CN1771135A - Reversible thermal recording medium - Google Patents
Reversible thermal recording medium Download PDFInfo
- Publication number
- CN1771135A CN1771135A CN 200380110298 CN200380110298A CN1771135A CN 1771135 A CN1771135 A CN 1771135A CN 200380110298 CN200380110298 CN 200380110298 CN 200380110298 A CN200380110298 A CN 200380110298A CN 1771135 A CN1771135 A CN 1771135A
- Authority
- CN
- China
- Prior art keywords
- thermosensitive recording
- reversible thermosensitive
- recording medium
- record
- reversible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/305—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers with reversible electron-donor electron-acceptor compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
A reversible thermal recording medium comprising a support and, superimposed thereon, a reversible thermal recording layer comprising a reversible thermal composition, the reversible thermal composition comprising an electron-donating color-forming compound and an electron-accepting compound and capable of forming relatively colored condition depending on a difference in heating temperature and/or cooling rate after heating, characterized in that the electron-accepting compound is a phenol compound of the general formula: (1) (wherein n is an integer of 1 to 3; X represents a bivalent group containing a N atom or an O atom; R1 represents a substituted or unsubstituted aliphatic hydrocarbon group having 2 or more carbon atoms; and R2 represents a C1-C14 aliphatic hydrocarbon group), and that when the reversible thermal recording medium is printed in an environment of 35 DEG C +- 2 DEG C and 70 to 90% relative humidity, the coloring density is 0.80 or greater while the decoloring density is 0.15 or less.
Description
Technical field
The present invention relates to use utilized and power sub-property colour generation compound and accept the invertibity temperature-sensitive color development composition of the color development reaction between the electronics compound, can form and eliminate the reversible thermosensitive recording medium of chromophore image by control heat energy.
Background technology
In the past, the sub-property colour generation compound of utilization power supply (below, be also referred to as colour former or leuco dye) and accept the electronics compound (below, be also referred to as developer) between the thermal recording material of color development reaction be widely known by the people, progress along with office automatic (OA) change, output paper as fax, word processor, science instrumentation machine etc. in addition, also is widely used as advance payment card or scored card equimagnetic temperature-sensitive card recently.But, these recording mediums in the past that are practical are on environmental problem, again close examination utilize again or the minimizing of use amount etc. extremely urgent, and, owing to be irreversible color development, the image that once writes down can not be eliminated and reused, therefore new information can only be write afterwards and do not had the part of document image, therefore, the area of the part that can write down is restricted.So actual conditions are that perhaps the information content of reduction record is perhaps made card again when not becoming posting field.Thereby, be background with garbage problem or the forest deterioration problem of discussing warmly in recent years, the expectation exploitation is the reversible thermosensitive recording medium of Palingraphia repeatedly.
Therefore, from these requirements, various reversible thermosensitive recording mediums have been proposed.The polymer electrolyte reversible thermosensitive recording medium (with reference to patent documentation 1,2) of the physical change that utilizes transparent gonorrhoea for example, is disclosed.In addition, also proposed to utilize again the dye-type reversible thermosensitive recording medium of chemical change.Particularly, the technology (for example with reference to patent documentation 3) of the combination of gallic acid and phloroglucin as developer of using disclosed, in developer, use the technology (for example with reference to patent documentation 4) of compounds such as phenolphthalein or thymolphthalein, the technology that contains the homogeneous solutrope of colour former and developer and carboxylate in the recording layer is (for example with reference to patent documentation 5,6,7), the technology of use ascorbic acid derivates (for example in developer, with reference to patent documentation 8), the technology of the salt of two (hydroxyphenyl) acetic acid of use or gallic acid and senior aliphatic amine is (for example, with reference to patent documentation 9 in developer, 10) etc.
Have again, present inventors have proposed following scheme: at first, in patent documentation 11, as developer, use has the organic phosphoric acid compound of long-chain fat family alkyl, aliphatic carboxylic acid compound or phenolic compounds, by with its with as the combination of the leuco dye of colour former, can easily carry out color development and colour killing by the heating cooling condition, its color development state and colour killing state can stably keep at normal temperatures, and, can carry out the invertibity temperature-sensitive color development composition of color development and colour killing repeatedly and it is used in the reversible thermosensitive recording medium of recording layer, in addition, then, about having the phenolic compounds of long-chain fat family alkyl, the material that has proposed to use specific structure again is (for example, with reference to patent documentation 12,13).
Yet, in actual use, though can under environment, use from low temperature and low humidity to hot and humid broad range, but, have and under low temperature and low humidity, cause easily and eliminate badly, and cause problems such as color development is bad under hot and humid, may not bring gratifying result.
In addition; in patent documentation 14, disclose by in the intermediate layer or protective layer add certain specific inorganic pigment; can make the moisture-proof keeping quality become good; but present situation is not reach and improve because the color development under the elimination under the low temperature and low humidity that the typewriting of elimination repeatedly under the environment that reality is used causes is bad or hot and humid is bad.
Moreover, appeal high speed, the miniaturization of printer in recent years, in the reversible thermosensitive recording material, colour killing is significant from the type of carrying out with ceramic heater to the transformation of the type of carrying out with thermal head, therefore expects the high speed of colour killing.
Patent documentation 1: the spy opens clear 63-107584 communique
Patent documentation 2: the spy opens flat 4-78573 communique
Patent documentation 3: the spy opens clear 60-193691 communique
Patent documentation 4: the spy opens clear 61-237684 communique
Patent documentation 5: the spy opens clear 62-138556 communique
Patent documentation 6: the spy opens clear 62-138568 communique
Patent documentation 7: the spy opens clear 62-140881 communique
Patent documentation 8: the spy opens clear 63-173684 communique
Patent documentation 9: the spy opens flat 2-188293 communique
Patent documentation 10: the spy opens flat 2-188294 communique
Patent documentation 11: the spy opens flat 5-124360 communique
Patent documentation 12: the spy opens flat 6-210954 communique
Patent documentation 13: the spy opens flat 10-95175 communique
Patent documentation 14: the spy opens flat 10-100541 communique
Therefore, the present invention is, that improvement promptly became problem in the past because bad at the bad or hot and humid color development of eliminating repeatedly under the environment that reality is used under the low temperature and low humidity that typewriting causes down of elimination, can provide stable quality, the selection invention of all right high speed colour killing.
And, problem of the present invention is, provide color development concentration and colour killing concentration not to be subjected to humidity effect, even have excellent high-contrast and use repeatedly, to the generation of the percussion mark (beating こ ん) of recording medium or change in concentration also seldom, excellent in te pins of durability and can use the reversible thermosensitive recording medium of the high speed colour killing excellence of thermal head colour killing.
Summary of the invention
Present inventors think in the reversible color development colour killing phenomenon of the composition of such colour former and developer, it is important making the ability and the intermolecular aggegation equilibrium of forces of the colour former color development of the developer with long fatty group, has therefore studied the compound of various structures.It found that, uses the phenolic compounds with ad hoc structure as developer, in addition, contain have the particular functional group compound as colour killing promoter, thus, can solve above-mentioned problem.
Promptly, above-mentioned problem can solve by following main points of the present invention: and (1) " a kind of reversible thermosensitive recording medium; this reversible thermosensitive recording medium is the reversible thermosensitive recording medium that has the reversible thermosensitive recording layer on support; described reversible thermosensitive recording layer contains and uses the sub-property colour generation compound of power supply and accept the electronics compound; and can relatively form the reversibly hot sensitive composition of color development state by the difference of the cooling velocity after heating-up temperature and/or the heating; it is characterized in that; this accepts the electronics compound is the phenolic compounds of representing with following general formula (1), and with this reversible thermosensitive recording medium at 35 ℃ ± 2 ℃, color development concentration when the environment of relative humidity 70%～90% is printed down is more than 0.80 or 0.80, colour killing concentration is below 0.15 or 0.15
(in the formula, n represents 1～3 integer, and X represents to contain the divalent group of N atom or O atom.In addition, R
1Expression can have substituent carbon number 2 or 2 above aliphatic alkyls, R
2The aliphatic alkyl of expression carbon number 1～14.) "; (2) " reversible thermosensitive recording medium according to above-mentioned (1) record is characterized in that the above-mentioned electronics compound of accepting is in general formula (1), to have R
1For carbon number is 10～16 aliphatic alkyl, R
2For carbon number 8～14 aliphatic alkyl R
1And R
2Phenolic compounds ", (3) " reversible thermosensitive recording medium according to above-mentioned (1) or (2) record is characterized in that the above-mentioned electronics compound of accepting is that in general formula (1), X is the phenolic compounds of urea base "; (4) " reversible thermosensitive recording medium according to any record in above-mentioned (1) Xiang Zhidi (3) item is characterized in that above-mentioned reversible thermosensitive recording layer contains the resin that is in cross-linked state "; (5) " according to above-mentioned (4) the record reversible thermosensitive recording medium, it is characterized in that, in the above-mentioned reversible thermosensitive recording layer hydroxyl value of contained resin be 70 (KOHmg/g) or more than 70 (KOHmg/g) "; (6) " reversible thermosensitive recording medium according to above-mentioned (4) or (5) record is characterized in that contained resin is the many alcohol resins of acrylic compounds in the above-mentioned reversible thermosensitive recording layer "; (7) " according to the reversible thermosensitive recording medium of any record in above-mentioned (1) Xiang Zhidi (3) item; it is characterized in that; the gel fraction of above-mentioned resin is more than 30% or 30% ", (8) " according to reversible thermosensitive recording medium of any record in above-mentioned (1) Xiang Zhidi (7) item; it is characterized in that; as colour killing promoter, comprise compound " with secondary amide base; (9) " according to the reversible thermosensitive recording medium of any record among above-mentioned (1) Xiang Zhidi (7); it is characterized in that, this recorded matter also contain have one or more-NHCO-base in the molecule at least ,-the colour killing promoter of OCONH-base "; (10) " according to the reversible thermosensitive recording medium of above-mentioned (9) record; it is characterized in that; have in the above-mentioned molecule one or more-NHCO-base ,-the colour killing promoter of OCONH-base is with in the compound of general formula (2)～(8) expression any one
R
1-NHCO-R
2…(2)
R
1-NHCO-R
3-OCNH-R
2…(3)
R
1-CONH-R
3-HNOC-R
2…(4)
R
1-NHOCO-R
2…(5)
R
1-NHOCO-R
3-OCOHN-R
3…(6)
R
1-OCONH-R
3-HNOCO-R
2…(7)
(in the formula, R
1, R
2, R
4The expression carbon number is 7～22 straight chained alkyl, branch's alkyl, unsaturated alkyl, R
3The expression carbon number is 1～10 divalent functional group, R
5The expression carbon number is 4～10 3 valency functional groups.) "; (11) " according to the reversible thermosensitive recording medium of any record in above-mentioned (1) Xiang Zhidi (10) item; it is characterized in that; the protective layer that this heat sensitive recording layer of protection is used is set on above-mentioned reversible thermosensitive recording layer, and this protective layer contains the resin that is in cross-linked state ".
In addition, above-mentioned problem can also solve by following main points of the present invention: (12) " a kind of parts with information storage part; it is characterized in that; these parts have information storage part and reversible display part, this reversible display part contain the reversible thermosensitive recording medium of any record in above-mentioned (1) Xiang Zhidi (11) at least "; (13) " parts with information storage part according to above-mentioned (12) record is characterized in that above-mentioned parts with information storage part and reversible display part are any one in card, disk, cartridge or the cassette tape ".
In addition, above-mentioned problem can solve by following main points of the present invention: (14) " a kind of reversible thermosensitive recording label; it is characterized in that; with the opposite face of the face of the reversible thermosensitive recording layer of the support that form to constitute above-mentioned reversible thermosensitive recording medium on bond layer or adhesive phase are set, described reversible thermosensitive recording medium is the reversible thermosensitive recording medium of any record in above-mentioned (1) Xiang Zhidi (11) ".
In addition, above-mentioned problem can solve by following main points of the present invention: (15) " according to the parts with information storage part of above-mentioned (12) or (13) record; it is characterized in that, are provided with the reversible display part of the reversible thermosensitive recording label that has used above-mentioned (14) record ".
In addition, above-mentioned problem can solve by following main points of the present invention: (16) " a kind of image processing method; it is characterized in that; this method is used any parts of being put down in writing with information storage part and reversible display part in the reversible thermosensitive recording label of the reversible thermosensitive recording medium of any record in above-mentioned (1) Xiang Zhidi (11), above-mentioned (14) record or above-mentioned (12), (13), (15) item, carries out the formation and/or the elimination of image by the reversible thermosensitive recording layer that heats this reversible display part "; (17) " image processing method according to above-mentioned (16) record is characterized in that, uses thermal head to form image at above-mentioned reversible display part "; (18) " image processing method according to above-mentioned (16) record is characterized in that, with thermal head or ceramic heater removal of images ".
Have again, above-mentioned problem can solve by following main points of the present invention: (19) " a kind of image processing apparatus; it is characterized in that; this device is the reversible thermosensitive recording medium that loads any record in above-mentioned (1) Xiang Zhidi (11); the reversible thermosensitive recording label of above-mentioned (14) record; or above-mentioned (12); (13), (15) any parts of being put down in writing in the item with information storage part and reversible display part, possessing the device that carries out image formation and/or eliminate forms "; (20) " according to above-mentioned (19) the image processing apparatus of being put down in writing, it is characterized in that, image processing system is a thermal head "; (21) " according to above-mentioned (19) the image processing apparatus of being put down in writing, it is characterized in that image eraser is thermal head or ceramic heater ".
The simple declaration of accompanying drawing
Fig. 1 is the figure that the color development colour killing characteristic of invertibity temperature-sensitive color development composition of the present invention is shown.
Fig. 2 illustrates the figure that reversible thermosensitive recording label is attached to the example on the cartridge of MD.
Fig. 3 illustrates the figure that reversible thermosensitive recording label is attached to the example on the CD-RW.
Fig. 4 is the figure that the example that uses as the display label of videocassette is shown.
Fig. 5 is the figure that the example of image processing apparatus of the present invention is shown.
The preferred plan that carries out an invention
In the reversible thermosensitive recording medium that uses developer in the past,, then there is the problem of color development concentration reduction and so on if under hot and humid environment, eliminate typewriting.Because reversible thermosensitive recording medium can relatively form color development state and colour killing state by the cooling velocity after heating-up temperature and/or the heating, therefore when cooling velocity is chilling, forms the color development state, forms the colour killing state during slow cooling.So the image under hot environment forms easily and moves to the slow cooling state, color development concentration is reduced.In addition, under high humidity environment, excessive hydrone can enter into reversible thermosensitive recording medium inside, owing to have developer and hydrogen bond, then hinders the open loop of leuco dye, and color development concentration is further reduced.Therefore, even reversible thermosensitive recording medium up to now can obtain color development concentration under ambient temperature and moisture be more than 0.8 or 0.8, colour killing concentration is below 0.15 or 0.15, but issues colour saturation less than 0.8 at hot and humid environment, can not obtain stable chromophore image.
What present inventors studied found that, by using the developer of above-mentioned general formula (1), is more preferably the compound of general formula (9) expression, can address the above problem a little.
(in the formula, m represents 10～16, and n represents 7～13.)
Promptly, with the developer of the general formula (1) that uses among the present invention, be more preferably general formula (9) though the reversible thermosensitive recording medium of the compound of expression near 35 ℃ or 35 ℃ of the temperature, under the environment of relative humidity 70%RH～90%RH, eliminate typewriting repeatedly, also with under ambient temperature and moisture, carry out resulting color development concentration and do not have difference, and, can obtain can not causing that colour killing is bad, the reversible thermosensitive recording medium of contrast excellence.That is, the color development concentration that reversible thermosensitive recording medium of the present invention has when typewriting under 35 ℃ ± 2 ℃, the environment of relative humidity 70%RH～90%RH at least is more than 0.80 or 0.80, and colour killing concentration is the performance below 0.15 or 0.15.
Have the urea base in the compound structure of general formula (9) expression, have interaction with hydrone from its hydrogen bond ability.In addition, the developer of general formula (9) causes by heat effect and the state variation of color development state and colour killing state shows the invertibity function thus, and the state variation of this moment is considered to utilize the elements collection power of the hydrogen bond ability of urea base to bring into play effect.Therefore, at the high environment of relative humidity, exist in a large number in the environment of hydrone around promptly, the urea base of developer itself each other hydrogen bond and the hydrogen bond of hydrone produce jointly, this is considered to destroy the major reason of the balance of color development state and colour killing state, thereby causes that color development is bad.
Therefore, in the developer of general formula (9), under the high environment of relative humidity,, must reduce interaction with hydrone for making color development in good condition.So in general formula (9), present inventors carry out various variations with the size of m, n, during the interactional situation of research and water, find m less than 10 o'clock, big with the interaction of hydrone, and m surpasses at 10 o'clock, diminish with the interaction of hydrone.In addition, present inventors find that also n is big with the interaction of hydrone greater than 13 o'clock, and n be 13 or 13 when following and the interaction of hydrone diminish.That is to say, the developer of general formula (9) can be by adjusting the influence that m, n adjust hydrone, consequently, even can obtain under the environment of 35 ℃ of temperature, relative humidity 70%RH～90%RH, eliminate typewriting repeatedly, also with under the ambient temperature and moisture environment, carry out resulting color development concentration and do not have difference, and can obtain can not causing that colour killing is bad, the reversible thermosensitive recording medium of contrast excellence.This is the phenomenon that does not have discovery in knowledge in the past, is the phenomenon of at first being found by present inventors.
On the other hand, m surpasses at 16 o'clock, and n is less than 7 o'clock, can maintain little state with the interaction of hydrone, but confirm the phenomenon of the remarkable deterioration of colour killing characteristic, therefore, selects 10～16 as the preferable range of m, and the preferable range of n selects 7～13.
In addition, the detailed mechanism of this phenomenon also imperfectly understands, but the influence of the moisture-absorption characteristics of developer compounds is tangible.
The feature of invertibity temperature-sensitive color development composition of the present invention is that the phenolic compounds that uses above-mentioned general formula (1) expression is as accepting the electronics compound.In above-mentioned general formula (1), aliphatic alkyl can be straight chain also the branch of being can be arranged, can also have unsaturated bond.As the substituting group on the alkyl hydroxyl, halogen atom, alkoxyl etc. are arranged.Because R
1, R
2The carbon atom sum reduce at the stability or the achromicity of 7 or 7 color developments when following, so more than carbon number preferred 8 or 8, be more preferably more than 11 or 11.
As R
1Preference, can enumerate the group that is shown in following table 1.
Table 1
-(CH
2)q- -(CH
2)q-CH＝CH-(CH
2)q′-
Among these, especially preferably-(CH
2) q-.In addition, the q in the formula, q ', q ", q " ' respectively expression satisfy above-mentioned R
1, R
2The integer of carbon number.
In addition, as R
2Preference, can enumerate the group that is shown in following table 2.
Table 2
-(CH
2)q-CH
3 -(CH
2)q-CH＝CH-(CH
2)q′-CH
3
Among these, especially preferably-(CH
2) q-CH
3In addition, the q in the formula, q ', q ", q " ' same as described above.
X represents to contain the divalent group of N atom or O atom, and it is divalent group more than 1 or 1 that preferred expression has the group shown in the table 3 at least.As its example, can enumerate the group that is shown in table 4.Among these, preferably be shown in the group of table 5.
Table 3
Table 4
-CH＝N- -N＝CH-
-O-
Table 5
Have again, as concrete phenolic compounds, can enumerate, for example Yi Xia material.As its example, in table 7 and table 8, enumerated the concrete example of the compound of representing with the general formula in the table 6.In addition, for the compound of representing with other general formulas in the table 6, also can enumerate same material.But the present invention is not limited to these.
Table 6
Table 7
Table 8-1
Table 8-2
If preferred material in the compound shown in table 7 and the table 8 when representing corresponding to the general formula in the table 6, then is that m is equivalent to 5～11, and n-1 is equivalent to 8～13 compound, can enumerate following compound as particularly preferred compound.
Reversible thermosensitive recording medium when the compound that will enumerate as above-mentioned particularly preferred compound uses as developer, color development concentration when any one is typewrited under the environment of hot and humid (35 ℃, 85%RH) is more than 1.00 or 1.00, colour killing concentration is below 0.14 or 0.14, in addition, this performance the time is compared almost with typewriting under the environment of ambient temperature and moisture and is not changed, and shows the very excellent performance of not meeting in the conventional art.
As the colour killing promoter of the present invention's use, by the secondary amide base that uses following general formula to represent, the colour killing promoter of the excellent that can be eliminated.
In the formula, from R
36To R
40Expression can have substituent saturated or undersaturated alkyl, R
36And R
37Also can form ring, the ring of formation also can be got involved nitrogen-atoms, oxygen atom or sulphur atom.In addition, as R
36To R
40In the preferred example that can have substituent alkyl that uses, can be straight chain, also branch can be arranged, also can get involved-O-,-S-,-CO-,-the COO-base.In addition, can also have aromatic ring, aliphatic ring.
Below, the preferred concrete example of the colour killing promoter that can use in the present invention is recited in table 9.But the colour killing promoter compound that can use in the present invention is not limited to these.
Table 9
In the table, n, n ', n ", n " ', n " " integer of expression 0～21.But all be not below 5 or 5.
Have, operable colour killing promoter also can have the associativity group shown in following table 10 more than 1 or 1 among the present invention again.
Table 10
In table 11, enumerate the preference of the colour killing promoter that can use in the present invention.But the colour killing promoter that can use in the present invention is not limited to these compounds.In the table, X represents above-mentioned associativity group, n, n ', n ", n " ', n " " expression 0～21 integer.But all be not below 5 or 5.
Table 11
The concrete example of the promoter of colour killing shown in the table 12, but the present invention is not limited to these compounds.
Table 12
Have again, by using developer simultaneously with above-mentioned feature, with contain at least in molecule as colour killing promoter one or more-NHCO-base ,-compound of OCONH-base, discovery is in the process that forms the colour killing state, can trigger molecule interphase interaction between colour killing promotion property compound and developer, make colour killing speed become especially fast.
As contain at least in the molecule that uses in the present invention one or more-NHCO-base ,-the colour killing promoter of OCONH-base, preferably use the compound of following general formula (2)～(8) expression.
R
1-NHCO-R
2 …(2)
R
1-NHCO-R
3-OCNH-R
2…(3)
R
1-CONH-R
3-HNOC-R
2…(4)
R
1-NHOCO-R
2…(5)
R
1-NHOCO-R
3-OCOHN-R
3…(6)
R
1-OCONH-R
3-HNOCO-R
2…(7)
(in the formula, R
1, R
2, R
4The expression carbon number is 7～22 straight chained alkyl, the alkyl that branch is arranged, unsaturated alkyl, R
3The expression carbon number is 1～10 divalent functional group, R
5The expression carbon number is 4～10 3 valency functional groups).
As R
1, R
2, R
4Preference, can enumerate heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, octadecyl, docosyl, oleyl etc.In addition, as R
3Preference, can enumerate, methylene, ethylidene, propylidene, butylidene, inferior heptyl, hexylidene, Ya Xinji ,-C
3H
6O C
3H
6-Ji ,-C
2H
4O C
2H
4-Ji ,-C
2H
4O C
2H
4O C
2H
4-Ji etc.In addition, as R
5Preference, can enumerate the group that is shown in following table 13.
Table 13
Concrete example as the compound of general formula (2)～(8) expressions can be enumerated following material.
C
11H
23CONHC
12H
25、C
15H
31CONHC
16H
33、C
17H
35CONHC
18H
37、、C
17H
35CONHC
18H
35、C
21H
41CONHC
18H
37、C
15H
31CONHC
18H
37、C
17H
35CONHCH
2HNOCC
17H
35、C
11H
23CONHCH
2HNOCC
11H
23、C
7H
15CONHC
2H
4HNOCC
17H
35、C
9H
19CONHC
2H
4HNOCC
9H
19、C
11H
23CONHC
2H
4HNOCC
11H
23、C
17H
35CONHC
2H
4HNOCC
17H
35、(CH
3)
2CHC
14H
35CONHC
2H
4HNOCC
14H
35(CH
3)
2、C
21H
43CONHC
2H
4HNOCC
21H
43、C
17H
35CONHC
6H
12HNOCC
17H
35、C
21H
43CONHC
6H
12HNOCC
21H
43、C
17H
33CONHCH
2HNOCC
17H
33、C
17H
33CONHC
2H
4HNOCC
17H
33、C
21H
41CONHC
2H
4HNOCC
21H
41、C
17H
33CONHC
6H
12HNOCC
17H
33、C
8H
17NHCOC
2H
4CONHC
18H
37、C
10H
21NHCOC
2H
4CONHC
10H
21、C
12H
25NHCOC
2H
4CONHC
12H
25、C
18H
37NHCOC
2H
4CONHC
18H
37、C
21H
43NHOCC
2H
4CONHC
21H
43、C
18H
37NHOCC
6H
12CONHC
18H
37、C
18H
35NHCOC
4H
8CONHC
18H
35、C
18H
35NHCOC
8H
16CONHC
18H
35、C
12H
25OCONHC
18H
37、C
13H
27OCONHC
18H
37、C
16H
33OCONHC
18H
37、C
18H
37OCONHC
18H
37、C
21H
43OCONHC
18H
37、C
12H
25OCONHC
16H
33、C
13H
27OCONHC
16H
33、C
16H
33OCONHC
16H
33、C
18H
37OCONHC
16H
33、C
21H
43OCONHC
16H
33、C
12H
25OCONHC
14H
29、C
13H
27OCONHC
14H
29、C
16H
33OCONHC
14H
29、C
18H
37OCONHC
14H
29、C
22H
45OCONHC
14H
29、C
12H
25OCONHC
12H
37、C
13H
27OCONHC
12H
37、C
16H
33OCONHC
12H
37、C
18H
37OCONHC
12H
37、C
21H
43OCONHC
12H
37、C
22H
45OCONHC
18H
37、C
18H
37NHCOOC
2H
4OCONHC
18H
37、C
18H
37NHCOOC
3H
6OCONHC
18H
37、C
18H
37NHCOOC
4H
8OCONHC
18H
37、C
18H
37NHCOOC
6H
12OCONHC
18H
37、C
18H
37NHCOOC
8H
16OCONHC
18H
37、C
18H
37NHCOOC
2H
4OC
2H
4OCONHC
18H
37、C
18H
37NHCOOC
3H
6OC
3H
6OCONHC
18H
37、C
18H
37NHCOOC
12H
24OCONHC
18H
37、C
18H
37NHCOOC
2H
4OC
2H
4OC
2H
4OCONHC
18H
37、C
16H
33NHCOOC
2H
4OCONHC
16H
33、C
16H
33NHCOOC
3H
6OCONHC
16H
33、C
16H
33NHCOOC
4H
8OCONHC
16H
33、C
16H
33NHCOOC
6H
12OCONHC
16H
33、C
16H
33NHCOOC
8H
16OCONHC
16H
33、C
18H
37OCOHNC
6H
12NHCOOC
18H
37、C
16H
33OCOHNC
6H
12NHCOOC
16H
33、C
14H
29OCOHNC
6H
12NHCOOC
14H
29、C
12H
25OCOHNC
6H
12NHCOOC
12H
25、C
10H
21OCOHNC
6H
12NHCOOC
10H
21、C
8H
17OCOHNC
6H
12NHCOOC
8H
17、
Table 14
Below, reversible thermosensitive recording medium of the present invention is described in more detail.
As the adhesive resin that is used to form the reversible thermosensitive recording layer, can enumerate, for example, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethyl cellulose, polystyrene, styrene copolymer, phenoxy resin, polyester, aromatic polyester, polyurethane, Merlon, polyacrylate, polymethacrylates, acrylic copolymer, maleic acid analog copolymer, polyvinyl alcohol, modified polyvinylalcohol, hydroxyethylcellulose, carboxymethyl cellulose, starch based etc.
The effect of these adhesive resins is, keeps each material of composition can not depart from owing to the heating of writing down elimination cause, and keeps homodisperse state.Therefore, preferably in adhesive resin, use the high resin of hear resistance.Also can make adhesive resin crosslinked with for example heat, ultraviolet ray, electron ray etc.
As the resin that can be used in cross-linked state of the present invention, particularly, can enumerate, the many alcohol resins of acrylic compounds, polyester polyol, the many alcohol resins of polyurethane, phenoxy resin, polyvinyl butyral resin, cellulose acetate propionate, cellulose acetate butyrate etc. have the resin of the group that reacts with crosslinking agent, or make and have and the monomer of the group of crosslinking agent reaction and the resin that the monomer copolymerization beyond it obtains etc., but the present invention is not limited to these compounds.
Have again, preferably contain the above resin (initial stage use) of hydroxyl value 70 (KOHmg/g) or 70 (KOHmg/g) among the present invention, and can use the many alcohol resins of acrylic compounds, polyester polyol resin, the many alcohol resins of polyurethane etc. as hydroxyl value 70 (KOHmg/g) or the above resin of 70 (KOHmg/g), but, particularly, preferably use the many alcohol resins of acrylic compounds from the having good stability of color development, viewpoint that achromicity is good.As hydroxyl value is 70 (KOHmg/g) or more than 70 (KOHmg/g), preferred especially 90 (KOHmg/g) or more than 90 (KOHmg/g).Because the size of hydroxyl value influence crosslink density, thus about the chemical proofing of filming, rerum natura etc.Present inventors find, hydroxyl value is 70 (KOHmg/g) or more than 70 (KOHmg/g), then durability, film coated surface hardness, splitting resistance improve.Can wait by the amount of analyzing residual hydroxyl amount and ehter bond and be confirmed to be that not to be to use hydroxyl value be the reversible thermosensitive recording material of the above resin of 70 (KOHmg/g) or 70 (KOHmg/g).
In addition, in the many alcohol resins of acrylic compounds, because the difference of structure, its characteristic is also different, as carboxylic monomer, can use hydroxyethylmethacry,ate (HEA), hydroxypropyl acrylate (HPA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxy propyl methacrylate (HPMA), 2-hydroxybutyl mono acrylic ester (2-HBA), 1,4-hydroxybutyl mono acrylic ester (1-HBA) etc., but the particularly splitting resistance of when use has the monomer of primary hydroxyl, filming or the viewpoint of good endurance, the preferable methyl 2-hydroxyethyl acrylate.
As the curing agent that can use in the present invention, can enumerate known in the past isocyanates, amine, phenol, epoxide etc.Wherein, preferably use the isocyanates curing agent.The isocyanate ester compound that can here use can be selected from modification bodies such as the urethane-modified body of known isocyanate-monomer, allophanate-modified body, the ester modified body of cyamelide, biuret modified body, carbodiimides modification body, blocked isocyanate.In addition, as the isocyanate-monomer that forms the modification body, can enumerate, toluene support vulcabond (TDI), 4,4 '-methyl diphenylene diisocyanate (MDI), xyxylene vulcabond (XDI), naphthalene diisocyanate (NDI), PPDI (PPDI), durol dimethyl vulcabond (TMXDI), hexylidene-1,6-vulcabond (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI), IPDI (IPDI), Lycine vulcabond (LDI), isopropylidene two (4-cyclohexyl isocyanate) (IPC), cyclohexyl diisocyanate (CHDI), vulcabond tolidine (TODI) etc., but the present invention is not limited to these compounds.
In addition, can use the catalyst that in this reaction, uses as crosslinking accelerator.As crosslinking accelerator, can enumerate, for example, and 1, metallic compounds such as tertiary amines, organo-tin compound such as 4-diaza-dicyclo [2,2,2] octane etc.In addition, the total amount that curing agent is added is carried out cross-linking reaction, also can not carry out cross-linking reaction.That is, can there be unreacted curing agent.Therefore this cross-linking reaction exists unreacted curing agent also not represent to react and does not carry out fully because passing is in time carried out, even detect unreacted curing agent, neither not have the resin of cross-linked state.In addition, be in the method for cross-linked state or non-crosslinked state, can be dipped in the high solvent of dissolubility by filming and distinguish as the polymer of difference among the present invention.That is, the polymer of non-crosslinked state because this polymer is understood stripping to solvent, and can not remain in the solute, therefore, as long as analyze the structure that has or not polymer in the solute.So, if can not confirm to exist in the solute polymer architecture, just we can say that this polymer is in the non-crosslinked state, can distinguish with the polymer phase of cross-linked state.Here, it can be represented with gel fraction.
So-called gel fraction is meant in solvent, and the resin solute is gathered the generation ratio of this gel when generating the state (gel) that solidifies by the forfeiture self-movement that interacts.More than the gel fraction of this resin preferred 30% or 30%, more than the comparative optimization 50% or 50%, be more preferably more than 70% or 70%, more than preferred more especially 80% or 80%.Gel fraction hour because durability reduces repeatedly, therefore, can mix the curable resin that is cured by heat, UV, EB etc. or resin itself is crosslinked for improving gel fraction in resin.
As the assay method of gel fraction, from the support stripping film, measure the initial stage weight of this film, afterwards, film is sandwiched in the 400 purpose woven wires, be dipped in the solvent of the resin of solubilized before crosslinked after 24 hours, carry out vacuum drying, measure dried weight.
The calculating of gel fraction is carried out according to following formula.
Gel fraction (%)=[dry back weight (g)/initial stage weight (g)] * 100
During with this computational methods compute gel fraction, remove the weight of organic low molecular substance particle beyond the resinous principle in the heat-sensitive layer etc., calculate again.At this moment, when not knowing organic low molecular substance weight in advance, can pass through the section of TEM, SEM etc. observes, by at per unit area shared area ratio and resin and organic low molecular substance proportion separately, obtain part by weight, calculate organic low molecular substance weight, obtain the gel fraction value.
In addition; when carrying out said determination; the reversible thermosensitive recording layer is set on support, thereon during other layers such as lamination protective layer; or when having other layers between support and the heat-sensitive layer; as mentioned above; at first observe by the section of above-mentioned TEM, SEM etc.; the thickness of investigation reversible thermosensitive recording layer and other layers; the surface of thickness ratio of pruning other layers; expose the reversible thermosensitive recording laminar surface; peel off the reversible thermosensitive recording layer simultaneously, similarly carry out gel fraction mensuration with the said determination method and get final product.
In addition; in the method; when the upper strata of reversible thermosensitive recording layer has protective layer of comprising ultraviolet curable resin etc. etc.; sneak into for preventing this layer as possible; must be in the thickness ratio of protective layer part of pruning; the reversible thermosensitive recording laminar surface also will be pruned a little, the value of gel fraction is exerted an influence preventing.
The example of the leuco dye that can use in the present invention is listed below, but the present invention is not limited to these.In addition, colourless fuel can be used alone or as a mixture.
2-anilino--3-methyl-glimmering the hydrocarbon of 6-diethylamino, the glimmering hydrocarbon of 2-anilino--3-methyl-6-two (normal-butyl amino), the glimmering hydrocarbon of 2-anilino--3-methyl-6-(N-n-pro-pyl-N-methylamino), the glimmering hydrocarbon of 2-anilino--3-methyl-6-(N-isopropyl-N-methylamino), the glimmering hydrocarbon of 2-anilino--3-methyl-6-(N-isobutyl group-N-methylamino), the glimmering hydrocarbon of 2-anilino--3-methyl-6-(N-n-pentyl-N-methylamino), the glimmering hydrocarbon of 2-anilino--3-methyl-6-(N-sec-butyl-N-methylamino), the glimmering hydrocarbon of 2-anilino--3-methyl-6-(N-n-pentyl-N-ethylamino), the glimmering hydrocarbon of 2-anilino--3-methyl-6-(N-isopentyl-N-ethylamino), the glimmering hydrocarbon of 2-anilino--3-methyl-6-(N-n-pro-pyl-N-isopropyl amino), the glimmering hydrocarbon of 2-anilino--3-methyl-6-(N-cyclohexyl-N-methylamino), the glimmering hydrocarbon of 2-anilino--3-methyl-6-(N-ethyl-para-totuidine base), the glimmering hydrocarbon of 2-anilino--3-methyl-6-(N-methyl-para-totuidine base), 2-(a trichloromethyl anilino-)-3-methyl-glimmering hydrocarbon of 6-diethylamino, 2-(trifluoro (ト リ Off Le ロ ロ) toluidine)-3-methyl-glimmering hydrocarbon of 6-diethylamino, 2-(a trichloromethyl the anilino-)-glimmering hydrocarbon of 3-methyl-6-(N-cyclohexyl-N-methylamino), 2-(2,4-dimethyl benzene amido)-3-methyl-glimmering hydrocarbon of 6-diethylamino, 2-(N-ethyl-para-totuidine the base)-glimmering hydrocarbon of 3-methyl-6-(N-ethylamino), 2-(N-ethyl-para-totuidine the base)-glimmering hydrocarbon of 3-methyl-6-(N-propyl group-para-totuidine base), the glimmering hydrocarbon of 2-anilino--6-(N-n-hexyl-N-ethylamino), 2-(o-chloraniline the base)-glimmering hydrocarbon of 6-diethylamino, 2-(o-chloraniline the base)-glimmering hydrocarbon of 6-dibutylamino, 2-(trifluoro (ト リ Off ロ ロ) the toluidine)-glimmering hydrocarbon of 6-diethylamino, 2,3-dimethyl-glimmering the hydrocarbon of 6-dimethylamino, the glimmering hydrocarbon of 3-methyl-6-(N-ethyl-para-totuidine base), the glimmering hydrocarbon of 2-chloro-6-diethylamino, the glimmering hydrocarbon of 2-bromo-6-diethylamino, the amino glimmering hydrocarbon of 2-chloro-6-dipropyl, the amino glimmering hydrocarbon of 3-chloro-6-cyclohexyl, the amino glimmering hydrocarbon of 3-bromo-6-cyclohexyl, the glimmering hydrocarbon of 2-chloro-6-(N-ethyl-N-isopentyl amino), the 2-chloro-3-methyl-glimmering hydrocarbon of 6-diethylamino, 2-anilino--glimmering the hydrocarbon of 3-chloro-6-diethylamino, the amino glimmering hydrocarbon of 2-(o-chloraniline base)-3-chloro-6-cyclohexyl, 2-(m-trifluoromethyl the anilino-)-glimmering hydrocarbon of 3-chloro-6-diethylamino, 2-(2,3-dichloro-benzenes amido)-the glimmering hydrocarbon of 3-chloro-6-diethylamino, 1,2 benzos-glimmering the hydrocarbon of 6-diethylamino, the glimmering hydrocarbon of 3-diethylamino-6-(m-trifluoromethyl anilino-), 3-(1-ethyl-2 methyl indole-3-yl)-3-(2-ethyoxyl-4-diethylamino phenyl)-4-azepine phthalein ketone, 3-(1-ethyl-2 methyl indole-3-yl)-3-(2-ethyoxyl-4-diethylamino phenyl)-7-azepine phthalein ketone, 3-(1-octyl group-2 methyl indole-3-yl)-3-(2-ethyoxyl-4-diethylamino phenyl)-4-azepine phthalein ketone, 3-(1-ethyl-2 methyl indole-3-yl)-3-(2-methyl-4-diethylamino phenyl)-4-azepine phthalein ketone, 3-(1-ethyl-2 methyl indole-3-yl)-3-(2-methyl-4-diethylamino phenyl)-7-azepine phthalein ketone, 3-(1-ethyl-2 methyl indole-3-yl)-3-(4-diethylamino phenyl)-4-azepine phthalein ketone, 3-(1-ethyl-2 methyl indole-3-yl)-3-(4-N-n-pentyl-N-methylamino phenyl)-4-azepine phthalein ketone, 3-(1-methyl-2 methyl indole-3-yl)-3-(the own oxygen base of 2--4-diethylamino phenyl)-4-azepine phthalein ketone, 3, two (2-ethyoxyl-4-diethylamino the phenyl)-4-azepine phthalein ketone of 3-, 3, two (2-ethyoxyl-4-diethylamino the phenyl)-7-azepine phthalein ketone of 3-.
The colour former that can use in the present invention can also be used alone or as a mixture known in the past leuco dye except that above-mentioned glimmering hydrocarbon compound, azepine phthalein ketonic compound.Its colour former is as follows.
The glimmering hydrocarbon of 2-(to the acetophenone amido)-6-(N-n-pentyl-N-normal-butyl amino), the glimmering hydrocarbon of 2-benzylamino-6-(N-ethyl-para-totuidine base), 2-benzylamino-6-(N-methyl-2,4-dimethyl benzene amido) glimmering hydrocarbon, 2-benzylamino-6-(N-ethyl-2,4-dimethyl benzene amido) glimmering hydrocarbon, the glimmering hydrocarbon of 2-benzylamino-6-(N-methyl-para-totuidine base), the glimmering hydrocarbon of 2-benzylamino-6-(N-ethyl-para-totuidine base), 2-(two pairs of methyl-benzyl the amino)-glimmering hydrocarbon of 6-(N-ethyl-para-totuidine base), 2-(α-phenylethyl the amino)-glimmering hydrocarbon of 6-(N-ethyl-para-totuidine base), the glimmering hydrocarbon of 2-methylamino-6-(methylphenylamine base), the glimmering hydrocarbon of 2-methylamino-6-(N-ethylaniline base), the glimmering hydrocarbon of 2-methylamino-6-(N propyl aniline base), the glimmering hydrocarbon of 2-ethylamino-6-(N-methyl-para-totuidine base), 2-methylamino-6-(N-methyl-2,4-dimethyl benzene amido) glimmering hydrocarbon, 2-ethylamino-6-(N-ethyl-2,4-dimethyl benzene amido) glimmering hydrocarbon, the glimmering hydrocarbon of 2-dimethylamino-6-(methylphenylamine base), the glimmering hydrocarbon of 2-dimethylamino-6-(N-ethylaniline base), the glimmering hydrocarbon of 2-diethylamino-6-(N-methyl-para-totuidine base), the glimmering hydrocarbon of 2-diethylamino-6-(N-ethyl-para-totuidine base), the glimmering hydrocarbon of 2-dipropyl amino-6-(methylphenylamine base), the glimmering hydrocarbon of 2-dipropyl amino-6-(N-ethylaniline base), the glimmering hydrocarbon of 2-amino-6-(methylphenylamine base), the glimmering hydrocarbon of 2-amino-6-(N-ethylaniline base), the glimmering hydrocarbon of 2-amino-6-(N propyl aniline base), the glimmering hydrocarbon of 2-amino-6-(N-methyl-para-totuidine base), the glimmering hydrocarbon of 2-amino-6-(N-ethyl-para-totuidine base), the glimmering hydrocarbon of 2-amino-6-(N-propyl group-para-totuidine base), 2-amino-6-(the N-methyl-to the ethylo benzene amido) glimmering hydrocarbon, 2-amino-6-(the N-ethyl-to the ethylo benzene amido) glimmering hydrocarbon, 2-amino-6-(the N-propyl group-to the ethylo benzene amido) glimmering hydrocarbon, 2-amino-6-(N-methyl-2,4-dimethyl benzene amido) glimmering hydrocarbon, 2-amino-6-(N-ethyl-2,4-dimethyl benzene amido) glimmering hydrocarbon, 2-amino-6-(N-propyl group-2,4-dimethyl benzene amido) glimmering hydrocarbon, the glimmering hydrocarbon of 2-amino-6-(N-methyl-parachloroanilinum base), the glimmering hydrocarbon of 2-amino-6-(N-ethyl-parachloroanilinum base), the glimmering hydrocarbon of 2-amino-6-(N-propyl group-parachloroanilinum base), 1, the glimmering hydrocarbon of 2-benzo-6-(N-ethyl-N-isopentyl amino), 1,2-benzo-glimmering the hydrocarbon of 6-dibutylamino, 1, the glimmering hydrocarbon of 2-benzo-6-(N-methyl-N-cyclohexyl amino), 1, the glimmering hydrocarbon of 2-benzo-6-(N-ethyl-N-toluene amido), other.
In reversible thermosensitive recording medium of the present invention, look necessity and can use in order to improve or to control the coating characteristics of recording layer or the additive of color development colour killing characteristic.These additives have, for example, and surfactant, conductive agent, filler, antioxidant, light stabilizer, color development stabilization agent etc.
The ratio of colour former and developer can be according to the combination of compounds of using in suitable range, but mol ratio roughly is that with respect to colour former 1, developer is 0.1～20 scope, preferred 0.2～10 scope.Developer lacks or how all can occur the problem of the concentration reduction of color development state than this scope.In addition, the ratio of colour killing promoter is with respect to the preferred 0.1 weight % of developer～300 weight %, more preferred 3 weight %～100 weight %.In addition, colour former and developer also can in wrap in the microcapsules and use.The color development composition in the reversible thermosensitive recording layer and the ratio of resin are preferred 0.1～10 with respect to color development composition 1, and than this scope after a little while, the calorific intensity deficiency of reversible thermosensitive recording layer than this scope for a long time, the problem that color development concentration reduces occurs.
In the formation of recording layer, use will comprise above-mentioned developer, colour former, various additive, curing agent and be in the resin of cross-linked state and the mixture of coating fluid solvent evenly mixes and disperses and coating fluid that modulation forms.
As the concrete example of the solvent that can be used for the coating fluid modulation, can give an example out water; Alcohols such as methyl alcohol, ethanol, isopropyl alcohol, n-butanol, the different carbitol of methyl; Ketones such as acetone, 2-butanone, EAK, DAA, isophorone, cyclohexanone; N, dinethylformamide, N, amide-types such as N-dimethylacetylamide; Ether, isopropyl ether, oxolane, 1,4-diox, 3,4-dihydro-ethers such as 2H-pyrans; Glycol ethers such as 2-methyl cellosolve, cellosolvo, butoxy ethanol, glycol dimethyl ether; Glycol ethers acetate esters such as 2-methoxy ethyl acetic acid esters, 2-ethoxyethyl group acetic acid esters, 2-butoxyethyl group acetic acid esters; Ester classes such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethylene carbonate; Arenes such as benzene,toluene,xylene; Aliphatic hydrocarbons such as hexane, heptane, isooctane, cyclohexane; Carrene, 1, halogenated hydrocarbons such as 2-dichloroethanes, dichloropropane, chlorobenzene; Sulfoxide classes such as dimethyl sulfoxide (DMSO); Pyrrolidinone compounds such as N-methyl-2 pyrrolidones, N-octyl group-2 pyrrolidones etc.
The coating fluid modulation can use known coating fluid dispersal devices such as coating oscillator, ball mill, vertical ball mill, three roller grinding mills, Ka Dishi grinder, puddle mixer, ダ イ ノ ミ Le, colloid mill to carry out.In addition, can use above-mentioned coating fluid dispersal device with each dispersion of materials in solvent, also can be dispersed in separately in the solvent again and mix.In addition, also can heating for dissolving separate out by chilling or slow cooling again.
Have no particular limits for the coating process that recording layer is set, can use, scraper coating, metal bar coating, spraying coating, airblade coating, steel wire soaking paste coating, curtain flow coat cloth, wheel change the gravure coating, roller is licked known methods such as coating, contrary roller coat cloth, dip coated, mouthful mould coating.
As the support of reversible thermosensitive recording medium of the present invention, can be paper, resin molding, PET film, synthetic paper, metal forming, glass or their complex etc., so long as can hold the record the layer get final product.In addition, can be with thick product optionally, separately or use such as applying.That is, can use from counting about μ m to the support of counting any thickness about mm.In addition, these supports also can have magnetic recording layer at the same one side and/or the opposing face of reversible thermosensitive recording layer.In addition, reversible thermosensitive recording medium of the present invention also can be paid on other media by subsides such as adhesive layers.Perhaps, one side at supports such as PET films is provided with back coating, the reverse side of this back coating is provided for the peel ply of thermal transfer ribbon, heat sensitive recording layer of the present invention is set on peel ply, have again, being provided with from the teeth outwards can the resin bed of transfer printing on paper, resin molding, PET film etc., also can be with the transfer printing of hot transfer printing typewriter.Reversible thermosensitive recording medium of the present invention can be processed into sheet or card-like, and its shape can be processed into arbitrary shape, in addition, can implement printing processing to dielectric surface.In addition, reversible thermosensitive recording medium of the present invention can use simultaneously with non-reversible heat sensitive recording layer, and at this moment, the color development tone of each recording layer can be the same or different.
The dry solidification method of recording layer optionally, is cured processing after the coating drying.Can use high temperature groove etc. to carry out the heat treatment of short time under than higher temperature, in addition, also can be through heat-treating for a long time under lower temperature.As the actual conditions of cross-linking reaction, from reactive aspect, preferably heating under the temperature conditions about 30 ℃～130 ℃ about 1 minute～150 hours.The temperature conditions that is more preferably at about 40 ℃～100 ℃ heated about 2 minutes～120 hours down.In addition, in the mill,, be difficult to guarantee therefore that crosslinked reaching fully finish the needed time because pay attention to productivity ratio.Therefore, so-called dry run also can be provided with crosslinked operation in addition.As the condition of crosslinked operation, preferred 40 ℃～100 ℃ temperature conditions heated about 2 minutes～120 hours down.
The scope of preferred 1～20 μ m of the thickness of reversible thermosensitive recording layer is more preferably 3～15 μ m.
For improving the cementability of reversible thermosensitive recording layer and protective layer; prevent from the intermediate layer to be set between because the additive rotten, that protective layer is contained of the recording layer that the coating of protective layer causes shifts to protective layer to recording layer transfer or the contained additive of recording layer.The scope of preferred 0.1～20 μ m of the thickness in intermediate layer is more preferably 0.3～10 μ m.The solvent that uses in the coating fluid in intermediate layer, the dispersal device of coating fluid, adhesive, coating process, dry solidification method etc. can be used the known method of using in above-mentioned recording layer.
In the formation of protective layer, the scope of preferred 0.1～20 μ m of the film thickness of protective layer is more preferably 0.3～10 μ m.The solvent that uses in the coating fluid of protective layer, the dispersal device of coating fluid, adhesive, coating process, dry solidification method etc. can be used the known method of using in above-mentioned recording layer.
Other the filler that does not have UV absorbing properties or ultraviolet ray shielding property can be in reversible thermosensitive recording layer, intermediate layer, protective layer, added,, inorganic filler and organic filler can be divided into as filler.Can enumerate calcium carbonate, magnesium carbonate, silicic acid anhydride, silicate hydrate, aluminium hydrosilicate, afwillite, aluminium oxide, iron oxide, calcium oxide, magnesia, chromium oxide, manganese oxide, silica, talcum, mica etc. as inorganic filler.As organic filler, can enumerate formaldehyde resin, plexiglass, vinyl chloride resins etc. such as acrylic resins such as styrene resin, vinylidene chloride acrylic acid, propylene uride, ethylene acrylic such as polyorganosiloxane resin, celluosic resin, epoxy resin, nylon resin, phenolic resins, polyurethane resin, Lauxite, melmac, mylar, polycarbonate resin, styrene, polystyrene, polystyrene isoprene, styrene ethylene base benzene, polyvinyl resin, benzo guanamine formaldehyde, melamine formaldehyde.In the present invention, can use filler separately, also can contain more than 2 kinds or 2 kinds.When multiple, there is no particular limitation to the combination technique of inorganic filler and organic filler.In addition,, can enumerate spherical, granular, tabular, needle-like etc. as shape.Filer content in the protective layer is calculated as 5～50 volume % with volume ratio.
Also can add lubricant,, can enumerate synthetic wax classes such as ester type waxes, paraffin, Tissuemat E as the concrete example of lubricant to reversible thermosensitive recording layer, intermediate layer, protective layer; Solidify castor bean wet goods vegetalitas wax class; Tallow solidifies wet goods animality wax class; Senior alcohols such as stearyl alcohol, behenyl alcohol; Senior fatty acids such as Heptadecanoic acide, laurate, the tetradecane (ミ ス チ レ Application) acid, hexadecanoic acid, stearic acid, behenic acid, the acid of Off ロ メ Application; Senior fatty acid esters such as the fatty acid ester of sorbitan; Amide-types such as stearic amide, oleamide, lauric amide, ethylenebis stearic amide, di-2-ethylhexylphosphine oxide stearic amide, methylol stearic amide etc.The content of the lubricant in the layer is calculated as 0.1～95% with volume ratio, more preferred 1～75%.
Reversible thermosensitive recording medium of the present invention can relatively form color development state and colour killing state by the cooling velocity after heating-up temperature and/or the heating.The basic color development colour killing phenomenon that comprises the composition that is used in colour former of the present invention and developer is described.Fig. 1 shows the color development concentration of this recording medium and the relation of temperature.In the time of will being in the recording medium intensification of colour killing state (A) initial stage, in the temperature T of beginning fusion
1Color development takes place, and becomes fusion color development state (B).If, then can reduce to room temperature, become the color development state (C) that solidifies with the former state of color development state from fusion color development state (B) chilling.Whether can obtain this color development state and depend on and speed from molten condition cooling under slow cooling, in temperature-fall period, can cause colour killing, form with the same colour killing state (A) of preliminary phase or than the relative low state of chilling color development state (C) concentration.On the other hand, if chilling color development state (C) is heated up once more, then in the temperature T lower than color development temperature
2Under cause colour killing (from D to E), if lower the temperature again from here, then turn back to and preliminary phase with colour killing state (A).Because actual color development temperature, colour killing temperature change to some extent according to the combination of developer that uses and colour former, therefore cooperate purpose to select.In addition, the color development concentration of the concentration of fusion color development state during with chilling may not be consistent, also has different situations.
In recording medium of the present invention, the color development state (C) that obtains from the molten condition chilling be developer and colour former can mix the state that obtains by catalytic state each other between the branch, it forms solid state mostly.This state is considered to developer and colour former aggegation and keeps the state of color development, makes the color development stabilisation by forming this agglutinate structure.On the other hand, the colour killing state is the state that both are separated.This state is considered to the elements collection of at least one side's compound, forms the state of microcell or crystallization, and by aggegation or crystallization, colour former separates the also state of stabilisation with developer.In the present invention, most cases can be separated by both, and the developer crystallization causes complete colour killing.The colour killing that causes by slow cooling from molten condition shown in Figure 1 and from the color development state because the colour killing that heats up and cause, any one all is that agglutinate structure changes under this temperature, causes to be separated or the crystallization of developer.
Reversible thermosensitive recording label of the present invention is on the face opposite with the face of the heat-sensitive layer of the support that form to constitute above-mentioned reversible thermosensitive recording medium, bond layer is set or adhesive phase forms.For this reversible thermosensitive recording label, type (nothing is peeled off paper mold) that forms bond layer or adhesive phase and the type (peeling off paper mold) that has peeling paper below this bond layer or adhesive phase arranged, can use heat molten type usually as the material that constitutes bond layer.
The material of bond layer or adhesive phase can use normally used material.Can enumerate, for example, Lauxite, melmac, phenolic resins, epoxy resin, the vinyl acetate resinoid, vinyl acetate-acrylic copolymer, ethylene-vinyl acetate copolymer, acrylic resin, the polyvinylether resinoid, the vinyl chloride-vinyl acetate analog copolymer, polystyrene resins, polyester resin, the polyurethanes resin, polyamide-based resin, the chloridized polyolefin resinoid, the polyvinyl butyral resin resinoid, acrylic acid esters co-polymer, the methyl acrylic ester copolymer, natural rubber, the cyanoacrylate resin, silicon resinoid etc., but be not limited to these.
Then the parts that have information storage part and reversible display part, contain the heat-sensitive layer that constitutes above-mentioned reversible thermosensitive recording medium as this reversible display part are described.
Have the parts of information storage part and reversible display part as this, roughly can be divided into following 3 kinds of parts.
(1), directly forms the parts of heat-sensitive layer with the part of parts support as reversible thermosensitive recording medium with information recording part.
(2) have on the parts of information recording part the parts of the support dignity of bonding other approach reversible thermosensitive recording medium that form, that on support, have heat-sensitive layer.
(3) having on the parts of information recording part, by bond layer or adhesive phase, the parts of bonding above-mentioned reversible thermosensitive recording label.
The situation of these (1) (2) (3), must make information storage part and reversible display part the performance separately function and set, like this, the desired location of information storage part can be arranged on the face with the opposite side of face of the heat-sensitive layer of the support that the thermal reversibility recording medium is set, also can be arranged between support and the heat-sensitive layer or on the part on the heat-sensitive layer.
There is no particular limitation as parts that these parts with information recording part use, but card, disk, cartridge or cassette tape are arranged usually.
As their example, citedly go out as following.
IC-card or photosensitive card uniform thickness quality card, floppy disc, the optical disc cartridge that magneto-optical recorder dish (MD) or DVD-RAW etc. can repeat to write the CD of stored information is equipped with in inside, CD-RW etc. do not use the CD of optical disk cartridge, erasable type CD such as CD-R, use the optical information recording medium (CD-RW) of phase-change type storage medium, videocassette etc., these have the two parts of reversible display part and information storage part, be that example is when describing with the card, be presented on the reversible thermosensitive recording layer by a part the information storage part canned data, the holder of card etc. does not need special device, only see that card just can confirmation, compare with the card that does not use reversible thermosensitive recording medium, its convenience significantly improves.
As long as information storage part can be stored necessary information, have no particular limits, but for example magnetic recording, contact-type IC, non-contact type IC or optical memory are useful.Magnetic recording layer can use resin of metallic compounds such as normally used iron oxide, barium ferrite and polyvinyl chloride-base, carbamates and nylon-type etc. to be coated on the support and form, perhaps can not use resin and use above-mentioned metallic compound, form by methods such as evaporation, sputters.In addition, the reversible thermosensitive recording layer on the reversible thermosensitive recording medium that also can will be used to show with bar code, 2 usings method such as dimension bar codes etc. uses as memory portion.
Example as the reversible thermosensitive recording label that uses above-mentioned (3), as with vinyl chloride fabrication of magnetic stripe etc., when as support being the thick quality support of coating difficulty of reversible thermosensitive recording layer, can bond layer or adhesive phase be set at it comprehensively or on the part.Thus, can show the part of magnetic stripe institute canned data etc., improve the convenience of this medium.
As this set the reversible thermosensitive recording label of bond layer or adhesive phase, not only go for the vinyl chloride card of above-mentioned band magnetic stripe, also go for IC-card or photosensitive card uniform thickness quality card.
In addition, this reversible thermosensitive recording label can be used as and substitutes inside and the display label that can repeat to write on the cartridge of disk of stored information of floppy disc, MD or DVD-RAM etc. is housed uses.Fig. 2 shows reversible thermosensitive recording label is attached to example on the cartridge of MD.Have, CD-RW etc. do not use under the situation of CD of optical disk cartridge, reversible thermosensitive recording label directly can be attached on the CD, or directly the reversible thermosensitive recording layer be set on CD again.Thus, can be applied to these changes according to memory contents changes in the purposes of displaying contents etc. automatically.
Fig. 3 shows reversible thermosensitive recording label is attached to example on the CD-RW.
Reversible thermosensitive recording label of the present invention is attached to reversible thermosensitive recording label on the erasable type CDs such as CD-R, can repeat to show a part that chases after the stored information that writes among the CD-R.
Have, as shown in Figure 4, the display label that also can be used as videocassette uses again.
As the method that the thermal reversibility writing function is set on thick quality card, cartridge, disk, except that the method for above-mentioned stickup reversible thermosensitive recording label, in addition the reversible thermosensitive recording layer directly is coated on the method on them, or on other supports, form the reversible thermosensitive recording layer in advance, again with the method for this heat sensitive recording layer transfer printing on thick quality card, cartridge, disk etc.
During transfer printing, the adhesive linkage or the adhesive layer of heat molten type etc. can be set on the reversible thermosensitive recording layer also.
On rigid objects such as thick quality card, disk, cartridge, cassette tape, paste reversible thermosensitive recording label, or when the reversible thermosensitive recording layer is set, be the contact of raising with thermal head, be formed uniformly image, preferably between the matrix of rigidity and label or reversible thermosensitive recording layer, be provided with have elastic force, as the layer or the sheet of buffering.
The present invention also provides a kind of image processing method, it is characterized in that, this method is used above-mentioned reversible thermosensitive recording medium, above-mentioned parts or above-mentioned label with information storage part, and realizes the formation and/or the elimination of image by heating; And a kind of image processing apparatus, it is characterized in that this device has above-mentioned reversible thermosensitive recording medium, above-mentioned parts or above-mentioned label with information storage part, realize the formation and/or the elimination of image by heating.
The formation of image can use thermal head, laser etc. can heat the image recorder of this medium on ground, image top.The elimination of image can be used hot bruisher (ホ Star ト ス Application プ), ceramic heater, hot-rolling, hot blast etc. or image abatement apparatus such as thermal head, laser.Wherein, preferably use ceramic heater.By using ceramic heater, can make equipment miniaturization, and obtain stable elimination state, obtain the contrast preferable image.The design temperature of ceramic heater is preferred more than 100 ℃ or 100 ℃, and comparative optimization is more preferably more than 115 ℃ or 115 ℃ more than 110 ℃ or 110 ℃.
In addition, by using thermal head as the image abatement apparatus, can the further miniaturization of operative installations, in addition, can reduce power consumption, also can become battery-driven mancarried device.If use to have concurrently and form a thermal head using and eliminate usefulness, then further miniaturization.When forming and eliminating with a thermal head, after can once original image all being eliminated, forming new image again, also can be that image changes the rewrite method that energy is then eliminated original image, form once new image at every turn.In rewrite method, will form and eliminate merging, time decreased, the speed of record improves.
When use has the card of reversible thermosensitive recording layer and information storage part, also in said apparatus, comprise the equipment of the storage of reading information storage part and the equipment that writes again.
Fig. 5 shows the example of image processing apparatus of the present invention.Fig. 5 illustrates according to the present invention, carries out the elimination of image respectively with ceramic heater, the synoptic diagram of the device when carrying out the formation of image with thermal head.
In the image processing apparatus of Fig. 5, at first, read the information of the magnetic recording layer that is stored in storage medium with magnetic head, then, eliminate the image that is recorded in the reversible thermosensitive recording layer with ceramic heaters heat, then, based on the information that reads with magnetic head, the fresh information of processing is recorded on the invertibity temperature-sensitive layer by thermal head.Afterwards, the information of magnetic recording layer also is rewritten as new information.
That is, in the image processing apparatus of Fig. 5, the thermal reversibility recording medium that is provided with magnetic recording layer at the opposition side of heat-sensitive layer is along transmitting to come and go the shown transmission route of arrow plot, or along transmitting route transmission in the other direction in device.
The thermal reversibility recording medium, between magnetic head (34) and transfer roller (40), carry out magnetic recording or record elimination at magnetic recording layer, between ceramic heater (38) and transfer roller (40), carry out the heat treated that removal of images is used, carrying out image between thermal head (53) and transfer roller (47) forms, afterwards, send out outside the device.Here, the writing again of magnetic recording can be before the image that adopts ceramic heater be eliminated, also can be after image is eliminated.In addition, according to expectation, after between ceramic heater (38) and the transfer roller (40), or after passing through between thermal head (53) and the transfer roller (47), can transmit in the other direction along transmitting route, implement to adopt the heat treatment once more of ceramic heater (38), the typewriting once more of employing thermal head (53) to handle.
Embodiment
Below, by embodiment the present invention is described in more detail.In addition, " part " among the embodiment and " % " all are benchmark with weight.
Embodiment 1
The making of＜reversible thermosensitive recording layer 〉
2 parts of the 2-anilino-s-glimmering hydrocarbon of 3-methyl-6-dibutylamino
8 parts of the developers of following structure
20 parts of vinyl chloride-vinyl acetate copolymers
(ユ ニ オ Application カ one バ イ ト society system, VYHH)
N, 0.4 part in N '-two (octadecyl) urea
90 parts of MEKs
Is 0.1～3 μ m with above-mentioned composition with ball mill grinding dispersion to average grain diameter.With the dispersion liquid modulation reversible thermosensitive recording layer coating fluid that obtains.
Be coated on this recording layer coating liquid of above-mentioned composition on the white PET film (big Japanese イ Application キ system) of the band magnetosphere of the about 250 μ m of thickness with metal bar, after under 115 ℃ dry 1 minute, 60 ℃ were heated 36 hours down, the reversible thermosensitive recording layer of the about 11.0 μ m of thickness are set.The gel fraction of the resin of this heat sensitive recording layer is about 92%.
Embodiment 2
2 parts of 3-(4-diacetylene amino-2-ethoxyl phenenyl)-3-(1-ethyl-2 methyl indole-3-yl)-4-azepine phthalein ketone
8 parts of the developers of following structure
150 parts of 15% MEK (MEK) solution of the many alcohol resins of acrylic compounds
(hydroxyl value: 133, acid number: 6.5, molecular weight: 7000, glass transition temperature: 34 ℃)
Except that using above-mentioned reversible thermosensitive recording layer dispersion liquid, the reversible thermosensitive recording layer is set similarly to Example 1.The gel fraction of the resin of this heat sensitive recording layer is about 89%.
Embodiment 3
2 parts of the 2-anilino-s-glimmering hydrocarbon of 3-methyl-6-diethylamino
8 parts of the developers of following structure
150 parts of the 15%THF solution of the many alcohol resins of acrylic compounds
(hydroxyl value: 70, acid number: less than 1.0, molecular weight: 35000, glass transition temperature: 52 ℃, carboxylic monomer: 2-hydroxyethyl methacrylate)
10 parts of コ ロ ネ one ト HL
Except that using above-mentioned reversible thermosensitive recording layer dispersion liquid, the reversible thermosensitive recording layer is set similarly to Example 1.The gel fraction of the resin of this heat sensitive recording layer is about 89%.
Embodiment 4
2 parts of 3-(4-diacetylene amino-2-ethoxyl phenenyl)-3-(1-ethyl-2 methyl indole-3-yl)-4-azepine phthalein ketone
8 parts of the developers of following structure
150 parts of the 15%THF solution of mylar
(hydroxyl value: 166, acid number: 2.2)
10 parts of コ ロ ネ one ト HL
8 parts of the colour killing promoter of following structure
Except that using above-mentioned reversible thermosensitive recording layer dispersion liquid, the reversible thermosensitive recording layer is set similarly to Example 1.The gel fraction of the resin of this heat sensitive recording layer is about 89%.
Have again; after using the metal bar coating to contain the protective layer coating solution of following composition on the reversible thermosensitive recording layer, can pass through with the transfer rate of 12m/ branch under the ultraviolet lamp of 80W/cm in irradiation, and solidify; the protective layer of thickness 3 μ m is set, makes reversible thermosensitive recording medium of the present invention.
The making of＜protective layer 〉
Urethane acrylate class uv curing resin
(the big Japanese イ Application キ system C7-157 of society) 10 parts
1.5 parts of silica (marshy land chemistry society system, P-527)
90 parts of ethyl acetates
Embodiment 5
2 parts of the 2-anilino-s-glimmering hydrocarbon of 3-methyl-6-diethylamino
8 parts of the developers of following structure
150 parts of Vinalac 5920 resins (the system BR102 of the レ of Mitsubishi one ヨ Application society)
10 parts of コ ロ ネ one ト HL
8 parts of the colour killing promoter of following structure
Except that using above-mentioned reversible thermosensitive recording layer dispersion liquid, the reversible thermosensitive recording layer is set similarly to Example 1.The gel fraction of the resin of this heat sensitive recording layer is about 89%.
In addition, protective layer is set similarly to Example 4.
Embodiment 6
150 parts of 15% MEK (MEK) solution of the many alcohol resins of acrylic compounds
(hydroxyl value: 108, acid number: less than 1.0, molecular weight: 107800, glass transition temperature: 80 ℃, carboxylic monomer: 2-hydroxyethyl methacrylate)
10 parts of コ ロ ネ one ト HL
Except that above-mentioned, the reversible thermosensitive recording layer is set similarly to Example 1.The gel fraction of the resin of this heat sensitive recording layer is about 89%.
The coating of use metal bar contains the intermediate layer coating fluid of following composition on this recording layer, and drying is after 1 minute down at 90 ℃, and 60 ℃ were heated 1 hour down, the intermediate layer of the about 2 μ m of thickness is set.
The making in＜intermediate layer 〉
100 parts of 10% MEK (MEK) solution of polyester polyol resin (the military field system ケ ラ of pharmaceutical industries society Star Network U-21)
10 parts in zinc oxide (Osaka, Sumitomo セ メ Application ト)
15 parts of コ ロ ネ one ト HL
In addition, protective layer is set similarly to Example 4 on the intermediate layer.
Embodiment 7
2 parts of the 2-anilino-s-glimmering hydrocarbon of 3-methyl-6-diethylamino
8 parts of the developers of following structure
150 parts of 15% MEK (MEK) solution of the many alcohol resins of acrylic compounds
(hydroxyl value: 100, acid number: less than 1.0, molecular weight: 107800, glass transition temperature: 80 ℃, carboxylic monomer: 2-hydroxyethyl methacrylate)
25 parts of コ ロ ネ one ト HL
Except that above-mentioned, the reversible thermosensitive recording layer is set similarly to Example 1.The gel fraction of the resin of this heat sensitive recording layer is about 89%.
Embodiment 8
2 parts of 3-(4-diacetylene amino-2-ethoxyl phenenyl)-3-(1-ethyl-2 methyl indole-3-yl)-4-azepine phthalein ketone
10 parts of the developers of following structure
150 parts of Vinalac 5920 resins (the system BR102 of the レ of Mitsubishi one ヨ Application society)
10 parts of コ ロ ネ one ト HL
8 parts of the colour killing promoter of following structure
Except that above-mentioned, the reversible thermosensitive recording layer is set similarly to Example 1.The gel fraction of the resin of this heat sensitive recording layer is about 89%.
In addition, intermediate layer, protective layer are set similarly to Example 6.
Embodiment 9
Use the reversible thermosensitive recording layer of embodiment 7, intermediate layer, protective layer are set similarly to Example 6.
Embodiment 10
Except that 8 parts of the developers that uses following structure, make reversible thermosensitive recording medium similarly to Example 1.
Embodiment 11
Except that 8 parts of the developers that uses following structure, make reversible thermosensitive recording medium similarly to Example 1.
Embodiment 12
Except that 8 parts of the developers that uses following structure, make reversible thermosensitive recording medium similarly to Example 1.
Comparative example 1
Except that 8 parts of the developers that uses following structure, make reversible thermosensitive recording medium similarly to Example 1.
Comparative example 2
Except that 8 parts of the developers that uses following structure, make reversible thermosensitive recording medium similarly to Example 1.
Comparative example 3
Except that 8 parts of the developers that uses following structure, make reversible thermosensitive recording medium similarly to Example 1.The gel fraction of the resin of the heat sensitive recording layer of these comparative examples 1～3 is more than 80% or 80%.
The temperature-sensitive typing apparatus that the recording medium of above making is made with the electric society in big storehouse, thermal head by 8 points/mm is typewrited under second at voltage 13.3V, pulse width 1.2m, with hot inclining experiment machine colour killing under 110 ℃, 1 second condition that Japan smart machine society makes, use Mike than thinking (マ Network ベ ス) densimeter RD-914 and measure the optical concentration of this typewriting portion and elimination portion and this bottom.It under ambient temperature and moisture (22 ℃, 60%RH) and hot and humid (35 ℃, 85%RH) environment, is typewrited and eliminate.
In addition, carry out 50 above-mentioned typewritings repeatedly down at the ambient temperature and moisture environment and eliminate,, use following grade evaluation with the state of visual observation image color and the state on recording medium surface.
Grade 1: image portion is good color development state, does not find percussion mark.
Grade 2: the state of image portion is bad, finds to have slightly percussion mark
Grade 3: the color development of image portion is inhomogeneous, and percussion mark takes place
Class 4: serious percussion mark, take place in the color development state extreme difference of image portion
The above following table 15 that the results are shown in
Table 15
| Ambient temperature and moisture | Hot and humid | Durability | ||||
| Color development concentration | Colour killing concentration | Background concentration | Color development concentration | Colour killing concentration | ||
| Embodiment 1 | 1.08 | 0.14 | 0.11 | 1.09 | 0.13 | Grade 1 |
| Embodiment 2 | 0.88 | 0.14 | 0.12 | 0.89 | 0.14 | Grade 1 |
| Embodiment 3 | 0.96 | 0.14 | 0.11 | 0.93 | 0.14 | Grade 1 |
| Embodiment 4 | 1.07 | 0.13 | 0.11 | 1.08 | 0.13 | Grade 1 |
| Embodiment 5 | 1.09 | 0.14 | 0.11 | 1.10 | 0.13 | Grade 1 |
| Embodiment 6 | 1.04 | 0.13 | 0.11 | 1.06 | 0.13 | Grade 1 |
| Embodiment 7 | 1.09 | 0.13 | 0.12 | 1.08 | 0.12 | Grade 1 |
| Embodiment 8 | 1.07 | 0.12 | 0.11 | 1.06 | 0.12 | Grade 1 |
| Embodiment 9 | 1.08 | 0.12 | 0.11 | 1.08 | 0.12 | Grade 1 |
| Embodiment 10 | 0.95 | 0.32 | 0.12 | 0.82 | 0.37 | Grade 1 |
| Embodiment 11 | 0.86 | 0.26 | 0.11 | 0.79 | 0.23 | Grade 1 |
| Embodiment 12 | 1.02 | 0.22 | 0.11 | 0.89 | 0.25 | Grade 1 |
| Comparative example 1 | 0.93 | 0.04 | 0.11 | 0.41 | 0.16 | Grade 2 |
| Comparative example 2 | 0.85 | 0.14 | 0.11 | 0.53 | 0.16 | Grade 2 |
| Comparative example 3 | 0.92 | 0.14 | 0.11 | 0.50 | 0.11 | Grade 2 |
For embodiment 1～12, all it doesn't matter with the influence of humidity in any environment, color development concentration and colour killing concentration stabilize.In addition, even for endurancing, also almost the do not typewrite reduction of concentration and the rising of colour killing concentration present the kilter of not printing vestige.
Embodiment 13
The making of＜reversible thermosensitive recording layer 〉
Use ball mill that following composition is pulverized and be dispersed to particle diameter 1～4 μ m.
[A liquid]
2 parts of the 2-anilino-s-glimmering hydrocarbon of 3-methyl-6-dibutylamino
8 parts of the developers of following structure
2 parts in the color development colour killing inhibitor of following structure
C
17H
35CONHC
18H
35
150 parts of 15% MEK (MEK) solution of the many alcohol resins of acrylic compounds
(hydroxyl value: 133, acid number: 6.5, molecular weight: 7000, glass transition temperature: 34 ℃)
10 parts of the コ ロ ネ one ト HL (adduct type hexamethylene diisocyanate 75% ethyl acetate solution) that interpolation Japanese polyurethane society makes in the dispersion liquid that obtains fully stir, the modulation recording layer coating liquid.Be coated on the recording layer coating liquid of above-mentioned composition on the white PET film (big Japanese イ Application キ system) of the band magnetosphere of the about 250 μ m of thickness with metal bar, after under 115 ℃ dry 1 minute, 60 ℃ were heated 36 hours down, the reversible thermosensitive recording layer of the about 11.0 μ m of thickness are set.The gel fraction of the resin of this heat sensitive recording layer is about 90%.
The coating of use metal bar contains the intermediate layer liquid of following composition on this recording layer, and drying is after 1 minute down at 90 ℃, and 60 ℃ were heated 2 hours down, the intermediate layer of the about 2.0 μ m of thickness is set.Have again, after using the metal bar coating to contain the protective layer liquid of following composition, can pass through with the transfer rate of 12m/ branch under the ultraviolet lamp of 80W/cm in irradiation, and solidify, the protective layer of thickness 3 μ m is set, make reversible thermosensitive recording medium of the present invention.
Intermediate layer liquid
100 parts of 10% MEK (MEK) solution of polyester polyol resin (the military field system ケ ラ of pharmaceutical industries society Star Network U-21)
10 parts in zinc oxide (Osaka, Sumitomo セ メ Application ト)
15 parts of コ ロ ネ one ト HL
Protective layer liquid
10 parts of urethane acrylate class uv curing resins
1.5 parts of silica (marshy land chemistry society system, P-527)
(the big Japanese イ Application キ system C7-157 of society)
90 parts of ethyl acetates
Embodiment 14～25
Except that the colour killing of using structure shown in the table 16 promotion property compound, make reversible thermosensitive recording medium similarly to Example 13.
Table 16
Embodiment 26
Except that 8 parts of the developers that uses following structure, make reversible thermosensitive recording medium similarly to Example 13.
Embodiment 27
Except that 8 parts of the developers that uses following structure, make reversible thermosensitive recording medium similarly to Example 13.
Embodiment 28
Except that 8 parts of the developers that uses following structure, make reversible thermosensitive recording medium similarly to Example 13.
Comparative example 4
Except that 8 parts of the developers that uses following structure, make reversible thermosensitive recording medium similarly to Example 1.
Comparative example 5
Except that 8 parts of the developers that uses following structure, make reversible thermosensitive recording medium similarly to Example 1.
Comparative example 6
Except that 8 parts of the developers that uses following structure, make reversible thermosensitive recording medium similarly to Example 1.
Use eight cities of the EUX-ET8A9AS1 face type thermal head (1152 ohm of resistance values) that adopts the manufacturing of society of National Electronics Research Centre to make temperature-sensitive typewriting シ ユ ミ レ one ダ one of manufacturing the reversible thermosensitive recording medium of above making, typewrite under the following conditions and eliminate, use Mike than thinking the optical concentration that densimeter RD-914 measures this typewriting portion, elimination portion, this bottom.
Concentration-the background concentration of the image portion after elimination residual concentration=elimination
Appreciation condition: pulse width 2ms, conveyer belt (ラ イ Application) cycle 2.86ms, typing speed 43.10mm/s, subscan density 8dot/mm
It under ambient temperature and moisture (22 ℃, 60%RH) and hot and humid (35 ℃, 85%RH) environment, is typewrited and eliminate.
In addition, under the ambient temperature and moisture environment, carry out 10 above-mentioned typewritings repeatedly and eliminate,, use following grade evaluation with the state of visual observation image color and the state on recording medium surface.
Grade 1: image portion is good color development state, does not find percussion mark.
Grade 2: the state of image portion is bad, finds to have slightly percussion mark
Grade 3: the color development of image portion is inhomogeneous, and percussion mark takes place
Class 4: the color development state of image portion extremely worsens, and serious percussion mark takes place
The above following table 17 that the results are shown in
Table 17
| Ambient temperature and moisture | Hot and humid | Durability | ||||
| Color development concentration | Colour killing concentration | Background concentration | Color development concentration | Colour killing concentration | ||
| Embodiment 13 | 1.07 | 0.14 | 0.11 | 1.05 | 0.14 | Grade 1 |
| Embodiment 14 | 1.06 | 0.14 | 0.12 | 1.06 | 0.15 | Grade 1 |
| Embodiment 15 | 1.18 | 0.13 | 0.11 | 1.15 | 0.13 | Grade 1 |
| Embodiment 16 | 1.21 | 0.17 | 0.12 | 1.20 | 0.17 | Grade 1 |
| Embodiment 17 | 1.15 | 0.16 | 0.11 | 1.11 | 0.15 | Grade 1 |
| Embodiment 18 | 1.18 | 0.13 | 0.11 | 1.18 | 0.14 | Grade 1 |
| Embodiment 19 | 1.10 | 0.16 | 0.12 | 1.09 | 0.16 | Grade 1 |
| Embodiment 20 | 1.05 | 0.16 | 0.11 | 1.03 | 0.15 | Grade 1 |
| Embodiment 21 | 1.00 | 0.18 | 0.12 | 0.98 | 0.19 | Grade 1 |
| Embodiment 22 | 1.05 | 0.16 | 0.11 | 1.00 | 0.17 | Grade 1 |
| Embodiment 23 | 1.10 | 0.12 | 0.10 | 1.11 | 0.13 | Grade 1 |
| Embodiment 24 | 1.09 | 0.14 | 0.11 | 1.02 | 0.15 | Grade 1 |
| Embodiment 25 | 1.02 | 0.13 | 0.11 | 1.00 | 0.13 | Grade 1 |
| Embodiment 26 | 1.05 | 0.29 | 0.10 | 0.92 | 0.31 | Grade 1 |
| Embodiment 27 | 0.95 | 0.27 | 0.11 | 0.89 | 0.30 | Grade 1 |
| Embodiment 28 | 1.08 | 0.27 | 0.10 | 1.00 | 0.29 | Grade 1 |
| Comparative example 4 | 1.06 | 0.15 | 0.11 | 0.51 | 0.14 | Grade 2 |
| Comparative example 5 | 1.00 | 0.17 | 0.11 | 0.60 | 0.15 | Grade 2 |
| Comparative example 6 | 1.02 | 0.17 | 0.11 | 0.61 | 0.15 | Grade 2 |
Industrial applicibility
To sum up, can understand from detailed and specific description, reversible thermosensitive recording medium of the present invention, even can provide color development concentration and colour killing concentration not to be subjected to humidity effect, have excellent high-contrast and Reusability, also rare percussion mark and change in concentration, the good reversible thermosensitive recording medium of durability to recording medium. Also providing can be with the reversible thermosensitive recording medium of the excellent high speed colour killing of having of thermal head colour killing.
Claims (21)
1. reversible thermosensitive recording medium, this reversible thermosensitive recording medium is, the reversible thermosensitive recording medium that on support, has the reversible thermosensitive recording layer, described reversible thermosensitive recording layer contains to use powers sub-property colour generation compound and accepts the electronics compound, can relatively form the reversibly hot sensitive composition of color development state by the difference of the cooling velocity after heating-up temperature and/or the heating, it is characterized in that, this accepts the electronics compound is the phenolic compounds of representing with following general formula (1), and this reversible thermosensitive recording medium is at 35 ℃ ± 2 ℃, color development concentration when the environment of relative humidity 70%～90% is printed down is more than 0.80 or 0.80, and colour killing concentration is below 0.15 or 0.15;
(in the formula, n represents 1～3 integer, and X represents to contain the divalent group of N atom or O atom, in addition, and R
1Expression can have substituent carbon number 2 or 2 above aliphatic alkyls, R
2The aliphatic alkyl of expression carbon number 1～14).
2. according to the reversible thermosensitive recording medium of claim 1 record, it is characterized in that the above-mentioned electronics compound of accepting is in general formula (1), to have R
1Be carbon number 10～16 and R
2Phenolic compounds for the aliphatic alkyl of carbon number 8～14.
3. according to the reversible thermosensitive recording medium of any record in claim 1 and 2, it is characterized in that the above-mentioned electronics compound of accepting is that in general formula (1), X is the phenolic compounds of urea base.
4. according to the reversible thermosensitive recording medium of any record in the claim 1 to 3, it is characterized in that above-mentioned reversible thermosensitive recording layer contains the resin that is in cross-linked state.
5. according to the reversible thermosensitive recording medium of claim 4 record, it is characterized in that contained resin hydroxyl value is 70 (KOHmg/g) or more than 70 (KOHmg/g) in the above-mentioned reversible thermosensitive recording layer.
6. according to the reversible thermosensitive recording medium of any record of claim 4 to 5, it is characterized in that contained resin is the many alcohol resins of acrylic compounds in the above-mentioned reversible thermosensitive recording layer.
7. according to the reversible thermosensitive recording medium of any record in the claim 1 to 3, it is characterized in that the gel fraction of above-mentioned resin is more than 30% or 30%.
8. according to the reversible thermosensitive recording medium of any record in the claim 1 to 7, it is characterized in that,, comprise compound with secondary amide base as colour killing promoter.
9. according to the reversible thermosensitive recording medium of any record in the claim 1 to 7, it is characterized in that, also contain have one or more-NHCO-base in the molecule at least ,-the colour killing promoter of OCONH-base.
10. according to the reversible thermosensitive recording medium of claim 9 record, it is characterized in that, have at least in the above-mentioned molecule one or more-NHCO-base ,-the colour killing promoter of OCONH-base is with in the compound of general formula (2)～(8) expression any one;
R
1-NHCO-R
2 …(2)
R
1-NHCO-R
3-OCNH-R
2 …(3)
R
1-CONH-R
3-HNOC-R
2 …(4)
R
1-NHOCO-R
2 …(5)
R
1-NHOCO-R
3-OCOHN-R
3 …(6)
R
1-OCONH-R
3-HNOCO-R
2 …(7)
(in the formula, R
1, R
2, R
4The expression carbon number 7～22 straight chained alkyl, branch's alkyl, unsaturated alkyl, R are arranged
3The divalent functional group of expression carbon number 1～10, R
53 valency functional groups of expression carbon number 4～10).
11. the reversible thermosensitive recording medium according to any record in the claim 1 to 10 is characterized in that, the protective layer that this heat sensitive recording layer of protection is used is set on above-mentioned reversible thermosensitive recording layer, this protective layer contains the resin that is in cross-linked state.
12. the parts with information recording part is characterized in that, these parts have information storage part and reversible display part, and this reversible display part contains the reversible thermosensitive recording medium of any record in the claim 1 to 11 at least.
13. the parts with information storage part according to claim 12 record is characterized in that above-mentioned parts with information storage part and reversible display part are any one in card, disk, cartridge or the cassette tape.
14. reversible thermosensitive recording label, it is characterized in that, with form to constitute claim 1 to 11 in the opposite face of face of reversible thermosensitive recording layer of support of reversible thermosensitive recording medium of any record on, at least one in bond layer and the adhesive phase is set.
15. the parts with information storage part according to any record in the claim 12 to 13 is characterized in that, the reversible display part of the reversible thermosensitive recording label that uses claim 14 record is set.
16. image processing method, it is characterized in that, use any parts of being put down in writing in the reversible thermosensitive recording label of reversible thermosensitive recording medium, claim 14 record of any record in the claim 1 to 11 and the claim 12,13 and 15 with information storage part and reversible display part, by the reversible thermosensitive recording layer that heats this reversible display part carry out the formation of image and eliminate at least any one.
17. the image processing method according to claim 16 record is characterized in that, uses thermal head to form image at above-mentioned reversible display part.
18. the image processing method according to claim 16 record is characterized in that, with thermal head or ceramic heater removal of images.
19. image processing apparatus, it is characterized in that, this device loads any parts of being put down in writing with information storage part and reversible display part in the reversible thermosensitive recording label of reversible thermosensitive recording medium, claim 14 record of any record in claim 1 to 11 and the claim 12,13 and 15, have carry out that image forms and eliminate at least any one equipment and constitute.
20. the image processing apparatus according to claim 19 is put down in writing is characterized in that, image forming apparatus is a thermal head.
21. the image processing apparatus according to claim 19 is put down in writing is characterized in that, the image abatement apparatus be in thermal head and the ceramic heater at least any one.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003077347A JP4030057B2 (en) | 2002-03-22 | 2003-03-20 | Reversible thermosensitive recording medium |
| JP77347/2003 | 2003-03-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1771135A true CN1771135A (en) | 2006-05-10 |
| CN100528596C CN100528596C (en) | 2009-08-19 |
Family
ID=33027945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801102981A Expired - Lifetime CN100528596C (en) | 2003-03-20 | 2003-10-24 | Reversible thermal recording medium |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1609616B1 (en) |
| CN (1) | CN100528596C (en) |
| WO (1) | WO2004082955A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102189766A (en) * | 2010-01-28 | 2011-09-21 | 株式会社东芝 | Image recording apparatus and image recording method |
| CN102265321A (en) * | 2009-01-06 | 2011-11-30 | 勃来迪环球股份有限公司 | Label media having a substrate and a two-sided releasable liner |
| CN103205250A (en) * | 2013-03-05 | 2013-07-17 | 上海市电力公司 | Reversible thermochromic material and application thereof |
| CN109278449A (en) * | 2018-09-30 | 2019-01-29 | 胡玉英 | A kind of waste and old paper recycle device |
| CN109996682A (en) * | 2016-11-18 | 2019-07-09 | 索尼公司 | Invertibity recording medium and external component |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0764117B2 (en) | 1985-04-15 | 1995-07-12 | 日本電信電話株式会社 | Rewritable optical recording method and rewritable optical recording medium |
| JPH07100769B2 (en) | 1985-12-11 | 1995-11-01 | パイロツトインキ株式会社 | Color memory paint |
| JPH078931B2 (en) | 1985-12-12 | 1995-02-01 | パイロットインキ 株式会社 | Color memory resin composition |
| JPH0659746B2 (en) | 1985-12-14 | 1994-08-10 | パイロツトインキ株式会社 | Color memory printed matter |
| JPH0829621B2 (en) | 1987-01-14 | 1996-03-27 | 株式会社リコー | Reversible recording material |
| JPH02188294A (en) | 1989-01-18 | 1990-07-24 | Toppan Printing Co Ltd | Reversible thermosensitive recording medium |
| JPH02188293A (en) | 1989-01-18 | 1990-07-24 | Toppan Printing Co Ltd | Reversible thermosensitive recording medium |
| JP2981558B2 (en) | 1990-12-26 | 1999-11-22 | 株式会社リコー | Reversible thermochromic composition, recording medium and recording method using the same |
| JP3380277B2 (en) | 1992-06-17 | 2003-02-24 | 三菱製紙株式会社 | Reversible thermosensitive recording material |
| JP3557076B2 (en) | 1996-06-06 | 2004-08-25 | 株式会社リコー | Reversible thermosensitive coloring composition and reversible thermosensitive recording medium using the same |
| JP3966585B2 (en) | 1996-08-07 | 2007-08-29 | 株式会社リコー | Reversible thermosensitive recording medium |
| JPH10315623A (en) * | 1997-05-20 | 1998-12-02 | Ricoh Co Ltd | Reversible thermal recording medium |
| JPH10315627A (en) * | 1997-05-21 | 1998-12-02 | Ricoh Co Ltd | Reversible thermal recording medium |
| JPH10315625A (en) * | 1997-05-21 | 1998-12-02 | Ricoh Co Ltd | Reversible thermal recording medium |
| JPH10315626A (en) * | 1997-05-21 | 1998-12-02 | Ricoh Co Ltd | Reversible thermal recording medium |
| US6261992B1 (en) | 1998-09-29 | 2001-07-17 | Ricoh Company, Ltd. | Reversible thermosensitive recording material and recording method and apparatus therefor |
| JP2001113829A (en) * | 1999-10-18 | 2001-04-24 | Mitsubishi Paper Mills Ltd | Reversible heat-sensitive recording material |
-
2003
- 2003-10-24 CN CNB2003801102981A patent/CN100528596C/en not_active Expired - Lifetime
- 2003-10-24 WO PCT/JP2003/013636 patent/WO2004082955A1/en active Application Filing
- 2003-10-24 EP EP03758884.5A patent/EP1609616B1/en not_active Expired - Lifetime
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| CN102265321A (en) * | 2009-01-06 | 2011-11-30 | 勃来迪环球股份有限公司 | Label media having a substrate and a two-sided releasable liner |
| CN102265321B (en) * | 2009-01-06 | 2014-12-24 | 勃来迪环球股份有限公司 | Label media having a substrate and a two-sided releasable liner |
| CN102189766A (en) * | 2010-01-28 | 2011-09-21 | 株式会社东芝 | Image recording apparatus and image recording method |
| CN103205250A (en) * | 2013-03-05 | 2013-07-17 | 上海市电力公司 | Reversible thermochromic material and application thereof |
| CN103205250B (en) * | 2013-03-05 | 2015-04-29 | 上海市电力公司 | Reversible thermochromic material and application thereof |
| CN109996682A (en) * | 2016-11-18 | 2019-07-09 | 索尼公司 | Invertibity recording medium and external component |
| CN109278449A (en) * | 2018-09-30 | 2019-01-29 | 胡玉英 | A kind of waste and old paper recycle device |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004082955A1 (en) | 2004-09-30 |
| CN100528596C (en) | 2009-08-19 |
| EP1609616A1 (en) | 2005-12-28 |
| EP1609616B1 (en) | 2014-12-03 |
| EP1609616A4 (en) | 2006-10-11 |
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