JPS5820417B2 - Dry imaging material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dry image forming material, and more particularly, to a dry image forming material that uses two types of organic halide compounds to increase the sensitivity and also improve the storage stability of raw film. The present invention relates to image forming materials.

Furthermore, the composition of the present invention is an image forming material whose sensitivity can be significantly improved by preheating before exposure.

Conventionally used wet silver salt photosensitive materials require complicated processing, such as the use of chemicals.

In order to improve this drawback, a photosensitive material comprising an organic silver salt oxidizing agent, a reducing agent for silver ions, and silver halide has been proposed as an image forming material that can be processed only by dry processing.

However, conventional dry image forming materials do not have sufficient sensitivity for practical use, or the storage stability of the raw film is poor and it is necessary to store it in a cool and dark place.

In order to overcome this drawback, the present inventors have conducted repeated research and have found an image forming material that has a sensorineural effect that can be used in practical use and can be stably stored in a normal room, and have accomplished the present invention. Yes.

The present invention comprises (1) an organic silver salt oxidizing agent and (ii) the general formula (
It contains as essential components an organic halide compound represented by 1), an organic halide compound represented by general formula (2) of the following formula (1v), and (1v) a reducing agent for silver ions.

component (ii), (at least one of the compounds of iiD)
The species is iodide, and the other type is bromide or salt salt, and the composition ratio is 0 to 10% bromide to iodine compound.
The total amount of bromide and chloride is 0.05 mol or more per 1 mol of iodide, and the sensitivity is superior to using them alone. , 8 and significantly improved storage stability.

The organic silver salt oxidizing agent of component (i) effective in the present invention includes:
Examples include long-chain fatty acid silver.

Examples include silver palmitate, silver stearate, silver araxinate, silver behenate, and the like.

Silver benztriazole, silver saccharinate, silver phthalazinone, silver phthalate, etc. can also be used.

Among these, silver behenate is the most preferred because of its low fogging.

The organic halide compound of component (11) has the following general formula %
Formula % X represents chlorine, bromine or iodine.

R1, R2 and R3 represent the following groups a) to c).

R1R2 and R3 may be the same or different.

a) Aryl group (including substituted aryl group) b) Alkyl group (including substituted alkyl group) C) Hydrogen atom Specifically, C6R5CH2X , (C6R5) 2 CHX , (
C6H5) sX.

etc. can be mentioned.

(X in the formula represents CI, B r + I, etc.

) The compound of component 011) is represented by the following general formula (2).

Here, e is Si, Ge, Sn, Pb, P, As+Sb
.

Indicates an element such as B + + Se - Te y Po.

R, R', R'' represent an unsubstituted or substituted aryl group, an unsubstituted or substituted alkyl group, an organic group containing a carbonyl group, or an aliphatic group;
n.

o, p is m + n + o 10 p = 3 or 4 or 5
The following combinations are possible.

X represents halogen, and the cases where X is chlorine, bromine, or iodine, respectively, are described as chloride, bromide, or iodide as described above.

These compounds include, for example, (C6H5)3GeX,
(C6H5)3PbX.

(C6H5CH2)25nX2. (C6H5) ASX
2.

(C6H5)3SnX, (C6H5)4ASX.

(CaHii)25eX2, (CH3+ CH2)
3 5nX2.

(C6H5) 5bX2, (CaH5)25nX
z-(C6H5)2GeX2-, (CaH5)
3 B rX21゛(C4H91)βeX2. (p-
C2H50C6H4COCH2)2TeX2゜(p(C
H3)2N C6H5)2TeX2.

(p-CH30-C6H5)2TeX2, (CH3
)2TeX2(p-CN-C6H5COCH2)
2 TeX2゜(C3H7COCH2COC3H7)2
TeX2゜(C6H5)3 PX2, (C6H5O)
3 PX2 (wherein X represents CI + Br, I, etc.), but is not particularly limited to the above.

For example, organic tellurium halide compounds containing Te other than those listed above include "The Organic Chemistry of Tellurium J", published by Gorton & Bleach Science, and written by Kruger Ilgorik.
(Covdonand Breach 5th century
ce Publishing 1 “Th” written by Kurt cT-Irgolic
eOrganic Chemistry of T
ellurium pages 70-76, 150-169, 1
Examples include organic tellurium halide compounds described on pages 79 to 183, pages 213 to 222, pages 225 to 226, etc., and these can be used in the present invention.

The total amount of the above organic halide compounds (ii) and (iii) can vary depending on the desired photosensitivity properties, but is approximately 0.00% per mole of the organic silver salt oxidizing agent.
01 mol to about 0.6 mol, preferably about 0.01 mol to
It is in the range of about 0.3 moles.

To this invention? As mentioned above, the organic halide compounds used as the activator are used as a mixture of two or more types, but in that case, bromide (organic iodide) is used as an essential component in It is preferable to use at least one of bromide) and chloride (organic chloride) in the following composition ratio.

That is, the bromide content is 0 to 19 moles and the chloride content is 0 to 3 moles per mole of the iodide, and the total amount of bromide and chloride is in the range of 0.05 mole or more per mole of the iodide.

In a binary mixture system, which is a composition of iodide and one of bromide or chloride, 10 to 50 moles of iodide and 5 moles of bromide are used.
The composition ratio is preferably in the range of 0 to 90 moles, or 50 to 90 moles of iodide and 10 to 50 moles of chloride.

Further, in a ternary mixed system of iodide, bromide, and chloride, a composition ratio that satisfies either or both of the composition ratios of the above-mentioned binary mixed system is preferred.

It has been found that when a mixed activator in such a composition ratio is used, both the photosensitivity and the storage safety are unexpectedly significantly improved.

Next, there are various reducing agents for the silver ion of component (IV) used in the present invention, but when the organic silver is developed in the presence of the exposed photosensitive silver compound, the organic silver Any substance that can reduce the salt oxidizing agent may be used.

Among these, those which are particularly suitable for the present invention are inhibiting phenols, such as 2,6-di-t-4-methylphenol, 2,2-methylenebis-(4-methyl-6
-t-butylphenol), 2.4.4-trimethylpentyl-bis-(2-hydroxy-3,5-dimethylphenyl)-methane, bis-(3,5-di-t-butyl-
4-hydroxybenzyl)-ether, 2,2'-methylenebis-(4-ethyl-6-1-butylphenol)
, 2,2'-methylene-bis(4-methyl-6-(1-
methylcyclohexyl)phenol, 2,6-methylenebis(2'-hydroxy-37-t-butyl-5'-methylbenzyl)-4-methylphenol, 2.4.6-
Examples include tris(3,5-di-t-butyl-4-hydroxybenzyl)phenol.

Others, halodroquinone, 2,2'-dihydroxy-1
, (2) L binaphthyl, methyl gallate, isoascorbic acid and the like are also preferred.

Two or more of the above reducing agents may be used in combination.

The amount of these reducing agents used varies depending on the type of organic silver salt oxidizing agent, reducing agent, and other additives, but generally it is about 0.01 mmole per 1 mole of organic silver salt oxidizing agent.
Moles, preferably about 0.1 moles to about 3 moles, are suitable.

Next, in addition to the above-mentioned components, a color toning agent, a heat fog preventive agent, a spectral sensitizing agent, etc. may be included as necessary.

As the color toning agent, phthalazinone or its derivatives, cyclic imides, etc. are preferred, and the amount used is 1:1 of the organic silver salt oxidizing agent.
The range is from about 0.0001 mole to over mol, preferably from about 0.0005 mol to over mol.

In addition, as heat fog preventive agents, mercury salts such as mercury acetate,
Zinc acetate, calcium acetate, etc. are effective, and the amounts used are the same as in the case of the above-mentioned color toning agents.

Further, as the spectral sensitizing dye, merocyanine dyes are particularly preferred, and among them, merocyanine dyes having an imino group or a carboxyl group are effective for spectral sensitization.

The amount of dye added is approximately 0.000 per mole of organic silver salt oxidizing agent.
01 to 0.1 mol, preferably o, oooi to 0.01
It is in the molar range.

Further, it is also possible to add the dye at the stage of synthesis of the organic silver salt oxidizing agent and use only the dye adsorbed to the organic silver salt oxidizing agent, as in Example 3 described later.

To the above invention? Each component and each additive can be used by being dispersed in various binders.

Examples of the binder include polyvinyl butyral, polyvinyl formal, polyvinylpyrrolidone, polystyrene polymethyl methacrylate, polyvinyl acetate, cellulose acetate butyrate, ethyl cellulose, cellulose acetate, cellulose acetate butyrate, polyvinyl alcohol, gelatin, collodion, and the like. can.

These can also be used in combination of two or more.

The amount of these binders to be used is in a weight ratio of about 10:1 to about 1:10, preferably about 4:1 to about 1:4, based on the weight of the organic silver hydrochloride.

Furthermore, the support on which the components and additives dispersed in the binder are coated is not particularly limited as long as it is stable against heat; Plastic films such as, metal foils such as aluminum, glass, various papers, etc. are suitable.

The composition of the present invention can also be coated onto an imaging material in which a thin layer of metal or semiconductor is provided on a transparent support, as described in JP-A-48-19303.

That is, an image formed using the dry image forming material of the present invention can be transformed into a semi-permanent image by transferring it onto the above-mentioned metal or semiconductor thin layer by flash light irradiation or the like.

When the composition of the present invention is dispersed in the binder and applied on a support, the dry thickness is 1 μ to 1000 μ,
Preferably it is 3μ to 20μ.

Moreover, each component and each additive of the composition of the present invention may be laminated into two or more layers.

When the composition of the present invention is preheated after coating and then exposed and developed, the sensitivity is significantly improved compared to the composition without preheating.

Although preheating varies depending on the composition, it is preferable to perform the preheating at a temperature in the range of 90 to 150°C.

In this case, the higher the heating temperature, the shorter the heating time.

The heating and developing temperature is usually in the range of about 100°C to about 160°C.

The heating time is arbitrarily adjusted, such as from 1 second or less to about 60 seconds.

In addition, compared to the case of a single organic element halide compound, the exposure time is about 1/2 to 1/10 shorter to obtain the same image density with the mixed organic element halide compound of the present invention. That's fine.

The above-mentioned heat pretreatment, heating force method for heat development, and exposure method can be any suitable method normally used in this field, and are not particularly limited.

The dry imaging material prepared in accordance with the present invention is characterized by extremely high photosensitivity and at the same time improved storage stability of the raw film.

Accordingly, the present invention provides a novel and useful imaging material in the field of photography.

The present invention will be explained in more detail by the following examples.
The present invention is not limited to these examples.

Example 1 A silver behenate suspension was prepared by ball milling 88 parts of a mixture of 12 parts of silver behenate and methyl ethyl ketone ditoluene (2:1% by weight) for 72 hours.

Using this suspension, the following composition was stirred and mixed and then coated on a polyester film.

Coating emulsion first layer Silver behenate suspension 6.0 g Polyvinyl butyral 0.729 Methyl ethyl ketone 4.0 g Mercury acetate (0.25
(weight ratio methanol liquid) 0.6 component (ii), (i
ii) Organic halide compound whose total amount is 1/ of silver behenate
10 equivalents Second layer Cellulose acetate 0.639 Acetone 8.3g Phthalazinone 0.14,92.2/-Methylenebis(6-t-buty 0.35.!i'ru4-
(Ethylphenol) Each component of the first layer composition is added in the above order, and the second layer is applied after the first layer has been applied and dried.

The above emulsion, preparation, coating, and other operations were performed in a bright room.

The organic halide compounds include a) α-chlorodiphenylmethane b) α-bromodiphenylmethane C) α-iododiphenylmethane d) bis(p-methoxyphenyl) dichlorothylide e) bis(p-methoxyphenyl) dibromothylide f) Bis-(p-methoxyphenyl) shortylide was used.

The photosensitivity when an organic halide compound was used was investigated using the above coated film.

The photosensitivity is determined by the optical density of 0.0 from the sum of the base and fog. D.

It is determined by the reciprocal of the exposure amount required to increase the amount of light to -0.6 or more.

Relative sensitivity was determined by setting the sensitivity of e) using bis(p-methoxyphenyl) dibromutilide alone to 1.0.

The results are shown in Table 1. The image forming conditions were preheating at 100°C for 2 seconds, and after exposure, development at 120°C for 3 seconds.

As seen in Table 1, a , b r Cy d r e
C+a, c+b, c+d, c+e, b+f, f+ compared to any one of +f alone or a combination of f)+c), etc.
Combinations such as a are excellent in terms of sensitivity.

In addition, the stability of the raw film after coating was investigated under the conditions of irradiation with a model XF-I Cannon Fade Meter manufactured by Suga Test Instruments Manufacturing Co., Ltd., and a temperature of 50°C and a humidity of 90%. Compared to the single system, the mixed system was found to be about 3 to 6 times more stable against light and 2 to 3 times more stable against heat and humidity.

Regarding storage stability, OJ), vtin, 0.1),
A comparison was made at a time when the change in rnrrr exceeded a factor of 10 compared to that not exposed to the above conditions.

Example 2 As the organic halide compound, a) as component (11) a) as triphenyl iodomethane component 010 b) triphenyl germanium chloride c) triphenyl germanium bromide d) diphenyl selenium dichloride e) diphenyl selenium dibromite is used Example 1 was repeated except that:

As a result of the sensitivity test, as in Example 1, the mixed system is about 5 to 20 times more sensitive than the single system.

Also, regarding storage stability, it was found to be 3 to 5 times more stable against light and 2 to 3 times more stable against heat and humidity.

Example 3 As an organic halide compound, a) p-xylylene Schiffite as component (i]) as component (b) p-xylylene diiodide C) diphenylmethane diiodide d) I-liphenyl iodomethane e) An emulsion having the same composition as in Example 1 was prepared except that triphenylphosphine diiodide was used and the amount of mercury was reduced to 1/10.

However, do everything in the dark and dry at 90℃ after applying the second layer.
This was done for 5 minutes.

Evaluation was made by heat development at 120° C. for 5 seconds.

In this case as well, it was found that the mixed system of iodide and bromide had a sensitivity 3 to 7 times higher than that of bromide, which had the highest sensitivity when used alone.

In addition, the stability under the conditions of temperature 50℃ and humidity 90% is 2~
It was found to be 3 times better.

Claims (1)

[Claims] 1 (1) represents an organic silver salt oxidizing agent and (11) a general formula. R, R2 and R3 represent the following groups a) to C). R1, R2, and R3 may be the same or different. a) Aryl group (including substituted aryl group) b) Alkyl group (including substituted alkyl group) C) Hydrogen atom) An organic halide compound (iiD general formula % Formula % indicates the elements Bi, Se, Te, Po, R, R', R
'' represents an unsubstituted or substituted aryl group, an unsubstituted alkyl group, an organic group containing a carbonyl group, or an aliphatic group, and m, n, o, p are m + n
+ o + p = 3, 4, or 5, and X is chlorine, bromine, or iodine. ); and (1v) a reducing agent for silver ions; At least one other type is chloride or bromide, and the composition ratio is 0 to 19 moles of bromide and 0 to 3 moles of chloride per 1 mole of iodide, and the total amount of bromide and chloride is 1 mole of iodine. 0.0 per mole.
A dry image forming material characterized in that the amount of the image forming material is 0.05 mol or more.