JPS59190886A - Thermal recording material - Google Patents

Abstract

PURPOSE:To obtain a thermal recording material excellent in live preservability and high in thermal color forming property, by a method wherein at least one main constituent is emulsified, and thereafter a wall of a high polymeric substance is formed around particles of the emulsified material to microencapsulate the latter, in a diazo base thermal recording material. CONSTITUTION:One or more of a diazo compound, a coupling component and a color forming adjuvant are dissolved or dispersed in a solvent such as a phosphoric acid ester or a phthalate, and a wall of a high polymeric substance is formed around the oily particles thus formed. Polyurethane, polyurea, a polyamide, a polyester or the like may be mentioned as the high polymeric substance. When using polyurethane, a polyvalent isocianate and a polyol are mixed into an oily liquid to be microencapsulated, the resultant mixture is emulsified or dispersed in water, and temperature is raised to induce a high polymer forming reaction at the interfaces of the oily particles, thereby producing walls of microcapsules. Components other than the core substance are incorporated in a photosensitive layer on the outside of the microcapsules. The thus obtained microcapsules permit each of the components to permeate therethrough with the result of a reaction, without being broken, when being heated.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-sensitive recording material, and particularly to a diazo-based heat-sensitive recording material in which M can be determined. More specifically, the present invention relates to a heat-sensitive recording material that has excellent storage stability before thermal recording, high color density during thermal recording, and is capable of light fixing after thermal recording.

The thermal recording method has the following advantages: (1) No phenomenon is required; (2) When the support is paper, the paper quality is similar to that of ordinary paper; (3) it is easy to handle; (4) the color density is high. (5) The recording device is simple and inexpensive, and (6) there is no noise during recording, so it has become rapidly popular in the field of facsimiles and printers in recent years. As the heat-sensitive recording material, a leuco color-forming heat-sensitive recording material, which is excellent in color development fatigue and color development speed, is mainly used.

However, leuco color-forming heat-sensitive recording materials suffer from adhesion of solvents during handling and heating after recording.fb, 17
However, it has the disadvantage of staining the recorded image, and also has the disadvantage of being discolored by the plasticizer in the cellophane tape. In order to prevent color development due to careless handling, granular wax is added (Tokuko Sho J-(
1; l-141331), or providing a coating layer to prevent the penetration of plasticizer (Utility Model Publication No. 3-t-72!36)
≠) etc. are known. However, the trench was not completely satisfactory, and it was not used for the purpose of preventing falsification after recording, and there was a strong desire for improvement. As a method for stopping color development in unnecessary areas after thermal recording, Japanese Patent Application Laid-open No. 5
Using a heat-sensitive recording material comprising a diazo compound, a coupling component, and an alkali generator or coloring aid as disclosed in JP-A No. 7-/KO30♂Otsu, JP-A-67-/2JO-2, etc. A known method is to irradiate light after recording to decompose unreacted diazo compounds and stop the release of Qk. However, pre-coupling of this recording material gradually progresses during storage, and undesirable gradual discoloration (fogging) may occur. For this purpose, any of the coloring components/blends are discontinuously grained.
F5 (solid fraction) is present in the form of F5 to prevent contact between the components and prevent pre-coupling. ) is still not sufficient, and there is a drawback that the heat release 11'l'i is reduced. Any other measures to minimize total contact between the components with the diazo compound and the coupler component? It is known that it separates as a separate layer. This method is for raw preservation.
Although the raw material is well-formed, the thermal color development is greatly reduced.
It is not practical because it cannot respond to speed recording with a short pulse width. Furthermore, as a method to satisfy both raw storage stability and thermal color development properties, either the cambling component or the color development aid may be replaced with a non-polar waxy substance (JP-A No. 7-≠G/No. 1, JP-A-J7-
/G No. 2636) and hydrophobic polymers
! It is known that W can be separated from other components by encapsulating it with l-7-/ri2 tag ≠ number). However, in these capsules, C microcapsules are formed by dissolving the wax or polymeric substance in the solvent and completely dissolving or dispersing the coloring component in the bath liquid. For this purpose, when the coloring component is dissolved and formed, the coloring component does not become the core material of the microcapsule, but mixes uniformly with the microcapsule material, and precoupling gradually occurs at the wall interface of the microcapsule during storage. This progresses to the point where one cow stored raw is not fully satisfied. In addition, when a color-forming component is dispersed and formed, the color-forming reaction does not occur unless the walls of the microcapsules are thermally melted, resulting in a decrease in thermal color-forming properties. Furthermore, there is a manufacturing problem in that the solvent used to dissolve the wax or polymer IW must be removed after forming the microcapsules, and this method is not completely satisfactory.

Therefore, the first object of the present invention is to provide a heat-sensitive recording material that has excellent shelf life and is thermochromic.

The second object of the present invention is to completely stop coloring in unpleasant coloring areas by photodegrading the diazo compound in the bed reaction after thermal recording (hereinafter referred to as
The object of the present invention is to provide a heat-sensitive recording material which can be called an electric layer.

A third object of the present invention is to provide a heat-sensitive recording material with excellent manufacturing suitability.

As a result of intensive research, the inventor of the present invention, Kishi, has found that diazo compounds, camping ingredients, and coloring aids can be contained in microcapsules, or both types can be contained in the same or separate microcapsules. The walls of the microcapsules were achieved by emulsifying the core material j- of the microcapsules and then using a heat-sensitive recording material made of a polymer material formed around the core material by polymerization.

The microcapsules of the present invention are destroyed by heat or pressure, as used in conventional recording materials, and react with the reactive substance contained in the core of the microcapsules and the biological chamber outside the microcapsules. This method does not cause a coloring reaction by contacting the microcapsules with each other, but by thermally melting the core of the microcapsule and the reactive substance present outside, the reaction material permeates through the microcapsule wall and causes a reaction. Until now, it has been known that when microcapsule walls are formed by a polymerization method, they do not become completely impermeable membranes but are permeable. The permeability of this microcapsule wall was known as a phenomenon in which low-molecular substances gradually permeate over a long period of time, but the phenomenon of instantaneous permeation due to heating as in the present invention was unknown. . Therefore, the microcapsule wall of the present invention must be melted or softened by heat, or
In fact, it has been found that the strength of the wall's high melting point results in superior shelf life.

Even when the microcapsule dispersion produced by the method of the present invention is removed and heated, the walls hardly melt or soften.

By selecting the material and film thickness of the microcapsule wall of the present invention, the core substance of the microcapsule can be in a solution state, a semi-solid state, or a solid state, but the solution state allows instantaneous permeation during thermal recording. Alternatively, it is preferable because it causes a color reaction. Therefore, it is preferable to use a high boiling point solvent that is liquid at room temperature as the core material component of the present invention.

The diazo compound used in the present invention (general formula ArN
It is a diazonium compound represented by z + (In the formula, Ar represents a substituted or unsubstituted aromatic moiety, N2+ represents a diazonium group, and X-
represents an acid anion. ) Concrete formula of diazonium compound which converts salt into form 11 and 1
- t-diazo-/-dimethylaminebenzene, guashiasi/-diethylaminobenzene, Hiro-diazo-
/-dipropyl-γminobenzene, ≠-diazo/-methylbenzylaminobenzene, ≠-diazo/-dibedylaminobenzene, Hiro-diazo/-ethylhydroxyethylaminobenzene, ≠-diazo l-diethylamino-3-methoxybenzene, gou diazo-/-dimethylamine-2-merhenpine, gou diazo/-penzoylamino-2, J-7 ethoxybenzene, ≠-thiazo/-morpholinobenzene, a-thiazo/-morpholino-, 2, J--jethoxybenzene, Hiro-diazo-
l-Morpholino-coatadibutoxybenzene, gusiacy/-7nilinobenzene, ≠-dino'cy/-tolylmercapto-2,J-jethoxybenzene, gauge ゛azo/, 4L-methoxyhencyylamino-λ, J
-diethoxybenzene and the like.

Specific examples of acid anions include “F2n-1-ICOO
-(n represents 3 to ri), CmF2rn-H8O3(
mId 2~J' fz), (CI!F2l-4
-ISO2)2CH- (l represents / to /l), C(CHa)s r -terBF4 +PF6, and the like.

Specific examples of the diazo compound (diazonium salt) include the following examples.

-/0- 0C2H5 OC2H5 C2H5 C4H9 The coupling component used in the present invention is one that forms a dye by coupling with a diazo compound (diazonium salt) in a basic atmosphere, and specific examples include resorcin, phloroglucin, 2゜Sodium 3-dihydroxynaphthalene-2-sulfonate, /-hydroxy-2-
Naphthoic acid morpholinopropylamide, /, j-dihydroxynaphthalene,! , 3-dihydroxynaphthalene,
Ko.

3-dihydroxy-6-sulfanylnaphthalene, co-hydroxy-3-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthoic acid anilide, non-hydroxy-3-naphthoic acid-λ'-methylanilide, non-hydroxy-3-naphthoic acid Acid ethanolamide, λ-hydroxy-3-naphthoic acid octylamide, no-hydroxy-3-naphthoic acid-N-dotecyl-oxy-probylamide, λ-hydroxy-3-naphthoic acid detradecylamide, acetanilide, acetoacetanilide, benzoyl Acetanilide, /-phenyl-3-methyl-
Yo-pyrazolone, /-(2', 4".

+ ' -+-lichlorophenyl)-3-benzamide-! -pyrazolone, /-(2',V',t'-trichlorophenyl)-3-anilino-j-pyrazolone, /-phenyl-3-phenylacetamide-/3--j-pyrazolone, and the like. Furthermore, by using two or more of these coupling components in combination, an image of any color tone can be obtained.

As the color development aid of the present invention, a poorly water-soluble or water-insoluble basic substance or a substance that generates an alkali when heated is used.

Color development aids include inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, virols, pyrimidines, piperazines,
Examples include nitrogen-containing complexes such as guanidines, indoles, imidazoles, imidacillines, triazoles, morpholines, piperidines, amidines, formazines, and pyridine. Specific examples of these include Example j id' ammonium acetate, tricyclohegycylamine, tribenzylamine, ophtatesolbenzylamine, stearylamine, allyl urea, thiourea, methylthiourea, allylthiourea, ethylenethiourea 1.2 −
Benzyl imidazole, ≠-phenylimitazole, cophenylene-Hiro-methyl-/Hiro-imidazole, λ-undecyl-imidacillin, λ, p
, t-triflyrucoimidazoline, /.

λ-diphenyl-V, V-dimethyl-,2-imidazo1
J71.2-Phenyl-λ-imidasoline,/.

λ, 3-triphenylguanidine, /, 2-ditolylguanidine, /, 2-dicyclohexylguanidine, /,
2.3-1-dicyclohexylguanidine, guanidine trichloroacetic acid + fi, N,N'-dibenzylpiperazine, F,4''-dithiomorpholine, morphonium trichloroacetate, suaminopenzothiazole, 2-benzoylhydra Dino-benzothiazole is one such coloring agent.Two or more of these coloring agents can also be used in combination.

In order to dissolve the core substance of the microcapsules of the present invention, i. Naphthalene, diarylethane, etc. are used.

Specific examples include tricresyl phosphate, trioctyl phosphate, octyldiphenyl phosphate, tricyclohexyl phosphate, dibutyl phthalate, dioctyl phthalate, dilaurate phthalate, dicyclohexyl phthalate, phthyl oleate, diethylene glycol dibenzoate, diotyl sepacate, Didutyl sebacate, dioctyl adipate, trioctinopectate trimellitate, acetyltriethyl trimellitate, octyl maleate, -f-propylbiphenyl, in-amyl biphenyl, chlorine f-hibarafine, diisopropylnaphthalene, diarylethane,
Examples include ≠-ditertiary aminophenol, N,N-)butyl-2-butoxy-j-tertiary octylaniline, and the like.

The microcapsules of the present invention are made by emulsifying a core material and then forming a wall of a polymeric material around the oil droplets.

During the daytime molecular substance formation, the actant is inside the oil droplet and/or
or added to the outside of the oil droplet.

Specific examples of polymeric substances include polyurethane, polyurea, polyamide, polyester, polycarbonate,
Examples include urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer, gelatin, polyvinylpyrrolidone, polyvinyl alcohol, and the like.

Two types of polymeric substances can also be used as overlays.

Preferred polymeric materials are polyurethanes, polyureas, polyamides, polyesters, polycarbonates, and historically preferred are polyurethanes and polyureas.

As the material of the polymeric material, a polymeric material having a melting point of J'00C or higher that does not melt at the temperature LS during thermal recording is preferable.

Among the diazo compound, coupling component, and coloring aid that are the main components used in the present invention, the core material of the microcapsule is the diazo compound, the coupling component, the coloring aid, the diazo compound and the camping component, and the diazo compound and coloring aid. Auxiliary agent or camping ingredient and coloring auxiliary agent? Can be used. When two types are used as the core material, they can be contained in the same microcapsule or in separate microcapsules.77- The components of the pond that are not used as the core material of the microcapsule can be contained in the photosensitive material outside the microcapsule.
used for.

The microcapsule wall of the present invention is particularly effective when using the microcapsule 1' method, which involves polymerization of a glue actant from inside an oil droplet. That is, capsules suitable as a recording material having uniform particle size and excellent life-saving σ-opening can be obtained within a short time.

This method and specific examples of 1-hi combinations can be found in U.S. Watch No. 3,72 Otsu, Go Hiro issue, No. 3,796. Akira N of Otsu No. 2
It is described in book a.

For example, when used as a capsule wall material with polyurethane [
11 polyvalent isocyanate 1 and a second substance (e.g. polyol) forming the anti-15L capsule wall with it ff:
By mixing the oil to be used in the capsule into a raw liquid, dispersing it in water, and then increasing the temperature, a sieve molecule forming reaction occurs at the oil-water interface to form a microcapsule wall. At this time, an auxiliary solvent with a low point and strong dissolving power can be used in the oily liquid.

-1g- In this case, regarding the polyisocyanate-1 used and the polyol and polyamine that react with it, US Patent No. 3/3 Tough/4, US Pat. Otsu 2! No. 37932
t1, special public show 4t and -'103≠7, same≠5'-2
F/j′ri issue, Tokukai Sho! J-foiyi, 4t, 1
'-,1' tI-Of J, and they can also be used.

Furthermore, tin salt or the like can also be used in combination to promote the urethane reaction.

When making microcapsules, water-soluble polymers can be used.Water-soluble polymers are water-soluble anionic polymers, nonionic polymers, both 1. raw polymers, gold-containing, and anionic polymers. Both natural and synthetic compounds can be used as C, and examples include those having -COO-1 to S〇- groups. Specific anionic natural polymers include gum arabic and alginic acid, while semi-synthetic products include carphomethylcellulose, metal-ceratin, sulfuric acid f-hytenbune, sulfuric acid f-hycellulose, and lignin sulfonic acid.

In addition, the products include maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers, and Examples include copolymers and carboxy-modified raw polyvinyl alcohols.

Examples of amphoteric compounds include t:1 gelanan.

These water bath 1 raw Satsuma molecules are used as an aqueous solution of 0.0/~/Ow t%. The particle size of microcapsules is 2
0μ to a! ! ! I feel sorry for myself. Generally, if the particle size exceeds λOμ, the quality of the printed image tends to be poor.

In particular, the heating film by the thermal head (41')
In the case of starting from scratch, gμ or less is preferable in order to avoid pressure fog.

One microcapsule can be made from an emulsion containing 2 tr, 2 wt % or more of the ingredients to be contained in the microcapsule.

Even if the diazo compound, carnobling component, and coloring aid used in the invention are contained in M of the microcapsule,
Alternatively, even if it is contained in the photosensitive T- outside of the microcapsule, the coupling component is used at a ratio of 0.7 to 10 parts by weight and the coloring aid is used at a ratio of 0.1 to 20 parts by weight relative to the diazo compound/heavy sensitive area. It is preferable to do so. Further, it is preferable that the diazo compound is O,OS~λ,09/m''f1.

When the diazo compound, coupling component, and coloring aid used in the present invention are not microencapsulated, it is preferable to disperse them in solid form using a sand mill or the like. in this case,
Each layer is separately dispersed in a water-soluble polymer solution. Preferred water-soluble polymers include water-soluble polymers used when making microcapsules. At this time, the concentration of the water-soluble polymer is 2 to 30w1%, and the diazo compound, coupling component, and coloring aid are each 3 to 'A Ow t% with respect to the water-soluble polymer solution of C. Injected.

The dispersed particle size is preferably 10 microns or more.

The heat-sensitive recording material of the present invention contains silica, barium oxide, titanium hydroxide, aluminum 2/-minilum hydroxide, zinc oxide, and carbonic acid for the purpose of improving the rainproofing and writing properties of statesking on the thermal head. Pigments such as calcium, fine powders such as styrene beads and urea-melamine resin can be used. Similarly, metal soaps can also be used to prevent sticking. The amount of these used is 0.2 to 7 g/m2.

Further, the heat-sensitive recording material of the present invention may contain a heat-melting shearing substance in order to increase the thermal recording density.

The heat-melting biomaterial is a substance that is solid at room temperature and has a melting point of SO~/jO0C that melts when heated by a thermal head, and is a substance that dissolves a diazo compound, a coupling component, or a coloring aid. The thermofusible M substance is 0. /~10μ
It is used in an amount of 0.2 to 797 m2 of solids by dispersing it in the form of particles. Specific examples of heat-melting substances include fatty acid amides, N-substituted fatty acid amides, ketone compounds, N-substituted carbamate ratios, urea compounds, esters, and the like.

The heat-sensitive recording material of the present invention may be coated with a suitable binder.

As a binder, polyvinyl alcohol, etc. 22
- Chillcellulose, carboxymethylcellulose, hydroxyprobylcellulose, gum arabic, gelatin, polyvinylpyrrolidone, casein, styrene-butadiene latex, acrylonitrile-getadiene latex, polyvinyl acetate, nisder polyacrylate, ethylene-vinyl acetate copolymer Various emulsions of , can be used. The amount used is solid content O, S - 2/m2.

In the present invention, in addition to the materials from the north, citric acid is used as an acid stabilizer.
n Acid, oxalic acid, boric acid, phosphoric acid, birophosphoric acid, all can be added.

The heat-sensitive recording material of the present invention includes a diazo compound, a camping component, a main component of a coloring aid, and other additives, which are added as an ingredient in microcapsules, or are dispersed in solid form, or dissolved in an aqueous solution. After mixing, a coating solution is created, which is coated and dried on a support such as paper or synthetic resin film using a coating method such as bar coating, blade coating, air knife coating, gravure coating, roll coating, spray coating, or tip coating. The solid content is 2゜j~/! j
A heat-sensitive layer of j/m2 is provided. Another method is to add the camping component, the main component of the coloring aid, and other additives as the core material of the microcapsules, or to partially separate them into solids, or to dissolve them as an aqueous solution and then mix them. Make a coating solution, apply it on the support, dry it, and reduce the solid content to 2.
A precoat 1- of ~109/m2 is provided, and the main component diazo compound and other additives are added thereon as core materials of microcapsules, or they are solid dispersed or dissolved as an aqueous solution and then mixed. It is also possible to apply a coating liquid prepared by the method and dry it to form a layered type with a solid content of 109/- and a coating r- of 2. At least a small amount of the diazo compound, camping component, and coloring aid which are the main components of these heat-sensitive recording materials are contained in the microcapsules. Product 1-type thermal recording material is product! A case where the order of - is opposite to the above-mentioned end layer is also 1:iT function, and as a coating method, successive repeating of lamination or simultaneous coating is also ijJ function.

This laminated heat-sensitive recording material exhibits particularly excellent long-term storage stability.

The heat-sensitive recording material of the present invention can be used as printer paper for facsimiles and electronic computers that require high-speed recording, and can be fixed by opening the light and decomposing unreacted diazo compounds after printing by heating. . In addition, it can also be used as a heat-developable copying paper.

Examples are shown below, but the present invention is not limited thereto. Note that "part" indicating the amount added represents 1 part by weight.

Example Using the following diazo compounds (1) to (3), add appropriate amounts of the diazo compound, xylylene diisocyanate, and trimethylolpropane (,?:/) adduct 70 in a dark room by changing the amount of each added. Addition I] was dissolved in a mixed solvent of 20 parts of diptyl phthalate and 5 parts of ethyl acetate. 5. The solution of this diazo compound was mixed into an aqueous polyvinyl alcohol solution in which 5.2 parts of polyvinyl alcohol was dissolved in Jg parts of water. Milk was dispersed using zooC to obtain a milk solution with an average particle size of 3μ.Add 10 parts of water to the obtained emulsion.
After 2 hours, three types of capsule liquids containing diazo compound as the core material were obtained.

Diazo compound (1) C4H9 diazo compound (2) N-azo compound (3) 2 t- To prepare a dispersion of the coupling component, the following coupling components (1) to (3) were used, respectively. Add to 700 parts of water at a ratio of 20 parts of the coupling component and 1 part of polyvinyl urea/L/coal j and disperse with a Sandomi I for about 2≠ hours to disperse three types of coupling components with an average grain size of about 3μ. I got something.

Campling component (1) 2-Hydroxy-3-naphthoic acid morpholinopropylamide Campling component (2) λ-hydroxy-3-naphthoic acid anilide coupling component (3) Cohydrohydric 3-naphthoic acid-2'-methyl anilide Next The λθ part of triphenylguanidine and the part of polyvinyl alcohol were added to 100 parts of water and dispersed in a sand mill for about 21 hours to obtain a dispersion of triphenylguanidine with an average grain size of about 3 μm.

Azo compound capsule liquid jO obtained as above
part, dispersion of coupling component/part and dispersion of triphenylguanidine lj part kj% zinc stearate 20
A coating solution was prepared by adding the following ingredients to the coating solution.

This coating solution was coated on a smooth high-quality paper (!; Recording materials (1) to (5) were obtained. The combinations of the types of diazo compounds and types of cold 710, @, and coupling components are shown in Table 2.

On the other hand, for comparison, a heat-sensitive recording material without encapsulating a diazo compound was prepared. In this case, use an appropriate amount of diazo compound and polyvinyl alcohol.

Add 2 parts to 30 g of water and disperse in a sand mill for about 2V to make a dispersion with an average particle size of 403 μm, 2j part of diazo compound dispersion, Ir part of campling component dispersion, and triphenylguanidine dispersion. Add 75 parts to 20 parts of j% zinc stearate to make a coating solution, and apply the mixture so that the coating amount of each diazo compound is the same to prepare a heat-sensitive recording material (
6) to (8) were obtained.

The combinations of the type of diazo compound, the amount of oxidation, and the type of camping component are shown in the table.

The heat-sensitive recording materials (1) to (8) obtained as described above were processed using GII mode (Panafax 7200) (Matsushita Densen).
Co., Ltd.) and then Ricovino Istar 14
The entire surface was exposed to light using a mold (manufactured by Ricoh ■) and fixed.

The blue density of the resulting recorded image was measured using a Macbeth reflectometer (7).The results are shown in Table 1.- When thermal recording was performed again on the fixed and fixed areas, no image was recorded and no image was fixed. It was confirmed that

Next, in order to check the raw shelf life, heat recording materials (1) to (1)
The background density (fog) of 8) and these were stored in a dark place for 2 hours under the conditions of 2ro, 0C1, relative humidity, O, and RH, and after performing a forced deterioration test, the fog was measured on the Macbeth reflection density side. I saw Weird Sio. -30- As can be seen from Table ■, all of the non-inventions in which Diasogo and the compound were encapsulated once had high image density, similar to the comparative example without encapsulated capsules, and furthermore, the fog after the forced inferiority test was low. The increase is small and the storage stability is much better than that of the comparative example without encapsulation.

Examples 9 to 16 In Examples 11 to 3, a capsule liquid of the coupling component was prepared by adding 5 parts of the camping component instead of the N'angohi compound in the method for preparing the capsule liquid, and a dispersion of the camping component was prepared. A suitable amount of a diazo compound is added in place of 20 parts of the coupling component in the method described above to prepare a dispersion of the zoazo compound, and 10 parts of the capsule liquid of the coupling component and a dispersion of the diazo compound/! parts, 15 parts of a dispersion of triphenylguanidine, and! Coating liquids containing 20 parts of zinc stearate were obtained in the same manner as in Examples (1) to (5) to obtain heat-sensitive recording materials (9) to 03). The types and additions of diazo compounds and the combinations of types of cutting components are shown in Table 3. On the other hand, for comparison, unlike the present invention,
A heat-sensitive recording material was prepared by a method of forming a capsule wall using commercially polymerized molecular substances. In this case, vinyl acetate-butyl methacrylate-styrene copolymer to@t is dissolved in θ part of cyclohexaphtha, j part of Cassilling component is completely dissolved in the center, and polyvinyl alcohol!
. It was added to a solution consisting of 2 parts and 1 part of water. This mixed solution was emulsified and dispersed by stirring at room speed at room temperature, and distilled under reduced pressure while stirring to remove cyclohexane to obtain a capsule liquid of the camping component. Next, capsule *-e was filtered, washed with water, and vacuum dried to obtain capsule powder. A coating solution was prepared by adding 5 parts of capsule powder to the obtained Cassicell powder in place of 60 parts of capsule solution in the camping component of the coating solution used for heat-sensitive recording materials (9) to (13) (7JI). Examples 1-B
Thermosensitive recording materials (14) to (Ili) were obtained in the same manner as above.

The combinations of types and amounts of diazo compounds and types of coupling components are shown in Table ■[.

The recorded image density, fog before forced deterioration, and fog after forced deterioration were measured for the heat-sensitive recording materials (9) to 06) obtained in the above manner in the same manner as in Examples 1 to 8, and the results are shown in Table H. show. Heat-sensitive recording material (9) - (3 for the fixing part of I fit)
2- Then, thermal recording was performed again, but it was confirmed that one area of the image was not recorded and was fixed.

As you can see from the table, the compulsory component is used as the core material in milk [Hishita Kumi, the capsule wall of the 3% molecular material is polymerized to open the core material? All of the inventions formed in 17
] After dissolving the polymerized polymer material, microcapsules are formed, and compared to the comparative example, the image density is higher and the forced degradation is less.
The increase in capri in Hitestokyo is also small, and its shelf life has been compromised.

EXAMPLES In Examples 1 to 8, triphenylguanidine was used instead of the diazo compound in the method for preparing capsule liquid! A capsule liquid was prepared by adding 17 parts. borrowed capsule liquid 60j
Miyako and Minoru! 1IjlU 75 parts of the dispersion of campling component (1) prepared in Examples 9 to 16 and 75 parts of the dispersion of diazo polymer (1) prepared in Examples 9 to 16! 320 parts of stearic acid was added to 320 parts of the stearic acid mixture and coated for one night.

This coating liquid was applied to the same cloth as the actual sister Y01-8 (E) to prepare a heat-sensitive recording material (17), and a test sample was prepared.

, the results are shown in Table 1■.

Laughing Ya'191118 Husband! In the method for preparing the capsule liquid of 141-8, diazo[polymerization'1lJ(1)
7 parts and 7 parts of coupling component (2) were added to prepare a capsule liquid. I was asked about the capsule liquid Otsuyu f Kou and Minoru 1#
, l-riphenylguanidine, which was present in Examples 1 to 8, 20
A coating solution was prepared by adding 7.5' parts of zinc stearate to 7.5' parts of zinc stearate, and a heat-sensitive recording material (18) was prepared and tested in the same manner as in Examples 1 to 8. The results are shown in Table IIIK.

Table■ In Table 11r, the heat sensitive record 4, Sea urchin family ((7) to (+), the main ingredient /P7:j is contained in the capsule of this book, but from Table 11r, sea urchin) , Image system 1 government is 1.” 1 is a trench, forced inferiority r barley capri paste 1
KAGAKOZA〈Yuen IIAE is excellent.

Example 19 In the method for preparing capsule liquids of diazo compounds in Examples 1 to 8, instead of 10 parts of the adduct of xyzolylene isocyanate and trimethylolpropane (3:/), the same compound and tolylene diisocyanate were used. Trimethylolpropane (J
A supplement liquid containing diazo compound (1) as the core material was obtained in the same manner except that the diazo compound (1) was used as the core material. 0 parts of the obtained capsule liquid and dispersion of coupling component (1) prepared in Examples 1 to 8 '<'II/J m and dispersion of triphenylguanidine/part digit zinc stearate 20 In addition to Part 1, Coating i was manufactured by A. This coating solution was applied in the same manner as in Examples 1 to 8 (2) A heat-sensitive recording material (+91) was prepared and tested.
Capri before and after hitest is Olo and 0. /
3, the image density was high, and the preservability was also good. Ou 9120 The bath liquid in which the diazo compound was dissolved in the method for making the capsule liquid of Examples 1 to 8 was milked. The same procedure was carried out except that instead of the aqueous solution of polyvinyl alcohol, a solution ♀ in which 2 parts of polyvinyl alcohol, 1 part of dried divinyl alcohol, and 1 part of water was dissolved was used. 50 parts of capsule liquid of diazo compound (1), 75 parts of dispersion of counseling component (1), and dispersion of triphenylguanidine/J
Partially added 20 parts of zinc stearate and 1 part of the coating solution.
2. All thermosensitive recording materials were prepared in the same manner as in Examples 11 to 8. When I tested this completely, the image IRm degree was /, /,
Forced % (capris before and after hitest are o and og respectively)
The image quality was 0/3, the image density was good, and the storage stability was excellent.

Example z1 A heat-sensitive recording material was prepared in the same manner as in Example 2() except that 0.2 part of prephthalic acid chloride was further added to the diazo (hypolysate) dissolved core material in the method for making the capsule liquid of Example 20. The capsule wall was made of polyamide and polyamide.

this! ``Tako'': A Japanese test, the test was 7, and the picture (the luminous intensity is /, /, wholesale) is inferior [Hitest's front and drinking capri are 00-3 - or and 7.0, respectively, and are further preserved. It had excellent properties.

Patent applicant Fuji Photo Film Co., Ltd. 37- Procedural amendment Showa! 1) Indication of the incident Showa TR year patent application No. tzoμ3
No. 2, Title of the invention Thermal recording material 3, Relationship with the case of the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Tomiko Rokushin Film Co., Ltd. t Target of amendment Invention of the specification The description of koji in "Detailed explanation of the invention" in the statement of contents of the amendment is amended as follows.

/) 6th member, 7th line “Hot bath melting” meeting 1 sword oil and correct it.

, 2) Page 7, line 3 "Dispersion" meeting 1-core substance-1 and correct it.

3) Correct "diazo-7-dibenzylaminobenzene" on page g, line j to "diazo-1-dibenzylaminobenzene."

μ) Page 1j, line 10 "Morphonium trichloroacetate" −/− Correct it to "Morpho 1)ium trichloroacetic acid".

Page 1j/line 1 “Dissolving the core substance” [Dissolution or dispersion of reactive substances] and correct it.

6) Row 76th "Dioctyl adipate" "Dioctyl adipate" and correct it.

7) 1st A member 10th row [Sia I)-Le 1 Tan” 1-/, /'-cyto11ruethane-1 and correct it.

t) 1st page/μth row Before “core substance” 1 reactivity 'al/J? l-contained.” Insert.

9) On page 17, lines 10 to 2, change "Polymeric substances...preferably 2." to -,
2- Delete.

IO) No. iz shell 1st row “I can make it happen.” "I can do it." and correct it.

//) The 20th day is the 1st row, etc. ” followed by r nonion 44, and the molecule is polyvinyl alcohol,
Examples include hydroxyethylcellulose and methylcellulose. , 1 Insert all.

/2) λth/mountain//line To Shun who is “used” "ru" ? r - insert.

/3) No. 25 Tei line 73 1 xylylene diisocyanate” meeting [Xy1) Diisocyanate” and correct it.

/ri 2nd j negative 7η stone "at a rate of" "ke" and correct it.

lj) th λ is the negative coth row "to" "Contained in" and correct it.

lt) Correct as "1-11 phenylguanidine" [1-phenyl-gumethyl imitasol 1] on page 3j, line 10.

/71 page 37, line j After “same compound” "Part 5" Insert.

it) Change the 30th animal to the attached sheet -/.

1) Insert page 31 into the attached sheet -λ and enter the procedural amendment, Showa July 2016, Personal Licensing Agency Commissioner's Palace 1, Indication of the case, Showa TR year patent application No. t, 5-01.
/-3 No. 2, Title of the invention Thermal recording material 3, Relationship to the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. 4, Subject of the amendment Specification The entire statement in the "Detailed Description of the Invention" column 5 of the "Detailed Description of the Invention" section of the Statement of Contents of the Amendment shall be amended as follows.

1) Page 39/line "/, 0" "O0/" and correct it.

Procedural Amendment], Indication of the case Showa rr year patent application No. 4j, 0kyu 3
No. 2, Title of the invention Thermal recording material 3, Relationship to the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji'j
fj"P': Film Co., Ltd. 4, Subject of amendment Column 5 of "Detailed explanation of the invention - 1" of the specification, Contents of amendment
- / page and replace with page 1O-2.

H Examples include BF, PF6-, and the like.

Specific examples of diazo compounds (diazonium salts) include f
Sleep] 1σ rishio 1 button reach μ is shifted.

-10-/- =455 QC4H9 -IO-2- H3

Claims (2)

[Claims] (1) In a heat-sensitive recording material in which a recording layer containing a diazo compound, a coupling component, and a coloring aid is provided on a support, one of the diazo compounds, the coupling component, and the coloring aid is Contained in microcapsules,
or two types are contained in the same or separate microcapsules, and the walls of the microcapsules are made of a polymer material formed around the core material by polymerization after emulsifying the core material of the microcapsule. heat-sensitive recording material. (2) The polymer material is at least one selected from polyurethane, polyurea, polyamide, and polyester.
The heat-sensitive recording material according to claim 1, characterized in that the heat-sensitive recording material is formed by forming a heat-sensitive recording material.