JP4669247B2 - filter - Google Patents

Description

  The present invention relates to a filter having a function of removing nitrogen oxides and / or sulfur oxides, and a mask using the same.

There are many substances that stimulate the respiratory tract and epidermis outdoors and indoors. Outdoors, air pollutants such as nitrogen dioxide (NO ₂ ) and sulfur dioxide (SO ₂ ) are listed. In particular, in recent years, with changes in transportation and distribution mechanisms, transportation means such as trucks and buses equipped with diesel engines have increased, and recreational vehicles equipped with diesel engines have also increased. A car equipped with a diesel engine has significantly more NO _X and SO _X emissions than a gasoline car, and thus air pollution in large urban areas has not been improved at all.

As a method for purifying exhaust gas containing NO _X and SO _X , Patent Document 1 describes a method and an apparatus for purifying exhaust gas using a titanium phosphate compound. However, a method capable of removing NO _X and SO _X a large apparatus without the need, moreover safely and efficiently is still sought.

By the way, it is already known that a phthalocyanine compound can be used as the NO _X sensor element (see Non-Patent Document 1). Patent Document 2 describes a deodorizing or deodorizing mask using a phthalocyanine compound.

JP 2004-130239 A Japanese Utility Model Publication No. 5-65354 Shiroyoshi Shirai and Nagao Kobayashi, "Phthalocyanine -Chemistry and Function-", published by IPC Inc., February 28, 1997, page 219

  The present invention has been made to solve the above-described problems, and an object thereof is to provide a filter having an excellent nitrogen oxide and / or sulfur oxide removing function, and a mask using the filter.

（式（ＩＩ）中、ＭはＦｅ、Ｃｏ、ＣｕおよびＮｉから選択される金属、Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ およびＲ ^４ は同一または異なるＣＯＯＨ基またはＳＯ _３ Ｈ基であり、ｎ１、ｎ２、ｎ３およびｎ４は０〜４で１≦ｎ１＋ｎ２＋ｎ３＋ｎ４≦８を満たす数）で示されるフタロシアニン化合物、またはその塩を担持した天然繊維、合成繊維、半合成繊維または再生繊維が含まれる硫黄酸化物除去繊維層を気体通過層とする請求項１に記載のフィルターである。 The filter according to claim 1, which has been made to achieve the above object, has the following chemical formula ( II ):

(In the formula ( II ), M is a metal selected from Fe, Co 2 , Cu and Ni , R ¹ , R ² , R ³ and R ⁴ are the same or different COOH groups or SO ₃ H groups, and n1, n2 , a phthalocyanine compound represented by the number) of n3 and n4 satisfying 1 ≦ n1 + n2 + n3 + n4 ≦ 8 0-4, or natural fibers carrying salt thereof, synthetic fibers, semisynthetic fibers or sulfur oxide that is part of the regenerated fibers The filter according to claim 1, wherein the removed fiber layer is a gas passage layer.

Also the invention described in claim 2, the formula (II) natural fiber that a phthalocyanine compound carrying 0.1 to 10% represented by the synthetic fiber, semi-synthetic fibers or sulfur oxide that is part of the regenerated fibers The filter according to claim 1, wherein the removed fiber layer is a gas passage layer.

Also the invention described in claim 3, a filter according to claim 1 for the formula (II) sulfur oxide removal fibrous layer of the phthalocyanine compound Ru includes carrying cellulose fibers represented by a gas passage layer is there.

Also the invention according to claim 4, filter according to claim 1, the apparent density of the sulfur oxide removal fibrous layer, characterized in that it is 0.04 g / cm ³ or more 0.2 g / cm ³ or less It is.

Also the invention of claim 5, before the Ki硫 yellow oxide removal fibrous layer, wherein the natural fibers carrying the phthalocyanine compound or a salt thereof, synthetic fibers, the weight ratio of semi-synthetic fiber or regenerated fiber is 30 wt% It is the above, It is a filter in any one of Claim 1 to 4 characterized by the above-mentioned.

Similarly, the invention according to claim 6 is a mask in which the sulfur oxide removing fiber layer according to any one of claims 1 to 5 is used as a human breath passage layer.

Similarly, the invention according to claim 7 has at least two layers of the human breath passage layer and an ultrafine fiber layer having an average fiber diameter of 10 μm or less, and the ultrafine fiber layer is disposed on the side close to the human skin. The mask according to claim 6 .

Similarly, in the invention according to claim 8 , a synthetic fiber layer having an average fiber diameter of more than 10 μm is disposed on one side or both sides of the breath passage layer of the person and the ultrafine fiber layer having an average fiber diameter of 10 μm or less. The mask according to claim 6 .
The invention according to claim 9 has an ultrafine fiber layer having an average fiber diameter of 10 μm or less as a saliva-impermeable or hardly-salivable layer, and has at least two layers of the human breath passage layer and the ultrafine fiber layer, The mask according to claim 6, wherein the ultrafine fiber layer is disposed on the side close to the human skin.

  The filter and mask of the present invention are used for removing nitrogen oxides and sulfur oxides safely and efficiently. Since the present invention adds a function of removing nitrogen oxides and sulfur oxides to the filter, nitrogen oxides and sulfur oxides can be efficiently removed without requiring a large-scale device, and production is also possible. Is also convenient.

The present invention gas passes through a nitrogen oxide (NO _X ) or / and sulfur oxide (SO _X ) -removed fiber layer containing natural fibers, synthetic fibers, semi-synthetic fibers or regenerated fibers carrying phthalocyanine compounds or derivatives thereof. It is a filter that forms a layer.

The filter of the present invention is a nitrogen oxide (NO _X ) containing natural fiber, synthetic fiber, semi-synthetic fiber or regenerated fiber carrying 0.1 to 10% by mass of the phthalocyanine derivative represented by the above formula (I) or / The sulfur oxide (SO _X ) -removed fiber layer may be a gas passage layer, and nitrogen oxide (NO _X ) or / and sulfur containing cellulose fibers carrying a phthalocyanine derivative represented by the above formula (I) The oxide (SO _X ) removal fiber layer may be a gas passage layer.

The natural fibers are preferably selected from cellulosic fibers such as cotton, hemp, wood pulp or bamboo pulp, and protein fibers such as wool or silk. The synthetic fiber is preferably selected from polyolefin fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyvinyl alcohol fibers, polyamide fibers, polyacryl fibers, polyester fibers, and polyurethane fibers. The semi-synthetic fiber is preferably a cellulosic fiber such as acetate rayon. The regenerated fiber is preferably selected from cellulosic fibers such as rayon exemplified by viscose rayon, solvent-spun rayon, and copper ammonia rayon. Examples of polyolefin fibers include polyethylene fibers and polypropylene fibers, examples of polyvinyl alcohol fibers include vinylon, examples of polyamide fibers include nylon, examples of polyester fibers include polyethylene terephthalate, and polyurethane fibers. Examples include spandex (registered trademark). Of these, cellulosic fibers are preferable, and rayon is particularly preferable. Since the cellulosic fiber is excellent in water retention, an environment in the presence of moisture can be easily created when the fiber carrying the phthalocyanine compound removes NO _X and SO _X. Moreover, if the said fiber is rayon, it not only is easy to carry | support a phthalocyanine compound, but it is excellent in the handleability at the time of producing a nonwoven fabric. The fineness of the fiber is not particularly limited, and varies depending on the type of fiber. For example, the fineness is 0.8 dtex to 10 dtex. When the fiber is rayon, the fineness is, for example, 0.8 dtex to 2.5 dtex.

The amount of the supported phthalocyanine compound may be 0.1% by mass or more and 10% by mass or less, preferably 0.3% by mass with respect to the natural fiber, synthetic fiber, semi-synthetic fiber or regenerated fiber. It may be 5% by mass or less, more preferably 0.5% by mass or more and 3% by mass or less. This is because if the amount of the phthalocyanine compound is 0.1% by mass or more and 10% by mass or less, the NO _X and SO _X removal ability is excellent, and the production of the fiber becomes easy or the cost is reduced.

  In addition to the natural fiber, synthetic fiber, semi-synthetic fiber or regenerated fiber carrying the phthalocyanine compound or derivative thereof, other fibers can be arbitrarily mixed in the gas passage layer. Examples thereof include natural fibers such as cotton, hemp, and pulp, recycled fibers such as viscose rayon, solvent-spun rayon, and cupra, synthetic fibers such as acrylic, polyester, polyamide, polyolefin, and polyurethane, and heat-adhesive synthetic fibers.

Moreover, the gas passage layer may contain fibers having other functionalities such as antibacterial properties and deodorizing properties as necessary. For example, the fiber having antibacterial properties includes a fiber carrying 0.1% by mass or more, preferably 1 to 5% by mass of metal ions such as copper, cobalt and iron. The content of the fibers having the antimicrobial is, for example, is 10 to 50 mass%, without compromising the removability of of the NO _X and SO _X of the nitrogen oxides and / or sulfur oxide removal fibrous layer, antibacterial Is preferable.

  The derivative of the phthalocyanine compound is preferably represented by the following chemical formula (II).

In the formula (II), M is a metal selected from Fe, Co, Cu and Ni, R ¹ , R ² , R ³ and R ⁴ are the same or different COOH groups or SO ₃ H groups, and n1, n2, n3 and n4 are numbers 0 to 4 that satisfy 1 ≦ n1 + n2 + n3 + n4 ≦ 8. In particular, R ¹ , R ² , R ³ and R ⁴ are the same and are a COOH group, and n1, n2, n3 and n4 are the same and are the compounds represented by the following chemical formula (III) Is more preferable.

In the formula (III), M is as described above, and more preferably Fe or Co.

  Although the said phthalocyanine compound can purchase a commercial item, it can also be manufactured by a conventionally well-known method. For example, iron phthalocyanine tetracarboxylic acid was obtained by adding trimellitic anhydride, urea, ammonium molybdate, and ferric chloride anhydride to nitrobenzene, stirring and heating to reflux to obtain a precipitate. The precipitate is obtained by adding an alkali to hydrolyze, and then adding an acid to make it acidic.

  As a method for supporting a metal phthalocyanine compound on natural fiber, synthetic fiber, semi-synthetic fiber or regenerated fiber, the gas passage layer may be formed after the metal phthalocyanine compound is previously supported on the fiber. After that, a metal phthalocyanine compound may be supported. As a method of supporting the metal phthalocyanine compound after forming the gas passage layer, a method of applying a metal phthalocyanine derivative solution containing a binder component to the gas passage layer by printing, spraying or using a coater, a fiber or a gas passage layer is used as the solution. There are methods such as soaking in a dye, direct dyeing, ion dyeing and other dyeing methods. For example, a cellulose fiber carrying a phthalocyanine compound can be produced by immersing a highly swellable cellulose fiber in an aqueous solution of the phthalocyanine compound.

  The gas passage layer is a mixture of natural fibers, synthetic fibers, semi-synthetic fibers or regenerated fibers carrying the phthalocyanine compound and other fibers as described above, if necessary, to produce ordinary woven fabrics and nonwoven fabrics. It can be manufactured by a method. As a manufacturing method of a nonwoven fabric, the hydroentanglement method; Thermal bond methods, such as an air through, a hot roll, and a heat embossing; Needle punch method is mentioned, for example.

Apparent density of the gas passage layer is preferably 0.04 g / cm ³ or more 0.2 g / cm ³ or less, more preferably 0.05 g / cm ³ or more 0.11 g / cm ³ or less. Within the apparent density of the range, it is possible to remove the NO _X and SO _X without compromising breathability. The apparent density can be calculated as follows from the fabric weight of the gas passage layer and the thickness at the time of 2.94 cN / cm ³ load.

Apparent density (g / cm ³ ) = weight per unit area (g / m ² ) / {thickness (mm) × 1000}

The nitrogen oxide or / and sulfur oxide-removed fiber layer may contain natural fibers, synthetic fibers, semi-synthetic fibers or regenerated fibers carrying a phthalocyanine compound or a derivative thereof, and the mass ratio of the fibers Is preferably 30% by mass or more. This is because, if the mass ratio is 30% by mass or more, the NO _X and SO _X removal properties are excellent. The mass ratio is more preferably 35% by mass or more. The mass ratio may be 100% by mass.

The filter of the present invention can be used as an air filter such as an air conditioner, a vacuum cleaner, and an air cleaner, and removes NO _X and SO _X that pass through the filter.

  In the mask of the present invention, the nitrogen oxide and / or sulfur oxide removing fiber layer described above is used as a human breath passage layer.

The nitrogen oxide and / or sulfur oxide removing fiber layer has the ability to remove NO _X and SO _X , but particularly in the presence of moisture, the ability to remove NO _X and SO _X. Will improve dramatically. However, if excessive moisture is present in the fiber layer so as to make it difficult to breathe when the mask is worn, the air permeability is remarkably lowered. In addition, when saliva generated by sneezing or coughing adheres to a natural fiber, synthetic fiber, semi-synthetic fiber or regenerated fiber carrying a phthalocyanine compound or a derivative thereof, a protein that is one of the components of saliva is adsorbed to the fiber. Thus, the function of removing NO _X and SO _X may be impaired.

The mask of the present invention uses the nitrogen oxide or / and sulfur oxide-removed fiber layer as a human breath passage layer, and includes at least a human breath passage layer and an ultrafine fiber layer having an average fiber diameter of 10 μm or less. It has two layers, and the ultrafine fiber layer is disposed on the side close to the human skin. The ultrafine fiber layer having an average fiber diameter of 10 μm or less is difficult to permeate saliva or does not permeate saliva, and therefore prevents saliva from coughing or sneezing from touching the nitrogen oxide or / and sulfur oxide removing fiber layer. , Suppresses a decrease in the ability to remove NO _X and SO _X. Furthermore, moisture contained in the breath released from the ultrafine fiber layer gives moisture to the nitrogen oxide and / or sulfur oxide removal fiber layer, so that the NO _X and SO _X removal properties of the fiber layer are improved, In addition, a mask with almost no breathing difficulty when worn can be obtained.

Apparent density of the person exhalation passage layer is preferably 0.04 g / cm ³ or more 0.2 g / cm ³ or less, more preferably 0.05 g / cm ³ or more 0.11 g / cm ³ or less. If the apparent density is 0.04 g / cm ³ or more, the human breath passage layer functions as a prefilter for the ultrafine fiber layer that is excellent in capturing foreign matters such as dust, and the voids due to the foreign matter in the ultrafine fiber layer Suppresses obstruction. When the apparent density is within the above range, it is difficult to feel breathlessness when wearing a mask.

  In the mask of the present invention, it is only necessary that the ultrafine fiber layer is disposed closer to the skin than the person's breath passage layer, and the other is between the person's breath passage layer and the ultrafine fiber layer. The fiber layer may be disposed.

  The fiber layer here includes, for example, one composed of one nonwoven fabric, two or more nonwoven fabrics laminated, one or more nonwoven fabrics and one or more fiber webs (fibers to be composed) In a state in which the fibers are closed and accumulated), and those that are joined by secondary processing, and those in which two or more fiber webs are stacked and joined by secondary processing. Further, the respective fiber layers may be simply overlapped, or may be bonded entirely or partially after being overlapped.

  A preferred form of the mask of the present invention is to further contain a heat-bonding synthetic fiber. The heat-bonding synthetic fiber is preferable when heat-sealing with an ultrasonic sewing machine or the like at the time of manufacturing the mask, and when the human breath-passing layer is a non-woven fabric, the strength of the non-woven fabric can be improved.

Examples of the heat-adhesive synthetic fiber include a single component type such as polypropylene fiber and polyethylene fiber, and a parallel type of polypropylene and polyethylene, and a core / sheath portion made of polypropylene / polyethylene (for example, “NBF (H ) "(Trade name) (Daiwabo Co., Ltd.)), polyester / polyethylene (for example," NBF (SH) "(trade name) (Daiwabo Co., Ltd.)), polyester / polypropylene, polyester / low-melting polyester, etc. A sheath type composite component type may be mentioned. As the thermoadhesive synthetic fiber, a composite component type is preferable, and a core-sheath type composite fiber is more preferable. This is because if the heat-adhesive synthetic fiber is a composite component type, the heat-adhesive synthetic fiber can be heat-bonded to improve the strength of the nonwoven fabric, so that it can be stably produced. The content of the heat-adhesive synthetic fiber is preferably 5 to 30% by mass, for example, because the nonwoven fabric strength and heat seal strength can be improved without impairing the NO _X and SO _X removal properties.

  The fineness of the heat-adhesive synthetic fiber is not particularly limited, and varies depending on the type of fiber. For example, the fineness is 1.5 to 3 dtex. Further, when the heat-adhesive synthetic fiber is a polypropylene fiber, the fineness is, for example, 1.5 dtex to 3 dtex, and when the heat-adhesive synthetic fiber is polypropylene / polyethylene, the fineness is, for example, 1.5 dtex to 3 dtex. It is.

  As the ultrafine fiber layer in the mask of the present invention, for example, a melt-blown nonwoven fabric, a spunbond nonwoven fabric, a non-woven fabric obtained by dividing a split-type composite fiber to express ultrafine fibers, and one component constituting a sea-island type composite fiber are eluted. A nonwoven fabric in which ultrafine fibers are expressed can be used. Among these, a melt blown nonwoven fabric is preferable. This is because the melt-blown nonwoven fabric is a dense nonwoven fabric with a low basis weight, so that it can physically remove dust and dust and has excellent air permeability, and therefore the mask of the present invention becomes more useful. . Note that the average fiber diameter is different from ordinary synthetic fibers produced by, for example, melt-roller stretching, such as a melt-blown nonwoven fabric.If the fineness is not always constant, the cross section of the nonwoven fabric is measured with an electron microscope or the like. It is enlarged and means an average of about 100 measured fiber diameters. Moreover, when the cross section of the ultrafine fiber that has been developed after splitting, such as a split-type composite fiber, is an irregular cross section, the cross section is regarded as a circular cross section because of its fineness.

The mask of the present invention preferably includes, for example, one or more melt-blown nonwoven fabrics as an ultrafine fiber layer and one or more phthalocyanine compound-supporting cellulose nonwoven fabrics as a human breath passage layer. Specifically, it is a mask including one phthalocyanine compound-supporting cellulose nonwoven fabric and one meltblown nonwoven fabric, and it is more preferable that the meltblown nonwoven fabric exists on the side close to the skin. This arrangement prevents the meltblown nonwoven fabric from becoming clogged due to clogged air in the case of dusty air. Further, it prevents the protein in saliva from adsorbing to the phthalocyanine compound-supporting cellulose non-woven fabric due to sneezing, coughing, etc., and reducing the NO _X and SO _X removal function.

  As said melt blown nonwoven fabric, what manufactured resin, such as a polypropylene, polyethylene, polybutene-1, and polyester, from a single component type and a composite component type is used, for example. The meltblown nonwoven fabric is usually a nonwoven fabric having a small fineness and containing fibers in a so-called ultrafine fiber region. Therefore, such a melt blown nonwoven fabric is preferable for physically removing dust, dust, pollen and the like as described above. The meltblown nonwoven fabric is preferably hydrophobic. The above-mentioned effect of not allowing permeation of saliva becomes more prominent, and water vapor generated when breathing through the nose or mouth can be permeated, so that appropriate moisture can be given to the breath passage layer of the person. It is.

  The mask of the present invention preferably includes a synthetic fiber layer having an average fiber diameter of more than 10 μm on one side or both sides of a human breath passage layer and an ultrafine fiber layer having an average fiber diameter of 10 μm or less. Examples of the synthetic fiber layer include a spunbond nonwoven fabric and a thermal bond nonwoven fabric including short fibers, and a spunbond nonwoven fabric is preferable. This is because the spunbond nonwoven fabric is low in cost and excellent in shape retention when used as a mask and after being used as a mask. As the spunbond nonwoven fabric, for example, a resin in which a resin such as polypropylene, polyethylene, or polyester is produced from a single component type or a composite component type is used, and polypropylene fibers are preferable. This is because the polypropylene fiber is low in cost, is hydrophobic, and has little fiber dropout.

  In the mask of the present invention, it is preferable that the synthetic fiber layer, the ultrafine fiber layer, and the human breath passage layer are arranged in this order from the side close to the skin. The synthetic fiber is preferably a so-called hydrophobic fiber having lower water retention than the human breath passage layer. By placing the synthetic fiber layer on the side close to the skin, when wearing a mask, moisture contained in breath when breathing from the nose or mouth, or moisture contained in saliva when sneezing or coughing, It is suppressed from being held by the fiber layer, and does not give discomfort to the mask wearer. Furthermore, since the synthetic fiber layer is a layer having an average fiber diameter larger than 10 μm, it has excellent breathability and does not give the wearer a short of breath.

  In the mask of the present invention, the synthetic fiber layer, the ultrafine fiber layer, the human breath passage layer, and the synthetic fiber layer may be disposed in this order from the side close to the skin. By disposing the synthetic fiber layer farthest from the skin, that is, on the inhalation side, it can function as a prefilter for the ultrafine fiber layer or the human breath passage layer.

  Specific examples of the mask of the present invention include, for example, one or more of the spunbond nonwoven fabric as a synthetic fiber layer, one or more of the phthalocyanine compound-supporting cellulose nonwoven fabric as a human breath passage layer, and the meltblown nonwoven fabric 1 as an ultrafine fiber layer. Those containing at least one sheet are preferred. In particular, it is more preferable that the spunbond nonwoven fabric, the meltblown nonwoven fabric, the phthalocyanine compound-supported nonwoven fabric, and the spunbond nonwoven fabric are arranged in this order from the side closest to the skin.

  In addition, the mask of the present invention only needs to include the breath passage layer of the person and the ultrafine fiber layer, and in addition, other sheets, for example, woven fabric such as gauze, nets, and electrets are optionally processed. You may laminate a nonwoven fabric. The human breath passage layer may be preliminarily provided with moisture within a range that does not impair air permeability.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

  Examples of manufacturing an air filter to which the present invention is applied are shown in Examples 1 and 2, and an example of manufacturing an air filter to which the present invention is not applied is shown in Comparative Example 1.

Example 1
(1) Production of cellulosic fiber carrying phthalocyanine compound For rayon (cellulosic fiber) having a temporary swelling degree of 300%, the bath ratio is 1:20, and the formula (III) [wherein M is Fe. The iron octacarboxylate phthalocyanine dyeing solution was prepared. The pH of the staining solution was adjusted to 10 by adding NaOH. In the overmeyer, the rayon and the staining solution were set, and 5 g / liter of sodium sulfate was added. Dyeing was performed at a temperature of 80 ° C. for 45 minutes. Acetic acid was added to stop the color. Oiling and drying were performed to obtain rayon fibers having a fineness of 2.2 dtex and a fiber length of 38 mm on which 1% by mass of the iron octacarboxylic acid phthalocyanine was supported.

(2) Manufacture of gas passage layer 80% by mass of the phthalocyanine compound-carrying rayon fiber, a heat-adhesive synthetic fiber having a sheath component of high-density polyethylene, a core component of polypropylene having a fineness of 2.2 dtex, and a fiber length of 51 mm 20% by mass of a composite fiber (manufactured by Daiwa Boseki Co., Ltd., “NBF (H)” (trade name)) was prepared, and a card web mixed uniformly was prepared using a card machine. Next, the card web is placed on the carrier support, and a high-pressure water stream is jetted from above the web at a water pressure of 3 MPa, the web is turned over, and a high-pressure water stream is jetted at a water pressure of 3 MPa, resulting in a basis weight of 50 g / m ² , 2 A hydroentangled nonwoven fabric having a thickness of 0.65 mm at a load of .94 cN / cm ² was produced. The amount of the phthalocyanine compound supported in the obtained gas passage layer is 1% by mass with respect to the cellulosic fiber, and the apparent density of the gas passage layer is 0.077 g / cm ^3. The mass ratio of the system fibers was 80% by mass.

(3) Manufacture of Air Filter As an ultrafine fiber layer, a polypropylene meltblown nonwoven fabric (Kuraray Co., Ltd., PC0020FH (trade name)) having an average fiber diameter of about 3 to 4 μm and a basis weight of 20 g / m ² was prepared. As a synthetic fiber layer arranged on both sides of the gas passage layer and the ultrafine fiber layer, a polypropylene spunbonded nonwoven fabric (Idemitsu Petrochemical Co., Ltd., RN) having a fineness of 3 to 4 dtex (average fiber diameter of 22 μm) and a basis weight of 20 g / m ² -2020 (trade name)).

  After each nonwoven fabric layer is cut into a size of 20cm in length x 80cm in width, it is laminated so as to become a spunbond nonwoven fabric layer, a meltblown nonwoven fabric layer, a gas passage layer, and a spunbond nonwoven fabric layer, and superimposed in three stages in the longitudinal direction. And the peripheral part of the nonwoven fabric layer was adhere | attached with the ultrasonic sewing machine, and the air filter was manufactured.

(Example 2)
As the gas passage layer, 40% by mass of the phthalocyanine compound-carrying rayon fiber and the rayon fiber (“Sniper” manufactured by Daiwabo Rayon Co., Ltd.) into which an anion group is introduced are immersed in an aqueous copper sulfate solution, washed with water, dehydrated and dried. Example 1 except that 40% by mass of antibacterial fibers (fineness 2.2 dtex, fiber length 38 mm) carrying about 1% by mass of the obtained copper ions and 20% by mass of the sheath-core type composite fiber were used. A gas passage layer was produced in the same manner as (2). An air filter was produced in the same manner as in Example 1 (3) except that the gas passage layer was used. The amount of the phthalocyanine compound supported in the obtained gas passage layer is 1% by mass with respect to the cellulosic fiber, and the apparent density of the gas passage layer is 0.073 g / cm ^3. The mass ratio of the cellulosic fibers was 40% by mass.

(Comparative Example 1)
Instead of the gas passage layer of Example 1, basis weight ^{50 g} / m 2, except that the thickness of an 2.94cN / cm ² load using a polyester nonwoven fabric of 0.65mm, the same procedure as in Example 1 (3) An air filter was manufactured.

(Evaluation)
1. NO _X and SO _X removal power The gas passage layer used in Examples 1 and 2 and the polyester nonwoven fabric used in Comparative Example 1 were used as samples, and the NO _X and SO _X removal powers were measured as follows.

Test method (SO ₂ )
The raw gas (SO ₂ ) was obtained by allowing 3 cc of 6N sulfuric acid to act on 2 g of metallic copper and collecting the generated gas by downward displacement. The capacity 5 liters pollution analysis bag (trade name Tedlar bag), placed in the magnitude of each sample in the vertical 10 cm × horizontal 10 cm, a mixture of the a raw gas (SO ₂₎ and odorless air, first SO ₂ Injection was performed so that the concentration was 30 ppm and the volume was 5 liters. The injection time was taken as the start time, and the SO ₂ concentration in the bag was measured with a gas detector tube every time.

Test method (NO ₂ )
The raw gas (NO ₂ ) was obtained by allowing 12 cc of 6N nitric acid to act on 2 g of metallic copper and collecting the generated gas by downward displacement. Put a sample 10cm long x 10cm wide in a pollution analysis bag (trade name Tedlar bag) with a capacity of 5 liters, mix the raw gas (NO ₂ ) and odorless air, and obtain the initial concentration of NO ₂ Of 30 ppm and a volume of 5 liters. The injection time was taken as the start time, and the NO ₂ concentration in the bag was measured with a gas detector tube every time.

  In addition, in order to reproduce the wet state of a gas passage layer, 80 mass% of water was wet with respect to the mass of a gas passage layer, and it was set as the time of wet.

  The measurement results are shown in Table 1.

From the obtained results, it was confirmed that the filter of the present invention was excellent in NO _X and SO _X removal power.

2. Antibacterial activity The antibacterial activity was measured as follows using the gas passage layer used in Example 2 and the polyester nonwoven fabric used in Comparative Example 1 as samples.

Test Method 1993 Journal of All Japan Hospital Association Vol. 5, no. 2, It carried out according to the evaluation method described in 192-196 pages. Specifically, a liquid containing a certain amount of bacteria is dripped onto a sample and cultured at 25 ° C. Immediately after dropping of the sample, 1 hour, 3 hours, 5 hours, and 24 hours later, One piece was taken out, extracted with PBS (phosphate buffered saline), the extracted solution was cultured, and the number of bacteria produced was measured (spot method).

  The measurement results are shown in Table 2.

  From the obtained results, the gas passage layer of Example 2 has a viable count reduced to 0.07% in 1 hour with respect to methicillin-resistant Staphylococcus aureus (MRSA), The antibacterial effect could be confirmed after 3 hours. On the other hand, in the nonwoven fabric of Comparative Example 1, the number of viable bacteria did not decrease even after 24 hours, and the antibacterial effect could not be confirmed.

  Next, an example in which a mask is manufactured using an air filter to which the present invention is applied is shown in Examples 3 and 4, and an example in which the arrangement of the breath exhalation layer of the mask of the present invention is changed is comparative example 2. Shown in

(Example 3)
The filter obtained in Example 1 was cut into a size of 9 cm (length) × 14.5 cm (width), and then the periphery was bonded together with an ear strap prepared in advance with an ultrasonic sewing machine to manufacture a mask.

Example 4
A mask was produced in the same manner as in Example 3 except that the filter obtained in Example 2 was used.

(Comparative Example 2)
A card web in which 50% by mass of the phthalocyanine compound-carrying rayon fiber and 50% by mass of the heat-adhesive synthetic fiber are mixed as a human breath-passing layer is heated and pressurized with an embossing roll / flat roll heated to 140 ° C. Thus, a hot embossed nonwoven fabric having a weight per unit area of 30 g / m ² and a thickness of 2.94 cN / cm ^{2 under} load of 0.35 mm was produced. A mask was produced in the same manner as in Example 3 except that the breath exhalation layer of the person was used to form a spunbond nonwoven fabric layer, a human breath passage layer, a meltblown nonwoven fabric layer, and a spunbond nonwoven fabric layer.

  When the masks of Example 3 and Example 4 were worn for 3 hours, they did not feel breathlessness. In addition, when a person's breath passage layer was taken out from the mask after wearing and confirmed, saliva or the like was not adhered, and the moisture content of the person's breath passage layer before and after wearing for 3 hours (of the mass of the nonwoven fabric before and after wearing) The value obtained by dividing the difference by the mass of the nonwoven fabric before wearing and multiplying by 100 was 50% by mass.

  When the mask of Comparative Example 2 was worn for 3 hours, the patient did not feel breathless, but when the breath passage layer of the person after wearing was taken out and confirmed, saliva was adhered.

The filter of the present invention was confirmed to be excellent in NO _X and SO _X removal power. In an environment where NO _X or SO _X exists outdoors or indoors, it can be effectively used as any filter for an air conditioner, a vacuum cleaner, an air cleaner, etc., and NO _X and SO _X can be efficiently removed. In addition, the mask using the filter of the present invention can be applied to a mask for preventing a disease considered to be caused by NO _X , SO _X, or the like.

Claims (9)

The following chemical formula ( II )

(In the formula ( II ), M is a metal selected from Fe, Co 2 , Cu and Ni , R ¹ , R ² , R ³ and R ⁴ are the same or different COOH groups or SO ₃ H groups, and n1, n2 , a phthalocyanine compound represented by the number) of n3 and n4 satisfying 1 ≦ n1 + n2 + n3 + n4 ≦ 8 0-4, or natural fibers carrying salt thereof, synthetic fibers, semisynthetic fibers or sulfur oxide that is part of the regenerated fibers A filter having a removed fiber layer as a gas passage layer. Formula (II) natural fiber that a phthalocyanine compound carrying 0.1 to 10% represented by the synthetic fibers, wherein the semi-synthetic fibers or Ru include regenerated fibers sulfur oxide removal fiber layer and the gas passage layer Item 10. The filter according to Item 1 . Filter according to claim 1, the sulfur oxide removal fibrous layer that is part of the carrying cellulose fibers phthalocyanine compound represented by Formula (II) and the gas passage layer. 2. The filter according to claim 1 , wherein an apparent density of the sulfur oxide-removed fiber layer is 0.04 g / cm ³ or more and 0.2 g / cm ³ or less. Claims before the Ki硫 yellow oxide removal fibrous layer, wherein the natural fibers carrying the phthalocyanine compound or a salt thereof, synthetic fibers, the weight ratio of semi-synthetic fiber or regenerated fiber is characterized in that at least 30 wt% The filter according to any one of 1 to 4 . The mask which uses the sulfur oxide removal fiber layer in any one of Claim 1 to 5 as a person's breath passage layer. 7. The apparatus according to claim 6 , comprising at least two layers of the human breath passage layer and an ultrafine fiber layer having an average fiber diameter of 10 μm or less, and the ultrafine fiber layer is disposed on the side close to the human skin. The mask described. According to claim 6, wherein said human exhalation passage layer, on one or both sides of the average fiber diameter 10μm or less of ultrafine fiber layer, further the average fiber diameter is arranged 10μm greater than the synthetic fiber layer mask of. An ultrafine fiber layer having an average fiber diameter of 10 μm or less is a saliva-impermeable or difficult-to-salivate layer, and has at least two layers of the human breath passage layer and the ultrafine fiber layer, and the ultrafine fiber layer is close to human skin The mask according to claim 6, wherein the mask is arranged on a side .