JPS5887092A - Diazo heat-sensitive recording material - Google Patents

Abstract

PURPOSE:To obtaifn a diazo heat-sensitive recording material which is excellent in high-speed chromogenic property and long-term storage stability and is suitable for valuable securities, admission tickets, certificates, etc., as sell as having excellet isolating effect, by using a rosin ester resin as an isolator for the diazo compound and a coupler. CONSTITUTION:In a diazo heat-sensitive recording material in which a diazo compound (e.g., a compound of the formula), a coupler (e.g., 2,6-dihydroxy-3,4- dibrom-4-methoxy benzoic acid, etc.), and a heat-meltable substance (e.g., stearic acid amide, etc., having a melting or softening point of 50-250 deg.C preferably) are supported on a supporter, a rosin ester resin (e.g., rosin-modified phenolic resin, etc.) is used as an isolator for the diazo compound and the coupler. EFFECT:No fogging phenomenon occurs.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-sensitive recording material, particularly to a photofixable heat-sensitive recording material. That is, in the present invention, when recording is performed with a thermal head at a certain temperature, color develops, and when further light is irradiated, the color development ability of the non-printed area disappears, and when heat is applied again, v1
This invention relates to an azo heat-sensitive recording material that does not develop color.

Thermosensitive recording materials are used as copy paper for books, documents, etc., as well as output recording paper for electronic calculators, notebooks, medical measuring machines, etc., as well as thermal recording magnetic ticket paper and thermal recording label paper. However, it is also considered to be used as paper for creating certificates, slips, etc.
In order to achieve high 111 recording reliability, the heat-sensitive recording side O1 must be capable of fixing 711 for such uses.

Conventionally, fixable heat-sensitive NIL records (A and 1) have been known that use diazo threads that utilize a color-forming reaction between a diazo compound and a coupler.However, conventional ones
For practical reasons, the thermal response to the thermal head is 1/
It cannot be said that it is the last one because it is childish. In particular, in fields such as Noaku Tsumiri, there is a strong demand for high-speed recording performance (high-speed color development) in order to reduce information transmission costs, but conventional diazo yarns do not meet these requirements. Still enough/i
It's something that adds j♂, Nakatsu/ζ.

By the way, in /azo-based thermal printing network 1, the color-forming reaction between the azo compound component and the coupler component during production and storage is prevented. A polymeric compound is used as a sequestering agent for both components.

In this case, the method of separating both components using a separating agent is as follows:
A separating agent is attached to the surface of the coupler or diazo compound in the form of a film (including microencapsulation), a separating agent layer is interposed as an intermediate layer between the coupler layer and the azo compound layer, or the separating agent is There are methods such as adding a zuplar or a diazo compound therein. In such isolation methods, when trying to lower the softening temperature of the isolation agent and improve the low-temperature color development of the product to make it suitable for high-speed recording, conventional isolation agents have problems with the long-term shelf life of the product before recording. The problem was that it was getting worse.

The present inventors have conducted extensive research to overcome these problems associated with the separation of couplers and azo compounds, and as a result, by using a rosin ester resin as a separation agent,
The present invention was completed based on the discovery that the high-speed color development and long-term storage stability of the product before recording can be improved.

That is, according to the present invention, in a diazo-based heat-sensitive recording material in which a diazo compound, a coupler and a heat-fusible substance are supported on supporting potting soil, a rosin ester resin is used as an isolating agent for the diazo compound and the coupler. 7 azo heat-sensitive "J12 records" will be provided.

The rosin Nisder resin used in the present invention is defined as a resin that is esterified with methyl, ethyl, or glycerin of abietic acid, which is the main component of J-syn, and these two resins include it, 1+11, and , I:, mJ-modified phenolic resins, polymerized 1 gin pentaerythritol nisdel, pentaerythritol ester of dimerinocresic acid, etc. are included.The JNJ rosin ester resin of the present invention includes 140 to It is preferable to use one with a softening point of ℃. It is used in the ratio of Shibe.

The rosin ester resin used in the present invention has very good fluidity when applied to a coating solution, and it is difficult to use conventional separating agents to form a high-quality film after drying by using a small amount of water. It exhibits a better isolation effect than that of other types, and provides enhanced rapid color development and long shelf life.

In the present invention, conventional barrier-1 agents, such as the resins shown below, can be used as part of the rosin ester resin, if necessary, as long as the purpose is not hindered by the bamboo.

Polyvinyl acetate, polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, polyacrylic ester, polystyrene, polybutadiene, polyacrylamide, styrene/butadiene/acrylic copolymer, petroleum resin, polyvinyl alcohol, polyacrylamide, casein, Ceratin, tenken and its derivatives, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, ethylcellulose, polyester (MW 100,000 or more), polystyrene (MW 100,000 or more 1), comb chloride, styrene-maleic anhydride copolymer, ino( or water-soluble, organic solvent-soluble, or aqueous dispersion type resin such as diiso)butylene-maleic anhydride copolymer, phenol resin, and melamine resin.

51 As the azo compound and coupler used in the present invention, those commonly used in diazo photosensitive paper are applicable, and examples include the following.

/Azo compound: As the diazo compound used in the present invention, a commonly used diazo compound, for example, one represented by the following general formula is used.

19 However, in general formulas [l], [11] and (m),
It, R6+ I%s Ire: Hydrogen, Haloken, (
The argyl group of 3l~Oi is also 6- ■c, tri, hydrogen, haloken, the alkyl group of 01~05 is an alkyl group, R4+ 115 is the same or r1 different, the argyl group of C1~05, hydrogin Alkyl group, or group or alkyl group mo is hydrogen, halogen, trifluoromethyl group, OI to C6
an alkyl group or an alkoxyl group, or (l(,
+4ν1t, 5ri n, , 6: Same as It, , , M
+ + M22M3 is an acid residue or an acid residue forming a double salt with all groups.

In this case, the acid residues include halokene ions and BP4+P.
For example, ZnCl2+ (bl□12+ 5nO
There are I,, etc. Y represents -(M2- or -(]〇-, and n is 0 or l.

For specifics 1 and 17 that correspond to general formula (1),
Examples include:

0CII,.

OC,,lI.

Specific examples of those corresponding to general formula [11] include the following.

= 9 = Specific examples of those corresponding to the general formula Cl1l) and 1~,
For example, the following can be mentioned:

002H.

OC,,U.

C113 In the present invention, in order to obtain a product with further improved long-term shelf life, when using a diazo compound and l-, -former Pa4 or -PF6
Advantageously, they are used in the form of water-insoluble salts such as fluorine-containing acids.

Coupler: Couplers used in the present invention include v41, phenol,
resolunon, methylresoruone, 4) 4-bisresoruone, furo[Jcurcun, resornoic acid, phloroglucin=, 2-methyl-5-methoxy113-dihydroxy/
Benzene, 5-nodoxy-1+ 3-dihydroquine benzene'+ 4-N + N) methylphenol,
2 flow dimethyl-1+ 3 + 5-trihydroginbenzene, 2a6-dihi l-'rgizobenzoin vinegar, 2jirou7hito1'gi/-:Ua5-・/fomu-4-methogi / Phenol visiting conductor with benzoic acid, α-naphthol, β-nanotol, 4-methogysol 1-naphtol,
2A 3-Hydrogynaphthalene, 2I3-/Hydrogynaphthalene-6-sulfonic acid nota, 2-Hl-Jxy-3-propylmorpholinonaphthoic acid, 2-Hydrogear 3-naphtho-〇-toluy/ 1,2-hydrogear 3-naphthoic acid morpholinopropylamide and other naphtho-
Of course, it is limited to these things, but there are 11 things that can be mentioned, such as conductors, and couplers for azo compounds. T It works! 4: arbitrarily applied j′1. Ru.

In the present invention, high-speed color development I■-, H'J3 A/
) In order to do this, a thermoplastic material is used, such as the following:

2-tribromoethanol, 2+2'/notyltrimethylene glycol, I+2-/Chlohegizan 7th edition-
Alcohols such as rutaric acid, maleic acid, methylmaleic acid-conducting conductors, beeswax, shellac, 4i/f physical properties such as carnauba wax, monothane wax, etc. Mineral waxes, paraffin wax, microcrystalline waxes, and other synthetic waxes, e.g.
-+primary-amide, condensate of fatty acid and amine, sil;
Combination of aromatics and amines, synthetic paraffin, J2i+! paraffins, metal salts of fatty acids, straight chain glycols, dialkyl 324-epoxyhexahydrophthalate,
N-alkylcarbamoylbenzene and the like.

In the present invention, it is preferable to use a self-heating fusible substance having a melting point or softening point in the range of 50 to 250°C. If the melting point or softening point is less than 50°C, the shelf life of the product tends to deteriorate, and if it exceeds 250°C, the thermal response of the product to the thermal head becomes unsatisfactory. These thermofusible substances used in the present invention have the advantage of producing a product with continuous color development (1 calf record). From the point, /
2 to 30 parts by weight per 1 part by weight of the azo compound, preferably 1 [7
It is used in a proportion of 5 to IO parts by weight. If this amount is less than the above range, the color development will be insufficient, and the resulting product will be unsuitable for recording materials for high-speed recording and F-. In the case of the present study, it is particularly preferable to use 5 parts by weight or more for high-speed output recording such as Noakumiri. On the other hand, if the amount added is too large, blurring of the image may occur during color development by heating, which is not preferable. Therefore, in the case of the present invention, = 13- The amount of the thermofusible substance added should be kept within the above I field.
love.

In addition, in the present invention, (1:J'.
It is possible to contain cheap polymers, bases, biomaterials, fillers and other substances.

Acidic substances: Acidic substances are added as necessary to prevent coupling reactions and for storage stability, and include the following.

4F-Carbonic acid, citric acid, boric acid, lactic acid, gluconic acid, sulfuric acid, etc.

Basic substance: A basic substance is added as necessary to cause a Cassilling reaction during heating, and examples of the basic substance include the following.

Caustic alkalis and alkali carbonates such as thorium hydroxide, cal/rum hydroxide, and potassium carbonate.

Substances that generate basicity when heated include urea, thiourea and their derivatives, -14 to alkali salts of tric-11 acetic acid, gelatinized anthene, anthene sulfate, and ammonium sodium citrate.

Filler: d,
911 Well, there are two things:

Fine particles of styrene resin, fine particles of urea-formalin condensate resin, solid particles of organic and inorganic yarns such as γ-luminium hydroxide, magnesium hydroxide, calcium carbonate, titanium, talc, kaolin, /rif 1, and alumina.

Other auxiliary ingredients include ill, to inhibit or assist color development, zinc chloride, zinc sulfate, sodium citrate, gubunicine sulfate, tunorsium dalconate, sorbitol,
Zatska rose is used.

In order to obtain the heat-sensitive delectable film according to the present invention, a layer-forming coating solution is prepared by dissolving or dispersing each of the above-mentioned components in an appropriate solvent, and this coating solution is applied to paper, synthetic paper, plastic film, etc. Each layer is coated on a conventional support such as a metal laminate to form a heat-sensitive coloring layer having a desired structure (1) and dried. 3 4 for this invention? The solvent for dispersing the layer-forming components in solution C or Kl is appropriately selected depending on the properties of the layer to be formed and the purpose of formation. With such a solvent [-, water or an organic solvent dissolved in water] aqueous solvent,
Bensen, Toruninin, Gisoren, ■-Hegisan, +1
- Nonpolar organic solvents such as hebutane, xane, and Kuden-1; polar solvents such as methylinobutyl ketone, methyl cellosolve, acetone, methyl ethyl carbon, and dimethyl ether; Examples include quantitative media. As a solvent for rhonone ester resin, /
Examples include 1-pebutane, methyl/1-pentane, 1-chlorhexane, methyl-chlorine, ethyl-7-chlorhegizan, etc.

In the present invention, the separation of the 1J horn silar and the azo compound is carried out in the same manner as in the conventional method, by adhering "l di/-" to ster resin on the surface of the coupler nike/and/azo compound. This can be achieved by interposing a rosin ester resin layer between a single layer of chair and a diazo compound layer.

The heat-sensitive recording material of the present invention can be advantageously applied in various heat-sensitive recording fields, especially as output recording paper for FAXOMI IJ and electronic computers that require high-speed recording.
Furthermore, after forming an image by heating the lifting platform of the present invention, the letters and images recorded on the surface thereof can be fixed by dissolving the unreacted azo compound with light. - Furthermore, the heat-sensitive recording material of the present invention has no clumps before recording and has excellent long-term storage stability. It can be applied to recording necessary beats and creating them.

Next, the present invention will be explained in more detail 1 by way of examples.

Example [Liquid A] =-17- Stearic acid amide 15
Gluconic acid 1
〃Charcoal 1 flight Cal/Rum
4% ttnk “Kohegizan”
54 l/The above composition was milled using a ball mill,
After dispersing for 12 hours, rosin-modified phenolic resin (';:'e
, Kawa Kagaku Co., Ltd. Manol 361) ] 5 Add part Eiii and mix and stir in step 1 to prepare dispersion A. [Liquid B] Polyvinyl alcohol (lO% water 1 byh) to
tt water
Dispersion B was prepared by dispersing the above composition in a ball mill for 124 hours at 1 to 18 hours.

[Liquid C]

Paraffin wax 3
Cyclohexane 88
Dispersion C was prepared by dispersing the above composition for 24 hours using a ball mill.

[Liquid D]

Phloroglucin 5 parts by weight Montan wax (Hex-i 01)-WAX)
2 1/Kaolin
2 Cyclohexane
87/l The above composition was dispersed for 24 hours using a ball mill to prepare a dispersion liquid.

(Liquid E) 2 + 3-/e 1 m Ki7 nanota v7-66 tun'rfMls 1 dose of sulfone Sodium trichloroacetic acid 5
//Magnesium stearate 7
〃water
71/l The above composition was milled in a ball mill for 1~
Dispersion E was prepared by dispersing for 24 hours.

[F liquid]

Stearic acid amide l O-
+lj Gane II Rosin modified phenol tree JIFr
5 ///Kurohegisan
85 〃''-The above composition was dispersed for 24 hours using a ball mill to prepare a dispersion liquid 1-.

Prepare the i- solution as described above and mix the ζA solution to 1 solution in Table 1 to make a can solution.'' - Quality paper (5 (l fl /7712)
, applied to the skin, dried, and then calendered 4.1
- A heat-sensitive recording material O.1 with a smoothness of 400 seconds was prepared (7
[The amount of adhesion for each reason is 2.0 to 3°02/m2 (for one convex shape)].

Clothing-1 Using the heat-sensitive recording material obtained as above as a sample, G-1
After printing in 1 mode, Kucobee High Start Type 4 [Co., Ltd.
Ricoh] was used to fully expose and fix the image. These materials developed color even when heated, and it was thought that the image would disappear if the organic solvent was slaked.

Next, the heat-sensitive recording materials described in 4 above were tested for color density and storage stability. The results are shown in Table-2.

Next, the solid print density of the color density gauge FAX 303 in the G-■ mode was measured using a Macbeth density meter (RD-514). 1.Storability is when the sample is stored at a temperature of 40°C and a humidity of 90% FL.
A forced deterioration test in which the sample was left in a dark place for 24 hours at a temperature of 60°C and a temperature of 0% 1 ull was tested.
− The skin concentration was measured. In this case, a Macbeth diagonal meter was used before and after the dll+foot density n1 test and after exposure.

Furthermore, in Comparative Example 100h3, polyester resin (MWW18O49) was used instead of the rosin-modified phenolic resin used in Example 1 + 2 + 3.

From the results shown in Table 2, Clothing 2, all of the products of the present invention were satisfactory in terms of color density and shelf life.

Patent applicant Ricoh Co., Ltd. Agent: Patent Attorney Toshiaki Ikeura =22=

Claims (1)

[Claims] (1) A diazo type thermosensitive recording phase separation system in which a diazo compound, a coupler and a heat-fusible substance are supported on a support, in which a rosin ester resin is used as a separating agent between the diazo compound and the coupler. Heat sensitivity record by month.