JP3482550B2 - Photosensitive and heat-sensitive recording material and recording method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light and heat sensitive recording material that develops a color by irradiating it with light after heating, and more particularly to a multicolor light and heat sensitive recording material and a recording method using the same.

[0002]

2. Description of the Related Art A thermal recording material using a thermal head has features that a recording apparatus is simple, no development is required, no noise is generated during recording, maintenance is unnecessary, and running cost is low. Therefore, it is widely used in various fields such as facsimiles and printers. Although ordinary heat-sensitive recording materials have the above-mentioned advantages, the color reaction occurs only by heating.Therefore, unnecessary color is not generated during storage, especially when placed in a place of high temperature and high humidity for a long period of time. It was inevitable to get up.

On the other hand, a light-sensitive recording material capable of obtaining a color image only by applying imagewise light irradiation has long been known as a free radical photograph. For example, Ph
ot. Sci. Eng ,. 5,98-103 (196
1), JP-B-43-29407, JP-A-55-553
35, JP-A-57-60329, and JP-A-62-66.
No. 254, etc., a photoaryl radical generated by irradiation of ultraviolet rays is used to obtain a color image by oxidizing various leuco dyes, or a reaction of the photohalogen radical generated with an aniline derivative is used to produce triarylmethane. A method of forming a dye of the system to obtain a color image is disclosed. Also,
There is also an image forming material such as Dylux ^R manufactured by Du Pont, which forms an image by exposing it to UV light and then activates the photoreducing substance with visible light to fix the image. Although it is possible to form an image only by irradiating light through the original, there is an advantage that the device and operation used are simple,
Since this also has the property of developing color only with light,
Its handling has the drawback that it requires a work in a dark room and has poor stability during storage.

As an example of applying these coloring principles to heat-sensitive recording, Japanese Patent Application Laid-Open No. 60-2393 discloses a photothermographic material containing a photo-free radical generator and an oxidative color-forming leuco dye in a state separated at room temperature. Recording materials are disclosed. In such a type of heat-sensitive recording material, the recording device may be equipped with a thermal head and a light source necessary for full exposure,
Recording can be performed by a simple operation without impairing the advantages of normal thermal recording.

However, in order to obtain a high color density in the above-mentioned light and heat sensitive recording material, it is necessary to sufficiently dissolve and mix the photo free radical generator and the leuco dye. Before receiving
As a result of the components that have been dissolved and mixed to cool down and separate out,
It has a drawback that the color developability is deteriorated.

Further, Japanese Patent Laid-Open No. 7-237354 discloses a light and heat sensitive recording material (hereinafter also simply referred to as a recording material) in which a specific pyrazolone compound and a specific phenol compound and a salicylic acid derivative as a color forming aid are dispersed and coated. ) Is disclosed. In this, the latent image can be colored by irradiation with ultraviolet rays after the three are mixed by heating to form a latent image. Although the coloring mechanism of this recording material is not clear, it is considered that the pyrazolone compound is decomposed to form a coloring dye, and the photodecomposition is promoted by the phenol compound and the salicylic acid derivative. None of the above three types of compounds is decomposed by light alone.

Further, as described in the above publication,
Under high temperature conditions, the pyrazolone compound alone decomposes and develops color, which also causes fog during long-term storage, especially when the temperature and humidity are high, and the background part becomes colored after image recording. It has been found that there is a drawback, and in this case as well, if the dissolution and mixing by heating with a thermal head are insufficient, the color density is lowered. Moreover, since none of the above-mentioned three types of compounds are decomposed by light when they exist alone before heating and mixing, the non-recorded portion is not fixed, and the uncolored portion is reheated and irradiated with light. By doing so, it is possible to easily falsify the records.

Further, the above-mentioned recording materials are known only for forming a color image in a single color, and there has been no application to a multicolor image.

As for the multicolor thermosensitive recording material, several methods have been devised up to now, but in order to independently develop each color, an element for recording and developing at low temperature is used. When recording at high temperature, it is necessary to fix it so that color development does not occur. As a multicolor heat-sensitive recording material that can be fixed, a recording material using a diazonium salt compound and a coupler has hitherto been developed. The next method was to stop the recording and record the next heat.

However, although the diazonium salt is stabilized by changing the substituents or the counter salt, it is basically an unstable compound and its stability due to heat is particularly poor and its storage stability is low. It wasn't good. Therefore, as a method of performing multicolor recording, a heat-sensitive recording material that is stable against heat and capable of fixing has been newly demanded.

JP-A-1-129247, 1-1432
No. 52, No. 3-10252, No. 3-1983 and the like disclose recording materials in which a photo-radical generator and a leuco dye are enclosed in a thermoresponsive microcapsule and a reducing agent is present outside the capsule. . In the recording material, a reducing agent outside the microcapsules is mixed with a photo free radical generating agent inside the microcapsules by thermal recording, and after the coloring property is stopped, the entire surface is exposed to color the non-heated part. The application to multicolor recording is also described.

However, in the above-mentioned recording material, the oxidative coloring type leuco dye which reacts with the photo-radical generating agent to form a color is mixed from the beginning, so that it is exposed to room light, sunlight or the like during storage, There is a drawback that fogging occurs due to the gradual decomposition of the photo free radical generator during storage for a certain period of time, and there has been a demand for a light and heat sensitive recording material and a recording method that can be more easily handled and can withstand long-term storage.

[0013]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is to solve the problems of the prior art described above, and to record a recorded image using two energies of heat and light. Provided are a light and heat sensitive recording material and a recording method capable of obtaining a good multicolor image with high color developability by forming, without causing fogging during storage, only by heating with a thermal head and simple exposure. is there. Further, the problem to be solved by the present invention is to provide a light and heat sensitive recording material having excellent fixability and a recording method using the same.

[0014]

The above object of the present invention can be achieved by the following constitutions.

1. At least two photochromic elements on the support
In the light and heat sensitive recording material provided with the kind, the photo-coloring element
After they are mixed by heat to form a latent image, they are illuminated by light.
The photochromic element is a color-developing element when exposed to light, and the photochromic element is composed of a compound that decomposes by light and an element that develops a color by reacting with a decomposition product thereof, and develops a color by reacting with the decomposition product. A light and heat sensitive recording material characterized in that the element comprises at least one photochromic element comprising a coupler and an aromatic primary amine compound. 2. In a light and heat sensitive recording material in which at least two kinds of photo-coloring elements are provided on a support, each of the photo-coloring elements is
After being mixed and a latent image is formed,
The color-developing element is composed of an element that develops a color by reacting with a compound that decomposes by light and a decomposition product thereof, wherein the compound that decomposes by light is an aromatic azide compound, At least one photochromic element in which the element that reacts with an object to develop a color is a coupler
A light and heat sensitive recording material characterized by containing various kinds.

3 . Two photochromic elements, said one or characterized by color development by light of different wavelengths
Or the light and heat sensitive recording material described in 2 .

4 . 3. The light and heat sensitive recording material as described in 1 or 2 above, wherein latent images are formed on the two types of photo-coloring elements by different thermal energies.

5 . 3. The light and heat sensitive recording material as described in 1 or 2 above, wherein the two kinds of photo-coloring elements respectively develop different color tones.

6 . 3. The light and heat sensitive recording material as described in 1 or 2 above, wherein the two types of photo-coloring elements develop different densities.

7 . The above-mentioned 1 or 2, wherein two types of photo-coloring elements are contained in different layers.
The light and heat sensitive recording material described.

8 . 3. The light and heat sensitive recording material as described in 1 or 2 above, wherein two types of photocoloring elements are contained in the same layer.

[0022]

9. 3. The light and heat sensitive recording material according to 1 or 2 above, wherein at least one of the compound that decomposes by light and the element that develops a color by reacting with the decomposition product is contained in microcapsules.

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

In the light and heat sensitive recording material of the present invention and the recording method using the same, at least two kinds of photochromic elements on the support are respectively mixed by heat and then irradiated with light to form a dye. To form an image. In the non-heated part, the two types of photochromic elements are not in a state where all of them are mixed. Therefore, even if light is irradiated, no dye-forming reaction occurs, only a decomposition reaction of a compound that is decomposed by light. Occurs. In such a light- and heat-sensitive recording material and a recording method using the same, the recording device may be a normal heat-sensitive recording device provided with a light source such as a fluorescent lamp, and a good color image can be formed without impairing the advantages of the heat-sensitive recording. Can be obtained.
In addition, the compound that decomposes by light and the element that reacts with its decomposition product to develop color are not mixed when not heated, so they are exposed to room light during storage, and unnecessary color development occurs even during long-term storage. Does not happen and its handling becomes easier.

The present invention will be described in detail below.

In the present invention, the photochromic element preferably comprises a compound which decomposes by light and an element which develops color by reacting with a decomposition product thereof.

The compound which is decomposed by light may be any compound which is decomposed by light such as ultraviolet light, visible light or infrared light, and includes, for example, a compound called a photo free radical generator and an azide compound. Examples of the photo free radical generator include 2,4,6-triarylimidazole dimer compounds described in JP-B-62-39728 and JP-B-63-2099, and 2-azidobenzoxazide described in U.S. Pat. No. 3,282,693. Azide compounds such as azoles, benzoyl azides, 2-azidobenzimidazoles, US Pat.
15568, 3'-ethyl-1-methoxy-2-
Pyridothiacyanine perchlorate, 1-methoxy-2
-Pyridinium compounds such as methylpyridinium-p-toluenesulfonate, N-bromosuccinimide, tribromomethylphenylsulfone, diphenyliodine, 2
-Trichloromethyl-5- (p-butoxystyryl)-
Organic halogen compounds such as 1,3,4-oxadiazole and 2,6-bis (trichloromethyl) -4- (p-methoxyphenyl) -s-triazine, carbonyl compounds such as benzophenone, thioxanthone, anthraquinone and benzoin ether. Examples thereof include azo compounds such as azobisisobutyronitrile, organic disulfide compounds such as alkyl disulfides and mercaptans, and phosphorus compounds such as triphenylphosphine.

The wavelength of light which is decomposed by the compound which is decomposed by light can be selected in consideration of easiness of handling as a recording material, availability of a light source to be used and cost.
The ease of handling as a recording material is subject to a constraint that it must be handled in a dark room because it has a problem in stability if it is sensitively exposed to light having a wavelength of about room light. In order to avoid such a restriction, it is preferable to use a region from the ultraviolet region to a part of visible light or infrared light. Among them, 300 nm, which does not require the strength of energy or the use of expensive materials such as quartz
It is preferable to use light in the region of 450 nm.

The compound which is decomposed by light is decomposed by light and then is reacted with the decomposition product to generate a color by the reaction with the element which is colored, and at this time, the decomposition product is formed by the dye. May be formed as a part of the above, or may be changed to a compound different from the dye only by being involved in the dye forming reaction. It depends on the combination of a compound that decomposes by light and an element that develops a color by reacting with the decomposition product, but it is selected in consideration of the generation efficiency, color tone, fastness, extinction coefficient, etc. of the dye formed by the reaction. .

Various reactions can be used as the reaction according to the present invention for reacting the photodegradable compound and the decomposition product thereof to form a coloring dye, but the following three types are preferable. .

[0038] (In the above reaction formula, A represents a photodegradable compound,
A'represents a photolysis product. Also, B, C and D are A '
Represents an element that develops color in response to. Also, D'B-C,
AC represents the formed coloring dye. Further, B'is a form in which B is changed by the reaction with A '. The above reaction formulas are schematic representations of each type of reaction, and are useful for understanding what the dye skeleton produced is derived from. In the above reaction formula, the element that develops color by reacting with A ′ is composed of a single compound (types 1 and 3) and two types of compounds (type 2).
However, it may be composed of three or more kinds.
Further, although an auxiliary component (for example, a base or an acid) that accelerates the dye-forming reaction is not described, it may be contained in the photo-coloring element. That is, in the case of type 1, D reacts with the photodegradation product of A and D to form a coloring dye by oxidation, decomposition, etc., and the basic skeleton of the coloring dye is derived from D. .

In the case of the type 2, B, which is one of the color-forming elements, is activated by a certain change (for example, oxidation or decomposition) due to the reaction with A ', and then the other color-forming element is activated. It reacts with C (for example, a coupling reaction or the like) to form a coloring dye. In this case, the basic skeleton of the coloring dye produced is derived from B and C.

In the case of type 3, A'reacts with C to form a coloring dye (for example, a coupling reaction), but unlike in type 1, the basic skeleton of the coloring dye produced is A. And C.

As an example of the type 1, a compound which decomposes by light is a photo free radical generator such as a 2,4,6-triarylimidazole dimer compound or an organic halogen compound, and its decomposition product. The case where the element that reacts with is like a leuco dye is mentioned. In this case, decomposition products generated by light irradiation are imidazolyl free radicals and halogen free radicals, which have strong oxidizing power. By utilizing the oxidizing power, for example, a leuco dye can be oxidized to form a coloring dye.
As the leuco dye that can be used, for example, those described in U.S. Pat. No. 3,445,234 can be used, and typical structures include the following.

1) Aminotriarylmethane 2) Aminoxanthene 3) Aminothioxanthene 4) Amino-9,10-dihydroacridine 5) Aminophenoxazine 6) Aminophenothiazine 7) Aminodihydrophenazine 8) Aminodiphenylmethane 9) Leucoin Damine 10) Aminohydrocinnamic acid (cyanoethane, leucomethine) 11) Hydrazine 12) Leucine digoid dye 13) Aminodihydroanthraquinone 14) 4,4'-biphenol 15) 2- (p-hydroxyphenyl) -4,5-diphenylimidazole 16) Phenethylaniline Specific examples of compounds include leuco crystal violet, tris (4-dimethylamino-o-tolyl) methane, bis (4-dimethylamino-o-tolyl) phenylmethane, bis (4-). Methylamino -o- tolyl) Chienirumetan, 2- (2-chlorophenyl-amino-6-
N, N-dibutylamino-9- (2-methoxycarbonyl) -phenylxanthene, 2-N, N-dibenzylamino-6-NN-diethylamino-9- (2-methoxycarbonyl) phenylxanthene, benzo [ a] -6
-N, N-diethylamino-9- (2-methoxycarbonyl) phenylxanthene, benzoylleucomethylene blue, benzoyl-3,7-diethylaminophenoxazine, benzoyl-3,7-diethylamino-9-phenyldihydrophenazine, 6,6 '. -Di-t-butyl-p, p'-bi-o-cresol and the like can be mentioned.

Among them, preferred leuco dyes are triarylmethane type leuco dyes such as tris (4-dimethylamino-o-tolyl) methane, benzoyl leuco methylene blue, benzoyl-3,7-diethylaminophenoxazine and benzoyl-3. Examples thereof include acylated leucoazine dyes such as 7,7-diethylamino-9-phenyldihydrophenazine.

As the photo-radical generator used in combination with the above leuco dye, a 2,4,6-triarylimidazole dimer compound, tribromomethylphenyl sulfone, 2,6-bis (trichloromethyl) is used. ) -4
Examples thereof include organic halogen compounds such as-(p-methoxyphenyl) -s-triazine.

Further, these photo-free radical generators can be sensitized with intrinsic sensitivity and spectral sensitivity by using various sensitizers together.

Typical sensitizers include, for example, "Sensitizers", edited by Katsumi Tokumaru and Shin Okawara, Kodansha, 1987 64-.
The compounds described on page 75 can be mentioned.

As an example of the type 2, a compound which is decomposed by light is a photo free radical generator having an oxidizing power similar to that of the type 1, and an element which reacts with the decomposition product to form a color,
The case where it is a coupler and an aromatic primary amine is mentioned. For example, an aromatic primary amine such as N, N-diethyl-p-phenylenediamine or 4-aminoantipyrine forms an azomethine dye by oxidative coupling with a phenol or an active methylene compound. As is well known in the field of photosensitive materials,
The above-mentioned free radicals can be used to cause an oxidative coupling reaction to produce a dye.

As aromatic primary amines that can be used, other than the above-mentioned amines, p-aminophenol,
N, N-diethyl-2-methyl-p-phenylenediamine, N-ethyl-N-methanesulfonylaminoethyl-
Examples thereof include 2-methyl-p-phenylenediamine and N, N-didodecyl-p-phenylenediamine. The above-mentioned aromatic primary amine can be used in the form of a hydrochloride, a sulfate, a tosylate, a perfluoroalkyl sulfonate, etc., if necessary. In addition, acyl compounds such as acetyl compounds, benzoyl compounds, p-toluenesulfonyl compounds,
The (2,4-di-t-pentyl-phenoxy) acetyl body and the p-dodecyloxyphenylsulfonyl body can also be used in the same manner. Among these, preferred aromatic primary amines include aminoantipyrine, perfluoroalkyl sulfonates of N, N-dialkylamino-p-phenylenediamine derivatives, and the like.

As the coupler for forming a dye by oxidative coupling with an aromatic primary amine, those known in the field of silver halide color photographic light-sensitive materials can be used. Examples of couplers that can be used include US Pat.
772, 162, 2, 895, 826, 3, 0
02,836, 3,034,892, 2,47
4,293, 2,423,730, 2,36
No. 7,531, No. 3,041,236, No. 4,33
3,999, 2,600,788, 2,36
9,869, 2,343,703, 2,31
1,082, 3,152,896, 3,51
9,429, 3,062,653, 2,90
8,573, 2,875,057, 2,40
7,210, 3,265,506, 2,29
8,443, 3,048,194, 3,44
No. 7,928 and Agfa Mitteilunge
Farbkuppler-eine Litera of n
turuberesiicht, Volume III 112-17
It is described in representative patents and publications such as page 5 (1961). Among them, examples of preferable couplers include phenols, naphthols, pyrazolones, pyrazolotriazoles, acylacetanilides and the like.

Further, both a so-called 2-equivalent coupler in which a leaving group is substituted at the active site of the coupler and a 4-equivalent coupler in which the active site is not substituted can be used.

The reaction with the coupler may be promoted by using a base, and a base may be used in combination if necessary. As the base, organic bases such as triphenylguanidine, trihexylamine, pyridine and quinoline, inorganic bases such as sodium hydrogencarbonate, potassium carbonate, potassium hydroxide and salicylic acid metal salts, or metal salts of organic acids can be used.

An example of the type 3 is a case where the compound which is decomposed by light is an aromatic azide, and the element which develops a color by reacting with the decomposition product is a coupler. When an aromatic azide compound is decomposed by light, nitrene is produced. The formed nitrene can form an azomethine dye by reacting with the above-mentioned coupler.

Examples of aromatic azide compounds that can be used include 4- (N, N-diethylamino) phenyl azide, 2,5-dibutoxy-4-morpholinophenyl azide, 2,5-dibutoxy-4-phenylthiophenyl azide, 4- (N-ethyl-N-methylsulfonylaminoethylamino) -2-methylphenyl azide, 4-diethylamino-3-dodecyloxycarbonylphenyl azide, 1-naphthyl azide, 2-naphthyl azide, anthranil azide, 3-quinoline azide, 9-acridine azide or the like can be used. Examples of preferred aromatic azides include p-dialkylaminophenyl azides.

As the coupler for forming a dye by coupling with an azide, the same ones as mentioned above can be mentioned.

In the present invention, the total number of carbon atoms of each component of the element that develops color by reacting with a compound that decomposes by light and its decomposition product should be 10 or more in order to increase the solubility in the organic solvent used. Is preferred. When the molecular weight becomes too high, the color density per unit weight tends to decrease, so that the total carbon number is more preferably in the range of 15 to 40.

In the present invention, at least two kinds of photo-coloring elements can be used in various forms as required. For example, an image can be formed with two types of colors by using two types of photo-coloring elements that emit different colors. At that time, it is possible to record two kinds of colors at the same time by simultaneously developing two kinds of colors by one-time thermal recording and one-time light irradiation, but recording two kinds of colors separately. You can also do it.

Recording two types of colors separately is two
This can be done by causing the different types of light-coloring elements to be colored with light of different wavelengths. That is, after the respective photochromic elements are mixed by thermal recording to form a latent image, the first photochromic element develops color at a specific portion, and the second photochromic element has a wavelength not affected. By irradiating light to cause the first photochromic element to develop color, and irradiating the other portion with light having a wavelength that the second photochromic element develops, two types of photochromic elements can be independently colored. it can. Further, it is also possible to irradiate light of a wavelength that develops both of the two types of photo-coloring elements to obtain a mixture of two types of colors. It can also be controlled by the wavelength.

The recording of the two types of colors separately can be performed by forming latent images by the two types of photo-color-forming elements with different thermal energies. That is, the latent image is formed only on one of the photo-coloring elements by the first heat energy, and the latent image is formed on the other photo-coloring element by the second heat energy. After that, by irradiating with light of a wavelength that the first photo-coloring element and the second photo-coloring element develop, two kinds of colors can be recorded separately. At that time, in the recording with the second thermal energy, a latent image is also formed on the first photo-coloring element, so that one of the obtained two-color recorded images is a color-recorded image of the first photo-coloring element. An image, and the other is a recorded image in which both the first photo-coloring element and the second photo-coloring element are colored.

Before recording by the second thermal energy, the first thermal energy causes a latent image to be formed on the first photo-coloring element, and light of a wavelength at which only the first photo-coloring element develops color. Is applied to cause the first photochromic element to develop color, and at the same time to stop the color developability of the non-recording portion of the first photochromic element, the second thermal energy causes the latent image to develop on the second photochromic element. By forming an image and color-developing the latent image by light irradiation, it is possible to independently output a color image by the first photo-coloring element and a color image by the second photo-coloring element.

Further, the two types of photo-coloring elements can be made to have the same color tone. For example, if the density of the image to be recorded can be finely reflected in the color density by the difference in the thermal energy applied, a more reproducible recorded image can be obtained, but a single color element can be used in a wider temperature range. There is a limit to how light and dark colors can be added. Therefore, a plurality of photo-coloring elements are provided, and colors are formed in substantially the same color tone, but by providing a photo-coloring element that causes higher density coloration at higher temperature recording, a more detailed color image can be obtained. Can be obtained.

In the present invention, the two types of photochromic elements are
If necessary, they can be contained in the same layer, or can be contained separately in two or more layers. For example, when two types of photo-coloring elements are colored simultaneously from the beginning to obtain a color mixture, or when the two types of photo-coloring elements have a common component, two types of light-coloring elements are generated by heat and / or light.
When it is possible to separately develop two types of photo-coloring elements, or to use photo-coloring elements having substantially the same color tone but different densities, the two types of photo-coloring elements are formed in the same layer. Can be included.

It is also possible to incorporate the two types of photochromic elements in separate layers. When the layers are separated to contain two types of photochromic elements, the layers are different, so that it is easy to separate each component, and the heat transfer state can be changed depending on the layers. Separation of the two colors becomes easier when the photochromic elements are mixed by thermal recording to develop color.

In the present invention, not all components are uniformly mixed in each photochromic element before heating. At least one component in the photochromic element must be separated from the other components by some means before heating. When it is heated by the thermal head, it is quickly mixed, and when it is irradiated with light, a color reaction occurs only at the mixed portion. When heated by the thermal head, the photochromic element is rapidly dissolved and mixed, and until the individual components can be kept in a dissolved state until they are exposed to light,
A high color density can be obtained. For that purpose, it is effective to disperse at least one component of the photo-coloring element together with an organic solvent.

The organic solvent used in the present invention preferably has a high boiling point. For example, phosphoric acid ester, phthalic acid ester, acrylic acid ester, methacrylic acid ester and other carboxylic acid ester, fatty acid amide, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene, diarylethane, dialkylphenol, etc. Used.

Specifically, JP-A-60-242094,
Those described in JP-A-62-75409 can be used. Specifically, JP-A-60-242094
JP-A-62-75409 and the like can be used.

The boiling point of the organic solvent used is preferably 100 ° C. because it is desired that it does not volatilize at room temperature.
The above is used. If the boiling point is too high, the viscosity tends to be high, and more preferably 120
Those in the range of ℃ to 500 ℃ are used.

In addition to the above high boiling point organic solvent, a low boiling point organic solvent such as ethyl acetate or methylene chloride may be used in combination as a dissolution aid.

As a usable isolation method, for example, each component can be emulsified and dispersed or solid-dispersed to avoid uniform mixing. Further, for more reliable isolation, the components to be isolated at the time of storage are divided into separate layers on the support and applied. It is also effective to provide an intermediate layer between each layer.

A more preferable form of isolation is to use microcapsules. The microcapsules preferred in the present invention prevent contact between substances inside and outside the capsule due to the substance separating action of the microcapsule wall at room temperature,
It increases the permeability of a substance when heated at a certain temperature. The temperature-dependent permeability of the microcapsules can be controlled by changing the glass transition temperature of the capsule wall depending on the capsule wall material, core substance, additive species, and the like.

As the wall material of the microcapsule which can be used in the present invention, polyurethane, polyurea, polyether polycarbonate, urea-formaldehyde resin, melamine-formaldehyde resin, polystyrene, styrene-methacrylate copolymer, gelatin, polyvinylpyrrolidone, Examples thereof include polyvinyl alcohol. A plurality of these wall materials may be used in combination.

In the present invention, among the above wall materials, polyurethane, polyurea, polyamide, polyester, polycarbonate, polyester and the like are preferable, and polyurea and polyurethane are particularly preferable. Details of the microcapsules which can be preferably used in the present invention are described in the specification of US Pat. No. 3,796,696.

The microcapsules used in the present invention are obtained by interfacial polymerization in which a core substance containing a substance to be encapsulated is emulsified, and then a wall of a polymer substance is formed around the oil droplets for microcapsulation. The method is preferred. At that time, it is preferable to use an organic solvent to form emulsified oil droplets as needed, and the organic solvent used can be generally selected appropriately from high boiling point organic solvents.

For example, phosphoric acid ester, phthalic acid ester, acrylic acid ester, methacrylic acid ester and other carboxylic acid ester, fatty acid amide, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin,
Alkylated naphthalene, diarylethane and the like are used. Specifically, JP-A-60-242094 and JP-A-6-24094
2-75409 etc. can be used.

In addition to the above high boiling point organic solvent, a low boiling point organic solvent such as ethyl acetate or methylene chloride may be used in combination as a dissolution aid. On the other hand, in the water layer that mixes with the oil layer,
A water-soluble polymer can be contained as a protective colloid, and for example, polyvinyl alcohol, gelatin, or cellulose derivative can be used.

When emulsifying and dispersing, a suitable surfactant can be selected from known surfactants to prevent precipitation or aggregation. Other color-developing elements to be present outside the microcapsules may be dispersed by either solid dispersion or emulsion dispersion, but they are preferably emulsion dispersed. In solid dispersion, emulsion dispersion, and dispersion of morphological hemorrhoids using microcapsules, the particle size thereof is preferably in the range of 0.1 μm to 20 μm from the viewpoint of image quality and color density. More preferably, it is in the range of 0.5 μm to 10 μm.

Further, in the present invention, a compound which is decomposed by light is heated and reacts with the decomposition product to generate a color reaction at a site mixed with an element, but the non-heated portion, that is, the decomposition product. In the part isolated from the element that reacts with and develops color, no color reaction occurs even when irradiated with light. Preferably, when the non-heated portion is exposed,
A compound that is decomposed by light is decomposed and converted into a substantially harmless compound by the reaction with surrounding compounds without participating in the color development reaction.

In the present invention, the amount of the compound that decomposes by light and the element that develops a color when reacted with the decomposition product is not particularly limited, but the film thickness when coated on a support, It is selected in consideration of coloring efficiency, coloring density, and the like. The preferred amount of use of each component is 4 × 1
The range is 0 ⁻⁴ mol / m ² to 2 × 10 ⁻² mol / m ² .

Further, the film thickness when applied on the support is not particularly limited, but considering the heat sensitivity and the sharpness of the image, the dry film thickness is 0.5 μm.
˜50 μm is preferable, and 1 μm to 20 μm is more preferable.

The light and heat sensitive recording material in the present invention can be prepared by coating and impregnating a support with a compound which decomposes by light and an element which develops a color by reacting with the decomposition product thereof. At this time, as the binder of the dispersion, various emulsions such as polyvinyl alcohol, gelatin, styrene-butadiene latex, carboxymethyl cellulose, gum arabic, polyvinylpyrrolidone, polyvinyl acetate, and polyacrylic acid ester can be used. Is 0.5 to 5 g / m ² in terms of solid content. In the recording material of the present invention, in consideration of image protection, prevention of adhesion between recording materials, prevention of adhesion to thermal head, writing property, smoothness, etc. It is preferable to provide a protective layer. As the binder for the protective layer, known binders can be used. For example, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, starches, gelatin, gum arabic, casein, styrene-
Maleic anhydride copolymer hydrolyzate, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, polyacrylamide derivative, polyvinylpyrrolidone, sodium polystyrenesulfonate, sodium alginate, styrene-butadiene latex, acrylonitrile-butadiene rubber latex, polyvinyl acetate emulsion, etc. Polymer, silicone resin, melamine resin, phenol resin, acrylic resin polyester resin, epoxy resin,
Binders such as fluororesin, nitrocellulose, cellulose acetate propionate, cellulose acetate, fluorinated vinylidene resin, and chlorinated rubber can be used.
As the filler for the protective layer, zinc oxide, calcium carbonate,
Barium sulfate, titanium oxide, lithobon, talc, rouxite,
Inorganic pigments such as kaolin, aluminum hydroxide, amorphous silica, colloidal silica, polystyrene, polymethyl methacrylate, polyethylene, vinyl acetate resin, vinyl sulfide resin, vinylidene sulfide resin, styrene-methacrylate copolymer, vinylidene chloride, polyurea, Organic pigments such as melamine-formaldehyde, zinc stearate,
Metal soaps such as calcium stearate and aluminum stearate, or waxes such as paraffin wax, microcrystalline wax, carnauba wax, methylol stearylamide, polyethylene wax and silicone can be added. These fillers may be used alone or in combination of two or more.

When the light and heat sensitive recording material of the present invention is coated on a support such as paper or a synthetic resin film, a generally well-known coating method can be used. For example, it may be applied by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a doctor coating method, a wire bar coating method, a slide coating method, a gravure coating method, a spin coating method or an extrusion coating method. it can. Examples of the support that can be used in the light and heat sensitive recording material of the present invention include papers, regenerated cellulose, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polyvinyl acetate, polyethylene naphthalate, and other films, glass, wood, and metal. Etc. are mentioned. The light source that can be used in the present invention may be any light source as long as it can decompose compounds that are decomposed by light, such as a fluorescent lamp, a high pressure mercury lamp, a halogen lamp, a xenon lamp,
It may be a tungsten lamp or sunlight.

[0081]

EXAMPLES Examples will be shown below, but the present invention is not limited thereto. Further, "part" indicating the addition amount indicates "part by weight".

Reference Example 1 (Preparation of Capsule Liquid A) Leuco Dye: Leuco Crystal Violet 1 part Walling agent: Xylylene diisocyanate / trimethylolpropane adduct (75% ethyl acetate solution) 20 parts Additive: Dodecylbenzenesulfonic acid 0 .4 parts Dissolution aid: Ethyl acetate 16 parts High boiling solvent: Diisopropylnaphthalene 5 parts were uniformly dissolved.

This solution was added to 54 parts of a 6% aqueous solution of polyvinyl alcohol and emulsified and dispersed at 20 ° C. using a homogenizer to obtain an emulsion having an average particle size of 1 μm. 60 parts of water was added to the obtained emulsion and stirring was continued at 40 ° C. for 3 hours. Then, it returned to room temperature and obtained the capsule liquid A. The glass transition temperature of the capsule wall was 80 ° C.

[0084] (Preparation of capsule liquid B) Leuco dye: 3,6-dimethoxy-9- (2-methoxycarbonyl)-             Phenylxanthene 1.5 parts Wall agent: Tolylene diisocyanate / trimethylol propane adduct                                      (75% ethyl acetate solution) 20 parts Dissolution aid: Ethyl acetate 5 parts High boiling solvent: diisopropyl naphthalene 5 parts Was dissolved uniformly.

This solution was added to 54 parts of a 6% aqueous solution of polyvinyl alcohol and emulsified and dispersed at 20 ° C. using a homogenizer to obtain an emulsion having an average particle size of 1 μm. 60 parts of water was added to the obtained emulsion and stirring was continued at 40 ° C. for 3 hours. Then, it returned to room temperature and obtained the capsule liquid B. The glass transition temperature of the capsule wall was 100 ° C.

(Preparation of Photo-Free Radical Generator Dispersion) 5 parts of tribromomethylphenyl sulfone, 2,2'-bis- (o
-Chlorophenyl) -4,4 ', 5,5'-tetraphenylimidazole (25 parts) was added to 150 parts of a 4% polyvinyl alcohol aqueous solution and dispersed by a sand mill to obtain a tribrumomethylphenyl sulfone dispersion having an average particle size of 1 μm. Obtained.

Next, a coating liquid A having the following composition was prepared.

Capsule liquid A 12 parts Capsule liquid B 12 parts Photo free radical generator dispersion 5 parts This coating liquid is applied to a fine paper with a wire bar so that the coating amounts of the capsule liquid A and the capsule liquid B leuco dye are 0. It was coated at 5 g / m ² and dried at 50 ° C. to obtain the light and heat sensitive recording paper of the present invention.

Using a thermal tilt tester (manufactured by Toyo Seiki), the obtained light and heat sensitive recording paper was heated to 90 ° C. and 110 ° C.
After heating at 0 ° C. for 5 seconds (0.5 kg / m ² ), the entire surface was exposed for 30 seconds using a high pressure mercury lamp. As a result, 90 ℃
The part heated by is a bright yellow color,
The part heated at ℃ exhibited a black color.

The non-heated part remained colorless.

After the above-mentioned whole surface exposure, the non-heated part of the light and heat sensitive recording paper was heated and exposed again, but no significant color development was observed.

The color of the leuco dye used in the capsule liquid A is yellow, and the color of the leuco dye used in the capsule liquid B is blue.
Only the leuco dye of Capsule Liquid A is colored by exposure on the part heated at 0 ° C, and the leuco dye of Capsule Liquid A and the leuco dye of Capsule Liquid B are colored simultaneously by exposure on the part heated at 110 ° C. It is thought that it has become.

Example 2 (Preparation of capsule liquid C) Coupler: 2,4-dichloro-3-ethyl-6- [2- (2,4-ditertiary) Lipentylphenyloxy) butanoylamino] phenol 1.5 parts Additive: Dodecylbenzenesulfonic acid 0.4 part Wall material: Xylylene diisocyanate / trimethylolpropane adduct             (75% ethyl acetate solution) 20 parts Dissolution aid: Ethyl acetate 5 parts High boiling point solvent: isopropyl biphenyl 5 parts Was dissolved uniformly.

This solution was added to 54 parts of a 6% aqueous solution of polyvinyl alcohol and emulsified and dispersed at 20 ° C. using a homogenizer to obtain an emulsion having an average particle size of 1 μm. 60 parts of water was added to the obtained emulsion and stirring was continued at 40 ° C. for 3 hours. Then, it returned to room temperature and obtained the capsule liquid C.

(Preparation of photo free radical generator / amine dispersion)
2,2'-bis- (o-chlorophenyl) -4,4 ',
5,5'-Tetraphenylimidazole 4 parts, 2,6-
Bistrichloromethyl-4-methoxyphenyl-s-triazine 2 parts, N, N-dioctylamino-p-phenylenediamine perfluorobutane sulfone salt 10 parts, triphenylguanidine 5 parts, methylene chloride 30 parts, tricresyl phosphate. 30 parts was added to 200 parts of a 4% aqueous solution of polyvinyl alcohol and ultrasonically dispersed to obtain a dispersion.

Next, a coating solution having the following composition was prepared.

[0097] (upper layer coating liquid) above capsule solution C10 parts The optical radical generating agent dispersion 20 parts (lower layer coating liquid) photolytic free radical generating agent dispersion prepared in Reference Example 1 capsule solution B10 parts Reference Example 1 was prepared by Liquid 3 parts This coating solution is applied to wood free paper with a wire bar so that the coating amount of the coupler in the upper layer coating liquid is 0.8 g / m ² and the amount of leuco dye in the lower layer coating liquid is 0.5 g / m ^2. Apply
It was dried at 50 ° C. to obtain a light and heat sensitive recording paper of the present invention.

The obtained light and heat sensitive recording paper was partially heated at 90 ° C. using a thermal tilt tester (manufactured by Toyo Seiki), and then light of 400 nm or less was cut using a filter. The surface of the high pressure mercury lamp was exposed for 30 seconds. The heated part had a bright cyan color. No color was observed in the non-heated part. After that, the unheated part is further heated at 110 ° C. for 5 seconds (0, 5 kg /
m ² ) After heating, the entire surface was exposed for 30 seconds using a high pressure mercury lamp. As a result, the reheated portion showed vivid yellow coloration, and the non-heated portion was colorless. The photo free radical generator dispersion liquid of the upper layer is exposed to light of 400 nm or more, and the portion heated by the amine and the coupler is colored to become cyan, and the photo free radical generator dispersion liquid used in the lower layer is 40
It is considered that yellow color was exhibited because it was exposed to light of 0 nm or less and reacted with the leuco dye.

Further, even if heating and exposure were performed after irradiation with light having a wavelength of 400 nm or more, the cyan color of the upper layer was not observed. It's clear that the outage is happening.

Example 3 (Preparation of capsule liquid D) Azide: 4-morpholino-2,5-dibutoxyphenyl azide 3 parts High boiling solvent: diisopropyl naphthalene 10 parts Wall material: Xylylene diisocyanate / trimethylolpropane adduct             (75% ethyl acetate solution) 20 parts Dissolution aid: Ethyl acetate 5 parts Was dissolved uniformly.

This solution was added to an 8% phthalated gelatin aqueous solution 4
This was added to 6 parts, and 18 parts of water and 2 parts of a 10% aqueous solution of sodium dodecylbenzenesulfonate were emulsified and dispersed at 20 ° C. using a homogenizer to obtain an emulsion having an average particle size of 1 μm. After adding 20 parts of water to the obtained emulsion and homogenizing,
Stirring was continued at 40 ° C. for 3 hours. Then, it returned to room temperature and obtained the capsule liquid D.

[0102] (Preparation of capsule liquid E) Azide: 4-morpholino-2,5-dibutoxyphenyl azide 6 parts High boiling solvent: diisopropyl naphthalene 10 parts Wall agent: Tolylene diisocyanate / trimethylol propane adduct             (75% ethyl acetate solution) 20 parts Dissolution aid: Ethyl acetate 5 parts Was dissolved uniformly.

This solution was mixed with an 8% phthalated gelatin aqueous solution 4
This was added to 6 parts, and 18 parts of water and 2 parts of a 10% aqueous solution of sodium dodecylbenzenesulfonate were emulsified and dispersed at 20 ° C. using a homogenizer to obtain an emulsion having an average particle size of 1 μm. After adding 20 parts of water to the obtained emulsion and homogenizing,
Stirring was continued at 40 ° C. for 3 hours. Then, it returned to room temperature and obtained the capsule liquid D.

Preparation of coupler dispersion 7-chloro-6-tert-butyl-3- (3-dodecylsulfonylpropyl) pyrazolo [3,2-c] triazole (4 parts) and tricresyl phosphate (1 part) were uniformly mixed. After mixing, 32 parts of gelatin (15% aqueous solution), 5 parts of dodecylbenzenesulfonic acid (10% aqueous solution) and 30 parts of water were added, and the mixture was emulsified and dispersed at 40 ° C. for 10 minutes using a homogenizer. The mixture was stirred at 0 ° C. for 2 hours to remove ethyl acetate, and then the volatilized ethyl acetate and water were supplemented with water to obtain a coupler dispersion.

Next, a coating solution having the following composition was prepared.

Capsule liquid D 3 parts Capsule liquid E 3 parts Coupler dispersion liquid 8 parts Gelatin (15% aqueous solution) 2 parts Water 4.5 parts This coating solution is applied to a high-quality paper with a wire bar at an azide coating amount of 0.5 g / Apply to m ² and dry at 50 ℃,
A light and heat sensitive recording paper of the present invention was obtained.

Example 4 The same amount of the capsule liquid D used in Example 3 as the capsule liquid E was used.
A light and heat sensitive recording paper of the present invention was obtained in the same manner as in Example 3 except that the above was replaced with.

The light and heat sensitive recording papers obtained in Example 3 and Example 4 were heated at 90 ° C., 100 ° C., 110 ° C. and 120 ° C., respectively, using a thermal tilt tester (manufactured by Toyo Seiki).
After heating for ² seconds (0.5 kg / m ² ), the entire surface was exposed for 30 seconds using a high pressure mercury lamp.

As a result, all the heating parts showed magenta color, and the density was measured as follows.

Heating temperature 90 ° C. 100 ° C. 110 ° C. 120 ° C. Example 3 0.22 0.50 0.73 1.20 Example 4 0.49 1.19 1.21 1.22 As apparent from the above results. By mixing two types of photo-coloring elements with different heat generation start temperature and color density,
The density gradation can be expressed in a wider range of thermal energy. This is advantageous when it is desired to record fine gradations.

Comparative Example 1 Preparation of Capsule Liquid A Leuco Crystal Violet 1 part 2,2'-Bis- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylimidazole 2 parts Tripromomethylphenylsulfone 2 , 5-di-tertiary octylhydroquinone 0.6 part p-toluenesulfonamide 0.2 part xylylene diisocyanate / trimethylolpropane 20 parts 75% by weight ethyl acetate solution of adduct, ethyl acetate 16 parts diisopropylnaphthalene 18 parts Was added to the mixed solvent of and dissolved. This solution was added to 54 parts of a 6 wt% aqueous solution of carboxy-modified polyvinyl alcohol and emulsified and dispersed at 20 ° C. to obtain an emulsion having an average particle size of 1 μm. 68 parts of water was added to the obtained emulsion, and the mixture was continuously stirred at 40 ° C. for 3 hours. Then, the mixture was returned to room temperature and filtered to obtain a capsule liquid F.

Preparation of capsule liquid G 3,6-dimethoxy-9- (2-methoxycarbonyl) -phenylxanthene 1.5 parts 2,2'-bis- (o-chlorophenyl) -4,4 ', 5,5 ′ -Tetraphenylimidazole 2 parts 2,6-ditrichloromethyl-4- (p-methoxyphenyl) -triazine 0.8 parts 2- (5′-methyl-2′-hydroxyphenyl) benzotriazole 4 parts Tolylene diisocyanate 20 parts of a 75 wt% ethyl acetate solution of a nato / trimethylolpropane adduct was added to a mixed solvent of 16 parts of ethyl acetate and 18 parts of diisopropylnaphthalene and dissolved. This solution was added to 54 parts of a 6 wt% aqueous solution of carboxy-modified polyvinyl alcohol and emulsified and dispersed at 20 ° C. to obtain an emulsion having an average particle size of 1 μm. 68 parts of water was added to the obtained emulsion, and the mixture was continuously stirred at 40 ° C. for 3 hours. Then, the mixture was returned to room temperature and filtered to obtain a capsule liquid B.

Preparation of reducing agent dispersion 1-phenylpyrazolidin-3-one (phenidone A)
30 parts by weight of carboxy-modified polyvinyl alcohol 4% by weight
In addition to 150 parts of the aqueous solution, it was dispersed in a horizontal sand mill to obtain a Phenidone A dispersion having an average particle size of 1 μm.

Next, a coating solution having the following composition was prepared.

Capsule liquid F 6.8 parts Capsule liquid G 6.8 parts Reducing agent dispersion liquid 6.0 parts 30% epoxidized polyamide resin 0.4 parts This coating liquid is applied to a high-quality paper with a wire bar. The leuco dye G was coated so that the coating amount was 0.5 g / m ² , and dried at 50 ° C. to obtain a comparative multicolor recording material.

The light and heat sensitive recording papers obtained in Examples 2 to 4 and Comparative Example 1 were subjected to high temperature and high humidity (50 ° C., 80 ° C., 80 ° C.) for 3 days.
%), The sample was heat-printed and exposed under conditions such that the maximum color density was obtained, and the maximum color density (Dm ′) and background density (Dmin ′) were measured. For each sample, the maximum color density (Dm) before storage and the density (Dmin) at the background portion were also measured, and the deterioration of the light and heat sensitive recording paper after storage under the forced deterioration condition is summarized in Table 1 below.

[0117]

[Table 1]

As is clear from Table 1, the light and heat sensitive recording material of the present invention and the recording method using the same show little deterioration in color developability and contamination of the background even when stored under high temperature and high humidity conditions. I understand.

[0119]

The light and heat sensitive recording material and the recording method according to the present invention form a recorded image by using two energies of heat and light, so that a thermal head can easily perform heating without causing fog during storage. Only exposure,
It is possible to obtain a good multicolor image having high color developability, and it has an effect of excellent fixing property.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenzo Nakazawa, Konica Co., Ltd., Hino-shi, Tokyo 1 Konica Co., Ltd. (72) Inventor Manabu Shibata 1, Sakura-cho, Hino, Tokyo Konica Co., Ltd. (72) Inventor Koji Shuji Konica Co., Ltd. 1 Sakura-cho, Hino-shi, Tokyo (56) Reference JP-A-2-4572 (JP, A) JP-A-7-237354 (JP, A) JP-A-2-93459 (JP, A) JP-A-3-288688 (JP, A) JP-A-62-55648 (JP, A) JP-A-63-159845 (JP, A) JP-A-60-2393 (JP, A) JP-A-60 -259493 (JP, A) JP 54-97048 (JP, A) JP 6-308660 (JP, A) JP 56-164340 (JP, A) (58) Fields investigated (Int.Cl) . ⁷ , DB name) B41M 5/26-5/34 G03C 1/675

Claims (9)

(57) [Claims] 1. At least two kinds of photochromic elements on a support.
A light- and heat-sensitive recording material provided withIs
Light is irradiated after each is mixed by heat to form a latent image
The above-mentioned light coloring element
Is a compound that decomposes by light and its decomposition products
It consists of elements that react and develop color, and reacts with the decomposition products.
The color-developing element is the combination of the coupler and the aromatic primary amine compound.
It is characterized by including at least one type of photo-coloring element consisting of
A light and heat sensitive recording material. 2. At least two photochromic elements on a support.
A light- and heat-sensitive recording material provided withIs
Light is irradiated after each is mixed by heat to form a latent image
The above-mentioned light coloring element
Is a compound that decomposes by light and its decomposition products
It consists of elements that react and develop color, and is decomposed by the light.
The compound is an aromatic azide compound, and the decomposition product
The light-coloring element whose element that reacts with and develops color is a coupler
Light and heat sensitive recording material containing at least one kind
Fee. 3. The two types of photochromic elements are different from each other.
A color is developed by light of a wavelength, wherein
Or 2. The light and heat sensitive recording material described in 2. 4. The two types of photochromic elements are different from each other.
Characterized by the latent image formed by thermal energy
The light and heat sensitive recording material according to claim 1 or 2. 5. The two types of photochromic elements are different from each other.
The color is developed in a color tone, according to claim 1 or 2.
Light and heat sensitive recording material. 6. The two types of photochromic elements are different from each other.
The color develops at a density, which is described in claim 1 or 2.
Light and heat sensitive recording material. 7. The two types of photochromic elements are different from each other.
The layer is contained in a layer.
The light- and heat-sensitive recording material described in. 8. Two kinds of photochromic elements are contained in the same layer.
The feeling according to claim 1 or 2, characterized in that
Photosensitive recording material. 9. A compound and its compound that decomposes by light.
Of the elements that develop color by reacting with the decomposition products of
One type is characterized by being encapsulated in microcapsules
The light and heat sensitive recording material according to claim 1 or 2.