KR101891377B1 - Active carbon fiber non-woven fabric, and element using said non-woven fabric - Google Patents

Abstract

The present invention provides an activated carbon fiber nonwoven fabric constituted by fibers having a fiber diameter capable of reducing the pressure loss of an element and having a tensile strength that is not damaged even when the filament is strongly wound on a cylinder. The activated carbon fiber nonwoven fabric of the present invention is produced by spinning a mixture of a phenol resin and at least one compound selected from the group consisting of fatty acid amides, phosphoric acid esters and cellulose, and curing the obtained phenolic fiber, Activated carbon fibers having a fiber diameter of from 21 탆 to 40 탆, a toluene adsorption rate of from 20% to 75%, and a tensile strength of the nonwoven fabric of not less than 4 N / cm ² .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an activated carbon fiber nonwoven fabric, an active carbon fiber nonwoven fabric, and an active carbon fibrous nonwoven fabric,

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

The continuous type gas adsorption treatment apparatus is preferably an element constituted by winding an activated carbon fiber nonwoven fabric around a cylinder in view of quick absorption and desorption speed and downsizing. In recent years, it has been desired to reduce the size of the element in order to reduce the installation space of the apparatus and to suppress the manufacturing cost.

As effective means for reducing the size of such an element, mention may be made of increasing the bulk density of the activated carbon fiber nonwoven fabric. However, with respect to the fibers constituting the activated carbon fiber nonwoven fabric, if the bulk density of the nonwoven fabric is increased while maintaining the monofilament fineness thereof constant (about 2 dtex to 3dtex) and the pressure loss of the element is increased, It is necessary to increase the capacity of the blower for the heat exchanger. As a result, there has been a case where the benefit of miniaturization of the element can not be sufficiently obtained.

Accordingly, the present inventors have developed a activated carbon fiber nonwoven fabric in which the pressure loss of the element is suppressed using a fiber having a monofilament fineness of 5 dtex or more, and applied for a patent to obtain the right (Patent Document 1).

On the other hand, if the fiber diameter of the fiber is increased, the pressure loss of the element becomes smaller, but the fiber becomes hard and tends not to be entangled. As a result, the resulting activated carbon fiber nonwoven fabric has a reduced tensile strength. For this reason, when the active carbon fiber nonwoven fabric is strongly wound around a cylinder to obtain an element having a high bulk density, the activated carbon fiber nonwoven fabric sometimes breaks.

Japanese Patent Laid-Open No. 2002-161439

Disclosure of the Invention The present invention has been made to solve the above problems and provides an activated carbon fiber nonwoven fabric comprising a fiber having a fiber diameter capable of reducing the pressure loss of an element and having a tensile strength that is not damaged even when the filament is strongly wound on a cylinder As a task.

As a result of extensive studies, the present inventors have found that the active carbon fiber nonwoven fabric having a predetermined fiber diameter obtained by using phenolic fibers can not only reduce the pressure loss of the element composed of the nonwoven fabric but also has a sufficient tensile strength Can be strongly wound around the cylinder, and the bulk density of the element can be increased, and the present invention has been accomplished.

That is, the activated carbon fiber nonwoven fabric of the present invention is a nonwoven fabric obtained by spinning and curing a mixture obtained by mixing a phenol resin with at least one compound selected from the group consisting of fatty acid amides, phosphoric acid esters, and cellulose, Characterized in that the activated carbon fibers constituting the activated carbon fibers have a fiber diameter of 21 탆 to 40 탆, a toluene adsorption ratio of 20% to 75%, and a tensile strength of the nonwoven fabric of 4 N / cm ² or more Carbon fiber nonwoven fabric.

In the activated carbon fiber nonwoven fabric of the present invention, those having a weight per unit area of 200 g / m ² to 800 g / m ² and a bulk density of 65 kg / m ³ to 100 kg / m ³ are all preferable embodiments.

The present invention includes an activated carbon fiber element comprising the activated carbon fiber nonwoven fabric and having a bulk density of 90 kg / m ³ to 170 kg / m ³ .

In the activated carbon fiber element of the present invention, the pressure loss is preferably 550 mmAq or less.

According to the present invention, there is provided a method for producing the above activated carbon fiber nonwoven fabric, comprising spinning a mixture of a phenol resin and at least one compound selected from the group consisting of fatty acid amides, phosphoric acid esters and cellulose, A process for producing an activated carbon fiber nonwoven fabric characterized by comprising the steps of: fabricating a fiber; processing the phenolic fiber to nonwoven fabric to produce an activated carbon fiber nonwoven fabric precursor; and carbonizing and activating the precursor; .

The active carbon fiber nonwoven fabric of the present invention can obtain an element having a low pressure loss because the fiber diameter of the fibers constituting the nonwoven fabric is large. Further, since the activated carbon fiber nonwoven fabric of the present invention has a large tensile strength and is hardly broken even when it is strongly wound on 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 탆 to 40 탆 and a toluene adsorption ratio of 20% to 75%, and has a tensile strength of 4 N / cm ² or more. Hereinafter, the activated carbon fiber nonwoven fabric of the present invention will be described in detail. Further, the activated carbon fiber may be simply referred to as ACF (Activated Carbon Fiber). Hereinafter, the activated carbon fiber nonwoven fabric may be reduced to be referred to as " ACF nonwoven fabric ".

(Fiber diameter)

The fibers constituting the ACF nonwoven fabric of the present invention have a fiber diameter of 21 mu m or more (preferably 22 mu m or more, more preferably 23 mu m or more, and further preferably 24 mu m or more). By setting the fiber diameter to 21 mu m 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 占 퐉 (preferably 35 占 퐉). In order to obtain an ACF nonwoven fabric having a fiber diameter exceeding 40 mu m, it is necessary to process nonwoven fabrics (fibers) having a monofilament fineness of more than 22 dtex and then to perform activation treatment, so that nonwoven fabrics of more than 22 dtex It may become 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) and 75% or less (Preferably 70% or less). By setting the adsorption rate of toluene to 20% or more, it is possible to exhibit sufficient gas adsorptive capacity even if the winding thickness of the ACF nonwoven fabric to the cylinder is reduced, so that the size of the element can be efficiently reduced. On the other hand, when the toluene adsorption rate exceeds 75%, the resulting ACF nonwoven fabric has an extremely small weight yield from the yarn, and the tensile strength of the ACF nonwoven fabric tends to be lowered.

(The tensile strength)

The tensile strength of the ACF non-woven fabric of the invention is 4N / cm ² or more (preferably from 4.5N / cm ^2, more preferably at least 5N / cm ^2). 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 hardly broken, and thus an element having 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 탆 to 40 탆.

(Weight per unit area)

The ACF nonwoven fabric of the present invention preferably has a weight per unit area of not less than 200 g / m ² (more preferably not less than 250 g / m ² , more preferably not less than 300 g / m ² ). By setting the weight per unit area to 200 g / m ² or more, an ACF nonwoven fabric having a tensile strength of 4 N / cm ² or more can be easily obtained. The upper limit of the weight per unit area is 800 g / m ² (more preferably 750 g / m ² , and still more preferably 700 g / m ² ). Even if an ACF nonwoven fabric having a weight per unit area of more than 800 g / m ² becomes difficult to fabricate or even if the nonwoven fabric can be produced, the effect of improving the tensile strength is not only limited but also lacks flexibility, It tends to become difficult to be wound around the cylinder at that time.

(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). When the bulk density is 65 kg / m < ³ > or more, an element having a high bulk density can be obtained even if the ACF nonwoven fabric winding tension against the cylinder at the time of manufacturing the element is lowered. The upper limit of the bulk density is 100 kg / m ³ (more preferably 95 kg / m ³ ). The ACF nonwoven fabric having a bulk density exceeding 100 kg / m ³ tends to have a high tensile strength, but lack flexibility and tend to become difficult to be wound around a cylinder.

(Pressure loss of ACF nonwoven fabric)

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, so that an element having a low pressure loss can be manufactured. The pressure loss coefficient of the ACF nonwoven fabric of the present invention is preferably 0.45 mmAq · s / cm ² or less (more preferably 0.40 mmAq · s / cm ² or less). If the pressure loss coefficient exceeds 0.5 mmAq.s / cm < ² >, the resistance at the time of gas passage becomes high, and the power loss of the air blower may increase.

(Production method of ACF nonwoven fabric)

The ACF nonwoven fabric of the present invention can be produced by subjecting an ACF nonwoven fabric precursor to a nonwoven fabric processing using phenolic fibers as a yarn, and then carbonizing and activating the precursor. Hereinafter, the method for producing the ACF nonwoven fabric of the present invention will be described in detail.

[Phenolic fiber]

The phenolic fiber used in the present invention is preferably a phenolic fiber 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, phosphoric acid esters and cellulose, . By adding the above-mentioned blend to the phenolic resin, the phenolic fibers can be smoothly finished, and it becomes possible to increase the intertwining property of the fibers when forming the nonwoven fabric. As a result, the entanglement of the fibers in the ACF nonwoven fabric obtained by carbonization and activation is also improved, so that the desired tensile strength can be imparted to the ACF nonwoven fabric.

<Phenolic resin>

Examples of the phenol resin include novolak type phenol resins obtained by reacting phenols and aldehydes in the presence of an acidic catalyst, resol type phenol resins obtained by reacting phenols and aldehydes in the presence of a basic catalyst, various modified phenol resins, .

Examples of the phenols include phenols such as phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 3,5- Butylphenol, o-butylphenol, resorcinol, hydroquinone, catechol, 3-methoxyphenol, 4-methoxyphenol, 3-methylcatechol, 4-methylcatechol, methylhydroquinone, 2-methylresorcinol, 2,3-dimethylhydroquinone, 2,5-dimethyl resorcinol, 2-ethoxyphenol, 4-methoxyphenol, 2-propenylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 3,4,5-trimethylphenol 2-allylphenol, 3,4,5-trimethoxyphenol, 4-isopropyl-3-methylphenol, pyrogallol, fluoroglucinol, 1, 2,4-benzenetriol, 5-isopropyl-3-methylphenol, 4 Butylphenol, 4-t-butylcatechol, t-butylhydroquinone, 4-t-pentylphenol, 2- , 3-phenoxyphenol, 4-phenoxyphenol, 4-hexyloxyphenol, 4-hexanoyl resorcinol, 3,5-diisopropyl catechol, 4-hexyl resorcinol, Di-t-butylphenol, 3,5-di-t-butylcatechol, 2,5-di-t-butylhydroquinone, di- Cyclopentylphenol, 4-cyclopentylphenol, bisphenol A, bisphenol F, and the like.

Among them, phenol, o-cresol, m-cresol, p-cresol, bisphenol A, 2,3-xylenol, 3,5-xylenol, m-butylphenol, , 4-phenylphenol, resorcinol are preferred, and phenol is most preferred. These phenols may be used singly or in combination of two or more.

Examples of the aldehydes include formaldehyde, trioxane, furfural, paraformaldehyde, benzaldehyde, methylhemiformate, ethylhemiformate, propylhemiformate, salicylaldehyde, butylhemiforme, phenylhemiforme, acetaldehyde Hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, m-hydroxybenzaldehyde, Nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde and pn-butylbenzaldehyde.

Among them, formaldehyde, paraformaldehyde, furfural, benzaldehyde and salicylaldehyde are preferable, and formaldehyde and paraformaldehyde are particularly preferable. These aldehydes may be used alone or in combination of two or more.

Examples of the acidic catalyst include salts with metals such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, butyric acid, lactic acid, benzenesulfonic acid, p- toluenesulfonic acid, boric acid, zinc chloride or zinc acetate. These acidic catalysts may be used alone or in combination of two or more.

Examples of the basic catalyst include hydroxides of alkali metals such as sodium hydroxide and lithium hydroxide; Hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide; Ammonium hydroxide; And amines such as diethylamine, triethylamine, triethanolamine, ethylenediamine, and hexamethylenetetramine. The basic catalyst may be used alone, or two or more of them may be used in combination.

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

In the present invention, it is preferable to use a novolak type phenol resin and a resol type phenol resin. The phenol resin may be used alone or in combination of two or more.

<Compounding>

The term "fatty acid amides" as used in the present invention means a non-polymerized structure in which at least one of hydrogen atoms bonded to the nitrogen atom of ammonia or amine is substituted with an acyl group, A secondary amide in which one hydrogen atom is bonded to the nitrogen atom, a tertiary amide in which the hydrogen atom is not bonded to the nitrogen atom, a lactam, and an amine in one molecule having two or more nitrogen atoms . Therefore, &quot; fatty acid amides &quot; in the present invention are different from polymers such as so-called aliphatic polyamides represented by nylon-6 and nylon-6,6. In addition, &quot; fatty acid amides &quot; are also referred to as fatty acid amides.

Examples of the primary amide include a compound represented by the formula &quot; R ¹ C (= O) NH _{2 &} quot ;.

Wherein R &lt; ¹ &gt; is a hydrocarbon group which may have a substituent. The term "optionally having a substituent" as used herein means that some or all of the hydrogen atoms of the hydrocarbon group may be substituted with a substituent. The hydrocarbon group of R &lt; ¹ &gt; may be saturated or unsaturated, and may be linear or branched. The number of carbon atoms thereof is preferably 5 to 31, more preferably 11 to 23. Provided that the number of carbon atoms of the hydrocarbon group of R &lt; ¹ &gt; does not include the number of carbon atoms in the substituents to be described later. Examples of the substituent which the hydrocarbon group may have include a hydroxyl group and a hydroxyalkyl group. The number of carbon atoms of the hydroxyalkyl group is preferably from 1 to 11.

Specific examples of the primary amides include caproic acid amide, caprylic acid amide, pelaric acid amide, lauric acid amide, myristyl acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, Saturated fatty acid monoamides such as seric acid amide; And unsaturated fatty acid monoamides such as oleic acid amide, erucic acid amide and ricinoleic acid amide.

Examples of the secondary amide include a compound represented by the formula &quot; R ¹ C (= O) NHR ^{2 &} quot ;.

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

Wherein R ² is a hydrocarbon group which may have a substituent, or -C (= O) R ³ . The hydrocarbon group in R ² may be saturated or unsaturated, may be linear or branched, has 1 to 23 carbon atoms, and more preferably 1 to 17 carbon atoms. Examples of the substituent which the hydrocarbon group may have include a hydroxyl group and the like.

R ³ is 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. Also, a compound wherein 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 stearamide, oleyl oleate, stearyl oleate, oleyl stearate, stearyl erucate and oleyl palmitate; And methylol amides such as methylol stearic acid amide and methyl oleic acid amide.

Examples of the tertiary amide include compounds represented by the formula &quot; R ¹ C (= O) NR ⁴ R ^{5 &} quot ;.

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

In the above formula, R ⁴ and R ⁵ are the same as R ² in the description of the secondary amide, and R ⁴ and R ⁵ may be the same or different from each other.

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

Preferred among lactams are those having 3 to 12 carbon atoms. Specific examples include 棺 -profiolactam, γ-butyrolactam (2-pyrrolidone), δ-valerolactam (2-piperidone), ε-caprolactam, undecalactam, Lauryllactam), and the like.

As having at least two nitrogen atoms of amine in the molecule, the formula ^{"R 11 C (= O) NH} -R 6 -NHC (= O) R 12 ", the compound represented by the formula "R ¹¹ NHC (= O ) -R ⁷ -C (= O) NHR ¹² ".

In the above formula, R ¹¹ and R ¹² each represent a hydrocarbon group which may have a substituent, and the same groups as those of R ¹ may be mentioned. R ⁶ and R ⁷ are each a divalent hydrocarbon group, and the number of carbon atoms thereof is preferably from 1 to 10, more preferably from 1 to 8.

Specific examples of the amines having two or more nitrogen atoms of amines in one molecule include methylenebisstearic acid amide, ethylenebisstearic acid amide, ethylene biscaprylic acid amide, ethylene bislauric acid amide, ethylene bisbehenic acid amide, methylene Hexamethylenebisstearic acid amide, hexamethylene bisbehenic acid amide, hexamethylenebishydroxystearic acid amide, and the like; N, N-distearyadipic acid amide, N, N-distearyl sebacic acid amide and the like.

Among the above-mentioned fatty acid amides, primary amides and secondary amides are preferable from the viewpoints of handleability, stability or radioactivity of the raw material mixture, more preferred are primary amides, saturated fatty acid monoamides, Amides are particularly preferred, among which the behenic amide is most preferred.

If the number of carbon atoms of the fatty acid amides is too small, the heat resistance of the phenol-based fibers may deteriorate. If the number of carbon atoms is too large, there is a fear that the compatibility with the phenol resin used for the raw material of the phenol-based fibers is lowered. Therefore, the fatty acid amide preferably has 12 to 30 carbon atoms, and more preferably 18 to 24 carbon atoms. The fatty acid amides may be used alone or in combination of two or more.

"Phosphoric acid" of the phosphoric acid ester used as a blend in the present invention is a general term of various oxo acids produced by hydrolysis of tetraoxide (P ₄ O ₁₀ ), and includes orthophosphoric acid (a) represented by the following formula, Phosphoric acid (biphosphoric acid) (b), triphosphoric acid (c), sine acid (d), metaphosphoric acid (e) and the like.

[Wherein m represents the number of repeats]

In the present invention, &quot; phosphoric acid esters &quot; means either one in which at least one of -OH in phosphoric acid is substituted with a group represented by the following formula (1) or a salt thereof.

Wherein R ¹³ is a hydrocarbon group having 4 or more carbon atoms which may have a hetero atom (an atom other than carbon and hydrogen), AO is an oxyalkylene group having 2 to 4 carbon atoms, n is an average addition mole number, &Lt; / RTI &gt;

Examples of the hydrocarbon group represented by R ¹³ in the formula (1) include an alkyl group, an alkenyl group, an aryl group, a group in which a part of the hydrogen atoms of the alkyl group is substituted with an aryl group, a group in which a part of the hydrogen atoms of the alkenyl group are substituted with an aryl group, have.

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

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

In the hydrocarbon group R ^13, if any, when the number of carbon atoms of R ¹³ exceeds the upper limit, it is easy to have compatibility with the phenol resin decreases. When R &lt; ¹³ &gt; is an aryl group, the compatibility with the phenol resin is relatively improved as compared with the case where R &lt; ¹³ &gt; is an alkyl group or an alkenyl group.

In the formula (1), AO may be an oxyethylene group, an oxypropylene group or an oxybutylene group. The phosphorus atom is bonded to the oxygen atom in the oxyalkylene group.

In the above formula (1), n is preferably 0 to 50, more preferably 0 to 10.

As the phosphoric acid esters, those in which at least one of -OH in orthophosphoric acid is substituted with a group represented by the above formula (1) (orthophosphoric ester ) Or a salt thereof is preferable.

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

Wherein R ¹³ , AO, and n are the same as defined above, and - (AO) _n OR ^{13, which} is present in a plurality of diesters and triesters, may be the same or different from each other;

Examples of salts of phosphoric acid esters include alkali metal salts, alkaline earth metal salts, ammonium salts and amine salts of phosphoric acid esters. The phosphoric acid esters may be used alone or in combination of two or more.

Examples of the cellulose used as a blend in the present invention include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like. The cellulose may be used singly or in combination of two or more kinds.

[Process for producing phenolic fiber]

The phenolic fiber used in the present invention can be produced by a raw material mixing step of mixing the phenol resin obtained by the above method with the above-mentioned blend and a spinning step of spinning the raw material mixture obtained in the raw material mixing step to obtain yarn.

<Raw Material Mixing Process>

When the phenol resin and the blend are melt-mixed and melt spinning, which is the most common spinning method in the spinning process to be described later, is carried out, both novolak type and resol type phenol resins can be used as the phenol resin. However, the resolved type thermoplastic resin has lower thermal stability than the novolac resin, and polymerization proceeds easily upon heating at the time of melting. Therefore, solidification in the melt spinning apparatus can not be avoided and it is difficult to continuously and stably radiate. Therefore, it is particularly preferable to select the novolac phenolic resin in consideration of easiness of processing and general versatility in the case of industrial production.

When mixing the phenol resin and the blend in the raw material mixing process, the amount of the phenol resin to be used is preferably such that the proportion of the phenol resin in the obtained raw material mixture is 55 mass% to 99.9 mass%, more preferably 70 mass% to 99 mass% By mass, and particularly preferably from 85% by mass to 95% by mass.

The amount of the compounding agent is preferably such that the proportion of the compounding agent in the obtained raw material mixture (when the compounding agent is used in plural species, the ratio of the total amount of the compounding agent) is from 0.1 mass% to 45 mass%, more preferably from 1 mass% By mass, more preferably 5% by mass to 15% by mass. If the proportion of the blend is more than the preferable lower limit value, the effect of improving the mechanical strength when the phenol-based fibers are hardened is liable to be obtained easily. On the other hand, if the proportion of the blend is below the preferable upper limit value, properties such as heat resistance, flame retardancy, and chemical resistance of the phenolic fiber are easily maintained.

Specifically, the amount of the fatty acid amides to be used is, for example, preferably such that the proportion of the fatty acid amides in the obtained raw material mixture is from 0.1% by mass to 45% by mass, more preferably from 1% by mass to 30% by mass , And 3% by mass to 10% by mass.

The amount of the phosphoric acid ester to be used is, for example, preferably such that the proportion of the phosphoric acid ester in the obtained raw material mixture is from 0.1% by mass to 45% by mass, more preferably from 1% by mass to 30% by mass, By mass to 20% by mass.

The amount of cellulose is preferably from 0.1% by mass to 45% by mass, more preferably from 1% by mass to 30% by mass, more preferably from 5% by mass to 5% by mass, By mass to 20% by mass.

Examples of the method of mixing the phenol resin and the blend include a method of melt mixing the two, and a method of dissolving and mixing the both using a solvent. Among them, a method of melting and mixing the two is preferable in terms of process complexity, environmental load, and economical efficiency. As such melt mixing, there is a method of heating and kneading both of them.

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

The temperature of the heat kneading may be appropriately selected depending on the properties of the raw material, and is preferably 200 占 폚 or lower, and more preferably 140 占 폚 to 180 占 폚. By adjusting the temperature of the heat kneading to a preferable upper limit value or less, it is easy to suppress heat denaturation and deterioration by exposing the raw material to a high temperature. By setting the temperature of the heat kneading to a preferable lower limit or more, it becomes possible to efficiently mix the two.

In the method of dissolving and mixing the phenol resin and the blend with a solvent, the both are dissolved and mixed in a solvent capable of dissolving the phenol resin and the solvent, and then the solvent is evaporated off to obtain a raw material mixture.

Examples of the solvent capable of dissolving both of them include a solvent obtained by mixing one kind or two or more kinds selected from a ketone type solvent, an ether type solvent, a nitrogen type type solvent, a hydrocarbon type solvent, an ester type solvent and an alcohol type solvent.

It is preferable that the dissolving and mixing of the phenol resin and the blend is carried out slowly with the phenol resin while stirring the solvent. At that time, it is effective to heat the phenolic resin or blend if it seems difficult to dissolve in the solvent. Further, by pressurization, it becomes possible to warm the solvent at the boiling point or more of the solvent at normal pressure, which is more effective. However, since exposure to the raw material at a high temperature may cause thermal denaturation or deterioration, heating is preferably performed finely until the raw material is completely dissolved.

The concentration of the phenol resin and the compound to be dissolved in the solvent is not particularly limited and may be set appropriately in consideration of the property of the raw material and the spinning method in the subsequent spinning process. In addition, the concentration of the phenol resin and the blend is preferably set as high as possible in consideration of the respective solubilities, because it takes much time and energy to recover the solvent to be evaporated off.

The method of mixing the phenol resin and the blend may be a method other than the melt mixing and the melt blending. For example, when a dry spinning method, a wet spinning method or a dry-wet spinning method is used as a spinning method in a subsequent spinning step, a raw material mixture solution obtained by dissolving and mixing both in a solvent capable of dissolving both a phenol resin and a compound . &Lt; / RTI &gt; The raw material mixture solution can be used directly as a spinning solution.

It is also effective to blend the components during the synthesis reaction of the phenol resin and mix them in the range that does not inhibit the synthesis reaction of the phenol resin and does not deteriorate the raw material at the temperature during the synthesis reaction.

In the raw material mixing step, known additives such as additives, plasticizers, compatibilizing agents, antioxidants, ultraviolet absorbers, penetrating agents, thickeners, antiseptics, dyes, pigments, fillers and the like are used, if necessary, It is possible.

Particularly, when a phenol resin and a fatty acid amide are melt-mixed, it is preferable to use a compatibilizer when the melt viscosity of the fatty acid amide is extremely different from that of the phenol resin. As a result, it is possible to prevent separation from occurring at the time of spinning.

<Radiation process>

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

As the method of spinning, a known method may be appropriately selected from the viewpoint of 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. Among them, melt spinning is preferable in terms of simplicity of apparatus and economical advantage. In the case of using melt spinning as a method of spinning, a general melt spinning device can be used.

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

In the 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 a preferable lower limit value or more, it is possible to efficiently spin. By setting the temperature condition to a preferable upper limit value or less, thermal denaturation and deterioration are easily suppressed, and the phenol resin and the compound are hardly separated.

As the spinneret, usual ones can be used. The pore 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 portion is preferably 0.5 or more and 10 or less , More preferably 1 or more and 5 or less. By setting the pore diameter and the L / D ratio within the above preferable range, it is possible to stably emit radiation.

In the case of a special fiber production method (for example, in the case of parallel conjugated fibers, SHEATH-CORE type conjugated fibers, sea-island conjugated fibers, etc.), side-by-side or cisco- May be used.

The spinning speed is preferably not less than 15 m / min and not more than 3000 m / min, more preferably not less than 30 m / min and not more than 2000 m / min, more preferably not less than 50 m / min and not more than 1600 m / min. By setting the spinning speed to a preferable lower limit value or more, it is possible to efficiently spin. By reducing the spinning speed to a preferable upper limit value or less, occurrence of yarn fragments at the time of spinning can be suppressed.

<Curing Process>

The step of producing the phenolic fiber preferably includes a curing step of curing the yarn obtained in the spinning step. By curing the yarn in the curing process, the mechanical strength of the phenol-based fiber largely increases because the phenol resin portion is mainly crosslinked.

In the case of using a novolac phenolic resin as the raw phenol resin, as a method for curing the yarn obtained in the spinning process, a yarn processed in a staple or a toe shape is immersed in a treatment solution in a reaction container and cured in a batch manner A method of curing the substrate by contacting the substrate with a treatment liquid in the form of a bobbin or a failed substrate, or a method of curing the substrate by continuously bringing the substrate into contact with the treatment liquid.

The treatment liquid includes a catalyst and aldehydes.

Examples of the catalyst include acidic catalysts and basic catalysts which are exemplified as being usable in the production of a phenol resin. Examples of the aldehydes include aldehydes which are exemplified as those which can be used in the production of phenol resins.

The curing is preferably carried out in a liquid phase at a temperature of 60 ° C or more and 110 ° C or less for 3 hours or more and 30 hours or less. In the present invention, it is also possible to cure by heating under a gas phase.

In the present invention, it is possible to carry out a known post-curing treatment such as washing with water after heating and drying and further curing by heating at a temperature of 100 to 300 ° C in an inert gas such as nitrogen, helium or carbonic acid gas. Thereafter, the crosslinking of the phenol resin portion in the yarn is further promoted by the curing treatment, and phenol-based fibers having sufficient strength can be obtained.

On the other hand, when a resol-type phenol resin is used as the raw phenol resin, it is possible to cure the yarn by performing a heat treatment by a wet heat method or a dry heat method.

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

The fineness degree of the phenolic fibers 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 phenolic fibers having a monofilament fineness of less than 7 dtex, the pressure loss of the element may be increased. When the monofilament fineness of phenolic fibers exceeds 22 dtex, it may be difficult to process nonwoven fabrics using the fibers.

The phenolic 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%). . By using the phenolic fibers having the tensile modulus and elongation in the above range, the nonwoven fabric can be easily processed even if the monofilament fineness thereof 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 preferably 130 mm or less (more preferably 100 mm or less, further preferably 80 mm or less). If the fiber length is less than 35 mm, the entanglement between the fibers can not be sufficiently achieved, and the tensile strength of the resultant ACF nonwoven fabric may be lowered. When the fiber length exceeds 130 mm, for example, fiber cutting or damage at the time of needle punching becomes severe, and the tensile strength may also be lowered.

The presence or absence of the crimp of the phenolic fiber is not particularly limited. The phenolic fibers may have a crimp in order to enhance the intermixing of the fibers. On the other hand, the phenol-based fibers including the blend have a large diameter, and the fibers themselves are smooth and excellent in interlocking property. Therefore, in the present invention, phenol-based fibers having no crimp can be used.

[Nonwoven Fabric Processing]

The nonwoven fabrics of the phenolic fibers are not particularly limited as long as they can prevent the cutting of the fibers during processing and can sufficiently entangle the fibers. For example, the needle punching method and the water punching method can be used . The needle punching method is preferable in that the needle density and the depth of the needle can be adjusted in accordance with the change of the fiber diameter and the density of the obtained nonwoven fabric can be adjusted.

When the nonwoven fabric is processed by the needle punching method, the needle density is preferably 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) More preferably not more than 20 mm). By making the needle density 370 / inch ² or more, the entanglement between the fibers increases, thereby increasing the bulk density of the ACF nonwoven fabric precursor. In addition, if the needle density is too high, pieces of fibers may be generated, and the bulk density or tensile strength of the resultant ACF nonwoven fabric may be rather lowered. Therefore, it is preferable that the upper limit of the needle density is 700 pieces / inch ² . In addition, when the depth of the needle is less than 5 mm, the ACF nonwoven fabric precursor sometimes becomes bulk. When the depth of the needle exceeds 30 mm, needle breakage tends to occur. In addition, the ACF nonwoven fabric precursor tends to have more streaks.

[Carbonization · Activation Treatment]

The carbonization / activation treatment of the ACF nonwoven fabric precursor is carried out, for example, in a carbonization furnace in an inert atmosphere such as nitrogen or argon at 400 ° C. to 1000 ° C. for 10 minutes to 120 minutes, and then in an activated gas atmosphere such as steam , And activating treatment at 800 DEG C or higher for 30 minutes to 180 minutes.

(Element)

The element of the present invention can be produced by winding an ACF nonwoven fabric obtained through the above process onto a cylinder. The winding tension of the nonwoven fabric is preferably set to about 1/3 or less of the tensile strength so that the ACF nonwoven fabric is not broken.

(Bulk density)

Since the ACF nonwoven fabric of the present invention has an excellent tensile strength, the tension at the time of winding the nonwoven fabric in the cylinder can be higher than the conventional one. Therefore, in the present invention, an element having a bulk density of 90 kg / m ³ to 170 kg / m ³ can be obtained.

As described above, since the element of the present invention has a large bulk density, it is possible to manufacture the element having the same adsorbing ability as that of the conventional element in a smaller size. In addition, by making the volume of the element of the present invention equal to the volume of the conventional element, it is possible to produce an element having better adsorbing ability. Further, since the element of the present invention has a large bulk density, it is not necessary to further adjust the bulk density after the production of the element, so that the ACF can be prevented from being dropped or scattered by the compression.

In addition, when the bulk density of the element exceeds 170 kg / m ³ , the pressure loss of the element may be increased. The bulk density of the element of the present invention is preferably 100 kg / m ³ to 150 kg / m ³ .

(Pressure loss of the element)

Since the element of the present invention is constituted by using the ACF nonwoven fabric composed of fibers having a large fiber diameter, the pressure loss is small, specifically, 550 mmAq or less. Therefore, even if the bulk density of the ACF nonwoven fabric is increased and the size of the element is reduced, it is not necessary to increase the capacity of the blower for blowing the gas to be processed to the element.

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 increase the fiber diameter of the fibers constituting the ACF nonwoven fabric, and it is difficult to manufacture a nonwoven fabric having such a fiber diameter.

The present application claims the benefit of priority based on Japanese Patent Application No. 2011-262483 filed on November 30, The entire contents of the specification of Japanese Patent Application No. 2011-262483 filed on November 30, 2011 are hereby incorporated by reference herein.

Example

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 suitably changed within a range that is suitable for the purpose described above and below, All of which are included in the technical scope of the present invention.

First, the monofilament fineness, tensile elastic modulus, elongation, "activated carbon fiber constituting ACF nonwoven fabric", fiber diameter, toluene adsorption ratio, and tensile strength of "ACF nonwoven fabric" of "phenolic fiber" , The weight per unit area, the bulk density, the pressure loss coefficient, and the method of measuring the bulk density and pressure loss of the &quot; element &quot;

(The fineness of phenolic fibers)

DC11B denier computer (manufactured by SEKI Co., Ltd.).

(Tensile Modulus of Phenolic Fibers)

The measurement was carried out in accordance with JIS L1015 using an RTG-1210 Tensilon universal testing machine (manufactured by A & D Co., Ltd.).

(Elongation degree of phenolic fiber)

The measurement was carried out in accordance with JIS L1015 using an RTG-1210 Tensilon universal testing machine (manufactured by A & D Co., Ltd.).

(Fiber diameter of activated carbon fiber constituting ACF nonwoven fabric)

The fiber diameter was measured using a high-precision digital microscope VH-6300 (manufactured by KEYENCE) according to JIS K1477 5.1 (fiber diameter test method).

(Toluene adsorption rate of activated carbon fibers constituting ACF nonwoven fabric)

The toluene adsorption ratio was measured in accordance with JIS K1477 &quot; 7.8 toluene adsorption performance &quot;.

(Tensile strength of ACF nonwoven fabric)

Five test pieces (25 mm in width and 100 mm in length) were cut out from the width direction and the length direction of the ACF nonwoven fabric, and the test pieces were cut with an Instron type tensile tester (e.g., "STM-T-200BP" manufactured by Toyo Baldwin Co., Ltd.) The both ends of the test piece were held with a chuck, and the fracture strength was measured with a chuck interval of 50 mm and a tensile speed of 20 mm / min (elongation rate of 40% / min), and the value was divided by the cross sectional area (width x thickness) (Unit N / cm ² ). Further, the thickness was measured by using a disk having an area of 4 cm ² , and the load applied to the ACF nonwoven fabric was 9 gf / cm ² . The average value of the tensile strengths of the test pieces cut in the width direction and the average value of the tensile strengths of the test pieces cut in the lengthwise direction, whichever is smaller, was defined as the tensile strength of the ACF nonwoven fabric of the present invention.

(Weight per unit area of ACF nonwoven fabric)

The mass per unit area of the ACF nonwoven fabric was measured and was expressed in units of g / m ² . Further, the mass was measured at 100 占 폚 in an absolutely dry state.

(Bulk density of ACF nonwoven fabric)

Bulk density was calculated in units of kg / m ³ by dividing the weight per unit area by the thickness. Further, the thickness was measured by using a disk having an area of 4 cm ² , and the load applied to the ACF nonwoven fabric was 9 gf / cm ² .

(Pressure loss coefficient of ACF nonwoven fabric)

The ACF nonwoven fabric was cut into a circle having a diameter of 72 mm and set on an air pressure loss measuring instrument. The air between the ACF nonwoven fabric having a diameter of 50.5 mm and the circular ACF nonwoven fabric having a diameter of 72 mm was firmly pressed with 0.1 MPa of compressed air, (Unit mmAq · s / cm ² ) by measuring the pressure loss when the air was spilled at 30 cm / sec and dividing the value by the wind speed and the thickness. The measurement was performed at a temperature of 25 캜 and a humidity of 50%. The thickness was measured in the same manner as the method used when measuring the bulk density.

(Bulk density of the element)

The mass of the element before winding the ACF nonwoven fabric at 100 占 폚 in a fully open state and the mass after winding were measured and the mass of the particle was divided by the volume of the ACF nonwoven fabric calculated from the winding diameter.

(Pressure loss of the element)

An ACF nonwoven fabric having a width of 1100 mm was wound into 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 so as to measure the pressure loss when an air velocity of 30 cm / Respectively.

(Production Example 1: Production of phenolic fiber 1)

1000 parts by mass of phenol, 733 parts by mass of 37% by mass of formalin and 5 parts by mass of oxalic acid were charged into a reaction vessel equipped with a reflux condenser, and the temperature was raised from room temperature to 100 캜 for 40 minutes and further reacted at 100 캜 for 4 hours. Lt; 0 &gt; C, dehydrated and concentrated, and then cooled to obtain a novolac-type phenolic resin.

475 kg of the novolak type phenolic resin and 25 kg of behenic acid amide were charged into a biaxial kneader (high-speed biaxial continuous mixer), kneaded (melt mixed) at 150 ° C and cooled to room temperature to obtain a pale yellow transparent blocky material. As the behenic acid amide, behenic acid amide (BNT-22H) manufactured by Nippon Seika Co., Ltd. was used.

Subsequently, this blocky material was coarsely pulverized, melted at 200 DEG C using a melt-spinning device (grid melter type), and the melt obtained by the melting was passed through a crucible having a pore size of 0.1 mm and L / D = 3, and spinning at a spinning speed of 75 m / min while maintaining a constant discharge amount from 10 odd spinnerets.

The resultant yarn was cut into a length of 70 mm, placed in a container, immersed in an aqueous solution of 14 mass% hydrochloric acid and 8 mass% formaldehyde for 30 minutes at room temperature, then heated to 98 ° C for 2 hours, maintained at 98 ° C for 2 hours Thereby performing curing.

Subsequently, the obtained cured product was taken out from the container, sufficiently washed with water, and neutralized with a 3 mass% ammonia aqueous solution at 60 캜 for 30 minutes. Thereafter, it was sufficiently washed with water again and dried at 90 DEG C for 30 minutes to obtain a phenol-based fiber 1 having a single fiber fineness of 11 dtex, a fiber length of 70 mm, and no fiber crimp.

The obtained phenolic fiber 1 had a tensile modulus of 395 kgf / mm ² and an elongation of 12%.

(Production Example 2: Production of phenolic fiber 2)

Phenol type fiber 2 having a single fiber fineness of 11 dtex, a fiber length of 70 mm and a fiber crimp was obtained in the same manner as in Production Example 1, except that oleic acid amide was used instead of behenic acid amide in Production Example 1. As the oleic acid amide, "Neutron (registered trademark)" manufactured by Nippon Seika Co., Ltd. was used.

The obtained phenolic fiber 2 had a tensile modulus of 386 kgf / mm ² and an elongation of 11%.

(Production Example 3: Production of phenolic fiber 3)

The same procedure was followed as in Production Example 1 except that the pore diameter of the spinneret when spinning the block-like material was changed to 0.15 mm and the amount of phenol-based fibers 3 without fiber crimp was 17 dtex and the fiber length was 70 mm, .

The obtained phenolic fiber 3 had a tensile modulus of 402 kgf / mm ² and an elongation of 8%.

(Production Example 4: Production of phenolic fiber 4)

Except that the pore diameter of the spinneret at the time of spinning the block material was changed to 0.07 mm and the discharge amount was reduced in the same manner as in Production Example 1 except that the single fiber fineness was 7.7 dtex and the fiber length was 70 mm, .

The obtained phenolic fiber 4 had a tensile modulus of 390 kgf / mm ² and elongation of 25%.

(Production Example 5: Production of phenolic fiber 5)

In Production Example 1, except that the mixing amount of the novolak type phenolic resin was 450 kg, and 50 kg of the phosphoric acid ester represented by the following chemical formula was used instead of 25 kg of behenic acid amide, the monofilament fineness was 11 dtex, A phenolic fiber 5 having a length of 70 mm and no fiber crimp was obtained. Phosphoric esters can be obtained by a method in which the mass ratio of monoester of the formula (1A) and diester of the formula (1B) shown below is 1 / 1B = 1/1 (manufactured by TOHOKAGAKU Co., Was used.

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

(Production Example 6: Production of phenolic fiber 6)

In Production Example 1, in the same manner as in Production Example 1 except that the mixing amount of the novolak type phenolic resin was 450 kg and 50 kg of diacetic acid cellulose was used instead of 25 kg of behenic acid amide, a single fiber fineness of 11 dtex, a fiber length of 70 mm, Free phenolic fiber 6 was obtained.

The obtained phenolic fiber 6 had a tensile modulus of 380 kgf / mm ² and an elongation of 11%.

(Production Example 7: Production of phenolic fiber 7)

In Production Example 1, in the same manner as in Production Example 1, except that 500 kg of a novolac phenolic resin was used in place of 450 kg of a novolak type phenol resin and 25 kg of behenic acid amide, a single fiber fineness of 11 dtex, a fiber length of 70 mm, Based fiber 7 was obtained.

The obtained phenolic fiber 7 had a tensile modulus of 469 kgf / mm ² and an elongation of 4%.

(Example 1)

Using the phenol-based fiber 1 produced in Production Example 1, a needle punching machine was used to perform surface treatment under conditions of a needle density of 500 pieces / inch ² , a needle depth of 12 mm (inside) and 7 mm (surface side) / m &lt; ² &gt; and a bulk density of 82.4 kg / m &lt; ³ &gt;.

The resultant ACF nonwoven fabric precursor was carbonized by heating to 890 DEG C at room temperature for 30 minutes in an inert atmosphere (nitrogen atmosphere), and then activated at a temperature of 890 DEG C for 100 minutes in an atmosphere containing 12 mass% of water vapor to obtain ACF nonwoven fabric .

The obtained ACF nonwoven fabric was wound on a cylindrical structure having an inner diameter of 200 mm and a length of 1100 mm at a tension of 1.47 N / cm ² until the mass of the element became 100 kg to obtain an element having a diameter of 1.09 m and a bulk density of 100 kg / m ³ . The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

(Example 2)

Using the phenol-based fiber 1 produced in Production Example 1, surface treatment was carried out by needle punching machine under conditions of a needle density of 500 pieces / inch ² , a needle depth of 12 mm (inside) and 7 mm (surface side) / m &lt; ² &gt; and a bulk density of 82.0 kg / m &lt; ³ &gt;.

The obtained ACF nonwoven fabric precursor was carbonized by heating to 890 캜 at room temperature over 36 minutes in an inert atmosphere and then activated at a temperature of 890 캜 for 12 minutes in an atmosphere containing 12% by mass of water vapor to obtain an ACF nonwoven fabric. The properties of the activated carbon fiber and ACF nonwoven fabric constituting the obtained ACF nonwoven fabric are shown in Table 1.

An element of the present invention was obtained in the same manner as in Example 1 except that the obtained ACF nonwoven fabric was used. The characteristics of the obtained elements are shown in Table 1.

(Example 3)

Using the phenol-based fiber 1 produced in Production Example 1, surface treatment was carried out under conditions of needle density of 500 pieces / inch ² , needle depth of 12 mm (inside) and 7 mm (surface side) by a needle punch machine, / m &lt; ² &gt; and a bulk density of 99.6 kg / m &lt; ³ &gt;.

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. The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

(Example 4)

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

(Example 5)

Using the phenol-based fiber 1 produced in Production Example 1, the surface treatment was carried out by a needle punching machine under the conditions of a needle density of 650 pieces / inch ² , a needle depth of 15 mm (inside) and 10 mm / m &lt; ² &gt; and a bulk density of 129 kg / m &lt; ³ &gt;.

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. The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

(Example 6)

The ACF nonwoven fabric obtained in Example 5 was wound on 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 mass of the element reached 150 kg. The characteristics of the obtained elements are shown in Table 1.

(Example 7)

The phenol-based fibers 2 produced in Production Example 2 were used instead of the phenol-based fibers 1 produced in Production Example 1 and carbonized by heating to 870 ° C at room temperature over 12 minutes in an inert atmosphere ACF nonwoven fabric and an element were obtained in the same manner as in Example 1, except that the ACF nonwoven fabric precursor, ACF nonwoven fabric, and the element were activated in an atmosphere containing 12 mass% of water vapor at a temperature of 870 캜 for 40 minutes. The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

(Example 8)

The phenolic fiber 3 produced in Production Example 3 was used in place of the phenol-based fiber 1 produced in Production Example 1, and a needle density of 600 pieces / inch ² and a needle depth of 13 mm The ACF nonwoven fabric precursor was used to obtain an ACF nonwoven fabric precursor having a weight per unit dry area of 778 g / m ² and a bulk density of 98.3 kg / m ³ , and the ACF nonwoven fabric precursor was used. In the same manner, an ACF nonwoven fabric and an element were obtained. The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

(Example 9)

In the same manner as in Example 1 except that the phenol-based fibers 4 produced in Production Example 4 were used in place of the phenol-based fibers 1 produced in Production Example 1, and the needle density was 450 pcs / inch ² and the needle depth was 12 mm The ACF nonwoven fabric precursor was dried under the same conditions as in Example 1 except that the ACF nonwoven fabric precursor having a weight per unit dry area of 535 g / m ² and a bulk density of 80.3 kg / m ³ was obtained. In the same manner, an ACF nonwoven fabric and an element were obtained. The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

(Example 10)

In Example 8, except that the obtained ACF nonwoven fabric precursor was carbonized by heating from room temperature to 870 캜 over 18 minutes in an inert atmosphere, and then activated at a temperature of 870 캜 for 60 minutes 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. The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

(Example 11)

In Example 1, the phenolic fiber 1 produced in Production Example 1 was subjected to front and back treatment under the conditions of a needle punching machine with a needle density of 600 pcs / cm ² , a needle depth of 13 mm (inside) and 9 mm (surface side) , An ACF nonwoven fabric precursor having a dry weight per unit area of 420 g / m ² and a bulk density of 81.7 kg / m ³ was obtained in the same manner as in Example 1, to obtain an ACF nonwoven fabric and an element. The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

(Example 12)

An ACF nonwoven fabric precursor, ACF nonwoven fabric, and an element were obtained in the same manner as in Example 1 except that the phenol-based fiber 5 obtained in Preparation Example 5 was used instead of the phenol-based fiber 1 used in Example 1. The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

(Example 13)

An ACF nonwoven fabric precursor, ACF nonwoven fabric, and an element were obtained in the same manner as in Example 1 except that the phenol-based fiber 6 obtained in Preparation Example 6 was used instead of the phenol-based fiber 1 used in Example 1. The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

(Comparative Example 1)

A needle density of 500 pcs / inch ² , a density of 500 pcs / cm ² , and a density of 500 pcs / cm 2 were measured with a needle punching machine using a phenolic fiber having a monofilament size of 5.6 dtex, a fiber length of 70 mm and a phenolic fiber without a fiber crimp (KYNOL KF- And a needle depth of 12 mm (inside) and 7 mm (front side), to obtain an ACF nonwoven fabric precursor having a weight per unit dry area of 385 g / m ² and a bulk density of 83.7 kg / m ³ .

The resultant ACF nonwoven fabric precursor was carbonized by heating to 890 캜 at room temperature over 18 minutes in an inert atmosphere and then activated at a temperature of 890 캜 for 60 minutes in an atmosphere containing 12% by mass of water vapor to obtain an ACF nonwoven fabric.

The obtained ACF nonwoven fabric was wound on a cylindrical structure having an inner diameter of 200 mm and a length of 1100 mm with a tensile force of 1.1 N / cm ² until the mass of the element became 100 kg to obtain an element having a diameter of 1.26 m and a bulk density of 75 kg / m ³ . The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

(Comparative Example 2)

The ACF nonwoven fabric obtained in Comparative Example 1 was wound on 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 mass of the element became 100 kg to obtain an element having a diameter of 1.09 m and a bulk density of 100 kg / m ³ . The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

(Comparative Example 3)

Using the phenol-based fibers 7 produced in Production Example 7, the surface treatment was carried out by needle punching machine under conditions of a needle density of 650 pieces / inch ² , a needle depth of 15 mm (inside) and 10 mm (surface side) / m &lt; ² &gt; and a bulk density of 115.0 kg / m &lt; ³ &gt;.

The resultant ACF nonwoven fabric precursor was carbonized by heating to 890 DEG C at room temperature over 30 minutes in an inert atmosphere, and then activated at a temperature of 890 DEG C in an atmosphere containing 12 mass% of water vapor for 100 minutes to obtain an ACF nonwoven fabric. The properties of the activated carbon fiber and ACF nonwoven fabric constituting the obtained ACF nonwoven fabric are shown in Table 1.

The obtained ACF nonwoven fabric was attempted to be wound in a cylindrical structure having an inner diameter of 200 mm and a length of 1100 mm at a tension of 1.1 N / cm ² , but the ACF nonwoven fabric had a low tensile strength and was broken and could not be wound.

(Comparative Example 4)

In Comparative Example 1, the surface treatment was carried out under the conditions of a needle punching machine with a needle density of 600 pieces / inch ² , a needle depth of 13 mm (inside), and 9 mm (surface side), and a weight per unit dry area of 575 g / m ² and a bulk density of 105.1 kg / m &lt; ³ &gt; was obtained in the same manner as in Comparative Example 1, except that an ACF nonwoven fabric precursor was obtained.

The obtained ACF nonwoven fabric was wound on a cylindrical structure having an inner diameter of 200 mm and a length of 1100 mm at a tension of 1.47 N / cm ² until the mass of the element became 100 kg to obtain an element having a diameter of 1.09 m and a bulk density of 100 kg / m ³ . The properties of the activated carbon fibers, ACF nonwoven fabric and the elements constituting the obtained ACF nonwoven fabric are shown in Table 1.

Claims (6)

The phenolic resin obtained by spinning and curing a mixture obtained by mixing a phenol resin with a mixture of at least one compound selected from the group consisting of fatty acid amides, phosphoric acid esters and celluloses is subjected to nonwoven fabrication and carbonization and activation, configuring the activated carbon fibers have a fiber diameter 21㎛ to 40㎛, toluene adsorption rate is 20% to 75%, the tensile strength of the non-woven activated carbon fiber nonwoven fabric, characterized in that at least 4N / cm ² to. The activated carbon fiber nonwoven fabric according to claim 1, wherein the weight per unit area is 200 g / m ² to 800 g / m ² . The activated carbon fiber nonwoven fabric according to claim 1 or 2, wherein the bulk density is 65 kg / m ³ to 100 kg / m ³ . An element comprising the activated carbon fiber nonwoven fabric according to claim 1 or 2 and having a bulk density of 90 kg / m ³ to 170 kg / m ³ . The element according to claim 4, wherein the pressure loss is 550 mmAq or less. A process for producing the activated carbon fiber nonwoven fabric according to any one of claims 1 to 3,
A step of spinning and curing a mixture obtained by mixing a phenol resin with at least one compound selected from the group consisting of fatty acid amides, phosphoric acid esters and cellulose, to prepare a phenolic fiber;
A step of fabricating the activated carbon fiber nonwoven fabric precursor by subjecting the phenolic fibers to nonwoven processing,
A step of carbonizing and activating the precursor
Wherein the activated carbon fiber nonwoven fabric has a surface roughness of less than 50 占 퐉.