JPS606493A - Thermal recording material - Google Patents

Abstract

PURPOSE:To enhance storage preservability by providing a recording layer, which contains a diazo compound, a coupling component and a color forming aid in such a state that one or more of said reactive components is contained in a microcapsule along with an org. solvent, on a support. CONSTITUTION:At least one of reactive substances such as a diazo compound, a coupling component, a color forming aid or the like is dissolved or dispersed in an org. solvent and the obtained solution or dispersion is microencapsulated. In this case, if the aforementioned three substances are contained in the same microcapsule along with an org. solvent, color fog is generated and, therefore, this method is not practical. The remaining reactive substances are dispersed in a solid form or mixed with the aforementioned microcapsule dispersion as an aqueous solution form to prepare a coating solution which is, in turn, applied to a support such as paper or a synthetic resin film by bar coating or blade coating and, after drying, a heat-sensitive layer with solid content of 2.5-15g/m<2> is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-sensitive recording material, and particularly to a fixable diazo-based heat-sensitive recording material. More specifically, the present invention relates to a 11& thermal recording material which has excellent storage stability before thermal recording, high color development during thermal recording, and is capable of light fixing after thermal recording.

Thermal recording methods are: (1) development is not required; (2) when the support is paper, the quality of the paper is similar to that of ordinary paper; (3) it is easy to handle; (4) the color development rate 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 fields of facsimiles and printers in recent years. As a heat-sensitive recording material for this,
Leuco color-forming heat-sensitive recording materials are mainly used, which are excellent in color development resistance and color development speed.

However, leuco color-forming heat-sensitive recording materials have the disadvantage that they develop color due to handling, heating, or adhesion of bath agents after recording, staining and staining the recorded image, and also decolorizing due to the plasticizer in cellophane tape. It also has the disadvantage of doing so. In order to prevent color development due to rough handling, a wax-like wax is added (
Tokuko Showa 10-/'! 7ta No. 31), and in order to prevent the penetration of plasticizer, provide a;Σ fish layer (Jitsukai Showyu t-/
2j331t'ri, -) Kasa is known. However, it is still not fully satisfactory, and it is not used particularly for the purpose of preventing falsification after recording, and an improvement is strongly desired. JP-A-7-23016, IC'r
Kaisho 57-/? A heat-sensitive recording material consisting of a diazo compound, a coupling component, and an alkali generator or a coloring aid as disclosed in JT092 etc., vl-=Ift: is used to perform light irradiation after thermal recording to remove unreacted diazo. A method of stopping color development by decomposing a compound is known. However, pre-coupling gradually progressed during storage of this recording material.
Undesirable coloring (fogging) may occur. To this end, it has been attempted to prevent contact between the components and prevent pre-coupling by making one of the color-forming components exist in the form of discontinuous particles (solid dispersion). A recording material with a storage stability of 1 (hereinafter referred to as raw storage stability) is not sufficient and has the disadvantage that thermal color development is reduced. As another measure, it is known to separate the diazo compound and the coupler component in separate layers to minimize contact between the components. Although this method improves raw storage stability, the thermal coloring properties are greatly reduced, and it cannot respond to high-speed recording with short pulse widths, making it impractical. Furthermore, as a method to satisfy both raw storage stability and thermal coloring property, either the coupling component or the coloring aid is mixed with a non-polar waxy substance (% Kaishoj7).
It is known that it can be isolated from other components by encapsulating it with a hydrophobic polymeric substance (JP-A No. 41-Hiro, JP-A-17-197-/μ2636) or a hydrophobic polymer substance (JP-A-67-/F-Koba-1). ing. However, in the encapsulation method described above, the wax or polymer substance is dissolved in the solvent, the coloring component is dissolved or dispersed in the solution, and then the solvent is removed by evaporation to form microcapsules. It is something that forms. In this encapsulation method, the coloring component is not completely encapsulated as the core material of the microcapsule, but is mixed uniformly with the microcapsule material, and pre-coupling progresses steadily during storage at the wall interface of the microcapsule, resulting in raw preservation. I'm not fully satisfied with my sex. Also, the walls of the microcapsules are thermally melted and f! Otherwise, no color-forming reaction occurs, 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 polymeric substance must be washed away after forming the microcapsules, which is not completely satisfactory.

Accordingly, a first object of the present invention is to provide a heat-sensitive recording material that has excellent shelf life and high color development speed and color density.

The second purpose of the present invention is to photodecompose the diazo compound irradiated with light after thermal recording to stop color development in unnecessary areas (hereinafter referred to as
The purpose of the present invention is to provide a heat-sensitive recording material that can be used as a heat-sensitive recording material.

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

The first object of the present invention is to provide a heat-developable recording material that decomposes the diazo compound in the lighted area by optical recording and then heats it to develop color in the unlighted area to form a visible image. be.

As a result of intensive research, the present inventors have found that if at least seven types of diazo compounds, coupling components, and coloring aids are microencapsulated together with an organic solvent and coated on a support together with the remaining components, it will be possible to achieve a very suitable purpose. The present invention was achieved by discovering that a heat-sensitive recording sheet can be heated.

In the present invention, as is done in conventional recording materials, the microcapsules are destroyed by heat or pressure to bring the reactive substance contained in the core of the microcapsules into contact with the reactive substance outside the microcapsules. It does not produce a coloring reaction, but reacts with reactive substances present in the core and outside of the microcapsules by passing through the microcapsule walls by heating. In this case, when an organic solvent coexists, the amount of color development during storage is dramatically reduced, and the color development rate and color development gar# are dramatically increased.

It is thought that the increase in color development speed and softness is due to the fact that the solvent swells the microcapsule walls during heating and promotes the permeation of reactive substances. In addition, the rate-determining step in the color-forming reaction is the mutual dissolution of actants, and in this case, the presence of an organic solvent increases the rate of mutual dissolution of actants during heating. It is thought that then.

The decrease in colored turnips during storage is contrary to common sense in this field, and the effect is surprising.

Permeation development of the microcapsule wall has been known as a development in which a low-molecular substance gradually erodes over a long period of time, but as in the present invention, it can be developed without destroying the microcapsule.
A phenomenon in which a reactive substance instantaneously permeates the υ microcapsule wall by heating has not been known.

Therefore, the microcapsule walls of the present invention do not need to be melted or softened by heat, and we have found that the higher the melting point of the walls, the better the shelf life.

In the present invention, after dissolving or dispersing at least seven types of reactive substances such as a diazo compound as a core material, a coupling component, or a coloring aid in an organic solvent, polymerization methods such as interfacial polymerization, external polymerization, and internal polymerization are performed. Preferably, the core material containing the reactive substance and the organic solvent is microencapsulated in the resulting wall material. More preferred wall materials include polyurethane, polyurea, polyamide, and polyester.

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

Tokukai Akira! 7-/As in Takohari, a heat-softening polymer such as a vinyl polymer was used as the material for the wall, and a microencapsulation method by precipitation of the polymer from a solvent was applied to the core material of the present invention. In this case, the heat-sensitive recording material that has been polished has a serious problem of fogging. 6. JP-A-Sho, t7.
- When the microencapsulation method of λ tag μ is applied, not only the color distortion is not improved, but also the coloring speed and coloring density are decreased, and a good heat-sensitive recording material cannot be obtained.

In addition, diazo compounds, coupling components, and coloring aids
When the seeds are contained in the same microcapsule together with an organic solvent, a color cast occurs and the method cannot be put to practical use.

The ion-containing solvent used for the core material in the present invention is a water-insoluble, high-boiling-point solvent, preferably having a boiling point of is'o'c or more. Esters, other carboxylic acids, fatty acids
Amide, alkyl biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene, diarylethane, etc. are used. Specific examples include tricresyl phosphate, trioctyl phosphate, octyldiphenyl phosphate, trichlorohexino' phosphate, dibutyl phthalate, dioctyl phthalate, phthalate dilaurate, dicyclohexyl phthalate, butyl oleate, diethylene glycol dibenzoate, Diotyl sepacate, diduter sepa7oate, dioctyl adipate, trioctyl trimellitate, acetyltriethyl citrate, octyl maleate, octyl maleate, isopropylbiphenyl, inamyl biphenyl, chlorinated paraffin, diimpropylnahumelene, l- l'-ditolylethane,
λ, 4! -ditertiaryaminophenol, N,N-dibutyl-2-butoxy-tarternaryoctylaniline, and the like. Among these, preferred are dibutyl phthalate, diethyl phthalate, dibutyl maleate, and the like.

The diazo compound used in the present invention has the general formula ArNz+
It is a diazonium salt represented by X-, and it is a compound that can develop a color by causing a coupling reaction with a coupling component, and can be decomposed by light.

(In the formula, Ar represents a 1ρ-substituted or unsubstituted aromatic moiety, N2+ represents a diazonium group, and X- represents an acid anion.) Specific examples of diazonium compounds that form salts include ≠
-diazo-l-dimethylaminobenzene, ≠-diazo-1-diethylaminobenzene, μm diazo-7-cypropylaminobenzene, diazo-l-methylbenzylaminobenzene, -diazo-7-dibenzylaminobenzene, μm siaso/- Etherhydroxyethelaminebenzene, φ-diazo 7-diethylamine-3-methoxybenzene, φ-diazo 7-dimethylamino-co-methylbenzene, μm diazo-l-benzoylamino-2,j-jethoxybenzene, ≠-diazo- 7-morpholinobenzene, gusia 7”-/-morpholinoco9
．． 5 Shedkinbenzene, -diazo-l-morpholino-! , j-dibutoxybenzene, l-diazo-7-anilinobenzene, l-diazo l-tolylmercaptoco, terdiethoxybenzene, l-diazo-7,≠-
Methoxybenzoylamino2. Examples include j-jethoxybenzene.

As a specific example of the acid anion, 'C is CnFZn+1cOo
-(n represents 3~?), cmF'2m+1so3
(m represents 2 to g), (αFzz+1SOs+)2
cH- (t represents 1 to /I), HC(C13)3Bli"4, PF6-, and the like.

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

The coupling component used in the present invention is one that forms a color by coupling with a diazo compound (diazonium salt) in a radical atmosphere, and the Jj monolithic side,! :Resorcin, phloroglucin, λ.

Sodium 3-dihydroxynaphthalene-6-sulfonate, l-hydroxy-2-naphthoic acid morpholinopropylamide, 1. ! -dihydroxynaphthalene, co, 3-
Dihydroquinaphthalene, 2゜3-dihydroxy-6-
Sulfanylnaphthalene, 2-hydroxy-3-naphthoic acid morpholinopropylamide, λ-hydroxy-3-
Naphthoic acid anilide, no-hydroxy-3-naphthoic acid Q
-2'-methylanilide, 2-hydroxy-3-naphthoic acid ethanolamide, 2-hydroxy-3-naphthoic acid octylamide, no-hydroxy-3-naphthoic acid C
'1l-N-dodecyl-oxy-probylamide, cohydroxy-3-naphthoic acid tetradecylamide, acetanilide, acetoacetanilide, benzoylacetanilide, l-phenyl-3-methyl-! -Pyrazolone, 7 (2/, da'ni/)lichlorophenyl)-
3-benzamide-y-pyranolone, /-(2', μ1
．． t, I) Lichlorophenyl)-3-anilino-
Examples include pyrazolone, l-phenyl-3-phenylacetamito-1-pyrazolone, and the like. Furthermore, by using two or more of these coupling components in combination, it is possible to obtain an image of any desired tone.

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.

Coloring aids include inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, virols, pyrimidines, piperazines,
Nitrogen-containing compounds such as guanidine, indoles, imidazoles, imidacillines, triazoles, morpholines, piperidines, amidines, formalizines, and pyridines can be mentioned. Specific examples of these are:
For example, ammonium acetate, tricyclohexylamine,
Tribenzylamine, octadecylbenzylamine, stearylamine, allyl urea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, cobenzylimidazole, gouphenylimidazole, 2-phenyl-4'-may-ruimidazole, λ - undecyl-imidacillin, λ, ≠, j-trifuryl-2-imidacillin, l cordiphenyl-≠, gage methyl-2-imidazole, 2-phenyl-corimidasoline, l.

2.3-triphenylguanidine, l, 2-ditolylguanidine, /, 2-synchrohexylguanidine, /,
2.3-) Synchhexylguanidine, guanidine trichloroacetate, N,N'-dibenzylpiperazine, μ
, ≠′-diteomorpholine, morpholinium tric I:
rr: I acetate, no-aminobenzene thiazole, 2
-benzoylhydrazino-benzotheazole. Two or more of these coloring agents can also be used in combination.

The microcapsules of the present invention are produced by emulsifying a core material and then forming a wall of a polymeric material around the oil droplets through a polymerization reaction. It is added to the inside of the reactor Hj oil droplet and/or to the outside of the oil droplet to form a polymeric substance. Specific examples of polymeric substances include polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polyvinyl acetal, and polymers of gelatin and aldehyde.

Two or more types of polymeric substances can also be used in combination.

Preferred polymeric materials are polyurethane, polyurea, polyamide, polyester, polycarbonate, and more preferred are polyurethane and polyurea.

Regarding the physical properties of the polymeric substance, it is preferable to use a polymeric substance that has a melting point of 75066 or higher and does not melt at the temperature during thermal recording.

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 coupling component, and the diazo compound and coloring aid. Coupling components and coloring aids can be used in various quantities. When the two types are used as core materials, the other components that are not used as the core materials of the microcapsules can be contained in the same microcapsule or in separate microcapsules, and are used in the photosensitive layer outside the microcapsules.

It is also possible to contain the diazo compound, the coupling component, and the color development aid in separate microcapsules, and this form is the best in terms of color development. In this case, at least the glaze among the above three components must be present in the microcapsule together with the organic bath agent.

The microcapsule wall of the present invention is particularly effective when using a microencapsulation method using the force of adhesive actant from inside the oil droplet. That is, it is possible to obtain capsules, which are desirable as a recording material and have a uniform particle size and excellent storage stability, within a short period of time.

This method and specific examples of compounds are described in U.S. Pat.
, 726. bC1: Towed in the book Φ:l 1i411 of s'oty- issue, 3,726, 66th issue.
For example, when polyurethane is used as a capsule wall material, polyvalent incyanate and a second substance (e.g., polyol) that reacts with it to form the capsule wall are mixed into the oily liquid to be encapsulated, emulsified and dispersed in water, and then heated to By raising 1-, sieve molecules are formed at the oil droplet interface, forming a microcapsule wall. At this time, a low boiling point and strong dissolving power supplementary agent can be added to the oily liquid.

In this case, which 7+5 isocyanate '1?
11" hand polyol, po') 7 mi 7 VC tweet ha rice I'jN'ir 3 i 3r 7
/ty4, same 7.2 g /3za3-, same 3≠
tl? No. 22, No. 377-979j, No. 379326
No. 1, equity 1'l': l '' g 'I 034!No.
/-J'-J'0/? It is also possible to use the tl temaru・su, tl, etc. disclosed in the same issue, 4'f-4Jort issue.

In addition, in order to promote the urethanization reaction, salt or the like can also be used in combination.

When making microcapsules, water-soluble polymers can be used for the purpose of emulsification and prevention of agglomeration of emulsions, but water-soluble polymers include water-soluble anionic polymers, nonionic polymers, and amphoteric polymers. Both natural and synthetic polymers can be used as anionic polymers.
For example, those having a -C00-1-SOa- group and the like can be mentioned. Specific anionic natural polymers include gum arabic and alginic acid, while semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, chain oxidized starch, tinned cellulose, and lignin sulfonic acid.

Synthetic products include maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers, Examples include carboquine-modified polyvinyl alcohol.

Examples of nonionic polymers include polyvinyl alcohol, hydroxyethyl cellulose, and methyl cellulose.

Examples of amphoteric compounds include gelatin.

These water-soluble polymers are used as an aqueous solution of O6θl to iowt%. The particle size of the microcapsules is adjusted to 20μ or less. Generally, if the particle size exceeds 2Qμ, the print quality tends to be poor.

In the patent, when heating with a thermal head is performed from the coating layer side, it is preferable that the temperature be less than rμ in order to avoid pressure distortion.

When making microcapsules, they can be made from an emulsion containing 0.2wt or more of the component to be microencapsulated.

The amount of coupling component is 0.0% per 1 part by weight of the diazo compound.
/-10 parts by weight, and the coloring aid is preferably used in a ratio of o, i to 10 parts by weight. The organic solvent is used in an amount of 25 parts by weight, preferably 25 parts by weight. Further, it is preferable to apply the diazo compound at a rate of 0.01-2°09/m2.

When the diazo compound, coupling component, and coloring aid used in the present invention are not microencapsulated, they are preferably used after being dispersed in solid form using a sand mill or the like. In this case, each is separately dispersed in a water-soluble polymer solution. Preferred water-soluble polymers include nonionic polymers used when making microcapsules. At this time, the concentration of the water-soluble polymer is 2 to 30 wt, and the diazo compound, coupling component,
Different coloring aids! ~ μθw t %.

The dispersed particle size is preferably 10 microns or less.

The heat-sensitive recording material of the present invention contains silica, barium chloride, titanium oxide, aluminum hydroxide, zinc oxide,
Pigments such as calcium carbonate, styrene beads, and fine powders such as urinary melamine resin can be used.

Similarly, metal soaps can also be used to prevent sticking. 1 inch of these uses is 0
62-79/m2.

Furthermore, a heat-melting substance can be used in the heat-sensitive recording material of the present invention in order to increase the degree of heat-recording haze.

The heat-melting substance is a substance that is solid at room temperature, has a melting point of 60 to 10°C and 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 substance is 0. /Dispersed in particles of ~10μ, solid content 0.2~71? / m2 is used. Specific examples of heat-melting substances include fatty acid amides, N-purchased fatty acid amides, ketone compounds, N-substituted carbamate compounds, urea compounds, esters, and the like.

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

As a binder, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, gum abyss, gelatin, polyvinylpyrrolidone, casein, styrene-butadiene latex, acrylonitrile-butadiene latex, polyvinyl acetate, polyacrylic acid ester, ethylene-vinyl acetate, etc. Various emulsions of polymers can be used. The amount used is solid content O,S~19/rn2.

In the present invention, in addition to the above materials, citric acid is used as an acid stabilizer.
Tartaric acid, oxalic acid, boric acid, phosphoric acid, pio IJ 7 acid can be added.

In the recording material of the present invention, at least one of the reactive substances such as a diazo compound, a coupling component, and a coloring aid is dissolved or dispersed in an organic solvent and then microencapsulated. The remaining reactive substances can be solid-dispersed or mixed with the above-mentioned microcapsule dispersion as an aqueous solution to prepare a coating solution, which can then be coated on a support such as paper or synthetic resin film with a bar or V-dot. It is coated by coating methods such as coating, air knife coating, gravure coating, roll coating, spray coating, and dip coating, and is dried to reduce the solid content.

A heat-sensitive layer of t~/2/m2 is provided. Another method includes a layered structure in which a microcapsule layer containing a reactive substance and a solvent is laminated with a layer containing the remaining reactive substance. The laminated structure is more
This is advantageous in terms of fogging during long-term storage. This "Yaiai",
In terms of sensitivity, it is more advantageous to place the microcapsule layer on top, and in terms of preventing color fog caused by destruction of the microcapsules due to pressure or scorching during handling, it is better to place the microcapsule layer on the bottom layer. It is more advantageous.

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 exposing it to light after heating and decomposing unreacted diazo compounds. . In addition, it can also be used as a heat transfer hoe type copying paper.

Examples are shown below, but the present invention is not limited thereto. R KIXJ is "parts by weight" which indicates the amount of added carcasses.
represents.

Examples 1 to 8 Using the following diazo compounds +11 to (3), add appropriate amounts of the diazo compound and the (j:/) adduct of xylylene/diisocyanate and trimethylolpropane 70 in a dark room by changing the amount of each added. 1 part was added to a mixture of 20 parts of dibutyl phthalate and 5 parts of ethyl acetate and dissolved. The solution of this diazo compound was mixed with polyvinyl alcohol,
The mixture was mixed with an aqueous polyvinyl alcohol solution in which 1 part was dissolved in 52 parts of water, and emulsified and dispersed at 206C to obtain a pre-emulsified product with an average particle size of 3 μm. IOO parts of water was added to the obtained emulsion, heated to 700°C while stirring, and after 2 hours, three types of capsule liquids containing a diazo compound as a core material were prepared.

Diazo Compound (1) Diazo Compound (2) Diazo Compound (3) C4H9 In order to make a dispersion of the coupling component, using the coupling components (3) below, each of them was mixed with 20 parts of the coupling component. and 3 parts of polyvinyl alcohol were added to 100 parts of water and dispersed in a sand mill for about 2 microns to obtain a dispersion of three types of coupling components with an average particle size of about 3 microns.

Coupling component +11 2- and doroquine-3-naphthoic acid morpholinopropylamide cabrileg component (2) 2-hydroxy-3-naphthoic acid anilide coupling component (3) 2-hydroxy-3-naphthoic acid 7toe-2 '-Methylanilide II) Add 20 parts of phenylguanidine and 5 parts of polyvinyl alcohol to 100 parts of water and mix with a Xandmill for about 2
A dispersion of triphenylguanidine having a time dispersion of 4 and an average particle size of about 3 .mu.m was obtained.

Diazo compound capsule liquid 10 obtained as above
parts, 13 parts of a dispersion of coupling components, and 13 parts of a dispersion of triphenylguanidine! Zinc titstearate 20
In addition to this, we added omega blood.

This repellent blood was coated on smooth high-quality paper (JO? 7 m2) using a coating rod 32 to give a dry weight of 14 tp/m2.
It was coated with a par-coat so that it became ≠joC and dried for 30 minutes to obtain heat-sensitive recording materials (1) to (5). Table 1 shows the combinations of types and amounts of diazo compounds and types of coupling components.

On the other hand, for comparison, a diazo compound was treated in the same manner as in (1) to (5) except that it was microencapsulated by the method of Example 1 of JP-A No. 7-7/Hiroshi Takota, and a heat-sensitive recording material was prepared. (
6) to (8) were obtained. Combinations of types of diazo compounds and types of coupling components are shown in Table 3.

The heat-sensitive recording materials (1) to (8) obtained as described above were thermally recorded using Gll mode () The entire surface was irradiated with four lights using a Ricoh Ysterdog model (manufactured by Ricoh ■) and fixed.The blue density of the recorded image was measured using a Macbeth reflection densitometer.The results are shown in Table I.On the other hand, When thermal recording was performed again on the fixed portions, it was confirmed that no images were recorded on any of them, indicating that they were fixed.

In order to check the shelf life in humans, heat-sensitive recording (-4 charges (11~
(8) Background density (fog) and Soshi1 etc. are jθ0C1 relative humidity? Keep in the dark for 2μ hours under the conditions of 0%ItI
After Schiff and forced deterioration tests, fog was measured using a Macbeth reflection densitometer to see changes in fog. The results are shown in Table 1.

As can be seen from Table I, the present invention in which the diazo compound is encapsulated has a high 0 degree image, similar to the comparative example without encapsulation, and furthermore, the increase in fog after the forced deterioration test is small and the comparative example without encapsulation It has much better shelf life.

Examples 9 to 16 In Examples 1 to 8, 3 parts of the coupling component was added instead of the diazo compound in the method for preparing the capsule liquid to make the capsule liquid of the coupling component g's blue, and the coupling component was dispersed. Coupling component 2 of the method for preparing the product
A suitable amount of the diazo compound is added in place of 0 part to prepare a dispersion of the diazo compound, and a capsule liquid of the coupling component,
to part, 15 parts of a dispersion of a diazo compound, 75 parts of a dispersion of triphenylguanidine, and 5 parts of zinc stearate 2θ
Heat-sensitive recording materials (9) to (1) were obtained by applying coating d consisting of parts in the same manner as in Examples (1) to 15). The combinations of the type of diazo compound, the type of added firewood, and the type of coupling component are shown in Table H. On the other hand, for comparison, unlike the present invention, microcapsules containing only a coupling component without containing an organic solvent in the microcapsules were prepared using the method of Example 1 of Yankaisho 67-/Takotagu. This was used to produce a heat-sensitive recording material.That is, vinyl acetate-butyl methacrylate-
Dissolve the styrene co-jR compound/Q part in the cyclohexane SO part, and further perform the coupling! 1 part was dissolved and added to a solution consisting of 3.2 parts of polyvinyl alcohol and r≠ parts of water. This mixed solution was stirred at high speed at room temperature to emulsify the fraction, and distilled under reduced pressure while stirring to remove cyclohexane to obtain a capsule liquid of the coupling component. Next, filter the capsule liquid,
It was washed with water and dried in air to obtain a capsule powder. The resulting capsule powder was added to the coupling component capsule solution of the coating solution used in the heat-sensitive recording materials (9) to (131)! J parts of capsule powder was added in place of θ part to prepare a coating solution.
Heat-sensitive recording material (]4-(1→f
f: Good. Types and Additions of Diazo Compounds” and Campling Ingredients 1! ! Table H shows the combinations of types.

e obtained as above, thermal recording material (91~(IT
The recorded image density, fog before forced deterioration, and fog after forced deterioration were measured in the same manner as in Examples 1 to 8, and are shown in Table H. Further, thermal recording was performed again on the fixed portions of thermosensitive recording materials (9) to 04, but no image was recorded in any of them, and it was confirmed that they were fixed. .

As shown in Table 2, after the coupling component is emulsified as a core material, polymerization If is formed around the core material.
(The present invention Q' in which the capsule wall of The increase is also small and the storage stability is low.

Example 17 A capsule liquid was prepared by adding 5 parts of cophenyl-g-methyl-imidazole in place of the diazo compound in the method for preparing a capsule liquid in Examples 1-8. 60 parts of the obtained capsule liquid, 15 parts of the dispersion of the coupling component (1) prepared in Examples 1 to 8, and 1 J part of the dispersion of the diazo compound (11) prepared in Examples 9 to 16. A coating solution was prepared by adding 20 parts of the solution.This coating solution was coated in the same manner as in Examples 1 to 8, and a heat-sensitive recording material (1η) was prepared and tested.

The results are shown in Table In.

Example 18 In the method for preparing capsule liquids of Examples 1 to 8, 7 parts of diazo compound (II) and 1 part of coupling component (2) were added instead of the diazo compound to prepare 6 capsules. Capsule By, ls part and fruit/Aj flll
Triphenylguanidine-2o tit used in s~8
A coating liquid was prepared by adding lj parts of zinc nutheate containing: s %, and 1 cask was prepared (thermosensitive recording) in the same manner as in Examples 1 to 8, and the M L was tested. The results are shown in Table ■.

Table ■ Table ■ Heat-sensitive recording material (1η ~ (l) 7 parts of the main component is contained in the capsule of the present invention,
The angle of view is as sharp as it is from ll! ff (high degree of 1), the increase in fog after forced deterioration is small and the storage stability is dfh.

Example 19 In the method for preparing capsule liquids of diazo compounds of Examples 1 to 8, instead of 10 parts of xylylene diiso7anate trimethylolpropane (J:/) adduct, 5 parts of the same compound and tolylene diincyanate were added. A supplement solution using the diazo compound fil as the core material was obtained in the same manner except that 5 parts of the trimeterolpronomine (3:/) adduct was used. 10 parts of the obtained capsule liquid, 13 parts of the dispersion of the cup link component (1) manufactured by J1 in Examples 1 to 8, and 75 parts of the dispersion of triphenylguanidine were added to 20 parts of zinc stearate and applied. A l'I solution was prepared. Using this coating solution in the same manner as in Examples 1 to 8, a ζ heat recorder was prepared and tested. , or and 0°73, the image coverage was high, and the storage stability was also excellent.

Example 20 Polyvinyl alcohol J was used in place of the polyvinyl alcohol water bath solution in which the solution in which the diazo compound was dissolved was emulsified in the method for preparing the capsule liquids of Examples 1 to 8.

2 parts and hexamethylene diamine-JiζL (dissolved in 1 part of water) were used in the same manner. 60 parts of capsule liquid of diazo compound (1) and dispersion % of coupling component (1) 3 parts of l Z and 13 parts of a dispersion of triphenylguanidine were added to stearin qt, -4!j lead 2
A heat-sensitive recording material was prepared by adding 0 part of lead to the coating solution and using the same procedure as Example 1, 111-8, and 1 River. When I tested this, the picture was 18! The concentration is 1. /, and the fog before and after the forced deterioration test was o, og and 0.13, respectively, the image density was high, and the storage stability was 1. φIt was a lewd thing.

Example 21 The ability to add 0.2 parts of terefucuric acid chloride to the core material in which the diazo compound is dissolved in the method for making capsule liquid in Example 20 is the same as in Example β1120. A heat-sensitive recording material was produced. The capsule wall at this time was made of polyurea and polyamide.

When this photosensitive material was tested, the seismic intensity was 1η, /
, the fog before and after the forced aging test is O0or, respectively.
and/, 0, and the storage stability was also excellent.

Examples 22-24 50 parts of the microcapsule liquid containing the diazo compound obtained in Examples 1-8 and the microcapsule liquid containing the coupling component (3) obtained in Examples 9-16? 5 parts of the microcapsule liquid containing copheny-l-methyl-imidazole obtained in Yube and Example 17! A coating solution was prepared by adding 20 parts of zinc stearate. This coating liquid was coated on a smooth high-quality paper with drying at a density of l'l 9/m2 and dried to obtain a heat-sensitive recording material (2/l).

The results of these tests are shown in Table ■.

Procedural amendment 1, indication of the case Showa N year patent application No. 1 iti-ysλ No. 2
, Title of the invention Thermal recording material 3, Relationship with the case of the person making the amendment Patent applicant office 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd. 4. Subject of amendment The description of the contents of the amendment in column 5 of "Detailed Description of the Invention" of the specification is amended as follows.

da page 0, line 1 “1.O] "0./J and correct it.

Procedural amendment, Commissioner of the Patent Office 1, Indication of the case Showa! Patent Application No. 1/≠732 2,
Title of the invention Thermal recording material 3, Relationship to the case of the person making the amendment Patent applicant Address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of the amendment In the "Claims" column of the specification, "Detailed description of the invention" ” column 5, the statement in the “Claims” section of the description of the contents of the amendment is amended as shown in Attachment-1.

The entire description in the "Detailed Description of the Invention" section of the specification will be amended as follows.

(1) From page 5, page 13 to Hiroyukime "at least a little bit" "In a recording material containing the diazo compound" and correct it.

(2) Page 6, line 10 "to swell" "becomes a rubber state, and the solvent" and correct it.

(3) Page 6, line 12 "rate-limiting stairs" "Rate-limiting stage" and correct it.

(4) Page 7, line j Delete "ya softening".

(5) Line 7 on page 7 From ", cup" on the to line of the same page Delete everything up to "1 type of spider".

(6) Page 7, line 1 "Hatondo" "At all outwardly" and correct it.

(Page ≠ ~ jth line "Reactive substance" "Diazo compound" and correct it.

(8) Delete the text from "Mata diazo compound" on the gth line to "Not provided" on the second line of the same page.

(9) iA page 16th line After "Dyptyl" ", tricresyl phosphate" Insert.

a groan page 10 line j Delete "compound".

Uυ On page 11, from line ``Polymer'' to line 7 of page 1, ``necessary.'' Of course, it is possible, but for the following reasons, it is best to encapsulate the diazo compound as a whole core material.Firstly, diazo compounds are generally expensive, and there are fewer cases when diazo compounds are encapsulated than in other cases. The same color density can be obtained with the amount used.Secondly, when dissolving the diazo compound in an organic solvent and encapsulating it in a capsule, the main reason is that the amount used is small as mentioned above; Establishment is quick and easy to complete.Thirdly, when stored for a long time under gentle conditions, there is little rise in turnip growth.
Moreover, the decrease in maximum concentration is also small. ” he corrected.

α2 Page 22, line 12 Delete "diazo compound,"

Q31 2nd No. Delete "When not microencapsulated".

α4) Page 22, line 16 "Dispersed." “It can be distributed, or it can be distributed at the same time.” and correct it.

a ■ Page 22, line 17 After being “used” Insert "ru".

(Ie 2nd II-page/Line I From “Diazo compound” to line JO on the same page Delete up to “Tomo 1 type”.

(17) Page 25! row After “remain” "Coupling components, color development aids, etc." Insert.

α8 Delete "Contains reactant and W l?lt Er medium" in line 2j of page 2.

σ9 2nd evening page 10th line "Remain" "other" and correct it.

(2) Correct the throughput of the attached sheet-λ from "Example 1-za" on page 26, line r to table (2) on page ≠1.

Attachment-l Claims 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,
A heat-sensitive recording material characterized in that the diazo compound is contained in microcapsules together with an organic solvent.

Attachment-2 Example 1 The following diazo compound (J: / 1 adduct of xylylene diisocyanate and trimethylolpropane)
r parts of total tricresyl phosphate were added to a mixed solvent of 1 λ parts, and dissolved. This solution of the diazo compound was added to an aqueous solution in which 3.2 parts of polyvinyl alcohol was dissolved in 5 g parts of water, and emulsified and dispersed at 1.2 to 10 cm. jμ
An emulsion was obtained.

Add i00 parts of water to the obtained emulsion, stir, and add i,o
After 2 hours, a capsule liquid containing a diazo compound in the core substance was obtained.

(Diazo Compound) C4Hg Next, 10 parts of euhydroxy-3-naphthoic acid anilide and 10 parts of triphenylguanidine were added to 100 parts of tl polyvinyl alcohol aqueous solution, and the mixture was milled in a sand mill for about 24 hours.
After time dispersion, a dispersion of the coupling component and triphenylguanidine with an average particle size of 3 μm was obtained.

Capsule liquid of diazo compound obtained as above 5
A coating liquid was prepared by adding 2≠ parts of a dispersion of a coupling component and triphenylguanidine to 0 parts.

This coating solution was coated on a smooth, high-quality paper (<109/m2) using a coating rod so that the dry weight was tg/rIL2, and dried for three parts at ≠00C to obtain a heat-sensitive recording material.

The resulting heat-sensitive recording material was thermally recorded using Gnl mode (Hifax 700; manufactured by Hitachi, Ltd.), and then the entire surface was exposed to light using Ricoh Suno ξ-Dry 100 (manufactured by Ricoh ■) and fixed. The blue density of the obtained recorded image was measured using a Macbeth reflection densitometer. Similarly, the yellow density of the background was measured. The results are shown in Table 1. On the other hand, when thermal recording was performed again on the fixed area, it was confirmed that image (2) was not recorded in any of the areas and was fixed.

Next, to determine the shelf life of the heat-sensitive recording material, we checked the background density (fog) of the heat-sensitive recording material and also determined the temperature of the heat-sensitive recording material.

It was stored in a dark place for tO days under the conditions of 0C1 relative humidity tO%RH, and after a forced deterioration test (f) was performed, fog was measured using a Macbeth reflection densitometer to observe changes in fog. The results are shown in Table 1.

Examples 2 to 6 Heat-sensitive recording materials λ to O were prepared in the same manner as in Example 1, except that the solvent shown in the table below was used instead of 12 parts of tricresyl phosphate in Example 1. Tested in the same manner. The results are shown in Table 1.

Comparative Example The diazo compound used in Example 1 and 3.1 parts of polyvinyl alcohol 3.2W5'5C water were dispersed in a sand mill for about 2+q to produce a dispersion with an average particle size of about 3μ.
A coating liquid was prepared by adding ≠j parts of the dispersion of the coupling component and triphenylguanidine prepared in Example t to this liquid.

This coating liquid was applied in the same manner as in Example 1 to prepare all heat-sensitive recording materials.

The obtained heat-sensitive recording material was tested in the same manner as in Example 1. The results are shown in Table 1.

Claims (1)

[Claims] 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,
At least seven of the diazo compound, the coupling component, and the color development aid are contained in the microcapsule together with an organic solvent (except when J41 is contained in the same microcapsule). A heat-sensitive recording material with a characteristic of %.