KR101616709B1 - Ultraviolet shielding resin compositions and synthetic fibers using thereof - Google Patents
Ultraviolet shielding resin compositions and synthetic fibers using thereof Download PDFInfo
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- KR101616709B1 KR101616709B1 KR1020150115600A KR20150115600A KR101616709B1 KR 101616709 B1 KR101616709 B1 KR 101616709B1 KR 1020150115600 A KR1020150115600 A KR 1020150115600A KR 20150115600 A KR20150115600 A KR 20150115600A KR 101616709 B1 KR101616709 B1 KR 101616709B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K3/0033—
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- C08K3/0041—
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- C08K3/005—
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
Abstract
The present invention relates to an ultraviolet barrier resin composition including metal oxide nanoparticles doped with synthetic resin and vanadium and having excellent barrier properties in a wide range of ultraviolet rays and having no deterioration of ultraviolet shielding performance permanently even in washing, Fiber.
Description
The present invention relates to a UV shielding resin composition and a synthetic fiber produced therefrom. More particularly, the present invention relates to an ultraviolet barrier resin composition excellent in barrier properties in a wide range of ultraviolet rays and having permanently excellent ultraviolet barrier properties without damaging ultraviolet barrier property against washing, and synthetic fibers prepared therefrom.
Ultraviolet rays are known to be a powerful cause of skin aging and there is a growing desire for the emergence of synthetic fibers with excellent ultraviolet barrier properties that can protect the human body from this.
The sunlight consists of gamma rays, X rays, ultraviolet rays, visible rays, infrared rays, and radio waves of different wavelengths. Among them, ultraviolet rays are ultraviolet rays I call it.
The ultraviolet rays are divided into UVA (320 to 400 nm), UVB (290 to 320 nm) and UVC (200 to 290 nm) according to the wavelength, UVA is again divided into UVA II (320 to 340 nm) 400 nm). Among them, UVC is absorbed and scattered in the ozone layer, water vapor, and dust in the air, so only UVA and UVB harmful to the human body are reached on the ground surface.
After a few hours after exposure to ultraviolet light, the redness of the skin becomes red after about 8 hours, then peaking and then gradually weakening, which is called sunburn. In addition, when exposed to a large amount of ultraviolet light, it may further develop and become blurred, such as blisters, which are mainly caused by UVB.
On the other hand, UVA can damage the immune system. This can be confirmed in cases of light allergic reaction, urticaria due to sunburn, and the like. Unlike UVB, which causes skin burns directly, UVA penetrates deeper into the skin and gradually creates spots and freckles, damaging the skin without you knowing. In other words, if UVB burns the outer surface of the skin, UVA penetrates into the skin to destroy the skin cells and also has a fatal effect on skin aging. UVA is associated with early aging of skin cells and skin cancer, and UVA blocking effect is strengthened especially in developed countries recently.
Recently, as a result of active leisure sports, there has been a lot of time for outdoor activities, and it is emphasized the necessity of a fiber for leisure sports clothing having excellent ultraviolet barrier property. As a representative method for producing such clothes, there is a post-processing method of coating or laminating an organic UV-blocking agent on a fabric or the like. Examples of effective organic UV-blocking agents in the UVB and UVA II regions include benzophenone-3, benzophenone-4, diethylhexyl butamido triazone, ethylhexyl salicylate, ethylhexyl triazone, homomethyl salicylate, isoamyl p-methoxycinnamate, octocrylene, phenylbenzimidazole sulfonic acid, 4-methylbenzylidene camphor, polysilicone-15. Examples of effective organic UV-blocking agents in the UVA I region include bis-ethylhexyloxyphenol methoxyphenyl triazine, butyl methoxydibenzoylmethane, diethylaminohydroxybenzoyl hexyl benzoate, disodium phenyl dibenimidazole tetrasulfonate, drometriazole trisiloxane, menthyl anthranilate, terephthalyidene dicamphor sulfonic acid methylene bis-benzotriazolyl tetramethylbutylphenol and the like.
The method of using the organic blockade agent has a disadvantage in that the manufacturing cost is high and there is a high possibility that an environmental problem due to the use of a solvent occurs, and in particular, the ultraviolet blocking effect is drastically lowered during use and washing.
In order to overcome such disadvantages, a method of dispersing an inorganic ultraviolet screening agent in a small amount during the polymerization of a synthetic resin or dispersing a mixture of a synthetic resin and an inorganic ultraviolet screening agent in a separate compounding step is spun to prepare synthetic fibers There is a way to get clothing. Representative examples of effective UV blocking agents in the UVB and UVA II regions include titanium dioxide nanoparticles. Representative examples of inorganic UV blocking agents effective in the UVA I region include zinc oxide and cerium oxide nanoparticles .
Since ultraviolet screening must exert its effects in all areas of UVB, UVA II, and UVA I, a method of using two or more of these ultraviolet screening agents is often adopted. Nevertheless, in the case of the organic and inorganic ultraviolet screening agents currently developed, ultraviolet ray shielding performance in the range of 360 to 400 nm adjacent to visible light in the UVA I region is low, and even when two or more ultraviolet screening agents are mixed, the overall ultraviolet screening property is insufficient The solution is urgent and urgent. That is, there is a need to develop a resin composition using a novel ultraviolet screening agent capable of realizing a permanent UV blocking effect over all areas of UVB, UVA II and UVA I, and a synthetic fiber prepared using the resin composition.
In order to solve the above problems, it is an object of the present invention to provide a resin composition which is superior in barrier properties in a wide range of ultraviolet rays, and which is permanently excellent in ultraviolet barrier property .
It is another object of the present invention to provide a synthetic fiber produced from the resin composition and having an excellent ultraviolet shielding performance.
In order to accomplish the above object, the present invention provides a UV-blocking resin composition comprising metal oxide nano-particles doped with synthetic resin and vanadium.
Further, the present invention provides an ultraviolet barrier synthetic fiber produced by melt spinning the ultraviolet barrier resin composition.
One of the important objectives of the present invention is to secure a permanent ultraviolet shielding performance. For this ultraviolet blocking performance, the present invention uses an inorganic blocker that is not an organic UV blocker. The present invention can permanently realize an excellent ultraviolet shielding effect over all areas of UVB, UVA II and UVA I by using a synthetic resin in the composition and a metal oxide nanoparticle doped with vanadium by using an inorganic blocker.
The present invention also provides a method for preparing a precipitate, comprising the steps of: (a) adding a solution of an alkali metal hydroxide to a mixture of a metal organic acid salt and a vanadium organic acid salt, reacting and reacting the obtained reaction product to obtain a precipitate; (b) adding a hydrogen peroxide solution to the precipitate Obtaining a solid phase precipitate, (c) filtering, washing and drying the solid phase precipitate to obtain a powder, and
(d) sintering the powder. The present invention also provides a method for producing vanadium-doped metal oxide nanoparticles.
The ultraviolet barrier resin composition according to the present invention has an advantage that ultraviolet barrier property can be permanently achieved over all the areas of UVB, UVA II and UVA I.
In addition, the synthetic fiber produced by using the ultraviolet barrier resin composition according to the present invention is excellent in ultraviolet shielding performance over the entire range of UVB, UVA II and UVA I, And it is very advantageous for various fields including clothing, especially leisure sports clothing by drastically improving ultraviolet shielding performance.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
The inventors of the present invention have surprisingly found that it is possible to permanently achieve excellent ultraviolet barrier properties over all the UVB, UVA II and UVA I regions by providing a UV barrier resin composition comprising metal oxide nanoparticles doped with synthetic resin and vanadium Thereby completing the present invention. Further, the present inventors have been able to manufacture synthetic fibers that have greatly improved ultraviolet shielding performance.
The present invention provides a UV-blocking resin composition comprising metal oxide nano-particles doped with a synthetic resin and vanadium.
In the ultraviolet barrier resin composition according to one embodiment of the present invention, the metal oxide may be at least one selected from the group consisting of cerium oxide, zinc oxide, and titanium dioxide.
In the UV-blocking resin composition according to one embodiment of the present invention, the amount of the metal oxide nanoparticles doped with vanadium may be 1 to 50 wt%.
In the ultraviolet barrier resin composition according to one embodiment of the present invention, the synthetic resin may be any one or more selected from the group consisting of polyester, polyamide, polyacrylonitrile, polyurethane, polypropylene, polyethylene and polyvinyl chloride have.
The ultraviolet barrier resin composition according to one embodiment of the present invention may contain 0.001 to 10 parts by weight of metal oxide nanoparticles doped with vanadium with respect to 100 parts by weight of synthetic resin.
The ultraviolet barrier resin composition according to an embodiment of the present invention may further comprise at least one additive selected from the group consisting of a dispersant, an antioxidant, a heat stabilizer, a pigment, a fluorescent whitening agent, an antibacterial agent, a deodorant, a flame retardant and an antistatic agent .
The present invention
(a) adding an alkali metal hydroxide aqueous solution to a mixture of a metal organic acid salt and a vanadium organic acid salt, reacting and reacting the obtained reaction product to obtain a precipitate,
(b) adding a hydrogen peroxide solution to the precipitate and reacting to obtain a solid phase precipitate,
(c) filtering, washing and drying the solid phase precipitate to obtain a powder; and
(d) sintering the powder
Doped metal oxide nanoparticles containing vanadium.
In the method for preparing vanadium-doped metal oxide nanoparticles according to an embodiment of the present invention, the reaction in step (a) may be performed at a pH in the range of 2 to 7.
The present invention provides an ultraviolet barrier synthetic fiber produced by melt spinning the resin composition.
Hereinafter, each configuration according to an embodiment of the present invention will be described in more detail.
In the present invention, "% " means "% by weight " unless otherwise specified.
In the present invention, " nanoparticles " means particles having an average particle diameter of up to 500 nm, preferably individual particles having an average particle diameter of up to 300 nm, unless otherwise specified.
One embodiment of the present invention is a UV shielding resin composition comprising metal oxide nanoparticles doped with synthetic resin and vanadium.
The synthetic resin is a resin used as a base material and is not particularly limited, but preferably includes polyester, polyamide, polyacrylonitrile, polyurethane, polypropylene, polyethylene, polyvinyl chloride and the like. Of these, polyester, polyamide, polyacrylonitrile and the like which are widely used for fiber use are more preferable.
In order to be able to apply to a fiber application and to achieve a desired effect, the polyester has a viscosity of 60 to 40 in an intrinsic viscosity (tetrachloroethane: phenol weight ratio = 60: 40) D-4603-96) of 0.5 to 0.8 is preferably used. The polyamide preferably has a relative viscosity (measured in accordance with ASTM D789 using 1 g of a resin component in 100 ml of 20% C 96% sulfuric acid) of 2.0 to 3.5.
In the present invention, the metal oxide nanoparticles are used for imparting an ultraviolet shielding function, and examples thereof include nano-sized titanium dioxide, zinc oxide, cerium oxide, zirconium dioxide, iron oxide, and the like.
According to the relationship between the wavelength of light and the energy, the ultraviolet region corresponds to an energy level of 3.1 eV or more. This is an energy corresponding to the energy gap between the valence electron band and the conduction band in the semiconductor material and the inorganic material having such an energy gap is preferable It is more preferable to use at least one selected from titanium dioxide, zinc oxide and cerium oxide.
The metal oxide nanoparticles according to the present invention are characterized by being vanadium-doped metal oxide nanoparticles.
The reason why the present invention includes vanadium-doped metal oxide nanoparticles can not be clearly understood. However, in order to exhibit ultraviolet shielding property in the range of 370 to 400 nm in the UVA I region which can not be exerted in the conventional ultraviolet screening agents, The shift of the energy gap between the band and the conduction band takes place, and ultraviolet ray absorbing performance is greatly improved, so that excellent ultraviolet ray blocking property can be realized in all areas of UVB, UVA II and UVA I.
The method for preparing vanadium-doped metal oxide nanoparticles according to the present invention comprises the steps of: (a) adding an alkali metal hydroxide aqueous solution to a mixture of a metal organic acid salt and a vanadium organic acid salt and then reacting the resulting reaction product to obtain a precipitate; ) Adding a hydrogen peroxide solution to the precipitate to obtain a solid phase precipitate, (c) filtering, washing and drying the solid phase precipitate to obtain a powder, and (d) sintering the powder.
Specifically, in step (a), a metal oxide such as titanium, zinc, cerium, or the like is selected and a metal organic acid salt selected from metal nitrate, metal sulfate, metal hydrochloride, metal nitrate, metal carbonate and the like is prepared. Further, a vanadium organic acid salt which can be selected from vanadium nitrate, vanadium sulfate, vanadium hydrochloride, vanadium acetate, vanadium carbonate and the like is prepared. The prepared metal organic acid salt and vanadium organic acid salt are mixed at a desired ratio, and an appropriate amount of an alkali metal hydroxide aqueous solution such as NaOH or KOH is added to adjust the pH, and the mixture is reacted at a constant temperature ranging from room temperature to 100 ° C.
In step (b), the reaction product obtained in the previous step reaction is filtered and washed several times with distilled water to obtain a precipitate. A proper concentration of hydrogen peroxide solution is added thereto, and the reaction is carried out at an appropriate temperature ranging from 50 to 100 ° C to obtain a solid oxide precipitate.
In step (c), the solid acid precipitate is filtered and washed with distilled water and dried to obtain a powder.
In the step (d), vanadium-doped metal oxide nanoparticles can be obtained by putting the powder obtained in the previous stage in the crucible and sintering at a temperature of 500 to 800 ° C. The size of the vanadium-doped metal oxide nanoparticles may vary greatly depending on the pH, and the particle size tends to increase with increasing pH. The pH is preferably 2 to 7, more preferably 3 to 5.
In the present invention, the amount of the metal oxide nanoparticles doped with vanadium is more preferably 1 to 50% by weight, and more preferably 5 to 30% by weight. When the amount of doping is less than 1 wt%, it may be difficult to achieve excellent UV blocking effect over UVB, UVA II and UVA I. If it exceeds 50 wt%, the absorption of visible light is considerably accompanied, When applied as a fiber, there is a problem that it is difficult to stain brightly due to opacity.
The shape of the metal oxide nanoparticles is not limited to a spherical shape, an acicular shape, a plate-like shape and the like. However, it is preferable that the spherical shape and the plate shape are wider in surface area per weight.
The average particle diameter of the metal oxide nanoparticles is not particularly limited, but is preferably 5 to 500 nm, more preferably 10 to 300 nm, and more preferably 50 to 250 nm. When the average particle diameter is less than 5 nm, the particle size is too small to cause scattering so that the ultraviolet blocking effect is lowered. If the average particle diameter is more than 500 nm, the ultraviolet ray shielding performance deteriorates, the particle dispersibility is poor, it's difficult.
The UV shielding resin composition according to the present invention preferably contains 0.001 to 10 parts by weight, preferably 0.1 to 7 parts by weight, of metal oxide nanoparticles doped with vanadium with respect to 100 parts by weight of synthetic resin, And more preferably 5 parts by weight. When the content of the nanoparticles is less than 0.001 parts by weight, it is difficult to secure a desired ultraviolet barrier property. When the content of the nanoparticles is more than 10 parts by weight, it is difficult to secure a clear coloring property due to transparency damage.
In order to improve the dispersibility of the metal oxide nanoparticles, the resin composition of the present invention may be prepared by mixing the synthetic resin and the metal oxide nanoparticles in an appropriate ratio, and mixing the mixture with a single screw extruder, a twin screw extruder, a mixing roll, It may be put into a hopper of a kneader and melt-kneaded and dispersed to prepare a compound pellet.
Alternatively, a master batch of metal oxide nanoparticles having a high concentration may be prepared, and the synthetic resin and metal oxide nanoparticle master batch pellets may be mixed by dry blending, or the mixture may be put into a hopper of a kneader and melt kneaded to form pellets to ensure dispersibility can do. Particularly, when the dispersibility is poor, the composition obtained due to agglomerated particle agglomerates may be cut off during melt spinning, resulting in a significant deterioration in spinning workability and a problem that the ultraviolet barrier property against the addition amount may be poor. .
The ultraviolet light shielding resin composition according to the present invention can be added to conventional additives in a range that does not impair the object of the present invention such as a dispersant, an antioxidant, a heat stabilizer, a pigment, a fluorescent whitening agent, an antimicrobial agent, a deodorant, , But the present invention is not limited thereto.
The dispersant is preferably added to improve the dispersibility of the nanoparticles. The dispersant may vary greatly depending on the type of the synthetic resin to be a base material, and a polymer dispersant that is more preferable than the low molecular weight dispersant is preferable in order to prevent the quality deficiency due to the transfer of the dispersant. For example, in the case of polyamide, polyethylene or polypropylene, a polyethylene-based ionomer is more preferable.
The amount of the dispersant is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 2 parts by weight based on 100 parts by weight of the synthetic resin. When the amount of the dispersant is less than 0.01 part by weight, the effect of improving the dispersibility of the desired nanoparticles is insignificant. When the amount of the dispersant is more than 5 parts by weight, the stiffness is weakened due to the excess dispersant that does not contribute to dispersion. May fall.
In addition, the present invention provides the ultraviolet barrier synthetic fiber obtained by the above-mentioned resin composition by a conventional fiber spinning method. For example, the UV-blocking resin composition pellets according to the present invention are dried in consideration of the characteristics of a matrix synthetic resin, then put into a hopper of an extruder, melt extruded, and then spun through a predetermined shape to cool and heat- The ultraviolet light shielding synthetic fiber can be produced.
Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not intended to limit the scope of the present invention.
The ultraviolet barrier property, ultraviolet barrier persistence and radiation workability of the ultraviolet barrier resin composition and the synthetic fiber of the present invention were evaluated by the following test methods.
(1) Ultraviolet barrier property
Considering that it is difficult to evaluate the ultraviolet barrier property by the fiber (filament) itself, it is made into a film having a thickness of 20 탆 (3 denier fiber diameter) using a sample resin, and the ultraviolet region (%) Was evaluated as the percentage of the non-permeable both. The ultraviolet barrier property was evaluated by distinguishing UVA I blocking property and total barrier property.
(2) Persistence of sun protection
KS K ISO 105-C06 (Textile Wash Fastness Test). A wash solution prepared by dissolving 4 g of the standard detergent in 1 L of water was prepared and put into a test bottle prepared beforehand. Then, a film sample having a thickness of 20 탆 (3 denier fiber diameter) used in the evaluation of the ultraviolet barrier property was immersed and the test bottle was set in a shaker After shaking for 30 minutes at 60 ℃, discard the washes and rinse twice with water. After repeating these operations 100 times, the film samples were dried and evaluated for UV resistance (%) using a UV-VIS Spectrometer, and the change rate (%) before and after washing was calculated and evaluated based on the criteria shown in Table 1 Respectively. UV protection persistence was evaluated only for total blocking.
[Table 1]
(3) Radial workability
The frequency (times / day) at which yarn breakage occurred was measured and the spinning workability was evaluated based on the criteria shown in Table 2 below.
[Table 2]
[Example 1]
A polyethylene terephthalate resin (PET-A) having an intrinsic viscosity of 0.65 was prepared as a polyester resin for fibers.
First, a 1.5 mol / L Ce (NO 3) 3 · 6H 2 O ( Compound A) VOSO 4 · 5H 2 O ( Compound B) an aqueous solution of 1.5 mol / L Preparation of an aqueous solution, and a vanadium organic acid salt as the metal organic acid salt Ready. The pH of the mixture was adjusted to 3.5 by adding 5 mol / L NaOH aqueous solution to 1 L of a mixture of 80% by weight of Compound A and 20% by weight of Compound B, and reaction was carried out at room temperature to form a white precipitate. The precipitate was filtered and washed three times with distilled water. g. A solid oxide precipitate was obtained by adding 0.5 L of a 30 wt% aqueous hydrogen peroxide solution and reacting at 50 ° C. The precipitate was filtered, washed three times with distilled water, and dried. The resulting powder was placed in a crucible and sintered at 600 ° C. for 6 hours , Cerium oxide nanoparticles (V / CeO 2 -A) doped with 6.9 wt% of vanadium having an average diameter of 30 nm were obtained.
100 parts by weight of the PET-A and 1.0 part by weight of V / CeO 2 -A were blended and dispersed in a L / D 42, 90Φ twin-screw extruder under the condition of a cylinder temperature of 280 ° C to obtain a resin composition (1) .
The obtained pellets of the resin composition (1) were dried to make a water content of 0.05% by weight or less, put into an extruder hopper, and melt extruded to prepare a spinning solution. The prepared spinning solution was spun through a spinneret having a circular cross-sectional structure at a spinning temperature of 285 DEG C and a spinning speed of 4,000 m / min, cooling the spinning at a wind speed of 0.5 m / min at a cooling rate of 20 DEG C, Thus, 3 denier synthetic fibers 1 were obtained. A film having a thickness of 20 탆 (3 denier fiber diameter) was prepared from the obtained resin composition (1) by using a hot press to measure the ultraviolet barrier property and ultraviolet barrier persistence. Using the resin composition (1) And the radiation workability was evaluated as the frequency of occurrence of yarn splicing during the obtaining of the synthetic fiber (1).
[Example 2]
A cerium oxide nanoparticle (V / V) doped with 13.8 wt% vanadium having an average diameter of 55 nm was prepared in the same manner as in Example 1 except that a mixture of 65 wt% of Compound A and 35 wt% of Compound B was used and the pH was adjusted to 5.0. CeO 2 -B).
(2) pellets and 3 denier synthetic fibers ((2)) were prepared in the same manner as in Example 1, except that 100 parts by weight of the PET-A and 1.0 parts by weight of V / CeO 2 -B were used. 2) were obtained, and the ultraviolet barrier property, persistence of UV shielding and radiation workability were evaluated.
[Example 3]
A cerium oxide nanoparticle doped with 22.9 wt% of vanadium having an average diameter of 110 nm (V / V) was prepared in the same manner as in Example 1 except that a mixture of 50 wt% of Compound A and 50 wt% of Compound B was used and the pH was adjusted to 6.5. CeO 2 -C).
(3) pellets and 3 denier synthetic fibers (3) were prepared in the same manner as in Example 1 except that the composition prepared by mixing 100 parts by weight of the PET-A and 1.0 part by weight of V / CeO 2 -C 3) were obtained, and the ultraviolet barrier property, UV blocking persistence and radiation workability were evaluated.
[Example 4]
The procedure of Example 1 was repeated except that a mixture of 40% by weight of Compound A and 60% by weight of Compound B was used and the pH was adjusted to 7.5 to prepare a cerium oxide nanoparticle (V / V) doped with 30.8% CeO 2 -D).
(4) pellets and 3 denier synthetic fibers (4) were prepared in the same manner as in Example 1, except that 100 parts by weight of the PET-A and 1.5 parts by weight of V / CeO 2 -D were used. 4) were obtained, and the ultraviolet barrier property, persistence of UV shielding and radiation workability were evaluated.
[Example 5]
Will first prepare a 1.5 mol / L ZnSO 4 · H 2 O ( Compound C) an aqueous solution of a metal organic acid salt, and a compound C 70 wt.%, Compound B 30% by weight of the mixture and adjust the pH to 7.0, except Example 1, zinc oxide nanoparticles (V / ZnO-A) doped with vanadium 21.3% by weight having an average diameter of 180 nm were obtained.
(5) pellets and 3 denier synthetic fibers (5) were prepared in the same manner as in Example 1 except that the composition prepared by mixing 100 parts by weight of PET-A and 1.5 parts by weight of V / ZnO-A was used. ), And the ultraviolet barrier property, persistence of UV shielding and radiation workability were evaluated.
[Example 6]
First, 1.5 mol / L of Ti (NO 3 ) 4 (Compound D) was prepared as a metal organic acid salt, and a mixture of 50 wt% of Compound D and 50 wt% of Compound B was used and the pH was adjusted to 3.8. Zinc oxide nanoparticles (V / TiO 2 -A) doped with 38.9 wt% of vanadium having an average diameter of 60 nm were obtained.
(6) pellets and 3-denier synthetic fibers (6) were prepared in the same manner as in Example 1, except that 100 parts by weight of PET-A and 2.0 parts by weight of V / TiO 2 -A were used. 6) were obtained, and the ultraviolet barrier property, persistence of UV shielding and radiation workability were evaluated.
[Example 7]
Polyamide 6 (PA-A) having a relative viscosity of 2.5 was prepared as a polyamide resin for fibers.
100 parts by weight of PA-A and 1.5 parts by weight of V / CeO 2 -D were used in the same manner as in Example 1 to obtain a resin composition (7) pellet. The melt spinning temperature was set at a spinning temperature of 255 , And 3 denier synthetic fibers (7) were obtained in the same manner as in Example 1 except that the ultraviolet barrier property, ultraviolet barrier persistence and radiation workability were evaluated.
[Example 8]
Zinc oxide nanoparticles doped with 29.6% by weight of vanadium having an average diameter of 45 nm (V) were prepared in the same manner as in Example 1 except that a mixture of 60% by weight of the compound C and 40% by weight of the compound B was used and the pH was adjusted to 3.7. / ZnO-B).
(15% by weight) methacrylic acid (15% by weight) neutralized with sodium ion (neutralization degree: 60%) and an ionomer as a copolymer of ethylene and (85% by weight) as a dispersant for metal oxide nanoparticles having a melt viscosity of 0.9 g / Surlyn 8920 (PEI) from DuPont was prepared.
(8) pellets and 3 deniers were prepared in the same manner as in Example 7, except that 100 parts by weight of PA-A, 1.5 parts by weight of V / ZnO-B and 1.0 part by weight of PEI were used. Of synthetic fiber (8) were obtained, and the ultraviolet shielding property, persistence of UV shielding and radiation workability were evaluated.
[Example 9]
Zinc oxide nanoparticles doped with 29.8% by weight of vanadium having an average diameter of 90 nm (V) were prepared in the same manner as in Example 1 except that a mixture of 60% by weight of the compound D and 40% by weight of the compound B was used and the pH was adjusted to 4.5. / TiO 2 -B).
(9) pellets and 3 deniers were prepared in the same manner as in Example 7, except that 100 parts by weight of PA-A, 2.0 parts by weight of V / ZnO-B and 2.0 parts by weight of PEI were used. (9) were obtained, and the ultraviolet shielding property, persistence of UV shielding, and radiation workability were evaluated.
[Example 10]
Polypropylene (PP-A) having a melt index of 15.0 (g / 10 min, 230 占 폚) was prepared as a polypropylene resin for fibers.
The pellets of the resin composition (10) were obtained in the same manner as in Example 1 except that 100 parts by weight of PP-A, 1.5 parts by weight of V / CeO 2 -D and 1.0 part by weight of PEI were used, 3 denier synthetic fibers (10) were obtained in the same manner as in Example 1 except that the temperature was set at 195 캜, and the ultraviolet barrier property, ultraviolet blocking persistency and radiation workability were evaluated.
[Example 11]
Except that 100 parts by weight of PP-A, 1.5 parts by weight of V / TiO 2 -B and 1.0 part by weight of PEI were used in the same manner as in Example 10 to prepare a resin composition (11) pellet and a 3 denier ) Of synthetic fibers (11) were obtained, and the ultraviolet barrier property, ultraviolet barrier persistence and radiation workability were evaluated.
[Comparative Example 1]
Plate-shaped cerium oxide (Degussa, CeO 2 -A) having an average particle diameter of 50 nm was prepared as nanoparticles.
The synthetic fibers (C1) of the PET-A 100 parts by weight, CeO 2 -A 3.0 parts by weight was used in a blend composition with the blending ratio, except in Example 1 in the same manner as in Resin composition (C1) pellets and 3 denier (denier) portion , And the ultraviolet barrier property, UV blocking persistence and radiation workability were evaluated.
[Comparative Example 2]
Spherical zinc oxide (BYK Co., ZnO-A) having an average particle diameter of 80 nm was prepared as the nanoparticles.
(C2) pellets and 3 denier synthetic fibers (C2) were prepared in the same manner as in Example 7, except that the composition obtained by mixing 100 parts by weight of PET-A and 3.0 parts by weight of ZnO-A was used. , And the UV barrier property, UV barrier persistence and radiation workability were evaluated.
[Comparative Example 3]
Spherical titanium dioxide (DuPont, TiO 2 -A) having an average particle size of 120 nm was prepared as the nanoparticles.
The synthetic fibers (C3) of the PET-A 100 parts by weight, TiO 2 -A 3.0 parts by weight was used in a blend composition with the blending ratio, except was carried out as Example 10, the resin composition (C3) pellets and 3 denier (denier) portion , And the ultraviolet barrier property, UV blocking persistence and radiation workability were evaluated.
[Comparative Example 4]
Benzophenone-3 (BASF, trade name Uninul M40) as an effective organic UV-blocking agent in the UVB and UVA II domains was prepared as drometriazol trisiloxane (BASF, Mexoryl XL) as an effective organic UV blocking agent in the UVA I region.
(C4) pellets and 3 deniers were prepared in the same manner as in Example 1 except that 100 parts by weight of PET-A, 2.5 parts by weight of benzophenone-3, and 2.5 parts by weight of drometriazole trisiloxane were used. Synthetic fiber (C4) was obtained and evaluated for its ultraviolet barrier property, UV protection persistence and radiation workability.
[Table 3]
EXAMPLES 1 to 11 are synthetic fibers prepared by using the resin composition containing the metal oxide nanoparticles doped with vanadium according to the present invention and having excellent ultraviolet shielding properties over all the UVB, UVA II and UVA I regions Able to know. In addition, it was confirmed that persistence of ultraviolet ray shielding is excellent, and permanent ultraviolet ray blocking property can be realized. This is in contrast to the fact that the organic or inorganic ultraviolet screening agent according to the prior art has a poor ultraviolet shielding property in the UVA I region and thus the ultraviolet screening property is insufficient. In Examples 8 to 11, it was confirmed that a suitable dispersing agent was used together, and the ultraviolet barrier property and radiation workability were further improved due to the improvement of the dispersibility of the nanoparticles.
It can be seen that Example 4 exhibits excellent UV blocking property even when the amount of cerium oxide nanoparticles doped with vanadium of the present invention is smaller than that of the conventional cerium oxide nanoparticles in Comparative Example 1. [ The same results can be confirmed also in the case of the comparison of Example 8, Comparative Example 2, Example 11, and Comparative Example 3. This is because when titanium dioxide, zinc oxide, cerium oxide nanoparticles, etc. according to the prior art are used, the barrier properties in the UVB and UVA II regions are somewhat good, but the ultraviolet shielding properties in the UVA I regions are poor, The results seem to have shown. In addition, in Comparative Example 4 using the organic UV-blocking agent, it was found that the ultraviolet shielding property in the UVA I region was poor and the ultraviolet shielding property was poor overall, and the ultraviolet ray shielding persistency was extremely poor.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and variations are possible in light of the above teachings.
Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .
Claims (9)
(b) adding hydrogen peroxide to the precipitate to obtain a solid phase precipitate,
(c) filtering, washing and drying the solid phase precipitate to obtain a powder; and
(d) sintering the powder
Wherein the metal oxide nanoparticles are doped with vanadium.
Wherein the reaction of step (a) is carried out in the range of pH 2 to 7.
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| KR102035041B1 (en) * | 2019-02-08 | 2019-11-18 | (주)폴리사이언텍 | Ultraviolet shielding resin compositions and synthetic fibers using thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003327431A (en) * | 2002-03-06 | 2003-11-19 | Ishihara Sangyo Kaisha Ltd | Rutile type titanium dioxide fine grain and production method thereof |
| KR20120123059A (en) * | 2009-12-23 | 2012-11-07 | 크로다 인터내셔날 피엘씨 | Particulate titanium dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003327431A (en) * | 2002-03-06 | 2003-11-19 | Ishihara Sangyo Kaisha Ltd | Rutile type titanium dioxide fine grain and production method thereof |
| KR20120123059A (en) * | 2009-12-23 | 2012-11-07 | 크로다 인터내셔날 피엘씨 | Particulate titanium dioxide |
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