JPS60222283A - Thermal recording material - Google Patents

Abstract

PURPOSE:To obtain a thermal recording material having a ground with a white color tone, excellent preservability before thermal recording and a high developed color density upon thermal recording and capable of being fixed after thermal recording, by a method wherein a diazo compound and a polymerizable compound having an ethylenically unsaturated bond are microencapsulated. CONSTITUTION:A diazo compound and a polymerizable compound having an ethylenically unsaturated bond are incorporated in microcapsules, in a thermal recording material in which a recording layer comprising a diazo compound, a coupling component and a basic substance is provided on a base. Accordingly, a thermal recording material having a white ground color tone, excellent preservation in raw state and a high thermal color forming property can be obtained. The polymerizable compound may be an unsaturated carboxylic acid, a salt thereof or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" 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 heat-sensitive recording material that has a white background, has excellent storage stability before thermal recording due to ρ, has high color density during thermal recording, and is capable of light fixing after thermal recording.

"Prior Art" A leuco coloring type heat-sensitive recording material is usually used as a recording material used in a heat-sensitive recording method. However, this heat-sensitive recording material is subject to harsh handling and heating after recording.
has the disadvantage that color develops in unexpected places due to the adhesion of solvents, staining the recorded image. In recent years, research has been actively conducted on diazo color-forming heat-sensitive recording materials as heat-sensitive recording materials that do not have these drawbacks. For example, JP-A Showa s7-/2
No. 3016, Journal of Painter's Electronics Society, //, λ Rio (IRI J Co), etc., and is a diazo compound.

A recording material that uses a coupling component and a basic component (including substances that become basic when heated) is thermally recorded, and then light is irradiated to decompose unreacted diazo compounds and stop color development. be. -Certainly, this method stops color development in areas that do not need to be recorded (hereinafter referred to as fixing)
I can do it.

However, this recording material also undergoes gradual pre-coupling during storage, and undesirable coloring (fogging) may occur. To this end, it has been attempted to prevent contact between the components and prevent pre-coupling by making some of the coloring components exist in the form of discontinuous particles (solid dispersion). 1! The e-recording material has disadvantages in that its shelf life (hereinafter referred to as raw shelf life) is not yet sufficient and that its thermal coloring properties are reduced. As another measure, it is known to separate the diazo compound and the coupling component as separate layers in order to minimize contact between the components (for example, as described in the above-mentioned Japanese Patent Application Laid-Open No. 7-/λ3ort). . Although this method greatly improves raw storage stability, it suffers from a large drop in thermal color development, and cannot be used for 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 basic substance is replaced with a non-polar waxy substance (JP-A-57-4qμl-@, JP-A-7
-/4AJ4J4) and hydrophobic polymer substances (JP-A-Sho!
It is known that it can be isolated from other components by encapsulating it with a 7-/9 Kota No. 4A4A).

However, these encapsulation methods involve dissolving wax or polymeric substances in their solvents, and dissolving or dispersing the color-forming components in these solutions to form capsules, which do not require the cylindrical part of the core material. This is different from the concept of a normal capsule covered with a shell.

For this purpose, if the coloring component is dissolved and formed.

The color-forming component does not become the core material of the capsule, but is uniformly mixed with the encapsulating material, and pre-coupling gradually progresses on the outer surface of the capsule wall during storage, resulting in unsatisfactory shelf life. In addition, when a color-forming component is dispersed and formed, the thermal color-forming properties are lowered because the walls of the capsules do not undergo a color-forming reaction when heated and fused. Furthermore, there is a manufacturing problem in which the wax or the solvent used to dissolve the polymeric substance must be removed after the capsules are formed, which is not completely satisfactory.

Therefore, in order to solve these problems, the core material contains at least one of the components that can replace the color reaction.
A method of forming a wall around this core substance by polymerization to form a microcapsule (Specification of % Ganshojt-tsoμ3)
We have discovered an excellent heat-sensitive recording material.

``Problems to be Solved by the Invention'' However, even with heat-sensitive recording materials made using this microencapsulation method, when photofixed after thermal recording, the background portion (other than the recorded image) remains.

The drawback of a slight yellowish tinge was unavoidable.

``Object of the Invention'' Therefore, the seventh object of the present invention is to provide a heat-sensitive recording material that has a white background tone, has excellent shelf life, and has high thermochromic properties.

1 The first object of the present invention is to provide a heat-sensitive recording material that can be fixed by photodecomposing unreacted diazo compounds after heat recording.

A third object of the present invention is to provide a heat-sensitive recording material with excellent manufacturing suitability.゛“Means for Solving the Problem” As a result of intensive research, the present inventors found that a support contains a diazo compound, a coupling component, and a basic substance (or a substance that becomes basic when heated). The problem was solved by a heat-sensitive recording material provided with a recording layer in which both the diazo compound and a polymerizable compound having an ethylenically unsaturated bond were contained in microcapsules.

"Operation" The microcapsules of the present invention can be exposed to heat or pressure, as used in conventional recording materials, to bring the reactive substances contained in the core of the microcapsules into contact with the reactive substances outside the microcapsules. Rather than causing a color reaction by heating the core of the microcapsule and the reactive substance present on the outside, the reaction mainly penetrates through the microcapsule wall and causes the reaction to occur. This reaction is called a coupling reaction, and a colored image is obtained by this reaction, but the diazo compound not used in the reaction is decomposed by light and the coupling reaction ability is changed to a tanned compound. At this time, the diazo compound generally becomes yellowish due to photodecomposition, but if a polymerizable compound is present as in the present invention, the diazo compound does not become yellowish due to photolysis and also loses its coupling reaction ability. Put it away.

Although the mechanism is not clear, the effect is not caused by the polymerization of a polymerizable compound, so a polymerization initiator is not necessarily required, and the effect can be seen even if it is not included to the extent that it hardens through polymerization. .

The present invention will be described in further detail.

In the present invention, the polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as a vinyl monomer) is a compound having at least one ethylenically unsaturated bond (vinyl group, vinylidene group, etc.) in its chemical structure. So, monomer, prepolymer.

That is, it has chemical forms such as λ-mer, trimer, other oligomers, mixtures thereof, and copolymers thereof. Examples thereof include unsaturated carboxylic acids and their salts, esters with aliphatic polyhydric alcohol compounds, amides with aliphatic polyhydric amine compounds, and the like.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and incrotonic acid.
These include maleic acid.

Salts of unsaturated carboxylic acids include sodium and potassium salts of the aforementioned acids.

Specific examples of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol triacrylate, and l.

3-butanediol diacrylate, tetramethylene glycol diacrylate, tetrapyrene glycol diacrylate, trimethylolpropane triacrylate,
Trimethylolethane triacrylate &'#'-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipenta Erythritol triacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate,
Examples include sorbitol hexaacrylate and polyester acrylate oligomer. Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate), /, J-butanediol dimethacrylate, and antaerythritol. Dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, sorbitol trimethacrylate t'-)s
Sorbitol tetramethacrylate, bis-(p-(
J-methacryloxy-λ-hydroxyzoloboxy)phenyl]dimethylmethane, bis-rp-(acryloxyethoxy)phenyl]dimethylmethane, and the like. Itaconic acid esters include ethylene glycol shitaconate, propylene glycol shitaconate, /, J
-butanediol diitaconate), /IA-butanediol shiitaconate, tetramethylene glycol shiitaconate, pentaerythritol shiitaconate, sorbitol tetratrataconate, and the like. Crotonic acid esters include ethylene glycol dicrotonate,
Examples include tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, n, rubitol tetracrotonate, etc. Examples of isocrotonic acid esters include ethylene glycol diincrotonate, pentaerythritol diincrotonate, and nrubitol tetraisocrotonate. Nisder maleate includes ethylene glycol simarate, triethylene glycol simarate, pentaerythritol simarate, sorbitol tetramaleate, and the like.

Furthermore, mixtures of the aforementioned esters may also be mentioned.

Specific examples of amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, and G-hexamethylene bis-acrylamide.

/, A-hexamethylene bis-methacrylamide, diethylene triamine tris-acrylamide, xylylene bis-acrylamide, xylylene bis-methacrylamide, and the like.

Other examples include Special Publication No. 447-441701,
Polyisocyanate compounds described in the publication that have two or more isocyanate groups in one molecule are added with a vinyl monomer containing a hydroxyl group represented by the following general formula. Examples include vinyl urethane compounds containing vinyl groups.

C)12=c (R) C00CR2CH(R')O
H (However, R and R' represent H or CH3.

Preferred vinyl monomers used in the present invention include:
They are monofunctional or polyfunctional methacrylates and polyvalent acrylates.

In addition, the vinyl monomer is O
It is used at a ratio of 6λ to 20 areas. Preferably /, 7
The proportion is 0 parts by weight.

The vinyl monomer is used by being contained in the core material of the microcapsule together with the diazo compound, but at this time, the solvent for the core material (
A part or all of the organic solvent used as a dispersion medium (or a dispersion medium) can be replaced with a vinyl monomer.

The diazo compound used in the present invention is a diazonium salt represented by the general formula ArN20X- (wherein aAr represents an aromatic moiety, hN2+ represents a diazonium group, and X- represents an acid anion); It is a compound that can develop a color by causing a coupling reaction with a coupling component, and can also be decomposed by light.

Specifically, as the aromatic moiety, those having the following general formula are preferable.

In the formula, YVi represents a substituted amino group, an alkoxy group, an arylthio group, an alkylthio group, or an acylamino group, and R
is an alkyl group, an alkoxy group, an arylamino group, or
Represents halogen (% Br, α, F).

The substituted amino group of Y includes a monoalkylamino group, a dialkylamino group, an arylamino group, a morpholino group,
A piperidino group, a pyrrolidino group, etc. are preferred.

Specific examples of diazonium compounds that form salts include diazo-7-diethylaminobenzene, 4-diazo-
7-diethylaminobenzene, diazo-7-dipropylaminobenzene, diazo-7-methylbenzylaminobenzene, diazo-7-dipendylaminobenzene% μm diazo-1-ethylhydroxyethylaminobenzene, μm diazo-7 -diethylamino-3-methoxybenzene, μm diazo-7-dimethylamino-comethylbenzene, μm diazo-l-penzoylaminoco, j-jethoxybenzene, μm diazo-7-morpholinobenzene% μm diazo-7-morpholino- 2,j
-jethoxybenzene, μm diazo-7-morpholino-
2,j-dibutoxybenzene, France-diazo-l-anilinobenzene, μm-azo/-)ruylmercabutoe J
, j-jethoxybenzene% hiro-diazo-l, 4A-methoxybenzoylamine, no-2,5-jethoxybenzene, μm diazo-7-pyrrolidino-λ-ethylbenzene, and the like.

A specific example of an acid anion is CnF2n+ICOO
-(n is an integer from J to f 3%CmF2m+1SOa-(
ml; JI number of tJ~f), (CzF2z+xSOz)
2CH- (t is an integer of /%/f).

H 803- (Integer from nt'iJ to 9) (n is an integer from 3 to ri) Examples include BF4-1PFe-.

In particular, as the acid anion, one containing a perfluoroalkyl group or a perfluoroalkenyl group, or PFa- is preferable because there is little increase in fog during raw storage.

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

C4H9 0C4H.

C4Hg C2H6 C(Q(a)) a OC2)15 C2H5 0Ca) 19 CzHs CaHe 0C4)i.

The coupling component used in the present invention is often one that forms a dye by coupling with a diazo compound (diazonium salt) in a basic atmosphere.

A body flJ to L, resorcinol, 70 loglucin, co.

Sodium 3-dihydroxyna7talene-6-sulfonate, l-hydroxy-2-naphthoic acid morpholinopropylamide% 7. j-dihydroxynaphthalene%2.3
-dihydroxynaphthalene, λ.

3-dihydroxy-4-sul7anylnaphthalene.

No-hydroxy-3-naphthoic acid morpholinopropylamide, No-hydroxy-3-naphthoic acid anilide, λ-
hydroxy-3-s7to-co'-methylanilide,
λ-Hydroxy-3-naphthoic acid ethanolamide, λ
-Hydroxy-3-naphthoic acid octylamide, λ-hydroxy-3-hexaphthoic acid-N-dodecyl-oxy-propylamide, 2-hydroxy-3-naphthoic acid tetradecylamide, acetanilide, acetoacetanilide, benzoylacetanilide, l-phenyl -3-Methyl-y-pyrazolone% /-[col,μIt'-trichlorophenyl)-3-benzamido-j-pyrazolone,
1-(2', μ', t'-trichlorophenyl)-3-
Anilino! -pyrazolone, l-phenyl-3-phenylacetamito s-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 basic substance of the present invention, tl, a poorly water-soluble or water-insoluble basic substance, and a substance that generates dialkali when heated are used.

Basic substances include inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, virols, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidacillins, and triazoles. morpholines, piperidines, amidines, formazines, l? Examples include nitrogen-containing compounds such as glycine. Specific examples of these include N, t, ammonium acetate, tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, allyl urea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, λ-benzylimidazole%a -Phenylimidazole, -Phenyl-[mu]m methyl-imidazole, [lambda]-Undecyl-imidacillin, [lambda],[mu],j-trif·°lyru-co-imidazole, l.

Kodiphenyl≠, lA-dimethyl=koimidazoly/, cophenyl-λ-imidacillin &'1λ, 3-trinoenylguanidine, 1.2-ditolylguanidine%
/j Kodicyclohexylguanidine% /, 2. ! −
・Tricyclohexylguanidi/%guanidine trichloroacetate, N,N'-dibenzylpiperazine, France, 4c
'-dithiomorpholine, morpholinium trichloroacetate, co-aminobenzothiazole, and cobenzoylhydrazinobenzothiazole. Two or more of these basic substances can also be used in combination.

The present invention involves dissolving or dispersing the diazo compound and vinyl monomer contained in the core material of the microcapsules in a water-insoluble organic solvent, emulsifying them, and then forming the microcapsule walls by polymerization. It is preferable that the boiling point is 1 tro0c or more. Specifically, phosphoric acid esters, heptatalic acid esters, other carboxylic acid esters, fatty acid amides, alkylated biphenyls,
Alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes, diarylethanes, etc. are used. Specific examples include tricresyl phosphate, trioctyl phosphate,
Octyl diphenyl phosphate, tricyclohexyl phosphate, dibutyl phthalate, dioctyl heptathalate, dilauryl heptathalate, cifuclohexyl phthalate, butyl oleate, diethylene glycol dibenzoate, dioctyl sepacate, dibutyl sepacate, dioctyl adipate , trioctyl trimellitate, acetyltriethyl citrate, octyl maleate, dibutyl maleate,
Isopropylbiphenyl, isoamyl biphenyl, chlorinated paraffin, diisopropylnaphthalene, /, /'-
Ditolylethane, 2.4! -ditertiary aminophenol, N,N-dibutyl-cobutoxyj-ter-7yarioctylaniline, and the like.

Among these, ester solvents such as dibutyl phthalate, tricresyl phosphate, diethyl phthalate, and dibutyl maleate are particularly preferred.

The microcapsules of the present invention are made by emulsifying a diazo compound and a vinyl monomer-containing "R" and then forming a wall of a polymer material around the oil droplets. is added to the inside of the oil droplet and/or to the outside of the oil droplet. Specific examples of polymeric substances include polyurethane, polyurea, polyamide, polyester, polycarbonate, formaldehyde resin, melamine resin, polystyrene, styrene methacrylate, etc. Examples include polymers, styrene-acrylate copolymers, gelatin, polyvinylpyrrolidone, polyvinyl alcohol, and the like.

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

Preferred sieve molecular materials are polyurethanes, polyureas, polyamides, polyesters, polycarbonates, more preferably polyurethanes and polyureas.

The microcapsule wall of the present invention is particularly effective when using a microencapsulation method in which adhesive actant is polymerized from inside the oil droplet. Capsules suitable as recording materials having uniform particle size and excellent shelf life can be obtained quickly and within a short period of time.

This method and specific examples of compounds are described in U.S. Pat.
, 724, go4A No. 3,724. It is described in the specification of No. j27.

For example, when polyurethane is used as a capsule wall material, a polyvalent isocyanate and a second substance (such as a polyol) that reacts with it to form the capsule wall are mixed into an oily liquid to be encapsulated, emulsified and dispersed in water, and then heated to a temperature. Instead of rising, a polymer formation reaction occurs at the oil droplet interface to form a microcapsule wall. At this time, an auxiliary solvent with a low boiling point and strong dissolving power can be used in the oily liquid.

In this case, regarding the polyisocyanate used and the polyol and polyamine to be reacted with it, U.S. Pat.
1str No., Tokuko Akihiro, Y-A0347, Tokuko μTurco μis No., Tokuko Akihiro T-1vtyi4+, Tokuko Akihiro 44t-
tuott, and they can also be used.

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

In particular, polyvalent incyanate is added to the first wall-forming substance, and 1
It is preferable to use a polyol as the wall-forming substance for gλ, since it has good shelf life. Furthermore, by combining the two, it is also possible to arbitrarily change the thermal permeability of the reactive substance.

Examples of the polyvalent incyanate which is the first wall film forming substance include 1m-7 22 diisocyanate, p-phenylene diinocya $-)h'+4-tolylene diisocyanate, 2. μ-tolylene diinocyanate, naphthalene/, 4A-diisocyanate, diphenylmethane
$, 4''-diisocyanate, 3.J'-dimethoxy-
France, μ′-biphenyl diisocyanate h J *
3 t-dimethyldiphenylmeth 7-4. #'-Diisocyanate, xylylene-/, 4A-diisocyanate.

μ, u'-diyenylp0/J-diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-7, λ-diisocyanate, butylene-7,2-diisocyanate, cyclohexylene-/, 2-diincyanate, cyclohexylene Shiren-I,
Diisocyanates, such as diisocyanates, μ′
, μ“-triphenylmethane triincyanate, toluene-!, <4.4-) triisocyanate such as diisocyanate h”*”-dimethyldiphenylmethane-co, 2',!,!'-tetra such as tetraincyanate Incyanate, adduct of hexamethylene diisocyanate and trimethylolpropane, λ, 4A-) adduct of lylene diisocyanate and trimethylolpropane, adduct of xylylene diisocyanate and trimethylolpropane, adduct of tolylene diisocyanate and hexanetriol There are isocyanates and prepolymers such as

Polyols that are λth wall film-forming substances include aliphatic and aromatic polyhydric alcohols, hydroxy polyesters, and hydroxy polyalkylene ethers. Preferred polyols include the following (I) and (■) between -2 hydroxyl groups.

Examples include polyhydroxy compounds having a group (III) or (IV) in their molecular structure and having a molecular weight of less than zooo.

(I) Aliphatic hydrocarbon group (N) − with carbon number co to j
0-Ar-C-Ar -0-where 1 mouth, (m), (
Ar in IV) represents a substituted or unsubstituted aromatic moiety, and the aliphatic hydrocarbon group in (I) is -CnH2n-
is the basic skeleton, and hydrogen groups may be substituted with other elements.

To give a specific example, as an example of (I).

Ethylene glycol, / J-i lopanediol, 7.
4A-butanediol, i,z-bentanediol, /
, 4-hexanediol, /, ? -hebutansinol, 'S'S otanediol, propylene glycol, λ
, 3-dihydroxybutane.

l,-monodihydroxybutane, 7.3-dihydroxybutane, λ, --dimethyl-/,! -pronotinediol%λ, Hirope/tanediol%co, j-hexanediol, 3-methyl-1,1-bentanediol, /, 4t
-cyclohexane dimetatool, dihydroxycyclohexane% diethylene glycol, /, J, j-) dihydroxyhexane, phenylethylene glycol% l,
1. l-Trimethylolpropane, hexanetriol.

Examples include intererythritol and glycerin.

Examples of (It) include condensation products of aromatic polyhydric alcohols and alkylene oxides such as b'=di(2-hydroxyethoxy)benzene and resorcinol dihydroxyethyl ether.

Examples of (III) include p-xylylene glycol,
Examples include m-gysylylene glycol, α, α'-dihydroxycoupyl p-diisopropylbenzene, and the like.

An example of (W) is 4! , 4A'-dihydroxy-
Diphenylmethane% λ-(pjp'-dihydroxydiphenylmethyl)benzyl alcohol, bisphenol AIC ethylene oxide adduct.

Examples include adducts of propylene oxide and bisphenol A. It is preferable to use the polyol at a ratio of 0.0 λ to λ mol of hydroxyl groups per 41 mol of incyane.

When making microcapsules, a water-soluble polymer can be used, but the water-soluble polymer may be either a water-soluble anionic polymer, a nonionic polymer, or an amphoteric polymer.
As the anionic polymer, both natural and synthetic polymers can be used, such as -coo-, -so''
; Examples include those having groups, etc. Specific anionic natural polymers include gum arabic and alginic acid, while semi-synthetic products include carboxymethyl cellulose and
Examples include phthalated gelatin, sulfated starch, sulfated 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 carboxy-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 a 0.6 t, 1 oyt aqueous solution. The particle size of the microcapsules is adjusted to 10 μm or less. Generally, if the particle size exceeds 0μ, the print quality tends to be poor.

In particular, when heating with a thermal head is performed from the coating I side, the thickness is preferably gμ or less in order to avoid pressure fog.

A diazo compound containing the main components used in the present invention.

The diazo compound among the coupling components and basic substances is used as the core material of the microcapsule, but the other type may be contained in the core material of the microcapsule or may be present outside the microcapsule.

When the diazo compound and other lai are contained in microcapsules, they may be in the same microcapsule or in separate microcapsules.

When the other two types are contained in a microcapsule, it is not possible to simultaneously contain three bridges in the same microcapsule, but there are various combinations.

Other ingredients not contained in the core material of microcapsules are:
Used for the heat-sensitive layer outside the microcapsule.

When making microcapsules, use 0.2w of diazo compound.
An emulsion ηλ containing t'1 or more can be prepared.

The coupling component and basic substance used in the present invention are:
Whether it is contained inside the microcapsules or in the heat-sensitive layer outside the microcapsules, the amount of the coupling component is 0.7 parts by weight per 7 parts by weight of the diazo compound. /, 10
It is preferable to use the coloring aid in an amount of 7 to 20 parts by weight, and the diazo compound to be used in an amount of 0.7 to 20 parts by weight. (7j-
It is preferable to apply 097 m2.

When the coupling component and basic substance used in the present invention are not microencapsulated, it is preferable to use them as a solid dispersion together with a water-soluble polymer using a sand mill or the like. Preferred water-soluble polymers include water-soluble polymers used when making microcapsules. At this time, the concentration of the water-soluble polymer is λ~J Ow t, and the coupling component and basic substance for this water-soluble polymer solution are:
They are each added in an amount of 5 to 4 Aowtqb.

The dispersed particle size is preferably IQ'μ or less.

The heat-sensitive recording material of the present invention contains silica, barium sulfate, titanium oxide, aluminum hydroxide, zinc oxide,
Pigments such as calcium carbonate.

Fine powders such as styrene beads, urea-methamine resin, etc. can be used.

Similarly, metal soaps can also be used to prevent sticking. The usage amount of these is O0
λ~7t”7m2.

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

As a heat-melting substance, it is solid at room temperature. - It is a substance with a melting point of SO~/ZOOC that melts when heated by a mulhead, and it is a substance that dissolves diazo compounds, coupling components, or basic substances. The thermofusible substance is 0. /, 1
It is used in an amount of 0.2 to 7 f/m 2 dispersed in particles with a % solid content of 0.2 to 7 f/m 2 . Specific examples of the heat-melting substance include fatty acid amide, N-substituted fatty acid amide, ketone compound, urea compound, Nyester, and the like.

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

Binders include polyvinyl alcohol, methylcellulose, and carboxymethylcellulose.

Various emulsions of hydroxyzolobylcellulose, gum arabic, gelatin, polyvinylpyrrolidone, casein, styrene-butadiene latex, acrylonitrile-butadiene latex, polyvinyl acetate, polyacrylic ester, and ethylene-vinyl acetate copolymer can be used. can. The amount used is solid content o,,t-,tt7
m”.

In the present invention, in addition to the above-mentioned electrical materials, enoic acid,
Tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrroline*% can be added.

Thermal recording material Fi1 of the present invention A coating solution containing a diazo compound, a coupling component, a basic substance as a main component, and other additives is coated onto a support such as paper or a synthetic resin film using a bar and a blade. Apply by coating methods such as coating, air knife coating, gravure coating, roll coating, spray coating, and Dayzo coating, and dry to reduce the solid content.
- Provide a heat-sensitive layer of 7m2. Another method is to add the coupling component, the main component of the basic substance, and other additives as the core material of the microcapsules.

Alternatively, a coating solution is prepared by solid dispersion, or by dissolving it as an aqueous solution and then mixing it, coating it on a support, drying it to form a precoat layer with a solid content of ~iot7m2, and further on top of that a precoat layer with a solid content of ~iot7m2. It is also possible to apply a coating solution prepared by using the compound and other additives as the core material of microcapsules and dry it to form a layered coating layer having a solid content of 1 to 11/m2. The layered heat-sensitive recording material may have a layered layer in the reverse order, and the coating method may include successive layering or simultaneous coating. This laminated type heat-sensitive recording material will soon have excellent long-term shelf life.

The paper used for the support is heat extracted pH 4 sized with a main sizing agent such as an alkyl ketene dimer.
The use of neutral paper (described in % Kaisho No. J-144271) is advantageous in terms of storage stability over time.

In addition, in order to prevent the coating liquid from penetrating into the paper and to improve the contact between the recording heat head and the heat-sensitive recording layer, Japanese Patent Application Laid-Open No. 57-t14
No. 6117.

In addition, paper having a Bekk smoothness of 0 seconds or more is advantageous.

In addition, paper with an optical surface roughness of t μ or less and a thickness of 30 to 75 μ as described in Japanese Patent Application Laid-open No. 5 R-I and ITA Octopus, and a paper with a density of 0°22 as described in JP-A No. 5 R-I and No. 1 / wound or less and the optical contact ratio is 13% or less, Canadian Standard P water content (JIS P#t2
Paper made from pulp beaten to 4'oca or more in i) to prevent penetration of coating liquid, published by JP-A-Sho! Ir
-4149! No. 1, the glossy surface of base paper made by Yankee machine is used as the coated surface to improve the color density and resolution, and the base paper is subjected to corona discharge treatment as described in the specification of Japanese Patent Application No. 77-44J1F7λ. , paper with improved coatability, etc. can also be used in the present invention with good results. In addition to these, any support commonly used in the field of heat-sensitive recording paper can be used as the support of the present invention.

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 moreover, after heating printing, it is fixed by decomposing unreacted diazo compounds with 'i4 light. I can do it. 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 "parts" indicating the amount added represent "parts by weight."

"Example" Example 1 The following diazo compound φ part and xylylene diisocyanate and trimethylolpropane (j: / ) mixture / f part t tricresyl phosphate 6 parts, trimethylolpropane trimethacrylate 17 parts, dichloromethane of the mixed solvent and dissolved.

This diazo compound solution was mixed with polyvinyl alcohol 5.
Add 1.2 parts to an aqueous solution in which 2 parts are dissolved in sr parts of water.
Emulsification and dispersion was carried out at 0°C to obtain an emulsion with an average particle size of jμ. Add 100 parts of water to the obtained emulsion and add tO while stirring.
After heating to oC for 2 hours, a capsule liquid containing the diazo compound tone core material was obtained.

oc4H.

Next, in addition to 10 parts of 2-hydroxy-3-su7tonic acid anilide and 100 parts of trinoenylguanidine lo part f1% polyvinyl alcohol aqueous solution, the mixture was dispersed in a sand mill for about 10 hours to form a coupling component with an average particle size of 3μ. A dispersion of triphenylguanidine was obtained.

Capsule liquid of diazo compound obtained as above
A coating liquid was prepared by adding a coupling component and a dispersion of triphenylguanidine λ to om.

This coating solution was coated on smooth high-quality paper (jOf/m 2 ) using a coating rod to a dry weight of 497 m'' and dried in an aooc for 30 minutes to obtain a heat-sensitive recording material.

The resulting heat-sensitive recording material was thermally recorded using GIII Sode (Hifax 7 (YO; manufactured by Hitachi, Ltd.), and then the entire surface was exposed to light using Ricopy Super Dry 100 (manufactured by Ricoh ■) for fixing. The resulting recorded image t Macbeth reflection density was measured using a needle.Similarly,
The yellow density of the background was measured. The results are shown in Table 7. On the other hand, when thermal recording was performed again on the fixed portion, it was confirmed that no image was recorded on any of the layers, but the image was fixed.

Next, to check the shelf life of the heat-sensitive recording material, the background density (fog) of the heat-sensitive recording material and the heat-sensitive recording material N were stored in a dark place under the conditions of The fog after the forced deterioration test was measured using a Macbeth reflection densitometer and the change in fog was observed. The results are shown in Table 1.

Examples 2 to 6 Heat-sensitive recording materials were prepared in the same manner as in Example 1, except that the vinyl monomers shown in the table below were used in place of trimethylolpropane trimethacrylate in Example 1. The test was conducted in the same manner as in 1. The results are shown in Table 1.

Example 7 Example 1 was repeated, except that 74 parts of the dispersion of p-benzyloxyphenol shown in Figure A below was further added to the capsule liquid, and the resulting coating liquid was coated to a dry weight of 197 m2. The heat-sensitive recording material was obtained in the same way as in the case of 5. The obtained recording material t- was tested in the same manner as in Example 1 and the results t-
It is shown in Table 7.

(Dispersion of p-benzyloxyphenol) p-benzyloxyphenol λθ part! In addition to loo part of a polyvinyl alcohol aqueous solution, disperse in a sand mill for about 24 L hours,
A dispersion with an average particle size of 3 μm was prepared.

Comparative Example 1 Fruit m91tKs-, trimethylolpropa7) except for remethacrylate, and tricresyl phosphate as a substitute.
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that the ≠ part was changed. The test results are shown in Table 1.

Comparative Example 2 Example 1iC, Th removed trimethylolpropane trimethacrylate and tricresyl phosphate, and replaced with dibutyl phthalate. A heat-sensitive recording material was obtained in the same manner as in Example 1 except that tJ was 1 part. The test results are shown in Table 1.

"Effects of the Invention" As is clear from Table 1, the yellow density of the background part of Comparative Examples 1 and 2 is quite high, but Examples 1 to 7f'i of the present invention
Yellow density was low and improved.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Letter, Mr. Commissioner of the Patent Office 1, Indication of the Case: 1975 Japanese Patent Application No. 72rJi 2, Title of the Invention: Thermal Recording Material 3, Relationship with the Amendment Person Case: Patent Applicant 4. Subject of amendment The description in column 5 of the "Detailed Description of the Invention" of the description and the "Detailed Description of the Invention" section of the description of the amendment shall be amended as follows.

(11 x 13 negative datakeme "Compound J Delete.

(2) After "preferable" in the 23rd negative line 10, "The shoulder solvent is added to the liquid part milked as a core material (diazo compound, organic solvent, capsule forming substance). It is preferable that the content be 70% by weight, and more preferably 120% by weight.''

(3) After the word "dekiru" on page 21, line 13, it is also possible to react with polyaxial isocyanate mineral water to form a polymer film. ” is inserted.

(4) Page 3-2, 2nd line "Color development aid" "Basic substance" and correct it.

Procedural amendment July 1920 and Japan Patent Office Commissioner Li1, Indication of the case Showa! 2013 Patent Application No. 7913/No. 2, Title of invention: Heat-sensitive recording material Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd. table Target of amendment The description in column 5 of "Detailed Description of the Invention" of the specification and the section of "Detailed Description of the Invention" of the description of the contents of the amendment will be under-amended as follows.

No.! After "Solved." on the page λO line, "The heat-sensitive recording material of the present invention can stop the color development of the diazo compound by photodegrading the unreacted diazo compound after it is thermally colored. It is also possible to first expose the image to light and then heat it uniformly to thermally color the unexposed areas.'' 1. Insert.

Claims (1)

[Claims] A heat-sensitive recording material in which a recording layer containing a diazo compound, a coupling component, and a basic substance or a substance that becomes basic by heat is provided on a support, in which the diazo compound and an ethylenically unsaturated bond are polymerizable. A heat-sensitive recording material characterized by containing both compounds in microcapsules.