JPS59149A - Heat-developable diazo copying material - Google Patents

Abstract

PURPOSE:To obtain an entitled copying material forming a high-density image with low temp. development, by forming the second layer contg. a diazo compd. and a filler having specified property on the first layer contg. a coupling component, an ionomer resin, and a heat meltable color forming aid. CONSTITUTION:The first layer contg. a coupling component, such as resorcinol or phloroglucin, an ionomer resin, such as an ethylene-acrylic acid copolymer with metal ions added, and a heat meltable color forming aid having 50-150 deg.C m.p., such as capronamide, is formed on a support, such as paper or plastics. On this layer, the second layer contg. a diazo compd., such as 4-diazo-1-dimethylaminobenzene, and a filler having <=100cc/100g oil absorptivity and <=20mum particle diameter, such as styrene-methacrylate resin or calcium carbonate, is formed to obtain the present intended thermodevelopable diazo copying material.

Description

[Detailed description of the invention] The present invention relates to heat-developable diazo copying materials.

Conventionally, the following are known as heat-developable diazo copying materials (or diazo heat-sensitive recording materials).

1) A photosensitive layer consisting mainly of a diazo compound, a coupling component, and an alkali generator such as urea or sodium trichloroacetate is provided on a support such as paper or plastic (Japanese Patent Publication No. 43-24726) 2) The above-mentioned l) Copying material [using a thermofusible coloring aid (melting point 48 to 150°C) such as higher fatty acid agdo instead of an alkali generator (Japanese Patent Publication No. 1983-839) 3) The copying material described in 2) above (in which the coupling component is encapsulated with a hydrophobic substance such as a resin (Japanese Patent Publication No. 41-2145)) However, the copying material described in 1) requires a high developing temperature of 1150 to 200°C. Therefore, it is necessary to use a diazo compound with high heat resistance, which is disadvantageous for forming high-density images, and also requires a high-temperature and high-precision heating device. 2) Copying materials Unlike beam copying materials, low-temperature development is possible, and therefore high-density images can be obtained;
The disadvantage is that the copying material itself has poor storage stability (hereinafter referred to as storage stability). In addition, in the case of 3) copying material, the coupling component is wrapped in a hydrophobic substance, so
Although the defect of copying material 2) can be improved, it has been difficult to obtain high-density images by low-temperature development.

An object of the present invention is to provide a heat-developable diazo copying material which can easily produce high-density images even though low-temperature development is possible, and which has excellent storage and memorization properties.

That is, the present invention provides a heat-developable diazo copying material in which a light-sensitive and heat-sensitive layer comprising a diazo compound, a coupling component, and a thermofusible coloring aid having a melting point of 50 to 150° C. as main components is provided on a support. A layer No. 11 containing a coupling component and an ionomer resin is provided on top, and a second layer containing a diazo compound as a main component is provided on top of the layer No. 11- containing a coupling component and an ionomer resin.
00 ee / 100 or less, and is characterized by containing filler with a particle size of 20 μ or less. Since the diazo copying material of the present invention is a heat-developable type, it can be used as a heat-sensitive recording material that prints with a thermal head, a thermal pen, or infrared rays as in the past. As the diazo compound used, those conventionally used in the field of two-component diazo copying materials can be used as they are.

That is, as a diazo compound, for example, 4-diazo-1-
Dimethylaminebenzene, 4-diazo-1-diethylaminobenzene, 4-diazo-1-dipropylaminobenzene, 4-diazo-1-methylbenzylaminobenzene, 4-diazo-1-dibenzylaminobenzene, 4-diazo- 1-ethylhydroxyethylaminobenzene, 4
-Diazo-1-diethylamino-3-methoxybenzene, 4-diazo-1-dimethylamino-2-methylbenzene, 4-diazo-1-hensoylamino-2,5-jethoxybenzene, 4-diazo-1- Morpholinobenzene, 4-diazo-1-morpholino-2,5-jethoxybenzene, 4-diazo-1-morpholino-2,5-dibutoxybenzene, 4-diazo-1-anilinobenzene, 4
-Diazo-1-dimethylamino-3-cardioxybenzene, 4-diazo-1-tolylmercapto-2,5-jethoxybenzene, 4-diazo-1,4-methoxybenzoylamino-2,5-jethoxy Double salts of chlorides of diazo compounds such as benzene with metal halides (e.g. zinc chloride, cadmium chloride, tin chloride, etc.), and salts of the diazo compounds with strong acids such as sulfuric acid, boron tetra7ide, hexafluorophosphoric acid, etc. Examples of coupling components include resorcin, phloroglucin, 2-methylresorcin, phenylmethylvinyl
Zolone, 2,5-dimethyl-4-morpholinomethylphenol, 3-hydroxycyanoacetanilide, norasulfoacetanilide, l-benzoylamino-8-hydroxynaphthalene-3,6-disulfonamide, 2,
2-dihydroxynaphthalene, z,r-dihydroxynaphthalene-3,6-sodium disulfonate, 2,3-dihydroxy-6-sodium sulfonate, 2,5-dihydroxynaphthalene-6-sodium sulfonate, l-hydroxynaphthalene- Sodium 4-sulfonate, 1-amino-3-
Hydroxynaphthalene-3,6-disulfonamide, Naphthol As, Su7tol A8-D.

2-hydroxynaphthalene-3-piguanide, 2-hydroxynaphthoic acid morpholinopropylamide, 2-hydroxynaphthoic acid ethanolamide, 2-hydroxynaphthoic acid [-N-dimethylaminopropylamide hydrochloride, 2,4,2'.

4'-tetrahydroxydiphenyl, 2,4.2'.

Examples include 4'-tetrahydroxydiphenyl sulfoxide.

In the present invention, an ionomer resin is used together with a coupling component in order to improve low-temperature developability (thermal sensitivity) while maintaining raw shelf life. Ionomer resin is known for its strength)
By adding metal ions to polymers having vd xyl groups, etc., ionic crosslinks are created between the polymers.

This ionic crosslinking is reversible to heat, and when heated, the ionic bonds become weaker, the network structure disappears, and the material becomes more fluid, and when it is cooled, ionic crosslinking occurs again. On the other hand, it is desirable that the binder used in this copying material has thermal properties such that it rapidly melts at a certain temperature or higher when heated. Traditionally used. Many binders gradually soften when heated, which is disadvantageous for the thermal sensitivity required for this copying material. In the present invention, as mentioned above, the thermal sensitivity is significantly improved by providing the ionomer resin with good heat meltability in the first layer together with the coupling component. Furthermore, for the reasons mentioned above, ionomer resins have good film-forming properties, excellent water resistance, and low moisture permeability, which significantly improves storage stability.

The ionomer resin used in the present invention is a common one, for example, ethylene and α, β-ethylenically unsaturated mono-1- or Cica/I/d? represented by the trade name Surlyn (manufactured by DuPont). There is a copolymer of ethylene and acrylic acid, such as ethylene and acrylic acid copolymer (manufactured by Asahi Dow Co., Ltd.), in which metal ions are added. The metal ions used are, for example, N
Monovalent ions such as a, K, Lt, Ag, Cu,
Mg, Cm, C'u, Nl, Zn 2
There are valent ions and trivalent ions such as Ap and Fs.

As mentioned above, a copying material with excellent low-temperature developability can be obtained by using an ionomer resin, but it is preferable to add a thermofusible auxiliary agent. The thermofusible coloring aid in the present invention is a thermofusible substance that is insoluble in water and has a melting point of 50 to 150°C, and that dissolves the diazo compound and the coupling component well when melted. Any one can be used. Further, these color development aids can be used in the first layer, the second layer, or both layers. For example, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, araxic acid amide, behenic acid amide, palmitoleic acid amide, oleic acid amide, eicosenoic acid amide , erucic acid amide, elaidic acid asado, trans-1゜1-eicosenoic acid amide, linoleic acid amide, linoleic acid amide, ricinoleic acid amide, N-methylpalmitic acid asdo, N-methylstearic acid amide, N -Propyl stearic acid amide, N-
Butyl stearic acid amide, stearic acid anilide, N
-Methylbehenic acid amide, N-ethylpehenic acid amide,
N-Butyl behenic acid amide, behenic acid anilide, N-methyl oleic acid amide, linoleic acid anilide, N-ethyl capric acid amide, N-butyl lauric acid 7-do, capric acid 〇-methoxyanilide, N-hexyl stearic acid Atakudo, N-octadecyl acetamide, N-octadecylbutyramide, N-octadecylpropionamide, N-oleylacetamide, N-oleylbenzamide, N-laurylbutyramide, N-2urylpenzado, N-behenylacetamide, N -Behenylpropion 7 Mi)', N-A=ybenzamide, N-i listylbenzamide, N-stearylbenzamide, N-stearylacetamide, N-stearylcyclohexylamide, N-stearyl-0-chlor4
lenses'famide, N-lumitylbenzamide, N-palmitylacetamide. Others include higher fat +11 and its esters, He realkylene glycol (eg, polyethylene glycol, polypropylene glycol, copolymers thereof, etc.).

All of the above compounds used as color development aids in the present invention are heat-fusible and poorly water-soluble or water-insoluble, and are used in the form of fine particles with a particle size of 0.1 to 10 μm. This coloring aid is 0.1 to 1001 for diazo compound type 1
i parts, preferably 1 to 50 parts by weight. As mentioned above, these coloring aids are used in the first layer and/or the second layer, but it is preferable to use these coloring aids in at least the first layer.

In the present invention, the second layer contains 7-iller for the purpose of improving the writing properties. The filler oil absorber used in the present invention is 100e.
e/10 (IIF or less; if it is larger than that, the storage stability will deteriorate.The particle size is preferably 20μ or less; if it is larger than that,
The clarity is poor. As for the material of the filler, both organic filler and inorganic filler can be used. For example, organic fillers include styrene-methacrylic resin, styrene-acrylic acid resin, and the like. Inorganic fibers include silicon dioxide,
Examples include calcium carbonate, magnesium hydroxide, magnesium silicate, and aluminum hydroxide.

The method of use is to apply a coating amount of 0.1 to 297 on the diazo layer (second layer).
It is preferable to apply the coating so that it becomes 0.117 m”.
If it is less than 21/-, there is no effect of fission, and if it is more than 21/-, the image density may decrease. Moreover, not only one type but also a mixture of two or more types may be used.

In addition to the above-mentioned materials, the present invention uses various additives that are used in ordinary heat-developable diazo copying materials.

For example, substances that generate alkali upon heating include urea, thiourea and their derivatives, alkali salts of trichloroacetic acid, ammonium chloride, 4i1f, ammonium acid, guanidine sulfate, ammonium citrate, sodium benzoate, imidazole and their derivatives. Sodium naphthalene monosulfonate, sodium naphthalene disulfonate, sodium naphthalene trisulfonate, sulfosalicylic acid, cadmium sulfate, magnesium sulfate, cadmium chloride, zinc chloride, etc. can be used as storage improvers. In addition, antioxidants such as thiourea and urea, solubilizing agents such as caffeine and theophylline, and acid stabilizers such as citric acid, tartaric acid, sulfuric acid, citric acid, boric acid, phosphoric acid, and hyrophosphoric acid, etc. A small amount of saponin can be added. Further, as a binder, polymeric substances such as starch, casein, polyvinyl acetate, polyvinyl alcohol, etc. can be used. Furthermore, inorganic or organic fine particles such as silica, starch, clay, and resin can be used as image density improvers.

To make the heat-developable diazo copying material of the present invention, first, a coating solution in which the ionomer resin, coupling component, and other additives are dissolved or dispersed is applied onto a support such as paper or film using a wire knife or the like. The first layer is formed by coating and drying the first layer, and then the second layer is formed by coating and drying a coating solution containing a diazo compound, filler, and other additives dissolved or dispersed at ℃ using a wire, etc. Just set it up. The adhesion acid for both the first layer and the second layer is suitably 0.2-15P/mt, and the ratio of the diazo compound to the coupling component is 20 parts by weight of the coupling component O, S to the diazo compound type 1 steep part. is appropriate. Here, the first layer may be dried by normal drying, but at the time of drying, heating is performed above the melting point of the thermofusible coloring aid in the first layer to melt and solidify the thermofusible coloring aid. There are two methods for forming an image on the heat-developable diazo copying material of the present invention. First, like general diazo copying materials, this heat-developable diazo copying material is image-wise exposed using a fluorescent lamp or mercury lamp, and then exposed to infrared rays, a heated roller, high frequency, etc.
The other method is to heat the heat-phenomenal diazo nuclear photographic material to a temperature of about 0 to 130°C in the same way as general heat-sensitive recording materials, using a thermal pen, thermal head, etc. to image the temperature. or heating the image after exposure to infrared light. In either method, unreacted diazo compounds in non-image areas can be separated and fixed by irradiating the entire surface with ultraviolet light using a fluorescent lamp or a mercury lamp, as with general diazo copying materials.

Examples are shown below.

Example 1 Naphthol As 5I!
Behenic acid amide 10g50
I! A liquid consisting of 100p of water is dispersed using a homogenizer to obtain a coating liquid, and this is coated onto the surface of a base paper for diazo copying paper using a wire 4- and dried (100°C) to adhere at 4.5 It/m.
” was formed. Next, t behenic acid amide 1op4
guanidine sulfate 5t polyvinyl alcohol 10% aqueous solution 01 oxalic acid 1 part water
A composition consisting of 100 tons was dispersed using a homogenizer, and this was applied onto the first layer using a wire nozzle and dried (100°C).
) to prepare a heat-developable diazo copying material (Sample A) by providing a second layer with an adhesion amount of 2.517 m''.

On the other hand, for comparison, a heat-developable diazo copying material was prepared in the same manner except that Thyroid-63 in the second layer was replaced with Thyroid-244 (Sample B). Furthermore, a heat-developable diazo copying material was prepared in the same manner except that UF filler was used instead of Thyroid-65. (Sample C).

Table 1 shows the physical properties of each filler.

Table 1 Next, each of the above samples was overlaid with an original and exposed to ultraviolet light, then heated using an infrared heater at 110° C. for 1 second to form a blue image, and its density was measured. Also to test raw shelf life.

After leaving each sample in a desiccator at 50°C and 15OIRH for 24 hours for forced deterioration, 1. The sample was taken out, and the entire surface was irradiated with a fluorescent lamp to decompose all the diazo compounds in the photosensitive layer, and the background density was measured, and this was compared with the background density measured in the same manner without forced deterioration. Note that the image density and background density are based on a Macbeth densitometer. The results are shown in Table-2.

(Hereinafter referred to as margins) As is clear from this table, the products of the present invention maintained image density and shelf life, improved writability, and produced clear copies.

Example 2 2-Hydroxynaphthoic acid morpholinopro2ruacht 40? Stearic acid amide 202 water
A composition consisting of 100 tons was dispersed at °C using a homogenizer, and this was applied onto the surface of a base paper for diazo copying paper using a wire 29 and dried to form a first layer with a coating weight of 4 g/m 1. After that, add 2 and 0.5 tartaric acid on top.
1 Hydroxyethyl cellulose 5% water FT solution 09 Imidazole lOt Ot Water 100#
A composition consisting of the following was coated using a wire pad and dried to give an adhesion amount of 1. The second layer of Ot7- was used as a heat-developable diazo copying material.

Next, a manuscript was placed on the resulting heat-developable diazo copying material (after exposure to ultraviolet rays, it was momentarily heated with a xenon flash lamp, and a clear, high-density blue image was formed). Also, lead flower.

G-Le Pen and fountain pen had excellent writing properties.

Example 3 Naphtho-/I'AS-D 3
0?57 A composition consisting of Behenic acid amide 20 and 100 tons of water was dispersed using a homogenizer to obtain a coating liquid, and this was coated on the surface of a base paper for diazo copying paper using a wire parlor and dried to obtain a coating weight of 4.57. After forming the first layer of 017 m'', a composition consisting of 5 t of 5% aqueous solution of methyl cellulose, 3 t of lauric acid amide, and 100 t of water was further dispersed using a homogenizer to form a coating solution at ℃, and a wire/, ?- Use [Apply and dry]
2. A second layer of O17m'' was formed to obtain a heat-developable diazo copying material.

Next, the original was placed on top of the heat-developable diazo copying material obtained in this way, exposed to ultraviolet light, and heated to 100°C using an infrared heater.
When heated for 5 seconds, a blue fk copy with an image density of 1.25 and excellent preservability and writability was obtained.

9 Qr.

Claims (1)

[Claims] 1. In a heat-developable diazo copying material in which a light-sensitive and heat-sensitive layer containing a diazo compound, a coupling component, and a heat-fusible coloring aid having a melting point of 60 to 150°C as main components is provided on a support. A @X layer containing a coupling component and a fluoromer resin is provided, and a second layer containing a diazo compound as a main component is provided thereon, and the second layer contains oil absorbing ji 100
A heat-developable diazo copying material containing a filler having a particle size of ee/10 G1 or less and a particle size of 20μ or less,