JP4584127B2 - Thermal transfer recording system - Google Patents

Description

  The present invention relates to a thermal transfer recording system, and more particularly to a thermal transfer recording system using a thermal printer that detects the temperature and environmental temperature of a thermal head and manages temperature fluctuations of the thermal head.

  In the thermal printer, the temperature of the thermal head is detected, and the voltage applied to the thermal head is controlled based on this detection signal to suppress temperature fluctuation. For example, as shown in Patent Document 1, when the temperature of the thermal head increases, the driving voltage of the thermal head is lowered, and conversely, when the temperature decreases, the driving voltage of the thermal head is increased. As a result, even if the temperature of the thermal head changes, the applied voltage of the head changes, so that thermal energy fluctuations are suppressed, and a heat generation temperature corresponding to a predetermined gradation can be obtained.

  In addition, the thermal energy applied to the thermal head is diffused to the ink ribbon (ink sheet), recording paper (heat-sensitive image-receiving sheet), platen drum, and the like. There is a problem that the thermal energy applied to the ink ribbon and the recording paper fluctuates due to the change, and the print density changes. For this reason, for example, as shown in Patent Document 2, in addition to the first temperature detecting means for detecting the temperature of the thermal head, a second temperature detecting means for detecting the environmental temperature is provided, and the amount of change in the environmental temperature is also measured. It is designed to take into account control.

  However, as shown in FIG. 8, even if the thermal head 2 is driven by the heating element 6 composed of the resistance layer 3 and the electrodes 4 and 5 and given a certain amount of heat, the temperature of the heating element 6 depends on the temperature of the glaze 7. Fluctuates, and a constant concentration cannot be obtained. Further, the head temperature detector 8 composed of a thermistor for detecting the temperature of the thermal head 2 is generally difficult to be disposed so as to come into contact with the glaze 7 due to problems in manufacturing the thermal head 2. A substrate 11 made of a ceramic plate 9, an aluminum plate 10 or the like is interposed. For this reason, there is a problem that the temperature of the glaze 7 cannot be directly detected by the head temperature detector 8. A heat sink 13 is attached to the substrate 11.

Therefore, the conventional one treats the output of the head temperature detector 8 of the thermal head 2 as if it were the temperature data of the glaze 7, and the drive voltage of the thermal head 2 is set so as to cancel out the long-term temperature fluctuation. The amount of heat applied to the thermal head 2 is controlled to obtain a predetermined density based on predetermined image data. However, such a control method has a problem that the target concentration cannot be obtained because the amount of heat is not controlled by the temperature of the glaze 7.
The long cycle refers to a period between the first and Nth sheets when the same image is printed, a period from the start of printing within one sheet to the end of printing, etc. Due to these long-term temperature fluctuations, density fluctuations also occur between the first and N-th sheets and within one sheet. The intermediate period is a temperature variation of a partial thermal head in the same image due to a pattern. For example, when a low density image area is recorded immediately adjacent to a high density image area, a low density This is the period of temperature fluctuation that occurs due to the influence of the high thermal head temperature during high density recording. Since it appears in the same image, density fluctuation between prints when printing the same image multiple times, density fluctuation between print start end and print end end in one print (both two are long The period is inevitably shorter than the density variation of the period.

Furthermore, the thermal energy applied to the thermal head varies greatly depending on the pattern to be printed, which appears as a temperature variation of the glaze. For this reason, there is also a problem that the print density changes due to temperature fluctuations based on the pattern.
JP-A-60-240271 JP-A-2-162060

  The present invention solves the above-mentioned problems, and accurately estimates the temperature of the glaze of the thermal head and controls the temperature based on this to improve the print quality and suppress temperature fluctuations due to the design. It is an object of the present invention to provide a thermal transfer recording system using a thermal printer that can suppress density fluctuations in the middle period even if high-speed processing is performed.

（一般式（９）中、Ｒ ⁷¹ およびＲ ⁷³ は各々独立に水素原子または置換基を表す。Ｒ ⁷² およびＲ ⁷⁴ 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Ｒ ⁷⁴ 又は複数のＲ ⁷² は各々同じでも異なっていてもよい。）

（一般式（１０）中、Ｒ ⁸¹ は水素原子または置換基を表す。Ｒ ⁸² およびＲ ⁸⁴ 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Ｒ ⁸⁴ 又は複数のＲ ⁸² は各々同じでも異なっていてもよい。）

（一般式（１１）中、Ｒ ⁹¹ は水素原子または置換基を表す。Ｒ ⁹² は置換基を表す。Ｒ ⁹³ およびＲ ⁹⁴ 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Ｒ ⁹² は同じでも異なっていてもよい。Ｚ ¹ およびＺ ² は、どちらか一方が＝Ｎ−であり、他方が＝Ｃ(Ｒ ⁹⁵ )−を表す。Ｚ ³ およびＺ ⁴ は各々独立に＝Ｎ−または＝Ｃ(Ｒ ⁹⁶ )−を表す。ここで、Ｒ ⁹⁵ およびＲ ⁹⁶ は各々独立に水素原子または置換基を表す。）

（一般式（１２）中、Ｒ ¹⁰¹ およびＲ ¹⁰² は各々独立に置換基を表す。Ｒ ¹⁰³ およびＲ ¹⁰⁴ 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Ｒ ¹⁰¹ 又は複数のＲ ¹⁰² は各々同じでも異なっていてもよい。）

（一般式（１３）中、Ｒ ¹¹¹ およびＲ ¹¹³ は各々独立に水素原子または置換基を表す。Ｒ ¹¹² およびＲ ¹¹⁴ 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Ｒ ¹¹⁴ 又は複数のＲ ¹¹² は各々同じでも異なっていてもよい。）
［２］前記感熱転写受像シートの受容層が、塩化ビニル系ラテックスを含有する受容層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。
［３］前記感熱転写受像シートの受容層中の塩化ビニル系ポリマーが、塩化ビニル共重合体であることを特徴とする［１］または［２］項に記載の熱転写記録システム。
［４］前記感熱転写受像シートの受容層にフッ素系離型剤化合物またはシリコーン系離型剤化合物を含むことを特徴とする［１］〜［３］のいずれか１項に記載の熱転写記録システム。
［５］前記感熱転写受像シートの受容層に固形ワックスと、フッ素系離型剤化合物またはシリコーン系離型剤化合物を含むことを特徴とする［１］〜［３］のいずれか１項に記載の熱転写記録システム。
［６］前記サーマルヘッドに取り付けられサーマルヘッドの温度を検出する第１の温度検出手段と、前記サーマルヘッドが取り付けられる筐体内の温度を検出する第２の温度検出手段とを設け、前記サーマルヘッドを、基板と、基板に形成したグレーズと、グレーズに形成した発熱素子と、基板に取り付けた前記第１の温度検出手段とから構成され、基板から第１温度検出手段までの熱抵抗と大気の熱抵抗との関係から、第１温度検出手段及び第２温度検出手段の温度信号に基づきグレーズ温度を推測し、この推測したグレーズ温度の変動を抑えるようにサーマルヘッドの発熱量を制御することを特徴とする［１］〜［５］のいずれか１項に記載の熱転写記録システム。
［７］前記サーマルヘッドの発熱量の制御が、ヘッド駆動電圧を制御して行われることを特徴とする［１］〜［６］のいずれか１項に記載の熱転写記録システム。
［８］前記サーマルヘッドの発熱量の制御が、画像データに基づく階調表現駆動パルスの幅又は個数を変更して行われることを特徴とする［１］〜［７］のいずれか１項に記載の熱転写記録システム。
［９］前記サーマルヘッドの発熱量の制御が、バイアスデータに基づくバイアス駆動パルスの幅又は個数を変更して行われることを特徴とする［１］〜［８］のいずれか１項に記載の熱転写記録システム。
［１０］前記インクシートのイエロー色素層に、下記一般式（７）で表される色素および下記一般式（８）で表される色素を含有することを特徴とする［１］〜［９］のいずれか１項に記載の熱転写記録システム。

（一般式（７）中、Ｒ ⁵¹ およびＲ ⁵² 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Ｒ ⁵¹ 又は複数のＲ ⁵² は各々同じでも異なっていてもよい。）

（一般式（８）中、Ｒ ⁶¹ は置換基を表し、Ｒ ⁶² 、Ｒ ⁶³ およびＲ ⁶⁴ 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Ｒ ⁶¹ は同じでも異なっていてもよい。） The problems of the present invention have been solved by the following means.
[1] A thermal transfer recording system using a thermal printer that superimposes ink sheets and drives each heating element provided in a line shape based on image data to record an image on a thermal transfer image-receiving sheet. seeking a change in temperature at the time of line recording of the thermal head when recording line from the image data, to control the amount of heat generated by the thermal head so as to suppress the temperature fluctuations, and the receiving layer of the thermal transfer image-receiving sheet of water which is formed is applied as the main medium, and has free thermoplastic resin in the receiving layer, at least one of the thermoplastic resin is a vinyl chloride polymer, the ink sheet, following generally the magenta dye layer It contains a dye represented by the formula (9), a dye represented by the following general formula (10), and a dye represented by the following general formula (11), respectively. Thermal transfer recording system which is characterized by containing the dye represented by the following general formula in the cyan dye layer (12), and the following general formula (13) dye represented by each.

(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.)

(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.
[2] The thermal transfer recording system according to item [1 ], wherein the receiving layer of the thermal transfer image-receiving sheet is a receiving layer containing a vinyl chloride latex.
[3] The thermal transfer recording system according to item [1] or [2], wherein the vinyl chloride polymer in the receiving layer of the thermal transfer image-receiving sheet is a vinyl chloride copolymer.
[4] The thermal transfer recording system according to any one of [1] to [3], 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. .
[5] Any one of [1] to [3], wherein the receiving layer of the heat-sensitive transfer image-receiving sheet contains a solid wax and a fluorine-based release agent compound or a silicone-based release agent compound. Thermal transfer recording system.
[6] A first temperature detection means for detecting the temperature of the thermal head attached to the thermal head, and a second temperature detection means for detecting the temperature in the housing to which the thermal head is attached are provided, and the thermal head Is composed of a substrate, a glaze formed on the substrate, a heating element formed on the glaze, and the first temperature detecting means attached to the substrate, and the thermal resistance from the substrate to the first temperature detecting means and the atmospheric temperature From the relationship with the thermal resistance, the glaze temperature is estimated based on the temperature signals of the first temperature detection means and the second temperature detection means, and the heat generation amount of the thermal head is controlled so as to suppress the fluctuation of the estimated glaze temperature. The thermal transfer recording system according to any one of [1] to [5].
[7] The thermal transfer recording system according to any one of [1] to [6], wherein the heat generation amount of the thermal head is controlled by controlling a head driving voltage.
[8] Any one of [1] to [7], wherein the heat generation amount of the thermal head is controlled by changing a width or number of gradation expression drive pulses based on image data. The thermal transfer recording system described.
[9] The heat generation amount of the thermal head is controlled by changing the width or the number of bias drive pulses based on bias data, according to any one of [1] to [8] Thermal transfer recording system.
[10] The yellow dye layer of the ink sheet contains a dye represented by the following general formula (7) and a dye represented by the following general formula (8) [1] to [9] The thermal transfer recording system according to any one of the above.

(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.)

  According to the present invention, the temperature fluctuation at the time of line recording of the thermal head when recording each line is obtained from the image data, and the heat generation amount of the thermal head is controlled so as to suppress this temperature fluctuation. Medium periodic temperature fluctuations can be suppressed. Therefore, the influence of image data at the time of recording each line can be prevented from appearing at the time of recording the next line, and the occurrence of tailing or the like can be suppressed. In particular, by using a specific heat-sensitive image-receiving sheet, medium-period density fluctuations can be suppressed even when high-speed processing is performed, and high-density transfer is possible. By using a specific heat-sensitive image-receiving sheet and a specific ink sheet in combination, it is possible to further suppress mid-cycle density fluctuations.

  The thermal head includes a substrate, a glaze formed on the substrate, a heating element formed on the glaze, and the first temperature detection means attached to the substrate, and heat from the substrate to the first temperature detection means. Since the glaze temperature was estimated based on the temperature signals of the first temperature detection means and the second temperature detection means from the relationship between the resistance and the thermal resistance of the atmosphere, the surface of the heating element of the thermal head regardless of the temperature around the thermal head The glaze temperature, which is the approximate value of the temperature, can be grasped almost accurately. Therefore, heat generation control faithful to the image data can be performed, and the print quality can be improved. That is, because of the structure of the thermal head, temperature detecting means such as a thermistor cannot be directly attached to the glaze, and conventionally, the temperature of the substrate such as an aluminum plate has been used as the surface temperature of the heating element of the thermal head. For this reason, the amount of heat generated by the heating element is not controlled by the temperature of the glaze, and the target concentration cannot be obtained, but this can be solved.

  In addition, since the amount of heat generated by the thermal head is controlled so as to suppress long-term fluctuations in the estimated glaze temperature, density fluctuations between prints when printing the same image multiple sheets can be suppressed, and one print can be printed. The density fluctuation (shading) between the print start end and the print end end is suppressed, and the print quality can be improved.

Furthermore, the thermal resistance r _AL from the substrate to the first temperature detecting means, the thermal resistance of the heat sink r _F, the thermal resistance of the air r _a, the temperature near the first temperature detector T _AL, the second temperature detection temperature near means (ambient temperature) is taken as T _a, the equation 1, since determine the glaze temperature Tg, it is possible to infer the temperature of accurately glaze.

Further, when the heat capacity from the substrate to the first temperature detecting means is C _AL , the correction amount for the amount of heat fluctuation due to the pattern is obtained by Equation 2, so that the density fluctuation due to the pattern can be suppressed with high accuracy.

  In addition, since the amount of heat generated by the thermal head is controlled by controlling the head drive voltage, it is possible to easily suppress fluctuations in the glaze temperature. In addition, since the heat generation amount of the thermal head is controlled by changing the width or number of bias pulses based on the bias data and the gradation expression drive pulses based on the image data, the temperature control of the heating elements is performed more finely. Can do.

Hereinafter, the present invention will be described in detail.
In the thermal printer used in the thermal transfer recording system of the present invention, the temperature fluctuation during line recording of the thermal head when recording each line is obtained from the image data. The amount of heat generated by the thermal head is controlled to suppress this temperature fluctuation. Furthermore, a steady glaze temperature is estimated from the relationship between the thermal resistance from the substrate to the first temperature detecting means and the atmospheric thermal resistance based on the temperature signals of the first temperature detecting means and the second temperature detecting means. Based on the estimated glaze temperature, the heat generation amount of the thermal head is controlled so that the long-term temperature fluctuation is suppressed. By using a specific heat-sensitive transfer image-receiving sheet containing a thermoplastic resin in the receiving layer, it is possible to perform high-speed processing while suppressing medium-period density fluctuations.

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.
In FIG. 3 which shows the outline of the monochrome thermal printer which implemented this invention, the platen drum 20 is attached to the rotating shaft 22 driven with the pulse motor 21, and rotates to the arrow direction at the time of printing. A heat-sensitive recording material (heat-sensitive image-receiving sheet) 23 is wound around the outer periphery of the platen drum 20, and its tip is fixed by a clamper 24. The clamper 24 is controlled to be opened and closed by a cam mechanism 25. The platen drum 20, the pulse motor 21, the clamper 24, the cam mechanism 25, and a pair of conveyance rollers (not shown) constitute a recording material conveyance unit 26. A thermal head 2 is disposed on the outer periphery of the platen drum 20. Furthermore, an environmental temperature detector 36 for detecting the environmental temperature in the housing 29 is disposed in the housing 29. When performing color recording, a magenta fixing ultraviolet lamp and a yellow fixing ultraviolet lamp are further arranged in order on the outer periphery of the platen drum 20.

  As shown in FIG. 3, a heating element array 27 is provided on the lower surface of the thermal head 2. In the heating element array 27, a large number of heating elements 6 (see FIG. 8) are formed in a line shape in the main scanning direction. Each heating element is composed of a resistance element, and this heating element is sensitive to bias thermal energy that heats up to just before color development and gradation expression thermal energy according to color density when one pixel is thermally recorded. The recording material 23 is given.

  FIG. 1 shows an electric circuit of a thermal printer. Image signals from a video camera, a video deck, a video game machine, and the like are input to the image processing unit 31 via the image input unit 30. The image processing unit 31 writes image data for one frame in the frame memory 32 after performing A / D conversion and gradation correction.

  The system controller 33 is composed of a microcomputer, and controls the recording material conveyance unit 26 and the printing unit 28 in sequence to record a monochrome halftone image on the thermal recording material 23 based on the image data to create a hard copy.

FIG. 2 shows an equivalent circuit in the automatic control system of the thermal head 2 of FIG. In FIG.
T _e : surface temperature of heating element 6 [° C.]
T _g : Glaze 7 temperature [° C.]
T _AL : Temperature near the head temperature detector (first temperature detecting means) 8 (temperature of the substrate 11) [° C.]
T _a : Temperature (environment temperature) in the vicinity of the environmental temperature detector (second temperature detecting means) 36 (see FIG. 1) [° C.]
r _g : Thermal resistance of glaze 7 [° C./kcal/min]
r _AL : Thermal resistance from the ceramic plate 9 to the head temperature detector 8 through the aluminum plate 10 [° C./kcal/min]
r _F : thermal resistance of the heat sink 13 [° C./kcal/min]
r _a : thermal resistance of the atmosphere [° C / kcal / min]
C _g : Glaze 7 heat capacity [kcal / ° C]
C _AL : Heat capacity [kcal / ° C.] from the ceramic plate 9 to the head temperature detector 8 through the aluminum plate 10
E _a : a heat source by the atmosphere in the casing, having a temperature Ta [° C.]

Here, since the glaze 7 is minute compared to the aluminum plate 10 and can be regarded as r _g · C _g << r _AL · C _AL , the temperature T _{g of the} glaze 7 can be obtained by the following equation.
(Formula 1) T _g = {(r _AL + r _F + r _a ) · (T _AL −T _a ) / (r _F + r _a )} + T _a

The temperature T _{g of the} glaze 7 changes depending on the heat storage, that is, the driving state of the thermal head 2, and this glaze temperature T _g can be estimated from the detected temperatures of the head temperature detector 8 and the environmental temperature detector 36 by Equation 1. Thus, as the guessed glaze temperature T _g constant, by adding the variation of the glaze temperature T _g in the center voltage command value of the driving voltage of the thermal head 2, the temperature variation of the long period of the thermal head 2 is suppressed It is done. Thereby, it is possible to prevent long-term temperature fluctuations from appearing in the print as density changes. Note that by construction of the substrate 11 of the thermal head 2 is changed, formulas are also modified to obtain the glaze temperature T _g correspondingly.

FIG. 4 is a block diagram of a system that automatically controls the drive voltage of the thermal head 2. The system controller 33 is based on a temperature detection signal T _AL, T _a from the temperature detectors 8,36, it detects a long-period variation of the glaze temperature T _g by the equation 1, so as to eliminate this variation, the center The correction voltage value for the voltage command value is obtained.

Further, the calorie data Q0 per time is obtained from the image data, and a correction voltage value for correcting the temperature fluctuation due to the picture is obtained from the calorie data Q0 per time according to Equation 2. The variation ΔQ of the amount of heat Q that appears in the temperature variation of the head temperature detector 8 is smaller than that of the aluminum plate 10 in the glaze 7 and can be regarded as r _g · C _g << r _AL1 · C _AL1. When displayed, it looks like this: According to the mathematical formula 2, it is possible to estimate the thermal energy fluctuation in the middle period that does not appear in the temperature detector from the total thermal energy fluctuation for one line.

(Formula 2) ΔQ = {(S · r _AL · C _AL ) / (1 + S · r _AL · C _AL )} · Q 0
Where r _AL is the thermal resistance [° C./kcal/min] from the substrate to the head temperature detector, and C _AL is the heat capacity [kcal / ° C.] from the substrate to the head temperature detector.

The heat quantity data Q0 per time is driven by image data having a density equal to or higher than a predetermined value when recording each line, the total heat quantity based on the image data of the previous line, the average value obtained by dividing the total heat quantity by the number of printing elements. It is preferable to use any of the number of heating elements. Further, it is preferable that an environmental temperature to which the thermal head is attached is detected by an environmental temperature detector, and a glaze temperature is estimated by the following Equation 3 based on the detected temperature by the head temperature detector and the environmental temperature detector.
(Expression 3) T _g = {(r _AL + r _F + r _a ) · (T _AL −T _a ) / (r _F + r _a )} + T _a
However, T _g: Temperature of the glaze [° C.], r _F: thermal resistance of the heat sink [° C. / kcal / min], r _a: thermal resistance of the atmosphere [° C. / kcal / min], T _AL: head temperature detector Temperature in the vicinity [° C.], _Ta : Temperature in the vicinity of the environmental temperature detector [° C.].

The amount of heat data Q0 per time is obtained by Equation 4 from the image data G _i (i is 1 to n (n is the total number of heating elements of the thermal head)) of the previous line when recording each line.

(Formula 4) Q0 = ΣG _i
The calorie data Q0 may be an average value obtained by dividing Equation 4 by n in addition to the total heat amount at the time of recording for one line as in Equation 4. Furthermore, the number of heating elements driven by image data having a density of a certain level or more may be used.

The voltage correction value for suppressing these long-period temperature fluctuations obtained as described above and the voltage correction value for suppressing medium-period temperature fluctuations appearing in the picture are added to the center voltage command value. Thus, the drive voltage command value of the thermal head is obtained. The obtained drive voltage command value is amplified by the amplifier 40 and sent to the drive voltage control unit 37. The calculation and amplification of the drive voltage command value are performed by the system controller 33. Specifically, the system controller 33, the temperature detection signal T _AL from the respective temperature detectors 8,36, the T _a after digitized by the A / D converter 41, the arithmetic processing of Equations 1 and 2 by CPU42 To calculate a drive voltage command value. Thereafter, the drive voltage command value is analogized by the D / A converter 43 and sent to the drive voltage control unit 37. In addition to calculating the correction voltage value each time based on Formula 1 or 2, the correction voltage value may be calculated in advance according to changes in each temperature signal, and stored as look-up table data. Therefore, it is not necessary to perform an operation each time, and the correction voltage value can be quickly obtained.

The drive voltage command value signal is sent to the voltage variable circuit 45 of the drive voltage control unit 37. The voltage variable circuit 45 changes the heating element drive voltage of the head power supply circuit 46 based on the drive voltage command value signal. As a result, long-term temperature fluctuations of the thermal head 2 are suppressed, and density fluctuations on the print due to this are reduced. That is, the temperature of the surface temperature and the glaze 7 of heating element 6 is substantially the same, by controlling the driving voltage of the heating element 6 on the basis of the glaze temperature T _g, the long periodic temperature variation of the heating elements 6 Can be suppressed. As a result, the occurrence of density fluctuations and shading between the first sheet and the Nth sheet when a plurality of the same images are printed can be suppressed.

  As shown in FIG. 5, the print controller 50 includes a line memory 50a. The print controller 50 sequentially reads image data for one line written in the line memory 50a, and compares the image data with the comparison data each time. Serial gradation drive data is generated. This drive data is “H” when recording, and “L” when not recording. Further, before creating the gradation drive data, the bias data for one line and the comparison data are compared, and serial bias drive data is generated based on the comparison data. Such serial drive data is sent to the thermal head drive unit 38. A method and apparatus for generating bias and gradation drive data by comparison with comparison data are described in detail in Japanese Patent Application Laid-Open Nos. 7-137320 and 7-137321.

The thermal head drive unit 38 shifts serial drive data by the shift register 52 based on the clock signal and converts it into a parallel signal. The drive data converted in parallel by the shift register 52 is latched in the latch array 53 in synchronization with the latch signal. The AND gate array 54 outputs a signal “H” when the drive data is “H” within a period in which the strobe signal is input from the strobe signal generation circuit 51 in the print controller 50. Transistors 55 _{1 to} 55 _n are connected to the output terminals of the AND gate array 54. These transistors 55 _{1 to} 55 _n are turned on when the output of the AND gate array 54 is “H”. The heating elements 6 _{1 to} 6 _n are connected to the transistors 55 _{1 to} 55 _n , so that the heating elements 6 _{1 to} 6 _n are driven so as to have a density corresponding to the image data. Thereafter, as shown in FIG. 3, the recording material transport unit 26 intermittently rotates the platen drum 20 by a predetermined amount to feed the thermal recording material 23 by one line. 26, each line is thermally recorded one after another.

  Next, the operation of the thermal printer of this embodiment will be described. As shown in FIG. 3, during sheet feeding, the platen drum 20 is stopped at the home position in which the clamper 24 is substantially vertical. Further, the clamper 24 is in an open state. In this state, the heat-sensitive recording material 23 is sent to the platen drum 20, and when the tip passes through the clamper 24, the clamper 24 is closed, and then the platen drum 20 starts to rotate. As a result, the heat-sensitive recording material 23 is wound around the outer periphery of the platen drum 20.

The system controller 33 starts thermal recording when each heating element 6 of the thermal head 2 is positioned at the recording start position of the thermal recording material 23. First, the print controller 50 generates drive data for each of the heating elements 6 _{1 to} 6 _n based on the image data in the line memory 50 a, and sends this to the thermal head drive unit 38. The thermal head drive unit 38 drives the heating elements 6 _{1 to} 6 _n based on the drive data. Note that bias heating is performed before the gradation expression heating so that the temperature is just before color development. As a result, an image for one line is thermally recorded at a density corresponding to the image data. In the same manner, images of each line are recorded one after another. When the thermal recording is completed, the platen drum 20 is reversed. By the reverse rotation of the platen drum 20, the rear end of the thermal recording material 23 is guided to the paper supply / discharge passage by a separation claw (not shown), and the recording material on which thermal recording has been completed is discharged to the paper discharge tray.

  When the glaze temperature Tg of the thermal head 2 fluctuates due to the image recording of each line, this is detected based on the output signals from the temperature detectors 8 and 36, and based on this, the drive voltage command value of the thermal head 2 is obtained. Thus, the voltage variable circuit 45 of the drive voltage control unit 37 changes the drive voltage to the heating element 6. As a result, the drive voltage of the heating element 6 is controlled so as to suppress long-term temperature fluctuations, so that density fluctuations for each sheet when a plurality of sheets are printed, and gentle density fluctuations in one sheet. Can be suppressed.

  Further, the amount of heat Q0 per time is obtained from the image data used at the time of previous line recording, and based on this, a drive voltage command value for suppressing the temperature fluctuation of the thermal head due to the picture is obtained by Equation 2, thereby obtaining a drive voltage control unit. A voltage variable circuit 45 37 changes the drive voltage to the heating element 6. As a result, the drive voltage of the heating element 6 is controlled so as to suppress medium-period temperature fluctuations due to the pattern, so that density fluctuations for each line can be suppressed and occurrence of tailing or the like can be reduced.

Then, instead of changing the driving voltage of the heating element 6, so as to suppress the long period and medium periodic variations of the glaze temperature T _g, the embodiment for changing the number of gradation driving pulses based on the image data explain. In this case, as shown in FIG. 6, with respect to the number of gradation expression driving pulses obtained from the image data, the number of correction pulses of the gradation expression driving pulse is set based on the temperature signal obtained from each temperature detector. The actual number of pulses is calculated by adding this to the number of gradation expression drive pulses obtained from the image data, and gradation expression recording is performed based on this. In addition to calculating the correction pulse number each time based on Equations 1 and 2, the correction pulse number may be calculated in advance according to changes in each temperature signal and stored as lookup table data. .

  Further, instead of suppressing the temperature fluctuation by changing the number of gradation expression driving pulses, the temperature fluctuation may be suppressed by changing the width of the gradation expression driving pulse. In this case, the strobe signal generation circuit 51 shown in FIG.

  Further, in addition to changing the number and width of the gradation expression drive pulses, as shown in FIG. 7, it is also possible to suppress the long period and medium period temperature fluctuations of the thermal head by changing the number of bias pulses. Good. Further, when one bias pulse is used, its width may be changed. Furthermore, when a large number of bias pulses are used, the width of each bias pulse may be changed by changing the strobe signal according to the temperature fluctuation.

  The above temperature fluctuations were calculated for each thermal head, but when suppressing periodic temperature fluctuations, the image data for each heating element was calculated so that the temperature fluctuation due to the design was calculated for each heating element and this temperature fluctuation was suppressed. A correction amount may be obtained and temperature fluctuations may be suppressed for each heating element based on the correction amount. In the above embodiment, image data at the time of previous line recording is used. However, the present invention is not limited to this, and image data at the time of previous and previous line recording may also be used. In this case, it is preferable to reduce the weighting of the previous image data as compared with the previous image data, and this makes it possible to suppress medium-period temperature fluctuations with higher accuracy.

  In the above-described embodiment, the present invention is applied to a monochrome type thermal printer. However, the present invention may be applied to a color thermal printer, another sublimation type, or a fusion type thermal transfer printer. In the case of a color thermal printer, as is well known, for example, a yellow image is thermally recorded and then light-fixed, then a magenta image is thermally recorded and then light-fixed, and finally a cyan image is thermally recorded. . In this case, the temperature variation of the thermal head during recording of each color can be suppressed, so that the occurrence of color unevenness can be suppressed. Further, the present invention may be implemented in a serial printer without being limited to a line printer.

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, the receiving layer is formed by applying water as a main medium, and the receiving layer contains a thermoplastic resin, and at least one of the thermoplastic resins is a vinyl chloride polymer.
The thermoplastic resin used in the acceptance layer, for example, polyvinyl chloride, poly halogenated polymer polyvinyl acetate-ethylene vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyacrylic ester of vinylidene chloride・ Vinyl resins such as polystyrene and polystyrene acrylic, acetal resins such as polyvinyl formal, polyvinyl butyral, and polyvinyl acetal, polyethylene terephthalate, polybutylene terephthalate, polycaprolactone (Placcel H-5, trade name, manufactured by Daicel Chemical Industries, Ltd.) ) And other polyester-based resins, polycarbonate-based resins, and cellulose-based resins and cellulose acetate butyrate (CAB551-0.2, CAB321) described in JP-A-4-296595 and JP-A-2002-264543. 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 such that isophthalic acid is 50 to 100 mol%, trimellitic acid 0 to 1 mol%, terephthalic acid 0 to 50 mol%, 1,4-cyclohexanedicarboxylic acid 0 to 15 mol%, and the total amount is 100 mol%. 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%.

Po Riesuteru resin, using the at least dicarboxylic acid and diol components, the molecular weight (weight average molecular weight (Mw)) of about 11000 or more, preferably about 15,000 or more, those more preferably polycondensed to have 17,000 or more use. 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.

Bisphenol A- polycarbonate are particularly preferred embodiments of the port polycarbonate, will be described in detail. The technique of unmodified polycarbonate, centered on bisphenol A-polycarbonate, is described in US Pat. No. 4,695,286. Po polycarbonate molecular weight (weight average molecular weight (Mw)) of about 1000 or more, preferably about 3000 or more, more preferably about 5,000 or more, particularly preferably used after polycondensation of 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 good preferable embodiment, the polyether block unit has a number molecular weight of about 4,000 to about 50,000, also bisphenol A- polycarbonate block unit has 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. Thus, the acceptance layer vinyl chloride - is superior vinyl acetate copolymer, vinyl chloride - not limited to vinyl acetate copolymer is not necessarily copolymerized only vinyl chloride component and vinyl acetate component body, It may contain a vinyl alcohol component, a maleic acid component, and the like in a range that does not interfere with 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. Further, components other than the elevation clogs vinyl chloride and vinyl acetate previously is preferably 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 phthalate esters, phosphate esters, adipic acid esters, and sebacic acid esters, and polyester plasticizers that are polymerized with 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 with respect to the resin, but its use amount 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 trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and examples of dimethyl silicone oil include KF50-100, KF54, KF56 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) 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 with the above compounds (catalyst poisons), the ability to hydrosilylate as a catalyst is lost, and the function as a curing catalyst is lost. 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 reduced. 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 foam layer is low, and the effect of forming the foam 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 and adversely affects the appearance and print quality. The total thickness of the 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. In this case, the surface of the foam layer is made 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 size 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 resins, ethyl cellulose resins, and cellulose acetate resins, 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.

The receiving layer of the thermal transfer image-receiving sheet of the present invention contains a vinyl chloride polymer, and the dye contained in the dye layer of the ink sheet in this case will be described later.
First, the case where the heat-sensitive transfer image-receiving sheet contains a polyester and / or polycarbonate polymer in the receiving layer will be described.
If it contains polyester and / or polycarbonate-based polymer in the receptor layer of the thermal transfer image-receiving sheet, the dye layer of the ink sheet to be needed use, at least one represented by the general formula as a yellow dye (1) or (3) It is preferable to contain a seed dye, and it is preferable to include at least one dye represented by the general formula (4) or (5) as a magenta dye, and represented by the general formula (6) as a cyan dye. It is preferable to include at least one dye.

In general formula (1), R ¹ , R ² and R ³ each independently represent 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 (the number of rings is not limited)), an alkenyl group (including a cycloalkenyl group (the number of rings is not limited)), 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.

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.

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 halogen atom, 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, R ⁷ is a substituted or unsubstituted carbon number 1 -12 dialkylamino group, R < ⁸ > is a substituted or unsubstituted C1-C6 alkoxycarbonyl group or a chlorine atom, n1 is an integer of 0-3, n2 is an integer of 0-3. 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 those mentioned 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). 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 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, 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 for 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 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. A cyano group, a carboxyl group, an alkoxycarbonyl group, and a carbamoyl group are more preferable, a cyano group, an alkoxycarbonyl group, and a carbamoyl group are more preferable, and a cyano group and a carbamoyl group are most preferable.

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, “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 includes a substituent that would be included in the range when measured based on the Hammett's rule. In addition, some of the above general formulas 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 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 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.

In the present invention, the heat-sensitive transfer image-receiving sheet of the receiving layer viewed contains a vinyl chloride polymer, the dye layer of the ink sheet used in the present invention, under following general formula as a yellow dye (7) or (8) preferably contains at least one dye represented by the below following general formula as magenta dye (9), comprise at least one dye represented by any one of (10) or (11) preferably, preferably comprise at least one dye represented by the following general formula (12) or (13) as a cyan dye Iga, in the present invention is represented by the following general formula in the magenta dye layer (9) A dye represented by the following general formula (10), a dye represented by the following general formula (11), and a dye represented by the following general formula (12) in the cyan dye layer; In general formula (13) Required to by containing dyes respectively.

  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. Z ^1, Z ² is either one of = the N-, the other is = C (R ⁹⁵⁾ - represents a. 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.

Below, with the specific example of the pigment | dye represented by either general formula (1) , (3) - (6), the pigment | dye represented by either of general formula (7)- (13) of this invention Although a specific example is shown below, the pigment | dye represented by either of General formula (7)-(13) used for this invention is not limited to the following example. In addition, the specific example ((1) -1-(1) -3, (3) -1-(3) -3) of the pigment | dye represented by either general formula (1), (3)-(6). , (4) -1 to (4) -4, (5) -1 to (5) -4, and (6) -1 to (6) -5) are all reference examples.

  Among the dyes represented by the general formulas (1) to (13), those not commercially available are disclosed in US Pat. Nos. 4,757,046, 3,770,370, and German Patent No. 2316755. 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 (Vylonal 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 weight Polystyrene (manufactured by Aldrich) 30 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 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 recording apparatus described in FIG. 3 of the present specification is used as the thermal transfer printer A, and the thermal fluctuation at the time of line recording of the thermal head when recording each line by the thermal printer as the thermal transfer printer B. A thermal transfer type printer which is obtained from image data and does not have a means for controlling the heat generation amount of the thermal head so as to suppress this temperature fluctuation 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.
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.
The output image was evaluated for tailing by using an image in which the highest density and the lowest density were repeated in the transport direction.
○: Trailing is hardly observed.
Δ: Trailing is observed ×: Trailing is clearly observed and is not acceptable.

  Each result is shown to Tables 1-4. Table 1 shows the result of density variation using the thermal transfer type printer A, and Table 2 shows the result of density variation using the thermal transfer type printer B. Table 3 shows the result of tailing in high-speed processing using the thermal transfer printer A, and Table 4 shows the result of tailing in 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, an unacceptable level of tailing is observed in the images output by performing high-speed processing using the thermal transfer printer B (Samples 111 to 419). Even if the image is output using the thermal transfer printer A, an unacceptable level of clear tailing is observed when the image is received by high-speed processing using the image receiving sheet R9 that does not contain a thermoplastic resin in the receiving layer. (Samples 109, 209, 309, 409).
On the other hand, in 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, the medium-period density fluctuation can be suppressed even at high speed processing. (Samples 101 to 108, Samples 201 to 208, Samples 301 to 308, Samples 401 to 408).
Particularly, 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 polyester polymer, polycarbonate polymer, or vinyl chloride polymer as the thermoplastic resin. In 304, Sample 306, Samples 401 to 404, and Sample 406, almost no tailing was observed.

It is a block diagram which shows the principal part of the electrical constitution of the thermal printer which implemented this invention. It is a diagram which shows the equivalent circuit in the automatic control system of the thermal head of the thermal printer. It is the schematic which shows the mechanical structure of the thermal printer. It is a block diagram which shows the characteristic in the system which controls the drive voltage of a thermal head automatically. It is a block diagram which shows a thermal head drive part. It is a block diagram which shows the characteristic of the automatic control system in the other embodiment which corrected the image data and eliminated the temperature fluctuation of a long period and a medium period. It is a block diagram which shows the characteristic of the automatic control system in the other embodiment which corrected the bias pulse number data and eliminated the temperature fluctuation of a long period and a medium period. It is sectional drawing which expands and shows the heat generating element of a thermal head.

Explanation of symbols

2 Thermal head 6 Heating element 7 Glaze 8 Head temperature detector 11 Substrate 20 Platen drum 23 Thermal recording material (thermal imaging sheet)
27 Heating element array 29 Housing 36 Environmental temperature detector 37 Drive voltage control unit 38 Thermal head drive unit

Claims (10)

A thermal transfer recording system using a thermal printer that superimposes ink sheets and drives each heating element provided in a line shape based on image data to record an image on a thermal transfer image-receiving sheet. Each line is recorded by the thermal printer. seeking a change in temperature at the time of line recording of the thermal head from the image data at the time of, to control the amount of heat generated by the thermal head so as to suppress the temperature fluctuations, and the receiving layer of the thermal transfer image-receiving sheet as a main medium of water which is formed is applied, and has free thermoplastic resin in the receiving layer, at least one of the thermoplastic resin is a vinyl chloride polymer, the ink sheet, the following general formula in the magenta dye layer (9 ), A dye represented by the following general formula (10), and a dye represented by the following general formula (11), Thermal transfer recording system which is characterized by containing the dye represented in the dye layer the following general formula (12), and the following general formula (13) dye represented by each.

(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.)

(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. 2. The thermal transfer recording system according to claim 1, wherein the receiving layer of the thermal transfer image-receiving sheet is a receiving layer containing a vinyl chloride latex. 3. The thermal transfer recording system according to claim 1, wherein the vinyl chloride polymer in the receiving layer of the thermal transfer image receiving sheet is a vinyl chloride copolymer. The thermal transfer recording system according to any one of claims 1 to 3 , wherein the receiving layer of the heat-sensitive transfer image-receiving sheet contains a fluorine-based release agent compound or a silicone-based release agent compound. The thermal transfer recording system according to claim 1, wherein the receiving layer of the heat-sensitive transfer image-receiving sheet contains a solid wax and a fluorine-based release agent compound or a silicone-based release agent compound. First temperature detection means for detecting the temperature of the thermal head attached to the thermal head, and second temperature detection means for detecting the temperature in the housing to which the thermal head is attached are provided, and the thermal head is mounted on the substrate. And a glaze formed on the substrate, a heating element formed on the glaze, and the first temperature detecting means attached to the substrate, and a thermal resistance from the substrate to the first temperature detecting means and a thermal resistance of the atmosphere. From this relationship, the glaze temperature is estimated based on the temperature signals of the first temperature detection means and the second temperature detection means, and the heat generation amount of the thermal head is controlled so as to suppress the fluctuation of the estimated glaze temperature. The thermal transfer recording system according to any one of claims 1 to 5 . The thermal transfer recording system according to any one of claims 1 to 6, wherein the control of the heating amount of the thermal head, characterized by being performed by controlling the head driving voltage. The thermal transfer recording system according to any one of claims 1 to 7 , wherein the heat generation amount of the thermal head is controlled by changing a width or the number of gradation expression drive pulses based on image data. . The thermal transfer recording system according to any one of claims 1 to 8 , wherein the heat generation amount of the thermal head is controlled by changing the width or number of bias drive pulses based on bias data. The yellow pigment layer of the ink sheet contains a pigment represented by the following general formula (7) and a pigment represented by the following general formula (8). The thermal transfer recording system described in 1.

(In the general formula (7), R ⁵¹ And R ⁵² Each independently represents a substituent. n8 represents an integer of 0 to 5. 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, a plurality of R ⁵¹ Or multiple R ⁵² May be the same or different. )

(In the general formula (8), R ⁶¹ Represents a substituent and R ⁶² , R ⁶³ And R ⁶⁴ Each independently represents a hydrogen atom or a substituent. 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. )

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