JP2003275288A - Deodorant and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deodorizing material which accomplishes excellent deodorizing performances for odors of ammonia, hydrogen sulfide, methyl thioalcohol, acetic acid, acetaldehyde and the like. <P>SOLUTION: A carrier 2 carries a deodorant composition containing a hydrazine derivative and a metallophthalocyanine complex. Preferably, the ratio by weight of the hydrazine derivative to the metallophthalocyanine complex is set at 75/25 to 95/5. The carrier 2 is immersed into a treatment agent containing the deodorant composition or preferably, the carrier 2 is coated with the treatment agent to produce the deodorizing material 1. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant material used as a deodorant sheet, a deodorant filter for an air conditioner or the like, and a method for producing the same.

[0002]

2. Description of the Related Art With the recent improvement of living environment, living odors such as ammonia, trimethylamine, hydrogen sulfide, methyl mercaptan, acetic acid and acetaldehyde are removed from the living space in order to ensure more comfortable living space. There is a strong interest in it.

In addition to such living odors, odors such as trimethylamine and methyl mercaptan remain in warehouses and containers for storing foods, and the residual odors are transferred to the foods to be stored next. There is a problem of reducing the commercial value, and there is a strong interest in removing such residual odor.

Various types of deodorant materials have been put on the market to solve such a problem of odor. For example, it is known that activated carbon is supported on the surface of the nonwoven fabric, but although such an adsorption type deodorant material has a sufficient fast-acting effect, it has a drawback that the deodorant effect has poor sustainability and a very short life. was there.

Therefore, in recent years, there have been proposed deodorant sheets obtained by supporting an iron phthalocyanine complex on a non-woven fabric, and those carrying a photocatalyst such as titanium oxide.

[0006]

However, the above-mentioned prior art has the following problems. That is, the former deodorant sheet in which the iron phthalocyanine complex is supported on the nonwoven fabric has not been sufficient in both deodorant performance and deodorant effect durability.

In addition, although the latter one carrying a photocatalyst has a feature that various odorous components can be decomposed at room temperature, the photocatalyst must be irradiated with ultraviolet rays of a specific wavelength in order to exert a decomposition action. There is a problem that the use environment as a deodorant is limited,
The deodorizing performance was also not sufficient.

The present invention has been made in view of the above technical background, and is capable of exhibiting excellent deodorizing performance against odors of ammonia, hydrogen sulfide, methyl mercaptan, acetic acid, acetaldehyde and the like. An object of the present invention is to provide a deodorant material that can maintain this excellent deodorant performance for a long time and a method for producing the same.

[0009]

[Means for Solving the Problems] The above object is to support a deodorant composition by treating the carrier with a treating agent containing a deodorant composition containing a hydrazine derivative and a metal phthalocyanine complex. This is achieved by a deodorant material characterized by being carried on the body.

According to the deodorant having the above structure, ammonia, hydrogen sulfide, methyl mercaptan, and hydrogen sulfide can be obtained by the synergistic action of the supported hydrazine derivative and the metal phthalocyanine complex.
The odor of acetic acid, acetaldehyde, etc. is sufficiently removed.
Further, the deodorant performance can be sufficiently maintained.

The weight ratio of hydrazine derivative / metal phthalocyanine complex in the above treating agent is 75/25 to 95/5.
The range is preferably When set in such a specific range, the synergistic action of the hydrazine derivative and the metal phthalocyanine complex is remarkably exhibited, and the deodorizing performance is remarkably improved.

The deodorant composition preferably further comprises a porous inorganic substance. Porous inorganic substances are excellent in the action of capturing odorous components, and the odorous components efficiently captured by this porous inorganic substance are sufficiently removed by the decomposition action of the hydrazine derivative / metal phthalocyanine complex. The deodorizing performance is improved by such a cooperative action.

Zeolite is preferably used as the porous inorganic substance. Zeolite has a particularly excellent adsorption and trapping ability, so that the deodorizing performance is further improved.

The deodorant composition preferably further contains a binder resin. Since other components in the deodorant composition (hydrazine derivative, metal phthalocyanine complex, porous inorganic substance, etc.) are firmly supported on the carrier by the binder resin, the components of these deodorant compositions from the carrier are Detachment is effectively prevented, and the durability of deodorant performance is further improved.

A cobalt phthalocyanine complex is preferably used as the metal phthalocyanine complex. If such a constitution is adopted, the deodorizing performance especially against methyl mercaptan and acetic acid is further improved.

The supported amount of the deodorant composition is preferably in the range of 0.1 to 10% by weight with respect to the carrier, from the viewpoint of ensuring sufficient deodorant performance without increasing the cost. .

When a non-woven sheet is used as the carrier, it can be used for building materials, for example, and since it is sheet-shaped, it does not take up space and can be flexibly deformed. Therefore, it can be applied to various uses and is excellent in versatility.

When a porous structure is used as the above-mentioned carrier, the contact surface area per unit volume is large, and therefore, for example, a deodorant filter for air conditioning equipment such as an air conditioner or a deodorant for various deodorizing devices. It can be suitably used as a filter or the like.

In the method for producing a deodorant according to the present invention, the carrier is immersed in a treatment agent containing a deodorant composition containing a hydrazine derivative and a metal phthalocyanine complex, and then the carrier is dried to remove the deodorant. The composition is carried on a carrier.

The deodorant produced by this production method is capable of sufficiently removing odors of ammonia, hydrogen sulfide, methyl mercaptan, acetic acid, acetaldehyde, and the like by the synergistic action of the supported hydrazine derivative and the metal phthalocyanine complex. The sustainability of performance is also good. Also,
Since the carrier is immersed in the treatment agent, the deodorant composition can be uniformly carried on the carrier.

In another method for producing a deodorant material of the present invention, a treatment agent containing a deodorant composition containing a hydrazine derivative and a metal phthalocyanine complex is coated on a sheet-shaped carrier and then dried. Thus, the deodorant composition is carried on a sheet-shaped carrier.

The deodorant material produced by the present production method is capable of sufficiently removing odors of ammonia, hydrogen sulfide, methyl mercaptan, acetic acid, acetaldehyde, etc. by the synergistic action of the supported hydrazine derivative and metal phthalocyanine complex, The sustainability of performance is also good. Also,
Since it is a coating method, the productivity can be remarkably improved, and the carried amount can be accurately controlled.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The deodorant material (1) according to the present invention is
The deodorant composition is supported on the carrier (2) by treating the carrier (2) with a treating agent containing a deodorant composition containing a hydrazine derivative and a metal phthalocyanine complex. The odor of ammonia, hydrogen sulfide, methyl mercaptan, acetic acid, acetaldehyde and the like can be sufficiently deodorized by the synergistic action of the supported hydrazine derivative and the metal phthalocyanine complex.

As the carrier (2), any carrier can be used as long as it can carry the deodorant composition, and examples thereof include a nonwoven fabric sheet and a porous structure.

The type of the non-woven fabric sheet is not particularly limited, and examples thereof include spun bond non-woven fabric, needle punched non-woven fabric, chemical bond non-woven fabric, and non-woven fabric manufactured by the melt blow method. The material of the fibers constituting these non-woven fabrics is not particularly limited, and examples thereof include synthetic fibers such as polyester, polyamide and polypropylene, regenerated fibers such as rayon, and natural fibers such as cotton and silk.
Further, the fibers constituting these non-woven fabrics may be short fibers or long fibers, and the length thereof is not particularly limited and the fiber thickness is not particularly limited.

As the porous structure, for example, a honeycomb structure, a resin foam, or flat sheets (3) and corrugated sheets (4) shown in FIGS. 1 and 2 are alternately laminated and integrated. A porous structure etc. can be illustrated.

Next, the deodorant composition used for constituting the deodorant material (1) of the present invention will be described. This deodorant composition contains a hydrazine derivative and a metal phthalocyanine complex as essential components. It goes without saying that other deodorants, odor scavengers, additives and the like may be used in combination with the hydrazine derivative and the metal phthalocyanine complex.

Examples of the hydrazine derivative include:
Examples thereof include those obtained by reacting a hydrazine compound with a long-chain aliphatic compound, and those obtained by reacting a hydrazine compound with an aromatic compound.

Among them, one or two compounds selected from the group consisting of hydrazine and semicarbazide, and a group consisting of monocarboxylic acids having 8 to 16 carbon atoms, dicarboxylic acids, aromatic monocarboxylic acids and aromatic dicarboxylic acids. A reaction product with one or more selected compounds, one or two compounds selected from the group consisting of hydrazine and semicarbazide, and a group consisting of a monoglycidyl derivative and a diglycidyl derivative having 8 to 16 carbon atoms. Reaction products with one or more compounds selected from the above are preferable. If such a hydrazine derivative is used, more excellent deodorant performance can be obtained. Specific examples of the reaction product include sebacic acid dihydrazide, dodecanedioic acid dihydrazide, and isophthalic acid dihydrazide, but are not particularly limited to these exemplified compounds.

The metal phthalocyanine complex is not particularly limited, but examples thereof include an iron phthalocyanine complex, a cobalt phthalocyanine complex, a nickel phthalocyanine complex, and a copper phthalocyanine complex. Among these, it is preferable to use a cobalt phthalocyanine complex, and in this case, especially methyl mercaptan,
There is an advantage that the deodorizing performance for acetic acid can be further improved.

The weight ratio of hydrazine derivative / metal phthalocyanine complex in the treating agent is 75/25 to 95/5.
The range is preferably When it is set in such a specific range, as is clear from the comparison data in the later examples, the synergistic effect of the hydrazine derivative and the metal phthalocyanine complex is remarkably expressed, whereas the deodorizing performance is significantly improved. However, if it deviates from these ranges, the deodorizing performance is lowered. Further, if the usage ratio of the metal phthalocyanine complex increases, the cost will increase, which is not preferable.

In the present invention, it is preferable that the deodorant composition further contains a porous inorganic substance. This porous inorganic substance is excellent in the action of capturing the odor component, and the odor component efficiently captured by this porous inorganic substance is sufficiently removed by the decomposition action of the hydrazine derivative / metal phthalocyanine complex, etc., The deodorizing performance is improved by such a linking action.

The porous inorganic substance is not particularly limited, but examples thereof include activated carbon and zeolite. Among them, it is preferable to use a zeolite having a particularly excellent adsorption and trapping ability, which makes it possible to further improve the deodorizing performance and also to improve the quick deodorizing effect.

Further, it is preferable that the deodorant composition further contains a binder resin, and this binder resin allows the other components (hydrazine derivative, metal phthalocyanine complex, porous inorganic substance, etc.) in the deodorant composition to be contained. Since it can be firmly supported on the carrier, separation of each component of these deodorant compositions from the carrier can be effectively prevented, and thus the durability of deodorant performance can be improved. There are advantages.

The binder resin is not particularly limited, and examples thereof include acrylic resin, methacrylic resin, urethane resin, silicone resin, glyoxal resin, vinyl acetate resin, vinylidene chloride resin, butadiene resin, melamine resin, epoxy resin, acrylic resin. Examples thereof include silicone copolymer resins, ethylene-vinyl acetate copolymer resins, isobutylene-maleic anhydride copolymer resins, ethylene-styrene-acrylate-methacrylate copolymer resins and the like. Two or more kinds of these resins may be mixed and used as a binder resin.

The amount of the deodorant composition supported on the carrier is preferably 0.1 to 10% by weight. 0.1
If it is less than 10% by weight, the deodorizing effect cannot be sufficiently obtained, and the effect is rapidly reduced, which is not preferable. On the other hand, if it exceeds 10% by weight, the cost increases, which is not preferable.

The deodorant material (1) according to the present invention can be manufactured, for example, as follows. First, a treating agent composed of an aqueous dispersion in which various components of the deodorant composition are dispersed in water is prepared. At this time, it is preferable to disperse these deodorant compositions as uniformly as possible. When a binder resin is used, it is preferable to form an emulsion state between the binder resin and water. As the dispersion medium, alcohol or the like can be used in addition to water, but water is preferable. The treatment agent may be mixed with various additives such as a dispersant and a thickener for improving the characteristics of the treatment agent.

The carrier is treated with the treating agent thus obtained to support the deodorant composition on the carrier.
The following two methods are suitable methods. The first production method is to support the deodorant composition on the carrier by immersing the carrier in a treatment agent and then drying the carrier. By adopting such an immersion method, the deodorant composition can be uniformly carried on the carrier, so that a high-quality deodorant can be manufactured.

The second manufacturing method is to coat the sheet-shaped carrier with the treating agent and then to dry the deodorant composition on the sheet-shaped carrier. Since the deodorant composition is applied by the coating method, the productivity can be remarkably improved and the carried amount can be controlled with high accuracy. The coating method is not particularly limited, and examples thereof include gravure roll processing, spray processing, roll coater processing, jet printing processing, transfer printing processing, and screen printing processing.

The drying means at the time of drying is not particularly limited, and may be air drying or heat treatment. Considering the efficiency of the drying treatment, drying by heat treatment is desirable. .

The treatment method is not particularly limited to the above-exemplified one, and, for example, a method of previously kneading the deodorant composition into the fibers constituting the non-woven sheet can be adopted.

The deodorant material (1) of the present invention can be used as:
Although not particularly limited, examples thereof include deodorant sheets for building materials, deodorant filters for air conditioners such as air conditioners, and deodorant filters for various deodorizing devices.

[0043]

EXAMPLES Next, specific examples of the present invention will be described.

Example 1 Sebacic acid dihydrazide 0.
After adding 45 parts by weight and 0.05 part by weight of cobalt phthalocyanine complex (sodium cobalt phthalocyanine polysulfonate) to 79.5 parts by weight of water, the mixture was stirred by a stirrer to obtain a dispersion liquid. A further 20 parts by weight of an acrylic resin (solid content: 50%) was added to this dispersion liquid and well stirred to obtain a uniform dispersion liquid (treatment liquid). A polyester spunbonded non-woven fabric (weight per unit area: 40 g / m ² ) was dipped in this treatment liquid, then taken out and squeezed with a mangle to dry it.
A deodorant sheet was obtained.

<Examples 2 to 7, Comparative Examples 1 and 2> A deodorant sheet was obtained in the same manner as in Example 1 except that the treatment agent having the constitution shown in Table 1 was used and the conditions shown in Table 1 were used. Got

[0046]

[Table 1]

<Example 8> As a carrier, a flat sheet (3) made of bleached kraft paper and a corrugated sheet (4) as shown in FIGS. Porous structure (43 mm x 55 mm)
(mm × thickness 12 mm) except that the deodorant material was obtained in the same manner as in Example 2.

<Example 9> A porous structure in which flat sheets and corrugated sheets made of bleached kraft paper as shown in FIGS. (Length 43 mm x width 55 mm x thickness 1
A deodorant material was obtained in the same manner as in Example 3 except that 2 mm) was used.

Example 10 0.45 parts by weight of dihydrazide sebacate and cobalt phthalocyanine complex (sodium cobalt phthalocyanine polysulfonate) 0.05
After adding 1 part by weight to 79.5 parts by weight of water, the mixture was stirred with a stirrer to obtain a dispersion liquid. A further 20 parts by weight of an acrylic resin (solid content: 50%) was added to this dispersion liquid and well stirred to obtain a uniform dispersion liquid (treatment liquid). This treatment liquid was dot-printed on a polypropylene non-woven fabric having a basis weight of 70 g / m ² (produced by the melt-blowing method) using a gravure roll processing machine, and then dried to obtain a deodorant sheet.

<Example 11> Example 1 was repeated except that the treating agent having the constitution shown in Table 2 was used under the conditions shown in Table 2.
A deodorant sheet was obtained in the same manner as in 0.

[0051]

[Table 2]

The deodorant performance of each of the deodorant materials produced as described above was evaluated according to the following test method. The results are shown in Tables 3 and 4.

<Deodorant Performance Test Method A (Performance Evaluation as Deodorant Sheet)> (Ammonia Deodorant Performance) Test pieces (10 × 10 cm square) cut out from each deodorant material were put in a bag having an internal capacity of 2 L. After the charging, ammonia gas was injected so that the concentration would be 100 ppm in the bag. The residual concentration of ammonia gas was measured 10 minutes after the injection, and the total amount of ammonia gas adsorbed and removed by each test piece was calculated from the measured value, and the ammonia gas removal rate (%) was calculated from this.

(Hydrogen sulfide deodorizing performance) Hydrogen sulfide gas was used in place of ammonia gas to obtain a concentration of 10 pp in the bag.
The removal rate (%) of hydrogen sulfide was calculated in the same manner as in the above-mentioned test except that the injection was performed so that m was obtained.

(Methyl mercaptan deodorizing performance) Except that methyl mercaptan gas was used instead of ammonia gas and the concentration was 10 ppm in the bag,
The removal rate (%) of methyl mercaptan was calculated in the same manner as in the above test.

(Acetic acid deodorizing performance) The acetic acid removal rate (%) was calculated in the same manner as in the above-mentioned test except that acetic acid gas was used instead of ammonia gas and the concentration was 10 ppm in the bag. .

(Acetaldehyde deodorizing performance) The acetaldehyde removal rate (%) was calculated in the same manner as in the above-mentioned test except that acetaldehyde gas was used instead of ammonia gas and the concentration was 10 ppm in the bag. .

Then, the removal rate of 95% or more is "A", the removal rate of 90% or more and less than 95% is "O", and the removal rate of 85% or more and less than 90% is " Δ ”, and the removal rate of less than 85% was evaluated as“ x ”.

[0059]

[Table 3]

<Deodorization Performance Test Method B (Performance Evaluation as Deodorization Filter)> A circular test piece (diameter 50 mm) cut out from each deodorization sheet was placed in a sample holder at an intermediate position of a long cylindrical tube. The odorous gas of the specified concentration was passed through from one end side of the cylindrical tube at a flow rate of 5 L per minute, and the gas concentration before passing through the sample holder and the gas concentration after passing through the sample holder were measured with a detector tube. The total amount of each odor gas adsorbed and removed by each test piece was calculated from the measured values, and the odor gas removal rate (%) was determined from this.

"◎" indicates that the removal rate is 70% or more,
Those with a removal rate of 50% or more and less than 70% were evaluated as “◯”, those with a removal rate of 45% or more and less than 50% were evaluated as “Δ”, and those with a removal rate of less than 45% were evaluated as “x”. .

The gas concentration before passing through the sample holder was set to 100 ppm for ammonia gas and 10 ppm for hydrogen sulfide, methyl mercaptan, acetic acid and acetaldehyde.

[0063]

[Table 4]

As is clear from Tables 3 and 4, the deodorant materials of Examples 1 to 11 according to the present invention have excellent deodorant performance against any of ammonia, hydrogen sulfide, methyl mercaptan, acetic acid and acetaldehyde. Can be demonstrated. In particular, the weight ratio of hydrazine derivative / metal phthalocyanine complex is 7
Examples 1 to 5 and 8 to 5/25 to 95/5
In No. 11, the deodorizing performance was remarkably excellent.

In contrast, in Comparative Example 1 using the metal phthalocyanine complex alone and Comparative Example 2 using the hydrazine derivative alone, sufficient deodorizing performance was not obtained.

[0066]

The deodorant material of the present invention can remove odors of ammonia, hydrogen sulfide, methyl mercaptan, acetic acid, acetaldehyde, etc. by the synergistic action of the hydrazine derivative and the metal phthalocyanine complex. Further, the deodorant performance can be sufficiently maintained.

When the weight ratio of the hydrazine derivative / metal phthalocyanine complex in the treatment agent is in the range of 75/25 to 95/5, the synergistic action of the hydrazine derivative and the metal phthalocyanine complex is remarkably exhibited, and the deodorant performance is improved. It can be greatly improved.

When the deodorant composition further contains a porous inorganic substance, the deodorant performance can be further improved.

When the porous inorganic substance is zeolite, the deodorizing performance can be further improved and the deodorizing effect can be sufficiently fast.

When the deodorant composition further contains a binder resin, it is possible to effectively prevent the deodorant composition from being released from the carrier, so that the durability of the deodorant performance is further improved. Can be made.

When the metal phthalocyanine complex is a cobalt phthalocyanine complex, the deodorizing performance for methyl mercaptan and acetic acid is further improved.

When the amount of the deodorant composition supported is in the range of 0.1 to 10% by weight based on the carrier, sufficient deodorant performance can be secured at a lower cost.

When a non-woven fabric sheet is used as a carrier, since it is sheet-shaped, it does not take up space and can be easily transformed into various shapes, so it can be applied to various uses. It is a deodorant with excellent versatility.

When the porous structure is used as the carrier, it has a large contact surface area and is suitable as a deodorizing filter for air conditioning equipment such as an air conditioner and a deodorizing filter for various deodorizing devices.

In the first production method of the present invention, the carrier is immersed in a treating agent containing a deodorizing composition containing a hydrazine derivative and a metal phthalocyanine complex, and then dried to form the deodorizing composition. Since it is carried on the carrier, the deodorant composition can be uniformly carried on the carrier.

In the second production method of the present invention, a treatment agent containing a deodorizing composition containing a hydrazine derivative and a metal phthalocyanine complex is coated on a sheet-shaped carrier and then dried to remove the agent. Since the odor composition is supported on the sheet-shaped carrier, the productivity can be remarkably improved and the amount of the carrier can be controlled with high precision, so that a high-quality deodorant can be manufactured at low cost.

In the above production method, the weight ratio of hydrazine derivative / metal phthalocyanine complex in the treating agent is 7
When it is in the range of 5/25 to 95/5, the synergistic action of the hydrazine derivative and the metal phthalocyanine complex is remarkably exhibited, and the deodorizing performance can be remarkably improved.

[Brief description of drawings]

FIG. 1 is a perspective view showing a deodorant material according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view taken along the line AA in FIG.

[Explanation of symbols]

1 ... Deodorant 2 ... Carrier 3 ... Flat sheet 4 ... Wavy sheet

Continued front page    (72) Inventor Yoshiharu Nishino             231-16 Ko, Minami-Nagai-cho, Nara F-term (reference) 4C080 AA06 BB02 CC01 HH05 HH09                       JJ03 JJ06 KK08 MM18 MM19                       NN04 NN23

Claims (12)

[Claims] 1. A deodorizing composition is supported on a carrier by treating the carrier with a treating agent containing a deodorizing composition containing a hydrazine derivative and a metal phthalocyanine complex. Characteristic deodorant material. 2. A hydrazine derivative / in the treating agent
The weight ratio of the metal phthalocyanine complex is 75/25 to 95 /
The deodorant material according to claim 1, which is in the range of 5. 3. The deodorant material according to claim 1, wherein the deodorant composition further contains a porous inorganic substance. 4. The deodorant material according to claim 3, wherein the porous inorganic substance is zeolite. 5. The deodorant material according to claim 1, wherein the deodorant composition further contains a binder resin. 6. The deodorant material according to claim 1, wherein the metal phthalocyanine complex is a cobalt phthalocyanine complex. 7. The amount of the deodorant composition supported is in the range of 0.1 to 10% by weight based on the carrier.
The deodorant material according to any one of 1. 8. The deodorant material according to claim 1, wherein a nonwoven fabric sheet is used as the carrier. 9. The deodorant material according to claim 1, wherein a porous structure is used as the carrier. 10. A carrier is immersed in a treatment agent containing a deodorizing composition containing a hydrazine derivative and a metal phthalocyanine complex, and then dried to support the deodorizing composition on the carrier. A method for producing a characteristic deodorant material. 11. A sheet-shaped carrier is coated with a treatment agent containing a deodorant composition containing a hydrazine derivative and a metal phthalocyanine complex, and then dried to form the sheet-shaped carrier with the deodorant composition. A method for producing a deodorant material, which comprises supporting the deodorant material. 12. The weight ratio of hydrazine derivative / metal phthalocyanine complex in the treating agent is 75/25 to 95.
The method for producing a deodorant material according to claim 10 or 11, which is in a range of / 5.