WO2013137243A1 - 感熱記録体 - Google Patents

感熱記録体 Download PDF

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Publication number
WO2013137243A1
WO2013137243A1 PCT/JP2013/056784 JP2013056784W WO2013137243A1 WO 2013137243 A1 WO2013137243 A1 WO 2013137243A1 JP 2013056784 W JP2013056784 W JP 2013056784W WO 2013137243 A1 WO2013137243 A1 WO 2013137243A1
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WIPO (PCT)
Prior art keywords
heat
recording material
sensitive recording
group
acrylic resin
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PCT/JP2013/056784
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English (en)
French (fr)
Japanese (ja)
Inventor
泰明 松森
平井　健二
荻野　明人
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日本製紙株式会社
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Priority claimed from JP2012060724A external-priority patent/JP2013193266A/ja
Priority claimed from JP2012069436A external-priority patent/JP2013199074A/ja
Priority claimed from JP2012073389A external-priority patent/JP2013202905A/ja
Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Publication of WO2013137243A1 publication Critical patent/WO2013137243A1/ja
Priority to FI20145896A priority Critical patent/FI127015B/fi

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    • 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
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/245—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing a polymeric component
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/315—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of heat to a heat sensitive printing or impression-transfer material
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/147—Copolymers of propene with monomers containing other atoms than carbon or hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides

Definitions

  • the present invention relates to a heat-sensitive recording material in which a heat-sensitive recording layer and a protective layer are provided on a support made of a plastic film, and more particularly to a heat-sensitive recording material using a plastic film as a support to reduce coating defects.
  • the heat-sensitive recording medium usually contains 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, After grinding and dispersing into fine particles, respectively, the two are mixed, and a coating solution obtained by adding a binder, a filler, a sensitivity improver, a lubricant and other auxiliaries is added to paper, synthetic paper, film, It is coated on a support such as plastic and is colored by an instantaneous chemical reaction by heating with a thermal head, hot stamp, thermal pen, laser beam, etc., and a recorded image is obtained.
  • a coating solution obtained by adding a binder, a filler, a sensitivity improver, a lubricant and other auxiliaries is added to paper, synthetic paper, film, It is coated on a support such as plastic and is colored by an instantaneous chemical reaction by heating with a thermal head
  • Thermosensitive recording media are widely used in facsimiles, computer terminal printers, automatic ticket vending machines, measurement recorders, and the like. Due to good dimensional stability and strength, thermal recording media using a plastic film as a support have increased (Patent Document 1, etc.), but when a plastic film is used as a support for the thermal recording media, In order to solve the problem that the coating layer peels due to the heat-sensitive recording layer, a thermal recording material has been developed in which a protective layer containing a polyolefin resin and a glossy layer are provided on the thermal recording layer (Patent Document 2). In addition, in a heat-sensitive recording material used for outdoor applications requiring durability and water resistance, a protective layer containing an acrylic resin emulsion is provided on the heat-sensitive recording layer (patent) Literature 3-6 etc.).
  • a protective layer is generally provided on the heat-sensitive recording layer in order to increase surface strength and water resistance.
  • plastic films are less water-absorbing than water and other solvents compared to paper, ripple-like coating defects occur due to the presence of water and other solvents in the thermal recording layer. Easy (see Comparative Example 2 described later, FIG. 1). Since this coating defect is caused by a difference in light transmission state, it is more noticeable when a transparent plastic film is used for the support. In addition, this problem becomes more prominent when a coating liquid that improves the adhesion and tackiness to the plastic film is used. This problem can be solved by including an olefin resin in the protective layer (Comparative Example 5 described later).
  • the present invention provides a thermal recording material in which a plastic film is used as a support, and a thermal recording layer and a protective layer as an outermost layer are sequentially provided on the plastic film, thereby reducing coating defects and excellent printing running properties (sticking).
  • An object is to provide a thermal recording material.
  • the present inventors have used a plastic film as the support, sequentially provided a heat-sensitive recording layer and a protective layer as the outermost layer, and this protective layer contains an acrylic resin and a polyolefin resin. It has been found that it exhibits normal performance with respect to water resistance and the like required for such a heat-sensitive recording material and can prevent the occurrence of coating defects, and has completed the present invention. That is, the present invention relates to a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting developer on a plastic film, and a heat-sensitive recording material having a protective layer as an outermost layer on the heat-sensitive recording layer.
  • the protective layer is a heat-sensitive recording material containing an acrylic resin and a polyolefin resin.
  • thermosensitive recording material (10.5 ⁇ 14 cm) produced in Comparative Example 2.
  • the support is a PET film, and rippled coating defects are generated on the surface of the protective layer.
  • a heat-sensitive recording layer is provided on a plastic film (support), and a protective layer is provided thereon as an outermost layer, and this protective layer contains an acrylic resin and a polyolefin-based resin.
  • plastic film used in the present invention examples include a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, and a polyethylene naphthalate (PEN) film.
  • PET polyethylene terephthalate
  • TAC triacetyl cellulose
  • PEN polyethylene naphthalate
  • examples include a norbornene-based film (trade name: ARTON film) manufactured by JSR, a cycloolefin-based film (trade name: ZEONOR film) manufactured by ZEON CORPORATION, and a composite film obtained by combining these films. it can.
  • the support when the support is used in applications requiring light transmittance, the support preferably has a total light transmittance of 30% or more, more preferably 70% or more, among the resin films described above.
  • the polyolefin resin used in the present invention is an olefin polymer such as ethylene or propylene, and may be a monopolymer or a copolymer with other vinyl compounds.
  • the polyolefin resin used in the present invention is preferably an olefin / unsaturated carboxylic acid copolymer.
  • As the olefin, ethylene, propylene, butylene and the like are preferable, and ethylene is particularly preferable.
  • the unsaturated carboxylic acid is preferably (meth) acrylic acid (that is, acrylic acid or methacrylic acid), maleic acid, itaconic acid, fumaric acid and the like, and more preferably (meth) acrylic acid.
  • the olefin / unsaturated carboxylic acid copolymer is preferably a copolymer of ethylene and (meth) acrylic acid or a copolymer of propylene and (meth) acrylic acid copolymer.
  • the weight average molecular weight of such a polyolefin resin is preferably 5,000 to 100,000, more preferably 10,000 to 50,000. If the weight average molecular weight is less than 5,000, blocking may occur. In addition, if the weight average molecular weight exceeds 100,000, there may be a problem in productivity.
  • Examples of the olefin / unsaturated carboxylic acid copolymer include Hitech S-3121, Hitech S-3123, Hitech S-3127 (manufactured by Toho Chemical Co., Ltd.), Seixen-A-GH, Seixen-AC, and Seixen. -N, Saixen-L (above, manufactured by Sumitomo Seika Co., Ltd.) and the like.
  • the acrylic resin used in the present invention comprises (meth) acrylic acid and a monomer component (excluding olefin) copolymerizable with (meth) acrylic acid.
  • (Meth) acrylic acid is preferably blended in an amount of 1 to 10 parts per 100 parts of the acrylic resin.
  • (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.
  • component copolymerizable with (meth) acrylic acid examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • Alkyl acrylate resins such as pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, epoxy resins, silicone resins, styrene or derivatives thereof
  • Modified alkyl acrylate resins such as the above-mentioned alkyl acrylate resins modified by (meth) acrylonitrile, acrylate esters, hydroxyalkyl acrylate esters can be exemplified, but in particular, (meth) acrylonitrile and / or methyl methacrylate are blended. It is preferable.
  • (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 glass transition point (Tg) of the acrylic resin in the present invention is higher than 50 ° C and not higher than 95 ° C. When Tg is 50 ° C. or lower, the water resistance is improved, but sufficient heat resistance cannot be obtained, so that sticking tends to occur.
  • the stick resistance and scratch resistance tend to be improved, but if the Tg is too high, the protective layer becomes brittle, and the water resistance, plasticizer resistance and solvent resistance are not sufficient. In some cases, the intended effect cannot be obtained.
  • the Tg of acrylic resin is measured by differential scanning calorimetry (DSC).
  • the acrylic resin used in the present invention is preferably a non-core shell type acrylic resin.
  • the core-shell type acrylic resin is frequently used because it has excellent heat resistance compared to the non-core-shell type acrylic resin and has excellent stick resistance when used in a coating layer.
  • the shell part of the core-shell type acrylic resin usually has a drawback that the color development sensitivity is poor because of its low thermal conductivity.
  • the normal non-core shell type acrylic resin has low heat resistance and has the disadvantage that sticks and head debris are likely to be generated, but the non-core shell type Tg used in the present invention is higher than 50 ° C. and lower than 95 ° C.
  • 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 protective layer of this invention does not contain a pigment.
  • the pigment include inorganic or organic fillers such as kaolin, calcined kaolin, aluminum hydroxide, silica, calcium carbonate, diatomaceous earth, talc, and titanium oxide.
  • the protective layer of the present invention includes fatty acid metal salts such as zinc stearate and calcium stearate, lubricants such as waxes and silicone resins, benzophenone-based and triazole-based UV absorbers, crosslinking agents, and dispersion agents. You may contain an agent, an antifoamer, antioxidant, fluorescent dye, etc., unless the effect of this invention is inhibited.
  • the blending amount of the polyolefin resin in the protective layer of the present invention is preferably 3 to 60% by weight, more preferably 5 to 30% by weight in terms of solid content.
  • the blending amount of the acrylic resin in the protective layer of the present invention is preferably 15 to 97% by weight, more preferably 50 to 95% by weight in terms of solid content.
  • the blending weight ratio (solid content) of the polyolefin resin / acrylic resin is preferably 3/97 to 50/50, more preferably 5/95 to 40/60.
  • the total amount of the polyolefin resin and the acrylic resin in the protective layer is preferably 20 to 100% by weight, more preferably 40 to 90% by weight, as a solid content.
  • the heat-sensitive recording layer of the present invention contains a leuco dye and a developer, and may further contain a sensitizer, a binder, a cross-linking agent, a lubricant, the above-described pigment, and other various components.
  • a leuco dye used in the present invention any known leuco dyes in the field of conventional pressure-sensitive or thermal recording paper can be used, and are not particularly limited, but include triphenylmethane compounds, fluoran compounds, fluorenes. And divinyl compounds are preferred. Specific examples of typical colorless or light leuco 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)
  • Examples of the developer used in the present invention include inorganic acidic substances such as activated clay, attapulgite, colloidal silica, aluminum silicate, 4,4′-isopropylidenediphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane.
  • inorganic acidic substances such as activated clay, attapulgite, colloidal silica, aluminum silicate, 4,4′-isopropylidenediphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane.
  • R 1 s may be the same or different, but are preferably the same and represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group.
  • the alkyl group or alkenyl group is an alkyl group or alkenyl group having 1 to 6 carbon atoms.
  • R 2 may be the same or different, but is preferably the same.
  • R 2 is a saturated or unsaturated, preferably saturated, linear or branched, preferably linear hydrocarbon having 1 to 12, preferably 3 to 7 carbon atoms, which may have an ether bond It may be a group.
  • Such hydrocarbon is preferably a polyalkylene oxide chain or an alkylene group, preferably a polyalkylene oxide chain.
  • R 3 represents a methylene group or an ethylene group. R 3 are preferably para to each other).
  • R 2 the following general formula (Wherein R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom). ). Among these, R 2 is preferably a saturated or unsaturated linear or branched hydrocarbon group having 1 to 12 carbon atoms, which may have an ether bond.
  • R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom).
  • R 2 is preferably a saturated or unsaturated linear or branched hydrocarbon group having 1 to 12 carbon atoms, which may have an ether bond.
  • the diphenylsulfone cross-linking compound represented by the above general formula (Formula 1) a compound represented by the following formula (manufactured by Nippon Soda Co., Ltd., D-90) is preferable.
  • R 5 and R 6 each independently represents an alkyl group or alkenyl group having 1 to 8 carbon atoms or a halogen atom
  • R 7 is a hydrogen atom or a straight chain having 1 to 4 carbon atoms.
  • a chain or branched saturated or unsaturated hydrocarbon is represented, and p and q each independently represents an integer of 0 to 3.
  • the diphenylsulfone compound represented by the general formula (Chemical Formula 4) is represented by the following general formula (Chemical Formula 6).
  • R 5 , R 6 , p and q are as defined above
  • the following general formula (Formula 7) (Wherein R 5 and R 6 each independently represents an alkenyl group having 1 to 4 carbon atoms, R 7 is as defined above, and p and q each independently represents an integer of 0 to 2) .) Is preferred.
  • Examples of the dihydroxydiphenylsulfone compound represented by the above general formula (Formula 6) include 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, and 4,4′-dihydroxy-3,3′-diallyldiphenyl.
  • Examples of the diphenylsulfone compound represented by the above general formula (Formula 7) include 4-hydroxy-4′-n-propoxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, and 4-hydroxy-4′-allyl.
  • 4-hydroxy-4′-n-propoxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, and 4-hydroxy-4′-allyloxydiphenylsulfone are preferable.
  • the 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane can be obtained, for example, as trade name JKY-214 manufactured by API Corporation.
  • the phenol condensation composition described in JP-A No. 2003-154760 is available, for example, under the trade name JKY-224 manufactured by API Corporation.
  • the compounds described in the above-mentioned WO 02/081229 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. These developers can be used alone or in combination of two or more.
  • the diphenylsulfone crosslinking type compound represented by Chemical Formula 1), the dihydroxydiphenylsulfone compound represented by General Formula (Chemical Formula 6), and the diphenylsulfone compound represented by General Formula (Chemical Formula 7) are preferable.
  • diphenylsulfone bridged compound represented by the formula 1) 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4′-allyloxydiphenylsulfone, and 4-hydroxy-4′-n-propoxy Diphenyl sulfone is more preferred.
  • sensitizer used in the present invention examples include fatty acid amides such as diphenylsulfone, stearamide, and palmitic acid amide, benzyloxynaphthalene, 1,2-di- (3-methylphenoxy) ethane, and dioxalate (p- Examples thereof include, but are not limited to, methylbenzyl). These sensitizers may be used alone or in combination of two or more.
  • the above acrylic resins fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, polyvinyl alcohols such as terminal alkyl-modified polyvinyl alcohol, hydroxyethyl cellulose, Cellulose ethers and derivatives thereof such as methylcellulose, ethylcellulose, carboxymethylcellulose, and acetylcellulose, starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (eg, hydroxyethylated starch), cationization Starch and other starches, polyacrylamide, cationic polyacrylamide, anionic polyacrylamide, amphoteric polyacrylate Polyamides such as amides, Polyurethane resins such as polyester polyurethane resins, polyether polyurethane resins, polyurethane
  • the binder used in the present invention is preferably an emulsion or latex of the above urethane resin or styrene-butadiene resin in order to improve the adhesion and tackiness to the plastic film.
  • Cross-linking agents include glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, magnesium chloride And borax, boric acid, alum, ammonium chloride, and the like.
  • lubricant examples include fatty acid metal salts such as zinc stearate and calcium stearate, waxes, and silicone resins.
  • fatty acid metal salts such as zinc stearate and calcium stearate
  • waxes such as waxes, and silicone resins.
  • silicone resins such as silicone resins.
  • 4,4′-butylidene (6-tert-butyl-3-methylphenol), 2,2′-di-tert-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, and the like can also be added.
  • leuco dyes, developers, sensitizers and other various components used in the present invention are determined according to the required performance and recording suitability, and are not particularly limited. Is usually 0.5 to 10 parts by weight of developer, 0.5 to 20 parts by weight of pigment, about 0.1 to 10 parts by weight of sensitizer, and 0.01 to 10 parts of stabilizer for 1 part by weight of leuco dye. About 10 parts by weight and 0.01 to 10 parts by weight of other components are used, and the binder is suitably about 5 to 50% by weight in the solid content of the heat-sensitive recording layer.
  • the leuco dye, color developer, and materials to be added as necessary are finely pulverized to a particle size of several microns or less with a pulverizer such as a ball mill, attritor or sand glider or an appropriate emulsifying device.
  • a pulverizer such as a ball mill, attritor or sand glider or an appropriate emulsifying device.
  • As the solvent used in the coating solution water, alcohol or the like can be used, and its solid content is about 20 to 40% by weight.
  • thermosensitive recording layer is usually about 2 to 10 g / m 2
  • coating amount of the protective layer is usually about 1 to 5 g / m 2 .
  • 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 developer dispersion liquid (A liquid), a leuco dye dispersion liquid (B liquid), and a sensitizer dispersion liquid (C liquid) having the following composition are each individually separated by a sand grinder to an average particle diameter of 0.5 microns. Until wet grinding.
  • Thermosensitive recording layer coating solution 1 (hereinafter referred to as “SBR formulation”)> Developer dispersion (liquid A) 36.0 parts Leuco dye dispersion (liquid B) 13.8 parts Sensitizer dispersion (liquid C) 9.0 parts Styrene / butadiene copolymer latex (solid content 48%) 16.0 parts Sodium dioctylsulfosuccinate (Kao Co., Perex OT-P, solid content 70%) 0.15 parts Water 15.0 parts ⁇ Coating liquid 2 for thermosensitive recording layer (hereinafter referred to as “PVA formulation”) )> Developer Dispersion (Liquid A) 36.0 parts Leuco Dye Dispersion (Liquid B) 13.8 parts Sensitizer Dispersion (Liquid C) 9.0 parts Completely saponified polyvinyl alcohol (Pura117, manufactured by Kuraray Co.,
  • Non-core shell type acrylic resin emulsion Mitsubishi Chemicals, ASN1004K, Tg 55 ° C., solid content 18%)
  • Self-emulsifying polyolefin resin emulsion Silicone stearate (manufactured by Chukyo Yushi Co., Ltd., Hydrin L536, solid content 40%)
  • 4.0 parts sodium dioctylsulfosuccinate manufactured by Kao Corporation, Perex OT-P, solid content 70%
  • ⁇ Coating liquid 2 for protective layer Non-core shell type acrylic resin emulsion (Mitsui Chemicals, ASN1004K, Tg 55 ° C., solid content 18%) 2
  • Example 1 Coating after drying the thermal recording layer coating liquid 1 (SBR formulation) on a polyethylene terephthalate film (manufactured by Teijin Ltd., Teijin Tetron 330, thickness 38 ⁇ m, total light transmittance 82%, hereinafter referred to as “PET film”). After coating and drying so that the amount is 5.0 g / m 2 , the coating liquid 1 for the protective layer is further coated and dried so that the coating amount after drying is 3.0 g / m 2. Was made.
  • SBR formulation thermal recording layer coating liquid 1
  • PET film polyethylene terephthalate film
  • Example 2 The same procedure as in Example 1 was conducted except that the PET film of Example 1 was replaced with a triacetyl cellulose film (Fuji Film, Fujitac, thickness 40 ⁇ m, total light transmittance 90%, hereinafter referred to as “TAC film”). A heat-sensitive recording material was produced.
  • TAC film a triacetyl cellulose film
  • a heat-sensitive recording material was prepared in the same manner as in Example 1 except that 15.0 parts of a self-emulsifying type polyolefin resin emulsion (manufactured by Sumitomo Seika Co., Ltd., Syxen-A-GH, solid content 24.4%) was used.
  • a thermosensitive recording material was produced in the same manner as in Example 1 except that the protective layer coating solution 2 was used instead of the protective layer coating solution 1.
  • Example 5 The same as in Example 1 except that the non-core shell type acrylic resin emulsion in the protective layer coating liquid 1 was replaced with a non-core shell type acrylic resin emulsion (manufactured by Mitsui Chemicals, XNP3, Tg 35 ° C., solid content 18%). Thus, a heat-sensitive recording material was produced.
  • Example 6 24.0 parts of the non-core shell type acrylic resin emulsion in the coating liquid 1 for the protective layer was replaced with 22.0 parts of a core shell type acrylic resin (Nippon Paint, N-538, Tg 100 ° C., solid content 20%). Except for the above, a heat-sensitive recording material was produced in the same manner as in Example 1.
  • thermosensitive recording material was prepared in the same manner as in Example 1 except that the blending parts of the non-core shell acrylic resin emulsion and the self-emulsifying polyolefin resin emulsion in the protective layer coating solution 1 were changed to 12.0 parts, respectively.
  • Example 8 Heat sensitive in the same manner as in Example 1 except that the blending part of the non-core shell acrylic resin emulsion in the protective layer coating liquid 1 was changed to 27.5 parts and the blending part of the self-emulsifying polyolefin resin emulsion was changed to 0.3 parts.
  • a recording body was produced.
  • thermosensitive recording material was produced in the same manner as in Example 1.
  • Example 10 2,4′-dihydroxydiphenylsulfone (manufactured by Nikka Chemical Co., Ltd., BPS-24C), instead of diphenylsulfone cross-linking compound (manufactured by Nippon Soda Co., Ltd., D-90) in the developer dispersion (liquid A)
  • a heat-sensitive recording material was produced in the same manner as in Example 1 using “24 BPS”.
  • Example 11 instead of the diphenylsulfone cross-linking compound (Nihon Soda Co., Ltd., D-90) in the developer dispersion (liquid A), 4-hydroxy-4'-allyloxydiphenyl sulfone (Nikka Chemical Co., Ltd., BPS-) A thermal recording material was prepared in the same manner as in Example 1 using MAE.
  • Example 12 4-hydroxy-4'-n-propoxydiphenyl sulfone (Api Corp., Tomillac) instead of diphenylsulfone cross-linking compound (Nippon Soda Co., Ltd., D-90) in the developer dispersion (liquid A)
  • a heat-sensitive recording material was prepared in the same manner as in Example 1 using KN).
  • Example 13 Instead of the diphenylsulfone cross-linking compound (Nihon Soda Co., Ltd., D-90) in the developer dispersion (liquid A), 4-hydroxy-4'-isopropoxydiphenyl sulfone (Nippon Soda Co., Ltd., D-8) ) was used to produce a thermosensitive recording material in the same manner as in Example 1.
  • Example 14 Instead of the diphenylsulfone cross-linked compound (Nippon Soda Co., Ltd., D-90) in the developer dispersion (liquid A), a compound represented by the following formula (Chemical Formula 8) (manufactured by API Corporation, SU727) was used to prepare a thermosensitive recording material in the same manner as in Example 1.
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the protective layer coating solution 3 was used instead of the protective layer coating solution 1. A photograph of the surface of the protective layer of the produced thermal recording material is shown in FIG. [Comparative Example 3] A heat-sensitive recording material was produced in the same manner as in Example 1 except that the protective layer was not provided.
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the self-emulsifying polyolefin resin emulsion of the protective layer coating liquid 1 was not blended and the number of blended parts of the non-core shell acrylic resin emulsion was 27.5 parts.
  • thermosensitive recording material was produced in the same manner as in Example 1 except that the non-core shell type acrylic resin emulsion of the coating liquid 1 for the protective layer was not blended, and the number of blended parts of the self-emulsifying polyolefin resin emulsion was 20.5 parts. .
  • thermosensitive recording material The following evaluation was performed about the produced thermosensitive recording material.
  • ⁇ Print density> Using the TH-PMD manufactured by Okura Electric Co., Ltd. (with a thermal recording paper printing tester and Kyocera thermal head installed), the printed thermal recording medium was solid printed at an applied energy of 0.42 mJ / dot and a printing speed of 50 mm / sec. did. The print density of the recording part was measured with a Macbeth densitometer (RD-914, using an amber filter).
  • thermosensitive recording medium was solid-printed with an applied energy of 0.20 mJ / dot under an environment of 0 ° C. using a printing tester (manufactured by Canon Inc., HT180). The printing state at this time was evaluated according to the following criteria. When the outermost layer of the recording material sticks (sticks) to the head of the printing tester, it cannot be printed partially.
  • ⁇ Plasticizer resistance> Using the TH-PMD manufactured by Okura Electric Co., Ltd. (with a thermal recording paper printing tester and Kyocera thermal head installed), the printed thermal recording medium was solid printed at an applied energy of 0.42 mJ / dot and a printing speed of 50 mm / sec. did.
  • a polyvinyl 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 material is placed on the paper tube so that the printed part is on the outer surface. It was wound around and fixed. After processing for 5 hours in an environment of 40 ° C.
  • Residual rate (%) (recording density after processing / recording density before processing) ⁇ 100 ⁇ Reprintability>
  • the produced thermal recording material was allowed to stand in an environment of 50 ° C. and 90% RH for 1 day, and then allowed to stand in an environment of 23 ° C. and 50% RH for 3 hours to obtain TH-PMD (thermal recording) manufactured by Okura Electric Co., Ltd.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
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Publication number Priority date Publication date Assignee Title
US9579916B2 (en) 2013-09-30 2017-02-28 Nippon Paper Industries Co., Ltd. Thermosensitive recording medium

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002331750A (ja) * 2001-05-11 2002-11-19 Mitsubishi Paper Mills Ltd 感熱記録媒体
JP2010247533A (ja) * 2009-03-24 2010-11-04 Nippon Paper Industries Co Ltd 感熱記録体
JP2011020352A (ja) * 2009-07-16 2011-02-03 Nippon Paper Industries Co Ltd 感熱記録体
JP2011156855A (ja) * 2010-01-07 2011-08-18 Nippon Paper Industries Co Ltd 感熱記録体
JP2013095105A (ja) * 2011-11-04 2013-05-20 Nippon Paper Industries Co Ltd 感熱記録体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002331750A (ja) * 2001-05-11 2002-11-19 Mitsubishi Paper Mills Ltd 感熱記録媒体
JP2010247533A (ja) * 2009-03-24 2010-11-04 Nippon Paper Industries Co Ltd 感熱記録体
JP2011020352A (ja) * 2009-07-16 2011-02-03 Nippon Paper Industries Co Ltd 感熱記録体
JP2011156855A (ja) * 2010-01-07 2011-08-18 Nippon Paper Industries Co Ltd 感熱記録体
JP2013095105A (ja) * 2011-11-04 2013-05-20 Nippon Paper Industries Co Ltd 感熱記録体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9579916B2 (en) 2013-09-30 2017-02-28 Nippon Paper Industries Co., Ltd. Thermosensitive recording medium

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