JP2011083756A - Aldehyde adsorbent and deodorizing fiber sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To inexpensively provide a deodorizing fiber sheet having performance of adsorbing VOC gases harmful to humans and aldehydes and aromatics contained in odors associated with daily living. <P>SOLUTION: An aldehyde adsorbent is used which comprises at least one zeolite selected from among types A and X, and a hydrazide compound. The weight ratio of the zeolite to the hydrazide compound is desirably in the range of 50:1 to 2:1. A fiber sheet is allowed to carry the aldehyde adsorbent to form a deodorizing fiber sheet. When the adsorbent contains a binder, the weight ratio of the zeolite to the binder is desirably in the range of 20:1 to 2:1. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an adsorbent composed of zeolite and a hydrazine derivative, and a deodorized fiber sheet carrying the adsorbent.

  Houses constructed in recent years have extremely high airtightness, and the effect of reducing the energy required for cooling and heating has been remarkably improved, but ventilation with natural airflow cannot be expected. This is also the case in automobiles, and manufacturers are making efforts to reduce VOC (volatile organic compound) gas generated from interior materials, adhesives essential for manufacturing, plastic moldings, and the like. VOC gas can be generated from any material, such as automobiles, home appliances, furniture, and housing materials, which are indispensable for the living environment of modern people.

On the other hand, various measures have been considered for living odors generated in the living environment surrounding us. For example, ammonia, hydrogen sulfide, mercaptan, aldehyde, acetic acid, and the like can be mentioned. Among them, ammonia, aldehyde, pyridine, and the like are taken up as typical malodors as components that cause tobacco odor.
In the VOC gas and the daily odor, aldehydes are a serious problem because they are particularly difficult to remove and their generation amount is large.

  Against this background, in recent years, there has been an increasing demand for products having an advanced deodorizing function. Taking textile products as an example, deodorant fibers (Patent Document 1) in which a poorly water-soluble hydrazide compound is kneaded into a fiber raw material, inorganic porous particles, zinc oxide, and a hydrazide compound are applied to a polyester fabric together with a binder and heat-treated. A deodorizing fabric (Patent Document 2) has been proposed. In addition, activated carbon materials and zeolites with finely controlled pore sizes have been actively developed. In particular, zeolite is being developed in a direction different from that of activated carbon, such as being able to realize monodispersed pores of various sizes depending on the synthesis conditions and further changing the properties of the pores by post-treatment.

  Zeolite is a crystalline aluminosilicate having a three-dimensional framework structure. As types of zeolite, there are A type, X type, Y type, L type, β type, ZSM-5 and the like. Of these, zeolites such as Y-type, β-type, and ZSM-5 are often used as gas adsorbents because of their excellent ability to adsorb gases such as aldehydes.

However, Y-type, β-type, ZSM-5 and the like have problems such as high synthesis temperature of zeolite and are expensive. When relatively inexpensive A-type and X-type zeolites are used, there is a problem that the gas adsorption capacity of aldehydes is not sufficient.
A relatively inexpensive deodorant product using a low-temperature synthesis and high industrial production and utilizing A-type and X-type zeolites has high economic merit and has been desired to be developed.

Japanese Patent No. 2818929 Japanese Patent No. 3605985

  In view of the above problems, an object of the present invention is to provide an inexpensive deodorized fiber sheet having adsorption performance for aldehydes and aromatics contained in VOC gas harmful to the human body and living odors.

As a result of intensive studies in order to achieve the above-mentioned problems, the inventors of the present invention have adsorbed aromatics inherent to zeolite by using a hydrazide compound in combination with at least one zeolite selected from A-type and X-type. The present invention was completed by finding that an adsorbent with dramatically improved adsorption performance of aldehyde compounds can be obtained without impairing the ability.
That is, the present invention is based on the following technique.

[1] An aldehyde adsorbent comprising at least one zeolite selected from A-type and X-type and a hydrazide compound.
[2] The aldehyde adsorbent according to [1], wherein a weight ratio of the zeolite to the hydrazide compound is in a range of 50: 1 to 2: 1.
[3] A fiber sheet on which the aldehyde adsorbent according to [1] is supported.
[4] The fiber sheet according to [3], wherein the adsorbent contains a binder, and the weight ratio of the zeolite to the binder is in the range of 20: 1 to 2: 1.

  By using a combination of A-type and X-type zeolites, which have been thought to have almost no ability to adsorb aldehydes, the hydrazide compound simply reacts with aldehydes to remove aldehyde gas. The present invention has been completed by finding out the performance of removing gas. The aldehyde adsorbent of the present invention has sufficient adsorption performance for aldehydes, and can be obtained industrially more advantageously than adsorbents made of zeolite such as Y-type, β-type, and ZSM-5, and is inexpensive. It becomes possible to provide.

  According to the inventions of the above [1] and [2], by using comparatively inexpensive zeolites such as A and X types, which have been evaluated to have a low adsorption effect on aldehydes, a remarkably high adsorption An adsorbent having performance can be produced.

  According to the inventions of [3] and [4], a deodorant fiber sheet having excellent durability can be produced, and various deodorant products are provided by cutting, molding, bonding, and sewing to an appropriate size. it can. In addition, a honeycomb filter can be manufactured by applying pleats and corrugated sheet processing.

  The present invention is an aldehyde adsorbent comprising at least one zeolite selected from A-type and X-type and a hydrazide compound, and a deodorant fiber sheet characterized by supporting the adsorbent.

[1. Zeolite]
The zeolite in the present invention is an A-type or X-type zeolite having a three-dimensional framework structure which is a crystalline aluminosilicate. A type and X type zeolites are produced, for example, by a hydrothermal synthesis method using a silica source such as sodium silicate, an alumina source such as sodium aluminate, a mineralizer such as sodium hydroxide and a raw material containing water. Can be manufactured. A-type and X-type zeolites are Y-type and β-type, and ZSM-5 and the like have lower synthesis temperatures during production than zeolites.
The average particle size of the zeolite used in the present invention is desirably 10 μm or less.

[2. Hydrazide Compound]
Examples of the hydrazide compound used in the present invention include form hydrazide, acetohydrazide, propionic acid hydrazide, lauric acid hydrazide, stearic acid hydrazide, salicylic acid hydrazide, benzoic acid hydrazide, p-hydroxybenzoic acid hydrazide, methylcarbazate, ethylcarbamate. Monohydrazide such as zet, semicarbazide hydrochloride, carbohydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, azelaic acid dihydrazide Terephthalic acid dihydrazide, isophthalic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, ita Acid dihydrazide, dodecanediohydrazide, hexadecanediohydrazide, 2,6-naphthoic acid dihydrazide, 1,4-naphthoic acid dihydrazide, 4,4'-bisbenzenedihydrazide, 2,6-pyridinedihydrazide, 1,4-cyclohexanedihydrazide Dihydrazides such as N, N′-hexamethylene bissemicarbazide, trihydrazide citrate, trihydrazide pyromellitic acid, 1,2,4-benzenetrihydrazide, nitriloacetic acid trihydrazide, trihydrazide such as cyclohexanetricarboxylic acid trihydrazide, Tetrahydrazides such as ethylenediaminetetraacetic acid tetrahydrazide and 1,4,5,8-naphthoic acid tetrahydrazide can be used. In particular, a hydrazide compound having two or more hydrazino groups is preferred.
In general, the hydrazine compound and acetaldehyde gas undergo an adsorption reaction with the following chemical formula.
-NH2 + CH3CHO → -NH (OH) CHCH3

[3. Base material]
The base material which comprises the fiber sheet of this invention is not specifically limited, For example, the base material which consists of natural fiber or a synthetic fiber can be used.

  Examples of natural fibers include cellulose fibers such as cotton, hemp, viscose rayon and cupra rayon; protein fibers such as wool and silk; natural polymer fibers such as algin fibers, chitin fibers and mannan fibers; Examples thereof include blended natural fibers composed of more than one kind of natural fibers.

  Synthetic fibers include, for example, polyamide fiber, nylon, polyester fiber, polyacrylonitrile fiber, polyvinyl alcohol fiber, polyolefin fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, polyurethane fiber, and polyurea fiber. A fiber etc. can be mentioned. Moreover, the water-absorbing synthetic fiber which provided water absorbency to these synthetic fibers, and the hydrophilic synthetic fiber which provided hydrophilicity can also be used.

As the water-absorbing synthetic fiber, water absorption performance is obtained by a method of imparting water absorption by a method in which a hydrophilic compound is kneaded and copolymerized in the synthetic fiber (chemical method), or by making the shape into an irregular cross section or a microporous structure. Can be obtained.
The hydrophilic synthetic fiber can be obtained by modifying the surface of the synthetic fiber to be hydrophilic by treatment with laser, plasma, electron beam or the like.

  In addition, the shape of the fabric is not particularly limited, such as a woven fabric, a knitted fabric, a nonwoven fabric, a three-dimensional fabric such as a tufted carpet or a moquette. These fabrics can be used in combination of one or more of the above fibers.

<Adsorbent>
The adsorbent consists of a zeolite and a hydrazide compound. The adsorbent can be produced, for example, by drying a treatment liquid in which zeolite and a binder resin are dispersed in a solvent. Further, as will be described later, the adsorbent may be directly formed on the substrate by drying the treatment liquid on the substrate.
The hydrazide compound only needs to be supported / present on the zeolite, for example, may be adhered to the surface of the zeolite, or may be in the pores present in the zeolite.

<Fiber sheet manufacturing method>
The method for causing the zeolite and hydrazide compound to exist on the surface and / or inside of the substrate is not particularly limited. For example, the treatment liquid in which zeolite is dispersed in a solvent is adhered to at least a part of the dough, and then dried. Can be manufactured. Alternatively, a treatment liquid in which zeolite and a binder are dispersed in a solvent may be used. At this time, when the zeolite and the binder resin are used as the treatment liquid, it is preferable to disperse the binder resin as much as possible.

The weight ratio of zeolite to hydrazide compound is preferably 50: 1 to 2: 1, more preferably 25: 1 to 4: 1.
When the weight ratio of zeolite to hydrazide compound exceeds 50: 1, the adsorption ability of acetaldehyde gas may be insufficient, and when it is less than 2: 1, the adsorption ability of other gases such as toluene gas may be insufficient. is there.

The binder resin is not particularly limited, and any kind of resin can be used. For example, acrylic resin, methacrylic resin, urethane resin, polyvinyl alcohol resin, silicon resin, and the like can be given. Two or more of these resins may be mixed. The weight ratio of the zeolite to the binder is preferably in the range of 20: 1 to 3: 1 from the viewpoint of the sticking property of the zeolite or hydrazide compound and the gas adsorption performance.
It is preferable to disperse the binder resin after dispersing the hydrazide-treated zeolite in the solvent in advance before blending.

  Examples of the method for supporting the treatment liquid on the dough include a dipping method and a coating method. As the dipping method, there is a method in which the dough is dipped in the treatment liquid, then squeezed with mangle and dried. If produced by this dipping method, the hydrazide-treated zeolite and the binder resin can be uniformly fixed to the dough.

  Examples of the coating method include a method in which the treatment liquid is applied and coated on at least a part of the dough and then dried. If it manufactures by the coating method, productivity can be improved notably and there exists an advantage which can control a sticking amount with high precision.

  Specific methods of the coating method are not particularly limited, and examples include gravure roll processing, spray processing, roll coater processing, transfer printing processing, screen printing processing, and the like.

  In addition to the above method, the deodorized dough can be thermoformed, or hydrazide-treated zeolite can be added to the plastic film or the surface of the molded body and the inside using the above-described coating technique.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Example 1]
Disperse 23.72g of A-type zeolite (Union Showa Molecular Sieve 4A, particle size of 10 microns or less) in 51.38g of distilled water, dissolve 1.19g of carbodihydrazide (Nippon Finechem, product name CDH), and stirrer at 20 ° C for 5 minutes. Stir with. A 10% aqueous solution of PVA binder (Denkapoval K-17EF manufactured by Denki Kagaku Kogyo) was prepared, 23.72 g was added to the aqueous solution, and the mixture was stirred for 30 minutes.
A cotton non-woven fabric (Nisshinbo 100% cotton non-woven fabric, weight per unit: 42.58g / m2, AM2040) is dipped in the above treatment solution, squeezed with mangle, dried and fixed with a pin tenter dryer at 120 ° C. Thus, a hydrazide-treated zeolite-impregnated nonwoven fabric was obtained.

[Example 2]
23.44 g of zeolite A (same as above) was dispersed in 50.78 g of distilled water, 2.34 g of carbodihydrazide (same as above) was dissolved, and stirred with a stirrer at 20 ° C. for 5 minutes. A 10% aqueous solution of PVA binder (same as above) was prepared, 23.44 g of the aqueous solution was added, and the mixture was stirred for 30 minutes.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment liquid, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a hydrazide-treated zeolite-impregnated nonwoven fabric was obtained.

Example 3
22.06 g of A-type zeolite (same as above) was dispersed in 51.47 g of distilled water, 4.40 g of carbodihydrazide (same as above) was dissolved, and stirred with a stirrer at 20 ° C. for 5 minutes. A 10% aqueous solution of PVA binder (same as above) was prepared, 22.06 g of the aqueous solution was added, and the mixture was stirred for 30 minutes.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment liquid, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a hydrazide-treated zeolite-impregnated nonwoven fabric was obtained.

Example 4
20.83 g of zeolite A (same as above) was dispersed in 52.08 g of distilled water, 6.25 g of carbodihydrazide (same as above) was dissolved, and stirred with a stirrer at 20 ° C. for 5 minutes. A 10% aqueous solution of PVA binder (same as above) was prepared, and 20.83 g was added to the aqueous solution, followed by stirring for 30 minutes.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment liquid, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a hydrazide-treated zeolite-impregnated nonwoven fabric was obtained.

Example 5
23.72 g of X-type zeolite (Union Showa Molecular Sieve 13X, particle size of 10 microns or less) was dispersed in 51.38 g of distilled water, 1.19 g of carbodihydrazide (same as above) was dissolved, and stirred with a stirrer at 20 ° C. for 5 minutes. A 10% aqueous solution of PVA binder (same as above) was prepared, 23.72 g of the aqueous solution was added, and the mixture was stirred for 30 minutes.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment liquid, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a hydrazide-treated zeolite-impregnated nonwoven fabric was obtained.

Example 6
23.44 g of X-type zeolite (same as above) was dispersed in 50.78 g of distilled water, 2.34 g of carbodihydrazide (same as above) was dissolved, and stirred with a stirrer at 20 ° C. for 5 minutes. A 10% aqueous solution of PVA binder (same as above) was prepared, 23.44 g of the aqueous solution was added, and the mixture was stirred for 30 minutes.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment liquid, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a hydrazide-treated zeolite-impregnated nonwoven fabric was obtained.

Example 7
X-type zeolite (same as above) (22.90 g) was dispersed in distilled water (49.61 g), carbodihydrazide (same as above) (4.58 g) was dissolved, and the mixture was stirred at 20 ° C. for 5 minutes. A 10% aqueous solution of PVA binder (same as above) was prepared, 22.90 g of the aqueous solution was added, and the mixture was stirred for 30 minutes.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was dipped in the treatment liquid, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a hydrazide-treated zeolite-impregnated nonwoven fabric was obtained.

Example 8
22.39 g of X-type zeolite (same as above) was dispersed in 48.51 g of distilled water, 6.72 g of carbodihydrazide (same as above) was dissolved, and stirred with a stirrer at 20 ° C. for 5 minutes. A 10% aqueous solution of PVA binder (same as above) was prepared, 22.39 g of the aqueous solution was added, and the mixture was stirred for 30 minutes.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was dipped in the treatment liquid, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a hydrazide-treated zeolite-impregnated nonwoven fabric was obtained.

[Reference Example 1]
Y type zeolite (Union Showa molecular sieve USKY-700, particle size 10 microns or less) 22.81g was dispersed in distilled water 53.23g, carbodihydrazide (same as above) 1.14g was dissolved and stirred with a stirrer at 20 ° C for 5 minutes. . A 10% aqueous solution of PVA binder (same as above) was prepared, and 22.81 g was added to the aqueous solution, followed by stirring for 30 minutes.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment liquid, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a hydrazide-treated zeolite-impregnated nonwoven fabric was obtained.

[Reference Example 2]
22.56 g of Y-type zeolite (same as above) was dispersed in 52.63 g of distilled water, 2.26 g of carbodihydrazide (same as above) was dissolved, and the mixture was stirred with a stirrer at 20 ° C. for 5 minutes. A 10% aqueous solution of PVA binder (same as above) was prepared, 22.56 g of the aqueous solution was added, and the mixture was stirred for 30 minutes.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment liquid, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a hydrazide-treated zeolite-impregnated nonwoven fabric was obtained.

[Comparative Example 1]
22.27 g of zeolite A (same as above) was dispersed in 55.46 g of distilled water and stirred with a stirrer at 20 ° C. for 5 minutes. A 10% aqueous solution of PVA binder (same as above) was prepared, and 22.27 g was added to the aqueous solution, followed by stirring for 30 minutes.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment solution, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a zeolite-impregnated nonwoven fabric was obtained.

[Comparative Example 2]
X-type zeolite (same as above) (23.00 g) was dispersed in 54.0 g of distilled water and stirred with a stirrer at 20 ° C. for 5 minutes. A 10% aqueous solution of PVA binder (same as above) was prepared, 23.00 g of the aqueous solution was added, and the mixture was stirred for 30 minutes.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment solution, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a zeolite-impregnated nonwoven fabric was obtained.

[Comparative Example 3]
20.00 g of Y-type zeolite (same as above) was dispersed in 60.00 g of distilled water and stirred with a stirrer at 20 ° C. for 5 minutes. A 10% aqueous solution of PVA binder (same as above) was prepared, 20.00 g was added to the aqueous solution, and the mixture was stirred for 30 minutes.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment solution, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a zeolite-impregnated nonwoven fabric was obtained.

[Comparative Example 4]
39.13 g of a 10% aqueous solution of PVA binder (same as above) was added to 43.47 g of distilled water and stirred for 30 minutes. 17.39 g of carbodihydrazide (same as above) was dissolved in the treatment solution and stirred. A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment solution, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a hydrazide-attached nonwoven fabric was obtained.

[Comparative Example 5]
41.86 g of a 10% aqueous solution of PVA binder (same as above) was added to 46.51 g of distilled water and stirred for 30 minutes. 11.62 g of carbodihydrazide (same as above) was dissolved in the treatment solution and stirred.
A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment solution, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a hydrazide-attached nonwoven fabric was obtained.

[Comparative Example 6]
44.55 g of a 10% aqueous solution of PVA binder (same as above) was added to 49.5 g of distilled water and stirred for 30 minutes. 5.94 g of carbodihydrazide (same as above) was dissolved in the treatment solution and stirred. A cotton nonwoven fabric (same as above) having a width of 20 cm and a length of 60 cm was immersed in the treatment solution, squeezed with a mangle, dried and fixed with a 120 ° C. pin tenter dryer, and a hydrazide-attached nonwoven fabric was obtained.

<Performance evaluation>
[Deodorization test]
The adsorbents described in Examples 1 to 8 and Comparative Examples 1 to 6 were cut into 2.5 cm x 1.25 cm sizes (about 0.03 g), sealed in a 5 L Tedlar pack together with 3 L of 40 ppm formaldehyde gas, and subjected to a deodorization test.
The residual formaldehyde gas concentration was measured using a gas detector tube manufactured by Gastec and Komyo Chemical Co., Ltd., and HPLC chromatography FRC-10A manufactured by Shimadzu.
The 70 ppm acetaldehyde gas was similarly deodorized.

  In Table 1 and FIG. 1, the processing liquid of Examples 1-8, Reference Examples 1-3 and Comparative Examples 1-6 is shown. Moreover, the deodorization test result of formaldehyde (FA) and acetaldehyde (AA) is shown in Table 2 and FIGS.

The adsorbents of Examples 1 to 8 have a remarkably high adsorption capacity with respect to formaldehyde and acetaldehyde gas as compared with the fiber sheets of Comparative Examples 1 to 3 containing only zeolite and Comparative Examples 4 to 6 containing only hydrazide. I can confirm.
In addition, an effect comparable to that obtained when Y-type zeolite, which is considered to have an excellent ability to adsorb aldehydes, is obtained (Reference Examples 1 and 2).

The use of the adsorbent and the fiber sheet of the present invention is not particularly limited. For example, in addition to interior fabrics such as curtains, carpets, wallpaper, and chair upholstery, the interiors of automobiles, vehicles, ships, aircrafts, etc. It can be widely and usefully used as a deodorizing material for fabrics and industrial filter materials such as honeycomb filters.
Further, when combined with other adsorbing substances such as a photocatalyst, activated carbon, and silica gel, it is possible to obtain a deodorant fabric having a higher-performance malodor removing function. It is also possible to add a commercially available flame retardant to impart flame retardancy to the deodorant fabric.

Claims (4)

  An aldehyde adsorbent comprising at least one zeolite selected from A-type and X-type and a hydrazide compound.   The aldehyde adsorbent according to claim 1, wherein the weight ratio of the zeolite to the hydrazide compound is in the range of 50: 1 to 2: 1.   A deodorant fiber sheet, wherein the aldehyde adsorbent according to claim 1 is supported.   The deodorant fiber sheet according to claim 3, wherein the adsorbent contains a binder, and the weight ratio of the zeolite to the binder is in the range of 20: 1 to 2: 1.