JP4744477B2 - Regeneration time indicator for light regenerating deodorant - Google Patents

Description

  The present invention relates to a regeneration timing display material for a light regeneration type deodorant, and more particularly to a display material for informing the regeneration timing of a deodorant having a light regeneration function.

In recent years, interest in odors has increased, and in particular, there has been an increasing demand for deodorizers that remove odors in living spaces.
Although various forms of deodorizers are commercially available, deodorizers such as activated carbon, silica gel and activated alumina are still used mainly because of their good performance and processability.
Activated carbon has various types such as granular, granular, and fibrous, and removes organic odorous substances by physical and chemical adsorption. Moreover, since the surface area is large, the sustainability of the effect is high.
Activated alumina and silica gel, which are inorganic deodorizers, are mainly granular or powder, but adsorbs highly polar molecules, for example, inorganic odorous substances such as ammonia and nitrogenous oxides. Can be used properly.

Recently, in order to increase the added value of a deodorizing agent, a form added with an antibacterial action and a photocatalytic function of a metal is seen.
A photocatalyst represented by titanium oxide has a property of oxidatively decomposing an organic substance to be contacted by irradiating ultraviolet rays.
Therefore, when a suitable adsorbent and a photocatalyst are combined, a light regeneration type deodorant having a light regeneration function can be produced.
Unlike the conventional deodorizer, this light regeneration type deodorizer can regenerate the deodorization function only by drying in the sun after the deodorization, and can be used repeatedly.
Therefore, it is more economical than conventional deodorizers, and the increase in waste that is becoming serious can be suppressed.
The mainstream of the light regeneration type deodorant is a combination of a deodorizer such as activated carbon or silica gel and titanium oxide having a high photocatalytic activity.
For example, corrugated non-woven fabric or paper filled with a mixed powder of deodorant and titanium oxide, or a substrate such as carbon fiber or activated carbon filter is incorporated as a deodorizing filter, and silica oxide or alumina sol is used to base titanium oxide. What was carried | supported on the material surface is known (refer patent document 1).
In addition, an inorganic component apatite processed into a deodorizing filter and combined with a photocatalyst is also known, and is also applied to an air purifier filter and the like.
These light-regenerating deodorizers can regenerate the deodorizing function by drying in the sun, but do not have a display function for promoting sun-drying (regeneration).
Therefore, the usage method of this light regeneration type deodorant is one in which the user sensuously judges the presence of odor and regenerates.
In addition, a method is also known in which a label that describes the date and time of start of use and the date and time of regeneration is attached to a deodorant, and then dried by sun drying after a certain period of time.
However, in the above two methods, the user often forgets the time to regenerate, and since it may be left without being regenerated, the function as a light regenerating deodorant has been impaired.

  It is known that when a paper impregnated with a photochromic substance such as tungstic acid and a water-soluble polymer compound such as polyvinyl alcohol is irradiated with light, it is colored blue and faded in the dark (see Patent Documents 2 to 3). However, it has not been known to use a method for controlling the fading period and a regeneration timing display material for a light regeneration type deodorant by controlling the fading period.

JP 2003-93485 A Japanese Patent Publication No. 5-71717 Japanese Patent No. 2919220

  The present invention has been made under such circumstances, and an object of the present invention is to provide a light regeneration type deodorant regeneration time display material that displays the light regeneration time of the light regeneration deodorant and can be used repeatedly. To do.

  As a result of intensive studies to achieve the above object, the present inventors impregnate a sheet-like base material with (A) a transition metal oxide having photochromism and (B) a water-soluble polymer compound. Or a coating layer containing the component (A) and the component (B) provided on the surface of the sheet-like base material is responsive and reversible in a short time even by weak ultraviolet rays such as sun-dried In particular, the present inventors have found that the blue color is regenerated and has high durability, and is useful as a regeneration time display material for a light regeneration type deodorant, and the present invention has been completed.

That is, the present invention
1. A display material for informing the regeneration timing of the light regenerating deodorant, wherein the sheet-like base material is impregnated with (A) a transition metal oxide having photochromism and (B) a water-soluble polymer compound, Or a regeneration time indicating material for a light regenerating deodorant, characterized in that a coating layer containing the component (A) and the component (B) is provided on the surface of the sheet-like substrate,
2. The content ratio of the component (A) and the component (B) is a regeneration time indicating material for the light regeneration deodorant according to the above 1, wherein the mass ratio is 50: 1 to 1:50,
3. Regeneration | regeneration of the optical regeneration type deodorizer of said 1 or 2 formed by impregnating a sheet-like base material with (A) component and (B) component so that the total amount may be 1-500 g / m < ² >. Time display material,
4). The reproduction | regeneration of the light reproduction type deodorizer of said 1 or 2 with which the coating layer containing (A) component and (B) component is provided in the sheet-like base material surface by the thickness of 0.1-10 micrometers. Time display material.
5. (A) The transition metal oxide having photochromism is at least one selected from oxides of metals belonging to Group 5 and Group 6 of the periodic table (long period type). Regeneration time display material for light regenerating deodorant
6). (A) The regeneration time indicating material for the light regenerating deodorant according to any one of 1 to 5 above, wherein the component is tungsten oxide and / or molybdenum oxide,
7). (B) The optical regeneration according to any one of 1 to 6 above, wherein the water-soluble polymer compound is at least one selected from polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethylene oxide, polyacrylamide, and sodium polyacrylate. Regeneration time indicator for mold deodorizer,
8). (B) Regeneration time display material of the light regeneration type deodorant according to any one of 1 to 7 above, wherein the component is polyvinyl alcohol and / or polyethylene glycol,
9. The light regeneration type deodorant used in a refrigerator, the light regeneration type deodorant regeneration time display material according to any one of 1 to 8 above,
10. The reproduction | regeneration time display material of the light reproduction | regeneration deodorant in any one of said 1-9 affixed on a light reproduction | regeneration deodorant is provided.

The regeneration timing display material for the light regeneration type deodorant according to the present invention is such that the blue color of the regeneration time display material is faded for a certain period of time in a dark room space at an average constant temperature and constant humidity. The time is displayed.
Therefore, when the regeneration timing display material is used by being attached to a case or a housing of the light regeneration type deodorant, it is possible to prompt the user to regenerate the light regeneration type deodorant due to blue fading.
Therefore, the light-regenerating deodorant to which the regeneration time display material is affixed can be sun-dried, etc., so that the regeneration of the period display material (colored in blue) and the regeneration of the deodorant can be performed simultaneously. it can.
In particular, the light regeneration type deodorant regeneration time indicating material of the present invention is useful when the light regeneration deodorant is used in a refrigerator.

The present invention is described in detail below.
The light regeneration type deodorant regeneration time display material of the present invention (hereinafter sometimes referred to as regeneration time display material) is a display material for informing the regeneration time of the light regeneration type deodorant, and is a sheet-like substrate. The material is impregnated with (A) a transition metal oxide having photochromism and (B) a water-soluble polymer compound, or on the surface of the sheet-like substrate, the component (A) and the component (B) The coating layer containing is provided.
[Light regeneration deodorant]
The light regeneration type deodorant to which the regeneration timing display material of the present invention is applied is not particularly limited and can be applied to various types conventionally known as light regeneration type deodorants.
This photoregenerative deodorant is basically obtained by impregnating or coating a porous substrate such as a nonwoven fabric or a woven fabric made of glass fiber with a photocatalyst material, an odor adsorbent that adsorbs an odor component, and an inorganic binder. It has a structure.
When the photocatalytic material is irradiated with light having energy higher than the band gap, it is excited to generate electrons in the conduction band and holes in the valence band.
The generated electrons reduce surface oxygen to generate superoxide anions (• O ²⁻ ), and holes oxidize surface hydroxyl groups to generate hydroxyl radicals (• OH). The active oxygen species exerts a strong oxidative decomposition function, and has a function of efficiently decomposing organic substances adhering to the surface of the photocatalytic material.
As such a photocatalytic material, anatase type, rutile type and brookite type titanium oxide crystals are known, and in general, anatase type titanium oxide is frequently used.
The odor adsorbent is not particularly limited, and examples thereof include activated carbon, alumina gel, silica gel, zeolite, and the like. When adsorbing odor components such as a refrigerator, activated carbon is used in the odor adsorbent. Is preferred.
On the other hand, as the inorganic binder, an amorphous type titania binder, a silica binder, an alumina binder, or the like can be used.
When the light-regenerating deodorant is used in a dark place such as a refrigerator, the deodorizing function decreases with time, and when a certain period of time elapses, the adsorbed amount of odor components becomes saturated and the deodorizing function is lost.
Therefore, when the deodorizing function is lowered to some extent, the photoregenerative deodorant is irradiated with ultraviolet rays to excite the photocatalyst material in the deodorant and take measures to decompose and regenerate the adsorbed odor components.
The ultraviolet irradiation is usually performed by a method of using ultraviolet rays in sunlight by drying the light-regenerating deodorant to be regenerated.
The regeneration timing display material of the present invention is a member that informs the regeneration timing of the light regeneration deodorant as described above.

[Sheet substrate]
The sheet-like base material in the regeneration time indicating material of the present invention has a sheet-like base for impregnation for impregnating the transition metal compound having the photochromism of the component (A) and the water-soluble polymer compound of the component (B). There are two modes of a sheet-like base material for coating for providing a coating layer containing a material and the component (A) and the component (B).
In addition, although it is conceivable to use the mixture containing the component (A) and the component (B) after film processing, in this case, from the viewpoint of mechanical strength, manufacturability, handleability, etc., the thickness is Usually, a thickness exceeding 10 μm is required.
However, when the thickness of the film exceeds 10 μm, the fading time becomes long as shown in Comparative Example 1 described later, and it is not suitable as a reproduction time display material.
Therefore, in the present invention, a sheet-like base material impregnated with the component (A) and the component (B) or a coating layer containing the component (A) and the component (B) is provided. Used as a material for indicating the regeneration time.

[Sheet substrate for impregnation]
As the sheet substrate for impregnation, a porous sheet substrate is usually used.
There are no particular restrictions on the porous sheet-like base material, such as non-woven fabrics made of natural fibers, synthetic fibers, glass fibers, carbon fibers, woven fabrics, knitted fabrics, foamed plastic sheets, and various paper base materials. There is.
As the impregnated sheet-like base material, a paper base material is preferable from the viewpoints of impregnation property, retainability, performance as a display material, and the like.
As the paper substrate, for example, craft paper, fine paper, glassine paper, thin paper, test filter paper, and the like can be used.
In the case of using a cloth base material such as a nonwoven fabric, a woven fabric, or a knitted fabric as the sheet-like base material for impregnation, the thickness is from the viewpoint of workability, handleability, stickability to a light regenerating deodorant, etc. The thickness is preferably 20 to 5000 μm, more preferably 50 to 2000 μm, and still more preferably 100 to 1000 μm.
Further, from the viewpoint of maintaining the components (A) and (B) in an amount capable of effectively exhibiting photochromism, the specific surface area is preferably 1 to 1000 m ² / g, and the porosity is preferably 20 ~ 80%.
In the case of using a paper base material, the thickness is preferably 20 to 3000 μm, more preferably 50 to 2000 μm, from the viewpoint of waist strength, stickability to a light-regenerating deodorant, impregnation property, and the like. More preferably, it is 100 to 1000 μm, and from the viewpoints of mechanical strength as a substrate, etc., while maintaining the components (A) and (B) in an amount capable of effectively exhibiting photochromism, the tension is preferably Is 0.4 to 1.3 g / cm 3, more preferably 0.45 to 1.0 g / cm 3.

[Sheet substrate for coating]
As a sheet-like substrate for coating, a paper substrate such as polyethylene laminated paper, art paper, coated paper, synthetic paper, etc., laminated with high-quality paper or glassine paper; metal foil such as aluminum foil or stainless steel foil; polyethylene Polyolefin resins such as polypropylene and poly-4-methylpentene-1, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate resins, polystyrene resins, polyvinyl chloride resins, acrylic resins, and cellulose resins. Plastic film; etc. can be used.
When using the plastic film as the sheet-like substrate for coating, for the purpose of improving the adhesion with the layer provided on the surface, an oxidation method, a concavo-convex method, etc. on one side or both sides as desired. Thus, surface treatment can be performed.
Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Examples include solvent processing methods.
These surface treatment methods are appropriately selected depending on the type of the base film, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.
A primer layer may be provided.
In the case of a paper base material or a plastic film, the thickness of the sheet-like base material for coating is usually about 10 to 300 μm, preferably from the viewpoint of mechanical strength, stickability to a light-regenerating deodorant, economy, and the like. Is 15 to 150 μm.
Further, in the case of a metal foil, it is preferable that the metal foil is thin as long as the handling property and the sticking property to the light regeneration type deodorant do not become defective.
The color tone of the impregnating sheet-like substrate and the coating sheet-like substrate is colorless, white, or light-colored in order to increase the contrast and make it easier to see when the reproduction time display material of the present invention is colored. It is preferable that

[(A) Transition metal oxide having photochromism]
In the reproduction time display material of the present invention, the transition metal oxide having photochromism used as the component (A) is not particularly limited as long as it has photochromism performance, and various transition metal oxides are used. .
The “photochromism” refers to a phenomenon in which a single chemical species reversibly forms two states having different absorption spectra by the action of light without changing the molecular weight.
The transition metal oxide referred to in the present invention includes a transition metal acid.
As the transition metal oxide having photochromism, oxides of metals belonging to Group 5 and Group 6 of the periodic table (long period type) are preferable, and specifically, oxidation of metals such as vanadium, niobium, molybdenum, tungsten, and the like. You can list things.

Examples of the vanadium oxide include vanadium pentoxide (V ₂ O ₅ ) and metavanadate (HVO ₃ ), and examples of the niobium oxide include niobium pentoxide (Nb ₂ O ₅ ) and niobic acid (Nb ₂ O ₅ · xH). ₂ O) and the like as molybdenum oxide, molybdenum trioxide (MoO ₃ ), orthomolybdic acid (H ₂ MoO ₄ or MoO ₃ .H ₂ O) and the like as tungsten oxide, and tungsten trioxide (WO ₃ ), orthotungstic acid (H ₂ WO ₄ or WO ₃ · H ₂ O) and the like.
In the present invention, these transition metal oxides may be used singly or in combination of two or more, but from the viewpoint of photochromic performance, among these, tungsten oxide and / or molybdenum. An oxide is preferable, and tungsten oxide is particularly preferable.
As materials having photochromism, in addition to the transition metal oxides that are the inorganic materials, there are organic materials such as azobenzenes, spiropyrans, spirooxazines, diarylethenes, fulgides, chromenes, etc. From the viewpoint of durability, for example, thermal stability and chemical stability, the above transition metal oxide is used.

[(B) Water-soluble polymer compound]
In the reproduction time indicating material of the present invention, the water-soluble polymer compound used as the component (B) has a function as a binder, dispersibility of the transition metal compound having the photochromism of the component (A), and the transition metal compound. It has a function to enhance color development.
The water-soluble polymer compound is not particularly limited as long as it has the functions described above, and various compounds can be used.
Specific examples include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethylene oxide, polyacrylamide and sodium polyacrylate, and these may be used singly or in combination of two or more. Of these, polyvinyl alcohol and / or polyethylene glycol are preferred from the viewpoint of sensitizing action.
In particular, polyvinyl alcohol is produced by saponification of polyvinyl acetate. By adjusting the degree of saponification and polymerization, various properties such as water solubility, mechanical properties, water resistance, adhesiveness, and surface activity can be obtained. This is preferable because the characteristics can be controlled.
When the polyvinyl alcohol is used, the degree of saponification is preferably 50 mol% or more, more preferably 80 to 99, from the viewpoint of the function as a binder, the dispersibility of the component (A), water solubility, color sensitization, and the like. The degree of polymerization is preferably 100 to 2000, more preferably 500 to 1800.
On the other hand, when polyethylene glycol is used, the molecular weight is preferably about 5,000 to 100,000 in terms of the function as a binder, the dispersibility of the component (A), the color sensitization, and the like.

[Regeneration time display material]
In the reproduction time indicating material of the present invention, the content ratio of the transition metal oxide having photochromism as the component (A) to the water-soluble polymer compound as the component (B) is the photochromism performance and color sensitization. From the viewpoints of dispersibility of the component (A) with respect to the component (B), impregnation with respect to the impregnated sheet-like substrate or coating property with respect to the coating-like sheet-like substrate, the mass ratio is preferably 50: 1 to 1:50. 1: 1 to 1:30 are more preferable.
Further, when the regeneration time indicating material of the present invention is obtained by impregnating the above-mentioned component (A) and component (B) into the sheet-like base material for impregnation, the component (A) and (B) The impregnation amount with the component is 1 to 500 g / m in terms of the total amount of the component (A) and the component (B) from the viewpoint of having good photochromic performance and effectively exhibiting the function as a display material. ² is preferred,
More preferably, it is 3-100 g / m < ² >.
On the other hand, when the reproduction time indicating material of the present invention is formed by forming a coating layer containing the component (A) and the component (B) on the surface of the sheet-like substrate for coating, the thickness of the coating layer The thickness is preferably 0.1 to 10 μm.
If the thickness of the coating layer is in the above range, it has good photochromic performance, and fading in a dark place is not too slow, and the function as a display material is effectively exhibited.

〔Production method〕
The regeneration time indicating material of the present invention comprises an impregnation liquid or a coating liquid containing the above-described transition metal oxide having a photochromism as the component (A) and the water-soluble polymer compound as the component (B) in the aforementioned ratio. Can be produced by impregnating the sheet-like substrate for impregnation, respectively, or by forming a coating layer on the surface of the sheet-like substrate for coating.
As the transition metal oxide having photochromism as the component (A), a colloidal transition metal acid formed by a sol-gel method is used from the viewpoint of uniform dispersibility with respect to the water-soluble polymer compound of the component (B). preferable.
This colloidal transition metal acid can be prepared as follows.
First, after preparing an aqueous solution of a water-soluble transition metal acid salt such as sodium transition metal acid, it is treated with a cation exchange resin, or a mineral acid such as hydrochloric acid or sulfuric acid is added to the aqueous solution to form a colloidal solution. Of free transition metal acids.
A method using a mineral acid is difficult to appropriately adjust pH, and has a problem that an anion is mixed as an impurity. Therefore, a method using a cation exchange resin which is simple and contains little impurity is preferable.
The concentration of the colloid liquid of the free transition metal acid thus obtained is preferably 0.05 to 30% by mass, more preferably 0.3 to 20% by mass, and further preferably 0.616% by mass.
When the concentration of the colloidal liquid is in the above range, the photochromic performance is exhibited well, and the colloidal free transition metal acid can be prevented from gelling.

On the other hand, an aqueous solution of a water-soluble polymer compound is prepared.
The concentration of the water-soluble polymer compound in this aqueous solution is preferably 0.5 to 30% by mass, preferably 3 to 25% by mass, and more preferably 5 to 20% by mass.
When an aqueous solution of a water-soluble polymer compound having such a concentration and the above-mentioned free transition metal acid colloid solution are mixed at a predetermined ratio to prepare an impregnation solution or a coating solution, the stability of the colloid is good. , Gelation is suppressed, and impregnation or coating is good.
In the present invention, the free transition metal acid colloid solution obtained as described above and the aqueous solution of the water-soluble polymer compound are mixed so that the ratios of the component (A) and the component (B) are as described above. Mix to prepare an impregnation solution or coating solution.
Next, the above-mentioned impregnation liquid is added to the sheet-like substrate for impregnation such as the paper substrate as described above so that the total amount of the component (A) and the component (B) is preferably 3 to 100 g / m ^2. After the impregnation, the regeneration time display material of the present invention can be obtained by heat treatment at a temperature of about 30 to 180 ° C. for about 1 to 300 minutes and drying.
In addition, when using a paper base material as a sheet-like base material for impregnation, the said impregnating liquid is added to the paper stock containing the beating pulp in a papermaking process, and papermaking is carried out, and the said (A) component and (B) component A paper base material impregnated with may be prepared.

On the other hand, the coating liquid is applied to the surface of the above-mentioned coating sheet-like base material by a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. It is used to apply a dry thickness of preferably 0.1 to 10 [mu] m, heat treatment at a temperature of about 30 to 180 [deg.] C., and drying to obtain the regeneration time indicating material of the present invention.
In the reproduction time display material of the present invention thus produced, the fading time is adjusted by adjusting the type of transition metal oxide (A) component having photochromism and the water-soluble polymer compound (B) component. And the content ratio thereof, and further, when impregnated with the component (A) and the component (B), the total impregnation amount per unit area, the coating containing the component (A) and the component (B) When the layer is provided, it can be carried out by changing the thickness of the coating layer.
The reproduction time indicating material of the present invention is prepared in advance so as to have a predetermined fading speed based on the reduction rate of the deodorizing effect in a place where the light regeneration type deodorant to which the reproduction time is applied is used. It is good to apply to regenerative deodorant.
When the regeneration time indicating material of the present invention is applied to a light regeneration type deodorant, it is preferable that the regeneration time indicating material is attached to the outside of the casing or case of the deodorizer so that the back side is in contact with the adhesive layer. Moreover, you may stick using a double-sided adhesive tape.
In the reproduction time display material of the present invention, the color fading time is constant particularly under constant temperature and humidity, so that it is particularly excellent when the deodorizing agent is used in a refrigerator.
When the regeneration time display material of the present invention is used in a refrigerator together with a light regeneration type deodorant, the light regeneration type deodorant is usually regenerated in about 14 to 45 days. It is better to set it to about 45 days.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The performance evaluation was performed according to the following measurement method.

Example 1
50 mL of a 4.95 mass% aqueous solution of sodium tungsten (VI) dihydrate (Na ₂ WO ₄ .2H ₂ O) was prepared.
Next, a glass column was filled with 18 cm ³ of a cation exchange resin [Rohm and Hass, trade name AMBERLITE IR120 PLUS (H)], and the aqueous solution of sodium tungstate (VI) was passed through the column. A colloidal solution of tungstic acid was prepared.
Separately, 50 mL of a 16% by mass aqueous solution of completely saponified polyvinyl alcohol (PVA) [trade name, Kuraray Poval 117S, manufactured by Kuraray Co., Ltd.] was prepared.
The aqueous PVA solution (20 mL) and the pretreated tungstic acid colloid solution (20 mL) were quickly mixed to obtain a uniform mixed solution.
Qualitative filter paper [manufactured by Toyo Filter Paper Co., Ltd., trade name ADVANTEC No. 2; 0.26 mm).
After 3 minutes, the filter paper was pulled up and dried in a dryer at 60 ° C. for 40 minutes.
After drying, the filter paper was cut to a size of 1 cm square and used as a regeneration time display material, and attached to the housing of the light regeneration deodorant with a double-sided adhesive tape.
When this filter paper display material was irradiated with ultraviolet light (intensity 0.78 mW / cm ² ) with black light to develop a blue color, the absorbance (λ: 600 nm) became constant after 6 hours.
Next, the filter paper regeneration time display material was allowed to stand in a refrigerator (3 ° C., 72.6% RH, dark room), and the fading behavior was examined.
The blue fading of the filter paper display material was measured for absorbance (λ: 600 nm) from the reflectance of the filter paper display material using a small spectroscope (Ocean Optics, USB2000).
Next, the discolored filter paper display material was again irradiated with ultraviolet light (intensity 0.78 mW / cm ² ) with a black light for 6 hours to develop a blue color, and in a refrigerator (3 ° C., 72.6% RH, dark room). The color fading behavior was examined by leaving it at rest. This operation was repeated twice.
The results are shown in Table 1.

Example 2
When the reproduction time display material made of filter paper having a size of 1 cm square in Example 1 was irradiated with ultraviolet light (intensity 0.78 mW / cm ² ) with a black light to develop a blue color, the absorbance (λ: 600 nm) was obtained after 6 hours. Became constant.
Next, this recycle time display material made of filter paper was left still in a refrigerator (3 ° C., 72.6% RH, dark room), and its fading behavior was examined.
The fading rate was calculated using the following formula.
Fading rate (%) = [[absorbance per elapsed day (600 μm)] / maximum absorbance (600 μm)] × 100
The results are shown in FIG.
In FIG. 1, the filter paper regeneration time display material is represented as paper, the horizontal axis represents the number of days, and the vertical axis represents the fading rate (%).

Comparative Example 1
In the same manner as in Example 1, 50 mL of a 4.95% by mass aqueous solution of sodium tungsten (VI) dihydrate (Na ₂ WO ₄ .2H ₂ O) was prepared, and then a cation was applied to a glass column. 18 cm ³ of an exchange resin [Rohm and Hass, trade name: AMBERLITE IR120 PLUS (H)] was packed, and this aqueous solution of sodium tungstate (VI) was passed through a column to prepare a colloidal solution of tungstic acid.
Separately, 50 mL of a 4% by mass aqueous solution of completely saponified polyvinyl alcohol (PVA) [manufactured by Kuraray Co., Ltd., trade name Kuraray Poval 117S] was prepared.
This aqueous PVA solution (10 mL) and the pretreated tungstic acid colloid solution (10 mL) were quickly mixed to obtain a uniform mixture.
When this mixed liquid (2 mL) was cast into a petri dish (diameter: 35 mm) and air-dried at room temperature, a transparent film (film thickness: 19 μm) with high peelability was obtained.
The obtained film was cut to a size of 1 × 2 cm, used as a film-like reproduction time display material, and fixed to a plastic cell plate with an adhesive tape.
When this film-like reproduction time display material was irradiated with ultraviolet light (intensity 0.78 mW / cm ² ) with black light to develop a blue color, the absorbance (λ: 600 nm) became constant after 6 hours.
Next, this film-like reproduction time display material was allowed to stand in a refrigerator (3 ° C., 72.6% RH, dark room), and its fading behavior was examined in the same manner as in Example 2.
The results are shown in FIG.
In addition, in FIG. 1, the film-like reproduction time display material was represented as a film.

From Table 1, the filter paper regeneration time display material of Example 1 has a constant fading time of about 20 days, and the change in fading rate, that is, the color change from blue to colorless is also constant and reproducible. And is excellent as a material for indicating the regeneration period.
Moreover, the reproduction time display material obtained by coating can obtain the same preferable effects as those obtained by impregnation in Example 1.
From FIG. 1, the filter paper regeneration time display material of Example 2 has a large change in fading rate, that is, a sharp color change from blue to colorless, and is excellent as a regeneration time display material.
On the other hand, the film-like reproduction time display material of Comparative Example 1 is inferior as a reproduction time display material because the change in fading rate is small and the color change from blue to colorless is slow.

  The regeneration time display material of the present invention is attached to the housing or case of the light regeneration type deodorant, and the regeneration of the indicator portion of the regeneration time display material and the regeneration of the deodorant can be performed at the same time. it can.

The relationship between the number of days (horizontal axis) and the fading rate (%) [vertical axis] of the reproduction time display materials of Example 2 and Comparative Example 1 is shown.

Claims (10)

  A display material for informing the regeneration timing of the light regenerating deodorant, wherein the sheet-like base material is impregnated with (A) a transition metal oxide having photochromism and (B) a water-soluble polymer compound, Or the reproduction | regeneration time display material of the optical reproduction type deodorizer characterized by providing the coating layer containing the said (A) component and (B) component on the surface of this sheet-like base material.   2. The regeneration time indicating material for a light regenerating deodorant according to claim 1, wherein the content ratio of the component (A) and the component (B) is 50: 1 to 1:50 in mass ratio. A sheet-like substrate, (A) component and (B) a component, the total amount of light reproduction type deodorant according to claim 1 or 2 impregnated composed so that 1 to 500 g / m ² that Reproduction time display material.   The photoregenerative deodorant according to claim 1 or 2, wherein a coating layer containing the component (A) and the component (B) is provided on the surface of the sheet-like substrate with a thickness of 0.1 to 10 µm. Reproduction time display material.   (A) The transition metal oxide having photochromism is at least one selected from oxides of metals belonging to Group 5 and Group 6 of the periodic table (long period type). Regeneration time display material of the light regeneration type deodorant as described.   (A) A component is a tungsten oxide and / or a molybdenum oxide, The reproduction | regeneration time display material of the optical reproduction type deodorizer in any one of Claims 1-5.   (B) The light according to any one of claims 1 to 6, wherein the water-soluble polymer compound is at least one selected from polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethylene oxide, polyacrylamide, and sodium polyacrylate. Regeneration time indicator for regenerative deodorants.   (B) A component is polyvinyl alcohol and / or polyethyleneglycol, The reproduction | regeneration time display material of the light reproduction type deodorizer in any one of Claims 1-7.   The light regeneration type deodorant is used in a refrigerator. The regeneration time indicating material for a light regeneration type deodorant according to any one of claims 1 to 8.   The reproduction | regeneration time display material of the light regeneration type deodorant in any one of Claims 1-9 affixed on a light regeneration type deodorant.

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