KR100378521B1 - The method for preparation of sun protecting complex powder - Google Patents

Abstract

The present invention is a hydrolysis of the titanium alkoxide by the sol-gel method to coat the nano-sized titanium oxide (TiO ₂ ) uniformly on the organic resin or inorganic powder or impregnated therein transparency caused by the aggregation between the conventional titanium oxide In addition, the present invention relates to a method for producing a functional composite powder for cosmetics, which has solved a phenomenon of lowering skin feel and skin adhesion and lowering ultraviolet ray shielding effect.

The present invention is an improvement of the conventional method of titanium alkoxide hydrolysis, and the organic resin and the inorganic powder is modified inside / outside to activate the reaction site, and the rate of hydrolysis reaction is controlled to slowly grow titanium oxide particles in / outside the powder By coating the nano-sized titanium oxide fine uniformly or impregnated therein.

Description

Manufacturing method of sunscreen composite powder {THE METHOD FOR PREPARATION OF SUN PROTECTING COMPLEX POWDER}

The present invention relates to a method for producing a sunscreen composite powder. More specifically, the present invention relates to a method for preparing UV-blocking composite powder in which nano-size titanium oxide is finely uniformly coated on the outside of an organic resin or an inorganic powder or impregnated therein by controlling the titanium alkoxide hydrolysis rate.

Recently, as the destruction of the ozone layer due to environmental pollution has increased, it is not only an environmental problem, but as a result, an excessive exposure to ultraviolet rays increases premature aging of the skin, skin cancer, and the like, and interest in sunscreens is increasing accordingly.

Generally, sunscreens used in cosmetics are classified into organic sunscreens and inorganic sunscreens, and the organic sunscreens of the PAsol MCX system having a conjugation bond capable of absorbing ultraviolet rays in the molecular structure (Chemical name: Octyl methoxycinnamate) UV absorbers are the predominant. However, Pasol MCX, an organic sunscreen, has disadvantages such as skin toxicity, allergies, and discoloration. Recently, inorganic sunscreens are used instead of organic sunscreens.

On the other hand, the inorganic sunscreen has a sunscreen effect mainly by scattering ultraviolet rays, as a representative inorganic sunscreen is a metal oxide having a high refractive index TiO ₂ , CeO ₂ , ZnO, ZrO ₂ and the like are used. Among these, TiO ₂ is relatively low cost and very high refractive index, but is often used such a powerful UV capabilities of a (2.5) reasons, the primary particles (nano size) by the TiO ₂ own bad skin texture and strong mutual cohesion of their By agglomerating with each other, secondary particles (micro size) are produced, and there is a problem in use that the skin adhesion and the sunscreen effect are sharply inferior.

Therefore, in order to prevent agglomeration of the TiO ₂ wateuna various studies on the emulsion of TiO ₂ particles is in progress, it is very difficult to painting a nanoscale TiO ₂ particles in water-based or oil-based as nanoscale particle state, and thus nanoscale TiO ₂ Even when the particles are emulsified, there are many problems in maintaining product stability when these nano-size TiO ₂ particles are blended into the finished cosmetic product.

In order to solve various problems when using the nano-sized TiO ₂ in cosmetics as a sunscreen material, in the present invention, nano-sized TiO ₂ is finely uniformly coated or impregnated inside the organic or inorganic powder, and the TiO ₂ particles It has been established that a method for producing a composite powder having agglomeration properties, excellent skin feel, skin adhesion, and high UV blocking ability.

Fine uniform nanoscale TiO ₂ to TiO ₂ by hydrolysis of the titanium alkoxide gel method An attempt has been made to coat the base material surface, the conventional inorganic powder and TiO _2, or an organic resin other than a simple mixing method of TiO _2, sol Due to the coating on the substrate and the secondary aggregation of the TiO ₂ particles produced, there was a limit in that the transparency, skin feel, skin adhesion, and ultraviolet shielding effect were not substantially improved compared to the simple mixing of the substrate and TiO ₂ . .

The present invention relates to a method for producing a functional composite powder for cosmetics having a higher UV protection effect while supplementing the disadvantages of the use and blending of UV protection material used in conventional cosmetics. The composite powder prepared according to the present invention can be applied to various sunscreen cosmetic products (sunscreen lotion, makeup products, skin care products, etc.).

An object of the present invention is to protect the skin from ultraviolet rays by producing a functional composite powder by impregnating or coating an inorganic powder having a sunscreen effect in / outside the cosmetic powder. Therefore, the technical problem to be achieved in the present invention is to activate nano-size TiO ₂ by controlling the rate of hydrolysis and activation inside and outside the reaction to hydrolyze titanium alkoxide to finely coat or impregnate TiO ₂ on the outside of the substrate. / Inorganic or organic substrate synthesis method.

The method for preparing functional composite powders having the above selective characteristics is 1. Raw material input, 2. Inorganic powder or organic resin in / outer activation, 3. TiO ₂ polymerization, 4. Slurry filtration, washing and drying, 5. Surface modification (Surface treatment and sintering), 6. It can be divided into six stages of manifestation of synergistic effect (UV synergy) by complexation.

In detail, the present invention comprises the steps of (1) activating the inorganic powder or organic resin inside / outside with an acid to generate the maximum OH group; (2) When hydrolysis of titanium alkoxide to inorganic powder or organic resin activated inside / outside, the molar ratio of water / titanium alkoxide and alcohol / titanium alkoxide is increased to make hydrolysis rate as slow as possible to coat TiO ₂ finely or uniformly. Impregnating; (3) filtering, washing, and drying the slurry; (4) A fatty acid soap of C ₈ to C ₂₂ was added to the composite powder impregnated with TiO ₂ and then coated with aluminum sulfate or aluminum chloride. Coating or treating the surface of the composite powder with silicone oil at pH 6-9 to control the photocatalytic properties of TiO ₂ ; And (5) relates to a method for producing a composite powder consisting of a step of mixing the organic or inorganic material having a UV blocking effect in the composite powder impregnated / coated with TiO ₂ exhibits a synergistic effect of UV protection. Each step will be described in more detail as follows.

1. Raw material input stage

The input raw materials include alcohol, distilled water, inorganic and organic powders, and titanium alkoxide. Alcohol used as a solvent dissolves titanium alkoxide, and methyl alcohol, ethyl alcohol, propyl alcohol and isopropyl alcohol. , Butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol and the like can be used.

The inorganic powder and the organic powder may be powder having an average particle size of 0.1 to 100 m. For the inorganic powder, both inorganic spherical or inorganic plate-like powder may be used. For example, silica, silica gel, alumina, mica, mica, Talc and the like, and as the organic powder, nylon, polymethylmethacrylate (hereinafter referred to as PMMA), polyethylene (hereinafter referred to as PE), polystyrene (hereinafter referred to as PS), and the like can be used. The titanium alkoxide used as starting material for TiO ₂ is Ti (OR) ₄ , where R has 1 to 6 carbon atoms. For example, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide and the like can be used.

2. Internal / External Activation Steps

The internal / external activation step consists of (1) removal of internal / external contaminants by washing and (2) reaction internal / external activation steps by internal / external reforming. The condensation reaction by titanium alkoxide hydrolysis may occur between the titanium hydroxide and the titanium hydroxide and the OH groups inside and outside the powder, so that the organic contaminants are physically removed during the washing process to hydrophilize the inside and the outside, The internal / external reforming process aims to expose as many OH groups as possible by cutting siloxane crosslinks in / outside the inorganic powder so that TiO ₂ polymerization can occur in / out of the powder. More specifically, the mixture is heated at a high temperature (80 ° C. or more) for at least 2 hours under acidic conditions such as nitric acid, hydrochloric acid, sulfuric acid, and hydrofluoric acid to hydrolyze the siloxane crosslinking, and the inorganic powder is filtered, washed, and dried.

3. TiO ₂ Polymerization

The most important point in the internal / external activation step is to make maximum TiO ₂ polymerization site in and out of the powder (internal / external activation), so that TiO ₂ produced by alkoxide hydrolysis reaction can grow uniformly in and out of the powder. It is to process the powder so that it can.

Thereafter, in the TiO ₂ polymerization step, the rate of titanium alkoxide hydrolysis is slowed down as much as possible so that TiO ₂ polymerization occurs gradually, thereby controlling the reaction rate to grow fine uniform TiO ₂ . The titanium alkoxide hydrolysis reaction is exothermic and the reaction rates are as follows.

V = k [H ₂ O] ² / [Ti (OR) ₄ ] / [ROH]

Reaction factors that can control the rate of hydrolysis are (1) molar ratio of [H ₂ O] / [Ti (OR) ₄ ], [H ₂ O] / [ROH], (2) solvent amount and type, (3 ) There are kinds of Ti (OR) ₄ , (4) reaction temperature, and (5) dosing method. By controlling these, TiO ₂ can be coated uniformly inside and outside the substrate. The reaction element is described in detail as follows.

(1) molar ratio of [H ₂ O] / [Ti (OR) ₄ ], [H ₂ O] / [ROH]

Water is the most important factor that determines the rate of hydrolysis of titanium alkoxide. If the molar ratio of [H ₂ O] / [Ti (OR) ₄ ] and [H ₂ O] / [ROH] are reduced, water and titanium alkoxide and water The hydrolysis reaction of is slowed down and the reaction rate at which TiO ₂ is formed is slowed down. Therefore, TiO ₂ may be finely and uniformly coated on the inside / outside of the substrate. If the hydrolysis reaction of the titanium alkoxide proceeds rapidly, secondary aggregation between TiO ₂ occurs and the coating is not uniformly coated inside / outside of the substrate, resulting in a decrease in transparency, skin feel and skin adhesion, and a decrease in UV shielding effect.

(2) solvent effect

The purpose of the solvent is to control the reaction of titanium alkoxide and water to give a homogeneous reaction. Depending on the amount and type of solvent, the rate of hydrolysis can be controlled.When the amount of solvent is used, the reaction with titanium alkoxide is physically slow, and when a solvent with a large molecular weight is used, the rate of hydrolysis is reduced by decreasing the fluidity of titanium alkoxide and water. Decreases. Therefore, if a large amount of solvent or a solvent having a large molecular weight is used, TiO ₂ may be finely and uniformly coated without secondary agglomeration in / out of the substrate.

(3) alkoxide effects

The type of alkyl group of the titanium alkoxide affects the rate of hydrolysis. The higher the molecular weight of the alkyl group, that is, the higher the alkyl group, the slower the hydrolysis rate because the alkyl group bound to titanium has a steric hindrance to the reaction.

(4) reaction temperature

In general, according to Arrhenius's equation, the higher the reaction temperature, the faster the reaction rate. The hydrolysis reaction of titanium alkoxide also increases as the temperature increases, but physically, it has been reported that the aggregation of TiO ₂ decreases.

The Arrhenius equation is

k = A exp (-Ea / RT)

(5) Input method

The rate of hydrolysis of titanium alkoxide can be controlled by adjusting the rate of titanium alkoxide addition. The slower the feed rate, the slower the rate of hydrolysis.

4. Slurry filtration, washing and drying

The washing step is performed in two steps, one step of removing unreacted titanium alkoxide and two steps of removing alcohol produced during the hydrolysis reaction of titanium alkoxide. In the first step, unreacted titanium alkoxide is removed by stirring at 25 ° C. for 2 hours using alcohol 5 times the total powder weight. In step 2, alcohol is removed by stirring for 2 hours using water 5 times the total powder weight.

The drying step is to remove the water and alcohol in the powder inside / outside to dry for 10 to 20 hours at 100 ~ 150 ℃ so that the residual amount of drying is less than 1% by weight.

5. Surface modification (surface treatment and sintering)

(1) surface treatment

Amorphous and rutile TiO ₂ have no photocatalytic activity, but anatase TiO ₂ has been reported to exhibit photocatalytic activity. Photocatalytic activity destroys skin cells and has a detrimental effect on the human body. In order to remove the photocatalytic activity of the anatase type TiO _2, the photocatalytic activity may be removed by coating a hydrophobic silicone oil, a fatty acid salt or an inorganic powder.

(2) sintering

Sintering acts to remove the photocatalytic activity of TiO ₂ and to raise the ultraviolet ray blocking effect. The structure of TiO ₂ was sintered at 800 ° C. to change from amorphous to rutile. When the structure of TiO ₂ is changed from amorphous to rutile type, the refractive index increases from 2.1 to 2.7, which increases the UV scattering effect and increases the UV blocking effect.

The results of UV protection before and after sintering showed the following results.

Porous Silica (% by weight) TiO _{2 support} (wt%) according to the present invention SPF (Sinter) SPF (After Sintering) 1-a 90 10 7 9 1-b 80 20 16 20 Porous Silica (% by weight) TiO ₂ coating (wt%) according to the present invention SPF (Sinter) SPF (After Sintering) 2-b 90 10 9 12 2-b 80 20 22 26

6. Expression of synergy of UV blocking by complexation

When the composite powder according to the present invention is mixed with TiO ₂ as a pigment, it shows superior UV blocking ability than TiO ₂ alone or composite powder alone, and the results are shown in the table below. In addition, when using ZnO as a mixture of Pasol MCX or pigment instead of TiO ₂ , the same increase in the sunscreen effect was shown.

Talc (% by weight) Pigment TiO ₂ Mix (wt%) TiO ₂ coating (wt%) according to the present invention SPF 1-a 70 15 15 24 1-b 70 30 0 8 1-c 70 0 30 14 Porous Silica (% by weight) Fasol MCX (% by weight) TiO ₂ coating (wt%) according to the present invention SPF 2-a 70 15 15 34 2-b 70 30 0 28 2-c 70 0 30 14 Sericite (% by weight) Pigment ZnO Mix (wt%) TiO ₂ coating (wt%) according to the present invention SPF 3-a 70 15 15 27 3-b 70 30 0 7 3-c 70 0 30 14

ηSPF (sun protection fater) measuring equipment and sample volume

Measuring Equipment: Optometrics 290 plus,

Sample volume: 1 mg / cm ²

According to the literature, it is reported that the UV-blocking area absorbed according to the TiO ₂ particle size is different, the small particle size effectively blocks the UV-B (290 ~ 320 nm) area, the larger the particle size UV-A (320 ~ 400nm) It effectively blocks the area. Therefore, TiO ₂ -coated composite powder blocks the UV-B region, and the pigment TiO ₂ blocks the UV-A region. In addition, since TiO ₂ has a smaller particle size than the coated composite powder, TiO ₂ serves to prevent voids between particles, thereby exhibiting a synergistic effect. Therefore, when TiO ₂ is mixed with TiO ₂ as a pigment in the composite coating fine uniform it is effectively block ultraviolet light.

The synergistic effect was not so high when the composite material coated with TiO ₂ on the porous spherical silica was uniformly coated with UV-B (290-320 nm). The synergistic effect was not very high because the composite material coated with TiO ₂ uniformly as the region and the UV blocking region coincide.

When ZnO is mixed as a pigment in a composite material coated with TiO ₂ finely uniformly on the surface of sericite, the composite material blocks the UV-B (290 to 320 nm) region, and ZnO is UV-A (320 to 400 nm). Blocking the area effectively blocks ultraviolet rays.

Hereinafter, the present invention will be described in detail with reference to the following Examples. The scope of the present invention is not limited to the examples and the scope is defined in detail in the claims.

Example 1

100 g of porous spherical silica (average particle size: 0.1-100 m) was added to a 1 L beaker with 450 g of distilled water and 50 g of nitric acid, and stirred at 60 ° C. for 1 hour, followed by filtration, washing, and drying. 880 g of ethanol and 65 g of distilled water were added to a 3-liter four-necked flask equipped with a stirrer, a thermometer, and a cooler, and 100 g of porous spherical silica (average particle size: 0.1 to 100 m), which was activated inside / outside, was stirred, and the slurry was 43 g of titanium alkoxide was added in a state and reacted at 30 to 78 ° C. for 8 hours. The slurry was filtered, washed, and dried to prepare a composite powder coated with TiO ₂ .

Example 2

100 g of porous spherical silica (average particle size: 0.1-100 m) was added to a 1 L beaker with 450 g of distilled water and 50 g of nitric acid, and stirred at 60 ° C. for 1 hour, followed by filtration, washing, and drying. 880 g of ethanol and 65 g of distilled water were added to a 3-liter four-necked flask equipped with a stirrer, a thermometer, and a cooler, and 100 g of porous spherical silica (average particle size: 0.1 to 100 m), which was activated inside / outside, was stirred, and the slurry was 43 g of titanium alkoxide was added in a state and reacted at 30 to 78 ° C. for 8 hours. The slurry was filtered, washed and dried, and then calcined at 200 to 1000 ° C. to prepare a composite powder coated with TiO ₂ .

Example 3

100 g of porous spherical silica (average particle size: 0.1-100 m) was added to a 1 L beaker with 450 g of distilled water and 50 g of nitric acid, and stirred at 60 ° C. for 1 hour, followed by filtration, washing, and drying. Into a 3-liter four-necked flask equipped with a stirrer, a thermometer and a cooler, 880 g of ethanol and 65 g of distilled water were added, and 100 g of porous spherical silica (average particle size: 0.1 to 100 m) with activated / external water was stirred with a slurry. 43 g of titanium alkoxide was added thereto and reacted at 30 to 78 ° C. for 8 hours. The slurry was filtered, washed, and dried to prepare a composite powder coated with TiO ₂ .

97 g of the composite powder thus prepared was placed in a 1 L beaker, 500 g of distilled water was added, 3 g of dimethylpolysiloxane was dispersed in 30 g of ethanol, and the mixture was stirred at room temperature for 6 hours. The slurry was filtered and dried to prepare a composite powder coated with dimethylpolysiloxane.

Example 4

100 g of porous spherical silica (average particle size: 0.1-100 m) was added to a 1 L beaker with 450 g of distilled water and 50 g of nitric acid, and stirred at 60 ° C. for 1 hour, followed by filtration, washing, and drying. Into a 3-liter four-necked flask equipped with a stirrer, a thermometer, and a cooler, 880 g of ethanol and 65 g of distilled water were added, and 100 g of porous spherical silica (average particle size: 0.1 to 100 m), which was activated inside / outside, was put into a slurry state. 43 g of titanium butoxide was added and reacted at 30 to 78 ° C. for 8 hours. The slurry was filtered, washed, and dried to prepare a composite powder coated with TiO ₂ .

1 L of distilled water and 0.7 g of sodium hydroxide were put into a 2 L four-necked flask, 2.4 g of stearic acid was added with stirring, and the mixture was reacted at 80 ° C for 1 hour. After adding 95 g of TiO ₂ coated composite powder, 1 g of aluminum sulfate was added and reacted at 80 ° C. for 1 hour. The slurry was filtered, washed, and dried to prepare a composite powder coated with TiO ₂ and aluminum stearate.

Example 5

100 g of porous spherical silica (average particle size: 0.1-100 m) was placed in a 1 L beaker with 450 g of distilled water and 50 g of nitric acid, followed by stirring at 60 ° C for 1 hour, followed by filtration, washing and drying. 880 g of ethanol and 65 g of distilled water were added to a 3-liter four-necked flask equipped with a stirrer, thermometer, and cooler, and 90 g of porous spherical silica (average particle size: 0.1 to 100 m) and 10 g of ZnO powder were stirred. After the addition, 43 g of titanium butoxide was added in a slurry state and reacted at 30 to 78 ° C. for 8 hours. The slurry was filtered, washed, and dried to prepare a composite powder coated with TiO ₂ and ZnO.

Example 6

100 g of porous spherical silica (average particle size: 0.1-100 m) was added to a 1 L beaker with 450 g of distilled water and 50 g of nitric acid, and stirred at 60 ° C. for 1 hour, followed by filtration, washing, and drying. Into a 3-liter four-necked flask equipped with a stirrer, a thermometer and a cooler, 880 g of ethanol 65 g of distilled water was added, and 100 g of titanium alkoxide was added to 100 g of porous spherical powder (average particle size: 0.1 to 100 m) activated inside and outside. Titanium alkoxide was supported in the powder to make a dough, which was then added to the reaction solution and reacted at 30 to 78 ° C. for 8 hours. The slurry was filtered, washed, and dried to prepare a composite powder having TiO ₂ coated therein.

Example 7

100 g of porous spherical silica (average particle size: 0.1-100 m) was added to a 1 L beaker with 450 g of distilled water and 50 g of nitric acid, and stirred at 60 ° C. for 1 hour, followed by filtration, washing, and drying. 1588 g of distilled water was added to a 3-liter four-necked flask equipped with a stirrer, a thermometer, and a cooler, and 100 g of titanium alkoxide was added to 100 g of porous spherical powder (average particle size: 0.1 to 100 m) activated inside / outside to make a dough. After supporting the titanium alkoxide in the powder, it was put in the reaction solution and reacted for 8 hours at 30 ~ 100 ℃. The slurry was filtered, washed, and dried to prepare a composite powder having TiO ₂ coated therein.

Example 8

100 g of porous spherical silica (average particle size: 0.1-100 m) was added to 450 g of distilled water and 50 g of nitric acid in a 1 L beaker and stirred at 60 ° C. for 1 hour, followed by filtration, washing and drying. 1588 g of distilled water was added to a 3-liter four-necked flask equipped with a stirrer, a thermometer, and a cooler, and 100 g of titanium alkoxide was added to 100 g of porous spherical powder (average particle size: 0.1 to 100 m) activated inside / outside to make a dough. After the titanium alkoxide was supported in the powder, it was added to the reaction solution and reacted at 30 to 100 ° C. for 8 hours. The slurry was filtered, washed, dried, and calcined at 200 to 1000 ° C. to prepare a composite powder coated with TiO ₂ therein.

Example 9

15 wt% of parsol MCX was dissolved in MC (methylene chloride) in the composite powder prepared in Example 1, and then loaded in the composite powder, reacted for 2 hours, and dried to prepare a composite powder having the parsol MCX.

Example 10

A TiO ₂ -coated composite powder was prepared in the same manner as in Example 1, except that hydrochloric acid was used instead of nitric acid.

Example 11

Except for using sulfuric acid instead of nitric acid was prepared in a composite powder coated with TiO ₂ in the same manner as in Example 1.

Example 12

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1 except that hydrofluoric acid was used instead of nitric acid.

Example 13

A TiO ₂ -coated composite powder was prepared in the same manner as in Example 1 except that silica gel was used instead of porous spherical silica.

Example 14

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1 except that alumina was used instead of porous spherical silica.

Example 15

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1 except that mica was used instead of porous spherical silica.

Example 16

A TiO ₂ -coated composite powder was prepared in the same manner as in Example 1, except that the mica was used instead of the porous spherical silica.

Example 17

A TiO ₂ -coated composite powder was prepared in the same manner as in Example 1 except that talc was used instead of porous spherical silica.

Example 18

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1 except that nylon was used instead of porous spherical silica.

Example 19

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1, except that PMMA was used instead of porous spherical silica.

Example 20

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1 except that PE was used instead of porous spherical silica.

Example 21

A TiO ₂ -coated composite powder was prepared in the same manner as in Example 1 except that PS was used instead of porous spherical silica.

Example 22

A TiO ₂ -coated composite powder was prepared in the same manner as in Example 1 except that the molar ratio of water and titanium butoxide was used in a range of 10 to 200.

Example 23

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1, except that titanium ethoxide was used instead of titanium butoxide.

Example 24

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1, except that titanium propoxide was used instead of titanium butoxide.

Example 25

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1, except that titanium isopropoxide was used instead of titanium butoxide.

Example 26

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1 except that titanium 2-ethylhexide was used instead of titanium butoxide.

Example 27

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1 except that methyl alcohol was used instead of ethyl alcohol.

Example 28

A TiO ₂ -coated composite powder was prepared in the same manner as in Example 1 except that propyl alcohol was used instead of ethyl alcohol.

Example 29

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1 except that isopropyl alcohol was used instead of ethyl alcohol.

Example 30

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1 except that butyl alcohol was used instead of ethyl alcohol.

Example 31

A TiO ₂ -coated composite powder was prepared in the same manner as in Example 1, except that pentyl alcohol was used instead of ethyl alcohol.

Example 32

A TiO ₂ -coated composite powder was prepared in the same manner as in Example 1 except that hexyl alcohol was used instead of ethyl alcohol.

Example 33

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1, except that heptyl alcohol was used instead of ethyl alcohol.

Example 34

TiO ₂ -coated composite powder was prepared in the same manner as in Example 1, except that octyl alcohol was used instead of ethyl alcohol.

Example 35

A composite powder was prepared in the same manner as in Example 3, except that cyclic dimethyl silicone fluid was used instead of dimethylpolysiloxane.

Example 36

A composite powder was prepared in the same manner as in Example 3, except that methyl hydrogen silicone was used instead of dimethylpolysiloxane.

Example 37

A composite powder was prepared in the same manner as in Example 3, except that methylphenyl siliconefluid was used instead of dimethylpolysiloxane.

Example 38

A composite powder was prepared in the same manner as in Example 3 except for using betaine modified silicone instead of dimethylpolysiloxane.

Example 39

A composite powder was prepared in the same manner as in Example 3, except that amino modified silicone was used instead of dimethylpolysiloxane.

Example 40

A composite powder was prepared in the same manner as in Example 3 except for using fluorine modified silicone instead of dimethylpolysiloxane.

Example 41

Except for using aluminum chloride instead of aluminum sulfate, TiO ₂ , aluminum stearate-coated composite powder was prepared in the same manner as in Example 4.

Example 42

A composite powder was prepared in the same manner as in Example 5, except that TiO ₂ powder was used instead of the ZnO powder.

Example 43

A composite powder was prepared in the same manner as in Example 5, except that the CeO ₂ powder was used instead of the ZnO powder.

Example 44

A composite powder was prepared in the same manner as in Example 5, except that ZrO ₂ powder was used instead of the ZnO powder.

Example 45

Instead of porous spherical silica, porous organic resin was prepared in the same manner as in Example 6 to prepare a composite powder coated with TiO _2.

Example 45

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1 except that the molar ratio of alcohol and titanium alkoxide was 200.

Example 46

A composite powder coated with TiO ₂ was prepared in the same manner as in Example 1 except that the molar ratio of alcohol and titanium alkoxide was 300.

The composite powder prepared according to the present invention is finely coated or impregnated with TiO ₂ on the outside of the substrate to have a better feeling than the conventional UV blocking composite powder and exhibit a higher UV blocking effect with a smaller amount of TiO ₂ . Composite powder can be prepared. In addition, when powders having different UV blocking effects are mixed, composite powders having much higher UV blocking effects can be prepared than when using powders having a single UV blocking effect due to synergy between two materials.

Claims (15)

Method for producing a composite powder, the method (1) activating an inorganic powder or organic resin inside / outside with an acid to generate maximum OH group; (2) Coating TiO ₂ finely and uniformly by increasing the molar ratio of water / titanium alkoxide and alcohol / titanium alkoxide to hydrolysis rate of titanium alkoxide to inorganic powder or organic resin activated inside / outside and proceeding the hydrolysis rate as slowly as possible. Making; And (3) filtration, washing, drying and surface modification of the slurry, Here, the inorganic powder is selected from inorganic spherical and inorganic plate-like powders such as silica, silica gel, alumina, mica, mica, talc, the organic resin is selected from nylon, polymethyl methacrylate, polyethylene, polystyrene, and the acid is And inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, and hydrofluoric acid. Method for producing a composite powder, the method (1) activating an inorganic powder or organic resin inside / outside with an acid to generate maximum OH group; (2) When hydrolysis of titanium alkoxide to inorganic powder or organic resin activated inside / outside, increase the molar ratio of water / titanium alkoxide and alcohol / titanium alkoxide to proceed the hydrolysis rate as slowly as possible to finely coat TiO ₂ Making; (3) filtering, washing, and drying the slurry; (4) TiO ₂ -coated composite powder is added to C ₈ ~ C ₂₂ fatty acid soap, and then aluminum sulfate or aluminum chloride is added to the fatty acid soap, and the fatty acid aluminum is finely coated on the surface of the composite powder. , by treating the surface of the composite powder with silicone oil at pH 6 ~ 9 to control the photocatalytic properties of TiO ₂ , Here, the inorganic powder is selected from inorganic spherical and inorganic plate-like powders such as silica, silica gel, alumina, mica, mica, talc, the organic resin is selected from nylon, polymethyl methacrylate, polyethylene, polystyrene, and the acid is And inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, and hydrofluoric acid. In the manufacturing method of the composite powder, the manufacturing method (1) activating an inorganic powder or organic resin inside / outside with an acid to generate maximum OH group; (2) coating the TiO ₂ finely and uniformly by increasing the molar ratio of water / titanium alkoxide and alcohol / titanium alkoxide to the hydrolysis rate of titanium / alkoxide to the inorganic powder or organic resin which activates the inside / outside to make the hydrolysis rate as slow as possible. ; (3) filtering, washing and drying the slurry; (4) TiO ₂ -coated composite powder is added to C ₈ ~ C ₂₂ fatty acid soap, and then aluminum sulfate or aluminum chloride is added to the fatty acid soap, and the fatty acid aluminum is finely coated on the surface of the composite powder. controlling the photocatalytic properties of TiO ₂ by treating the surface of the composite powder with silicone oil at a pH of 6 to 9; And (5) consisting of a step of exhibiting a synergistic effect of ultraviolet rays by mixing an organic or inorganic substance having an ultraviolet ray blocking effect to the composite powder coated with TiO ₂ , Here, the inorganic powder is selected from inorganic spherical and inorganic plate-like powders such as silica, silica gel, alumina, mica, mica, talc, the organic resin is selected from nylon, polymethyl methacrylate, polyethylene, polystyrene, and the acid is And inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, and hydrofluoric acid. In the manufacturing method of the composite powder, the manufacturing method (1) activating an inorganic powder or organic resin inside / outside with an acid to generate maximum OH group; (2) When hydrolysis of titanium alkoxide to inorganic powder or organic resin activated inside / outside, the molar ratio of water / titanium alkoxide and alcohol / titanium alkoxide is increased to make hydrolysis rate as slow as possible to coat TiO ₂ uniformly. step; (3) filtering, washing and drying the slurry; And (4) consists of a step of firing at 200 ~ 1000 ℃, Here, the inorganic powder is selected from inorganic spherical and inorganic plate-like powders such as silica, silica gel, alumina, mica, mica, talc, the organic resin is selected from nylon, polymethyl methacrylate, polyethylene, polystyrene, and the acid is And inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, and hydrofluoric acid. The molar ratio of water / titanium alkoxide is 10 to 500, and the molar ratio of alcohol / titanium alkoxide is 150 according to any one of claims 1 to 4, in which the titanium alkoxide is supported in the porous inorganic powder or the porous organic resin in two steps. A method for producing a composite powder in which 1-30% by weight of TiO ₂ is uniformly supported inside the powder by hydrolysis at ˜300. The first to the method according to any one of claims 4, carrying a titanium alkoxide in a porous inorganic powder, or a porous organic resin in step 2, the molar ratio of water / titanium alkoxide is from 10 to 500, 1 to 30% by weight of TiO ₂ Method for producing a composite powder to support finely uniformly in the powder. delete The preparation of the composite powder according to any one of claims 1 to 4, wherein the titanium alkoxide is selected from titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide and titanium 2-ethylhexoxide. Way. delete delete The method of claim 3, wherein the material having a sunscreen effect is selected from parsol MCX, CeO ₂ , ZnO, and ZrO ₂ . The method for producing a composite powder according to any one of claims 1 to 4, wherein the content of TiO ₂ in two steps is 1 to 30% by weight. The method for producing a composite powder according to any one of claims 1 to 4, wherein the molar ratio of water and titanium alkoxide is 10 to 500. The method for producing a composite powder according to any one of claims 1 to 3, wherein the molar ratio of alcohol and titanium alkoxide is 150 to 300. The complex according to claim 2 or 3, wherein the silicone oil is selected from dimethylpolysiloxanes, methylhydrogen silicones, cyclic dimethyl silicone fluids, methylphenyl silicone fluids, betaine modified silicones, amino modified silicones, florin modified silicones. Method for producing powder.