Thermally reversible color forming composition and thermally reversible recording medium using the thermally reversible color forming composition

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a thermally reversible color forming composition and a thermally reversible recording medium using the thermally reversible color forming composition. More particularly, the present invention relates to thermally reversible color forming compositions which involves a color forming reaction between an electron-donating chromophoric compound and an electron-accepting compound, and thermally reversible recording media using the thermally reversible color forming composition, by which a formation and a deletion of an image may be carried out by adjusting thermal energy applied to the composition.
2. Description of the Related Art
Thermal recording media which use a color producing reaction between an electron-donating chromophoric compound (hereinafter also referred to as a "color-producing agent" or "leuco dye") and an electron-accepting compound (hereinafter also referred to as a "color developer") in a recording layer is well known in the art. These recording media are generally used for a printer of a facsimile, a word processor, a scientific instrument and so on.
However, all of the conventional recording media which are practically used are non-reversible type recording media. That is, once a color is produced on the recording medium, it is non-reversibly fixed on the medium. Therefore, it is not possible to delete an image picture on the medium and to use the medium repeatedly.
On the other hand, a thermally reversible recording medium which can perform a reversible formation and a deletion of a colored image is disclosed in Japanese Laid-Open Patent Application No.60-193691 in which a combination of gallic acid and fluoroglucinol is used as the color developer, Japanese Laid-Open Patent Application No.61-237684 in which compounds such as phenol phthalene and thymol phthalene are used as the color developer, Japanese Laid-Open Patent Application Nos.62-138556, 62-138568 and 62-140881 in which a homogeneous mixture of a color-producing agent, a color developer and a carboxylate is contained in a recording layer, Japanese Laid-Open Patent Application No.63-173884 in which a derivative of ascorbic acid is used as a color developer, and Japanese Laid-Open Patent Application Nos.2-188293 and 2-18294 in which a salt of bis(hydroxyphenyl) acetic acid or gallic acid with higher aliphatic amine is used as a color developer.
However, these conventional thermally reversible recording media have problems such as compatibility in color-producing stability and color deletion ability, sufficient concentration of produced colors, and stability when used repeatedly. Therefore, these thermally reversible media are generally not suitable for practical use.
It is disclosed, in Japanese Laid-Open Patent Application No.5-124360, a thermally reversible color forming composition comprising an organic phosphate compound having a long-chain aliphatic hydrocarbon group, an aliphatic carboxylic acid or a phenol compound as a color developer and a leuco dye as a color producing agent. By using the above composition, it is possible to carry out a formation and deletion of colors relatively easily, and a stability of such formation and deletion of colors may be maintained during repeated use. In the above Patent Application No.5-124360, a thermally reversible recording medium using the thermally reversible color forming composition in a recording layer is also disclosed. The recording medium has an advantage, compared with other conventional recording media, in that an excellent stability of color formation, color deletion, and a concentration of produced colors may be achieved. However, its color deletion rate is rather slow for practical use. Thus, development of thermally reversible recording medium in which a colored image once formed can be deleted at a practically sufficient speed and yet provide stability so that colors can be maintained is desired.
SUMMARY OF THE INVENTION
Accordingly, it is a general object of the present invention to provide a thermally reversible color forming composition and a thermally reversible recording medium using the thermally reversible color forming composition.
A more specific object of the present invention is to provide a thermally reversible color forming composition and a thermally reversible recording medium using the thermally reversible color forming composition, by which a stability in color formation and color deletion may be maintained, and a sufficient deletion speed of a colored image may be attained.
It is another object of the present invention to provide a thermally reversible color forming composition involving a color forming reaction between an electron-donating chromophoric compound and an electron-accepting compound, and a thermally reversible recording medium using the thermally reversible color forming composition, by which a formation and a deletion of an image may be carried out by adjusting thermal energy applied to the composition.
The objects described above are achieved by a thermally reversible color forming composition comprising an electron-donating chromophoric compound and an electron-accepting compound, by which a color may be formed and deleted depending on at least one of a temperature for the thermally reversible color forming composition and a cooling rate for the thermally reversible color forming composition after heating the thermally reversible color forming composition, wherein a carboxylic acid compound having the following general formula:
R.sub.1 --X--R.sub.2 --COOH
(wherein, X represents a divalent group having at least one hetero atom,
R.sub.1 represents a hydrocarbon group which may be substituted and
R.sub.2 represents an aliphatic hydrocarbon group, which may be substituted and whose principle chain containing less than 6 carbon atoms) is used as the electron-accepting compound.
The objects described above are also achieved by the thermally reversible color forming composition, wherein R.sub.1 is substituted by a substituent selected from a group consisting of a hydroxy group, halogens and alkoxy groups.
The objects described above are also achieved by the thermally reversible color forming composition, wherein R.sub.2 is substituted by a substituent selected from a group consisting of a hydroxy group and halogens.
The objects described above are also achieved by the thermally reversible color forming composition, wherein R.sub.1 is substituted by a substituent selected from a group consisting of a hydroxy group, halogens and alkoxy groups and R.sub.2 is substituted by a substituent selected from a group consisting of a hydroxy group and halogens.
The objects described above are also achieved by the thermally reversible color forming composition, wherein the carboxylic acid compound has the following general formula:
CH.sub.3 (CH.sub.2).sub.m-1 --X--(CH.sub.2).sub.n --COOH
wherein m represents an integer between 8 and 22 and n represents an integer between 0 and 6.
The objects described above are also achieved by the thermally reversible color forming composition, wherein the --X-- in the formula of the carboxylic acid compound may be expressed as:
--Y--(R.sub.3 --Y').sub.r --
wherein Y and Y' represents, respectively, a divalent group having at least one hetero atom,
R.sub.3 represents a divalent hydrocarbon group whose principle chain may contain a non-limiting number of carbon atoms, a portion of which may form aromatic ring(s), and
.sub.r represents an integer between 1 and 4, and when .sub.r is more than 2, R.sub.3 and Y', respectively, may be the same or different.
The objects described above are also achieved by the thermally reversible color forming composition, wherein the carboxylic acid compound has a general formula selected from the group consisting of following:
R.sub.1 --Y--R.sub.3 --Y'--R.sub.2 --COOH
R.sub.1 --Y--R.sub.3 --Y'--R.sub.3 '--Y"--R.sub.2 --COOH
R.sub.1 --Y--R.sub.3 --Y'--R.sub.3 '--Y"--R.sub.3 "--Y"'--R.sub.2 --COOH,
and
R.sub.1 --Y--R.sub.3 --Y'--R.sub.3 '--Y"--R.sub.3 "--Y"'--R.sub.3 "'--Y""--R.sub.2 --COOH
wherein R.sub.3 ', R.sub.3 " and R.sub.3 "', respectively, has the same definition as R.sub.3 and they may be one of the same and different from each other, and
Y", Y"' and Y"" has the same definition as Y, and they may be one of the same and different from each other.
According to the above thermally reversible color forming compositions, a stability in color formation and color deletion may be maintained even after repeated use, and a practically sufficient deletion speed of an colored image may be obtained.
The objects described above are also achieved by a thermally reversible recording medium comprising a supporting layer and a recording layer formed on the supporting layer, wherein the recording layer is comprised, as a main component, of a thermally reversible color forming composition comprising an electron-donating chromophoric compound and an electron-accepting compound, by which a color may be formed and deleted depending on at least one of a temperature for the thermally reversible color forming composition and a cooling rate for the thermally reversible color forming composition after heating the thermally reversible color forming composition, wherein a carboxylic acid compound having the following general formula:
R.sub.1 --X--R.sub.2 --COOH
(wherein X represents a divalent group having at least one hetero atom,
R.sub.1 represents a hydrocarbon group which may be substituted and
R.sub.2 represents an aliphatic hydrocarbon group, which may be substituted and whose principle chain containing less than 6 carbon atoms) is used as the electron-accepting compound.
The objects described above are also achieved by the thermally reversible recording medium, wherein the carboxylic acid compound has the following general formula:
CH.sub.3 (CH.sub.2).sub.m-1 --X--(CH.sub.2).sub.n --COOH
wherein m represents an integer between 8 and 22 and n represents an integer between 0 and 6.
The objects described above are also achieved by the thermally reversible recording medium, wherein the --X-- in the formula of the carboxylic acid compound may be expressed as:
--Y--(R.sub.3 --Y').sub.r --
wherein Y and Y' represents, respectively, a divalent group having at least one hetero atom,
R.sub.3 represents a divalent hydrocarbon group whose principle chain may contain a non-limiting number of carbon atoms, a portion of which may form aromatic ring(s), and
.sub.r represents an integer between 1 and 4, and when .sub.r is more than 2, R.sub.3 and Y', respectively, may be the same or different.
The objects described above are also achieved by the thermally reversible recording medium as claimed in claim 10, wherein the carboxylic acid compound has a general formula selected from the group consisting of following:
R.sub.1 --Y--R.sub.3 --Y'--R.sub.2 --COOH
R.sub.1 --Y--R.sub.3 --Y'--R.sub.3 '--Y"--R.sub.2 --COOH
R.sub.1 --Y--R.sub.3 --Y'--R.sub.3 '--Y"--R.sub.3 "--Y"'--R.sub.2 --COOH,
and
R.sub.1 --Y--R.sub.3 --Y'--R.sub.3 '--Y"--R.sub.3 "--Y"'--R.sub.3 "'--Y""--R.sub.2 --COOH
wherein R.sub.3 ', R.sub.3 " and R.sub.3 "', respectively, have the same definition as R.sub.3 and they may be one of the same and different from each other, and
Y", Y"' and Y"" has the same definition as Y, and they may be one of the same and different from each other.
According to the above thermally reversible recording medium, a stability in color formation and color deletion may be maintained even after repeated use, and a practically sufficient deletion speed of an colored image may be obtained. Also, the thermally reversible recording medium has a high contrast and a high durability which is sufficient to be a practical excellent thermally reversible recording medium.
Other objects and further features of the present invention will be apparent from the following detailed description when read in conjunction with the accompanied drawing.

BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph showing a color formation/deletion characteristics of a thermally reversible color forming composition according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A thermally reversible color forming composition and a recording medium using the composition according to the present invention will be described in detail hereinafter.
The inventors of the present invention have made a discovery that a balance between the color developing ability of a color developer having a long chain aliphatic group for a color producing agent and a cohesive force among molecules is very important for a reversible color-forming and color-deleting phenomenon caused by a composition comprising a color producing agent and a color developer. Based on this finding, various kinds of compounds were examined and, as a result, it was found that the above-mentioned problems associated with the conventional thermally reversible color forming compositions and thermally reversible recording media using the compositions may be solved by using a carboxylic acid compound having a certain structure as the electron-donating compound.
According to the present invention, a carboxylic acid compound having the following general formula (1):
R.sub.1 --X--R.sub.2 --COOH (1)
(wherein X represents a divalent group having at least one hetero atom,
R.sub.1 represents a hydrocarbon group which may be unsubstituted or substituted and
R.sub.2 represents an aliphatic hydrocarbon group, which may be unsubstituted or substituted and whose principle chain containing less than 6 carbon atoms), is used as an electron-accepting compound for a thermally reversible color forming composition. According to the present invention, a colored image is produced by a reversible coloration reaction between the electron-accepting compound and an electron-donating chromophoric compound.
Now, the above-mentioned carboxylic acid compound having the formula (1) will be described in detail.
As described above, R.sub.1 represents a hydrocarbon group which may be unsubstituted or substituted by a substituent. R.sub.1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group or may be a hydrocarbon group comprising both the aromatic moiety and the aliphatic moiety. Also, the aliphatic hydrocarbon group may be of a straight chain or may be branched, and can contain unsaturated bonds. Examples of a typical substituent for the hydrocarbon group include a hydroxy group, halogens, alkoxy groups and so on.
Further, since the stability in a color formation and a color deletion ability of the composition according to the present invention will be decreased if R.sub.1 contains less than 7 carbon atoms, it is preferable that R.sub.1 contains more than 8 carbon atoms and it is more preferable that R.sub.1 contains more than 11 carbon atoms.
Preferable examples of R.sub.1 include: ##STR1## wherein p, p', p" and p"', respectively, preferably represents an integer which satisfies the above mentioned number of carbons for R.sub.1.
R.sub.2 represents an aliphatic hydrocarbon group, which may be unsubstituted or substituted and whose principle chain contains less than 6 carbon atoms. The aliphatic hydrocarbon group may be of a straight chain or may be branched, and can contain unsaturated bonds. Examples of a typical substituent for the hydrocarbon group include a hydroxy group, halogens and so on.
Also, since the color producing ability of the composition according to the present invention will be decreased if R.sub.2 contains more than 7 carbon atoms, it is preferable that R.sub.2 contains less than 6 carbon atoms.
Preferable examples of R.sub.2 include: ##STR2## wherein q and p', respectively, preferably represents an integer which satisfies the above mentioned number of carbons for R.sub.2, and q" and q"', represents an integer which is not particularly limited but preferable less than 5.
X represents a divalent group having at least one hetero atom. Non-limiting examples of X, according to the present invention, include: ##STR3##
Examples of preferable carboxylic acid compound having the above formula (1) according to the present invention include a compound having the following formula (2):
CH.sub.3 (CH.sub.2).sub.m-1 --X--(CH.sub.2).sub.n --COOH (2)
wherein m represents an integer between 8 and 22 and n represents an integer between 0 and 6.
Examples of carboxylic acid compound having the above formula (1) according to the present invention are shown in the following Tables 1-1 through 1-14. However, they are not by any means to restrict the present invention.
TABLE 1______________________________________Compound No. CH.sub.3 (CH.sub.2).sub.m-1 -- --X-- --(CH.sub.2).sub.n --______________________________________1 CH.sub.3 (CH.sub.2).sub.7 -- --NHCO-- --CH.sub.2 --2 CH.sub.3 (CH.sub.2).sub.11 -- --NHCO-- --CH.sub.2 --3 CH.sub.3 (CH.sub.2).sub.13 -- --NHCO-- --CH.sub.2 --4 CH.sub.3 (CH.sub.2).sub.15 -- --NHCO-- --CH.sub.2 --5 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --CH.sub.2 --6 CH.sub.3 (CH.sub.2).sub.19 -- --NHCO-- --CH.sub.2 --7 CH.sub.3 (CH.sub.2).sub.21 -- --NHCO-- --CH.sub.2 --8 CH.sub.3 (CH.sub.2).sub.7 -- --NHCO-- --(CH.sub.2).sub.2 --9 CH.sub.3 (CH.sub.2).sub.11 -- --NHCO-- --(CH.sub.2).sub.2 --10 CH.sub.3 (CH.sub.2).sub.13 -- --NHCO-- --(CH.sub.2).sub.2 --11 CH.sub.3 (CH.sub.2).sub.15 -- --NHCO-- --(CH.sub.2).sub.2 --12 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.2 --13 CH.sub.3 (CH.sub.2).sub.19 -- --NHCO-- --(CH.sub.2).sub.2 --14 CH.sub.3 (CH.sub.2).sub.21 -- --NHCO-- --(CH.sub.2).sub.2 --15 CH.sub.3 (CH.sub.2).sub.7 -- --NHCO-- --(CH.sub.2).sub.3 --16 CH.sub.3 (CH.sub.2).sub.11 -- --NHCO-- --(CH.sub.2).sub.3 --17 CH.sub.3 (CH.sub.2).sub.13 -- --NHCO-- --(CH.sub.2).sub.3 --18 CH.sub.3 (CH.sub.2).sub.15 -- --NHCO-- --(CH.sub.2).sub.3 --19 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.3 --20 CH.sub.3 (CH.sub.2).sub.19 -- --NHCO-- --(CH.sub.2).sub.3 --21 CH.sub.3 (CH.sub.2).sub.21 -- --NHCO-- --(CH.sub.2).sub.3 --22 CH.sub.3 (CH.sub.2).sub.7 -- --NHCO-- --(CH.sub.2).sub.4 --23 CH.sub.3 (CH.sub.2).sub.11 -- --NHCO-- --(CH.sub.2).sub.4 --24 CH.sub.3 (CH.sub.2).sub.13 -- --NHCO-- --(CH.sub.2).sub.4 --25 CH.sub.3 (CH.sub.2).sub.15 -- --NHCO-- --(CH.sub.2).sub.4 --26 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.4 --27 CH.sub.3 (CH.sub.2).sub.19 -- --NHCO-- --(CH.sub.2).sub.4 --28 CH.sub.3 (CH.sub.2).sub.21 -- --NHCO-- --(CH.sub.2).sub.4 --29 CH.sub.3 (CH.sub.2).sub.11 -- --NHCO-- --(CH.sub.2).sub.5 --30 CH.sub.3 (CH.sub.2).sub.13 -- --NHCO-- --(CH.sub.2).sub.5 --31 CH.sub.3 (CH.sub.2).sub.15 -- --NHCO-- --(CH.sub.2).sub.5 --32 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.5 --33 CH.sub.3 (CH.sub.2).sub.11 -- --NHCO-- --(CH.sub.2).sub.6 --34 CH.sub.3 (CH.sub.2).sub.13 -- --NHCO-- --(CH.sub.2).sub.6 --35 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.6 --36 CH.sub.3 (CH.sub.2).sub.7 -- --NHCONH-- --CH.sub.2 --37 CH.sub.3 (CH.sub.2).sub.11 -- --NHCONH-- --CH.sub.2 --38 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONH-- --CH.sub.2 --39 CH.sub.3 (CH.sub.2).sub.15 -- --NHCONH-- --CH.sub.2 --40 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --CH.sub.2 --41 CH.sub.3 (CH.sub.2).sub.19 -- --NHCONH-- --CH.sub.2 --42 CH.sub.3 (CH.sub.2).sub.21 -- --NHCONH-- --CH.sub.2 --43 CH.sub.3 (CH.sub.2).sub.7 -- --NHCONH-- --(CH.sub.2).sub.2 --44 CH.sub.3 (CH.sub.2).sub.11 -- --NHCONH-- --(CH.sub.2).sub.2 --45 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONH-- --(CH.sub.2).sub.2 --46 CH.sub.3 (CH.sub.2).sub.15 -- --NHCONH-- --(CH.sub.2).sub.2 --47 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.2 --48 CH.sub.3 (CH.sub.2).sub.19 -- --NHCONH-- --(CH.sub.2).sub.2 --49 CH.sub.3 (CH.sub.2).sub.21 -- --NHCONH-- --(CH.sub.2).sub.2 --50 CH.sub.3 (CH.sub.2).sub.7 -- --NHCONH-- --(CH.sub.2).sub.3 --51 CH.sub.3 (CH.sub.2).sub.11 -- --NHCONH-- --(CH.sub.2).sub.3 --52 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONH-- --(CH.sub.2).sub.3 --53 CH.sub.3 (CH.sub.2).sub.15 -- --NHCONH-- --(CH.sub.2).sub.3 --54 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.3 --55 CH.sub.3 (CH.sub.2).sub.19 -- --NHCONH-- --(CH.sub.2).sub.3 --56 CH.sub.3 (CH.sub.2).sub.21 -- --NHCONH-- --(CH.sub.2).sub.3 --57 CH.sub.3 (CH.sub.2).sub.7 -- --NHCONH-- --(CH.sub.2).sub.4 --58 CH.sub.3 (CH.sub.2).sub.11 -- --NHCONH-- --(CH.sub.2).sub.4 --59 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONH-- --(CH.sub.2).sub.4 --60 CH.sub.3 (CH.sub.2).sub.15 -- --NHCONH-- --(CH.sub.2).sub.4 --61 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.4 --62 CH.sub.3 (CH.sub.2).sub.19 -- --NHCONH-- --(CH.sub.2).sub.4 --63 CH.sub.3 (CH.sub.2).sub.21 -- --NHCONH-- --(CH.sub.2).sub.4 --64 CH.sub.3 (CH.sub.2).sub.11 -- --NHCONH-- --(CH.sub.2).sub.5 --65 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONH-- --(CH.sub.2).sub.5 --66 CH.sub.3 (CH.sub.2).sub.15 -- --NHCONH-- --(CH.sub.2).sub.5 --67 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.5 --68 CH.sub.3 (CH.sub.2).sub.11 -- --NHCONH-- --(CH.sub.2).sub.6 --69 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONH-- --(CH.sub.2).sub.6 --70 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.6 --71 CH.sub.3 (CH.sub.2).sub.7 -- --NHSO.sub.2 -- --CH.sub.2 --72 CH.sub.3 (CH.sub.2).sub.11 -- --NHSO.sub.2 -- --CH.sub.2 --73 CH.sub.3 (CH.sub.2).sub.13 -- --NHSO.sub.2 -- --CH.sub.2 --74 CH.sub.3 (CH.sub.2).sub.15 -- --NHSO.sub.2 -- --CH.sub.2 --75 CH.sub.3 (CH.sub.2).sub.17 -- --NHSO.sub.2 -- --CH.sub.2 --76 CH.sub.3 (CH.sub.2).sub.19 -- --NHSO.sub.2 -- --CH.sub.2 --77 CH.sub.3 (CH.sub.2).sub.21 -- --NHSO.sub.2 -- --CH.sub.2 --78 CH.sub.3 (CH.sub.2).sub.7 -- --NHSO.sub.2 -- --(CH.sub.2).sub.2 --79 CH.sub.3 (CH.sub.2).sub.11 -- --NHSO.sub.2 -- --(CH.sub.2).sub.2 --80 CH.sub.3 (CH.sub.2).sub.13 -- --NHSO.sub.2 -- --(CH.sub.2).sub.2 --81 CH.sub.3 (CH.sub.2).sub.15 -- --NHSO.sub.2 -- --(CH.sub.2).sub.2 --82 CH.sub.3 (CH.sub.2).sub.17 -- --NHSO.sub.2 -- --(CH.sub.2).sub.2 --83 CH.sub.3 (CH.sub.2).sub.19 -- --NHSO.sub.2 -- --(CH.sub.2).sub.2 --84 CH.sub.3 (CH.sub.2).sub.21 -- --NHSO.sub.2 -- --(CH.sub.2).sub.2 --85 CH.sub.3 (CH.sub.2).sub.7 -- --NHSO.sub.2 -- --(CH.sub.2).sub.3 --86 CH.sub.3 (CH.sub.2).sub.11 -- --NHSO.sub.2 -- --(CH.sub.2).sub.3 --87 CH.sub.3 (CH.sub.2).sub.13 -- --NHSO.sub.2 -- --(CH.sub.2).sub.3 --88 CH.sub.3 (CH.sub.2).sub.15 -- --NHSO.sub.2 -- --(CH.sub.2).sub.3 --89 CH.sub.3 (CH.sub.2).sub.17 -- --NHSO.sub.2 -- --(CH.sub.2).sub.3 --90 CH.sub.3 (CH.sub.2).sub.19 -- --NHSO.sub.2 -- --(CH.sub.2).sub.3 --91 CH.sub.3 (CH.sub.2).sub.21 -- --NHSO.sub.2 -- --(CH.sub.2).sub.3 --92 CH.sub.3 (CH.sub.2).sub.7 -- --NHSO.sub.2 -- --(CH.sub.2).sub.4 --93 CH.sub.3 (CH.sub.2).sub.11 -- --NHSO.sub.2 -- --(CH.sub.2).sub.4 --94 CH.sub.3 (CH.sub.2).sub.13 -- --NHSO.sub.2 -- --(CH.sub.2).sub.4 --95 CH.sub.3 (CH.sub.2).sub.15 -- --NHSO.sub.2 -- --(CH.sub.2).sub.4 --96 CH.sub.3 (CH.sub.2).sub.17 -- --NHSO.sub.2 -- --(CH.sub.2).sub.4 --97 CH.sub.3 (CH.sub.2).sub.19 -- --NHSO.sub.2 -- --(CH.sub.2).sub.4 --98 CH.sub.3 (CH.sub.2).sub.21 -- --NHSO.sub.2 -- --(CH.sub.2).sub.4 --99 CH.sub.3 (CH.sub.2).sub.11 -- --NHSO.sub.2 -- --(CH.sub.2).sub.5 --100 CH.sub.3 (CH.sub.2).sub.13 -- --NHSO.sub.2 -- --(CH.sub.2).sub.5 --101 CH.sub.3 (CH.sub.2).sub.15 -- --NHSO.sub.2 -- --(CH.sub.2).sub.5 --102 CH.sub.3 (CH.sub.2).sub.17 -- --NHSO.sub.2 -- --(CH.sub.2).sub.5 --103 CH.sub.3 (CH.sub.2).sub.11 -- --NHSO.sub.2 -- --(CH.sub.2).sub.6 --104 CH.sub.3 (CH.sub.2).sub.13 -- --NHSO.sub.2 -- --(CH.sub.2).sub.6 --105 CH.sub.3 (CH.sub.2).sub.17 -- --NHSO.sub.2 -- --(CH.sub.2).sub.6 --106 CH.sub.3 (CH.sub.2).sub.7 -- --NHCSNH-- --CH.sub.2 --107 CH.sub.3 (CH.sub.2).sub.11 -- --NHCSNH-- --CH.sub.2 --108 CH.sub.3 (CH.sub.2).sub.13 -- --NHCSNH-- --CH.sub.2 --109 CH.sub.3 (CH.sub.2).sub.15 -- --NHCSNH-- --CH.sub.2 --110 CH.sub.3 (CH.sub.2).sub.17 -- --NHCSNH-- --CH.sub.2 --111 CH.sub.3 (CH.sub.2).sub.19 -- --NHCSNH-- --CH.sub.2 --112 CH.sub.3 (CH.sub.2).sub.21 -- --NHCSNH-- --CH.sub.2 --113 CH.sub.3 (CH.sub.2).sub.7 -- --NHCSNH-- --(CH.sub.2).sub.2 --114 CH.sub.3 (CH.sub.2).sub.11 -- --NHCSNH-- --(CH.sub.2).sub.2 --115 CH.sub.3 (CH.sub.2).sub.13 -- --NHCSNH-- --(CH.sub.2).sub.2 --116 CH.sub.3 (CH.sub.2).sub.15 -- --NHCSNH-- --(CH.sub.2).sub.2 --117 CH.sub.3 (CH.sub.2).sub.17 -- --NHCSNH-- --(CH.sub.2).sub.2 --118 CH.sub.3 (CH.sub.2).sub.19 -- --NHCSNH-- --(CH.sub.2).sub.2 --119 CH.sub.3 (CH.sub.2).sub.21 -- --NHCSNH-- --(CH.sub.2).sub.2 --120 CH.sub.3 (CH.sub.2).sub.7 -- --NHCSNH-- --(CH.sub.2).sub.3 --121 CH.sub.3 (CH.sub.2).sub.11 -- --NHCSNH-- --(CH.sub.2).sub.3 --122 CH.sub.3 (CH.sub.2).sub.13 -- --NHCSNH-- --(CH.sub.2).sub.3 --123 CH.sub.3 (CH.sub.2).sub.15 -- --NHCSNH-- --(CH.sub.2).sub.3 --124 CH.sub.3 (CH.sub.2).sub.17 -- --NHCSNH-- --(CH.sub.2).sub.3 --125 CH.sub.3 (CH.sub.2).sub.19 -- --NHCSNH-- --(CH.sub.2).sub.3 --126 CH.sub.3 (CH.sub.2).sub.21 -- --NHCSNH-- --(CH.sub.2).sub.3 --127 CH.sub.3 (CH.sub.2).sub.7 -- --NHCSNH-- --(CH.sub.2).sub.4 --128 CH.sub.3 (CH.sub.2).sub.11 -- --NHCSNH-- --(CH.sub.2).sub.4 --129 CH.sub.3 (CH.sub.2).sub.13 -- --NHCSNH-- --(CH.sub.2).sub.4 --130 CH.sub.3 (CH.sub.2).sub.15 -- --NHCSNH-- --(CH.sub.2).sub.4 --131 CH.sub.3 (CH.sub.2).sub.17 -- --NHCSNH-- --(CH.sub.2).sub.4 --132 CH.sub.3 (CH.sub.2).sub.19 -- --NHCSNH-- --(CH.sub.2).sub.4 --133 CH.sub.3 (CH.sub.2).sub.21 -- --NHCSNH-- --(CH.sub.2).sub.4 --134 CH.sub.3 (CH.sub.2).sub.11 -- --NHCSNH-- --(CH.sub.2).sub.5 --135 CH.sub.3 (CH.sub.2).sub.13 -- --NHCSNH-- --(CH.sub.2).sub.5 --136 CH.sub.3 (CH.sub.2).sub.15 -- --NHCSNH-- --(CH.sub.2).sub.5 --137 CH.sub.3 (CH.sub.2).sub.17 -- --NHCSNH-- --(CH.sub.2).sub.5 --138 CH.sub.3 (CH.sub.2).sub.11 -- --NHCSNH-- --(CH.sub.2).sub.6 --139 CH.sub.3 (CH.sub.2).sub.13 -- --NHCSNH-- --(CH.sub.2).sub.6 --140 CH.sub.3 (CH.sub.2).sub.17 -- --NHCSNH-- --(CH.sub.2).sub.6 --141 CH.sub.3 (CH.sub.2).sub.12 -- --CONH-- --CH.sub.2 --142 CH.sub.3 (CH.sub.2).sub.14 -- --CONH-- --CH.sub.2 --143 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --CH.sub.2 --144 CH.sub.3 (CH.sub.2).sub.20 -- --CONH-- --CH.sub.2 --145 CH.sub.3 (CH.sub.2).sub.12 -- --CONH-- --(CH.sub.2).sub.2 --146 CH.sub.3 (CH.sub.2).sub.14 -- --CONH-- --(CH.sub.2).sub.2 --147 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.2 --148 CH.sub.3 (CH.sub.2).sub.20 -- --CONH-- --(CH.sub.2).sub.2 --149 CH.sub.3 (CH.sub.2).sub.12 -- --CONH-- --(CH.sub.2).sub.3 --150 CH.sub.3 (CH.sub.2).sub.14 -- --CONH-- --(CH.sub.2).sub.3 --151 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.3 --152 CH.sub.3 (CH.sub.2).sub.20 -- --CONH-- --(CH.sub.2).sub.3 --153 CH.sub.3 (CH.sub.2).sub.12 -- --CONH-- --(CH.sub.2).sub.4 --154 CH.sub.3 (CH.sub.2).sub.14 -- --CONH-- --(CH.sub.2).sub.4 --155 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.4 --156 CH.sub.3 (CH.sub.2).sub.20 -- --CONH-- --(CH.sub.2).sub.4 --157 CH.sub.3 (CH.sub.2).sub.12 -- --CONH-- --(CH.sub.2).sub.5 --158 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.5 --159 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.6 --160 CH.sub.3 (CH.sub.2).sub.14 -- --COO-- --CH.sub.2 --161 CH.sub.3 (CH.sub.2).sub.16 -- --COO-- --CH.sub.2 --162 CH.sub.3 (CH.sub.2).sub.20 -- --COO-- --CH.sub.2 --163 CH.sub.3 (CH.sub.2).sub.12 -- --COO-- --(CH.sub.2).sub.2 --164 CH.sub.3 (CH.sub.2).sub.14 -- --COO-- --(CH.sub.2).sub.2 --165 CH.sub.3 (CH.sub.2).sub.16 -- --COO-- --(CH.sub.2).sub.2 --166 CH.sub.3 (CH.sub.2).sub.14 -- --COO-- --(CH.sub.2).sub.3 --167 CH.sub.3 (CH.sub.2).sub.16 -- --COO-- --(CH.sub.2).sub.3 --168 CH.sub.3 (CH.sub.2).sub.20 -- --COO-- --(CH.sub.2).sub.3 --169 CH.sub.3 (CH.sub.2).sub.12 -- --COO-- --(CH.sub.2).sub.4 --170 CH.sub.3 (CH.sub.2).sub.14 -- --COO-- --(CH.sub.2).sub.4 --171 CH.sub.3 (CH.sub.2).sub.16 -- --COO-- --(CH.sub.2).sub.4 --172 CH.sub.3 (CH.sub.2).sub.14 -- --COO-- --(CH.sub.2).sub.5 --173 CH.sub.3 (CH.sub.2).sub.16 -- --COO-- --(CH.sub.2).sub.5 --174 CH.sub.3 (CH.sub.2).sub.14 -- --COO-- --(CH.sub.2).sub.6 --175 CH.sub.3 (CH.sub.2).sub.16 -- --COO-- --(CH.sub.2).sub.6 --176 CH.sub.3 (CH.sub.2).sub.12 -- --CONHCO-- --CH.sub.2 --177 CH.sub.3 (CH.sub.2).sub.14 -- --CONHCO-- --CH.sub.2 --178 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCO-- --CH.sub.2 --179 CH.sub.3 (CH.sub.2).sub.20 -- --CONHCO-- --CH.sub.2 --180 CH.sub.3 (CH.sub.2).sub.12 -- --CONHCO-- --(CH.sub.2).sub.2 --181 CH.sub.3 (CH.sub.2).sub.14 -- --CONHCO-- --(CH.sub.2).sub.2 --182 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCO-- --(CH.sub.2).sub.2 --183 CH.sub.3 (CH.sub.2).sub.20 -- --CONHCO-- --(CH.sub.2).sub.2 --184 CH.sub.3 (CH.sub.2).sub.12 -- --CONHCO-- --(CH.sub.2).sub.3 --185 CH.sub.3 (CH.sub.2).sub.14 -- --CONHCO-- --(CH.sub.2).sub.3 --186 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCO-- --(CH.sub.2).sub.3 --187 CH.sub.3 (CH.sub.2).sub.20 -- --CONHCO-- --(CH.sub.2).sub.3 --188 CH.sub.3 (CH.sub.2).sub.12 -- --CONHCO-- --(CH.sub.2).sub.4 --189 CH.sub.3 (CH.sub.2).sub.14 -- --CONHCO-- --(CH.sub.2).sub.4 --190 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCO-- --(CH.sub.2).sub.4 --191 CH.sub.3 (CH.sub.2).sub.20 -- --CONHCO-- --(CH.sub.2).sub.4 --192 CH.sub.3 (CH.sub.2).sub.12 -- --CONHCO-- --(CH.sub.2).sub.5 --193 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCO-- --(CH.sub.2).sub.5 --194 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCO-- --(CH.sub.2).sub.6 --195 CH.sub.3 (CH.sub.2).sub.14 -- --COS-- --CH.sub.2 --196 CH.sub.3 (CH.sub.2).sub.16 -- --COS-- --CH.sub.2 --197 CH.sub.3 (CH.sub.2).sub.20 -- --COS-- --CH.sub.2 --198 CH.sub.3 (CH.sub.2).sub.12 -- --COS-- --(CH.sub.2).sub.2 --199 CH.sub.3 (CH.sub.2).sub.14 -- --COS-- --(CH.sub.2).sub.2 --200 CH.sub.3 (CH.sub.2).sub.16 -- --COS-- --(CH.sub.2).sub.2 --201 CH.sub.3 (CH.sub.2).sub.14 -- --COS-- --(CH.sub.2).sub.3 --202 CH.sub.3 (CH.sub.2).sub.16 -- --COS-- --(CH.sub.2).sub.3 --203 CH.sub.3 (CH.sub.2).sub.20 -- --COS-- --(CH.sub.2).sub.3 --204 CH.sub.3 (CH.sub.2).sub.12 -- --COS-- --(CH.sub.2).sub.4 --205 CH.sub.3 (CH.sub.2).sub.14 -- --COS-- --(CH.sub.2).sub.4 --206 CH.sub.3 (CH.sub.2).sub.16 -- --COS-- --(CH.sub.2).sub.4 --207 CH.sub.3 (CH.sub.2).sub.14 -- --COS-- --(CH.sub.2).sub.5 --208 CH.sub.3 (CH.sub.2).sub.16 -- --COS-- --(CH.sub.2).sub.5 --209 CH.sub.3 (CH.sub.2).sub.14 -- --COS-- --(CH.sub.2).sub.6 --210 CH.sub.3 (CH.sub.2).sub.16 -- --COS-- --(CH.sub.2).sub.6 --211 CH.sub.3 (CH.sub.2).sub.12 -- --CO-- --CH.sub.2 --212 CH.sub.3 (CH.sub.2).sub.14 -- --CO-- --CH.sub.2 --213 CH.sub.3 (CH.sub.2).sub.16 -- --CO-- --CH.sub.2 --214 CH.sub.3 (CH.sub.2).sub.20 -- --CO-- --CH.sub.2 --215 CH.sub.3 (CH.sub.2).sub.12 -- --CO-- --(CH.sub.2).sub.2 --216 CH.sub.3 (CH.sub.2).sub.14 -- --CO-- --(CH.sub.2).sub.2 --217 CH.sub.3 (CH.sub.2).sub.16 -- --CO-- --(CH.sub.2).sub.2 --218 CH.sub.3 (CH.sub.2).sub.20 -- --CO-- --(CH.sub.2).sub.2 --219 CH.sub.3 (CH.sub.2).sub.12 -- --CO-- --(CH.sub.2).sub.3 --220 CH.sub.3 (CH.sub.2).sub.14 -- --CO-- --(CH.sub.2).sub.3 --221 CH.sub.3 (CH.sub.2).sub.16 -- --CO-- --(CH.sub.2).sub.3 --222 CH.sub.3 (CH.sub.2).sub.16 -- --CO-- --(CH.sub.2).sub.4 --223 CH.sub.3 (CH.sub.2).sub.16 -- --CO-- --(CH.sub.2).sub.5 --224 CH.sub.3 (CH.sub.2).sub.16 -- --CO-- --(CH.sub.2).sub.6 --225 CH.sub.3 (CH.sub.2).sub.12 -- --SO.sub.2 -- --CH.sub.2 --226 CH.sub.3 (CH.sub.2).sub.14 -- --SO.sub.2 -- --CH.sub.2 --227 CH.sub.3 (CH.sub.2).sub.16 -- --SO.sub.2 -- --CH.sub.2 --228 CH.sub.3 (CH.sub.2).sub.20 -- --SO.sub.2 -- --CH.sub.2 --229 CH.sub.3 (CH.sub.2).sub.12 -- --SO.sub.2 -- --(CH.sub.2).sub.2 --230 CH.sub.3 (CH.sub.2).sub.14 -- --SO.sub.2 -- --(CH.sub.2).sub.2 --231 CH.sub.3 (CH.sub.2).sub.16 -- --SO.sub.2 -- --(CH.sub.2).sub.2 --232 CH.sub.3 (CH.sub.2).sub.20 -- --SO.sub.2 -- --(CH.sub.2).sub.2 --233 CH.sub.3 (CH.sub.2).sub.12 -- --SO.sub.2 -- --(CH.sub.2).sub.3 --234 CH.sub.3 (CH.sub.2).sub.14 -- --SO.sub.2 -- --(CH.sub.2).sub.3 --235 CH.sub.3 (CH.sub.2).sub.16 -- --SO.sub.2 -- --(CH.sub.2).sub.3 --236 CH.sub.3 (CH.sub.2).sub.16 -- --SO.sub.2 -- --(CH.sub.2).sub.4 --237 CH.sub.3 (CH.sub.2).sub.16 -- --SO.sub.2 -- --(CH.sub.2).sub.5 --238 CH.sub.3 (CH.sub.2).sub.16 -- --SO.sub.2 -- --(CH.sub.2).sub.6 --239 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCONH-- --CH.sub.2 --240 CH.sub.3 (CH.sub.2).sub.20 -- --CONHCONH-- --CH.sub.2 --241 CH.sub.3 (CH.sub.2).sub.14 -- --CONHCONH-- --(CH.sub.2).sub.2 --242 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCONH-- --(CH.sub.2).sub.2 --243 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCONH-- --(CH.sub.2).sub.3 --244 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCONH-- --(CH.sub.2).sub.4 --245 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCONH-- --(CH.sub.2).sub.5 --246 CH.sub.3 (CH.sub.2).sub.11 -- --NHCOO-- --CH.sub.2 --247 CH.sub.3 (CH.sub.2).sub.13 -- --NHCOO-- --CH.sub.2 --248 CH.sub.3 (CH.sub.2).sub.15 -- --NHCOO-- --CH.sub.2 --249 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOO-- --CH.sub.2 --250 CH.sub.3 (CH.sub.2).sub.13 -- --NHCOO-- --(CH.sub.2).sub.2 --251 CH.sub.3 (CH.sub.2).sub.15 -- --NHCOO-- --(CH.sub.2).sub.2 --252 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOO-- --(CH.sub.2).sub.2 --253 CH.sub.3 (CH.sub.2).sub.21 -- --NHCOO-- --(CH.sub.2).sub.2 --254 CH.sub.3 (CH.sub.2).sub.11 -- --NHCOO-- --(CH.sub.2).sub.3 --255 CH.sub.3 (CH.sub.2).sub.15 -- --NHCOO-- --(CH.sub.2).sub.3 --256 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOO-- --(CH.sub.2).sub.3 --257 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOO-- --(CH.sub.2).sub.4 --258 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOO-- --(CH.sub.2).sub.5 --259 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOO-- --(CH.sub.2).sub.6 --260 CH.sub.3 (CH.sub.2).sub.13 -- --NHCOS-- --CH.sub.2 --261 CH.sub.3 (CH.sub.2).sub.15 -- --NHCOS-- --CH.sub.2 --262 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOS-- --CH.sub.2 --263 CH.sub.3 (CH.sub.2).sub.21 -- --NHCOS-- --CH.sub.2 --264 CH.sub.3 (CH.sub.2).sub.13 -- --NHCOS-- --(CH.sub.2).sub.2 --265 CH.sub.3 (CH.sub.2).sub.15 -- --NHCOS-- --(CH.sub.2).sub.2 --266 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOS-- --(CH.sub.2).sub.2 --267 CH.sub.3 (CH.sub.2).sub.21 -- --NHCOS-- --(CH.sub.2).sub.2 --268 CH.sub.3 (CH.sub.2).sub.11 -- --NHCOS-- --(CH.sub.2).sub.3 --269 CH.sub.3 (CH.sub.2).sub.15 -- --NHCOS-- --(CH.sub.2).sub.3 --270 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOS-- --(CH.sub.2).sub.3 --271 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOS-- --(CH.sub.2).sub.4 --272 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOS-- --(CH.sub.2).sub.5 --273 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOS-- --(CH.sub.2).sub.6 --274 CH.sub.3 (CH.sub.2).sub.15 -- --OCONH-- --CH.sub.2 --275 CH.sub.3 (CH.sub.2).sub.17 -- --OCONH-- --CH.sub.2 --276 CH.sub.3 (CH.sub.2).sub.15 -- --OCONH-- --(CH.sub.2).sub.2 --277 CH.sub.3 (CH.sub.2).sub.17 -- --OCONH-- --(CH.sub.2).sub.2 --278 CH.sub.3 (CH.sub.2).sub.17 -- --OCONH-- --(CH.sub.2).sub.3 --279 CH.sub.3 (CH.sub.2).sub.17 -- --OCONH-- --(CH.sub.2).sub.4 --280 CH.sub.3 (CH.sub.2).sub.17 -- --OCONH-- --(CH.sub.2).sub.5 --281 CH.sub.3 (CH.sub.2).sub.11 -- --NHCOCONH-- --CH.sub.2 --282 CH.sub.3 (CH.sub.2).sub.13 -- --NHCOCONH-- --CH.sub.2 --283 CH.sub.3 (CH.sub.2).sub.15 -- --NHCOCONH-- --CH.sub.2 --284 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOCONH-- --CH.sub.2 --285 CH.sub.3 (CH.sub.2).sub.13 -- --NHCOCONH-- --(CH.sub.2).sub.2 --286 CH.sub.3 (CH.sub.2).sub.15 -- --NHCOCONH-- --(CH.sub.2).sub.2 --287 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOCONH-- --(CH.sub.2).sub.2 --288 CH.sub.3 (CH.sub.2).sub.21 -- --NHCOCONH-- --(CH.sub.2).sub.2 --289 CH.sub.3 (CH.sub.2).sub.11 -- --NHCOCONH-- --(CH.sub.2).sub.3 --290 CH.sub.3 (CH.sub.2).sub.15 -- --NHCOCONH-- --(CH.sub.2).sub.3 --291 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOCONH-- --(CH.sub.2).sub.3 --292 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOCONH-- --(CH.sub.2).sub.4 --293 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOCONH-- --(CH.sub.2).sub.5 --294 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOCONH-- --(CH.sub.2).sub.6 --295 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONHNH-- --CH.sub.2 --296 CH.sub.3 (CH.sub.2).sub.15 -- --NHCONHNH-- --CH.sub.2 --297 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHNH-- --CH.sub.2 --298 CH.sub.3 (CH.sub.2).sub.21 -- --NHCONHNH-- --CH.sub.2 --299 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONHNH-- --(CH.sub.2).sub.2 --300 CH.sub.3 (CH.sub.2).sub.15 -- --NHCONHNH-- --(CH.sub.2).sub.2 --301 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHNH-- --(CH.sub.2).sub.2 --302 CH.sub.3 (CH.sub.2).sub.21 -- --NHCONHNH-- --(CH.sub.2).sub.2 --303 CH.sub.3 (CH.sub.2).sub.11 -- --NHCONHNH-- --(CH.sub.2).sub.3 --304 CH.sub.3 (CH.sub.2).sub.15 -- --NHCONHNH-- --(CH.sub.2).sub.3 --305 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHNH-- --(CH.sub.2).sub.3 --306 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHNH-- --(CH.sub.2).sub.4 --307 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHNH-- --(CH.sub.2).sub.5 --308 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHNH-- --(CH.sub.2).sub.6 --309 CH.sub.3 (CH.sub.2).sub.15 -- --NHCONHNHCO-- --CH.sub.2 --310 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHNHCO-- --CH.sub.2 --311 CH.sub.3 (CH.sub.2).sub.15 -- --NHCONHNHCO-- --(CH.sub.2).sub.2 --312 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHNHCO-- --(CH.sub.2).sub.2 --313 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHNHCO-- --(CH.sub.2).sub.3 --314 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHNHCO-- --(CH.sub.2).sub.4 --315 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHNHCO-- --(CH.sub.2).sub.5 --316 CH.sub.3 (CH.sub.2).sub.11 -- --OCO-- --CH.sub.2 --317 CH.sub.3 (CH.sub.2).sub.13 -- --OCO-- --CH.sub.2 --318 CH.sub.3 (CH.sub.2).sub.15 -- --OCO-- --CH.sub.2 --319 CH.sub.3 (CH.sub.2).sub.17 -- --OCO-- --CH.sub.2 --320 CH.sub.3 (CH.sub.2).sub.13 -- --OCO-- --(CH.sub.2).sub.2 --321 CH.sub.3 (CH.sub.2).sub.15 -- --OCO-- --(CH.sub.2).sub.2 --322 CH.sub.3 (CH.sub.2).sub.17 -- --OCO-- --(CH.sub.2).sub.2 --323 CH.sub.3 (CH.sub.2).sub.21 -- --OCO-- --(CH.sub.2).sub.2 --324 CH.sub.3 (CH.sub.2).sub.11 -- --OCO-- --(CH.sub.2).sub.3 --325 CH.sub.3 (CH.sub.2).sub.15 -- --OCO-- --(CH.sub.2).sub.3 --326 CH.sub.3 (CH.sub.2).sub.17 -- --OCO-- --(CH.sub.2).sub.3 --327 CH.sub.3 (CH.sub.2).sub.17 -- --OCO-- --(CH.sub.2).sub.4 --328 CH.sub.3 (CH.sub.2).sub.17 -- --OCO-- --(CH.sub.2).sub.5 --329 CH.sub.3 (CH.sub.2).sub.17 -- --OCO-- --(CH.sub.2).sub.6 --330 CH.sub.3 (CH.sub.2).sub.13 -- --OCOO-- --CH.sub.2 --331 CH.sub.3 (CH.sub.2).sub.15 -- --OCOO-- --CH.sub.2 --332 CH.sub.3 (CH.sub.2).sub.17 -- --OCOO-- --CH.sub.2 --333 CH.sub.3 (CH.sub.2).sub.21 -- --OCOO-- --CH.sub.2 --334 CH.sub.3 (CH.sub.2).sub.13 -- --OCOO-- --(CH.sub.2).sub.2 --335 CH.sub.3 (CH.sub.2).sub.15 -- --OCOO-- --(CH.sub.2).sub.2 --336 CH.sub.3 (CH.sub.2).sub.17 -- --OCOO-- --(CH.sub.2).sub.2 --337 CH.sub.3 (CH.sub.2).sub.21 -- --OCOO-- --(CH.sub.2).sub.2 --335 CH.sub.3 (CH.sub.2).sub.11 -- --OCOO-- --(CH.sub.2).sub.3 --339 CH.sub.3 (CH.sub.2).sub.15 -- --OCOO-- --(CH.sub.2).sub.3 --340 CH.sub.3 (CH.sub.2).sub.17 -- --OCOO-- --(CH.sub.2).sub.3 --341 CH.sub.3 (CH.sub.2).sub.17 -- --OCOO-- --(CH.sub.2).sub.4 --342 CH.sub.3 (CH.sub.2).sub.17 -- --OCOO-- --(CH.sub.2).sub.5 --343 CH.sub.3 (CH.sub.2).sub.17 -- --OCOO-- --(CH.sub.2).sub.6 --344 CH.sub.3 (CH.sub.2).sub.15 -- --SCO-- --CH.sub.2 --345 CH.sub.3 (CH.sub.2).sub.17 -- --SCO-- --CH.sub.2 --346 CH.sub.3 (CH.sub.2).sub.15 -- --SCO-- --(CH.sub.2).sub.2 --347 CH.sub.3 (CH.sub.2).sub.17 -- --SCO-- --(CH.sub.2).sub.2 --348 CH.sub.3 (CH.sub.2).sub.17 -- --SCO-- --(CH.sub.2).sub.3 --349 CH.sub.3 (CH.sub.2).sub.17 -- --SCO-- --(CH.sub.2).sub.4 --350 CH.sub.3 (CH.sub.2).sub.17 -- --SCO-- --(CH.sub.2).sub.5 --351 CH.sub.3 (CH.sub.2).sub.7 -- --NH-- --CH.sub.2 --352 CH.sub.3 (CH.sub.2).sub.11 -- --NH-- --CH.sub.2 --353 CH.sub.3 (CH.sub.2).sub.13 -- --NH-- --CH.sub.2 --354 CH.sub.3 (CH.sub.2).sub.15 -- --NH-- --CH.sub.2 --355 CH.sub.3 (CH.sub.2).sub.17 -- --NH-- --CH.sub.2 --356 CH.sub.3 (CH.sub.2).sub.19 -- --NH-- --CH.sub.2 --357 CH.sub.3 (CH.sub.2).sub.21 -- --NH-- --CH.sub.2 --358 CH.sub.3 (CH.sub.2).sub.7 -- --NH-- --(CH.sub.2).sub.2 --359 CH.sub.3 (CH.sub.2).sub.11 -- --NH-- --(CH.sub.2).sub.2 --360 CH.sub.3 (CH.sub.2).sub.13 -- --NH-- --(CH.sub.2).sub.2 --361 CH.sub.3 (CH.sub.2).sub.15 -- --NH-- --(CH.sub.2).sub.2 --362 CH.sub.3 (CH.sub.2).sub.17 -- --NH-- --(CH.sub.2).sub.2 --363 CH.sub.3 (CH.sub.2).sub.19 -- --NH-- --(CH.sub.2).sub.2 --364 CH.sub.3 (CH.sub.2).sub.21 -- --NH-- --(CH.sub.2).sub.2 --365 CH.sub.3 (CH.sub.2).sub.7 -- --NH-- --(CH.sub.2).sub.3 --366 CH.sub.3 (CH.sub.2).sub.11 -- --NH-- --(CH.sub.2).sub.3 --367 CH.sub.3 (CH.sub.2).sub.13 -- --NH-- --(CH.sub.2).sub.3 --368 CH.sub.3 (CH.sub.2).sub.15 -- --NH-- --(CH.sub.2).sub.3 --369 CH.sub.3 (CH.sub.2).sub.17 -- --NH-- --(CH.sub.2).sub.3 --370 CH.sub.3 (CH.sub.2).sub.19 -- --NH-- --(CH.sub.2).sub.3 --371 CH.sub.3 (CH.sub.2).sub.21 -- --NH-- --(CH.sub.2).sub.3 --372 CH.sub.3 (CH.sub.2).sub.7 -- --NH-- --(CH.sub.2).sub.4 --373 CH.sub.3 (CH.sub.2).sub.11 -- --NH-- --(CH.sub.2).sub.4 --374 CH.sub.3 (CH.sub.2).sub.13 -- --NH-- --(CH.sub.2).sub.4 --375 CH.sub.3 (CH.sub.2).sub.15 -- --NH-- --(CH.sub.2).sub.4 --376 CH.sub.3 (CH.sub.2).sub.17 -- --NH-- --(CH.sub.2).sub.4 --377 CH.sub.3 (CH.sub.2).sub.19 -- --NH-- --(CH.sub.2).sub.4 --378 CH.sub.3 (CH.sub.2).sub.21 -- --NH-- --(CH.sub.2).sub.4 --379 CH.sub.3 (CH.sub.2).sub.11 -- --NH-- --(CH.sub.2).sub.5 --380 CH.sub.3 (CH.sub.2).sub.13 -- --NH-- --(CH.sub.2).sub.5 --381 CH.sub.3 (CH.sub.2).sub.15 -- --NH-- --(CH.sub.2).sub.5 --382 CH.sub.3 (CH.sub.2).sub.17 -- --NH-- --(CH.sub.2).sub.5 --383 CH.sub.3 (CH.sub.2).sub.11 -- --NH-- --(CH.sub.2).sub.6 --384 CH.sub.3 (CH.sub.2).sub.13 -- --NH-- --(CH.sub.2).sub.6 --385 CH.sub.3 (CH.sub.2).sub.17 -- --NH-- --(CH.sub.2).sub.6 --386 CH.sub.3 (CH.sub.2).sub.7 -- --O-- --CH.sub.2 --387 CH.sub.3 (CH.sub.2).sub.11 -- --O-- --CH.sub.2 --388 CH.sub.3 (CH.sub.2).sub.13 -- --O-- --CH.sub.2 --389 CH.sub.3 (CH.sub.2).sub.15 -- --O-- --CH.sub.2 --390 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --CH.sub.2 --391 CH.sub.3 (CH.sub.2).sub.19 -- --O-- --CH.sub.2 --392 CH.sub.3 (CH.sub.2).sub.21 -- --O-- --CH.sub.2 --393 CH.sub.3 (CH.sub.2).sub.7 -- --O-- --(CH.sub.2).sub.2 --394 CH.sub.3 (CH.sub.2).sub.11 -- --O-- --(CH.sub.2).sub.2 --395 CH.sub.3 (CH.sub.2).sub.13 -- --O-- --(CH.sub.2).sub.2 --396 CH.sub.3 (CH.sub.2).sub.15 -- --O-- --(CH.sub.2).sub.2 --397 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --(CH.sub.2).sub.2 --398 CH.sub.3 (CH.sub.2).sub.19 -- --O-- --(CH.sub.2).sub.2 --399 CH.sub.3 (CH.sub.2).sub.21 -- --O-- --(CH.sub.2).sub.2 --400 CH.sub.3 (CH.sub.2).sub.7 -- --O-- --(CH.sub.2).sub.3 --401 CH.sub.3 (CH.sub.2).sub.11 -- --O-- --(CH.sub.2).sub.3 --402 CH.sub.3 (CH.sub.2).sub.13 -- --O-- --(CH.sub.2).sub.3 --403 CH.sub.3 (CH.sub.2).sub.15 -- --O-- --(CH.sub.2).sub.3 --404 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --(CH.sub.2).sub.3 --405 CH.sub.3 (CH.sub.2).sub.19 -- --O-- --(CH.sub.2).sub.3 --406 CH.sub.3 (CH.sub.2).sub.21 -- --O-- --(CH.sub.2).sub.3 --407 CH.sub.3 (CH.sub.2).sub.7 -- --O-- --(CH.sub.2).sub.4 --408 CH.sub.3 (CH.sub.2).sub.11 -- --O-- --(CH.sub.2).sub.4 --409 CH.sub.3 (CH.sub.2).sub.13 -- --O-- --(CH.sub.2).sub.4 --410 CH.sub.3 (CH.sub.2).sub.15 -- --O-- --(CH.sub.2).sub.4 --411 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --(CH.sub.2).sub.4 --412 CH.sub.3 (CH.sub.2).sub.19 -- --O-- --(CH.sub.2).sub.4 --413 CH.sub.3 (CH.sub.2).sub.21 -- --O-- --(CH.sub.2).sub.4 --414 CH.sub.3 (CH.sub.2).sub.11 -- --O-- --(CH.sub.2).sub.5 --415 CH.sub.3 (CH.sub.2).sub.13 -- --O-- --(CH.sub.2).sub.5 --416 CH.sub.3 (CH.sub.2).sub.15 -- --O-- --(CH.sub.2).sub.5 --417 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --(CH.sub.2).sub.5 --418 CH.sub.3 (CH.sub.2).sub.11 -- --O-- --(CH.sub.2).sub.6 --419 CH.sub.3 (CH.sub.2).sub.13 -- --O-- --(CH.sub.2).sub.6 --420 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --(CH.sub.2).sub.6 --421 CH.sub.3 (CH.sub.2).sub.7 -- --S-- --CH.sub.2 --422 CH.sub.3 (CH.sub.2).sub.11 -- --S-- --CH.sub.2 --423 CH.sub.3 (CH.sub.2).sub.13 -- --S-- --CH.sub.2 --424 CH.sub.3 (CH.sub.2).sub.15 -- --S-- --CH.sub.2 --425 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --CH.sub.2 --426 CH.sub.3 (CH.sub.2).sub.19 -- --S-- --CH.sub.2 --427 CH.sub.3 (CH.sub.2).sub.21 -- --S-- --CH.sub.2 --425 CH.sub.3 (CH.sub.2).sub.7 -- --S-- --(CH.sub.2).sub.2 --429 CH.sub.3 (CH.sub.2).sub.11 -- --S-- --(CH.sub.2).sub.2 --430 CH.sub.3 (CH.sub.2).sub.13 -- --S-- --(CH.sub.2).sub.2 --431 CH.sub.3 (CH.sub.2).sub.15 -- --S-- --(CH.sub.2).sub.2 --432 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --(CH.sub.2).sub.2 --433 CH.sub.3 (CH.sub.2).sub.19 -- --S-- --(CH.sub.2).sub.2 --434 CH.sub.3 (CH.sub.2).sub.21 -- --S-- --(CH.sub.2).sub.2 --435 CH.sub.3 (CH.sub.2).sub.7 -- --S-- --(CH.sub.2).sub.3 --436 CH.sub.3 (CH.sub.2).sub.11 -- --S-- --(CH.sub.2).sub.3 --437 CH.sub.3 (CH.sub.2).sub.13 -- --S-- --(CH.sub.2).sub.3 --438 CH.sub.3 (CH.sub.2).sub.15 -- --S-- --(CH.sub.2).sub.3 --439 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --(CH.sub.2).sub.3 --440 CH.sub.3 (CH.sub.2).sub.19 -- --S-- --(CH.sub.2).sub.3 --441 CH.sub.3 (CH.sub.2).sub.21 -- --S-- --(CH.sub.2).sub.3 --442 CH.sub.3 (CH.sub.2).sub.7 -- --S-- --(CH.sub.2).sub.4 --443 CH.sub.3 (CH.sub.2).sub.11 -- --S-- --(CH.sub.2).sub.4 --444 CH.sub.3 (CH.sub.2).sub.13 -- --S-- --(CH.sub.2).sub.4 --445 CH.sub.3 (CH.sub.2).sub.15 -- --S-- --(CH.sub.2).sub.4 --446 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --(CH.sub.2).sub.4 --447 CH.sub.3 (CH.sub.2).sub.19 -- --S-- --(CH.sub.2).sub.4 --448 CH.sub.3 (CH.sub.2).sub.21 -- --S-- --(CH.sub.2).sub.4 --449 CH.sub.3 (CH.sub.2).sub.11 -- --S-- --(CH.sub.2).sub.5 --450 CH.sub.3 (CH.sub.2).sub.13 -- --S-- --(CH.sub.2).sub.5 --451 CH.sub.3 (CH.sub.2).sub.15 -- --S-- --(CH.sub.2).sub.5 --452 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --(CH.sub.2).sub.5 --453 CH.sub.3 (CH.sub.2).sub.11 -- --S-- --(CH.sub.2).sub.6 --454 CH.sub.3 (CH.sub.2).sub.13 -- --S-- --(CH.sub.2).sub.6 --455 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --(CH.sub.2).sub.6 --456 CH.sub.3 (CH.sub.2).sub.7 -- --CH.dbd.N-- --CH.sub.2 --457 CH.sub.3 (CH.sub.2).sub.11 -- --NH.dbd.C-- --CH.sub.2 --458 CH.sub.3 (CH.sub.2).sub.13 -- --CH.dbd.N-- --CH.sub.2 --459 CH.sub.3 (CH.sub.2).sub.15 -- --NH.dbd.C-- --CH.sub.2 --460 CH.sub.3 (CH.sub.2).sub.17 -- --C.dbd.NH-- --CH.sub.2 --461 CH.sub.3 (CH.sub.2).sub.19 -- --CH.dbd.N-- --CH.sub.2 --462 CH.sub.3 (CH.sub.2).sub.21 -- --NH.dbd.C-- --CH.sub.2 --463 CH.sub.3 (CH.sub.2).sub.7 -- --CH.dbd.N-- --(CH.sub.2).sub.2 --464 CH.sub.3 (CH.sub.2).sub.11 -- --NH.dbd.C-- --(CH.sub.2).sub.2 --465 CH.sub.3 (CH.sub.2).sub.13 -- --C.dbd.NH-- --(CH.sub.2).sub.2 --466 CH.sub.3 (CH.sub.2).sub.15 -- --CH.dbd.N-- --(CH.sub.2).sub.2 --467 CH.sub.3 (CH.sub.2).sub.17 -- --NH.dbd.C-- --(CH.sub.2).sub.2 --468 CH.sub.3 (CH.sub.2).sub.19 -- --CH.dbd.N-- --(CH.sub.2).sub.2 --469 CH.sub.3 (CH.sub.2).sub.21 -- --NH.dbd.C-- --(CH.sub.2).sub.2 --470 CH.sub.3 (CH.sub.2).sub.7 -- --C.dbd.NH-- --(CH.sub.2).sub.3 --471 CH.sub.3 (CH.sub.2).sub.11 -- --CH.dbd.N-- --(CH.sub.2).sub.3 --472 CH.sub.3 (CH.sub.2).sub.13 -- --NH.dbd.C-- --(CH.sub.2).sub.3 --473 CH.sub.3 (CH.sub.2).sub.15 -- --CH.dbd.N-- --(CH.sub.2).sub.3 --474 CH.sub.3 (CH.sub.2).sub.17 -- --NH.dbd.C-- --(CH.sub.2).sub.3 --475 CH.sub.3 (CH.sub.2).sub.19 -- --C.dbd.NH-- --(CH.sub.2).sub.3 --476 CH.sub.3 (CH.sub.2).sub.21 -- --CH.dbd.N-- --(CH.sub.2).sub.3 --477 CH.sub.3 (CH.sub.2).sub.7 -- --NH.dbd.C-- --(CH.sub.2).sub.4 --478 CH.sub.3 (CH.sub.2).sub.11 -- --CH.dbd.N-- --(CH.sub.2).sub.4 --479 CH.sub.3 (CH.sub.2).sub.13 -- --NH.dbd.C-- --(CH.sub.2).sub.4 --480 CH.sub.3 (CH.sub.2).sub.15 -- --C.dbd.NH-- --(CH.sub.2).sub.4 --481 CH.sub.3 (CH.sub.2).sub.17 -- --CH.dbd.N-- --(CH.sub.2).sub.4 --482 CH.sub.3 (CH.sub.2).sub.19 -- --NH.dbd.C-- --(CH.sub.2).sub.4 --483 CH.sub.3 (CH.sub.2).sub.21 -- --CH.dbd.N-- --(CH.sub.2).sub.4 --484 CH.sub.3 (CH.sub.2).sub.11 -- --NH.dbd.C-- --(CH.sub.2).sub.5 --485 CH.sub.3 (CH.sub.2).sub.13 -- --C.dbd.NH-- --(CH.sub.2).sub.5 --486 CH.sub.3 (CH.sub.2).sub.15 -- --CH.dbd.N-- --(CH.sub.2).sub.5 --487 CH.sub.3 (CH.sub.2).sub.17 -- --NH.dbd.C-- --(CH.sub.2).sub.5 --488 CH.sub.3 (CH.sub.2).sub.11 -- --CH.dbd.N-- --(CH.sub.2).sub.6 --489 CH.sub.3 (CH.sub.2).sub.13 -- --NH.dbd.C-- --(CH.sub.2).sub.6 --490 CH.sub.3 (CH.sub.2).sub.17 -- --C.dbd.NH-- --(CH.sub.2).sub.6 --______________________________________
Also, in the above formula (1), more than two X (i.e., a divalent group having at least one hetero atom) may be present via a hydrocarbon group such as alkylene group. That is, the carboxylic acid compound of the present invention may have a structure in which X in the above formula has a structure of:
--Y--(R.sub.3 --Y').sub.r --
wherein Y and Y' represents, respectively, a divalent group having at least one hetero atom,
R.sub.3 represents a divalent hydrocarbon group whose principle chain may contain a non-limiting number of carbon atoms, a portion of which may form aromatic ring(s), and
.sub.r represents an integer between 1 and 4 (note that when .sub.r is more than 2, R.sub.3 and Y', respectively, may be the same or different.
Examples of preferable compounds of the above include compounds having the following formulae (3) to (6):
R.sub.1 --Y--R.sub.3 --Y'--R.sub.2 --COOH (3)
R.sub.1 --Y--R.sub.3 --Y'--R.sub.3 '--Y"--R.sub.2 --COOH (4)
R.sub.1 --Y--R.sub.3 --Y'--R.sub.3 '--Y"--R.sub.3 "--Y"'--R.sub.2 --COOH(5)
R.sub.1 --Y--R.sub.3 --Y'--R.sub.3 '--Y"--R.sub.3 "--Y"'--R.sub.3 "'--Y""--R.sub.2 --COOH (6)
wherein R.sub.3 ', R.sub.3 " and R.sub.3 "', respectively, has the same definition as R.sub.3 and they can be the same or different, and
Y", Y"' and Y"" has the same definition as Y, and they can be the same or different.
Examples of the above compounds wherein R.sub.3, R.sub.3 ', R.sub.3 " and R.sub.3 "', respectively, is an alkylene group may be as follows:
CH.sub.3 (CH.sub.2).sub.m-1 --Y--(CH.sub.2).sub.w --Y'--(CH.sub.2).sub.n --COOH (7)
CH.sub.3 (CH.sub.2).sub.m-1 --Y--(CH.sub.2).sub.w --Y'--(CH.sub.2).sub.x --Y"--(CH.sub.2).sub.n --COOH (8)
CH.sub.3 (CH.sub.2).sub.m-1 --Y--(CH.sub.2).sub.w --Y'--(CH.sub.2).sub.x --Y"--(CH.sub.2).sub.y --Y"'--(CH.sub.2).sub.n --COOH (9)
CH.sub.3 (CH.sub.2).sub.m-1 --Y--(CH.sub.2).sub.w --Y'--(CH.sub.2).sub.x --Y"--(CH.sub.2).sub.y --Y"'--(CH.sub.2).sub.z --Y""--(CH.sub.2).sub.n --COOH (10)
wherein .sub.w' x' y and .sub.z' respectively, represents an integer between zero and 8 preferably but not particularly limited.
Examples of carboxylic acid compound having the above formula (7) according to the present invention are shown in the following Tables 2-1 through 2-5. Although examples of carboxylic acid compounds having the above formulae (8) to (10) are not shown, the same Y, Y', Y", Y"' and Y"" shown in Tables 2-1 through 2-5 may be applied to these compounds. However, they are not by any means to restrict the present invention.
TABLE 2__________________________________________________________________________CompoundNo. CH.sub.3 (CH.sub.2).sub.m-1 -- --Y-- --(CH.sub.2).sub.w -- --Y'-- --(CH.sub.2).sub.n --__________________________________________________________________________491 CH.sub.3 (CH.sub.2).sub.21 -- --NH-- --(CH.sub.2).sub.4 -- --NHCO-- --CH.sub.2 --492 CH.sub.3 (CH.sub.2).sub.17 -- --NH-- --(CH.sub.2).sub.2 -- --NHCO-- --(CH.sub.2).sub.2 --493 CH.sub.3 (CH.sub.2).sub.16 -- --CO-- --(CH.sub.2).sub.2 -- --NHCO-- --(CH.sub.2).sub.2 --494 CH.sub.3 (CH.sub.2).sub.16 -- --CO-- --CH.sub.2 -- --NHCO-- --(CH.sub.2).sub.2 --495 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --(CH.sub.2).sub.5 -- --NHCO-- --(CH.sub.2).sub.5 --496 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --(CH.sub.2).sub.2 -- --NHCO-- --(CH.sub.2).sub.2 --497 CH.sub.3 (CH.sub.2).sub.11 -- --O-- --(CH.sub.2).sub.4 -- --NHCO-- --(CH.sub.2).sub.3 --498 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --(CH.sub.2).sub.3 -- --NHCO-- --CH.sub.2 --499 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --(CH.sub.2).sub.4 -- --NHCO-- --CH.sub.2 --500 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 -- --(CH.sub.2).sub.2 -- --NHCO-- --(CH.sub.2).sub.2 --501 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 -- --(CH.sub.2).sub.5 -- --NHCO-- --(CH.sub.2).sub.5 --502 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOO-- --CH.sub.2 -- --NHCO-- --(CH.sub.2).sub.2 --503 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.3 -- --NHCO-- --CH.sub.2 --504 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.4 -- --NHCO-- --CH.sub.2 --505 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.2 -- --NHCO-- --(CH.sub.2).sub.2 --506 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONH-- --(CH.sub.2).sub.6 -- --NHCO-- --(CH.sub.2).sub.2 --507 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONH-- --(CH.sub.2).sub.4 -- --NHCO-- --(CH.sub.2).sub.3 --508 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.4 -- --NHCO-- --CH.sub.2 --509 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.3 -- --NHCO-- --CH.sub.2 --510 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 NH-- --(CH.sub.2).sub.3 -- --NHCO-- --(CH.sub.2).sub.3 --511 CH.sub.3 (CH.sub.2).sub.21 -- --NHCSNH-- --(CH.sub.2).sub.4 -- --NHCO-- --(CH.sub.2).sub.2 --512 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCONH-- --(CH.sub.2).sub.3 -- --NHCO-- --(CH.sub.2).sub.3 --513 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCO-- --CH.sub.2 -- --NHCO-- --CH.sub.2 --514 CH.sub.3 (CH.sub.2).sub.16 -- --COO-- --(CH.sub.2).sub.2 -- --NHCO-- --(CH.sub.2).sub.2 --515 CH.sub.3 (CH.sub.2).sub.20 -- --COO-- --(CH.sub.2).sub.3 -- --NHCO-- --(CH.sub.2).sub.3 --516 CH.sub.3 (CH.sub.2).sub.16 -- --COS-- --(CH.sub.2).sub.4 -- --NHCO-- --(CH.sub.2).sub.6 --517 CH.sub.3 (CH.sub.2).sub.15 -- --CH.dbd.N-- --(CH.sub.2).sub.6 -- --NHCO-- --(CH.sub.2).sub.2 --518 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHCO-- --(CH.sub.2).sub.2 -- --NHCO-- --CH.sub.2 --519 CH.sub.3 (CH.sub.2).sub.16 -- --CONHNHCO-- --(CH.sub.2).sub.3 -- --NHCO-- --(CH.sub.2).sub.5 --520 CH.sub.3 (CH.sub.2).sub.16 -- --NHNHCONH-- --(CH.sub.2).sub.4 -- --NHCO-- --CH.sub.2 --521 CH.sub.3 (CH.sub.2).sub.21 -- --NH-- --(CH.sub.2).sub.4 -- --NHCONH-- --CH.sub.2 --522 CH.sub.3 (CH.sub.2).sub.17 -- --NH-- --(CH.sub.2).sub.2 -- --NHCONH-- --(CH.sub.2).sub.2 --523 CH.sub.3 (CH.sub.2).sub.16 -- --CO-- --(CH.sub.2).sub.2 -- --NHCONH-- --(CH.sub.2).sub.2 --524 CH.sub.3 (CH.sub.2).sub.16 -- --CO-- --CH.sub.2 -- --NHCONH-- --(CH.sub.2).sub.2 --525 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --(CH.sub.2).sub.5 -- --NHCONH-- --(CH.sub.2).sub.5 --526 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --(CH.sub.2).sub.2 -- --NHCONH-- --(CH.sub.2).sub.2 --527 CH.sub.3 (CH.sub.2).sub.11 -- --O-- --(CH.sub.2).sub.4 -- --NHCONH-- --(CH.sub.2).sub.3 --528 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --(CH.sub.2).sub.3 -- --NHCONH-- --CH.sub.2 --529 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --(CH.sub.2).sub.4 -- --NHCONH-- --CH.sub.2 --530 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 -- --(CH.sub.2).sub.2 -- --NHCONH-- --(CH.sub.2).sub.2 --531 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 -- --(CH.sub.2).sub.5 -- --NHCONH-- --(CH.sub.2).sub.5 --532 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOO-- --CH.sub.2 -- --NHCONH-- --(CH.sub.2).sub.2 --533 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.3 -- --NHCONH-- --CH.sub.2 --534 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.4 -- --NHCONH-- --CH.sub.2 --535 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.2 -- --NHCONH-- --(CH.sub.2).sub.2 --536 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONH-- --(CH.sub.2).sub.6 -- --NHCONH-- --(CH.sub.2).sub.2 --537 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONH-- --(CH.sub.2).sub.4 -- --NHCONH-- --(CH.sub.2).sub.3 --538 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.4 -- --NHCONH-- --CH.sub.2 --539 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.3 -- --NHCONH-- --CH.sub.2 --540 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 NH-- --(CH.sub.2).sub.3 -- --NHCONH-- --(CH.sub.2).sub.3 --541 CH.sub.3 (CH.sub.2).sub.21 -- --NHCSNH-- --(CH.sub.2).sub.4 -- --NHCONH-- --(CH.sub.2).sub.2 --542 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCONH-- --(CH.sub.2).sub.3 -- --NHCONH-- --(CH.sub.2).sub.3 --543 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCO-- --CH.sub.2 -- --NHCONH-- --CH.sub.2 --544 CH.sub.3 (CH.sub.2).sub.16 -- --COO-- --(CH.sub.2).sub.2 -- --NHCONH-- --(CH.sub.2).sub.2 --545 CH.sub.3 (CH.sub.2).sub.20 -- --COO-- --(CH.sub.2).sub.3 -- --NHCONH-- --(CH.sub.2).sub.3 --546 CH.sub.3 (CH.sub.2).sub.16 -- --COS-- --(CH.sub.2).sub.4 -- --NHCONH-- --(CH.sub.2).sub.6 --547 CH.sub.3 (CH.sub.2).sub.15 -- --CH.dbd.N-- --(CH.sub.2).sub.6 -- --NHCONH-- --(CH.sub.2).sub.2 --548 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHCO-- --(CH.sub.2).sub.2 -- --NHCONH-- --CH.sub.2 --549 CH.sub.3 (CH.sub.2).sub.16 -- --CONHNHCO-- --(CH.sub.2).sub.3 -- --NHCONH-- --(CH.sub.2).sub.5 --550 CH.sub.3 (CH.sub.2).sub.16 -- --NHNHCONH-- --(CH.sub.2).sub.4 -- --NHCONH-- --CH.sub.2 --551 CH.sub.3 (CH.sub.2).sub.21 -- --NH-- --(CH.sub.2).sub.4 -- --CONH-- --CH.sub.2 --552 CH.sub.3 (CH.sub.2).sub.17 -- --NH-- --(CH.sub.2).sub.2 -- --CONH-- --(CH.sub.2).sub.2 --553 CH.sub.3 (CH.sub.2).sub.16 -- --CO-- --(CH.sub.2).sub.2 -- --CONH-- --(CH.sub.2).sub.2 --554 CH.sub.3 (CH.sub.2).sub.16 -- --CO-- --CH.sub.2 -- --CONH-- --(CH.sub.2).sub.2 --555 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --(CH.sub.2).sub.5 -- --CONH-- --(CH.sub.2).sub.5 --556 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --(CH.sub.2).sub.2 -- --CONH-- --(CH.sub.2).sub.2 --557 CH.sub.3 (CH.sub.2).sub.11 -- --O-- --(CH.sub.2).sub.4 -- --CONH-- --(CH.sub.2).sub.3 --558 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --(CH.sub.2).sub.3 -- --CONH-- --CH.sub.2 --559 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --(CH.sub.2).sub.4 -- --CONH-- --CH.sub.2 --560 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 -- --(CH.sub.2).sub.2 -- --CONH-- --(CH.sub.2).sub.2 --561 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 -- --(CH.sub.2).sub.5 -- --CONH-- --(CH.sub.2).sub.5 --562 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOO-- --CH.sub.2 -- --CONH-- --(CH.sub.2).sub.2 --563 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.3 -- --CONH-- --CH.sub.2 --564 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.4 -- --CONH-- --CH.sub.2 --565 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.2 -- --CONH-- --(CH.sub.2).sub.2 --566 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONH-- --(CH.sub.2).sub.6 -- --CONH-- --(CH.sub.2).sub.2 --567 CH.sub.3 (CH.sub.2).sub.13 -- --NHCONH-- --(CH.sub.2).sub.4 -- --CONH-- --(CH.sub.2).sub.3 --568 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.4 -- --CONH-- --CH.sub.2 --569 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.3 -- --CONH-- --CH.sub.2 --570 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 NH-- --(CH.sub.2).sub.3 -- --CONH-- --(CH.sub.2).sub.3 --571 CH.sub.3 (CH.sub.2).sub.21 -- --NHCSNH-- --(CH.sub.2).sub.4 -- --CONH-- --(CH.sub.2).sub.2 --572 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCONH-- --(CH.sub.2).sub.3 -- --CONH-- --(CH.sub.2).sub.3 --573 CH.sub.3 (CH.sub.2).sub.16 -- --CONHCO-- --CH.sub.2 -- --CONH-- --CH.sub.2 --574 CH.sub.3 (CH.sub.2).sub.16 -- --COO-- --(CH.sub.2).sub.2 -- --CONH-- --(CH.sub.2).sub.2 --575 CH.sub.3 (CH.sub.2).sub.20 -- --COO-- --(CH.sub.2).sub.3 -- --CONH-- --(CH.sub.2).sub.3 --576 CH.sub.3 (CH.sub.2).sub.16 -- --COS-- --(CH.sub.2).sub.4 -- --CONH-- --(CH.sub.2).sub.6 --577 CH.sub.3 (CH.sub.2).sub.15 -- --CH.dbd.N-- --(CH.sub.2).sub.6 -- --CONH-- --(CH.sub.2).sub.2 --578 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONHCO-- --(CH.sub.2).sub.2 -- --CONH-- --CH.sub.2 --579 CH.sub.3 (CH.sub.2).sub.16 -- --CONHNHCO-- --(CH.sub.2).sub.3 -- --CONH-- --(CH.sub.2).sub.5 --580 CH.sub.3 (CH.sub.2).sub.16 -- --NHNHCONH-- --(CH.sub.2).sub.4 -- --CONH-- --CH.sub.2 --581 CH.sub.3 (CH.sub.2).sub.21 -- --O-- --(CH.sub.2).sub.4 -- --NHCSNH-- --CH.sub.2 --582 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --(CH.sub.2).sub.2 -- --NHCSNH-- --(CH.sub.2).sub.2 --583 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.2 -- --NHCSNH-- --(CH.sub.2).sub.2 --584 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --CH.sub.2 -- --NHCSNH-- --(CH.sub.2).sub.2 --585 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.5 -- --NHCSNH-- --(CH.sub.2).sub.5 --586 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 -- --(CH.sub.2).sub.2 -- --NHCSNH-- --(CH.sub.2).sub.2 --587 CH.sub.3 (CH.sub.2).sub.12 -- --COO-- --(CH.sub.2).sub.4 -- --NHCSNH-- --(CH.sub.2).sub.3 --588 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOO-- --(CH.sub.2).sub.3 -- --NHCSNH-- --CH.sub.2 --589 CH.sub.3 (CH.sub.2).sub.17 -- --NHSO.sub.2 -- --(CH.sub.2).sub.4 -- --NHCSNH-- --CH.sub.2 --590 CH.sub.3 (CH.sub.2).sub.17 -- --NHNHCONH-- --(CH.sub.2).sub.2 -- --NHCSNH-- --(CH.sub.2).sub.2 --591 CH.sub.3 (CH.sub.2).sub.17 -- --O-- --(CH.sub.2).sub.5 -- --SO.sub.2 -- --(CH.sub.2).sub.5 --592 CH.sub.3 (CH.sub.2).sub.17 -- --S-- --CH.sub.2 -- --SO.sub.2 -- --(CH.sub.2).sub.2 --593 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.3 -- --SO.sub.2 -- --CH.sub.2 --594 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.4 -- --SO.sub.2 -- --CH.sub.2 --595 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.2 -- --SO.sub.2 -- --(CH.sub.2).sub.2 --596 CH.sub.3 (CH.sub.2).sub.13 -- --SO.sub.2 -- --(CH.sub.2).sub.6 -- --SO.sub.2 -- --(CH.sub.2).sub.2 --597 CH.sub.3 (CH.sub.2).sub.12 -- --COO-- --(CH.sub.2).sub.4 -- --SO.sub.2 -- --(CH.sub.2).sub.3 --598 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOO-- --(CH.sub.2).sub.4 -- --SO.sub.2 -- --CH.sub.2 --599 CH.sub.3 (CH.sub.2).sub.17 -- --NHSO.sub.2 -- --(CH.sub.2).sub.3 -- --SO.sub.2 -- --CH.sub.2 --600 CH.sub.3 (CH.sub.2).sub.17 -- --NHNHCONH-- --(CH.sub.2).sub.3 -- --SO.sub.2 -- --(CH.sub.2).sub.3 --601 CH.sub.3 (CH.sub.2).sub.21 -- --O-- --(CH.sub.2).sub.4 -- --S-- --(CH.sub.2).sub.2 --602 CH.sub.3 (CH.sub.2).sub.15 -- --S-- --(CH.sub.2).sub.3 -- --S-- --(CH.sub.2).sub.3 --603 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --CH.sub.2 -- --S-- --CH.sub.2 --604 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.2 -- --S-- --(CH.sub.2).sub.2 --605 CH.sub.3 (CH.sub.2).sub.20 -- --CONH-- --(CH.sub.2).sub.3 -- --S-- --(CH.sub.2).sub.3 --606 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 -- --(CH.sub.2).sub.4 -- --S-- --(CH.sub.2).sub.6 --607 CH.sub.3 (CH.sub.2).sub.16 -- --COO-- --(CH.sub.2).sub.6 -- --S-- --(CH.sub.2).sub.2 --608 CH.sub.3 (CH.sub.2).sub.17 -- --NHCOO-- --(CH.sub.2).sub.2 -- --S-- --CH.sub.2 --609 CH.sub.3 (CH.sub.2).sub.17 -- --NHSO.sub.2 -- --(CH.sub.2).sub.3 -- --S-- --(CH.sub.2).sub.5 --610 CH.sub.3 (CH.sub.2).sub.17 -- --NHNHCONH-- --(CH.sub.2).sub.4 -- --S-- --CH.sub.2 --611 CH.sub.3 (CH.sub.2).sub.21 -- --S-- --(CH.sub.2).sub.4 -- --OCO-- --CH.sub.2 --612 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 -- --(CH.sub.2).sub.2 -- --OCO-- --(CH.sub.2).sub.2 --613 CH.sub.3 (CH.sub.2).sub.16 -- --CONH-- --(CH.sub.2).sub.2 -- --OCO-- --(CH.sub.2).sub.2 --614 CH.sub.3 (CH.sub.2).sub.16 -- --NHCONH-- --CH.sub.2 -- --OCO-- --(CH.sub.2).sub.2 --615 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.5 -- --NHCO2-- --(CH.sub.2).sub.5 --616 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 -- --(CH.sub.2).sub.2 -- --NHSO2-- --(CH.sub.2).sub.2 --617 CH.sub.3 (CH.sub.2).sub.11 -- --NHCO-- --(CH.sub.2).sub.4 -- --CO-- --(CH.sub.2).sub.3 --618 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.3 -- --CO-- --CH.sub.2 --619 CH.sub.3 (CH.sub.2).sub.17 -- --SO.sub.2 -- --(CH.sub.2).sub.4 -- --O-- --CH.sub.2 --620 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.2 -- --O-- --(CH.sub.2).sub.2 --621 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.5 -- --O-- --(CH.sub.2).sub.5 --622 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --CH.sub.2 -- --CONHCO-- --(CH.sub.2).sub.2 --623 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.3 -- --NHCONHCO-- --CH.sub.2 --624 CH.sub.3 (CH.sub.2).sub.17 -- --NHCONH-- --(CH.sub.2).sub.4 -- --CONHCONH-- --CH.sub.2 --625 CH.sub.3 (CH.sub.2).sub.17 -- --NHCO-- --(CH.sub.2).sub.2 -- --NHNHCONH-- --(CH.sub.2).sub.2 --626 CH.sub.3 (CH.sub.2).sub.13 -- --OCO-- --(CH.sub.2).sub.6 -- --N.dbd.CH-- --(CH.sub.2).sub.2 --__________________________________________________________________________
The thermally reversible color forming compounds according to the present invention comprises the above-mentioned color developer and a color producing agent. The color producing agent, as mentioned previously, is an electron donating compound and is a dye precursor (leuco dye) having no color or pale color. The color producing agent that may be used in the present invention is not particularly limited and can be selected from the known color producing agents such as phthalide type compounds, azaphthalide type compounds, fluoran type compounds, phenothiazine type compounds, leuco auramine type compounds and so on. Examples of the color producing agents that may be used in the present invention are as follows: ##STR4## wherein R.sub.1 represents a hydrogen or an alkyl group having 1 to 4 carbon atoms; R.sub.2 represents an alkyl group having 1 to 6 carbon atoms, cycloalkyl group, or phenyl group which may be unsubstituted or substituted by an alkyl group such as methyl and ethyl, an alkoxy group such as methoxy and ethoxy, or a halogen; R.sub.3 represents a hydrogen, an alkyl group having 1 to 2 carbon atoms, an alkoxy group, or a halogen; R.sub.4 represents a hydrogen, methyl group, halogen, or an amino group which may be unsubstituted or substituted by an alkyl group, an aryl group which may be substituted by an alkyl group, a halogen, or an alkoxy group, or an aralkyl group which may be substituted by an alkyl group, a halogen, or an alkoxy group.
Examples of the above-mentioned color producing agents include:
2-anilino-3-methyl-6-diethylaminofluoran,
2-anilino-3-methyl-6-di(n-butylamino)fluoran,
2-anilino-3-methyl-6-(N-n-propyl-N-methylamino)fluoran,
2-anilino-3-methyl-6-(N-isopropyl-N-methylamino)fluoran,
2-anilino-3-methyl-6-(N-isobutyl-N-methylamino)fluoran,
2-anilino-3-methyl-6-(N-n-amyl-N-methylamino)fluoran,
2-anilino-3-methyl-6-(N-sec-butyl-N-methylamino)fluoran,
2-anilino-3-methyl-6-(N-n-amyl-N-ethylamino)fluoran,
2-anilino-3-methyl-6-(N-iso-amyl-N-ethylamino)fluoran,
2-anilino-3-methyl-6-(N-n-propyl-N-isopropylamino)fluoran,
2-anilino-3-methyl-6-(N-cyclohexyl-N-methylamino)fluoran,
2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran,
2-anilino-3-methyl-6-(N-methyl-p-toluidino)fluoran,
2-(m-trichloromethylanilino)-3-methyl-6-diethylaminofluoran,
2-(m-trifluoromethylanilino)-3-methyl-6-diethylaminofluoran,
2-(m-trichloromethylanilino)-3-methyl-6-(N-cyclohexyl-N-methylamino)fluoran
2-(2,4-dimethylanilino)-3-methyl-6-diethylaminofluoran,
2-(N-ethyl-p-toluidino)-3-methyl-6-(N-ethylanilino)fluoran,
2-(N-ethyl-p-toluidino)-3-methyl-6-(N-propyl-p-toluidino)fluoran,
2-anilino-6-(N-n-hexyl-N-ethylaminofluoran,
2-(o-chloroanilino)-6-diethylaminofluoran,
2-(o-chloroanilino)-6-dibutylaminofluoran,
2-(m-trifluoromethylanilino)-6-diethylaminofluoran,
2-(p-acetylanilino)-6-(N-n-amyl-N-n-butylamino)fluoran,
2-benzylamino-6-(N-ethyl-p-toluidino)fluoran,
2-benzylamino-6-(N-methyl-2,4-dimethylanilino)fluoran,
2-benzylamino-6-(N-ethyl-2,4-dimethylanilino)fluoran,
2-benzylamino-6-(N-methyl-p-toluidino)fluoran,
2-(di-p-methylbenzylamino)-6-(N-ethyl-p-toluidino)fluoran,
2-(.alpha.-phenylethylamino)-6-(N-ethyl-p-toluidino)fluoran,
2-methylamino-6-(N-methylanilino)fluoran,
2-methylamino-6-(N-ethylanilino)fluoran,
2-methylamino-6-(N-propylanilino)fluoran,
2-ethylamino-6-(N-methyl-p-toluidino)fluoran,
2-methylamino-6-(N-methyl-2,4-dimethylanilino)fluoran,
2-ethylamino-6-(N-ethyl-2,4-dimethylanilino)fluoran,
2-dimethylamino-6-(N-methylanilino)fluoran,
2-dimethylamino-6-(N-ethylanilino)fluoran,
2-diethylamino-6-(N-methyl-p-toluidino)fluoran,
2-diethylamino-6-(N-ethyl-p-toluidino)fluoran,
2-dipropylamino-6-(N-methylanilino)fluoran,
2-dipropylamino-6-(N-ethylanilino)fluoran,
2-amino-6-(N-methylanilino)fluoran,
2-amino-6-(N-ethylanilino)fluoran,
2-amino-6-(N-propylanilino)fluoran,
2-amino-6-(N-methyl-p-toluidino)fluoran,
2-amino-6-(N-ethyl-p-toluidino)fluoran,
2-amino-6-(N-propyl-p-toluidino)fluoran,
2-amino-6-(N-methyl-p-ethylanilino)fluoran,
2-amino-6-(N-methyl-p-ethylanilino)fluoran,
2-amino-6-(N-ethyl-p-ethylanilino)fluoran,
2-amino-6-(N-propyl-p-ethylanilino)fluoran,
2-amino-6-(N-methyl-2,4-dimethylanilino)fluoran,
2-amino-6-(N-ethyl-2,4-dimethylanilino)fluoran,
2-amino-6-(N-propyl-2,4-dimethylanilino)fluoran,
2-amino-6-(N-methyl-p-chloroanilino)fluoran,
2-amino-6-(N-ethyl-p-chloroanilino)fluoran,
2-amino-6-(N-propyl-p-chloroanilino)fluoran,
2,3-dimethyl-6-dimethylaminofluoran,
3-methyl-6-(N-ethyl-p-toluidino)fluoran,
2-chloro-6-diethylaminofluoran,
2-bromo-6-diethylaminofluoran,
2-chloro-6-dipropylaminofluoran,
3-chloro-6-cyclohexylaminofluoran,
3-bromo-6-cyclohexylaminofluoran,
2-chloro-6-(N-ethyl-N-isoamylamino)fluoran,
2-chloro-3-methyl-6-diethylaminofluoran,
2-anilino-3-chloro-6-diethylaminofluoran,
2-(o-chloroanilino)-3-chloro-6-cyclohexylaminofluoran,
2-(m-trifluoromethylanilino)-3-chloro-6-diethylaminofluoran,
2-(2,3-dichloroanilino)-3-chloro-6-diethylaminofluoran,
1,2-benzo-6-diethylaminofluoran,
1,2-benzo-6-(N-ethyl-N-isoamylamino)fluoran,
1,2-benzo-6-dibutylaminofluoran,
1,2-benzo-6-(N-methyl-N-cyclohexylamino)fluoran,
1,2-benzo-6-(N-ethyl-N-toluidino)fluoran, and so on.
Other examples of the color producing agents which may be preferably used in the present invention include:
2-anilino-3-methyl-6-(N-2-ethoxypropyl-N-ethylamino)fluoran,
2-(p-chloroanilino)-6-(N-n-octylamino)fluoran,
2-(p-chloroanilino)-6-(N-n-palmitylamino)fluoran,
2-(p-chloroanilino)-6-(di-n-octylamino)fluoran,
2-benzoylamino-6-(N-ethyl-p-toluidino)fluoran,
2-(o-methoxybenzoylamino)-6-(N-methyl-p-toluidino)fluoran,
2-dibenzylamino-4-methyl-6-diethylamino)fluoran,
2-dibenzylamino-4-methoxy-6-(N-methyl-p-toluidino)fluoran,
2-dibenzylamino-4-methyl-6-(N-ethyl-p-toluidino)fluoran,
2-(.alpha.-phenylethylamino)-4-methyl-6-diethylaminofluoran,
2-(p-toluidino)-3-(t-butyl)-6-(N-methyl-p-toluidino)fluoran,
2-(o-methoxycarbonylamino)-6-diethylaminofluoran,
2-acetylamino-6-(N-methyl-p-toluidino)fluoran,
3-diethylamino-6-(m-trifluoromethylanilino)fluoran,
4-methoxy-6-(N-ethyl-p-toluidino)fluoran,
2-ethoxyethylamino-3-chloro-6-dibutylaminofluoran,
2-dibenzylamino-4-chloro-6-(N-ethyl-p-toluidino)fluoran,
2-(.alpha.-phenylethylamino)-4-chloro-6-diethylaminofluoran,
2-(N-benzyl-p-trifluoromethylanilino)-4-chloro-6-diethylaminofluoran,
2-anilino-3-methyl-6-pyrrolidinofluoran,
2-anilino-3-chloro-6-pyrrolidinofluoran,
2-anilino-3-methyl-6-(N-ethyl-N-tetrahydrofurfurylamino)fluoran,
2-mesidino-4',5'-benzo-6-diethylaminofluoran,
2-(m-trifluoromethylanilino)-3-methyl-6-pyrrolidinofluoran,
2-(.alpha.-naphtylamino)-3,4-benzo-4'-bromo-6-(N-benzyl-N-cyclohexylamino)fluoran,
2-piperidino-6-diethylaminofluoran,
2-(N-n-propyl-p-trifluoromethylanilino)-6-morphorinofluoran,
2-(di-N-p-chlorophenyl-methylamino)-6-pyrrolidinofluoran,
2-(N-n-propyl-m-trifluoromethylanilino)-6-morphorinofluoran,
1,2-benzo-6-(N-ethyl-N-n-octylamino)fluoran,
1,2-benzo-6-diallylamino)fluoran,
1,2-benzo-6-(N-ethoxyethyl-N-ethylamino)fluoran, benzoleuco-methylene blue,
2-�3,6-bis(diethylamino)!-6-(o-chloroanilino)xanthyl benzoic acid lactam,
2-�3,6-diethylamino!-9-(o-chloroanilino)xanthyl benzoic acid lactam,
3,3-bis(p-dimethylaminophenyl)-phthalide,
3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (Crystal violet lacton),
3,3-bis-(p-dimethylaminophenyl)-6-diethylaminophthalide,
3,3-bis-(p-dimethylaminophenyl)-6-chlorophthalide,
3,3-bis-(p-dibutylaminophenyl)phthalide,
3-(2-methoxy-4-dimethylaminophenyl)-3-(2-hydroxy-4,5-dichlorophenyl)phthalide,
3-(2-hydroxy-4-dimethylaminophenyl)-3-(2-methoxy-5-chlorophenyl)phthalide,
3-(2-hydroxy-4-dimethoxyaminophenyl)-3-(2-methoxy-5-chlorophenyl)phthalide,
3-(2-hydroxy-4-dimethylaminophenyl)-3-(2-methoxy-5-nitrophenyl)phthalide,
3-(2-hydroxy-4-diethylaminophenyl)-3-(2-methoxy-5-methylphenyl)phthalide,
3-(2-methoxy-4-dimethylaminophenyl)-3-(2-hydroxy-4-chloro-5-methoxyphenyl)phthalide,
3,6-bis(dimethylamino)fluorenespiro(9,3')-6'-dimethylaminophthalide,
3-(1-ethyl-2-methylindole-3-yl)-3-(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide,
3-(1-octyl-2-methylindole-3-yl)-3-(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide,
3-(1-ethyl-2-methylindole-3-yl)-3-(2-ethoxy-4-diethylaminophenyl)-7-azaphthalide,
3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide,
3,3-bis(2-ethoxy-4-diethylaminophenyl)-7-azaphthalide,
6'-chloro-8'-methoxy-benzoindolino-spiropyran,
6'-bromo-2'-methoxy-benzoindolino-spiropyran, and so on.
The thermally reversible color forming composition according to the present invention has a characteristic in that there are a color forming state and a non-color state depending on a temperature and/or a cooling rate after the composition is heated to a certain temperature.
FIG. 1 is a graph showing the relationship between a color density and a temperature of the thermally reversible color forming composition according to the present invention. As shown in FIG. 1, by heating the composition in a non-color state, indicated by the letter A, a coloration reaction takes place at a temperature, T.sub.1, at which the composition starts to melt, and the composition enters into a color forming state (liquid) indicated by B. From this color forming state, B, if the composition is cooled rapidly, the colored state of the composition may be maintained even at a room temperature and the composition enters into a color forming state (solid) (i.e., most of the cases it is considered as a solid state) indicated by C. On the other hand, if the composition is cooled gradually from the color forming state B, its color is lost during the temperature decline and the composition reverts to the non-color state A (i.e., the original state) or enters into a state in which its color density is relatively low compared with the color forming state C.
When the temperature of the composition is increased again from the color forming state C, a color deletion of the composition starts at a temperature, T.sub.2, which is a temperature lower than T.sub.1, as indicated by a dotted line (from D to E), and if the temperature is lowered from the point E, the composition reverts to the non-color state A (the original state). Thus, the thermally reversible color forming composition according to the present invention may have either a colored state or a non-colored state when it is in a solid state, depending on the cooling rate from the melting liquid state.
The actual color forming temperature and color deletion temperature, respectively, varies depending on the combination of the color producing agent and the color developer actually used. Thus, a suitable combination of the color producing agent and the color developer may be selected according to the desired temperature for color formation and/or color deletion. Also, the color density of the composition in the color forming state (liquid) and that of the composition in the color forming state (solid) are not always the same and may be different depending on such factors as the combination of the color producing agent and the color developer, etc.
In the color forming state C, the molecules of the color producing agent and those of the color developer are mixed in a state (solid state in most cases, as mentioned above) in which they may be contacted and thus reacted with each other. In this state, the color producing agent and the color developer are cohered and the color forming state is maintained. It is considered that the stability in color formation of the compound according to the present invention depends on the cohesive structure of the color producing agent and the color developer.
In the non-color state A, on the other hand, the color producing agent and the color developer are phase-separated. In this state, molecules of at least one of the color producing agent and the color developer forms domains or is crystallized and it is considered that the composition is stabilized by a separation of the color producing agent from the color developer due to this formation of domains or crystals. According to the present invention, a complete deletion of colors is often performed by the phase separation of the color producing agent from the color developer and the crystallization of the color developer. Both the deletion of color from the color forming state B due to a gradual cooling and the deletion of color from the color forming state C due to a temperature increase followed by a temperature decrease shown in FIG. 1 are caused by the phase-separation of the constituents of the composition or the crystallization of the color developer, both of which involve an alteration of cohesive structure of the molecules.
When the thermally reversible color forming composition of the present invention is used in a thermally reversible recording medium, a colored image may be produced by heating the medium (composition) to a temperature at which the composition of the present invention melts by using a heating means such as a thermal head and then rapidly cooling the medium. The deletion of the produced colored image may be performed by gradually cooling the medium (composition) from a heating state or by heating the medium (composition) to a temperature a little less than the coloration temperature of the composition. This means that the composition is temporarily maintained at a temperature at which the composition is phase-separated or at least one of the color producing agent and the color developer is crystallized. The reason that the medium (composition) is rapidly cooled to form a colored image is that the medium (composition) is not maintained at the phase-separation temperature or the crystallization temperature. The terms "rapid cooling" and "gradual cooling" used in this specification are relative terms and the boundary between the two terms varies depending on a combination of the color producing agent and the color developer used.
Although the ratio of the color producing agent and the color developer present in the thermally reversible color forming composition according to the present invention varies depending on the combination of the two compounds, it is generally 1:0.1-20 and preferably 1:0.2-10. If the amount of the color developer is more or less than the above range, the density of formed color will be decreased and the formation of resulting colored image become problematic.
The thermally reversible recording medium according to the present invention comprises a supporting layer and a recording layer formed on the supporting layer, the recording layer including the above-explained thermally reversible color forming composition as a main component.
Any materials which can support the recording layer can be used as the supporting layer. Such materials include paper, resin film, synthesized paper, metal foil, glass and composite materials made of these.
Any kind of recording layer which contains the thermally reversible color forming composition of the present invention may be used for the thermally reversible recording medium. In general, the recording layer is comprised of a binder resin in which fine particles of a color producing agent and a color developer are dispersed homogeneously. The particles of the color producing agent and the color developer may be particulate particles, however, they are preferably in a composite state. This state of the particles may be achieved by melting or dissolving the color producing agent and the color developer.
The thermally reversible recording medium may be formed by dissolving and dispersing each of the constituents of the recording layer in a respective solvent and then mixing each of the solutions followed by an application of the resulting solution onto a supporting layer and drying, or by mixing each of the constituents of the recording layer in a solvent and then applying the resulting dispersed or dissolved solution onto a supporting layer followed by drying. It is possible to envelop the color producing agent and the color developer in microcapsules.
Additives which may improve a color forming/deleting characteristic or an application characteristic of the recording layer can be added to the thermally reversible recording medium of the present invention if necessary. Examples of such additives include dispersing agents, surfactants, conductivity agents, fillers, lubricants, anti-oxidants, light stabilizers, ultraviolet ray absorbents, color forming stabilizers, and color deletion accelerating agents.
Examples of the binder resin which may be used in the recording layer include poly(vinyl chloride), poly(vinyl acetate), vinyl chloride-vinyl acetate copolymer, ethyl cellulose, polystyrene, styrene copolymer, phenoxy resin, polyester, aromatic polyester, polyurethane, polycarbonate, polyacrylate, polymethacrylate, acrylic acid copolymer, maleic acid copolymer, poly(vinyl alcohol), denatured poly(vinyl alcohol), hydroxyethyl cellulose, carboxymethyl cellulose, starch and so on. These binder resins are capable of maintaining a homogeneously dispersed state of each of the constituents of the compositions used for the recording layer even when a thermal energy is applied to the recording layer for recording/deleting an image. Therefore, it is preferable that a resin having an excellent heat resistance capacity is used for the binder resin. Also, it is possible to cross-link a binder resin using, for instance, heat, ultraviolet ray or an electron beam in order to increase its heat resistance.
As mentioned above, the thermally reversible recording medium according to the present invention is basically comprised of a supporting layer and a recording layer formed on the supporting layer. However, the thermally reversible recording medium of the present invention may further include protective layers, adhesive layers, intermediate layers, undercoating layers, backcoating layers, etc., in order to improve its performance as a recording medium.
Now, a surface of the recording layer may be deformed due to heat and/or pressure when a thermal head is used for an image formation. In order to prevent the deformation of the recording layer, it is preferable to provide a protective layer with the recording layer. Examples of the substances which may be used for the protective layer include poly(vinyl alcohol), styrene-maleic anhydride copolymer, carboxy denatured polyethylene, melamine-formaldehyde resin, urea-formaldehyde resin, ultraviolet-cure resin and electron beam-cure resin. Also, it is possible to include additives such as an ultraviolet absorber in the protective layer.
It is preferable to provide an intermediate layer between the recording layer and the protective layer in order to improve adhesibility of the recording layer and the protective layer, to prevent a denaturation of the recording layer due to the application of the protective layer, and to prevent a transfer of the additives contained in the protective layer to the recording layer. Also, it is preferable to use a resin which has a low oxygen permeability for the protective layer and the intermediate layer provided on the recording layer because, in that manner, it is possible to prevent or decrease oxidation of the color producing agent and the color developer contained in the recording layer.
Moreover, it is possible to provide an adiabatic undercoating layer between the supporting layer and the recording layer in order to effectively use the heat applied to the recording medium. The adiabatic undercoating layer may be formed by applying organic or inorganic hollow fine particles using binder resin. Further, it is possible to form an undercoating layer which improves adhesibility of the supporting layer with the recording layer or prevents permeation of recording layer constituents into the supporting layer.
The same resin used for the recording layer may also be used for the intermediate layer and the undercoating layer. Moreover, it is possible to include filler such as calcium carbonate, magnesium carbonate, titanium oxide, silicon oxide, aluminium hydroxide, kaolin and talc in the protective layer, intermediate layer, recording layer and undercoating layer. Other additives such as lubricants and surfactants may also be included in such layers.
In order to produce a colored image using the thermally reversible medium according to the present invention, the medium is heated to a temperature higher than its coloration temperature and then it is rapidly cooled. In practice, when the recording layer is heated for a relatively short time by a thermal head or laser beam, the temperature of a portion of the recording layer may be increased locally to a temperature higher than its coloration temperature and as the application of the heat is stopped, the temperature of the portion of the recording layer is lowered rapidly by diffusion of heat and the colored image is fixed.
In order to delete the formed image, on the other hand, it is necessary to heat the recording layer for a relatively long time using an appropriate heat source and then cool it, or temporarily heat the recording layer at a temperature a little lower than its coloration temperature. That is, if the recording layer is heated for a relatively long time, the temperature of a large area of the recording medium is increased and so it takes a relatively long time to decrease the temperature of it. Thus, the colored image of the recording layer may be deleted during the slow cooling process.
Examples of the above-mentioned heat source that may be used for the slow cooling process of the recording medium include a thermal roller, a thermal stamp and thermal heat. It is possible to use a thermal head for long-time heating. In order to control the temperature of the thermal head, an applied voltage or pulse width for the thermal head may be adjusted so that an applied energy to the recording layer become a little lower than the applied energy which is used during a recording process. By using this method, only a thermal head is necessary for formation/deletion of colored images and thus a so-called overwriting can be performed.
EXAMPLES
The present invention is described in detail using examples hereinafter. Note that the terms "parts" and "%" used in the following examples are based on weight unless otherwise it is noted.
Example 1
A thermally reversible color forming composition according to the present invention was prepared using 2-anilino-3-methyl-6-dibutylaminofluoran as a color producing agent and N'-n-octadecylureido acetic acid as a color developer. The actual preparation procedure of the composition was carried out as follows. First, a mixture of the color producing agent and the color developer (1:3 molar ratio) was ground in a mortar and the powder of the mixture obtained was put on a glass plate with thickness of 1.2 mm. The glass plate was heated to a temperature of 190.degree. C. using a hot plate and the mixture was melted. A cover glass was put on the melted mixture in order to uniformly spread the mixture and the glass plate together with the cover glass was immediately immersed in ice water to rapidly decrease the temperature of the mixture. After that the glass plate was taken out of the water and dried to obtain the composition of the present invention as a colored thin film.
When this colored composition was put on a hot plate heated to a temperature of 120.degree. C., the color of the composition immediately disappeared. After that, when this non-color composition was heated to a temperature of 190.degree. C., the composition turned into a black color.
Thus, it was confirmed that the composition according to the present invention had a reversible color formation/deletion characteristic from the above experiment.
Example 2
The above described procedure used in the Example 1 was repeated except that 3-(N'-n-octadecylureido)propionic acid was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 3
The above described procedure used in the Example 1 was repeated except that 4-(N'-n-octadecylureido)butyric acid was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 4
The above described procedure used in the Example 1 was repeated except that 4-(N'-n-octadecylureido)-3-hydroxybutyric acid was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 5
The above described procedure used in the Example 1 was repeated except that N'-(n-octadecylaminocarbonyl)glycylglycine was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 6
The above described procedure used in the Example 1 was repeated except that N'-(n-octadecylaminocarbonyl)glycylglycylglycine was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 7
The above described procedure used in the Example 1 was repeated except that stearylthioglycolic acid was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 8
The above described procedure used in the Example 1 was repeated except that stearylthiopropionic acid was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 9
The above described procedure used in the Example 1 was repeated except that stearoylglycine was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 10
The above described procedure used in the Example 1 was repeated except that stearoylalanine was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 11
The above described procedure used in the Example 1 was repeated except that monodecylamido adipate was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 12
The above described procedure used in the Example 1 was repeated except that monostearylamido adipate was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 13
The above described procedure used in the Example 1 was repeated except that stearylsulfonyl propionic acid was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 14
The above described procedure used in the Example 1 was repeated except that eicocylsulfonyl propionic acid was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 15
The above described procedure used in the Example 1 was repeated except that stearylsulfonylglycol acid was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 16
The above described procedure used in the Example 1 was repeated except that eicosylsulfonyl glycol acid was used as a color developer instead of N'-n-octadecylureido acetic acid. It was confirmed that the composition prepared in this Example also has the reversible color formation/deletion characteristic.
Example 17
The above described procedure used in the Examples 1-16 was repeated except that 2-anilino-3-methyl-6-N-ethyl-N-p-tolylaminofluoran was used as a color producing agent instead of 2-anilino-3-methyl-6-dibutylaminofluoran. It was confirmed that all the compositions prepared in this Example also has the reversible color formation/deletion characteristic.
Example 18
A solution for applying a thermally reversible recording medium to a recording layer according to the present invention was prepared by a grinding dispersion of the following compounds using a ball mill until a particle size in the range of between 1 and 4 .mu.m was obtained:
______________________________________2-anilino-3-methyl-6-dibutylaminofluoran 2 partsN'-n-octadecylureido acetic acid 8 partsvinyl chloride-vinyl acetate copolymer (Union Carbide Co., 20 partsVYHH)methylethylketone 45 partstoluene 45 parts______________________________________
The solution thus produced was applied to a polyester film of 100 .mu.m thickness using a wired-bar, dried, and a thermally reversible recording medium according to the present invention comprising a recording layer of 6.0 .mu.m thickness was produced.
Example 19
The above described procedure used in the Example 18 was repeated except that 3-(N'-n-octadecylureido)propionic acid was used instead of N'-n-octadecylureido acetic acid and a thermally reversible recording medium of the present invention was prepared.
Example 20
The above described procedure used in the Example 18 was repeated except that 4-(N'-n-octadecylureido)propion was used instead of N'-n-octadecylureido acetic acid and a thermally reversible recording medium of the present invention was prepared.
Example 21
The above described procedure used in the Example 18 was repeated except that 4-(N'-n-octadecylureido)-3-hydroxybutyric acid was used instead of N'-n-octadecylureido acetic acid and a thermally reversible recording medium of the present invention was prepared.
Example 22
The above described procedure used in the Example 18 was repeated except that N'-(n-octadecylaminocarbonyl)glycylglycine was used instead of N'-n-octadecylureido acetic acid and a thermally reversible recording medium of the present invention was prepared.
Example 23
The above described procedure used in the Example 18 was repeated except that N'-(n-octadecylaminocarbonyl)glycylglycylglycine was used instead of N'-n-octadecylureido acetic acid and a thermally reversible recording medium of the present invention was prepared.
Example 24
The above described procedure used in the Example 18 was repeated except that stearoylglycine was used instead of N'-n-octadecylureido acetic acid and a thermally reversible recording medium of the present invention was prepared.
Example 25
The above described procedure used in the Example 18 was repeated except that stearoylalanine was used instead of N'-n-octadecylureido acetic acid and a thermally reversible recording medium of the present invention was prepared.
Example 26
The above described procedure used in the Example 18 was repeated except that monodecylamido adipate was used instead of N'-n-octadecylureido acetic acid and a thermally reversible recording medium of the present invention was prepared.
Example 27
The above described procedure used in the Example 18 was repeated except that monostearylamido adipate was used instead of N'-n-octadecylureido acetic acid and a thermally reversible recording medium of the present invention was prepared.
Example 28
The above described procedure used in the Example 18 was repeated except that stearylsulfonyl propionic acid was used instead of N'-n-octadecylureido acetic acid and a thermally reversible recording medium of the present invention was prepared.
Example 29
The above described procedure used in the Example 18 was repeated except that eicocylsulfonyl propionic acid was used instead of N'-n-octadecylureido acetic acid and a thermally reversible recording medium of the present invention was prepared.
Example 30
The above described procedure used in the Example 18 was repeated except that 2-anilino-3-methyl-6-diethylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and a thermally reversible recording medium of the present invention was prepared.
Example 31
The above described procedure used in the Example 19 was repeated except that 2-anilino-3-methyl-6-diethylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and a thermally reversible recording medium of the present invention was prepared.
Example 32
The above described procedure used in the Example 20 was repeated except that 2-anilino-3-methyl-6-diethylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and a thermally reversible recording medium of the present invention was prepared.
Example 33
The above described procedure used in the Example 21 was repeated except that 2-anilino-3-methyl-6-diethylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and a thermally reversible recording medium of the present invention was prepared.
Example 34
The above described procedure used in the Example 21 was repeated except that 2-anilino-3-methyl-6-N-ethyl-N-p-tolylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and a thermally reversible recording medium of the present invention was prepared.
Example 35
The above described procedure used in the Example 21 was repeated except that 2-(o-chloroanilino)-3-methyl-6-dibutylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and a thermally reversible recording medium of the present invention was prepared.
Example 36
The above described procedure used in the Example 22 was repeated except that 2-anilino-3-methyl-6-diethylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and a thermally reversible recording medium of the present invention was prepared.
Example 37
The above described procedure used in the Example 23 was repeated except that 2-anilino-3-methyl-6-diethylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and a thermally reversible recording medium of the present invention was prepared.
Example 38
The above described procedure used in the Example 18 was repeated except that 2-anilino-3-methyl-6-N-ethyl-N-p-tolylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and stearylthioglycol acid was used instead of N'-n-octadecylureido acetic acid, and a thermally reversible recording medium of the present invention was prepared.
Example 39
The above described procedure used in the Example 18 was repeated except that 2-anilino-3-methyl-6-N-ethyl-N-p-tolylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and eicosylsulfonyl glycol acid was used instead of N'-n-octadecylureido acetic acid, and a thermally reversible recording medium of the present invention was prepared.
Example 40
The above described procedure used in the Example 18 was repeated except that 2-anilino-3-methyl-6-N-ethyl-N-p-tolylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and stearylthioglycol acid was used instead of N'-n-octadecylureido acetic acid, and a thermally reversible recording medium of the present invention was prepared.
Example 41
The above described procedure used in the Example 18 was repeated except that 2-anilino-3-methyl-6-N-ethyl-N-p-tolylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and stearylthiopropionic acid was used instead of N'-n-octadecylureido acetic acid, and a thermally reversible recording medium of the present invention was prepared.
Example 42
The above described procedure used in the Example 18 was repeated except that 2-anilino-3-methyl-6-N-ethyl-N-p-tolylaminofluoran was used instead of 2-anilino-3-methyl-6-dibutylaminofluoran and stearoyl-amino-methyl-thiopropionic acid was used instead of N'-n-octadecylureido acetic acid, and a thermally reversible recording medium of the present invention was prepared.
Using the recording media prepared in each of the Examples 18 to 42, a colored image was obtained by carrying out a printing under the following conditions:
Thermal head dot density: 8 dot/mm,
Applied voltage: 13.3 V, and
Applied Pulse width: 1.2 msec.
The optical color density of the colored image on each of the recording media was measured using the Macbeth densitometer RD-914. Then, the color density of each of the colored recording media after heating it for one second using a thermal inclination detector at the temperature shown in the column of "color deleting temperature" (abbreviated as color dele. temp.) in Table 3 for each Example was measured. The results obtained are also shown in Table 3. As can be seen from Table 3, it is clear that the color density of each of the recording medium according to the present invention is decreased to an almost initial color density level of the medium after the one second of heating. Also, it is shown that stable color formation and deletion can be achieved after 10 times of repeated use. Thus, each the recording media according to the present invention is demonstrated to be a thermally reversible recording medium which can perform a fast speed deletion of colored image.
Comparative Example 1
The above described procedure used in the Example 18 was repeated except that eicosyl phosphonic acid was used as a color developer and 2-anilino-3-methyl-6-(N-ethyl-N-p-tolylamino)fluoran was used as a leuco dye, and a recording medium was prepared. Using this recording medium, formation of a colored image (printing) and deletion of the image were performed in the same manner as described in the Example 18. As shown in Table 3, the color of the medium could not be deleted completely after one second of heating. As a matter of fact, it was necessary to heat the medium for one minute to lower its color density to 0.16 which is almost the same as its initial color density.
Comparative Example 2
The above described procedure used in the Example 18 was repeated except that 2-(eicosylthio) succinic acid was used as a color developer, and a recording medium was prepared. Using this recording medium, formation of a colored image (printing) and deletion of the image were performed in the same manner as described in the Example 18. As shown in Table 3, the color of the medium could not be deleted completely after one second of heating. As a matter of fact, it was necessary to heat the medium for ten seconds to lower its color density to 0.21 which is almost the same as its initial color density.
Comparative Example 3
The above described procedure used in the Example 18 was repeated except that .alpha.-hydroxyoctadecanoic acid was used as a color developer, and a recording medium was prepared. Using this recording medium, formation of a colored image (printing) and deletion of the image were performed in the same manner as described in the Example 18. As shown in Table 3, the color of the medium could not be deleted completely after one second of heating. As a matter of fact, it was necessary to heat the medium for ten seconds to lower its color density to 0.17 which is almost the same as its initial color density.
Comparative Example 4
The above described procedure used in the Example 18 was repeated except that octadecylmalonic acid was used as a color developer and 2-(o-chloroanilino)-6-dibutylaminofluoran was used as a leuco dye, and a recording medium was prepared. Using this recording medium, formation of a colored image (printing) and deletion of the image were performed in the same manner as described in the Example 18. As shown in Table 3, the color of the medium could not be deleted completely after one second of heating. As a matter of fact, one minute of heating was insufficient for the medium to lower its color density to its initial density.
TABLE 3______________________________________ 1st. time Aft. 10 timescolor init. form. dele. form. dele.dele. color color color color colortemp. dens. dens. dens. dens. dens.______________________________________Ex 18 110.degree. C. 0.09 0.71 0.09 0.70 0.09Ex 19 110.degree. C. 0.09 0.82 0.09 0.80 0.10Ex 20 110.degree. C. 0.09 0.84 0.09 0.82 0.10Ex 21 110.degree. C. 0.10 1.16 0.10 1.15 0.11Ex 22 120.degree. C. 0.10 0.72 0.10 0.70 0.11Ex 23 120.degree. C. 0.09 0.68 0.09 0.66 0.10Ex 24 100.degree. C. 0.11 0.92 0.11 0.88 0.11Ex 25 100.degree. C. 0.11 0.86 0.11 0.84 0.11Ex 26 100.degree. C. 0.11 0.77 0.11 0.75 0.11Ex 27 100.degree. C. 0.11 0.83 0.11 0.80 0.11Ex 28 100.degree. C. 0.12 1.05 0.13 1.02 0.13Ex 29 100.degree. C. 0.12 1.12 0.12 1.08 0.12Ex 30 110.degree. C. 0.10 0.74 0.10 0.72 0.11Ex 31 110.degree. C. 0.09 0.85 0.09 0.82 0.10Ex 32 110.degree. C. 0.10 0.89 0.10 0.88 0.10Ex 33 110.degree. C. 0.11 1.21 0.11 1.20 0.12Ex 34 110.degree. C. 0.09 1.10 0.09 1.08 0.10Ex 35 110.degree. C. 0.09 1.08 0.09 1.06 0.11Ex 36 120.degree. C. 0.10 0.77 0.10 0.74 0.11Ex 37 120.degree. C. 0.10 0.71 0.10 0.70 0.11Ex 38 100.degree. C. 0.14 1.45 0.15 1.43 0.15Ex 39 100.degree. C. 0.14 1.58 0.14 1.52 0.14Ex 40 60.degree. C. 0.12 0.82 0.12 0.80 0.12Ex 41 60.degree. C. 0.11 0.81 0.11 0.79 0.11Ex 42 60.degree. C. 0.12 0.86 0.12 0.84 0.12CE 1 80.degree. C. 0.15 1.10 0.45 1.08 0.48CE 2 70.degree. C. 0.20 1.46 0.36 1.43 0.38CE 3 70.degree. C. 0.16 0.39 0.20 0.38 0.21CE 4 70.degree. C. 0.22 1.70 1.29 1.67 1.28______________________________________ (Ex = Example, CE = Comparative Example, color dele. temp. = color deleting temperature, init. color dens. = initial color density, form. color dens. = formed color density, dele. color dens. = deleted color density)
It is obvious that the present invention is not limited to the above-mentioned embodiments, and variations and modifications may be made without departing from the scope of the present invention.

Number	Date	Country
8-035720	Jan 1996	JPX
8-065385	Feb 1996	JPX
8-065386	Feb 1996	JPX
8-065387	Feb 1996	JPX
8-065388	Feb 1996	JPX
8-191557	Jul 1996	JPX
9-020999	Jan 1997	JPX

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Thermally reversible color forming composition and thermally reversible recording medium using the thermally reversible color forming composition

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