JPH1134495A - Recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording material such as thermal recording material or photographic photosensitive material having excellent coating suitability and light resistance. SOLUTION: The recording material containing a primary coating layer and sensitive material layer on a support comprises low viscosity gelatin having 10 to 30 mP of viscosity of a PAGI method and 15 to 70 g of jelly strength of the PAGI method and a laminar inorganic compound. The inorganic compound is water swelling synthetic mica, and its aspect ratio is desirably 100 or more. As the swelling inorganic laminar compound, swelling viscosity mineral and the like such as bentonite, hectorite or montmorillonite, swelling synthetic mice or swelling synthetic smectite is used. Of them, the bentonite and swelling synthetic mice are preferable and particularly the swelling synthetic mica is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material, and more particularly to a recording material excellent in coating suitability and a recording material excellent in coating suitability and having improved light fastness.

[0002]

2. Description of the Related Art Thermal recording has recently been developed because its recording apparatus is simple, highly reliable, and requires no maintenance. As the heat-sensitive recording material, those utilizing a reaction between an electron-donating dye precursor and an electron-accepting compound,
Those utilizing a reaction between a diazonium salt compound and a coupler are widely known. In recent years, as a heat-sensitive recording material, researches on (1) improvement in characteristics such as color density and color sensitivity (2) robustness of a color former have been earnestly conducted. However, the heat-sensitive recording material has a drawback that when exposed to sunlight for a long time or when posted for a long time in an office or the like, the background portion is colored by the light or the image portion is discolored or faded. I was Various methods have been proposed to improve the coloring of the background portion and the discoloration and fading of the image portion, but a sufficient effect has not always been obtained.

In the case of a photographic light-sensitive material having a silver halide emulsion layer, if the light resistance is insufficient, discoloration or fading of a background portion or an image portion occurs, and the commercial value of the photographic light-sensitive material decreases.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording material such as a heat-sensitive recording material or a photographic light-sensitive material which is excellent in coating suitability. A second object of the present invention is to provide a recording material such as a heat-sensitive recording material or a photographic light-sensitive material which is excellent in coating suitability and light resistance, particularly light resistance in a white background.

[0005]

SUMMARY OF THE INVENTION The first object described above is intended to provide:
On a support, the viscosity of the PAGI method is 10 mP to 30 mP,
The recording material is characterized by having at least one layer containing gelatin having a jelly strength of 15 g to 70 g according to the PAGI method. As such a recording material, for example, on a support, an undercoat layer, a thermosensitive recording material having a photosensitive material layer, a recording material such as a photographic photosensitive material,
It is desirable that the PAGI method contains gelatin having a viscosity of 10 mP to 30 mP and the PAGI method having a jelly strength of 15 g to 70 g, and it is particularly desirable that the undercoat layer contains the above gelatin.

A second object of the present invention is to provide a recording material having an undercoat layer and a light-sensitive material layer on a support, in a layered state with gelatin having a viscosity of 10 mP to 30 mP according to the PAGI method and a jelly strength of 15 g to 70 g according to the PAGI method. And an inorganic compound of the formula (1). As the layered inorganic compound, water-swellable synthetic mica is desirable, and in particular, water-swellable synthetic mica having an aspect ratio of 100 or more is desirable.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The support in the recording material of the present invention may be transparent or opaque. Examples of the transparent support include, for example, polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose derivative films such as cellulose triacetate film, polyolefin films such as polystyrene films, polypropylene films, and polyethylene films, polyimide films, and polyvinyl chloride films. And synthetic polymer films such as polyvinylidene chloride film, polyacrylic acid copolymer film and polycarbonate film.

In addition to the above-mentioned synthetic polymer film, paper, synthetic paper, paper having a plastic resin layer, and the like can be used, and a support having a plastic resin layer is particularly preferable. As the paper having a plastic resin, it is preferable that the thermoplastic resin is formed on both sides of the base paper, or at least the surface on which the recording layer is formed. Examples of such a support include, for example, (1) a base paper having a thermoplastic resin melt-extruded and coated thereon, and (2) a base paper having a melt-extruded thermoplastic resin coated thereon with a gas barrier layer. (3) a base paper to which a plastic film having low oxygen permeability is adhered, (4) a base paper to which a thermoplastic resin is provided by melt extrusion on the surface of the base paper to which the plastic film is adhered, (5) ) A method in which a thermoplastic resin is melt-extruded on a base paper and then coated with a plastic film.

The thermoplastic resin applied to the base paper by melt extrusion coating includes olefin resins, for example, α-olefin homopolymers such as polyethylene and polypropylene, and mixtures of these various polymers, or ethylene and vinyl alcohol. Is preferred. Examples of polyethylene include LPDE (low-density polyethylene), HDPE (high-density polyethylene), L-LPDE
(Linear low-density polyethylene) and the like can be used.

As a method of laminating the base paper and the plastic film, a known lamination method as described in "New Laminating Handbook" edited by Processing Technology Research Group can be appropriately selected and employed. Lamination, solventless dry lamination, dry lamination using an electron beam or ultraviolet curable resin, or hot dry lamination is desirable.
In the present invention, in the case of a heat-sensitive recording material, the most preferable support is a paper base having natural pulp as a main component and both surfaces coated with an olefin resin.

In the present invention, the viscosity of the PAGI method is 10
mP-30mP, PAGI jelly strength 15g-7
It is desirable to have at least one layer containing 0 g of gelatin and a layered inorganic compound, and it is particularly desirable that the undercoat layer provided on the support contains the above gelatin and the layered inorganic compound.

Here, the viscosity of the PAGI method and the jelly strength of the PAGI method are measured based on a test by the Pagui's Method: Photographic Gelatin Test Method, 7th edition (1992 edition), issued by the Joint Review Board for Photographic Gelatin Test Methods. It was done. In the present invention, gelatin is obtained by reducing the molecular weight of known gelatin (ordinary gelatin) produced by a usual method. However, the term "normal gelatin" used herein means, for example, "raw glue and gelatin (edited by Abiko Yoshihiro, Nippon Niwa, published by Gelatin Industry Association (1987), such as cow bone, cow skin, pig skin, etc.) Is produced by treating lime with an acid or the like, and has much higher viscosity and jelly strength than the gelatin of the present invention.

[0013] Ordinary gelatin is characterized by conditions such as raw materials, processing method (for example, lime treatment or acid treatment) and extraction conditions (temperature and number of extractions). The gelatin of the present invention may be obtained by reducing the molecular weight based on any gelatin. However, those having a low extraction temperature and a small number of extractions are preferred because both low viscosity and jelly strength can be achieved. As a method for reducing the molecular weight of gelatin, there is a method using an enzyme, heat, or the like. Of these, a method using an enzyme is preferable. As the enzyme, for example, papain is preferable. Lowering the molecular weight by heat is disadvantageous because when the viscosity is reduced to a preferable value, the jelly strength decreases.

The gelatin of the present invention has a viscosity of 10 mP to 30 mP according to the PAGI method and a jelly strength of 15 g according to the PAGI method.
When the viscosity of the PAGI method is less than 10 mP, the viscosity of the coating liquid is greatly reduced, and the dispersion state of the pigment (mica) in the coating liquid is deteriorated, while the viscosity of the PAGI method is low. Is greater than 30 mP, the viscosity of the coating liquid increases, and coating failure is likely to occur. Also,
When the jelly strength of the PAGI method is less than 15 g, the strength of the coating film is reduced and the adhesive strength with the support is reduced.
If the jelly strength of the GI method is greater than 70 g, the curl of the coating film increases due to environmental changes.

The gelatin of the present invention may be crosslinked using a hardening agent, if necessary. As the hardener, a known hardener used as a hardener for gelatin can be used. Specific examples of the hardener include a vinyl sulfone compound,
There are active halogen compounds, isocyanate compounds, epoxy compounds and the like, and among them, epoxy compounds are particularly preferable. Examples of the epoxy compound include the following.

[0016]

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The amount of gelatin applied to the undercoat layer is 0.5 g / m ^{2 in} order to suppress Plister (a fine swelling phenomenon due to the heat of the printer thermal head during printing).
The above is desirable.

The layered inorganic compound in the present invention is preferably a swellable inorganic layered compound. Examples of these compounds include swelling of bentonite, hectorite, saponite, beederite, nontronite, stevensite, beidellite, montmorillonite and the like. Minerals, swellable synthetic mica, swellable synthetic smectite, and the like. These swellable inorganic layered compounds have a laminated structure composed of a unit crystal lattice layer having a thickness of 10 to 15 angstroms, and the substitution of metal atoms in the lattice is significantly larger than other clay minerals. As a result, the lattice layer is deficient in positive charge, and cations such as Na ⁺ , Ca ²⁺ , and Mg ²⁺ are adsorbed between the layers to compensate for this. The cations interposed between these layers are called exchangeable cations and exchange with various cations. In particular, the cations between the layers are Li ⁺ , Na ⁺
In such a case, since the ionic radius is small, the bond between the layered crystal lattices is weak, and the layer swells greatly with water. When shear is applied in this state, it is easily cleaved and forms a stable sol in water. Bentonite and swellable synthetic mica have a strong tendency and are preferred for the purpose of the present invention. In particular, swellable synthetic mica is preferred.

As the swellable synthetic mica used in the present invention, Na tetrathick mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ Na or Li teniolite (NaLi) Mg ₂ (Si ₄ O
₁₀₎ F ₂ Na or Li hectorite (NaLi) / 3Mg ₂ / 3L
i _1/3 Si ₄ O ₁₀ ) F _{2 and the} like.

The swellable synthetic mica preferably used in the present invention has a thickness of 1 to 50 nm and a surface size of 1.
２０20 μm. For diffusion control, the thinner the better, the better, and the planar size is better as long as the smoothness and transparency of the coated surface are not deteriorated. Therefore, the aspect ratio is 100 or more, preferably 200 or more, particularly preferably 50 or more.
0 or more.

When ordinary gelatin is used, as the ratio of mica (to gelatin 1.5 to 10 or more) increases, the viscosity and gelation progress at a certain solid content concentration (for example, 5% to 10%). To reduce the viscosity using normal gelatin,
There is a method of lowering the concentration, but lowering the concentration increases the drying load of the coating film, and there is a problem that the coated surface due to thick coating deteriorates. There is also a method of adding urea, salt, or the like to the coating solution, but the viscosity cannot be sufficiently reduced, and the surface after coating is poor. The gelatin in the present invention can significantly reduce thickening and gelation without causing such adverse effects.Especially, in the case of the low-molecular-weight gelatin of the present invention, the thickening and gelling can be achieved even when used in combination with mica. It can be significantly reduced.

The content of the water-swellable synthetic mica in the undercoat layer is such that the weight ratio of mica / gelatin is 1/20 to 1
/ 2 is desirable. If the content of the water-swellable synthetic mica is less than 1/20, the undercoat layer will not function sufficiently as an oxygen barrier layer, and if it is more than 1/2, the coating properties such as coatability will deteriorate. The amount of mica applied to the undercoat layer is preferably 0.01 g / m ² or more, and more preferably 0.02 g / m ² or more. The amount of mica applied is 0.
When the amount is less than 01 g / m ² , the oxygen-blocking ability of the undercoat layer is reduced, so that the characteristics of the present invention such as prevention of background coloring or the like cannot be exhibited.

As the color-forming component used in the heat-sensitive recording layer, conventionally known color-forming components can be used. In the heat-sensitive recording material of the present invention, a material utilizing a reaction between a diazonium salt compound and a coupler, and Those utilizing a reaction between a donor colorless dye and an electron accepting compound are also preferable,
The compound used in the heat-sensitive recording layer containing a diazonium salt compound and a coupler which reacts with the diazonium salt compound when heated to form a color, is a diazonium salt compound, a coupler capable of reacting with the diazonium salt compound to form a dye, and Basic substances that promote the reaction between the diazonium salt compound and the coupler are exemplified. The diazonium salt compound is a compound represented by the following, and can control the maximum absorption wavelength depending on the position and type of the substituent in the Ar portion.

[0024]

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[0025] Ar is an aryl group, X ^- represents an acid anion.

Specific examples of the diazonium salt compound in the present invention include 4- (N- (2- (2,4-di-
tert-amylphenoxy) butyryl) piperazino)
Benzenediazonium, 4-dioctylaminobenzenediazonium, 4- (N- (2-ethylhexanoyl)
Piperazino) benzenediazonium, 4-dihexylamino-2-hexyloxybenzenediazonium, 4-
N-ethyl-N-hexadecylamino-2-ethoxybenzodiazonium, 3-chloro-4-dioctylamino-2-octyloxyobenzenediazonium, 2,5
-Dibutoxy-4-morpholinobenzenediazonium,
2,5-octoxy-4-morpholinobenzenediazonium, 2,5-dibutoxy-4- (N- (2-ethylhexanoyl) piperazino) benzenediazonium, 2,
5-diethoxy-4- (N- (2- (2,4-di-te
acid anion salts such as rt-amylphenoxy) butyryl) piperazino) benzenediazonium, 2,5-dibutoxy-4-tolylthiobenzenediazonium, 3- (2-octyloxyethoxy) -4-morpholinobenzenediazonium; Diazonium salt compound D-1
~ 5. Particularly, hexafluorophosphate salt, tetrafluoroborate salt and 1,5-naphthalene sulfonate salt are preferable.

[0027]

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Among these diazonium salt compounds, particularly preferred compounds in the present invention are 300 to 400.
4- (N- (2-
(2,4-di-tert-amylphenoxy) butyryl) piperazino) benzenediazonium, 4-dioctylaminobenzenediazonium, 4- (N- (2-ethylhexanoyl) piperazino) benzenediazonium,
4-dihexylamino-2-hexyloxybenzenediazonium, 4-N-ethyl-N-hexadecylamino-2-ethoxybenzodiazonium, 2,5-dibutoxy-4- (N- (2-ethylhexanoyl) piperazino) Benzenediazonium, 2,5-diethoxy-4-
(N- (2- (2,4-di-tert-amylphenoxy) butyryl) piperazino) benzenediazonium and the compounds shown in the above specific examples D-3 to D-5. The maximum absorption wavelength of the diazonium salt compound as referred to herein is a spectrophotometer (Shimazu MPS-200) obtained by coating each compound with a coating film of 0.1 g / m ² to 1.0 g / m ^2.
0).

Examples of the coupler used in the present invention, which reacts with the diazonium salt upon heating to give a color, include resorcin, flurgurcine, and 2,3-dihydroxynaphthalene-6.
Sodium sulfonate, 1-hydroxy-2-naphthoic acid morpholinopropylamide, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-
Dihydroxy-6-sulfanylnaphthalene, 2-hydroxy-3-naphthoic acid anilide, 2-hydroxy-3
-Naphthoic acid ethanolamide, 2-hydroxy-3-
Naphthoic acid octylamide, 2-hydroxy-3-naphthoic acid-N-dodecyloxypropylamide, 2-hydroxy-3-naphthoic acid tetradecylamide, acetanilide, acetoacetanilide, benzoylacetanilide, 2-chloro-5-octylacetate Acetanilide, 1-phenyl-3-methyl-5-pyrazolone, 1-
(2′-octylphenyl) -3-methyl-5-pyrazolone, 1- (2 ′, 4 ′, 6′-trichlorophenyl)
-3-benzamide-5-pyrazolone, 1- (2 ',
4 ', 6'-trichlorophenyl) -3-anilino-5
-Pyralone, 1-phenyl-3-phenylacetamido-5-pyrazolone, and the following compounds C-1 to C-6. These couplers can be used in combination of two or more to obtain a desired color hue.

[0030]

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The basic substance in the heat-sensitive recording layer includes, in addition to an inorganic or organic basic compound, a compound which decomposes upon heating to release an alkaline substance. Representatives are organic ammonium salts, organic amines, amides, ureas and thioureas and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles , Morpholines,
Examples include nitrogen-containing compounds such as piperidines, amidines, formazines, and pyridines. Specific examples of these include tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine,
Allyl urea, thiourea, methyl thiourea, allyl thiourea, ethylene thiourea, 2-benzylimidazole, 4
-Phenylimidazole, 2-phenyl-4-methylimidazole, 2-undecylimidazoline, 2,4,5
-Trifuryl-2-imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-triphenylguanidine, 1,2-dicyclohexylguanidine, 1, 2,
3-tricyclohexylguanidine, guanidine trichloroacetate, N, N'-dibenzylpiperazine, 4,
4'-dithiomorpholine, morpholinium trichloroacetate, 2-aminobenzothiazole, 2-benzoylhydrazinobenzothiazole and the like. These can be used in combination of two or more.

As the electron donating dye used in the present invention, an electron donating dye precursor can be used. Examples of the precursor include a triarylmethane compound, a diphenylmethane compound, a thiazine compound, a xanthene compound, and spiropyran. And triarylmethane compounds and xanthene compounds are particularly useful because of their high color density. To illustrate some of these,
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (that is, crystal violet lactone), 3,3-bis (p-dimethylamino) phthalide, 3- (p-dimethylaminophenyl) -3 − (1,
3-dimethylindol-3-yl) phthalide, 3-
(P-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (o-methyl-p
-Diethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 4,4'-bis (dimethylamino) benzhydrin benzyl ether, N-halophenylleucouramine, N-2,4,5 -Trichlorophenylleuco auramine, rhodamine-B-anilinolactam, rhodamine (p-nitroanilino) lactam, rhodamine-B- (p-chloroanilino) lactam, 2-benzylamino-6-diethylaminofluoran, 2-anilino-6 -Diethylaminofluoran, 2
-Anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-cyclohexylmethylaminofluoran, 2-anilino-3-methyl-6
-Isoamylethylaminofluoran, 2- (o-chloroanilino) -6-diethylaminofluoran, 2-octylamino-6-diethylaminofluoran, 2-ethoxyethylamino-3-chloro-2-diethylaminofluoran, 2- Anilino-3-chloro-6-diethylaminofluoran, benzoylleucomethylene blue,
p-Nitrobenzyl leucomethylene blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, 3-benzylspirodinaphthopyran, 3-propyl-spiro-dibenzopyran And the like.

Examples of the electron-accepting compound include phenol derivatives, salicylic acid derivatives, and hydroxybenzoic acid esters. Particularly, bisphenols and hydroxybenzoates are preferred. Some examples of these include 2,2-bis (p-hydroxyphenyl) propane (ie, bisphenol A), 4,4 ′-(p-phenylenediisopropylidene) diphenol (ie, bisphenol P), 2,2-bis (p-hydroxyphenyl) pentane, 2,2-bis (p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl)
Butane, 2,2-bis (4'-hydroxy-3 ', 5'
-Dichlorophenyl) propane, 1,1- (p-hydroxyphenyl) cyclohexane, 1,1- (p-hydroxyphenyl) propane, 1,1- (p-hydroxyphenyl) pentane, 1,1- (p-hydroxyphenyl) ) -2-Ethylhexane, 3,5-di (α-methylbenzyl) salicylic acid and its polyvalent metal salts, 3,5-di (tert-butyl) salicylic acid and its polyvalent metal salts, 3-α, α- Dimethylbenzyl salicylic acid and its polyvalent metal salts, butyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, p-hydroxybenzoic acid
2-ethylhexyl, p-phenylphenol, p-cumylphenol and the like can be mentioned.

As the sensitizer, a low-melting organic compound having an aromatic group and a polar group in the molecule is preferable.
benzyl p-benzyloxybenzoate, α-naphthyl benzyl ether, β-naphthyl benzyl ether, β-
Naphthoic acid phenyl ester, α-hydroxy-β-naphthoic acid phenyl ester, β-naphthol- (p-chlorobenzyl) ether, 1,4-butanediol phenyl ether, 1,4-butanediol-p-methylphenyl ether, 1,4-butanediol-p-ethylphenyl ether, 1,4-butanediol-m-methylphenyl ether, 1-phenoxy-2- (p-tolyloxy) ethane, 1-phenoxy-2- (p-ethylphenoxy) ) Ethane, 1-phenoxy-2- (p-chlorophenoxy) ethane, p-benzylbiphenyl and the like.

In the present invention, use forms of the above-mentioned diazonium salt compound, a coupler, a basic substance, a colorless electron-donating dye, an electron-accepting compound, and a sensitizer which react with the diazonium salt compound to give a color when heated. Is not particularly limited. (1) a method using solid dispersion, (2) a method using emulsification dispersion, (3) a method using polymer dispersion, (4) a method using latex dispersion,
(5) There is a method of microencapsulation and the like, and among these, the method of microencapsulation is particularly preferable from the viewpoint of storage stability. Particularly, in a color system using a reaction between a diazonium salt compound and a coupler, When the diazonium salt compound is microencapsulated, it is preferable to microencapsulate the electron donating colorless dye in a color forming system utilizing the reaction between the electron donating colorless dye and the electron accepting compound.

In the present invention, the above-mentioned heat-sensitive recording layers may be laminated, and a multi-color heat-sensitive recording material can be obtained by changing the hue of each heat-sensitive recording layer. Although the layer configuration is not particularly limited, it is particularly preferable that the layers having different photosensitive wavelengths have different wavelengths.
Thermal recording using two types of diazonium salt compounds, two thermosensitive recording layers combining couplers that react with each diazonium salt compound when heated to develop different colors, and a thermosensitive recording layer combining an electron-donating colorless dye and an electron-accepting compound. A multicolor heat-sensitive recording material in which layers are laminated is preferred. That is, a thermosensitive recording layer A containing an electron-donating colorless dye and an electron-accepting compound on a support, a diazonium salt compound having a maximum absorption wavelength of 360 ± 20 nm, and a coupler which reacts with the diazonium salt compound when heated to give a color. Thermosensitive recording layer B-1 containing a diazonium salt compound having a maximum absorption wavelength of 400 ± 20 nm and a thermosensitive recording layer B-2 containing a coupler which reacts with the diazonium salt compound when heated to form a color. A color heat-sensitive recording material is desirable.

In the recording method of this multicolor heat-sensitive recording material, first, the heat-sensitive recording layer B-2 is heated so that the diazonium salt compound and the coupler contained in the layer are colored. Then 400 ± 20
After irradiating light of nm to decompose the unreacted diazonium salt compound contained in the heat-sensitive recording layer B-2, sufficient heat is applied to the heat-sensitive recording layer B-1 to develop a color, and The contained diazonium salt compound and the coupler are colored. At this time, the heat-sensitive recording layer B-2 is also strongly heated, but does not develop color because the diazonium salt compound has already been decomposed and the color-forming ability has been lost. 360 ± 20
The diazonium salt compound contained in the heat-sensitive recording layer B-1 is decomposed by irradiating light with a wavelength of nm, and finally, sufficient heat for the heat-sensitive recording layer A to develop color is applied to develop the color. At this time, the heat-sensitive recording layers B-2 and B-1 are also strongly heated at the same time, but do not develop color because the diazonium salt compound has already been decomposed and the coloring ability has been lost.

Further, a multi-color thermosensitive recording in which three thermosensitive recording layers in which three kinds of diazonium salt compounds having different photosensitive wavelengths and a coupler which reacts with each of the diazonium salt compounds upon heating and develops a different hue are combined is laminated. Materials are also preferred. That is, the heat-sensitive recording layer A-1 containing a diazonium salt compound having a maximum absorption wavelength of 350 nm or less, preferably 340 nm or less, and a coupler that reacts with the diazonium salt compound when heated to form a color on the support. A thermosensitive recording layer B-1 containing a diazonium salt compound having a wavelength of 360 ± 20 nm and a coupler which reacts with the diazonium salt compound when heated to form a color, and has a maximum absorption wavelength of 400 ± 2
A multicolor heat-sensitive recording material in which a diazonium salt compound having a thickness of 0 nm and a heat-sensitive recording layer B-2 containing a coupler which reacts with the diazonium salt compound when heated to form a color is preferably laminated.
In these examples, a full-color image can be recorded by selecting the coloring hues of each heat-sensitive recording layer so as to be three primary colors, yellow, magenta, and cyan in the subtractive color mixing.

When laminating thermosensitive coloring layers having different hues, an intermediate layer for preventing color mixing or the like can be provided between the thermosensitive recording layers. In the intermediate layer, as a water-soluble polymer compound, for example, polyvinyl alcohol, modified polyvinyl alcohol, methyl cellulose, sodium polystyrene sulfonate, styrene-maleic acid copolymer,
Those composed of gelatin and / or zetiran derivatives, polyethylene glycol and / or polyethylene glycol derivatives are desirable. In addition, by including an inorganic layered compound in the intermediate layer, mass transfer between layers is suppressed.
Prevention prevents color mixing, and suppresses supply of oxygen, thereby improving raw storability and color image storability.

In the present invention, it is desirable to provide a protective layer containing a pigment, a release agent and the like on the heat-sensitive recording layer in order to protect the heat-sensitive recording layer from sticking and solvents. An inorganic layered compound containing mica or the like may be used as a pigment in the protective layer, but other pigments may be used in combination. Examples of such pigments include calcium oxide, zinc oxide, titanium oxide, aluminum hydroxide, kaolin, synthetic silicate, amorphous silica, and urea formalin resin powder.

In the heat-sensitive recording material of the present invention, a light transmittance adjusting layer can be provided. The light transmittance adjusting layer contains a component that functions as a precursor of an ultraviolet absorber, and does not function as an ultraviolet absorber before irradiation with light having a wavelength in a region necessary for fixing. When the fixing type thermosensitive recording layer is fixed, the wavelength in the region required for fixing is sufficiently transmitted, and the transmittance of visible light is high, so that there is no trouble in fixing the thermosensitive recording layer.

The precursor of the ultraviolet absorber is converted into an ultraviolet absorber by reacting with light or heat after light irradiation of a wavelength necessary for fixing of the light fixing type thermosensitive recording layer by light irradiation is completed. As a result, most of the light in the wavelength range necessary for fixing in the ultraviolet region is absorbed by the ultraviolet absorber, the transmittance is reduced, and the light resistance of the heat-sensitive recording material is improved. Because there is no absorption effect,
The visible light transmittance is not substantially changed.

At least one light transmittance adjusting layer can be provided in the light-fixing type heat-sensitive recording material. Most preferably, it is formed between the light-fixing type heat-sensitive recording layer and the protective layer. The rate adjusting layer may be used also as the protective layer.

By changing the hue of each heat-sensitive recording layer in the heat-sensitive recording layer, a multi-color heat-sensitive recording material can be obtained.
That is, a full-color image can be recorded by selecting the coloring hues of the respective heat-sensitive recording layers so as to be three primary colors, yellow, magenta, and cyan in the subtractive color mixing. In this case, the coloring mechanism of the heat-sensitive recording layer directly laminated on the support surface (the lowermost layer of the heat-sensitive recording layer) is not limited to the combination of the electron-donating dye and the electron-accepting dye. Any of a diazo coloring system, a base coloring system that forms a color by contacting with a basic compound, a chelating coloring system, and a coloring system that reacts with a nucleophile to cause a desorption reaction to form a color from a coupler that reacts with a diazonium salt to form a color. Alternatively, two heat-fixable heat-sensitive recording layers each containing a diazonium salt compound having a different maximum absorption wavelength and a coupler that reacts with the diazonium salt compound to form a color may be provided on the heat-sensitive recording layer. It is desirable to sequentially provide a transmittance adjusting layer and a protective layer.

In the present invention, examples of the precursor of the ultraviolet absorbent contained in the light transmittance adjusting layer include the following general formula 1.

[0046]

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In the above general formula 1, m represents 1 or 2. A represents —SO ₂ —R, —CO—R, when m = 1 in the general formula (1) and in the general formulas (2) to (4).
_{-CO 2 -R, -CONH-R,} -POR 1 R 2, -C
H ₂ R ₃ or —SiR ₄ R ₅ R ₆ , wherein R
Represents an alkyl group or an aryl group, R ₁ and R ₂ represent an alkoxy group, an aryloxy group, an alkyl group or an aryl group, R ₃ represents a phenyl group substituted by at least one nitro group or methoxy group, R ₄ , R _{4 5} and R ₆ represent an alkyl group or an aryl group, and m = 2 in the general formula (1).
A represents -SO ₂ R ₇ SO _2- , -CO-, -CO
_{CO -, - COR 7 CO -} , - SO 2 - or -SO-
And R ₇ represents an alkylene group or an arylene group.

X is represented by the general formulas (1), (3) and (4).
Hydrogen, alkyl, alkoxy, aryl
In general formula (2),
Alkylene group, -OR₇ O- or -OCOR₇ CO_Two 
Represents-. W is in general formulas (1), (2) and (4)
Represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl
In the general formula (3), the group or the halogen atom is represented by-
OR ₇ O- or -OCOR₇ CO_Two Represents-. Y is one
In general formulas (1), (2) and (3), a hydrogen atom,
Alkyl group, alkoxy group, aryl group or halogen source
Is represented by -OR in the general formula (4).₇O-, -OC
OR₇ CO_Two -, -CH_Two CH_Two CO_Two R₇ OCOCH
_Two CH_Two -, -CH_Two CH_Two OCOR₇ CO_Two CH_Two C
H_Two -Or -CH_Two CH_Two CON (R₈ ) R₇ N (R
₈ ) COCH_Two CH_Two -Is R₈ Is a hydrogen atom or al
Represents a kill group. Z is a hydrogen atom, a halogen atom, an alkyl
Represents a group or an alkoxy group.

Of the above substituents, the alkyl group may be linear or branched, and may have an unsaturated bond.
Further, these alkyl groups may be substituted with an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl group, a hydroxy group, or the like. The aryl group may be further substituted with an alkyl group, an alkoxy group, or a halogen atom.

Of the above substituents, the alkylene group may be linear or branched, and may contain an unsaturated bond, an oxygen atom, a sulfur atom, or a nitrogen atom. The alkylene group may be further substituted with an alkoxy group, a hydroxy group, an aryloxy group, or an aryl group.

Of the above substituents, the arylene group may be further substituted with an alkyl group, an alkoxy group, a halogen atom and the like.

Among the substituents represented by X, Y and W, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms,
To 18 alkoxy groups, 6 to 18 carbon atoms, aryl groups, fluorine atoms, chlorine atoms, and bromine atoms are preferred. Among them, particularly preferred are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a 1 to 1 carbon atom. Twelve alkoxy groups, phenyl groups or chlorine atoms are preferred.

Among the substituents represented by Z, a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms are preferable. , Chlorine atom, 1-6 carbon atoms
And an alkoxy group having 1 to 6 carbon atoms is preferred.

Among the substituents represented by R, those having 1 carbon atom
Preferred are an alkyl group having 18 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms, and among these, an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms are particularly preferred.

Of the substituents represented by R ₁ and R ₂ ,
An alkoxy group having 1 to 12 carbon atoms, 6 to 1 carbon atoms
An aryloxy group of 2, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms are preferable.

Among the substituents represented by R ₃ , a 2-nitrophenyl group, a 3,5-dimethoxyphenyl group, a 3,4,
A 5-trimethoxyphenyl group is preferred.

Among the substituents represented by R ₄ , R ₅ and R ₆ , an alkyl group having 1 to 12 carbon atoms and a carbon atom having 6 carbon atoms
~ 12 aryl groups are preferred. Among them, an alkyl group having 1 to 8 carbon atoms and a phenyl group are particularly preferable.

The compound represented by the general formula 1 can be used in the following forms: (1) a method of using a solid dispersion, (2) a method of using an emulsified dispersion, (3) a method of using a polymer, (4) Latex dispersed method, (5)
Although there is a method of microencapsulation and the like, it is particularly preferable to use emulsified dispersion or microencapsulation.

As a method of emulsifying and dispersing, first, the compound represented by the general formula 1 is dissolved in oil. The oil may be solid or liquid at room temperature or a polymer. Low-boiling co-solvents such as acetate, methylene chloride, cyclohexanone and / or phosphates, phthalates, acrylates, methacrylates, other carboxylates, fatty acid amides, alkylated biphenyls, alkylated terphenyls, Examples thereof include alkylated naphthalene, diarylethane, chlorinated paraffin, alcohol, phenol, ether, monoolefin, and epoxy. Specific examples include tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tricyclohexyl phosphate, dibutyl phthalate, dioctyl phthalate, dilaurate phthalate,
Dicyclohexyl phthalate, butyl olefin, diethylene glycol benzoate, dioctyl sebacate, dibutyl sebacate, dioctyl adipate, trioctyl trimellitate, acetyl triethyl citrate, octyl maleate, dibutyl maleate, isoamyl biphenyl, chlorinated paraffin, diisopropyl naphthalene 1,1,1′-ditolylethane, 2,4-dita-
High-boiling oils such as shariamylphenol, N, N-dibutyl-2-butoxy-5-tert-octylaniline, 2-ethylhexyl hydroxybenzoate, and polyethylene glycol, among which alcohols and phosphates are particularly preferred. System, carboxylic acid ester system, alkylated biphenyl, alkylated terphenyl, alkylated naphthalene, and diarylethane are preferred. Furthermore, hindered phenol,
An anti-carbonizing agent such as hindered amine may be added. Further, as the oil using the compound of the general formula 1, oil having an unsaturated fatty acid is particularly desirable, and examples thereof include α-methylstyrene dimer. The α-methylstyrene dimer includes, for example, MSD100 (trade name of Mitsui Toatsu Chemical).

An oil solution containing the compound of the above general formula 1 is added to an aqueous solution of a water-soluble polymer, and emulsified and dispersed using a colloid mill, a homogenizer, or ultrasonic waves. As the water-soluble polymer used at this time, a water-soluble polymer such as polyvinyl alcohol is used, but an emulsion or latex of a hydrophobic polymer may be used in combination. As the water-soluble polymer, polyvinyl alcohol,
Silanol-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amino-modified polyvinyl alcohol, itaconic acid-modified polyvinyl alcohol, styrene-maleic anhydride copolymer, butadiene maleic anhydride copolymer, ethylene maleic anhydride copolymer, isobutylene maleic anhydride copolymer Examples include polymers, polyacrylamide, polystyrenesulfonic acid, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, and gelatin. At this time, a conventionally known surfactant or the like may be added as necessary.

As a method for microencapsulation of the diazonium salt compound or the compound of the general formula 1, a conventionally known microcapsule method can be used. That is, a diazonium salt compound or a compound of the general formula 1 and a microcapsule wall precursor are dissolved in a water-insoluble or insoluble organic solvent, added to an aqueous solution of a water-soluble polymer, and emulsified and dispersed using a homogenizer or the like. Then, the polymer substance which becomes the microcapsule wall when the temperature is raised can be prepared by forming a wall film on the oil / water interface. Specific examples of the high molecular substance serving as the wall film of the microcapsules include, for example, polyurethane resin, polyurea resin, polyamide resin,
Examples include polyester resin, polycarbonate resin, aminoaldehyde resin, melamine resin, polystyrene resin, styrene-acrylate copolymer resin, styrene-methacrylate copolymer resin, gelatin, and polyvinyl alcohol. Among these, a particularly preferred wall material is a microcapsule having a wall film made of a polyurethane / polyurea resin.

A microcapsule having a wall film made of a polyurethane / polyurea resin is prepared by mixing a microcapsule wall precursor such as polyvalent isocyanate in a core material to be encapsulated, and emulsifying the mixture in an aqueous solution of a water-soluble polymer such as polyvinyl alcohol. It is produced by dispersing, raising the liquid temperature and causing a polymer forming reaction at the oil droplet interface.

Here, some specific examples of the polyvalent isocyanate compound are shown below. For example, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-
Tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,
3'-diphenylmethane-4,4'-diisocyanate, xylene-1,4-diisocyanate, 4,4'-
Diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,
Diisocyanates such as 2-diisocyanate, cyclohexylene-1,2-diisocyanate and cyclohexylene-1,4-diisocyanate; 4,4 ', 4 "-triphenylmethane triisocyanate; toluene-2,
Triisocyanates such as 4,6-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2 ',
Tetraisocyanates such as 5,5'-tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, adducts of 2,4-tolylenediisocyanate and trimethylolpropane, and xylylenediisocyanate and trimethylolpropane Isocyanate prepolymers such as adducts and adducts of tolylene diisocyanate and hexanetriol, and the like. If necessary, two or more kinds can be used in combination. Of these, particularly preferred are those having three or more isocyanate groups in the molecule.

In the microencapsulation method, an oil represented by emulsified dispersion can be used as an organic solvent for dissolving the diazonium salt compound or the compound represented by the general formula 1. The same applies to a water-soluble polymer.

The particle size of the microcapsules is 0.1 to 1.0
μm is preferred, and more preferably in the range of 0.2 to 0.7 μm.

In the present invention, the following known antioxidants can be used in order to further improve the light fastness. For example, EP-A-310551,
German Patent No. 3435443, European Patent No. 310552, Japanese Patent Application Laid-Open No. 3-121449.
JP-A-59-41616, JP-A-2-262654, JP-A-2-71262, JP-A-63-163351, U.S. Pat. No. 4,814,262, and JP-A-54-48535. ,
JP-A-5-61166, JP-A-5-119449
No., US Pat. No. 4,980,275, JP-A-63
JP-A-113536, JP-A-62-262047, EP-A-223239, EP-A-309402, and EP-A-309401.
Specifically, the following are mentioned.

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It is also effective to use various additives which are already known as heat-sensitive recording materials and pressure-sensitive recording materials. Some of these antioxidants are described in JP-A-60-12.
No. 5,470, JP-A-60-125471, JP-A-60-125472, JP-A-60-2874
No. 85, JP-A-60-287486, JP-A-60-287487, JP-A-62-146680
JP, JP-A-60-287488, JP-A-60-287488
JP-A-282885, JP-A-63-89877, JP-A-63-88380, JP-A-63-08
JP-A-8381, JP-A-01-239282, JP-A-04-291885, JP-A-04-2916
No. 84, JP-A-05-188687, JP-A-05-188686, JP-A-05-110490
JP, JP-A-05-1108437, JP-A-05-1108437
JP-A-5-170361, JP-A-63-203372, JP-A-63-224789, JP-A-63-267594, JP-A-63-182484, JP-A-60-107384 JP-A-60-1
07383, JP-A-61-160287,
JP-A-61-185483, JP-A-61-2111
No. 079, JP-A-63-251282, JP-A-63-051174, JP-B-48-04329.
No. 4, JP-B-48-033212 and the like.

Specific examples include 6-ethoxy-1-phenyl-
2,2,4-trimethyl-1,2-dihydroquinoline,
6-ethoxy-1-octyl-2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1-phenyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, 6-ethoxy-1-octyl-2,
2,4-trimethyl-1,2,3,4-tetrahydroquinoline, nickel cyclohexanoate, 2,2-bis-4
-Hydroxyphenylpropane, 1,1-bis-4-hydroxyphenyl-2-ethylhexane, 2-methyl-
4-methoxy-diphenylamine, 1-methyl-2-phenylindole. These antioxidants are
It can be added to the heat-sensitive recording layer or the intermediate layer, the light transmittance adjusting layer, and the protective layer.

Next, the light-sensitive material layer provided on the undercoat layer may be a silver halide emulsion layer. The silver halide in the silver halide emulsion layer may be any of silver iodobromide, silver bromide, silver chlorobromide, silver iodochloride, silver chloride, and silver iodochlorobromide. The size of a silver halide grain is calculated as 0.
1-2 μm, particularly preferably 0.2-1.5 μm.

The silver halide grains used in the present silver halide emulsion layer may have a hexagonal or rectangular tabular shape. Among them, the aspect ratio is 2 or more, preferably 8 or more, and more preferably. 20 or more tabular grains are preferable, and in such tabular grains, 50% or more, preferably 80% or more, and more preferably 90% of the projected area of all grains.
It is preferable to use an emulsion occupying the above.

Also, US Pat. No. 5,494,789,
Nos. 5,503,970, 5,503,971, 5,536,632 and the like.
Particles thinner than 07 μm and having a higher aspect ratio can also be preferably used. Also, U.S. Pat.
No. 463, No. 4, 713, 323, No. 5, 217, 8
High silver chloride tabular grains having a (111) plane as a main plane described in US Pat.
No. 337, 5, 292, 632, 5, 310, 6
High silver chloride tabular grains having a (100) plane as a main plane described in JP-A No. 35 or the like can also be preferably used.

Examples of actually using these silver halide grains are disclosed in Japanese Patent Application Nos. 8-46822 and 8-97344.
No. 8-238672. It is preferable that the emulsion of the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization, a chalcogen sensitization method using a sulfur, selenium or tellurium compound, a noble metal sensitization method using gold, platinum, iridium, or the like, or a compound having an appropriate reducing property during grain formation is used. Thus, a so-called reduction sensitization method for obtaining high sensitivity by introducing a reducing silver nucleus can be used alone or in various combinations.

As the spectral sensitization, cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar dyes, hemicyanine dyes, which are adsorbed on silver halide grains to have sensitivity in the absorption wavelength range of the silver halide grains, are provided. A so-called spectral sensitizing dye such as a styryl dye or a hemioxonol dye is used alone or in combination, and is preferably used together with a supersensitizer.

In the silver halide emulsion, nitrogen-containing heterocyclic compounds such as azaindenes, triazoles, tetrazoles, purines and the like, mercaptotetrazole, mercapto are used for the purpose of preventing fogging and improving the stability during storage. It is preferable to add various stabilizers such as mercapto compounds such as triazoles, mercaptoimidazoles, and mercaptothiadiazoles.

Photographic additives for silver halide emulsions are described in Research Disclosure Magazine No. 17643 (197).
No. 18716 (November 1979)
), No. 307105 (November 1989), and No. 38957 (September 1996) can be preferably used. The photosensitive silver halide is preferably used in an amount of 0.05 to ²⁰ g / m ^{2 in} terms of silver, and more preferably 0.1 to 10 g / m ² .

The binder for the light-sensitive material layer is preferably hydrophilic. Examples of the binder include the research disclosure described in the preceding section and JP-A-64-13546.
~ 75 pages. Among them, gelatin and gelatin and other water-soluble binders,
For example, a combination with polyvinyl alcohol, modified polyvinyl alcohol, a cellulose derivative, an acrylamide polymer, or the like is preferable. Binder coating amount is 1 to 20 g
/ M ² , more preferably ² to 15 g / m ² ,
More preferably, 3 to 12 g / m ² is appropriate. Among them, gelatin is 50% to 100%, preferably 70%.
% To 100%.

As the color developing agent, p-phenylenediamines or p-aminophenols may be used, but sulfonamidophenol, sulfonylhydrazine, carbamoylhydrazone and the like are preferable.

As the color developing agent, one or a combination of a plurality of the above compounds is used. Separate developing agents may be used for each layer. The total amount of these developing agents used is 0.05 to 20 mmol / m ² , preferably 0.1 to 1 mmol / m ² .
0 mmol / m ² . For the light-sensitive material layer, a coupler that forms a dye by a coupling reaction with an oxidized form of the color developing agent is used. Preferred examples thereof include active methylene,
Examples include compounds generally referred to as 5-pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole. A specific example is Research Disclosure N
o. No. 38957 (September 1996), pages 616 to 624 can be preferably used. A particularly preferred example is described in JP-A-8-110608.
Pyrazoloazole couplers as described in
Examples include pyrrolotriazole couplers described in JP-A-8-122994 and Japanese Patent Application No. 8-45564. These couplers are available in 0.05 to 10 mmo for each color.
1 / m ² is preferred, more preferably 0.1 to 5 mm
ol / m ² .

Further, colored couplers for correcting unnecessary absorption of color-forming dyes, residues of photographically useful compounds which react with oxidized developing agents, for example, compounds (including couplers) which release development inhibitors, etc. Can also be used.

The light-sensitive material layer is usually composed of three or more photosensitive layers having different color sensitivity. Each light-sensitive layer contains at least one silver halide emulsion layer, but typical examples include
It comprises a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The light-sensitive layer is a single light-sensitive layer having color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, generally, the arrangement of the single light-sensitive layer is generally used. Are sequentially provided from the support side in the order of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. The total thickness of the photosensitive layer is 1 to 20 μm.
And more preferably 3 to 15 μm.

The silver halide, the color developing agent and the coupler may be contained in the same photosensitive layer or in different layers. In addition to the photosensitive layer, a non-photosensitive layer such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer may be provided, and a back layer may be provided on the back side of the support. The thickness of the entire coating film on the photosensitive layer side is preferably from 3 to 25 μm, and more preferably from 5 to 20 μm.

In the light-sensitive material layer, a hardener, a surfactant, a photographic stabilizer, an antistatic agent, a slipping agent, a matting agent, a latex, a formalin scavenger, a dye, a UV absorber and the like may be used for various purposes. it can. Examples of these are disclosed in the aforementioned Research Disclosure and Japanese Patent Application No. 8-3010.
No. 3 and the like. Examples of particularly preferred antistatic agents include ZnO, TiO ₂ , Al ₂ O ₃ , and In.
₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂ O
_{5 and the} like.

In the above description, an example is shown in which the undercoat layer of the light-sensitive material layer contains low-viscosity (low-molecular-weight) gelatin and water-swellable synthetic mica. Even if swellable mica is contained in the above-described light-sensitive material layer in addition to the undercoat layer, the sensitivity of the light-sensitive material layer can be enhanced by its ability to block oxygen to the light-sensitive material layer.

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[Example 1]

<Preparation of coating layer> Preparation of gelatin solution Enzymatically degraded gelatin (average molecular weight: 10,000, PAGI
(Method viscosity: 15 mP, PAGI method jelly strength: 20 g), 40 parts and water (60 parts) were added, and the mixture was stirred and dissolved at 40 ° C. Preparation of Mica Dispersion Eight parts of water-swellable synthetic mica (aspect ratio: 1000, trade name: Somasif ME100, manufactured by Corp Chemical) and water 9
After mixing with 2 parts, the mixture was wet-dispersed with a biscomil to obtain a mica dispersion having an average particle diameter of 2.0 μm. Water was added to this dispersion so that the mica concentration was 5% by weight, and the mixture was mixed uniformly to obtain a mica dispersion. Gelatin hardener E-1 gelatin hardener 1.66% by weight ethylene oxide surfactant

A 40% by weight gelatin solution 1 at 40 ° C.
After adding 120 parts of water and 556 parts of methanol to 00 parts and sufficiently stirring and mixing, 208 parts of 5% by weight of the mica dispersion liquid is added and sufficiently stirred and mixed, and 9.8 parts of 1.66% by weight of a surfactant is added. Add. And the liquid temperature is 35 ℃ to 40 ℃
7.3 parts of a gelatin hardener is added to obtain an undercoat layer solution (5.7% by weight).

This was adjusted to a coating amount of mica of 0.2 g / m ² and coated on a photographic paper support in which a polyester film was laminated on both sides of a high-quality paper to provide a mica undercoat layer.

Preparation of Solution A for Thermosensitive Recording Layer (Preparation of Capsule Solution for Electron-donating Dye Precursor) Crystal violet lactone as an electron-donating dye precursor
0 parts were dissolved in 20 parts of ethyl acetate, and 20 parts of alkylnaphthalene, which is a high boiling point solvent, was added, and the mixture was heated and uniformly mixed. As a capsule wall material, 20 parts of an xylylene diisocyanate / trimethylolpropane adduct was further added to this solution, and the mixture was stirred uniformly. Separately, 54 parts of a 6% by weight aqueous solution of gelatin were prepared, and the above-mentioned electron-donating dye precursor solution was added thereto, followed by emulsification and dispersion with a homogenizer.
After 68 parts of water was added to the obtained emulsion to homogenize it, the temperature was raised to 50 ° C. with stirring, and an encapsulation reaction was performed for 3 hours to obtain a desired capsule liquid. The average particle size of the capsule is 1.6
μm.

(Preparation of Electron-Accepting Compound Dispersion) As an electron-accepting compound, 30 parts of bisphenol A was added to gelatin 4
It was added to 150 parts by weight of an aqueous solution and dispersed by a ball mill for 24 hours to prepare a dispersion. The average particle size of the electron-accepting compound in the dispersion was 1.2 μm.

(Preparation of Coating Solution) Next, the above-mentioned capsule solution of the electron-donating dye precursor and the dispersion liquid of the electron-accepting compound were adjusted so that the ratio of the electron-donating dye precursor / electron-accepting compound was 1/2. The mixture was mixed to prepare a target coating solution.

Preparation of Solution B for Thermosensitive Recording Layer (Preparation of Capsule Solution for Diazonium Salt Compound) As the diazonium salt compound, 4- (N- (2- (2,4-di-te) was used.
Dissolve 2.0 parts of rt-amylphenoxy) butyryl) piperazinobenzenediazonium hexafluorophosphate in 20 parts of ethyl acetate, add 20 parts of alkylnaphthalene, which is a high-boiling point solvent, and heat to mix uniformly. did. As a capsule wall material, 15 parts of an adduct of xylylene diisocyanate / trimethylolpropane was further added to this solution, and the mixture was stirred uniformly. Separately, 54 parts of a 6% by weight aqueous solution of gelatin were prepared, the above diazonium salt compound solution was added, and the mixture was emulsified and dispersed with a homogenizer. After 68 parts of water was added to the obtained emulsion to homogenize it, the temperature was raised to 40 ° C. with stirring, and an encapsulation reaction was performed for 3 hours to obtain a desired capsule liquid. The average particle size of the capsule is 1.1 μm
Met.

(Preparation of Coupler Emulsion) 2 parts of 1- (2′-octylphenyl) -3-methyl-5-pyrazolone, 2 parts of 1,2,3-triphenylguanidine, 1,1- ( 2 parts of p-hydroxyphenyl) -2-ethylhexane, 4 parts of 4,4 ′-(p-phenylenediisopropylidene) diphenol, 2-ethylhexyl-
4-hydroxybenzoate 4 parts, tricresyl phosphate 0.3 part, diethyl maleate 0.1 part, 70%
1 part of a calcium dodecylbenzenesulfonate methanol solution is dissolved in 10 parts of ethyl acetate, and this solution is added to 80 parts of an 8% aqueous gelatin solution and emulsified with a homogenizer for 10 minutes. Then, ethyl acetate is removed to obtain a desired emulsion. Obtained.

(Preparation of Coating Liquid) Next, the above-mentioned diazonium salt compound capsule liquid and coupler dispersion liquid were mixed such that the ratio of the diazonium salt compound to the coupler became 2/3 to prepare a target coating liquid. Preparation of Liquid for Sensitizing Recording Layer C (Preparation of Capsule Solution of Diazonium Salt Compound) As a diazonium salt compound, 3.0 parts of 2,5-dibutoxy-4-tolylthiobenzenediazonium hexafluorophosphate was dissolved in 20 parts of ethyl acetate. Further, 20 parts of alkylnaphthalene, which is a high boiling point solvent, was added, and the mixture was heated and uniformly mixed. As a capsule wall material, 15 parts of an adduct of xylylene diisocyanate / trimethylolpropane was further added to this solution, and the mixture was stirred uniformly. Separately, 54 parts of a 6% by weight aqueous solution of gelatin were prepared, the above diazonium salt compound solution was added, and the mixture was emulsified and dispersed with a homogenizer. After 68 parts of water was added to the obtained emulsion to homogenize it, the temperature was raised to 40 ° C. with stirring, and an encapsulation reaction was performed for 3 hours to obtain a desired capsule liquid. The average particle size of the capsule was 1.0 μm.

(Preparation of Coupler Dispersion) 2 parts of 2-chloro-5- (3- (2,4-di-tert-pentyl) phenoxypropylamino) acetoacetanilide as a coupler, 1,2,3-triphenylguanidine Two copies,
1, l- (p-hydroxyphenyl) -2-ethylhexane 2 parts, 4,4 '-(p-phenylenediisopropylidene) diphenol 4 parts, 2-ethylhexyl-4-hydroxybenzoate 4 parts, tricresyl 0.3 part of phosphate, 0.1 part of diethyl maleate and 1 part of a 70% calcium methanol solution of dotesylbenzenesulfonate are dissolved in 10 parts of ethyl acetate, and this solution is added to 80 parts of an 8% aqueous gelatin solution and homogenized. After emulsification for 10 minutes, ethyl acetate was removed to obtain a target emulsion.

(Preparation of Coating Liquid) Next, the above-mentioned diazonium salt compound capsule liquid and coupler dispersion liquid were mixed so that the ratio of diazonium salt compound / coupler was 4/5 to prepare a target coating liquid.

Adjustment of Light Transmittance Adjusting Layer (Adjustment of UV Absorber Precursor Capsule Solution) Ethyl acetate 3
0 parts, as an ultraviolet absorber precursor [2-allyl-6-
(2H-benzotriazol-2-yl) -4-t-octylphenyl] benzenesulfonate 10 parts, 2,5
-Di-t-octyl-hydroquinone 3 parts, tricresyl phosphate 2 parts, α-methylstyrene dimer 4
Parts were dissolved. As a capsule wall material, 20 parts of an xylylene diisocyanate / trimethylolpropane adduct was further added to this solution, and the mixture was stirred uniformly. Separately, 200 parts of an 8% aqueous solution of itaconic acid-modified polyvinyl alcohol was prepared, and the ultraviolet absorbent precursor solution was added thereto, followed by emulsification and dispersion with a homogenizer. After 120 parts of water was added to the obtained emulsion to homogenize it, the temperature was raised to 40 ° C. while stirring,
The encapsulation reaction was carried out for a time to obtain a desired capsule liquid.
The average particle size of the capsule was 0.3 μm.

(Preparation of Coating Solution) To 100 parts of the capsule solution of the above-mentioned ultraviolet absorber precursor, 10 parts of a 2% aqueous solution of sodium 4-nonylphenoxytrioxyethylene] butylsulfonate was added, and a light transmittance adjusting layer solution was prepared. I got Preparation of Intermediate Layer Solution To 100 parts of a 10% aqueous gelatin solution, 2 parts of 2% sodium (4-nonylphenoxytrioxyethylene) butylsulfonate was added to prepare an intermediate layer solution.

Preparation of protective layer solution 5.0% ethylene-modified polyvinyl alcohol aqueous solution 61
2.0 parts by weight of a 20.5% zinc stearate dispersion (Hydrin F115, manufactured by Chukyo Yushi Co., Ltd.)
(4-Nonylphenoxytrioxyethylene) 8.4 parts of an aqueous solution of sodium butyl sulfonate, 8.0 parts of a fluorine-based release agent (ME-313, manufactured by Daikin Co., Ltd.), and 0.5 part of flour starch are added and uniformly stirred. Then, a PVA solution was prepared.
Separately, 20% by weight chaogross (Shiraishi Industry Co., Ltd.) aqueous solution 1
2.5 parts, 10% by weight polyvinyl alcohol (PVA1
05: Kuraray Co., Ltd.) 1.25 parts, 2% by weight aqueous solution of sodium dodecylsulfonate 0:39 parts were mixed and dispersed by Dynomill to prepare a pigment liquid. 4.4 parts of the pigment liquid was added to 80 parts of the PVA liquid to obtain a protective layer liquid.

Coating of heat-sensitive recording layer On a photographic paper support laminated with a polyethylene provided with a mica-containing undercoat layer, a heat-sensitive recording layer A, an intermediate layer, a heat-sensitive recording layer B, an intermediate layer, a heat-sensitive recording layer C, The light transmittance adjusting layer and the protective layer are successively applied in order of 7 layers at a coating speed of 60 m / min in the order of 30 ° C.-30% and 40 ° C.-30%
And dried under the same conditions to obtain a multicolor heat-sensitive recording material. The coating amount of the solid content was 6.0 g / m ^{2 for} the heat-sensitive recording layer A, and 3 for the intermediate layer.
0 g / m ^2, the heat-sensitive recording layer B6.0g / m ^2, the intermediate layer 3.
0 g / m ^2, the heat-sensitive recording layer C5.0g / m ^2, the light transmittance adjusting layer 3.0 g / m ^2, was coated to a protective layer 1.5 g / m ^2.

Example 2 Example 1 was repeated except that the amount of mica applied was 0.01 g / m ^2.
In the same manner as in the above, a heat-sensitive recording material was produced.

Example 3 A thermosensitive recording material was produced in the same manner as in Example 1 except that the number of mica was 100 parts and the weight ratio of mica / gelatin was 0.5 / 10.

Example 4 A thermosensitive recording material was prepared in the same manner as in Example 1 except that the number of mica was 400 parts and the weight ratio of mica / gelatin was 5.0 / 10.

Example 5 Instead of gelatin in Example 1, the viscosity was measured by the PAGI method.
A thermosensitive recording material was produced in the same manner as in Example 1, except that gelatin of 10 mP, PAGI method jelly strength: 15 g was used.

Example 6 Instead of gelatin in Example 1, use the PAGI method.
A thermosensitive recording material was produced in the same manner as in Example 1, except that gelatin of 30 mP, PAGI method jelly strength: 70 g was used.

Example 7 Instead of the mica in Example 1, the aspect ratio was 100.
A thermosensitive recording material was produced in the same manner as in Example 1 except that mica was used.

Example 8 A heat-sensitive recording material was produced in the same manner as in Example 1 except that the amount of mica applied was changed to 0.005 g / m ² .

Example 9 A thermosensitive recording material was produced in the same manner as in Example 1 except that mica was not contained.

Example 10 A thermosensitive recording material was produced in the same manner as in Example 1, except that mica having an aspect ratio of 40 was used instead of mica.

Comparative Example 1 Instead of gelatin in Example 1, the viscosity was measured by the PAGI method.
A heat-sensitive recording material was produced in the same manner as in Example 1 except that 60 mP, PAGI method jelly strength: 185 g of zetirane was used. Performance evaluation was performed on each of the obtained heat-sensitive recording materials.

(Evaluation of Light Resistance) A sample (a sample obtained by exposing a thermosensitive recording material to an ultraviolet lamp having a luminescence center wavelength of 356 nm for 5 seconds and fixing) under an illuminance of 27000 LUX from a plurality of commercially available fluorescent lamps was processed for 10 days The degree of coloring of the background was measured with an X-rite densitometer, and the density difference before and after the treatment was determined. It is a desirable value that the density change is less than 0.10 because the density change is small. (Measurement of viscosity of coating liquid) Measured with a B-type viscometer at a measurement liquid temperature of 38 ° C. If the coated surface after coating exceeds 20 CPS, a streak is formed. Table 1 shows the results.

[0114]

[Table 1]

From Table 1, it is found that Examples 1 to 10 corresponding to the recording material of claim 1 have a viscosity of 10 mP according to the PAGI method.
~ 30mP, PAGI jelly strength is 15g ~ 70g
It can be seen that the coating liquid maintains a low viscosity and is excellent in coating suitability without using the gelatin of No. 3 without increasing the viscosity and gelling of the coating liquid. In Examples 1 to 7 corresponding to the recording material of the fifth aspect, the viscosity of the PAGI method was 10%.
mP-30mP, PAGI jelly strength 15g-7
0 g of gelatin and water-swellable synthetic mica are used, the coating solution maintains low viscosity without causing viscosity increase and gelation of the coating solution, and is excellent in application suitability, and the background portion It can be seen that the coloring of is extremely small.

As described above, the viscosity of the PAGI method is 10
mP-30mP, PAGI jelly strength 15g-7
When 0 g of low-viscosity gelatin is used, the viscosity of the coating solution does not increase and the gelling does not occur, the coating solution maintains the store viscosity, the coating suitability is excellent, and the viscosity of the PAGI method is 10 mP.
~ 30mP, PAGI jelly strength is 15g ~ 70g
When gelatin and water-swellable synthetic mica are used, the viscosity of the coating solution does not increase and the gelling does not occur, the coating solution maintains a low viscosity, is excellent in application suitability, and the coloring of the background portion is improved. Extremely small and excellent in light resistance.

Claims (12)

[Claims] 1. A support having a viscosity of 10 m according to a PAGI method on a support.
P ~ 30mP, PAGI jelly strength is 15g ~ 70
A recording material comprising at least one layer containing g of gelatin. 2. A recording material having an undercoat layer and a light-sensitive material layer on a support, having a viscosity of 10 mP to 30 Pag by a PAGI method.
2. The recording material according to claim 1, wherein the recording material contains gelatin having a jelly strength of 15 g to 70 g according to the mP / PAGI method. 3. The undercoat layer has a viscosity of 1 according to a PAGI method.
0mP ~ 30mP, PAGI method jelly strength is 15g ~
3. The composition according to claim 2, which contains 70 g of gelatin.
Recording material described in 1. 4. The recording material according to claim 1, wherein the gelatin is gelatin whose molecular weight has been reduced using an enzyme. 5. A recording material having an undercoat layer and a light-sensitive material layer on a support, having a viscosity of 10 mP to 30 according to the PAGI method.
A recording material comprising gelatin having a jelly strength of 15 g to 70 g according to mP and PAGI method and a layered inorganic compound. 6. The recording material according to claim 5, wherein the layered inorganic compound is water-swellable synthetic mica. 7. The recording material according to claim 6, wherein the water-swellable synthetic mica has an aspect ratio of 100 or more. 8. The recording material according to claim 6, wherein the weight ratio of the water-swellable synthetic mica / gelatin in the undercoat layer is 1/20 to 1/2. 9. The recording material according to claim 6, wherein the amount of the water-swellable synthetic mica of the undercoat layer is 0.01 g / m ³ or more. 10. The heat-sensitive recording layer is a heat-sensitive recording layer, wherein the heat-sensitive recording layer contains an electron-donating dye precursor and an electron-accepting compound, a diazonium salt compound and the diazonium salt. The recording material according to any one of claims 5 to 9, wherein the recording material has at least one thermosensitive coloring layer B containing a coupler that reacts with a compound to form a color. 11. The recording material according to claim 5, wherein said light-sensitive material layer is a silver halide emulsion layer. 12. The support according to claim 3, wherein a paper base mainly composed of natural pulp is coated on both sides with a hot-melt polyolefin resin.
Recording material described in 1.