JPH09215737A - Deodorant and deodorizing member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant and deodorizing member which are long in life and low in the cost and are capable of efficiently removing malodorous components and have an excellent antimicrobial performance. SOLUTION: This deodorant contains a Ti oxide and SiO2 and further contains an Na compd. at 0.01 to 5.00wt.% in terms of Na and a K compd. at 0.01 to 5.00wt.% in terms of K. The content of the Ti compd. is preferably 30 to 40wt.% in terms of TiO2 and the content of the SiO2 10 to 50wt.%. The deodorization performance is further improved if the ignition loss (Ig.loss) measured after drying for one hour at 80 deg.C is 0.1 to 15.0wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a deodorant used for refrigerators and the like, which is used for removing hydrogen sulfide, methyl sulfides, organic amines, ammonia and the like, which cause malodor in the refrigerator, or for preventing the growth of various bacteria. And a deodorizing member.

[0002]

2. Description of the Related Art Conventionally, it is known that activated carbon is used as a deodorant in refrigerators and the like. However,
Since activated carbon has a short life as a deodorant and is frequently replaced, there has been an increasing demand for extending the life of the deodorant.

Therefore, a deodorizing method using ozone has been proposed (Japanese Patent Publication No. 5-86253, Japanese Patent Publication No. 5-281).
48). In this ozone deodorization method, ozone is generated by an ozone generator, and a malodorous component is catalytically decomposed using a catalyst in the presence of ozone.

A thermal decomposition deodorizing method using a platinum catalyst has also been proposed. The thermal decomposition deodorization method is a method in which a thermal decomposition catalyst such as platinum is applied to an adsorbent to adsorb the odor in the refrigerator for a certain period of time and then heated by a heater to decompose the odorous substance.

The ozone deodorizing method and the thermal decomposition deodorizing method can maintain the deodorizing ability for a long time as compared with the deodorizing agent using activated carbon.

[0006]

However, since the ozone deodorizing method requires an ozone generator and the thermal decomposition deodorizing method requires a heater for heating, the manufacturing cost of the deodorizing apparatus is high and the apparatus is large. There is a problem that it becomes a scale.

The present invention has been made in view of the above problems, and has a long service life and a low cost, can efficiently remove a malodorous component, and has an excellent antibacterial property, and a deodorant and a deodorant member. The purpose is to provide.

[0008]

Means for Solving the Problems The deodorant according to the present invention is
It is characterized by containing a Ti oxide and SiO ₂ , and further containing a Na compound in an amount of 0.01 to 5.00% by weight in terms of Na and a K compound in an amount of 0.01 to 5.00% by weight in terms of K. And

The loss on ignition (Ig.loss) measured after drying at 80 ° C. for 1 hour is 0.1 to 15.
It is preferably 0% by weight. Furthermore, it is preferred that some or all the SiO ₂ is added as a high-silica zeolite is SiO ₂ / Al ₂ O ₃ molar ratio of 5 or more.

Further, the content of Ti oxide is 30 to 40% by weight in terms of TiO ₂ , and the SiO ₂ content is 10.
It is preferably from 50 to 50% by weight.

Furthermore, manganese oxide is 5 to 30% by weight in terms of MnO, copper oxide is 1 to 10% by weight in terms of CuO, and magnesium oxide is 0.1 to 10% in terms of MgO.
It is preferable to contain 01 to 5.00% by weight and 0.001 to 15% by weight of Ag or a silver compound in terms of Ag.

The deodorizing member according to the present invention is characterized in that the deodorizing agent is applied to a carrier.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies conducted by the present inventors in order to solve the above-mentioned problems, Ti oxide, SiO ₂ , Na compound and K compound were used as components of a deodorant. It was found that the deodorizing performance can be improved and a long-life deodorant can be obtained by adjusting the content of the deodorizing agent to an appropriate amount. In addition, water of crystallization (Ig.l
If the manganese oxide, the copper oxide or the magnesium oxide and the proper amount of Ag are added, the deodorization efficiency is further improved.

The deodorant of the present invention can be used as it is in powder form, but it is preferable to use it as a molded product in the form of pellets or honeycombs. Further, in the present invention, the deodorizing member can also be constituted by applying a deodorizing agent in which the components and the composition are regulated to proper amounts to the carrier. Therefore, in the present invention, the chemical components and composition in the deodorant based on the total weight of the deodorant are defined.

The chemical components contained in the deodorant in the present invention and the reasons for limiting the composition thereof will be described below. However, the chemical composition is a value measured after drying the sample at 80 ° C. for 1 hour.

Na compound (Na conversion value): 0.01 to
5.00 wt% Na is a component that improves the deodorizing performance. N in deodorant
When the compound a is less than 0.01 wt% in terms of Na,
In particular, the deodorizing effect on acidic substances such as hydrogen sulfide decreases. On the other hand, the Na compound in the deodorant is 5.0 in Na conversion value.
When it exceeds 0% by weight, it reacts with the catalyst component and changes into an inactive substance, so that the deodorizing performance is deteriorated. Therefore, the Na compound content relative to the total weight of the deodorant is 0.01 to 5.00% by weight in terms of Na. The Na compounds include inorganic compounds such as sodium oxide, sodium peroxide, sodium carbonate, sodium phosphate, sodium chloride, sodium sulfate, sodium hydroxide and sodium perchlorate, and sodium citrate, sodium acetate and sodium oxalate. There are organic compounds such as.

K compound (K conversion value): 0.01 to 5.
00 wt% K, like Na, is a component that improves deodorizing performance. When the K compound in the deodorant is less than 0.01% by weight in terms of K value, the deodorizing effect on acidic substances such as hydrogen sulfide is particularly deteriorated. On the other hand, if the K compound in the deodorant exceeds 5.00% by weight in terms of K value, it reacts with the catalyst component and changes to an inactive substance, so that the deodorizing performance deteriorates. Therefore, the K compound based on the total weight of the deodorant is 0.0 in terms of K.
1 to 5.00% by weight. Examples of the K compound include inorganic compounds such as potassium oxide, potassium peroxide, potassium carbonate, potassium phosphate, potassium chloride, potassium sulfate, potassium hydroxide and potassium perchlorate, and potassium citrate, potassium acetate and potassium oxalate. There are organic compounds such as.

Ignition loss (Ig.loss): 0.1 to 15.
The 0% by weight loss on ignition can determine the amount of water of crystallization in minerals, and this water of crystallization has an effect of improving the deodorizing performance especially for water-soluble hydrogen sulfide and trimethylamine. When the loss on ignition is less than 0.1% by weight, the deodorizing performance with respect to hydrogen sulfide and trimethylamine deteriorates. On the other hand, when the loss on ignition exceeds 15.0% by weight, the strength required for forming a molded product decreases. Therefore,
The loss on ignition (Ig.loss) relative to the total weight of the deodorant is preferably 0.1 to 15.0% by weight.

The ignition loss (Ig.loss) is defined by JIS
As shown in the feldspar analysis method of M8853, it refers to the weight loss when a dried sample is ignited at 1000 ° C. to a constant weight.

Ti oxide (TiO ₂ conversion value): 30 to
The 40 wt% Ti oxide is a component that improves the deodorizing performance especially for basic gas. If the amount of Ti oxide in the deodorant is less than 30% by weight, the deodorizing performance especially against trimethylamine deteriorates. On the other hand, the Ti oxide content in the deodorant is 40% by weight.
When it exceeds, the strength required for forming a molded product decreases. Therefore, Ti oxide is T based on the total weight of the deodorant.
It is preferably 30 to 40% by weight in terms of iO ₂ .

SiO ₂ : 10 to 50 wt% SiO ₂ is a component that improves deodorizing performance. If the amount of SiO ₂ in the deodorant is less than 10% by weight, the deodorizing performance especially against methyl sulfide and trimethylamine deteriorates.
On the other hand, when the SiO ₂ content in the deodorant exceeds 50% by weight, the strength required for forming a molded article becomes insufficient, and
It becomes easy to powder. Therefore, Si based on the total weight of the deodorant
The O ₂ content is preferably 10 to 50% by weight.

The high-silica zeolite, which is a source of a part or all of this SiO ₂ , has the effect of improving the deodorizing performance for methyl sulfide. Therefore, it is desirable that a part of SiO ₂ or the whole is added to the high-silica zeolite is SiO ₂ / Al ₂ O ₃ molar ratio of 5 or more.

Mn oxide (MnO conversion value): 5 to 30
The wt% Mn oxide is a component that improves the deodorizing performance.
The coexistence of the Mn oxide and the copper oxide significantly improves the deodorizing performance. If the Mn oxide content in the deodorant is less than 5% by weight in terms of MnO, a sufficient deodorizing effect cannot be obtained. On the other hand, the Mn oxide content is 30 in terms of MnO.
When the content is more than weight%, the strength required for forming a molded product is lowered and the powder is easily pulverized. Therefore, the Mn oxide based on the total weight of the deodorant is 5 to 3 in MnO conversion value.
It is preferably 0% by weight.

Copper oxide (CuO conversion value): 1 to 10 layers
The amount% copper oxide is a component that improves deodorizing performance and antibacterial property, and as described above, the coexistence of copper oxide and Mn oxide significantly improves the deodorizing performance. When the copper oxide content in the deodorant is less than 1% by weight in terms of CuO, sufficient deodorizing and antibacterial effects cannot be obtained. On the other hand, when the Cu oxide content exceeds 10% by weight in terms of CuO, the strength required for forming a molded body is lowered and the powder is easily pulverized. Therefore, Cu oxide is CuO based on the total weight of the deodorant.
The converted value is preferably 1 to 10% by weight.

Mg oxide (MgO conversion value): 0.01
To 5.00 wt% Mg oxide is a component that improves antibacterial performance. If the Mg oxide content in the deodorant is less than 0.01% by weight in terms of MgO, a sufficient antibacterial effect cannot be obtained. on the other hand,
When the Mg oxide content exceeds 5.00% by weight in terms of MgO, the strength required for forming a molded body is lowered and the powder tends to be pulverized. Therefore, it is preferable that the Mg oxide content based on the total weight of the deodorant is 0.01 to 5.00 wt% in terms of MgO.

Silver or silver compound (Ag conversion value): 0.00
If 1 to 15% by weight of silver or a silver compound is added at the same time as Mg oxide, the interaction between the two can improve the antibacterial performance. The silver or silver compound in the deodorant is 0.00 in terms of Ag.
If it is less than 1% by weight, a sufficient antibacterial effect cannot be obtained. On the other hand, if the silver or silver compound exceeds 15% by weight in terms of Ag, the strength required for forming a molded article decreases and the powder is easily pulverized. Therefore, the silver or silver compound relative to the total weight of the deodorant is 0.001 to 15 in terms of Ag.
It is preferable to set the weight%. As the Ag in the deodorant, there are Ag-containing substances and the like in addition to Ag and Ag compounds.
The term "Ag-containing material" refers to a material obtained by exchanging ions in an ion exchanger such as zeolite and hydroxylapatite for Ag so as to contain Ag.

[0027]

EXAMPLES Examples of the deodorant according to the present invention will be specifically described below in comparison with its comparative example.

First, a deodorant was mixed with various components, and the chemical composition of each deodorant was analyzed. In the analysis of each chemical component, the sample was subjected to a drying treatment at 80 ° C. for 1 hour as a pretreatment and then analyzed by the method shown in Table 1 below.

[0029]

[Table 1]

Regarding the loss on ignition (Ig.loss),
As described above, in accordance with the feldspar analysis method of JIS M8853, the weight loss of the dried sample was measured when it was ignited at 1000 ° C. to a constant weight.

Next, each deodorant was evaluated for deodorizing performance, compressive strength and antibacterial performance. These evaluation methods are as follows.

The deodorizing performance was evaluated by using the deodorizing agent formed in honeycomb as a sample and using the deodorizing performance evaluation apparatus shown in FIG. As shown in FIG. 1, the gas supplied from the air cylinder 8 and the malodorous gas cylinder 7 is mixed by the gas mixer 6, and then the mixed gas is supplied into the constant temperature and humidity apparatus 2 via the flow meter 5. Are arranged as follows. An inlet concentration measuring device 3 and an outlet concentration measuring device 4 are arranged in the constant temperature and humidity device 2, and a sample 1 is arranged between the measuring devices 3 and 4.

Using the deodorizing performance evaluation apparatus thus constructed, the sample 1 is placed between the inlet concentration measuring instrument 3 and the outlet concentration measuring instrument 4 in the thermo-hygrostat 2, and the inlet concentration measuring instrument is used. The mixed gas is supplied from the side, and the malodor concentration at the inlet Ci (p
pm) and the malodor concentration at the outlet Co (ppm) were measured. However, the inlet malodor concentration Ci is 100 ppm, and the SV (Space Ve
The locity; space velocity) was 90,000 hr ^-1 , the temperature inside the apparatus 2 was 25 ° C, and the humidity was 60%. The SV is a volume of a malodorous gas that passes through in a unit time with respect to a unit catalyst volume, which is one of evaluation conditions for deodorizing performance, and can be calculated by the following mathematical formula 1.

[0034]

[Formula 1] SV (hr ^-1 ) = treatment gas amount (m ³ / hr) / catalyst amount (m ³ )

In this example, 1.7 liters / minute of a malodorous gas was flowed to a catalyst having a size of 12 mm and a thickness of 10 mm, and the deodorizing performance of Sample 1 was calculated by the following mathematical formula 2. .

[0036]

[Equation 2] Deodorizing performance = (1-Co / Ci) × 100 (%)

CH ₃ is used as a source of malodorous gas.
SH, H ₂ S, (CH ₃ ) ₂ S and (CH ₃ ) ₃ N are contained. For CH ₃ SH, H ₂ S and (CH ₃ ) ₃ N, deodorization performance of 80% or more is considered good. , (CH ₃ ) ₂ S, 70% or more was regarded as good, and 80% or more was regarded as the best.

Regarding the compressive strength, as shown in FIG. 2, honeycomb-formed 20 mm × 20 mm × 20 m
A sample 1 having a size of m was used, a load was applied in the ventilation direction, and the maximum load P (N) with respect to the cross-sectional area A (m ² ) of the sample when the sample 1 broke was measured. Then, the compressive strength σ of Sample 1 was calculated by the following mathematical formula 3.

[0039]

(3) Compressive strength σ = P / A (MPa)

Further, regarding the antibacterial performance, JIS Z291 was used under the condition that the culture temperature condition for evaluating the antibacterial performance was 6 to 10 ° C.
According to 1, the development of hyphae was visually evaluated. The molds used in this antibacterial performance test are shown in Table 2 below.

[0041]

[Table 2]

In this example, the sample was inoculated with hyphae, and if the growth of hyphae was not observed in that portion, the antibacterial performance was good (○), and the other ones were bad (x). And

The chemical components of the deodorant were analyzed in this manner, and the results of the analysis are shown in Tables 3 to 4 below, with all items falling within the scope of the present invention as examples. 5 shows. However, in the SiO ₂ / Al ₂ O ₃ molar ratio column of high silica zeolite in Table 4, − indicates that high silica zeolite is not used, and the value in parentheses is the high silica zeolite based on the total weight of the deodorant. The content of is shown.

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

As shown in Tables 3 to 5 above, Example N
o. 1 to 16 are all chemical components in the deodorant and Ig. l
Since the oss was within the range of the present invention, the deodorizing performance for all malodorous components was high, and the strength and antibacterial performance were excellent. In addition, Example No. 1 to 3, 7, 8, 10, 1
Since 2, 14 and 16 use high silica zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 5 or more, the deodorizing performance for methyl sulfide is further improved.

Next, the analysis results and evaluation results of Comparative Examples in which the Na and K contents are out of the range of the present invention among the chemical components in the deodorant are shown in Tables 6 to 8 below.

[0049]

[Table 6]

[0050]

[Table 7]

[0051]

[Table 8]

As shown in Tables 3 to 8 above, Comparative Example N
o. Since Nos. 17 and 19 had Na and K contents below the range of the present invention, the deodorizing performance for hydrogen sulfide was lower than that of the Examples. Also, in Comparative Example No. Regarding Nos. 18 and 20, since the Na and K contents exceeded the range of the present invention, the deodorizing performance was lowered for all malodorous components.

Next, Ig. Tables 9 to 11 below show the analysis results and evaluation results of comparative examples whose loss is outside the range of the present invention, that is, comparative examples not satisfying claim 2.

[0054]

[Table 9]

[0055]

[Table 10]

[0056]

[Table 11]

As shown in Tables 3 to 5 and 9 to 11, Comparative Example Nos. 21 is Ig. Since the loss was less than the range of the present invention, the deodorizing performance for water-soluble hydrogen sulfide and trimethylamine was decreased as compared with the examples. Also, in Comparative Example No. No. 22, Ig. los
Since s exceeds the range of the present invention, the compressive strength was lowered.

TiO ₂ which is an essential component in the deodorant is also used.
Tables 12 to 14 show the analysis results and evaluation results of Comparative Examples in which SiO ₂ and SiO ₂ are outside the scope of the present invention, that is, Comparative Examples not satisfying claim 3.

[0059]

[Table 12]

[0060]

[Table 13]

[0061]

[Table 14]

As shown in Tables 3 to 5 and 12 to 14, Comparative Example Nos. In No. 23, since the content of TiO ₂ is less than the range of the present invention, the deodorizing performance for the compressive strength trimethylamine is reduced as compared with the examples. On the other hand, in Comparative Example No. 24 and 26 had a TiO ₂ content exceeding the range of the present invention, so that the compressive strength was lowered. Also, in Comparative Example No. In No. 25, since the SiO ₂ content was less than the range of the present invention, the deodorizing performance for methyl sulfide and trimethylamine was lowered.

Further, among the chemical components in the deodorant, MnO,
Tables 15 to 17 below show the analysis results and evaluation results of comparative examples having CuO and MgO contents outside the range of the present invention, that is, comparative examples not satisfying at least one of claims 4 to 6.

[0064]

[Table 15]

[0065]

[Table 16]

[0066]

[Table 17]

As shown in Tables 3 to 5 and 15 to 17, Comparative Example Nos. No. 27 has a MnO content less than the range of the present invention, so the deodorizing performance is lower than in the Examples, and Comparative Example No. In No. 29, since the CuO content was less than the range of the present invention, the deodorizing performance and the antibacterial performance were deteriorated. Also, in Comparative Example No. In No. 31, the MgO content was less than the range of the present invention, so the antibacterial performance was lowered. On the other hand, Comparative Example N
o. Nos. 28, 30 and 32 had a MnO, CuO or MgO content exceeding the range of the present invention, so that the compressive strength decreased. Furthermore, among the chemical components in the deodorant, a comparative example in which the Ag content is out of the scope of the present invention, that is, in Claim 7,
Tables 18 to 20 below show the analysis results and evaluation results of the comparative examples that do not satisfy the above.

[0068]

[Table 18]

[0069]

[Table 19]

[0070]

[Table 20]

As shown in Tables 3 to 5 and 18 to 20, the comparative example Nos. In No. 33, since the Ag content was less than the range of the present invention, the antibacterial performance was lowered. Comparative Example N
o. For No. 34, the Ag content was beyond the range of the present invention, so the compressive strength decreased.

[0072]

As described in detail above, according to the present invention,
In the deodorant containing Ti oxide and SiO ₂ , N
Since the a and K contents are regulated to proper amounts, the malodorous components can be efficiently removed without using an auxiliary device other than the deodorant, and the life is long and the cost is low, and the antibacterial performance is An excellent deodorant and deodorizing member can be obtained. In addition, Ig. When the content of loss and other chemical components is regulated to an appropriate amount, deodorizing performance, strength and antibacterial performance are further improved.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a structure of a deodorizing performance evaluation device.

FIG. 2 is a schematic diagram showing a method for measuring compressive strength σ.

[Explanation of symbols]

 1; Sample 2; Constant temperature and humidity device 3, 4; Concentration measuring device 5; Flow meter 6; Gas mixer 7; Malodorous gas cylinder 8; Air cylinder

Claims (9)

[Claims] 1. A Ti compound and SiO ₂ are contained, and further, a Na compound is 0.01 to 5.00% by weight in terms of Na and a K compound is 0.01 to 5.00% by weight in terms of K. A deodorant characterized by containing. 2. The loss on ignition (Ig.loss) measured after drying at 80 ° C. for 1 hour is 0.1 to 1.
The deodorant according to claim 1, which is 5.0% by weight. Wherein some or all of the SiO ₂ is SiO ₂
A high silica zeolite having a molar ratio of / Al ₂ O ₃ of 5 or more is added as a high silica zeolite.
2. The deodorant according to 1. 4. The Ti oxide is 30 in terms of TiO _2.
The deodorant according to any one of claims 1 to 3, wherein the deodorant is 10 to 40% by weight and the SiO ₂ is 10 to 50% by weight. 5. The deodorant according to claim 1, further comprising 5 to 30% by weight of manganese oxide in terms of MnO. 6. The deodorant according to any one of claims 1 to 5, further comprising 1 to 10% by weight of copper oxide in terms of CuO. 7. The deodorant according to claim 1, further containing 0.01 to 5.00% by weight of magnesium oxide in terms of MgO. 8. The deodorant according to any one of claims 1 to 7, further comprising 0.001 to 15% by weight of Ag or a silver compound in terms of Ag. 9. A deodorizing member, characterized in that the deodorizing agent according to any one of claims 1 to 8 is applied to a carrier.