KR20140128493A

KR20140128493A - The molten cellulose derivative composition and fiber

Info

Publication number: KR20140128493A
Application number: KR1020130046226A
Authority: KR
Inventors: 임성수; 오영일; 신동수; 김도현
Original assignee: 도레이케미칼 주식회사
Priority date: 2013-04-25
Filing date: 2013-04-25
Publication date: 2014-11-06

Abstract

The present invention relates to a fused cellulose derivative composition and a fused cellulose derivative fiber, and more particularly, to a fused cellulose derivative composition and a fused cellulose derivative fiber which are capable of melt spinning without using an organic solvent toxic to the environment and human body, And it is possible to provide a molten cellulose derivative composition and a fused cellulose derivative fiber which are capable of high temperature radiation, prevent oxidation during processing and prevent oxidation in the atmosphere, and have a low defective rate.

Description

The molten cellulose derivative composition and the molten cellulose derivative fiber (the molten cellulose derivative composition and fiber)

The present invention relates to a fused cellulose derivative composition and a fused cellulose fiber, and more particularly to a fused cellulose derivative composition having excellent strength and excellent color, and to a fused cellulose fiber will be.

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, When the tenter work is carried out, it has various disadvantages such as hardening and brittle characteristic.

Cellulosic materials are biodegradable resource-recycling biomass materials that can be produced in pulp and are therefore produced in the largest amount on the earth without the need for separate cultivated land and water. 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, (KR 2002-0080821), which has been used for a long time.

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 fibers prepared therefrom are known.

On the other hand, conventionally, there has been a problem in that thermal decomposition occurs in the process of thermoplasticizing the cellulose ester and spinning the plasticized cellulose ester, so that it is difficult to spin the cellulose ester at a high temperature.

Further, after the cellulose fiber is produced, oxidation occurs in the air, and the color of the cellulose fiber is poor or the defect rate is high.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to prevent the thermal decomposition and oxidation occurring during the processing of cellulose derivative fibers, A cellulose derivative composition and a cellulose derivative fiber which can be used as a cellulose derivative can be provided.

In order to solve the above-described problems, the present invention relates to a cellulose ester, a plasticizer, There is provided a molten cellulose derivative composition comprising a radical generation inhibitor and a radical activity inhibitor.

According to a preferred embodiment of the present invention, the radical generation inhibitor may be a water insoluble compound including a phenol group, preferably tetrakis methylene (3,5-di-t-butyl-4-hydroxycinnamate) Methane.

According to a preferred embodiment of the present invention, the radical activity inhibitor may be a water-insoluble compound containing phosphorus at the terminal, preferably tris (2,4-di-t-butylphenyl) phosphite.

The plasticizer may include at least one selected from the group consisting of polyethylene glycol, glycerin, tributyl sebacate, triacetin and triethyl citrate, and the cellulose ester may be 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 and cellulose acetate oleate And the like.

According to a preferred embodiment of the present invention, the cellulose ester may have a degree of substitution of 2.2 to 2.6, and the composition may include 5 to 30% by weight of a plasticizer, and the radical generating 0.2 to 1.5 parts by weight of an inhibitor, and 0.2 to 1.5 parts by weight of a radical activity inhibitor. More preferably, 0.2 to 0.5 parts by weight of the radical generation inhibitor and 0.2 to 0.5 parts by weight of the radical activity inhibitor may be added to 100 parts by weight of the cellulose ester.

Another aspect of the present invention provides a fused cellulose derivative fiber prepared by the fused cellulose derivative composition provided in the present invention.

Another aspect of the present invention provides a fused cellulose fiber comprising a radical formation inhibitor and a radical activity inhibitor, and may comprise 0.2 to 0.5% by weight of the radical generation inhibitor and 0.2 to 0.5% by weight of a radical activity inhibitor.

The melted cellulose derivative composition and the melted cellulose derivative fiber of the present invention can spin the composition at a high temperature and the spun fiber can provide a molten cellulose derivative composition and a molten cellulose derivative fiber having excellent strength and excellent color and defective ratio .

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

As described above, conventionally, there has been a problem that thermal degradation occurs in the process of thermally or thermally oxidizing cellulosic ester or in the process of radiating plasticized cellulose ester, and oxidation occurs in the atmosphere after the cellulose fiber is produced, resulting in a high defect rate .

Thus, according to one aspect of the present invention, cellulose ester; Plasticizers; Radical generation inhibitors; And a radical activity inhibitor, to solve the above-mentioned problems. This prevents pyrolysis and oxidation which occur during the processing of the cellulose derivative fibers, as well as prevents the oxidation of the cellulose derivative fibers in the atmosphere, thereby lowering the defective rate of the cellulose derivative fibers.

First, the cellulose ester will be described.

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.

As the plasticizer is mixed effectively, it can interfere with strong hydrogen bonding due to cellulose hydroxyl groups and melt spinning becomes possible.

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 following radical formation inhibitors are described.

The radical formation inhibitor of the present invention plays a role of preventing decomposition by heat in the process of thermally and thermosetting a cellulose ester and plasticizing cellulose ester, and inhibiting the generation of radicals generated when the chain is broken.

The radical generation inhibitor may be in the form of a liquid or solid phase which is easily mixed with the cellulose ester and the plasticizer, preferably a water-insoluble compound containing a phenol group, more preferably tetrakis methylene (3,5-di- t-butyl-4-hydroxycinnamate) methane. Examples of the radical formation inhibitor that can be used in the present invention include the above-mentioned tetrakis methylene (3,5-di-t-butyl-4-hydroxycinnamate) methane and include Anox 20 (Chemtura Co.), Iganox 1010 (Ciba Specialty Chemicals, Inc.) and Songnox 1010 (Songwon International Co., Ltd.).

The amount of the radical generation inhibitor may be 0.2 to 1.5 parts by weight, preferably 0.2 to 0.5 parts by weight, based on 100 parts by weight of the cellulose ester. If the amount is less than 0.2 parts by weight, The cellulose ester may be pyrolyzed during the digestion or spinning process, and if it exceeds 1.5 parts by weight, there may be a problem in spinning workability as a cause of an increase in pack pressure.

In the present invention, by including the radical generation inhibitor, it is possible to melt-spin at a temperature of 250 to 300 ° C, prevent thermal oxidation during processing, and provide a fused cellulose derivative fiber having excellent chromaticity.

On the other hand, the fused cellulose derivative composition of the present invention can provide not only a radical generation inhibitor but also a radical activity inhibitor, thereby providing a fused cellulose derivative fiber having a low defective rate and excellent chromaticity (see Table 2).

The following radical active inhibitors are described.

The radical activity inhibitor of the present invention prevents oxidization from occurring in the air after the cellulose derivative fiber is prepared, and plays a role of inhibiting the radical generation generated by breaking of the cellulose main chain.

The radical activity inhibitor may be in the form of a liquid or solid phase which is easily mixed with the cellulose ester and the plasticizer. The radical activity inhibitor may be preferably a water-insoluble compound containing phosphorus at the terminal, more preferably tris (2,4-di -t-butylphenyl) phosphite. Examples of the radical activity inhibitor that can be used in the present invention include Alkanox 240 (Chemtura Co.), Igafos 168 (Ciba Specialty Chemicals, Inc.), which contains tris (2,4- , And Songnox 1680 (Songwon Industrial Co., Ltd).

In the present invention, both the radical generation inhibitor and the radical activity inhibitor should be included to prevent the oxidation of the cellulose derivative composition and to prevent the oxidation of the cellulose derivative fiber, thereby reducing the defective rate. (See Table 2)

In particular, a radical containing a radical formation inhibitor comprising tetrakis methylene (3,5-di-t-butyl-4-hydroxycinnamate) methane and a radical comprising tris (2,4- It is necessary to simultaneously contain an active inhibitor so that the radiation workability is excellent even at a high temperature radiation, so that the prevention of oxidation during processing and the prevention of oxidation in the atmosphere can be very effective. Therefore, cellulose derivative fibers excellent in the strength and chromaticity can be produced (see Examples 1 to 5).

On the other hand, even when two or more kinds of radical generation inhibitors or two or more kinds of radical activity inhibitors are included, it is difficult to radiate high temperature, and the strength and chromaticity (See Comparative Examples 1 to 6).

Therefore, as the radical generation inhibitor and the radical activity inhibitor are mixed, the prevention of thermal decomposition during spinning is very effective, and not only the melt cellulose fiber with improved strength can be produced, but also the high temperature radiation can be achieved during melt spinning, have.

Describe the following plasticizers.

The plasticizer is not particularly limited as long as it is mixed with a cellulose derivative to inhibit strong hydrogen bonding due to cellulose hydroxyl groups and melt-emit, but it is more preferable to use a low molecular weight of 1000 or less so that plasticization can be promoted.

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; poly 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 plasticizer of the present invention may preferably include at least one plasticizer selected from the group consisting of polyethylene glycol, glycerin, tributyl sebacate, triacetin, and triethylcitrate.

The molten cellulose derivative composition of the present invention may contain 5 to 30% by weight of a plasticizer. Specifically, when the amount of the plasticizer is less than 5% by weight, the effect of interfering with strong hydrogen bonding of cellulose may be insufficient and melt spinning may not be possible. If it exceeds 30% by weight, a problem of fuming may occur during melt spinning , Bleeding-out of the plasticizer to the fiber surface may occur.

The present invention also provides a fused cellulose derivative fiber made from the above-mentioned fused cellulose derivative composition.

Another aspect of the present invention is a composition comprising a radical generation inhibitor; And a radical activity inhibitor, wherein the radical generation inhibitor may comprise 0.2 to 0.5 wt%, and the radical activity inhibitor may comprise 0.2 to 0.5 wt%.

The radical generation inhibitor may most preferably be tetrakis methylene (3,5-di-t-butyl-4-hydroxycinnamate) methane. If the amount of the radical generation inhibitor is less than 0.2% by weight, the cellulose ester may be thermally decomposed in the thermoplastic or radial process. When the radical generation inhibitor is used in an amount of more than 1.5% by weight, There may be sexual problems.

Next, the radical activity inhibitor of the present invention plays a role of preventing oxidization in the atmosphere after the cellulose derivative fiber is produced and inhibiting the generation of radicals generated by breaking of the cellulose main chain.

The radical activity inhibitor may most preferably be tris (2,4-di-t-butylphenyl) phosphite. If the amount of the radical activity inhibitor is less than 0.2% by weight, the cellulose ester may be thermally decomposed in the thermoplastic or radial process. When the radical activity inhibitor is used in an amount of more than 1.5% by weight, There may be sexual problems.

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 ]

Example One

To obtain a fused cellulose acetate composition, 30 parts by weight of polyethylene glycol (polyethylene glycol) as a plasticizer was added to 100 parts by weight of cellulose acetate having an average degree of substitution of cellulose hydroxyl group of 2.4 and an average molecular weight of 40,000 (Eastman Co.) 0.5 part by weight of kis methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane (Anox 20, Camtura Corporation / Chemtura Corporation) Di-t-butylphenyl) phosphate (Alcanox 240, Camtura Corporation) were mixed and mixed for 2 minutes using a supermixer. The mixed mixture was dried at 80 ° C. for 24 hours in a hot air drier, fixed at 25 kg / hr of a circle feeder and 270 rpm of a kneader using a kneader equipped with a twin-screw extruder, and then kneaded at a kneader die (DIE) Over 5 minutes to give a fused cellulose acetate composition with a final end temperature of 200 < RTI ID = 0.0 > C < / RTI >

The thermoplastic cellulose acetate composition prepared above was spin-cast at a stretching ratio of 3 times under the conditions of a composition discharge rate of 33 g / min, a spinning speed of 2,500 mpm, and a spinning temperature of 275 캜 to a melt emitter equipped with a 24-hole knife to prepare fibers.

Example 2 to 7 and Comparative Example 1 to 6

A fiber was prepared in the same manner as in Example 1, except that the numerical values in Table 1 were used.

division Cellulose ester Plasticizer Radical generation inhibitor Radical activity inhibitor Kinds content Kinds content Example 1 100 parts by weight 35 parts by weight A 0.5 parts by weight C 0.5 parts by weight Example 2 100 parts by weight 35 parts by weight A 0.3 parts by weight C 0.5 parts by weight Example 3 100 parts by weight 35 parts by weight A 0.5 parts by weight C 0.3 parts by weight Example 4 100 parts by weight 35 parts by weight B 0.5 parts by weight C 0.5 parts by weight Example 5 100 parts by weight 35 parts by weight A 0.5 parts by weight D 0.5 parts by weight Example 6 100 parts by weight 35 parts by weight A 1 part by weight D 1 part by weight Example 7 100 parts by weight 35 parts by weight A 1.5 parts by weight D 1.5 parts by weight Comparative Example 1 100 parts by weight 35 parts by weight X X X X Comparative Example 2 100 parts by weight 35 parts by weight A 0.5 parts by weight X X Comparative Example 3 100 parts by weight 35 parts by weight X X C 0.5 parts by weight Comparative Example 4 100 parts by weight 35 parts by weight A 0.5 parts by weight X X B 0.5 parts by weight X X Comparative Example 5 100 parts by weight 35 parts by weight X X C 0.5 parts by weight X X D 0.5 parts by weight Comparative Example 6 100 parts by weight 35 parts by weight P 0.5 parts by weight Q 0.5 parts by weight A: Anox 20 / B: Iganox 1010 / C: Alkanox 240 / D: Igafos 168 /
X: None / P: Tablet wax / Q: Epoxidized Soybean oil

Experimental Example One

1. Measurement of River and Shinto

Steel fiber and elongation of the fiber were measured using an automatic tensile tester (Textechno) at a speed of 50 cm / m and a grip distance of 50 cm.

Strength and elongation are defined as the elongation (%) of the initial length of the elongated length as a percentage (g / de) divided by the denier when the fiber is stretched until it is cut with a constant force. Respectively.

2. Radiation workability

To evaluate the possibility of high - speed radiation, the radiation workability was determined as follows.

X: Not spinning,?: Five minutes inside,?: Ten minutes inside,?: Good

3. Chromaticity measurement

The colorimetric measurements of the fibers were carried out by using a colorimeter L * a * b, index ASTM E313-73, color difference equations DELTA E * ab (CIE 1976), DELTA E * 94 (CIE 194) and Brightness, saturation, and color.

4. Defect rate measurement

In the case of the primary antioxidant, the defect rate is measured by the frequency of the filament yarn and the discoloration of the fiber when the filament is spun. The defect standard is bad when the filament frequency is at least once / 1 hr and the fiber b value (colorimetric value) In the case of the second antioxidant, it is measured by the change with time of the yarn. The criteria for measuring the elapsed time change is judged as the rate of deterioration of the physical properties of the yarn.

Spinning speed
(mpm) Radiation workability burglar
(g / de) Shindo
(%) Chromaticity Final fiber Defect rate
(%) standard Comparison value (end) (I) Example 1 2500 ◎ 0.95 31 7 5.73 0.3 0.35 1.1 Example 2 2500 ◎ 0.89 29 7 6.19 0.22 0.31 1.3 Example 3 2500 ◎ 0.92 30 7 5.98 0.31 0.24 1.4 Example 4 2500 ◎ 0.85 28 7 6.35 0.3 0.3 1.9 Example 5 2500 ◎ 0.87 29 7 6.74 0.38 0.37 1.9 Example 6 2500 ◎ 0.85 28 7 6.64 0.6 0.58 4.2 Example 7 2500 ◎ 0.86 29 7 6.54 1.2 0.8 7.9 Comparative Example 1 2500 △ 0.55 24 7 8.28 X X 78.2 Comparative Example 2 2500 ○ 0.64 30 7 7.27 0.4 X 49.1 Comparative Example 3 2500 ○ 0.59 28 7 7.71 X 0.3 52.2 Comparative Example 4 2500 △ 0.68 30 7 6.92 0.8 X 44.7 Comparative Example 5 2500 △ 0.62 29 7 6.75 X 0.9 47.1 Comparative Example 6 2500 △ 0.41 11 7 8.98 0.4 0.4 81.2 (A): Residual rate of radical formation inhibitor in the final fiber (% by weight)
(B): Residual rate of radical activity inhibitor in final fiber (% by weight)

As can be seen from Table 1, Examples 1 to 7 are superior to Comparative Examples 1 to 6 in spinning workability, excellent in chromaticity and strength, and significantly lower in defective rate.

Specifically, when the radical generation inhibitor A and the radical activity inhibitor C were used together, the defective rate was the lowest, and the defective rate was also low when the radical production inhibitor B radical activity inhibitor C was used.

On the other hand, when all of the radical activity inhibitor and the radical generation inhibitor were not used, the defect rate was not good, and even when none of the radical activity inhibitor or the radical generation inhibitor was introduced, the defective rate was high. Even when two kinds of radical activity inhibitors were used, the defective rate was high.

In Examples 6 and 7, the contents of the radical formation inhibitor and the radical activity inhibitor were relatively higher than those of Examples 1 to 5, so that the content of the radical formation inhibitor and the radical activity inhibitor remained in the final fiber was high, Somewhat higher.

Claims

Cellulose esters; Plasticizers; Radical generation inhibitors; And a radical activity inhibitor.

The method according to claim 1,
Wherein the radical generation inhibitor is a water insoluble compound containing a phenol group.

The method according to claim 1,
Wherein the radical activity inhibitor is a water insoluble compound containing phosphorus at the terminal.

3. The method of claim 2,
Wherein the radical generation inhibitor is tetrakis methylene (3,5-di-t-butyl-4-hydroxycinnamate) methane.

The method of claim 3,
Wherein the radical activity inhibitor is tris (2,4-di-t-butylphenyl) phosphite.

The method according to claim 1,
Wherein the plasticizer is at least one selected from the group consisting of polyethylene glycol, glycerin, tributyl sebacate, triacetin and triethyl citrate.

The method according to claim 1,
The cellulose esters include 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 and cellulose acetate And an oleate. The molten cellulose derivative composition according to claim 1,

The method according to claim 1,
Wherein the cellulose ester has a degree of substitution of 2.2 to 2.6.

The method according to claim 1,
Wherein the composition comprises 5 to 30% by weight of a plasticizer.

The method according to claim 1,
0.2 to 1.5 parts by weight of the radical generation inhibitor and 0.2 to 1.5 parts by weight of a radical activity inhibitor based on 100 parts by weight of the cellulose ester.

The method according to claim 1,
0.2 to 0.5 parts by weight of the radical generation inhibitor and 0.2 to 0.5 parts by weight of a radical activity inhibitor based on 100 parts by weight of the cellulose ester.

A fused cellulose derivative fiber prepared by the composition of any one of claims 1-11.

A fused cellulose derivative fiber comprising a radical formation inhibitor and a radical activity inhibitor

14. The method of claim 13,
0.2 to 0.5% by weight of the radical generation inhibitor, and 0.2 to 0.5% by weight of a radical activity inhibitor.