WO2018124399A1 - 고휘도 재귀반사 섬유소재 제조를 위한 uv 경화코팅방법 - Google Patents

고휘도 재귀반사 섬유소재 제조를 위한 uv 경화코팅방법 Download PDF

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Publication number
WO2018124399A1
WO2018124399A1 PCT/KR2017/003998 KR2017003998W WO2018124399A1 WO 2018124399 A1 WO2018124399 A1 WO 2018124399A1 KR 2017003998 W KR2017003998 W KR 2017003998W WO 2018124399 A1 WO2018124399 A1 WO 2018124399A1
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WO
WIPO (PCT)
Prior art keywords
yarn
acrylate
ultraviolet
curing coating
fiber
Prior art date
Application number
PCT/KR2017/003998
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English (en)
French (fr)
Korean (ko)
Inventor
진성우
김경돈
구광회
최영록
박준섭
박종혁
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주식회사 소포스
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Priority to JP2018558381A priority Critical patent/JP6850814B2/ja
Publication of WO2018124399A1 publication Critical patent/WO2018124399A1/ko

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D06B3/04—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of yarns, threads or filaments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06Q—DECORATING TEXTILES
    • D06Q1/00—Decorating textiles
    • D06Q1/10—Decorating textiles by treatment with, or fixation of, a particulate material, e.g. mica, glass beads
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/12—Reflex reflectors

Definitions

  • the present invention relates to a UV curing coating method for producing a high brightness retroreflective fiber material.
  • Applied technology is applied to protect our precious life and property from various safety accident logos that can occur in everyday life and industrial sites by using the characteristics of light in sportswear, night road construction sites, security guards, police officers and firemen's clothes. It is becoming. Line-shaped and various reflective stickers found in such garments are generally called retroreflective materials.
  • the retroreflective material is characterized by having the property of retroreflective reflection of reflected light in the direction of incident light.
  • Retroreflective sheets using the principle of retroreflective are classified into two types: glass beads and microprisms.
  • a fine glass bead or triangular pyramid-shaped lens is applied evenly on a fabric or film to return incident light in the direction of the light source. The incident light is refracted at the back of the bead and then reflected in the same direction as the light came in. .
  • the method of manufacturing a retroreflective material is classified into an enclosed type and an encapsulated type according to whether glass beads are exposed to air.
  • the glass beads are evenly applied on the PET layer coated with thermoplastic polyethylene (PE) at a temperature above the PE melting point.
  • PE thermoplastic polyethylene
  • the aluminum deposition is carried out under uniform conditions, the polyurethane adhesive is uniformly applied, and the fabric or film is attached and then the PET layer is removed.
  • the encapsulated lens retroreflective sheet evenly spreads the glass beads on the PET layer coated with the acrylic transparent adhesive, coated with acrylic, and then uniformly deposits aluminum.
  • a release paper coated with an adhesive is prepared.
  • the glass bead is divided into various processes such as adhesive and glass bead coating, deposition, and adhesive reapplication, thereby lowering productivity and lowering cost competitiveness.
  • high temperature thermal energy is used for the use of resins containing volatile organic solvents or fusion by heat or volatilization of organic solvents, CO 2 generation and volatilization of used organic solvents may cause problems such as workplace environment, air pollution and consumer safety. I have a problem.
  • the process of manufacturing a retroreflective fiber material is prepared by mixing glass beads in a thermosetting resin and coating or injecting glass beads into the hollow while spinning in a hollow form during fiber spinning.
  • the hollow retroreflective material is a kind of encapsulated lens type, but glass beads are not separated from the fiber, but the retroreflective property is markedly lower than 5 cd / lx ⁇ m 2 due to incident light transmission and scattered reflected light.
  • the retroreflective fibrous material mixed with the coating of glass beads and coated with the coating liquid is a capsule lens type, and the retroreflective performance is expressed up to 20 cd / lx ⁇ m 2 or less, but the beads are separated from the fiber, resulting in poor durability of the retroreflective performance.
  • Patent Document 1 Korean Patent Registration No. 10-1503508 (announced March 18, 2015)
  • the present invention after preparing the first UV-curable coating liquid mixed 40-59% by weight of the UV-curable monomer, 40-59% by weight of the UV-curable oligomer and 0.5-1% by weight of the photoinitiator,
  • the ultraviolet cured coating solution was semi-cured
  • a UV curing coating method for manufacturing a high-brightness retroreflective fibrous material characterized in that to cure the second ultraviolet ray-curing coating solution by irradiating the fiber yarn with an ultraviolet ray having a wavelength range of 260 ⁇ 395nm.
  • UV curing coating method for manufacturing a high-brightness retroreflective fiber material of the present invention is impregnated in the second ultraviolet ray hardening coating liquid after impregnating the fiber yarn in the first ultraviolet curing coating liquid to form a semi-cured thin coating layer and then applying the beads It relates to a method of curing the ultraviolet curing coating solution after.
  • Fiber yarn to be coated in the present invention cellulose yarn, wool yarn, silk yarn, polyester yarn, nylon yarn, glass fiber yarn, modacrylic (Modacrylic) yarn, polyethylene (Polyethylene, PE) fiber yarn, polypropylene (Polypropylene) , PP) fiber yarn, Ultra High Molecular Weigh Polyethylene (UHMWPE) fiber yarn, aramid fiber yarn, carbon fiber yarn, polyimide (PI) fiber yarn, polybenzoxazole (Polybenzoxazole, PBO) fiber yarn , Polybenzimidazole (PBI) fiber yarn and any one or more selected from dyeing yarns thereof may be used, and is not particularly limited.
  • the first UV curable coating solution for coating the fiber yarn is a first UV curable coating solution in which 40 to 59% by weight of UV curable monomer, 40 to 59% by weight of UV curable oligomer, and 0.5 to 1% by weight of photoinitiator are mixed. And semi-cured by UV curing.
  • the first UV-curable coating solution of the present invention uses a mixture of 40-59 wt% of UV-curable monomers, 40-59 wt% of UV-curable oligomers, and 0.5-1 wt% of photoinitiators. If the oligomer exceeds 59% by weight, the oligomer content is high, the viscosity is increased, and the thickness of the coating layer is increased to increase the fineness of the fiber as the excess glass beads are applied. Retroreflective materials made of fineness of 500 denier or more can cause poor weaving and have limited application development.
  • the viscosity is low, so that the coating amount is decreased, thereby reducing the coating amount of the glass beads. This may cause a problem that the retroreflective brightness is lowered.
  • the ultraviolet curable monomer in the primary ultraviolet curable coating solution is hydroxyethyl methacrylate, isobornyl methacrylate, hydroxybutyl methacrylate, methoxy methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate It is preferable to use one or more of stearyl methacrylate and isopropyl methacrylate to form the semi-hardened coating layer.
  • the UV-curable oligomer of the primary UV-curable coating solution is a polyurethane acrylate, epoxy acrylate, acrylic acrylate, polyester acrylate using a polyurethane and an acrylic acrylate as one or more of the oligomers of the viscosity of the UV-curable coating solution It is easy to adjust and is preferable to increase durability through improved adhesion of glass beads.
  • the photoinitiator of the UV-curable coating solution is benzophenone, ⁇ -Hydroxyketone system (Irgacure 184, 500, 1173, 2959, etc.), Phenylglyoxylate system (Darocure MBF, Irgacure 754, etc.), Benzyldimethyl-ketal system (BDK, Irgacure 651), ⁇ 0.5 to 1% by weight of any one or more of aminoketone (Irgacure 369, 907, 1300, etc.), Phosphine oxide (Darocure TPO, Irgacure 819, 2022, 2100, etc.), Isopropylthioxantone (ITX), Metallocene, Iodonium salt It is preferable to use as. This is to facilitate the adhesion of the glass beads by maintaining the surface Tacky properties while adjusting the curing rate in the process of applying the glass beads.
  • the glass beads in addition to the glass beads, by further dispersing 1-30 parts by weight of silver (Ag) or aluminum (Al) paste having a particle size of 1 to 30 ⁇ m relative to 100 parts by weight of the first ultraviolet curable coating solution, thereby improving retroreflective properties of the glass beads.
  • the glass bead used is aluminum deposited, but the glass bead applied to the primary UV-curable coating layer in which the aluminum paste is dispersed is reflected by the incident light because the aluminum paste is located opposite to the incident light. It is easy to increase the retroreflective brightness.
  • the primary coating solution is sprayed onto the fiber yarn semi-cured by UV curing and coated so that the glass beads adhere to the semi-cured coating layer, and then a portion of the glass beads is passed through a pressing roller having a constant pressure. It is fixed to the semi-cured layer of the ultraviolet coating solution.
  • Application of the glass beads is preferably carried out by spray or vibration.
  • the pressing roller part for fixing a portion of the bead to the semi-cured layer of the first ultraviolet coating liquid should be made of a rubber or silicone material of a flexible material capable of pressure control.
  • Pressure control of the pressing roller is a device for controlling the thickness of the primary coating layer and the adhesion of the glass bead on the surface of the fiber seal.
  • the glass bead coating layer is not uniform when the high pressure is pressed, and the glass bead and the first when the pressure is pressed at the low pressure. Adhesion may be lowered to the secondary UV-curable coating layer.
  • the retroreflective brightness is not increased by the diffuse reflection, but only the fineness of the retroreflective fiber material is increased. Therefore, a process of separating excess glass beads by adding an air curtain or spray process is required for uniform application of the glass beads.
  • the semi-cured layer of the first ultraviolet coating solution was impregnated with the fiber yarn in a second ultraviolet curing coating solution containing 60 to 79 wt% of an ultraviolet curing monomer, 20 to 39 wt% of an ultraviolet curing oligomer, and 1 to 5 wt% of a photoinitiator.
  • the second ultraviolet ray curing coating solution is cured by irradiating the fiber yarn with ultraviolet rays having a wavelength range of 260 to 395 nm.
  • the glass beads dispersed in the ultraviolet curing coating liquid have a particle diameter of 20 to 100 ⁇ m and a refractive index of 1.9 to 2.2 to improve retroreflective brightness (cd / lx ⁇ m 2).
  • glass beads having a refractive index of 1.9 to 2.2 among the beads and to deposit silver (Ag) or aluminum (Al) on the glass beads to increase the luminance of retroreflective light. good.
  • the UV curable monomer in the secondary UV curable coating solution is hydroxyethyl acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, ethylene glycol acrylate, hydroxybutyl acrylate, lauryl acrylate, stearyl acrylate At least one of isopropyl acrylate, ethoxyethoxyethyl acrylate, cyclohexyl acrylate, hexanediol diacrylate, butanediol diacrylate, trimethylolpropane triacrylate and pentaerythritol (tetra) triacrylate
  • the monomer it is preferable to use a monofunctional and polyfunctional monomer having a relatively high curing rate for complete curing of the primary coating layer and the secondary coating layer.
  • the UV curable oligomer of the primary UV curable coating liquid and the secondary UV curable coating liquid is polyurethane and acrylic acrylate as one or more oligomers of polyurethane acrylate, epoxy acrylate, acrylic acrylate and polyester acrylate. It is preferable to increase the durability of the UV-curable coating liquid by easily adjusting the viscosity and improving the adhesion of the glass beads. However, the second ultraviolet curable coating solution is preferable to maintain a low viscosity because the coating layer of the thin film should be formed in order to minimize the refraction and scattering of the incident or reflected light.
  • the photoinitiator in the secondary UV-curable coating solution is benzophenone, ⁇ -Hydroxyketone system (Irgacure 184, 500, 1173, 2959, etc.), Phenylglyoxylate system (Darocure MBF, Irgacure 754, etc.), Benzyldimethyl-ketal system (BDK, Irgacure 651 ), ⁇ -Aminoketone (Irgacure 369, 907, 1300, etc.), Phosphine oxide (Darocure TPO, Irgacure 819, 2022, 2100, etc.), Isopropylthioxantone (ITX), metallocene, Iodonium salt of any one or more It is preferable to use it at 5% by weight. This is to achieve complete curing of the first and second ultraviolet curable coating layers and for retroreflectivity and durability of the glass beads.
  • inorganic fine particles which are either silicon-based or titanium-based particles having a particle diameter of 10 nm to 100 ⁇ m, relative to 100 parts by weight of the UV-curable coating solution or the second UV-curing coating solution.
  • Dispersion can improve retroreflectivity.
  • the addition of the inorganic fine particles is for preparing an ultraviolet curable coating liquid similar to the refractive index of the glass beads, and the retroreflectivity may be improved by reducing scattering or diffuse reflection of light incident or reflected depending on the refractive index of the coating liquid.
  • a color may be added by adding any one of a dye, a pigment, and an ink ⁇ to the secondary UV-curable coating liquid.
  • Dye, pigment, ink added to the UV-curable coating liquid is preferably used an organic dye having a discoloration durability against ultraviolet rays, any one of azo-based, naphthol-based, phthalocyanine-based.
  • the coated fiber yarn is irradiated with ultraviolet rays having a wavelength range of 260 to 395 nm to completely cure the second ultraviolet curing coating solution.
  • the ultraviolet irradiation is a mercury lamp, in which at least one metal material of Fe, Ga, and Mg is added. It is preferable to use a metal halide lamp and an ultraviolet LED capable of irradiating the longest wavelength (395 nm) of ultraviolet rays, which is irradiated with longer wavelengths than mercury lamps, so that the coating layer can be cured within seconds to minutes to improve productivity. Can be.
  • UV LED is easy to apply to heat-sensitive fiber material because it can be cured at room temperature (20 ⁇ 30 °C) when irradiated.
  • an infrared drying unit may be installed before and after the ultraviolet irradiation process to perform an infrared drying process, which may be used to dry the moisture contained or to increase the degree of curing through moisture drying when a water-soluble or aqueous dispersion is used. The purpose is to improve.
  • the coated yarn having the retroreflective coating of the fiber yarn is surrounded by the first ultraviolet ray cured coating layer 20, and a part of the beads 30 is the first ultraviolet ray hardened coating layer as shown in FIG. 1. 20), and the rest of the beads and the outer wall of the first ultraviolet coating layer are completely covered by the second ultraviolet ray hardening coating layer 40.
  • the retroreflective brightness and durability can be improved by the first and second ultraviolet curable coating layers, thereby making it possible to manufacture a high-brightness, highly durable retroreflective fiber material.
  • the present invention it is possible to express a soft touch in an eco-friendly process without using carbon dioxide emission without using an organic solvent, and excellent in weaving (fabrication) and stretch (stretch) while maintaining the durability of retroreflective 20cd / It is possible to manufacture high-brightness retroreflective fiber yarns of lx ⁇ m2 or more and to provide woven fabrics and applications.
  • FIG. 1 is a cross-sectional view showing the cross-sectional structure of the retroreflective fiber yarn by the UV curing coating method for producing a high-brightness retroreflective fiber material of the present invention
  • Figure 2 is a side photograph of the retroreflective fiber yarns by the UV curing coating method for producing a high brightness retroreflective fiber material of the present invention
  • FIG. 3 is a cross-sectional photograph of a retroreflective fiber yarn by the UV curing coating method for producing a high brightness retroreflective fiber material of the present invention
  • Figure 4 is a process schematic diagram of the UV curing coating method for producing a high brightness retroreflective fiber material of the present invention.
  • UV curing coating method for producing a high brightness retroreflective fiber material of the present invention is non-limiting examples of the UV curing coating method for producing a high brightness retroreflective fiber material of the present invention.
  • the glass After irradiating with an ultraviolet lamp having a wavelength range of 260 to 395 nm, the glass was semi-cured, and aluminum was deposited, glass beads having a refractive index of 1.93 and a particle diameter of 60 ⁇ m were sprayed and applied by spraying, and then excess glass beads were detached from the air curtain.
  • fiber yarn 20 the first ultraviolet curing coating layer

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Decoration Of Textiles (AREA)
  • Paints Or Removers (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
PCT/KR2017/003998 2016-12-29 2017-04-13 고휘도 재귀반사 섬유소재 제조를 위한 uv 경화코팅방법 WO2018124399A1 (ko)

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JP2018558381A JP6850814B2 (ja) 2016-12-29 2017-04-13 高輝度再帰反射繊維素材製造のためのｕｖ硬化コーティング方法

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KR1020160181881A KR101725407B1 (ko) 2016-12-29 2016-12-29 고휘도 재귀반사 섬유소재 제조를 위한 uv 경화코팅방법
KR10-2016-0181881 2016-12-29

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109096518A (zh) * 2018-10-25 2018-12-28 杭州晴朗体育设施有限公司 带有投影功能的天然草坪保护板

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Publication number Priority date Publication date Assignee Title
KR102201584B1 (ko) * 2020-01-31 2021-01-12 주식회사 소포스 Uv 경화코팅방법을 이용한 전기전도성 쉬스코어형섬유소재의 제조방법

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JPH0812786A (ja) * 1994-06-28 1996-01-16 Dainippon Printing Co Ltd 多層の薄膜を有する反射防止シート
KR100951509B1 (ko) * 2007-05-16 2010-04-07 광 석 서 자외선 경화형 대전방지 코팅 조성물
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109096518A (zh) * 2018-10-25 2018-12-28 杭州晴朗体育设施有限公司 带有投影功能的天然草坪保护板
CN109096518B (zh) * 2018-10-25 2023-05-26 杭州晴朗体育设施有限公司 带有投影功能的天然草坪保护板

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