KR102120081B1 - Titanium dioxide composition - Google Patents

Abstract

The titanium dioxide composition of the present invention contains 1 to 15 parts by weight of titanium dioxide particles containing copper (Cu)-magnesium (Mg) with respect to 100 parts by weight of water.

Description

Titanium dioxide composition {TITANIUM DIOXIDE COMPOSITION}

The present invention relates to a titanium dioxide composition. Specifically, the titanium dioxide composition of the present invention contains 1 to 15 parts by weight of titanium dioxide particles containing copper (Cu)-magnesium (Mg) with respect to 100 parts by weight of water.

Titanium dioxide particles are advantageous for plant growth, such as sterilization effect and decomposition effect of toxic organic substances, and research to apply them to plants is actively conducted, and there are increasing cases of application.

However, despite the effect of titanium dioxide, recent research has shown that titanium dioxide can degrade the immune system of rats, and France is taking steps to exclude titanium dioxide from food additives.

On the other hand, when the plant is separated from the root for the purpose of ornamental, it quickly withers. To increase the ornamental time, it is necessary to delay the wilting of the plant or to extend the life of the plant.

Therefore, there is a need for a composition that is easy to remove titanium dioxide, not only extends the life of the plant, but is also environmentally friendly and has excellent herbicidal, anti-insect, and growth promoting effects for plants.

An object of the present invention is to provide a titanium dioxide composition that is easy to remove titanium dioxide and can extend the life of plants.

Another object of the present invention is to provide a titanium dioxide composition that is environmentally friendly, but has excellent herbicidal effect, anti-insect and pesticidal effect, and growth promoting effect.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the invention relates to a titanium dioxide composition.

According to one embodiment, the titanium dioxide composition comprises 1 to 15 parts by weight of titanium dioxide particles containing copper (Cu)-magnesium (Mg), based on 100 parts by weight of water.

In addition, the composition is 0.1 to 5 parts by weight of pyrethrin (pyrethrin); Penoxsulam 0.01 to 2.0 parts by weight; 0.001 to 0.5 part by weight of isoxaben; And orizalin (orizalin) 0.001 to 0.5 parts by weight; may further include.

In addition, the composition may further include 25 to 50 parts by weight of a neutral fertilizer.

In addition, the composition may further include 0.001 to 2 parts by weight of TPA (Thermal polyaspartic acid, thermally condensed polyaspartic acid).

In addition, the composition may further include 0.01 to 0.5 parts by weight of liquid sulfur.

In addition, the copper (Cu)-magnesium (Mg)-containing titanium dioxide particles may have a weight ratio of the copper (Cu) and magnesium (Mg) of 10:90 to 20:80.

In addition, the copper (Cu)-magnesium (Mg)-containing titanium dioxide particles may have a weight of 5 to 50% by weight of the copper (Cu) and magnesium (Mg) among the particles.

In addition, the titanium dioxide particles containing copper (Cu)-magnesium (Mg) may have an average particle diameter (D50) of 1 mm to 10 mm.

The present invention has an effect of providing a titanium dioxide composition that is easy to remove titanium dioxide, not only extends the life of the plant, but is also environmentally friendly, and has excellent herbicidal effect, prevention of disease and pest, and promoting growth.

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

In describing the present invention, when it is determined that detailed descriptions of related known technologies may unnecessarily obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.

When'include','have','consist of', etc. mentioned in the specification are used, other parts may be added unless'~man' is used. When a component is expressed as a singular number, the plural number is included unless otherwise specified.

In addition, in analyzing the components, it is interpreted as including an error range even if there is no explicit description.

In addition, in this specification,'X to Y'indicating a range means'X or more and Y or less'.

Titanium dioxide composition

The titanium dioxide composition according to an embodiment of the present invention includes copper (Cu)-magnesium (Mg)-containing titanium dioxide particles. As a result, plants and soil containing vegetables and agricultural products coated with the titanium dioxide composition of the present invention have high resistance to various pathogens, and the yield of plants is excellent. In an embodiment, the titanium dioxide composition of the present invention may be applied as a fertilizer composition, but is not limited thereto.

The copper (Cu)-magnesium (Mg)-containing titanium dioxide (TiO ₂ ) particles may have an average particle diameter (D50) of 1 mm to 10 mm, specifically 2 mm to 8 mm, and more specifically 3 mm to 7 mm. . In the above average particle size range, copper (Cu)-magnesium (Mg)-containing titanium dioxide (TiO ₂ ) particles are easy to clean and have an advantage of minimizing residual amount by washing after application.

The copper (Cu)-magnesium (Mg) containing titanium dioxide (TiO ₂ ) particles are formed of a mixture comprising titanium dioxide (TiO ₂ ) powder, copper (Cu) and magnesium (Mg), and heat treating the mixture It may be manufactured by a manufacturing method including a step.

The titanium dioxide powder may have an average particle diameter (D50) of 1 nm to 100 nm, specifically 5 nm to 80 nm.

The titanium dioxide powder may include two or more types of titanium dioxide powders having different average particle diameters (D50). In this case, durability and resistance to pathogens are improved according to the compactness of the copper (Cu)-magnesium (Mg)-containing titanium dioxide (TiO ₂ ) particles.

For example, the titanium dioxide (TiO ₂ ) powder includes first and second titanium dioxide (TiO ₂ ) powders having different average particle sizes (D50), and the first titanium dioxide (TiO ₂ ) powder has an average particle size ( D50) is 1 nm to 70 nm, specifically 10 nm to 50 nm, and the second titanium dioxide (TiO ₂ ) powder may have an average particle diameter (D50) of 20 nm to 100 nm, specifically 20 nm to 80 nm. . In addition, the average particle diameter (D50) ratio of the first titanium dioxide (TiO ₂ ) powder and the second titanium dioxide (TiO ₂ ) powder may be 1:0.4 to 1:0.6. In the average particle diameter ratio range, the titanium dioxide particles containing copper (Cu)-magnesium (Mg) may be more dense and maximize durability and resistance to pathogens.

The titanium dioxide (TiO ₂ ) powder may be included in 50 to 95% by weight, specifically 60 to 90% by weight of the copper (Cu)-magnesium (Mg)-containing titanium dioxide particles. In the above content range, while being able to exert sufficient pathogen resistance, other effects, such as durability and particle formability, can be simultaneously exhibited.

The copper (Cu) and magnesium (Mg) are contained in the copper (Cu)-magnesium (Mg)-containing titanium dioxide particles to increase the light absorption in the visible region, and thus the copper (Cu)-magnesium (Mg)-containing titanium dioxide particles In addition to having an effect of improving efficiency, it is possible to improve the binding power of titanium dioxide (TiO ₂ ) powder and other components. In addition, it is possible to exert a catalytic activity even at a lower current, or even at the same current, the catalytic activity may be higher, so that resistance to pathogens is excellent.

Particularly, the copper (Cu)-magnesium (Mg)-containing titanium dioxide particles of the present invention have a weight ratio of copper (Cu) and magnesium (Mg) close to the eutectic point, specifically 10:90 to 20:80. By applying in the range of 12:88 to 16:84, it is possible to significantly lower the temperature of the process for manufacturing titanium dioxide particles containing copper (Cu)-magnesium (Mg), which can minimize the transition to the rutile crystal structure, Pathogen resistance efficiency can be maximized. In this case, the copper (Cu) and magnesium (Mg) may be partially or more eutectic. At this time, the copper (Cu) and magnesium (Mg) components can improve the bonding strength between the particles of titanium dioxide particles containing copper (Cu)-magnesium (Mg), and titanium dioxide containing copper (Cu)-magnesium (Mg) It serves to enable particles to be molded to a specific particle diameter range. Specifically, the particle size of the titanium dioxide particles containing copper (Cu)-magnesium (Mg) may be determined according to the content of the copper (Cu) and magnesium (Mg) components.

The copper (Cu) and magnesium (Mg) may be included in 5 to 50% by weight, specifically 10 to 45% by weight, and more specifically 15 to 40% by weight of the titanium dioxide particles containing copper (Cu)-magnesium (Mg). have. In the above content range, copper (Cu)-magnesium (Mg)-containing titanium dioxide particles not only improve the catalytic efficiency and pathogen resistance at lower currents, which can improve pathogen resistance in the visible region, but also copper (Cu) -Magnesium (Mg)-containing titanium dioxide particles can be prepared to have an appropriate particle diameter, so the particles are easy to clean, and there is an advantage of minimizing the residual amount by washing after application.

The titanium dioxide particles containing copper (Cu)-magnesium (Mg) of the present invention may be prepared by a process of heat-treating a mixture containing the titanium dioxide (TiO ₂ ) powder, copper (Cu), and magnesium (Mg).

Specifically, the heat treatment may be performed at 400°C to 900°C, specifically 450°C to 750°C, and more specifically 460°C to 550°C in an H ₂ /Ar atmosphere. Copper (Cu) and magnesium (Mg) contained in the titanium dioxide particles containing copper (Cu)-magnesium (Mg) of the present invention is applied at a weight ratio of 10:90 to 20:80, at least partially eutectic in the heat treatment temperature range It is possible to add sufficient binding force between the components constituting the catalyst.

In particular, the content of the copper (Cu) and magnesium (Mg) components may affect the particle size of the titanium dioxide containing copper (Cu)-magnesium (Mg), specifically, the copper (Cu) and magnesium (Mg) The average particle diameter (D50) of the copper (Cu)-magnesium (Mg)-containing titanium dioxide particles contained in 5 to 50% by weight of the copper (Cu)-magnesium (Mg)-containing titanium dioxide particles was controlled to 1 mm to 10 mm. Can be. It is easy to wash in the above average particle diameter range, and there is an advantage of minimizing the residual amount by washing after application.

In other embodiments, the mixture may further include zirconia (ZrO ₂ ).

The zirconia (ZrO ₂ ) is included in the titanium dioxide particles containing copper (Cu)-magnesium (Mg), and may serve to improve stability and durability. Specifically, the zirconia (ZrO ₂ ) is a heat-resistant material having a high melting temperature (about 2,700°C), and exhibits excellent material properties such as low thermal conductivity, wide chemical resistance from acidic to alkaline regions, low thermal expansion, and high hardness. Carry

The zirconia (ZrO ₂ ) can be used together with titanium dioxide powder to maximize catalyst efficiency, as well as improve durability of copper (Cu)-magnesium (Mg)-containing titanium dioxide particles, so that copper (Cu)-magnesium (Mg) containing titanium dioxide particles can be minimized the phenomenon of breaking or peeling.

The zirconia (ZrO ₂ ) may have an average particle diameter (D50) larger than that of titanium dioxide (TiO ₂ ) powder. In this case, the titanium dioxide particles containing copper (Cu)-magnesium (Mg) have excellent durability improvement effect. Specifically, as the zirconia (ZrO ₂ ), an average particle diameter (D50) of more than 100 nm and less than 800 nm may be used in the range of 200 nm to 500 nm.

The zirconia (ZrO ₂ ) may be included in 2 to 20% by weight, specifically 5 to 15% by weight, among the titanium dioxide particles containing copper (Cu)-magnesium (Mg). In the above range, the pathogen resistance and durability improvement effect of the copper (Cu)-magnesium (Mg)-containing titanium dioxide particles is excellent.

The mixture may further include at least one of titanium (Ti), platinum (Pt), silver (Ag), alumina (Al ₂ O ₃ ), silicon oxide (SiO ₂ ), and manganese (Mn) as additional components. The additional component may be included in the titanium dioxide particles containing copper (Cu)-magnesium (Mg) to improve the light absorption ability of visible light to further improve pathogen resistance, or to improve durability by increasing binding strength between components. .

The copper (Cu)-magnesium (Mg)-containing titanium dioxide particles may be included in 1 to 15 parts by weight, specifically 5 to 13 parts by weight, and more specifically 8 to 12 parts by weight with respect to 100 parts by weight of water. In the above content range, there is an advantage of excellent drag without deteriorating the growth of plants.

The pyrethrin (CAS No.121-21-1, (1S)-2-methyl-4-oxo-3-[(2Z)-2,4-pentadien-1-yl]-2-cyclopenten-1 -yl (1R, 3R)-2,2-dimethyl-3-(2-methyl-1-propen-1-yl)cyclopropanecarboxylate) is a natural insecticidal component extracted from asteraceae petals, pests such as mites, moths, mosquitoes, etc. It is a component that eliminates the causes of pests such as fungi and viruses. The pyrethrin does not affect the earthworms, ants, etc., which are beneficial to the soil, and can also solve problems caused by residuals because it decomposes rapidly in oxygen or sunlight. The pyrethrin may be commercially available under the trade name Chungchungguk, but is not limited thereto.

The content of the pyrethrin may be included in 0.1 to 5.0 parts by weight, specifically 0.3 to 2 parts by weight based on 100 parts by weight of water. In the above-mentioned content range, it is possible to prevent an effect of preventing pests, yellowing of grass, and death.

The phenoxlam (penoxsulam, CAS No.219714-96-2, 2-(2,2-Difluoroethoxy)-N-(5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidin- 2-yl)-6-(trifluoromethyl)benzenesulfonamide) is a triazolopyrimidinesulfonamide herbicide. The phenoxlam is a selective herbicide that treats the stems and leaves of 1-year and perennial broad-leaved weeds after weeding, is absorbed through the roots, stems, or leaves of broad-leaved weeds and accumulates in the dividing tissues of plants to show activity. Specifically, it is known to exhibit herbicidal activity by inhibiting the basic cell division and growth of plants by inhibiting the action of an enzyme (Acetolactate synthase). The phenoxlam may be used as a commercially available product called Salchodae-cheop, but is not limited thereto.

The content of phenoxylam may be included in an amount of 0.01 to 2.0 parts by weight, specifically 0.01 to 1 part by weight based on 100 parts by weight of water. The weed removal effect is excellent in the above range, but it is possible to minimize the adverse effect on grass growth.

The isoxaben (isoxaben, CAS No.82558-50-7, 2,6-Dimethoxy-N-[3-(3-methyl-3-pentanyl)-1,2-oxazol-5-yl]benzamide) As an amide herbicide, it serves to remove broad-leaved weeds. The Isoxaben has excellent soil adsorption property and is not easily lost, so it does not cause environmental pollution and has excellent sustaining effect. The iSoxaben may be used as what is currently commercially available as a catch pool, but is not limited thereto.

The content of the isoxaben may be 0.001 to 0.5 parts by weight, specifically 0.01 to 0.3 parts by weight with respect to 100 parts by weight of water. In this range, the balance of herbicidal effect and duration of drug efficacy is excellent and it is possible to minimize the inhibition of turf growth.

The orizallin (oryzalin, CAS No.19044-88-3, 4-(Dipropylamino)-3,5-dinitrobenzenesulfonamide) is a dinitroaniline-based herbicide that inhibits cell division of the division tissue of annual weeds and is associated with germination of seeds. It exhibits activity by affecting physiological mechanisms. Orizalin also has a long lasting effect, so it has a long-lasting effect, and it is possible to use what is currently marketed under the trade name SUPRAN, but is not limited thereto.

The content of the orissaline may be 0.001 to 0.5 parts by weight, specifically 0.01 to 0.3 parts by weight with respect to 100 parts by weight of water. Weed removal and duration in the above content range is appropriate, and it is possible to minimize adverse effects that can be given to surrounding trees.

The composition may further include a neutral fertilizer.

The neutral fertilizer may include one or more of nitrogen, phosphoric acid, and potassium, and the components are mixed to form a neutral layer and prevent acidification of the soil and serve to supply nutrients to the grass. The neutral fertilizer is not particularly limited in the present invention, and commercially available ones can be purchased and used.

The content of the neutral fertilizer may be included in 25 to 50 parts by weight, specifically 30 to 40 parts by weight with respect to 100 parts by weight of water. It is possible to prevent the weeds from being activated while providing sufficient nutrient supply to the grass in the above range.

In another embodiment, the composition may further include TPA (Thermal polyaspartic acid, heat condensation polyaspartic acid).

The TPA is a L-aspartic acid heat condensate, which has an amide bond and a very high cation substitution capacity, and is a biodegradable eco-friendly material that is non-bioaccumulative and has low ecological toxicity and promotes rooting and fertilizer absorption.

The copper (Cu)-magnesium (Mg)-containing titanium dioxide particles and TPA may be included in a weight ratio of 15:1 to 25:1 in the titanium dioxide composition of the present invention. In the weight ratio range, the plant growth effect and the pathogen resistance effect balance is excellent, and the plant yield is maximized.

The TPA may be represented by Formula 1 below.

[Formula 1]

The TPA may be included in an amount of 0.001 to 2 parts by weight, specifically 0.01 to 1 part by weight based on 100 parts by weight of water in the composition. In the above content range, there is an advantage of excellent rooting and fertilizer absorption effect without increasing the manufacturing cost.

In another embodiment, the composition may further include liquid sulfur.

The liquid sulfur is made by mixing 1 to 1.5 parts by weight of the legal sulfur powder in 100 parts by weight of impediment, and serves to further improve the control effect of the titanium dioxide composition.

The liquid sulfur may be included in an amount of 0.01 to 0.5 parts by weight, specifically 0.1 to 0.3 parts by weight based on 100 parts by weight of the composition. It has the advantage of not being toxic in the above content range and having excellent control effect.

The titanium dioxide composition of the present invention may further include at least one antidote, pesticide, fungicide and mite pesticide for the desired effect, and each content may range from 0.001 to 1 part by weight.

The titanium dioxide composition of the present invention may be used in a liquid form applied to plants.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is provided as a preferred example of the present invention and cannot be interpreted as limiting the present invention by any means.

The contents not described here will be sufficiently technically inferred by those skilled in the art, and thus the description thereof will be omitted.

Preparation of titanium dioxide particles containing copper (Cu)-magnesium (Mg)

Preparation Example 1

80% by weight of titanium dioxide powder (TiO2, Aldrich), 2.8% by weight of copper (Cu) and 17.2% by weight of magnesium (Mg) were mixed, the mixture was introduced into a tube furnace, and in an H2/Ar atmosphere at 530°C for 5 hours. While heating. Then, the mixture was stirred in a 1.0M HCl solution for 24 hours, washed with water to remove the acid, and then dried to prepare copper (Cu)-magnesium (Mg)-containing titanium dioxide particles. The average particle diameter (D50) of the titanium dioxide catalyst was 5.2 mm.

Preparation Example 2

The same method as in Production Example 1, except that 70 wt% of titanium dioxide powder (TiO2, Aldrich), 2.8 wt% of copper (Cu) and 17.2 wt% of magnesium (Mg), and 10 wt% of zirconia (ZrO ₂ ) were mixed As a result, titanium dioxide particles containing copper (Cu)-magnesium (Mg) were prepared. The average particle diameter (D50) of the titanium dioxide catalyst was 5.5 mm.

Example: Preparation of titanium dioxide composition

Example 1

With respect to 100 parts by weight of water, 10 parts by weight of titanium dioxide particles containing copper (Cu)-magnesium (Mg) of Preparation Example 1, 1 part by weight of pyrethrin, 0.5 part by weight of penoxsulam, isoxaben (isoxaben) 0.1 parts by weight, orizalin (orizalin) 0.2 parts by weight, and neutral fertilizer 35 parts by weight to prepare a titanium dioxide composition.

Example 2

The same method as in Example 1, except that the copper (Cu)-magnesium (Mg) containing titanium dioxide particles of Preparation Example 2 were used instead of the copper (Cu)-magnesium (Mg) containing titanium dioxide particles of Preparation Example 1. Titanium dioxide composition was prepared.

Example 3

A titanium dioxide composition was prepared in the same manner as in Example 1, except that 0.5 part by weight of TPA was added to Example 1.

Example 4

A titanium dioxide composition was prepared in the same manner as in Example 1, except that 0.2 parts by weight of liquid sulfur was further mixed in Example 1.

Comparative Example 1

A titanium dioxide composition was prepared in the same manner as in Example 1, except that titanium dioxide powder (TiO2, Aldrich) was applied instead of the titanium dioxide particles containing copper (Cu)-magnesium (Mg) in Example 1.

Comparative Example 2

A titanium dioxide composition was prepared in the same manner as in Example 1, except that the titanium dioxide particles containing copper (Cu)-magnesium (Mg) were not included in Example 1.

Property evaluation method

1) Concentration of titanium dioxide (ppm): 2 ml of titanium dioxide composition is applied to chrysanthemums (scientific name: Chrysanthemum morifolium) and lettuce (length of about 23 cm) from which roots have been removed, and after 24 hours, dip in 10 L water for 1 hour to wash. Then, the concentration of titanium dioxide contained in the water was measured by ICP mass spectrometry, a quantitative analysis device, and shown in Table 1 below. It means that the higher the concentration of carbon dioxide, the easier it is to wash, and the lower the residual amount in plants.

2) Observation of life (%): 2 ml of titanium dioxide composition was applied to chrysanthemums (scientific name: Chrysanthemum morifolium) and lettuce (about 23 cm in length) from which roots were removed, and withered every 24 hours at 18°C and 60% humidity (ocher color) The area ratio of) was measured and shown in Table 1 below. The larger the rate of increase in the area ratio, the faster it means to wither.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Concentration of chrysanthemum titanium dioxide (ppm) 13 14 14 13 6 - Concentration of lettuce titanium dioxide (ppm) 14 14 14 13 7 - Chrysanthemum life observation
(%) 24h 0.1 0.2 0.1 0.1 0.8 One 48h 0.5 0.6 0.8 0.2 4 5 72h 1.1 1.5 1.1 0.6 6 7 96h 2.1 2.3 2.9 1.2 9 13 120h 3.7 4.6 5.0 2.9 12 19 144h 5.0 6.1 7.4 4.3 18 28 168h 8.1 9.0 10.2 7.9 23 45 Lettuce life observation
(%) 24h 0.1 0.1 0.2 0.1 1.5 3 48h 0.6 0.9 0.8 0.4 5 8 72h 2.0 2.3 3.0 1.0 9 11 96h 4.5 3.9 4.6 3.1 16 21 120h 6.1 5.0 7.0 4.8 20 33 144h 10.6 7.8 9.9 6.2 23 46 168h 13.3 11.1 13.8 10.8 33 61

As shown in Table 1, Examples 1 to 4 to which the titanium dioxide composition of the present invention was applied not only had a low concentration of residual titanium dioxide, but also had an effect of extending the life of the plant, while comparing titanium dioxide as a powder. Example 1 is not easy to remove titanium dioxide, but also has a slight life extension effect, and Comparative Example 2, which does not include the copper (Cu)-magnesium (Mg)-containing titanium dioxide particles of the present invention, is a titanium dioxide composition of the present invention It can be seen that it withered faster than the plants to which it was applied.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, and may be manufactured in various different forms, and those skilled in the art to which the present invention pertains have technical spirit of the present invention. However, it will be understood that other specific forms may be practiced without changing essential features. Therefore, it should be understood that the above-described embodiments are illustrative in all respects and not restrictive.

Claims (8)

For 100 parts by weight of water,
1 to 15 parts by weight of titanium dioxide particles containing copper (Cu)-magnesium (Mg);
0.1 to 5 parts by weight of pyrethrin;
Penoxsulam 0.01 to 2.0 parts by weight;
0.001 to 0.5 part by weight of isoxaben;
Orizalin 0.001 to 0.5 parts by weight;
25 to 50 parts by weight of neutral fertilizer; And
TPA (Thermal polyaspartic acid, heat condensation polyaspartic acid) 0.001 to 2 parts by weight;
Including,
The copper (Cu)-magnesium (Mg)-containing titanium dioxide particles have a weight ratio of the copper (Cu) and magnesium (Mg) of 10:90 to 20:80,
The copper (Cu)-magnesium (Mg)-containing titanium dioxide particles have a titanium dioxide composition having an average particle diameter (D50) of 1 mm to 10 mm.
delete delete delete According to claim 1,
The composition is a titanium dioxide composition further comprising 0.01 to 0.5 parts by weight of liquid sulfur.
delete According to claim 1,
The copper (Cu)-magnesium (Mg)-containing titanium dioxide particles are titanium dioxide compositions having a weight of 5 to 50% by weight of the copper (Cu) and magnesium (Mg) among the particles.
delete