JPS59160136A - Diazo copying material - Google Patents

Abstract

PURPOSE:To form an image having superior fastness by blending a diazonium salt with a specified hydrazone compound and a metallic salt capable of chelating with a coupled product. CONSTITUTION:A diazo copying material is formed by blending a diazonium salt with a hydrazone compound capable of causing an electrophilic reaction with the diazonium salt and represented by the formula and a metallic salt capable of chelating with a coupled product. A stable image having high fastness and causing no fading due to light, heat, air, etc. can be obtd. by using the hydrazone compound as a coupler for the diazonium salt. Two or three kinds of metallic salts may be used to obtain easily a black image without changing the combination of the hydrazone compound with the diazonium salt. Since the resulting dye is a stable chelate compound because of the presence of the metallic salt, an image having high fastness is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD The present invention relates to diazo copying materials, and more particularly to diazo copying materials.
The present invention relates to a diazo copying material capable of forming images with excellent fastness that do not fade due to air, heat, etc.

BACKGROUND ART Conventionally, it has been known to use a hydrazone compound as a coupler 1 of a diazonium salt in diazo copying materials (see Japanese Patent Publication No. 30023/1983, Japanese Patent Publication No. 35723, and Japanese Patent Publication No. 35724). These couplers are
Although it is possible to obtain a stable gray or bluish black image even if the developing conditions vary slightly, for example,
Images obtained using the diazo copying material disclosed in Japanese Patent Publication No. 4-35723 are extremely susceptible to oxidative decomposition due to light, air, heat, and the like.

That is, formazan dyes that do not undergo chelation are less stable than α,β-naphthol dyes, resulting in images fading and deterioration of sharpness over time. In addition, in Japanese Patent Application No. 165859/1985 filed by the present applicant, image stability is improved using a metal compound that can chelate with a formazan dye produced by a coupling reaction between a diazonium salt and a hydrazonium compound. Diazo copying materials have also been proposed. This is because when a metal salt is used, the formazan dye formed by coupling and the metal salt coordinate to form a more stable 6-membered ring chelate compound, which easily fades due to light, air, heat, etc. This is to form a stable image that does not. However, the hydrazone compounds described in the application are SO+Na, COONa.

It has a CO01-1 group, which acts as an electron-withdrawing group to weaken the intramolecular hydrogen bond of the formazan dye and reduce the chelation rate. Furthermore, if the hydrazone compound contains a diethylamino group or a diethylamino group, the coupler causes background staining, impairing the clarity of the image.

Purpose The purpose of the present invention is to solve the above-mentioned conventional drawbacks,
In particular, the objective is to provide a diazo i photographic material with excellent image stability, in which the resulting image does not fade due to light, air, heat, etc., and furthermore, it is possible to provide a diazo i photographic material with excellent image stability by using a combination of multiple metal salts. The object of the present invention is to provide a diazo copying material that can be used.

Structure As a result of intensive research in view of the above-mentioned object of the present invention, the present inventors have found that when a compound represented by the following general formula (I) is used as a hydrazone compound, it is possible to obtain an image with high image stability and color fastness. It turns out that 14 will be awarded.

That is, the present invention comprises a diazonium salt, a hydrazone compound capable of electrophilic reaction with the diazonium salt, and a metal salt capable of chelating with a coupling product, wherein the hydrazone compound is represented by the following general formula (I). This article summarizes a diazo copying material characterized by being a compound represented by:

General formula (I) R1-CH,=N-Nl-l-R7 [wherein, RI: CH-kuhi Cl-17]
) However, n: an integer of 0 to 20 Examples of the hydrazone compound used in the present invention include hydrazone compounds represented by the general formula (I) such as 1"1".

Further, examples of the diazonium salt used in the present invention include diazonium salts represented by the following general formula.

R1;)'', C1-5 alkyl group or aralkyl group R3, R4: C+~5 alkoxy group X: BFa, BFs, CI Specifically, the following are exemplified.

4-dimethylaminobenzenediazonium chloride
1/2 zinc chloride, 4-diethylaminobenzine diazonium chloride
1/2 zinc chloride, 4-morpholinobenzine diazonium chloride, 1/2
Zinc dichloride, 4-pyridinobenzenediazonium chloride 1/2
Zinc chloride, 4-diethylamino-2,5-die I~xybenzenediazonium chloride 1/2 zinc chloride, 4-dipropylamino-2,5-dibutoxybenzene siazonium chloride 1/2 JN+zinc chloride Zinc-pyrazine-2,5-dibutoxybenzenediazonium chloride, 1/2 zinc chloride, 4-pyrazine-2,5
- Dib 1 ~ xybenzenediazonium chloride co/
Zinc dichloride, 4-pyridine-2,5-dibu1-xybenzenediazonium chloride, 1/2 zinc chloride, and the formazan dye and Kire-1 produced by camping the hydrazone compound of the present invention and diazonium salt. Metal salts that can be converted into zinc, nickel, thallium, and cobal]
Any inorganic or organic salt of a divalent metal can be used, such as
Specific examples include hydrochlorides, sulfates, nitrates, tin nitrites, acetates, benzenesulfonates, and carbonates of these metals. Examples of complex salts include Ako complex, Ammin Ako Meiho, Aretoazedyl button. body, ethylenediamine complex, cyano complex, tetrano J rubonyl button body, thiA cyanane 1 complex, isocyane 1~! Examples include ii form, nitro complex, nitrilo complex, and the like.

Table 1 (In this table, the maximum absorption wavelength (/!n1aX) of the formazan dye formed by the 1-razone compound represented by the formula (I) of the present invention and a typical diazonium salt)
, and (υ large absorption wavelength (λmax)) of the KIRE-1 compound formed from the dye and the metal ions shown in the same table.

Table 1 Compound NOλmax (mμ) Ni” Cr2
"Co"2 4
75 603 540 5303
475 610
535 5354
480 610 540. 5
455 480
609 5130 5406
500 640 5
60 5357
530 620 565 5508
540 6+
5 570 5709
550 620 585
58510 560
625 585 570 As is clear from the above table, this 5L method uses two or three types of metal salts in combination (this J, the same H1~Razon compound,
Black images can be easily obtained from the combination of diazonium salts.

Therefore, it is not necessary to use a plurality of diazoniums and couplers to form dyes of different tones, as in the conventional method, and to produce a black tone as a mixed tone of these dyes. In addition, the obtained dyes are stabilized by the metal salts, and can produce highly fast images that do not fade due to light, heat, air, etc. The speed is extremely fast because the hydrazone type is extremely fast, and it coordinates with the metal ion to form a stable 6-membered ring.The metal salt used is 1 m of formazan dye, 4 L at 0°C, and 0.5 ~1
A usage range of 0mo and e is desirable.

The present invention will be explained in detail below.

Example 1 Auxiliary agent; Tartar 0 sa 2. Og thiourea
1. Og isopropyl alcohol
1.0! ] After mixing and dissolving the above auxiliary agents in 90% water (I), the following components were dissolved in the order of hydrazone coupler, metal salt, and diazonium salt, and 1.2 g of silica was added and dispersed to prepare a photosensitive liquid.

n-Propyl-2-pyridylhydrazone 1, Oq Nickel benzenesulfonate 2.0 g Cobalt acetate 1.0 g 4-Dimedylaminobenzenediazonium chloride 1/2 Zn Cl 2
1. O (1) The photosensitive solution obtained in this way was placed on diazo base paper (scale ff 158 g/m2) at a concentration of 0.01 to 0.
．． After coating at 0.02f/llI2, the paper was dried with hot air at about 100° C. until the moisture content became about 40% to obtain the diazo copying paper of the present invention. Using the obtained diazo copying paper, a latent image was formed using Coby 5M-1500 manufactured by Ricoh Co., Ltd., and then ammonia development was performed. When the image quality of the obtained image was measured using a Macbeth densitometer, it was found to be a high-density black image with a reflection density of 1.40.

Example '2'' A diazo copying paper was obtained in the same manner as in Example 1 except that n-propyl-2-pyridylhydrazone was changed to 1)-propyl-2-benzothiazolylhydrazone in a3.
When an image was formed in the same manner as above, the reflection was 1.4.
A high density black image of 0 was obtained.

Example 3 3yloid -244 ('Hatashi Davison) 0.2
g Japan Acrylic 5C-61 Emulsion 0.1 g PVA-205 (East) 0.05 (1 water)
100
g was dispersed and coated on the same diazo base paper as in Example 1 at a coating amount of 0.066 to 0.03°C/g.
It was dried with hot air at 30°C. Next, a photosensitive liquid was prepared in the same manner as in Example 1 except that silica was removed, and the photosensitive liquid was coated on the base paper and dried to obtain diazo copying paper. (An image was formed in the same manner as in Example 1 using the diazo?!2 photo paper, and a high-density black image with a reflection density of 1.30 was obtained.

The images obtained in Examples 1 to 3 above were sent to Ska Test Instruments Co., Ltd.
As a result of irradiating the image with light for 12 hours using a manufactured fade meter, no fading was observed in the image.

Effects As explained above, the diazo copying material of the present invention uses the specific hydrazone compound represented by the general formula (I>) as a coupler, so that the diazo copying material of the present invention does not fade due to light, heat, air, etc. It is possible to form a highly stable image with high durability.Also, by using a plurality of metal salts, a black image can be easily obtained.

Patent applicant: Ricoh Co., Ltd. Agent: Patent attorney: Hidetake Komatsu

Claims (1)

[Scope of Claims] A diazonium salt, a hydrazone compound capable of electrophilic reaction with the diazonium salt, and a metal salt capable of chelating a coupling product, the hydrazone compound being represented by the following general formula (I): A diazo copying material characterized in that it is a compound. General formula (I) R+ CH=N NHR2 [wherein, R+: CH3+CH2)η, where n:O
~20v) integer