JPH1044618A - New developer composed of bis(p-toluenesulfonylamino carbonylamino)-diphenyl derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a new developer by using a developer composed of a bis(p-toluenesulfonylamino carbonylamino)-diphenyl derivative. SOLUTION: A developer is composed of a bis(p-toluenesulfonylamino carbonylamino)-diphenyl derivative represented by the formula (in the formula, A represents a group selected from the groups consisting of -NH-, -NHCONH- and -O-R-O-, and R represents -(CH2 )3 or -(CH2 )4 -). The developer is used at the ratio of 1mol, preferably 1.5mol or more to a developing agent of 1mol, and generally approximately 5-10 times of mol is prefferred. As a heat-sensitive coloring matter to which the developer can be applied, no particular restrictions are applied as far as the developer is a heat-sensitive coloring matter, and as an example, a phthalide dye, a thiofluoran dye, a fluoren dye, a triarylmethane dye, a diphenylmethane dye, a thiazine dye, a spiro dye or the like is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel color developer comprising a bis (p-toluenesulfonylaminocarbonylamino) -diphenyl derivative.

[0002]

2. Description of the Related Art Hitherto, as a color developer comprising a bis (p-toluenesulfonylaminocarbonylamino) -diphenyl derivative, those in which A is --CH _2- are known, but A is used in the present invention. There is no technique for using a compound having a simple structure as a color developer.

[0003]

An object of the present invention is to provide a novel color developer.

[0004]

According to the present invention, there is provided the following general formula [1]:

Embedded image [Wherein, A represents -NH-, -NHCONH-, -OR-
A group selected from the group consisting of O-, wherein R is-(C
H ₂ ) ₃ — or — (CH ₂ ) ₄ —].
The present invention relates to a developer comprising a diphenyl derivative.

The following are specific examples of the above compounds.

Embedded image

The compound of the present invention can be obtained, for example, by the following method.

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The compounds of the present invention are useful as developers for various electron-donating thermosensitive dyes (so-called leuco dyes).

The developer of the present invention is used in an amount of 1 mol or more, preferably 1.5 mol or more, per 1 mol of the color former, but is generally preferably about 5 to 10 times the molar amount.

The heat-sensitive dye to which the color developer of the present invention can be applied is not particularly limited as long as it is a heat-sensitive dye. For example, JP-A-51-21035, JP-A-51-21037, JP-A-51-21038, No. 55-115448, 5
No. 5-115449, No. 55-115450, No. 55
-115451, 55-115452, 55-
No. 115456, No. 57-167979, No. 58-1
No. 57779, No. 60-8364, No. 60-2758
No. 9, phthalide dyes described in each of the publications; thiofluorane dyes described in JP-A-59-148595; JP-A-59-199757; European Patent Application Publication No. 124377; -371
No. 58, No. 63-109086, No. 63-14536
No. 6, fluorene dyes, triarylmethane dyes, diphenylmethane dyes, thiazine dyes, spiro dyes, and the like.

Specific dye names include the following. That is, as the fluorene-based dye, 2-dibenzylamino-6-diethylaminofluoran, 2-anilino-6-diethylaminofluoran,
2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-cyclohexylmethylaminofluoran, 2-o-chloroanilino-6
-Diethylaminofluoran, 2-m-chloroanilino-6-diethylaminofluoran, 2- (3,4-dichloroanilino) -6-diethylaminofluoran, 2-
Octylamino-6-diethylaminofluoran, 3-
Diethyl-6-methyl-7-anilinofluoran, 2-
Dihexylamino-6-diethylaminofluoran, 2
-M-trifluoromethylanilino-6-diethylaminofluoran, 2-butylamino-3-chloro-6-diethylaminofluoran, 2-ethoxyethylamino-3
-Chloro-6-diethylaminofluoran, 2-anilino-3-chloro-6-diethylaminofluoran, 2-
Diphenylamino-6-diethylaminofluoran, 2
-Anilino-3-methyl-6-diphenylaminofluoran, 2-phenyl-6-diethylaminofluoran,
3- (4'-phenylaminophenylamino) -6-methyl-7-chlorofluoran, 3- (4'-phenylaminophenylamino) -7-methylfluoran, 3-
[4 '-(4 "-methoxyphenylamino) phenylamino] -5,6-benzofluoran, 3- [4'-
(4 "-methoxyphenylamino) phenylamino]-
6-chlorofluorane, 3- [4 '-(4 "-phenylaminophenylamino) phenylamino] -6-methyl-7-chlorofluoran, 3- [4'-(4" -phenylaminophenylamino) Phenylamino] -7-methylfluoran, 3- [4 '-(4 "-phenylaminophenylamino) phenylamino] -6-benzylfluoran, 3- [4'-(4" -phenylaminophenylamino) Phenylamino] -7-cycloalkylfluoran, 3- [4 ′-(4 ″ -phenylaminophenylamino) phenylamino] -7-chlorofluoran, 3-
[4 '-(4 "-phenylaminophenylamino) phenylamino] -6-chlorofluoran, 3- [4'-
(4 "-phenylaminophenylamino) phenylamino] -5,7-dichlorofluoran, 3- [4'-
(4 "-phenylaminophenylamino) phenylamino] -7-sec-octylfluoran, 3- [4'-
(4 "-phenylaminophenylamino) phenylamino] -7-phenylfluoran, 3- [4 '-(4"-
Phenylaminophenylamino) phenylamino]-
6,7-dimethylfluoran, 3- [4 '-(4 "-phenylaminophenylamino) phenylamino] -5
6-benzofluoran, 3- [4 '-(4 "-phenylaminophenylamino) phenylamino] -7,8-benzofluoran, 3- [4'-(4" -phenylaminophenylamino) -2 '-Methylphenylamino] -6
-Methyl-7-chlorofluoran, 3- [4 '-(4 "
-Phenylaminophenylamino) phenylamino]-
7-methoxyfluoran, 3- [4 '-(4 "-phenylamino-3" -methoxy-6 "-methylphenylamino) phenylamino] -7-chlorofluoran, 3-
[4 '-(4 "-phenylamino-3" -methylphenylamino) -2'-methylphenylamino] -6-methyl-7-chlorofluoran, 3- [4'-(4 "-phenylaminophenyl Amino) -2 ', 6'-dichlorophenylamino) -7-methylfluoran, 2-methyl-
6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2,3-dimethyl-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 3-
Methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-chloro-3-methyl-6
p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran, 2,3-dimethyl-6-p- (p-phenyl Aminophenyl) aminoanilinofluoran, 3-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran, 2-chloro-3-methyl-6-p- (p-phenylaminophenyl) amino Anilinofluoran and the like, as triarylmethane compounds, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (that is, crystal violet lactone), 3,3-bis (p-
Dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,3-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindole- 3-yl) phthalide and the like, as diphenylmethane compounds,
4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, N
-2,4,5-trichlorophenyl leuco auramine and the like; thiazine compounds such as benzoyl leucomethylene blue and p-nitrobenzyl leucomethylene blue; spiro compounds such as 3-methyl-spiro-dinaphthopyran and 3- Ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran,
3-benzylspiro-dinaphthopyran, 3-methyl-naphtho- (3-methoxy-benzo) spiropyran, 3-propyl-spiro-dibenzopyran and the like.

[0011]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by this.

Example 1 Part 1: Synthesis of 4,4'-bis (p-toluenesulfonylaminocarbonylamino) diphenylamine

Embedded image The flask was charged with 10.0 g of 4,4'-diaminodiphenylamine and dissolved in 300 ml of acetonitrile. 21.8 g from a dropping funnel while stirring this solution.
Of p-toluenesulfonyl isocyanate was added dropwise.
A white solid precipitated with the addition. The mixture was further stirred and filtered to obtain 21.2 g of white crystals.

Part 2: Production of thermosensitive recording paper A developer dispersion and a dye dispersion having the following compositions were prepared and treated with a sand grinder until the respective average particle diameters became 2.5 μm. Developer dispersion White crystals obtained in Part 1 above 2.0 parts by weight 10 wt% aqueous solution of polyvinyl alcohol 20.0 parts by weight Water 20.0 parts by weight Dye dispersion 3-diethylamino-6-methyl-7-anilino- Fluoran (trade name: ODB-1 manufactured by Yamamoto Kasei Co., Ltd.) 7.0 parts by weight 10 wt% aqueous solution of polyvinyl alcohol 40.0 parts by weight Water 10.0 parts by weight Both liquids are uniformly dispersed and mixed for 30 minutes using a paint conditioner. And a white slurry. 50g of this
/ M ² high-quality paper on one side using a bar coater No-14 (winding 0.35 mm) and a dye coating amount of 1.5 g / m ²
, And then processed so as to have a smoothness of 600 seconds to obtain a thermosensitive recording paper. The self-coloring density of the thermal recording sheet thus prepared was measured using a Macbeth reflection densitometer RD-51.
The measurement was performed using a type 4 black filter (Ratten # 106). Table 1 shows the results. The prepared heat-sensitive recording sheet was heated at 135 ° C and 2 kgf / c using a heat block printer.
By heating at m ² for 3 seconds, a good black-colored image was obtained. The maximum color density was measured with a Macbeth reflection densitometer RD-514 type black filter (Ratten # 106). Table 1 shows the results.

Example 2 Part 1: Synthesis of 4,4'-bis (p-toluenesulfonylaminocarbonylamino) diphenylurea

Embedded image The flask was charged with 10.0 g of 4,4'-diaminodiphenylurea and dissolved in 300 ml of acetonitrile.
While stirring this solution, 17.9 g of p was dropped from the dropping funnel.
-Toluenesulfonyl isocyanate was added dropwise. A white solid precipitated with the addition. The mixture was further stirred and filtered to obtain 22.3 g of white crystals.

Part 2: Manufacture of heat-sensitive recording paper Developer dispersion The same as the developer dispersion of Example 1 except that the developer was changed to the developer dispersion of Example 2 in the composition of the developer dispersion of Example 1. Same dye dispersion The dye of Example 1 was replaced with 2'-anilino-6 '-(dibutylamino) -3'-methylspiro [phthalide-3,9'-xanthene] [Yamamoto Kasei Co., Ltd., ODB-2] A thermosensitive recording paper was prepared in the same manner as in Example 1 using the same two dispersions as in Example 1, and the color was developed by the same means. As a result, a clear black color was formed. The data is shown in Table 1.

Example 3 Part 1: Synthesis of 1,3-bis [4 '-(p-toluenesulfonylaminocarbonylamino) phenyloxy] propane

Embedded image The flask was charged with 10.0 g of 1,3-bis (p-aminophenyloxy) propane and dissolved in 300 ml of acetonitrile. While stirring this solution, 16.8 g of p-toluenesulfonyl isocyanate was added dropwise from a dropping funnel. A white solid precipitated with the addition. The mixture was further stirred and filtered to obtain 23.6 g of white crystals.

Part 2: Manufacture of heat-sensitive recording paper Developer dispersion The same as Example 1 except that in the composition of the developer dispersion of Example 1, the developer was changed to the developer dispersion of Example 3. Same Dye Dispersion Same as Example 1 A thermosensitive recording paper was prepared in the same manner as in Example 1 by using both dispersions, and was colored by the same means. As a result, a clear black color was formed. The data is shown in Table 1.

[0018]

[Table 1]

[0019]

According to the present invention, a wide variety of developers can be obtained.

Claims (1)

[Claims] [Claim 1] The following general formula [1] [Wherein, A represents -NH-, -NHCONH-, -OR-
A group selected from the group consisting of O-, wherein R is-(C
H ₂ ) ₃ — or — (CH ₂ ) ₄ —].
A developer comprising a diphenyl derivative.