KR20210121762A - Preparing method of germanium solution - Google Patents

Abstract

Disclosed is a method for manufacturing a germanium solution having an antibacterial effect and far-infrared emitting effect. The present invention includes: a first reaction step of mixing and reacting formalin, methanol, sodium hydroxide, triethanolamine, hexamine and melamine; a second reaction step of mixing and reacting formalin, glyoxal, phosphate, triethanolamine, hexamine and melamine with a first reactant; a third reaction step of mixing and reacting N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane) and methyltrimethoxysilane to a second reactant; a fourth reaction step of mixing and reacting ammonium chloride and water with a third reactant; a fifth reaction step of mixing and reacting gadolinium (III) complex (Gd(DOTA-FPG)(H_2O)) with a fourth reactant; a sixth reaction step of mixing and reacting water, sodium hydroxide, triethanolamine, hydrogen peroxide (H_2O_2) and germanium with a fifth reactant; and a step of mixing and stirring water and methanol to a sixth reactant.

Description

Germanium solution manufacturing method {Preparing method of germanium solution}

The present invention relates to a method for preparing a germanium aqueous solution, and more particularly, to a method for stably obtaining an aqueous germanium solution.

Germanium with an atomic number of 32 and an atomic weight of 72.59 is a silver-gray metalloid with intermediate properties between a metal and a non-metal. It is concentrated in coal and is contained in soil, plants, and mineral waters. It has been found that the high germanium content of spring water or hot springs, which is highly effective in treating incurable diseases, has been revealed and various therapeutic effects have been revealed. It was first discovered by a German scientist named Winkler, who named it Germanium after his homeland.

This germanium component has been known to have the effect of increasing immunity by supplying oxygen to the cells to purify the blood, at the same time discharging heavy metals from the body, and activating macrophages that surround pathogens. In particular, when heat is applied to germanium oxide (GeO2), a considerable amount of germanium far-infrared radiation is emitted. It is known to have excellent efficacy in preventing various adult diseases, such as disappearing. Far-infrared rays are infrared rays with a longer wavelength than visible rays, and refer to invisible rays with a wavelength of 5 to 25 µm. Because far-infrared rays have a long wavelength, they penetrate deeply into an object, and the penetrating far-infrared rays easily vibrate the molecules of a substance and generate heat on their own.

In addition, the germanium component is known to have an excellent antibacterial, antibacterial, antifungal, and harmful gas adsorption and decomposition action to keep the surrounding environment pleasant.

Therefore, attempts to develop functional materials by processing ores containing germanium are continued, but for example, even in the case of particles of germanium as a material emitting far-infrared rays, such germanium is not pure germanium, but inorganic materials including other minerals. As germanium, not only has the potential to adversely affect the human body, but also its content has to be at a level below the concentration (ppm) that exists in nature, so that it could not exhibit sufficient far-infrared function.

On the other hand, metal germanium or germanium oxide is not soluble in water, so its use is very limited. In Japan, there is a case where carboxyethyl germanium sesquioxide, a water-soluble organic synthetic germanium, was successfully synthesized and applied to a living body, but there is a problem that it is somewhat expensive.

[Prior Patent Literature]

- Korean Patent Registration No. 10-0567229 (March 28, 2006)

An object of the present invention is to provide a method for stably obtaining an aqueous germanium solution as a method for aqueous solution of germanium.

In order to solve the above problems, the present invention is a primary for mixing and reacting formalin, methanol, sodium hydroxide, triethanolamine, hexamine and melamine. reaction step; Secondary reaction step of mixing and reacting formalin, glyoxal, phosphate, triethanolamine, hexamine and melamine with the reactant generated in the first reaction ; Mix N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (N-(β-Aminoethyl)-γ-aminopropyltrimethoxysilane) and methyltrimethoxysilane with the reactant generated in the secondary reaction and a third reaction step of reacting; a quaternary reaction step of mixing and reacting ammonium chloride and water with the reactant generated in the tertiary reaction; A fifth reaction step of mixing and reacting a gadolinium complex represented by the following Chemical Formula 1 (Gd(DOTA-FPG)(H ₂ O)) with the reactant generated in the fourth reaction;

[Formula 1]

A sixth reaction step of mixing and reacting water, sodium hydroxide, triethanolamine, hydrogen peroxide (H ₂ O ₂ ) and germanium (Germanium) to the reactant generated in the fifth reaction; and mixing and stirring water and methanol to the reactants generated in the sixth reaction;

In addition, formalin (Formalin) 500 to 1,500 parts by weight, methanol (Methanol) 100 to 500 parts by weight, sodium hydroxide (Sodium hydroxide) 10 to 50 parts by weight, triethanolamine (Triethanolamine) 5 to 20 parts by weight, hexamine (Hexamine) 1 A first reaction step of mixing and reacting to 10 parts by weight and 300 to 1,000 parts by weight of melamine; In the reactant generated in the first reaction, 1,000 to 2,000 parts by weight of formalin, 300 to 1,000 parts by weight of glyoxal, 1 to 15 parts by weight of phosphate, 5 to 20 parts by weight of triethanolamine A secondary reaction step of mixing and reacting 1 to 10 parts by weight of hexamine and 500 to 2,000 parts by weight of melamine; 5 to 30 parts by weight of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (N-(β-Aminoethyl)-γ-aminopropyltrimethoxysilane) and methyltrimethoxysilane in the reactant generated in the secondary reaction (Methyltrimethoxysilane) a third reaction step of mixing and reacting 5 to 30 parts by weight; a fourth reaction step of mixing and reacting 20 to 100 parts by weight of ammonium chloride and 100 to 500 parts by weight of water to the reactant generated in the third reaction; A fifth reaction step of mixing and reacting 100 to 1,000 parts by weight of a gadolinium complex represented by the following Chemical Formula 1 (Gd(DOTA-FPG)(H _{2 O)) with the reactant generated in the fourth reaction} ;

[Formula 1]

10 to 100 parts by weight of water, 10 to 100 parts by weight of sodium hydroxide, 5 to 50 parts by weight of triethanolamine, and 20 to 100 parts by _{weight of hydrogen peroxide (H 2} O _{2 ) to the reactant generated in the fifth reaction} A sixth reaction step of mixing and reacting parts and 1 to 10 parts by weight of germanium; and mixing and stirring 500 to 5,000 parts by weight of water and 500 to 3,000 parts by weight of methanol to the reactant generated in the sixth reaction;

In addition, the germanium aqueous solution provides a method for producing a germanium aqueous solution, characterized in that used for fibers.

According to the present invention, a series of solution preparation steps for aqueous solubility of germanium are performed, and a step of mixing and reacting a specific material for waterproofing, improving fiber adhesion, and improving far-infrared emission performance is performed, and the reaction component and content ratio of each step In particular, it is possible to provide an innovative method for stably preparing an aqueous germanium solution having excellent antibacterial effect and far-infrared ray emission effect.

1 is a photograph showing the results of the initial (a) and 24 hours after (b) as the results of the antibacterial activity test against E. coli of the germanium aqueous solution in Test Example 2 of the present invention;
Figure 2 is a photograph showing the results of the initial (a) and 24 hours (b) as the results of the antibacterial activity test against Staphylococcus in the germanium aqueous solution in Test Example 2 of the present invention.

Hereinafter, the present invention will be described in detail through preferred embodiments. Prior to this, the terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor should properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention. Accordingly, since the configuration of the embodiments described in the present specification is only the most preferred embodiment of the present invention and does not represent all the technical spirit of the present invention, various equivalents and modifications that can be substituted for them at the time of the present application It should be understood that there may be In addition, throughout the specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

The germanium aqueous solution manufacturing method according to the present invention is a primary reaction of mixing and reacting formalin, methanol, sodium hydroxide, triethanolamine, hexamine and melamine. step; Secondary reaction step of mixing and reacting formalin, glyoxal, phosphate, triethanolamine, hexamine and melamine with the reactant generated in the first reaction ; Mix N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (N-(β-Aminoethyl)-γ-aminopropyltrimethoxysilane) and methyltrimethoxysilane with the reactant generated in the secondary reaction and a third reaction step of reacting; a quaternary reaction step of mixing and reacting ammonium chloride and water with the reactant generated in the tertiary reaction; A fifth reaction step of mixing and reacting a gadolinium complex represented by the following Chemical Formula 1 (Gd(DOTA-FPG)(H ₂ O)) with the reactant generated in the fourth reaction;

[Formula 1]

A sixth reaction step of mixing and reacting water, sodium hydroxide, triethanolamine, hydrogen peroxide (H ₂ O ₂ ) and germanium (Germanium) to the reactant generated in the fifth reaction; and mixing and stirring water and methanol to the reactants generated in the sixth reaction.

The first reaction step and the second reaction step are steps for preparing a solution capable of soluble germanium ore, and in the present invention, a first solution and a second solution are prepared through a series of two steps.

In the first reaction step, formalin, methanol, sodium hydroxide, triethanolamine, hexamine and melamine are mixed and reacted to prepare a first solution, At this time, the mixing ratio is 500 to 1,500 parts by weight of formalin, 100 to 500 parts by weight of methanol, 10 to 50 parts by weight of sodium hydroxide, 5 to 20 parts by weight of triethanolamine, hexamine (Hexamine) 1 to 10 parts by weight and melamine (Melamine) can be applied under the conditions of 300 to 1,000 parts by weight, preferably formalin (Formalin) 800 to 1,200 parts by weight, methanol (Methanol) 200 to 400 parts by weight, sodium hydroxide (Sodium hydroxide) 20 to 40 parts by weight, triethanolamine (Triethanolamine) 5 to 15 parts by weight, hexamine (Hexamine) 1.5 to 5 parts by weight, and melamine (Melamine) 400 to 600 parts by weight It can be applied under conditions.

In the first reaction step, each component is weighed at room temperature and stirred for 10 to 100 minutes, preferably 30 to 40 minutes, so that the reaction is carried out.

In the second reaction step, formalin, glyoxal, phosphate, triethanolamine, hexamine and melamine are mixed and reacted with the reactant generated in the first reaction. A second solution is prepared, and the mixing ratio is 1,000 to 2,000 parts by weight of formalin, 300 to 1,000 parts by weight of glyoxal, and 1 to 15 parts by weight of phosphate to the reactant generated in the first reaction. , 5 to 20 parts by weight of triethanolamine, 1 to 10 parts by weight of hexamine, and 500 to 2,000 parts by weight of melamine, preferably to the reactant generated in the first reaction Formalin (Formalin) 1,400 to 1,800 parts by weight, glyoxal (Glyoxal) 400 to 800 parts by weight, phosphate (phosphate) 3 to 10 parts by weight, triethanolamine (Triethanolamine) 5 to 15 parts by weight, hexamine (Hexamine) 1.5 to 5 It can be applied in terms of parts by weight and 1,000 to 1,500 parts by weight of melamine.

In the second reaction step, each component is weighed at room temperature and stirred for 10 to 100 minutes, preferably 30 to 40 minutes, so that the reaction is performed.

The tertiary reaction step is a step for imparting waterproofness that prevents moisture from permeating into the product when the aqueous solution solution is applied as a product in the future. This is the reaction step.

That is, in the third reaction step, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (N-(β-Aminoethyl)-γ-aminopropyltrimethoxysilane) and methyltri A tertiary solution is prepared by mixing and reacting methoxysilane (Methyltrimethoxysilane), and the mixing ratio is N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (N -(β-Aminoethyl)-γ-aminopropyltrimethoxysilane) 5 to 30 parts by weight and methyltrimethoxysilane 5 to 30 parts by weight can be applied under conditions, preferably N- to the reactant generated in the secondary reaction (β-aminoethyl)-γ-aminopropyltrimethoxysilane (N-(β-Aminoethyl)-γ-aminopropyltrimethoxysilane) 10 to 20 parts by weight and methyltrimethoxysilane 10 to 20 parts by weight applied under conditions can do.

In the third reaction step, each component is weighed at room temperature and stirred for 10 to 100 minutes, preferably 50 to 70 minutes, so that the reaction is carried out.

The fourth reaction step is a step for increasing the electrical conductivity of the aqueous solution solution to increase the adhesion to the product when it is applied to products such as fibers and fabrics in the future. It is a step of mixing and reacting specific substances for imparting.

That is, in the quaternary reaction step, a quaternary solution is prepared by mixing and reacting ammonium chloride and water with the reactant generated in the tertiary reaction, wherein the mixing ratio is to the reactant generated in the tertiary reaction. 20 to 100 parts by weight of Ammonium Chloride and 100 to 500 parts by weight of water may be applied, and preferably 30 to 70 parts by weight of Ammonium Chloride and 200 parts by weight of water to the reactant generated in the tertiary reaction to 400 parts by weight.

In the fourth reaction step, each component is weighed at room temperature and stirred for 10 to 100 minutes, preferably 30 to 40 minutes, so that the reaction is carried out.

The fifth reaction step is a step of mixing and reacting a specific material that maximizes far-infrared emission of germanium because the aqueous solution is not oxidized in air and has high magnetic field characteristics.

That is, in the fifth reaction step, a gadolinium complex represented by the following formula 1 (Gadolinium (III) Complex) (Gd (DOTA-FPG) (H ₂ O)) is mixed and reacted with the reactant generated in the fourth reaction. A fifth solution is prepared, and the mixing ratio is a gadolinium complex represented by the following Chemical Formula 1 in the reactant generated in the fourth reaction (Gd(DOTA-FPG)(H ₂ O)) 100 to It can be applied under the condition of 1,000 parts by weight, and preferably, a gadolinium complex represented by the following Chemical Formula 1 in the reactant generated in the quaternary reaction (Gd(DOTA-FPG)(H ₂ O)) 300 to 500 parts by weight.

[Formula 1]

In the fifth reaction step, each component is weighed at room temperature and stirred for 10 to 100 minutes, preferably 20 to 40 minutes, so that the reaction is carried out.

The sixth reaction step is a step of preparing a germanium solution, and is a step of water-soluble by adding germanium.

In the sixth reaction step, water, sodium hydroxide, triethanolamine, hydrogen peroxide (H ₂ O ₂ ) and germanium are mixed and reacted with the reactant generated in the fifth reaction to react the sixth solution In this case, the mixing ratio is 10 to 100 parts by weight of water, 10 to 100 parts by weight of sodium hydroxide, 5 to 50 parts by weight of triethanolamine, and hydrogen peroxide (H) to the reactant generated in the fifth reaction. ₂ O ₂ ) 20 to 100 parts by weight and 1 to 10 parts by weight of germanium may be applied, preferably 30 to 50 parts by weight of water, sodium hydroxide to the reactant produced in the fifth reaction 30 to 50 parts by weight, 10 to 30 parts by weight of triethanolamine _{, 40 to 60 parts by weight of hydrogen peroxide (H 2} O ₂ ), and 2 to 6 parts by weight of germanium.

In the sixth reaction step, after weighing each component at room temperature, the reaction may be carried out by stirring for 0.5 to 5 hours, preferably for 1 to 3 hours. Here, in the sixth reaction step, after dissolving the water in the sodium hydroxide and preheating it to 30 to 60 °C, preferably 40 to 50 °C, germanium is added thereto for 20 to 50 minutes, preferably 30 to 40 It is more preferable to react by mixing the other components after reacting for a minute.

As a final step after the sixth reaction, a step of adjusting the viscosity of the final aqueous solution is performed. That is, the final step is a step of performing viscosity adjustment by mixing and stirring a specific material with the reactant generated in the sixth reaction.

The viscosity adjustment step may be applied to the reactant produced in the sixth reaction under the conditions of 500 to 5,000 parts by weight of water and 500 to 3,000 parts by weight of methanol, and preferably, 1,000 to 1,000 parts by weight of water to the reactant produced in the sixth reaction. to 3,000 parts by weight and 700 to 1,500 parts by weight of methanol may be applied.

The viscosity adjustment step may be performed by weighing each component at room temperature and then stirring for 10 to 100 minutes, preferably 50 to 60 minutes.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

Example

Formalin (Formalin) 967 parts by weight, methanol (Methanol) 313 parts by weight, sodium hydroxide (Sodium hydroxide, 40% by weight) 28.3 parts by weight, triethanolamine (Triethanolamine) 9.67 parts by weight, hexamine (Hexamine) 2.44 parts by weight and melamine ( Melamine) 488 parts by weight was mixed and stirred at room temperature for 30 to 40 minutes to prepare a first solution.

After that, 1,620 parts by weight of formalin, 586 parts by weight of glyoxal, 7 parts by weight of phosphate, 9.6 parts by weight of triethanolamine, 2.26 parts by weight of hexamine and melamine in the first solution (Melamine) 1,295 parts by weight was mixed and stirred at room temperature for 30 to 40 minutes to prepare a secondary solution.

Then, 15 parts by weight of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (N-(β-Aminoethyl)-γ-aminopropyltrimethoxysilane) (DSL8340 or KBM603) and methyltrimethoxysilane in the secondary solution (Methyltrimethoxysilane) (DSL8113) 15 parts by weight was mixed, and stirred at room temperature for 60 minutes to prepare a tertiary solution.

Then, 54 parts by weight of ammonium chloride and 300 parts by weight of water were mixed with the tertiary solution, and stirred at room temperature for 30 to 40 minutes to prepare a quaternary solution.

Then, 400 parts by weight of the gadolinium complex (Gadolinium(III) Complex) (Gd(DOTA-FPG)(H ₂ O)) was mixed with the fourth solution, and stirred at room temperature for 30 minutes to prepare a fifth solution.

After that, 40 parts by weight of water is dissolved in 38.8 parts by weight of sodium hydroxide (Sodium hydroxide, 50% by weight) and preheated to 40 to 50° C., and then the fifth solution and 21.1 parts by weight of triethanolamine, hydrogen peroxide (H ₂ O ₂ ) 57.2 parts by weight and 3.8 parts by weight of germanium were mixed, and stirred at room temperature for 2 hours to prepare a sixth solution.

Then, 2,000 parts by weight of water and 1,000 parts by weight of methanol were added to the sixth solution and stirred at room temperature for 60 minutes to adjust the viscosity, thereby preparing a final germanium aqueous solution.

Test Example 1

In order to check the emissivity of far-infrared radiation and the amount of radiant energy of the prepared germanium aqueous solution, it was tested by the method of KFIA-FI-1005 at the Korea Far Infrared Application Evaluation Institute affiliated with the Korea Far Infrared Association, and the prepared germanium aqueous solution was mixed with polyester. A test specimen coated with a thickness of 5 to 10 μm on a material film was tested. This test was tested at 37°C, and the far-infrared emissivity and the amount of radiant energy were confirmed through the measurement results compared to a black body using an infrared spectrophotometer (FT-IR Spectrometer), and the test results are shown in Table 1 below.

emissivity
(5 ~ 20 ㎛ wavelength) radiant energy
(W/m2 μm, 37℃) 0.893 3.44×10 ²

Referring to Table 1, it can be seen that the germanium aqueous solution prepared according to the present invention exhibits excellent far-infrared radiation characteristics.

Test Example 2

In order to confirm the antibacterial activity of the prepared germanium aqueous solution, the antibacterial test by E. coli and Staphylococcus, which are representative food poisoning bacteria, was requested by the Korea Far Infrared Application Evaluation Institute affiliated with the Korea Far Infrared Association, and was tested by the method of KFIA-FI-1003, and the prepared The test was conducted by spraying an aqueous germanium solution. As strains used, Escherichia coli ATCC 25922 and Staphylococcus aureus ATCC 6538 were used. Blank was measured in a state in which no sample was put, and the number of bacteria on the medium was calculated by multiplying the dilution factor, and the test results are shown in Table 2, FIG. 1 (antibacterial activity test result against E. coli) and FIG. results).

Test Items Sample classification initial concentration
(CFU/ml) concentration after 24 hours bacteriostatic reduction rate
(%) Antibacterial test by E. coli Blank 3.3×10 ⁵ 7.5×10 ⁶ - Germanium aqueous solution spray < 1.0×10 ² 99.9 Antibacterial test by Staphylococcus aureus Blank 1.2×10 ⁵ 4.1×10 ⁶ - Germanium aqueous solution spray < 1.0×10 ² 99.9

Referring to Table 1, Figures 1 and 2, it can be seen that the germanium aqueous solution prepared according to the present invention exhibits excellent antibacterial properties.

Preferred embodiments of the present invention described above are disclosed to solve the technical problem, and various modifications, changes, additions, etc. will be possible within the spirit and scope of the present invention by those skilled in the art to which the present invention pertains. , such modifications and changes should be regarded as belonging to the following claims.

Claims (3)

A first reaction step of mixing and reacting formalin, methanol, sodium hydroxide, triethanolamine, hexamine and melamine;
Secondary reaction step of mixing and reacting formalin, glyoxal, phosphate, triethanolamine, hexamine and melamine with the reactant generated in the first reaction ;
Mix N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (N-(β-Aminoethyl)-γ-aminopropyltrimethoxysilane) and methyltrimethoxysilane with the reactant generated in the secondary reaction and a third reaction step of reacting;
a quaternary reaction step of mixing and reacting ammonium chloride and water with the reactant generated in the tertiary reaction;
A fifth reaction step of mixing and reacting a gadolinium complex represented by the following Chemical Formula 1 (Gd(DOTA-FPG)(H ₂ O)) with the reactant generated in the fourth reaction;
[Formula 1]

A sixth reaction step of mixing and reacting water, sodium hydroxide, triethanolamine, hydrogen peroxide (H ₂ O ₂ ) and germanium (Germanium) to the reactant generated in the fifth reaction; and
mixing and stirring water and methanol to the reactants generated in the sixth reaction;
A method for preparing an aqueous solution of germanium comprising a. Formalin (Formalin) 500 to 1,500 parts by weight, methanol (Methanol) 100 to 500 parts by weight, sodium hydroxide (Sodium hydroxide) 10 to 50 parts by weight, triethanolamine (Triethanolamine) 5 to 20 parts by weight, hexamine (Hexamine) 1 to A first reaction step of mixing and reacting 10 parts by weight and 300 to 1,000 parts by weight of melamine;
In the reactant generated in the first reaction, 1,000 to 2,000 parts by weight of formalin, 300 to 1,000 parts by weight of glyoxal, 1 to 15 parts by weight of phosphate, 5 to 20 parts by weight of triethanolamine A secondary reaction step of mixing and reacting 1 to 10 parts by weight of hexamine and 500 to 2,000 parts by weight of melamine;
5 to 30 parts by weight of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (N-(β-Aminoethyl)-γ-aminopropyltrimethoxysilane) and methyltrimethoxysilane in the reactant generated in the secondary reaction (Methyltrimethoxysilane) a third reaction step of mixing and reacting 5 to 30 parts by weight;
a fourth reaction step of mixing and reacting 20 to 100 parts by weight of ammonium chloride and 100 to 500 parts by weight of water to the reactant generated in the third reaction;
A fifth reaction step of mixing and reacting 100 to 1,000 parts by weight of a gadolinium complex represented by the following Chemical Formula 1 (Gd(DOTA-FPG)(H _{2 O)) with the reactant generated in the fourth reaction} ;
[Formula 1]

10 to 100 parts by weight of water, 10 to 100 parts by weight of sodium hydroxide, 5 to 50 parts by weight of triethanolamine, and 20 to 100 parts by _{weight of hydrogen peroxide (H 2} O _{2 ) to the reactant generated in the fifth reaction} A sixth reaction step of mixing and reacting parts and 1 to 10 parts by weight of germanium; and
mixing and stirring 500 to 5,000 parts by weight of water and 500 to 3,000 parts by weight of methanol to the reactant generated in the sixth reaction;
A method for preparing an aqueous solution of germanium comprising a. 3. The method of claim 1 or 2,
The germanium aqueous solution is a germanium aqueous solution manufacturing method, characterized in that used for fibers.

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