Heat sensitive recording material

Abstract: A heat-sensitive recording material excelled in surface gloss and printing concentration is disclosed. The disclosed heat-sensitive recording material with a heat-sensitive color-developing layer formed on a supporting member features provision on the surface of the heat-sensitive color-developing layer of a protective coating containing crosslinked microfine particles (B) having substantially no glass transition temperature, 0.5 µ m or less in mean particle size and 0.05 or less in the difference in refractive index from the solid content of aqueous resin despersion which are obtainable by emulsion-polymerizing vinyl-containing monomers containing 15 weight % or more of polymeric multifunctional monomers together with the aqueous resin dispersion (A).

Description: The present invention relates to a heat-sensitive recording material and especially a heat-sensitive recording material excelled in surface gloss, printing concentration, sticking resistance and resistance to water and solvent. A heat-sensitive recording material having a dyestuff type heat-sensitive color-developing layer represented by combination of a leuco dye and a phenolic acidic substance is now being widely used in the field of thermal printers, facsimiles, measuring instruments recorders and, with its developing property, paper whiteness, applicability to various recording devices and economic feature highly appreciated, new uses are still being developed even now and, as a result, the requirement for improvement in quality of heat-sensitive recording material is being variegated and being further raised. Conventional heat-sensitive recording materials made by applying heat-sensitive color-developing coating to a supporting member have defects of printed image area being erased or non-image area being developed when they are exposed to some of the known solvents, water, light and plasticizers. The same tendency is noted when they are stored for a long time, hence desired is improvement of storage stability of heat-sensitive recording material. As a method of eliminating the aforementioned defects there has been developed a method of providing a protective coating on the heat-sensitive color-developing layer. As a binder for forming this protective coating has hitherto been known water-soluble high polymers such as polyvinyl alcohol, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, starches, caseins, polyacrylamide-type polymers, styrene-anhydrous maleic acid copolymer and polyacrylate and aqueous emulsions such as SBS latex but since protective coatings using some of the aforementioned coating compositions are not so good in sticking resistance, noise is apt to be caused during image formation, and in some cases the coating adheres to the thermal head, this often resulting in failure to obtain a proper image. For eliminating the aforementioned defects and improving the sticking resistance there have been proposed methods of using in combination inorganic pigments, cellulose powder, microfine glass particles, colloidal silica, thermosetting resin and silicone type compounds (for example, JP-B-58-35874, JP-B-63-63397, JP-A-No.57-120489, JP-A-60-18385, JP-A-62-156990 and JP-A-No. 62-244693). By the use of the aforementioned additives it was indeed possible to improve the sticking resistance, but this caused such other problems as poor gloss and low printing concentration. According to the English language abstract of JP-A-59-143683 published in Patent Abstracts of Japan, vol. 8, No. 274 (M-345) [1711] on December 14, 1984, a heat-sensitive luminous layer is disclosed which contains fine particles of a copolymer obtained from styrene and a cross-linking agent and/or a copolymer obtained from styrene, a monomer copolymerizable with styrene and a cross-linking agent. The monomer copolymerizable with styrene is disclosed as simple or a mixture of acrylnitrile, methyl (metha)acrylate, etc., and the cross-linking agent is described as including oil-soluble multi-functional unsaturated monomers or multi-functional unsaturated prepolymers in a mixing ratio of cross-linking agent to the "whole components" of 0.02 weight percent. It is stated that the objective is to prevent the adherence and sticking phenomenon of dregs. In view of the aforementioned circumstances, it is the object of the present invention to provide a heat-sensitive recording material excelled in surface gloss and printing concentration as well as sticking resistance, resistance to water or solvent. The aforementioned object of the present invention is accomplished by providing a heat-sensitive recording material comprising a heat-sensitive color-developing layer formed on a supporting member and protective layer, and more specifically to a heat-sensitive recording material excellent in surface gloss and printing density, in which the aforementioned protective coating is obtainable by coating the heat-sensitive color-developing layer with a coating composition containing an aqueous resin dispersion (A) and crosslinked particles (B) having substantially no glass transition temperature and a mean particle size of not more than 0.5 µm obtainable by emulsion-polymerization of molecules of a vinyl group-containing monomer containing not less than 15 weight % of molecules of a multifunctional monomer. As the supporting member according to the present invention e.g. paper, plastic films, synthtic papers may possibly be used. The heat-sensitive color-developing layer formed on the supporting member is obtainable by applying a liquid coating composition prepared by dispersing in a binder known leuco dye/s, developer/s and various additives and/or auxiliaries described below, this followed by drying. As the aforementioned leuco dyes, known leuco compound may be usable, for example, triphenylmethane-type, fluoran-type, phenothiazine-type, auramine-type, spiropyran-type and indolinophthlide-type. As leuco dyes may be cited such as 3,3-bis(p-dimethylaminophenyl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide [Crystal Violet lactone], 3,3-bis(p-dimethylaminophenyl)-5-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl)-6-chlorophthalide, 3,3-bis(p-dibutylaminophenyl)phthalide, 3-cyclohexylamino-6-chlorofluoran, 3-dimethylamino-5,7-dimethylfluran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-7-methylfluoran, 3-diethylamino-7,8-benzfluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-(N-p-tolyl-N-ethylamino)-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 2-[N-(3'-trifluoromethylphenyl)amino]-6-diethylaminofluran, 2-[3,6-bis(diethylamino)9-(o-chloroanilino)xanthylactambenzoate], 3-diethylamino-6-methyl-7-(m-trichloromethylanilino)fluoran, 3-dimethylamino-7-(o-chloroanilino)fluoran, 3-dibutylamino-7-(o-chloroanilino)fluoran, 3-N-methyl-N-amylamino-6-methyl-7-anilinofluran, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, benzoylleucomethyleneblue, 6'-chloro-4'-methoxy-benzoindolinopyrylospiran, 5'-bromo-3'-methoxy-benzoindolinopyrylospiran, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-chlorophenyl)phthalide, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-nitrophenyl)phthalide, 3-(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy-5'-methylphenyl)phthalide, 3-(2'-methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy-4'-chloro-5'-methylphenyl)phthalide, 3-morpholino-7-(N-propyl-trifluoromethylanilino)fluoran, 3-pyrrolidino-7-trifluoromethylanilinofluoran, 3-diethylamino-5-chloro-7-(N-benzil-trifluoromethylanilino)fluoran, 3-pyrrolidino-7-(di-p-chlorophenyl)methylaminofluoran, 3-diethylamino-5-chloro-7-(α-phenylethylamino)fluoran, 3-(N-ethyl-p-toluidino)-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-(α-methoxycarbonylphenylamino)fluoran, 3-diethylamino-5-methyl-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-piperidinofluoran, 2-chloro-3-(N-methyltoluidino)-7-(p-n-butylanilino)fluoran, 3-(N-benzil-N-cyclohexylamino)-5,6-benzo-7-α-naphthylamino-4'-bromofluoran, 3-diethylamino-6-methyl-7-mesidino-4',5'-benzofluoran. As the aforementioned developers to be incorporated in the liquid coating composition are chemicals which act to develop the aforementioned leuco dyes through reaction therewith under heating may be used, for example, phenolic compounds, organic or inorganic substances or their esters and salts. For example, gallic acid, salicylic acid, 3-isopropylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-tertbutylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, 4,4'-isopropylidenediphenol, 4,4'-isopropylidenebis(2-chlorophenol), 4,4'-isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dichlorophenol), 4,4'-isopropylidene-bis(2-methylphenol), 4,4'-isopropylidenebis(2,8-dimethylphenol), 4,4'-isopropylidene-bis(2-tert-butylphenol), 4,4'-secbutylidenediphenol, 4,4'-cyclohexylidenebis(2-methylphenol), 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, α-naphtol, β-naphtol, 3,5-xylenol, thymol, methyl-4-hydroxybenzoate, 4-hydroxyacetophenone, novolak-type-phenolic resin, 2,2'-thiobis(4,6-dichlorophenol), catechol, resorcine, hydroquinone, pyrogallol and phloroglycinecarboxylic acid, 4-tert-octylcatechol, 2,2'-methylenebis(4-chlorophenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-dihydroxy-diphenyl, p-hydroxyethylbenzoate, p-hydroxypropylbenzoate, p-hydroxybutylbenzoate, p-hydroxybenzylbenzoate, p-hydroxybenzoate-p-chlorobenzyl, p-hydroxybenzoate-o-chlorobenzyl, p-hydroxybenzoate-p-methylbenzyl, p-hydroxybenzoate-n-octyl, benzoic acid, zinc salicylate, 1-hydroxy-2-naphthoic acid, 2-hydroxy-5-naphthoic acid, 2-hydroxy-6-zinc naphthoate, 4-hydroxydiphenylsulfone, 4-hydroxy-4'-chlorodiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 2-hydroxy-p-toluic acid, 3,5-di-tert-butylzinc salicylate, 3,5-di-tert-butyltin salicylate, tartaric acid, oxalic acid, maleic acid, citric acid, succinic acid, stearic acid, 4-hydroxyphthalic acid, boric acid and thiourea derivatives may be usable. As the binder mentioned above for example, polyvinyl alcohol, starches, starch derivatives, cellulose derivatives [e.g. methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose), polyacrylic sodium, polyvinylpyrrolidone, acrylamide/acrylate copolymer, acrylamide/acrylate/methacrylic acid terpolymer, styrene/anhydrous maleic acid copolymer alkali salt, isobutylene/anhydrous maleic acid copolymer alkali salt, polyacrylamide, alginic sodium, gelatin and casein may be usable. The aforementioned liquid coating composition containing the leuco dyes, developers and binders may further contain, as necessary, usual additives such as sensitizers, fillers, surfactants and thermofusing substances. As fillers may be cited inorganic microfine powders such as calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, surface-treated calcium and silica, and organic microfine powders such as urea-formaldehyde resin, styrene-methacrylic acid copolymer and polystyrene resin. As thermofusing substances may be cited, among others, higher fatty acids or their esters, amides or their metallic salts, various waxes, mixtures of aromatic carboxylic acids and amines, benzoic acid phenyl esters, higher linear glycols, 3,4-epoxy-hexahydrophthalic dialkyl, higher ketons and other thermofusing organic compounds 50 to 200°C in melting point. The protective coating formed on the heat-sensitive color-developing layer is obtainable through application of a liquid coating composition containing the aqueous resin dispersion (A) and the crosslinked particles (B) The individual components of the liquid coating composition are described below. Aqueous resin dispersion (A) is a binder component of the liquid coating composition and any one of the conventional binders may be used as such. For example, an acrylic emulsion, styrene-acrylic emulsion, styrene-vinylacetate emulsion and SBS emulsion may well be usable. Also preferred are the so-called self-crosslinking type emulsion disclosed in JP-A-63-258193 or 64-38405, being improved in sticking resistance. Further, preferred is one with its aqueous resin dispersion (A) being an acrylic type emulsion, which is suited for manufacturing a heat-sensitive recording paper excellent in surface gloss and printing concentration. There is no particular limitation on the dose of the aqueous resin dispersion but normally it is in a range from 20 to 400 weight %. As aqueous resin dispersion (A) which acts as the binder component of the liquid coating composition it is preferred to use the aforementioned acrylic type emulsion unmixed but it is possible to use it in combination with some of the binder components illustrated for the heat-sensitive color-developing layer on condition that it does not adversely influence the performance of the protective coating. The crosslinked particles (B) having substantially no glass transition temperature and a mean particle size of not more than 0.5 µm obtainable by emulsion-polymerization of molecules of a vinyl group-containing monomer containing not less than 15 weight % of molecules of a multifunctional monomer used in the present invention are for improvement of protective coating sticking resistance. By one having substantially no glass transition temperature is meant one showing no sharp endothermic peak when measurement is taken by the use of a differential scanning calorimeter. Inorganic pigments, cellulose powder, microfine glass powder, colloidal silica, thermosetting resin such as urea formaldehyde resin and silicone type compounds were not suited for forming a protective coating of high transparency and good sticking resistance, because such substances are themselves opaque, too large in particle size and/or lack in adhesion to the binder component. In contrast thereto, the crosslinked particles (B) allow compatibility of sticking resistance with transparency of the protective coating when they are used together with the aqueous resin dispersion (A), this giving a heat-sensitive recording material excellent in both surface gloss and printing density. As the multifunctional monomer usable for synthesis of crosslinked particles may be cited, among others, multifunctional (meth)acrylates having more than one unsaturated group in the molecule such as multi-esterification [e.g. di-, triesterification or more] products of (meth)acrylic acid with polyhydric alcohols such as ethyleneglycol, 1,3-butyleneglycol, diethyleneglycol, 1,6-hexanediol, neopentylglycol, polyethyleneglycol, propyleneglycol, polypropyleneglycol, neopropyleneglycol, trimethylolpropane, pentaerythritol and dipentaerythritol; (meth)acrylamides having more than one unsaturated group in the molecule such as methylenebis(meth)acrylamide; multifunctional allyl compounds having more than one unsaturated group in the molecule such as diallylphthalate, diallylmaleate and diallylfumarate; allyl(meth)acrylate and divinylbenzene, any one or more than one thereof in combination. As another monomer usable for synthesis of crosslinked particles may be cited, styrene derivatives [e.g. styrene, vinyltoluene, α-methylstyrene and chloromethylstyrene]; (meth)acrylamide derivatives [e.g. (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide and N,N-dimethyl(meth)acrylamide]; (meth)acrylate such as esterification products of C 1 to C 18 alcohols with (meth)acrylic acids such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate; hydroxy group-containing (meth)acrylate such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate and monoesters of (meth)acrylic acid and polypropyleneglycol; vinylacetate, (meth)acrylonitrile; polymerizable basic monomers, such as dimethylaminoethyl(meth)acrylate, dimethyl-aminoethyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide, vinylpyridine, vinylimidazole and vinylpyrrolidone; crosslinkable (meth)acrylamide, such as N-methylol(meth)acrylamide and N-butoxymethyl(meth)acrylamide; monomers are having hydrolyzable silicon group directly bound to the silicon atom, such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-(meth)acryloyloxypropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane and allyltriethoxysilane; epoxy group-containing monomers, such as glycidylacrylate, allylglycidyl ether; oxazoline group-containing monomers, such as 2-isopropenyl-2-oxazoline and 2-vinyloxazoline; aziridine group-containing monomers, such as 2-aziridinylethyl(meth)acrylate and (meth)acryloylaziridine; vinylfluoride, vinylidenefluoride, vinylchloride and vinylidenechloride. These may be used either singly or in the form of a mixture of two or more. In order to obtain crosslinked particles (B) having substantially no glass transition temperature, however, the glass transition temperature of the polymer made of monomers other than multifunctional monomers is preferred to be not less than 70°C , and more preferably not less than 90°C. when it is less than 70°C, it may be possible in some cases that the crosslinked particles having a sufficient heat resistance so as not to have substantially any glass transition temperature are obtainable even when multifunctional monomers are added. The crosslinked particles (B) used in the present invention are obtainable through emulsion-polymerization by a known method of molecules of a vinyl group-containing monomer containing not less than 15 weight % of the aforementioned molecules of a multifunctional monomer in an aqueous medium, that is, by any of the known methods of emulsion-polymerization. As such methods may be cited, among others, methods of polymerizing a mixture of known polymerization initiators, emulsifiers, water and monomers, the so-called monomer dropping method, pre-emulsion method, seed polymerization method and multi-step polymerization method. As the known polymerization initiators may be cited, for example, persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate; water-soluble azo-type compounds such as 2,2'-azobis(2-aminodipropane)dichlorate and 4,4'-azobis(4-cyanopentanoic acid); and hydrogen peroxide. As emulsifiers used for emulsion-polymerization are known, among others, anionic emulsifiers such as sodium dodecylbenzene sulfonate and sodium dodecyl sulfate; nonionic emulsifiers such as polyethylene oxide having nonylphenyl groups and block copolymers of polypropylene and polyethyleneoxide; and cationic emulsifiers such as trimethylstearyl ammonium chloride. Polymerizing temperature is in a range of 0 to 100°C, preferably in a range of 50 to 80°C , and polymerization time is 1 to 10 hours. Addition of some hydrophilic solvent in the course of emulsion-polymerization is feasible on condition that it does not adversely influence the physical properties of the crosslinked particles (B). The refractive index of the crosslinked particles (B) used in the present invention is adjustable through modification of the composition of the vinyl group-containing monomer but, in order to keep the transparency of the protective coating high to thereby obtain a heat-sensitive recording material excellent in surface gloss and printing density, it is preferable to keep the difference between their refractive index and that of the polymer of the aqueous resin dispersion (A) not more than 0.05, more preferably not more than 0.02. The transparency of the protective coating increases, the printed image visible through the protective coating becomes more clear, the printing density increases and the surface gloss increases, too, as the difference in refractive index decreases. It is already emphasized that, to obtain a heat-sensitive recording material excellent in printing density and surface gloss, it is important to pay attention to the refractive index and try to improve the transparency of the protective coating, but it is no less important to try to prevent diffused reflection of light. Hence, it is important to control the mean particle size of the crosslinked particles (B) to be not more than 0.5 µm, preferably not more than 0.2 µm. If the mean particle size should exceed 0.5 µm, the diffused reflection of light is bound to increase. Even if the mean particle size is less than 0.5 µm, crosslinked particles including coarse particles larger than 1 µm, in particle size interfere with preparation of heat-sensitive recording materials excellent in both surface gloss and printing concentration. Generally, the particle size of polymers obtainable by emulsion-polymerization is 0.05 to 0.5 µm and the particle size distribution is narrow. Conversely, the particle size of polymers obtained by suspension polymerization is 1 µm, or more, the particle size distribution being relatively wide. Hence, the crosslinked particles (B) used in the present invention is required to be prepared by emulsion-polymerization. Although the crosslinked particles (B) are to be used instead of conventional fillers, it is also possible to use them in combination with some of the fillers enumerated above as good for the heat-sensitive color-developing layer on condition that it does not adversely influence the performance of the protective coating. The protective coating of the present invention requires the aforementioned aqueous resin dispersion (A) and crosslinked particles (B) as essential components but, beside these, additives such as known thermofusing substances, pH adjusters, viscosity adjusters and crosslinking agents may be useful in the manufacture of a heat-sensitive recording material on condition that any thereof does not adversely influence the performance of the protective coating. These additives can be added by some of the known methods and can be mixed with and dispersed in a coating composition by the use of, for example, a stirrer, mixer or dispersing device. The heat-sensitive recording material of the present invention is obtained by first forming a heat-sensitive color-developing layer on a supporting member such as paper, plastic film or synthetic paper by a known method, then applying thereon the aforementioned coating composition, drying and, if necessary, forming thereafter a protective coating by calendering. There is no particular limitation on the thickness of the protective coating but it may preferably be in a range of 1 to 10 µm and more preferably in a range of 2 to 5 µm. Examples of the present invention are given below. These are, however, given for the purpose of illustration and are by no means limiting on the scope of the invention. Parts and percentages (%) given in the description below mean parts by weight and weight %, respectively. Reference Example 1 (Example of manufacture of crosslinked particles) 170 parts of ion exchanged water and 0.2 parts of 25% aqueous solution of Hitenol N-08 (anionic emulsifier of Daiichi Kogyo Seiyaku Co., Ltd.) were charged into a flask equipped with a dropping funnel, stirrer, nitrogen inlet pipe, thermometer and condenser and the mixture was heated to 70°C with nitrogen gas being flowed slowly. Then 10 parts of 5% aqueous solution of ammonium persulfate was added and thereafter a pre-emulsion of monomer prepared in advance by pre-emulsifying 140 parts of methylmethacrylate and 60 parts of divinylbenzene in 21 parts of 25% aqueous solution of Hitenol N-08 and 83 parts of ion-exchange water was dropped over 2 hours from the dropping funnel. After completion of dropping, the temperature was raised to 85°C , stirring was continued for 1 hour and then the temperature was lowered to conclude polymerization. The crosslinked particles (1) thus obtained as the reaction product had a solids concentration of 42.3%, were 1.523 in refractive index at 25 °C, 0.21 µm in mean particle size as determined by the light scattering measurement, and had substantially no glass transition temperature when tested by differential scanning calorimetry (DSC). Reference Example 2 (Example of manufacture of crosslinked particles) 170 parts of ion exchanged water and 0.1 part of SN-4 (anionic emulsifier of Sumitomo Naugatuck Co., Ltd., solid content 45± 1%) were charged into the same flask as used in Reference Example 1 and the mixture was heated to 70°C with nitrogen gas being flowed slowly. Then 5 parts of 5% aqueous solution of 2,2'-azobis(2-amidinopropane)dihydrochloride and thereafter a pre-emulsion of monomer prepared in advance by pre-emulsifying 112 parts of methylmethacrylate, 30 parts of styrene, 30 parts of trimethylolpropanetrimethacrylate, 8 parts of vinyltrimethoxysilane and 20 parts of ethylacrylate in 15 parts of anionic emulsifier SN-4 and 83 parts of ion exchanged water was dropped over 3 hours from the dropping funnel. After completion of dropping the temperature was raised to 85°C , stirring was continued for 1 hour and then the temperature was lowered to conclude polymerization. The cross-linked particles (2) thus obtained as reaction product had a solid content of 43.9%, were 1.504 in refractive index at 25°C, 0.27 µm in mean particle size as determined by the light scattering measurement, and a very slight endothermic peak was noted at 130°C when tested by differential scanning calorimetry (DSC). Reference Examples 3∼5 (Examples of manufacture of crosslinked particles) In the same flask as used in Reference Example 1 crosslinked particles (3) to (5) were obtained by the same procedure as in Reference Example 1 except that the composition and quantity of the monomer were as indicated in Table 1. The result of the measurement of the physical properties is also shown in Table 1. Comparative Example 1 (Example of manufacture of crosslinked particles for comparison) Crosslinked particles for comparison (1') 42.1% in solid content were obtained by the same procedure as in Reference Example except that the composition of the monomer used as material was 190 parts of methylmethacrylate and 10 parts of divinylbenzene. The physical properties thereof were 1.496 in refractive index at 25°C, 0.30 µm in mean particle size as measured by the light scattering measuring method and approximately 115°C in glass transition temperature. Comparative Example 2 (Example of manufacture of crosslinked particles for comparison) 250 parts of ion exchanged water and 7 parts of 5% aqueous solution of PVA-205 (Kuraray Co., Ltd.) were charged into a flask equipped with a stirrer, nitrogen inlet pipe, thermometer and reflux condenser, 49 parts of methylmethacrylate and 21 parts of divinylbenzene were then added and the mixture was stirred and dispersed by a homogenizer. After introduction of nitrogen gas for 20 minutes the reaction mixture was heated to 60°C to initiate polymerization. The temperature was lowered 4 hours later to conclude polymerization and crosslinked particles for comparison (2') were obtained by subsequent filtration and drying. The physical properties thereof were 1.523 in refractive index at 25°C and 3 µm in mean particle size as measured by Coulter Counter® (Coulter Counter Limited.), and substantially no glass transition temperature was noticeable when tested by differential scanning calorimetry. Reference Example 6 (Manufacture of coating) Coating compositions [I] to [V] and coating compositions for comparison [I'] to [VI'] were prepared with the crosslinked particles (1) and (2) obtained in Reference Examples 1 to 5 and the crosslinked particles for comparison (1', 2') were obtained in Comparative Examples 1 and 2 as material by the recipes shown in Table 2. Example 1 [Liquid composition A] 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran 30 parts 10% aqueous solution of polyvinyl alcohol 30 parts Water 40 parts [Liquid composition B] Bisphenol A 30 parts 10% aqueous solution of polyvinyl alcohol 25 parts Water 45 parts [Liquid composition C] Amide stearate 25 parts Calcium carbonate 30 parts 10% aqueous solution of polyvinyl alcohol 20 parts Water 25 parts The above compositions were dispersed by sand mill until the particle size was reduced to 1 µm and the liquid compositions A, B and C were obtained. Then 20 parts of the liquid composition A, 70 parts of the liquid composition B and 10 parts of the liquid composition C were mixed to prepare a coating for heat-sensitive color-developing layer and the coating so prepared was applied to one side of a quality paper 50 g/m 2 in basis weight. Then each of the coating compositions [I]∼[V] prepared in Reference Example 6 and coating compositions for comparison [I']∼[VI'] was diluted with water to a solid concentration of 15%, applied on the heat-sensitive color-developing layer to a dry specific weight of 3 g/m 2 and a protective coating was formed by subsequent drying. The surface of the protective coating was then finished by super calender to a smoothness of not less than 3,000 seconds for preparation of heat-sensitive recording material 1'∼6'. Heat-sensitive recording material for comparison 7' was prepared by super-calendering the surface of the heat-sensitive color-developing layer without forming the protective coating. The sticking resistance, the gloss of the surface printed full in black (incident angle 75°) and the blackness of these samples were measured by the use of the following instruments. The result was as shown in Table 3. * Sticking resistance: After full-printing in black by the use of the copying function of FACOM FAX evaluation was made against the following 5-step scale. 5: No sticking sound 4: Sticking sound low 3: Sticking sound medium 2: Sticking sound high, skipping of print noted partially 1: Sticking sound high, skipping of print noted all over * Gloss of printed surface: Gloss of the surface printed full in black was measured by the use of Gloss-meter-VG-ID (Nippon Denshoku Kogyo, Ltd.) at an incident angle of 75° . * Blackness: Measurement was taken by the use of Macbeth densimeter RD914 (Kollmorgen Co.). Heatsensitive recording material No. Coating composition No. Sticking resistance Gloss of printed surface Blackness 1 [I] 5 79 1.60 2 [II] 5 70 1.59 3 [III] 4 83 1.63 4 [IV] 4 80 1.61 5 [V] 5 88 1.67 For comp'n For comp'n 1' [I'] 2 78 1) 1.50 2' [II'] 4 42 1.13 3' [III'] 4 30 1.25 4' [IV'] 4 38 1.23 5' [V'] 5 28 1.03 6' [VI'] 4 43 1.19 7' - 2 9 1.40 The heat-sensitive recording material of the present invention features the improvement of the transparency of the protective coating attainable by reducing the particle size of the crosslinked particles to 0.5 µm or less and also reducing the difference in refractive index between the polymer of the aqueous resin dispersion and the crosslinked particles, hence with it images improved in surface gloss and high in printing density compared with the conventional heat-sensitive recording materials are attainable. As shown in the examples, the images so obtained are excellent compared with not only those with a conventional protective coating but also those without a protective coating for preventing the superficial diffused reflection coating, being higher in printing density and improved in contour sharpness. Needless to say, the heat-sensitive recording material is improved in resistance to solvents, water, plasticizers, pressure et cetera definitely better than with any of the conventional protective coatings. Particularly excellent in surface gloss and printing density as it is, the heat-sensitive recording material of the present invention is very suited for such variety of uses as printing papers for printers of computers and word processors, facsimiles and various measuring instruments, prepaid cards, tickets, labels and the like that can be printed thermally.

Claims: A heat-sensitive recording material with a heat-sensitive color-developing layer formed on a supporting member characterized in that there is provided on the surface of said heat-sensitive color-developing layer a protective coating obtainable by coating the heat-sensitive color-developing layer with a coating composition containing an aqueous resin dispersion (A) and cross-linked particles (B) obtainable by emulsion-polymerizing molecules of a vinyl group-containing monomer containing not less than 15 weight % of molecules of a multi-functional monomer, said crosslinked particles having a mean particle size of not more than 0.5 µm and having substantially no glass transition temperature. A heat-sensitive recording material according to claim 1, wherein the difference in refractive index between said crosslinked particles and the solid content of said aqueous resin dispersion (A) is not more than 0.05. A heat-sensitive recording material according to claim 1 or 2, wherein said multifunctional monomer is a multifunctional (meth)acrylate having more than one vinyl group in the molecule which is a product of (meth)acrylic acid esterified with a polyhydric alcohol. A heat-sensitive recording material according to claim 1 or 2, wherein said multifunctional monomer is an aromatic compound having more than one vinyl group in the molecule. A heat-sensitive recording material according to claim 3 or 4, wherein said vinyl group containing monomer is at least one of (meth)acrylates, styrene derivatives and vinyltrialkoxysilane.

Inventors: KATSUYUKI KONO, KIYOSHI KAWAMURA, MASATOSHI YOSHIDA, KATSUYUKI, KONO, KIYOSHI, KAWAMURA, MASATOSHI, YOSHIDA
Applicants: NIPPON CATALYTIC CHEM IND, NIPPON SHOKUBAI CO., LTD.
Application year: 1991
Main classification: B41M5
IPC codes: B41M5