FI127015B - HEALTH SENSITIVE REGISTRAR - Google Patents

HEALTH SENSITIVE REGISTRAR Download PDF

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Publication number
FI127015B
FI127015B FI20145896A FI20145896A FI127015B FI 127015 B FI127015 B FI 127015B FI 20145896 A FI20145896 A FI 20145896A FI 20145896 A FI20145896 A FI 20145896A FI 127015 B FI127015 B FI 127015B
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FI
Finland
Prior art keywords
thermosensitive recording
recording medium
acrylic resin
parts
meth
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Application number
FI20145896A
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Finnish (fi)
Swedish (sv)
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FI20145896A (en
Inventor
Yasuaki Matsumori
Kenji Hirai
Akihito Ogino
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Jujo Paper Co Ltd
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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 Jujo Paper Co Ltd filed Critical Jujo Paper Co Ltd
Publication of FI20145896A publication Critical patent/FI20145896A/en
Application granted granted Critical
Publication of FI127015B publication 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Description

THERMOSENSITIVE RECORDING MEDIUM
FIELD OF THE INVENTION
The present invention relates to a thermosensitive recording medium comprising a thermosensitive recording layer and a protective layer, which are installed on a support made of plastic film, and more particularly to a thermosensitive recording medium with a support made of plastic film showing reduced coating defects.
BACKGROUND OF THE INVENTION A thermosensitive recording medium is obtained by grinding a colorless or pale colored basic leuco dye (henceforth referred to as "leuco dye") and an electron accepting color developing agent (henceforth referred to as "color developing agent") each into fine particles, preparing dispersions, blending the dispersions, preparing a coating solution by adding a binder, a filler, a sensitivity improving agent, a lubricant and other aids and applying the coating solution on a support material such as paper, synthetic paper, film, plastic and the like. The color is developed instantaneously through a chemical reaction when heated using a thermal head, hot stamp, thermal pen, laser beam and the like to yield a recorded image. The thermosensitive recording medium is being used extensively in facsimiles, terminal printers of computers, automatic ticket vending machines, measurement recorders and the like.
The thermosensitive recording medium using a support made of a plastic film has become used widely, since its dimensional stability and strength are good (Reference 1 etc.). However, when using a plastic film as a support, a problem occurs in which the coating layer is peeled off by moisture. A protective layer comprising a polyolefin resin and a gloss layer are installed on a thermosensitive recording layer in the order to solve this problem (Reference 2).
Further, in a thermosensitive recording medium which is used in outdoor condition requiring durability and water resistance, a protective layer containing an acrylic resin emulsion is installed on a thermosensitive recording layer (References 3-6 etc.).
Reference 1: Japanese Patent Application Public Disclosure 2007-130991 Reference 2: Japanese Patent Application Public Disclosure 2001-150813
Reference 3: International Publication WO2010/110209
Reference 4: International Publication W02007/049621
Reference 5: Japanese Patent Application Public Disclosure H06-262853
Reference 6: Japanese Patent Application Public Disclosure 2004-74531
PROBLEMS TO BE SOLVED BY THE INVENTION
When using a plastic film as a support of a thermosensitive recording medium, a protective layer is generally installed on a thermosensitive recording layer to increase water resistance and surface strength.
However, when using a plastic film as a support, coating defects with ripplelike coating often occur (see Comparative Example 2 and Figure 1 described later) because a plastic film absorbs less water or other solvents compared with a paper, then water or other solvents contained in the coating solution tend to remain in the thermosensitive recording layer. Since this coating defect is due to the unevenness of the transmission of light, the coating defect becomes more significant when using a transparent plastic film. Further, the coating defect becomes more significant when using a coating solution which enhances adhesion or stickiness to a plastic film.
Although this problem can be solved by incorporating an olefin resin in a protective layer (Comparative Example 5 described later), printing run-ability (sticking) becomes worse, since the surface strength and the heat resistance become inferior when using an olefin resin. It is proposed to install another coating layer further on a protective layer in the order to solve this problem (Reference 2).
Therefore, the objective of the present invention is to provide a thermosensitive recording medium with installing a thermosensitive recording layer and a protective layer as the outermost layer in the order on a support, showing a reduced coating defects and a superior printing run-ability (less sticking).
MEANS TO SOLVE THE PROBLEMS
As a result of an intensive study by the present inventors, the inventors found that a thermosensitive recording medium prevents the coating defects while showing a normal performance of water resistance and other properties, when using a plastic film as an support, installing a thermosensitive recording layer and a protective layer in the order on a support, and having this protective layer contain an acrylic resin and a polyolefin resin.
That is, the present invention is a thermosensitive recording medium having a thermosensitive recording layer, comprising a colorless or pale colored basic leuco dye and an electron accepting developing agent, on a plastic film and a protective layer as the outermost layer on the thermosensitive recording layer, wherein the protective layer comprises an acrylic resin and a polyolefin resin.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a photograph of the surface of the protective layer of the thermosensitive recording medium (10.5 χ 14cm) prepared in Comparative Example 2. The support is a PET film and the surface of the protective layer shows a coating defect like a ripple.
DETAILED DESCRIPTION OF THE INVENTION
The thermosensitive recording medium of the present invention has a thermosensitive recording layer on a plastic film (support) and a protective layer as the outermost layer on the thermosensitive recording layer. And the protective layer comprises an acrylic resin and a polyolefin resin.
The plastic film used in the present invention may include, for example, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, polyethylene naphthalate (PEN) film, and the like. As the plastic film, specifically, nor-bornene films (trade name: ARTON Film) manufactured by JSR Corporation, cycloolefin film (trade name: ZEONOR Film) manufactured by Nippon Zeon Co., Ltd., and a composite film prepared by combining these films. In particular, when used for applications requiring optical transparency, the total light transmittance of the plastic film as a support is preferably more than 30 percent, more preferably more than 70%.
The polyolefin resin used in the present invention is a polymer of olefin(s), such as ethylene, propylene, etc., and the polyolefin resin may be a monopolymer or a copolymer with another vinyl compound.
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 preferred and ethylene is particularly preferred. As the unsaturated carboxylic acid, (meth) acrylic acid (i.e. acrylic acid or methacrylic acid), maleic acid, itaconic acid, fumaric acid, etc. are preferred and (meth) acrylic acid is more preferred.
As the olefin-unsaturated carboxylic acid copolymer, a copolymer of ethylene and (meth) acrylic acid and a copolymer of propylene and (meth) acrylic acid are preferred.
The weight average molecular weight of the polyolefin resin is preferably from 5,000 to 100,000, more preferably from 10,000 to 50,000. In the cases where the weight average molecular weight is less than 5,000, a blocking problem may possibly occur. In the cases where the weight average molecular weight is higher than 100,000, a problem may possibly occur in the productivity.
As the olefin-unsaturated carboxylic acid copolymer, for example, High-Tech S-3121, High Tech S-3123, High Tech S-3127 (TOHO Chemical Industry Co.,Ltd.), Zaikthene-A-GH, Zaikthene-AC, Zaikthene -N, Zaikthene-L (Sumitomo Seika Chemicals Co., Ltd.) are cited.
The acrylic resin used in the present invention comprises (meth)acrylic acid and a monomer (except olefin) that can be copolymerized with the (meth)acrylic acid. The amount of (meth)acrylic acid in the acrylic resin is preferably from 1 to 10 parts by weight per 100 parts by weight of acrylic resin. The (meth)acrylic acid is soluble in alkali and has a characteristic activity of converting an acrylic resin to a water soluble resin by adding a neutralizer. By converting an acrylic resin to a water soluble resin, the affinity to pigments becomes improved, when a protective layer contains pigments, which makes the protective layer have a superior strength even in the presence of large amount of pigments. The monomer element that can be copolymerized with (meth)acrylic acid includes, for example, acrylic acid alkyl resin, such as me-thyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, iso-butyl(meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethyl hexyl (meth)acrylate, octyl (meth)acrylate and the like, modified acrylic acid alkyl resin, such as acrylic acid alkyl resin as above that is modified with epoxy resin, silicone resin, styrene or derivatives thereof, (meth)acrylonitrile, acrylic ester and hydroxy-alkyl acrylic ester. Among these, (meth)acrylonitrile and/or methyl (meth)acrylate are preferred. The amount of (meth)acrylonitrile in the acrylic resin is preferably from 15 to 70 parts by weight per 100 parts by weight of acrylic resin and the amount of methyl (meth)acrylate in the acrylic resin is preferably from 20 to 80 parts by weight per 100 parts by weight of acrylic res in. When (meth)acrylonitrile and methyl (meth)acrylate are contained, the amount of (meth)acrylonitrile in the acrylic resin is preferably from 15 to 18 parts by weight per 100 parts by weight of acrylic resin and the amount of methyl (meth)acrylate in the acrylic resin is preferably from 20 to 80 parts by weight per 100 parts by weight of acrylic resin.
The glass transition temperature (Tg) of the acrylic resin of the present invention is higher than 50 degree C and lower than or equal to 95 degree C. When the Tg is lower than or equal to 50 degree C, sufficient heat resistance cannot be attained and sticking problem occurs, although water resistance is improved. On the contrary, when an acrylic resin with higher Tg is contained, sticking resistance and scratching resistance are tend to be improved. However, when the Tg of the acrylic resin is too high, the protective layer becomes brittle and the water resistance, plasticizer resistance and solvent resistance become insufficient, then the objective effect of the present invention may not be attained. 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. In general, a core-shell type acrylic resin is widely used since a core-shell type acrylic resin is superior to a non-core-shell type acrylic resin in thermal resistance and sticking resistance when used in coating layer. However, a core-shell type acrylic resin also have a disadvantage, that is, color developing sensitivity is inferior because the thermal-conductivity of the shell portion of a core-shell type acrylic resin is low. On the other hand, a non-coreshell type acrylic resin is normally less heat resistant and has a disadvantage that sticking problems and head debris problems often occur. However, a noncore-shell type acrylic resin with Tg of higher than 50 degree C and lower than or equal to 95 degree C is superior in heat resistance, and therefore has an advantage that sticking resistance and prevention of head debris are superior.
Preferably, the protective layer of the present invention does not contain pigment. As the pigment, inorganic or organic fillers and the like such as kaolin, calcined kaolin, aluminum hydroxide, silica, calcium carbonate, diatomaceous earth, talc, titanium oxide, and the like may be cited.
Other than the components described above, the protective layer of the present invention may contain a slipping agent, such as fatty acid metal salts including zinc stearate, calcium stearate and the like, waxes, silicone resins and the like, UV absorption agents, such as benzophenone type and triazole type UV absorption agents, crosslinking agents, dispersion agents, defoaming agents, oxidation inhibitors, fluorescent dye and the like in the range that do not interfere with the desired effects for the objectives of the present invention.
The amount of polyolefin resin in the protective layer of the present invention is, in terms of solid content, preferably from 3 to 60 weight %, more preferably from 5 to 30 weight %.
The amount of acrylic resin in the protective layer of the present invention is, in terms of solid content, preferably from 15 to 97 weight %, more preferably from 50 to 95 weight %.
The weight ratio (solid content) of polyolefin resin / acrylic resin is preferably from 3/97 to 50/50, more preferably from 5/95 to 40/60.
The total amount of polyolefin resin and acrylic resin in the protective layer is, in terms of solid content, preferably from 20 to 100 weight %, more preferably from 40 to 90 weight %.
The thermosensitive recording layer of the present invention contains essentially a leuco dye and a color developing agent and may contain sensitizers, binders, crosslinking agents, slipping agents, pigments described above and the other components.
All of the leuco dyes well known in the conventional field of pressure sensitive and thermosensitive recording media may be used as the leuco dye in a thermosensitive recording medium of the present invention. Although the leuco dye is not particularly restricted, triphenylmethane type compounds, fluorane type compounds, fluorene type compounds, divinyl type compounds and the like are preferred as the leuco dye. Specific examples of the typical colorless to pale colored basic colorless leuco dye (precursor of dye) are shown below. In addition, these precursor of dye may be used individually or also in mixtures of at least two of them.
Triphenylmethane type leuco dyes 3,3-bis(p-dimethyl aminophenyl)-6-dimethylaminophthalide [alternate name: crystal violet lactone] and 3,3-bis(p-dimethyl aminophenyl) phthalide [alternate name: malachite green lactone]
Fluorane type leuco dyes 3-Diethylamino-6-methylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-(o,p-dimethylanilino)fluorane, 3-diethylamino-6-methyl- 7-chlorofluoran, 3-diethylamino-6-methyl-7-(m-trifluoromethylanilino) fluorane, 3- diethylamino-6-methyl-7-(o-chloroanilino) fluorane, 3-diethylamino- 6- methyl-7-(p- chloroanilino) fluorane, 3-diethylamino-6-methyl-7-(o-fluoroanilino) fluorane, 3- diethylamino-6-methyl-7-(nn-nnethylanilino) fluorane, 3-diethylamino-6-methyl-7-n- octylanilino fluorane, 3-diethylamino-6-methyl-7-n-octylamino fluorane, 3-diethylamino-6- methyl-7-benzylamino fluorane, 3-diethylamino-6-methyl-7-dibenzylamino fluorane; 3-diethylamino-6-chloro-7-methyl fluorane, 3-diethylamino-6-chloro-7-anilino fluorane, 3-diethylamino-6-chloro-7-p-methylanilino fluorane, 3-diethylamino-6-ethoxyethyl-7- anilino fluorane, 3-diethylamino-7-methyl fluorane, 3-diethylamino-7-chloro fluorane, 3-diethylamino-7-(m-trifluoromethylanilino) fluorane, 3-diethylamino-7-(o-chloroanilino) fluorane, 3-diethylamino-7-(p-chloroanilino) fluorane, 3-diethylamino-7-(o-fluoroanilino) fluorane, 3-diethylamino-benz[a] fluorine; 3-diethylamino-benz[c] fluorane, 3-dibutylamino-6-methyl-fluorane, 3-dibutylamino-6-methyl-7-anilino fluorane, 3-dibutylamino-6-methyl-7-(o,p-dimethylanilino) fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3-butylamino-6-methyl-7-(p-chloroanilino) fluorane, 3-dibutylamino-6-methyl-7-(o-fluoroanilino) fluorane, 3-dibutylamino-6-methyl-7-(m- fluoroanilino) fluorane, 3-dibutylamino-6-methyl-chloro fluorane, 3-dibutylamino- 6-ethoxyethyl-7-anilino fluorane, 3-dibutylamino-6-chloro-7-anilino fluorane, 3-dibutylamino-6-methyl- 7- p-methylanilino fluorane, 3-dibutylamino-7-(o-chloroanilino) fluorane, 3- dibutylamino-7-(o-fluoroanilino) fluorane, 3-di-n-pentylamino-6-methyl-7- anilino fluorane, 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-anilino fluorane, 3-di-n-pentylamino-7-(p-chloroanilino) fluorane, 3-pyrolidino-6-methyl-7-anilino fluorane, 3-piperidino-6-methyl-7-anilino fluorane, 3-(N-methyl-N-propylamino)-6- methyl-7-anilino fluorane, 3-(N-methyl-N-cyclohexylamino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-cyclohexylamino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-xylylamino)-6- methyl-7-(p-chloroanilino) fluorane, 3-(N-ethyl-p-toluidino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-isoamylamino)-6- chloro-7-anilino fluorane, 3-(N-ethyl-N- tetrahydrofurfurylamino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N- isobutylamino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N- ethoxypropylamino)-6-methyl-7-anilino fluorane, 3-cyclohexylamino-6-chloro fluorane, 2-(4-oxahexyl)-3-dimethylamino-6-methyl-7-anilino fluorane, 2-(4-oxahexyl)-3- di-ethylamino-6-methyl-7-anilino fluorane, 2-(4-oxahexyl)-3-dipropylamino-6- me-thyl-7-anilino fluorane, 2-methyl-6-p-(p-dimethylanninophenyl) aminoanilino fluorane, 2-methoxy-6-p-(p-dimethylanninophenyl) aminoanilino fluorane, 2-chloro-3-methyl-6- p-(p-phenylaminophenyl) aminoanilino fluorane, 2-chloro-6-p-(p-dimethylaminophenyl) aminoanilino fluorane, 2-nitro-6-p-(p-diethylaminophenyl) aminoanilino fluorane, 2-amino-6-p-(p-diethylaminophenyl) aminoanilino fluorane, 2-diethylamino-6-p-(p- diethyla-minophenyl) aminoanilino fluorane, 2-phenyl-6-methyl-6-p-(p- phenylamino-phenyl) aminoanilino fluorane, 2-benzyl-6-p-(p-phenylaminophenyl) aminoanilino fluorane, 2-hydroxy-6-p-(p-phenylaminophenyl)aminoanilino fluorane, 3-methyl-6-p-(p-dimethylaminophenyl) aminoanilino fluorane, 3-diethylamino-6-p-(p-diethylaminophenyl) aminoanilino fluorane, 3-diethylamino-6-p-(p- dibutyl-aminophenyl) aminoanilino fluorane and 2,4-dimethyl-6-[(4-dimethylamino) anilino] fluorane.
Fluorene type leuco dye 3.6.6- Tris(dimethylamino) spiro[fluorene-9,3'-phthalide] and 3,6,6'-tris (diethyl-amino) spiro[fluorene-9,3'-phthalide].
Divinyl type leuco dyes 3,3-bis-[2-(p-dimethyl aminophenyl)-2-(p-methoxyphenyl) ethenyl]-4,5,6,7- tet-rabromophthalide, 3,3-bis-[2-(p-dimethylaminophenyl)-2-(p-methoxyphenyl) ethenyl]- 4,5,6,7-tetrachlorophthalide, 3,3-bis-[1,1-bis(4-pyrolidinophenyl) eth-ylene-2-yl]-4,5,6,7- tetrabromophthalide and 3,3-bis-[1-(4-methoxyphenyl)-1-(4-pyrolydinophenyl) ethylene- 2-yl]-4,5,6,7-tetrchlorophthalide.
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-cyclohexyl ethylamino-2-methoxyphenyl)-3-(1 -ethyl-2-methylindol-3-yl)-4- azaphthalide, 3,3-bis(1 -ethyl-2-methylindol-3-yl)phthalide, 3.6- bis(diethylamino)fluorane- y-(3'-nitro)anilinolactam, 3,6- bis(diethylamino)fluorane-y-(4'-nitro) anilinolactam, 1,1-bis-[2',2',2",2"-tetrakis- (p-dimethylaminophenyl)-ethenyl]-2,2-dinitrilethane, 1,1 -bis-[2',2',2",2"-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2-p-naphthoylethane, 1,1 -bis-[2',2',2",2"-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2,2-diacetylethane and bis-[2,2,2',2'-tetrakis-(p-dimethylaminophenyl)-ethenyl]-methylmalonic acid dimethyl ester.
The color development agents used in the present invention includes, for example, inorganic acidic substances such as activated clay, attapulgite, colloidal silica, aluminum silicate and the like, 4,4'-isopropylidene diphenol, 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'-methyl diphenyl sulfone, 4-hydroxyphenyl-4'-benzyloxy diphenyl sulfone, 3,4-dihydroxyphenyl-4'-methyl phenyl sulfone, 1-[4-(4-hydroxyphenylsulphonyl) phenoxy] -4-[4-(4-isopropoxyphenylsulphonyl) phenoxy] butane, phenol condensation composition described in JP 2003-154760, amino benzene sulfonamide derivatives described in JP-H8-59603, bis (4-hydroxyphenyl thioethoxy) methane, 1,5-di (4-hydroxyphenylthio) -3-oxapentane, bis (p-hydroxyphenyl) butyl acetate, bis (p-hydroxyphenyl)methyl acetate, 1,1-bis (4-hydroxyphenyl) -1-phenyl ethane, 1,4-bis [a-methyl-a-(4'-hydroxyphenyl) ethyl] benzene, 1,3-bis [a-methyl-a-(4'-hydroxyphenyl) ethyl] benzene, di(4-hydroxy-3-methylphenyl) sulfide, 2,2'-thiobis (3-tert-octylphenol), 2,2'- thiobis (4-tert-octylphenol), compounds described in W002/081229 or JP2002-301873, thiourea compounds such as N, N'-di-m-chlorophenyl thiourea and the like, p-chlorobenzoic acid, octadecyl gallate, bis[4-(n-octyloxycarbonylamino) zinc salicylate] dihydrate, 4-[2-(p-methoxyphenoxy) ethyloxy] salicylic acid, 4-[3-(p-tolylsulfonyl) propyloxy] salicylic acid, salts of polyvalent metal salts, such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel and the like, and aromatic carboxylic acid of 5-[p-(2-p-methoxyphenoxyethoxy) cumyl] salicylic acid and aromatic carboxylic acids thereof, antipyrine complex of zinc thiocyanate, complex zinc salt of terephthal-ic aldehyde acid and other aromatic carboxylic acid, diphenyl sulfone cross-link type compound represented by the following formula (formula 1)
wherein R1, R2, m and m are defined later, dihydroxy diphenyl sulfone compound represented by the following formula (formula 4)
wherein R5, R6, R7, p and q are defined later.
In the formula (formula 1), R\ which may be identical or different, preferably identical, represents a halogen atom, or an alkyl group or an alkenyl group having 1 to 6 carbon atoms.
This alkyl group or alkenyl group is an alkyl or alkenyl group having 1-6 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, iso-hexyl, 1-methylpentyl, 2-methylpentyl, vinyl, allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 2-methyl-2-propenyl and the like.
The halogen atom includes chlorine atom, bromine atom, fluorine atom or iodine atom, preferably represents chlorine atom or bromine atom. m, which may be identical or different, preferably identical, represents an integer of from 0 to 4, preferably 0. OH group and -0R20- group preferably locate in a para-position to SO2 group, n is an integer of from 1 to 11.
This compound is preferably a mixture of those in which p are from 1 to 11. R2, which may be identical or different, is preferably identical. R2 may be a hydrocarbon group having 1 to 12, preferably 3 to 7 carbon atoms, which may have an ether bond, which may be saturated or unsaturated, preferably saturated, which may be linear or branched, preferably linear. Such hydrocarbons includes a polyalkylene oxide chain or an alkylene group, preferably is a polyalkylene oxide chain. When R2 is a polyalkylene oxide chain, -0R20- includes -0-(CaH2a0)i ~ 3- in which a is 2 to 4, preferably 2 to 3, more preferably 2. The alkylene group includes -CbH2t>-, in which b is 1 to 12, preferably 3 to 7. R2 may be a substituted phenylene group represented by a general formula below:
In the formula, R3 represents a methylene group or ethylene group. R3 preferably are in a para position each other.
In addition, R2 may be a divalent group represented by a general formula below:
In the formula, R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom.
Among these, R2 preferably is a hydrocarbon group having 1 to 12 carbon atoms, which may have an ether bond, which may be saturated or unsaturated, which may be linear or branched, as described above.
As such a diphenyl sulfone cross-link type compound represented by the above formula 1, a compound represented by the formula below (D-90 manufactured by Nippon Soda Co., Ltd.) is preferred.
In the formula (Formula 4), R5 and R6 independently represent a halogen atom, or an alkyl group or an alkenyl group having 1 to 8 carbon atoms. R7 represents a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon having 1 to 4 carbon atoms, p and q independently represent an integer of 0 to 3.
As a dihydroxy diphenyl sulfone compound represented by the general formula (formula 4), preferred are a dihydroxy diphenyl sulfone compound represented by the general formula (Formula 6)
wherein R5, R6, p and q are defined above, and a diphenyl sulfone compound represented by the general formula (Formula 7),
wherein R5 and R6 independently represent an alkenyl group having 1 to 4 carbon atoms, R7 is defined above, and p and q independently represent an integer of 0 to 2.
As the dihydroxy diphenyl sulfone compound represented by the general formula (Formula 6), 4,4'-dihydroxy diphenyl sulfone, 2,4'-dihydroxy diphenyl sulfone, 4,4'-dihydroxy-3,3'-diallyl diphenyl sulfone, 3,3'-dimethyl-4, 4'- dihydroxydiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-dihydroxy diphenyl sulfone, 2,2'-bis(4-chlorophenol) sulfone, 4-hydroxyphenyl-3'-isopropyl-4'- hydroxyphenyl sulfone, bis-(3-ethyl-4-hydroxyphenyl) sulfone, 2,2'-bis(p-t-butylphenol) sulfone, 2,2'-bis(p-t-pentylphenol)sulfone, 2,2'-bis(p-t-octylphenol) sulfone and the like are cited.
Among these, 4,4'-dihydroxy diphenyl sulfone, 2,4'-dihydroxy diphenyl sulfone, and 4,4'-dihydroxy-3,3'-diallyl diphenyl sulfone are preferred.
As the dihydroxy diphenyl sulfone compound represented by the general formula (Formula 7), 4-hydroxy-4'-n-propoxy diphenyl sulfone, 4-hydroxy-4'-isopropoxy diphenyl sulfone, 4-hydroxy-4'-allyloxydiphenyl sulfone, 4-hydroxy-4'-2-propylexy diphenyl sulfone, 4-hydroxy-4'-1-propenyl diphenyl sulfone, 4-hydroxy-4'-ethoxy diphenyl sulfone, 4-hydroxy-4'-n-butoxydiphenyl sulfone are cited.
Among these, 4-hydroxy-4'-n-propoxy diphenyl sulfone, 4-hydroxy-4'-isopropoxy diphenyl sulfone, and 4-hydroxy-4'-allyloxy diphenyl sulfone are preferred.
Above 1 -[4-(4-hydroxyphenylsulphonyl) phenoxy]-4-[4-(4- isopropoxyphen-ylsulphonyl) phenoxy] butane is available, for example, as JKY-214 of API Corporation (Japan). And the phenol condensation composition described in JP 2003-154760 is available, for example, as JKY-224 of API Corporation (Japan).
The compound described in International Publication W002/081229 is also available under the trade names of NKK-395 and D-100 produced by Nippon Soda Co., Ltd. In addition, high molecular weight aliphatic acid metal complex salts described in Japanese Patent Application Public Disclosure No. H10-258577 and metal chelate type color development components such as polyvalent hydroxy aromatic compounds and the like may also be present.
These color developing agents may be used solely or as a mixture thereof.
Among these color developing agents, diphenyl sulfone cross-link type compound represented by the following formula (formula 1), dihydroxy diphenyl sulfone compound represented by the general formula (Formula 6), and diphenyl sulfone compound represented by the general formula (Formula 7) are preferred, and diphenyl sulfone cross-link type compound represented by the following formula (formula 1), 4-hydroxy-4'-isopropoxy diphenyl sulfone, 4-hydroxy-4'-allyloxy diphenyl sulfone and 4-hydroxy-4'-n-propoxy diphenyl sulfone are more preferred, because the thermosensitive recording medium is superior in record density, stable against plasticizer, and low in deterioration of recording property after storage (record density after storage at high temperature and high humidity) when using these.
The sensitizer that can be used in the present invention includes diphenyl sulfone, aliphatic acid amides such as stearic acid amide, palmitic acid amide and the like, benzyloxy naphthalene, 1,2-di-(3-methylphenoxy) ethane, di-(p-methylbenzyl) oxalate and the like. However, the sensitizer is not particularly restricted to the examples listed. The sensitizers may be used solely or as mixtures of at least two of them.
As the binder, the acrylic resin described above, polyvinyl alcohols such as completely saponified poly(vinyl alcohol), partially saponified poly(vinyl alcohol), carboxyl modified poly(vinyl alcohol), silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohols, terminal alkyl-modified polyvinyl alcohol and the like, cellulose ether and derivatives thereof such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, acetyl cellulose and the like, starches such as starch, enzyme modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (for example, hydroxyethyl starch), cationic starch and the like, polyacrylamides such as polyacrylamide, cationic polyacrylamide, anionic polyacrylamide, amphoteric polyacrylamide, and the like, urethane resins such as polyester polyurethane resins, polyether polyurethane resins, polyurethane ionomer resins, and the like, styrene-butadiene resins such as styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-butadiene- acryl copolymer, and the like, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid esters, gum Arabic, polyvinyl bu-tyral, polystyrol, and copolymer thereof, silicone resins, petroleum resins, ter-pene resins, ketone resins, cumaron resins and the like may be listed as examples. These can be used in combination thereof.
As a binder used in the present invention, emulsion or latex of above urethane resins and above styrene-butadiene resins are preferred because these increase adhesion or stickiness to a plastic film.
As the crosslinking agent, glyoxal, methylol melamine, melamine formaldehyde resins, melamine urea resins, polyamine epichlorohydrin resins, polyamide epichlorohydrin resins, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, magnesium chloride, borax, boric acid, alum, ammonium chloride and the like may be listed as examples.
As the slipping agent, fatty acid metal salts such as zinc stearate, calcium stearate and the like, wax, silicone resins and the like may be cited.
As stabilizers in the present invention that impart oil resistance and the like to recorded images, 4,4’-butylidene (6-t-butyl-3-methylphenol), 2,2’-di-t-butyl-5,5’-dimethyl-4,4’-sulfonyl diphenol, 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-methyl propoxy)diphenylsulfone and the like may be used.
In addition, UV absorption agents, such as benzophenone type and triazole type UV absorption agents dispersion agents, defoaming agents, oxidation inhibitors, fluorescent dye and the like may also be used.
The type and amount of the leuco dye, color developing agent, sensitizer, and other various ingredients used in the present invention are determined according to the performance and recording suitability required and are not particularly restricted. Ordinarily, however, in the thermosensitive recording layer, 0.5 to 10 parts of color developing agent, 0.5 to 20 parts of pigment, 0.1 to 10 parts of sensitizer, 0.01 to 10 parts of stabilizer and 0.01 to 10 parts of the other in gredients are used per one part of a leuco dye. 5 to 50 weight % of binder is suitably used in the solid content of the thermosensitive recording layer.
The leuco dye, the color developing agent and other materials added as needed are finely ground into particles with several microns or smaller in size, using a grinder or a suitable emulsification device such as ball mills, attriters, sand grinders and the like, and a coating solution is prepared by adding a binder and various additive materials depending on the objective. Water or alcohol and the like may be used as the solvent for preparing the coating solution, and the solid content of the coating solution is 20 to 40% by weight.
The targeted thermosensitive recording medium can be obtained by applying the coating solution described above on a plastic film support.
In order to coat each layer, air knife coating, a rod blade coating, bent blade coating, bevel blade coating, roll coating, slot-type curtain coating, slide-type curtain coating, slide hopper type curtain coating, bead-type curtain coating, spray coating, die coating and the like can be used. And the coating method is appropriately selected from these coating methods.
The coating amount of the thermosensitive recording layer is ordinarily in the range of from 2 g/m2 to 10 g/m2, and the coating amount of the protective layer is ordinarily in the range of from 1 g/m2 to 5 g/m2.
Furthermore, various technologies known in the thermosensitive recording medium field may be used as needed, for example, a flattening treatment such as super calendaring and the like can be conducted after coating individual coating layers.
EXAMPLES
The following examples will illustrate the present invention, but these are not intended to restrict the present invention. In the following description, the terms parts and % indicate parts by weight and wt.%, respectively. A color development agent dispersion (solution A), a leuco dye dispersion (solution B) and a sensitizer dispersion (solution C) with the following formulation were separately wet ground using sand grinders until the average particle size was about 0.5 pm.
Color development agent dispersion (solution A)
Diphenyl sulfone cross-link type compound (Nippon Soda Co., Ltd. D-90) 6.0 parts 10% Aqueous solution of polyvinyl alcohol 18.8 parts
Water 11.2 parts
Leuco dye dispersion (solution B) 3-Dibutylamino-6-methyl-7-anilinofluorane (Yamamoto Chemicals Inc. ODB-2) 3.0 parts 10% Aqueous solution of polyvinyl alcohol 6.9 parts
Water 3.9 parts
Sensitizer dispersion (solution C)
Oxalic acid bis (p-methylbenzyl) (DIC Corporation, HS3520) 1.5 parts 10% Aqueous solution of polyvinyl alcohol 4.7 parts
Water 2.8 parts
Next the dispersions were blended in the proportion described below to prepare a coating solution for thermosensitive recording layer.
Thermosensitive recording layer coating solution 1 (referred to as “SBR formulation”)
Color development agent dispersion (solution A) 36.0 parts
Leuco dye dispersion (solution B) 13.8 parts
Sensitizer dispersion (solution C) 9.0 parts
Styrene-butadiene copolymer latex (solid content 48%) 16.0 parts
Dioctyl sodium sulfosuccinate (Kao Corporation, Pelex OT-P, solid content 70%) 0.15 parts
Water 15.0 parts
Thermosensitive recording layer coating solution 2 (referred to as “PVA formulation”)
Color development agent dispersion (solution A) 36.0 parts
Leuco dye dispersion (solution B) 13.8 parts
Sensitizer dispersion (solution C) 9.0 parts 12% Aqueous solution of completely saponified polyvinyl alcohol (Kuraray Co., Ltd. PVA117) 25.0 parts
Then protective layer coating solutions were prepared by mixing the following ingredients in the proportion described below.
Protective layer coating solution 1
Non-core-shell type acrylic resin emulsion (Mitsui Chemicals, Inc., ASN1004K, Tg 55 degree C, solid content 18%) 24.0 parts
Self-emulsifying type polyolefin resin emulsion (Sumitomo Seika Chemicals Co., Ltd., Zaikthene-A-GH, solid content 24.4%) 3.0 parts
Zinc stearate (Chukyo Yushi Co., Ltd.: Hydrin L536, solid content 40%) 4.0 parts
Dioctyl sodium sulfosuccinate (Kao Corporation, Pelex OT-P, solid content 70%) 0.07 parts
Water 30.0 parts
Protective layer coating solution 2
Non-core-shell type acrylic resin emulsion (Mitsui Chemicals, Inc., ASN1004K, Tg 55 degree C, solid content 18%) 24.0 parts
Self-emulsifying type polyolefin resin emulsion (Sumitomo Seika Chemicals Co., Ltd., Zaikthene-AC, solid content 30.0%) 2.5 parts
Zinc stearate (Chukyo Yushi Co., Ltd.: Hydrin L536, solid content 40%) 4.0 parts
Dioctyl sodium sulfosuccinate (Kao Corporation, Pelex OT-P, solid content 70%) 0.07 parts
Water 30.0 parts
Protective layer coating solution 3 12% aqueous solution of completely saponified polyvinyl alcohol (Kuraray Co., Ltd. PVA117) 42.0 parts
Glyoxal (40% aqueous solution) 5.0 parts
Zinc stearate (Chukyo Yushi Co., Ltd.: Hydrin L536, solid content 40%) 4.0 parts
Water 27.0 parts
Example 1
The thermosensitive recording layer coating solution 1 (SBR formulation) was applied on a polyethylene terephthalate film (Teijin Ltd., TEIJIN TETORON 330, thickness: 38pm, total light transmittance: 82%, referred to as “PET film”) with a coating amount (dried) of 5.0 g/m2 and was dried, and then the protective layer coating solution 1 was applied with a coating amount (dried) of 3.0 g/m2 and was dried to prepare a thermosensitive recording medium.
Example 2 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of replacing the PET film with a triacetyl cellulose film (Fujifilm Corporation, FUJITAC, thickness: 40pm, total light transmittance: 90%, referred to as “TAC film”).
Example 3 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of replacing 16.0 parts of styrene-butadiene resin latex (solid content 48%) with 6.0 parts of styrene-butadiene resin latex (solid content 48%) and 15.0 parts of self-emulsifying type polyolefin resin emulsion (Sumitomo Seika Chemicals Co., Ltd., Zaikthene-A-GH, solid content 24.4%) in the thermosensitive recording layer coating solution 1 (SBR formulation).
Example 4 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of using the protective layer coating solution 2 instead of the protective layer coating solution 1.
Example 5 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of replacing the non-core-shell type acrylic resin emulsion with a non-core-shell type acrylic resin emulsion (Mitsui Chemicals, Inc., XNP3, Tg 35 degree C, solid content 18%) in the protective layer coating solution 1.
Example 6 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of replacing 24.0 parts of the noncore-shell type acrylic resin emulsion with 22.0 parts of a core-shell type acrylic resin emulsion (Nippon Paint Co., Ltd, N-538, Tg 100 degree C, solid content 20%) in the protective layer coating solution 1.
Example 7 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of changing the formulating amounts of the non-core-shell type acrylic resin emulsion and the self-emulsifying type polyolefin resin emulsion to 12.0 parts each in the protective layer coating solution 1.
Example 8 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of changing the formulating amounts of the non-core-shell type acrylic resin emulsion and the self-emulsifying type polyolefin resin emulsion to 27.5parts and 0.3 parts respectively in the protective layer coating solution 1.
Example 9 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of replacing the diphenyl sulfone cross-link type compound (Nippon Soda Co., Ltd., D-90) with 4,4'-dihydroxy diphenyl sulfone (Nicca Chemical Co., Ltd., BPS-P (R), referred to as “44BPS”) in the color development agent dispersion (solution A).
Example 10 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of replacing the diphenyl sulfone cross-link type compound (Nippon Soda Co., Ltd., D-90) with 2,4'-dihydroxy diphenyl sulfone (Nicca Chemical Co., Ltd., BPS-24C, referred to as “24BPS”) in the color development agent dispersion (solution A).
Example 11 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of replacing the diphenyl sulfone cross-link type compound (Nippon Soda Co., Ltd., D-90) with 4-hydroxy-4'-allyloxydiphenyl sulfone (Nicca Chemical Co., Ltd., BPS-MAE) in the color development agent dispersion (solution A).
Example 12 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of replacing the diphenyl sulfone cross-link type compound (Nippon Soda Co., Ltd., D-90) with 4-hydroxy-4'-n-propoxy diphenyl sulfone (API Corporation, TOMILAC KN) in the color development agent dispersion (solution A).
Example 13 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of replacing the diphenyl sulfone cross-link type compound (Nippon Soda Co., Ltd., D-90) with 4-hydroxy-4'-isopropoxy diphenyl sulfone (Nippon Soda Co., Ltd., D-8) in the color development agent dispersion (solution A).
Example 14 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of replacing the diphenyl sulfone cross-link type compound (Nippon Soda Co., Ltd., D-90) with the compound represented by the general formula below (formula 8, API Corporation, SU727) in the color development agent dispersion (solution A).
Comparative Example 1
The thermosensitive recording layer coating solution 2 (PVA formulation) was applied on a support paper (with 60 g/m2 of basic weight) with a coating amount (dried) of 5.0 g/m2 and was dried, and then the protective layer coating solution 3 was applied with a coating amount (dried) of 3.0 g/m2 and was dried to prepare a thermosensitive recording medium.
Comparative Example 2 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of using the protective layer coating solution 3 instead of the protective layer coating solution 1. Figure 1 shows the photograph of the surface of the protective layer of the prepared thermosensitive recording medium.
Comparative Example 3 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of not installing the protective layer.
Comparative Example 4 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of not formulating the self-emulsifying type polyolefin resin emulsion, and changing the amount of the non-core-shell type acrylic resin emulsion to 27.5 parts in the protective layer coating solution 1.
Comparative Example 4 A thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of not formulating the non-core-shell type acrylic resin emulsion, and changing the amount of the self-emulsifying type polyolefin resin emulsion to 20.5 parts in the protective layer coating solution 1.
The prepared thermosensitive recording media were evaluated as follows: Record density
The prepared thermosensitive recording media were recorded solidly by using a printing tester for thermosensitive recording paper (Okura Engineering Co. LTD., TH-PMD equipped with a thermal head by Kyocera Corporation.) at recording energy of 0.42 mJ/dot and recording speed of 50 mm/sec. The density of the recorded image was measured by using Macbeth Densitometer (RD-914, with Amber filter).
Coating defects
The prepared thermosensitive recording medium was visually inspected to evaluate if there are coating defects (ripple-like coating) on the surface. The coating defect was evaluated by the following criteria:
Excellent: No ripple-like coating found
Good: Almost no ripple-like coating found
Fair: Slight ripple-like coating found
Poor: Much ripple-like coating found
Water resistance
The prepared thermosensitive recording medium was immersed in water at 23 degree C and 50% Rh for 24 hours, and was visually inspected. The water resistance was evaluated by the following criteria:
Excellent: No peeling nor cracking found
Good: Almost no peeling nor cracking found
Fair: Slight peeling and/or cracking found
Poor: Many peeling and/or cracking found
Printing run-ability
The prepared thermosensitive recording media were recorded solidly by using a printing tester (Canon Inc. HT180) at recording energy of 0.20 mJ/dot at 0 degree C. “Unprinted area” and “noise” are caused because the outermost layer of the medium sticks to the head of the printing tester. The recorded condition was evaluated by the following criteria:
Excellent: No unprinted area in the solidly recorded area and no noise Good: No unprinted area in the solidly recorded area and slight noise
Fair: Some unprinted areas in the solidly recorded area and slight noise
Poor: A lot of unprinted areas in the solidly recorded area and large noise
Plasticizer resistance
The prepared thermosensitive recording media were recorded solidly by using a printing tester for thermosensitive recording paper (Okura Engineering Co. LTD., TH-PMD equipped with a thermal head by Kyocera Corporation.) at recording energy of 0.42 mJ/dot and recording speed of 50 mm/sec. A paper tube was wrapped once with polyvinyl chloride wrap (Mitsui Toatsu Chemical: High Wrap KMA) and the thermosensitive recording medium was placed on the wrapped paper tube so that the recorded face is the outer face. Furthermore, the tube was wrapped 3 times with polyvinyl chloride wrap and was left standing at 40°C and 50%RH for 5 hours. The record density of the recorded section was measured by using Macbeth densitometer (RD-914, with amber filter), and the residual ratio was calculated from the measured value before and after the treatment according to the following equation:
Residual ratio (%) = (record density after the treatment / record density before the treatment) x 100
Recording property after storage
The prepared thermosensitive recording media were left standing at 50°C and 90%RH for 24 hours and then were left standing at 23°C and 50%RH for 3 hours. Then the thermosensitive recording media were recorded solidly by using a printing tester for thermosensitive recording paper (Okura Engineering Co. LTD., TH-PMD equipped with a thermal head by Kyocera Corporation.) at recording energy of 0.42 mJ/dot and recording speed of 50 mm/sec. The density of the recorded image was measured by using Macbeth Densitometer (RD-914, with Amber filter).
Results are shown in Table 1 below:
Table 1

Claims (8)

1. Lämpöherkkä tallennusväline, jossa on muovikalvon päällä lämpö-herkkä tallennuskerros, joka käsittää väritöntä tai vaaleanväristä emäksistä leukoväriainetta ja elektroneja vastaanottavaa kehitettä, ja uloimpana kerroksena lämpöherkän tallennuskerroksen päällä suoja-kerros, jolloin suojakerros käsittää akryylihartsia ja polyolefiinihartsia, jolloin polyolefiinihartsin/akryylihartsin painosuhde (kiintoainepitoisuus) on 5/95-40/60, jossa akryylihartsi käsittää (i) (met)akryylihappoa ja (ii) (met)akrylonitriiliä ja/tai metyyli(met)akrylaattia ja (met)akryylihappon, (met)akrylonitriilin ja metyyli(met)akrylaatin määrät ovat samassa järjestyksessä 1-10 paino-osaa, 15-70 paino-osaa (jos sitä on) ja 20-80 paino-osaa (jos sitä on) jokaista akryylihartsin 100 paino-osaa kohden.A thermosensitive recording medium having a thermosensitive recording layer on a plastic film comprising a colorless or pale basic leuco dye and an electron accepting developer, and an outer layer on a thermosensitive recording layer comprising a protective layer comprising a protective layer comprising an acrylic ) is 5 / 95-40 / 60 wherein the acrylic resin comprises (i) (meth) acrylic acid and (ii) (meth) acrylonitrile and / or methyl (meth) acrylate and (meth) acrylic acid, (meth) acrylonitrile and methyl (meth) ) acrylate amounts are in the order of 1-10 parts by weight, 15-70 parts by weight (if present) and 20-80 parts by weight (if present) for each 100 parts by weight of acrylic resin. 2. Patenttivaatimuksen 1 mukainen lämpöherkkä tallennusväline, jolloin polyolefiinihartsi on olefiini-tyydyttömätön karboksyylihappokopoly-meeri.The thermosensitive recording medium of claim 1, wherein the polyolefin resin is an olefinically unsaturated carboxylic acid copolymer. 3. Patenttivaatimuksen 1 tai 2 mukainen lämpöherkkä tallennusväline, jolloin akryylihartsin lasittumislämpötila on suurempi kuin 50 °C ja pienempi tai yhtä suuri kuin 95 °C.The thermosensitive recording medium of claim 1 or 2, wherein the acrylic resin has a glass transition temperature greater than 50 ° C and less than or equal to 95 ° C. 4. Jonkin patenttivaatimuksista 1-3 mukainen lämpöherkkä tallennusväline, jolloin akryylihartsi on muu kuin ydin-kuorityyppinen akryylihartsi.The thermosensitive recording medium according to any one of claims 1 to 3, wherein the acrylic resin is a non-core-shell type acrylic resin. 5. Jonkin patenttivaatimuksista 1-4 mukainen lämpöherkkä tallennusväline, jolloin suojakerroksessa olevan akryylihartsin määrä on kiintoai-nepitoisuutena 3-60 paino-%.The thermosensitive recording medium of any one of claims 1 to 4, wherein the amount of acrylic resin in the protective layer is in the range of 3 to 60% by weight solids. 6. Jonkin patenttivaatimuksista 1-5 mukainen lämpöherkkä tallennusväline, jolloin suojakerroksessa olevan akryylihartsin määrä on kiintoai-nepitoisuutena 15-97 paino-%.The thermosensitive recording medium according to any one of claims 1 to 5, wherein the amount of acrylic resin in the protective layer is in a solids content of 15 to 97% by weight. 7. Jonkin patenttivaatimuksista 1-6 mukainen lämpöherkkä tallennusväline, jolloin lämpöherkkä tallennuskerros sisältää uretaanihartsien tai styreeni-butadieenihartsien emulsiota tai lateksia.The thermosensitive recording medium of any one of claims 1 to 6, wherein the thermosensitive recording layer comprises an emulsion or latex of urethane resins or styrene-butadiene resins. 8. Jonkin patenttivaatimuksista 1-7 mukainen lämpöherkkä tallennusväline, jolloin värikehite on ainakin jokin, joka on valittu ryhmästä, johon kuuluvat (i) tyypiltään silloitettu difenyylisulfoniyhdiste, joka on esitetty seuraa-valla kaavalla (kaava 1)The thermosensitive recording medium according to any one of claims 1 to 7, wherein the color developer is at least one selected from the group consisting of (i) a diphenylsulfone type crosslinked compound represented by the following formula (formula 1) jossa R1, joka voi olla samanlainen tai erilainen, on halogeeniatomi tai alkyyliryhmä tai alkenyyliryhmä, jossa on 1-6 hiiliatomia, m, joka voi olla samanlainen tai erilainen, on kokonaisluku 0-4, n on kokonaisluku 1-11, R2, joka voi olla samanlainen tai erilainen, on hiilivetyryhmä, jossa on 1-12 hiiliatomia, jossa voi olla eetterisidos, joka voi olla tyydyttynyt tai tyydyttymätön, joka voi olla suoraketjuinen tai haaroittunut, substi-tuoitu fenyleeniryhmä, joka on esitetty alla olevalla yleiskaavalla:wherein R 1, which may be the same or different, is a halogen atom or an alkyl or alkenyl group having 1 to 6 carbon atoms, m which may be the same or different is an integer from 0 to 4, n is an integer from 1 to 11, the same or different, is a hydrocarbon group having from 1 to 12 carbon atoms, which may have an ether linkage, which may be saturated or unsaturated, which may be a linear or branched, substituted phenylene group represented by the following general formula: jossa kaavassa R3 on metyleeniryhmä tai etyleeniryhmä tai kaksiarvoinen ryhmä, joka on esitetty alla olevalla yleiskaavalla:wherein R 3 is a methylene group or an ethylene group or a divalent group represented by the following general formula: jossa kaavassa R4 on vetyatomi tai alkyyliryhmä, jossa on 1-4 hiiliatomia, ja (ii) dihydroksidifenyylisulfoniyhdiste, joka on esitetty seuraavalla kaava (kaava 4)wherein R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and (ii) a dihydroxydiphenylsulfone compound represented by the following formula (formula 4) jossa R5 ja R6 ovat toisistaan riippumatta halogeeniatomi tai alkyyliryhmä tai alkenyyliryhmä, jossa on 1-8 hiiliatomia, R7 on vetyatomi tai suoraketjuinen tai haaroittunut, tyydyttynyt tai tyydyt-tymätön hiilivety, jossa on 1-4 hiiliatomia, ja p ja q ovat toisistaan riippumatta kokonaisluku 0-3.wherein R5 and R6 are each independently a halogen atom or an alkyl group or an alkenyl group having 1 to 8 carbon atoms, R7 is a hydrogen atom or a straight or branched, saturated or unsaturated hydrocarbon having from 1 to 4 carbon atoms, and p and q are independently 0-3.
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