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    • 专利摘要:
    The invention relates to a thermal transfer sheet (10) which comprises, in the order mentioned, a substrate (1), a colored layer (2) and an adhesion layer (3) and which is characterized in that the colored layer contains a coloring material, a polyester A resin and a polyester B resin, the number average molecular weight of the polyester A resin is not less than 15000, the average molecular weight of number of the polyester-based resin B is not greater than 5000, the ratio of the mass contents of the polyester-based resin A to the polyester-based resin B in the colored layer is not less than 2 And 3 and not more than 9/1, and the adhesion layer comprises a polyester-based resin. The thermal transfer sheet according to the invention has excellent resistance to organic solvents and excellent printability for fine lines, and at the same time prevents the occurrence of transfer defects.
    公开号:FR3046381A1
    申请号:FR1750101
    申请日:2017-01-05
    公开日:2017-07-07
    发明作者:Yuzu Imakura
    申请人:Dai Nippon Printing Co Ltd；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION
    Field of the Invention [0001]
    The present invention relates to heat transfer sheets, and more particularly to heat transfer sheets which have excellent resistance to organic solvents and excellent printability for fine lines, which heat transfer sheets prevent the occurrence of transfer defects like burrs.
    Background [0002]
    A hot melt transfer system is conventionally known as a printing system which uses a heat transfer sheet, which hot melt transfer system uses a heat transfer sheet which carries a colored layer obtained by dispersion of a coloring material such as a pigment or a dye in a wax or resin on a substrate such as a plastic film. The colored layer is transferred onto a material on which printing is to be applied such as paper or plastic sheet by applying energy according to image information by means of a heating device such as a thermal head. The printing image formed by the hot melt transfer system has a high density and excellent sharpness, and this system is suitable for recording binary image formats such as letters and line art.
    In addition, according to the hot melt transfer system, variable information typically illustrated by the allocation information such as addresses, customer information, numberings and barcodes can be easily issued to and recorded on the material on which printing must be done using a computer and a thermal transfer printer.
    [0003]
    Such a heat transfer sheet should have high adhesiveness to the material on which printing is to be applied and high printability for fine lines. In addition, it must prevent the occurrence of transfer defects such as burrs at the time of transfer.
    In order to meet these requirements, the patent document 1 discloses a heat transfer sheet comprising, in the order mentioned, a release layer, a colored layer and an adhesion layer on a support, where the adhesion layer contains a polyester-based resin with a glass transition temperature of not less than 70 ° C and not more than 80 ° C.
    [0004]
    Furthermore, in cases where such a heat transfer sheet is used in an environment in which an organic solvent such as isopropyl alcohol (AIP) is used, it is necessary that the letters and the like which are formed by the transfer of the colored layer are not erased by the organic solvent used. That is, the heat transfer sheet must have resistance to organic solvents.
    However, conventional heat transfer sheets, including the heat transfer sheet described in Patent Document 1, do not have adequate adhesiveness between the adhesion layer and the material on which printing is to be applied. The adhesion layer also does not come into close contact with the colored layer in an adequate manner. The organic solvent used penetrates into the interstices thus formed so that improvements are possible with respect to the resistance to organic solvents. REFERENCES OF THE PRIOR ART Patent Document [0005]
    Patent Document 1: Japanese Patent Application Publication No. 11-321116 SUMMARY OF THE INVENTION Problems to be Solved by the Invention [0006]
    The Applicant has recently discovered that the organic solvent resistance of the heat transfer sheets can be substantially improved by providing, on a substrate, a colored layer containing a polyester-based resin which has a number average molecular weight which is not less than 15000 and a polyester-based resin which has a number average molecular weight of not more than 5000 in a specific ratio, and an adhesion layer containing a polyester-based resin.
    It has also discovered that, thanks to this thermal transfer sheet, it is possible to print in fine lines without causing a weak impression and a crushed impression, ie to improve the printability for printing. thin lines, and prevent the occurrence of transfer defects such as burrs.
    [0007]
    Therefore, it is an object of the present invention to provide heat transfer sheets which exhibit excellent resistance to organic solvents and excellent printability for fine lines, which heat transfer sheets make it possible to prevent the occurrence of transfer defects like burrs. Means for solving problems [0008]
    The thermal transfer sheet according to the present invention comprises, in the order mentioned, a substrate, a colored layer and an adhesion layer, and is characterized in that the colored layer contains a coloring material, a polyester-based resin A and a polyester-based resin B, the number-average molecular weight of the polyester-A-based resin is not less than 15,000, the number-average molecular weight of the polyester-B-based resin is not greater than 5000, the ratio of the mass contents of the polyester A resin to the polyester B resin (polyester A resin / polyester B resin) in the colored layer is not less than at 2/3 and not more than 9/1; and the adhesion layer comprises a polyester-based resin.
    [0009]
    Preferably, the ratio of the mass contents of the polyester A resin to the polyester B resin (polyester A resin / polyester B resin) in the colored layer is not less than 1/1 and not more than 4/1.
    [0010]
    Preferably, the thickness of the colored layer is not less than 0.2 μm and not greater than 0.8 μm.
    [0011]
    Preferably, the number average molecular weight of the polyester-based resin contained in the adhesion layer is not less than 2000 and not more than 25,000.
    [0012]
    Preferably, the heat transfer sheet further comprises a separation layer between the substrate and the colored layer.
    EFFECTS OF THE INVENTION
    [0013]
    According to the present invention, thermal transfer sheets which have a high resistance to organic solvents can be provided, where the letters and the like formed by transfer of the colored layer are not erased by an organic solvent.
    In addition, it is possible to provide thermal transfer sheets which have excellent printability for fine lines and which prevent the occurrence of transfer defects such as burrs.
    DESCRIPTION OF THE DRAWINGS
    [0014]
    Fig. 1 is a schematic cross-sectional view showing an embodiment of the thermal transfer sheet of the present invention.
    Fig. 2 is a figure which shows a printing pattern used in the evaluation of the printability for fine lines in the examples.
    Fig. 3 is a figure showing a printing pattern used in the evaluation of burrs in the examples.
    Fig. 4 is a figure which shows a printing pattern used in the evaluation of resistance to organic solvents in the examples.
    DETAILED DESCRIPTION
    [0015]
    Thermal transfer sheet
    As shown in FIG. 1, the thermal transfer sheet 10 according to the present invention comprises, in the order mentioned, a substrate 1, a colored layer 2 and an adhesion layer 3.
    In addition, in one embodiment, the heat transfer sheet 10 may comprise a separation layer 4 between the substrate 1 and the colored layer 2.
    Further, in one embodiment, the thermal transfer sheet 10 may comprise a backing layer 5 on the other surface of the substrate 1, this surface being opposite the surface which is provided with the separation layer 2.
    Each of the layers composing the thermal transfer sheet according to the present invention will be explained below.
    [0016]
    substratum
    Any substrate may be used provided that it is a conventionally known substrate which has a certain degree of thermal resistance and mechanical strength; and examples of such substrates include resin films such as polyethylene terephthalate (PET) films, 1,4-polycyclohexylene dimethylene terephthalate films, polyethylene naphthalate (PEN) films, phenylene polysulfide films, films, and the like. of polystyrene (PS), polypropylene (PP) films, polysulfone films, aramid films, polycarbonate films, polyvinyl alcohol films, cellulose derivatives such as cellophane and cellulose, polyethylene (PE) films, poly (vinyl chloride) films, nylon films, polyimide films and ionomer films.
    [0017]
    The above substrate may be surface treated to improve adhesiveness to a neighboring layer. As a surface treatment of this type, it is possible to apply known techniques for modifying the surface of resins such as a corona discharge treatment, a flame treatment, an ozone treatment, an ultraviolet treatment, a treatment by radiation, treatment conferring surface roughness, chemical treatment, plasma treatment or grafting treatment. Of these surface treatments, corona discharge treatment or plasma treatment is preferred in the present invention because it is inexpensive. It is possible to apply one type of treatment among the surface treatments mentioned above or two or more types of these treatments.
    [0018]
    In addition, the substrate may, as necessary, comprise an underlayer (base layer) on one of its surfaces or on both surfaces. The base layer can be formed by coating. In addition, the base layer can also be formed, for example, by applying a base coat liquid to an unstretched plastic film at the time of its melt extrusion deposition, after which a treatment of stretching is performed. Such a base layer can be formed, for example, from the following organic materials and inorganic materials.
    Examples of organic materials include polyester resins, polyurethane resins, (meth) acrylic resins, polyamide resins, polyether resins, polystyrene resins, resins, and the like. polyvinyl resins, cellulose resins and polyolefin resins.
    Examples of inorganic materials include ultrafine particles of inorganic colloidal pigments such as silica (colloidal silica), alumina or alumina hydrates (such as alumina sol, colloidal alumina, cationic aluminum oxides or the like). their hydrates, pseudo-boehmite), aluminum silicates, magnesium silicates, magnesium carbonate, magnesium oxide and titanium oxide.
    In addition to these, a polymer that has an organic backbone that is formed from an organic titanate, for example, tetrakis (2-ethylhexyl) titanate, bis (ethyl-3-oxobutanolate-01.03 bis (2-propanolate) titanium, or isopropyl titanate and triisostearoyl titanate, or which is formed from a titanium alkoxide, for example titanium tetraisopropoxide or titanium tetra-n-butoxide, can be used as the base layer material.
    [0019]
    Preferably, the thickness of the substrate is not less than 2 μm and not more than 25 μm and more preferably not less than 3 μm and not more than 10 μm.
    [0020]
    Colorful layer
    The colored layer preferably contains a coloring material, a polyester-based resin A (which may be referred to in some cases in the following as high molecular weight polyester resin) which has a number average molecular weight (Mn) which is not less than 15000, and a polyester B-based resin (which may be referred to in some cases as low molecular weight polyester resin) which has an Mn of not more than 5000.
    In addition, the colored layer may contain two or more types of polyester A-based resins or may contain two or more types of polyester B-based resins.
    Preferably, the Mn of the polyester-based resin A is not less than 15000 and not more than 40000 and more preferably not less than 15000 and not more than 25000.
    Preferably, the Mn of the polyester-based resin B is not less than 2000 and not more than 5000.
    Due to the fact that the colored layer contains a polyester A-based resin and a polyester-based resin B which have the above Mn, the occurrence of burrs or the like at the time of heat transfer can be prevented and at the same time the organic solvent resistance of the heat transfer sheet can be improved.
    It should be noted that Mn is a value obtained by gel permeation chromatography with polystyrene (GPC) according to JIS K 7252-1 (2008).
    [0021]
    It should be noted that in the present description, a "polyester-based resin" means an ester group-containing polymer obtained by polycondensation of a polyfunctional carboxylic acid with a polyhydric alcohol; and examples of such resins include PET, polyethylene isophthalate, polybutylene terephthalate, polypropylene terephthalate, polycyclohexanedimethylene terephthalate and PEN.
    In addition, examples of polyfunctional carboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, decanedicarboxylic acid, azelaic acid, dodecanedicarboxylic acid and cyclohexanedicarboxylic acid.
    In addition, examples of polyalcohols include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, decanediol, 2-ethyl-butyl-1-propanediol and bisphenol. AT.
    In addition, the polyester-based resin may be a resin obtained by copolymerization of three or more of three types of polyfunctional carboxylic acids and polyalcohols above, or it may be a copolymer thereof with a monomer or a polymer such as diethylene glycol, triethylene glycol or polyethylene glycol.
    In addition, in the present description, the polyester-based resin also includes the modified products of such a resin. Examples of modified products of the polyester-based resin include urethane-modified polyester resins.
    [0022]
    The ratio of the mass contents of the polyester A resin to the polyester B resin (polyester A resin / polyester B resin) in the colored layer is preferably a ratio which is not not less than 2/3 and not more than 9/1. More preferably, this ratio of the contents is not less than 1/1 and not more than 4/1.
    Because the colored layer contains the polyester A resin and the polyester B resin, ie the high molecular weight polyester resin and the low polyester resin. In the above ratio, the occurrence of burrs or the like at the time of heat transfer can be prevented and, at the same time, the resistance to organic solvents of the heat transfer sheet can be further improved.
    [0023]
    Preferably, the glass transition temperature (Tg) of the polyester-based resins A and B is not less than 20 ° C and not more than 90 ° C and more preferably not less than 50 ° C. ° C and not more than 80 ° C.
    By adjusting the Tg of the polyester-based resin A and the polyester-based resin B which are contained in the colored layer in the range of numerical values above, the occurrence of a contact adhesion can be sufficiently eliminated. or reduced while the transferability of the heat transfer sheet is fully maintained.
    It should be noted that Tg can be determined on the basis of a measurement of changes in heat quantity by DSC (differential scanning calorimetry) (DSC method) according to JIS K 7121 (2012).
    [0024]
    Preferably, the total content of the polyester A resin and the polyester B resin in the colored layer is not less than 30% by weight and not more than 90% by weight and more preferably it is not less than 40% by mass and not more than 70% by mass.
    By adjusting the total content of the polyester A resin and the polyester B resin in the colored layer in the above numerical range, the colored layer can come into closer contact with the polyester layer. adhesion, so that the resistance to organic solvents and the resistance to friction can be improved. In addition, a high print density can be obtained.
    [0025]
    The colored layer may contain another resin to the extent that the effects of the present invention are not degraded. Examples of such resins include acrylic resins, polyurethane resins, vinyl resins, cellulose resins, melamine resins, polyamide resins, polyolefin resins, and polyurethane resins. resins based on styrene.
    From the point of view of obtaining a high resistance to organic solvents, preferably, the content of the other resin in the colored layer is not more than 20% by weight and, more preferably, it does not is not more than 5% by mass. Particularly preferably, the colored layer does not contain other resins.
    [0026]
    The coloring matter contained in the colored layer may be selected as appropriate, depending on the required color hue, among carbon black, inorganic pigments and organic pigments or dyes for use. For example, particularly in the case of barcode printing, the preferred dyestuffs are those which have a sufficient black color density and which do not undergo color change or weakening under the action of light, heat or the like. Examples of such dyestuffs include carbon black such as lamp black, graphite and nigrosine dyes. In addition, in cases where color printing is required, dyes or pigments having other color colors are used.
    [0027]
    The colored layer may contain an additive such as inorganic fine particles, organic fine particles, a mold release agent, a dispersant or an antistatic agent to the extent that the effects of the present invention are not degraded.
    [0028]
    Preferably, the thickness of the colored layer is not less than 0.2 μm and not more than 0.8 μm and more preferably not less than 0.3 μm and not more than 0 μm. , 7 pm.
    By adjusting the thickness of the colored layer in the range of numerical values above, its printability for fine lines can be improved.
    [0029]
    The colored layer may be formed by dissolving the above material, as necessary, in a suitable solvent such as acetone, methyl ethyl ketone, toluene or xylene to obtain a colored layer coating liquid, application of this liquid on a substrate by a printing process or a suitable coating process commonly used as gravure coating, roll coating and wire bar coating, and then heating and drying the resultant product to a substrate. temperature not less than 30 ° C and not more than 80 ° C.
    [0030]
    Membership layer
    The adhesion layer is disposed on the colored layer and contains a polyester-based resin.
    Due to the fact that the adhesion layer contains a polyester-based resin, its adhesiveness to the material on which printing is to be applied and to the colored layer is improved so that its resistance to organic solvents can be improved.
    [0031]
    Preferably, the Mn of the polyester-based resin contained in the adhesion layer is not less than 2000 and not more than 25,000 and more preferably not less than 3000 and not more than 20,000. .
    By adjusting the Mn of the polyester-based resin contained in the adhesion layer in the range of numerical values above, the resistance to organic solvents and the resistance to friction can be improved, while the transferability of the polyester-based resin can be improved. the heat transfer sheet is maintained.
    [0032]
    In addition, preferably, the Tg of the polyester-based resin is not less than 20 ° C and not more than 90 ° C and more preferably not less than 50 ° C and not more than at 80 ° C.
    By adjusting the Tg of the polyester-based resin in the range of numerical values above, the occurrence of a contact adhesion can be sufficiently eliminated or reduced, while the transferability of the thermal transfer sheet is fully maintained.
    [0033]
    Preferably, the content of the polyester-based resin in the adhesion layer is not less than 50% by weight and not more than 100% by weight and, more preferably, it is not less than 70% by weight. % by weight and not more than 100% by mass.
    By adjusting the content of the polyester-based resin in the adhesion layer in the range of numerical values above, the adhesiveness of the adhesion layer to a material on which an impression is to be made applied can be increased, and the adhesion layer can come into closer contact with the colored layer. Thus, resistance to organic solvents can be improved.
    [0034]
    The adhesion layer may contain another resin to the extent that the effects of the present invention are not degraded.
    Examples of such resins include acrylic resins, polyurethane resins, vinyl resins, cellulose resins, melamine resins, polyamide resins, polyolefin resins, and polyurethane resins. resins based on styrene.
    [0035]
    Preferably, the thickness of the adhesion layer is not less than 0.1 μm and not more than 0.6 μm and more preferably not less than 0.2 μm and not more than at 0.5 pm.
    By adjusting the thickness of the adhesion layer in the range of numerical values above, the printability for fine lines can be improved.
    [0036]
    The adhesion layer may be formed by dissolving the above material, as necessary, in a suitable solvent such as acetone, methyl ethyl ketone, toluene or xylene to obtain a coating liquid for the coating layer. adhesion, application of this liquid to a substrate by a printing process or a suitable coating method commonly used as gravure coating, roll coating and coating by means of a wire bar, and then heating and drying the resulting product at a temperature of not less than 30 ° C and not more than 80 ° C.
    [0037]
    Separation layer
    The separating layer is disposed between the substrate and the colored layer and is transferred, with the colored layer, onto a material on which printing is to be applied when heat transfer is performed.
    [0038]
    The separating layer may contain, for example, a cellulose-based resin, a vinyl resin, a polyurethane resin, a silicone-based resin, a fluororesin, a silicone wax or a modified resin or wax with fluoride. Examples of waxes include microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylenes, Japanese wax, beeswax, spermaceti wax, insect wax, wool wax, shellac wax, candelilla wax, petrolatum, partially modified waxes, fatty acid esters and fatty acid amides. Among them, the use of carnauba wax makes it possible to obtain a better separation from the substrate and the net formation of thin lines and the like. At the same time, this use allows the appropriate transfer of heat from the thermal head to the colored layer and makes it possible to obtain a good transfer on a material on which an impression must be applied.
    [0039]
    Preferably, the thickness of the separation layer is not less than 0.4 μm and not greater than 1.2 μm; and, more preferably, it is not less than 0.5 μm and not more than 1.0 μm. By adjusting the thickness of the separating layer in the above numerical value range, the printability on a material to which an impression is to be applied which has a lack of uniformity on its surface can be improved. and at the same time the occurrence of burrs can be prevented.
    [0040]
    The separating layer may be formed by dissolving the above material, as necessary, in a suitable solvent such as acetone, methyl ethyl ketone, toluene or xylene to obtain a separating layer coating liquid. applying this liquid to a substrate by a commonly used printing process or coating method commonly used, such as gravure coating, roll coating and wire bar coating, and then heating and drying the product resulting in a temperature of not less than 30 ° C and not more than 80 ° C.
    [0041]
    Back layer
    In the present invention, the backing layer 5 is a layer which is provided, if desired, for the purpose of preventing negative effects such as the occurrence of adhesion or wrinkling due to heating from the dorsal surface of the substrate (side of the substrate on which the colored layer is not arranged) when a heat transfer is performed. Due to the presence of the backing layer, heat transfer can be achieved without causing adhesion even in a thermal transfer sheet which has as a substrate a plastic film having poor thermal resistance; and it is possible to obtain the advantages that are attributed to plastic films as the fact that they cut with difficulty and that they are easy to implement.
    [0042]
    The backing layer may comprise a binder resin; and examples of such resins include cellulose based resins, styrene resins, vinyl resins, polyester resins, polyurethane resins, silicone modified urethane resins, fluorine-modified urethane resins and acrylic resins. Of these, styrene-based resins, specifically styrene-acrylonitrile copolymer resins, are preferably used to avoid calcination and adhesion of the thermal head to the backing layer and to prevent formation of debris.
    In addition, a bicomponent curable resin that can be cured with an isocyanate compound or the like can be contained as a binder resin. Examples of such resins include polyvinyl acetal resins and polyvinyl butyral resins.
    The isocyanate compound is not particularly limited and it is possible to use conventionally known isocyanate compounds. Of these, it is desirable to use aromatic isocyanate adducts. Examples of aromatic polyisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, toluidine diisocyanate, p-phenylene diisocyanate, trans-cyclohexane-1,4-diisocyanate, xylylene diisocyanate, triphenylmethane triisocyanate and tris (isocyanato-phenyl) thiophosphate; and, in particular, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate or a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is preferred.
    [0043]
    In addition to the above component, inorganic or organic fine particles may be added to the backing layer for auxiliary adjustment of the lubricating properties. Examples of inorganic fine particles include clay minerals such as talc and kaolin; carbonates such as calcium carbonate and magnesium carbonate; hydroxides such as aluminum hydroxide and magnesium hydroxide; sulphates of calcium sulphate; oxides such as silica; and inorganic fine particles such as graphite, saltpetre and boron nitride. Examples of organic fine particles include fine organic resin particles composed of acrylic resins, Teflon resin (registered trademark), silicone resins, lauroyl resins, phenolic resins, acetal resins, resins of polystyrene, nylon resins, or the like; or the fine particles of cross-linked resin obtained by reaction thereof with a crosslinking agent. Of the inorganic or organic fine particles above, talc can be suitably used.
    [0044]
    Preferably, the thickness of the backing layer is not less than 0.03 μm and not more than 1.0 μm and more preferably not less than 0.05 μm and not more than 0 μm. , 5 pm. By adjusting the thickness of the backing layer in the range of numerical values above, negative effects such as occurrence of adhesion or wrinkling can be prevented, while heat transfer from the thermal head is maintained for obtain sufficient printing density.
    [0045]
    The backing layer can be formed by dissolving the above material in a suitable solvent such as acetone, methyl ethyl ketone, toluene or xylene to obtain a backcoat coating liquid, applying this liquid to a substrate by a printing method or a suitable coating method commonly used as gravure coating, roll coating and coating by means of a wire bar, and then heating and drying the resulting product at a temperature not lower than at 30 ° C and not higher than 110 ° C.
    [0046]
    Other layer
    In one embodiment, the thermal transfer sheet of the present invention may include a release layer between the substrate and the release layer. The release layer is a layer that remains on the substrate when the heat transfer is performed.
    In addition, in one embodiment, the thermal transfer sheet according to the present invention may comprise an intermediate layer which improves the adhesiveness between any layers.
    [0047]
    In the present invention, the thickness of each of the layers composing the heat transfer sheet has been measured by means of a method of inclusion in a resin.
    Specifically, a heat transfer sheet (sample) was cut and then included in an epoxy resin; a cross section was formed by cutting the sample in the direction of its thickness by means of an ultrafine cutting process (cutting with a microtome and a diamond cutting device); this cross section was subjected to the action of an ion spray device (manufactured by Hitachi High-Technologies Corporation, trade name: E-1045, target: Pt, electric current: 15 mA, 10 seconds); a cross-sectional image of the sample was then acquired by means of a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, trade name: S-4800 TYPE I, acceleration voltage: 3.0 kV, emission current: 10 μΑ, working distance: 8 mm, detector: Mix); and the thickness was measured from this image.
    EXAMPLES
    [0048]
    The present invention will now be described in more detail by way of examples; however, the present invention is not limited to these examples. It should be noted that, unless otherwise indicated, the parts or% are in mass.
    [0049]
    Example 1 To a surface of a substrate sheet consisting of a PET film which was 4.5 μm thick, which had been treated to improve adhesion, a backcoat coating liquid which had the composition The underside was applied in such a way that the amount of coating was 0.3 g / m 2 in terms of solids content and then dried to form a backing layer. It will be noted that the thickness of the backing layer was 0.3 μm.
    Dorsal coating liquid copolymer resin styrene-acrylonitrile 11 parts linear saturated polyester resin 0.3 part zinc stearyl phosphate 6 parts melamine resin powder 3 parts methyl ethyl ketone 80 parts [0050]
    Then, at a portion of the other surface of the substrate sheet, which surface was opposed to the surface provided with the backing layer, a release layer coating liquid having the composition below was applied in such a manner that the amount of coating on a dry basis was 0.6 g / m 2 in terms of solids content and then dried to thereby form a separating layer. It will be noted that the thickness of the separation layer formed was 0.6 μm.
    Separation layer coating liquid 1 carnauba wax 100 parts water 450 parts AIP 450 parts [0051] To the thus formed separation layer, a colored layer coating liquid which had the composition below was applied in such a manner that the amount of coating on a dry basis was 0.45 g / m 2 and then dried to thereby form a colored layer. The mixing ratio (Al / Bl) of the high molecular weight polyester resin (Al) to the low molecular weight polyester resin (B1) was 1/1. It will be noted that the thickness of the colored layer formed was 0.4 μm.
    Coating liquid for carbon black colored layer 33.4 parts polyester resin Al 33.3 parts (Mn: 17000, Tg: 67 ° C) Polyester resin Bl 33.3 parts (Mn: 3000, Tg : 53 ° C) toluene 450 parts methyl ethyl ketone 450 parts [0052] To the colored layer thus formed, an adhesion layer coating liquid which had the composition below was applied in such a way that the amount of coating on a Dry base was 0.3 g / m 2, then dried to form an adhesion layer, thereby preparing a heat transfer sheet. It will be noted that the thickness of the adhesion layer formed was 0.3 μm.
    Polyester based resin adhesion layer coating liquid X 100 parts (Mn: 5000, Tg: 70 ° C) water 450 parts AIP 450 parts [0053]
    Example 2
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the polyester-based resin B1 contained in the colored coat liquid was replaced by the polyester-based resin. B2 (Mn: 3000, Tg: 53 ° C).
    [0054]
    Example 3
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the amount of polyester-based resin Al and the amount of polyester-based resin B1 contained in the coating liquid for color layer were modified to be equal to 53.36 parts and 13.34 parts, respectively, to bring the mixing ratio (Al / Bl) of the high molecular weight polyester resin (Al) to the resin to Low molecular weight polyester base (Bl) to be 4/1.
    [0055]
    Example 4
    A heat transfer sheet was prepared in the same manner as described in Example 3 except that the polyester-based resin B1 contained in the colored coat liquid was replaced by the polyester-based resin. B2.
    [0056]
    Example 5
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the amount of polyester-based resin Al and the amount of polyester-based resin B1 contained in the coating liquid for color layer were modified to equal 26.68 parts and 40.02 parts, respectively, to bring the mixing ratio (Al / Bl) of the high molecular weight polyester resin (Al) to the resin to Low molecular weight polyester base (Bl) to be 2/3.
    [0057]
    Example 6
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the amount of polyester-based resin Al and the amount of polyester-based resin B1 contained in the coating liquid for color layer were modified to be equal to 60.03 parts and 6.67 parts, respectively, to bring the mixing ratio (Al / Bl) of the high molecular weight polyester resin (Al) to the resin to low molecular weight (Bl) polyester base to be 9/1.
    [0058]
    Example 7
    A heat transfer sheet was prepared in the same manner as that described in Example 1 except that the polyester-based resin X contained in the coating liquid for the adhesion layer was replaced by the resin-based polyester Y (Mn: 8000, Tg: 77 ° C).
    [0059]
    Example 8
    A heat transfer sheet was prepared in the same manner as that described in Example 1 except that the polyester-based resin X contained in the coating liquid for the adhesion layer was replaced by the resin-based polyester Z (Mn: 18000, Tg: 67 ° C).
    [0060]
    Example 9
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the composition of the colored coating liquid was modified as follows. The mixing ratio of the high molecular weight polyester resins (Al and A3) to the low molecular weight polyester resin (B1) ((Al + A3) / B1) was 2/1.
    Coating liquid for carbon black colored layer 33.4 parts Al polyester resin 22.2 parts (Mn: 17000, Tg: 67 ° C) A3 polyester resin 22.2 parts (Mn: 22000, Tg 72 ° C.) B 22.2 parts polyester resin (M n: 3000, T g: 53 ° C) 450 parts methyl ethyl ketone toluene 450 parts [0061]
    Example 10
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the thickness of the release layer was changed to 1.0 μm, the thickness of the The colored layer was modified to 0.8 μm and the thickness of the adhesion layer was changed to 0.2 μm.
    [0062]
    Example 11
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the thickness of the colored layer was changed to 0.2 μm and the thickness of the layer adhesion has been changed to 0.4 μm.
    [0063]
    Example 12
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the composition of the colored coating liquid was modified as follows. The mixing ratio of the high molecular weight polyester resin (A2) to the low molecular weight polyester resin (B1) (A2 / B1) was 1/1.
    Coating liquid for black carbon colored layer 33.4 parts polyester resin A2 33.3 parts (Mn: 15000, Tg: 60 ° C) Polyester resin Bl 33.3 parts (Mn: 3000, Tg : 53 ° C) toluene 450 parts • methyl ethyl ketone 450 parts [0064]
    Example 13
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the composition of the colored coating liquid was modified as follows. The mixing ratio of the high molecular weight polyester resin (A3) to the low molecular weight polyester resin (B1) (A3 / B1) was 1/1.
    Coating liquid for colored layer 1 carbon black 33.4 parts polyester-based resin A3 33.3 parts (Mn: 22000, Tg: 60 ° C) polyester-based resin Bl 33.3 parts (Mn: 3000, Tg: 53 ° C) toluene 450 parts methyl ethyl ketone 450 parts [0065]
    Comparative Example 1
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the composition of the colored coating liquid was modified as follows.
    Coating liquid for carbon black colored layer 33.4 parts acrylic resin 33.3 parts (Mn: 20000, Tg: 100 ° C) copolymer vinyl chloride-vinyl acetate 33.3 parts (degree of polymerization: 400, Tg : 70 ° C) toluene 450 parts methyl ethyl ketone 450 parts [0066]
    Comparative Example 2
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the polyester-based resin B1 contained in the colored coat liquid was replaced by the polyester-based resin. B3 (Mn: 8000, Tg: 65 ° C).
    [0067]
    Comparative Example 3
    A heat transfer sheet was prepared in the same manner as described in Example 3 except that the polyester-based resin B1 contained in the colored coat liquid was replaced by the polyester-based resin. B3 (Mn: 8000, Tg: 65 ° C).
    [0068]
    Comparative Example 4
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the amount of polyester-based resin Al and the amount of polyester-based resin B1 contained in the coating liquid for color layer were modified to equal 20.1 parts and 46.69 parts, respectively, to bring the mixing ratio (Al / Bl) of the high molecular weight polyester resin (Al) to the resin to Low molecular weight polyester base (Bl) to be 3/7.
    [0069]
    Comparative Example 5
    A heat transfer sheet was prepared in the same manner as described in Example 1 except that the composition of the colored coating liquid was modified as follows.
    Coating liquid for colored layer 1 carbon black 33.3 parts polyester-based resin Al 66.7 parts (Mn: 17000, Tg: 67 ° C) toluene 450 parts methyl ethyl ketone 450 parts [0070] [Table 11
    [TITLE 2]
    [0072] TTablet 31
    [0073]
    The heat transfer sheets obtained in the Examples and Comparative Examples were subjected to the following tests for evaluation. The evaluation results of each test are presented in Table 4.
    [0074]
    Printability for fine lines
    One print was made one step at a time using a Zebra 96XIII printer (thermal head 600 dpi (dots per inch (1 inch = 2.54 cm), 236 dots per centimeter) manufactured by Zebra Technologies at one time. printing speed of 4 PPS (inches per second; 10 centimeters per second) with print energy ranging from 20 to 30. Bar codes in stakes including fine lines having a width of one point (see Figure 2) were printed as a printing pattern using a silver PET label (manufactured by Avery Dennison, trade name: 72826) as the material to be printed on, the printed material was visually assessed. evaluation were as follows.
    Evaluation Criteria 3: Thin line printing without weak printing and dot gain can be achieved with print energy of not less than 2. 2: Fine line printing without a weak print and without fattening point can be achieved with a print energy of 1. 1: No print energy range is available; a weak impression or a fattening of the point occurs; and fine line printing is impossible.
    [0075]
    burr
    Printing was done using a TEC B-SX5T label printer manufactured by Toshiba Tec Corporation at a print speed of 76.2 mm / s (3 PPS) with print energy of 0. Codes Ladder bars (see Fig. 3) were printed using a white PET label (manufactured by Avery Dennison, trade name: 72825) as the material on which printing is to be applied.
    The printed material obtained using the heat transfer sheets of the Examples and Comparative Examples was evaluated for the presence of burrs by means of a Quick Check 850 Barcode Checker (manufactured by Honeywell). The evaluation criteria were as follows.
    Evaluation Criteria 3: There is no burr and the result determined by the barcode checker is A or B. 2: Burrs occur slightly and the result determined by the barcode checker is C or D. 1: Burrs occur and the result determined by the barcode verifier is F or non-determinable.
    Resistance to organic solvents (resistance to ΓΑΙΡ)
    Stake bar codes (see Figure 4) were printed on a white PET label (material to be printed on, manufactured by Avery Dennison, Trade Name: 72825) using the heat transfer sheets of the examples. and comparative examples and a Zebra 105SL printer (manufactured by Zebra Technologies). At this point, the print speed was set at 4 PPS and the print energy was set at 26.
    Subsequently, the printed surface of the material on which printing was to be applied was rubbed back and forth 100 times by a FR-2S type color-resistance tester ( manufactured by Suga Test Instruments Co., Ltd., conforms to a type II friction tester of JIS L 0849 (2013)) with a cotton fabric saturated with 0.5 cm 3 of isopropyl alcohol (AIP) with a load of 800 g. The condition of the printed surface after rubbing was evaluated for organic solvent resistance using a Quick Check 850 barcode checker (manufactured by Honeywell). The evaluation criteria were as follows.
    It should be noted that the evaluation of the resistance to organic solvents was carried out after it was ensured that all the evaluation results obtained with the bar code verifier before the friction corresponded to a grade of A.
    Evaluation Criteria 3: The result determined by the Bar Code Verifier after friction gives a score of A. 2: The result determined by the Bar Code Verifier after friction gives a score of B or C. 1: The result determined by the bar code checker after rubbing gives a rating of D or less.
    [Table]
    Description of symbols [0078] 1 Substrate 2 Color layer 3 Adhesion layer 4 Separation layer 5 Back layer 10 Thermal transfer sheet
    权利要求:
    Claims (5)
    [1" id="c-fr-0001]
    A thermal transfer sheet (10) comprising, in the order mentioned, a substrate (1), a colored layer (2) and an adhesion layer (3), characterized in that said colored layer comprises a coloring material , a polyester-based resin A and a polyester-based resin B, the number-average molecular weight of said polyester-based resin A is not less than 15000, the number-average molecular weight of said resin-based of polyester B is not more than 5000, the ratio of the mass contents of said polyester-based resin A to said polyester-based resin B (polyester-based resin A / polyester-based resin B) in said colored layer is not less than 2/3 and not more than 9/1, and said adhesion layer comprises a polyester-based resin.
    [2" id="c-fr-0002]
    Thermal transfer sheet according to claim 1, characterized in that said ratio of the mass contents of said polyester-based resin A to said polyester-based resin B (polyester-based resin A / polyester-based resin B). ) in said colored layer is not less than 1/1 and not more than 4/1.
    [3" id="c-fr-0003]
    3. Heat transfer sheet according to claim 1 or 2, characterized in that the thickness of said colored layer is not less than 0.2 μm and not greater than 0.8 μm.
    [4" id="c-fr-0004]
    Thermal transfer sheet according to any one of claims 1 to 3, characterized in that the number-average molecular weight of said polyester-based resin contained in said adhesion layer is not less than 2000 and not greater than at 25000.
    [5" id="c-fr-0005]
    5. Heat transfer sheet according to any one of claims 1 to 4 characterized in that it further comprises a separating layer (4) between said substrate and said colored layer.
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    同族专利:
    公开号 | 公开日
    US20170190203A1|2017-07-06|
    JP2017121734A|2017-07-13|
    JP6587143B2|2019-10-09|
    FR3046381B1|2021-05-14|
    CN107020855A|2017-08-08|
    CN107020855B|2019-04-16|
    US9956803B2|2018-05-01|
    引用文献:
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    JPH02160584A|1988-12-14|1990-06-20|Ricoh Co Ltd|Thermosensitive transfer recording medium|
    JPH11321116A|1998-05-08|1999-11-24|Dainippon Printing Co Ltd|Thermal transfer recording medium|
    WO2000060418A1|1999-04-02|2000-10-12|Sanyo Chemical Industries, Ltd.|Dry toners|
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    JP4359712B2|2000-10-31|2009-11-04|フジコピアン株式会社|Thermal transfer recording medium|
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    JP4404136B2|2007-12-17|2010-01-27|富士ゼロックス株式会社|Toner for developing electrostatic image, method for producing the same, electrostatic image developer, toner cartridge, process cartridge, and image forming apparatus|
    CN102950924B|2012-11-22|2015-05-06|福州艾瑞数码影像有限公司|Computer-cut heat transfer film and producing process for same|
    CN204506172U|2015-01-19|2015-07-29|广东希贵光固化材料有限公司|A kind of hot transfer printing transfer film|JP6828848B2|2018-03-16|2021-02-10|大日本印刷株式会社|Thermal transfer sheet, combination of intermediate transfer medium and thermal transfer sheet, and method for manufacturing printed matter|
    JPWO2020026467A1|2018-07-30|2021-08-02|大日本印刷株式会社|Thermal transfer sheet|
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    法律状态:
    2017-12-15| PLFP| Fee payment|Year of fee payment: 2 |
    2018-12-18| PLFP| Fee payment|Year of fee payment: 3 |
    2019-11-01| PLSC| Publication of the preliminary search report|Effective date: 20191101 |
    2019-12-18| PLFP| Fee payment|Year of fee payment: 4 |
    2020-12-14| PLFP| Fee payment|Year of fee payment: 5 |
    2022-01-19| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2016001258A|JP6587143B2|2016-01-06|2016-01-06|Thermal transfer sheet|
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