CN1230712C - Dimercaptofurodiazole stabilizer and preparation method thereof - Google Patents

Abstract

The present invention relates to a photosensitive material emulsion stabilizing agent, specifically to a disulfhydryl oxdiazole stabilizing agent and a preparation method thereof. The structural formula of the agent is formula I or formula II in which R1 refers to an alkoxyl, R2 refers to hydrogen or a hydrophilic metallic ion, and R3 refers to a hydrophilic metallic ion. The agent has the advantages of preventing the photographic fog of emulsion from increasing, preventing the sensitivity of emulsion from decreasing and preventing other sensitive performance from changing during maturation and preservation.

Description

A kind of Shuan mercapto oxdiazole class stabilizing agent and preparation method thereof

Technical field

The present invention relates to photosensitive material emulsion stabilizing agent, specifically a kind of Shuan mercapto oxdiazole class stabilizing agent and preparation method thereof.

Background technology

Stabilizing agent is adsorbed on the surface of silver halide particle or is adsorbed on the surface of active centre, stops these centers further to be reacted when preserving or develop.Oxadiazole class stabilizing agent is in existing document (DE1,447,569; JP 62-153,850 etc.) existing corresponding report in, for example: 2-sulfydryl-5-aryl-1.3.4-oxadiazole and derivant; But when this class stabilizing agent uses separately, can influence performances such as light sensitivity and contrast, need add fluorine-containing surfactant or primary amine, secondary amine compound simultaneously.

Summary of the invention

The object of the present invention is to provide a kind of being used in separately in the photographic emulsion, can effectively reduce photographic fog in the emulsion coating, increase stability, improve Shuan mercapto oxdiazole class stabilizing agent of light sensitivity and preparation method thereof.

For achieving the above object, the stabilizing agent of the technical solution used in the present invention for being provided, its structural formula of compound is:

Wherein: R ₁For-CH ₂O-, R ₂Be hydrogen or hydrophilic metal ion Na or K; Or

Wherein: R ₃Be hydrophilic metal ion Na or K.

Its preparation method is:

1) preparation of intermediate hydrazides: add 1 grammol raw material phenol in the reaction vessel, 7～9 molar absolute ethyl alcohols, stir, normal temperature drips 2～2.8 grammol sodium methoxides, stir and (make abundant reaction, time is about 0.5～1 hour), cooling bath drips 2～2.8 grammol bromoacetates down, added in about 30～60 minutes, normal-temperature reaction 1～4 hour, after be warming up to and refluxed 2～8 hours, cooling, cooling bath drips 2～4 grammol hydrazine hydrates down, adds in about 30～60 minutes, is warming up to after adding and refluxes 5～8 hours; Reaction back cooling is separated out, and filter the back more than 10 hours, and ethanol, water wash are colourless to filtrate, filtration cakes torrefaction; Weigh yield 50%～80%.

The preparation of 2) oxadiazoles: add 2～4 grammol KOH, 30～60 grammol water, 20～40 grammol ethanol in the there-necked flask, add 1 grammol hydrazides after the stirring and dissolving, normal temperature drips 2～8 grammol CS down ₂Solution, normal-temperature reaction 1～2 hour, back temperature rising reflux 8～20 hours is poured surplus solution in the frozen water into, adds 15～30 grammol hydrochloric acid while stirring, separates out white solid, and filter the back more than 10 hours, is washed to neutrality, and filtration cakes torrefaction is a product; Yield 70%～90%.

The preparation of 3) oxadiazole sodium salt Huo oxadiazole sylvite: with 1 Ke Fen oxadiazole, 2～3 grammol sodium methoxide or potassium methoxides, 30～50 grammol ethanol place reactor, heated and stirred 1～2 hour, the elimination insolubles boils off alcohol solvent, add 20～40 grammol acetone, after stirring, filter, filtration cakes torrefaction is a product; Yield: about 70%～80%.

The present invention has following advantage:

1. novel structure.Compound provided by the present invention is the disymmetry type, especially structural formula I compound " CH ₂O-" introducing, belong to innovation structure.

2. cost is low.Compound provided by the present invention its raw material is simple and easy to, and technology is simple relatively, rationally; Especially its cost of structural formula I compound even be lower than 4～5 times of formula II compounds.

3. effect is good.Its performance of compound provided by the present invention has reached or near a kind of benzimidazole stabilizing agent (abbreviating BM as) that generally uses at present, partial properties also is better than this product greatly, and purity can reach application requirements; And with this class benzimidazole stabilizing agent and comparing with class oxadiazole stabilizing agent, the present invention adds in the photographic emulsion, can prevent growth and sensitivity decrease and other photosensitive property the variation when storing of lactifuge at photographic fog between maturation and storage life; From effect, can improve various photographic properties, increase emulsion stability, improve light sensitivity.

4. good water solubility.The compounds of this invention is soluble in water, can use separately.

Embodiment

Embodiment 1 general structure I example compound

1.4-two (5-sulfydryl-1,3,4-oxadiazole-2-methoxyl)-benzene (being called for short SA) synthetic method and synthetic route are as follows:

(1) intermediate is to the preparation of benzene dioxy base acetyl two hydrazines:

Reaction equation:

Method of operating:

Add p-dihydroxy-benzene 110g in the there-necked flask, absolute ethyl alcohol 500ml starts stirring, the water-bath cooling; Drip sodium methoxide 108g about 20 ℃, stir after half an hour dripping bromine ethyl acetate 334g under the cooling bath, added in about 30 minutes, insulation reaction 2 hours, after be warming up to and refluxed 5 hours; Cooling, cooling bath drips hydrazine hydrate 160ml down, adds in about 30 minutes, is warming up to after adding and refluxes 7 hours, reacted and poured beaker into, cooling is separated out, and filters after 12 hours, earlier with after the ethanol drip washing, wash with water to filtrate colourlessly again, filtration cakes torrefaction is weighed, yield about 60%.

(2) preparation of two (5-sulfydryl-1,3,4-oxadiazole-2-the methoxyl)-benzene of stabilizing agent 1.4-:

Reaction equation:

Method of operating:

Add 32gKOH, 100ml water, 500ml ethanol in the there-necked flask, add benzene dioxy base acetyl two hydrazine 25g, Dropwise 5 0ml CS under normal temperature after the stirring and dissolving ₂, normal-temperature reaction 1 hour, after be warming up to and steam most of solvent after refluxing 10 hours, surplus solution is poured in the frozen water, add concentrated hydrochloric acid 75ml while stirring, add back solution and be highly acid, separate out white solid, placement is spent the night, filter next day, is washed to neutrality, and filtration cakes torrefaction is a crude product.The crude product ethyl alcohol recrystallization, product purity 〉=95%, yield are 80%.

The infrared spectrum of SA (the instrument model is PE983G), mass spectrum (the instrument model is BIELEXIII) and proton nmr spectra (the instrument model is ARX-300 (DMSO)) spectrum elucidation result is referring to table 1～3.

Table 1, the IR spectrum of SA

Name of product	IR/cm -1
		SA	821；1056；1152；1231；1476；1502；1640

Table 2, the mass spectrum result of SA

Name of product	MS/(m/z)
			SA	M-H +(actual measurement)	M (theory)
337	338

Table 3, SA's ¹H-NMR spectrum (DMSO)

Name of product	1H-NMR(δ/ppm)
		SA	5.19(s，4H)；7.02(s，4H)；14.69(s，2H)

Product (SA) detects through instrumental analysis such as infrared, nuclear-magnetism, mass spectrums, proves that its structure is correct.

Performance Detection:

In view of being of wide application of stabilizing agent, therefore adopting different emulsion that it is carried out the test of photographic property, and it is done the contrast experiment with contrast sample BM, with the exposure of honourable CGG type exposure instrument; Its result is referring to table 4～7.

Table 4 is used for the yellow layer of the high sense of colour film emulsion

Sample		BM	?SA
				Photographic property	Photographic fog D 0	0.28	?0.32
Contrast γ	2.05	?2.20
			Light sensitivity S		340	?300
Maximal density D max	2.40	?2.15

Table 5 is used in the low sense of the colour film product layer emulsion

Sample		?BM	?SA
				Photographic property	Photographic fog D 0	?0.13	?0.15
Contrast γ	?1.90	?1.90
			Light sensitivity S		?240	?260
Maximal density D max	?2.55	?2.42

Table 6 is used for black and white high-speed chip emulsion

Sample		?BM	?SA
				Photographic property	Photographic fog D 0	?0.29	?0.30
Contrast γ	?1.25	?1.05
			Light sensitivity S		?175	?360
Maximal density D max	?2.60	?2.20

Artificial ageing performance: be used for artificially-aged emulsion for the low sense of product layer emulsion, investigate the relative stability of stabilizing agent sample to environmental baseline.The artificial ageing condition is: 50 ℃ of temperature, relative humidity 85%.

Table 7 is used for artificially-aged emulsion

Sample		BM			SA
								Digestion time		0 day	2 days	3 days	0 day	2 days	3 days
Photographic property	Photographic fog D 0	0.13	0.12	0.14	0.13	0.14	0.15
								Contrast γ	2.00	2.20	1.70	2.20	2.10	1.90
	Light sensitivity S	220	210	255	230	255	245
								Maximal density D max	2.75	2.35	2.37	2.52	2.17	2.23

Embodiment 2 general structure II example compound

1.4-two (benzene of 5-sulfydryl-1.3.4-oxadiazole-2-), double sodium salt (be called for short: SB) synthetic method and synthetic route are as follows:

(1) preparation of intermediate terephthaloyl dihydrazide:

Reaction equation:

Method of operating:

Add the 25g diethyl terephthalate in the there-necked flask, the 150ml absolute ethyl alcohol starts stirring, and suitably heating makes it molten entirely, and the back drips the 15g hydrazine hydrate, continues to be warming up to and refluxes 7 hours, filters, and filter cake is colourless to filtrate with ethanol drip washing, and filtration cakes torrefaction is weighed.Yield is more than 80%.

(2) intermediate 1.4-pair (the 5-sulfydryl-1.3.4-oxadiazole-2-) preparation of benzene:

Reaction equation:

Method of operating:

Add 15.7g KOH, 75ml water, 400ml ethanol in the there-necked flask, add the 19.4g terephthaloyl dihydrazide after the stirring and dissolving, normal temperature drips 40ml CS down ₂, normal-temperature reaction 1 hour is warming up to backflow and steams most of solvent after 10 hours, and surplus solution is poured in the frozen water, the hydrochloric acid that adds 60ml while stirring adds back solution and is highly acid, separates out white solid, and placement is spent the night, filter next day, is washed to neutrality, and filtration cakes torrefaction is a product.Yield is about 50%.

(3) stabilizing agent 1.4-two (benzene of 5-sulfydryl-1.3.4-oxadiazole-2-), double sodium salt (be called for short: preparation SB):

Reaction equation:

Method of operating:

Two (250ml ethanol places there-necked flask, heated and stirred 1 hour for the benzene of 5-sulfydryl-1.3.4-oxadiazole-2-), 11.9g sodium methoxide with 27.8g 1.4-, the elimination insolubles boils off alcohol solvent, adds acetone 250ml during fast evaporate to dryness, after stirring, filter, filtration cakes torrefaction is a product.Purity: 〉=95% yield: about 80%.

The infrared spectrum of SB (the instrument model is PE983), mass spectrum (the instrument model is BIELEXIII) and proton nmr spectra (the instrument model is ARX-300) spectrum elucidation result are referring to table 8～10.

The IR spectrum of table 8SB

Name of product	IR/cm -1
		SB	840；1086；1156；1498；1577

The mass spectrum result of table 9SB

Name of product	MS/(m/z)
			SB	M-Na +(actual measurement)	M (theory)
299	322

Table 10SB's ¹H-NMR spectrum (MeOH)

Name of product	1H-NMR(δ/ppm)
		SB	8.01(s，4H)

Product (SB) detects through instrumental analysis such as infrared, nuclear-magnetism, mass spectrums, proves that its structure is correct.

Performance Detection:

Adopt different emulsion that it is carried out the test of photographic property, and it is done the contrast experiment with contrast sample BM, with the exposure of honourable CGG type exposure instrument; Its result is referring to table 11～14.

Table 11 is used for the yellow layer of the high sense of colour film emulsion

Sample		BM	?SB
				Photographic property	Photographic fog D 0	0.28	?0.48
Contrast γ	2.05	?1.60
			Light sensitivity S		340	?360
Maximal density D max	2.40	?2.02

Table 12 is used in the low sense of the colour film product layer emulsion

Sample		?BM	?SB
				Photographic property	Photographic fog D 0	?0.13	?0.17
Contrast γ	?1.90	?1.90
			Light sensitivity S		?240	?250
Maximal density D max	?2.55	?2.30

Table 13 is used for colour film black and white high-speed chip emulsion

Sample		BM	?SB
				Photographic property	Photographic fog D 0	0.29	?0.55
Contrast γ	1.25	?1.40
			Light sensitivity S		175	?440
Maximal density D max	2.60	?2.52

Artificial ageing performance: be used for artificially-aged emulsion for the low sense of product layer emulsion, investigate the relative stability of stabilizing agent sample to environmental baseline; The artificial ageing condition is: 50 ℃ of temperature, relative humidity 85%.

Table 14 is used for artificially-aged emulsion

Sample		BM			?SB
								Digestion time		0 day	2 days	3 days	0 day	2 days	3 days
Photographic property	Photographic fog D 0	0.13	?0.12	?0.14	?0.15	?0.17	?0.17
								Contrast γ	2.00	?2.20	?1.70	?2.20	?2.30	?2.10
	Light sensitivity S	220	?210	?255	?255	?255	?260
								Maximal density D max	2.75	?2.35	?2.37	?2.30	?2.23	?2.38

Claims (1)

1. two mercapto oxdiazole stabilizing agent, it is characterized in that: structural formula of compound is:

Wherein: R ₁For-CH ₂O-, R ₂Be selected from a kind of among H, Na or the K;

Or

Wherein: R ₃Be Na or K.