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United States Patent (19) (11) 4,232,552 Hof Et Al

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United States Patent (19) (11) 4,232,552 Hof Et Al United States Patent (19) (11) 4,232,552 Hof et al. 45 Nov. 11, 1980 54 TEMPERATURE INDICATING 3,631,720 1/1972 Weinstein ............................... 73/356 COMPOSITIONS OF MATTER 3,665,770 5/1972 Sagi et al. ... ... 73/358 3,688,582 9/1972 Gradisher .... ... 73/358 (75) Inventors: Craig R. Hof, Hopatcong; Roy A. 3,700,603 10/1972 Rembaum ... ... 73/356 Ulin, Wyckoff, both of N.J. 3,704,985 12/1972 Pickett et al. .......................... 73/358 3,828,612 8/1974 Eriksson et al. ... 73/358 73) Assignee: Akzona Incorporated, Asheville, 3,929,021 12/1975 Pecorella ............................... 73/358 N.C. 3,946,612 3/1976 Sagi et al. .............................. 73/358 3,956,153 5/1976 Chadha ..., ... 116/207 (21) Appl. No.: 946,935 3,960,753 6/1976 Cerrabee ................................ 73/356 1a. 3,980,581 9/1976 Godsey et al. ... 252/408 22 Filed: Sep. 28, 1978 4,042,336 8/1977 Larsson .................................. 73/356 4,128,007 12/1978 Uun ........................................ 73/356 Related U.S. Application Data 4,138,357 2/1979 Icaraski .................................. 73/356 (63) Continuation-in-part of Ser. No. 895,422, Apr. 13, : A: E. et al. - a 23/230 R 1978, abandoned, which is a continuation-in-part of 4, 151748a wWy 5/1979 Baumindquist ... 16/2773/356 Ser. No. 844,334, Oct. 21, 1977, abandoned, which is a 4,154,106 5/1979 Inoue et al. continuation-in-part of Ser. No. 796,492, May 12, 1977, 4,154,107wity 5/1979 Giezennoue et et al. all ............................ 73/356 abandoned. 4,163,427 8/1979 Cooperman et al. .................. 73/358 51 Int. Cl. ..................... G01K 11/06; G01K 11/08; 4,189,942 2/1980 Giezen et al. .......................... 73/356 G01K 11/12; G01K 11/16; G09K 3/00 FOREIGN PATENT DOCUMENTS 52 U.S. Cl. ................................... 73/356; 23/230 R; 73/358; 116/201; 116/206; 116/207; 116/216; : 8, 12: E. E. SAY - - - - - - - - - - - - - A: 116/217; 252/408; 422/55; 422/56;o E. - 3640 of 1898 Uniteded. Kep. Kingdom ermany ...................... ............. 73/358 551783 3/1943 United Kingdom. ... 16/207 58) Field of Search .................. 73/356, 358; 252/408; 904846 8/1962 United Kingdom ... ... 116/217 23/230 R; 116/201, 206, 207,216, 217, 219; 1367703 9/1974 United Kingdom ...................... 73/356 422/55, 56, 57, 58, 119 56) Refeferences CitedUte OTHER PUBLICATIONS Larsson, R., BMS Interoffice Memorandum, dated Jun. U.S. PATENT DOCUMENTS 27, 1975, (unpublished). 1,951,650 3/1934 Diack ..................................... 73/356 2, 193,439 3/1940 Van Doren. ... 73/356 Primary Examiner-Teddy S. Gron 2,261,473 11/1941 Jennings .......... ... 252/408 Attorney, Agent, or Firm-Robert H. Falk; Charles A. 2,379,459 7/1945 Schreiber et al. .. ... 73/358 Wendel; Francis W. Young 2,490,933 12/1949 Tornquist et al. ...... ... 73/356 2,560,537 7/1951 Andersen ........ ... 73/358 (57) ABSTRACT 2,710,274 6/1955 Kuehl ....... ... 73/356 2,799,167 7/1957 Loconti ... ... 73/356 Novel and stable compositions of matter are disclosed 2,809, 16 10/1957 Laskowski ... 73/356 which change color sharply upon a transition from a 2,846,829 8/1958 Eskin........ ... 73/356 liquid state to a solid state or from a solid state to a 2,850,393 9/1958 Romito ........ ... 73/356 liquid state, which change of state is at substantially a 2,932,971 4/1960 Moore et al. ... 73/356 predetermined temperature corresponding to a temper 3,038,812 6/1962 Berman ........... 116/206 ature to be measured. 3, 175,401 3/1965 Celdmacher ... 73/356 3,465,590 9/1969 Kluth et al. ..... ... 73/358 The constituents of the novel compositions of matter 3,576,604 4/1971 Hammond . ... 73/356 comprise: 3,597,976 8/1971 Fryar ..................................... 73/358 1. a solvent (I) consisting of a single substance or a 4,232,552 Page 2 mixture of substances and adapted to change from (I) passes from the solid to the liquid phase or a solid state at substantially a predetermined tem- from the liquid to the solid phase. perature to a liquid state and 2. an indicator system (II) consisting of one or more Thermometers containing said stable compositions of substances different from (I), characterized in that matter are also disclosed. (a) (II) is soluble in (I) when the latter is in the liquid phase, and (b) (II) changes color visible to the naked eye when 89 Claims, 18 Drawing Figures U.S. Patent Nov. 11, 1980 Sheet 1 of 7 4,232,552 O5 O4 4O O3 S- 39 O2 D o s s Z l ol C - H 38 OO 99 37 98 97 36 96 O 2O 4O 6O 8O OO WEGH / ORTHO-BROMONTROBENZENE IN THE SOLD SOLUTION U.S. Patent Nov. 11, 1980 Sheet 2 of 7 4,232,552 S WO1\ ZYaaaaaaaaaaaaaaaaaZZZZZazaarara23-3 3. U.S. Patent Nov. 11, 1980 Sheet 3 of 7 4,232,552 90°F IOOF of 120°F (30°F 140°F STORAGE TEMPERATURECD EXCEEDED F RED - DO NOT USE TR O6 O F. G. 8 U.S. Patent Nov. 11, 1980 Sheet 4 of 7 4,232,552 U.S. Patent Nov. 11, 1980 Sheet 5 of 7 4,232,552 U.S. Patent Nov. 11, 1980 Sheet 6 of 7 4,232,552 N O S. 4,232,552 1. 2 in plants and refineries, the user must ordinarily reach TEMPERATURE INDICATING COMPOSITIONS into inexcessible places to locate the thermometer, and OF MATTER." because of the extreme difference between said rela tively high temperatures and the outside ambient tem RELATED APPLICATIONS 5 perature, readings from conventional thermometers are This application is a continuation-in-part of U.S. Ser. often in extreme error seconds after the withdrawal of No. 895,422, filed Apr. 13, 1978, abandoned in favor of the mercury thermometer. this appication, which is a continuation-in-part of U.S. Accordingly, for many years persons have attempted Ser. No. 844,334, filed Oct. 21, 1977, abandoned in favor to construct an inexpensive device of mixtures or mate of Ser. No. 895,422, which is a continuation-in-part of 10 rials of any kind which would change in some charac U.S. Ser. No. 796,492, filed May 12, 1977, abandoned in teristic visible to the naked eye at substantially the tem favor of Ser. No. 844,334, all entitled “TEMPERA perature to be measured so that the inconveniences of TURE INDICATING COMPOSITIONS OF MAT the conventional mercury thermometer could be TER,” for which benefit is claimed under 35 USC avoided. For instance, Ramsden in British Pat. No. 3640 $120. This application is also related by subject matter 15 (1897) provided a piece of paper, celluloid, metal or to (1) U.S. Ser. No. 869,406 (Ulin), filed Jan. 16, 1978, other suitable material which would be (1) coated with, now U.S. Pat. No. 4,128,007, entitled "SUPPORT MEMBER FOR A DISPOSABLE THERMOME or (2) formed with a hollow or recess containing a sub TER', disloosing a rectal adapter similar to that de stance, mixture of material which would change in scribed in the DESCRIPTION OF THE PRE 20 opacity at the temperature for the indication of which FERRED EMBODIMENTS below and FIGS. 14-16 the appliance is intended to be used (see page 1, lines herein, and (2) an application entitled "TEMPERA 24-38; page 5, lines 23-45 of British Pat. No. 3640). TURE INDICATING DEVICE USING A PRES Ramsden desired a substance or material (see page 2, SURE SENSITIVE ADHESIVE SEAL’, Ser. No. lines 9-23) that would change in color at the predeter 896,114 by E. A. Giezen, G. D. B. van Houwelingen 25 mined temperature, but did not indicate any in his speci and M. Cramer, filed on Apr. 13, 1978, now U.S. Pat. fication; he only indicated several substances, generally No. 4,189,942, and based upon Netherlands Application fatty acids, which would change in opacity or change No. 7,704,765 filed May 2, 1977in the Netherlands, bot from being opaque to transparent upon change in phases (1) and (2) incorporated herein. from solid to liquid or vice versa (see page 3, lines 30 11-18), so that indicator layers, dyes, etc., would have BACKGROUND OF THE INVENTION to be employed in the device. 1. Field of the Invention After Ramsden, the art primarily pursued only those The invention relates to the field of temperature heat-sensitive substances which would change from indicating compositions and devices therefor, and in being opaque to transparent at the phase interface in particular, the sub-fields of disposable thermometers 35 devices (hereinafter described as "opaque thermome and compositions of matter which change characteris ters') that would employ indicator layers having dyes tics with change in phases for use in disposable ther that would only be apparent when the heat-sensitive moneters. - substance had changed from opaque to transparent and 2. Description of the Prior Art would mix with the heat-sensitive compounds upon a For many years the conventional mercury thermom change in phases. For example, U.S. Pat. No. 3,175,401 eter has been the primary temperature-indicating device issued to Geldmacher (1965) describes a thermometer which has been used in clinical applications for the with several cavities, each containing a different ther measurement of temperature in the human body and mally-indicating composition melting at a different tem other animal bodies, and for the measurement of tem perature range. Each of the thermally-indicating com perature of gases, liquids, and even solids in commercial 45 positions employed by Geldmacher is normally opaque and industrial applications.
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