WO2011145545A1 - Support d'impression sensible à la chaleur - Google Patents

Support d'impression sensible à la chaleur Download PDF

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Publication number
WO2011145545A1
WO2011145545A1 PCT/JP2011/061150 JP2011061150W WO2011145545A1 WO 2011145545 A1 WO2011145545 A1 WO 2011145545A1 JP 2011061150 W JP2011061150 W JP 2011061150W WO 2011145545 A1 WO2011145545 A1 WO 2011145545A1
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WO
WIPO (PCT)
Prior art keywords
heat
sensitive recording
protective layer
recording material
layer
Prior art date
Application number
PCT/JP2011/061150
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English (en)
Japanese (ja)
Inventor
健 高木
健二 平井
昌也 登坂
勝人 大瀬
Original Assignee
日本製紙株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2010114090A external-priority patent/JP2011240574A/ja
Priority claimed from JP2010206393A external-priority patent/JP2012061652A/ja
Priority claimed from JP2010288328A external-priority patent/JP2012135896A/ja
Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Publication of WO2011145545A1 publication Critical patent/WO2011145545A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds

Definitions

  • the present invention relates to a heat-sensitive recording material produced using a cast coating method, and more specifically, produced using a cast coating method, having a high gloss surface, printing image quality, water resistance, plasticizer resistance,
  • the present invention relates to a heat-sensitive recording material excellent in scratch resistance and background color development.
  • a heat-sensitive recording medium is usually a colorless or light-colored electron-donating leuco dye (hereinafter also referred to as “leuco dye”) and an electron-accepting developer (hereinafter also referred to as “developer”) such as a phenolic compound.
  • leuco dye an electron-donating leuco dye
  • developer an electron-accepting developer
  • a paint obtained by adding a binder, a filler, a sensitivity improver, a lubricant and other auxiliaries to paper, synthetic paper, film, It is coated on a support such as plastic, and develops color by an instantaneous chemical reaction by heating with a thermal head, hot stamp, thermal pen, laser light, etc., and a recorded image is obtained.
  • Thermal recording media are widely used in facsimiles, computer terminal printers, automatic ticket vending machines, measurement recorders, and the like.
  • thermal recording media has expanded to various types of tickets, receipts, labels, bank ATMs, gas and electricity meter readings, car tickets, and so on.
  • severe characteristics such as water resistance and scratch resistance, which have not been a problem in the past, have begun to be demanded.
  • it is often used outdoors, and it can withstand use in harsh environments compared to conventional products so that it is not difficult to read the recorded area due to moisture, moisture, or rubbing such as rain. Performance is required.
  • high gloss for producing a high-class feeling is preferred.
  • a protective layer is provided on the heat-sensitive recording layer, and a carboxyl group-containing resin, epichlorohydrin resin, modified polyamine / amide resin (Patent Document 1) and acrylic resin (patent) By including the literature 2), performance such as water resistance is improved.
  • the outermost layer of the heat-sensitive recording material is formed by a cast coating method (Patent Documents 3 to 6 and the like).
  • a wet or plastic coating layer is pressure-bonded to a mirror-finished heating drum (hereinafter also referred to as “cast drum”), and the mirror surface is simultaneously dried. This is a method of obtaining a high gloss surface by copying the finished surface.
  • the present invention has a heat-sensitive recording layer on the support and a protective layer that is the outermost layer, is manufactured using a cast coating method, and is a heat-sensitive recording material having a high gloss surface, and has a print image quality, water resistance, It is an object of the present invention to provide a heat-sensitive recording material excellent in plasticizer resistance, scratch resistance and background color development.
  • Patent Documents 1, 2 and the like In order to improve the water resistance of the heat-sensitive recording material, a carboxyl group-containing resin is usually added to the protective layer, which is the outermost layer (Patent Documents 1, 2 and the like).
  • Patent Documents 1 and 2 As a result of intensive studies to solve the above problems, the present inventors have made a heat-sensitive recording material in which a carboxyl group-containing resin is contained in a protective layer, which is the outermost layer, in order to improve water resistance (Patent Documents 1 and 2). It was found that the performance such as water resistance is further improved by producing using a cast coating method.
  • the surface of the cast drum is usually 100 ° C. because the coating layer is pressed against a heated drum (cast drum) with a mirror finish on the wet or plastic coating layer.
  • the present invention has a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting developer on a support, and a protective layer as an outermost layer, and the protective layer is a carboxyl group.
  • the heat-sensitive recording material of the present invention has a structure having a heat-sensitive recording layer on a support and a protective layer as an outermost layer on the heat-sensitive recording layer.
  • An intermediate layer may be provided between the heat-sensitive recording layer and the protective layer in order to provide an oxygen permeation preventing effect or the like.
  • the protective layer of the present invention contains a carboxyl group-containing resin.
  • the carboxyl group-containing resin include acrylic resins, oxidized starch, carboxymethyl cellulose, carboxy-modified polyvinyl alcohol in which a carboxyl group is introduced into polyvinyl alcohol, and acrylic resin and carboxy-modified polyvinyl alcohol are particularly preferable.
  • the protective layer contains a carboxyl group-containing resin
  • the protective layer in a wet state is pressed against the cast drum and dried, the bond between the carboxyl group-containing resin and other materials is strengthened, and Since a compact protective layer is formed, the excellent effect of the present invention can be obtained.
  • the carboxyl group-containing resin is an acrylic resin
  • the protective layer is pressed against the cast drum and dried without excessive intake of moisture during the rewetting process by the rewetting cast method (rewetting method) described later. This is preferable because the adhesion to the cast drum is optimized and a good surface is obtained.
  • the protective layer when the carboxyl group-containing resin is carboxy-modified polyvinyl alcohol, when the protective layer further contains an epichlorohydrin resin and a polyamine / amide resin (excluding epichlorohydrin resin), a polyamine / amide Since the system resin exhibits fluidity due to heat, it is preferable because the protective layer has good adhesion to the cast drum when pressed and dried to the cast drum, and a good surface can be obtained.
  • the acrylic resin used in the present invention contains (meth) acrylic acid and a monomer component copolymerizable with (meth) acrylic acid, and (meth) acrylic acid is 1 to 10 weights per 100 parts by weight of the acrylic resin.
  • Part. (Meth) acrylic acid is alkali-soluble and has the property of making an acrylic resin a water-soluble resin by the addition of a neutralizing agent.
  • components copolymerizable with (meth) acrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate,
  • alkyl acrylate resins such as pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and epoxy resins, silicone resins, styrene or derivatives thereof
  • Modified alkyl acrylate resins such as the above-mentioned alkyl acrylate resins, (meth) acrylonitrile, acrylate esters, and hydroxyalkyl acrylate esters can be exemplified, but in particular, (meth) acrylonitrile and / or methyl methacrylate is blended.
  • (Meth) acrylonitrile is preferably blended in an amount of 15 to 70 parts per 100 parts of the acrylic resin. Further, methyl methacrylate is preferably contained in 20 to 80 parts per 100 parts of acrylic resin. When (meth) acrylonitrile and methyl methacrylate are included, it is preferable to blend 15 to 18 parts of (meth) acrylonitrile in 100 parts of acrylic resin and 20 to 80 parts of methyl methacrylate in 100 parts of acrylic resin.
  • the acrylic resin contained in the protective layer preferably has a glass transition point (Tg) higher than 30 ° C, more preferably higher than 30 ° C and lower than or equal to 130 ° C, and Tg higher than 50 ° C. More preferably, it is 95 ° C. or lower.
  • Tg glass transition point
  • the water resistance is sufficient, but the heat resistance is not sufficient, so that the protective layer in the wet state is pressed against the cast drum, and a good surface cannot be obtained when dried.
  • Insufficient stick resistance resistance to the occurrence of “out-of-white” or invisible “noise” in the printer due to the outermost layer of the thermal recording medium sticking to the printer head. is there.
  • Tg stick resistance and scratch resistance tend to be improved.
  • Tg is higher than 130 ° C.
  • the protective layer becomes brittle and water resistance, plasticizer resistance and solvent resistance are not sufficient. , The desired effect may not be obtained.
  • the Tg of acrylic resin is measured by differential scanning calorimetry (DSC).
  • the acrylic resin contained in the protective layer is preferably a non-core shell type.
  • the core-shell type acrylic resin is frequently used because it has better heat resistance than the non-core-shell type acrylic resin, and has excellent stick resistance when used in a coating layer.
  • the shell portion of the core-shell type acrylic resin usually has a low thermal conductivity, it also has the disadvantage of poor color development sensitivity.
  • the normal non-core shell type acrylic resin has low heat resistance and has the disadvantage that sticks and head debris are easily generated.
  • the non-core shell type has a Tg of 30 ° C. or higher and 130 ° C. or lower. Acrylic resins are excellent in heat resistance, and therefore have the advantage of good color development sensitivity and good stick resistance and head residue resistance.
  • the content (dry weight) of the acrylic resin contained in the protective layer is not particularly limited, but 1 weight in 100 parts by weight of the total protective layer (dry weight) from the viewpoint of water resistance. Or more. If it is less than 1 part by weight, a sufficient film for protecting the thermosensitive recording layer located in the lower layer cannot be formed, and good water resistance, plasticizer resistance, etc. cannot be obtained.
  • the carboxy-modified polyvinyl alcohol used in the present invention is a reaction product of polyvinyl alcohol and a polycarboxylic acid such as fumaric acid, phthalic anhydride, melittic anhydride, itaconic anhydride, or an esterified product of these reactants, and further vinyl acetate. And a saponified product of a copolymer of maleic acid, fumaric acid, itaconic acid, crotonic acid, acrylic acid, methacrylic acid and the like, and an ethylenically unsaturated dicarboxylic acid. Specifically, for example, the production method exemplified in Example 1 or 4 of JP-A-53-91995 can be mentioned.
  • the saponification degree of the carboxy-modified polyvinyl alcohol is preferably 72 to 100 mol%, and the polymerization degree is 500 to 2400, more preferably 1000 to 2000.
  • the protective layer of the present invention preferably contains an epichlorohydrin resin and a polyamine / amide resin (excluding epichlorohydrin resin; the same applies hereinafter).
  • the protective layer containing carboxy-modified polyvinyl alcohol further contains an epichlorohydrin-based resin and a polyamine / amide-based resin
  • the carboxy-modified polyvinyl alcohol and the epichlorohydrin-based resin have a polar cross-linking reaction; It is considered that excellent water resistance and plasticizer resistance are exhibited in order to attract the amine / amide sites of the polyamine / amide resin and protect the cross-linked polar sites.
  • the epichlorohydrin resin used in the present invention include polyamide epichlorohydrin resin, polyamine epichlorohydrin resin, and the like, and they can be used alone or in combination.
  • an amine which exists in the principal chain of an epichlorohydrin-type resin the thing from a primary to a quaternary can be used, and there is no restriction
  • the degree of cationization and the molecular weight preferably have a cationization degree of 5 meq / g ⁇ Solid (measured value at pH 7) and a molecular weight of 500,000 or more because of good water resistance.
  • Sumire Resin 650 (30), Sumire Resin 675A, Sumire Resin 6615 (manufactured by Sumitomo Chemical Co., Ltd.), WS4002, WS4020, WS4024, WS4030, WS4046, WS4010, CP8970 (above, manufactured by Starlight PMC) ) And the like.
  • Polyamine / amide resins used in the present invention include polyamide urea resins, polyalkylene polyamine resins, polyalkylene polyamide resins, polyamine polyurea resins, modified polyamine resins, modified polyamide resins, polyalkylene polyamine urea formalin resins, polyalkylene polyamine polyamide polys.
  • a urea resin etc. are mentioned. Specific examples include Sumire Resin 302 (manufactured by Sumitomo Chemical: polyamine polyurea resin), Sumire Resin 712 (manufactured by Sumitomo Chemical: polyamine polyurea resin), Sumire Resin 703 (manufactured by Sumitomo Chemical: polyamine polyurea).
  • polyamine resins polyalkylene polyamine resin, polyamine polyurea resin, modified polyamine resin, polyalkylene polyamine urea formalin resin, polyalkylene polyamine polyamide polyurea resin.
  • the content (dry weight) of the carboxy-modified polyvinyl alcohol, epichlorohydrin resin and polyamine / amide resin contained in the protective layer is not particularly limited, but from the viewpoint of water resistance. It is desirable that it is 1 part by weight or more in 100 parts by weight of the total protective layer (dry weight). If it is less than 1 part by weight, a sufficient film for protecting the thermosensitive recording layer located in the lower layer cannot be formed, and good water resistance, plasticizer resistance, etc. cannot be obtained.
  • the blending amount (dry weight) of epichlorohydrin resin and polyamine / amide resin with respect to carboxy-modified polyvinyl alcohol is 100 parts by weight of carboxy-modified polyvinyl alcohol with respect to epichlorohydrin resin and polyamine / amide resin.
  • the total amount of the resin is preferably 1 to 100 parts by weight. When the total amount of epichlorohydrin resin and polyamine / amide resin is less than 1 part by weight, good water resistance and plasticizer resistance cannot be obtained. The gelation and viscosity increase of the coating liquid are remarkable and the operability is inferior.
  • the cast coating method includes (1) a wet casting method (direct method) in which the coating layer is pressed against the cast drum while the coating layer is in a wet state, and (2) a rewetting liquid on the surface of the coating layer once dried.
  • a wet casting method direct method
  • rewetting liquid By applying (rewetting liquid), the wet coated layer surface is pressed against the cast drum and dried, the rewet cast method (rewetting method), and (3) the wet coated layer is solidified.
  • examples thereof include a gelled cast method (coagulation method) in which a plastic material is brought into pressure contact with a cast drum and dried.
  • the coating layer may be applied and performed in a state before drying.
  • the rewet liquid is usually an aqueous solution containing a release agent, and as the release agent, fatty acids such as stearic acid and oleic acid or salts thereof, polyethylene wax And lecithin.
  • the rewet liquid includes fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy modified polyvinyl alcohol, amide modified polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, butyral modified polyvinyl alcohol, and olefin modified polyvinyl alcohol.
  • Rewetting liquid is a surfactant, fluorescent dye, dye, ink fixing agent, colloidal pigment, pigment dispersant, water retention agent, thickener, antifoaming agent, antiseptic, colorant as necessary.
  • Water resistant agents, wetting agents, ultraviolet absorbers, cationic polymer electrolytes and other additives may be included.
  • the coating layer is made into a plastic state, that is, a gel state by applying a coagulating liquid to the coating layer in a wet state (coagulation treatment).
  • a coagulating liquid is formic acid such as calcium formate, acetic acid, citric acid, tartaric acid, lactic acid, hydrochloric acid, sulfuric acid, etc. and salts such as calcium, magnesium, zinc, etc. and coagulants such as boric acid, borax etc. dissolved in water.
  • the coating layer usually contains polyvinyl alcohols that react with the coagulant and coagulate.
  • a rewet cast method (rewetting method) among the cast coating methods.
  • the amount of moisture to be dried by the cast drum is large, that is, the drying load is large, because the cast layer is pressed and dried while the entire coating layer is in a wet state. If the temperature of the cast drum is raised to enhance drying, so-called ground color development may occur where the white paper portion of the thermal recording medium develops color. To enhance drying without raising the temperature of the cast drum, Need to slow down.
  • the rewet cast method the surface of the dried coating layer is rewet with the rewet liquid and then pressed against the cast drum and dried. If the entire coating layer is dried first, The amount of moisture to be dried is small, that is, the drying load is small. Therefore, it is possible to increase the coating speed as compared with the wet cast method and the gelled cast method.
  • the surface temperature of the cast drum when the protective layer in a wet state or plasticity is pressed against the cast drum and dried is not particularly limited, and is appropriately adjusted.
  • the surface temperature of the cast drum is usually 30 to 130 ° C., preferably 60 to 100 ° C.
  • the pressure to be pressed is a linear pressure of 50 to 300 kN / m, preferably 100 to 250 kN / m. If the surface temperature of the cast drum is too low, drying of the protective layer is insufficient, and if it is too high, so-called ground color development in which the white paper portion of the heat-sensitive recording material is colored may occur.
  • the protective layer will not have sufficient adhesion when copying the mirror-finished surface of the cast drum, making it impossible to obtain a heat-sensitive recording material having good surface properties, and the pressure will be too high. As a result, the heat-sensitive recording layer of the heat-sensitive recording material may be crushed and color developability may be reduced.
  • the carboxyl group-containing resin contained in the protective layer is the acrylic resin
  • the effect of the present invention can be achieved by adjusting the surface temperature of the cast drum to a temperature higher than the glass transition point (Tg) of the acrylic resin. Is remarkably exhibited, and a heat-sensitive recording material having particularly good surface properties can be obtained, which is preferable.
  • binders, cross-linking agents, pigments and the like can be used in the protective layer as long as they do not impair the desired effect on the above problems. Yes, it can be used for each coating layer provided as necessary.
  • the heat-sensitive recording material of the present invention has a heat-sensitive recording layer containing a leuco dye and a developer on a support, and a protective layer as an outermost layer.
  • the heat-sensitive recording medium is heated by the pressure-contacting and drying.
  • a so-called ground color development occurs in which the portion develops color, and the whiteness of the blank paper portion may decrease.
  • the color developer has high heat resistance, the color development of the ground color is suppressed, but the color development sensitivity (print density under low applied energy conditions) decreases.
  • the developer contained in the heat-sensitive recording layer is 4-hydroxy-4′-n-propoxydiphenylsulfone
  • the color development of the ground color is suppressed, the whiteness of the white paper portion of the heat-sensitive recording material is good, and the color is developed. Sensitivity is also good. Further, since the plasticizer resistance is particularly good, an excellent heat-sensitive recording material can be obtained.
  • the heat-sensitive recording layer of the present invention may contain a developer other than 4-hydroxy-4′-n-propoxydiphenylsulfone as a developer, and further includes a sensitizer, a binder, a crosslinking agent, a pigment, a lubricant, A stabilizer or the like may be included.
  • a developer other than 4-hydroxy-4′-n-propoxydiphenyl sulfone used in the present invention those known in the field of conventional pressure-sensitive or thermal recording paper can be used as long as they do not inhibit the desired effect in the present invention. All are usable, and are not particularly limited.
  • developers other than 4-hydroxy-4′-n-propoxydiphenylsulfone include activated clay, attapulgite, colloidal silica, inorganic silicate materials such as aluminum silicate, 4,4′-isopropylidenediphenol, 1, 1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 4,4′-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4 , 4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-n -Butoxydiphenyl sulfone, 4- Hydroxy-4'-methyldiphenylsulfone, 4-hydroxyphenyl-4'-benzy
  • the diphenylsulfone cross-linking compound described in WO97 / 16420 is available as trade name D-90 manufactured by Nippon Soda Co., Ltd.
  • the compounds described in WO02 / 081229 and the like are available as trade names NKK-395 and D-100 manufactured by Nippon Soda Co., Ltd.
  • a metal chelate color-developing component such as higher fatty acid metal double salts and polyvalent hydroxyaromatic compounds described in JP-A-10-258577 can also be contained.
  • R 1 represents a linear or branched saturated or unsaturated hydrocarbon having 1 to 12, preferably 1 to 5, more preferably 1 to 4 carbon atoms.
  • R 2 each independently represents a halogen atom or an alkyl or alkenyl group having 1 to 12 carbon atoms.
  • Each n is an integer of 0 to 4, preferably 0 to 2, and more preferably 0.
  • Each A independently represents a linear or branched saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms which may have an ether bond. Examples of the saturated hydrocarbon group for A include linear or branched saturated hydrocarbons having 1 to 12, preferably 2 to 6, more preferably 3 to 4 carbon atoms.
  • m is an integer of 0 to 5, preferably 0 to 2, and more preferably 0.
  • the diphenylsulfone derivative may be a compound having a specific m in the general formula (Chemical Formula 1), or may be a mixture in an arbitrary ratio of compounds having different m in the general formula (Chemical Formula 1).
  • this diphenylsulfone derivative 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane is preferable.
  • the content of 4-hydroxy-4′-n-propoxydiphenylsulfone depends on the heat-sensitive recording.
  • the total color developer (including 4-hydroxy-4′-n-propoxydiphenyl sulfone) contained in the layer is preferably 50% by weight or more, and more preferably 90% by weight or more.
  • the thermal recording layer of the present invention contains 4-hydroxy-4′-n-propoxydiphenylsulfone and a developer of the general formula (Formula 1), 4-hydroxy-4′-n-propoxydiphenylsulfone And the total developer (4-hydroxy-4′-n-propoxydiphenylsulfone and general formula (Chemical Formula 1)) contained in the heat-sensitive recording layer. And 90% by weight or more of the above (including the developer).
  • any known ones in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used, although not particularly limited, a triphenylmethane compound, Fluorane compounds, fluorene compounds, divinyl compounds and the like are preferable.
  • Specific examples of typical colorless or light-colored dyes (dye precursors) are shown below. These dye precursors may be used alone or in combination of two or more.
  • Triphenylmethane leuco dye 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide (also known as malachite green lactone)
  • sensitizer As the sensitizer usable in the heat-sensitive recording material of the present invention, a conventionally known sensitizer can be used.
  • sensitizers include fatty acid amides such as stearamide, palmitic acid amide, ethylene bisamide, montanic acid wax, polyethylene wax, 1,2-di- (3-methylphenoxy) ethane, p-benzylbiphenyl, ⁇ - Benzyloxynaphthalene, 4-biphenyl-p-tolyl ether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, di (p-chlorobenzyl) oxalate, di (p-methylbenzyl) oxalate, Dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, phenyl- ⁇ -naphthyl carbonate, 1,4-diethoxynaphthalen
  • the binder usable in the heat-sensitive recording material of the present invention includes fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, and butyral-modified.
  • These polymer substances are used by dissolving them in solvents such as water, alcohol, ketones, esters, hydrocarbons, etc., and are used in the state of being emulsified or pasted in water or other media to achieve the required quality. It can also be used in combination.
  • crosslinking agent examples include glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, Examples thereof include sodium sulfate, ferric chloride, magnesium chloride, borax, boric acid, alum, and ammonium chloride.
  • Examples of the pigment that can be used in the heat-sensitive recording material of the present invention include inorganic or organic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, and aluminum hydroxide.
  • inorganic or organic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, and aluminum hydroxide.
  • kaolin, calcined kaolin, and aluminum hydroxide are preferable in consideration of the wearability of the thermal head.
  • the aspect ratio of the pigment is an average value of the ratio of the diameter to the length (thickness) of the shortest axis for 100 pigment particles.
  • Kaolin with an aspect ratio of 30 or more is very flat compared to pigments that are generally used as papermaking materials, and is necessary to cover the same area as when using pigments with a smaller aspect ratio
  • the amount of kaolin used is reduced. That is, since the protective layer can be made thin, it is considered that a decrease in thermal conductivity to the heat-sensitive recording layer can be suppressed, and excellent color development sensitivity and image quality can be obtained.
  • the preferred aspect ratio of kaolin used in the present invention is 30 to 100, more preferably 30 to 75.
  • the kaolin desirably has an average diameter of 4 ⁇ m or less.
  • the average diameter of kaolin having an aspect ratio of 30 or more is larger than 4 ⁇ m, the surface smoothness of the protective layer is lowered, which may cause problems such as deterioration in recording image quality.
  • the kaolin used in the present invention usually has an oil absorption of 50 to 80 ml / 100 g and a BET specific surface area of 10 to 30 m 2 / g.
  • mica (mica) having an aspect ratio of 100 or more has a low ability to absorb water and solvent with 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.
  • the kaolin having an aspect ratio of 30 or more according to the present invention can be obtained by classifying the delaminated kaolin by special grinding.
  • kaolin having an aspect ratio of 30 or more in the protective layer is preferably used singly because of its specific shape, but a plurality of pigments in the protective layer may be used in combination. Good.
  • the proportion of kaolin having an aspect ratio of 30 or more is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, in 100 parts by weight of the total amount of the pigment in the protective layer.
  • lubricant examples include fatty acid metal salts such as zinc stearate and calcium stearate, waxes, and silicone resins.
  • 4,4′-butylidene (6-tert-butyl-3-methylphenol) is used as an image stabilizer exhibiting the oil resistance effect of a recorded image within a range not inhibiting the desired effect on the above problems.
  • 2,2′-di-t-butyl-5,5′-dimethyl-4,4′-sulfonyldiphenol 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) Butane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 4-benzyloxy-4 ′-(2,3-epoxy-2-methylpropoxy) diphenylsulfone, etc.
  • benzophenone or triazole ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, fluorescent dyes, and the like can be used.
  • the leuco dye, developer, sensitizer and materials added as necessary for the heat-sensitive recording layer of the heat-sensitive recording material of the present invention are added by a pulverizer such as a ball mill, an attritor or a sand glider, or an appropriate emulsifying device. It is atomized until the particle diameter becomes several microns or less, and various additive materials are added according to the binder and purpose to obtain a coating solution.
  • the amount of the material is determined according to the required performance and recordability and is not particularly limited.
  • the developer is 0.5 to 10 parts by weight and the sensitizer 0.5 to 1 part by weight based on 1 part by weight of the leuco dye. The amount is preferably about 10 parts by weight.
  • a thermal recording layer having the above composition was applied to an arbitrary support such as paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, nonwoven fabric, and a composite sheet combining these.
  • the protective layer is provided, and the protective layer in a wet state is pressed and dried so that the surface of the protective layer is in contact with the cast drum.
  • the coating amount of the heat-sensitive recording layer is not particularly limited, but is preferably in the range of 2 to 12 g / m 2 in terms of solid content.
  • the coating amount of the protective layer provided on the heat-sensitive recording layer is not particularly limited, but it is preferably in the range of 0.5 to 5 g / m 2 in terms of solid content.
  • an undercoat layer containing the pigment, binder and the like can be provided under the heat-sensitive recording layer. It is also possible to correct the curl by providing a backcoat layer on the surface of the support opposite to the thermosensitive recording layer.
  • the means for coating each layer such as the undercoat layer, the heat-sensitive recording layer, the protective layer, and the backcoat layer is not particularly limited, and can be applied according to a well-known conventional technique.
  • Coating methods for each layer include air knife method, rod blade method, vent blade method, bevel blade method, roll method, slot type curtain method, slide type curtain method, slide hopper type curtain method, bead type curtain method, spray method
  • the die method and the like can be exemplified, and these coating methods are appropriately selected and used.
  • various known techniques in the heat-sensitive recording material field can be added as appropriate, such as applying a smoothing process such as supercalendering after coating each layer.
  • a composition comprising the following composition was stirred and dispersed to prepare an undercoat layer coating solution.
  • thermosensitive recording layer coating liquid was mixed at the following ratio to prepare a thermosensitive recording layer coating liquid.
  • ⁇ Protective layer coating solution 1 Engineered kaolin (Imeris: Konza 1500, aspect ratio 60) 50% dispersion 12.0 parts
  • Non-core shell acrylic resin Mitsubishi Chemicals: ASN1004K, Tg
  • Zinc stearate manufactured by Chukyo Yushi Co., Ltd .: Hydrin L536, solid content 40%
  • Surfactant manufactured by Nissin Chemical Co., Ltd .: Surfynol 104P, solid content 50%
  • ⁇ protective layer coating solution 2 Engineered kaolin (Imeris, Conza 1500, aspect ratio 60) 50% dispersion 12.0 parts Carboxy-modified polyvinyl alcohol aqueous solution (Kuraray, KL118, (Solid content 12%) 26.7 parts Polyamide epichlorohydrin resin solution (manufactured by Se).
  • a re-wetting liquid was prepared by stirring and dispersing a composition having the following composition.
  • a composition comprising the following composition was stirred and dispersed to prepare a coagulation liquid.
  • Example 1 After coating the undercoat layer coating solution on one side of the support (basic weight 60 g / m 2 ) by the vent blade method so that the coating amount is 10.0 g / m 2 in solid content, Drying was performed to obtain an undercoat layer-coated paper. Next, the thermal recording layer coating solution 1 was applied on the undercoat layer of the undercoat layer-coated paper by the rod blade method so that the coating amount was 5.0 g / m 2 in terms of solid content, and then dried. The heat-sensitive recording layer-coated paper was obtained.
  • Example 1 After coating the protective layer coating liquid 1 on the heat-sensitive recording layer of the heat-sensitive recording layer-coated paper by a slot type curtain method so that the coating amount is 3.0 g / m 2 in solid content, Drying was carried out, and the coated surface was treated with a super calender so that the smoothness of the coated surface became 1000 to 2000 seconds, and a heat-sensitive recording material was produced. Next, 50 g / m 2 of rewetting liquid 1 was applied on the protective layer of the heat-sensitive recording material, and the rewetting protective layer was formed on the cast drum having a surface temperature of 70 ° C. while the protective layer was wet.
  • the heat-sensitive recording material of Example 1 was produced by making contact with the cast drum side and performing pressure treatment and heating (drying) treatment at a linear pressure of 100 kN / m using a rubber roll (rewet cast treatment).
  • Example 2 6.0 parts of 4-hydroxy-4′-n-propoxydiphenylsulfone (JKY-146) in the developer dispersion (liquid A) was added to 4-hydroxy-4′-n-propoxydiphenylsulfone (JKY-146). 5.0 parts and 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane (manufactured by API Corporation: JKY-214) 1.0 A heat-sensitive recording material was obtained in the same manner as in Example 1 except that the parts were changed.
  • Example 3 6.0 parts of 4-hydroxy-4′-n-propoxydiphenylsulfone (JKY-146) in the developer dispersion (liquid A) was added to 4-hydroxy-4′-isopropoxydiphenylsulfone (manufactured by API Corporation). : NYDS) A heat-sensitive recording material was obtained in the same manner as in Example 1 except that the content was changed to 6.0 parts.
  • Example 4 A heat-sensitive recording material was obtained in the same manner as in Example 2 except that the rewetting liquid 1 was changed to the rewetting liquid 2.
  • Example 5 On one side of the support (basic weight 60 g / m 2 base paper), the undercoat layer coating solution is applied so that the coating amount is 10.0 g / m 2 in solids, and then dried. Undercoat layer coated paper was obtained. Next, the thermal recording layer coating solution 2 is applied onto the undercoat layer of the undercoat layer-coated paper with a blade coater so that the solid content is 5.0 g / m 2 and then dried. A heat-sensitive recording layer-coated paper was obtained.
  • the protective layer coating solution 2 is applied onto the heat-sensitive recording layer of the heat-sensitive recording layer-coated paper with a blade coater so that the coating amount is 3.0 g / m 2 in terms of solid content, followed by drying.
  • a heat-sensitive recording material was prepared by treating the coated surface with a super calender so that the smoothness of the coated surface was 1000 to 2000 seconds.
  • 50 g / m 2 of rewetting liquid 3 was applied on the protective layer of the heat-sensitive recording material, and the rewetting protective layer was formed on the cast drum having a surface temperature of 70 ° C. while the protective layer was wet.
  • Example 6 A heat-sensitive recording material was produced in the same manner as in Example 5 except that warm water (40 to 50 ° C.) was used instead of the rewetting liquid 3.
  • Example 7 After coating the undercoat layer coating solution on one side of the support (basic weight 60 g / m 2 ) by the vent blade method so that the coating amount is 10.0 g / m 2 in solid content, Drying was performed to obtain an undercoat layer-coated paper. Next, the thermal recording layer coating solution 1 was applied on the undercoat layer of the undercoat layer-coated paper by the rod blade method so that the coating amount was 5.0 g / m 2 in terms of solid content, and then dried. The heat-sensitive recording layer-coated paper was obtained.
  • the protective layer coating solution 3 is applied on the heat-sensitive recording layer of the heat-sensitive recording layer-coated paper by a roll method so that the coating amount is 3.0 g / m 2 in terms of solid content, and then the protective layer.
  • the coagulating liquid was applied on the protective layer using a roll method to obtain a plastic state (gel state).
  • the protective layer while the protective layer is in a gel state, it is brought into contact with the cast drum having a surface temperature of 70 ° C. so that the protective layer is on the cast drum side, and pressure treatment and heating at a linear pressure of 100 kN / m using a rubber roll ( (Drying) treatment (gelation cast treatment) to produce a thermal recording material of Example 4.
  • thermosensitive recording medium was prepared in the same manner as in Example 5 except that the carboxy-modified polyvinyl alcohol aqueous solution of the protective layer coating solution 2 was replaced with an acetoacetyl-modified polyvinyl alcohol aqueous solution (manufactured by Nippon Synthetic Chemical Co., Ltd .: Z100, solid content 12%). Obtained.
  • ⁇ Print density> The produced heat-sensitive recording material was solid-printed with an applied energy of 0.41 mJ / dot or 0.35 mJ / dot using a printing tester (manufactured by Okura Electric Co., Ltd .: TH-PMD, equipped with a thermal head manufactured by Kyocera Corporation). The density of the printed portion was measured with a Macbeth densitometer (RD-914, using an amber filter) to evaluate the print density.
  • thermosensitive recording medium was solid-printed at an applied energy of 0.27 mJ / dot using a printing tester (Okura Electric Co., Ltd .: TH-PMD, equipped with a Kyocera thermal head).
  • the density of the printed part was measured with a Macbeth densitometer (RD-914, using an amber filter), and the color development sensitivity was evaluated.
  • thermosensitive recording medium was solid-printed at an applied energy of 0.27 mJ / dot using a printing tester (Okura Electric Co., Ltd .: TH-PMD, equipped with a Kyocera thermal head).
  • the image quality after printing was visually evaluated according to the following criteria. Good: Unevenness is not seen at all. Good: Slight unevenness is observed. Impossible: Unevenness is observed.
  • ⁇ Ground color development> The density of the blank paper portion of the produced thermal recording material was measured with a Macbeth densitometer (RD-914, using an amber filter), and the background color development (coloration of the background portion (fogging)) by the casting process was evaluated.
  • thermosensitive recording material was measured for 75 degree gloss on the surface of the protective layer using a gloss meter (Nippon Denshoku Industries Co., Ltd .: VG7000) according to JIS-P8142. The higher the value, the higher the gloss and the better the quality.
  • the produced thermal recording medium was solid-printed with an applied energy of 0.41 mJ / dot using a printing tester (Okura Electric Co., Ltd .: TH-PMD, equipped with a Kyocera thermal head). After immersion in water at 23 ° C and 50% Rh for 24 hours, the print density of the printed part is measured with a Macbeth densitometer (RD-914, using an amber filter), and the residual rate is calculated from the values before and after the treatment. The water resistance was evaluated.
  • Residual rate (%) (printing density after processing / printing density before processing) ⁇ 100 ⁇ Abrasion resistance>
  • the protective layer surface was rubbed with the steel wool which added the load of 1000 gf / cm ⁇ 2 >, and the color development was visually evaluated on the following reference
  • the produced thermal recording medium was solid-printed with an applied energy of 0.41 mJ / dot using a printing tester (Okura Electric Co., Ltd .: TH-PMD, equipped with a Kyocera thermal head).
  • a vinyl chloride wrap (manufactured by Mitsui Toatsu Co., Ltd .: High Wrap KMA) is wrapped around a paper tube in a single layer, and the thermal recording medium is placed on the paper so that the printed part is on the outer surface.
  • the print density of the printed part was measured with a Macbeth densitometer (RD-914, using an amber filter), and the residual rate (from above) was measured. ) And the plasticizer resistance was evaluated.
  • the heat-sensitive recording material of the present invention has a high gloss surface, no background color development, and good water resistance.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

L'invention porte sur un support d'impression sensible à la chaleur, lequel support comprend un support, une couche d'impression sensible à la chaleur et une couche protectrice qui constitue la couche située le plus à l'extérieur, ladite couche d'impression sensible à la chaleur et ladite couche protectrice étant formées sur le support, lequel support d'impression est produit par le procédé de couchage au glacis, a un brillant élevé qui lui est communiqué, et présente de bonnes qualités d'impression, une résistance à l'eau élevée, une résistance aux plastifiants élevée, une résistance au frottement élevée et une résistance élevée vis-à-vis du développement de couleur de fond. Dans le procédé de couchage au glacis, dans lequel une couche protectrice dans un état humide ou plastique est séchée par pression de la couche protectrice contre un tambour chaud à fini spéculaire (tambour de couchage), on craint qu'un précurseur de colorant dans une couche d'impression sensible à la chaleur réagisse avec un révélateur en provoquant un développement de couleur dans une partie blanche d'une feuille de papier, à savoir, ce que l'on appelle un développement de couleur de fond. Par l'addition d'une résine contenant un groupe carboxyle à la couche protectrice, non seulement des propriétés telles que la résistance à l'eau sont améliorées, mais, également, le phénomène de développement de couleur de fond peut être empêché. Il est décrit un support d'impression sensible à la chaleur qui comprend, sur un support, une couche d'impression sensible à la chaleur, qui contient un colorant leuco donneur d'électrons sans couleur ou de couleur pâle et un révélateur accepteur d'électrons, et une couche protectrice qui constitue la couche située le plus à l'extérieur, ladite couche protectrice comprenant une résine contenant un groupe carboxyle et ladite couche protectrice étant formée par le procédé de couchage au glacis.
PCT/JP2011/061150 2010-05-18 2011-05-16 Support d'impression sensible à la chaleur WO2011145545A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2010114090A JP2011240574A (ja) 2010-05-18 2010-05-18 感熱記録体
JP2010-114090 2010-05-18
JP2010206393A JP2012061652A (ja) 2010-09-15 2010-09-15 感熱記録体
JP2010-206393 2010-09-15
JP2010-288328 2010-12-24
JP2010288328A JP2012135896A (ja) 2010-12-24 2010-12-24 感熱記録体

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015046305A1 (fr) 2013-09-30 2015-04-02 日本製紙株式会社 Support de gravure thermique
WO2020189183A1 (fr) * 2019-03-20 2020-09-24 日本製紙株式会社 Corps d'enregistrement thermosensible

Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2003127543A (ja) * 2001-10-23 2003-05-08 Oji Paper Co Ltd 感熱記録体
WO2007049621A1 (fr) * 2005-10-24 2007-05-03 Mitsui Chemicals, Inc. Materiau d’enregistrement thermique
JP2010058467A (ja) * 2008-09-05 2010-03-18 Nippon Paper Industries Co Ltd 感熱記録体

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2003127543A (ja) * 2001-10-23 2003-05-08 Oji Paper Co Ltd 感熱記録体
WO2007049621A1 (fr) * 2005-10-24 2007-05-03 Mitsui Chemicals, Inc. Materiau d’enregistrement thermique
JP2010058467A (ja) * 2008-09-05 2010-03-18 Nippon Paper Industries Co Ltd 感熱記録体

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015046305A1 (fr) 2013-09-30 2015-04-02 日本製紙株式会社 Support de gravure thermique
KR20160045879A (ko) 2013-09-30 2016-04-27 닛폰세이시가부시키가이샤 감열 기록체
US9579916B2 (en) 2013-09-30 2017-02-28 Nippon Paper Industries Co., Ltd. Thermosensitive recording medium
WO2020189183A1 (fr) * 2019-03-20 2020-09-24 日本製紙株式会社 Corps d'enregistrement thermosensible
CN113423583A (zh) * 2019-03-20 2021-09-21 日本制纸株式会社 热敏记录体
US11945249B2 (en) 2019-03-20 2024-04-02 Nippon Paper Industries Co., Ltd. Thermosensitive recording medium

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