CN110652973B

CN110652973B - Sheet-like adsorbent and method for producing same

Info

Publication number: CN110652973B
Application number: CN201811455319.8A
Authority: CN
Inventors: 田村勇记; 久米哲也; 谷信幸; 吉村里惠
Original assignee: Cataler Corp
Current assignee: Cataler Corp
Priority date: 2018-06-28
Filing date: 2018-11-30
Publication date: 2022-11-25
Anticipated expiration: 2038-11-30
Also published as: CN110652973A; JP2020000999A; JP7139166B2

Abstract

The present invention aims to provide a sheet-like adsorbent having an excellent removal rate of aldehydes such as formaldehyde and acetaldehyde, and a method for producing the same. According to an embodiment of the present invention, there is provided a sheet-like adsorbent including a sheet-like air-permeable substrate, and a coating material containing a porous adsorbent and a binder, wherein the porous adsorbent is bonded to the sheet-like air-permeable substrate via the binder. The porous adsorbent is obtained by loading organic compound chemically reacting with aldehydes on porous carrier, and is loaded in an amount of 1cm ³ The density of the coating material in the sheet-like adsorbent is 0.10 to 0.25g/cm ³ 。

Description

Sheet-like adsorbent and method for producing same

Technical Field

The present invention relates to a sheet-like adsorbent and a method for producing the same.

Background

In the air, there are many chemical substances that can irritate various mucous membranes, such as nasal mucosa, ocular mucosa, pharyngeal mucosa, etc., and thus the skin. Among them, aldehydes such as formaldehyde and acetaldehyde generated in building materials and vehicles are considered to be causes of chemical substance allergy and sick building syndrome, and are subject to emission regulations and the like. In addition, in recent years, along with the remarkable improvement of living standards, there is a demand for more comfortable living environments and working environments, in which aldehydes are typical malodorous components and odor is easily perceived even at low concentrations, and thus there is an increasing demand for removal of aldehydes.

As one of means for removing aldehydes in air, various aldehyde scavengers have been developed in which chemical substances that react with aldehydes to make them harmless are dissolved or dispersed in a solvent such as water. For example, patent document 1 discloses the following technique: the surface of a sheet pad made of a flexible polyurethane foam is coated with an aldehyde scavenger, thereby suppressing the release of volatile organic compounds such as formaldehyde and acetaldehyde from the sheet pad.

However, when the aldehyde scavenger is used, a large amount of the aldehyde scavenger needs to be applied to the substrate to obtain the effect. Further, when the aldehyde scavenger is applied to the entire surface of the sheet mat as in patent document 1, not only the amount of the aldehyde scavenger used increases, but also the drying time becomes long, and the workability becomes poor. Further, there is a problem that the aldehyde scavenger remains on the metal or the fabric product, causing discoloration.

As another means for removing chemical substances in the air, there is physical adsorption by a porous body such as activated carbon having a large surface area and pore volume. For example, sheets coated with activated carbon are used for removing volatile organic compounds such as formaldehyde and acetaldehyde discharged from new houses, new electric appliances, and the like. However, the sheet coated with activated carbon has a problem that although volatile organic compounds are adsorbed to some extent, the amount of desorption is also large. In particular, the effect on lower aldehydes having low boiling points is insufficient.

Since there is a limit to physical adsorption of chemical substances by the porous body, a porous adsorbent in which a chemical adsorbent is supported on the porous body may be used as a component for performing chemical adsorption in an auxiliary manner. For example, patent document 2 discloses a sheet-like adsorbent in which a porous adsorbent carrying an azole compound and/or hydrazide compound is fixed to a sheet-like substrate with a binder as a sheet-like adsorbent having excellent adsorption properties on aldehydes and desorption inhibition ability after adsorption.

As a sheet-like adsorbent material specifically used for applications in which a gas to be treated is dynamic as in the air cleaner applications, patent document 3 discloses a fibrous sheet in which inorganic particles such as porous silica (excluding activated carbon), acid hydrazide, and a moisture absorbent having an amino group (for example, urea, a urea derivative, a guanidine salt, and an aminoguanidine salt) are present on a substrate.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2005-124743

Patent document 2: japanese laid-open patent publication No. 2014-133220

Patent document 3: japanese patent laid-open No. 2008-138300

Disclosure of Invention

In order to improve the performance of removing chemical substances such as aldehydes from the porous body or the chemical adsorbent, for example, the chemical adsorbent or the porous body held on the substrate is generally weighted per unit area, that is, the substrate is generally weighted per 1m ² The amount of retention of (b) is adjusted to an appropriate range, and the like.

However, according to the study of the present inventors, it was found that: only an appropriate range of the weight per unit area of the chemisorbent or porous material held in the substrate was found, and the removal rate of the aldehydes was not increased to a certain level or more. As described above, there is an increasing demand for removing aldehydes. Under such circumstances, development of a sheet-like adsorbent having a higher removal rate of aldehydes has been desired.

The present invention aims to provide a sheet-like adsorbent having an excellent removal rate of aldehydes such as formaldehyde and acetaldehyde, and a method for producing the same.

The reason why the removal rate of aldehydes is not increased to a certain level or more even if an appropriate range of the weight per unit area of the porous adsorbent held in the sheet-like substrate is found is intensively studied, and the following is found. That is, in order to increase the removal rate of aldehydes to a high level, it is important to make the contact state between the gas to be treated containing aldehydes and the porous adsorbent fixed to the sheet-like substrate via the binder good. Further, the density of the coating material containing the porous adsorbent and the binder held in the sheet-like adsorbent (hereinafter, also referred to as "coating density") becomes an important factor. The present invention has been developed based on such findings, and has the following embodiments, for example.

< embodiment 1 >

A sheet-like adsorbent comprising a sheet-like air-permeable substrate and a coating material containing a porous adsorbent and a binder, wherein the porous adsorbent is bonded to the sheet-like air-permeable substrate via the binder, wherein the porous adsorbent is obtained by supporting an organic compound that chemically reacts with aldehydes on a porous carrier, and the porous adsorbent is supported on a porous carrier at a concentration of 1cm ³ The density of the coating material in the sheet-like adsorbent is 0.10 to 0.25g/cm ³ . The density of the coating material may be 0.10 to 0.21g/cm ³ And may be 0.10 to 0.15g/cm ³ Or alternatively 0.10 to 0.13g/cm ³ 。

< embodiment 2 >

The sheet-like adsorbent according to embodiment 1, wherein the porosity is 65 to 85%. The porosity may be 68 to 85%, 75 to 85%, or 79 to 85%.

< embodiment 3 >

The sheet-like adsorbent according to embodiment 1 or 2, wherein the adhesive has a Mallon test value (1251090, \1252525. The above-mentioned Marlon test value may be 0.13% or less, may be 0.06% or less, or may be 0.03% or less.

< embodiment 4 >

The sheet-shaped adsorbent according to any one of embodiments 1 to 3, wherein at least an azole compound is contained as the organic compound.

< embodiment 5 >

The sheet-shaped adsorbent according to any one of embodiments 1 to 4, wherein at least 4-amino-1, 2, 4-triazole is contained as the organic compound.

< embodiment 6 >

The sheet-like adsorbent according to any one of embodiments 1 to 5, wherein the porous support is activated carbon.

< embodiment 7 >

The sheet-like adsorbent according to any one of embodiments 1 to 6, wherein the sheet-like air-permeable substrate is made of a material containing at least polyethylene terephthalate.

< embodiment 8 >

The sheet-like adsorbent according to any one of embodiments 1 to 7, wherein the porous adsorbent does not contain an acid hydrazide.

< embodiment 9 >

A process for producing a sheet-like adsorbent comprising a sheet-like air-permeable base material and a coating material containing a porous adsorbent and a binder, wherein the porous adsorbent is bonded to the sheet-like air-permeable base material via the binder, and the porous adsorbent is obtained by supporting an organic compound that chemically reacts with aldehydes on a porous carrier, and the porous adsorbent is supported per 1cm ³ The density of the coating material in the sheet-like adsorbent is 0.10 to 0.25g/cm ³ The manufacturing method comprises the following steps:

a step of bringing the sheet-like air-permeable substrate into contact with a slurry containing the porous adsorbent and a binder;

squeezing the sheet-like air-permeable base material that has contacted the slurry;

and drying the sheet-like air-permeable base material having undergone the squeezing step.

The density of the coating material may be 0.10 to 0.21g/cm ³ And may be 0.10 to 0.15g/cm ³ Or alternatively 0.10 to 0.13g/cm ³ 。

< embodiment 10 >

The method for producing a sheet adsorbent according to embodiment 9, wherein the sheet adsorbent has a porosity of 65 to 85%. The porosity may be 68 to 85%, 75 to 85%, or 79 to 85%.

< embodiment 11 >

The method for producing a sheet-like adsorbent according to embodiment 9 or 10, wherein the above binder has a marlon test value of 0.15% or less. The above-mentioned marlon test value may be 0.13% or less, may be 0.06% or less, or may be 0.03% or less.

< embodiment 12 >

The method for producing a sheet-like adsorbent according to any one of embodiments 9 to 11, wherein the sheet-like adsorbent contains at least an azole compound as the organic compound.

< embodiment mode 13 >

The method for producing a sheet-like adsorbent according to any one of embodiments 9 to 12, wherein the sheet-like adsorbent contains at least 4-amino-1, 2, 4-triazole as the organic compound.

< embodiment 14 >

The method for producing a sheet-like adsorbent according to any one of embodiments 9 to 13, wherein the porous support is activated carbon.

< embodiment 15 >

The method for producing a sheet-like adsorbent according to any one of embodiments 9 to 14, wherein the sheet-like air-permeable substrate is made of a material containing at least polyethylene terephthalate.

< embodiment 16 >

The method for producing a sheet-shaped adsorbent according to any one of embodiments 9 to 15, wherein the porous adsorbent does not contain an acid hydrazide.

According to the present invention, a sheet-like adsorbent having an excellent removal rate of aldehydes and a method for producing the same are provided.

Drawings

FIG. 1 is an enlarged photograph showing the surface of a sheet-like adsorbent material according to an embodiment of the present invention.

FIG. 2 is a diagram showing an example of the influence of the density of a coating material on the removal rate of aldehydes.

FIG. 3 is a view showing an example of the influence of the porosity of the sheet-like adsorbent on the removal rate of aldehydes.

FIG. 4 is a diagram showing an example of the influence of the amount of the trapping agent supported on the porous carrier on the removal rate of aldehydes.

FIG. 5 is a view showing an example of the influence of the Marlon test value of the adhesive on the density of the coating material.

FIG. 6 is a diagram showing an example of the influence of the Mallon test value of the binder on the removal rate of aldehydes.

Detailed Description

Hereinafter, embodiments of the present invention will be described.

A sheet-like adsorbent according to an embodiment of the present invention includes a sheet-like air-permeable substrate (hereinafter also referred to as "sheet-like substrate"), and a coating material containing a porous adsorbent and a binder. The porous adsorbent is obtained by loading an organic compound chemically reacting with aldehydes on a porous carrier, and is used for adsorbing organic compounds per 1cm ³ The density of the coating material in the sheet-like adsorbent (coating density) is 0.10 to 0.25g/cm ³ 。

In the present invention, 1cm ³ The coating density of the sheet-shaped adsorbing material is 0.10-0.25 g/cm ³ As described above, this is found in view of the fact that the contact state between the gas to be treated and the porous adsorbent is improved.

However, it is not always easy to set the coating density held in the sheet adsorbent to a desired range. That is, for example, even if the amount, concentration, or the like of the adsorbent-containing slurry applied to the sheet substrate is optimized, a sheet-like adsorbent having a desired adsorbent density cannot necessarily be obtained.

In order to adjust the coating density maintained in the sheet-like adsorbent to a desired range, it has been newly found that the value of the Mallon test of the binder used becomes an important factor. The binder used was selected with attention paid to the value of the malan test, and the influence of the application density on the removal rate of aldehydes was examined, and as a result, it was found that: the coating density is 0.10-0.25 g/cm ³ In the range of (1), the gas to be treated in the sheet-like adsorbent is adsorbed to the porous portionThe contact area of the adsorbent increases, and the removal rate of the aldehydes dramatically increases.

Here, the coating density is 1cm per unit ³ The amount of the coating material retained in the sheet-like adsorbent is a value determined by the following formula (I).

[ number 1]

Fig. 1 is an enlarged photograph showing the surface of a sheet-like adsorbent material according to an embodiment of the present invention. From the magnified photograph, it is understood that: between fibers of the sheet-like air-permeable substrate, there are portions where the porous adsorbent is present in a film shape, and a plurality of portions are aggregated to form a block, and there are also void portions where the porous adsorbent is not present in a film shape. The coating density is 0.10-0.25 g/cm ³ When the amount of (b) is within the range (b), a good balance between the porous adsorbent and the voids between the fibers of the sheet-like air-permeable substrate can be obtained. The result is presumed to be: the gas to be treated can reach the inside of the sheet-like adsorbent and can be brought into contact with a sufficient amount of the porous adsorbent, and the removal rate of the aldehydes can be dramatically increased.

When the coating density exceeds 0.25g/cm ³ In the case of (3), since the voids are insufficient, the contact between the gas to be treated and the porous adsorbent is deteriorated, and the desired removal rate of the aldehydes cannot be obtained. In addition, the coating density is lower than 0.10g/cm ³ In the case of (3), the amount of the porous adsorbent is insufficient, and the desired removal rate of the aldehydes cannot be obtained.

In one embodiment of the present invention, each 1cm ³ The coating density of the sheet-like adsorbent may be 0.10 to 0.21g/cm ³ And may be 0.10 to 0.15g/cm ³ Or alternatively 0.10 to 0.13g/cm ³ 。

About every 1m ² The coating material in the sheet-like air-permeable base material has a coating density of 0.10 to 0.25g/cm ³ Within the range of (b), the range of (c) can be appropriately set. For example, in such a manner that the coating density does not exceed 0.25g/cm ³ The method (1) can further increase the removal rate of the aldehyde by increasing the coating amount (for example, see examples 4A and 7A described later). In one mode, every 1m ² The amount of the sheet-like adsorbent to be coated (weight per unit area) may be 200 to 600g/m ² And may be 200 to 450g/m ² Or may be 200 to 320g/m ² 。

In one embodiment of the present invention, the mixing ratio of the porous carrier and the binder contained in the coating material may be 19 to 41g, 25 to 35g, or 27 to 33g of the binder to 100g of the porous carrier.

In one embodiment of the present invention, the porosity of the sheet-like adsorbent may be 65 to 85%, 68 to 85%, 75 to 85%, or 79 to 85%. When the porosity is within the above range, the effective contact of the gas to be treated with the porous adsorbent can be promoted. Here, the porosity of the sheet-like adsorbent is a percentage of the gap per unit volume, and is a value determined by the following equation.

Number 2

A

B

^＊ Product sheet-like adsorbent

Substrate sheet-like air-permeable substrate

< porous adsorbent >

The porous adsorbent is an adsorbent in which an organic compound (hereinafter, referred to as "chemisorbent" or "trapping agent") that chemically reacts with an aldehyde is supported on a porous carrier. As the porous adsorbent, 1 or more may be used.

(porous carrier)

As the porous carrier, any carrier having a plurality of fine pores may be used. For example, as the porous support, any porous substance of an inorganic porous support and an organic porous support can be used.

Specific examples of the inorganic porous carrier include: active carbon, sepiolite, palygorskite, zeolite, active carbon fiber, active alumina, sepiolite mixed paper, silica gel, active clay, vermiculite and diatomite. In addition, as the organic porous carrier, there can be mentioned: paper pulp, fiber and polymer porous carrier. Among these porous carriers, activated carbon is preferable because it has excellent adsorption characteristics particularly for aldehydes. Here, the "adsorption characteristics" as used in the present specification means a property of adsorbing the adsorbed component more and making it difficult for the adsorbed component to desorb once adsorbed.

The shape of the porous support is not particularly limited as long as it is a shape that can be contacted with a gas to be treated containing aldehydes. For example, a granular, powdery, or fibrous porous carrier may be used. In the case where the porous support is applied to the sheet-like air-permeable substrate, the porous support is preferably used in the form of a slurry, and in this case, the porous support after crushing and/or pulverization may be selected. The type or shape of the porous carrier used in the present invention may be selected depending on the type of the aldehyde to be removed or depending on the place where the sheet-like adsorbent is installed.

For example, the particle diameter (median diameter: D50) of the porous support is preferably small for forming a slurry, and may be, for example, 150 μm or less, 50 μm or less, or 25 μm or less. The porous carrier generally has a larger BET specific surface area, which is more preferable, and may be 400m, for example ² A ratio of 700m or more per g ² Is more than or equal to 1000 m/g or ² More than g.

(Capture reagent)

The trapping agent that is an organic compound chemically reacting with the aldehyde may be any organic compound that chemically reacts with the aldehyde to exhibit a trapping effect.

However, in the case of using activated carbon as the porous support, it is preferable not to use acid hydrazide as the scavenger. Here, the acid hydrazide means having-CO-NHNH derived from a carboxylic acid and hydrazine ₂ The acid hydrazide group compound is shown. When the acid hydrazide is used in combination with activated carbon, the acid hydrazide is deactivated and the reactivity with aldehydes is lowered. Therefore, in the case of using activated carbon as the porous support, the porous adsorbent is preferably substantially free of acid hydrazide, more preferably free of acid hydrazide. Here, "substantially not containing" means that such a case is not excluded: the acid hydrazide is contained in a trace amount to the extent that the effect of the present invention is not impaired.

In one embodiment, an azole compound may be used as the scavenger. Here, the azole compound means a compound of: the compound is a five-membered ring aromatic compound containing at least 1 heteroatom, at least 1 of the heteroatoms being a nitrogen atom, and has a desired adsorption property particularly to aldehydes.

The azole compound includes oxadiazole, triazole, tetrazole, and the like, and specific examples thereof include: pyrazolone compounds such as 3-methyl-5-pyrazolone, 1, 3-dimethyl-5-pyrazolone, 3-methyl-1-phenyl-5-pyrazolone, 3-phenyl-6-pyrazolone, and 3-methyl-1- (3-sulfophenyl) -5-pyrazolone; pyrazole compounds such as pyrazole, 3-methylpyrazole, 1, 4-dimethylpyrazole, 3, 5-dimethyl-1-phenylpyrazole, 3-aminopyrazole, 5-amino-3-methylpyrazole, 3-methylpyrazole-5-carboxylic acid methyl ester, 3-methylpyrazole-5-carboxylic acid ethyl ester, and 3, 5-methylpyrazole dicarboxylic acid; 1,2, 3-triazole, 1,2, 4-triazole, 3-n-butyl-1, 2, 4-triazole, 3, 5-dimethyl-1, 2, 4-triazole, 3, 5-di-n-butyl-1, 2, 4-triazole, 3-mercapto-1, 2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole, 5-amino-3-mercapto-1, 2, 4-triazole, 3-amino-5-phenyl-1, 2, 4-triazole, 3, 5-diphenyl-1, 2, 4-triazole, 1,2, 4-triazole-3-one, urazole (3, 5-dioxy-1, 2, 4-triazole), 1,2, 4-triazole-3-carboxylic acid, 1-hydroxybenzotriazole, 5-hydroxy-7-methyl-1, 3, 8-triaza triazine, 1H-benzotriazole, 1H-methyl-triazole, and the like compounds; thiadiazole compounds such as 2-amino-5-ethyl-1, 3, 4-thiadiazole, 5-amino-2-mercapto-1, 3, 4-thiadiazole, 2, 5-dimercapto-1, 3, 4-thiadiazole, 5-tert-butyl-2-methylamino-1, 3, 4-thiadiazole, 2-amino-5-methyl-1, 3, 4-thiadiazole and 2-amino-1, 3, 4-thiadiazole.

As the azole compound, 3-aminopyrazole, 5-amino-3-methylpyrazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole, 5-amino-3-mercapto-1, 2, 4-triazole, 3-amino-5-phenyl-1, 2, 4-triazole, 2-amino-5-ethyl-1, 3, 4-thiadiazole, 5-amino-2-mercapto-1, 3, 4-thiadiazole, 5-tert-butyl-2-methylamino-1, 3, 4-thiadiazole, 2-amino-5-methyl-1, 3, 4-thiadiazole, 2-amino-1, 3, 4-thiadiazole are particularly preferable, and among them, 4-amino-1, 2, 4-triazole is preferable.

As long as the excellent performance of adsorbing aldehydes is not lost and once the aldehydes are adsorbed, it is possible to use 1 or more kinds of azole compounds, and it is also possible to use 1 or more kinds of other trapping agents in combination.

The method of supporting the trapping agent on the porous carrier is not particularly limited, and for example, the trapping agent may be dissolved in water or another solvent, and the porous carrier may be impregnated with the obtained chemical solution and supported.

The amount of the scavenger to be supported may be appropriately determined depending on the kind, concentration, and the like of the aldehyde contained in the gas to be treated. In one mode, every 1m ² The amount of the scavenger supported on the porous carrier having a BET specific surface area may be 0.00002 to 0.00050g, 0.00003 to 0.00030g, or 0.00002 to 0.00020g. That is, for example, 1000m relative to the BET specific surface area ² For 100g of the porous carrier per g, 4 to 20g, 6 to 12g, or 6 to 10g of the trapping agent may be used.

< sheet-like air-permeable substrate >

The sheet-like air-permeable substrate is not particularly limited as long as it has air permeability to the gas to be treated. As the sheet-like air-permeable substrate, a substrate in which a slurry containing a porous adsorbent can permeate into the inside of the substrate in the production process is preferable.

Specific examples of the sheet-like air-permeable substrate include: foamed resin, reticulated resin, porous resin film, woven fabric, nonwoven fabric, paper, inorganic fiber, and the like. As the material, polyolefin such as polyethylene and polypropylene, polyester such as polyethylene terephthalate and polybutylene terephthalate, synthetic fiber such as polyurethane, nylon, polyvinyl chloride, polyvinylidene chloride, fluorine resin, vinylon, aramid, polyacrylic polymer, cellulose acetate, and Promix; semi-synthetic fibers; regenerated fibers such as rayon; natural fibers such as cotton, hemp, silk and the like: or inorganic fibers. Alternatively, the sheet-like air-permeable base material may be a woven fabric woven with fine metal wires. From the viewpoint of recovery or compression elasticity in the drying step after the extrusion step described later, a sheet-like base material such as a nonwoven fabric made of a material containing polyethylene terephthalate can be suitably used.

The weight per unit area of the sheet-like air-permeable substrate may be, for example, 10 to 400g/m ² 、30～300g/m ² Or 50 to 200g/m ² . As used herein, the "basis weight of the substrate" means the weight per 1m ² The quality of the sheet-like air-permeable substrate (2).

< adhesive >

As the binder, any binder capable of binding the porous adsorbent and the sheet-like air-permeable substrate, for example, an organic binder such as a polymer material, may be used.

In order to bond the porous adsorbent to the sheet-like air-permeable substrate using the binder, for example, the following steps are performed. That is, a binder is added to a slurry containing a porous adsorbent, the slurry is stirred for a predetermined time to obtain a slurry containing the porous adsorbent and the binder, and the sheet-like air-permeable substrate is brought into contact with the slurry and dried. Here, the contact between the slurry and the substrate may be performed by, for example, coating, impregnating, coating, or the like the slurry on the sheet-like air-permeable substrate.

The sheet-like base material after contact with the slurry is restored in the thickness direction in the subsequent drying step. Depending on the type of the adhesive, the adhesive may inhibit the recovery of the sheet-like base material in thickness, which may cause difficulty in adjusting the coating density to a desired range. Thus, in one embodiment of the invention, an adhesive with a low marlon test value is used. The marlon test value is a parameter for evaluating mechanical stability, and a lower marlon test value indicates more excellent mechanical stability. Here, it functions as an index indicating the degree of recovery in thickness of the sheet-like base material after contact with the slurry.

In the process for the production of articles, the following steps are generally included: the sheet-like base material after contact with the slurry is extruded by an extrusion device such as a roller mill (mangle) to remove excess components of the slurry. In this case, the adhesive is broken when the porous support and the adhesive are rubbed against each other in the extrusion step, and adhesiveness is developed before drying. Therefore, in the sheet-like adsorbent produced through the extrusion step, in particular, the sheet-like base material is greatly hindered from recovery. By using a binder having a low value of the "marlon test", the binder can be stably held even after the extrusion step, and the inhibition of recovery of the thickness of the sheet-like base material can be suppressed. Therefore, it is particularly effective to use a binder having a low marlon test value in the sheet-like adsorbent produced through the extrusion step.

In one embodiment, the adhesive may have a nylon test value of 0.15% or less, 0.13% or less, or 0.06% or less. By selecting a binder having a low value of the Malone test, the coating density or the porosity of the sheet-like adsorbent can be easily adjusted to a preferable range.

Examples of the organic binder include emulsion-type organic binders, and in particular, acrylic emulsions such as acrylic resins, acrylic-styrene resins, acrylic-silicone resins, acrylic-urethane resins, vinyl acetate-acrylic resins, and silicone-acrylic resins, and latex-type emulsions such as butadiene resins can be used. In one embodiment, the binder is preferably a binder which hardly remains in the pores of the porous adsorbent, for example, an aqueous acrylic resin.

The amount of the binder (solid content) added may be, for example, 10 to 80% by mass or 20 to 40% by mass relative to the porous adsorbent, but is not limited to this range.

The slurry containing the aldehyde adsorbent may further contain a thickener. Such a thickener is particularly preferably used when it is difficult to constantly stir the slurry or when the slurry is separated into an emulsion containing water or a resin component and a porous adsorbent when the slurry is brought into contact with the sheet-like air-permeable substrate.

Examples of such a thickener include: sodium polyacrylate, acrylic copolymer, polyacrylic acid, carboxylic acid copolymer (ammonium salt), carboxylic acid copolymer (for example, sodium salt of carboxylic acid copolymer such as sodium carboxymethylcellulose), crosslinked sodium polyacrylate, crosslinked acrylic polymer, crosslinked polyacrylic acid, and the like. The amount of the thickener to be added may be, for example, 0.1 to 10 mass%, 0.5 to 5 mass%, or 1.0 to 3 mass% relative to the porous carrier, but is not limited to this range.

The sheet-like air-permeable substrate after contacting with the slurry, or further after the extrusion step, may be dried for a predetermined time. Since the azole compound as a preferable chemical adsorbent is an organic substance, the drying step is preferably performed under drying conditions under which the chemical adsorbent is not thermally deteriorated. For example, the drying step may be performed at 150 ℃ or lower, 110 ℃ or lower, or 80 ℃ or lower.

The sheet-shaped adsorbent according to the embodiment of the present invention can be preferably used as an article for removing Volatile Organic Compound (VOC) components such as aldehydes. Particularly, it is preferably used for adsorbing VOC by natural diffusion in a stationary state such as in a car or in a room. Intended to be applied to various devices or parts in a vehicle or a room, and is preferably disposed in the vicinity of a VOC component generating source. The sheet-shaped adsorbent of the present embodiment may be used in various forms depending on the application, the member to which the sheet-shaped adsorbent is applied, and the like, and for example, the sheet-shaped adsorbent is attached to or inserted into the member, or the sheet-shaped adsorbent is mixed with the member of the cut product.

[ examples ] A method for producing a compound

The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to these examples.

< preparation of slurry 1 >

8g of 4-amino-1, 2, 4-triazole were dissolved in 238g of water. The BET specific surface area is about 1000m ² 100g of powdered coconut shell activated carbon having a median diameter (D50) of 25 μm was immersed in the chemical solution and sufficiently stirred. Slurry 1 was prepared by adding 2g of a water-soluble tackifier, then 61g of an acrylic emulsion binder (solid content 50%, nylon test value 0.057%) and stirring. Acrylic emulsion adhesives used were 125081253167125886 (manufactured by DIC corporation).

The marlon test value is a value measured by the following method.

[ method for measuring Malong test value (mechanical stability) ]

50g of the emulsion sample was weighed in a vessel of a Marlon-type stability tester, and mechanical shear was applied for 10 minutes at a temperature of 25 ℃ and a load of 10kg at a rotation speed of 2000 rpm. Thereafter, the resultant aggregate was filtered through a 200-mesh wire gauze. The Marlon test value indicating mechanical stability was calculated in accordance with the following formula.

Malon test value (mechanical stability) (%) = (absolute mass of aggregate/absolute mass of emulsion) × 100

< example 1A >)

The weight per unit area is 95g/m ² The nonwoven fabric (E-90 made by processing woven fibers) was impregnated in the slurry 1. Subsequently, the nonwoven fabric was squeezed by a roll mill to adjust the coating amount, and dried at 100 ℃ for 1 hour, thereby producing a sheet-like adsorbent 1A. The basis weight (coating amount) of the coating material, the density (coating density) of the coating material, and the porosity were measured by the methods described below. As a result, the amount of the sheet-shaped adsorbent 1A coated was 245g/m ² Coating density of 0.110g/cm ³ The porosity was 83%.

< example 2A >)

The weight per unit area is 95g/m ² The nonwoven fabric (E-90 made by processing woven fibers) was impregnated in the slurry 1. Next, to adjust the amount of coating, examples1A the pressure of the roll mill was changed to squeeze the nonwoven fabric, and the nonwoven fabric was dried at 100 ℃ for 1 hour, thereby producing a sheet-like adsorbent 2A. The amount of the coated sheet-like adsorbent 2A was 263g/m ² Coating density of 0.134g/cm ³ The porosity was 79%.

< example 3A >)

The weight per unit area is 95g/m ² The nonwoven fabric (E-90 made by processing woven fibers) was impregnated in the slurry 1. Next, in order to adjust the amount of coating, the nonwoven fabric was squeezed by changing the pressure of the calender in example 1A, and dried at 100 ℃ for 1 hour, thereby producing a sheet-like adsorbent 3A. The amount of coating of the sheet-like adsorbent 3A was 318g/m ² Coating density of 0.146g/cm ³ The porosity was 77%.

< example 4A >

The weight per unit area is 95g/m ² The slurry 1 was impregnated with the nonwoven fabric (E-90 produced by tow processing). Subsequently, in order to adjust the amount of coating, the nonwoven fabric was squeezed by changing the pressure of the calender in example 1A, and dried at 100 ℃ for 1 hour to produce a sheet-like adsorbent 4A. The amount of coating of the sheet-like adsorbent 4A was 460g/m ² Coating density of 0.214g/cm ³ The porosity was 68%.

< example 5A >)

The weight per unit area is 95g/m ² The nonwoven fabric (E-90 made by processing woven fibers) was impregnated in the slurry 1. Next, in order to adjust the coating amount, the nonwoven fabric was squeezed by changing the pressure of the calender roll in example 1A, and dried at 100 ℃ for 1 hour, thereby producing a sheet-like adsorbent 5A. The coating amount of the sheet-like adsorbent 5A was 568g/m ² The coating density was 0.235g/cm ³ The porosity was 65%.

< example 6A >)

The weight per unit area is 140g/m ² The slurry 1 was impregnated with the nonwoven fabric (RFN-150P made by housing fiber processing). Subsequently, in order to adjust the amount of coating, the nonwoven fabric was squeezed by changing the pressure of the calender in example 1A, and dried at 100 ℃ for 1 hour to produce a sheet-like adsorbent 6A. The amount of coating of the sheet-like adsorbent 6A was 385g/m ² Coating density of 0.102g/cm ³ The porosity is 84%。

< example 7A >)

The weight per unit area is 140g/m ² The slurry 1 was impregnated with the nonwoven fabric (RFN-150P made by housing fiber processing). Next, in order to adjust the amount of coating, the nonwoven fabric was squeezed by changing the pressure of the calender in example 1A, and dried at 100 ℃ for 1 hour, thereby producing a sheet-like adsorbent 7A. The sheet-shaped adsorbing material 7A was coated in an amount of 883g/m ² Coating density of 0.214g/cm ³ The porosity was 68%.

< example 1B >)

The weight per unit area is 95g/m ² The slurry 1 was impregnated with the nonwoven fabric (E-90 produced by tow processing). Next, in order to adjust the amount of coating, the nonwoven fabric was squeezed by changing the pressure of the calender in example 1A, and dried at 100 ℃ for 1 hour, thereby producing a sheet-like adsorbent 1B. The amount of coating of the sheet-shaped adsorbent 1B was 45g/m ² The coating density is 0.020g/cm ³ The porosity was 95%.

< example 2B >)

The weight per unit area is 95g/m ² The nonwoven fabric (E-90 made by processing woven fibers) was impregnated in the slurry 1. Next, in order to adjust the amount of coating, the nonwoven fabric was squeezed by changing the pressure of the calender roll in example 1A, and dried at 100 ℃ for 1 hour, thereby producing a sheet-like adsorbent 2B. The amount of coating of the sheet-like adsorbent 2B was 148g/m ² The coating density was 0.077g/cm ³ The porosity was 87%.

< example 3B >)

The weight per unit area is 95g/m ² The slurry 1 was impregnated with the nonwoven fabric (E-90 produced by tow processing). Next, in order to adjust the amount of coating, the nonwoven fabric was squeezed by changing the pressure of the calender roll in example 1A, and dried at 100 ℃ for 1 hour, thereby producing a sheet-like adsorbent 3B. The amount of coating of the sheet-like adsorbent 3B was 173g/m ² Coating density of 0.094g/cm ³ The porosity was 84%.

< example 4B >

The weight per unit area is 95g/m ² The slurry 1 was impregnated with the nonwoven fabric (E-90 produced by tow processing). Then, in order to adjust the coating amount,for example 1A, the pressure of a roll mill was changed to squeeze the nonwoven fabric, and the nonwoven fabric was dried at 100 ℃ for 1 hour, thereby producing a sheet-like adsorbent 4B. The amount of the coated sheet-like adsorbent 4B was 498g/m ² Coating density of 0.262g/cm ³ The porosity was 61%.

< example 5B >)

The weight per unit area is 95g/m ² The nonwoven fabric (E-90 made by processing woven fibers) was impregnated in the slurry 1. Next, in order to adjust the amount of coating, the nonwoven fabric was squeezed by changing the pressure of the calender roll in example 1A, and dried at 100 ℃ for 1 hour, thereby producing a sheet-like adsorbent 5B. The sheet-shaped adsorbent 5B was coated in an amount of 633g/m ² The coating density was 0.279g/cm ³ The porosity was 58%.

< example 6B >

The weight per unit area is 95g/m ² The nonwoven fabric (E-90 made by processing woven fibers) was impregnated in the slurry 1. Subsequently, in order to adjust the amount of coating, the nonwoven fabric was squeezed by changing the pressure of the calender in example 1A, and dried at 100 ℃ for 1 hour to produce a sheet-like adsorbent 6B. The amount of coating of the sheet-like adsorbing material 6B was 743g/m ² The coating density was 0.345g/cm ³ The porosity was 48%.

< example 7B >)

The weight per unit area is 140g/m ² The slurry 1 was impregnated with the nonwoven fabric (RFN-150P made by housing fiber processing). Subsequently, in order to adjust the amount of coating, the nonwoven fabric was squeezed by changing the pressure of the calender in example 1A, and dried at 100 ℃ for 1 hour to produce a sheet-shaped adsorbent 7B. The amount of the sheet-like adsorbent 7B coated was 255g/m ² The coating density is 0.069g/cm ³ The porosity was 88%.

< example 8B >

Weight per unit area of 95g/m ² Instead of the slurry 1, an aqueous triazole solution in which 8g of 4-amino-1, 2, 4-triazole was dissolved in 238g of water was sprayed on the nonwoven fabric (E-90 produced by cabin fiber processing) to dry the resultant at 100 ℃ for 1 hour, thereby producing a sheet-like adsorbent 8B. The amount of the coated sheet-like adsorbent 8B was 16g/m ² The coating density is 0.007g/cm ³ The porosity was 97%.

< example 9B >)

Weight per unit area 95g/m ² Instead of the slurry 1, an aqueous triazole solution in which 8g of 4-amino-1, 2, 4-triazole was dissolved in 238g of water was sprayed on the nonwoven fabric (E-90 produced by cabin fiber processing) to dry the resultant at 100 ℃ for 1 hour, thereby producing a sheet-like adsorbent 9B. The amount of the coated sheet-like adsorbent 9B was 24g/m ² Coating density of 0.010g/cm ³ The porosity was 97%.

< evaluation >

[ method for measuring coating Density ]

The mass of the produced sheet-like adsorbing material was measured by an electronic balance. The mass of the sheet-like air-permeable base material of known mass was subtracted from the measured value to determine the mass of the coating material held in the sheet-like adsorbent. The lengths of the sheet-like adsorbent in the longitudinal direction, the transverse direction and the thickness direction were measured with an electronic vernier caliper, and the volume thereof was determined. From the calculated mass and volume, the density (g/cm) of the coating material was calculated in accordance with the above formula (I) ³ )。

[ method of measuring void fraction ]

First, the density of the produced sheet-like adsorbent was calculated. That is, the density (a) of the sheet-like adsorbent is calculated from the mass and volume of the sheet-like adsorbent measured as described above according to the above formula (IIa).

Then, the theoretical density (void-free density) of the sheet-like adsorbent was calculated according to the above formula (IIb). That is, the theoretical density (B) of the sheet adsorbent is calculated by determining the composition ratios of the sheet-shaped air-permeable base material and the coating material in the sheet adsorbent from the mass of the sheet-shaped air-permeable base material and the mass of the coating material in the sheet adsorbent, multiplying the respective densities (i.e., the base material density or the coating density) by the respective composition ratios, and summing the resultant densities.

Next, according to the above formula (II), a value obtained by subtracting the percentage of the actual density (a) of the sheet-shaped adsorbent to the theoretical density (B) from 100% is calculated as a porosity (%).

[ removal Rate of acetaldehyde ]

According toNumber of samples to be filled in 5L bags with 4L N ₂ The latter samples. Each sheet-like adsorbent was cut into 2cm × 2cm and sealed in each bag. Mixing the mixture by weight of 1.68ppm (≈ 3000 μ g/m) ³ ) The acetaldehyde (2) was injected into each bag in which a sheet-like adsorbent was sealed, and the bag was allowed to stand in a chamber at 25 ℃ and 50% RH for 1 hour to measure the acetaldehyde concentration. The amount of acetaldehyde adsorbed during 1 hour was calculated from the difference from the initial concentration, and the acetaldehyde removal rate (ppm/h) was determined under static conditions.

The measurement results for examples 1A to 7A and 1B to 9B are summarized in table 1, fig. 2, and fig. 3. In examples 1A to 7A, the coating density was 0.10 to 0.25g/cm ³ In examples 1B to 9B, the coating density was outside the range.

[ TABLE 1]

TABLE 1

As shown in table 1 and fig. 2, it can be seen that: the coating density is 0.10-0.25 g/cm ³ Examples 1A to 7A within the range are more excellent in the removal rate of acetaldehyde than examples 1B to 9B having coating densities outside the range. Further, as shown in Table 1 and FIG. 3, the coating density was 0.10 to 0.25g/cm ³ In examples 1A to 7A within the range, the porosity is in a preferable range of 65 to 85%, and it is presumed that: the gas to be treated can be effectively contacted with the porous adsorbent.

< example 10B >

Slurry 2 was prepared under the same conditions as slurry 1, except that 4-amino-1, 2, 4-triazole was not used. A sheet adsorbent 10B having a coating density almost the same as that of the sheet adsorbent 2A of example 2A was obtained by producing the sheet adsorbent under the same conditions as in example 2A except that the slurry 2 was used instead of the slurry 1.

< example 8A >)

Slurry 3 was prepared under the same conditions as slurry 1 except that the amount of 4-amino-1, 2, 4-triazole used was changed from 8g to 4g (4 parts by mass). A sheet adsorbent was produced under the same conditions as in example 2A except that the slurry 3 was used instead of the slurry 1, and a sheet adsorbent 8A having a coating density almost the same as that of the sheet adsorbent 2A of example 2A was obtained.

< example 9A >)

Slurry 4 was prepared under the same conditions as slurry 1 except that the amount of 4-amino-1, 2, 4-triazole used was changed from 8g to 6g (6 parts by mass). A sheet adsorbent 9A having a coating density almost the same as that of the sheet adsorbent 2A of example 2A was obtained by producing the sheet adsorbent under the same conditions as those of example 2A except that the slurry 4 was used instead of the slurry 1.

< example 10A >)

Slurry 5 was prepared under the same conditions as slurry 1 except that the amount of 4-amino-1, 2, 4-triazole used was changed from 8g to 12g (12 parts by mass). A sheet adsorbent 10A having a coating density almost the same as that of the sheet adsorbent 2A of example 2A was obtained by producing the sheet adsorbent under the same conditions as in example 2A except that the slurry 5 was used instead of the slurry 1.

< example 11A >)

Slurry 6 was prepared in the same formulation as slurry 1, except that the amount of 4-amino-1, 2, 4-triazole used was changed from 8g to 20g (20 parts by mass). A sheet adsorbent was produced under the same conditions as in example 2A except that the slurry 6 was used instead of the slurry 1, and a sheet adsorbent 11A having a coating density almost the same as that of the sheet adsorbent 2A of example 2A was obtained.

In examples 8A to 11A and 10B, the coating density, the porosity and the removal rate of aldehyde were measured by the same methods as described above. The results are summarized in table 2 and fig. 4. In examples 2A, 8A and 11A, the coating density was 0.10 to 0.25g/cm ³ In example 10B, the coating density was within this range, but the trapping agent was not contained.

[ TABLE 2]

TABLE 2

The amount is indicated by the number of parts of 100 parts by mass of activated carbon

As shown in Table 2 and FIG. 4, the coating density was adjusted to 0.10 to 0.25g/cm in the sheet-like adsorbent using various porous adsorbents having different amounts of the capturing agent supported thereon ³ In the above range, it was confirmed that the removal rate of acetaldehyde was excellent.

< example 12A >)

Slurry 7 was prepared under the same conditions as slurry 1 except that the acrylic emulsion adhesive was changed from AB-886 (manufactured by DIC corporation, mallon test value 0.057%) to AB-782-E (manufactured by DIC corporation, mallon test value 0.128%). A sheet adsorbent was produced under the same conditions as in example 3A except that the slurry 7 was used instead of the slurry 1, and a sheet adsorbent 12A having a coating density almost the same as that of the sheet adsorbent 3A of example 3A was obtained.

< example 11B >)

Slurry 8 was prepared under the same conditions as slurry 1 except that the acrylic emulsion binder was changed from AB-886 (manufactured by DIC corporation, mallon test value of 0.057%) to AB-795 (manufactured by DIC corporation, mallon test value of 1.660%). A sheet-shaped adsorbent was produced under the same conditions as in example 3A except that the slurry 8 was used instead of the slurry 1, and a sheet-shaped adsorbent 11B was obtained.

In examples 12A and 11B, the coating density, the porosity, and the removal rate of aldehyde were measured by the same methods as described above. The results are summarized in table 3, fig. 5 and fig. 6. In examples 3A and 12A, the coating density was 0.10 to 0.25g/cm ³ In example 11B, the coating density was not in this range.

[ TABLE 3]

TABLE 3

As shown in table 3, fig. 5 and fig. 6, canKnowing: in examples 3A and 12A using a binder having a Marlon test value of less than 0.15%, the coating density was 0.10 to 0.25g/cm ³ In the range of (1), the removal rate of aldehyde is excellent. On the other hand, it is known that: in example 11B in which a binder having a Malone test value exceeding 0.15% was used, the removal rate of aldehyde was poor when the coating density was outside this range.

The present invention is not limited to the above embodiments, and various modifications may be made without departing from the spirit and scope of the invention. Further, the respective embodiments may be combined as appropriate, and in this case, combined effects can be obtained. Further, the above-described embodiments include various inventions, and various inventions can be extracted from combinations selected from a plurality of disclosed constituent elements. For example, even if some of the constituent elements shown in the embodiments are deleted, the problem can be solved and the effect can be obtained, and the configuration from which the constituent elements are deleted can be extracted as an invention.

Claims

1. A sheet-shaped adsorbent comprising a sheet-shaped air-permeable substrate and a coating material containing a porous adsorbent and a binder, the porous adsorbent being bonded to the sheet-shaped air-permeable substrate via the binder, wherein,

the porous adsorbent is obtained by loading organic compound chemically reacting with aldehydes on porous carrier, and has a pore diameter of 1cm ³ The density of the coating material in the sheet-shaped adsorbing material is 0.10 to 0.25g/cm ³ ，

The adhesive has a Marlon test value of 0.15% or less,

at least an azole compound is contained as the organic compound,

the binder includes an emulsion-based organic binder,

the porous support is activated carbon and does not use acid hydrazide as the organic compound,

the marlon test value is a value determined by the following method:

50g of a binder was weighed in a vessel of a Marlon-type stability tester, mechanical shearing was applied for 10 minutes under conditions of a temperature of 25 ℃, a load of 10kg, a rotation speed of 2000rpm, and then the resultant aggregate was filtered through a 200-mesh wire gauze, and a Marlon test value representing mechanical stability was calculated according to the following formula,

a malon test value (%) = (absolute dry mass of aggregate/absolute dry mass of adhesive) × 100%.

2. The sheet-shaped adsorbing material according to claim 1, wherein the porosity is 65 to 85%.

3. The sheet adsorbent material according to claim 1 or 2, which contains at least 4-amino-1, 2, 4-triazole as the organic compound.

4. The sheet-like adsorbent according to claim 1 or 2, wherein the sheet-like air-permeable substrate is composed of a material containing at least polyethylene terephthalate.

5. A method for producing a sheet-like adsorbent comprising a sheet-like air-permeable base material and a coating material containing a porous adsorbent and a binder, wherein the porous adsorbent is bonded to the sheet-like air-permeable base material via the binder, and wherein the porous adsorbent is obtained by supporting an organic compound that chemically reacts with aldehydes on a porous support, and the porous adsorbent is formed per 1cm ³ The density of the coating material in the sheet-shaped adsorbing material is 0.10 to 0.25g/cm ³ ，

The adhesive has a Marlon test value of 0.15% or less,

at least an azole compound is contained as the organic compound,

the binder includes an emulsion-based organic binder,

the marlon test value is a value determined by the following method:

malong test value (%) = (oven dried mass of aggregate/oven dried mass of adhesive) × 100%

The manufacturing method comprises the following steps:

a step of bringing the sheet-like air-permeable substrate into contact with a slurry containing the porous adsorbent and the binder;

squeezing the sheet-like air-permeable base material that has been brought into contact with the slurry;

and a step of drying the sheet-like air-permeable base material after the squeezing step.

6. The method for producing a sheet-like adsorbent according to claim 5, wherein the sheet-like adsorbent has a void ratio of 65 to 85%.

7. The method for producing a sheet-shaped adsorbent according to claim 5 or 6,

the sheet-like adsorbent material contains at least 4-amino-1, 2, 4-triazole as the organic compound.

8. The method for producing a sheet-like adsorbent according to claim 5 or 6,

the sheet-like air-permeable substrate is composed of a material containing at least polyethylene terephthalate.