JPS60142332A - 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 X is -(CH=CH2)n-CH3, (n) being 1, 2, or 3, or furyl. This coupler 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] The present invention 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 is yellow or 'a-yellow, it has the disadvantage of causing background coloration and poor 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 the diazo copying material comprising a diazonium salt, a hydrazone coupler, a coupling product, and a metal salt capable of converting into chelate, a pyridine derivative represented by the following general formula is used as the hydrazone coupler. A diazo copying material is provided which is characterized in that:

[In the formula, X is -(CH'=CH''''rVCH3 (in the formula, n
is an integer of 1 to 3) or a furyl group] The coupler represented by the general formula (1) used in the present invention is itself pale yellow in color compared to conventional general hydrazone couplers. It has the advantage of providing clear images without background coloration, and since it is water-soluble, it also has the advantage that the photosensitive layer forming liquid can also be an aqueous solution. The coupler also reacts quickly with the diazonium salt to give a bright red coupling product (formazan dye).

The diazo copying material of the present invention comprises a diazonium salt, a hydrazone coupler represented by the general formula (I), and a metal salt capable of chelating the coupling product (formazan dye). Formazan dye, which is a coupling product obtained by the coupling reaction between a diazonium salt and a hydrazone coupler, has a problem of poor light resistance, but this problem can be solved by chelating the formazan dye with a metal salt. be done. That is, the formazan dye chelated with a metal salt is
It exhibits significantly increased stability and improved light resistance compared to its non-chelated counterpart.

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 coupled 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 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-dibutylaniline, 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 liquid has poor wettability, it may be necessary to place it on the support before applying the photosensitive layer forming liquid. It is preferable to perform a treatment such as providing a treatment layer (precoat layer, adhesive layer).

The amount of the coupler used when preparing the photosensitive layer forming liquid is preferably 2.0=1.0 mofi per 1 mo Q of the diazo compound. 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 coloring. give an image.

〔Example〕

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

Example 1 A photosensitive layer forming liquid was prepared by mixing the following components.

Tartaric acid 82g Caffeine = 2g Naphthalene-1.3.6-trisulfonic acid 21g Sodium 4-diazo-2,5-dibutoxyphenyl = 1g Morpholine chloride Nickel benzenesulfonate: 1g Saponin: 0.1g Water: 100mA The above-mentioned hydrazone compound is obtained by reacting hydrazinopyridine and propylenedehyde at a temperature of 20° C. in a solvent consisting of methanol/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.

Example 2 A diazo copying material was obtained in the same manner as in Example 1 except that the hydrazone coupler represented by the following formula was used.

Note that this hydrazone compound was obtained by reacting hydrazinopyridine and furfural in a THF solvent at 25°C.

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 (SD-
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 sample was placed 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.
When the change in image density over time was measured using a Macbeth reflection densitometer (maximum sensitivity: 550 nm), the results shown in the following table were obtained.

From the results shown in Table 1 above, the images obtained with the diazo copying material of the present invention are clear blue images with no background coloring, 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 3 In Example 1, as a hydrazone coupler.

Diazo copying material was prepared in the same manner except that .

When an image was formed, as in Example 1, a stable blue image with no background coloration was obtained.

The hydrazone compound is obtained by reacting hydrazinopyridine and hexadienaldehyde in an ethanol water solvent at 30°C.

Example 4 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 1, a stable blue image without background coloring was obtained.

The hydrazone is prepared by mixing hydrazinopyridine and octa-1 to octa-aldehyde in a dioxane solvent.
It was obtained by reacting at 5°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, X is -fCH= CH'jF CH3 (in the formula, n
is an integer of 1 to 3) or a furyl group]