CA2030837C

CA2030837C - Deodorant porous polymer and a deodorant fibrous material using the same

Info

Publication number: CA2030837C
Application number: CA 2030837
Authority: CA
Inventors: Tohru Yamamoto
Original assignee: Individual
Current assignee: Individual
Priority date: 1990-11-26
Filing date: 1990-11-26
Publication date: 1999-02-23
Anticipated expiration: 2010-11-26
Also published as: CA2030837A1

Abstract

A deodorant porous polymer having excellent deodorant effects is provided. The deodorant porous polymer is in the shape of substantially uniform particulates or an aggregate thereof, and is obtained by the hydrolysis and polycondensation of at least one alkoxide selected from the group consisting of inorganic alkoxides and metal alkoxides through the use of a sol-gel method. Also provided is a deodorant fibrous material that includes a fibrous substrate and a deodorant porous polymer as mentioned above, which is combined with the fibrous substrate in the physically-combined state and/or the chemically-combined state.

Description

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B~cKaRouND OF THE INVENTION

1. Fleld of the invention:
Th1s lnvention relates to a deodorant poly-mer, and more particularly, to a porous polymer havingexcellent deodorant effects which is obtained by the hydrolysis and polycondensatlon of inorganic alkoxides and/or ~etal alkoxides by a sol-gel method. This lnvention also relates to a deodorant fibrous material obtained by combining such a deo~orant porou~ polymer wlth a fibrous substrate.

2. Description of the prior art:
In recen~ years, with the im~rovements in the s~andard of llving, there have been strong dem~n~s to remove any displeasing odors in order to live a comfortable ~lfe. For example, various deodorizers are ~sed in order to remove or mask an odor ln places with high airt~shtness, such as bathrooms, toilets, cars, and refrigerators.

A~ong the deodorizer~, those having strong odors themselves such as perfumes or balsams are often u~ed to mask an odor in places wlth hlgh airtightness, such as to~lets and cars. However, these deodorlzers are llmited to specific applications because of their own strong smells. On the other hand, there are chemi-cal deodorizers that deodorize by chemical decomposi-tion of odoriferou~ co~pounds. Such deadorizer~ usual-ly oontain, as the maln component, a substanc~ extract-ed frcm plants or synthetic compound, and used, for example, in a spsay, for chemlcally decomposing a bad smell of trash or deodorlz$ng body odor. However, 20~fJ8 ~7 these chemical deodorlzers ha~e the disadvantages of havlng smell themselves and the capability to decompose only speclfic odors.

Other deodorlzers include absorptive deodor-izars such as, active carbon and siltc~ gel. Th~se deodorizers are composed of porous particles ln which odors are adsorbed, thereby achieving deodorization.
Silica gel used as a moisture absorbent can also show deodorant effec~s. Powders of s~lica gel manu~actured by a conventional method, however, have lar~e psre sizes and the psrosity (the proportion of pores to the total volume) is relati~ely small, thereby making it impossible to obtain satisfactory deodorant e~fects.
Even when active carbon with a relatively large deodor-izing activlty is used, it 1~ impossible to obtain satisfactory deodorant e~fects, because the pore size is not u~iform and the particle 8iZ~ iS relatively larse.

Recently, attem~ts have been made ~o sive deodorant effects to fibrous materlals such as in-80~ e~, ~anitary items, and underclothes. In a m thod for produaing such daodorant fibrous materials, for example, thin layers of deodorant powder~ are sealed into a cl~th of flbrou~ mat~rial~. ~owever, the product o~ai.ned by this method is bulky and cannot be used for underclothes and the like. ~ preferable method ~or produclng deodorant ~ibrous materials is to comblne deodorant materlals with a ~1brou~ substrate.
However, active carbon which ls belteved to have the highest deodorant activlty has a black-colored ap-pearance, and therefore, t~e applications of active 2 ~ 3 7 carbon are limited. As described above, deodorant f~brous materlals having excellent deodorant effects which can be readily produced are not yet obtalnable.

SUMMA~Y OF T~IE INVENTION

The deodorant porous polymer of this inven-tion, which overcomes the above.-discussed and numerous other dlsadvantages and deficiencies Or the prior art, ls a porous polymer in the shape of sub~tantially uniform particulates or an aggregate thereof, which is obta~ ned by the hydrolys~.s and polyconden~ation of at least one alkoxide selected from the group ccns~sting of inorganic alkoxides and metal alkoxides t~roush the use of a sol-gel method.
The method ~or producing a deodorant porous polymer o~ this lnvention comprises the step of hydro-lysing and polycondensing at least one ~lko~de selec~-ed from the group con~isting of inorganic alkoxides andmetal alkoxides by ~he use of catalyst for a sol-gel method so as to o~tain a porous polymer in the shape of substantlally uniform particulates or an aggregate ther~of.
In a preferred embodiment, the aforementioned catalyst fo:r the sol-gel method is a base catalyst.

The deodorant flbrous materlal of this inven-tlon comprlses a fibrous substrate and a deodor~ntporous polymer in the shape of substantially uniform particulates or an aggregate thereof the porous polyme.r belng prepared ~rom at least one alkoxlde selected from 2 ~ 8 ~ ~

the group consi~ting of inorganic alko~ides and metal alkoxides and a silane coupling agent through the use of a sol-gel method, and the porous polymer being combined with the f ibrous sub~trate in the physically-5 combined tate and~or the chemically-combined state.

In a preferred embodiment, th~ aforementioned silane coupling asent has an epoxy group.

~he ~ethod for produ~ing a deodorant fibrous material of this ~nvention comprises the steps of preparing the composit~on containing at least one alkoxide selected from the group consisting of inorgan-ic alkoxides ~nd metal alkoxides, a silane coupling agent, a catalyst for a sol-gel method, and a solvent, impregnatin~ a fibrous substrate with said composition ln a sol state, ~nd converting said ~ompositlon into a gel state to f orm a poroU~ polymer .

In a preferred embodiment, the aforementioned catalyst for the sol-gel method comprises an acid catalyst and a base ca~al~st.

In a more pre4erred embodiment, the aforemen-tioned bas~ catalyst for the sol-gel method is a ter-tiary amine which is substantially lnsoluble ln water and soluble in organic solvents.

In a more preferred ~bod~ent, the aforemen-tioned ~ilane couplins agent has an epoxy group.
Thus, the lnvention described herein makespossible the objective~ of (1) providing a deodorant 2~3~,ct~

porous polymer having excellent deodorant effects; (2~
providing a method for readily producing such a deodor-ant porou~ polymer: (3) providing a deodorant fibrous material ln which ~ deodorant porous polymer having 5 axcellent deodorant ef fects as mentioned above is strongly combined wlth a fibrous substrate; and (4~
providing a method for readily producing such a deodor-ant fibrou~ material.

DESCRIPTION OF THE PR~F~RRED EMBOD~MENTS

~he inorganic or metal alkoxides which can be used ln this invention are expressed by the general formula M( OR )m, where M ls an inorganic atom, such as 15 ~i, Na, Cu, Mg, Ca, Sr, Ba, Zn, 8, Al, Ga, Y, Si, Ge, Pb, P, Sb, Ta, W, La, Nd, and Ti; F~ is a lower ~lkyl containing one to four carbon atoms; and m is a valence number of M. Specif ic ~xamples of the alkoxides ln-c ud~ Si(0C2H5)4, Al(O-lso-C3}{7)3, Ti(0-lso-C3~7~4, zr(0-n-C3~7)A~ zr(o-t-C4Hg)4~ zr(0-n-C4H9)4~
Ca(~C2~5)2~ Fe(~C2HS)3, V(O-iso-C3H7)4, Sn(O-t-C4~9)4, L1(0C2H5~ ~e(OC2~5~3, B(O~2Hs)~, P(OC2Hs~3, P(OCH3)3, Mg(OCH3)2, and Mg(OC~5)2. Alkoxides containing two kinds of metals, such as Mg~Al(lso-OC3H7)4]2 and 2~ N~Al(iso-OC3~l7)4]2, can also be used. Particularly, Si(OC2~5)4, Ca(~C2H5)2, Zr(O-t-C4,Hg)4~ Zr(O-n-C4Hg)4, and Mg(OC2H5)2 are prefarred. Two or more kinds of these alkoxides can be used as a mixture. Particular-ly, it is preferred to use calcium alkoxide and/or magneslum alkoxide together with other alkoxide, ~or example, silane alkoxide. The deodorant porous pol~ner of thls invention can adsor~ both acid and 21kali substances effectively. In cases where calcium alkox-O ~i J 7 ide or magnesiurn alkoxide is used, acid su~tances are more readily adsorbed, because the Ca- or Mg-containing portion of the porous polymer obtained acts as a Brc~nsted base or a Lewis base.
s The silane coupling agent used in this inven-tion, i ~ needed, can b~ any of the well-known silane coupling agent~, such as ~-glycidoxyyLo~yl)trimethox-ysilane, (~-glycidoxypropyl~-methyldiethoxysilane, ~
(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltrime-thoxysilane, vinyltrichlorosilane, vinyltris(~-methoxy-ethoxy)s~lane, vinyltriacetoxysilane, (~-methacryloxy-p~opyl~trimethoxysilane, N-~-(N-vinylbenzylamtno~thyl)-~-aminopropyltrimethoxysilane hydrochloride, ~-amlno-propyltriethoxysilane, ~-phenyl~ minopro~yltrimethox-ysilane, ~-(2~aminoethyl)amlnopropyltrimethoxysllane, ~-~2-aminoethyl)aminopropylmsthyldlmethoxysilane, ~-m~rcaptopropyltrimethoxysilane, ~-merca~topropylmethyl-dime~hoxysllane, methyltrimethoxysilane, methyltri-e~hoxysilane, hexa~e~hyldisilazane, ~-anilinopro~yl-trimethoxysilane, ~-chloropropyl~rimethoxysilane, ~-chloropropylmethyldimethoxysilane, methyltrlchlorosi-lane, dlmethyldichlorosilane, trimethylchlorosilane, octadecyldimethyl[3-(trimethoxysylil)propyl]~ _ntum-chlorlde, and a mixture of amlnosllanes.

Particularly, in cases where dsodoran~ porous polym~rs are prepared, silane coupling a~ents contain-lng epoxy or vinyl groups are preferred. In cases where deodorant fibrous materials are prepared, silane coupling agznts containing epoxy or v~nyl groups are als~ preferred. Tha amoun~ o~ ~ilane coupling ~g~n~
to be used is no~ more than 10 parts by wei~ht, and ~n~0~7 mora prefsrably, about 3 parts by weight, for every 100 parts b~ weight of the aforementioned alkoxide. I~
cases where deodorant fibrous materials are prepared, it is desirable to use 1 to 10 parts by welght of silane coupliny agent, and more preferabl~, about 3 par~s by weight of sil~ne coupllng agent, for every 10~
parts by weight o~ the aforement~oned alkoxide. When the silane coupling a~ent is used in an amount of more than 10 parts by weight, the rigidity of the deodorant ~o~ous polymer obtained increases. Therefore, for example, when combining the deodorant porous polymer wi~h a fibrous substrate, the flexibility of the fibers is decreased. In cases where deodorant fibrous materi-als are prepared, when the amount of silane coupling agent to be added is less than l part by weight, the combined stren~th is decreased and the amount of deodorant porou~ polymer is prone to decrease. When silane coupllng agent-~ containing vinyl groups are used, irradiation with electron beams i~ re~uired dur~ng the production prooess.
In order to produce the deodcrant porou~
polymer of this invention, an acid catalyst is used, if necessary, a~ a catalyst ~or the sol-~el method. As the acid catalyRt, an inorganlc acld such as hydro-chloric acid, sulfuric acld, or nitric acid is usually used. Tt is posslble to obtain the same effects by bubbling a hydrogen chloride g218 into the xe~ctlon solution. Organic acids or thair anhydrides can also 30 be used. Examples thereo~ include tartaric acid, ~htha~ic acid, maleic acid, dodecylsuccinic acid, hexahydrophthalic acid, methyl endic acid, pyromellitic acid, benzophenonetetracarboxylic acid, dichlorosuccin-2~)~0~37 ~ ~

ic acid, chlorendic acid, phthalic znhydride, malelc anhydride, dodP.cylsuccinic anhydride, hexahydrophthalic a~hydride, methyl endic anhydride, pyromellltic dianhy-dride, benzophenonetetracarboxylic anhydride, dichloro-su~cinlc anhydrlde, and chlorendic anhydride. Forevery mole of the a~orementioned alkoxide, 0.5 mol or lass of these aclds are used. In case~ where deodor-ant fibrous mate_ials are prepa~ed, 0.001 mol or more of these acids, preferably 0.003-0.005 mol of ~hese acids, are used for every mole of th~ aforementioned alkoxide. Xf the amount of the acid is too lar~e, the polycondensation of the alkoxi~es proceeds too far and the polymer particles become too large, and the pore si~e of the polymer particles become large because of a high de~ree of orosslinklng, thereby det~riorating the deodorant effects of the polymer particles.

The bass cataly~t for the sol-gel method employed ~n this invention can be either an in~rganic 2~ base or an organic base. Examples of the inorganic base catalyst includes potassium hyd~oxide, sodium hydroxlde, lithium hydroxide, rubidium hydroxide, magnesium hydroxide, and ammonia. Examples of the organic base catalys~ includes primary am~e~, second-ary amines, tertlary amlnes, polyamine~, and complexcompounds of amines, such a~ ethylenediamine, di-ethylenetriamine, ethanolamins, butylam~ne, tri-ethylenetetramlne, dlethylaminopropylamin~, N-amlno-ethylpiperazine, N,N-dimethylb~nzylamine, tripropyl-amine, tributylamine, trlpentylamine, tris(dlmethyl-aminomethyl )phenol, math2phenylenediamine, di-aminodiphenylmethane, diamlnodipAenylsul~one, pQlyamide resins, dicyandiamide, boron trl~luoride-monoethylamine 2 O ? O ~ v~ 7 complexes, menthanediamine, xylylenediamlne, and ethylmethylimidazole.

Among the aforementioned base catalysts, a porous polymer in the shape of particulates can be obtained by tha use of ammonia, particularly an ammonia gas. More pref~rred ls a ter~iary amine that is su~-stantlally insoluble in water and soluble in organic solvents. Examples of the tertiary amlnes which can be used as a bass catalyst include N,N-dimethylbenzyl-amine, tripropylamine, tributylamine, and tripentyl-amine, with N,N-dimethylbenz~lamine being particularly preferred.

The amount of base catalyst to bs used ls in the rznge of from 0.002 to 1.5 mol for eve~y mole of ths alkoxide. In cases where the aforementioned tertiary amine that is substantia~ly insolubl~ in water and soluble ln organic solvents is used, the amount thereof is 0.002 ~ol or m~re, and more preferably in the ran~e of from 0.004 to 0.008 mol, for every mole of the alkoxide. In other cases, the base catalyst is usually used in an amount of from 0.1 to 1.5 mol.

As a solvent that can be used in the produc-tion of a deodorant porous polymer, there is a mlxture of water (used in hydrolysls~ and an organic ~olvent that can be miscible with water or an organic solvent that aan b~ partly dissolved in water. Exam-3~ ples of the organlc solvents lnclude methanol, ethanol,butanol, propanol, pentanol, hexanol, acetone, methyl ethyl ketone, and formamide. The amount o~ water to ~e used is lO mol or less, preferably 1 to 10 ~ol, more 2n3r~8~7 pre~erably 1 to 6 mol, and stlll more prefe~ably abou~

4 mol, for every mole of the alkoxide. I~ there is too llttle water, the hydrolysis of the alkoxide proceed~
slowly and ~he polyconden~ation is retarded. However, the hydrolysis proceeds gradually wi~h water present ln the air, so it is not necessary to add water to the solvent. Particularly, in cases where zlrconium-containing alkoxides having a higher moisture absorp-tion are used, it is not necessary to add water. If there is too much water, the deodorant effects of the deodorant porous polymer obtained will be decreased.

In order to produce a deodorant porous polymer according to the method of this invention, the ino~ganic al~oxide and/or the metal alkoxi~e are mixzd with a solvent. The concentration of alkoxlde is preferably in the r~nge of from 300 to ~00 g/l. To thls ~ixture, an acid catalyst for the ~ol-gel method is added, if needed. ~owever, the aforementioned acid catalyst is not necessarlly added, b~caus~ as the mixture is ~igorously stirred, carbonic acld is pro-duced by incarporatlon of carbon dioxide present in the alr in~o the mixturo. With thls treatment, hydrol-ysis is substantially complete. Then, a base catalyst for the sol-gel method ls added to thls mixture.
Although this mixture is aither a 901 mixture or an emulslon, gelatlon occurs as the polycondensation react~on of the hydrolyzed product proceeds by the aid of the base catalyst. The period of gelation can be ln the range o~ from several seconds ta hours by adJusting the amount of the base catalyst. It is also possible to proceed the reaction by mixlng the alkoxide, the catalyst for the sol-gel method, and the solvent at the 2n30837 same time. Xf needed, silane coupling agents can be added to the mixture together with ~he alkoxide. Par-ticularly, in cases where the deodorant porous polymer is combined with a fibrous substrate, plastlc sub-strate, or the like, the addition of si1ane couplingagents is preferrad~

The porous polymer of this invention is prepared as follows. Wlth the use of the aforemen-tioned sol mlxture or emulsion (includingprecipitates), or alt~rnatively a gel. When using a gel, a deodorant porous polymer in the shape of partic-ulates is obtained after grinding and heating to de-water the gel. When using a soi mixture, the period oi gelation is preferably set to be about 5 hours by ad~usting the pH of the mlxture to about 6-8 and using a small amount of base catalyst. For example, a deodorant porous polymer in the shape of partlculates is obtained by spray drying or fresze drying of the sol mixture. It is also possl~le to use a precipitation method or an evaporating decomposition method. In addition, the aforementioned mlxture in the sol state can be formed in~o a film by drying and remov~ng the solvent. Th~3 film obtained ~s cut into approprlate sizes to use as a deodorant film. This f$1m, like the a~orement~oned polymer in the shape o4 partlculates, is porous and h~s excellent deodorant effects~

The deodorant porous polyme~ of thls inven-tion can be used in the shape of particulates as men-tloned above. Moreover, the deodorant porous polymer can be combined with various kinds of films, fibrous ma~erials, plastic ma~erials, tim~ers and the like, as ~f33~

a substrate. In a preferred method for combinins various materials with the deodorant porous polymer of this ~nventlon, the afo~ementioned mixture in the sol state is applled to the substrate or, the substrate is S impregnated with the aforementioned mixture in the sol state, followed by drying the substrate. For example, a deodorant fibrous material is produced as follows.

The fibrous substrate used for the deodorant fibrous materials can be made of natural fiber, arti-ficial fiber, or semi-arti~icial fiber. More specifi-cally, fibrous materials such as fabric, nonwoven ~abric, thread, and pape~ can be used as the ~ibrous substrate. Alternatively, fibrous materials such as unspun cotton can be used as the fibrous substrate.

In ordPr to produce a deodorant ~ibrous matPrials according t~ the metho~ of this invention, a composition contalning alkox~des, a silane coupling agent, a catalyst for the sol~gel method, and a solvent is ~irst prepared as a mixture in the sol state. The concentra~ion o~ the alko~ide in the mixturP is prefer-ably in the range of from 200 to 300 g/l. When this mixture is left as it is, the hydrolysls of alkoxide, the polycondensation of the hydrolyzed product, and the reaction of the hydrolyzed product wlth the silane coupling agent proceed, resulting in a gelatlon. The time until gelation ls completed ti.e., gelation time) depends on the amount of water used, the amount of catalyst for the sol-gel method, and the pH o~ the composition. It is preferred to ad;ust the p~ to a~out 4-5 so that the gelation time becomes approximately 5 hours.

2n308 ~7 Next, the ~ibrous substrate is impregnated with the aforementioned composition in the sol sta~e.
Impregnation of the fibrous substrate can be achieved by immersing ~he fibrous substrate in a tank filled S wlth ths sol mixture or by spraying the sol mixtuxe onto the fibrous sub~trate, followed by passing the substrate through a mangle. Preferably, th~ 5 process is repeated several times, thereby sufficiently impreg-nating the fibrous substrate with the sol mixture.
When silane coupling agents containing vinyl groups are present in the sol mixture, the fibrous substrate impregnated with the sol mixture is irradiated during the production process.

By leaving this fibrous substrate in the air, the gelation of the mixture occurs to form a porous polymer, resuLting ln a deodo~ant fibrous material in which the porous polymer is combined with the fibrous substrate.
In the method of this invention, alkoxide is hydrolyzed by the aid of an acid catalyst ~i.e., alkoxy groups are converted into hydroxyl groups~, and the hydrolyzed alkoxides cause polycondensation with each other by the aid of a base catalyst, thereby forming a polymer. Whe:n a silans coupling agent is used together with alkoxides, the inorganic portion of the silane coupling agent is hydrolyzed (l.e., alkoxy groups are converted into hydroxyl groups) and cause polyconden-3~ sation with the hydrolyzed alkoxides. When the sllanecoupling agent cont~ins epoxy yroups, the cleavage of the epoxy groups occurs, and ~he ~olycondensation reac-tion proceeds ~etween the hydroxyl groups produced and 2~, 0'~ '~7 ~he hydroly~ed alkoxides. ~n the method of thls inven-tion, since the condensation reactlon proceeds in a uniform solution and a small amount of catalyct is used, the polymer particles obtained (i.e., primary particulates) has a small particle d$ameter a~d their size is uniform. These primary particulates have fine pores of 40 to 200 angstroms and the size of the partl-cles is in the range of from 10 to 15 nm. As the polycondensation proceeds, the particles combine wlth each other, thereby forming polymer particles with a ~hree-dimenslonal structure ~i.e., secondary particu-lates). The porosity of the polymer particles is about 60~. The porous polymer thus formed has a uni-form particle diamet~r and the adsorb~ng surface area in the pores of the polymer particles and ln the spaces ~ormed between the particles is several times lar~er than that of active carbon, thereb~ ma~ing it possible to efficiently adsorb odor substanc~s. There-fore, the porous polymer has excellent deodorant effects, The deodorant porous pol~ex of ~his inven-tion can eff~ctively adsorb both acid and alkaline substances. When calcium alkoxide or magn~sium alkox-~de is used, ecid substances are more readily adsorbed,because the Ca- or Mg-containing portion of the porous polymer obtained acts as a Br0nsted base or a Lewis base. Therefoxe, a substance such as lsova~eric acid which is particularly d~ficult to be ~dsorbed by silica gel or active carbon can be readily adsoxbe~.

In the deodorant fibrous material of this invention, the fibrous substrate ls impregnated with 2Q3~3837 the sol mixture and the polymer particles as mentioned above are formed in the fibrous substrate. There~o~, the polymer particles permeate inside of the fibrous substrate and combine strongly with the fibrous substrate in a physically-co~bined state. Furthermore, protons of hydroxyl groups in the fibrous substrate are ta~en away by the action of the catalyst in forming the polymer. Therefore, the polymer particles and the fibrous substrate are chemically combined with each other throush an oxygen bond. Particularly, when the polymer particles are formed using a silane coupling agent, the polymer particles readily combine w$th the ~i~ ~U~ ~U~ ~L d I ~, ~il~* ~i1~ ~r,~LvLll~y ~~
organic portion of the silane coupling agent with the flbrous material ls relatively high. Some fibrous materlals (e.g., polyamide fibers and glass fibers) have a possibility tha~ the fiber molecules may react to combine chemically with the hydrolyzed alkoxides, the sllane coupling agent, and the cleaved epoxy zo groups. Since the porous polymer is ~trongly combined with the fibrous substrate ln the physically-comblned state and/or -the chemically-com~ined state, the deo-dorant fibrous materlal of this invention has no tend-ency for the porous polymer to drop. In addition, the 2 softness and flexibil.tty of the fibrous substrate is not substantially affected. Furthermore, since the porous polymer is colorless, it is possible to give deodorant effects without affecting the color and pattern of the ~ibrous substrate.
As described abovs, the deodorant porous polymer of this invention has excellent deodorant effects and can be readily prepared by the sol-~el !~J ~ t ~ ~ ~;3 U 7 method. In additlon~ the deodorant flbrous material obtained by com~ining this deodorant porous polymer with a f ibrous substrate ha~ excellent deodorant ef-fects and no tendency for the porous polymer to drop.
Therefore, the deodorant fibrous material of this invention can be widely used for deodorant products, such as curtains, carpets, car interiors, insoles, sanitary i~ems, and underclothes.

The invention will be further explained with re~erence to the following exa~ples.

Example l The components shown in Table l, except N,N-dimethylben~ylamine, were mixed with stirring, thereby obtalnlng a suspension of ethylsilicate. N,N-dimethyl-benzylamine was added to this suspension with stirring.

Table 1 Components Amount (wt%) Ethylsilicat~ 42.28 Ethanol 39.2g Water 14.61 N,N-dimethylbenzylamine 3.82 By leaving the reaction mixture for 2 hours, porous monodisperse particulates were produced and these particulates gathered to ~orm a precipitate. The precipitate was filtered and dewatered, t~ereby obtain-ing a porous polymer ln the shape of particulates. The 2~3~g37 particulates thus obtained have an averaga particle dlameter o 200 nm and are porous particles having pores with a diameter o~ approximately 200 angstroms.

The porous polymer was ~xamined for d~odorant effects on trimethylamine, ammonla, and isovaleric acid. The results are shown in Table 4, together with the results obta~ned in Examples 2 to 4, and Compara-tive Example 1.
[Deodorant test using trlmethylamine]
First, 20 g of the deodorant porous polymer is pl~ced in an airt~ ght container of 350 ml, and 1 ml of 1.5~ aqueous trimethylamine solution is added there-to. The container is made a$rtight and left for 1 hour. Then, l ml of gas in the airtight container is taken out and sub~ected to a gas chromatography analy-sis, by which the peak area corresponding to trimethy-lamine ~s determined.
The same procedure is repeated, as a control, except that the deodorant porous polymer is not used.
The peak area corresponding to tri~ethylamine obtainad in this procedure is taken as 100% and the peak area corresponding to trimethylamine obtained by using the aforementioned deodorant porous polymer is calculated.
The rate of pea~ area decrease is determined as the rate of tri~ethylamine adsorption with respect to the test polymer.
[Deodorant test using ammonia~
First, 20 g of the ~eodorant porous polymer is placed in an airtight container of 350 ml, 1 ml of ~03~ 7 0.5% a~ueous ammonia solution is added thereto. The container is made airtight and left for 1 hour. Then, 10 ml of gas in th~ airtight container is taken out and bubbled lnto 10 ml of aqueous boric acid solution so as to ~e absorbed thereby. The absorbance at 630 nm i~
measured by an indophenol method to determine the amount of ammonia in the solution.

The same procedure is repeated, as a control, except that the deodorant porous polymer is not used.
The amount of ammonia obtained in this procedure is taken as 100% and the percentage of the ammcnia concen-tration obtained by using the aforementioned deodorant porous polymer is calculated. The rate of ammonia lS concentration decrease ls determined as the rate of ammonia adsorption wlth respect to the test polymer.

~Deodosan~ test using isovaleric acid]
Ftrst, 20 ~ of tha deodorant porous polymer is placed in an airtight container of 350 ml, and 5 ~1 of isovalerlc acid is added thereto. The container is made airtight and left for 1 hou~ ln a thermostat at 50~C. Thsn, 1 yl of gas in the airtight container is taken out and sub~ected to a gas chromatography analy-25 5is, by which the peak area cor~espor.dln~ to isovaleric acid is dstermined.

The same procedure is repeated, as a control, except tha~ the deodorant porous polymer is not usPd.
30 The peak area corresponding to isovaleric acid obtained t n this procedure is taken as 100~ and the correspond-ing ~o isovaleric acid ob~ained by using the aforemen-tioned deodorant porous polymer is calculated. The 2~30~ ~7 ra e of peak area decrease is determined as the rate of isovaleric acid adsorption with respect to the test polymer.

Example 2 The same procedurs was repeated as in Example 1, except that aqueous ammonia solu~ion t28%) was used instead of N,N-dime~hylbenzylamine. The porous polymer in the shape of particulates similar to that obtained ln Example 1 was obtained.

Example 3 Among the components shown in Table 2, ethyl-silicate and ethanol was mixed. ~he amount of water shown in Table 2 was added dropwise to the solution, whlle adJusting the rate of addltion so that the solu-tion did not become cloudy. Ammonia gas wa~ bubbled into the mixture so tha~ the amount o~ ammonia shown in Table 2 was added thereto. The mixture was sprayed on a plastic film as liquid drops of approxlmately 10 to 20 nm by the use of a spray. The film was dried while heati~g to about 30-70~C, so that the fine powders (porous polymer) remained on the film. These porous pol~mer particulates have a si~ilar structure to that of the porous polymer particulates obtained in Example 1. The par~iculates were colleo~ed and evaluated in the same manner as in Example 1. The results of the deodorant tests are shown in Table 4.

~'n30~7 Table ~

Components Amount (wt~) Ethylsilicate 42.28 Ethanol 40.01 Water 14.61 Ammonia 3.10 Example 4 The components shown in Table 3, except N,N-dimethylbenzylamine, were mixed with stirring, thereby obtaining a suspension containing ethylsillcate and calcium methoxide. N,~-dimethyl~enzyla~ine was added to the suspension with sti~rlng, and the gelation o~
the mixture occurred in about 10 minutes.

Table 3 C~mponents Amount (wt%) Ethylsilicate 42.28 Ethanol 37.91 2S 2N hydroch}oric acid 0.17a) Water 14.61 Calcium methoxide 1.21 Ethanol solution of 3.82 N,N-dimethylbenzylamine (3.2 wt~) a) In terms o~ the amount of HCl ~030~

~ he mixture in the soft-ge1 state was ground and dried, thereby obtaining powders having an average particle diameter of 1.85 ~m. The deodorant effects were evaluated in the same manner as in Example 1. The results are shown in Table 4.

~omparative Example 1 The same procedure was repeated as in E~ample 1, except that active carbon was used instead o~ the 7 ~ deodorant porous polymer. The results of the deodorant tests are shown in Tablc 4.

Table 4 Example ~o. Rate of odor substance adsorption ~%) Trimethylamine Ammonia Isovaleric acid Example 1 99.9 98.8 90.8 Example 2 99.9 96.4 92.3 ~xample 3 99.9 99.6 89.4 Example 4 g9.9 98.7 96.5 Comparative Example 1 3.0 14.8 Example 5 The components shown in Table 5 we~e mixed with stirrlng, thereb~ obtaining a mixture in the so~
~tate.

X ~.' 7 Next, a cuprammonium rayon cloth (~2.6 g~m2) was immersed in the aforementioned mixture, followed ~y passlng the cloth through a mangle. ~his process was repeated twice, thereby sufficiently impregnatin~
the m~xture into the cloth. Next, this cloth was dried at 13Q~C for 5 minutes, thereby obtaining a cloth in which the components of the aforementioned mixture were contained at ratio of 11 g/m~ (solid content).

Table 5 Components Amount (wt~) Ethylsi icate 20.22 Ethanol 20.22 2-N hydrochlorlc acid 0.14 Watsr 6.90 ~Glycydoxy propylmethoxysilane (Toray Silicon SH 6040) 3.16 Methanol 47.46 Ethanol solution of N,N-dimethylbenzylamine (3.2 wt%) 1.90 The dried cloth was cut into 15 x 20 cm swatches as a test piece of deodorant fibrous material.
This test plece was used instead of a porous polymer, and the deodorant effçcts on trimethylamine, ammonia, and isovaleric aoid were ev~luated, in the same manner as in Example 1. In each test, an untreated cloth was use~ as a control. The results are shown in Table 6, together wit~ the results obtained in Examples 6 and 7, and Comparative Example 2.

20'~Q~7 Example 6 ~he same procedure was repeated as in Example 5, except that a polyester oloth (64. 2 g/m~ ) was used as a f ibrous substrate, thereby obtaining a deodorant fibrous materlal in which a porous polymer was combined with the fibrous su~strate at the rate of 10 g/m2 (solld content). The deodoran~ effects of the fibrous material thus obtained was evaluated. The results are shown in Table 6.

Example 7 The sam~ procedure was repeated as in Example 5, except that a T-cloth (138.5 g/m2) was used as a fibrous substrate, thereby obtaining a deodorant fi-brous material in which a porous polymer was combined with the fibrous substrate at the rate of 22 g/m2 (solid content). The deodorant effects of the fibrous material thus obtained was evaluated. ~he results are shown in Table 6.
Comparative Example 2 The same procedure was repeated as in Example 5, exsQpt that 150 g of active carbon was used instead of the deodorant fibrous material. The results of the deodorant tests are shown in Table 6.

2~30~37 Table 6 Example No. Rate c~ odor substance adsorption ~) ~fibrous material) Trimethylamine Ammonia Isovaleric acid Example 5 (cuprammonium rayon) 99.8 96.6 84.9 Example 6 (polyester)96.1 92.~ 80.7 Example 7 (~-cloth) 99.1 94.8 80.5 Comparative Example 21) 3.0 15.4 1) Active carbon particles were used as a deodor-ant material.

It is understood ~hat various other modifica-tions will be apparent to and can readily be made by those skilled in the art without departing from the scope and spir:it of ~his inventlon. Accordingly, it ls not intended that the scope of the claims appended hereto be limited to the description as set forth herein, but rather that the claims be construed as encompassing all the features of patentable novelty that reside in the present invention, including all ~eatures that would be treated as equivalents thereof by those skilled in the art to which this invention pertains.

Claims

1. A deodorant porous polymer in the shape of substantially uniform particulates or an aggregate thereof, which is obtained by the hydrolysis and polycondensation of at least one alkoxide selected from the group consisting of inorganic alkoxides and metal alkoxides through the use of a sol-gel method, the hydrolysis and polycondensation involving combining said selected alkoxide with a catalyst for a sol-gel method in the presence of a solvent.

2. A method for producing a deodorant porous polymer comprising the step of:
hydrolyzing and polycondensing at least one alkoxide selected from the group consisting of inorganic alkoxides and metal alkoxides by the use of a catalyst for a sol-gel method so as to obtain a porous polymer in the shape of substantially uniform particulates or an aggregate thereof.

3. A method according to claim 2, wherein said catalyst for the sol-gel method is a base catalyst.

4. A deodorant fibrous material comprising a fibrous substrate and a deodorant porous polymer in the shape of substantially uniform particulates or an aggregate thereof, said porous polymer being prepared from at least one alkoxide selected from the group consisting of inorganic alkoxides and metal alkoxides and a silane coupling agent through the use of a sol-gel method involving combining said selected alkoxide and said silane coupling agent with a catalyst for a sol-gel method in the presence of a solvent, and said porous polymer being combined with said fibrous substrate in the physically-combined state and/or the chemically-combined state.

5. A deodorant fibrous material according to claim 4, wherein said silane coupling agent has an epoxy group.

6. A method for producing a deodorant fibrous material of claim 4, comprising the steps of:
preparing a composition containing at least one alkoxide selected from the group consisting of inorganic alkoxides and metal alkoxides, a silane coupling agent, a catalyst for a sol-gel method, and a solvent;
impregnating a fibrous substrate with said composition in a sol state; and, converting said composition into a gel state to form a porous polymer.

7. A method according to claim 6, wherein said catalyst for the sol-gel method comprises an acid catalyst and a base catalyst.

8. A method according to claim 7, wherein said base catalyst for the sol-gel method is a tertiary amine which is substantially insoluble in water and soluble in organic solvents.

9. A method according to claim 6, wherein said silane coupling agent has an epoxy group.