JPS5840543A - Positive type photosensitive and heat sensitive recording material - Google Patents

Abstract

PURPOSE:To obtain a positive image with superior sensitivity and contrast by using a hydrazine deriv. and a basic substance as fog imparting substances. CONSTITUTION:An org. silver salt such as silver behenate is dispersed in a solvent, and a binder and silver halide or a halogenating agent such as N- bromosuccinic acid imide or sodium chloride are added. A basic substance such as sodium hydroxide, potassium carbonate or ammonia and hydrazine or a hydrazine deriv. such as phenylhydrazine or 1-acetyl-2-phenylhydrazine are further added to the dispersion and heated at 50 deg.C for 1hr. A toning agent such as phthalazinone and a reducing agent such as p-phenylphenol or hydroquinone are then added, and the resulting coating liq. is applied to a support to form a photosensitive and heat sensitive layer. The surface of the layer is imagewise exposed and heated to 80-150 deg.C to obtain a positive image.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a direct positive light and heat sensitive recording material capable of obtaining images with excellent sensitivity and contrast by exposure/dry development.

As recording materials, silver salt photosensitive materials, electrophotographic S photomaterials a,
Diazo photosensitive materials and dry silver are known. However, these recording materials have various problems and no satisfactory material has yet appeared. Although silver salt photosensitive materials have high sensitivity, they are wet-type and cannot be used to obtain images in real time. Although electrophotographic materials have high sensitivity and can obtain images in real time, they are
The process of exposure, development, transfer and cleaning is complicated, the equipment is large and the handling of consumables such as toner is troublesome. Diazo photosensitive materials are inexpensive, but have low sensitivity and require a developer. Dry silver is an improved silver salt material, and is a dry type that can be heated immediately after exposure to obtain an image, but only a negative image can be obtained.

As mentioned above, dry-type silver salt photography (product name Dry Silver) has been known for organic silver salt systems for a long time, but since this is a negative type and it is difficult to control the emulsion, positive types of this system have yet to appear. I haven't.

Therefore, as a result of various studies on the above-mentioned problems, the present inventor succeeded in developing a rotary type light and heat sensitive recording material by introducing the idea of the direct positive method known for wet silver salt into a heat-developable organic silver salt material. did.

That is, the positive-working photosensitive/thermal material of the present invention is a photosensitive/thermal material mainly containing silver halogenide, an organic silver salt, and a reducing agent, which is capped in advance with a fogging substance consisting of hydrazine or a hydrazine derivative and a basic substance. The percentage sign is that it is given.

Each component used in the present invention will be explained below.

Silver halides form latent images when exposed to light, and specific examples include silver chloride, silver bromide, silver iodide, silver iodobromide,
Examples include silver chlorobromide, silver iodochloride, and a mixture thereof.

Organic complex salts are selectively reduced in the latent part during heating to form an image, and specific examples include silver k-hentate, silver arachinate, silver stearate, silver palmitate, and di-uri/acid. Examples include silver salts of long-chain fatty acids such as nabe, saccharin silver, benzotriazole silver, futa 2 dino/kama, etc. The appropriate amount to be used is 10 to 106 moles per mole of silver halogenide.

Furthermore, instead of using silver halide prepared in advance as described above, part of the organic silver salt can be made into silver halide during emulsion preparation. That is, the halogenating agent may be added to the organic silver salt emulsion and stirred at 50 to 80°C for an appropriate period of time. The amount of halogenating agent added is organic silver salt 1
0.001 to 5 moles of CL per mole is suitable.

Examples of halogenating agents include hydrogen chloride, water bromide, ammonium chloride, ammonium bromide, sodium chloride, sodium bromide, sodium iodide, calcium chloride, calcium bromide, calcium iodide, others, magnesium, and chloride.
halides such as zinc, N-chloroconolimide, N-promuconotoriimide, N-bromphthalimide, N-bromoacedoachito-N-iodosuccinimide, N-promphthalazone, N-bromo Examples include oxacillinone. is a benzotriazole substituted with an alkyl group, a nitro group, a halogen atom, an imido group, or an amino group.
- Halides are also effective. Other examples include N-no)-ro-gen compounds of ninzoimidazole.

Further, there are other halogen-containing compounds such as triphenylmethyl chloride, triphenylmethyl bromide, 2-bromoacetic acid, 2-bromoethanol, and benzophenone dichloride.

Next, the reducing agent can be appropriately selected from the following compounds.

(1) Monohydroxybenzenes, (2) Dihydroxybiphenyls, (3) Polyhydroxybenzenes, (4; Naphthols, naphthylamines and aminonaphthols, (5) Hydroxybinaphthyls, (6) Aonophenols, +7JP-phenylenediamines, (8) alkylene bisphenols, (9) ascorbic acid and its spinant 6Q pyrazolidones More specifically, they are as follows.

(1) Monohydroxybenzenes p-phenylphenol, 0-phenylphenol, p
-ethylphenol, p-t-butylphenol, p-
aec-1 tylphenol, p-t-7 tylphenol, p-methoxyphenol, p-ethoxyphenol,
p-cresol, 2,6-di-t-butyl-p-cresol, 2,4-xylenol, 2,6-xylenol,
3.4-xylenol, p-acetylphenol, 1,
4-dimethoxyphenol, 2,6-simethoxyphenol, hydroquinone mono-p-hexyl ether, hydroquinone monobenzyl ether, chlorthymol, etc.

(2) Dihydroxybiphenyls 3.5',5.5'-tetra-1-butyl-4,l-dihydroxybenzene (3) Polyhydroxybenzenes hydroquinone, methylhydroquinone, t-butylhydroquinone, 2.5 -dimethylhydroquinone, 2,
6-dimethylhydroquinone, t-ol't-droquinone, phenylhydroquinone, methoxyhydroginone, ethoxyhydroquinone, chlorohydroquinone, bromohydroquinone, several hydroquinone monosulfone groups, catechol, 3-cyclohexylcatechol,
Resorcinol, gallic acid, methyl gallate, gallic acid-
n-propyl etc.

(4) Naphthols, naphthylamines and aminonaphthols α-naphthol, β-naphthol, 1-hydroxy-4
-methoxynaphthalene, 1-hydroxy-4-ethoxynaphthalene, 1,4-dihydroxynaphthalene, 1,5
-dihydroxynaphthalene, 1-hydroxy-2-phenyl-4-methoxynaphthalene, 9-hydroxy-2-
Methyl-4-methoxynaphthalene, 1-7i)-2-t
Potassium 7toll-6-sulfonate, 1-hydroxy-
4-amine naphthalene, 1-naphthylamino-7-sulfonic acid, etc.

(5) Hydroxybinaphthyls 1.1'-dihydroxy-2,z-binaphthyl, 4.1
-';)) Kishi-1,1'-shihi)'o Kishi2. '
-binaphthyl, 6,6'-dibromo-2,z-dihydroxy-1,1'-binaphthyl, 6,6'-dinitro-2
,7-cyhydroxy-1,1'-binaphthyl, bis(2
-hydroxy-1-naphthyl)methane, etc.

(6) Aminophenols p-aminophenol, 0-1 minophenol, 2,4
-diaminophenol, N-methyl-p-7 minophenol, 2-β-hydroxyethyl-4-aminophthols.

(7) p-phenylenediamines y, N'-diethyl-p-phenylenediamine, N, N
'-dibenzylidene-p-phenylenediamine, etc.

(8) Alkylene bisphenols 1.1-bis(
2-Hydroxy-3-t-butyl-5-methylphenyl)methane, 1,1'-bis(2-hydroxy-3,5-
dimethylphenyl)-3,5,5-)limethylhexane, 1,1-bis(2-hydroxy-3,5-di-t-
butylphenyl)-2-methylpropane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4
, 4-his(4-hydroxy-3-methylphenyl)hebutane, 2,2-bis(4-hydroxy-3-isopropylphenyl)furopane, 2,2-bis(4-hydroxy-6-methylphenyl)furopane , 1.1-bis(4
-hydroxy-3-methylphenyl)cyclohexane,
2.2-bis(4-hydroxy3,5-cy)tylphenyl)propane, 2.2-bis(4-hydroxy-3-
1-butyl-5-methylphenyl)furopane, 3,3-
Bis(4-hydroxy-5-t-dodecylphenyl)hexane, 4,4'-dihydroxy-3-methyldiphenyl)-2,2-propane, (4,l-dihydroxy-5-1-octyldiphenyl) -2,2-propane, (4,dihydroxy-5-t-butyldiphenyl)-4-methyl-2,2-pentane, (4,4'-dihydroxy-3-methyl-3'-1-butyldiphenyl) )
-2,2-propane, (4,4'-dihydroxy-3-
Methyl-5-t-butyldiphenyl)-2,2-pronone, 2,2-bis(4-hydronophenyl)propane,
(4,4'-dihydroxy-s,g,s-t,limethyldiphenol)-5,5-pentane, N~(4-hydroxyphenyl)salicylamide, 2,2-bis(3,
5-dibromo-4-hydroxyphenyl)propane, bis(6-methyl-4-hydroxy-5-t-butylphenyl)sulfide, and the like.

(9) Ascorbic acid and its derivative 1-7scorbic acid; esters such as ethyl 1-ascorbate and diethyl 1-ascorbate.

QQ Pyrazolidones 1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-phenyl-6-pyrazolidone, etc.

Two or more of these reducing agents can be used in combination. This type of reducing agent largely depends on the reducibility of the silver salt oxidizing agent used, so for example, a reducing agent with strong reducing power is used for complex salts that are extremely difficult to reduce, such as nizotriazole. For example, ascorbic acids are suitable. Furthermore, the stronger the reducing agent is required for silver salts of higher fatty acids, the greater the number of carbon atoms. p for lauric acid scissors
- Relatively weak reducing agents such as phenylphenol are suitable, but for silver behenate e.g. 1,1'-bis(
A combination of relatively strong reducing agents such as 2- and methane (5-1-butyl-5-methylphenyl)methane is preferred.

The effective range of the amount of reducing agent to be used as described above is generally specific to the combination of oxidizing agent and reducing agent and cannot be determined unambiguously, but A suitable amount is 0.1 to 10 moles.

In the present invention, in addition to the above-mentioned components, the following binders are used to bind these components and form a layer. Specific examples include gelatin, phthalated gelatin, polyvinyl butyral, polyacryl azide, cellulose aceftophthalate, cellulose acetate propionate, polymethyl methacrylate, polyvinyl pyrrolidone, polystyrene, ethyl cellulose, bilibinyl chloride, chlorinated rubber, and polyester. Isobutylene, butadiene/~styrene cobo'rimer, vinylchlor2-F~vinyl acetate copolymer, vinyl acetate~vinylq2ide~maleic acid copolymer, polyvinylalz
-ol, polyacetate 18k'yl, benzylcellulose, cellulose diacetate, cellulose triacetate, cellulose pluvionate, cellulose acedate phthalate and mixtures thereof.

The amount of binder used is 1:1 by weight to the organic silver salt.
A ratio of 100 to 100:1 is suitable.

Further, the light and heat sensitive recording material of the present invention may further contain a sensitizer, a color toning agent and the like.

As the sensitizing color chart, cyanine-based, merocyanine-based, logcyanine-based, styryl-based dyes, and acidic dyes such as erythrosin, eosin, and fluorescein are used. As a specific example, p-carboxyphenyl-5-[β-ethyl-2-(6-inzokitzolylidene)ethylythene]rhodanine, 5-((3-β-carboxyethyl-2-(5- Thiazolininidene) ethyritene]
-3-ethylrhodanine, 3'-, turboxymethyl-5
-((3-methylthiazolinyritene)-α-ethylethyrythene]rhodanine, 1-carboxymethyl-5-((
3-ethyl-2-(3H)-<nzoxazolilidene)
ethylidene)-5-7 aer-2-thiohita/toin,
5-((3-ethyl-2-penzoxazonylidene)-
1-Methyl-ethylidene]-6-C(5-viroline-1
-yl)propyl]rhodanine, 3-ethyl-5-[1-
Ethyl-2-(3H)-benzothiazolylidene) isopropylidene-2-thio-2,4-oxazolidinedione is mentioned.

As a color toning agent, phthalazinones such as 2-arytyl phthalazinone, phthalazinone, 2-phthalyl phthalazinone;
7-talimides such as N-hydroxy 7-talimide, N
- Potassium 7-thalimide, 7-thalimide; succinimide; phthalic anhydride; quinazolines; pyrazolines. The amount used is α001 per mole of organic silver salt.
~0.3 mol is suitable.

Next, the fogging substance used in the first shot 11 will be explained below.

The fogging substance is composed of hydrazine or a hydrazine derivative and a basic substance.

Examples of hydrazine derivatives include phenylhydrazine, 4
-methylphenylhydrazine, 1-formyl-2-(4
-methylphenyl)hydrazine, 1-7 cetyl-2-phenylhydrazine, 1-7 cetyl-2-(4-acetamidophenyl)hydrazine, 1-methylsulfonyl-2
Examples include -phenylhydrazine, 1-benzoyl-2-phenylhydrazine, 1-methylsulfonyl-2-(3-phenylsulfonadophenyl)hydrazine, and formaldehyde phenylhydrazine. In addition, basic substances include alkali metal hydroxides and carbonates such as lithium hydroxide, sodium hydroxide,
Potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, ammonia, ammoniums, and the like can be used. The fogging substance of the present invention can also be used together with known chemical fogging agents. Examples of known chemical fogging agents include stannous chloride, thioelectric formalin dioxide, alkali aruzenite, gold salts such as potassium chloroaurate, and platinum salts such as potassium chloroplatinate.

The photosensitive and thermosensitive recording material of the present invention is generally prepared by coating an organic solvent dispersion containing each of the above components onto a support such as paper or film.
It is possible to produce sea bream by drying and providing a light and heat sensitive layer. The appropriate thickness of the photosensitive and thermosensitive layer is 1 to 100 microns.

In order to form a positive image using the recording material of the present invention, it is sufficient to heat it to about 80 DEG to 150 DEG C. after applying light to the light-sensitive and heat-sensitive layer.

The light- and heat-sensitive recording material of the present invention has high sensitivity and high contrast, and can obtain a positive image in real time by heat development.Furthermore, it is a dry type and requires few consumables, so it can be easily applied to a high-sensitivity copying machine. Expected to be used.

Hereinafter, the present invention will be specifically explained using examples together with comparative examples, but the present invention is not limited thereto.

Example 1 Silver behenate crystal 57.5 f isopy2
．． R-nor 500-toluene
150- Disperse the above ingredients in a ball mill. Next, the following ingredients: polyvinyl butyral 150t isopropanol 750wIt toluene
Add 490- to t and further disperse 2 balls. This dispersion is A
It is called liquid.

To 40 f of this solution A, a 2-aryuton solution 2- of N-bromo-hakuimide was added in the dark, and the mixture was kept at 50° C. and stirred for 2 hours. Note that all subsequent operations were performed in the dark.

Next, 2 mg of a 1-titanol solution of sodium hydroxide was added, and 1 g of an ethanol solution of 10-IM/l of hydrazine was added, and the mixture was heated at 50° C. for 1 hour. Furthermore, K
Add 410'M/l of AuCl ethanol aspirate to 50
After heating at ℃ for 1 hour, a 10% solution of behenic acid in propyl alcohol in toluene was added and stirred for about 5 minutes. A solution of 45-methyl cellosolve of taladinone was added and further added with 1.1% as a reducing agent. -bis(2-hydroxy-5-teyt, butyl-5-methylphenyl)
A solution of methane in 10-aryltone was added and stirred.

The solution prepared above was spread onto a 75μ thick Mylar film using a 4 mil blade, and
A recording material of the present invention was obtained by drying at .degree. C. for 10 minutes to form a 7.mu. thick light and heat sensitive layer.

When this recording material was exposed through a step wedge that had been exposed to a white fluorescent lamp for a few seconds and then developed on a hot plate at 120°C for 10 seconds, a positive image was obtained that showed a characteristic curve as shown in curve 1 of the attached drawing. Ta.

Comparative Example 1 A recording material was prepared and developed in the same manner as in Example 1 except that sodium hydroxide was not added as the basic substance, and a characteristic curve as shown in Fig. 112 of the attached drawing was obtained. Only the images shown were obtained.

Example 2 and Example 5 Example 1 except that phenylhydrazine and ammonia are used in place of hydrazine in Example 1, respectively.
A recording material was prepared and developed in the same manner as in Example 1, and the results were the same as in Example 1.

Example 4 Positive characteristics were obtained in the same manner as in Example 1 except that instead of sodium hydroxide, a solution 3- in which 5591 Ampo Niazui 3- was dissolved in 100 sd of ethanol was added.

[Brief explanation of the drawing]

The accompanying drawings are characteristic curves showing the relationship between the optical density and the exposure amount of the light and heat sensitive recording material of the present invention on an arbitrary scale.

Claims (1)

[Claims] In a light and heat sensitive recording material which is mainly composed of halogenated scissors, an organic silver salt and a reducing agent and which has been capricated in advance, it is possible to use a method in which the left bristle-imparting substance is composed of hydrazine or a human 2 zine derivative and a basic substance. Type light and heat sensitive recording material.