KR20200123934A - Polyester Composite Fibers Using materials from biomass and Method Preparing Same - Google Patents

Abstract

The present invention relates to polyester composite fibers using a biomass-derived raw material containing a polyethylene furanoate (PEF) resin and a polytrimethylene furanoate (PTF) resin and, more specifically, to polyester composite fibers having very excellent crimp rate and elasticity, and to side-by-side polyester-based composite fibers formed of a polytrimethylene furanoate (PTF) resin of a high viscosity resin and a polyethylene furanoate (PEF) resin of a low viscosity resin.

Description

Polyester Composite Fibers Using materials from biomass and Method Preparing Same}

The present invention relates to a side-by-side type polyester composite fiber using a biomass-derived raw material, and relates to a polyester composite fiber using a biomass-derived raw material using furandicarboxylic acid, a material derived from biomass.

The discovery and application of eco-friendly materials has been steadily progressing as global warming accelerates. Polymers produced from fossil fuels, represented by petroleum, have a limit in their reserves, and the emission of carbon dioxide is high, so it is urgent to replace them with eco-friendly materials. However, as products have been developed with a focus on biodegradability, existing eco-friendly materials have a disadvantage that there are many areas that need improvement in actual commercialization due to the inherent properties of the material, such as hydrolysis, poor radioactivity, and hard touch.

Recently, the development of textile products using eco-friendly materials using biomass has been actively progressing, and is being released as a product. Biomass is a generic term for organic substances possessed by living organisms in nature, but may refer to organic raw materials that can be specially converted to energy or substituted for petrochemical-derived substances through a substance cycle.

Petroleum, which accounts for a large portion of the current energy source, is expected to be depleted in the near future, and with the second oil shock that began at the end of 1978, studies on the use of biomass have become active in countries around the world. .

Due to these social phenomena, the environmental burden is low in the textile industry, and various fibers and textile materials are attracting attention by using biomass.

For example, polytrimethylene terephthalate (PTT), a polyester-based compound, can be prepared by esterification and condensation polymerization of terephthalic acid (TPA) or an ester-forming derivative thereof and 1,3-propanediol. And a technology for obtaining 1,3-propanediol from biomass is being developed.

In this regard, U.S. Patent No. 8,415,496 synthesizes terephthalic acid from muconic acid, a biomass through the following route, and replaces terephthalic acid, a raw material based on petrochemicals, as a raw material derived from biomass. I have disclosed the technology to do.

Polyethylenefuranoate (PEF) is in the spotlight as a next-generation ester-based polymer material that can replace polyester (PET), which is currently widely used, and this is where the existing polyester is a petrochemical raw material, terephthalic acid. TPA), whereas polyethylene furanoate is an eco-friendly resin that applies furandicarboxylic acid (FDCA) produced by dehydration, oxidation, and purification processes of sugar syrup extracted from plants.

Examples of resins commercialized as eco-friendly resins similar to this include biopolyester polymerized using ethylene glycol derived from biomass, or polytrimethylene terephthalate (PTT) polymerized with propanediol (PDO) extracted from corn. The technology of yarns made using these has already been commercialized, but there is a problem that they are not 100% biomass.

Japanese Patent Laid-Open No. 2016-531186 discloses a processing method and such a method for providing articles such as containers formed of polyethylene furanoate and polyethylene furanoate, but for various products using polyethylene furanoate It is not disclosed.

The present invention is invented to solve the above problems, and provides a side-by-side type polyester composite fiber using a biomass-derived raw material using a polyethylene furanoate (PEF) resin polymerized with a material derived from biomass. It aims to do.

In addition, it is an object of the present invention to provide a stretchable polyester-based composite fiber derived from 100% biomass by using the polyethylene furanoate (PEF) resin and polytrimethylene furanoate (PTF) resin.

The present invention provides a polyester composite fiber using a biomass-derived raw material, characterized in that it contains a polyethylene furanoate (PEF) resin and a polytrimethylene furanoate (PTF) resin.

In addition, the polyester-based composite fiber is a side-by-side composite fiber formed of a high-viscosity resin and a low-viscosity resin, and the high-viscosity resin is a biomass-derived furandicarboxylic acid (FDCA) and a biomass-derived 1, Polytrimethylenefuranoate resin (PTF) formed by polymerizing 3-propanediol, and the low viscosity resin is formed by polymerizing furandicarboxylic acid (FDCA) derived from biomass and ethylene glycol derived from biomass. It provides a polyester composite fiber using a raw material derived from biomass, characterized in that the low viscosity polyethylene furanoate (PEF) resin.

In addition, the high viscosity resin has an intrinsic viscosity (IV) of 0.6 to 1.2 dl/g, and the low viscosity resin has an intrinsic viscosity (IV) of 0.40 to 0.60 dl/g. Provides composite fibers.

In addition, it provides a polyester composite fiber using a biomass-derived raw material, characterized in that the difference in intrinsic viscosity between the high viscosity resin and the low viscosity resin is 0.20 ~ 0.80dl / g.

In addition, the high viscosity resin and the low viscosity resin provides a polyester composite fiber using a biomass-derived raw material, characterized in that the weight ratio of 3:7 to 7:3.

As described above, the polyester composite fiber using the biomass-derived raw material according to the present invention is an organic raw material obtained from natural biomass of all polymer resins of polytrimethylenefuranoate resin (PTF) and polyethylene furanoate (PEF) resin. As the bio-carbon content is over 98%, it has an environmentally friendly effect.

In addition, through the high-viscosity resin and the low-viscosity resin, the side-by-side type composite fiber has a very excellent crimp rate and elasticity.

Hereinafter, a preferred embodiment of the present invention will be described in detail. First, in describing the present invention, detailed descriptions of related known functions or configurations are omitted so as not to obscure the subject matter of the present invention.

The terms'about','substantially', etc. of the degree used in the present specification are used at or close to the numerical value when manufacturing and material tolerances specific to the stated meaning are presented, and are used in the sense of the present invention. To assist, accurate or absolute figures are used to prevent unfair use of the stated disclosure by unscrupulous infringers.

In the present invention, biomass-derived refers to organic raw materials obtained from natural biomass, not raw materials produced from petrochemical origin.

The present invention relates to a polyester composite fiber using a raw material derived from biomass, characterized in that it contains a polyethylene furanoate (PolyEthylene Furanoate, PEF) resin and a polytrimethylene furanoate (PolyTrimethylene Furanoate, PTF) resin.

The polyethylene furanoate resin is a polymer resin formed by polymerizing furandicarboxylic acid (FDCA) prepared using sugar syrup extracted from plants and ethylene glycol derived from biomass, and the poly PolyTrimethylene Furanoate (PTF) resin is a polymer resin formed by polymerizing furandicarboxylic acid (FDCA) and biomass-derived ethylene glycol. The polyester composite fiber of the present invention is 100% biomass. It is a fiber made from derived raw materials.

The polyester composite fiber using the biomass-derived raw material according to the present invention as described above may be formed of a side-by-side composite fiber formed of a high-viscosity resin and a low-viscosity resin, thereby imparting a stretchable function.

The high viscosity resin is a polytrimethylene furanoate resin (PTF) formed by polymerizing biomass-derived furandicarboxylic acid (FDCA) and biomass-derived 1,3-propanediol, and the low viscosity resin is It may be composed of a low viscosity polyethylene furanoate (PEF) resin formed by polymerizing mass-derived furandicarboxylic acid (FDCA) and biomass-derived ethylene glycol.

The high viscosity resin, polytrimethylene furanoate (PTF) resin, has an intrinsic viscosity (IV) of 0.6 to 1.2 dl/g, and the low viscosity resin, low viscosity polyethylene furanoate (PEF) resin, has intrinsic viscosity (IV) It would be desirable to be between 0.40 and 0.60 dl/g.

The intrinsic viscosity of the polyethylene furanoate (PEF) resin and the polytrimethylene furanoate (PTF) resin may be controlled by controlling the degree of polymerization and molecular weight.

The difference in intrinsic viscosity between the high-viscosity resin and the low-viscosity resin is preferably 0.20 to 0.80 dl/g.If the intrinsic viscosity difference is less than 0.20 dl/g, the elasticity of the composite fiber may be lowered, and the intrinsic viscosity difference is 0.80 dl/g. If it exceeds, the spinning processability may be degraded due to howitzer during spinning.

The weight ratio of the high-viscosity resin and the low-viscosity resin may be adjusted according to the purpose of use, but it is preferable that the weight ratio is 3:7 to 7:3 for the elasticity of the formed polyester composite fiber.

The side-by-side type polyester composite fiber formed of polytrimethylene furanoate (PTF) resin, which is a high viscosity resin and low viscosity polyethylene furanoate (PEF) resin, which is a low viscosity resin, is a general high viscosity, low viscosity poly It may be produced in the same way as the side-by-side type composite fiber formed of ester resin.

As described above, the polyester composite fiber using the biomass-derived raw material of the present invention is an organic raw material in which all polymer resins forming the composite fiber are obtained from natural biomass, and is a very eco-friendly fiber with a biocarbon content of 98% or more.

Hereinafter, an example of a method for producing a polyester composite fiber using a biomass-derived raw material according to the present invention is shown, but the present invention is not limited to the examples.

Example 1 to 6

Polytrimethylenefuranoate (PTF) resin polymerized with biomass-derived furandicarboxylic acid (FDCA) and biomass-derived 1,3 propane diol was used as a high-viscosity resin, and as a low-viscosity resin, biomass-derived Polyethylene furanoate (PEF) resin polymerized with furandicarboxylic acid (FDCA) and biomass-derived ethylene glycol is used to produce polyester composite fibers using biomass-derived raw materials through a general side-by-side composite spinning method. It was manufactured.

In Examples 1 to 6, polyester composite fibers were prepared by varying the intrinsic viscosity and weight ratio of the high and low viscosity resins according to the Examples, and the intrinsic viscosity and weight ratio are shown in Table 1.

Comparative Example 1

A side-sided composite fiber was prepared in the same manner as in Example 1, but a polytrimethylene terephthalate (PTT) resin polymerized with terephthalic acid derived from petrochemical and 1,3 propane diol derived from petrochemical as a high viscosity resin was used.

Table 1 shows the intrinsic viscosity and weight ratio of the high viscosity resin and the low viscosity resin.

Comparative Example 2

A side-sided composite fiber was prepared in the same manner as in Example 4, but a polyethylene terephthalate (PET) resin polymerized with terephthalic acid derived from petrochemical and ethylene glycol derived from petrochemical as a high viscosity resin was used.

Table 1 shows the intrinsic viscosity and weight ratio of the high viscosity resin and the low viscosity resin.

division High viscosity resin Low viscosity resin Suzy IV(dl/g) Weight ratio Suzy IV(dl/g) Weight ratio Example 1 PTF 1.0 50 PEF 0.45 50 Example 2 PTF 1.0 70 PEF 0.45 30 Example 3 PTF 1.0 30 PEF 0.45 70 Example 4 PTF 0.65 50 PEF 0.4 50 Example 5 PTF 1.0 90 PEF 0.45 10 Example 6 PTF 0.65 50 PEF 0.55 50 Comparative Example 1 PTT 1.0 50 PEF 0.45 50 Comparative Example 2 PET 0.64 50 PEF 0.45 50

◎ Property evaluation method

The physical properties of the polyester composite fibers of Examples 1 to 6 and Comparative Examples 1 and 2 prepared above were measured and shown in Table 2.

* Intrinsic Viscosity (IV): After each polymer was sufficiently dissolved in ortho-chlorophenol at 120°C at a concentration of 1%, it was measured using a Woberod type viscometer in a thermostat at 30°C.

* Fairness evaluation: Grade 1 production/total production*100 = yield (based on weight)

* Bio-carbon content: measured by ASTM D6866-16.

ASTM D6866, which measures the content of bio-carbon, measures the ratio of radiocarbon (14C) in a sample to radiocarbon in the current reference material with the same concept as the radiocarbon dating technique. This ratio is expressed in units called pMC (percent modern carbon). If the current radiocarbon and fossil carbon (ie, no radiocarbon) of the sample to be analyzed are measured, the pMC value obtained here is directly related to the biocarbon content of the sample.

* Crimping rate (Tc, %): This is a measurement of the crimp rate of the examination. Take a sample with a 1m long skein as long as 3,000 ÷ fineness ÷ 4. When this sample is subjected to hot water treatment, it is treated for 20 minutes in hot water (100°C) under a load of 1 g, which is a load that does not cause entanglement of each fiber strand, and then the load is removed and left for 4 hours. And let it air dry. After natural drying, a load of 6g is applied to the sample, the length L1 is measured after 1 minute, and a load of 600g is applied, and the length L2 is measured after 1 minute. The value measured in this way is calculated for the crimp rate by the following equation.

Crimp rate (%) = (L2-L1)/L2 × 100

5. Elasticity: 1m length of fabric is collected in the horizontal and vertical directions, immersed in distilled water at 60℃, boiled for 15 minutes, then boiled for 15 minutes, immersed in erkantol BX aqueous solution of 60℃, 2g/l for 30 seconds, and take out again. Measure X ₁ after ₁ min of 0.2g/D load in a wet state, dry for 1hr at 50~60℃, cool for 1hr, measure X ₂ after 1 min of 0.002g/D load, and calculate the elasticity by the following equation.

Elasticity(%)=((X ₁ -X ₂ )/ X ₁ )100

division Radiation fairness (%) Bio carbon content (%) Crimp rate (%) Flexibility(%) Example 1 95 99.4 50 38 Example 2 93 99.2 46 32 Example 3 92 98.7 42 30 Example 4 94 99.2 38 24 Example 5 Non-radiation - - - Example 6 92 98.7 17 8 Comparative Example 1 95 44.4 48 33 Comparative Example 2 94 35.8 14 6

As shown in Table 2, Examples 1 to 6 according to the present invention spun except for Example 5 had a biocarbon content of 98%, but Comparative Examples 1 and 2 were 50% or less, so that the polyester composite fiber of the present invention was very It can be seen that it is an eco-friendly fiber.

In addition, as in Example 5, when the content of the high-viscosity resin is too high, it is preferable that the content of the high-viscosity resin is 70% by weight or less, as it is impossible to spin because the howitzer occurs in the spinning process.

In addition, as in Example 6, when the difference in intrinsic viscosity of the high-viscosity resin and the low-viscosity resin is less than 0.20, it can be seen that the crimp rate and elasticity are deteriorated.

In addition, when comparing Example 1 and Comparative Example 1 and Example 4 and Comparative Example 2, when the difference in intrinsic viscosity and weight ratio of the high-viscosity resin and the low-viscosity resin are similar, polytrimethylenefuranoate (PTF) as a high-viscosity resin It can be seen that Example 1 and Example 4 using a resin are more excellent in crimp rate and elasticity.

Claims (5)

Polyester composite fiber using a biomass-derived raw material, characterized in that it contains a polyethylene furanoate (PEF) resin and a polytrimethylene furanoate (PTF) resin. The method of claim 1,
The polyester-based composite fiber is a side-by-side composite fiber formed of a high viscosity resin and a low viscosity resin,
The high viscosity resin is a polytrimethylene furanoate resin (PTF) formed by polymerizing biomass-derived furandicarboxylic acid (FDCA) and biomass-derived 1,3-propanediol, and the low viscosity resin is Polyester composite fiber using a biomass-derived raw material, characterized in that it is a low viscosity polyethylene furanoate (PEF) resin formed by polymerizing mass-derived furandicarboxylic acid (FDCA) and biomass-derived ethylene glycol. The method of claim 1,
The high viscosity resin has an intrinsic viscosity (IV) of 0.6 to 1.2 dl/g, and the low viscosity resin has an intrinsic viscosity (IV) of 0.40 to 0.60 dl/g. . The method of claim 2,
Polyester composite fibers using biomass-derived raw materials, characterized in that the difference in intrinsic viscosity between the high-viscosity resin and the low-viscosity resin is 0.20 ~ 0.80dl/g. The method of claim 2,
The high-viscosity resin and the low-viscosity resin are polyester composite fibers using a biomass-derived raw material, characterized in that the weight ratio is 3:7 to 7:3.