CN103940522A - Polymeric form time-temperature indicator and application in military food of the same - Google Patents

Abstract

The invention belongs to the technical field of measurement and instruction, and especially relates to a polymeric form time-temperature indicator and application in military food time-temperature indicator of the polymeric form time-temperature indicator. The polymeric form time-temperature indicator comprises, by weight ratio, 6 : 1 - 1 : 6 between two toluidine formic acid-2, 4-diyne-1, 6-hexanedioic ester and two pair fluorine benzene sulfonic acid-2, 4- diyne-1, and 6-hexanedioic ester. According to the polymeric form time-temperature indicator, connection two alkyne class polymerization reaction activation energy generating in the component is matched with the military food quality change activation energy, and the reaction speed of the two activation energies are similar to each other. Meanwhile, the polymerization reaction color change is significant, and pink is turned into black. The indicator made of the polymeric form time-temperature indicator is attached to the military food outer package, the accumulated experience of time-temperature effect of the two activation energies is consistent, and food quality status can be indicated.

Description

A kind of aggretion type time-temperature indicator and the application in military food thereof

Technical field

The invention belongs to and measure and pointing technology field, relate in particular to a kind of aggretion type time-temperature indicator and the application in military food Time-temperature indicateing arm thereof.

Background technology

(1) food quality

Food quality refers to the edible performance of food and the regulation of characteristic conforms related standards and meets the degree that consumer requires.Food quality is combined by multiple qualitative factor, mainly comprises hygienic quality, nutritional quality, aesthetic quality and other additional masss etc.Food quality is a kind of attribute that affects the dynamic complexity of its Consumers' Acceptance, after processing just in a dynamic process for continuous decline.Food quality variation comprises color and luster, local flavor, matter structure, nutritive value, safe and sanitary etc.Because most food all comes from animals and plants product, these raw materials not only contain large quantity of moisture, and contain abundant nutriment.The unsettled nutritional labeling of these physicochemical properties had both easily been subject to the infringement of microorganism, the easy effect in environmental factor issues biochemical or physical change again, numerous food product also contains multiple enzyme, in the situation that environmental baseline is suitable, many kinds of enzymatic reactions easily occur, and all these all can cause food quality to change.Food quality changes the impact that is subject to food component and environmental factor, and its rate of change can represent in order to minor function:

dQ/dt＝F(C _i,E _j)

Wherein Ci represents food internal factor, the physiological change and the microorganism that comprise fresh and alive food change, as the respiration of vegetables and after-ripening, livestock and poultry fish stiff, after-ripening, self-dissolving and corruption after death, and the various physicochemical change of food composition generation, as nutritional labeling loss, pigment decompose, are hydrolyzed variation etc., internal factor is the particular attribute of food, determines the quality of raw material.For packaged food, the variation of environmental factor is the leading factor that food quality changes.Ej refers to environmental factor, comprises the negative effect to food quality such as pollution in temperature, relative humidity, general pressure, gaseous tension, illumination, microbial contamination, the insect pest plague of rats, production, packing and circulation, mechanical damage.Wherein on food quality impact, comparatively generally the fat oxidation due to the composite factor such as temperature, light oxygen becomes sour, age of starch, protein denaturation, vitamin destroys and evaporation, the absorption of moisture, shift, condense etc.

(2) effective period of food quality

Shelf-life theory results from modern food technology and packing technique, comprises bromatology, packing, materialogy, many-sided technical know-how such as the marketing in shelf-life concept.The length of shelf life of products, depends primarily on quality, technology of the package and the material of product itself and the environmental baseline of products in circulation process etc., and its influence factor is numerous, forms mechanism and mutual relationship also comparatively complicated.

Effective period of food quality is a time limit, under specific storage requirement, and food consumption safety, the time limit that quality can be accepted by consumer.In society, there is no the unified standard definition shelf-life.The definition of shelf-life and assay method are along with food variety and purposes and change.

Different from civilian food, military food is at production reserve at ordinary times, under the special emergency such as wartime or manoeuvre, outer instruction, oceangoing voyage and frontier defense patrol, just can use, so military food must possess longer storage period, and color, smell, taste and shape and nutritional labeling remain unchanged substantially within storage period.For example, 10 people and 4 people of the British army combine grain ration, in the storage period of Temperate Region in China, are 3 years, 2 ℃ of temperature, relative humidity 60% compared with under Cool Condition, can reach 5 years storage period.My army's military food at normal temperatures general storage period all more than 2 years, as to the regulation of the shelf-life of military tinplate can and storage life being: under the Ku Changwen of ground, meat, fowl, 30 months aquatic product can shelf-lifves, storage life 36 months.24 months shelf-lifves such as fruits and vegetables class, storage life 30 months.It is different being stored in south and northern military food shelf-life, and the shelf-life of the military food that the north stores will be grown.Therefore, how accurately indicating food quality is an important topic of military food.

(3) time-temperature indicator technology

Time-temperature indicator (Time-Temperature Indicator, TTI) can be defined as the simple easy quality record device of a class, can monitor and record the part key parameter in the whole shelf life of commodity, then the cumulative effect indication food temperature by Time-temperature changes course and residue shelf information.TTI can demonstrate continuous Time-temperature reaction, and can carry out integration to whole Time-temperature courses in measurement, " the effectively medial temperature " of indication sales process.

(the Time-Temperature Indicator of time-temperature indicator the earliest, TTI) can trace back to during World War II, AUS quartermaster regiment is placed on ice cube in frozen food case, if ice cube disappears, just mean that the temperature control in transportation storage process is improper, the ice cube of using is here exactly a kind of simple TTI.1993, first TTI patent was born in the world.Subsequently, Honeywell company (Minneapolis, MN) has developed first TTI that can use in business, and still the price due to it is very high, volume is excessive, so never really use in business.

The people such as Ramstad developed and have manufactured a TTI that the packaging bag that can be permeated by animal glue and oxygen forms in nineteen fifty.Colloid contains oxidase and colourless oxybenzene compound, once colloid dissolves, colourless oxybenzene compound will react overstrike.The time length that browning degree indication food exposes at harmful temperature and the mass change situation of food.Browning rate can be controlled by adding the vitamin C of varying level.At 4.4 ℃, the time that this indicator brown stain needs is 6 hours, needs 24 hours after adding 0.1% vitamin C.

At twentieth century beginning of the seventies, the research and development of TTI become a focus.It is basic TTI that AUS Natick has invented in laboratory a kind of variable color of take oxidation system, and its principle is to affect by temperature the amount of oxygen that sees through film, and then causes color change.Through reaching 2 years on probation, show that they likely drop into practical application.At present, " buphthalmos " label that the MRE grain ration that a new generation of U.S. army can preserve 10 years is being used is the aggretion type TTI according to this principle development.

By 1976, have Liu Jia TTI manufacturer: Artech company, Check Spot company, Tempil company, I-Point company, He3M company of Bio-Medical Science company.Wherein, I-Point company produces is a kind ofly to take enzyme reaction as basic TTI, and what 3M company produced is a kind of to be diffused as basic TTI.

Twentieth century is early stage the eighties, has I-Piont, 3M, Ambitemp and tetra-kinds of business TTI systems of Tempchron on market.The principle of work of Ambitemp and Tempchron is to utilize liquid flowing in kapillary, is produced, for the marketing system of frozen food by Andover Labs.

The people such as Singh in 1985 study the grow variations such as organoleptic feature of demurrage, tomato of thermoduric bacteria in response time of finding I-Point label and the quality in freezing hamburger, the organoleptic attribute that is stored in-12 ℃ of strawberries under condition and vitamin C, fresh milk good correlativity.The people such as Wells in 1988 study and find that the hardness of tomato and the response of color and I-Point2340 type and two kinds of indicating cards of Lifelines Freshness Monitor57 type are significant correlation; At the temperature of 5 ℃ and 10 ℃, I-Point2340 type indicating card can be good at indicating the aesthetic quality of lettuce to change; Be mixed with the cake of dry fruit and the response of indicating card used does not have correlativity; Between the response of the coconut taste of UHT sterilization milk and whiteness and Lifelines Freshness Monitor11,21 type indicating cards, be significant correlation.The people such as Cherng in 1989 find the response of TTI and the taste of pasturising milk, pyschrophile number and the acidity value significant correlation of Lifelines, can the mass change of effective monitoring milk in transportation and sale process.Nineteen ninety Labuza and Taoukis utilize product remaining shelf life information in cold chain that TTI provides to optimize control and the inventory turnover of circulation at first.The people such as Shell in 1991 utilize I-Point4014 type and 4021 type indicating cards to monitor chemistry and the microbiological indicator of farmer cheese, and research shows that the response of I-Point4014 type indicating card and the chemistry of farmer cheese and the variation of microbiological indicator have good correlativity.The people such as Taoukis are applied to Boque fish to TTI in 1999 and are studied.This research is usingd two microbiological indicators of fish and an organoleptic indicator as evaluation index, utilizes Arrhenius equation and Belehradek equation to analyze.2000, the Sock-In Hong of Korean foods research institute and Wan-Soo Park used TTI to monitor the fermentation situation that Chinese cabbage is made Pickles, and research finds that some TTI can be used as a kind of intelligent packaging system, the fermentation of monitoring Chinese cabbage.Through test, TTI product can also be applied to refrigerated vegetables, frozen strawberry, mushroom, cooling instant salad, Frozen Pork and chicken, freezing sausage, cooling orange juice, pasteurize milk wet goods.

In patent US2553369, mentioning the potassium triiodide of hydration, soluble starch and diastase thereof can be for the Time-temperature indication of frozen food.When environment temperature is during higher than the thaw point of food, starch is hydrolyzed under diastatic effect, because the existence of potassium triiodide presents blueness.In patent US2892798, mercuric iodixde, cupric iodide are mixed in to liquid metal alkyl iodide solution, when frozen food start to thaw time, this mixed solution will present the variation of color.Patent US3545400 shows that the device that a kind of dyestuff can be filled is used to indicate solidifying point and melting temperature.In patent US3768976, mentioning in the process that the aqueous solution of orchil can be permeated gradually at oxygen oxidation becomes and colourlessly indicates perishable commodity to have a very long time to be placed under higher temperature conditions.In patent US3844718, when contacting with the ink (this ink invests on hygroscopic substrate) of solubility, water or water vapor can indicate the thaw point of food.In patent US3078182, a kind of label of pressure sensibility change color indication can be used to indicate the sterilization operation process of product.The research of conjugation diacetylene compounds is shown to conjugation diacetylene compounds also can be for the indication of Time-temperature, and continuous process that can presentative time-temperature variation.TTI has been applied in the fields such as food, medical product (as vaccine, serum), tobacco, pet food, cosmetics, electronic product at present.

Military food, in transportation and storage, is subject to the impact of environment temperature, and food quality constantly declines or be deteriorated, even can not eat.Judgement food quality mainly relies on date of manufacture and shelf-life at present.Owing to not knowing that between the storage life, environment temperature is high or low, only rely on the storage time, be difficult to accurately judge food quality state.The time-temperature indicator of prior art mainly refers to the fresh food that the things shelf-life is shorter, for longer tinned food of shelf-life and military food, studies at present fewerly, and proven technique and product are difficult to see especially.

Summary of the invention

For solving the deficiencies in the prior art, the invention provides a kind of aggretion type time-temperature indicator, the company's diyne type of polymerization energy of activation occurring in its component mates with the energy of activation of military food mass change, and the two reaction velocity is close.Meanwhile, secondary response change color is remarkable, from pink, becomes black.Indicateing arm with its making sticks in military food external packing, and the Time-temperature effect of accumulation experience is consistent, can indicate food quality state.

An aggretion type time-temperature indicator, comprises that weight ratio is two meta-aminotoluene base formic acid-2 of 6:1～1:6,4-diine-1, the own diester of 6-and two pairs of fluorobenzene sulfonic acid-2,4-diine-1, the own diester of 6-.

Preferably, described aggretion type time-temperature indicator, two meta-aminotoluene base formic acid-2 wherein, 4-diine-1, the own diester of 6-and two pairs of fluorobenzene sulfonic acid-2,4-diine-1, the weight ratio of the own diester of 6-is 3:1～1:3.

Diacetylene compounds (RC ≡ CC ≡ CR, R is substituted radical) can carry out solid-state Isosorbide-5-Nitrae-polyaddition reaction under heating or energy-rich radiation condition, and reaction expression is as follows:

Generally, monomer is all that colourless, partially polymerized monomer shows blue or red, and the diacetylene compound of polymerization presents metallic luster completely.Chain polymer has color to cause in the structural delocalization of conjugation chain because of pi-electron, and the color of polymkeric substance is that the plane degree by the length of conjugated chain and polymer backbone is determined.No matter same two acetylene compounds are under colourless free state, under partially polymerized blue color states or under the red status of polymerization completely, their composition, molecular weight and NMR collection of illustrative plates are identical.There are some researches show, the compound of blue color states is that free radical causes.The mechanism transforming between the acetylene compound of three kinds of states is as follows: the monomer of white forms blue cumulene free radical under illumination, then the in the situation that of heating, changes into the acetylene compound of red status.

Conjugation acetylene class TTI can utilize irreversible, the obvious color change process of its in time-temperature indicate easy corrupt deteriorating item whether be in people in the bad change process of less desirable Time-temperature.No matter this compounds is ring-type, chain, symmetrical, asymmetric, diine, three alkynes, four alkynes ... all comprise two or more conjugation acetylene groups, the change of its color is to be caused by the solid-state Isosorbide-5-Nitrae-polyaddition reaction in temperature or optical radiation situation.

Property research to conjugation acetylene compound shows, these compounds, can also be for other side except for making TTI.In patent US3923622 by this compounds for the synthesis of annular stepped type polymkeric substance; It is synthetic for what react that these compounds also can be used as crosslinking chemical; In patent US4788151, also mention the material that can indicate acetylene metalloid complex compound as environment.And to this compounds most study, or the change color based on its in time-temperature.

In patent US4737363, conjugation diacetylene class salt compound can be used as photoactive Time-temperature indicating label.Conjugation diacetylene class salt compound forms conjugation diacetylene class carboxylic acid under optical radiation condition, thereby is activated, and corresponding color change occurs along with the variation of Time-temperature, this compounds be mainly used in indicating frozen food in time-the bad change process of temperature.

Patent US3999946 is explained in detail for TTI this compounds.But the TTI of this type must be stored under very low chilling temperature before using, and will avoid the radiation of light, because it is once finished product, just oneself,, through activating, has polymerization metachromasia.Such a condition of storage will increase the cost of TTI, and can attract some uncertain factors, thereby causes finally indicating the inaccuracy of result.

Patent US4228126 has done improvement to the TTI research of US3999946.Conjugation diacetylene class TTI compound has stable and unsettled two class forms.In patent US4228126, the acetylene compound existing with stable form can be used as TTI and uses, its maximum advantage is exactly stable conjugation diacetylene compounds can be in general at room temperature in daylight preservation, before using as TTI, only need can change active TTI compound into through simple and quick melting recrystallization process cooling or solvent, carry out the indication of Time-temperature.The condition that the acetylene compound of reason that two kinds of unstable with stable form change color of same conjugation diacetylene compounds are different and two kinds of forms transforms has mutually been pointed out in this patent the inside.

Amido formate and sulfonic acid esters conjugation diacetylene type TTI compound are the typical acetylene class of the tool TTI compounds of two classes.Wherein representational compound is: two meta-aminotoluene base formic acid-2, and 4-diine-1, the own diester of 6-, english abbreviation is HDmTU, the structural formula of HDmTU and PFBS is as follows.

Two pairs of fluorobenzene sulfonic acid-2,4-diine-1, the own diester of 6-, can be through the polymerisation induced process of one period of long period as TTI compound, and finally the blast polyreaction through interlock type produces color change.Can utilize this feature that it is instructed for foodsafety, at food, soon can not before edible, to people, point out; Also can reduce on the other hand the waste of food resource, effectively instruct and produce and sell and consumption.

These compounds have the induction period in polymerization of different time length separately, can be respectively used to indicate the consistent perishable farm products of change color process with it in time-quality of temperature changes course.

The colour developing cycle of PFBS and HDmTU is different, if make TTI, only uses a kind of monomer, and the TTI indication cycle of producing is fixed, and the scope of application is narrower.Can by two kinds of monomers are mixed mutually produce the different colour developing cycle TTI to expand its range of application, be convenient to screening simultaneously and want that with food shelf model the TTI that mates fills a prescription.

The present invention also provides a kind of food Time-temperature indicateing arm, it at least comprises the base version of marker and the described marker of carrying, the quality percentage composition of the component of described marker and each component is: 0.001%～0.006% two meta-aminotoluene base formic acid-2,4-diine-1, the own diester of 6-, two pairs of fluorobenzene sulfonic acid-2 of 0.001%～0.006%, 4-diine-1, the own diester of 6-, 8.100%～10.000% bonding agent, surplus is auxiliary agent.

Preferably, the quality percentage composition of the component of described marker and each component is: 0.001%～0.003% two meta-aminotoluene base formic acid-2,4-diine-1, the own diester of 6-, two pairs of fluorobenzene sulfonic acid-2 of 0.001%～0.003%, 4-diine-1, the own diester of 6-, 8.100%～10.000% bonding agent, surplus is auxiliary agent.

Preferably, the described bonding agent of described marker is selected from one or more the mixing in polystyrene, polycarbamate or Corvic.

Preferably, the described auxiliary agent of described marker is methylene chloride.

Food Time-temperature indicateing arm provided by the present invention can be used as military food Time-temperature indicateing arm.

The present invention also provides a kind of Time-temperature indicateing arm of compressed foods, it at least comprises the base version of marker and the described marker of carrying, the quality percentage composition of the component of described marker and each component is: 0.001% two meta-aminotoluene base formic acid-2,4-diine-1, the own diester of 6-, two pairs of fluorobenzene sulfonic acid-2 of 0.003%, 4-diine-1, the own diester of 6-, 9.100% bonding agent, surplus is auxiliary agent, and the OD value of the terminal colour of its standard colors is set to 2.0.This Time-temperature indicateing arm is particularly useful for military 09 formula compacted ration.

Wherein, described bonding agent is selected from one or more the mixing in polystyrene, polycarbamate or Corvic, and described auxiliary agent is methylene chloride.

Accompanying drawing explanation

Fig. 1 is the aggretion type TTI change color trend map of 2.5 years formulas.

Fig. 2 is the aggretion type TTI change color trend map of 4 years formulas.

Fig. 3 is PFBS monomer and HDmTU grey scale change curve map under 100 degree respectively.

Fig. 4 is the graph of a relation of PFBS proportion and Mean Value value.

Fig. 5 is different formulations Mean Value temporal evolution curve map under 100 degree.

Fig. 6 is for formula 7 is at Mean Value value temporal evolution curve map at each temperature.

Fig. 7 is for formula 4 is at Mean Value value temporal evolution curve map at each temperature.

Fig. 8 be under different temperatures TTI-A label OD value along with the variation diagram of period of storage.

Fig. 9 is the time dependent matched curve of OD value at 48 ℃.

Figure 10 is the time dependent matched curve of OD value at 58 ℃.

Figure 11 is the time dependent matched curve of OD value at 68 ℃.

Figure 12 is the logarithm of reaction rate constant and the linear relationship chart of 1/T.

Figure 13 be under different temperatures TTI-B label OD value along with the variation diagram of period of storage.

Figure 14 is the time dependent matched curve of OD value at 48 ℃.

Figure 15 is the time dependent matched curve of OD value at 58 ℃.

Figure 16 is the time dependent matched curve of OD value at 68 ℃.

Figure 17 is the logarithm of reaction rate constant and the linear relationship chart of 1/T.

Figure 18 be under different temperatures TTI-B label OD value along with the variation diagram of period of storage.

Figure 19 is the time dependent matched curve of OD value at 48 ℃.

Figure 20 is the time dependent matched curve of OD value at 58 ℃.

Figure 21 is the time dependent matched curve of OD value at 68 ℃.

Figure 22 is the logarithm of reaction rate constant and the linear relationship chart of 1/T.

Embodiment

Below principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.

Embodiment

1. experimental apparatus and experimental drug

1.1 characterize instrument

1.1.1 infrared spectrum: Shimadzu IR-208 infrared spectrometer (KBr compressing tablet).

1.1.21HNMR:Varian Mercury VX300 nuclear magnetic resonance analyser (TMS do in mark).

1.1.3 fusing point: X-4 type digital micro-analysis melting point apparatus (thermometer is not proofreaied and correct).

1.2 experimental drug

Stannous chloride, propilolic alcohol, methyl alcohol, pyridine, concentrated hydrochloric acid (37%), tetrahydrofuran, triethylamine, fluorobenzene, sulfonic acid chloride, a toluene diisocyanate, methylene chloride, sherwood oil (30～60 ℃), ethyl acetate, potassium hydroxide, dioxane, p-N, N dimethylamine yl pyridines, acetone etc. are commercially available analytical reagent.

Tetrahydrofuran, processes through sodium, heavily steams.Triethylamine, uses potassium hydroxide dried overnight, filters.

Synthesizing of 2.TTI monomer

2.12,4-diine-1,6-bis-hexanols

In 100mL there-necked flask, add successively stannous chloride 2.4g(0.024mol), propilolic alcohol 24ml(0.4mol), methyl alcohol 40mL, pyridine 12mL, pass into air, stir 7h.Potpourri, with ice-cooled, and is added to 20mL concentrated hydrochloric acid, and then add 100mL saturated sodium-chloride water solution, potpourri is placed in refrigerator overnight.By the solid suction filtration of separating out, filter cake is washed with frozen water, and dry, obtains yellow crude product 11.6g, yield 52.7%.By methylene chloride, recrystallizing methanol, obtain white crystal.Fusing point 111-112 ℃.

1HMNR(DMSO-d6,ppm)：5.43(1H,t,J6Hz,CH2OH),4.17(2H,d,J6Hz,CH2OH)。

FT-IR(KBr,cm-1):3500-2600,2363,1618,1478,1351,1032,914,663.

2.2 pairs of fluorobenzene sulfonic acid chlorides

In 250mL there-necked flask by fluorobenzene 46.6mL(0.5mol) dropwise add in 100mL (1.5mol) chlorosulfonic acid, about 1h, keeping temperature in reaction bulb is 20-25 ℃.Dropwise, continue reaction 2h..Reactant liquor is poured in frozen water, had solid to separate out.Filter, filter cake is washed with frozen water, yield 90%.It is stand-by that solid is put refrigerator.

2.32,4-hexadiine-1,6-glycol-bis--meta-aminotoluene carbamate (HDmTU)

In 100mL there-necked flask, add successively 2,4-diine-1,6-bis-hexanol 1.3g(0.012mol) anhydrous tetrahydrofuran solution, a toluene diisocyanate 3.2g(0.024mol) anhydrous tetrahydrofuran solution, stir, dropwise add triethylamine 4mL.According to TLC measured reaction progress.After reaction finishes, reactant liquor is dropwise added in 200mL sherwood oil.Dropwise static several minutes.Precipitation is leached, and wash with sherwood oil, filter and obtain white solid.

1HMNR(CDCl3,ppm)：9.83(1H,s,NH)，7.27-7.14(3H,m,aryl?H)，6.84(1H,d,J6.9Hz,2-aryl?H)，4.9(2H,s,CH2)，2.26(3H,s,CH3)。

FT-IR(KBr,cm-1):3300,2360,1715,1617,1557,1426,1224,1076,617.

2.42,4-hexadiine-1,6-glycol-bis--to fluorobenzene sulphonic acid ester (PFBS)

Under ice bath, (0 ℃) adds 2,4-diine-1 successively, 6-bis-hexanol 0.5g(0.045mol), tetrahydrofuran 30mL, to fluorobenzene sulfonic acid chloride 2.53g (0.013mol), stir.Potassium hydroxide 0.8g(0.014mol) be dissolved in 15mL water, dropwise potassium hydroxide solution added (0 ℃) in reaction bulb, continue to stir TLC point plate measured reaction progress.After reacting completely, in reaction mixture, add appropriate frozen water, stir.Standing, find to have pink insolubles and occur.Filtration obtains pink solid 1.9g, yield 90%.

1HMNR(CDCl3,ppm)：7.95(2H,m,aryl?H)，7.25(2H,m,aryl?H)，4.79(2H,s,CH2O)。

FT-IR(KBr,cm-1):3500,2800-3000,1494,1383,950,840,550.

3. aggretion type TTI basic performance tests

3.1 test materials and equipment

3.1.1 test drug and reagent

PFBS, HDmTU, tygon, polystyrene, methylene chloride

3.1.2 test key instrument and equipment

JC101 type electric drying oven with forced convection, IKA C-MAG HS7 heating stirrer, Shimadzu IR-208 infrared spectrometer, Varian Mercury VX300 nuclear magnetic resonance analyser, X-4 type digital micro-analysis melting point apparatus.Miscellaneous equipment is laboratory conventional equipment.

3.2 contents of the test and method

3.2.1 color composition performance

PFBS and the HDmTU synthesizing of take is research object, analyzes it respectively under 85 degree conditions, along with the situation of the variation colour developing of time, and the colour developing activity of two kinds of colour developing monomers carried out to preliminary overview.

Fig. 3 is PFBS monomer and HDmTU grey scale change curve map under 100 degree respectively.

As can be seen from Figure 3, under same temperature, along with the prolongation of time, the gray-scale value of the colour developing label made from PFBS monomer, HDmTU monomer respectively also increases gradually, and PFBS monomer colour developing speed is fast, and colour developing terminal is short.Surveyed experimental data is carried out to regretional analysis by indicial equation, obtains the kinetic model that the gray-scale value of 85 two kinds of TTI while spending changes with developing time and be respectively:

The grey scale change kinetic model of table 1100 degree aggretion type monomer TTI

Through linear regression analysis data, find the R of two kinds of TTI models ²all be greater than 0.9, the correlativity of matching is higher, can infer that these two kinds of TTI variable colors are that first order kinetics changes, and monomer whose polyreaction is first order kinetics reaction.

3.2.2 monomer formula is analyzed aggretion type TTI color developing

The colour developing cycle of PFBS and HDmTU is different, if make TTI, only uses a kind of monomer, and the TTI indication cycle of producing is fixed, and the scope of application is narrower.Can produce the TTI in different colour developing cycle and expand its range of application by two kinds of monomers are mixed mutually, be convenient to screening simultaneously and want that with food shelf model the TTI mating fills a prescription.

The TTI that potpourri with HDmTU and PFBS different proportion is made into, preliminary by the corresponding relation of index Mean Value INT and color, judge the relationship of the two, scanned picture is processed through Quantity one software, the data obtained after Origin software is processed as shown in Figure 4.

Fig. 4 is the graph of a relation of PFBS proportion and Mean Value value.

As we know from the figure, along with PFBS proportion increases, Mean Value value reduces gradually, and the processing through 100 degree 4h, the recruitment of Mean Value also increases with the increase of PFBS proportion, by illustrating, can, by regulating the ratio of HDmTU and PFBS, control TTI change color.

Fig. 5 is different formulations Mean Value temporal evolution curve map under 100 degree.

As shown in Figure 5, the TTI of 11 kinds of deployed formulas is carried out to colour test, data of each formula after Origin software is processed as shown in Figure 5.As can be seen from Figure 5, growth along with the time, Mean Value desired value is at 100 degree, sharply increase at first, increase gradually subsequently and progressively tend towards stability, and can find out, the TTI indication cycle of different formulations is different, surveyed data are carried out to linear regression analysis according to indicial equation, and the time dependent kinetic model of variation that obtains the Mean Value value of 100 TTI of different formulations while spending is respectively shown in following table 2:

Table 2 different formulations TTI is at the time dependent kinetic model of variation of 100 degree Mean Value values

Through regretional analysis data, each model R2 is all greater than 0.91, and the correlativity of matching is higher, can infer that the change color of aggretion type TTI meets first order kinetics variation, and monomer polymerization reactions is first order kinetics reaction.By various formulas kinetic model and military food quality variation model when 100 spend are matched, result shows to fill a prescription 2, formula 4, formula 7 can mate with food model.

To filling a prescription 2, formula 7 aggretion type TTI carry out colour test at 100 degree, 85 degree, 45 degree respectively, the data of various formulas after Origin software is processed as shown in Figure 6, Figure 7.

Fig. 6 is for formula 7 is at Mean Value value temporal evolution curve map at each temperature.

Fig. 7 is for formula 4 is at Mean Value value temporal evolution curve map at each temperature.

As shown in Figure 6, Figure 7, along with the growth of time, Mean Value value raises first quick and back slow gradually.Contrast two kinds of formulas and find, it is 7 longer that formula 4 variable color terminal times are filled a prescription.Surveyed data are carried out to regretional analysis by indicial equation, and the time dependent kinetic model of Mean Value value variation that obtains 45 degree, 85 degree, 100 TTI of aggretion type while spending is respectively:

The change kinetics model of table 3 formula 7Mean Value value

The change kinetics model of table 4 formula 4Mean Value value

Through regretional analysis data, find, the R2 of various models is all greater than 0.90, and the correlativity of matching is higher, can infer that the change color of aggretion type TTI meets first order kinetics variation, and monomer polymerization reactions is first order kinetics reaction.

4 aggretion type indicateing arm preparation methods

4.1 test materials and equipment

4.1.1 test drug and reagent

PFBS, HDmTU, tygon, polystyrene foam, methylene chloride, ethyl acetate, valve bag, preservative film, freshness protection package

4.1.2 test key instrument and equipment

JC101 type electric drying oven with forced convection, IKA C-MAG HS7 heating stirrer, Shimadzu IR-208 infrared spectrometer, Varian Mercury VX300 nuclear magnetic resonance analyser, X-4 type digital micro-analysis melting point apparatus, X-rite528 light splitting Density Measuring Instrument, white wool brush

Miscellaneous equipment is laboratory conventional equipment.

4.2 experiment contents and method

4.2.1 the selection of adhesive

The fact that polyfoam can be dissolved based on some organic solvents, we dissolve compound monomer and polyfoam with methylene chloride simultaneously, then organic solvent volatilizees and film forming naturally, research for developing the color and testing after pruning size, can, by controlling the amount of polyfoam and the amount of compound monomer, study its colour developing situation.Therefore, we determined aggretion type TTI most suitable be adhesive---polyfoam.

4.2.3 dissolving-volatility process

4.2.3.1 aggretion type TTI formula

Table 5 aggretion type TTI formula

4.2.3.2 preparation process

Control M total=0.0090g, 6cm double dish weighs PFBS and HDmTU by following form, then mixes.

Claim 9.6g polyfoam, with 48mL methylene chloride, dissolve, preparation 0.2g/mL polyfoam dichloromethane solution.

Successively load weighted potpourri is dissolved with 2mL methylene chloride respectively, add 2mL new system 0.2g/mL polyfoam dichloromethane solution, after stirring, dry the demoulding, one of 6 groups of data of plastic packaging film-making.

4.2.3.3 information recording and processing

The good film of plastic packaging is placed in respectively under 45 ℃, 85 ℃, 100 ℃ conditions, regularly observes change color, and use scanner scanning picture, record gray scale, OD, Mean value information.

Recorded data all carries out analyzing and processing with Origin.

4.2.4 dissolving-rubbing method

4.2.4.1 aggretion type TTI formula

Table 6 aggretion type TTI formula

4.2.4.2 preparation process

Control M total=0.0090g, 6cm double dish weighs PFBS and HDmTU by following form, then mixes.

Claim 9.6g polyfoam, with 48mL methylene chloride, dissolve, preparation 0.2g/mL polyfoam dichloromethane solution.

Successively load weighted potpourri is dissolved with 2mL methylene chloride respectively, add 2mL new system 0.2g/mL polyfoam dichloromethane solution, after stirring, dry the demoulding, one of 6 groups of data of plastic packaging film-making.

4.2.4.3 information recording and processing

The good film of plastic packaging is placed in respectively under 45 ℃, 85 ℃, 100 ℃ conditions, regularly observes change color, and use scanner scanning picture, record the information such as gray scale, OD, Mean value.

Recorded data all carries out analyzing and processing with Origin.

4.3 test results and analysis

4.3.1 dissolving-volatility process is prepared material property analysis

Aggretion type TTI label film advantage prepared by dissolving-volatility process is that thickness controllability is strong, and quantitative test error is little.Be both and also have following shortcoming: the solvent evaporates time is long, easy bubble, die edge waste of material, cutting difficulty (mould has obstruction), inefficiency.

4.3.2 dissolving-rubbing method is prepared material property analysis

With solvent, the potpourri that develops the color in formula is dissolved and is mixed with certain concentration solution, with wide brush, brush on glass plate, brushed one deck and after drying, brushed the second layer until solution has been brushed, the inner surfacing of such TTI label film is without bubble, cut out conveniently, can be applicable to a large amount of making.But the film that this method is made can be owing to exerting oneself inhomogeneous but colour development material skewness.

5. aggretion type indicateing arm storage period Time-temperature model determination

The aggretion type TTI that contains different proportioning colour developing monomers making is first gone out to f at high temperature by colour developing cycle and military food storage cycle matching degree preliminary screening, measure its change color situation over time.

5.1TTI-A label

TTI-A label OD value changes as shown in Figure 8 with storage temperature, and wherein the formula of TTI-A label is corresponding to the formula 1 in " table 5 aggretion type TTI formula ":

Fig. 8 be under different temperatures TTI-A label OD value along with the variation diagram of period of storage.

Along with the prolongation of period of storage, the OD value of TTI-A label constantly increases, and temperature is higher, and the speed that OD value increases is faster.Utilize Origin software with the variation of period of storage, by indicial equation, to carry out regretional analysis to TTI-A label OD value under different temperatures, its matched curve is as shown in Fig. 8, Fig. 9, Figure 10:

Fig. 9 is the time dependent matched curve of OD value at 48 ℃.

Figure 10 is the time dependent matched curve of OD value at 58 ℃.

Figure 11 is the time dependent matched curve of OD value at 68 ℃.

Obtain TTI-A label OD value change kinetics model as shown in the table:

Table 7TTI-A label OD value change kinetics model

From above three linear regression model (LRM)s, regression coefficient is higher, the good matching of each model OD value variation tendency.

The logarithm of rate constant and the linear relationship of 1/T are as shown in figure 12 at each temperature:

Figure 12 is the logarithm of reaction rate constant and the linear relationship chart of 1/T.

The regression coefficient of this matched curve is 0.9064, and equation is y=-9617.59x+27.66 good relationship.Fitting data is processed, and trying to achieve reaction activity is that 80KJ/mol. pre-exponential factor is 1.029 * 1012D-1.Therefore, the Arrhenius equation of OD value is:

$k_a=k_{a0}{e}^{-\frac{E_A}{\mathrm{RT}}}=1.029\×{1012e}^{-79.96\×1000/\mathrm{RT}}$

Further known TTI-A material OD value kinetic model is:

$1.6599-A=A_0{e}^{k_{a}t}=A_0{e}^{k_{a0}{e}^{-E_a/{\mathrm{RT}}_t}}=0.70e^{-(1.029\×{10}^{12}{e}^{-79.96\×1000/\mathrm{RT}})t}$

5.2TTI-B label

TTI-B label OD value changes as shown in figure 13 with storage temperature, and wherein the formula of TTI-B label is corresponding to the formula 9 in " table 5 aggretion type TTI formula ":

Figure 13 be under different temperatures TTI-B label OD value along with the variation of period of storage.

From Fig. 5-146, along with the prolongation of period of storage, the OD value of TTI-B label constantly increases, and temperature is higher, and the speed that OD value increases is faster.Utilize Origin software with the variation of period of storage, by indicial equation, to carry out regretional analysis to TTI-B label OD value under different temperatures, its matched curve is as shown below:

Figure 14 is the time dependent matched curve of OD value at 48 ℃.

Figure 15 is the time dependent matched curve of OD value at 58 ℃.

Figure 16 is the time dependent matched curve of OD value at 68 ℃.

Obtain TTI-B label OD value change kinetics model as shown in the table:

Table 8TTI-B label OD value change kinetics model

From above three linear regression model (LRM)s, regression coefficient is higher, the good matching of each model OD value variation tendency.

The logarithm of rate constant and the linear relationship of 1/T are as shown in figure 17 at each temperature:

Figure 17 is the logarithm of reaction rate constant and the linear relationship chart of 1/T.

The regression coefficient of this matched curve is 0.9866, and equation is y=-11258.39x+32.95 good relationship.Fitting data is processed, and trying to achieve reaction activity is that 93.6KJ/mol. pre-exponential factor is 2.042 * 1014D-1.Therefore, the Arrhenius equation of OD value is:

$k_a=k_{a0}{e}^{-\frac{E_A}{\mathrm{RT}}}=2.042\×{1014e}^{-93.6\×1000/\mathrm{RT}}$

Further known kinetic model is:

$1.8442-A=A_0{e}^{k_{a}t}=A_0{e}^{k_{a0}{e}^{-E_a/{\mathrm{RT}}_t}}=0.76e^{-(2.042\×{10}^{14}{e}^{-93.6\×1000/\mathrm{RT}})t}$

5.3TTI-C label

TTI-C label OD value changes as shown in figure 18 with storage temperature, and wherein the formula of TTI-C label is corresponding to the formula 3 in " table 5 aggretion type TTI formula ":

Figure 18 be under different temperatures TTI-B label OD value along with the variation diagram of period of storage.

Along with the prolongation of period of storage, the OD value of TTI-C label constantly increases, and temperature is higher, and the speed that OD value increases is faster.Utilize Origin software with the variation of period of storage, by indicial equation, to carry out regretional analysis to TTI-C label OD value under different temperatures, its matched curve is as shown below:

Figure 19 is the time dependent matched curve of OD value at 48 ℃.

Figure 20 is the time dependent matched curve of OD value at 58 ℃.

Figure 21 is the time dependent matched curve of OD value at 68 ℃.

Obtain TTI-A label OD value change kinetics model as shown in the table:

Table 9TTI-A label OD value change kinetics model

From above three linear regression model (LRM)s, regression coefficient is higher, the good matching of each model OD value variation tendency.

The logarithm of rate constant and the linear relationship of 1/T are as shown in figure 22 at each temperature:

Figure 22 is the logarithm of reaction rate constant and the linear relationship chart of 1/T.

The regression coefficient of this matched curve is 0.9597, and equation is y=-9635.45x+27.72 good relationship.Fitting data is processed, and trying to achieve reaction activity is that 80.1KJ/mol. pre-exponential factor is 1.093 * 1012D-1.Therefore, the Arrhenius equation of OD value is:

$k_a=k_{a0}{e}^{-\frac{E_A}{\mathrm{RT}}}=1.093\×{1012e}^{-80.1\×1000/\mathrm{RT}}$

Further known kinetic model is:

$1.8690-A=A_0{e}^{k_{a}t}=A_0{e}^{k_{a0}{e}^{-E_a/{\mathrm{RT}}_t}}={0.98e}^{-(1.093\×{10}^{12}{e}^{-80.1\×1000/\mathrm{RT}})t}$

6. the matching of aggretion type indicateing arm storage period

Through the screening to lot of materials, to pick out three kinds of formula aggretion type TTI labels and can be used as military food indicateing arm storage period, Time-temperature-OD value change kinetics model of these several formula materials is as follows:

Table 10 Time-temperature-OD value change kinetics model

Known according to TTI response theory, when causing that the energy of activation of main chemical reactions of food generation qualitative change and the energy of activation of TTI are consistent, this indicateing arm just can be in this series products.

So, the kinetic model of TTI: F (X)=k ₁exp (E ₁/ RT _eff) t must with the kinetic model of military food mass change: there is identical energy of activation.That is to say:

Research in conjunction with 09 compacted ration mass change is known, and the kinetic model of its Time-temperature-mass change can be expressed as:

$A=0.025e^{(6.79\×{10}^{10}{e}^{-77.93\×1000/\mathrm{RT}})t}$

Contrasting 09 compacted ration mass change kinetic model and thermo-sensitive material kinetics model of color is not difficult to find, TTI-B is comparatively approaching for formula, military food indicateing arm storage period that it is prepared into can be comparatively approaching the mass change situation of indication 09 compacted ration, if its formula is further adjusted, should prepare the on all four material of energy of activation.

According to research above, when storage temperature is 25 ℃, be that 09 compacted ration shelf life is 1600 days.By the kinetic model of these two parameter substitution TTI-B change color, the OD value that just can calculate its terminal time is 2.0.Therefore, when the terminal colour OD value of standard colors is set, be 2.0, can use by indicateing arm storage period using TTI-A as 09 compacted ration.

Aggretion type TTI change color trend map provided by the present invention is as shown in Figure 1, 2:

Fig. 1 is the aggretion type TTI change color trend map of 2.5 years formulas, and from left to right, the color of color lump is as RGB(238,208,182), RGB(231,163,126), RGB(146,71,52), RGB(122,47,42), RGB(109,52,43), RGB(114,69,50).

Fig. 2 is the aggretion type TTI change color trend map of 4 years formulas, and from left to right, the color of color lump is as RGB(235,205,177), RGB(237,152,111), RGB(178,80,53), RGB(154,53,43), RGB(179,53,39), RGB(139,44,42).

The foregoing is only better embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (7)

1. an aggretion type time-temperature indicator, comprises that weight ratio is two meta-aminotoluene base formic acid-2 of 6:1～1:6,4-diine-1, the own diester of 6-and two pairs of fluorobenzene sulfonic acid-2,4-diine-1, the own diester of 6-.

2. aggretion type time-temperature indicator according to claim 1, described two meta-aminotoluene base formic acid-2,4-diine-1, the own diester of 6-and two pairs of fluorobenzene sulfonic acid-2,4-diine-1, the weight ratio of the own diester of 6-is 3:1～1:3.

3. a food Time-temperature indicateing arm, it at least comprises the base version of marker and the described marker of carrying, the quality percentage composition of the component of described marker and each component is: 0.001%～0.006% two meta-aminotoluene base formic acid-2,4-diine-1, the own diester of 6-, two pairs of fluorobenzene sulfonic acid-2 of 0.001%～0.006%, 4-diine-1, the own diester of 6-, 8.100%～10.000% bonding agent, surplus is auxiliary agent.

4. food Time-temperature indicateing arm according to claim 3, the quality percentage composition of the component of described marker and each component is: 0.001%～0.003% two meta-aminotoluene base formic acid-2,4-diine-1, the own diester of 6-, two pairs of fluorobenzene sulfonic acid-2 of 0.001%～0.003%, 4-diine-1, the own diester of 6-, 8.100%～10.000% bonding agent, surplus is auxiliary agent.

5. according to the food Time-temperature indicateing arm described in claim 3 or 4, it is characterized in that: the described bonding agent of described marker is selected from one or more the mixing in polystyrene, polycarbamate or Corvic.

6. according to the food Time-temperature indicateing arm described in claim 3 or 4, it is characterized in that: the described auxiliary agent of described marker is methylene chloride.

7. the Time-temperature indicateing arm of compressed foods, it at least comprises the base version of marker and the described marker of carrying, the quality percentage composition of the component of described marker and each component is: 0.001% two meta-aminotoluene base formic acid-2,4-diine-1, the own diester of 6-, two pairs of fluorobenzene sulfonic acid-2 of 0.003%, 4-diine-1, the own diester of 6-, 9.100% bonding agent, surplus is auxiliary agent, and the OD value of the terminal colour of its standard colors is set to 2.0.