JPS59140447A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To enhance fixing sensitivity by adding a specified acid component and polyether as a color developing adjuvant to a color developing layer in a photosensitive compsn. capable of photocolor development and thermofixation. CONSTITUTION:A photosensitive compsn. comprises a fixing layer composed of a fixing agent of one of guanidine derives. and alkylenediamines and a binder, and a color developing layer composed of a color developing agent of a leucotriarylemethane type dye, a photooxidant of a hexaarylbiimidazole, and a binder. Color developing adjuvants further added to said color developing layer are one of mineral acids and aromatic sulfonic acids represented by formulae I , II and one of polyethers represented by formula III in which R1, R2 are each H, Cl, Br, methyl, ethyl, or nitro, and R3 is H or methyl, and n is an integer of 10- 500. As a result, free radicals generated by irradiation of UV rays oxidizes said dye, a visible image perfectly color developed with said adjuvants are formed, and this image part is permanently fixed by thermofixation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention directly prints out a colored image using a light irradiation machine.
The present invention relates to a photosensitive composition that is then heated to obtain a fixed image.

Free radical photography is a typical non-silver salt photographic material that develops color upon irradiation with light, but it has the drawback of the toxicity of organic halogen compounds.

As a solution to this drawback, the Special Publication No. 43-19161
Publication No. 45-40150, Special Publication No. 47-
As seen in Japanese Patent Laid-Open No. 17855 and Japanese Patent Application Laid-Open No. 1287-1987, attention has been paid to the dry recording side inclination of a photochromic-photofixing circuit. For example, the photosensitive composition described in Japanese Patent Publication No. 43-19161 No. 14 uses hexaarylbiimidazole as a photooxidizing agent, a leuco dye as a coloring agent, and a redox couple as a fixing agent, and develops color with ultraviolet rays and fixes with visible light. is the turning part. However, it has the disadvantage that the fixing sensitivity is low compared to the color development sensitivity.

Also, Proceedings of the 43rd Spring Annual Meeting of the Chemical Society of Japan I, P2S
5. Collection of Abstracts of the 1981 Annual Conference of the Photographic Society of Japan P1
1OK introduces a photosensitive composition that can be photochromed and heat-fixed. It consists of tehexaarylbiimidazole as a photooxidizing agent, indigo-based or phenothenazine-based leuco dye as a coloring agent, and guanidines or alkylene diamines as a fixing agent.The color is developed by ultraviolet rays, and then fixed by heating. However, triphenylmethane-based leuco dyes, which are the most common, have the disadvantage of fading during heat fixing.

The present inventors completed the present invention as a result of intensive research to improve the first drawback. That is, the present invention comprises a fixing layer made of a fixing agent and a binder made of a guanidine rust conductor or an alkylene diamine, and a coloring layer made of a leucotriarylmethane dye as a coloring agent, hexaarylbiimidazole as a photooxidizing agent, and a binder. In the photosensitive composition constituted, the color forming W4 contains a mineral acid as a coloring aid, a, 5F component, or general formula I or ■ [I]
[Shoulder] (In the formula, R, is a hydrogen atom, a chlorine atom, a bromine atom,
aromatic sulfonic acids represented by a methyl group, an ethyl group, or a nitro group; b, a general formula weight of 3 HO-(--CB-CH, Represents an atom or methyl group, n is 1
This is a photosensitive composition that is photochromic, heat-fixed, and re-extended, and is characterized in that it contains a polyether represented by the formula (representing an integer from 0 to 500).

In the coloring layer of the present invention, free radicals are generated from hexaarylbiimidazole by the action of ultraviolet rays, and this all
The t group oxidizes the leucotriarylmethane dye, and it can be completely colored using mineral acid or aromatic sulfonic acids and polyneedle as a coloring aid (after forming 2, it can be fixed by heating) The fixing agent in the layer can penetrate into the color forming layer, inactivate the photooxidizing agent, and permanently fix the image area.

Specifically regarding the photosensitive composition of the present invention, examples of the fixing agent include 1,3-diphenylguanidine, phenylguanidine,
Guanidines such as 1.3-di-0-tolylguanidine, 1-0-tolylbiguanide, N-benzylidene-guanidinoamine, or hexamethylenediamine, 1.8-diaminooctane, 1,1.2-diami)vdecane, etc. alkylene diamines can be used.

As the binder for the fixing layer, a resin that is insoluble in the coloring solution #7FIK<e used can be used. For example, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, ethylcellulose, acetylcellulose, etc. can be used.

As a photo-oxidizing agent, a residue selected from the following general formula (IV), a lower alkoxy group having 1 to 6 carbon atoms, a chloro atom, a bromo atom, a fluoro atom group,
Hexaarylbiimidazole represented by (two substituent groups at adjacent positions on the phenyl ring may be bonded to form a benzo ring) can be used, for example, as disclosed in Japanese Patent Publication No. 41-5545.
Compounds described in JP-A-47-12879 I1HC can be used.

Specifically, 2,2'-di(2-chlorophenyl)-4,
5,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-di(2-chlorophenyl)-4
,5,4',5'-tetrakis(3-methoxyphenyl)-1,2'-biimidazole,2,2'-di(2-chloro-4-methoxyphenyl)-4,4',5.5 '
-tetraphenyl-1,2'-biimidazole and the like can be used.

The coloring agent has the following general formula (V) (where BP and RIL are lower alkyl groups having 1 to 4 carbon atoms, 2-cyanoethyl group% 2-human 0oxyethyl group).

R is a hydrogen atom, methyl group, ethyl group, lower alkoxy group, chloro atom, bromo atom, A is phenyl &, t1
1! ! Oxidative color-forming leukotriarylmethane dyes represented by phenyl, naphthyl, chenyl, and inidyl groups, such as Japanese Patent Publication No. 45-40150.
Compounds described in Japanese Patent Publication No. 47-17855 F can be used. Specifically, tris(4-diethylamino-0-tolyl)methane, bis(4-diethylamino-0-tolyl)phenylmethane, bis(4-diethylamine-〇-tolyl)thenyl-2-methane, bis(2- ?rj low 4
-diethylaminophenyl) phenylmethane and other triarylmethane compounds can be used. Furthermore, mineral acid salts or aromatic sulfonate salts of the above-mentioned oxidative color-forming leukotriarylmethane dyes can also be used.

The e component of the color development aid is hydrochloric acid and hydrobromic acid.

Mineral acids such as sulfuric acid, nitric acid, phosphoric acid, or general formula (1) or (
II) (1) (n) (In the formula, R1 and R7 are a hydrogen atom, a chlorine atom, and an okusui atom.

methyl group, ethyl group, nitro group), such as p-toluenesulfonic acid, benzenesulfonic acid, p-ricj benzenesulfonic acid, o-nitrobenzenesulfone #, nl-nitrobenzenesulfonic acid, 1 -Aromatic sulfonic acids such as naphthalenesulfonic acid and 2-naphthalenesulfonic acid can be used. Polyether 51 is polyethylene glycol with an average molecular difference of 600 to 20,000, and an average molecular difference of 1.000 to 4.000.
Polypylene glycol and the like can be used.

The binder in the coloring layer is a material that cannot prevent penetration of the fixing agent, such as polystyrene, polyvinyl butyral, polyvinyl chloride, polymethyl methacrylate, polyvinyl chloride-vinyl acetate comonomer, polycarbonate,
Styrene-butadiene copolymers, acetyl cellulose, etc. may be used. In addition, paper, baryta paper,
Synthetic paper or synthetic resin film can be used.

Preferred solvents preferably used in this case include toehabenzene, toluene, xylene, tetrahydrofuran, acetone, methyl ethyl ketone, cyclohexanone, acrylonitrile, methanol, ethanol, methyl chloride, ethyl cellosolve, ethyl acetate, and dimexane. Furthermore, a mixed solvent of these is also suitable.
C can be used.

Incidentally, preferred proportions of each component used in carrying out the present invention are as follows.

Hereinafter, the present invention will be explained in detail with reference to Examples, but these are not intended to limit the scope of the present invention.

Note that parts in Examples and Reference side represent parts by weight unless otherwise specified. The image density and fog density are measured using a Macbeth reflection densitometer model RD-514.

Example 1 The solutions of 1 and Oboro were prepared separately, and percoder 0
．． 5 m/m and coated paper kit liquid for 15 f.
Apply at a rate of ~ and dry. Furthermore, add Kl liquid to 109
Apply at a rate of ~ and dry. The resulting photosensitive negative original plates were stacked and exposed for 5 minutes in a vacuum printing frame (p-115-B, manufactured by Dainippon Screen Mfg. Co., Ltd.), resulting in a blue color.

After this, heat fixing was carried out at 100° C. for 5 minutes, and a permanent image was obtained which no longer developed color even after re-exposure. As a reference example, the composition of solution (1) of Example 1 was obtained by excluding p-)luenesulfone monohydrate (Reference Example 1), and excluding polyethylene glycol (average molecular fit 600) (Reference Example 2). ), p-1 luene sulfonate and polyethylene glycol (average molecular μ600) were removed (reference example!), treated in the same manner as in Example 1, and heat-fixed at 100°C for 5 minutes to form a blue image. The above results are shown below.
Show IK.

Table 1 From the results in Table 1, the effect of adding p-)luenesulfonic acid and polyethylene glycol (average molecular weight 600) is clear.

Example 2 In solution (1) of Example 1, bis(4-thie'f-ruamino-0-
A photosensitive paper was obtained in the same manner as in Example 1 except that 0.54 part of tolyl) phenylmethane ester salt was used. A green permanent image was obtained when the image (#: 8) was heat-fixed in the same manner as in Example 1. As a reference example, a solution obtained by removing polyethylene glycol (average molecular μ600) from the coloring solution of Example 2 was prepared. , and treated in the same manner as in Example 2 (Reference Example 4).The above results are shown in Table 2.

Table-2 From the results of Table-2, polyethylene glycol (average content - p
The effect of adding I7.H600) is clear. It is recognized to be effective as a color development aid.

Example 3 e Bis(N-ethyl-N-β-hydroxyethylamino-0-)lyl)chenyl-2-methane 0.50 as colorant
A coloring solution similar to that in Example 1 was prepared using 1 part of polypropylene glycol (average molecular weight: 1. g OO) as the polyether and polyether. 1iIIIP was obtained. As a reference example, a solution obtained by removing polypropylene glycol (average molecular weight Jt 1.000) and p-)luenesulfonic acid from the coloring solution of Example 3 was prepared and treated in the same manner as in Example 3 (Reference Example 5). The above results are shown in Table 3.

Table 3 From the results in Table 3, it is clear that polypropylene glycol (average molecular weight 1.000) and p-toluenesulfonic acid are effective as coloring aids.

Example 4 Solutions of the first stage [■] and (IV) were prepared separately, and the (IV) solution was applied in the same manner as in Example 1, followed by the [Rin] solution to obtain photosensitive paper. After image exposure and heat fixing in the same manner as in Example 1, a blue permanent image was obtained.

Reference examples include the composition of solution [1] of Example 4 except that 1-naphthalenesulfonic acid was removed (Reference Example 6), the solution excluding polyethylene glycol (average molecular weight 91.000) (Reference Example 7), A sample (Reference Example 8) excluding 7talenesulfonic acid and polyethylene glycol (average molecular weight 1.000) was prepared and processed in the same manner as in Example 4 to obtain a blue image. The above results are shown in Table 4.

Table 4 From the results in Table 4, it is clear that 1-naphthalenesulfonic acid and polyethylene glycol (average molecular f#1,000) (7) are effective as coloring aids.

Example 5 In the composition of the solution of Example 4, bis(2-diethylamino-0-tolyl)-4-diethyl 1ξnophenylmethane and 1-naphthalenesulfonic acid were used.
A photosensitive paper was obtained in the same manner as in Example 4, except that 0.72 parts of -chloro-4-diethylaminophenyl-4-diethylaminophenylmethane nitrate was used. After image exposure and heat fixing in the same manner as in Example 4, a blue permanent image was obtained. As a reference example, a solution was prepared by removing polyethylene glycol (average molecular weight 1.000) from the coloring solution of Example 5 and treated in the same manner as in Example 5 (Reference Example 9). The above results are shown in Table-5.

Table 5 From the results in Table 5, the effect of adding polyethylene glycol (average molecular weight 1.000) is clear.

Example 6 In the solution of Example 4, 1-naphthalenesulfonic acid and polyethylene glycol (average molecular weight 1,000
), p-ri σ lobenzenesulfone felt 0
．． 42 parts and polypropylene glycol (average molecule 1
A photosensitive paper was obtained in the same manner as in Example 4 except that 1.0 part of 4000) was used. After image exposure and heat fixing in the same manner as in Example 4, a blue permanent image was obtained. As a reference example, a solution was prepared by removing p-chlorobenzenesulfonic acid from the coloring solution of Example 6, and treated in the same manner as in Example 6 (Reference Example 10).
).

The above results are shown in Table-6.

Table 6 From the results in Table 6, the effect of adding p-chlorobenzenesulfonic acid is clear.

Example 7 Bis(4-diethylai)-〇-tolyl)-4-diethylaminophenylmethane, 1- in solution (1) of Example 4
Naphthalene sulfonic acid and polyethylene glycol (
average molecular weight 1.000), 11.36 parts of linibis(4-dimethylaminophenyl)phenylmethane, 0-
A photosensitive paper was obtained in the same manner as in Example 4, except that 45 parts of nitrobenzenesulfonic acid α and 1.00 parts of polyethylene glycol (average molecular weight 2.000) were used. After image exposure and heat fixing in the same manner as in Example 4, a green permanent image was obtained. As a reference example, from the coloring solution of Example 7, 0-=
A solution excluding cole (average molecular weight zooo) was prepared and treated in the same manner as in Example 7 (Reference Example 11).

The above results are shown in Table 7iC.

Table 7 Example 8 The above solutions (V) and (Vl) were prepared separately, and in the same manner as in Example 1, the (Vl) solution was applied and then the (V) solution was applied to obtain a photosensitive paper. A permanently colored image was obtained by image exposure and heat fixing in the same manner as in Example 1. As a reference example, from the composition of solution (V) in Example 8, 1-nitronaphthalene-5
- Sulfonic acid removed (Reference Example 12), polyethylene glycol (average molecule #600) & removed (
Reference Example 13), 1-nitronaphthalene-5-sulfonic acid and polyethylene glycol (average molecular weight 600)
A sample from which the water had been removed (Reference Example 14) was prepared and processed in the same manner as in Example 8 to obtain a blue image. The above results are shown in Table-8.

Table 8 From the results in Table 8, 1-nitronaphthalene-5-sulfonic acid and polyethylene glycol (average molecular weight 600
) is clearly effective.

Example 9 In the composition of solution (V) of Example 8, bis(4-diethylamino-0-tolyl)-4-dimethylaminophenylmethane and 1-nitronaphthalene-5-sulfonic acid b
Example except that 1.14 parts of IJ K bis(4-(N-ethyl-N-β-hydroxyethyl)amino-0-tolyl]-4-diethyl abanophenylmethane and 0.46 parts of concentrated hydrochloric acid were used) A photosensitive paper was obtained by processing in the same manner as in Example 8. After image exposure and heat fixation in the same manner as in Example 8, a blue permanent 1iF
An iI image was obtained. As a reference example, concentrated hydrochloric acid and polyethylene glycol (average molecular weight 600
) was prepared and treated in the same manner as in Example 9 (Reference Example 15). The above results are shown in Table-9.

Table 9 From the results in Table 9, the effect of adding concentrated hydrochloric acid and polyethylene glycol (average molecular weight Ji600) is clear.

Example 10 In the composition of solution (V) of Example 8, bis(4-diethylamino-0-tolyl)-4-dimethylaminophenylmethane, 2'-di(4-methoxyphenyl)-4,
5,4',5'-tetraphenyl-1,22-biimidazole and concentrated tJ! Bis[4-(N-
Ethyl-N-β-cyanoethyl)amino-0-tolyl]
1.18 parts of -4-diethylaminophenylmethane, 2.
2'-di(1-naphthyl) ' * 5+ 'Z5'
-Tetraphenyl 1.2'-Biba Meso-41F6
A photosensitive paper was obtained in the same manner as in Example 8, except that 7 ml of 0-bromobenzene sulfo and 1.04 ml of 0-bromobenzene sulfo were used. After image exposure and heat fixing in the same manner as in Example 8, a blue permanent image was obtained. Example 1017) Coloring liquid twist 0 as a reference example
- A solution excluding bromobenzenesulfonic acid and polyethylene glycol (average molecular weight t6o) was prepared and treated in the same manner as in Example 10 (Reference Example 16). The above results are shown in Table-10.

Table 10 From the results in Table 10, the effect of adding 0+ bromobenzenesulfonic acid and polyethylene glycol (average molecular weight 600) is clear.

Hodogaya Chemical Industry Co., Ltd.

Claims (1)

[Scope of Claims] A fixing layer consisting of a guanidine derivative or alkylene diamine and a binder, and a coloring layer consisting of a leucotriarylmethane dye capable of converting into VcP, hexaarylbiimidazole as a photooxidizing agent, and a binder. In the photosensitive composition, the coloring layer contains a as a coloring aid, a mineral acid as an acid component, or general formula I or [■]
Aromatic sulfonic acids represented by (t, R, R, represents a hydrogen atom, chlorine atom, bromine atom, methyl group, ethyl group, nido a group) and b, general formula part 3) 10-4--CH-CH,-0-H [layer] (In the formula, R3 represents a hydrogen atom or a methyl group, and n is 10
1. A photochromic and heat-fixable photosensitive composition, characterized in that it contains a polyether represented by the formula (representing an integer from 500 to 500).