KR20140010737A

KR20140010737A - The thermoplastic cellulose derivative and thereby made fiber

Info

Publication number: KR20140010737A
Application number: KR1020120077427A
Authority: KR
Inventors: 김도현; 신동수; 손정아; 임성수; 김민웅
Original assignee: 웅진케미칼 주식회사
Priority date: 2012-07-16
Filing date: 2012-07-16
Publication date: 2014-01-27

Abstract

The present invention relates to a thermoplastic cellulose derivative composition and fibers produced by using the same, which enables melt spinning without using an organic solvent toxic to environment and a human body, improves productivity by high-speed spinning, and provides cellulose fibers with improved strength, elongation, and biodegradability.

Description

Thermoplastic cellulose derivative composition and the fiber produced by the same

The present invention relates to a thermoplastic cellulose derivative composition and a fiber produced therefrom, and more particularly, to an eco-friendly cellulose derivative composition and fiber which can be melt-spun without dissolving in an organic solvent and is well 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.

Among them, products such as polylactic acid (PLA) or starch have recently been spotlighted as raw materials supplied from nature, which is a biomass system.However, it is impossible to dye at high temperature for fiber and it is vulnerable to hydrolysis. When tenter work is carried out, there are various disadvantages such as hardening to have brittle characteristics, and it is difficult to proceed spinning at a discharge speed of 4000 mpm in a spinning apparatus that radiates existing polyester.

Cellulose materials are the most biodegradable, resource-cycling biomass materials produced 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. In addition, it is difficult to use in general fields such as clothing products due to problems such as high speed spinning of 4,000mpm, which not only decreases productivity, but also stiffness and inflexibility, and is easily damaged when fabricated due to lack of elongation. There was this.

The present invention has been made to solve the above problems, it is possible to melt spinning without using an organic solvent toxic to the environment and the human body, to improve the elongation and biodegradation, high-speed spinning to increase productivity It is an object of the present invention to provide a thermoplastic cellulose derivative composition which can be obtained and the fibers produced therefrom.

In order to solve the above problems, the present invention,

A first resin comprising a cellulose ester and a plasticizer; And a second resin prepared by mixing an acid component including an aromatic polyvalent carboxylic acid, an aliphatic polyvalent carboxylic acid, and a sulfonic acid metal salt and a diol component having 2 to 14 carbon atoms and esterifying and polycondensing it. It provides a thermoplastic cellulose derivative composition.

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

According to another preferred embodiment of the present invention, the first resin may include 70 to 90% by weight of cellulose ester and 10 to 30% by weight of a plasticizer.

According to another preferred embodiment of the present invention, tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane and tris (2, It may further comprise 0.1 to 0.5 parts by weight of any one or more antioxidants selected from the group consisting of 4-di-t-butylphenyl) phosphate.

According to another preferred embodiment of the present invention, the cellulose ester is cellulose acetate, cellulose acetate propionate, cellulose acetate butylate, cellulose acetate phthalate, cellulose acetate caprylate, cellulose acetate caprylate, cellulose acetate triulate, cellulose At least one selected from the group consisting of acetate palmitate, cellulose acetate stearate and cellulose acetate oleate.

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

According to another preferred embodiment of the present invention, the plasticizer may be any one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, polyglycolic acid and polybutyl adipate having an average molecular weight of 1000 or less.

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

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

In addition, the present invention is a biodegradable polyester and cellulose prepared by mixing and esterifying and polycondensing an acid component and an aromatic divalent carboxylic acid, an aliphatic polycarboxylic acid and a sulfonic acid metal salt and a diol component having 2 to 14 carbon atoms. It provides a thermoplastic cellulose derivative fiber comprising an ester.

According to a preferred embodiment of the present invention, the fiber may comprise 50 to 80% by weight of biodegradable polyester.

According to another preferred embodiment of the present invention, the acid component is polymerized to include 70 to 89 mol% of aromatic polyvalent carboxylic acid, 10 to 30 mol% of aliphatic polyvalent carboxylic acid and 0.1 to 3.0 mol% of sulfonic acid metal salt. Can be.

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 2.0 g / de or more and an elongation of 30% or more.

The thermoplastic cellulose derivative composition of the present invention is capable of melt spinning without using an organic solvent toxic to the environment and the human body, thereby providing cellulose fibers with improved elongation and biodegradability.

In addition, high-speed spinning is possible and productivity can be increased, and it can be practically used in yarn, cotton, non-woven fabric, fabric, sheet and the like.

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

As described above, the conventional thermoplastic cellulose derivative composition and the fiber produced therefrom are not capable of high-speed spinning, resulting in poor productivity, stiffness, inflexibility, and easily damaged when fabricated due to lack of elongation.

In the present invention, the first resin comprising a cellulose ester and a plasticizer; And a second resin prepared by mixing an acid component including an aromatic polyvalent carboxylic acid, an aliphatic polyvalent carboxylic acid, and a sulfonic acid metal salt and a diol component having 2 to 14 carbon atoms and esterifying and polycondensing it. To solve the above problems by providing a thermoplastic cellulose derivative composition. This enables high-speed spinning, thereby increasing productivity, and improving ductility and biodegradation of cellulose fibers.

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 plasticizer included in the first resin of the present invention is not particularly limited as long as the plasticizer is mixed with the cellulose derivative to prevent strong hydrogen bonds caused by the cellulose hydroxyl group and melt-spin, but more preferably 1000 or less so as to promote plasticization. Low molecular weight of can be used.

Examples of the plasticizer include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dihexyl phthalate, dioctyl phthalate, dimethoxyethyl phthalate, ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate, tetraoctyl pyromellitate, Aromatic dicarboxylic acid esters such as dibutyl adipate, dibutyl adipate, dibutyl sebacate, dioctyl sebacate, diethyl azelate, dibutyl azelate and dioctyl azelate; and aromatic dicarboxylic acid esters such as dibutyl adipate, Aromatic polycarboxylic acid esters, lower fatty acid esters of polyhydric alcohols such as glycerin triacetate and diglycerin tetraacetate, phosphoric acid esters such as triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, tricresyl phosphate and the like Alone or in combination.

Examples of relatively high molecular weight plasticizers include aliphatic polyesters composed of glycols and dibasic acids such as polyethylene glycol, polypropylene glycol, polyethylene adipate, polybutylene adipate, polyethylene succinate, and polybutylene succinate; Aliphatic polyesters composed of oxycarboxylic acids such as glycolic acid, aliphatic polyesters composed of lactones such as polycaprolactone, polypropiolactone and polar valerolactone, vinyl polymers such as polyvinylpyrrolidone Or mixed form.

The first resin may include 70 to 90% by weight of cellulose ester and 10 to 30% by weight of a plasticizer. If the plasticizer is contained in less than 10% by weight, melt spinning may not be possible due to strong hydrogen bonding of cellulose, and if it exceeds 30% by weight, there may be a problem of fuming during melt spinning, and bleed out of the plasticizer to the fiber surface. There may be a problem with this.

The first resin of the present invention may further include an antioxidant, which serves to prevent decomposition by heat when thermally plasticizing the cellulose ester and in the process of spinning the plasticized cellulose ester.

Such antioxidants are preferably alone such as tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane and tris (2,4-di-t-butylphenyl) phosphate Or it may be in a mixed form, it 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 1.10 to 1.25 η, a melt specific gravity (MD) of 1.05 to 1.09 g / cc, and a melt flow index (MI) of 50.0 to 80.5 g / 10 min.

The present invention is a biodegradable poly acrylate prepared by mixing an acid component including an aromatic polyhydric carboxylic acid, an aliphatic polyhydric carboxylic acid and a sulfonic acid metal salt and a diol component having 2 to 14 carbon atoms to esterify and polycondensate the first resin. The composition which mixed the 2nd resin which is ester is provided. Such a composition of the present invention is capable of high-speed melt spinning by mixing the second resin of the biodegradable polyester to the first resin, the thermoplastic cellulose derivative fibers thus prepared can be improved in elongation and biodegradability.

When the conventional polyester is mixed in addition to the modified polyester according to the present invention, cellulose fibers may be improved in elongation, but high-speed spinning may not be possible, resulting in poor productivity and rapid degradation of biodegradation.

Acid components used in the biodegradable polyester polymerization may include 70 to 89 mol% of aromatic polyvalent carboxylic acids, 10 to 30 mol% of aliphatic polyvalent carboxylic acids and 0.1 to 3.0 mol% of sulfonic acid metal salts.

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. The aliphatic acid is preferably used in the range of 10 to 30 mol%, when the amount of the aliphatic acid is used less than 10 mol%, there may be a disadvantage in not having biodegradability, on the contrary exceeds 30 mol% If so, there may be a problem that the mechanical properties during the molding process is very poor.

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, An aliphatic divalent glycol such as decamethylene glycol, undecamethylene glycol, dodecamethylene glycol, tridecamethylene glycol, and tetradecamethylene glycol, and particularly preferably an ethylene glycol having 2 to 6 carbon atoms and an even number of 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 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 enables high-speed melt spinning to increase productivity by mixing an appropriate amount of a second resin, which is a biodegradable polyester, with a first resin containing a cellulose ester and a plasticizer, thereby increasing productivity. And biodegradability can be improved.

Preferred mixing weight ratio of the first resin and the second resin may be 2: 8 to 4: 6, if out of the above range, the formation of strands during compounding is not smooth, the incidence of trimming during the spinning process, high strength and elongation There may be a problem that the improvement is degraded.

In addition, the composition comprising a mixture of the first resin and the second resin may further include a compatibilizer, the compatibilizer is a special limitation as long as it improves the compatibility of the first resin and the second resin to facilitate spinning. It may preferably comprise 0.1 to 1.0 parts by weight based on 100 parts by weight of the total composition. If the compatibilizer is less than 0.1 parts by weight, the compounding and spinning operation is insufficient due to the lack of compatibility, and finally, the threading probability may be high when yarn is manufactured. Action or a sharp rise in viscosity can cause spin pack pressure rise, which can cause problems with spinning operation.

The cellulose ester is a part or all of the hydroxyl group of the cellulose is substituted with an ester bond, more preferably cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate caponate, cellulose acetate caprylate , Cellulose acetate triulate, cellulose acetate palmitate, cellulose acetate stearate or cellulose acetate oleate, or the like, or a mixture thereof.

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 is lowered and the strength may be lowered when wet, if it exceeds 2.6 there may be a problem that the biodegradability is lowered.

The acid component used in the biodegradable polyester polymerization may include 70 to 89 mol% of aromatic polyhydric carboxylic acid, 10 to 30 mol% of aliphatic polyhydric carboxylic acid and 0.1 to 3.0 mol% of 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 may be used as the remaining amount excluding the amounts of the aliphatic acid and the sulfonic acid metal salt in the total weight of the acid component, but when the amount of the aromatic acid is too small, less than 70 mol%, the biodegradable polyester obtained There may be a problem that the radioactivity for application to the textile product group is not good, and if too much in excess of 89 mol%, there is a problem that the decomposition and composting of the biodegradable polyester obtained is difficult.

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. The aliphatic acid is preferably used in the range of 10 to 30 mol%, when the amount of the aliphatic acid is used less than 10 mol%, there may be a disadvantage in not having biodegradability, on the contrary exceeds 30 mol% In this case, there may be a problem that the mechanical properties during the molding process is very poor.

The biodegradable polyester of the present invention may be prepared by mixing the polyhydric carboxylic acid component and the diol component having 2 to 14 carbon atoms in a weight ratio of 1.0: 1.0 to 1.4 by an esterification process and a polycondensation process.

The fiber of the present invention may comprise 50 to 80% by weight of biodegradable polyester. When the biodegradable polyester is included in less than 50% by weight, there is a problem that the yarn elongation is significantly insufficient due to the lack of elongation of spinning and fiber formation is impossible, and when the biodegradable polyester exceeds 80% by weight, the biodegradability may be reduced.

Such a fiber of the present invention comprises a first resin comprising a cellulose ester and a plasticizer; And a second resin which is a biodegradable polyester prepared by esterification and polycondensation by mixing an acid component including an aromatic polyvalent carboxylic acid, an aliphatic polyvalent carboxylic acid and a sulfonic acid metal salt and a diol component having 2 to 14 carbon atoms. It can be prepared by mixing at a weight ratio of 8: 8 to 4: 6 and melt spinning at 200 to 300 ° C spinning temperature and 4000 to 4500mpm spinning speed.

The thermoplastic cellulose derivative fiber prepared as described above may have a strength of 2.0 g / de or more and an elongation of 30% or more.

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.

&Lt; Example 1 >

Substitution degree 2.4, 75 weight% of cellulose acetate (Eastman Co., Ltd.) whose average molecular weight is 40,000, and 25 weight% of water-soluble plasticizer polyethyleneglycol of the average molecular weight 600 were prepared. In order to prevent thermal decomposition when thermally plasticizing with a compound, tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane (Anox 20, CAMPURA CORPORATION / Chemtura Corporation) and Tris (2,4-di-t-butylphenyl) phosphate (Alcanox240, Chemtura Corporation) as a secondary antioxidant to prevent thermal decomposition in the spinning process with plasticizer chips After adding 0.1 parts by weight to 100 parts by weight of a resin containing cellulose acetate and polyethylene glycol, using a kneader equipped with a twin extruder fixed at 25kg / hr, kneader motor speed of 270Rpm kneader die ( DIE) The thermoplastic cellulose acetate resin (1) was obtained after blending for 5 minutes at a starting temperature of 170 ° C. and giving a final terminal temperature of 200 ° C. over 5 steps.

After adding 10 mol% of adipic acid, 89 mol% of terephthalic acid, and 1 mol% of sulfonic acid metal salt (alkaline earth metal) in the reaction molar ratio as an acid component in a 250 ml flask equipped with a stirrer and a condenser, the amount of ethylene glycol was added to the acid component. : After adding ethylene glycol in a weight ratio of 1: 1.2, 400 ppm of lithium acetate was added as an esterification catalyst, and the temperature in the reactor was elevated to 120 ° C. over 30 minutes from room temperature to 30 ° C. while stirring, and then heated up to 250 ° C. for 120 minutes. I was. Subsequently, after adding 300 ppm of phosphoric acid as a heat stabilizer and 300 ppm of antimony trioxide as a catalyst, the mixture was gradually reduced in pressure to 0.5 mmHg over 40 minutes, and stirred for 180 minutes while the temperature was raised to 280 ° C. Agitation was stopped and discharged to obtain a biodegradable polyester resin (2).

After mixing the thermoplastic cellulose ester resin (1) prepared above and the biodegradable polyester resin (2) at 7: 3, a compatibilizer, that is, a chain extender, ADR-4300 (BASF Corporation) was used as the thermoplastic cellulose ester resin (1) and Add 0.5 parts by weight to 100 parts by weight of the mixed composition of the biodegradable polyester resin (2) and fix the circle feeder with a kneader equipped with twin extruders at a fixed feed speed of 20 kg / hr and a motor speed of 135 rpm, followed by a die temperature of 260 degrees and a polymer temperature of 269. It was blended in the figure to prepare a composite resin (3).

Based on the resin (3) thus prepared, spinning was performed at a draw ratio of three times the draw ratio under a condition of a discharge rate of 33 g / min, a discharge rate of 4,000mpm, and a spinning temperature of 265 ° C. in a molten spinning machine equipped with 24Hole detention.

&Lt; Example 2 >

Preparation was carried out in the same manner as in Example 1 except that the resin (1) and the resin (2) were mixed in a weight ratio of 5: 5.

&Lt; Example 3 >

Preparation was carried out 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.

A compatibilizer ADR-4300 (BASF Corporation) was prepared in the same manner as in Example 3 except for including 3.0 parts by weight.

&Lt; Example 5 >

It was prepared in the same manner as in Example 3 except that the compatibilizer ADR-4300 (BASF) was not included.

&Lt; Example 6 >

Tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane as a primary antioxidant and tris (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant Except that it was prepared in the same manner as in Example 3.

&Lt; Example 7 >

It was prepared in the same manner as in Example 3 except for including cellulose acetate propionate in place of cellulose acetate.

Example 8

It was prepared in the same manner as in Example 3 except that triacetin was used instead of polyethylene glycol as a plasticizer.

Example 9

The preparation of Resin (2) was carried out in the same manner as in Example 3, except that 59 mol% of terephthalic acid, 40 mol% of adipic acid, and 1 mol% of sulfonic acid metal salt were used as acid components.

&Lt; Comparative Example 1 &

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

&Lt; Comparative Example 2 &

60 mole% of terephthalic acid and 40 mole% of succinic acid were mixed as an acid component in the preparation of the resin (2), except that the sulfonic acid metal salt was not used.

&Lt; Comparative Example 3 &

It was prepared in the same manner as in Example 3 except that PET prepared by polymerizing terephthalic acid and ethylene glycol was mixed instead of the resin (2).

Resin (1) Resin (2) Acid Component
(mole%) Resin (1): Resin (2) Antioxidant
(1st / 2nd) Compatibilizer
(Parts by weight) cellulose Plasticizer Example 1 CA PEG TPA (89) / AA (10) / DMS (1) 7: 3 0.1 / 0.1 0.5 Example 2 CA PEG TPA (89) / AA (10) / DMS (1) 5: 5 0.1 / 0.1 0.5 Example 3 CA PEG TPA (89) / AA (10) / DMS (1) 3: 7 0.1 / 0.1 0.5 Example 4 CA PEG TPA (89) / AA (10) / DMS (1) 3: 7 0.1 / 0.1 3.0 Example 5 CA PEG TPA (89) / AA (10) / DMS (1) 3: 7 0.1 / 0.1 0 Example 6 CA PEG TPA (89) / AA (10) / DMS (1) 3: 7 0/0 0.5 Example 7 CAP PEG TPA (89) / AA (10) / DMS (1) 3: 7 0.1 / 0.1 0.5 Example 8 CA TA TPA (89) / AA (10) / DMS (1) 3: 7 0.1 / 0.1 0.5 Example 9 CA PEG TPA (59) / AA (40) / DMS (1) 3: 7 0.1 / 0.1 0.5 Comparative Example 1 CA PEG - 1: 0 0.1 / 0.1 0.5 Comparative Example 2 CA PEG TPA (60) / SA (40) 3: 7 0.1 / 0.1 0.5 Comparative Example 3 CA PEG TPA (100) 3: 7 0.1 / 0.1 0.5

CA: cellulose acetate, CAP: cellulose acetate propionate

PEG: polyethylene glycol, TA: triacetin

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

1. Biodegradation evaluation

After the sample was put into distilled water at 100 ℃, it was hydrolyzed for 96 hours and the intrinsic viscosity of each spinning sample before and after hydrolysis was measured. The intrinsic viscosity is a value that represents the molecular weight of the polymer, and the fact that a large amount of hydrolysis is performed means that the decrease in the molecular weight is increased.

The biodegradation mechanism is hydrolysis of the polymer main chain due to the first reaction, resulting in low molecular weight, and decomposed into CO ₂ , water and biomass by the microorganism in the second reaction.

Compounding
Operability radiation
Operability Fineness
(De) burglar
(g / de) Shindo
(%) Biodegradability
(%) Example 1 ○ ○ 74.4 2.5 35 94.6 Example 2 △ △ 74.2 1.8 33 92.1 Example 3 ◎ ◎ 74.8 3.5 38 87.5 Example 4 △ X - - - - Example 5 △ X - - - - Example 6 △ △ 75.6 1.5 28 88.1 Example 7 ◎ ○ 75.9 3.2 35 87.6 Example 8 ◎ △ 74.5 1.2 25 85.1 Example 9 ◎ X - - - - Comparative Example 1 ◎ △ 145.2 0.8 23 87.1 Comparative Example 2 ◎ X - - - - Comparative Example 3 X X - - - -

Compounding operability

X: No compounding work, △: Cut within 5 minutes after strand formation, ○: Cut within 10 minutes, ◎: Good

X: No radiation, △: Trimming within 5 minutes, ○: Trimming within 10 minutes, ◎: Good

As can be seen from the table, the strength and elongation of the example in which the resin 2 was mixed according to the present invention was significantly improved as compared with Comparative Example 1 in which the resin 2 was not mixed.

Specifically, Example 3 having a mixing ratio of Resin (1) and Resin (2) of 3: 7 was the best in compounding and spinning operations, and the best in terms of strength and elongation. If the compatibilizer is not mixed or included in an excessive amount, it was impossible to spin, and when the antioxidant is not included, compounding and spinning are difficult as well as the physical properties of the fiber are lowered.

In the case of Example 9 in which the resin (2) polymerized with an acid component outside the scope of the present invention and Comparative Example 2 in which the resin (2) was polymerized without the sulfonate metal salt were mixed, spinning could not proceed. In addition, in Comparative Example 3 in which the general PET was mixed, compounding was not possible due to the problem that PET was not melted at a temperature of 260 ° C., which compounded the resin 1 and PET, and when the temperature was raised to 290 ° C., the resin ( Compounding was not possible due to thermal decomposition of 1).

Claims

A first resin comprising a cellulose ester and a plasticizer; And
A second resin prepared by mixing an acid component including an aromatic polyhydric carboxylic acid, an aliphatic polyvalent carboxylic acid and a sulfonic acid metal salt and a diol component having 2 to 14 carbon atoms and esterifying and polycondensing it; Thermoplastic Cellulose Derivative Composition.

The method of claim 1,
The composition is a thermoplastic cellulose derivative composition, characterized in that the mixing weight ratio of the first resin and the second resin is 2: 8 to 4: 6.

The method of claim 1,
The first resin is a thermoplastic cellulose derivative composition, characterized in that it comprises 70 to 90% by weight of cellulose ester and 10 to 30% by weight of a plasticizer.

The method of claim 1,
Tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane and tris (2,4-di-t-butylphenyl) phosphate based on 100 parts by weight of the first resin Thermoplastic cellulose derivative composition, characterized in that it further comprises 0.1 to 0.5 parts by weight of any one or more antioxidants selected from the group.

The method of claim 1,
The cellulose ester is cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate caponate, cellulose acetate caprylate, cellulose acetate triacrylate, cellulose acetate palmitate, cellulose acetate acetate and cellulose acetate. The thermoplastic cellulose derivative composition, characterized in that any one or more selected from the group consisting of oleate.

The method of claim 1,
The cellulose ester has a degree of substitution of 2.2 to 2.6 thermoplastic cellulose derivative composition, characterized in that.

The method of claim 1,
The plasticizer is a thermoplastic cellulose derivative composition, characterized in that any one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, polyglycolic acid and polybutyl adipate having an average molecular weight of 1000 or less.

The method of claim 1,
The acid component is a thermoplastic cellulose derivative composition comprising 70 to 89 mol% of aromatic polyhydric carboxylic acid, 10 to 30 mol% of aliphatic polyvalent carboxylic acid and 0.1 to 3.0 mol% of sulfonic acid metal salt.

The method of claim 1,
The acid component and the diol component is a thermoplastic cellulose derivative composition, characterized in that the polymerization by mixing in a weight ratio of 1.0: 1.0 to 1.4.

Biodegradable polyesters and cellulose esters prepared by mixing an acid component containing an aromatic polyvalent carboxylic acid, an aliphatic polyvalent carboxylic acid and a sulfonic acid metal salt and a diol component having 2 to 14 carbon atoms and esterifying and polycondensing them Characterized in that the thermoplastic cellulose derivative fiber.

The method of claim 10,
The fiber is a thermoplastic cellulose derivative fiber, characterized in that it comprises 50 to 80% by weight of biodegradable polyester.

The method of claim 10,
The acid component is a thermoplastic cellulose derivative fiber characterized in that the polymerization comprises 70 to 89 mol% of aromatic polyvalent carboxylic acid, 10 to 30 mol% of aliphatic polyvalent carboxylic acid and 0.1 to 3.0 mol% of sulfonic acid metal salt.

The method of claim 10,
The acid component and the diol component is a thermoplastic cellulose derivative fiber, characterized in that the polymerization by mixing in a weight ratio of 1.0: 1.0 to 1.4.

The method of claim 10,
The thermoplastic cellulose derivative fiber has a strength of 2.0 g / de or more and an elongation of 30% or more.