WO2004108424A1 - Reversible heat-sensitive recording medium and fluorine atom-substituted alcohol - Google Patents

Abstract

A reversible heat-sensitive recording medium comprising a supporting sheet and a heat-sensitive recording layer which is formed on the supporting sheet and contains a colorless or pale dye precursor and a developer for reversibly developing and decoloring the dye precursor is characterized in that the developer is a compound having such a structure wherein at least one fluorine atom is bonded to a carbon atom in the β-position and/or Ϝ-position relative to an alcoholic hydroxyl group. Also disclosed is such a fluorine atom-substituted alcohol.

Description

 Description Reversible thermosensitive self-recorded body and fluorine-substituted alcohol

Technical field

 TECHNICAL FIELD The present invention relates to an irreversible thermosensitive recording medium capable of performing coloring and decoloring by controlling heating conditions, and maintaining the colored and decolored states at room temperature. More specifically, the present invention forms a color-developed image on a white background, has a high contrast, does not decrease the color density after repeated color development / decoloration, and has a low density after color erasure. It relates to a reversible thermosensitive recording medium that is stable in some places. Background art

 The advantages of thermal recording media are that the recording device is compact and relatively inexpensive, the recording speed is fast, no consumables such as ink other than recording paper are required, and the recording method is a dry process, making maintenance easy. It is widely used as output paper for computers, measuring instruments, cash registers, CD'ATMs, fax machines, vending machines, handy terminals, etc. However, conventional thermosensitive recording media are irreversible, so information can be added, but once recorded, information cannot be erased, rewritten, or reused.

 Against the background of the garbage problem and deforestation issues that have been actively discussed in recent years, thermal recording paper is also required to be recycled into paper.However, in general, thermal recording paper is a contraindicated product when recycling used paper. It is difficult to recycle it as paper because it is treated as paper.

On the other hand, heat-sensitive recording media are also used as information display materials for magnetic recording cards such as prepaid cards and point cards. These magnets In the thermal card, the magnetic information is rewritten each time it is used, but the thermal recording information is not rewritten, so the updated information is added to the part where no image is recorded. However, since the area of the part that can be thermally recorded is limited, the actual situation is that the amount of information to be thermally recorded is unavoidably reduced or a card is reissued when the recording area is exhausted.

 As a means to solve the above problems, reversible thermosensitive recording media that can be rewritten many times have been developed. Furthermore, with the spread of IC cards in recent years, the demand for visualization of information recorded on cards has become increasingly strong, and expectations for reversible thermosensitive recording media have increased.

 Against these backgrounds, various reversible thermosensitive recording media have been proposed. For example, a polymer type reversible thermosensitive recording medium utilizing a change in transparency due to a difference in heating conditions has been disclosed (for example, JP-A-2000-141916, JP-A-20 0 1 — 19 19 651, see Japanese Patent Publication No. 2000-2, 18 7 366.) However, this method has the disadvantage that visibility in dark places is poor. In addition, there is a disadvantage that a white image is recorded on a colored background, and it is difficult to obtain a so-called paper-like recording medium on which a colored image is recorded on a white background.

 As a method for solving these ^) problems, a dye-type reversible thermosensitive recording medium that enables reversible recording while using a dye used in a conventional thermosensitive recording medium has been proposed. The dye-type reversible thermosensitive recording medium can record a color image on a white background, and has a relatively high contrast because it is a recording method using a change in absorption wavelength due to heating conditions. For example, the following method is known as a dye type reversible thermosensitive recording medium.

A method using an ascorbic acid derivative as a developer (for example, see Japanese Patent Application Laid-Open No. Sho 63-173,684) is disclosed. It has the disadvantage of not coloring. Also, a method of reversibly controlling color development and decoloration using an amphoteric compound having both an acidic group and a basic group in a molecule as a color developer (see, for example, Japanese Patent Application Laid-Open No. 8-150783) ) And a method in which an acidic substance and a basic substance are mixed and used as a color-developing / decoloring controlling agent (see, for example, JP-A-10-32940). However, since the coloring reaction and the decoloring reaction are competitive reactions, the contrast between the coloring state and the decoloring state is not clear, and the visibility is poor.

 A method has been proposed in which a compound having both an electron-accepting structure and a straight-chain aliphatic group in the molecule is used as a developer, and the property that the straight-chain aliphatic group is aggregated for decoloring is used. For example, a method using an organic phosphoric acid structure as an electron-accepting structure has been disclosed (for example, see Japanese Patent Application Laid-Open No. 7-46959). have. On the other hand, the method using a carboxyl group as the electron-accepting structure (for example, see Japanese Patent Application Laid-Open No. 2000-247Q34) has a drawback that the color developability is insufficient. .

 In a method in which a phenolic compound having a straight-chain aliphatic group is used as a color developer (see, for example, JP-A-6-210954), a comparative color-developing and decoloring balance is obtained. Although a reversible thermosensitive recording medium with a good color removal can be obtained, the color erasability is still insufficient. To obtain a practical level of color erasability, a color erasing aid is required (see, for example, 0 1—1 1 1 3 8 3 1 and Japanese Patent Application Laid-Open No. 2002-248600). However, the addition of the decoloring aid causes a problem that the storage stability of the print is reduced.

Therefore, in the reversible thermosensitive recording medium using these materials, the information remaining after the erasing operation and the newly printed information are overlapped to deteriorate the visibility, or the storage stability is insufficient. When stored under conditions However, since the density of the printed area decreases and the visibility deteriorates, for example, when applied to a point card, the card issuer limits the number of times of repeated printing and erasing or uses it for the card. In fact, it is necessary to take measures such as setting a deadline, and improvements are desired.

 In order to solve these problems, the present inventors have proposed in the past a color developer which is excellent in coloring property and decoloring property and has high storage stability (for example, Japanese Patent Application Laid-Open No. 2001-20559). However, there is still room for improvement in terms of stability against repeated printing and erasing many times.

 Also, in the field of temperature indication, reversible thermochromic compositions using a specific fluoroalcohol compound as a color-forming substance have already been proposed (for example, Japanese Patent Application Laid-Open No. H11-192579). See section 2). This composition can exhibit reversible color development and decoloration by combining a compound having a linear aliphatic group with a dye and a color-forming substance. However, the color development state occurs only when heated, and cannot be maintained when not heated, which is different from the technical field of the present invention. Further, it does not disclose a compound having both a fluoroalcohol group and a linear aliphatic group and / or a hydrogen bonding group in the same molecule as in the present invention. Disclosure of the invention

The present invention provides a reversible thermosensitive recording medium having a high contrast, capable of forming a color-developed image on a white background by using a small device, performing color development and decoloring only by a difference in heating conditions, and having a high contrast. That is what we are trying to do. In particular, it provides a product that is stable in places where the density after erasing is low and has high durability against repeated printing and erasing. In order to obtain a reversible thermochromic recording medium capable of performing color development and decoloring only by heating and having a high contrast between the color developing part and the color erasing part, and a color erasable reversible thermosensitive recording medium, Focusing on a dye-type reversible thermosensitive recording system composed of a colorless or pale-colored dye precursor and a developer as main components, as a result of intensive studies, it was found that as a developer, the 3rd- It has been found that a desired reversible thermosensitive recording medium can be obtained by using a compound in which at least one fluorine atom is bonded to a carbon atom at the T position, and the present invention has been completed. .

 The present invention includes the following embodiments.

[1] A sheet-like support, and a colorless or light-colored dye precursor formed on the sheet-like support, and a heat-sensitive recording layer containing a color developing agent for reversibly coloring and decoloring the precursor. Wherein the developer is a compound having a structure in which at least one fluorine atom is bonded to a carbon atom at position 3 and / or γ of the alcoholic hydroxyl group. A reversible thermosensitive recording medium characterized by the following.

[2] The reversible thermosensitive recording material according to [1], wherein the developer is a compound having at least one straight-chain aliphatic group having 8 to 30 carbon atoms in a molecule.

[3] The above-mentioned developer has the following structural formula (I) in the molecule:

 [1] or [2], which is a compound containing at least one straight-chain aliphatic group having 8 to 30 carbon atoms and containing one member selected from monovalent groups represented by Reversible thermosensitive recording medium.

[4] The developer is represented by the following general formula (II.):

(In the above formula, e represents an integer of 0 or 1. In addition, R ¹ and R ² are independently selected from a hydrogen atom, a methyl group, and a phenyl group. R ³ represents a hydrogen atom or a trifluoromethyl group. R ⁴ and R ⁵ independently represent a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ represents a monovalent linear aliphatic group having 8 to 30 carbon atoms. Further, X ¹ and X ² are each independently a single bond or the following structural formula (III)

H 9 H 〇

 -N-C- — S-N— -S-O- -C-O-

O O O 0 (I I I)

Represents a member selected from the divalent groups represented by, but does not include those in which X ¹ and X ² are simultaneously a single bond. )

 The reversible thermosensitive recording material according to any one of [1] to [3], which is a compound represented by the formula:

 [5] The developer has the following general formula (IV):

R 11 (I v)

(In the above formula, f represents an integer of 1 or 2, g represents an integer of 1 to 3. R ⁷ and R ^s each independently represent a member selected from a hydrogen atom, a methyl group, and a phenyl group. R ⁹ and R ^{1 U} each independently represent a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, R ¹¹ represents a monovalent linear aliphatic group having 8 to 30 carbon atoms. In addition, X ³ X ⁴ are each independently a single bond or the following structural formula (III):

N H

NH

Represents a member selected from the divalent groups represented by, but does not include those in which X ³ and X ⁴ are simultaneously a single bond, and those in which an atom other than a carbon atom is connected to the difluoromethyl group. )

 The reversible thermosensitive recording material according to any one of [1] to [3], which is a compound represented by the following formula:

 [6] The developer is represented by the following general formula (V):

-C——C- (V)

Ϋ ¹ Ϋ ²

(However, in the above general formula, Y ¹ and Y ² independently represent an oxygen atom or a sulfur atom.)

 The reversible thermosensitive recording material according to [1], which is a compound containing a divalent group represented by:

[7] The developer has the following structural formula (I) in the molecule:

 Including a member selected from a monovalent group represented by the following general formula (V):

 H H

 ■ N—— C——C—— Ν · (V)

 丫 1 γ: 2

(However, in the above general formula, Υ ¹ and Υ ² each independently represent an oxygen atom or a sulfur atom.)

 Is a compound containing one member selected from divalent groups represented by

The reversible thermosensitive recording medium according to [1] or [6].

[8] The developer is represented by the following general formula (VI):

H H H H H

 -N-C-N- -N-C-N- -C-N-C-

Represents one member selected from the divalent groups represented by OSOO. Y ³ and Y ⁴ independently represent an oxygen atom or a sulfur atom. )

 A reversible thermosensitive recording medium of any of [1], [6] and [7], which is a compound represented by the formula: .

[9] The developer is represented by the following general formula (VII):

(However, in the above formula, in OoSnM, m represents an integer of 1 or 2, n represents an integer of 1 to 3. In addition, R ¹⁸ and R ¹⁹ are independently selected from a hydrogen atom, a methyl group, and a phenyl group. R ^2Q represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ²¹ is a single bond or 1 to 2 carbon atoms.

0 represents a divalent hydrocarbon group, and R o ²² represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Et al is, X ^s is a single bond or the following structural formula (III): one

H H

-NC- -SN- -CO- 0 O (III)

H H H H H

 -N-C-N— -N-C-N- -C-N-C-

O S 0 0

Represents one member selected from the divalent group represented by. Y ⁵ and Y ⁶ independently represent an oxygen atom or a sulfur atom. )

 A reversible thermosensitive recording medium of any of [1], [6] and [7], which is a compound represented by the formula:

[10] The developer is represented by the following general formula (VIII):

(In the above general formula, p represents an integer of 0 to 5. R ²³ represents a hydrogen atom or a trifluoromethyl group, and R ²⁴ represents the following general formula (IX):

(However, R ²⁵ represents a member selected from a methyl group, a methoxy group, an acetyl group, and a halogen atom. In addition, q represents an integer of 0 to 5, and when q is 2 or more, a plurality of R ²⁵ are the same. Or may be different.)

 Represents a member selected from the monovalent group represented by. )

 The reversible thermosensitive recording material of any one of [1], [6], [7] and [8], which is a compound represented by the following formula:

 [11] The following general formula (II):

R ¹ R ³

^{HO- hC- -C- ■ R 4 ~~ X} 1 - R 5 one X ^s (II

(In the above formula, e represents an integer of 0 or 1. In addition, R ¹ and R ² are independently selected from a hydrogen atom, a methyl group, and a phenyl group. And R ³ represents a hydrogen atom or a trifluoromethyl group. R ′ ¹ and R ⁵ independently represent a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ represents a monovalent linear aliphatic group having 8 to 30 carbon atoms. Further, X ¹ and X ² are each independently a single bond or the following structural formula (III)

(III)

H H H H

 — N-C-O- -N-C-S- ■ N-C-O- ■ N-C-S- O O S S

H H H H H

 -N-C-N- -N-C-N- -C-N-C-

O S 0 0

Represents a member selected from the divalent groups represented by, but does not include those in which X ¹ and X ² are simultaneously a single bond. )

 A compound represented by

[1 2] The following general formula (IV):

(In the above formula, f represents an integer of 1 or 2, g represents an integer of 1 to 3. R ⁷ and R ⁸ are each independently a member selected from a hydrogen atom, a methyl group, and a phenyl group. the stands, R ⁹ and R ^{1 G} represents a divalent hydrocarbon group of a single bond or a number 1-2 0 carbon independently of each other, R ¹¹ is a monovalent linear aliphatic 0 8-3 carbon atoms And X ³ And X ⁴ are each independently a single bond or the following structural formula (III)

N H

 c

NH

H H H

 -N-C-N- -C-N-C-

Represents one member selected from the divalent groups represented by OS 00, but X ³ and X ⁴ are single bonds at the same time, and those in which an atom other than a carbon atom is connected to the difluoromethyl group Not included. )

 A compound represented by

[13] The following general formula (VI): — R ¹⁶ -X ⁵ -R ¹⁷ (VI)

(In the above formula, k represents an integer of 0 or 1. Further, R ¹² and R ¹³ independently represent a hydrogen atom, a member selected from a methyl group and a phenyl group, and R ¹⁴ represents a hydrogen atom. R ¹⁵ and R ¹⁶ independently represent a single bond or a divalent hydrocarbon group having 120 carbon atoms, and R ¹⁷ represents a hydrogen atom or 1 20 carbon atoms. X ⁵ represents a single bond or the following structural formula (III): (III)

H H H H H

 — N-C-N— — N-C-N— -C-N-C-

6 S 0 0

Represents one member selected from the divalent group represented by. Y ³ and Y ⁴ independently represent an oxygen atom or a sulfur atom. )

 A compound represented by

[14] The following general formula (V I I):

(However, in the above formula, m represents an integer of 1 or 2, n represents an integer of 1 to 3. Further, R ¹⁸ and R ¹⁹ are independently selected from a hydrogen atom, a methyl group, and a phenyl group. R ²⁰ represents a divalent hydrocarbon group having 1 to ²⁰ carbon atoms, R ²¹ represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ²² represents a hydrogen atom. Or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and X ⁶ is a single bond or the following structural formula (III): -

(III)

H H H H

-NCO- -NCS- -NC-0- -NCS- O 〇 SS

Represents one member selected from the divalent group represented by. Y ⁵ and Y ⁶ independently represent an oxygen atom or a sulfur atom. )

 A compound represented by

[15] The following general formula (V I I I):

(In the above general formula, p represents an integer of 0 to 5. R ²³ represents a hydrogen atom or a trifluoromethyl group, and R ²⁴ represents the following general formula (IX):

(However, R ²⁵ is a methyl group, a methoxy group, an acetyl group, a halogen atom Represents a member selected from In addition, q represents an integer of 0 to 5. When q is 2 or more, a plurality of R ²⁵ may be the same or different. )

 Represents a member selected from the monovalent group represented by. )

 A compound represented by

 The method for reversible thermal coloring and decoloring of the reversible thermosensitive recording medium according to the present invention includes the steps of: heating the thermosensitive coloring layer of the recording body to record an image by performing heating; and after using the recording, the thermosensitive coloring is performed. The layer is heated at a temperature lower than the color heating temperature to erase the color image.

 The reversible thermosensitive recording medium of the present invention forms a color image on a white background, and has high contrast. In particular, the color density after repeated color development and decolorization does not decrease, and is stable where the density after color erasure is low. Therefore, the reversible thermosensitive recording medium of the present invention has extremely high practical value. BEST MODE FOR CARRYING OUT THE INVENTION

 In the reversible thermosensitive recording medium of the present invention, the thermosensitive recording layer containing a color-forming component containing a leuco dye and a color developer as a main component is heated to a temperature higher than the temperature at which the color-forming component melts, and rapidly cooled by being rapidly cooled. It develops its color and this state of color development is maintained at room temperature. On the other hand, the coloring portion held at room temperature is heated to a temperature at which the color forming complex, which is a solid solution of the color forming component, is melted and then gradually cooled, or is cooled to a temperature at which the color forming complex is melted. It can be erased by heating, and the decolored state is maintained even when cooled to room temperature. The color developer of the present invention is a compound having a structure in which at least one fluorine atom is bonded to the] 3 and Z or γ carbon atoms of the alcoholic hydroxyl group.

Although the mechanism of this color development / decolorization is not clear, The alcoholic hydroxyl group is activated by a fluorine atom-bonded alkyl group having a high electronegativity, so that it exhibits a strong color developing ability to a basic leuco dye and develops color. In operation

It is considered that the cohesive force of the linear aliphatic group and Z or hydrogen bonding group in the developer molecule induces crystallization of the developer, and the dye and the developer are separated and decolorized. The temperature required to melt the color-forming component depends on the melting point of the color developer and the like, but is generally 120 to 240 ° C. In general, color development is achieved by heating in a few milliseconds and accompanying thermal heads, which facilitate rapid cooling. In general, the decoloration is performed by heating the color-forming component at a temperature higher than the melting temperature and then gradually cooling it, or at 60 to 180 ° C and below the temperature at which the color-forming component melts, for several tens of minutes. This is done by heating for milliseconds or more. For decoloring, a heat stamp or heat par, which can be easily heated and cooled slowly, is used. '

 In the reversible thermosensitive recording medium of the present invention, as a developer, the above-mentioned general formula (11), (IV), (VI), (VII), (VIII)

) Is preferably used. As specific examples, compounds No. (1) to (400) are shown below, but are not limited thereto. These compounds may be used alone or in combination of two or more.

H H

-N— C-C-C N— (CH ₂ ) ₁₇ CH ₃ (5) OO

-N— C- C— N— (CH ₂ ) ₂₁ CH ₃ (6) II II

0 o

H

-C-N— (CH ₂ ) ₂₁ CH ₃ (8) O

H H

-C-N— N—C— (CH ₂ ) ₂₀ CH ₃ (10) HH2 ^

(12)

H H H

-NC— (CH ₂ ) ₅ -N— C— — (CH ₂ ) i ₇ CH ₃ (15)

O O

(16)

H H H

-NC— (CH ₂ ) ₅ -N— C— C— N— (CH ₂ ) i ₇ CH ₃ (17)

OOO

H H

-C-N— (CH ₂ ) ₅ -C-N—— (CH ₂ ) ₁₇ CH ₃ (19)

OO

 | _ |

-N— C- (CH ₂ ) ₇ CH ₃ (43) O

NCCN— (CH ₂ ) nCH ₃ (51)

II II

 O 0

-N— CC— — (CH ₂ ) i ₈ CH ₃ (58) OO

 H | _ | H

HO-C- C- N- N- C- ( CH 2) 20 CH 3 (70) CF 3 0 〇 HHHHH

 oooo

 9 UTC UTCC UllTCIII—

-NC- (CH ₂ ) ₆ -CNNC- (CH ₂ ) i ₆ CH ₃ (73) 0 0 0

H H H

-N- C ~ (CH ₂ ) ₈ -C- N- N- C- (CH ₂ ) i ₆ CH ₃ (74)

OOO

H H H

-N—C— (CH ₂ ) ₅ -N— C— N— (CH ₂ ) ₂₁ CH ₃ (76)

O O

(77)

 H H H

-N— C- (CH ₂ ) ₅ — N— C— C— N— (CH ₂ ) ₂₁ CH ₃ (78)

0 O

H H H

-CN— (CH ₂ ) ₅ -CNNC— (CH ₂ ) ₆ CH ₃ (80)

〇 0 0

 H

H H

HO-C NCCN— (CH ₂ ) ₂ iCH ₃ (90) CF ₃ O 〇

H H

-C-N— N— C— (CH ₂ ) ₂₀ CH ₃ (110)

II II

oo

CH ₃

H HO-C. -N- -C- (CH ₂ ) ₁₆ CH ₃ (121) CF ₃₀

CF ₃

HO-C-CH ₂ --CN- (CH ₂ ) ₂₁ CH ₃ (142)

 O

CF ₃

HH HO— C— CH ₂ --CNNC— ₂ ) ₁₆ CH ₃ (143)

 II II CF, 〇 o

C ₃

 H

H0-C-CH ₂ --C- N--CNNC- (CH ₂ ) ₂₀ CH ₃ (150)

II CF 〇 〇 〇

CH ₃

HO-C— CH ₂ --C--(CH ₂ ) ₁₇ CH ₃ (161) I

CF ₃₀

CH ₃

 I

HO-C-CH ₂ --CN- (CH ₂ ) ₂₁ CH ₃ (162) I

CF ₃ O

(163)

CH ₃

HH HO— C— CH ₂ --C-N— N— C- (CH ₂ ) ₂₀ CH ₃ (164) CF OO

(171)

H

HO— CH ₂ -C— C— C— N— CH _{2 17} CH ₃ (172)

 F F 0

! f ί H H H

HO-CH -CCCCN- -CN— NC— (CH ₂ ) i ₆ CH ₃ (180)

III II II II FFFO oo

H H

HO-CH ₂ CH ₂ -C— C— C— C— — -C— (CH ₂ ), ₆ CH ₃ (185)

 F F F O O

₁₆ CH ₃ (191)

CF ₃ U | _ |

HO-CH ₂ -C- -N— C— N— (CH ₂ ) i ₇ CH ₃ (192)

CF ₃ O

HO-CH ₂ -C---C- (CH ₂ ) ₁₆ CH ₃ (221) 〇

H H

HO-CH ₂ -C- -N— C— N— (CH ₂ ) ₁₇ CH ₃ (222)

H H

HO-CH ₂ -C- -C-N— N— C— (CH ₂ ) ₁₆ CH ₃ (225)

 II II

oo

H

HO-CH ₂ -c- -N— C- -NC— (CH ₂ ) ₁₆ CH ₃ (227)

 II

 o O

H H

HO— CH ₂ — C--CH CH9— C— N— N— C— (CH ₂ ) ₁₆ CH ₃ (228)

 II II

 o o

CH ₃

HO-C—— C- -NC— (CH ₂ ) ₁₆ CH ₃ (232) CH ₃ FO

HO—? C— C ί C- —— (CH ₂ ) ₁₇ CH ₃ (242)

 0

9

0 contract Zdf / e) d ο

() 722

() 283

The

 Ο

 o

HHOCI 2H C0-

) (363



() 382

Further, as the color developing body of the present invention, the C-position of the alcoholic hydroxyl group or

] As the compound having at least one trifluoromethyl group at the carbon atom at the 3-position, the compound represented by the above general formula (II) or (VI) is preferably used, and has good color-forming property and decoloring property. Is shown.

 Specific examples of the compound represented by the general formula (II) include compounds No. (1) to (170), and particularly preferable are compounds N0. To (100). Specific examples of the compound represented by the general formula (VI) include compounds (251) to (340), and particularly preferred is compound No. (281). To (310) Further, as the compound having a difluoromethylene group, a compound represented by the above general formula (V) or (VII) is preferably used. Specific examples of the compound represented by the general formula (V) include the compounds N 0. (171) to (190) and (221) to (230). Particularly preferred are compounds N 0. (2 21) to (2 30). Specific examples of the compound represented by the general formula (VII) include the compounds (341) to (400), and particularly preferred is the compound No. (341). To (360).

 Of the compounds represented by the general formulas (II) and (VI) according to the present invention, 2,2,2 which is the main skeleton of the compound having one trifluoromethyl group at the α-position of the alcoholic hydroxyl group — Trifluoro-1-hydroxyxethyl group is generally represented by the following reaction formula (X):

H-

(The aldehyde compound is reacted with trifluoromethyltrimethylsilane (Rupate reagent) and then acid-hydrolyzed to give 2, 2, 2 2 _ Trifluoroethanol derivative is obtained. In this reaction, as the catalyst, triethylamine, tetra-n-butylammonium fluoride, or potassium fluoride is preferably used. As the solvent, a non-protonic polar solvent such as tetrahydrofuran or N, N'-dimethylformamide is preferably used, and is appropriately selected depending on the catalyst used. )

 Or the following reaction formula (X I):

³ ^ HO-C— (XI)

CF ₃

(By reducing the trifluoroacetyl group, a 2,2,2-trifluoroethanol derivative is obtained. In this reaction, a metal hydride is preferably used as a reducing agent, , More preferably sodium borohydride.The solvent is appropriately selected depending on the reducing agent used.)

 It can be synthesized by such methods as described above, but is not limited to these methods.

 For example, among the compounds represented by the general formula (VIII), in the case of a compound having one trifluoromethyl group at the position of the alcoholic hydroxyl group, the following reaction formula (XIII):

(In the presence of a catalyst, P-nitrobenzene aldehyde is reacted with Rupert's reagent, and then acid-hydrolyzed. Then, the obtained 1-1p-2-nitrophenyl 2,2,2— Catalytic reduction of trifluoroethanol to convert nitro groups to amino groups, followed by dehydration condensation with oxamonoamide derivatives . ) Can be synthesized.

 Further, among the compounds represented by the general formulas (II) and (VI) according to the present invention, hexafluoroyl which is a main skeleton of a compound having two trifluoromethyl groups at the α-position of an alcoholic hydroxyl group. The isopropyl group is generally represented by the following reaction formula (XIII):

_CF3 ~ ¾— ^R —, HO-iR (XIII)

(Hexafluoresoprono and phenol derivatives can be obtained by reacting a Grignard reagent with hexafluoroaceton and then hydrolyzing it.) However, the present invention is not limited to these methods.

 For example, among the compounds represented by the general formula (VIII), in the case of a compound having two trifluormethyl groups at the α-position of an alcoholic hydroxyl group, the following reaction formula (XIV):

_Μ α Hexafluoroacetone Η ₂₀

 (Hexafluoracetone is reacted with the Grignard reagent obtained by the reaction of p-amino benzene with metallic magnesium, and then hydrolyzed. Then, it is dehydrated and condensed with the oxamonoamide derivative. It can be synthesized by a method such as

Further, the compounds represented by the general formulas (IV) and (VII) according to the present invention can be obtained by using the following reaction formula (2) using a (2-hydroxy-11,1-difluoroethyl) benzene derivative as a starting material. XV):

(After reacting an aromatic compound with one trifluoromethyl group and a metal magnesium, carbon dioxide gas is blown into the reaction solution or the reaction solution is dropped on dry ice. A difluoroacetic acid derivative is generated, and a 2,2-difluoroethanol derivative can be synthesized by reducing the carboxyl group of the difluoroacetic acid derivative to alcohol using a reducing agent. As the solvent, a non-protonic polar solvent is preferably used, and a metal hydride is preferably used in the latter stage of the carboxyl group reduction reaction. In the case of the compound represented by the formula (IV), starting from 2,2-difluoro-1-hydroxypropionic acid ester, the following reaction formula (XVI): R′-NH ₂

HO HO-CH ₂ -C— C0 ₂ R HO— CH. --0C Τ 一 — CC—— W—- R '(XV Τ 1

 t ROH I U

 It can be synthesized by a method such as FFO, but is not limited to these methods.

 In the thermosensitive recording layer of the reversible thermosensitive recording medium of the present invention, examples of the compound used as a dye precursor include triphenylmethane-based, fluoran-based, and diphenylmethane-based compounds. You can choose from known ones.

These dye precursors include, for example, 3— (4-Jetylamino 2-1-ethoxyphenol) 1-3— (1-Echinolane 2—Methynolein Donolé 13—yl) 14-azaphthalide, 3, 3—bis (p—methylami 6-dimethylaminophthalide, 3-phenethylamino 7-dibenzylaminovenzo [α] fluoran, 3- (1-ethylethyl 2-methylindole-3-yl) _3- () 4-Jethylamino 1 2— η—Hexyloxyphen 4 1-azaphthalide, 3— (1 1-ethyl 1 2-methinolein Donoret 1 3-inole) 1 3— (4—Jetylamino 2 2-methylphenyl 2 4 —Azaphthalide, 3— (4-diethylaminophenyl) 1-3— (1 ethyl-12-methylindole-3-yl) phthalide, 3— (2-methyl-1 1 _η— Octylindole 1-3-yl) 1-3- (4-tert-amino2 -ethoxyphenyl) 14-azaphthalide, 0.3- (Ν-ethylyl-isopentylamino) 1-6-methyl-7- Anilino Fluoran, 3— 1-methyl-6-methyl-7-anili-nofluoran, 3-ethyl-6-methyl-7- (ο, ρ-dimethylanilino) fluoran, 3-(—- ethyl-Ν_ρ-toluidino) _6-methyl-7 —A diinofluoran, 3—pyrrolidinol 6 _methyl-17-anilinofluoran, 3-dibutylamino 6-methyl-7-anilinofluoran, 3— (Ν-cyclohexyl Ν-methylamino) 1-6—methyl 1 7—anilinofluorinated, 3—getylamino 7— (0—coupling roaniline) fluoran, 3—getylamino 7— (m—trifluoromethylaniline) fluoran, 3 —Di (n-pentyl) amino 6-methyl-7-anilinofluoran, 3- [N- (3-ethoxypropyl) -1-N-ethylamino] — 6-methyl_7-ani Fluoran, 3- (N-n-hexyl-N-ethylamino) _ 7 1 (o-chloroanilino) Fluoran, 3- (N-ethyl-N-2-2-tetrahydrofurfurylamino) 6-Methyl-1 7-anilino-no-leorane, 2,2-bis {4- [6,-(N-cyclohexyl-1-N-methylamino) -1 3'-methylspiro [phthalidol 3,9'- Santen] 1 2 '—ilamino] fenir} propane and 3-dibutylamino 7- (0-chloroanilino) fluoran.

 Also, 3,6-Dimethoxyfluoran, 3-Pyrrolidine 6-Chlorofluoran, 3-Jetylamino_6-methyl-7-Chlorofluoran, 3-Jetylamino 7-Chlorofluoran, 3- 1,7-methylbenzoylorane, 3-ethylamino, 6,7-dimethylfluoran, 3- (N-methyl-p-toluidino) — 7-methylfluoran, 3 _ (N-methyl-N-a Soamylamino 1-7,8-benzofluoran, 3,3,1-bis (l-n-amyl-2-methylindole-3-yl) phthalide, 3- (N-methyl N-isoamylami 1) 7-phenoxyfluoran, 3,3'-bis (1-n-butyl-2-methylindole-3-yl) phthalide, 3,3,1-bis (1-ethynolei-2-methylin) Dole 3 Phthalide, 3, 3'-bis (p-dimethylaminophenyl) phthalide, 3- (N-ethyl_N_p-tolylamino) 1- (N-phenylamino-methylamino) fluoran, 3 —Jetylamino 7-anilino fluoran, 3-ethylamino 7-benzylamino fluoran, 3-pyrrolidinol 7-dibenzylamino fluoran, etc., but the present invention is not limited to these. Alternatively, two or more kinds may be used in combination.

The reversible thermosensitive recording medium of the present invention can contain a conventionally known thermofusible substance generally known as a photosensitive agent in the thermosensitive recording layer. Typical examples thereof are m-terphenyl, 1-hydroxy-12-naphthenic acid phenyl ester, p-benzyloxybenzoic acid benzyl, benzylnaphthyl ether, dibenzyl terephthalate, and diphenyl carbonate. , Ditolyl carbonate, diphenylsulfone, 1,2-bis (m-trinoleoxy) ethane, p-benzylbiphenyl, 1,5-bi (P-methoxyphenoxy) -13-oxapentane, oxalic acid diesters, di (4-methylbenzyl) oxalate, 1,4-bis (P-tolyloxy) benzene, 1,4-bis [2— ( 4-Methylbenzyloxy) ethoxy] benzene and the like, but these compounds have the ability to enable high-density color development of a reversible thermosensitive recording medium with relatively low applied energy.

 In addition, the reversible thermosensitive recording medium of the present invention contains a thermofusible substance having a long-chain alkyl group, which is generally known as a color erasure accelerator, in the thermosensitive recording layer as long as the desired effect is not impaired. be able to. Examples of such discoloration accelerators include hexadecanamide, octadecyl peryl, dioctadecyl perylene, docosanoylhydrazide, N, N, 1dicosyloxadiamide, and the like.

 These compounds, in addition to their ability to enable high-density color development of reversible thermosensitive recording materials with relatively low applied energy, accelerate the decolorization reaction even at relatively low temperatures during image erasing operations, and enhance reversibility. Has the ability to improve.

 Further, the heat-sensitive recording layer according to the present invention may contain waxes and pigments within a range that does not impair the effects of the present invention. Further, in order to fix these components to the support, a binder is usually contained. It is.

 As the waxes, for example, known waxes such as paraffin, amide wax, bisimide wax, and metal salts of higher fatty acids can be used. However, when a metal salt of a higher fatty acid is added, the color erasure density increases as the color is repeatedly formed and erased, and the erasure of a color image may be incomplete. It is preferably 1% by mass or less of the dry mass of the heat-sensitive recording layer.

Examples of pigments include silica, clay, calcined clay, talc, calcium carbonate, zinc oxide, titanium oxide, aluminum hydroxide, and hydroxyl. Inorganic fine powders such as zinc oxide, parium sulfate, and surface-treated calcium carbonate, and organic materials such as urea-formalin resin, styrene / methacrylic acid copolymer, and polystyrene resin System fine powder can be given. However, when zinc oxide is added, the color erasure density increases with repeated color development and color erasure, and the erasure of color images may become incomplete.Therefore, the content of zinc oxide is the dry weight of the heat-sensitive recording layer. It is preferably 1% by mass or less of the total.

 The binder can be selected from water-soluble polymers, water-dispersible polymers, water-insoluble polymers, active energy ray-curable compounds, and the like.

Examples of the water-soluble polymers and the water-dispersible polymers include polybutyl alcohols and derivatives thereof having various molecular weights (for example, acetoacetyl-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, and sulfonyl group). Denatured polyvinyl alcohol, etc.), starch and its derivatives (eg, oxidized starch, vinyl acetate starch, aldehyde-modified starch, etc.), cellulose derivatives (methoxenolerose, canoleboxy methinoresenorelose, methinoreserenolorose, ethylcellulose, etc.) ), Poly (sodium acrylate), polyvinylpyrrolidone, acrylamide acrylate copolymer, acrylamide / acrylic ester / methacrylic acid terpolymer, styrene / Maleic anhydride copolymer Water-soluble polymer materials such as sodium chloride, polyacrylamide, sodium alginate, gelatin, and casein; and polyvinyl acetate, polyurethane, styrene / butadiene copolymer, and polyacrylic acid. Latexes such as styrene, polyacrylic acid ester, vinyl chloride / biel acetate copolymer, polybutyl methacrylate, ethylene / vinyl acetate copolymer, and styrene Z-butadiene acryl-based copolymer can be used. it can. These polymers can be used alone or Alternatively, two or more of them may be used in combination, and the present invention is not limited to the examples listed here.

 Examples of water-insoluble polymers include phenoxy resin, luroacetate butylate resin, polyurethane resin, polyester resin,

(Meth) acrylic resin, styrene z (meth) acrylic copolymer, vinyl chloride / vinyl acetate copolymer, polycarbonate resin, etc. These are usually used by dissolving them in an appropriate organic solvent. . These resins may be used alone or as a mixture of two or more thereof, and are not limited to the examples described here.

 In addition, a resin modified to have a hydroxyl group in these polymers is used, and a compound having a plurality of isocyanate groups in the molecule is added as a crosslinking agent to cure the resin. Thus, a reversible thermosensitive recording medium having excellent durability can be obtained. The amount of the crosslinking agent to be added is appropriately determined according to the amount of the hydroxyl group in the resin and the number of the isocyanate groups of the crosslinking agent to be used.

Examples of the compounds used as the cross-linking agent include 2,41-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene diisocyanate Socinate, 1,5—naphthalene diisocyanate, p—phenylene diisocyanate, 4,4, diphenylmethanediisocyanate, 3,3,1-dimethyl-4,4,1-diphenylmethanediisocyanate, 4 , 4'-Biphenylenediisocyanate, hexamethylenediisosocyanate, isophoronediisocyanate, dicyclohexylmethanediisocyanate, methylenebis (4-cyclohexenylisocyanate), hydrogenated diphenylmethanediisocyanate , 2,2,4-Trimethylhexamethylene diisocyanate , Bis (2-isocyanah-t チ ル il) fumarate, 6 _isopirpir 1,3—hue Elgiy ssociate, 4-diphenyl isopropyl thiocyanate, lysine ii ssociate, triphenyl meth ate li ssinate, polymethylene polyphenylisocyanate and the like. These crosslinking agents may be used alone or in combination of two or more, and are not limited to the examples listed here.

 Examples of the active energy ray-curable compounds can be selected from the following compounds, and these may be used alone or as a mixture of two or more thereof. It is not limited to.

 (1) Aliphatic, alicyclic, and aromatic alcoholic and polyalkylene glycol acrylates (or metalylates). (2) Aliphatic, alicyclic, and aromatic acrylate (or methacrylate) compounds obtained by adding an alkylene oxide to an alcohol. (3) Polyacryloyl (or methacryloyl) alkyl phosphates. (4) A reaction product of a polybasic acid, a polyol and an acrylic (or methacrylic) acid. (5) The reaction product of an isocyanate, a polyol, and an acrylic (or methacrylic) acid. (6) The reaction product of an epoxy compound and acrylic (or methacrylic) acid. (7) A reaction product of an epoxy compound, a polyol, and acrylic (or methacrylic) acid. (8) An amide composed of aliphatic, alicyclic, and aromatic amines or a nitrogen-containing cyclic compound and acrylic acid (or methacrylic acid).

 When the active energy ray-curable compounds are cured by ultraviolet irradiation, an appropriate amount of a photoinitiator is added, and an ultraviolet irradiation device having a high-pressure mercury lamp, a xenon lamp, and a metal halide lamp is used as an irradiation light source. The placement is determined as needed.

Examples of photoinitiators include acetophenone, benzophenone, benzene Zion ethers, chloroacetophenone, ethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, benzylmethylketal, thioxanthone, —acinoleoximeester, acylphosphonoxide, glyoxylate —Keto coumarin, 2—Ethilan anthraquinone, camphorquinone, benzyl, Michla ketone, etc., but are not limited thereto.

 When the active energy ray-curable compounds are cured by electron beam irradiation, the electron beam accelerator to be used is not particularly limited, and examples thereof include a Van de Graff type scanning method and a double scanning method. An electron beam irradiation apparatus such as a curtain beam method or a curtain beam method can be used. Among them, a curtain beam method which is relatively inexpensive and can obtain a large output is effectively used. The acceleration voltage at the time of electron beam irradiation is preferably from 100 to 300 kV, and the absorbed dose is preferably from 0.1 to 9 Mrad. The oxygen concentration in the atmosphere during electron beam irradiation is preferably 500 ppm or less. If the oxygen concentration exceeds 500 ppm, oxygen acts as a polymerization retarder, and the curing of the electron beam-curable resin may be insufficient.

In the thermosensitive recording layer of the reversible thermosensitive recording medium according to the present invention, the content of the dye precursor is generally preferably 5 to 40% by mass of the dry mass of the thermosensitive recording layer, and the content of the developer Is generally preferably 5 to 50% by mass of the dry mass of the heat-sensitive recording layer. If the content of the color developer is less than 5% by mass, the color developing ability is insufficient, and even if it is used in a large amount exceeding 50% by mass, the color developing capability is saturated, and the color density and the erasure are reduced. special improvement con Trust in color density was not observed, sometimes force ^s is economically disadvantageous. When waxes and pigments are contained in the heat-sensitive recording layer, their contents are preferably 2 to 20% by mass and 5 to 50% by mass, respectively. 5 to 70% by mass.

The support used in the reversible thermosensitive recording medium of the present invention includes paper (including acidic paper and neutral paper) used for conventional thermosensitive recording media, and a coated surface coated with pigment, latex, or the like. Paper, laminated paper, synthetic paper made from polyolefin resin, plastic films such as polyolefin, polyester, polyimide, etc., as well as glass plates and conductive rubber sheets can be selected. A coating solution containing a mixture of the above-mentioned required components is applied on at least one surface of such a support, and dried to produce a reversible thermosensitive recording medium. The coating amount is preferably 1 to: I 5 g / m ² , and 2 to: L 0 g Z m ² in a state where the coating liquid layer was dried. '

 In the present invention, an undercoat layer may be provided below the reversible thermosensitive coloring layer. Also, on the back side of the reversible thermosensitive recording medium, it is possible to prevent blocking at the time of contact between the front side and the front side, to suppress penetration of water or oil from the back side, and to provide a pack layer for curl control. it can.

 Furthermore, in order to improve heat resistance, light resistance, printability, abrasion resistance, and repeated durability of coloring and decoloring, coating such as a protective layer and a printing layer on the reversible thermosensitive coloring layer. Layers can also be formed. Further, by using a cured layer containing an active energy ray-curable compound as a main component for the protective layer, the abrasion resistance, the repeated coloring and the decoloring durability can be drastically improved.

In the present invention, at least one of a water-soluble polymer, a water-dispersible polymer, a thermosetting resin, and an active energy ray-curable compound is provided between the heat-sensitive recording layer and the coating layer by a binder. It is preferable to have at least one intermediate layer containing the following. In addition, by including an ultraviolet absorbing inorganic pigment such as titanium oxide or an organic ultraviolet absorber in the intermediate layer, light resistance can be improved.

 In the present invention, the reversible thermosensitive recording medium may be further processed in order to increase the added value of the reversible thermosensitive recording medium, and may be provided with a higher function. For example, the back side is treated with adhesive, rewet adhesive, or delayed tack type adhesive to make adhesive paper, rewet adhesive paper, delayed tack paper, or magnetically processed to enable reversible magnetic recording It can be a thermosensitive recording medium. The back side can be used as a recording paper that can be used for recording on both sides by providing the functions of thermal transfer paper, injection paper, carbonless paper, electrostatic recording paper, and xerography paper. . Of course, it is also possible to use a two-sided reversible thermosensitive recording medium. '

 The device for recording (coloring) and erasing (erasing) images can be selected from thermal heads, thermostats, heating rollers, hot pens, sheet heating elements, laser light, infrared light, etc., depending on the purpose of use. However, the present invention is not particularly limited to these.

Example

 Hereinafter, the present invention will be described specifically with reference to Examples.

 Unless otherwise specified, “parts” and “%” represent “parts by mass” and “% by mass”, respectively.

 The developers used in the examples were synthesized as follows. `` Synthesis example of color developer ''

In the following synthesis examples, unless otherwise specified, all reaction vessels used were flasks equipped with a reflux condenser, all organic solvents used had been subjected to dehydration such as distillation, and distilled water was used for water. did. The synthesis was performed under an inert gas stream unless otherwise specified. Synthesis Example 1>

 1— (p—stearoylamino) phenyl 2,2,2—Trifluoroethanol (compound No. 41) synthesis method:

4Dissolve 12-nitrobenzaldehyde (15.lg) and triethylamine (2.0 g) in dimethylformamide (100 mL), and add trifluoromethyltrimethylsilane (14.2). g) is added dropwise. After stirring at room temperature for 17 hours, 3N hydrochloric acid (1 O mL) is added, and the mixture is stirred at room temperature for 30 minutes. After adding water (200 mL), extract with ethyl acetate (150 mL) three times (use a total of 450 mL). The organic layer is collected, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to a volume of about 100 mL. Activated carbon-supported palladium (5.0 g) is stirred in this solution for 3 hours under a pressure of 200 kPa of hydrogen gas by a pressurized reactor. After the reaction solution is filtered, the filtrate is concentrated under reduced pressure until the filtrate becomes about 5 OmL, and n-hexane (100 mL) is added to the residue while stirring, whereby crystals are precipitated. The precipitated crystals were collected by filtration and dried under reduced pressure to give an intermediate (p-aminophenyl) _2,2,2-trifluoroethanol as a colorless powder (14.3 g). Can be (Yield based on p-2-nitrobenzaldehyde is 75%) The above intermediate 1 — (p-aminophenol) _2,2,2-trifluoroethanol (9.56 g) Was dissolved in tetrahydrofuran (100 mL), pyridine (7.91 g) was further added, and stealic acid chloride (15.1 g) was added dropwise while cooling this solution on ice. I do. After completion of the dropwise addition, the reaction solution is returned to room temperature, and further stirred for 24 hours. 3N hydrochloric acid (2 O mL) is added dropwise to the reaction mixture, and this solution is further poured into a beaker containing water (500 mL) and stirred for 30 minutes. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure to obtain the desired product, p- (stearoylamino) phenyl 2,2,2-trifluoretano. (Compound No. 41) is obtained as a white solid (21.7 g). (Yield: 95% based on 11- (p-aminophenol) 1,2,2,2-trifluorethanol)

 The analytical values of this crystal are as follows.

Melting point; 1 18.6 ° C

 NMR measurement (in DMS O-d6) (numbers are ppm); δθ.84 (t, 3H), 1.22 (s, 30H), 1.56 (bs, 2) H), 2.28 (t, 2H), 5.05 (m, 1H), 6.72 (d, 2H), 7.37 (d, 2H), 7.5 9 (d, 2H), 9.9 1 (s, 1H)

<Synthesis example 2>

 1- {71- (Stearoylhydrazinocarbonyl) -heptanoylamino)}-2,2,2-Trifluoretanol (compound No. 73):

11- (p-Aminophenyl) -12,2,2-trifluoroethanol (9.56 g) synthesized according to Synthesis Example 1 above was dissolved in tetrahydrofuran (100 mL). Then add pyridine (7.91 g). While cooling this solution on ice, methyl 8-chloro-1-oxo-titanate (10.3 g) is added. After completion of the dropwise addition, the mixture is stirred for 30 minutes under ice-cooling, and then the reaction solution is returned to room temperature and stirred for 17 hours. To the reaction solution is added a 4N aqueous solution of potassium hydroxide (25 mL), and the mixture is stirred at room temperature for 2 hours. The reaction solution is neutralized with 3N hydrochloric acid (35 mL). Ethyl acetate (500 mL) is added to this solution, and the organic matter is extracted. The organic layer is collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate is concentrated under reduced pressure. Next, the residue and stearyl hydrazide (13.4 g) were dissolved in tetrahydrofuran (150 mL), and 1-hydroxybenzotriazole (6.89 g) was dissolved with stirring. ). Sa Then, N, N, diisopropyl carpoimide (5.55 g) is added dropwise, and the mixture is stirred at room temperature for 1 hour and at 60 ° C for 2 hours. After the temperature of the reaction solution is returned to room temperature, it is poured into a beaker containing water (700 mL) and stirred for 1 hour. The precipitated solid is collected by filtration, washed with water, and dried under reduced pressure to give the desired product, 1— {7— (stearoylhydrazinocarbonyl) -heptanoylamino)} 1,2,2,2-trifluoroethanol (Compound No. 73) is obtained as a white solid (27.9 g). (1 — (p -aminophenyl) 1, 2,2 — Yield based on trifluoroethanol 91 1%)

 The analytical values of this crystal are as follows.

Melting point: 142.7 ° C

 NMR measurement (in DMS O-d6) (numbers are ppm); δθ.84 (t, 3), 1.22 (s, 30Η) ', 1.28 (s, 4H), 1.49 (m, .2H), 1.56 (m, 2H), 2.08 (m, 4H), 2.28 (t, 2H), 5 .0 5 (m, 1 H), 6

. 7 1 (d, 2H) 7.31 (d, 2H), 7.59 (d, 2H), 9.61 (s, H), 9.92 (s, 1H) )

Synthesis Example 3>

 N- {p- (1-hydroxy-1,2,2,2-trifluoro) ethyl} phenyl-1-N, —n-decyloxadiamid (Compound No. 49):

1- (p-Aminophenyl) -2,2,2-trifluoroethanol (5.75 g) and pyridine (4.75 g) synthesized according to Synthesis Example 1 above were added to tetrahydrofuran. Dissolve in (30 mL), cool to 0, and add ethyl chloroglyoxylate (4.10 g) dropwise. After completion of the dropping, the reaction solution is returned to room temperature, stirred for 17 hours, and then added with a prescribed potassium hydroxide aqueous solution (30 mL) and stirred for 4 hours. . After adding 3N hydrochloric acid (60 mL) to the reaction solution, the organic matter was extracted with ethyl acetate (30 mL), the organic layer was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was depressurized. Concentrate. Hexane is added to the residue, and the precipitated crystals are collected by filtration and dried under reduced pressure. The intermediate, N- {p- (1-hydroxy-1,2,2,2-trifluoroethyl) phenyl} oxamic acid, is colorless. Obtained as a powder (5.68 g). (Yield based on 1- (P-aminophenyl) -1,2,2,2-trifluoroethanol is 72%)

 The above intermediate N— {p- (1-hydroxy-2-, 2,2-tritrifluoromethyl) phenyl) oxamic acid (5.26 g) and 1-aminodecane (3.14) g) was suspended in tetrahydrofuran (100 mL), 1-hydroxybenzotriazole monohydrate (3.12 g) was added, and the mixture was stirred for 15 minutes, and then N, N, diisopro '. Pilcarpositimide (2.78 g) was added, and the mixture was stirred at room temperature for 30 minutes. The reaction solution is further heated to 60 ° C. and stirred for 2 hours, then returned to room temperature and stirred for 17 hours. The reaction solution was poured into water (100 mL), and the precipitated crystals were washed with water to obtain the target compound, {{p-N- (n-dodecylaminoxoxalyl) amino) amino} 2, 2,2-Trifluoroethanol is obtained as colorless crystals (7.64 g). (The yield based on N— {p- (1—hydroxy-2,2,2-tritrifluoroethyl) phenyl} oxamate is 95%.)

 The analytical values of this crystal are as follows.

Melting point: 1 5 1.8 ° C

NMR measurement (in DMS O-d6) (number is ppm); δ 0.84 (t, 3 3), 1.23 (s, 14 1), 1.48 (bs, 2) H), 3.17 (m, 2H), 5.10 (m, 1H), 6.78 (d, 2H), 7.44 (d, 2H), 7.8 1 (d, 2H) , 8.96 (s, 1 H), 10.6.6 (s, 1 H)

 <Synthesis example 4>

 N— {p- (1-hydroxy2,2,2-tritrifluoro) ethyl} phenyl-N'-n-octadecyloxadiamid (Compound N 0.57) :

 N_ {p- (1-hydroxy2,2,2_trifluoroethyl) phenyl} oxamic acid (5.26 g) and n-octadecylamine (5.39) synthesized according to Synthesis Example 3 above. g) is dissolved in n-tetradecylamine (4.27 g) in tetrahydrofuran (20 mL), and 1-hydroxybenzotriazole (3.06 g) is added with stirring. . Further, N, N'-diisopropylcarpoimide (2.78 g) was added dropwise, and the mixture was stirred at room temperature for 1 hour and at 60 ° C for 4 hours. The reaction solution is returned to room temperature and stirred for 17 hours, then poured into water (300 mL) and stirred for 1 hour. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure to obtain the desired product as a white solid (8.85 g). (The yield based on N— {p— (1—hydroxy-1,2,2,2-trifluoroethyl) phenyl} oxamic acid is 86%)

 The analytical values of this crystal are as follows.

Melting point; 1 39.6 ° C

 NMR measurement (in DMS O-d6) (number is ppm); δ 0.83 (t, 3 3), 1.22 (s, 30Η), 1.48 (bs, 2) H), 3.16 (m, 2H), 5.09 (m, 1H), 6.

7 7 (d, 2H), 7.43 (d, 2H), 7.80 (d, 2H)

, 8.966 (s, 1H), 10.6.6 (s, 1H)

 <Synthesis example 5>

N-{p-(1 -hydroxy 2,2,2-trifluoro) ethyl} Feneru N '— 2 -phenylethyloxaxamide (compound No.2 9 3):

 N- {p- (1-hydroxy2,2,2-trifluoroethyl) phenyl} oxamic acid (13.2 g) and j3-phenethylamine (2.42) synthesized according to Synthesis Example 3 above. g) is dissolved in tetrahydrofuran (20 mL), and 1-hydroxybenzotriazole (3.06 g) is added with stirring. Further, N, N'-diisopropylcarbodiimide (2.78 g) was added dropwise, and the mixture was stirred at room temperature for 1 hour and further at 60 ° C for 4 hours. After the temperature of the reaction solution is returned to room temperature, it is poured into a beaker containing water (300 mL) and stirred for 1 hour. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure to obtain the desired product as a white solid (6.89 g). (N_ {p- (1-hydroxy-1,2,2,1-trifluoroethyl) phenyl) Oxamic acid yield 94%) The analytical values of this crystal are as follows. '

Melting point: 1 9 1.9 ° C

 NMR measurement (in DMS O-d6) (numbers are ppm); δ 2.83 (t, 2), 3.43 (m, 2Η), 5.10 (m, 1Η) ), 6.79 (s, 1Η), 7.20 (m, 3Η), 7.29 (m, 2Η), 7.44 (d, 2Η), 7.81 (d, 2Η), 9.03 (m, 1Η), 10.6.7 (s, 1Η)

<Example 1>

 A reversible thermosensitive recording medium was prepared by the following operations (1) to (5). (1) Preparation of dispersion Α

 ^ Section

3-dibutylamino 6-methyl-7 7 _

Anilino Fnoleorane 20 Polyvinyl alcohol 10% aqueous solution 10 Water 70 The above composition was pulverized using a sand grinder until the average particle size became 1.1 μm.

 (2) Preparation of dispersion B

 ^ Section

1 One (p-stearoylamino) phenyl

One, two, two—Trifluoroethanore

 (Compound No. 41, Synthesis Example 1) 20 Polyvinyl alcohol 10% aqueous solution 10 Water 70 The above composition was prepared using a sand grinder to have an average particle size of 1.

and crushed to m.

 (3) Formation of reversible thermosensitive recording layer

100 parts of the above solution A, 250 parts of solution B, and 250 parts of a 10% aqueous polyvinyl alcohol solution were mixed and stirred to obtain a coating solution. This coating solution on one surface of a PET film having a thickness of 1 5 0 / m, the coating amount after drying 5. 0 g Zm ² become due to sea urchin coated, to form a reversible thermosensitive recording layer by drying .

 (4) Formation of intermediate layer

60 parts of a 50% dispersion of force-orientate clay and 200 parts of a 10% aqueous polyvinyl alcohol solution were mixed and stirred to prepare a coating solution for an intermediate layer. This coating solution was applied onto the reversible thermosensitive recording layer of (3) so that the coating amount after drying was 1.5 g / m ^2, and dried to form an intermediate layer.

 (5) Formation of overcoat layer

Polyester acrylate (trade name: Aronics M-830, manufactured by Toa Gosei Co., Ltd.) 40 parts, Polyester acrylate (trade name: 一 口 タ ス タ ス M-620, manufactured by Toa Gosei Co., Ltd.) 40 parts, calcium carbonate (Product name: Lyton A, Bihoku Powder Chemical Industry Co., Ltd.) 20 parts were mixed and stirred, and the mixture was applied on the intermediate layer of (4) so that the coating amount was ^2.5 g / m ² . . The obtained coating layer was irradiated with an electron beam under the conditions of an oxygen concentration of 300 ppm or less in the electron beam irradiation chamber, an acceleration voltage of 175 kV, and an absorbed dose of 3 Mrad to form an overcoat layer. A reversible thermosensitive recording medium was obtained.

 (6) Color development and decoloration test

 The reversible thermosensitive recording medium thus obtained was printed with a printing voltage of 21.7 v and a printing pulse of 1.0 ms using a thermal coloration tester TH PMD manufactured by Oshoku Denki. The print color density was measured with a Macbeth reflection densitometer RD_914.

The colored sample was heated using a thermal gradient tester manufactured by Toyo Seiki at a heating temperature of 100 ° C, a pressure of 1 kg / cm ² , and a heating time of 1.0 second. Was measured with a Macbeth reflection densitometer RD 914. Table 1 shows the test results.

 (7) Repeated color development / decolorability test

 Printing after repeating the color development and color erasure tests in section (6) above 20 times The color density and the color erasure were measured with a Macbeth reflection densitometer RD-914. Table 1 shows the test results.

<Example 2>

 A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. However, in the preparation of the dispersion B, 1_ (p-docosanoylamino) instead of 1- (p-stearoylamino) phenyl-2,2,2-trifluoroethanol / re (compound No. 41) (F) Phenyl 2,2,2-trifluoroethanol (compound No. 42) was used. Table 1 shows the test results.

Example 3>

A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. In preparing Dispersion B, instead of 1- (p-stearoylamino) phenyl 2,2,2_trifluoroethanol (compound No. 41), 1— { 7— (Stearoylhydrazinocarbonyl) heptanoylamino)} — 2,2,2-trifluoroethanol (Compound N 0.73, Synthesis Example 2) was used. Table 1 shows the test results.

 <Example 4>

 A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. In preparation of the dispersion B, N— {instead of 1- (p-stearoylamino) phenyl 2,2,2-tritrifluoroethanol (compound No. 41) was used. p- (1-Hydroxy-2,2,2-trifluoro) ethyl} phenyl N, 1-n-octadecyloxaxamide (Compound No. 57, Synthesis Example 4) Was. Table 1 shows the test results.

Example 5>

 A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. In preparing Dispersion B, instead of 1- (p-stearoylamino) phenyl 2,2,2-trifluoroethanol (compound No. 41), N— {p -(1-Hydroxy-2,2,2-trifluoro) ethyl} phenyl N, 1-n-decyloxadiamid (Compound No. 49, Synthesis Example 3) was used. The test results are shown in Table 1.

A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. However, in the preparation of the dispersion B, instead of 11- (p-stearoylamino) phenyl 2,2,2-tritrifluoroethanol (compound No. 41), N- {p -(1—hydroxy-1,2,2—tri Fusleole) ethinole} Pheninole N, 12-phenylenoletin oxadiamide (Compound No. 293, Synthesis Example 5) was used. Table 1 shows the test results.

Example 7>

 A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. However, in the preparation of the dispersion B, instead of 11 (p-stearoylamino) phenyl 2,2,2-tritrifluoroethanol (compound No. 41), N— {p -(1 -Hydroxy- 1, 2,2,2-trifluoro) ethyl} Feninole N, hexyloxaxamide (Compound No.287) was used. Table 1 shows the test results. <Example 8>

 A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. However, in preparing the dispersion B, instead of 11- (p-stearoylamino) phenyl-2,2,2-trifluoroethanol (compound No.41), N- {p- 2- (2-hydroxy-1,1,1,1,3,3,3_hexafluoro) propyl} phenylu N, 12-fluoroniruethyloxadiamid (compound No. 2 6 3) was used. Table 1 shows the test results.

Example 9>

 A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. However, in the preparation of the dispersion B, instead of 11- (P-stearoylamino) phenyl 2,2,2-tritrifluoroethanol (compound No. 41), N- {p -2-(2-Hydroxy-1,1,1,1,3,3,3-hexafluoro) propyl} Fenil N, cyclohexyloxadiamide (Compound No.257) Was used. Table 1 shows the test results.

<Comparative Example 1> A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. However, when preparing the dispersion B, instead of 1_ (p-stearoylamino) phenyl-2,2,2-tritrifluoroethanol (compound No. 41), 1— (P— Stearoylamino) phenylethanol (having a methyl group instead of the trifluoromethyl group of compound No. 41) was used. Table 1 shows the test results.

<Comparative Example 2>

 A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. However, when preparing the dispersion B, instead of 1- (p-stearoylamino) phenyl 2,2,2-tritrifluoroethanol (compound No. 41), 1- (p-stearoylamino) —Propanoylamino) Fe2,2,2— Trifluoroethanol (having no linear aliphatic group having 11 to 30 carbon atoms and represented by the general formula (V) 2 (A compound having no valence group). Table 1 shows the test results.

<Comparative Example 3>

 A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. However, in preparing Dispersion B, p-stearoylamino was used in place of 11- (p-stearoylamino) phenyl 2,2,2-trifluoroethanol (compound No. 41). Nophenol (a compound having a phenolic hydroxyl group and a linear aliphatic group) was used. Table 1 shows the test results.

Comparative Example 4>

A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. However, in preparing Dispersion B, instead of 1- (p-stearoylamino) phenyl 2,2,2-trifluoroethanol (compound No. 41), N-p- Droxyphenyl mono-N, -2-phenylethyloxadiamide (phenolic hydroxyl group and general formula (V) A compound having a divalent group represented by: Table 1 shows the test results.

 <Comparative Example 5>

 A reversible thermosensitive recording medium was prepared and tested in the same manner as in Example 1. However, in the preparation of the dispersion B, instead of 1- (p-stearoylamino) phenyl 2,2,2—trifluoroethanol (compound No. 41), 3—fluoro A mixture (reversible thermochromic material) of 4 parts of propanol and 16 parts of neopentyl stearate was used. Table 1 shows the test results. Item No. Color density Density Density Repeat test

Example 1 1.50 0.11 1.50 '0.11 Example 2 1.51 0.10 1.50 0.10 Example 3 1.50 0.09 1.50 0. 09 Example 4 1.50 0.10 1.50 0.10 Example 5 1.50 0.10 1.51 0.10 Example 6 1.51 0.10 1.51 0.10 Example 7 1.50 0.10 1.50 0.10 Example 8 1.52 0.11 1.52 0.11 Example 9 1.51 0.11 1.51 0.11 Comparative Example 1 0.10 0.10 10 0.10 0.10 Comparative Example 2 1.55 1.55 1.55 1.55 Comparative Example 3 1.50 0.17 1.49 0.25 Comparative Example 4 1.53 1.53 1.53 1 . 53 Comparative Example 5 • 0. 11 0. 11 0. 11 0. 11 As is clear from the comparison between Examples 1 to 9 and Comparative Example 1, the alcoholic hydroxyl group activated by the fluorocarbon group showed a strong color developing ability with respect to the basic leuco dye. As is clear from comparison of Examples 1 to 4 with Comparative Example 2 or Examples 4 to 9 with Comparative Examples 2 and 4, the color developer of the present invention has a linear aliphatic group in the molecule. Alternatively, by having a hydrogen bonding group represented by the general formula (V), reversible coloring and decoloring are possible.

 As is clear from comparison of Examples 1 to 9 with Comparative Example 3, the image formed on the reversible thermosensitive recording medium of the present invention shows a phenolic compound having a linear aliphatic group. Compared to a color image obtained using a colorant, it has a higher contrast and is excellent in repeatability of color development and decoloration.

 Further, the reversible thermochromic material used in Comparative Example 5 cannot maintain the color development state after the printing operation as shown in Examples 1 to 9. Industrial potential

 The reversible thermosensitive recording medium of the present invention forms a color image on a white background and has a high contrast. In particular, the color density after repeated coloring and decoloring does not decrease, and is stable in places where the density after decoloring is low. Therefore, the reversible thermosensitive recording medium of the present invention has extremely high practical value.

Claims

The scope of the claims '

1. A sheet-like support and a heat-sensitive recording layer formed on the sheet-like support and containing a colorless or light-colored dye precursor, and a developer for reversibly coloring and decoloring the dye precursor In the reversible thermosensitive recording medium having the above, the color developing agent is the j8-position of the alcoholic hydroxyl group and Z or

A reversible thermosensitive recording material characterized in that it is a compound having a structure in which at least one fluorine atom is bonded to a carbon atom at the T / position.

 '2. The developer has at least a straight-chain aliphatic group having 8 to 30 carbon atoms.

The reversible thermosensitive recording material according to claim 1, which is a compound contained in one molecule.

3. The developer has the following structural formula (I) in the molecule:

 (I)

F h F F

 -C— C— OH C—C—OH — C— C— CH OH

 I I I I I I

F CH ₃ F Ph FF

3. The reversible compound according to claim 1, wherein the compound is a compound containing at least one straight-chain aliphatic group having 8 to 30 carbon atoms and containing one member selected from a monovalent group represented by Thermosensitive recording medium.

 4. The developer has the following general formula (II):

R ¹ R ³

HOH-C- -C- -FT> ⁴ —— X ¹ —— R ⁵ —— X ² —— R ⁶ (II)

R CF

(In the above formula, e represents an integer of 0 or 1. In addition, R ¹ and R ² are independently selected from a hydrogen atom, a methyl group, and a phenyl group. R ³ represents a hydrogen atom or a trifluoromethyl group. : ⁴ and R ⁵ each independently represent a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ represents a monovalent linear aliphatic group having 8 to 30 carbon atoms. X ¹ and X ² are each independently a single bond or

—

〇 (III)

H H H H

 ■ N-C-0- ■ N-C-S— -N-C-O- — N-C-S- 0 O S S

H H H H H

 — N-C-N— — N-C-N— -C ,,-N-C-

Represents one member selected from the divalent groups represented by OS 00, but does not include those in which X ¹ and X ² are simultaneously a single bond. )

 The reversible thermosensitive recording material according to any one of claims 1 to 3, which is a compound represented by the following formula:

5. The developer has the following general formula (IV):

(In the above formula, f represents an integer of 1 or 2, g represents an integer of 1 to 3. R ⁷ and R ⁸ are each independently a member selected from a hydrogen atom, a methyl group, and a phenyl group. R 9 and R ^{1 (3} each independently represent a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, R ¹¹ represents a monovalent linear aliphatic group having 8 to 30 carbon atoms. X and X ⁴ are each independently a single bond or the following structural formula (III)

〇

 OOSH

H Η

 One N-C one -S-N- -C-O- 0 〇 (I I I)

■

〇

H H H H H

-NCN— -NC ,,-N- -C ,,-NC _n o o-snn

 O S 0 0

Represents a member selected from divalent groups represented by the following formulas, wherein X ³ and X ⁴ are simultaneously a single bond, and those in which an atom other than a carbon atom is connected to the difluoro methyl group Not included. )

 The reversible thermosensitive recording material according to any one of claims 1 to 3, which is a compound represented by the following formula:

 6. The developer has the following general formula (V):

(In the above general formula, Y ¹ and Y ² each independently represent an oxygen atom or a sulfur atom.)

 The reversible thermosensitive recording material according to claim 1, which is a compound containing a divalent group represented by:

7. The developer has the following structural formula (I) in the molecule:

CH ₃ CF ₃

― C ϊ -CH ₂ 0H — — C— CH ₂ 〇H — C Γ— CH ₂ OH —— C— CH ₂ OH

 1

3 ^Γ 3 3 3

 N H

—— N H

— CH0CH OH

Contains a member selected from the monovalent radicals represented by

Equation (v)

 ■ c ~ c--(V)

Ϋ ¹ Ϋ ²

(However, in the above general formula, Υ ¹ and Υ ² each independently represent an oxygen atom or a sulfur atom.)

 7. The reversible thermosensitive recording material according to claim 1, which is a compound containing one member selected from divalent groups represented by:

8. The developer has the following general formula (VI) (VI)

(However, 0 S

 In the above, k represents an integer of 0 or 1. Also, R

N

1 ² and R ¹³ are each independently a hydrogen atom, a member selected from methyl, phenyl group, R ¹⁴ represents a hydrogen atom or Application Benefits Furuoromechiru group. R ¹⁵ and R ¹⁶ each independently represent a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and R〇HN ¹⁷ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Represent. In addition, X ⁵ is a single bond or the following structure:

Model (I I I):

—〇 一 -S- HN

esn

 s

 H 0 H

 -N-C- -C-0- 0 0 (I I I)

H H

 -N-C-0- -N-C-S- c-o- 0 O s

H H H H H

 — N-C-N— — N-C-N— -C-N-C-

O S 6 O

Represents one member selected from the divalent group represented by Υ ³ and Υ ⁴ independently represent an oxygen atom or a sulfur atom. )

 The reversible thermosensitive recording material according to claim 1, wherein the thermosensitive recording material is a compound represented by the following formula:

9. The developer has the following general formula (VII):

(However, in 9δ in the above formula, m represents an integer of 1 or 2, n represents an integer of 1 to 3. R ¹⁸ and R ¹⁹ are independently selected from a hydrogen atom, a methyl group and a phenyl group. R ^2Q represents a divalent hydrocarbon group having 1 to 20 carbon atoms, R ²¹ represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ²² represents Represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and X ⁶ is a single bond or the following structural formula (III):

Η 0

 H

 ■ N-C- -S-N- -S-0- -C-0- 0 0 0 (I I I)

H H H H

 -N-C-0- -N-C-S- -N-C-0- — N-C-S- 0 〇 S S

H H H H H

 -N-C-N- -N-C-N -.- C-N-C-

Represents one member selected from the divalent group represented by OS 00. Y ⁵ and Y ⁶ independently represent an oxygen atom or a sulfur atom. )

 The reversible thermosensitive recording material according to claim 1, which is a compound represented by the following formula:

10. The developer is represented by the following general formula (VIII):

(However, in the above general formula, p represents an integer of 0 to 5. R ²³ represents a hydrogen atom or a trifluoromethyl group, and R ²⁴ represents the following general formula (IX):

 (I X)

(However, R ²⁵ represents a member selected from a methyl group, a methoxy group, an acetyl group, and a halogen atom. In addition, q represents an integer of 0 to 5, and when q is 2 or more, a plurality of R ²⁵ are the same. Or may be different.)

 Represents a member selected from the monovalent group represented by. )

 The reversible thermosensitive recording material according to any one of claims 1, 6, 7, and 8, which is a compound represented by the following formula:

 1 1. The following general formula (II):

(In the above formula, e represents an integer of 0 or 1. In addition, R ¹ and R ² are independently selected from a hydrogen atom, a methyl group, and a phenyl group. And R ³ represents a hydrogen atom or a trifluoromethyl group. R ⁴ and R ⁵ independently represent a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ represents a monovalent linear aliphatic group having 8 to 30 carbon atoms. Further, X ¹ and X ² are each independently a single bond or the following structural formula (III):

 OoSHn

 H H H H

 ■ N-C-0- -N-c-s— -N-C-O- -N-C-S- 0 o s S

H H H H H

 -N-C-N- -N-C-N- -C-N-C-

O S O 〇

Represents a member selected from the divalent groups represented by, but does not include those in which X ¹ and X ² are simultaneously a single bond. )

 A compound represented by

 1 2. The following general formula (IV):

R ⁷ F

HO— fC- ■ C-) ~ R ⁹ ——X ³ —— R10— χ--R "(IV)

(In the above formula, f represents an integer of 1 or 2, g represents an integer of 1 to 3. R ⁷ and R ⁸ are each independently a member selected from a hydrogen atom, a methyl group, and a phenyl group. R ⁹ and R ^{1 Q} each independently represent a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ represents a monovalent linear aliphatic group having 8 to 30 carbon atoms. And X ³ And X ⁴ are each independently a single bond or the following structural formula (III)

S

H H H H H

 -N-C-N- ■ N-C-N- -C-N-C-

Represents one member selected from the divalent groups represented by OSOO, including those in which X ³ and X ⁴ are simultaneously a single bond, and those in which an atom other than a carbon atom is connected to the difluoromethyl group Absent. ) '

 A compound represented by

 1 3. The following general formula (VI):

(In the above formula, k represents an integer of 0 or 1. Further, R ¹² and R ¹³ independently represent a member selected from a hydrogen atom, a 'methyl group and a phenyl group, and R ¹⁴ represents a hydrogen atom or R ¹⁵ and R ¹⁶ each independently represent a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁷ represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms. X ⁵ represents a single bond or the following structural formula (III): ' HN HN HN

H H H H H

 — N-C-N— — N-C-N— -C-N-C-

O S O O

Represents one member selected from the divalent group represented by '. Y ³ and Y ⁴ independently represent an oxygen atom or a sulfur atom. )

 A compound represented by

 1 4. The following general formula (V I I): esn u

HOH- _N _ _R 21_ _X 6_ _R 22 _(V ! D

(In the above formula, m represents an integer of 1 or 2, n represents an integer of 1 to 3. R ¹⁸ and R ¹⁹ are each independently a member selected from a hydrogen atom, a methyl group, and a phenyl group. R ^2Q represents a divalent hydrocarbon group having 1 to 20 carbon atoms, R ²¹ represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ²² represents a hydrogen atom or Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and X ⁶ is a single bond or the following structural formula (III): H

Represents one member selected from the divalent group represented by Also, Y ⁵お = s = n

And Y each independently represent an oxygen atom or a sulfur atom. )

 A compound represented by

 1 5. The following general formula (V I I I): esn

(In the above general formula, p represents an integer of 0 to 5. R ²³ represents a hydrogen atom or a trifluoromethyl group, and R ²⁴ represents the following general formula (IX):

(IX)

(However, R ²⁵ is a methyl group, a methoxy group, an acetyl group, a halogen atom Represents a member selected from In addition, q represents an integer of 0 to 5, and when q is 2 or more, a plurality of R ²⁵ may be the same or different. )

 Represents a member selected from the monovalent group represented by. )

 A compound represented by