JPS60249141A - Diazo copying material - Google Patents

Abstract

PURPOSE:To obtain a diazo copying material having bluish violet color tone of a formazan metallic chelate dye by combining a specified diazo compd., a Ni compound, and a hydrazone coupler. CONSTITUTION:A diazo compd. expressed by the general formula is mixed with a hydrazone coupler and an Ni compd. capable of forming a chelate compd. with the coupled product to prepare a soln. for forming a photosensitive layer. A soln. for forming a precoated layer is coated on the white raw paper for the sensitized paper to form a precoated layer, and the above described soln. for forming the photosensitive layer is coated thereon which is dried to prepare a diazo copying paper.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diazo copying material exhibiting a formazan metal chelate dye of blue-violet color.

BACKGROUND OF THE INVENTION A diazonium salt, a hydrazone coupler capable of electronically reacting with the diazonium salt, and a coupling product and a hydrazone coupler.
Diazo copying materials have been developed that contain divalent transition metal compounds that can be converted into monomers.

Careful attention has been paid to the color tones of diazo copies so that they match the human sensibilities and do not feel out of place with conventional products.

However, when examining the spectral absorption characteristics of the above-mentioned diazo copying materials experimentally, it is easy to find a combination of compounds that have exactly the same properties as the dyes (λwax 570-580rv) used in conventional diazo copying materials. It wasn't. That is, all color tones have long wavelengths (λmay, 60
0nm or more) side, and short wavelength (λmax 600nm
On the lower)' side, the color tone is still unsatisfactory, there is a risk of dichroism depending on the development conditions, and quality such as light resistance is affected, making adjustment difficult.

The problem to be solved by the present invention is to obtain a desired color tone of a diazo copying material using a hydrazone coupler.

Means for Solving the Problems The present invention provides a diazo copying material characterized in that a diazo compound represented by the following general formula, a hydrazone coupler, and a nickel compound capable of chelating with the coupling product are used on a support. It is.

(R3 and R4 are C1-3 alkyl groups) R2: H, -
CB +-15, C00Rs, C0Rs (Rs-11,
Alkyl group of 01 to 3) X: An acid residue or an acid residue forming a double salt with a metal salt.

Note that the acid residue of X is a halogen ion or BF4-
, PF6-, etc. are preferable, while metal salts that form double salts with acid residues include, for example, Zn C12, Cd C12, Sn C
There are 12 etc. Specific examples of the compound of the above general formula include the following. Here, the equivalent of X is C
1.1/2 Zn C12.

Moreover, the following are illustrated as a nickel compound.

Nickel penzesulfonate, nickel acetate (tetrahydrate)
, nickel (II) acetyl acetate, nickel ammonium chloride, nickel ammonium sulfate, nickel benzoate, nickel bromide, nickel carbonate (ji-based), nickel chloride, nickel citrate, nickel cyclohexane butyrate, dihydrogen hypophosphite nickel formate, nickel hydroxide, nickel hypophosphite, nickel primary iodide, nickel nitrate, kerosene, nickel oleate, nickel oxalate, nickel phosphate, nickel phthalocyanine, potassium nickel cyanide, potassium nickel sulfate, Nickel selenate (hexahydrate), nickel stearate, nickel sulfamate, nickel sulfate (monohydrate), nickel sulfate (hexahydrate), nickel tartrate, nickel thiocyanate.

Examples of hydrazone couplers used in the present invention include the following.

1. 2.4-dihydroxybenzaldehyde 112-
Hydroxybenzaldehyde 172-Hydroxybenzaldehyde-2-benzothiazolylhydrazone sodium salt 180
-Sulfobenzaldehyde-2-benzothiazolylhydrazone sodium increase-2-
Byridylhydrazonalium salt 41 Acetaldehyde-2-quinolylhydrazone 42 1-Propylaldehyde-2-quinolylhydrazone The present invention will be explained in more detail with reference to the following examples.

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

Tartaric acid 1.5g 2X10-3 moles Thiourea 0.5g Nickel benzenesulfonate 5x10-”mol saponin o, ig The above composition was made up to a total volume of 100 mβ with water.

Apply the following pre-coat layer forming liquid to white photosensitive paper base paper,
Form a pre-coat layer (dry weight 1.5 (+/11')
) The above-mentioned photosensitive layer forming liquid was applied onto L/2 and dried to prepare diazo copying paper.

Precoat layer forming liquid Silica (particle size 1 to 5μ) 50g Polyvinyl acetate emulsion (solid content 40%) 100 () Methylene blue 0.01 (1) The original image with the image was superimposed on this diazo copying paper and commercially available diazo semi-dry copying was performed. After exposure, the image was developed using a machine (Ricobee 5D-205) (visual liquid adhesion amount: 1.5 g/m 2 ) and the image was made into 1 q. The results are described below.

Color tone dual maximum absorption wavelength (blue violet) 570nl
l1 Reflection density (measured with a Macbeth densitometer, using a green filter): Maximum density in the image area 1.20 Density in the background area 0.11 The above sample was measured using a fade meter equipped with a carbon arc light (Long Life Fade Meter manufactured by Suga Test Instruments ■) FA-3 model) for 12 hours, and the change over time of the image mi at the maximum absorption wavelength was measured, and the results shown in a in the figure were obtained. As the results clearly show, the image was very clear in both image density and contrast at the initial stage of image formation. Also, sufficient visual density was maintained over time.

Example 2 A photosensitive layer forming liquid having the following components was prepared and treated in the same manner as in Example 1 to prepare diazo copying paper, and a copy image was obtained in the same manner as in Example 1.

Tartaric acid 1.5g 2X10-3 moles C8-’2 0.5g Nickel benzenesulfonate 5X10-3 mole Saponin 0.1g The total volume of the above composition was made up to 100 m 12 with water.

The results are described below.

Color tone: Maximum absorption wavelength (blue violet) 75 nm Reflection density: (same as Example 1) Maximum density in image area 1.23 Density in background area 0.11 Discoloration and fading property = (Measured in the same manner as Example 1) Results are shown in the figure. The following results were obtained: Image III and Contrast I were both very clear images, and sufficient visual density was maintained even over time.

Example 3 Diazo copying paper was obtained in the same manner as in Example 1, except that diazo compound was used instead of the diazo compound, and the same tests as in Example 1 were conducted. The results are as follows.

Color tone: 577r++n Reflection density: Maximum density in image area 1.20 Density in background area 0.11 Discoloration and fading property: Same as Example 1 Example 4 Same as Example 2 except that (instead of the diazo compound) A diazo copying paper was obtained, and the same test as in Example 2 was conducted.The results are as follows.

Color tone: 580rv Reflection density: Image area maximum 11 degrees 1.23 Background area density 0
．． 10 Discoloration and fading property: Same as Example 2 Comparative Example 1 The following components were mixed to prepare a photosensitive layer forming liquid.

Tartaric acid 1.5g Caffeine 1g 2xlO-"mol 08-2 0.5g Zn C+ 2 5X '10-"mol Saponin 0.
1g The total amount of the above composition was made 10011IJ2 with water.

Diazo copying paper was obtained in the same manner as in Example 1, and Example 1
I did a similar test. The results are listed below.

Color tone: Maximum absorption wavelength (blue violet) 75 nm Reflection density: Image area maximum density 1.20 Background density 0.11 The above sample was measured for the change in image density over time using a fade meter in the same manner as in Example 1. The results showed about three times the deterioration of Example 1.2, and the visual density was insufficient, that is, it was a problem as a copied image.

Comparative Example 2 The diazonium salt in the photosensitive layer forming liquid component of Example 1 was replaced with the diazonium salt shown below, and the same treatment as in Example 1 was performed to prepare diazo copying paper, and a copy image was obtained in the same manner as in Example 1. Ta.

The results are described below.

Color tone dual maximum absorption wavelength (blue) 15 nm Reflection m thin: Image area maximum density 1.18 Background density 0.11 As mentioned above, the desired color tone (λmax 570 to 590 nm) could not be obtained because the color tone λl1lax shifted toward the long wavelength side. Ta.

Discoloration and fading properties: The results shown in Figure d were obtained, and in terms of visual density, sufficient density was maintained as in Example 1.2.

Comparative Example 3 A photosensitive layer forming liquid having the following components was prepared, and diazo copying paper was prepared in the same manner as in Example 1, and a copy image was obtained in the same manner as in Example 1.

Tartaric acid 1.5g Thiourea 0.5g Zn　C+　2　5X10-'mol Saponin 0.1g The results are described below.

Color wI: Maximum absorption wavelength (blue) eeon+11 reflection density: Image area maximum density 1.21 Background density 0.11 As mentioned above, the desired color tone (λ1llaX 570 to 570 nl) could not be obtained because the color tone λmax was biased toward the long wavelength side. Ta.

Comparative Example 4 A solution was prepared in which the metal compound nickel benzenesulfonate in the photosensitive layer forming liquid component of Example 1 was replaced with zinc chloride, and the same treatment as in Example 1 was performed to prepare diazo copying paper. A copy image was obtained in the same manner.

The results were as follows.

Color tone: Maximum absorption wavelength (blue) 630 nm As mentioned above, the color tone (λl1lax) was biased toward the long wavelength side, and the desired color tone (λmax 570 to 590 nm) could not be obtained.

Effects of the Invention According to the present invention, by combining a specific diazo compound, a nickel compound, and a hydrazone coupler, an image with a desired color tone (λwax'5γ0 to 590 nm) can be easily obtained, and its light resistance is also improved. , as shown in the above test results, are satisfactory.

[Brief explanation of drawings]

The figure is a graph showing test results in Examples and Comparative Examples of the present invention. Patent applicant Rico Co., Ltd. - Agent Patent attorney Hide Komatsu Agent Patent attorney Hiroshi Asahi 0 4 8 12

Claims (1)

[Scope of Claims] A diazo copying material characterized in that a diazo compound represented by the following general formula, a hydrazone coupler, and a nickel compound capable of chelating with a coupling product are used on a support. (R3 and R4 are C1-3 alkyl groups) R2: H, -
C6H5, C00Rs, -CORs (Rs = H, C1-3 alkyl group) X: An acid residue or an acid residue forming a double salt with a metal salt.