CN101811027A - Gas adsorption agent and gas adsorption substrate - Google Patents

Gas adsorption agent and gas adsorption substrate Download PDF

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Publication number
CN101811027A
CN101811027A CN200910007865A CN200910007865A CN101811027A CN 101811027 A CN101811027 A CN 101811027A CN 200910007865 A CN200910007865 A CN 200910007865A CN 200910007865 A CN200910007865 A CN 200910007865A CN 101811027 A CN101811027 A CN 101811027A
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Prior art keywords
adsorbent
gas
gas adsorption
reactant liquor
adsorption substrate
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竹内齐久
米元笃史
笹田祥弘
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Nicca Chemical Co Ltd
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Nicca Chemical Co Ltd
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Abstract

The invention relates to a gas adsorption agent which is formed by loading organic silicon compounds containing amino groups and/or imino groups on a carrier, wherein partial or all the amino groups and/or the imino groups are obtained by neutralizing at least one of carbonic acid, formic acid and acetic acid.

Description

Adsorbent and gas adsorption substrate
Technical field
The present invention relates to adsorbent and gas adsorption substrate, in more detail, relate to the adsorbent and the gas adsorption substrate of acid class foul gas such as can adsorbing acetic acid and aldehydes foul gas.
Background technology
In the past, as the gas absorption agent material that is used to adsorb, remove various foul smell gases, the active carbons that adopt cheapness more.In addition, except that active carbon, porous materials such as silica, aluminium oxide also can be used as adsorbent.Yet these materials are to the absorption of foul smell gas, and are main by the physisorption to many minute apertures, therefore according to the kind of gas, can not get sufficient adsorbance sometimes.In addition, physical absorption, odorous substance is adsorbed easily, and on the other hand, the gas of absorption has the tendency of easy disengaging.Therefore, to above-mentioned material, more require the raising of performance as adsorbent.
At this problem, people attempt the surface of porous materials such as active carbon or silica, also to make to present chemisorption by the chemical treatment change except that physisorption, improve absorption property.For example, in following patent literature 1~3, proposed on porous material load and had an adsorbent of amino organo-silicon compound.And, by the modification of such amino, can think the absorption property of acid class foul gas such as effective raising Dichlorodiphenyl Acetate and aldehydes foul gas.
(patent documentation 1) spy opens flat 8-257346 communique
(patent documentation 2) spy opens the 2000-218159 communique
(patent documentation 3) spy opens the 2006-312164 communique
Summary of the invention
Adsorbent also can adopt its original form, for example, with filter and gas absorption sheet etc., also can be used as the material of gas adsorption substrate as air cleaner sometimes.Most gas adsorption substrates are normally made by give adsorbent on the base material of regulation.
But, when the adsorbent of record is made gas adsorption substrate in adopting above-mentioned patent documentation 1~3, can not get sometimes and the corresponding gas absorption performance of its use amount.According to the inventor's research, found out when making gas adsorption substrate heat treatment and through the time be subjected to thermal history, the absorption property of adsorbent significantly reduces.
The present invention proposes in view of above-mentioned problem of the prior art, purpose is to provide the absorption property excellence of acid class foul gas such as Dichlorodiphenyl Acetate and aldehydes foul gas, and, because of the gas absorption performance due to the heat reduces very little adsorbent and the gas adsorption substrate that adopts this adsorbent.
The inventor etc. for solve above-mentioned problem concentrate one's attention on research found that, above-mentioned such existing adsorbent is because of the gas absorption performance due to the heat reduces, and results from from the amino that contains amino silicon compound of load very big because of the modification due to the heat.In addition, find that based on this what the inventor etc. studied found that; by adopting specific acid to protect amino, can effectively present the absorption property of adsorbent, simultaneously; can fully prevent because of the gas absorption performance due to the heat reduces, thereby finish the present invention.
Promptly, gas absorbent of the present invention, it is characterized in that, be on carrier load have organo-silicon compound of amino and/or imino group, above-mentioned amino and/or imino group one one or all adopt at least a kind of acid that is selected from carbonic acid, formic acid and acetate to neutralize to obtain.
According to the present invention, by adopting above-mentioned amino of above-mentioned acid neutralization and/or imino group one one or all, can realize the excellent absorption property of acid class foul gas such as Dichlorodiphenyl Acetate and aldehydes foul gas, and, because of the adsorbent of the very little excellent heat resistance of the gas absorption performance reduction due to the heat.
In addition,, when the manufacturing of gas adsorption substrate, can keep sufficient gas adsorbability, make gas adsorption substrate efficiently with excellent gas adsorbability even heat-treat also according to adsorbent of the present invention.
In adsorbent of the present invention, the preferred active carbon of above-mentioned carrier or have the metal oxide of hydroxyl.
In addition, the preferred silica of metal oxide that has hydroxyl.At this moment, the load capacity with organo-silicon compound of amino and/or imino group guarantees fully that easily higher levels of gas adsorbability is easy to get.
In addition, in the adsorbent of the present invention, from further guaranteeing to obtain the viewpoint of sufficient gas adsorbability, the preferred 1nm of the average grain diameter of above-mentioned carrier~5 μ m.
In addition, the invention provides and on base material, give the gas adsorption substrate that adsorbent of the present invention forms.According to gas adsorption substrate of the present invention,, can effectively adsorb acid class foul gas and aldehydes foul gas such as acetic acid by giving adsorbent of the present invention.In addition, according to gas adsorption substrate of the present invention, when the manufacturing of base material and the man-hour of adding, by heat treatment or through the time have and be fully suppressed by the reduction of the gas adsorbability due to the thermal history, productivity ratio or processability and gas absorption performance all also are in high level with existing comparing, and can reach to make the best of both worlds.
According to the present invention, provide aldehydes foul gas such as formaldehyde and acetaldehyde, and organic acids such as acetic acid and butyric acid are that the absorption property of acid foul gas of representative is very excellent, reduce than existing also little adsorbent because of the gas absorption performance due to the heat simultaneously.In addition, according to the present invention, even provide heat treatment or through the time when being subjected to thermal history, still can keep than existing also high gas adsorption substrate the absorption property of above-mentioned foul gas.
The specific embodiment
Adsorbent of the present invention is having organo-silicon compound load on carrier of amino and/or imino group, amino and/or imino group one one or all adopt at least a kind of acid that is selected from carbonic acid, formic acid and acetate to neutralize to obtain.
Adsorbent of the present invention, for example, as carrier and above-mentioned organo-silicon compound, the compound of selecting interreaction can carry out combination, make their reactions after, neutralizing by above-mentioned acid obtains.After organo-silicon compound and the carrier reaction, fully there are not the person in amino and/or imino group on carrier be preferred.
As above-mentioned carrier, from considering, can adopt compound with hydroxyl with the reactive good viewpoint of organo-silicon compound with amino and/or imino group, the metal oxide that adopts active carbon or have a hydroxyl is preferred.As metal oxide, for example, can enumerate silica, aluminium oxide, titanium dioxide, zirconium dioxide and zinc oxide etc. with hydroxyl.
Active carbon and have the metal oxide of hydroxyl, its surface adopt hydroxide, carboxylate, ammonia, aliphatic or aromatic amine at alkali metal or alkaline-earth metal, contain impregnating method in the amino alkali such as macromolecule, carry out alkali treatment and also can.
In the present invention, even among above-mentioned carrier, it is preferred adopting the metal oxide with hydroxyl.At this moment, give base material with adsorbent and when obtaining gas adsorption substrate, can be littler to the form and aspect influence of base material.In addition, silica because the surface is rich in hydroxyl, can increase the load capacity of organo-silicon compound with amino and/or imino group, so be particularly preferred.
In addition, the scope of the scope of the preferred 1nm of the average grain diameter of the carrier that uses among the present invention~5 μ m, 1nm~1 μ m is that scope preferred, 1nm~500nm is that scope especially preferred, 1nm~200nm is most preferred.When the average grain diameter of carrier during less than 1nm, the ability that load has the organo-silicon compound of amino and/or imino group lacks, and the tendency that is difficult to obtain sufficient gas adsorbability is arranged.In addition, even average grain diameter greater than 5 μ m, because the surface area of carrier reduces, has the tendency that is difficult to obtain sufficient gas adsorbability.In addition, the average grain diameter of carrier then to the form and aspect influences very little (particularly suppressing albinism) of base material, can be made gas adsorption substrate simultaneously as being in the above-mentioned scope.In addition, when with adsorbent attached to base material on the time, process with spray-on process sometimes, in the time of in average grain diameter is in above-mentioned scope, the hole plug of sprayer is difficult to take place, and can improve the spraying flexibility (adaptability) of operation of adsorbent.Also have, the so-called average grain diameter among the present invention means and accumulates 50% meta particle diameter.
As organo-silicon compound used among the present invention, preferably have amino and/or imino group more than 1 and functional group's reaction that can have with carrier and the functional group's that combines compound with amino and/or imino group.When carrier has hydroxyl, the functional group as combining with this hydroxyl reaction, for example, can enumerate-SiOH is basic to be reached-SiOR base (here, R represents alkyl, the alkyl of preferred carbon number 1~3).
As organo-silicon compound with such functional group, for example, can enumerate 3-aminopropyl ortho-siliformic acid, methoxyl group (3-aminopropyl) dihydroxy silane, ethyoxyl (3-aminopropyl) dihydroxy silane, γ-An Bingjisanjiayangjiguiwan, gamma-aminopropyl-triethoxy-silane, γ-aminopropyl methyl dimethoxysilane, γ-aminopropyl methyldiethoxysilane, γ-aminopropyl dimethylethoxysilane, γ-(2-aminoethyl) aminopropyl trimethoxysilane, γ-(2-aminoethyl) aminopropyl triethoxysilane, γ-(2-aminoethyl) aminopropyl methyl dimethoxysilane, γ-(2-aminoethyl) aminopropyl methyldiethoxysilane, γ-(2-aminoethyl) aminopropyl dimethyl methyl TMOS, γ-(2-aminoethyl) aminopropyl dimethylethoxysilane, γ-(2-aminoethyl amino) propyl group (isopropoxy) dimethoxy silane, 2-(2-aminoethyl)-silane coupling agents such as 3-aminopropyl trimethoxysilane.
The organo-silicon compound that have amino and/or imino group for load on carrier, for example, the aqueous solution (usually, about 5~40 quality %) that can enumerate to above-mentioned organo-silicon compound adds above-mentioned carrier, in the method for stirring at room about 10 minutes~5 hours.The use amount of organo-silicon compound, relatively carrier 1g reach 0.1~5g be preferred, to reach 0.5~2g be preferred.
In addition, for with amino and/or imino group one one or all adopt at least a kind of acid that is selected from carbonic acid, formic acid and acetic acid to neutralize, for example, can enumerate in the above-mentioned aqueous solution that obtains, add neutralizing more than a kind in carbon dioxide, dry ice, formic acid and the acetic acid, make pH from originally 11~12 reach 4~10, preferred 6~10 method.Neutralisation treatment through such can obtain the aqueous dispersions that contains the gas adsorbent of the present invention.Also have, after neutralization, also can add original known compositions such as dispersant (preferred nonionic surfactants), thickener, anticorrisive agent as required.In addition, also can remove the water of aqueous dispersions, obtain pulverous adsorbent.
Adsorbent of the present invention, by will be from load on the carrier the amino and/or the imino group of organo-silicon compound, the acid more than a kind that employing is selected from carbonic acid, formic acid and acetic acid neutralizes, even heat-treat or through the time when being subjected to thermal history, still have the excellent heat resistance that the gas adsorbability of acid class gases such as Dichlorodiphenyl Acetate and gaseous aldehyde can fully keep.Specifically, so-called heat treatment is meant in 200 ℃ and carries out about 5 minutes, in addition, so-called through the time be subjected to thermal history, be meant in 100 ℃ and carry out about 100 hours, can fully keep gas adsorbability.
The gas adsorbability of adsorbent of the present invention presents stable on heating mechanism, and the inventor etc. are presumed as follows.That is, depickling also takes place even be heated in amino and/or the imino group from the organo-silicon compound that adopt above-mentioned acid to neutralize, becomes free amino and imino group, is difficult to carry out sex change thus.Therefore, can think that the amino and/or the imino group that still have abundant amount after heat treatment are residual, keep gas adsorbability.
Also have, in the present invention, the amino of the organo-silicon compound that have been used to neutralize and/or the acid of imino group from load on the carrier, to adopt the acid more than a kind that is selected from carbonic acid, formic acid and acetic acid be important.As neutralizing acid, when adopting organic acids such as strong acid, citric acid or malic acid such as hydrochloric acid or sulfuric acid etc., can not can not get effect of the present invention.Its reason can be thought: because neutralized salt is firm, and the step-down of gas adsorbability own, the hear resistance that is produced by above-mentioned depickling simultaneously also is difficult to present.
Adsorbent of the present invention does not have sufficient gas adsorbability even do not heat-treat yet, so can former state directly adopt yet.
Secondly, gas adsorption substrate of the present invention is described.
Gas adsorption substrate of the present invention is that the adsorbent of giving the invention described above on base material forms, give adsorbent after, also can carry out suitable air-dry or heat treatment.
As base material, for example, can enumerate fiber, plastics, paper, glass, active carbon, pottery etc.Base material as fiber is not particularly limited, and can enumerate the natural fiber of cotton, fiber crops, wool, silk etc., synthetic fibers such as polyester, nylon, acrylic compounds, polyolefin, semisynthetic fibres such as acetic acid esters, regenerated fiber and these composite fibres such as artificial silk.
Shape to base material is not particularly limited, and can suitably select to be suitable for using the shape of form.In addition, after gas adsorption substrate is made, also can carry out suitable processing and forming as required.
As the method for base material being given adsorbent, can enumerate: adopt adsorbent former state of the present invention, or water or pure equal solvent in addition suitably dilution or the dispersion liquid that concentrates, adopt the method that known method such as spraying or coating are coated with and the method for dipping etc.At this moment, also can in adsorbent or its dispersion liquid, add suitable adhesive.As adhesive, can adopt original known and be not particularly limited, for example, can enumerate polyvinyl alcohol, acrylic emulsions, vinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, methylcellulose, acrylic acid ethylene emulsion, polyurethanes emulsion, organic silicon emulsion etc.
In addition, as mentioned above, adsorbent of the present invention when the dispersion liquid as moisture equal solvent obtains, can remove the pulverous adsorbent that desolvates and obtain from the dispersion liquid distillation and mix with above-mentioned adhesive, and this mixture is coated on the base material.
To the use amount of adhesive, when adhesive was too much, gas adsorbability reduced sometimes.Therefore, the use amount of adhesive considers that from the viewpoint that adsorbent retentivity and gas adsorbability to base material reach balance adsorbent 1g reaches 0.1g relatively, preferably reaches 0.02~0.5g.
After giving adsorbent to base material, can adopt suitable condition to implement heat treatment according to the kind and the amount of giving of base material.
In addition, while the manufacture method of gas adsorption substrate of the present invention illustrated concrete example describe.For example, when base material is fibre, during in particular for cloth and silks such as fabric, braid or nonwoven, preparation contains the treatment fluid of gas adsorbent, this treatment fluid is coated on the base material, or base material is immersed in the method for treatment fluid, can give adsorbent base material.Then, by the heat drying base material, can obtain gas adsorption substrate.As the decentralized medium of the adsorbent in the treatment fluid, consider that from environment and security aspect lower alcohols such as water, methyl alcohol or ethanol are preferred.
The concentration of the adsorbent in the treatment fluid can suitably be set according to the purpose and the purposes of the gas adsorption substrate of making, when considering gas adsorbability and adaptability, outward appearance etc., adsorbent contain proportional preferred 0.001~3 quality %.
In addition, in the above-mentioned treatment fluid, except that adsorbent of the present invention, can suitably contain the original known composition that uses in the fiber process, for example antiseptic, fire retardant, antistatic additive, softening agent, anti-creasing agent etc.
The condition of heat drying can adopt the heat-treat condition of common fibre.In the present invention, even when under 200 ℃ of heat-treat conditions that reach about 5 minutes, carrying out heat drying, still can obtain excellent gas adsorbability.
Gas adsorption substrate of the present invention, for example,, can in the space that must carry out gas absorption, use with various members such as ornament materials as gas absorption such as interior automotive trim material such as built-in material, car pad, top material such as air cleaner filter, gas absorption sheet, wallpaper, curtain, carpets.These members that constitute by gas adsorption substrate of the present invention, though heat-treat or through the time when being subjected to thermal history, the absorption of acid class gas and gaseous aldehyde is removed the comparable original highland of ability and is kept.In addition, above-mentioned member, even implement heat treatment in its manufacturing process, gas adsorbability still can be maintained than original high level, it is excellent that productivity ratio and processing characteristics become.
Embodiment
Be described more specifically the present invention below by embodiment, but the present invention is not subjected to the qualification of these embodiment again.
The manufacturing of<gas adsorption substrate 〉
(embodiment 1)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 30 ", average grain diameter 10~20nm, dioxide-containing silica 30 quality %) 437g, add the reactant liquor of γ-(2-aminoethyl) aminopropyl trimethoxysilane 67g, about 2 hours in stirring at room.Then, be blown into carbon dioxide toward this reactant liquor, make the pH of reactant liquor reach 9, implement to add water 496g again after the neutralisation treatment, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.Also have, the pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, the above-mentioned aqueous dispersions that obtains is diluted to 50 times, adjust to the adsorbent aqueous dispersions (treatment fluid) of 0.4 quality %, polyester 100% black stained clot-h ((strain) look dyes society and makes), carry out impregnation process therein with absorbent (ピ Star Network ア Star プ) 50 quality % (the relative cloth of the amount of giving of gas absorbent reaches the condition of 0.4 quality % * 50 quality %=0.2 quality %).And, be distributed in 160 ℃ of dryings 2 minutes after the impregnation process, obtain gas adsorption substrate thus.
(embodiment 2)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 30 ", average grain diameter 10~20nm, dioxide-containing silica 30 quality %) 437g, add the reactant liquor of γ-aminopropyl methyl dimethoxysilane 67g, about 2 hours in stirring at room.Then, be blown into carbon dioxide toward this reactant liquor, make the pH of reactant liquor reach 9, implement to add water 496g again after the neutralisation treatment, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.Also have, the pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(embodiment 3)
In cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 20L ", average grain diameter 50nm, dioxide-containing silica 20 quality %) 665g, add the reactant liquor of γ-aminopropyl methyl dimethoxysilane 67g, about 2 hours in stirring at room.Then, add formic acid toward this reactant liquor and implement neutralisation treatment, make the pH of reactant liquor reach 9 after, add water 268g again, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.Also have, the pH of the reactant liquor before the neutralisation treatment is 11.4.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(embodiment 4)
Be diluted to 50 times operating the aqueous dispersions that obtains similarly to Example 1, adjustment reaches the adsorbent aqueous dispersions (treatment fluid) of 0.4 quality %, polyester 100% black stained clot-h ((strain) look dyes society and makes), 50 quality % carry out impregnation process with absorbent therein.And, be distributed under the room temperature air-dry 1 round the clock after the impregnation process, obtain gas adsorption substrate.
(embodiment 5)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス PS-S ", average grain diameter 100nm, dioxide-containing silica 20 quality %) 665g, add the reactant liquor of γ-(2-aminoethyl) aminopropyl trimethoxysilane 67g, about 2 hours in stirring at room.Then, be blown into carbon dioxide toward this reactant liquor, make the pH of reactant liquor reach 9, implement to add water 268g again after the neutralisation treatment, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.Also have, the pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(embodiment 6)
Toward silica (eastern rope silica (strain) system, trade name: the about 1 μ m of " E-220A ", particle diameter) add water 300g among the 133g and stir, yearn for the reactant liquor wherein added γ-(2-aminoethyl) aminopropyl trimethoxysilane 67g, about 2 hours in stirring at room.Then, add formic acid toward this reactant liquor and implement neutralisation treatment, make the pH of reactant liquor reach 9.In addition, the pH of the reactant liquor before the neutralisation treatment is 11.Reactant liquor after the neutralisation treatment adds " セ ロ Port-Le PC-300 " as dispersant, and (Sanyo changes into (strain) and makes, trade name) (ロ-デ イ ア solar corona (strain) is made for 15g, " ロ-De Port-Le 23 ", trade name) (Japanese catalyst (strain) is made for 10 quality % aqueous solution 20g and " ソ Off タ ノ-Le 120 ", trade name) 10g and water 455g, they are fully stirred, and the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(embodiment 7)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 30 ", average grain diameter 10~20nm, dioxide-containing silica 30 quality %) 437g, add the reactant liquor of γ-(2-aminoethyl) aminopropyl methyl dimethoxysilane 67g, about 2 hours in stirring at room.Then, be blown into carbon dioxide toward this reactant liquor, make the pH of reactant liquor reach 9, implement to add water 496g again after the neutralisation treatment, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.Also have, the pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(embodiment 8)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 30 ", average grain diameter 10~20nm, dioxide-containing silica 30 quality %) 437g, add the reactant liquor of γ-(2-aminoethyl) aminopropyl dimethoxy silane 67g, about 2 hours in stirring at room.Then, be blown into carbon dioxide toward this reactant liquor, make the pH of reactant liquor reach 9, implement to add water 496g again after the neutralisation treatment, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.Also have, the pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(embodiment 9)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 30 ", average grain diameter 10~20nm, dioxide-containing silica 30 quality %) 437g, add the reactant liquor of γ-An Bingjisanjiayangjiguiwan 67g, about 2 hours in stirring at room.Then, be blown into carbon dioxide toward this reactant liquor, make the pH of reactant liquor reach 9, implement to add water 496g again after the neutralisation treatment, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.Also have, the pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(embodiment 10)
In cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 0 ", average grain diameter 10~20nm, dioxide-containing silica 20 quality %) 665g, add the reactant liquor of γ-An Bingjisanjiayangjiguiwan 67g, about 2 hours in stirring at room.Then, be blown into carbon dioxide toward this reactant liquor, make the pH of reactant liquor reach 6, implement to add water 268g again after the neutralisation treatment, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.Also have, the pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(comparative example 1)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 30 ", average grain diameter 10~20nm, dioxide-containing silica 30 quality %) 437g, add the reactant liquor of γ-(2-aminoethyl) aminopropyl trimethoxysilane 67g, in stirring at room after about 2 hours, add water 496g again, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(comparative example 2)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 30 ", average grain diameter 10~20nm, dioxide-containing silica 30 quality %) 437g, add the reactant liquor of γ-(2-aminoethyl) aminopropyl trimethoxysilane 67g, about 2 hours in stirring at room.Then, add hydrochloric acid toward this reactant liquor and make the pH of reactant liquor reach 9, carry out neutralisation treatment after, add water 496g again, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.The pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(comparative example 3)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 30 ", average grain diameter 10~20nm, dioxide-containing silica 30 quality %) 437g, add the reactant liquor of γ-(2-aminoethyl) aminopropyl trimethoxysilane 67g, about 2 hours in stirring at room.Then, add citric acid toward this reactant liquor and make the pH of reactant liquor reach 9, carry out neutralisation treatment after, add water 496g again, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.The pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(comparative example 4)
Toward silica (eastern rope silica (strain) system, trade name: the about 1 μ m of " E-220A ", particle diameter) add water 300g among the 133g and stir, with toward the reactant liquor that has wherein added γ-(2-aminoethyl) aminopropyl trimethoxysilane 67g, in stirring at room about 2 hours.Then, (Sanyo changes into (strain) and makes to add " セ ロ Port-Le PC-300 " as dispersant toward this reactant liquor, trade name) (ロ-デ イ ア solar corona (strain) is made for 15g, " ロ-De Port-Le 23 ", trade name) (Japanese catalyst (strain) is made for 10 quality % aqueous solution 20g and " ソ Off タ ノ-Le 120 ", trade name) 10g and water 455g, they are fully stirred, and the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(comparative example 5)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 30 ", average grain diameter 10~20nm, dioxide-containing silica 30 quality %) 437g, add the reactant liquor of γ-(2-aminoethyl) aminopropyl methyl dimethoxysilane 67g, about 2 hours in stirring at room.Then, add hydrochloric acid toward this reactant liquor and make the pH of reactant liquor reach 9, carry out neutralisation treatment after, add water 496g again, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.The pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(comparative example 6)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 30 ", average grain diameter 10~20nm, dioxide-containing silica 30 quality %) 437g, add the reactant liquor of γ-(2-aminoethyl) aminopropyl methyl dimethoxysilane 67g, about 2 hours in stirring at room.Then, add citric acid toward this reactant liquor and make the pH of reactant liquor reach 9, carry out neutralisation treatment after, add water 496g again, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.The pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(comparative example 7)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 30 ", average grain diameter 10~20nm, dioxide-containing silica 30 quality %) 437g, add the reactant liquor of γ-(2-aminoethyl) aminopropyl dimethyl methyl TMOS 67g, about 2 hours in stirring at room.Then, add hydrochloric acid toward this reactant liquor and make the pH of reactant liquor reach 9, carry out neutralisation treatment after, add water 496g again, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.The pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(comparative example 8)
To in cataloid (daily output chemistry (strain), trade name: " ス ノ-テ Star Network ス 30 ", average grain diameter 10~20nm, dioxide-containing silica 30 quality %) 437g, add the reactant liquor of γ-An Bingjisanjiayangjiguiwan 67g, about 2 hours in stirring at room.Then, add hydrochloric acid toward this reactant liquor and make the pH of reactant liquor reach 9, carry out neutralisation treatment after, add water 496g again, the concentration that obtains adsorbent is the aqueous dispersions of 20 quality %.The pH of the reactant liquor before the neutralisation treatment is 11.6.
Secondly, except that adopting the above-mentioned aqueous dispersions that obtains, operate similarly to Example 1, obtain gas adsorption substrate.
(reference example 1)
Be diluted to 50 times operating the aqueous dispersions that obtains equally with comparative example 1, adjustment reaches 0.4 quality % adsorbent aqueous dispersions (treatment fluid), polyester 100% black stained clot-h ((strain) look dyes society and makes), 50 quality % carry out impregnation process with absorbent therein.And, be distributed under the room temperature air-dry 1 round the clock after the impregnation process, obtain gas adsorption substrate.
[the spraying processing applicability evaluation of adsorbent]
To the adsorbent aqueous dispersions that obtains in embodiment and the comparative example, adopt following method evaluation spraying processing applicability.The results are shown in table 1.
Is the concentration of adsorbent the adsorbent aqueous dispersions 50mL of 20 quality %, put into hand and hold spray bottle (trade name " ス プ レ イ ヤ-Port Application プ Z-305-101 ", (strain) three paddy バ Le Block are made), carry out spray operation repeatedly, to having made adsorbent.From the stopping state of sparger holes at this moment,, judge spraying processing applicabilities with 3 grades according to following benchmark.
Zero: initial stage and last resistance in test do not change, and adsorbent can be sprayed fully.
△: the resistance of adsorbent when sprayer comes out strengthens gradually, but adsorbent can be sprayed fully.
*: sparger holes stops up, and adsorbent can not be sprayed fully.
(table 1)
Spraying processing applicability
Embodiment 1 ??○
Embodiment 2 ??○
Embodiment 3 ??○
Embodiment 5 ??○
Embodiment 6 ??△
Embodiment 7 ??○
Embodiment 8 ??○
Embodiment 9 ??○
Embodiment 10 ??○
Comparative example 1 ??○
Comparative example 2 ??○
Comparative example 3 ??○
Comparative example 4 ??△
Spraying processing applicability
Comparative example 5 ??○
Comparative example 6 ??○
Comparative example 7 ??○
Comparative example 8 ??○
[evaluation of gas adsorption substrate]
To the gas adsorption substrate that obtains in the above embodiments and the comparative example, estimate gas adsorbability and form and aspect by following method.The results are shown in table 2.
(gas adsorbability)
In 5L examination bag, pack into obtain be cut into 10cm * 10cm (100cm 2) big or small gas adsorption substrate, seal, with air ejector air is wherein removed fully.Contain the initial concentration 50ppm of acetic acid or the nitrogen 3L of acetaldehyde initial concentration 20ppm toward wherein enclosing, after room temperature is placed 2 hours, measure the concentration of acetic acid or acetaldehyde, ask its slip by following formula.
(form and aspect)
The form and aspect of gas adsorption substrate detect by an unaided eye, and divide 3 grades to judge by following benchmark.
Zero: with the unprocessed polyester 100% black equal tone of stained clot-h.
△: do not observe spot, white powder, but all substrate surface is as seen white slightly.
*: substrate surface is seen hickie, or sees white powder.
(table 2)
As shown in table 2, confirmed from adopt load on the silica the amino of organo-silicon compound, the adsorbent that obtains with the carbonic acid neutralization, the gas adsorption substrate of the embodiment 1 that makes, no matter whether implement heat treatment, the gas adsorbability of Dichlorodiphenyl Acetate and acetaldehyde (embodiment 4) when not implementing heat treatment keeps same degree in its manufacture process.In addition, the amino of the organo-silicon compound of having confirmed from load on the silica with carbonic acid or formic acid neutralization, adopts the gas adsorption substrate of the embodiment 2~10 that obtains the adsorbent manufacturing, and the gas adsorbability of Dichlorodiphenyl Acetate and acetaldehyde is abundant.
On the other hand, employing to from load on the silica the gas adsorption substrate of comparative example 1 of amino unneutralized adsorbent manufacturing of organo-silicon compound, in its manufacture process, implemented heat treatment, (reference example 1) do not compared when heat-treating, and the gas adsorbability of known Dichlorodiphenyl Acetate and acetaldehyde obviously reduces.In addition, known with hydrochloric acid neutralized amino comparative example 2,5,7 and 8, with citric acid neutralized amino comparative example 3 and 6, all the gas adsorbability of Dichlorodiphenyl Acetate and acetaldehyde reduces.
(embodiment 11)
Be diluted to 10 times operating the aqueous dispersions that obtains similarly to Example 1, adjustment reaches the adsorbent aqueous dispersions (treatment fluid) of 2 quality %, polyester 100% black stained clot-h ((strain) look dyes society's system), carry out impregnation process (the relative cloth of the amount of giving of gas absorbent reaches the condition of 2 quality % * 50 quality %=1 quality %) therein with absorbent 50 quality %.And, be distributed in 160 ℃ of dryings 2 minutes after the impregnation process, obtain gas adsorption substrate.
(embodiment 12)
Except that the aqueous dispersions that obtains is operated in employing similarly to Example 5, operate similarly to Example 11, obtain gas adsorption substrate.
(embodiment 13)
Except that the aqueous dispersions that obtains is operated in employing similarly to Example 6, operate similarly to Example 11, obtain gas adsorption substrate.
(embodiment 14)
Except that the aqueous dispersions that obtains is operated in employing similarly to Example 7, operate similarly to Example 11, obtain gas adsorption substrate.
(comparative example 9)
Except that employing and comparative example 4 are operated the aqueous dispersions that obtains equally, operate obtaining gas adsorption substrate similarly to Example 11.
To the gas adsorption substrate that obtains in embodiment 11~14 and the comparative example 9, adopt said method to estimate form and aspect.As a result, the result of embodiment 1,5,6 and 7, comparative example 4 is shown in table 3 in the lump.
(table 3)
The concentration of the adsorbent in the treatment fluid (quality %) Form and aspect
Embodiment 1 ??0.4 ??○
Embodiment 11 ??2 ??○
Embodiment 5 ??0.4 ??○
Embodiment 12 ??2 ??○
Embodiment 6 ??0.4 ??○~△
Embodiment 13 ??2 ??△
Embodiment 7 ??0.4 ??○
Embodiment 14 ??2 ??○
Comparative example 4 ??0.4 ??△~×
Comparative example 9 ??2 ??×
As shown in table 3, even known embodiment 1,5,6 and 7 adsorbent many to the adhesion amount of base material, almost do not have the influence of the form and aspect of base material.On the other hand, the adsorbent of known comparative example 4, adhesion amount is many, and the form and aspect of base material change bigger, during as built-in material, poor practicability.
As mentioned above, the adsorbent that the present invention relates in the manufacture process of gas adsorption substrate, also can be brought into play excellent gas adsorbability even implement heat treatment.Also have, the original adsorbent of comparative example 1 is not implemented heat treatment when gas adsorption substrate is made, can bring into play sufficient gas adsorbability.Yet when adopting the adsorbent aqueous dispersions to process various base material usually, high-speed in order to seek operation, it is indispensable evaporating the water by heat treatment etc.Relative therewith, as adopting the adsorbent that the present invention relates to of excellent heat resistance, then can effectively make gas adsorption substrate with excellent gas adsorbability.
According to the present invention, provide aldehydes foul gas such as formaldehyde, acetaldehyde, and organic acids such as acetic acid, butyric acid are that the absorption property of acid foul gas of representative is very excellent, reduce than original little adsorbent because of the gas absorption performance due to the heat simultaneously.In addition, according to the present invention, even provide heat treatment or through the time when being subjected to thermal history, the absorption property of above-mentioned foul gas is kept than original high gas adsorption substrate.
In addition, according to gas adsorption substrate of the present invention, though when base material is made heat-treat the man-hour of adding or through the time be subjected to thermal history, the reduction of gas absorption performance also can fully be suppressed, productivity ratio or processability, gas absorption performance all are in high level than originally, can make the best of both worlds.Gas adsorption substrate of the present invention, be representative mainly at home-use or for motor vehicle air cleaner filter, can in interior automotive trim materials such as built-in materials such as wallpaper, curtain, carpet, car pad, top material, use, the absorption of acid class gas and gaseous aldehyde is removed, can be than reaching with high efficiency originally.

Claims (5)

1. adsorbent, this adsorbent is the organo-silicon compound that load has amino and/or imino group on carrier, above-mentioned amino and/or imino group one one or all adopt at least a kind of acid that is selected from carbonic acid, formic acid and acetate to neutralize to obtain.
2. according to the described adsorbent of claim 1, above-mentioned carrier is active carbon or the metal oxide with hydroxyl.
3. according to the described adsorbent of claim 2, above-mentioned metal oxide is a silica.
4. according to any one described adsorbent in the claim 1~3, the average grain diameter of above-mentioned carrier is 1nm~5 μ m.
5. gas adsorption substrate, this gas adsorption substrate entitle on base material requires that any one described adsorbent forms in 1~4.
CN200910007865A 2009-02-20 2009-02-20 Gas adsorption agent and gas adsorption substrate Pending CN101811027A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110652973A (en) * 2018-06-28 2020-01-07 株式会社科特拉 Sheet-like adsorbent and method for producing same
CN111971075A (en) * 2018-03-30 2020-11-20 尤尼吉可株式会社 Deodorizing material, method for producing the same, deodorizing method, and deodorizing sheet

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111971075A (en) * 2018-03-30 2020-11-20 尤尼吉可株式会社 Deodorizing material, method for producing the same, deodorizing method, and deodorizing sheet
CN110652973A (en) * 2018-06-28 2020-01-07 株式会社科特拉 Sheet-like adsorbent and method for producing same

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Application publication date: 20100825