JP2007114013A - Flavor change detector - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technique capable of the confirmation of the quality of a beverage or the like, which requires various meters such as a pH meter, an electroconductivity meter, a sugar clock, a chlorine densitometer, etc., by one detector. <P>SOLUTION: A change in sugar content is subjected to linear approximation by electrolysis, so that the state of a measuring target and the state of the measuring target at the point of time of next measurement are estimated. Further, with a viewpoint to raise the precision of electroconductivity, the application condition of electrochemical potential is changed to measure individual change quantities on the basis of oxidation-reduction potential. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to detection of flavor change in food and beverage equipment.

In the current system, there are 800,000 restaurants in Japan, and 200,000 cup vending machines have various usage environments such as the number of sales, installation environment temperature, years of equipment used, brands to be sold, etc. . Moreover, it can be said that there is a limit to the current management method that depends on the skills of the personnel handled as the business expands.
On the other hand, in order to realize uniform taste in commercial beverage extraction devices, several types of raw material recipes, ratio setting of concentrated syrup and diluted water, storage by heat retention, hygiene management such as washing, taste, The odor setting method had to be implemented.

  Therefore, first of all, the equipment structure to make the flavor uniform, the method of checking the flavor, the washing to make the flavor uniform, etc. are implemented using the extraction device equipped with the coffee liquid storage container, the post mix, the premix beverage supply device as an example If there is no problem, sort out the problems.

  The explanation of the equipment and the influence of the flavor change will be described by taking the coffee brewing apparatus 1 provided with the coffee liquid storage container as an example. 1 includes a main body 1, a filter 2, and a coffee liquid storage container 3 called a decanter. The main body 1 includes a hot water tank 4 and a hot water heater 5. A filter 2 containing a paper filter and coffee powder is detachably attached.

  The coffee beverage extractor 1 is the most widely used in the coffee extractor, and is used to extract 10 g of coffee powder per cup in a 1.8 L decanter 2 into a 140 mL cup at a time.

  However, since this method is a method in which a predetermined amount is stored in the decanter 3, the time is managed by many restaurant kitchen timers so that the coffee is not boiled. It is necessary to manage the amount of coffee beans, the amount of hot water, and the temperature of hot water to be extracted.

  When the extracted coffee is kept warm, the sugar is decomposed (aminocarbonyl reaction) by keeping the coffee heated. This remarkable change in flavor change due to heating is kept warm for about 30 minutes at a temperature of 90 ° C. or higher. In this background, the restaurant measures 30 minutes with a timer or the like and discards the coffee remaining in the decanter 3 to achieve a uniform taste.

  Further, representative examples of automated equipment include a cup-type vending machine and a beverage supply device called a beverage dispenser shown in FIG. Beverage supply equipment is a machine that pours beverages such as tea, juice, cola, coffee, etc. in a beverage maker's factory in advance by pouring them into a cup directly from the machine or by cooling the beverage. Say that.

  As the method, the water and raw materials (concentrated syrup, powder, beans) shown in FIG. 2 are separately stored and mixed, diluted, dissolved and extracted immediately before drinking, and the beer shown in FIG. There is equipment such as premix that only keeps cold with beverages that have been mixed in the factory in advance, like Chuhai. The following explains the mechanism of extraction, dilution, cooling, etc. for premic and premix equipment.

  First, the equipment description of the post-mix type beverage supply device and the beverage quality securing method will be described. As a feature of the post-mix type beverage supply device, there are many methods of cooking beverages from the time when money is put into the vending machine and the button is pressed, and a method of cooking and serving one by one when customers purchase is adopted. ing.

  In many cases, the post-mix type beverage supply device uses water supplied from a water supply, and extracts concentrated syrup diluted or coffee. These dilution waters 6 always contain sterilizing chlorine, so that the tap water can be drunk safely. However, as an improvement in the flavor of tap water, an activated carbon type water purifier 10 that can provide a delicious beverage is required by removing the odor of lime, mold, red water, and the like.

  The activated carbon type water purifier 10 produces delicious water, but reduces chlorine effective for sterilization to chlorine ions having no sterilization effect. In particular, in the cup-type vending machine, the water piping is an open circuit due to the water supply law, so in the SIS TURN 11, there is a high possibility that bacteria will be mixed from the outside into the atmosphere, and hygiene management becomes a problem.

  In general, since tap water that has passed through the activated carbon water purifier 10 does not contain chlorine, microorganisms are likely to be mixed therein. In order to improve the sanitary condition in these dilution waters, FIG. 3 shows an apparatus called a chlorine generator 9 for converting chlorine ions having no sterilizing effect into chlorine having a strong sterilizing effect by electrolysis.

  In this device, two electrodes 12 are arranged in the container, and when direct current is passed, chlorine ions are changed to chlorine on the anode side and have a sterilizing effect, and the raw water having the same standard as tap water is diluted in the cup machine. The water 6 and the carbonated water 13 can be protected from bacterial contamination, microbial contamination can be prevented, and dilution water can be provided as a basis for providing a delicious beverage.

  Assurement of beverage quality accompanying the chlorine concentration management of the dilution water 6 is realized by setting the current supply time 20 of the chlorine generator 9. The chlorine generator 9 refers to a device that reactivates chlorine deactivated by the activated carbon water purifier 10 by electrolysis. In order to reactivate, the tap water characteristics (electric conductivity 100-500μs, chlorine concentration 5-50ppm or less) in Japan are different. Must. Therefore, if the settings of the chlorine generator are different, there is a possibility of causing an odor problem in the beverage, which requires setting by an expert and periodic check.

  In order to extract coffee with a cup-type vending machine, the diluted water 6 is used to boil hot water in advance with a heater installed in the hot water tank 17, and the brewer 19 and the canister 8 storing the coffee powder. A coffee powder is agitated with air in a so-called extractor, and pressure is applied for about 10 seconds.

  Sugar, cream, etc. are dispensed at a predetermined rotation from the canisters 14, 15. The coffee extracted from the brewer 19 and the sugar, cream, etc. dispensed from the canister are mixed in a mixing device called a mixing bowl 21. Beverage quality is ensured by selling in cups.

  For the coffee flavor setting of the cup type vending machine, the predetermined raw material amount, hot water amount, stirring time, hot water temperature, etc., previously entered by the equipment manager are determined by sensory inspection, and the determined values are entered into the vending machine. This makes the taste uniform. Furthermore, whether or not the cup-type vending machine is in operation with the set input value is confirmed by performing product quality inspections such as microbiological inspection and recipe confirmation about 1 to 4 times a year.

  On the other hand, as a method for supplying a cooled beverage such as a soft drink, a method of instantly cooling the diluted syrup 6 or the carbonated water 13 and the concentrated syrup from the syrup tank 7 stored at room temperature in which the beverage is enclosed is adopted. ing. As a mechanism for cooling at that moment, FIG. 4 shows the internal structure of the beverage supply apparatus.

  In this apparatus, a cooling coil 23 instantaneously cools a pipe that enables instant cooling of a beverage, diluted water 6 or carbonated water 13 concentrated syrup 7. The cooling coil 23 shown in FIG. 4 is a cylinder or an oval / cylindrical cylinder, and is formed as a hollow three-dimensional pipe by an electric sewing tube (seam pipe) having an inner diameter of about 5 mm and an outer diameter of about 6 mm. As shown in the figure, the cooling coil 23 installed in the water tank 22 inside the machine is buried in an approximately 20 L water tank 22 cooled and iced 21 by a cooling device to perform heat exchange.

  The cooling coil 23 made of stainless steel for beverages, which is generally used, takes about 10 seconds for the fluid to pass through the coil, during which time the fluid at 30 ° C. is rapidly cooled to about 2 ° C. at the time of outflow. The In addition, in the ice heat storage, when there is no sale around the cooler in the water tank 22, about 6 kg of ice 21 is generated, and the water in the water tank is agitated by a stirrer (propeller) 24 to exchange heat.

  When there is no sale, the water temperature of the aquarium 22 is almost 0 ° C. due to coexistence with the ice 6, but if the sale continues, the brine 25 which is a heat transfer material such as beverage, cooling coil 23, water stored in the aquarium. Due to the heat transfer medium called the heat transfer of ice, the water temperature of the water tank 22 becomes about 2 ° C. and the ice is melted.

  Concentrated syrups such as Coca-Cola supplied by this method, particularly sugar-based beverages, pay attention to changes in the sugar amount of beverage quality and detect changes in the measured product. A BRIX meter (sugar meter) is known as a quality confirmation device used at that time. The BRIX meter has a minimum incident angle (critical angle) at which the light is totally reflected when a low-refractive-index material from a crystal with a high refractive index enters the measurement medium. The critical angle is obtained by measuring the amount of reflected light with a light receiving element, and the numerical value converted into the concentration of the measurement medium is confirmed.

  Concentrated oolong tea and iced coffee, etc., which have a neutral pH and are almost free of sugar, even in the same concentrated syrup, are supplied by a special device. FIG. 5 shows a system for selling sugar-free beverages. A syrup concentrated in advance in a factory is enclosed in a container called a back-in box 26 and supplied to a restaurant. A system is adopted in which the concentrated syrup is squeezed out by a predetermined amount by a pump called a tube pump 27 and mixed with diluted water for sale.

  The quality of back-in-box beverages is almost zero, so the beverage quality is confirmed by separately extracting the concentrated syrup and dilution water, called the ratio cup shown in Fig. 6, and checking the dilution ratio. Has been.

  On the other hand, unlike the post-mix method of cooking each time, the equipment description and beverage quality assurance of the beverage supply device for beer, which is a typical example of a beverage supply device that is pre-mixed as a beverage at the factory and is said to be only cooled Is described below.

  The beer beverage supply device 29 shown in FIG. 7 passes through the service pipe 30 from the tank 28, the beer supplied to the beverage supply device passes through the cooling coil 23, passes through the water hammer mitigating tetron hose 32 and passes through the valve 31. To be supplied. This system has a small number of parts as a system for forming a heat exchanger, is compact and can satisfy the requirements in a very short time at the time of sale. However, the tank 28 that is stored at room temperature, the nozzle 31 that is in contact with the atmosphere, the service pipe 30, etc. are exposed to microbial contamination, and dirt inside the pipe causes problems even from the viewpoint of beverage flavor change and hygiene. .

  Unlike the postmix, the premix is prepared in advance at a beverage manufacturer's factory. Therefore, factors that adversely affect beverage quality can be attributed to contamination by microorganisms. In view of these circumstances, a beverage quality securing method for a beverage supply device on the premise of mixing of microorganisms will be described. As a method of removing microorganisms, auto sanitation, parts cleaning, etc. are carried out as daily hygiene management methods, cleaning with chemicals about once every six months, and product quality inspections such as microbiological inspection and recipe confirmation once a year or four times By implementing, the uniform taste is realized by human factors.

  We will refer to the legal regulations related to microbial contamination of these beverage supply devices and how beverage quality is affected. In general, when handling beverages with beverage supply equipment, in addition to “soft drinks” indicated in Article 4 of the Water Supply Act, Ministry of Health and Welfare Notification No. 98, “Ministerial Ordinance on Component Standards for Milk and Dairy Products”, We must comply with laws such as the standards for the Tokyo Metropolitan Ordinance. Furthermore, after satisfying these laws and regulations, the flavor of the beverage must be satisfied.

  Then, the hygiene technique management method directly linked to the flavor will be described using the premix beverage feeder described above as an example. The beverage supply apparatus for draft beer instantaneously cools a beer that has been placed in a tank in a beer company in advance, like bottles and cans, placed at room temperature. This system is used in the market about 90% because a large amount of sales can be instantly cooled and compact.

  The instant cooling method has the advantage of using compact and simple equipment as described above, but the problem is that when replacing tanks, beer with a sugar content of about 5% is suspended in the air. There is a risk that yeast or the like may enter the pipe and deteriorate the flavor of the beverage.

  Beer is low at about pH 4 and is kept anaerobic by carbon dioxide, and the hop resin has some antibacterial properties. No problem arises because pupae, etc. do not grow.

  However, there is a possibility of contamination by hop-resistant anaerobic, facultative anaerobic bacteria, and wild yeast, and turbidity, off-flavors, and off-flavors may be generated in the beer by the propagated cells and metabolites. Representative of these harmful germs that can be propagated are gram-positive, such as lactic acid bacteria, and the genus Lactobacillus and Cocci Pediococcus (the only cocci that grow in beer) are easy to acquire anaerobic and hop resistance even in a carbon dioxide environment. It produces turbidity, off-flavor (acidity), off-flavor, and polysaccharides. On the other hand, the genus Acetobacter and Acetomonas, which are acetic acid bacteria, are said to not reproduce as long as they remain anaerobic.

  Of these microorganisms mixed in beer, wild yeast is the easiest to breed in beer, 80% of which is said to be of the genus Saccharomyces. This yeast assimilate sugars, which are nutrients in beer, and the propagated wild yeast is sticky and adheres to the inside of the pipes, causing off-flavors and turbidity.

  Table 1 shows the conditions under which the contaminated parts of parts that are affected by microbial contamination and proliferation of equipment actually operating in the market are compared.

This shows the liquid contact part through which beer passes, as shown in FIG. 7. Dispense head 33: internal capacity about 3.5 ml, service pipe 30: internal capacity about 35 ml, cooling coil 23: internal capacity about 350 ml, and nozzle 31 are combined. This compares the parts that are cleaned with and parts that are not cleaned, and confirms the status of microbial contamination.

  The used equipment is an example in which equipment having a width of 250 mm, a height of 480 mm, and a depth of about 480 mm is used. According to this result, it can be said that the service pipe 2 is the most subject to microbial contamination.

  The reason that many service pipes 30 are contaminated with microorganisms is that they have a large storage capacity and are placed at room temperature, and microorganisms mixed from the dispense head 33 are accumulated in the pipes when the beverage replaces the tank 28. It is thought that. In order to reduce these influences, the resin hose used in the service pipe 30 is replaced and discarded in about one month because olefinic or fluororesin is used in the wetted part.

  On the other hand, naturally, deposits adhering to the service pipe 30 pass through the cooling coil 23 located downstream, but it is difficult to discard the cooling coil 23 in consideration of cost and the like. Inside the cooling coil 23 installed in the cooling tank 22 shown in FIG. 2, a saturated solubility difference or the like occurs due to a rapid temperature difference of the fluid passing therethrough.

  As a result, as shown in FIG. 8, precipitates (tartar or the like) 34 adhere to the inner surface of the pipe like arteriosclerosis. These precipitates 34 are often seen at the outlet when the inlet and outlet of the cooling coil 23 are compared. This means that since the beverage left at room temperature rapidly exchanges heat with the cooled brine 25, deposits are likely to deposit near the inlet of the cooling coil 23.

  These precipitates 34 are said to be tartar and are said to be inorganic substances such as calcium oxalate in which a potassium salt or a calcium salt is bound to a dicarboxylic acid having two carboxyl groups in the molecule. In addition to the microorganisms flowing in from the service pipe 30, the inorganic substance deposited by heat exchange in the cooling coil 23 becomes a hotbed of the microorganisms and impairs the taste of beer. Therefore, it is necessary to periodically check the deposits adhering to the inside of the cooling coil 23 so as to replace the service pipe 30.

  Specifically, Table 2 shows daily cleaning methods recommended by beverage manufacturers in order to reduce the deterioration of beverage quality in a beverage supply device for beer.

If the beverage supply apparatus is not cleaned according to these recommended methods, it presents various problems. FIG. 9 shows the number of microorganisms in the case where cleaning is not performed. The result of FIG. 9 shows that the beverage quality deteriorates in about two weeks. However, even when not washing for two weeks or three weeks, if several cups of beverages are sold, the number of microorganisms is drastically reduced and the beverage quality is deteriorated. It can be said that it will disappear.

  On the other hand, problems when the cleaning is periodically performed according to the standard manual will be described below. FIG. 9 also investigates the quality of the first and several cups provided at the restaurant after washing. According to this, in about 35% of restaurants, washing water remains in the piping, and there is a possibility that the quality of beverages to be sold may be significantly deteriorated.

  As described above, various knowledge is necessary for the restaurant and the beverage store to handle the beverage supply device based on various regulations. In addition, for uniform taste, it was difficult to create a condition where the operating environment could be constantly monitored based on the experience so far, with provisions in terms of management and handling of equipment.

  A possible reason for this is that the content beverage such as beer remaining in the beverage feeder must be discarded when washing is performed. Specifically, it is mentioned that about 1.5 cups (about 600 mL) stored in the cooling coil 23 in the beverage feeder must be discarded as profit loss of the restaurant. In particular, restaurants that have a small daily sales volume often hesitate to do so.

  In addition, beverage quality confirmation by a beverage maker is performed irregularly, and it is difficult to monitor the daily operation status of vending machines and beverage supply machines installed in restaurants.

  For these reasons, there is a need for a system that monitors the daily operation status, easily confirms the reference raw material settings, confirms the degree of flavor reduction during storage, optimizes the chlorine concentration, and confirms the sanitary condition.

  In response to these demands, Patent Document 1 is known as a method for detecting a change in flavor state using a beverage such as coffee as a measurement object. The beverage quality determination device according to Patent Document 1 is a beverage quality determination device that determines the quality of a beverage that is cooked by transporting an extract extracted by passing water through a raw material by an extractor through a transport passage. It is.

  As shown in FIG. 10 and FIG. 11, this apparatus is provided with a concentration sensor that detects the concentration of the extract liquid that is provided in the transfer path and flows through the transfer path, and the extract solutions that are detected at a plurality of different timings by the concentration sensor. A parameter calculating means for calculating a parameter representing a change state of the concentration based on the concentration of the beverage, and determining the quality of the beverage by comparing the calculated parameter with a predetermined reference value, that is, a difference quality determining means for the electrical conductivity It is characterized by having.

  However, when measuring the state change due to electrolysis in this device, the applied voltage is high, and it is outside the range where unnecessary electrochemical reaction does not occur, so unnecessary electrochemical reaction other than coffee occurs. There's a problem.

  For example, in order not to be affected by this, when a platinum electrode is used as the working electrode and the counter electrode, an applied potential range in which electrolysis of water molecules, components in the buffer solution, and redox reaction of the supporting electrolyte does not occur. Setting is required from 5V to + 1.3V. However, since this apparatus uses 5V and 12V, it is obvious that it is affected by unnecessary electrolysis. In addition, this flavor change detector has not been verified for storage of beverages, optimization of extraction conditions, detection of microbial contamination, cleaning time, disposal time, and the like.

  On the other hand, FIG. 12 shows a method of introducing a short electric pulse to an electrode and recording a current or voltage, or a transient response of current and voltage for a specific number of pulses, which is introduced in Patent Document 2. A plurality of pulses having different voltages are used for each of the test sequences for detecting the flavor component. The resulting signal is then recognized or compared by a computer pattern recognition program to see if the liquid material, for example beer or milk, is within set quality limits.

According to this method, (1) a pulse voltage measurement method for obtaining information (transient response curve), (2) various electrode materials or modified electrodes or pulse voltages for obtaining various chemical reactions that vary the transient response. Use (3) Use of curve fitting methods to extract or sample information from the obtained transient response, (4) Use of various multivariate analysis signal processing methods to interpret the obtained information. It is done.

  However, since this method has not been analyzed for chemical reaction by electrolysis, and furthermore, since the obtained information is a method of performing batch processing, the linearity of the system has not been discussed. Complex processing such as multivariate analysis is required, and it can be said that it is difficult to detect flavor with a simple device.

  Therefore, the following will explain how to measure beverages such as coffee, tea, Japanese tea, beer, etc. according to the measurement object and detection purpose, such as optimization of extraction conditions for each measurement object, microbial contamination, and detection of washing time. In general, it can be said that sugar is involved in the most important reaction between components such as quality formation and deterioration of food, for example, a phenomenon in which food is colored and browned during its processing and storage.

  In the case of black tea, polyphenol components such as tannin are oxidized by the action of oxidase and polymerize to brown. It is said that essential fatty acids such as linoleic acid are converted into peroxides by the action of the enzyme lipoxygenase as an essential fatty acid oxidation, and aldehydes produced by the decomposition thereof cause browning.

  On the other hand, unlike the case of degrading enzymes, non-enzymatic browning involves almost all major food components such as sugars, phenols, fats and oils, ascorbic acid, amino acids, peptides, and proteins. Oxidative decomposition by heating of oil and polymerization, browning by dehydration, decomposition reaction by dehydration, caramel reaction that browns when sugar or glucose is heated and at the same time a sweet aroma, reducing sugars such as glucose and fructose coexist in food , Maillard reaction (aminocarbonyl reaction) in which glucose reacts with peptides, proteins, etc. to cause glycolysis and browning. Considering these theoretical approaches, it can be said that sugar consumption is related to the setting of standard ingredients for beverages and the degree of flavor reduction during storage, and it is possible to form a system with this sugar content as one index. It suggests.

  Next, as a specific example, the relationship between extraction, storage (storage), and washing time for tea and coffee as an example will be described below with respect to the amount of change in sugar and the amount of change in flavor. The tea leaves of tea and black tea contain caffeine, theanine, tannin or polyphenol (generically including catechin and other catechin derivatives). These components have the property that catechins are reduced by oxidative polymerization during the production process, and fresh tea leaves exhibit a strong bitter taste.

  On the other hand, with regard to the color of black tea, the reddish brown color of fermented black tea leaves is due to theaflavin and thearvidin in which catechin is oxidized. For example, the light blue color of black tea is determined by the content ratio of theaflavin and thealvidin, and orange-red when there is a lot of theaflavin, and brown when it is abundant. Regarding the deterioration of tea quality over 3 months after production, especially when it absorbs moisture, catechin, theaflavin, thearvidin, amino acids that characterize the taste and color decrease, the color and taste deteriorate, and the aroma also volatilizes. Ingredients decrease.

  For Japanese tea, it is said that the total nitrogen and amino acids, especially theanine and arginine content in tea exudate are highly correlated with quality. (Teaken 78: 53-60, 1993) Since tea infusion contains a large amount of reducing substances such as catechin and ascorbic acid, it can be said that the dissolved oxygen concentration is low. That is, the degree of beverage extraction can be confirmed by a redox reaction.

  Next, the flavor-forming elements of coffee are exhibited by bitterness, sourness, sweetness, aroma, richness, miscellaneous taste, aggregation due to humic acid, and turbidity, and the relationship to the components will be described with reference to FIG.

  The main components of bitterness are those obtained by caramelizing saccharides and carbonizing organic substances including saccharides. For proteins and cellulose, amino acid compounds and carbonyl compounds such as glucose and fructose are dehydrated by heat to cause Maillard reaction. The main component of coffee acidity is the acidity of organic acids such as citric acid, malic acid, lactic acid, caffeic acid and quinic acid, and is produced by heating.

  On the other hand, a sour taste with an off-flavor is a result of oxidation of lipid in addition to organic acids such as formic acid, acetic acid and oxalic acid. Sweetness is derived from monosaccharides such as glucose and fructose, and disaccharides (small sugars) such as sucrose and maltose. The scent component is an aromatic compound such as caffeic acid or an aromatic fatty acid. It is based on tannin (generic name for chlorogenic acids) that binds protein, alkaloids and metal ions of astringency and astringency, and forms a sparingly soluble salt. Chlorogenic acid and tannin are all contained in polyphenols. Each component amount in the coffee extract is shown in FIG.

  These coffees are composed of caffeic acid and quinic acid, such as 5-caffeoylquinic acid in which the hydroxyl group (-OH) of quinic acid and the carboxylic acid (-COOH) of caffeic acid are ester-bonded. Chlorogenic acid was present.

  Chlorogenic acid is hydrolyzed and reduced to caffeic acid and quinic acid by heat during roasting. Caffeic acid and quinic acid produced by hydrolyzing chlorogenic acid are greatly involved in the taste and aroma of coffee and have bitterness, astringency and sourness.

  Another effect on flavor is humic acid. Humic acid is produced by the hydrolysis of proteins, especially when it contains carbohydrates and is hydrolyzed with acids. Humic acid has a molecular weight of 2000 to tens of thousands, and has many hydroxyl groups [—OH] and carboxyl groups [—COOH] as functional groups.

  As described above, the aminocarbonyl reaction, which is an oxidation reaction, is also involved in coffee, and it exhibits a rich coffee flavor in the case of an appropriate amount due to the decomposition of sugar. However, deviating from the proper amount means that the quality is deteriorated.

  Furthermore, for example, the phenomenon that the coffee liquor becomes turbid when it is cooled when coffee beans are extracted can be explained by the generation of unnecessary complex salts due to the characteristics of humic acid. Specifically, it is very inhomogeneous in mass, structure, and shape, and its characteristics are dissipated, but it is insoluble in acid and soluble in neutral to alkali, and an aqueous solution is brown to dark. As a characteristic of humic acid, it forms complex salts that are insoluble in water by combining with divalent or higher metals (Fe2 +, Fe3 +, Ca2 +, Mg2 +, etc.).

  As described above, it can be said that sugar is closely involved in flavor formation, liquid turbidity during cooling of coffee, etc., pH reduction during storage, and the like. Furthermore, even during storage, coffee causes amino acid + sugar-> aldehyde + enaminol [strecker decomposition (amino-carbonyl reaction)] enaminol-> pyrazine [cyclization reaction], and the pH is reduced during storage due to decomposition of the sugar. Reduces and adversely affects flavor.

  On the other hand, it can be said that the amount of sugar, which is an energy source required for growth, is also involved in the flavor change due to the growth of microorganisms. Microorganisms metabolize carbohydrates and interact with fatty acids, amino acids and other metabolism to perform various important functions as nutrients.

  FIG. 15 shows a cycle of yeast with beer alcohol fermentation. Virpinate decarboxylase decarboxylates and converts it to aldehyde, and further produces ethanol in the presence of alcohol dehydrogenase.

  Regarding the deterioration of beer, the active carbonyl group of high molecular weight melanoidin becomes an electron acceptor in beer and oxidizes higher alcohols to aldehydes, causing browning and flavor deterioration. appear. As described above, contamination by yeast is produced in all yeasts during the fermentation process, and proceeds to the process of production and decomposition of diacetyl shown in FIG.

  Diacetyl produces α-acetolactic acid by acetaldehyde and pyruvic acid in yeast cells. This α-acetolactic acid goes out of the yeast and is oxidized to diacetyl. Both lactic acid bacteria and yeast metabolize one glucose molecule into two molecules of pyruvate, and yeast metabolizes pyruvate into acetaldehyde in the presence of Mg ++ and metabolizes into ethyl alcohol in the presence of Zn ++.

  As a result, two molecules of ethyl alcohol are generated from one molecule of glucose. In this case, the flavor (butter odor, scotch butter odor, pickle odor) brought about by yeast is (1) alcohol, (2) acetaldehyde, (3) ester: a combination of alcohol and acid.

  On the other hand, as microbial contamination other than yeast, in the case of lactic acid bacteria contamination, diacetyl is produced at the end of fermentation, and only diacetyl remains at a high concentration. If there is lactic acid bacteria contamination, diacetyl is generated in the aged beer, and as the contamination progresses, the acidity increases and turbidity appears in the beer. Lactic acid bacteria are collectively called bacteria that produce 50% or more of lactic acid per consumed sugar. If classified according to shape, it is classified into cocci, bacilli and spore bacteria, with Lactobacillus and Pediococcus as representative examples.

  Regarding whether or not the estimation of sugar utilization as a nutrient source by these microorganisms is correct, and further about the change in the flavor component as a result of the utilization, the Saccharomyces cerevisiae NBRC 1439 strain of SPOILED BEER yeast was used as a test sample, and the YM liquid medium (Glucose 1%, Peptone 0.5%, Yeast extract 0.3%, Malt extract 0.3%, pH 5.6) Inoculate yeast into 2 mls and culture at 30 ° C for 2 days The medium was changed once).

  One is replaced with YM liquid medium, the other is filled with beer, cultured overnight (about 19 hours) at 30 ° C, the cells are collected by centrifugation, suspended in sterile distilled water, washed twice, The washed cells were suspended in 40 ml of beer.

  30 samples of yeast beer suspension samples (hereinafter referred to as YM samples) using yeast cultivated only in a YM liquid medium (yeast beer suspension) using yeasts accustomed to beer overnight. Incubated at 0 ° C.

  Next, in the experiment, 1 ml suspension was sampled and inoculated every 2 hours up to 8 hours after 5 hours. Centrifugation of the inoculated liquid and filtration through a 0.45 μm pore size membrane is performed using high-performance liquid chromatography column: Shodex Asahipak NH 2P-504E, mobile phase: acetonitrile / water = 6/4 (v / v), flow rate : 0.8 ml / min, Temperature: 40 ° C., Detection: Differential refractometer (RI) conditions.

  FIG. 16 shows that the amount of change in the sugar content assimilated by microbial contamination under the above conditions was detected by high performance liquid chromatography. Elution pattern of high performance liquid chromatography When compared with the elution pattern of beer as a control, no change was observed in the elution pattern after 8 hours for either sample of beer or YM. There was almost no difference.

  On the other hand, the peak at 10.45 min of this elution time is clearly reduced in the analysis of the sample after 5 hours in 2 days, although the other peaks are almost the same as the original beer and the sample after 8 hours. , It changes to about a quarter of the original beer peak.

  Under the above conditions, it can be seen that in the beer fermentation process, polysaccharides having a sugar amount of 7 or more are assimilated by yeast, but side chain yeasts cannot be assimilated. In general, microorganisms have a property of starting to decompose from a sugar that is easily assimilated, and this result means that the process of glycolysis starts from a linear substance hexaose with a sugar content of less than 7.

  FIG. 17 shows a comparison of beer immediately after opening and beer contaminated with microorganisms with respect to the flavor component, pH, electrical conductivity, color difference meter, physical property values, and the like. As a result, it can be seen that succinic acid, acetic acid, acetic acid odor, and ethanol odor are increasing as flavor changes of the beverage due to microbial contamination.

  The reason why the flavor component of beer changes due to microbial contamination is as follows. The amount of change between beer immediately after opening and beer contaminated with microorganisms is about 78% for hexasauce, 9.3% for glucose, and BRIX. It became 9.25%, and it became clear that sugar was decomposed by microorganisms and nutrition was supplied. Further, as the liquid characteristics of beer contaminated with microorganisms, the electrical conductivity, pH, and color difference change with electrical conductivity of 21%, pH of 14.6%, and color difference L value of about 2%.

  As described above, it has been explained that various beverage quality degradations can be measured by analyzing the sugar content. Next, an apparatus capable of detecting the deterioration of beverage quality by specifically focusing on the sugar content will be described.

  In general, when measuring the degree of deterioration of beverage quality, a sugar meter using a refractive index used in a quality confirmation method for a sugar-based beverage can be imagined as a detection device. However, since the sugar content meter using refractive index is detected in combination with glucose, isomerized sugar, isomerized sugar, invert sugar, lactose, maltose, citric acid, acetic acid, etc., various factors are intertwined. On the other hand, when sugar is used as a nutrient source for coffee or microorganisms with a small amount of sugar, it is necessary to capture the entire saccharide as a whole with minute changes. In other words, in the sugar content meter, since various sugar contents are measured in combination, there is a high possibility that the numerical change is buried.

  Therefore, in food / beverage production facilities, Patent Document 3 reports a system that focuses on the presence of HMF produced by the reaction of sugar and amino acids in food (aminocarbonyl reaction), which is one of the causes of browning. Has been. HMF is generated and increased during the heating, processing, storage, etc. of food, especially when the storage temperature is high, HMF increases, causing browning of food and degrading the quality of food. It is. However, in order to confirm HMF as an index, it is common to use a large apparatus such as high performance liquid chromatography, and it is difficult to easily confirm the quality at a restaurant.

  On the other hand, (1) selectivity is excellent. (Specifically measures a certain sugar.) (2) Not affected by coloring, turbidity, etc. (3) Operates under mild conditions at normal temperature and near neutrality (4) Simple operation (5) Rapid measurement (15 Can be measured in seconds). (6) The result can be obtained by direct electrical signals. (7) The blood glucose shown in Patent Document 4 that introduced the use of a biosensor in which the enzyme shown in FIG. 18 is immobilized as a small portable and personal use sensor. A value meter, urine sugar meter, lactic acid meter, etc. are known.

The blood glucose level and the like are measured by an enzyme reaction and an electrode reaction for measuring sugar (glucose) in urine or blood, in which hydrogen peroxide is generated when glucose is oxidized by the action of an enzyme. Glucose + oxygen ⇒ gluconolactone + H ₂ O ₂ as an enzyme reaction, and electrons are generated when hydrogen peroxide is oxidized on the electrode, and H ₂ O ₂ ⇒ hydrogen ion + oxygen + electron electrode reaction as an electrode reaction. The measurement principle is to detect the electrode reaction at the working electrode and the counter electrode, and the potential of the solution at the reference electrode.

Furthermore, when a constant voltage (for example, 700 mV) is applied to the working electrode with respect to the reference electrode, an oxidation reaction of hydrogen peroxide occurs on the working electrode, an oxidation current is generated, and a current flows from the working electrode to the counter electrode. At that time, the potential between the working electrode and the reference electrode is controlled to be constant.

  However, this method is a method that selectively (specifically) measures glucose required for the measurement purpose, for example, in the case of a pedometer. On the other hand, for example, the flavor change that is affected by the growth of microorganisms, which is the object of the present invention, is a method with selectivity when considering the fact that the sugars to be assimilated differ in various ways and the measurement target is different. , Likely to inhibit the use range.

JP 2004-46714 A Special table 2001-516052 gazette JP 2000-4867 A JP 2004-233294 A Tea Research Bulletin 78: 53-60, 1993

  The present invention has been made in view of the above matters, and its purpose is to provide a technology for solving problems such as storage of beverages and foods, optimization of extraction conditions, detection of microbial contamination, cleaning time, and disposal time. is there.

  It is an object to compare the changing factors specified in advance by the rule of data against those having a reference value, to determine that a change exceeding the threshold value has occurred, and to determine that a flavor change has occurred.

  In addition, it is not a method of expanding and extracting only a certain amount of change in sugar (those having selectivity) like an enzyme-immobilized membrane used in a blood glucose meter, etc. It is an object of the present invention to not require the membrane selectivity in which is immobilized.

  In order to solve the problem, the present invention is characterized by linearly approximating a change in the amount of sugar by electrolysis and estimating the state of the measurement target and the state at the next measurement time point. Furthermore, from the standpoint of increasing the accuracy of electrical conductivity, it is characterized by changing the application condition of the electrochemical potential and measuring the individual change amount by the oxidation-reduction potential.

  The present invention is characterized in that a single detector can perform quality confirmation that required various instruments such as a pH meter, an electric conductivity meter, a sugar clock, and a chlorine concentration meter. Furthermore, it is not an enzyme immobilization that gives attention to a specific amount of sugar, but also solves problems such as food storage, optimization of extraction conditions, detection of microbial contamination, washing time, and disposal time.

  It is characterized by detecting microbial contamination by flavor change, and it grows as a nutrient source by assimilation of saccharides by microorganisms. Therefore, the change in the amount of sugar to be assimilated is measured and taken as a flavor change amount. Based on these quantifications, it is judged that the quality has deteriorated due to microbial contamination, and the cleaning time can be detected.

  By looking at the quality of the whole beverage, it is possible to detect the identification of brands, abnormal operation, etc., and check whether the food is cooked according to the amount of recipes prepared in advance.

  Furthermore, it is possible to detect a change in flavor by measuring the degree of oxidation related to heating, storage time, etc. due to the aminocarbonyl reaction by the amount of sugar. In addition, the chlorine generation concentration can be confirmed by electrolysis, and the beverage quality of the diluted water can be improved.

  Embodiments of the invention will be described below with reference to the drawings.

  As a first embodiment, a three-electrode cell type flavor change detection apparatus shown in FIG. 19 will be described. In this system, an auxiliary electrode is used as the third electrode, and the electric potential of the working electrode is measured and controlled with respect to the reference electrode, and in order to ensure the accuracy of the electric potential, almost no current flows through the reference electrode. This is a method in which when an oxidation reaction occurs at the working electrode, an electron received by the working electrode is reduced at the auxiliary electrode.

  First, FIG. 20 shows the results of collecting coffee sold at a major coffee store and measuring a certain amount of sugar and electrical conductivity. According to this result, the electrical conductivity is about 45% lower than the reference value for coffee extraction, and it can be seen that there is a limit in the current operation method. The reason for this is that in many major coffee stores, store operations such as coffee extraction are performed according to a predetermined manual. In order to operate as if the setting is correct, it is highly likely that the coffee purchaser will sell in large quantities until the customer makes a complaint, as in the case of the measurement conducted this time.

  As a result of FIG. 21, the characteristics of the coffee solution show that the eluted sugar amount and electric conductivity are almost dual, and the elution of the sugar amount by extraction can be substituted by measuring the electric conductivity.

  Based on the above premise, a potential step called chronoamperometry shown in FIG. 22 was applied to the triode cell apparatus shown in FIG. 19 and the transient response of the current was measured. As measurement conditions, a current value of T1 = 10 seconds was measured, the electrode used was a carbon electrode, and the contact area with the solution was 7.07 mm 2. According to this, when measuring extraction conditions such as coffee, it can be seen that the extraction conditions can be measured by electrical conductivity.

  FIG. 23 is a measurement using a triode cell device and chronoamperometry for different brands and different coffee concentrations. (1) in FIG. 23 shows the beverage characteristics for the electrical conductivity 2000 μs and the brand A. On the other hand, (2) is optimally extracted with electrical conductivity 2111 μs, brand B and brand B. On the other hand, (3) has an electric conductivity of 1767 μs, which is a slightly thinner coffee than (2).

  First, with respect to (2) in FIG. 23, the applied voltage and the current value have a linear relationship, the R-2 power value is 0.9923, and the current value = slope × applied voltage + intercept linear function. It can be expressed. Furthermore, (1), (2), and (3) show that the shade of extraction can be estimated by an intercept (the slope is almost the same), and that the slopes of beverages and bean varieties can be said to change.

  In general, it is said that the electrical conductivity needs to be corrected for temperature. Therefore, FIG. 24 shows the characteristics of electric conductivity and temperature, and the R-2 value for the linearity of temperature and electric conductivity is 0.9629, which indicates that temperature correction can be performed using an approximate expression.

FIG. 25 shows the changes in beer flavor caused by microorganisms other than the extraction conditions, with the pH and electrical conductivity as management indices. FIG. 26 shows the electrical conductivity and pH of beer brand A and brand B over time. In addition, the figure
27 shows the rate of change in electrical conductivity and pH. According to this, it can be seen that the two management parameters change greatly from a point in time exceeding a certain time, in this case, 80 hours (three days). Therefore, as for the change in the flavor of the beverage due to a certain microorganism, it is possible to determine that it has an adverse effect on the flavor if it exceeds a certain threshold as in the case of coffee extraction.

  FIG. 28 shows a flowchart of system construction based on these concepts. When a control system is constructed according to this flowchart, the slopes that differ depending on the types of beverages and beans, etc., are called from preset brands, and only the initial sales are used to calculate the slope. It becomes possible to estimate sequentially. Due to the difference between the estimated value and the actually obtained value, it is possible to diagnose abnormality with respect to flavor change and improve the quality of beverages provided to customers.

  The control signal is detected and controlled according to the flowchart of FIG. 28, and the above-described extraction conditions can be optimized, and the cleaning time due to microbial contamination, microbial contamination, contaminants, and the like can be detected. Furthermore, the electrical conductivity and pH are also effective indexes for the deterioration of the coffee extraction due to heat retention shown in FIG. 29, and it is possible to detect problems such as storage of food and detection of disposal time in the first embodiment. It is.

  In the present invention, the detection method using the triode cell device has been mainly described. However, the current pH measurement can be performed by using a conventional glass electrode together with an ISFET which is a kind of MOSFET. It is.

  In the first embodiment, flavor alteration can be easily confirmed, but it takes time to transition from a transient response to a steady state. Therefore, the transient response is improved, that is, the charging current time is shortened by optimizing the potential application conditions, the contribution of the charging current is reduced (improvement of microanalysis accuracy), the current sampling time is changed and the electrode reaction is changed. A second embodiment will be described as a method for precise analysis.

  As a second example, the method was called square wave voltammetry, in which a pulse-like potential slightly different each time was periodically applied, and the current was measured at fixed time intervals. In this method, since the contribution of the charging current of the solution is small, a minute amount analysis is possible, and since the Faraday current component can be extracted, the electrode reaction can be performed precisely.

  FIG. 30 shows the results of measuring beer microbial contamination and sugar concentration change by square wave voltammetry. The electrode is a carbon electrode (GC), and the used beer is compared immediately after opening (good) and left for two days (bad). The good property was BRIX 5.5%, pH 4.22, electric conductivity 1429 μs, and the bad was BRIX 5.5%, pH 4.27, electric conductivity 1514 μs. On the other hand, the voltage application conditions of square wave voltammetry are: square wave amplitude = 0.025V, step potential = 0.004V, and pulse width = 30 Hz.

  In this method, the scanning time is 2 seconds, the entire system is measured, and substrate concentration difference, that is, significant redox reaction occurs in A part and B part. In (1) and (2) shown in FIG. By detecting that component, it can be said that it can be estimated even for a specific change or a minute amount.

  A block diagram of a sensor embodying the first and second embodiments is shown in FIG.

  In the first and second embodiments, the plateau region where the diffusion current becomes flat near the applied voltage of −0.1 V shown in FIG. 32 is used, and the diffusion current depending on the concentration changes even if the applied voltage changes. It is also possible to carry out a chlorine concentration measurement using a polarogram method using characteristics that do not.

  As mentioned above, although the drink supply apparatus has been mainly described as an example, the product of the present invention can be applied to food-related applications such as oil deterioration and cooking of juice. The explanation is based on the example of Japanese buckwheat soup. Soy sauce, sugar, and mirin, which are ingredients for buckwheat soup, all have quite strong properties. It happens in between and can make a savory juice.

  As the role of soy saccharides in the maple, first, a chemical reaction occurs between the amino acids contained in soy sauce and the saccharides contained in sugar or mirin, and melanoidin is produced.

Glutamic acid contained in soy sauce works synergistically with the umami taste of inosinic acid, is strong against taste, and produces a unique umami taste. In particular, since rich soy sauce contains a large amount of glutamic acid derived from soybeans, this produces a umami that works synergistically with the umami of inosinic acid contained in bonito.

  On the other hand, the role of mirin in maple has an action of eliminating the raw odor in addition to sugar. Mirin is made by adding shochu to the tank, ripening it and adding steamed rice. At this time, gonococcus is called self-digestion and decomposes the microbial cells with its own enzyme, but at that time it creates a substance that has the power to quench the fishy odor.

  In addition, the booklet is made by heating soy sauce, but it is in various states depending on how it is heated, how sugar is added, and the heating time. Soy sauce and sugars rapidly undergo a chemical reaction when the temperature reaches 80 ° C. or higher, and melanoidin is produced. The reason why the temperature adjustment and the heating time are important at the time of making the maple is to prevent the formation reaction of melanoidin from proceeding excessively and becoming strong brown.

  By paying attention to the amount of sugar that is the basis of food and drink in this way, development into various foods becomes possible. For example, in the case of deployment to a cooking method called a central kitchen, which is currently used in chain-type restaurants, etc. And uniform flavor. Furthermore, since BSE occurs in Japan, problems and scandals such as camouflage labeling, additives, and agricultural chemicals have frequently occurred, and consumers are increasingly worried about food. In order to restore food trust, the restaurant industry can link to legal compliance of companies, thorough traceability and hygiene management in food procurement, and display and information disclosure.

Structure of the storage type coffee extractor Postmic cup vending machine structure Chlorine generator and constant current conduction conditions Cooling system in beverage dispenser Back-in-box postmix beverage supply device Ratio cup Premix beverage supply device Inorganic deposits in cooling coils Comparison of the number of microorganisms with and without washing Prior art flavor detection apparatus Flow chart of flavor detection apparatus in the prior art Voltage application condition of flavor detection device in the prior art Coffee flavor change process Amount of coffee ingredients Microbial fermentation process in beer Measurement of sugar content during microbial growth by high-performance liquid chromatography Changes in flavor components due to microbial growth Immobilized enzyme membrane sensor chip for blood glucose meter 3-pole cell device Quality check of coffee drinks in a major coffee chain Relationship between sugar content and electrical conductivity in coffee Voltage application conditions for chronoamperometry according to an embodiment of the present invention Quality confirmation of coffee measured by chronoamperometry according to one embodiment of the present invention Temperature and electrical conductivity confirmation according to an embodiment of the present invention Beer quality check in the market Confirmation of beer quality deterioration due to microbial contamination according to an embodiment of the present invention Confirmation of beer quality deterioration degree (%) due to microbial contamination according to one embodiment of the present invention 1 is a flowchart of a chronoamperometry apparatus according to an embodiment of the present invention. Insulation time and beverage quality of coffee according to one embodiment of the present invention Square wave pulse voltammetry according to one embodiment of the present invention. Square wave pulse voltammetry apparatus according to one embodiment of the present invention Chlorine concentration measuring device by polarogram method

Claims (2)

    A determination apparatus that detects a change in a measurement target without having selectivity with respect to a change in sugar amount. A determination apparatus characterized by preliminarily estimating a state of a measurement target and a state at the next measurement time point by linearly approximating a sugar amount change.