KR101485686B1 - The dyeing method of ultra-high-strength-fiber with high dye fastness using electronic beam accelerator - Google Patents

Abstract

The present invention relates to a method for a high-fastness dyeing method of ultra high strength fiber by processing with an electron bean accelerator. According to the present invention, provided is a processing method for improving dyeing property of an existing ultra high strength fiber and fixation property of dyes through a surface modification effect and a technology of fixing a dye having at least one double bond or a ring system, which can be polymerized, on the fiber by processing the ultra high strength fiber with the electron beam accelerator.

Description

[0001] The present invention relates to a high-strength fiber fabric for use in an electronic beam accelerator,

The present invention relates to a high-strength dyeing method of an ultra-high-strength fiber fabric by an electron beam accelerator treatment, wherein a dye having at least one double bond or a ring system capable of polymerizing by treating an ultra- To improve the dyeability of the existing ultrahigh strength fiber and improve the fixability of the dye through the surface modification effect.

As demand for ultra-high-strength fibers such as aramid fibers or ultra high molecular weight polyethylene (UHMWPE) is rapidly increasing, researches on dye synthesis and dyeing techniques have been actively carried out, but they are mainly carried out in large companies developing aramid fabrics, dyes and formulations Dyestuffs such as dyed by original dyeing, aramid modification, dyeing by solvent, dyeing by supercritical method are under study. However, P-aramid and ultrahigh molecular weight polyethylene (UHMWPE) I have not been able to.

A study on the research trends related to dyeing processing of domestic aramid fiber has confirmed that most of m-aramid-based technology development has been conducted. The research trends related to P-aramid dyeing are "Reactive dying of photografted (UHMWPE), the most common technique for dyeing ultra-high-molecular-weight polyethylene (UHMWPE) It is nothing but a technology for product development.

In dyeing of ultrahigh strength fibers by the circle method, the fastness is good, but since the pigment has to be incorporated into the polymer in producing the fiber, it is difficult to change the color due to contamination, and a single color must be produced at a time. In addition, it is difficult to produce a small amount of various colors, and it is required to select a pigment having heat resistance, and it has a disadvantage that the physical properties of the yarn are lowered due to pigment incorporation between the polymers.

The dyeing technique of ultrahigh strength fiber material by carrier dyeing is a dyeing method which improves the dyeability by modifying the polymer to make the fiber relaxed structure by using a large amount of solvent to make the fiber structure more loosened. In the case of m-aramid among the aramid composite materials to be commercialized, a variety of colors and dyeability are secured. In the case of p-aramid, however, It is difficult to achieve various colors and coloring properties, and therefore, p-aramid fibers are core and mulled to minimize surface exposure of aramid fibers.

The dyeing technique by ultra-high-temperature high-pressure dyeing requires high heat-resistant dye because it is treated at an ultra-high temperature of 190 ° C or more, requires additional equipment for ultrahigh-temperature high-pressure dyeing, and has a disadvantage of high energy consumption.

Therefore, in the present invention, an existing ultrahigh-strength fiber material, which is difficult to dye and functionalize by complementing the existing wet pretreatment and post-treatment processes in dyeing and surface modification of ultrahigh strength fiber materials, The surface is modified to reduce the surface energy to facilitate functional complexation and dyeing. The electron beam accelerator treatment improves the rate of coloring, color fastness and fastness of ultrahigh strength fibers, and develops materials for protection, safety and composite materials. It is a technical object of the present invention to provide an electron beam accelerator treatment process capable of high-performance salt-forming and printing, composite materials, and post-processing.

Therefore, according to the present invention, in the surface treatment of an ultrahigh strength fiber fabric with an electron beam accelerator having a maximum acceleration energy of 0.1 to 0.7 MeV, a beam power of 5 to 28 KW, a beam current of 10 to 40 mA, and an SF ₆ gas supply system, A high-strength fiber fabric by an electron beam accelerator treatment is provided, which is characterized in that it is subjected to a surface treatment without using a disperse dye and then is dyed with a disperse dye.

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

The high-intensity dyeing method of an ultra-high strength fiber fabric by the electron beam accelerator treatment of the present invention is characterized in that an ultra-high strength fiber fabric is treated through an electron beam accelerator to form a macroscopic (micro-pit) The surface is modified by increasing the number of nano irregularities, the active part is introduced into the surface of the fiber, and the affinity with water is increased to increase the amount of the dye to be dyed, thereby improving the color saturation.

In the present invention, an ultra-high strength fiber fabric is surface-treated with an electron beam accelerator equipped with a maximum acceleration energy of 0.1 to 0.7 MeV, a beam power of 5 to 28 KW, a beam current of 10 to 40 mA, and an SF ₆ (sulfur hexafluoride) Dyeing using disperse dyes to increase salt loading with dyes to improve the color saturation.

The super high strength fiber fabric is supplied to an electron beam accelerator to be surface modified. The electron beam accelerator can use an electron beam accelerator known from Korean Patent No. 10-0687220. The super high strength fiber fabric may be any one of aramid fiber, ultra high molecular weight polyethylene (UHMWPE) fiber, polyester fiber, carbon fiber and glass fiber.

In the present invention, an electron beam having a maximum acceleration energy of 0.1 to 0.7 MeV, a beam power of 5 to 28 KW, a beam current of 10 to 40 mA, and an SF ₆ (sulfur hexafluoride) gas supply system using the simultaneous irradiation method and the co- However, when the beam power is out of the range of 5 to 28 KW, there is a problem that the intrinsic property of the fiber material is deteriorated due to strong electron beam intensity. When the beam current is out of 10 to 40 mA, There is a problem that the material burns, and stabilization can be achieved by using the DSF ₆ (sulfur hexafluoride) gas supply system.

 In particular, the present invention can improve the dyeability without using a photoinitiator and a monomer at the time of surface treatment of the ultra high strength fiber fabric. In the present invention, since the energy of the electron beam irradiated on the super high strength fiber fabric surface is heat- It is possible.

In the present invention, the surface of the ultra-high-strength fiber cloth is pretreated before the surface treatment with the electron beam accelerator to remove contamination which may occur during the spinning and weaving process, thereby performing a more efficient etching process. After immersing in a hot-water refining bath containing 3 to 10 g / l of scouring agent (SS-30), 2 to 6 g / l of SCELAN 606 and 1 to 5 g / l of NaOH at 90 to 100 ° C for 30 to 60 minutes Cold water washing and hot water washing are repeated twice.

Therefore, according to the present invention, it is possible to modify the surface of a fiber by using an electron beam accelerator process capable of continuous processing of an existing ultrahigh strength fiber material, which is difficult to dye and functionalize, to reduce surface energy to facilitate functional complexing and dyeing, To improve the dyeing rate, coloring and fastness of ultrahigh strength fibers and to develop materials for protection, safety and composite materials, and to achieve high performance penetration, printing, fusing composite material and post processing. Process can be provided.

1 is a photograph of a fiber surface of Example 1,
2 is a photograph of the fiber surface of Example 2,
3 is a result of ESR analysis of fibers according to the electron beam irradiation of Example 1,
Fig. 4 shows the results of ESR analysis of fibers according to the electron beam irradiation of Example 2,
FIG. 5 shows a result of CCM (computer color matching) measurement of the first embodiment,
FIG. 6 shows the results of computer color matching (CCM) measurement according to the second embodiment.

The following embodiments are non-limiting examples of the electron beam accelerator processing method of the present invention.

[Examples 1 to 2, Comparative Examples 1 to 2]

1. Preprocessing

The fabric shown in Table 1 was immersed for 30 minutes in a hot water / refining bath at 90 占 폚 containing 3 g / l of an anionic scouring agent (SS-30), 6 g / l of an acryl-based foaming agent (SCLEAN 606) and 1 g / The three and the heat cycle were repeated twice.

2. Electron beam accelerator processing

The electron beam accelerator was used in the electron beam accelerator disclosed in Korean Patent No. 10-0687220 without using monomers and additives. Specifications and conditions of the electron beam accelerator are summarized in Table 1 below.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Fiber type Para-aramid filament yarn
(Kevlar ^® 49, 600denier from Dupont) Fabrics
(Slope: 34, weft: 34, plain weave) Ultra high molecular weight polyethylene filament yarn (UHMWPE: DSM's Dyneema ^® SK65, 400denier) fabric
(Slope: 29, weft: 29, plain weave) Para-aramid filament yarn
(Kevlar ^® 49, 600denier from Dupont) Fabrics
(Slope: 34, weft: 34, plain weave) Ultra high molecular weight polyethylene filament yarn (UHMWPE: DSM's Dyneema ^® SK65, 400denier) fabric
(Slope: 29, weft: 29, plain weave) Electron energy 0.7 MeV Untreated Max. beam power 40kW Max. 방사 전류 40mA Beam extraction window 980 x 75 mm Differential pressure of SF6 1.1 MPa Moisture absorption dose 300 kGy Volume of the insulation vessel 2.43 ㎥ Consumption power 65 kVA

3. Property Analysis

end. Analyzer

FE-SEM (Hitachi, SU-70) analysis was performed to observe the surface change of the fabric by electron beam irradiation. The changes of carbon and oxygen elements were analyzed by EA analysis (ThermoFisher, Flash 2000) And analyzed quantitatively. In addition, ESR analysis (JEOL, JES-TE300) was performed to measure the change of the radical intensity formed on the fabric surface. Also, tensile properties were measured using a universal tensile tester (SHIMADZU, AUTOGRAPH AG-X series) to examine the change in the physical properties of the fabric before and after electron beam irradiation.

I. Surface change of fiber

1) Surface observation through SEM analysis of textile materials

Field Emission Scanning Electron Microscope (FE-SEM, Hitachi, S-4800) analysis was performed to observe the changes of the constituent fiber surface by electron beam irradiation. The intensity and the energy of the irradiated electron beam were adjusted to 50, 100, 200, and 300 kGy by varying the amount of current through the control system of the control room, which is installed separately from the electron beam irradiation room.

As shown in FIGS. 1 and 2, the shape of the fiber surface did not change with time depending on the absorbed dose of the fiber.

2) Determination of radical generation through ESR analysis of textile materials

Table 2 shows the results of quantitative analysis of changes in carbon and oxygen elements through EA analysis (ThermoFisher, Flash 2000) to examine the elemental changes of each fiber.

p-aramid UHWMPE Carbon hydrogen Nitrogen Carbon hydrogen Nitrogen Comparative Example 65.950 4.209 10.903 83.863 14.333 0 Example 66.820 4.256 11.130 80.651 13.713 0

In the case of p-aramid, quantitative elemental analysis results were not different according to the electron beam treatment. However, in the case of UHMWPE fiber, the carbon content tended to decrease with increasing electron beam absorbed dose.

3) ESR analysis of textile materials to determine whether they produce radicals

To measure the change in the intensity of the radicals formed on the surface of the fiber material according to the electron beam absorbed dose measured by ESR (Electron Spin Resonance) analysis, which is a method of analyzing the phenomenon in which electrons lying in a high frequency magnetic field absorb energy resonated at a specific frequency Respectively. The experimental conditions were as follows: Magnetic center field: 325mT, microwave frequency: 9.13 GHz, modulation: 100 kHz, microwave power: 1.9 mW, time constant: 0.03 sec , And sweep time 4 min.

In order to confirm the formation of radicals in the structure of the chemical, the influence of various electron beam intensities on the change of the ESR spectrum of each fiber material was measured. As a result, as shown in FIGS. 3 and 4, And showed a symmetric ESR signal. If a radical is generated in the fiber by electron beam irradiation, a triplet signal should be identified along with a symmetrical ESR graph. In this experiment, however, the triplet was not confirmed, and even if the radical was generated, And thus, it is judged that the result is not confirmed.

C) Tensile strength change of fiber material after electron beam accelerator treatment

In order to confirm the change of properties of aramid and UHMWPE using universal tensile tester (UTM), the change of tensile strength was applied according to ISO 13934-1. The detailed conditions were load cell 100kN, constant speed The CRE cross-head speed was 20 mm / min. The nominal gage length of the test specimen was 150 mm. Five test specimens and five untreated specimens were selected and the mean value was calculated. Also, a capstan type jig was used to suppress a slip with a jig during the experiment.

As shown in Table 3, the UHMWPE fiber tends to have a 10% decrease in properties from 300 kGy compared to untreated specimens. In the case of UHMWPE, it was judged that the physical properties were deteriorated due to the heat generated due to the long electron beam irradiation time, and the result was also related to the result of the above element analysis.

p-aramid UHWMPE Modulus of elasticity
(N / tex) Maximum load
(N) Maximum variation
(mm) Modulus of elasticity
(N / tex) Maximum load
(N) Maximum variation
(mm) Comparative Example 6362.99 69.77 11.70 6429.83 59.52 26.03 Example 6031.84 65.79 11.08 5564.34 51.13 15.32

D) Dyeing experiment using electron beam accelerator

Although the surface treatment effect of the fiber was not observed in the case of using the electron beam accelerator, the dyeability of each fiber was improved by the electron beam accelerator in the dyeing experiment as shown in FIGS. 5 and 6. In spite of the fact that macroscopic changes can not be observed on the surface of the fiber, it is considered that the reason why the dyeability is improved is that the electron beam is a change due to heat treatment of the fiber due to energy of high efficiency.

Claims (2)

Surface treatment without using photoinitiators and monomers in surface treatment of ultra-high strength fiber fabrics with electron beam accelerators with maximum acceleration energy of 0.1 ~ 0.7 MeV, beam power of 5 ~ 28KW, beam current of 10 ~ 40mA and SF ₆ gas supply system And then dyed with a disperse dye. The method according to claim 1, delete

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