JP2649976B2 - Recording material - Google Patents

Description

The present invention relates to a mono-sheet type recording material using a leuco dye as a color former.

[Conventional technology]

A pressure-sensitive paper is known as a recording material using microcapsules containing a leuco dye as a color former, and a mono-sheet type in which a developer is coated on the same layer as the capsule is also commercially available.

A monosheet type photosensitive recording material in which a microcapsule containing a polymerizable compound, a photopolymerization initiator and a color former and a developer are provided on the same support is described in JP-B-64-7378. .

Further, a mono-sheet type high-sensitivity photosensitive recording material in which a microcapsule containing a silver halide, a reducing agent, a polymerizable compound and a color former and a developer are provided on the same support is disclosed in
62-209444.

As the developer used in the recording material as described above,
It is preferable to use those having excellent color developing ability from the top of the color density, and a metal salt of a salicylic acid derivative is often used.
Those exhibiting particularly excellent performance are described in the above two publications. It is zinc 3,5-di-α-methylbenzylsalicylate.

Examples of using a metal salt of a salicylic acid derivative as a developer are described in JP-B-52-1327, US 3,864,146, US 3,871,900.
No., US3,896,255, US3,900,215, US3,924,027, U
These are described in S3,934,070, US Pat. No. 3,983,292, and US Pat. No. 4,046,941.

[Problems to be solved by the invention]

When zinc 3,5-di-α-methylbenzylsalicylate is used as the color developer, the color density is considerably high, but the color of the color developer itself during storage is particularly yellowish under the influence of light. It became clear that it had the fault. Therefore, the image obtained from the recording material produced using this developer has a problem that the whole is colored yellow-brown over time and becomes poor.

SUMMARY OF THE INVENTION An object of the present invention is to provide a mono-sheet type recording material using a leuco dye as a coloring agent, which has a high coloring density and does not become yellowish brown over time.

[Means for solving the problem]

As a result of various studies, the above object has been achieved by a microcapsule containing a leuco dye and a monosheet type recording material having a salicylic acid derivative represented by the general formula (I) or a metal salt thereof on the same support.

General formula (I) In the general formula (I), R ₁ and R ₂ each represent a hydrogen atom,
Represents an alkyl group, an aryl group, or a tertiary aralkyl group, and R ₃ represents an alkyl group or an aryl group. However, when R ₂ is a hydrogen atom, R ₁ represents a tertiary aralkyl group.

According to the study of the present invention, a salicylic acid derivative or a metal salt thereof is excellent in the color developing ability of a leuco dye and gives an image having a high coloring density, but the salicylic acid at the third or fifth position is α
When substituted with an aralkyl group having a hydrogen atom at its position, it was found that the salicylic acid derivative or its metal salt was oxidized by oxygen in the air, especially under light irradiation, and gradually changed to a yellow-brown colored substance . Therefore, it is preferable that the 3- or 5-position is substituted by other than an aralkyl group having a hydrogen atom at the α-position. On the other hand, the substituents at the 3- and 5-positions of salicylic acid affect the color developing ability of the leuco dye, and the color developing ability increases in the order of a hydrogen atom, an aryl group, an alkyl group, and a tertiary aralkyl group. Accordingly, it is preferable that the 3- or 5-position is substituted with these groups, and particularly when the 5-position is a hydrogen atom, it is preferably a 3- or tertiary aralkyl group.

On the other hand, it was found that the substitution of an alkyl group or an aryl group at the 6-position of salicylic acid with a hydrogen atom was more excellent in color density. This is probably because the presence of the substituent at the 6-position increases the solubility of the color developer in the oil in which the color former is dissolved.

That is, in the general formula (I) R ₁ and R ₂ each represent a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
-Butyl group, sec-butyl group, tert-butyl group, sec-amyl group, tera-amyl group, cyclohexyl group, tert-hexyl group, 2-ethylhexyl group, tert-octyl group,
tert-nonyl group and the like) aryl group (for example, phenyl group,
A tolyl group, a p-methoxyphenyl group, an m-acetylphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a tertiary aralkyl group (for example, an α, α-dimethylbenzyl group, an α, α-diethylbenzyl group) , Α-methyl-α-
Ethylbenzyl group, α-methyl-α-propylbenzyl group, α-methyl group-α-iso-butylbenzyl group, etc.)
Represents a methyl group, a tert-butyl group, t-
Amyl group, tert-octyl group, phenyl group, α, α-dimethylbenzyl group and the like are preferable. When R ₂ is a hydrogen atom, R ₁ is preferably the above-mentioned tertiary aralkyl group.

R ₃ represents a hydrogen atom and an alkyl group or an aryl group selected from the same group as R ₁ and R _2, and a methyl group is particularly preferable.

Hereinafter, specific examples of the salicylic acid derivative represented by the general formula (I) will be shown.

In the recording material of the present invention, the salicylic acid derivative represented by the general formula (I) may be used as it is as a color developer, but it is more preferable to use a metal salt because the color developing ability becomes higher.

Examples of the metal used for the metal salt include Group Ib metals such as copper and silver, Group IIa metals such as magnesium and calcium, zinc,
Cadmium, group IIb metal such as mercury, group IIIb metal such as aluminum and potassium, group IVb metal such as soot and lead, group VIb metal such as chromium and molybdenum, group VIIa metal such as manganese, cobalt, Group VIII metals such as nickel are exemplified. Of these, zinc, tin, aluminum and nickel are preferred.

The color developer described above can be used for both mono-sheet type pressure-sensitive paper, photopolymerizable photosensitive recording materials as described above, and high-sensitivity photosensitive recording materials using silver halide. In each case, the microcapsules containing the color developer and the leuco dye are provided on the same support. However, the color developer and the microcapsules may be in the same layer or in different layers. Further, the developer is preferably used as fine particles with a dynomill or the like in a state containing a hydrophilic polymer. The developer is preferably contained in the range of 0.1 g to 50 g / m ² . More preferably from 0.5 g to 20 g / m ²
Range.

Hereinafter, a silver halide, a reducing agent, a polymerizable compound, a leuco dye, microcapsules, other additives, and a support will be described in the order of a high-sensitivity recording material using silver halide as an example.

In the light-sensitive material, any of silver chloride, silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide can be used as silver halide. .

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

The grain size of the silver halide may be fine grains of about 0.01 micron or less or large grains having a projected area diameter of up to 10 microns, and may be a polydisperse emulsion or U.S. Pat.
And monodispersed emulsions described in US Pat. No. 3,655,394 and British Patent No. 1,413,748.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Katoff, Photographic Science and Engineerin (Gutoff, Photographic Science and Engineerin).
g), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,226
No. 4,414,310, 4,433,048, 4,439,520, and British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Further, two or more kinds of silver halide grains having different halogen compositions, crystal habits, grain sizes and the like can be used in combination.

The silver halide photographic emulsion that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparati
on and types) ”and No. 18716 (November 1979),
It can be prepared using the method described on page 648 and the like.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical thermal sensitization and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table. Additive type RD17643 RD18716 Chemical sensitizer page 23, page 648, right column Sensitivity enhancer Same as above Spectral sensitizer page 23-24, page 648, right column- Supercolor amplifier, page 649, right column Antifoggant page 24-25, page 649, right Columns and stabilizers The above silver halide grains are described in JP-A-63-6863.
It is preferable to use silver halide grains having a relatively low fog value as in the light-sensitive material described in JP-A-830-830.

The reducing agent that can be used in the light-sensitive material has a function of reducing silver halide and / or a function of accelerating (or suppressing) polymerization of a polymerizable compound. There are various kinds of substances as the reducing agent having the above function. Examples of the reducing agent include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, and 4-amino-5.
-Pyrazolones, 5-aminouracils, 4,5, -dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols,
2,4-disulfonamidophenols, 2,4-disulfonamidonaphthols, o- or p-acylaminophenols, 2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamide Indole, sulfonamidopyrazolobenzimidazoles, sulfonamidopyrazolotriazoles, α-sulfonamidoketones, hydrazines and the like. By adjusting the type and amount of the reducing agent, the polymerizable compound in a portion where a latent image of silver halide is formed or a portion where a latent image is not formed can be polymerized. In a system in which a polymerizable compound in a portion where a silver halide latent image is not formed is polymerized, 1-phenyl-3-pyrazolidones, hydroquinones, and sulfonamidophenols are particularly preferable as a reducing agent.

The various reducing agents having the above functions are described in JP-A-61-183640, JP-A-61-188535, JP-A-61-228441, and JP-A-62-70836 and JP-A-62-86354. ,same
62-86355, 62-206540, 62-264041, 62
-109437, 63-254442, Japanese Patent Application 63-97379, 6
Nos. 3-296774, 63-296775, Japanese Patent Application Nos. 1-27515, 1-54101, 1-91162, 1-90087, and the like, and are described in the specification. (Including those described as a developing agent or a hydrazine derivative.) The reducing agent is described in “The Theory of the Photographic” by T. James.
Process, 4th Edition, pp. 291-334 (1977), Research Disclosure, Vol. 170, No. 17029, June 1978 (pages 9-15), and Vol. 176, No. 176, Dec. 1978. 176
No. 43 (pp. 22-31) is also described. Also, JP-A-62-21
As in the light-sensitive material described in JP-A No. 4446, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base or the like may be used instead of the reducing agent.

The amount of the reducing agent added can vary widely, but is generally 0.1 to 1500 mol%, preferably 10 to 300 mol%, based on the silver salt.

The polymerizable compound used for the light-sensitive material is generally a compound having an addition polymerization property or a reductive polymerization property. The compound having addition polymerizability includes a compound having an ethylenically unsaturated group, and the compound having reversible polymerization is a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable.

Compounds having an ethylenically unsaturated group that can be used in the photosensitive material include acrylic acid and salts thereof, acrylic esters, acrylamides, methacrylic acid and salts thereof, methacrylic esters, methacrylamides, and maleic anhydride. Acids, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers,
Allyl esters and their derivatives.

Specific examples of the polymerizable compound that can be used in the light-sensitive material include acrylates, such as n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, and tricycloacrylate. Decanyloxy acrylate, nonylphenyloxyethyl acrylate, 1,3-dioxolane acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, trimethylolpropane triacrylate,
Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, diacrylate of polyoxyethylenated bisphenol A, 2- (2-hydroxy-
1,1-dimethylethyl) -5-hydroxymethyl-5-
Ethyl-1,3-dioxane diacrylate, 2- (2-
(Hydroxy-1,1-dimethylethyl) -5,5-dihydroxymethyl-1,3-dioxane triacrylate, triacrylate of propylene oxide adduct of trimethylolpropane, polyacrylate of hydroxy polyether, polyester acrylate, polyurethane acrylate, etc. Can be mentioned.

As other specific examples, methacrylates, methyl methacrylate, butyl methacrylate,
Ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate,
Examples thereof include pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and dimethacrylate of polyoxyalkylenated bisphenol A.

The above polymerizable compounds may be used alone or in combination of two or more. Photosensitive materials using two or more polymerizable compounds in combination are described in JP-A-62-210445. Note that a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of the reducing agent described above can also be used as the polymerizable compound. As described above, the use of a substance that serves both as a reducing agent and a polymerizable compound is naturally included in the embodiment of the photosensitive material.

The leuco dye used in the photosensitive material is not particularly limited, and various substances including known substances can be used. For well-known leuco dyes, see Moriga and Yoshida, "Dyes and Chemicals" 9 , p. 84 (Chemical Products Industry Association, 1964); "New Dye Handbook", p. 242 (Maruzen, 1970); R. Garner, "Reports on the
Chem., 56 , 199 (1971); Dyes and Chemicals, 19 , 230 (Chemicals Industry Association, 1974).

Leuco dyes can be structurally classified into several systems.
Examples of the system preferably used in the light-sensitive material of the present invention include diarylphthalide, fluoran, indolylphthalide, acylleukoazine, leucouramine, spiropyran, rhodamine lactam, triarylmethane, and chromene. And the like.

Incidentally, JP-A-62-209436, 62-288827, 62-2888
No. 28, 63-112190, 63-251278, 63-251279, 63
-251280, 63-53542, 63-112188, 63-113446
No. 64-25148, JP-A-1-213636, Japanese Patent Application No. 63-195
The leuco dyes described in each of the publications No. 761 are also preferably used. It is preferable that the leuco dye is contained at 0.5 to 50% by weight based on the polymerizable compound. Further, the leuco dye is preferably contained on the support in a range of 0.1 g / m ² to 10 g / m ² .

The above components, ie, silver halide, a reducing agent, a polymerizable compound, and a leuco dye are contained in microcapsules. In order for silver halide to be uniformly contained in the microcapsules, it is preferable to dissolve a copolymer composed of a hydrophilic repeating unit and a hydrophobic repeating unit in the polymerizable compound. For details, see
It is described in JP-A-62-209450 and JP-A-63-287844.

Various known techniques can be applied to the microcapsules without any particular limitation. Examples include methods using coacervation of hydrophilic wall-forming materials described in U.S. Pat. Nos. 2,800,457 and 2,800,458; U.S. Pat. No. 3,287,154 and U.S. Pat.
And JP-B Nos. 38-19574 and 42-446 and 42-771
No. 3,418,250 and US Pat. No. 3,660,304 by precipitation of polymer; US Pat. No. 3,796,669, using isocyanate-polyol wall material; US Pat. No. 391451
A method using the isocyanate wall material described in No. 1;
U.S. Pat.Nos. 4001140, 4087376 and 408980
No. 2, a method using a urea-formaldehyde-based or urea formaldehyde-resylcinol-based wall-forming material; a method using a melamine-formaldehyde resin described in U.S. Pat. Insitu method by polymerization of monomers described in JP-B-36-9168 and JP-A-51-9079; polymerization dispersion cooling method described in British Patent Nos. 927807 and 965074; U.S. Patent No. 3111407 And the spray drying method described in each specification of British Patent No. 930422. The method of microencapsulating oil droplets of the polymerizable compound is not limited to the above, but a method of emulsifying a core substance and then forming a polymer film as a microcapsule wall is particularly preferable. Japanese Patent Application Laid-Open No. 62-209437 discloses a photosensitive material using a microcapsule having an outer shell made of a polyamide resin and / or a polyester resin.
Japanese Patent Application Laid-Open No. 62-209438 discloses a photosensitive material using microcapsules having an outer shell made of a polyurethane resin.
Discloses a photosensitive material using a microcapsule having an outer shell made of an amino-aldehyde resin.
JP-A-62-209439 discloses a photosensitive material using microcapsules having an outer shell made of gelatin.
Japanese Patent Application Laid-Open No. 62-2094 discloses a photosensitive material using a microcapsule having an outer shell made of an epoxy resin.
No. 41, for a photosensitive material using a microcapsule having a composite resin shell containing a polyamide resin and a polyurea resin, JP-A-62-209447 has a composite resin shell containing a polyurethane resin and a polyester resin. Japanese Patent Application Laid-Open No. Sho 62-20 describes photosensitive materials using microcapsules.
No. 9442 describes each.

Silver halide is preferably present in the wall material constituting the outer shell of the microcapsule. The photosensitive material containing silver halide in the wall material of the microcapsule is disclosed in
It is described in JP-A-62-169147.

Further, Japanese Patent Application No. Hei 1-37782 discloses a reaction product of a water-soluble polymer having a sulfinic acid group and a polymerizable compound having an ethylenically unsaturated group in order to obtain a capsule having particularly excellent wall denseness. A microcapsule in which a polymer wall of a high molecular compound is provided around a membrane formed is disclosed and is preferably used.

The photosensitive material may further contain a base or a base precursor as an image formation accelerator.

As the base and the base precursor that can be used, an inorganic base and an organic base, or a base precursor thereof (a decarboxylation type, a thermal decomposition type, a reaction type and a complex salt forming type, etc.) can be used.

Preferred base precursors are described in JP-A-59-1805.
No. 49, No. 59-180537, No. 59-195237, No. 61-32844
No. 61-36743, No. 61-51140, No. 61-52638,
61-52639, 61-53631, 61-53634, 61
-53635, 61-53636, 61-53637, 61-536
No. 38, No. 61-53639, No. 61-53640, No. 61-55644
No. 61-55645, No. 61-55646, No. 61-84640,
No. 61-107240, No. 61-219950, No. 61-251840, No.
61-252544, 61-313431, 63-316740, 64
No.-68746 and Japanese Patent Application No. 62-209138, organic acids and base acids which are decarboxylated by heating,
JP-A-59-157637, JP-A-59-166943, and JP-A-63-96159 each disclose a compound capable of eliminating a base by heating.

The base precursor preferably releases the base at 50 ° C to 200 ° C, more preferably at 180 ° C instead of 80 ° C.

When a base or a base precursor is used for the light-sensitive material, the base or the base precursor may be present outside the microcapsules.

As a method of incorporating a base or a base precursor outside a microcapsule, JP-A-62-209521 and JP-A-62-2095
No. 22, 62-209526, 63-65437, 63-97943
Nos. 62-209523, 62-253140 and 63-32546.

Bases or base precursors can be used in the photosensitive material in a wide range. The base or base precursor is suitably used in an amount of 100% by weight or less in terms of the weight of the coating film of the photosensitive layer, and more preferably in the range of 0.1% by weight to 40% by weight. The base and / or the base precursor may be used alone or as a mixture of two or more.

Further, a base or a base precursor may be contained in the photosensitive microcapsule. As a method of incorporating the base precursor into the capsule, JP-A-64-32251,
As described in Japanese Patent Application No. 63-92686, it may be introduced in the form of a solid dispersion directly in a polymerizable compound.
No. and Japanese Patent Application No. 1-160148,
The base precursor may be introduced in a state of being dispersed in water and emulsified in the polymerizable compound.

The light-sensitive material of the present invention may further contain a white pigment, a binder and other additives.

As the white pigment, for example, as an inorganic white pigment, silicon oxide, titanium oxide, zinc oxide, magnesium oxide,
Oxides such as aluminum oxide, alkaline earth metal salts such as magnesium sulfate, barium sulfate, calcium sulfate, magnesium carbonate, barium carbonate, calcium carbonate, calcium silicate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate; Other examples include aluminum silicate, aluminum hydroxide, zinc sulfide, various clays, talc, kaolin, zeolite, acid clay, activated clay, and glass. Organic white pigments include polyethylene, polystyrene, benzoguanamine resin, urea-formalin resin, melamine-formalin resin, polyamide resin and the like. These white pigments may be used alone or in combination, but those having a high oil absorption to the polymerizable compound are preferred.

As the binder, a water-soluble polymer, a polymer latex, a polymer soluble in an organic solvent, or the like can be used. Examples of the water-soluble polymer include carboxylmethyl cellulose, hydroxyethyl cellulose, cellulose derivatives such as methyl cellulose, gelatin, phthalated gelatin, casein, proteins such as ovalbumin, dextrins, starches such as etherified starch, polyvinyl alcohol, and polyvinyl alcohol moiety. Acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, synthetic polymers such as polystyrenesulfonic acid, etc., locust bean gum,
Pullulan, alkane gum, sodium alginate and the like can be mentioned.

Examples of the polymer latex include styrene-butadiene copolymer latex and methyl methacrylate.
Examples thereof include a butadiene copolymer latex, a polymer of an acrylate and / or a methacrylate, a copolymer latex, and an ethylene / vinyl acetate copolymer latex.

Examples of the polymer soluble in an organic solvent include a polyester resin, a polyurethane resin, a polyvinyl chloride resin, and a polyacrylonitrile resin.

Two or more binders can be used in combination, and two or more binders can be used together in such a ratio as to cause phase separation.

The average particle size of the white pigment is 0.1-20μ, preferably
0.1 to 10 μ, and the coating amount is 0.1 g to 60 g / m ² , preferably
The range is from 0.5 g to 30 g / m ² . The weight ratio of the white pigment to the binder is preferably in the range of 0.01 to 0.4, more preferably 0.03 to 0.3, based on 1 of the pigment.

The support for the light-sensitive material of the present invention is not particularly limited, but it is preferable to use a material that can withstand the processing temperature during development.

Materials that can be used for the support include glass,
Paper, woodfree paper, baryta paper, coated paper, cast-coated paper, synthetic paper, metal and its analogs, polyester, polyethylene, polypropylene, acetylcellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate,
Examples include films made of polyimide or the like, and paper laminated with a resin material or a polymer such as polyethylene.

Incidentally, when a porous support such as paper is used,
209529, 63-38934, 63-81339, 63-8134
The supports described in JP-A Nos. 63-97941, 64-88543 and 64-88544 can be used.

 Hereinafter, a method of using the photosensitive material will be described.

The photosensitive material is used after being subjected to a development treatment simultaneously with or after the imagewise exposure.

As the above-mentioned exposure method, various exposure means can be used. In general, a latent image of silver halide is obtained by imagewise exposure to radiation containing visible light. The type of light source and the exposure amount can be selected according to the photosensitive wavelength of silver halide (in the case of dye sensitization, the sensitized wavelength) and the sensitivity. The original image may be a black and white image or a color image.

The photosensitive material is subjected to a heat development treatment simultaneously with or after the imagewise exposure. As the heating method, various conventionally known methods can be used. Also, JP-A-61-
As in the light-sensitive material described in JP-A-294434, a light-emitting material may be provided with a heating element layer and used as a heating means. Also,
As in the image forming method described in JP-A-62-210461,
The heat development treatment may be performed while suppressing the amount of oxygen present in the photosensitive layer. The heating temperature is generally 50 ° C to 200 ° C,
Preferably it is 60 ° C to 150 ° C. The heating time is generally 1 second or longer, preferably 1 second to 5 minutes, and more preferably 1 second to 1 minute.

The photosensitive material is subjected to the heat development treatment as described above to polymerize the polymerizable compound in the portion where the silver halide latent image is formed or in the portion where the silver halide latent image is not formed.

By pressing the photosensitive material that has been subjected to the heat development processing,
When the uncured microcapsules rupture and the color former and the developer come into contact, a color image is obtained.

As the above-mentioned pressurizing method, a conventionally known method can be used.

For example, the photosensitive material and the image receiving material may be sandwiched between press plates such as a presser, or pressurized while being conveyed using a pressure roller such as a nip roll. The pressure may be intermittently applied by a dot impact device or the like.

Further, air pressurized to a high pressure can be wiped by an air gun or the like, or can be pressurized by an ultrasonic generator, a piezoelectric element, or the like.

The light-sensitive material has many uses such as a light-sensitive material for color photographing and printing, a light-sensitive material for printing, a light-sensitive material for computer graphic hard copy, and a light-sensitive material for copying machines.

Next, when the recording material of the present invention is used as a photosensitive recording material described in JP-B-64-7378, a microcapsule containing a leuco dye, a polymerizable compound, a photopolymerization initiator and a compound of the general formula (I) Wherein the salicylic acid derivative represented by or a metal salt thereof is provided on the same support.

As the polymerizable compound, the same as the above-described high-sensitivity photosensitive material is used.

Examples of the photopolymerization initiator include α-alkoxyphenyl ketones, polycyclic quinones, benzophenones and substituted benzophenones, xanthones, thioxanthones, halogenated compounds (eg, chlorosulfonyl and chloromethyl polynuclear aromatic compounds, Chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylbenzophenones, and fluorenones), haloalkanes, α-halo-α-phenylacetophenones, photoreducing dyes-reducing redox couples, halogenation Paraffins (eg, bromide or chlorinated paraffins), benzoylalkyl ethers, and lophine dimer-mercapto compound couples, and organic boron compound anion salts of organic cationic compounds described in JP-A-62-143044 It can be mentioned.

Specific examples of preferred photopolymerization initiators include benzoylbutyl, 2,2-dimethoxy-2-phenylacetophenone, 9,10-anthraquinone, benzophenone, Michler's ketone, 4,4'-diethylaminobenzophenone, xanthone, chloroxanthone, thioxanthone, Chlorothioxanthone, 2,4-diethylthioxanthone, chlorosulfonylthioxanthone, chlorosulfonylanthraquinone, chloromethylanthracene, chloromethylbenzothiazole, chlorosulfonylbenzoxazole, chloromethylquinoline, chloromethylbenzophenone, chlorosulfonylbenzophenone, fluorenone, tetrabromide Carbon, benzoin butyl ether, benzoin isopropyl ether, 2,2'-bis (o-chlorophenyl)-
Examples include a combination of 4,4 ', 5,5'-tetraphenylbiimidazole and 2-mercapto-5-methylthio-1,3,4-thiadiazole.

As the photopolymerization initiator, the compounds described above may be used alone or in combination of several kinds.

The photopolymerization initiator is used for the polymerizable compound used.
Preferably, it is used in the range of 0.5 to 30% by weight. A more preferred use range is from 2 to 20% by weight.

As the leuco dye and the microcapsule, the same ones as the above-mentioned high-sensitivity photosensitive material are used.

After the photosensitive material has been exposed to an image, the microcapsules in the unexposed portions can be destroyed by applying pressure to form a color.

Alternatively, the microcapsules can be developed by applying pressure to form an image and then exposing the entire surface to harden and stabilize (fix) the unbroken microcapsules.

The recording material of the present invention can be used as pressure-sensitive paper (non-carbon paper). In this case, a microcapsule containing a leuco dye and a salicylic acid derivative represented by the general formula (I) or a metal salt thereof are provided on the same support, and the microcapsules can be broken by applying pressure to develop a color. In this case, the same leuco dye and microcapsule as the above-described high-sensitivity photosensitive material are used.

Examples 1 to 3 and Comparative Example 1 [Dispersion of color developer] Four types of zinc salts of color developer shown in Table 1 (3 according to the present invention)
44 g of seeds and zinc 3,5-di-α-methylbenzylsalicylate as a comparative example were weighed and ground in a mortar. 44g of a 10% solution of PVA205 (made by Kuraray)
After adding 0.22 g of each type of surfactant and 131 g of water, the mixture was roughly dispersed with a polytron for 5 minutes, and further dispersed with a Dynomill for 10 minutes. The particle size of the developer was 1 μm or less.

[Preparation of microcapsule solution] 5 g of a partial sodium salt of polyvinylbenzenesulfonic acid (VERSA TL502, manufactured by National Starch) in 95 g of water
Was dissolved. This was adjusted to pH 4.0 with a 20% sodium hydroxide solution. On the other hand, 4g of crystal violet lactone
A hydrophobic solution obtained by heating and dissolving in 100 g of KMC-113 (manufactured by Kureha Chemical Co., Ltd., alkyl naphthalene containing diisopropyl naphthalene as a main component) was emulsified and dispersed in 100 g of a 5% aqueous solution of a partial sodium salt of the polyvinylbenzenesulfonic acid. average
An emulsion with a particle size of 4.5μ was obtained. Separately melamine 6
g, 37% by weight formaldehyde aqueous solution 11g, water 83g at 60 ℃
After 30 minutes of heating and stirring, a clear initial condensate of melamine and formaldehyde was obtained. This was added to and mixed with the above emulsion, and the pH was adjusted to 6.0 with a 20% phosphoric acid solution while stirring, the temperature of the solution was raised to 65 ° C, and stirring was continued for 90 minutes. Then 20%
After adjusting the pH to 4.0 with phosphoric acid, 30 g of a 40% aqueous urea solution was added, and stirring was continued for a further 40 minutes at 65 ° C., and the microcapsule solution was adjusted to pH 9.0 with 20% sodium hydroxide. Obtained.

(Preparation of pressure-sensitive recording material)

Caumium carbonate 574g, Poise 520 (Kao dispersant) 11.
9g and 1650g of water are mixed, and the particle size is 1-2μ with Dynomill.
Dispersed until 10 g of this calcium carbonate dispersion, P
VA117 (manufactured by Kuraray) 8% aqueous solution 3 g, the developer dispersion 10
g, and 10 g of the microcapsule solution were mixed, and 80 g / m ²
Was coated with a coating rod so that the coating amount became 10 g / m ² for the solid part, and dried to prepare a mono-sheet type pressure-sensitive recording material.

[Evaluation of pressure-sensitive recording material]

The yellow density when the pressure-sensitive recording material is used as it is and when irradiated with a fluorescent light of 25,000 lux for 3 weeks,
The cyan density when passed through a nip roller at a pressure of 0 kg / cm ² was read by a Macbeth reflection densitometer. Table 1 shows the results.

As shown in Table 1, the color developer of the present invention is superior to the conventional color developer in both color density and yellow-brown coloration by light irradiation.

Examples 4 to 6 and Comparative Example 2 [Preparation of Photosensitive Microcapsule Solution] Trimethylolpropane triacrylate was added to 35 g of 2-
Mercapto-5-methylthio-1,3,4, -thiadiazole
0.7 g was added and dissolved with an ultrasonic dispersing machine. On the other hand, methyl chloride 6g, 4,4'-bis (diethylamino) benzophenone
0.7 g, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,
2.1 g of 5'-tetraphenylbiimidazole and 2.1 g of a color former, 3-diethylamino-6-chloro-7-anilinofluoran, were dissolved and added to the above solution to form an oil phase.

On the other hand, a mixture of 17.5 g of a 10% aqueous solution of Alivia gum, 18.8 g of a 12% aqueous solution of isobutyl / maleic anhydride, and 26.8 g of distilled water was adjusted to pH 3.5 with sulfuric acid, and 4.6 g of urea and resorcinol were further added.
0.6 g was added, and the oil phase was emulsified and dispersed in this solution.
μ. Then, 12.9 g of 36% formalin was added, the temperature was raised to 60 ° C. with stirring, 9.0 g of a 5% aqueous ammonium sulfate solution was added after 1 hour, and the mixture was stirred for 1 hour while maintaining the temperature at 60 ° C., and then cooled. Thereafter, the pH was adjusted to 9.0 with NaOH.

(Preparation of photosensitive recording material)

10 g of the calcium carbonate dispersion prepared in Examples 1 to 3, P
3 g of 8% aqueous solution of VA117 (manufactured by Kuraray), and Examples 1 to 3
Then, 10 g of each of the four types of developer dispersion liquids prepared in Comparative Example 1 and 10 g of the microcapsule liquid were mixed.
Various types of photosensitive liquids were obtained. These liquids were applied to a 80 g / m ² cardboard with a coating rod so that the applied amount was 12 g / m ² in solid content, and dried to prepare a mono-sheet type photosensitive recording material.

[Evaluation of photosensitive recording material]

The photosensitive recording material was exposed imagewise using a high pressure mercury lamp. Next, after passing through a nip roller of 500 kg / cm ² ,
A black positive image was obtained. The lowest density part of this image (Dm
in) and the black density of the highest density portion (Dmax) were measured with a Macbeth reflection densitometer. The image was irradiated with a fluorescent lamp having an illuminance of 25,000 lux for 3 weeks, and the yellow density of Dmin was measured. Table 2 shows the results.

As shown in Table 2, the color developer of the present invention is superior to the conventional colorant in both color density and yellow-brown coloring due to light irradiation.

Examples 7 to 15 and Comparative Example 3 [Dispersion of developer] The zinc salts of the developer shown in Table 3 were dispersed in exactly the same manner as in Examples 1 to 3.

[Preparation of Photosensitive Microcapsule Solutions (3 Types)] Preparation of Silver Halide Emulsion (EB-1) Aqueous gelatin solution (16 g of gelatin and 0.5 g of sodium chloride in 1500 ml of water were added, and pH 3.2 with IN sulfuric acid). And an aqueous solution containing 1 g of potassium bromide and an aqueous solution of silver nitrate (100 g of silver nitrate dissolved in 300 ml of water) simultaneously added at an equal flow rate over a period of 50 minutes. One minute after completion of the addition, 430 mg of sensitizing dye (SB-1) was added, and 15 minutes after the addition, 100 ml of an aqueous solution containing 2.9 g of potassium iodide and an aqueous solution of silver nitrate (3 g of silver nitrate dissolved in 100 ml of water) Was added at an equal flow rate over 5 minutes. To this emulsion was added 1.2 g of poly (isobutylene-mono-sodium maleate), which was precipitated, washed with water and desalted. 4 g of gelatin was added and dissolved, and 0.5 mg of sodium thiosulfate was further added. 50 ℃
460 g of monodisperse tetrahedral silver iodobromide emulsion (EB-1) having an average grain size of 0.22 μm and a variation coefficient of 20%.
Was prepared.

Preparation of silver halide emulsion (EG-1) To an aqueous gelatin solution (20 g of gelatin and 0.5 g of sodium chloride in 1600 ml of water, adjusted to pH 3.2 with IN sulfuric acid, and kept at 42 ° C.) 200 ml of an aqueous solution containing 71 g of potassium bromide and an aqueous solution of silver nitrate (100 g of silver nitrate in 200 ml of water)
Was dissolved at the same time over 30 minutes. One minute after the end of the conversion, a sensitizing dye (SG
-1) 480 mg was added, and 10 minutes after the addition of the sensitizing dye, 100 mg of an aqueous solution containing 2.9 g of potassium iodide and an aqueous solution of silver nitrate (3 g of silver nitrate dissolved in 100 ml of water) were simultaneously added over 5 minutes. To this emulsion was added 1.2 g of poly (isobutylene-monosodium maleate), sedimented, washed with water and desalted, dissolved with 4.5 g of gelatin, further added with 0.7 mg of sodium thiosulfate, Chemical sensitization at ℃ 15 minutes, average particle size 0.12μm Coefficient of variation
460 g of a 21% monodisperse tetrahedral silver iodobromide emulsion (EG-1) was prepared.

Preparation of silver halide emulsion (ER-1) 20 g of gelatin and 0.5 g of sodium chloride were added to an aqueous solution of gelatin (1600 ml of water), adjusted to pH 3.5 with IN sulfuric acid, and heated to 45 ° C.
200 ml of an aqueous solution containing 71 g of potassium bromide and an aqueous solution of silver nitrate (100 g of silver nitrate dissolved in 200 ml of water) at the same time over 30 minutes. One minute after completion of the addition, the sensitizing dye (SR-
1) and 15 minutes after the addition of the sensitizing dye, 100 ml of an aqueous solution containing 3.65 g of potassium iodide and an aqueous solution of silver nitrate (100 m of water)
l of silver nitrate 0.022 g) was added at a constant flow rate over 5 minutes. This emulsion was mixed with poly (isobutylene-
After adding 1.2 g of mono-sodium co-maleate, sedimentation, washing with water and desalting, dissolving by adding 3.5 g of gelatin, further adding 0.45 mg of sodium thiosulfate, and adding 20 g at 55 ° C.
After sensitization for one minute, 460 g of a monodisperse tetrahedral silver iodobromide emulsion (ER-1) having an average grain size of 0.13 μm and a variation coefficient of 24% was prepared.

Preparation of solid dispersion (KB-1) 3% aqueous solution of gelatin 160 in a 300 ml dispersion container
g, base precursor (BG-1) 40 g and diameter 0.5-0.7
Add 200 ml of 5 mm glass beads and use a dyno mill to add 30 ml.
The mixture was dispersed at 00 rpm for 30 minutes to obtain a solid dispersion (KB-1) having a particle size of 1.0 μm or less.

Preparation of Photosensitive Composition (PB-1) To 83 g of the polymerizable compound (MN-1) was added a copolymer (1P-
37 g of (SV-1) 20% (wt%) solution of 1) and 20 g of yellow image forming substance (RY-1) were dissolved. To 51.6 g of this solution, (RD-1) 2.42 g, (RD-2) 3.29 g, (FF
-1) 0.006 g was added to prepare an oily solution.

To this solution, 4.5 g of a silver halide emulsion (EB-1) and 38 g of a solid dispersion (KB-1) were added, and the mixture was stirred at 15,000 rpm for 5 minutes using a homogenizer while keeping the temperature at 50 ° C. O
An emulsion photosensitive composition (PB-1) was obtained.

Preparation of Photosensitive Composition (PG-1) To 83 g of the polymerizable compound (MN-1) was added a copolymer (1P-
37 g of a (SV-1) 20% (wt%) solution of 1) and 20 g of a magenta image forming substance (RM-1) were dissolved. To 51.6 g of this solution, 2.42 g of (RD-1), 3.29 g of (RD-2), and (FF-
1) 0.006 g was added to prepare an oily solution.

To this solution, 4.5 g of a silver halide emulsion (EG-1) and 38 g of a solid dispersion (KB-1) were added, and the mixture was stirred at 15,000 rpm for 5 minutes using a homogenizer while keeping the temperature at 50 ° C. O
An emulsion photosensitive composition (PG-1) was obtained.

Preparation of Photosensitive Composition (PR-1) To 83 g of the polymerizable compound (MN-1) was added a copolymer (1P-
37% of a 20% (wt%) solution of (SV-1) of 1) and 20 g of an image forming substance (RC-1) were dissolved. To 51.6 g of this solution, 2.42 g of (RD-1), 3.29 g of (RD-2), and 0.006 g of (FF-1)
Was added to prepare an oily solution.

To this solution, 4.5 g of a silver halide emulsion (ER-1) and 38 g of a solid dispersion (KB-1) were added, and the mixture was stirred at 15,000 rpm for 5 minutes using a homogenizer while keeping the temperature at 50 ° C. O
An emulsion photosensitive composition (PR-1) was obtained.

Preparation of Photosensitive Microcapsule Dispersion (CB-1) 10g of 15% aqueous solution of polymer (2P-1) and polymer (2P
A mixture of 162 g of a 7.1% aqueous solution of -2) was adjusted to pH 5.0.
The photosensitive composition (PB-1) was added to this mixture, and the mixture was stirred at 50 ° C. and 3000 rpm for 30 minutes using a dissolver.
An emulsion in the form of a W / O / W emulsion was obtained.

Separately, 14.8 g of melamine in 37% formaldehyde aqueous solution 2
0.0 g and 76.3 g of distilled water were added, heated to 60 ° C., and stirred for 40 minutes to obtain a transparent aqueous solution of a melamine / formaldehyde precondensate.

69.3% of an aqueous solution of this initial condensate was added to the W / O / W emulsion, and the pH was adjusted to 5.0 using a 10% aqueous solution of sulfuric acid. It was then heated to 60 ° C. and stirred for 120 minutes. Further, the pH is adjusted using a 10% aqueous sodium hydroxide solution.
Was adjusted to 6.5 and melamine. Photosensitive microcapsule dispersion liquid with formaldehyde resin as capsule wall (CB-
1) was prepared.

Preparation of Photosensitive Microcapsule Dispersion (CG-1) In preparation of Photosensitive Microcapsule Dispersion (CB-1), instead of Photosensitive Composition (PB-1), Photosensitive Composition (PG-1) Was used to prepare a photosensitive microcapsule dispersion liquid (CG-1).

Preparation of Photosensitive Microcapsule Dispersion (CR-1) In the preparation of Photosensitive Microcapsule Dispersion (CB-1), the photosensitive composition (PR-1) was used instead of the photosensitive composition (PB-1). A photosensitive microcapsule dispersion liquid (CR-1) was prepared in the same manner except that the dispersion was used.

Polymer (2P-1) Potassium polyvinylbenzenesulfinate Polymer (2P-2) Polyvinylpyrrolidone K-90 (Wako Pure Chemical Industries, Ltd.) [Preparation of photosensitive recording material] Calcium carbonate dispersion prepared in Examples 1 to 3 15g, P
4.5 g of 8% aqueous solution of VA117 (manufactured by Kuraray), and 5 g of the above-mentioned photosensitive microcapsule dispersion (CB-1), 5 g of (CG-1),
(CR-1) 5 g was mixed. Further, 15 g of a developer dispersion was mixed. This solution to the cardboard 80 g / m ^2, the coating amount in solid content 15
g / m ² was applied with a coating rod and dried to obtain a mono-sheet type full-color photosensitive recording material. The above was similarly carried out for the ten types of developers shown in Table 3.

(Preparation of photosensitive recording material)

Each of the above photosensitive recording materials was imagewise exposed using a tungsten bulb. After heating to a surface temperature of 135 ° C. on a hot plate for 10 seconds, the mixture was passed through a nip roller of 500 kg / cm ² to obtain a positive image. The lowest density part of this image (Dmi
n) The yellow density and the black density of the highest density part (Dmax) were measured with a Magbeth reflection densitometer. The image was irradiated with a fluorescent lamp having an illuminance of 25,000 lux for 3 weeks, and the yellow density of Dmin was measured. Table 3 shows the results.

As shown in Table 3, the color developer of the present invention is superior to the conventional colorant in both color density and yellow-brown coloring due to light irradiation.

Claims (3)

(57) [Claims] 1. A mono-sheet type recording material comprising a microcapsule containing at least a leuco dye and a salicylic acid derivative represented by the general formula (I) or a metal salt thereof on the same support. General formula (I) In the general formula (I), R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an aryl group, or a tertiary aralkyl group, and R ₃ represents an alkyl group or an aryl. Where R ₂
When is a hydrogen atom, R ₁ represents a tertiary aralkyl group. 2. The mono-sheet type recording material according to claim 1, wherein the microcapsules further contain a polymerizable compound and a photopolymerization initiator. 3. The mono-sheet type recording material according to claim 1, wherein the microcapsules further contain a silver halide, a reducing agent, and a polymerizable compound.