WO2013137243A1 - Thermosensitive recording medium - Google Patents

Thermosensitive recording medium 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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WO
WIPO (PCT)
Prior art keywords
heat
recording material
sensitive recording
group
acrylic resin
Prior art date
Application number
PCT/JP2013/056784
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French (fr)
Japanese (ja)
Inventor
泰明 松森
平井　健二
荻野　明人
Original Assignee
日本製紙株式会社
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Filing date
Publication date
Priority claimed from JP2012060724A external-priority patent/JP2013193266A/en
Priority claimed from JP2012069436A external-priority patent/JP2013199074A/en
Priority claimed from JP2012073389A external-priority patent/JP2013202905A/en
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/en
Priority to FI20145896A priority Critical patent/FI127015B/en

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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.

Abstract

　[Problem] Plastic films have a lower liquid absorbency than paper for water and other solvents. As a result, residual water or other solvent in a coating liquid in a thermosensitive recording layer makes it easy for ripple-shaped coating defects to occur (fig. 1). To address this problem, the present invention uses a plastic film as a support, on top of which a thermosensitive recording layer and a protective layer as the outermost layer are provided in that order. This makes it possible to provide a thermosensitive recording medium with reduced coating defects.　[Solution] By using a plastic film as a support, providing a thermosensitive recording layer and a protective layer an outermost layer in that order, and by having this protective layer contain an acrylic resin and a polyolefin resin, normal performance with respect to water resistance required of such a thermosensitive recording medium is exhibited, and it is possible to prevent the occurrence of coating defects.　

Description

感熱記録体Thermal recording material
　この発明は、プラスチックフィルムから成る支持体上に感熱記録層と保護層を設けた感熱記録体に関し、より詳細には、プラスチックフィルムを支持体として、塗工欠陥が減少した感熱記録体に関する。 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.
　感熱記録体は通常無色ないし淡色の電子供与性ロイコ染料（以下、「ロイコ染料」ともいう）とフェノール性化合物等の電子受容性顕色剤（以下、「顕色剤」ともいう）とを、それぞれ微細な粒子に磨砕分散した後、両者を混合し、バインダー、充填剤、感度向上剤、滑剤及びその他の助剤を添加して得られた塗工液を、紙、合成紙、フィルム、プラスチック等の支持体に塗工したものであり、サーマルヘッド、ホットスタンプ、熱ペン、レーザー光等の加熱による瞬時の化学反応により発色し、記録画像が得られる。感熱記録体は、ファクシミリ、コンピューターの端末プリンター、自動券売機、計測用レコーダー等に広範囲に使用されている。
　寸法安定性や強度が良いことから、支持体にプラスチックフィルムを用いた感熱記録体が増加しているが（特許文献１等）、感熱記録体の支持体にプラスチックフィルムを用いた場合に、水分により塗工層が剥離する問題を解決するために、感熱記録層上にポリオレフィン系樹脂を含む保護層と光沢層を設けた感熱記録体が開発されている（特許文献２）。
　また、耐久性や耐水性を要求される屋外用途で使用される感熱記録体においては、感熱記録層の上にアクリル系樹脂のエマルションを含有させた保護層を設けることが行なわれている（特許文献３～６等）。 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. 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.).
特開２００７－１３０９９１JP2007-130991 特開２００１－１５０８１３JP2001-50813A 国際公開ＷＯ２０１０／１１０２０９International publication WO2010 / 110209 国際公開ＷＯ２００７／０４９６２１International Publication WO2007 / 049621 特開平６－２６２８５３JP-A-6-262853 特開２００４－７４５３１JP 2004-74531 A
　感熱記録体の支持体にプラスチックフィルムを用いた場合、表面強度や耐水性を高めるために、一般に感熱記録層上に保護層を設ける。
　しかし、プラスチックフィルムは、紙に比べて水やその他の溶媒の吸液性がないため、感熱記録層に塗工液中の水などの溶媒が残存することにより、さざ波状の塗工欠陥が生じやすい（後述の比較例２、図１参照）。この塗工欠陥は光の透過状態の差異に起因することから、支持体に透明なプラスチックフィルムを用いた場合、より顕著に視認される。また、この問題は、プラスチックフィルムへの接着性や粘着性を向上させる塗工液を用いた場合には、さらに顕著になる。
　この問題は、保護層にオレフィン系樹脂を含有させることにより解消することができるが（後述の比較例５）、その一方で、オレフィン系樹脂は耐熱性や表面強度が弱いため、印字時に印字走行性（スティッキング）の問題が生じる。保護層上に更に塗工層を設けることにより、この問題を解決することが提案されている（特許文献２）。
　そのため、本発明は、プラスチックフィルムを支持体とし、その上に順次感熱記録層と最外層として保護層を設けた感熱記録体において、塗工欠陥が減少し、印字走行性（スティッキング）の優れた感熱記録体を提供することを目的とする。 When a plastic film is used as the support for the heat-sensitive recording material, a protective layer is generally provided on the heat-sensitive recording layer in order to increase surface strength and water resistance.
However, since 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). On the other hand, since the olefin resin is weak in heat resistance and surface strength, printing travels during printing. The problem of sex (sticking) arises. It has been proposed to solve this problem by further providing a coating layer on the protective layer (Patent Document 2).
For this reason, 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.
　本発明者らは鋭意検討の結果、支持体としてプラスチックフィルムを用い、順次感熱記録層と最外層として保護層を設け、この保護層にアクリル系樹脂及びポリオレフィン系樹脂を含有させることにより、このような感熱記録体に要求される耐水性等について通常の性能を示し、かつ塗工欠陥の発生を防ぐことができることを見出し、本願発明を完成させるに至った。
　すなわち、本発明は、プラスチックフィルム上に、無色ないし淡色の電子供与性ロイコ染料及び電子受容性顕色剤を含有する感熱記録層及び該感熱記録層上に最外層として保護層を有する感熱記録体において、該保護層がアクリル系樹脂及びポリオレフィン系樹脂を含有する感熱記録体である。 As a result of intensive studies, 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. In the above, the protective layer is a heat-sensitive recording material containing an acrylic resin and a polyolefin resin.
比較例２で作製した感熱記録体(１０．５×１４ｃｍ)の保護層表面の写真である。支持体はＰＥＴフィルムであり、保護層表面にさざ波状の塗工欠陥が生じている。4 is a photograph of the surface of a protective layer of a 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.
　本発明の感熱記録体は、プラスチックフィルム（支持体）上に感熱記録層を設け、その上に最外層として保護層を設け、この保護層がアクリル系樹脂及びポリオレフィン系樹脂を含有する。 In the heat-sensitive recording material of the present invention, 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.
　本発明で用いるプラスチックフィルムとしては、例えば、ポリエチレンテレフタレート（ＰＥＴ）フィルム、トリアセチルセルロース（ＴＡＣ）フィルム、ポリエチレンナフタレート（ＰＥＮ）フィルム等が挙げられる。また、具体的には、ＪＳＲ社製ノルボルネン系フィルム（商品名：ＡＲＴＯＮフィルム）、日本ゼオン社製シクロオレフィン系フィルム（商品名：ゼオノアフィルム）、これらのフィルムを組み合わせた複合フィルムを例示することができる。特に、光透過性を要求される用途に用いられる場合には、支持体は前述の樹脂フィルムのうち、全光線透過率が３０％以上のものが好ましく、７０％以上であることがより好ましい。 Examples of the plastic film used in the present invention include a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, and a polyethylene naphthalate (PEN) film. Specifically, 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. In particular, 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.
　本発明で用いるポリオレフィン系樹脂は、エチレンやプロピレン等のオレフィンの重合体であり、モノポリマーでも、これら以外のビニル化合物とのコポリマーでもよい。
　本発明で用いるポリオレフィン系樹脂としては、オレフィン・不飽和カルボン酸共重合体が好ましい。オレフィンとしては、エチレン、プロピレン、ブチレン等が好ましく、エチレンが特に好ましい。不飽和カルボン酸としては、好ましくは（メタ）アクリル酸（即ち、アクリル酸又はメタクリル酸）、マレイン酸、イタコン酸、フマル酸等、より好ましくは（メタ）アクリル酸である。オレフィン・不飽和カルボン酸共重合体としては、エチレンと（メタ）アクリル酸の共重合体やプロピレンと（メタ）アクリル酸共重合体の共重合体が好ましい。
　このようなポリオレフィン系樹脂の重量平均分子量は、好ましくは５,０００～１００,０００、より好ましくは１０,０００～５０,０００である。重量平均分子量が５,０００未満であると、ブロッキングが生じることがある。また、重量平均分子量が１００,０００を越えるものは生産性に問題が生じることがある。
　オレフィン・不飽和カルボン酸共重合体としては、例えば、ハイテックＳ－３１２１、ハイテックＳ－３１２３、ハイテックＳ－３１２７（以上、東邦化学工業株式会社製）、ザイクセン－Ａ－ＧＨ、ザイクセン－ＡＣ、ザイクセン－Ｎ，ザイクセン－Ｌ（以上、住友精化株式会社製）等が挙げられる。 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.
　本発明で用いるアクリル系樹脂は、（メタ）アクリル酸及び、（メタ）アクリル酸と共重合可能な単量体成分（オレフィンを除く）から成る。（メタ）アクリル酸は、アクリル系樹脂１００部中１～１０部配合することが好ましい。（メタ）アクリル酸は、アルカリ可溶性であり、中和剤の添加によりアクリル系樹脂を水溶性樹脂にする特性を有している。アクリル系樹脂を水溶性樹脂に変化させることによって、特に保護層中に顔料を含有する場合、顔料への結合性が著しく向上し、多量の顔料含有下でも優れた強度を有する保護層を形成することができる。（メタ）アクリル酸と共重合可能な成分としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸－２－エチルへキシル、（メタ）アクリル酸オクチルなどのアクリル酸アルキル樹脂及びエポキシ樹脂、シリコーン樹脂、スチレン又はその誘導体によって変性された上記アクリル酸アルキル樹脂などの変性アクリル酸アルキル樹脂、（メタ）アクリロニトリル、アクリル酸エステル、ヒドロキシアルキルアクリル酸エステルを例示できるが、特に（メタ）アクリロニトリル及び／又はメタクリル酸メチルを配合することが好ましい。（メタ）アクリロニトリルはアクリル系樹脂１００部中１５～７０部配合することが好ましい。また、メタクリル酸メチルはアクリル系樹脂１００部中２０～８０部含むことが好ましい。（メタ）アクリロニトリル及びメタクリル酸メチルを含む場合、（メタ）アクリロニトリルをアクリル系樹脂１００部中１５～１８部、メタクリル酸メチルをアクリル系樹脂１００部中２０～８０部配合することが好ましい。
　本発明におけるアクリル系樹脂のガラス転移点（Ｔｇ）は５０℃より高く９５℃以下である。Ｔｇが５０℃以下であると、耐水性は向上するが、十分な耐熱性が得られないため、スティックを生じやすくなる。一方、Ｔｇが高いアクリル系樹脂を含有させると耐スティック性や耐擦過性は向上する傾向だが、Ｔｇが高すぎると保護層が脆くなり、耐水性、耐可塑剤性や耐溶剤性が十分ではなくなり、目的とする効果が得られない場合がある。なお、アクリル系樹脂のＴｇは示差走査熱量測定（ＤＳＣ）によって測定する。 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. By changing the acrylic resin to a water-soluble resin, particularly when a pigment is contained in the protective layer, the binding property to the pigment is remarkably improved, and a protective layer having excellent strength even when containing a large amount of pigment is formed. be able to. Examples of the component copolymerizable with (meth) acrylic acid 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. On the other hand, if an acrylic resin having a high Tg is contained, 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).
　本発明で使用するアクリル系樹脂は、好ましくは非コアシェル型アクリル系樹脂である。一般に、コアシェル型アクリル系樹脂は、非コアシェル型アクリル系樹脂に比べて耐熱性が優れ、塗工層に用いた場合に耐スティック性に優れるため多用されている。しかし、コアシェル型アクリル系樹脂のシェル部は、通常熱伝導性が低いために発色感度が悪いという欠点も併せ持っている。一方、通常の非コアシェル型アクリル系樹脂は耐熱性が低く、スティックやヘッドカスなどが発生しやすい欠点を持っていたが、本願発明で使用するＴｇが５０℃より高く９５℃以下である非コアシェル型アクリル系樹脂は、耐熱性に優れているため、発色感度が良好であるとともに、耐スティック性や耐ヘッドカス性が良好であるという利点がある。 The acrylic resin used in the present invention is preferably a non-core shell type acrylic resin. In general, 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. However, 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. On the other hand, 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.
　また、本発明の保護層は、顔料を含まないことが好ましい。顔料としては、カオリン、焼成カオリン、水酸化アルミニウム、シリカ、炭酸カルシウム、ケイソウ土、タルク、酸化チタンなどの無機又は有機充填剤などが挙げられる。
　また、本発明の保護層は、上記成分以外に、ステアリン酸亜鉛、ステアリン酸カルシウム等の脂肪酸金属塩、ワックス類、シリコーン樹脂類などの滑剤、ベンゾフェノン系やトリアゾール系の紫外線吸収剤、架橋剤、分散剤、消泡剤、酸化防止剤、蛍光染料等を、本願発明の効果を阻害しない限り、含有してもよい。 Moreover, it is preferable that the protective layer of this invention does not contain a pigment. Examples of the pigment include inorganic or organic fillers such as kaolin, calcined kaolin, aluminum hydroxide, silica, calcium carbonate, diatomaceous earth, talc, and titanium oxide.
In addition to the above components, 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.
　本発明の保護層中の、ポリオレフィン系樹脂の配合量は、固形分で、好ましくは３～６０重量％、より好ましくは５～３０重量％である。
　本発明の保護層中の、アクリル系樹脂の配合量は、固形分で、好ましくは１５～９７重量％、より好ましくは５０～９５重量％である。
　ポリオレフィン系樹脂／アクリル系樹脂の配合重量比（固形分）は、好ましくは３／９７～５０／５０、より好ましくは５／９５～４０／６０である。
　保護層中のポリオレフィン系樹脂とアクリル系樹脂の合計配合量は、固形分として、好ましくは２０～１００重量％、より好ましくは４０～９０重量％である。 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.
　本発明の感熱記録層は、ロイコ染料及び顕色剤を含有し、更に増感剤、バインダー、架橋剤、滑剤、上記の顔料、その他の各種成分を含有してもよい。
　本発明で使用するロイコ染料としては、従来の感圧あるいは感熱記録紙分野で公知のものは全て使用可能であり、特に制限されるものではないが、トリフェニルメタン系化合物、フルオラン系化合物、フルオレン系、ジビニル系化合物等が好ましい。以下に代表的な無色ないし淡色のロイコ染料（染料前駆体）の具体例を示す。また、これらの染料前駆体は単独又は２種以上混合して使用してもよい。
＜トリフェニルメタン系ロイコ染料＞
　３，３－ビス（ｐ－ジメチルアミノフェニル）－６－ジメチルアミノフタリド〔別名クリスタルバイオレットラクトン〕；　３，３－ビス（ｐ－ジメチルアミノフェニル）フタリド〔別名マラカイトグリーンラクトン〕 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.
As the 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)
＜フルオラン系ロイコ染料＞
　３－ジエチルアミノ－６－メチルフルオラン；　３－ジエチルアミノ－６－メチル－７－アニリノフルオラン；　３－ジエチルアミノ－６－メチル－７－（ｏ，ｐ－ジメチルアニリノ）フルオラン；　３－ジエチルアミノ－６－メチル－７－クロロフルオラン；　３－ジエチルアミノ－６－メチル－７－（ｍ－トリフルオロメチルアニリノ）フルオラン；　３－ジエチルアミノ－６－メチル－７－（ｏ－クロロアニリノ）フルオラン；　３－ジエチルアミノ－６－メチル－７－（ｐ－クロロアニリノ）フルオラン；　３－ジエチルアミノ－６－メチル－７－（ｏ－フルオロアニリノ）フルオラン；　３－ジエチルアミノ－６－メチル－７－（ｍ－メチルアニリノ）フルオラン；　３－ジエチルアミノ－６－メチル－７－ｎ－オクチルアニリノフルオラン；　３－ジエチルアミノ－６－メチル－７－ｎ－オクチルアミノフルオラン；　３－ジエチルアミノ－６－メチル－７－ベンジルアミノフルオラン；　３－ジエチルアミノ－６－メチル－７－ジベンジルアミノフルオラン；３－ジエチルアミノ－６－クロロ－７－メチルフルオラン；　３－ジエチルアミノ－６－クロロ－７－アニリノフルオラン；　３－ジエチルアミノ－６－クロロ－７－ｐ－メチルアニリノフルオラン；　３－ジエチルアミノ－６－エトキシエチル－７－アニリノフルオラン；　３－ジエチルアミノ－７－メチルフルオラン；　３－ジエチルアミノ－７－クロロフルオラン；　３－ジエチルアミノ－７－（ｍ－トリフルオロメチルアニリノ）フルオラン；　３－ジエチルアミノ－７－（ｏ－クロロアニリノ）フルオラン；　３－ジエチルアミノ－７－（ｐ－クロロアニリノ）フルオラン；　３－ジエチルアミノ－７－（ｏ－フルオロアニリノ）フルオラン；　３－ジエチルアミノ－ベンゾ〔ａ〕フルオラン；　３－ジエチルアミノ－ベンゾ〔ｃ〕フルオラン；　３－ジブチルアミノ－６－メチル－フルオラン；　３－ジブチルアミノ－６－メチル－７－アニリノフルオラン；　３－ジブチルアミノ－６－メチル－７－（ｏ，ｐ－ジメチルアニリノ）フルオラン；　３－ジブチルアミノ－６－メチル－７－（ｏ－クロロアニリノ）フルオラン；　３－ジブチルアミノ－６－メチル－７－（ｐ－クロロアニリノ）フルオラン；　３－ジブチルアミノ－６－メチル－７－（ｏ－フルオロアニリノ）フルオラン；　３－ジブチルアミノ－６－メチル－７－（ｍ－トリフルオロメチルアニリノ）フルオラン；　３－ジブチルアミノ－６－メチル－クロロフルオラン；　３－ジブチルアミノ－６－エトキシエチル－７－アニリノフルオラン；　３－ジブチルアミノ－６－クロロ－７－アニリノフルオラン；　３－ジブチルアミノ－６－メチル－７－ｐ－メチルアニリノフルオラン；　３－ジブチルアミノ－７－（ｏ－クロロアニリノ）フルオラン；　３－ジブチルアミノ－７－（ｏ－フルオロアニリノ）フルオラン；　３－ジ－ｎ－ペンチルアミノ－６－メチル－７－アニリノフルオラン；　３－ジ－ｎ－ペンチルアミノ－６－メチル－７－（ｐ－クロロアニリノ）フルオラン；　３－ジ－ｎ－ペンチルアミノ－７－（ｍ－トリフルオロメチルアニリノ）フルオラン；　３－ジ－ｎ－ペンチルアミノ－６－クロロ－７－アニリノフルオラン；　３－ジ－ｎ－ペンチルアミノ－７－（ｐ－クロロアニリノ）フルオラン；　３－ピロリジノ－６－メチル－７－アニリノフルオラン；　３－ピペリジノ－６－メチル－７－アニリノフルオラン；　３－（Ｎ－メチル－Ｎ－プロピルアミノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－メチル－Ｎ－シクロヘキシルアミノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－シクロヘキシルアミノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－キシルアミノ）－６－メチル－７－（ｐ－クロロアニリノ）フルオラン；　３－（Ｎ－エチル－ｐ－トルイディノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－イソアミルアミノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－イソアミルアミノ）－６－クロロ－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－テトラヒドロフルフリルアミノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－イソブチルアミノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－エトキシプロピルアミノ）－６－メチル－７－アニリノフルオラン；　３－シクロヘキシルアミノ－６－クロロフルオラン；　２－（４－オキサヘキシル）－３－ジメチルアミノ－６－メチル－７－アニリノフルオラン；　２－（４－オキサヘキシル）－３－ジエチルアミノ－６－メチル－７－アニリノフルオラン；　２－（４－オキサヘキシル）－３－ジプロピルアミノ－６－メチル－７－アニリノフルオラン；　２－メチル－６－ｐ－（ｐ－ジメチルアミノフェニル）アミノアニリノフルオラン；　２－メトキシ－６－ｐ－（ｐ－ジメチルアミノフェニル）アミノアニリノフルオラン；　２－クロロ－３－メチル－６－ｐ－（ｐ－フェニルアミノフェニル）アミノアニリノフルオラン；　２－クロロ－６－ｐ－（ｐ－ジメチルアミノフェニル）アミノアニリノフルオラン；　２－ニトロ－６－ｐ－（ｐ－ジエチルアミノフェニル）アミノアニリノフルオラン；　２－アミノ－６－ｐ－（ｐ－ジエチルアミノフェニル）アミノアニリノフルオラン；　２－ジエチルアミノ－６－ｐ－（ｐ－ジエチルアミノフェニル）アミノアニリノフルオラン；　２－フェニル－６－メチル－６－ｐ－（ｐ－フェニルアミノフェニル）アミノアニリノフルオラン；　２－ベンジル－６－ｐ－（ｐ－フェニルアミノフェニル）アミノアニリノフルオラン；　２－ヒドロキシ－６－ｐ－（ｐ－フェニルアミノフェニル）アミノアニリノフルオラン；　３－メチル－６－ｐ－（ｐ－ジメチルアミノフェニル）アミノアニリノフルオラン；　３－ジエチルアミノ－６－ｐ－（ｐ－ジエチルアミノフェニル）アミノアニリノフルオラン；　３－ジエチルアミノ－６－ｐ－（ｐ－ジブチルアミノフェニル）アミノアニリノフルオラン；　２，４－ジメチル－６－〔（４－ジメチルアミノ）アニリノ〕－フルオラン <Fluoran leuco dye>
3-diethylamino-6-methylfluorane; 3-diethylamino-6-methyl-7-anilinofluorane; 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluorane; 3-diethylamino- 3-diethylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane; 3-diethylamino-6-methyl-7- (o-chloroanilino) fluorane; Diethylamino-6-methyl-7- (p-chloroanilino) fluorane; 3-diethylamino-6-methyl-7- (o-fluoroanilino) fluorane; 3-diethylamino-6-methyl-7- (m-methylanilino) fluorane 3-diethylamino-6-methyl-7-n-octylanilinofluorane; 3-diethylamino-6-methyl-7-n-octylaminofluorane; 3-diethylamino-6-methyl-7-benzylaminofluorane; 3-diethylamino-6-methyl-7-dibenzylaminofluorane; 3-diethylamino-6-chloro-7-anilinofluorane; 3-diethylamino-6-chloro-7-p-methylanilinofluorane; 3-diethylamino-6 3-Ethoxyethyl-7-anilinofluorane; 3-diethylamino-7-methylfluorane; 3-diethylamino-7-chlorofluorane; 3-diethylamino-7- (m-trifluoromethylanilino) fluorane; Diethylamino-7- (o-chloroanilino) fluorane; 3-diethylamino 3-diethylamino-7- (o-fluoroanilino) fluorane; 3-diethylamino-benzo [a] fluorane; 3-diethylamino-benzo [c] fluorane; 3-dibutylamino 3-dibutylamino-6-methyl-7-anilinofluorane; 3-dibutylamino-6-methyl-7- (o, p-dimethylanilino) fluorane; 3-dibutylamino- 6-methyl-7- (o-chloroanilino) fluorane; 3-dibutylamino-6-methyl-7- (p-chloroanilino) fluorane; 3-dibutylamino-6-methyl-7- (o-fluoroanilino) fluorane 3-dibutylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane; 3-dibutylamino-6-methyl-chlorofluorane; 3-dibutylamino-6-ethoxyethyl-7-anilinofluorane; 3-dibutylamino-6-chloro-7-anilinofluorane; 3-dibutylamino -6-methyl-7-p-methylanilinofluorane; 3-dibutylamino-7- (o-chloroanilino) fluorane; 3-dibutylamino-7- (o-fluoroanilino) fluorane; 3-di-n 3-pentylamino-6-methyl-7-anilinofluorane; 3-di-n-pentylamino-6-methyl-7- (p-chloroanilino) fluorane; 3-di-n-pentylamino-7- (m -Trifluoromethylanilino) fluorane; 3-di-n-pentylamino-6-chloro-7-anilinofluorane; 3-di-n-pentyl Mino-7- (p-chloroanilino) fluorane; 3-pyrrolidino-6-methyl-7-anilinofluorane; 3-piperidino-6-methyl-7-anilinofluorane; 3- (N-methyl-N- Propylamino) -6-methyl-7-anilinofluorane; 3- (N-methyl-N-cyclohexylamino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-cyclohexylamino) ) -6-Methyl-7-anilinofluorane; 3- (N-ethyl-N-xylamino) -6-methyl-7- (p-chloroanilino) fluorane; 3- (N-ethyl-p-toluidino)- 6-methyl-7-anilinofluorane; 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-isoamyl) Amino) -6-chloro-7-anilinofluorane; 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-isobutyl) Amino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-ethoxypropylamino) -6-methyl-7-anilinofluorane; 3-cyclohexylamino-6-chlorofluorane; 2- (4-oxahexyl) -3-dimethylamino-6-methyl-7-anilinofluorane; 2- (4-oxahexyl) -3-diethylamino-6-methyl-7-anilinofluorane; 2 -(4-oxahexyl) -3-dipropylamino-6-methyl-7-anilinofluorane; 2-methyl-6-p- (p-dimethylaminophenyl) aminoani 2-Fluoro-6-p- (p-dimethylaminophenyl) aminoanilinofluorane; 2-chloro-3-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane; Chloro-6-p- (p-dimethylaminophenyl) aminoanilinofluorane; 2-nitro-6-p- (p-diethylaminophenyl) aminoanilinofluorane; 2-amino-6-p- (p- 2-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane; 2-phenyl-6-methyl-6-p- (p-phenylaminophenyl) aminoani Linofluorane; 2-benzyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane; 2-hydroxy-6-p- (p-phenylaminophenyl) aminoanilinofluorane; 3-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluorane; 3-diethylamino-6-p- (P-diethylaminophenyl) aminoanilinofluorane; 3-diethylamino-6-p- (p-dibutylaminophenyl) aminoanilinofluorane; 2,4-dimethyl-6-[(4-dimethylamino) anilino] -Fluoran
＜フルオレン系ロイコ染料＞
　３，６，６'－トリス（ジメチルアミノ）スピロ〔フルオレン－９，３'－フタリド〕；　３，６，６'－トリス（ジエチルアミノ）スピロ〔フルオレン－９，３'－フタリド〕
＜ジビニル系ロイコ染料＞
　３，３－ビス－〔２－（ｐ－ジメチルアミノフェニル）－２－（ｐ－メトキシフェニル）エテニル〕－４，５，６，７－テトラブロモフタリド；　３，３－ビス－〔２－（ｐ－ジメチルアミノフェニル）－２－（ｐ－メトキシフェニル）エテニル〕－４，５，６，７－テトラクロロフタリド；　３，３－ビス－〔１，１－ビス（４－ピロリジノフェニル）エチレン－２－イル〕－４，５，６，７－テトラブロモフタリド；　３，３－ビス－〔１－（４－メトキシフェニル）－１－（４－ピロリジノフェニル）エチレン－２－イル〕－４，５，６，７－テトラクロロフタリド <Fluorene leuco dye>
3,6,6′-tris (dimethylamino) spiro [fluorene-9,3′-phthalide]; 3,6,6′-tris (diethylamino) spiro [fluorene-9,3′-phthalide]
<Divinyl leuco dye>
3,3-bis- [2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrabromophthalide; 3,3-bis- [2- (P-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrachlorophthalide; 3,3-bis- [1,1-bis (4-pyrrolidinophenyl) ) Ethylene-2-yl] -4,5,6,7-tetrabromophthalide; 3,3-bis- [1- (4-methoxyphenyl) -1- (4-pyrrolidinophenyl) ethylene-2- Yl] -4,5,6,7-tetrachlorophthalide
＜その他＞
　３－（４－ジエチルアミノ－２－エトキシフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド；　３－（４－ジエチルアミノ－２－エトキシフェニル）－３－（１－オクチル－２－メチルインドール－３－イル）－４－アザフタリド；　３－（４－シクロヘキシルエチルアミノ－２－メトキシフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド；　３，３－ビス（１－エチル－２－メチルインドール－３－イル）フタリド；　３，６－ビス（ジエチルアミノ）フルオラン－γ－（３'－ニトロ）アニリノラクタム；　３，６－ビス（ジエチルアミノ）フルオラン－γ－（４'－ニトロ）アニリノラクタム；　１，１－ビス－〔２'，２'，２''，２''－テトラキス－（ｐ－ジメチルアミノフェニル）－エテニル〕－２，２－ジニトリルエタン；　１，１－ビス－〔２'，２'，２''，２''－テトラキス－（ｐ－ジメチルアミノフェニル）－エテニル〕－２－β－ナフトイルエタン；　１，１－ビス－〔２'，２'，２''，２''－テトラキス－（ｐ－ジメチルアミノフェニル）－エテニル〕－２，２－ジアセチルエタン；　ビス－〔２，２，２'，２'－テトラキス－（ｐ－ジメチルアミノフェニル）－エテニル〕－メチルマロン酸ジメチルエステル <Others>
3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide; 3- (4-diethylamino-2-ethoxyphenyl) -3- ( 1-octyl-2-methylindol-3-yl) -4-azaphthalide; 3- (4-cyclohexylethylamino-2-methoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl)- 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide; 3,6-bis (diethylamino) fluorane-γ- (3′-nitro) anilinolactam; 3,6 -Bis (diethylamino) fluorane-γ- (4'-nitro) anilinolactam; 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p-dimethyla Nophenyl) -ethenyl] -2,2-dinitrileethane; 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2- β-naphthoylethane; 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2,2-diacetylethane; bis- [2, 2,2 ′, 2′-Tetrakis- (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester
　本発明で用いる顕色剤としては、例えば、活性白土、アタパルジャイト、コロイダルシリカ、珪酸アルミニウムなどの無機酸性物質、４，４’－イソプロピリデンジフェノール、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、２，２－ビス（４－ヒドロキシフェニル）－４－メチルペンタン、４，４’－ジヒドロキシジフェニルスルフィド、ヒドロキノンモノベンジルエーテル、４－ヒドロキシ安息香酸ベンジル、４－ヒドロキシ－４’－メチルジフェニルスルホン、４－ヒドロキシフェニル－４’－ベンジルオキシフェニルスルホン、３，４－ジヒドロキシフェニル－４’－メチルフェニルスルホン、１－［４－（４－ヒドロキシフェニルスルホニル）フェノキシ］－４－［４－（４－イソプロポキシフェニルスルホニル）フェノキシ］ブタン、特開２００３－１５４７６０号公報記載のフェノール縮合組成物、特開平８－５９６０３号公報記載のアミノベンゼンスルホンアミド誘導体、ビス（４－ヒドロキシフェニルチオエトキシ）メタン、１，５－ジ（４－ヒドロキシフェニルチオ）－３－オキサペンタン、ビス（ｐ－ヒドロキシフェニル）酢酸ブチル、ビス（ｐ－ヒドロキシフェニル）酢酸メチル、１，１－ビス（４－ヒドロキシフェニル）－１－フェニルエタン、１，４－ビス［α－メチル－α－（４’－ヒドロキシフェニル）エチル］ベンゼン、１，３－ビス［α－メチル－α－（４’－ヒドロキシフェニル）エチル］ベンゼン、ジ（４－ヒドロキシ－３－メチルフェニル）スルフィド、２，２’－チオビス（３－tert－オクチルフェノール）、２，２’－チオビス（４－tert－オクチルフェノール）、
ＷＯ０２／０８１２２９号あるいは特開２００２－３０１８７３号公報記載の化合物、またＮ，Ｎ’－ジ－ｍ－クロロフェニルチオウレア等のチオ尿素化合物、ｐ－クロロ安息香酸、没食子酸ステアリル、ビス［４－（ｎ－オクチルオキシカルボニルアミノ）サリチル酸亜鉛］２水和物、４－［２－（ｐ－メトキシフェノキシ）エチルオキシ］サリチル酸、４－［３－（ｐ－トリルスルホニル）プロピルオキシ］サリチル酸、５－［ｐ－（２－ｐ－メトキシフェノキシエトキシ）クミル］サリチル酸の芳香族カルボン酸、及びこれらの芳香族カルボン酸の亜鉛、マグネシウム、アルミニウム、カルシウム、チタン、マンガン、スズ、ニッケル等の多価金属塩との塩、さらにはチオシアン酸亜鉛のアンチピリン錯体、テレフタルアルデヒド酸と他の芳香族カルボン酸との複合亜鉛塩、
下記一般式（化１）：
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ１、Ｒ２、ｍ及びｎの定義は後述する。）で表されるジフェニルスルホン架橋型化合物、下記一般式（化４）で表されるジヒドロキシジフェニルスルホン化合物
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ５、Ｒ６、Ｒ７、ｐ及びｑの定義は後述する。）等が挙げられる。 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. 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 4,4′-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4-hydroxy-4′-methyldiphenyl sulfone, 4-hydroxyphenyl-4′-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4′-methylphenylsulfone, 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4- Isopropoxyphenylsulfonyl) phenoxy ] Butane, a phenol condensation composition described in JP-A-2003-154760, an aminobenzenesulfonamide derivative described in JP-A-8-59603, bis (4-hydroxyphenylthioethoxy) methane, 1,5-di (4 -Hydroxyphenylthio) -3-oxapentane, butyl bis (p-hydroxyphenyl) acetate, methyl bis (p-hydroxyphenyl) acetate, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1, 4-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, 1,3-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, di (4-hydroxy- 3-methylphenyl) sulfide, 2,2′-thiobis (3-tert-octylphenol), 2,2′-thiobis (4-te rt-octylphenol),
Compounds described in WO02 / 081229 or JP2002-301873, thiourea compounds such as N, N′-di-m-chlorophenylthiourea, p-chlorobenzoic acid, stearyl gallate, bis [4- (n -Octyloxycarbonylamino) salicylate zinc] dihydrate, 4- [2- (p-methoxyphenoxy) ethyloxy] salicylic acid, 4- [3- (p-tolylsulfonyl) propyloxy] salicylic acid, 5- [p- (2-p-methoxyphenoxyethoxy) cumyl] aromatic carboxylic acids of salicylic acid and salts of these aromatic carboxylic acids with polyvalent metal salts such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel Furthermore, antipyrine complex of zinc thiocyanate, terephthalaldehyde acid and others Complex zinc salts with aromatic carboxylic acids,
The following general formula (Formula 1):
Figure JPOXMLDOC01-appb-C000005
 (Wherein definitions of R 1 , R 2 , m and n will be described later), a diphenylsulfone bridged compound represented by the following general formula (Formula 4)
Figure JPOXMLDOC01-appb-C000006
 (Wherein, definitions of R 5 , R 6 , R 7 , p and q will be described later).
　上記一般式（化１）において、Ｒ１は、それぞれ同じであっても異なってもよいが、好ましくは同一であり、ハロゲン原子、炭素数が１～６のアルキル基又はアルケニル基を表す。
　このアルキル基又はアルケニル基は、炭素数が１～６のアルキル基又はアルケニル基であり、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、イソへキシル基、１－メチルペンチル基、２－メチルペンチル基、ビニル基、アリル基、イソプロペニル基、１－プロペニル基、２－ブテニル基、３－ブテニル基、１，３－ブタンジエニル基、２－メチル－２－プロペニル基等が挙げられる。
　又はロゲン原子としては塩素、臭素、フッ素又はヨウ素、好ましくは塩素又は臭素を表す。
　ｍは、それぞれ同じであっても異なってもよく、好ましくは同一であり、０～４、好ましくは０を表す。
　ＯＨ基及び－ＯＲ２Ｏ－基は、ＳＯ２基に対して、パラ位にあることが好ましい。
　ｎは１～１１である。この化合物はｎが１～１１の混合物であることが好ましい。 In the above general formula (Formula 1), 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. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert group, -Butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, vinyl group, allyl group, isopropenyl Group, 1-propenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 2-methyl-2-propenyl group and the like.
Or as a rogen atom, it represents chlorine, bromine, fluorine or iodine, preferably chlorine or bromine.
Each m may be the same or different, and is preferably the same and represents 0 to 4, preferably 0.
The OH group and —OR 2 O— group are preferably in the para position with respect to the SO 2 group.
n is 1 to 11. This compound is preferably a mixture of n = 1-11.
　Ｒ２は、それぞれ同じであっても異なってもよいが、好ましくは同一である。
　Ｒ２としては、エーテル結合を有してもよい炭素数１～１２、好ましくは３～７の飽和若しくは不飽和の、好ましくは飽和の、直鎖若しくは分枝の、好ましくは直鎖の炭化水素基であってもよい。このような炭化水素としては、ポリアルキレンオキシド鎖やアルキレン基、好ましくはポリアルキレンオキシド鎖が好ましい。Ｒ２がポリアルキレンオキシド鎖の場合、－ＯＲ２Ｏ－としては、－Ｏ－（ＣｏＨ２ｏＯ）１～３－（式中、ｏ＝２～４、好ましくは２～３、より好ましくは２）が挙げられる。アルキレン基としては、－ＣｐＨ２ｐ－（式中、ｐ＝１～１２、好ましくは３～７）が挙げられる。 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. When R 2 is a polyalkylene oxide chain, —OR 2 O— includes —O— (C o H 2 o O) 1 to 3 — (where o = 2 to 4, preferably 2 to 3, more preferably 2). Examples of the alkylene group include —C p H 2p — (wherein p = 1 to 12, preferably 3 to 7).
　またＲ２としては、下記一般式
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｒ３はメチレン基又はエチレン基を表す。Ｒ３は互いにパラ位にあることが好ましい。）で表される置換フェニレン基であってもよい。 As R 2 , the following general formula
Figure JPOXMLDOC01-appb-C000007
 (In the formula, R 3 represents a methylene group or an ethylene group. R 3 are preferably para to each other).
　更に、Ｒ２としては、下記一般式
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ４は水素原子又は炭素数が１～４のアルキル基、好ましくは水素原子を表す。）で表される２価基を表す。）であってもよい。
　Ｒ２としては、これらの中で、上記のエーテル結合を有してもよい炭素数１～１２の飽和若しくは不飽和の直鎖若しくは分枝の炭化水素基が好ましい。
　上記一般式（化１）で表されるジフェニルスルホン架橋型化合物として、下式で表される化合物（日本曹達（株）製、Ｄ－９０)が好ましい。
Figure JPOXMLDOC01-appb-C000009
 Further, as R 2 , the following general formula
Figure JPOXMLDOC01-appb-C000008
 (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.
As 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.
Figure JPOXMLDOC01-appb-C000009
　上記一般式（化４）において、Ｒ５及びＲ６はそれぞれ独立して炭素数が１～８のアルキル基若しくはアルケニル基又はハロゲン原子を表し、Ｒ７は水素原子又は炭素数１～４の直鎖若しくは分岐の飽和若しくは不飽和炭化水素を表し、ｐ及びｑはそれぞれ独立して０～３の整数を表す。
　上記一般式（化４）で表されるジフェニルスルホン化合物としては下記一般式（化６）
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ５、Ｒ６、ｐ及びｑは上記定義したとおりである。）で表されるジヒドロキシジフェニルスルホン化合物、及び下記一般式（化７）
Figure JPOXMLDOC01-appb-C000011
 （式中、Ｒ５及びＲ６はそれぞれ独立して炭素数１～４のアルケニル基を表し、Ｒ７は上記定義したとおりであり、ｐ及びｑはそれぞれ独立して０～２の整数を表す。）で表されるジフェニルスルホン化合物が好ましい。 In the above general formula (Formula 4), R 5 and R 6 each independently represents an alkyl group or alkenyl group having 1 to 8 carbon atoms or a halogen atom, and 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).
Figure JPOXMLDOC01-appb-C000010
 (Wherein R 5 , R 6 , p and q are as defined above) and the following general formula (Formula 7)
Figure JPOXMLDOC01-appb-C000011
 (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.
　上記一般式（化６）で表されるジヒドロキシジフェニルスルホン化合物としては、４、４’－ジヒドロキシジフェニルスルホン、２、４’－ジヒドロキシジフェニルスルホン、４，４’－ジヒドロキシ－３，３’－ジアリルジフェニルスルホン、３，３’－ジメチル－４，４’－ジヒドロキシジフェニルスルホン、３，３’，５，５’－テトラメチル－４，４’－ジヒドロキシジフェニルスルホン、２，２’－ビス（４－クロロフェノール）スルホン、４－ヒドロキシフェニル－３’－イソプロピル－４’－ヒドロキシフェニルスルホン、ビス－（３－エチル－４－ヒドロキシフェニル）スルホン、２，２’－ビス（ｐ－ｔ－ブチルフェノール）スルホン、２，２’－ビス（ｐ－ｔ－ペンチルフェノール）スルホン、２，２’－ビス（ｐ－ｔ－オクチルフェノール）スルホン等が挙げられる。
　中でも、４，４’－ジヒドロキシジフェニルスルホン、２，４’－ジヒドロキシジフェニルスルホン、４，４’－ジヒドロキシ－３，３’－ジアリルジフェニルスルホンが好ましい。 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. Sulfone, 3,3′-dimethyl-4,4′-dihydroxydiphenylsulfone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylsulfone, 2,2′-bis (4-chloro) Phenol) sulfone, 4-hydroxyphenyl-3′-isopropyl-4′-hydroxyphenylsulfone, bis- (3-ethyl-4-hydroxyphenyl) sulfone, 2,2′-bis (pt-butylphenol) sulfone, 2,2′-bis (pt-pentylphenol) sulfone, 2,2′-bis (pt-octylphenol) Sulfone, and the like.
Of these, 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, and 4,4′-dihydroxy-3,3′-diallyldiphenylsulfone are preferable.
　上記一般式（化７）で表されるジフェニルスルホン化合物としては、４－ヒドロキシ－４’－ｎ－プロポキシジフェニルスルホン、４－ヒドロキシ－４’－イソプロポキシジフェニルスルホン、４－ヒドロキシ－４’－アリルオキシジフェニルスルホン、４－ヒドロキシ－４’－２－プロピレキシジフェニルスルホン、４－ヒドロキシ－４’－１－プロペニルジフェニルスルホン、４－ヒドロキシ－４’－エトキシジフェニルスルホン、４－ヒドロキシ－４’－ｎ－ブトキシジフェニルスルホン等が挙げられる。
　中でも、４－ヒドロキシ－４’－ｎ－プロポキシジフェニルスルホン、４－ヒドロキシ－４’－イソプロポキシジフェニルスルホン、４－ヒドロキシ－４’－アリルオキシジフェニルスルホンが好ましい。 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. Oxydiphenyl sulfone, 4-hydroxy-4′-2-propylexidiphenyl sulfone, 4-hydroxy-4′-1-propenyl diphenyl sulfone, 4-hydroxy-4′-ethoxydiphenyl sulfone, 4-hydroxy-4′-n -Butoxydiphenyl sulfone and the like.
Of these, 4-hydroxy-4′-n-propoxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, and 4-hydroxy-4′-allyloxydiphenylsulfone are preferable.
　上記１－［４－（４－ヒドロキシフェニルスルホニル）フェノキシ］－４－［４－（４－イソプロポキシフェニルスルホニル）フェノキシ］ブタンは、例えば、株式会社エーピーアイコーポレーション製商品名ＪＫＹ－２１４として入手可能であり、特開２００３－１５４７６０号公報記載のフェノール縮合組成物は、例えば、株式会社エーピーアイコーポレーション製商品名ＪＫＹ－２２４として入手可能である。
　また、上記ＷＯ０２／０８１２２９号等に記載の化合物は、日本曹達（株）製商品名ＮＫＫ－３９５、Ｄ－１００として入手可能である。この他、特開平１０－２５８５７７号公報記載の高級脂肪酸金属複塩や多価ヒドロキシ芳香族化合物などの金属キレート型発色成分を含有することもできる。
　これらの顕色剤は、単独又は２種以上混合して使用することもできる。 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. In addition, 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.
　これらの顕色剤の中で、印字濃度に優れ、可塑剤に対する高い安定性を有し、再印字性（高温高湿下での保管後の印字濃度）の低下が小さいため、前記一般式（化１）で表されるジフェニルスルホン架橋型化合物、前記一般式（化６）で表されるジヒドロキシジフェニルスルホン化合物、前記一般式（化７）で表されるジフェニルスルホン化合物が好ましく、前記一般式（化１）で表されるジフェニルスルホン架橋型化合物、並びに、４－ヒドロキシ－４’－イソプロポキシジフェニルスルホン、４－ヒドロキシ－４’－アリルオキシジフェニルスルホン、及び４－ヒドロキシ－４’－ｎ－プロポキシジフェニルスルホンがより好ましい。 Among these developers, since the printing density is excellent, the plasticizer has high stability, and the reprintability (printing density after storage under high temperature and high humidity) is small, the above general formula ( 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. And a diphenylsulfone bridged compound represented by the formula 1), and 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4′-allyloxydiphenylsulfone, and 4-hydroxy-4′-n-propoxy Diphenyl sulfone is more preferred.
　本発明で使用する増感剤としては、ジフェニルスルホン、ステアリン酸アミド、パルミチン酸アミド等の脂肪酸アマイド、ベンジルオキシナフタレン、１，２－ジ－（３－メチルフェノキシ）エタン、シュウ酸ジ（ｐ－メチルベンジル）などを例示することができるが、この限りではない。これらの増感剤は、単独又は２種以上混合して使用してもよい。 Examples of the sensitizer used in the present invention 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.
　バインダーとしては、上記アクリル系樹脂、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、カルボキシル変性ポリビニルアルコール、シラノール変性ポリビニルアルコール、カチオン変性ポリビニルアルコール、末端アルキル変性ポリビニルアルコールなどのポリビニルアルコール類、ヒドロキシエチルセルロース、メチルセルロース、エチルセルロース、カルボキシメチルセルロース、アセチルセルロースなどのセルロースエーテル及びその誘導体、澱粉、酵素変性澱粉、熱化学変性澱粉、酸化澱粉、エステル化澱粉、エーテル化澱粉（例えば、ヒドロキシエチル化澱粉など）、カチオン化澱粉などの澱粉類、ポリアクリルアミド、カチオン性ポリアクリルアミド、アニオン性ポリアクリルアミド、両性ポリアクリルアミドなどのポリアクリルアミド類、ポリエステルポリウレタン系樹脂、ポリエーテルポリウレタン系樹脂、ポリウレタン系アイオノマー樹脂などのウレタン系樹脂、スチレン－ブタジエン共重合体、スチレン－ブタジエン－アクリロニトリル共重合体、スチレン－ブタジエン－アクリル共重合体などのスチレン－ブタジエン系樹脂、ポリ酢酸ビニル、塩化ビニル－酢酸ビニル共重合体、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリアクリル酸エステル、アラビヤゴム、ポリビニルブチラール、ポリスチロース及びそれらの共重合体、シリコーン樹脂、石油樹脂、テルペン樹脂、ケトン樹脂、クマロン樹脂などを例示することができる。これらは併用してもよい。
　本発明で使用するバインダーとしては、プラスチックフィルムへの接着性や粘着性を向上させるために、上記ウレタン系樹脂やスチレン－ブタジエン系樹脂のエマルションやラテックスが好ましい。 As the binder, 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 ionomer resins, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile copolymers, styrene-butadiene-acrylic copolymers Styrene-butadiene resins such as polymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid esters, arabic rubber, polyvinyl butyral, polystyrose and copolymers thereof, Silicone resin, petroleum resin, terpene resin, ketone resin, coumarone resin and the like can be exemplified. These may be used in combination.
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.
　架橋剤としては、グリオキザール、メチロールメラミン、メラミンホルムアルデヒド樹脂、メラミン尿素樹脂、ポリアミンエピクロロヒドリン樹脂、ポリアミドエピクロロヒドリン樹脂、過硫酸カリウム、過硫酸アンモニウム、過硫酸ソーダ、塩化第二鉄、塩化マグネシウム、ホウ砂、ホウ酸、ミョウバン、塩化アンモニウムなどを例示することができる。 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.
　滑剤としては、ステアリン酸亜鉛、ステアリン酸カルシウム等の脂肪酸金属塩、ワックス類、シリコーン樹脂類などが挙げられる。
　また、記録画像の耐油性効果などを示す画像安定剤として、４，４'－ブチリデン（６－ｔ－ブチル－３－メチルフェノール）、２，２'－ジ－ｔ－ブチル－５，５'－ジメチル－４，４'－スルホニルジフェノール、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－シクロヘキシルフェニル）ブタン、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、４－ベンジルオキシ－４'－（２，３－エポキシ－２－メチルプロポキシ）ジフェニルスルホン等を添加することもできる。
　このほかにベンゾフェノン系やトリアゾール系の紫外線吸収剤、分散剤、消泡剤、酸化防止剤、蛍光染料等を使用することができる。 Examples of the lubricant include fatty acid metal salts such as zinc stearate and calcium stearate, waxes, and silicone resins.
Further, as image stabilizers showing the oil resistance effect of recorded images, 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.
In addition, benzophenone and triazole ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, fluorescent dyes, and the like can be used.
　本発明に使用するロイコ染料、顕色剤、増感剤、その他の各種成分の種類及び量は、要求される性能及び記録適性に従って決定され、特に限定されるものではないが、感熱記録層においては、通常ロイコ染料１重量部に対して顕色剤０．５～１０重量部、顔料０．５～２０重量部、増感剤０．１～１０重量部程度、安定化剤０．０１～１０重量部程度、その他の成分０．０１～１０重量部が使用され、バインダーは感熱記録層固形分中５～５０重量％程度が適当である。 The types and amounts of 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.
　ロイコ染料、顕色剤並びに必要に応じて添加する材料は、ボールミル、アトライター、サンドグライダーなどの粉砕機あるいは適当な乳化装置によって数ミクロン以下の粒子径になるまで微粒化し、バインダー及び目的に応じて各種の添加材料を加えて塗液とする。この塗液に用いる溶媒としては水あるいはアルコール等を用いることができ、その固形分は２０～４０重量％程度である。 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. Add various additive materials to make a coating solution. 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.
　上記塗液を、プラスチックフィルムの支持体に塗工することによって目的とする感熱記録体が得られる。
　各層の塗工方法としては、エアーナイフ法、ロッドブレード法、ベントブレード法、ベベルブレード法、ロール法、スロット型カーテン法、スライド型カーテン法、スライドホッパー型カーテン法、ビード型カーテン法、スプレー法、ダイ法などを例示することが可能であり、これらの塗工方法から適宜選択され使用される。
　感熱記録層の塗工量は通常２～１０ｇ／ｍ２程度であり、保護層の塗工量は通常１～５ｇ／ｍ２程度である。
　また、各層の塗工後にスーパーカレンダー掛けなどの平滑化処理を施すなど、感熱記録体分野における各種公知の技術を必要適宜付加することができる。 By applying the coating liquid onto a support of a plastic film, a desired heat-sensitive recording material can be obtained.
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.
The coating amount of the thermosensitive recording layer is usually about 2 to 10 g / m 2 , and the coating amount of the protective layer is usually about 1 to 5 g / m 2 .
Further, 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.
　以下、実施例にて本発明を例証するが本発明を限定することを意図するものではない。なお説明中、部及び％はそれぞれ重量部及び重量％を示す。
　まず、下記配合の顕色剤分散液（Ａ液）、ロイコ染料分散液（Ｂ液）及び増感剤分散液（Ｃ液）を、それぞれ別々にサンドグラインダーで平均粒子径０．５ミクロンになるまで湿式磨砕を行った。
　顕色剤分散液（Ａ液）
　　ジフェニルスルホン架橋型化合物（日本曹達社製、Ｄ－９０）６．０部
　　ポリビニルアルコール　１０％水溶液　　　　　　　　　　１８．８部
　　水　　　　　　　　　　　　　　　　　　　　　　　　　　１１．２部
　ロイコ染料分散液（Ｂ液）
　　３－ジブチルアミノ－６－メチル－７－アニリノフルオラン
　（山本化成社製、ＯＤＢ２）　　　　　　　　　　　　　　　　３．０部
　　ポリビニルアルコール　１０％水溶液　　　　　　　　　　　６．９部
　　水　　　　　　　　　　　　　　　　　　　　　　　　　　　３．９部
　増感剤分散液（Ｃ液）
　　シュウ酸ビス（ｐ-メチルベンジル）（大日本インキ社製、ＨＳ３５２０）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部
　　ポリビニルアルコール　１０％水溶液　　　　　　　　　　　４．７部
　　水　　　　　　　　　　　　　　　　　　　　　　　　　　　２．８部 The following examples illustrate the invention but are not intended to limit the invention. In the description, parts and% represent parts by weight and% by weight, respectively.
First, 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.
Developer dispersion (liquid A)
Diphenylsulfone crosslinkable compound (Nihon Soda Co., Ltd., D-90) 6.0 parts Polyvinyl alcohol 10% aqueous solution 18.8 parts Water 11.2 parts Leuco dye dispersion (liquid B)
3-Dibutylamino-6-methyl-7-anilinofluorane (Yamamoto Kasei Co., Ltd., ODB2) 3.0 parts Polyvinyl alcohol 10% aqueous solution 6.9 parts Water 3.9 parts Sensitizer dispersion (liquid C)
Bis (p-methylbenzyl) oxalate (Dainippon Ink, HS3520)
1.5 parts polyvinyl alcohol 10% aqueous solution 4.7 parts water 2.8 parts
　次いで、下記の割合で分散液を混合して感熱記録層用塗液を調製した。
＜感熱記録層用塗液１（以下「ＳＢＲ処方」という。）＞
　顕色剤分散液（Ａ液）　　　　　　　　　　　　　　　　　　３６．０部
　ロイコ染料分散液（Ｂ液）　　　　　　　　　　　　　　　　１３．８部
　増感剤分散液（Ｃ液）　　　　　　　　　　　　　　　　　　　９．０部
　スチレン・ブタジエン共重合体ラテックス(固形分４８％)　　１６．０部
　ナトリウムジオクチルスルホサクシネート(花王社製、ペレックスＯＴ－Ｐ、固形分７０％）　　　　　　　　　　　　　　　　　　　　　０．１５部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　１５．０部
＜感熱記録層用塗液２（以下「ＰＶＡ処方」という。）＞
　顕色剤分散液（Ａ液）　　　　　　　　　　　　　　　　　　３６．０部
　ロイコ染料分散液（Ｂ液）　　　　　　　　　　　　　　　　１３．８部
　増感剤分散液（Ｃ液）　　　　　　　　　　　　　　　　　　　９．０部
　完全ケン化型ポリビニルアルコール（クラレ社製、ＰＶＡ１１７）１２％水溶液　　　　　　　　　　　　　　　　　　　　　　　　　　２５．０部 Subsequently, the dispersion liquid was mixed at the following ratio to prepare a thermal recording layer coating solution.
<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., Ltd.) ) 12% aqueous solution 25.0 parts
　次いで、下記割合からなる配合物を混合して保護層用塗液とした。
＜保護層用塗液１＞
　非コアシェル型アクリル樹脂エマルション（三井化学社製、ＡＳＮ１００４Ｋ、Ｔｇ５５℃、固形分１８％）　　　　　　　　　　　　　２４．０部
　自己乳化型ポリオレフィン樹脂エマルション(住友精化社製、ザイクセン－Ａ－ＧＨ、固形分２４．４％)　　　　　　　　　　　　　　　　　３．０部
　ステアリン酸亜鉛（中京油脂社製、ハイドリンＬ５３６、固形分４０％）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４．０部
　ナトリウムジオクチルスルホサクシネート(花王社製、ペレックスＯＴ－Ｐ、固形分７０％）　　　　　　　　　　　　　　　　　　　　　０．０７部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　３０．０部
＜保護層用塗液２＞
　非コアシェル型アクリル樹脂エマルション（三井化学社製、ＡＳＮ１００４Ｋ、Ｔｇ５５℃、固形分１８％）　　　　　　　　　　　　　２４．０部
　自己乳化型ポリオレフィン樹脂エマルション　(住友精化社製、ザイクセン－ＡＣ、固形分３０．０％)　　　　　　　　　　　　　　　　　　２．５部
　ステアリン酸亜鉛（中京油脂社製、ハイドリンＬ５３６、固形分４０％）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４．０部
　ナトリウムジオクチルスルホサクシネート(花王社製、ペレックスＯＴ－Ｐ、固形分７０％）　　　　　　　　　　　　　　　　　　　　　０．０７部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　３０．０部
＜保護層用塗液３＞
　完全ケン化型ポリビニルアルコール（クラレ社製、ＰＶＡ１１７）１２％水溶液　　　　　　　　　　　　　　　　　　　　　　　　　　４２．０部
　グリオキザール（４０％水溶液）　　　　　　　　　　　　　　５．０部
　ステアリン酸亜鉛（中京油脂社製、ハイドリンＬ５３６、固形分４０％）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　２７．０部 Subsequently, the composition which consists of the following ratio was mixed and it was set as the coating liquid for protective layers.
<Protective layer coating solution 1>
Non-core shell type acrylic resin emulsion (Mitsui Chemicals, ASN1004K, Tg 55 ° C., solid content 18%) 24.0 parts Self-emulsifying polyolefin resin emulsion (Sumitomo Seika Co., Ltd., Seixen-A-GH, solid content 24.4) %) 3.0 parts Zinc 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%) 0.07 parts water 30.0 parts <Coating liquid 2 for protective layer>
Non-core shell type acrylic resin emulsion (Mitsui Chemicals, ASN1004K, Tg 55 ° C., solid content 18%) 24.0 parts Self-emulsifying polyolefin resin emulsion (Sumitomo Seika Co., Ltd., Syxen-AC, solid content 30.0%) 2.5 parts zinc stearate (manufactured by Chukyo Yushi Co., Ltd., Hydrin L536, solid content 40%)
4.0 parts sodium dioctyl sulfosuccinate (Kao Co., Perex OT-P, solid content 70%) 0.07 parts water 30.0 parts <Coating liquid 3 for protective layer>
Completely saponified polyvinyl alcohol (Kuraray Co., Ltd., PVA117) 12% aqueous solution 42.0 parts Glyoxal (40% aqueous solution) 5.0 parts Zinc stearate (manufactured by Chukyo Yushi Co., Ltd., Hydrin L536, solid content 40%)
4.0 parts water 27.0 parts
［実施例１］
　ポリエチレンテレフタレートフィルム（帝人社製、テイジンテトロン３３０、厚さ３８μｍ、全光線透過率８２％。以下「ＰＥＴフィルム」という。）上に、感熱記録層用塗液１（ＳＢＲ処方）を乾燥後の塗布量が５．０ｇ／ｍ２となるように塗布、乾燥したのち、さらに保護層用塗液１を乾燥後の塗布量が３．０ｇ／ｍ２となるように塗布、乾燥して感熱記録体を作製した。
［実施例２]
　実施例１のＰＥＴフィルムをトリアセチルセルロースフィルム(富士フイルム社製、フジタック、厚さ４０μｍ、全光線透過率９０％。以下「ＴＡＣフィルム」という。）に代えた以外は実施例1と同様にして感熱記録体を作製した。
［実施例３]
　感熱記録層用塗液１（ＳＢＲ処方）中のスチレン・ブタジエン共重合体ラテックス(固形分４８％)１６．０部を、スチレン・ブタジエン共重合体ラテックス(固形分４８％)６．０部と自己乳化型ポリオレフィン樹脂エマルション(住友精化社製、ザイクセン－Ａ－ＧＨ、固形分２４．４％)１５．０部とした以外は、実施例１と同様にして感熱記録体を作製した。
［実施例４]
　保護層用塗液１に代えて保護層用塗液２を用いた以外は、実施例１と同様にして感熱記録体を作製した。 [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 μm, 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.
[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 μm, total light transmittance 90%, hereinafter referred to as “TAC film”). A heat-sensitive recording material was produced.
[Example 3]
16.0 parts of the styrene / butadiene copolymer latex (solid content 48%) in the thermal recording layer coating liquid 1 (SBR formulation) was replaced with 6.0 parts of styrene / butadiene copolymer latex (solid content 48%). 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.
[Example 4]
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.
［実施例５]
　保護層用塗液１中の非コアシェル型アクリル樹脂エマルションを、非コアシェル型アクリル樹脂エマルション（三井化学社製、ＸＮＰ３、Ｔｇ３５℃、固形分１８％）に代えた以外は、実施例１と同様にして感熱記録体を作製した。
［実施例６]
　保護層用塗液１中の非コアシェル型アクリル樹脂エマルション２４．０部を、コアシェル型アクリル系樹脂（日本ペイント社製、Ｎ－５３８、Ｔｇ１００℃、固形分２０％）２２．０部に代えた以外は、実施例１と同様に感熱記録体を作製した。
［実施例７]
　保護層用塗液１中の非コアシェル型アクリル樹脂エマルションと自己乳化型ポリオレフィン樹脂エマルションの配合部数を、それぞれ１２．０部に代えた以外は実施例１と同様にして感熱記録体を作製した。
［実施例８]
　保護層用塗液１中の非コアシェル型アクリル樹脂エマルションの配合部数を２７．５部、自己乳化型ポリオレフィン樹脂エマルションの配合部数を０．３部に代えた以外は実施例１と同様にして感熱記録体を作製した。 [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.
[Example 7]
A 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.
［実施例９]
　顕色剤分散液（Ａ液）中のジフェニルスルホン架橋型化合物（日本曹達社製、Ｄ－９０）に代えて、４，４’－ジヒドロキシジフェニルスルホン（日華化学社製、ＢＰＳ－Ｐ（Ｔ）、以下「４４ＢＰＳ」ともいう。）を用いて実施例１と同様にして感熱記録体を作製した。
［実施例１０]
　顕色剤分散液（Ａ液）中のジフェニルスルホン架橋型化合物（日本曹達社製、Ｄ－９０）に代えて、２，４’－ジヒドロキシジフェニルスルホン（日華化学社製、ＢＰＳ－２４Ｃ、以下「２４ＢＰＳ」ともいう。）を用いて実施例１と同様にして感熱記録体を作製した。
［実施例１１]
　顕色剤分散液（Ａ液）中のジフェニルスルホン架橋型化合物（日本曹達社製、Ｄ－９０）に代えて、４－ヒドロキシ－４’－アリルオキシジフェニルスルホン（日華化学社製、ＢＰＳ－ＭＡＥ）を用いて実施例１と同様にして感熱記録体を作製した。
［実施例１２]
　顕色剤分散液（Ａ液）中のジフェニルスルホン架橋型化合物（日本曹達社製、Ｄ－９０）に代えて、４－ヒドロキシ－４’－ｎ－プロポキシジフェニルスルホン（エーピーアイコーポレーション社製、トミラックＫＮ）を用いて実施例１と同様にして感熱記録体を作製した。
［実施例１３]
　顕色剤分散液（Ａ液）中のジフェニルスルホン架橋型化合物（日本曹達社製、Ｄ－９０）に代えて、４－ヒドロキシ－４’－イソプロポキシジフェニルスルホン（日本曹達社製、Ｄ－８）を用いて実施例１と同様にして感熱記録体を作製した。 [Example 9]
Instead of the diphenylsulfone cross-linking compound (Nippon Soda Co., Ltd., D-90) in the developer dispersion (liquid A), 4,4′-dihydroxydiphenyl sulfone (manufactured by Nikka Chemical Co., Ltd., BPS-P (T ), Hereinafter also referred to as “44 BPS”), a 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.
［実施例１４]
　顕色剤分散液（Ａ液）中のジフェニルスルホン架橋型化合物（日本曹達社製、Ｄ－９０）に代えて、下式（化８）で表される化合物（エーピーアイコーポレーション社製、ＳＵ７２７）を用いて実施例１と同様にして感熱記録体を作製した。
Figure JPOXMLDOC01-appb-C000012
 [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.
Figure JPOXMLDOC01-appb-C000012
［比較例１］
　紙支持体（坪量６０ｇ／ｍ２の基紙）上に、感熱記録層用塗液２（ＰＶＡ処方）を乾燥後の塗布量が５．０ｇ／ｍ２となるように塗布、乾燥したのち、さらに保護層用塗液３を乾燥後の塗布量が３．０ｇ／ｍ２となるように塗布、乾燥して感熱記録体を作製した。
［比較例２]
　保護層用塗液１に代えて保護層用塗液３を用いた以外は、実施例１と同様にして感熱記録体を作製した。作製した感熱記録体の保護層表面の写真を図1に示す。
［比較例３]
　保護層を設けなかった以外は、実施例１と同様にして感熱記録体を作製した。
［比較例４]
　保護層用塗液１の自己乳化型ポリオレフィン樹脂エマルションを配合せず、非コアシェル型アクリル樹脂エマルションの配合部数を２７.５部とした以外は、実施例１と同様にして感熱記録体を作製した。
［比較例５]
　保護層用塗液１の非コアシェル型アクリル樹脂エマルションを配合せず、自己乳化型ポリオレフィン樹脂エマルションの配合部数を２０.５部とした以外は、実施例１と同様にして感熱記録体を作製した。 [Comparative Example 1]
After coating and drying the thermal recording layer coating liquid 2 (PVA formulation) on a paper support (basic weight 60 g / m 2 base paper) so that the coating amount after drying is 5.0 g / m 2. Further, the protective layer coating liquid 3 was applied and dried so that the coating amount after drying was 3.0 g / m 2 to prepare a heat-sensitive recording material.
[Comparative Example 2]
A 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.
[Comparative Example 4]
A 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. .
[Comparative Example 5]
A 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. .
　作製した感熱記録体について、下記評価を行った。
＜印字濃度＞
　作製した感熱記録体について、大倉電機社製のＴＨ－ＰＭＤ（感熱記録紙印字試験機、京セラ社製サーマルヘッドを装着）を用い、印加エネルギー０．４２ｍＪ／ｄｏｔ、印字速度５０ｍｍ／ｓｅｃでベタ印字した。記録部の印字濃度を、マクベス濃度計（ＲＤ－９１４、アンバーフィルター使用）で測定した。
＜塗工欠陥＞
　作製した感熱記録体について、塗工面の塗工欠陥（さざ波状）を目視にて下記の基準で評価した。
　優：さざ波状の塗工欠陥が見られない。
　良：さざ波状の塗工欠陥がほとんどない。
　可：さざ波状の塗工欠陥が僅かに見られる。
　不可：さざ波状の塗工欠陥が多く見られる。 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).
<Coating defects>
About the produced thermal recording body, the coating defect (ripple shape) of the coating surface was visually evaluated on the following reference | standard.
Excellent: Rippled coating defects are not seen.
Good: Almost no ripple coating defects.
Good: Rippled coating defects are slightly seen.
Impossible: Many rippled coating defects are observed.
＜耐水性＞
　作製した感熱記録体について、２３℃、５０％Ｒｈの環境下で２４時間水浸漬処理した後、目視にて塗工層の状態を観察した。
　優：割れや剥離が見られない。
　良：割れや剥離がほとんどない。
　可：割れや剥離が僅かに見られる。
　不可：割れや剥離が多く見られる。
＜印字走行性＞
　作製した感熱記録体について、印字試験機（キヤノン社製、ＨＴ１８０）を用い、０℃の環境下で印加エネルギー０．２０ｍＪ／ｄｏｔでベタ印字した。この時の印字状態について、下記の基準で評価した。記録体の最表層が印字試験機のヘッドに粘着（スティッキング）して、部分的に印字できないことを「白飛び」と言い、最表層が印字試験機のヘッドに粘着（スティッキング）することにより引き起こされる印字試験機のノイズを「騒音」という。
　優：ベタ印字部に白飛びが発生せず、騒音もほとんどない。
　良：ベタ印字部に白飛びが発生しないが、騒音が少し発生する。
　可：ベタ印字部に白飛びが若干発生し、騒音は少し発生する。
　不可：ベタ印字部に白飛びが頻発し、騒音も大きい。 <Water resistance>
The produced thermal recording material was immersed in water for 24 hours in an environment of 23 ° C. and 50% Rh, and then the state of the coating layer was visually observed.
Excellent: No cracking or peeling.
Good: Almost no cracking or peeling.
Good: Slight cracking or peeling.
Impossible: Many cracks and peeling are observed.
<Printability>
The produced 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. This is called “out-of-white” and is caused by the outermost layer sticking (sticking) to the head of the printing tester. The noise of the printing tester is called “noise”.
Excellent: No whiteout occurs in the solid print area and there is almost no noise.
Good: No whiteout occurs in the solid print area, but a little noise is generated.
Possible: Some whitening occurs in the solid printing part, and a little noise is generated.
Impossible: White spots frequently occur in the solid print area, and noise is high.
＜耐可塑剤性＞
　作製した感熱記録体について、大倉電機社製のＴＨ－ＰＭＤ（感熱記録紙印字試験機、京セラ社製サーマルヘッドを装着）を用い、印加エネルギー０．４２ｍＪ／ｄｏｔ、印字速度５０ｍｍ／ｓｅｃでベタ印字した。紙管に塩化ビニルラップ（三井東圧社製、ハイラップＫＭＡ）を１重に巻き付け、その上に印字部が外面となるように前記感熱記録体を置き、更にその上に前記塩化ビニルラップを３重に巻き付けて固定した。４０℃、５０％ＲＨの環境下で５時間処理した後、印字部の記録濃度をマクベス濃度計（ＲＤ－９１４、アンバーフィルター使用）で測定し、処理前後の値から残存率を算出した。
　残存率（％）＝（処理後の記録濃度／処理前の記録濃度）×１００
＜再印字性＞
　作製した感熱記録体について、５０℃、９０％ＲＨの環境下に１日間静置した後、２３℃、５０％ＲＨ環境下に３時間静置し、大倉電機社製のＴＨ－ＰＭＤ（感熱記録紙印字試験機、京セラ社製サーマルヘッドを装着）を用い、印加エネルギー０．４２ｍＪ／ｄｏｔ、印字速度５０ｍｍ／ｓｅｃでベタ印字した。記録部の印字濃度を、マクベス濃度計（ＲＤ－９１４、アンバーフィルター使用）で測定した。 <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. and 50% RH, the recording density of the printed portion was measured with a Macbeth densitometer (RD-914, using an amber filter), and the residual ratio was calculated from the values before and after the processing.
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. Using a paper printing tester and a Kyocera thermal head), solid printing was performed at an applied energy of 0.42 mJ / dot and a printing speed of 50 mm / sec. The print density of the recording part was measured with a Macbeth densitometer (RD-914, using an amber filter).
　評価結果を表１に示す。
Figure JPOXMLDOC01-appb-T000013
 The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000013

Claims (9)

  1. プラスチックフィルム上に、無色ないし淡色の電子供与性ロイコ染料及び電子受容性顕色剤を含有する感熱記録層並びに該感熱記録層上に最外層として保護層を有する感熱記録体において、該保護層がアクリル系樹脂及びポリオレフィン系樹脂を含有する感熱記録体。 A heat-sensitive recording layer comprising 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 comprising: A heat-sensitive recording material containing an acrylic resin and a polyolefin resin.
  2. 前記ポリオレフィン系樹脂が、オレフィン・不飽和カルボン酸共重合体である請求項１に記載の感熱記録体。 The heat-sensitive recording material according to claim 1, wherein the polyolefin resin is an olefin / unsaturated carboxylic acid copolymer.
  3. 前記アクリル系樹脂が、ガラス転移点が５０℃より高く９５℃以下であるアクリル系樹脂である請求項１又は２に記載の感熱記録体。 The heat-sensitive recording material according to claim 1, wherein the acrylic resin is an acrylic resin having a glass transition point higher than 50 ° C. and 95 ° C. or lower.
  4. 前記アクリル系樹脂が、非コアシェル型アクリル系樹脂である請求項１～３のいずれか一項に記載の感熱記録体。 The heat-sensitive recording material according to any one of claims 1 to 3, wherein the acrylic resin is a non-core-shell acrylic resin.
  5. 前記保護層中の、ポリオレフィン系樹脂の配合量（固形分）が、３～６０重量％である請求項１～４のいずれか一項に記載の感熱記録体。 The heat-sensitive recording material according to any one of claims 1 to 4, wherein a blending amount (solid content) of the polyolefin resin in the protective layer is 3 to 60% by weight.
  6. 前記保護層中の、アクリル系樹脂の配合量（固形分）が、１５～９７重量％である請求項１～５のいずれか一項に記載の感熱記録体。 The heat-sensitive recording material according to any one of claims 1 to 5, wherein a blending amount (solid content) of the acrylic resin in the protective layer is 15 to 97% by weight.
  7. 前記ポリオレフィン系樹脂／アクリル系樹脂の配合重量比（固形分）が、３／９７～５０／５０である請求項１～６のいずれか一項に記載の感熱記録体。 The heat-sensitive recording material according to any one of claims 1 to 6, wherein a blending weight ratio (solid content) of the polyolefin resin / acrylic resin is 3/97 to 50/50.
  8. 前記感熱記録層が、ウレタン系樹脂又はスチレン－ブタジエン系樹脂のエマルション若しくはラテックスを含有する請求項１～７のいずれか一項に記載の感熱記録体。 The thermosensitive recording material according to any one of claims 1 to 7, wherein the thermosensitive recording layer contains an emulsion or latex of a urethane resin or a styrene-butadiene resin.
  9. 前記顕色剤が、下記一般式（化１）
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１は、それぞれ同じであっても異なってもよく、ハロゲン原子、炭素数が１～６のアルキル基又はアルケニル基を表し、ｍは、それぞれ同じであっても異なってもよく、０～４の整数を表し、ｎは１～１１の整数を表し、Ｒ２は、それぞれ同じであっても異なってもよく、エーテル結合を有してもよい炭素数１～１２の飽和若しくは不飽和の直鎖若しくは分枝の炭化水素基、下記一般式
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ３はメチレン基又はエチレン基を表す。）で表される置換フェニレン基、又は下記一般式
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ４は水素原子又は炭素数が１～４のアルキル基を表す。）で表される２価基を表す。）で表されるジフェニルスルホン架橋型化合物、下記一般式（化４）
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒ５及びＲ６はそれぞれ独立して炭素数が１～８のアルキル基若しくはアルケニル基又はハロゲン原子を表し、Ｒ７は水素原子又は炭素数１～４の直鎖若しくは分岐の飽和若しくは不飽和炭化水素を表し、ｐ及びｑはそれぞれ独立して０～３の整数を表す。）で表されるジフェニルスルホン化合物から成る群から選択される少なくとも１種である請求項１～８のいずれか一項に記載の感熱記録体。     The developer is represented by the following general formula (Formula 1)
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 s may be the same or different and each represents a halogen atom, an alkyl group or an alkenyl group having 1 to 6 carbon atoms, and m may be the same or different) , Represents an integer of 0 to 4, n represents an integer of 1 to 11, and R 2 s may be the same or different and each may have an ether bond, Unsaturated linear or branched hydrocarbon group, the following general formula
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 3 represents a methylene group or an ethylene group), or a substituted phenylene group represented by the following general formula:
    Figure JPOXMLDOC01-appb-C000003
     (Wherein R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Diphenylsulfone crosslinkable compound represented by the following general formula (Formula 4)
    Figure JPOXMLDOC01-appb-C000004
     (Wherein R 5 and R 6 each independently represents an alkyl or alkenyl group having 1 to 8 carbon atoms or a halogen atom, and R 7 represents a hydrogen atom or a linear or branched saturated group having 1 to 4 carbon atoms) Or an unsaturated hydrocarbon, and p and q each independently represent an integer of 0 to 3.) and at least one selected from the group consisting of diphenylsulfone compounds The heat-sensitive recording material according to any one of the above.
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US9579916B2 (en) 2013-09-30 2017-02-28 Nippon Paper Industries Co., Ltd. Thermosensitive recording medium

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JP2002331750A (en) * 2001-05-11 2002-11-19 Mitsubishi Paper Mills Ltd Heat-sensitive recording medium
JP2010247533A (en) * 2009-03-24 2010-11-04 Nippon Paper Industries Co Ltd Heat-sensitive recording material
JP2011020352A (en) * 2009-07-16 2011-02-03 Nippon Paper Industries Co Ltd Heat-sensitive recording medium
JP2011156855A (en) * 2010-01-07 2011-08-18 Nippon Paper Industries Co Ltd Heat-sensitive recording medium
JP2013095105A (en) * 2011-11-04 2013-05-20 Nippon Paper Industries Co Ltd Heat-sensitive recording medium

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JP2002331750A (en) * 2001-05-11 2002-11-19 Mitsubishi Paper Mills Ltd Heat-sensitive recording medium
JP2010247533A (en) * 2009-03-24 2010-11-04 Nippon Paper Industries Co Ltd Heat-sensitive recording material
JP2011020352A (en) * 2009-07-16 2011-02-03 Nippon Paper Industries Co Ltd Heat-sensitive recording medium
JP2011156855A (en) * 2010-01-07 2011-08-18 Nippon Paper Industries Co Ltd Heat-sensitive recording medium
JP2013095105A (en) * 2011-11-04 2013-05-20 Nippon Paper Industries Co Ltd Heat-sensitive recording medium

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* 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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