CN101222944A - Deodorant - Google Patents
Deodorant Download PDFInfo
- Publication number
- CN101222944A CN101222944A CNA2005800346028A CN200580034602A CN101222944A CN 101222944 A CN101222944 A CN 101222944A CN A2005800346028 A CNA2005800346028 A CN A2005800346028A CN 200580034602 A CN200580034602 A CN 200580034602A CN 101222944 A CN101222944 A CN 101222944A
- Authority
- CN
- China
- Prior art keywords
- deodorizer
- deodorization
- deodorant
- mass parts
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002781 deodorant agent Substances 0.000 title claims abstract description 85
- 239000000203 mixture Substances 0.000 claims abstract description 78
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 14
- 238000004332 deodorization Methods 0.000 claims description 126
- 239000007789 gas Substances 0.000 claims description 75
- 239000000463 material Substances 0.000 claims description 54
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- NMRHMBPYSDZGGI-UHFFFAOYSA-N NC(=N)N.NNC(NN)=O Chemical compound NC(=N)N.NNC(NN)=O NMRHMBPYSDZGGI-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 150000003463 sulfur Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 39
- 230000001877 deodorizing effect Effects 0.000 abstract description 18
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical class NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 abstract description 16
- KPTSBKIDIWXFLF-UHFFFAOYSA-N 1,1,2-triaminoguanidine Chemical class NN=C(N)N(N)N KPTSBKIDIWXFLF-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- JGGFDEJXWLAQKR-UHFFFAOYSA-N 1,2-diaminoguanidine Chemical class NNC(N)=NN JGGFDEJXWLAQKR-UHFFFAOYSA-N 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
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- 229910000323 aluminium silicate Inorganic materials 0.000 description 41
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- 239000012212 insulator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- GGROONUBGIWGGS-UHFFFAOYSA-N oxygen(2-);zirconium(4+);hydrate Chemical compound O.[O-2].[O-2].[Zr+4] GGROONUBGIWGGS-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 125000005624 silicic acid group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
Landscapes
- Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
A deodorant for an aldehyde-based gas which comprises at least one selected from a monoaminoguanidine salt, a diaminoguanidine salt and a triaminoguanidine salt; a deodorant-carrying article for an aldehyde-based gas which comprises a carrier and the above deodorant carried thereon; and a deodorant composition which comprises at least one substance selected from a deodorant for a sulfur-containing gas, a deodorant for a basic gas and a deodorant for an organic acidic gas and the above deodorant for an aldehyde-based gas and/or the above deodorant-carrying article. The above deodorant for an aldehyde-based gas and the above deodorant-carrying article for an aldehyde-based gas are excellent in the deodorizing performance capability for an aldehyde-based gas and the above deodorant-carrying article for an aldehyde-based gas is also excellent in the resistance to water, and a deodorizing product containing the above deodorant also exhibits excellent deodorizing performance capability.
Description
Technical field
The present invention relates to the deodorizer of gaseous aldehyde and contain deodorant compositions this deodorizer, that various stenches are had excellent deodoriging properties.Also relate to the deodorization goods such as various fibers, coating, sheet material and molding product that to bring into play excellent deodoriging properties by containing this deodorizer or deodorant compositions.
Background technology
In recent years, consumer is for being the deodorant demand rapid growth of object with Nicotiana tabacum L. foul smell etc. especially.Acetaldehyde is the main component of this Nicotiana tabacum L. foul smell.In addition, the dwelling house syndrome that the is regarded as causing a disease/building syndrome that causes a disease etc. are such, and the Health cost of being brought by formaldehyde also receives publicity.As the remover of these gaseous aldehydes, mainly studied the aldehyde remover of forming by amines.
The affinity height of known amine chemical compound and gaseous aldehyde contacts with the liquid that is dissolved with amines by the aerofluxus that will contain gaseous aldehyde, can remove the gaseous aldehyde (for example, referring to Patent Document 1) in the aerofluxus.But liquid amines is owing to emit intensive unhappy foul smell, thus be not suitable for being applied to living space, for example with in the daily life headed by living room, the kitchen.
In addition, known have amines is carried on gas absorbent on the inorganic matter.This gas absorbent has and is adding resin to, can tolerate the feature of heat treated when copying paper and thin film.
For example, known have in active carbon load ammonium salt, aniline etc. (for example, refer to Patent Document 2, refer to Patent Document 3) or the load intramolecularly has a primary amine groups in the magnesia clay mineral of silicic acid chemical compound is (for example, refer to Patent Document 4) or at the gas absorbent (for example, with reference to non-patent literature 1) of the interlayer load polyamino compound of layered phosphates (α zirconium phosphate).
In addition, as gaseous aldehyde deodorizer, known have 25 ℃ of dissolubility to water be below 5g/ rises hydrazine derivate (for example, refer to Patent Document 5), (for example have deodorizer that the chemical compound of primary amine groups forms by magnesium silicate clay mineral and intramolecularly, refer to Patent Document 6), comprise the compositions (for example, referring to Patent Document 7) of hydrazine compound in the synthetic resin.But these gas absorbents not only do not reach realistic scale to the absorbability of gaseous aldehyde, and by adding fiber or coating to, the aldehyde absorbability further reduces.
In addition, known to contain amino organo-silicon compound in the silica surface load, show deodoriging properties (for example, referring to Patent Document 8) to acetaldehyde.With regard to this material, if with it when the effective deodorizer of alkaline gas or sulfur class gas is used simultaneously, also can't give full play to the deodoriging properties that should bring into play.
In addition, provided and be used for the filter of clean air, the medicament that will be used to remove aldehydes is carried on the carrier such as active carbon and the article that form are used to remove the medicament of aldehydes as this, illustration Guanidine nitrate (1:1), aminoguanidine sulfate (for example, referring to Patent Document 9).
Zero existing document
Patent documentation 1: Japanese kokai publication sho 51-44587 communique
Patent documentation 2: Japanese kokai publication sho 53-29292 communique
Patent documentation 3: Japanese kokai publication sho 56-53744 communique
Patent documentation 4: Japanese kokai publication hei 9-28778 communique
Patent documentation 5: Japanese kokai publication hei 8-280781 communique
Patent documentation 6: Japanese kokai publication hei 9-28778 communique
Patent documentation 7: Japanese kokai publication hei 10-36681 communique
Patent documentation 8: Japanese kokai publication hei 9-173830 communique
Patent documentation 9: Japanese kokai publication hei 10-235129 communique
Non-patent literature 1: tunami Gu etc., PHARM.TECH.JAPAN, 1996,12 volumes, No. 12, p.77-87
Summary of the invention
Invent problem to be solved
Problem of the present invention is to provide a kind of deodorizer of the deodoriging properties excellence to gaseous aldehydes such as acetaldehyde, formaldehyde and the deodorant compositions that contains this deodorizer, and is provided at the article that also can bring into play excellent deodoriging properties in the deodorization goods such as fiber, coating, sheet material and molding product that contain this deodorizer or deodorant compositions.
The method of dealing with problems
The inventor studies intensively in order to address the above problem, found that and contain the gaseous aldehyde deodorizer that is selected from the above material of at least one in the group that mono amino guanidinesalt, diaminourea guanidinesalt and triamido guanidinesalt formed, it is to the absorption property excellence of gaseous aldehydes such as acetaldehyde and formaldehyde, thereby has finished the present invention.In addition, discovery will be selected from the above material of at least one in the group that mono amino guanidinesalt, diaminourea guanidinesalt and triamido guanidinesalt formed and be carried on gaseous aldehyde deodorizer carrier on the carrier, it is to the deodoriging properties excellence of gaseous aldehydes such as acetaldehyde and formaldehyde, and the resistance to water of this deodorizer carrier is also excellent, thereby has finished the present invention.A kind of deodorant compositions also is provided, and it contains the above material of at least one and the gaseous aldehyde deodorizer of above-mentioned record and/or the gaseous aldehyde deodorizer carrier of above-mentioned record that is selected from the agent of sulfur class eliminating malodours from gases, alkaline gas deodorizer and the agent of organic acidity eliminating malodours from gases.In addition, find to contain the deodorization goods such as fiber, coating, sheet material and molding product of deodorizer of the present invention, deodorizer carrier or deodorant compositions, its deodoriging properties is also excellent.
Illustration of the present invention is as follows.
(1) a kind of gaseous aldehyde deodorizer, it contains the above material of at least one that is selected from the group that mono amino guanidinesalt, diaminourea guanidinesalt and triamido guanidinesalt formed.
(2) a kind of gaseous aldehyde deodorizer carrier wherein, is carried on above-mentioned 1 described gaseous aldehyde deodorizer on the carrier.
(3) a kind of deodorant compositions, it contains the above material of at least one and above-mentioned 1 described gaseous aldehyde deodorizer and/or the above-mentioned 2 described gaseous aldehyde deodorizer carriers that are selected from the agent of sulfur class eliminating malodours from gases, alkaline gas deodorizer and the agent of organic acidity eliminating malodours from gases.
(4) a kind of deodorization goods, it contains above-mentioned 1 described gaseous aldehyde deodorizer and/or above-mentioned 2 described gaseous aldehyde deodorizer carriers.
(5) a kind of deodorization goods, it contains above-mentioned 3 described deodorant compositions.
The invention effect
Gaseous aldehyde deodorizer of the present invention and/or gaseous aldehyde deodorizer carrier, because to the deodoriging properties excellence of gaseous aldehyde, thereby can be from the gaseous aldehyde of removing effectively such as indoor.In addition, deodorant compositions of the present invention is not only keeping deodoriging properties of the excellence of sulfur class gas, alkaline gas or organic acidity gas etc., and can give full play to the deodoriging properties to gaseous aldehyde.
The specific embodiment
Below the present invention is described in detail.
Zero aminoguanidinium salts
The mono amino guanidinesalt that uses among the present invention, diaminourea guanidinesalt and triamido guanidinesalt are generically and collectively referred to as aminoguanidinium salts.
Concrete example as the mono amino guanidinesalt, aminoguanidine sulfate, aminoguanidine monohydrochloride and aminoguanidin carbonate etc. are arranged, in addition, diaminoguanidine hydrochlorate and diaminoguanidine sulfate etc. are arranged as the diaminourea guanidinesalt, in addition, as the triamido guanidinesalt triaminoguanidine hydrochlorate etc. is arranged.These all can be used alone or as a mixture.In addition, aminoguanidine monohydrochloride, aminoguanidine sulfate, diaminoguanidine hydrochlorate or triaminoguanidine hydrochlorate be because the resistance to water height, thereby preferred, more preferably diaminoguanidine hydrochlorate or triaminoguanidine hydrochlorate.In addition, aminoguanidine monohydrochloride, aminoguanidine sulfate, diaminoguanidine hydrochlorate or triaminoguanidine hydrochlorate be because the resistance to water height when being supported on the carrier is therefore preferred, more preferably diaminoguanidine hydrochlorate or triaminoguanidine hydrochlorate.Preferred aminoguanidine monohydrochloride or aminoguanidine sulfate when in addition, considering the safety of chemical compound.In addition, use, can improve deodorization by aminoguanidinium salts is mixed the back with the silicic acid attaclay.
Zero carrier
The carrier of load aminoguanidinium salts among the present invention is so long as can improve water-proof material just without limits.Concrete carrier can the illustration silicate compound, tetravalent metal phosphate chemical compound, zeolite, silica gel and active carbon etc., preferred silicate compound, tetravalent metal phosphate chemical compound, zeolite and silica gel, especially silicate compound, tetravalent metal phosphate chemical compound or zeolite are preferred because of obtaining high resistance to water.
Zero silicate compound
As the silicate compound of load aminoguanidinium salts among the present invention, just be not particularly limited so long as can improve water-proof chemical compound.Particularly, preferred aluminium silicate or magnesium silicate are from improving resistance to water aspect, more preferably noncrystalline silicic acid aluminum or noncrystalline silicic acid magnesium.In addition, these can be natural materials or synthetic.For example synthetic aluminium silicate is the material shown in the following formula (1).
Al
2O
3·nSiO
2·mH
2O (1)
Wherein, n is the positive number 6 or more in the formula (1), more preferably n be 6～50 and m be 1～20 positive number, especially preferably n be 8～15 and m be 3～15.
Magnesium silicate is the material shown in the following formula (2) in addition.
MgO·nSiO
2·mH
2O (2)
Wherein, n is the positive number 1 or more in the formula (2), more preferably n be 1～20 and m be 0.1～20 positive number, further preferred n be 1～15 and m be 0.3～10, especially preferably n be 3～15 and m be 1～8.
The silicate compound of composite for example can synthesize by the following method.Aqueous solution with the aqueous solution and the silicate base slaine of aluminum salt or magnesium salt, under room temperature, atmospheric pressure, add acid or alkali as required, keep about 3～about 7 the condition of pH and make its co-precipitation, with its in for example about 40 ℃～about 100 ℃ of left and right sides ripenings or not ripening just with coprecipitate washing, dehydration, drying, can synthesize thus.
In aluminium silicate synthetic, the use amount of the water soluble salt of aluminum and silicate base slaine may be selected to be: SiO
2/ Al
2O
3Mol ratio be more than 6, for example in 6～50 scope, more preferably in 8～15 scope.
In magnesium silicate synthetic, the use amount of the water soluble salt of magnesium and silicate base slaine is chosen as: SiO
2The mol ratio of/MgO is more than 1, for example in 1～20 scope, more preferably in 1～15 scope.
In addition, as other synthetic method, for example can form: in silica gel, add the aqueous solution of aluminum salt or magnesium salt, then, utilize acid or alkali by following method, the pH of system is maintained about 3～7, fully mix homogeneously then, is warmed to for example about 40 ℃～about about 100 ℃, ripening or not ripening are washed afterwards, are dewatered, dry and form.At this moment, the use amount of the water soluble salt of silica gel and aluminum or magnesium, can with above-mentioned SiO
2/ Al
2O
3, SiO
2/ MgO similarly selects.Explanation so far is with noncrystalline silicic acid aluminum and noncrystalline silicic acid magnesium synthetic individually example respectively, can also be by the synthetic chemical compound that contains two kinds of metals of mixed aqueous solution of the water soluble salt of aluminum and magnesium.
As above-mentioned water soluble salt, for example can illustration sulfate, the water soluble salt of nitrate, chlorate, iodized salt, Bromide and so on.
Further, as at above-mentioned alkali or the sour example that uses in synthetic, can the illustration sodium hydroxide, bases such as potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, acids such as hydrochloric acid, sulphuric acid, nitric acid.
Zero tetravalent metal phosphate chemical compound
Tetravalent metal phosphate chemical compound among the present invention is the tetravalent metal phosphate chemical compound to water-insoluble or slightly solubility, as preferred concrete example, zirconium phosphate, titanium phosphate, phosphoric acid stannum etc. is arranged.The crystalloid material and the noncrystalline material of various crystallographic systems such as these chemical compounds have and have alpha type crystal, β type crystal, γ type crystal, Nasicon type crystal all can use.Wherein, the alpha type crystal chemical compound is owing to can improve water-proof degree height and have the deodoriging properties of ammonia, and is therefore preferred.
Zero zeolite
Zeolite among the present invention can be natural materials or synthetic.The structure of zeolite is various, can use the zeolite of known arbitrary structure.As this structure, A type, X type, Y type, α type, β type, ZSM-5 etc. are for example arranged.
Zero silica gel
Silica gel has the silica gel with various characteristics according to manufacture method adjustment form area and/or fine pore, can use known any silica gel.As its Production Example, can in waterglass, add sulphuric acid and obtain gel and washing, crushed after being dried makes silica gel.
Zero active carbon
The known active carbon that has Treatment with activating agent timber, brown charcoal, peat etc. such as using zinc chloride, phosphoric acid and dry distilling to obtain, or the active carbon that uses water vapour that activation such as Linesless charcoal are obtained can use known any active carbon.As its concrete example, the activated coco nut charcoal of being made by the shell of Cortex cocois radicis is arranged.
The manufacture method of zero deodorizer carrier
Autofrettage to deodorizer carrier of the present invention is carried out illustration.
Carrier is stirred on the limit, the limit drips or the solution of spraying aminoguanidinium salts, at 60～120 ℃, preferably dry under 80～110 ℃, can obtain deodorizer carrier of the present invention thus then.In order further to improve resistance to water, can be illustrated in this drying post-heating to 140～240 ℃, preferably be heated to 160 ℃～220 ℃ methods of making.This aminoguanidine solution can be that aqueous solution also can use organic solvents such as ethanol, methanol, is preferably aqueous solution.
In addition, can illustration use Henschel mixer etc. with behind carrier and the aminoguanidinium salts uniform mixing, the method for heating manufacturing under the temperature below the decomposition temperature of aminoguanidinium salts.Situation about heating behind concrete heating-up temperature and dropping or the spray solution is identical.
And then, can also following processing: after carrying out that the carrier compounds effective as aminoguanidinium salts adhered to the operation that is worked on the deodorization goods that are made of filter, fiber or paper etc. in advance, to the solution of its dropping or spraying aminoguanidinium salts.
Aminoguanidinium salts is 0.1～80 mass parts to the relative 100 mass parts carriers of the load capacity of various carriers, is preferably 3～50 mass parts, more preferably 10～30 mass parts.When the load capacity of aminoguanidinium salts is less than 0.1 mass parts, can't obtain sufficient deodorizing effect, when load capacity is more than 80 mass parts in addition, since can't the abundant load of suppressed by vector, when washings such as water, the effective ingredient stripping, not only can't expect deodorizing effect corresponding to addition, and with gaseous aldehyde deodorizer beyond deodorizer when mixing, often cause the deodorizing effect reduction of the blended deodorizer of institute, so not preferred.
Zero with the mixing of other deodorizer
Deodorizer of the present invention and deodorizer carrier are effective to gaseous aldehyde, as gaseous aldehyde, acetaldehyde, formaldehyde, nonenyl aldehyde etc. are for example arranged.As the using method of reality, separately that gaseous aldehyde is few as the situation of object, often with can eliminate gaseous aldehyde beyond malodorous deodorizer mixes (deodorant compositions) or use simultaneously.In addition, use, can improve deodorization by in deodorant compositions, mixing the silicic acid attaclay.
As object lesson, the deodorant alkaline gas deodorizer that is used for alkaline gas such as ammonia, trimethylamine can be mixed use with deodorizer of the present invention and/or deodorizer carrier.For example, use tetravalent metal phosphate chemical compound to water-insoluble or slightly solubility, and it is mixed with deodorizer of the present invention and/or deodorizer carrier, thereby can make deodorant compositions as alkaline gas deodorizer.As the preferred concrete example of this tetravalent metal phosphate chemical compound, zirconium phosphate, titanium phosphate, phosphoric acid stannum etc. are arranged.In these chemical compounds, have and have alpha type crystal, material and amorphous material of the crystalloid of various crystallographic systems such as β type crystal, γ type crystal, Nasicon type crystal, so long as have the material of gas adsorbability, all can mix with deodorizer of the present invention and/or deodorizer carrier.
In addition, the deodorant sulfur class eliminating malodours from gases agent that is used for sulfur class gases such as hydrogen sulfide, methanthiol can be mixed use with deodorizer of the present invention and/or deodorizer carrier.For example, load can there be tetravalent metal phosphate chemical compound, zinc oxide or the zinc silicate of the above metal ion of at least one that is selected from copper, zinc, the manganese to mix, thereby make deodorant compositions with deodorizer of the present invention and/or deodorizer carrier.In the metal ion on being carried on this tetravalent metal phosphate chemical compound, especially copper ion is because to the deodorizing effect height of hydrogen sulfide etc., and is therefore preferred.
For metal ion being carried on the tetravalent metal phosphate chemical compound, the tetravalent metal phosphate chemical compound is contacted with the saline solution of metal ion and waiting load to get final product by ion exchange.
The load capacity of metal ion as long as in the ion exchange capacity of tetravalent metal phosphate chemical compound, then can freely be adjusted to 100% according to expectation.
In addition, for zinc oxide, cupric silicate and zinc silicate, the material deodoriging properties height that specific surface area is big, therefore preferred.
The malodorous organic acidity eliminating malodours from gases agent that is used to remove acetic acid, isovaleric acid, butanoic acid etc. can be mixed use with deodorizer of the present invention and/or deodorizer carrier.For example, hydrous zirconium oxide(HZO), hydrous titanium oxide, brucite or brucite sinter can be mixed with deodorizer of the present invention and/or deodorizer carrier, thereby make deodorant compositions.
Hydrous zirconium oxide(HZO) can contain zirconium solution manufacturing by hydrolysis zirconium oxychloride aqueous solutions such as water, alkaline solution etc.In addition, hydrous zirconium oxide(HZO) has various sayings such as zirconyl hydroxide, zirconium hydroxide, oxidizing aqueous zirconium, Zirconium oxide hydrate, is identical with hydrous zirconium oxide(HZO).
The silicic acid attaclay is to be the clay mineral of main constituent with the magnesium silicate, owing to the pore with the about 1nm in aperture has the gas absorption performance.Be added with deodorizer of the present invention, deodorizer carrier or the deodorant compositions of silicic acid attaclay, can further improve deodoriging properties alkaline foul gas, acid foul gas, gases containing stench sulphureous gases, aldehyde gas.Therefore, preferably in deodorizer, deodorizer carrier or deodorant compositions, add the silicic acid attaclay among the present invention.Particularly, by adding the silicic acid attaclay, improved the deodoriging properties of pyridine to one of Nicotiana tabacum L. foul smell main constituent, nicotine etc.
As the concrete example of silicic acid attaclay used in the present invention, can enumerate meerschaum, silotile, raphrynite and attapulgite etc.
Relative 100 mass parts deodorizer of the present invention preferably mixes 0.2～20 mass parts silicic acid attaclay, further preferred 0.5～10 mass parts of mixing.When the silicic acid attaclay is less than 0.2 mass parts, can't expect to improve deodoriging properties sometimes, even and if mix more than 20 mass parts, also can't improve deodoriging properties sometimes or cause deodoriging properties to other foul gas to become sometimes and worsen.Combined amount to the silicic acid attaclay of deodorizer carrier and deodorant compositions is identical with above-mentioned record.
Above-mentioned deodorizer of the present invention, deodorizer carrier or deodorant compositions all obtain with Powdered usually, and preferred mean diameter is 0.01～50 μ m, more preferably 0.02～20 μ m.During mean diameter less than 0.01 μ m, there are difficult treatment, such problem that reassociates easily, therefore not preferred.In addition, during greater than 50 μ m, there are the following problems: it is scattered in the surface conditioning agents such as binding agent and is difficult to homodisperse in surface conditioning agent when carrying out post-treatment in fiber etc., when adding molding resin to, cause the plugged filter of make-up machine or cause disperse bad etc., not preferred.
In addition, can be according to application target, with deodorizer of the present invention, deodorizer carrier or deodorant compositions pelletize.At this moment, the per a kind of composition of deodorizer can be distinguished pelletize, perhaps can be with the deodorant compositions pelletize.The manufacture method of shot-like particle can be used common any means with the powder pelletize.The method of using alumina sol, clay etc. to make shot-like particle as binding agent is for example arranged.Particle diameter can be adjusted into various according to the hardness of shot-like particle, density, crush strength etc., and from the easy degree of handling, particle diameter is preferably 0.1～3mm.
The invention provides a kind of deodorant compositions, it is mixed with: gaseous aldehyde deodorizer, it contains the above material of at least one that is selected from the group that mono amino guanidinesalt, diaminourea guanidinesalt and triamido guanidinesalt formed, and/or gaseous aldehyde deodorizer, its load is by the above material of at least one that is selected from the group that mono amino guanidinesalt, diaminourea guanidinesalt and triamido guanidinesalt formed; And be selected from down the group in the above material of at least one: the tetravalent metal phosphate chemical compound, zinc silicate, load has the tetravalent metal phosphate chemical compound of the above metal ion of at least one that is selected from copper, zinc and the manganese, hydrous zirconium oxide(HZO), hydrous titanium oxide, zinc oxide, brucite and brucite sinter etc.The mixed proportion of these materials is not particularly limited, and can change according to the fitness of environment that uses deodorant compositions.
Zero resistance to water
Deodorizer of the present invention has the high advantage of resistance to water.So-called resistance to water is meant that with deodorizer with after water contacts at least 1 time, the reduction of deodoriging properties is few.For example, its benchmark is: deodorizer in water after the impregnation process 1 time, when measuring the deodoriging properties to acetaldehyde, is compared with the deodorization before the impregnation process, and reduction rate is below 50%.Further specify experimental condition, at room temperature 1g deodorizer is added in the 100ml Purified Water and fully stirs and obtain suspension,, and then, under 110 ℃, be dried with the cleaning of 1000ml Purified Water with suspension filtered.To this deodorant activities of having carried out deodorizer mensuration aldehydes gas of washing, can confirm resistance to water thus.
Zero purposes
Deodorizer of the present invention and deodorizer carrier have deodorizing effect to gaseous aldehydes such as acetaldehyde, formaldehyde, nonenyl aldehydes.In addition, with the deodorant compositions that deodorizer of the present invention and/or deodorizer carrier and other deodorizer mix, except that deodorization, also excellent to various malodorous deodorizing effects such as ammonia, hydrogen sulfide, methanthiol to gaseous aldehyde.Therefore, deodorizer of the present invention or deodorant compositions are in the various fields of using existing deodorizer such as active carbon, and fields such as for example Nicotiana tabacum L. foul smell deodorization, the deodorization of life foul smell, body odor deodorization, the deodorization of fecaluria foul smell, refuse odor deodorization are effective.
In addition, deodorizer of the present invention and/or deodorizer carrier, by using it for material that base material self produces aldehyde, for example laminate, plywood, flooring material, flakeboard, heat-barrier material, carpet, silencing pad, vibration-absorptive material, seat, head rest, arm rest, vehicle door interior trim panel, molding roof, sky shade, Rear Parcel Shelf, instrumental panel, dash insulator etc., can reduce from the evaporable aldehyde of base material self.And then deodorant compositions also can be used for these purposes.
Deodorizer of the present invention, deodorizer carrier or deodorant compositions can use powder, granule or granulous material as the deodorization goods.For example powder, granule or the shot-like particle of deodorizer, deodorizer carrier or deodorant compositions can be filled in and make the deodorization goods in the tube.In addition, can also make the deodorizer of spray form, its used deodorizer of the present invention aqueous solution, be dispersed with the liquid of deodorizer powder, deodorizer support powder or deodorant compositions powder.In addition, also can in various goods, contain or be coated with interpolation deodorizer of the present invention, deodorizer carrier or deodorant compositions and make various deodorization processed goods.
The deodorization goods that contain deodorizer of the present invention, deodorizer carrier or deodorant compositions can example illustrate deodorization fiber, deodorization coating, deodorization sheet material and deodorization synthetic resin etc.
The deodorization fiber that contains deodorizer of the present invention, deodorizer carrier or deodorant compositions can use in needing the various fields of deodorization.For example, this deodorization fiber can be used for the multiple fibre headed by clothes, underwear, stocking, socks, quilt, quilt cover, mat, woollen blanket, carpet, curtain, sofa, cover, coverlet, seat, the air filter.In addition, contain the odour remover coating of deodorizer of the present invention, deodorizer carrier or deodorant compositions, can in needing the various fields of deodorization, use.For example, this odour remover coating can be used for inwall, the outer wall of building, inwall of rail truck etc.In addition, contain the deodorization sheet material of deodorizer of the present invention, deodorizer carrier or deodorant compositions, can in needing the various fields of deodorization, use.For example, this deodorization sheet material can be used for medical wrapping paper, food wrapping paper, tin foil, dress material made of paper, air cleanness filter, wallpaper, tissue paper, toilet paper, non-woven fabrics, paper, filter, thin film etc.In addition, contain the deodorization molding product of deodorizer of the present invention, deodorizer carrier or deodorant compositions, can in needing the various fields of deodorization, use.For example, these deodorization molding product can be used for household appliances such as air cleaner, refrigerator; Common household articles such as refuse bin, water control device; Various nursing materialss such as Porta Potti; Articles for daily use etc.
＜embodiment 〉
Below, the present invention is further specified, but be not limited thereto.In addition, % is quality %.
The various evaluation test methods and the result thereof of the sample modulator approach of deodorizer, deodorizer carrier and deodorant compositions and gained sample are as follows.
Zero aluminium silicate
SiO when the employed aluminium silicate of embodiment is synthetic
2: Al
2O
3Mol ratio be 9: 1 material.
Embodiment 1
Stir 100 mass parts aluminium silicate, at room temperature to the aminoguanidine monohydrochloride aqueous solution that wherein adds 25 mass parts 20%.After the adding, be stirred to evenly.Then, 100 ℃ dry 30 minutes down, 180 ℃ of following heat treated 30 minutes, obtain deodorizer A then.
Embodiment 2
Stir 100 mass parts aluminium silicate, at room temperature to the aminoguanidine sulfate aqueous solution that wherein adds 25 mass parts 20%.After the adding, be stirred to evenly.Then, 100 ℃ dry 30 minutes down, 210 ℃ of following heat treated 30 minutes, obtain deodorizer B then.
Embodiment 3
Stir 100 mass parts aluminium silicate, at room temperature to the diaminoguanidine hydrochlorate aqueous solution that wherein adds 25 mass parts 20%.After the adding, be stirred to evenly.Then, 100 ℃ dry 30 minutes down, 180 ℃ of following heat treated 30 minutes, obtain deodorizer C then.
Embodiment 4
Stir 100 mass parts aluminium silicate, at room temperature to the triaminoguanidine hydrochlorate aqueous solution that wherein adds 25 mass parts 20%.After the adding, be stirred to evenly.Then, 100 ℃ dry 30 minutes down, 180 ℃ of following heat treated 30 minutes, obtain deodorizer D then.
Embodiment 5
Replace aluminium silicate and use the α zirconium phosphate, in addition, operation obtains deodorizer E similarly to Example 1.
Embodiment 6
Replace aluminium silicate and use the α zirconium phosphate, in addition, operation obtains deodorizer F similarly to Example 2.
Embodiment 7
Replace aluminium silicate and use the α zirconium phosphate, in addition, operation obtains deodorizer G similarly to Example 3.
Embodiment 8
Replace aluminium silicate and use the α zirconium phosphate, in addition, operation obtains deodorizer H similarly to Example 4.
Embodiment 9
Replace aluminium silicate and use zeolite ZSM5 (marshy land chemical industry (strain) MIZUKA SIEVES Si/Al=30), in addition, operation obtains deodorizer I similarly to Example 1.
Embodiment 10
Replace aluminium silicate and use zeolite ZSM5 (marshy land chemical industry (strain) MIZUKA SIEVES Si/Al=30), in addition, operation obtains deodorizer J similarly to Example 2.
Embodiment 11
Replace aluminium silicate and use zeolite ZSM5 (marshy land chemical industry (strain) MIZUKASIEVES Si/Al=30), in addition, operation obtains deodorizer K similarly to Example 3.
Embodiment 12
Replace aluminium silicate and use zeolite ZSM5 (marshy land chemical industry (strain) MIZUKASIEVES Si/Al=30), in addition, operation obtains deodorizer L similarly to Example 4.
Embodiment 13
Zero adopts the manufacturing of the deodorizer A1 of dry type load
At room temperature mix 100 mass parts aluminium silicate and 25 mass parts aminoguanidine monohydrochloride, 180 ℃ of following heat treated 30 minutes, obtain deodorizer A1 then.
Embodiment 14
Zero adopts the manufacturing of the deodorizer B1 of dry type load
At room temperature mix 100 mass parts aluminium silicate and 25 mass parts aminoguanidine sulfates, 210 ℃ of following heat treated 30 minutes, obtain deodorizer B1 then.
Embodiment 15
Zero adopts the manufacturing of the deodorizer C1 of dry type load
At room temperature mix 100 mass parts aluminium silicate and 25 mass parts diaminoguanidine hydrochlorates, 180 ℃ of following heat treated 30 minutes, obtain deodorizer C1 then.
Embodiment 16
Zero adopts the manufacturing of the deodorizer D1 of dry type load
At room temperature mix 100 mass parts aluminium silicate and 25 mass parts triaminoguanidine hydrochlorates, 180 ℃ of following heat treated 30 minutes, obtain deodorizer D1 then.
Embodiment 17
Zero adopts the manufacturing of the deodorizer E1 of dry type load
Replace aluminium silicate and use the α zirconium phosphate, in addition, operation obtains deodorizer E1 similarly to Example 13.
Embodiment 18
Zero adopts the manufacturing of the deodorizer F1 of dry type load
Replace aluminium silicate and use the α zirconium phosphate, in addition, operation obtains deodorizer F1 similarly to Example 14.
Embodiment 19
Zero adopts the manufacturing of the deodorizer G1 of dry type load
Replace aluminium silicate and use the α zirconium phosphate, in addition, operation obtains deodorizer G1 similarly to Example 15.
Embodiment 20
Zero adopts the manufacturing of the deodorizer H1 of dry type load
Replace aluminium silicate and use the α zirconium phosphate, in addition, operation obtains deodorizer H1 similarly to Example 16.
Embodiment 21
Zero adopts the manufacturing of the deodorizer I1 of dry type load
Replace aluminium silicate and use zeolite ZSM5 (marshy land chemical industry (strain) MIZUKASIEVES Si/Al=30), in addition, operation obtains deodorizer I1 similarly to Example 13.
Embodiment 22
Zero adopts the manufacturing of the deodorizer J1 of dry type load
Replace aluminium silicate and use zeolite ZSM5 (marshy land chemical industry (strain) MIZUKASIEVES Si/Al=30), in addition, operation obtains deodorizer J1 similarly to Example 14.
Embodiment 23
Zero adopts the manufacturing of the deodorizer K1 of dry type load
Replace aluminium silicate and use zeolite ZSM5 (marshy land chemical industry (strain) MIZUKASIEVES Si/Al=30), in addition, operation obtains deodorizer K1 similarly to Example 15.
Embodiment 24
Zero adopts the manufacturing of the deodorizer L1 of dry type load
Replace aluminium silicate and use zeolite ZSM5 (marshy land chemical industry (strain) MIZUKASIEVES Si/Al=30), in addition, operation obtains deodorizer L1 similarly to Example 16.
Embodiment 25
70 mass parts deodorizer A, 10 mass parts α type bedded zirconium phosphates, 10 mass parts copper bonding type α type bedded zirconium phosphate and the 10 mass parts hydrous zirconium oxide(HZO)s made in the at room temperature abundant mix embodiment 1 are made deodorant compositions A.
Embodiment 26
Replace deodorizer A and use the deodorizer B that makes among the embodiment 2, deodorant compositions B is made in operation similarly to Example 25.
Embodiment 27
Replace deodorizer A and use the deodorizer C that makes among the embodiment 3, deodorant compositions C is made in operation similarly to Example 25.
Embodiment 28
Replace deodorizer A and use the deodorizer D that makes among the embodiment 4, deodorant compositions D is made in operation similarly to Example 25.
Embodiment 29
Replace aluminium silicate and use silica gel (Fuji Silysia Chemical Ltd., the SYLYSIA740 of manufacturing), in addition, operation obtains deodorizer M similarly to Example 1.
Embodiment 30
Replace aluminium silicate and use silica gel (Fuji Silysia Chemical Ltd., the SYLYSIA740 of manufacturing), in addition, operation obtains deodorizer N similarly to Example 2.
＜comparative example 1 〉
Replace aluminium silicate and use calcium silicates CSH (Calx industry (strain) manufacturing is closed in the river), in addition, sample a is made in operation similarly to Example 1.
＜comparative example 2 〉
Replace using aluminium silicate and use calcium silicates CSH (Calx industry (strain) manufacturing is closed in the river), in addition, operate similarly to Example 2 and make sample b.
＜comparative example 3 〉
Replace using aluminium silicate and use calcium silicates CSH (Calx industry (strain) manufacturing is closed in the river), in addition, operate similarly to Example 3 and make sample c.
＜comparative example 4 〉
Replace using aluminium silicate and use calcium silicates CSH (Calx industry (strain) manufacturing is closed in the river), in addition, operate similarly to Example 4 and make sample d.
＜comparative example 5 〉
Behind mixed at room temperature aluminium silicate and the aminoguanidine monohydrochloride, the material that does not carry out heat treated is as sample e in embodiment 13.
＜comparative example 6 〉
Behind mixed at room temperature aluminium silicate and the aminoguanidine sulfate, the material that does not carry out heat treated is as sample f in embodiment 14.
＜comparative example 7 〉
Behind mixed at room temperature aluminium silicate and the diaminoguanidine hydrochlorate, the material that does not carry out heat treated is as sample g in embodiment 15.
＜comparative example 8 〉
Behind mixed at room temperature aluminium silicate and the triaminoguanidine hydrochlorate, the material that does not carry out heat treated is as sample h in embodiment 16.
＜comparative example 9 〉
Behind mixed at room temperature α zirconium phosphate and the aminoguanidine monohydrochloride, the material that does not carry out heat treated is as sample i in embodiment 17.
＜comparative example 10 〉
Behind mixed at room temperature α zirconium phosphate and the aminoguanidine sulfate, the material that does not carry out heat treated is as sample j in embodiment 18.
＜comparative example 11 〉
Behind mixed at room temperature α zirconium phosphate and the diaminoguanidine hydrochlorate, the material that does not carry out heat treated is as sample k in embodiment 19.
＜comparative example 12 〉
Behind mixed at room temperature α zirconium phosphate and the triaminoguanidine hydrochlorate, the material that does not carry out heat treated is as sample 1 in embodiment 20.
＜comparative example 13 〉
Behind mixed at room temperature zeolite ZSM5 and the aminoguanidine monohydrochloride, the material that does not carry out heat treated is as sample m in embodiment 21.
＜comparative example 14 〉
Behind mixed at room temperature zeolite ZSM5 and the aminoguanidine monohydrochloride, the material that does not carry out heat treated is as sample n in embodiment 22.
＜comparative example 15 〉
Behind mixed at room temperature zeolite ZSM5 and the diaminoguanidine hydrochlorate, the material that does not carry out heat treated formation is as sample o in embodiment 23.
＜comparative example 16 〉
Behind mixed at room temperature zeolite ZSM5 and the triaminoguanidine hydrochlorate, the material that does not carry out heat treated is as sample p in embodiment 24.
＜comparative example 17 〉
Replace 20% aqueous solution of aminoguanidine monohydrochloride and use 20% aqueous solution of 50 mass parts guanidinesalt hydrochlorates, in addition, sample q is made in operation similarly to Example 1.
＜comparative example 18 〉
At room temperature fully mix 70 mass parts sample a, 10 mass parts α type bedded zirconium phosphates, 10 mass parts copper bonding type α type bedded zirconium phosphate and the 10 mass parts hydrous zirconium oxide(HZO)s made in the comparative example 1, make sample composition a.
＜comparative example 19 〉
Replace sample a and use the sample e of comparative example 5 manufacturings, operate manufacturing sample composition e with comparative example 18 equally.
＜comparative example 20 〉
Replace sample a and use the sample q of comparative example 17 manufacturings, operate manufacturing sample composition q with comparative example 18 equally.
Embodiment 31
The Water Resistance Test of zero deodorizer
After the deodorizer A～L of embodiment 1～12 manufacturing cleaned with Purified Water respectively, measure deodorant activities to aldehydes gas.That is, in the 100ml Purified Water, add 1g deodorizer A and abundant the stirring 1 minute under the room temperature.After this suspension filtered, reuse 1000ml Purified Water cleans, and is dry down at 110 ℃.This has been carried out the deodorant activities of deodorizer A mensuration of washing to aldehydes gas.Equally, other deodorizer is also carried out this washing handle, and the deodorizer after the washing is measured deodorant activities.In addition, the sample to comparative example 1～4 and comparative example 17 manufacturings also carries out same washing processing and measures deodorant activities.
The mensuration of zero deodorizing effect
Being determined as of deodorizing effect: each 0.02g sample that will carry out Water Resistance Test, putting into the ethylene fluoride bag respectively (uses ethylene fluoride made membrane processing pouch, hereinafter referred to as Tedlar gas sampling bag), to wherein injecting the air that 1L contains the 100ppm aldehydes gas, at room temperature placed 2 hours.After 2 hours, measure the aldehydes gas concentration that residues in the Tedlar gas sampling bag with gas detecting tube ((strain) GASTEC company makes, and below uses with company's goods).Its measurement result is shown in table 1 (ppm).In addition, reagent aminoguanidine monohydrochloride, aminoguanidine sulfate, diaminoguanidine hydrochlorate or each 1mg of triaminoguanidine hydrochlorate are directly added the result that this appraisement system is measured deodorant activities, this moment, the concentration of acetaldehyde was respectively 22ppm, 24ppm, 10ppm and 8ppm.
Table 1
| Before washing is handled | After washing is handled | |
| Deodorizer A | ＜0.2 | 10 |
| Deodorizer B | ＜0.2 | 10 |
| Deodorizer C | ＜0.2 | 2 |
| Deodorizer D | ＜0.2 | 3 |
| Deodorizer E | ＜0.2 | 14 |
| Deodorizer F | ＜0.2 | 12 |
| Deodorizer G | ＜0.2 | 4 |
| Deodorizer H | ＜0.2 | 4 |
| Deodorizer I | ＜0.2 | 32 |
| Deodorizer J | ＜0.2 | 30 |
| Deodorizer K | ＜0.2 | 14 |
| Deodorizer L | ＜0.2 | 10 |
| Sample a | ＜0.2 | 85 |
| Sample b | ＜0.2 | 80 |
| Sample c | ＜0.2 | 72 |
| Sample d | ＜0.2 | 72 |
| Sample q | 88 | 95 |
As can be known from the results of Table 1, compare with the sample q that aminoguanidinium salts is carried on the sample a～d on the calcium silicates and the guanidinesalt hydrochlorate is carried on the aluminium silicate, aminoguanidinium salts is carried on the deodorizer carrier resistance to water excellence of the present invention on the carriers such as aluminium silicate, α zirconium phosphate or zeolite.
Its reason is, even if deodorizer carrier of the present invention is washed processing, and the also less reduction of deodorant activities, and odor removal efficient excellence.The excellent in te pins of durability that shows deodorizer carrier of the present invention thus.
Embodiment 32
The performance evaluation of the deodorizer of zero dry type load
0.1g deodorizer A1 is put into Tedlar gas sampling bag, to wherein injecting the air that 1L contains 600ppm acetaldehyde.At room temperature placed 2 hours, and measured the concentration that residues in the acetaldehyde in the Tedlar gas sampling bag with gas detecting tube then.It the results are shown in table 2.In addition, deodorizer B1～L1, sample e～p are also carried out same mensuration, it the results are shown in table 2 (ppm).
Table 2
| Before washing is handled | After washing is handled | |
| Deodorizer A1 | ＜0.1 | 55 |
| Deodorizer B1 | ＜0.1 | 60 |
| Deodorizer C1 | ＜0.1 | 35 |
| Deodorizer D1 | ＜0.1 | 35 |
| Deodorizer E1 | ＜0.1 | 60 |
| Deodorizer F1 | ＜0.1 | 60 |
| Deodorizer G1 | ＜0.1 | 40 |
| Deodorizer H1 | ＜0.1 | 38 |
| Deodorizer I1 | ＜0.1 | 110 |
| Deodorizer J1 | ＜0.1 | 120 |
| Deodorizer K1 | ＜0.1 | 82 |
| Deodorizer L1 | ＜0.1 | 80 |
| Sample e | ＜0.1 | 325 |
| Sample f | ＜0.1 | 325 |
| Sample g | ＜0.1 | 220 |
| Sample h | ＜0.1 | 220 |
| Sample i | ＜0.1 | 325 |
| Sample j | ＜0.1 | 350 |
| Sample k | ＜0.1 | 280 |
| Sample l | ＜0.1 | 260 |
| Sample m | ＜0.1 | 425 |
| Sample n | ＜0.1 | 475 |
| Sample o | ＜0.1 | 370 |
| Sample p | ＜0.1 | 350 |
As can be known from the results of Table 2, by with aminoguanidinium salts and carrier mixing post-heating, even if wash processing, the also less reduction of its deodorant activities, and odor removal efficient excellence.In addition, for the sample e～p that does not carry out heat treated, although with the amount of washing the identical molal quantity of deodorizer A1～L1 before handling it is dropped into the deodorization appraisement system, deodorizer carrier of the present invention demonstrates more excellent deodorant activities.
This expression: deodorizer carrier of the present invention, even if it washes processing, the also less reduction of deodorant activities, and odor removal efficient excellence.Show deodorizer carrier excellent in te pins of durability of the present invention thus.
Embodiment 33
The Water Resistance Test of zero deodorant compositions
In the 100ml Purified Water, add 1g deodorant compositions A under the room temperature, fully stirred 1 minute.After filtering this suspension, reuse 1000ml Purified Water cleans, and is dry down at 110 ℃.This has been carried out the deodorant activities of deodorant compositions A mensuration of washing to aldehydes gas, ammonia, hydrogen sulfide gas and acetic gas.Equally, for deodorant compositions B～D, also measure the deodorant activities carried out after should washing processing.In addition, sample composition a, e, the q that makes in the comparative example 18～20 also carried out same washing and handle and measure deodorant activities.
The mensuration of zero deodorizing effect
Being determined as of deodorizing effect, to carry out each 0.02g sample of above-mentioned Water Resistance Test and put into Tedlar gas sampling bag respectively, to wherein injecting the air that 1L contains 20ppm aldehydes gas, 40ppm ammonia, 10ppm hydrogen sulfide gas and 40ppm acetic gas, at room temperature placed 2 hours.After 2 hours, measure residual gas concentration in the Tedlar gas sampling bag respectively with corresponding gas detecting tube.It the results are shown in table 3 (ppm).
Table 3
| Ammonia | Acetaldehyde | Hydrogen sulfide | Acetic acid | |
| Deodorant compositions A | ＜0.2 | ＜0.2 | 6 | 2 |
| Deodorant compositions B | ＜0.2 | ＜0.2 | 6 | 2 |
| Deodorant compositions C | ＜0.2 | ＜0.2 | 6 | 2 |
| Deodorant compositions D | ＜0.2 | ＜0.2 | 6 | 2 |
| Sample composition a | ＜0.2 | 14 | 8 | 2 |
| Sample composition e | ＜0.2 | 5 | 8 | 2 |
| Sample composition q | ＜0.2 | 19 | 6 | 2 |
The deodorant compositions of the present invention that deodorizer of the present invention and other stench deodorizer are mixed as can be known, its reduction to the deodoriging properties of acetaldehyde is compared little with comparative example.
Embodiment 34
The manufacturing of zero deodorization fiber A1
100 mass parts Purified Waters are added 3 mass parts deodorizer A, the 3 mass parts acrylic adhesives of making among the embodiment 1 (KB-1300, East Asia synthetic (strain) makes), make suspension.100 mass parts polyester fibers are coated with this suspension of 50 mass parts, obtain deodorization fiber A1 (content of the deodorizer that relative 100 mass parts resins are contained is 1.5 parts) 150 ℃ of following dryings.
Embodiment 35
The manufacturing of zero deodorization fiber A2
100 mass parts Purified Waters are added 3 mass parts deodorant compositions A, the 3 mass parts acrylic adhesives of making among the embodiment 25 (KB-1300, East Asia synthetic (strain) makes), make suspension.100 mass parts polyester fibers are coated with this suspension of 50 mass parts, obtain deodorization fiber A2 (content of the deodorizer that relative 100 mass parts fibers are contained is 1.5 mass parts) 150 ℃ of following dryings.
Embodiment 36
The manufacturing of zero deodorization fiber A3
100 mass parts Purified Waters are dissolved 1 mass parts aminoguanidine monohydrochloride obtain aqueous solution, 100 mass parts polyester fibers are coated with this aqueous solution of 50 mass parts, obtain deodorization fiber A3 (content of the aminoguanidine monohydrochloride that relative 100 mass parts fibers are contained is 0.5 mass parts) 150 ℃ of following dryings.
Embodiment 37
The manufacturing of zero deodorization fiber A4
Replace aminoguanidine monohydrochloride and use the diaminoguanidine hydrochlorate, obtain deodorization fiber A4 (content that relative 100 mass parts fibers contain the diaminoguanidine hydrochlorate is 0.5 mass parts) with embodiment 36 same operations.
Embodiment 38
The manufacturing of zero deodorization fiber A5
Replace aminoguanidine monohydrochloride and use the triaminoguanidine hydrochlorate, obtain deodorization fiber A5 (content of the triaminoguanidine hydrochlorate that relative 100 mass parts fibers are contained is 0.5 mass parts) with embodiment 36 same operations.
＜comparative example 21 〉
The manufacturing of fiber q1 of zero comparative example
100 mass parts Purified Waters are added 3 mass parts sample q, the 3 mass parts acrylic adhesives of making in the comparative example 17 (KB-1300, East Asia synthetic (strain) makes), make suspension.100 mass parts polyester fibers are coated with this suspension of 50 mass parts, obtain comparative example with fiber q1 (content of the deodorizer that relative 100 mass parts fibers are contained is 1.5 parts) 150 ℃ of following dryings.
＜comparative example 22 〉
The manufacturing of fiber q2 of zero comparative example
100 mass parts Purified Waters are added 3 mass parts sample q, the 3 mass parts acrylic adhesives of making in the comparative example 20 (KB-1300, East Asia synthetic (strain) makes), make suspension.100 mass parts polyester fibers are coated with this suspension of 50 mass parts, obtain comparative example with fiber q2 (content of the deodorizer that relative 100 mass parts fibers are contained is 1.5 parts) 150 ℃ of following dryings.
Embodiment 39
The mensuration of the deodorizing effect of zero pair of deodorization fiber
Deodorization fiber A1～A5, comparative example are put into Tedlar gas sampling bag respectively with fiber q1 and each 10g of q2, inject 1 liter of foul gas (containing 20ppm aldehydes gas, 40ppm ammonia, 10ppm hydrogen sulfide gas and 40ppm acetic gas), measure the residual gas concentration in the Tedlar gas sampling bag after 2 hours.
It the results are shown in table 4 (ppm).In addition, the ND in the table represents to estimate.Below same.
Table 4
| Ammonia | Acetaldehyde | Hydrogen sulfide | Acetic acid | |
| Deodorization fiber A1 | ND | 4 | ND | ND |
| Deodorization fiber A2 | ＜0.2 | 6 | 3 | ＜1 |
| Deodorization fiber A3 | ND | 4 | ND | ND |
| Deodorization fiber A4 | ND | 4 | ND | ND |
| Deodorization fiber A5 | ND | 4 | ND | ND |
| Comparative example fiber q1 | ND | 18 | ND | ND |
| Comparative example fiber q2 | ND | 4 | ND | ND |
Embodiment 40
The manufacturing of zero deodorization steel plate A1
100 mass parts dimethylbenzene are mixed the deodorizer A that makes among 70 mass parts acrylic resins (J-500 SCJohnson Polymer company (strain) manufacturing), 3 mass parts dispersants (BYK-110BYK Chemie (strain) manufacturing), 2 mass parts thickening agents (manufacturing of Bentone SD2Wilbur-Ellis company), the 200 mass parts embodiment 1, obtain paste composition with the abundant mixing dispersion of the mixer of three rollers.With dimethylbenzene it is diluted to 10 times, with coating of 100 μ m thickness and air-dry 1 evening, makes deodorization steel plate A1 on the two sides of the galvanized steel plain sheet of 70 * 150mm.
Embodiment 41
The manufacturing of zero deodorization steel plate A2
Replace deodorizer A and use deodorant compositions A, in addition, operate equally, make deodorization steel plate A2 with embodiment 40.
Embodiment 42
The manufacturing of zero deodorization steel plate A3
Replace deodorizer A and use 20 mass parts aminoguanidine monohydrochloride, in addition, operate equally, make deodorization steel plate A3 with embodiment 40.
Embodiment 43
The manufacturing of zero deodorization steel plate A4
Replace deodorizer A and use 20 mass parts diaminoguanidine hydrochlorates, in addition, operate equally, make deodorization steel plate A3 with embodiment 40.
Embodiment 44
The manufacturing of zero deodorization steel plate A4
Replace deodorizer A and use 20 mass parts triaminoguanidine hydrochlorates, in addition, operate equally, make deodorization steel plate A4 with embodiment 40.
＜comparative example 23 〉
Zero relatively uses the manufacturing of steel plate q1
Replace deodorizer A and use sample q, in addition, operate equally, make and relatively use steel plate q1 with embodiment 40.
＜comparative example 24 〉
Zero relatively uses the manufacturing of steel plate q2
Replace deodorizer A and use sample composition q, in addition, operate equally, make and relatively use steel plate q2 with embodiment 40.
Embodiment 45
The mensuration of the deodorizing effect of zero pair of deodorization steel plate
With deodorization steel plate A1～A5, relatively with steel plate q1 and relatively with steel plate q2 each 1 put into Tedlar gas sampling bag respectively, inject 1 liter of foul gas (containing 20ppm aldehydes gas, 40ppm ammonia, 10ppm hydrogen sulfide gas and 40ppm acetic gas), measure the residual gas concentration in the gas sampling bag after 2 hours.It the results are shown in table 5 (ppm).The ND of table 5 is identical with table 4.
Table 5
| Ammonia | Acetaldehyde | Hydrogen sulfide | Acetic acid | |
| Deodorization steel plate A1 | ND | 8 | ND | ND |
| Deodorization steel plate A2 | 2 | 10 | 6 | 2 |
| Deodorization steel plate A3 | ND | 7 | ND | ND |
| Deodorization steel plate A4 | ND | 6 | ND | ND |
| Deodorization steel plate A5 | ND | 6 | ND | ND |
| Comparative example steel plate q1 | ND | 19 | ND | ND |
| Comparative example steel plate q2 | 12 | 20 | 8 | 5 |
Embodiment 46
The manufacturing of zero deodorization polyurethane A
Manufacturing contains the aqueous dispersion of 4.0% deodorizer A and 4.4% urethane adhesive KB-3000 (East Asia synthetic (strain) makes resinous principle 30%).Then, this aqueous dispersion is coated polyurethane system vibration-absorptive material and the drying that automobile inside is used, make deodorization polyurethane A.At every 1m
2Be added with 6g deodorizer A, 2g binding agent KB-3000 (in resinous principle) among this deodorization polyurethane A.
Embodiment 47
The manufacturing of zero deodorization polyurethane B～N
Replace deodorizer A and use deodorizer B～N respectively, in addition, operate equally, make deodorization polyurethane B～N with embodiment 46.
Embodiment 48
The manufacturing of zero deodorization polyurethane O
Replace deodorizer A and use aminoguanidine monohydrochloride, in addition, operate equally, make deodorization polyurethane O with embodiment 46.
Embodiment 49
The manufacturing of zero deodorization polyurethane P
Replace deodorizer A and use aminoguanidine sulfate, in addition, operate equally, make deodorization polyurethane P with embodiment 46.
＜comparative example 25 〉
Zero relatively uses the manufacturing of polyurethane
Replace deodorizer A and use sample a～d, q respectively, in addition, operate equally, make and relatively use polyurethane a～d, q with embodiment 46.
In addition, except that not using deodorizer A, relatively use polyurethane r with embodiment 46 same operation manufacturings.
Embodiment 50
The mensuration of the deodorizing effect of zero pair of deodorization polyurethane
A cuts out 10cm * 10cm with deodorization polyurethane, puts it into Tedlar gas sampling bag, injects 500mL nitrogen, places 2 hours down at 65 ℃.Measure concentration of formaldehyde and the acetaldehyde concentration in the Tedlar gas sampling bag after 2 hours.It the results are shown in table 6 (ppm).
To deodorization polyurethane B～P and relatively operate too, measure concentration of formaldehyde and acetaldehyde concentration with polyurethane a～d, q, r.It the results are shown in table 6 (ppm).
Table 6
| Formaldehyde | Acetaldehyde | |
| Deodorization polyurethane A | ＜0.1 | 0.3 |
| Deodorization polyurethane B | ＜0.1 | 0.3 |
| Deodorization polyurethane C | ＜0.1 | 0.2 |
| Deodorization polyurethane D | ＜0.1 | 0.2 |
| Deodorization polyurethane E | ＜0.1 | 0.4 |
| Deodorization polyurethane F | ＜0.1 | 0.4 |
| Deodorization polyurethane G | ＜0.1 | 0.3 |
| Deodorization polyurethane H | ＜0.1 | 0.3 |
| Deodorization polyurethane I | ＜0.1 | 0.4 |
| Deodorization polyurethane J | ＜0.1 | 0.4 |
| Deodorization polyurethane K | ＜0.1 | 0.4 |
| Deodorization polyurethane L | ＜0.1 | 0.4 |
| Deodorization polyurethane M | ＜0.1 | 0.2 |
| Deodorization polyurethane N | ＜0.1 | 0.2 |
| Deodorization polyurethane O | ＜0.1 | 1.2 |
| Deodorization polyurethane P | ＜0.1 | 1.2 |
| Relatively use polyurethane a | 0.2 | 2.2 |
| Relatively use polyurethane b | 0.2 | 2.2 |
| Relatively use polyurethane c | 0.2 | 1.9 |
| Relatively use polyurethane d | 0.2 | 1.9 |
| Relatively use polyurethane q | 1.4 | 2.6 |
| Relatively use polyurethane r | 2.0 | 2.9 |
Deodorizer of the present invention and deodorizer carrier can suppress to generate aldehyde gas from the polyurethane in automobile inside material etc.
Embodiment 51
The manufacturing of zero deodorization flakeboard A
Manufacturing contains the aqueous dispersion of 4.0% deodorizer A and 3.3% urethane adhesive KB-3000 (East Asia synthetic (strain) makes resinous principle 30%).Then, this aqueous dispersion is coated flakeboard and dry, make deodorization flakeboard A.Every 1m
2Be added with 2g deodorizer, 0.5g binding agent KB-3000 (in resinous principle) among this deodorization flakeboard A.
Embodiment 52
The manufacturing of zero deodorization flakeboard B～N
Replace deodorizer A and use deodorizer B～N respectively, in addition, operate equally, make deodorization flakeboard B～N with embodiment 51.
Embodiment 53
The manufacturing of zero deodorization flakeboard O
Replace deodorizer A and use aminoguanidine monohydrochloride, in addition, operate equally, make deodorization flakeboard O with embodiment 51.
Embodiment 54
The manufacturing of zero deodorization flakeboard P
Replace deodorizer A and use aminoguanidine sulfate, in addition, operate equally, make deodorization flakeboard P with embodiment 51.
＜comparative example 26 〉
Zero relatively uses the manufacturing of flakeboard
Replace deodorizer A and use sample a～d, q respectively, in addition, operate equally, make and relatively use flakeboard a～d, q with embodiment 51.
In addition, except that not using deodorizer A, relatively use flakeboard r with embodiment 51 same operation manufacturings.
Embodiment 55
The mensuration of the deodorizing effect of zero pair of deodorization flakeboard
A cuts out 15cm * 30cm with the deodorization flakeboard, puts into the box (internal volume 40L) of acroleic acid resin system with the beaker of having put into the 20ml pure water, places 24 hours down at 20 ℃.Afterwards, with the concentration of formaldehyde in the acetylacetone method mensuration pure water.It the results are shown in table 7 (mg/L).
To deodorization flakeboard B～P and relatively operate too, measure the concentration of formaldehyde in the pure water with flakeboard a～d, q, r.It the results are shown in table 7 (mg/L).
Table 7
| Formaldehyde | |
| Deodorization flakeboard A | ＜0.1 |
| Deodorization flakeboard B | ＜0.1 |
| Deodorization flakeboard C | ＜0.1 |
| Deodorization flakeboard D | ＜0.1 |
| Deodorization flakeboard E | ＜0.1 |
| Deodorization flakeboard F | ＜0.1 |
| Deodorization flakeboard G | ＜0.1 |
| Deodorization flakeboard H | ＜0.1 |
| Deodorization flakeboard I | ＜0.1 |
| Deodorization flakeboard J | ＜0.1 |
| Deodorization flakeboard K | ＜0.1 |
| Deodorization flakeboard L | ＜0.1 |
| Deodorization flakeboard M | ＜0.1 |
| Deodorization flakeboard N | ＜0.1 |
| Deodorization flakeboard O | ＜0.1 |
| Deodorization flakeboard P | ＜0.1 |
| Relatively use flakeboard a | 0.2 |
| Relatively use flakeboard b | 0.2 |
| Relatively use flakeboard c | 0.2 |
| Relatively use flakeboard d | 0.2 |
| Relatively use flakeboard q | 1.0 |
| Relatively use flakeboard r | 1.7 |
Deodorizer of the present invention and deodorizer carrier can suppress to generate aldehyde gas from the flakeboard that is used for automobile inside material etc.
Industrial utilizability
Deodorant of the present invention and deodorant carrier, much less monomer whose is to the deodoriging properties excellence of the gaseous aldehydes such as acetaldehyde, even if mix (deodorant compositions) use with other deodorant to excellent deodoriging properties of demonstration such as alkaline gas and sulphur class gases, also can keep the deodoriging properties to the excellence of alkaline gas and sulphur class gas, and can give full play to the gaseous aldehyde deodoriging properties. Therefore, deodorant of the present invention, deodorant carrier and deodorant compositions can be given excellent deodoriging properties to fiber, coating, sheet material, products formed, processed goods etc., can be with these as deodorizing products.
Claims (5)
1. gaseous aldehyde deodorizer, it contains the above material of at least one that is selected from the group that mono amino guanidinesalt, diaminourea guanidinesalt and triamido guanidinesalt formed.
2. a gaseous aldehyde deodorizer carrier wherein, is carried on the described gaseous aldehyde deodorizer of claim 1 on the carrier.
3. deodorant compositions, it contains the above material of at least one and described gaseous aldehyde deodorizer of claim 1 and/or the described gaseous aldehyde deodorizer of claim 2 carrier that is selected from the agent of sulfur class eliminating malodours from gases, alkaline gas deodorizer and the agent of organic acidity eliminating malodours from gases.
4. deodorization goods 1, it contains described gaseous aldehyde deodorizer of claim 1 and/or the described gaseous aldehyde deodorizer of claim 2 carrier.
5. deodorization goods, it contains the described deodorant compositions of claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004315426 | 2004-10-29 | ||
| JP315426/2004 | 2004-10-29 |
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| Publication Number | Publication Date |
|---|---|
| CN101222944A true CN101222944A (en) | 2008-07-16 |
Family
ID=36227853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800346028A Pending CN101222944A (en) | 2004-10-29 | 2005-10-26 | Deodorant |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4997974B2 (en) |
| CN (1) | CN101222944A (en) |
| WO (1) | WO2006046611A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP4997974B2 (en) | 2012-08-15 |
| WO2006046611A1 (en) | 2006-05-04 |
| JPWO2006046611A1 (en) | 2008-05-22 |
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