WO2011027752A1 - 感熱記録ラベル - Google Patents
感熱記録ラベル Download PDFInfo
- Publication number
- WO2011027752A1 WO2011027752A1 PCT/JP2010/064862 JP2010064862W WO2011027752A1 WO 2011027752 A1 WO2011027752 A1 WO 2011027752A1 JP 2010064862 W JP2010064862 W JP 2010064862W WO 2011027752 A1 WO2011027752 A1 WO 2011027752A1
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- WIPO (PCT)
- Prior art keywords
- group
- resin
- heat
- recording label
- polyamine
- Prior art date
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Classifications
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/08—Fastening or securing by means not forming part of the material of the label itself
- G09F3/10—Fastening or securing by means not forming part of the material of the label itself by an adhesive layer
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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
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- 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]
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- 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
- B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
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- 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
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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
- B41M5/30—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
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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
- B41M5/30—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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- 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
- B41M5/41—Base layers supports or substrates
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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
Definitions
- the present invention relates to a thermal recording label provided with a printable thermal recording layer and an adhesive layer, and more particularly to a thermal recording label having excellent water resistance.
- the main component is a colorless or light-colored electron-donating leuco dye (hereinafter also referred to as “dye”) and an electron-accepting developer (hereinafter also referred to as “developer”) that reacts with the dye to develop color.
- the heat-sensitive recording material having the heat-sensitive recording layer is widely put into practical use. In order to perform recording on this thermal recording medium, a thermal printer with a built-in thermal head is usually used. Compared to other recording systems, this thermal recording system has no noise during recording, does not require development and fixing, is maintenance-free, the equipment is relatively inexpensive, and is compact. It is widely used for facsimiles, computer terminal printers, automatic ticket vending machines, measurement recorders, handy terminals used outdoors, and the like. On the other hand, pressure-sensitive adhesive labels having a pressure-sensitive adhesive layer on one side of paper are widely used for label applications such as price display labels, product display labels, weighing display labels, and advertising labels.
- a thermal recording label in which a thermal recording medium and an adhesive label are combined has a configuration in which an adhesive layer containing an adhesive as a main component is provided on the opposite side of the normal thermal recording layer.
- Thermosensitive recording label (Patent Document 1) using an adhesive, thermosensitive recording label using a thermoactive adhesive containing a thermoplastic resin and a solid plasticizer as an adhesive (Patent Document 2), thermal efficiency during heating of the thermoactive adhesive
- Patent Document 3 using an intermediate layer provided between the base paper and the heat-activatable pressure-sensitive adhesive layer and using a hollow plastic pigment as a main component of the intermediate layer is disclosed.
- thermosensitive recording labels have been increasingly used under severe conditions such as frozen food labels, warning labels affixed outdoors in extreme heat, and distribution labels.
- the demand for weather resistance is increasing.
- a method of improving the water resistance and weather resistance of the thermosensitive recording label by providing a protective layer on the thermosensitive recording layer is employed (Patent Documents 4 to 6, etc.).
- an object of the present invention is to provide a thermosensitive recording label having water resistance and weather resistance that are remarkably superior to conventional ones.
- thermosensitive recording label a novel configuration in which a thermosensitive recording layer and an adhesive layer are sequentially provided on a transparent film support.
- the outermost layer becomes a transparent film support, and therefore, it has been found that excellent water resistance and weather resistance are possible.
- the heat-sensitive recording layer and the pressure-sensitive adhesive layer are in contact with each other, and the components of the pressure-sensitive adhesive layer may invade the heat-sensitive recording layer, which may adversely affect the color development sensitivity or the film strength of the heat-sensitive recording layer.
- the present invention provides a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting developer on a transparent film support, and an adhesive is the main component on the heat-sensitive recording layer.
- a heat-sensitive recording label provided with an adhesive layer.
- This pressure-sensitive adhesive is preferably not sticky at normal temperature, and is particularly preferably of a type that exhibits pressure-sensitive adhesiveness when heated to a temperature between 40 and 100 ° C.
- the thermal recording label of the present invention When the thermal recording label of the present invention is applied to an adherend, the transparent film, the thermal recording layer, the pressure-sensitive adhesive layer, and the adherend are arranged in order from the outermost layer. Since the heat-sensitive recording layer is hardly affected by oxygen in the air, the stability of the image area (light resistance, etc.) is also improved. Since the thermal recording label of the present invention can be used for a warning label, a physical distribution label and the like attached outdoors, its practical value is extremely high.
- the heat-sensitive recording label of the present invention has a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting developer on one side of a transparent film as a support, and an adhesive is mainly formed thereon. It has the structure of having an adhesive layer as a component. An intermediate layer may be provided between the heat-sensitive recording layer and the pressure-sensitive adhesive layer.
- the transparent film used in the present invention is obtained by forming a polymer raw material into a thin film, and when it is printed on a heat-sensitive recording layer provided on one side of the film, the transparency is at least visually from the opposite side of the film. It is sufficient that the printed characters and patterns are legible.
- the total light transmittance of the transparent film is preferably 60% or more, more preferably 70% or more, and most preferably 90% or more. This transparent film may be colored.
- the thickness of the transparent film is preferably 20 ⁇ m to 100 ⁇ m.
- films examples include ionomer film (IO), polyethylene film (PE), polyvinyl chloride film (PVC), polyvinylidene chloride film (PVDC), polyvinyl alcohol film (PVA), polypropylene film (PP), and polyester.
- Film polyethylene terephthalate film (PET), polyethylene naphthalate film (PEN), polycarbonate film (PC), polystyrene film (PS), polyacrylonitrile film (PAN), ethylene vinyl acetate copolymer film (EVA), ethylene vinyl Alcohol copolymer film (EMAA), nylon film (NY), polyamide film (PA), triacetyl cellulose film (TAC), norbornenef Lum (NB), such as Arton film can be exemplified.
- PET, PEN, TAC, NB, and Arton film are preferable from the viewpoints of transparency and rigidity when label processing is performed, and PET and PEN having a small surface undulation are particularly preferable from the manufacturing method. Furthermore, it is desirable to provide an easy-adhesion layer by applying polyester resin, silicone resin, or the like to the surface of the film, or to improve the adhesion of the coating layer by corona treatment of the film surface.
- PET films include Toyobo Ester (registered trademark) films E5107, E5100, E5101, Cosmo Shine (registered trademark) A4100, A4300, A8300, etc. manufactured by Toyobo Co., Ltd.
- Teonex (registered trademark) Q51, Q51DW, Q65F, Q65FA and the like. These transparent films may contain additives such as various UV absorbers, antioxidants, flame retardants, heat stabilizers, colorants, mold release agents, softening materials, and antistatic agents.
- a rubber-based pressure-sensitive adhesive an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a pressure-sensitive adhesive having a viscosity at room temperature, such as a urethane-based pressure-sensitive adhesive, without stickiness at room temperature
- examples include hot-melt pressure-sensitive adhesives that are activated by heating and melting at the time of use, and heat-sensitive pressure-sensitive adhesives mainly composed of a thermoplastic resin and a solid plasticizer, but are not limited thereto.
- the thermal recording label consists of a film support, thermal recording layer, adhesive layer, and separate paper (release paper). Therefore, very high energy is required to develop sufficient color developability.
- the adhesive is not adhesive at normal temperature.
- the heat-sensitive recording label is composed of a film support, a heat-sensitive recording layer, and a pressure-sensitive adhesive layer, and energy can be applied from the pressure-sensitive adhesive layer side to obtain good color development. Can do.
- the adhesive development temperature of hot melt adhesives is usually high at 100 to 180 ° C., and therefore, there is a possibility that sufficient adhesiveness may not be exhibited with energy optimal for color development, and conversely, sufficient adhesiveness is exhibited. When energy is applied, the entire heat-sensitive recording layer may be colored.
- the pressure-sensitive adhesive used in the present invention preferably has no pressure-sensitive adhesive at room temperature, and a heat-active pressure-sensitive adhesive that exhibits pressure-sensitive adhesiveness when heated to a temperature between 45 and 100 ° C., preferably 50 to 90 ° C. Further preferred.
- a heating method for developing adhesiveness the entire thermosensitive recording label may be heated by a heating furnace or hot air, but the pressure-sensitive adhesive layer may be partially heated by a heating head or the like. . The latter case is preferable because the heat-sensitive recording layer is not heated.
- the heat-sensitive recording layer usually develops color when heated at 90 ° C. for about 5 minutes or more, and so-called background coloring (background fogging) may occur.
- thermoplastic resin and a solid plasticizer as main components and optionally containing a tackifier is preferable. Since this heat activation adhesive can adjust heat activation temperature suitably, it can obtain the quality which made adhesiveness and coloring property compatible.
- thermoplastic resin used for the thermoactive adhesive examples include methyl methacrylate (105 ° C.), ethyl acrylate ( ⁇ 22 ° C.), butyl acrylate ( ⁇ 54 ° C.), 2-ethylhexyl acrylate ( ⁇ 85 ° C.), carboxypolycaprolactone Vinyl aromatic compounds such as acrylate ( ⁇ 41 ° C.), monohydroxyethyl acrylate succinate ( ⁇ 40 ° C.), styrene (100 ° C.), vinyl halides such as vinyl chloride (80 ° C.), vinylidene chloride ( ⁇ 20 ° C.) And vinyl esters such as vinyl acetate (30 ° C.) and vinyl propionate (10 ° C.), olefin monomers such as ethylene ( ⁇ 125 ° C.) and butadiene ( ⁇ 109 ° C.), and other acrylonitrile (130 ° C.). It is done. The glass transition point is shown in parentheses.
- a benzoic acid ester compound for example, a benzoic acid ester compound, a hindered phenol ester compound and the like are preferably used.
- the benzoic acid ester compound include sucrose benzoate, diethylene glycol benzoate, glyceryl benzoate, pentaerythritol benzoate, trimethylolethane benzoate, and trimethylolpropane benzoate. Esters are particularly preferably used.
- Another preferred solid plasticizer is a hindered phenol ester compound.
- solid plasticizers include triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] and thiobis [ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate].
- solid plasticizers can also be used as a mixture of two or more.
- An aqueous dispersion of a solid plasticizer needs to maintain a dispersed particle size of a certain level or less in order to prevent sedimentation and maintain the smoothness of a coated product. Therefore, it is pulverized and dispersed by a ball mill, handy mill, etc. as necessary.
- tackifier used in the thermally active adhesive examples include rosin, hydrogenated rosin and derivatives thereof, rosin resins such as resin acid dimer, terpene resin, aromatic modified terpene resin, hydrogenated terpene resin, terpene-phenol.
- rosin resins such as resin acid dimer, terpene resin, aromatic modified terpene resin, hydrogenated terpene resin, terpene-phenol.
- terpene resins such as resins, aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, styrene resins, and phenol resins. These resins are used alone or in combination of two or more.
- the thermally active pressure-sensitive adhesive composition uses the above thermoplastic resin, an aqueous dispersion of a solid plasticizer and an aqueous dispersion of a tackifier such as rosin ester, and the mass ratio of the solid content is 20 to 40:50. ⁇ 70: 10-20 is preferred.
- thermally active adhesives include Heat Magic DW1040W (manufactured by Toyo Ink Co., Ltd., thermal activation temperature 50 ° C.), Eco Brid 5610 (thermal activation temperature 70 ° C.), Eco Brid TM-1 (thermal activation) Eco Brid S-1 (thermal activation temperature 90 ° C.), Eco Brid TM-100 (thermal activation temperature 70 ° C.), Eco Brid 5635 (thermal activation temperature 70 ° C.), Eco Brid 5640 (thermal activation temperature 70) ° C) (manufactured by Daicel Finechem Co., Ltd.), Dick Seal DLA-820K (thermal activation temperature 80 ° C), Dick Seal ED-920K (thermal activation temperature 90 ° C) (manufactured by DIC Corporation), and the like.
- the thermal activation temperature in the parenthesis was allowed to stand for 2 minutes in a blast dryer maintained at a constant temperature, and the lowest temperature at which the tack
- a surfactant an antifoaming agent, a lubricant, a colorant, a filler, and the like may be blended as necessary within a range that does not impair the object of the present invention.
- the coating amount of the pressure-sensitive adhesive of the present invention is small, the initial adhesion to the adherend is insufficient, and if it is too large, it is difficult to obtain a smooth coated surface, and the drying property is also reduced.
- the heat-sensitive recording layer of the present invention contains a dye and a developer, and may further contain a sensitizer, a binder, a crosslinking agent, a stabilizer, a pigment, a lubricant, and the like as necessary.
- various materials used for the thermosensitive recording layer of the present invention will be exemplified.
- the electron-donating leuco dye used in the present invention those known in the conventional pressure-sensitive or heat-sensitive recording paper field can be used, and are not particularly limited, but include triphenylmethane compounds, fluorane compounds. Compounds, fluorene compounds, divinyl compounds and the like are preferable. Specific examples of typical colorless or light-colored dyes (dye precursors) are shown below.
- 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)
- Inorganic acidic substances such as 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, 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4-hydroxy-4 ' -Isopropoxydiphenyl sulfone, 4-hydroxy-4 -N-propoxydiphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'-methyl
- the pressure-sensitive adhesive is used to prevent the color development ability from decreasing over time due to the effect of the pressure-sensitive adhesive, and to develop the pressure-sensitive adhesive in the structure of the thermal recording label of the present application.
- R 3 may be the same or different, but is preferably the same and represents a hydrogen atom, a halogen atom, an alkyl group or an alkenyl group having 1 to 6 carbon atoms, preferably a hydrogen atom.
- the alkyl group or alkenyl group is an alkyl group or alkenyl group having 1 to 6 carbon atoms.
- the halogen atom represents chlorine, bromine, fluorine or iodine, preferably chlorine or bromine.
- o independently represents 0 to 4, preferably 0.
- the OH group and —OR 4 O— group are preferably in the para position with respect to the SO 2 group.
- p is 1 to 11. This compound is preferably a mixture having p of 1 to 11.
- R 4 may be the same or different, but is preferably the same.
- R 4 is a saturated or unsaturated, preferably saturated, linear or branched, preferably linear hydrocarbon having 1 to 12 carbon atoms, 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.
- Examples of the alkylene group include —C b H 2b — (b is an arbitrary integer).
- R 4 the following general formula (In the formula, R 5 represents a methylene group or an ethylene group. R 5 is preferably in the para position with respect to each other.)
- R 4 the following general formula (Wherein R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom). ). Of these, R 4 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 in this diphenylsulfone cross-linking compound examples include the following. Methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, methylmethylene group, dimethylmethylene Group, methylethylene group, methyleneethylene group, ethylethylene group, 1,2-dimethylethylene group, 1-methyltrimethylene group, 1-methyltetramethylene group, 1,3-dimethyltrimethylene group, 1-ethyl-4 -Methyl-tetramethylene group, vinylene group, propenylene group, 2-butenylene group, ethynylene group, 2-butynylene group, 1-vinylethylene group, ethyleneoxyethylene group, tetramethyleneoxytetramethylene group, ethyleneoxyethyleneoxyethylene group , E
- the diphenylsulfone crosslinking type compound may be used by mixing several kinds of substituents (R 3 ) and / or p having different numbers, and the content ratio is arbitrary.
- the mixing method is not particularly limited, such as mixing in powder, mixing in the state of a dispersion dispersed in water or the like, and a method of simultaneously producing and containing a plurality of types of diphenylsulfone cross-linking compounds depending on production conditions.
- Examples of the compound represented by the general formula (Formula 1) include 4,4′-bis [4- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2-trans-butenyloxy] diphenylsulfone; '-Bis [4- (4-hydroxyphenylsulfonyl) phenoxy-4-butyloxy] diphenylsulfone; 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-3-propyloxy] diphenylsulfone; 4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethyloxy] diphenylsulfone; 4- [4- (4-hydroxyphenylsulfonyl) phenoxy-4-butyloxy] -4 '-[4- (4 -Hydroxyphenylsulfonyl) phenoxy-3-propyloxy] di 4- [4- (4-hydroxy
- a particularly preferable composition contains two or more types in which R 3 is the same and only the value of p is different. To do. If it is such a compound, a manufacturing method is also simple and the compound from which the value of p differs by changing the reaction ratio of a raw material can be synthesize
- R 1 represents a linear or branched saturated or unsaturated hydrocarbon having 1 to 12, preferably 1 to 5, more preferably 1 to 4 carbon atoms.
- saturated hydrocarbon group examples include: Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isoamyl and the like.
- the unsaturated hydrocarbon group preferably has 2 to 5 carbon atoms, and examples of the unsaturated hydrocarbon group include ethylene, 1-n-propylene, 2-n-propylene, isopropylene, and 1-n-butylene. 2-n-butylene, 3-n-butylene and the like.
- R 2 each independently represents a halogen atom, or an alkyl or alkenyl group having 1 to 12 carbon atoms.
- the halogen atom include chlorine, bromine, fluorine, and iodine. preferable.
- This alkyl group is a linear or branched saturated hydrocarbon having 1 to 12, preferably 1 to 5, more preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group.
- the alkenyl group is a straight chain or branched unsaturated hydrocarbon having 2 to 12 carbon atoms, such as a 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, among which vinyl group and allyl group are preferable.
- n represents an integer of 0 to 4, preferably 0 to 2, and more preferably 0.
- R 2 bonded to one benzene ring may be the same or different, but is preferably the same.
- A each independently represents a linear or branched saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms which may have an ether bond, but has a straight ether bond.
- the saturated hydrocarbon which may be sufficient is preferable, and the saturated hydrocarbon which does not have a linear ether bond is still more preferable.
- Examples of the saturated hydrocarbon group for A include linear or branched saturated hydrocarbons having 1 to 12, preferably 2 to 6, more preferably 3 to 4 carbon atoms.
- saturated hydrocarbon groups include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, Dodecamethylene group, methylmethylene group, dimethylmethylene group, methylethylene group, methyleneethylene group, ethylethylene group, 1,2-dimethylethylene group, 1-methyltrimethylene group, 1-methyltetramethylene group, 1,3- Examples thereof include dimethyltrimethylene group and 1-ethyl-4-methyl-tetramethylene group.
- saturated hydrocarbons having 2 to 6 carbon atoms such as ethylene group, trimethylene group, tetramethylene group, pentamethylene group and hexamethylene group. Groups are preferred.
- unsaturated hydrocarbon group for A include linear or branched unsaturated hydrocarbons having 1 to 12, preferably 2 to 6, and more preferably 2 to 4 carbon atoms.
- Specific examples of the unsaturated hydrocarbon group include a vinylene group, an ethynylene group, a propenylene group, a 2-butenylene group, a 2-butynylene group, a 1-vinylethylene group, and the like. Among them, a propenylene group, a 2-butenylene group, etc.
- Aromatic hydrocarbon groups are preferred.
- the hydrocarbon group having an ether bond include an ethyleneoxyethylene group, a tetramethyleneoxytetramethylene group, an ethyleneoxyethyleneoxyethylene group, an ethyleneoxymethyleneoxyethylene group, and a 1,3-dioxane-5,5-bismethylene group.
- ethyleneoxyethylene group and ethyleneoxyethyleneoxyethylene group are preferable.
- n represents an integer of 0 to 5, preferably 0 to 2, and more preferably 0.
- the diphenylsulfone derivative may be a compound having a specific m in the general formula (Chemical Formula 6), or may be a mixture in an arbitrary ratio of compounds having different m in the general formula (Chemical Formula 6).
- diphenylsulfone derivative examples include, but are not limited to, the following compounds.
- 1- (4- (4-hydroxyphenylsulfonyl) phenoxy) -4- (4- (4-isopropoxyphenylsulfonyl) phenoxy) butane is preferred from the viewpoint of the balance between color development sensitivity and storage stability.
- diphenylsulfone derivatives 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane is, for example, JKY-214 manufactured by API Corporation. Is available as
- sensitizer used in the present invention a conventionally known sensitizer can be used.
- sensitizers include fatty acid amides such as stearamide, palmitic acid amide, ethylene bisamide, montanic acid wax, polyethylene wax, 1,2-di- (3-methylphenoxy) ethane, p-benzylbiphenyl, ⁇ - Benzyloxynaphthalene, 4-biphenyl-p-tolyl ether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, di (p-chlorobenzyl) oxalate, di (p-methylbenzyl) oxalate, Dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, phenyl- ⁇ -naphthyl carbonate, 1,4-diethoxynaphthalene, 1-hydroxy-2-naphth, fatty
- 4,4′-butylidene (6-tert-butyl-3-methylphenol), 2 as a stabilizer exhibiting the oil resistance effect of a recorded image and the like within a range not hindering the desired effect on the above problems.
- the binder used in the present invention includes fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy modified polyvinyl alcohol, amide modified polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, butyral modified polyvinyl alcohol, and olefin modified.
- Polyamide resin, silicone resin, petroleum resin, terpene resin, ketone resin, coumaro resin and the like can be exemplified.
- These polymer substances are used by dissolving them in solvents such as water, alcohol, ketones, esters, hydrocarbons, etc., and are used in the state of being emulsified or pasted in water or other media to achieve the required quality. It can also be used in combination.
- crosslinking agent used in the present invention examples include glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, chloride chloride
- examples include ferric iron, magnesium chloride, borax, boric acid, alum, ammonium chloride and the like.
- pigment used in the present invention include inorganic or organic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, and aluminum hydroxide.
- lubricant used in the present invention 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, and silicone resins.
- benzophenone and triazole ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, fluorescent dyes, and the like can be used.
- the type and amount of the dye, developer, and other various components used in the heat-sensitive recording layer of the present invention are determined according to the required performance and recording suitability, and are not particularly limited.
- 0.5 to 10 parts of developer, 0.5 to 10 parts of sensitizer, 0.01 to 10 parts by weight of stabilizer, and 0.01 to 10 parts by weight of other components are used.
- Dye, developer, and materials to be added as needed 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 emulsifier, and depending on the binder and purpose.
- Various additive materials are added to form 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.
- the intermediate layer of the present invention usually comprises a pigment and a binder, and a crosslinking agent may be added.
- a pigment organic pigments such as polyethylene resin, styrene / butadiene copolymer resin, and styrene / acryl copolymer resin may be used in addition to the pigment that can be used in the heat-sensitive recording layer.
- the organic particles may be hollow, and the average particle size is preferably about 5.0 ⁇ m or less.
- the binder or the crosslinking agent a binder or a crosslinking agent that can be used in the heat-sensitive recording layer can be used. Among these, it is preferable that this intermediate layer contains (a) a carboxyl group-containing resin, (b) an epichlorohydrin resin, and (c) a polyamine / amide resin.
- carboxyl group-containing resin monofunctional acrylic monomers having a carboxyl group such as methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc.
- examples thereof include resins containing styrene, oxidized starch, carboxymethylcellulose, carboxyl-modified polyvinyl alcohol in which a carboxyl group is introduced into polyvinyl alcohol, and the like.
- carboxyl-modified polyvinyl alcohol having excellent heat resistance and plasticizer resistance is used. Is preferred.
- the carboxyl-modified polyvinyl alcohol used in the present invention is a reaction product of polyvinyl alcohol and a polycarboxylic acid such as fumaric acid, phthalic anhydride, mellitic anhydride, itaconic anhydride, or an esterified product of these reactants, and vinyl acetate. And a saponified product of a copolymer of maleic acid, fumaric acid, itaconic acid, crotonic acid, acrylic acid, methacrylic acid and the like, and an ethylenically unsaturated dicarboxylic acid. Specifically, for example, the production method exemplified in Example 1 or 4 of JP-A-53-91995 can be mentioned.
- the saponification degree of carboxyl-modified polyvinyl alcohol is preferably 72 to 100 mol%, and the polymerization degree is 500 to 2400, more preferably 1000 to 2000.
- the epichlorohydrin-based resin examples include polyamide epichlorohydrin resin, polyamine epichlorohydrin resin, and the like, which can be used alone or in combination.
- an amine which exists in the principal chain of an epichlorohydrin-type resin the thing from a primary to a quaternary can be used, and there is no restriction
- the degree of cationization and the molecular weight preferably have a cationization degree of 5 meq / g ⁇ Solid (measured value at pH 7) and a molecular weight of 500,000 or more because of good water resistance.
- Sumire Resin 650 (30), Sumire Resin 675A, Sumire Resin 6615 (manufactured by Sumitomo Chemical Co., Ltd.), WS4002, WS4020, WS4024, WS4030, WS4046, WS4010, CP8970 (above, manufactured by Starlight PMC) ) And the like.
- polyamide urea resin polyalkylene polyamine resin, polyalkylene polyamide resin, polyamine polyurea resin, modified polyamine resin, modified polyamide resin, polyalkylene polyamine urea formalin resin, polyalkylene polyamine polyamide polyurea
- Sumire Resin 302 manufactured by Sumitomo Chemical: polyamine polyurea resin
- Sumire Resin 712 manufactured by Sumitomo Chemical: polyamine polyurea resin
- Sumire Resin 703 Sumire Resin 703 (Sumitomo Chemical Co., Ltd.).
- Polyamine resin (polyalkylene polyamine resins, polyamine polyurea type resins, modified polyamine resins, polyalkylene polyamine urea formalin resin, polyalkylene polyamine polyamide polyurea tree) be used preferably.
- the blending amount of these components in the intermediate layer is not particularly limited, but the binder is usually about 10 to 40 parts by weight in solid content with respect to 100 parts by weight of the pigment.
- the blending amount of the carboxyl group-containing resin is preferably 1 to 80 parts by weight, more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the pigment.
- the content of the epichlorohydrin resin and the polyamine / amide resin is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the carboxyl group-containing resin.
- the coating amount of the intermediate layer is about 1 to 15 g / m 2 . If necessary, a water-resistant agent, an antifoaming agent, a lubricant and the like may be added to the intermediate layer.
- a general-purpose coating machine such as a gravure coater, a roll coater, a lip coater, or a bar coater can be used for coating the heat-sensitive recording layer, the thermally active adhesive layer, and the intermediate layer.
- liquids A to C were prepared, and wet grinding was performed with a sand grinder separately until the average particle size became 0.5 ⁇ m.
- Liquid A developer dispersion
- -Diphenylsulfone cross-linking compound Nippon Soda Co., Ltd., trade name: D90
- 6.0 parts-10% aqueous solution of polyvinyl alcohol 18.8 parts-water 11.2 parts solution
- B basic colorless dye dispersion
- -3-dibutylamino-6-methyl-7-anilinofluorane Yamamoto Kasei Co., Ltd., ODB-2
- 3.0 parts-polyvinyl alcohol 10% aqueous solution 6.9 parts-water 3.9 parts
- C solution (Sensitizer dispersion) -1,2-bis (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd., KS232 6.0 parts-polyvinyl alcohol 10%
- the obtained dispersion was mixed at the following ratio to obtain a thermal recording layer coating solution.
- Liquid A developer dispersion
- Liquid B basic colorless dye dispersion
- Liquid C sensitizer dispersion
- Silica manufactured by Mizusawa Chemical, P537) 25 % Dispersion 17.5 parts
- Thermally active adhesive coating solution -Ecobrid S-1 (manufactured by Daicel Finechem Co., Ltd., thermal activation temperature 90 ° C) 100.0 parts-Thickener (San Nopco Co., Ltd., SN thickener 929S) 0.5 parts
- Intermediate layer coating solution 1 -Acrylic resin (Mitsui Chemicals, Barrier Star B1000) 90 parts-Polyamide epichlorohydrin resin (manufactured by Seiko PMC, WS4030) 10 parts intermediate layer coating solution 2: -Carboxyl-modified PVA (manufactured by Kuraray Co., Ltd., PVA-KL318) 85 parts of a 10% solution-polyamide epichlorohydrin resin (manufactured by Seiko PMC, WS4030) 15 parts intermediate layer coating solution 3: -Carboxyl-modified PVA (manufactured by Kuraray Co., Ltd., PVA-KL318) 85 parts of a
- Example 1 Coating and drying the thermal recording layer coating solution on one side of a PET film (A4300 manufactured by Toyobo Co., Ltd., thickness 38 ⁇ m, total light transmittance 90%) with a Meyer bar to a coating amount of 4.0 g / m 2. (Blow dryer, 60 ° C., 2 minutes). On this, the heat-active adhesive coating liquid was applied and dried (Meyer bar at 50 ° C. for 5 minutes) with a Meyer bar so that the coating amount was 10 g / m 2 to prepare a heat-sensitive recording label.
- Example 2 A thermosensitive recording label was produced in the same manner as in Example 1 except that the developer in the thermosensitive recording layer coating liquid of Example 1 was changed to a urea urethane compound (Kemipro Kasei UU).
- Example 3 The developer in the heat-sensitive recording layer coating liquid of Example 1 was 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane (Inc. A heat-sensitive recording label was produced in the same manner as in Example 1 except that JKY-214) manufactured by API Corporation was used. [Example 4] Example 1 with the exception that the thermally active adhesive was changed to Heat Magic DW1040W (manufactured by Toyo Ink Manufacturing Co., Ltd., thermal activation temperature 50 ° C.) and the drying temperature after application of the thermal active adhesive coating liquid was 40 ° C. Similarly, a thermosensitive recording label was produced.
- Heat Magic DW1040W manufactured by Toyo Ink Manufacturing Co., Ltd., thermal activation temperature 50 ° C.
- Example 5 Example 1 except that the heat active adhesive was changed to Eco Brid 5610 (manufactured by Daicel Finechem Co., Ltd., heat activation temperature 70 ° C.) and the drying temperature after application of the heat active adhesive coating liquid was 45 ° C. Thus, a thermosensitive recording label was produced.
- Example 6 The same as in Example 1 except that the developer in the heat-sensitive recording layer coating liquid of Example 1 was changed to 4-hydroxy-4′-allyloxydiphenylsulfone (manufactured by Nikka Chemical Co., Ltd., BPS-MAE). Thus, a thermosensitive recording label was produced.
- Example 7 On the heat-sensitive recording layer of the PET film coated with the heat-sensitive recording layer coating liquid obtained in Example 6, an acrylic pressure-sensitive adhesive (manufactured by Soken Chemical Co., Ltd., SK Dyne 701) was applied instead of the heat-active pressure-sensitive adhesive coating liquid. The heat-sensitive recording label was obtained by coating so that the work amount was 10 g / m 2 . The obtained label was bonded to a separate paper (silicone-treated 11 ⁇ m thick PET film) and stored.
- Example 8 On the heat-sensitive recording layer of the PET film coated with the heat-sensitive recording layer coating liquid obtained in Example 1, the intermediate layer coating liquid 1 is applied and dried with a Meyer bar so that the coating amount is 2.0 g / m 2. (Blow dryer, 60 ° C., 2 minutes). On this, the heat-active adhesive coating liquid was applied and dried with a Meyer bar so that the coating amount was 10 g / m 2 (fan dryer 50 ° C., 5 minutes) to obtain a heat-sensitive recording label. [Example 9] A thermosensitive recording label was produced in the same manner as in Example 8 except that the intermediate layer coating liquid 1 was changed to the intermediate layer coating liquid 2.
- thermosensitive recording label was produced in the same manner as in Example 8 except that the intermediate layer coating liquid 1 was changed to the intermediate layer coating liquid 3.
- the intermediate layer coating liquid 3 was applied with a Mayer bar so that the coating amount was 2.0 g / m 2 and dried. (Blow dryer, 60 ° C., 2 minutes). On this, the heat-active adhesive coating liquid was applied and dried with a Meyer bar so that the coating amount was 10 g / m 2 (fan dryer 50 ° C., 5 minutes) to obtain a heat-sensitive recording label.
- a recording label was prepared.
- a PET film (A4300, manufactured by Toyobo Co., Ltd.) was applied to the thermal recording layer coating solution in which the developer was changed to 4-hydroxy-4'-allyloxydiphenylsulfone (manufactured by Nikka Chemical Co., Ltd., BPS-MAE).
- the heat-sensitive recording layer coating solution was applied and dried with a Meyer bar so that the coating amount was 4.0 g / m 2 (blow dryer, 60 ° C., 2 minutes).
- the protective layer coating solution was coated and dried (fan dryer 60 ° C., 2 minutes) so that the coating amount after drying with a Meyer bar was 4 g / m 2 .
- a thermally active adhesive coating solution was applied to the back surface with a Meyer bar so that the coating amount was 10 g / m 2 (drying at 50 ° C. for 5 minutes) to prepare a thermosensitive recording label.
- RD-914 Macbeth densitometer
- thermo recording paper printing tester equipped with Okura Electric Co., Ltd. TH-PMD, Kyocera Thermal Head
- a checkerboard pattern was printed with / dot.
- the heat-sensitive recording label of Example 7 was printed in the same manner from a separate paper.
- the heat-sensitive recording labels of Comparative Examples 1 and 2 were printed in the same order in the order of the heat-sensitive recording layer surface and the heat-active adhesive layer surface (that is, twice).
- These thermal recording labels were affixed to a polyolefin wrap (manufactured by Nippon Paper Pack Co., Ltd., one wrap), soaked in tap water, and left for 24 hours.
- a thermal recording label printed in the same manner as in the water resistance test is affixed to a polyolefin wrap (manufactured by Nippon Paper Pack Co., Ltd., one wrap), and processed at 24 W for 24 hours at an output of 67 W / m 2 with an Atlas Ci3000F type xenon fade meter. went.
- the prepared thermal label was allowed to stand for 7 days in an environment of 40 ° C.
- the thermal recording labels of the examples other than Example 7 were used with a thermal recording paper printing tester (equipped with Okura Electric Co., Ltd. TH-PMD, Kyocera Thermal Head).
- the adhesive coated surface was in contact with the thermal head.
- the separate paper was in contact with the thermal head.
- the thermal recording label was set so that the coated surface of the thermal recording layer was in contact with the thermal head, and a checkerboard pattern was printed at an applied energy of 0.39 mJ / dot.
- the color density of the printed part was measured, and the color developing ability before and after the treatment was evaluated by the following formula.
- the density of the recording part was measured and evaluated with a Macbeth densitometer (RD-914).
- (Desensitization preventing property) (Color density after standing for 7 days) / (Color density before standing for 7 days) ⁇ 100% Excellent: Desensitization prevention 85% or more Good: Desensitization prevention 75% or more and less than 85% Possible: Desensitization prevention 65% or more but less than 75% Impossibility: Desensitization prevention 65% or less
- thermosensitive recording label of Example 7 Solid printing is performed on the adhesive-coated surface of the thermal recording labels of Examples and Comparative Examples 1 and 2 with a thermal printer (140XiIII, brightness +20, printing speed 51 mm / second, manufactured by Zebra Co., Ltd.) to give energy and provide adhesiveness. Expressed. These thermal recording labels were allowed to stand for 10 seconds and then attached to a polyolefin wrap (manufactured by Nippon Paper Pack Co., Ltd., one wrap). For the thermosensitive recording label of Example 7, the separate paper was peeled off and affixed. After pasting, after standing for 5 days in an environment of 23 ° C.
- thermosensitive recording label of Example 7 the separate paper was peeled off and affixed. Immediately after bonding and after standing for 24 hours in an environment of 23 ° C. and 50% RH, a peel test was performed and evaluated according to the following criteria: Good: Bonded No: Not bonded
- composition of the thermal recording label is shown in Table 1, and the evaluation results are shown in Table 2.
- the heat-sensitive recording labels having the configurations of Examples 1 to 7 have a lower color density than the heat-sensitive recording labels having the configurations of Comparative Examples 1 and 2, but are at a level that is not problematic for practical use. Is far superior, so it can be said that the thermal recording label has an excellent structure.
- the thermosensitive recording labels having the constitutions of Examples 1 to 5 using a specific developer have a color density lower than that of the thermosensitive recording labels using other developers (Example 6). On the other hand, it is a problem-free level. On the other hand, desensitization prevention and print image remaining rate are excellent, color development ability decreases with time, and by heating the adhesive to develop the adhesive. The influence on the heat-sensitive recording layer is reduced.
- thermosensitive recording label (Example 10) having a specific binder or crosslinking agent in the intermediate layer is further excellent in desensitization and print image remaining rate, and color development sensitivity, desensitization, and print image remaining. The balance of rate, adhesiveness, blocking property, etc. is considered to be the best.
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Abstract
Description
一方、紙の片面に粘着剤層を設けた粘着ラベルは価格表示用ラベル、商品表示用ラベル、計量表示用ラベル、広告宣伝用ラベル等のラベル用途に広く用いられている。
近年、このような感熱記録ラベルの用途は、冷凍食品のラベル、酷暑の屋外で貼付される警告ラベルや物流ラベルなどのように過酷な条件で使用されることが多くなってきており、耐水性や耐候性に対する要求は高まっている。
そのため、通常は感熱記録層上に保護層を設けることで、感熱記録ラベルの耐水性や耐候性を向上させる方法がとられている(特許文献4~6等)。
そこで、本発明は従来よりも格段に優れた耐水性や耐候性を有する感熱記録ラベルを提供することを目的とする。
さらに、この構成では、感熱記録層と粘着剤層が接し、粘着剤層の成分が感熱記録層に侵潤することにより発色感度や感熱記録層の膜強度などに悪影響を及ぼす可能性があるが、粘着剤層を構成する粘着剤として、常温で粘着性ではないものや、特に40~100℃の間の温度に加熱することにより粘着性を発現するものを選択することにより、このような点を改善できることを見いだした。
即ち、本願発明は、透明フィルム支持体上に無色ないし淡色の電子供与性ロイコ染料と電子受容性顕色剤とを含有する感熱記録層を設け、該感熱記録層上に、粘着剤を主成分とする粘着剤層を設けてなる感熱記録ラベルである。
この粘着剤は、常温で粘着性ではないことが好ましく、特に40~100℃の間の温度に加熱することにより粘着性を発現するタイプのものが好ましい。
本発明の感熱記録ラベルは、屋外で貼付される警告ラベルや物流ラベルなどに使用できるため、実用的価値が極めて高い。
PETフィルムとしては、東洋紡績株式会社の東洋紡エステル(登録商標)フィルムE5107、E5100、E5101、コスモシャイン(登録商標)A4100、A4300、A8300などが挙げられ、PENフィルムとしては、帝人デュポンフィルム株式会社のテオネックス(登録商標)Q51、Q51DW、Q65F、Q65FA等が挙げられる。
これらの透明フィルムは、各種のUV吸収剤、酸化防止剤、難燃剤、熱安定剤、着色剤、離型剤、軟化材、帯電防止剤、等の添加剤を含有してもよい。
常温で粘着性を有している粘着剤を使用した場合の感熱記録ラベルは、フィルム支持体、感熱記録層、粘着剤層、セパレート紙(剥離紙)の構成となり、断熱性の高いフィルムあるいは紙を通して印字することとなるため、十分な発色性を発現させるには非常に高いエネルギーが必要となる。そのため、粘着剤が常温で粘着性ではないことが好ましい。
また、ホットメルト粘着剤を使用した場合の感熱記録ラベルは、フィルム支持体、感熱記録層、粘着剤層の構成となり、粘着剤層側からエネルギーを加えることができるため良好な発色性を得ることができる。しかしながら、ホットメルト粘着剤の粘着性発現温度は通常100~180℃と高いため、発色性に最適なエネルギーでは十分な粘着性を発現しない可能性があり、逆に、粘着性を十分に発現させるエネルギーを加えた場合には感熱記録層全体が発色してしまう可能性がある。
粘着性を発現させるための加熱方法としては、加熱炉や温風などにより感熱記録ラベル全体を加熱してもよいが、加熱ヘッドなどにより粘着剤層を短時間で部分的に加熱してもよい。後者の場合には、感熱記録層が加熱されないため好ましい。
感熱記録層は、通常90℃で5分程度以上加熱すると、発色して、いわゆる地肌発色(地肌カブリ)が生じることがあり、好ましくない。
したがって、熱活性粘着剤を用いる場合には、粘着性発現温度が上記の温度範囲であるタイプのものを使うことにより、熱活性粘着剤の粘着性を発現させるための加熱による発色の問題を避けることができる。
「常温で粘着性がない」とは、常温で粘着面を乾いた指で触ってもべたつかない程度の粘着性をいい、例えば、JIS-Z-0237に定める粘着性(ボールタック)がボールタック2未満の場合である。
「粘着性を発現する」とは、粘着面を乾いた指で触るとべたつく程度の粘着性をいい、例えば、JIS-Z-0237に定める粘着性がボールタック2以上である。
熱活性粘着剤に用いる熱可塑性樹脂としては、例えばメチルメタクリレート(105℃)、エチルアクリレート(-22℃)、ブチルアクリレート(-54℃)、2-エチルヘキシルアクリレート(-85℃)、カルボキシーポリカプロラクトンアクリレート(-41℃)、コハク酸モノヒドロキシエチルアクリレート(-40℃)、スチレン(100℃)等のビニル芳香族化合物、塩化ビニル(80℃)、塩化ビニリデン(-20℃)等のハロゲン化ビニル、酢酸ビニル(30℃)、プロピオン酸ビニル(10℃)等のビニルエステル、エチレン(-125℃)、ブタジエン(-109℃)等のオレフィン系単量体及びその他アクリロニトリル(130℃)等が挙げられる。括弧内はガラス転移点を示す。
これらの固形可塑剤は二種類以上の混合物としても使用することができる。固形可塑剤の水性分散液は沈降を防止し、塗工物の平滑性を保つためにも一定以下の分散粒径を保つ必要があり、そのため必要に応じてボールミル、ハンディミル等により粉砕分散される。
以下、本発明の感熱記録層に使用される各種材料を例示する。
本発明で使用する電子供与性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〕
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
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
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
ここで、R3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、水素原子、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、好ましくは
水素原子を表す。
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。
また、ハ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。
oは、それぞれ独立して、0~4、好ましくは0を表す。
OH基及び-OR4O-基は、SO2基に対して、パラ位にあることが好ましい。
pは1~11である。この化合物はpが1~11の混合物であることが好ましい。
R4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。ポリアルキレンオキシド鎖(-OR4O-)としては、-O-(CaH2aO)1~3-(a=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、-CbH2b-(bは任意の整数)が挙げられる。
R4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。
このような化合物は、例えば、日本曹達社製D90(下式)として入手可能である。
ここで、R1は、炭素数が1~12、好ましく1~5、より好ましくは1~4の直鎖又は分岐の飽和又は不飽和炭化水素を表すが、飽和炭化水素基としては、例えば、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、t-ブチル、イソアミル等が挙げられる。また、不飽和炭化水素基の炭素数は好ましくは2~5であり、不飽和炭化水素基として、例えば、エチレン、1-n-プロピレン、2-n-プロピレン、イソプロピレン、1-n-ブチレン、2-n-ブチレン、3-n-ブチレン等が挙げられる。
このアルキル基は、炭素数が1~12、好ましく1~5、より好ましくは1~4の直鎖又は分岐の飽和炭化水素であり、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、t-ブチル基、n-ペンチル基、イソペンチル基、ネオペンチル基、t-ペンチル基、n-ヘキシル基、イソヘキシル基、1-メチルペンチル基、2-メチルペンチル基等が挙げられる。
このアルケニル基は、直鎖又は分岐の炭素数が2~12の不飽和炭化水素であり、例えば、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、中でもビニル基、アリル基が好ましい。
Aの飽和炭化水素基としては、炭素数が1~12、好ましくは2~6、より好ましくは3~4の直鎖又は分岐の飽和炭化水素が挙げられる。
飽和炭化水基の具体例としては、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、ウンデカメチレン基、ドデカメチレン基、メチルメチレン基、ジメチルメチレン基、メチルエチレン基、メチレンエチレン基、エチルエチレン基、1,2-ジメチルエチレン基、1-メチルトリメチレン基、1-メチルテトラメチレン基、1,3-ジメチルトリメチレン基、1-エチル-4-メチル-テトラメチレン基等が挙げられ、中でもエチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基等の炭素数2~6の飽和炭化水素基が好ましい。
Aの不飽和炭化水素基としては、炭素数が1~12、好ましくは2~6、より好ましくは2~4の直鎖又は分岐の不飽和炭化水素が挙げられる。不飽和炭化水素基の具体例としては、ビニレン基、エチニレン基、プロペニレン基、2-ブテニレン基、2-ブチニレン基、1-ビニルエチレン基等が挙げられ、中でもプロペニレン基、2-ブテニレン基等の芳香族炭化水素基が好ましい。
エーテル結合を有する炭化水素基としては、例えば、エチレンオキシエチレン基、テトラメチレンオキシテトラメチレン基、エチレンオキシエチレンオキシエチレン基、エチレンオキシメチレンオキシエチレン基、1,3-ジオキサン-5,5-ビスメチレン基等が挙げられ、中でもエチレンオキシエチレン基、エチレンオキシエチレンオキシエチレン基が好ましい。
上記ジフェニルスルホン誘導体は、一般式(化6)において特定のmを有する化合物であってもよいし、一般式(化6)においてmの異なる化合物の任意の割合の混合物であってもよい。
1-[4-(4-ヒドロキシフェニルスルホニル)フェノキシ]-2-[4-(4-イソプロポキシフェニルスルホニル)フェノキシ]エタン、1-[4-(4-ヒドロキシフェニルスルホニル)フェノキシ]-3-[4-(4-イソプロポキシフェニルスルホニル)フェノキシ]プロパン、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、1-[4-(4-ヒドロキシフェニルスルホニル)フェノキシ]-5-[4-(4-イソプロポキシフェニルスルホニル)フェノキシ]ペンタン、1-[4-(4-ヒドロキシフェニルスルホニル)フェノキシ]-6-[4-(4-イソプロポキシフェニルスルホニル)フェノキシ]ヘキサン、1-[4-(4-ヒドロキシフェニルスルホニル)フェノキシ]-7-[4-(4-イソプロポキシフェニルスルホニル)フェノキシ]ヘプタン、1-[4-(4-ヒドロキシフェニルスルホニル)フェノキシ]-8-[4-(4-イソプロポキシフェニルスルホニル)フェノキシ]オクタン、4-(4-[4-(4-ヒドロキシフェニルスルホニル)フェノキシ]ブトキシ)-4'-(4-[4-(4-メトキシフェニルスルホニル)フェノキシ]ブトキシ)ジフェニルスルホン、4-(4-(2-(4-(4-(2-(4-(4-(2-(4-(4-メトキシフェニルスルホニル)フェノキシ)ブトキシ)フェニルスルホニル)フェノキシ)ブトキシ)フェニルスルホニル)フェノキシ)ブトキシ)フェニルスルホニル)フェノールなどが挙げられる。この中で、発色感度と保存性のバランスの点から、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)ブタンが好ましい。
このジフェニルスルホン誘導体のうち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JKY-214として入手可能である。
本発明で使用する顔料としては、シリカ、炭酸カルシウム、カオリン、焼成カオリン、ケイソウ土、タルク、酸化チタン、水酸化アルミニウムなどの無機又は有機充填剤などが挙げられる。
本発明で使用する滑剤としては、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。
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。
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。
顔料としては、上記感熱記録層に使用できる顔料のほか、ポリエチレン系樹脂、スチレン/ブタジエン共重合樹脂、スチレン/アクリル共重合樹脂などの有機粒子を用いてもよい。この有機粒子は中空であってもよく、平均粒子径は好ましくは5.0μm以下程度である。
バインダーや架橋剤としては、上記感熱記録層に使用できるバインダーや架橋剤を使用できる。
このなかで、この中間層が、(a)カルボキシル基含有樹脂、(b)エピクロロヒドリン系樹脂、及び(c)ポリアミン/アミド系樹脂を含有することが好ましい。
カルボキシル基含有樹脂の配合量としては、顔料100重量部に対して1~80重量部配合することが好ましく、より好ましくは10~60重量部である。
エピクロロヒドリン系樹脂及びポリアミン/アミド系樹脂の含有量は、カルボキシル基含有樹脂100重量部に対してそれぞれ1~100重量部であることが好ましく、より好ましくは5~50重量部である。
また、中間層の塗工量は1~15g/m2程度である。
この中間層には、必要に応じて、耐水化剤、消泡剤、滑剤などを添加してもよい。
下記のA液~C液を用意し、それぞれ別々にサンドグラインダーで平均粒子径が0.5μmになるまで湿式磨砕を行った。
A液(顕色剤分散液)
-ジフェニルスルホン架橋型化合物(日本曹達社製、商品名:D90)
6.0部
-ポリビニルアルコール 10%水溶液 18.8部
-水 11.2部
B液(塩基性無色染料分散液)
-3-ジブチルアミノ-6-メチル-7-アニリノフルオラン(山本化成株
式会社製、ODB-2) 3.0部
-ポリビニルアルコール 10%水溶液 6.9部
-水 3.9部
C液(増感剤分散液)
-1,2-ビス(3-メチルフェノキシ)エタン(三光社製、KS232
) 6.0部
-ポリビニルアルコール 10%水溶液 18.8部
-水 11.2部
A液(顕色剤分散液) 36.0部
B液(塩基性無色染料分散液) 13.8部
C液(増感剤分散液) 36.0部
シリカ(水澤化学社製、P537)25%分散液 17.5部
ポリビニルアルコール(10%溶液) 25.0部
熱活性粘着剤塗液:
-エコブリッドS-1(ダイセルファインケム株式会社製、熱活性温度
90℃) 100.0部
-増粘剤(サンノプコ株式会社製、SNシックナー929S) 0.5部
中間層塗液1:
-アクリル樹脂(三井化学社性、バリアスターB1000) 90部
-ポリアミドエピクロロヒドリン樹脂(星光PMC社製、WS4030)
10部
中間層塗液2:
-カルボキシル変性PVA(株式会社クラレ製、PVA-KL318)
10%溶液 85部
-ポリアミドエピクロロヒドリン樹脂(星光PMC社製、WS4030)
15部
中間層塗液3:
-カルボキシル変性PVA(株式会社クラレ製、PVA-KL318)
10%溶液 85部
-ポリアミドエピクロロヒドリン樹脂(星光PMC社製、WS4030)
8部
-変性ポリアミン樹脂(住友化学社製、スミレーズレジンSPI-102
A) 7部
保護層塗液:
-カルボキシル変性PVA(株式会社クラレ製、PVA-KL318)
10%溶液 90部
-ポリアミドエピクロロヒドリン樹脂(星光PMC社製、WS4030)
10部
PETフィルム(東洋紡績株式会社製A4300、厚さ38μm、全光線透過率90%)の片面に感熱記録層塗液をマイヤーバーで塗工量4.0g/m2になるように塗工・乾燥(送風乾燥機、60℃、2分間)した。この上に熱活性粘着剤塗液をマイヤーバーで塗工量10g/m2となるように塗工・乾燥(送風乾燥機50℃、5分間)し、感熱記録ラベルを作製した。
[実施例2]
実施例1の感熱記録層塗液中の顕色剤を、ウレアウレタン系化合物(ケミプロ化成製UU)に変更した以外は、実施例1と同様にして感熱記録ラベルを作製した。
実施例1の感熱記録層塗液中の顕色剤を、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(株式会社エーピーアイコーポレーション製JKY-214)に変更した以外は、実施例1と同様にして感熱記録ラベルを作製した。
[実施例4]
熱活性粘着剤をヒートマジックDW1040W(東洋インキ製造株式会社製、熱活性温度50℃)に変更し、熱活性粘着剤塗液の塗工後の乾燥温度を40℃とした以外は実施例1と同様にして感熱記録ラベルを作製した。
[実施例5]
熱活性粘着剤をエコブリッド5610(ダイセルファインケム株式会社製、熱活性温度70℃)に変更し、熱活性粘着剤塗液の塗工後の乾燥温度を45℃とした以外は実施例1と同様にして感熱記録ラベルを作製した。
実施例1の感熱記録層塗液中の顕色剤を、4-ヒドロキシ-4'-アリルオキシジフェニルスルホン(日華化学株式会社製、BPS-MAE)に変更した以外は、実施例1と同様にして感熱記録ラベルを作製した。
[実施例7]
実施例6で得た感熱記録層塗液を塗工したPETフィルムの感熱記録層上に、熱活性粘着剤塗液の代わりにアクリル系粘着剤(綜研化学株式会社製、SKダイン701)を塗工量10g/m2になるように塗工して感熱記録ラベルを得た。得られたラベルをセパレート紙(シリコーン加工した厚さ11μmのPETフィルム)に貼り合わせて保管した。
実施例1で得た感熱記録層塗液を塗工したPETフィルムの感熱記録層上に、中間層塗液1をマイヤーバーで塗工量2.0g/m2になるように塗工・乾燥(送風乾燥機、60℃、2分間)した。この上に熱活性粘着剤塗液をマイヤーバーで塗工量10g/m2となるように塗工・乾燥(送風乾燥機50℃、5分間)し、感熱記録ラベルを得た。
[実施例9]
中間層塗液1を中間層塗液2に変更した以外は、実施例8と同様にして感熱記録ラベルを作製した。
[実施例10]
中間層塗液1を中間層塗液3に変更した以外は、実施例8と同様にして感熱記録ラベルを作製した。
[実施例11]
実施例6で得た感熱記録層塗液を塗工したPETフィルムの感熱記録層上に、中間層塗液3をマイヤーバーで塗工量2.0g/m2になるように塗工・乾燥(送風乾燥機、60℃、2分間)した。この上に熱活性粘着剤塗液をマイヤーバーで塗工量10g/m2となるように塗工・乾燥(送風乾燥機50℃、5分間)し、感熱記録ラベルを得た。
顕色剤を、4-ヒドロキシ-4'-アリルオキシジフェニルスルホン(日華化学株式会社製、BPS-MAE)に変更した感熱記録層塗液を、PETフィルム(東洋紡績株式会社製A4300)の片面にマイヤーバーで塗工量4.0g/m2になるように塗工・乾燥(送風乾燥機、60℃、2分間)した。次に、感熱記録層と反対の面に熱活性粘着剤塗液をマイヤーバーで塗工量10g/m2となるように塗工・乾燥(送風乾燥機50℃、5分間)して、感熱記録ラベルを作製した。
[比較例2]
顕色剤を、4-ヒドロキシ-4'-アリルオキシジフェニルスルホン(日華化学株式会社製、BPS-MAE)に変更した感熱記録層塗液を、PETフィルム(東洋紡績株式会社製A4300)の片面に感熱記録層塗液をマイヤーバーで塗工量4.0g/m2になるように塗工・乾燥(送風乾燥機、60℃、2分間)した。この上に、保護層塗液をマイヤーバーで乾燥後の塗工量4g/m2となるように塗工・乾燥(送風乾燥機60℃、2分間)した。次いで、裏面に熱活性粘着剤塗液をマイヤーバーで塗工量10g/m2となるように塗工・乾燥(送風乾燥機50℃、5分間)し、感熱記録ラベルを作製した。
<発色濃度>
感熱記録紙印字試験機(大倉電気株式会社製TH-PMD、京セラ社製サーマルヘッドを装着)を用い、実施例7を除く実施例の感熱記録ラベルについては粘着剤塗工面がサーマルヘッドに接するように、実施例7の感熱記録ラベルについてはセパレート紙がサーマルヘッドに接するように、また比較例1と2の感熱記録ラベルについては感熱記録層塗工面がサーマルヘッドに接するように、感熱記録ラベルをセットして、印加エネルギー0.39mJ/dotで市松模様を印字した。
マクベス濃度計(RD-914)を用いて、実施例1~10の感熱記録ラベルについてはフィルム面の印字濃度、比較例1と2の感熱記録ラベルについては感熱記録層塗工面の印字濃度を測定した。
感熱記録紙印字試験機(大倉電気株式会社製TH-PMD、京セラ社製サーマルヘッドを装着)を用いて、実施例7を除く実施例の感熱記録ラベルについて粘着剤層面に、印加エネルギー0.39mJ/dotで市松模様を印字した。実施例7の感熱記録ラベルについてはセパレート紙上から、同様に印字した。比較例1と2の感熱記録ラベルについては感熱記録層面と熱活性粘着剤層面の順に(即ち2度)、同様に印字した。
これらの感熱記録ラベルを、ポリオレフィンラップ(日本紙パック株式会社製、ワンラップ)に貼付し、水道水にどぶ漬けし、24時間放置した。処理前後の発色部濃度を測定し、残存率(=処理後の発色濃度/処理前の発色濃度×100(%))を算出した。
記録部の濃度は、マクベス濃度計(RD-914)で測定し評価した。
良:残存率90%以上
不可:残存率90%未満
耐水性試験と同様に印字した感熱記録ラベルを、ポリオレフィンラップ(日本紙パック株式会社製、ワンラップ)に貼付し、アトラス社製Ci3000F型キセノンフェードメーターにて、出力67W/m2で24時間処理を行った。処理前後の発色部濃度を測定し、残存率(=処理後の発色濃度/処理前の発色濃度×100(%))を算出した。
良:残存率90%以上
不可:残存率90%未満
<減感防止性>
作成した感熱ラベルを40℃、80%RHの環境下で7日間静置した後、感熱記録紙印字試験機(大倉電気株式会社製TH-PMD、京セラ社製サーマルヘッドを装着)を用い、実施例7を除く実施例の感熱記録ラベルについては粘着剤塗工面がサーマルヘッドに接するように、実施例7の感熱記録ラベルについてはセパレート紙がサーマルヘッドに接するように、また比較例1と2の感熱記録ラベルについては感熱記録層塗工面がサーマルヘッドに接するように、感熱記録ラベルをセットして、印加エネルギー0.39mJ/dotで市松模様を印字した。印字部の発色濃度を測定し、処理前後の発色能力を、下記式で評価した。なお、記録部の濃度は、マクベス濃度計(RD-914)で測定し評価した。
(減感防止性)=(7日間静置後の発色濃度)/(7日間静置前の発色濃度)×100%
優:減感防止性85%以上
良:減感防止性75%以上85%未満
可:減感防止性65%以上75%未満
不可:減感防止性65%以下
実施例及び比較例1、2の感熱記録ラベルの粘着剤塗工面に感熱プリンタ(ゼブラ株式会社製、140XiIII、明度+20、印字速度51mm/秒)にてベタ印字を行い、エネルギーを与え粘着性を発現させた。これらの感熱記録ラベルを、10秒間放置した後、ポリオレフィンラップ(日本紙パック株式会社製、ワンラップ)に貼付した。実施例7の感熱記録ラベルについてはセパレート紙を剥離して貼付した。貼付後、23℃、50%の環境下で5日間静置した後、処理前後の発色部濃度を測定し、残存率(=5日間静置後の発色濃度/5日間静置前の発色濃度×100(%))を算出した。
優:残存率85%以上
良:残存率70%以上85%未満
可:残存率50%以上70%未満
不可:残存率50%以下
<接着性>
実施例7を除く実施例及び比較例1、2の感熱記録ラベルの粘着剤塗工面に感熱プリンタ(ゼブラ株式会社製、140XiIII、明度+20、印字速度51mm/秒)にてベタ印字を行い、エネルギーを与え粘着性を発現させた。これらの感熱記録ラベルを、10秒間放置した後、ポリオレフィンラップ(日本紙パック株式会社製、ワンラップ)に貼付した。実施例7の感熱記録ラベルについてはセパレート紙を剥離して貼付した。
接着直後と23℃、50%RHの環境下で24時間静置した後に剥離試験を行い、下の基準で評価した:
良:接着している
不可:接着していない
実施例7を除く実施例及び比較例1、2の感熱記録ラベルを3インチ紙管に巻き付け、40℃、80%RHの環境下で24時間静置、もしくは50℃、80%RHの環境下で24時間静置した。その後、感熱記録ラベルを紙管から剥がし、その剥がした時の抵抗感(耐ブロッキング性)を評価した。実施例7の感熱記録ラベルについては評価しなかった。
良:抵抗なく紙管から感熱記録ラベルが剥がれる
可:剥がすときにやや抵抗感があるが、紙管の表面が毛羽立つ程度であり、紙管が紙むけしたり、感熱記録ラベルが破れることはない
不可:剥がすときに抵抗感があり、無理に剥がすと紙管が紙むけしたり、感熱記録ラベルが破れる
特定の顕色剤を用いた実施例1~5の構成の感熱記録ラベルは、それ以外の顕色剤を用いた感熱記録ラベル(実施例6)に比べて、発色濃度は下がるが、実用に問題ないレベルであり、その一方で減感防止性や印字画像残存率が優れており、経時で発色能力が低下することや、粘着剤に粘着性を発現させるために粘着剤を加熱することによる感熱記録層への影響が低減されている。
中間層を設けた実施例8~11の構成の感熱記録ラベルは、中間層を設けない実施例1~7の構成の感熱記録ラベルに比べて、減感防止性や印字画像残存率が優れている。特に中間層に特定のバインダーや架橋剤を含む構成の感熱記録ラベル(実施例10)は、減感防止性や印字画像残存率が更に優れており、発色感度、減感防止性、印字画像残存率、接着性、ブロッキング性等のバランスが最も良いと考えられる。
Claims (11)
- 透明フィルム支持体上に無色ないし淡色の電子供与性ロイコ染料と電子受容性顕色剤とを含有する感熱記録層を設け、該感熱記録層上に、粘着剤を主成分とする粘着剤層を設けてなる感熱記録ラベル。
- 前記粘着剤が、常温で粘着性ではないことを特徴とする請求項1に記載の感熱記録ラベル。
- 前記粘着剤を一定温度に保った送風乾燥機内に2分間静置し、この粘着剤が粘着性を発現する最低温度が40~100℃の間にある請求項2に記載の感熱記録ラベル。
- 更に、前記感熱記録層と前記粘着剤層との間に中間層を設けた請求項1~3のいずれか一項に記載の感熱記録ラベル。
- 前記中間層が顔料及びバインダーからなる請求項4に記載の感熱記録ラベル。
- 前記中間層が、(a)カルボキシル基含有樹脂、(b)エピクロロヒドリン系樹脂、及び(c)ポリアミン/アミド系樹脂を含有する請求項4に記載の感熱記録ラベル。
- 前記(c)ポリアミン/アミド系樹脂が、ポリアミド尿素系樹脂、ポリアルキレンポリアミン樹脂、ポリアルキレンポリアミド樹脂、ポリアミンポリ尿素系樹脂、変性ポリアミン樹脂、変性ポリアミド樹脂、ポリアルキレンポリアミン尿素ホルマリン樹脂、又はポリアルキレンポリアミンポリアミドポリ尿素樹脂である請求項6に記載の感熱記録ラベル。
- 前記(a)カルボキシル基含有樹脂がカルボキシル変性ポリビニルアルコールである請求項6又は7に記載の感熱記録ラベル。
- (b)エピクロロヒドリン系樹脂及び(c)ポリアミン/アミド系樹脂の含有量が、(a)カルボキシル基含有樹脂100重量部に対してそれぞれ1~100重量部である請求項6に記載の感熱記録ラベル。
- 前記電子受容性顕色剤が、下記一般式
である請求項1~9のいずれか一項に記載の感熱記録ラベル。
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US13/393,827 US8722576B2 (en) | 2009-09-03 | 2010-09-01 | Thermosensitive recording label |
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WO2024078971A1 (de) | 2022-10-11 | 2024-04-18 | Koehler Innovation & Technology Gmbh | Wärmeempfindliches aufzeichnungsmaterial |
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US8722576B2 (en) | 2009-09-03 | 2014-05-13 | Nippon Paper Industries Co., Ltd. | Thermosensitive recording label |
US20140193633A1 (en) * | 2013-01-10 | 2014-07-10 | Ricardo MILLARES-NEYRA | Non-transparent art paper which prevents ink seepage |
US10864703B2 (en) | 2013-01-10 | 2020-12-15 | Ricardo MILLARES-NEYRA | Non-transparent art paper which prevents seepage |
JP2014151611A (ja) * | 2013-02-13 | 2014-08-25 | Oji Holdings Corp | 感熱記録体 |
JP2014218024A (ja) * | 2013-05-09 | 2014-11-20 | 大阪シーリング印刷株式会社 | 感熱記録体 |
US9902131B2 (en) | 2013-07-26 | 2018-02-27 | Osaka Sealing Printing Co., Ltd. | Transparent adhesive sheet |
US9579916B2 (en) | 2013-09-30 | 2017-02-28 | Nippon Paper Industries Co., Ltd. | Thermosensitive recording medium |
US9878567B2 (en) | 2013-11-15 | 2018-01-30 | Osaka Sealing Printing Co., Ltd. | Thermal recording sheet |
US10000083B2 (en) | 2014-06-16 | 2018-06-19 | Nippon Paper Industries Co., Ltd. | Thermosensitive recording medium |
CN106536210A (zh) * | 2014-07-14 | 2017-03-22 | 大阪希琳阁印刷株式会社 | 热敏记录体 |
US10005306B2 (en) | 2014-07-14 | 2018-06-26 | Osaka Sealing Printing Co., Ltd. | Thermosensitive recording body |
WO2016009462A1 (ja) * | 2014-07-14 | 2016-01-21 | 大阪シーリング印刷株式会社 | 感熱記録体 |
JP2016093961A (ja) * | 2014-11-14 | 2016-05-26 | 大阪シーリング印刷株式会社 | 包装シート、ならびにこれを用いた包装容器および包装方法 |
JP2019001141A (ja) * | 2016-06-28 | 2019-01-10 | 株式会社リコー | 感熱記録媒体、及び物品 |
Also Published As
Publication number | Publication date |
---|---|
JP5340394B2 (ja) | 2013-11-13 |
CN102483886B (zh) | 2015-10-07 |
EP2474963A4 (en) | 2013-02-27 |
JPWO2011027752A1 (ja) | 2013-02-04 |
EP2474963A1 (en) | 2012-07-11 |
EP2474963B1 (en) | 2013-11-13 |
US8722576B2 (en) | 2014-05-13 |
CN102483886A (zh) | 2012-05-30 |
US20120208698A1 (en) | 2012-08-16 |
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