JP2008266325A - Novel diphenylsulfone derivative and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosensitive recording material excellent in the storage stability (particularly plasticizer resistance) of images and the storage stability of the ground and a new diphenylsulfone derivative to be used therefor. <P>SOLUTION: The diphenylsulfone derivative is represented by formula (III) (wherein each simbol has a respective predetermined meaning). The thermosensitive recording material comprises a thermosensitive recording layer containing a colorless or pale basic leuco dye and a color developing agent for color-developing the basic leuco dye, on a support, and at least one kind of the diphenylsulfone derivative represented by the above formula (III) as the color developing agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a heat-sensitive recording material for obtaining a recorded image by utilizing a color development reaction by heat between a colorless or light-colored basic leuco dye and a developer, and a novel diphenylsulfone derivative that can be used as the developer. .

  In general, a heat-sensitive recording material that obtains a recorded image by utilizing a color development reaction by heat between a colorless or light-colored basic leuco dye and a developer is very clear in color, and there is no noise during recording. Due to the advantages of being relatively inexpensive, compact, and easy to maintain, it has been widely put into practical use in the fields of facsimiles, computers, various measuring instruments and the like. As these recording apparatuses are diversified and have higher performance, the required quality for heat-sensitive recording materials has become higher. With respect to the color development sensitivity, it is required that a clear color image with a high density can be obtained even with minute heat energy as the apparatus is miniaturized and the recording speed is increased. Furthermore, in recent years, it has been used in large quantities in fields where reliability of recorded images such as labels is important, and storage stability against plasticizers and oils and the like contained in organic polymer materials used for packaging. There is a strong demand for a recording material having a high color image. In addition, for use in labels, for which demand has been increasing in recent years, not only image storage stability, but particularly stability of the unprinted portion against heat is required.

In response to these requirements, for example, urea urethane compounds disclosed in Patent Document 1 and Patent Document 2, Patent Document 3 and Patent Document 4, and Patent Document 5 are disclosed in order to improve storage stability. There is a method of using a high-storing developer such as a diphenylsulfone cross-linking compound alone, but these highly-storing developers have a certain degree of storage stability to plasticizers compared to general-purpose developers. Although improved, a heat-sensitive recording material that can sufficiently satisfy other storage stability has not yet been obtained.
International Publication No. 00/14058 Pamphlet JP 2002-332271 A JP-A-8-333329 Japanese Patent Laid-Open No. 10-29969 JP 2003-212841 A

  The present invention has been made in view of such circumstances, and the problem to be solved is a heat-sensitive recording material excellent in the storage stability of images (particularly plasticizer resistance) and the storage stability of the background, and the use thereof. It is to provide a novel diphenylsulfone derivative for the purpose.

  As a result of intensive research to solve the above problems, the present inventors have made a thermal recording layer in which a thermal recording layer containing a colorless or pale basic dye and a developer as main components is provided on a support. It has been found that the above problems can be solved by including at least one diphenylsulfone derivative having a specific structure as a developer in the material, and the present invention has been completed.

That is, the present invention has the following features.
[1] The following general formula (I):

[Where:
R ^{1 to} R ⁶ each independently represent a halogen atom, a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
R represents a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
p, q, r, s, t, and u each independently represent an integer of 0 to 4, and in the case of 2 or more, R ^{1 to} R ⁶ may be the same or different,
n is 0;
A is a linear or branched C1-12 saturated or unsaturated hydrocarbon group which may have an ether bond, or the following formulas (a) to (c):

(In the formula, each X independently represents a methylene group or an ethylene group, Y represents a hydrogen atom or a C1-4 alkyl group, and Z represents an arylene group or a C1-10 alkylene group). Is shown). ]
At least one diphenylsulfone derivative (I) represented by:
The following general formula (II):

[Where:
R ^{11 to} R ¹⁶ each independently represent a halogen atom, a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
R ^a represents a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
p1, q1, r1, s1, t1, and u1 each independently represent an integer of 0 to 4, and in the case of 2 or more, R ^{11 to} R ¹⁶ may be the same or different,
n1 represents an integer of 1 to 5,
A ¹ is a linear or branched C 1-12 saturated or unsaturated hydrocarbon group that may have an ether bond independently, or the following formulas (a1) to (c1):

(Wherein, X ¹ independently represents a methylene group or an ethylene group, Y ¹ represents a hydrogen atom or a C1-4 alkyl group, and Z ¹ represents an arylene group or C1-10) Represents an alkylene group). ]
A diphenylsulfone derivative mixture containing at least one diphenylsulfone derivative (II) represented by:
[2] A is a linear and diphenyl sulfone derivative (I) is a saturated or unsaturated hydrocarbon group of or branched C1-12, saturated or unsaturated A ¹ is C1-12 linear or branched And a diphenylsulfone derivative (II) which is a hydrocarbon group of the diphenylsulfone derivative mixture according to [1],
[3] The diphenylsulfone derivative mixture according to [1] or [2], wherein the amount of the diphenylsulfone derivative (II) is 0.05 to 99% by weight with respect to the total weight of the diphenylsulfone derivative,
[4] The following general formula (III):

[Where:
R ^{21 to} R ²⁶ each independently represent a halogen atom, a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
R ^b represents a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
p2, q2, r2, s2, t2, and u2 each independently represent an integer of 0 to 4, and in the case of 2 or more, R ^{21 to} R ²⁶ may be the same or different,
n2 represents an integer of 0 to 5,
A ² is independently a linear or branched C 1-12 saturated or unsaturated hydrocarbon group which may have an ether bond, or the following formulas (a2) to (c2):

(Wherein, X ² independently represents a methylene group or an ethylene group, Y ² represents a hydrogen atom or a C1-4 alkyl group, and Z ² represents an arylene group or C1-10) Represents an alkylene group). However, in the case of n2 = 0, a saturated or unsaturated hydrocarbon group of the in ^{A 2} C1-12 has an ether bond. ]
A diphenylsulfone derivative represented by:
[5] a n2 = 0, and a saturated hydrocarbon group, or unsaturated C1~12 straight-chain or branched ^{A 2} is an ether bond, or the following formula (a2) ~ (c2):

(Wherein, X ² independently represents a methylene group or an ethylene group, Y ² represents a hydrogen atom or a C1-4 alkyl group, and Z ² represents an arylene group or C1-10) The diphenylsulfone derivative according to [4], which represents an alkylene group of
[6] n2 is an integer from 1 to 5, and, ^{A 2} is a saturated or unsaturated hydrocarbon group of C1~12 straight-chain or branched, [4] diphenyl sulfone derivative described,
[7] Furthermore, the following general formula (IV)

[Where:
R ^{31 to} R ³⁶ each independently represent a halogen atom, a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
R ^c represents a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
p3, q3, r3, s3, t3, u3 are independently an integer of 0 to 4, and if ^more, R 31 ^{to R 36} may be different from each other in the same,
n3 represents an integer of 0 to 5,
A ³ is independently a linear or branched C 1-12 saturated or unsaturated hydrocarbon group which may have an ether bond, or the following formulas (a3) to (c3):

(Wherein, X ³ independently represents a methylene group or an ethylene group, Y ³ represents a hydrogen atom or a C1-4 alkyl group, and Z ³ represents an arylene group or C1-10) Represents an alkylene group). ]
And at least one diphenylsulfone derivative (IV) represented by the formula: and a diphenylsulfone derivative mixture according to any one of [1] to [3] or any one of [4] to [6]. And a diphenylsulfone derivative mixture.
[8] The diphenylsulfone derivative mixture according to [7], wherein the content of the diphenylsulfone derivative (IV) is 0.01 to 10% by weight based on the total weight of the diphenylsulfone derivative,
[9] A thermosensitive recording material provided with a thermosensitive recording layer containing a colorless or light-colored basic leuco dye and a developer for coloring the basic leuco dye on a support, A heat-sensitive recording material containing, as a colorant, the diphenylsulfone derivative mixture according to any one of [1] to [3] or [7] to [8],
[10] A thermosensitive recording material provided with a thermosensitive recording layer containing a colorless or light-colored basic leuco dye and a developer for coloring the basic leuco dye on a support, A heat-sensitive recording material containing the diphenylsulfone derivative according to any one of [4] to [6] as a colorant.

  According to the present invention, there is provided a heat-sensitive recording material in which image storage stability, in particular, image storage stability in plasticizer resistance and background storage stability at high temperatures are compatible at a high level. Further, a novel diphenylsulfone derivative capable of easily obtaining a heat-sensitive recording material having such performance and a mixture containing the same are provided.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
(Diphenylsulfone derivative)
First, definitions of symbols in each formula used in this specification will be described.
Examples of the halogen atom in R ^{1 to} R ⁶ , R ^{11 to} R ¹⁶ , R ^{21 to} R ^26, and R ^{31 to} R ³⁶ include chlorine, bromine, fluorine, and iodine. Among these, chlorine and bromine are preferable.
The alkyl groups in R ^{1 to} R ⁶ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ and R ^{31 to} R ^{36 and} R, R ^a , R ^b and R ^c are straight if they have 1 to 12 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n- An alkyl group having 1 to 6 carbon atoms such as a hexyl group, isohexyl group, 1-methylpentyl group, and 2-methylpentyl group is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
The alkenyl groups in R ^{1 to} R ⁶ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ and R ^{31 to} R ^{36 and} R, R ^a , R ^b, and R ^c are straight if they have 2 to 12 carbon atoms. For example, vinyl group, allyl group, isopropenyl group, 1-propenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 2-methyl-2-propenyl group, etc. An alkenyl group having 2 to 4 carbon atoms is preferred.

R ^{1 to} R ⁶ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ and R ^{31 to} R ³⁶ and the aryl group in R, R ^a , R ^b, and R ^c are a monocyclic ring having 6 to 14 carbon atoms A tricyclic aromatic hydrocarbon group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like, and among them, a phenyl group is preferable. The aryl group may be substituted with, for example, the above alkyl group, the above aryl group, a hydroxyl group or a halogen atom, and the position and number of the substituent are arbitrary and are not particularly limited. When substituted with two or more substituents, the substituents may be the same or different. Examples of substituted aryl groups include tolyl groups, phenylmethyl groups (benzyl groups), phenylethyl groups (trityl groups), diphenylmethyl groups, 3-phenylpropyl groups, 2-phenylpropyl groups, 4-phenylbutyl groups, biphenyl groups, A biphenylmethyl group, a naphthylmethyl group, etc. are mentioned, Especially, C6-C8 alkyl substituted aryl groups (aralkyl group), such as a benzyl group, are suitable.

p, q, r, s, t, u, p1, q1, r1, s1, t1, u1, p2, q2, r2, s2, t2, u2, p3, q3, r3, s3, t3 and u3 are 0 to 0. Although the integer of 4 is shown, Preferably it is 0-2, More preferably, it is 0. However, p, q, r, s, t, u, p1, q1, r1, s1, t1, u1, p2, q2, r2, s2, t2, u2, p3, q3, r3, s3, t3 and u3 are In the case of 2 to 4, R ^{1 to} R ⁶ may be the same or different and are preferably the same.
n represents 0, n1 represents an integer of 1 to 5, n2 represents an integer of 0 to 5, and n3 represents an integer of 0 to 5. Among these, n1 is preferably 1 to 2, more preferably. 1, n2 and n3 are preferably 0 to 2, more preferably 0 or 1.

A, A ¹ , A ² and A ³ are linear or branched saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms which may have an ether bond. Examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, methylmethylene. Group, dimethylmethylene group, methylethylene group, methyleneethylene group, ethylethylene group, 1,2-dimethylethylene group, 1-methyltrimethylene group, 1-methyltetramethylene group, 1,3-dimethyltrimethylene group, 1 -Ethyl-4-methyl-tetramethylene group, etc., among which ethylene group, trimethylene group, tetramethyl group A saturated hydrocarbon group having 2 to 6 carbon atoms such as a len group, a pentamethylene group and a hexamethylene group is preferred. Specific examples of the unsaturated hydrocarbon group include vinylene group, ethynylene group, propenylene group, 2-butenylene group, 2-butynylene group, 1-vinylethylene group, 1,2-xylyl group, 1,4-xylyl group. Examples thereof include aromatic hydrocarbon groups such as 1,2-xylyl group and 1,4-xylyl group.

  Examples of the hydrocarbon group having an ether bond include an ethyleneoxyethylene group, a tetramethyleneoxytetramethylene group, an ethyleneoxyethyleneoxyethylene group, an ethyleneoxymethyleneoxyethylene group, and a 1,3-dioxane-5,5-bismethylene group. Among them, ethyleneoxyethylene group and ethyleneoxyethyleneoxyethylene group are preferable. In the case of n1 = 1 to 4 or n2 = 1 to 4, the saturated hydrocarbon group or the unsaturated hydrocarbon group can optionally have an ether bond, but when n2 = 0, the saturated hydrocarbon group Alternatively, the unsaturated hydrocarbon group has an ether bond.

A ² may be a divalent group selected from the following formulas (a2) to (c2). In the formula, X ² represents a methylene group or an ethylene group, Y ² represents a hydrogen atom or a C1-C4 alkyl group, Z ² represents an arylene group or a C1-C10 (preferably C2-C6) alkylene group. . Incidentally, A, the following formula is also in ^{A 1} and ^{A 3} (a2) 2 divalent groups corresponding to ~ (c2) (a) ~ (c), (a1) ~ (c1) and (a3) ~ (c3) Can be adopted.

  Specifically, 1,3-xylyl group, 1,4-xylyl group, 2-hydroxytrimethylene group, 2-hydroxy-2-ethyltrimethylene group, 2-hydroxy-2-propyltrimethylene group, 2- Hydroxy-2-isopropyltrimethylene group, 2-hydroxy-2-butyltrimethylene group, 1,3-benzenedicarbonyl group, 1,4-benzenedicarbonyl group, ethanedicarbonyl group, propanedicarbonyl group, butane Examples include carbonyl group, pentanedicarbonyl group, hexanedicarbonyl group, etc. Among them, 1,4-xylyl group, ethanedicarbonyl group, propanedicarbonyl group, butanedicarbonyl group, pentanedicarbonyl group, hexanedicarbonyl group Is preferred.

Specific examples of the typical compound in the diphenylsulfone derivative (I) and the diphenylsulfone derivative (III) when n2 = 0 include the following compounds, but are not limited thereto. Absent.
2- [4- (4-Hydroxyphenylsulfonyl) phenoxy] -2 ′-[4- (4-methoxyphenylsulfonyl) phenoxy] -diethyl ether, 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2 '-[4- (4-Ethoxyphenylsulfonyl) phenoxy] -diethyl ether, 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2'-[4- (4-n-propoxyphenylsulfonyl) phenoxy] -Diethyl ether, 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2 '-[4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether, 2- [4- (4-hydroxyphenylsulfonyl) ) Phenoxy] -2 '-[4- (4-n-butoxyphenylsulfonyl) Phenoxy] -diethyl ether, 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2 ′-[4- (4-t-butoxyphenylsulfonyl) phenoxy] -diethyl ether, 2- [4- (4- Hydroxyphenylsulfonyl) phenoxy] -2 '-[4- (4-allyloxyphenylsulfonyl) phenoxy] -diethyl ether, 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2'-[4- (4 -Benzyloxyphenylsulfonyl) phenoxy] -diethyl ether

  1- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -2- (2- [4- (4-methoxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1- (2- [4- (4-Hydroxyphenylsulfonyl) phenoxy] ethoxy) -2- (2- [4- (4-ethoxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy ] Ethoxy) -2- (2- [4- (4-n-propoxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -2- (2- [4- (4-Isopropoxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1- (2- [4- (4- Droxyphenylsulfonyl) phenoxy] ethoxy) -2- (2- [4- (4-n-butoxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy ] Ethoxy) -2- (2- [4- (4-t-butoxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -2- (2- [4- (4-Allyloxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -2- (2- [4- ( 4-Benzyloxyphenylsulfonyl) phenoxy] ethoxy) -ethane

  3- [4- (4-Methoxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester, 3- [4- (4-ethoxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester, 3- [4- (4-n-propoxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester, 3- [4- (4- Isopropoxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester, 3- [4- (4-n-butoxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-hydroxyphenyl) Sulfonyl) Phenyl ester, 3- [4- (4-t-butoxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester, 3- [4- (4-allyloxyphenylsulfonyl) phenoxy] Carbonylpropionic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester, 3- [4- (4-benzyloxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester

  5- [4- (4-Methoxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester, 5- [4- (4-ethoxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester, 5- [4- (4-n-propoxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester, 5- [4- (4- Isopropoxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester, 5- [4- (4-n-butoxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-hydroxyphenyl) Sulfonyl) phenyl ester Ter, 5- [4- (4-t-butoxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester, 5- [4- (4-allyloxyphenylsulfonyl) phenoxy] carbonyl Examples include pentanoic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester and 5- [4- (4-benzyloxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-hydroxyphenylsulfonyl) phenyl ester.

  Among them, 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2 ′-[4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether, 1- (2- [4- (4-hydroxyphenyl) Sulfonyl) phenoxy] ethoxy) -2- (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy)- 2- (2- [4- (4-Allyloxyphenylsulfonyl) phenoxy] ethoxy) -ethane is preferred.

Specific examples of typical compounds in the case where n = 1 in the diphenylsulfone derivative (II) or n2 = 1 in the diphenylsulfone derivative (III) include the following compounds, but are not limited thereto.
4- (2- [4- (4-Hydroxyphenylsulfonyl) phenoxy] ethoxy) -4 '-(2- [4- (4-methoxyphenylsulfonyl) phenoxy] ethoxy) diphenylsulfone, 4- (3- [4 -(4-Hydroxyphenylsulfonyl) phenoxy] propoxy) -4 '-(3- [4- (4-methoxyphenylsulfonyl) phenoxy] propoxy) diphenylsulfone, 4- (4- [4- (4-hydroxyphenylsulfonyl) ) Phenoxy] butoxy) -4 '-(4- [4- (4-methoxyphenylsulfonyl) phenoxy] butoxy) diphenylsulfone, 4- (5- [4- (4-hydroxyphenylsulfonyl) phenoxy] pentoxy) -4 '-(5- [4- (4-Methoxyphenylsulfonyl) phenoxy] pentoxy) diphenylsulfone, 4- (6- [4- (4-hydroxyphenylsulfonyl) fur NOXY] hexoxy) -4 '-(6- [4- (4-methoxyphenylsulfonyl) phenoxy] hexoxy) diphenylsulfone, 4- (7- [4- (4-hydroxyphenylsulfonyl) phenoxy] heptoxy) -4' -(7- [4- (4-Methoxyphenylsulfonyl) phenoxy] heptoxy) diphenylsulfone, 4- (8- [4- (4-hydroxyphenylsulfonyl) phenoxy] octoxy) -4 '-(8- [4- (4-Methoxyphenylsulfonyl) phenoxy] octoxy) diphenylsulfone

  4- (2- [4- (4-Hydroxyphenylsulfonyl) phenoxy] ethoxy) -4 '-(2- [4- (4-ethoxyphenylsulfonyl) phenoxy] ethoxy) diphenylsulfone, 4- (3- [4 -(4-Hydroxyphenylsulfonyl) phenoxy] propoxy) -4 '-(3- [4- (4-ethoxyphenylsulfonyl) phenoxy] propoxy) diphenylsulfone, 4- (4- [4- (4-hydroxyphenylsulfonyl) ) Phenoxy] butoxy) -4 '-(4- [4- (4-ethoxyphenylsulfonyl) phenoxy] butoxy) diphenylsulfone, 4- (5- [4- (4-hydroxyphenylsulfonyl) phenoxy] pentoxy) -4 '-(5- [4- (4-Ethoxyphenylsulfonyl) phenoxy] pentoxy) diphenylsulfone, 4- (6- [4- (4-hydroxyphenylsulfonate) ) Phenoxy] hexoxy) -4 '-(6- [4- (4-ethoxyphenylsulfonyl) phenoxy] hexoxy) diphenylsulfone, 4- (7- [4- (4-hydroxyphenylsulfonyl) phenoxy] heptoxy) -4 '-(7- [4- (4-Ethoxyphenylsulfonyl) phenoxy] heptoxy) diphenylsulfone, 4- (8- [4- (4-hydroxyphenylsulfonyl) phenoxy] octoxy) -4'-(8- [4 -(4-Ethoxyphenylsulfonyl) phenoxy] octoxy) diphenylsulfone

  4- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -4 '-(2- [4- (4-n-propoxyphenylsulfonyl) phenoxy] ethoxy) diphenylsulfone, 4- (3- [4- (4-Hydroxyphenylsulfonyl) phenoxy] propoxy) -4 ′-(3- [4- (4-n-propoxyphenylsulfonyl) phenoxy] propoxy) diphenylsulfone, 4- (4- [4- (4 -Hydroxyphenylsulfonyl) phenoxy] butoxy) -4 '-(4- [4- (4-n-propoxyphenylsulfonyl) phenoxy] butoxy) diphenylsulfone, 4- (5- [4- (4-hydroxyphenylsulfonyl) Phenoxy] pentoxy) -4 '-(5- [4- (4-n-propoxyphenylsulfonyl) phenoxy] pentoxy) diphenylsulfone, 4- (6- [4- (4-hydroxy) Phenylsulfonyl) phenoxy] hexoxy) -4 ′-(6- [4- (4-n-propoxyphenylsulfonyl) phenoxy] hexoxy) diphenylsulfone, 4- (7- [4- (4-hydroxyphenylsulfonyl) phenoxy] Heptoxy) -4 '-(7- [4- (4-n-propoxyphenylsulfonyl) phenoxy] heptoxy) diphenylsulfone, 4- (8- [4- (4-hydroxyphenylsulfonyl) phenoxy] octoxy) -4' -(8- [4- (4-n-propoxyphenylsulfonyl) phenoxy] octoxy) diphenylsulfone

  4- (3- [4- (4-hydroxyphenylsulfonyl) phenoxy] propoxy) -4 '-(3- [4- (4-isopropoxyphenylsulfonyl) phenoxy] propoxy) diphenylsulfone, 4- (4- [ 4- (4-hydroxyphenylsulfonyl) phenoxy] butoxy) -4 '-(4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butoxy) diphenylsulfone, 4- (5- [4- (4-hydroxy Phenylsulfonyl) phenoxy] pentoxy) -4 ′-(5- [4- (4-isopropoxyphenylsulfonyl) phenoxy] pentoxy) diphenylsulfone, 4- (6- [4- (4-hydroxyphenylsulfonyl) phenoxy] hexoxy ) -4 '-(6- [4- (4-Isopropoxyphenylsulfonyl) phenoxy] hexoxy) diphenylsulfone, 4- (7- [4- (4 -Hydroxyphenylsulfonyl) phenoxy] heptoxy) -4 '-(7- [4- (4-isopropoxyphenylsulfonyl) phenoxy] heptoxy) diphenylsulfone, 4- (8- [4- (4-hydroxyphenylsulfonyl) phenoxy ] Octoxy) -4 '-(8- [4- (4-isopropoxyphenylsulfonyl) phenoxy] octoxy) diphenylsulfone

  4- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -4 '-(2- [4- (4-n-butoxyphenylsulfonyl) phenoxy] ethoxy) diphenylsulfone, 4- (3- [4- (4-Hydroxyphenylsulfonyl) phenoxy] propoxy) -4 '-(3- [4- (4-n-butoxyphenylsulfonyl) phenoxy] propoxy) diphenylsulfone, 4- (4- [4- (4 -Hydroxyphenylsulfonyl) phenoxy] butoxy) -4 '-(4- [4- (4-n-butoxyphenylsulfonyl) phenoxy] butoxy) diphenylsulfone, 4- (5- [4- (4-hydroxyphenylsulfonyl) Phenoxy] pentoxy) -4 '-(5- [4- (4-n-butoxyphenylsulfonyl) phenoxy] pentoxy) diphenylsulfone, 4- (6- [4- (4-hydroxypheny) Sulfonyl) phenoxy] hexoxy) -4 ′-(6- [4- (4-n-butoxyphenylsulfonyl) phenoxy] hexoxy) diphenylsulfone, 4- (7- [4- (4-hydroxyphenylsulfonyl) phenoxy] heptoxy ) -4 '-(7- [4- (4-n-butoxyphenylsulfonyl) phenoxy] heptoxy) diphenylsulfone, 4- (8- [4- (4-hydroxyphenylsulfonyl) phenoxy] octoxy) -4'- (8- [4- (4-n-Butoxyphenylsulfonyl) phenoxy] octoxy) diphenylsulfone

  4- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -4 '-(2- [4- (4-isobutoxyphenylsulfonyl) phenoxy] ethoxy) diphenylsulfone, 4- (3- [ 4- (4-hydroxyphenylsulfonyl) phenoxy] propoxy) -4 '-(3- [4- (4-isobutoxyphenylsulfonyl) phenoxy] propoxy) diphenyl sulfone, 4- (4- [4- (4-hydroxy Phenylsulfonyl) phenoxy] butoxy) -4 ′-(4- [4- (4-isobutoxyphenylsulfonyl) phenoxy] butoxy) diphenylsulfone, 4- (5- [4- (4-hydroxyphenylsulfonyl) phenoxy] pentoxy ) -4 '-(5- [4- (4-Isobutoxyphenylsulfonyl) phenoxy] pentoxy) diphenyl sulfone, 4- (6- [4- (4-hydroxy) Enylsulfonyl) phenoxy] hexoxy) -4 '-(6- [4- (4-isobutoxyphenylsulfonyl) phenoxy] hexoxy) diphenylsulfone, 4- (7- [4- (4-hydroxyphenylsulfonyl) phenoxy] heptoxy ) -4 '-(7- [4- (4-Isobutoxyphenylsulfonyl) phenoxy] heptoxy) diphenylsulfone, 4- (8- [4- (4-hydroxyphenylsulfonyl) phenoxy] octoxy) -4'-( 8- [4- (4-Isobutoxyphenylsulfonyl) phenoxy] octoxy) diphenylsulfone

  4- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -4 '-(2- [4- (4-t-butoxyphenylsulfonyl) phenoxy] ethoxy) diphenylsulfone, 4- (3- [4- (4-Hydroxyphenylsulfonyl) phenoxy] propoxy) -4 ′-(3- [4- (4-t-butoxyphenylsulfonyl) phenoxy] propoxy) diphenylsulfone, 4- (4- [4- (4 -Hydroxyphenylsulfonyl) phenoxy] butoxy) -4 '-(4- [4- (4-t-butoxyphenylsulfonyl) phenoxy] butoxy) diphenylsulfone, 4- (5- [4- (4-hydroxyphenylsulfonyl) Phenoxy] pentoxy) -4 '-(5- [4- (4-t-butoxyphenylsulfonyl) phenoxy] pentoxy) diphenylsulfone, 4- (6- [4- (4-hydroxypheny) Sulfonyl) phenoxy] hexoxy) -4 '-(6- [4- (4-t-butoxyphenylsulfonyl) phenoxy] hexoxy) diphenylsulfone, 4- (7- [4- (4-hydroxyphenylsulfonyl) phenoxy] heptoxy ) -4 '-(7- [4- (4-t-butoxyphenylsulfonyl) phenoxy] heptoxy) diphenylsulfone, 4- (8- [4- (4-hydroxyphenylsulfonyl) phenoxy] octoxy) -4'- (8- [4- (4-t-Butoxyphenylsulfonyl) phenoxy] octoxy) diphenylsulfone

  4- (2- [4- (4-Hydroxyphenylsulfonyl) phenoxy] ethoxy) -4 '-(2- [4- (4-allyloxyphenylsulfonyl) phenoxy] ethoxy) diphenylsulfone, 4- (3- [ 4- (4-hydroxyphenylsulfonyl) phenoxy] propoxy) -4 '-(3- [4- (4-allyloxyphenylsulfonyl) phenoxy] propoxy) diphenyl sulfone, 4- (4- [4- (4-hydroxy Phenylsulfonyl) phenoxy] butoxy) -4 ′-(4- [4- (4-allyloxyphenylsulfonyl) phenoxy] butoxy) diphenylsulfone, 4- (5- [4- (4-hydroxyphenylsulfonyl) phenoxy] pentoxy ) -4 '-(5- [4- (4-allyloxyphenylsulfonyl) phenoxy] pentoxy) diphenyl sulfone, 4- (6- [4- (4-hydroxy) Enylsulfonyl) phenoxy] hexoxy) -4 '-(6- [4- (4-allyloxyphenylsulfonyl) phenoxy] hexoxy) diphenylsulfone, 4- (7- [4- (4-hydroxyphenylsulfonyl) phenoxy] heptoxy ) -4 ′-(7- [4- (4-allyloxyphenylsulfonyl) phenoxy] heptoxy) diphenylsulfone, 4- (8- [4- (4-hydroxyphenylsulfonyl) phenoxy] octoxy) -4 ′-( 8- [4- (4-Allyloxyphenylsulfonyl) phenoxy] octoxy) diphenylsulfone

  4- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -4 '-(2- [4- (4-benzyloxyphenylsulfonyl) phenoxy] ethoxy) diphenylsulfone, 4- (3- [ 4- (4-hydroxyphenylsulfonyl) phenoxy] propoxy) -4 '-(3- [4- (4-benzyloxyphenylsulfonyl) phenoxy] propoxy) diphenylsulfone, 4- (4- [4- (4-hydroxy Phenylsulfonyl) phenoxy] butoxy) -4 ′-(4- [4- (4-benzyloxyphenylsulfonyl) phenoxy] butoxy) diphenylsulfone, 4- (5- [4- (4-hydroxyphenylsulfonyl) phenoxy] pentoxy ) -4 '-(5- [4- (4-benzyloxyphenylsulfonyl) phenoxy] pentoxy) diphenyl sulfone, 4- (6- [4- (4-H Roxyphenylsulfonyl) phenoxy] hexoxy) -4 '-(6- [4- (4-benzyloxyphenylsulfonyl) phenoxy] hexoxy) diphenylsulfone, 4- (7- [4- (4-hydroxyphenylsulfonyl) phenoxy] Heptoxy) -4 '-(7- [4- (4-benzyloxyphenylsulfonyl) phenoxy] heptoxy) diphenylsulfone, 4- (8- [4- (4-hydroxyphenylsulfonyl) phenoxy] octoxy) -4'- (8- [4- (4-Benzyloxyphenylsulfonyl) phenoxy] octoxy) diphenylsulfone

  4- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -4 '-(2- (2- [4- (4-methoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) Diphenylsulfone, 4- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -4 '-(2- (2- [4- (4-ethoxyphenylsulfonyl) phenoxy] ethoxy) ) Ethoxy) diphenylsulfone, 4- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -4 '-(2- (2- [4- (4-n-propoxyphenyl) Sulfonyl) phenoxy] ethoxy) ethoxy) diphenylsulfone, 4- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -4 '-(2- (2- [4-- 4-Isopropoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) diphenylsulfone, 4- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -4 '-(2- (2- [4- (4-n-Butoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) diphenylsulfone, 4- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -4 '-( 2- (2- [4- (4-Isobutoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) diphenylsulfone, 4- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy)- 4 ′-(2- (2- [4- (4-tert-butoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) diphenylsulfone, 4- (2- 2- [4- (4-Hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -4 ′-(2- (2- [4- (4-allyloxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) diphenylsulfone, 4- (2- (2- [4- (4-Hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -4 ′-(2- (2- [4- (4-benzyloxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) diphenyl Sulfone

  4- (2- (2- (2- [2- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -4 '-(2- (2- (2- [4- (4-methoxyphenyl) Sulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) diphenyl sulfone, 4- (2- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -4 '-(2- ( 2- (2- [4- (4-Ethoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) diphenylsulfone, 4- (2- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ) Ethoxy) ethoxy) -4 '-(2- (2- (2- [4- (4-n-propoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) diphenylsulfone, 4- (2- (2- ( 2- [ -(4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -4 '-(2- (2- (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) diphenylsulfone 4- (2- (2- (2- [2- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -4 '-(2- (2- (2- [4- (4-n -Butoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) diphenylsulfone, 4- (2- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -4 '-( 2- (2- (2- [4- (4-Isobutoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) diphenyl sulfone, 4- (2- (2- (2- [4- [4- (4-hydro Siphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -4 '-(2- (2- (2- [4- (4-tert-butoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) ethoxy) diphenylsulfone, 4- (2- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -4 '-(2- (2- (2- [4- (4-allyloxyphenylsulfonyl) ) Phenoxy] ethoxy) ethoxy) ethoxy) diphenylsulfone, 4- (2- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -4 '-(2- (2 -(2- [4- (4-Benzyloxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) diphenylsulfone and the like.

  Among them, 4- (4- [4- (4-hydroxyphenylsulfonyl) phenoxy] butoxy) -4 ′-(4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butoxy) diphenylsulfone, 4- (2 -(2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -4 '-(2- (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) diphenylsulfone, 4- (2- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -4 '-(2- (2- (2- [4- (4-isopropoxy) Phenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) diphenylsulfone, 4- (2- (2- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) Ethoxy) -4 '- (2- (2- (2- [4- (4-allyl-oxy) phenoxy] ethoxy) ethoxy) ethoxy) diphenyl sulfone are preferred.

In the diphenylsulfone derivative (IV), specific examples of typical compounds in the case where n3 = 0 include the following compounds, but are not limited thereto.
2,2′-bis [4- (4-methoxyphenylsulfonyl) phenoxy] -diethyl ether, 2,2′-bis [4- (4-ethoxyphenylsulfonyl) phenoxy] -diethyl ether, 2,2′-bis [4- (4-n-propoxyphenylsulfonyl) phenoxy] -diethyl ether, 2,2′-bis [4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether, 2,2′-bis [4- (4-n-Butoxyphenylsulfonyl) phenoxy] -diethyl ether, 2,2′-bis [4- (4-t-butoxyphenylsulfonyl) phenoxy] -diethyl ether, 2,2′-bis [4- (4 -Allyloxyphenylsulfonyl) phenoxy] -diethyl ether, 2,2′-bis [4- (4-benzyloxyphenylsulfonyl) pheno Xyl] -diethyl ether

  1,2-bis (2- [4- (4-methoxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1,2-bis (2- [4- (4-ethoxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1,2-bis (2- [4- (4-n-propoxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1,2-bis (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) -Ethane, 1,2-bis (2- [4- (4-n-butoxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1,2-bis (2- [4- (4-tert-butoxyphenylsulfonyl) Phenoxy] ethoxy) -ethane, 1,2-bis (2- [4- (4-allyloxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1,2-bis (2- [4- 4-benzyloxy-phenylsulfonyl) phenoxy] ethoxy) - ethane

  3- [4- (4-Methoxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-methoxyphenylsulfonyl) phenyl ester, 3- [4- (4-ethoxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-Ethoxyphenylsulfonyl) phenyl ester, 3- [4- (4-n-propoxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-n-propoxyphenylsulfonyl) phenyl ester, 3- [4- ( 4-Isopropoxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-isopropoxyphenylsulfonyl) phenyl ester, 3- [4- (4-n-butoxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4 -N-Butoxyphenylsulfonyl) Nyl ester, 3- [4- (4-tert-butoxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-tert-butoxyphenylsulfonyl) phenyl ester, 3- [4- (4-allyloxyphenylsulfonyl) phenoxy ] Carbonylpropionic acid-4- (4-allyloxyphenylsulfonyl) phenyl ester, 3- [4- (4-benzyloxyphenylsulfonyl) phenoxy] carbonylpropionic acid-4- (4-n-benzyloxyphenylsulfonyl) phenyl ester

  5- [4- (4-Methoxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-methoxyphenylsulfonyl) phenyl ester, 5- [4- (4-ethoxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-Ethoxyphenylsulfonyl) phenyl ester, 5- [4- (4-n-propoxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-n-propoxyphenylsulfonyl) phenyl ester, 5- [4- ( 4-Isopropoxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-isopropoxyphenylsulfonyl) phenyl ester, 5- [4- (4-n-butoxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4 -N-Butoxyphenylsulfonyl) phenyl Ester, 5- [4- (4-t-butoxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-t-butoxyphenylsulfonyl) phenyl ester, 5- [4- (4-allyloxyphenylsulfonyl) phenoxy ] Carbonylpentanoic acid-4- (4-allyloxyphenylsulfonyl) phenyl ester, 5- [4- (4-benzyloxyphenylsulfonyl) phenoxy] carbonylpentanoic acid-4- (4-benzyloxyphenylsulfonyl) phenyl ester, etc. Is mentioned.

  Among them, 2,2′-bis [4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether, 1,2-bis (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) -ethane 1,2-bis (2- [4- (4-allyloxyphenylsulfonyl) phenoxy] ethoxy) -ethane is preferred.

In the diphenylsulfone derivative (IV), specific examples of typical compounds in the case of n3 = 1 include the following compounds, but are not limited thereto.
4,4′-bis (2- [4- (4-methoxyphenylsulfonyl) phenoxy] ethoxy) -diphenylsulfone, 4,4′-bis (3- [4- (4-methoxyphenylsulfonyl) phenoxy] propoxy) -Diphenylsulfone, 4,4'-bis (4- [4- (4-methoxyphenylsulfonyl) phenoxy] butoxy) -diphenylsulfone, 4,4'-bis (5- [4- (4-methoxyphenylsulfonyl) Phenoxy] pentoxy) -diphenylsulfone, 4,4′-bis (6- [4- (4-methoxyphenylsulfonyl) phenoxy] hexoxy) -diphenylsulfone, 4,4′-bis (7- [4- (4- Methoxyphenylsulfonyl) phenoxy] heptoxy) -diphenylsulfone, 4,4′-bis (8- [4- (4-methoxyphene) Nylsulfonyl) phenoxy] octoxy) -diphenylsulfone

  4,4′-bis (2- [4- (4-ethoxyphenylsulfonyl) phenoxy] ethoxy) -diphenylsulfone, 4,4′-bis (3- [4- (4-ethoxyphenylsulfonyl) phenoxy] propoxy) -Diphenylsulfone, 4,4'-bis (4- [4- (4-ethoxyphenylsulfonyl) phenoxy] butoxy) -diphenylsulfone, 4,4'-bis (5- [4- (4-ethoxyphenylsulfonyl) Phenoxy] pentoxy) -diphenylsulfone, 4,4′-bis (6- [4- (4-ethoxyphenylsulfonyl) phenoxy] hexoxy) -diphenylsulfone, 4,4′-bis (7- [4- (4- Ethoxyphenylsulfonyl) phenoxy] heptoxy) -diphenylsulfone, 4,4′-bis (8- [4- (4-e Carboxymethyl) phenoxy] Okutakishi) - diphenylsulfone

  4,4′-bis (2- [4- (4-n-propoxyphenylsulfonyl) phenoxy] ethoxy) -diphenylsulfone, 4,4′-bis (3- [4- (4-n-propoxyphenylsulfonyl) Phenoxy] propoxy) -diphenylsulfone, 4,4′-bis (4- [4- (4-n-propoxyphenylsulfonyl) phenoxy] butoxy) -diphenylsulfone, 4,4′-bis (5- [4- ( 4-n-propoxyphenylsulfonyl) phenoxy] pentoxy) -diphenylsulfone, 4,4′-bis (6- [4- (4-n-propoxyphenylsulfonyl) phenoxy] hexoxy) -diphenylsulfone, 4,4′- Bis (7- [4- (4-n-propoxyphenylsulfonyl) phenoxy] heptoxy) -diphenylsulfone 4,4'-bis (8- [4- (4-n- propoxyphenyl) phenoxy] Okutakishi) - diphenylsulfone

  4,4′-bis (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) -diphenylsulfone, 4,4′-bis (3- [4- (4-isopropoxyphenylsulfonyl) phenoxy] Propoxy) -diphenylsulfone, 4,4′-bis (4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butoxy) -diphenylsulfone, 4,4′-bis (5- [4- (4-iso Propoxyphenylsulfonyl) phenoxy] pentoxy) -diphenylsulfone, 4,4′-bis (6- [4- (4-isopropoxyphenylsulfonyl) phenoxy] hexoxy) -diphenylsulfone, 4,4′-bis (7- [ 4- (4-Isopropoxyphenylsulfonyl) phenoxy] heptoxy) -diphenylsulfone 4,4'-bis (8- [4- (4-isopropoxyphenyl sulfonyl) phenoxy] Okutakishi) - diphenylsulfone

  4,4′-bis (2- [4- (4-n-butoxyphenylsulfonyl) phenoxy] ethoxy) -diphenylsulfone, 4,4′-bis (3- [4- (4-n-butoxyphenylsulfonyl) Phenoxy] propoxy) -diphenylsulfone, 4,4′-bis (4- [4- (4-n-butoxyphenylsulfonyl) phenoxy] butoxy) -diphenylsulfone, 4,4′-bis (5- [4- ( 4-n-butoxyphenylsulfonyl) phenoxy] pentoxy) -diphenylsulfone, 4,4′-bis (6- [4- (4-n-butoxyphenylsulfonyl) phenoxy] hexoxy) -diphenylsulfone, 4,4′- Bis (7- [4- (4-n-butoxyphenylsulfonyl) phenoxy] heptoxy) -diphenylsulfone, 4,4′-bis (8 [4- (4-n- butoxy) phenoxy] Okutakishi) - diphenylsulfone

  4,4′-bis (2- [4- (4-isobutoxyphenylsulfonyl) phenoxy] ethoxy) -diphenylsulfone, 4,4′-bis (3- [4- (4-isobutoxyphenylsulfonyl) phenoxy] Propoxy) -diphenylsulfone, 4,4′-bis (4- [4- (4-isobutoxyphenylsulfonyl) phenoxy] butoxy) -diphenylsulfone, 4,4′-bis (5- [4- (4-iso Butoxyphenylsulfonyl) phenoxy] pentoxy) -diphenylsulfone, 4,4′-bis (6- [4- (4-isobutoxyphenylsulfonyl) phenoxy] hexoxy) -diphenylsulfone, 4,4′-bis (7- [ 4- (4-Isobutoxyphenylsulfonyl) phenoxy] heptoxy) -diphenylsulfone, 4,4′- Scan (8- [4- (4-isobutoxyphenyl) phenoxy] Okutakishi) - diphenylsulfone

  4,4′-bis (2- [4- (4-tert-butoxyphenylsulfonyl) phenoxy] ethoxy) -diphenylsulfone, 4,4′-bis (3- [4- (4-tert-butoxyphenylsulfonyl) Phenoxy] propoxy) -diphenylsulfone, 4,4′-bis (4- [4- (4-tert-butoxyphenylsulfonyl) phenoxy] butoxy) -diphenylsulfone, 4,4′-bis (5- [4- ( 4-tert-butoxyphenylsulfonyl) phenoxy] pentoxy) -diphenylsulfone, 4,4′-bis (6- [4- (4-tert-butoxyphenylsulfonyl) phenoxy] hexoxy) -diphenylsulfone, 4,4′- Bis (7- [4- (4-tert-butoxyphenylsulfonyl) phenoxy] heptoxy) -diphenylsulfone, 4,4 - bis (8- [4- (4-tert- butoxyphenyl) phenoxy] Okutakishi) - diphenylsulfone

  4,4′-bis (2- [4- (4-allyloxyphenylsulfonyl) phenoxy] ethoxy) -diphenylsulfone, 4,4′-bis (3- [4- (4-allyloxyphenylsulfonyl) phenoxy] Propoxy) -diphenylsulfone, 4,4′-bis (4- [4- (4-allyloxyphenylsulfonyl) phenoxy] butoxy) -diphenylsulfone, 4,4′-bis (5- [4- (4-allyl) Oxyphenylsulfonyl) phenoxy] pentoxy) -diphenylsulfone, 4,4′-bis (6- [4- (4-allyloxyphenylsulfonyl) phenoxy] hexoxy) -diphenylsulfone, 4,4′-bis (7- [ 4- (4-allyloxyphenylsulfonyl) phenoxy] heptoxy) -diphenylsulfone, 4,4′- Scan (8- [4- (4-allyl-oxy) phenoxy] Okutakishi) - diphenylsulfone

  4,4′-bis (2- [4- (4-benzyloxyphenylsulfonyl) phenoxy] ethoxy) -diphenylsulfone, 4,4′-bis (3- [4- (4-benzyloxyphenylsulfonyl) phenoxy] Propoxy) -diphenylsulfone, 4,4′-bis (4- [4- (4-benzyloxyphenylsulfonyl) phenoxy] butoxy) -diphenylsulfone, 4,4′-bis (5- [4- (4-benzyl) Oxyphenylsulfonyl) phenoxy] pentoxy) -diphenylsulfone, 4,4′-bis (6- [4- (4-benzyloxyphenylsulfonyl) phenoxy] hexoxy) -diphenylsulfone, 4,4′-bis (7- [ 4- (4-Benzyloxyphenylsulfonyl) phenoxy] heptoxy) -diphenylsulfone 4,4'-bis (8- [4- (4-benzyloxy) phenoxy] Okutakishi) - diphenylsulfone

  4,4′-bis (2- (2- [4- (4-methoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -diphenylsulfone, 4,4′-bis (2- (2- [4- (4- Ethoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -diphenylsulfone, 4,4′-bis (2- (2- [4- (4-n-propoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -diphenylsulfone, 4, 4'-bis (2- (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -diphenylsulfone, 4,4'-bis (2- (2- [4- (4-n -Butoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -diphenylsulfone, 4,4'-bis (2- (2- [4- (4-tert-butoxyphenylsulfonyl) ) Phenoxy] ethoxy) ethoxy) -diphenylsulfone, 4,4′-bis (2- (2- [4- (4-allyloxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -diphenylsulfone, 4,4′-bis (2- (2- [4- (4-Benzyloxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) -diphenylsulfone

  4,4′-bis (2- (2- (2- [4- (4-methoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -diphenylsulfone, 4,4′-bis (2- (2- ( 2- [4- (4-Ethoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -diphenylsulfone, 4,4′-bis (2- (2- (2- [4- (4-n-propoxyphenylsulfonyl) ) Phenoxy] ethoxy) ethoxy) ethoxy) -diphenylsulfone, 4,4′-bis (2- (2- (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -diphenylsulfone 4,4′-bis (2- (2- (2- [4- (4-n-butoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -diphenylsulfone, 4,4′-bis (2- (2- (2- [4- (4-t-butoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -diphenylsulfone, 4,4′-bis (2- (2 -(2- [4- (4-Allyloxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -diphenylsulfone, 4,4'-bis (2- (2- (2- [4- (4-benzyloxy) Phenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -diphenylsulfone and the like.

  Among them, 4,4′-bis (4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butoxy) -diphenylsulfone, 4,4′-bis (2- (2- [4- (4-isopropoxy) Phenylsulfonyl) phenoxy] ethoxy) ethoxy) -diphenylsulfone, 4,4′-bis (2- (2- (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -diphenylsulfone 4,4′-bis (2- (2- (2- [4- (4-allyloxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy) -diphenylsulfone is preferred.

The compound of diphenylsulfone derivative (I) and the compound of n2 = 0 of diphenylsulfone derivative (III) are, for example, 4-alkyloxy-4′-hydroxydiphenylsulfone or 4-alkenyl in the presence of alkali metal or alkaline earth metal. Synthesis such as reacting a compound obtained by reacting oxy-4′-hydroxydiphenylsulfone with bis (chloroalkyl) ether or bis (chloroalkoxy) alkane with an alkali salt of 4,4′-dihydroxydiphenylsulfone Easily obtained by the method.
As a solvent used for the reaction and purification, an appropriate organic solvent which can dissolve the raw materials and reaction products and is inert to the reaction, for example, water, alcohol, halogen, amide, sulfoxide, aromatic hydrocarbon Ketone-based, ether-based, and nitrile-based solvents are used, and amide-based and sulfoxide-based solvents are particularly preferable.

The reaction temperature is usually 0 to 150 ° C, and 60 to 120 ° C is particularly preferable. The reaction time is usually several hours to several tens of hours, with 2 to 10 hours being preferred.
After completion of the reaction, the above solvent is added to the reaction solution and washed with an aqueous sodium hydrogen carbonate solution, etc., and then an aqueous alkali solution is added to form an alkali salt, which is extracted into an aqueous layer. The yield can be obtained. Further, recrystallization may be performed as necessary.

Similarly, the compound of n1 = 1 of the diphenylsulfone derivative (II) and the compound of n2 = 1 of the diphenylsulfone derivative (III) are prepared by using the compound of n2 = 0 obtained by the above synthesis method as a raw material. Reaction of a compound obtained by reacting with a dihalogenoalkane, bis (chloroalkyl) ether, or bis (chloroalkoxy) alkane in the presence of a metal or alkaline earth metal with an alkali salt of 4,4′-dihydroxydiphenylsulfone It can be easily obtained by a synthesis method such as
A compound having n1 = 2 or more of diphenylsulfone derivative (II) and a compound having n2 = 2 or more of diphenylsulfone derivative (III) can be produced by the same method as described above.

  The compound of n3 = 0 of the diphenylsulfone derivative (IV) is, for example, 2 equivalents of 4-alkyloxy-4′-hydroxydiphenylsulfone or 4-alkenyloxy-4′-hydroxy in the presence of alkali metal or alkaline earth metal. It can be easily obtained by a synthesis method such as reacting diphenylsulfone with 1 equivalent of bis (chloroalkyl) ether or bis (chloroalkoxy) alkane. As a solvent used for the reaction and purification, an appropriate organic solvent which can dissolve the raw materials and reaction products and is inert to the reaction, for example, water, alcohol, halogen, amide, sulfoxide, aromatic hydrocarbon Ketone-based, ether-based, and nitrile-based solvents are used, and amide-based and sulfoxide-based solvents are particularly preferable.

The reaction temperature is usually 0 to 150 ° C, and 60 to 120 ° C is particularly preferable. The reaction time is usually several hours to several tens of hours, with 2 to 10 hours being preferred.
After completion of the reaction, the solvent can be added to the reaction solution, washed with an aqueous sodium hydroxide solution and the like, and the organic layer can be concentrated to obtain a high yield. Further, recrystallization may be performed as necessary.

The compound of n3 = 1 of the diphenylsulfone derivative (IV) is prepared by using, for example, a compound of n2 = 0 of the diphenylsulfone derivative (III) as a raw material, and dihalogenoalkane, bis (chloro Alkyl) ether or a compound obtained by reacting with bis (chloroalkoxy) alkane is converted to 4-alkyloxy-4′-hydroxydiphenylsulfone or 4-alkenyloxy-4′-hydroxydiphenylsulfone 4,4′-dihydroxy. It can be easily obtained by a synthesis method such as reacting with an alkali salt of diphenylsulfone.
The compound of n3 = 2 or more of the diphenylsulfone derivative (IV) can be produced by the same method as described above.

(Thermal recording material)
The heat-sensitive recording material of the present invention comprises, for example, a heat-sensitive recording layer containing a colorless or light-colored basic leuco dye and a developer for coloring the basic leuco dye on a support. .
In the present invention, as the developer, the diphenylsulfone derivative (III) may be used alone, or if it contains at least one diphenylsulfone derivative (III), it is used in combination with other diphenylsulfone derivatives. Also good.
Examples of the diphenylsulfone derivative (III) include 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2 ′-[4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether, 1- (2- [ 4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -2- (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 1- (2- [4- (4-hydroxyphenyl) Sulfonyl) phenoxy] ethoxy) -2- (2- [4- (4-allyloxyphenylsulfonyl) phenoxy] ethoxy) -ethane is preferably used.

  As another diphenylsulfone derivative to be combined with the diphenylsulfone derivative (III), at least one diphenylsulfone derivative (IV) is suitable. Specifically, 2,2′-bis [4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether, 1,2-bis (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy ) -Ethane, 1,2-bis (2- [4- (4-allyloxyphenylsulfonyl) phenoxy] ethoxy) -ethane, 4,4′-bis [4- (4-isopropoxyphenylsulfonyl) phenoxy] butoxy -Diphenylsulfone, 4,4'-bis (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy-diphenylsulfone, 4,4'-bis (2- (2- [4- (4 -Isopropoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy) ethoxy-diphenylsulfone, 4,4'-bis (2- (2- [4- 4-allyl-oxy) phenoxy] ethoxy) ethoxy) ethoxy - diphenyl sulfone are preferred. For example, when 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2 ′-[4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether is used as the diphenylsulfone derivative (III), 2, From 2′-bis [4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether and 4,4′-bis (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy-diphenylsulfone It is preferable to combine with at least one selected. Thereby, melting | fusing point fall occurs and a standup sensitivity can be improved further. In addition, it is possible to more reliably maintain a good plasticizer resistance state. The content of the diphenylsulfone derivative (IV) is preferably 0.01 to 10% by weight, more preferably 0.05 to 10% by weight, most preferably 0.05, based on the total weight of the diphenylsulfone derivative. ~ 5% by weight.

  Further, as a method of combining the diphenylsulfone derivative (III) and the diphenylsulfone derivative (IV), a method of mixing each compound with a powder and preparing a dispersion, a method of mixing a dispersion of each compound, or diphenyl Examples of the method for synthesizing the sulfone derivative (III) include a method in which the production conditions are partially changed to obtain a mixture as a powder and then a dispersion.

  Further, the compound represented by the diphenylsulfone derivative (II) may be used in combination with the compound represented by the diphenylsulfone derivative (I). Thereby, not only the storage stability of the image in the plasticizer resistance test and the storage stability of the background portion in the heat resistance test, but also the storage stability of the image in the heat resistance test can be improved. Although the content ratio in the case of using in combination is arbitrary, it is preferable that the compound represented by diphenyl sulfone derivative (II) is 0.05 to 99 weight% with respect to the total weight of the diphenyl sulfone derivative. Further, it is particularly preferably 5 to 90% by weight, specifically 5 to 50% by weight.

  As a method of combining the compound represented by the diphenylsulfone derivative (II) and the compound represented by the diphenylsulfone derivative (I), a method of mixing each compound with a powder and then preparing a dispersion, Examples thereof include a method of mixing the dispersion.

In the present invention, a known color developer conventionally used in the field of pressure-sensitive or heat-sensitive recording paper can be used without particular limitation as long as it contains at least one diphenylsulfone derivative (III). it can.
Specifically, inorganic acidic substances such as activated clay, attapulgite, colloidal silica, aluminum silicate;
4,4′-isopropylidenediphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 4,4′-dihydroxydiphenyl sulfide, hydroquinone Monobenzyl ether, benzyl 4-hydroxybenzoate, 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4′-n- Propoxydiphenylsulfone, 4-hydroxy-4'-ethoxydiphenylsulfone, 4-hydroxybenzenesulfonanilide, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'-allyloxydiphenylsulfone, 4-hydroxy -4'- Tildiphenylsulfone, 4-hydroxyphenyl-4′-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4′-methylphenylsulfone, bis (4-hydroxyphenylthioethoxy) methane, 1,5-di (4- Hydroxyphenylthio) -3-oxapentane, butyl bis (p-hydroxyphenyl) acetate, methyl bis (p-hydroxyphenyl) acetate, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,4 -Bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, 1,3-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, di (4-hydroxy-3) -Methylphenyl) sulfide, 2,2'-thiobis (3-tert-octylphenol), 2,2'-thio Phenolic compounds such as bis (4-tert-octylphenol), a formalin condensate of 4-tert-butylphenol described in WO 2005/118526, and a diphenylsulfone cross-linking compound described in WO 97/16420;
4,4′-bis (3- (phenoxycarbonylamino) methylphenylureido) diphenylsulfone (trade name: UU manufactured by Chemipro Kasei Co., Ltd.), described in International Publication No. 02/081229 pamphlet, Japanese Patent Application Laid-Open No. 2002-301873 A compound (manufactured by Nippon Soda Co., Ltd., trade name: D-100), a compound described in Japanese Patent No. 3456679 and Japanese Patent No. 3612746, an aminobenzenesulfonamide derivative described in JP-A-8-59603, N, Thiourea compounds such as N′-di-m-chlorophenylthiourea;
p-chlorobenzoic acid, stearyl gallate, zinc bis [4- (n-octyloxycarbonylamino) salicylate] dihydrate, 4- [2- (p-methoxyphenoxy) ethyloxy] salicylic acid, 4- [3- Aromatic carboxylic acid compounds such as (p-tolylsulfonyl) propyloxy] salicylic acid and 5- [p- (2-p-methoxyphenoxyethoxy) cumyl] salicylic acid and zinc, magnesium of these aromatic carboxylic acid compounds, Salts with polyvalent metals such as aluminum, calcium, titanium, manganese, tin, nickel;
An antipyrine complex of zinc thiocyanate; a complex zinc salt of terephthalaldehyde acid and other aromatic carboxylic acid can be used. These developers can be used alone or in combination of two or more.

  In the present invention, as the basic dye to be included in the heat-sensitive recording layer, any colorless or light-colored basic dye known in the pressure-sensitive or heat-sensitive recording paper field can be used, and is not particularly limited. Preferred are leuco dyes such as triphenylmethane, fluoran, fluorene, and divinyl. Specific examples of suitable basic dyes are shown below. In addition, you may use these basic dyes individually or in combination of 2 or more types.

<Triphenylmethane leuco dye>
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide (also known as malachite green lactone), etc.

<Fluoran leuco dye>
3-diethylamino-6-methylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluorane, 3-diethylamino- 6-methyl-7-chlorofluorane, 3-diethylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane, 3-diethylamino-6-methyl-7- (o-chloroanilino) fluorane, 3- Diethylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-diethylamino-6-methyl-7- (o-fluoroanilino) fluorane, 3-diethylamino-6-methyl-7- (m-methylanilino) fluorane 3-diethylamino-6-methyl-7-n-octylanilinofluorane, 3-di Tilamino-6-methyl-7-n-octylaminofluorane, 3-diethylamino-6-methyl-7-benzylaminofluorane, 3-diethylamino-6-methyl-7-dibenzylaminofluorane, 3-diethylamino- 6-chloro-7-methylfluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-diethylamino-6-chloro-7-p-methylanilinofluorane, 3-diethylamino-6-ethoxy Ethyl-7-anilinofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7- (m-trifluoromethylanilino) fluorane, 3-diethylamino- 7- (o-chloroanilino) fluorane, 3-diethylamino-7- (p Chloroanilino) fluorane, 3-diethylamino-7- (o-fluoroanilino) fluorane, 3-diethylamino-benzo [a] fluorane, 3-diethylamino-benzo [c] fluorane, 3-dibutylamino-6-methyl-fluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7- (o, p-dimethylanilino) fluorane, 3-dibutylamino-6-methyl-7- ( o-chloroanilino) fluorane, 3-dibutylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-dibutylamino-6-methyl-7- (o-fluoroanilino) fluorane, 3-dibutylamino-6 -Methyl-7- (m-trifluoromethylanilino) fluorane, 3-dibutylamino- 6-methyl-chlorofluorane, 3-dibutylamino-6-ethoxyethyl-7-anilinofluorane, 3-dibutylamino-6-chloro-7-anilinofluorane, 3-dibutylamino-6-methyl- 7-p-methylanilinofluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-fluoroanilino) fluorane, 3-di-n-pentylamino-6 -Methyl-7-anilinofluorane, 3-di-n-pentylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-di-n-pentylamino-7- (m-trifluoromethylani Lino) fluorane, 3-di-n-pentylamino-6-chloro-7-anilinofluorane, 3-di-n-pentylamino-7- (p-chloroani) C) fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-propylamino) -6-methyl -7-anilinofluorane, 3- (N-methyl-N-cyclohexylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-cyclohexylamino) -6-methyl-7 -Anilinofluorane, 3- (N-ethyl-N-cyclohexylamino) -6-methyl-7- (p-chloroanilino) fluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7 -Anilinofluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamylamino) -6-chloro-7 Anilinofluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isobutylamino) -6-methyl-7- Anilinofluorane, 3- (N-ethyl-N-ethoxypropylamino) -6-methyl-7-anilinofluorane, 3-cyclohexylamino-6-chlorofluorane, 2- (4-oxahexyl)- 3-dimethylamino-6-methyl-7-anilinofluorane, 2- (4-oxahexyl) -3-diethylamino-6-methyl-7-anilinofluorane, 2- (4-oxahexyl) -3 -Dipropylamino-6-methyl-7-anilinofluorane, 2-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluorane, 2-methoxy-6 -P- (p-dimethylaminophenyl) aminoanilinofluorane, 2-chloro-3-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane, 2-chloro-6-p- ( p-dimethylaminophenyl) aminoanilinofluorane, 2-nitro-6-p- (p-diethylaminophenyl) aminoanilinofluorane, 2-amino-6-p- (p-diethylaminophenyl) aminoanilinofluor Oran, 2-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane, 2-phenyl-6-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane, 2-benzyl -6-p- (p-phenylaminophenyl) aminoanilinofluorane, 2-hydroxy-6-p- (p-pheny Aminophenyl) aminoanilinofluorane, 3-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluorane, 3-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane, 3-diethylamino-6-p- (p-dibutylaminophenyl) aminoanilinofluorane, 2,4-dimethyl-6-[(4-dimethylamino) anilino] -fluorane

<Fluorene leuco dye>
3,6,6′-tris (dimethylamino) spiro [fluorene-9,3′-phthalide], 3,6,6′-tris (diethylamino) spiro [fluorene-9,3′-phthalide]

<Divinyl leuco dye>
3,3-bis- [2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrabromophthalide, 3,3-bis- [2- (P-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrachlorophthalide, 3,3-bis- [1,1-bis (4-pyrrolidinophenyl) ) Ethylene-2-yl] -4,5,6,7-tetrabromophthalide, 3,3-bis- [1- (4-methoxyphenyl) -1- (4-pyrrolidinophenyl) ethylene-2- Yl] -4,5,6,7-tetrachlorophthalide

<Other basic dyes>
3- (4-Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- ( 1-octyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-cyclohexylethylamino-2-methoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl)- 4-azaphthalide, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3,6-bis (diethylamino) fluorane-γ- (3′-nitro) anilinolactam, 3,6 -Bis (diethylamino) fluorane-γ- (4'-nitro) anilinolactam, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p-dimethylamino) Enyl) -ethenyl] -2,2-dinitrileethane, 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2- β-naphthoylethane, 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2,2-diacetylethane, bis- [2, 2,2 ′, 2′-Tetrakis- (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester

  In the present invention, a conventionally known sensitizer can be contained in the heat-sensitive recording layer as long as the effects of the present invention are not impaired or in order to further enhance the effects of the present invention. Such sensitizers include ethylene bisamide, montanic acid wax, polyethylene wax, p-benzylbiphenyl, β-benzyloxynaphthalene, 4-biphenyl-p-tolyl ether, m-terphenyl, 4,4′-ethylenedioxy. -Bis-benzoic acid dibenzyl ester, dibenzoyloxymethane, bis [2- (4-methoxy-phenoxy) ethyl] ether, methyl p-nitrobenzoate, dibenzyl oxalate, di (p-chlorobenzyl) oxalate, Di (p-methylbenzyl) oxalate, dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, phenyl-α-naphthyl carbonate, 1,4-diethoxynaphthalene, 1-hydroxy-2- Naphthoic acid phenyl ester, 4- (m-methyl) Examples thereof include, but are not limited to, phenoxymethyl) biphenyl, orthotoluenesulfonamide, paratoluenesulfonamide, 1,2-diphenoxyethane, 1,2-di (3-methylphenoxy) ethane and the like. It is not a thing. These sensitizers may be used alone or in combination of two or more.

  In the present invention, examples of other components that can be contained in the heat-sensitive recording layer include pigments and binders (so-called binders).

  Examples of the pigment include inorganic or organic fillers such as colloidal silica, silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, aluminum hydroxide, and plastic pigment. Among these, the use of amorphous silica is preferable because it can improve the color density and prevent the adhesion of head debris. Further, it is more preferable to add calcium carbonate together with amorphous silica because an effect of preventing head scum and sticking can be more easily obtained. In addition, when mix | blending amorphous silica and calcium carbonate, those compounding sum ratios (weight ratio) have preferable about 1: 10-10: 1.

  As the binder, those generally known can be used as long as the desired effects of the present invention are not impaired in order to improve the fluidity of the paint. Specifically, fully saponified polyvinyl alcohol having a degree of polymerization of 200 to 1900, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, and other modified polyvinyl alcohols , Cellulose derivatives such as hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, ethylcellulose, acetylcellulose, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylate , Polyvinyl butyllar, polystyrene and their copolymers, polyamide resin, silicon resin, petroleum resin, terpene resin Ketone resin, can be exemplified Khumalo resin. These polymer substances are used by dissolving them in water, alcohol, ketones, esters, hydrocarbons and other solvents, and are used in the form of emulsification or paste dispersion in water or other media to achieve the required quality. It is also possible to use it together.

  Further, a stabilizer for imparting oil resistance and the like to the recorded image can be contained in the heat-sensitive recording layer as long as the effect of the present invention is not impaired. Such stabilizers include 4,4′-butylidene (6-tert-butyl-3-methylphenol), 2,2′-di-tert-butyl-5,5′-dimethyl-4,4′-sulfonyldi. Phenol, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenylbutane, 4 -Benzyloxy-4 '-(2,3-epoxy-2-methylpropoxy) diphenyl sulfone, epoxy resin and the like.

  In addition to stabilizers, lubricants such as waxes, UV absorbers such as benzophenone and triazole, water-resistant agents such as glyoxal, dispersants, antifoaming agents, antioxidants, fluorescent dyes, etc. are contained in the thermal recording layer. can do.

  In the present invention, the types and blending amounts of the basic leuco dye, the developer, and other various components (materials) are determined according to the required performance and recordability, and are not particularly limited. A coloring agent is about 0.5-10 weight part with respect to 1 weight part of basic leuco dyes, Preferably it is about 1-5 weight part. The pigment is usually about 0.5 to 10 parts by weight with respect to 1 part by weight of the basic leuco dye, and the sensitizer is usually about 0.5 to 10 parts by weight with respect to 1 part by weight of the basic leuco dye. About another component, it can select suitably and use in the range which does not injure the effect of this invention.

  In order to obtain the heat-sensitive recording material of the present invention, for example, for each of a dye, a developer, a sensitizer and the like, a dispersion is prepared by dispersing it together with a binder, and other necessary additives such as a filler are added to these dispersions. It can be produced by mixing to prepare a coating liquid (coating liquid for forming a heat-sensitive recording layer), applying this to a substrate (support) and drying to form a heat-sensitive recording layer. As a solvent used for this coating solution, water, alcohol, or the like can be used. The solid content of the coating liquid is preferably about 15 to 40% by weight. The dispersion of each component (material) is wet-ground using a pulverizer such as a ball mill, attritor or sand glider or a suitable emulsifying device until each component (material) has a particle size of several microns or less. It is preferable to do this.

  As the support, paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, nonwoven fabric and the like can be used. Moreover, you may use the composite sheet which combined these as a support body.

The application means of the coating liquid is not particularly limited, and can be applied according to well-known and commonly used coating techniques. For example, various coaters such as an air knife coater, rod blade coater, bill blade coater, roll coater, curtain coater, etc. An off-machine coating machine or an on-machine coating machine provided with is appropriately selected and used. The coating amount of the heat-sensitive recording layer is not particularly limited, but is usually ² to 12 g / m ² by dry weight.

  The heat-sensitive recording material of the present invention is provided with an overcoat layer on the heat-sensitive recording layer for the purpose of further improving the storage stability, and for the purpose of increasing the color development sensitivity, an undercoat layer such as a polymer substance containing a pigment is heat-sensitive recorded. It may be provided under the layer. It is also possible to correct the curl by providing a backcoat layer on the opposite side of the support from the thermosensitive recording layer. Also, various known techniques in the heat-sensitive recording material field, such as applying a smoothing process such as supercalendering after coating each layer, can be added as appropriate.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example. The structure of the compound was identified by MS, NMR and IR measurements, and the purity was determined by analysis by high performance liquid chromatography (HPLC) under the following conditions and represents area%. In the description, “parts” represents parts by weight, and “%” represents percent by weight unless otherwise specified.

Column: Inertsil ODS-2
Particle size: 5μm
Column: 4.6mmΦ × 15cm
Eluent: Acetonitrile: 0.05% phosphoric acid aqueous solution = 70: 30 (vol)
Flow rate: 0.8 mL / min
Wavelength: 254 nm
Injection volume: 1.0 μL
Column temperature: 40 ° C
Sample concentration: about 2500ppm

(1) Synthesis of diphenylsulfone derivative (Example 1)
Synthesis of 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2 ′-[4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether Four-neck reaction equipped with stirrer, thermometer and dropping funnel A container is charged with 70 g (0.24 mol) of 4-hydroxy-4′-isopropoxydiphenylsulfone and 9.6 g (0.24 mol) of sodium hydroxide, dissolved in 75 g of N, N-dimethylformamide, and stirred well. However, it was kept at 90 ° C. Bis (2-chloroethyl) ether 171.2 g (1.20 mol) was added dropwise, and the mixture was stirred at 90 ° C. for 6 hours. After completion of the reaction, toluene and an aqueous sodium hydroxide solution were added to the reaction solution and washed with water. The organic layer was concentrated, unreacted bis (2-chloroethyl) ether was distilled off, and 65.2 g of 2-chloro-2 ′-[4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether white crystals. Got.

  Next, 27.2 g (0.07 mol) of 2-chloro-2 ′-[4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether was added to a four-necked reaction vessel equipped with a stirrer and a thermometer. , 4'-dihydroxydiphenyl sulfone (171.0 g, 0.68 mol) and sodium hydroxide (27.3 g, 0.68 mol) were charged, dimethyl sulfoxide (350 g) was charged, and the reaction was carried out at 110 ° C for 5 hours. After completion of the reaction, toluene was added to the reaction solution and washed several times with an aqueous sodium hydrogen carbonate solution to remove unreacted 4,4'-dihydroxydiphenyl sulfone. An aqueous sodium hydroxide solution was added, and the target product was extracted into an aqueous layer. Acetic acid was added and acidified to obtain 28.2 g of white crystals. The purity was 99.2% and the melting point was 160 ° C.

This white crystal was confirmed to have vibrational stretching of the hydroxyl group at 3320 cm ⁻¹ in IR (ATR). As a result of ¹ H-NMR (270 MHz, DMSO-d ₆ ) measurement, δ = 10.6 ppm (s, 1H), 7.80 ppm (m, 8H), 7.10 ppm (m, 6H), 6.90 ppm (d, 2H), 4.70 ppm (m, 1H), 4.17 ppm (m, 4H), 3.80 ppm (m , 4H) and 1.25 ppm (d, 6H), respectively. In MS (ESI / POSITOV), m / z = 613 [M + H] ⁺ was observed, and 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2 ′-[4- (4-iso Propoxyphenylsulfonyl) phenoxy] -diethyl ether.

(Example 2)
Synthesis of 1- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -2- (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) -ethane Used in Example 1 The same operation as in Example 1 was performed using 1,2-bis (2-chloroethoxy) ethane in place of bis (2-chloroethyl) ether to obtain 28.1 g of white crystals. The purity was 97.9% and the melting point was 110 ° C.
This white crystal was confirmed to undergo vibrational stretching of the hydroxyl group at 3410 cm ⁻¹ in IR (ATR). As a result of ¹ H-NMR (270 MHz, DMSO-d ₆ ) measurement, δ = 7.79 ppm (m, 6H), 7.71 ppm (d, 2 H), 6.90 ppm (m, 8 H), 4.60 ppm (m, 1 H), 4.11 ppm (m, 4 H), 3.83 ppm (m, 4 H), 3.71 ppm (s , 4H) and 1.33 ppm (d, 6H), respectively. Further, m / z = 656 [M + H] ⁺ was also observed in MS (ESI / NEGATIV), and 1- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -2- (2- Identified as [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) -ethane.

(Example 3)
Synthesis of 1- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy) -2- (2- [4- (4-allyloxyphenylsulfonyl) phenoxy] ethoxy) -ethane Used in Example 1 Instead of 4-hydroxy-4′-isopropoxydiphenylsulfone and bis (2-chloroethyl) ether, 4-allyloxy-4′-hydroxydiphenylsulfone and 1,2-bis (2-chloroethoxy) ethane are used, The same operation as in Example 1 was performed to obtain 32.3 g of white crystals. The purity was 99.1% and the melting point was 125 ° C.
This white crystal was confirmed to undergo vibrational stretching of the hydroxyl group at 3427 cm ⁻¹ in IR (ATR). As a result of ¹ H-NMR (270 MHz, DMSO-d ₆ ) measurement, δ = 7.77 ppm (m, 8H), 7.09 ppm (m, 6H), 6.90 ppm (d, 2H), 6.01 ppm (m, 1H), 5.35, ppm (dd, 2H), 4.64 ppm (d, 2H), 4.12 ppm Peaks were observed at (m, 4H), 3.72 ppm (m, 4H), and 3.56 ppm (s, 4H), respectively, and 1- (2- [4- (4-hydroxyphenylsulfonyl) phenoxy] ethoxy)- It was identified as 2- (2- [4- (4-allyloxyphenylsulfonyl) phenoxy] ethoxy) -ethane.

Example 4
2,2′-bis [4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether and 4,4′-bis (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy-diphenyl Synthesis of 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2 ′-[4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether mixture containing sulfone According to Example 1, unreacted 4 The same operation was performed until 4,4′-dihydroxydiphenylsulfone was removed. The obtained organic layer was concentrated and recrystallized from acetonitrile, and 2,2′-bis [4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether and 4,4′-bis (2- [4- 2- [4- (4-Hydroxyphenylsulfonyl) phenoxy] -2 ′-[4- (4-isopropoxyphenylsulfonyl) phenoxy] containing (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy-diphenylsulfone -15.6 g of white crystals of diethyl ether mixture were obtained. The components of the mixture were 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2 ′-[4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether 91.0%, 2,2′-bis [ 4- (4-isopropoxyphenylsulfonyl) phenoxy] -diethyl ether 4%, 4,4′-bis (2- [4- (4-isopropoxyphenylsulfonyl) phenoxy] ethoxy) ethoxy-diphenylsulfone 4%. It was. The melting point was 124 ° C.

(Example 5)
Synthesis of 4- (4- [4- (4-hydroxyphenylsulfonyl) phenoxy] butoxy) -4 ′-(4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butoxy) diphenylsulfone Used in Example 1 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenyl) instead of 4-hydroxy-4′-isopropoxydiphenylsulfone and bis (2-chloroethyl) ether [Sulfonyl) phenoxy] butane (compound of Comparative Example 3) and 1,4-dibromobutane were used in the same manner as in Example 1 to obtain 24.5 g of white crystals. The purity was 90.0% and the melting point was 185 ° C.
This white crystal was observed to undergo vibrational stretching of the hydroxyl group at 3410 cm ⁻¹ in IR (ATR) and m / z = 900 [M + H] ⁺ in LC-MS (APCI / NEGATIV). 4- (4- [ 4- (4-Hydroxyphenylsulfonyl) phenoxy] butoxy) -4 ′-(4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butoxy) diphenylsulfone was identified.

(Example 6)
4- (4- [4- (4-hydroxyphenylsulfonyl) phenoxy] butoxy) -4 ′-(4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butoxy) diphenyl sulfone obtained in Example 5 5 g and 5 g of 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane (compound of Comparative Example 3) were mixed by powder, A diphenylsulfone derivative mixture having a composition of 50:50 was obtained.

(Example 7)
4- (4- [4- (4-hydroxyphenylsulfonyl) phenoxy] butoxy) -4 ′-(4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butoxy) diphenyl sulfone obtained in Example 5 2.5 g and 7.5 g of 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane (compound of Comparative Example 3) were mixed with powder. Thus, a diphenylsulfone derivative mixture having a composition of 25:75 was obtained.

(Example 8)
4- (4- [4- (4-hydroxyphenylsulfonyl) phenoxy] butoxy) -4 ′-(4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butoxy) diphenyl sulfone obtained in Example 5 1.5 g and 8.5 g of 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane (compound of Comparative Example 3) were mixed with powder. Thus, a diphenylsulfone derivative mixture having a composition of 15:85 was obtained.

Example 9
4- (4- [4- (4-hydroxyphenylsulfonyl) phenoxy] butoxy) -4 ′-(4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butoxy) diphenyl sulfone obtained in Example 5 0.5 g and 9.5 g of 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane (compound of Comparative Example 3) were mixed with powder. Thus, a diphenylsulfone derivative mixture having a composition of 5:95 was obtained.

(2) Production of thermosensitive recording material (Example 10)
For each material of the dye, developer, and sensitizer, dispersions having the following blending ratios were prepared in advance, and wet grinding was performed with a sand grinder until the average particle size became 0.5 μm.

<Dye dispersion>
3-di-n-butylamino-6-methyl-7-anilinofluorane (trade name: ODB-2 manufactured by Yamamoto Kasei Co., Ltd.) 10.0 parts 10% polyvinyl alcohol aqueous solution 20.0 parts water 15.0 parts

<Developer dispersion>
Diphenylsulfone derivative of Example 1 10.0 parts 10% aqueous polyvinyl alcohol solution 25.0 parts Water 15.0 parts

<Sensitizer dispersion>
Dibenzyl oxalate 10.0 parts

10% polyvinyl alcohol aqueous solution 30.0 parts Water 20.0 parts

Coating solution prepared by mixing the following formulation (the heat-sensitive recording layer-forming coating solution) was prepared, as the coating amount after drying the coating liquid to wood free paper having a basis weight of 50 g / m ² is 8 g / m ² The coating was dried and processed with a super calendar so that the Beck smoothness was 200 to 600 seconds to obtain a heat-sensitive recording material.

<Coating solution>
Dye dispersion 6.00 parts Developer dispersion 15.00 parts Sensitizer dispersion 15.00 parts Zinc stearate (manufactured by Chukyo Yushi Co., Ltd., trade name: Hydrin Z-7-30, solid content 30%) 3 0.0 part amorphous silica (manufactured by Mizusawa Chemical Co., Ltd., trade name: Mizukasil P537) 25% dispersion
10.0 parts calcium carbonate (trade name: Tunex E, manufactured by Shiraishi Calcium Co., Ltd.) 50% dispersion
5.0 parts 10% polyvinyl alcohol aqueous solution 10.0 parts Water 2.0 parts

(Example 11)
A heat-sensitive recording material was obtained in the same manner as in Example 10 except that the diphenylsulfone derivative of Example 2 was used as a developer instead of the diphenylsulfone derivative of Example 1.

(Example 12)
A thermosensitive recording material was obtained in the same manner as in Example 10 except that the diphenylsulfone derivative of Example 3 was used as a developer instead of the diphenylsulfone derivative of Example 1.

(Example 13)
A thermosensitive recording material was obtained in the same manner as in Example 10 except that the diphenylsulfone derivative mixture of Example 4 was used as a developer instead of the diphenylsulfone derivative of Example 1.

(Example 14)
A heat-sensitive recording material was obtained in the same manner as in Example 10 except that the diphenylsulfone derivative of Example 5 was used as a developer instead of the diphenylsulfone derivative of Example 1.

(Example 15)
A thermosensitive recording material was obtained in the same manner as in Example 10 except that the diphenylsulfone derivative mixture of Example 6 was used as a developer instead of the diphenylsulfone derivative of Example 1.

(Example 16)
A thermosensitive recording material was obtained in the same manner as in Example 10 except that the diphenylsulfone derivative mixture of Example 7 was used as a developer instead of the diphenylsulfone derivative of Example 1.

(Example 17)
A thermosensitive recording material was obtained in the same manner as in Example 10 except that the diphenylsulfone derivative mixture of Example 8 was used as a developer instead of the diphenylsulfone derivative of Example 1.

(Example 18)
A thermosensitive recording material was obtained in the same manner as in Example 10 except that the diphenylsulfone derivative mixture of Example 9 was used as a developer instead of the diphenylsulfone derivative of Example 1.

(Comparative Example 1)
A heat-sensitive recording material was obtained in the same manner as in Example 5 except that 4-isopropoxy-4′-hydroxydiphenylsulfone was used as a developer instead of the diphenylsulfone derivative of Example 1.

(Comparative Example 2)
A thermosensitive recording material was prepared in the same manner as in Example 5 except that a diphenylsulfone crosslinked derivative (trade name: D-90, manufactured by Nippon Soda Co., Ltd.) was used as a developer instead of the diphenylsulfone derivative of Example 1. Obtained.

(Comparative Example 3)
In place of the diphenylsulfone derivative of Example 1, 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane (Japanese Patent Laid-Open No. 2003-212841) A diphenylsulfone derivative compound) was used as a developer to obtain a thermosensitive recording material in the same manner as in Example 5.

(3) Evaluation test The following evaluation was performed about the thermosensitive recording material obtained in Examples 5-8 and Comparative Examples 1-2. The results are shown in Table 1.

[Plasticizer resistance]
Using a TH-PMD made by Okura Electric Co., Ltd., heat-sensitive recording material printed at an applied energy of 0.34 mJ / dot was adhered to a vinyl chloride wrap film (Mitsui Toatsu Co., Ltd., High Wrap KMA) at 20 ° C. for 2 hours. Then, the image density of the recording part was measured with a Macbeth densitometer, and the image residual ratio was calculated by the following formula (A).
Image residual ratio (%) = density after test / density before test × 100 (A)

[Heat-resistant]
After leaving a thermal recording material printed with an applied energy of 0.34 mJ / dot for 24 hours in an environment of 60 ° C., 80 ° C. and 90 ° C. using TH-PMD manufactured by Okura Electric Co., The image density at 80 ° C. and 90 ° C. was measured with a Macbeth densitometer. The recording unit measured the image density at 60 ° C. with a Macbeth densitometer, and calculated the image residual ratio (%) according to the formula (A).

  The measured values excluding the background portion in Tables 1 and 2 indicate that the larger the value, the higher the color density, and the higher the remaining rate, the less the fading. Further, the measured value of the background portion indicates that the smaller the value is, the more white the color is kept (the color is not developed).

  As is apparent from the results in Table 1, the conventional developer achieves a high level of both image storage stability, particularly image storage stability in plasticizer resistance, and background storage stability at high temperatures. A thermosensitive recording material having good performance could not be obtained. However, by using the novel diphenylsulfone derivative according to the present invention as a developer, it is possible to provide a heat-sensitive recording material that not only has good storage stability against plasticizers, but also has good storage stability against heat. Was confirmed. Further, from the results of Table 2, by adding the compound of the diphenylsulfone derivative (I) to the compound of the diphenylsulfone derivative (II), while satisfying the storage stability to the plasticizer and the storage stability of the background to heat, It was confirmed that the image storage stability against heat was also improved.

Claims (10)

The following general formula (I):

[Where:
R ^{1 to} R ⁶ each independently represent a halogen atom, a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
R represents a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
p, q, r, s, t, and u each independently represent an integer of 0 to 4, and in the case of 2 or more, R ^{1 to} R ⁶ may be the same or different,
n is 0;
A is a linear or branched C1-12 saturated or unsaturated hydrocarbon group which may have an ether bond, or the following formulas (a) to (c):

(In the formula, each X independently represents a methylene group or an ethylene group, Y represents a hydrogen atom or a C1-4 alkyl group, and Z represents an arylene group or a C1-10 alkylene group). Is shown). ]
At least one diphenylsulfone derivative (I) represented by:
The following general formula (II):

[Where:
R ^{11 to} R ¹⁶ each independently represent a halogen atom, a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
R ^a represents a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
p1, q1, r1, s1, t1, and u1 each independently represent an integer of 0 to 4, and in the case of 2 or more, R ^{11 to} R ¹⁶ may be the same or different,
n1 represents an integer of 1 to 5,
A ¹ is a linear or branched C 1-12 saturated or unsaturated hydrocarbon group that may have an ether bond independently, or the following formulas (a1) to (c1):

(Wherein, X ¹ independently represents a methylene group or an ethylene group, Y ¹ represents a hydrogen atom or a C1-4 alkyl group, and Z ¹ represents an arylene group or C1-10) Represents an alkylene group). ]
A diphenylsulfone derivative mixture containing at least one diphenylsulfone derivative (II) represented by A linear or a diphenyl sulfone derivative is a saturated or unsaturated hydrocarbon group of C1-12 branched (I), the hydrocarbon saturated or unsaturated C1-12 A ¹ is a straight-chain or branched The diphenylsulfone derivative mixture according to claim 1, which contains the group diphenylsulfone derivative (II).   The diphenylsulfone derivative mixture according to claim 1 or 2, wherein the amount of the diphenylsulfone derivative (II) is 0.05 to 99% by weight based on the total weight of the diphenylsulfone derivative. The following general formula (III):

[Where:
R ^{21 to} R ²⁶ each independently represent a halogen atom, a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
R ^b represents a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
p2, q2, r2, s2, t2, and u2 each independently represent an integer of 0 to 4, and in the case of 2 or more, R ^{21 to} R ²⁶ may be the same or different,
n2 represents an integer of 0 to 5,
A ² is independently a linear or branched C 1-12 saturated or unsaturated hydrocarbon group which may have an ether bond, or the following formulas (a2) to (c2):

(Wherein, X ² independently represents a methylene group or an ethylene group, Y ² represents a hydrogen atom or a C1-4 alkyl group, and Z ² represents an arylene group or C1-10) Represents an alkylene group). However, in the case of n2 = 0, a saturated or unsaturated hydrocarbon group of the in ^{A 2} C1-12 has an ether bond. ]
The diphenyl sulfone derivative represented by these. n2 = 0, and a saturated or unsaturated hydrocarbon group of C1~12 straight-chain or branched ^{A 2} is an ether bond, or the following formula (a2) ~ (c2):

(Wherein, X ² independently represents a methylene group or an ethylene group, Y ² represents a hydrogen atom or a C1-4 alkyl group, and Z ² represents an arylene group or C1-10) The diphenylsulfone derivative according to claim 4, which represents an alkylene group of n2 is an integer from 1 to 5, and, A ² is a saturated or unsaturated hydrocarbon group of C1~12 straight-chain or branched, diphenyl sulfone derivatives according to claim 4, wherein. Furthermore, the following general formula (IV)

[Where:
R ^{31 to} R ³⁶ each independently represent a halogen atom, a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
R ^c represents a C1-12 alkyl group or alkenyl group, or a substituted or unsubstituted aryl group;
p3, q3, r3, s3, t3, u3 are independently an integer of 0 to 4, and if ^more, R 31 ^{to R 36} may be different from each other in the same,
n3 represents an integer of 0 to 5,
A ³ is independently a linear or branched C 1-12 saturated or unsaturated hydrocarbon group which may have an ether bond, or the following formulas (a3) to (c3):

(Wherein, X ³ independently represents a methylene group or an ethylene group, Y ³ represents a hydrogen atom or a C1-4 alkyl group, and Z ³ represents an arylene group or C1-10) Represents an alkylene group). ]
At least one of the diphenylsulfone derivatives (IV) represented by: and the diphenylsulfone derivative mixture according to any one of claims 1 to 3 or the diphenylsulfone derivative according to any one of claims 4 to 6. A diphenylsulfone derivative mixture containing.   The diphenylsulfone derivative mixture according to claim 7, wherein the content of the diphenylsulfone derivative (IV) is 0.01 to 10% by weight based on the total weight of the diphenylsulfone derivative.   A heat-sensitive recording material provided on a support with a heat-sensitive recording layer comprising a colorless or light-colored basic leuco dye and a developer for coloring the basic leuco dye, the developer as the developer A heat-sensitive recording material comprising the diphenylsulfone derivative mixture according to any one of claims 1 to 3 or 7 to 8.   A heat-sensitive recording material provided on a support with a heat-sensitive recording layer comprising a colorless or light-colored basic leuco dye and a developer for coloring the basic leuco dye, the developer as the developer A heat-sensitive recording material containing the diphenylsulfone derivative according to any one of claims 4 to 6.