CN1925755B - Using carbon dioxide regulators to extend the shelf life of plastic packaging - Google Patents

Abstract

A method for replenishing carbon dioxide gas in a carbonated beverage container where a carbon dioxide regulator releases carbon dioxide at a rate approximately equal to the rate of carbon dioxide loss from said container. Also disclosed is packaging system for maintaining a consistent pressure of a carbonated beverage comprising a closure, a plastic container, and a carbon dioxide regulator. Also disclosed is a method for making a packaging system for maintaining a consistent pressure in a carbonated beverage comprising overmolding a preform around an assembly for a carbon dioxide regulator, or blending a carbon dioxide regulator into the plastic material used to form the body of a container for said carbonated beverage. Also disclosed is carbon dioxide regulator composition for replenishing carbon dioxide gas in a carbonated beverage container comprising polymeric carbonates, organic carbonates, or materials that absorb and subsequently release carbon dioxide.

Description

Use carbon dioxide regulators to prolong the plastics packed preservation life-span

The cross reference of related application

The application requires the priority of following patent application: the temporary patent application 60/548 that on February 27th, 2004 submitted to, the temporary patent application of " the using carbon dioxide regulators to prolong the plastics packed preservation life-span " by name of submitting in the temporary patent application 60/628,737 that on November 17th, 286 and 2004 submitted to and on February 24th, 2005.

Background of invention

Needing ease for operation, low weight and be difficult in the bottled drink field of brokenness, plastics and canister have replaced glass.Plastics package, particularly PETG (PET) bottle has been widely used in packing the carbonated product as beer, soft drink, distilled water and some dairy products.These products all have optimum carbonating or carbon dioxide (to be known as " CO herein sometimes in its packing separately ₂") pressure, to keep its optimum quality.In conventional plastics package, be difficult in long-time CO ₂Pressure remains on this optimal level.

CO ₂Can permeate plastics package, thereby pressure of the inside of a bottle is reduced in time.Finally, after a certain amount of carbonic acid gas loss, this product will no longer be suitable for using, and this is usually expressed as flavour or obvious and unacceptable change takes place taste.The time point that this situation takes place has determined the preservation life-span of packing usually.CO ₂Temperature when loss speed depends on the weight of packing and size and its storage to a great extent.Lighter, thinner bottle can lose carbonic acid gas quickly and can not keep high interior pressure, thereby the shorter preservation life-span is arranged.When plastic bottle diminished, the relative speed of carbonic acid gas loss became faster.Infiltration is faster under the higher temperature, and this has shortened the preservation life-span and made under hot weather and has stored soda and still keep reasonably preserving the life-span difficulty that becomes in plastic containers.Longlyer preserve the life-span, lighter, more cheap plastic bottle and need not to cool off promptly more muchly that the ability of storage bottle has a lot of economic advantages.

The problems referred to above have been adopted the whole bag of tricks.A kind of short-cut method that prolongs soda is to add extra carbon dioxide when loading.This method generally is used for carbonated soft drink and beer, but because percarbonic acidization is obstructed its effect to the influence of product quality and the negative effect to the bottle physical property that causes thus.The fine difference of pressing in the packing all can cause the obvious difference of the foaming quality of beverage.The CO of dissolving ₂Also can influence taste.These accurate requirements are different because of product.

Percarbonic acidization also can be obstructed because of the pressure limit of packing.Feasible way is to make bottle more withstand voltage, but this need use other material or need more outstanding more high performance plastics in bottle structure.

Can be by reducing CO ₂Infiltration rate and keep carbonating.This generally include to the PET bottle use second barrier coat, use, more difficult infiltration more expensive than PET polymer, make the bottle structure of multilayer or be used in combination said method.The method costliness that these manufacture methods are used in all producing than common polyester bottles many, and usually produce the new particularly problem of recirculation.

In the prior art, the existing preservation life-span that the carbon dioxide generating material is used to prolong soda.Molecular sieve with carbon dioxide treatment is used to soda by the carbon dioxide of institute's combination and the reaction of water.

U.S. Patent application 2004/0242746 A1 that authorizes the United States Patent (USP) 6,852,783 of Hekal and authorize Freedman etc. has recorded and narrated a kind of CO ₂Discharge composition, said composition can be impregnated in or insert in the packing of soda.The composition of these lists of references has been recorded and narrated and will have been sneaked into to thermoplastic as carbon dioxide source above the inorganic carbonate of 25% weight.The 32g PET bottle of having filled 25% sodium acid carbonate has the potentiality that discharge the 4.5g carbon dioxide.This amount that needs in approximately using than PET beer bottle exceeds ten times, thereby may cause the dangerous supercharging of packing.Thereby and these structure release of carbon dioxide too fast can't be in long-time adjusting pressure, if particularly described structure is under the situation about being made by PETG, and compare all the more so by having the structure that the polyethylene of low humidity impervious speed more makes.Have been found that so high loadings is not suitable for using, because it has the possibility that discharges too much carbon dioxide in packing.

Summary of the invention

The present invention relates in carbonated beverage container, replenish the method for carbon dioxide.This method comprises in container for drink or in the lid of container inserts carbon dioxide regulators, and discharges carbon dioxide by chemical reaction from described carbon dioxide regulators.The rate of release of carbon dioxide is adjusted to and approximates the speed of carbon dioxide from described container loss.

The invention still further relates to the method for in carbonated beverage container, replenishing carbon dioxide.This method comprise in container or the lid of container in insert carbon dioxide regulators, the rate adaptation that will discharge carbon dioxide subsequently from described carbon dioxide regulators is to approximating the speed of carbon dioxide from described container loss.

The invention still further relates to the packaging system of the pressure consistency that is used to keep soda, it comprises lid, plastic containers and carbon dioxide regulators.

The invention still further relates to the method for the packaging system of making the pressure consistency be used to keep soda, this method is included in molded again (overmolding) performing member (prerorm) around the assembly that is used for carbon dioxide regulators.

The invention still further relates to the method for the packaging system of making the pressure consistency be used to keep soda, this method comprises sneaks into carbon dioxide regulators in the plastic material that is used to form described carbonated beverage container body.

The invention still further relates to the carbon dioxide regulators composition that is used for replenishing at carbonated beverage container carbon dioxide, said composition comprises independent Merlon, independent organic carbonate or its combination.

The invention still further relates to the carbon dioxide regulators composition that is used for replenishing at carbonated beverage container carbon dioxide, said composition comprises and absorbs and the material of release of carbon dioxide subsequently.

" soda " of Shi Yonging is a kind of aqueous solution herein, and wherein with regard to carbonated soft drink, the carbon dioxide dissolved gas flow is about 2 to about 5 volume CO ₂/ volume H ₂O, preferred about 3.3 to about 4.2 volume CO ₂/ volume H ₂O, with regard to beer, the carbon dioxide dissolved gas flow is about 2.7 to about 3.3 volume CO ₂/ volume H ₂O.

" carbon dioxide regulators " of Shi Yonging is a kind of composition herein, said composition or slowly discharge CO by controlled chemical reaction process ₂, or by physical process absorption and release CO ₂, wherein the speed of this release approximates the CO of packing greatly ₂Loss speed, thus make the pressure carbon dioxide in the packing keep more constant within a certain period of time.

Appropriate C O ₂Conditioning agent comprises: Merlon, cyclic organic carbonates, organic carbonate, for example alkyl carbonate, ethylene carbonate, propylene carbonate, poly (propylene carbonate), ethylene carbonate, carbonic acid glyceride, butylene carbonate, diethyl carbonate, coke acetoacetic ester, coke acid methyl esters, dialkyl dicarbonate or its mixture; Inorganic carbonate is as sodium acid carbonate, ferrous carbonate, calcium carbonate, lithium carbonate and its mixture; Molecular sieve, zeolite, activated carbon, silica gel and Coordination Polymers, metal organic frame (" MOF ' s ") and with netted (isorecticular) metal organic frame (" IRMOF ' s ").CO ₂The use amount of conditioning agent depends on the burst size of required carbon dioxide, and the burst size of required carbon dioxide depends on the holding time passage of container the amount of carbon dioxide of loss from container.

Can place CO ₂The bottle zone of conditioning agent includes but not limited to: bottle cap, bottleneck/bottleneck, the bottle end or sneak in the plastic resin that constitutes bottle.

The accompanying drawing summary

Fig. 1 has described carbon dioxide regulators to PET beer bottle Effect on Performance.

Fig. 2 has described carbon dioxide regulators to carbonated soft drink bottle Effect on Performance.

Fig. 3 has described the carbon dioxide regulators lid that has dish-shaped insert and liner.

Fig. 4 has described the carbon dioxide regulators assembly that has dish and liner.

Fig. 5 has described and has had the carbon dioxide regulators lid that inserts plug-assembly.

Fig. 6 has described carbon dioxide regulators bottleneck plug-in package.

Fig. 7 has described organic carbonate by the carbon dioxide output of steam activation.

Fig. 8 has described the influence of prebagged material to the carbon dioxide rate of release.

Fig. 9 has described the carbon dioxide loss by the pressure of the inside of a bottle performance.

Figure 10 has described the presaturation of carbon dioxide in 20 ounces of bottles.

Detailed Description Of The Invention

Many compositions can be used as carbon dioxide regulators. These compositions are divided into two classes. The first kind is by controlled chemical reaction generation or the composition of release of carbon dioxide. These compositions comprise: a) such as the polymer of aliphatic polyketones, produce carbon dioxide as the dehydration accessory substance when itself and oxygen reaction, perhaps when hydrolysis, especially produce the organic of release of carbon dioxide and DIC acid group in the presence of acid. Catalyst, adhesive and other additive can be with these material combinations, with auxiliary control release of carbonate dioxide process; And b) organic carbonate such as alkyl carbonate, ethylene carbonate, propylene carbonate, poly (propylene carbonate), ethylene carbonate, carbonic acid glyceride, butylene carbonate, diethyl carbonate, coke acetoacetic ester, coke acid methyl esters, cyclic carbonate acrylate such as trimethylolpropane propylene carbonate acid esters, and dialkyl dicarbonate, it discharges carbon dioxide in when hydrolysis, can by with strengthen this hydrolysis such as the acid reaction of citric acid or phosphoric acid.

Equations of The Second Kind is the sorbent combinations thing, and these composition storage carbon dioxide enter release of carbonate dioxide in the container when carbon dioxide loses from packing subsequently again. These compositions comprise: sorbent such as silica gel; Molecular sieve, zeolite, clay, activated alumina, activated carbon and Coordination Polymers, metal organic frame or title " MOF ' s " and with net metal organic frame or title " IRMOF ' s ", described " MOF ' s " and " IRMOF ' s " be and metal oxide like the zeolites and organic acid crystalline material. These materials can be processed to various apertures and various carbon dioxide storage capacity.

Above-mentioned various carbon dioxide generate agent and can be sneaked in the polymer of making container or lid. It also can layer form be present in multilayer lid, liner or the bottle. Perhaps, they can be molded into insert or dish, and described insert or dish can be placed in the bottle cap top or be placed in the insert that can insert the container finish zone. Fig. 3-6 shows like this some designs.

Adopting moisture adjusting CO₂In the system of rate of release, this carbon dioxide regulators can mix with suitable polymer encapsulated or with it, and the selection of polymer depends on that it is to moisture and CO₂Permeability. By selecting suitably encapsulation or barrier polymers, the speed of moisture infiltration can be used to control CO₂Rate of release and with the packing CO₂Loss speed is complementary, thereby obtains to make in a period of time CO₂Interior pressure keeps near constant packing. Be known as during this period of time the adjusting phase.

Regulate CO at employing oxygen₂In the system of rate of release, this carbon dioxide regulators can encapsulate with suitable polymer or mix with it, and its oxygen and CO depended in the selection of polymer₂Permeability. Same by suitable selection, CO₂Generating rate can be adjusted to and the CO that packs₂Loss speed is complementary, and makes CO in a period of time₂Interior pressure keeps near constant.

When by CO₂When sorbing material makes carbon dioxide regulators, can will prolong by percarbonic acid when loading and preserve required extra CO of life-span₂Mix. This packing can be used the accurately required CO of amount₂Come percarbonic acid, this consumption is based on packing increase, adjusting time and the CO in desired preservation life-span₂Permeability. This CO₂Regulating material must be because of too much CO₂Cause before these too much CO of quick adsorption of packing distortion₂ This absorption should be in about six hours, preferably took place in about one hour. This CO₂After the conditioning agent should with than carbon dioxide from the speed of packing loss lower or preferably approximately the speed identical with it with the release of carbonate dioxide of absorption. This can guarantee to keep all even stable CO₂Interior pressure. The performance of particular adjustments agent composition can be by suitable drying, flood and create conditions and obtain optimization, and these methods all are well-known to those skilled in the art. Preferably the volume with carbon dioxide regulators minimizes, thereby the space of packing can be utilized effectively.

Perhaps, carbon dioxide regulators can be inserted CO₂Gaseous environment makes its absorption and stores enough CO₂Gas, thus CO used₂Pre-filled carbon dioxide regulators is so that substitute the from container CO of loss in the normal use of container₂。

Carbon dioxide regulators can be incorporated in the packing with any method. These methods include but not limited to: or be placed in the cuvette or as the dish that makes this conditioning agent put into lid. These are shown in accompanying drawing 3-5. These designs have several parts: lid, carbon dioxide regulators material and carrying carbon dioxide regulators also can be with itself and the separated liner of package contents or glass materials. Gasket material can be designed to the CO of auxiliary control carbon dioxide regulators material₂Loss speed, method is directly to control CO₂Infiltration rate or control activator can contact the speed of carbon dioxide regulators. Water and steam can be as the activator in many systems. The amount of carbon dioxide regulators can change with the needs of packing. For the situation in a small amount of raising preservation life-span, thin insert can be inserted in the lid. To improve to a greater degree the situation of preserving the life-span, can use cup or plug-cover design so that the great amount of carbon dioxide conditioning agent obtains using for the more carbon dioxide regulators of needs.

Can after making carbon dioxide regulators, thereby being inserted a bottle interior correct position, matrix band realize carbon dioxide regulators is inserted in the bottle. This as shown in Figure 6. A kind of method is in blowing or blowing is placed in short tubular piece in the groove of bottleneck drape forming afterwards. Another kind method can be mold-formed bottle performing member again around the carbon dioxide regulators assembly in the following way: assembly is placed on the centrepin of conventional injection mold, uses afterwards as the polymer of PET carries out molded to performing member on every side at this assembly again. Can adopt afterwards the performing member that conventional equipment will contain the carbon dioxide regulators assembly to blow out bottle. Another kind of idea is to use stretching rod that the conditioning agent assembly is placed bottle in blowing.

This carbon dioxide regulators also can be sneaked in the plastics that are used to form package body or lid. Use subsequently conventional equipment that the performing member that this contains the carbon dioxide regulators assembly is blown out bottle. For such system, to packing when being loaded carbon dioxide regulators just aobvious activity be more favourable.

Also the form of this carbon dioxide regulators with layer can be added in the multilayer manufacturing part, it can be used as the layer of bottle, the layer of lid or the layer of liner. Can make this layer by the common manufacturing technology of multilayer extrusion method and this area of any routine, described manufacturing technology comprises that multilayer manufacturing, multilayer film are extruded, coating and lamination. The number of plies in the final packaging formed body can be two to ten layers, preferred three to five layers.

Can by with film lamination, apply this carbon dioxide regulators assembly and maybe this carbon dioxide regulators sneaked into another kind of material, particularly sneaked in the plastics, thereby further control the rate of release of carbon dioxide regulators from carbonic acid gas.This also can conveniently manufacture the form that the present invention uses that is suitable for carbon dioxide regulators.A kind of method comprises sneaks into the carbon dioxide regulators material in the polymer that is used to form cap packing or the carbon dioxide regulators material is sneaked into the material that is used for making lid itself.

Molecular sieve is preferred carbon dioxide regulators of the present invention.Pure, unpressed molecular sieve has the absorption high levels of CO ₂Ability.The molecular sieve of 13X absorbs the CO of its 18% weight approximately under bottle pressure ₂Therefore, for for 12 ounces of carbonated soft drink bottles of carbonating to 4.0 volume, need the CO of about 0.525g ₂Gas is to substitute from the CO of packing loss ₂Thereby, make the preservation life-span become twice.Suitable molecular sieve as carbon dioxide regulators includes but not limited to: common general knowledge is the aluminosilicate of 13X, 3A, 4A and 5A sieve, faujasite and borosilicate sieve.These materials can be by the ion-exchange modification changing its physical property, and can same filler, adhesive and other processing aids combine.

Another group carbon dioxide regulators is Coordination Polymers, metal organic frame (" MOF ' s ") and with net metal organic frame (" IRMOF ' s ").Thereby these materials are to form the polymer architecture that the open type loose structure makes by metal and organometallic reagent with the organic spacer molecular reaction.Anyly make and can adsorb with in the relevant high porosity lattice system of release of carbon dioxide all should be included in by this reaction.

Another group carbon dioxide regulators comprises organic and inorganic carbonate.These materials form carbon dioxide with the water reaction, especially when acid catalyst exists.Thereby these materials being sneaked among the PET and load this with acidic beverages and pack and make its activation, is a preferred embodiment of the present invention.Suitable inorganic carbonate comprises sodium acid carbonate, calcium carbonate and ferrous carbonate.Suitable Merlon comprises the cyclic carbonate ester copolymer, as poly-(vinyl alcohol) cyclic carbonate and poly-cyclic carbonate acrylate, perhaps linear aliphatic carbonate polymer.Should poly-(vinyl alcohol) cyclic carbonate be that catalytic reaction by polyvinyl alcohol and diethyl carbonate makes.Poly-cyclic carbonate acrylate can make the acrylate monomer polymerization of trimethylolpropane carbonic ester, and this monomer is by 2-ethyl-2 (methylol)-1, and the catalytic reaction between ammediol (trimethyl propane) and the diethyl carbonate makes.

Another group carbon dioxide regulators is the polymer that oxidation forms carbon dioxide.An example of these polymer is aliphatic polyketones, and this example comprises the polymer that ethene and/or propylene and reaction of carbon monoxide make.

To optimizing one of important parameters of the present invention is to make CO ₂CO in the source ₂The density maximization.Per unit volume CO ₂The CO of molal quantity ₂Source density is high more, then can be with many more CO ₂Be incorporated in the packing and preserve the life-span, make CO simultaneously to prolong ₂The volume that the source occupies minimizes.Various materials and its CO ₂Density is as shown in table 1 below.

Table 1

The carbon dioxide source concentration of material

		Effective density	CO 2Density
							g/cc	g/cc
Solid, CO 2
					Temperature=-80 ℃		1.565	1.565
Liquid, CO 2
					Temperature=0 ℃, vapour pressure=490 pound/square inch		0.929	0.929
Celsius temperature=25, vapour pressure=917 pound/square inch		0.713	0.713
					Gaseous state, CO 2
Temperature=0 ℃, pressure=44.07 pound/square inch		0.008	0.008
					Sorbent
Absorption: 0.8g/gIRMOF-1@-77C		0.620	0.496

Absorption: 0.18g/g 13X compression Fen Zishai @22C		0.766	0.139
					Absorption: the amorphous PET@22C of 0.022g/g, 20 crust		1.335	0.030
					The stoichiometry pairing				Ionization
Inorganic carbonate	Acid
					Sodium acid carbonate, NaHCO 3	Ascorbic acid, C 6H 8O 6	1.797	0.304	Single
Sodium acid carbonate, NaHCO 3	Benzoic acid C 7H 6O 2	1.578	0.337	Single
					Sodium acid carbonate, NaHCO 3	Citric acid C 6H 8O 7	1.696	0.270	Single
Sodium acid carbonate, NaHCO 3	Fumaric acid C 4H 4O 4	1.833	0.403	Single
					Sodium acid carbonate, NaHCO 3	Maleic acid C 4H 4O 4	1.799	0.396	Single
Sodium acid carbonate, NaHCO 3	Oxalic acid C 2H 2O 4	1.836	0.384	Single
					Sodium acid carbonate, NaHCO 3	Butanedioic acid C 4H 6O 4	1.693	0.369	Single
Sodium acid carbonate, NaHCO 3	Terephthalic acids C 8H 6O 4	1.688	0.297	Single
					Superpower Alka Seltzer	Citric acid, non-stoichiometric	1.574	0.121	Single
Ferrous carbonate (divalence), CFeO 3	Citric acid, C 6H 8O 7	2.040	0.275	Single
					Ferrous carbonate (divalence), CFeO 3	Fumaric acid, C 4H 4O 4	2.353	0.414	Single

Lithium carbonate, Li 2CO 3	Citric acid, C 6H 8O 7	1.667	0.276	Single
					Saleratus, KHCO 3	Citric acid, C 6H 8O 7	1.712	0.258	Single
Sodium acid carbonate, NaHCO 3	Citric acid, C 6H 8O 7	1.792	0.438	Two
					Sodium acid carbonate, NaHCO 3	Fumaric acid, C 4H 4O 4	1.928	0.597	Two
Calcium carbonate (calcite), CaCO 3	Citric acid, C 6H 8O 7	1.714	0.301	Two
					Calcium carbonate (calcite), CaCO 3	The DL-malic acid	1.828	0.418	Two
Calcium carbonate (calcite), CaCO 3	Dl-tartaric acid, C 4H 6O 6	1.886	0.398	Two
					Calcium carbonate (calcite), CaCO 3	Fumaric acid, C 4H 4O 4	1.885	0.476	Two
Dolomite, CaOMgO2CO 2	Citric acid, C 6H 8O 7	1.815	0.28	Two
					Dolomite, CaOMgO2CO 2	Fumaric acid, C 4H 4O 4	2.020	0.427	Two
					Organic carbonate				Hydration
Ethylene carbonate, C 3H 4O 3		1.344	0.671	Single
					Propylene carbonate, C 4H 6O 3		1.204	0.519	Single

Butylene carbonate, C 5H 8O 3		1.146	0.434	Single
					Carbonic acid glyceride, C 4H 6O 4		1.390	0.518	Single
Vinylene carbonate, C 3H 2O 3		1.353	0.692	Single
					Pyrocarbonic acid diethyl ester, C 6H 10O 5		1.122	0.304	Single

Pyrocarbonic acid diethyl ester, C 4H 6O 5		1.122	0.609	Two
					The coke dimethyl phthalate, C 4H 6O 5		1.250	0.410	Single
The coke dimethyl phthalate, C 4H 6O 5		1.250	0.820	Two
					Diethyl carbonate, C 5H 10O 3		0.976	0.364	Single

Another challenge is to regulate CO ₂From CO ₂The release in source makes it usually corresponding to the CO from the packing loss ₂Speed.Can be by selecting CO ₂Source, control CO ₂The activation of release reaction or by selecting suitable barrier film, coating or film with CO ₂Source and beverage separate, thereby make CO ₂Release obtains optimization.The whole bag of tricks embodiment partial interpretation below.

Another is to generate capacity CO to optimizing important parameters of the present invention ₂The volume of required carbon dioxide regulators or thickness.In order to calculate the carbon dioxide regulators insert or the thickness of various reaction materials, be transformed into CO at supposition carbonic acid reactant 100% ₂The basis on carried out series of computation.Two or trifunctional organic acid situation under, can make the reaction of one or more acid groups, but, suppose and have only an acid group reaction for the calculating in the following table.CaCO ₃Be used to finer and close (the higher CO of every volume of proof with fumaric combination ₂Output) effect of reactant pairing.At last, ethylene carbonate is used as the example in organic carbonate source and illustrates, and itself and water decompose and do not need acidifying when reacting.Following table 2 has shown the influence of reactant to insert thickness.

Table 2

Reactant is to the influence of insert thickness

Bottle	Type	Reactant	The insert thickness that calculates
				12 ounces	CSD	1mol?NaHCO 3+ 1mol citric acid	0.2889″
12 ounces	CSD	1mol?CaCO 3+ 1mol fumaric acid	0.1602″

12 ounces	Beer	1mol?NaHCO 3+ 1mol citric acid	0.1134″
				12 ounces	Beer	1mol?CaCO 3+ 1mol fumaric acid	0.0628″
12 ounces	Beer	Ethylene carbonate	0.0423″
16 ounces	Beer	1mol?NaHCO 3+ 1mol citric acid	0.0758″
				16 ounces	Beer	1mol?CaCO 3+ 1mol fumaric acid	0.0420″
16 ounces	Beer	Ethylene carbonate	0.0283″

In last table, suppose that the cumulative volume that is single ionization and insert or dish also increases with adding non-reacted adhesive.

Some carbon dioxide regulators can be placed CO ₂In the compression ring border, make its absorption and store enough CO ₂Gas, thus CO used ₂The pre-filling makes to substitute from the CO of container loss in the normal use of container ₂Preferably, this CO ₂The speed that discharges from carbon dioxide regulators approximates from the CO of container loss ₂Infiltration rate.

Use CO ₂A kind of method of filling arbon dioxide conditioning agent is, lid or bottleneck that the dish or the insert of carbon dioxide regulators composition are put into carbonated drink bottle are preserved the life-span to desired target and the CO that needs with prolonging container afterwards ₂This bottle of gas flow overvoltageization.Excessive CO ₂Immediately by the carbon dioxide regulators fast Absorption, thereby make no longer excessively pressurized of bottle.Afterwards as products C O ₂CO during from the packing loss ₂Air pressure reduces, at this moment absorbed CO ₂Be released into the top of soda.Another method is to use CO ₂The dish or the insert of pre-filling arbon dioxide conditioning agent, and the dish that will fill in advance in bottle and/or cap processing is put into lid or bottleneck.

Embodiment

Embodiment 1

Test various carbon dioxide regulators, test organic carbonate specifically, activate to determine whether it can and not exist under the organic acid situation by independent steam.Presentation of results shown in the accompanying drawing 7, steam activation by hydrolysis CO that cause, that be derived from organic carbonate ₂Generate, do not need organic acid.

Embodiment 2

Test various gasket materials, with the permeability of determining gasket material to CO ₂The influence of generating rate.The mixture of sodium acid carbonate and citric acid is sealed in the unsettled pouch, and this unsettled pouch is positioned at the top of air-tight bottle 25mL water.This sack is made by three kinds of different materials with DIFFERENT WET permeability to gas: papery tea-bag, PLA and polyethylene.Result in the accompanying drawing 8 proves, extremely low moisture barrier makes CO ₂Generating rate the fastest, and provide the slowest speed by the more high humidity barrier layer that polyethylene provides.Therefore, the moisture barrier layer material that is between carbon dioxide regulators composition and the soda can be used for controlling CO ₂Generating rate.

Embodiment 3-CO absorption ₂Saturated and discharge

Test various carbon dioxide and generate agent, particularly sorbing materials, under high pressure store and discharge CO to determine it ₂Therefore and prolong the ability that soda is preserved the life-span.At first with selected sorbing material at high pressure CO ₂Saturation under the environment.Then this sorbing material is inserted in 20 ounces of bottles, and with dry ice should bottle quick carbonating and cover valve protection cap.Molecular sieve is obtained by the commercial channel, and or is directly used or be dried by heating under vacuum.The 13X molecular sieve of discussing below obtains from Aldrich Chemical Company, and or is directly used or dry under vacuum before use.Record CO ₂The speed of from bottle, losing in time.Show in result's table 3 below.

Table 3

CO ₂The summary of saturation experiments

Sample	% preserves the life-span and improves
		Control bottle (not having saturated additive)	-
The saturated film bottle of w/8416	32.6％

W/4A molecular sieve bottle	104.2％
		W/13x molecular sieve bottle	61.4％
Yu Baohe @300 pound/square inch CO 2Bottle	0.2％

The result proves, can pass through CO ₂Saturated goods are put into bottle and the preservation life-span of prolongation soda, and molecular sieve is effective especially conditioning agent.

Experiment 4 will have and be filled with CO ₂Molecular sieve the bottle overvoltageization

Carry out this experiment for testing following idea: store excessive CO with the bottle overvoltageization, in molecular sieve ₂, and with the CO that absorbs ₂Discharge back in the top of bottle.Four groups of 12 ounces of bottles are tested, and each bottle contains the water of 15cc and uses the dry ice carbonating.First group is control bottle, only charges into the CO of 4.0 volumes ₂Second group of bottle charges into the CO of 4.75 volumes ₂, and the 13X molecular sieves of about 3 gram fine powderizations are also sealed within the bottle, this molecular sieve under vacuum by in dry mistake and be accommodated in the test tube.The 3rd group of bottle charges into the CO of 4.75 volumes ₂, and the not dry 13X molecular sieve of crossing and be contained in the fine powderization in the test tube of about 3 grams is also sealed within the bottle.

Result shown in the accompanying drawing 9 shows, the CO of control bottle ₂Loss speed is normal.Yet two groups of bottles that contain molecular sieve show initial CO ₂Pressure descends fast, this means CO ₂Absorbed by molecular sieve.Afterwards the bottle top CO ₂Level rises, because molecular sieve is with CO ₂Discharge back in the bottle.Compare with control bottle, these two groups of bottles have shown nominal increase the preservation life-span in 11 weeks.

In the following examples, can use conventional injection-blow moulding to make the PET bottle.This PET bottle is made by conventional PET bottle resin.Carbonated soft drink (CSD) bottle weighs 26.5 grams and volume is 12 ounces.The beer bottle weight that is used for the following example is 37 grams, and volume is 500mL, has at the bottom of the champagne bottle and 1716 bottlenecks, and this bottleneck is the bottleneck and the bottle neck of bottle, and has used conventional CSD lid.

By of the influence of following test carbon dioxide regulators: the conditioning agent sample of weighing inserted in the test tube and with test tube put into the PET bottle to pressing in the PET bottle.In bottle, add ten ml waters as follows: have only steam to contact with sorbent.According to United States Patent (USP) 5,473, the method for 161 instructions is with this bottle carbonating then.The equal triplicate of the bottle of all tests is estimated.

Use FT-IR, according to United States Patent (USP) 5,473, the amount of carbon dioxide during 161 methods of recording and narrating are measured under the permission of Coca-Cola bottle.This is directly corresponding to the CO in the bottle ₂The interior pressure.Regularly measure with tracking and remain in CO in the bottle ₂Amount.Adopt the conversion coefficient of signal to convert FT-IR result to CO ₂Volume, this term are commonly used in packing business to describe the amount of carbonating in the soda.One volume CO ₂Be under 20 ℃, to make packing increase the amount that atmospheric pressure is required.Definite method of conversion constant is: with the CO of known quantity ₂Put into bottle and measure CO in one hour sealing time ₂Concentration.Under various pressure, conversion constant is measured, found that this constant is constant in test accuracy.

By CO in the packing ₂Pressure is reduced to minimum acceptable value required time and determines to preserve the life-span.Different to this requirement of preserving the life-span with the product of packaging.For carbonated soft drink, need to use the initial carbonization level of about 4.0 volumes, and minimum acceptable level is about 3.3-3.4 volume.This is the loss amount of 15-17.5%.For beer, minimum carbonization level normally 2.7 volumes and initial concentration is 3.0 volumes.By after sealing, measuring the CO in the packing at once ₂Level, thus determine the initial carbonization level that each is tested.Preserve in the no show of off-test fashion under the situation in life-span, this value is determined by extrapolation as illustrated in fig. 1 and 2.Major part be packaged in its reach all use before the final preservation life-span good.

For product quality, make a large amount of packings in use its carbonization level to keep extremely consistent be very important.With CO ₂The interior pressure keeps constant relatively timing definition to become the adjusting time.This has obtained illustrating in attached Fig. 1 and 2.

Comparative Examples 5

PET beer bottle carbonating to the 3.3 volume CO that will have 1716 bottlenecks and CSD lid ₂Level.This conventional initial carbonization level with industry is compared higher slightly.In beer, the preservation life-span stops when carbonization level reaches 2.7 volumes.Preserve life-span and CO ₂The result is shown in table 4 and accompanying drawing 2 for loss speed.

Comparative Examples 6

12 ounces of CSD bottle carbonating to 4.0 volume CO that will have the CSD lid ₂Level.For soft drink, at 3.3-3.4 volume CO ₂The Shi Baocun life-span promptly stops.The result is as shown in table 4.

Embodiment 5:13X sieve is preserved the influence in life-span to the PET beer bottle

One gram 13X molecular sieve dry powder is inserted in vitro, and this test tube is arranged in PET bottle-lid identical with Comparative Examples 5 and makes up.Do not having to add CO under the situation of sorbent ₂, make to reach 3.6 volume CO ₂Carbonization level.The result is shown in Fig. 1 and table 4.To the carbonating persistent surveillance, be 2.7 volume CO until the minimum demand that reaches beer ₂Sorbent is inserted the CO that causes in the packing in the bottle ₂The mensuration level reduces rapidly, thereby the preservation life-span of packing has been extended 36 days than Comparative Examples 5.

Embodiment 6:13X molecular sieve is preserved the influence in life-span to 12 ounces of CSD bottles

Except that using 12 ounces of CSD bottles and CSD lid, carry out this experiment in the mode identical with embodiment 5.One gram molecule sieve dry powder is inserted the test tube that is arranged in identical PET bottle.Do not having to add CO under the situation of sorbent ₂, make to reach 4.35 volume CO ₂Carbonization level.Carbonization level is monitored at any time.The result is shown in Fig. 2 and table 4.Sorbent is put into packing cause free CO ₂Reduce rapidly, thereby the preservation life-span of packing has been extended 42 days than Comparative Examples 6.

Table 4

Sorbent is to preserving life-span and CO ₂The influence that interior crushing loses

Example	Add volume (CO 2Volume)	Initial volume (the CO that records 2Volume)	Terminal point volume (CO 2Volume)	The adjusting phase (my god)	Preserve the life-span (my god)
						Comparative Examples 5	3.30	3.34	2.7	0	80

Comparative Examples 6	4.0	3.98	3.4	0	60
						Embodiment 5	3.60	3.38	2.7	30	116
Embodiment 6	4.35	3.89	3.4	34	91

The contrast of various molecular sieves

Adopt gram molecule sieve in a manner described various commercially available molecular sieves (shown in each letter in the following table) to be tested.These materials derive from each manufacturer (representing with " Mfr ") and are directly used in following table.In having 12 ounces of CSD bottles that PCO (only vinyl cover) bottleneck and carbon dioxide addition are 4.5 volumes carbon dioxide, each material of gram is tested.Load and measured initial pressure carbon dioxide in back 1 hour.The relevant data of these molecular sieves is as shown in table 5.

Table 5

Adopt the preservation life-span prolongation amount of various molecular sieves

Obtain channel	Molecular sieve type	Add volume (CO 2Volume)	Initial pressure (CO 2Volume)	The adjusting phase (my god)	Preserve the life-span (my god)
						4.0 contrast	-	4.0	4.0	0	62
Aldrich	13X	4.5	4.1	44	102
						Mfr1	A	4.5	4.2	44	114
Mfr1	B	4.5	4.2	44	110
						Mfr2	C	4.5	4.2	44	100
Mfr2	D	4.5	4.3	44	100
						Mfr3	E	4.5	4.1	44	110
Mfr3	F	4.5	4.2	44	110
						Mfr3	G	4.5	4.3	44	114

Baking temperature keeps Effect on Performance also to obtain test to carbon dioxide.Molecular sieve is carried out drying can improve its adsorption capacity usually.Molecular sieve is descended dry 15.5 hours at 120 ℃, and test by above-mentioned.The result is as shown in table 6.

Table 6

The performance of 120 ℃ of dry back molecular sieves

Obtain channel

Molecular sieve type

Add volume (CO 2Volume)

Initial pressure (CO 2Volume)

The adjusting phase (my god)

Preserve the life-span (my god)

4.0 contrast	-	4.0	4.0	0	62
						Aldrich	13X	4.5	4.2	46	105
Mfr1	A	4.5	4.2	46	105
						Mfr1	B	4.5	4.2	46	110
Mfr2	C	4.5	4.2	46	112
						Mfr2	D	4.5	4.3	46	99
Mfr3	E	4.5	4.2	46	114
						Mfr3	F	4.5	4.1	46	105
Mfr3	G	4.5	4.3	46	110

Molecular sieve is dry down also as above-mentioned tests at 240 ℃.The result is as shown in table 7.

Table 7

The performance of 240 ℃ of dry back molecular sieves

Modifier material	Add volume (CO 2Volume)	Initial pressure (CO 2Volume)	The adjusting phase (my god)	Preserve the life-span (my god)
					There is not conditioning agent	4.0	4.0	0	56
There is not conditioning agent	4.4	4.4	0	80
					The 13X molecular sieve	4.4	4.2	14	71

Surface area is to Effect on Performance

Use Spex Mill grinder that 13X molecular sieve powder sample is ground, to reduce its particle diameter and to increase its surface area.The surface area and the particle diameter of the Aldrich 13X molecular sieve before and after grinding are as shown in table 8.

Table 8

The surface area and the particle diameter of Aldrich 13X molecular sieve before and after grinding

Measure	Unit	Initially	After the grinding
				The volume weighting average diameter	Micron	5.91	8.45
Surface weighted average diameter	Micron	3.41	3.17

Specific area

Meters squared per gram

1.7618

1.8919

Employing has 12 ounces of CSD bottles of PCO bottleneck and gram molecule sieve, by above-mentioned material property is tested.The result is as shown in table 9.

Table 9

The influence that the molecular sieve surface area keeps carbonating

The modifier material type	Specific area (meters squared per gram)	Add volume (CO 2Volume)	Initial pressure (CO 2Volume)	The adjusting phase (my god)	Preserve the life-span (my god)
						There is not conditioning agent	-	4.0	4.0	0	56
The 13X molecular sieve	1.7618	4.5	4.3	44	140
						The 13X molecular sieve	1.8919	4.5	4.1	44	140

The effect of sheet molecular sieve

Molecular sieve is pressed into sheet, and these small pieces are exposed to the vapor space of bottle or small pieces be impregnated in the water that is arranged in container, thereby test.The result is as shown in table 10.

Table 10

The contrast of molecular sieve sheet and powder

The conditioning agent type	The molecular sieve form	Add volume (CO 2Volume)	Initial pressure (CO 2Volume)	The adjusting phase (my god)	Preserve the life-span (my god)
						There is not conditioning agent	-	4.0	4.0	0	62
The 13X molecular sieve	Powder	4.5	4.1	46	102
						The 13X molecular sieve	Sheet	4.5	4.1	46	104

Coating is to the modified effect of molecular sieve piece performance

Make the molecular sieve sheet by compression with 125 ℃ of following dryings.GeneralElectric Silicon RTV615A 01P solution with 2% applies, and this solution is to form by 10 parts of elastomers of mixing and 1 part of curing agent in heptane.The molecular sieve sheet is immersed in the applying liquid and at room temperature in air drying.Coating and uncoated molecular sieve sheet are placed into the top of 12 ounces of CSD bottles and as above-mentioned the test, the result is as shown in table 11.

Table 11

Silicone-coated is to the influence of molecular sieve piece performance

The conditioning agent type

The molecular sieve form

Apply

Add volume (CO 2Volume)

Initial pressure (CO 2Volume)

The adjusting phase (my god)

Preserve the life-span (my god)

There is not conditioning agent	-	-	4.0	4.0	0	62
							The 13X molecular sieve	Sheet	Uncoated	4.5	4.0	46	102
The 13X molecular sieve	Sheet	Apply	4.5	4.1	40	-

Molecular sieve effect in the lid insert

The cup that can be fitted in the lid and also serve as gasket seal carries out injection molding, thereby makes little insert.This cup contains the 1g molecular screen material, and can be fitted in the bottleneck of 12 ounces of CSD bottles.By polyethylene and polypropylene these cups are carried out injection molding, and keep performance to test to the carbonating of inserting the molecular sieve in the cup by above-mentioned.Data are as shown in table 12.

Table 12

Molecular sieve is inserted effect in the lid insert

The conditioning agent type	The cup material	Add volume (CO 2Volume)	Initial pressure (CO 2Volume)	The adjusting phase (my god)	Preserve the life-span (my god)
						There is not conditioning agent	There is not cup	4.0	4.0	0	62
There is not conditioning agent	There is not cup	4.5	4.5	0	98
						There is not conditioning agent	70-7931	4.5	4.5	0	100
There is not conditioning agent	9551	4.5	4.4	0	92
						The 13X molecular sieve	Powder	4.5	4.2	20	76
The 13X molecular sieve	Sheet	4.5	4.2	0	82

Annotate: 70-7931 is the polypropylene that obtains from BP

The 9551st, from the low density polyethylene (LDPE) of Dow Chemical acquisition

The contrast of ascarite and molecular sieve

To the 13X molecular sieve with as the ascarite of carbon dioxide absorbing material, each adopts the 1g material to carry out performance relatively by above-mentioned.The result is as shown in table 13.

Table 13

The carbonating of molecular sieve and ascarite keeps property comparison

The conditioning agent type	Add volume (CO 2Volume)	Initial pressure (CO 2Volume)	The adjusting phase (my god)	Preserve the life-span (my god)
					There is not conditioning agent	4.0	4.0	0	62

Ascarite	4.5	4.5	0	44
					The 13X molecular sieve	4.5	4.5	44	108

The conditioning agent system of acid activation

Regulate CO ₂A kind of facilitated method that discharges is that packing is contacted with beverage.A lot of carbonated soft drinks are highly acid, therefore make acidity become the carbon dioxide regulators from mix PET bottle or lid to discharge CO ₂Facility cause mechanism.Common acid comprises phosphoric acid and citric acid in the beverage.

The suitable carbon dioxide regulators that is used for this design comprises the inorganic carbonate as calcium carbonate, organic carbonate ester oligomer and polymer as shown in table 14, with and combination.Inorganic carbonate and organic carbonate ester oligomer are to obtain from Aldrich Chemical Company.The cyclic carbonate ester polymer is the Morton professor H.Litt acquisition from Case Western Reserve University polymer science and engineering department.

With PET and various carbon dioxide source dry blend, and on the laboratory scale double screw extruder of APV, mix to form shrend line (water quenched strand).It is 2 phosphoric acid solution that the materials of about three grams are inserted the pH value that is arranged in 155mL overhead bottle, and seals with blind nut (crimp top) silicone cushion.Generation with the GC monitor carbon dioxide.The carbon dioxide mL number that every day, every gram modifier material generated is as shown in table 14.Also illustrate in the table for conventional 12 ounces of carbonated soft drinks containers, with CO ₂The conditioning agent approximate quantity that rate of release is complementary.

Table 14

From the PET mixture, discharge CO ₂Speed

Sample	Carbonate compound weight %	Molecular sieve weight %	PET weight %	Temperature ℃	CO 2Generate ml/g conditioning agent/sky	Satisfy the aequum g of target
							The PET that fills
13X molecular sieve powder among the PET	0	5	95	22	0.55	7.4
							Butylene carbonate among the PET	5	0	95	22	0.39	10.5
Have the butylene carbonate among the PET of 13X molecular sieve	5	5	91	22	0.25	16.5
							Pyrocarbonic acid diethyl ester among the PET	4	0	96	22	1.92	2.1
Have the pyrocarbonic acid diethyl ester among the PET of 13X	4	5	91	22	0.39	10.5
							Carbonic acid glyceride among the PET	4	0	96	22	0.54	7.6

Propylene carbonate among the PET	5	0	95	22	0.52	7.9
							Have the propylene carbonate among the PET of 13X molecular sieve	5	5	91	22	0.37	11.1
Sodium acid carbonate NaHCO among the PET 3	5	0	95	22	8.13	0.5
							Have the sodium acid carbonate NaHCO among the PET of 13X molecular sieve 3	5	5	91	22	8.76	0.5
The inferior ethene of carbonic acid among the PET	1	0	99	22	2.35	1.8
							Butylene carbonate among the PET	5	0	95	52.2	0.69	6.0

Have the diethyl carbonate among the PET of 13X molecular sieve	5	5	91	52.2	0.72	5.7
							The inferior ethene of carbonic acid among the PET	1	0	99	52.2	7.60	0.5
The cyclic carbonate ester polymer	5	0	95	23	0.13	30.9
							The cyclic carbonate ester polymer	5	0	95	22	0.15	27.4

Pre-saturated effect

Preparation has the small pieces that PET makes the 4A extrusion sheet of adhesive, and with its presaturationization.11.3 gram 4A molecular sieves are used with 4.8 gram PET.These two kinds of materials are mixed, and in about 100-120 ℃ temperature, forming cylindric compressor under 10000 pounds/square inch the pressure.Under room temperature and 300 pounds/square inch with small pieces CO ₂Saturated 36 hours.Small pieces on average adsorb the CO of 1.47 grams ₂Small pieces are cut in half, it can be placed in the bottle.Bottle (6) is sealed and monitor.Accompanying drawing 10 shows that use 4A presaturation material has prolonged the preservation life-span.CO in the bottle in the test ₂Maximum appears in level, and it has shown from the 4A material emits CO ₂Slow process.

Make the 13X sheet by similar method.The 13X (the same with 4A all available from Aldrich) and 4.8 of 3.2 gram powdered are restrained PET be configured as sheet, cut in half, and under room temperature, 300 pounds/square inch, use CO ₂Saturated 36 hours.Saturated sheet material is put into the PET bottle and monitored CO ₂Level.Extra CO ₂Prolonged the preservation life-span.Small pieces have on average adsorbed the CO of 0.52 gram ₂

With 5.25 square inches, 10 mil thick and the PET film that do not stretch saturation 36 hours under room temperature and 300 pounds/square inch.In each bottle, distribute 29 gram films.Under room temperature and 300 pounds/square inch with PET film CO ₂Saturation 36 hours.Film has on average adsorbed the CO of 0.99 gram ₂Film put into PET bottle (6) and to inner CO ₂Level monitors.As shown in Figure 10, the CO that from the PET film, discharges ₂Prolonged the preservation life-span.

Embodiment 5 and 6 further discussion

Suitable sorbent is put into the PET carbonated drink bottle can make extra CO to be added ₂Can not cause the rising of pressing in the bottle.This finds out from embodiment 5 and 6 easily.In embodiment 5, add CO ₂Produce the carbonization level of 3.6 volumes, but only record 3.38 volumes after the sealing.In embodiment 6, added 4.35 volumes but only recorded 3.89 volumes in after sealing one hour.Under every kind of situation, CO ₂All adsorbed fast, thereby prevented bottle generation percarbonic acidization.

The CO of absorption ₂Afterwards along with the time is slowly released in the bottle, the CO in causing packing ₂Pressure is more stable.Embodiment 5 and adjusting phase of 6 are respectively 30 days and three fortnights.This just in time is in the time range of and sale packaged at most of high volume sodas.

Embodiment 5 and final preservation life-span of 6 are more much longer than the time of seeing in Comparative Examples.The preservation life-span all was extended above 30 days under every kind of situation.Various different molecular sieves as the carbon dioxide regulators basis are estimated.As shown in table 5, find that a lot of materials all are effective.

The inventor has detected baking temperature to the carbon dioxide regulators Effect on Performance.Find unnecessary the molecular screen base conditioning agent to be carried out drying obtaining premium properties, and be dried than 120 ℃ of these materials of conventional drying lower temperature and can improve its performance.To cause the adjusting phase significantly to shorten in 240 ℃ of following dryings of higher temperature.Avoiding dry these molecular sieves before using all is favourable for a lot of carbon dioxide regulators designs.

As shown in table 5, increase the particle diameter of sorbent and the CO that surface area causes carbon dioxide regulators to adsorb ₂Amount significantly increases.For specific carbon dioxide regulators, optimization particle diameter and surface area are items in the routine experiment.

The physical aspect of conditioning agent is very important in the optimized carbon dioxide regulators of exploitation.The inventor finds that the molecular sieve that is pressed into sheet can be and the same effectively conditioning agent of molecular sieve powder.The form of optimization conditioning agent and shape also are items in the routine experiment.

It is the method for especially effectively making conditioning agent that coating molecular sieve sheet is contemplated to.A key character of this coating is to make CO in the process bottled filling out ₂Fast absorption, thus convenient for the overvoltageization of introducing the additional carbon dioxide method.As shown in table 11, the inventor finds that silicone coatings is effective.

Insert cup assembly and represented a kind of practical approach of making the carbon dioxide regulators system.As shown in table 12, the inventor finds that it is effective that polyvinyl inserts cup.Other polyolefin that is applicable to this assembly comprises: thermoplastic polyolefin elastomer, ethylene copolymer such as straight-chain low density polyethylene and ultra-low density polyethylene, ethylene-propylene copolymer, propylene copolymer and styrene thermoplastic elastomer.The more soft polyolefin material that can form the surface of package sealing is preferred.Determine to insert cup or the optimal size of other conditioning agent form and the item that material is routine test.

As shown in table 13, the material of a lot of absorbing carbon dioxides is not easy to form the conditioning agent system.Ascarite is the inorganic matter that adsorbs great amount of carbon dioxide easily, but pure ascarite is not easy to form suitable carbon dioxide regulators, because CO ₂The same CO of rate of release ₂Speed dissmilarity from the packing loss.

Those skilled in the art can recognize have several factors can further improve the present invention.It is favourable that sorbent has high as far as possible absorbing carbon dioxide ability.Adsorption capacity characterizes with the adsorbable carbon dioxide weight of the sorbent of Unit Weight.Has higher CO ₂The sorbent of adsorption capacity is preferred because so can be in packing interpolation sorbent still less to prolong the required preservation life-span.

Operating condition also is important.Well-known is thereby that the heating molecular sieve can be removed the material that is captured and makes adsorption capacity stronger.Surprised is that super-dry can be destroyed these as CO ₂The material property of conditioning agent.

Molecular sieve may need with the adhesive material combination, is made into facility to be suitable for the parts that the present invention uses.Required adhesive type depends on the performance of molecular sieve and finally makes the required performance of parts.This adhesive comprises: be generally used for improving the inorganic bond of molecular sieve mechanical performance, the organic polymer that can sneak into sorbent, the low-molecular-weight resin that can disperse sorbent and oligomer.It can be natural thermosetting or thermoplastic, and can comprise the material as silicone rubber, polyolefin, epoxy resin, unsaturated polyester (UP) and polyester oligomer.

The control CO absorption ₂The speed that from sorbent, discharges, prevent that liquid water from causing CO absorption ₂Unexpected release, the losing or allow packing composition to contact of sensation component that prevents beverage with conditioning agent with controlled manner, be very important to the present invention.This can reach in the following way: sorbent is put into the low polymer of water permeability, or insert the film of this polymer between beverage and sorbent material.Require this material can see through CO ₂Thereby adsorb percarbonic acidization easily, it can be by semipermeable membrane, permeable membrane or high CO ₂Infiltrative material with and the combination and constitute.Suitable material comprises polyolefin, as low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, ethylene-propylene elastomeric, vinyl-vinyl acetate copolymer, and silicone rubber.Suitable membrane material comprises: as the impenetrable liquid/ventilative body material of Gore-Tex or similar structures.The particularly preferred embodiment of the present invention is that sorbent is sneaked in the suitable polymers, and uses this material to make bottle cap itself, and the sorbent dish that makes is inserted in the lid of cap liner back, uses CO ₂Permeable thin polymer film or coating protection quasi-tube insert or by sorbent and CO ₂The combination of permeable polymer is carried out molded to quasi-tube insert.The method of preferably sorbent being put into its performance of bottle neutralization optimization is the item of further experiment.

As shown in table 14, carbon dioxide regulators also can pass through CO ₂Releasable material is sneaked among the PET and is formed.For such carbon dioxide regulators, importantly before to the packing filling, do not discharge CO ₂Thereby the performance of carbon dioxide regulators can not lost in bottle stores.Various inorganic and organic carbonate compounds can be lower than 20 weight %, preferably sneak among the PET less than the concentration of 10 weight %, thereby obtain equaling conventional PET packing CO ₂The CO of loss speed ₂Rate of release.These materials are activated by inserting in the water with the similar pH scope of many carbonated soft drinks.

One aspect of the present invention is to make soda store the longer time in thermal environment and need not more expensive coating or the cold condition of depositing.In thermal environment, storing temperature may be very high, so and the synthermal CO that is directly proportional of the carbon dioxide permeability of bottle ₂Loss speed also can be higher.And the interior pressure in the bottle also can reach danger level because of these temperature.Therefore, it is particularly advantageous keeping stable and consistent interior pressure and prolongation to preserve the system in life-span.

The present invention alleviates the weight of existing carbonated drink bottle and keeps its existing preservation life-span.The infiltration rate of packing is inversely proportional to the thickness of package wall.It as far as possible gently is favourable economically making packed weight, but this causes wall thickness to reduce.The system that prolongs the conventional packing preservation life-span can make the packing than thin-walled have with the conventional suitable preservation life-span of packing.In the application that present technique relates to, the packing of many bottles all is that light getting can not be light again, but does not cause preserving shortening of life-span, also uses more expensive system bottle technology.

Another aspect of the present invention is can keep for more time more optimizing and more stable carbonization level, thereby produces more consistent product taste and quality.The carbon dioxide dissolved amount is that pressure with carbon dioxide in the container is directly proportional in the beverage.The pH value of carbon dioxide dissolved concentration affects beverage and other performance.The dissolved carbon dioxide of stable quantity will be equal to more consistent beverage products taste.

Another aspect of the present invention is the rate of release of control carbon dioxide, makes this speed be no more than the infiltration rate of packing in fact.The overvoltageization of carbonated drink bottle is a big problem, and it can cause this economy of breakage of packing and safety problem.Any effective CO of carbonated drink bottle ₂Regulating system, the speed of its release of carbon dioxide necessarily can not be significantly greater than losing CO from packing ₂Speed.Ideally, this rate of release should equal or be slightly less than from the speed of packing infiltration and should not surpass 125% of packing infiltration rate.It also must as one man discharge CO in long-time desirable ₂, be up to three months during this period of time and minimum be two weeks.

Another aspect of the present invention is that it can the self-control with the thermal environment of packing, thereby loses when higher when carbonic acid in warm environment, and this conditioning agent discharges naturally more that the volume carbon dioxide comes replenish lost.

Another aspect of the present invention provides a kind of packaging system, and it allows percarbonic acidization and pressure in the packing that do not raise, and makes that lighter bottle also can be used for adorning soda.When filling add too much carbonic acid gas be one very economical, be used to prolong this soda and preserve method of life, still be used to pack soft drink and beer now.But its ability of being packed the higher initial pressure level of maintenance limits.Absorption and the system that discharges this carbon dioxide again can improve the percarbonic acid amount when filling, thereby can promote the use to lower resistance to pressure container.

Carbon dioxide is regulated the use that has also promoted the container of lower modulus.It is because it can not contain high interior pressure that produces with carbonated soft drinks that many plastics are not suitable for the packing soda.Typical example is as polyacrylic polyolefin.With the carbonic acid conditioning agent be used in combination such as polyacrylic lower modulus plastics, make the container of lower modulus more generally be used to pack soda.

As above only the present invention has been made illustrative with some embodiment.But it should be understood that those skilled in the art to various changes, interpolation, improvement and the adjustment of enumerating embodiment all within the scope and spirit of the present invention.

Claims (16)

1. the method for carbon dioxide in the additional carbonated beverage container, it comprises:

I. in described container or in the lid of described container, insert carbon dioxide regulators; With

Ii. will be from described carbon dioxide regulators the rate adaptation of release of carbon dioxide to approximating the speed of carbon dioxide from described container loss,

Wherein said carbon dioxide regulators is to absorb also the sorbent of carbon dioxide gas subsequently.

2. the process of claim 1 wherein before being inserted into described carbon dioxide regulators in the described container, to the pre-filling arbon dioxide of this carbon dioxide regulators.

3. the process of claim 1 wherein and as follows described carbon dioxide regulators is filled: the insert of described carbon dioxide regulators is inserted in the lid or bottleneck of described container, and the carbon dioxide of using appropriate amount subsequently is to described container overvoltageization.

4. the process of claim 1 wherein that described carbon dioxide regulators is selected from molecular sieve.

5. the process of claim 1 wherein that described carbon dioxide regulators is selected from silica gel, molecular sieve, clay, activated alumina, zeolite, Coordination Polymers and metal organic frame.

6. the process of claim 1 wherein that the insertion that step (i) takes place makes described carbon dioxide regulators not contact with described soda.

7. the process of claim 1 wherein described carbon dioxide regulators is directly sneaked in the material of described container or described lid.

8. packaging system that is used to keep the pressure consistency of soda, it comprises lid, plastic containers and carbon dioxide regulators,

Wherein said carbon dioxide regulators is to absorb also the sorbent of carbon dioxide gas subsequently.

9. the packaging system of claim 8, wherein said lid comprises any material that is used to seal described plastic containers.

10. the packaging system of claim 8, wherein said lid further comprise the gasket material in it.

11. the packaging system of claim 10 is wherein sneaked into described carbon dioxide regulators any material that is used for making described plastic containers, described lid or described gasket material.

12. the packaging system of claim 8 is wherein inserted described carbon dioxide regulators in described plastic containers or the described lid with the form that is suitable for described plastic containers.

13. the packaging system of claim 8 wherein by adopting PET molded again performing member around a conditioning agent assembly, makes described carbon dioxide regulators become the part of described conditioning agent assembly.

14. the packaging system of claim 13 is wherein made plastic containers with described performing member.

15. the packaging system of claim 8 wherein is added to described carbon dioxide regulators in the described plastic containers with layer form.

16. the packaging system of claim 8 wherein is added to described carbon dioxide regulators in the described lid with layer form.

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