KR0150177B1 - Method of manufacturing polyester fiber with anti-microbial property - Google Patents

Abstract

In the present invention, in the preparation of a polyester by reacting an acid component with a diol component, 0.2 to 2.0 mol% of a compound represented by the following general formula (I) or (II) is produced as a melt viscosity improving agent during the ester reaction. In addition, during the polycondensation reaction, the compound represented by the following general formula (III) or (IV) is added to 0.1 to 1.5 mol% of the resulting polyester to prepare a polymer, and at any stage before spinning, the antibacterial and deodorizing compound The present invention relates to a method for producing a polyester for textiles having excellent antibacterial and deodorizing properties, characterized by compounding phosphonium phosphate.

Wherein R ₁ is the same as or different from each other, selected from C ₄ H ₉ , C ₆ H ₅ , H, R ₂ is C _n H _2n (2n10), and X is hydrogen, methyl, n-butyl or a phenyl group and, R ₃ is hydrogen, chlorine, methyl or phenyl, R ₄ is hydrogen, methyl or phenyl, R ₅ is a t- butyl group.

Description

Manufacturing method of polyester for fiber excellent in antibacterial deodorization

The present invention relates to a method for producing a polyester for antibacterial and deodorizing fibers having a higher spinning viscosity than a conventional polymer and excellent in spinning workability. As a further improving agent, a compound represented by the following general formula (I) or (II) is added, and a compound represented by the general formula (III) or (IV) is added during the polymerization reaction to prepare a polymer,絲 Previous) The present invention relates to a method for producing a polyester for an antibacterial and deodorizing fiber having a good melt viscosity by compounding an antibacterial and deodorizing conic phosphate in which an ion-exchangeable ion is replaced with an antimicrobial metal ion at any stage.

Wherein R ₁ is the same as or different from each other, selected from C ₄ H ₉ , C ₆ H ₅ , H, R ₂ is C _n H _2n (2n10), and X is hydrogen, methyl, n-butyl or a phenyl group and, R ₃ is hydrogen, chlorine, methyl or phenyl, R ₄ is hydrogen, methyl or phenyl, R ₅ is a t- butyl group.

Recently, especially among the synthetic fibers, the antibacterial and deodorant fibers include beddings such as duvets, matrices, cushions, clothing fields such as underwear, socks, sportswear, interior fields such as wallpaper, carpets, curtains, household goods such as towels, towels, In addition, the situation is widely used for industrial materials such as filtration blower.

By the way, microorganisms such as bacteria and fungi exist in human living environment, and these microorganisms cause skin disorders by making them easily adhere to the human body or clothes through breeding media or degenerate the fiber to embrittle them, and give off odors. Sometimes.

In particular, since synthetic fibers have low absorption of sweat, garments made of synthetic fibers may cause bad smell by breeding or decaying microorganisms such as bacteria and mold on skin and clothing due to sweating when worn. Sometimes it can do harm. Therefore, there is an urgent need for the development of polymers to obtain cleaner, more comfortable and hygienic polyester fibers.

In order to solve the problems caused by microorganisms such as bacteria and fungi, a method of obtaining a polymer for antibacterial and deodorizing fibers by adding an antimicrobial additive during synthesis or compounding is known, for example, Japanese Patent Publication Although H1-42288 introduces a method of preparing a slurry by adding an antimicrobial deodorant to the reaction monomer in the polymerization process, the additive is agglomerated during the polymerization reaction or acts as a catalyst to prevent the There are many disadvantages of single yarn (斷 絲) occurrence during the weaving process, and antimicrobial additives are distributed inside the cross-section of the fiber when manufacturing the fiber has a problem of inferior antimicrobial properties.

In addition, Japanese Patent Publication No. 54-38951 discloses antimicrobial properties by forming ion-exchangeable polyester fibers and treating them with aqueous solutions such as copper salts and silver salts. The problem is that the touch becomes worse.

In case of general polyester chip, it has melt viscosity of about 2800 ~ 3000 poise when measuring melt viscosity under the condition of 100Rad / Sec at 285 ℃, but spinning by adding more than 3.0% by weight of antimicrobial inorganic fine particles to polyester chip In this case, the melt viscosity is rapidly lowered to 1000 poise or less, and thus the hardness is lower than that of general polyester chips, and the pack pressure decreases rapidly when the chip is injected into the extruder process. Not only can not be obtained, but also severely causes non-ejection, tip pressure hunting, dropping and single yarn occurrence, and causes the work efficiency to be greatly reduced.

It is an object of the present invention to provide a method for producing an antibacterial deodorizing polymer excellent in melt viscosity in order to solve this problem.

Therefore, in the present invention, a polymer is obtained by adding a compound represented by the following general formula (I) or (II) and a compound represented by the following general formula (III) or (IV) as a melt viscosity improving agent during polyester production, By compounding antibacterial and deodorizing conic phosphate, it is easy to obtain polyester for antibacterial and deodorizing fibers having good physical properties with good antimicrobial deodorizing properties and high melt viscosity when spinning and stretching to produce fibers.

The present invention will be described in detail as follows.

The polyester for the antimicrobial deodorant fiber of the present invention reacts a common acid component with a diol component to prepare a polyester. During ester reaction, zinc acetate is dissolved in ethylene glycol as a catalyst to an oligomer, and the following general formula (I) or ( 0.2-2.0 mol% of the viscosity improving agent represented by II) is added with respect to produced | generated polyester, and the viscosity improver represented by following General formula (III) or (IV) is 0.1-1.5 mol with respect to the produced polyester at the time of polycondensation reaction. The reaction was carried out by the addition of% to prepare a polymer and compounded with phosphonium phosphium as an antimicrobial deodorizing compound at any stage before spinning.

Wherein R ₁ is the same as or different from each other, selected from C ₄ H ₉ , C ₆ H ₅ , H, R ₂ is C _n H _2n (2n10), and X is hydrogen, methyl, n-butyl or a phenyl group and, R ₃ is hydrogen, chlorine, methyl or phenyl, R ₄ is hydrogen, methyl or phenyl, R ₅ is a t- butyl group.

The antimicrobial deodorant conium phosphate used in the present invention is obtained by partially or completely replacing ion exchangeable ions with antimicrobial deodorant metal ions.

The antimicrobial deodorant conium phosphate used in the present invention is an example of the antimicrobial deodorant metal ions include silver, copper, zinc or bismuth, in particular in consideration of the antibacterial deodorizing effect, by using silver, copper, zinc It was possible to obtain conium phosphate having better antibacterial deodorization.

The antimicrobial metal ions may be contained in an amount of 0.1 to 17% relative to the phosphonium phosphate. In particular, in the present invention, 0.01 to 10% of copper ions, 0.05 to 10% of zinc ions, and 0.01 to 6.5% of silver ions are used to obtain an excellent antibacterial deodorizing effect. Contained antibacterial and deodorant conium phosphate was used (% indicating the content of metal ions means the weight percent based on the weight of the conic phosphate after drying at 120 ℃).

The amount of the antimicrobial deodorant conium phosphate used is preferably 0.05 to 10% by weight, preferably 0.05 to 3% by weight, based on the produced polyester, in terms of antibacterial deodorization and physical properties of the master batch.

The antimicrobial deodorant conium phosphate used in the present invention is effective in that the particle size is as small as possible, but in consideration of economic aspects, it is preferable that the range of 0.01 ~ 5μ.

If the addition amount of the compound of the general formula (I) or (II) is less than 0.2 mol% or the addition amount of the compound of the general formula (III) or (IV) is less than 0.1 mol%, the melt viscosity improvement effect is weak. ) Or (II) when the amount of the compound added exceeds 2.0 mol% or the amount of the compound of the general formula (III) or (IV) exceeds 1.5 mol% due to a sharp increase in the melt viscosity and poor physical properties of the produced fiber Will not.

The polyester resin for the antimicrobial deodorant fiber of the present invention was prepared by using the compounds of the general formulas (I) to (IV) which are viscosity improvers and injecting the antimicrobial deodorant conic phosphate at any stage before spinning.

All known methods may be used for the method of adding the compounds of the general formulas (I) to (IV), but in the ester reaction, zinc slurry is used as a catalyst to dissolve in ethylene glycol, and a slurry added with a viscosity improver is added or condensation polymerization. It is preferred to add together with the polycondensation catalyst in the reaction.

Polyester for the antimicrobial deodorant fiber of the present invention is prepared by a known method, for example, ester reaction at 240 ~ 250 ℃ and after the addition of a polymerization catalyst polycondensation reaction at 280 ~ 285 ℃, pre-drying 110 ℃, It was prepared by vacuum drying for 5 hours at 130 ℃.

In addition, the temperature of the spreader zones A, B, C, gear pump and spin block of the spinning device is set to 250, 260, 270, 280, and 290 ° C, respectively, and is radiated at a spinning speed of 1370 m / min. Good results were obtained.

The following examples and comparative examples illustrate the invention in more detail, but do not limit the scope of the invention.

Example 1

Structural formula for the polyethylene terephthalate 4780g oligomer obtained by esterification of terephthalic acid and ethylene glycol (addition ratio 1: 1.3)

After dissolving 88.7 g of a compound represented by 25.6 g of zinc acetate in 3% ethylene glycol and esterifying at 245 ° C. for 1 hour and 15 minutes,

78.7 g of the compound and triethyl phosphate, cobalt acetate, and 80.5 g of a mixed catalyst of antimony trioxide and butylene maleate were added to condense for 2 hours at 280-285 ° C. to prepare a polyester, followed by predrying 110 ° C., Vacuum drying at 130 ° C. for 5 hours to measure melt viscosity and intrinsic viscosity at 285 ° C. and 100 Rad / Sec, and the results are shown in Table 1, and the prepared polyester chip and copper-zinc-silver having an average particle diameter of 0.4 μm. Compounding 38 g of phosphate conium (copper 8%, zinc 8%, silver 6.5%) and spinning at a spinning speed of 1370m / min, evaluating the degree of non-emission, tip pressure hunting, dropping, single yarn, carbonaceous material, and wind surface The results are shown in Table 2.

Example 2

In Example 1, the following compound

24.3 g of zinc acetate and 26.4 g of zinc acetate were added and dissolved in 3% ethylene glycol, followed by esterification at 245 ° C. for 1 hour and 10 minutes, followed by 78.2 g of a mixed catalyst of triethyl phosphate, cobalt acetate, antimony trioxide and butylene maleate. The following compound

Except for producing polyester by condensation polymerization at 280 ~ 285 ℃ for 2 hours and 5 minutes with 43.6g, the same procedure was followed to evaluate the physical properties and properties of polyester and fiber. It is described in.

Comparative Example 1

In Example 1, the following compound was contained in an amount of 19.7 mol of an oligomer.

After adding 3.8 g and 28.6 g of zinc acetate for ester reaction at 245 ° C. for 1 hour and 10 minutes, 62.4 g of mixed catalyst of Example 1 was added to polycondensate at 280 to 285 ° C. for 2 hours and 10 minutes to prepare polyester. Except for one, the properties and properties of polyesters and fibers were evaluated and listed in Tables 1 and 2.

Comparative Example 2

Except that in Example 1, without using a melt viscosity improver, 71.9 g of the mixed catalyst of Example 1 was added to 22.3 mol of the oligomer, and condensation polymerization at 280 ~ 285 ℃ for 2 hours and 5 minutes to prepare a polyester In the same manner, the physical properties and properties of the polyesters and fibers were evaluated and listed in Tables 1 and 2.

Comparative Example 3

In Example 1, the following compound was contained in an amount of 19.7 mol of an oligomer.

6.58 g and 28.6 g of zinc acetate were added for ester reaction at 245 ° C. for 1 hour and 10 minutes, and then 62.4 g of the mixed catalyst of Example 1 was added to polycondensate at 280 to 285 ° C. for 2 hours and 10 minutes to prepare polyester. Except for one, the properties and properties of polyesters and fibers were evaluated and listed in Tables 1 and 2.

[Comparative Example 4]

In Example 1, the following compound was added to 22.3 mol of an oligomer.

5.8 g and 71.9 g of the mixed catalyst of Example 1 were added thereto, followed by condensation polymerization at 280 to 285 ° C. for 2 hours and 5 minutes to prepare a polyester. The properties and properties of the polyester and the fiber were evaluated. 1 and Table 2.

[Comparative Example 5]

In Example 1, the amount of the oligomer was 21.9 mol.

After adding 9.3 g and 24.5 g of zinc acetate for ester reaction at 245 ° C. for 1 hour and 20 minutes, 58.1 g of the mixed catalyst of Example 1 was added thereto, followed by polymerization for 2 hours and 15 minutes at 280˜285 ° C. to prepare polyester. Except for one, the properties and properties of polyesters and fibers were evaluated and listed in Tables 1 and 2.

※ How to measure properties

1. Melt Viscosity: Measured by parallel plate method at 285 ℃ and 100Rad / Sec.

2. Intrinsic Viscosity: A mixture of phenol and tetrachloroethanol 1: 1 and the sample were stirred and dissolved in an aqueous bath at 100 ° C., and then measured by a Ubelrod viscometer in a thermostat.

※ Visually determined by non-emergence, linear pressure hunting, dropping, single yarn, carbonized material, and wind surface

(Circle): It does not occur at all. △: slightly occurs. X: Very badly generated.

Claims (3)

In preparing polyester by reacting an acid component with a diol component, 0.2 to 2.0 mol% of a compound represented by the following general formula (I) or (II) is added to the resulting polyester as a melt viscosity improving agent during the ester reaction, During the polycondensation reaction, a compound represented by the following general formula (III) or (IV) is added to 0.1 to 1.5 mol% of the resulting polyester to prepare a polymer, and as an antimicrobial deodorizing compound at any stage before spinning, A method for producing a polyester for textiles having excellent antibacterial and deodorizing property, characterized by compounding um. Wherein R ₁ is the same as or different from each other, selected from C ₄ H ₉ , C ₆ H ₅ , H, R ₂ is C _n H _2n (2n10), and X is hydrogen, methyl, n-butyl or a phenyl group and, R ₃ is hydrogen, chlorine, methyl or phenyl, R ₄ is hydrogen, methyl or phenyl, R ₅ is a t- butyl group. The method of claim 1, wherein the antimicrobial deodorizing corn phosphate is an antibacterial room, characterized in that the metal ion is substituted with copper (0/01 ~ 10%), zinc (0.05 ~ 10%) and silver (0.1 ~ 6.5%) A method for producing polyester for brittleness. The method of claim 1, wherein the amount of the antimicrobial deodorant conium phosphate used is 0.05 to 10% by weight based on the produced polyester.