JPS60110487A - Heat developing diazo type recording body - Google Patents

Abstract

PURPOSE:To obtain a high sensitivity film free of discoloration and fading, by forming a heat developer from a salt of a specific monobasic or polybasic salt and specific alkyl substituted guanidine and higher fatty acid amide. CONSTITUTION:A recording layer containing a diazonium compound, and coupler, an acid stabilizer, a heat developer and a m.p. lowering agent for lowering the m.p, of the heat developer is provided on a support to constitute a heat development diazo type recording body. In this case, the heat developer comprises a salt of a monobasic or polybasic acid of which the primary dissociation constant is 2X10<-1>-1X10<-4> and alkyl substituted guanidine represented by formula I and, as the m.p. lowering agent for lowering the m.p. of the heat developer, higher fatty acid amide represented by the formula II and selected from ones having m.p. range of 60-110 deg.C is used. By this method, the heat development diazo type recording body high in thermal color forming sensitivity and excellent in storage stability is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-developable diazo type recording material which is capable of a process in which colored portions do not recolor due to heat.

The present inventors have previously developed a recording material using a salt of a certain type of alkyl-substituted guanidine and an acid having a certain dissociation constant as a thermal developer as an alkali precursor type heat-developable photofixing diazo type recording material. developed and applied for a patent. this is,
As explained in detail in JP-A-58-12889jS, good heat-sensitive color development, 7'. discovered that a certain type of fatty acid amide, which has been conventionally used as a melting point lowering agent for coupling agents, is compatible with this thermal developer and also lowers the melting point of this thermal developer. For this reason,
When this fatty acid amide is used together with the heat developer disclosed in JP-A-58-128896, the melting points of both the coupling agent and the heat developer are lowered, resulting in more heat-sensitive coloring than simply lowering the melting point of the coupling agent. Sensitivity is improved.

The present invention has been made based on the above knowledge, namely, a diaznium compound i; a coupling agent, an acid stabilizer, a heat developer, and a melting point depressant that lowers the melting point of the heat developer are provided on a support. A recording medium provided with a recording layer containing a thermal developer having a primary dissociation constant of 2×10 −1 to 1×10 ′ and a monobasic or polybasic acid of the following general formula (Tl At least one of them is C8-
A salt with an alkyl-substituted guandun represented by a C24 alkyl group, the others being a hydrogen atom or an alkyl group of 01 or more, and a melting point depressant that lowers the melting point of the thermal developer,
A higher fatty acid amide represented by the following general formula (Ill (where R1 is a C5-C24 alkyl group, R2 is a hydrogen atom or a C5 or higher alkyl group) and has a melting point selected from the range of 60°C to 110°C A heat-developable diazo type recording material characterized by comprising:

The heat-developable diazo type recording material of the present invention is an alkali precursor type, and uses a salt selected from the alkyl-substituted guanicines described above as a heat developer and a melting point depressant to lower the melting point of the heat developer. , is characterized by using the higher fatty acid amide described above. Such a heat-developable diazo type recording medium not only achieved high sensitivity recording, which had been difficult to put into practical use, by lowering the melting point of the salt of alkyl-substituted guanisine with a higher fatty acid amide, but also achieved high-sensitivity recording, which had been difficult to put into practical use. The use of guanicine salt provides good storage stability. In this way, the present invention provides a heat-developable diazo type recording material for high-sensitivity recording that has not been seen before.

The thermal developer used in the present invention has a -order dissociation constant of 2X1
0'~lX10. ' polybasic acid and the following general formula (1) % formula % (However, at least one of R1 and R2 is C8-C
24 alkyl groups, the others are hydrogen atoms or C1 or higher alkyl groups). Such alkyl-substituted guanidine has extremely low solubility in water, of the order of several square meters or less per 100 +++ l of an aqueous solution.

That is, guanidine compounds have more hydrophobic properties than hydrophilic properties. As an acid capable of forming an appropriate salt with such an alkyl-substituted guanidine exhibiting hydrophobicity, it can have a first-order dissociation constant of 21×10'4-.

More specifically, examples of the alkyl-substituted guanidine include octylguanidine, nonylguanidine, decylguanidine, undecylguanidine, laurylguanidine,
Tridecylguanidine, myristylguanidine, hexadecyldaanidine, octadecylguanidine, icosylguanidine, tocosylguanidine, dioctylguanidine, dioctadecylguanidine, N-methyl-N-octadecylguanidine, N-methyl-N-decylguanidine, N , N-didecylguanidine, and the like.

On the other hand, leic acid, phosphoric acid, citric acid, malonic acid, tartaric acid, malic acid, lactic acid, etc., which form salts with alkyl-substituted guanidines, are suitable.

Furthermore, the alkyl-substituted daanidine salt used in the present invention can be synthesized by a known method.

That is, a solution of alkyl-substituted guanidine dissolved in a suitable solvent is heated for 50' cvc, and while stirring, a stoichiometric amount of the dissolved solution is added dropwise. Approximately 100% by continuing to stir for about 10 minutes after the completion of dropping.
can be produced with a yield of .

Further, the melting point depressant for lowering the melting point of the alkyl-substituted guanicine salt used in the present invention has the general formula % (wherein, R1 is a C3 to C34 alkyl group, and u2 is a hydrogen atom or an alkyl group of 01 or more). It is a higher fatty acid amide selected from the range of 60°C to 110°C with a melting point represented by

Here, when a melting point depressant that lowers the melting point of the salt of alkyl-substituted guanisine is used, it is pointless if the storage stability of the heat-developable recording material is impaired.

In this respect, the higher fatty acid amide described above can improve the thermal coloring sensitivity without impairing storage stability. Examples of these higher fatty acid amides include hexanoic acid amide, lauric acid amide, mystic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, N-stearylacetamide, and N-stearylacetamide. , N-oleyl erucamide, N-oleyl behenic acid amide, N-lauryl erucamide, and the like.

Here, instead of describing the effect of the actual melting point depressing agent, the melting point was measured. As can be seen, the melting point of 100% octadecylguanidine oxalate (5) is around 185°C, whereas (A):
When Bl=6o:40, the melting point is approximately 105°C, and even if the amount of stearic acid amide (B) is increased further, the melting point will not drop much.

So, (5):([1l=100:0, and prisoner:
(Recording bodies were prepared using each of the mixtures of E31 = 60:40, and the color density when heated at various temperatures for 1 second at a pressure of 2 kg/i is shown in Fig. 2. The horizontal axis is the heating temperature, and the vertical axis is the optical density (0°D, ). ) = 60: 40 items are shown.

In this way, the present invention improves the thermal sensitivity (decreases the melting point) of a thermal developer, that is, an alkyl-substituted guanicine, by using a melting point depressant, that is, a higher fatty acid amide.
was effectively carried out, and a heat-developable diazo type recording material having high heat-sensitive color development sensitivity and excellent storage stability was obtained. This is because the phenomenon of melting point depression occurs due to the compatibility between the thermal developer, alkyl-substituted guanisine, and the melting point depressant, higher fatty acid amide. This is thought to be because it is difficult to dissolve in water (and cannot cause fogging).

In addition, as mentioned above, when the ratio is 60:40, the melting point of this mixture is the same as that of stearamide (B) alone (but instead of stearamide, a fatty acid amide with a lower melting point) is used. If a fatty acid with a high melting point is used, it is easy to accidentally develop color during storage before using the recording material (before heat development or photofixing) or when drying after coating the recording layer.On the contrary, fatty acids with a high melting point Naturally, when an amide is used, the coloring sensitivity during heat development is inferior.From this point of view, the melting point of fatty acid amide is 60°C to 110°C.
The melting point of the mixture of the thermal developer and the fatty acid amide can be adjusted by the melting point of the fatty acid amide used and the mixing ratio thereof.

The heat-developable diazo type recording material according to the present invention has satisfactory storage stability and heat-sensitive coloring sensitivity, both of which were difficult to put into practical use, due to the properties of the alkyl-substituted guanidine and higher fatty acid amide described above. can be applied.

For example, it is a particularly effective recording medium as a computer output printer, a data communication terminal, or as a ticket, card, or stickerless commuter pass that requires counterfeit prevention.

The heat-developable diazo type recording material of the present invention is characterized by the above-mentioned heat developer and melting point depressant, and any other recording material used in known diazo photosensitive papers can be used. It can be used and is not limited in any way to the present invention.

Hereinafter, the thermal developer used in the present invention and the recording material other than the melting point depressant that lowers the melting point of the thermal developer will be described in detail.

Various known diazo compounds can be used as the diazo compound used in the present invention. For example, various phenylenediamine N-N-substituted compounds (4-diazo-N-N-diethylaniline et, c), Amituno 1-hydroquinone ether type (4-di1azo-2-5-diptoxy-N-N-diethylaniline) , 4-diazo-2-chloro-5methoxy-N-benzoylaniline, etc.), aminodiphenyl, aminodiphenylamine, and similar compounds (4-diazo-2-5-4Llyl-sidifinylamine, etc.)
, a derivative of heterocyclic amine (4-diazo-2
-5-Diacrylic acid N-phenylmorpholine etc.
) etc. The diazo compounds described above are used as diazonium salts, which are relatively stable as sulfates or hydrochlorides, or as double salts with zinc chloride or the like.

Further, stabilization methods such as diazonium sulfonate, diazonium borofluoride, and diazonilla cold phosphorus fluoride can also be used.

Further, as the coupling agent used in the present invention, any coupling agent that is normally used for diazo photosensitive paper can be used.

For example, resorcinol, 2,2'-4,4'-tetrahydroxydiphenyl sulfide, phloroglucin, 1-
sodium hydroxy-naphthalene-6-sulfonate,
Sodium 2,3-dihydroxynaphthalene-6-sulfonate, 2,3-dihydroxynaphthalene-6-sulfo-N,N-diethylamide, Sodium 2-hydroxynaphthalene-3,6-disulfonate, 1-(3-aminobenzamide) )-4-naphthol, 1-(6-aminobenzamido)-7-naphthol, 2,6-dihydroxynaphthalene, 2,3-dihydroxy-6-sulfanylnaphthalene, 1-carboxy-2,3-dihydroxynaphthalene, 1. 4-dichloro-2,3-dihydroxynaftabine, 2,6-dihydroxybenzoitucamide,
2-hydroxy-3-naphthoic acid, 2-hydroxy-3
- Naphthoic acid morpholinoglopioic acid, 2-hydroxy-6-naphthoic acid 2-hydroxy-6-naphthoic acid dimethylamine propylamide, 2-hydroxynaphthalene-5-carbonylphenyl ester, 2-hydroxynaphthalene-5-power Rubonyl-4'-methoxyanilide, 2-hydroxynaphthalene-6-carbonyl-3'-
Nitroanilide, 2-hydroxynaphthalene-3-carbonyl-4-hydroxyanilide IJ)', 2-hydroxynaphthalene-3-carbonyl-2L methylanilide, 2-hydroxynaphthalene-3-carbonyl-2'-ethoxyanilide, 2-hydroxynaphthalene -3-Carbonyl-2'-methoxyanilide, 2-hydroxynaphthalene-3-carbonyl-27-nodoxy-5L nitroanilide, 2-hydroxynaphthalene-3-carbonyl-2'
-Methyl-4'-chloranilide, 2-hydroxynaphthalene-3-carbonyl-2'-methoxy-4'-chloranilide, 2-hydroxynaphthalene-6-carbonyl-3ζ 6fudimethoxy4'-chloranilide,
2-hydroxynaphthalene-6-carbonyl-6'-
Chlor-4-6'-dimethoxyanilide, 1-human 20
xinaphthalene-2-carbonyl-phenyl ester,
Examples include acetoacetanilide.

As the acid stabilizer used in the present invention, various known nonvolatile acids used for diazo type materials can be used. Examples include citric acid, gluconic acid, oxalic acid, tartaric acid, sulfamic acid, hydroxylamine hydrochloride, boric acid, phosphoric acid, and the like. In addition, thiourea, L-ascorbic acid,
Even if urea, allyl isothiocyanate, etc. are used, the color development sensitivity and storage stability of the recording medium of the present invention will not be impaired.

The polymer binder used in the present invention is used to improve the adhesion between the recording material and the support, the coating uniformity, or the water resistance. (However, the properties of the recording medium of the present invention are not impaired in any way. Examples of the polymer binder include polyvinyl alcohol, hydroxyethyl cellulose, polyvinyl alcohol-gum arabic, polyvinyl acetate emulsion, methyl cellulose, ethyl cellulose, Examples include polyvinyl butyral, polyvinyl acetate, polystyrene, nitrocellulose, cellulose acetate butyrate polymer, salt-and-acetate picopolymer, and polymethacrylic acid ester.

Next, a known method can be used to coat the recording layer on the support in the present invention.

Specifically, a solution prepared in advance is prepared by dissolving a recording agent consisting of a diazo compound, a coupling agent, an acid stabilizer, an antioxidant, and, if necessary, a polymeric binder in water or an organic solvent. A coating solution containing a heat developer and a dispersion containing a melting point depressant that lowers the melting point of the heat developer is coated onto a support such as paper, glass, or film using a wire bar and dried at a low temperature. By doing so, a heat-developable diazo type recording material can be manufactured. In addition, when the recording layer has a two-layer structure, a thermal developer, a melting point depressant that lowers the melting point of the thermal developer, a coupling agent, and a polymer binder are uniformly dispersed in water or an organic solvent. After drying, a recording agent consisting of a diazo compound, an acid stabilizer, an antioxidant, and if necessary a polymeric binder is added to the layer using water or an organic binder. A heat-developable diazo type recording material can be manufactured by applying a solution dissolved in a solvent using a wire bar or the like and drying it. However, some of the thermal developers used in the present invention are soluble in organic solvents, so even if they are not used as a dispersion liquid and are used in a solution type, the characteristics of the recording medium of the present invention will not be affected in any way. There's nothing to lose.

The method for recording the heat-developable diazo recording material thus obtained is as follows:
An image is formed on the recording layer of the recording body using thermal energy, and then the entire surface is irradiated with light energy and fixed to form a permanent image, or a transparent original is brought into close contact with the recording layer of the recording body. irradiate with light energy to form a latent image,
Next, it is possible to apply heat energy to the entire surface and develop it to form a permanent image. As a thermal energy source used here, a thermal head, a thermal pen, an infrared ray, a laser beam, a thermal roll, etc. can be used. Further, as a light source that generates optical energy, a mercury lamp, a xenon lamp, a tungsten lamp, a xenon flood, and a laser shade can be used.

Examples of the present invention will be shown below. In each example, "part" means part by weight.

(Example 1) Oleic acid amide 10 parts 2.3-dihydroxynaphthalene-6-sulfo soda 4 parts Polyvinyl alcohol 10 parts Water/isopropyl alcohol (7/3) Loo part [B
[Liquid] Oxalic acid 05 parts P-toluenesulfonic acid 01 parts Water/isopropyl alcohol (7/3) 1 oo parts First, the above composition [Liquid A] was prepared, pulverized for 24 hours using a ball mill, and further uniformly dispersed. To 50 parts of the obtained dispersion liquid A, 25 parts of liquid B prepared in advance was added to prepare a coating liquid.

The coating solution was applied onto high-quality paper using a No. 24 wire coater and dried in a hot air dryer at 60° C. to produce a heat-developable diazo type recording paper.

This recording paper was first transferred to Mitsubishi MELFAS 600 (G-I
When printing in G-11t mode with L[) and exposing and fixing the entire surface using Riffy High Start Type 4 [manufactured by Ricoh], a bluish-purple image with an optical density of 1.0 is formed on a pale background. Ta. Also Mitsubishi ME LFA S60 o, (
After printing with G-II), do not expose the gold surface to light, leave at 30°C relative humidity 20% for 6 months, leave at 30°C relative humidity 90% for 1 month, then fully expose with Recopy High Start 4 type to cause discoloration and fading of the image. When looking at the level of fogging on the base and under the upper condition, there was no discoloration or fading of the image, and no capri on the base.

As described above, it was possible to provide an excellent, highly sensitive heat-developable diazo type recording paper having properties that can withstand practical use.

(Example 2) Stearic acid amide 1 part hydrochloric acid picopolymer 8 parts methyl ethyl ketone 70 @ [Liquid B] Oxalic acid 04 parts hydrochloric acid picopolymer 2s Methyl ethyl ketone 50 parts First, liquid B having the above composition was placed on a 300μ polyester film with a No. 8 wire. Coat using a bar, 100℃
Dry at the following temperatures: On top of that layer, a dispersion liquid A obtained by preparing the above composition [liquid A] in advance, pulverizing it for 24 hours using a ball mill, and uniformly dispersing it, was applied using a wire bar of wire No. 24.
A heat-developable diazo type recording film was prepared by drying in a hot air dryer in an atmosphere of °C.

This recording film was printed using a Toshiba thermal printer (printing conditions 0.6W, path width/m5), and then the entire surface was exposed with a xenon flash (exposure energy 450J), and when it was fixed, it had a pale color syncretic density. A black image with an optical density of 1.2 was formed against a background of 0°15). Also,
10 in an atmosphere of raw film at 40℃ and 90% relative humidity.
After being left for a day, printing and fixing were performed in the same manner as above, and a black image with an optical density of 11 was formed against a pale color background (optical density of 020), indicating that it was a recording film with excellent storage stability. Furthermore, after fixing, no discoloration or fading of the image was observed even when the image was rubbed with gauze soaked in water or ethyl alcohol.

As described above, it was possible to provide a highly sensitive recording film with properties that can withstand practical use.

[Brief explanation of drawings]

FIG. 1 is a graph showing the melting point depression of oxalate of octadecylguanidine, which is one of the heat developing agents, by stearamide. Figure 2 shows the heat-sensitive color development sensitivity curves of the heat-developable diazo type recording material 20- with octadecylguanidine as a heat developing agent and with the addition of stearic acid amide as a melting point depressant (bl and without (a)). Patent applicant Toppan Printing Co., Ltd. Figure 1 I ratio (wt”) Figure 2 70] OO130 Temp ('C)

Claims (1)

[Claims] (1) A recording body provided with a recording layer containing a diazonium compound, a coupling agent, an acid stabilizer, a thermal developer, and a melting point depressant that lowers the melting point of the thermal developer on a support (provided that R' and R2 A salt with an alkyl-substituted guanicine represented by a small number (one is a C8 to C24 alkyl group, the others are a hydrogen atom or a C1 or higher alkyl group), and a melting point depressant that lowers the melting point of the thermal developer. The following general formula (It) (However, R is C3-C2a(1') a/l/ya,, group,
R2 is a hydrogen atom or an alkyl group of C1 or higher), and a higher fatty acid amide having a melting point in the range of 60 to 110°C.