JPH06210962A - Thermal transfer ink sheet and thermal transfer recording material using the same - Google Patents

Abstract

PURPOSE:To easily obtain an image excellent in heat resistance, solvent resistance, chemical resistance and abrasion resistance by low applied energy. CONSTITUTION:In a thermal transfer ink sheet, the heat-meltable colorant layer provided on a support contains an epoxy resin, a compd. having a mercapto group being an epoxy resin crosslinking agent and tertiary amine being a crosslinking reaction accelereator or a salt thereof. These components are separately added to an ink sheet and an image receiving sheet to obtain a thermal recording material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to obtaining an image excellent in heat resistance, solvent resistance, abrasion resistance and the like with a heat-sensitive transfer ink sheet, and is mainly used for FA bar code labels which are greatly required for such applications. It is used when printing.

[0002]

2. Description of the Related Art Unlike a heat-sensitive recording paper in which a recorded image is easily erased due to environmental changes such as heat or light, a heat-sensitive transfer ink sheet has a feature that it can be printed on plain paper and can be stored for a long period of time. Since it is possible to output the document information created by a computer, a word processor, etc. at a low cost and with little noise, it has become popular rapidly in recent years.

Further, due to the development of FA, not only the basic function of the heat-sensitive transfer ink sheet such that it can be easily stored for a long period of time, but also higher heat resistance, solvent resistance, abrasion resistance and the like are more advanced. Requests have come to be demanded.

In order to meet such demands, three-dimensional crosslinking of the heat-meltable colorant layer-constituting resin is indispensable, and the simplest method is to transfer the whole heat-meltable colorant-layer-constituting resin in the heat-sensitive transfer ink sheet before transfer. There is a method of crosslinking all of them, but in this method, it takes heat and time to crosslink all the heat-meltable colorant layer-forming resin, and if the heat rises sharply, a heat-sensitive transfer ink sheet is formed. There is a risk that the ink sheet itself will block and many wrinkles will occur, which will adversely affect the printed image. Further, since all the heat-meltable colorant layer-constituting resins are cross-linked, a large amount of heat-applying energy is required when transferring the heat-meltable colorant layer, which makes it difficult to improve the sensitivity and has recently emerged. It is difficult for a high-speed printing printer to transfer at a momentary low applied energy. In addition, the heat application energy tends to increase in order to increase the print density, and the heat rays of the thermal head may be cut off.

In order to solve such a problem, many studies have been made in the past for a method of instantly crosslinking at the time of transfer. The research is roughly classified into two types. One is a method in which a reactive polymer compound and a crosslinkable resin are divided into two layers and instantaneously three-dimensionally crosslinked by the transfer energy of a thermal head.
No. 212389, Japanese Patent Laid-Open No. 63-254093, and another one is a method in which a photoinitiator is put into a layer and instantly three-dimensionally crosslinked by natural light or special light. , JP-A-62-1
There is a publication such as Japanese Patent No. 23784.

As another method, there is a method in which a heat-fusible colorant layer of an ink sheet and a crosslinkable resin and a crosslinker on the surface of an image receiving sheet are separated and combined when printing, and the latter method is preferable. Since it is said that the crosslinkable resin and the crosslinking agent can be separated relatively easily, many studies have been conducted in this method.

[0007] As its main constituent, a cross-linking agent (isocyanate) that cross-links with one constituent material of the hot melt material in the colorant layer is contained on the surface layer of the image receiving sheet.
87389, and JP-A-2-41289 in which a curable polymer (polyol) and a curing agent (isocyanate) are divided into a heat-fusible colorant layer and an image receiving sheet. There is also a method in which a colorant layer-constituting resin is crosslinked by using a specific image-receiving sheet such as Japanese Patent Laid-Open No. 63-212588, in which isocyanate and thermoplastic polyol which are microencapsulated on the surface of the image-receiving sheet are used. By the way, the above-mentioned JP-A-60-212.
As seen in Japanese Patent No. 389, the reactive polymer and the crosslinkable resin are divided into two layers, and even if methyl ethyl ketone peroxime, which is the most easily dissociated, is used to dissociate the isocyanate in the blocked isocyanate, the temperature is 130 ° C.
It is necessary to heat for 30 minutes or more, and it is impossible to instantly dissociate the isocyanate and crosslink the resin with the applied energy at the time of thermal transfer. Even if the amine is microencapsulated to control the reaction, the particle size of the microcapsules alone is estimated to be 5 to 10 μm, and the coating film thickness of the entire heat-melting property becomes very large. Then, the microcapsules are ruptured by the pressure applied when the ink sheet is wound up and the reaction inside the ink sheet proceeds, resulting in the need to increase the applied energy during thermal transfer.

In Japanese Patent Application Laid-Open No. 63-254093, a primary amine or an acid anhydride is used as a crosslinking agent, but considering the reactivity of the primary amine, the crosslinking reaction occurs at the contact interface with the resin even if the layers are layered. It is unlikely that the resin and the cross-linking agent react with each other and cross-link only during thermal transfer. And even if acid anhydride is cross-linked, only linear cross-linking occurs instead of three-dimensional cross-linking, so heat resistance, solvent resistance,
Images with excellent abrasion resistance cannot be obtained.

JP-A-60-13 with a photoinitiator incorporated in the layer
In Japanese Patent Laid-Open No. 2790 and Japanese Patent Laid-Open No. 62-23784, it is necessary to irradiate natural light for at least about half a day, and a special printer device equipped with a special light source is required for instantaneous reaction after thermal transfer. It becomes essential and extremely lacking in generality.

Next, as disclosed in JP-A-62-87389, if a crosslinking agent that crosslinks with one constituent material of the hot melt material in the colorant layer is included on the surface layer of the image receiving sheet, a primary amine, A cross-linking agent such as an acid anhydride deteriorates on the surface of an image-receiving sheet during long-term storage due to its reactivity and its effect remarkably decreases during printing. Further, as seen in JP-A-2-41289, if the curable polymer and the curing agent are simply separated into the heat-fusible colorant layer and the image-receiving sheet, the curable polymer and the curing agent can be successfully separated. Even if the isocyanate compound of the curing agent is extremely unstable by itself, it easily reacts with moisture in the air and self-crosslinks, so that it may react with a polyethylene-vinyl acetate copolymer having a hydroxyl group during thermal transfer. It is unlikely that sufficient isocyanate groups remain.

As disclosed in JP-A-63-212588, if microcapsulated isocyanate and thermoplastic polyol are formed on the surface of the image-receiving sheet, the microcapsules are broken by the pressure applied by the platen roller during printing. Crosslinking occurs on the surface of the image-receiving sheet, and there is a risk that the transferred material from the important ink sheet will not be fixed, and a clear transferred image cannot be obtained.

Further, as a method for defining the softening temperature of the ink layer constituent resin, an ink layer composed of an epoxy resin and a colorant having a softening temperature of 60 ° C. to 110 ° C. is used.
There is a method disclosed in Japanese Patent Application Laid-Open No. 0-59159, but in this method, a printed image is dropped when rubbed in a high temperature atmosphere exceeding 100 ° C.

[0013]

DISCLOSURE OF THE INVENTION The present invention eliminates the equipment and time necessary for enabling sensitivity reduction and crosslinking due to the crosslinking of the hot melt layer before recording, which is a major drawback of the prior art.
The three-dimensional cross-linking of the heat-melt layer instantaneously only during thermal transfer makes it sensitive even at momentary low printing energies in high-speed printing, and at the proper printing density, heat resistance, solvent resistance, chemical resistance, and abrasion resistance. The object is to form a heat-sensitive transfer recording material capable of obtaining an image having excellent properties.

Others In the present invention, the storage stability of the cross-linking agent, which is a major drawback of the prior art, is maintained until the time of thermal transfer, and at the time of thermal transfer, the heat-fusible colorant layer in the ink sheet and the surface of the image-receiving sheet are respectively formed on the surface of the image-receiving sheet. The three types of contained substances are melt-mixed and instantly three-dimensionally crosslinked, so that it is sensitive even at momentary low printing energy in high-speed printing, and also has heat resistance, solvent resistance, chemical resistance even at an appropriate printing density. The purpose is to form a heat-sensitive transfer recording material capable of obtaining an image excellent in resistance and abrasion resistance.

[0015]

The structure of the present invention for solving the above-mentioned problems is a heat-sensitive transfer ink sheet as described in the claims and a heat-sensitive transfer recording material using the same.

More specifically, the heat-fusible colorant layer of the heat-sensitive transfer recording medium of the present invention has three kinds of components relating to the crosslinking reaction of the constituent resins, and can be instantly melted and mixed even with heat of about the applied energy of the thermal printer. A cross-linking epoxy resin, a compound having a mercapto group as an epoxy resin cross-linking agent, and a tertiary amine or a salt thereof as a cross-linking reaction accelerator, which are characterized in that they are described in claims 1 to 3. In the heat-sensitive transfer ink sheet, the heat-fusible colorant layer instantly undergoes three-dimensional cross-linking only by the applied energy during heat transfer.

The heat-fusible colorant layer in the heat-sensitive transfer recording medium used in the present invention comprises two or three layers, the epoxy resin and the compound having a mercapto group are always in separate layers, and the tertiary amine or its salt is not. It is contained in two or more layers separately from the above two and contains a colorant and a heat-melting or heat-softening substance added as necessary, and the colorant is counted from the base material except for the first layer. It is preferably added to the layer.

The heat-sensitive transfer recording medium of the present invention according to claim 10 essentially comprises three components such as an epoxy resin which is instantly crosslinked when melt-mixed, a compound having a mercapto group, and a tertiary amine or a salt thereof. The components are contained in the heat-meltable colorant layer in the ink sheet and the surface of the image-receiving sheet, respectively, and (i) the heat-meltable colorant layer in the ink sheet contains an epoxy resin and a tertiary amine as a crosslinking reaction accelerator or a compound thereof. Those containing a salt and containing a compound having a mercapto group as an epoxy resin crosslinking agent on the surface of the image receiving sheet as an image receiving sheet, (ii) containing an epoxy resin in the heat-meltable colorant layer in the ink sheet, Further, as the image receiving sheet, a compound having a mercapto group as an epoxy resin crosslinking agent on the surface of the image receiving sheet and a three-dimensional compound as a crosslinking reaction accelerator. A compound containing an amine or a salt thereof, (iii) an epoxy resin and a compound having a mercapto group as an epoxy resin cross-linking agent are contained in the heat-fusible colorant layer in the ink sheet, and the surface of the image receiving sheet is used as an image receiving sheet. A compound containing a tertiary amine or a salt thereof as a crosslinking reaction accelerator, and (iv) an image-receiving sheet containing a compound having a mercapto group as an epoxy resin crosslinking agent in the heat-meltable colorant layer in the ink sheet. As an image-receiving sheet containing an epoxy resin and a tertiary amine or a salt thereof as a crosslinking reaction accelerator,
(V) The heat-meltable colorant layer in the ink sheet contains a compound having a mercapto group as an epoxy resin crosslinking agent and a tertiary amine or a salt thereof as a crosslinking reaction accelerator,
Further, as an image receiving sheet, an epoxy resin is contained on the surface of the image receiving sheet, (vi) the heat-meltable colorant layer in the ink sheet contains a tertiary amine or a salt thereof as a crosslinking reaction accelerator, and as an image receiving sheet By the applied energy at the time of thermal transfer, which is characterized in that it is formed from those containing a compound having a mercapto group as an epoxy resin and an epoxy resin crosslinking agent on the surface of the image receiving sheet,
On the surface of the image receiving sheet, these three kinds of substances are mixed and melted and three-dimensionally crosslinked.

The epoxy resin used in the present invention has two or more epoxy groups in one molecule and has a softening point of 4
0 ° C to 160 ° C, epoxy equivalent is 50 to 500 (g
/ Eq) is used, and a novolac type or bisphenol type epoxy resin is preferable. Specifically, orthocresol novolac type, novolac type phenol novolac type brominated phenol novolac type, bisphenol A type, bisphenol F type,
Examples thereof include bisphenol type epoxy resins such as bisphenol S type. Further, an epoxy compound having a boiling point of 80 ° C. to 200 ° C. can be mixed and used with these epoxy resins.

Examples of the epoxy compound include neopentyl glycol diglycidyl ether and the like. These epoxy resins and epoxy compounds can be used as follows.

(1) A mixture of an epoxy resin having a softening point or a melting point of less than 60 ° C. and an epoxy resin having a softening point or a melting point of 111 ° C. or more, wherein the epoxy resin having a melting point of less than 60 ° C. is 5% of the whole epoxy resin. It is preferable that the proportion is ˜35%. (2) A mixture of an epoxy resin having a softening point or a melting point of 50 ° C to 120 ° C and an epoxy resin having a boiling point of 80 to 200 ° C, the epoxy resin having a boiling point of 80 to 200 ° C is 1 to 10 of the whole epoxy resin. % Is preferable. (3) In the heat-fusible colorant layer, the epoxy resin content is preferably 25 to 55% of the components excluding the colorant.

The compound having a mercapto group used in the present invention may be any compound as long as it has two or more mercapto groups in its molecule and has a melting point of 40 ° C to 200 ° C. Include 1,4-benzenedithiol, 1,4-dimercapto-2,3-butanediol, bis- {4-mercaptophenol} ether,
Examples include 4,4′-thiodibenzenethiol, 2,5-dimethylcapto-1,3,4-thiadiazole, bis- {2-mercaptopropoxyoxyethoxy} biphenyl, and meso-2,3-dimercaptosuccinic acid. .

The tertiary amine used in the present invention may be any one as long as it has two nitrogen atoms in its molecule, specifically 1,8-diazabicyclo {5,4,0} -7-.
Undecene, 1,4-bis (2-hydroxyethyl)-
Piperazine, triethylenediamine, 1,5-diazabicyclo {4,3,0} non-5-ene, pyrazine, tetramethylpyrazine, quinazoline, 4-phenylpyrimidine, 4-pyrrolidinopyridine, 4-piperidinopyridine, 1 , 7-phenanthroline, 5-methyl-1,10
-Phenanthroline, 1-methyl-2-phenylbenzimidazole, tetramethylguanidine and the like. In addition, these phenols, octylic acid,
A salt of p-toluenesulfonic acid, formic acid or the like can also be used.

As the heat-melting or heat-softening substance added in the present invention as required, any substance may be used as long as it does not interfere with the transferability of the heat-melting colorant layer. Specifically, paraffin wax, Waxes such as carnauba wax, microcrystalline wax, castor wax, beeswax, selenium wax; low molecular weight high molecular weight materials such as low molecular weight polyethylene, rosin, petroleum resin, terpene resin, stearic acid, palmitic acid, lauric acid, stearin Aluminum acid, lead stearate, barium stearate,
Higher fatty acid salts such as zinc stearate, zinc palmitate, methyl hydroxystearate and glycerol monohydroxystearate or their metal salts, derivatives such as esters; polyethylene, polypropylene, polyisobutylene, polytetrafluoroethylene, ethylene-acrylic acid Examples thereof include homopolymers or copolymers of olefins such as ester copolymers and ethylene-vinyl acetate copolymers or derivatives thereof, which are appropriately added to the heat-meltable colorant layer. When an epoxy resin having a softening point of less than 60 ° C. is used, it is preferable to add a wax having a melting point of 75 ° C. or higher. The preferable addition amount of these is about 0 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin, and if it exceeds 80 parts by weight, the effect of the present invention cannot be obtained.

As the colorant used in the present invention, inorganic and organic dyes or pigments used in printing ink dyes and the like can be used, and the color of the colorant is not limited. In addition, specific examples include carbon black, red iron oxide,
Examples include direct dyes such as disazo yellow, brilliant carmine 6B, lake red C, fast sky blue, phthalocyanine green, oil-based dyes, and basic dyes, which are preferably added to the layers other than the first layer counting from the base.

As the support used in the present invention, any support may be used as long as it has heat resistance and strength capable of withstanding continuous printing, and a film having a thickness of 3 μm to 10 μm is desirable. Specifically, plastic film such as polyester, polypropylene, cellophane, polycarbonate, cellulose acetate, polyethylene, polyvinyl chloride, polystyrene, nylon, polyimide, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, polyethylene naphthalate, or condenser paper, paraffin paper. Can be given.

A backside layer can be formed on the backside of these supports. As the back layer, any material may be used as long as it has appropriate lubricity and heat resistance, and specifically, silicone resin, fluorine resin, polyimide resin, phenol resin, melamine resin, urethane resin, nitrocellulose or Examples thereof include modified resins. The back layer is preferably one that does not react with the hot-melt colorant layer from the viewpoint of preventing blocking because the contact time with the hot-melt colorant layer during storage is long. In addition, if the support alone has suitable lubricity and heat resistance, it is not necessary to coat the back layer.

As a coating method for coating the heat-sensitive transfer material of the present invention, a solvent coating method is preferable, reverse roll coating,
Gravure coat, lot coat, air doctor coat,
A usual coating method such as blade coating can be used without requiring special equipment.

The solvent used in the present invention may be any solvent which is convenient for the dispersion of each material in coating the hot-melt colorant layer and the back layer. Specific examples include the following. Alcohol-based methanol, ethanol, isopropyl alcohol, butanol, isobutanol, etc .; Ketone-based methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; Aromatic-based toluene, xylene, etc .; Halogen-based dichloromethane, trichloroethane, etc .; Ester-based Examples thereof include ethyl acetate, and examples of other include dioxane, tetrahydrofuran and the like, which may be used alone or as a mixture of the same system at a constant ratio.

These solvents have different polarities from the viewpoint of preventing blocking between the back layer and the hot-melt colorant layer, which are considered to have the longest contact time during storage, and have different polarities. It is desirable to use one.

[0031]

EXAMPLES The present invention will be described in detail below with reference to examples. Of course, these examples are only a part of the effects of the present invention, and the effects of the present invention are not limited to the examples. All parts shown in the examples are parts by weight.

Example I-1 Liquid A Colorant: Carbon black 25 parts Epoxy resin Orthocresol novolac type epoxy resin EOCN-1020 (softening point: 70.7 ° C., epoxy equivalent: 199 g / eq) [Nippon Kayaku Co., Ltd.] Made by the company] 100 parts Tertiary amine 1,8-diazabicyclo {5,4,0} 7-undecene (number of nitrogen in the molecule: 2) 20 parts Methyl ethyl ketone 400 parts Methyl isobutyl ketone 40 parts B liquid heat fusible substance: carnauba Wax 200 parts Compound having mercapto group 1,4-benzenedithiol (number of mercapto groups in molecule: 2, melting point: 98 ° C.) 100 parts Toluene 400 parts These solutions A and B are continuously heated at room temperature using a sand mill 6 The coating liquids were prepared by dispersing for a time.

Silicon modified urethane resin on the back side is 0.5
4.5μ which has already been coated as a back layer with an adhesion amount of g / m ^2.
Liquid B is applied to the surface of a polyethylene terephthalate film having a thickness of m so that the amount of adhesion is 2.5 ± 0.3 g / m ² , and then 3.0 ± 0.3 g / m ² is adhered on it. Liquid A was applied so as to be a material and dried to form a heat-meltable colorant layer, to prepare a heat-sensitive transfer ink sheet.

Example I-2 The tertiary amine: 1,8-diazabicyclo {5,4,0} 7-undecene in the liquid A in Example I-1 was converted to 1,5-
A thermal transfer ink sheet was prepared in the same manner as in Example I-1, except that diazabicyclo {4,3,0} non-5-ene was used.

Example I-3 Example I-1 except that the tertiary amine: 1,8-diazabicyclo {5,4,0} 7-undecene in solution A in Example I-1 was changed to triethylenediamine. A thermal transfer ink sheet was prepared in the same manner as in.

Example I-4 Compound having mercapto group in solution B in Example I-1, 1,4-benzenedithiol was converted into 4,4'-thiodibenzenethiol (the number of mercapto groups: 2, melting point 116)
A heat-sensitive transfer ink sheet was produced in the same manner as in Example I-1 except that the temperature was changed to (° C).

Example I-5 Epoxy resin in solution A in Example I-1: Orthocresol novolac type epoxy resin, EOCN-102
Brominated phenol novolac type epoxy resin, BR
EN-S (softening point: 80 ° C., epoxy equivalent 280 g / e
q) Example I except that it was changed to [Nippon Kayaku Co., Ltd.]
A thermal transfer film ink sheet was prepared in the same manner as in -1.

Comparative Example I-1 Same as Example I-1, except that the tertiary amine: 1,8-diazabicyclo {5,4,0} 7-undecene in solution A in Example I-1 was omitted. A thermal transfer ink sheet was prepared.

Comparative Example I-2 The tertiary amine: 1,8-diazabicyclo {5,4,0} 7-undecene in the liquid A in Example I-1, benzyldimethyl containing only one nitrogen in the molecule. A thermal transfer ink sheet was prepared in the same manner as in Example I-1, except that the amine was changed.

Comparative Example I-3 A thermal transfer ink sheet was prepared in the same manner as in Example I-1, except that the compound having a mercapto group: 1,4-benzenedithiol in the solution B in Example I-1 was omitted. .

Comparative Example I-4 Compound having mercapto group in solution B in Example I-1: 1,4-benzenedithiol 2-mercaptopyridine containing only one nitrogen in the molecule (melting point: 128
A thermal transfer ink sheet was prepared in the same manner as in Example I-1, except that the temperature was changed to 130 ° C.

Comparative Example I-5 Epoxy resin in solution A in Example I-1: Orthocresol novolac type epoxy resin, EOCN-102
Example I-1 except that 0 was changed to paraffin wax
A thermal transfer ink sheet was prepared in the same manner as in.

Comparative Example I-6 Epoxy Resin in Solution A in Example I-1: Orthocresol Novolac Epoxy Resin, EOCN-102
Example I except that 0 was changed to one having a softening point of 200 ° C.
A thermal transfer ink sheet was prepared in the same manner as in -1.

The 11 types of heat-sensitive transfer films produced as described above were evaluated by the following method and the results are shown in Table 1.
Shown in.

In all the printing tests, label-coated mirror-coated paper with the back side being glued was used as the receiving paper.

"Evaluation conditions" 1. Printing conditions Thermal head used: Partial Grace thin film head type Platen load pressure: 150 g / cm Peeling angle of thermal transfer recording medium: 30 against receiving paper
Detachment torque value: 200 g Applied energy: 10 to 35 mj / mm ² Printing speed: 4 inches / second Printing pattern: Bar code Code 3/9 2. Thermal sensitivity The minimum applied energy at which the barcode decoding rate becomes 100% after printing on a thermal transfer recording medium. Conditions for evaluating solvent resistance and chemical resistance A cotton swab containing 0.5 ml of each of the following solvents and chemicals 3
A rub test was performed for each chemical under a load of 0 g / mm ^{2 and} the number of times required to expose the surface layer of the receiving paper was recorded. Solvents / chemicals used: ethanol, brake oil, kerosene,
Car wax, toluene, xylene, percrain 4. Heat resistance After printing on a thermal transfer recording medium, place a corrugated cardboard on the printing surface in an atmosphere of 100 ° C. and apply a load of 100 g / cm ² 30
A reciprocal love test was performed at a speed of cm / sec and the number of times the image became unreadable was recorded. 5. Hardness and abrasion resistance (2H) After printing on a thermal transfer recording medium, a rub test was conducted on the printed surface with an objective having a hardness of 2H of about 1 t / cm ² and the number of times the image became unreadable was recorded.

[0047]

[Table 1]

Example II-1 Liquid A Colorant: Carbon black 25 parts Epoxy resin Orthocresol novolac type epoxy resin, EOCN-1020 (softening point: 70 ° C., epoxy equivalent: 199 g / eq) [Nippon Kayaku Co., Ltd.] Made] 100 parts Methyl ethyl ketone 400 parts Methyl isobutyl ketone 40 parts Liquid B Thermofusible substance: Carnauba wax 200 parts Tertiary amine 1,8-diazahicyclo {5,4,0} 7-undecene (number of nitrogen atoms in the molecule: 2) 20 parts Toluene 400 parts C solution Compound having mercapto group 1,4-benzenedithiol (Number of mercapto groups in molecule: 2, melting point: 98 ° C.) 100 parts Methyl ethyl ketone 400 parts Methyl isobutyl ketone 40 parts These A solution and B solution respectively Disperse the mixture using a sand mill at room temperature for 6 hours continuously. To prepare a layer coating solution, respectively.

Silicon modified urethane resin on the back side is 0.5
4.5μ which has already been coated as a back layer with an adhesion amount of g / m ^2.
Solution B was applied and dried on the surface of a polyethylene terephthalate film having a thickness of m so that the amount of adhesion was 2.5 ± 0.3 g / m ² , and then 3.0 ± 0.3 g / m ² Liquid A was applied so that the amount of adhesion would be applied and dried to form a heat-fusible colorant layer, to prepare a heat-sensitive transfer ink sheet. Solution C dissolves well, and 1. on the image receiving sheet (mirror coated paper).
A dedicated image-receiving sheet was prepared by applying the solution so that the adhesion amount was 0 ± 0.3 g / m ² and drying.

Example II-2 The tertiary amine: 1,8-diazabicyclo {5,4,0} 7-undecene in the liquid B in Example II-1 was changed to 1,5-
A heat-sensitive transfer ink sheet and a dedicated image-receiving sheet were produced in the same manner as in Example II-1 except that diazabicyclo {4,3,0} non-5-ene was used.

Example II-3 Example II-1 except that the tertiary amine: 1,8-diazabicyclo {5,4,0} 7-undecene in solution B in Example II-1 was changed to triethylenediamine. A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as in.

Example II-4 Compound having mercapto group in liquid C in Example II-1: 1,4-benzenedithiol was converted to 4,4'-thiodibenzenethiol (the number of mercapto groups: 2, melting point: 116)
A heat-sensitive transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-1 except that the temperature was changed to (° C).

Example II-5 Epoxy resin in solution A in Example II-1: orthocresol novolac type epoxy resin, EOCN-102
Brominated phenol novolac type epoxy resin, BR
EN-S (softening point: 80 ° C., epoxy equivalent: 280 g /
eq) Example except that it was changed to [Nippon Kayaku Co., Ltd.]
A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as in II-1.

Example II-6 Compound having mercapto group in solution C in Example II-1: 1,4-benzenedithiol was converted to bis- {2-mercaptopropoxyoxyethoxy} biphenyl (mercapto group number: 2, melting point: 83). Example except that the temperature was changed to
A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as in II-1.

Example II-7 Epoxy resin in solution A in Example II-1: orthocresol novolac type epoxy resin, EOCN-102
0 is phenol novolac type epoxy resin, EPPN-
A thermal transfer film and a dedicated image-receiving sheet were formed in the same manner as in Example II-1 except that 201 (68 ° C., epoxy equivalent: 187 g / eq) [manufactured by Nippon Kayaku Co., Ltd.] was used.

Example II-8 Liquid D Colorant: Carbon black 25 parts Epoxy resin Orthocresol novolac type epoxy resin EOCN-1020, (softening point: 70.7 ° C., epoxy equivalent: 199 g / eq) [Nippon Kayaku Co., Ltd.] Made by company] 100 parts Methyl ethyl ketone 400 parts Methyl isobutyl ketone 40 parts E liquid heat-melting substance: carnauba wax 200 parts Compound having mercapto group 1,4-benzenedithiol (number of mercapto groups in molecule: 2, melting point: 98 ° C) 100 Part Toluene 400 parts F liquid Tertiary amine 1,8-diazabicyclo {5,4,0} 7-undecene (number of nitrogen in the molecule: 2) 20 parts Methyl ethyl ketone 400 parts Methyl isobutyl ketone 40 parts These D liquid and E liquid Disperse each for 6 hours continuously at room temperature using a sand mill. Adjusting the respective coating liquid.

Silicon modified urethane resin on the back side is 0.5
Adhesion amount of g / m ² 4.5 μm which has been coated as a back layer
Liquid E is applied to the surface of a polyethylene terephthalate film having a thickness of 2.5 ± 0.3 g / m ² to dry it, and then 3.0 ± 0.3 g / m ² is deposited on it. The liquid D was applied in an amount of the desired amount and dried to form a heat-fusible colorant layer to prepare a heat-sensitive transfer ink sheet. The F liquid dissolves well and is applied onto the image receiving sheet (mirror coated paper) so that the amount of adhesion is 1.0 ± 0.3 g / m ² ,
It was dried to prepare a dedicated image-receiving sheet.

Example II-9 The tertiary amine: 1,8-diazabicyclo {5,4,0} 7-undecene in the liquid F in Example II-8 was converted to 1,5-
A thermal transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-8 except that diazabicyclo {4,3,0} non-5-ene was used.

Example II-10 Example II-8 except that the tertiary amine: 1,8-diazabicyclo {5,4,0} 7-undecene in the liquid F in Example II-8 was changed to triethylenediamine. A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as in.

Example II-11 Compound having mercapto group in solution E in Example II-8: 1,4-benzenedithiol was converted into 4,4'-thiodibenzenethiol (the number of mercapto groups: 2, melting point: 11)
A thermal transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-8 except that the temperature was changed to 6 ° C.

Example II-12 Epoxy resin in liquid D in Example II-8: orthocresol novolac type epoxy resin, EOCN-102
Brominated phenol novolac type epoxy resin, BR
EN-S (softening point: 80 ° C., epoxy equivalent: 280 g /
eq) Example except that it was changed to [Nippon Kayaku Co., Ltd.]
A heat-sensitive transfer film and a dedicated image-receiving sheet were prepared in the same manner as II-8.

Example II-13 Compound having mercapto group in solution E in Example II-8: 1,4-benzenedithiol was converted into bis- {2-mercaptopropoxyoxyethoxy} biphenyl (mercapto group number: 2, melting point: 83). Example except that the temperature was changed to
A thermal transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as II-8.

Example II-14 Epoxy resin in liquid D in Example II-8: orthocresol novolac type epoxy resin, EOCN-102
0 is phenol novolac type epoxy resin, EPPN-
201 (softening point: 68 ° C., epoxy equivalent: 187 g / e
q) Example II except that it was changed to [Nippon Kayaku Co., Ltd.]
A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as in -8.

Example II-15 G liquid Colorant: carbon black 25 parts Compound having mercapto group 1,4-benzenedithiol (number of mercapto groups in molecule: 2, melting point: 98 ° C.) 100 parts methyl ethyl ketone 400 parts methyl isobutyl ketone 40 parts H liquid Thermofusible substance: carnauba wax 200 parts Tertiary amine 1,8-diazabicyclo {5,4,0} 7-undecene (number of nitrogen atoms in the molecule: 2) 20 parts Toluene 400 parts Liquid I epoxy resin ortho Cresol novolac type epoxy resin, EOCN-1020 (softening point: 70.7 ° C., epoxy equivalent: 199 g / eq) [Nippon Kayaku Co., Ltd.] 100 parts Methyl ethyl ketone 400 parts Methyl isobutyl ketone 40 parts These G liquid and H liquid Disperse continuously for 6 hours at room temperature using a sand mill. Adjusting the respective coating liquid Te.

Silicon modified urethane resin on the back side is 0.5
4.5μ which has already been coated as a back layer with an adhesion amount of g / m ^2.
Liquid H is applied to the surface of a polyethylene terephthalate film having a thickness of m so that the amount of adhesion is 2.5 ± 0.3 g / m ² , and then 3.0 ± 0.3 g / m ² is applied thereon.
The G liquid was applied so that the amount of adhesion would be and dried to form a heat-fusible colorant layer, to prepare a heat-sensitive transfer ink sheet. Solution I was dissolved well and applied on an image-receiving sheet (mirror-coated paper) so as to have an adhesion amount of 1.0 ± 0.3 g / m ² , and dried to prepare a dedicated image-receiving sheet.

Example II-16 Tertiary amine in liquid H in Example II-15: 1,8-
Diazabicyclo {5,4,0} 7-undecene was added to 1,5
A heat-sensitive transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-15, except that the diazabicyclo {4,3,0} non-5-ene was used.

Example II-17 Tertiary amine in liquid H in Example II-15: 1,8-
A heat-sensitive transfer ink sheet and a dedicated image-receiving sheet were produced in the same manner as in Example II-15, except that diethylenebicyclo {5,4,0} 7-undecene was changed to triethylenediamine.

Example II-18 Compound having mercapto group in liquid G in Example II-15: 1,4-benzenedithiol was converted to 4,4'-thiodibenzenethiol (the number of mercapto groups: 2, melting point: 1)
A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as in Example II-15 except that the temperature was changed to 16 ° C.

Example II-19 Epoxy resin in solution I in Example II-15: orthocresol novolac type epoxy resin, EOCN-10
20 is brominated phenol novolac type epoxy resin, B
REN-S (softening point: 80 ° C., epoxy equivalent: 280 g
/ Eq) A thermal transfer ink sheet and a dedicated image-receiving sheet were produced in the same manner as in Example II-15 except that it was changed to [Nippon Kayaku Co., Ltd.].

Example II-20 Compound having mercapto group in liquid G in Example II-15: 1,4-benzenedithiol was converted into bis- {2-mercaptopropoxyoxyethoxy} biphenyl (mercapto group number: 2, melting point: 83). A heat-sensitive transfer ink sheet and a dedicated image-receiving sheet were produced in the same manner as in Example II-15 except that the temperature was changed to (° C).

Example II-21 Epoxy resin in solution I in Example II-15: orthocresol novolac type epoxy resin, EOCN-10
A thermal transfer ink sheet and a dedicated image-receiving were prepared in the same manner as in Example II-15 except that 20 was changed to phenol novolac, EPPN-201 (softening point: 68 ° C., epoxy equivalent: 187 g / eq) [manufactured by Nippon Kayaku Co., Ltd.]. A sheet was prepared.

Example II-22 100 parts of EOCN-1020 orthocresol novolac type epoxy resin in Example II-1 was replaced with 100 parts of bisphenol A type epoxy resin Epicoat 1007 (softening point:
128 ° C.) [made by Yuka Shell Epoxy Co., Ltd.] 70 parts and modified bisphenol S type epoxy resin EBPS-300
(Softening point: 55 ° C.) [manufactured by Nippon Kayaku Co., Ltd.] A thermal transfer ink sheet and an image receiving sheet were prepared in the same manner as in Example II-1 except that the content was changed to 30 parts.

Example II-23 100 parts of the ortho-cresol novolac type epoxy resin EOCN-1020 in Example II-1 was replaced with 95 parts of ortho-cresol novolac type epoxy EOCN-1020 (softening point: 70.7 ° C.) and neopentyl. A thermal transfer ink sheet and an image receiving sheet were prepared in the same manner as in Example II-1 except that the amount of glycol diglycidyl ether (boiling point: 98 ° C.) was changed to 5 parts.

Example II-24 100 parts of the orthocresol novolac type epoxy resin, EOCN-1020 in Example II-1 was modified with bisphenol S type epoxy resin: EBPS-300 (softening point: 55 ° C.) 40 parts, carnauba wax. A thermal transfer ink sheet and an image receiving sheet were produced in the same manner as in Example II-1 except that the CW-1 (softening point: 73 ° C.) [Noda Wax Co., Ltd.] was changed to 60 parts.

Example II-25 100 parts of the ortho-cresol novolac type epoxy resin EOCN-1020 in Example II-8 was replaced with bisphenol A type epoxy resin Epicoat 1007 (softening point: 1
28 ° C.) 70 parts and modified bisphenol S type epoxy resin EBPS-300 (softening point: 55 ° C.) 30 parts, except that a thermal transfer ink sheet and an image receiving sheet were prepared in the same manner as in Example II-8.

Example II-26 Orthocresol novolac type epoxy resin in Example II-8, 100 parts of EOCN-1020 was replaced with orthocresol novolac type epoxy resin EOCN-1020.
A thermal transfer ink sheet and an image receiving sheet were prepared in the same manner as in Example II-8 except that the content was changed to 95 parts (softening point: 70.7 ° C.) and 5 parts neopentyl glycol diglycidyl ether (boiling point: 98 ° C.). .

Example II-27 Orthocresol novolac type epoxy resin in Example II-8, 100 parts of EOCN-1020 is modified bisphenol S type epoxy resin: EBPS-300 (softening point: 55 ° C.) 40 parts, carnauba wax CW -1 (softening point: 73 ° C.) [manufactured by Noda Wax Co., Ltd.] A thermal transfer ink sheet and an image receiving sheet were produced in the same manner as in Example II-8 except that the amount was changed to 60 parts.

Example II-28 100 parts of the orthocresol novolac type epoxy resin EOCN-1020 in Example II-15 was replaced with bisphenol A type epoxy resin Epicoat 1007 (softening point:
128 ° C.) 70 parts and modified bisphenol S type epoxy resin EBPS-300 (softening point: 55 ° C.) 30 parts were used to prepare a thermal transfer ink sheet and an image receiving sheet in the same manner as in Example II-15.

Example II-29 Orthocresol novolac type epoxy resin in Example II-15, 100 parts of EOCN-1020 was replaced with orthocresol novolac type epoxy resin EOCN-102.
0 (softening point: 70.7 ° C.) 95 parts and neopentyl glycol diglycidyl ether (boiling point: 98 ° C.) 5 parts were prepared in the same manner as in Example II-15 to prepare a heat-sensitive transfer ink sheet and an image receiving sheet. did.

Example II-30 Orthocresol novolac type epoxy resin in Example II-15, 100 parts of EOCN-1020 was modified with bisphenol S type epoxy resin: EBPS-300 (softening point: 55 ° C.) 40 parts, carnauba wax CW -1 (softening point: 73 ° C.) [manufactured by Noda Wax Co., Ltd.] A thermal transfer ink sheet and an image receiving sheet were produced in the same manner as in Example II-15 except that the amount was changed to 60 parts.

Comparative Example II-1 Same as Example II-1 except that the tertiary amine: 1,8-diazabicyclo {5,4,0} 7-undecene in solution B in Example II-1 was omitted. A thermal transfer ink sheet and a dedicated image receiving sheet were prepared.

Comparative Example II-2 Tertiary amine: 1,8-diazabicyclo {5,4,0} 7-undecene in solution B in Example II-1 was benzyldimethyl containing only one nitrogen atom in the molecule. A heat-sensitive transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-1 except that the amine was used.

Comparative Example II-3 A thermal transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-1 except that the coating of liquid C in Example II-1 was not performed.

Comparative Example II-4 Compound having mercapto group in solution C in Example II-1: 2-mercaptopyridine (melting point: 129, 1,4-benzenedithiol containing only one mercapto group in the molecule) A heat-sensitive transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-1 except that the temperature was changed to (° C).

Comparative Example II-5 Epoxy Resin in Solution A of Example II-1: Orthocresol Novolac Epoxy Resin, EOCN-102
Example II-1 except that 0 was changed to paraffin wax
A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as in.

Comparative Example II-6 Epoxy resin in solution A in Example II-1: Orthocresol novolac type epoxy resin, EOCN-102
Example II except that 0 was changed to one having a softening point of 200 ° C.
A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as in No. -1. Comparative Example II-7 A compound having a mercapto group in the liquid C in Example II-1: 1,4-benzenedithiol, except that the melting point was changed to 1,2-dimercaptobenzene having a melting point of 27 ° C.
A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as in II-1. Comparative Example II-8 A thermal transfer ink as in Example II-8 except that the tertiary amine: 1,8-diazabicyclo {5,4,0} 7-undecene in the F liquid in Example II-8 was omitted. A sheet and a dedicated image receiving sheet were prepared.

Comparative Example II-9 The tertiary amine in the liquid F in Example II-8: 1,8-diazabicyclo {5,4,0} 7-undecene was benzyldimethyl containing only one nitrogen in the molecule. A heat-sensitive transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-8 except that the amine was changed.

Comparative Example II-10 A thermal transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-8 except that the coating of the liquid E in Example II-8 was not performed.

Comparative Example II-11 Compound having mercapto group in solution E in Example II-8: 2-mercaptopyridine (melting point: 129, 1,4-benzenedithiol containing only one mercapto group in the molecule A heat-sensitive transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-8 except that the temperature was changed to (° C).

Comparative Example II-12 Epoxy resin in liquid D in Example II-8: orthocresol novolac type epoxy resin, EOCN-102
Example II-8 except that 0 was changed to paraffin wax
A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as in.

Comparative Example II-13 Epoxy Resin in Liquid D in Example II-8: Orthocresol Novolac Epoxy Resin, EOCN-102
Example II except that 0 was changed to one having a softening point of 200 ° C.
A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as in -8. Comparative Example II-14 Example having the mercapto group-containing compound in solution E in Example II-8: 1,4-benzenedithiol was changed to 1,2-dimercaptobenzene having a melting point of 27 ° C.
A thermal transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as II-8. Comparative Example II-15 Tertiary amine in solution H in Example II-15: 1,8-
A thermal transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-15 except that diazabicyclo {5,4,0} 7-undecene was omitted.

Comparative Example II-16 Tertiary amine in solution H in Example II-15: 1,8-
A thermal transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-15, except that diazabicyclo {5,4,0} 7-undecene was changed to benzyldimethylamine containing only one nitrogen atom in the molecule.

Comparative Example II-17 A thermal transfer ink sheet and a dedicated image-receiving sheet were prepared in the same manner as in Example II-15 except that the liquid I was not applied in Example II-15.

Comparative Example II-18 Compound having mercapto group in liquid G in Example II-15: 2-mercaptopyridine (melting point: 129, 1,4-benzenedithiol containing only one mercapto group in the molecule A heat-sensitive transfer ink sheet and a dedicated image-receiving sheet were produced in the same manner as in Example II-15 except that the temperature was changed to (° C).

Comparative Example II-19 Epoxy resin in solution I in Example II-15: orthocresol novolac type epoxy resin, EOCN = 10
Example II-except that 20 was changed to paraffin wax
A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as in No. 15. Comparative Example II-20 Epoxy resin in solution I in Example II-15: orthocresol novolac type epoxy resin, EOCN-10
Example except that the softening point of 20 was changed to 200 ° C.
A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as II-15.

Comparative Example II-21 Compound having a mercapto group in liquid G in Example II-15: 1,4-benzenedithiol Example except that 1,2-dimercaptobenzene having a melting point of 27 ° C. was changed.
A thermal transfer ink sheet and a dedicated image receiving sheet were prepared in the same manner as II-15.

The 51 types of heat-sensitive transfer films formed as described above were evaluated by the following methods, and Examples are shown in Tables 2 and 3, and Comparative Examples are shown in Table 4.

[0098]

[Table 2]

[0099]

[Table 3]

[0100]

[Table 4]

In the printing test, the dedicated image-receiving sheet was used in which the label-coated mirror-coated paper having the back surface glued was applied on the image-receiving sheet in each of Examples and Comparative Examples.

“Evaluation conditions” 1. Printing conditions Thermal head used: Partial Grace thin film head type Platen load pressure: 150 g / cm Peeling angle of thermal transfer recording medium: 30 against receiving paper
Detachment torque value: 200 g Applied energy: 10 to 35 mj / mm ² Printing speed: 4 inches / second Printing pattern: Bar code Code 3/9 2. Thermal sensitivity The bar code decoding rate is 100 after printing on the thermal transfer recording medium.
The lowest applied energy that becomes% 3. Conditions for evaluating solvent resistance and chemical resistance A cotton swab containing 0.5 ml of each of the following solvents and chemicals 3
A rub test was performed for each chemical under a load of 0 g / mm ² and the number used to expose the surface layer of the receiving paper was recorded.

Solvents / chemicals used: ethanol, brake oil, kerosene, car wax, toluene, xylene, percrain 4. Heat resistance After printing on a thermal transfer recording medium, place a corrugated cardboard on the printing surface in an atmosphere of 100 ° C. and apply a load of 100 g / cm ² 30
A reciprocal love test was performed at a speed of cm / sec and the number of times the image became unreadable was recorded.

5. Hardness and abrasion resistance (2H) After printing on a thermal transfer recording medium, a rub test was performed on the printed surface with an objective having a hardness of 2H of about 1 t / cm ² and the number of times the image became unreadable was recorded.

[0105]

When the heat-sensitive transfer recording medium of the present invention is used, the resin is three-dimensionally cross-linked after transfer, so that the heat-transfer resistance is low and the heat-resistance and solvent resistance are low compared to the conventional heat- and solvent-resistant heat-transfer recording media. Images with excellent solvent resistance, chemical resistance, and abrasion resistance can be obtained.

Claims (10)

[Claims] 1. A heat-fusible colorant layer provided on a support contains an epoxy resin, a compound having a mercapto group as an epoxy resin crosslinking agent, and a tertiary amine or a salt thereof as a crosslinking reaction accelerator. A heat-sensitive transfer ink sheet characterized by. 2. A heat-fusible colorant layer is formed from two layers, an epoxy resin and a compound having a mercapto group are contained in separate layers, and a tertiary amine or a salt thereof is contained in one or both layers. The heat-sensitive transfer ink sheet according to claim 1, wherein the heat-sensitive transfer ink sheet is contained in. 3. The heat-fusible colorant layer is formed of three layers, and the epoxy resin, the compound having a mercapto group, and the tertiary amine or a salt thereof are contained in separate layers. Item 3. A heat-sensitive transfer ink sheet according to item 1. 4. The epoxy resin has a softening point or a melting point of 6
The thermal transfer ink sheet according to any one of claims 1 to 3, wherein the thermal transfer ink sheet has a softening point or a melting point of 111 ° C or higher and a temperature of lower than 0 ° C. 5. The heat-sensitive transfer ink sheet according to claim 4, wherein the epoxy resin having a softening point or a melting point of less than 60 ° C. is 5% to 35% of the entire epoxy resin. 6. The softening point or melting point of the epoxy resin is 5
The boiling point of epoxy resin from 0 ℃ to 120 ℃ is 80 ℃ to 2 ℃.
The thermal transfer ink sheet according to any one of claims 1 to 3, wherein an epoxy compound at 00 ° C is added. 7. The thermal transfer ink sheet according to claim 6, wherein the epoxy compound having a boiling point of 80 to 200 ° C. is 1 to 10% of the whole epoxy resin. 8. The heat-sensitive transfer ink according to claim 1, wherein the heat-meltable colorant layer contains an epoxy resin having a softening point of less than 60 ° C. and a wax having a melting point of 75 ° C. or more. Sheet. 9. An epoxy resin having a softening point of less than 60 ° C.,
The heat-sensitive transfer ink sheet according to claim 8, wherein 25 to 55% of the component excluding the colorant is present in the heat-meltable colorant layer. 10. A thermal transfer recording material comprising a thermal transfer ink sheet and an image receiving sheet, which essentially comprises an epoxy resin, a compound having a mercapto group as an epoxy resin crosslinking agent, and a tertiary amine or a salt thereof as a crosslinking reaction accelerator. Of the three components, one or two components are contained in the heat-fusible colorant layer of the ink sheet, and the remaining components are contained on the surface of the image-receiving sheet, the thermal transfer recording material.