KR102035041B1 - Ultraviolet shielding resin compositions and synthetic fibers using thereof - Google Patents

Abstract

The present invention relates to an ultraviolet-shieldable resin composition comprising a synthetic resin and a mixed particle of cerium-doped titanium dioxide nanoparticle and cerium-doped zinc oxide nanoparticle or a titanium dioxide/zinc oxide nanocomposite particle doped with cerium; and to a synthetic fiber prepared therefrom. The resin composition and synthetic fiber exhibit excellent UV shieldability without reduction in the ultraviolet-shieldability permanently even after being washed.

Description

UV Resistant Resin Composition and Synthetic Fiber Using the Same {ULTRAVIOLET SHIELDING RESIN COMPOSITIONS AND SYNTHETIC FIBERS USING THEREOF}

The present invention relates to a sunscreen resin composition and a synthetic fiber prepared therefrom. More particularly, the present invention relates to a UV-blocking resin composition and synthetic fibers prepared therefrom, which are excellent in blocking performance in a wide range of ultraviolet rays, and implement excellent UV-blocking properties permanently without damaging UV-blocking properties even when washed.

Ultraviolet rays are known to be a powerful culprit of skin aging, and there is a growing desire for the emergence of synthetic fibers with excellent UV protection to protect the human body from them.

The sunlight consists of gamma (γ) rays, X (X) rays, ultraviolet rays, visible rays, infrared rays, and radio waves, which have different wavelengths. Among them, ultraviolet rays are called UV (ultraviolet) in the sense of being shorter than the violet color of visible rays. Call.

UV light is divided into UVA (320-400 nm), UVB (290-320 nm) and UVC (200-290 nm) depending on the length of the wavelength. UVA is again divided into UVA II (320-340 nm) and UVA I (340-400 nm). 400 nm). Among them, UVC is absorbed and scattered in the ozone layer, water vapor, dust, etc. in the air, so only UVA and UVB harmful to the human body reach the surface, so UVA and UVB are usually blocked.

A few hours after exposure to UV light, the skin becomes red after eight hours of peaking and then gradually weakens and persists. This is called sun burn. In addition, when exposed to a large amount of ultraviolet light may be further developed to cause a burn state such as blisters, which are mainly caused by UVB.

UVA, on the other hand, can damage the immune system. This can be confirmed in the occurrence of photoallergic reactions, hives caused by sunlight, and the like. Unlike UVB, which burns directly on the skin and can feel it immediately, UVA penetrates deep into the skin, gradually creating blemishes and freckles and destroying the skin without your knowledge. In other words, if UVB burns the outer skin, UVA penetrates into the skin and destroys skin cells, and has a fatal effect on skin aging. UVA is deeply related to premature aging of skin cells and skin cancer, which has recently strengthened UVA blocking effects in advanced countries.

Recently, with the activation of leisure sports, outdoor activities have increased, and the necessity of the fiber for leisure sports clothing having excellent UV protection is emphasized. Representative methods for producing such garments include a post-processing method of coating or laminating organic sunscreens on fabrics and the like. Examples of organic sunscreens effective 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, and examples of organic sunscreens effective in the UVA I region include bis-ethylhexyloxyphenol methoxyphenyl triazine, butyl metoxydibenzoylmethane, dietylamino hydroxybenzoyl hexyl benzoate, disodium phenyl dibenimidazole tetrasulfonate, drometriazol trisiloxane, menthyl anthonicydeoxymethane terephthalate and bis-benzotriazolyl tetramethylbutylphenol.

The method of using the organic sunscreen is expensive to manufacture and there is a high risk of environmental problems caused by the use of a solvent, in particular, there is a disadvantage that the sunscreen effect is sharply lowered during use or washing.

In order to solve these disadvantages, a small amount of inorganic sunscreen is added during the polymerization of the resin to disperse or a mixture of the resin and the inorganic sunscreen is spun into a resin composition obtained through a separate compounding process to prepare synthetic fibers. There is a way to get clothing. Among the inorganic sunscreens, a representative example of an effective sunscreen agent in the UVB and UVA II regions may include titanium dioxide nanoparticles, and zinc oxide may be a representative example of the inorganic sunscreen effective in the UVA I region.

Since UV protection should exert effects in all areas of UVB, UVA II and UVA I, a method of mixing two or more of the above sunscreens is generally adopted. Nevertheless, the currently developed organic and inorganic sunscreens have low UV protection in the range of 360 ~ 400 nm adjacent to visible light in the UVA I region, and there is a lack of overall UV protection even when two or more sunscreens are mixed. The solution is very urgent and desperate. In other words, there is a need for technology development for a resin composition using a novel sunscreen agent and a synthetic fiber produced using the same, which can realize permanent sunscreen effects over all areas of UVB, UVA II and UVA I.

In order to solve the above problems, an object of the present invention is to provide a resin composition that is excellent in blocking properties in a wide range of ultraviolet rays, and does not deteriorate UV blocking performance even after washing, permanently providing excellent UV blocking properties. .

In addition, an object of the present invention is to provide a synthetic fiber having excellent ultraviolet blocking performance prepared from the resin composition.

In order to achieve the above object, the present invention provides a UV-blocking resin composition comprising a mixed resin and a synthetic resin of titanium dioxide nanoparticles doped with cerium and zinc oxide nanoparticles doped with cerium.

The present invention also provides a sunscreen resin composition comprising a cerium-doped titanium dioxide / zinc oxide nanocomposite particles and synthetic resin.

The present invention also provides a UV-blocking synthetic fiber prepared by melt spinning the UV-blocking resin composition.

One of the important objects in the present invention is to ensure excellent and excellent UV protection performance permanently. For this UV protection, the present invention uses an inorganic sunscreen, not an organic sunscreen. The present invention relates to a mixed particle of cerium-doped titanium dioxide nanoparticles and cerium-doped zinc oxide nanoparticles or a combination of cerium-doped titanium dioxide / zinc oxide nanocomposite particles and synthetic resin using an inorganic barrier agent. UVB, UVA II and UVA I Permanently provide excellent UV protection across all areas.

In addition, the present invention (a) preparing a titanium organic acid solution and cerium organic acid solution, (b) a suspension reactant obtained by adding an alkali metal hydroxide aqueous solution to the mixture of the titanium organic acid solution and cerium organic acid solution (C) adding a solid peroxide to the precipitate and reacting to obtain a solid precipitate, (d) separating the solid precipitate to powder It provides a method of producing a cerium-doped titanium dioxide nanoparticles comprising the step of obtaining, (usually the powder can be obtained by filtration, washing and drying the precipitate) and (e) sintering the powder. .

The present invention also provides a suspension phase reactant obtained by (a) preparing a zinc organic acid solution and a cerium organic acid solution, and (b) adding an alkali metal hydroxide aqueous solution to the mixture of the zinc organic acid solution and cerium organic acid solution. Separating the precipitate from the (precipitate can be filtered and washed to obtain a precipitate) (c) adding hydrogen peroxide to the precipitate and reacting to obtain a solid precipitate, (d) separating the solid precipitate to obtain a powder It provides a method for producing zinc oxide nanoparticles doped with cerium comprising the step of obtaining, (usually the powder can be obtained by filtration, washing and drying the precipitate) and (e) sintering the powder.

In addition, the present invention comprises the steps of (a) preparing a titanium organic acid solution, zinc organic acid solution and cerium organic acid solution, (b) an alkali metal hydroxide aqueous solution in a mixture of the titanium organic acid solution and zinc organic acid solution Obtaining a suspended phase reactant, (c) mixing a cerium organic acid solution with the suspended phase reactant, adding an aqueous alkali metal hydroxide solution to obtain a precipitate from the suspended phase reactant, and (usually, the precipitate is subjected to the suspended phase reactant). Obtained by filtration and washing) (d) adding hydrogen peroxide to the precipitate and reacting to obtain a solid precipitate, (e) obtaining a powder from the solid precipitate, (usually, the powder is filtered, washed and And (f) cerium-doped titanium dioxide / zinc oxide nanocomposites comprising the step of sintering said powder. It provides a method for producing party.

The sunscreen resin composition according to the present invention has the advantage of realizing excellent UV protection permanently over all areas of UVB, UVA II, UVA I.

In addition, the synthetic fiber prepared using the UV-blocking resin composition according to the present invention is permanently excellent UV protection across all areas of UVB, UVA II, UVA I without washing and damage to the UV protection performance even after washing As to implement, by dramatically improving the UV protection performance has a very useful advantage in a variety of fields, including clothing, especially leisure sports clothing.

Hereinafter, the present invention will be described with reference to one embodiment for detailed description of the present invention, but the present invention is not necessarily limited thereto.

The inventors of the present invention provide a mixture of nanoparticles selected from (A) a mixed particle of cerium doped titanium dioxide nanoparticles and cerium doped zinc oxide nanoparticles or a cerium doped titanium dioxide / zinc oxide nanocomposite particle and (B The present invention was completed by surprisingly discovering that by providing a UV-blocking resin composition including a synthetic resin, it is possible to realize excellent UV protection permanently over all areas of UVB, UVA II, and UVA I.

In addition, the present inventors can use this to produce a synthetic fiber that significantly improved the UV blocking performance.

Specifically, the present invention provides a UV-blocking resin composition comprising a mixed resin and a synthetic resin of titanium dioxide nanoparticles doped with cerium and zinc oxide nanoparticles doped with cerium.

The present invention also provides a sunscreen resin composition comprising a cerium-doped titanium dioxide / zinc oxide nanocomposite particles and synthetic resin.

In the UV-protective resin composition according to an embodiment of the present invention, the mixed particles are 5 to 500 parts by weight of the cerium-doped zinc oxide nanoparticles without limitation, based on 100 parts by weight of the titanium dioxide nanoparticles doped with cerium. It may be included.

In the sunscreen resin composition according to an embodiment of the present invention, the nanoparticles or nanocomposite particles may be 1 to 50% by weight, without limitation, doped with cerium.

In the sunscreen resin composition according to an embodiment of the present invention, the synthetic resin is not particularly limited as long as it achieves the desired effect of the present invention, for example polyester, polyamide, polyacrylonitrile, polyurethane , Polypropylene, polyethylene and polyvinyl chloride may be any one or more selected from the group consisting of, but is not limited thereto.

In the sunscreen resin composition according to an embodiment of the present invention, the resin composition is not limited so long as the object to be achieved in the present invention is achieved, for example, 100 parts by weight of synthetic resin doped with cerium dioxide A mixed particle of titanium nanoparticles and cerium-doped zinc oxide nanoparticles may be included in an amount of 0.001 to 10 parts by weight, but is not limited thereto.

In the sunscreen resin composition according to an embodiment of the present invention, the resin composition is not limited so long as the object to be achieved in the present invention is achieved, for example, 100 parts by weight of synthetic resin doped with cerium dioxide Titanium / zinc oxide nanocomposite particles may be included in 0.001 to 10 parts by weight, but is not limited thereto.

In the sunscreen resin composition according to an embodiment of the present invention, the resin composition is any one selected from the group consisting of dispersants, antioxidants, heat stabilizers, pigments, optical brighteners, antibacterial agents, deodorants, flame retardants and antistatic agents. It may further include the above additives.

In addition, the present invention

(a) preparing a titanium organic acid solution and a cerium organic acid solution,

(b) separating and obtaining a precipitate from the suspension phase reactant obtained by adding an alkali metal hydroxide aqueous solution to a mixture of the titanium organic acid solution and cerium organic acid solution;

(c) adding hydrogen peroxide to the precipitate and reacting to obtain a solid precipitate,

(d) separating the solid phase precipitate to obtain a powder; and

(e) sintering the powder

It provides a method for producing a cerium-doped titanium dioxide nanoparticles comprising a.

In addition, the present invention

(a) preparing a zinc organic acid solution and a cerium organic acid solution,

(b) separating the precipitate from the suspension phase reactant obtained by adding an alkali metal hydroxide aqueous solution to the mixture of the zinc organic acid solution and the cerium organic acid solution, and

(c) adding hydrogen peroxide to the precipitate and reacting to obtain a solid precipitate,

(d) separating the solid phase precipitate to obtain a powder; and

(e) sintering the powder

It provides a method for producing zinc oxide nanoparticles doped with cerium containing.

In addition, the present invention

(a) preparing a titanium organic acid solution, a zinc organic acid solution and a cerium organic acid solution,

(b) adding an alkali metal hydroxide aqueous solution to the mixture of the titanium organic acid solution and the zinc organic acid solution to obtain a suspended phase reactant,

(c) mixing a cerium organic acid solution with the suspension phase reactant and adding an alkali metal hydroxide aqueous solution to obtain a precipitate from the suspension phase reaction obtained;

(d) adding hydrogen peroxide to the precipitate and reacting to obtain a solid precipitate,

(e) obtaining a powder from said solid phase precipitate, and

(f) sintering the powder

It provides a method for producing a cerium-doped titanium dioxide / zinc oxide nanocomposite particles comprising a.

The present invention provides a UV-blocking synthetic fiber prepared by melt spinning the UV-blocking 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, "nanoparticle" or nanocomposite particle "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-blocking resin composition comprising a mixed resin and a synthetic resin of the cerium-doped titanium dioxide nanoparticles and cerium-doped zinc oxide nanoparticles.

Another embodiment of the present invention is a sunscreen resin composition comprising a cerium-doped titanium dioxide / zinc oxide nanocomposite particles and synthetic resin.

The synthetic resin is a resin used as a base material, but is not particularly limited, preferably polyester, polyamide, polyacrylonitrile, polyurethane, polypropylene, polyethylene, polyvinyl chloride and the like. It is more preferable to use polyester, polyamide, polyacrylonitrile, etc. which are widely used for a fiber use among these.

As one specific example, in the case of adopting polyester in order to achieve the desired effect by applying to fiber, the polyester is not particularly limited, but the polyester has an intrinsic viscosity (tetra chloroethane: phenol weight ratio = 60: It is preferable to use a mixed solvent of 40 and use a viscosity tube at 35 ° C., measured according to ASTM D-4603-96), of 0.5 to 0.8.

In addition, in the case of adopting polyamide, the polyamide has a relative viscosity of 2.0 to 3.5 using a relative viscosity (measured according to ASTM D789 using 1 g of a resin component in 100 ml of 20% 96% sulfuric acid). It is preferable, but this is preferred in consideration of various physical properties such as processability and fiber spinning, but not limited to those of the category.

In the present invention, the mixed particles of the titanium dioxide nanoparticles doped with cerium and the zinc oxide nanoparticles doped with cerium or the titanium dioxide / zinc oxide nanocomposite particles doped with cerium are used to impart UV protection.

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 higher, which is the energy gap of the valence and conduction bands in the semiconductor material. An inorganic material having such an energy gap is preferable. It is not clear why the cerium-doped titanium dioxide nanoparticles and cerium-doped zinc oxide nanoparticles or mixed particles of cerium-doped titanium dioxide / zinc oxide nanocomposite particles according to the present invention. It has an energy gap of the valence band and conduction band, and the UV absorption performance is greatly improved so that UV blocking ability can be exhibited in the range of 370 to 400 nm, which is the UVA I region that could not be exhibited. Excellent sun protection can be achieved.

In the present invention, the method for preparing the cerium-doped titanium dioxide nanoparticles includes (a) preparing a titanium organic acid solution and a cerium organic acid solution, and (b) alkali in a mixture of the titanium organic acid solution and cerium organic acid solution. Obtaining a precipitate from the suspension phase reacted by adding a metal hydroxide aqueous solution to react, (c) adding hydrogen peroxide to the precipitate and reacting to obtain a solid precipitate, (d) separating the solid precipitate to obtain a powder And (e) sintering the powder.

Specifically, in step (a), a titanium organic acid salt solution prepared by dissolving a titanium organic acid salt selected from titanium nitrate, titanium sulfate, titanium hydrochloride, titanium acetate, titanium carbonate, and the like in a solvent (mainly water, alcohol or a mixture thereof) is prepared.

In addition, a cerium organic acid solution prepared by dissolving a cerium organic acid salt selected from cerium nitrate, cerium sulfate, cerium hydrochloride, cerium acetate, cerium carbonate and the like in a solvent (mainly water, alcohol or a mixture thereof) is prepared.

In the step (b), the prepared titanium organic acid solution and cerium organic acid solution are mixed at a predetermined ratio, and an appropriate amount of an alkali metal hydroxide solution such as NaOH and KOH is added to adjust the pH to control the reaction at a constant temperature ranging from room temperature to 100 ° C. To obtain the suspended reaction product. Specifically, the obtained suspended phase reactant is filtered and washed several times with distilled water to obtain a precipitate.

In step (c), an appropriate concentration of hydrogen peroxide is added to the precipitate and reacted at an appropriate temperature ranging from 50 to 100 ° C. to obtain a solid phase precipitate.

In step (d), the solid precipitate is filtered, washed with distilled water and dried to obtain a powder.

In step (e), the powder obtained in the previous step is put in a crucible and fired. The firing temperature is not particularly limited as long as the particles to be obtained in the present invention can be obtained, but preferably, titanium dioxide nanoparticles doped with cerium can be obtained through a sintering process at a temperature condition in the range of 500 to 800 ° C.

The size of the cerium-doped titanium dioxide nanoparticles can vary greatly by the adjustment of pH, and the particle size tends to increase with increasing pH. Preferably said pH is 2-7, More preferably, it is 3-6.

In the present invention, the method for preparing the cerium-doped zinc oxide nanoparticles includes (a) preparing a zinc organic acid solution and a cerium organic acid solution, and (b) alkali in a mixture of the zinc organic acid solution and cerium organic acid solution. Obtaining a precipitate from the suspension phase reacted by adding a metal hydroxide aqueous solution to react, (c) adding hydrogen peroxide to the precipitate and reacting to obtain a solid precipitate, (d) separating the solid precipitate to obtain a powder And (e) sintering the powder.

Specifically, in step (a), a zinc organic acid solution prepared by dissolving a zinc organic acid salt selected from zinc nitrate, zinc sulfate, zinc hydrochloride, zinc acetate, zinc carbonate and the like in a solvent (mainly water, alcohol or a mixture thereof) is prepared.

In addition, a cerium organic acid solution prepared by dissolving a cerium organic acid salt selected from cerium nitrate, cerium sulfate, cerium hydrochloride, cerium acetate, cerium carbonate and the like in a solvent (mainly water, alcohol or a mixture thereof) is prepared.

In the step (b), the prepared zinc organic acid solution and cerium organic acid solution are mixed at a predetermined ratio, and an appropriate amount of an alkali metal hydroxide solution such as NaOH and KOH is added to adjust the pH to control the reaction at a constant temperature ranging from room temperature to 100 ° C. To obtain the suspended reaction product. Specifically, the obtained suspended phase reactant is filtered and washed several times with distilled water to obtain a precipitate.

In step (c), an appropriate concentration of hydrogen peroxide is added to the precipitate and reacted at an appropriate temperature ranging from 50 to 100 ° C. to obtain a solid phase precipitate.

In step (d), the solid precipitate is filtered, washed with distilled water and dried to obtain a powder.

In step (e), the powder obtained in the previous step is placed in a crucible and subjected to a sintering process at a temperature condition in the range of 500 to 800 ° C., thereby obtaining zinc oxide nanoparticles doped with cerium. The size of the cerium-doped zinc oxide nanoparticles can vary greatly by the adjustment of pH, and the particle size tends to increase with increasing pH. Preferably said pH is 2-7, More preferably, it is 3-6.

In the present invention, the method of preparing the cerium-doped titanium dioxide / zinc oxide nanocomposite particles includes (a) preparing a titanium organic acid solution, a zinc organic acid solution and a cerium organic acid solution, and (b) the titanium organic acid solution. And adding an aqueous alkali metal hydroxide solution to the mixture of zinc organic acid solution and reacting to obtain a suspended phase reactant, (c) adding a suspension of the cerium organic acid solution to the suspended phase reactant and adding an aqueous alkali metal hydroxide solution to react the suspended phase reactant. Obtaining a precipitate from (d) adding hydrogen peroxide to the precipitate and reacting to obtain a solid precipitate, (e) obtaining a powder from the solid precipitate, and (f) sintering the powder.

Specifically, in step (a), a titanium organic acid solution, zinc nitrate, dissolved in a solvent (mainly water, alcohol or a mixture thereof) in a titanium organic acid salt selected from titanium nitrate, titanium sulfate, titanium hydrochloride, titanium acetate, titanium carbonate, etc. Zinc organic acid solution dissolved in a solvent (mainly water, alcohol or a mixture thereof) in zinc organic acid salt selected from zinc sulfate, zinc hydrochloride, zinc acetate, zinc carbonate, and cerium nitrate, cerium sulfate, cerium sulfate, cerium acetate, cerium A cerium organic acid solution prepared by dissolving a cerium organic acid salt selected from carbonate or the like in a solvent (mainly water, alcohol or a mixture thereof) is prepared.

In the step (b), the prepared titanium organic acid solution and zinc organic acid solution are mixed at a desired ratio, and an appropriate amount of an alkali metal hydroxide solution such as NaOH and KOH is added to adjust the pH to control the pH at a temperature ranging from room temperature to 100 ° C. To obtain the suspended reaction product.

In the step (c), the suspension reactant obtained by mixing a cerium organic acid solution with the suspended reactant, adding an aqueous alkali metal hydroxide solution, and filtering the solution is washed several times with distilled water to obtain a precipitate.

In step (d), hydrogen peroxide is added to the precipitate and reacted at an appropriate temperature ranging from 50 to 100 ° C. to obtain a solid phase precipitate.

In step (e), the solid phase precipitate is filtered, washed and dried to obtain a powder.

In step (f), the powder obtained in the previous step is put in a crucible and calcined, but the firing temperature is not particularly limited, but preferably, when the sintering process is performed at a temperature condition in the range of 500 to 800 ° C., titanium dioxide / zinc oxide doped with cerium Nanocomposite particles can be obtained. The size of the cerium-doped titanium dioxide / zinc oxide nanocomposite particles can vary greatly by the adjustment of pH, and the particle size tends to increase with increasing pH. Preferably said pH is 2-7, More preferably, it is 3-6.

In the present invention, the mixed particles of the cerium-doped titanium dioxide nanoparticles and the cerium-doped zinc oxide nanoparticles specifically include a cerium-doped zinc oxide nanoparticles based on 100 parts by weight of the cerium-doped titanium dioxide nanoparticles. 5 to 400 parts by weight, preferably 20 to 400 parts by weight may be included, but is not limited thereto.

In addition, the nanoparticles or nanocomposite particles in the present invention is more preferably 1 to 50% by weight, preferably 5 to 30% by weight of the doped cerium. Within the above range, excellent UV protection effect can be obtained in all areas of UVB, UVA II, and UVA I, and the absorption of visible light is less, so that the transparency is less damaged, and thus, the bright dye due to opacity is more preferred.

The shape of the nanoparticles or nanocomposite particles is not particularly limited, such as spherical, needle-like, plate-like, but is preferably better in terms of spherical and plate-like, the surface area per the same weight can be induced more light scattering.

In addition, the nanoparticles or nanocomposite particles are not particularly limited in average particle diameter, but preferably 5 to 500 nm, preferably 10 to 300 nm, and more preferably 30 to 250 nm. Within the range of 5 to 500 nm, light scattering occurs well, so that the effect of blocking ultraviolet rays is further enhanced, particle dispersibility is excellent, and transparency is not impaired, so it is more preferred in dyeing property.

The UV-protective resin composition according to the present invention contains 0.001 to 10 parts by weight, preferably 0.1 to 7 parts by weight of mixed particles of cerium-doped titanium dioxide nanoparticles and cerium-doped zinc oxide nanoparticles based on 100 parts by weight of the synthetic resin. Part is preferably included, more preferably 0.2 to 5 parts by weight is more preferably included but is not necessarily limited thereto. In the above composition ratio, excellent UV blocking properties, transparency is not impaired, it is possible to secure a clear dyeing is more preferred.

In addition, the sunscreen 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 titanium dioxide / zinc oxide nanocomposite particles doped with cerium, based on 100 parts by weight of the synthetic resin. Preferably 0.2 to 5 parts by weight is more preferably included, but is not necessarily limited thereto. In the above composition ratio, excellent UV blocking properties, transparency is not impaired, it is possible to secure a clear dyeing is more preferred.

In order to increase the dispersibility of nanoparticles or nanocomposite particles, the sunscreen resin composition according to the present invention is mixed with a mixture of synthetic resin and nanoparticles at an appropriate ratio, such as a screw screw extruder, a twin screw extruder, a mixing roll, a balbaric mixer, and a kneader. Into the hopper of the kneader, etc., and melt kneading and dispersing can be prepared in the form of compound pellets.

Alternatively, a high concentration of mixed particles or nano composite particle master batches may be prepared and the synthetic resin and nano particle mixture master batch pellets may be mixed by dry blending, or the mixture may be introduced into a hopper of a kneader and melt kneaded to produce pellets to form a dispersibility. It can be secured. In particular, if the dispersibility is poor, the composition obtained due to the aggregated particles may be cut off during melt spinning, which may greatly impair the radioworkability, and may also cause a problem of inferior UV protection to the amount added. It is preferable.

The sunscreen resin composition according to the present invention is a conventional additive, for example, a dispersant, an antioxidant, a heat stabilizer, a pigment, a fluorescent brightener, an antimicrobial agent, a deodorant, a flame retardant, an antistatic agent, etc., without impairing the object of the present invention. Including may be further included, but is not necessarily limited thereto.

The content of the additive is not particularly limited in the range of achieving the effect for the purpose of the present invention, but may preferably be used in the range of 0.001 to 5 parts by weight based on 100 parts by weight of the synthetic resin. In particular, the dispersant in the additive is preferably added to improve the dispersibility of the nanoparticles or nanocomposite particles. The dispersant may vary depending on the type of synthetic resin used as the base material, and a polymer dispersant capable of a low molecular weight dispersant is preferable in order to prevent poor quality due to transition of the dispersant. For example, in the case of polyamide, polyethylene, and polypropylene, polyethylene-based ionomer is more preferable.

The dispersant is contained in an amount of 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. If the amount of the dispersant is less than 0.01 parts by weight, the effect of improving the dispersibility of the desired nanoparticles or nanocomposite particles is insignificant. If the dispersant is more than 5 parts by weight, the stiffness is weakened due to the excess dispersant which does not contribute to the dispersion and the detergent There is a fear that washing fastness may decrease due to affinity.

The present invention also provides a UV-blocking synthetic fiber obtained by the fiber manufacturing method by the conventional melt spinning the resin composition. For example, the UV-protective resin composition pellets according to the present invention are dried in consideration of the characteristics of the matrix synthetic resin and then melt-extruded by injecting into a hopper of an extruder, and then spun through a mold of a constant shape, cooled, heat-set, stretched and post-processed. UV-blocking synthetic fibers can be prepared through the process.

Hereinafter, the present invention will be described in more detail with reference to Examples, which are intended only for understanding the constitution and effects of the present invention and are not intended to limit the scope of the present invention.

The UV blocking property, UV blocking persistence and radiation workability of the UV blocking resin composition and the synthetic fiber of the present invention were evaluated by the following test method.

(1) UV protection

In consideration of the fact that it is difficult to evaluate the UV ray blocking property of the fiber (filament) itself, it is made into a film having a thickness of 20 μm (3 denier fiber diameter level) using a sample resin, and the UV region for the sample film using a UV-VIS Spectrometer. UV protection (%) was assessed as the percentage of impermeable amount in.

(2) UV blocking persistence

KS K ISO 105-C06 (Fiber Wash Fastness Test Method) was applied mutatis mutandis. Prepare a wash solution dissolved in 4 g of standard detergent in 1 liter of water, add it to a test bottle prepared in advance, and dip a sample of a film having a thickness of 20 μm (3 denier fiber diameters) used for evaluating the UV protection property and place the test bottle in a shaker. After installation, shake for 30 minutes at 60 ℃, discard the wash solution and rinse twice with water. After repeating this operation 100 times, the film sample was dried and the UV protection rate (%) was evaluated using a UV-VIS Spectrometer to calculate the change rate (%) before and after washing. It was. UV protection was evaluated by classifying UVA I barrier and overall barrier.

division ◎ (excellent) ○ (good) △ (normal) X (bad) Change rate of sunscreen before and after washing (%) Less than 1 1 or more
Less than 5 5 or more
Less than 10 over 10

(3) spinning workability

The frequency (times / day) of trimming at the time of spinning was measured to evaluate the radio workability according to the criteria shown in Table 2 below.

division ◎ (excellent) ○ (good) △ (normal) X (bad) Frequency of trimming when spinning (times / day) Less than 1 One 2 to 3 4 or more

Example 1

As a polyester resin for fibers, polyethylene terephthalate resin (PET-A) having an intrinsic viscosity of 0.65 was prepared.

First, 1.0 mol / L TiCl ₄ (Compound A) as titanium organic acid salt, 1.0 mol / L ZnSO ₄ H ₂ O (Compound B) as zinc organic acid salt, 1.0 mol / L Ce (NO ₃ as cerium organic acid salt) ) _{3 ·} 6H ₂ O (Compound C) aqueous solution was prepared. 5 mol / L NaOH aqueous solution was added to 1 L of the mixture of 80% by weight of Compound A and 20% by weight of Compound C to adjust the pH to 3.5 and reacted at room temperature. A white precipitate was formed, which was filtered and washed three times with distilled water. 385 g was obtained separately. When 0.5 L of 30 wt% aqueous hydrogen peroxide solution is added and reacted at 60 ° C., a solid oxide precipitate is obtained. The resultant is filtered, washed three times with distilled water, and dried to obtain a powder obtained from a crucible and sintered at 700 ° C. for 6 hours. As a result, titanium dioxide nanoparticles (Ce / TiO ₂ -A) doped with 6.4 wt% of cerium having an average diameter of 35 nm were obtained. In addition, 5 mol / L NaOH aqueous solution was added to 1 L of a mixture of 75 wt% Compound B and 25 wt% Compound C to adjust the pH to 3.5 and reacted at room temperature to produce a white precipitate, which was filtered and washed three times with distilled water. 360 g of precipitate was isolated. After adding 0.5 L of 30 wt% aqueous hydrogen peroxide solution and reacting at 50 ° C., a solid oxide precipitate was obtained. The powder obtained by filtration, washing with distilled water three times and dried was put in a crucible and sintered at 800 ° C. for 12 hours. As a result, zinc oxide nanoparticles (Ce / ZnO-A) doped with 8.9 wt% of cerium having an average diameter of 35 nm were obtained.

100 parts by weight of PET-A, 2.0 parts by weight of Ce / TiO ₂ -A and 0.5 parts by weight of Ce / ZnO-A were mixed and kneaded under conditions of a cylinder temperature of 280 ° C. in an L / D 42, 90Φ twin screw extruder. It disperse | distributed and the resin composition (1) pellet was obtained.

The obtained resin composition (1) pellets were dried to a moisture content of 0.05% by weight or less, charged into an extruder hopper, and melt-extruded to prepare a spinning solution. The spinning solution is spun under a circular cross-section spinneret at a spinning temperature of 285 ° C and a spinning speed of 4,000 m / min, and cooled by blowing air at 20 ° C at a wind speed of 0.5 m / min. After that, 3 denier synthetic fibers (1) were obtained. The obtained resin composition (1) was prepared using a heating press to produce a film having a thickness of 20 μm (3 denier fiber diameter level), and the UV ray blocking property and the UV blocking persistence were measured, and the resin composition (1) was melted and spun to synthetic fibers. During (1), radioworkability was evaluated as the frequency of trimming during spinning. The results are shown in Table 3.

Example 2

The resin composition was carried out in the same manner as in Example 1 except that the composition (2) mixed at 100 parts by weight of PET-A, 1.5 parts by weight of Ce / TiO ₂ -A and 1.0 parts by weight of Ce / ZnO-A was used. ) Pellets and 3 denier synthetic fibers (2) were obtained and their UV protection, UV persistence and radioworkability were evaluated. The results are shown in Table 3.

Example 3

The resin composition was carried out in the same manner as in Example 1 except that the composition (3) mixed at 100 parts by weight of PET-A, 1.0 parts by weight of Ce / TiO ₂ -A and 1.5 parts by weight of Ce / ZnO-A was used. ) Pellets and 3 denier synthetic fibers (3) were obtained and their UV protection, UV persistence and radioworkability were evaluated. The results are shown in Table 3.

Example 4

The resin composition (4) was carried out in the same manner as in Example 1 except that the composition (4) mixed at 100 parts by weight of PET-A, 0.5 parts by weight of Ce / TiO ₂ -A and 2.0 parts by weight of Ce / ZnO-A was used. ) Pellets and 3 denier synthetic fibers (4) were obtained and their UV protection, UV persistence and radioworkability were evaluated. The results are shown in Table 3.

Example 5

First, 1.0 mol / L TiCl ₄ (Compound A) as titanium organic acid salt, 1.0 mol / L ZnSO ₄ · H ₂ O (Compound B) as zinc organic acid salt, 1.0 mol / L Ce (NO ₃ as cerium organic acid salt) ) _3. 6H ₂ O (Compound C) aqueous solution was prepared. 50 mol% of Compound A and 50 wt% of Compound B were added with 5 mol / L aqueous NaOH solution to adjust the pH to 4.0 and reacted at 60 ° C. to obtain a suspension phase reaction. Compound C was added thereto, followed by addition of 5 mol / L NaOH aqueous solution to adjust pH to 5.0 and reaction at 70 ° C., resulting in a suspension white precipitate which was filtered and washed three times with distilled water to give 412 g of precipitate. It was separated. After adding 0.5 L of 30 wt% aqueous hydrogen peroxide solution and reacting at 60 ° C., a solid oxide precipitate was obtained. The resultant was filtered, washed three times with distilled water, and dried to obtain a powder obtained from a crucible and then sintered at 800 ° C. for 12 hours. As a result, titanium dioxide / zinc oxide nanocomposite particles (Ce / TiO ₂ / ZnO-A) doped with 14.8 wt% of cerium having an average diameter of 42 nm were obtained.

The resin composition (5) pellets and 3 denier synthetic fibers were carried out in the same manner as in Example 1, except that the composition (5) mixed at 100 parts by weight of PET-A and 2.0 parts by weight of Ce / TiO ₂ ZnO-A was used. (5) was obtained and evaluated for UV protection, UV persistence and radioworkability. The results are shown in Table 3.

Example 6

First, 1.0 mol / L of Ti (NO ₃ ) ₄ (compound D) as titanium organic acid salt, 1.0 mol / L of Zn (NO ₃ ) ₂ .6H ₂ O (compound E) as zinc organic acid salt, 1.0 as cerium organic acid salt. A mol / L aqueous solution of Ce (NO ₃ ) ₃ .6H ₂ O (Compound C) was prepared. To 1 L of a mixture of 40% by weight of Compound D and 60% by weight of Compound E was added a 5 mol / L aqueous NaOH solution to adjust the pH to 4.5 and reacted at 65 ° C. to obtain a suspension phase reaction. The compound C was added thereto, followed by addition of 5 mol / L NaOH aqueous solution to adjust the pH to 5.5, followed by reaction at 80 ° C., which produced a white precipitate which was filtered and washed three times with distilled water to give 431 g of precipitate. It was separated. After adding 0.5 L of 30 wt% aqueous hydrogen peroxide solution and reacting at 60 ° C., a solid oxide precipitate was obtained. The powder obtained by filtration, washing three times with distilled water and drying was put in a crucible and then sintered at 800 ° C. for 12 hours. As a result, titanium dioxide / zinc oxide nanocomposite particles (Ce / TiO ₂ / ZnO-B) doped with 13.9% by weight of cerium having an average diameter of 34 nm were obtained.

The same procedure as in Example 1 was carried out except that 100 parts by weight of PET-A and 2.0 parts by weight of Ce / TiO ₂ ZnO-B were used. (6) was obtained and evaluated for UV protection, UV persistence and radiation workability. The results are shown in Table 3.

Example 7

As a polyamide resin for fibers, polyamide 6 (PA-A) having a relative viscosity of 2.5 was prepared.

The PA-A 100 parts by _{weight, Ce / TiO 2 ZnO-B} 0.5 parts by weight of Ce / TiO ₂ ZnO-B 1.5 parts by weight was used in the composition mixed at mixing ratios portion other than the same manner as in Example 1 carried out in the resin composition (7 ) Pellets were obtained, and the same as in Example 1 except that the melt spinning temperature was set at the spinning temperature of 255 ° C., to obtain 3 denier synthetic fibers (7). Was evaluated. The results are shown in Table 3.

Example 8

DuPont, an ionomer, is a copolymer of methacrylic acid (15% by weight) and ethylene (85% by weight) neutralized with sodium ions (neutrality 60%) as a dispersant for the nanoparticle mixture. Surlyn 8920 (PEI) was prepared.

A pellet of the resin composition (8) was obtained in the same manner as in Example 1 except that the composition mixed at 100 parts by weight of PA-A, 1.5 parts by weight of Ce / TiO ₂ ZnO-B and 1.0 parts by weight of PEI was used. Except that the spinning temperature was set to 255 ℃ spinning was carried out in the same manner as in Example 1 to obtain a three-denier synthetic fiber (8), to evaluate the UV protection, UV persistence and spinning workability. The results are shown in Table 3.

Example 9

As a polypropylene resin for fibers, polypropylene (PP-A) having a melt index of 15.0 g / 10 minutes (230 ° C.) was prepared.

The PP-A 100 parts by _{weight, Ce / TiO 2 ZnO-A} 0.5 parts by _{weight, Ce / TiO 2 ZnO-B} 1.0 parts by weight carried out in the same manner as in Example 1 except that the composition mixed at the compounding ratio PEI 1.0 parts by weight of To obtain a resin composition (9) pellets were obtained in the same manner as in Example 1 except that the melt spinning temperature was set to a spinning temperature of 255 ℃, to obtain a synthetic fiber (9) of 3 denier, UV protection, UV blocking Persistence and radioworkability were evaluated. The results are shown in Table 3.

Comparative Example 1

As a nanoparticle, plate-shaped cerium oxide (CeO ₂ -A, Degussa Co., Ltd.) of an average particle diameter of 50 nm was prepared.

The resin composition (C1) pellets and 3 denier synthetic fibers (C1) were obtained in the same manner as in Example 1 except that 100 parts by weight of PET-A and 2.5 parts by weight of CeO ₂ -A were used. UV protection, UV persistence and radiation workability were evaluated. The results are shown in Table 3.

Comparative Example 2

As nanoparticles, spherical zinc oxide (BYK, ZnO-A) having an average particle diameter of 80 nm was prepared.

The resin composition (C2) pellets and 3 denier synthetic fibers (C2) were obtained in the same manner as in Example 7, except that 100 parts by weight of PA-A and 2.5 parts by weight of ZnO-A were used. UV protection, UV persistence and radiation workability were evaluated. The results are shown in Table 3.

Comparative Example 3

As nanoparticles, spherical titanium dioxide (DuPont, TiO ₂ -A) having an average particle diameter of 120 nm was prepared.

The resin composition (C3) pellets and 3 denier synthetic fibers (C3) were obtained in the same manner as in Example 9, except that 100 parts by weight of PP-A and 2.5 parts by weight of TiO ₂ -A were used. UV protection, UV persistence and radiation workability were evaluated. The results are shown in Table 3.

[Comparative Example 4]

Benzophenone-3 (BASF, trade name Uninul M40) as an effective organic sunscreen in the UVB and UVA II region was prepared as drometriazol trisiloxane (BASF, Mexoryl XL) as an effective organic sunscreen in the UVA I region.

100 parts by weight of PET-A, 2.0 parts by weight of benzophenone-3, 2.0 parts by weight of drometriazol trisiloxane was mixed in the same manner as in Example 1 except that the resin composition (C4) pellets and 3 denier synthetic fibers ( C4) was obtained and the UV protection, UV persistence and radioworkability were evaluated. The results are shown in Table 3.

[Comparative Example 5]

As nanoparticles, spherical titanium dioxide (DuPont, TiO ₂ -A) with an average particle diameter of 120 nm, spherical zinc oxide (BYK, ZnO-A) with an average particle diameter of 80 nm and plate-like cerium oxide (Degussa, with an average particle diameter of 50 nm) CeO ₂ -A) was prepared.

1.5 parts by weight of TiO ₂ -A, 1 part by weight of ZnO-A and 0.5 parts by weight of CeO ₂ -A were added to 100 parts by weight of PET-A, and pelletized in the same manner as in Example 1. And also spun to make fibers. The results are shown in Table 3.

division Composition (part by weight) UV-rays
% Blocking UV-rays
Block persistence radiation
Workability Synthetic resin Sunscreen Dispersant UVA I all Example 1 PET-A (100) Ce / TiO ₂ -A (2.0)
Ce / ZnO-A (0.5) - 91 98 ◎ ○ Example 2 PET-A (100) Ce / TiO ₂ -A (1.5)
Ce / ZnO-A (1.0) - 94 98 ◎ ○ Example 3 PET-A (100) Ce / TiO ₂ -A (1.0)
Ce / ZnO-A (1.5) - 97 99.5 ◎ ○ Example 4 PET-A (100) Ce / TiO ₂ -A (0.5)
Ce / ZnO-A (2.0) - 100 100 ◎ ○ Example 5 PET-A (100) Ce / TiO ₂ /ZnO-A(2.0) - 92 98 ◎ ○ Example 6 PET-A (100) Ce / TiO ₂ /ZnO-B(2.0) - 100 100 ◎ ○ Example 7 PA-A (100) Ce / TiO ₂ /ZnO-A(0.5)
Ce / TiO ₂ /ZnO-B(1.5) - 100 100 ◎ ○ Example 8 PA-A (100) Ce / TiO ₂ /ZnO-B(1.5) PEI (1.0) 100 100 ◎ ◎ Example 9 PP-A (100) Ce / TiO ₂ /ZnO-A(0.5)
Ce / TiO ₂ /ZnO-B(1.0) PEI (1.0) 100 100 ◎ ◎ Comparative Example 1 PET-A (100) CeO ₂ -A (2.5) - 45 77 ○ ○ Comparative Example 2 PA-A (100) ZnO-A (2.5) - 33 71 ○ ○ Comparative Example 3 PP-A (100) TiO ₂ -A (2.5) - 11 62 ○ ○ Comparative Example 4 PET-A (100) Enzophenone-3
(2.0)
Drometrizole Trisiloxane
(2.0) - 51 76 X ◎ Comparative Example 5 PET-A (100) TiO ₂ (1.5) / ZnO (1.0) / CeO ₂ (0.5) - 72 83 ○ ○

As can be seen from Examples 1 to 9, mixed particles of cerium-doped titanium dioxide nanoparticles and cerium-doped zinc oxide nanoparticles or cerium-doped titanium dioxide / zinc oxide nanocomposite particles and synthetic resins Synthetic fibers prepared using a sunscreen resin composition comprising a UVB, UVA II, UVA I can be seen that the total UV protection over all areas are very excellent. In addition, it was confirmed that the excellent UV blocking persistence can implement a permanent UV blocking. In particular, synthetic fibers prepared using the organic or inorganic sunscreen according to the prior art according to Comparative Examples 1 to 4 is greatly contrasted with the large lack of overall UV protection due to the weak UV protection in the UVA I region. . In addition, the comparative example 5 is superior to the comparative examples 1 to 4, but compared to the embodiment of the present invention showed a significantly lower UV protection and persistence and radiation workability.

In addition, Example 8 and Example 9 was used in conjunction with a suitable dispersant, it was confirmed that due to the improved dispersibility of the nanoparticle mixture, the ultraviolet ray shielding and radiation workability is further improved.

As described above in the present invention has been described by a limited embodiment, but this is only provided to help a more general understanding of the present invention, the present invention is not limited to the above embodiments, the present invention is not limited to the common knowledge Those having a variety of modifications and variations are possible from these descriptions.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and all the things that are equivalent to or equivalent to the claims as well as the following claims will belong to the scope of the present invention. .

Claims (10)

(A) a mixture of nanoparticles selected from cerium-doped titanium dioxide nanoparticles and cerium-doped zinc oxide nanoparticles, or a cerium-doped titanium dioxide / zinc oxide nanocomposite particle, and (B) a synthetic resin ,
The nanoparticles and nanocomposite particles have an average particle diameter of 5 to 500 nm, a content of doped cerium is 1 to 50% by weight,
Ultraviolet ray-protective resin composition containing 0.001 to 10 parts by weight of the nanoparticle mixture with respect to 100 parts by weight of the synthetic resin. The method of claim 1,
The mixed particles are UV-blocking resin composition containing 5 to 400 parts by weight of the cerium-doped zinc oxide nanoparticles based on 100 parts by weight of the cerium-doped titanium dioxide nanoparticles. delete The method of claim 1,
The synthetic resin is any one or more selected from the group consisting of polyester, polyamide, polyacrylonitrile, polyurethane, polypropylene, polyethylene and polyvinyl chloride. delete The method of claim 1,
The resin composition further comprises at least one additive selected from the group consisting of dispersants, antioxidants, heat stabilizers, pigments, optical brighteners, antibacterial agents, deodorants, flame retardants and antistatic agents. delete delete delete A sunscreen synthetic fiber prepared by melt spinning the sunscreen resin composition of any one of claims 1, 2, 4 and 6.