JPS60153042A - Diazo copying material - Google Patents

Abstract

PURPOSE:To rapidly form an image superior in light fastness by forming a layer contg. a diazo compd., a specified coupler, and a transition metal capable of forming a chelate compd. with a dye to be formed by the coupling of them on a support. CONSTITUTION:A layer formed on a support contains a diazo compd., a coupler having a pyrone ring represented by any of formulae I , II, and III (R1 is 1-5C alkyl, phenyl, benzyl, pyridinyl, or benzothiazolyl; R2 is pyridyl or benzothiazolyl; R3 is -COONa, -CN, -SO3Na, or -COOR4; and R4 is H, 1-4C alkyl), and a transition metal capable of forming a chelate compd. with an azo dye to be formed between them. In such a coupler, =C=O<-> in an ionized state rapidly couples with the diazo compd., and further, chelates with said transition metal to form a stable image. The image thus formed does not fade against irradiation of UV rays, etc., and has good light fastness.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a diazo copying material, and more particularly, it provides a diazo copying material capable of forming stable images with excellent light fastness by using a specific coupler. There is a particular thing.

As the photosensitive paper used in the conventional diazo copying method,
A two-component photosensitive paper that uses a diazo component and a coupling component in the photosensitive paper and an alkaline agent as a developer, and a developer that uses only a diazo component in the photosensitive paper, a 7J Tubbling component, and an alkaline agent. There is also one-component photosensitive paper that is developed with C phenol derivatives and nanotol conductors are conventionally known as the coupling components, but these conventional coupling components may cause yellowing of the background part of the photosensitive paper or the formation of azo dyes. This method has the disadvantage that the snoring properties of the image deteriorate over time due to instability of the image. Therefore, JP-A-49'-6936
No., JP-A-50-75435, JP-A-54-3572
No. 3, JP-A No. 54-35724 describes a method of stabilizing an azo dye formed by these nokotsubring components and a diazo component by chelating it, but generally phenol and naphthol derivatives are used. Azo dyes formed using as a coupling component are difficult to chelate, and even if chelated, the chelate bond is likely to break off due to p)-1 changes or changes in environmental conditions (humidity), making it unstable. .

Maruko is also inferior to light solidity 1. Furthermore, photosensitive paper using a phenylhydrazine-based coupling component as a coupling component is also known, but in this case, the solution becomes cloudy when the photosensitive solution is prepared, making it practically unusable.

Also, a coupler having a pyrone ring was previously filed, and the above-mentioned drawbacks were greatly improved. However, the previously applied coupler with a pyrone ring had a problem with the chelation rate and required high energy for chelation, and was hampered by many constraints (environment, pH 1 development conditions, etc.) Practical use as paper is fraught with difficulties.

Purpose The purpose of the present invention is to overcome the above-mentioned conventional drawbacks,
Particularly, it is an object of the present invention to provide a diazo copying material which can form an image quickly and has a light fastness that prevents the resulting image from fading due to ultraviolet rays or the like.

Structure In view of the purpose of the present invention, after an azo dye is formed with a diazo compound and a compound having a pyrone ring shown below as a coupler, using a compound having a pyrone ring shown below as a coupler. It has been found that images with high light fastness can be obtained by forming a Kir-1 compound with the dye and a transition metal, leading to the present invention.

That is, the present invention relates to a diazo compound and the following drawing formulas A) to D).
A coupler having a pyrone ring represented by any one of
The present invention provides a diazo copying material characterized in that an azo dye produced by the two-component Nokotsu bling and a transition metal salt capable of forming a chelate compound are used on a support.

+7. S, ili! Formula [R+: alkyl group of C+ to CS, [R2: pyridine,
) 2-methylpyrone, benzyl group, or benzodeazolecopyridine, henzodiazole] C> Specific examples of the couplers having the above pyrone ring include: 1.5 < 61-1) 2-methylpyrone, 1.5
<' 61-1 ) 2-methylpyrone, i, 5 (
61-1) 2-progorvirone, 1.5 (6H) 2-butylpyrone, 1.5 (6H) 2-pendelpyrone, 1.5 (,
6H) 2-benzylpyrone, 1.5 (61-1>
2-pyridyl bicon, 1.5(6f-1) benzothiazylpyrone, 1 (21-1) -3pyridyl6-hydro:1-ruby1]n, 1(2H13benzothiazyl6-hy1-1) xypyrone, 4-human] 5-carboxycoumarin, 4-hydroxy5-methoxynofulvonylcoumarin, 4-hydroxy5-ethoxycarbonylcoumarin, 4-hydroxy5-propoxycarbonylcoumarin, 4-hydroxy5-phthoxycarbonylcoumarin, Examples include 4-hydroxy 5-cyanocoumarin, 4-hydroxysulfonic acid sotacoumarin, 4-hydroxy 5-carboxylic acid sotacoumarin, and the like.

Mizugen 11tl Near 3 IT, azo dyes produced with diazo compounds and couplers have a lower electron density of the azo group due to chelation with transition metal compounds, and from the perspective of stereochemistry, the azo dyes are di- to tridentate. It is thought that a chelate compound having a polyhedral 1f4 structure that is chelated between conformations is produced. Unlike the conventional formazan complex obtained by contacting a diazo compound with a phenylhydrazone to form a chelate compound, the chelate compound obtained in the present invention does not change much in color depending on the transition metal compound used. , even if it changes, the maximum absorption wavelength is 5 Q
The difference is about n1ll. Moreover, the sharpness of the present invention
The compound No. 1 has high light fastness and does not fade due to ultraviolet rays or the like. This is because, for example, in conventional naphthol-based or phenol-based couplers, the 8r-OH is an electron donor in the resonance effect, but the induced effect 5 becomes an electron-withdrawing group and the coupling becomes R. On the other hand, in the case of the coupler of the present invention that has a pyrone ring, >C-Q- in a state in which the electric charge has been released quickly forms a coupling link, and at the same time, the chelation with the transition metal is completed, and it is no longer possible to react with light. This seems to be to form a stable image that does not change. Also, when compared with JIA synthesis of polmazan dyes using hydrazone couplers, the coupling and chelate formation of the couplers of the present invention are faster and more complete, and the resulting chelate compounds are therefore more stable. ing. .

This means that in the diazo copying process of the present invention (change in color density over time to Bron 1), the color tone of the azo dye is hardly visible before it shifts to the color tone of the Kirel dye. It is also clear that no terminal chelate dye remains, indicating that conversion to chelate-1 occurs immediately after coupling.

The components other than the above-mentioned coupler used in the diazo copying method of the present invention will be explained.As for the diazo compound, any diazo compound used in this field can be used, and it can be used in an aqueous system. When used in non-aqueous systems, sulfate, sulfonic acid jn, and double salts of zinc chloride, cadmium chloride, and soot chloride can be used, and when used in non-aqueous systems, salts of boron tetrafluoride, boron hexafluoride, etc. can be used. .

Transition metals include zinc, mercury, copper, cadmium, niracle, palladium, platinum, silver, gold, manganese, dechnedium, rhenium, chromium, diarybdenum, tungsten, vanadium, di-Al, kurtan, titanium, zirconium,
Examples include hanonium, scandium, yttrium, etc., preferably niracle, zinc, chromium, manganese,
To prepare the diazo copying agent of the present invention using the ingredients mentioned above, which are copper, cadmium, etc., the ingredients and commonly used auxiliary agents are usually dispersed and dissolved in an appropriate solvent. Then, prepare a photosensitive layer solution, apply the pulse wave onto a support, and dry.The support can be paper, cloth, etc. If the wettability of the photosensitive layer liquid is poor, 1. Before applying the photosensitive layer liquid, apply a pretreatment layer (coat layer, adhesive layer) to the support (2).

The use of a coupler in the preparation of photosensitive E-waves is preferably 1.5 to 1.0 mol per 1 mol of the diazo compound.On the other hand, the amount of transition metal salt used is Considering whether is a bidentate or a triad, it is preferable to use 0.5 to 10 mol per diazo compound 1...01.Also, in the case of providing one layer in Pretreatment 1] , this transition metal salt may be added into the pretreatment layer.

Examples of the present invention will be described below.

Example 1 A photosensitive layer HRΔ having the following composition was stirred and dissolved Ffl, and then coated on a support of diazo copying paper (tsubo Ei + 62 Cl/m 2 ) at a rate of 12.5 ml/m 2 .
A diazo copying material 1 was prepared by drying with hot air at 80°C.

Photosensitive solution △: tartaric acid 10 g, isopropyl alcohol iog i, 5 (6 l-l) 2 methylviron 10q4-morpholino-2,5-dibu] ~ xybenzenediazonium chlorite-1/2 Zn Cl 2 12 (] zinc III acid 3 g Water 55 g The diazo copying material 1 obtained in the above manner was layered with the original using a Ricoh Copy SM-1500,
Current 1 ((As a result, the maximum absorption wavelength λm a x 590
A blue image of 1'1m is 1q. This test is carried out by Suga Test Machine (
(Future Meter R manufactured by A◇) Although the image was irradiated with ultraviolet rays for 12 hours, no change was observed at the maximum absorption wavelength λmaX of 590 nm, and the image had a stable image color tone and high light fastness.

Example 2 After dispersing pretreatment liquid 1 with the following composition using a scrubber for 1 hour per month,
It was coated on a support of diazo copying paper (basis weight C: 12 g/m 2 ) at a coating rate of 15 ml/m 2 and dried with hot air at 100° C. (moisture content: 5%).

Pretreatment liquid 1 Silica fine particles (trade name, S VIOid-244, manufactured by Fuji Devson) 25 Lipolyvinyl alcohol (PVA-205 Kuraray Co., Ltd.! I!J) [1 (] Water
Gog Next, the photosensitive layer liquid Δ of Example 1 was applied to prepare a diazo copying material. When an image was formed in the same manner as in (J), similar excellent results were obtained.

Example 3 After stirring and dissolving the photosensitive layer liquid B having the composition in 1 below, it was coated on a support of diazo copying paper (basis weight 62 g/m 2 )ff11
Apply with 2.5ml/m2 and with hot air at 80℃ (+2
After drying, diazo complex 4J iil was obtained.

Photosensitive solution B: tartaric acid 1 og isopropyl alcohol iog i, 5 (61-1>phenylpyrone 10 g 4-dimethylaminebenzenediazonium chloride sulfate 10 (]nickel Hensensulfonate 5Q water 55 g) 1 q of the diazo copying material prepared as above. Shi?zo+l
The maximum absorption wavelength λmax is 57 as a result of overlapping exposure and development of original documents using a Z-type copying machine (P5M1500 manufactured by Taisuko).
A 0 nm reddish-purple image was obtained.

This test was carried out using a sword tester ((wooden fade meter 412
11; When irradiated with external radiation for a period of 'j, the maximum absorption wavelength /+
There was no change at m a x 570 nm, and the image had high light fastness with <1 change in color tone.

Example 4 After stirring pretreatment liquid 2 with the following composition, synthetic paper (manufactured by -] Bo Co., Ltd.)
0.15 ml/m2 on the support
After applying C and IJ, it was dried with hot air at 50° and 70°.

Pre-treatment liquid 2: 1 to 80! ] 1]-Butyl methacrylate (Nippon Yuka MA) 10 g Silica fine particles (described above) 10 g Next, photosensitive layer liquid C having the following composition was stirred and dispersed, and the coating amount was 12 m1/m 2 on the pretreated support. 'rfi
After 2 times of erasing, it was dried with hot air at 80°C to obtain 1 piece of diazo copying material.

Photosensitive liquid C: Methyl cellosolve 80 (J Cellulose acetate (manufactured by Kiyu Kagaku) 10q Silica fine powder (mentioned above) j, -g 4-morpholino-2,5-dibu I ~ xyhengendiazonium boron tetrafluoride 10 1.5< 6l-1) 2 biridyl bi[-ln 10θ
Zinc acetate 5++ Example 5 Pretreatment liquid 1 of Example 2 was applied onto a support of diazo copying paper (basis weight 62 g/H2).

The coating and drying strips 1'1 are the same as in Example 2.

Next, a photosensitive layer liquid having the following composition was applied to give a diazo copying material of 1:7. The coating amount and drying conditions are the same as in Example 1.

Photosensitive solution D; tartaric acid 10 g isopropyl alcohol iog i (21-1)-3 pyridyl 6-hydroxypyrone 10 g 1 mole small benzenediazonium chloride-1/27n Cl 2 12 (nickel monochloride 5 g water 53 g Example In step 5, photosensitive layer liquid E having the following composition was used as the photosensitive layer liquid.
, F were used in the same manner as in Example 6.7.

Photosensitive liquid E: Tartaric acid 10 (j Isopropyl alcohol 10 g 1 (21-1> -3 benzodeazyl 6-hydroxypyrone 10 g p-morpholinohengendiazonium chlorite 1/2 ZIT Cl 2 12 (j Nickel chloride 5q Water 539 Examples 7 Photosensitive solution F: Tartaric acid 10-isopropyl alcohol 10g 4-hydroxy 5-carboxylic acid soda coumarin 10g 1]-Morbolinebenzene-2,5-dipoxybenzenediazonium chloride 1/2 Zn Cl 2' 12a Nickel benzenesulfonate 4g Water 5 ().

To Example 4, the 1q diazo copying material obtained in 7 was transferred to a diazo dry copying machine ((44 Ricobee 5D-20!i manufactured by Ricoh Co., Ltd.).
When I exposed it over the original and developed it, I got a blue-colored image. A light fastness test was performed on these images by applying ultraviolet rays for 12 hours in the same manner as in Example 1, and the results were used in Examples 1 to 3.
The results are also shown in the table below along with the results of a light fastness test of a commercially available diazo photosensitive paper for semi-dry development.

The image 1%'a degree is Macbeth RD-514 (λmax60
It is expressed as a reflection density value measured at 0).

As described above, the light fastness of the pyrone ring coupler of the present invention is extremely excellent, and the IC image is stabilized to 11? It turned out that it was a gift. Regarding the developing method, dry method, wet method, and heat development method ((thermal head method)) can be used.

Effects As explained above, the diazo copying material of the present invention has 1! By using a compound having a pyrone ring with a certain structural formula, an image can be formed quickly and an image with extremely high light fastness without photofading can be provided.
sell.

Patent applicant Rico Co., Ltd. Agent Patent Attorney Hidetake Komatsu Agent Patent Attorney Hiroshi Asahi

Claims (1)

[Claims] A chelate compound can be formed with a diazo compound, a coupler having a pyrone ring represented by any of the following structural formulas A) to C), and an azo dye produced by coupling the two components. A diazo copying material characterized by using a transition metal salt on a support. [R+: C+ to C5 alkyl group, [R2: pyridine,
phenyl group, benzyl group, or benzodeazolecopyridine, benzothiazole] C) R30H [R3: sodium carboxylate, -ON, ω-OC
0OR4, R4-to1, Sodium sulfonate, ^ V1 size ρ, +ρ-σY7c, soil n, m-1