JP7301431B1 - Method for producing functional ingredient emitter particles - Google Patents

Abstract

【Theme】
An object of the present invention is to provide functional ingredient-releasing particles capable of controlling the release amount of functional ingredients such as antioxidants, and filters and fibers to which the particles are adhered.
[Solution]
The functional ingredient-releasing particle of the present invention is a network structure impregnated with a functional ingredient,
The network structure consists of porous spheres composed of aggregates of _WO3 needle-like crystals,
The release amount of the functional ingredient is controlled by controlling the density of the _WO3 needle crystals.
Further, the filter of the present invention is characterized by adhering the functional ingredient-releasing particles.
Further, the fiber of the present invention is characterized by kneading the functional ingredient-releasing particles.
[Selection drawing] Fig. 3

Description

The present invention relates to functional ingredient-releasing particles in which a functional ingredient is impregnated in a network structure made of _WO3 , and the release amount of the functional ingredient to be released is controlled by controlling the density of the _WO3 needle crystals. The present invention relates to a method for producing controllable functional ingredient release particles .
In this specification, tungsten trioxide and tungsten oxide are expressed as " _WO3 ".

Conventionally, methods such as deodorization and sterilization have been proposed by releasing functional ingredients such as vitamins and fragrances into the vehicle using devices such as vehicle air filters.
Proposals have also been made to suppress various oxidizing substances generated in the living environment by releasing functional ingredients indoors from air conditioners, air purifiers, and the like.
When functional ingredients with antioxidant functions are released into the air, chemical reactions reduce oxidizing substances from the room.In addition, if the functional ingredients have moisturizing properties, the released ingredients are absorbed by the skin. It is expected to exhibit a moisturizing effect and improve rough skin.
Examples of functional ingredients having such an antioxidant function include L-ascorbic acid (vitamin C) and its derivatives, which are used in pharmaceuticals, health supplements, cosmetics, clothing, etc. It is also used for wearing clothes.
As a technique using functional ingredients, for example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2004-51521) discloses that the substance contained is one or more selected from collagen derivatives and vitamins, A rayon nonwoven fabric is described which is blended with agent-containing silk.
In addition, Patent Document 2 (Japanese Unexamined Patent Application Publication No. 2006-45491) describes that when a sheet member carrying an active ingredient is employed as an air filter, the active ingredient contained in the air filter is released. there is

However, in Patent Document 2, there is a description that two or more materials are mixed to maintain performance over a long period of time. There is a problem that the
In addition, an air filter is considered suitable for continuous contact between an antioxidant substance and an oxidizing substance in the air. are easily oxidized and degraded, and are oxidized in a short period of time by being released into the air. Therefore, the conventional technology is not suitable for long-term use.

JP-A-2004-51521 JP 2006-45491 A

Accordingly, an object of the present invention is to provide a method for producing functional ingredient-releasing particles capable of controlling the release amount of a functional ingredient consisting of ascorbic acid .

The present invention has the following features.
(1) The present invention is
In a method for producing functional ingredient-releasing particles impregnated with a functional ingredient,
Using tungsten hydroxide as a starting material,
Using an autoclave device,
Hydrothermal reaction with controlled pressure, temperature and time
producing a network of porous spheres _of WO3 needles,
In this network structure,
A functional ingredient consisting of ascorbic acid,
an inorganic binder;
mixed with water to form a slurry liquid,
A method for producing functional ingredient-releasing particles in which this slurry liquid is granulated using a spray dryer,
In the autoclave device,
Adjusting the density of aggregates of WO3 needle crystals _generated by changing the concentration of the tungsten hydroxide ,
The concentration of aggregates of WO3 needle crystals _mixed in the slurry liquid is
It is characterized by being 17.5% to 27.5%.

The functional ingredient-releasing particles of the present invention have a network structure impregnated with a functional ingredient, and the network structure comprises porous spheres composed of aggregates of _WO3 needle crystals. , by controlling the density of the _WO3 needle crystals, the release amount of the functional ingredient is controlled,
The release amount and release period of the functional ingredient can be controlled, and the effect of the functional ingredient release is sustained over a long period of time.
In addition, air filters and fibers to which the emitting particles are adhered maintain functionality such as antioxidant performance for a long period of time.

FIG. 1 shows the oxidation produced in the autoclave process when the concentration of tungsten hydroxide, which is the starting material, is varied, with the horizontal axis being the tungsten hydroxide concentration (%) and the vertical axis being the _WO3 crystallization rate (%). 4 is a graph showing percentages (%) of tungsten network structures. FIG. 2 is a schematic diagram of a spray dryer processing apparatus for producing functional ingredient ejector particles. FIG. 3 shows a particle micrograph of the functional ingredient emitter particles of the embodiment of the present invention. (a) is a 20,000-fold photograph of the emitter particles produced by adjusting the concentration of _WO3 mixed in the slurry to 12.5% and using a spray dryer. (b) is a photograph of the emitter particles of (a). , Photo (c) with a magnification of 45000 times is the _WO3 concentration mixed in the slurry adjusted to 17.5% and made into particles with a spray dryer. A photograph (e) of the particles at a magnification of 45,000 times is a photograph (f) of particles made into particles with a spray dryer by adjusting the concentration of _WO3 mixed in the slurry to 22.5% . ) is magnified 45,000 times (g) is a photograph (h) of 20,000 times the WO ₃ concentration mixed in the slurry is adjusted to 27.5% and made into particles with a spray dryer. , (g) at 45,000 times magnification. FIG. 4 shows the relationship between the production density (porosity) of needle-like crystals in the functional ingredient-ejecting particles formed by spray dryer processing when the blending ratio of the _WO3 network structure mixed in the slurry liquid is changed. It is a graph showing the relationship. FIG. 5 is a graph showing the relationship between tungsten oxide (WO ₃ ) crystal density and vitamin C (ascorbic acid) release performance. FIG. 6 is a schematic explanatory view showing a process of producing a filter after the functional ingredient-releasing particles are supported on a nonwoven fabric by dipping. FIG. 7 is a graph comparing and evaluating the sustained performance of the vitamin (functional ingredient) release amount of non-woven fabric filters obtained by changing the concentration of tungsten oxide. FIG. 8 is an explanatory diagram of a vitamin (functional ingredient) release performance evaluation device. FIG. 9 shows the results of the release performance evaluation performed using the release performance evaluation device. FIG. 10 is an explanatory diagram of a net filter manufactured using fibers kneaded with the functional ingredient-releasing particles of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.
<Functional ingredient emitter particles>
The functional ingredient-releasing particle of the present invention is a network structure impregnated with a functional ingredient,
The network structure consists of porous spheres composed of aggregates of _WO3 needle-like crystals,
By controlling the density of the _WO3 needle crystals,
It is characterized by controlling the release amount of the functional ingredient.
An opening communicating with the impregnated functional ingredient is formed on the surface of the functional ingredient-releasing particles, and the functional ingredient is released to the outside through the opening.

<Mesh structure>
The network consists of porous spheres composed of aggregates of _WO3 needle-like crystals.
Such a network of WO ₃ needle crystals can be produced by a hydrothermal reaction of tungsten hydroxide in an autoclave apparatus, as shown below.
For example, when hydrothermal synthesis is performed in an autoclave apparatus having a high temperature and high pressure (for example, around 200° C. and a vapor pressure of about 15 to 18 kg/cm ² ), needle-like crystals of WO ₃ are produced from tungsten hydroxide, which is the starting raw material. be.
( _H2WO4 +heat _{→ H2O} + _WO3 )
WO ₃ is a needle-like crystal called tungsten trioxide (or tungsten oxide), which is representative of tungsten oxide.
Water is added to the tungsten hydroxide raw material to adjust the liquid mixture so that the Blaine value has a liquid viscosity in the range of 3000 cm ² /g to 15000 cm ² /g,
As an example, it is preferable to prepare a mixed solution in which water is mixed and dispersed so as to have a concentration of 5 to 20%, preferably 10 to 15% by mass.
This mixed solution is charged into an autoclave apparatus, and hydrothermally synthesized with stirring at a temperature of, for example, 150 to 210° C. for 10 to 12 hours to produce WO ₃ having an average particle size of 5 nm to 30 nm.
Amorphous silica having a Blaine value of 3000 cm ² /g or more (for example, diatomaceous earth, silica fume, microsilica, etc.) can be added to the mixed liquid for viscosity adjustment.

<Tungsten hydroxide concentration and _WO3 crystallinity>
Adjust the density of aggregates of _WO3 needle crystals (proportion of production = _WO3 crystallization rate) by changing the blending ratio of tungsten hydroxide, which is the starting material, in the mixed solution fed into the autoclave device. be able to.
In FIG. 1, the horizontal axis is tungsten hydroxide concentration (%) and the vertical axis is _WO3 crystallization rate (%).
1 is a graph showing the proportion (%) of a tungsten oxide network formed in autoclave processing when the concentration of tungsten hydroxide, which is the starting material, is varied.
As shown in Fig. 1, the density of aggregates of _WO3 needle-like crystals produced in autoclave processing indicates that the higher the tungsten hydroxide concentration (%) in the autoclave, the higher the _WO3 crystallinity (%). I understand.

<Functional ingredients>
Examples of functional ingredients that impregnate the network structure include vitamins, collagen, astaxanthin, hyaluronic acids, fragrances, catechins, tannins, natural moisturizing factors, plant-derived oils, and the like. Combinations of these can be used.
Depending on the purpose of use, the functional component to be impregnated is appropriately determined.
Examples of vitamins include vitamins, vitamin derivatives, and vitamin-like substances that act like vitamins.
Vitamins include ascorbic acid, retinol, dl-tocopherol, pantothenic acid, nicotinamide, biotin, phytonadione, folic acid.
Vitamin derivatives include ethyl ascorbyl, ascorbyl glucoside, sodium (ascorbyl/cholesteryl) phosphate, potassium (ascorbyl/tocopheryl) phosphate, ascorbyl methylsilanol pectin, ascorbyl phosphate (Mg/K), ascorbyl phosphate (Mg/Na ), ascorbyl phosphate (Mg/zinc), Ca ascorbyl phosphate, Na ascorbyl phosphate, and other ascorbic acid derivatives are preferably applied.

<Functional ingredient emitter particles>
The functional ingredient emitter particles of the embodiment are impregnated with a functional ingredient in a network structure consisting of porous spheres composed of aggregates of _WO3 needle crystals,
By controlling the density of the _WO3 needle crystals, the release amount of the functional ingredient can be controlled.
In addition, an opening communicating with the impregnated functional ingredient is formed on the surface of the functional ingredient-releasing particles, and the functional ingredient is released to the outside from the opening.

<Spray dryer processing>
Such functional ingredient release particles are produced, for example, by granulating a slurry liquid prepared as described below using a spray dryer processing apparatus as described below.

<Slurry liquid>
A slurry liquid consisting of the following formulation and water is introduced into the spray dryer apparatus.
(a) autoclaved _WO3 network (b) functional ingredients such as vitamins impregnated into the network (c) inorganic binder (e.g. colloidal silica)
An inorganic binder is mixed to immobilize the functional ingredient ejector particles formed in the spray dryer.
Examples of inorganic binders include silicate-based colloidal silica, calcium silicate, ethyl silicate, sodium silicate (water glass), potassium silicate, lithium silicate, alumina-based calcium aluminate, β-alumina, Inorganic materials such as boehmite, alumina sol, and phosphoric acid-based calcium phosphate, aluminum phosphate, and magnesium phosphate can be used.
Among them, colloidal silica and sodium silicate (water glass) are commercially available in the form of aqueous suspensions and are readily available, so they are preferably used.
As the _WO3 network structure, particles having a diameter of 100 μm or less,
As the inorganic binder, particles having a diameter of 500 nm or less,
The total solid content of the slurry liquid is preferably 5 to 20 parts by mass per 100 parts by mass to which the solvent (water, etc.) is added, from the viewpoint of manufacturing handling.
However, the concentration of the slurry liquid is not particularly specified,
It is appropriately determined in consideration of manufacturing conditions such as spraying and drying conditions in a spray dryer processing device.
The solvent of the slurry liquid contains water as the main solvent, but may contain an organic solvent such as alcohol in order to ensure dispersion stability.
In addition, the inorganic binder can also be put into an autoclave device.

<Spray dryer processing equipment>
FIG. 2 is a schematic diagram of a spray dryer processing apparatus for producing functional ingredient ejector particles.
As shown in FIG. 2, the spray dryer processing apparatus has a slurry liquid tank 21, an atomizing air blower 22, a nozzle 23, a drying chamber 24, an air heater 26, a cyclone 27, a bag filter 28, and an exhaust fan 29.
In the spray dryer processing device, the slurry liquid supplied from the slurry liquid tank 21 collides with the ejected air supplied from the atomization air blower 22 at the nozzle 23 to spray fine droplets. .

The drying chamber 24 is a hollow cylindrical dryer.
A nozzle 23 is arranged at the upper portion, and an air blowing port through which air is introduced from the atomization air blowing device 22 is open.
An air heater 26 capable of heating the air introduced into the drying chamber 24 to a predetermined temperature is provided between the air blower 22 and the air outlet. The slurry liquid is sprayed with air from the atomizing air blower 22 and atomized in the drying chamber 24 .

The outlet of drying chamber 24 is connected to cyclone 27 .
The outlet of cyclone 27 is connected to bag filter 28 .
An exhaust fan 29 is connected to the bag filter 28 .
Below the cyclone 27 and the bag filter 28, boxes (Product 1, Product 2) for collecting the granulated functional ingredient emitter particles are provided.

Air blown from the atomizing air blower 22 is heated by the heater 26 and introduced into the drying chamber 24 .
In the drying chamber 24, the atomized slurry droplets are brought into contact with heated air (for example, 100° C. or higher and 300° C. or lower) heated by the air heater 26, and the slurry droplets are dried to form functional ingredient ejector particles. is manufactured.

<Functional ingredient emitter particles>
FIG. 3 shows a micrograph of the functional ingredient emitter particles of the embodiment of the present invention.
(a) is a 20,000-fold photograph of the emitter particles produced by adjusting the concentration of _WO3 mixed in the slurry to 12.5% and using a spray dryer. (b) is a photograph of the emitter particles of (a). , Photo (c) with a magnification of 45000 times is the _WO3 concentration mixed in the slurry adjusted to 17.5% and made into particles with a spray dryer. A photograph (e) of the particles at a magnification of 45,000 times is a photograph (f) of particles made into particles with a spray dryer by adjusting the concentration of _WO3 mixed in the slurry to 22.5% . ) is magnified 45,000 times (g) is a photograph (h) of 20,000 times the WO ₃ concentration mixed in the slurry is adjusted to 27.5% and made into particles with a spray dryer. , (g) at 45,000 times magnification.
As can be seen from the micrograph of FIG. 3, needle _- like crystals of WO3 are exposed on the surface of the ejector particles produced by the spray dryer process, and from the exposed needle-like crystals of _WO3 , It can be seen that the functional ingredient impregnated inside can be released to the outside air.
In terms of handling, it is desirable that the ejected particles after spray drying have a bulk specific gravity of 0.5 to 1.5 and an average diameter of 0.5 to 10 μm.

<Relationship between _WO3 concentration in slurry and production density of needle crystals>
FIG. 4 is a graph showing the relationship between the production density of needle-like crystals in the functional ingredient-emitting particles formed by spray dryer processing when the blending ratio of the _WO3 network structure mixed in the slurry liquid is changed. is.
It can be seen that the higher the blending ratio of the _WO3 network structure, the higher the production density of needle-like crystals in the functional ingredient-releasing particles formed by the spray dryer process.

The release amount of the functional ingredient-releasing particles can also be controlled by changing the mixing ratio of the inorganic binder in the slurry liquid.
In other words, the release amount of the functional ingredient release particles can be controlled not only by the density of the _WO3 generated in the autoclave device, but also by adjusting the mixing ratio of the inorganic binder in the slurry liquid to be fed into the spray dryer device. can be done.

<Relationship between _WO3 crystal density and ascorbic acid release performance>
FIG. 5 is a graph showing the relationship between tungsten oxide (WO ₃ ) crystal density and vitamin C (ascorbic acid) release performance.
The data shown in Figure 5 show that vitamin C (ascorbic acid) was blended in slurries with different concentrations of _WO3 (12.5%, 17.5%, 22.5%, 27.5%) at the same rate. , Put 10 g each of the functional ingredient-released particles of the same size obtained by spray drying into a beaker containing 90 g of ion-exchanged water, stir with a magnetic stirrer at 500 rpm for 10 minutes, place in a beaker A 10 ml portion was sampled from the sample, added to the DPPH reagent preparation solution, and the degree of color development was measured and compared with a spectrophotometer.
Further, 10 ml of the same beaker was collected every hour until 6 hours had passed, and the sample was added with the DPPH reagent preparation solution and measured with a spectrophotometer.
According to the data shown in FIG. 5, it can be seen that even in the functional ingredient-releasing particles processed by the spray dryer, the lower the blended _WO3 concentration (12.5%), the higher the rate of elution into ion-exchanged water.

<Filter>
Next, the filter of Example 1 using the functional ingredient-releasing particles of the present invention will be described.
FIG. 6 is a schematic explanatory view showing the process of manufacturing a filter after attaching functional ingredient-releasing particles to a non-woven fabric by a dipping process (in this specification, it may be referred to as "carrying").
The functional ingredient-releasing particles carried on the nonwoven fabric are obtained by adding 20 to 30 parts by mass of ascorbic acid to tungsten oxide (solid content: 10 to 20 parts by mass),
5 to 10 parts by mass of colloidal silica with a concentration of 30%,
Furthermore, 60 to 90 parts by mass of water was added to adjust the viscosity of the slurry liquid, which was processed by a spray dryer and manufactured using a nozzle having an average particle size of 1 μm.
10 to 25 parts by mass of the obtained functional ingredient-releasing particles,
10 to 30 parts by mass of acrylic emulsion or urethane emulsion,
A dipping liquid was prepared by mixing 70 to 90 parts by mass of water.
The dipping liquid was placed in a tray or bucket as shown in FIG. 6, and a nonwoven fabric, cotton cloth, or the like was dipped and adhered to the nonwoven fabric.
The dipping process refers to a process in which a substrate such as a nonwoven fabric is immersed in a dipping liquid, and the functional ingredient-releasing particles are adhered to the nonwoven fabric in a uniform and specified amount.
After dipping, it is dried by heating to about 100 to 130° C. and once wound into a roll.
This nonwoven fabric was pleated to form a filter to be mounted on humidifiers, air cleaners, car air conditioners, etc. (see FIG. 6).

<Comparison of sustained performance of vitamin (functional ingredient) release amount>
FIG. 7 is a graph comparing and evaluating the sustained performance of the vitamin (functional ingredient) release amount of non-woven fabric filters obtained by changing the concentration of tungsten oxide.
This comparative evaluation was carried out as follows.
In other words, we made prototype filters for car air conditioners under the following conditions, installed them in car air conditioners, and created an evaluation device so that we could collect all the air containing vitamins emitted from car air conditioners when they were operated under the same conditions. bottom.

FIG. 8 is an explanatory diagram of a release performance evaluation device used for the above performance comparison.
Using this evaluation device, the air released from the car air conditioner was connected to a bubbling container containing 100 g of pure water, sucked by a vacuum pump, and bubbled into the pure water.
The concentration of ascorbic acid dissolved in pure water was quantitatively analyzed with a spectrophotometer as the vitamin release concentration from the numerical method of the amount of reduction of DPPH radicals.
The bubbling test was conducted for 3 hours, and the concentration of dissolved ascorbic acid in the bubbling pure water was calculated assuming that almost 100% of the ascorbic acid was dissolved.
This 3 hour bubbling was performed every 24 hours and repeated for 6 days.
<Conditions for adhesion to nonwoven fabric>
Nonwoven fabric basis weight: 40 g/m ²
Functional ingredient release particle adhesion amount; 10 g/m ²
WO ₃ concentration; 4 types of 12.5%, 17.5%, 22.5%, 27.5% Functional ingredient concentration in WO ₃ ; 30% as ascorbic acid conversion
<Evaluation conditions>
Wind speed; 1.6 m/s, flow rate; 10 L/min

FIG. 9 shows the results of the release performance evaluation performed using the above release performance evaluation device.
From the evaluation data shown in FIG. 9, the vitamin concentration contained in the released air is
The lower the _WO3 concentration, the more
It can be seen that the higher the _WO3 concentration, the longer it lasts.
The concentration of dissolved ascorbic acid in the bubbling pure water was calculated on the assumption that almost 100% of the ascorbic acid was dissolved.
This 3 hour bubbling was performed every 24 hours and repeated for 6 days.

<Fiber, net filter using it>
Next, the fiber of Example 2 using the functional ingredient-releasing particles of the present invention and the net filter using the same will be described.
FIG. 10 is an explanatory diagram of a net filter manufactured using fibers kneaded with the functional ingredient-releasing particles of the present invention.
That is, the functional ingredient-releasing particles kneaded into the fiber are
Tungsten oxide (10 to 20 parts by mass of solids reacted in an autoclave),
10 to 30 parts by mass of ascorbic acid (vitamin C),
Furthermore, the slurry liquid whose viscosity is adjusted by adding 60 to 90 parts by mass of water is processed into particles by a spray dryer using a nozzle having an average particle size of 1 μm.
5 to 10 parts by mass of the obtained functional ingredient-releasing particles are uniformly blended with a resin (for example, PP) powder,
While melting at 150 to 220° C. with a pelletizer, compound pellets of about 1 to 3 mm were obtained.
A PP compound obtained by mixing 10 to 30 parts by mass of a combination of one or more of these is put into a melt extruder (extruder) and melted while being heated by a gear pump (a small extrusion pump with a meter). It was extruded into a fibrous form from a nozzle (orifice) with many holes, wound up, and drawn (stretched in the length direction) to obtain a monofilament fiber kneaded with functional ingredient-releasing particles.
The obtained monofilament fibers kneaded with the functional ingredient-releasing particles are knitted as warp/weft or heat-sealed to form a net-like sheet in the next step.
A sheet of a suitable size was punched out from the sheet, and a frame was attached to the sheet by heat-sealing to form a net filter for air conditioners and air purifiers.
Functional ingredients kneaded into the net filter include L-ascorbic acid, magnesium L-ascorbic acid phosphate, vitamin B1, vitamin B2, niacin, pantothenic acid, vitamin B6, vitamin B12, folic acid, biotin and the like.

The functional ingredient-releasing particle of _the present invention is a network structure impregnated with a functional ingredient, and is composed of porous spheres composed of aggregates of _WO3 needle crystals. By controlling the density, the release amount of the functional ingredient can be controlled, so the release amount and release period of the functional ingredient can be controlled, and the effect of the functional ingredient release can be maintained over a long period of time. .
In addition, air filters and kneaded fibers to which the ejector particles are adhered can maintain functionality such as antioxidant performance for a long period of time, and have high industrial applicability.

21 slurry liquid tank 22 atomization air blower 23 nozzle 24 drying chamber 26 air heater 27 cyclone 28 bag filter 29 exhaust fan

Claims (1)

In a method for producing functional ingredient-releasing particles impregnated with a functional ingredient,
Using tungsten hydroxide as a starting material,
Using an autoclave device,
Hydrothermal reaction with controlled pressure, temperature and time
WO ₃ generating a network structure composed of porous spheres of needle-like crystals,
In this network structure,
A functional ingredient consisting of ascorbic acid,
an inorganic binder;
mixed with water to form a slurry liquid,
A method for producing functional ingredient-releasing particles in which this slurry liquid is granulated using a spray dryer,
In the autoclave device,
WO generated by changing the concentration of the tungsten hydroxide ₃ Adjusting the density of aggregates of needle-like crystals,
WO to be mixed with the slurry liquid ₃ The concentration of aggregates of needle-like crystals is
17.5% to 27.5%. A method for producing functional ingredient releasing particles.

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