JPH0242677B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a two-color light and heat sensitive recording material and a recording method using the same.

Two-color thermosensitive recording materials are known which are composed of a combination of a color forming agent, a color developing agent, and a color erasing agent. This uses a first coloring agent that develops color at low temperatures and disappears at high temperatures, and a second coloring agent that develops color at high temperatures. However, when using such a two-color heat-sensitive recording material, if the two coloring temperatures are approximated, the coloring on the low temperature side will occur around the coloring area on the high temperature side, which is undesirable. There is a risk of further color re-coloring due to some kind of heating, which is not preferable. Furthermore, in order to prevent recoloring, it is known to use a recording layer containing a diazosulfonate and a coupling agent, and to perform a photoactivation-thermal recording-photofixing operation. However, although fixing is possible in such a system, two-color development is not possible.

The present invention is aimed at solving the drawbacks of the above-mentioned conventional techniques, and by having the structure set forth in the claims, a recording material and a recording method capable of both two-color development and fixing have been completed. be.

The present invention will be explained in detail below.

The diazosulfonate used in the present invention has the general formula R ₁ , R ₂ , R ₄ and R ₅ represent hydrogen, halogen, alkyl group, alkoxy group, R ₃
is hydrogen, halogen, alkyl group, alkoxy group,
Amino group, benzoylamino group, morpholino group,
represents a tolylmercapto group and a pyrrolidino group,
M represents an alkali metal such as K or Na or ammonium.

Next, as the diazonium salt used in the present invention, a diazonium salt having the general formula of the diazosulfonate described above in which SO ₃ M of the sulfonate is replaced with a borofluoride salt or a zinc chloride double salt can be used.

Next, as a coupling agent used in combination with the above-mentioned diazosulfonate or diazonium salt, any one of a large number of known compounds can be selected and used. Examples of coupling agents are listed below.

Resorcinol and its derivatives 4-benzoylresorcinol, 2-methylresorcinol, 5-
Methylresorcinol, diresorcinol and diresorcinol sulfide, phlorogrecin and its derivatives, fluoroglyside formate ester, fluoroglyside acetate ester, polyresorcin pyrazolone, a birazolan class, 1
-Phenyl-3-methylpyrazolone, 4,4'-bis(1-phenyl-3-methyl-5-pyrazolone), and naphthols include 2-hydroxy-3-
Naphthoic acid-2'-ethoxyanilide, 2-hydroxy-3-naphthoic acid-2',5'-dimethoxyanilide, 2-hydroxy-3-naphthoic acid-2'-methoxy-5-nitroanilide, 2-hydroxy-
3-naphthoic acid-2-methyl-4-chloroanilide, 2-hydroxy-3-naphthoic acid-morpholinopropioamide, 2-hydroxy-3-naphthoic acid ethanolamide, dihydroxynaphthalene, 2-hydroxy-3-naphthoic acid Naphthamide, Sodium 1,8-dihydroxynaphthalene-3(or 4)-sulfonate, Sodium 1-hydroxy-8-benzoylaminonaphthalene-3-sulfonate, 1-Hydroxy-8-phenylaminonaphthalene-4-sulfonic acid sodium,
1-Hydroxy-8-methylaminonaphthalene-
Sodium 5-sulfonate, sodium 4-hydroxynaphthalene-4-sulfonate, sodium 2,8-dihydroxynaphthalene-6-sulfonate.

As acidic coupling agents, 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-1-naphthoic acid, 2,6
-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,
4,6-trihydroxybenzoic acid and cyanoacetic acid, others, m-hydroxyphenyluric acid,
N,N-ethylenebisacetoacetamide, 2,
6-dihydroxyacetophenone, acetoacetanilide, 2,4,6-trihydroxyacetophenone, N-benzylacetamide, catechol, 5,5-dimethyl-1,3-cyclohexanedione, acetoacetic benzamide, or alternatively, 2 , 4-dihydroxybenzoic acid ethanolamide, 3,5-dihydroxybenzoic acid ethanolamide, 4-hydroxycoumarin, 2,5-dimethyl-4-morpholinomethylphenol, 8-oxyquinoline, and the like can also be used.

In order to form a light and heat sensitive recording layer and a heat sensitive recording layer using diazosulfonic acid, diazonium salt, coupling agent, etc. as described above, there is a method of forming a coating using an appropriate binder and coating it on an appropriate support. It will be done. As binders, cellulose derivatives such as ethyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetate propionate, nitrocellulose, and cellulose acetate, styrene resins and styrene copolymer resins such as polystyrene, polyα-methylstyrene, polymethyl methacrylate, and polyethyl methacrylate are used as binders. , acrylic or methacrylic resin alone or copolymer resin such as polyethyl acrylate, polybutyl acrylate, etc.
Rosin, rosin-modified maleic acid resin, rosin-modified phenolic resin, rosin ester resin such as polymerized rosin, polyvinyl acetate resin, coumaron resin, vinyl toluene resin, vinyl chloride resin, polyester resin, polyurethane resin, butyral resin, polyamide resin, chloride One or more types are selected and used from vinyl-vinyl acetate copolymer resins and the like.

As a binder, it can be used for diazosulfonate, diazonium salt, coupling agent, etc.
For example, it is preferable to use a binder that is not significantly affected by pH, and examples of such binders include acrylic or methacrylic resins, polyvinyl acetate, polyvinyl alcohol, vinyl acetate resins and their derivatives such as polyvinyl formal and polyvinyl butyral, and cellulose derivatives. , vinyl polymers of nitrogen-containing compounds such as polyvinylpyrrolidone and polyvinylcarbazole, and polycarbonates are preferred, and it is more practical to use those having a glass transition point of 70°C to 150°C.
If the glass transition point is below 70°C, it will adhere to the thermal head etc. during recording, and if it is above 150°C, the movement of molecules necessary for color development will be hindered. Further, when a binder with a pH close to basicity is used, color development is improved, and a binder having a quaternary ammonium base in its side chain is particularly preferred.

Such binders having a quaternary ammonium base in their side chains include poly(2-hydroxy-3-methacryloxypropyltrimethylammonium chloride), poly(vinylbenzyltrimethylammonium chloride), poly(N-vinyl chloride-
Poly(2,3-dimethylimidazolium), poly(N-acrylamidopropyl-3-trimethylammonium chloride), poly(vinylmerimethylammonium chloride), poly(allyltrimethylammonium chloride), and the like can be used.

Similarly, a so-called alkali generator may be added for the purpose of improving color development, and examples of the alkali generator include ammonium carbonate, ammonium acetate, ammonium formate, or amines such as hexamethylenetetramine or triethanolamine. Alternatively, urea etc. can also be used.

The following method is exemplified for forming a light- and heat-sensitive recording layer and a heat-sensitive recording layer using the above-mentioned diazosulfonate, diazonium salt, coupling agent, binder, and the like.

First, to form a heat-sensitive recording layer, 1 part by weight of a diazonium salt, 1 to 4 parts by weight of a coupling agent, 1 to 80 parts by weight of a binder, especially when using a binder containing a quaternary ammonium base in its side chain, 5 parts by weight Add ~30 parts by weight, and further add plasticizers, stabilizers, surfactants, wax/grease, etc. as necessary.
Desiccant, auxiliary desiccant, curing agent, emulsifier, thickener,
Add fillers, dispersants, solvents and diluents as appropriate,
The kneaded paint is used to coat or print on a suitable support by a known coating/printing method.
Known coating and printing methods include gravure coating,
Roll coating, air knife coating, kiss coating, spray coating, continuous coating, dip coating, spinner coating, wheeler coating, brush coating, solid coating by silk screen, wire bar coating, flow coating, gravure printing, gravure offset printing, lithographic offset printing , die lithographic printing, letterpress printing, intaglio printing, jet printing, silk screen printing, electrostatic printing and the like.

The method for providing the photosensitive and heat-sensitive recording layer is the same as the method for providing the heat-sensitive recording layer described above, and the diazonium salt may be replaced with a diazosulfonate in the formulation of the paint used to provide the heat-sensitive recording layer.

Supports include paper such as tissue paper, ledger paper, and paperboard, polyethylene film, polypropylene film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film,
Polyethylene terephthalate film, polycarbonate film, nylon film, polystyrene film, ethylene vinyl acetate copolymer film, ethylene vinyl alcohol copolymer film, plastic film such as ionomer, metal foil such as aluminum or copper, or a composite of each of the above materials. If necessary, a primer layer may be applied or an appropriate oxidation treatment may be performed to improve adhesion.

The order in which the heat-sensitive recording layer and light-sensitive heat-sensitive recording layer are provided on such a support is as follows:
It is preferable to first provide the heat-sensitive recording layer on the support, and then provide the light-sensitive and heat-sensitive recording layer, but if the base material is transparent and can be viewed from the back side of the base material, it may be difficult to provide the heat-sensitive recording layer in the reverse order. There isn't.

The two-color light and heat sensitive recording material, which is the first invention of the present invention, is essentially produced as described above.
In addition to the above description, the light and heat sensitive recording layer and/or the heat sensitive recording layer may be provided not on the entire surface of the support but partially in a striped, circular, elliptical or square shape, and furthermore, on the back surface of the support. The magnetic recording layer may be provided on the entire surface or in the form of stripes, or
The support, light and heat sensitive recording layer, heat sensitive recording layer and magnetic layer may be appropriately printed, and a primer layer for printing or a protective layer for protecting each layer exposed on the surface may be provided. Good too.

The two-color photosensitive and heat-sensitive recording material of the present invention as described above is capable of producing two colors by using both activation-thermal recording with light and simple thermal recording, and it is possible to develop two colors on the entire surface after thermal recording. Fixation is possible by exposure.

Recording using the two-color photosensitive and thermosensitive recording material produced in this way is usually done by thermally developing the color with a diazonium salt and a coupling agent using a thermal head, and then fixing it by irradiating it with light preferably having a wavelength of 300 to 450 nm. However, if you want to develop a color in a different hue than that produced by the above method, photoactivation is performed by irradiating the desired area with light with a wavelength of 300 to 520 nm, and then thermal recording is performed. Let's do it. Photoactivation may be performed using a slit or the like, or an array of light emitting diodes that emit light with a wavelength of 300 to 520 nm may be used to apply light in a desired pattern before printing or image recording with a thermal head. Activation is performed, and then an array of light emitting diodes is used to synchronize the photoactivated area and a thermal head is used to print or record an image.
Only desired characters or images can be colored in a different color.

Examples are given below to more specifically explain the present invention.

Example 1 After applying an acrylic polyol and isocyanate primer to a polyester film (manufactured by Toray Industries, Inc., Lumirror, thickness 100 μm), the following liquid A was applied using a roll coating method so that the dry coating amount was 1.5 g/m ² After drying at 60°C for 1 minute, the following liquid B was applied using the same coating amount, coating method, and drying conditions as liquid A.

Part A 4-Tolylmercapto-2,5-diethoxybenzenediazonium borofluoride salt...1.0g 2-hydroxy-1-naphthoic acid...3.0g Methyl ethyl ketone...80.0g Cellulose acetate butyrate...6.0g Part B 4-Tolylmercapto-2 , Sodium 5-diethoxybenzenediazosulfonate...1.0g 2-hydroxy-3-naphthoic acid...3.0g Methyl cellosolve...80.0g Polymethyl methacrylate...6.0g Cover half of the obtained yellow recording sheet with black paper, 50 mJ/cm ² using a metal halide lamp for diazocopy (manufactured by Ricoh, Ricoh High Start 4)
After photoactivating the diazosulfonate with a dose of
KH30 type...7 segments, applied voltage 15V, application time 50msec) was used to perform thermal printing, and the same light source as above was used to irradiate at 500mJ/ ^cm2 . The areas that were not covered with black paper were colored red due to the color development of the light and heat sensitive recording layer, and the areas that were not covered with black paper were colored due to the color development of the heat sensitive recording layer.
Characters of each color were obtained in a slightly reddish blue color, and the diazonium salt and diazosulfonate were decomposed in areas other than the characters, and the original yellow color disappeared.

Claims (1)

[Scope of Claims] 1. Two-color color development characterized by having two layers: a light- and heat-sensitive recording layer containing at least a diazosulfonate and a coupling agent, and a heat-sensitive recording layer containing at least a diazonium salt and a coupling agent. Type light and heat sensitive recording material. 2. A light- and heat-sensitive recording layer containing a diazosulfonate and a coupling agent; and a heat-sensitive recording layer containing at least a diazonium salt and a coupling agent.
A step of photoactivating the light and heat sensitive recording layer by irradiating a desired portion of a two-color light and heat sensitive recording material with actinic rays, a step of performing thermal recording, and a step of photofixing by irradiating a fixing light beam. A recording method characterized by performing a step of performing.