KR100757103B1 - Wax composition with dispersed titanium dioxide nanoparticles and preparing method thereof - Google Patents

Abstract

An environmentally friendly wax composition, and a method for preparing the wax composition are provided to improve antibacterial effect and to decompose the harmful components such as ammonia, formaldehyde, etc. contained in a wax or air. A wax composition comprises 100 parts by weight of a wax particle; 200-350 parts by weight of water; 2-15 parts by weight of a titanium dioxide(TiO2) nanoparticle having an average diameter of 5 nm or less dispersed in the wax particle or water; 90-200 parts by weight of an ether-based plasticizer containing a functional group represented by -(O-(CH2)n-O)m- (wherein n is 2 or 3; and m is an integer of 1-5); and 8-20 parts by weight of any one plasticizer selected from a phthalate-based plasticizer, a phosphate-based plasticizer, an adipate-based plasticizer, a sebacate-based plasticizer, an azelate-based plasticizer, a citrate-based plasticizer, a glycolate-based plasticizer, a trimellitate-based plasticizer, a linoleate-based plasticizer, a polyester-based plasticizer, an epoxy-based plasticizer, a chlorine-based plasticizer, and their mixture.

Description

Wax composition with dispersed titanium dioxide nanoparticles and preparing method

1 is a schematic diagram showing a polar surface of hydrated titanium dioxide.

FIG. 2 is a schematic diagram showing that in a wax composition in which titanium dioxide (TiO ₂ ) nanoparticles are dispersed, a polar surface of titanium dioxide is surrounded by EDG (diethylene glycol monoethyl ether) and is nonpolarized.

3 is a schematic diagram showing that in the wax composition in which titanium dioxide (TiO ₂ ) nanoparticles are dispersed, a polar surface of titanium dioxide is surrounded by DPM (dipropylene glycol monomethyl ether) and is nonpolarized.

The present invention relates to a wax composition in which titanium dioxide (TiO ₂ ) nanoparticles are dispersed and a preparation method thereof.

Wax is a compound of several hundreds of molecular weight which is solid at room temperature and turns into a fluid when the temperature is increased. It has a gloss, lubrication, waterproofing, and antiseptic effect. Used in combination with It is also widely used as a raw material for candles, adhesives, inks and surfactants.

There are many types of waxes, but they are divided into low melting wax (normal paraffin wax, beeswax, etc.) and high melting wax (microcrystalline wax, carnauba wax, synthetic wax, etc.) depending on the melting point. It is also classified as wax (paraffin, microcrystalline wax), animal natural wax, vegetable natural wax, synthetic wax, and the like. In addition, waxes in the broad sense include semi-flowing petrolatum (waserine, Petrolatum), liquid flow paraffin, liquid paraffin and the like. Thus, some waxes may be semi-fluid or full fluid at room temperature. There is also a gel wax, but it is difficult to classify the original wax because it is mainly a mixture of the fluidized wax and the gel-forming polymer resin.

Synthetic wax has the highest melting point among waxes, and has high temperature stability and fast hardening property. Molecular properties are similar to low-molecular polyethylene, and there are also waxes obtained from syngas through Fischer-Tropsch synthesis. PE wax is obtained by polymerizing ethylene obtained by decomposing natural gas or naphtha. Is obtained. In many cases, a pyrolysis wax obtained by thermally decomposing PE (HDPE, LDPE) and a low molecular by-product in the PE polymerization process (primarily HDPE) are purified.

By the way, such a wax composition is used for the use of polish agents such as deluxe tiles, antifouling agents, etc., the wax composition for coating includes a variety of chemicals (for example, leveling agents, plasticizers, surfactants, binders, etc.) The unpleasant odor after application is due to the evaporation of volatiles that may be present in these chemicals. These chemicals affect the ease of processing of the wax composition, the physical properties of the wax after coating the composition, etc., and thus have a problem due to their odors.

Therefore, an object of the present invention is to solve the problems of the prior art, titanium dioxide nanoparticles photocatalyst that decomposes harmful substances in the air as well as harmful substances such as ammonia and formaldehyde, which may be included in the wax composition, and also exhibits an antibacterial effect. It is to provide a dispersed wax composition.

Another object of the present invention is to provide a method for preparing a wax composition in which the titanium dioxide (TiO ₂ ) nanoparticles are dispersed.

The present invention to achieve the above object,

100 parts by weight of wax particles; 250 parts by weight to 350 parts by weight of water; And 2 parts by weight to 15 parts by weight of titanium dioxide (TiO ₂ ) nanoparticles having an average particle diameter of 5 nm or less dispersed in the water or wax particles.

The present invention to achieve the above other object,

As a method for producing a wax composition in which titanium dioxide (TiO ₂ ) nanoparticles are dispersed,

(a) 200 parts by weight to 350 parts by weight of water

Mixing by mixing 100 parts by weight to 400 parts by weight of 10,000 ppm to 100,000 ppm aqueous solution of titanium dioxide (TiO ₂ ) nanoparticles having an average particle diameter of 5 nm or less;

(b) adding and mixing 110 parts by weight to 210 parts by weight of a plasticizer, and

(c) adding 100 parts by weight of wax to mix

It provides a method for producing a wax composition comprising.

One embodiment of the present invention to achieve the above object,

As a method of manufacturing a wax composition in which titanium dioxide (TiO ₂ ) nanoparticles are dispersed,

Mixing by mixing 0.1 parts by weight to 1 parts by weight of a dispersant between the steps (a) and (b);

Mixing 0.5 parts by weight to 20 parts by weight of a fluorine-based surfactant between steps (b) and (c);

Mixing 0.3 part by weight to 7 parts by weight of a leveling agent; And

After the step (c) it provides a wax composition, characterized in that it further comprises the step of mixing by mixing 350 parts by weight to 1000 parts by weight and 10 parts by weight to 45 parts by weight of the rosin (rosin).

Due to the titanium dioxide photocatalyst dispersed in the wax, the wax composition according to the present invention not only decomposes harmful substances such as ammonia and formaldehyde and harmful substances in the atmosphere that may be included in the wax, but also shows antibacterial effects. to be.

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

The wax composition of the present invention comprises 200 parts by weight to 350 parts by weight of water, 100 parts by weight of wax particles and 2 parts by weight to 15 parts by weight of titanium dioxide (TiO ₂ ) nanoparticles having an average particle diameter of 5 nm or less dispersed in the water or wax particles. Characterized in that.

Water is preferably 200 parts by weight to 350 parts by weight with respect to 100 parts by weight of wax as a solvent and a dispersant. If the amount of water is less than 200 parts by weight or greater than 350 parts by weight, there is a problem that titanium dioxide is not dispersed well.

1 shows a polar surface of hydrated titanium dioxide. Referring to Figure 1, it can be seen that the surface of the titanium dioxide is polar.

Titanium dioxide can be used semi-permanently because it does not change even when it receives light, and since most organic substances are oxidized and decomposed into carbon dioxide and water, there is little secondary pollution and is effective for removing bleach and odor. Titanium dioxide with a photocatalytic function is largely divided into anatase and rutile according to the crystalline form. In general, the rutile type has a problem that the crystal state is stable but the activity is inferior, and the anatase type has a high photocatalytic activity and thus may be a more preferable form in the photocatalyst field. The decomposition of organic matter by the photocatalyst generates electrons and holes when light energy above band gap energy is irradiated to the photocatalyst, and is adsorbed on the surface of the photocatalyst by the strong oxidizing power of the hydroxyl radical (-0H) generated by the photocatalyst. This is due to the oxidation reaction in which the gaseous or liquid organic matter is decomposed.

Since reactions such as decomposition of organic matter and removal of odor as a catalyst of titanium dioxide occur on the surface of titanium dioxide, activity increases as the surface area of titanium dioxide increases, and there is a method of decreasing the particle size by increasing the surface area.

The titanium dioxide of the wax composition according to the present invention has a particle size of 5 nm or less, preferably 1 nm to 5 nm particle size, more preferably 3 nm to 5 nm particle size, and the amount is from 2 parts by weight to 100 parts by weight of titanium dioxide wax. It is preferable that it is 15 weight part.

When the particle size of titanium dioxide exceeds 5 nm, the surface area value of titanium dioxide is small and the activity is rapidly dropped as a photocatalyst as compared to the titanium dioxide input amount in removing odor. In the content of titanium dioxide, when the amount of titanium dioxide is less than 2 parts by weight with respect to 100 parts by weight of wax, the catalytic activity is relatively low in the whole wax composition, and when it is larger than 15 parts by weight, the concentration of titanium dioxide is too large. Not only can phase separation occur, but also the workability is poor.

On the other hand, in order to maintain the good activity in the wax composition, the particle size of titanium dioxide needs to be well dispersed in the wax composition to maintain a large surface area. Since the wax is basically a nonpolar compound as a hydrocarbon compound, titanium dioxide having a polar surface is It is difficult to distribute well. Therefore, treatment of the polar surface of titanium dioxide is required.

The plasticizer increases the flexibility, elasticity, etc. of the blend in the polymer resin, thereby increasing processability and formability. The plasticizer plays a similar role for the wax composition of the present invention including a relatively high molecular weight compound such as wax and binder. In addition to these roles, ether-based plasticizers, in particular the functional group-(O- (CH ₂ ) _n -O) _m-, also serve to make the polar surface of titanium dioxide nonpolar.

The wax composition of the present invention is ether based on the functional group-(O- (CH ₂ ) _n -O) _m- (n is 2 or 3 as an integer, m is 1 to 5 as an integer) based on 100 parts by weight of wax Plasticizer 90 to 200 parts by weight and phthalic acid ester plasticizer, phosphate ester plasticizer, adipic acid ester plasticizer, sebacic acid ester plasticizer, azaline acid ester plasticizer, Plasticizer of any one of citric acid ester plasticizer, glycolic acid ester plasticizer, trimellitic acid ester plasticizer, linoleic acid ester plasticizer, polyester plasticizer, epoxy plasticizer, chlorinated plasticizer or mixtures thereof It is preferable to include from 20 parts by weight. Functional group- (O- (CH ₂ ) _n -O) _m- (where n is 2 or 3 as an integer and m is 1 to 5 as an integer) means that -CH ₂ -units between oxygen and oxygen are n It is repeated, meaning that there are m units of repeating n -CH ₂ -units between such oxygen and oxygen.

Ether-based plasticizers containing a functional group-(O- (CH ₂ ) _n -O) _m- , for example, tris (2-butoxyethyl) phosphate (TBEP), diethylene glycol monoethyl ether (EDG), diethylene glycol monomethyl (MDG) ether) and DPM (dipropylene glycol monomethyl ether), but are not limited thereto. The structure of each formula is shown below.

FIG. 2 is a view showing that in a wax composition in which titanium dioxide (TiO ₂ ) nanoparticles according to the present invention are dispersed, a polar surface of titanium dioxide is surrounded by EDG and nonpolarized. Referring to FIG. 2, the hydrogen bond between the unshared electron pair of EDG oxygen and the titanium dioxide surface OH in Formula 1 and the interaction between the unshared electron pair of EDG oxygen and the empty d-orbital function orbital of the transition metal Ti (that is, with metal EDG covers the polar surface of titanium dioxide due to coordination between ligands), resulting in nonpolarity under the influence of the —CH ₂ CH ₂ — group, which is a nonpolar portion of the EDG.

The ether-based plasticizer comprising the functional group-(O- (CH ₂ ) _n -O) _m -is preferably 90 parts by weight to 200 parts by weight with respect to 100 parts by weight of the wax. If the amount of plasticizer is less than 90 parts by weight with respect to 100 parts by weight of wax, there is a problem that the surface of the titanium dioxide is not sufficiently polarized. If the amount of the plasticizer is greater than 200 parts by weight, the flexibility of the wax composition is increased too much, which is a problem in the coating operation. .

As the phthalic ester plasticizer, for example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate (DBP), dihexyl phthalate, di-n-octyl phthalate, di-2-ethyl hexyl phthalate, diisooctyl Phthalate, dicapryl phthalate (DCP), dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclo Hexyl phthalate, butylbenzyl phthalate, octyldecyl phthalate, butyloctyl phthalate (BOP), octylbenzyl phthalate, n-hexyl-n-decyl phthalate and n-octyl-n-decyl phthalate.

Phosphoric acid ester plasticizers include, for example, tricresyl phosphate, trioctyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, octyldiphenyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl Diphenyl phosphate and trichlor-ethyl phosphate.

Adipic acid ester plasticizers include, for example, dioctyl adipate, di-2-etherhexyl adipate, diisooctyl adipate, didecyl adipate, di-isodecyl adipate, n- Octyl-n-decyl adipate (NODA) and n-heptyl-n-nonyl adipate and the like.

Examples of sebacic acid ester plasticizers include bis (2-ethylhexyl) sebacate, dioctyl sebacate, diisooctyl sebacate and butylbenzyl sebacate (BBS). have.

Azeline acid ester plasticizers include, for example, dioctyl azelate, dihexyl azelate, diisooctyl azelate and di-2-ethyl hexyl azelate.

Citric acid ester plasticizers include, for example, triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate (ATBC) and acetyl trioctyl citrate.

Glycolic acid ester plasticizers include, for example, methyl phthalyl ethyl glycollate, ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate.

Trimellitic acid ester plasticizers include, for example, trioctyl trimellitate and tri-n-octyl-n-decyl trimellitate.

Linoleic acid ester plasticizers include, for example, methyl acetyl ricinolate and butyl acetyl ricinolate.

Polyester plasticizers include, for example, polypropylene adipate and polypropylene sebacate.

Epoxy plasticizers include, for example, epoxidized oil, epoxy butyl stearate and epoxy octyl stearate.

Examples of chlorinated plasticizers include chlorinated paraffins and chlorinated fatty acid esters.

Phthalic acid ester plasticizer, phosphate ester plasticizer, adipic acid ester plasticizer, sebacic acid ester plasticizer, azaline acid ester plasticizer, citric acid ester plasticizer, glycolic acid ester The amount of the plasticizer of any one of a plasticizer, a trimellitic acid ester plasticizer, a linoleic acid ester plasticizer, a polyester plasticizer, an epoxy plasticizer, a chlorinated plasticizer or a mixture thereof is not particularly limited, but is more than 8 parts by weight. If it is small, the flexibility of the wax composition is poor, and if it is more than 20 parts by weight, the flexibility of the wax composition increases too much, which is a problem in the coating operation.

The wax composition according to the present invention is 0.1 to 1 parts by weight of an alkyl alcohol (n = 1 to 10) of C _n H _{2n + 1} OH or a mixture of these alcohols and ethylene glycol as a surfactant, based on 100 parts by weight of wax. 0.5 parts by weight to 20 parts by weight of a fluorine-based surfactant including a substituent, 0.3 parts by weight to 7 parts by weight of a leveling agent, 350 parts by weight to 1000 parts by weight of an aqueous acrylic emulsion of methyl methacrylate, styrene and butyl acrylate copolymer as an acrylic binder. It is preferred to further comprise 10 parts by weight to 45 parts by weight of rosin and rosin.

The dispersant is preferably 0.1 parts by weight to 1 parts by weight with respect to 100 parts by weight of the wax as an alkyl alcohol (n = 1 to 10) of C _n H _{2n +1} OH or a mixture of these alcohols. Examples of dispersants include methanol, ethanol, isopropyl alcohol, propyl alcohol and octyl alcohol. If the amount of the dispersant is less than 0.1 part by weight or greater than 1 part by weight, there is a problem that the durability of the wax is lowered.

In addition to the dispersing function, the surfactant also acts as a thickener, and the evaporation rate may be controlled by adjusting the amount of the surfactant. The surfactant of the wax composition of the present invention is preferably 0.5 parts by weight to 20 parts by weight based on 100 parts by weight of the wax as a fluorine-based surfactant including an ethylene glycol substituent. If the amount of the surfactant is less than 0.5 parts by weight, there is a problem that the viscosity during processing is lowered, and if it is more than 20 parts by weight, there is a problem that the amount of volatile ammonia in the surfactant component is too large.

The leveling agent (leveling agent) is to improve the leveling and appearance of the wax coating film, and may include, for example, polyacrylate-based, silicone-based, polyester-based, amine-based leveling agent, the amount of the leveling agent is based on 100 parts by weight of the wax It is preferable that it is 0.3 weight part-7 weight part. If the amount is less than 0.3 parts by weight, the leveling effect is insignificant, and if it is more than 7 parts by weight, the leveling effect is not significantly better than the amount to be added.

The acrylic binder is preferably 350 parts by weight to 1000 parts by weight with respect to 100 parts by weight of the wax as an aqueous acrylic emulsion of methyl methacrylate, styrene and butyl acrylate copolymers. As the acrylic binder serves as a protective colloid, colloid formation is not performed properly when smaller than 350 parts by weight or larger than 1000 parts by weight, resulting in a non-uniform composition.

Rosin is a resin compound that can be crosslinked by a radical initiator such as active oxygen in the air, thereby enhancing the film strength of the applied wax composition. The amount used is 10 parts by weight to 100 parts by weight of the wax. It is preferable that it is 45 weight part. If it is less than 10 parts by weight, there is a problem that the film strength is weak, and if it is larger than 45 parts by weight, the film strength is too large compared to the film elasticity, and there is a problem that the film is easily broken by external force.

Hereinafter, the manufacturing method of the wax composition of this invention is demonstrated.

Method for producing a wax composition in which the titanium dioxide (TiO ₂ ) nanoparticles of the present invention is dispersed, (a) 10,000 ppm of titanium dioxide (TiO ₂ ) nanoparticles with an average particle diameter of 5 nm or less in 200 parts by weight to 350 parts by weight of water Mixing 100 parts by weight to 400 parts by weight of an aqueous solution of 100,000 ppm; (b) adding and mixing 110 parts by weight to 210 parts by weight of a plasticizer; And (c) characterized in that it comprises the step of mixing by adding 100 parts by weight of wax.

Examples of the wax include paraffin wax, beeswax, microcrystalline wax, carnauba wax, synthetic wax and the like, but PE wax is particularly preferable. Since the wax is intrinsically nonpolar, in order to disperse the polar titanium dioxide well, a plasticizer for nonpolarizing the surface of the titanium dioxide should be added after the titanium dioxide input step, followed by a nonpolar wax.

According to one embodiment of the invention, the plasticizer in the method for producing a wax composition preferably comprises a functional group-(O- (CH ₂ ) _n -O) _m- . Examples and amounts of ether-based plasticizers containing the functional group-(O- (CH ₂ ) _n -O) _m -are as described above (n is 2 or 3 as an integer and m is 1 to 5 as an integer).

According to another embodiment of the present invention, in the method for preparing a wax composition, the plasticizer input step may include at least two kinds of plasticizers including a functional group-(O- (CH ₂ ) _n -O) _m -at intervals of 10 minutes to 1 hour. It is preferable to add sequentially (n is 2 or 3 as an integer, m is 1-5 as an integer).

3 is a schematic diagram showing that in the wax composition in which titanium dioxide (TiO ₂ ) nanoparticles according to the present invention are dispersed, a polar surface of titanium dioxide is surrounded by DPM (dipropylene glycol monomethyl ether) to be non-polarized. Referring to FIG. 3, since the actual surface of the titanium dioxide particles is not an ideal spherical surface but a surface that is somewhat curved and deformed, a slight change in the length of -CH _2- , which is a nonpolar portion of the plasticizer, is required to make the surface nonpolar. Because it is necessary to give, use two or more kinds of plasticizers. Thus, while FIG. 3 shows that DPM makes the titanium dioxide surface nonpolar, in this way, the actual titanium dioxide polar surface Comprising-(O- (CH ₂ ) _n -O) _m -corresponding to the surface with bending and deformation It can be seen that various kinds of plasticizers can nonpolarize the titanium dioxide surface.

On the other hand, in the method for producing a wax composition, the interval between the input step of each of two or more plasticizers containing a functional group-(O- (CH ₂ ) _n -O) _m -is preferably 10 minutes to 1 hour (n Is 2 or 3 as an integer and m is 1 to 5) as an integer. When the interval between each plasticizer input step is shorter than 10 minutes, the efficiency of nonpolarizing titanium dioxide is low, there is a problem that the phase separation of the wax composition occurs later, when the interval between each plasticizer step is longer than 1 hour There is no change in the efficiency of nonpolarizing titanium dioxide.

The method for preparing a wax composition in which the titanium dioxide (TiO ₂ ) nanoparticles of the present invention is dispersed comprises mixing 0.1 parts by weight to 1 part by weight of a dispersant between steps (a) and (b); Mixing 0.5 parts by weight to 20 parts by weight of a fluorine-based surfactant between steps (b) and (c); Mixing 0.3 part by weight to 7 parts by weight of a leveling agent; And (c) adding 350 parts by weight to 1000 parts by weight of the acrylic binder and 10 parts by weight to 45 parts by weight of rosin. In addition to the step of adding water, titanium dioxide, plasticizer and wax, respectively, for the purpose of adjusting the viscosity of the wax composition, the strength and leveling of the coating, and the like, a step of adding a dispersant, a surfactant, a leveling agent, an acrylic binder, and the like is further included.

According to one embodiment of the invention, the plasticizer in the method of producing a wax composition includes a functional group-(O- (CH ₂ ) _n -O) _m- , the plasticizer input step is 10 minutes to 1 or more types of plasticizer Preference is given to sequentially feeding at time intervals (n is 2 or 3 as an integer and m is 1 to 5 as an integer).

Hereinafter, the present invention will be described in more detail, but the following examples are provided for the purpose of explanation and are not intended to limit the present invention.

The shape of stirring apparatuses, such as the stirrer used by this invention, is not specifically limited, The stirring apparatus conventionally used for wax composition manufacture conventionally can be used.

Example 1

70 g of water was added to a 1 L beaker, followed by 40 minutes of stirring, and 200 g of an aqueous solution of titanium dioxide sol (20,000 ppm) having an average particle diameter of 5 nm or less was added thereto. Next, 0.12 g of methanol was added as a dispersant, and the mixture was stirred at 60 rpm for 2 hours, and then stirred at high speed at 180 rpm for 4 hours. Next, while stirring the mixture, 10 g of plasticizer TBEP, 60 g of EDG, 30 g of MDG, 11.5 g of DPM, and 10 g of DBP were each added in sequence of 30 minutes. After the addition of the plasticizer, 8 g of a fluorine-based surfactant (manufacturer: Du Pont, product name: “ZONYL” FSE Fluorosurfactant) was added and stirred for 1 hour. Next, 0.3 g of a leveling agent (manufacturer: Air Products and Chemicals, product name: DYNOL ® 607 SURFACTANT) was added and stirred for 1 hour.

At this time, after confirming that the delamination occurs, and proceeds to the next step (if the delamination occurs, stirred for 30 minutes to 1 hour more).

After checking whether the layers were separated, 10 g of rosin, 80 g of wax (PE-Wax), and 520 g of acrylic binder (AC-12) were added thereto, stirred for 6 hours, and then aged for at least 12 hours to prepare a wax composition.

Examples 2-6

Plasticizer containing water, titanium dioxide, methanol, functional group-(O- (CH ₂ ) _n -O) _m- , TBEP, EDG, MDG and DPM, functional group-(O- (CH ₂ ) _n -O) _m Plasticizers without fluorine-based surfactants (manufacturer: Du Pont, product name: “ZONYL” FSE Fluorosurfactant), leveling agent (manufacturer: Air Products and Chemicals, product name: DYNOL ® 607 SURFACTANT), rosin, wax and acrylic binder A wax composition was prepared in the same manner as in Example 1, except that the amount of was changed as shown in Table 1 below.

Drug name Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Water (g) 70 193.5 139.5 180 170 214 Methanol (g) 0.12 0.11 0.11 0.11 0.1 0.1 TBEP (g) 10 14 13 16 10 10 EDG (g) 60 50 40 57 60 65 MDG (g) 30 - 35 6.4 26 15 DPM (g) 11.5 25 10 - 10 10 Other plasticizers ^{1 )} (g) DBP 10 BOP ^{3 )} 10 DCP ^{4 )} 9 NODA ^{5 )} 10 BBS ^{6 )} 10 ATBC ^{7 )} 9 Surfactant (g) 8 0.5 One 10 10 0.5 Leveling agent (g) 0.3 0.9 1.4 0.5 4 0.4 Rosin (g) 10 13 20 35 10 29 PE-wax (g) 80 66 50 80 65 94 AC-12 (g) 520 487 490 395 495 362 Titanium dioxide ^{2 )} (g) 200 (20,000 ppm) 150 (20,000 ppm) 200 (70,000 ppm) 200 (10,000 ppm) 140 (100,000 ppm) 200 (20,000 ppm)

1) Plasticizers that do not contain functional groups-(O- (CH ₂ ) _n -O) _m-

2) The parenthesis shows the concentration of the titanium dioxide aqueous solution

3) Butyloctyl phthalate

4) Dicapryl Phthalate

5) n-octyl n-decyl adipate

6) Butylbenzyl Sebacate

7) Acetyl Tributyl Citrate

Comparative Example (Wax Composition according to the Prior Art without Titanium Dioxide)

43.9 g of water was added to a 1 L beaker, followed by stirring for 40 minutes. : EFP-200) 2.04g was added and stirred for 30 minutes. Next, 0.03 g of a silicone antifoaming agent (manufacturer: WACKER, product name: SILFOAM® SE 21) was added while stirring the mixture, and the mixture was stirred for 20 minutes. Subsequently, 0.04 g of fluorine resin (manufacturer: eco-friendly polymer, product name: EFP-250L) and 0.02 g of preservative were added thereto, followed by stirring for 30 minutes. Since plasticizer EDG (manufacturer: Hannong Chemical Co., Ltd., EDG) 6.5g was added and stirred for 1 hour, 1g plasticizer TBEP and 0.45g DBP was added and stirred for 1 hour. Finally, 9.4 g of wax (PE-Wax) and 35.8 g of an acrylic binder (manufacturer: Eco-friendly polymer, product name: MC-010) were added thereto, stirred for 6 hours, and then aged for 12 hours to prepare a wax composition.

Deodorizing power  And antimicrobial activity test

Deodorizing and antimicrobial activity was tested by the following method.

1) Ammonia deodorization rate and formaldehyde deodorization rate were carried out by the gas detection tube method under the following conditions.

a) Test piece: 10 cm × 10 cm

b) gas bag: 5L

c) Gas volume in the gas bag: 3L

d) Measurement time: after 2 hours

e) Initial concentration: 15 ppm

f) Deodorization rate (%) = ((Cb-Cs) / Cb) × 100

Cb: blank, concentration of test gas remaining in test gas bag after 2 hours

Cs: concentration of sample gas remaining in test gas bag after 2 hours

2) The antimicrobial activity was performed under the following conditions by the film adhesion method of JIS Z 2801-2000.

a) Standard film: Stomacher 400 POLY -BAG

b) Test conditions: Test bacteria were measured at (35 ± 1) ℃, RH 90% for 24 hours after incubation.

c) Test strain used: Strain 1-Staphylococcus aureus ATCC 6538P

Strain 2-Escherichia coli ATCC 8739

e) Antibacterial effect: 2.0 log or more of antimicrobial activity

Table 2 and Table 3 below shows the deodorizing rate and antimicrobial activity of the noxious substances of the wax composition of the comparative example according to the prior art without containing the wax composition of the present invention and titanium dioxide.

Deodorization Rate Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example Formaldehyde Deodorization Rate (%) 36.7 45.0 40.0 39.5 38.4 41.2 5.9 Ammonia Deodorization Rate (%) 54.5 55.0 56.1 53.9 55.3 54.9 43.2

Antimicrobial activity Example 1 Example 2 Example 3 BLANK sample BLANK sample BLANK sample  Strain 1 Initial bacterial count (bacterial number / ml) 3.8 × 10 ⁵ 3.8 × 10 ⁵ 3.7 × 10 ⁵ 3.7 × 10 ⁵ 3.9 × 10 ⁵ 3.9 × 10 ⁵ After 24 hours (Bacteria / ml) 8.5 × 10 ⁴ <10 8.6 × 10 ⁴ <10 8.6 × 10 ⁴ <10 Antimicrobial activity (log) - 3.9 - 3.8 - 4.0  Strain 2 Initial bacterial count (bacterial number / ml) 2.4 × 10 ⁵ 2.4 × 10 ⁵ 2.3 × 10 ⁵ 2.3 × 10 ⁵ 2.1 × 10 ⁵ 2.1 × 10 ⁵ After 24 hours (Bacteria / ml) 2.3 × 10 ⁷ <10 2.1 × 10 ⁷ <10 2.5 × 10 ⁷ <10 Antimicrobial activity (log) - 6.4 - 6.0 - 6.3

Example 4 Example 5 Example 6 Comparative example BLANK sample BLANK sample BLANK sample BLANK sample 3.8 × 10 ⁵ 3.8 × 10 ⁵ 3.8 × 10 ⁵ 3.8 × 10 ⁵ 3.6 × 10 ⁵ 3.6 × 10 ⁵ 3.6 × 10 ⁵ 3.6 × 10 ⁵ 8.7 × 10 ⁴ <10 8.5 × 10 ⁴ <10 1.4 × 10 ⁵ <10 1.4 × 10 ⁵ 9.5 × 10 ² - 4.0 - 3.8 - 3.9 - 2.2 2.4 × 10 ⁵ 2.4 × 10 ⁵ 2.6 × 10 ⁵ 2.6 × 10 ⁵ 2.2 × 10 ⁵ 2.2 × 10 ⁵ 1.9 × 10 ⁵ 1.9 × 10 ⁵ 2.2 × 10 ⁷ <10 2.0 × 10 ⁷ <10 2.2 × 10 ⁷ <10 2.2 × 10 ⁷ 1.3 × 10 ⁴ - 6.4 - 6.5 - 6.2 - 3.2

In Table 3, the wax composition according to the present invention showed a greater antimicrobial activity than Staphylococcus aureus (strain 1) than the wax composition of the comparative example (since log scale), and was significantly larger than E. coli (strain 2) than the wax composition of the comparative example. The activity value shows that the antibacterial activity is excellent.

The wax composition according to the present invention not only decomposes harmful substances such as ammonia and formaldehyde and harmful substances in the atmosphere due to the titanium dioxide photocatalyst dispersed in the wax, and also shows an antibacterial effect, which is very environmentally friendly. .

Claims (8)

100 parts by weight of wax particles; 200 parts by weight to 350 parts by weight of water; ₂ to 15 parts by weight of titanium dioxide (TiO ₂ ) nanoparticles having an average particle diameter of 5 nm or less dispersed in the water or wax particles; 90 parts by weight to 200 parts by weight of an ether-based plasticizer comprising a functional group-(O- (CH ₂ ) _n -O) _m- (n is 2 or 3 as an integer and m is 1 to 5) as an integer; And phthalic acid ester plasticizers, phosphate ester plasticizers, adipic acid ester plasticizers, sebacic acid ester plasticizers, azaline acid ester plasticizers, citric acid ester plasticizers, and glycolic acid esters. 8 to 20 parts by weight of any one of a plasticizer, a trimellitic acid ester plasticizer, a linoleic acid ester plasticizer, a polyester plasticizer, an epoxy plasticizer, a chlorinated plasticizer or a mixture thereof The wax composition characterized by the above-mentioned. delete The wax composition according to claim 1, wherein the wax composition is 0.1 to 1 parts by weight of an alkyl alcohol (n = 1 to 10) of C _n H _{2n + 1} OH or a mixture of these alcohols as a dispersant based on 100 parts by weight of wax. 0.5 parts by weight to 20 parts by weight of a fluorine-based surfactant containing an ethylene glycol substituent, 0.3 parts by weight to 7 parts by weight of a leveling agent, 350 parts by weight of an aqueous acrylic emulsion of methyl methacrylate, styrene and butyl acrylate copolymers as an acrylic binder. To 1000 parts by weight and rosin (rosin) 10 to 45 parts by weight of the wax composition further comprising. As a method of manufacturing a wax composition in which titanium dioxide (TiO ₂ ) nanoparticles are dispersed, (a) 200 parts by weight to 350 parts by weight of water Mixing by mixing 100 parts by weight to 400 parts by weight of 10,000 ppm to 100,000 ppm aqueous solution of titanium dioxide (TiO ₂ ) nanoparticles having an average particle diameter of 5 nm or less; (b) adding and mixing 110 parts by weight to 210 parts by weight of a plasticizer, and (c) adding 100 parts by weight of wax to mix Method for producing a wax composition comprising. The plasticizer of claim 4, wherein the plasticizer comprises an ether-based plasticizer comprising a functional group-(O- (CH ₂ ) _n- O) _m- (n is 2 or 3 as an integer and m is 1 to 5 as an integer). Wax composition production method characterized in that. The method of claim 5, wherein the plasticizer input step is at least two kinds containing a functional group-(O- (CH ₂ ) _n -O) _m- (n is 2 or 3 as an integer, m is 1 to 5 as an integer) Method for producing a wax composition, characterized in that the ether-based plasticizer is sequentially added at intervals of 10 minutes to 1 hour. The method of claim 4, further comprising: mixing 0.1 parts by weight to 1 parts by weight of a dispersant between steps (a) and (b); Mixing 0.5 parts by weight to 20 parts by weight of a fluorine-based surfactant between steps (b) and (c); Mixing 0.3 part by weight to 7 parts by weight of a leveling agent; And After the step (c) 350 parts by weight to 1000 parts by weight of the acrylic binder and rosin (rosin) 10 to 45 parts by weight of the wax composition manufacturing method further comprising the step of mixing. 8. The plasticizer of claim 7, wherein the plasticizer comprises an ether plasticizer comprising a functional group-(O- (CH ₂ ) _n -O) _m- (n is 2 or 3 as an integer and m is 1 to 5 as an integer). And, The plasticizer input step is a wax composition manufacturing method characterized in that the two or more ether-based plasticizers are sequentially added at intervals of 10 minutes to 1 hour.

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