JPS60142334A - Diazo copying material - Google Patents

Abstract

PURPOSE:To obtain a sharp image superior in light resistance, free from background coloring, and high in density by using a combination of a specified hydrazone type coupler and a metal salt capable of forming a chelate with a coupling product. CONSTITUTION:A diazo copying material is composed of a diazonium salt, a metal salt capable of forming a chelate with a coupling product, and as a hydrazone type coupler, a pyridine deriv. represented by formula I in which R<1> is lower alkylene, and R<2> is lower alkyl. This coupler is high in coupling tendency, and rapidly reacts with the diazonium salt to give a sharp red coupling product (formazan dye). Metallic salt including a complex salt capable of forming a chelate with said dye is, generally, the salts of transition metals, such as Ni, Zn, Co, Cu, Mn, Ag, Ti, Mo, W and Ge.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] This 1f3tlJl relates to a diazo copying material comprising a diazonium salt, a hydrazone coupler, and a metal salt capable of chelating the coupling product.

[Prior art]

Conventionally, diazo copying materials utilizing a coupling reaction between a diazonium salt and a coupler comprising a compound with which the diazonium salt can undergo an electronic reaction have been widely known and have been used as diazo photosensitive papers and the like. In such diazo copying materials, a phenol or naphthol compound is generally used as a coupler, but when such a phenol or naphthol compound is used as a coupler, a coupling reaction between the diazonium salt and the coupler may occur. The coupling product formed by (
Azo dyes) have the disadvantage of insufficient lightfastness.

On the other hand, it is also known to use hydrazone compounds as couplers for diazonium salts (for example, JP-A Nos. 54-35723, 54-35724, 5
4-30023, etc.). Diazo copying materials that utilize a coupling reaction between a diazonium salt and a hydrazone coupler produce a stable clear black image with a gray or blue tinge even if the development conditions vary slightly. Since it has a yellow or deep yellow color, it has the disadvantage of causing background coloration and poor single image clarity.

〔the purpose〕

An object of the present invention is to provide a diazo copying material that utilizes a coupling reaction between a diazonium salt and a hydrazone coupler and has excellent light resistance without developing background color.

〔composition〕

According to the present invention, in a diazo copying material comprising a diazonium salt, a hydrazone coupler, a coupling product, and a metal salt capable of chelating, a pyridine derivative represented by the following general formula is used as the hydrazone coupler. A diazo copying material is provided which is characterized by:

In the above formula, R1 is a lower alkylene group, and the number of carbon atoms] ~
4 is preferably used, and R2 is a lower alkyl group, and those having 1 to G carbon atoms such as methyl, ethyl, propyl, butyl, and pentyl are usually used.

Specific examples of the hydrazone compound represented by the above general formula include the following.

The caniplar represented by the general formula (1) used in the present invention has the advantage that it is pale yellow in color compared to the conventional general hydrazone coupler, and therefore provides a clear image without background coloration. Since it is water-soluble, it has the advantage that the photosensitive layer forming liquid can also be made into an aqueous solution.

The coupler also reacts quickly with the diazonium salt to give a bright red coupling product (formazan dye).

Furthermore, the coupler exhibits high coupling properties,
It is characterized by an extremely rapid coupling reaction with diazonium salts.

The diazo copying material of the present invention comprises a diazonium salt, a hydrazone coupler represented by the general formula (1), and a metal salt capable of chelating a coupling product (formazan dye). Formazan dye, which is a camping product obtained by the camping reaction between a diazonium salt and a hydrazone coupler, is
Although there is a problem of poor light resistance, this problem can be solved by chelating the formazan dye with a metal salt. That is, formazan dyes chelated with metal salts are significantly more stable and exhibit improved lightfastness than those that are not chelated.

Metal salts (including complex salts) that can chelate with formazan dyes are generally salts of transition metals, such as nickel, zinc, cobalt, copper, manganese, europium, iron,
Included are salts of metals such as silver, cadmium, chromium, titanium, molybdenum, tungsten, and germanium. Further, as the metal salt, various salts of inorganic acids and organic acids can be used, such as sulfates, nitrates, hydrochlorides, benzenesulfonates, acetates, carbonates, and complex salts. Examples include aco complexes, amine aco complexes, acetoacetyl complexes, ethylenediamine complexes, cyano complexes, tetracarbonyl complexes, thiocyanate complexes, isocyanate complexes, and nitrilo complexes. When such a metal salt is camped with a hydrazone coupler and a diazonium salt, it instantly undergoes a chelation reaction with the formed formazan dye, producing a bright, high-density blue image. The amount of metal salt to be used may be at least the stoichiometric amount, and is generally 0.5 to 1 mole of formazan dye.
~10 moles.

As the diazonium salt used in the present invention, any diazo compound used in ordinary diazo copying materials can be used, and representative ones are as follows.

4-diazo-2,5-dimethoxyphenylmorpholine,
4-diazo-2,5-jethoxyphenylmorpholine,
4-diazo-2,5-dipropoxyphenylmorpholine, 4-diazo-2,5-dibutoxyphenylmorpholine,
4-Diazo-2,5-dibutoxy-N-benzyl-N-
Nithylaniline, 4-diazo-2,5-dibutoxy-N, N-dibutyla 4-diazo 2,5-dibutoxy-N-benzyl-N-
Hydroxyethylaniline, 4-diazo-2,5-dibutoxyphenylpiperidine.

4-Diazo-3-methoxyphenylpiperidine, 4-diazo-2,5-jethoxyphenylpyrrolidine, 4-diazo-2,5-dipropoxyphenylpiperazine, 4-diazo-N,N-dimethylaniline, 4-diazo −
N,N-diethylaniline, 4-diazo-N-ethyl-
N-hydroxyethylaniline, 4-diazo-N,N-dipropylaniline, 4-diazo-phenylmorpholine, 4-diazo-phenylpyrrolidine, 4-diazo-2-methylphenylpyrrolidine, etc.

Further, in the present invention, known additives can be used in order to improve the storage stability of recorded images.

As the additive, sodium naphthalene mono-, di- or tri-sulfonate, sulfosalicylic acid, urea, thiourea, tartaric acid, citric acid, malic acid, malonic acid, caffeine, theophylline, saponin, etc. are used.

In order to produce the diazo copying material of the present invention, a photosensitive layer forming solution is prepared using the above-mentioned components, and this is coated on a support and dried. Any conventionally used support such as paper or cloth can be used, but if the photosensitive layer solution has poor wettability, it is necessary to pre-treat the support before applying the photosensitive layer forming solution. It is preferable to perform a treatment such as providing a layer (precoat layer, adhesive layer).

The amount of coupler used when preparing the photosensitive layer forming liquid is 2.0 to 1.0 to 1 mo Il of the diazo compound. Omon
is preferred. Furthermore, when a pretreatment layer is provided, at least a portion of the metal salt or coupler can be contained in the pretreatment layer.

〔effect〕

The diazo copying material of the present invention uses a specific hydrazone coupler as well as a coupling product and a metal salt that can be chelated, so that it has excellent light resistance and a clear, high-density image with no background coloration. give an image.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example I A photosensitive layer forming liquid was prepared by mixing the following components.

Tartaric acid: 2g Caffeine 2g Naphthalene-1.3.6-trisulfonic acid: 1g Sodium 4-diazo-2,5-dibutoxyphenyl: 1g Morpholine chloride Nickel benzenesulfonate: 1g Saponin: 0.1g Water: 100mn In addition, the above-mentioned hydrazone compound is prepared by combining 2-pyridylhydrazine and 2-methoxyacetaldehyde in ethanol/
It was obtained by reacting at a temperature of 20°C in a solvent consisting of water.

The above photosensitive layer forming liquid was applied to a white base paper for a diazo copying material and dried to obtain a two-component diazo copying material.

Comparative Example A diazo copying material was obtained in the same manner as in Example 1 except that sodium 2,3-dihydroxynaphthalene-6-sulfonate, which is commonly used as a diazo coupler, was used instead of the hydrazone coupler.

The copying material thus obtained was transferred to a diazo copying machine (50-
450 (manufactured by Ricoh) to form a blue complex image, the resulting image was a clear image with no background coloring, and the image quality did not deteriorate over time.

Next, the above sample was set in a fade meter (manufactured by Suga Test Instruments Co., Ltd., Long Life Fade Meter FA-3 model) equipped with a carbon arc lamp for 12 hours, and was placed in a Macbeth reflection densitometer (sensitivity λmax = 550 mm).
), the change in image density over time was measured, and the results shown in the following table were obtained.

Table 1 From the results shown in the table above, the images obtained with the diazo copying material of the present invention are clear blue images without background coloration, and are stable images with good light resistance that do not deteriorate in image quality over time. It can be seen that it is.

Furthermore, since the hydrazone coupler used in the present invention has high water solubility, the photosensitive layer coating solution has good storage stability, and crystals do not precipitate even after a long period of time.

Example 2 A diazo copying material was prepared in the same manner as in Example 1 except that the following was used as the hydrazone coupler, and an image was formed. As in Example 1, a stable blue image without background coloring was obtained. .

The hydrazone compound is prepared by mixing 2-pyridylhydrazine and 2-ethyl-xyacetaldehyde in ethanol/
It was obtained by reacting at 20°C in an aqueous solution.

Example 3 A diazo copying material was prepared in the same manner as in Example 1 except that a hydrazone coupler was used, and an image was formed. As in Example I, a stable blue image without background coloring was obtained.

The hydrazone is obtained by reacting hydridinopyridine and 3-methoxypropyl aldehyde in a methanol/water solvent at 20°C.

Claims (1)

[Claims] (1) A diazo copying material comprising a diazonium salt, a hydrazone coupler, a coupling product, and a metal salt capable of chelating, wherein a pyridine derivative represented by the following general formula is used as the hydrazone coupler. Copying materials. (In the formula, 1 (1 is a lower alkylene group, R2 is a lower alkyl group)