JPS5821254B2 - Diazoshikifukushiyazairiyo - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a copying method using a two-component diazo light-sensitive material, and more specifically, the present invention relates to a copying method using a two-component diazo light-sensitive material, and more particularly, to a two-component diazo light-sensitive material containing a color tone stabilizer that also acts as a development accelerator, an organic Relating to a two-component diazo copying method that enables quick and high-density development by applying a solution containing a base and an organic acid alkali metal salt under mild conditions such as room temperature or slight heating. .

A two-component diazo photosensitive material consisting of a photosensitive diazonium salt, an azo coupling component capable of coupling with the diazonium salt, and an acid stabilizer has low copying costs;
In addition, it is widely used in various copying fields because it is a simple copying operation and relatively large-sized copies can be easily obtained.

A conventionally known two-component diazo photosensitive material is introduced into a developing chamber after being given the necessary exposure via an original, and is developed under conditions such that ammonia-steam vapor condenses on the photosensitive material.

In commercial copying machines, it is virtually impossible to completely prevent ammonia from leaking from the developing chamber, and in currently used copying machines, ammonia leaks from the developing chamber and fills the machine. Steam is discharged outdoors using an exhaust fan and an exhaust duct.

In recent years, strict standards have been set for emissions into the atmosphere to protect the living environment, and it is inevitable that ammonia used in the diazo copying method will also be subject to strict regulations as a substance that pollutes the atmosphere.

The advantage of the so-called dry diazo copying method in which a two-component diazo photosensitive material is developed with ammonia-steam is that ammonia, which is the developer necessary to couple the reazonium salt and the azo coupling component, is volatile. There is virtually no residual on subsequent copy paper, and therefore there is almost no change over time such as red discoloration (coloring of the remaining coupler) in copies during storage, and this two-component diazo copy has a dye image that is uniform. Compared to dye images of component-based diaso-sensitive materials, it is clearer and has better white background.

Therefore, the ability to obtain diazo copies that have the advantages of the dry development method described above without producing air-polluting emissions such as ammonia is extremely important in terms of environmental health in the field of diazo copying. This is desirable.

Conventionally, a two-component diazo photosensitive material, which is known per se, has been used as a method for developing a two-component diazo photosensitive material with a developer other than ammonia to produce a diazo copy with excellent storage stability, that is, with less discoloration due to residual coupler. After exposure, the diazo photosensitive material is coated with an aqueous solution containing an organic base such as mono-, di-, or tri-ethanolamine, and the photosensitive material coated with this developer is heated to a high temperature of 100°C or higher to develop both. Methods of forming dye images in which components are coupled are known.

This method is excellent in that it can produce diazo copies with good contrast and color tone and less tendency to discolor during storage without using ammonia, but it requires the use of an amine aqueous solution during development. This method is still not fully satisfactory in that unless the coated photosensitive paper is heated to a fairly high temperature, the coupling rate is extremely low and copies with good color development cannot be obtained.

For example, when the above amine aqueous solution is contained in the developing section of a so-called wet-type commercially available copying machine that uses a liquid developer, and a commercially available two-component diazo copying paper is supplied to the copying machine to perform a copying operation, Almost no dye image has been formed on the copy discharged from the copying machine, and a visible dye image is formed for the first time by heating the copy to a high temperature.

Thus, although the formulation of conventionally known two-component diazo photosensitive materials can form a dye that is satisfactory when developed with ammonia, it is difficult to develop with an aqueous solution of an organic base or other weakly basic substance at room temperature. In this case, the coupling rate between the diazonium salt and the azo coupling component was extremely low, and was still unsatisfactory for the purpose of rapidly obtaining diazo copies with high contrast and image density.

Therefore, an object of the present invention is to apply a thin aqueous solution of an organic base or the like to a two-component diazo photosensitive material and develop it under mild conditions such as room temperature or slight heating. It is an object of the present invention to provide a diazo copying method capable of maintaining a coupling rate with a coupling component at a relatively high level and obtaining a clear image with high density.

Another object of the present invention is to produce a diazo type copying machine that does not require a special heating device during development and can obtain copies using a normal diazo wet type copying machine even when the above-described developing method is used. We are here to provide you with a method.

According to the present invention, a photosensitive diazonium salt, an azo coupling component consisting of a polyhydroxyaryl derivative, an acid stabilizer consisting of an oxycarboxylic acid having a dissociation constant of 1 x 10-3 or more, and at least an equivalent amount per photosensitive diazonium field are provided. A two-component diazo-sensitive material containing a molar amount of an alkaline earth metal salt is exposed through an original, and a thin layer of a solution containing both an organic base and an organic acid alkali metal salt is applied to the exposed material. A diazo copying method is provided, which is characterized in that the diazo copying method is applied in a form and developed at room temperature or with slight heating.

An important feature of the present invention is that a two-component diazo-sensitive material comprising a photosensitive diazonium salt, a polyhydroxyaryl derivative, a color tone stabilizer, and 1-1 alkaline earth metal salt and an acid stabilizer is It consists in developing with a thin layer of a solution containing both a base and an alkali organic acid.

That is, in addition to its well-known effect as a color tone stabilizer, this alkaline earth metal salt, in combination with the developer, significantly promotes the coupling between the diazonium salt and the polyhydroxyaryl derivative, and can be used at room temperature or with a slight addition of heat. It exhibits a development-promoting effect that enables rapid formation of high-density images even at high temperatures.

Further, by using a combination of an organic base and an alkali organic acid, the advantage is achieved that the development speed is further increased and the image density is higher than when either one of these is used alone.

Traditionally, photosensitive diazonium salts have generally been used in the form of double salts of zinc chloride to improve their shelf life.
Furthermore, it is widely practiced that diazo photosensitive compositions contain zinc chloride in free form for the purpose of stabilizing the color tone of the dye formed by coupling with an azo coupling component.

However, when such a diazo photosensitive layer containing zinc chloride is developed with a solution of the above-mentioned organic base or alkali metal salt of an organic acid, the coupling rate, that is, the development rate is extremely slow, and it is impossible to produce satisfactory copies at room temperature. I can't get it.

In the case of diazo copies, it is preferable that the dye image formed has a deep color tone from the viewpoint of image density and contrast, and for this purpose, couplers having a plurality of hydroxy groups,
That is, it is generally recommended to use polyhydric phenol derivatives, but these polyhydroxyaryl derivatives
When developed with an organic base solution in the presence of the aforementioned color stabilizer consisting of zinc chloride, the coupling rate tends to be extremely low.

The alkaline earth metal salt such as magnesium chloride used in the present invention is a well-known material along with ordinary salt chloride as a color tone stabilizer for two-component diazo light-sensitive materials. The present inventors discovered for the first time the fact that development speed is significantly increased when a thin layer of a mixed solution is applied. (
The use of an oxycarboxylic acid having a Ka 25 ) of 1.0×10” or more is also important in terms of the hue, image density, and contrast of the image formed.

In the present invention, the color stabilizer made of an alkaline earth metal salt includes alkaline earth metal halides such as magnesium chloride, calcium chloride, and barium chloride; alkaline earth metal sulfur oxyacids such as magnesium sulfite; : Alkaline earth metal nitrogen oxylates such as magnesium nitrate and calcium nitrate; Magnesium acetate,
Examples include organic acid salts of alkaline earth metals such as calcium acetate.

Of course, these inorganic or organic acid salts of alkaline earth metals must be water-soluble.

In the present invention, a particularly preferred alkaline earth metal salt in terms of coupling speed and image clarity is magnesium salt, particularly magnesium chloride.

These color stabilizers consisting of alkaline earth metal salts may be used alone or in combination of two or more, and each photosensitive diazonium salt may contain:
It is also important to use at least equimolar amounts, more preferably 3 to 20 moles, especially 6 to 15 moles, per photosensitive diazonium salt.

When an alkaline earth metal salt is not blended or is blended in an amount less than equimolar, the coupling rate when developing with a solution of an alkali metal salt of an organic base and an organic acid is lower than that in the present invention. As the size becomes smaller, the formed image tends to have a duller hue.

On the other hand, even when the alkaline earth metal salt is used in an amount greater than 20 times by mole, no particular increase in effect is observed.

In the two-component diazo light-sensitive material of the present invention, many of the types of diazonium salts conventionally used in two-component diazo light-sensitive materials can be used by incorporating a color tone stabilizer consisting of the above-mentioned alkaline earth metal salt. However, the photosensitive diazonium salt that can be used in the present invention is not limited thereto.

Examples of such diazonium compounds are as follows:
It is as follows.

◎Paraphenylenediamine N-N substituted compound general formula % Formula % R4R "Nearlyphatic group Z, Y: group that can be introduced into benzene) 4-Diazo-N-N-dimethylaniline (abbreviation MA salt) 4-Diazo -N-N-diethylaniline (abbreviated as EA Nord) 4-Diazo-N-ethyl-N-β-hydroxyethylaniline (abbreviated as EH salt) 4-Diazo-N-N-bis-β-hydroxyethylaniline 4 -Diazo-N-methyl-N-β-hydroxyethylaniline 4-thia7” -N-ethyl-N-β-hydroxypropylaniline (other N-by alkyl or hydroxyalkyl)
mono- or N-N substituted paraphenylenediamine diazonium salt) 4-thia7”-N-ethyl-N-(β-diethylamino)
-Ethylaniline 4-diazo-2-chloro-N-N-diethylaniline 4-diazo-2-methyl-N-N-diethylaniline 4-diazo-2-iodo-N-N-diethylaniline 4-diazo-2 -4! JFluoromethyl-N-Ndiethylaniline 4-thiasoN-[-thyl-N-benzylaniline 4-
Shea 7”-N-methyl-N-benzylaniline (abbreviation: methylbenzyl) ◎Aminodiphenyl or aminodiphenylamine-based rosediazodiphenylamine ◎Heterocyclic amine derivatives (A:O [morpholine type], S [thiomorpholine type]) Methylene group [phenylpiperidine type] single bond [phenylpyrrolidine type]) 4-diazo-2.
5-dibutoxy-N-phenylmorpholine 4-diazo-2,5-jethoxy-N-phenylmorpholine 4-diazo-2-methoxy-N-thiomorpholine 4-Schiff 7”-N-phenylpiperidine 4-sia 7”
-N-phenylpyrrolidine 4-diazo-2,5-di-
n-Butoxy-N-phenylpiperidine and other 4-diazo N-phenyl, derivatives of heterocyclic amines 2-diazo-4-methylmercapto-N-N'-dimethylaniline 2-diazo-5-benzoylamino-N-N '-Dimethylaniline 2-diazo-1-naphthol-5-sulfonic acid ◎In the following general formula, R is a lower alkylene group; Y is a hydrogen atom, having 8 carbon atoms
The following acyloxy group or benzene-based aromatic sulfonyloxy group; 2 is a hydrogen atom, an acyloxy group with 8 or less carbon atoms or a benzene-based aromatic sulfonyloxy group: X is an anion; Y: an acyl group with 8 or less carbon atoms or a benzene-based It is an aromatic sulfonyloxy group; n is a number of 1 or 2.

A diazonium salt or its double salt represented by:

4-Sia/”-N-β-benzoyloxyethyl-N-
Ethylaniline chloride, 4-Diazo-N-N-di-β-benzoyloxyethylaniline chloride, 4-Diazo-N-N-di-β-acetyloxyethylaniline chloride.

The diazo compounds mentioned above are used as sulfates or hydrochlorides, and are used as relatively stable diazonium salts, or as double salts with zinc chloride, tin chloride, aluminum sulfate, etc.

Further, stabilization methods such as allylsulfonate (diazonium salt of aromatic sulfonic acid) and diazosulfonate can also be used.

In this case, when the diazonium salt is used as a double salt of zinc chloride, it is permissible to use zinc chloride as a double salt with a molar ratio of . Care will generally be required to ensure that zinc is not included.

Of course, in the present invention, an alkaline earth metal salt such as magnesium chloride used as a color stabilizer can be used to form a double salt with a diazonium salt, in which case an excess of magnesium chloride is added to form the double salt. It is also possible to form a composition of the diazonium salt/magnesium chloride double salt and the color tone stabilizer all at once using the above method.

In the present invention, it is important to use a polyhydroxyaryl derivative as an azo coupling component for the purpose of forming a diazo copy having a deep color hue and high image density and contrast. It is an important feature of the invention that sharp copies are obtained under mild conditions even when using such couplers which are significantly smaller under development conditions using solutions of alkali metal salts of organic acids.

Suitable examples of such polyhydroxyaryl derivatives are as follows.

3,3',5-) Rihydroxydiphenyl 3,3
',5,5'-tetrahydroxydiphenyl 2,2',4,4'-tetrahydroxydiphenyl2,4,4'-trihydroxydiphenyl-2'-sulfonic acid 2,4,6, 3', 5'-pentahydroxydiphenyl 2,2', 4,4'-tetrahydroxydiphenyl sulfide 2,3-dihydroxynaphthalene 2,6-dihydroxynaphthalene 2,7-dihydroxynaphthalene 2,3-dihydroxynaphthalene 6-sulfonic acid 2,7-dihydroxynaphthalene-3-sulfonic acid 2,8-dihydroxynaphthalene-6-sulfonic acid l,8-dihydroxynaphthalene-8-sulfonic acid 2,7-dihydroxynaphthalene-3,6-disulfone Acid ■ 8-dihydroxynaphthalene-6-sulfonic acid bis-[5-hydroxy-7-sulfonaphthyl (2)
] Amine N-N-bis[1-hydroxy-3-sulfonaphthyl(6)]-thiourea In the present invention, among the above-mentioned polyhydroxyallyl derivatives, dihydroxynaphthalenesulfonic acid can be used as the azo coupling component. Preferably, especially 2.
3-dihydroxynaphthalene-6-sulfonic acid or 2
- The best results are obtained when using 7-dihydroxynaphthalene-3,6-disulfonic acid.

The above-mentioned azo coupling component is preferably used in an amount of 1 mole or more, particularly preferably 2 to 4 moles, per diazonium salt.

In the present invention, the acid stabilizer has a dissociation constant of 1Xl.
The use of oxycarboxylic acids of O-3 or higher is important in order to obtain copies with vivid hues; for example, conventional acid stabilizers such as citric acid have a dissociation constant of 1 x 10
When using such an oxycarboxylic acid, the hue tends to become dull.

Examples of oxycarboxylic acids having a dissociation constant (Kr) of 1×10 −3 or more include hydroacrylic acid, tartronic acid, 0-oxybenzoic acid, and tartaric acid.

It is desirable to use these acid stabilizers in an amount of 1 mole or more, more preferably 2 to 4 moles, relative to the diazonium salt.

The two-component diazo photosensitive material of the present invention is produced by coating a photosensitive composition containing the above-described photosensitive diazonium salt, azo coupling component, acid stabilizer, and color tone stabilizer on a suitable substrate. .

In addition to the above-mentioned components, other conventional compounding agents such as wetting agents, stabilization aids, development accelerators, extenders, dispersants, dyes, etc. are used in this photosensitive composition, of course, according to a recipe known per se. be able to.

Hereinafter, representative examples of the prescription will be given and explained.

Photosensitive composition for organic base development Diazonium salt 0.1-4.0% Azo coupling component 0.1-5.0% Acid stabilizer
2-10.0% color stabilizer 0.8
~15.0% Development accelerator 0~10.0
% Stabilizer 0~10.0% Extender 0~10.0% Dispersant
0-1.0% dye
As the 0-0.003% stabilizing aid, sodium p-toluenesulfonate, sodium 1,3,6-naphthalene trisulfonate, thiourea, etc. can be used, and as the development accelerator,
Polyhydric alcohols such as glycerin, ethylene glycol, and diethyl glycol can be used.

Further, as the extender, dextrin, gum arabic, colloidal silica, polyvinyl acetate resin emulsion, starch, etc. are used.

As the coloring matter, blue dyes such as methylene blue and patent blue, or fluorescent whitening agents are suitably used to clarify the photosensitive surface or further increase the whiteness of the badge ground.

In the above photosensitive composition, a binder can be used in an amount of 0.2 to 2%, depending on the type of base substrate, in order to improve its adhesion.

The base substrate on which the photosensitive composition is applied includes various papers such as ordinary thin paper, art paper, and coated paper; synthetic resin film; synthetic paper obtained by matting or foaming film;
A non-woven fabric or woven fabric; metal formic acid or a laminated structure thereof is used, and the photosensitive composition is applied onto these base substrates by means known per se, such as a coating roller, an air knife coater, or a bar coater. , blade coater, reverse coater, kitsu coater, spraying,
Apply by dipping or other means.

The amount of the photosensitive composition applied to the substrate varies depending on the type of substrate and its purpose, but it is important to consider the amount of the photosensitive composition applied to the photosensitive layer in terms of storage stability (pre-coupling resistance), image density and contrast of the diazo photosensitive layer. The amount of diazonium salt is 0.1 to 0.2
5S'/m, especially 0.125 to 0.1759/vt
It is best to keep it within the range of .

The two-component diazo photosensitive material of the present invention is prepared by applying appropriate exposure through an original using a light source such as a fluorescent lamp, an incandescent lamp, a low-pressure or high-pressure mercury lamp, or sunlight, and then applying an organic base solution and an organic Develop using a solution of an alkali metal salt of an acid.

As the organic base, used are primary, secondary or tertiary aliphatic, alicyclic or aromatic amines; guanidines; hydrazines, among others mono- and di-.

or alkanolamines such as triethanolamine; morpholine, pyrrolidine, piperidine, piperazine,
Saturated heterocyclic amines such as thiomorpholine; pyridine; cyclohexylamine and the like are suitable, with di- or triethanolamine or morpholine being particularly suitable.

In addition, alkali metal salts of organic acids include acetic acid, formic acid,
Alkali metal salts of aliphatic carboxylic acids such as propionic acid and aromatic carboxylic acids such as benzoic acid, phthalic acid, and terephthalic acid, such as sodium salts and potassium salts, can be used.
Among these, sodium salts and potassium salts of acetic acid, monoformic acid and benzoic acid are particularly preferred.

It is also important to use a combination of the above-mentioned organic base and alkali carboxylate as a developer, and generally 2 to 15% of the organic base and 10 to 30% of the alkali carboxylate are used.
% mixed aqueous solution.

According to the present invention, the development speed is significantly increased compared to the case where only one of the components is used.

1 The two-component diazo photosensitive material of the present invention can be developed under relatively mild conditions such as room temperature to 100°C or lower, especially 80°C or lower, even when developing a thin layer with the above-mentioned aqueous solution of an organic base and an alkali carboxylate. It is a remarkable feature that a sufficient coloring effect can be obtained and the color fastness of copies is improved.

In order to apply the developer to the photosensitive material after exposure, a known thin layer development method such as roller development (roller coating) or spray development can be adopted, and if desired, the photosensitive material coated with the developer can be , passed through a heated iron roll, exposed to infrared radiation, or heated air from an exposure cylinder.

The two-component diazo photosensitive material of the present invention has storage stability (pre-coupling resistance) comparable to that of known two-component diazo photosensitive materials containing zinc chloride as a color stabilizer, and also The coupling rate when developing with a solution of an alkali metal salt of an organic acid, that is, the development rate, is unexpectedly higher than that of known two-component diazo light-sensitive materials.

Moreover, the two-component diazo photosensitive material of the present invention uses ammonia even though it is wet-developed due to the combination of a color tone stabilizer made of an alkaline earth metal salt and an azo coupling component made of a polyhydroxyaryl compound. It has a clear color tone comparable to that of conventional dry-developed diazo copies, and high image density and contrast, and these effects have never been achieved with conventional wet-developed diazo copies.

Furthermore, the two-component diazo photosensitive material of the present invention is compared to the conventional wet diazo copying method in that when it is developed with a solution of an organic base and an alkali metal salt of an organic acid, there is almost no discoloration due to residual coupler when the copies are stored. In addition, it is superior to the conventional dry diazo copying method in that it does not emit air polluting substances such as ammonia.

Furthermore, the two-component diazo photosensitive material of the present invention uses a solution of an organic base and an alkali metal salt of an organic acid, and can produce clear copies at room temperature or with slight heating. It has the advantage that a diazo copy can be obtained by being able to use it in a machine as it is or by making some changes.

The two-component diazo photosensitive material of the present invention can be applied not only to ordinary monochrome copying but also to the diazo multicolor copying method described in Japanese Patent Publication No. 47-43658, in which case separation is good. It is possible to obtain multicolor copies.

The invention is illustrated in the following examples.

Comparative Experimental Example The two-component diazo photosensitive material of the present invention has significantly superior copying performance (color development speed, image density, contrast, storage stability, and color tone stability) compared to conventional two-component diazo photosensitive materials. The following comparative experiment was conducted to demonstrate that

Comparative Experiment 1 (Effect of using color stabilizer) An organic photosensitive material was prepared using a two-component diazo photosensitive material containing the alkaline earth metal salt of the present invention as a color stabilizer and a conventional two-component photosensitive agent containing zinc chloride. The following experiment shows that the copy performance is significantly superior when developed with a developer containing a base.

■-1, Experimental method comparison As a two-component diazo photosensitive paper for experiments, 4-diazo-N=ethyl-N- β-hydroxyethylaniline...15 y
Chloride 3AZnC12 2,3 dihydroxynaphtha V7 ・352-6-sulfonic acid Sodium tartaric acid 302 Color stabilizer (compounds in Table I below, -0 and -150f compounds are used) Urea・・・・・・50
P ■・3・6 naphthalene tristle 00111.307
Sodium phonate methylene blue B concrete ゛・・・・・・ 0.1
f Add water to bring the total volume to 11.

Each photosensitive solution with this composition was applied to base paper for photosensitive paper (Daishowa Paper Co., Ltd.; HKG 68kg base) under certain coating conditions using an air knife coater, and dried to obtain sample diazo photosensitive sheets A and B for comparison experiments. , C, D, E, F,
G, H and ■.

Next, a translucent document sheet with an opaque image was superimposed on this sample diazo photosensitive sheet so as to face the photosensitive layer, and a diazo copying machine (manufactured by Mita Kogyo Co., Ltd.; Copister Dyna) equipped with a built-in mercury lamp was placed on top of the sample diazo photosensitive sheet so as to face the photosensitive layer. A-I),
After forming a latent image of the diazonium salt, a developer having the following formulation was applied to the surface of the photosensitive sheet by roller coating.
, 3y/A4 size and developed to obtain a copy.

The copy performance of this copy is measured using the measurement method shown below.

Developer prescription Sodium benzoate 30f Sodium formate 50f Diethanolamine 80ml Diethylene glycol 10ml Add water and bring the total volume to 11! shall be.

■-2. Method for Measuring Copying Performance (1) Image Density The image density of the unexposed area of the copy obtained by the above experimental method was measured using a color difference meter manufactured by Nippon Denshoku Co., Ltd. according to the color measurement method of JIS-Z-8722. (C8-4A type) to measure the value of Y and convert the image density to -1og Y.

(2) Color Development Speed When each sample photosensitive sheet is developed using the experimental method described above, the time from immediately after development until the color development efficiency reaches approximately 80% is measured using a stopwatch.

However, the judgment was made by visual inspection using limit samples.

The color development efficiency was calculated using the following formula.

(3) Contrast The copies obtained by the above experimental method were visually observed.

(4) Storage stability Each unexposed sample photosensitive sheet prepared by the above experimental method was placed in a constant temperature and humidity chamber at 50°C and RH = 70%, and after processing for 6 hours, each sample was Two types of samples were prepared and used as measurement samples: one unexposed and developed in contact with N ammonia water vapor gas, and one completely exposed and developed.

Separately, each unprocessed sample photosensitive sheet is developed and processed in the same manner as described above to prepare an unprocessed measurement sample.

Regarding the obtained prepared samples before and after treatment (
Using the method for measuring image density in section 1), measure 1logY of the fully exposed area and the unexposed area, and calculate the density change (Δlog
Y) is calculated using the following formula and the storage stability is compared.

(5) Stability of color tone Image density (lo
gYl) and UC8 unit Lla, b according to JIS-Z-8
Manufactured by Nippon Denshoku Co., Ltd. (C8-4
Type A) Measure with a color difference meter.

Separately, each sample photosensitive sheet was exposed in the same manner as in the experimental method section to form a latent image of the diazonium salt, and then
A copy is obtained by contacting a mixed gas of ammonia and water vapor.

The image density (-1ogY2) and a and b of the resulting copies were measured using the same colorimetric method as described above, and the values of each sample photosensitive paper were determined in the case of development with an organic base and in the case of development with ammonia water vapor. The image density difference (Δ-1ogY) and color difference (ΔE) between the two cases were calculated using the following equations, and the stability of the color tone was compared.

Comparative Experiment 2 (Effect of using acid stabilizer) The acid stabilizer contained together with the alkaline earth metal salt in the two-component diazo photosensitive material of the present invention has a dissociation constant of 1.
The following experiment was conducted to demonstrate that oxycarboxylic acids of ×10 −3 or higher are significantly superior in copying performance.

2-1. Experimental method comparison 4-diazo-N-ethyl-N-β-hydroxyethylaniline as a two-component diazo photosensitive paper for experiments 15
rchloride 3AZ n C12 2,3 hydroxynaphthalene---935r6-
Sulfonic acid and sodium acid stabilizers (compounds in the following table-■ are referred to as -8-1 and -30P) Color tone stabilizers (compounds in the following table-■ as 19.16.5o).

) 1.3.6 Naphthalene tristle -1-0-30r Sodium thiourea phonate ・・・・・・50
P Methylene blue B Conc ・・・・・・ o
, add ir water to bring the total volume to 11.

Each of the photosensitive liquids having this composition was applied in the same manner as in Comparative Experiment 1, dried, and sample photosensitive sheets a, b, and c for comparative experiment.
Let them be l and d.

This photosensitive sheet was exposed to light in the same manner as in Comparative Experiment 1.
After developing and obtaining a copy, its performance is measured and compared using the same measuring method as in Comparative Experiment 1 described above.

Comparative Experiment 3 (Development Performance with Various Developers) When the two-component diazo photosensitive material of the present invention was developed with a developer mainly containing an organic base and an alkali metal salt of an organic acid,
The following experiment was conducted to demonstrate that the developing performance was significantly superior.

3-1. Experimental method As the two-component diazo photosensitive paper of the present invention, 4-diazo-N-ethyl-N-β-hydroxyethylaniline...152% chloride ZnCl2 2,3-dihydroxynaphthalene-1,-35P 6
- Sodium sulfonate tartaric acid ・・・・・・30
f Magnesium chloride ・・・・・・50
Guthiourea ・・・・・・50
11.3.6 Naphthalene Tristle ------30P
Sodium phonate methylene blue B conc...°°・ 0.1
Add S' water to bring the total volume to 11.

(Note) This formulation is exactly the same as formulations B and b of Comparative Experiments 1 and 2.

A photosensitive liquid with this composition was applied in the same manner as in Comparative Experiment 1,
It is dried and used as a sample photosensitive sheet for comparison experiments.

This photosensitive sheet was exposed in the same manner as in Comparative Experiment 1 to form a latent image of diazonium salt, and then developed with a developer having the following formulation. The results were measured and compared using the measurement method shown below.

Developer prescription (a): Developer agent mainly composed of organic base Jetanolamine Add 13wLl water and bring the total amount to 100mA! shall be.

Developer recipe (b): Developer solution mainly consisting of alkali metal salts of organic acids Sodium acetate 20 gbenzoic acid 1 of I diethylene glycol lQmA' Add water to make a total volume of 100 ml Developer recipe 0 →; Organic base and organic acid Mixed developer of alkali metal salts of Jetanolamine 7ml Sodium formate 10y Diethylene glycol l0rILl Add water to bring the total volume to 100rrLl.

(For developer formulation); Developer solution mainly composed of inorganic base Potassium carbonate 15f Sodium thiosulfate
5g potassium tetraborate
57 Add water to bring the total volume to 11.

Developer treatment phase: Ammonia/steam mixed gas 25% ammonia water is used.

Development method The above developer formulations (A) to (→ are applied using a roller coating method so that the amount of adhesion to the surface of the sample photosensitive sheet is approximately 0.3 f/A4.
It was developed and processed to the desired size.

Also, regarding the formulation (strength), it was developed by contacting with a mixed gas of ammonia and water vapor.

Method for measuring development performance (1) Image density; Method for measuring copying performance in comparative experiment 1 (1)
) by a similar method.

(2) Color development speed; method for measuring copying performance in comparative experiment 1 (2)
), except that the two developing conditions were one where the film was left at room temperature after development, and the other where it was heated with a heater roll at 60 to 70°C].

(3) Discoloration (lightfastness) of copies;
After irradiating the surface of the copy with an 800 W mercury lamp for 3 hours from a distance of 0.771 m, the state of discoloration of the image area and non-image area was measured using the color measurement method of JIS-Z-8722 by Nippon Denshoku Co., Ltd. A and b are measured using a colorimeter (model C8-4A) using the UC8 color system, and the color difference (ΔE) from the unprocessed copy is calculated using the following formula.

(4) Image flow during development The state of image flow is visually observed for the copies developed with the above-mentioned various developers.

(5) Contrast of copies The contrast of the developed copy is visually observed.

Experimental results 1. Effect of using color stabilizer 2. Effect of using acid stabilizer 3. Development Performance with Various Developers Conclusion and Discussion From the above results, it is clear that the two-component diazo photosensitive paper of the present invention has significantly superior copying performance compared to conventional two-component diazo photosensitive paper. .

For example, as is clear from Comparative Experiment 1, the photosensitive paper containing an alkaline earth metal salt as a color tone stabilizer of the present invention has a fast development speed at room temperature, with a color development efficiency of 80% in 10 to 20 seconds.
In contrast, photosensitive paper using conventional color tone stabilizers has a reddish tone and is about half the image density when developed with ammonia. It shows only a moderate amount of color and is very poor.

Furthermore, the color tone stability (ΔE) of the photosensitive paper of the present invention is within the range of 9 to 20, and the image density has reached a density close to that of the ammonia-developed paper, whereas the conventional photosensitive paper has a ΔE of 4.
3.6, the stability of color tone is very poor.

Furthermore, in terms of storage stability, the photosensitive paper of the present invention is almost the same as the conventional photosensitive paper in terms of density differences due to fog.

From the results of Comparative Experiment 2 (effects of using acid stabilizers), it is clear that oxycarboxylic acids having a dissociation constant of 1 x 10-3 or more are effective as acid stabilizers.

For example, in the case of citric acid, which is a conventional acid stabilizer, not only the color development rate is very slow but also the color tone stability is very poor, but the photosensitive paper b) using the combination of alkaline earth metal salt and tartaric acid of the present invention is It can be seen that the color development speed, image density, contrast and stability of color tone are significantly superior.

Comparative experiment 3. (Development performance with various developing solutions) When the two-component diazo photosensitive paper of the present invention is developed with a developer containing an organic base and an alkali metal salt of an organic acid, the development performance is significantly superior. is obvious.

That is, when photosensitive paper is developed according to the present invention with a developer containing an organic base and an alkali metal salt of an organic acid, the color development speed is fast, the image density is high, and the reproduction is particularly excellent in terms of discoloration. On the other hand, in the case of a developer containing an inorganic base as a main component, the color development speed is rather slow, the image density and contrast are rather poor, and in particular, the discoloration of copies is very poor.

Furthermore, compared to the use of an organic base or organic acid alkali alone, development speed and image density are improved.

Claims (1)

[Claims] 1 Azo coupling component consisting of a photosensitive diazonium salt and a polyhydroxyaryl derivative, with a dissociation constant of lXl
A two-component diazo photosensitive material containing an acid stabilizer consisting of 0-3 or more oxycarboxylic acid and an alkaline earth metal salt in an equimolar amount per the photosensitive diazonium group is exposed through an original, and exposed. A diazo copying method characterized in that a solution containing both an organic base and an alkali metal salt of an organic acid is applied in the form of a thin layer to the subsequent material and developed at room temperature or with slight heating.