CN101195477A - Energy-activated compositions for controlled sustained release of a gas - Google Patents

Abstract

The present invention provides a composition for energy-controlled generation and release of at least one gas, which includes an energy-activated catalyst capable of being activated by electromagnetic energy, and a solid or a liquid containing anions capable of being oxidized by the activated catalyst or reacted with species generated during activation of the catalyst to generate at least one gas. The composition, when exposed to electromagnetic energy, is capable of generating and releasing the gas after activation of the catalyst and oxidation or reaction of the anions.

Description

The energy-activated compositions that is used for the controlled, sustained release of gas

Background of the present invention

The present invention relates generally to a kind of by electromagnetic energy activation with controlled, sustained generation with discharge the composition of at least a gas.The present invention be more particularly directed to a kind of anionic composition that comprises energy-activated catalyzer and can be produced gas by this deactivated catalyst surface or reaction product oxidation subsequently, by discharging gas or gaseous mixture, as dioxide peroxide, sulfurous gas, nitrogen peroxide, nitric oxide, nitrous oxide, carbonic acid gas, hydrogen sulfide, prussic acid, chlorine monoxide, chlorine or ozone and be used to delay, control, kill or suppress microbial contamination (as, bacterium, fungi, virus, mould, algae, and protozoon), deodorizing, increase aquatic foods, and/or delay, suppress or the control chemotaxis.

Photocatalyst generally is used for catalyzed oxidation and reduction reaction, as the degraded of the organic compound of polluted air or water.If be exposed to ultraviolet ray in the presence of semi-conductive, water, oxygen and oxyhydroxide negatively charged ion can change into superoxide anion and oh group.These materials can be further and organic compound reaction, finally forms carbonic acid gas and water.Carbonic acid gas produces by organic decomposition rather than by anionic oxidation.

Photocatalyst increases the decomposition of the generation of oh group with the catalysis organic compound.If photon is absorbed by semiconductor light-catalyst, electronics to conduction band, produces the valence band hole by valence.Hole and electrons spread can be carried out chemical reaction respectively at this to the surface of photocatalyst granular.The absorbed water molecules of valence band hole oxidation of organic compounds or oxidation is to produce oh group.This examples of applications of photocatalyst comprises people's such as Nachtman United States Patent (USP) 5868924 (by water is reduced total content of organic carbon through a water purifier chamber that comprises photocatalyst); The United States Patent (USP) 5501801 of Matthews (method that is used for the organic pollutant of photochemical catalytic oxidation fluid wherein contacts fluid with decomposing pollutant with the surface of photocatalyst coating); People's such as Tanaka United States Patent (USP) 5658841 (by liquid exposure is changed into carbonic acid gas in photocatalyst with organism); People's such as Heller United States Patent (USP) 5616532,5849200 and 5854169 (comprising the composition of photocatalyst and the binding agent of non-oxidizable basically of the removal organic polluter that is used for getting on) from air, water or the surface that scribbles said composition; People's such as Watanabe United States Patent (USP) 5874701 (contact scribble a kind of wall of photoactivation film or the bacterium on floor or the photolysis of gas loading matter); And people's such as people's such as Mouri United States Patent (USP) 5872072 and Linkous United States Patent (USP) 5880067 (be used for deodorizing or purify the photocatalyst on surface, by decomposition contact should the surface air or the stench in the liquid such as ammonia or hydrogen sulfide or microorgranic contaminant such as algae, fungi or bacterium).

Photocatalyst also has been used for electro-chemical photocell, utilizes electric current to produce gas in electrolyte solution.People such as Inoue are at " TiO ₂Competition photosensitized oxidation on the light anode ", Chemical communication, 1073-1076 (1977) has described halide ions, as the photo-electro chemical oxidation of chloride anion in electrolyte solution.

Dioxide peroxide and other are killed livestock thing gas also by using activator to produce and discharging, and this activator provides the oxonium ion that can form gas subsequently with precursors reaction.People such as Ripley have described bicomponent system in United States Patent (USP) 5736165, comprise, comprise liquid ingredient and activator component such as the transition metal or the acid of chlorine dioxide precursor such as metal chlorite.These components were separated in case the too early formation of dioxide peroxide before using always.If these components are merged, oxonium ion and chlorine dioxide precursor reaction form dioxide peroxide.

Moisture-activated produces and the composition that discharges chlorine dioxide or other gas is described in people's such as Wellinghoff United States Patent (USP) 5360609,5631300,5639295,5650446,5668185,5695814,5705092,5707739 and 5888528 and pending trial U.S. Patent application series № 08/651876,08/724907,08/858860,08/921357,08/924684 and 09/138219.These compositions comprise the negatively charged ion that can produce and discharge gas with the oxonium ion reaction.These compositions need be protected in case produce too early and discharge gas at moisture in production, storage and transportation.

Need a kind ofly can activate easily to begin to produce and discharge the inert compositions of dioxide peroxide or another gas in use.Food product pack, modified atmospheres packing needs a kind of composition with other occasion that material is wherein absorbed or contacts by the people, except wherein being used to produce the negatively charged ion of gas, said composition is only by the material that can be used for food or be commonly considered as safety or those materials of inert substance are formed and reacted and obtain the resistates only be made up of them.Although people's such as Wellinghoff moisture-activated composition is effective biocides and reodorant, need a kind of easier manufacturing, easily activation and deactivation with better controlled or handiness is provided in controlled, sustained generation with when discharging gas and also using before transportation and store, need not to avoid being exposed to the composition of atmospheric water easily.Also need a kind of composition that can produce and discharge gas in being completely enclosed in hydrophobic material the time.

Summary of the present invention

Therefore, in purpose of the present invention, as can be seen, provide a kind of and can produce and discharge its concentration and be enough to eliminating bacteria, fungi, mould, algae, protozoon and the dioxide peroxide of virus or the composition of other thing gas of killing livestock; A kind of composition that can produce and discharge finite concentration gas is provided, and this gas can delay, prevents, suppresses or control biochemical the decomposition, and control breathing delays, prevents or controls chemotaxis, increases aquatic foods or deodorizing; Provide a kind of and can after photoactivation, produce and discharge the composition that this gas concentration object height reaches the several months; The composition that a kind of easy storage is provided and not influenced by atmospheric water; Provide a kind of and can after the electromagnetic energy activation, in several seconds, several minutes, a few hours, a couple of days, several weeks or several months, under controlled or lasting condition, begin to discharge the composition of gas; Provide a kind of can deactivation to postpone to produce gas and subsequent reactivation to produce the composition of gas once more; A kind of composition with higher gas release efficient of comparing with known compositions is provided; Provide a kind of except wherein being used to produce the negatively charged ion of thing gas of killing livestock, only comprising the composition that is allowed to be used for the material that the people exposes; A kind of composition of odorless is provided; Provide a kind of unrestricted flow and easily before using with other composition blended powder; A kind of powder that can permeate porous surface is provided; Provide a kind of preparation continue discharging the method for compositions that needs less reaction or physical process when dioxide peroxide or other are killed livestock thing gas; Provide a kind of can high temperature process or use powder and can the pyrolysated method; Provide a kind of employing the cheap method of starting raw material to minimize cost; And the ordinary method that a kind of and preparation dioxide peroxide release composition be provided mutually specific energy reduce the method for producing harm and processing requirements.

The present invention relates to a kind of composition that is used for the controlled generation of electromagnetic energy and discharges at least a gas, comprise a kind of can by the energy-activated catalyzer of electromagnetic energy activatory and a kind of comprise can oxidation or reaction produce the anionic solid of at least a gas or contain the suspension of solid matter.Said composition can produce and release gas after the activation of catalyzer and anionic oxidation or reaction when being exposed to electromagnetic energy.

Another embodiment of the present invention relates to a kind of composition that is used for the controlled generation of electromagnetic energy and discharges at least a gas, comprise a kind of can by the energy-activated catalyzer of electromagnetic energy activatory and a kind of comprise can oxidation or reaction produce at least a negatively charged ion that is selected from the gas of dioxide peroxide, sulfurous gas, hydrogen sulfide, chlorine monoxide, prussic acid, nitrogen peroxide and nitric oxide.Said composition can produce and release gas after the activation of catalyzer and anionic oxidation or reaction when being exposed to electromagnetic energy.Preferably, this negatively charged ion is the chlorite negatively charged ion.

The invention still further relates to a kind of powder that is used for controlled, sustained generation and discharges at least a gas, wherein said powder comprises one, and comprise can be by the nuclear of the energy-activated catalyzer of electromagnetic energy activatory and at the lip-deep particle of described nuclear or layer.This particle or layer comprise can oxidation or reaction produce the negatively charged ion of at least a gas.This powder can produce and release gas after the activation of catalyzer and anionic oxidation or reaction when being exposed to electromagnetic energy.Preferably, this particle or layer comprise the chlorite negatively charged ion.

This powder is made by a kind of like this method: with energy-activated catalyzer and comprise can oxidation or the reaction anionic particle and the solvent that produce at least a gas form a kind of suspension, form powder by this suspension then.This powder can produce and release gas after the activation of catalyzer and anionic oxidation or reaction when being exposed to electromagnetic energy.

Another aspect of the present invention relate to a kind of by provide comprise energy-activated catalyzer and can oxidation or reaction produce the anionic solid of at least a gas or contain the suspension of solid matter, then this solid or the suspension that contains solid matter are exposed to electromagnetic energy to activate described catalyzer and described negatively charged ion oxidation or reaction produced and to discharge gas, come controlled generation and discharge the method for at least a gas.

The invention still further relates to a kind of in the method that delays, kills, prevents on the surface of material, in material or in the atmosphere of this material of encirclement or controlling microbial is polluted, promptly, this material is placed on the adjacent composition place that does not produce and discharge the thing gas of killing livestock under a kind of situation that is not having an electromagnetic energy, and said composition is exposed to electromagnetic energy to produce from said composition and to discharge at least a thing gas of killing livestock to the atmosphere of surrounding this material.

Another embodiment of the present invention relates to a kind of method that delays, prevents, suppresses or control biochemical decomposition on the surface of material or in material, promptly, this material is placed on adjacent under a kind of situation that is not having an electromagnetic energy, do not produce and discharge the biochemical composition place that suppresses gas that decomposes, and said composition is exposed to electromagnetic energy suppresses gas to the atmosphere of surrounding this material at least a biochemical the decomposition to produce from said composition and to discharge.

Another embodiment of the present invention relates to the method that a kind of control material is breathed, promptly, this material is placed on the adjacent composition place that does not produce and discharge respiratory control gas under a kind of situation that is not having an electromagnetic energy, and said composition is exposed to electromagnetic energy to produce from said composition and to discharge at least a respiratory control gas to the atmosphere of surrounding this material.

The invention still further relates to and a kind of material surface or material surrounding atmosphere are carried out deodorizing or material is increased bright method, promptly, this material is placed on adjacent under a kind of situation that is not having an electromagnetic energy, do not produce and discharge composition place, and said composition is exposed to electromagnetic energy to produce from said composition and to discharge at least a odour that removes to the atmosphere of surrounding this material except that odour.

Another embodiment of the present invention relates to and a kind ofly delays, prevents, suppresses or control the method that organism attracts the chemotactic of material, promptly, with this material be placed on adjacent under a kind of situation that is not having an electromagnetic energy, do not produce and discharge stink hide in gas or the stink and the composition place of gas, and with said composition be exposed to electromagnetic energy with produce from said composition and discharge at least a stink hide gas or the stink and gas in the atmosphere of surrounding this material.

The invention still further relates to and a kind ofly delay, prevent or the method for the biological pollution of controlled atmosphere, that is, said composition is exposed to electromagnetic energy to produce from said composition and to discharge at least a Purge gas to the atmosphere of surrounding said composition.

Another embodiment of the present invention relates to a kind of delaying, kill, prevent or the controlling microbial pollution, or on the surface of material, in material or in the atmosphere of surrounding this material, delay, prevent, suppress or the biochemical decomposition of control, material surface or material surrounding atmosphere are carried out deodorizing, material is increased aquatic foods, or delay, prevent, inhibition or control organism are to the method for the chemotactic attraction of material, promptly, this material is placed on the adjacent composition place that does not produce and discharge chlorine dioxide under a kind of situation that is not having an electromagnetic energy, and said composition is exposed to electromagnetic energy to produce from said composition and to discharge chlorine dioxide to the atmosphere of surrounding this material.

Another embodiment of the present invention relates to a kind of gas that comprises and produces being used for the controlled generation of electromagnetic energy and discharging the complex body of at least a gas of layer and isolation layer.This gas produce layer comprise a kind of can by the energy-activated catalyzer of electromagnetic energy activatory and can oxidation or reaction produce the negatively charged ion of at least a gas.This isolation layer is adjacent to the surface that gas produces layer, electromagnetic energy can be transferred to gas and produce layer and this gas is not seen through or semi-transparent mistake.This gas produces layer and can produce and release gas after the activation of catalyzer and anionic oxidation or reaction when being exposed to electromagnetic energy.

Another embodiment of the present invention relates to a kind of composition that is used for the controlled and controlled generation of moisture of electromagnetic energy and discharges at least a gas.Said composition comprise a kind of can be by the energy-activated catalyzer of electromagnetic energy activatory; Can be when catalyst activation and the proton substance reaction or can oxidation to produce the negatively charged ion of at least a gas; With sour releasing agent; And the negatively charged ion that can produce at least a gas with the oxonium ion reaction.Said composition can produce and release gas after the hydrolysis of the activation of catalyzer, sour releasing agent and anionic oxidation or reaction when being exposed to electromagnetic energy and moisture.

Other purpose of the present invention and advantage can be from following detailed description as seen.

Brief description of the drawings

Fig. 1 a-1c is the particulate synoptic diagram that is used for controlled, sustained generation and discharges gas.

Fig. 2-the 11st, the gas concentration of various powder compositions is as the figure of the function of time.

Figure 12-the 19th, the gas concentration of various polymeric films that has added gas release composition of the present invention is as the figure of the function of time.

Detailed description of the preferred embodiments

According to the present invention, have been found that when a kind of when comprising energy-activated catalyzer and anionic composition and being exposed to electromagnetic energy such as visible or UV-light, can be by the gas of controlled, sustained release dioxide peroxide of said composition and so on.Negatively charged ion both can be activated catalyst oxidation, also can react to produce gas with the material that produces in the catalyst activation process.The generation of gas can delay by stopping that said composition is exposed to electromagnetic energy, and recovers by at this said composition being exposed to electromagnetic energy.Said composition can be according to desired application required mode repetition of activation and deactivation.Be different from the moisture-activated material that produces oxonium ion, this energy-activated compositions can be processed the anionic decomposition that prevents to be used to produce gas under high pH value.Said composition preferably includes a kind of photoactive catalyst with the negatively charged ion photoxidation.But said composition preferably is mixed with a kind of easy preparation and former state and uses or add various end-use products, as the powder in film, tackiness agent, granular blend, wax, resin, polymkeric substance, plastics, powder composition and shaped object such as tablet and the tubing.This powder also can be made up of inorganic materials fully, and it is with regard to odorless like this.

What the present composition preferably comprised about 50-99.99% weight can be activated catalyst oxidation or react to produce the negative ion source of gas with the material that produces when the catalyst activation by the energy-activated catalyzer of electromagnetic energy activatory and about 0.01-50% weight, the more preferably from about negative ion source of the energy-activated catalyzer of 80-98% weight and about 2-20% weight, the most preferably from about negative ion source of the energy-activated catalyzer of 86-96% weight and about 4-14% weight.If said composition is exposed to electromagnetic energy, this energy-activated catalyzer is activated and negatively charged ion is oxidized or react with generation and discharge gas.

Be not limited to particular theory of the present invention, it is believed that said composition passes through one or more following mechanism and produce gas.Energy-activated catalyzer absorbs the photon that energy surpasses band gap when being exposed to electromagnetic energy.Electronics to conduction band, produces the valence band hole by valence.Valence band hole and electrons spread are carried out chemical reaction respectively at this to the surface of energy-activated catalyzer.When electronics was transferred to the valence band hole by negatively charged ion, this negatively charged ion was activated the oxidation of catalyst surface institute, formed gas.It is believed that dioxide peroxide or nitrogen peroxide are produced by this transfer to the valence band hole of chlorite or nitrate anions by electronics.It is believed that, these and other gas, also can utilize from water, chemisorption hydroxyl or some other hydration material as ozone, chlorine, carbonic acid gas, nitric oxide, sulfurous gas, nitrous oxide, hydrogen sulfide, prussic acid and chlorine monoxide and to capture electronics, form by the reaction of negatively charged ion with the proton material that produces when the catalyst activation.Gas is diffused into by composition and reaches about 6 months in the surrounding atmosphere and be positioned near the said composition material with influence.Can every centimetre ³Discharge several ppm gases at least 1 day, the composition in 1 week, 1 month or 6 months can be prepared by the inventive method, be used for various end-uses, comprise deodorizing, increase aquatic foods, control, postpone or prevent that chemotaxis is as reducing or suppressing insect infestation, control, reduce or prevent biochemical decomposition, respiratory control and control, postpone, destroy or prevent microorganism such as bacterium, mould, fungi, algae, protozoon and viral growth on various materials.Although these compositions are by controlled lasting gas release, said composition can be prepared at specific end-use as required, and gas can discharge within 1 day like this.

Said composition can be a solid, as powder, film, tablet or coating or liquid as the suspension that contains solid matter (as, dispersion, emulsion).In a preferred embodiment, said composition is a kind of powder of being made up of a plurality of particles 10 as shown in Figure 1, comprising the nuclear 12 that has layer 14 on the outside surface 16 of nuclear.In addition, said composition is a kind of powder of being made up of a plurality of particles 18 shown in Fig. 1 b, comprising the nuclear 12 that has particle 20 on the outside surface 16 of nuclear.In another preferred embodiment, said composition is a kind of powder of being made up of a plurality of particles 22 shown in Fig. 1 c, comprising the nuclear 12 that has layer 14 and particle 20 on the outside surface 16 of nuclear.Nuclear 12 comprises energy-activated catalyzer.Layer 14 and particle 20 comprise and can be activated catalyst oxidation or react to produce the negatively charged ion of gas with the material that produces when the catalyst activation.Although layer 14 preferably continuously and even basically, the particle 10 or 22 with lipostrat 14 of variable thickness provides acceptable lasting gas release.This powder is preferably about 50 dusts to about 1 mm size.

Powder of the present invention preferably comprises can being activated catalyst oxidation or reacting to produce the negative ion source of gas with the material that produces when the catalyst activation of the energy-activated catalyzer of about 50-99.99% weight and about 0.01-50% weight, the more preferably from about negative ion source of the energy-activated catalyzer of 80-98% weight and about 2-20% weight, the most preferably from about negative ion source of the energy-activated catalyzer of 86-96% weight and about 4-14% weight.If this powder is exposed to electromagnetic energy, this energy-activated catalyst core is activated and the negatively charged ion on this nuclear is oxidized or react with generation and discharge gas.

If suspension is exposed to electromagnetic energy, this energy-activated catalyzer is activated, and negatively charged ion is oxidized or react to produce gas with the material that produces when catalyzer activates, and gas is by this suspension diffusion and discharge then.

Can be activated catalyst oxidation or all can be used for said composition with anionic source that the material that produces reacts to produce gas any comprising when catalyzer activates.If anionic oxidation potential makes it can transfer an electron to the valence band hole of energy-activated catalyzer, this negatively charged ion can be activated catalyst oxidation to produce gas.Preferably, solid comprises negatively charged ion.Suitable solid comprises the salt of negatively charged ion and counter ion; Inert material such as vitriol, zeolite or be impregnated with anionic clay; Polyelectrolyte such as polyoxyethylene glycol, ethylene oxide copolymer or tensio-active agent; Solid electrolyte or from aggressiveness such as nylon or Nafion ^TM(Dupont); Or sosoloid.If said composition is a kind of suspension that comprises solid matter, salt is dissolved in the solvent forming a kind of solution that comprises negatively charged ion and counter ion, and with energy-activated catalyst suspension in this solution.Powder can be for example, by this suspension is dry or by solid (as, salt particle) is formed with the blend of energy-activated granules of catalyst physics.

Be suitable for the salt of making negative ion source and comprise alkali metal chlorite, the alkaline-earth metal chlorite, transition metal ion, protonated primary, the second month in a season or tertiary amine, or the chlorite of quaternary ammonium, the basic metal hydrosulphite, the alkaline-earth metal hydrosulphite, transition metal ion, protonated primary, the second month in a season or tertiary amine, or the hydrosulphite of quaternary ammonium, alkali metal sulfite, alkaline-earth metal sulfite, transition metal ion, protonated primary, the second month in a season or tertiary amine, or the sulphite of quaternary ammonium, alkali metalsulphide, alkaline earth sulfide, transition metal ion, protonated primary, the second month in a season or tertiary amine, or the sulphide salt of quaternary ammonium, alkali metal hydrocarbonate, alkali metal bicarbonates, transition metal ion, protonated primary, the second month in a season or tertiary amine, or the supercarbonate of quaternary ammonium, alkaline carbonate, alkaline earth metal carbonate, transition metal ion, protonated primary, the second month in a season or tertiary amine, or the carbonate of quaternary ammonium, alkali metal hydrosulfide, the alkaline-earth metal sulfhydrate, transition metal ion, protonated primary, the second month in a season or tertiary amine, or the sulfhydrate salt of quaternary ammonium, alkali metal nitrites salts, alkaline earth metal nitrite, transition metal ion, protonated primary, the second month in a season or tertiary amine, or the nitrite of quaternary ammonium, the alkaline metal hypochlorite, the alkaline-earth metal hypochlorite, transition metal ion, protonated primary, the second month in a season or tertiary amine, or the hypochlorite of quaternary ammonium, alkali metal cyanide, the alkaline-earth metal prussiate, transition metal ion, protonated primary, the second month in a season or tertiary amine, or the cyanide salt of quaternary ammonium, alkali metal peroxide, alkaline earth metal peroxide, or transition metal ion, protonated primary, the second month in a season or tertiary amine, or the superoxide salt of quaternary ammonium.Preferred salt comprises sodium, potassium, calcium, lithium or the ammonium salt of chlorite, hydrosulphite, sulphite, sulfide, sulfhydrate, supercarbonate, carbonate, hypochlorite, nitrite, prussiate or superoxide.The chlorite that be fit to use and the commercial form of other salt can comprise other salt and additive, as tin compound with catalytic gas reforming.

The gas that is discharged by said composition depends on negatively charged ion oxidized or reaction.Lose electronics by negatively charged ion, the proton material that produces by negatively charged ion and electromagnetic energy reacts, by reducing positively charged ion in oxidation/reduction reaction, or molecular oxygen, oxide compound or hydroxyl by negatively charged ion and chemisorption react any gas of forming and all can be produced and discharged by said composition.This gas is preferably dioxide peroxide, sulfurous gas, hydrogen sulfide, prussic acid, nitrogen peroxide, nitric oxide, nitrous oxide, carbonic acid gas, chlorine monoxide, chlorine or ozone.

Chlorine dioxide produces when said composition comprises the chlorite negatively charged ion and discharges.The suitable chlorous acid Yanyuan that can add said composition comprises alkali metal chlorite such as Textone or potassium chlorite; Alkaline-earth metal chlorite such as calcium chlorite; Or chlorite such as chlorous acid ammonium, trialkyl chlorous acid ammonium and the quaternary ammonium chlorite of transition metal ion, protonated primary, second month in a season or tertiary amine or quaternary ammonium.If add in the composition of the present invention, suitable chlorous acid Yanyuan such as Textone are stable surpassing under about 90 ℃ processing temperature, can process under comparatively high temps like this.The composition that discharges dioxide peroxide can be used for deodorizing, increase aquatic foods, delay, prevent or control chemotaxis, delay, prevent or control and biochemically decomposes, delay, prevent or control biological pollution (as, deactivation biological pollutant after biological war) or kill, delay, control or prevent bacterium, mould, fungi, algae, protozoon and viral growth.

If described composition comprises bisulfite or inferior sulfate radical negatively charged ion, can produce and discharge sulfurous gas.The bisulfite Yanyuan that can add described composition comprises the hydrosulphite of basic metal hydrosulphite such as sodium bisulfite or Potassium hydrogen sulfite, alkaline-earth metal hydrosulphite such as calcium sulfite or transition metal ion, protonated primary, second month in a season or tertiary amine or quaternary ammonium.These hydrosulphite are free bisulfite negatively charged ion and the possible inferior sulfate radical negatively charged ion of forming in solution.The composition that discharges sulfurous gas can be used for food antiseptic (as, suppress biochemical and decompose as the brownization of the product of production), sterilize and the inhibitory enzyme catalyzed reaction.Said composition also can be used for the reduction chlorine gas concentration in the catalysis cycle, wherein uses aluminium or iron powder flush away chlorine optionally from the mixture of chlorine and dioxide peroxide.Said composition also can be exposed to electromagnetic energy to produce sulfurous gas with said composition by powder is placed in the packing, seals this packing then, generation sulfurous gas atmosphere this packing in and be used for modified atmospheres and pack.

Hydrogen sulfide produces from comprise the anionic composition of sulfhydrate or sulfide and discharges.Acceptable sulfhydrate negative ion source comprises the sulfhydrate salt of alkali metal hydrosulfide such as sodium sulfhydrate or potassium hydrosulfide, alkaline-earth metal sulfhydrate such as calcium hydrosulfide or transition metal ion, protonated primary, second month in a season or tertiary amine or quaternary ammonium.Acceptable sulfide negative ion source comprises the sulphide salt of alkali metalsulphide such as sodium sulphite or potassium sulphide, alkaline earth sulfide such as sulfurated lime or transition metal ion, protonated primary, second month in a season or tertiary amine or quaternary ammonium.Reductive agent or sulphur source when the composition that discharges hydrogen sulfide can be used as manufacturing chemistry product and be used as polymerization inhibitor.

Chlorine and chlorine monoxide produce from comprise the anionic composition of hypochlorite and discharge.Acceptable hypochlorite negative ion source comprises the hypochlorite of alkaline metal hypochlorite such as clorox, alkaline-earth metal hypochlorite such as Losantin or transition metal ion, protonated primary, second month in a season or tertiary amine or quaternary ammonium.The composition of release chlorine can be used for manufactured meat, fish and production product, also can be used as biocide.The composition that discharges chlorine monoxide can be used as biocide.

Prussic acid produces from comprise the ionogenic composition of cyanide anion and discharges.Suitable cyanide anion ion source comprises the cyanide salt of alkali metal cyanide such as sodium cyanide or potassium cyanide, alkaline-earth metal prussiate such as calcyanide or transition metal ion, protonated primary, second month in a season or tertiary amine or quaternary ammonium.The composition that discharges prussic acid can be used as generation agent or rodenticide.

Carbon dioxide produces from the composition that comprises supercarbonate or anion, carbonate and discharges.Suitable supercarbonate source in the described composition be can add and the supercarbonate such as the bicarbonate of ammonia of alkali metal hydrocarbonate such as sodium bicarbonate, saleratus or lithium bicarbonate, alkali metal bicarbonates or transition metal ion, protonated primary, second month in a season or tertiary amine or quaternary ammonium comprised.This supercarbonate can dissociate into bicarbonate anion and possible carbonate anion in solution.The composition of release of carbon dioxide can be used for the greenhouse,, it is administered to soil surface with denseization plant ambient air that is.The composition of release of carbon dioxide also can be exposed to electromagnetic energy to produce carbonic acid gas with said composition by composition is placed in the packing, seals this packing then, generation carbon dioxide atmosphere this packing in and be used for modified atmospheres and pack.This packing can be used for controlling the breathing in storage and transportation of production product, cut-flower or other plant subsequently, or delays, prevents, suppresses or control the biochemistry decomposition of food.

Nitrogen oxide such as nitrogen peroxide and nitric oxide produce from comprise the anionic composition of nitrite anions and discharge.Suitable nitrite anions negative ion source comprises the nitrite of alkali metal nitrites salts such as Sodium Nitrite or potassium nitrite, alkaline earth metal nitrite such as calcium nitrite or transition metal ion, protonated primary, second month in a season or tertiary amine or quaternary ammonium.The composition that discharges nitrogen peroxide or nitric oxide can be used for improving the biocompatibility of biomaterial and is used for the modified atmospheres packing.

Ozone produces from the composition that comprises superoxide anion and discharges.The suitable superoxide anion source that can add composition comprises the superoxide salt of alkali metal peroxide such as sodium peroxide or Potassium peroxide, alkaline earth metal peroxide such as calcium peroxide or transition metal ion, protonated primary, second month in a season or tertiary amine or quaternary ammonium.The composition that discharges ozone can be used for deodorizing, increases aquatic foods, delays, prevents, suppresses or control chemotaxis, delays, prevents, suppresses or control the biochemical growth of decomposing or killing, delay, controlling or preventing bacterium, mould, fungi, algae, protozoon and virus.

In some cases, composition comprises two or more different negatively charged ion, discharges two or more different gas with different rates like this.The release of gas has different purposes, or a kind of thus gas can strengthen the effect of other gas.For example, comprise that the anionic composition of chlorous acid hydrogen salt and chlorite can discharge that sulfurous gas is used for food antiseptic and dioxide peroxide is used for deodorizing, increases aquatic foods, control chemotaxis or controlling microbial.

Any electromagnetic-energy that can activate this energy-activated catalyzer all can be used for producing gas by said composition.In other words, it all is suitable providing any electromagnetic-energy of the photon that energy surpasses energy-activated catalyzer band gap.For the photoactivation of composition, preferred electromagnetic-energy comprises light such as daylight, fluorescence and UV-light.UV-light and the visible light except incandescence such as blue light are preferred electromagnetic-energies.Restriction is transferred to the wavelength region of energy-activated catalyzer if desired, and additive such as UV blocker also can be included in said composition.Also can add the absorbing wavelength of photosensitizers, particularly the uv-absorbing wavelength be moved to the visible absorbance wavelength, can improve the activation of room light like this with mobile said composition.The UV absorption agent can be added in the composition and produce and rate of release to slow down gas.

By any semi-conductor of electromagnetic energy activatory or add this semi-conductive particle or other material can be used as energy-activated catalyzer of the present invention.These semi-conductors generally are metal, pottery, inorganic or polymer materials, by the whole bag of tricks known in the art, make as sintering.Semi-conductor also can be carried out surface treatment by the material of silica or alumina and so on or seal to improve semi-conductive weather resistance, dispersiveness or other characteristic.Be used for catalyzer of the present invention and can buy relative broad range from nano particle to granula.Representational energy-activated catalyzer comprises metal oxide such as anatase octahedrite, rutile or amorphous titania (TiO ₂), zinc oxide (ZnO), tungstic oxide (WO ₃), ruthenium dioxide (RuO ₂), iridium dioxide (IrO ₂), tindioxide (SnO ₂), strontium titanate (SrTiO ₃), barium titanate (BaTiO ₃), tantalum oxide (Ta ₂O ₅), calcium titanate (CaTiO ₃), ferric oxide (III) (Fe ₂O ₃), molybdic oxide (MoO ₃), Columbium pentoxide (NbO ₅), three Indium sesquioxide (In ₂O ₃), Cadmium oxide (CdO), hafnia (HfO ₂), zirconium white (ZrO ₂), Manganse Dioxide (MnO ₂), cupric oxide (Cu ₂O), vanadium pentoxide (V ₂O ₅), chromium trioxide (CrO ₃), three ytterbium oxide (YO ₃), silver suboxide (Ag ₂O) or Ti _xZr _1-xO ₂, wherein x is 0-1; Metallic sulfide such as Cadmium Sulfide (CdS), zinc sulphide (ZhS), indium sulfide (In ₂ ³), cupric sulfide (Cu ₂S), tungsten disulfide (WS ₂), three bismuth sulfide (BiS ₃) or curing zinc cadmium (ZnCdS ₂); Metal chalcogenide such as zinc selenide (ZnSe), cadmium selenide (CdSe), indium selenide (In ₂Se ₃), selenizing tungsten (WSe ₃) or cadmium telluride (CdTe); Metal phosphide such as indium phosphide (InP); Metal arsenide such as gallium arsenide (GaAs); Nonmetal semi-conductor such as silicon (Si), carbocyclic ring silicon (SiC), diamond, germanium (Ge), germanium dioxide (GeO ₂) and tellurium germanium (GeTe); Photoactivation is with polyanionic such as W ₁₀O ₃₂ ^-4Photoactivation heteropolyanion such as XM ₁₂O ₄₀ ^-nOr X ₂M ₁₈O ₆₂ ^-7, wherein x is Bi, Si, Ge, P or As, M is Mo or W, and n is the integer of 1-12; With polymer semiconductor such as polyacetylene.Transition metal oxide such as titanium dioxide and zinc oxide are preferred because their chemically stables, nontoxic, cheap, have highlight catalytic active, and can obtain the nano particle that can be used for preparing transparent moulding or extrude plastic prod.

Can change in every way by the speed of any composition release of the present invention gas, activation and the release rate profile that said composition begins gas release, for example change energy-activated catalyzer or the negative ion source concentration in composition, in said composition, add alkali, tensio-active agent, thinner or optical filtering additive, the material that adds silicate and so on is to cooperate the active surface position, in catalyzer, introduce electric charge, lattice or surface imperfection (as, the Ti in the Ti-base catalyst ³⁺Impurity), change the working method of composition, light modulated wavelength and intensity, or change the order of addition(of ingredients) of each composition when the preparation composition.

The present composition can comprise any conventional powder, film, coating or the catalytic additive based on composition gross weight the highest about 99%.These additives comprise tinting material and dyestuff, spices, filler, lubricant, stablizer, accelerator, delayer, toughener, blend auxiliary agent, controlled release agent, antioxidant, UV blocker, releasing agent, softening agent, biocide, flow promotor, anti-caking agent, processing aid and lightscreening agent.

The additive that is preferred for pilot-gas release comprises alkali, tensio-active agent and lightscreening agent.Alkali it is believed that can be in the course of processing stabilization negatively charged ion and help the oh group of negatively charged ion oxidation to participate in transfer transport by generation.The amount of alkali in composition can be regulated with the time that changes gas release and be strengthened the thermostability of said composition.For example, long if desired gas release postpones, and the concentration of alkali can raise.The present composition preferably comprises the alkali based on the highest about 50% weight of composition gross weight.Suitable alkali includes, but is not limited to the hydroxide salt such as the ammonium hydroxide of alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide or magnesium hydroxide, transition metal ion, protonated primary, second month in a season or tertiary amine or quaternary ammonium.

Tensio-active agent it is believed that and can produce the movable ion layer on the surface of composition to quicken the charge transfer between negatively charged ion and the valence band hole.Can in composition, add any tensio-active agent that can change rate of gas release.Representational tensio-active agent comprises Triton X-301  (a kind of sulfated ethoxylated alkylphenol of being made by Union Carbide) and TritonX-100  (a kind of alkyl aryl ethoxylates of being made by Union Carbide).

Optical filtering additive may command incident light is transferred in the composition, to reduce rate of gas release.Suitable optical filtering additive comprises silicate and clay.Any silicate of the aqueous solution of water soluble or water miscibility organic materials all can be used for preparing composition of the present invention.Suitable silicate comprises water glass, sodium metasilicate, sodium sesquisilicate, source water glass, borosilicate and aluminosilicate.The commercial form that is fit to these silicate of use generally comprises sodium and potassium cationic.With SiO ₂The silicon of measuring with M ₂The ratio of alkali metal cation in silicate granules that O measures is about 2.0-4.0, preferably about 2.3-3.5, and 2.5-3.2 more preferably from about, wherein M is selected from sodium and potassium.

Composition of the present invention can be made into various forms, comprises powder, film, coating, tablet, emulsion and suspension.Suspension is preferably made by energy-activated catalyzer, solvent and chlorite, hydrosulphite, sulphite, sulfide, supercarbonate, carbonate, sulfhydrate, nitrite, hypochlorite or cyanide salt are mixed.Preferably, this salt forms a kind of solution and energy-activated catalyzer is mixed formation suspension with this solution with solvent.This suspension is not exposed to therein that (that is, under the dark condition of photoactivation catalyzer) stores under the condition of electromagnetic energy of catalyst activation wavelength.In addition, energy-activated catalyzer and solvent can mix a kind of slurry of formation and salt can be added this slurry with formation suspension, or with energy-activated catalyzer and salt while and solvent, then their are mixed formation suspension.

If prepare suspension can be used ultrasonic mixing, high shear mixing or any conventional homogenize method.The solvent that is used to form this suspension is any liquid of this salt of solubilized, as water or the miscible organic materials of water as alcohol, ketone (as, acetone), polyacrylic ester (as, polymethylmethacrylate) or the acid amides aqueous solution of (as, dimethyl formamide).

Powder shown in Fig. 1 a-1c is preferably made by this suspension of spraying drying.Also can use other removal of solvents technology to form powder, comprise that filtration, centrifugal treating, dry this suspension make salt by energy-activated granules of catalyst chemisorption, or any other solid-liquid separating method.The gas release efficient of powder of the present invention is 50-95% normally.This powder stores at (that is, under the dark condition of photoactivation catalyzer) under the condition of the electromagnetic energy that is not exposed to the catalyst activation wavelength.

In case formation suspension can be spray dried to powder by any method known in the art, for example comprises any known atomising method such as nozzle or rotating disk.Usually, temperature in and temperature out are maintained at about 250-350 ℃ and about 100-150 ℃ respectively for aqeous suspension, and known in the art can the suspension that comprise other solvent the variation.General take place (for example, within about 60 seconds) rapidly of drying process with atomizing.If desired, powder can be further dry by any ordinary method subsequently.

The form of any powder of the present invention can be by changing reinforced solution particle diameter, solid substance concentration or each component relative ratios, viscosity, surface tension or temperature, feed rate, the residence time, air velocity, air themperature, flow direction in the moisture eliminator or be used for the nozzle of spray-drying process or the kind of spraying gun changes, these are known in the art.For example, when the enough height of anion concentration make negatively charged ion on the surface of nuclear during crystallization, the powder of Fig. 1 b forms.Under low anion concentration, form the powder of Fig. 1 a.The powder of Fig. 1 c is forming under the anion concentration in the middle of one, negatively charged ion this moment cocrystallization on the nuclear surface.

Powder of the present invention can be made as fluidization process by aforesaid method or the coating process by any routine.In fluidization process, coating material carries out aerosolization like this: this material is added in the chamber of fluidized-bed energy-activated catalyst core particle of its bump fluidizing at this by nozzle of small diameter.By contacting with the energy-activated catalyst core particle of fluidizing, this powder just forms along with the evaporation of salts solution.This particle can be packed in the container of an electromagnetic energy of having blocked energy-activated catalyst activation wavelength subsequently.This particle also can pulverize or micronization to reduce its particle diameter, form thinner powder and pack.Powder of the present invention also can be made by mechanical blending salt particle and energy-activated catalyzer, machinery-fluidisation blend and other known preparation method of powder as described in embodiment 1 and 3.

The purposes of said composition is various.These compositions almost can be used for any environment that electromagnetic energy exposes occurring.These powder can be solid by molding or sinter molding.These powder also can dipping, melt, sintering, with other admixture of powder or add in addition in the various materials, obtain being used for film, fiber, coating, tablet, resin, polymkeric substance, plastics, pipe material, film, engineering materials, paint and the tackiness agent of various end-use.These powder are particularly useful for making any injecting products, press moulded product, thermoforming product or extrusion moulding product such as casting film or blown film.The thermostability of these powder makes them can be used for Shooting Technique.

Powder of the present invention preferably added in the plastic prod of injection moulding, compression moulding, thermoforming or extrusion moulding before the moulding of routine or moulding technology, wherein utilizes conventional equipment that powder is carried out compounding and granulation and pellet is mixed with a kind of material.Be applicable to that the material that forms these products comprises any polymkeric substance, multicomponent polymeric such as multipolymer, ter-polymers or oligopolymer and polymer alloy or its blend or any wax.Representative polymers is drawn together polyolefine such as polyethylene and polypropylene, polyethylene terephthalate, polyvinyl chloride, urethane, metallocene polymers, polyester, polyacrylic ester, acrylic acid polymer, polystyrene, polycarbonate, polymeric amide, polyesteramide, vinyl-vinyl acetate copolymer, ethylene-methyl acrylate multipolymer and polyacetal.Suitable wax comprises Microcrystalline Wax, paraffin and synthetic wax, and as chlorinated wax, polyethylene wax, polyoxyethylene glycol and polypropylene glycol.

This moulding or layered product preferably include the powder of the present invention of about 0.1-70% weight and this material of about 30-99.9% weight, more preferably from about this material of the powder of the present invention of 1-50% weight and about 50-99% weight, most preferably from about this material of the powder of the present invention of 2-50% weight and about 50-98% weight.

This moulding maybe can be made by the polymer processing method of any routine.For example, powder of the present invention or powder pellet and this material can mix in mixing tank such as Henschel mixing tank, are fed to then in the forcing machine operated under being no more than about 200 ℃ temperature or the mold apparatus to form melt.But this melt casting film forming is shaped to pellet by the cooling of dry air on shaker conveyer, or is shaped to required shape by casting, thermoforming or the compression molding of routine.

This melt can use that hot melt, dip-coating, spraying, the curtain known are coated with, dried wax, wet wax and laminating method and be administered on the surface as film.Following examples 10 and 11 have been described the manufacturing of casting film and blown film.If the present composition is form of nanoparticles (as, 50 angstroms dias), can form transparent film.

Conventional film for additive can add in the described material as required.These additives comprise linking agent, UV stablizer, fire retardant, emulsifying agent, expanding material, lubricant, antioxidant, tinting material and dyestuff.

Can form multilayer composite, in the shell that forms by this complex body, produce gas like this.This species complex comprises that gas produces layer and isolation layer.This gas produce layer comprise a kind of can be by the energy-activated catalyzer of electromagnetic energy activatory and can oxidation or the negatively charged ion of generated reactive gas.This isolation layer is placed on the adjacent surface that produces layer in gas.This isolation layer is transparent to electromagnetic energy, and it can be transferred to energy gas and produce layer like this.But isolation layer is to producing gas impermeable or the only semi-transparent mistake that layer produces and discharges by gas.This gas produces layer can produce and discharge gas after catalyst activation and negatively charged ion oxidation or reaction when being exposed to electromagnetic energy.

Gas release powder of the present invention, suspension or other composition can be used for delaying, kill, preventing or be controlled on the material surface, in the material or the microbial contamination in the material surrounding atmosphere, promptly, this material is placed on adjacent in a kind of composition of the present invention, and said composition is exposed to electromagnetic energy, discharge in the atmosphere of thing gas around this material of killing livestock by said composition.

The gas release composition can be used for delaying, prevent, suppress be controlled on the material surface or material in biochemistry decompose, promptly, this material is placed on adjacent in a kind of composition of the present invention, and said composition is exposed to electromagnetic energy, produce and discharge by said composition and suppress in the atmosphere of gas around this material a kind of biochemical decomposition.This material is preferably the product of production such as fruit or vegetables or other food.This food preferably stores or transports in modified atmospheres packing, like this can be by delaying, prevent or controlling biochemical the decomposition or preservation period that microbial contamination prolongs this food.

This gas release composition also can be used for the respiration of control material, promptly, this material is placed on adjacent, and said composition is exposed to electromagnetic energy, produce and discharge in the atmosphere of a kind of respiratory control gas around this material by said composition in a kind of composition of the present invention.This material is preferably the product of production such as fruit, vegetables, meat, meat product, seafood, seafood prods or other plant or flower or other plant.The respiratory control of food and flower generally realizes by food or flower are stored or transport in modified atmospheres packing or selective gas infiltration packing.

This gas release composition also can be used for the atmosphere deodorizing of the surface of material or encirclement material is maybe increased aquatic foods with this material, promptly, this material is placed on adjacent in a kind of composition of the present invention, and said composition is exposed to electromagnetic energy, produce and discharge a kind of removing in the atmosphere of odour around this material by said composition.

This gas release composition also can be used for delaying, prevent, suppress or controls organism the chemotaxis of material is attracted, promptly, this material is placed on adjacent in a kind of composition of the present invention, and said composition is exposed to electromagnetic energy, by said composition produce and discharge that a kind of stink hides or stink in and in the atmosphere of gas around this material.

This gas release composition also can be used for delaying, preventing or controls atmospheric biological pollution,, said composition is exposed to electromagnetic energy that is, is produced and is discharged in the atmosphere of a kind of Purge gas around the said composition by said composition.Said composition also can be used for delaying, prevent or the biological pollution of control material, that is, this material is placed on adjacent to said composition, and said composition is exposed to electromagnetic energy, produced and discharged in the atmosphere of a kind of Purge gas around this material by said composition.This Purge gas is for example used with deactivation biological pollutant (as, anthrax) after biological war or is used for other military purification.

The composition that the present invention is used for aforesaid method is preferably solid or liquid as comprising the suspension of solid matter.

In aforesaid method, material surface or whole material can be full of or apply said composition with powder of the present invention, and said composition can be mixed with this material, and said composition is salable in airtight container, or this material and said composition are salable in container.If said composition is sealed in the container, this container can sealing by fusing or the part sealing make some gas by this container leakage.

For example, the powder of release dioxide peroxide can be filled to the container that is used for storing food, soap, cloth-washing detergent, file, clothing, paint, seed, Medical Instruments, equipment and supplies, personal care product, medical treatment or biological waste, sports shoes, ostomy bag, footwear and refuse.The parcel of this powder, pouch, " tea-bag " or other gas-permeable container can be included in the storage vessel, to produce the little atmosphere of dioxide peroxide by activation.The powder that discharges dioxide peroxide also can be filled to paper or polymer materials (as, the end, bandage material, cutting board, food packaging article, food product packets sabot or seed pouch in shower mats, Box Toe, inset or the footwear); Add and be applied in cardboard packaging or other lip-deep wax or the polymeric coating; Add film such as packing film; Be shaped to porous member with water sterilization; Mix with material, produce the little atmosphere of dioxide peroxide on every side at material (as, soil); Or with other powder mixes with kill microorganisms, increase aquatic foods or deodorizing (as, foot-powder, bath powder, be used to handle jock itch powder, be used to handle pressure release surface powder such as carpet powder, be used to remove the siccative of moisture).

This powder also can form the tablet that can be dissolved in use in the water with the conventional compressing tablet material mixing of tackiness agent or other, produces and discharge the sterilization of preservation that dioxide peroxide is used for flower, surface sterilization, medical facilities or as mouth wash shua.Suspension of the present invention also can be packaged into the alternate products of these end-uses.

Suspension of the present invention can be used for above for the determined purposes of powder.For example, embodiment 12 described suspension can be administered on nail or the sufficient first preventing, reduce, to suppress or to control fungal growth or to brighten nail, or can be included in the bright first prescription for this reason.These suspension preferably include the polymkeric substance of the powder of the present invention of about 0.1-50% weight, about 20-50% weight such as solvent such as water (for water-soluble prescription) or the methyl alcohol or the methylethylketone (for non-water prescription) of polymethylmethacrylate or polyvinyl alcohol and the highest about 79.9% weight.Suspension of the present invention also can be used for the dentistry occasion, is used for the partly sterilised in oral cavity, for example said composition is administered on the dental surface, then ultraviolet curing adhesive is exposed to UV-light to solidify this tackiness agent and to form tooth filling.UV-light is with said composition activation generation and discharge a kind of sterilizing gas.Composition of the present invention also can add the lotion that is used for of short duration, permanent or semipermanent mouth care.

Except deodorizing with in and the stench, said composition also can be used for delaying, prevent, suppressing or controls chemotaxis (that is, living organism being attracted to certain chemical substance).For example, food smell can be with attract insects to food.If food is placed on and adjacent covers the present composition of gas in discharging stink, the smell that is discharged by this food is just not obvious or can not perception to insect so.The present composition also can be used for discharging in the stink and gas, and the smell that is discharged by food just reduces or eliminates like this, so insect does not just attracted on this food.

These powder also are particularly useful for animal-feed.Make and treating processes in, the bacterium that the animal-feed that is used for single abdomen animal such as chicken, pig, cat, dog, rabbit, mouse, mouse etc. often can be infected animal pollutes.If powder of the present invention is made by edible component, comprise edible protein coat, this powder can be in any stage of producing, before transportation or storing feed so, or before using feed, add in the animal-feed, dioxide peroxide can reduce or eliminate the bacterium in this feed like this.Controlled, sustained release powder also can reduce the amount of bacteria in the intestines of these single abdomen animals.

The present composition discharges gas effectively under the general temperature that runs into of above purposes, comprise refrigerating temperature.The composition that discharges dioxide peroxide can for example be used for the refrigeration of packing needs material is carried out disinfection or de-odorised medical treatment supplies, food or other material.The multilayer film that comprises isolation layer also can be used for forming the packing that for example is used for medical supplies or food.Isolation layer is trapped in other that is produced in the packing, for example is used for extending shelf life and prevents in the mould growth of food or strengthen sterilization to medical supplies.

Composition of the present invention can with the United States Patent (USP) 5360609,5631300,5639295,5650446,5668185,5695814,5705092,5707739 that for example is described in people such as Wellinghoff and 5888528 and the moisture-activated gas release composition of pending trial U.S. Patent application series № 08/651876,08/724907,08/858860,08/921357,08/924684 and 09/138219 carry out blend, obtain a kind of moisture and/or energy-activated compositions that is used for those known application of such use and moisture-activated composition.A kind of composition that is used for the controlled and controlled generation of moisture of electromagnetic energy and discharges at least a gas comprises can be by energy-activated catalyzer of electromagnetic energy activatory and at least a negative ion source.This negatively charged ion can with the proton substance reaction that produces when the catalyst activation or can oxidation to produce at least a gas.This negatively charged ion can also with the oxonium ion generated reactive gas.In addition, can have different negatively charged ion (that is, second negative ion source), they can produce at least a gas that first negative ion source discharges that is different from the oxonium ion reaction.Said composition also comprises the sour releasing agent that for example is described in above-mentioned United States Patent (USP) and application.The acid releasing agent is material (that is, with the material that is diffused into the water reaction formation acid in the composition) or its mixture that a kind of acid, a kind of hydrolyzable become acid.Deriving from acid-hydrolyzed oxonium ion diffuses through said composition and produces gas with anionic reactive.If be exposed to electromagnetic energy and moisture, said composition can produce and discharge one or more gas after catalyst activation and negatively charged ion oxidation or reaction.Energy-activated compositions or moisture and energy-activated compositions also can be used in combination with the trapping agent of gas such as ethene and oxygen, are used to strengthen control that biological food is decomposed, reduce or prevent effect.This composition is described in embodiment 13.

Following examples are used to describe the preferred embodiments of the invention and purposes, unless described in the claims, they also are not used in qualification the present invention.

Embodiment 1

Be suspended in titanium dioxide (2 gram, 99.9% rutile (Aldrich Chemical)) in the water and use the 0.1N aqueous sodium hydroxide solution that the pH value of this suspension is adjusted to 8.0.Be placed on this suspension on the glass Petri dish and in dark stink cupboard, evaporate and spend the night to form a kind of white powder.This powder (1.9015 gram) and Textone (2.0798 grams, technical grade (Aldrich Chemical)) are mixed, pour into immediately in 500 milliliters of wide-necked bottles, and monitor with 0-10ppm dioxide peroxide detector.As shown in Figure 2, when this powder does not expose, in initial 22.2 hours of test, do not discharge dioxide peroxide from white powder.But when this powder is exposed to the fluorescence visible light, observe rapid generation dioxide peroxide.

Embodiment 2

With titanium dioxide (0.5101 gram, 99.9% rutile (Aldrich Chemical)) with Textone (0.5084 gram, technical grade (Aldrich Chemical)) mixes a kind of physics powder blend of formation, pour into immediately in 500 milliliters of wide-necked bottles, and monitor with 0-10ppm dioxide peroxide detector.As shown in Figure 3, even be exposed to after the fluorescence visible light 3 hours, do not discharge dioxide peroxide from white powder.Compare with the physical blending thing of embodiment 1, this tests hint, and the physical blending thing can not produce dioxide peroxide, unless there is surface hydroxyl.

Embodiment 3

Titanium dioxide (2 grams, 99.9% rutile (Aldrich Chemical)) is suspended in the water (15 gram).Be placed on this suspension on the glass Petri dish and in dark stink cupboard, evaporate and spend the night to form a kind of white powder.This powder (1.9607 gram) and Textone (2.0157 grams, technical grade (Aldrich Chemical)) are mixed a kind of physics powder blend of formation, pour into immediately in 500 milliliters of wide-necked bottles, and monitor with 0-100ppm dioxide peroxide detector.As shown in Figure 4, in being exposed to initial 6.95 hours processes of fluorescence visible light, discharge dioxide peroxide by white powder.Dioxide peroxide discharges by powder being kept in the dark and suspending at 6.95-23.85 hour.Dioxide peroxide produces by powder being exposed to the fluorescence visible light once more and recovered at 23.85-31.83 hour.At 31.83-47.93 hour, powder is kept producing in the dark and not dioxide peroxide once more.Chlorine dioxide produced when experiment finishes at 47.93 hours once more by powder being exposed to the fluorescence visible light.

Embodiment 4

Be suspended in titanium dioxide (2 gram, 99.9% rutile (Aldrich Chemical)) in the water (11 gram) and be placed on the glass Petri dish.The solution and the stirring that add Textone (2.0606 grams, technical grade (Aldrich Chemical)) and water (7.0411 gram).The pH value of gained suspension is 10-11.Suspension evaporated in dark stink cupboard spend the night, form a kind of white powder that comprises some residual water.This powder is poured in 500 milliliters of wide-necked bottles, and monitored with 0-100ppm dioxide peroxide detector.As shown in Figure 5, when this powder does not expose, do not produce dioxide peroxide from this white powder at initial 14.7 hours that test.But when this powder is exposed to the fluorescence visible light, under alkaline condition, observed carbonic acid gas and produce rapidly at 14.7-89.1 hour.When powder kept in the dark, carbonic acid gas is released in 89.1-94.8 hour to be stopped rapidly, recovered at 94.8-95 hour when being exposed to the fluorescence visible light then.Compare with the physics powder blend of embodiment 3, observe higher chlorine dioxide burst size, because the powdery components contact is tightr above 4 times.

Embodiment 5

With titanium dioxide (35 grams, 99.9% rutile (Aldrich Chemical)) with Textone (35 gram, technical grade (Aldrich Chemical)) and the aqueous solution of water (300 gram) form a kind of suspension, then immediately under 100 ℃ of 200 ℃ of temperature ins and temperature outs, under the dim light condition, carry out spraying drying, form a kind of white powder (36 gram).This powder (2 gram) is poured in 500 milliliters of wide-necked bottles, and monitored with 0-100ppm dioxide peroxide electrochemical sensor.As shown in Figure 6, when this powder is exposed to the fluorescence visible light, in initial 17.2 hours of test, produce and discharge dioxide peroxide from white powder.When powder kept in the dark, gas release was suspended at 17.2-17.7 hour, recovered at 17.7-22.1 hour when this powder is exposed to the fluorescence visible light, suspended once more at 22.1-24 hour when powder keeps in the dark then.

Embodiment 6

With titanium dioxide (88 grams, 99.9% rutile (DuPont R-700)) is suspended in the aqueous solution of water (300 gram) and sodium hydroxide (2 gram), then with Textone (10 grams, technical grade (Aldrich Chemical)) mixes a kind of suspension of formation, then immediately under 120 ℃ of 230 ℃ of temperature ins and temperature outs, under the dim light condition, carry out spraying drying, form a kind of white powder.This powder (1 gram) is poured in 500 milliliters of wide-necked bottles, and monitored with 0-100ppm dioxide peroxide electrochemical sensor.As shown in Figure 7, when this powder is exposed to the fluorescence visible light, in initial 2.75 days of test, produce and discharge dioxide peroxide from white powder.When powder kept in the dark, gas release was suspended at 2.75-2.95 days, recovered at 2.95-3.65 days when this powder is exposed to the fluorescence visible light then.

Use following ratio according to above-mentioned other powder of preparing.Dioxide peroxide discharges from all powder.

NaClO 2(g)	NaOH(g)	TiO 2(g)	TiO 2The source
				10	0.5	89.5	Aldrich
10	1	89	Aldrich
				10	2	88	Aldrich
10	2	88	DuPont R-700 1
				10	2	88	DuPont R-700 2
10	2	88	DuPont Ti- Pure R-706
				10	2	88	Nanophase (Chicago，IL)
10	2	78	Aldrich 3
				10	5	85	Aldrich

¹With suspension filtered and drying but not spraying drying

²Not aging suspension during preparation, aging 1 or 24 hour

³Suspension comprises 10 gram sodium sulfate thinners

Embodiment 7

With titanium dioxide (86 grams, 99.9% rutile (Aldrich Chemical)) is suspended in water (300 gram), sodium hydroxide (2 gram) and Triton X-301  (2 grams, 20% solution from 5 grams) in the aqueous solution, then with Textone (10 grams, technical grade (AldrichChemical)) mixes a kind of suspension of formation, immediately under 120 ℃ of 230 ℃ of temperature ins and temperature outs, under the dim light condition, carry out spraying drying then, form a kind of white powder.This powder (1 gram) is poured in 500 milliliters of wide-necked bottles, and monitored with 0-100ppm dioxide peroxide electrochemical sensor.Dioxide peroxide discharges from powder.

Prepare powder according to the following ratio of above-mentioned use in addition.Notice that suspension comprises TritonX-100  rather than Triton X-301 .Dioxide peroxide discharges from all powder.

NaClO 2(g)	NaOH(g)	Triton X-100 (g)	TiO 2(g)	TiO 2The source
					10	2	2	86	DuPont R-700
10	2	0.5	87.5	DuPont R-700
					10	0.5	0.5	8 9	DuPont R-700
2	0.5	97	0.5	DuPont R-700

Embodiment 8

Titanium dioxide (89.9 gram, 99.9% rutile (Aldrich Chemical)) is suspended in water (300 gram) and water glass, and (0.1 gram is from 0.26 38% solution that restrains; SiO ₂/ Na ₂O ratio=3.22) in the aqueous solution, mix forming a kind of suspension then with Textone (10 gram, technical grade (AldrichChemical)), then immediately under 120 ℃ of 230 ℃ of temperature ins and temperature outs, under the dim light condition, carry out spraying drying, form a kind of white powder.This powder (1 gram) is poured in 500 milliliters of wide-necked bottles, and monitored with 0-100ppm dioxide peroxide electrochemical sensor.Dioxide peroxide discharges from powder.

Titanium dioxide (99.9% rutile (Aldrich Chemical)) is suspended in the aqueous solution of water (300 gram) and Triton X-100 , then with Textone (10 grams, technical grade (Aldrich Chemical)) mixes a kind of suspension of formation, immediately according to the above-mentioned spraying drying of carrying out, form following powder then.Dioxide peroxide discharges from all powder.Fig. 9 has provided the release profile of 89 gram titanium dioxide/0.5 gram silicate (2.5 ratio).

Silicate (g)	TiO 2(g)	TiO 2The source	Triton X-100 (g)
				(0.5 2.5 ratio)	87.5	DuPont R-700	2
(0.5 3.2 ratio)	89	DuPont R-700	0.5
				(0.5 2.5 ratio)	89	DuPont R-700	0.5
(0.2 3.2 ratio)	89.3	DuPont R-700	0.5
				(0.2 2.5 ratio)	89.3	DuPont R-700	0.5

Prepare three kinds of other powder according to the method described above, wherein the amount of titanium dioxide and water glass is respectively 89.5 grams, 88 grams and 85 grams and 0.5 gram, 2 grams and 5 grams.In Fig. 8, the release profile of these three kinds of powder and the powder that does not contain silicate of Fig. 7 are compared.The dioxide peroxide rate of release descends along with the increase of powder mesosilicic acid sodium content.

Use following ratio according to above-mentioned other powder of preparing.Dioxide peroxide discharges from all powder.

NaClO 2(g)	Silicate (g)	TiO 2(g)	TiO 2The source
				10	10 (3.2 ratios)	80	Aldrich
10	(0.5 3.2 ratio)	89.5	DuPont R-700
				10	(0.5 2.5 ratio)	89.5	DuPont R-700

Embodiment 9

According to the following ratio of listing, titanium dioxide (Aldrich Chemical) is suspended in mixes a kind of suspension of formation in water (300 gram) solution and with Textone (Aldrich Chemical), then immediately under 120 ℃ of 230 ℃ of temperature ins and temperature outs, under the dim light condition, carry out spraying drying, form a kind of white powder.This powder (1 gram) is poured in 500 milliliters of wide-necked bottles, and monitored with 0-100ppm dioxide peroxide electrochemical sensor.Dioxide peroxide discharges from powder.

NaClO 2(g)	TiO 2(g)
		50	50
20	80
		10	90
10	80 1
		5	95

¹Suspension comprises 10 gram sodium sulfate thinners

According to the above-mentioned powder of preparing, wherein suspension comprises zinc oxide (90 grams in addition; Technical grade).As shown in figure 10, dioxide peroxide produces and release from this powder when exposure.

According to the above-mentioned powder of preparing, wherein suspension comprises titanium dioxide (90 grams in addition; 99.9% rutile (Aldrich Chemical)) and 10 gram yellow soda ash (Aldrich Chemical), S-WATs (Aldrich Chemical) or Sodium Nitrite (Aldrich Chemical) with release of carbon dioxide, sulfurous gas and nitric oxide respectively.As shown in figure 11, nitrogen peroxide produces and discharges from powder when exposure.

Embodiment 10

Pellet forms:Using melt index is 2 linear low density polyethylene (LLDPE) resin (being made by Rexene), under the concentration of 20% powder and 80% resin, the spray-dried powders compounding of embodiment 5 is become pellet.In making the pellet process, use low-level incandescent lighting.Pellet is stored in aluminium foil/plastic lamination container and does not expose with protection.

Film forming: with melt index is that 2 Rexene LLDPE resin (50% dilution) is with the pellet blown film.That is, the gained film comprises embodiment 5 powder of about 10% weight.In making the pellet process, use low-level incandescent lighting.Pellet is stored in aluminium foil/plastic lamination container and does not expose with protection.

The photoactivation of film under wet condition:4.3 gram membrane samples are placed in 500 milliliters of wide-necked bottles (comprising that 0.5 milliliter of saturated ammonium sulphate solution is to produce 80% relative humidity), wherein 0-10ppm dioxide peroxide electrochemical detector are connected to and cover, and cover about 2.85 days to get rid of light with aluminium foil.In this process, do not produce dioxide peroxide.With light-illuminating sample in the fluorescent ventricle on every side, produce high-load dioxide peroxide as shown in figure 12 immediately.Signal raises slowly in dark process, and this is the artefact of detector hydration but not produces dioxide peroxide because before the detector under the low humidity condition life-time service.

Figure 13 has provided near the dioxide peroxide rate of release illumination.In film exposure 15 minutes, chlorine dioxide concentration surpasses the detector limit.In 1 hour, film has discharged the chlorine dioxide of a hundreds of ppm.

Notice that in whole should the experiment, dioxide peroxide discharges to be tested under the marginal illumination condition.Titanium dioxide is a kind of ultraviolet thinner.The used sample wide-necked bottle of whole experiment is a soft glass, and it absorbs about 95% incident uv.Fluorescent ventricle's intraoral illumination has some UV-light, but incandescence mainly provides visible light.Therefore, this experiment has provided at the suitable dioxide peroxide that is lower than under the optimal illumination condition and has discharged.

Film is along with the photoactivation of light round-robin:1 gram membrane sample is placed in 500 milliliters of wide-necked bottles, wherein 0-10ppm dioxide peroxide electrochemical detector is connected to and covers, and cover about 10 minutes to get rid of light with aluminium foil.In this process, do not produce dioxide peroxide.About 10-30 minute with light-illuminating sample in the fluorescent ventricle on every side, produce dioxide peroxide immediately.About 30 minutes to 2.6 hours, about 2.8-3.7 hour, about 4.1-4.9 hour and covered this film with paper tinsel in about 6.6-23.2 hour, in this process, do not produce dioxide peroxide as shown in figure 14.About 2.8-3 hour, 3.7-4.1 hour, 4.9-6.6 hour and 23.2-26 hour, film is exposed to room light and produces dioxide peroxide.As can be seen, be exposed to dark (during 6.6-23.2 hour) for a long time afterwards, the higher rate of release when initial discharges dioxide peroxide to this film to be higher than.

Film circulates along with light and the photoactivation of light leak greatly:1 gram membrane sample is placed in 500 milliliters of wide-necked bottles, wherein 0-10ppm dioxide peroxide electrochemical detector is connected to and covers, this lid has a hole (about 1 centimetre) as leaky hole, and covers about 10 minutes to get rid of light with aluminium foil.In this process, do not produce dioxide peroxide.About 10-31 minute with light-illuminating sample in the fluorescent ventricle on every side, produce dioxide peroxide immediately.Cover this film at about 31 minutes to 1.1 hours and about 1.7-2.6 hour with paper tinsel, shown in Fig. 15, do not producing dioxide peroxide in this process.At about 1.1-1.7 hour and 2.6-3.4 hour, film is exposed to room light and produces dioxide peroxide.

Chlorine detects:Membrane sample (1 gram) is placed on is furnished with barrier film but not in 500 milliliters of wide-necked bottles of electrochemical detector.Fused silica mass spectrograph sampling circuit is inserted in this wide-necked bottle, along with sample is placed on the about 1 foot far away soft incandescence bulb irradiation of distance, the concentration of monitoring dioxide peroxide and chlorine.As shown in figure 16, detect the very chlorine of low levels (under mass spectrometric detection limit).Chlorine and ozone produce under intense light source, cause the dioxide peroxide photolysis.Using not too strong light source, during as soft incandescence, do not detect chlorine and ozone.

Repeat this experiment, wherein the sample wide-necked bottle is refrigerated down but not test at room temperature at 5 ℃, test the temperature sensitivity of this sample.Equally, detect the chlorine (referring to Figure 17) of low levels.At about 2.3-3.3 hour, turn off light source, be expressed as the shade line in the accompanying drawing.This film has stopped producing dioxide peroxide, but finds that the rate of disappearance of dioxide peroxide descends in the dark.This sample at room temperature and when refrigeration discharges dioxide peroxide effectively, and the temperature-insensitive of said composition has been described.

Embodiment 11

Reduce generation too early and discharge under the low incandescence condition of gas as far as possible, under full concentration, with the pellet casting film forming of embodiment 10.The gained film comprises embodiment 5 powder of about 20% weight like this.This film is stored in aluminium foil/plastic lamination container and does not expose with protection.When exposure, chlorine dioxide produces in film.

Under light conditions, be that 2 Rexene LLDPE resin (50% dilution) with pellet casting film forming, forms a kind of film that comprises embodiment 5 powder of about 10% weight with melt index.This film is stored in aluminium foil/plastic lamination container and does not expose with protection.When exposure, chlorine dioxide produces in film.

In addition under light conditions, with UV stablizer, Tinunin ^TM783 FDL are (based on 0.2% weight of melt gross weight; Ciba Geigy) casting pellet under full concentration forms a kind of film that comprises embodiment 5 powder of about 19.96% weight.This film is stored in aluminium foil/plastic lamination container and does not expose with protection.When exposure, chlorine dioxide produces in film.

In addition under light conditions, with UV stablizer, Tinunin ^TM783 FDL are (based on 1% weight of melt gross weight; Ciba Geigy) casting pellet under full concentration forms a kind of film that comprises embodiment 5 powder of about 19.96% weight.This film is stored in aluminium foil/plastic lamination container and does not expose with protection.When exposure, chlorine dioxide produces in film.Figure 18 has compared the dioxide peroxide release of the film that does not contain the UV stablizer and has comprised the film of 0.2% weight or 1.0% weight UV stablizer.

Embodiment 12

Suspension passes through polymethylmethacrylate (PMMA; 25 grams) be dissolved in methylethylketone (MEK; 75 grams) and under agitation add the powder (25 gram) of embodiment 5 subsequently and make.Gained suspension comprises the powder of 20% weight, the PMMA of 20% weight and the MEK of 60% weight.Be placed on a small amount of suspension in the testing tube and be exposed to fluorescence.The indicator strips that comprises potassiumiodide becomes purple in fluorescence exposes 5 minutes, show to have chlorine dioxide.This suspension is fit to coating finger or toe to delay, prevent, to suppress or to control fungal growth.

Embodiment 13

Pellet forms: with Microsphere ^TM(derive from BernardTechnologies, Inc.of Chicago is IL) with the resin (Microsphere of 20% weight for 2500 moisture-activated powder ^TMThe new LDPE (film grade) UC 9820 of 2500 powder, 72% weight, 8% linear low density polyethylene UC 1537) carry out blend and granulation.These pellets and embodiment 10 pellets are carried out blend according to 50: 50 ratio.In making the pellet process, use low-level incandescent lighting.Pellet is stored in aluminium foil/plastic lamination container and does not expose with protection.

Film forming: the film that the pellet casting is become 10 mil thick.The gained film comprises the photoactivation powder of 10% weight and the moisture-activated powder of 10% weight.In making the pellet process, use low-level incandescent lighting.Pellet is stored in aluminium foil/plastic lamination container and does not expose with protection.

The photoactivation of film under wet condition:3.2 gram membrane samples are placed in 500 milliliters of wide-necked bottles (comprising that 0.5 milliliter of saturated ammonium sulphate solution is to produce 80% relative humidity), wherein 0-10ppm dioxide peroxide electrochemical detector are connected to and cover.This film does not discharge dioxide peroxide in several minutes.As shown in figure 19, in the time of 5, with fluorescence indoor light several minutes around the sample shielding.The generation of dioxide peroxide and discharging because of of short duration unglazed the minimizing shows that this film produces by light and moisture-activated and discharges dioxide peroxide.

Although the present invention can carry out various improvement and alternative transforms, its particular has provided by the example in the accompanying drawing and has obtained in this article describing in detail.But should be appreciated that this does not also mean that and limit the invention to particular forms disclosed, on the contrary, the present invention includes and fall into the purport of the present invention that is indicated in the appended claims and all improvement, equivalent and the surrogate in the scope.

Claims (10)

1. composition that is used for the controlled and controlled generation of moisture of electromagnetic energy and discharges at least a gas comprises:

Can be by the energy-activated catalyzer of electromagnetic energy activatory,

Can with the proton substance reaction that produces when the catalyst activation or can oxidation with the chlorite, nitrite anions or the superoxide anion that produce at least a gas and

The acid releasing agent,

Said composition can produce and release dioxide peroxide, nitrogen oxide or ozone after the hydrolysis of the activation of catalyzer, sour releasing agent and anionic oxidation or reaction when being exposed to electromagnetic energy and moisture.

2. one kind in the method that delays, kills, prevents on the surface of material, in material or in surrounding the atmosphere of this material or controlling microbial is polluted, comprise, this material is placed on the neighbour in the composition place of claim 1, and said composition is exposed to electromagnetic energy to produce from said composition and to discharge at least a thing gas of killing livestock to the atmosphere of surrounding this material.

3. one kind delays, prevents, suppresses or control biochemical method of decomposing on the surface of material or in material, comprise, this material is placed on the neighbour in the composition place of claim 1, and said composition is exposed to electromagnetic energy to produce from said composition and to discharge at least a biochemical inhibition gas that decomposes to the atmosphere of this material of encirclement.

4. the method that control material is breathed comprises, this material is placed on the neighbour in the composition place of claim 1, and said composition is exposed to electromagnetic energy to produce from said composition and to discharge at least a respiratory control gas to the atmosphere of surrounding this material.

5. the atmosphere to material surface or encirclement material is carried out deodorizing or material is increased bright method, comprise, this material is placed on the neighbour in the composition place of claim 1, and said composition is exposed to electromagnetic energy to produce from said composition and to discharge at least a odour that removes to the atmosphere of surrounding this material.

6. one kind delays, prevents, suppresses or control the method that organism attracts the chemotactic of material, comprise, this material is placed on adjacent to the composition place of claim 1, and with said composition be exposed to electromagnetic energy with produce from said composition and discharge at least a stink hide gas or the stink and gas in the atmosphere of surrounding this material.

7. one kind delays, prevents or the method for the biological pollution of controlled atmosphere, comprises, the composition of claim 1 is exposed to electromagnetic energy to produce from said composition and to discharge at least a Purge gas to the atmosphere of surrounding said composition.

8. one kind delays, prevents or the method for the biological pollution of control material, comprise, this material is placed on the neighbour in the composition place of claim 1, and said composition is exposed to electromagnetic energy to produce from said composition and to discharge at least a Purge gas to the atmosphere of surrounding this material.

9. one kind is delaying, is killing, is preventing on the surface of material, in material or in the atmosphere of this material of encirclement or the controlling microbial pollution, or delay, prevent, suppress or control biochemistry and decompose, material surface or material surrounding atmosphere are carried out deodorizing, material is increased aquatic foods, or delay, prevent, suppress or control the method that organism attracts the chemotactic of material, comprise, this material is placed on the neighbour in the composition place of claim 1, and said composition is exposed to electromagnetic energy to produce from said composition and to discharge chlorine dioxide to the atmosphere of surrounding this material.

10. complex body that is used for the controlled generation of electromagnetic energy and discharges at least a gas comprises:

Gas produces layer, comprise can by the energy-activated catalyzer of electromagnetic energy activatory and can oxidation or reaction produce chlorite, nitrite anions or the superoxide anion of at least a gas; With

Adjacent produce the isolation layer on the surface of layer in described gas, described isolation layer can be transferred to electromagnetic energy that gas produces layer and be impermeable or semi-transparent mistake to described gas;

Described gas produces layer and can produce and release dioxide peroxide, nitrogen oxide or ozone after the activation of catalyzer and anionic oxidation or reaction when being exposed to electromagnetic energy.

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