KR101292654B1 - Degradating polyester composite fiber for screen fabfic - Google Patents

Abstract

The present invention relates to a biodegradable polyester composite fiber for screen fabric, and more particularly, to an acid component comprising an aliphatic acid containing a carboxylic acid group and an aromatic acid containing a phenylene group in a polyester ciscore type composite fiber. , A polyester prepared by mixing esterified and polycondensed by mixing a sulfonic acid metal salt and a diol component having 2 to 14 carbon atoms, the core part 10 to 20 mol% of aliphatic acid, 80 to 90 mol% of aromatic acid and 0.5 to 1.5 mol of sulfonic acid metal salt % Is mixed, the ratio of the substance and diol component containing acid and metal sulfonic acid salt is mixed in a weight ratio of 1.0: 1.0 to 1.4, the cis part 10-20 aliphatic acid of any of adipic acid, succinic acid and glutaric acid Mol%, terephthalic acid 40 to 60 mol%, isophthalic acid 20 to 40 mol% and sulfonic acid metal salt 0.5 to 1.5 mol%, the ratio of the substance and diol component containing the acid component and sulfonic acid metal salt is 1.0 Provides biodegradable polyester composite fiber for screen fabric, which is mixed at a weight ratio of 1.2 to 1.4.

Description

Biodegradable polyester composite fiber for screen fabric

The present invention relates to a biodegradable polyester composite fiber for screen fabrics and a method for producing the same, and more particularly, to a polyester composite fiber manufactured by changing a composition during polyester fiber production so as to be well decomposed.

Polymer resins have been widely used for various purposes because of their excellent mechanical properties, chemical resistance, and durability. However, conventional plastics, namely synthetic resins, do not decompose themselves in nature, and thus induce harmful substances when incinerated. It has its drawbacks. Recently, as environmental pollution problem has become a big problem in society, research on biodegradable resins that can be completely decomposed in nature has been actively carried out and has attracted worldwide interest.

Conventional biodegradable resins, ie, polybutylene succinate, polyethylene succinate, polylactic acid, etc., are excellent in biodegradability, but lack economical efficiency at a high price, or are limited to molding injection molding products which have a low melting point. It is not possible to develop a product line that must maintain thermal stability in the production of products like the fiber product group. Existing biodegradable polymers have limited mechanical properties, chemical resistance, and low durability, and are limited to disposable packaging materials, that is, injection molding products.

In addition, the use of diethylene glycol (DEG) as a raw material used in the polymerization leads to the disadvantage that it is difficult to secure the drying conditions in the drying step before the spinning step for producing the fiber product group, Because of the aluminum acetate base, which is a common nocatalyst, there is a drawback that spinning workability is difficult due to initial pack pressure during spinning. In addition, the resulting polymer has a color tone b value of 9 or more, which is not suitable for use in a textile product group.

In this regard, such as the Republic of Korea Patent Application No. 2006-7002339, the name of the invention "biodegradable polyester mixture" and No. 2001-0055645, the name of the invention "biodegradable polyester resin composition reinforced with tear strength" Efforts are being made to improve. In particular, in Korean Patent Application No. 2010-0075068, aromatic copolyester compounds which can be produced by a fiber product group have been prepared, but the color tone b value is not less than 9, and since the initial packing pressure is high during spinning, There is a shortage of products for textile applications.

To solve this problem, Japanese Unexamined Patent Application Publication Nos. 4-189822 and 189823 disclose a process for esterifying an aliphatic dicarboxylic acid and an aliphatic dicarboxylic glycol followed by a polycondensation reaction, adding an isocyanate compound again, To improve the molecular weight and melt viscosity, thereby improving the physical properties of the aliphatic polyester, but failing to secure the physical properties of fibers or films.

In addition, when adding a material having improved degradability in order to increase the biodegradability, there was a problem that the product is impossible to manufacture or produce a poor mechanical properties due to problems such as spinning during fiber production.

On the other hand, the screen fabric currently being used has a problem that does not decompose for a long time when the decomposition is weak.

Therefore, when manufacturing the fabric for screen fabric, it was required to develop a biodegradable fabric that can be decomposed under composting conditions while maintaining the mechanical properties of the fiber itself.

In order to solve the above problems, an object of the present invention is to provide a polyester composite fiber with improved spinning and elongation and degradability by changing the composition of the feedstock using aliphatic acid and aromatic acid.

It is also an object of the present invention to provide a biodegradable polyester composite fiber that can produce a biodegradable polyester in the optimum manufacturing conditions.

It is also an object of the present invention to provide a composite fiber with improved degradability, but to provide a fiber that can be used for screen fabric as a fiber that can maintain mechanical properties.

In order to achieve the above object, the present invention provides a polyester ciscore type composite fiber comprising an acid component, a sulfonic acid metal salt, and a diol having 2 to 14 carbon atoms, including an aliphatic acid containing a carboxylic acid group and an aromatic acid including a phenylene group. A polyester produced by esterification and polycondensation by mixing components, wherein the core portion is mixed with 10-20 mol% aliphatic acid, 80-90 mol% aromatic acid, and 0.5-1.5 mol% sulfonic acid metal salt, and acid component and sulfonic acid metal salt. The ratio of the substance and diol component containing 1.0 is mixed in a weight ratio of 1.0: 1.0 ~ 1.4,

The cis moiety is mixed with 10-20 mol% of aliphatic acid, 40-60 mol% of terephthalic acid, 20-40 mol% of isophthalic acid and 0.5-1.5 mol% of sulfonic acid metal salt, which is any of adipic acid, succinic acid and glutaric acid. Provided is a biodegradable polyester composite fiber for a screen fabric in which the ratio of the diol component and the material containing the powder and the sulfonate metal salt is mixed in a weight ratio of 1.0: 1.2 to 1.4.

In the present invention, the aliphatic acid of the core part is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, suberic acid, and suberic acid. acid), citric acid, pimeric acid, azelaic acid, sebasic acid, nonanoic acid, decanoic acid, dodecanoic acid ( It provides a biodegradable polyester composite fiber for screen fabric, characterized in that at least one selected from the group consisting of Dodecanoic acid) and hexanodecanoic acid (Hexadecanoic acid).

In another aspect, the present invention provides a biodegradable polyester composite fiber for screen fabric, characterized in that the sulfonic acid metal salt is an alkali metal or alkaline earth metal.

In addition, the present invention is the diol ethylene glycol having 2 to 14 carbon (Ethylene Glycol), propylene glycol (Propylene Glycol), trimethyl glycol (Trimethyl Glycol), tetramethylene glycol (Tetramethylene Glycol), pentamethyl glycol (Pentamethyl Glycol), Hexamethylene Glycol, Heptamethylene Glycol, Octamethylene Glycol, Nonnamethylene Glycol, Decamethylene Glycol, Undecamethylene Glycol, Undecamethylene Glycol It provides a biodegradable polyester composite fiber for screen fabrics, characterized in that at least one selected from the group consisting of domethylene glycol (Dodecamethylene Glycol), tridecamethylene glycol (Tridecamethylene Glycol) and tetradecamethylene glycol (Tetradecamethylene Glycol).

In another aspect, the present invention provides a biodegradable polyester composite fiber for screen fabric, characterized in that the weight ratio of the core portion and the sheath portion is 3: 7 ~ 7: 3.

Polyester composite fiber according to the present invention has the effect that the polyester resin can provide a biodegradable fiber that can be spun and improved stretchability.

In addition, the polyester composite fiber according to the present invention can be produced in the optimum manufacturing conditions, it is possible to practical use as yarn, cotton, nonwoven fabric, fabric, sheet and the like.

In addition, the physical properties of the fiber in the polyester composite fiber according to the present invention is characterized in that the strength is 2.5 ~ 3.5g / de, elongation 35 ~ 45%.

The composite fiber prepared according to the present invention is excellent in biodegradability by maintaining a hydrolysis rate of 80% or more, and has an effect of providing a fiber that can be utilized for screen fabric.

Hereinafter, preferred embodiments of the present invention will be described in detail. In describing the present invention, detailed descriptions of related well-known functions or configurations are omitted in order not to obscure the subject matter of the present invention.

The terms " about ", " substantially ", etc. used to the extent that they are used herein are intended to be taken to mean an approximation to or in the numerical value of the manufacturing and material tolerances inherent in the meanings mentioned, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

The biodegradable polyester composite fiber according to the present invention is esterified by mixing an acid component, a sulfonic acid metal salt, and a diol component having 2 to 14 carbon atoms, including an aliphatic acid including a carboxylic acid group and an aromatic acid including a phenylene group. To prepare a polyester resin prepared by polycondensation, to prepare a polyester composite fiber.

In the composite fiber according to the present invention, looking at the core portion in the sheath core type,

10-20 mol% of aliphatic acid, 80-90 mol% of aromatic acid, and 0.5-1.5 mol% of sulfonic acid metal salt are mixed, and the ratio of the substance and diol component containing an acid component and a sulfonic acid metal salt is mixed at a weight ratio of 1.0: 1.0-1.4. By esterification and polycondensation.

The aliphatic acid is preferably used in the range of 10-20 mol% in the total mole% of the acid component and sulfonic acid metal salt in the core portion of the composite fiber. When the amount of the aliphatic acid used is less than 10 mol%, there may be a disadvantage in that it does not have a decomposability, on the contrary, if the amount of the aliphatic acid exceeds 20 mol%, there may be a problem that the mechanical properties during the molding process is poor. .

The aliphatic acid in the acid component is preferably, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, subberin Suberic acid, citric acid, pimeric acid, azelaic acid, sebasic acid, nonanoic acid, decanoic acid and dodeic Can be selected from the group consisting of Dodecanoic acid (Dodecanoic acid), hexanodecanoic acid (Headecanoic acid). The aliphatic acid is particularly preferably used by mixing one or two or more of even-numbered oxalic acid, succinic acid, adipic acid, sebacic acid, etc., which has an excellent physical property when reacting with a divalent glycol. Have

The aromatic acid of the acid component, preferably, may be at least one selected from the group consisting of terephthalic acid, isophthalic acid, dimethyl terephthalate and dimethyl isophthalate. . The amount of the aromatic acid may be used as a limited residual amount of the aliphatic acid and the sulfonic acid metal salt in the total weight of the acid component, but if the amount of the aromatic acid is too small, applying the biodegradable polyester obtained as a fiber product group There may be a problem that the radioactivity for the poor, and on the contrary too many, there is a problem that the decomposition and composting of the biodegradable polyester obtained is difficult.

In addition, in the present invention, the sulfonic acid metal salt may improve the biodegradability by using an alkali metal or alkaline earth metal, and the sulfonic acid metal salt may be included in the core portion.

In addition, the sulfonic acid metal salt in the core portion is preferably mixed with 0.5 to 1.5 mol% sulfonic acid metal salt in the total mol% of the acid component and sulfonic acid metal salt.

Next, when looking at the cis part, 10 to 20 mol% of aliphatic acid, any one of adipic acid, succinic acid and glutaric acid, 40 to 60 mol% of terephthalic acid, 20 to 40 mol% of isophthalic acid and 0.5 to 1.5 mol of sulfonic acid metal salt It is preferable that the ratio of the substance and the diol component containing the acid component and the sulfonate metal salt is mixed in a ratio of 1.0: 1.2 to 1.4 by weight.

The aliphatic acid may be used as any one of adipic acid, succinic acid and glutaric acid, and the amount of the aliphatic acid is preferably in an amount of 10 to 20 mol% based on the total mole% of the acid component and the metal salt of sulfonic acid. When the amount of the aliphatic acid, which is any one of the adipic acid, succinic acid and glutaric acid, is used in an amount less than 10 mol%, there may be a disadvantage in that it does not have degradability. There may be a problem that the mechanical properties are poor at the time.

In addition, the cis portion may include terephthalic acid and isophthalic acid among aromatic acids. It is preferable that they are 40-60 mol% of terephthalic acid and 20-40 mol% of isophthalic acid in the total mol% of an acid component and sulfonic acid metal salt.

If the amount of the aromatic acid is too small, there may be a problem that the radioactivity for applying the biodegradable polyester obtained to the fiber product group, on the contrary, if too large, the decomposition and composting of the biodegradable polyester obtained There may be problems that become difficult.

In addition, in the present invention, the sulfonic acid metal salt may improve the biodegradability by using an alkali metal or alkaline earth metal, and the sulfonic acid metal salt may be included in the core portion.

The sulfonic acid metal salt is preferably mixed with 0.5 to 1.5 mol% of sulfonic acid metal salt in the total mole% of the acid component and the sulfonic acid metal salt.

When the sulfonic acid metal salt contained in the core portion is less than the above range, there may be a problem in that the biodegradability is lowered and the biodegradability of the biodegradable polyester is lowered, and when the sulfonate metal salt is in the above range, the moldability is deteriorated. .

On the other hand, the diol component is ethylene glycol, propylene glycol, trimethyl glycol, tetramethylene glycol, pentammethyl glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, nonmethylene glycol, decamethylene glycol, Undeca having 2 to 14 carbon atoms As aliphatic dihydric glycols of methylene glycol, dodecamethylene glycol, tridecamethylene glycol, tetradecamethylene glycol, ethylene glycol, tetramethylene glycol, hexamethylene glycol and the like having 2 to 6 carbon atoms and even numbered ones, great.

The mixing ratio of the acid component of the aromatic acid, aliphatic acid and the sulfonic acid metal salt material and the diol component may be mixed in a weight ratio of 1.0: 1.2 to 1.4.

Next, to carry out the esterification step, the esterification step is to proceed to each composite fiber component. That is, it is natural to perform the esterification process of the cis type polyester resin and the core type polyester resin which produce a cis core type composite fiber, respectively.

First, in the polyester resin for preparing the core portion, the esterification process is to prepare the oligomer at 210 ~ 330 minutes, 40 ~ 80 rpm at 200 ~ 260 ℃, the reaction temperature is less by-products to proceed at 260 ℃ or less Pyrolysis of raw materials can be prevented.

The polycondensation step is to produce a polyester by polycondensing the oligomer prepared by the ester process at 240 ~ 285 ℃ 180 ~ 210 minutes, 40 ~ 100rpm.

In the present invention, the reaction is carried out at a high temperature of 240 to 285 ° C in order to prepare an aromatic copolyester polymer.

Next, in the polyester resin for preparing the sheath portion, the esterification step is subjected to an esterification reaction step of esterifying at 240-260 ° C. reaction temperature for 2 to 4 hours under a pressure of 2.0 to 2.5 kgf / cm 2.

The polycondensation step is a polycondensation step of polymerizing the ester reactant for 40 to 100 minutes at a high temperature of 275 ~ 285 ℃ at 0.1 ~ 1 Torr pressure.

The polycondensation process of the core part and the sheath part is carried out at a high temperature, wherein the selection of the catalyst and the heat stabilizer is important.

In the polymerization process, a titanium catalyst or an antimony catalyst may be used as the polymerization catalyst. This can be applied to both the core resin and the sheath polyester resin.

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 the two catalysts. When the titanium catalyst and the antimony catalyst are mixed and used, a titanium catalyst and an antimony catalyst are used. It would be preferable to use a mixture of 75 to 50:50.

As the catalyst used in the polymerization reaction in the present invention, an antimony compound was used, a phosphorus compound was used to suppress discoloration at high temperatures, and as an antimony compound, antimony oxides such as antimony trioxide, antimony tetraoxide, antimony pentoxide, etc. Halogenated antimony, such as antimony trisulfide, antimony trifluoride, antimony trichloride, antimony triacetate, antimony benzoate, antimony tristearate, and the like were used, and antimony trioxide, antimontriacetate, and the like are preferred because they exhibit excellent effects. The amount is most effective when 100 to 600 ppm is used based on the total weight of the polymer as a theoretical value obtained after the polymerization.

It is preferable to use phosphoric acid and derivatives thereof such as phosphoric acid, monomethyl phosphate trimethyl phosphate and tributyl phosphate, and among these, trimethyl phosphate or triphenyl phosphite is preferable, and the amount of phosphorus compound is preferably used. It is most effective when using 100 to 500 ppm based on the total weight of the polymer as a theoretical value obtained after the polymerization.

Next, it is possible to produce a composite fiber by spinning the polyester resin prepared above. It can produce a composite fiber by spinning at a spinning temperature of 260 ~ 275 ℃, to produce a composite fiber by proceeding with a draw ratio of 2 to 4 times at a spinning speed 3500 ~ 4500rpm.

The ratio of the core part and the sheath part may be formed in a weight ratio of 3: 7 to 7: 3. The prepared composite fiber is characterized in that the strength is 3.0 ~ 4.0g / de, elongation 30 ~ 70%.

Hereinafter, examples of the biodegradable polyester composite fiber of the present invention are shown, but are not limited thereto.

Example  One

Preparation of Resin of Polyester

After adding 10 mol% of adipic acid, 89 mol% of terephthalic acid, and 1 mol% of sulfonic acid metal salt (alkaline earth metal) as a reaction molar ratio into a 250 ml flask equipped with a stirrer and a condenser, the amount of ethylene glycol added was Substance of sulfonic acid metal salt (alkaline metal): Ethylene glycol is added at a weight ratio of 1: 1.2, and then 400 ppm of lithium acetate is added as an esterification catalyst, and the temperature in the reactor is raised to 120 ° C. over 30 minutes from room temperature and stirred. The reaction was heated to 250 ° C. for 120 minutes. 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. The stirring was stopped and discharged to obtain a polyester resin (1) in the core portion.

In the same manner as described above, a polyester resin (2) of the cis portion was prepared, wherein the acid component and the sulfonic acid metal salt (alkaline earth metal) were used as 10 mol% of adipic acid, 69 mol% of terephthalic acid, 20 mol% of isophthalic acid, and 1 mol% of sulfonic acid metal salt. ),

The esterification process is subjected to an esterification reaction of esterification for 2 hours at a reaction temperature of 260 ° C. under a pressure of 2.5 kgf / cm 2, followed by polymerization of the ester reactants at a temperature of 285 ° C. at 0.1 Torr for 100 minutes. The combining step was carried out to obtain a polyester resin (2).

Preparation of Composite Fiber

On the basis of the polyester resin (1) and the polyester resin (2) prepared above, a cis-core composite fiber of 50D / 24F (50 denier / 24 filaments) was prepared. The polyester resin (1) was a core type. And polyester resin (2) were made into the sheath type as the weight ratio of 7: 3 (polyester resin (1): polyester resin (2)).

Preparation of the composite fiber was carried out under the condition of spinning temperature 265 ℃, spinning speed 4500rpm, elongation ratio 3.0.

Example  2

The same procedure as in Example 1 was carried out, except that the polyester resin (2) of the cis portion was 10 mol% of adipic acid, 62 mol% of terephthalic acid, 27 mol% of isophthalic acid, and 1 mol% of sulfonic acid metal salt, and an acid component and a sulfonic acid metal salt (alkaline earth metal). ) Was mixed.

Example  3 and Example  4

Example 1 and Example 2 were carried out in the same manner, but a composite fiber was prepared using a weight ratio of polyester resin (1) to polyester resin (2) 5: 5.

Example  5 and Example  6

In the same manner as in Example 1 and Example 2, respectively, 75D / 24F (75 denier / 24 filaments) of a composite fiber was prepared.

Example  7 and Example  8

In the same manner as in Example 3 and Example 4, respectively, 75D / 24F (75 denier / 24 filaments) of a composite fiber was prepared.

-Hydrolysis rate measuring method

After injecting the sample into distilled water at 100 ° C, hydrolysis was performed for 96 hours, and the inherent viscosity before and after hydrolysis of each sample was measured. Intrinsic viscosity is a value that represents the molecular weight of a polymer, and a lot of hydrolysis means that the molecular weight decreases.

The reason for quoting the degree of hydrolysis is to confirm the degree of biodegradability. The biodegradation mechanism is hydrolysis of the main chain of the polymer in the first reaction, resulting in low molecular weight and then decomposed into CO ₂ , water, and biomass by the microorganism in the second reaction. Will.

division Specifications De ' Strength (g / de) Shinto (%) Hydrolysis Rate (%) Example 1 50D / 24F 49.1 3.5 35.5 81 Example 2 50D / 24F 49.7 3.6 35.5 84 Example 3 50D / 24F 50.2 3.4 30.7 83 Example 4 50D / 24F 50.1 3.4 33.6 82 Example 5 75D / 24F 75.1 3.6 34.6 80 Example 6 75D / 24F 75.2 3.4 34.8 83 Example 7 75D / 24F 74.5 3.2 30.8 81 Example 8 75D / 24F 74.8 3.5 36.1 84

The polyester resin used in the composite fiber according to the present invention belongs to the glass transition temperature range of 50 ~ 65 ℃ and all can be spun alone.

The composite fiber produced according to the present invention has a high strength, maintaining a hydrolysis rate of 80% or more, and also has excellent biodegradability.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be obvious to the person.

Claims (5)

In the polyester sheath core type composite fiber,
A polyester produced by mixing an acid component comprising an aliphatic acid containing a carboxylic acid group and an aromatic acid containing a phenylene group, a sulfonic acid metal salt, and a diol component having 2 to 14 carbon atoms, followed by esterification and polycondensation,
The core portion is mixed with 10-20 mol% of aliphatic acid, 80-90 mol% of aromatic acid, and 0.5-1.5 mol% of sulfonic acid metal salt, and the ratio of the substance and diol component containing an acid component and a sulfonic acid metal salt is 1.0: 1.0-1.4 by weight. Mixed with
The cis moiety is mixed with 10-20 mol% of aliphatic acid, 40-60 mol% of terephthalic acid, 20-40 mol% of isophthalic acid and 0.5-1.5 mol% of sulfonic acid metal salt, which is any of adipic acid, succinic acid and glutaric acid. Biodegradable polyester composite fiber for screen fabrics in which the ratio of the substance containing diol and the sulfonate metal salt and the diol component is mixed in a weight ratio of 1.0: 1.2 to 1.4.
The method of claim 1,
The aliphatic acid of the core portion is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, citric acid (Citric acid), pimeric acid, azelaic acid, sebasic acid, nonanoic acid, decanoic acid, dodecanoic acid and Biodegradable polyester composite fiber for screen fabrics, characterized in that at least one selected from the group consisting of hexanodecanoic acid (Hexadecanoic acid).
The method of claim 1,
The sulfonic acid metal salt is biodegradable polyester composite fiber for screen fabric, characterized in that the alkali metal or alkaline earth metal.
The method of claim 1,
Ethylene Glycol, Propylene Glycol, Trimethyl Glycol, Tetramethylene Glycol, Pentamethyl Glycol, Hexamethylene Glycol having 2 to 14 carbon atoms Hexamethylene Glycol, Heptamethylene Glycol, Octamethylene Glycol, Nonamethylene Glycol, Decamethylene Glycol, Undecamethylene Glycol, Dodecamethylene Glycol Dodecamethylene Glycol), tridecamethylene glycol (Tridecamethylene Glycol) and tetradecamethylene glycol (Tetradecamethylene Glycol) Biodegradable polyester composite fiber for screen fabrics, characterized in that at least one selected from the group consisting of.
The method of claim 1,
Biodegradable polyester composite fiber for a screen fabric, characterized in that the weight ratio of the core portion and the sheath portion is 3: 7 ~ 7: 3.