid (PLA) are contained at a weight ratio of 4: 6 to 9: 1 and melt spinning at a spinning temperature of 200 to 300 캜.

The thermoplastic cellulose derivative fiber thus produced may have a strength of 2.5 g / de or more and an elongation of 30% or more.

Most preferably, the mixing ratio by weight of the first resin and the second resin is from 2: 8 to 4: 6, and the weight ratio of the water-soluble plasticizer of the first resin and the polylactic acid (PLA) is from 7: 3 to 9: The fiber is capable of high-speed spinning of 4000mpm or more, which can increase the productivity, does not generate a dyed yarn, and is excellent in dyeability. Also, it satisfies a strength of not less than 3.5 g / de and an elongation of not less than 35%, and it is possible to spin at three denier of 80 denier or less.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

< Example 1 >

75% by weight of cellulose acetate having an average degree of substitution of 2.4 and an average molecular weight of 40,000 (Eastman), 10% by weight of a water-soluble plasticizer polyethylene glycol having an average molecular weight of 600, and polylactic acid having an average molecular weight of 140,000 as a biomass plasticizer (NatureWorks Co., 15% by weight.

(3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane (Anox 20, manufactured by Tosoh Corporation), which is a primary antioxidant, is added to prevent thermolysis when thermally- Tetris (2,4-di-t-butylphenyl) phosphate (Alcanox 240, Chemtura Corporation), a secondary antioxidant, was used to prevent thermal decomposition in the plasticizer- Was added in an amount of 0.1 part by weight to 100 parts by weight of a resin containing cellulose acetate and polyethylene glycol. After that, the mixture was fixed at 25 kg / hr using a kneader equipped with a twin extruder at a kneader speed of 270 rpm, (DIE) The thermoplastic cellulose acetate resin (1) was obtained by blending for five minutes at a starting temperature of 170 占 폚 over five steps while applying a temperature to a final terminal temperature of 200 占 폚.

A 250 ml flask equipped with a stirrer and a condenser was charged with 10 mol% of adipic acid, 89 mol% of terephthalic acid and 1 mol% of a sulfonic acid metal salt (alkaline earth metal) as an acid component in the reaction molar ratio, : Ethylene glycol was added so that the weight ratio of ethylene glycol was 1: 1.2. Then, 400 ppm of lithium acetate was added as an esterification catalyst. The temperature in the reactor was elevated from room temperature to 120 deg. C over 30 minutes, . Subsequently, 300 ppm of phosphoric acid as a heat stabilizer and 300 ppm of antimony trioxide as a catalyst were added, and the pressure in the tube was gradually reduced to 0.5 mmHg over 40 minutes, and the reaction was carried out for 180 minutes while the temperature in the tube was raised to 280 ° C Stirring was stopped and the mixture was discharged to obtain a biodegradable polyester resin (2).

The thermoplastic cellulose ester resin (1) and the biodegradable polyester resin (2) prepared above were mixed in a ratio of 7: 3, and a compatibilizer, that is, ADR-4300 (BASF Corporation) as a chain extender was mixed with the thermoplastic cellulose ester resin 0.5 part by weight based on 100 parts by weight of the mixed composition of the biodegradable polyester resin (2) was added, and the mixture was fixed with a circulator feeder at a rate of 20 kg / hr and a motor speed of 135 rpm using a kneader equipped with a twin extruder. Lt; 0 &gt; C to prepare a composite resin (3).

Based on the resin (3) thus produced, spinning was carried out at a resin spinning temperature of 265 DEG C in a melt spinning machine equipped with a 24Hole cage. The obtained fibers were washed with water at 40 占 폚 for 10 minutes to remove the water-soluble plasticizer, and then dried at 60 占 폚.

< Example 2 >

Was prepared in the same manner as in Example 1, except that the resin (1) and the resin (2) were mixed at a weight ratio of 5: 5.

< Example 3 >

Was prepared in the same manner as in Example 1, except that the resin (1) and the resin (2) were mixed in a weight ratio of 3: 7.

< Example 4 >

The procedure of Example 1 was repeated except that 20% by weight of polyethylene glycol and 5% by weight of polylactic acid were contained in the preparation of Resin (1).

< Example 5 >

Was prepared in the same manner as in Example 4, except that the resin (1) and the resin (2) were mixed at a weight ratio of 5: 5.

< Example 6 >

Was prepared in the same manner as in Example 4, except that the resin (1) and the resin (2) were mixed in a weight ratio of 3: 7.

< Example 7 >

The procedure of Example 1 was repeated except that 15% by weight of polyethylene glycol and 10% by weight of polylactic acid were contained in the preparation of Resin (1).

< Example 8 >

Was prepared in the same manner as in Example 7, except that the resin (1) and the resin (2) were mixed at a weight ratio of 5: 5.

< Example 9 >

Was prepared in the same manner as in Example 7 except that the resin (1) and the resin (2) were mixed in a weight ratio of 3: 7.

< Example 10 >

The procedure of Example 6 was repeated except for using 59 mol% of terephthalic acid, 40 mol% of adipic acid, and 1 mol% of metal sulfonate as acid components in the production of resin (2).

< Comparative Example 1 >

Was prepared in the same manner as in Example 1, except that the resin (2) as a biodegradable polyester was not mixed.

< Comparative Example 2 >

Was prepared in the same manner as in Example 4, except that the resin (2) as a biodegradable polyester was not mixed.

< Comparative Example 3 >

Was prepared in the same manner as in Example 7, except that the resin (2) as a biodegradable polyester was not mixed.

< Comparative Example 4 >

The procedure of Example 3 was repeated except that 60 mol% of terephthalic acid and 40 mol% of succinic acid were mixed as an acid component in the production of Resin (2) and no sulfonic acid metal salt was used.

< Comparative Example 5 >

Was prepared in the same manner as in Example 6, except that PET prepared by polymerizing terephthalic acid and ethylene glycol in place of resin (2) was mixed.

< Comparative Example 6 >

A resin (1) was prepared in the same manner as in Example 6, except that 75% by weight of cellulose acetate and 25% by weight of polyethylene glycol were used.

< Experimental Example >

1. Evaluation of dyeability

Dyeability was evaluated by dyeing the disperse dye at a temperature of 120 ° C at a heating rate of 2 minutes in a salt solution of 0.3 wt%, pH 4.5, relative to the weight of the fabric, and then reducing and cleaning the solution at 2 g / L of Na 2 SO 3 and 2 g / And the dyeability was evaluated by the presence of a dyke.

division Resin (1) Mixing ratio of plasticizer (% by weight) Resin (2) Acid component
(mole%) Resin (1): Resin (2) PEG 600 PLA Example 1 10 15 TPA (89) / AA (10) / DMS (1) 7: 3 Example 2 10 15 TPA (89) / AA (10) / DMS (1) 5: 5 Example 3 10 15 TPA (89) / AA (10) / DMS (1) 3: 7 Example 4 20 5 TPA (89) / AA (10) / DMS (1) 7: 3 Example 5 20 5 TPA (89) / AA (10) / DMS (1) 5: 5 Example 6 20 5 TPA (89) / AA (10) / DMS (1) 3: 7 Example 7 15 10 TPA (89) / AA (10) / DMS (1) 7: 3 Example 8 15 10 TPA (89) / AA (10) / DMS (1) 5: 5 Example 9 15 10 TPA (89) / AA (10) / DMS (1) 3: 7 Example 10 20 5 TPA (59) / AA (40) / DMS (1) 3: 7 Comparative Example 1 10 15 - 1: 0 Comparative Example 2 20 5 - 1: 0 Comparative Example 3 15 10 - 1: 0 Comparative Example 4 20 5 TPA (60) / SA (40) 3: 7 Comparative Example 5 20 5 TPA (100) 3: 7 Comparative Example 6 25 0 TPA (89) / AA (10) / DMS (1) 3: 7

PEG: polyethylene glycol, PLA: polylactic acid

TPA: terephthalic acid, AA: adipic acid, SA: succinic acid, DMS: sulfonic acid metal salt

Compounding
Operability radiation
Operability Spinning speed
(mpm) Properties Dyeability Radiation of three fibers Fineness burglar Shindo Example 1 ○ △ 1500 145.2 1.5 22 △ Impossible Example 2 △ △ 1000 150.1 1.2 23 △ Impossible Example 3 ○ ○ 3000 100.5 2.9 38 ○ possible Example 4 ○ △ 1900 144.8 2.0 30 △ Impossible Example 5 △ △ 1500 151.1 1.8 28 △ Impossible Example 6 ◎ ◎ 4,500 75.1 3.8 37 ◎ possible Example 7 ○ △ 1800 145.1 1.9 25 △ Impossible Example 8 △ △ 1500 143.5 1.5 28 △ Impossible Example 9 ○ ○ 3100 75.8 3.0. 35 ○ possible Example 10 ○ X - - - - - No spinning Comparative Example 1 △ △ 800 150.1 1.2 24 X Impossible Comparative Example 2 △ △ 1500 145.2 1.5 25 X Impossible Comparative Example 3 △ △ 1200 143.7 1.4 22 X Impossible Comparative Example 4 ○ X - - - - - No spinning Comparative Example 5 X X - - - - - No spinning Comparative Example 6 ◎ ◎ 4,000 74.8 3.5 38 △ possible

<Compounding workability>

X: No compounding is performed, △: Cutting is performed within 5 minutes after strand formation, ∘: Cutting is performed within 10 minutes, ◎ Workability is excellent

<Spreadability>

X: no spinning,?: Free spinning 2,

○: 3,000mpm can be emitted, but not in 5 minutes, ◎: More than 4,000mpm can be emitted

<Dyeability>

 X: Dyeing impossible,?: Significant occurrence of a dyestuff,?: Occurrence of some dyestuffs,?: Good

As can be seen from the above table, the strength and elongation of the resin mixed with the resin (2) according to the present invention were significantly improved as compared with Comparative Examples 1 to 3 in which the resin (2) was not mixed. The effects of the water-soluble plasticizers PEG and PLA in the mixing ratio of the resin 1 and the resin 2 vary depending on the content ratio of the water-soluble plasticizer PEG and PLA and the mixing ratio of the resin 1 and the resin 2 is 3: It has the best pounding and spinning ability, and is also excellent in strength and dyability. Most preferably, Example 6 in which the weight ratio of water-soluble plasticizer PEG and PLA is 8: 2 and the mixing ratio of resin (1) and resin (2) is 3: 7 is the most excellent in compounding and spinnability, High speed spinning and spinning of less than 100De were possible, and especially excellent in dyeability. Comparative Example 6, which did not contain PLA, was similar to that of the light source, but the water-soluble plasticizer was eluted on the surface and the surface was found to be dyed due to occurrence of the surface vibrations.

In Comparative Example 4 in which Example 10 in which the resin (2) polymerized with the acid component deviating from the scope of the present invention was mixed with Resin (2) polymerized without containing the sulfonic acid metal salt, spinning could not proceed. In Comparative Example 5 in which general PET was mixed, there was a problem that the PET did not melt at a temperature of 260 占 폚 at which the resin (1) and PET were compounded, and compounding was impossible. When the temperature was raised to 290 占 폚, Compounding was not possible due to pyrolysis of 1).

Claims (6)

delete delete delete A thermoplastic cellulose acetate resin comprising a cellulose ester, a water-soluble plasticizer and a polylactic acid; And
By mixing 10 to 30 mol% of an aliphatic polycarboxylic acid, 0.1 to 3.0 mol% of a sulfonic acid metal salt, and an acid component containing a residual amount of an aromatic polycarboxylic acid and a diol component having 2 to 14 carbon atoms, Of biodegradable polyester at a weight ratio of 2: 8 to 4: 6 Including,
Wherein the thermoplastic cellulose acetate resin comprises 70 to 90% by weight of the cellulose ester, the water soluble plasticizer and the polylactic acid in a weight ratio of 7: 3 to 9: 1,
Wherein the fiber has a fineness of 80 deg. Or less, a strength of 3.0 g / de or more, and an elongation of 30% or more.
5. The method of claim 4,
Wherein the acidic component and the diol component are mixed at a weight ratio of 1: 1.0 to 1.4, and polymerized.
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