JPH013176A - Phenoxazine compound and transfer material for thermal recording - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel phenoxazine compound and a video printer, etc. that forms an image by heating with a thermal head, which is characterized by using the phenoxazine compound. The present invention relates to a sublimation transfer type heat-sensitive recording transfer body to be used.

[Conventional technology and its problems]

The sublimation transfer type thermal recording method is a method in which a transfer material coated with a color material layer and a receiving paper are placed opposite each other, and an image is obtained by heating the transfer paper from the back side with a thermal head, etc. The equipment is simple and video recording is possible. It has been put into practical use in printers, etc. Disperse dyes with high sublimation properties or basic color formers are used as pigments.When using disperse dyes, a polymer film such as polyester or acetate is formed as an image-receiving layer on the transfer paper, but it is not sufficient. Although the light fastness of the disperse dye was good, there was a problem with the stability of the image in this respect. On the other hand, in basic color formers, the image-receiving layer is formed of clay, activated clay, etc., and the hue is clear and the color density is high, but there is a problem in the light resistance of the image. However, among these, phenoxazine compounds are basic color formers that provide images with good light resistance, and have been developed as sublimation color formers. Special Public Service 1975-1
4.427 discloses a 10-acylphenoxazine compound, but although this compound has excellent storage stability as a color former, it has the problem of slow color development. JP-A-57-80454 discloses a 10-alkylcarbamoylphenoxazine compound, but although this compound has improved color development, it has a problem in stability as a color former.

=3- [Means for solving the problem] The present inventors have developed a color former that has high stability and
As a result of intensive research into a sublimation color former that has a fast sublimation color development rate and develops a clear, high-density cyan color with good light resistance, we found that the general formula % formula % (where R1 and R2 are carbon atoms 1 to 4 R3 represents an alkyl group or aryl group having 1 to 4 carbon atoms, and Y represents 1 carbon atom which may have a halogen atom, an alkoxy group, or a dialkylamino group as a substituent. An alkyl group, an aryl group, or an aralkyl group having ~8 alkyl groups.

By using one or two of these phenoxazine compounds, a cyan-colored image with excellent gradation, high density color development, clearness, and good light resistance was obtained.

=5- Also, the phenoxazine compound has the general formula (wherein R4 and R5 represent a methyl group or an ethyl group, and zl, Z2, and z3 are a methyl group, an ethyl group, a propyl group, or a halogen-substituted methyl group) , represents an ethyl group, a propyl group or a phenyl group.

), the speed of color development on the transfer paper during sublimation transfer was even faster.

To synthesize the phenoxazine compound of the present invention, the following (1)
), (2), and (3).

(1) A phenoxacinium chloride compound represented by the general formula (Ri, R'', R3 represents the same meaning as above) is dissolved in water by heating, and 1,2-dichloroethane, toluene, etc. are immiscible with water. In the presence of a solvent, for example, an alkaline non-reducing reaction is carried out with sodium hydrosulfide to reduce the leuco form represented by the general formula (R1, R2, R3 have the same meanings as above).Weakly basic deoxidizing agent After adding , a chloroformate compound represented by the general formula % (Y represents the same meaning as in the city code) is added dropwise to perform 10-alkoxycarbonylation, purification and crystallization to form the general formula ( A phenoxazine compound represented by 1) is obtained.

(2) The phenoxacinium chloride compound represented by the general formula (IIT) is converted into the leuco form (IV) in the same manner as in (1).
A dicarbonate compound represented by the general formula % (a) (Y represents the same meaning as above) is added to obtain a phenoxazine compound represented by the general formula (1).

(3) The phenoxacinium chloride compound represented by the general formula (m) is reduced to the leuco form (IV) in the same manner as in (1), and after adding a weakly basic deoxidizing agent, phosgene gas is added to the organic solvent layer. A 10-chlorocarbonylphenoxazine compound represented by the general formula (R1, R2, and R3 have the same meanings as above) is obtained by introducing a phosgene solution or by dropping a phosgene solution. This 10-chlorocarbonylphenoxazine compound is redissolved in 1-toluene, and an alkoxide compound represented by the general formula % () (Y represents the same meaning as above and M represents an alkali metal) is added. then 1
Derivatization to 0-alkoxycarbonyl compound. The phenoxazine compound represented by the general formula (1) is obtained by purification and crystallization.

Specific examples of the phenoxazine compound represented by the general formula (1) synthesized in this way include 10-methoxycarbonyl-3,7-bis(diethylamino)phenoxazine, 10-trichloromethoxycarbonyl-amino ) phenoxazine, 10-ethoxycarbonyl 3
,7-bis(diethylamino)phenoxazine,],C
)-(2,2.2-1 hefluoroethoxycarbonyl)-3.7-bis(diethylamino)phenoxazine-10-(2-chloroethoxycarbonyl)-3.7
-bis(diethylamino)phenoxazine, 10-(2
-ethoxycarbonyl)-3.7-bis(diethylamino)phenoxazine, 10-(2-dimethylaminoethoxycarbonylxazine, 1-0-isopropoxycarbonyl 3,7-bis(diethylamino)phenoxazine, 1,0 −(n
-butoxycarbonyl)-3.7-bis(diethylamino)phenoxazine, 10-(2-butoxycarbonyl)-3.7-bis(diethylamino)phenoxazine,
1. 0-(tert-butoxycarbonyl)-3
．． 7-bis(diethylamino)phenoxazine, 10-
(2-Methyl-2-butoxycarbonyl)-3.7-bis(diethylamino)phenoxazine, 10-(3-methyl-3-pentyloxycarbonyl)-3.7-bis(
diethylamino)phenoxazine, 10-(2,4-dimethyl-3-pentyloxycarbonyl)-3.

7-bis(diethylamino)phenoxazine, 10-phenoxycarbonyl-3,7-bis(diethylamino)
Phenoxazine, 10-(3.5-dimethylphenoxycarbonyldiethylamino)phenoxazine, 10-benzyloxycarbonyl-3,7-bis(diethylamino)phenoxazine, 1.0-(4-chlorobesidyloxycarbonyl)3,7-bis (diethylamino)phenoxazine, 1
0-(/1-methoxybenzyloxycarbonyl)3,7
-bis(diethylamino)phenoxazine, 1O-(2
-Phenyl-2-propoxycarbonyl)-3,7-bis(diethylamino)phenoxazine, 1O-(2-phenethyloxycarbonyl)-3,7-bis(diethylamino)phenoxazine, 10-methoxycarbonyl-3
-diethylamino-7-dimethylaminophenoxazine, 10-ethoxycarbonyl-3-diethylamino-7
-dimethylaminophenoxazine, 10-impropoxycarbonyl 3-diethylamino-7-dimethylaminophenoxazine, IQ-(tert-butoxycarbonyl)-3-diethylamino-7-dimethylaminophenoxazine, 10-(2-methyl- 2-Butoxycarbonyl)-3-diethylamino-7-dimethylaminophenoxazine, 10-phenoxycarbonyl-3-diethylamino-7-dimethylaminophenoxazine, 1
0-benzyloxycarbonyl-3-diethylamino-7
-dimethylaminophenoxazine, 10-ethoxycarbonyl-3-diethylamino-7-(N-ethyl-N-
phenylamino)phenoxazine, 10-(2-butyroxycarbonyl)-3-diethylamino-7-(N-ethyl-N-phenylamino)phenoxazine, IQ
- (tert-butoxycarbonyl)-3-diethylamino-7-(N-ethyl-N-phenylamino)phenoxazine and the like. A coating solution is prepared by dissolving these phenoxazine compounds together with a binder in a solvent, and the coating solution is coated on a transfer paper and dried to prepare a transfer body for thermal recording.

As a binder, polysulfone, polycarbonate,
Suitable materials include polyester, polyether sulfone, polyacrylonitrile styrene, and cellulose derivatives.

A solvent suitable for dissolving the phenoxazine compound and the binder is used, for example.

Toluene, chlorobenzene, 1,2-dichloroethane,
These include tricrene, methyl ethyl ketone, and tetrahydrofuran. Use polyethylene terephthalate film or condenser paper as the transfer paper. A clear cyan image can be obtained by placing the thus prepared transfer body for thermal recording facing a transfer paper such as clay paper and heating the transfer body from the back side.

Next, the present invention will be explained by examples.

Example 1 6.0 g (0.1 mol) of 3,7-bis(diethylamino)phenoxacinium chloride 3 was added to 500 liters of water.
It was added to nQ and dissolved by heating to 80°C. 500 mQ of toluene was added to the female, nitrogen gas was introduced into the recording phase, the air was replaced with nitrogen gas, and then 87 g (0.5 mol) of sodium hydrosulfide and 40 m of water were added at 60°C.
8 g (0.2 mol) of sodium hydroxide dissolved in Q were added. The reduction reaction was carried out at the same temperature for 10 minutes with vigorous stirring. The dye was completely bleached and became colorless. After cooling to room temperature, 16.8 g of sodium hydrogen carbonate (
0.2 mol) Add phosgene 1 4.8 quickly, being careful not to let the contents boil over due to foaming.
g (0.

A toluene solution in which 15 mol) of 15 moles) was dissolved was added dropwise over 1.5 hours. The mixture was stirred at room temperature for 1 hour and left for 1 day. The reaction mixture was separated, and the toluene layer was washed five times with 500 mρ of water, dried over anhydrous sodium sulfate, and purified by decolorization by adding 8 g of activated carbon. The toluene solution was concentrated and dried, and 200 mQ of ethanol and 10 mQ of toluene were added and heated.
After dissolution, the mixture was cooled and allowed to stand for crystallization. After filtration and washing with a small amount of cold ethanol, the product was dried under reduced pressure to obtain 31.8 g (yield: 82, 0%) of a dark blue, grayish white powder of 10-chlorocarbonyl-3,7-bis(diethylamino)phenoxazine. Melting point, 1 2 3.5-124.5°C 10-chlorocarbonyl-3,7-bis(diethylamino)phenoxazine 1 9.4 g (0-05
mol) in 150 mfl of dry toluene and, with stirring, 8.4 g (0.0 molar) of potassium tert-butoxide.
075 mol) was added portionwise over 15 minutes at room temperature. After stirring for 1 hour, 100 mβ of water was added to dissolve the precipitated potassium chloride. After separation and washing five times with 100 mfl of water, the toluene layer was dried over anhydrous sodium sulfate and purified with 5 g of activated carbon. Concentrate, dry and add 2 ethanol to the concentrate
Crystallization was performed by adding 0mM. Cool to complete precipitation of crystals, filter, wash with cold ethanol, and dry under reduced pressure.
16.2 g (yield: 88.2%) of off-white crystals of 〇-(tert-butoxycarbonyl)-3,7-bis(diethylamino)phenoxazine were obtained. Melting point, 136°5~
138.5°C Example 2 Add several drops of pyridine to 300 mQ of toluene, 40-50
Trichloromethyl chloroformate was heated to 4.9°C.
．． 5 g (0.25 mol) were added dropwise over 30 minutes and stirred for ]-hours. After cooling to 30°C, N.

29.05 g (0.25 mol) of 2,4-dimethyl-3-pentanol mixed with 50 mQ of toluene and 0.5 nlt of N,N',N'-tetramethylurea was added dropwise over 30 minutes. After stirring at the same temperature for 2 hours, excess phosgene was removed by aeration with nitrogen gas, and the mixture was washed three times with 150 mQ of cold water. After drying over anhydrous sodium sulfate, the mixture was concentrated to a half-distilled volume to obtain a 2,4-dimethyl-3-pentylchloroformate toluene solution.

3,7-bis(diethylamino)phenoxacinium chloride 36-Og (0.1 mol) was reduced in the same manner as in Example 1 to obtain a 3,7-bis(diethylamino)phenoxazine toluene solution. To this, 21.0 g (0.25 mol) of sodium hydrogen carbonate was quickly added, taking care not to cause the contents to boil over due to foaming, to form the 2,4-dimethyl-3-bentylchloroform. A toluene solution of 1 to 1 was added dropwise to 1 over 30 minutes at room temperature, and the mixture was stirred at the same temperature for 2 hours. The reaction mixture was separated into layers, and the toluene layer was washed five times with 500 mM water, dried over anhydrous sodium sulfate, and decolorized and purified by adding 8 g of activated carbon.

The toluene solution was concentrated, mixed with 200 mΩ of ethanol and heated to dissolve the solution, then cooled and allowed to stand for crystallization. After filtering and washing with a small amount of cold ethanol, dry under reduced pressure.
30.4 g of greenish white crystals of O-(2,4-dimethyl-3-pentyloxycarbonyl)-3,7-bis(diethylamino)phenoxazine (yield: 65.0%)
I got it. Melting point, 101-102.56C 15-Example 3 44.0 g of dehydrated 2-methyl-2-butanol (0
, 5 mol) was added, and the mixture was heated to 50°C under a stream of dry nitrogen gas and stirred until all the sodium metal was dissolved. 19.4 g (0.05 mol) of 10-chlorocarbonyl-3,7-bis(diethylamino)phenoxazine was dissolved in 200 ml (l) of dry toluene, and the above slurry of sodium 2-methyl-2-butoxide was added to the solution. was added in 5 portions at room temperature over 5 minutes. After stirring for 1 hour, 200 nIQ of water was added to dissolve the precipitated sodium chloride. After separation and washing with 200 mQ of water 5 times, toluene was added. The layer was dried over anhydrous sodium sulfate and purified with 5 g of activated carbon. Concentrated, and the concentrate was treated with JSO-Proper Tool 10.
Add 0mQ and concentrate again at normal pressure, the distillate is 70IIIQ
It was concentrated until The concentrate was cooled to 0-5°C and kept cold. The precipitated crystals were filtered, washed with cold ethanol, and dried under reduced pressure to give 5.1 g (yield: 68.7%).

Melting point, 95.5-97.5°C Example 4 A coating solution having the following composition was prepared using the phenoxazine compounds shown in Table-1.

Note 1) Apply the coating solution of TYRIL783 (Asahi Kasei product) to a 9 μm thick consansor paper after drying, and the solid content type plate is 0.
It was coated with a bar coater to a coating weight of 5 g/rl and dried to prepare a transfer material for thermal recording.

Layer the coated surface of this thermal recording transfer material on commercially available clay paper,
Stamp coloring machine (manufactured by Kumagai Riki Kogyo) with surface pressure of 0 and 4
kg/cJ for 3 seconds. The results are shown in Table-1.

■ Coo-Y Table-1 Note 2) Heating temperature (°C) to achieve a color density of 1.0.

Shows good color development sensitivity at low temperatures. The color density was measured using a Macbeth reflection densitometer model RD-514 through a red filter (Wratten Nα25).

Example 5 A coating solution having the following composition was prepared using the phenoxazine compounds shown in Table-2.

Note 3) Tokyo Kasei ■ reagent (viscosity when added at 5% to a mixed solution of toluene and ethanol (80:20) is 45 to 55 cps at 25°C) The following procedure was performed in the same manner as in Example 4.

The results are shown in Table-2.

Table 2 19-Example 6 A coating solution having the following composition was prepared using the phenoxazine compounds shown in Table 3.

Note 4) Needel P-1700 (Nissan Chemical Industry ■ product) Hereinafter, the same procedure as in Example 4 was carried out to conduct a light emission test using a fluorescent lamp. The results are shown in Table-3.

COO-Y Note 5) Fluorescent lamp 40,000 lux, 48 hours, 40°C, standard nibble scale.Furthermore, a heat-sensitive recording transfer material prepared in the same manner was heated for 6 months.
After storage in a dark place, a sublimation color development test was conducted under the same conditions.

The results are shown in Table 4.

Table 4 [Effects of the Invention] As is clear from the above examples, the phenoxazine compound of the present invention has a fast sublimation color development rate, and develops a clear cyan color with high density and good light emitting properties. Further, the heat-sensitive recording transfer material using the phenoxazine compound of the present invention is stable even after long-term storage, and the sublimation color development sensitivity does not decrease.

Patent applicant: Hodogaya Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R^1 and R^2 represent an alkyl group having 1 to 4 carbon atoms, and R^ 3 represents an alkyl group or aryl group having 1 to 4 carbon atoms, Y is a halogen atom,
It represents an alkyl group, an aryl group, or an aralkyl group having 1 to 8 carbon atoms which may have an alkoxy group or a dialkylamino group as a substituent. ) A phenoxazine compound represented by 2. In a transfer body of a sublimation transfer type thermal recording method in which an image is obtained by heating a transfer body coated with a sublimation color former with a thermal head or the like and transferring the sublimation color former to a separate sheet of paper to be transferred, the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^1 and R^2 represent an alkyl group having 1 to 4 carbon atoms, and R^3 has 1 to 4 carbon atoms. represents an alkyl group or an aryl group, Y is a halogen atom,
It represents an alkyl group, an aryl group, or an aralkyl group having 1 to 8 carbon atoms which may have an alkoxy group or a dialkylamino group as a substituent. ) A transfer material for thermal recording, characterized in that it uses one or more kinds of phenoxazine compounds represented by the following. 3. The phenoxazine compound has the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R^4, R^5 represent a methyl group or an ethyl group, Z^1, Z^2, Z^3 is a methyl group, an ethyl group,
Represents a propyl group, or a halogen-substituted methyl, ethyl, propyl, or phenyl group. ) The transfer body for thermal recording according to claim 2.