TW201206720A - Heat-sensitive recording medium - Google Patents

Abstract

Provided is a heat-sensitive recording medium which comprises a support, a heat-sensitive recording layer and a protective layer that is the outermost layer, said heat-sensitive recording layer and protective layer being formed on the support, is produced by the cast coating method, has high glossiness imparted thereto, and shows good print qualities, high waterproofness, high plasticizer resistance, high rubfastness and high resistance against ground color development. In the cast coating method wherein a protective layer in a wet or plastic state is dried by pressing the protective layer against a specular-finished heat drum (cast drum), it is feared that a dye precursor in a heat-sensitive recording layer reacts with a developer to cause color development in a white part of a paper sheet, i.e., so-called ground color development. By adding a carboxyl group-containing resin to the protective layer, not only properties such as waterproofness are improved but also the phenomenon of ground color development can be inhibited. Disclosed is a heat-sensitive recording medium comprising, on a support, a heat-sensitive recording layer, which contains a colorless or pale-colored electron-donating leuco dye and an electron-accepting developer, and a protective layer that is the outermost layer, wherein said protective layer comprises a carboxyl group-containing resin and said protective layer is formed by the cast coating method.

Description

201206720 VI. Description of the Invention: [Technical Field] The present invention relates to a thermosensitive recording body manufactured by a cast coating method, and more particularly to a method using a cast coating method, which has a high surface gloss and a printed image. A thermosensitive recording material excellent in quality, water repellency, plasticizer properties, abrasion resistance, and color. [Prior Art] In general, a thermosensitive recording material is usually an electron-accepting color developing agent such as a colorless or light-colored electron-donating leuco dye (hereinafter also referred to as "leuco dye") and a desired compound ( The following is also referred to as "developer"). After being ground into fine particles and dispersed, the two are mixed, and a binder, a filler, a sensitivity enhancer, a lubricant, and other additives are added to obtain the obtained coating. Coated on a support such as paper, synthetic paper, film, or plastic, and developed by a transient chemical reaction generated by heating with a heat-sensitive head, hot stamping, hot tip, laser light, or the like, thereby Obtain a recorded image. The thermal recording medium is widely used in fax machines, computer terminal printers, automatic ticket vending machines, measurement recorders, and the like. In recent years, the use of thermal recordings has also been extended to various types of coupons, receipts, labels, ATMs for banks, gas or electrical needles, and cash coupons for tickets, etc. The body requires strict characteristics such as water resistance and abrasion resistance that have not been previously problematic. In the case of such use, it is more used outside the house, and must be able to withstand the quality performance of the use in an environment that is too harsh compared to the previous one, so as not to be wet due to rain or the like, or 100117338 3 201206720 moisture, friction, etc. It is difficult to read the recording unit. Further, in the use of a ticket or a cash voucher, it is preferably a high gloss for expressing a high-grade feeling. In response to such a request, a protective layer is provided on the thermosensitive recording layer, and the protective layer contains a carboxyl group-containing resin, an epichlorohydrin resin, and a modified polyamine/melamine resin (Patent Document 1) or an acrylic resin. (Patent Document 2), thereby improving performance such as water repellency. Further, in order to make the recording surface of the thermosensitive recording material have a high gloss, the outermost layer of the thermosensitive recording material is formed by a cast coating method (Patent Documents 3 to 6, etc.). The casting method is a method of laminating a wet state or a plasticized state to a mirror-polished heating drum (hereinafter also referred to as a "casting drum"), and drying and coating. The layer simultaneously replicates the above-mentioned mirror-polished surface, thereby obtaining a high-gloss surface. [Prior Art Document] International Publication No. WO2006/075467 [Patent Document] Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Patent Document 6 [Summary of the Invention] Japanese Patent Laid-Open No. 2010-247533 -217609 PCT Patent Laid-Open No. Sho 63-147683, JP-A-2007-130874, JP-A-2009-113264 (Problem to be Solved by the Invention) 100117338 4 201206720 It is an object of the present invention to provide a thermal recording body. It is made of a heat-sensitive recording layer and a protective layer as the outermost layer on the support, and is manufactured by a cast coating method, and has a high gloss on the surface; and print image quality, water resistance, plasticizer resistance, financial friction, and wealth The background color is excellent. (Means for Solving the Problem) In order to improve the water repellency of the thermosensitive recording material, etc., a resin containing a carboxyl group in the protective layer as the outermost layer is usually used (Patent Documents 1, 2, etc.). In order to solve the above problems, the present inventors have made an effort to improve the water repellency and the like, and have found that a heat-sensitive recording material containing a carboxyl group-containing resin in a protective layer as the outermost layer is produced by a cast coating method (Patent Document 1) 2), the performance such as water resistance is further improved. Since the casting method presses the coating layer in a wet state or a plasticized state to the mirror-polished heating drum (casting drum), thereby drying the coating layer, and thus the surface of the casting drum The temperature is usually from about 100 ° C to about 120 ° C. Therefore, there is a so-called background color development in which the dye precursor in the thermosensitive recording layer reacts with the developer to cause color development of the white paper portion. Therefore, when forming the outermost layer of the thermosensitive recording material, the casting method is not usually used (Patent Document 2, etc.). On the other hand, in the case of using the cast coating method, it is necessary to select a color developing agent which does not cause coloring of the ground color (Patent Document 4). However, the inventors of the present invention have found that when a heat-sensitive recording material containing a carboxyl group-containing resin in a protective layer is produced by a cast coating method, not only the water repellency but also the general effect obtained by the casting method is obtained. The advantages of gloss, printed image quality 100117338 5 201206720 or improvement in sensitivity, etc., and the use of the cast coating method to suppress the coloration of the underlying color, as described above, & The invention is a heat sensitive note to complete the invention. Recorded with colorless or light-colored electron supply: on the support body: contains the thermal recording layer, and as the material layer ^; read the sub-receptive color developer containing the county _; and the system, the butterfly _ The heat-sensitive recording material of the present invention is carried out by means of a heat-sensitive recording medium of the present invention, in which the heat-sensitive recording body of the present invention is carried out by means of a heat-sensitive recording and pressure-receiving of the surface of the surface of the film Guu; the structure of the heat-sensitive recording layer on the support body. The intermediate layer may also be provided to have an effect of preventing oxygen from being provided as the outermost layer on the heat-sensitive layer to ensure penetration between the heat-sensitive recording layer and the protective layer. The sloping towel of the present invention contains a lion containing a county. It is expected that the money base tree may be exemplified by acrylic acid resin, oxidation, temple powder, carboxymethyl cellulose, and the conductive wire of polyvinyl alcohol in the polyvinyl alcohol, etc. Return: Resin and carboxyl modified polyvinyl alcohol. ^ In the present invention, 'if the protective layer contains a carboxyl group-containing resin, when the protective laminate in a wet state is joined to the casting drum and dried, the bond between the resin containing the edge & The reinforcing layer is formed to form a more compact protective layer, thereby obtaining the excellent effects of the present invention. Further, when the resin containing a plurality of groups is an acrylic resin, the moisture is not excessively obtained when the rewetting treatment is performed by the rewetting casting method (Rewet) in the following 100117338 6 201206720, thereby protecting the laminate from the casting drum and It is preferable to optimize the adhesion of the tungsten tumbler during drying to obtain a good surface. Further, the resin containing a plurality of groups on the right side is a thiol-modified polyethylidene alcohol, and further contains a surface alcohol resin and a polyamine/melamine resin (other than epichlorohydrin resin) in the protective layer. In this case, the polyamine/melamine-based resin exhibits fluidity by heat generation. Therefore, the adhesion to the casting drum when the laminate is bonded to the casting drum and dried is good, and a good surface is obtained. Therefore, it is better. The acrylic resin used in the present invention preferably contains (meth)acrylic acid and a monomer component copolymerizable with (meth)acrylic acid, and in 100 parts by weight of the acrylic resin, (mercapto)acrylic acid is 1 to 10 parts by weight. (Meth)acrylic acid is alkali-soluble and has a property of making the acrylic resin a water-soluble resin by the addition of a neutralizing agent. By changing the acrylic resin to a water-soluble resin, especially when the pigment is contained in the protective layer, the binding property to the pigment is remarkably improved, and even when a large amount of the pigment is contained, excellent strength can be formed. (four) layer. As a component copolymerizable with (?)acrylic acid, for example, (fluorenyl) decyl acrylate, (mercapto) acrylic acid ethyl ester, (meth)acrylic acid propyl vinegar, (mercapto) butyl acrylate Vinegar, (mercapto) acetoacetate, isobutyl vinegar, (mercapto) acrylic acid vinegar, (mercapto) hexyl acrylate, (methyl) acrylic acid _2_ethyl hexanoic acid, (meth) acrylate Acetate and other acrylic acid-based vinegar resin, epoxy resin, linaloyl resin, II modified by the stupid ethylene or its derivatives, the above-mentioned acrylic acid lysine, etc. Resin, (meth) propyl 100117338 7 201206720 Nitrile, acrylate, hydroxyalkyl acrylate, especially preferably formulated (fluorenyl) acrylonitrile and / or methyl methacrylate. The (mercapto) acrylonitrile is preferably blended in an amount of 15 to 70 parts in 100 parts of the acrylic resin. Further, the oxime methacrylate is preferably contained in an amount of from 2 to 80 parts per part of the acrylic resin. In the case of containing (fluorenyl) acrylonitrile and decyl methacrylate, it is preferred to formulate 15 to 18 parts of (indenyl) acrylonitrile in 1 part by weight of the acrylic resin, and 1 part of acrylic resin. Parts · Mix with 20 to 8 parts of methyl methacrylate. In the present invention, the acrylic acid-based resin contained in the protective layer preferably has a glass transition point (Tg) of 30 C, more preferably higher than and lower than i30 ° C, and further preferably has a Tg of more than 50. °c and below 95. (: When Tg is 3 or less, the water repellency is sufficient, but the heat resistance is insufficient. Therefore, when the protective laminate in a wet state is attached to the casting drum and dried, a good surface is not obtained. And the sufficient anti-adhesive property is not obtained (the outermost layer of the thermal recording material is adhered to the head of the printer, thereby causing some "high light overflow" which cannot be printed or the "alpha" sound of the printer). On the other hand, if the Tg is high, the anti-sticking property or the rubbing resistance tends to be improved. However, if the Tg is at 13 Å, the protective layer becomes brittle, water-repellent, plasticizer-resistant or solvent-resistant. In the case where the effect of the target is not sufficient, the Tg of the acid tree is measured by differential scanning calorimetry (DSC). - In the present invention, the protective layer + is contained. The acrylic resin is preferably a non-core-shell type. Generally, the f' core-shell type acrylic resin is superior in heat resistance to a non-core-shell type acrylic resin, and is anti-adhesive when used for a coating layer. 100117338 201206720 Excellent, so it is used more. However, due to the core shell The shell portion of the acrylic resin generally has a low thermal conductivity, and therefore has the disadvantage of poor color development sensitivity. On the other hand, the non-core-shell type acrylic resin generally has low heat resistance and is liable to cause adhesion or head slag. And other disadvantages, but used in the invention of the present invention

Tg is at 3 weeks. (: and less than 13 (the non-core-shell type acrylic resin of TC is excellent in heat resistance, and therefore has excellent color development sensitivity and good anti-stick property or scum prevention property. In the present invention, the above protective layer is used. The content of the acrylic resin to be contained (dry weight) is not particularly limited, but in terms of water repellency, it is preferably 1 part by weight or more based on 100 parts by weight of the total protective layer (dry weight). When the amount is 1 part by weight, a sufficient film for protecting the heat-sensitive recording layer located in the lower layer cannot be obtained, and good water repellency or plasticizer resistance is not obtained. The carboxy-modified polyvinyl alcohol system used in the present invention is a reaction product of a polyhydric carboxylic acid such as polyvinyl alcohol with methacrylic acid, phthalic anhydride, benzene hexaphthalic anhydride or itaconic anhydride or an esterified product of the reactants, further comprising vinyl acetate and cis. It is obtained in the form of a saponified product of a copolymer of ethylenically unsaturated direhearic acid such as diacyl acid, fumaric acid, itaconic acid, crotonic acid, acrylic acid or methacrylic acid. Specifically, how can it be mentioned in Japan? Patent special opening 53- The production method exemplified in the embodiment 1 or 4 of the publication No. 91995. Further, the degree of saponification of the carboxy-modified polyvinyl alcohol is preferably 72 to 100 mol%, and the degree of polymerization is 500 to 2400', more preferably 1,000 to 2 Å. Preferably, in the protective layer of the present invention, in addition to the carboxyl modified polyvinyl alcohol, 100117338 201206720, an epichlorohydrin resin and a polyamine/melamine resin are also contained (except for the epichlorohydrin resin). The same applies to the case where the protective layer containing the slow-modified polyvinyl alcohol further contains a surface alcohol resin and a polyamine/melamine resin, and it is considered to have a carboxyl modified polyethylene and a surface alcohol. The resin is subjected to the polarity of the crosslinking reaction and the amine/melamine moiety of the polyamine/melamine resin to associate with each other, and to protect the portion having the polarity of the crosslinking reaction, exhibits excellent water repellency and plasticizer resistance. Specific examples of the surface gas alcohol-based resin used in the present invention include polyamine-based epichlorohydrin resin and polyamine epichlorohydrin resin, and may be used singly or in combination. The amine of the main chain of the gas alcohol resin can be used from i to 4 The cationization degree and the molecular weight are preferably cationization degree of 5 meq/g. Solid or less (measured value at pH 7) and molecular weight of 500,000 or more. Specific examples include Sumirez Resin 650 (30), Sumirez Resin 675A, Sumirez Resin 6615 (above, manufactured by Sumitomo Chemical Co., Ltd.), WS4002, WS4020, WS4024, WS4030, WS4046, WS4010, and CP8970 (the above are Starlight PMC Corporation). (Manufacturing), etc. As the polyamine/melamine-based resin used in the present invention, polyammonium urea resin, polyalkylene polyamine resin, polyalkylene polyamine resin, polyamine polyurea Resin, modified polyamine resin, modified polyamine resin, polyalkylene polyamine urea fumarin resin, polyalkylene polyamine polyamine polyurea resin, and the like. Specific examples include Sumirez Resin 302 (a polyamine poly 100117338 201206720 urea resin manufactured by Sumitomo Chemical Co., Ltd.), Sumirez Resin 712 (manufactured by Sumitomo Chemical Co., Ltd., polyamine polyurea resin), and Sumirez Resin 703 (manufactured by Sumitomo Chemical Co., Ltd., polyamine polyglycan). Urea resin), Sumirez Resin 636 (manufactured by Sumitomo Chemical Co., Ltd., polyamine polyurea resin), Sumirez Resin SPI-100 (manufactured by Sumitomo Chemical Co., Ltd., modified polyamine tree grease), Sumirez Resin SPI-102A (manufactured by Sumitomo Chemical Co., Ltd., modified Polyamine* resin), Sumirez Resin SPI-106N (manufactured by Sumitomo Chemical Co., Ltd.), Sumirez Resin SPI-203 (50) (manufactured by Sumitomo Chemical Co., Ltd.), Sumirez Resin SPI-198 (manufactured by Sumitomo Chemical Co., Ltd.) ), Printive A-700 (made by Asahi Kasei Corporation), Printive A-600 (made by Asahi Kasei Corporation), PA6500, PA6504, PA6634, PA6638, PA6640, PA6644, PA6646, PA6654, PA6702, PA6704 (above, manufactured by Starlight PMC) The alkyl polyamine polyamine polyurea resin is not particularly limited, and these may be used alone or in combination of two or more. From the aspect of color development sensitivity, it is desirable to use a polyamine resin (polyalkylene polyamine resin, polyamine polyurea resin, modified polyamine resin, polyalkylene polyamine urea fumarin resin, poly Alkyl polyamine polyamine polyurea resin). In the present invention, the content (dry weight) of the carboxyl group-modified polyvinyl alcohol, the surface gas alcohol resin, and the polyamine/melamine resin contained in the protective layer is not particularly limited, and in terms of water repellency It is desirable that the total protective layer (dry-weight) is 1 part by weight or more in 1 part by weight. If it is less than 1 part by weight, a sufficient film for protecting the heat-sensitive recording layer located in the lower layer cannot be obtained, and good water repellency or plasticizer resistance or the like is not obtained. 100117338 201206720 Further, the blending amount (dry weight) of the 'epichlorohydrin resin and the polyamine/melamine resin relative to the carboxy-modified polyvinyl alcohol is preferably 100 parts by weight relative to the slow-modified polyethylene glycol. The total of the gas alcohol resin and the polyamine/melamine resin is 1 to 100 parts by weight. If the blending amount of the epigas alcohol-based resin and the polyamine/melamine-based resin is less than 1 part by weight, good water repellency or plasticization resistance is not obtained|j)·sheng et al. In the case of 1 part by weight, the gelation or viscosity of the coating liquid of the protective layer is markedly increased, and the workability is poor. The body and the 'pray coating method can be cited: (1) in the wet state of the coating layer d to the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The surface of the temporarily dried coating layer is coated with a Rewet Liquid, thereby crimping the coating layer in a flat state to the casting drum and drying it by re-casting: (re-surface method); (3) The coating layer in a wet state is subjected to a gelation casting method (coagulation method) in which a plasticized state is formed by a solidification process to be pressed against a casting drum and dried. ▲ In the wet casting method (direct method), the coating layer may be applied and dried in a state before drying. In the U scale; ^ method (return to the method), the rewetting liquid is usually called the water-soluble night containing the de-plating, as the de- _, which can be mentioned as: stearic acid, (four) or its "1 B, (4) fat Wait. Further, it is preferred that the re-wetting liquid contains completely 4-polyvinyl alcohol, partially saponified polyethylene glycol, ethyl acetylated poly(ethylene), base modified Wei Yi riding, guanamine modified polyvinyl alcohol, Acid modified polyethylene glycol, butyric acid modified polyethylene riding, olefin modified poly 100117338 12 201206720 Vinyl alcohol, nitrile modified polyvinyl alcohol, pyrrolidone modified polyvinyl alcohol, anthrone modified polyvinyl alcohol, Other modified polyvinyl alcohols such as polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose, decyl cellulose, ethyl cellulose, carboxy fluorenyl cellulose, ethyl cellulose, and acetyl cellulose, oxidized Starch such as starch, etherified starch, dialdehyde starch, esterified starch, water-soluble polymer such as casein or Arabian rubber. In particular, if polyvinyl alcohol is contained, a good surface is obtained, and high gloss is obtained, and the quality of the printed image or the whiteness of the white paper portion is good, which is preferable. Rewet Liquid may also contain surfactants, fluorescent dyes, dyes, ink fixatives, colloidal pigments, pigment dispersants, humectants, tackifiers, defoamers, preservatives, colorants, if desired. Additives such as water repellent, wetting agent, UV absorber, and cationic polymer electrolyte. In the gelation casting method (coagulation method), by applying the coagulating liquid to the coating layer (coagulation treatment) in a wet state, the coating layer can be made into a plasticized state, that is, a gel state. . In the present specification, such a coating layer is also in a plasticized state and is also contained in a wet state. The coagulation liquid is obtained by dissolving a salt such as citric acid such as calcium citrate, acetic acid, citric acid, tartaric acid, lactic acid, hydrochloric acid or sulfuric acid with calcium, magnesium or zinc, or a coagulant such as boric acid or borax in water. It is also necessary to contain the above additives such as a release agent or a surfactant. Further, in the coating layer, a polyvinyl alcohol or the like which is solidified by the reaction with the coagulant is usually contained. In the present invention, among the above casting methods, it is preferred to use a rewet casting method (rewet method). Due to the wet casting method or the gel casting method, the coating layer is 100117338 13 201206720. During the wet state, the body is pressed against the casting drum and dried, so that the water content is dried by using the rotating drum, That is, the drying load is large. If the temperature of the casting drum is increased for the purpose of strengthening the dryness, there is a possibility that the color of the white paper portion of the thermosensitive recording body is developed, and the color of the stomach is colored, and the drying is performed for the temperature of the rotating drum, and the coating must be slowed down. Cloth speed. On the other hand, the re-wet prayer method uses the rewetting liquid to close the surface layer of the temporarily dried coating layer, secretly casting the drum and drying it, so if the entire coating layer is dried first, then Casting the drum and drying the water content is less, that is, the dry (four) load is smaller. Therefore, the coating speed can be increased as compared with the wet casting method or the gel casting method. In the present invention, the surface temperature and the pressure of the crimping before the binding of the protective laminate in the wet state or the plasticized state to the casting drum are not particularly limited, and it is desirable to carry out Appropriate adjustment, usually the surface temperature of the casting drum is 30~13 (TC, preferably 6〇~1〇〇°c. The line pressure of the crimping force is 50~300 kN/m, preferably 1〇 〇~, kN/m. The surface temperature of the right casting drum is too low, and the drying of the protective layer is insufficient. If it is too same, there is a so-called background coloring that produces the white color of the thermal recording body. If the pressure of Lai is too low, the adhesion of the protective layer to the mirror-polished surface of the casting drum is insufficient, and a thermosensitive recording body having a good surface property cannot be obtained. If the pressure is too high, there is a thermal recording of the thermal recording body. If the lamination is bad and the color rendering property is lowered, in the case where the resin containing the repellent contained in the protective layer is the above-mentioned C 100117338 201206720 olefinic resin, the surface temperature of the casting drum is adjusted. a glass transition point (Tg) higher than the above acrylic resin The temperature of the present invention clearly shows the effect of the present invention, and it is preferable to obtain a thermosensitive recording material having particularly good surface properties. Then, various materials used in the thermosensitive recording layer of the thermosensitive recording material of the present invention are exemplified. In the range which does not impair the desired effect of the above-mentioned problems, the binder, the parent agent, and the pigment may be used exclusively for the protective layer, and also for each coating layer provided as needed. It is used as the heat-sensitive recording layer of the present invention. The developer is preferably 4—transalkyl-4′·n-propoxydiphenyl. The sensible s recording of the present invention is characterized in that it has a leuco dye and a color developing agent on the support. The thermal recording layer and the protective layer as the outermost layer, and the protective layer in the wet state is pressed and dried in a manner that the protective layer contacts the casting drum, thereby (4), but if the heat sensitive record When the color developing agent contained in the layer has low heat resistance, there is a so-called background color development in which the color of the heat-sensitive recording material is developed by the above-mentioned pressure bonding and drying, and the whiteness of the white paper portion. decline On the other hand, if the color of the developer is high, the color of the undertone is suppressed, but the coloration (printing density under low applied energy) is lowered. If the color is contained in the thermal recording layer The color developing agent is 4-pyridyl-n-propoxy diphenyl hydrazine, and the above-mentioned background color is changed, and the whiteness of the white paper portion of the secret is good, and the color development sensitivity is also good. Pharmacological change 100117338 15 201206720 得 =Γ子', so you can get excellent _ record body. Shifeng χ χ χ Γ Γ Γ Γ Γ 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可a sensitizer, a binder, a pigment, a lubricant, a stabilizer, etc. As a 4_ thio- 4, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In addition to the present invention, as long as the desired effect is not impeded, all the known persons in the field of pressure sensitive or thermal recording paper may not have a special color developing agent other than n-propoxy diphenyl stone. For example, it can be miscellaneous white 4 soil, erbium stone, colloidal dioxotomy, (four) Ming and other inorganic propyl (4) U·bis(4·min phenyl)cyclohexene, ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Benzoic acid (tetra), M, _ dihydroxydiphenyl stone, 2'4-indolyl-phenyl hard, bis(3-propylpropyl phenyl) stone, 4_ propyl-4-isopropyl Oxydiphenyl phenyl, 4 _ _ _ 4, _ n-butoxy diphenyl n via _ 4 ' _ methyl diphenyl fluorene, 4 · minus phenyl · 4, _ oxyphenyl Hard, 3,4-di-p-phenyl- 4'-fluorenyl phenyl stone, aminoaniline derivative, bis(tetra)phenylthioethoxy)methane I'5 disclosed in Japanese Patent Laid-Open No. Hei 8-5-3 — (4-Hydroxyphenylthio)·3-oxapentane, bis(p-hydroxyphenyl)=acid butyl vinegar, bis(p-phenyl)acetic acid? Vinegar, u•bis(tetra)-phenylidene diphenylene, 1,4-bis[α_曱-based (4,_pyridyl)ethyl]benzene, bis-indenyl-α_(4- Phenyl phenyl)ethyl] stupid, bis(4-di-carbylmethylphenyl)sulfide 100117338 16 201206720 Ether, 2,2·-thiobis(3-trioctylphenol), 2,2,- Thiobis (4_t-octylphenol), an indulgent compound of a diphenylsulfone cross-linking compound disclosed in WO97/16420, WO 02/081229 or Japanese Patent Laid-Open No. 2〇〇2_3〇1873 Compounds disclosed, in addition, thiourea compounds such as n, n, _ di-m-phenyl thiourea, p-chlorobenzoic acid, octadecyl gallate, bis [4_(n-octyloxycarbonylamine) Zinc salicylate]dihydrate, 4-[2-(p-methoxyphenoxy)ethoxy]salicylic acid, 4-[3-(p-carbyl-branched) propoxy Salicylic acid, [(2_p-methoxyphenoxyethoxy) cumyl] sulphate, aromatic tracism, and such aromatic wei acid with zinc, magnesium, Shao, Ma, Salts of polyvalent metal salts such as titanium, lanthanum, tin, and etc., and antipyrine complex of zinc thiocyanate, p-benzoic acid and other aromatic carboxylic acids The compound rhetoric and so on. These developers may be used singly or in combination of two or more. The diphenylsulfone cross-linking compound disclosed in WO97/16420 can be obtained in the form of the trade name D-90 manufactured by Nippon Soda Co., Ltd. Further, the compounds disclosed in the 'W002/081229 and the like can be obtained in the form of NKK-395 and D-100 manufactured by Nippon Soda Co., Ltd. Further, it may contain a metal chelate-type coloring component such as a fatty acid metal double salt or a polyvalent aryl aromatic compound disclosed in Japanese Laid-Open Patent Publication No. Hei 10-258577. Among the developers other than the 4-hydroxy-4f-n-propoxydiphenyl group, the above crimping is carried out by using together with 4-hydroxy-4·-n-propoxydiphenyl sulfone. The color development of the above-mentioned background caused by the heating during drying is effectively suppressed, the whiteness of the white paper portion of the thermosensitive recording material is particularly good, and the plasticizer resistance becomes extremely excellent, so that it is preferably used under the condition of 100117338 17 201206720 The general formula (formation of diphenyl hindered derivatives as color-developing, j. [Chem. 1] Here, R1 represents a carbon number of 1 to 12, a car-crossing ^ 5, more preferably a linear chain of 4 or A saturated or unsaturated hydrocarbon in a branched chain. R2 represents an atom of i, or a filament or a dilute group of carbon number 12. η is an integer of 〇~4, preferably 〇~2, more preferably 〇. ΑIndependently, Table 4 may contain a direct bond or a branched saturated or unsaturated hydrocarbon group of the carbon number of the face bond. The saturated hydrocarbon group of A may be a carbon number of 1 to 12, preferably 2 to 6, More preferably, it is a linear or branched saturated hydrocarbon of $3 to 4. m is an integer of 0 to 5, preferably 〜2, more preferably 〇. The above diphenyl hydrazine derivative may be a general formula (chemical hydrazine) Have specific The compound may also be a mixture of any of the different compounds in the formula (Chemical Formula 1). As the diphenyl pro-organism, preferably phenyl ... phenyl phenolate] phenoxy]-4 -[4-(4-Isopropoxysulfonyl)phenoxy]butane. In order to make the sensible s recording layer of the present invention contain 4-carbyl-4,_n-propoxybiphenyl In the case of a color developer other than the slate wind, the content of 4_county·4,_n-propoxy oxime is preferably a full developer (containing 4_hydroxy-4) contained in the thermosensitive recording layer. 5% by weight or more, more preferably 9% by weight or more, more preferably 9% by weight or more. 100117338 201206720 Further, the thermosensitive recording layer of the present invention contains 4-hydroxy-4'-positive propylene In the case of oxydiphenyl hydrazine and a color former of the formula (Chemical Formula 1), the total content of 4-hydroxy-4'-n-propoxydiphenyl sulfone and the color developing agent of the formula (Chemical Formula 1) It is preferably 90% by weight or more of the total color developing agent (containing a 4-hydroxy-4'-n-propoxydiphenyl sulfone and a color developing agent of the formula (Chemical Formula 1)) contained in the heat-sensitive recording layer. As no use in the thermal recording material of the present invention The dye may be used in all of the known pressure sensitive or thermal recording papers, and is not particularly limited, and is preferably a triphenyl decane compound, a fluorescent yellow mother system compound, an anthraquinone system, a divinyl compound or the like. Specific examples of the representative colorless or light-colored dyes (dye precursors). These dye precursors may be used singly or in combination of two or more kinds. <Triphenyl decane-based leuco dye> 3 ,3-bis(p-diodecylaminophenyl)-6-dimercaptodecanolide [alias crystal violet lactone], 3,3-bis(p-didecylaminophenyl)decanolide [ Alias malachite lactone] &lt;fluorescent yellow mother system leuco dye&gt; 3-diethylamino-6-fluorenyl glory yellow mother, 3-diethylamino-6-mercapto-7-anilino Fluorescent yellow mother, 3-diethylamino-6-fluorenyl-7-(o-, p-diphenylanilino) fluorescent yellow precursor, 3-diethylamino-6-methyl-7- Gas-fluorescent yellow mother, 3-diethylamino-6-methyl-7-(m-tris-decylphenylamino) glory yellow mother, 3-diethylamino-6-mercapto-7-( O-chloroanilino) Fluorescent Yellow Mother, 3-Diethylamino-6-indenyl-7-(p-chloro Amino)fluorescent yellow mother, 3-diethylamino-6-mercapto-7-(o-fluoroanilino) campan yellow mother, 3-diethylamino-6-methyl 100117338 19 201206720 base- 7-(m-decylanilide) laurel yellow mother, 3-diethylamino-6-methyl-7-n-octylanilide fluorescent yellow mother, 3-diethylamino-6-anthracene Base-7-n-octylamine glory yellow mother, 3-diethylamino-6-fluorenyl-7-carbylamino glory yellow mother, 3-diethylamino-6-mercapto-7 -dibenzylaminofluorenyl yellow mother, 3_diethylamino-6-chloro-7-fluorenyl glory yellow mother, 3-diethylamino-6-chloro-7-aniline fluorescent yellow mother , 3-diethylamino-6-chloro-7-p-nonylanilinyl fluorescent yellow precursor, 3-diethylamino-6-ethoxyethyl-7-aniline-based campanescent yellow precursor, 3-Diethylamino-7-fluorenylfluorescent yellow mother, 3-diethylamino-7-chlorofluorescent yellow mother, 3-diethylamino-7-(m-trifluorodecyl aniline Fluorescent yellow mother, 3-diethylamino-7-(o-chloroanilino)fluorescent yellow mother, 3-diethylamino-7-(p-anilide) glory yellow mother, 3- Diethylamino-7-(o-fluoroanilino)fluorescent yellow matrix, 3- Ethylamino-benzo[a]fluorescent yellow mother, 3-diethylamino-benzo[c]fluorescent yellow mother, 3-dibutylamino-6-fluorenyl-fluorescent yellow matrix , 3-di-n-butylamino-6-fluorenyl-7-anilinofluorescent yellow precursor, 3-dibutylamino-6-fluorenyl-7-(o-, p-dimethylanilinyl) Fluorescent yellow mother, 3-dibutylamino-6-mercapto-7-(o-chloroanilino)fluorescent yellow mother, 3-dibutylamino-6-mercapto-7-(p-chloroaniline Fluorescent yellow mother, 3, dibutylamino-6-methyl-7-(o-fluoroanilino) fluorescent yellow mother, 3-dibutylamino-6-fluorenyl-7- Trifluoromethylanilino)fluorescent yellow mother, 3-dibutylamino-6-fluorenyl-7-chlorofluorescent yellow mother, 3-dibutylamino-6-ethoxyethyl-7 - anilino fluorescent yellow mother, 3-dibutylamino-6-chloro-7-anilinyl fluorescent yellow mother, 3-dibutylamino-6-methyl-7-p-methylanilinyl Light yellow precursor, 3-dibutylamino-7-(o-100117338 20 201206720 gas aniline) fluorescent yellow mother, 3-dibutylamino-7-(o-fluoroanilino) fluorescent yellow matrix, 3 -di-n-decylamino-6-mercapto-7-anilinyl glory yellow mother, 3_di-n-pentyl -6-mercapto-7-(p-anilide) fluorescent yellow matrix, 3-di-n-pentylamino-7-(m-trifluorodecylphenylamino)fluorescent yellow matrix, 3-di- n-Pentylamino-6-gas-7-anilinofluorescent yellow mother, 3-di-n-pentylamino-7-(p-chloroanilino)fluorescent yellow mother, 3-pyridyl-6 - mercapto-7-anilinofluorescent yellow mother, 3-piperidinyl-6-fluorenyl-7-anilinofluorescent yellow mother, 3-(N-methyl-N-propylamino)-6 - mercapto-7-anilinyl fluorescent yellow precursor, 3-(N-fluorenyl-N-cyclohexylamino)-6-fluorenyl-7-anilinyl fluorescent yellow precursor, 3-(N-ethyl -N-cyclohexylamino)-6-fluorenyl-7-anilinofluorescent yellow precursor, 3-(N-ethyl-N-hexylamino)-6-mercapto-7-(p-chloroanilinyl) Fluorescent yellow mother, 3-(N-ethyl-p-anilino)-6-fluorenyl-7-anilinofluorescent yellow mother, 3-(N-ethyl-N-isoamylamino) -6-mercapto-7-anilinofluorescent yellow mother, 3-(N-ethyl-N-isoamylamino)_6_qi-7-aniline glory yellow mother, 3-(N-ethyl -N-tetraosylamino)-6-methyl-7-anilinofluorescent yellow mother, 3-(N-ethyl-N-isobutylamino)-6-methyl-7- stupid Amine-based glory yellow mother, 3-(N-ethyl-N-B Propylamino)-6-fluorenyl-7-anilinofluorescent yellow mother, 3-cyclohexylamino-6-chlorofluorescent yellow mother, 2-(4-oxahexyl)-3-dioxin Aminoamino-6-mercapto-7-aniline-based campan yellow precursor, 2-(4-oxahexyl)-3-diethylamino-6-methyl-7-anilinyl fluorescent yellow precursor, 2-(4-oxahexyl)-3-dipropylamino-6-fluorenyl-7-anilinyl glory yellow precursor, 2-mercapto-6-p-(p-didecylaminophenyl)amine Alkylanilide fluorescent yellow mother, 2-decyloxy-6-p-(p-didecylaminophenyl)aminoaniline fluorescent yellow 100117338 21 201206720 Parent, 2-chloro-3-methyl-6- (p-Phenylaminophenyl)aminoanilinyl fluorescent yellow precursor, 2-chloro-6-p-(p-dimethylaminophenyl)aminoanilinyl fluorescent yellow precursor, 2-nitro- 6-p-(p-Diethylaminophenyl)aminoaniline-based fluorescent yellow precursor, 2-amino-6-p-(p-diethylaminophenyl)aminoanilinyl fluorescent yellow precursor, 2 -diethylamino-6-p-(p-diethylaminophenyl)amino-phenylamino-fluorescent yellow precursor, 2-phenyl-6-mercapto-6-p-(p-phenylaminobenzene) Aminoaniline-based fluorescent yellow mother, 2-benzyl-6-p-(p-phenylamino) Aminoaniline-based fluorescent yellow mother, 2-hydroxy-6-p-(p-phenylaminophenyl)aminoanilinyl fluorescent yellow precursor, 3-mercapto-6-pair (p-didecylamine) Phenylphenyl)aminoaniline-based fluorescent yellow mother, 3-diethylamino-6-p-(p-diethylaminophenyl)aminoanilinyl fluorescent yellow precursor, 3-diethylamino -6-p-(p-Dibutylaminophenyl)aminoanilinyl fluorescent yellow precursor, 2,4-dimercapto-6-[(4-dimethylamino)anilino]-fluorescent yellow Maternal &lt;Digital leuco dye&gt; 3,6,6'-tris(didecylamino) snail [9,3, succinct], 3,6,6, _tri(diethyl Amino) snail [荞-9,3'-駄内|], &lt;divinyl leuco dye&gt; 3,3_bis-[2-(p-didecylaminophenyl)_2_(曱Oxyphenyl)ethylidene]_4,5,6,7-tetracodone, 3,3-bis-[2-(p-didecylaminophenyl)-2-(p-methoxyl) Phenyl)vinyl]_4,5,6,7_tetragen enthalpy, 3,3·bis-[U-bis(4-oxaridinyl)-ethyl-2-yl]_4 ,5,6,7 tetrabromoindole and [丨(4·decyloxyphenyl)-1-(4-°pyrrolidylphenyl)-extended ethyl-2-100117338 22 201206720 base]- 4,5,6,7-four Chlorolactone &lt;Other&gt; 3-(4-Diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4- Azaindole, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-octyl-2-methylin-3-yl)-4-aza Azlactone, 3-(4-cyclohexylethylamino-2-indolyl)-3-(1-ethyl-2-indolyl 〇 η-3-yl)-4-aza Ugly, 3,3-bis(1-ethyl-2-indenyl σ 弓 _3 stomach base) 酜, 3,6· bis (diethylamino) fluorescent yellow mother nitrate 'Base' aniline decylamine, 3,6-bis(diethyl benzyl) fluorescein yellow mother-γ-(4'-nitro)aniline decylamine, 1,1_bis_[2', 2',2",2"-tetra-(p-dimethylaminophenyl)-vinyl]_2,2.dicarbonitrile, 1,1-bis-[2,,2',2", 2,,-tetra-(p-didecylaminophenyl)-vinyl]_2_/3·naphthyl ethane, 1,1-bis-[2',2,,2&quot;,2"- Tetra-(p-diodecylaminophenyl)-vinyl]-2,2-diethyl ethane, bis-[2,2,2^2,-tetra-(p-didecylaminophenyl) -Ethyl]dimethyl methacrylate as a heat sensitive recordable body of the present invention Sensitizers, can be used to cut off the feet of the well-known sensitizer. The sensitizer may, for example, be a fatty acid guanamine such as decylamine stearate or decyl palmitate, ethyl bis-indoleamine, montanic acid wax, polyvinyl hydrazine or 1,2-di-(3-methyl group). Stupidoxy)ethane, p-benzylbiphenylbenzyloxynaphthalene, 4-biphenyl-p-phenylene ether, cross-linked tris, diphenoxyethane, dibenzyl oxalate, oxalic acid di(p-chlorobenzyl) Base ester), bis(p-methylbenzyl oxalate), dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-phenylene carbonate, phenyl-α-naphthalene carbonate , 1,4-diethoxynaphthalene, hydrazine hydroxy-2-naphthoic acid benzene 100117338 23 201206720 vinegar, o-xylene-bis-(benzene, 4 (m-methylphenoxymethyl) biphenyl , 4,4, Ethyldioxy-bis-benzoic acid dibenzyl ester, benzotrimethoxymethane, H bis(3-methylphenoxy) acetonitrile, bis[2_(4_f oxy) The phenoxyethyl ester, the p-nitrobenzoic acid, and the benzoic acid are not particularly limited. These sensitizers may be used singly or in combination of two or more. The adhesive which can be used in the thermosensitive recording material of the present invention can be exemplified by: fully saponified polyethylene Return to alcohol, partially-interested polyvinyl alcohol, ethylene-acetylated polyethylene glycol, county modified polyethylene glycol, Lai modified polyethyl alcohol, sulfonic acid modified polyvinyl alcohol, butyric acid modified poly Vinyl alcohol, olefin modified polyethylene glycol, nitrile modified polyvinyl alcohol &quot; than slightly modified to change polystyrene, (four) modified f polyethylene glycol, other modified polyvinyl alcohol m ethyl cellulose, methyl Cellulose, ethyl cellulose buffer methyl cellulose, styrene-cis-sebacic acid needle copolymer, styrene-butadiene copolymer and such as ethyl cellulose, acetyl cellulose Cellulose derivatives, road protein, arabin rubber, cerium oxide powder, gelatinized starch, dialdehyde starch, esterified starch, polyvinyl chloride, polyvinyl acetate, polypropylene decylamine, polypropylene _, polyethylene dingjun Polyphenylene (10) and these copolymers 'polyamine resin, linaloyl resin, petroleum resin, betaene resin, g-resin, acridine resin, etc. These polymer materials are dissolved in water, alcohol, ketone. In the case of using solvents such as esters, esters, and hydrocarbons, it may be emulsified or dispersed in a paste or water in water or other medium. It is used in combination with the required quality. As the crosslinking agent which can be used in the thermosensitive recording material of the present invention, glyoxal, methylol melamine, melamine-furfural resin, trimerization 100117338 24 201206720 cyanide can be exemplified. Amine gland resin, polyamine epichlorohydrin tree, uranium chloride, ammonium persulfate, sodium persulfate, &amp; 丨 know, over ^ 酉 civilization climbing, gasification materials, money iron, magnesium gasification, Butter, boric acid, ^ can be used in the face of the present invention (4) _ '可兴出 oxygen cut, carbonated mother, kaolin, calcined high resident, two titanium oxide inorganic or organic fillers, etc. = abrasion resistance of the heat-sensing head, etc.: is metakaolin, calcined kaolin, aluminum hydroxide. In the present invention, by making the kaolin contained in the above protective layer, it is possible to use Jiangyan #撂思 a '匕 for 30 or more. A finer 'more excellent quality money _. In the present invention

The aspect ratio of the left 'material' refers to the powder taken by the _f submicroscope. For the == cut particle, the calculation formula is used (the aspect ratio is 1 diameter/thickness; the value of the average is obtained by busy output, and the value of the aspect ratio is obtained. The larger the pigment, the larger the fan production will be. The aspect ratio of (4) is the average of the ratio of the length (thickness) of the shortest axis of 1G. The details are for the kaolin and the general use of paper materials. The pigment phase*' is compared with the case where the Lai view is smaller, and the amount of kaolin required for the same area is reduced. That is, it is considered that the thin layer can be used because of the thin layer energy (4). Lowering 'and obtaining the _color $ sensitivities and image products f.*, the preferred aspect ratio of the high genus used in the present invention is 3 〇 to 〇〇, more preferably 30 to 75. When the aspect ratio becomes larger than the cut, the coating liquid may be 100117338 25 201206720, the moisture retention property is lowered, the coating suitability is remarkably lowered, and the protective layer is locally densified, and the color development sensitivity is uneven. Further, the kaolin is ideally The average diameter is 4 / xm or less. If the aspect ratio is more than 30, the average diameter of kaolin is greater than 4 /mi, the surface smoothness of the protective layer is lowered, and there is a problem that the quality of the recorded image is lowered. Further, the kaolin used in the present invention usually has an oil absorption of 50 to 80 ml/100 g, and the BET specific surface area is 10 to 30 m2/g. In contrast, mica (Mica) having an aspect ratio of 100 or more has an oil absorption of about 10 to 30 ml/100 g, and a BET specific surface area of about 2 to 10 m 2 /g, thereby absorbing water or The ability of the solvent is low. The use of the kaolin of the present invention is superior to the case of using mica, and the heat sensitive recording material is excellent in water repellency, solvent solubility, and anti-crushing property. The kaolin having an aspect ratio of 30 or more in the present invention can be borrowed. It is obtained by special pulverization to classify the layered kaolin, etc. Kaolin having an aspect ratio of 30 or more in the protective layer exerts an effect by its specific shape, and therefore it is preferably used alone, but the pigment in the protective layer is used. When a combination of other pigments is used, the aspect ratio of kaolin having an aspect ratio of 30 or more is preferably 50 parts by weight or more, more preferably 50 parts by weight or more, more preferably 100 parts by weight of the total number of the pigments in the protective layer. for 80% by weight or more. The lubricant to be used in the thermosensitive recording material of the present invention may, for example, be a fatty acid metal salt such as zinc stearate or calcium stearate, a wax or an oxime ketone resin, etc. 100117338 26 In addition, in the present invention, the 4,4'-butylene group (6-) which is an image stabilizer which exhibits the oil resistance effect of the recorded image, is added to the range which does not impair the desired effect of the above-mentioned problem. Second butyl-3-methyl sulphonate), 2,2, _-first butyl-5,5'-dimercapto-4,4,-sulfonyl bisphenol, 1,1,3- Tris(2_曱基冰经美•-5-cyclohexylphenyl) butadiene, 1, U-bis(2-indolyl-4-yl)-second-butylphenyl)butane, oxy -4'-(2,3-epoxy-2-methylpropoxy)diphenyl hard, etc. Further, a benzophenone-based or triazole-based ultraviolet absorber, a dispersant, an antifoaming agent, or the like may be used. Antioxidants, fluorescent dyes, etc. The material used in the thermosensitive recording layer of the thermosensitive recording medium of the present invention, the ninth material, the color developing agent, the sensitizing agent and the material added as needed are dyed by a ball mill, such as a grinder, a sand mill, or the like. The emulsifying device is micronized until it becomes a particle diameter of several micrometers or less, and a binder is added and various kinds of reinforcing materials for the purpose are added to prepare a coating liquid. The amount of the above materials is determined according to the required properties and lack of adaptability. 'It is not particularly limited, and it is preferably 0.5 to 10 parts by weight relative to the benefit material and parts by weight, and the sensitive agent is 0.5~1〇About heavy denier. In the present invention, after coating the heat-sensitive recording layer containing the above composition on any of the paper, the recycled paper, the synthetic paper, the film, the plastic film, the non-woven fabric, and the composite sheet of the composite material. The moisturizing state will be accompanied by the protective layer, and the protective shield will be crimped and bonded by the material layer contact to obtain the target coating surface of the thermosensitive recording layer, minus __ The range of parts 100117338 27 201206720. Further, the coating amount of the protective layer provided on the thermosensitive recording layer is not particularly limited, but is preferably in the range of 0.5 to 5 g/m 2 in terms of solid content. In order to improve the printing density, etc., the thermal recording material of the present invention may be provided with an undercoat layer containing the above pigment, binder, or the like under the thermal recording layer. Further, a back coating layer may be provided on the opposite side of the heat-sensitive recording layer of the support to realize curling. The means for applying the respective layers such as the undercoat layer, the thermal recording layer, the protective layer, and the post-coat layer is not particularly limited, and it can be applied according to a well-known conventional technique. As the coating method of each layer, an air knife method, a bending knife method, a skew knife method, a roll method, a groove type curtain method, a slide type curtain method, a slide funnel type curtain method, and a droplet type can be exemplified. The curtain method, the spray method, the die method, and the like are appropriately selected from these coating methods and used. In addition, various known techniques in the field of the thermosensitive recording material using a smoothing treatment such as a super calender or the like can be appropriately added after the application of each layer. [Examples] The following examples are exemplified by the examples, but are not intended to limit the invention. Further, parts and % represent parts by weight and % by weight, respectively. The undercoat layer coating liquid was prepared by stirring and dispersing a formulation containing the following formulation amount. &lt;Undercoat Coating Liquid&gt; Calcined Kaolin (Ansylex 90, manufactured by Engelhard Co., Ltd.) 100 parts of styrene-butadiene copolymer latex (manufactured by Z本Ze〇n Co., Ltd.: 100117338 28 201206720 ST5526, solid portion 48〇) /0) 40 parts of π fully saponified polyethylstilbene alcohol solution (manufactured by Kuraray Co., Ltd.: pVAl17, solid content 10%) 3 parts water: 160 parts • The following formulation amount of developer dispersion (solution A), The leuco dye dispersion (B liquid) and the sensitizer dispersion (C liquid) were each wet-ground by a sand mill until the average particle diameter became 0.5 μm. Reagent dispersion (solution A) 4-hydroxy-4,-n-propoxy diphenyl sulfone (manufactured by Api c〇卬〇rati〇n: JKY-146) 6.0 parts of fully saponified polyvinyl alcohol aqueous solution ( Made by Kuraray Co., Ltd.: PVA117, solid content 10%) 18.8 parts water 11.2 parts leuco dye dispersion (solution B) 3-dibutylamino-6-mercapto-7-aniline fluorescent yellow mother (Yamada Chemical Co., Ltd. Manufacture: ODB-2) 3.0 parts of fully saponified polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd.: PVA117, solid content 10%) 6.9 parts water 3.9 parts sensitizer dispersion (liquid C) diphenyl sulfone 6.0 parts completely saponified Type polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd.: PVA117, 100117338 29 201206720 18.8 parts solids 1%%;)

U.2 U and then 'mixed dispersion in the following ratios> Sensitive recording layer coating liquid 1> Developer dispersion (A solution) Achromatic dye dispersion (B solution) Sebacin dispersion (Hydrazine Chemical Co., Ltd. solid content) 50〇/〇), Preparation of Thermal Sensing Recording Layer Coating Liquid Preparation 36.0 parts 13.8 parts: Mizukasil P-604, 20.0 parts of fully saponified polyvinyl alcohol aqueous solution (manufactured by 玎乐丽公司: PVA1H, solid content 10%) 10.0 parts water 25.0 parts &lt;sensible recording layer coating liquid 2&gt; developer dispersion (solution A) 36.0 parts of leuco dye dispersion (solution B) 13.8 parts of sensitizer dispersion (liquid C) 36.0 parts of fully saponified polyethylene Aqueous alcohol solution (10% solid content manufactured by Kuraray Co., Ltd.): PVA117, 10.0 parts of water 25.0 parts, then mixed with the constitutive contact, prepared protective layer coating &lt;protective layer coating liquid 1&gt; Engineering kaolin (ImeryS Company··生. I k · Contourl50〇, aspect ratio 100117338 201206720 60) 50% dispersion 12.0 parts non-core-shell acrylic resin (manufactured by Mitsui Chemicals Co., Ltd.: ASN1004K, Tg55°C 'solid content 18%) 30. Zinc stearate Manufactured by the company: Hydrin L536, 40% solids) 2.0 parts of surfactant (made by Rixin Chemical Co., Ltd.: Surfynoll04P, solid content 5〇%) (U parts 69.0 parts &lt; protective layer coating liquid 2 &gt; engineering 焉岭土(Manufactured by Imerys: C〇nt〇ur 1500, aspect ratio 60) 50% dispersion 12 〇 carboxy modified polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd.: KL118, solid content 12%) 26.7 parts of polyamine gas Alcohol resin solution (manufactured by Starlight PMC: WS4030, solid content 25%) 3.8 parts modified 1 amine resin solution (Sumitomo Chemical Co., Ltd.: Sumirez Resin SPI102, solid content 45%) 2.1 parts zinc stearate (Zhongjing Oil Company) Manufacture: Hydrin L536, solid content 40%) 3.8 parts surfactant (made by Rixin Chemical Co., Ltd.: Surfynoll04P, solid content 50%) 0.1 parts 7jC 69.0 parts 100117338 31 201206720 &lt;Protective layer coating liquid 3&gt; Engineering kaolin (Imerys Company manufacturing: Contour 1500, aspect ratio 60) 50% dispersion 12.0 parts of carboxyl modified polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd.: KL118, solid content 12%) 10.2 parts of zinc stearate (made by Zhongjing Oil Company: Hydrin L5 36, solid content 40%) 3.8 parts of surfactant (made by Rixin Chemical Co., Ltd.: Surfynoll04P, 50% solid content) 〇·1 part of water 28.8 parts, and then the formulation consisting of the following formula is stirred and dispersed, and then prepared. Wetting fluid. &lt;Re-wetting solution 1&gt; Release agent (manufactured by St. Nopco: ΡΕΜ-17, solid content 40%) 1.25 parts of surfactant (manufactured by St. Nopco: SN-WET-L, solid content 100%) ) 0.1 part of water 96.4 parts &lt;rehumidation liquid 2&gt; Fully saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd.: PVA117, solid content 12%) 2.7 parts of release agent (manufactured by St. Nopco: PEM-17, solid form) 40%) 100117338 32 201206720 1.25 parts surfactant (manufactured by St. Nopco: SN-WET-L, 100% solids) 〇·1 part water 93.7 parts &lt;rehumidification liquid 3&gt; Release agent Manufactured by Nopco: ΡΕΜ-17, 40% solids) 0.5 part of surfactant (manufactured by St. Nopco: SN-WET-L, 100% solids) 〇·1 part of water 96.7 parts, then will contain The formulation of the following formulation was stirred and dispersed to prepare a coagulating liquid. &lt;coagulating liquid&gt; Borax 2.0 parts of boric acid 2.0 parts of malic acid 0.5 parts of mold release agent (made by Nisshin Chemical Research Co., Ltd.: DEF-002, solid content 20%) 2.5 parts of water 93.0 parts [Example 1] Using a machete The undercoat layer coating liquid was applied onto one surface of a support (base paper having a basis weight of 60 g/m 2 ), and the coating amount was set to 10.0 g/m 2 in terms of a solid content, followed by drying to obtain a primer. Layer coated paper. Then, the photosensitive layer 100117338 33 201206720 recording layer coating liquid 1 was applied onto the undercoat layer of the above-mentioned undercoat coated paper by a bar knife method, and the coating amount was made to be 5.0 g/m 2 in terms of solid content. Drying was carried out to obtain a heat sensitive recording layer coated paper. Then, the protective layer coating liquid i is applied onto the thermosensitive recording layer of the above-mentioned heat sensitive s recording layer coated paper by a groove type curtain method, and the coating amount is set to 3.0 g/m in terms of solid content. The drying was carried out, and the smoothness of the coated surface was changed to (9) to 2 〇〇〇·sec., and the calorimeter was processed to produce a thermosensitive recording material. Then, a coating of 5 〇g/m 2 of the rewet liquid is applied to the protective layer of the thermal recording material, and the protective layer is brought into contact with the surface temperature in a manner to become a casting drum side. (The rc casting drum was subjected to pressure treatment and heating (drying) treatment at a line pressure of 100 kN/mT using a rubber roller, and a heat sensitive recording body of Example 制作 was produced. [Example 2] Replacing 6.0 parts of 4-formyl-4,-n-propoxydiphenyl sulfone (JKY-146) of the developer dispersion (solution A) with 4-hydroxyl-n-propoxydiphenyl sulfonium (JKY) -146) 翏0 parts and 1-[4_(4-hydroxyphenyl hydrazinyl)phenoxy^(4)4·isopropoxyphenylsulfonyl)aloxy]butane (Api Cor-manufactured :JKY-214) 1_0 parts In the same manner as in the example j, a thermosensitive recording material was obtained. [Example 3], except that the reagent solution dispersion (liquid A) was replaced with 4 parts of 4-hydroxyl-propoxyphene-diphenyl (JKY-146) (4K). Phenyl barrier (10) 100117338 34 201206720 in conjunction with Example 1 and Example 2

Manufactured by Corporation: NYDS) 6. In addition to the same method, a thermosensitive recording material is obtained. [Example 4] A thermosensitive recording material was obtained in the same manner except that the rewetting liquid 1 was replaced with the rewetting liquid 2. [Example 5] On the one side of the support (base paper having a basis weight of 60 g/m 2 ), the coating liquid on the dry top of the substrate was made to have a coating amount of 1 〇.〇g/m2 in terms of solid content. De, A〆^ is dried to obtain a base coat coated paper 'then' using a knife coater, and the heat sensitive recording layer coating liquid 2 is applied onto the undercoat layer of the undercoat coated paper to After the coating amount of the solid 幵 a a 成为 5 became 5. G g / m 2 , it was dried to obtain a heat-sensitive recording layer coated paper. Then, the protective layer coating liquid 2 was applied onto the thermosensitive recording layer of the above-mentioned salty heat recording layer coated paper by a knife coater, and the coating amount was changed to 3. 〇g/m2 in terms of solid content. The film was dried and processed by a super calender so that the smoothness of the coated surface was 1 〇〇〇 to 2 sec., and a thermosensitive recording material was produced. Then, 5 〇g/m 2 of the rewet liquid 3 is applied to the protective layer of the thermal recording material, and when the protective layer is wet, the rewet protective layer is contacted with the surface to become the casting drum side. The heat-sensitive recording material was produced by performing a pressure treatment and a heating (drying) treatment (rewetting casting treatment) on a casting drum having a temperature of 7 〇〇c at a linear pressure of 100 kN/m. [Example 6] A thermosensitive recording material was produced in the same manner as in Example 100117338 35 201206720 except that warm water (40 to 50 ° C) was used instead of the rewetting liquid 3. [Example 7] The undercoat layer coating liquid was applied to one surface of a support (base paper having a basis weight of 6 〇g/m 2 ) by a scimitar method, and the coating amount was set to 1 以 in terms of solid content. After 〇g/m2, the crucible was dried to obtain a base coat coated paper. Then, the hot-sensitive recording layer coating liquid 1 is applied onto the undercoat layer of the primer-coated coated paper by a bar knife method, and the coating amount is made to be 5.0 coffee 2 in a solid content, and dried. A heat sensitive recording layer coated paper was obtained. Then, the protective layer coating liquid 3 was applied onto the thermosensitive recording layer of the above-mentioned thermosensitive recording layer coated paper by a roll method, and the coating amount was 3.0 2 g/m in terms of solid content, and then the protective layer was wet. In the state, the coagulating liquid is applied to the protective layer by a roll method to have a plasticized state (gel state). Then, when the protective layer is in a gel state, the protective layer is brought into contact with the casting drum having a surface temperature of 70 ° C in the manner of becoming a casting drum side, and is pressurized at a linear pressure of 100 kN/mT using rubber. The heat-sensitive recording material of Example 4 was produced by treatment and heating (drying) treatment (gelation casting treatment). [Comparative Example 1] A thermosensitive recording material was obtained in the same manner as in Example 1 except that the rewet casting treatment was not carried out. [Comparative Example 2] A thermosensitive recording material was obtained in the same manner as in Example 5 except that the rewet casting treatment was not carried out. 100117338 36 201206720 [Comparative Example 3] In addition to replacing the carboxyl group-modified polyethylene glycol aqueous solution of the protective layer coating liquid 2 with the ethyl brewing base modified polyvinyl alcohol water> liquid (manufactured by Nippon Synthetic Chemical Co., Ltd.: Z100, A thermosensitive recording material was obtained in the same manner as in Example 5 except for 12% of the solid content. The following evaluation tests were conducted on the thermosensitive recording materials obtained in the above Examples and Comparative Examples. &lt;Printing Density&gt; For the thermal recording material to be produced, a printing tester (manufactured by Ogura Electric Co., Ltd., TH-PMD 'installation hall, heat-sensing head manufactured by Seiko Co., Ltd.) was used, and energy was applied at 0.41 mJ/dot or 0.35. Physical printing is performed under mJ/d〇t. The printing density was evaluated by measuring the concentration of the printing portion using a Mcbeth concentration meter (RD-914, using an amber filter). &lt;Color development sensitivity (printing density under conditions of low energy application)&gt; For the thermal recording material to be produced, a printing tester (manufactured by Ogura Electric Co., Ltd.: TH-PMD, a thermal induction head manufactured by Kyocera Corporation) was used. Physical printing was performed with an applied energy of 0.27 mJ/dot. The concentration of the printed portion was measured using a Macbeth densitometer (RD-914, using an amber filter) to evaluate the color development sensitivity. &lt;Printed image quality&gt; For the thermal recording material to be produced, a printing tester (manufactured by Okura Electric Co., Ltd.: TH-PMD, a heat-sensitive head manufactured by Kyocera Corporation) was used, and an energy of 0.27 mJ/ was applied to the application 100117338 37 201206720. Physical printing under dot. The image quality after printing was evaluated by visual observation using the following criteria. Good: No unevenness was observed at all. Yes: A slight unevenness was observed. No: Unevenness is observed. &lt;Background color development&gt; For the thermosensitive recording material to be produced, the concentration of the white paper portion was measured using a Macbeth densitometer (RD-914, using an amber filter), and the color of the underlying color caused by the casting treatment was evaluated ( The color of the bottom part (fog)). The smaller the value, the less the background color is developed and the better the quality. &lt;Gloss&gt; For the heat-sensitive recording material to be produced, a 75-degree gloss of the surface of the protective layer was measured in accordance with JIS-P8142 using a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd.: VG7000). The larger the value, the higher the gloss and the better the quality. &lt;Whiteness&gt; The whiteness (%) of the white paper portion was measured using a spectroscopic color/whiteness meter (manufactured by Nippon Denshoku Industries Co., Ltd.: PF-10). The larger the value, the higher the whiteness and the better the quality. &lt;Water repellency&gt; The heat-sensitive recording material to be produced was subjected to a printing tester (manufactured by Okura Electric Co., Ltd.: TH-PMD, a heat-sensitive head manufactured by Kyocera Corporation), and an entity was applied at an energy of 41 mJ/dot. print. After 24 hours of water immersion treatment at 23 ° C, 50% Rh ring 100117338 38 201206720 i, the printing density of the printing part was measured by a Macbeth concentration meter (RD-914, using an amber filter), according to The residual value was calculated by the value after the treatment, and the water repellency was evaluated. Residual rate (%) == (printing density after treatment/printing density before treatment) xl 〇〇 &lt; rubbing resistance&gt; For the thermosensitive recording material produced, a steel thief to which a load of 1000 gf/cm 2 was applied was used. The surface of the protective layer was rubbed, and line color development was evaluated by visual observation using the following criteria. Good: almost no color development: thinner color development is not possible: more intense color development &lt; and ten plasticizer properties> For the thermal recording material produced, use a printing test machine (manufactured by Okura Electric Co., Ltd. TH-PMD , installed Beijing: is the company's thermal sensor head), physical printing at 0.41 mJ / dot. The enamel layer of vinyl chloride coating material (manufactured by Mitsui Tosoh Co., Ltd.: mghwrap KMA) was wound on a paper tube, and the above-mentioned heat sensitive recording body was placed thereon in such a manner that the printing portion became the outer surface, and then three layers were wound thereon. The above-mentioned ethylene-ethylene coating material is fixed. Then, after treating for 2 hours in an environment of 40 ° C and 50% RH, the printing density of the printing portion was measured by a Macbeth concentration meter (RD·914 ' using amber-axis coloring mirror), and the value was calculated based on the value after the processing. Residual rate (above), evaluation of plasticizer resistance. 100117338 39 201206720 The results of the evaluation are shown in the table below. 100117338 201206720

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Claims (1)

201206720 VII. Patent application scope: 1. A thermosensitive recording body having a thermosensitive recording layer containing an electron-donating leuco dye and an electron-accepting color developer, which are colorless or light-colored, and As the outermost protective layer, and the protective layer contains a carboxyl group-containing resin; and the heat sensitive recording body in which the protective layer is wet, the protective layer is brought into contact with the mirror-polished heating drum to be crimped and It is dried and formed thereby. 2. The thermosensitive recording material according to the first aspect of the invention, wherein the carboxy group-containing resin is an acrylic resin. 3. The thermosensitive recording material according to claim 2, wherein the acrylic resin is a non-core-shell type acrylic resin having a glass transition point (Tg) higher than 30 °C. 4. The thermosensitive recording material according to claim 1, wherein the carboxyl group-containing resin is a carboxyl-modified polyvinyl alcohol. 5. The thermosensitive recording material according to the fourth aspect of the invention, wherein the protective layer further comprises an epichlorohydrin resin and a polyamine/melamine resin (other than a surface alcohol resin). 6. The thermosensitive recording material according to claim 1, wherein the thermosensitive recording material contains 4-hydroxy-4'-n-propoxydiphenyl sulfone as a color developing agent. 7. The thermosensitive recording material according to claim 2, wherein the thermosensitive recording material contains 4-hydroxy-4'-n-propoxydiphenyl sulfone as a color developing agent. 8. The thermosensitive recording material according to item 4 of the patent application, wherein the sensible heat 100117338 43 201206720 contains 4-hydroxy-4'-n-propoxydiphenyl sulfone as a color developing agent. 9. The thermosensitive recording material according to claim 6, wherein the thermosensitive recording material contains at least two kinds of color developing agents, and contains 50% by weight or more of 4-hydroxy-4'-positive with respect to the total amount of the color developing agent. Propoxydiphenyl sulfone. 10. The thermosensitive recording material according to any one of claims 1 to 9, wherein the protective layer in the wet state is wetted by applying a rewetting liquid to the surface of the temporarily dried protective layer. 100117338 44 201206720 IV. Designation of representative drawings: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: No 100117338 2