JPS6260435B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the field of temperature indicating compositions and devices therefor. The color changes sharply during the transition from a liquid state to a solid state or from a solid state to a liquid state, but the change in state is substantially predetermined and corresponds to the temperature to be measured. We describe novel and stable compositions that occur at elevated temperatures. The components of this novel composition consist of: 1 a single substance or a mixture of substances adapted to change from a solid state to a liquid state at a substantially predetermined temperature; 2 An indicator system () consisting of a solvent () that An indicator system () characterized in that () undergoes a visible color change when it moves from a solid to a liquid phase or from a liquid to a solid phase. Among other uses, various proportions of the organic components constituting the novel compositions may be placed and provided in a plurality of discrete regions, preferably equally spaced and corresponding to increasing temperatures, such as a grid. The thermometer is formed by being able to determine the same predetermined temperature within a defined temperature range. When these areas are exposed to a certain temperature within the temperature range, one or more areas containing the composition change from a solid state to a liquid state and change color correspondingly to the nearest Indicates the temperature within that temperature range for a temperature increase. The novel temperature indicating device described comprises a thermally conductive carrier having one or more recesses each substantially filled with a novel composition, or alternatively a top portion of the indicating member residing at the bottom of the recess. and comprises a thermally conductive carrier having one or more recesses substantially filled with a composition that changes from opaque to transparent with a corresponding solid-to-liquid change. The composition, whether new or not, includes a material substantially between the bottom of the recess and a transparent cover sheet member sealingly engaged with a thermally conductive carrier member overlying the recess. Contains a spherical cavity.
Its spherical cavity serves to magnify the color change.
Preferably, the transparent cover sheet and the thermally conductive carrier member are bonded to each other by a layer of pressure sensitive adhesive consisting entirely or substantially of polyisobutylene. For some time now people have been developing inexpensive devices that eliminate the inconvenience of traditional mercury thermometers, essentially using substances or mixtures of substances of a type that produce a color change of some characteristic visible to the naked eye at the temperature to be measured. I've been trying to make it. U.S. Pat. No. 3,946,612 discloses a thermally conductive carrier having a plurality of spaced depressions each containing at least two different organic compounds (o-chloronitrobenzene and o-bromonitrobenzene).
The use of thermally conductive carriers with corresponding solid solution layers of organic layers deposited in their recesses in various composition ratios is described. These organic layers change from opaque to transparent with a phase change from solid to liquid phase. This organic layer is sandwiched between an indicator layer and an overlying or opaque layer.
When the cavity is heated to a predetermined temperature,
The composition changes from a solid to a liquid, allowing the dye to pass through the indicator and enter the opaque layer, changing the color of the opaque layer to the color of the dye. Such a device with three internal layers in the cavity is difficult to make and very expensive. Sometimes the organic composition does not completely change from liquid to solid, resulting in nucleation points remaining in the organic layer, so that resolidification occurs as soon as the thermometer is removed, and not all of the dye is transferred to the upper or opaque layer. It may not always penetrate. Because of the size of the layers, it is sometimes difficult to make a color change visible if only some of the dye migrates to the opaque layer. U.S. Pat. No. 3,700,603 describes the use of paired materials in thermometers that change color with a change in phase. However, suitable solvent systems are not used and, as a result, a large number of different pairs of substances are required for almost any temperature range that is to be measured. This also applies to the acceptor-donor compound mixtures described in US Pat. No. 3,576,604, which are used to detect thermal effects by color change. However, the color change occurs in the absence of a solvent. Now, an organic compound (described in more detail later) forms a solid solution that changes state from solid to liquid at precisely predetermined temperatures, with an accompanying color change that is visible to the naked eye. Also, a liquid solution that changes state from liquid to solid and causes a corresponding change in color that is visible to the naked eye.
was discovered to form. The present invention comprises at least: 1 a solvent consisting of a single substance or a mixture of substances which is adapted to convert from a solid state to a liquid state at a substantially predetermined temperature; ) is an indicator system () consisting of one or more substances different from or an indicator system (), characterized in that () undergoes a macroscopic color change upon transition from a liquid to a solid phase; Although all the color changes discovered have not yet been studied, based on the experimental results we have found, the other requirements for novel compositions in most cases are:
When the solvent () is in the solid phase, the solubility of the indicator system () in the solvent () is equal to () when () is in the liquid phase.
The solubility of () in () is much lower than that of (), so that () partially or completely separates while () moves from the liquid phase to the solid phase. The term "solid solution" is well known and usually refers to a homogeneous solution of one solid in another. The novel solid solution aimed at in the present invention includes two or more types of compounds containing at least two types of compounds forming the solid solution in various proportions,
Preferably, it consists of three or four different organic compounds. This solid solution forms a solvent for one or more of the indicator compounds in liquid form. Each new solid solution undergoes a rapid change of state at or substantially near a precisely predetermined temperature. "Color change that is visible to the naked eye" of the source material
This word means that the intensity of the luminous flux surrounding it is about 5
lumen/ft ² (ft-c) or more (from about 3900 Å to 3900 Å before or after, or preferably both) (Relating to light from sources that disperse or reflect energy within the electromagnetic spectrum of approximately 7600 Å). In most cases, this change in luminous flux wavelength to the eye will be at least about 175 Å, preferably at least about 500 Å. Preferably, the novel composition comprises: (A) a suitable solvent used to convert from a solid state to a liquid state at a predetermined temperature; and (B) one or more solvents that are soluble in said solvent in the liquid state. Suitable organic moieties, which are used to cause a macroscopic color change in the composition upon a change in the state of said solvent at a substantially predetermined temperature, are of the following groups: (i) of the following types: compounds, namely monoazo, disazo, triarylmethane, xanthene, sulfonophthalein, acridine, quinoline, azine, oxazine, thiazine, anthraquinone,
Indigoids, and the following individual compounds: Aurantia, Orasol Orange RLN, Diamin Green B, Direct Green G, Fast Red Salt 3GL, Fast Blue Salt BB, First Garnet Salt GBC, Carta Yellow G180%, Murexide, Savinyl Blue
GLS, Irgalith Blue GLSM,
Phthalocyanine and Alcannin
(ii) a mixture of (a) one or more organic acid compounds having a pK of less than about 4; and (b) one or more basic dyes or basic indicators; iii) a mixture of (a) one or more organic acids with a pK of less than about 2; and (b) one or more acidic dyes or acidic indicators; (iv) (a) one or more organic acids with a pK of less than about 4; and (b) one or more compounds from group (); (v) (a) one or more basic dyes or basic indicators; and (b) one or more compounds from group (). (vi) (a) one or more dyes having a molecular structure that includes a lactone group; and (b) one or more acids having a pK of about 8 to about 12. an effective amount of one or more suitable organic moieties selected from one or more of the group consisting of; The compounds mentioned in group () are
Published by of Dyers & Colourists
Color Index 3rd edition (1971) and Conn's
Classified according to Biological Stains 9th edition (1977). Preferred monoazo dyes are: 4-(p-ethoxyphenylazo)-m-phenylenediamine, mono-hydrochloride, Orazol navy blue, Organol orange, Janus. Green, Ilgaris Red P4R, Dimethyl Yellow, First Yellow, Methyl Red Sodium Salt, Alizarin Yellow R,
Eriochrome Black T, Chromotrope 2R, Ponceau 6R, Yellow Orange S, Brilliant Ponceau 5R, Chrysoidin G, Eriochrome Black A,
Benzyl Orange, Ponsou G/R/2R and Chromolan Yellow. Preferred diazo dyes are: Fat Red BS, Sudan Red B,
Bismarck Brown G, Fatbruck, Resorcin Brown, Benzofast Pink 2BL and Oil Red
EGN. Preferred triarylmethane dyes are: Methyl Bialez, Xylene Cyanol FF, Erioglaucine,
Fuchsin NB, Fuchsin, Parafuchsin, Aurintricarboxylicacid Ammonium Salt, Patent Blue, Victoria
Blue R, Crystal Vialette and Ilgaris Blue TNC. Preferred xanthene dyes are: Phloxin B, Fluorescein sodium salt, Rhodamine B, Rhodamine B base, Rhodamine 6G, Pyronin G, Magenta TCB, ilgaris pink
TYNC, Eosin Scarlet, Eosin Yellow, Erythrosin Extra Blue,
4′,5′-dibromofluorescin, ethyleosine, Gallein, Phloxine, erythrosin
Blend and Cyanosin B. Preferred sulfonphthaleins are: cresol red, chlorophenol red, chlorophenol blue, bromophenol blue, bromocresol purple and chlorocresol green. Preferred acridine dyes are: Coriphosphine O, Acriflavine and Acridine Orange. Preferred quinoline dyes are: Pinacyanol chloride, pinacyanol bromide, pinacyanol iodide, Quinaldine red, Cryptocyanine, 1,1'-diethyl-2,2'-cyanine iodide, 2. -(p-
dimethylaminostyryl)-1-ethyl-pyridinium iodide, 3,3'-diethyl-thiadicarbocyanine iodide, ethylredo, dicyanine A, Merocyanine 540 and Neo cyanine. Preferred azine dyes are: Neutral Red Chloride, Neutral Red Iodide, Nigrosine, Sabinyl Blue B, Orazol Blue BLN Safranine O, Azocarmine G, Pheno Safranine, Azocarmine BX and Rhoduline vialets. Preferred oxazine dyes are: Solophenyl Brilliant Blue.
BL, Nile Blue A, Gallocyanine, Gallamine Blue and Celestine Blue. Preferred thiazine dyes are: methylene blue, thionine, toluidine blue O,
Methylene Green and Azure A/
B/C. Preferred anthraquinone dyes are: Sabinyl Green B, Sabinyl Green
RS, D+C Green 6, Blue VIF Organol, Alizarin, Alizarin Cyanine 2R, Celliton Blue Extra, Alizarin Blue S, Nitro First Green
GSB, Alizarin Red S, Chinalizarin, Oil Blue N, Solway Purple and Purpurin Preferred indigoid dyes are:
Ciba Blue, Indigo Synthetic, Cromophtal Bordeaux RS and Thioindigo Red. The most preferred dyes are pinacyanol iodide, chlorophenol red and alizarin blue S. A small but effective amount (generally about
0.005 to about 0.2 wt. It has been found that, together with , it is possible to obtain the temperature of change of state with color change of a large number of solid solutions at intervals of about 1/10 °C. That is, a change in the state of one novel temperature-sensitive composition is compared with a change in the state of another novel composition in an adjacent region containing different proportions of the same organic moieties in o-chloronitrobenzene and o-bromonitrobenzene. It can be made to occur at a temperature that is 1/10°C different from the temperature of . For example, for human body temperature, about 35℃ to about 42℃, especially
Temperatures in the range of 35.5°C to 40.5°C are usually desired. In the latter case, 50 different solid solutions (prepared from the same two components, but differing only in their percentage composition) are heated at 35.5°C at intervals of 1/10°C.
It is possible to provide all necessary temperature steps from 35.6℃, 35.7℃, ...40.4℃. A solution of o-chloronitrobenzene and o-bromonitrobenzene is
When o-bromonitrobenzene varies from 56.2% to 96.0% by weight, it becomes an excellent starting mixture for determining temperatures in the human body temperature range. the normal group () or other organic moieties (hereinafter sometimes referred to as "organic moieties")
) does not significantly affect the melting point of the solid solution. The melting point of the organic moiety is preferably higher than that of the solvent system. If the indicating system consists of a mixture of compounds,
Preferably, the melting point of each of the components is substantially higher than the melting point of the selected solvent system, and it is even more preferred that the compounds melt at a temperature greater than 60° above the melting point of the solvent system. Regardless of the solvent system selected for a given predetermined temperature range, the organic moiety selected for color change may be present in a small but effective amount, e.g., sufficient to cause a macroscopic color change. at least a sufficient amount, preferably from about 0.005 to about 0.2% by weight of the solvent material
occupies the amount of If too little of the organic moiety is used, the color and color change will be too weak; if too much is used, the color change will be difficult to discern and may affect the acuity of the melting point. There is sex. The organic portion should be substantially free of impurities and it is generally accepted that such impurities should be kept below 0.3% of the total composition. One or more groups used in novel compositions
Instead of the compounds, mixtures can be used. The group of organic acidic compounds having a pK of less than about 4 consists of organic acids and/or halogenated sulfonphthaleins that are soluble in the chosen solvent when it is liquid. Examples of such acids include: Oxalic acid, maleic acid, dichloroacetic acid, trichloroacetic acid, 2-naphthalenesulfonic acid, chloroacylic acid, bromophenol blue, bromothymol blue, chlorophenol red, bromochlorophenol blue, bromocresol green, 3,4,5,6 -tetrabromophenolsulfonphthalein, bromophenol red, chlorocresol green, chlorophenol blue, bromocresol purple, and 2,
4-Dinitrobenzenesulfonic acid. The group of basic dyes or basic indicators generally includes:
amino-triphenylmethane, also known as triarylmethane, or soluble salts thereof;
8-hydroxyquinoline and quinoline dyes, preferably cyanines. Examples include: basic fuchsin, pinacyanol iodide, pinacyanol chloride, piacyanol bromide, 2-p(dimethylaminostyryl)-1-ethyl-pyridinium iodide, crystal baia. Retto, cryptocyanin, dicyanin A, 3,3'-diethylthiacarbocyanine iodide, 1,1'-diethyl-2,
2'-cyanine iodide, ethyl ret, quinaldine ret, ethyl viaret, brilliant green, pararoseaniline, parazoleaniline acetate, 8-hydroxyquinoline, 1
-ethylpyridinium iodide and 5-(p
-dimethylaminobenzylidene) rhodanine. Preferably, the weight of the acidic compound is about three times or more the weight of the basic compound. The pK values mentioned above refer to pK values measured in water. Generally acidic compounds
Preferably, the pK is lower than the corresponding pK value of the basic compound. Preferably, the acidic compound has a pK value of less than about 4 and the basic compound has a pK value of less than about 5. When the basic compound consists only of one or more aminotriphenylmethanes or soluble salts thereof, the acidic compound is selected from the group consisting of tetrahalogenated sulfonphthaleins and other organic acids having a pK of less than about 2. It should be noted that A preferred combination of an acidic compound with a pK of less than about 4 and a basic dye or indicator is bromophenol blue/basic fuchsin,
They are chlorophenol blue/ethyl red and trichloroacetic acid/3,3'-diethylthiadicarbocyanine iodide. pK of less than about 2 used in novel compositions
A mixture of one or more organic acids with one or more dyes or acidic indicators undergoes a color change when the solvent changes from solid to liquid phase or vice versa. In this combination, the acid dye used is preferably a halogenated sulfonophthalein. A mixture of one or more organic dyes having a molecular structure containing lactone groups and one or more acids having a pK of about 8 to about 12 can also be used in a solvent to transform the solvent from a solid phase to a liquid phase or vice versa. A color change occurs when changing to . Preferred compounds in the combination are crystal viaret lactone and one or more acids such as phenol, bisphenol A, pyrocatechol or 3-nitrophenol. Sometimes, in fortuitous circumstances, the solvent system may consist of only one type of compound, but in most cases (as will be understood by those skilled in the art), the temperature to be determined will be
It may not be easily obtained unless two or more organic compounds are mixed in the solvent system. Therefore, for a temperature indicating device, the presence of two or more related organic compound components in a solvent is particularly useful for measuring more than 40 temperatures located in regular steps. From the above, it can be seen that the selection of one or more inert solvents for the organic moieties used in the novel compositions includes:
It is clear that it requires astute and careful examination. This is because not all organic compounds are useful for this purpose and many fall outside the desired temperature range. Suitable solvents may be those that are inert towards the organic moieties and such that the organic moieties are soluble therein when the solvent is in the liquid phase. thus have similar chemical structures (e.g. analogs, homologues and optical isomers), have substantially similar molecular volumes or similar crystal structures (e.g. isomorphism), and for purposes of the present invention. Solvent system components used to prepare novel composition grids for use at predetermined temperatures for determining the temperature within said range at which aromatic organic compounds form novel solid solutions useful for have been found to be particularly useful. Furthermore, it is particularly preferred that the solvent solution has a linear or substantially linear temperature composition liquidus curve over a desired temperature range, such as over the human body temperature range. Examples of aromatic solvents include: o-chloronitrobenzene, o-bromonitrobenzene, naphthalene, 2
-Ethoxybenzamide, 1-thymol, 2-naphthol, o-iodonitrobenzene, m-iodonitrobenzene, p-iodonitrobenzene, p-chloronitrobenzene, m-bromonitrobenzene, p-bromonitrobenzene, p-dibromonitrobenzene and p-toluic acid. In some cases, simple alcohols, other organic substances and even water may be suitable rather than polar, weakly polar or non-polar aromatic compounds. In addition to aromatic compounds, t-butanol, stearic acid, 1-tetradecanol, n-tetracosane,
Color changes were also observed with aliphatic compounds such as lauryl alcohol, formamide and paraffin, and with heterocyclic compounds such as dioxane, symmetric trioxane, indole and dibenzofuran. Of course, it should be noted that a suitable solvent useful for one selection of organic moieties may not be useful for another. It is well within the knowledge of those skilled in the art to find a suitable solvent for a given temperature range to be measured and desired color change. It is made from a binary mixture of o-chloronitrobenzene and o-bromonitrobenzene, and o-
A solid solution having a ratio of chloronitrobenzene to o-bromonitrobenzene of about 43.8-56.2 to about 4.0-96.0 has been found to be most preferred for use in temperature measurements in the body temperature range. In studying the compositions according to the invention, it has been found that in many cases the indicator substance or mixture thereof becomes at least partially separated from the liquid solvent during its solidification. When viewing the solidifying composition under a microscope, it is observed that the indicator substance is significantly expelled from the growing solvent crystals and concentrated in the remaining liquid phase. As the solidification process progresses, the concentration of the indicator substance increases until the solvent is completely solidified. The indicator substance is then highly expelled from the solvent. While the indicator concentration in the liquid portion of the solvent increases, ie, while the indicator is actually expelled from the solvent, the indicator changes its color. Upon subsequent heating, the solvent crystals melt and redissolve the indicator again, returning the original color. An example of a particularly preferred group () compound is pinacyanol iodide at a concentration of 0.025% by weight. When dissolved in the o-chloronitrobenzene/o-bromonitrobenzene (OCNB/OBNB) solvent, the liquid composition takes on an eye-catching brilliant blue color. While the OBNB/OCNB solvent solidifies at room temperature, pinacyanol iodide increases in concentration in a progressively decreasing liquid fraction. The pinacyanol iodide increases in concentration until the solidification of the composition is complete, at which point the pinacyanol is isolated as small particles around the crystalline structure of the OBNB/OCNB solvent and, to the observer's eye, the entire composition The color of objects appears to change to an attractive rose color. When viewing the solidified composition under any type of microscope, it appears that spheres of pinacyanol iodide particles quickly crowd the surface of the crystallizing solvent. When the solidified composition is heated to melting, the pinacyanol iodide immediately redissolves, thereby returning to its brilliant blue color. It is not yet completely understood why pinacyanol iodide separates from the solvate. The color change may be caused by intermolecular interactions between the pinacyanol ion and the opposing ion. The pinacyanol iodide crystals formed by solvent separation appear to have a columnar structure in which positive dye ions are stacked with opposing negative ions. Such a structure might result in significant changes in resonance compared to the unperturbed state of dissolved pinacyanol iodide. Other examples of particularly preferred group () compounds include about
Chlorophenol red at a concentration of 0.05% by weight. When dissolved in solvents such as OCNB/OBNB, dibenzofuran, para-toluic acid and other halogen nitrobenzenes, the liquid composition turns yellow.
During solidification of the composition, the chlorophenol lead is concentrated in the remaining liquid portion of the solvent. When solidification is complete, the solid is bright red in color. Microscopic examination of the solid composition revealed that the chlorophenol red particles were substantially free of the solvent. In our opinion, when the chlorophenol red is dissolved in a liquid solvent, the intermolecular rearrangement of the sultone group into a quinone structure may be responsible for this color change when the chlorophenol red is separated. Seem. When the indicator system consists of more than one component, the color change will often be caused by a chemical reaction between the indicator compounds. An example of a preferred mixture of a basic dye and an acid having a pK of less than about 4 consists of chlorophenol blue and ethyl red. Compounds such as
When dissolved in OCNB/OBNB to a total concentration of about 0.05% and with a weight ratio of chlorophenol blue/ethyl red of 3:1, the liquid phase exhibits a red color. As the composition moves from liquid to solid state, a noticeable color change from red to yellow is observed. In the above case, an acid-base reaction is probably occurring. When the composition is in liquid phase, the chlorophenol blue and ethyl red are in a diluted state, so that the ethyl red is in its basic red form. Therefore, the liquid shows a red color. During solidification of the solvent, the indicator is concentrated in the liquid phase and the chlorophenol donates a proton to the ethyl red, thereby converting the latter into its colorless acid form. As a result, the solidified composition becomes yellow. According to the above theory, halogenated sulfonophthaleins are considered to be acids. Similar reactions will occur when simple organic acids such as sulfonic acid, trichloroacetic acid, and basic dyes are used. Since many sulfonphthaleins already undergo a color change when applied as a single compound, this color change may not influence the color change obtained from the acid-base reaction. Probably. Preferably, the composition according to the invention is substantially free of impurities that might induce resolidification immediately after melting. Generally impurities are less than 0.3% by weight of the total composition, thereby allowing the composition to be supercooled. If a given composition reaches 100% liquid after melting, then only that liquid needs to remain liquid for more than a few seconds when removed from the object whose temperature is to be measured. There is. If the melting is less than 100%, the composition will almost immediately return to its solid state when removed from the object. It is only by such means that commercially useful compositions as disposable thermometers can significantly advance the state of the art. Although the best way to obtain supercooling properties for each of the novel compositions of the present invention is for them to be substantially free of impurities, the supercooling effect is caused by different mechanisms. There is no doubt that this is true. For example, there are some organic solvents for organic moieties (high molecular weight aliphatic alcohols) that suddenly become very viscous in the liquid state close to solidification, so that they become superfluous despite the presence of some impurities. Has cooling properties. Therefore, this limited number of solvents is the same as the common solvents used in the present invention that are substantially free of impurities. In some cases, when a supercooled liquid composition resolidifies at a predetermined temperature, for example after being accidentally heated above its melting point during storage or shipping,
It is advantageous to recrystallize the composition. It has been found that 0.001 to 10.0% by weight of soluble or insoluble nucleating agent enables the compositions of the present invention to be recrystallized at substantially predetermined temperatures. Preferred nucleating agents are anthraquinone, talc, aluminum oxide, silicon dioxide,
These are modified silica, boron, titanium carbide, diamond, and molybdenum disulfide. A particularly preferred nucleating agent is talc with a particle size of 0.1 to 10 micrometers. In addition to being used as a disposable oral thermometer,
The novel compositions of the present invention can detect engine overheating;
Detection of leaks from steam traps (by placing the indicator on an uninsulated section of tubing directly below the steam trap), detection of high temperatures around computers, home furnaces, appliances, other food packaging, etc. , can be used as a temperature indicator for the forehead, skin and rectum. The present invention uses the same number of defined different compositions to determine the same number of predetermined temperatures within a predetermined temperature range in one or more isolated areas. a thermally conductive carrier having defined areas therein, wherein said composition is contained by a transparent cover sheet member sealingly engaged with said carrier, and each of said areas are deposited with a composition with only one of said predetermined temperatures, and the compositions used are novel compositions as described in the previous part of this specification. The present invention relates to a temperature indicating device. Preferably, the aforementioned areas are depressions in the thermally conductive layer. Preferably, the compositions used have an essentially linear melting point versus composition relationship over the temperature range represented by the plurality of compositions. filling the cavities with a composition having a predetermined melting point to a level of about 60% of the volume of each cavity;
A preferred device is obtained when the transparent cover sheet member is sealingly fitted to the carrier. In this case, each of said compositions that have entered a particular cavity are
Filling the cavity except for the substantially spherical cavity within the cavity. The spherical cavity serves to magnify the color change within the cavity. The compositions used in the apparatus of the invention may be as described above, including compositions that include one or more nucleating agents to enable the composition to be recrystallized at a substantially predetermined temperature. Consisting of a new composition. As an alternative to the nucleating agents described above, the surface of the thermally conductive carrier may be treated by anodization or chemical passivation to generate nucleation points. Anodization may be carried out under sulfuric or phosphoric acid or other conditions as known to those skilled in the art. Chemical passivation of the surface can be accomplished by etching with 2% sodium hydroxide followed by treatment with 10% nitric acid and washing with water. Another preferred temperature device is one or more isolated depressions in which the same number of respective predetermined depressions are arranged to determine the same number of predetermined temperatures within a predetermined temperature range. a thermally conductive carrier member having recesses containing different heat-sensitive compositions with one of a defined temperature, an indicator member disposed at the bottom of each of said recesses, in intimate contact with said carrier member; mating transparent cover sheet members for covering each recess to form an enclosure between the recess and the transparent member; The temperature indicating device consists of each of said compositions substantially filling the cavity except for the spherical cavity. In a preferred embodiment of this device, the spherical cavity has a diameter slightly less than (a) the depth of the depression - (b) the width of the indicator member. The heat-sensitive composition used in the above device is a classical composition. By "classical composition" is meant a composition commonly used as a simple thermometer that changes from opaque to transparent with a phase change from solid to liquid. In the above device, the instruction member placed at the bottom is
It consists of a layer of absorbent material or a paint layer impregnated with a dye or colorant. Sometimes crystals of classical composition are
The opacity is insufficient so that the color of the indicator is visible when the heat-sensitive composition is in the solid phase. To prevent this, there is preferably a thin layer of absorbent material between the cover sheet and the heat-sensitive composition. In order to read the device after removal from the temperature source to be measured, classical compositions must have supercooling properties. This is achieved by keeping the impurities in each well below about 0.3% by weight of the weight of the composition associated with the well. Whether novel or classical, the composition used in the temperature indicating device, which is incidentally heated above the melting point of said composition, must have the property of being able to resolidify at a temperature below its melting point. In order to recrystallize the composition at a substantially predetermined temperature, the heat-sensitive composition contains from 0.001 to 10.0% by weight of a soluble or insoluble nucleating agent. Besides potassium ethyl sulfate or potassium pyrosulfate, preferred nucleating agents are anthraquinone, talc, aluminum oxide, silicon dioxide, modified silica, boron, titanium carbide, diamond and molybdenum disulfide. A particularly preferred nucleating agent is talc with a particle size of 0.1 to 10 micrometers. 0.1% by weight of talc was added to pinacyanol iodide used for thermometers and
When added to a composition consisting of an OCNB/OBNB mixture, the composition can be easily recrystallized at a temperature of -6°C. In the same manner as described above, the carrier layer surface may be treated by anodization or passivation to generate nucleation points when using classical heat-sensitive compositions. The present invention uses the same number of defined different compositions to determine the same number of predetermined temperatures within a predetermined temperature range in one or more isolated areas. a thermally conductive carrier having defined areas therein, wherein said composition is contained by a transparent cover sheet member sealingly engaged with said carrier, and each of said areas are deposited with a composition with only one of said predetermined temperatures, and the compositions used are novel compositions as described in the previous part of this specification. and a temperature indicating device in which the transparent cover sheet member and the thermally conductive carrier are sealed together by an adhesive layer of pressure sensitive adhesive consisting entirely or substantially of polyisobutylene. Additionally, polyisobutylene can similarly be used as an adhesive in temperature indicating devices such as those made of: (a) a thermally conductive carrier member having one or more recesses with an indicator member in at least one of the recesses, which melts at a predetermined temperature and is o-
a thermally conductive carrier member filled with a classical composition consisting of a mixture of chloronitrobenzene and o-bromonitrobenzene; (b) a transparent cover sheet sealingly engaged with the carrier member over each of said recesses; . From US Pat. No. 3,002,385 a temperature indicating device is known, in which a low temperature adhesive such as a silicone-based pressure sensitive adhesive material or an epoxy resin is used. Due to various reasons such as insufficient resistance to the chemicals used, release of low molecular weight components that adversely affect durability, temperature indication and reproducibility, and insufficient immutability to chemical substances. , those adhesives have been found to be unsuitable. Polyisobutylene used as pressure sensitive adhesive has a range of 50,000 to 5,000,000, especially 150,000 to
Preferably it has an average molecular weight in the range 4,000,000. A very favorable combination of adhesive strength and resistance to chemicals present in the recesses is that the adhesive layer contains 30 to 70% by weight of polyisobutylene with an average molecular weight of 70,000 to 100,000 and an average molecular weight of 1,000,000 to 1,000,000.
3,500,000 in a mixture with 70-30% by weight of polyisobutylene. Preferably, the mixture consists of substantially equal parts by weight of each component. The adhesion between the carrier layer and the pressure sensitive adhesive can be further improved in various ways. Such an improvement is obtained when the carrier layer consists of an aluminum foil with an etched surface. Improvements in adhesive strength can also be achieved by utilizing a carrier layer of aluminum foil coated with a polyisobutylene surface layer applied as a solution in an organic solvent. As an example of a suitable solvent, mention may be made of hexane. Such a surface layer is 2
Preferably it has a thickness of ~10 micrometers. The polyisobutylene used in such a surface layer preferably has an average molecular weight in the range 2,000,000 to 3,500,000. By using a carrier layer with a surface modified in this way, it is possible to obtain good adhesive strength even when using polyisobutylene with a relatively high molecular weight. Therefore, a carrier layer coated with a surface layer of polyisobutylene,
It is preferred to use a pressure sensitive adhesive layer of polyisobutylene having an average molecular weight in the range of 2,000,000 to 3,500,000 to adhere the carrier layer to the transparent cover layer. The pressure-sensitive adhesive used according to the invention can be applied as a thin layer to one side of the film material used as the transparent layer, for example a polyester film. This can be carried out, for example, as a solution in hexane or as a melt. The thickness of the adhesive layer thus formed is as a rule from 10 to 100 micrometers, preferably from 20 to 60 micrometers. The polyisobutylene-coated side of the transparent cover layer is brought into contact with the carrier layer on the side of the indentation to be closed, and the adhesive is applied by applying pressure without increasing the temperature. The applied adhesive pressure is generally in the range 1 to 50 kg/cm ² . A variety of polyisobutylenes are suitable for use for this purpose. The average molecular weight of polyisobutylene is
Preferably, it is in the range of 50,000 to 5,000,000. The average molecular weight refers to the viscosity average molecular weight. It is calculated from the intrinsic viscosity, which means that a solution with a concentration of 1 g/dl in isooctane is
It is determined by the flow rate through the capillary tube of the viscometer at a temperature of 20°C. The following formula is used for this calculation. [n]=n _sp /c/1+0.31n _sp =3.06×10 ^-4
× _V ⁰ . In the formula ⁶⁵ , [n] = intrinsic viscosity n _sp = t/t _p -1 = specific viscosity t = solution flow rate corrected according to Hagenbach-Couette t _p = solvent flow rate corrected according to Hagenbach-Couette flow rate c = concentration of solution (g/dl) _V = average molecular weight The polyisobutylene used has good resistance to the chemicals present in the cavity, does not affect their melting point and has almost no chemical content. It does not absorb or pass through. Next, I will describe the attached figures. With reference to FIG. 2, the bottom of a depression "A" in a flat thermally conductive carrier member 2 of width (thickness) 6 which is substantially filled with "classical" solid solution 5 is filled with colorant 1. You can see that it is. The depression “A” is
Immediately surrounding it and covering the solid solution 5 filling it, it is covered by a transparent cover sheet 4 which fits in a sealing manner with the thermally conductive carrier member 2. In the solid solution 5 there is a substantially spherical cavity 3, which has a diameter 10 slightly smaller than the width 12 of the depression minus the small width of the colorant 1. The preferred embodiment shown in FIG. 2 has a trapezoidal shape rotated about an axis, with a large diameter 8 at the top of the depression and a small diameter 9 at the bottom of the depression. Preferably, the width 7 of the transparent film 4 is substantially equal to the width 6 of the thermally conductive carrier member 2. The thermally conductive carrier member 2 has a high thermal conductivity and a relatively large contact surface area with the subject, and has structural integrity such that heat is rapidly transferred into the recess as shown in FIG. must be as thin as possible while maintaining In a particularly advantageous embodiment, the thermally conductive carrier element 2 is preferably constructed from aluminum or an alloy thereof, which always conducts heat effectively. The colorant 1 may be a "dye layer" or a layer of material impregnated with a dye. Examples of dyes suitable as indicating materials are dyes such as Croceine Scarlet SS and Polynal Blue, both manufactured by Allied Chemical.
Manufactured by Corporation. When composition 5 first melts, dye 1 becomes wet;
This results in substantially immediate dye migration from layer 1 throughout composition 5. However, it is only necessary to use colorant material 1, which is simply a paint on the bottom of the depression "A". Preferably they are blue or black. The spherical cavity 3 in the depression serves to magnify the device when the colorant 1 is viewed from above. The transparent cover film member 4 may be made of polypropylene, Mylar, nitrocellulose, polyvinyl chloride, or the like. In FIG. 2, the transparent cover film member 4 is
Heat-sensitive materials such as nylon 6 (Allied
Chemical Co.) and Surlyn 1652
(manufactured by EIDuPont de Nemours & Co.) may also be a co-extruded film. That film is
Manufactured by Pierson Industries Incorporated and later laminated to polypropylene by Millprint Company of Milwaukee, Wisconsin. 3 and 4 show cross-sections along line 3--3 of FIG. 2 as viewed by an observer from above the recess of FIG. 2. Figure 3 shows the cavity A when it is not filled with the composition, whereas Figure 4 shows the cavity filled with the classical composition as it melts and becomes transparent, resulting in observation. person is hollow A
The indentation is shown after Colorant 1 can be seen at the bottom. In this case, the entire recess A is partially adsorbed. When recess A is filled with composition 5, which composition is in solid solution before melting,
The opacity of the composition completely obscures the colorant 1 at the bottom of well A. That is, it is only when the composition is melted that one can see the colorant 1 at the bottom of recess A or throughout recess A. If the novel compositions described above are used (instead of the classical compositions which change from opaque to transparent with a change from solid to liquid), the layer of colorant 1 can be omitted. Figures 5 and 6 each show a thermally conductive carrier member C, which is a thermometer with a Celsius scale (only one grid showing indentations from 35.5°C to 37.9°C), which is an embodiment of the present invention. FIG. 2 shows a partial plan view from above and a plan view from above of a similar component of the same chemical thermometer with a Fahrenheit scale formed with a rectangular grid, which is a particularly advantageous embodiment of the invention; ,
(preferably 35.5°C to 37.9°C for Celsius scale)
and has two sub-grids for 38.0℃~40.5℃, 96.0〓~99.8〓 and 100.0〓~ for Fahrenheit scale.
104.8〓), in this case each recess 13 has a structure as shown in FIG. is clearly connected. In Figures 5 and 6, each indentation 13 uses the same colorant [1 in Figure 2], so that when the thermometer is tested within a predetermined temperature range, the composition One or more depressions in the liquid phase,
It will be seen that the composition becomes clearly distinguishable from the remaining depressions of the solid phase. The operation of the thermometer of FIG. 5 (or FIG. 6) is as follows. Looking at FIG. 5 together with the indentation substantially made as shown in FIG. 2, we see that the handle portion B of FIG.
5] is held between the fingers, the part C with the indentation 13 is inserted into the mouth and held under the tongue for a relatively short period of time, about 30 seconds to 1 minute. During this time various depressions with melting points lower than the temperature in the mouth 1
3 of the compositions are all melted, and the colorant in each well is 1.
It shows a color change that is visible to the naked eye. Since the melting composition is of such pure nature that it exhibits a stable supercooled state for at least several minutes, the user simply removes the thermometer of Figures 5 and 6 and inserts it into the grid above it. The temperature can then be clearly seen with the selected accuracy, ie 0.2〓 or 0.1〓 intervals. The colorant 1 for each of the depressions 13 in FIG. 5 is of the same color, and the depressions all have a composition selected from the graph as shown in FIG.
〓 or have melting points separated by equal intervals of 0.1℃
Preferably, it is filled with an OCNB/OBNB composition. FIG. 7 shows the method for testing temperatures at 10 〓 intervals using the novel composition described above. In this case the coloring material of FIG. 2 is unnecessary (for example, the composition changes from orange 103 to red 10
(changes to 4). 7, the transparent cover plate member 101 is shown in a sealing fit, preferably a vacuum seal fit, with the thermally conductive carrier member 102, with each of the six recessed perimeters being shown. It will be readily apparent to those skilled in the art that the novel composition may be used not only in the novel temperature indicating device as shown in FIG. 2, but also in other forms as shown in FIG. In the latter case, a single indentation is used with the same novel composition of FIG. 7 (which has already melted and turned red) to detect whether the material during storage has exceeded the safe temperature. Figures 9 and 10 show, as another preferred embodiment, a 96.0 to 104.8 degree Fahrenheit grid (as in Figure 6) indentation 36 (as shown in Figure 6) bonded to a plastic (preferably polystyrene, polypropylene or polyethylene) handle 35. 2 shows a perspective view of a flat thermally conductive carrier member 37 (here aluminum) having a carrier member 37 (as shown in FIG. 2). Until use, the carrier member 37 is secured to the casing 32 (preferably made of the same material as the handle 35) by a roller and paper, plastic or other retaining member 31 exerting this force downwardly thereon. It is held stably inside the handle 35.
The carrier member 37 cannot be accidentally removed from the case 32 unless force is intentionally applied to remove it. Although not shown in FIG. 9, there is a closure member at the end of the carrier member 37 (nearest the handle 34) that will cause the carrier member to close unless a force of sufficient magnitude is intentionally applied to break the closure member. 37 and the case 32 are fitted in a vacuum-tight manner. The handle 35 may also be notched and formed with a tooth pattern 34 to provide a firm grip for a user who wishes to remove the carrier member 37 from the case 32. In FIG. 10, a transparent cover sheet 39, also in the form of a plastic transparent sheet or a plastic transparent cover member, is in a sealing fit, preferably a vacuum seal fit, with a carrier member 37 overlying the recess 36, each of which There is also a sealing fit around the recess. FIG. 11 is a horizontal cross-sectional view taken along line 11-11 of FIG.
FIG. The transparent cover sheet member 39 has a sealing fit with the aluminum thermally conductive carrier member 37 and also has a sealing fit around each recess. A similar base plate member 40 is a sealing fit with the thermally conductive carrier member 37 and also sealingly fits around each of the recesses. A similar base plate member 40 is adapted to sealingly mate with the thermally conductive carrier member 37 to provide a flat surface for the thermometer. Bottom plate 40 helps maintain the structural integrity of carrier member 37;
It has the same width as the entire surface of the carrier member 37. 12 and 13, another preferred embodiment of the present invention is shown, which comprises the novel composition of the present invention (preferably OCNB: OBNB/pinacyanol iodide) and FIG. It is intended to measure temperatures from 96.0〓 to 104.8〓 at intervals of 0.2〓 by combining the new depressions of 〓 without using an indicator layer. Unlike those shown in Figures 9 and 10, the embodiment shown in Figures 12 and 13 does not have a case and is therefore cheaper to manufacture. FIG. 12 is a plan view of an oral temperature indicating device which, as can be seen above, is substantially flat. Again, the thermometer has an aluminum thermally conductive carrier member 44 of width 47, which serves not only as the main support structure but also at the same time as the grid "G" of multiple depressions in FIG. 2 (horizontal axis in FIG. x and vertical axis y
The centers of adjacent depressions along are spaced apart by a distance 52 and serve to provide a rapid uniform temperature distribution across the spatula section "F" (width 54) including the depressions each having a diameter 57. Each depression contains a new composition, each 0.2 from 96.0〓 to 104.8〓.
At intervals related to the predetermined temperature to be measured, each novel composition has a substantially spherical cavity within its cavity. The "spatula" portion F of the device of FIG. 12 has rounded corners for safety purposes, so that a distance 56 is left between the front row of recesses and the edge of the device. Those skilled in the art will recognize that if a classical composition were to be used in place of the novel composition of the present application, each recess would need to use an indicator layer such as layer 1 of FIG. Referring again to FIG. 12, the aluminum thermally conductive carrier member covers the entire handle "E" portion of the thermometer device by means of a top plastic layer 42 of width 54, preferably made from a plastic such as polystyrene, polypropylene or polyethylene. You will see that it is covered against the 13 along line 13-13 in Figure 12.
As shown, base plate member 46 of width 49 extends along the entire length 53 of the thermometer device. The top layer 42 terminates in the spatula section "F" of the thermometer device;
A grid G of depressions is revealed, with dark indicia 45 (preferably blue or black ink) indicating the predetermined temperature to be measured for each depression, and a heat-sensitive transparent cover film member 43 as a carrier member 44. and overlies each recess to form an enclosure between each recess and the transparent cover film member 43. It is important that the cover film member 43 has an airtight, vacuum-tight fit around the carrier member 44 so that each recess does not lose the composition therein. Therefore, partly for appearance purposes, some minimum distance 55 is
A space is provided between the leading edge of the row of depressions and the edge of the thermometer device. Heat-sensitive transparent cover film member 4
3 preferably consists of a band covering only a narrow area surrounding the recess (in FIG. 13 the transparent cover film member is shown as two bands of width 51 each, which cover the recess). ). It will be apparent to those skilled in the art that the heat-sensitive transparent cover film member may cover the entire spatula portion F of the device. The heat-sensitive transparent cover film member 43 is manufactured by Bio-Medical, Fairfield, New Zealand.
Webb Model manufactured by Sciences, Inc.
A machine such as No. 2 may be used to provide a sealing fit with the aluminum carrier member 44. Also in FIG. 12, the handle E is pressed from below to form two ridges, ribs or pedestals 41a on the device, which extend beyond the carrier member 44 by a nominal distance approximately the same as the width 47 of the carrier member 44. You can see that it is made to stick out at the top. Similarly, the device has two depressions 41b in the carrier member 44 parallel to the ridges 41a. As will be appreciated by those skilled in the art, devices such as those shown in Figures 12 and 13 can be combined with pinacyanol iodide in an amount of 0.05% by weight to form a thermometer according to the novel composition of the present invention. Using o-chloronitrobenzene and o-bromonitrobenzene in the solvent system, it is particularly suitable for measuring human temperatures in the range 96.0 to 104.8. Although not shown, a thermometer similar to the one shown in FIGS. 12 and 13 was attached to the bottom plate member (FIG.
6) from the spatula part F of the device and insert each recess into a carrier member (4 in Figures 12 and 13).
4) It may be made so that it protrudes throughout.
A bottom heat-sensitive and transparent cover film member may be sealingly engaged with the carrier member and around each recess to allow observation of color changes in the novel composition as it is used. Additionally, those skilled in the art will understand that peak 41a in FIG. 12 is not necessarily required. In fact, many minor changes can be made in the apparatus shown in FIGS. 12 and 13 without departing from the essence of the invention. In a preferred embodiment, peak 41a may be omitted in practical applications (disposable thermometers from Organon Inc., West Orange, N.J.).
TEMPA-DOT READY-STRIP). FIG. 14 is a plan view of a support member (preferably transparent) for a disposable thermometer such as that shown in FIG. 10 or FIGS. 12-13. Preferably, the support member is made from highly translucent polypropylene, but alternatively the support member is made of a material that is sufficiently flexible to support the thermometer but not allow the user to disturb delicate tissue. Those skilled in the art will readily recognize that it may be made of any suitable malleable soft material to provide a The support member is particularly contemplated for rectal thermometer readings on infants and adults or those who cannot adequately undergo oral insertion. The member can be placed in any cavity in the body that is large enough to accommodate one that is indicative of body temperature. With respect to FIG. 14 and also FIGS. 15-16 as previously described, it will be appreciated that FIGS. 14-16 are taken from a vertical perspective. In particular, FIG. 15 shows a plan view of the translucent support member, provided that it is in sealing fit with a disposable thermometer with Fahrenheit scales in 0.2° intervals from 96.0 to 104.3°, as shown in FIG. Exclude points. Figure 16 is similar to Figure 15, but
The difference is that a Celsius scale from 35.5°C to 40.4°C is used in 0.1°C intervals. The body 61 of the member is located between portions "H" and "I" which are used to securely and sealingly fit into the spatula portion F and handle portion 42, respectively, of the disposable thermometer of FIG. Works as a bridge. Part I has a handle portion 64 with ridges or indentations as seen from above, which in FIG. 14 is oriented towards the user, but in FIGS. 15-16 it is oriented away. That is, the members in FIG. 14 are
As shown in Figure 16, it is simply rotated 180 degrees around the axis in order to insert a Fahrenheit thermometer. Mine 63
are connected into the body 61 as ridges or indentations 62, which extend across the entire support member on both sides of the member into portion "H". The peak is wide enough to receive the thermometer stably, and the 10th
Alternatively, the disposable thermometer of FIG. 12 has leeway to ensure a secure fit with the member. The tip 65 of the spatula in section H is smoothly rounded with the outer edge of the member so as not to damage delicate tissue when the thermometer is inserted. The spatula portion H is suitably constructed with a window or space so that the thermometer grate, such as grate G of FIG. 10, can be removed from the subject and clearly viewed by the user. In FIG. 17, the cover layer 66 is an adhesive layer 68.
It is coupled to the carrier layer 67 by. This adhesive layer 68 consists of a pressure sensitive adhesive consisting entirely or substantially of polyisobutylene and can be applied to the carrier layer 67 without exceeding the melting point of the heat sensitive composition 69 in the recess. In FIG. 18, carrier layer 67 is also provided with a surface layer 70 of polyisobutylene.
The latter comprises a pressure-sensitive polyisobutylene of adhesive layer 68 consisting essentially of polyisobutylene and a carrier layer 6.
It functions to improve the adhesion between materials No.7. Surface layer 70 is generally obtained by providing the carrier layer material with a thin coating of a solution of polyisobutylene in an organic solvent, such as hexane, and then evaporating the solvent. Heat sensitive composition 69 of Figures 17 and 18 is preferably selected from the novel compositions of the present invention. When the heat-sensitive composition 69 is a classic composition, it is used with an indicator (not shown in Figures 17 and 18), which indicator can be any indicator member known in the art, such as an indentation. It may be a paint layer located at the bottom of the thermosensitive composition, a dye dispersed in the heat sensitive composition, or an indicator layer of absorbent material located above the heat sensitive composition. In yet another preferred embodiment of the invention and another example using the substantially spherical cavity of FIG.
A circular layer of bibulous absorbent material impregnated with all or part of the novel composition present within the recess of the figure may be used. As can be seen from the above,
As shown in FIG. 5, each depression 13 appears to be a fully colored dot. Of course, the hygroscopic material must be inert to the phenomena of the new composition and consists of hydrophobic synthetic paper. One material that has been found to be particularly suitable is EIDuPont de
Nemours &Company's Spun
bonded) polyolefin TYVEK. Other suitable materials include agglomerated inorganic powders, fiberglass paper, ordinary cellulose paper, or polystyrene or other permeable polymeric materials. Another advantage of using a hygroscopic material is that the transparent cover film member 43 (13th
If the device (Figure) is accidentally broken, for example by the user's teeth, the hygroscopic material will not spill the liquid contents into the surrounding area. The hygroscopic material loaded with the novel composition can be used in many other applications, for example as a filling material for the recesses of temperature indicating devices when cut into small pieces. Another preferred temperature indicating device consists of a layer of absorbent material (hygroscopic material) imbibed with the novel composition, which is surrounded by two sealingly fitted transparent cover sheets. Additionally, hygroscopic materials have been found to act as recrystallization promoting materials, particularly when they are used as carriers for containing finely divided insoluble nucleating agents. Such loading can be accomplished by passing a hygroscopic web through a dispersion of powder and then evaporating the solvent. The perforated hygroscopic material holds a known, predetermined amount of nucleating agent and can be used in the well of a thermometer or other device using the novel composition. In preferred embodiments, film-forming materials such as gelatin, polyvinyl alcohol and water-soluble cellulose derivatives are used in the novel compositions of the present invention, especially
It has been found that OCNB/OBNB is a good wall for containing small particles or droplets of the solvent composition. After this microencapsulation, a dry particulate material is formed, which can be easily subjected to various mechanical treatments. A typical microencapsulated novel composition is an OCNB/OBNB containing 0.035% by weight pinacyanol iodide coacervated with acacia and surrounded by a layer of gelatin fixed with glutaraldehyde.
It is a solution. By using these novel microencapsulated compositions, temperature sensing devices can be applied with greater flexibility. For example, the new microencapsulated compositions can be formulated into pressure sensitive adhesives from which temperature indicating tapes can be made. The novel microencapsulated compositions can be incorporated into printed materials that provide any form of temperature sensitive area, including temperature sensitive communications. Exposure of the thermometer to temperatures above 35.5°C will render it useless for further temperature measurements unless effective recrystallization methods are used. Protective packaging will often be required during shipping. The protective packaging of heat-labile products can be significantly improved by the use of certain salts, particularly sodium sulfate decahydrate, such as Glauber's salt, as a freezing agent.
Grover's salt acts as a freezing agent as follows: Grover's salt has a melting point of 32.8°C. TEMPA-DOT
READY-STRIP begins to show a temperature of 35.2°C.
When a TEMPA-DOT READY-STRIP thermometer is packaged with Grover's salt and exposed to a high temperature, for example 50°C, the temperature of the package increases until it reaches 32.28°C. At that temperature Grover's salt begins to melt and approx.
Absorbs heat (energy) with a capacity of 54 cal/g. The package will remain at approximately 32°C until the salt is completely melted. In addition to sodium sulfate decahydrate, calcium chloride hexahydrate is likewise suitable. Additionally, organic compounds with a melting point of 32°C, e.g.
OCNB may also be used. Generally, the cryogen should be selected to have a melting point of 3-5°C below the temperature at which it becomes unstable. A preferred method of packaging the new cryogen is to absorb the molten fresh cryogen into an absorbent material such as open cellular foam, paper, natural or synthetic sponge, etc., and seal it to prevent contamination and protect it from hydrated salts. For example, wrapping the structure in a flexible plastic bag eliminates water vapor exchange. An example of such a packaged novel cryogen is sodium sulfate decahydrate imbibed in a block of open cellular phenol formaldehyde foam and heat sealed in a closed polyethylene bag. When placed in an insulated container, the new cryogen block protects its contents from exposure to high temperatures in the same manner as unsupported Grover's salt. Although the present invention has been described with respect to the above-mentioned specific embodiments, many changes and modifications can be made without departing from the essence of the present invention, as described in the claims and as shown in the following examples. will be clear to those skilled in the art. Example 1 A mixture of o-chloronitrobenzene and o-bromonitrobenzene (o-chloronitrobenzene
25% by weight and o-bromonitrobenzene 25% by weight)
A solution of about 0.05% by weight of pinacyanol iodide in was prepared by adding pinacyanol iodide to a beaker containing a liquid solvent mixture at about 50°C. After dissolving the pinacyanol iodide by mechanical stirring, a new composition was obtained. This blue liquid was cooled and, using artificial nucleation, the blue liquid was transformed into a light greenish-pink solid at approximately 38°C. When the solidified material was heated to its melting point, it became a blue liquid again. This example shows that novel compositions using compounds of group () change color when passing from liquid to solid state or vice versa. Example 2 A solution of about 0.05% by weight chlorophenol red in dibenzofuran was prepared by adding the chlorophenol red to liquid benzofuran at 95°C. After dissolving the chlorophenol lead,
A yellow liquid was obtained. When this liquid is cooled to about 87°C, it begins to solidify and when solidification is complete,
A red solid was obtained. When the red solid was heated, it changed back to a yellow liquid. This example illustrates the use of group () compounds when dissolved in a heterocyclic solvent to give a color change upon transition from liquid to solid or vice versa. Example 3 0.0375% by weight of chlorophenol red
A solution of 0.0125% by weight ethyl red was prepared in Example 1.
It was prepared by dissolving it in a mixture of o-bromonitrobenzene and o-chloronitrobenzene (weight ratio 3:1) as described in . Upon cooling and artificial nucleation, the red liquid turned into a yellow solid at 37.5°C. Upon heating, the yellow solid turned red again at 38.0°C. An example of this is that using a combination of an acid with a pK of less than about 4 and a basic indicator in a suitable aromatic solvent system results in a color change in response to a change in state from liquid to solid or vice versa. This is an example. Example 4 In the same manner as described in Example 1, a solution of 0.037 wt. ) was prepared by dissolving it in a mixture of The liquid solution was green, whereas the solid solution obtained by artificial nucleation at 38°C was yellow. When the composition was heated to melting point, a green liquid was obtained. This example illustrates that the combination of an aminotriphenylmethane dye with an acid having a pK of less than about 2 causes a color change upon transition from liquid to solid state or vice versa. Example 5 This example illustrates the use of a combination of a dye having a molecular structure containing lactone groups and an acid having a pK of about 8 to about 12. By the same method as described in Example 1, 0.05
0.05 wt% Crystal Viarez Tolactone
% by weight of phenol, o-bromonitrobenzene and o-chloronitrobenzene (weight ratio 3:
It was prepared by dissolving in the mixture of 1).
The liquid solution is yellow, and it is made by artificial nucleation to 37.5
When it completely solidified at °C, it turned blue. When the composition was heated, it turned yellow again. Example 6 (Comparative Example) This example deals with a dye that is exemplary of the scope of the present invention. In the same manner as described in Example 1, a solution of Fast Blue Salt B was prepared with o-bromonitrobenzene and o-chloronitrobenzene (3:1 weight ratio).
was prepared by dissolving it in a mixture of The color of the liquid was yellow and did not change even after completely solidifying the solvent. Example 7 This example shows that dyes are present at various concentrations in various solvents.
Those dyes tested for suitability as group () compounds are described. The results are shown in the table.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

TABLE Example 8 This example describes combinations tested for color change in various solvents and at various concentrations. Such combinations include: (a) mixtures of compounds of group (); (b) mixtures of acids with a pK of less than about 4 and basic dyes or basic indicators; (c) mixtures of organic acids and acidic dyes or basic indicators with a pK of less than about 2. (d) mixtures of group () compounds with organic acid compounds having a pK of less than about 4; (e) mixtures of group () compounds with basic dyes or basic indicators; (f) lactones; A mixture of a dye and an acid with a molecular structure containing groups. The results are shown in the table.

【table】

【table】

【table】

【table】

EXAMPLE 9 This example illustrates the use of an insoluble nucleating agent in a temperature indicating device so that the composition can be recalculated at a predetermined temperature. A number of wells formed in the aluminum carrier layer were filled with a mixture of o-bromonitrobenzene and o-chloronitrobenzene containing iodide in 0.025% by weight pinacyanol with the addition of varying amounts of nucleating agent. The cavity thus filled was filled with a heat-sensitive transparent Surlyn 1652 film (USA, EIDuPont de
Nemours & Company) was installed. After recrystallizing the chemicals at -40°C, the indicator was heated at about 55°C for 1 hour (similar to storage at elevated temperatures). The indicator was then cooled to −6° C. and the % of the depression in which the mixture had recrystallized was determined. In a second series of experiments, an indicator device containing the recrystallization mixture was brought to a temperature just above the melting point of the chemicals (approximately 38 degrees Celsius) to mimic measuring the temperature of the human body.
Heat in water bath for 45 seconds. The indicator device was then cooled to room temperature and the % of depressions in which the chemical crystallized was determined. In each case 170 wells were filled for each nucleator studied. For comparison, the indentations were made using the same OBNB/OCNB containing 0.025% by weight pinacyanol iodide.
Filled with mixture. However, the nucleating agent was excluded. The results are shown in Table 1. Addition of nucleating agent is -6
It can be seen that it has a positive effect on recrystallization at °C, while it has no effect on supercooling at room temperature.

【table】

EXAMPLE 10 This example illustrates the use of a pretreated aluminum carrier layer to allow the composition to recrystallize at a predetermined temperature. The indented aluminum carrier layer was cleaned by washing the aluminum with acetone, soaking it in 2% sodium hydroxide, and then soaking it in 10% nitric acid.
Passivation was achieved by immersion in boiling water for 5 minutes. The well was filled with a mixture of o-chloronitrobenzene and o-bromonitrobenzene (1:3 weight ratio) containing 0.025% by weight of pinacyanol iodite. Further example 9 fills the hollow
Processed as described in . For comparison, cavities formed in untreated aluminum were filled with the above mixture and treated in the same manner. The results are shown in the table.

[Table] Passivation of aluminum carrier layer is -6
It can be seen that this has a favorable influence on recrystallization at ℃. Example 11 Transparent polyester film with adhesive layer of polyisobutylene (supplied by ICI)
Melinex) was pressed together with an aluminum layer foil. The force required to peel the polyester film from the aluminum foil at a speed of 30 cm/min was measured in g/cm and used as a measure of adhesive strength. This force should be at least about 150 g/cm. The influence on the magnitude of the peel force was determined by the nature of the aluminum surface (rough, smooth, etched), the type of polyisobutylene (molecular weight, mixture), and the adhesive pressure (5 and 50 Kg/cm ² ).
I looked into it. The type of polyisobutylene used was from Ludwigschaufen, West Germany.
It is obtained from BASF and is commercially available under the trade name Oppanol. List the results in a table.

[Table] Example 12 Polyisobutylene was examined for its permeability to chemicals used in temperature indicating devices. A polyisobutylene film was formed from a solution applied onto paper. A bag of about 60 cm ² was made from the film thus obtained, filled with 2.5 g of a mixture of o-chloronitrobenzene and o-bromonitrobenzene (weight ratio 62:38) and sealed. After weighing, the bags were stored at 32° C. in a room with air circulation and the weight loss was determined after various times. Summarize the results in a table.

[Table] Symbols PIB1, PIB2 and PIB3 have the same meaning as in Example 11. For comparison, results obtained for a film (45 μm thick) of the ionomer adhesive Surlyn 1652 are also shown. It can be seen that the polyisobutylene sample is much less permeable than the ionomer adhesive. Example 12 Recesses formed in the aluminum carrier layer were filled with a mixture of o-chloronitrobenzene and o-bromonitrobenzene and sealed with a cover layer consisting of a polyester film with a layer of polyisobutylene adhesive. The test objects thus obtained were stored at 20 °C and 32 °C in order to determine whether the chemicals were dissolved in the adhesive layer, disappeared from their recesses, or turned into a liquid. , examined using a stereomicroscope. Observations were conducted for 40 days. The results are shown in the table.

[Table] From this table, it can be seen that if the adhesion to the aluminum foil is maintained, the chemical will not leak or dissolve. High molecular weight polyisobutylene (PIB4) is the least unstable to viscous deformation. Example 14 This example shows the reproducibility of temperature readings. In the numerous depressions formed in the aluminum carrier layer,
-Chloronitrobenzene, o-bromonitrobenzene and 0.1% by weight Orazol Blue BLN
(Solvent Blue 49) is a mixture consisting of
A series of mixtures of increasing melting point by 0.1° C. were filled. The wells thus filled were then filled with Whatman chromatography paper.
No. 1 and then sealed with polyester film (Melinex) with a polyethylene pressure sensitive adhesive layer. The polyisobutylene used was Opanol.
B15 (average molecular weight 77000-92000) and opanol
It is a mixture of equal parts of B100 (average molecular weight 1.08-1.46×10 ⁶ ). The test object was stored at 28℃, and
After 10 weeks, each indicator layer was placed in a water bath at a specific temperature to determine the temperature at which color change occurred. The results obtained as the average values of the four temperature indicating devices are shown in the table.

[Table] It can be seen that the temperature index as a function of time changes little or not at all. Example 15 (Comparative Example) A number of known adhesives whose adhesive layers can be formed at room temperature were tested in the manner described in Example 13. Etch the aluminum foil to be used in advance. The results summarized in the table show that among the adhesives investigated, which are all outside the scope of the present invention, none are suitable for use for this purpose.

【table】 [Brief explanation of the drawing]

FIG. 1 shows the liquidus curve of a solid solution of o-chloronitrobenzene and o-bromonitrobenzene over the human body temperature range. FIG. 2 is a partial horizontal sectional view of a novel flat or tapered thermally conductive carrier with defined depressions. the recess is covered by sealingly engaging the carrier member with a transparent cover sheet member overlying the thermally conductive carrier member and overlying the recess;
Forming an enclosure for temperature-sensitive "classical" compositions in it. The figure also shows a substantially spherical cavity within the temperature sensitive composition. Figure 3 shows
3 is a cross-sectional view taken along line 3-3 of FIG. 2; FIG. When the colored material is in the indicating member at the bottom of the recess,
FIG. 3 is a partial plan view of the depression seen from above the depression of FIG. 2; FIG. 4 is a cross-sectional view taken along line 4--4 of FIG. 2 is a partial plan view from above of the depression of FIG. 2 when the pigmented material is enlarged by the spherical cavities in the "classical" composition when it is melted; FIG. FIG. 5 is a partial plan view from above of a thermometer spanning a portion of the human body temperature range (° C.) in accordance with the principles of the present invention. FIG. 6 is a top plan view of a thermometer spanning the human body temperature range (ⓓ) according to the principles of the present invention. FIG. 7 is a plan and cross-sectional view of a 10 mm interval thermometer using the new composition of the present invention in commercial applications. FIG. 8 shows a top view and horizontal cross-section of a label for indicating a temperature above a predetermined safety limit using the novel composition of the present invention. Figure 9 shows
1 is a partially cutaway perspective view of a thermometer consisting of a thermally conductive carrier member with a grid of recesses inserted into the case so that only the handle of the thermally conductive carrier member sticks out; FIG. Figure 10 shows the shape of the grid of depressions in the thermally conductive carrier member from 96.0〓 to
9 is a perspective view of the thermometer as in FIG. 9 with the case of FIG. 9 removed, except that it shows a body temperature scale of 104.8°C; FIG. FIG. 11 is a horizontal cross-section along line 11-11 of FIG. 10 showing several recesses in the thermally conductive carrier member each surrounded by a transparent cover sheet and a bottom transparent base plate member; . 1st
FIG. 2 is a top plan view of a flat plate temperature indicator without a case, consisting of a thermally conductive carrier member with a grid of recesses. FIG. 13 is a horizontal cross-sectional view taken along the line 13-13 in FIG.
The carrier member, the recess therein, the transparent cover sheet member and the bottom plate member are shown. Figure 14 shows the first
FIG. 14 is a top plan view of a transparent indicator for the disposable thermometer of either FIG. 0 or FIGS. 12-13; Figure 15 shows 96.0〓 with an interval of 0.2〓.
No. 10 with graduated Fahrenheit scale from to 104.8〓
15 is a plan view from above of a transparent support member as shown in FIG. 14, except in sealing engagement with a disposable thermometer as shown; FIG. Figure 16 shows
A disposable thermometer as shown in Figure 10, except that it is fitted sealingly with a Celsius scale from 35.5°C to 40.4°C in 0.1°C intervals.
FIG. 15 is a plan view from above of the transparent support member as in FIG. 14; FIG. 17 shows the novel composition of the present invention or the classic temperature-sensitive composition therein when the recess is covered with a transparent cover sheet member bonded to the carrier layer with an adhesive layer of polyisobutylene. 2 is a partial horizontal cross-sectional view of a thermally conductive carrier with defined depressions forming an enclosure; FIG. 18th
The figure is a partial horizontal cross-sectional view similar to FIG. 17, but in the case where the carrier layer is also provided with a surface layer of polyisobutylene.

Claims (1)

[Scope of Claims] 1. At least 1. a solvent () consisting of a single substance or a mixture of substances, which is compatible with changing from a solid state to a liquid state at a substantially predetermined temperature; , 2 An indicator system () consisting of one or more substances different from (), in which (a) () is soluble in () when () is in a liquid phase, and (b) () changes from a solid to a liquid phase. an indicator system (), characterized in that () undergoes a macroscopic color change upon transition from liquid to solid phase, and wherein said solvent () is , o-chloronitrobenzene, o-bromonitrobenzene, 1-thymol,
2-naphthol, 2-ethoxybenzamide, naphthalene, p-dichlorobenzene, o-iodonitrobenzene, m-iodonitrobenzene, p
- iodonitrobenzene, p-chloronitrobenzene, m-bromonitrobenzene, p-bromonitrobenzene, p-dipromonitrobenzene,
selected from the group consisting of p-toluic acid, n-tetracosane, 1-tetradecanol, stearic acid, t-butanol, lauryl alcohol, formamide, paraffin, dioxane, symmetric trioxane, indole, dibenzofuran, and water. and the indicator system () is a solvent of the following groups: (i) monoazo, disazo, triarylmethane, xanthene, sulfonphthalein, acridine, quinoline, azine, oxazine, thiazine, anthraquinone, indigoid, and Individual compounds of: Aurantia,
Orasol Orange RLN, Diamin Green B, Direct
Green G, Fast red salt
3GL, First Blue Salt BB, First Garnet Salt GBC, Carta Yellow
Compounds of a single compound group consisting of G180%, Murexide, Savinyl Blue GLS, Irgalith Blue GLSM, Phthalocyanine and Alcannin; (ii) (a) having a pK of less than about 4; (b) one or more basic dyes or basic indicators; (iii) (a) one or more organic acids having a pK of less than about 2; (b) one or more acidic dyes or indicators; (iv) (a) one or more organic acid compounds having a pK of less than about 4; and (b) one or more compounds from group (). (v) a mixture of (a) one or more basic dyes or basic indicators and (b) one or more compounds from the compounds of group (); (vi) (a) containing a lactone group; (b) one or more acids having a pK of about 8 to about 12; an effective amount of one or more suitable organic acids selected from the group consisting of: 1. Said composition consisting essentially of: 2 When the solvent () is in the solid phase, the solubility of the indicator system () in the solvent () is the same as () when () is in the liquid phase.
much lower than the solubility in () of
The composition according to item 1, wherein () partially or completely separates during the transition of () from a liquid phase to a solid phase. 3 Monoazo dyes include 4-(p-ethoxyphenylazo)-m-phenylenediamine, mono-hydrochloride, Orazol navy blue, Organol orange, Janus green, Ilgaris Red P4R, dimethyl Yellow, Fast Yellow, Methyl Red Sodium Salt, Alizarin Yellow R, Eriochrome Black T, Chromotrope 2R, Ponceau 6R,
Yellow Orange S, Brilliant
Ponsou 5R, Chrysoidin G,
Eriochrome Black A, Benzyl Orange,
The composition according to item 1, which is Ponsou G/R/2R and Chromolan Yellow. 4 Disazo dyes include Fat Red BS, Sudan Red B, Bismarck Brown G, Fat Black, Resorcin Brown, Benzofast Pink 2BL, and Oil Red EGN.
The composition according to item 1 above. 5 Triarylmethane dyes include methyl biallet, xylene cyanol FF, eriogloucin, fuchsin NB, fuchsin, parafuchsin,
The composition according to item 1, which is aurintricarboxylic acid ammonium salt, Patent Blue, Victoria Blue R, Crystal Vialect, and Ilgaris Blue TNC. 6 The xanthene dye is Phloxin.
B, Fluorescein sodium salt, Rhodamine B, Rhodamine B base, Rhodamine 6G, Pyronin
G, Ilgaris Magenta TCB, Ilgaris Pink TYNC, Eosin Scarlet, Eosin Yellow, Erythrosin Extra Blue, 4',5'-Dibromo Fluorescin, Ethyl Eosin, Gallein, Floxain ( 2. The composition according to item 1, wherein the composition is Phloxine), Erythrosin Yellow Dust Blend, and Cyanosin B. 7. The composition according to item 1, wherein the sulfonphthalein dyes are cresol red, chlorophenol red, chlorophenol blue, bromophenol blue, bromocresol purple and chlorocresol green. 8. The composition according to item 1 above, wherein the acridine dyes are Coriphosphine O, Acriflavine and Acridine Orange. 9 Quinoline dyes include pinacyanol chloride, pinacyanol bromide, pinacyanol iodide, quinaldine, cryptocyanine, 1,1'-diethyl-2,2'-
Cyanine iodide, 2-(p-dimethyl
aminostyryl)-1-ethyl-pyridinium
Iodide, 3,3'-diethyl-thiadicarbocyanine The composition according to item 1, which is iodide, ethyl red, dicyanine A, Merocyanine 540 and Neo cyanine. 10 Azine dyes are neutral Red Chloride, Neutral Red Iodide, Nigrosine, Sabinyl Blue B, Orazol Blue BLN Safrnine O, Azocarmine
G, Pheno Safranin, Azocarmine
A composition according to paragraph 1, which is BX and Rhoduline vialets. 11. The composition according to item 1, wherein the oxazine dyes are Solophenyl Brilliant Blue BL, Nile Blue A, Gallocyanine, Gallamine Blue and Celestine Blue. 12 The first thiazine dye is methylene blue, thionine, toluidine blue O, methylene green and Azure A/B/C.
The composition described in Section. 13 Anthraquinone dyes include Sabinyl Green B, Sabinyl Green RS, D+C Green 6, Blue VIF Organol, Alizarin, Alizarin Cyanine 2R, Celliton Blue Extra, Alizarin Blue S, Nitro Fast Green GSB, Alizarin Red S, Chinalizarin , Oil Blue N, Solway Purple and Purpurin. 14. A composition according to paragraph 1, wherein the indigoid dyes are Ciba Blue, Indigo Synthetic, Cromophtal Bordeaux RS and Thioindigo Red. 15 The organic acid having a pK of less than about 4 is a halogenated sulfonophthalein, and the basic dye or indicator is aminotriphenylmethane and/or its soluble salts, 8-hydroxyquinoline and cyanine. Yes, but if the basic compound consists only of one or more aminotriphenyl methane or their soluble salts,
The composition of paragraph 1, wherein the acidic compound is selected from the group consisting of tetrahalogenated sulfonphthalein and other organic acids having a pK of less than about 2. 16. The composition of paragraph 1, wherein the acidic dye or acidic indicator in a mixture with one or more organic acids having a pK of less than about 2 is a halogenated sulfonophthalein. 17 Organic acid compounds having a pK of less than about 4 include oxalic acid, maleic acid, dichloroacetic acid, trichloroacetic acid, 2-naphthalenesulfonic acid, chloroanilic acid, bromophenol blue, bromothymol blue, chlorophenol red, bromochlorophenol. blue, bromocresol
Green, 3,4,5,6-tetrabromophenol sulfonphthalein, bromophenol
The composition according to item 1, wherein the composition is red, chlorocresol green, chlorophenol blue, bromocresol purple, and 2,4-dinitrobenzenesulfonic acid. 18 The basic dye or basic indicator is basic fuchsin, pinacyanol iodide, pinacyanol chloride, piacyanol bromide, 2-p (dimethylaminostyryl)-1
-Ethyl-pyridinium iodide, crystal viarez, cryptocyanin, dicyanine A, 3,3'-diethylthiacarbocyanine iodide, 1,1'-diethyl-2,2'-cyanine iodide, ethyl red, quinaldine red, ethyl viarez, brilliant
Green, pararoseaniline, pararoseaniline acetate, 8-hydroxyquinoline, 1
-ethylpyridinium iodide and 5-
The composition according to item 1 above, which is (p-dimethylaminobenzylidene)rhodanine. 19. The dye having a molecular structure containing a lactone group is crystal vial lactone, and the acid having a pK of about 8 to about 12 is 3-nitrophenol, bisphenol A, pyrocatechol, and phenol. Composition of. 20. The composition of item 1 above, wherein the selected organic acid is piacyanol iodide. 21 The selected organic moiety is chlorophenol
The composition according to item 1 above, which is a red. 22. The composition of item 1 above, wherein the selected organic moiety is Alizarin Blue S. 23 The selected organic moiety is bromophenol
The composition according to item 1 above, which is blue and salt fuchsin. 24 The selected organic moiety is chlorophenol
The composition according to item 1 above, which is blue and ethyl red. 25. The composition of paragraph 1, wherein the selected organic moieties are trichloroacetic acid and 3,3'-diethylthiadicarbocyanine iodide. 26 1 a solvent used to change from a solid state to a liquid state at a substantially predetermined temperature; consisting essentially of an effective amount of an indicator compound selected from the following indicator systems used to cause a macroscopic color change in the composition upon change in the state of said solvent at a defined temperature, over a period of at least several minutes. solid state when the composition is in the solid state; A composition according to claim 1 forming: a mixture of the indicator compounds chlorophenol and ethyl red, a mixture of bromochlorophenol blue and ethyl violet, a mixture of bromophenol blue and basic fuchsin, bromophenol red. mixture of bromochlorophenol blue and pinacyanol chloride, mixture of 3,3'-diethylthiadicarbocyanine iodide and bromocresol purple, 3,3'-diethylthiadicarbocyanine iodide mixture of pinacyanol chloride and 3,4,5,6-tetrabromophenolsulfonaphthalene, mixture of pinacyanol chloride and bromocresol purple, mixture of ethyl red and bromochlorophenol blue, pinacy Mixture of anol chloride and chlorocresol green, pinacyanol iodide, quinaldine red, 1,1'-diethyl-2,2'-cyanine iodide, mixture of bromophenol blue and ethyl red, chlorophenol red, ethyl red and 3, Mixture of 4,5,6-tetrabromophenolsulfonaphthalene, Mixture of ethyl red and bromophenol red, Mixture of ethyl red and bromophenol blue, Mixture of crystal violet and bromophenol blue, Mixture of bromochlorophenol blue and bromophenol green mixture, mixture of naphthalene sulfonic acid and ethyl violet, mixture of naphthalene sulfonic acid and crystal violet, mixture of naphthalene sulfonic acid and ethyl violet, mixture of trichloroacetic acid and cryptocyanine, mixture of trichloroacetic acid and ethyl violet, 3-ethyl -2-[5-(3-ethyl-2-benzothiazolinylidene)-1,3-pentadienyl]-Mixture of benzothiazolium iodide and trichloroacetic acid, mixture of chloroanilic acid and basic fuchsin, chloro Mixture of phenol red and dicyanin A, mixture of chlorophenol red and cryptocyanin, bromochlorophenol blue and dicyanin A
a mixture of 5-p-dimethylaminobenzilidine rhodanine and dicyanine A; a mixture of 5-p-dimethylaminobenzilidine rhodanine and cryptocyanine. 27. The composition of any one of paragraphs 1-26, wherein the weight percent of the organic moiety soluble in the solvent is from about 0.005% to about 0.2% of the weight of the solvent and the soluble organic moiety. 28. The composition according to any one of paragraphs 1 to 27, wherein the predetermined temperature is about 35°C to about 42°C. 29. The composition according to any one of items 1 to 28 above, wherein the solvent is a binary mixture of o-chloronitrobenzene and o-bromonitrobenzene. 30 The first to second compositions have an impurity content of less than 0.3% and are capable of supercooling.
9. The composition according to any one of Item 9. 31 Soluble or insoluble nucleating agent from 0.001 to
30. A composition according to any one of the preceding clauses, comprising 10.0% by weight, thereby allowing recrystallization at a substantially predetermined temperature. 32 The nucleating agent is anthraquinone, talc, aluminum oxide, silicon dioxide, modified silica, boron,
32. The composition according to item 31, which is titanium carbide, diamond, and molybdenum disulfide. 33. A composition according to paragraph 32, wherein the nucleating agent is talc having a particle size of 0.1 to 10 micrometers. 34. In one or more isolated areas, the same number of different prescribed compositions are contained in order to determine the same number of predetermined temperatures within a predetermined temperature range. a thermally conductive carrier having defined areas in which said composition is contained by a transparent cover sheet member sealingly engaged with said carrier, each said area having said composition in said carrier; a single composition with a single predetermined temperature is deposited;
If those compositions used are at least 1 composed of a single substance or a mixture of substances, a solvent () compatible with converting the solid state into the liquid state at a substantially predetermined temperature; 2. An indicator system () consisting of one or more substances different from (), in which (a) () is soluble in () when () is in a liquid phase, and (b) () is soluble in () when () is in a liquid phase. an indicator system (2), characterized in that (2) undergoes a macroscopic color change when transferred to or from a liquid phase, and (2) a composition consisting essentially of said solvent (2); is o-chloronitrobenzene, o-bromonitrobenzene, 1-thymol,
2-naphthol, 2-ethoxybenzamide, naphthalene, p-dichlorobenzene, o-iodonitrobenzene, m-iodonitrobenzene, p
- iodonitrobenzene, p-chloronitrobenzene, m-bromonitrobenzene, p-bromonitrobenzene, p-dibromonitrobenzene,
selected from the group consisting of p-toluic acid, n-tetracosane, 1-tetradecanol, stearic acid, t-butanol, lauryl alcohol, formamide, paraffin, dioxane, symmetric trioxane, indole, dibenzofuran, and water. and the indicator system () is a solvent of the following groups: (i) monoazo, disazo, triarylmethane, xanthene, sulfonphthalein, acridine, quinoline, azine, oxazine, thiazine, anthraquinone, indigoid, and Individual compounds of: Aurantia,
Orasol Orange RLN, Diamin Green B, Direct
Green G, Fast red salt
3GL, First Blue Salt BB, First Garnet Salt GBC, Carta Yellow
Compounds of a single compound group consisting of G180%, Murexide, Savinyl Blue GLS, Irgalith Blue GLSM, Phthalocyanine and Alcannin; (ii) (a) having a pK of less than about 4; (b) one or more basic dyes or basic indicators; (iii) (a) one or more organic acids having a pK of less than about 2; (b) one or more acidic dyes or indicators; (iv) (a) one or more organic acid compounds having a pK of less than about 4; and (b) one or more compounds from group (). (v) a mixture of (a) one or more basic dyes or basic indicators and (b) one or more compounds from the compounds of group (); (vi) (a) containing a lactone group; (b) one or more acids having a pK of about 8 to about 12; an effective amount of one or more suitable organic acids selected from the group consisting of: A temperature indicating device, wherein the composition consists essentially of: 35. The device of claim 34, wherein the region is recessed in the thermally conductive carrier. 36. The apparatus of paragraph 34 or 35, wherein the compositions have an essentially linear melting point versus composition relationship over the temperature range represented by the plurality of compositions. 37. A device according to any one of the preceding clauses 34 to 36, wherein the surface of the thermally conductive carrier member is anodized or passivated. 38. The device of any one of the preceding clauses 35-37, wherein each of the compositions associated with a particular depression fills the depression except for a substantially spherical cavity within that depression. . 39. In one or more isolated depressions, one of the same number of respective predetermined temperatures is determined to determine the same number of predetermined temperatures within a predetermined temperature range. a thermally conductive carrier member having defined recesses containing different defined heat-sensitive compositions; an indicator member disposed at the bottom of each of said recesses; an indicator member sealingly engaged with said carrier member; a transparent cover sheet member for covering each recess to form an enclosure between the recess and the transparent member; and a transparent cover sheet member for covering each recess to form an enclosure between the recess and the transparent member; a temperature indicating device comprising each of said compositions substantially filling the recess excluding voids, and said composition comprising at least one single substance or a mixture of substances; (a) an indicator system () consisting of a solvent () suitable for changing the state from a liquid state to a liquid state at a substantially predetermined temperature, and one or more substances different from (2) (); (b) When () is in the liquid phase, () is soluble in (), and (b) when () is transferred from solid to liquid phase, or from liquid to solid phase, () undergoes a visible color change. A composition consisting essentially of an indicator system (), characterized in that the solvent () is o-chloronitrobenzene, o-bromonitrobenzene, 1-thymol,
2-naphthol, 2-ethoxybenzamide, naphthalene, p-dichlorobenzene, o-iodonitrobenzene, m-iodonitrobenzene, p
- iodonitrobenzene, p-chloronitrobenzene, m-bromonitrobenzene, p-bromonitrobenzene, p-dibromonitrobenzene,
selected from the group consisting of p-toluic acid, n-tetracosane, 1-tetradecanol, stearic acid, t-butanol, lauryl alcohol, formamide, paraffin, dioxane, symmetric trioxane, indole, dibenzofuran, and water. and the indicator system () is a solvent of the following groups: (i) monoazo, disazo, triarylmethane, xanthene, sulfonphthalein, acridine, quinoline, azine, oxazine, thiazine, anthraquinone, indigoid, and Individual compounds of: Aurantia,
Orasol Orange RLN, Diamin Green B, Direct
Green G, Fast red salt
3GL, First Blue Salt BB, First Garnet Salt GBC, Carta Yellow
Compounds of a single compound group consisting of G180%, Murexide, Savinyl Blue GLS, Irgalith Blue GLSM, Phthalocyanine and Alcannin; (ii) (a) having a pK of less than about 4; (b) one or more basic dyes or basic indicators; (iii) (a) one or more organic acids having a pK of less than about 2; (b) one or more acidic dyes or indicators; (iv) (a) one or more organic acid compounds having a pK of less than about 4; and (b) one or more compounds from group (). (v) a mixture of (a) one or more basic dyes or basic indicators and (b) one or more compounds from the compounds of group (); (vi) (a) containing a lactone group; (b) one or more acids having a pK of about 8 to about 12; an effective amount of one or more suitable organic acids selected from the group consisting of: The temperature indicating device is the composition consisting essentially of: 40. Said No. 39, wherein the spherical cavity has a diameter slightly smaller than (a) the depth of the recess - (b) the width of the indicator member.
The equipment described in section. 41. The device according to item 39 or 40, wherein the indicating member is a paint layer. 42. A device according to any one of the preceding clauses 39 to 41, wherein the indicating member is a layer of material impregnated with a dye. 43. A device according to any one of the preceding clauses 34 to 42, wherein there is a layer of absorbent material between the cover sheet and the composition. 44. Nos. 39-4, wherein the impurities in each depression are less than about 0.3% by weight of the composition in the depression.
The apparatus according to any one of clauses 3 to 3. 45. Each heat-sensitive composition comprises 0.001 to 10.0% by weight of a soluble or insoluble nucleating agent, such that the composition can be recrystallized at a substantially predetermined temperature. Apparatus according to any one of paragraphs 39 to 44. 46 The nucleating agent is anthraquinone, talc, aluminum oxide, silicon dioxide, modified silica, boron,
46. The device of clause 45, wherein the device is selected from the group consisting of titanium carbide, diamond, and molybdenum disulfide. 47. The device of paragraph 46, wherein the nucleating agent is talc having a particle size of 0.1 to 10 micrometers. 48. The device according to any one of paragraphs 34 to 47, wherein the heat-sensitive composition is a binary mixture of o-chloronitrobenzene and o-bromonitrobenzene. 49. Any one of the preceding paragraphs 34 to 48, wherein the transparent cover sheet member and the thermally conductive carrier are sealed together by an adhesive layer of pressure sensitive adhesive consisting entirely or substantially of polyisobutylene. The device described. 50 (a) A thermally conductive carrier member having one or more recesses, having an indicator member in at least one of the recesses and containing o-chloronitrobenzene and o-bromonitrobenzene melted at a predetermined temperature. (b) a transparent cover sheet over each of said recesses and sealingly engaged with the carrier member; A temperature indicating device characterized in that the transparent cover sheet and the carrier member are bonded to each other by an adhesive layer of pressure sensitive adhesive consisting entirely or substantially of polyisobutylene. 51 The average molecular weight of polyisobutylene is 50,000 ~
50. Apparatus according to any one of the preceding clauses 49 to 50, within the range of 5,000,000. 52 The average molecular weight of polyisobutylene is 150,000~
52. Apparatus according to clause 51, within the range of 4,000,000. 53 The adhesive layer comprises 30 to 70% by weight of polyisobutylene having an average molecular weight within the range of 70,000 to 100,000;
53. The device according to claim 52, comprising a mixture with 70-30% by weight of polyisobutylene having an average molecular weight in the range 1,000,000-3,500,000. 54 Adhesive layer is practically equivalent weight part, 70000~
54. A device according to clause 53, comprising polyisobutylene with an average molecular weight in the range of 100,000 and polyisobutylene with an average molecular weight in the range of 1,000,000 to 3,500,000. 55. A device according to any one of the preceding clauses 49 to 54, wherein the carrier layer comprises an aluminum foil having an etched surface. 56. A device according to any one of the preceding clauses 49 to 54, wherein the carrier layer consists of an aluminum foil provided with a polyisobutylene surface layer applied as a solution in an organic solvent. 57. The device of claim 56, wherein the polyisobutylene surface layer applied to the carrier layer has a thickness of 2 to 10 micrometers. 58 If the surface layer applied to the carrier layer is
58. A device according to any one of the preceding clauses 56 or 57, wherein the polyisobutylene has an average molecular weight in the range of 2,000,000 to 3,500,000. 59. The device of claim 58, wherein the carrier layer comprising a polyisobutylene surface layer is bonded to the transparent cover sheet by a pressure sensitive adhesive layer of polyisobutylene having an average molecular weight in the range of 2,000,000 to 3,500,000. 60 Temperature comprising a layer of absorbent material into which the composition according to any one of paragraphs 1 to 33 has been absorbed, and two transparent cover sheets encasing the absorbent material and fitting hermetically to each other. indicating device. 61 The fourth item wherein the absorbent material is hydrophobic synthetic paper
3 or 60.