JP2013136865A - Active carbon fiber nonwoven fabric and element including the nonwoven fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active carbon fiber nonwoven fabric that is configured by using a fiber having a fiber diameter which can reduce pressure loss of an element and has a tensile strength which prevents the active carbon fiber nonwoven fabric from being damaged when the fabric is strongly wound around a cylinder.SOLUTION: The active carbon fiber nonwoven fabric is obtained by spinning and hardening a mixture in which at least one compound selected from the group consisting of fatty acid amide, phosphate ester and cellulose is mixed in a phenol resin to obtain a phenolic fiber, processing the obtained hardened phenolic fiber into a nonwoven fabric, and then carbonizing and activating the nonwoven fabric. The constituent active carbon fiber has a fiber diameter of 21 μm to 40 μm and a toluene absorption rate of 20% to 75%. The nonwoven fabric has a tensile strength of 4 N/cmor more.

Description

  The present invention relates to an activated carbon fiber nonwoven fabric and an element using the nonwoven fabric.

  In a continuous gas adsorption processing apparatus, an element constituted by wrapping an activated carbon fiber nonwoven fabric around a cylinder is suitably used because the adsorption / desorption speed is high and the size can be reduced. In recent years, miniaturization of elements has been desired in order to reduce the installation space of the apparatus and to reduce manufacturing costs.

  An effective means for reducing the size of such elements is to increase the bulk density of the activated carbon fiber nonwoven fabric. However, with regard to the fibers constituting the activated carbon fiber nonwoven fabric, if the bulk density of the nonwoven fabric is increased while maintaining the single fiber fineness as before (about 2 dtex to 3 dtex), the pressure loss of the element increases, and the element is treated. It is necessary to increase the capacity of the blower for blowing gas. As a result, there are cases where the benefits associated with the miniaturization of the elements cannot be fully enjoyed.

  Therefore, the present inventors have developed a patent application for an activated carbon fiber nonwoven fabric using a fiber having a single fiber fineness of 5 dtex or more to suppress the pressure loss of the element, and have already obtained the right (Patent Document 1). ).

  On the other hand, when the fiber diameter of the fiber is increased, the pressure loss of the element is reduced, but the fiber becomes hard and is not easily entangled, and the resultant activated carbon fiber nonwoven fabric has a reduced tensile strength. For this reason, when the activated carbon fiber nonwoven fabric is strongly wound around the cylinder to obtain an element having a high bulk density, the activated carbon fiber nonwoven fabric may be damaged.

JP 2002-161439 A

  The present invention has been made in order to solve the above-mentioned problems, and is composed of fibers having a fiber diameter that can reduce the pressure loss of the element, and has activated carbon having a tensile strength that does not break even when strongly wound around a cylinder. Providing a fiber nonwoven fabric was raised as an issue.

  As a result of diligent investigations, the inventors of the present invention have not only been able to reduce the pressure loss of an element composed of the nonwoven fabric, but the activated carbon fiber nonwoven fabric obtained using a phenol-based fiber having a predetermined fiber diameter can not only reduce the pressure loss of the element. It has been found that it has sufficient tensile strength and can be strongly wound around a cylinder and the bulk density of the element can be increased, and the present invention has been completed.

That is, the activated carbon fiber nonwoven fabric of the present invention is obtained by spinning and curing a mixture in which a phenol resin is mixed with at least one compound selected from the group consisting of fatty acid amides, phosphate esters, and celluloses. The obtained activated carbon fiber is obtained by carbonizing and activating the non-woven fabric after processing the non-woven fabric, the fiber diameter is 21 μm to 40 μm, the toluene adsorption rate is 20% to 75%, and the nonwoven fabric has a tensile strength of 4 N / cm ^2. It is the activated carbon fiber nonwoven fabric characterized by the above.

In the activated carbon fiber nonwoven fabric of the present invention, and it basis weight is ^{200g / m 2 ~800g / m 2} , it bulk density of 65kg / m ³ ~100kg / m ³ are all preferred embodiments.

In this invention, it is comprised from the said activated carbon fiber nonwoven fabric, and a bulk density is 90 kg / m < ³ > -170.
An activated carbon fiber element characterized by being kg / m ³ is included.

  In the activated carbon fiber element of the present invention, it is a preferred embodiment that the pressure loss is 550 mmAq or less.

  The present invention provides a method for producing the activated carbon fiber nonwoven fabric, which comprises spinning a mixture in which at least one compound selected from the group consisting of fatty acid amides, phosphate esters, and celluloses is mixed with a phenol resin. And curing to produce phenolic fiber, processing the phenolic fiber into a nonwoven fabric to produce an activated carbon fiber nonwoven fabric precursor, and carbonizing and activating the precursor. The manufacturing method of the activated carbon fiber nonwoven fabric characterized by this is included.

  Since the activated carbon fiber nonwoven fabric of the present invention has a large fiber diameter of the fibers constituting the nonwoven fabric, an element with low pressure loss can be obtained. Moreover, since the activated carbon fiber nonwoven fabric of the present invention has a high tensile strength and is not easily damaged even when strongly wound around a cylinder, an element having a high bulk density can be obtained.

The activated carbon fiber nonwoven fabric of the present invention is a nonwoven fabric composed of activated carbon fibers having a fiber diameter of 21 μm to 40 μm and a toluene adsorption rate of 20% to 75%, and has a tensile strength of 4 N / cm ² or more. Features. Hereinafter, the activated carbon fiber nonwoven fabric of the present invention will be described in detail. In some cases, the activated carbon fiber is simply referred to as ACF (Activated Carbon Fiber). Hereinafter, the activated carbon fiber nonwoven fabric may be omitted and referred to as “ACF nonwoven fabric”.

(Fiber diameter)
The fiber diameter of the fibers constituting the ACF nonwoven fabric of the present invention is 21 μm or more (preferably 22 μm or more, more preferably 23 μm or more, and further preferably 24 μm or more). By setting the fiber diameter to 21 μm or more, the pressure loss of the element obtained using the ACF nonwoven fabric of the present invention can be sufficiently suppressed. The upper limit of the fiber diameter is 40 μm (preferably 35 μm). In order to obtain an ACF nonwoven fabric having a fiber diameter exceeding 40 μm, it is necessary to process a raw yarn (fiber) having a single fiber fineness exceeding 22 dtex, and then to activate the raw yarn. Then, the raw yarn exceeding 22 dtex is processed into a nonwoven fabric. May be difficult.

(Toluene adsorption capacity)
The activated carbon fiber constituting the ACF nonwoven fabric of the present invention has a toluene adsorption rate of 20% or more (preferably 30% or more, more preferably 40% or more), 75% or less, which is one of the indices representing the degree of activation. (Preferably 70% or less). By setting the toluene adsorption rate to 20% or more, even if the winding thickness of the ACF nonwoven fabric around the cylinder is reduced, sufficient gas adsorption ability can be exhibited, so that the element can be efficiently downsized. On the other hand, when the toluene adsorption rate exceeds 75%, the weight yield from the raw yarn of the obtained ACF nonwoven fabric becomes extremely small, and the tensile strength of the ACF nonwoven fabric tends to decrease.

(Tensile strength)
Tensile strength of the ACF nonwoven fabric of the present invention, 4N / cm ² or more (preferably 4.5 N / cm ² or more, more preferably 5N / cm ² or more). If the tensile strength is 4 N / cm ² or more, even if the tension when the ACF nonwoven fabric is strongly wound around the cylinder is increased, the nonwoven fabric is not easily damaged, so that an element with a high bulk density can be obtained. The upper limit of the tensile strength is not particularly limited, but it is difficult to realize a tensile strength exceeding 20 N / cm ² in an ACF nonwoven fabric having a fiber diameter of 21 μm to 40 μm.

(Weight)
The ACF nonwoven fabric of the present invention preferably has a basis weight of 200 g / m ² or more (more preferably 250 g / m ² or more, more preferably 300 g / m ² or more). By setting the basis weight to 200 g / m ² or more, an ACF nonwoven fabric having a tensile strength of 4 N / cm ² or more can be obtained. The upper limit of the basis weight is 800 g / m ² (more preferably 750 g / m ² , still more preferably 700 g / m ² ). An ACF nonwoven fabric having a basis weight of more than 800 g / m ² is difficult to produce, or even if the nonwoven fabric can be produced, the effect of improving the tensile strength has reached its peak and lacks flexibility. When producing an element, it tends to be difficult to wind the element around a cylinder.

(The bulk density)
The ACF nonwoven fabric of the present invention preferably has a bulk density of 65 kg / m ³ or more (more preferably 67 kg / m ³ or more, and further preferably 70 kg / m ³ or more). If the bulk density is 65 kg / m ³ or more, an element with a high bulk density can be obtained even if the ACF nonwoven fabric winding tension around the cylinder when producing the element is lowered. The upper limit of the bulk density is 100 kg / m ³ (more preferably 95 kg / m ³ ). An ACF nonwoven fabric having a bulk density exceeding 100 kg / m ³ has a tendency to be difficult to wind around a cylinder due to lack of flexibility although tensile strength is increased.

(Pressure loss of ACF nonwoven fabric)
Since the ACF nonwoven fabric of the present invention having the above characteristics can have a pressure loss coefficient of 0.5 mmAq · s / cm ² or less, an element having a low pressure loss can be produced. Pressure loss coefficient of the ACF nonwoven fabric of the present invention is preferably a 0.45mmAq · s / cm ² or less (more preferably 0.40mmAq · s / cm ² or less). When the pressure loss coefficient exceeds 0.5 mmAq · s / cm ² , the resistance during gas passage is high, and the power loss of the ventilation blower may increase.

(Method for producing ACF nonwoven fabric)
The ACF nonwoven fabric of the present invention can be produced by processing a nonwoven fabric using phenolic fibers as a raw yarn to produce an ACF nonwoven fabric precursor, and then carbonizing and activating the precursor. Hereinafter, the manufacturing method of the ACF nonwoven fabric of this invention is demonstrated in detail.

[Phenol fiber]
The phenol fiber used in the present invention is obtained by spinning a mixture obtained by mixing a phenol resin with at least one compound (compound) selected from the group consisting of fatty acid amides, phosphate esters, and celluloses. Phenol fiber is preferably used. By adding the compound to the phenolic resin, the phenolic fiber can be finished soft, so that the entanglement of the fiber can be enhanced when forming the nonwoven fabric. Thereby, since the entanglement property of the fiber in the ACF nonwoven fabric obtained by carbonization and activation is improved, desired tensile strength can be imparted to the ACF nonwoven fabric.

<Phenolic resin>
As the phenol resin, a novolac type phenol resin obtained by reacting phenols and aldehydes in the presence of an acidic catalyst, or a resol type phenol obtained by reacting phenols and aldehydes in the presence of a basic catalyst Examples thereof include resins, various modified phenolic resins, and mixtures thereof.

  The phenols are not particularly limited as long as they can be reacted with aldehydes in the presence of an acidic or basic catalyst to obtain each phenol resin. Phenol, o-cresol, m-cresol, p-cresol, 2, 3 -Xylenol, 3,5-xylenol, m-ethylphenol, m-propylphenol, m-butylphenol, p-butylphenol, o-butylphenol, resorcinol, hydroquinone, catechol, 3-methoxyphenol, 4-methoxyphenol, 3-methyl Catechol, 4-methylcatechol, methylhydroquinone, 2-methylresorcinol, 2,3-dimethylhydroquinone, 2,5-dimethylresorcinol, 2-ethoxyphenol, 4-ethoxyphenol, 4-ethylresorcinol, 3-e Xyl-4-methoxyphenol, 2-propenylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 3,4,5-trimethylphenol, 2-isopropoxyphenol, 4-propoxyphenol, 2-allyl Phenol, 3,4,5-trimethoxyphenol, 4-isopropyl-3-methylphenol, pyrogallol, phloroglucinol, 1,2,4-benzenetriol, 5-isopropyl-3-methylphenol, 4-butoxyphenol, 4-t-butylcatechol, t-butylhydroquinone, 4-t-pentylphenol, 2-t-butyl-5-methylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3-phenoxyv Nord, 4-phenoxyphenol, 4-hexyloxyphenol, 4-hexanoylresorcinol, 3,5-diisopropylcatechol, 4-hexylresorcinol, 4-heptyloxyphenol, 3,5-di-t-butylphenol, 3,5 -Di-t-butylcatechol, 2,5-di-t-butylhydroquinone, di-sec-butylphenol, 4-cumylphenol, nonylphenol, 2-cyclopentylphenol, 4-cyclopentylphenol, bisphenol A, bisphenol F, etc. Can be mentioned.

  Among them, phenol, o-cresol, m-cresol, p-cresol, bisphenol A, 2,3-xylenol, 3,5-xylenol, m-butylphenol, p-butylphenol, o-butylphenol, 4- Phenylphenol and resorcinol are preferred, with phenol being most preferred. The said phenols may be used individually by 1 type, and may use 2 or more types together.

  Examples of the aldehydes include formaldehyde, trioxane, furfural, paraformaldehyde, benzaldehyde, methyl hemiformal, ethyl hemiformal, propyl hemiformal, salicylaldehyde, butyl hemiformal, phenyl hemiformal, acetaldehyde, propylaldehyde, phenylacetaldehyde, α- Phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p -Ethylbenzaldehyde, pn-butylbenzaldehyde, etc. are mentioned.

  Of these, formaldehyde, paraformaldehyde, furfural, benzaldehyde, and salicylaldehyde are preferable, and formaldehyde and paraformaldehyde are particularly preferable. The aldehydes may be used alone or in combination of two or more.

  Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, succinic acid, butyric acid, lactic acid, benzenesulfonic acid, p-toluenesulfonic acid, boric acid, and salts with metals such as zinc chloride or zinc acetate. It is done. The said acidic catalyst may be used individually by 1 type, and may use 2 or more types together.

  Examples of the basic catalyst include alkali metal hydroxides such as sodium hydroxide and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; ammonium hydroxide; diethylamine, triethylamine, Examples include amines such as ethanolamine, ethylenediamine, and hexamethylenetetramine. The said basic catalyst may be used individually by 1 type, and may use 2 or more types together.

  Examples of the various modified phenol resins include those obtained by modifying a novolak-type or resol-type phenol resin by known techniques such as boron modification, silicon modification, heavy metal modification, nitrogen modification, sulfur modification, oil modification, rosin modification and the like.

  In the present invention, it is preferable to use a novolac type phenol resin or a resol type phenol resin. A phenol resin may be used individually by 1 type, and may use 2 or more types together.

<Formulation>
The fatty acid amides used as a blend in the present invention means a non-polymer having a structure in which one or more hydrogen atoms bonded to the nitrogen atom of ammonia or amine are substituted with an acyl group. A primary amide in which two atoms are bonded, a secondary amide in which one hydrogen atom is bonded to the nitrogen atom, a tertiary amide in which no hydrogen atom is bonded to the nitrogen atom, a lactam, and one molecule Includes those having two or more amine nitrogen atoms. Therefore, the “fatty acid amides” in the present invention are different from polymers such as so-called aliphatic polyamides typified by nylon-6 and nylon-6,6. “Fatty acid amides” are also referred to as fatty acid amides.

Examples of the primary amide include compounds represented by the general formula “R ¹ C (═O) NH ₂ ”.

In the above formula, R ¹ is a hydrocarbon group which may have a substituent. Here, “may have a substituent” means that a part or all of the hydrogen atoms of the hydrocarbon group may be substituted with a substituent. The hydrocarbon group for R ¹ may be saturated or unsaturated, and may be linear or branched, and the carbon number thereof is preferably 5 to 31, and more preferably 11 to 23. However, the carbon number of the hydrocarbon group of R ¹ does not include the carbon number in the substituent described later. Examples of the substituent that the hydrocarbon group may have include a hydroxy group and a hydroxyalkyl group. The hydroxyalkyl group preferably has 1 to 11 carbon atoms.

  Specific examples of primary amides include caproic acid amide, caprylic acid amide, pelargonic acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, lignoceric acid amide, etc. Saturated fatty acid monoamides such as oleic acid amide, erucic acid amide, and ricinoleic acid amide.

Examples of secondary amides include compounds represented by the general formula “R ¹ C (═O) NHR ² ”.

In the above formula, R ¹ is the same as R ¹ in the description of the primary amide.

In the formula, R ² is a hydrocarbon group which may have a substituent, or —C (═O) R ³ . The hydrocarbon group for R ² may be saturated or unsaturated, and may be linear or branched, and the carbon number thereof is preferably 1 to 23, and more preferably 1 to 17. Examples of the substituent that the hydrocarbon group may have include a hydroxy group.

R ³ may be the same as R ¹ in the description of the primary amide, and R ¹ and R ³ may be the same as or different from each other. A compound in which R ² is —C (═O) R ³ is also referred to as an imide.

  Specific examples of secondary amides include substituted amides such as stearyl stearic acid amide, oleyl oleic acid amide, stearyl oleic acid amide, oleyl stearic acid amide, stearyl erucic acid amide, oleyl palmitic acid amide; methylol stearic acid amide, methylol And methylolamide such as behenic acid amide.

Examples of the tertiary amide include compounds represented by the general formula “R ¹ C (═O) NR ⁴ R ⁵ ”.

In the above formula, R ¹ is the same as R ¹ in the description of the primary amide.

In the formula R ^4, R ⁵ are each like can be mentioned as R ² in the description of the secondary amide, may be different from one another identical R ⁴ and R ^5.

  Specific examples of the tertiary amide include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide and the like.

  Among the lactams, preferred are those having 3 to 12 carbon atoms. Specifically, β-propiolactam, γ-butyrolactam (2-pyrrolidone), δ-valerolactam (2-piperidone), ε-caprolactam, undecaractam, dodecaractam (lauro / laurylactam) and the like can be mentioned. It is done.

Examples of compounds having two or more amine nitrogen atoms in one molecule include compounds represented by the general formula “R ¹¹ C (═O) NH—R ⁶ —NHC (═O) R ¹² ”, the general formula “R ¹¹ NHC (═O) —R ⁷ —C (═O) NHR ¹² ”.

In the formula, R ¹¹ and R ¹² are each a hydrocarbon group which may have a substituent, and examples thereof include those similar to R ¹ described above. R ⁶ and R ⁷ are each a divalent hydrocarbon group, and the number of carbon atoms thereof is preferably 1 to 10, and more preferably 1 to 8.

  Specific examples of compounds having two or more amine nitrogen atoms in one molecule include methylenebisstearic acid amide, ethylene bisstearic acid amide, ethylene biscaprylic acid amide, ethylene bislauric acid amide, and ethylene bisbehenic acid amide. , Methylene bishydroxy stearic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis behenic acid amide, hexamethylene bis hydroxy stearic acid amide; N, N-distearyl adipic acid amide, N, N-distearyl sebacic acid amide, etc. Is mentioned.

  Among the above fatty acid amides, primary amides and secondary amides are preferable, primary amides are more preferable, saturated fatty acid monoamides, non-volatile amides from the viewpoints of handleability, stability and spinnability of the raw material mixture. Saturated fatty acid monoamides are particularly preferred, with behenamide being most preferred.

  Moreover, as fatty acid amides, if the carbon number is too small, the heat resistance of the phenolic fiber may be reduced, and if the carbon number is too large, the compatibility with the phenol resin used as the raw material for the phenolic fiber is reduced. There is a fear. Therefore, as for fatty acid amides, that whose carbon number is 12-30 by the whole molecule is preferred, and what is 18-24 is more preferred. Fatty acid amides may be used alone or in combination of two or more.

“Phosphoric acid” of the phosphoric acid esters used as a blend in the present invention is a general term for various oxo acids generated by hydrolysis of tetraphosphorus decaoxide (P ₄ O ₁₀ ), and is represented by the following chemical formula. Orthophosphoric acid (a), pyrophosphoric acid (diphosphoric acid) (b), triphosphoric acid (c), tetraphosphoric acid (d), metaphosphoric acid (e) and the like.

[Wherein m represents the number of repetitions. ]

  In the present invention, the “phosphate esters” mean those in which one or more of —OH in phosphoric acid is substituted with a group represented by the following general formula (1) (phosphate esters) or salts thereof.

[Wherein R ¹³ is a hydrocarbon group having 4 or more carbon atoms which may have a hetero atom (atom other than carbon and hydrogen), AO is an oxyalkylene group having 2 to 4 carbon atoms, n Is the average number of moles added and represents a number from 0 to 100. ]

In the formula (1), as the hydrocarbon group for R ¹³ , an alkyl group, an alkenyl group, an aryl group, a group in which a part of hydrogen atoms of the alkyl group is substituted with an aryl group, or a part of hydrogen atoms in an alkenyl group Are groups substituted with an aryl group.

When the hydrocarbon group for R ¹³ is an alkyl group or an alkenyl group, R ¹³ preferably has 4 to 22 carbon atoms, and more preferably 8 to 18 carbon atoms.

When the hydrocarbon group of R ¹³ is an aryl group, the carbon number of R ¹³ is preferably 6 to 35, and more preferably 6 to 27. Specific examples include a phenyl group, a naphthyl group, a benzyl group, a tolyl group, and a xylyl group.

Regardless of the hydrocarbon group of R ¹³ , if the number of carbon atoms of R ¹³ exceeds the upper limit, compatibility with the phenol resin tends to decrease. When R ¹³ is an aryl group, the compatibility with the phenol resin is relatively better than when R ¹³ is an alkyl group or an alkenyl group.

  In the formula (1), examples of AO include an oxyethylene group, an oxypropylene group, and an oxybutylene group. Note that an oxygen atom in the oxyalkylene group is bonded to the phosphorus atom.

  In said formula (1), 0-50 are preferable and, as for n, 0-10 are more preferable.

  As phosphate esters, since mechanical strength is likely to increase particularly when a large-diameter phenolic fiber is used, at least one of —OH in orthophosphoric acid is substituted with the group represented by the above formula (1). (Orthophosphoric acid ester) or a salt thereof is preferred.

  Specific examples of the orthophosphoric acid ester include monoesters (f), diesters (g), and triesters (h) of orthophosphoric acid represented by the following general formula. Of these, monoesters and diesters of orthophosphoric acid are preferable.

[Wherein, R ¹³ , AO and n are the same as defined above. In the diester and triester, a plurality of — (AO) _n OR ¹³ may be the same or different from each other. ]

  Examples of the phosphate ester salt include alkali metal salts, alkaline earth metal salts, ammonium salts and amine salts of phosphate esters. Phosphate esters may be used alone or in combination of two or more.

  Examples of celluloses used as a blend in the present invention include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like. Cellulose may be used independently or may use 2 or more types together.

[Process for producing phenolic fiber]
The phenolic fiber used in the present invention is a raw material mixing step of mixing the phenol resin obtained by the above method and the above blend, and the raw material mixture obtained in the raw material mixing step is spun to obtain a yarn. It can be produced through a spinning process.

<Raw material mixing process>
When melt-spinning, which is the most common spinning method in the spinning process described later, is performed by melt-mixing a phenol resin and a blend, either a novolak-type or resol-type phenol resin can be used as the phenol resin. However, the resol type is inferior in thermal stability to the novolak type, and the polymerization proceeds easily by heating during melting, so solidification in the melt spinning apparatus is inevitable, and continuous and stable spinning is performed. It ’s difficult. Therefore, it is particularly preferable to select a novolac type phenol resin in consideration of the ease of the process in industrial production and versatility.

  In the raw material mixing step, when the phenol resin and the compound are mixed, the amount of the phenol resin used is such that the proportion of the phenol resin in the obtained raw material mixture is 55% by mass to 99.9% by mass. The amount is preferably 70% by mass to 99% by mass, and more preferably 85% by mass to 95% by mass.

  The amount of the compound used is such that the ratio of the compound in the raw material mixture obtained (the ratio of the total of the compounds when using a plurality of compounds) is 0.1% by mass to 45% by mass. The amount is preferably 1% by mass to 30% by mass, and more preferably 5% by mass to 15% by mass. If the proportion of the blend is equal to or greater than the preferred lower limit, the effect of improving the mechanical strength when the phenolic fiber is increased in diameter is likely to be obtained. On the other hand, if the proportion of the blend is less than or equal to the preferable upper limit value, it is easy to maintain the characteristics such as heat resistance, flame retardancy, and chemical resistance of the phenol fiber.

  Specifically, the amount of fatty acid amides used is preferably an amount such that the ratio of fatty acid amides in the obtained raw material mixture is 0.1% by mass to 45% by mass, and preferably 1% by mass to 30% by mass. % Is more preferable, and an amount of 3% by mass to 10% by mass is particularly preferable.

  The amount of phosphate esters used is preferably, for example, an amount such that the proportion of phosphate esters in the obtained raw material mixture is 0.1% by mass to 45% by mass, and 1% by mass to 30% by mass. It is more preferable that the amount is 5% by mass to 20% by mass.

  The amount of cellulose used is, for example, preferably an amount such that the ratio of cellulose in the obtained raw material mixture is 0.1% by mass to 45% by mass, and an amount of 1% by mass to 30% by mass. It is more preferable that the amount is 5% by mass to 20% by mass.

  Examples of the method of mixing the phenol resin and the compound include a method of melting and mixing the two, a method of dissolving and mixing both using a solvent, and the like. Among these, from the viewpoint of complexity of the process, environmental load, and economical efficiency, a method of melt-mixing both is preferable. An example of such melt mixing is a method of kneading both.

  The heat-kneading of the phenol resin and the compound can be performed using a known kneading apparatus, and examples of the kneading apparatus include an extruder-type kneader, a mixing roll, a Banbury mixer, and a high-speed biaxial continuous mixer. .

  What is necessary is just to select the temperature of heat-kneading suitably with the property of a raw material, etc., 200 degrees C or less is preferable and 140 to 180 degreeC is more preferable. By setting the temperature of the heat-kneading to a preferable upper limit value or less, thermal denaturation and deterioration due to exposure of the raw material to a high temperature can be easily suppressed. By setting the temperature of the heat-kneading to a preferable lower limit value or more, it becomes possible to efficiently mix both.

  In the method of dissolving and mixing a phenol resin and a blend using a solvent, the raw material mixture is obtained by dissolving and mixing both in a solvent that can dissolve both, and then removing the solvent by evaporation.

  Examples of the solvent capable of dissolving both include a solvent obtained by mixing one or two or more selected from ketone solvents, ether solvents, nitrogen-containing solvents, hydrocarbon solvents, ester solvents, alcohol solvents, and the like. It is done.

  In the dissolution and mixing of the phenol resin and the blend, it is preferable to gradually add the phenol resin and the blend while stirring the solvent. At that time, heating is effective if the phenol resin or the compound is hardly dissolved in the solvent. Further, by applying pressure, it is possible to heat the solvent at a temperature higher than the boiling point of the solvent at normal pressure, which is further effective. However, since exposure to the raw material at a high temperature may cause thermal denaturation and deterioration, it is preferable to perform the heating limitedly until the raw material is completely dissolved.

  The concentration of the phenol resin and the compound dissolved in the solvent is not particularly limited, and may be set as appropriate in consideration of the properties of the raw materials and the spinning method in the subsequent spinning step. In addition, from the point that it takes a lot of time and energy to recover the solvent to be removed by evaporation, it is preferable to set the concentrations of the phenol resin and the compound as high as possible in consideration of their respective solubilities.

  As a method of mixing the phenol resin and the compound, a method other than the melt mixing and dissolution mixing described above may be used. For example, when using a dry spinning, wet spinning or dry / wet spinning method as a spinning method in the subsequent spinning step, a raw material mixture solution obtained by dissolving and mixing both in a solvent capable of dissolving both the phenol resin and the compound is used. It may be prepared. The raw material mixture solution can be used directly as a stock solution for spinning.

  It is also effective to mix and mix the compound in the middle of the phenol resin synthesis reaction so long as the raw material does not deteriorate at the temperature during the synthesis reaction without inhibiting the synthesis reaction of the phenol resin. It is.

  In the raw material mixing step, even if any method is used to obtain the raw material mixture, known additives, plasticizers, compatibilizers, antioxidants, ultraviolet absorbers, penetrants, if necessary. Thickeners, antifungal agents, dyes, pigments, fillers and the like may be used.

  In particular, when the phenol resin and the fatty acid amides are melt-mixed and the melt viscosity of the fatty acid amides is extremely different from that of the phenol resin, it is preferable to use a compatibilizing agent. This can prevent separation during spinning.

<Spinning process>
In the spinning step, the raw material mixture obtained in the raw material mixing step is spun to obtain a yarn.

  As the spinning method, a known method can be appropriately selected in view of the properties of the raw material mixture, and examples thereof include wet spinning, dry spinning, dry / wet spinning, melt spinning, gel spinning, and liquid crystal spinning. . Of these, melt spinning is preferred because of the simplicity of the apparatus and economic advantages. When melt spinning is used as a spinning method, a general melt spinning apparatus can be used.

  As a melting apparatus of the melt spinning apparatus, a grid melter type, a single screw extruder method, a twin screw extruder method, a tandem extruder method, or the like can be used. In order to prevent oxidation of the molten raw material mixture, nitrogen substitution in the melt spinning apparatus may be performed, or an operation of removing a trace amount of residual solvent or monomers is performed using an extruder equipped with a vent. May be.

  In melt spinning, the temperature condition is preferably 120 ° C to 200 ° C, more preferably 140 ° C to 170 ° C. By setting the temperature condition to be equal to or higher than the preferable lower limit, spinning can be performed efficiently. By setting the temperature condition to a preferable upper limit value or less, thermal denaturation and deterioration can be easily suppressed, and the phenol resin and the compound are hardly separated.

  As the spinneret, a normal one can be used, and the hole diameter is preferably 0.05 mm or more and 1 mm or less, more preferably 0.07 mm or more and 0.5 mm or less, and the L / D (length / diameter) of the capillary part is 0.5 or more and 10 or less are preferable, and 1 or more and 5 or less are more preferable. By setting the pore diameter and L / D within the above preferred ranges, stable spinning can be achieved.

  In the case of a special fiber manufacturing method (for example, in the case of side-by-side conjugate fiber, core-sheath type conjugate fiber, sea-island type conjugate fiber, etc.), a conjugate base that combines a side-by-side type or seascore type or a third component polymer. Can also be used.

  The spinning speed is preferably 15 m / min or more and 3000 m / min or less, more preferably 30 m / min or more and 2000 m / min or less, and further preferably 50 m / min or more and 1600 m / min or less. By setting the spinning speed to a preferable lower limit value or more, spinning can be performed efficiently. By setting the spinning speed to a preferable upper limit value or less, the occurrence of yarn breakage during spinning can be suppressed.

<Curing process>
It is preferable that the step of producing the phenol fiber includes a curing step of curing the yarn obtained in the spinning step. By curing the yarn in the curing step, the phenol resin portion is mainly cross-linked, so that the mechanical strength of the thickened phenol fiber increases.

  When a novolac type phenol resin is used as a raw material phenol resin, a method of curing the yarn obtained in the spinning step is to immerse the yarn processed into a staple shape or a tow shape in the treatment liquid in the reaction vessel. A batch-type curing method, a bobbin-like or skein-like processed product is brought into contact with the treatment liquid, or a tow-like processed product is continuously brought into contact with the treatment liquid and cured. The method etc. are mentioned.

  The treatment liquid is composed of a catalyst and aldehydes.

  As a catalyst, the acidic catalyst and basic catalyst which were illustrated as what can be used when manufacturing a phenol resin are mentioned. Moreover, as aldehydes, the aldehydes illustrated as what can be used when manufacturing a phenol resin are mentioned.

  Curing is preferably performed in the liquid phase by heating at a temperature of 60 ° C. to 110 ° C. for 3 hours to 30 hours. Moreover, in this invention, you may harden | cure by heating in a gaseous phase.

  In the present invention, after the heating, washing with water and drying, and performing a known post-curing treatment such as further curing by heating at a temperature of 100 to 300 ° C. in an inert gas such as nitrogen, helium, carbon dioxide, etc. Can do. By this post-curing treatment, the cross-linking of the phenol resin portion in the yarn further proceeds, and a phenol fiber having sufficient strength can be obtained.

  On the other hand, when a resol type phenol resin is used as a raw material phenol resin, the yarn can be cured by heat treatment by a wet heat method or a dry heat method.

  As heat treatment conditions, the temperature is preferably 100 to 220 ° C, more preferably 120 to 180 ° C, and the treatment time is preferably 5 to 120 minutes, more preferably 20 to 60 minutes.

  The single fiber fineness of the phenolic fiber used in the present invention is preferably 7 dtex or more (more preferably 8 dtex or more), and preferably 22 dtex or less (more preferably 17 dtex or less). When an ACF nonwoven fabric having a high bulk density is produced using a phenol fiber having a single fiber fineness of less than 7 dtex, the pressure loss of the element may increase. When the single fiber fineness of the phenol fiber exceeds 22 dtex, it may be difficult to process the nonwoven fabric using the fiber.

The phenol fiber used in the present invention has a tensile modulus of 370 to 410 kgf / mm ² (more preferably 380 to 400 kgf / mm ² ) and an elongation of 10 to 20% (more preferably 15 to 19%). Preferably there is. By using phenolic fibers having a tensile elastic modulus and elongation in this range, the nonwoven fabric can be easily processed even if the single fiber fineness is 7 dtex or more.

  The fiber length of the phenolic fiber is preferably 35 mm or more (more preferably 50 mm or more), and is preferably 130 mm or less (more preferably 100 mm or less, more preferably 80 mm or less). If the fiber length is less than 35 mm, the fibers cannot be sufficiently entangled, and the resulting ACF nonwoven fabric may have a low tensile strength. When the fiber length exceeds 130 mm, for example, fiber cutting or damage during needle punching becomes severe, and the tensile strength may also be lowered.

  The presence or absence of the crimp of the phenol fiber is not particularly limited. In order to enhance the entanglement of the fiber, the phenolic fiber may have a crimp. On the other hand, the phenolic fiber containing the blend is soft even if it has a large diameter, and is excellent in confounding property. Therefore, in the present invention, a phenolic fiber having no crimp can be used.

[Nonwoven fabric processing]
The method for processing a phenol-based fiber into a nonwoven fabric is not particularly limited as long as it can prevent fiber breakage at the time of processing and can sufficiently entangle between fibers, and examples thereof include a needle punch method and a water punch method. It is done. The needle punch method is preferable because the density of the nonwoven fabric obtained can be adjusted by adjusting the needle density and the needle depth according to the change in the fiber diameter.

When the nonwoven fabric processing is performed by the needle punch method, the needle density is 370 / inch ² or more (more preferably 450 / inch ² or more), the needle depth is 5 mm or more (more preferably 7 mm or more), 30 mm or less (more Preferably it is 20 mm or less. By setting the needle density to 370 / inch ² or more, the entanglement between the fibers increases, and the bulk density of the ACF nonwoven fabric precursor increases accordingly. If the needle density is too high, fiber breakage may occur, and the resulting ACF nonwoven fabric may have a lower bulk density and tensile strength. Therefore, the upper limit of the needle density is preferably 700 / inch ² . Moreover, when the needle depth is less than 5 mm, the ACF nonwoven fabric precursor may be bulky. When the needle depth exceeds 30 mm, needle breakage is likely to occur. Further, the ACF nonwoven fabric precursor tends to have more stripes.

[Carbonization / activation process]
Carbonization and activation treatment of the ACF nonwoven fabric precursor is, for example, carbonized at 400 ° C. to 1000 ° C. for 10 minutes to 120 minutes in an inert atmosphere such as nitrogen and argon in a carbonization furnace, and then in an activation furnace, It can be performed by activation treatment at 800 ° C. or higher for 30 minutes to 180 minutes in an activation gas atmosphere such as water vapor.

(element)
The element of the present invention can be produced by winding the ACF nonwoven fabric obtained through the above steps around a cylinder. The winding tension of the nonwoven fabric is preferably about 1/3 or less of the tensile strength so that the ACF nonwoven fabric is not damaged.

(The bulk density)
Since the ACF nonwoven fabric of this invention has the outstanding tensile strength, the tension | tensile_strength at the time of winding the said nonwoven fabric around a cylinder can be raised conventionally. Therefore, in the present invention, it is possible to bulk density is obtained an element of ^{90kg / m 3 ~170kg / m 3} .

  Thus, since the element of the present invention has a large bulk density, an element having the same adsorption ability as that of a conventional element can be manufactured with a smaller size. In addition, if the volume of the element of the present invention is made equal to the volume of the conventional element, an element with even more excellent adsorbability can be produced. Furthermore, since the element of the present invention has a large bulk density, it is not necessary to adjust the bulk density by further compressing the element after the element is manufactured. Therefore, the ACF can be prevented from dropping or scattering due to the compression.

When the bulk density of the element exceeds 170 kg / m ³ , the pressure loss of the element may increase. The bulk density of the element of the present invention is preferably ^{100kg / m 3 ~150kg / m 3} .

(Element pressure loss)
Since the element of this invention is comprised using the ACF nonwoven fabric comprised from a fiber with a large fiber diameter, a pressure loss is small, specifically, it can be set to 550 mmAq or less. Therefore, even if the bulk density of the ACF nonwoven fabric is increased to reduce the size of the element, it is not necessary to increase the capacity of the blower for blowing the gas to be processed to the element, so that the benefits associated with the downsizing of the element can be fully enjoyed. .

  The pressure loss of the element of the present invention is preferably 500 mmAq or less (more preferably 400 mmAq or less). The lower limit of the pressure loss is not particularly limited, but is preferably 100 mmAq or more (more preferably 110 mmAq or more). In order to make the pressure loss of the element less than 100 mmAq, it is necessary to further increase the fiber diameter of the fibers constituting the ACF nonwoven fabric, and it is difficult to produce a nonwoven fabric having such a fiber diameter.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples, and can be implemented with appropriate modifications within a range that can be adapted to the above and the gist described below. These are all included in the technical scope of the present invention.

  First, the single fiber fineness, tensile elastic modulus, elongation, fiber diameter of “activated carbon fiber constituting ACF nonwoven fabric”, toluene adsorption rate, “ACF nonwoven fabric” The tensile strength, basis weight, bulk density, pressure loss (pressure loss) coefficient, and the bulk density and pressure loss measurement method of the “element” will be described below.

(Single fiber fineness of phenol fiber)
It measured using DC11B denier computer (made by search Co., Ltd.).

(Tensile modulus of phenol fiber)
It measured based on JISL1015 using RTG-1210 Tensilon universal testing machine (made by A & D Co., Ltd.).

(Elongation of phenolic fiber)
It measured based on JISL1015 using RTG-1210 Tensilon universal testing machine (made by A & D Co., Ltd.).

(Fiber diameter of activated carbon fiber constituting ACF nonwoven fabric)
The fiber diameter (fiber diameter) was measured using a high-definition digital microscope VH-6300 (manufactured by KEYENCE) in accordance with JIS K1477 5.1 (fiber diameter test method).

(Toluene adsorption rate of activated carbon fiber constituting ACF nonwoven fabric)
The toluene adsorption rate was measured according to JIS K1477 “7.8 Toluene adsorption performance”.

(Tensile strength of ACF nonwoven fabric)
Five test pieces (25 mm in width and 100 mm in length) were cut from the width direction and the length direction of the ACF nonwoven fabric, respectively, and an Instron type tensile tester (for example, “STM-T-200BP” manufactured by Toyo Baldwin Co., Ltd.) ), Grip both ends of the test piece with a chuck, measure the breaking strength with a chuck interval of 50 mm and a tensile speed of 20 mm / min (elongation rate 40% / min), and the value is the cross-sectional area of the test piece (width × thickness). ) (Unit N / cm ² ). The thickness was measured using a disk with an area of 4 cm ^{2 and} a load applied to the ACF nonwoven fabric of 9 gf / cm ² . Of the average value of the tensile strength of the test piece cut in the width direction and the average value of the tensile strength of the test piece cut in the length direction, the smaller value was taken as the tensile strength of the ACF nonwoven fabric of the present invention.

(ACF nonwoven fabric weight)
The mass per unit area of the ACF nonwoven fabric was measured and determined in units of g / m ² . The mass was measured in a completely dry state at 100 ° C.

(Bulk density of ACF nonwoven fabric)
The bulk density was determined in units of kg / m ³ by dividing the basis weight by the thickness. The thickness was measured using a disk with an area of 4 cm ^{2 and} a load applied to the ACF nonwoven fabric of 9 gf / cm ² .

(Pressure loss coefficient of ACF nonwoven fabric)
The ACF nonwoven fabric is cut out into a perfect circle with a diameter of 72 mm and set in a ventilation pressure loss measuring jig. Between the true circle with a diameter of 50.5 mm and the perfect circle with a diameter of 72 mm is 0.1 MPa. The pressure loss was measured by pressing with compressed air and flowing air with a wind speed of 30 cm / sec, and the value was determined by dividing the value by the wind speed and thickness (unit: mmAq · s / cm ² ). The measurement was performed at a temperature of 25 ° C. and a humidity of 50%. The thickness was measured in the same manner as that used when measuring the bulk density.

(Element bulk density)
It was determined by measuring the mass of the element before winding the ACF nonwoven fabric and the mass after winding in a state completely dried at 100 ° C., and dividing the difference mass by the volume of the ACF nonwoven fabric calculated from the winding diameter. .

(Element pressure loss)
The pressure when an ACF nonwoven fabric having a width of 1100 mm is wound around a cylindrical element having an inner diameter of 200 mm and a length of 1100 mm so as to have a predetermined element mass and a predetermined element bulk density, and air at a wind speed of 30 cm / sec is flowed from the inside to the outside of the element. Loss was measured.

(Production Example 1 Production of phenol fiber 1)
1000 parts by weight of phenol, 733 parts by weight of formalin 733 parts by weight and 5 parts by weight of oxalic acid were charged into a reaction vessel equipped with a reflux condenser, heated from room temperature to 100 ° C. over 40 minutes, and further reacted at 100 ° C. for 4 hours. Then, the mixture was heated to 200 ° C., dehydrated and concentrated, and then cooled to obtain a novolac type phenol resin.

  475 kg of the above-mentioned novolak type phenol resin and 25 kg of behenamide are charged into a biaxial kneader (high-speed biaxial continuous mixer), kneaded (melted and mixed) at 150 ° C., cooled to room temperature, and light yellow transparent A block-like product was obtained. In addition, behenic acid amide (BNT-22H) manufactured by Nippon Seika Co., Ltd. was used as the behenic acid amide.

  Next, this block-like product is coarsely pulverized and melted at 200 ° C. using a melt spinning apparatus (grid melter type), and the melt obtained by the melting has a pore diameter of 0.1 mm maintained at 170 ° C., A yarn was obtained by spinning (melt spinning) at a spinning speed of 75 m / min while maintaining a constant discharge rate from a spinneret with L / D = 3 and 10 holes.

  The obtained yarn was cut into a length of 70 mm, placed in a container, immersed in an aqueous solution of 14% by mass hydrochloric acid and 8% by mass formaldehyde for 30 minutes at room temperature, heated to 98 ° C. in 2 hours, and further 98 Curing was performed by holding at 2 ° C. for 2 hours.

Subsequently, after taking out the hardened | cured material obtained from the said container and fully washing with water, neutralization was performed for 30 minutes at 60 degreeC with 3 mass% ammonia aqueous solution. Thereafter, it was thoroughly washed with water again and dried at 90 ° C. for 30 minutes to obtain a phenol fiber 1 having a single fiber fineness of 11 dtex, a fiber length of 70 mm, and no fiber crimp.
The phenolic fiber 1 obtained had a tensile modulus of 395 kgf / mm ² and an elongation of 12%.

(Production Example 2 Production of phenolic fiber 2)
In Production Example 1, phenolic fiber 2 having a single fiber fineness of 11 dtex, a fiber length of 70 mm, and no fiber crimp was obtained in the same manner as in Production Example 1 except that oleic acid amide was used in place of behenamide. As the oleic amide, “Nutron (registered trademark)” manufactured by Nippon Seika Co., Ltd. was used.
The obtained phenol fiber 2 had a tensile modulus of 386 kgf / mm ² and an elongation of 11%.

(Production Example 3 Production of phenolic fiber 3)
A single fiber fineness of 17 dtex, a fiber length of 70 mm, and a fiber crimp-free phenol, except that the diameter of the spinneret when spinning the block-like material was changed to 0.15 mm and the discharge rate was increased. A system fiber 3 was obtained.
The obtained phenol fiber 3 had a tensile modulus of 402 kgf / mm ² and an elongation of 8%.

(Production Example 4 Production of phenolic fiber 4)
A single fiber fineness of 7.7 dtex, a fiber length of 70 mm, and no fiber crimping were carried out in the same manner as in Production Example 1 except that the diameter of the spinneret at the time of spinning the block-like material was changed to 0.07 mm and the discharge amount was reduced. Of phenol fiber 4 was obtained.
The obtained phenol fiber 4 had a tensile modulus of 390 kgf / mm ² and an elongation of 25%.

(Production Example 5 Production of phenol fiber 5)
In the production example 1, the mixing amount of the novolak type phenol resin was 450 kg, and the single fiber fineness was 11 dtex in the same manner as in the production example 1 except that the phosphate ester represented by the following formula was changed to 50 kg instead of the behenamide 25 kg. A phenol fiber 5 having a fiber length of 70 mm and no fiber crimp was obtained. The phosphoric acid ester is “Phosphanol (registered trademark) SM-172” (manufactured by Toho Chemical Industry Co., Ltd .; the mass ratio of the monoester of the following formula (1A) to the diester of the following formula (1B) is 1A / 1B = 1. / 1 mixture).

The obtained phenol fiber 5 had a tensile modulus of 427 kgf / mm ² and an elongation of 10%.

(Production Example 6 Production of phenolic fiber 6)
In Production Example 1, the mixing amount of the novolak-type phenol resin was 450 kg, and the same procedure as in Production Example 1 except that 50 kg of cellulose diacetate was used instead of 25 kg of behenamide, the single fiber fineness 11 dtex, the fiber length 70 mm, the fiber A phenolic fiber 6 without crimp was obtained.
The obtained phenol fiber 6 had a tensile modulus of 380 kgf / mm ² and an elongation of 11%.

(Production Example 7 Production of phenol fiber 7)
In Production Example 1, a single fiber fineness of 11 dtex, a fiber length of 70 mm, and no fiber crimping were performed in the same manner as in Production Example 1 except that 450 kg of novolak type phenol resin and 25 kg of behenamide were used instead of 500 kg of novolak type phenol resin. A phenol fiber 7 was obtained.
The obtained phenol fiber 7 had a tensile modulus of 469 kgf / mm ² and an elongation of 4%.

Example 1
Using the phenolic fiber 1 produced in Production Example 1, the back and front treatment was performed with a needle punch machine under the conditions of a needle density of 500 / inch ² , a needle depth of 12 mm (back) and 7 mm (front), and a dry basis weight of 540 g / An ACF nonwoven fabric precursor with m ² and a bulk density of 82.4 kg / m ³ was obtained.

  The obtained ACF nonwoven fabric precursor was carbonized by heating from normal temperature to 890 ° C. over 30 minutes in an inert atmosphere (nitrogen atmosphere), and then at a temperature of 890 ° C. in an atmosphere containing 12% by mass of water vapor. Activation for a minute gave an ACF nonwoven fabric.

The obtained ACF nonwoven fabric was wound around a cylindrical structure having an inner diameter of 200 mm and a length of 1100 mm with a tension of 1.47 N / cm ² until the element mass reached 100 kg, and had a diameter of 1.09 m and a bulk density of 100 kg / m ³ . Got the element. Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric.

(Example 2)
Using the phenolic fiber 1 produced in Production Example 1, the back and front treatment was performed with a needle punch machine under the conditions of a needle density of 500 / inch ² , a needle depth of 12 mm (back), and 7 mm (front), and a dry basis weight of 520 g / An ACF nonwoven fabric precursor with m ² and bulk density of 82.0 kg / m ³ was obtained.

  The obtained ACF nonwoven fabric precursor was heated from normal temperature to 890 ° C. over 36 minutes in an inert atmosphere to be carbonized, and then activated for 120 minutes at a temperature of 890 ° C. in an atmosphere containing 12% by mass of water vapor. ACF nonwoven fabric was obtained. Table 1 shows the characteristics of the activated carbon fiber and the ACF nonwoven fabric constituting the obtained ACF nonwoven fabric.

  Except having used the obtained ACF nonwoven fabric, it carried out similarly to Example 1, and obtained the element of this invention. The characteristics of the obtained element are shown in Table 1.

(Example 3)
Using the phenolic fiber 1 produced in Production Example 1, the back and front treatment was performed with a needle punch machine under the conditions of a needle density of 500 / inch ² , a needle depth of 12 mm (back), and 7 mm (front), and a dry basis weight of 1254 g / An ACF nonwoven fabric precursor with m ² and a bulk density of 99.6 kg / m ³ was obtained.

  An ACF nonwoven fabric and an element of the present invention were obtained in the same manner as in Example 1 except that the obtained ACF nonwoven fabric precursor was used. Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric, and the elements constituting the obtained ACF nonwoven fabric.

Example 4
The ACF nonwoven fabric produced in Example 1 was wound around a cylindrical structure having an inner diameter of 200 mm and a length of 1100 mm with a tension of 2.2 N / cm ² until the element mass reached 100 kg. The characteristics of the obtained element are shown in Table 1.

(Example 5)
Using the phenolic fiber 1 produced in Production Example 1, the back and front treatment was performed with a needle punch machine under the conditions of a needle density of 650 needles / inch ² , a needle depth of 15 mm (back) and 10 mm (front), and a dry basis weight of 540 g / An ACF nonwoven fabric precursor with m ² and bulk density of 129 kg / m ³ was obtained.

  An ACF nonwoven fabric and an element of the present invention were obtained in the same manner as in Example 1 except that the obtained ACF nonwoven fabric precursor was used. Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric, and the elements constituting the obtained ACF nonwoven fabric.

(Example 6)
The ACF nonwoven fabric obtained in Example 5 was wound around a cylindrical structure having an inner diameter of 200 mm and a length of 1100 mm with a tension of 2.2 N / cm ² until the element mass reached 150 kg. The characteristics of the obtained element are shown in Table 1.

(Example 7)
In Example 1, in place of the phenolic fiber 1 produced in Production Example 1, the phenolic fiber 2 produced in Production Example 2 was used and heated from room temperature to 870 ° C. over 12 minutes in an inert atmosphere. ACF non-woven fabric precursor, ACF non-woven fabric, and element were obtained in the same manner as in Example 1 except that carbonization was performed and then activated for 40 minutes at 870 ° C. in an atmosphere containing 12% by mass of water vapor. Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric, and the elements constituting the obtained ACF nonwoven fabric.

(Example 8)
In Example 2, instead of the phenolic fiber 1 produced in Production Example 1, the phenolic fiber 3 produced in Production Example 3 was used, and the needle density was 600 needles / inch ² and the needle depth was measured with a needle punch machine. Except that the ACF nonwoven fabric precursor having a dry basis weight of 778 g / m ² and a bulk density of 98.3 kg / m ³ was obtained by performing the back and front treatment under the conditions of 13 mm (back) and 9 mm (front), except that the ACF nonwoven fabric precursor was used. In the same manner as in Example 2, an ACF nonwoven fabric and elements were obtained. Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric, and the elements constituting the obtained ACF nonwoven fabric.

Example 9
In Example 1, in place of the phenolic fiber 1 produced in Production Example 1, the phenolic fiber 4 produced in Production Example 4 was used, and the needle density was 450 needles / inch ² and the needle depth by a needle punching machine. Except that the ACF nonwoven fabric precursor having a dry basis weight of 535 g / m ² and a bulk density of 80.3 kg / m ³ was obtained by performing the back and front treatment under the conditions of 12 mm (back) and 7 mm (front), and the ACF nonwoven fabric precursor was used. In the same manner as in Example 1, an ACF nonwoven fabric and an element were obtained. Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric, and the elements constituting the obtained ACF nonwoven fabric.

(Example 10)
In Example 8, the obtained ACF nonwoven fabric precursor was carbonized by heating from normal temperature to 870 ° C. over 18 minutes in an inert atmosphere, and then at a temperature of 870 ° C. in an atmosphere containing 12% by mass of water vapor. An ACF nonwoven fabric and an element were obtained in the same manner as in Example 8 except that activation was performed for 60 minutes. Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric, and the elements constituting the obtained ACF nonwoven fabric.

(Example 11)
In Example 1, using the phenolic fiber 1 produced in Production Example 1, the back and front treatment was performed with a needle punching machine under the conditions of a needle density of 600 / cm ² , a needle depth of 13 mm (back), and 9 mm (front). An ACF nonwoven fabric and an element were obtained in the same manner as in Example 1 except that an ACF nonwoven fabric precursor having a dry basis weight of 420 g / m ² and a bulk density of 81.7 kg / m ³ was obtained. Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric, and the elements constituting the obtained ACF nonwoven fabric.

(Example 12)
An ACF nonwoven fabric precursor, an ACF nonwoven fabric, and an element were obtained in the same manner as in Example 1 except that the phenolic fiber 5 obtained in Production Example 5 was used instead of the phenolic fiber 1 used in Example 1. . Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric, and the elements constituting the obtained ACF nonwoven fabric.

(Example 13)
An ACF nonwoven fabric precursor, an ACF nonwoven fabric, and an element were obtained in the same manner as in Example 1 except that the phenolic fiber 6 obtained in Production Example 6 was used instead of the phenolic fiber 1 used in Example 1. . Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric, and the elements constituting the obtained ACF nonwoven fabric.

(Comparative Example 1)
A monofilament fineness of 5.6 dtex, a fiber length of 70 mm, a phenolic fiber (Kinei Chemical Industry Co., Ltd., Kynol KF-0570) without fiber crimp is used, and a needle density of 500 / inch ^{2 is obtained} by a needle punch machine. The back and front treatment was performed under the conditions of needle depth 12 mm (back) and 7 mm (front) to obtain an ACF nonwoven fabric precursor having a dry basis weight of 385 g / m ² and a bulk density of 83.7 kg / m ³ .

  The obtained ACF nonwoven fabric precursor was heated from normal temperature to 890 ° C. for 18 minutes in an inert atmosphere to be carbonized, and then activated for 60 minutes at a temperature of 890 ° C. in an atmosphere containing 12% by mass of water vapor. ACF nonwoven fabric was obtained.

The obtained ACF nonwoven fabric was wound around a cylindrical structure having an inner diameter of 200 mm and a length of 1100 mm with a tension of 1.1 N / cm ² until the element mass reached 100 kg, and had a diameter of 1.26 m and a bulk density of 75 kg / m ³ . Got the element. Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric, and the elements constituting the obtained ACF nonwoven fabric.

(Comparative Example 2)
The ACF nonwoven fabric obtained in Comparative Example 1 was wound around a cylindrical structure having an inner diameter of 200 mm and a length of 1100 mm with a tension of 1.47 N / cm ² until the element mass reached 100 kg, and had a diameter of 1.09 m and a bulk density of 100 kg. An element of / m ³ was obtained. Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric, and the elements constituting the obtained ACF nonwoven fabric.

(Comparative Example 3)
Using the phenolic fiber 7 produced in Production Example 7, a back and front treatment was performed with a needle punch machine under the conditions of a needle density of 650 needles / inch ² , a needle depth of 15 mm (back) and 10 mm (front), and a dry basis weight of 580 g / An ACF nonwoven fabric precursor having a m ² and a bulk density of 115.0 kg / m ³ was obtained.

  The obtained ACF nonwoven fabric precursor was heated from normal temperature to 890 ° C. for 30 minutes in an inert atmosphere to be carbonized, and then activated for 100 minutes at a temperature of 890 ° C. in an atmosphere containing 12% by mass of water vapor. ACF nonwoven fabric was obtained. Table 1 shows the characteristics of the activated carbon fiber and the ACF nonwoven fabric constituting the obtained ACF nonwoven fabric.

The obtained ACF nonwoven fabric was tried to be wound around a cylindrical structure having an inner diameter of 200 mm and a length of 1100 mm with a tension of 1.1 N / cm ² , but the tensile strength of the ACF nonwoven fabric was low, and it was broken and wound. I couldn't.

(Comparative Example 4)
In Comparative Example 1, the back and front treatment was performed with a needle punch machine under the conditions of a needle density of 600 / inch ² , a needle depth of 13 mm (back), and 9 mm (front), a dry basis weight of 575 g / m ² , a bulk density of 105.1 kg / An ACF nonwoven fabric was obtained in the same manner as in Comparative Example 1 except that an m ³ ACF nonwoven fabric precursor was obtained.

The obtained ACF nonwoven fabric was wound around a cylindrical structure having an inner diameter of 200 mm and a length of 1100 mm with a tension of 1.47 N / cm ² until the element mass reached 100 kg, and had a diameter of 1.09 m and a bulk density of 100 kg / m ³ . Got the element. Table 1 shows the characteristics of the activated carbon fiber, the ACF nonwoven fabric, and the elements constituting the obtained ACF nonwoven fabric.

Claims (6)

A phenolic fiber obtained by spinning and curing a mixture in which at least one compound selected from the group consisting of fatty acid amides, phosphate esters, and celluloses is mixed with a phenolic resin is processed into a non-woven fabric, and then carbonized. Activated carbon fibers obtained by activation and constituting have a fiber diameter of 21 μm to 40 μm, a toluene adsorption rate of 20% to 75%, and a nonwoven fabric having a tensile strength of 4 N / cm ² or more. Non-woven fabric. Basis weight activated carbon fiber nonwoven fabric according to claim 1 is a ^{200g / m 2 ~800g / m 2} . Bulk density of 65kg / m ³ ~100kg / m ³ active carbon fiber nonwoven fabric according to claim 1 or 2. Is constructed using the activated carbon fiber nonwoven fabric according to any one of claims 1 to 3, elements, wherein the bulk density of ^{90kg / m 3 ~170kg / m 3} .   The element according to claim 4, wherein the pressure loss is 550 mmAq or less. A method for producing the activated carbon fiber nonwoven fabric according to any one of claims 1 to 3,
Spinning a phenol resin and a mixture of at least one compound selected from the group consisting of fatty acid amides, phosphate esters, and celluloses and curing to produce phenolic fibers;
A step of processing the phenolic fiber into a nonwoven fabric to produce an activated carbon fiber nonwoven fabric precursor;
And a step of carbonizing and activating the precursor. A method for producing an activated carbon fiber nonwoven fabric, comprising: