JP2007168404A - Heat transfer recording system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat transfer recording system which excels in the durability of a head and which can be processed at an elevated temperature and a high speed using a color thermal printer which inhibits getting damaged by a platen roller at both ends of a heating element array which overflows an ink sheet and a thermosensitive transfer receiver sheet which were stuck face to face. <P>SOLUTION: The heat transfer recording system using a thermal printer keeps a pair of protection belts 18 and 19 arranged as they remain coiled partly around both the sides of the platen roller 12 about the thermal printer, makes the pair of the protection belts catch both the ends of the heating element array 13a bulged out from both the sides of the ink sheet and the thermosensitive transfer receiver sheet 10 so that they do not contact the platen roller, and includes a thermoplastic resin in the acceptance layer of the thermosensitive transfer receiver sheet to be used. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thermal transfer recording system, and more particularly to a thermal transfer recording system using a thermal printer in which a heating element array of a thermal head is prevented from being damaged by a platen roller.

  In a thermal printer, a thermal head is disposed so as to face a hard rubber platen roller. When recording is performed by the dye diffusion transfer recording method, the ink layer of a thermal transfer sheet (hereinafter also referred to as an ink sheet) containing a pigment and the image receiving layer of a thermal transfer image receiving sheet (hereinafter also referred to as an image receiving sheet) face each other. In this case, the images are pressed and heated by the heating element array of the thermal head when this is conveyed on the platen roller of the thermal printer, and an image is recorded in color.

  By the way, if the pressing force when the thermal head is pressed against the bonded ink sheet and heat-sensitive transfer image-receiving sheet is small, the heat transfer coefficient becomes small. Will be lower. Therefore, in order to obtain a sufficient pressing force, the thermal head is strongly pressed against the ink sheet and the thermal transfer image receiving sheet so that the ink sheet and the thermal transfer image receiving sheet slightly sink on the surface of the platen.

  If the heating element array of the thermal head is larger than the width of the ink sheet and the thermal transfer image receiving sheet, the thermal head is located at both ends of the heating element array when the thermal head is pressed against the ink sheet and the thermal transfer image receiving sheet. Since the heating element is in direct contact with the platen, this portion may be damaged.

  The present invention uses a color thermal printer in which both ends of a heating element array protruding from an ink sheet and a thermal transfer image receiving sheet that are bonded to each other are prevented from being damaged by a platen roller. An object is to provide a thermal transfer recording system capable of high-speed processing.

The problems of the present invention have been solved by the following means.
[1] A thermal head is disposed facing the platen roller, and the ink sheet and the thermal transfer image-receiving sheet which are bonded to each other on the platen roller are pressed by the heating element array of the thermal head, and the ink sheet and the above-described thermal sensor are pressed. A thermal transfer recording system using a thermal printer that records an image by heating with a heating element array while conveying a thermal transfer image-receiving sheet, wherein the thermal printer has a pair of protections partially wrapped around both sides of the platen roller. A belt is arranged so that both ends of the heating element array protruding from both sides of the ink sheet and the thermal transfer image-receiving sheet are received by a pair of protective belts so as not to come into contact with the platen roller. A thermal transfer recording system comprising a thermoplastic resin in a receiving layer of a thermal transfer image receiving sheet.
[2] The thermal transfer recording system according to item [1], wherein at least one of the thermoplastic resins contained in the receiving layer of the thermal transfer image-receiving sheet is a polyester and / or polycarbonate polymer.

（一般式（１）中、Ｒ¹、Ｒ²およびＲ³は各々独立に水素原子または置換基を表す。Ａ¹は結合している両端の炭素原子と共にヘテロ環を形成する原子団を表す。Ｂ¹は結合している両端の炭素原子、窒素原子と共にヘテロ環を形成する原子団を表す。）

（一般式（３）中、Ｒ¹¹、Ｒ¹³およびＲ¹⁴は各々独立に水素原子または置換基を表す。Ｒ¹²は置換基を表す。Ａ²は結合している両端の炭素原子と共にヘテロ環を形成する原子団を表す。ｎ３は０〜４の整数を表す。ここで、ｎ３が２〜４の整数を表すとき複数のＲ¹²は同じでも異なっていてもよい。） [3] The item [2], wherein the ink sheet used in an overlapping manner with the heat-sensitive transfer image-receiving sheet contains at least one dye represented by the following general formula (1) or (3): The thermal transfer recording system described.

(In the general formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent. A ¹ represents an atomic group which forms a heterocycle with carbon atoms bonded to each other. B ¹ represents an atomic group that forms a heterocycle together with the carbon and nitrogen atoms at both ends to which it is bonded.

(In the general formula (3), R ¹¹ , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a substituent. R ¹² represents a substituent. A ² is a heterocycle together with carbon atoms at both ends to which it is bonded. N3 represents an integer of 0 to 4. Here, when n3 represents an integer of 2 to 4, a plurality of R ¹² may be the same or different.

（一般式（４）中、Ｄはジアゾニウム塩由来の芳香環基または芳香族へテロ環基を表す。Ｒ¹⁵は置換基を表し、Ｒ¹⁶およびＲ¹⁷は各々独立に水素原子または置換基を表す。ｎ４は０〜４の整数を表す。ここで、ｎ４が２〜４の整数を表すとき複数のＲ¹⁵は同じでも異なっていてもよい。）

（一般式（５）中、Ａ³は結合している両端の炭素原子と共にヘテロ環を形成する原子団を表す。ＥＷＧ¹は電子吸引基を表す。Ｒ¹⁸は置換基を表し、Ｒ¹⁹およびＲ²⁰は各々独立に水素原子または置換基を表す。ｎ５は０〜４の整数を表す。ここで、ｎ５が２〜４の整数を表すとき複数のＲ¹⁸は同じでも異なっていてもよい。） [4] The ink sheet used by being superimposed on the thermal transfer image-receiving sheet contains at least one dye represented by the following general formula (4) or (5) [2] or [ The thermal transfer recording system according to item 3].

(In the general formula (4), D represents an aromatic ring group or an aromatic heterocyclic group derived from a diazonium salt. R ¹⁵ represents a substituent, and R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a substituent. N4 represents an integer of 0 to 4. Here, when n4 represents an integer of 2 to 4, a plurality of R ¹⁵ may be the same or different.

(In General Formula (5), A ³ represents an atomic group that forms a heterocycle with carbon atoms bonded to both ends. EWG ¹ represents an electron-withdrawing group, R ¹⁸ represents a substituent, R ¹⁹ and R ²⁰ are each .n5 represents a hydrogen atom or a substituent independently represents an integer of 0 to 4. here, the plurality of R ¹⁸ when n5 represents an integer of 2 to 4 may be the same or different. )

（一般式（６）中、ＥＷＧ²は電子吸引基を表す。Ｒ²¹およびＲ²⁴は各々独立に置換基を表し、Ｒ²²、Ｒ²³およびＲ²⁵は各々独立に水素原子または置換基を表す。ｎ６およびｎ７は各々独立に０〜４の整数を表す。ここで、ｎ６が２〜４の整数を表すとき又はｎ７が２〜４の整数を表すとき、複数のＲ²¹又は複数のＲ²⁴は各々同じでも異なっていてもよい。）
［６］前記感熱転写受像シートの受容層に含まれる熱可塑性樹脂の少なくとも１種が塩化ビニル系ポリマーであることを特徴とする［１］項に記載の熱転写記録システム。 [5] Any one of [2] to [4], wherein the ink sheet used by being overlapped with the thermal transfer image-receiving sheet contains at least one dye represented by the following general formula (6): The thermal transfer recording system according to claim 1.

(In General Formula (6), EWG ² represents an electron-withdrawing group. R ²¹ and R ²⁴ each independently represent a substituent, and R ²² , R ^23, and R ²⁵ each independently represent a hydrogen atom or a substituent. N6 and n7 each independently represents an integer of 0 to 4. Here, when n6 represents an integer of 2 to 4 or when n7 represents an integer of 2 to 4, a plurality of R ²¹ or a plurality of R ²⁴ May be the same or different.)
[6] The thermal transfer recording system according to item [1], wherein at least one thermoplastic resin contained in the receiving layer of the thermal transfer image-receiving sheet is a vinyl chloride polymer.

（一般式（７）中、Ｒ⁵¹およびＲ⁵²は各々独立に置換基を表す。ｎ８は０〜５の整数を表す。ｎ９は０〜４の整数を表す。ここで、ｎ８が２〜５の整数を表すとき又はｎ９が２〜４の整数を表すとき、複数のＲ⁵¹又は複数のＲ⁵²は各々同じでも異なっていてもよい。）

（一般式（８）中、Ｒ⁶¹は置換基を表し、Ｒ⁶²、Ｒ⁶³およびＲ⁶⁴は各々独立に水素原子または置換基を表す。ｎ１０は０〜４の整数を表す。ここで、ｎ１０が２〜４の整数を表すとき複数のＲ⁶¹は同じでも異なっていてもよい。） [7] The item [6], wherein the ink sheet used by being superimposed on the heat-sensitive transfer image-receiving sheet contains at least one dye represented by the following general formula (7) or (8): The thermal transfer recording system described.

(In the general formula (7), R ⁵¹ and R ⁵² each independently represent a substituent. N8 represents an integer of 0 to 5. n9 represents an integer of 0 to 4. Here, n8 is 2 to 5). Or when n9 represents an integer of 2 to 4, the plurality of R ⁵¹ or the plurality of R ⁵² may be the same or different.

(In the general formula (8), R ⁶¹ represents a substituent, R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or a substituent. N10 represents an integer of 0 to 4. Here, n10 And when R represents an integer of 2 to 4, a plurality of R ⁶¹ may be the same or different.)

（一般式（９）中、Ｒ⁷¹およびＲ⁷³は各々独立に水素原子または置換基を表す。Ｒ⁷²およびＲ⁷⁴は各々独立に置換基を表す。ｎ１１は０〜４の整数を表す。ｎ１２は０〜２の整数を表す。ここで、ｎ１１が２〜４の整数を表すとき又はｎ１２が２を表すとき、複数のＲ⁷⁴又は複数のＲ⁷²は各々同じでも異なっていてもよい。）

（一般式（１０）中、Ｒ⁸¹は水素原子または置換基を表す。Ｒ⁸²およびＲ⁸⁴は各々独立に置換基を表す。ｎ１３は０〜４の整数を表す。ｎ１４は０〜２の整数を表す。ここで、ｎ１３が２〜４の整数を表すとき又はｎ１４が２を表すとき、複数のＲ⁸⁴又は複数のＲ⁸²は各々同じでも異なっていてもよい。）

（一般式（１１）中、Ｒ⁹¹は水素原子または置換基を表す。Ｒ⁹²は置換基を表す。Ｒ⁹³およびＲ⁹⁴は各々独立に水素原子または置換基を表す。ｎ１５は０〜２の整数を表す。ここで、ｎ１５が２を表すとき複数のＲ⁹²は同じでも異なっていてもよい。Ｚ¹およびＺ²は、どちら一方が＝Ｎ−であり、他方が＝Ｃ(Ｒ⁹⁵)−を表す。Ｚ³およびＺ⁴は各々独立に＝Ｎ−または＝Ｃ(Ｒ⁹⁶)−を表す。ここで、Ｒ⁹⁵およびＲ⁹⁶は各々独立に水素原子または置換基を表す。） [8] The ink sheet used by being superimposed on the heat-sensitive transfer image-receiving sheet contains at least one dye represented by any one of the following general formulas (9), (10), and (11). The thermal transfer recording system according to [6] or [7].

(In General Formula (9), R ⁷¹ and R ⁷³ each independently represents a hydrogen atom or a substituent. R ⁷² and R ⁷⁴ each independently represent a substituent. N11 represents an integer of 0 to 4. n12 Represents an integer of 0 to 2. Here, when n11 represents an integer of 2 to 4 or when n12 represents 2, a plurality of R ⁷⁴ or a plurality of R ⁷² may be the same or different.

(In General Formula (10), R ⁸¹ represents a hydrogen atom or a substituent. R ⁸² and R ⁸⁴ each independently represents a substituent. N13 represents an integer of 0 to 4. n14 represents an integer of 0 to 2. Here, when n13 represents an integer of 2 to 4 or when n14 represents 2, the plurality of R ⁸⁴ or the plurality of R ⁸² may be the same or different.

(In the general formula (11), R ⁹¹ represents a hydrogen atom or a substituent. R ⁹² represents a substituent. R ⁹³ and R ⁹⁴ each independently represents a hydrogen atom or a substituent. Represents an integer, wherein when n15 represents 2, a plurality of R ⁹² may be the same or different, and ^one of Z ¹ and Z ² is ═N— and the other is ═C (R ⁹⁵ ). Z ³ and Z ⁴ each independently represent ═N— or ═C (R ⁹⁶ ) —, wherein R ⁹⁵ and R ⁹⁶ each independently represent a hydrogen atom or a substituent.

（一般式（１２）中、Ｒ¹⁰¹およびＲ¹⁰²は各々独立に置換基を表す。Ｒ¹⁰³およびＲ¹⁰⁴は各々独立に水素原子または置換基を表す。ｎ１６およびｎ１７は各々独立に０〜４の整数を表す。ここで、ｎ１６が２〜４の整数を表すとき又はｎ１７が２〜４の整数を表すとき、複数のＲ¹⁰¹又は複数のＲ¹⁰²は各々同じでも異なっていてもよい。）

（一般式（１３）中、Ｒ¹¹¹およびＲ¹¹³は各々独立に水素原子または置換基を表す。Ｒ¹¹²およびＲ¹¹⁴は各々独立に置換基を表す。ｎ１８は０〜４の整数を表す。ｎ１９は０〜２の整数を表す。ここで、ｎ１８が２〜４の整数を表すとき又はｎ１９が２を表すとき、複数のＲ¹¹⁴又は複数のＲ¹¹²は各々同じでも異なっていてもよい。） [9] The ink sheet used by being superimposed on the thermal transfer image-receiving sheet contains at least one dye represented by the following general formula (12) or (13) [6] to [6] [8] The thermal transfer recording system according to any one of [8].

(In General Formula (12), R ¹⁰¹ and R ¹⁰² each independently represent a substituent. R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom or a substituent. N16 and n17 each independently represent 0 to 4; Wherein n16 represents an integer of 2 to 4 or n17 represents an integer of 2 to 4, a plurality of R ¹⁰¹ or a plurality of R ¹⁰² may be the same or different.

(In the general formula (13), R ¹¹¹ and R ¹¹³ each independently represents a hydrogen atom or a substituent. R ¹¹² and R ¹¹⁴ each independently represent a substituent. N18 represents an integer of 0 to 4. n19 Represents an integer of 0 to 2. Here, when n18 represents an integer of 2 to 4 or when n19 represents 2, a plurality of R ¹¹⁴ or a plurality of R ¹¹² may be the same or different.

[10] The thermal transfer recording system according to any one of [2] to [9], wherein the receiving layer of the thermal transfer image-receiving sheet contains a fluorine-based release agent compound or a silicone-based release agent compound. .
[11] Any one of [1] to [10], wherein each of the protective belts is hung on two rollers in addition to the platen roller, and the shape viewed from the side surface forms a triangle. 2. The thermal transfer recording system according to item 1.
[12] The two rollers are flanged rollers that are movable in the axial direction of the platen roller, and the distance between the pair of protective belts can be changed according to the width of the ink sheet and the thermal transfer image-receiving sheet. The thermal transfer recording system according to item [11], wherein
[13] The thermal transfer recording system according to any one of [1] to [12], wherein the receiving layer of the thermal transfer image-receiving sheet is formed by applying water as a main medium.

  According to the present invention, a pair of protective belts are hung on the platen so as to receive both ends of the heating element array protruding from the bonded ink sheet and thermal transfer image receiving sheet. The part does not touch the platen and get scratched. By using a specific heat-sensitive transfer image-receiving sheet, the head is not damaged even when high-temperature high-speed processing is performed, and both durability of the head and high-temperature high-speed processing can be achieved. In particular, by using a specific heat-sensitive transfer image-receiving sheet and a specific ink sheet in combination, high-temperature and high-speed processing can be performed even better.

  In addition, since the pair of protective belts are movable in the axial direction of the platen in accordance with the widths of the ink sheet and the thermal transfer image receiving sheet, the thermal transfer recording system of the present invention is an ink sheet having various widths. And can be used for thermal transfer image-receiving sheets.

The present invention will be described in detail below.
In the thermal printer used in the thermal transfer recording system of the present invention, a pair of protective belts are arranged in a state of being partially wound on both sides of the platen roller, and the bonded ink sheet and thermal transfer image-receiving sheet (hereinafter referred to as “this specification”). A pair of heat-sensitive recording sheets) is supported by a pair of protective belts so that both ends of the heating element array protruding from both sides of the heating element array do not come into contact with the platen roller. Even in a narrow case, both ends of the heating element array are not in direct contact with the platen roller, so that this portion is not damaged.

  First, a preferred embodiment of a thermal printer used in the thermal transfer recording system of the present invention will be described in detail with reference to the accompanying drawings. In the description of each drawing, the same elements are denoted by the same reference numerals.

  As shown in FIG. 1, the pair of thermal recording sheets 10 in which the ink sheet and the thermal transfer image receiving sheet are bonded together are nipped by the conveyance roller pair 11 and conveyed on the platen roller 12. The conveying roller pair 11 and the platen roller 12 are rotated by a pulse motor (not shown). The conveying roller pair 11 and the platen roller 12 rotate intermittently or continuously at the same speed in the same direction to convey a pair of thermal recording sheets 10.

  A vertical thermal head 13 is provided opposite to the platen roller 12. The thermal head 13 is formed with a heating element array 13a in which a large number of heating elements are arranged in a line in the main scanning direction, and each heating element generates thermal energy according to the density of the pixel. The thermal head 13 presses the pair of thermal recording sheets 10 supported on the platen roller 12 during conveyance of the pair of thermal recording sheets 10.

  In the case of a pair of narrow thermal recording sheets, since the heating element array 13a contacts the platen roller 12, the heating element array 13a is rubbed and damaged. Therefore, the protective belt 18 is hung in a triangle on one side of the platen roller 12 and the rollers 25 and 26. Similarly, the protective belt 19 is also hung on the other side of the platen roller 12 and the rollers 27 and 28.

  As shown in FIG. 2, the rollers 25 and 26 are attached to the moving base 30. These rollers 25 and 26 are formed with roller bodies 25a and 26a and flanges 25b to 26b. Since the rollers 27 and 28 are the same, only the reference numerals are given and the description is omitted.

  The protection belts 18 and 19 are in close contact with the substantially half circumference of the surface of the platen roller 12 and rotate together with the rollers 25 to 28 when the platen roller 12 rotates. The protective belts 18 and 19 are prevented from falling off by the flanges 25b to 28b.

  The moving bases 30 and 31 are movably attached to the guide bars 32 and 33. A drive shaft 36 driven by a motor 35 is provided between the guide bars 32 and 33. The drive shaft 36 is formed with two feed screws 36a and 36b having different lead directions, and the screws formed on the moving bases 30 and 31 are screwed to the feed screws 36a and 36b.

  When the motor 35 is driven to rotate the drive shaft 36 in the direction of the arrow, the moving bases 30 and 31 move in the direction of the arrow along the guide rods 32 and 33, so that the protection belts 18 and 19 slide on the platen roller 12. Move to increase the interval. Further, when the drive shaft 36 rotates in the direction opposite to the arrow direction, the distance between the protective belts 18 and 19 becomes narrower.

  For example, polyethylene terephthalate is used as the protective belts 18 and 19. Further, in order to make good contact between the heating element array 13a and the pair of thermosensitive recording sheets 10, a very thin one having a thickness of 0.1 mm or less is used. The protection belts 18 and 19 are arranged at intervals slightly shorter than the paper width L of the pair of thermal recording sheets 10, and the ends 10 a of the pair of thermal recording sheets 10 overlap the protection belts 18 and 19 during printing. It is done. Since the distance between the protection belts 18 and 19 can be set in a stepless manner within the range in which the moving bases 30 and 31 move the drive shaft 36, it can correspond to thermal recording sheets of various paper width sizes.

  The pair of heat-sensitive recording sheets 10 having an overall thickness of 0.20 to 0.25 mm is used. However, since the protective belts 18 and 19 are extremely thin as described above, the pair of heat-sensitive recording sheets 10 is used. There is almost no excitement where the overlapping parts become steps. Further, since the outside of the recording area of the pair of thermal recording sheets 10 is superimposed on the protection belts 18 and 19, there is no influence on the printed image.

  Further, while the protection belts 18 and 19 are rotating, they are in contact with the heating element array 13a of the thermal head 12, but since the surfaces of the protection belts 18 and 19 are smoother than the platen roller 12, the heating element array 13a. Will not hurt. A lubricant layer is preferably formed on the surface of the protective belts 18 and 19.

  Before and after the thermal head 13, a yellow UV lamp 37 that emits UV light with an emission peak of approximately 420 nm for photofixing the yellow dye, and an UV light emission with an emission peak of approximately 365 nm for photofixing the magenta dye. A magenta ultraviolet lamp 38 is disposed. Each of the ultraviolet lamps 37 and 38 has a rod shape, and reflectors 39 and 40 are provided behind them.

  The operation of the color thermal printer configured as described above will be described. When the switch is turned on according to the paper width of the pair of thermal recording sheets 10, the motor 35 rotates while this switch is on. The drive shaft 36 is rotated by the motor 35, and the moving bases 30 and 31 move along the guide bars 32 and 33. If the switch is turned OFF when the appropriate distance between the protective belts 18 and 19 is reached, the motor 35 stops. The pulse motor is driven while the movement bases 30 and 31 are moving, and the platen roller 12 is fed in an idle manner. Therefore, the protection belts 18 and 19 move smoothly on the surface of the platen roller 12 without being pulled excessively. The protection belts 18 and 19 are set at an interval slightly narrower than the paper width L of the pair of thermal recording sheets 10.

  When the print start switch is turned on, the conveyance roller pair 11 and the platen roller 12 start to rotate clockwise. A pair of thermal recording sheets 10 are sent from a paper feed cassette (not shown). When the leading ends of the pair of thermal recording sheets 10 reach the conveyance roller pair 11, the pair of thermal recording sheets 10 are nipped by the conveyance roller pair 11 and sent onto the platen roller 12.

  When the pair of thermal recording sheets 10 reaches the platen roller 12, both ends 10a of the pair of thermal recording sheets 10 get on the protective belts 18 and 19. Immediately before the recording area of the pair of thermal recording sheets 10 passes through the heating element array 13a of the thermal head 13, the thermal head 13 is lowered and the heating element array 13a is pressed against the pair of thermal recording sheets 10. Since both ends of the heating element array 13a protruding from the thermal recording sheet 10 are on the protective belts 18 and 19, it is possible to prevent the platen roller 12 from being directly contacted and damaged.

  When the heating element array 13a reaches the recording area of the pair of thermal recording sheets 10, each heating element is colored at a temperature that takes into consideration the coloring characteristics of the yellow dye, and a yellow image is thermally recorded line by line on the thermal recording sheet 10. The When the portion of the thermal recording sheet 10 on which the yellow image has been thermally recorded reaches the yellow ultraviolet lamp 37, the ultraviolet light of approximately 420 nm is irradiated and the yellow dye is photofixed.

  When the yellow image recording is completed and the rear ends of the pair of thermosensitive recording sheets 10 reach the conveying roller 11, the rotation of the conveying roller 11 and the platen roller 12 is temporarily stopped. Next, the conveyance roller 11 and the platen roller 12 rotate in the clockwise direction, and the pair of thermal recording sheets 10 are conveyed in the opposite directions. During this conveyance, a magenta image is thermally recorded line by line on the thermal recording sheet 10 by the thermal head 13. When the portion of the thermal recording sheet 10 on which the magenta image is thermally recorded reaches the magenta ultraviolet lamp 38, the magenta dye is photofixed by the ultraviolet rays of approximately 365 nm irradiated from here.

  After the light fixing of the magenta dye is completed, the rotation directions of the transport roller 11 and the platen roller 12 are switched again. A cyan image is thermally recorded while the recording area of the pair of thermal recording sheets 10 passes through the thermal head 13, and a full color image is formed on the thermal recording sheet 10 by three-color surface sequential recording.

  FIG. 3 shows a case where the protective belts 51 and 52 are arranged at the same or slightly wider interval as the paper width L of the pair of thermal recording sheets 53. In this case, protective belts 51 and 52 having a thickness of 0.15 to 0.25 mm are used. Since both ends of the heating element array 54a of the thermal head 54 are supported by the protection belts 51 and 52, the contact between the platen roller 55 and the thermal head 54 is prevented. In this embodiment, since the pair of heat-sensitive recording sheets 53 do not ride on the protection belts 51 and 52, no step is generated.

  The above embodiment is a three-pass one-head color thermal printer, but can also be applied to a drum-type color thermal printer that records a color thermal recording material while being wound around a platen drum. In addition to the 3-pass 1-head type, the invention can also be applied to a 3-head 1-pass type color thermal printer. Further, all of the protective belt may be wound around the platen. In this case, the protective belt cannot be moved according to the paper width, but the structure becomes simple.

Next, a thermal transfer image receiving sheet (image receiving sheet) used in the thermal transfer recording system of the present invention will be described.
The heat-sensitive transfer image-receiving sheet used in the present invention has a dye-receiving layer (receiving layer) formed on a support. A base layer is preferably formed between the receptor layer and the support. For example, a white background adjustment layer, a charge adjustment layer, an adhesive layer, and a primer layer are formed. Moreover, it is preferable that the heat insulation layer is formed between the base layer and the support body. Furthermore, a curl adjusting layer, a writing layer, and a charge adjusting layer are preferably formed on the back side of the support. Each layer is applied by a general method such as roll coating, bar coating, gravure coating, or gravure reverse coating. The receptor layer is preferably formed by applying water as a main medium. Here, the meaning that water is the main medium means that 40% by mass or more, preferably 60 to 95% by mass of water is contained in the entire medium.

<Receptive layer>
[Thermoplastic resin]
In the present invention, examples of the thermoplastic resin used in the receiving layer include halogenated polymers such as polyvinyl chloride and polyvinylidene chloride, polyvinyl acetate, ethylene vinyl acetate copolymer, vinyl chloride vinyl acetate copolymer, Polyacrylic ester, polystyrene, polystyrene acrylic and other vinyl resins, polyvinyl formal, polyvinyl butyral, polyvinyl acetal and other acetal resins, polyethylene terephthalate, polypropylene terephthalate, polycaprolactone (Placcel H-5, trade name, Daicel Chemical Industries ( Made of polyester resin, polycarbonate resin, cellulose resin and cellulose acetate butyrate (CAB551-0... Described in JP-A-4-296595 and JP-A-2002-264543. , CAB321-0.1, trade names, manufactured by Eastman Chemical Company) cellulose resins such as polyolefin resins such as polypropylene, polyamide resins such as urea resins, melamine resins, benzoguanamine resins. These resins can be arbitrarily blended and used within a compatible range. JP-A-57-169370, JP-A-57-207250, JP-A-60-25793, etc. also disclose resins having a receiving layer formed therein.

  Among the above polymers, it is more preferable to contain polycarbonate, polyester, polyurethane, polyvinyl chloride and a copolymer thereof, styrene-acrylonitrile copolymer, polycaprolactone or a mixture thereof, and polycarbonate, polyester, polyvinyl chloride and a copolymer thereof. A combination or a mixture thereof is particularly preferred. Polycarbonate, polyester, and polyvinyl chloride will be described in more detail. The above polymers can be used alone or as a mixture thereof.

(Polyester resin)
The polyester resin used for the receiving layer will be described in more detail. Polyester is obtained by polycondensation of a dicarboxylic acid component (including derivatives thereof) and a diol component (including derivatives thereof). The polyester resin contains an aromatic ring and / or an alicyclic ring. Regarding the technology of alicyclic polyester, the technology described in JP-A-5-238167 is effective in terms of dye uptake ability and image stability.

  The dicarboxylic acid component is selected from isophthalic acid, trimellitic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, and a mixture of two or more thereof. Preferably, it is selected from isophthalic acid, trimellitic acid, terephthalic acid, or a mixture of two or more thereof. Inclusion of an alicyclic component as the dicarboxylic acid component is more desirable from the viewpoint of improving light resistance. More preferably, 1,4-cyclohexanedicarboxylic acid and isophthalic acid are used. The dicarboxylic acid component is used in a proportion of 50 to 100 mol% of isophthalic acid, 0 to 1 mol% of trimellitic acid, 0 to 50 mol% of terephthalic acid, and 0 to 15 mol% of 1,4-cyclohexanedicarboxylic acid. To do.

  The diol component can be selected from ethylene glycol, polyethylene glycol, tricyclodecane dimethanol, 1,4-butanediol, bisphenol, or a mixture of two or more thereof. Preferably, it is selected from ethylene glycol, polyethylene glycol, and tricyclodecane dimethanol. It is more desirable to include an alicyclic component as a diol component from the viewpoint of improving light resistance. In addition to tricyclodecane dimethanol, alicyclic diol components such as cyclohexane diol, cyclohexane dimethanol, and cyclohexane diethanol can be used. A preferred alicyclic diol component is tricyclodecane dimethanol. The diol component is ethylene glycol 0 to 50 mol /%, polyethylene glycol 0 to 10 mol /%, tricyclodecane dimethanol 0 to 90 mol /%, preferably 30 to 90 mol /%, more preferably 40 to 90 mol /%, 4-butanediol is used at a ratio of 0 to 50 mol /% and bisphenol A 0 to 50 mol /% so that the total amount is 100 mol%.

  The polyester resin used in the present invention uses at least the dicarboxylic acid component and the diol component, and has a molecular weight (weight average molecular weight (Mw)) of about 11,000 or more, preferably about 15000 or more, more preferably about 17,000 or more. Use polycondensation. If a material having a very low molecular weight is used, the elastic modulus of the receiving layer formed is low and the heat resistance is insufficient, so that it is difficult to ensure the releasability between the thermal transfer sheet and the image receiving sheet. The molecular weight is preferably as large as possible from the viewpoint of increasing the elastic modulus, and it may not be dissolved in the coating solution solvent when forming the receiving layer, or adverse effects such as adversely affecting the adhesion to the base sheet after coating and drying the receiving layer. Unless otherwise specified, it is not particularly limited, but it is preferably about 25,000 or less, and at most about 30000. In addition, what is necessary is just to use the conventionally well-known method for the synthesis | combining method of ester resin.

  Examples of saturated polyesters are Byron 200, Byron 290, Byron 600, etc. (all trade names, manufactured by Toyobo Co., Ltd.), KA-1038C (trade names, manufactured by Arakawa Chemical Industries, Ltd.), TP220, TP235 (all products) Name, manufactured by Nippon Synthetic Chemical Co., Ltd.).

(Polycarbonate)
The polycarbonate resin used for the receiving layer will be described in more detail. Polycarbonate means polyester having units of carbonic acid and diol, and can be synthesized by a method of reacting diol with phosgene or a method of reacting carbonate ester.

  Diol components include bisphenol A, ethylene glycol, propylene glycol, diethylene glycol, butanediol, pentanediol, hexanediol, 1,4-cyclohexanedimethanol, nonanediol, 4,4'-bicyclo (2,2,2) hept 2-ylidenebisphenol, 4,4 ′-(octahydro-4,7-methano-5H-indene-5-ylidene) bisphenol and 2,2 ′, 6,6′-tetrachlorobisphenol A, and bisphenol A, ethylene glycol, diethylene glycol, butanediol and pentanediol are preferred, bisphenol A, ethylene glycol and butanediol are more preferred, and bisphenol A and ethylene glycol are particularly preferred. The polycarbonate used in the present invention uses at least the above-mentioned one kind of diol component, but a plurality of diols may be mixed and used.

  The bisphenol A-polycarbonate, which is a particularly preferred embodiment of the polycarbonate used in the present invention, will be described in detail. The technique of unmodified polycarbonate, centered on bisphenol A-polycarbonate, is described in US Pat. No. 4,695,286. The polycarbonate used in the present invention is a polycondensate having a molecular weight (weight average molecular weight (Mw)) of about 1000 or more, preferably about 3000 or more, more preferably about 5000 or more, and particularly preferably about 10,000 or more. Polycarbonates such as Makrolon-5700 (trade name, Bayer AG) and LEXAN-141 (trade name, General Electric) can be mentioned as examples.

  A technique for modifying polycarbonate by mixing bisphenol A and a diol such as ethylene glycol is described in US Pat. No. 4,927,803. The polyether block unit can be formed from a linear aliphatic diol having from 2 to about 10 carbon atoms, but is preferably formed from ethylene glycol. In a preferred embodiment of the present invention, the polyether block units have a number molecular weight of about 4,000 to about 50,000 and the bisphenol A-polycarbonate block units have a number molecular weight of about 15,000 to about 250,000. The overall molecular weight of the block copolymer is preferably from about 30,000 to about 300,000. Makrolon KL3-1013 (trade name, Bayer AG) can be mentioned as an example.

  It is also preferable to mix these unmodified and modified bisphenol A-polycarbonates, and it is preferable to blend unmodified bisphenol A-polycarbonates and polyether-modified polycarbonates in a mass ratio of 80:20 to 10:90, improving fingerprint resistance. From the viewpoint of mass ratio, a mass ratio of 50:50 to 40:60 is particularly preferable. The blending technology of unmodified and modified bisphenol A-polycarbonate is also described in JP-A-6-227160.

  A preferred embodiment of the thermoplastic resin used in the receiving layer is a blend system of the polycarbonate and the polyester. In this blend system, it is preferable that the compatibility between the polycarbonate and the polyester can be ensured. The polyester preferably exhibits a glass transition temperature (Tg) of about 40 to about 100 ° C, and the polycarbonate exhibits a Tg of about 100 to about 200 ° C. The polyester preferably exhibits a lower Tg than polycarbonate and acts as a polymer plasticizer for the polycarbonate. The Tg of the final polyester / polycarbonate blend is preferably 40 ° C to 100 ° C. Higher Tg polyester and polycarbonate polymers can also be useful by adding plasticizers.

  In a further preferred embodiment, the unmodified bisphenol A-polycarbonate and the polyester polymer are blended in a mass ratio that will bring the final blend Tg to the desired value and minimize cost. The polycarbonate and polyester polymer can be conveniently blended in a mass ratio of about 75:25 to 25:75, but more preferably in a mass ratio of about 60:40 to about 40:60. Japanese Patent Application Laid-Open No. 6-227161 discloses a technique of blending polycarbonate and polyester.

  In the polycarbonate used in the receiving layer, a polymer network structure is formed in the receiving layer by reacting the polycarbonate having an average molecular weight of about 1000 to about 10,000 having at least two hydroxyl groups with a crosslinking agent that reacts with hydroxyl groups. It may be formed. As disclosed in JP-A-6-155933, a technique of a crosslinking agent such as a polyfunctional isocyanate is also disclosed, and the adhesion to a dye donor after transfer can be improved. Further, as disclosed in JP-A-8-39942, a technique is disclosed in which a dye-receiving element for thermal dye transfer using dibutyltin diacetate is used in the crosslinking reaction between polycarbonate and isocyanate. Not only can the crosslinking reaction be accelerated, but image stability and fingerprint resistance can be improved.

(Polyvinyl chloride copolymer)
The polyvinyl chloride copolymer used for the receiving layer will be described in more detail. The polyvinyl chloride copolymer preferably has a vinyl chloride component content of 85 to 97% by mass and a polymerization degree of 200 to 800. The monomer copolymerized with vinyl chloride is not particularly limited, as long as it can be copolymerized with vinyl chloride, and vinyl acetate is particularly preferable. Therefore, in the present invention, vinyl chloride-vinyl acetate copolymer is excellent for the receiving layer, but the vinyl chloride-vinyl acetate copolymer is not necessarily limited to a copolymer of only a vinyl chloride component and a vinyl acetate component. First, it may contain a vinyl alcohol component, a maleic acid component, and the like within a range not impeding the object of the present invention. Other monomer components constituting such a copolymer comprising vinyl chloride and vinyl acetate as main monomers include vinyl alcohol, vinyl alcohol derivatives such as vinyl propionate, acrylic acid and methacrylic acid, and their Acrylic and methacrylic acid derivatives such as methyl, ethyl, propyl, butyl, 2-ethylhexyl ester, maleic acid derivatives such as maleic acid, diethyl maleate, dibutyl maleate, dioctyl maleate, methyl vinyl ether, butyl vinyl ether, 2-ethylhexyl Examples thereof include vinyl ether derivatives such as vinyl ether, acrylonitrile, methacrylonitrile, and styrene. The components of vinyl chloride and vinyl acetate incorporated in the copolymer may be in any ratio, but the vinyl chloride component is preferably 50% by mass or more in the copolymer. Moreover, it is preferable that components other than vinyl chloride and vinyl acetate mentioned above are 10 mass% or less.

Examples of such vinyl chloride-vinyl acetate copolymers include SOLBIN C, SOLBIN CL, SOLBIN CH, SOLBIN CN, SOLBIN C5, SOLBIN M, SOLBIN MF, SOLBIN A, SOLBIN AL, SOLBIN TA5R, SOLBIN TAO, SOLBIN, KOL, SOLB6 SOLBIN TA2 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), ESREC A, ESREC C, ESREC M (all trade names, manufactured by Sekisui Chemical Co., Ltd.), Vinylite VAGH, Vinylite VYHH, Vinylite VMCH, VINYLITE VYHD, VINYLITE VYLF, VINYLITE VYNS, VINYLITE VMCC, VINYLITE VMCA, VINYLITE VAGD, VINYLITE VERR, VINYLITE VROH (all trade names, Union Carby) Company, Ltd.), DENKAVINYL 1000GKT, DENKAVINYL 1000L, DENKAVINYL 1000CK, DENKAVINYL 1000A, DENKAVINYL 1000LK _2, DENKAVINYL 1000AS, DENKAVINYL 1000MT _2, DENKAVINYL 1000CSK, DENKAVINYL 1000CS, DENKAVINYL 1000GK, DENKAVINYL 1000GSK, DENKAVINYL 1000GS, DENKAVINYL 1000LT _3, DENKAVINYL 1000D, DENKAVINYL 1000W (both are trade names, manufactured by Denki Kagaku Kogyo Co., Ltd.) and the like.

[Plasticizer]
In order to improve the sensitivity of the receiving layer, a plasticizer may be added. Examples of such plasticizers include monomeric plasticizers such as phthalic acid esters, phosphoric acid esters, adipic acid esters, and sebacic acid esters, and polyester-type plasticizers obtained by polymerizing adipic acid, sebacic acid, and propylene glycol. In general, those which can be used as plasticizers for vinyl chloride resins are mentioned. The plasticizers mentioned above generally have a low molecular weight, but in addition, olefin-based special copolymer resins used as vinyl chloride polymer plasticizers can also be used. Resins used for such applications are commercially available as Elvalloy 741, Elvalloy 742, Elvalloy HP443, Elvalloy HP553, Elvalloy EP4015, Elvalloy EP4043, Elvalloy EP4051 (all trade names, manufactured by Mitsui DuPont Polychemical Co., Ltd.). You can use what you have. Such a plasticizer can be added in an amount of about 100% by mass relative to the resin, but the amount used is preferably 30% by mass or less in terms of bleeding of the printed matter.

  The receptor layer can be cast by extrusion coating the melt of the polymer resin, without solvent application. The technology of this extrusion coating is described in Encyclopedia of Polymer Science and Engineering, Volume 3 (John Wiley, New York), 1985, 563, Volume, 1986, page 608. Japanese Patent Application Laid-Open No. 7-179075 also discloses a technique relating to a thermal dye transfer material, and this technique can also be suitably used. As the polymer resin, a copolymer obtained by condensing cyclohexane dicarboxylate and a 50/50 mol% mixture (COPOL; registered trademark) of ethylene glycol / bisphenol A-diethanol is particularly preferable.

[Release agent]
If the image-receiving surface of the thermal transfer image-receiving sheet does not have sufficient peeling performance, the ink sheet (thermal transfer sheet) and the thermal transfer image-receiving sheet (image-receiving sheet) are fused by heat from the thermal head during image formation, and a large peeling sound is generated during peeling. There arises a problem of so-called abnormal transfer that occurs, the dye layer is transferred with the layer, or the receiving layer is peeled off from the substrate. As a method for solving the above problem of releasability, there are known a method of internally adding various release agents into the receiving layer or a method of separately providing a release layer on the receiving layer. In the present invention, it is preferable to use a release agent in the receiving layer in order to ensure the releasability between the thermal transfer sheet and the image receiving sheet during image printing.
Examples of the release agent include solid waxes such as polyethylene wax, amide wax, and Teflon powder; silicone oil, phosphate ester compounds, fluorine surfactants, silicone surfactants, and other known in the art. A mold release agent can be used, and silicone compounds such as fluorine compounds represented by fluorine surfactants, silicone surfactants, silicone oils and / or cured products thereof are preferably used.

  As the silicone oil, straight silicone oil, modified silicone oil or a cured product thereof can be used. Straight silicone oils include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil. Examples of dimethyl silicone oil include KF96-10, KF96-100, KF96-1000, KF96H-10000, KF96H-12500, and KF96H. -100,000 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and as dimethyl silicone oil, KF50-100, KF54, KF56 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Can be mentioned.

  The modified silicone oil can be classified into a reactive silicone oil and a non-reactive silicone oil. The reactive silicone oil includes amino modification, epoxy modification, carboxyl modification, hydroxy modification, methacryl modification, mercapto modification, phenol modification, one-terminal reactivity and heterofunctional modification. As amino-modified silicone oil, KF-393, KF-857, KF-858, X-22-3680, X-22-3801C, KF-8010, X-22-161A, KF-8012 (all trade names, Shin-Etsu Chemical Co., Ltd.) and the like, and epoxy-modified silicone oils include KF-100T, KF-101, KF-60-164, KF-103, X-22-343, X-22-3000T ( All of them are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the carboxyl-modified silicone oil include X-22-162C (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the hydroxy-modified silicone oil include X-22-160AS, KF-6001, KF-6002, KF-6003, X-22-170DX, X-22-176DX, X-22-176D, X-22-176DF (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) X-22-164A, X-22-164C, X-24-8201, X-22-174D, X-22-2426 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. .

  The reactive silicone oil can be used after being cured, and can be classified into a reaction curable type, a photo curable type, a catalyst curable type, and the like. Of these, reaction-curable silicone oils are particularly preferable. As the reaction-curable silicone oils, those obtained by reaction-curing amino-modified silicone oil and epoxy-modified silicone oil are preferable. Further, as the catalyst curable type or photo curable type silicone oil, KS-705F-PS, KS-705F-PS-1, KS-770-PL-3 [catalyst curable type silicone oil: all trade names, Shin-Etsu Chemical Co., Ltd. KS-720, KS-774-PL-3 [photocured silicone oil: trade names, manufactured by Shin-Etsu Chemical Co., Ltd.], and the like. The addition amount of these curable silicone oils is preferably 0.5 to 30% by mass of the resin constituting the image receiving layer. The release agent is used in an amount of 2 to 4% by mass, preferably about 2 to 3% by mass, based on 100 parts by mass of the polyester resin. If the amount is too small, the releasability cannot be ensured, and if the amount is too large, the protective layer will not be transferred to the image receiving sheet.

  Non-reactive silicone oils include polyether modification, methylstyryl modification, alkyl modification, higher fatty acid ester modification, hydrophilic special modification, higher alkoxy modification, fluorine modification and the like. Examples include polyether-modified silicone (KF-6012, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and methylstil-modified silicone silicone oil (24-510, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Can be mentioned. Moreover, the modified silicone represented by either of the following general formulas 1-3 can also be used.

  In General Formula 1, R represents a hydrogen atom, an aryl group, or a linear or branched alkyl group that may be substituted with a cycloalkyl group. m and n represent an integer of 2000 or less, and a and b represent an integer of 30 or less.

  In General Formula 2, R represents a hydrogen atom, an aryl group, or a linear or branched alkyl group which may be substituted with a cycloalkyl group. m represents an integer of 2000 or less, and a and b represent an integer of 30 or less.

  In General Formula 3, R represents a hydrogen atom, an aryl group, or a linear or branched alkyl group which may be substituted with a cycloalkyl group. m and n represent an integer of 2000 or less, and a and b represent an integer of 30 or less.

Silicone oils such as those described above are described in “Silicone Handbook” (published by Nikkan Kogyo Shimbun Co., Ltd.), and are described in JP-A-8-108636 and JP-A-2002-264543 as curing technologies for curable silicone oils. The technique can be preferably used.
Note that abnormal transfer may occur in which the dye binder is taken on the receiving layer in the highlight portion of the monochromatic print. In addition, conventionally, addition polymerization type silicones generally proceed with a curing reaction in the presence of a catalyst, and almost all of iron group and platinum group 8 transition metal complexes are effective as curing catalysts. However, in general, platinum compounds are most efficient, and platinum catalysts which are platinum complexes soluble in silicone oil are usually preferably used. As an addition amount necessary for the reaction, about 1 to 100 ppm is sufficient.

  This platinum catalyst has a strong interaction with organic compounds containing multiple bonds, such as organic compounds containing N, P, S, etc., heavy metal ionic compounds such as Sn, Pb, Hg, Bi, As, acetylene groups, etc. When used together with the above compounds (catalyst poisons), the ability to hydrosilylate as a catalyst is lost, and the function as a curing catalyst is lost, so there is a drawback of causing poor curing of the silicone ("Silicone Handbook" Nikkan Kogyo). Newspaper company). Therefore, such a poorly cured addition polymerization type silicone does not exhibit any peeling performance even when used in the receiving layer. It is conceivable to use an isocyanate compound as a curing agent that reacts with active hydrogen, and this isocyanate compound and the organotin compound as a catalyst thereof are catalyst poisons of a platinum catalyst. Therefore, conventionally, the addition polymerization type silicone is not used in combination with an isocyanate compound, and thus is not used in combination with a modified silicone having active hydrogen that exhibits a peeling performance when cured with an isocyanate compound. .

  However, the ratio of the reactive group equivalent of the curing agent that reacts with active hydrogen to the reactive group equivalent of both the thermoplastic resin and the modified silicone having active hydrogen is 1: 1 to 10: 1. 2) Addition polymerization type By setting the platinum catalyst amount with respect to silicone to 100 to 10,000 ppm as platinum atoms of the platinum catalyst, it is possible to prevent curing of the addition polymerization type silicone. When the reactive group equivalent of the curing agent that reacts with the active hydrogen of 1) is 1 or less, the curing amount of the active hydrogen-containing silicone and the active hydrogen of the thermoplastic resin is small, and good release performance is obtained. Absent. On the other hand, when the equivalent ratio is 10 or more, the usable time of the ink of the receiving layer coating liquid is short and practically unusable. Further, when the platinum catalyst amount of 2) is 100 ppm or less, the activity is lost due to the catalyst poison, and when it is 10000 ppm or more, the ink usable time of the receiving layer coating liquid is short and cannot be used.

The coating amount of the receiving layer is preferably 0.5 to 10 g / m ² (in terms of solid content, hereinafter the coating amount in the present invention is a numerical value in terms of solid content unless otherwise specified).

<Release layer>
The cured modified silicone oil may be formed on the receptor layer as a release layer without being added to the receptor layer. In this case, the receiving layer may be formed using one or more kinds of thermoplastic resins as described above, or a receiving layer to which silicone is added may be used. The release layer contains a curable modified silicone, and the type and usage of the silicone used are the same as those used for the receiving layer. Further, when a catalyst or a retarder is used, it is the same as that added to the receiving layer. The release layer may be formed only of silicone, or may be used as a binder resin by mixing with a resin having good compatibility. The thickness of the release layer is about 0.001 to 1 g / m ^2.

  Fluorosurfactants include Fluorad FC-430 and FC-431 (both trade names, manufactured by 3M).

<Underlayer>
A base layer is preferably formed between the receptor layer and the support. For example, a white background adjustment layer, a charge adjustment layer, an adhesive layer, and a primer layer are formed. These layers can be formed in the same manner as described in, for example, Japanese Patent No. 3585599 and Japanese Patent No. 2925244.

<Insulation layer>
The heat insulating layer (foamed layer) plays a role of protecting the support from heat during heat transfer using a thermal head. Moreover, since it has high cushioning properties, a thermal transfer image-receiving sheet with high printing sensitivity can be obtained even when paper is used as the substrate.
The heat insulating layer is formed from a resin and a foaming agent. As the resin for the heat insulating layer, a known resin such as urethane resin, acrylic resin, methacrylic resin, modified olefin resin, or a blend thereof can be used. A heat insulating layer is formed by coating a resin obtained by dissolving and / or dispersing these resins in an organic solvent or water. The heat insulating layer coating liquid is an aqueous coating liquid that does not affect the foaming agent. For example, water-soluble, water-dispersible, or SBR latex, urethane emulsion, polyester emulsion, emulsion of vinyl acetate and its copolymer, emulsion of acrylic copolymer such as acrylic and acrylic styrene, vinyl chloride Emulsions such as emulsions, or dispersions thereof can be used. However, in the case where microspheres described later are used as the foaming agent, an emulsion of vinyl acetate and its copolymer, acrylic and Emulsion of acrylic copolymer such as acrylic styrene It is preferable to use.

  Since these resins can easily control the glass transition point, flexibility, and film-forming property by changing the type of monomer to be copolymerized and their blending ratio, plasticizers and film-forming aids are added. Even if it is not, it is suitable in that the desired physical properties can be obtained, the color change is small during storage in various environments after film formation, and the physical properties change little over time. Of the above-mentioned resins, SBR latex is not preferred because it generally has a low glass transition point and is likely to cause blocking, and yellowing is likely to occur after film formation or during storage. Many urethane-based emulsions contain solvents such as NMP and DMF, and are not preferable because they easily affect the foaming agent. Polyester emulsions, dispersions, and vinyl chloride emulsions are generally not preferred because of their high glass transition points and poor microsphere foaming properties. Although some of them are soft, they are preferably not used because they are given flexibility by adding a plasticizer.

  The foaming performance of the foaming agent is greatly influenced by the hardness of the resin. In order for the foaming agent to expand to a desirable expansion ratio, a glass transition point of −30 to 20 ° C. or a film forming temperature of 20 ° C. or lower is desirable. When the glass transition point is 20 ° C. or higher, the flexibility is insufficient and the foaming performance of the foaming agent is degraded. In addition, those having a glass transition point of −30 ° C. or lower may cause blocking (generated at the foam layer and the back surface of the base material when the base material after the foam layer is wound) or thermal transfer. When the image receiving sheet is cut, a defect (such as when the image receiving sheet is cut, the resin of the foam layer is stuck to the blade of the cutter, the appearance is deteriorated, and the size of the cutting is confounded). Sometimes. Moreover, when the minimum film-forming temperature is 20 ° C. or higher, film-forming defects occur during coating and drying, and defects such as surface cracks occur.

  Defoaming agents such as dinitropentamethylenetetramene, diazoaminobenzene, azobisisobutyronitrile, azodicarboxamide, etc. that decompose when heated to generate gases such as oxygen, carbon dioxide and nitrogen Examples thereof include known foaming agents such as microspheres in which a low boiling point liquid such as butane or pentane is covered with a resin such as polyvinylidene chloride or polyacrylonitrile to form microcapsules. Among these, microspheres in which a low-boiling liquid such as butane and pentane is covered with a resin such as polyvinylidene chloride and polyacrylonitrile to form microcapsules are preferably used. These foaming agents are foamed by heating after forming the foamed layer, and have high cushioning properties and heat insulation properties after foaming. The amount of the foaming agent used is preferably in the range of 0.5 to 100 parts by mass per 100 parts by mass of the resin forming the foamed layer. If it is 0.5 parts by mass or less, the cushioning property of the foamed layer is low, and the effect of forming the foamed layer cannot be obtained. If it is 100 parts by mass or more, the hollow ratio after foaming becomes too large, the mechanical strength of the foamed layer is lowered, and it becomes impossible to withstand normal handling. In addition, the foam layer surface loses smoothness, which adversely affects the appearance and print quality. The thickness of the entire foam layer is preferably 30 to 100 μm. When it is 30 μm or less, cushioning properties and heat insulation are insufficient, and when it is 100 μm or more, the effect of the foamed layer is not improved and the strength is lowered. Moreover, as a particle size of a foaming agent, that whose volume average particle diameter before foaming is about 5-15 micrometers and whose particle diameter after foaming is 20-50 micrometers is preferable. When the volume average particle size before foaming is 5 μm or less and the particle size after foaming is 20 μm or less, the cushion effect is low, the volume average particle size before foaming is 15 μm or more, and the particle size after foaming is 20 to 50 μm or more. Such a material is not preferable because the surface of the foam layer is uneven, which adversely affects the image quality of the formed image.

  Particularly preferred among the foaming agents are low-temperature foaming type microspheres having a partition wall softening temperature and foaming start temperature of 100 ° C. or lower and an optimal foaming temperature (the temperature at which the foaming ratio becomes the highest with a heating time of 1 minute) of 140 ° C. or lower. It is preferable that the heating conditions during foaming be as low as possible. By using microspheres having a low foaming temperature, thermal wrinkles and curling of the base material during foaming can be prevented. The microsphere having a low foaming temperature can be obtained by adjusting the blending amount of a thermoplastic resin such as polyvinylidene chloride or polyacrylonitrile that forms the partition walls. The volume average particle diameter is 5 to 15 μm. The foam layer using this microsphere is such that the bubbles obtained by foaming are closed cells, foamed by a simple process of heating alone, the thickness of the foam layer can be easily controlled by the amount of microspheres, etc. There are advantages.

  However, this microsphere is weak against an organic solvent, and when a coating solution using an organic solvent is used as the foam layer, the partition walls of the microsphere are eroded and the foamability is lowered. Therefore, when microspheres such as those described above are used, organic solvents that attack the partition walls, for example, ketones such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate, and organic solvents such as lower alcohols such as methanol and ethanol It is better to use a water-based coating solution that does not contain water. Accordingly, an aqueous coating solution, specifically, a resin using a water-soluble or water-dispersible resin, or a resin emulsion, preferably an acrylic styrene emulsion or a modified vinyl acetate emulsion may be used. In addition, even if the foamed layer is formed with an aqueous coating solution, the addition of high-boiling and highly polar solvents such as NMP, DMF, and cellosolve as co-solvents, film-forming aids, and plasticizers will affect the microspheres. Therefore, it is necessary to pay attention to the composition of the aqueous resin to be used, the amount of the high-boiling solvent added, and to confirm whether the microcapsules are adversely affected.

<Support>
As the support, coated paper, WP paper (double-sided laminated paper), or the like can be used.

-Coated paper-
The coated paper is a paper obtained by coating various sheets of resin, rubber latex, or polymer material on one side or both sides of a sheet such as a base paper, and the coating amount varies depending on the application. Examples of such coated paper include art paper, cast coated paper, Yankee paper, and the like.

  As the resin applied to the surface of the base paper or the like, it is appropriate to use a thermoplastic resin. Examples of such a thermoplastic resin include the following thermoplastic resins (a) to (h).

(A) Polyolefin resins such as polyethylene resins and polypropylene resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, acrylic resins, and the like.
(B) A thermoplastic resin having an ester bond. For example, a dicarboxylic acid component (these dicarboxylic acid components may be substituted with a sulfonic acid group, a carboxyl group, etc.) and an alcohol component (these alcohol components may be substituted with a hydroxyl group, etc.) Polyester resin, polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate and other polyacrylic acid ester resins or polymethacrylic acid ester resins, polycarbonate resins, polyvinyl acetate resins, styrene acrylate resins, styrene -Methacrylic acid ester copolymer resin, vinyl toluene acrylate resin, etc. are mentioned.
Specific examples include those described in JP-A Nos. 59-101395, 63-7971, 63-7972, 63-7773, and 60-294862. it can.
Commercially available products include Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130 manufactured by Toyobo Co., Ltd., Tufton NE-382, Tufton manufactured by Kao Corporation U-5, ATR-2009, ATR-2010; Elitel UE3500, UE3210, XA-8153, KZA-7049, KZA-1449 manufactured by Unitika Ltd., Polyester TP-220 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. R-188; various types of high-loss series thermoplastic resins (all trade names) manufactured by Seiko Chemical Industry Co., Ltd., and the like.

(C) Polyurethane resin etc. are mentioned.
(D) Polyamide resin, urea resin, etc. are mentioned.
(E) Polysulfone resin and the like.
(F) Polyvinyl chloride resin, polyvinylidene chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl propionate copolymer resin, and the like.
(G) Cellulose resins, such as polyol resin, ethyl cellulose resin, cellulose acetate resin, etc., such as polyvinyl butyral.
(H) Polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin, polyether resin, epoxy resin, phenol resin and the like.
In addition, the said thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.

  Further, the thermoplastic resin may contain pigments or dyes such as brighteners, conductive agents, fillers, titanium oxide, ultramarine blue, and carbon black as required.

-Laminated paper-
The laminated paper is a paper obtained by laminating various resins, rubber or polymer sheets or films on a sheet such as a base paper. Examples of the laminate material include polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, polyimide, triacetyl cellulose, and the like. These resins may be used alone or in combination of two or more.

  In general, the polyolefin is often formed using low density polyethylene, but in order to improve the heat resistance of the support, polypropylene, a blend of polypropylene and polyethylene, high density polyethylene, high density polyethylene and low density polyethylene, It is preferable to use a blend of In particular, it is most preferable to use a blend of high-density polyethylene and low-density polyethylene from the viewpoint of cost, suitability for lamination, and the like.

The blend of the high density polyethylene and the low density polyethylene is used, for example, in a blend ratio (mass ratio) of 1/9 to 9/1. The blend ratio is preferably 2/8 to 8/2, and more preferably 3/7 to 7/3. When forming a thermoplastic resin layer on both surfaces of the support, the back surface of the support is preferably formed using, for example, high-density polyethylene or a blend of high-density polyethylene and low-density polyethylene. The molecular weight of polyethylene is not particularly limited, but the melt index is 1.0 to 40 g / 10 min for both high-density polyethylene and low-density polyethylene and has extrudability. preferable.
In addition, you may perform the process which gives white reflectivity to these sheets or films. Examples of such a treatment method include a method of blending a pigment such as titanium oxide in these sheets or films.

  The thickness of the support is preferably 25 μm to 300 μm, more preferably 50 μm to 260 μm, and still more preferably 75 μm to 220 μm. Various stiffnesses can be used according to the purpose, and the support for a photographic image receiving sheet for electrophotography is close to a support for color silver halide photography. Those are preferred.

<Curl adjustment layer>
If the support is exposed as it is, the heat-sensitive transfer image-receiving sheet may be curled due to the humidity and temperature in the environment. Therefore, it is preferable to form a curl adjusting layer on the back side of the support. The curl adjusting layer not only prevents the image receiving sheet from curling but also serves as a waterproof. For the curl adjusting layer, polyethylene laminate, polypropylene laminate, or the like is used. Specifically, it can be formed in the same manner as described in, for example, JP-A-61-110135 and JP-A-6-202295.

<Writing layer / Charge adjustment layer>
An inorganic oxide colloid, an ionic polymer, or the like can be used for the writing layer and the charge adjusting layer. As the antistatic agent, for example, a cationic antistatic agent such as a quaternary ammonium salt or a polyamine derivative, an anionic antistatic agent such as an alkyl phosphate, or a nonionic antistatic agent such as a fatty acid ester can be used. . Specifically, it can be formed in the same manner as that described in, for example, Japanese Patent No. 3585585.

  In addition, the thermal transfer image receiving sheet can be applied to various uses such as a sheet- or roll-shaped thermal transfer image-receiving sheet capable of thermal transfer recording, cards, and a sheet for preparing a transmission type document by appropriately selecting a support. it can.

Next, the ink sheet (thermal transfer sheet) used in the present invention will be described.
In the thermal transfer image formation, the ink sheet used in combination with the above-described thermal transfer image receiving sheet is provided with a dye layer containing a diffusion transfer dye on a support. The dye layer is applied by a general method such as roll coating, bar coating, gravure coating, or gravure reverse coating.

When the heat-sensitive transfer image-receiving sheet contains a polyester and / or polycarbonate polymer in the receiving layer, the dye layer of the ink sheet used in the present invention is represented by the general formula (1) or (3) as a yellow dye. It is preferable to include at least one dye, and it is preferable to include at least one dye represented by the general formula (4) or (5) as a magenta dye, and to be represented by the general formula (6) as a cyan dye. It is preferable to include at least one dye.
First, the dye represented by the general formula (1) will be described in detail.

In general formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent.
Here, the substituent will be described in more detail. Examples of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group (any number of rings)), an alkenyl group (including a cycloalkenyl group (any number of rings)), an alkynyl group, and an aryl group. , Heterocyclic group, cyano group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonyl Amino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, Sill group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl- or heterocyclic azo group, and a imide group, each group may further have a substituent.

Hereinafter, R ¹ , R ² and R ³ will be described in more detail.
Examples of the halogen atom represented by R ¹ , R ² and R ³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable.

The alkyl group represented by R ¹ , R ² or R ³ includes a cycloalkyl group and a bicycloalkyl group. The alkyl group includes a straight-chain, branched substituted or unsubstituted alkyl group. The linear, branched substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, or 2-ethylhexyl. The cycloalkyl group includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 3 to 30 carbon atoms. Examples include cyclohexyl, cyclopentyl, and 4-n-dodecylcyclohexyl. The bicycloalkyl group is a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Examples include bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl). Further, it includes a tricyclo structure having many ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group.
The alkenyl group represented by R ¹ , R ² or R ³ includes a cycloalkenyl group and a bicycloalkenyl group. The alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. As the alkenyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms is preferable. Examples include vinyl, allyl, prenyl, geranyl, oleyl. The cycloalkenyl group is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms. Examples include 2-cyclopenten-1-yl and 2-cyclohexen-1-yl. The bicycloalkenyl group includes a substituted or unsubstituted bicycloalkenyl group. The bicycloalkenyl group is preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. Examples include bicyclo [2,2,1] hept-2-en-1-yl and bicyclo [2,2,2] oct-2-en-4-yl.

The alkynyl group represented by R ¹ , R ² or R ³ is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl.

The aryl group represented by R ^1, R ² or R ³ is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, e.g., phenyl, p- tolyl, naphthyl, m- chlorophenyl, o- hexadeca Noylaminophenyl is mentioned.

The heterocyclic group represented by R ¹ , R ² or R ³ is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. Preferably, they may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples of the heterocyclic group include, but are not limited to, substitution positions (ie, exemplified as a ring): pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, Furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, Examples include imidazolidine and thiazoline.

The alkoxy group represented by R ¹ , R ² or R ³ includes a substituted or unsubstituted alkoxy group. As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group represented by R ¹ , R ² or R ³ is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.

R ^1, R ² or a formyloxy group represented by R ^3, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms preferably. Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.

The carbamoyloxy group represented by R ^1, R ² or R ³ is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. Examples of carbamoyloxy groups include N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy and the like. Can be mentioned.

The alkoxycarbonyloxy group represented by R ¹ , R ² or R ³ is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy and the like.

The aryloxycarbonyloxy group represented by R ¹ , R ² or R ³ is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

The amino group represented by R ¹ , R ² or R ³ includes an alkylamino group and an arylamino group. The amino group is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms and a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Examples of amino groups include, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino, 3,5-dicarboxyanilino, etc. Can be mentioned.

The acylamino group represented by R ¹ , R ² or R ³ is a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. Groups are preferred. Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino and the like.

The aminocarbonylamino group represented by R ¹ , R ² or R ³ is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. Examples of the aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

The alkoxycarbonylamino group represented by R ¹ , R ² or R ³ is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

Aryloxycarbonylamino group represented by R ^1, R ² or R ³ is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

The sulfamoylamino group represented by R ¹ , R ² or R ³ is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.

The alkyl or arylsulfonylamino group represented by R ¹ , R ² or R ³ is a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms. Groups are preferred. Examples of the alkylsulfonylamino group and arylsulfonylamino group include methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like.

Alkylthio group represented by R ^1, R ² or R ³ is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.

The sulfamoyl group represented by R ^1, R ² or R ³ is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. Examples of sulfamoyl groups include N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl) and the like.

R ^1, an alkyl or arylsulfinyl group represented by R ² or R ³ is a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 to 30 substituted or unsubstituted arylsulfinyl group. Examples of the alkyl or arylsulfinyl group include, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.

R ^1, an alkyl or arylsulfonyl group represented by R ² or R ³ is a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, 6 to 30 or a substituted or unsubstituted arylsulfonyl group is preferable. Examples of the alkyl or arylsulfonyl group include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

The acyl group represented by R ¹ , R ² or R ³ is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, carbon A heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom of several 4 to 30 is preferred. Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

Aryloxycarbonyl group represented by R ^1, R ² or R ³ is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl and the like.

The alkoxycarbonyl group represented by R ¹ , R ² or R ³ is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

The carbamoyl group represented by R ¹ , R ² or R ³ is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like.

Examples of the aryl or heterocyclic azo group represented by R ¹ , R ² or R ³ include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo, and the like. Can be mentioned.

Examples of the imide group represented by R ¹ , R ² or R ³ include N-succinimide and N-phthalimide.

R ¹ and R ² are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, substituted Or an unsubstituted acylamino group, a substituted or unsubstituted aminocarbonylamino group, a substituted or unsubstituted alkoxycarbonylamino group, or a substituted or unsubstituted amino group, more preferably a hydrogen atom, substituted or unsubstituted alkyl It is a group.

R ³ is preferably a hydrogen atom, or a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group. A hydrogen atom or a substituted or unsubstituted alkyl group is more preferable.

A ¹ represents an atomic group that forms a heterocycle with carbon atoms at both ends to which A ¹ is bonded. A ¹ is particularly preferably an atomic group that forms an acidic nucleus. James, The Theory of the Photographic Process, 4th edition, Macmillan, 1977, p. 198; M.M. Defined by Harmer, Heterocyclic Compounds-Cyanine Dies and Related Compounds, John & Wiley & Sons, New York, London, 1964. Preferably, A ¹ represents a 5- or 6-membered nitrogen-containing heterocycle. These may be further condensed with a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, a thiophene ring or the like. Specific examples of the ring (nucleus) formed by A ¹ include 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2 -Iminooxazolidin-4-one, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, isorhodanine, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one -1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, 3, 4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4- ON, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolopyridone, 3-dicyanomethylidenyl-3-phenylpropionitrile, Meldrum A nucleus such as an acid is exemplified, and 2-pyrazolin-5-one is preferable. These may further have a substituent.

B ¹ represents an atomic group that forms a heterocycle together with carbon atoms and nitrogen atoms at both ends. B ¹ is preferably an atomic group forming a 5- or 6-membered nitrogen-containing heterocyclic ring. These may be further condensed with a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, a thiophene ring or the like. B ¹ includes an oxazole nucleus having 3 to 25 carbon atoms (for example, 3-methyloxazol-2-yl), a thiazole nucleus having 3 to 25 carbon atoms (for example, 3-methylthiazol-2-yl), 25 imidazole nucleus (eg, 1,3-diethylimidazol-2-yl), C10-30 indolenine nucleus (eg, 3,3-dimethylindolenine), C9-25 quinoline nucleus (eg, 1-methylquinolin-2-yl), a C 3-25 selenazole nucleus (eg, 3-methylbenzoselenazol-2-yl), a C 5-25 pyridine nucleus (eg, 2-pyridyl), Thiazoline nucleus, oxazoline nucleus, selenazoline nucleus, tellurazoline nucleus, tellurazole nucleus, benzotelrazole nucleus, imidazoline nucleus, imidazo [4,5-quinoxaline] , It can be exemplified oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, an atomic group necessary for forming a pyrimidine nucleus. These may further have a substituent.

  Of the dyes represented by the general formula (1), a dye represented by the following general formula (2) is preferable. Hereinafter, the dye represented by the following general formula (2) will be described in detail.

In the general formula (2), R ^1, R ² and R ³ have the same meanings as R ^1, R ² and R ³ in the general formula (1), and the preferred range is also the same. R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a substituent. Examples of the substituent include those described above for R ¹ , R ² and R ³ . n1 represents an integer of 0 to 4, and n2 represents an integer of 0 to 5. Here, when n1 represents an integer of 2 to 4 or n2 represents an integer of 2 to 5, a plurality of R ⁴ or a plurality of R ⁸ may be the same or different.

R ⁴ and R ⁸ are preferably each independently a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxy group Carbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, alkylthio group, sulfamoyl group An alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, or a carbamoyl group, more preferably a hydrogen atom, Logen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino Group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylthio group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, more preferably a halogen atom, a substituted or unsubstituted alkyl group, substituted or An unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably a substituted or unsubstituted alkyl group.

R ⁵ and R ⁶ are preferably the same as R ¹ and R ² in the general formula (1), and more preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group. , A substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably a hydrogen atom or a substituted or unsubstituted alkyl group.

R ⁷ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group A substituted or unsubstituted acylamino group, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acylamino group.

  Regarding the preferred combination of substituents of the dye represented by the general formula (2), a compound in which at least one of various substituents is the preferred group is preferred, and a compound in which more various substituents are the preferred groups More preferred are compounds in which all substituents are the preferred groups.

Specific examples of preferred combinations are as follows: R ¹ is a hydrogen atom, R ² is a hydrogen atom, R ³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁴ is a substituted or unsubstituted carbon number 1 to 1. 6 alkyl groups, R ⁵ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁷ is a substituted or unsubstituted carbon number 1 A combination of ˜12 dialkylamino group, R ⁸ is a substituted or unsubstituted alkoxycarbonyl group having 1 to 6 carbon atoms or a chlorine atom, n1 is an integer of 0 to 3, and n2 is an integer of 0 to 3. More preferable examples of the combination are as follows: R ¹ is a hydrogen atom, R ² is a hydrogen atom, R ³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁵ is a substituted or unsubstituted carbon atom having 1 to 6 carbon atoms. A combination in which R ⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁷ is a substituted or unsubstituted dialkylamino group having 1 to 12 carbon atoms, and n1 and n2 are both 0.

The dye represented by the general formula (3) will be described in detail.

In the general formula (3), R ¹¹ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, and R ¹² represents a substituent. Examples of the substituent in R ^{11 to} R ¹⁴ include those described for R ¹ , R ² and R ³ described above. A ² represents an atomic group that forms a heterocycle with carbon atoms at both ends to which A ² is bonded. n3 represents an integer of 0 to 4. Here, when n3 represents an integer of 2 to 4, a plurality of R ¹² may be the same or different.

R ¹¹ is preferably the same as R ^{1 in the} general formula (1). More preferably, they are a hydrogen atom, a C1-C6 substituted or unsubstituted alkyl group. Most preferably, it is a hydrogen atom.

R ¹² is preferably the same as R ⁴ and R ^{8 in} the general formula (2). More preferably, they are a C1-C6 substituted or unsubstituted alkyl group, a C1-C6 alkoxy group, and a halogen atom.

R ¹³ and R ¹⁴ are preferably the same as those described for R ³ in the general formula (1), and the preferred range is also the same as R ³ . More preferably, they are a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

Specific examples of A ² include those described for A ¹ in formula (1), and preferred substituents are also the same.

  As for the preferred combination of substituents of the dye represented by the general formula (3), a compound in which at least one of various substituents is the above preferred group is preferred, and a compound in which more various substituents are the above preferred groups More preferred are compounds in which all substituents are the preferred groups.

Specific examples of preferred combinations include 2-pyrazolin-5-one having a substituent as A ² , R ¹¹ is a hydrogen atom, R ¹² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted group. A substituted alkoxy group having 1 to 6 carbon atoms, R ¹³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ¹⁴ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and n3 is 0 to 2 It is a combination that is an integer. More preferable examples of the combination include A ² is 2-pyrazolin-5-one having a substituent, R ¹¹ is a hydrogen atom, R ¹² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted group. An alkoxy group having 1 to 6 carbon atoms, R ¹³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ¹⁴ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and n3 is 0 or 1 It is a combination.

  The dye represented by the general formula (4) will be described in detail.

In General Formula (4), D represents an aromatic ring group derived from a diazonium salt or an aromatic heterocyclic group. R ¹⁵ represents a substituent, and R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a substituent. Examples of the substituent in R ^{15 to} R ¹⁷ include those described for R ¹ , R ² , and R ³ described above. n4 represents an integer of 0 to 4. Here, a plurality of R ¹⁵ when n4 represents an integer of 2 to 4 may be the same or different.

  Here, the azo dye will be described in detail. An azo dye is a dye synthesized by reacting an aryl or heteroaryl diazonium salt (diazo component) with a compound (coupler component) having an acidic hydrogen atom that forms an azo coupling reaction with the diazonium salt. It is.

  D is an aromatic ring group or an aromatic heterocyclic group that can be derived from a diazonium salt, and the aromatic ring group or the aromatic heterocyclic group may have a substituent. That is, D is a diazo component. The diazo component is a partial structure that can be introduced by converting a heterocyclic compound having an amino group as a substituent or a benzene derivative into a diazo compound (diazonium salt) and diazo coupling reaction with a coupler. It is a frequently used concept in the field. In other words, it is an amino-substituted aromatic heterocyclic compound capable of diazotization reaction or a substituent that is a monovalent group by removing the amino group of the aromatic compound.

Examples of the aromatic heterocyclic group include, but are not limited to, substitution positions (that is, exemplified as a ring). A pyrrole ring, a pyrazole ring, a triazole ring, a thiazole ring, an isothiazole ring, a benzothiazole ring, 1, 3, 4-thiadiazole ring, 1,2,4-thiadiazole ring, oxazole ring, benzoxazole ring, imidazole ring, benzoisothiazole ring, thiophene ring, benzothiophene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, indole ring Quinoline ring, purine ring, carbazole ring and acridine ring. An isothiazole ring, a 1,3,4-thiadiazole ring and a 1,2,4-thiadiazole ring are preferred. Each heterocyclic ring may further have a substituent and may be further condensed.
Examples of the aromatic group include a phenyl group and a naphthyl group, which may have a substituent and may be further condensed.

R ¹⁵ is preferably the same as R ^{1 in the} general formula (1). More preferred are amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group.

R ¹⁶ and R ¹⁷ are preferably those mentioned for R ³ in the general formula (1), and the preferred range is also the same as R ³ . More preferably, it is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

  Regarding preferred combinations of substituents of the dye represented by the general formula (4), compounds in which at least one of various substituents is the above preferred group are preferred, and compounds in which more various substituents are the above preferred groups More preferred are compounds in which all substituents are the preferred groups.

Examples of particularly preferred combinations include a monovalent group derived from a substituted isothiazole ring or a monovalent group derived from a 1,3,4-thiadiazole ring having a substituent, R ¹⁵ Is an acylamino group, R ¹⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ¹⁷ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and n4 is a combination of 0 to 4 . Examples of more preferred combinations are those in which D is a monovalent group derived from a substituted isothiazole ring or a monovalent group derived from a 1,3,4-thiadiazole ring having a substituent, and R ¹⁵ is an acylamino group. group, R ¹⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ¹⁷ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, with respect to substituted positions azo group n4 is 1, R ¹⁵ It is a combination that is in the o-position.

  The dye represented by the general formula (5) will be described in detail.

In the general formula (5), A ³ represents an atomic group that forms a heterocycle together with carbon atoms at both ends to which it is bonded. EWG ¹ represents an electron withdrawing group, R ¹⁸ represents a substituent, R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a substituent, and the substituents in R ^{18 to} R ²⁰ are the above-described R Examples described in ¹ , R ² and R ³ can be given. n5 represents an integer of 0 to 4. Here, when n5 represents an integer of 2 to 4, a plurality of R ¹⁸ may be the same or different.

Specific examples of A ³ include those described for A ¹ in formula (1), and preferred substituents are also the same.

In EWG ¹ , an electron withdrawing group having a Hammett's substituent constant σ _p value of 0 or more represents substitution. EWG ¹ is preferably an electron-withdrawing group having a σ _p value of 0.30 or more, more preferably an electron-withdrawing group of 0.45 or more, and particularly preferably an electron-withdrawing group of 0.60 or more. Examples of electron withdrawing groups having a σ _p value of 0.60 or more include nitro group, cyano group, methanesulfonyl group, trifluoromethanesulfonyl group, trifluoroacetyl group, dimethylaminosulfonyl group, sulfamoyl group, and the like. Examples of electron withdrawing groups having a σ _p value of 0.45 or more include alkoxycarbonyl groups, acyl groups, and carboxy groups, and examples of electron withdrawing groups having a σ _p value of 0.30 or more are sulfo groups. And a carbamoyl group. More preferred are a cyano group, a carboxyl group, an alkoxycarbonyl group, and a carbamoyl group, still more preferred are a cyano group, an alkoxycarbonyl group, and a carbamoyl group, and most preferred are a cyano group and a carbamoyl group.

Here, Hammett's substituent constant σ _p value will be described briefly. Hammett's rule is described in 1935 by L.L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by the Hammett rule include a σ _p value and a σ _m value, and these values can be found in many general books. A. Dean's “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemical Fields” No. 122, 96-103, 1979 (Nankodo). In the present specification, each substituent is limited or explained by Hammett's substituent constant σ _p, but this is limited only to a substituent having a known value that can be found in the above-mentioned book. Needless to say, even if the value is unknown, it also includes a substituent that would be included in the range when measured based on the Hammett rule. The general formula includes those that are not benzene derivatives, but the σ _p value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In this specification, the σ _p value is used in this sense.

Preferable examples of R ¹⁸ include substituents as described for R ⁴ and R ⁸ in the general formula (2). More preferably, they are a hydrogen atom, a C1-C6 alkyl group, and a C1-C6 alkoxy group.

Preferred examples of R ¹⁹ and R ²⁰ include substituents as described for R ³ in the general formula (1), and preferred ranges are also the same. More preferably, each independently is a hydrogen atom, or a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably a hydrogen atom or a substituted Or it is an unsubstituted alkyl group.

  Regarding the preferred combination of substituents of the dye represented by the general formula (5), a compound in which at least one of various substituents is the preferred group is preferred, and a compound in which more various substituents are the preferred groups More preferred are compounds in which all substituents are the preferred groups.

Specific examples of preferred combinations include a group in which A ³ forms a substituted 2-pyrazolin-5-one ring, EWG ¹ is a cyano group, R ¹⁸ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. A group or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, R ¹⁹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²⁰ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, A combination in which n5 is an integer of 0 to 4. Examples of more preferable combinations include a group in which A ³ forms a substituted 2-pyrazolin-5-one ring, EWG ¹ is a cyano group, R ¹⁹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, A combination in which R ²⁰ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms and n5 is 0.

  The dye represented by the general formula (6) will be described in detail.

In General Formula (6), EWG ² represents an electron-withdrawing group, R ²¹ and R ²⁴ each independently represent a substituent, R ²² , R ²³ and R ²⁵ each independently represent a substituent, R Examples of the substituent in ^{21 to} R ²⁵ include those described for R ¹ , R ² and R ³ described above. n6 and n7 each independently represents an integer of 0 to 4. Here, when n6 represents an integer of 2 to 4 or n7 represents an integer of 2 to 4, the plurality of R ²¹ or the plurality of R ²⁴ may be the same or different.

Specific examples of EWG ² include those described in EWG ¹ of the general formula (5), and preferred ranges are also the same. EWG ² is preferably an electron-withdrawing group having a σ _p value of 0.30 or more, more preferably 0.45 or more. Specifically, a cyano group and a substituted or unsubstituted carbamoyl group having 1 to 6 carbon atoms are more preferable, and an unsubstituted carbamoyl group is more preferable.

Examples of R ²¹ , R ²⁴ and R ²⁵ include substituents as described for R ⁴ and R ⁸ in the general formula (2), and preferred ranges are also the same. More preferably, there are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, and an acylamino group, more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, Acylamino group. Most preferably, it is a hydrogen atom.

Examples of R ²² and R ²³ include substituents as described for R ³ in the general formula (1), and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

  Regarding the preferred combination of substituents of the dye represented by the general formula (6), a compound in which at least one of various substituents is the preferred group is preferred, and a compound in which more various substituents are the preferred groups More preferred are compounds in which all substituents are the preferred groups.

Specific examples of preferred combinations are as follows: EWG ² is a substituted carbamoyl group, R ²¹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²⁴ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²⁵ is a hydrogen atom, n6 is an integer of 0 to 4, and n7 is A combination that is an integer of 0 to 4. More preferable examples of the combination are as follows: EWG ² is a substituted carbamoyl group, R ²² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²⁵ Is a hydrogen atom, and n6 and n7 are both 0.

  Further, when the receiving layer of the thermal transfer image-receiving sheet contains a vinyl chloride polymer, the dye layer of the ink sheet used in the present invention has at least the yellow dye represented by the general formula (7) or (8). It is preferable to include one kind of dye, and it is preferable to include at least one kind of dye represented by the general formula (9), (10) or (11) as a magenta dye, It is preferable to include at least one dye represented by formula (12) or (13).

  The dye represented by the general formula (7) will be described in detail.

In the general formula (7), R ⁵¹ and R ⁵² each independently represent a substituent, and examples of the substituent include those described above for R ¹ , R ² and R ³ . n8 represents an integer of 0 to 5, and n9 represents an integer of 0 to 4. Here, when n8 represents an integer of 2 to 5 or n9 represents an integer of 2 to 4, the plurality of R ⁵¹ or the plurality of R ⁵² may be the same or different.

Examples of R ⁵¹ include substituents as described for R ⁴ and R ⁸ in formula (2), and preferred ranges are also the same. More preferably, they are a hydrogen atom and a C1-C6 alkyl group. Most preferably, it is a C1-C6 alkyl group.

Examples of R ⁵² include substituents as described for R ⁴ and R ⁸ in formula (2), and preferred ranges are also the same. Preferred are an aryloxycarbonyl group having 6 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a substituted or unsubstituted carbamoyl group, and more preferred is a substituted carbamoyl group.

  As for the preferable combination of substituents of the dye represented by the general formula (7), a compound in which at least one of various substituents is the above-mentioned preferable group is preferable, and a compound in which more various substituents are the above-mentioned preferable groups More preferred are compounds in which all substituents are the preferred groups.

Specific examples of preferred combinations include R ⁵¹ is an alkyl group having 1 to 6 carbon atoms, R ⁵² is a substituted or unsubstituted carbamoyl group, an aryloxycarbonyl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. A combination of a carbonyl group, n8 is an integer of 0 to 3, and n9 is an integer of 0 to 3. Examples of more preferable combinations include R ⁵¹ is an alkyl group having 1 to 6 carbon atoms, R ⁵² is a substituted or unsubstituted carbamoyl group, an aryloxycarbonyl group having 6 to 10 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms. , N8 is an integer from 0 to 2, and n9 is an integer from 0 to 2. More preferable examples of the combination are as follows: R ⁵¹ is an alkyl group having 1 to 6 carbon atoms, R ⁵² is a substituted or unsubstituted carbamoyl group, an aryloxycarbonyl group having 6 to 10 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms. , N8 is 0 or 1, and n9 is a combination of 0 to 2.

  The dye represented by the general formula (8) will be described in detail.

In the general formula (8), R ⁶¹ represents a substituent. R ⁶² , R ⁶³ and R ⁶⁴ each independently represents a hydrogen atom or a substituent. Examples of the substituent in R ^{61 to} R ⁶⁴ include those described above for R ¹ , R ² , and R ³ . n10 represents an integer of 0 to 4. Here, when n10 represents an integer of 2 to 4, a plurality of R ⁶¹ may be the same or different.

Examples of R ⁶¹ include substituents as described for R ⁴ and R ⁸ in formula (2), and preferred ranges are also the same. More preferably, they are a hydrogen atom and a C1-C6 alkyl group. Most preferably, it is a C1-C6 alkyl group.
Examples of R ⁶² and R ⁶³ include substituents as described for R ³ in the general formula (1), and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
Examples of R ⁶⁴ include substituents as described for R ¹ and R ² in the general formula (1). Preferably they are a hydrogen atom and a C1-C6 alkyl group, More preferably, it is a hydrogen atom.

  As for the preferred combination of substituents of the dye represented by the general formula (8), a compound in which at least one of various substituents is the preferred group is preferred, and a compound in which more various substituents are the preferred groups More preferred are compounds in which all substituents are the preferred groups.

Specific examples of preferred combinations include R ⁶¹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁶² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁶³ is substituted or unsubstituted. A combination having 1 to 6 carbon atoms, R ⁶⁴ is a hydrogen atom, and n10 is an integer of 0 to 4. Examples of more preferable combinations include R ⁶¹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁶² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁶³ is a substituted or unsubstituted carbon group. number 1-6 alkyl group, R ⁶⁴ is a hydrogen atom, a combination n10 is 0 or 1.

  The dye represented by the general formula (9) or (10) will be described in detail.

In the general formula (9), R ⁷¹ and R ⁷³ each independently represent a hydrogen atom or a substituent, and R ⁷² and R ⁷⁴ each independently represent a substituent. n11 represents an integer of 0 to 4. n12 represents the integer of 0-2. Here, when n11 represents an integer of 2 to 4 or n12 represents 2, a plurality of R ⁷⁴ or a plurality of R ⁷² may be the same or different. Examples of the substituent in R ^{71 to} R ⁷⁴ include those described for R ¹ , R ² and R ³ described above.

Examples of R ⁷¹ and R ⁷³ include substituents as described for R ³ in the general formula (1), and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted C1-C6 alkyl group, More preferably, it is a hydrogen atom.

Examples of R ⁷² and R ⁷⁴ include substituents as described for R ⁴ and R ⁸ in the general formula (2). An alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, and an aryloxycarbonyloxy group are preferable, and an alkoxy group and an aryloxy group are more preferable. Each group may have a substituent.

In the general formula (10), R ⁸¹ represents a hydrogen atom or a substituent. R ⁸² and R ⁸⁴ each independently represents a substituent. n13 represents an integer of 0 to 4, and n14 represents an integer of 0 to 2. Here, when n13 represents an integer of 2 to 4 or n14 represents 2, the plurality of R ⁸⁴ or the plurality of R ⁸² may be the same or different. ^Examples of the substituent in R ⁸¹ , R ⁸² , and R ⁸⁴ include those described above for R ¹ , R ² , and R ³ .

Examples of R ⁸¹ include substituents as described for R ³ in the general formula (1), and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted C1-C6 alkyl group, More preferably, it is a hydrogen atom.

Examples of R ⁸² and R ⁸⁴ include substituents as described for R ⁴ and R ⁸ in the general formula (2). An alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, and an aryloxycarbonyloxy group are preferable, and an alkoxy group and an aryloxy group are more preferable. Each group may have a substituent.

  Regarding the preferred combination of substituents of the dye represented by the general formula (9) or (10), a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

Specifically, examples of preferable combinations of substituents in the general formula (9) are R ⁷¹ is a hydrogen atom, R ⁷² is an aryloxy group, R ⁷³ is a hydrogen atom, n11 is 0, and n12 is an integer of 0 to 2. It is a combination. A more preferable combination is a combination in which R ⁷¹ is a hydrogen atom, R ⁷² is an aryloxy group, R ⁷³ is a hydrogen atom, n11 is 0, and n12 is 2.
Specifically, a preferred combination example of the substituents in the general formula (10) is a combination in which R ⁸¹ is a hydrogen atom, R ⁸² is an aryloxy group, n13 is 1 or 2, and n14 is 0. A more preferable combination is a combination in which R ⁸¹ is a hydrogen atom, R ⁸² is an aryloxy group, n13 is 1, and n14 is 0. A more preferred combination is a combination in which R ⁸¹ is a hydrogen atom, R ⁸² is an aryloxy group, n13 is 1, n14 is 0, and R ⁸² is substituted at the o-position with respect to the amino group.

  The dye represented by the general formula (11) will be described in detail.

In the general formula (11), R ⁹¹ represents a hydrogen atom or a substituent. R ⁹³ and R ⁹⁴ each independently represents a hydrogen atom or a substituent. R ⁹² represents a substituent. n15 represents an integer of 0 to 2. Here, when n15 represents 2, a plurality of R ⁹² may be the same or different. One of Z ¹ and Z ² represents ═N—, and the other represents ═C (R ⁹⁵ ) —. Z ³ and Z ⁴ each independently represent ═N— or ═C (R ⁹⁶ ) —. R ⁹⁵ and R ⁹⁶ each independently represents a hydrogen atom or a substituent. Examples of the substituent in R ^{91 to} R ⁹⁶ include those described for R ¹ , R ² and R ³ described above.

R ⁹¹ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group. And more preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms and a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

Examples of R ⁹² include substituents as described for R ⁴ and R ⁸ in the general formula (2), and preferred ranges are also the same. More preferably, they are a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

Examples of R ⁹³ and R ⁹⁴ include substituents as described for R ³ in the general formula (1), and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted C1-C6 alkyl group, More preferably, they are a substituted or unsubstituted C1-C6 alkyl group.

Examples of R ⁹⁵ include substituents as described for R ⁴ and R ⁸ in formula (2), and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted alkyl group.

  As for the preferred combination of substituents of the dye represented by the general formula (11), a compound in which at least one of various substituents is the above preferred group is preferred, and a compound in which more various substituents are the above preferred groups More preferred are compounds in which all substituents are the preferred groups.

Specific examples of preferred combinations are: Z ¹ = C (R ⁹⁵ )-or = N-, Z ² = N- or = C (R ⁹⁵ )-, Z ³ = C (R ⁹⁶ )-, Z ⁴ is ═N—, R ⁹¹ is a substituted or unsubstituted alkyl group, R ⁹² is a substituted or unsubstituted alkyl group, R ⁹³ is a substituted or unsubstituted alkyl group, R ⁹⁴ is a substituted or unsubstituted alkyl group R ⁹⁵ is a hydrogen atom or a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, R ⁹⁶ is a hydrogen atom or a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and n15 is 0. It is a combination. Examples of more preferable combinations are: Z ¹ = C (R ⁹⁵ )-, Z ² = N-, Z ³ = C (R ⁹⁶ )-, Z ⁴ = N-, R ⁹¹ is substituted or unsubstituted R ⁹² is a substituted or unsubstituted alkyl group, R ⁹³ is a substituted or unsubstituted alkyl group, R ⁹⁴ is a substituted or unsubstituted alkyl group, R ⁹⁵ is a hydrogen atom or a substituted or unsubstituted alkyl group Or a substituted or unsubstituted aryl group, R ⁹⁶ is a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and a combination in which n15 is 0.

  The dye represented by the general formula (12) or (13) will be described in detail.

R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom or a substituent. Examples of the substituent in R ^{101 to} R ¹⁰⁴ include those described above for R ¹ , R ^2, and R ³ . n16 and n17 each independently represents an integer of 0 to 4. Here, when n16 represents an integer of 2 to 4 or n17 represents an integer of 2 to 4, the plurality of R ¹⁰¹ or the plurality of R ¹⁰² may be the same or different.

Examples of R ¹⁰¹ include substituents as described for R ⁴ and R ⁸ in formula (2), and preferred ranges are also the same. More preferably an amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, substituted or An unsubstituted alkyl group, a halogen atom or an acylamino group, more preferably an acylamino group. Preferred substitution positions are those in which an acylamino group is substituted at the o-position with respect to ═O.
Examples of R ¹⁰² include substituents as described for R ⁴ and R ⁸ in the general formula (2), and preferred ranges are also the same. More preferably, they are a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkoxy group.
Examples of R ¹⁰³ and R ¹⁰⁴ include substituents as described for R ³ in the general formula (1), and preferred ranges are also the same. A substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is more preferred, and a substituted or unsubstituted alkyl group is more preferred.

Specific examples of preferred combinations are as follows: R ¹⁰¹ is a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or an acylamino group, and R ¹⁰² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted group. Or an unsubstituted alkoxy group having 1 to 6 carbon atoms, R ¹⁰³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ¹⁰⁴ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and n16 is 0 It is the combination whose integer of -4 and n17 are integers of 0-2. More preferable examples of the combination are as follows: R ¹⁰¹ is a chlorine atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or an acylamino group (the substitution position value is o-position with respect to carbonyl), and R ¹⁰² is substituted or unsubstituted. An alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, R ¹⁰³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ¹⁰⁴ is a substituted or unsubstituted carbon group A combination in which n1 is an alkyl group of 1 to 6, n16 is an integer of 1 to 3, and n17 is 0 or 1.

In general formula (13), R ¹¹¹ and R ¹¹³ each independently represents a hydrogen atom or a substituent. R ¹¹² and R ¹¹⁴ each independently represent a substituent. n18 represents an integer of 0 to 4, and n19 represents an integer of 0 to 2. Here, when or where n19 when n18 represents an integer of 2 to 4 represents 2, a plurality of R ¹¹⁴ or R ¹¹² may be the same or different from each other. Examples of the substituent in R ^{111 to} R ¹¹⁴ include those described for R ¹ , R ² and R ³ described above.

Examples of R ¹¹¹ and R ¹¹³ include substituents as described for R ³ in the general formula (1), and preferred ranges are also the same. More preferred are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aryl group.

Examples of R ¹¹² and R ¹¹⁴ include hydrogen atoms and substituents as described for R ⁴ and R ⁸ in formula (2), and preferred ranges are also the same. More preferably, it is a hydrogen atom.

  Regarding the preferred combination of substituents of the dye represented by the general formula (12) or (13), a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are preferable. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

Specific examples of preferred combinations include R ¹¹¹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ¹¹³ is a substituted or unsubstituted carbon number. A combination of 1 to 6 alkyl groups or substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, and n18 and n19 are both 0; More preferable examples of the combination are as follows: R ¹¹¹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ¹¹³ is a substituted, substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and n18 and n19 are both 0. It is a certain combination.

  Specific examples of the dyes represented by the general formulas (1) to (13) are shown below, but the dyes used in the present invention are not limited to the following examples.

  Among the dyes represented by the general formulas (1) to (13), those not commercially available are disclosed in U.S. Pat. Nos. 4,757,046, 3,770,370, and German Patent No. 2,316,755. JP, JP-A-2004-51873, JP-A-7-137455, JP-A-61-31292, and J. Org. Chem. Soc. Perkin transfer I, 2047 (1977), by Champan, “Merocyanine Dye-Doner Element Used in Thermal Dye Transfer”.

  The dyes represented by the general formulas (1) to (13) are each preferably contained in the dye layer of the ink sheet in an amount of 10 to 90% by mass, and more preferably 20 to 80% by mass.

The coating amount of the pigment layer of the ink sheet is preferably 0.1 to 1.0 g / m ² (in terms of solid content, hereinafter the coating amount in the present invention is a numerical value in terms of solid content unless otherwise specified). More preferably, it is 0.15-0.60 g / m < ² >. The thickness of the dye layer is preferably 0.1 to 2.0 μm, more preferably 0.1 to 1.0 μm.

The support for the ink sheet can be the same as the support for the heat-sensitive transfer image-receiving sheet, and polyethylene terephthalate or the like can be used.
The thickness of the support is preferably 1 to 10 μm, and more preferably 2 to 10 μm.

  The image forming method can be performed in the same manner as described in, for example, JP-A-2005-88545. In the present invention, the printing time is preferably less than 15 seconds, and more preferably 5 to 12 seconds, from the viewpoint of shortening the time until the printed matter is provided to the consumer.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these. In Examples, “part” or “%” is based on mass unless otherwise specified.

[Preparation of ink sheet]
(Preparation of ink sheet D1)
A polyester film having a thickness of 6.0 μm (Lumirror, trade name, manufactured by Toray Industries, Inc.) was used as a base film. A heat-resistant slip layer (thickness 1 μm) was formed on the back side of the film, and yellow, magenta and cyan compositions having the following compositions were applied to the surface side in a single color (coating amount 1 g / m ² during dry film formation).
Yellow ink Dye (1) -1 2.2 parts Dye (3) -1 2.3 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts Magenta ink Dye (4) -1 2.2 parts Dye (5) -1 2.3 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts cyan ink Dye (6) -1 2.2 parts Dye (6) -4 2.3 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, Sekisui Chemical Co., Ltd.)
90 parts of methyl ethyl ketone / toluene (mass ratio 1/1)

(Preparation of ink sheet D2)
Only the monochromatic ink layer had the following composition, and the others were produced in the same manner as Sample D1.
Yellow ink Dye (1) -2 2.2 parts Dye (3) -2 2.3 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts Magenta ink Dye (4) -2 2.2 parts Dye (5) -2 2.3 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts cyan ink Dye (6) -2 2.2 parts Dye (6) -5 2.3 parts Polyvinyl butyral resin 4.5 parts (Esreck BX-1, trade name, Sekisui Chemical Co., Ltd.)
90 parts of methyl ethyl ketone / toluene (mass ratio 1/1)

(Preparation of ink sheet D3)
Only the monochromatic ink layer had the following composition, and the others were produced in the same manner as Sample D1.
Yellow ink Dye (7) -1 2.5 parts Dye (8) -1 2.0 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts Magenta ink Dye (9) -1 1.0 part Dye (10) -1 1.0 part Dye (11) -1 2.5 parts Polyvinyl butyral resin 4.5 (S-LEC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts Cyan ink Dye (12) -1 2.0 parts Dye (13) -1 2.5 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, Sekisui Chemical Co., Ltd.)
90 parts of methyl ethyl ketone / toluene (mass ratio 1/1)

(Preparation of ink sheet D4)
Only the monochromatic ink layer had the following composition, and the others were produced in the same manner as Sample D1.
Yellow ink Dye (7) -2 2.5 parts Dye (8) -2 2.0 parts Polyvinyl butyral resin 4.5 parts (ESREC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts Magenta ink Dye (9) -2 1.0 part Dye (10) -2 1.0 part Dye (11) -2 2.5 parts Polyvinyl butyral resin 4.5 (S-LEC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts Cyan ink Dye (12) -2 2.0 parts Dye (13) -2 2.5 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, Sekisui Chemical Co., Ltd.)
90 parts of methyl ethyl ketone / toluene (mass ratio 1/1)

[Production of image receiving sheet]
(Production of image receiving sheet R1)
Synthetic paper (YUPO FPG200, thickness 200 μm, trade name, manufactured by YUPO CORPORATION) was used as a support, and this one surface was coated with a bar coater in the order of a white intermediate layer having the following composition and a receiving layer. . The coating amount at the time of each drying was coated as a white intermediate layer 1.0 g / m ^2, the receiving layer 4.0 g / m ^2, drying each layer 110 ° C., it was carried out for 30 seconds.
White intermediate layer Polyester resin (Byron 200, trade name, manufactured by Toyobo Co., Ltd.) 10 parts by weight Fluorescent whitening agent 1 part by weight (Uvitex OB, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Titanium oxide 30 parts by weight Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts by weight Receptor layer Vinyl chloride-vinyl acetate resin 100 parts by weight (Solvine A, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Amino-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-3050C)
5 parts by mass of epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-300E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass

(Production of image receiving sheet R2)
Only the receiving layer had the following composition, and the others were produced in the same manner as the image receiving sheet R1.
Receiving layer 100 parts by mass of polyester resin (Byron 200, trade name, manufactured by Toyobo Co., Ltd.)
Amino-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-3050C)
5 parts by mass of epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-300E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass

(Production of image receiving sheet R3)
The receiving layer was changed to one having the following composition, and the reaction was performed at 100 ° C. for 2 minutes. Other than that, it produced similarly to image receiving sheet R1.
Receptor layer 1100 parts by weight of vinyl chloride latex (Viniblanc 900, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Montanate ester wax (J537, trade name, manufactured by Chukyo Yushi Co., Ltd.) 100 parts by weight Fluorosurfactant 1 part by weight (Fluorad FC-170C, trade name, manufactured by 3M Corporation)
Polyvinyl alcohol (PVA-105, trade name, manufactured by Kuraray Co., Ltd.) 25 parts by mass Distilled water 1000 parts by mass

(Preparation of image receiving sheet R4)
The receiving layer was changed to one having the following composition, and the others were prepared in the same manner as the image receiving sheet R3.
Receptor layer Polyester latex 2180 parts by mass (Vaironal MD-1480, trade name, manufactured by Toyobo Co., Ltd.)
Montanate ester wax (J537, trade name, manufactured by Chukyo Yushi Co., Ltd.) 100 parts by weight Fluorosurfactant 1 part by weight (Fluorad FC-170C, trade name, manufactured by 3M Corporation)
Polyvinyl alcohol (PVA-105, trade name, manufactured by Kuraray Co., Ltd.) 25 parts by mass Distilled water 500 parts by mass

(Preparation of image receiving sheet R5)
The receiving layer was changed to one having the following composition, and the others were prepared in the same manner as the image receiving sheet R3.
Receptor layer SBR latex 910 parts by mass (LX-416, trade name, manufactured by Nippon Zeon Co., Ltd.)
Montanate ester wax (J537, trade name, manufactured by Chukyo Yushi Co., Ltd.) 100 parts by weight Fluorosurfactant 1 part by weight (Fluorad FC-170C, trade name, manufactured by 3M Corporation)
Polyvinyl alcohol (PVA-105, trade name, manufactured by Kuraray Co., Ltd.) 25 parts by mass Distilled water 1000 parts by mass

(Production of image receiving sheet R6)
The receiving layer was changed to one having the following composition, and the others were prepared in the same manner as the image receiving sheet R1.
Receiving layer 30 parts by weight of polycarbonate resin (LEXAN-141, trade name, manufactured by General Electric)
70 parts by mass of polyester resin (Byron 200, trade name, manufactured by Toyobo Co., Ltd.)
Amino-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-3050C)
5 parts by mass of epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-300E)
400 parts by mass of methylene chloride

(Preparation of image receiving sheet R7)
The receiving layer was changed to one having the following composition, and the others were prepared in the same manner as the image receiving sheet R1.
Receiving layer Polybutyl acrylate (manufactured by Aldrich) 30 parts by weight Polymethyl methacrylate (manufactured by Aldrich) 70 parts by weight Amino-modified silicone 5 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-3050C)
5 parts by mass of epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-300E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass

(Preparation of image receiving sheet R8)
The receiving layer was changed to one having the following composition, and the others were prepared in the same manner as the image receiving sheet R1.
Receiving layer Polyvinyl acetate (manufactured by Aldrich) 70 parts by mass Polystyrene (manufactured by Aldrich) 30 parts by mass Amino-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-3050C)
5 parts by mass of epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-300E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass

(Preparation of image receiving sheet R9)
The receiving layer was changed to one having the following composition, and the others were prepared in the same manner as the image receiving sheet R3. Polyvinyl alcohol having a high degree of saponification is an example of a material having high crystallinity and substantially no thermoplasticity.
Receiving layer 1 part by mass of fluorosurfactant (Fluorad FC-170C, trade name, manufactured by 3M Corporation)
Polyvinyl alcohol (PVA-105, trade name, manufactured by Kuraray Co., Ltd.) 150 parts by weight Distilled water 1000 parts by weight

[Thermal transfer recording]
The ink sheets D1 to D4 and the image receiving sheets R1 to R9 were overlapped so that the former ink layer and the latter receiving layer were in contact with each other, and an image was output using the thermal transfer printer A or B. Here, the thermal printer shown in FIG. 1 of the present specification is used as the thermal transfer printer A, and the thermal printer not shown in FIG. A printer was used.
As the output image, 30 images of five general scenes were used, and the image evaluation was performed by observing three image quality and density variations of each image, and evaluated as follows.
A: Almost no change is observed.
○: A slight change is observed, but there is substantially no change.
(Triangle | delta): A slight change is seen and variation can be recognized.
X: The variation is clearly seen.
XX: Density unevenness more coarse than X is observed.
Furthermore, the control voltage at the time of the maximum density output of the thermal transfer printer A and the thermal transfer printer B is increased by 15%, and when output at this control voltage, the maximum density is the same value as the maximum density under the original conditions. The speed was increased and a high-speed processing test was conducted.

  Each result is shown to Tables 1-4. Table 1 shows the results using the thermal transfer printer A, and Table 2 shows the results using the thermal transfer printer B. Table 3 shows the results of high-speed processing using the thermal transfer printer A, and Table 4 shows the results of high-speed processing using the thermal transfer printer B.

As is apparent from the results of Tables 1 and 2, the images output using the thermal transfer printer B have large variations in image quality and density (samples 111 to 419), and are output using the thermal transfer printer A. Even in the case of an image, when the image receiving sheet R9 containing no thermoplastic resin in the receiving layer was used, the image quality and density varied greatly (Samples 109, 209, 309, and 409).
On the other hand, the image by the thermal transfer recording system of the present invention output to the image receiving sheet containing the thermoplastic resin in the receiving layer using the thermal transfer type printer A has small variations in image quality and density (Samples 101 to 108, Sample 201 to 201). 208, Samples 301-308, Samples 401-408). Furthermore, Samples 101 to 104, Sample 106, Samples 201 to 204, Sample 206, and Sample 301 using image receiving sheets R1 to R4 and R6 containing a polyester polymer, a polycarbonate polymer, or a vinyl chloride polymer as the thermoplastic resin. 304, Sample 306, Samples 401 to 404, and Sample 406 were even smaller in variation. In particular, the image receiving sheet R2, R4, or R6 containing polyester and / or polycarbonate polymer as the thermoplastic resin, and the ink sheet D1 containing at least one dye represented by any one of the general formulas (1) to (6). Or sample 102, sample 104, sample 106, sample 202, sample 204 and sample 206 combined with D2, and image receiving sheet R1 or R3 containing a vinyl chloride polymer as the thermoplastic resin and the general formulas (7) to (7) The sample 301, the sample 303, the sample 401, and the sample 403 using the ink sheet D3 or D4 containing at least one dye represented by any one of 13) had the smallest image variation.

Further, as apparent from the results of Tables 3 and 4, the images output by performing high-speed processing using the thermal transfer printer B have large variations in image quality and density, and uneven density unevenness is observed (Sample 111). 419), and even if the image is output by high-speed processing using the thermal transfer type printer A, when the image receiving sheet R9 that does not contain the thermoplastic resin in the receiving layer is used, the image quality and density vary greatly and are rough. Concentration unevenness was observed (Samples 109, 209, 309, and 409).
On the other hand, the image by the thermal transfer recording system of the present invention, which is output to the image receiving sheet containing the thermoplastic resin in the receiving layer using the thermal transfer type printer A, is small and uniform in image quality and density even when processed at high speed. Processing could be performed (Samples 101 to 108, Samples 201 to 208, Samples 301 to 308, Samples 401 to 408).

  When 3000 samples of the running test of the sample 101 were performed by the printer B and then a sample wider than the sample subjected to the running test was output, streak-like image failures were observed at both ends. Similarly, when the same evaluation was performed with the printer A, almost no streak-like failure was observed. From this result, it was found that the printer B without the protective belt is inferior in durability of the head.

1 is a perspective view showing a color thermal printer used in a thermal transfer recording system of the present invention. 1 is a plan view showing an outline of a color thermal printer used in a thermal transfer recording system of the present invention. It is explanatory drawing which shows the embodiment which made the space | interval of a protective belt wider than the paper width of a pair of thermosensitive recording sheet.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Pair of thermal recording sheet 12 Platen roller 13 Thermal head 13a Heating element array 18, 19 Protection belt 53 Pair of thermal recording sheet 54 Thermal head 54a Heating element array 55 Platen roller

Claims (13)

  A thermal head is disposed facing the platen roller, and the ink sheet and the thermal transfer image receiving sheet bonded together facing each other on the platen roller are pressed by a heating element array of the thermal head, and the ink sheet and the thermal transfer image receiving sheet described above. A thermal transfer recording system using a thermal printer that records an image by heating with a heating element array while transporting an image of the thermal printer, wherein a pair of protective belts are arranged in a state of being partially wound on both sides of the platen roller. The heat transfer image receiving sheet is used so that both ends of the heating element array protruding from both sides of the ink sheet and the heat transfer image receiving sheet are received by a pair of protective belts so as not to contact the platen roller. A thermal transfer recording system comprising a thermoplastic resin in the receiving layer.   2. The thermal transfer recording system according to claim 1, wherein at least one of the thermoplastic resins contained in the receiving layer of the thermal transfer image receiving sheet is a polyester and / or a polycarbonate polymer. 3. The thermal transfer recording system according to claim 2, wherein the ink sheet used by being superimposed on the thermal transfer image receiving sheet contains at least one dye represented by the following general formula (1) or (3). .

(In the general formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent. A ¹ represents an atomic group which forms a heterocycle with carbon atoms bonded to each other. B ¹ represents an atomic group that forms a heterocycle together with the carbon and nitrogen atoms at both ends to which it is bonded.

(In the general formula (3), R ¹¹ , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a substituent. R ¹² represents a substituent. A ² is a heterocycle together with carbon atoms at both ends to which it is bonded. N3 represents an integer of 0 to 4. Here, when n3 represents an integer of 2 to 4, a plurality of R ¹² may be the same or different. The ink sheet used by being superimposed on the heat-sensitive transfer image-receiving sheet contains at least one dye represented by the following general formula (4) or (5). Thermal transfer recording system.

(In the general formula (4), D represents an aromatic ring group or an aromatic heterocyclic group derived from a diazonium salt. R ¹⁵ represents a substituent, and R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a substituent. N4 represents an integer of 0 to 4. Here, when n4 represents an integer of 2 to 4, a plurality of R ¹⁵ may be the same or different.

(In General Formula (5), A ³ represents an atomic group that forms a heterocycle with carbon atoms bonded to both ends. EWG ¹ represents an electron-withdrawing group, R ¹⁸ represents a substituent, R ¹⁹ and R ²⁰ are each .n5 represents a hydrogen atom or a substituent independently represents an integer of 0 to 4. here, the plurality of R ¹⁸ when n5 represents an integer of 2 to 4 may be the same or different. ) 5. The ink sheet used by being superimposed on the heat-sensitive transfer image-receiving sheet contains at least one dye represented by the following general formula (6). Thermal transfer recording system.

(In General Formula (6), EWG ² represents an electron-withdrawing group. R ²¹ and R ²⁴ each independently represent a substituent, and R ²² , R ^23, and R ²⁵ each independently represent a hydrogen atom or a substituent. N6 and n7 each independently represents an integer of 0 to 4. Here, when n6 represents an integer of 2 to 4 or when n7 represents an integer of 2 to 4, a plurality of R ²¹ or a plurality of R ²⁴ May be the same or different.)   2. The thermal transfer recording system according to claim 1, wherein at least one of the thermoplastic resins contained in the receiving layer of the thermal transfer image receiving sheet is a vinyl chloride polymer. 7. The thermal transfer recording system according to claim 6, wherein the ink sheet used by being superimposed on the thermal transfer image receiving sheet contains at least one dye represented by the following general formula (7) or (8). .

(In the general formula (7), R ⁵¹ and R ⁵² each independently represent a substituent. N8 represents an integer of 0 to 5. n9 represents an integer of 0 to 4. Here, n8 is 2 to 5). Or when n9 represents an integer of 2 to 4, the plurality of R ⁵¹ or the plurality of R ⁵² may be the same or different.

(In the general formula (8), R ⁶¹ represents a substituent, R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or a substituent. N10 represents an integer of 0 to 4. Here, n10 And when R represents an integer of 2 to 4, a plurality of R ⁶¹ may be the same or different.) The ink sheet used by being superimposed on the heat-sensitive transfer image-receiving sheet contains at least one dye represented by any one of the following general formulas (9), (10), and (11). Item 8. The thermal transfer recording system according to Item 6 or 7.

(In General Formula (9), R ⁷¹ and R ⁷³ each independently represents a hydrogen atom or a substituent. R ⁷² and R ⁷⁴ each independently represent a substituent. N11 represents an integer of 0 to 4. n12 Represents an integer of 0 to 2. Here, when n11 represents an integer of 2 to 4 or when n12 represents 2, a plurality of R ⁷⁴ or a plurality of R ⁷² may be the same or different.

(In General Formula (10), R ⁸¹ represents a hydrogen atom or a substituent. R ⁸² and R ⁸⁴ each independently represents a substituent. N13 represents an integer of 0 to 4. n14 represents an integer of 0 to 2. Here, when n13 represents an integer of 2 to 4 or when n14 represents 2, the plurality of R ⁸⁴ or the plurality of R ⁸² may be the same or different.

(In the general formula (11), R ⁹¹ represents a hydrogen atom or a substituent. R ⁹² represents a substituent. R ⁹³ and R ⁹⁴ each independently represents a hydrogen atom or a substituent. Represents an integer, wherein when n15 represents 2, a plurality of R ⁹² may be the same or different, and ^one of Z ¹ and Z ² is ═N— and the other is ═C (R ⁹⁵ ). Z ³ and Z ⁴ each independently represent ═N— or ═C (R ⁹⁶ ) —, wherein R ⁹⁵ and R ⁹⁶ each independently represent a hydrogen atom or a substituent. The ink sheet used by being superimposed on the heat-sensitive transfer image-receiving sheet contains at least one kind of dye represented by the following general formula (12) or (13). 2. The thermal transfer recording system according to item 1.

(In General Formula (12), R ¹⁰¹ and R ¹⁰² each independently represent a substituent. R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom or a substituent. N16 and n17 each independently represent 0 to 4; Wherein n16 represents an integer of 2 to 4 or n17 represents an integer of 2 to 4, a plurality of R ¹⁰¹ or a plurality of R ¹⁰² may be the same or different.

(In the general formula (13), R ¹¹¹ and R ¹¹³ each independently represents a hydrogen atom or a substituent. R ¹¹² and R ¹¹⁴ each independently represent a substituent. N18 represents an integer of 0 to 4. n19 Represents an integer of 0 to 2. Here, when n18 represents an integer of 2 to 4 or when n19 represents 2, a plurality of R ¹¹⁴ or a plurality of R ¹¹² may be the same or different.   The thermal transfer recording system according to any one of claims 2 to 9, wherein the receiving layer of the thermal transfer image-receiving sheet contains a fluorine-based release agent compound or a silicone-based release agent compound.   Each said protection belt is hung on two rollers other than a platen roller, The shape seen from the side surface forms the triangle, The one of Claims 1-10 characterized by the above-mentioned. Thermal transfer recording system.   The two rollers are flanged rollers that are movable in the axial direction of the platen roller, and the interval between the pair of protective belts can be changed according to the width of the ink sheet and the thermal transfer image-receiving sheet. The thermal transfer recording system according to claim 11. The thermal transfer recording system according to any one of claims 1 to 12, wherein the receiving layer of the thermal transfer image receiving sheet is formed by applying water as a main medium.

Images