CN109843431A - Household appliance and its operating method with self-cleaning catalytically active surface - Google Patents

Household appliance and its operating method with self-cleaning catalytically active surface Download PDF

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Publication number
CN109843431A
CN109843431A CN201780056641.0A CN201780056641A CN109843431A CN 109843431 A CN109843431 A CN 109843431A CN 201780056641 A CN201780056641 A CN 201780056641A CN 109843431 A CN109843431 A CN 109843431A
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China
Prior art keywords
household appliance
polyoxometallate
group
water
cations
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Granted
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CN201780056641.0A
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Chinese (zh)
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CN109843431B (en
Inventor
M·C·阿塔尔拉奥斯
A·比朔夫
M·A·布努埃尔玛格达莱娜
A·哈瑙
H·米朔
J·桑斯纳瓦尔
K·施珀斯
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BSH Hausgeraete GmbH
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BSH Bosch und Siemens Hausgeraete GmbH
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Priority claimed from EP16382432.9A external-priority patent/EP3296016B1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
    • A61L2/232—Solid substances, e.g. granules, powders, blocks, tablets layered or coated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic System compounds without a metal-carbon linkage
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F35/00—Washing machines, apparatus, or methods not otherwise provided for
    • D06F35/005—Methods for washing, rinsing or spin-drying
    • D06F35/008—Methods for washing, rinsing or spin-drying for disinfecting the tub or the drum
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/42—Details
    • A47L15/4276—Arrangements to detect or remove bad smells or odours
    • 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
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
    • A61L2/183—Ozone dissolved in a liquid
    • 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
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
    • A61L2/186—Peroxide solutions

Abstract

The present invention relates to a kind of household appliance (1), there is the household appliance at least one to contain the self-cleaning catalytically active surface (17) of polyoxometallate, contain polymer-type organic or inorganic adhesive in the surface, described adhesive is selected from acrylate-based adhesives, urethane based adhesives and Silicone-based adhesives, and the polyoxometallate has chemical formula (I) or (II): A3PZ4O24(I), Aq+3PVqZ12‑qO40(II), wherein, Z is Mo or W, q is 0,1,2 or 3, and A is selected from one or more cations, and one or more cations are selected from the group by (XR1R2R3R4)+form, wherein, at least one of group R1, R2, R3 and R4 are after replacing or unsubstituted containing at least one heteroatomic alkyl, alkoxyalkyl or naphthenic base and at least five carbon atom, wherein at least one described hetero atom is selected from O, S, N or P and X is nitrogen or phosphorus.

Description

Household appliance and its operating method with self-cleaning catalytically active surface
Technical field
The present invention relates to a kind of household appliance and its operating method with self-cleaning catalytically active surface.Particularly, The present invention relates to a kind of household appliance of self-cleaning catalytically active surface for containing polyoxometallate at least one and Its operating method.
Background technique
Household appliance may touch dust, dirt, food, moisture or human skin.This may lead on long terms Hygienic issues are caused, because microorganism may be deposited on household appliance and may be proliferated.
In addition, food stains be in household appliance it is common, they can lead to the problem of many.In general, on external component Spot presence it is related with bad hygienic sense.Some surfaces for example by the surface that stainless steel and glass are constituted are difficult to keep clear It is clean.Some spots, the spot for example burnt need consumer to pay very big effort.Food stains in culinary art place, (bake by stone or metal plate for standing a stove on as a precaution against fire Case) in can be found, but also can be also found in the storage class household appliance of such as refrigerating appliance.
In addition, the article made dirty in various ways usually cleans in containing water-bearing household appliance.Therefore, can go out in dish-washing machine Existing food residual, and dirt range possessed by the clothing being washed in washing machine is usually bigger.All aqueous household devices Tool is had in common that: in moist and warm atmosphere, especially at inaccessible position, dirt can be generated and be accumulated It is poly-.This dirt may be the good nutrition culture medium of microorganism such as bacterium and fungi.
Hygienic issues are particularly present in household appliance in the case where water.Therefore, it does washing in clothes treatment device, for example In machine, when using water storage part or when the frequent washing procedure used by means of cold liquid, in the case where door is closed or unfavorable Placement under the conditions of for a long time do not use period, dirt may be generated, especially formed include organic substance such as microorganism and nutrition The biomembrane of object.The biomembrane leads to niff and/or visible dirt.Possibly even generate pathological effect.It is raw Object film can especially be formed in following regions of washing machine: in that region, water exists for a long time, i.e., deposits without using period ?.These regions include the folding at the region of improper ventilation, such as flank, pocket, sealing, and water flows into and outflow portion, most In particular for being generated in storage washing and rinse cycle so as to the ash that reuses in subsequent washing or rinse cycle The water storage part of water.Therefore, it is intended that the formation of biomembrane is carried out disinfection and prevented to the water in household appliance.
The other household appliances that may be susceptible to microbial contamination are, for example, cooking-fume exhauster or dust catcher.
It regardless of the type of household appliance, all has the following problems: in order to control household appliance, it is often necessary to by user Touch operation panel.In this way, operation panel may microbial contamination, when household appliance by multiple people in use, this Biology may be spread slightly.
In order to keep the impeccable state of health, a variety of methods currently in use in household appliance.Particularly, from The many kinds of measures known in the state of the art for being used to remove and/or prevent biomembrane.In containing water-bearing household appliance, in some cases Machine cleaning procedure is provided, the machine cleaning procedure is by means of detergent at high temperature and in some cases by means of mentioning The drum rotation speed of high liquid level and/or raising, the dirt that accumulation is removed by means of the input of increased mechanical energy.Also Know using ozone and removes organic dirt.
In methods generally known, propose to use antimicrobial acivity composition, such as silver ion in surface.However, The shortcomings that these methods is that antimicrobial acivity composition can be removed gradually from surface and is therefore depleted.In addition, working as Ag+Or Cu+From Son is used for when containing water-bearing household appliance, when being used for example on the material surface that cleaning solution neutralization is contacted with cleaning solution, can also generate dirt Contaminate the adverse effect of underground water and water route.However, even if these active constituents are not rushed from the carrier material of household surface Wash off, they the effect of it is most of relatively low so that can still be formed on the surface in the long run microorganism even biomembrane And negatively affect the hygienic state of household appliance.
It had previously also proposed to remove organic dirt using full flowing (thorough-flow) principle by means of UV-C radiator Dirt, wherein locating removal is implemented as so that the microorganism in these dirts is finally killed by destroying its inhereditary material.
Other methods are related to improving by direct or indirect energy transfer (water, steam, microwave) to be contacted with cleaning solution Temperature at component surface is to heat-killed existing any microorganism.
Photocatalysis method is also known, such as is carried out using catalysis active compound, particularly coating of titanium dioxide Deodorization, disinfection and cleaning.In the method, catalyst needs often by means of UV radioactivation.These compounds support micro- life The oxidation modification or destruction of object, so that under the best circumstances all being removed microorganism by oxidation.However, this method is logical It is often only worked in a manner of limited, is especially only acted as in a manner of limited in the case where also needing UV light other than oxidation With.
The shortcomings that these known methods and measure be high-energy using and sometimes high equipment and/or operating cost to realize Significant effect.In certain methods, potential health hazard factor, such as ozone or UV has been used to radiate, to need volume Outer safety measure.
It is intended to reduce the attachment of dirt using the specific surface structure of lotus-effect and is intended to so that surface cleaning more holds Easily.These surfaces usually not anti-microbial effect.The one of all these methods is big the disadvantage is that they are all locally to make very much With.Therefore, there is no long-range anti-microbial effect for the Free water of water storage container.
Application of the polyoxometallate in multiple fields is known, such as in analysis and clinical chemistry, is being catalyzed In (including photocatalysis), in biochemistry (inhibit electronic transfer process), in medicine (antitumor and antiviral activity) and In the fabrication of integrated circuits.Polyoxometallate, which is known, is used in papermaking and plastics industry as most of oxidation catalyst In.
1 141 210 B1 of open source literature EP discloses a kind of method for bleaching washing articles or household surface, In, the detergent containing polyoxometallate and contaminated substrate contact.Air is used to float as the main source of oxygen atom It is white.
10 2,009 026 712 A1 of open source literature DE discloses a kind of household appliance at least one component, institute Stating at least one component has the surface that can be influenced by organic dirt, and the surface has photochemical catalyst, for reactivity electricity The light source that magnetic radiation irradiates photochemical catalyst is associated with the surface, and the surface is formed by the first material that primary is formed, light Catalyst is dispersed in first material.Material with titanium dioxide and its modifier is as photochemical catalyst by public in detail It opens.
2 761 073 B1 and US2014/231363 A1 of open source literature EP discloses a kind of containing water-bearing household appliance, tool There are the container for receiving stay clean object and at least one inner surface for containing catalytic active substance, the inner surface setting exists In household appliance, wherein catalytic active substance is polyoxometallate, and the inner surface during the operation of household appliance It is contacted with water to be cleaned.Preferably, polyoxometallate is tungstates, and more preferably tungstates is modified by titanium.
Open source literature WO2015/0787737A1 discloses a kind of water-bearing household appliance, has for storing a certain amount of ash The storage bin of water and processing unit for handling the buck being stored in storage bin.The water-bearing household appliance is configured for Determine the amount for the buck being stored in storage bin and for operating based on the amount of the determination for the buck being stored in storage bin Processing unit.
2014/154432 A1 of open source literature DE 10 2,013 205 302 A1 and WO discloses a kind of household appliance, Include at least one catalysis active principle in surface, wherein the catalysis active principle is included in the interior table of household appliance Polyoxometallate in face and/or outer surface, if household appliance is containing with the container for receiving stay clean object Water-bearing household appliance, then polyoxometallate includes at least in the outer surface of household appliance.
Open source literature WO2014/122225A1 discloses the miscellaneous polyoxometallic acid with chemical formula (I), (II) or (III) The purposes of salt:
Aq+3PVqZ12-qO40(I),
A6P2Z18O62(II), or
A3PZ4O24 (Ⅲ)
Wherein, Z is Mo or W,
Amount mark q=0,1,2 or 3, and
A is selected from one or more cations and includes at least one of following cations cation: quaternary ammonium cation, season Phosphine cation and tertiary sulfonium cation；The heteropolyoxometallate is used for substrate or substrate surface at least partly or to painting Layer provides automatically cleaning, removing, disinfection, certainly disinfection, biocidal, antimicrobial and/or smell removal behavior, or is used for organic material The decomposition and/or degradation of material.In chemical formula (I), Z is preferably Mo and q=2, and in chemical formula (III), Z is preferably W.
2 765 136 A1 of open source literature EP discloses the miscellaneous polyoxometallic acid with chemical formula (I), (II) or (III) Salt:
Aq+3PVqZ12-qO40(I),
A6P2Z18O62(II), or
A3PZ4O24 (Ⅲ)
Wherein, Z is Mo or W,
Q is 1,2 or 3, and
A is selected from one or more cations and includes at least one quaternary ammonium cation, and condition is compound [(n-C4H9)4N]3PMo12O40[(n-C6H9)4N]3PMo12O40It is excluded.Most preferably heteropolyoxometallate [[n-C4H9]4N]3PW4O24[(n-C6H13)4N]3PW4O24。
Summary of the invention
In light of this situation, the purpose of the present invention is to provide a kind of household appliances and one kind for operating this household device The method of tool, wherein growth of the microorganism on household appliance or in household appliance is prevented from or is at least obstructed.Preferably, It can be simply and especially to remove or prevent dirt in a manner of health, or at least largely remove or prevent dirt. Preferably, it can remove or prevent the dirt with microorganism.Keeping hygienic state should be readily, because from cleaning Range and frequency on for cleaning pay should very little.In the ideal case, it should be that can completely avoid cleaning.
Above-mentioned purpose according to the present invention by a kind of household appliance of the feature with corresponding independent claims and its Operating method is realized.The preferred embodiment of household appliance according to the present invention is disclosed in the corresponding subordinate claims.I.e. Make not clearly state herein, the preferred embodiment of household appliance according to the present invention also corresponds to according to the method for the present invention Preferred embodiment, and preferred embodiment according to the method for the present invention corresponds to the preferred implementation of household appliance according to the present invention Example.
Therefore, preferably a kind of to contain water-bearing household appliance the present invention relates to a kind of household appliance comprising for accommodate to The cylinder of clean article and at least one contain the self-cleaning catalytically active surface of polyoxometallate, wherein the surface Containing polymer-type organic or inorganic adhesive, described adhesive be selected from acrylate-based adhesives, urethane based adhesives and Silicone-based adhesives, and polyoxometallate has chemical formula (I) or (II):
A3PZ4O24(I),
Aq+3PVqZ12-qO40 (II)
Wherein, Z is Mo or W,
Q is 0,1,2 or 3, and
A is selected from one or more cations, and one or more cations are selected from by (XR1R2R3R4)+The group of composition, In, group R1、R2、R3And R4At least one of be replace after or it is unsubstituted containing at least one heteroatomic alkyl, alkane Oxyalkyl (alkyloxoalkyl) or naphthenic base simultaneously have at least five, preferably at least 6, more preferably at least 7 carbon atoms, and And X is selected from nitrogen or phosphorus, at least one described hetero atom is selected from O, S, N or P.
Preferably, polyoxometallate is the polyoxometallate with chemical formula (I'), (II') or (III'):
A3PW4O24(I'),
Aq+3PVqMo12-qO40(II'), or
Aq+3PVqW12-qO40 (III')
Wherein, 0,1 or 2 q.
In an advantageous embodiment, polyoxometallate is:
Aq+3PVqMo12-qO40(II'), or
Aq+3PVqW12-qO40 (III')
Wherein, q is 1 or 2.
In a particularly preferred embodiment of household appliance, polyoxometallate is:
A3PW4O24 (I')。
For following household appliances it is preferable that in the household appliance, cation is selected from (NR1R2R3R4)+The group of composition, In, group R1、R2、R3And R4At least one of be after there is the substitution of at least eight carbon atom or unsubstituted alkyl, alkane Oxyalkyl or naphthenic base.
In a preferred embodiment of household appliance, cation is selected from by (PR1R2R3R4)+The group of composition, wherein group R1、R2、R3And R4At least one of be after there is the substitution of at least eight carbon atom or unsubstituted alkyl, alkoxyalkyl or Naphthenic base.
Moreover it is preferred that polyoxometallate includes different cation.In this regard, it is highly preferred that polyoxometallate Include chemical formula be (XR1R2R3R4)+Different cations, wherein group R1、R2、R3And R4At least one of have extremely Few 10 carbon atoms.It is highly preferred that cation has chemical formula (NR1R2R3R4)+And the group R of different cations1、R2、R3 Or R4With eight and ten carbon atoms.The advantageous mixture of cation is, for example, Aliquat 336 (catalyst of Stark), Wherein, cation contains octyl chain and decyl chain, and octyl chain and decyl chain are namely respectively provided with the alkane of 8 and 10 carbon atoms Base chain.
In household appliance of the invention, polyoxometallate is used in certainly together with polymer-type organic or inorganic adhesive In cleaning type catalytically active surface, described adhesive is selected from acrylate-based adhesives, urethane based adhesives and organic silicon substrate Adhesive.
Suitable acrylate-based adhesives are, for example:Company2K-Acryllack, Worl é eCryl A1220, the Covestro company of Worl é e Chemie companyA145, water-dilutable Hydroxyl-functional polyacrylic acid dispersion and Covestro companyA265BA。
Suitable polyurethane (PUR) based adhesive is the ATCOAT Atrepur 340 of such as ATCOAT company.
Suitable organosilicon aliphatic radical adhesive is for example from Evonik companyEF, Dow is come from The 2577Low Voc of Corning company or Bluesil RES 991 from Bluesil company.
In the manufacture of household appliance according to the present invention, the self-cleaning containing polyoxometallate will be provided with and be catalyzed The component of active surface can be obtained for example and by component dip-coating into the liquid containing adhesive and polyoxometallate.
Household appliance is unrestricted.However, household appliance preferably contains water-bearing household appliance.In general, containing water-bearing household appliance It is the household appliance for using water during operation.Article to be cleaned especially can be tableware or clothing.According to the present invention, it cleans It will be also be appreciated that meaning to refresh.Therefore, it is also possible to dryer containing water-bearing household appliance.
In in the case where containing water-bearing household appliance, it is preferred that the surface is household appliance internal to be arranged in, in household The inner surface contacted during the operation of utensil with flowing or static water.What contact was commonly necessary, because of household appliance water In organic substance by contacted with the surface containing polyoxometallate can just be oxidized and and then be decomposed.
In in the case where containing water-bearing household appliance, it is preferred that at least one inner surface is arranged in water inlet system.Additionally Or alternatively, it is preferable that at least one described inner surface is arranged in water storage part.And then advantageously, water storage part includes circulation Element and/or air feed element.
It in a preferred embodiment, is dish-washing machine or clothes treatment device or coffee machine containing water-bearing household appliance.
It in a further advantageous embodiment, is to belong to the group being made of washing machine and drying and washing machine containing water-bearing household appliance Clothes treatment device.
Household appliance of the invention makes for example enough with efficient, economical and environmental-friendly containing the water energy in water-bearing household appliance Mode is handled, so that the organic substance of such as microorganism and nutrients is decomposed and can avoid in household appliance Form biomembrane.In the present invention, polyoxometallate, particularly the spy described herein for not needing to activate by radiating The characteristic as oxidation catalyst or as oxidant of fixed polyoxometallate is used.The effect of polyoxometallate can To be twice, the degree of these effects is related to used specific polyoxometallate.
For example, the reason of disinfection, may is that polyoxometallate when organic substance and polyoxometallate directly contact Autoxidation organic substance.Then polyoxometallate itself can be reduced.Based on degree of oxidation, this oxidation may cause micro- Biological moieties or fully convert.If microorganism can be converted into the state that can not continue breeding, sometimes even right The minimum oxidation of microorganism is also likely to be enough.
However, importantly, catalytic action is played on the surface containing polyoxometallate in the oxidation reaction.It is anti-in oxidation Ying Zhong, polyoxometallate are typically used as the oxidation catalyst cooperated with oxidant.According to the present invention, oxidant is unrestricted. It is preferable to use oxygen containing oxidants.It is particularly preferred that oxygen, inorganic or organic peroxide and/or ozone serve as oxidant.At this In a little substances, oxygen is particularly preferred oxidant, this is because can be avoided additional input may be harmful or interfering Substance.Air preferably acts as source of oxygen.However, oxygen may exist, for example be dissolved in water.In addition, passing through the corresponding of water It is mobile, the mixing of air and water can occur, such as forming bubble in water, and such air-can be made Aqueous mixtures are contacted with the surface containing polyoxometallate, wherein aerial oxygen is preferably used as oxidant.It is particularly preferred that Air feeds element and provides the oxygen of sufficient amount in water to be processed.
The polyoxometallate (POM) being discussed herein can have antimicrobial property by three kinds of different effects.That is, Catalytic action, wherein particularly advantageously POM can aoxidize some organic substances, such as bacterium or fungi.After POM reduction, Its reduction form can pass through oxygen recovery.In this process, superoxide ion O2 -It is generated as secondary substance.Super oxygen Object ion is also unusual highly effective oxidizer.In addition, OH-Free radical can be used as other strong oxidizer and be formed.
In another embodiment, use peroxide or ozone as oxidant.
In the household appliance with ozone generator, ozone is preferably used as oxidant.This household appliance is preferably also With ozone removal device.Then, the surface containing polyoxometallate is arranged such that the surface can be with water and smelly Oxygen contact.For example, the surface containing polyoxometallate is respectively disposed in the washing machine that ozone can be introduced into outer shell In outer shell.
If using peroxide as oxidant, it is preferable to use the peroxidating being already present in laundry care product Object.This saves the additions to other peroxide.
It is dried in a preferred household appliance of the invention, particularly containing water-bearing household appliance, more particularly washing machine or laundry In dry machine, the self-cleaning catalytically active surface containing polyoxometallate is arranged in detergent distributor disk or outer shell, such as Fruit peroxide is used as oxidant, then is particularly preferably arranged in outer shell.Reason for this is that peroxide especially exists In strong detergent and bleaching agent, although especially bleaching agent is typically directly added in roller.
Preferably, the user of the clothes treatment device of the embodiment of household appliance according to the present invention can pass through selection Button designates whether to be added to strong detergent or bleaching agent.Alternatively, it can be sensed by the one or more in washing machine The presence of device monitoring strong oxidizer such as peroxide or ozone.There are ozone or peroxide, it can save and follow Loop member or air feed the operation of element.
As described above, there are oxidant such as oxygen, hydrogen peroxide or ozone, no matter household appliance contains The self-cleaning surface of polyoxometallate is inner surface or outer surface, oxygen radical (or oxygen radical, it is united herein Referred to as " oxygen radical ") it can all be formed at the surface.When these highly reactive form of oxygen free radicals connect with the organic substance for including microorganism When touching, oxidation reaction occurs, this leads to the pathologic process in the decomposition and/or microorganism of organic substance.In this way, it resists The formation of biomembrane.For example, being contacted with the inner surface coated with polyoxometallate as described herein containing water-bearing household appliance Water in organic substance be decomposed, so as to avoid the formation of biomembrane.
In order to carry out continuous oxidation reaction, oxidation material is for example containing more metals as oxidation catalyst The oxygen radical generated at the surface of oxygen hydrochlorate preferably has enough sports levels.This can for example be recycled by means of pump Water-bearing media is realized.In the case where usually not flowing around the surface containing polyoxometallate, natural diffuseness is utilized Or it may be sufficient there are temperature difference using convection current.It is first on surface itself, such as sanitary control when first having to At part realize needed for disinfection when and can save the distant effect by reactive oxygen species, for example to the complete of surrounding medium In the case where totally disappeared poison, then enough motilities at surface can be saved.
In addition, should have the sufficiently high oxidant of concentration, in water to be processed to obtain enough hygiene effects.
In household appliance of the invention, it is preferred that self-cleaning catalytically active surface, which has, contains polyoxometallic acid The upper layer of salt, the upper layer with a thickness of 0.01mm to 1.5mm, preferably 0.01mm to 0.5mm, more preferably 0.02mm are extremely 1mm, more more preferable 0.05mm to 0.5mm.
According to the present invention, polyoxometallate and acrylate-based adhesives, urethane based adhesives or organic siliconresin The adhesive of base is used together.Preferably, coating layer thickness is in the range of 10nm to 500 μm, more preferably at 20nm to 200 μm In range.
It is furthermore preferred that the polyoxometallic acid salt content in the upper layer on surface is by weight percentage in household appliance Be calculated as 0.5% to 50%, more preferably in the range of 1% to 15% (weight percent), more more preferably 1% to 10%, for these weight percent are the weight (being hereinafter also referred to as " superficial layer ") based on upper layer.
Advantageously, polyoxometallate as much as possible is present in the surface containing polyoxometallate, because more The effect of oxometallate is typically limited to surface.When the application purpose of polyoxometallate is not only disinfecting surface but also wants It is particularly true when carrying out disinfection to surrounding medium.For the surface of target especially disinfecting surface, less mostly gold can be used Belong to oxygen hydrochlorate, such as the content of (weight percent) 10% in superficial layer, even 1% (weight percent) may be sufficient, For these weight percent are the weight based on superficial layer.
Self-cleaning catalytically active surface containing polyoxometallate can be formed in any way, as long as may be implemented Catalytic effect according to the present invention.For example, the surface can be by forming the film containing polyoxometallate come shape At, such as formed by the way that polyoxometallic acid salt particle to be arranged at the surface of porous material, both modes To use suitable adhesive.Position of the manufacture of self-cleaning catalytically active surface containing polyoxometallate usually with surface It sets and the usage mode of household appliance is related.
Week is dissolved into order to which polyoxometallate to be maintained at surface and in order to prevent due to contacting with surrounding medium It encloses in liquid medium or any other mode exhausts, it is important that use certain cationic described herein.With long-chain Organic ion be particularly suitable, as described herein.The particularly preferred example of organic ion with long-chain is methyl three Octyl ammonium cation and tributyl myristyl phosphine cation.
It should be noted that realizing additional anti-microbial effect by using cation described herein.
Polyoxometallate described herein can be combined on a variety of surfaces by suitable adhesive composition Salt.In addition, polyoxometallate can with surface bearing object manufacture before with the rest part of surfacing, for example including polyamide Or the organic polymer material mixing of polyalkylene (such as polypropylene).
Furthermore, it is possible to prepare foil, wherein polyoxometallate is combined with suitable carrier material and adhesive, so that The polyoxometallate of relatively small amount, which may only be needed, can cover big surface region.This foil can be applied to household device Associated components in tool, such as by glued or melt bonded apply.In addition, this foil can be directly placed at injection mold In and thus be directly used in manufacture household appliance component.
In household appliance according to the present invention, any surface can all contain polyoxometallate in principle.These surfaces It can be inner surface or outer surface.
Surface containing polyoxometallate can be handle, knob, handlebar, the outer surface of controller or switch, institute State switch e.g. lamp switch, handrail, sliding block, control key, slip controller or touch-sensitive (sensor effect) surface.
In the dryer according to the present invention as household appliance, the surface, which can be, for example receives object to be dried The container and condensate of product.In general, all in household appliance containing wet part, for example including its shell, pipeline, valve Pump may include the surface containing polyoxometallate.
Inner surface containing polyoxometallate can be the water container containing water-bearing household appliance and/or in passage component Wall.
Water container can be the water container of such as coffee percolator.In addition, the institute with the contacts such as water or milk of percolation filter There are other parts to can have the self-cleaning surface containing polyoxometallate.
Household appliance according to the present invention can also include internal container, wherein waste, rubbish or used, rotten Food can be temporarily stored in the internal container.
Other purposes of the invention are for carrying out disinfection to the surface in scale or balance, to avoid turning for pathogenic microorganism It moves.Therefore, scale and balance also belong to household appliance according to the present invention.
In the case where household appliance is washing machine, here it is particularly advantageous that outer shell, which has, includes polyoxometallate.It avoids The formation of biomembrane, and can activate filtering in the process of washing procedure.Another component in washing machine is detergent Distributor disk can also be formed in detergent distributor disk to avoid biomembrane.
In the dish-washing machine as household appliance of the invention, the surface containing polyoxometallate can contribute to bleach The disinfection of the activation of agent, the decomposition of organic material and operation and storage water.
Herein broadly in the cooling device including freezer unit, the present invention can be used for disappearing for inner surface and condensate Poison, condensate are likely to be present on inner surface and in condensate and pipeline.
Household appliance according to the present invention can also be dust catcher or the device for cleaning or safeguarding floor, wherein contain There is the surface of polyoxometallate particular in the region of filter and non-woven cloth and anther (anther) and for protecting In the region for holding the device of anther.
Household appliance of the invention can also be oven, microwave device or steamer, stove or table, by containing this paper institute The polyoxometallate stated and surface hygiene can be made.
The other examples of household appliance according to the present invention are flow model heaters；Steam station and vapour iron；Household is empty Gas humidifier and air-conditioning equipment.In these cases, the disinfection of surface and hot water to be added is important.It is generally important that It, can be to avoid the propagation of possible harmful microorganism or fungi in the case where skin contact by the disinfection on surface.
In the case where another exemplary cooking-fume exhauster as household appliance according to the present invention, surface disappears Poison, particularly include the air in the disinfection of mesh and filter pad in this household appliance and this household appliance Disinfection treatment be important.
Another important use is the surface of filter unit.Self-cleaning surface as described herein can be dust mistake Surface in the fluffing portion of filter.
Moreover, it relates to a kind of method for operating household appliance, wherein household appliance is aqueous household device Tool comprising for accommodate article to be cleaned, such as washing articles cylinder and at least one contain polyoxometallate Self-cleaning catalytic activity inner surface, the inner surface can contact during the operation of household appliance with water or cleaning solution, wherein The surface includes polymer-type organic or inorganic adhesive, and described adhesive is selected from acrylate-based adhesives, polyurethane The adhesive of adhesive and organic silicon substrate, polyoxometallate have chemical formula (I) or (II):
A3PZ4O24(I),
Aq+3PVqZ12-qO40 (II)
Wherein, Z is Mo or W,
Q is 0,1,2 or 3, and
A is selected from one or more cations, and one or more cations are selected from by (XR1R2R3R4)+The group of composition, In, group R1、R2、R3And R4At least one of be replace after or it is unsubstituted containing at least one heteroatomic alkyl, alkane Oxyalkyl or naphthenic base simultaneously have at least five carbon atom, and X is selected from nitrogen or phosphorus, at least one described hetero atom is selected from O, S, N Or P, water to be cleaned or cleaning solution are contacted with the surface containing polyoxometallate.
The present invention has the advantages that with simple and cost-effective mode provide household appliance easy to clean, particularly Contain water-bearing household appliance to what the neurological susceptibility of dirt (more particularly to the dirt of microorganism) was substantially reduced.
It is particularly advantageous in that in surface, particularly inner surface using one of polyoxometallate as described herein: institute Stating surface can use as catalyst system operation for many years without any additional activation or additional energy.It is only attached The use that the circulating element or air that add feed element will need additional energy, but with the filtering of such as film or electrochemical process Other method for treating water compared to being still a small amount of.Furthermore, it is not necessary that additive is added, and the work of catalyst can be saved Change, such as the activation radiated by UV.Of the invention has the self-cleaning surface as described herein containing polyoxometallate The further advantage of specific embodiment of household appliance be: using bleaching agent, polyoxometallate can be passed through Activation improve the effect of bleaching agent.In addition, polyoxometallate as described herein can have the effect of killing the virus.Therefore, lead to Cross the present invention, provide it is a kind of for household appliance, hardly with continue cost and with the long life water process System.
Pass through specific self-cleaning surface as described herein, it might even be possible to avoid cleaning.It can be clear with lower frequency It is clean or do not need even to clean at all.In addition, the present invention provides long-range effect, rather than just making containing polyoxometallic acid The surface of salt is protected or from microorganism.The oxidation reaction occurred at the surface containing polyoxometallate can be with It additionally influences to need in household appliance to antimicrobial adjacent domain.
Detailed description of the invention
Hereinafter, the preferred embodiment that the present invention will be described in more detail will be carried out with reference to Fig. 1 of attached drawing.
It is that the currently associated component of embodiment of washing machine shows that Fig. 1, which is household appliance as the construction of non-limiting example, It is intended to.
Specific embodiment
The washing machine 1 of the present embodiment has outer shell 2, and roller 3 is rotatably installed in outer shell 2 and can be by driving motor 15 drivings.For ergonomic reasons, the rotation axis 4 of roller 3 is oriented relative to horizontal direction one angle of inclination upwards, To be easier to pass in and out and check the inside of roller 3.By this arrangement, then cooperates and be especially formed at the inner surface of cylinder shell Clothing blender 5 and dip device 6 for cleaning solution 7, cleaning solution 7 or foam water 7 wearing to washing articles 8 can be enhanced Stream.
Washing machine 1 also has water inlet system, and the water inlet system includes the water connection dress for life water feeder 9 It sets, electrically-controlled valve 10 and water inlet pipe 11, water inlet pipe 11 extend to outer shell 2 and supplied via detergent distributor disk 12, wherein Detergent part can be conveyed to outer shell 2 from detergent distributor disk 12 by the liquid of feed.
Heating device 14 is also disposed in outer shell 2.Valve 10 and heating device 14 can be based on journey by program control system 13 Sequence carries into execution a plan to control, and described program executive plan can link to time-program(me) and/or link to the parameter in washing machine 1 The particular measurement value of (such as liquid level, fluid temperature, the rotation speed etc. of roller 3) reaches.16 indicate for the liquid in outer shell 2 The pump of body, particularly cleaning solution 7.
Water storage part 18 can store the buck for having been used to rinsing washing materials product 8.The buck can be used for subsequent wash Wash the period.For this purpose, water storage part 18 is connected to valve 10 by pipeline (" water inlet pipe for rinse liquid ") 19, valve 10 is also adjusted Save the feed of fresh water.It is provided with circulating element 20 in water storage part 18 and air feeds element 21, circulating element 20 and air Feeding element 21 can also be controlled by program control system 13.It, can be at the inner surface 17 of water storage part 18 by these measures Carry out particularly efficient oxidation reaction.
Contain A3PW4O24Inner surface 17 be used in detergent distributor disk 12, in outer shell 2 and in water storage part, wherein A be cationic trioctylammonium or tributyl myristyl phosphine, or mixtures thereof.
Reference signs list
1 household appliance contains water-bearing household appliance, washing machine
2 (outer) cylinders
3 laundry drums
The rotation axis of 4 rollers
5 clothing blenders
6 dip device
7 cleaning solutions
8 washing articles
9 life water feeders
10 valves
11 water inlet pipes
12 detergent distributor disks
13 program control systems
14 heating devices
15 driving motors
16 pumps
17 inner surfaces containing polyoxometallate
18 water storage parts
19 are used for the water inlet pipe of rinse water
20 circulating elements
21 air feed element

Claims (14)

1. a kind of household appliance (1), the self-cleaning catalysis that there is the household appliance at least one to contain polyoxometallate Active surface (17), which is characterized in that the surface (17) contains polymer-type organic or inorganic adhesive, described adhesive choosing From acrylate-based adhesives, urethane based adhesives and Silicone-based adhesives, and the polyoxometallate has change Formula (I) or (II):
A3PZ4O24(I),
Aq+3PVqZ12-qO40 (II)
Wherein, Z is Mo or W,
Q is 0,1,2 or 3, and
A is selected from one or more cations, and one or more cations are selected from by (XR1R2R3R4)+The group of composition, wherein Group R1、R2、R3And R4At least one of be replace after or it is unsubstituted containing at least one heteroatomic alkyl, alcoxyl Alkyl or cycloalkyl simultaneously has at least five carbon atom, wherein at least one described hetero atom is selected from O, S, N or P and X is nitrogen Or phosphorus.
2. household appliance (1) according to claim 1, which is characterized in that the polyoxometallate is:
A3PW4O24 (I')。
3. household appliance (1) according to claim 1 or 2, which is characterized in that the cation is selected from by (NR1R2R3R4)+Composition Group, wherein group R1、R2、R3And R4At least one of be replace after or it is unsubstituted, at least eight carbon atom Alkyl, alkoxyalkyl or naphthenic base.
4. household appliance (1) according to any one of claim 1 to 3, which is characterized in that it is described cation selected from by (PR1R2R3R4)+The group of composition, wherein group R1、R2、R3And R4At least one of be replace after or it is unsubstituted, have Alkyl, alkoxyalkyl or the naphthenic base of at least eight carbon atom.
5. household appliance according to any one of claim 1 to 4, which is characterized in that the polyoxometallate includes Different cations.
6. household appliance according to claim 5, which is characterized in that the polyoxometallate includes with chemical formula (XR1R2R3R4)+Different cations, wherein group R1、R2、R3And R4At least one of have at least ten carbon atom.
7. household appliance according to claim 6, which is characterized in that the cation has chemical formula (NR1R2R3R4)+, And the group R of the different cation1、R2、R3Or R4It is respectively provided with 8 and 10 carbon atoms.
8. household appliance (1) according to any one of claim 1 to 7, which is characterized in that the household appliance is aqueous Household appliance (1), and the surface (17) are that setting is transported in the household appliance (1) inside, in the household appliance (1) The inner surface (17) contacted between the departure date with flowing or static water (7).
9. household appliance (1) according to claim 8, which is characterized in that the inner surface (17) is arranged in water storage part (18) in.
10. household appliance (1) according to any one of claim 1 to 9, which is characterized in that the household appliance is to wash Bowl machine or clothes treatment device or coffee machine.
11. household appliance (1) according to claim 10, which is characterized in that the household appliance is selected from by washing machine (1) and drying and washing machine composition group clothes treatment device.
12. household appliance (1) according to any one of claim 1 to 11, which is characterized in that the surface (17) has Upper layer containing polyoxometallate, the upper layer with a thickness of 0.01mm to 0.5mm.
13. household appliance (1) according to claim 12, which is characterized in that mostly golden in the upper layer of the surface (17) Belong to oxygen phosphate content is 0.5% to 50% by weight percentage, for which is the weight based on the upper layer 's.
14. method of the one kind for operating household appliance (1), wherein the household appliance is to contain water-bearing household appliance, described aqueous Household appliance includes for accommodating the cylinder of article to be cleaned (8) (2) and at least one self-cleaning for containing polyoxometallate Catalytic activity inner surface (17), the inner surface can contact during household appliance is run with water or cleaning solution (7), and feature exists Contain polymer-type organic or inorganic adhesive in, the inner surface (17), described adhesive be selected from acrylate-based adhesives, Urethane based adhesives and Silicone-based adhesives, and the polyoxometallate has chemical formula (I) or (II):
A3PZ4O24(I),
Aq+3PVqZ12-qO40 (II)
Wherein, Z is Mo or W,
Q is 0,1,2 or 3, and
A is selected from one or more cations, and one or more cations are selected from by (XR1R2R3R4)+The group of composition, wherein Group R1、R2、R3And R4At least one of be replace after or it is unsubstituted containing at least one heteroatomic alkyl, alcoxyl Alkyl or cycloalkyl simultaneously has at least five carbon atom, wherein at least one described hetero atom is selected from O, S, N or P and X is nitrogen Or phosphorus,
Wherein, water or cleaning solution (7) to be cleaned are contacted with the inner surface (17) containing polyoxometallate.
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