WO2017221996A1

WO2017221996A1 - Carrier body, attached sheet member, air filter, carrier body production method, and attached sheet member production method

Info

Publication number: WO2017221996A1
Application number: PCT/JP2017/022930
Authority: WO
Inventors: 充哲渡辺
Original assignee: 倉敷繊維加工株式会社
Priority date: 2016-06-24
Filing date: 2017-06-21
Publication date: 2017-12-28
Also published as: CN109312209A; CN109312209B; JPWO2017221996A1; JP6289781B1

Abstract

The purpose of the present invention is to provide: a carrier body that is able to release a functional substance over a prolonged period of time; an attached sheet member attached with said carrier body; and an air filter using said attached sheet member. This carrier body comprises a core body containing a functional substance and a coating layer that covers the surface of the core body, the carrier body being characterized in that: the coating layer comprises a vitrified inorganic binder and an inorganic aggregate dispersed within the inorganic binder; the surface of the coating layer is provided with microcracks that are formed therein so as to have openings connecting to the functional substance constituting the core body so that the functional substance is released to the outside through the microcracks.

Description

Carrier, attachment sheet member, air filter, carrier manufacturing method, and attachment sheet member manufacturing method

The present invention relates to a carrier comprising a core made of a functional substance and a coating layer covering the surface of the core, an attachment sheet member to which the carrier is attached, an air filter using the carrier, a method for producing the carrier, and attachment The present invention relates to a method for manufacturing a sheet member.

Conventionally, for the purpose of keeping freshness, which suppresses oxidative deterioration that lowers the freshness of fresh food products such as vegetables, fruits, fish, meat, etc., a method of restraining by incorporating an antioxidant functional substance in a refrigerator storage etc. or using equipment Etc. have been proposed. Proposals have also been made to suppress various oxidizing substances generated in living environments by applying suppression methods using these materials and equipment to air conditioners and air purifiers. In addition, when a functional substance having an antioxidant function is diffused into the air, the oxidized substance is reduced from the room by a chemical reaction. In addition, if the functional substance has a moisturizing function, the diffused component is the skin. It is absorbed from the skin, exerts a moisturizing effect, and can be expected to improve rough skin.
Examples of such a functional substance having an antioxidant function include L-ascorbic acid (vitamin C) and its derivatives. For the purpose of preventing rough skin and health management, health supplements such as pharmaceuticals, cosmetics, clothing It is directly absorbed and used by ingesting these substances and wearing clothing.
As a technique using a functional substance, for example, in Patent Document 1 (Japanese Patent Laid-Open No. 2004-51521), the substance contained is one or more selected from collagen derivatives and vitamins, and thickening is performed. A rayon nonwoven fabric mixed with silk containing an agent is described.
Patent Document 2 (Japanese Patent Laid-Open 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 diffused. Yes.

However, in the fields of pharmaceuticals and cosmetics, when an antioxidant such as vitamin C is used alone, its effect is poor and only one effect can be expected. In addition, when taking directly, there is a problem that it must be taken consciously, and if it is forgotten, it cannot be taken continuously. In order to keep the antioxidant substance and the oxidizing substance in the air in contact with each other, the air filter is considered suitable. However, when the antioxidant substance is singly attached to the air filter, for example, vitamin C or the like. Is prone to oxidative degradation and is oxidized in a short period of time by being diffused into the air. Therefore, the conventional technology is not suitable for long-term use.
In Patent Document 2, there is a description that two or more kinds of materials are mixed for maintaining performance over a long period of time. However, the amount of the functional substance to be diffused cannot be controlled, and the amount added is long for extending the life. There is a problem of becoming.
Moreover, it is described that antioxidant substances, such as vitamin C, change the amount of diffusion with the humidity in the air. Although dispersibility at low humidity can be maintained by providing a humidifying means, it is necessary to install a humidifier.
Furthermore, in the cabin air filter, a reduction in safety due to fogging of the window due to excessive humidification is not allowed, and humidification control becomes complicated.

JP 2004-51521 A JP 2006-45491 A

Accordingly, an object of the present invention is to provide a carrier that can easily disperse a functional substance such as an antioxidant over a long period of time without using a humidifier or other humidification technique.
Another object of the present invention is to provide an attachment sheet member to which the carrier is attached and an air filter using the attachment sheet member.
Furthermore, the other object of this invention is to provide the manufacturing method of the said support body, and the manufacturing method of an attachment sheet | seat member.

(1) The carrier of the present invention is a carrier comprising a nucleus composed of a functional substance and a coating layer covering the surface of the nucleus, the coating layer comprising a vitrified inorganic binder and its coating It consists of an inorganic aggregate dispersed in an inorganic binder, and on the surface of the coating layer, a microcrack having an opening communicating with the functional substance serving as the core is formed,
The functional substance is diffused to the outside from the microcracks.
(2) In the carrier of the present invention, in (1) above, the inorganic aggregate dispersed in the coating layer is silica or alumina particles having a particle size of 0.1 to 1.0 μm,
The inorganic binder is characterized by comprising one kind of colloidal silica, colloidal tungsten lithium silicate, potassium silicate, or sodium silicate, or a combination thereof.
(3) The attachment sheet member of the present invention is characterized in that the carrier of the above (1) or (2) is attached.
(4) The air filter of the vehicle air conditioner of the present invention is characterized in that the attachment sheet member of (3) is used.
(5) The method for producing a carrier according to the present invention comprises a nucleus composed of a functional substance and a coating layer covering the surface of the nucleus, the coating layer comprising a vitrified inorganic binder and its inorganic bond And the coating layer surface is formed with microcracks communicating with the functional substance serving as the core, and the functional substance is diffused to the outside from the microcracks. A method for producing a carrier, wherein the core, the inorganic binder, and the inorganic aggregate are mixed to produce a slurry, and the slurry is sprayed by a spray dryer processing method to form the surface of the core And coating the inorganic binder and the inorganic aggregate to produce a precursor carrier, placing the precursor carrier in a furnace in an inert gas or hydrogen atmosphere, and firing the precursor carrier. Before The inorganic binder as well as vitrification, and having a step of forming microcracks in the coating layer is cooled.
(6) The method for producing an attachment sheet member of the present invention includes a step of mixing the carrier produced in (5) above with an attaching resin to produce a chemical solution, and a step of attaching the chemical solution to the surface of the substrate. And a step of drying the base material to which the chemical solution is adhered and attaching the carrier to the base material.

The carrier of the present invention comprises a nucleus composed of a functional substance and a coating layer covering the surface of the nucleus, and the coating layer is composed of a vitrified inorganic binder and an inorganic material dispersed in the inorganic binder. A microcrack is formed on the surface of the coating layer and communicates with the functional substance serving as the core, so that the functional substance is dissipated to the outside from the microcrack. Therefore, by adjusting the number and size (opening ratio) of the microcracks formed in the coating layer, the amount and duration of the functional substance can be controlled, and the functional substance can be released over a long period of time. The effect is sustained.
In addition, the attachment sheet member and the air filter to which the carrier is attached can maintain the functionality such as the antioxidant performance over a long period of time, and can extend the replacement interval of the air filter.

It is a schematic diagram explaining the attachment sheet | seat member of this invention. It is a specific photograph explaining (a) an attachment sheet member and (b) a substrate of the present invention. It is a figure which shows the spray dryer processing apparatus which is an example of the apparatus for manufacturing the support body which concerns on this invention. It is a photograph explaining the state of the surface of the carrier according to the present invention. It is a figure explaining the apparatus of a dipping method in adhesion to the base material of the attachment chemical | medical solution which concerns on this invention. It is a photograph explaining the example of the air filter using the attachment sheet | seat member of this invention. It is a figure explaining the radiation performance evaluation apparatus in the Example of this invention. It is a figure which shows the evaluation result of the antioxidant performance of the air filter in the Example of this invention. It is a figure explaining the vehicle air conditioner which attached the air filter which concerns on this invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The same symbol is attached to the same member and the same part.
Below, the form of the support body which concerns on this invention, and its manufacturing method are demonstrated. In addition, this invention is not limited to embodiment shown below.

<Supporter>
The carrier comprises a core made of a functional substance and a coating layer covering the surface of the core, the coating layer comprising an inorganic binder that has been vitrified after melting and an inorganic bone dispersed in the inorganic binder. It consists of materials. On the surface of the coating layer, a microcrack having an opening communicating with a functional substance serving as a nucleus is formed, and the functional substance is diffused to the outside from the microcrack.

<Functional substance that is the core of the carrier>
Examples of the functional substance include vitamins, catechins, tannins, natural moisturizing component factors, plant-derived oil or hyaluronic acids, and these can be used alone or in combination. The functional substance to be used is appropriately determined depending on the purpose of use of the sheet member.
Vitamins include vitamins, vitamin derivatives, and vitamin-like substances that work like vitamins.
Examples of vitamins include L-ascorbic acid, retinol, dl-tocopherol, pantothenic acid, nicotinic acid amide, biotin, phytonadione, and folic acid.
As vitamin derivatives, ascorbyl ethyl, ascorbyl glucoside, (ascorbyl / cholesteryl) sodium phosphate, (ascorbyl / tocopheryl) potassium phosphate, ascorbyl methylsilanol pectin, ascorbyl phosphate (Mg / K), ascorbyl phosphate (Mg) Ascorbic acid derivatives such as / Na), ascorbyl phosphate (Mg / zinc), ascorbyl phosphate Ca, and ascorbyl phosphate Na are preferably used.
As other volatile antioxidants, in addition to the above, ascorbyl phosphate Mg, ascorbyl phosphate 3Na, ascorbyl aminopropyl phosphate, calcium ascorbate, Mg ascorbate, tetrahexyldecyl ascorbate, ascorbic acid polypeptide, sulfuric acid ascorbate 2Na, ascorbyl stearate, L-ascorbyl tetra-2-hexyldecanoate, chitosan ascorbic acid, panthenyl ethyl, pantothenic acid MEA, pantothenic acid polypeptide, ethyl dicarboethoxy pantothenate, tocopherol phosphate 2Na, pyridoxine dicaprylate, phosphorus Pyridoxal acid, hexyl nicotinate, tocopherol nicotinate, benzyl nicotinate, methyl nicotinate and the like can also be used.

Catechins include tea-derived catechins. The main components of tea-derived catechin are epigallocatechin, epigallocatechin gallate, epicatechin, epicatechin gallate and the like.

As the tannins, commercially available refined tannic acid, extracts of tannic acid-containing natural plants such as pentaploids and gallic pods, or semi-purified products thereof can be used as they are. Pyrogallol, gallic acid, and gallic acid esters can also be used. As the tannins, purified tannic acid is particularly preferable because it does not contain impurities. The average particle size of the functional substance serving as the nucleus is related to the target release time, but is preferably 1 to 20 μm in terms of production.

<Coating layer>
The coating layer covering the core includes an inorganic binder and an inorganic aggregate, and has microcracks on the surface thereof. The coating layer is made of an inorganic material that does not disappear by firing in an inert gas atmosphere such as hydrogen or nitrogen.

<Microcrack>
The coating layer is formed with open microcracks, and the microcracks communicate with a functional substance serving as a nucleus.

<Inorganic aggregate>
In the coating layer, an inorganic aggregate serving as a starting point of occurrence of microcracks is dispersed.
Examples of the inorganic aggregate include ceramic particles such as silica and alumina having a melting point higher than that of the inorganic binder described later. This is because even if the inorganic binder is baked at 800 ° C., the inorganic aggregate does not melt, but serves as a starting point when microcracks are formed during cooling.
From this viewpoint, the average particle diameter (diameter) of the inorganic aggregate is preferably 0.1 to 1.0 μm. If it is smaller than 0.1 μm, the starting point of the microcrack is not generated and the amount of the functional substance diffused is small, and if it exceeds 1.0 μm, the gap of the microcrack becomes large and the amount of the functional substance diffused becomes too large.

<Inorganic binder>
As the inorganic binder constituting the coating layer, for example, silica colloidal silica, calcium silicate, ethyl silicate, sodium silicate (water glass), potassium silicate, lithium silicate, alumina calcium aluminate , Β-alumina, boehmite, alumina sol, phosphoric acid based calcium phosphate, aluminum phosphate and magnesium phosphate.
The inorganic binder is mixed with the inorganic aggregate and coated on the surface of the functional substance. By making the inorganic binder material close to the above-mentioned inorganic aggregate, a coating layer is formed on the surface of the carrier. It can be formed uniformly. In addition, in the firing step described later, when the microcracks are formed in the coating layer, it can be bonded to the surface of the inorganic aggregate, and the peeling off of the inorganic aggregate from the coating layer can be suppressed. Among these, colloidal silica and sodium silicate (water glass) are commercially available as aqueous suspensions and are easily used, and thus are preferably used.

<Particle size of carrier>
The size (average particle diameter) of the support is preferably 1 μm to 20 μm. If the average particle size of the carrier is smaller than 1 μm, the carrier is buried in the resin to be attached when the carrier is attached to the base material of the sheet, and the diffusion of the functional substance into the air is greatly reduced. Because it ends up. On the other hand, when the average particle diameter exceeds 20 μm, the carrier is settled and separated in the liquid holding tank or the impregnating pad when the adhering chemical mixed with the carrier is processed into the base material, so that the amount of chemical addition is stable. Because it will not.

<Attached sheet member>
FIG. 1 shows a schematic explanatory diagram in which the attachment sheet member 10 according to the embodiment of the present invention is enlarged.
As shown in FIG. 1, the attachment sheet member 10 is a member in which a carrier 13 is attached to a base material 11 via an attachment resin 12.
In the present invention, the attachment sheet member (FIG. 1 (10)) refers to a thin and large-area member in which a carrier is attached on a substrate (FIG. 1 (11)). What was wound up in roll shape may be sufficient, and the planar shape cut | disconnected by the predetermined dimension may be sufficient, and the form is not limited.
The manufacturing method will be described later.

FIG. 2A is a specific photograph of the attachment sheet member (FIG. 1 (10)), and FIG. 2 (b) is a specific image of the base material (FIG. 1 (11)) constituting the base. It is a photograph.

<Base material>
The base material 11 is a sheet-like material made of natural fibers such as pulp and cotton; synthetic fibers such as polypropylene, polyethylene, polyester, nylon, rayon, and polyvinyl alcohol. Can be used as a mixture.
In addition, the type of sheet is not limited, but non-woven fabrics are good because of air permeability, shape retention, ease of procurement, etc., and can be selected according to applications such as spunbond, meltblown, short fiber nonwoven fabric, wet nonwoven fabric, etc. it can.

<Air filter>
Next, an air filter capable of gradually diffusing a functional substance into the air using the attachment sheet member of the embodiment will be described. In producing the air filter, the attachment sheet member is appropriately cut and processed into a flat plate shape or a pleated shape, and a frame is additionally processed as necessary to form an air filter (unit) (see FIG. 6 described later).

Next, a method for manufacturing the carrier according to the present invention will be described. The manufacturing method generally includes the following steps.

<Preparation of slurry liquid>
First, a functional substance, an inorganic binder, and an inorganic aggregate are mixed at a predetermined mass ratio, and a solvent is added to the mixture. The concentration of the slurry liquid is not particularly defined, and is appropriately determined in consideration of manufacturing conditions such as spraying and drying conditions in a spray dryer processing apparatus.
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.

<Preparation of precursor support>
The precursor carrier can be produced by introducing the slurry liquid into the spray dryer processing apparatus shown in FIG. 3 to form droplets and drying the slurry (in this specification, the one before firing is referred to as a precursor carrier). ).
Next, the produced slurry liquid is sprayed and dried with a spray dryer processing apparatus.
In the spray dryer processing step, the slurry liquid has a droplet forming step (atomization) for making fine droplets, and a drying step (drying) for drying the fine droplets by contacting with hot air, It is possible to obtain a precursor carrier in which a coating layer made of an inorganic binder and an inorganic aggregate is formed on the surface of a functional substance serving as a nucleus.

<Spray dryer processing equipment>
FIG. 3 is a schematic view of a spray dryer processing apparatus, which is an example of an apparatus for producing a precursor carrier. As shown in FIG. 3, the spray dryer processing apparatus includes a slurry liquid tank 21, an air blower 22, a nozzle 23, a drying chamber 24, a heater 26, a cyclone 27, a bag filter 28, and an exhaust air blower 29.
The nozzle 23 is disposed in the upper part of the drying chamber 24. The nozzle 23 includes a slurry liquid supply path 21 a that opens into the drying chamber 24 and an air supply path (not shown). A slurry liquid tank 21 for supplying the slurry liquid is connected to the slurry liquid supply path 21a, and a blower for supplying air is connected to the air supply path (not shown).
The slurry liquid supplied from the slurry liquid supply path 21a and the blown air supplied from the air supply path (not shown) collide at the nozzle 23, whereby the slurry liquid is sprayed into fine droplets.

The drying chamber 24 is a cylindrical dryer having a hollow inside. A nozzle 23 is disposed at the top, and a blower opening 22a through which air is introduced from the blower blower 22 is opened.
In addition, a heater 26 capable of heating the air introduced into the drying chamber 24 to a predetermined temperature is provided between the blower blower 22 and the blower opening 22a.
That is, the slurry liquid is supplied to the nozzle 23 through the liquid supply path 21 a, and simultaneously atomized by supplying air from the air supply path to the nozzle 23 and sprayed into the drying chamber 24.

The discharge port of the drying chamber 24 is connected to a cyclone 27. The outlet of the cyclone 27 is connected to the bag filter 28. A wind exhaust blower 29 is connected to the bag filter 28.
The lower part of the cyclone 27 and the bag filter 28 is provided with a discharge port capable of collecting the product.

(Drop formation process).
Next, the air from the blower blower 22 is heated by the heater 26 and introduced into the drying chamber 24. In the drying chamber 24, the atomized slurry droplets and the heated air come into contact with each other, and the slurry droplets are dried. At the same time, a coating layer made of an inorganic material is formed on the surface of the functional substance particles. A carrier is produced (drying step).

The air temperature in the drying step is preferably set to 100 ° C. or more and 300 ° C. or less at the inlet temperature.

The prepared precursor carrier falls in the drying chamber 24 together with hot air and is sent to the cyclone 27, and most of the precursor carrier is collected. The precursor carrier that has not been collected is sent to the bag filter 28 and collected. The state of the surface of the precursor carrier thus produced is shown in FIG.

<Firing, cooling, microcrack formation>
The precursor carrier produced as described above is fired in an inert gas atmosphere such as hydrogen or nitrogen to form microcracks in the coating layer. At this time, the ratio (opening ratio) of microcracks formed in the coating layer can be adjusted by the mass ratio of the inorganic aggregate and the inorganic binder blended in the coating layer. By controlling the aperture ratio, it is possible to adjust the diffusion amount of the functional substance. In addition, by firing the precursor support in an atmosphere of hydrogen or an inert gas, the microcracks are formed in a state having a function of diffusing the functional material without causing the functional material to be oxidized and disappeared from the opening. Can do. That is, when the precursor support is fired in an oxidizing atmosphere, the functional substance (for example, an antioxidant substance such as L-ascorbic acid) is oxidized and burned out, and the dissipating function is lost.
Although the firing temperature and time are not specified, it is sufficient if the inorganic binder in the coating layer is melted and vitrified and microcracks can be formed in the coating layer during cooling. For example, firing at 700 to 900 ° C. is suitable. is there.

FIGS. 4 (1) to (6) show the state of the surface of the carrier that has been cooled after firing and has formed microcracks in the coating layer. As shown in FIG. 4, many micro cracks can be observed in the coating layer. The size and number of microcracks on the surface of the support can be adjusted by controlling the mass ratio between the inorganic aggregate and the inorganic binder in the coating layer and controlling the cooling conditions.
If the precursor carrier is not baked, microcracks are not formed in the coating layer (FIG. 4 (7)), and it is difficult to disperse the functional substance.

<The process of preparing a chemical for attachment by mixing the carrier with an attachment resin>
The carrier prepared in the previous step is mixed with a resin for attachment in order to attach it to the base material to prepare a chemical for attachment.

<Plastic resin>
The sheet member is produced by attaching a carrier to a base material via an attaching resin. Examples of the resin to be attached include water-dispersed emulsion resins and water-soluble resins, and examples thereof include ethylene vinyl acetate resins, acrylate resins, vinyl chloride resins, CMC, and polyvinyl alcohol. Can be used. Among these, vinyl chloride resins and acrylic resins are preferable because they have low odor and good stability.
Further, the resin to be attached can be satisfactorily processed without being dropped when the resin having the characteristic that the minimum film forming temperature is between 0 ° C. and 40 ° C. is used, and the finished product is not sticky.

<Mass ratio of carrier and resin for attachment>
The mass ratio of the carrier and the resin to be attached is
It is preferable to prepare a carrier at a mass ratio in the range of carrier: resin to be attached = 15: 1 to 1: 1.
If it is this range, there will be little drop-off | omission of a support body and it will be less likely to prevent dispersion | distribution of a functional substance with the covering resin for covering.
Further, it is preferable that the mass ratio of the support: the resin to be attached = 10: 1 to 5: 1.
That is, if the mass ratio of the resin to be attached is lower than the above range, the carrier is difficult to attach to the base material and falls off and is not suitable for use.
On the other hand, if the mass ratio of the resin to be attached exceeds the above range, the resin to be attached covers the surface of the carrier, and the diffusion of the functional substance is hindered.

<Pickup amount of attached chemicals>
The pick-up amount in the case of adhering processing of the attached chemical is suitable if it is adjusted to 100 to 300% by mass of the basis weight of the base material because adhesion of the adhering chemical is stable, and is adjusted to 150 to 250% by mass. Further preferred.

<Concentration of attached chemicals>
The concentration of the attached chemical solution is inevitably determined from the amount of the attached chemical solution and the pick-up amount of the attached chemical solution, but when formulated at 5 to 40% by mass, it is easy to prepare the attached chemical solution and the stability of the attached chemical solution. Further, it is preferable to prepare at 10 to 30% by mass.

<Fabrication of attached chemicals and production of sheet member by drying>
The attachment chemical solution in which the carrier and the resin to be attached are mixed is attached to the base material by a dipping method, a spray method, a coating method, or the like, and becomes a sheet member to which the carrier is attached through a drying process. Among these methods, there is a problem that the coating method tends to cause a decrease in air permeability because it is applied to the surface, and the spray method has a problem that it is difficult to control the amount of spraying due to a large scattering loss. Therefore, it is preferable to use a dipping method that allows easy management of the amount of adhesion.

FIG. 5 shows an example of a dipping method apparatus. In the dipping method, the base material is dipped and attached to the attachment chemical solution in which the carrier and the attachment resin are mixed, and then passed through a mangle squeezing device composed of a plurality of nip rolls. The adhesion amount of the chemical solution to be attached on the substrate is adjusted to a constant value, wound through a drying process, and an attachment sheet member to which a carrier is attached is produced.

<Drying after dipping>
Drying after dipping is preferably performed within 2 minutes with a hot air dryer of 150 ° C. or lower in order to suppress thermal deterioration of the functional substance.
When drying with a cylinder dryer, the roll surface temperature should be 130 ° C. or lower for 2 minutes or less, and further 120 ° C. or lower for 1 minute or less to deteriorate the functional material. Is further suppressed.

<Attached amount of carrier>
In the present invention, the attachment sheet member according to the embodiment does not specify the attachment amount of the carrier attached to the sheet member, but when used in an air filter or the like, the attachment amount of the carrier having antioxidation property Is preferably 3 to 30 g / m ² , and more preferably 5 to 20 g / m ² . If the loading amount of the carrier is less than 3 g / m ² , there is no diffusing effect, while if it is more than 30 g / m ² , the airflow resistance increases, which is not suitable for an air filter.

FIG. 6 shows an example of an air filter using an attachment sheet member. In this example, the sheet member is used after being pleated.

<Example of air conditioner>
FIG. 9 is a schematic view in which the air filter of the embodiment is attached to the vehicle air conditioner. By switching the intake door 36, the vehicle air conditioner 30 receives the airflow 37 of the vehicle exterior air or the vehicle interior air by the blower 32 and passes the air filter 33 of the vehicle air conditioner according to the present embodiment. The airflow 35 containing the functional substance in the air filter 33 can pass through the evaporator 34 and be diffused into the vehicle.

<Other uses>
Since the attached sheet member of the present invention has air permeability, it can also be applied to a mask.
The mask to which the attached sheet member of the present invention is applied can be used as a sanitary mask by shaping the sheet member into a pleated shape or a three-dimensional shape.
In addition to the original functions of a commercially available sanitary mask, a mask to which the attached sheet member of the present invention is applied can impart functional substance effects, antioxidant effects, moisturizing effects, and the like. For example, when an L-ascorbic acid derivative is used as a functional substance, the substance is gradually released, so that it can be aspirated or brought into contact over a long period of time, and is considered effective for moisturizing.

Examples of the present invention are shown below.
First, in the preparation of the slurry, a carrier having a changed coating layer thickness was prepared by changing the ratio of the functional substance (nuclear body) and the inorganic material (coating layer) to be mixed.
Table 1 shows Sample 1 to Sample 19.
Samples 1 to 4 are samples in which the functional layer (L-ascorbic acid) is 20% by mass: inorganic material (inorganic aggregate + inorganic binder) is 80% by mass and the coating layer is relatively thick.
On the other hand, Samples 16 to 19 are samples in which the functional layer (L-ascorbic acid) is 80% by mass and the inorganic material (inorganic aggregate + inorganic binder) is 20% by mass to make the coating layer relatively thin. It is.
The other samples 5 to 15 have the ratios shown in Table 1.

Samples 1 to 19 were spray-dried and calcined at 800 ° C. in a hydrogen furnace. Under the cooling conditions shown in Table 3, carriers 1 to 19 having an average particle diameter of 1 to 20 μm (carriers 9 to 12 are averages) Particle size 1 μm) was produced.
<Processing conditions>
Spray dryer temperature: 230 ° C (in air)
Firing temperature: 800 ° C. (hydrogen atmosphere)
Rapid cooling condition: 800 ° C to 500 ° C region below temperature (4 steps of 150 ° C, 200 ° C, 250 ° C, 300 ° C)
The region of 500 ° C. or lower was gradually cooled at 100 ° C./min.
The raw materials used were as follows.
Nucleus: L-ascorbic acid coating layer Inorganic binder: Colloidal silica (Snowtex 30: Solid content 30%)
Inorganic aggregate: Amorphous silica particles (average particle size = 0.1 to 1.0 μm)
Inorganic binder: inorganic aggregate = mixed in the slurry at a ratio of 85:15.

Next, a carrier having a changed composition of the coating layer was produced.
Table 2 shows Sample 20 to Sample 28.

In samples 20 to 28, in the slurry,
Functional substance (L-ascorbic acid): inorganic material = 60% by mass: fixed to 40% by mass of inorganic material, and the ratio of inorganic binder: inorganic aggregate in the inorganic material was changed.
These samples 20 to 28 were spray-dried and fired at 800 ° C. in a hydrogen furnace to produce supports 20 to 28. Under the cooling conditions shown in Table 3, the supports 20 to 20 having an average particle diameter of 1 to 20 μm were produced. 28 was produced.
<Processing conditions>
Spray dryer temperature: 230 ° C (in air)
Firing temperature: 800 ° C. (hydrogen atmosphere)
Rapid cooling conditions: The region of 800 ° C. to 500 ° C. is controlled at a rate of temperature decrease of 250 ° C./min. The region of 500 ° C. or lower is gradually cooled at 100 ° C./min.

The raw materials used were as follows.
Nucleus: L-ascorbic acid coating layer Inorganic binder: colloidal silica (Snowtex 30: aqueous suspension with a solid content of 30%)
Inorganic aggregate: amorphous silica particles (average particle size = 0.1, 0.3, 1.0 μm)

[Examples 1 to 28]
The produced carriers 1 to 28 were mixed with an acrylate emulsion resin having a minimum film forming temperature of 30 ° C. at a ratio of 5: 1 and diluted with water to obtain a 30% attachment chemical solution.
After dipping a polyester non-woven fabric base material having an average fiber diameter of 6 denier and a basis weight of 40 g / m ² into this attachment chemical solution, it is mangled and dried in a hot air dryer at 130 ° C. for 1 minute, and antioxidant An attachment sheet member having a substance attachment amount of 5 g / m ² was produced.
Using this attached sheet member, an air filter having a width of 50 mm, a length of 50 mm, and a peak height of 20 mm and a number of peaks of 20 was prepared, and a functional substance (L-ascorbic acid) was added to water using a diffusion performance evaluation apparatus shown in FIG. And the antioxidant performance was evaluated by the DPPH radical scavenging method. The evaluation results are shown in FIGS. 8 (a) and 8 (b).
The amount of the antioxidant substance attached was adjusted by the pick-up amount of mangle.

[Comparative Example 1]
L-ascorbic acid (average particle size of 1.0 μm made water-insoluble by surface treatment) is prepared as a functional substance, silica particles having an average particle size of 0.5 μm as an inorganic aggregate, and an inorganic binder as a coating layer Colloidal silica (trade name Snowtex 30: aqueous suspension with a solid content concentration of 30%) was prepared.
A functional substance, an inorganic aggregate, and an inorganic binder (water suspension with a solid content concentration of 30%) were mixed so as to have the same ratio as that of the sample 9, and water was added to the mixed liquid to prepare a slurry liquid. .
The slurry liquid was atomized with a spray dryer and dried with hot air at 230 ° C. to obtain a precursor carrier.
Since this precursor carrier is unfired, no microcracks are formed on the surface (precursor carrier of FIG. 4 (7)).
Subsequent production conditions and methods were the same as in Examples, and an air filter was produced and the antioxidant performance was observed. However, L-ascorbic acid was hardly detected.

[Comparative Example 2]
In an aqueous solution in which L-ascorbic acid (having an antioxidant function) is dissolved in 40% by mass as a functional substance, an acrylic acid ester emulsion resin having a minimum film-forming temperature of 30 ° C. as an attaching resin is in a ratio of 5: 1. The mixture was mixed and diluted with water to obtain a 30% accessory drug.
After dipping a polyester non-woven fabric base material having an average fiber diameter of 6 deniers and a basis weight of 40 g / m ² , this attachment agent was mangled and dried in a hot air dryer at 130 ° C. for 1 minute, A sheet member having an attachment amount of 5 g / m ² was produced.
Comparative Example 2 is an example in which a functional substance is simply attached to a base material without going through the step of forming a precursor support, unlike the above-described example.
Subsequent production conditions and methods were the same as in the examples, and air filters were produced to evaluate the antioxidant performance.
Initially, it showed an L-ascorbic acid concentration of about 2.5 mg / L, but it became almost undetectable after 40 days.

<Evaluation method>
The above evaluation method will be described below.
FIG. 7 shows an apparatus used for measuring the emission characteristics of functional substances for the air filters of the examples and comparative examples. This apparatus includes a duct for fixing an air filter, a bubbling container for capturing a functional substance released from the filter, a pump for sucking air, and a flow rate regulator.

Measurement is performed by installing the apparatus shown in FIG. 7 in a constant temperature and humidity box and continuously operating, and the amount of the functional substance released into the air is evaluated by the DPPH radical elimination method every 7 days.

In this evaluation method, the vacuum pump and the flow rate regulator are used to flow a constant flow of air through a duct and a bubbling device incorporating the evaluation filter.
Further, the bubbling container for capturing the functional substance blocked light in order to suppress the oxidation of the functional substance, and pure water was used as the absorbing liquid. The functional substance was assumed to be absorbed 100% in pure water.
In this evaluation method, a functional substance (L-ascorbic acid solution) with a known concentration was prepared, a calibration curve was prepared with a spectrophotometer, and then the bubbling solutions collected for the air filters of Examples and Comparative Examples were similarly used. The concentration was calculated from the calibration curve.

The conditions for measuring the emission from the air filter used in this evaluation method are as follows.
・ Aspiration amount: 0.5m3 / min
-Absorption time in bubbling liquid at each measurement: 60 minutes-Temperature and humidity in constant temperature and humidity BOX: Temperature: 25 ° C, Humidity: 55%

<Calculation of the amount of functional substances released>
The amount of functional substance released is calculated by the DPPH radical elimination method.
DPPH (1,1-diphenyl-2-picrylhydrazyl) used in this method has a radical in the material structure, and if there is contact with a functional substance, the radical present in DPPH disappears. To do. At that time, the liquid color of the DPPH solution changes from purple to yellow according to the degree. By measuring the change with a spectrophotometer and comparing it with a standard solution, a value indicating the degree of antioxidant performance is obtained.

<Preparation of DPPH solution>
DPPH (manufactured by Wako Pure Chemicals: 1,1-diphenyl-2-picrylhydrazyl) was dissolved in ethanol to a concentration of 0.125 mmol, and placed in a constant temperature shaking water bath at 30 ° C. did.

<Creation of calibration curve>
L-ascorbic acid was used as a standard functional substance and dissolved in pure water to prepare four standard aqueous solutions having concentrations of 0.50, 1.00, 1.50, and 2.00 mg / L.
4 mL of the prepared standard aqueous solution was added to 5 mL of DPPH solution kept at 30 ° C. to prepare a 4-point calibration curve sample. In addition, a sample for preparing a calibration curve was prepared using pure water instead of the standard aqueous solution.
The prepared five calibration curve preparation samples were measured with a spectrophotometer to prepare a calibration curve.

<Measurement of Antioxidation Performance of Examples and Comparative Examples>
1 mL was collected from the bubbling solution collected in Examples and Comparative Examples, added to 5 mL of the above-mentioned DPPH solution, measured with a spectrophotometer, and the concentration of the functional substance was measured from a calibration curve.

<Verification of Examples>
FIGS. 4 (1) to 4 (6) show photographs showing the surface state of the carrier produced in the example.
As shown in FIG. 4 (7), the precursor carrier shown in Comparative Example 1 is in a state where its surface is covered with a coating layer immediately after spray dryer processing (unfired), and microcracks are formed. Not.
Thereafter, the support is fired and rapidly cooled in a hydrogen atmosphere to form microcracks in the coating layer (FIGS. 4 (1) to (6)).
Furthermore, as shown in FIGS. 4 (1) to (6), by changing the blending ratio of the inorganic aggregate and the inorganic binder in the coating layer, various opening ratios (size, number, etc.) are formed in the coating layer of the carrier. ) Can be formed, and a carrier suitable for the purpose of use can be produced.

Next, the results of the emission test of the functional substance of the air filter produced in the examples and comparative examples are collectively shown in FIGS. 8 (a) and 8 (b).
The vertical axes of FIGS. 8A and 8B indicate the concentration of the functional substance (antioxidant component) per liter of bubbling water, and the higher the value, the greater the amount of functional substance released from the air filter. It shows that.
The horizontal axis indicates the elapsed time (days).

As shown in FIGS. 8A and 8B, the microcracks of the carrier can be changed by changing the ratio of the inorganic aggregate and the inorganic binder in the coating layer or changing the manufacturing conditions of the carrier. It can be seen that the amount and the duration of the functional substance can be controlled by controlling the size and the number of the particles.

In Comparative Example 1, the amount of functional substance released was small from the beginning, and there was no antioxidant effect. This is presumably because the macromolecules are not formed on the surface of the carrier, and thus the functional material is not sufficiently diffused.

In Comparative Example 2, there is no coating layer covering the functional substance, and since it is in direct contact with the air, the amount of the functional substance is initially large, but the functional substance is removed after more than one month. It is presumed that it was used up and no longer emitted.

[Air filters for vehicles]
Using the attachment sheet member using the carrier 11 of the example, the air filter for a vehicle was manufactured by pleating into a size of 200 mm × 200 mm × 28 mm (number of peaks 30).
This vehicle air filter was attached to the vehicle air conditioner illustrated in FIG.
As a result, as a result of the acceleration test, it was found that the functional material is diffused from the air diffused into the vehicle through the vehicle air filter over a long period of one year or more.

The carrier of the present invention, and an attachment sheet member attached thereto, can be used for home appliances such as a vehicle air conditioner filter, an automobile cabin cleaning filter, a refrigerator, a mask, and the like to disperse a functional substance over a long period of time. Can be used and has high industrial applicability.

DESCRIPTION OF SYMBOLS 10: Sheet | seat member 11: Base material 12: Resin for attachment 13: Carrier 21: Slurry liquid tank 21a: Slurry liquid supply path 22: Blower blower 22a: Blower outlet 23: Nozzle 24: Drying chamber 26: Heater 27: Cyclone 28 : Bag filter 29: Exhaust blower 30: Vehicle air conditioner 32: Blower 33: Air filter 34: Evaporator 35: Purified air flow 36: Intake door 37: Air flow

Claims

A carrier composed of a nucleus composed of a functional substance and a coating layer covering the surface of the nucleus,
The coating layer comprises a vitrified inorganic binder and an inorganic aggregate dispersed in the inorganic binder,
And, on the surface of the coating layer, a microcrack having an opening communicating with the functional substance serving as the core is formed,
The functional substance is
A carrier that is diffused to the outside from the microcracks.
The inorganic aggregate dispersed in the coating layer is silica or alumina particles having a particle size of 0.1 to 1.0 μm,
The inorganic binder is
2. The carrier according to claim 1, comprising one kind of colloidal silica, colloidal tungsten lithium silicate, potassium silicate, or sodium silicate, or a combination thereof.
An attached sheet member, wherein the carrier according to claim 1 or 2 is attached on a base material of the sheet member.
An air filter for a vehicle air conditioner using the attachment sheet member according to claim 3.
It consists of a core made of a functional material and a coating layer covering the surface of the core,
The coating layer comprises a vitrified inorganic binder and an inorganic aggregate dispersed in the inorganic binder,
And, on the surface of the coating layer, microcracks that lead to the functional substance serving as the core are formed,
A method of manufacturing a carrier in which the functional substance is diffused to the outside from the microcracks,
Mixing the core, the inorganic binder and the inorganic aggregate to produce a slurry;
The slurry is processed by a spray dryer process.
A step of producing a precursor carrier by coating the core with the inorganic binder and inorganic aggregate;
Place the precursor carrier in an inert gas or hydrogen atmosphere furnace,
While firing the precursor carrier to vitrify the inorganic binder,
Cooling to form microcracks in the coating layer;
A method for producing a carrier, comprising:
A step of mixing the carrier produced in claim 5 with an attaching resin to produce a chemical,
Attaching the chemical to the surface of the substrate;
And a step of drying the base material to which the chemical solution is adhered to attach the carrier onto the base material.