JP3906355B2 - Environmental protection composition - Google Patents

Description

【００２２】
【表２】

【００２３】
（４）塗料の調製
表１の実施例１２の試料を水及び有機系バインダーと混合して塗料を調製した。次いで、これをビルの外壁に塗布して３ヶ月放置したところ、本発明のアパタイトでは汚れが全く付かなかった。
更に、これを食品容器に塗布して、パンを入れて１週間放置したところ、市販品は黴が３日目から発生したが、本発明のアパタイトでは黴は発生しなかった。
【００２４】
【発明の効果】
以上詳述したように、本発明は、リン酸カルシウムクラスターが存在する擬似体液中で析出したことを特徴とする光活性のあるリンとカルシウムからなる化合物を含む環境浄化組成物、及び塗料に係り、本発明により以下のような効果が奏される。
（１）通常のリンとカルシウムからなる化合物と比べて、著しく活性が高い新規な光活性を有するリンとカルシウムからなる化合物を含む環境浄化組成物を提供することができる。
（２）上記組成物は、環境浄化材として十分な光活性を発現する。
（３）上記組成物は、吸着性、光活性及び生体親和性が高い。
（４）上記組成物は、抗菌・抗かび、脱臭、汚れ防止、大気や水の浄化作用を有する。
（５）上記組成物は、安全で無害であり、食品容器、人工観葉植物などの各種物品に塗布して使用することができる。
（６）上記組成物は、建材（外装、内装）、車両（自動車、列車）などに塗布して使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an environmental purification composition containing a compound composed of photoactive phosphorus and calcium, and more specifically includes a compound composed of phosphorus and calcium that expresses cell affinity, adsorption characteristics, and photoactivity. The present invention relates to an environmental purification composition.
The present invention also relates to a paint using the above-mentioned compound comprising phosphorus and calcium, which is useful for environmental purification and prevention of food corrosion.
In the present invention, the environmental purification composition is defined as a composition used for various types of environmental purification applications such as antibacterial / antifungal, deodorization, contamination prevention, and purification of air and water.
[0002]
[Prior art]
In recent years, products using apatite have attracted attention. Apatite has a function of adsorbing bacteria and proteins, and has been commercialized as, for example, an influenza prevention mask, a protein separation column, a hand cream, and the like using its characteristics. The function of adsorbing apatite nitrogen oxides and aldehydes is expected especially as an environmental purification material.
However, since apatite only adsorbs a substance and does not decompose, it has a disadvantage that it will saturate someday and stop functioning. Until now, it has been mainly a disposable method of use. Therefore, it has been difficult to use it as an environmental purification material, for example, for building materials.
[0003]
Furthermore, as a method for producing apatite, for example, as a method for producing metal-decorated apatite, apatite such as hydroxyapatite and a metal oxide having a photocatalytic action are combined, that is, one of the metal ions in the apatite crystal. A composite technique at the atomic level has been proposed, in which part is ion exchanged with a metal ion of a metal oxide having a photocatalytic action (for example, titanium ion in the case of titanium oxide) (Japanese Patent Laid-Open No. 2000-327315). . As a result, a metal oxide having a photocatalytic action is formed in the apatite crystal structure by ion exchange, thereby further developing the catalytic function exhibited by various apatites including calcium hydroxyapatite and developing a novel photocatalytic function. At the same time, there is provided a metal-modified apatite capable of maintaining an excellent specific adsorption property for a specific adsorbed substance such as an organic substance derived from apatite over a long period of time. However, this method has a fundamental problem that a photocatalytic function is hardly exhibited because a photocatalytic metal oxide such as titanium dioxide is compounded in the apatite crystal. Therefore, it becomes difficult to obtain sufficient photocatalytic activity necessary as an environmental purification material, etc., and the effect of the photocatalyst is diminished. is needed.
[0004]
On the other hand, a composite material in which apatite is coated on titanium dioxide having a photocatalytic action and applied as an environmental purification material has been proposed (Japanese Patent Laid-Open No. 10-244166).
This environmental purification material can be formed by immersing a substrate with titanium oxide film or titanium oxide particles in a simulated body fluid whose composition, pH, etc. are adjusted so that a porous calcium phosphate film is easily formed. it can. This is expected to be maintenance-free and semi-permanent because apatite adsorbs the substance and titanium dioxide decomposes it.
Furthermore, recently, it has been reported that hydroxyapatite itself has so-called photoactivity that activates oxygen under light irradiation to generate active oxygen. However, the photoactive function of this apatite can be confirmed by measuring it at the laboratory level, so to speak, so far, it is far from being applicable and practically cannot be used. . In any case, for this reason, in the art, it has been strongly desired to impart photoactivity to apatite having an adsorption function of various substances as a trump card for a new maintenance-free environmental purification material.
[0005]
[Problems to be solved by the invention]
In the situation as described above, the present inventor has found that these materials having higher activity compared to a compound composed of ordinary phosphorus and calcium can be used as an environmental purification material and the like, and further from the simulated body fluid. A compound of phosphorus and calcium such as apatite that has a plate-like or ribbon-like shape is significantly more active than a compound of phosphorus and calcium, and exhibits sufficient photoactivity as an environmental purification material. As a result, the present invention has been completed.
An object of the present invention is to provide an environmental purification composition containing a compound composed of phosphorus and calcium having an adsorption function and sufficient photoactivity for environmental purification.
Moreover, an object of this invention is to provide the coating material containing the compound which consists of the said phosphorus and calcium, and the articles | goods which apply | coated it.
[0006]
[Means for Solving the Problems]
The present invention for solving the above-described problems comprises the following technical means.
(1) a environmental remediation composition comprising a compound composed of phosphorus and calcium with a photoactive, 1) the compound, calcium phosphate clusters (Ca 9 _{(PO 4) 6)} which is precipitated in simulated body fluid present 2) a particle size of 1 nm to 10 microns and a specific surface area of 5 m ² / g or more, 3) a photo-oxidation degree obtained by measuring an oxygen absorption rate by a liquid phase oxidation reaction of tetralin is 2 or more, An environmental purification composition comprising a photoactive phosphorus and calcium compound characterized by having sufficient adsorptivity, photoactivity and biocompatibility as an environmental purification material.
(2) Composition of simulated body fluid ^{is, Na + 120~1000mM, K + 1~200mM} , Ca 2+ 0.5~50mM, Cl - 80~2000mM, HCO 3 - 0.5~300mM, HPO 4 2- 1~ One or more metal ions such as 200 mM, SO ₄ ² -0.1 to 200 mM, F ^- 0.5 mM, Fe, Cr, Zr, Al, etc. are 0.1 to 20 mM, as described in (1) above An environmental purification composition comprising a compound comprising phosphorus and calcium.
(3) The environmental purification composition comprising a compound comprising phosphorus and calcium according to (1) above, wherein the photoactivity obtained using the measured value of the photooxidation index as an index is 0.02 or more.
( 4 ) From the above (1), wherein the compound of phosphorus and calcium is calcium phosphate comprising at least one selected from hydroxyapatite, fluoroapatite, chloroapatite, tricalcium phosphate, and 8 calcium phosphate. 3 ) The environmental purification composition containing the compound which consists of phosphorus and calcium in any one.
( 5 ) A paint comprising the photoactive phosphorus and calcium compound according to any one of (1) to ( 4 ).
( 6 ) An article coated with a paint containing the phosphorous and calcium compound having photoactivity as described in ( 5 ) above.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in more detail.
The present invention comprises a photoactive phosphorus and calcium having a photoactivity of 2 or more, preferably 5 or more, more preferably 8 or more, and precipitated in a simulated body fluid in which a calcium phosphate cluster is present. It is an environmental purification composition containing the compound which consists of phosphorus and calcium in the shape of a plate or a ribbon. Moreover, this invention is articles | goods, such as these powders and thin films for apply | coating to articles | goods, or the coating material containing this, the building material which apply | coated these, artificial plants, and a food container.
[0008]
The compound comprising photoactive phosphorus and calcium according to the present invention will be described as follows with reference to preferred embodiments thereof, and the present invention is not limited to the following embodiments.
In the present invention, as specifically shown in the examples described later, the photoactivity can be measured, and the photoactivity can be quantified using the numerical value as an index.
If this photoactivity is 0.005 or more, it can adsorb and decompose organic chemicals at low concentrations of 1 ppm or less such as bacteria and viruses in the air and water, aldehydes, nitrogen oxides, pigments, It can be used as an environmental purification material. More preferably, if it is 0.02 or more, organic chemical substances having a concentration of 2 ppm or less can be adsorbed and decomposed, and more preferably 0.2 or more, most organic chemical substances can be adsorbed and decomposed. it can.
[0009]
Next, in the present invention, as shown in Examples described later, the photooxidation degree can be measured, and the photoactivity can be quantified using the numerical value as an index.
If the degree of photooxidation is 2 or more, it can adsorb and decompose organic chemicals at low concentrations of 1 ppm or less such as bacteria and viruses in the air and water, aldehydes, nitrogen oxides, pigments, etc. It can be used as a material. More preferably, if it is 5 or more, an organic chemical substance having a concentration of 2 ppm or less can be adsorbed and decomposed, and more preferably 8 or more, most organic chemical substances can be adsorbed and decomposed.
[0010]
For the production of such apatite, a method of precipitation in a simulated body fluid in which calcium phosphate clusters are present is used.
The simulated body fluid is obtained by dissolving NaCl, NaHCO ₃ , KCl, K ₂ HPO ₄ .3H ₂ O, MgCl ₂ .6H ₂ O, CaCl ₂ and Na ₂ SO ₄ or NaF, FeSO ₄ , FeCl _{3 and the} like in water. Prepared. Further, it is preferable to adjust the pH with HCl or _{(CH 2} OH) 3CNH 2 like 7-8, in particular 7.4.
The composition of the simulated body fluid used in the present invention is such that the composition of the simulated body fluid is Na ⁺ 120 to 1000 mM, K ^{+ 1 to} 200 mM, Ca ²⁺ 0.5 to 100 mM, Mg ²⁺ 0.5 to 50 mM, Cl ⁻ 80 to 2000 mM, ^{_{HCO 3 - 0.5~300mM, HPO 4 2-}} 1~200mM, SO 4 2- 0.1~200mM, F - 0.5mM, Fe, Cr, Zr, metal ions of one or more such as Al 0.1 ~ 20 mM is preferred. With this composition, the presence of calcium phosphate clusters (Ca ₉ (PO ₄ ) ₆ ) in the solution causes the clusters to assemble and produce a compound composed of phosphorus and calcium. If the concentration is lower than this, it takes time to precipitate the compound composed of phosphorus and calcium, and if the concentration is higher than this, the precipitation of the compound composed of phosphorus and calcium occurs suddenly, making it difficult to control the shape and particle size. Become.
[0011]
The temperature of the simulated body fluid is preferably 30 to 100 ° C. If the temperature is lower than this, it takes time to precipitate the compound composed of phosphorus and calcium, and if the temperature is higher than this, the particle size and the porosity cannot be controlled due to the evaporation of the simulated body fluid. Most preferably, the temperature is 30 to 60 ° C. The time is preferably 1 minute to 18 days. If the time is shorter than this, the precipitation of the compound composed of phosphorus and calcium is insufficient, and if the time is longer than this, the shape and the particle size become too large.
Photoactivity, shape and particle size can be controlled by changing the composition, temperature and time of the simulated body fluid. When the phosphorus or calcium content is reduced, the temperature is lowered, or the time is shortened, a compound composed of phosphorus and calcium having a small particle size is formed. When the content of phosphorus or calcium is increased or the temperature is increased, the particle size of the compound composed of phosphorus and calcium is increased. The photoactivity increases with a compound having a small particle size and a large specific surface area.
The compound composed of phosphorus and calcium thus precipitated may be amorphous or crystalline, and may be 3 calcium phosphate, 8 calcium phosphate, hydroxyapatite, fluoroapatite, chloroapatite, or the like. It may be calcium phosphate such as apatite, and is composed of one or more of these.
Moreover, when actually used, it may be used after being filtered or centrifuged and washed, or depending on the application, it may be used as it is or after being concentrated.
[0012]
As one form of the calcium phosphate by this invention, it can represent with the following general formulas, for example.
A _x (BO _y ) _z X, wherein A represents various metal atoms such as Ca, Co, Ni, Cu, Al, La, Cr, Fe, Mg, B represents an atom of P , X is a hydroxyl group (—OH), a halogen atom (eg, F, Cl), or the like. Examples of such calcium phosphate include, but are not limited to, apatite, hydroxyapatite, fluoroapatite, chloroapatite, tricalcium phosphate, calcium hydrogen phosphate, and the like. In the present invention, the apatite that can be suitably used is hydroxyapatite or fluorinated apatite in which X in the above formula is a hydroxyl group or fluorine, and more preferably, X in the above formula is a hydroxyl group, and A is It is apatite which is calcium (Ca). Furthermore, it may be partially substituted with Co, Ni, Cu, Al, La, Cr, Fe, Mg, or the like.
[0013]
Furthermore, the shape of the plate or ribbon is preferable because it is excellent in photocatalytic activity and adsorption function. Usually, for example, apatite has a shape like a hexagonal columnar pencil, but a plate shape is particularly preferable. However, since the shape is originally a hexagonal column, even if it is initially plate-like at the time of manufacture, it grows to become a hexagon when the particles grow. Therefore, if the shape of the originally generated particles is plate-like, the function is sufficiently exhibited even with a compound of phosphorus and calcium having a process shape that is going to be changed into a hexagonal prism shape and a halfway shape. For example, the ratio of the thinnest part to the longest part may be 1.2 or more. If it is smaller than this, the photoactivity becomes small, more preferably 1.5 or more.
[0014]
The smaller the particle size, the higher the activity and the better the biocompatibility. Therefore, a method of generating in a simulated body fluid from which a fine phosphorus and calcium compound is obtained is preferable. The compound of phosphorus and calcium prepared by this method has a small particle size and a large surface area, and therefore has very good adsorptivity, photoactivity and biocompatibility. The apatite according to the present invention thus obtained has an action of adsorbing proteins, amino acids, bacteria, viruses and the like and has good biocompatibility. The particle size is preferably 1 nm to 10 microns. If it is smaller than this, handling is difficult, and if it is larger than this, the photoactivity and the adsorptivity become worse. The specific surface area is preferably 5 m ² / g or more, and if it is smaller than this, the photoactivity and the adsorptivity deteriorate.
[0015]
The phosphorous and calcium compound thus produced is used as an environmental purification composition containing the same, and as a paint containing the same for antibacterial / antifungal, deodorizing, antifouling, purification of air and water, etc. Can do. For example, the paint can be applied to disposable food containers and trays such as polyethylene, tableware and lunch boxes to be used repeatedly, and kitchen equipment. Using these applied equipment, antibacterial, antifungal and deodorizing can be applied. effective. At this time, the binder may be organic or inorganic, and the paint may be mixed with a conventional paint. In particular, calcium phosphate is excellent in adsorption of bacteria and proteins, is safe and harmless, and can be applied to food containers and artificial houseplants. Therefore, the powder may be applied as it is, or may be mixed with an organic or inorganic binder to form a paint. Moreover, you may mix and use for resin, paper, a tile, ceramics, etc.
[0016]
[Action]
The present invention is an environmental purification composition comprising a photoactive phosphorus and calcium compound characterized by being precipitated in a simulated body fluid in which calcium phosphate clusters are present, and the compound preferably has a particle size of 1 nm to 10 microns, specific surface area of 5 m ² / g or more, photoactivity of 0.02 or more, photooxidation degree of 2 or more, high adsorptivity, photoactivity and biocompatibility, It exhibits antibacterial and antifungal, deodorizing, dirt prevention, and air and water purification.
[0017]
【Example】
Next, the present invention will be specifically described based on examples, but the present invention is not limited to the examples.
Example 1-17
(1) Photoactivity The photoactivity was measured as follows. In the experiment for depigmenting the dye, apatite was applied to glossy paper dyed with hematoporferrin, and the color change was measured by irradiating it with light.
For the paper to be dyed, the back side of the glossy film dedicated to EPSON Superfine for inkjet printers, SIGMA H-5518 for hematoporferin, 0.1% hematoporferin ethanol solution (0.1 g / 100 ml) using a special grade reagent for ethanol After immersing the film in, it was cut into 9 × 50 mm to obtain a sample. A halogen lamp light source device (manufactured by Ushio Electric Co., Ltd.) was used for light irradiation (light source device: model JCR12V-100WC, wavelength 380-460 nm, power 100 W, irradiation energy 204 mW / cm ² at the above wavelength) . As the color difference meter, OFC-300A (manufactured by Nippon Denshoku Industries Co., Ltd.) was used. Apply 40 mg of apatite 0.06% aqueous solution on paper, irradiate the tip of the optical cable of the irradiator with light at 3 mm for 1 minute, wash the sample piece with distilled water, wipe off the moisture well, and color difference meter Measured with This was repeated 5 times. The L * value was 61 before the experiment.
L * value after experiment−L * value before experiment / L * value before experiment was defined as photoactivity.
[0018]
(2) Photooxidation degree The photooxidation degree was measured as follows. Masuo, Kato Referring to the Industrial Chemical Journal, 1960, No. 5, pp 748-751, 20 ml of tetralin and 0.02 g of a compound consisting of phosphorus and calcium were sealed in a sealed heat-resistant glass reaction vessel with a capacity of 100 ml. While maintaining the reaction temperature constant, irradiation with ultraviolet rays was performed, and the oxygen absorption rate by the liquid phase oxidation reaction of tetralin was determined. That is, the pressure in the reactor at every predetermined time was read with a differential pressure gauge, and the change in pressure was taken as (mmH ₂ O / min) oxygen absorption rate as a measure of the photooxidation degree.
[0019]
(3) Preparation of compound consisting of phosphorus and calcium As simulated body fluid, NaCl, NaHCO ₃ , KCl, K ₂ HPO ₄ .3H ₂ O, MgCl ₂ .6H ₂ O, CaCl ₂ and Na ₂ SO ₄ or NaF, FeSO ₄ , FeCl _{3 and the} like, and distilled water were used to prepare an aqueous solution having a pH of 7.4 with the composition shown in Examples 1 to 17 in Table 1 and left.
In Table 1, compositions 1 to 9 of the simulated body fluid are as shown in 1 to 9 in Table 2 .
For comparison, commercially available hydroxyapatite manufactured by Wako Co., Ltd. was used. This was apatite with relatively good crystallinity, and the shape was spherical.
[0020]
As a result, as shown in Table 1, it was found that the apatite produced using the simulated body fluid showed a very large photocatalytic activity as compared with a commercially available product.
[0021]
[Table 1]

[0022]
[Table 2]

[0023]
(4) Preparation of paint A paint was prepared by mixing the sample of Example 12 in Table 1 with water and an organic binder. Next, when this was applied to the outer wall of the building and allowed to stand for 3 months, the apatite of the present invention was not stained at all.
Furthermore, when this was applied to a food container and left in a pan for 1 week, wrinkles occurred on the commercial product from the third day, but no wrinkles occurred in the apatite of the present invention.
[0024]
【The invention's effect】
As described above in detail, the present invention relates to an environmental purification composition containing a photoactive phosphorus and calcium compound characterized by being precipitated in a simulated body fluid in which calcium phosphate clusters are present, and a paint, The invention has the following effects.
(1) It is possible to provide an environmental purification composition containing a compound of phosphorus and calcium having a novel photoactivity that is significantly higher in activity than a compound of ordinary phosphorus and calcium.
(2) The composition exhibits sufficient photoactivity as an environmental purification material.
(3) The composition has high adsorptivity, photoactivity, and biocompatibility.
(4) The composition has antibacterial / antifungal, deodorizing, antifouling, and air and water purification actions.
(5) The composition is safe and harmless, and can be applied to various articles such as food containers and artificial houseplants.
(6) The composition can be applied to building materials (exterior, interior), vehicles (automobiles, trains) and the like.

Claims (6)

An environmental purification composition comprising a photoactive phosphorus and calcium compound, wherein 1) the compound is precipitated in a simulated body fluid in which calcium phosphate clusters (Ca ₉ (PO ₄ ) ₆ ) are present , 2) The particle size is 1 nm to 10 microns, the specific surface area is 5 m ² / g or more, 3) the degree of photooxidation obtained by measuring the oxygen absorption rate by the liquid phase oxidation reaction of tetralin is 2 or more, and the environmental purification material An environmental purification composition comprising a photoactive phosphorus and calcium compound, characterized by having sufficient adsorptivity, photoactivity and biocompatibility . The composition of the simulated body fluid ^{is, Na + 120~1000mM, K + 1~200mM} , Ca 2+ 0.5~50mM, Cl - 80~2000mM, HCO 3 - 0.5~300mM, HPO 4 2- 1~200mM, SO The phosphorus and calcium according to claim 1, wherein one or more metal ions such as ₄ ² -0.1 to 200 mM, F ^- 0.5 mM, Fe, Cr, Zr, and Al are 0.1 to 20 mM. An environmental purification composition comprising a compound comprising: 2. The environmental purification composition comprising a compound comprising phosphorus and calcium according to claim 1, wherein the photoactivity obtained by using the measured value of the photooxidation index as an index is 0.02 or more. Compounds of phosphorus and calcium, hydroxyapatite, fluorapatite, chloro apatite, tricalcium phosphate, in any one of claims 1 to 3, characterized in that the calcium phosphate consisting of one or more selected from phosphate 8 Calcium The environmental purification composition containing the compound which consists of description of phosphorus and calcium. A paint comprising the photoactive phosphorus and calcium compound according to any one of claims 1 to 4 . 6. An article to which a paint containing the phosphorous and calcium compound having photoactivity according to claim 5 is applied.