KR100839892B1 - Method for preparing of spherical titanium dioxide powder - Google Patents

Abstract

The present invention relates to a method for producing spherical titanium dioxide powder, and in particular, to disperse titanium dioxide in an aqueous phase to produce a titanium dioxide aqueous dispersion, and then to prepare the titanium dioxide aqueous dispersion and water glass to mix titanium dioxide in silicon dioxide. A method for producing a spherical titanium dioxide powder to be impregnated.

The spherical titanium dioxide powder according to the present invention not only has excellent UV blocking ability not only in the ultraviolet B region but also in the ultraviolet A region, but at the same time has excellent hiding power and usability, nano-sized titanium dioxide for coloring and hiding feeling in conventional cosmetics It can replace spherical silicon dioxide for

Titanium dioxide powder, silicon dioxide, UV protection, hiding power, feeling

Description

Manufacturing method of spherical titanium dioxide powder {METHOD FOR PREPARING OF SPHERICAL TITANIUM DIOXIDE POWDER}

1 is a SEM photograph of the final spherical titanium dioxide powder impregnated with titanium dioxide in silicon dioxide prepared according to an embodiment of the present invention.

Figure 2 is a graph showing the UV blocking effect in the ultraviolet B region and the ultraviolet A region of the final titanium dioxide powder impregnated with titanium dioxide in silicon dioxide prepared according to an embodiment of the present invention.

3 is a graph showing the UV blocking effect in the ultraviolet B region and the ultraviolet A region of the spherical titanium dioxide powder used in the existing cosmetic raw materials.

Figure 4 is the final spherical titanium dioxide powder impregnated with titanium dioxide in silicon dioxide prepared according to an embodiment of the present invention, spherical titanium dioxide powder used in conventional cosmetic raw materials, and for the pigment used as a conventional cosmetic raw material It is a photograph measuring the hiding power of nanoparticle titanium dioxide (nano TiO ₂ ).

The present invention relates to a method for producing spherical titanium dioxide powder, and more particularly, not only has excellent UV blocking ability in the ultraviolet B region as well as the ultraviolet B region, but also has excellent hiding power and feeling at the same time for hiding power in conventional cosmetics. It relates to a method for producing a spherical titanium dioxide powder that can replace the nano-sized titanium dioxide for pigment and the spherical silicon dioxide for the feeling of use.

Skin damage to the human body by sunlight has been observed for a long time, and various drawings have been proposed to protect the skin from such damage.

In general, harmful ultraviolet light (UV) from sunlight passing through the ultra-high atmosphere and reaching the earth's surface can be classified as follows.

First, there is a strong physiological pathological activity on the skin and energy-rich UV-B rays (wavelengths 290-320 nm), which are absorbed directly above the dermal layer, causing erythema and the deposition of skin pigments.

Second, UV-A rays (wavelength 320-400 nm) that penetrate deep into the skin (dermis and its interior), the energy of this line is much lower and its photobiological effects last much longer, causing suburn to promote skin aging. Let's do it.

Conventional anti-UV cosmetics are generally formulated into creamy and latex products by combining water-soluble and water-insoluble UV-absorbers with ultra-fine particles for the purpose of UV scattering. In the case of such creamy or latex products, oils and waxes Due to the heavy use, the feeling is heavy and oily, so if you use these products in the summer with a lot of sweat and high temperature, the sun protection effect can be given, but it is difficult to give a fresh feeling and there was a considerable burden on the skin.

Japanese Patent Laid-Open Publication No. Hei 1-165517 is a formulation that does not contain oils and waxes. Ultrafine titanium dioxide and about 5-20% of ethanol and a large amount of purified water are included to scatter ultraviolet rays to prevent ultraviolet rays. Although this has been introduced, there is a problem that the ultraviolet light that is not scattered penetrates the skin as it is, because there is only a UV scattering function and there is no function to absorb ultraviolet light, and the actual UV block index (SPF) is also low. In addition, Japanese Laid-Open Patent Publication No. Hei 180819 discloses a method of blocking ultraviolet rays by dispersing titanium dioxide and a water-soluble polymer (such as xanthan gum) in an aqueous phase and an alcohol phase, but in the case of water-soluble polymer (xanthan gum, etc.) In order to facilitate the dispersion of titanium, since the material does not have the actual ultraviolet scattering or absorbing function, there is a problem that effectively blocks the ultraviolet light because it does not have the function of absorbing ultraviolet light as well.

In addition, Japanese Patent Application Laid-Open No. Hei-2279621 has introduced an attempt to protect the skin from ultraviolet rays as a formulation of a lotion containing a powder by combining a water-soluble ultraviolet absorber, ultrafine particles of 3 to 20 µm and a clay component. However, the water-soluble UV absorber is typically difficult to contain a large amount due to the stability and stability of the product, there is a problem in that the UV absorbing ability is lower than the water-insoluble UV absorber.

Despite these proposals, there is a need for sunscreen compositions that have a wide range of protection (ie, both UV-A and UV-B), high efficiency and sufficient stability in the UV region.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a method for producing spherical titanium dioxide powder having excellent UV blocking ability in the ultraviolet B region as well as the ultraviolet B region.

Another object of the present invention is to provide a method for producing spherical titanium dioxide powder which can replace the nano-sized titanium dioxide for coloring and the spherical silicon dioxide for the feeling of use in the conventional cosmetics with excellent hiding power and feeling. .

In order to achieve the above object, the present invention provides a method for producing a spherical titanium dioxide powder,

a) dispersing titanium dioxide in an aqueous phase to produce an aqueous titanium dioxide dispersion; And

b) impregnating titanium dioxide into silicon dioxide by mixing the titanium dioxide aqueous dispersion prepared in the above step with water glass

It provides a method for producing a spherical titanium dioxide powder comprising a.

In addition, the present invention is a method for producing spherical titanium dioxide powder,

a) dispersing titanium dioxide in an aqueous phase to produce an aqueous titanium dioxide dispersion;

b) impregnating titanium dioxide into silicon dioxide by mixing the titanium dioxide aqueous dispersion prepared in the above step with water glass; And

c) Titanium dioxide powder prepared by using a silicone oil or fatty acid soap

Surface modification

It provides a method for producing a spherical titanium dioxide powder comprising a.

In another aspect, the present invention provides a spherical titanium dioxide powder having excellent ultraviolet blocking ability in the ultraviolet A (320 ~ 400 nm) region by the above method.

In another aspect, the present invention provides a cosmetic composition characterized in that the spherical titanium dioxide (TiO ₂ ) impregnated in spherical silicon dioxide (SiO ₂ ) is applied.

Hereinafter, the present invention will be described in detail.

The present inventors have a wide range of UV-blocking area as a raw material for sunscreen protection, spherical titanium dioxide powder excellent in use while replacing titanium dioxide (nano TiO ₂ ) of pigment nanoparticles as a make up cosmetic raw material ( While researching to produce TiO ₂ powder, spherical titanium dioxide (TiO ₂ ) was impregnated into spherical silicon dioxide (SiO ₂ ) to produce spherical titanium dioxide powder (TiO ₂ powder), resulting in a wide range of UV blocking regions. And, it was confirmed that the hiding power and the feeling is excellent, to complete the present invention based on this.

The spherical titanium dioxide powder of the present invention is prepared by dispersing titanium dioxide in an aqueous phase to prepare a titanium dioxide aqueous dispersion and by mixing the titanium dioxide aqueous dispersion prepared in the above step with water glass to impregnate titanium dioxide in silicon dioxide. It is characterized by.

Hereinafter, the method for preparing the spherical titanium dioxide powder of the present invention will be described in detail.

a) Titanium dioxide aqueous dispersion preparation

This step is to prepare a titanium dioxide aqueous dispersion by dispersing titanium dioxide in the water phase.

The titanium dioxide (TiO ₂ ) acts as a pigment for giving hiding power when the spherical titanium dioxide powder of the present invention is applied to the cosmetic composition.

The titanium dioxide is stable when applied to human skin as an inorganic sunscreen raw material, it can be used a conventional titanium dioxide used in the art having a sunscreen effect.

The titanium dioxide is preferably contained in 10 to 70% by weight in the aqueous phase to be dispersed, if it is within the above range can simultaneously satisfy the hiding power, UV blocking effect and dispersibility when mixed with water glass.

The water phase may be stable water, distilled water and the like when applied to the human skin.

Titanium dioxide is added to the aqueous phase and dispersed as described above, wherein the mixture is first dispersed using a homomixer when the mixture is in a constant suspension state, and then, when the first dispersion is completed, through a high speed disperser. The second dispersion may be used to prepare a final titanium dioxide (TiO ₂ ) aqueous dispersion.

b) titanium dioxide impregnation

This step is a step of impregnating titanium dioxide into silicon dioxide by mixing the titanium dioxide aqueous dispersion prepared in step a) and water glass.

The water glass is an aqueous solution of an alkali silicate salt obtained by melting silicon dioxide and an alkali, and the alkali may be Na or K, and specific examples thereof include 10 to 30% by weight of commercially available water. The containing thing can be used.

In addition, the silicon dioxide may be used a conventional silicon dioxide used in the art that is stable when applied to human skin.

The titanium dioxide aqueous dispersion prepared in the above step and the water glass are mixed at an optimum ratio. Specifically, the titanium dioxide aqueous dispersion and the water glass are preferably mixed at a weight ratio of 10 to 70:90 to 30. When the titanium dioxide aqueous dispersion and silicon dioxide are mixed at the above ratios, the titanium dioxide aqueous dispersion and silicon dioxide are better in feeling and UV protection.

The mixture of the titanium dioxide aqueous dispersion and the water glass mixed as described above may be emulsified by adjusting the emulsion rpm, the emulsification time to the particle size of the desired size by adding to the homomixer container in which the emulsifier is dissolved in kerosene. Preferably the temperature during the emulsification is preferably managed at 40 ℃ or less, more preferably 20 to 30 ℃.

Then, when the emulsification is completed, the emulsion is added to sulfuric acid, hydrochloric acid or carbonic acid or a salt solution thereof, and stirred and reacted. The reaction time is preferably 12 hours or more, preferably 12 to 18 hours.

The reaction is subjected to acid treatment with nitric acid (HNO ₃ ) (pH 3.0 or less). After the acid treatment, neutralized with ammonia (NH ₄ OH), dehydration and drying. Then, the dried product is pulverized using an atomizer and sieved using a sieve of about 325 mesh to prepare a final spherical titanium dioxide powder impregnated with titanium dioxide in silicon dioxide. .

The prepared final titanium dioxide impregnated titanium dioxide powder is composed of silicon dioxide having an average diameter of 0.5 to 20 ㎛ and titanium dioxide of 50 to 400 nm, preferably silicon dioxide has an average diameter of 0.5 to 10 ㎛, Titanium dioxide powder is preferably composed of 150 ~ 300 nm. In addition, the content ratio is preferably composed of 30 to 90% by weight of silicon dioxide and 10 to 70% by weight of titanium dioxide, respectively.

c) surface modification

In addition, the prepared titanium dioxide powder may be coated with silicone oil or fatty acid soap to remove photocatalytic activity and to be applied to the actual cosmetic composition formulation. When coating with the silicone oil or fatty acid soap, the coating method may be applied to a conventional method that can be applied in the art.

Silicone oil used to modify the surface of the powder in the present invention is not particularly limited in its kind, and preferably, dimethylpolysiloxane, cyclomethicone, dimethicone, betaine modifide silicone, methylphenyl silicone fluid ( methylphenyl silicone fluid) is recommended.

In addition, the type of fatty acid soap is not particularly limited, but preferably, aluminum stearate, magnesium stearate, and zinc stearate may be used.

In addition, the present invention is prepared by impregnating the spherical titanium dioxide (TiO ₂ ) in the spherical titanium dioxide powder and the spherical silicon dioxide (SiO ₂ ) prepared in the ultraviolet A (320 ~ 400 ㎚) region having excellent UV blocking ability It provides a cosmetic composition to which the titanium dioxide powder is applied. Preferably, the cosmetic composition is a cosmetic composition comprising titanium dioxide powder, spherical silicon dioxide (SiO ₂ ) is impregnated with titanium dioxide (TiO ₂ ) is spherical titanium dioxide powder 1% to 30% by weight, more It is preferable to contain 5% to 18% by weight. If it is in the above range can be satisfied at the same time excellent UV protection ability, hiding power and usability. The spherical titanium dioxide (TiO ₂ ) is impregnated into the spherical silicon dioxide (SiO ₂ ), and the spherical titanium dioxide powder may be prepared by the method for producing the spherical titanium dioxide powder of the present invention.

Cosmetic composition according to the present invention is not only excellent in the ultraviolet ray B region but also in the ultraviolet ray A region can provide a wide range of ultraviolet ray blocking region, as well as a nanoparticle titanium dioxide for pigment (pigment) to give a hiding power as a cosmetic raw material It can replace (nano TiO ₂ ), and can give a good feeling that the nanoparticle titanium dioxide does not have without using a spherical silicon dioxide for the feeling of use.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

(Titanium Dioxide Aqueous Solution)

2,500 mL of water was added to a 5,000 mL beaker, and titanium dioxide (TiO ₂ ), an inorganic UV protection material, was added to 55 wt% in water, and the suspension was dispersed using a high speed disperser to prepare an aqueous dispersion of titanium dioxide (TiO ₂ ). .

(Manufacture of spherical titanium dioxide powder)

The titanium dioxide aqueous dispersion prepared above and water glass were mixed in a weight ratio of 30:70, and then put into a homomixer container in which an emulsifier was dissolved in kerosene, and emulsified to have a particle size of 0.5 to 20 μm.

When the emulsification is completed, an emulsion is added to the ammonium bicarbonate (NH ₄ HCO ₃ ) solution, stirred and reacted, and then acid treated with nitric acid (HNO ₃ ) (pH 3.0 or less). Neutralized with ammonia (NH ₄ OH) (pH 6.0-8.0).

After dehydration and drying (105 ° C.), the dried product is crushed using an atomizer, and sieved using a sieve of about 325 mesh to impregnate titanium dioxide in silicon dioxide. The final spherical titanium dioxide powder was prepared (FIG. 1).

Example 2

Surface modification was performed on the final spherical titanium dioxide powder impregnated with titanium dioxide in silicon dioxide prepared in Example 1 as follows. First, 97 g of the spherical titanium dioxide powder prepared above was put in a 1L beaker, followed by filling with 250 g of water, and 3 g of dimethicone was added thereto and coated at 70-90 ° C. for 12 hours.

The slurry was filtered and dried to prepare a final spherical titanium dioxide powder coated with dimethicone.

Comparative Example 1

A spherical titanium dioxide powder (TiO ₂ ) used as a conventional cosmetic raw material was used.

Comparative Example 2

The dye nanoparticle titanium dioxide (nano TiO ₂ ) used as a conventional cosmetic raw material was used.

The titanium dioxide of Example 1 and Comparative Example 1 was applied to a cosmetic raw material to measure the UV blocking effect (SPF) in the ultraviolet B region and the ultraviolet A region, and the results are shown in FIGS. 2 and 3.

As shown in Figures 2 and 3, the spherical titanium dioxide powder of Example 1 prepared by impregnating titanium dioxide in silicon dioxide according to the present invention exhibits excellent ultraviolet blocking effect not only in the ultraviolet B region but also in the ultraviolet A region. , It was confirmed that the spherical titanium dioxide powder of Comparative Example 1 used in the existing cosmetic raw materials exhibits an ultraviolet blocking effect only in the ultraviolet B region.

In addition, as a result of measuring the hiding power by applying the titanium dioxide of Example 1 and Comparative Examples 1 and 2 to the cosmetic raw material, Example 1 prepared by impregnating titanium dioxide in silicon dioxide according to the present invention as shown in FIG. The spherical titanium oxide powder of showed similar hiding power as titanium nanoparticle titanium dioxide which is used for conventional hiding power, and can provide excellent hiding power without using pigment nanoparticle titanium dioxide in cosmetic raw materials. And it was found. On the other hand, the spherical titanium dioxide powder of Comparative Example 1 had a hiding power of 30.57 was significantly lower than the spherical titanium dioxide powder of Example 1 according to the present invention.

In addition, in order to determine the titanium dioxide and the feeling of use of Example 2 and Comparative Example 2 to prepare a cosmetic composition of Examples 2 to 10 and Comparative Examples 3 to 6 with the composition as shown in Tables 1 to 4 to measure the hiding power and feeling. The unit of component content is parts by weight.

TABLE 1

No Ingredients INCI Name Comparative Example 3 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 One Abil EM 90 Cetyl PEG / PPG- 10/1 Dimethicone 5.2 5.2 5.2 5.2 5.2 5.2 5.2 2 DC 5225C Cyclopentasilxane & PEG / PPG18 / 18 Dimethicone 8.1 8.1 8.1 8.1 8.1 8.1 8.1 3 KSG-16 Dimethicone & Dimethcone vinyl copolymer 7.0 7.0 7.0 7.0 7.0 7.0 7.0 4 KF 995 Cyclomethicone 49.4 49.4 49.4 49.4 49.4 49.4 49.4 5 Olivem 900 Sorbitan Olivate 3.3 3.3 3.3 3.3 3.3 3.3 3.3 6 Bentone Gel ISDV Isododecane & Quaterium-18 Hectorite & Propylene Carbonate 5.5 5.5 5.5 5.5 5.5 5.5 5.5 7 KF-6017 PEG-10 Dimethicone 2.0 2.0 2.0 2.0 2.0 2.0 2.0 8 Talc J-DS Talc & Dimethicone & Methicone 4.5 4.5 4.5 4.5 4.5 4.5 4.5 9 SUNSIL-130 Spherical Silicon Dioxide For Usability 8.0 - - - - - - 10 TiO2 Nanoparticle Titanium Dioxide <Comparative Example 2> 7 5 4 3 2 One - 11 TinUVAB Spherical Titanium Dioxide Powder <Example 2> - 10 11 12 13 14 15 WHITENESS INDEX 74.13 77.98 76.69 75.78 73.93 68.16 64.70 Feeling Standard Similar to standard Similar to standard Superior to Standard Superior to Standard Superior to Standard Superior to Standard

Table 2 Example of Manufacturing Sunscreen Combined Makeup Base

NO Ingredients INCI Name Comparative Example 4 Example 8 One Emalex SS- 5050K - 3.7 3.7 2 KF96 (6CS)      Dimethicone 5.0 5.0 3 KF-995    Cyclomethicone 7.0 7.0 4 TALC-AS    Talc & Triethoxy caprylylsilane 3.0 3.0 5 TiO2-SS Nanoparticle Titanium Dioxide for Feeling and Silver Penetration 3.5 - 6 MT100TV Nanoparticle Titanium Dioxide for Feeling and Silver Penetration 3.0 - 7 SUNSIL- 130SC Spherical Silicon Dioxide For Usability 7.0 - 8 TinUVAB Spherical Titanium Dioxide Powder <Example 2> - 13.5 9 ABIL-EM90 Cetyl PEG / PPG- 10/1 Dimethicone 2.0 2.0 10 KSG 16 Dimethicone & Dimethcone vinyl copolymer 2.0 2.0 11 PARSOL MCX - 7.0 7.0 12 AEROSIL R972 - 0.8 0.8 13 1.3-B.G - 10.0 10.0 14 D.I WATER Distilled water 45.0 45.0 15 NaCL Salt 1.0 1.0 Whiteness index 62.8 60.9 Feeling Standard Similar to Standard

Table 3 Example of Manufacturing Makeup Base

NO Ingredients INCI Name Comparative Example 5 Example 9 One Emalex SS- 5050K - 3.2 3.2 2 KF96 (6CS)      Dimethicone 3.0 3.0 3 KF-995    Cyclomethicone 12.0 12.0 4 TALC-AS    Talc & Triethoxy caprylylsilane 3.0 3.0 5 TiO2-SS Nanoparticle Titanium Dioxide for Feeling and Silver Penetration 3.5 - 6 SUNSIL- 130SC Spherical Silicon Dioxide For Usability 7.0 - 7 TinUVAB Spherical Titanium Dioxide Powder <Example 2> - 10.5 8 ABIL-EM90 Cetyl PEG / PPG- 10/1 Dimethicone 2.0 2.0 9 KSG 16 Dimethicone & Dimethcone vinyl copolymer 2.0 2.0 10 DC200F 10CS - 2.0 2.0 11 TCG-M - 2.0 2.0 12 CETIOL-LC 2.0 2.0 13 AEROSIL R972 - 0.3 0.3 14 1.3-B.G - 8.0 8.0 15 D.I WATER Distilled water 49.0 49.0 16 NaCL Salt 1.0 1.0 Whiteness index 60.91 58.33 Feeling Standard Similar to Standard

Table 4 Example of two-way cake

NO Ingredients INCI Name Comparative Example 6 Example 10 One MICA - 29.0 29.0 2 SERI-AS             Mica & Triethoxy caprylylsilane 13.85 13.85 3 TiO2 / SERICITE SS    Nanoparticle Titanium Dioxide for Usability 8.0 8.0 4 TiO2 / MICA SS                  Nanoparticles Titanium Dioxide for Silver Penetration 19.0 - 5 MICA-SS - 4.0 4.0 6 SUNPMMA Spherical Polymethylmethacrylate for Usability 6.0 6.0 7 SUNSIL- 130SC Spherical Silicon Dioxide For Usability 7.0 - 8 TinUVAB Spherical Titanium Dioxide Powder <Example 2> - 26.0 9 IOY-SS Ferric Oxide for Pigmentation 2.15 2.15 10 IOR-SS Ferric Oxide for Pigmentation 0.5 0.5 11 IOB-SS Ferric Oxide for Pigmentation 0.3 0.3 12 M.P Preservative 0.1 0.1 13 SQUALAN - 1.0 1.0 14 Vaseline Vaseline 1.0 1.0 15 COSMOL 222 - 1.0 1.0 16 SILICONE 200F / 10CS      Dimethicone 2.5 2.5 17 SILICONE 200F / 100CS      Dimethicone 4.5 4.5 Cloaking force (after skin application) Standard Similar to standard Feeling Standard Similar to standard

As shown in Tables 1 to 4, the cosmetic composition of the example prepared according to the present invention was found to not only provide a hiding power comparable to that of titanium dioxide of the conventionally used dye nanoparticles, as well as an excellent feeling.

The cosmetic composition according to the present invention is not only excellent in ultraviolet ray B region but also in the ultraviolet ray A region, which can provide a wide range of ultraviolet ray blocking region, as well as providing a hiding power as a raw material for cosmetics. Carbon (nano TiO ₂ ) can be replaced, and there is an effect that can give excellent feeling that the nanoparticle titanium dioxide does not have without using a spherical silicon dioxide for the feeling of use.

The present invention described above is not limited to the above-described embodiment and the accompanying drawings, and various substitutions, modifications, and changes are possible within the scope of the technical spirit of the present invention. It is obvious to one with ordinary knowledge.

Claims (8)

In the manufacturing method of the spherical titanium dioxide powder, a) dispersing titanium dioxide in an aqueous phase to produce an aqueous titanium dioxide dispersion; And b) impregnating titanium dioxide into silicon dioxide by mixing the titanium dioxide aqueous dispersion prepared in the above step with water glass Method of producing a spherical titanium dioxide powder comprising a. In the manufacturing method of the spherical titanium dioxide powder, a) dispersing titanium dioxide in an aqueous phase to produce an aqueous titanium dioxide dispersion; b) impregnating titanium dioxide into silicon dioxide by mixing the titanium dioxide aqueous dispersion prepared in the above step with water glass; And C) Titanium dioxide powder prepared above with silicone oil or fatty acid soap Surface modification Method of producing a spherical titanium dioxide powder comprising a. The method according to claim 1 or 2, Method for producing a spherical titanium dioxide powder, characterized in that the titanium dioxide is dispersed in 10 to 70% by weight in the water phase. delete The method according to claim 1 or 2, The impregnation of the titanium dioxide emulsifies the mixture of the aqueous dispersion of titanium dioxide and water glass, and after the completion of the emulsification, an emulsion is added to sulfuric acid, hydrochloric acid, carbonic acid or a salt solution thereof, stirred and reacted, and then acid-treated and neutralized. Process for producing spherical titanium dioxide powder, characterized in that carried out by dehydration, drying, and grinding. A spherical titanium dioxide powder produced by the method according to claim 1. In a cosmetic composition comprising a titanium dioxide powder, Cosmetic composition, characterized in that it contains 1% to 30% by weight of spherical titanium dioxide (TiO ₂ ) in spherical silicon dioxide (SiO ₂ ). delete

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