JP2002332271A - Novel color developer and recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel color-developing agent having excellent record image preservability and high color concentration, a recording material, particularly a thermal recording material using the same. SOLUTION: The objective novel color-developing agent includes urea- urethane of a molecular weight of <=5,000, represented by the general formula c (wherein R is a residual group of aliphatic compound; A1 and A2 are each independently aromatic residues in which the N atom in the urea group directly bonds to the carbons of the aromatic rings of A1 and A2 and A1 and A2 may be substituted) and a colorless or light coloring dye precursor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel ureaurethane compound. The present invention also relates to a novel color former using a urea urethane compound and a recording material using the same. The color former of the present invention is useful, for example, as a color former of a recording material using recording energy such as heat and pressure, and in particular, a color former which has improved storage stability of an uncolored portion (background) and a color image, and The present invention relates to a recording material using the same, particularly to a thermal recording material.

[0002]

2. Description of the Related Art Conventionally, many chemical color forming systems using recording energy such as heat and pressure are known. Among them, a color forming system comprising a two-component color forming system of a colorless or pale color dye precursor and a color developing agent which forms a color in contact with the dye precursor has been known for a long time, and widely applied to recording materials. Have been. For example, there are a pressure-sensitive recording material using pressure energy, a heat-sensitive recording material using heat energy, and a photosensitive recording material using light energy.

[0003] A pressure-sensitive recording material using pressure energy has been very commonly used as if it were plain paper. In general, a pressure-sensitive recording material is obtained by dissolving a dye precursor in an appropriate solvent, emulsifying the solution to several microns, and then performing microencapsulation. The upper paper formed by applying the microcapsules on a support and the lower paper formed by applying a developer layer containing a color developer on another support are coated on the microcapsule-coated surface and the developer-coated surface. Are superposed so that they face each other, and when a pen pressure or a pressing pressure is applied, the microcapsules are broken and the inclusions containing the dye precursor are released. The dye precursor is transferred to the color developer layer and comes into contact with the color developer, causing a color development reaction to record an image.

In recent years, for example, various information devices such as facsimile machines, printers, recorders, and the like, have often adopted a thermal recording system in which recording is performed using thermal energy. The heat-sensitive recording material used in the heat-sensitive recording system has many excellent properties such as high whiteness, good appearance and feel close to plain paper, good recording suitability such as color sensitivity, etc. Has the advantages of small size, no maintenance, no noise, and a wide range of applications such as measurement recorders, facsimile machines, printers, computer terminals, labels, and automatic ticket vending machines such as ticketing. Applications have been expanded to the field of

[0005] The thermal recording method mainly uses a recording material in which a color-forming layer containing a two-component color-forming agent is provided on a support.
In this method, heat is applied as recording energy by a heat-sensitive head, a hot stamp, a laser beam, or the like, so that heat-sensitive agent components are brought into contact with each other on a recording material to perform color recording. Many color formers use a colorless or light-colored electron-donating dye precursor (particularly a leuco dye) and an acidic developer such as a phenolic compound. As a recording material using a dye precursor, for example, a thermal paper (see U.S. Pat. No. 3,539,375) using crystal violet lactone and 4,4'-isopropylidene diphenol (bisphenol A) as a thermosensitive coloring agent is exemplified. No.

As a dye precursor and a color developer used in these recording systems, an electron donating compound and an electron accepting compound are mainly used, respectively. This is because the dye precursor, which is an electron-donating compound, and the developer, which is an electron-accepting compound, come into contact with each other, so that a color image with high density can be obtained instantaneously, and an appearance close to white can be obtained. This is because they have excellent characteristics such as obtaining various color hues such as red, orange, yellow, green, blue, and black. However, on the other hand, the obtained color image has poor chemical resistance, and when it comes into contact with a plasticizer contained in a plastic sheet or an eraser or a chemical contained in food or cosmetics, the record is easily lost, Due to poor storage stability of the record, such as fading or even disappearing of the record due to short-term sunlight exposure, the color former consisting of the dye precursor and the developer is subject to certain restrictions in use. Therefore, the improvement is strongly desired.

In recent years, the use of phenolic compounds represented by bisphenol A has been considered a problem due to the problem of environmental hormones, and non-phenolic color developers have been demanded. In response to such a demand, as recording materials having good storability, for example, JP-A-59-11587 and U.S. Pat. No. 4,521,793 disclose a coloring agent comprising an aromatic isocyanate compound and an imino compound. A recording material comprising a combination is disclosed. In the present invention,
2 by applying recording energy such as heat, pressure, light, etc.
Various recording materials in which various color formers are brought into contact with and reacted with each other have been disclosed. Also, by appropriately selecting the color former,
It describes that various colors such as red, orange, yellow, brown, and brown can be developed. However, black color, which is strongly demanded of recording materials widely used at present, is still insufficient.

Further, as a heat-sensitive recording material using a non-phenol type developer, JP-A-8-2111 and JP-A-8-2112 contain a colorless or pale color dye precursor and a urea compound. A thermosensitive recording medium having a coloring layer is disclosed. However, these recording materials had low color density and insufficient storage stability. In addition, Japanese Patent Application Laid-Open No. 5-1164
No. 59 discloses a thermosensitive recording medium having a thermosensitive coloring layer containing a colorless or pale color dye precursor and a sulfonylurea compound. However, these recording materials had low whiteness and insufficient storage stability.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel ureaurethane compound or ureaurethane composition which exhibits excellent performance when used as a color developer. Further, the present invention provides a novel color former excellent in image storability and color density by using various urea urethane compounds or urea urethane compositions, and a recording material using the same, particularly a heat-sensitive recording material. As an issue. Further, the present invention relates to a novel color former which is obtained by adding various additives to a urea urethane compound or a urea urethane composition and a dye precursor to further improve the performance, and a recording material using the same.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the synthesis of various color former compounds, and as a result, have found that a specific compound exhibits surprisingly excellent performance, thereby completing the present invention. Reached. In addition, they have found that a specific compound exhibits surprisingly excellent performance in combination with a specific dye precursor, and have completed the present invention. That is, the present invention is as follows. The first of the invention is
A urea urethane compound represented by the following formula (c) and having a molecular weight of 5,000 or less.

[0011]

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(Wherein, R represents an aliphatic compound residue;
₁ and A ₂ each independently represent an aromatic compound residue, the nitrogen atom of the urea group is directly bonded to the carbon atom of the aromatic ring of A ₁ and A ₂ , and R, A ₁ and A 2 ₂ may have a substituent. A second aspect of the present invention is a urea urethane compound represented by the following formula (d).

[0013]

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(Wherein, R represents an aliphatic compound residue, the hydrogen atom of the benzene ring may be substituted, and the substituent may be an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Groups are preferred, but hydroxyl, nitro, nitrile, carbamoyl, sulfamoyl, carboxyl, nitroso, amino, oxyamino, nitroamino, hydrazino, ureido, isocyanato, mercapto, sulfo groups Or R may have a substituent.) A third aspect of the present invention is represented by the following formula (e) or (f), wherein the number of urethane groups is A urea urethane compound characterized in that the total number of urea groups is 3 or more and 10 or less and the molecular weight is 5000 or less.

[0015]

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(Wherein R represents an aliphatic compound residue;
Represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, and α ₁ represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound having a valence of 2 or more different from Y. Represents a compound residue, n represents an integer of 2 or more, and each residue may have a substituent. )

[0017]

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(Wherein Z ₁ and Y each independently represent an aromatic compound residue or a heterocyclic compound residue, and β ₁ is 2
Represents an aliphatic compound residue having a valence of at least 2, and n is 2
It represents the above integer, and each residue may have a substituent. A fourth aspect of the present invention is a urea urethane compound represented by the following formula (g) or (h).

[0019]

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(In the formula, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue, but is preferably a hydroxyl group, a nitro group, A nitrile group, a carbamoyl group,
Sulfamoyl group, carboxyl group, nitroso group, amino group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanato group, mercapto group, may be substituted by a sulfo group or a halogen atom, β
₁ represents an aliphatic compound residue having a valence of 2 or more,
n represents an integer of 2 or more, and each residue may have a substituent. )

[0021]

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(Wherein each R independently represents an aliphatic compound residue, even if the hydrogen atom of the benzene ring is substituted by an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Well, each residue may have a substituent, and γ ₁ is -SO _2- , -O-,-(S) _n -,-
(CH ₂ ) _n- , -CO-, -CONH-, -NH-,-
CH (COOR ₁ )-, -C (CF ₃ ) _2- , -CR ₂ R ₃
-And one selected from the group consisting of any of the groups represented by formula (a),

[0023]

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Or R ₁ , R ₂
And R ₃ each represents an alkyl group, and n is 1 or 2. A fifth aspect of the present invention is a urea urethane composition comprising a urea urethane compound and a diluent. In a sixth aspect of the present invention, the fifth diluent of the present invention comprises a urea compound and / or
Or the urea urethane composition according to the fifth aspect of the present invention, which is a urethane compound. A seventh aspect of the invention is the ureaurethane composition according to the fifth aspect, wherein the fifth diluent of the invention is a compound obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound.

An eighth aspect of the present invention is a urea urethane composition obtained by reacting a polyisocyanate compound with a hydroxy compound and an amino compound, wherein at least one urea group and at least one urethane group are present in the molecular structure. Total 2
A urea urethane composition comprising 50 to 10% by weight of a urea urethane compound having a molecular weight of 5000 or less. A ninth aspect of the present invention is the ureaurethane composition according to the eighth aspect, wherein the hydroxy compound is a phenol compound. A tenth aspect of the present invention is the urea urethane composition according to the eighth aspect, wherein the hydroxy compound is an alcohol compound. An eleventh aspect of the invention is the ureaurethane composition according to any one of the eighth to tenth aspects of the invention, wherein the amino compound is an aromatic amino compound.

A twelfth aspect of the invention is the eighth aspect of the invention, wherein the polyisocyanate compound is an aromatic polyisocyanate compound.
The urea urethane composition according to any one of items 1 to 11, wherein A thirteenth aspect of the present invention relates to a method of preparing a polyisocyanate compound and a hydroxy compound, wherein the number of moles of the polyisocyanate compound /
The ratio of the number of hydroxyl equivalents of the hydroxy compound is from 100/1 to 1
/ 2 to form a urethane group from a part of the isocyanate group of the polyisocyanate compound, and then add an amino compound to react the remaining isocyanate group of the polyisocyanate compound with the amino compound. A urea group to form a urea group.

In a fourteenth aspect of the present invention, the ratio of the number of moles of the polyisocyanate compound / the number of equivalents of the amino group of the amino compound is from 100/1 to 100%.
After reacting under a condition of 1/2 to form a urea group from a part of the isocyanate group of the polyisocyanate compound, a hydroxy compound is added, and the remaining isocyanate group of the polyisocyanate compound is reacted with the hydroxy compound. A method for producing a urea urethane composition, comprising reacting to form a urethane group.

A fifteenth aspect of the present invention is the method for producing a ureaurethane composition according to the thirteenth or fourteenth aspect of the invention, wherein the reaction for forming a urethane group and the reaction for forming a urea group are carried out continuously. is there. A sixteenth aspect of the present invention provides a polyisocyanate adduct obtained by reacting a polyisocyanate compound with a hydroxy compound, and an amino compound, wherein the isocyanate group / amino group equivalent ratio is 2/1 to 1
/ 100 is a method for producing a urea urethane composition in which an unreacted amino compound is removed after a urea group is formed by a reaction at 100/100.

A seventeenth aspect of the present invention is to react a polyisocyanate adduct obtained by reacting a polyisocyanate compound with an amino compound with a hydroxy compound at an isocyanate group / hydroxyl equivalent ratio of 2/1 to 1/100. This is a method for producing a urea urethane composition in which an unreacted hydroxy compound is removed after the formation of a urethane group.
An eighteenth aspect of the present invention provides a reaction for forming a urethane group and / or
Or any one of the thirteenth to seventeenth aspects of the invention, wherein the reaction for forming a urea group is performed without a solvent, or the reaction for forming a urethane group and the reaction for forming a urea group are performed using the same solvent. A method for producing the urea urethane composition described above.

A nineteenth aspect of the present invention is directed to the thirteenth to first aspects of the invention, wherein the reaction for forming a urethane group and / or the reaction for forming a urea group are carried out at a temperature of 0 to 300 ° C.
8. A method for producing the urea urethane composition according to any one of items 8. The twentieth aspect of the invention is the method for producing a urea urethane composition according to any one of the thirteenth to nineteenth aspects of the invention, wherein the reaction for forming a urethane group and / or the reaction for forming a urea group are performed in the presence of a catalyst.

A twenty-first aspect of the invention is characterized in that the reaction for forming a urethane group and / or the reaction for forming a urea group are carried out using a solvent having a solubility parameter value (δ) of 7 to 15. 21. A method for producing a urea urethane composition according to any one of 13 to 20. Second of the invention
No. 2 is the method for producing a urea urethane composition according to the 21st aspect of the present invention, wherein the reaction is carried out using a solvent having a solubility parameter value (δ) of 7 to 8.8. A twenty-third aspect of the present invention is the method for producing a urea urethane composition according to the twenty-second aspect of the invention, wherein the reaction is carried out using a solvent having a solubility parameter value (δ) of 8.9 to 21 in combination. is there.

A twenty-fourth aspect of the present invention is a color former containing a color developer containing a urea urethane compound. Twenty-fifth aspect of the invention
A color developer containing a urea urethane compound and a color former containing a colorless or pale color dye precursor. Twenty-sixth invention
Is a color former according to the twenty-fifth aspect of the present invention, wherein the colorless or pale color dye precursor is a leuco dye. In a twenty-seventh aspect of the present invention, the developer is the urea urethane compound according to any one of the first to fourth aspects of the invention, the urea urethane composition according to any one of the fifth to twelfth aspects of the invention, or the thirteenth aspect of the invention. 23. The coloring agent according to any one of Items 24 to 26 of the invention, which is a composition produced by the production method according to any one of Items 23 to 23.

In a twenty-eighth aspect of the present invention, the leuco dye is at least one selected from a triarylmethane leuco dye, a fluoran leuco dye, a fluorene leuco dye, and a diphenylmethane leuco dye. 28. The color forming agent according to any one of Items 26 to 27. Twenty-ninth aspect of the present invention is a leuco dye represented by the following formula (i-1)
A twenty-sixth aspect of the invention, which is a compound represented by the formula:
28. The color forming agent according to any one of Items 27 to 27.

[0034]

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(Where Y ₂ and Y ₃ both represent an alkyl group or an alkoxyalkyl group, Y ₄ represents a hydrogen atom, an alkyl group, or an alkoxy group; and Y ₅ and Y ₆ represent a hydrogen atom, A halogen atom, an alkyl group or an alkoxy group is represented.) In a thirtieth aspect of the invention, the leuco dye is a compound represented by the following formula (i-2):
The coloring agent according to any one of the above.

[0036]

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(Here, P ₂ and P ₃ both represent an alkyl group or an alkoxyalkyl group, and at least one of P ₂ and P ₃ is a group having 5 or more carbon atoms.
₄ represents a hydrogen atom, an alkyl group, or an alkoxy group. P ₅ and P ₆ represent a hydrogen atom, a halogen atom, an alkyl group, a halogen-substituted alkyl group or an alkoxy group. A thirty-first aspect of the invention is a composition according to the twenty-sixth to twenty-seventh aspects, wherein the leuco dye is a compound represented by the following formula (i-3).
The coloring agent according to any one of the above.

[0038]

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(Where Q ₂ and Q ₃ both represent an alkyl group or an alkoxyalkyl group, Q ₄ represents a hydrogen atom, an alkyl group, or an alkoxy group; and Q ₅ and Q ₆ represent a hydrogen atom a halogen atom, an alkyl group, but a halogen-substituted alkyl group or an alkoxy group, Q ₅
And at least one of Q ₆ is a halogen atom,
It is an alkyl group or a halogen-substituted alkyl group. A thirty-second aspect of the invention is the color former according to any one of the twenty-sixth to twenty-seventh aspects of the invention, wherein the leuco dye is a compound represented by the following formula (j).

[0040]

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[Wherein R ₅ and R ₆ represent either a group represented by the formula (k) or the formula (l)].

[0042]

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[0043] (wherein, R ₁₁ to R ₁₅ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, .R ₁₆ showing a -NR ₁₆ R _17, R ₁₇ is an alkyl group having 1 to 8 carbon atoms.)

[0044]

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(Here, R ₁₈ and R ₁₉ represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.)
_{7 to} R ₁₀ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, -NR ₂₀ R
Indicates ₂₁ . R ₂₀ and R ₂₁ are an alkyl group having 1 to 8 carbon atoms. The thirty-third invention has a melting point of the urea urethane compound developer,
The color former according to any one of the twenty-fourth to thirty-second aspects of the invention, which is at least 40 ° C. and no more than 500 ° C. The thirty-fourth aspect of the invention is characterized in that the urea urethane compound developer has the following general formula (V) Or the color forming agent according to any one of Items 24 to 32 of the invention, which is any one selected from (VI).

[0046]

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(Wherein the hydrogen atom of the benzene ring is a residue of an aromatic or aliphatic compound or a residue of a heterocyclic compound,
A nitro group, hydroxyl group, carboxyl group, nitroso group, nitrile group, carbamoyl group, ureido group, isocyanato group, mercapto group, sulfo group, sulfamoyl group or a halogen atom may be substituted, and each residue is a substituent. Γ is -SO _2- , -O
_{-, - (S) n -} , - (CH 2) n -, - CO -, - CO
One selected from the group consisting of NH- and any of the groups represented by formula (a),

[0048]

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Or n is absent, and n is 1 or 2
It is. ),as well as

[0050]

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(Wherein the hydrogen atom of the benzene ring is an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue or a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group , Amino group, oxyamino group, nitroamino group, hydrazino group,
Ureido group, isocyanato group, mercapto group, may be substituted by a sulfo group or a halogen atom,
Each residue may have a substituent, and δ is -SO _2- ,
_{-O -, - (S) n} -, - (CH 2) n -, - CO -, -
CONH -, - NH -, - CH (COOR 1) -, - C
One selected from the group consisting of (CF ₃ ) ₂ — and —CR ₂ R ₃ — or absent; R ₁ , R ₂ and R ₃ each represent an alkyl group, and n is 1 or 2 is there. )

A thirty-fifth aspect of the invention is the twenty-fourth to thirty-second aspects of the invention, wherein the urea urethane compound developer is any one selected from the following structural formulas (XX) and (XXI). A coloring agent according to any one of the above.

[0053]

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[0054]

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A thirty-sixth aspect of the invention is the color former according to any one of the twenty-fourth to thirty-fifth aspects of the invention, further comprising a heat-fusible substance. In a thirty-seventh aspect of the present invention, the heat-fusible substance is β-naphthylbenzyl ether, p-benzylbiphenyl, 1,2-
Di (m-methylphenoxy) ethane, di-p-oxalate
36. The color forming agent according to item 36, wherein the color forming agent is at least one selected from methylbenzyl ester, 1,2-diphenoxymethylbenzene, metaterphenyl, and stearamide. The thirty-eighth aspect of the invention is:
The color former according to Item 36, wherein the heat-fusible substance is represented by the following structural formula (XVIII).

[0056]

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(Where Y is -SO ₂ -,-(S) _n -,-
O -, - CO -, - CH 2 -, - CH (C 6 H 5) -, -
_{C (CH 3) 2 -,} - COCO -, - CO 3 -, - COC
_{H 2 CO -, - COOCH 2} -, - CONH -, - OCH
_It represents either-or -NH-. n is 1 or 2. The hydrogen atom of the benzene ring includes a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanato group, an isothiocyanato group, a mercapto group, a sulfamoyl group, a sulfone group, an amino group, an aromatic compound residue, and an aliphatic compound. It may be substituted by a residue or a heterocyclic compound residue. A thirty-ninth aspect of the present invention is directed to a method for producing a thermo-fusible substance, wherein
A color forming agent according to the thirty-eighth aspect of the invention, which is represented by X).

[0058]

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(The hydrogen atom of the benzene ring in the formula is a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group,
Isocyanato group, isothiocyanato group, mercapto group,
It may be substituted by a sulfamoyl group, a sulfone group, an amino group, an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue. )

A forty-third aspect of the invention is the color former according to any one of the twenty-fourth to thirty-ninth aspects of the invention, further comprising an isocyanate compound. A forty-first aspect of the invention is the color former according to any one of the twenty-fourth to thirty-ninth aspects of the invention, further comprising an isocyanate compound and an imino compound. A forty-second aspect of the invention is the color former according to any one of the twenty-fourth to forty-first aspects of the invention, further comprising an amino compound. A forty-third aspect of the invention is the color former according to any one of the twenty-fourth to forty-second aspects of the invention, wherein the developer further contains an acidic developer.

A forty-fourth aspect of the invention is that the acidic developer is 2,2-
Bis (4-hydroxyphenyl) propane, 4-isopropyloxyphenyl-4′-hydroxyphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone,
The color former according to the forty-third aspect of the invention, which is at least one selected from 4,4 ′-[oxybis (ethyleneoxy-p-phenylenesulfonyl)] diphenol.

A forty-fifth aspect of the invention is the color former according to any one of the twenty-fourth to forty-fourth aspects of the invention, further comprising a fluorescent dye. A forty-sixth aspect of the present invention is the color former according to any one of the twenty-fourth to forty-fifth aspects of the invention, further comprising a preservative.
A forty-seventh aspect of the present invention is directed to a ureaurethane compound according to any one of the first to fourth aspects of the invention, or a ureaurethane composition according to any one of the fifth to twelfth aspects of the invention, or a twenty-fourth aspect of the invention.
47. A recording material comprising a support, on which a color-forming layer containing the color-forming agent according to any one of items 46 to 46 is provided.

A forty-eighth aspect of the invention is the recording material according to the forty-seventh aspect, wherein a protective layer for the coloring layer is provided on the coloring layer. Forty-ninth aspect of the invention is the recording material according to the forty-eighth aspect of the invention, wherein the protective layer contains a water-soluble polymer. In a fiftieth aspect of the invention, the protective layer contains an inorganic pigment and / or an organic pigment.
50. The recording material according to any one of items 1 to 49.

A fifty-first aspect of the invention is the recording material according to any one of the forty-eighth to fifty-fifth aspects, wherein the protective layer contains a lubricant. A fifty-second aspect of the invention is the recording material according to the forty-seventh aspect, wherein an intermediate layer is provided on a support, and a coloring layer is provided on the intermediate layer. Invention No. 53
(52) The recording material according to the item (52), wherein the intermediate layer contains a water-soluble polymer. Invention 54
The recording material according to any one of Items 52 to 53, wherein the intermediate layer contains an inorganic pigment and / or an organic pigment.

A fifty-fifth aspect of the invention is the recording material according to the forty-seventh aspect, wherein a back coat layer is provided on the back surface of the surface of the support on which the coloring layer is provided. Invention No. 56
A recording material according to item 55, wherein the backcoat layer contains a water-soluble polymer. A fifty-seventh aspect of the invention is the recording material according to any one of the 55-56th aspects of the invention, wherein the back coat layer contains an inorganic pigment and / or an organic pigment.

A fifty-eighth aspect of the present invention is the fifty-fourth to fifty-seventh aspects of the invention wherein at least one selected from a water-soluble polymer and an anionic surfactant is used as a dispersant for the urea urethane compound. A recording material according to any one of the above. A fifty-ninth aspect of the present invention is directed to a polyvinyl alcohol, a modified polyvinyl alcohol, methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalene sulfonate, a polycarboxylic acid ammonium salt, a water-soluble low molecular weight copolymer and
A forty-seventh aspect of the invention wherein at least one selected from the group consisting of sodium ethylhexyl sulfosuccinate is used.
58. The recording material according to any one of the above items.

A 60th aspect of the present invention is characterized in that as the dispersant for the dye precursor, at least one selected from a water-soluble polymer, a nonionic surfactant and an anionic surfactant is used. 60. A recording material according to any one of Items 47 to 59 of the invention. A sixty-first aspect of the invention is a method for dispersing a dye precursor such as methylcellulose, hydroxypropylmethylcellulose, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether sulfate,
60. The recording material according to any one of Items 47 to 59 of the invention, wherein at least one selected from sodium ethylhexylsulfosuccinate is used.

A thirty-second aspect of the invention is the recording material according to any one of the thirty-seventh to sixty-first aspects, wherein the recording material is a thermosensitive recording material. A thirty-second aspect of the invention is the heat-sensitive recording material according to the sixty-second aspect, wherein the urea urethane compound has an average particle size of 0.05 μm or more and 5 μm or less. A sixty-fourth aspect of the invention is that the liquid temperature at the time of grinding the urea urethane compound is 60
The heat-sensitive recording material according to any one of Items 62 to 63, wherein the temperature is not higher than 0 ° C. A 65th invention is the thermosensitive recording material according to any of the 62th to 64th inventions, wherein the pH at the time of grinding the urea urethane compound is 5 to 10. The 66th invention is any of the 62nd to 65th inventions, wherein at least one selected from a water-soluble polymer and an anionic surfactant is used as a dispersant for a heat-fusible substance. The heat-sensitive recording material described in Crab.

The sixty-seventh aspect of the present invention is that a polyvinyl alcohol, a modified polyvinyl alcohol, methylcellulose, hydroxypropylmethylcellulose, condensed sodium naphthalenesulfonate, a polycarboxylate ammonium salt, a water-soluble low molecular weight copolymer and −
The 62nd invention of the present invention characterized in that at least one selected from the group consisting of sodium ethylhexylsulfosuccinate is used.
65. A heat-sensitive recording material according to any one of the above items. A thirty-eighth aspect of the invention is the thermosensitive recording material according to any one of the sixty-sixth to sixty-sixth aspects of the invention, wherein the urea urethane compound and the heat-fusible substance are pulverized simultaneously. Invention 69
The pH of the surface of the support on which the heat-sensitive recording layer of the heat-sensitive recording material is coated is 3 to 9;
8. The heat-sensitive recording material according to any one of 8.

A seventy-seventh aspect of the present invention is that the heat-sensitive coating solution for forming the heat-sensitive recording layer of the heat-sensitive recording material has a pH of 5 to 12 and is coated on a support. And a method for producing a heat-sensitive recording material as described above. Seventh invention
No. 1 of the invention wherein the recording material is a thermosensitive magnetic recording material.
Recording material. A seventy-second aspect of the invention is the seventy-first aspect of the invention, wherein a heat-sensitive recording layer containing a urea urethane compound developer is provided on one surface of the support, and a magnetic recording layer is provided on the other surface. It is a thermosensitive magnetic recording material of the description. A thirty-seventh aspect of the present invention is a ticket which is the thermosensitive magnetic recording material according to any one of the seventy-first to seventy-second aspects. A seventy-fourth aspect of the invention is a ticket voucher which is the thermosensitive magnetic recording material according to any one of the seventy-first and seventy-second aspects.

A seventy-fifth aspect of the present invention is the recording material according to the forty-seventh aspect, wherein the recording material is a label for thermal recording. The 76th invention is the 75th invention wherein the heat-sensitive recording layer containing the urea urethane compound color developer is provided on one surface of the support, and the adhesive layer is provided on the other surface. Is a label for thermal recording. The seventy-seventh aspect of the invention is the seventh aspect of the invention.
6. A heat-sensitive recording label according to 6, wherein a back coat layer is provided between the pressure-sensitive adhesive layer and the support of the heat-sensitive recording label. A thirty-eighth aspect of the invention is a thermal recording label, wherein an intermediate layer is provided between the thermosensitive recording layer and the support of the thermosensitive recording label according to any one of the 76th to 77th aspects of the invention. A seventy-ninth aspect of the present invention is a thermal recording label, wherein a protective layer is provided on the thermal recording layer of the thermal recording label according to any one of the seventy-sixth to seventy-eighth aspects of the invention.

An eighteenth aspect of the invention is the recording material according to the forty-seventh aspect, wherein the recording material is a multicolor heat-sensitive recording material. An eighteenth aspect of the present invention provides the multicolor heat-sensitive recording material according to the eighteenth aspect of the invention, wherein at least two heat-sensitive recording layers are provided on one surface of the support, wherein at least one of the heat-sensitive recording layers comprises a urea urethane compound. A multicolor heat-sensitive recording material comprising a coloring agent. The 82nd invention is the multicolor heat-sensitive recording material according to the 81st invention, wherein an intermediate layer is provided between the heat-sensitive recording layers. In the 83rd invention, two heat-sensitive recording layers each having a different coloring temperature and a different color are formed by laminating on one surface of the support, and the upper or lower heat-sensitive recording layer is provided with a developer or a color-reducing agent. A multicolor heat-sensitive recording material containing a reversible color developer and a urea urethane compound color developer in a lower heat-sensitive recording layer.

An eighty-fourth aspect of the invention is a low-temperature coloring layer in which the two heat-sensitive recording layers are colored at an upper layer at a low temperature and decolored at a high temperature.
The multicolor heat-sensitive recording material according to Item 83, wherein the lower layer is a high-temperature coloring layer that develops color at a high temperature. An eighty-fifth aspect of the invention is an article for laser marking, comprising a heat-sensitive recording layer containing a urea urethane compound developer on the surface of the article. No. 86 of the invention is an article for laser marking, comprising a heat-sensitive recording layer containing a colorless or pale color dye precursor, a urea urethane compound developer, and a recording sensitivity improver on the surface of the article. The 87th aspect of the present invention is the laser marking according to any one of the 85th to 86th aspects of the invention, wherein a protective layer containing an aqueous binder having a glass transition point of 20 to 80 ° C. is provided on the heat-sensitive recording layer. Goods.

The 88th invention is the article for laser marking according to the 86th invention, wherein the recording sensitivity improver is at least one selected from aluminum hydroxide, white mica, wollastonite and kaolin. An eighty-ninth aspect of the invention is the laser marking article according to any one of the eighty-eighth to eighty-eighth aspects of the invention, wherein the laser marking article is a label, a packaging material, and a container. A ninety-ninth aspect of the present invention is a method for producing an article for laser marking, comprising applying a color-forming marking agent containing a urea urethane compound developer to a substrate and drying the coating.

A ninety-first aspect of the present invention is characterized in that a colorless or pale-colored dye precursor, a urea urethane compound developer, and a recording sensitivity improver are applied to a base material, and the resultant is dried. This is a method for producing an article for laser marking. The 92nd of the invention is the 85th to 89th of the invention.
5. A method for marking an article, comprising irradiating a laser beam to the heat-sensitive recording layer of the article for laser marking according to any one of the above. A ninety-third aspect of the invention is a color marking agent comprising a urea urethane compound color developer. A ninety-fourth aspect of the invention is a color-forming marking agent containing a colorless or pale-colored dye precursor, a urea urethane compound developer, and a recording sensitivity improver.

[0076]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The raw materials and starting materials of the urea urethane compound and the urea urethane composition of the present invention may be used alone or in combination of two or more. The first to fourth urea urethane compounds of the present invention have at least one of both a urea group and a urethane group.

In the first to fourth urea urethane compounds of the present invention, an aliphatic compound residue is bonded to the oxygen atom terminal of the urethane group, whereby physical and chemical stability, particularly heat stability, is excellent. A urea urethane compound is obtained. Further, a urea urethane compound can be obtained using a relatively inexpensive material. Furthermore, the alcohol compound, which is the raw material of the aliphatic compound residue at the oxygen atom terminal of the urethane group, can be easily removed even if it remains as unreacted during the synthesis reaction of the urea urethane compound, and a highly pure urea urethane compound can be obtained. can get.

The preferred form of both ends of the urea group differs depending on the size of the molecule. In the urea urethane compound represented by the formula (c), it is necessary that the urea group be bonded to an aromatic compound residue. Preferably, it is an aromatic ring represented by the formula (d). Here, the aliphatic compound residue represented by R in the formula (d) preferably has 1 to 7 carbon atoms.
The following urea urethane compounds (S-1) to (S-6) or (S-36) to (S-41) are preferable because a highly sensitive recording material is obtained.

In the comparatively large urea urethane compounds represented by the formulas (e) to (f), both ends of the urea group are, for example, those represented by the formula (e) in which an aromatic compound residue, a heterocyclic compound residue, an aliphatic Any of compound residues may be used, and formula (f) may be any of an aromatic compound residue and a heterocyclic compound residue. In both equations (e) and (f),
Aromatic compound residues are preferred. The urea group and the urethane group are adjacent via at least one compound residue (hereinafter, such a structural part is referred to as a urea urethane structural part). Preferably, only one compound residue exists between the urethane group and the urea group, and more preferably, the residue is an aromatic ring. In particular, a urea urethane compound represented by the formula (g) is preferable because a highly sensitive recording material is obtained, and the aliphatic compound residue represented by β ₁ in the formula (g) has 2 to 15 carbon atoms. It is more preferable that the number of carbon atoms is 2 to 10, and further, (S-32), (S-34) and
(S-35), (S-67), (S-69), (S-7)
The compound of 0) is preferred.

Although the specific mechanism by which the first to fourth ureaurethane compounds of the present invention have a function as a color developing agent is not clear, it may be due to the interaction between the urea group and the urethane group in the ureaurethane structure. It is guessed. In the formulas (e) to (f), the number of the urea urethane structure parts is two or more, whereas in the urea urethane compound represented by the formula (c) or (d), the number of the urea urethane structure parts is one. May be. At this time, in the urea urethane compound represented by the formula (c) or (d), in order to exhibit a certain function as a color developer, residues at both ends to be bonded to the urea group are most preferably aromatic. Group (e)-(f)
Then, it is conceivable that the residue may not necessarily be an aromatic compound residue.

The urea urethane structure has one molecule per molecule.
The number is preferably 10 to 10, preferably 1 to 5, and more preferably 2 to 4. One molecule of the urea urethane compound may have other urea groups or urethane groups in addition to the urea urethane structure. The aliphatic in the first to fourth aspects of the present invention includes an alicyclic. The first of the present invention
The aliphatic compound residue referred to in 4 is a group bonded by a carbon atom of an aliphatic hydrocarbon moiety in the residue, and the aromatic compound residue is an aromatic compound such as a benzene ring in the residue. It is a group bonded by a ring carbon atom, and a heterocyclic compound residue is a group bonded by a carbon atom forming a heterocyclic ring in the residue.

Preferred substituents for the aliphatic compound residue, the heterocyclic compound residue and the aromatic compound residue include an alkyl group, a cycloalkyl group, a phenyl group, an amide group, an alkoxyl group, a nitro group and a nitrile group. , A halogen atom,
Examples include a formyl group, a dialkylamino group, a toluenesulfonyl group, and a methanesulfonyl group. Further, considering that the urea urethane compound according to the first to fourth aspects of the present invention is used as a color developer or a heat-sensitive recording material, the molecular structure of the urea urethane compound according to the first to fourth aspects of the present invention is The number of aliphatic urethane groups and the total number of urea groups present are 2 or more and 11 or less, preferably 3 or more and 11 or less, more preferably 4 or more and 11 or less, and the ratio of urethane groups to urea groups is 1 : 3 to 3: 1, preferably 1: 2
２2: 1 is more preferable, and 1: 1 is even more preferable. Further, the molecular weight is 5,000 or less, preferably 2,000 or less.

In the heat-sensitive recording material, a compound having a melting point is preferable, and the melting point of the urea urethane compound according to the first to fourth aspects of the present invention is preferably from 40 ° C. to 500 ° C.
C, more preferably from 60C to 300C, even more preferably from 60 to 250C. The method for synthesizing the urea urethane compounds according to the first to fourth aspects of the present invention is not particularly limited, but a method of preparing an urea urethane compound by reacting an isocyanate compound with an alcohol compound and an amine compound is easy and preferable.

That is, equation (c) according to the first aspect of the present invention.
The ureaurethane compound of formula (I) is not limited to a production method. For example, an alcohol compound of the following formula (m), an isocyanate compound of the following formula (n), and an amine compound of the following formula (o) are reacted with, for example, the following reaction formula (A ′). ) Or (B ′).

[0085]

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(Wherein R represents an aliphatic compound residue;
May have a substituent. )

[0087]

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(Wherein A ₁ represents an aromatic compound residue;
A ₁ may have a substituent. )

[0089]

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(Wherein A ₂ represents an aromatic compound residue;
A ₂ may have a substituent. )

[0091]

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[0092]

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The production method of the ureaurethane compound of the formula (d) according to the second aspect of the present invention is not limited. For example, an alcohol compound of the formula (m), an isocyanate compound of the following formula (p) and a compound of the following formula (q) Can be obtained, for example, by reacting according to the following reaction formula (C ′) or (D ′).

[0094]

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(Wherein the hydrogen atom of the benzene ring is an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue or a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group ,
Amino group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanato group, mercapto group, may be substituted by a sulfo group or a halogen atom,
Each residue may have a substituent. )

[0096]

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(Wherein the hydrogen atom of the benzene ring may be substituted by an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, and each residue may have a substituent. good.)

[0098]

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[0099]

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The urea urethane compound of the formula (e) according to the third aspect of the present invention is not particularly limited in the production method. For example, an alcohol compound of the general formula (m), an isocyanate compound of the following general formula (r) and a compound of the following general formula It can be obtained by reacting the amine compound (s) according to, for example, the following reaction formula (E ′) or (F ′).

[0101]

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(In the formula, Y represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, and each residue may have a substituent.)

[0103]

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(In the formula, α ₁ represents an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue having a valence of 2 or more; n represents an integer of 2 or more; May have a substituent.)

[0105]

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[0106]

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The ureaurethane compound of the formula (f) according to the third aspect of the present invention is not particularly limited in the production method. For example, an amine compound of the following general formula (t), an isocyanate compound of the general formula (r) and An alcohol compound of the formula (u)
For example, it can be obtained by reacting according to the following reaction formula (G ′) or (H ′).

[0108]

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(In the formula, Z ₁ represents an aromatic compound residue or a heterocyclic compound residue, and each residue may have a substituent.)

[0110]

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(In the formula, β ₁ represents an aliphatic compound residue which may have a substituent having a valence of 2 or more, and n represents an integer of 2 or more.)

[0112]

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[0113]

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The ureaurethane compound of the formula (g) according to the fourth aspect of the present invention is not limited to the production method, but may be, for example, a compound of the formula (u)
And the isocyanate compound of the formula (p) and the amine compound of the formula (q), for example, according to the following reaction formula (i ′) or (J ′).

[0115]

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[0116]

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The ureaurethane compound of the formula (h) according to the fourth aspect of the present invention is not particularly limited in the production method, but may be, for example, the following formula (XV
It can be obtained by reacting the amine compound of II) with the isocyanate compound of the formula (p) and the alcohol compound of the general formula (m) according to, for example, the following reaction formula (K ′) or (L ′).

[0118]

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(Wherein the hydrogen atom of the benzene ring is converted to an aromatic group)
Compound residue or aliphatic compound residue or heterocyclic compound residue,
Nitro group, hydroxyl group, carboxyl group, nitroso group, nitro
Ryl group, carbamoyl group, ureido group, isocyanato
Group, mercapto group, sulfo group, sulfamoyl group or
May be substituted by a halogen atom.
May have a substituent. γ₁Is -SO_Two-, -O
-,-(S) n-,-(CH _Two) N-, -CO-, -C
ONH-, -NH-, -CH (COOR₁)-, -C
(CF_Three)_Two-, -CR_TwoR_Three-And represented by formula (a)
One selected from the group consisting of any of the groups:

[0120]

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Or R ₁ , R ₂
And R ₃ each represents an alkyl group, and n is 1 or 2. )

[0122]

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[0123]

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The compounds of the formulas (m) to (u) which can be used when synthesizing the ureaurethane compounds represented by the above formulas (c) to (h) will be described in more detail.
Examples of the alcohol compound represented by the general formula (m) include O
Any compound may be used as long as it is an alcohol compound having an H group bonded to a carbon atom of an aliphatic compound. For example, a solvent handbook (published by Kodansha Scientific, ninth printing, 1989)
Alcohols described in p. 327-420, p. 772-817, and methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-
Butanol, pentanol, cyclopentanol, te
rt-amyl alcohol, 2-pentanol, isoamyl alcohol, hexanol, 3-hexanol, cyclohexanol, cyclohexylmethanol, 4-methyl-2-pentanol, heptanol, isoheptanol, octanol, 2-ethyl-1-hexanol, Aliphatic alcohols such as caprylic alcohol, nonyl alcohol, isononyl alcohol, decanol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, and isostearyl alcohol; allyl alcohol; 2-methyl -2-propene-1
-Unsaturated aliphatic alcohols such as all, crotyl alcohol, propargyl alcohol, benzyl alcohol,
Aliphatic alcohols to which aromatic compound residues such as cinnamyl alcohol are bonded, and aliphatic alcohols to which heterocyclic compound residues such as 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol and furfuryl alcohol are bonded , 2-chloroethanol, 1-chloro-3-
Halogenated aliphatic alcohols such as hydroxypropane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether , Ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, Ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether,
Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol monophenyl ether, ethylene glycol, diethylene glycol , Triethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol Diols such as hexylene glycol, 1,9-nonanediol, neopentyl glycol and methylpentanediol; Serine, castor oil, trimethylol propane, trimethylol ethane, hexane triol, pentaerythritol, alpha-methyl glucoside, sorbitol, aliphatic polyols such as shoe closed,
Polyethylene glycol, polypropylene glycol,
Polytetramethylene glycol, adipate-based polyol, epoxy-modified polyol, polyetherester polyol, polycarbonate polyol, polycaprolactonediol, amine-modified polyol, polyhydric alcohol such as glycerin or propylene glycol, alone or in mixture with alkylene such as ethylene oxide and propylene oxide Polyether polyols, acrylic polyols, fluorinated polyols, polybutadiene polyols, polyhydroxy polyols, castor oil-based polyols, polymer polyols, halogen-containing polyols, polyols such as phosphorus-containing polyols obtained by adding an oxide alone or a mixture thereof, N , N-dialkylethanolamine, N, N-dialkylisopropanolamine, N
-Alkyldiethanolamine, N-alkyldiisopropanolamine, triethanolamine, triisopropanolamine, N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine,
Alkanolamines such as N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine. Among the alcohol compounds, monoalcohols having one OH group are preferred, and aliphatic alcohols having 10 or less carbon atoms and glycol ethers are more preferred.

The isocyanate compound of the formula (n) is not particularly limited as long as it is an aromatic isocyanate having two or more isocyanate groups bonded to carbon atoms. For example, p-phenylene diisocyanate M-phenylene diisocyanate, o-phenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6
-Toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 3,3
'-Dimethyl-4,4'-diphenylmethane diisocyanate, triphenylmethane triisocyanate, tris (4-phenyl isocyanate) thiophosphate,
4,4 ', 4 "-triisocyanato-2,5-dimethoxytriphenylamine, 4,4', 4" -triisocyanatotriphenylamine and the like. Further, diisocyanate dimer such as toluene diisocyanate dimer N, N '(4,4'-dimethyl-3,3
'-Diphenyldiisocyanato) uretdione (trade name Desmodur TT) and trimers such as 4,4', 4 '
'-Trimethyl-3,3', 3 "-triisocyanato-2,4,6-triphenylcyanurate may be used.
Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,
3-bis (3-isocyanato-4-methylphenyl) urea or a polyol adduct such as trimethylolpropane adduct of toluene diisocyanate (trade name Desmodur L, trade name Coronate L) or an amine adduct may be used. Also, isocyanate compounds and isocyanate adduct compounds described in JP-A-10-76757 and JP-A-10-95171 (the contents of these publications are incorporated herein by reference). Among them, those having two or more isocyanato groups may be used.

Of these, aromatic isocyanates having an isocyanato group bonded to a benzene ring are preferred.
-Phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,4
-Toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-
Trizine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, triphenylmethane triisocyanate, N, N '(4
4′-dimethyl-3,3′-diphenyldiisocyanato) uretdione (trade name Desmodur TT), 4,
4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,6-triphenylcyanurate, 1,3-bis (3-isocyanato-4-methylphenyl) urea And trimethylolpropane adduct of toluene diisocyanate (trade name Desmodur L, trade name Coronate L) are more preferable, and a particularly preferable example is toluene diisocyanate.
Toluene diisocyanate is preferably 2,4-toluene diisocyanate. In addition, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available and is available at a low cost. It is possible, but this is fine.

The amine compound of the general formula (o) includes aniline, o-toluidine, m-toluidine, p-toluidine,
Toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,
4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol,
m-aminophenol, p-aminophenol, 2,3
-Xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile,
Anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene , O-ethylaniline, o-chloroaniline, m
-Chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline,
N-butylaniline, acetoacetic anilide, trimethylphenylammonium bromide, 4,4'-diamino-3,
3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,
4 'diaminodiphenylmethane, 3,3'-dimethyl-
4,4'-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate , P-aminobenzoic acid n
-Propyl, isopropyl p-aminobenzoate, p-
Butyl aminobenzoate, dodecyl p-aminobenzoate,
Benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino- 4-methylbenzamide,
3-amino-4-methoxybenzamide, 3-amino-
4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5 (N
-Phenylcarbamoyl) aniline, 2-methoxy-5
-[N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2 '
-Chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino)
Aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-
Benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2-
(N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole,
4-aminodiphenyl sulfone, 2-chloro-5-N-
Phenylsulfamoylaniline, 2-methoxy-5
N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline,
2-methoxy-5-benzylsulfonylaniline, 2-
Phenoxysulfonylaniline, 2- (2′-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) ) Phenyl] sulfone, bis [3-methyl-
4- (p-aminophenoxy) phenyl] sulfone,
3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5
'-Dimethoxybiphenyl, 2,2', 5,5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4'-diaminobiphenyl, 2,
2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl -4,4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-
Diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4 ′
-Diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4-diaminodiphenylamine,
4,4'-ethylenedianiline, 4,4'diamino-
2,2′-dimethyldibenzyl, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone,
1,4-bis (4-aminophenoxy) benzene, 1,
3-bis (4-aminophenoxy) benzene, 1,3-
Bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4
-Aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, 3,3 ',
4,4'-tetraaminodiphenyl ether, 3,3
', 4,4'-tetraaminodiphenylsulfone, 3,
3 ', 4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methylenebis-O-toluidine, 4,4'-(p-phenyleneisopropylidene ) -Bis- (2,6-xylysine), o-chloro-p
-Nitroaniline, o-nitro-p-chloroaniline,
2,6-dichloro-4-nitroaniline, 5-chloro-
2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-
Nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, metol, 2,4-diaminophenol,
N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanylic acid, 4B acid, C acid,
2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline,
m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-
Bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, , 4 '
-Diaminostilbene-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthonic acid, tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1, And aromatic amines such as 4-diamino-2,3-dichloroanthraquinone.

Examples of the aromatic isocyanate compound of the formula (p) include 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.
Toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, o-phenylene diisocyanate, and the like. Of these,
Toluene diisocyanate is preferred, and 2,4-toluene diisocyanate is more preferred.

The aromatic amine compound of the formula (q) is not particularly limited as long as it has at least one amino group directly bonded to a carbon atom of a benzene ring. Group residue or aliphatic compound residue or heterocyclic compound residue or hydroxyl group, nitro group,
It may be substituted with a nitrile group, carbamoyl group, sulfamoyl group, carboxyl group, nitroso group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanato group, mercapto group, sulfo group or halogen atom. For example, aniline, o-toluidine, m-
Toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminoacetanilide which is a carboxyl-substituted aniline -Aminobenzoic acid, o-aminophenol which is a hydroxyl-substituted aniline, m-aminophenol, p-aminophenol, 2-amino-4-chlorophenol, and the like, 2,3-xylidine, 2,4-xylidine, 3,4 -Xylidine, 2,6-xylidine, 4-aminobenzonitrile which is a nitrile-substituted aniline, anthranilic acid, p-cresidine, 2,5-dichloroaniline which is a halogen-substituted aniline, 2,6-dichloroaniline, 3,4- Dichloroaniline, 3,5-dichloroaniline, 2,4 - trichloro aniline, o- chloroaniline, m- chloroaniline, p- chloroaniline,
α-naphthylamine, aminoanthracene, o-ethylaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, p-
-Iso-propyl aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o -Aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, and p- ( N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N
-Phenylcarbamoyl) aniline, 2-methoxy-5
-[N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2 '
Carbamoylanilines such as -chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, and 4- Sulfamoylaniline, 3-sulfamoylaniline, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-
Sulfamoylanilines such as N-phenylsulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-amino Diphenyl sulfone, 2
O- which is -methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, nitro-substituted aniline
Chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5
-Chloro-2-nitroaniline, o-nitroaniline,
m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine,
2-amino-5-nitrobenzonitrile, sulfanilic acid, metanylic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline , 2,
Aromatic monoamines such as 3,4-trifluoroaniline, m-aminobenzotrifluoride, 2-amino-3-bromo-5-nitrobenzonitrile, and carboxyl, nitroso, oxyamino, and nitroamino groups Aromatic monoamines having a substituent such as hydrazino group, ureido group, isocyanato group, mercapto group, sulfo group, 4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4′-diaminobenzanilide, 3,
5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, dianisidine, bis [4- (m- Aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3′-dimethoxy-4,
4'-diaminobiphenyl, 3,3'dimethyl-4,4
'-Diaminobiphenyl, 2,2'-dichloro-4,4
'-Diamino-5,5'-dimethoxybiphenyl, 2,
2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,
4'-diaminobiphenyl, 2,2'-dichloro-4,
4'-diaminobiphenyl, 3,3'-dichloro-4,
4'-diaminobiphenyl, 2,2'-dimethyl-4,
4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether,
3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4- Diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4'-
Diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4 -Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy)
Benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl)
Aromatic diamines such as propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, and 3,3'-dichlorobenzidine are exemplified. Among these, preferably aromatic monoamines, more preferably,
Aniline or an aniline derivative is used.

The isocyanate compound of the formula (r) is not particularly limited as long as it has two or more isocyanato groups bonded to carbon atoms. For example, p-phenylene diisocyanate, m- Phenylene diisocyanate, o-phenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4
-Toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-
Trizine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3'-dimethyl-
4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate,
4,4 ', 4 "-triisocyanato-2,5-dimethoxytriphenylamine, 4,4', 4" -triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate, dimer Acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate and the like. Further, diisocyanate dimer, for example, N, N '(4,4'
-Dimethyl-3,3'-diphenyldiisocyanato) uretdione (trade name Desmodur TT) and trimers such as 4,4 ', 4 "-trimethyl-3,3', 3"
-Triisocyanato-2,4,6-triphenylcyanurate and the like. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-
Methylphenyl) urea and polyol adducts, for example, trimethylolpropane adduct of toluene diisocyanate (trade name Desmodur L, trade name Coronate L)
Or an amine adduct. Also, JP-A-10-76
Among the isocyanate compounds and isocyanate adduct compounds described in JP-A-757 and JP-A-10-95171 (the contents of these publications are incorporated herein by reference), isocyanate groups May be two or more.

Of these, an aromatic isocyanate having an isocyanato group bonded to a benzene ring is preferable.
-Phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,4
-Toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-
Trizine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, triphenylmethane triisocyanate, N, N '(4
4′-dimethyl-3,3′-diphenyldiisocyanato) uretdione (trade name Desmodur TT), 4,
4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,6-triphenylcyanurate, 1,3-bis (3-isocyanato-4-methylphenyl) urea And trimethylolpropane adduct of toluene diisocyanate (trade name Desmodur L, trade name Coronate L) are more preferable, and a particularly preferable example is toluene diisocyanate.
Toluene diisocyanate is preferably 2,4-toluene diisocyanate. In addition, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available and is available at a low cost. It is possible, but this is fine.

The amine compound represented by the general formula (s) is not particularly limited as long as it has two or more amino groups. For example, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4 ' -Diaminobenzanilide,
3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, dianisidine, bis [4- ( m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3′-dimethoxy-4, 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5 5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4
'-Diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, , 3'-Diaminodiphenyl ether, 3,4 '
-Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,
4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,
4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4
'-Diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis ( 4-aminophenyl)
Fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4′-bis (4-aminophenoxy) diphenyl, dianisidine, 3,3′-dichlorobenzidine, trizine base, o-phenylenediamine,
aromatic amines such as m-phenylenediamine and p-phenylenediamine; furthermore, guanamine, acetoguanamine, 2,4-diamino-6- [2′-methylimidazolyl- (1)] ethyl-S-triazine, 3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-
Heterocyclic compounds such as triaminopyridine and bis (aminopropyl) piperazine amines, methanediamine, 1,2
-Diaminopropane, 1,3-diaminopropane, 1,
4-diaminobutane, 1,3-diamino-2-hydroxypropane, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-methyl-3,3'-iminobis (propylamine), hexamethylenediamine, bis ( Aminomethyl)
Examples thereof include aliphatic amines such as cyclohexane, isophoronediamine, isopropylidenebis (aminocyclohexane), 4,4′-diaminodicyclohexylmethane, and xylylenediamine. Among the above amine compounds, aromatic amines are preferable, and particularly, the following formula (VIII)
An aniline derivative having at least two amino groups, such as

[0133]

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(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, halogen, an alkyl group, an alkoxy group or an amino group, and X ₁ and X ₂ each independently represent Represents an amino group or a group represented by the formula (b),

[0135]

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Y ₁ represents —SO ₂ —, —O—, — (S) _n —,
_{- (CH 2) n -,} - CO -, - CONH -, - NH-,
—CH (COOR ₁ ) —, —C (CF ₃ ) ₂ —, —CR ₂ R
_3- , any of the groups represented by formula (a),

[0137]

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[0138] Or, the case where it does not exist is shown. R ₁ , R ₂
And R ₃ each represents an alkyl group, and n is 1 or 2. In addition, as the amine compound of the general formula (t), aniline,
o-toluidine, m-toluidine, p-toluidine, o
-Anisidine, p-anisidine, p-phenetidine,
N, N-dimethyl-p-phenylenediamine, N, N-
Diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p -Aminophenol, 2,3-xylysine,
2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline,
6-dichloroaniline, 3,4-dichloroaniline,
3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o
-Ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N
-Ethylaniline, N-propylaniline, N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, acetoacetic anilide, trimethylphenylammonium bromide, 4,4'-diamino-3 , 3'-diethyldiphenylmethane, 4,4'-
Diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, o-phenylenediamine , M-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, p-aminobenzoic acid Isopropyl,
butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide P-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p- [ N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5
-(N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N
-(2'-chlorophenyl) carbamoyl] aniline,
5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,5- Dimethoxy-4-
(N-benzoylamino) aniline, 2-methoxy-4
-(N-benzoylamino) -5-methylaniline, 4
-Sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy -5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2-
(2′-chlorophenoxy) sulfonylaniline, 3-
Anilinosulfonyl-4-methylaniline, bis [4-
(M-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone,
Bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2, 2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ',
5,5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-
Diaminobiphenyl, 2,2'-dichloro-4,4'-
Diaminobiphenyl, 3,3'-dichloro-4,4'-
Diaminobiphenyl, 2,2'-dimethyl-4,4'-
Diaminobiphenyl, 4,4'-thiodianiline, 2,
2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3 '
-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-
Amino-4-chlorophenyl) sulfone, bis (3,4
-Diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3
'-Diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4
'Diamino-2,2'-dimethyldibenzyl, 3,3'
-Diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene ,
9,9-bis (4-aminophenyl) fluorene, 2,
2-bis (4-aminophenoxyphenyl) propane,
4,4'-bis (4-aminophenoxy) diphenyl,
3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminodiphenylsulfone, 3,3 ', 4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, -Phenoxyaniline, 3-phenoxyaniline, 4,4'-methylenebis-O-toluidine, 4,4 '-(p-phenyleneisopropylidene) -bis- (2,6-xylysine), o-chloro-p-nitro Aniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-
Chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2- Amino-5
Nitrobenzonitrile, methol, 2,4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanylic acid, 4B
Acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,
4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3,3′-dichlorobenzidine,
4,4'-diaminostilbene-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthionate, tobias acid, H acid, J acid,
Phenyl J acid, 1,4-diamino-anthraquinone,
Aromatic amines such as 1,4-diamino-2,3-dichloroanthraquinone, 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino -Ε-caprolactam, acetoguanamine, 2,4-diamino-6- [2
'-Methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N-
Heterocyclic compound amines such as (3-aminopropyl) morpholine are exemplified, and among them, aromatic monoamines are preferably used.

The alcohol compound of the general formula (u) is not particularly limited as long as it is a polyol compound having two or more OH groups, but ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, , 2-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, hexylene glycol, 1,9-nonanediol, neo Diols such as pentyl glycol and methylpentanediol, glycerin, castor oil, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, α-methylglucoside, sorbitol, and sucrose, etc. Polyols, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, adipate polyol, epoxy-modified polyol, polyetherester polyol, polycarbonate polyol, polycaprolactonediol, amine-modified polyol, polyhydric alcohol such as glycerin and propylene glycol alone Or a mixture of ethylene oxide, polyether polyol obtained by adding a single or mixture of alkylene oxides such as propylene oxide, acrylic polyol, fluorinated polyol, polybutadiene polyol, polyhydroxy polyol,
Polyols such as castor oil-based polyol, polymer polyol, halogen-containing polyol, phosphorus-containing polyol, N
-Alkyldiethanolamine, N-alkyldiisopropanolamine, triethanolamine, triisopropanolamine, N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine,
Alkanolamines such as N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine are exemplified, and among them, diols, aliphatic polyols, alkanolamines, and polyols having a molecular weight of 2000 or less are preferably used. Can be

The amine compound of the general formula (XVII) includes 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide,
3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, dianisidine, bis [4- ( m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3′-dimethoxy-4, 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'dimethoxybiphenyl, 2,2 ', 5,5 '-Tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4
'-Diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3, 3'-diaminodiphenyl ether, 3,4 '
-Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,
4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,
4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4
'-Diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis ( 4-aminophenyl)
Aromatic diamines such as fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4′-bis (4-aminophenoxy) diphenyl, dianisidine, and 3,3′-dichlorobenzidine; Preferably, γ ₁ is a sulfonyl group or a methylene group.

In order to obtain the urea urethane compounds according to the first to fourth aspects of the present invention, the reactants are mixed and reacted with the isocyanate in an organic solvent or without a solvent, followed by filtration, crystallization, desolvation or the like. The desired product can be obtained by taking out the crystals. In addition, the reaction may be performed by a method in which a substance having two or more groups in one molecule is made into a large excess, and a substance to be reacted with the group is added little by little to this. This allows only one of the two or more groups to react. When adding
It is desirable to stir the system well so that the additives are well dispersed immediately after addition. The same applies to any of the urea urethane compounds exemplified in the present invention. The method is not limited to this, as long as a similar result can be obtained. The reactants may be used alone or in combination depending on the purpose. The solvent may be anything that does not cause a reaction with the isocyanato group and the functional group of the reactant,
Examples include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, ketones, esters and the like. . Particularly, methyl ethyl ketone, toluene, acetone, ethyl acetate, phosphates, and the like, which dissolve the isocyanate and have low solubility of the product, are preferable.
The product obtained by the above-mentioned reaction operation is not necessarily a single product, and may be obtained as a mixture of compounds having different substituent positions.

The following compounds can be exemplified as specific examples of the first to fourth ureaurethane compounds of the present invention. ((S-1) to (S-70))

[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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The urea-urethane compositions according to the fifth to twelfth aspects of the present invention and the urea-urethane compositions produced by the thirteenth to twenty-third production methods of the present invention each have a urethane group (—NHCOO— group) and a urea group in one molecule. Group (-NHCONH
-Group), each having at least one, the total number of which is 2 to 10, and the molecular weight of the urea urethane compound is preferably 50% by weight or more, more preferably 60% by weight or more. , 70% by weight or more. Such a urea urethane composition,
By using together with a colorless or pale color dye precursor,
It can be a coloring agent such as a heat-sensitive recording material or a pressure-sensitive recording material. This coloring agent has an effect that the coloring ability is excellent and the storage stability of printing is excellent.

The urea urethane compound which is a main component of the urea urethane composition has one or more urea groups and urethane groups in one molecule. It is desirable that the urea group and the urethane group are adjacent to each other via at least one compound residue (hereinafter, such a portion is referred to as a urea urethane structure portion). The total number of urethane groups and urea groups is 2 or more and 1
0 or less, preferably 3 or more and 10 or less,
4 or more and 10 or less are more preferable. The ratio of urethane groups to urea groups in one molecule of the urea urethane compound is 1: 3 to
3: 1 is preferable, 1: 2 to 2: 1 is more preferable,
1: 1 is more preferred. The molecular weight of the urea urethane compound is 5,000 or less, more preferably 2,000 or less.

The content of the urea urethane compound in the urea urethane compositions according to the fifth to twenty-third aspects of the present invention is as follows:
50% by weight or more. Such a urea urethane composition can be produced by a relatively simple production method, but has a high ratio of a urea urethane compound capable of exhibiting excellent coloring ability required for a color former and storage performance. , Can exhibit excellent performance. The urea urethane compound may be used alone or as a mixture of two or more kinds including isomers. Further, a mixture of two or more urea urethane compounds including isomers may be used for the purpose of improving color sensitivity and storage performance.

On the other hand, the ureaurethane compounds of the present invention
Dilution with a substance that does not inhibit the effects of the present invention can be arbitrarily performed. Examples of such a diluent include a heat-fusible substance, an acidic developer, an amine compound,
Examples include isocyanate compounds, urea compounds, and urethane compounds. Among these, urea compounds and urethane compounds having a structure similar to that of the urea urethane compound are preferable because the sensitivity can be improved. Further, a compound obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound is preferable. These diluents are preferably contained in an amount of 0.0001 to 50% by weight based on the total weight of the urea urethane compound and the diluent. The content of the diluent is more preferably 40% by weight or less, and further preferably 30% by weight or less, from the viewpoint of exhibiting storage performance. Further, the content of the diluent is more preferably 0.01% by weight or more, and further preferably 1% by weight.
The above conditions are preferable for improving the sensitivity. Further, these diluents may be generated during the synthesis reaction of the urea urethane compound, but when they are added, they are preferably added during the synthesis reaction in order to improve the sensitivity.

For example, in a urea urethane compound developer comprising a urea urethane compound having at least one or more urea groups and at least one urethane group in the molecular structure in total and having a molecular weight of 5,000 or less and a diluent, ,
A urea urethane compound developer containing a diluent in an amount of 0.0001 to 50% by weight. The same effect is obtained by the eighth to twelfth compositions of the present invention and the thirteenth composition of the present invention.
To 23. The composition produced by any one of the production methods described above is also recognized.

The urea urethane compositions according to the fifth to twenty-third aspects of the present invention are useful from the viewpoint of being useful for heat-sensitive recording materials.
A colorless or light-colored solid having a melting point is desirable, and the melting point of the composition is preferably from 40 ° C to 300 ° C, more preferably from 60 ° C to 260 ° C.
In the method for producing a urea urethane composition according to the fifth to twentieth aspects of the present invention, a urethane group is formed from at least one isocyanate group of a polyisocyanate compound and a hydroxyl group of a hydroxy compound, and the remaining polyisocyanate compound A method of forming a urea group from the unreacted isocyanate group of the amino compound and the amino group of the amino compound, or forming a urea group from at least one of the isocyanate group of the polyisocyanate compound and the amino group of the amino compound to form the same polyisocyanate A method of forming a urethane group from the remaining unreacted isocyanato group of the compound and the hydroxyl group of the hydroxy compound is preferred.

When a urethane group is formed from a polyisocyanate compound and a hydroxy compound, the amount of the polyisocyanate compound is made larger than the number of hydroxyl groups, and one molecule of the polyisocyanate compound is bonded to one hydroxyl group of the hydroxy compound to form an isocyanate group. Reacting only one of the groups to leave at least one isocyanate group of the polyisocyanate compound unreacted, and then reacting the remaining unreacted isocyanate group with the amino compound to form a urea group, The urea urethane composition can be obtained efficiently. In this case, the ratio of the number of moles of the polyisocyanate compound / the number of hydroxyl equivalents of the hydroxy compound is 100 /
It is preferable to form a urethane group by reacting at a ratio of 1 to 1/2. Further, the ratio of the number of equivalents of isocyanate groups of the polyisocyanate compound to the number of equivalents of hydroxyl groups of the hydroxy compound is 1
The reaction is preferably performed at 000/1 to 1/1 to form a urethane group.

In order to add a hydroxy compound to the polyisocyanate compound, it is preferable that the hydroxy compound is added little by little and that the polyisocyanate compound always exists in excess in the reaction system in excess of the hydroxyl group. In particular,
When the ratio of the number of moles of the polyisocyanate compound / the number of hydroxyl equivalents of the hydroxy compound is close to 1/1, for example, 5 /
When the reaction is carried out at a ratio of 1 to 1/2, it is preferable to add in this manner. Similarly, when forming a urea group from a polyisocyanate compound and an amino compound, the polyisocyanate compound is added in excess of the amino group, and one molecule of the polyisocyanate compound is added to one amino group of the amino compound. Bonding to react one of the isocyanate groups to form at least one of the polyisocyanate compounds.
The unreacted isocyanato group is left unreacted, and then the remaining unreacted isocyanato group is reacted with a hydroxy compound to form a urethane group, whereby a ureaurethane composition can be obtained efficiently. Also in this case, it is preferable to form a urea group by reacting the polyisocyanate compound in a molar ratio of the amino compound equivalent number of the amino compound of 100/1 to 1/2. Further, it is preferable to form a urea group by reacting the polyisocyanate compound at a ratio of isocyanate group equivalent number / amino compound equivalent number of amino compound of 1000/1 to 1/1.

In order to add an amino compound to the polyisocyanate compound, it is preferred that the amino compound is added little by little and that the polyisocyanate compound always exists in excess in the reaction system in excess of the amino group. In particular, when the ratio of the number of moles of the polyisocyanate compound / the number of equivalents of the amino group of the amino compound is close to 1/1, for example, 5/1 to 1 /
When the reaction is carried out in 2, it is preferable to add in this manner. In the method for producing a urea urethane composition according to the fifth to twentieth aspects of the present invention, the reaction of reacting a polyisocyanate compound with a hydroxy compound to form a urethane group is carried out without using a solvent or a polyisocyanate diluted or dispersed with a solvent. In the nate compound, it is desirable to carry out by adding or dropping or injecting a hydroxy compound diluted or dispersed in a solvent-free or solvent continuously or dividedly, similarly, by reacting a polyisocyanate compound with an amino compound. The reaction for forming a urea group may be performed without a solvent, or an amino compound diluted or dispersed with or without a solvent may be continuously or dividedly added to a polyisocyanate compound diluted or dispersed with a solvent. Alternatively, it may be performed by dropping or pouring. Furthermore, a hydroxy compound having low reactivity with the polyisocyanate compound is allowed to coexist in the polyisocyanate compound, and the amino compound diluted or dispersed with or without a solvent or a solvent is continuously or dividedly added or dropped or injected. May be performed.

The above production method in which a hydroxy compound or an amino compound is added little by little to a polyisocyanate compound is particularly effective in the reaction step of producing a urea urethane composition, in which at least one of the isocyanate groups in the polyisocyanate compound molecule is used. It is preferable to form a urethane group or a urea group by reacting another isocyanato group with a hydroxy compound or an amino compound while leaving one. Further, a hydroxy compound having two or more hydroxyl groups or two or more amino groups This is preferable when the amino compound having the polyisocyanate compound is reacted with a polyisocyanate compound having two or more isocyanate groups.

In the above reaction, it is desirable to stir the system well so that the hydroxy compound or amino compound added or dropped or injected into the polyisocyanate is immediately and sufficiently dispersed. It is desirable to adjust the stirring speed in the reaction vessel, select a stirring blade, install a baffle plate, and the like to sufficiently stir the reaction system. It is preferable to use the raw material polyisocyanate compound, hydroxy compound, and amino compound that do not contain water. It is preferably at most 0.5% by weight, more preferably 0.5% by weight.
It is preferably at most 2% by weight.

It is preferable that the urethane group forming reaction and the urea group forming reaction be performed separately and sequentially. If they are performed simultaneously, the content of the urea urethane compound in the urea urethane composition decreases, which is not preferable. Further, the urethane group forming reaction and the urea group forming reaction are preferably performed continuously. In the method of the present invention, there is no need for intermediate separation and purification steps,
By continuously performing the two steps, the production can be simplified. In the production of the urea urethane compositions according to the fifth to twentieth aspects of the present invention, when a polyisocyanate adduct of a polyisocyanate and a hydroxy compound, which is an isocyanate already having a urethane group in the molecule, is used as an amino compound Is reacted to obtain a urea urethane composition. In this case, the reaction is carried out at an isocyanato group / amino group equivalent ratio of 2/1 to 1/100 to form a urea group. Preferably, it is removed.

In the production of the ureaurethane compositions according to the fifth to twentieth aspects of the present invention, when a polyisocyanate adduct of a polyisocyanate and an amino compound, which is an isocyanate having a urea group in the molecule, is used. A urea urethane composition can be obtained by reacting this with a hydroxy compound. In this case, a urethane group is formed by reacting the isocyanato group / hydroxyl equivalent ratio at 2/1 to 1/100 to form a urethane group. Preferably, the hydroxy compound is removed.

In the production of the ureaurethane compositions according to the fifth to twentieth aspects of the present invention, when a solvent is used in the reaction, there is no particular limitation as long as it does not react with an isocyanato group or the like. Hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, ketones, acetates, phosphates and the like. .
Particularly, methyl ethyl ketone, acetone, toluene, ethyl acetate and the like, which dissolve the isocyanate and have low solubility of the product, are preferable. When dissolving power is required, phosphate esters, especially trimethyl phosphate, are preferred. When a solvent is used, the solvent may be reused or the urea group formation reaction and the urethane group formation reaction may be easily performed continuously. However, if necessary, a plurality of types of solvents may be used in combination.

In the production of the ureaurethane compositions according to the twenty-first to twenty-third aspects of the present invention, Hild
It is preferable to use a solvent having a solubility parameter value of ebrand solvent of 7 to 15. Further, those having a solubility parameter value of 7 to 8.8 are particularly preferable because they dissolve the reaction raw material and have low solubility of the product. Further, by using a polar solvent having a solubility parameter value of 8.9 to 21 in combination with a solvent having a solubility parameter value of 7 to 8.8, the dissolution state of the reaction raw material and the product is controlled, and urea is obtained in high yield. A urethane composition can sometimes be obtained, which is preferable. In this case, when a hydroxy compound which is a urethane group-forming raw material is used as the polar solvent to be used in combination, the hydroxy compound is consumed in the reaction, and a solvent having a solubility parameter value of 7 to 8.8 is used alone. This is advantageous and preferable in the reuse of the solvent. As the hydroxy compound, a phenolic compound is preferable, and phenol is particularly preferable.

The solubility parameter (δ) according to the present invention is defined by the following equation. δ = (ΔE / V) (where ΔE is the molecular cohesion energy (cal / mol) and V
Indicates a molecular volume (ml / mol). That is, δ corresponds to the square root of the cohesive energy density. The solubility parameter (δ) according to the present invention is, for example,
One example is described in p39 of the Solvent Handbook (Kodansha Scientific, 9th edition, 1989).

In the production of the urea urethane compositions according to the twenty-first to twenty-third aspects of the present invention, in particular, after a hydroxy compound or an amino compound is added little by little to a polyisocyanate compound to form a urethane group or a urea group,
Subsequently, it is preferable to obtain an urea urethane composition by adding an amino compound or a hydroxy compound that only reacts with the remaining isocyanate groups. In this case, a urea urethane composition can be obtained only by distilling off the reaction solvent, which is advantageous in productivity, reuse of the solvent, and the like.

The urea urethane compositions according to the twenty-first to twenty-third aspects of the present invention may contain a diluent generated during the reaction in addition to the urea urethane compound. Further, as an example of a more preferable production method, the reaction can be substantially performed without a solvent by using a hydroxy compound as a urethane group-forming raw material as a reaction solvent. In this case, after the amino compound is added little by little to the polyisocyanate compound dissolved in the hydroxy compound to form a urea group, a catalyst is subsequently added, and the hydroxy compound already added as a solvent is reacted to make the urea urethane A compound can be obtained. In this case, the entire reaction liquid can be made into a urea urethane composition by using an equivalent amount of the hydroxy compound to the isocyanate group remaining after the formation of the urea group.

The reaction temperature at which the polyisocyanate is reacted with the hydroxy compound and / or the amino compound to form a urethane group and / or a urea group is 0 ° C. to 300 ° C.
° C, preferably 5 ° C to 200 ° C, and 10 ° C to 150 ° C.
C is more preferred. The reaction temperature is appropriately adjusted according to the selected polyisocyanate compound, hydroxy compound, and amino compound. It is also possible to carry out urethane group formation and urea group formation at different temperatures suitable for each.

A catalyst may be used in the reaction of reacting the polyisocyanate with a hydroxy compound and / or an amino compound to form a urethane group and / or a urea group. Examples of the catalyst include tertiary amine compounds such as triethylamine, hexamethylenetetramine, and 1,4-diazabicyclo (2,2,2) octane; organic acid tin salts such as dibutyltin dilaurate; and 2-ethylhexanoic organic metal salts. And acetylacetone-based organic metal salts, gluconic acid-based organic metal salts, and the like. The catalyst concentration is usually from 1 to 10,000 based on the isocyanate compound.
ppm, preferably 10 to 2000 ppm.
Of these, tertiary amine compounds are preferred.

By repeating the steps of the production method of the present invention a plurality of times using an amino compound having two or more amino groups or a hydroxy compound having two or more hydroxy groups, the urea urethane structure Is 1
A urea urethane composition containing a plurality of urea urethane compounds in the molecule can be obtained. Since the reaction yield in each step can be made sufficiently high, in the production method of the present invention, a high-performance ureaurethane composition can be obtained relatively easily.

The polyisocyanate compound used in the fifth to fifth aspects of the present invention is not particularly limited as long as it has two or more isocyanate groups bonded to carbon atoms.
-Phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,5
-Dimethoxybenzene-1,4-diisocyanate,
2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethanediisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenyl isocyanate) thiophosphate, 4,4 ′, 4 ″ -triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ′, 4 ″ -triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate, diisocyanate diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methyl Cyclohexane diisocyanate and the like. Further, diisocyanate dimer such as toluene diisocyanate dimer N, N '(4,
4'-dimethyl-3,3'-diphenyldiisocyanato) uretdione (trade name Desmodur TT) and trimers such as 4,4 ', 4 "-trimethyl-3,3',
3 ''-triisocyanato-2,4,6-triphenylcyanurate may be used. Further, water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea and polyol adducts such as trimethylolpropane adduct of toluene diisocyanate (trade name: Dess) Module L, trade name Coronate L), amine adduct, and the like may be used. Also, Japanese Patent Application Laid-Open No. Hei 10
Of the isocyanate compound and the isocyanate adduct compound described in JP-A-76757 and JP-A-10-95171 (the contents of these publications are incorporated herein by reference). It may have two or more groups. They are,
They may be used alone or in combination of two or more.

Among them, aromatic polyisocyanates having an isocyanate group bonded to a benzene ring, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,4-toluene diisocyanate , 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, triphenylmethane triisocyanate, N, N '(4 , 4'-
Dimethyl-3,3'-diphenyldiisocyanato) uretdione (trade name Desmodur TT), 4,4 ', 4
"" -Trimethyl-3,3 ', 3 "-triisocyanato-2,4,6-triphenylcyanurate, 1,3
-Bis (3-isocyanato-4-methylphenyl) urea and trimethylolpropane adduct of toluene diisocyanate (trade name Desmodur L, trade name Coronate L) are preferred, and toluene diisocyanate is particularly preferred. it can. Toluene diisocyanate is preferably 2,4-toluene diisocyanate. In addition, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available and is available at a low cost. It is possible, but this is fine.

Examples of the hydroxy compound which reacts with the polyisocyanate compound to form a urethane group include a phenol compound and an alcohol compound. Examples of the phenol compound include phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2-
Cyclohexylphenol, 2-allylphenol, 4
-Indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane,
2,2-bis (hydroxyphenyl) pentane, 2,2
-Bis (hydroxyphenyl) heptane, catechol,
3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxy Phenyl) benzyl acetate,
Bis (4-hydroxyphenyl) sulfone, bis (3-
Methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-
Methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone,
Bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, Bis (2-methyl-
3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether,
4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis ( 4-hydroxy-3-methylphenyl)
Sulfide, bis (4- (2-hydroxy) phenyl)
Sulfone, 2,4-dihydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate,
-Hydroxybenzoic acid (4'-chlorobenzyl), 1,
Ethyl 2-bis (4'-hydroxybenzoate), 1,5
-Bis (4'-hydroxybenzoic acid) pentyl, 1,6
-Bis (4'-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, -N-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-
Octyloxycarbonylaminosalicylic acid, 4-n-
And octanoyloxycarbonylaminosalicylic acid.

Among the above phenol compounds, phenol, phenol derivatives represented by the following formula (w) and phenol derivatives represented by the following formula (XV)
Diphenol compounds such as I) are preferred.

[0178]

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(Where the hydrogen atom of the benzene ring is an alkyl group, a cycloalkyl group, a phenyl group, an amide group, an alkoxyl group, a nitro group, a nitrile group, a halogen atom, a formyl group, a dialkylamino group, a toluenesulfonyl group, (It may be substituted with a methanesulfonyl group or an OH group.)

[0180]

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(In the formula, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, but is preferably a hydroxyl group, a nitro group, A nitrile group, a carbamoyl group,
It may be substituted by a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanato group, a mercapto group, a sulfo group or a halogen atom. Further, each residue may have a substituent. δ is -SO
_2- , -O-,-(S) _n -,-(CH2) _n- , -CO
-, - CONH -, - NH -, - CH (COOR 1)
—, —C (CF ₃ ) ₂ — and —CR ₂ R ₃ — represent one selected from the group consisting of-, -C (CF ₃ ) ₂ -and -CR ₂ R _3- , or absent. R1, R
2 and R3 each independently represent an alkyl group, and n is 1 or 2. )

It is to be noted that the aliphatics referred to in Nos. 5 to 23 of the present invention include alicyclics. In addition, the fifth to twenty-third of the present invention
The aliphatic compound residue referred to in the above is a group bonded by a carbon atom of an aliphatic hydrocarbon moiety in the residue, and the aromatic compound residue is an aromatic ring such as a benzene ring in the residue. And a heterocyclic compound residue is a group that is bonded to a carbon atom forming a heterocyclic ring in the residue. Preferred substituents of the aliphatic compound residue, the heterocyclic compound residue, and the aromatic compound residue include an alkyl group, a cycloalkyl group, a phenyl group, an amide group, an alkoxyl group, a nitro group, a nitrile group, and a halogen atom. , A formyl group, a dialkylamino group, a toluenesulfonyl group, and a methanesulfonyl group.

Examples of the alcohol compound include compounds in which an OH group is bonded to a carbon atom of an aliphatic compound. For example, pp. 327 to 42 of Solvent Handbook (published by Kodansha Scientific, ninth print, 1989).
0, alcohols described in p772 to 817,
For example, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, se
c-butanol, tert-butanol, pentanol, cyclopentanol, tert-amyl alcohol, 2-pentanol, isoamyl alcohol, hexanol, 3-hexanol, cyclohexanol, cyclohexylmethanol, 4-methyl-2-pentanol, heptanol , Isoheptanol, octanol,
2-ethyl-1-hexanol, caprylic alcohol,
Aliphatic alcohols such as nonyl alcohol, isononyl alcohol, decanol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, and isostearyl alcohol; allyl alcohol; 2-methyl-2- Unsaturated aliphatic alcohols such as propen-1-ol, crotyl alcohol and propargyl alcohol; aliphatic alcohols to which aromatic compound residues such as benzyl alcohol and cinnamyl alcohol are bonded; 2-pyridinemethanol; Aliphatic alcohols to which heterocyclic compound residues such as pyridine methanol, 4-pyridine methanol, and furfuryl alcohol are bonded;
Halogenated aliphatic alcohols such as -chloroethanol, 1-chloro-3-hydroxypropane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene Glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethyl Glycol monohexyl ether, diethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, propylene glycol monophenyl ether , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol monophen Glycol ethers such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, Diols such as 5-pentanediol, 1,6-hexanediol, hexylene glycol, 1,9-nonanediol, neopentyl glycol, methylpentanediol, glycerin, castor oil, trimethylolpropane, trimethylolethane, hexanetriol , Pentaerythritol, α-methylglucoside, sorbitol, aliphatic polyols such as sucrose, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Polyols, adipate-based polyols, epoxy-modified polyols, polyetherester polyols, polycarbonate polyols, polycaprolactone diols, amine-modified polyols, polyhydric alcohols such as glycerin and propylene glycol alone or in mixtures of ethylene oxide and alkylene oxides such as propylene oxide. Polyether polyol obtained alone or by adding a mixture, acrylic polyol, fluorinated polyol, polybutadiene polyol, polyhydroxy polyol,
Castor oil-based polyols, polymer polyols, halogen-containing polyols, polyols such as phosphorus-containing polyols,
N, N-dialkylethanolamine, N, N-dialkylisopropanolamine, N-alkyldiethanolamine, N-alkyldiisopropanolamine, triethanolamine, triisopropanolamine, N, N, N ', N'-tetrakis (2- Alkanolamines such as (hydroxyethyl) ethylenediamine and N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine.

Among the above alcohol compounds, one having 1 carbon atom
0 or less aliphatic alcohols, glycol ethers,
Diols, aliphatic polyols, polyols having a molecular weight of 2000 or less, and alkanolamines are preferred. These alcohol compounds and phenol compounds may be used alone or in combination of two or more.

The amino compound which forms a urea group by reacting with the polyisocyanate compound may be any compound having an amino group bonded to a carbon atom.
For example, aniline, o-toluidine, m-toluidine, p
-Toluidine, o-anisidine, p-anisidine, p-
Phenetidine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine,
2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol,
2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline , 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,
5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butyl Aniline, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, acetoacetic anilide, trimethylphenylammonium bromide,
4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether,
3,3'-dichloro-4,4'diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, o-phenylenediamine,
m-phenylenediamine, p-phenylenediamine, 2
-Chloro-p-phenylenediamine, dianisidine, p
-Methyl aminobenzoate, ethyl p-aminobenzoate,
n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o
-Aminobenzophenone, m-aminoacetophenone,
p-aminoacetophenone, m-aminobenzamide,
o-aminobenzamide, p-aminobenzamide, p
-Amino-N-methylbenzamide, 3-amino-4-
Methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p-
(N-phenylcarbamoyl) aniline, p- [N-
(4-chlorophenyl) carbamoyl] aniline, p-
[N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl)
Aniline, 2-methoxy-5- [N- (2'-methyl-
3'-chlorophenyl) carbamoyl] aniline, 2-
Methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2,5 -Diethoxy-4- (N-benzoylamino) aniline, 2,5
-Dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5
-Methylaniline, 4-sulfamoylaniline, 3-
Sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-N -Phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2 -Phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-amino Phenoxy) phenyl] sulfone, bis [ -Methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4
'-Diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, , 3'-Diaminodiphenyl ether, 3,4 '
-Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,
4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,
4-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4 '
-Diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4 -Aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, 3,3 ', 4,4'-tetraaminodiphenyl ether, 3, 3 ', 4,4'-tetraaminodiphenyl sulfone, 3,3', 4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4 '
-Methylenebis-O-toluidine, 4,4 '-(p-phenyleneisopropylidene) -bis- (2,6-xylidine), o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2, 6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-
Nitroaniline, p-nitroaniline, 2-methyl-4
-Nitroaniline, m-nitro-p-toluidine, 2-
Amino-5-nitrobenzonitrile, methol, 2,4
-Diaminophenol, N- (β-hydroxyethyl)
-O-aminophenol sulfate, sulfanilic acid, metanylic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, , 3,4-
Trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2- Methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, 4,4'-diaminostilbene-2,2 '
Disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthionate, tobias acid,
Aromatic amines such as H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2,3-dichloroanthraquinone, and 3-amino-1,
2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2,4-diamino-
6- [2'-methylimidazolyl- (1)] ethyl-S
Triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1
Heterocyclic compounds such as -amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine, amines, methylamine, ethylamine, dimethylamine; Diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine , Di-2
-Ethylhexylamine, 3- (dibutylamino) propylamine, t-butylamine, propylamine, 3-
(Methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methyl Cyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-
1-propanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3-diamino-2-
Examples thereof include aliphatic amines such as hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, and hexamethylenediamine.

Further, among the above-mentioned amino compounds, aromatic amines are preferable, and particularly, the following formula (z) or (VII)
An aniline derivative having at least one amino group as in I) is preferable.

[0187]

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(Wherein R ₁ and R ₂ each independently represent hydrogen, halogen, an alkyl group, an alkoxy group or an amino group)

[0189]

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(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, halogen, an alkyl group, an alkoxy group or an amino group, and X ₁ and X ₂ each independently represent Represents an amino group or a group represented by the formula (b),

[0191]

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Y ₁ represents —SO ₂ —, —O—, — (S) _n —,
_{- (CH 2) n -,} - CO -, - CONH -, - NH-,
—CH (COOR ₁ ) —, —C (CF ₃ ) ₂ —, —CR ₂ R
_3- , any of the groups represented by formula (a),

[0193]

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[0194] Or, the case where it does not exist. R ₁ , R ₂
And R ₃ each represents an alkyl group, and n is 1 or 2. These amine compounds may be used alone or in combination of two or more. The urea urethane compound as a developer according to the 24th to 25th aspects of the present invention has a urea group (—NHC
An ONH-group) and a urethane group (-NHCOO- group).

It has been known that a compound having a urea group exhibits a color developing effect, but it is not practical because of low color density and low storage stability. However, surprisingly, a urea urethane compound in which a urea group and a urethane group are simultaneously present in one molecule is an excellent colorless or light-colored dye precursor, and a color former containing both of them is used. The recording material has a high color density and excellent storage stability. The mechanism by which such a urea urethane compound exhibits an excellent color developing effect is unknown, but is presumed to be due to the interaction between a urea group and a urethane group in the molecule.

The urea urethane compound as a developer according to the twenty-fourth to twenty-fifth aspects of the present invention has a urea group (—NHC
Any compound may be used as long as it has both an ONH-group) and a urethane group (-NHCOO-group), but is preferably an aromatic compound or a heterocyclic compound. Further, it is preferable that an aromatic compound residue or a heterocyclic compound residue is directly bonded to both ends of a urea group and a urethane group. More preferably, in addition to a urea group (-NHCONH- group) and a urethane group (-NHCOO- group), a sulfone group (-SO ₂ -group) or an amide group (-NHCO- group) in the molecule is more preferable.
Alternatively, it is desirable that the isopropylidene group (—C (CH 3) ₂ — group) be present without directly bonding to the urea group.

The molecular weight of the urea urethane compound is 5
It is preferably 2,000 or less, more preferably 2,000 or less. The total number of urea groups and urethane groups in the urea urethane compound is preferably 20 or less, and more preferably 10 or less. Further, the ratio of the urea group to the urethane group in the molecular structure of the urea urethane compound is preferably 1: 3 to 3: 1, and particularly preferably 1: 2 to 2: 1. In the heat-sensitive recording material, a urea urethane compound having a melting point is preferable, and the melting point is preferably in the range of 40 ° C. to 500 ° C., particularly preferably in the range of 60 ° C. to 300 ° C.
The method for synthesizing the urea urethane compound as a developer according to the twenty-fourth to twenty-fifth aspects of the present invention is not particularly limited as long as a urea group (-NHCONH- group) and a urethane group (-NHCOO- group) are generated. However, a method of preparing the isocyanate compound by reacting the compound with an OH group-containing compound and an amine compound is easy and preferable.

That is, the urea urethane compound as a color developer according to the present invention starts with an isocyanate having at least two or more isocyanate groups, and leaves at least one isocyanate group of the isocyanate other than the isocyanate group. The group can be reacted with an OH group-containing compound to form a urethane group, and then the remaining isocyanate group can be reacted with an amine compound to form a urea group. Alternatively, a urea group may be formed by first reacting an isocyanate group with an amine compound, and then a urethane group may be formed by reacting the remaining isocyanate group with an OH group-containing compound.

The starting isocyanate is not particularly limited as long as it has two or more isocyanate groups.
For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-
Toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole −
3,6-diisocyanate, 3,3′-dimethyl-4,
4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
Triphenylmethane triisocyanate, tris (4-
Phenyl isocyanate) thiophosphate, 4,4
', 4 "-triisocyanato-2,5-dimethoxytriphenylamine, 4,4', 4" -triisocyanatotriphenylamine, meta-xylylene diisocyanate, lysine diisocyanate, diisocyanate diisocyanate And isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate and the like. Further, diisocyanate dimers, for example, N, N '(4,4'-dimethyl-3,3'-diphenyldiisocyanato) uretdione (trade name Desmodur TT) which is a dimer of toluene diisocyanate, A trimer, for example, 4,4 ′, 4 ″ -trimethyl 3,3 ′, 3 ″ -triisocyanato-2,4,6-triphenyl cyanurate may be used. Further, water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, for example, 1,3-bis (3-isocyanato-4-methylphenyl) urea and polyol adducts, for example, trimethylolpropane adduct of toluene diisocyanate (products) It may be a name death module L) or an amine adduct. Further, among the isocyanate compounds and isocyanate adduct compounds described in Japanese Patent Application Nos. 8-225445 and 8-250623, those having two or more isocyanate groups may be used.

A particularly preferred example is toluene diisocyanate. As the toluene diisocyanate, 2,4-toluene diisocyanate is preferable, and in addition, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available and is available at a low cost. It is possible to do this, but this is also acceptable.

The amine compound for forming a urea group by reacting with an isocyanate which is a starting material of a urea urethane compound as a color developer may be any compound having an amino group, for example, aniline, o -Toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-phenylenediamine,
N, N-diethyl-p-phenylenediamine, 2,4-
Dimethoxyaniline, 2,5-dimethoxyaniline,
3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-
Aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine,
2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4 , 5-Trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-
Butylaniline, N, N-diglycidylaniline, N,
N-diglycidyl-o-toluidine, acetoacetic anilide, trimethylphenylammonium bromide, 4,4'-
Diamino-3,3'-diethyldiphenylmethane, 4,
4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-
Dichloro-4,4'diaminodiphenylmethane, 3,3
'-Dimethyl-4,4'-diaminodiphenylmethane,
Trizine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-
p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate Benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N
-Methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-
Amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-
5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N
-(2'-chlorophenyl) carbamoyl] aniline,
5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,5- Dimethoxy-4-
(N-benzoylamino) aniline, 2-methoxy-4
-(N-benzoylamino) -5-methylaniline, 4
-Sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy -5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2-
(2′-chlorophenoxy) sulfonylaniline, 3-
Anilinosulfonyl-4-methylaniline, bis [4-
(M-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone,
Bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2, 2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ',
5,5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-
Diaminobiphenyl, 2,2'-dichloro-4,4'-
Diaminobiphenyl, 3,3'-dichloro-4,4'-
Diaminobiphenyl, 2,2'-dimethyl-4,4'-
Diaminobiphenyl, 4,4'-thiodianiline, 2,
2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3 '
-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-
Amino-4-chlorophenyl) sulfone, bis (3,4
-Diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3
'-Diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4
'Diamino-2,2'-dimethyldibenzyl, 3,3'
-Diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene ,
9,9-bis (4-aminophenyl) fluorene, 2,
2-bis (4-aminophenoxyphenyl) propane,
4,4'-bis (4-aminophenoxy) diphenyl,
3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminodiphenylsulfone, 3,3 ', 4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, -Phenoxyaniline, 3-phenoxyaniline, 4,4'-methylenebis-O-toluidine, 4,4 '-(p-phenyleneisopropylidene) -bis- (2,6-xylysine), o-chloro-p-nitro Aniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-
Chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2- Amino-5
Nitrobenzonitrile, methol, 2,4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanylic acid, 4B
Acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,
4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine,
Dianisidine, 3,3'-dichlorobenzidine, 4,4
'-Diaminostilbene-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine,
Sodium naphthionate, tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-
Aromatic amines such as diamino-2,3-dichloroanthraquinone, 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam , Acetoguanamine, 2,4-diamino-6- [2'-methylimidazolyl- (1)] ethyl-S-triazine, 2,
3-diaminopyridine, 2,5-diaminopyridine,
Heterocyclic compounds such as 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, and N- (3-aminopropyl) morpholine Amines,
Methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine,
2-ethylhexylamine, ethanolamine, 3-
(2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, t
-Butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4
-Diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine,
2-bromoethylamine, 2-methoxyethylamine,
2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine And aliphatic amines such as hexamethylenediamine.

Further, among the above-mentioned amine compounds, an aniline derivative having at least one amino group represented by the following formula (VIII) is particularly preferred.

[0203]

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(Wherein, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, halogen, an alkyl group, an alkoxy group or an amino group, and X ₁ and X ₂ each independently represent Represents an amino group or a group represented by the formula (b),

[0205]

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Y ₁ represents —SO ₂ —, —O—, — (S) _n —,
— (CH ₂ ) _n —, —CO—, —CONH—, any of the groups represented by the formula (a),

[0207]

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[0208] Or, the case where it does not exist is shown. n is 1 or 2
It is. As the OH group-containing compound that reacts with an isocyanate to form a urethane group, any compound having an OH group may be used. Examples thereof include phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, and resorcinol. , P-tert-butylphenol, p-tert-octylphenol,
2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p
-Nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane,
2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, bis ( 4-hydroxyphenyl) butyl acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-) (Hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-isopropyl Oxyphenyl- '-Hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4' -Isopropoxydiphenyl sulfone, bis (2
-Methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxy Phenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4- (2-hydroxy)
Phenyl) sulfone, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, 4-
Methyl hydroxybenzoate, benzyl 4-hydroxybenzoate, (4′-chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis (4′-hydroxybenzoate), 1,5-bis (4′-hydroxy Pentyl benzoate, hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (benzyloxy) Phenol, 4
-Hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-
Phenols such as n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid. . However, those having an amino group are not preferred as these phenols. Since the amino group has a higher reactivity with the isocyanate group than the OH group, the amino group reacts with the isocyanate group first,
In some cases, it is difficult to obtain the desired compound.

Also, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, 2-pentanol, 3-hexanol Tert-butanol, tert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, phenyl cellosolve, furfuryl alcohol, cyclo Hexanol, cyclohexylmethanol,
Alcohols such as cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin, glycerol, polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol, polycarbonate polyol Polyether polyols such as polycaprolactone diol, phenolic polyol and amine-modified polyol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexaneglycol, 1,9-nonanediol, Lil polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyols, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol,
Polyols such as polymer polyols, methylpentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, α-methylglucoside, sorbitol, and souce rose.

As the urea urethane compound as a developer according to the twenty-fourth to twenty-fifth aspects of the present invention, the number of urea groups (A) and the number of urethane groups (B) in the molecular structure satisfy the following formula: Is preferred. 10 ≧ (A + B) ≧ 3 (where A and B are integers equal to or greater than 1)
≧ (A + B) ≧ 3 (where A and B are integers of 1 or more)
The urea urethane compound that satisfies the above condition has at least one or more urea group (—NHCONH— group) and at least one urethane group (—NHCOO— group) in the molecular structure, respectively, and the total number of the urea group and the urethane group is 3 or more; It is a compound present in 10 or less.

Heretofore, such a compound has not been known and is a completely novel compound. This novel compound is useful for a recording material using recording energy such as heat and pressure. When the number of urea groups (A) and the number of urethane groups (B) are expressed by the following formula: 10 ≧ (A + B) ≧ 3 (where A and B
Is an integer of 1 or more), the synthesis method of the urea urethane compound is a urea group (-NHCONH- group) and a urethane group (-NHCOO-
Group) and the total number of urea groups and urethane groups is 3 to 10
The method is not particularly limited as long as the method is such that it is formed as follows. However, a method of making an isocyanate compound with an OH group-containing compound and an amine compound is easy and preferable.

That is, the urea urethane compound as a color developer according to the twenty-fourth to twenty-fifth aspects of the present invention uses, for example, an isocyanate having at least two or more isocyanate groups as a starting material, and at least one of the isocyanates is used. Leaving other groups with other isocyanato groups
Reacting with an H group-containing compound to form a urethane group,
Next, the remaining isocyanato groups of the two molecules of the urethane compound are reacted with each other with water to bond them, whereby a urea urethane compound having a total number of urea groups and urethane groups of at least 3 can be obtained.

Also, for example, an isocyanate having at least two or more isocyanate groups is used as a starting material,
An urethane group is formed by reacting another isocyanate group with an OH group-containing compound while leaving at least one isocyanate group of the isocyanate, and then an amine compound having the remaining isocyanate group and two or more amino groups. To form a urea group, and further reacting the remaining amino group with an isocyanate compound, whereby a urea urethane compound having a total number of urea groups and urethane groups of at least 3 can be obtained.

Also, first, a urea group is formed by reacting an isocyanate group with an amine compound, and then, a urethane group is formed by reacting the remaining isocyanate group with an OH group-containing compound having two or more OH groups. Then, by further reacting the isocyanate compound, a urea urethane compound having a total number of urea groups and urethane groups of at least 3 can be obtained. At this time, an isocyanate compound having two or more isocyanate groups is used as an isocyanate to be reacted last, and an OH-containing compound having a remaining isocyanate group and two or more OH groups or an amino acid having two or more amino groups is used. By sequentially repeating the operation of reacting the compound, a urea urethane compound having a total number of urea groups and urethane groups of 3 to 10 can be obtained.

The starting material isocyanate is not particularly limited as long as it has two or more isocyanate groups.
For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-
Toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole −
3,6-diisocyanate, 3,3′-dimethyl-4,
4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
Triphenylmethane triisocyanate, tris (4-
Phenyl isocyanate) thiophosphate, 4,4
', 4 "-triisocyanato-2,5-dimethoxytriphenylamine, 4,4', 4" -triisocyanatotriphenylamine, meta-xylylene diisocyanate, lysine diisocyanate, diisocyanate diisocyanate And isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate and the like.

Further, diisocyanate dimers, for example, N, N 'which is a dimer of toluene diisocyanate
(4,4'-dimethyl-3,3'-diphenyldiisocyanato) uretdione (trade name Desmodur TT) or a trimer such as 4,4 ', 4 "-trimethyl-3,3
', 3''-triisocyanato-2,4,6-triphenylcyanurate and the like. Further, water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, for example, 1,3-bis (3-isocyanato-4-methylphenyl) urea and polyol adducts, for example, trimethylolpropane adduct of toluene diisocyanate (trade name) A death module L) or an amine adduct body may be used. The isocyanate compounds and isocyanate adduct compounds described in JP-A-10-76757 and JP-A-10-95171 (the contents of these publications are incorporated herein by reference). Among them, those having two or more isocyanate groups may be used.

A particularly preferred example is toluene diisocyanate. As the toluene diisocyanate, 2,4-toluene diisocyanate is preferable, and in addition, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available and inexpensive. It is available and may be this. These toluene diisocyanate isomer mixtures are liquid at room temperature.

The amine compound for forming a urea group by reacting with an isocyanate which is a starting material of a urea urethane compound may be any compound having an amino group. Examples thereof include aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethylaniline,
N, N-diethylaniline, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,
4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5
-Dichloroaniline, 2,6-dichloroaniline, 3,
4-dichloroaniline, 3,5-dichloroaniline,
2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline , N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, acetoacetic anilide, trimethylphenylammonium bromide, 4,4'-diamino-3,3'-diethyldiphenylmethane, , 4'-diaminobenzanilide,
3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, o-phenylenediamine, m-phenylene Diamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, iso-propyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide , P-ami -N- methylbenzamide, 3-
Amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p
-[N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl]
Aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- ( 2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2
-Methoxyaniline, 4-acetylaminoaniline, 4
-(N-methyl-N-acetylamino) aniline, 2,
5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, 4- Sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4
-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [ 4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy)
Phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diamino Biphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4
'-Diaminobiphenyl, ortho-tolidine sulfone,
2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-
Dichloro-4,4'-diaminobiphenyl, 3,3'-
Dichloro-4,4'-diaminobiphenyl, 2,2'-
Dimethyl-4,4'-diaminobiphenyl, 4,4'-
Thiodianiline, 2,2'-dithiodianiline, 4,4
'-Dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone,
4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane,
4,4-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,
4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4′-bis (4-aminophenoxy) diphenyl, 3,3 ′, 4,4′-tetraaminodiphenyl ether, 3,3 ′, 4,4′-tetraaminodiphenyl sulfone, 3,3 ′, 4,4′-tetraaminobenzophenone, 3-aminobenzonitrile,
-Phenoxyaniline, 3-phenoxyaniline, 4,
4'-methylenebis-O-toluidine, 4,4 '-(p
-Phenyleneisopropylidene) -bis- (2,6-xylidine), o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2 -Nitroaniline, 2-
Amino-4-chlorophenol, o-nitroaniline,
m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine,
2-amino-5-nitrobenzonitrile, methol,
2,4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanylic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3- Chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,
3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylation Diphenylamine, 2-methyl-4
-Methoxydiphenylamine, N, N-diphenyl-p
-Phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, 4,4'-diaminostilbene-2,
2'-disulfonic acid, benzylethylaniline, 1,8
Aromatic amines such as naphthalenediamine, sodium naphthionate, tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2,3-dichloroanthraquinone; and 3 -Amino-
1,2,4-triazole, 2-aminopyridine, 3-
Aminopyridine, 4-aminopyridine, α-amino-ε
-Caprolactam, acetoguanamine, 2,4-diamino-6- [2'-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5
-Diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine and the like Heterocyclic compound amines, methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3 -Ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino)
Propylamine, t-butylamine, propylamine,
3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, -Methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-
Examples thereof include aliphatic amines such as amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, and hexamethylenediamine.

Further, among the above-mentioned amine compounds, an aniline derivative having at least one amino group represented by the following formula (VIII) is particularly preferable.

[0220]

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(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, halogen, an alkyl group, an alkoxy group or an amino group, and X ₁ and X ₂ each independently represent Represents an amino group or a group represented by the formula (b),

[0222]

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Y ₁ represents —SO ₂ —, —O—, — (S) _n —,
— (CH ₂ ) _n —, —CO—, —CONH—, any of the groups represented by the formula (a),

[0224]

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[0225] Or, the case where it does not exist is shown. n is 1 or 2
It is. In addition, as the OH group-containing compound that reacts with an isocyanate to form a urethane group, any compound having an OH group may be used. For example, phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2 -Bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,
2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, catechol, 3-
Methyl catechol, 3-methoxy catechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) Benzyl acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3
5-dimethyl-4-hydroxyphenyl) sulfone, 4
-Hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-
4'-methylphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone,
-Hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, bis (2-methyl-3-t
tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,
4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl)
Hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4- (2-hydroxy) phenyl) sulfone, 2,4- Dihydroxybenzophenone, 2,2
', 4,4'-Tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-
Hydroxybenzoic acid (4'-chlorobenzyl), 1,2
-Bis (4'-hydroxybenzoic acid) ethyl, 1,5-
Bis (4'-hydroxybenzoic acid) pentyl, 1,6-
Hexyl bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-hydroxybenzaldehyde n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-
Octyloxycarbonylaminosalicylic acid, 4-n-
And phenols such as octanoyloxycarbonylaminosalicylic acid. However, as these phenols, those having an amino group are not preferred. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound. In addition, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isoheptanol,
2-ethyl-1-hexanol, 1-decanol, 2-
Pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methyl cellosolve,
Butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol,
Cyclohexylmethanol, cyclopentanol, 2-
Alcohols such as chloroethanol, 1-chloro-3-hydroxypropane, glycerin, glycerol, polypropylene glycol, polytetramethylene ether glycol, adipate-based polyol, epoxy-modified polyol, polyetherester polyol, polycarbonate polyol, polycaprolactonediol, phenol Polyols, polyether polyols such as amine-modified polyols, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,6-hexaneglycol, 1,9-nonanediol, acrylic polyol, fluorine Triol, polybutadiene polyols, polyhydroxy polyols, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol,
Polyols such as castor oil-based polyols, polymer polyols, methylpentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, α-methylglucoside, sorbitol, and sucrose are exemplified.

The urea urethane compound as a color developer according to the twenty-fourth to twenty-fifth aspects of the present invention further includes a compound represented by the general formula (I):
The urea urethane compound represented by any one of (VII) to (VII) is also preferable.

[0227]

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(Wherein, X and Z each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue; each residue may have a substituent; ₀ represents one selected from the group consisting of a tolylene group, a xylylene group, a naphthylene group, a hexamethylene group, and a -φ-CH ₂ -φ- group, and -φ- represents a phenylene group.)

[0229]

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(In the formula, X and Y each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, and each residue may have a substituent. Good.),

[0231]

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(Wherein, X and Y each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, and α represents a residue having a valence of 2 or more. , N represents an integer of 2 or more, and each residue may have a substituent.),

[0233]

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(Wherein, Z and Y each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, and β represents a residue having a valence of 2 or more. , N represents an integer of 2 or more, and each residue may have a substituent.),

[0235]

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(In the formula, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue, and is preferably a nitro group, a hydroxyl group, Carboxyl group, nitroso group, nitrile group, carbamoyl group, ureido group, isocyanato group,
Mercapto group, a sulfo group, may be substituted by sulfamoyl group or a halogen atom, and each residue may have a substituent, gamma is _{-SO 2 -, - O -,} -
(S) _n -,-(CH ₂ ) _n- , -CO-, -CONH-
And one selected from the group consisting of any of the groups represented by formula (a):

[0237]

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Or the case where none is present, wherein n is 1 or 2
It is. ),as well as

[0239]

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(In the formula, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue, but is preferably a hydroxyl group, a nitro group, Nitrile group, carbamoyl group, sulfamoyl group, carboxyl group, nitroso group, amino group,
An oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanato group, a mercapto group, a sulfo group or a halogen atom may be substituted, and each residue may have a substituent; δ is -SO ₂ -, - O
_{-, - (S) n -} , - (CH 2) n -, - CO -, - CO
NH -, - NH -, - CH (COOR 1) -, - C (C
One selected from the group consisting of F ₃ ) ₂ — and —CR ₂ R ₃ —, or absent; R ₁ , R ₂ and R ₃ each represent an alkyl group, and n is 1 or 2 . ),as well as

[0241]

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(In the formula, X, Y and Z each independently represent an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, and each residue may have a substituent. Here, X, Y and Z are preferably an aromatic compound residue or a heterocyclic compound residue.) The urea urethane compounds of the general formulas (I) to (VII) are also completely novel compounds. This novel compound is, for example,
It is useful for recording materials using recording energy such as heat and pressure. The urea urethane compounds of the formula (I) according to the twenty-fourth to twenty-fifth aspects of the present invention are not limited to a specific production method. It can be obtained by reacting with an amine compound of the formula (XI), for example, according to the following reaction formula (A).

[0243]

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[0244]

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[0245]

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(XI) (wherein, X and Z each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, and each residue may have a substituent. .Y ₀
Represents one selected from the group consisting of a tolylene group, a xylylene group, a naphthylene group, a hexamethylene group, and a -φ-CH ₂ -φ- group, and -φ- represents a phenylene group. In the present invention, the term "aliphatic" also includes alicyclic.

[0247]

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Among the urea urethane compounds represented by the formula (I), the following (E-1) and (E-8) are particularly preferable since a highly sensitive recording material is obtained. Twenty-fourth to twenty-fifth aspects of the invention
The urea urethane compound of the formula (II) according to the present invention is not limited to a production method. It can be obtained by reacting according to (B).

[0249]

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(In the formula, Y represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. Each residue may have a substituent.)

[0251]

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Formula (III) according to the twenty-fourth to twenty-fifth aspects of the present invention.
The production method of the ureaurethane compound of formula (IX) is not limited. For example, an OH group-containing compound of formula (IX)
I) an isocyanate compound represented by the following general formula (XII)
It can be obtained by reacting with the amine compound of I) according to, for example, the following reaction formula (C) or (D).

[0253]

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(In the formula, α represents a residue having a valence of 2 or more, and n represents an integer of 2 or more.)

[0255]

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[0256]

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The ureaurethane compounds of the formula (IV) according to the twenty-fourth to twenty-fifth aspects of the present invention are not limited in the production method. It can be obtained by reacting the OH group-containing compound of the general formula (XIV) with, for example, the following reaction formula (E) or (F).

[0258]

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(In the formula, β represents a residue having a valence of 2 or more, and n represents an integer of 2 or more.)

[0260]

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[0261]

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The compounds of the general formulas (IX) to (XIV) which can be used when synthesizing the ureaurethane compounds represented by the above formulas (I) to (IV) will be described in more detail. The OH group-containing compound represented by the general formula (IX) is not particularly limited as long as it has one or more OH groups. For example, phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, Resorcinol, p-tert-butylphenol,
p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 4
-Phenylphenol, 4-hydroxyphenyl-4 '
-Methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, 4-hydroxyphenyl -4'-
Benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate,
-Hydroxybenzoic acid (4'-chlorobenzyl), 1,
Ethyl 2-bis (4'-hydroxybenzoate), 1,5
-Bis (4'-hydroxybenzoic acid) pentyl, 1,6
-Bis (4'-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, 4-methoxyphenol,
4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid,
4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid,
Monophenols such as 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid are exemplified. Also, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, catechol, -Methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, 4,4'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) ) Benzyl acetate, bis (4-hydroxyphenyl)
Sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl-4′methylphenylsulfone, bis (2-allyl-4)
-Hydroxyphenyl) sulfone, bis (2-methyl-
3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether,
4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis ( 4-hydroxy-3-methylphenyl)
Diphenols such as sulfides are also included. However,
As these OH group-containing compounds, those having an amino group are not preferred. When an amino group coexists, the reactivity with an isocyanato group is higher than that of an OH group. Therefore, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound. In addition, methanol, ethanol, propanol, butanol, pentanol, hexanol,
Heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, 2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carb Tall, allyl alcohol, 2-methyl-2
-Propen-1-ol, benzyl alcohol, 4-pyridine methanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexyl methanol, cyclopentanol, 2-chloroethanol,
Monoalcohols such as -chloro-3-hydroxypropane, glycerin and glycerol are also included. Polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenol polyol and amine modified polyol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexaneglycol, 9-nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trime Ethane, hexane triol, phosphoric acid, neopentyl glycol, pentaerythritol,
Polyols such as castor oil-based polyols, polymer polyols, methylpentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, α-methylglucoside, sorbitol, and shoe rose may be used.
Of these, monophenols are preferably used.

Examples of the isocyanate compound of the general formula (X) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and 1,5-naphthylene diisocyanate. Isocyanate, meta-xylylene diisocyanate and the like can be mentioned. Of these, toluene diisocyanates are preferred.

The isocyanate compound of the general formula (XII) is not particularly limited as long as it has two or more isocyanate groups. For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene- 1,4
-Diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole-3,6
-Diisocyanate, 3,3'-dimethyl-4,4'-
Diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate, 4,4 ', 4'
'-Triisocyanato-2,5-dimethoxytriphenylamine, 4,4', 4 "-triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isopropylidene Bis-4-cyclohexyl isocyanate, dicyclohexyl methane diisocyanate, methylcyclohexane diisocyanate and the like can be mentioned. Further, diisocyanate dimer, for example, N, N '-(4,4'-dimethyl-3,3'-diphenyldiisocyanate) uretdione (trade name Desmodur TT) which is a dimer of toluene diisocyanate ) And trimers, such as 4,
4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,6-triphenylcyanurate may be used. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, for example, 1,3-bis (3-isocyanato-4-methylphenyl) urea and polyol adducts, for example, trimethylolpropane adduct of toluene diisocyanate ( The trade name may be Death Module L) or an amine adduct. Further, Japanese Patent Application Laid-Open Nos.
Of the isocyanate compounds and isocyanate adduct compounds described in the specification of -95171, those having two or more isocyanate groups may be used. A particularly preferred example is toluene diisocyanate.

The amine compound of the general formula (XI) is not particularly limited as long as it has one or more amino groups. Examples thereof include aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine. , P-anisidine, p-phenetidine, 2,4-dimethoxyaniline,
2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p
-Aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine,
4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, p
-Isopropyl aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-amino Benzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3
-Amino-4-methylbenzamide, 3-amino-4-
Methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline,
p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [ N- (2 '
-Methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2
-Methoxyaniline, 4-acetylaminoaniline, 2
-Methoxy-4- (N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylamino Sulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2 , 5-Dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4 -Methylaniline, o
-Chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline,
5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, -Amino-5
-Nitrobenzonitrile, sulfanilic acid, metanylic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o
-Fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, 2
Aromatic monoamines such as -amino-3-bromo-5-nitrobenzonitrile, 4,4'-diamino-3,3'-
Diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenylether, 3,3'-dichloro-4,4'-
Diaminodiphenylmethane, 3,3'-dimethyl-4,
4'-diaminodiphenylmethane, trizine base, dianisidine, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy)
Phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diamino Biphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4
'-Diaminobiphenyl, ortho-tolidine sulfone,
2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-
Dichloro-4,4'-diaminobiphenyl, 3,3'-
Dichloro-4,4'-diaminobiphenyl, 2,2'-
Dimethyl-4,4'-diaminobiphenyl, 4,4'-
Thiodianiline, 2,2'-dithiodianiline, 4,4
'-Dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone,
4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane,
4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone,
4,4'-diaminobenzophenone, 1,4-bis (4
-Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis And aromatic diamines such as (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, and 3,3'-dichlorobenzidine. Further, 3-amino-1,2,4-triazole, 2
-Aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2,4-diamino-6- [2′-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3
Heterocyclic compounds such as 5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine amines, methyl Amine, ethylamine, stearylamine, allylamine, isopropylamine, 2-ethylhexylamine,
Ethanolamine, 3- (2-ethylhexyloxy)
Propylamine, 3-ethoxypropylamine, 3-
(Diethylamino) propylamine, 3- (dibutylamino) propylamine, t-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, -Methylbutylamine,
Methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-
Methoxyethylamine, 2-ethoxymethylamine, 2
-Amino-1-propanol, 2-aminobutanol,
Examples thereof include aliphatic amines such as 3-amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, and hexamethylenediamine. Of these, aromatic monoamines are preferably used.

The amine compound of the general formula (XIII) is not particularly limited as long as it has two or more amino groups. For example, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4 '-Diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'
-Diaminodiphenylmethane, trizine base, dianisidine, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) ) Phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5 , 5'-Dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'
-Diaminobiphenyl, ortho-tolidine sulfone,
2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-
Dichloro-4,4'-diaminobiphenyl, 3,3'-
Dichloro-4,4'-diaminobiphenyl, 2,2'-
Dimethyl-4,4'-diaminobiphenyl, 4,4'-
Thiodianiline, 2,2'-dithiodianiline, 4,4
'-Dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone,
4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane,
4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone,
4,4'-diaminobenzophenone, 1,4-bis (4
-Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine, trizine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine And the like. Further, among the above-mentioned amine compounds, an aniline derivative having at least two amino groups represented by the following formula (VIII) is particularly preferable.

[0267]

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(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, halogen, an alkyl group, an alkoxy group or an amino group, and X ₁ and X ₂ represent an amino group or a formula (B)
Represents a group represented by

[0269]

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Y ₁ represents —SO ₂ —, —O—, — (S) _n —,
— (CH ₂ ) _n —, —CO—, —CONH—, any of the groups represented by the formula (a),

[0271]

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[0272] Or, the case where it does not exist is shown. n is 1 or 2
It is. ) Further, as the OH group-containing compound of the general formula (XIV), OH
There is no particular limitation as long as the compound has two or more groups. For example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2
2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, catechol, 3-
Methyl catechol, 3-methoxy catechol, pyrogallol, hydroquinone, methyl hydroquinone, p, p'-
Biphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate,
Bis (4-hydroxyphenyl) sulfone, bis (3-
Methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone , Bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4 '
-Dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone,
Diphenols such as 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, and bis (4-hydroxy-3-methylphenyl) sulfide; Can be However, those having an amino group are not preferred as these diphenols. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound. Polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenol polyol and amine modified polyol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexaneglycol, 9-nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trime Ethane, hexane triol, phosphoric acid, neopentyl glycol, pentaerythritol,
Polyols such as castor oil-based polyols, polymer polyols, methylpentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, α-methylglucoside, sorbitol, and sucrose are exemplified.

The ureaurethane compounds of the formula (V) according to the twenty-fourth to twenty-fifth aspects of the present invention are not limited to a specific production method. Can be obtained, for example, by reacting according to the following reaction formula (G) or (H).

[0274]

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(In the formula, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue, and is preferably a nitro group, a hydroxyl group, Carboxyl group, nitroso group, nitrile group, carbamoyl group, ureido group, isocyanato group,
It may be substituted by a mercapto group, a sulfo group, a sulfamoyl group or a halogen atom. Further, each residue may have a substituent. γ is -SO _2- , -O-,-
(S) _n -,-(CH ₂ ) _n- , -CO-, -CONH
-, Any of the groups represented by formula (a),

[0276]

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Or, the case where it does not exist is shown. n is 1 or 2
It is. )

[0278]

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[0279]

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The ureaurethane compounds of the formula (VI) according to the twenty-fourth to twenty-fifth aspects of the present invention are not particularly limited in the production method. Can be obtained, for example, according to the following reaction formula (J) or (K).

[0281]

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(In the formula, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, but is preferably a hydroxyl group, a nitro group, It may be substituted with a nitrile group, carbamoyl group, sulfamoyl group, carboxyl group, nitroso group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanato group, mercapto group, sulfo group or halogen atom. each residue may have a substituent .δ is _{-SO 2 -, - O -,} -
(S) _n -,-(CH ₂ ) _n- , -CO-, -CONH
-, - NH -, - CH (COOR 1) -, - C (CF 3)
_{2 -, - CR 2 R 3} - shows the case where not one or presence of. R ₁ , R ₂ and R ₃ each independently represent an alkyl group, and n is 1 or 2. )

[0283]

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[0284]

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The compounds that can be used for synthesizing the ureaurethane compounds of the formulas (V) and (VI) according to the twenty-fourth to twenty-fifth aspects of the present invention are described in detail below.
The phenol compound that can be used when synthesizing the urea urethane compound of the formula (V) is not particularly limited as long as it is a compound having one or more OH groups on the benzene ring. An aromatic compound residue other than an OH group or an aliphatic compound residue or a heterocyclic compound residue, a nitro group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group,
It may be substituted by a mercapto group, a sulfo group, a sulfamoyl group or a halogen atom. Preferred phenol compounds include, for example, phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol Thymol, 2-naphthol, nitro-substituted phenol p-nitrophenol, halogen-substituted phenol o-chlorophenol, p-chlorophenol, 4-phenylphenol, 4-hydroxyphenyl-4'-methylphenylsulfone, 3 -Chloro-4-
Hydroxyphenyl-4'-methylphenylsulfone,
4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, 4-hydroxyphenyl-
4'-benzyloxyphenyl sulfone, 4-isopropylphenyl-4'-hydroxyphenyl sulfone, 4
-Hydroxy-4'-isopropoxydiphenyl sulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), dimethyl 3-hydroxyphthalate , 4-methoxyphenol, 4- (benzyloxy) phenol, 4-
Hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n
-Pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid,
4-n-octyloxycarbonylaminosalicylic acid,
Phenols such as 4-n-octanoyloxycarbonylaminosalicylic acid are exemplified. Further, a phenol compound having a substituent such as a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanato group, a mercapto group, a sulfo group, and a sulfamoyl group may be used. However, as these phenols, those having an amino group are not preferred. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound.

The aromatic diisocyanate compound which can be used when synthesizing the urea urethane compounds of the formulas (V) and (VI) is an aromatic diisocyanate having two isocyanate groups bonded to a benzene ring. There is no particular limitation as long as it is present. For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate
2,6-toluene diisocyanate and the like. Particularly preferred examples include toluene diisocyanates. As the toluene diisocyanate, 2,4-toluene diisocyanate is preferred,
In addition, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate
Mixtures of toluene diisocyanates are generally commercially available and can be obtained at low cost, but this is also acceptable. These toluene diisocyanate isomer mixtures are liquid at room temperature.

The diamine compound of the general formula (XV) which can be used when synthesizing the ureaurethane compound of the formula (V) includes, for example, 4,4'-diamino-3,3
'-Diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4
'-Diaminodiphenylmethane, 3,3'-dimethyl-
4,4'-diaminodiphenylmethane, tolidine base, dianisidine, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4-
(P-Aminophenoxy) phenyl] sulfone, 3,3
'-Dimethoxy-4,4'-diaminobiphenyl, 3,
3'-dimethyl-4,4'-diaminobiphenyl, 2,
2'-dichloro-4,4'-diamino-5,5'dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-
4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,
2'-dichloro-4,4'-diaminobiphenyl, 3,
3'-dichloro-4,4'-diaminobiphenyl, 2,
2'-dimethyl-4,4'-diaminobiphenyl, 4,
4 ′ thiodianiline, 2,2′-dithiodianiline,
4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 '
-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenylsulfone, 3,3
'-Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'
-Ethylenedianiline, 4,4'diamino-2,2'-
Dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4
-Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4 ' -Bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-
And aromatic diamines such as dichlorobenzidine.

The aniline derivative that can be used when synthesizing the urea urethane compound of the formula (VI) is not particularly limited as long as it is an aniline compound having one or more amino groups on a benzene ring. Hydrogen atom of benzene ring is aromatic compound residue or aliphatic compound residue or heterocyclic compound residue or hydroxyl group, nitro group, nitrile group, carbamoyl group, sulfamoyl group, carboxyl group, nitroso group, amino group, oxyamino group , Nitroamino group, hydrazino group, ureido group, isocyanato group,
It may be substituted by a mercapto group, a sulfo group or a halogen atom. Preferred aniline compounds include, for example, aniline, o-toluidine, m-toluidine, p-
Toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,
4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, carboxyl-substituted aniline p-aminobenzoic acid, hydroxyl-substituted aniline o-aminophenol, m-aminophenol, 2-amino-4-chlorophenol, p-aminophenol, and the like, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6
-Xylidine, 4-aminobenzonitrile which is a nitrile-substituted aniline, anthranilic acid, p-cresidine, 2,5-dichloroaniline which is a halogen-substituted aniline,
Α-naphthylamine, such as 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, o-chloroaniline, m-chloroaniline, and p-chloroaniline; Aminoanthracene, o-ethylaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, p-aminobenzoic acid Dodecyl, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N
-Methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-
Amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4
-Aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2
-Methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5
Carbamoylanilines such as-[N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, , 5-Diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, , 4-sulfamoylaniline, 3-sulfamoylaniline, 2
-Chloro-5-N-phenylsulfamoylaniline,
Sulfamoylanilines such as 2-methoxy-5-N, N-diethylsulfamoylaniline and 2,5-dimethoxy-4-N-phenylsulfamoylaniline;
(N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole,
4-aminodiphenylsulfone, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, and nitro-substituted aniline o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-
Dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino −5-
Nitrobenzonitrile, p-fluoroaniline, o-
Fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, 2
-Amino-3-bromo-5-nitrobenzonitrile and the like.

Further, an aniline derivative having a substituent such as a carboxyl group, a nitroso group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanato group, a mercapto group or a sulfo group may be used. The formula (V
Examples of the dihydroxy compound of the general formula (XVI) that can be used when synthesizing the urea urethane compound of I) include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,
2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, 4,4′-biphenol, butyl bis (4-hydroxyphenyl) acetate,
Benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5
-Dimethyl-4-hydroxyphenyl) sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4
'-Dihydroxybenzophenone, 2,2-bis (4-
Hydroxyphenyl) hexafluoropropane, 4,4
'-Dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-
And diphenols such as methylphenyl) sulfide. However, those having an amino group are not preferred as these diphenols. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound.

The formula (VII) according to the twenty-fourth to twenty-fifth aspects of the present invention.
The method of synthesizing the urea urethane compound of formula (I) is not particularly limited. The following reaction formula (L)
By reacting according to the following formula.

[0291]

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The substituent of X bonded to the urethane group of the urea urethane compound of the general formula (VII) includes an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an amide group, an alkoxyl group and a nitro group. , Nitroso group, nitrile group, toluenesulfonyl group, methanesulfonyl group, acetyl group, halogen atom, formyl group,
Dialkylamino groups and isocyanato groups are preferred. Among these urea urethane compounds as the color developers of the general formulas (I) to (VII), preferred are the general formulas (II) to (II).
The compound of the formula (VI), and particularly preferred are the compounds of the general formulas (V) to (VI). Further, a compound of the following structural formula (XX) or (XXI) is particularly preferred.

[0293]

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[0294]

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In the urea urethane compounds as the color developers according to the twenty-fourth to twenty-fifth aspects of the invention and the urea urethane compounds as the color developers of the formulas (I) to (IV) and (VII), a urea group or a urethane group When the residue bonded to the group is an aliphatic compound residue, the coloring density and print storage performance may be reduced, and the residue bonded to the urea group or the urethane group is an aromatic compound residue or It is preferably a heterocyclic compound residue. However, the reduction in color density and print storage performance that may be caused by the introduction of an aliphatic compound residue into the compound is reduced by increasing the number of urea groups and urethane groups, and the formula (II)
In the compounds of the formulas (I) and (IV), even if an aliphatic compound residue is present in the residue bonded to the urea group or the urethane group, there is almost no problem in performance.

In order to obtain the urea urethane compounds according to the twenty-fourth to twenty-fifth aspects of the present invention, the reactants may be mixed with an isocyanate in an organic solvent or without a solvent and reacted, and then the crystals may be taken out by filtration. Then, the organic solvent may be simply removed by drying to take out the crystal. The reactants may be used alone or in combination depending on the purpose. The isocyanate and the reactant preferably contain no water. However, in order to obtain a high-purity ureaurethane compound, the water content of each of the isocyanate and the reactant is preferably 0. It is preferably at most 5% by weight, more preferably at most 0.2% by weight. The solvent may be any solvent as long as it does not react with the isocyanato group and the functional group of the reactant. Examples thereof include an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a chlorinated aliphatic Examples include hydrogen, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, ketones, esters, and the like. Particularly, methyl ethyl ketone, acetone, toluene, ethyl acetate and the like, which dissolve the isocyanate and have low solubility of the product, are preferable.

Further, it is preferable that the solubility parameter value of the Hildebrand solvent is 7 to 15. Moreover,
Those having a solubility parameter value of 7 to 8.8 are particularly preferable because they dissolve the reaction raw materials and have low solubility of the product. Further, the value of the solubility parameter is 8.9 to 21.
When the polar solvent is used in combination with a solvent having a solubility parameter value of 7 to 8.8, the dissolution state of the reaction raw material and the product can be controlled, and the urea urethane composition can be obtained in a high yield, which is preferable. . In this case, when a hydroxy compound which is a urethane group-forming raw material is used as the polar solvent to be used in combination, the hydroxy compound is consumed in the reaction, and the value of the solubility parameter is substantially 7 to 10.
The solvent of 8.8 is used alone, which is advantageous and preferable in recycling the solvent. As the hydroxy compound, a phenolic compound is preferable, and phenol is particularly preferable. The product obtained by the above-mentioned reaction operation is not necessarily a single product, and may be obtained as a mixture of compounds having different substituent positions. Twenty-fourth of the present invention
Specific examples of the urea urethane compound according to No. 25 include the following compounds. ((E-1) ~
(E-43))

[0298]

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[0299]

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[0300]

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[0301]

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[0302]

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[0303]

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[0304]

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[0305]

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[0306]

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[0307]

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[0308]

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The urea urethane compound as a color developer of the present invention is a colorless or pale color compound which is usually a solid at room temperature.
The molecular weight of the urea urethane compound as the color developer of the present invention is preferably 5,000 or less, more preferably 200 or less.
It is preferably 0 or less. The total number of urea groups and urethane groups in the urea urethane compound as a color developer of the present invention is preferably 20 or less, and more preferably 1 or less.
It is preferably 0 or less. Further, the ratio of the urea group to the urethane group in the urea urethane compound molecular structure,
1: 3 to 3: 1, preferably 1: 2 to 2: 1. In preparing a recording material using a urea urethane compound as a color developer, one kind of the urea urethane compound may be used, or two or more kinds thereof may be used as needed. In the heat-sensitive recording material, a compound having a melting point is more preferable, and the melting point of the urea urethane compound as a color developer of the present invention is preferably from 40 ° C. to 500 ° C.
° C, particularly preferably in the range of 60 ° C to 300 ° C.

The colorless or light-colored dye precursor according to the twenty-fifth aspect of the present invention is a compound which is already known as a color former used in a pressure-sensitive recording material or a heat-sensitive recording material, and is not particularly limited. Leuco dyes are preferable, and triarylmethane leuco dyes, fluoran leuco dyes, fluorene leuco dyes, diphenylmethane leuco dyes, and the like are more preferable. The following are representative leuco dyes. (1) Triarylmethane compound 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide, 3- ( p-dimethylaminophenyl) -3-
(1,2-dimethylindol-3-yl) phthalide,
3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindole-
3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindole-3-
Yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5 -Dimethylaminophthalide, 3-p
-Dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide and the like.

(2) Diphenylmethane compounds 4,4-bis-dimethylaminophenylbenzhydryl benzyl ether, N-halophenyl leuco auramine, N-2,4,5-trichlorophenyl leuco auramine and the like. (3) Xanthene compound rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, 3-dimethylamino-6-methyl-7- (m-trifluoromethylanilino) fluoran, 3-diethylamino-6- Methyl-fluoran, 3
-Diethylamino-7-methyl-fluoran, 3-diethylamino-7-chloro-fluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-7 -Octylaminofluoran, 3-diethylamino-7-phenylfluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-p-methylanilinofluoran, 3 -Diethylamino-6-methyl-7-m-methylanilinofluoran, 3-diethylamino-6-chloro-7-methylfluoran, 3-diethylamino-7
-(3,4-dichloroanilino) fluoran, 3-diethylamino-7- (2-chloroanilino) fluoran,
3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluoran, 3-diethylamino-6-
Methyl-7- (2,6-xyridino) fluoran, 3-
(N-ethyl-N-isobutylamino) -6-methyl-
7-anilinofluoran, 3- (N-ethyl-N-ethoxypropylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino-6
Methyl-7-phenethylfluoran, 3-diethylamino-7- (o-fluoro) anilinofluoran, 3-diethylamino-7-trifluoromethylanilinofluoran, 3-diethylamino-7- (4-nitroanilino) fluoran , 3-diethylamino-6-methyl-7
-(M-trifluoromethylanilino) fluoran, 3
-Diethylamino-6-methyl-7- (o-chloroanilino) fluoran, 3-diethylamino-6-methyl-
7- (p-chloroanilino) fluoran, 3-diethylamino-6-methyl-7- (o-fluoroanilino) fluoran, 3-diethylamino-6-methyl-7- (p
-N-butylanilino) fluoran, 3-diethylamino-6-methyl-7-n-octylaminofluoran,
3-diethylamino-6-chloro-7-anilinofluoran, 3-diethylamino-6-ethoxyethyl-7-
Anilinofluoran, 3-diethylamino-benzo [a] fluoran, 3-diethylamino-benzo [c]
Fluoran, 3-diethylamino-6-methyl-7-benzylaminofluoran, 3-diethylamino-6-methyl-7-dibenzylaminofluoran, 3-diethylamino-7-di (p-methylbenzyl) aminofluoran, 3-diethylamino-6-methyl-7-diphenylmethylaminofluoran, 3-diethylamino-7-dinaphthylmethylaminofluoran, 10-diethylamino-4-dimethylaminobenzo [a] fluoran, 3-
Diethylamino-7,8-benzfluoran, 3-diethylamino-6-methyl-7- (m-trichloroanilino) fluoran, 3-diethylamino-7- (o-chloroanilino) fluoran, 3-dibutylamino-7-
(O-chloroanilino) fluoran, 3-diethylamino-6-methyl-7- (2 ', 4'-dimethylanilino) fluoran, 3- (N, N-diethylamino) -5
-Methyl-7- (N, N-dibenzylamino) fluoran, 3-morpholino-7- (N-propyltrifluoromethylanilino) fluoran, 3-pyrrolidino-7-trifluoromethylanilinofluoran, 3- Diethylamino-5-chloro-7- (N-benzyl-trifluoromethylanilino) fluoran, 3-pyrrolidino-7-
(Di-p-chlorophenyl) methylaminofluoran,
3-diethylamino-5-chloro-7- (α-phenylethylamino) fluoran, 3- (N-ethyl-Np
-Toluidino) -7- (α-phenylethylamino) fluoran, 3-diethylamino-7- (o-methoxycarbonylphenylethyl) fluoran, 3-diethylamino-5-methyl-7- (α-phenylethylamino)
Fluoran, 3-diethylamino-7-piperidinoaminofluoran, 2-chloro-3- (N-methyltoluidino) -7- (p-N-butylanilino) fluoran, 3
-(N-ethyl-N-cyclohexylamino) -5,6
-Benzo-7-α-naphthylamino-4′-bromofluorane, 3-diethylamino-6-methyl-7-mesitidino-4 ′, 5′-benzofluoran, 3-dibutylamino-6-methyl-fluoran, 3-dibutylamino-
6-methyl-7-chlorofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-p-methylanilinofluoran, 3-dibutylamino- 6-methyl-7- (o, p-
Dimethylanilino) fluoran, 3-dibutylamino-
6-methyl-7- (m-trifluoromethylanilino)
Fluoran, 3-dibutylamino-6-methyl-7-
(o-chloroanilino) fluoran, 3-dibutylamino-6-methyl-7- (p-chloroanilino) fluoran, 3-dibutylamino-6-methyl-7- (o-fluoroanilino) fluoran, 3-dibuethyl Amino-
7- (o-fluoroanilino) fluoran, 3-dibutylamino-6-methyl-7- (pn-butylanilino) fluoran, 3-dibutylamino-6-methyl-7
-N-octylaminofluoran, 3-dibutylamino-6-chloro-7-anilinofluoran, 3-dibutylamino-6-ethoxyethyl-7-anilinofluoran, 3-di-n-pentylamino-6 -Methyl-7-anilinofluoran, 3-di-n-pentylamino-6-methyl-7- (o, p-dimethylanilino) fluoran, 3-
Di-n-pentylamino-6-methyl-7- (m-trifluoromethylanilino) fluoran, 3-di-n-pentylamino-6-methyl-7- (o-chloroanilino) fluoran, 3-di-n-pentyl Amino-6-methyl-7
-(P-chloroanilino) fluoran, 3-di-n-pentylamino-6-methyl-7- (o-fluoroanilino) fluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3-piperidino -6-methyl-7-
Anilinofluoran, 3-cyclohexylamino-6-
Chlorofluorane, 3-dimethylamino-5,7-dimethylfluoran, 3- (N-methyl-N-isoamylamino) -6-methyl-7-anilinofluoran, 3-
(N-methyl-NN-propylamino) -6-methyl-7-anilinofluoran, 3- (N-methyl-N-amylamino) -6-methyl-7-anilinofluoran,
3- (N, N-di-n-amylamino) -6-methyl-
7-anilinofluoran, 3- (N-methyl-N-is
o-propylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-Nn-propylamino)
-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-iso-propylamino) -6-methyl-7
-Anilinofluoran, 3- (N-ethyl-NN-butylamino) -6-methyl-7-anilinofluoran,
3- (N-ethyl-N-iso-butylamino) -6
Methyl-7-anilinofluoran, 3- (N-ethyl-
Nn-hexylamino) -6-methyl-7-p-methylanilinofluoran, 3- (N-ethyl-Nn-hexylamino) -6-methyl-7- (o, p-dimethylani Rino) fluorane, 3- (N-ethyl-N-n-hexylamino) -6-methyl-7- (m-trifluoromethylanilino) fluoran, 3- (N-ethyl-Nn
-Hexylamino) -6-methyl-7- (o-chloroanilino) fluoran, 3- (N-ethyl-N-iso-
Amylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-iso-amylamino)-
6-chloro-7-anilinofluoran, 3- (N-ethyl-N-3-methylbutylamino) -6-methyl-7-
Anilinofluoran, 3- (N-ethyl-Np-toluidino) -6-methyl-7-anilinofluoran, 3-
(N-ethyl-Np-toluidino) -6-methyl-7
-(P-methylanilino) fluoran, 3- (N-ethyl-N-p-toluidino) -6-methyl-7- (o, p-dimethylanilino) fluoran, 3- (N-ethyl-N-
Tetrahydrofurfurylamino) -6-methyl-7-anilinofluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran,
3- (N-cyclohexyl-N-methylamino) -7-
Anilinofluoran, 3- (N-ethyl-N-3-methoxypropylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-3-ethoxypropylamino) -6 Methyl-7-anilinofluoran, 2-
(4-oxahexyl) -3-dimethylamino-6-methyl-7-anilinofluoran, 2- (4-oxahexyl) -3-diethylamino-6-methyl-7-anilinofluoran, 2- ( 4-oxahexyl) -3-dipropylamino-6-methyl-7-anilinofluoran,
3,6-bis (diethylamino) fluoran-γ- (2 ′
-Nitro) anilinolactam, 3,6-bis (diethylamino) fluoran-γ- (3′-nitro) anilinolactam, 3,6-bis (diethylamino) fluoran-
γ- (4′-nitro) anilinolactam, 3,6-bis (diethylamino) fluoran-γ-anilinolactam and the like.

(4) Thiazine compounds Benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue and the like. (5) Spiro compound 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3-methoxybenzo) Spiropyran, 3-propylspirobenzopyran and the like.

Further, 3,6-bis (dimethylamino) fluorene-9-spiro-3 ′-(6′-dimethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3′- (6′-dimethylaminophthalide), 3,6-bis (diethylamino) fluorene-9-spiro-3 ′-(6′-dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9- Spiro-3 ′-(6′-dimethylaminophthalide), 3-dibutylamino-6-diethylaminofluorene-9-spiro-3 ′-(6′-dimethylaminophthalide), 3,6-bis (dimethylamino) ) Fluorene-9-spiro-3 '-(6'-diethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3'-(6'-di Butylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3 ′-(6′-diethylaminophthalide), 3,6-bis (diethylamino) fluorene-9-spiro-3′- (6′-diethylaminophthalide), 3,6-bis (dimethylamino) fluorene-9
-Spiro-3 '-(6'-dibutylaminophthalide),
3-dibutylamino-6-diethylaminofluorene-
9-spiro-3 '-(6'-diethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3'-(6'-dibutylaminophthalide), 3,3-bis [2 -(4-Dimethylaminophenyl) -2- (4-methoxyphenyl) ethenyl]-
Compounds having an absorption region in the near infrared, such as 4,5,6,7, -tetrachlorophthalide.

Of these, triarylmethane leuco dyes, fluoran leuco dyes, fluorene leuco dyes, and diphenylmethane leuco dyes are particularly preferred from the viewpoints of sensitivity and plasticizer resistance.
Compounds having the structure of 1) or (j) are preferred.

[0315]

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(Where Y ₂ and Y ₃ both represent an alkyl group or an alkoxyalkyl group, Y ₄ represents a hydrogen atom, an alkyl group, or an alkoxy group; and Y ₅ and Y ₆ represent a hydrogen atom , A halogen atom, an alkyl group or an alkoxy group.)

[0317]

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[Wherein, R ₅ and R ₆ represent either a group represented by the formula (k) or the formula (l)].

[0319]

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(Where R₁₁~ R₁₅Is a hydrogen atom, halo
Gen atom, C₁~ C₈An alkyl group of C ₁~ C₈Alcoqui
Si group, -NR₁₆R₁₇Is shown. R₁₆, R₁₇Is C₁~ C₈of
It is an alkyl group. )

[0321]

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(Where R ₁₈ and R ₁₉ are a hydrogen atom, C ₁
Alkyl group -C _8, a phenyl group. ) In addition, R ₇ ~
R ₁₀ represents a hydrogen atom, a halogen atom, an alkyl group of C ₁ -C _8, alkoxy group of C ₁ -C _8, a -NR ₂₀ R _21.
R ₂₀ and R ₂₁ are a C ₁ -C ₈ alkyl group. Further, a compound having a structure represented by the following chemical formula (i-2) or (i-3) is preferable since a recording material having excellent whiteness can be obtained.

[0323]

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(Here, P ₂ and P ₃ both represent an alkyl group or an alkoxyalkyl group, and at least one of P ₂ and P ₃ is a group having 5 or more carbon atoms.
₄ represents a hydrogen atom, an alkyl group, or an alkoxy group. P ₅ and P ₆ represent a hydrogen atom, a halogen atom, an alkyl group, a halogen-substituted alkyl group or an alkoxy group. )

[0325]

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(Wherein Q ₂ and Q ₃ both represent an alkyl group or an alkoxyalkyl group, Q ₄ represents a hydrogen atom, an alkyl group, or an alkoxy group; and Q ₅ and Q ₆ represent a hydrogen atom a halogen atom, an alkyl group, but a halogen-substituted alkyl group or an alkoxy group, Q ₅
And at least one of Q ₆ is a halogen atom,
It is an alkyl group or a halogen-substituted alkyl group. ) Further, 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7
-Anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-7
-(2-chloroanilino) fluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran, 3-di-n-pentylamino-6-methyl-7-anilinofluoran, 3- (N-methyl-N- n-propylamino)-
6-methyl-7-anilinofluoran, 3- (N-ethyl-N-iso-amylamino) -6-methyl-7-anilinofluoran, 3- (N-cyclohexyl-N-methylamino) -6 -Methyl-7-anilinofluoran,
3-dibutylethyl-7- (o-fluoroanilino)
Fluoran, 3- (N-ethyl-Np-toluidino)
-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-m-methylanilinofluoran, 3-diethylamino-6-methyl-7-m-methylanilinofluoran, 3- Diethylamino-6-methyl-7- (2,6-xyridino) fluoran, 3- (N-
Ethyl-N-isobutylamino) -6-methyl-7-anilinofluoran, 3-diethylamino-7- (o-fluoro) anilinofluoran, 3- (N-ethyl-N-
Tetrahydrofurfurylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-ethoxypropylamino) -6-methyl-7-anilinofluoran, 3-diethylamino-7-trifluoro Methylanilinofluoran is preferably used.

These colorless or light-colored dye precursors can be used in combination of two or more as necessary.
The urea urethane compound as a color developer is preferably used in an amount of 5 to 1000 parts by weight, more preferably 20 to 500 parts by weight, based on 100 parts by weight of the colorless or pale dye precursor. 5 urea urethane compounds as color developers
When the amount is at least part by weight, it is sufficient to cause the dye precursor to develop color, and the coloring density is high. If the amount of the urea urethane compound as a color developer is 1000 parts by weight or less, an excessive amount of the urea urethane compound as a color developer hardly remains, which is economically advantageous and preferable.

The urea urethane compound or urea urethane composition as a developer according to the twenty-seventh aspect of the present invention includes the first to fourth urea urethane compounds of the present invention and the fifth to twelfth urea urethane compositions of the present invention. Alternatively, the compositions produced by the production methods described in the thirteenth to twenty-third aspects of the present invention can be used. The synthesis method is as already described in detail in the first to twelfth explanations of the present invention. Preservability is improved by further adding an isocyanate compound to the color former of the present invention. The isocyanate compound used in addition to the color former of the present invention refers to a colorless or pale-colored aromatic isocyanate compound or a heterocyclic isocyanate compound which is a solid at room temperature, for example, one or more of the following isocyanate compounds are used. Can be

2,6-dichlorophenyl isocyanate, p-chlorophenyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-dimethylbenzene-4,6-diisocyanate, 1,4-dimethylbenzene-2,5-diisocyanate, 1-methoxybenzene-2,4-diisocyanate, 1-methoxybenzene-2,5-diisocyanate, 1-ethoxybenzene-2,4- Diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,5-diethoxybenzene-1,4-diisocyanate, 2,5-dibutoxybenzene-1,4
-Diisocyanate, azobenzene-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-
2,6-diisocyanate, naphthalene-2,7-diisocyanate, 3,3'-dimethyl-biphenyl-4,
4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, benzophenone-
3,3'-diisocyanate, fluorene-2,7-diisocyanate, anthraquinone-2,6-diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, pyrene-3,8-diisocyanate Nate, naphthalene-1,3,7-triisocyanate, biphenyl-
2,4,4'-triisocyanate, 4,4 ', 4''
-Triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ', 4 "-triisocyanatotriphenylamine, p-dimethylaminophenylisocyanate, tris (4-phenylisocyanate) thiophosphate and the like. . These isocyanates may be used, if necessary, in the form of so-called block isocyanates, which are addition compounds with phenols, lactams, oximes, etc., and diisocyanate dimers such as 1
-Methylbenzene-2,4-diisocyanate may be used in the form of dimers and trimers of isocyanurate, or may be used as a polyisocyanate adducted with various polyols and the like. It is. Also, water adduct isocyanates such as 2,4-toluene diisocyanate and diphenylmethane diisocyanate, for example, 1,3-bis (3-isocyanato-4-methylphenyl) urea and polyol adducts, for example, toluene diisocyanate Methylol propane adduct (trade name Desmodur L), phenol adduct isocyanate, amine adduct isocyanate, etc.
The isocyanate compound and the isocyanate adduct compound described in JP-A-76757 and JP-A-10-95171 may also be used.

The isocyanate compound is preferably used in an amount of 5 to 500 parts by weight, more preferably 20 to 200 parts by weight, per 100 parts by weight of the colorless or pale color dye precursor. When the amount of the isocyanate compound is 5 parts by weight or more, the effect of improving the preservability is sufficient, and the coloring density is high. Also, when the isocyanate compound is 500 parts by weight or less, an excess of the isocyanate compound hardly remains, which is economically advantageous and preferable. Further, by adding an imino compound thereto, the storage stability is further improved.

The imino compound which can be added to the color forming agent of the present invention is a compound having at least one imino group, and is a colorless or pale-colored compound which is solid at room temperature. Two or more imino compounds can be used in combination depending on the purpose. Examples of these imino compounds are disclosed in
No. 142032 can be mentioned,
The contents of the publication are incorporated herein by reference. Among these, iminoisoindoline derivatives are particularly preferred, and 1,3-diimino-4,
5,6,7-tetrachloroisoindoline, 3-imino-4,5,6,7-tetrachloroisoindoline-1-
On, 1,3-diimino-4,5,6,7-tetrabromoisoindoline is preferred.

The imino compound is preferably used in an amount of 5 to 500 parts by weight, more preferably 20 to 200 parts by weight, per 100 parts by weight of the colorless or pale color dye precursor.
When the amount of the imino compound is 5 parts by weight or more, the effect of improving storage stability is exhibited. When the amount of the imino compound is 500 parts by weight or less, an excess of the imino compound hardly remains, which is economically advantageous and preferable. Further, by adding an amino compound to the color former of the present invention, the background and the storage stability of the print are improved. Amino compounds which can be added are colorless or pale-colored substances having at least one primary, secondary or tertiary amino group. Examples of these amino compounds include those described in JP-A-9-142032. Among them, the following formula (VII)
An aniline derivative having at least one amino group as in I) is preferred.

[0333]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, halogen, an alkyl group, an alkoxy group or an amino group, and X ₁ and X ₂ represent an amino group or a group represented by the formula (B)
Represents a group represented by

[0335]

Embedded image

Y ₁ represents —SO ₂ —, —O—, — (S) _n —,
— (CH ₂ ) _n —, —CO—, —CONH—, any of the groups represented by the formula (a),

[0337]

Embedded image

[0338] Or, the case where it does not exist is shown. n is 1 or 2
It is. The amino compound may be used alone or as a mixture of two or more kinds. In order to improve the print preservability in plasticizer resistance, 1 to 100 parts by weight of a colorless or pale color dye precursor is used. Preferably it is 500 parts by weight. When the content of the amino compound is at least 1 part by weight with respect to the urea urethane compound, improvement in print preservability can be obtained. If the amount is 500 parts by weight or less, the performance is sufficiently improved and the cost is advantageous. In the color former of the present invention, by further adding an acidic developer, the sensitivity is improved and a color former having a clear color is obtained.

When the color former of the present invention is used as a heat-sensitive recording material, as the acidic developer, a generally used electron accepting substance is used. Particularly, a phenol derivative, an aromatic carboxylic acid derivative or a metal compound thereof is used. , Salicylic acid derivatives or metal salts thereof, N, N-diarylthiourea derivatives, sulfonylurea derivatives and the like are preferred. Particularly preferred are phenol derivatives, specifically, 2,2
-Bis (4-hydroxyphenyl) propane, 2,2-
Bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4- (Hydroxyphenyl) -4-methylpentane, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-
Isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4
'-Benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, methyl 4-hydroxybenzoate, 4-hydroxybenzoic acid Benzyl, 4-hydroxybenzoic acid (4'-chlorobenzyl), 1,2-bis (4
'-Hydroxybenzoic acid) ethyl, 1,5-bis (4'
-Hydroxybenzoic acid) pentyl, 1,6-bis (4 ′
-Hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate and the like. As salicylic acid derivatives, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octoctanoyloxysalicylic acid, 4-n- Octyloxycarbonylaminosalicylic acid, 4-n-octanoyloxycarbonylaminosalicylic acid and the like are also included. As an example of the sulfonylurea derivative, 4,4-bis (p
-Toluenesulfonylaminocarbonylamino) diphenylmethane, 4,4-bis (o-toluenesulfonylaminocarbonylamino) diphenylmethane, 4,4-bis (p-toluenesulfonylaminocarbonylamino)
Compounds containing one or more arylsulfonylaminoureido groups such as diphenyl sulfide, 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenyl ether, and N- (p-toluenesulfonyl) -N'-phenylurea are also included. Furthermore, 4, 4'-
[Oxybis (ethyleneoxy-p-phenylenesulfonyl)] diphenol and a mixture containing the same as a main component (for example, D-90: trade name, manufactured by Nippon Soda Co., Ltd.) may be used.

Among them, particularly, 2,2-bis (4-hydroxyphenyl) propane, 4-isopropyloxyphenyl-4′-hydroxyphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone,
2,4'-dihydroxydiphenyl sulfone, 4,4
'-[Oxybis (ethyleneoxy-p-phenylenesulfonyl)] diphenol is preferred because a heat-sensitive recording material having improved sensitivity and vivid coloration can be obtained.

Further, in order to improve background covering and thermal responsiveness, N-stearyl-N '-(2-hydroxyphenyl) urea, N-stearyl-N'-(3-hydroxyphenyl) urea, N-stearyl-N '-(3-hydroxyphenyl) urea Stearyl-N ′-(4-hydroxyphenyl) urea, p-stearoylaminophenol, o-stearoylaminophenol, p-lauroylaminophenol, p-butyrylaminophenol, m-acetylaminophenol, o-acetylaminophenol, p-acetylaminophenol, o-butylaminocarbonylphenol, o-stearylaminocarbonylphenol, p-stearylaminocarbonylphenol, 1,1,3-tris (3-tert-
Butyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tris (3-tert-butyl-4-
(Hydroxy-6-ethylphenyl) butane, 1,1,3
-Tris (3,5-di-tert-butyl-4-hydroxyphenyl) butane, 1,1,3-tris (3-te
rt-butyl-4-hydroxy-6-methylphenyl)
Propane, 1,2,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane,
1,3-tris (3-phenyl-4-hydroxyphenyl) butane, 1,1,3-tris (3-cyclohexyl-4-hydroxy-5-methylphenyl) butane, 1,
1,3-tris (3-cyclohexyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tetra (3-phenyl-4-hydroxyphenyl) propane,
1,1,3,3-tetra (3-cyclohexyl-4-hydroxy-6-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxy-6-methylphenyl) butane, It is also possible to add a phenol compound such as 1-bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) butane.

The acid developer is preferably used in an amount of 5 to 500 parts by weight, more preferably 20 to 200 parts by weight, based on 100 parts by weight of the colorless or pale color dye precursor. When the amount of the acidic developer is 5 parts by weight or more, the color development of the dye precursor is good and the color density is high. Also, an acidic developer 50
When the amount is 0 part by weight or less, the acidic developer hardly remains, which is economically advantageous and preferable. Also when the color former of the present invention is used as a pressure-sensitive recording material, the addition of an acidic developer improves the image density and makes it possible to obtain a clear color-developed pressure-sensitive recording material.

As the acidic developer, an electron-accepting substance is used, and examples thereof include acid clay,
Activated clay, attapulgite, benite, zeolite, colloidal silica, magnesium silicate, talc,
Inorganic compounds such as aluminum silicate, or phenol,
Cresol, butylphenol, octylphenol,
Phenylphenol, chlorophenol, salicylic acid or the like, or an aldehyde condensed novolak resin derived therefrom and a metal salt thereof, 3-isopropylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-t-butylsalicylic acid, 3,5-
Di (α-methylbenzyl) salicylic acid, 3,5-di-t
Salicylic acid derivatives such as -octylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3,5-di (α, α-dimethylbenzyl) salicylic acid, and 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid; Metal salts and the like.

By adding a fluorescent dye to the color former of the present invention, whiteness is improved. As the fluorescent dye used in addition to the color former of the present invention, various known dyes can be used, and examples thereof include a stilbene derivative, a coumarin derivative, a pyrazoline derivative, a bisstyryl biphenyl derivative, a naphthalimide derivative, and a bisbenzooxazolyl derivative. Although not limited to these, diaminostilbene disulfonic acid derivatives are particularly preferred. The amount of the fluorescent dye used was 0.0% based on the total solid content of the color former.
It is preferably present in an amount of 1 to 3% by weight, more preferably in the range of 0.1 to 2% by weight. If the amount of the fluorescent dye exceeds 3% by weight, the color former may be colored. If the amount is less than 0.01% by weight, the effect on whiteness is reduced.

Next, the color former of the present invention may contain a preservative. The preservability-imparting agent according to the present invention is an additive such as an image stabilizer, a light stabilizer and an antioxidant. By using these preservatives in combination with a urea urethane compound developer (a developer containing a urea urethane compound) and a colorless or pale dye precursor, the light resistance of the color former can be improved, A recording material having excellent properties can be obtained.

The image stabilizer as a preferable example of the preservative imparting agent used in the present invention includes, for example,
1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-
Methyl-4-hydroxy-5-cyclohexylphenyl) butane, 4,4′-butylidenebis (2-tert-butyl-5-methylphenol), 4,4′-thiobis (2
-Tert-butyl-5-methylphenol), 2,2'-
Thiobis (6-tert-butyl-4-methylphenol),
Hindered phenol compounds such as 2,2′-methylenebis (6-tert-butyl-4-methylphenol);
Benzyloxy-4 '-(2-methylglycidyloxy) diphenylsulfone, 4,4'-diglycidyloxydiphenylsulfone, 1,4-diglycidyloxybenzene, sodium-2,2'-methylenebis (4,6
-Di-tert-butylphenyl) phosphate, 2-propanol derivative, salicylic acid derivative and the like. These image stabilizers are usually preferably 5 to 1000 parts by weight based on 100 parts by weight of a colorless or pale color dye precursor. Department,
More preferably, 10 to 500 parts by weight are used. When the amount of the image stabilizer is 5 parts by weight or more, the light resistance is good and the color density is high. Further, if the amount of the image stabilizer is more than 1000 parts by weight, the effect on light fastness is not improved, and it is economically disadvantageous.

As a light stabilizer as a preferred example of the preservability-imparting agent used in the present invention, for example, 2- (2 ′)
-Hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-t
-Butyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-5 '-(1,1,3,
3-tetramethylbutyl) phenyl] benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2-
(3'-t-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2-
(2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'-di-t-pentyl-2'-hydroxyphenyl) benzotriazole,
-(3'-tert-butyl-2'-hydroxy-5'-octyloxycarbonylethylphenyl) -5-chlorobenzotriazole and the like; 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy- , 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'
-Trihydroxy, 2'-hydroxy-4,4'-dimethoxy- or 4- (2-ethylhexyloxy)
4-hydroxybenzophenone derivative; 4-t-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-t-butylbenzoyl) resorcinol, 2,4-di-t-butylphenyl 3, 5-di-t-
Butyl-4-hydroxybenzoate, hexadecyl 3,5-di-t-butyl-4-hydroxybenzoate and the like; ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α -Carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate and the like; bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6) -Tetramethyl-4-piperidyl) succinate, bis (1,2,2
2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) adipate and the like; 4,4'-di-octyloxyoxanilide, 2,2'-diethoxyoxyoxanilide, 2,
2'-di-octyloxy-5,5'-di-t-butyloxanilide, 2,2'-di-dodecyloxy-5
5'-di-t-butyl oxanilide, 2-ethoxy-
2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxanilide, 2-ethoxy-5
-T-butyl-2'-ethoxyoxanilide and the like; 2,
4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethyl Phenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl)
-1,3,5-triazine, 2- (2-hydroxy-4
-Dodecyloxyphenyl) -4,6-bis (2,4-
Dimethylphenyl) -1,3,5-triazine and the like. These light stabilizers are generally used in an amount of preferably 5 to 100 parts by weight of a colorless or pale color dye precursor.
-1000 parts by weight, more preferably 10-500 parts by weight. When the amount of the light stabilizer is 5 parts by weight or more, the light resistance is good and the color density is high. The image stabilizer is 100
If it exceeds 0 parts by weight, the effect on light resistance is not improved, and it is economically disadvantageous.

Antioxidants as preferred examples of the preservability-imparting agent used in the present invention include, for example, 2,6-
Di-t-butyl-4-methylphenol, 2-t-4,
6-dimethylphenol, 2,6-di-t-butyl-4
-Ethylphenol, 2,6-di-t-butyl-4-n
-Butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-
Methylphenol, 2- (α-methylcyclohexyl)
-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-dinonyl-4-methylphenol, 2,6-di-t-butyl -4-methoxymethylphenol, 2,4-dimethyl-6- (1'-methyl-
Undeca-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-heptadec-1'-yl)-
Phenol, 2,4-dimethyl-6- (1'-methyl-
Trideca-1'-yl) -phenol and mixtures thereof; 2,4-di-octylthiomethyl-6-t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-di-octyl Thiomethyl-6
Ethylphenol, 2,6-di-dodecylthiomethyl-
4-nonylphenol and mixtures thereof; 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-
t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4 -Hydroxyanisole, 3,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate, bis (3,5-di-t- Butyl-4-
(Hydroxyphenyl) adipates and mixtures thereof;
2,4-bis-octylmercapto-6- (3,5-di-t-butyl-4-hydroxyanilino) -1,3,5
-Triazine, 2-octylmercapto-4,6-bis (3,5-di-t-butyl-4-hydroxyanilino)
-1,3,5-triazine, 2-octylmercapto-
4,6-bis (3,5-di-t-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5
-Tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-tris (4
-T-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 2,4,6-tris (3
5-di-t-butyl-4-hydroxyphenylethyl)
-1,3,5-triazine, 1,3,5-tris (3,
5-di-t-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine,
3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) -isocyanurate and the like; 2,2'-methylenebis (6-t-butyl-4-methylphenol), 2,2'-methylenebis (6- t-butyl-4-
Ethylphenol), 2,2'-ethylidenebis (4,
6-di-t-butylphenol), 2,2'-ethylidenebis (6-t-butyl-4-isobutylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4 '-Methylenebis (6-t-butyl-2-methylphenol), 1,1-bis (5-t
-Butyl-4-hydroxy-2-methylphenyl) butane, ethylene glycol bis [3,3'-bis (3'-
t-butyl-4'-hydroxyphenyl) butyrate]
1,3,5-tris (3,5-di-t-butyl-4)
-Hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2, 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) -phenol and the like can be mentioned. These antioxidants are usually preferably 5 to 5 parts by weight of a colorless or pale color dye precursor.
1000 parts by weight, more preferably 10 to 500 parts by weight, is used. When the amount of the antioxidant is 5 parts by weight or more, the light resistance is good and the color density is high. In addition, when the antioxidant is 1000
If the amount is more than the weight part, the effect on light resistance is not improved, and it is economically disadvantageous.

A recording material can be obtained by forming a color-forming layer on a support by using the color-forming agent of the present invention by a method such as coating. The configuration differs depending on the type of recording material. The coloring agent of the present invention can be used as various recording materials such as a heat-sensitive recording material and a pressure-sensitive recording material, and is particularly suitable as a heat-sensitive recording material. When the recording material is a heat-sensitive recording material, a heat-sensitive recording layer for coloring by heating is provided on the support. Specifically, the urea urethane compound, a colorless or light-colored dye precursor such as a leuco dye,
It is necessary to apply a heat-fusible substance or the like described below in the form of a dispersion to a support together with other necessary components to form a heat-sensitive recording layer. The dispersion is prepared by finely pulverizing one or more of these compounds in an aqueous solution containing a compound having a dispersing ability such as a water-soluble polymer or a surfactant using a sand grinder or the like. . The particle diameter of each dispersion is preferably 0.1 to 10 μm, particularly preferably about 1 μm. Specific examples of the compound having a dispersing ability that can be used in the present invention include water-soluble polymers such as polyvinyl alcohol, carboxylic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, methylcellulose, hydroxypropylmethylcellulose, and hydroxypropylcellulose, and condensation. Naphthalene sulfonate, polyoxyethylene alkyl ether sulfate (eg, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate), sodium dialkyl sulfosuccinate, alkyl phosphorus Acid salts (for example, diethanolamine alkyl phosphate, potassium alkyl phosphate) and special carboxylic acid type polymers Surfactants, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, polyethylene glycol fatty acid ester, dicyanamide polyamine, tertiary amine Salt, fourth
And cationic surfactants such as quaternary ammonium salts. Among these, polyvinyl alcohol, carboxylic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, and methylcellulose are particularly preferable. These can be used alone or in combination.

In the case where the urea urethane compound developer according to the present invention is used in a heat-sensitive recording material, by setting the average particle diameter of the urea urethane compound developer to 0.05 μm or more and 5 μm or less, sufficient color sensitivity and color development can be obtained. The recorded image thus obtained is remarkably stable, and a thermosensitive recording material having good plasticizer resistance can be obtained. More preferably, the average particle size is 0.1.
1 μm or more and 3 μm or less. Average particle size 0.05
If it is less than μm, the storability of the skin against the plasticizer will be poor.
On the other hand, when the average particle diameter is 5 μm or more, the sensitivity of the heat-sensitive recording material decreases. In particular, when the urea urethane compound is wet-pulverized in an aqueous medium, the liquid temperature of the aqueous medium is preferably 60 ° C. or lower. When the urea urethane compound developer comes into contact with water during pulverization, hydrolysis of urethane groups may proceed depending on conditions, and the sensitivity of the heat-sensitive recording material using the urea urethane compound developer may decrease. is there. In particular, when the liquid temperature at the time of pulverization is higher than 60 ° C., the sensitivity is greatly reduced. The liquid temperature during pulverization is more preferably 4
0 ° C. or less. In the case of pulverizing the urea urethane compound developer, it is desirable to pulverize in a neutral region having a pH of 5 to 10. If the pH at the time of pulverization is less than 5, inorganic pigments and the like may be decomposed at the time of preparing the heat-sensitive coating liquid, and the sensitivity may be reduced. On the other hand, if the pH is higher than 10, hydrolysis of the urea urethane compound developer may occur, and the sensitivity may decrease.

Specific examples of the dispersant which can be used in the present invention to pulverize the urea urethane compound developer to form a dispersion include polyvinyl alcohol, carboxylic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, Water-soluble polymers such as methylcellulose, hydroxypropylmethylcellulose and hydroxypropylcellulose, condensed naphthalene sulfonates, polyoxyethylene alkyl ether sulfates (for example, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, poly Sodium oxyethylene alkyl phenyl ether sulfate), sodium dialkyl sulfosuccinate, alkyl phosphates (eg, diethanolamine alkyl phosphate, Anionic surfactants such as potassium ruphosphate), special carboxylic acid type polymers, nonionic surfactants such as polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, polyethylene glycol fatty acid ester, dicyan Cationic surfactants such as amidopolyamines, tertiary amine salts and quaternary ammonium salts can be mentioned. Among these, a water-soluble polymer and an anionic surfactant can obtain a highly sensitive thermosensitive recording material regardless of the conditions under which the urea urethane compound developer is dispersed, and the average particle diameter of the urea urethane compound developer is obtained. Regardless of the size, a heat-sensitive recording material having improved background preservability against a plasticizer can be obtained, which is preferable. Further, polyvinyl alcohol, modified polyvinyl alcohol, methylcellulose, hydroxypropylmethylcellulose, condensed sodium naphthalenesulfonate, ammonium polycarboxylate, water-soluble low molecular weight copolymer and sodium 2-ethylhexylsulfosuccinate are preferred. Among them, methylcellulose, hydroxypropylmethylcellulose, condensed sodium naphthalenesulfonate, and a water-soluble low molecular weight copolymer are preferable, and hydroxypropylmethylcellulose is particularly preferable. These can be used alone or in combination.

As the dispersant which can be used in the present invention to pulverize the colorless or pale color dye precursor to form a dispersion, the same compounds as those used for dispersing the urea urethane compound developer can be used. Can be used. Among them, a water-soluble polymer, an anionic surfactant and a mixed dispersant of both are particularly preferred from the viewpoint of improving the sensitivity of the heat-sensitive recording material and the storability of the plasticizer against the background. Further, a mixed dispersant in which the water-soluble polymer is methylcellulose or hydroxypropylmethylcellulose and the anionic surfactant is polyoxyethylene alkyl ether sulfate or sodium 2-ethylhexylsulfosuccinate is preferred. Particularly preferred is a mixed dispersant of hydroxypropylmethylcellulose and sodium 2-ethylhexylsulfosuccinate. The pH of the coating solution containing the urea urethane compound and the colorless or pale color dye precursor is preferably 5 to 12.

In addition, the thermal recording layer contains diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin and the like as pigments. You can also. In addition, for the purpose of preventing head abrasion and sticking, zinc stearate, higher fatty acid metal salts such as calcium stearate, paraffin,
Waxes such as paraffin oxide, polyethylene, polyethylene oxide, stearic acid amide, caster wax, etc .; dispersants such as dioctyl sodium sulfosuccinate; ultraviolet absorbers such as benzophenone and benzotriazole; surfactants and fluorescent dyes Etc. can be contained as needed.

Examples of the binder that can be used for forming the heat-sensitive recording layer include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, acrylamide / acrylic acid Water-soluble binders such as ester copolymers, acrylamide / acrylate / methacrylic acid terpolymers, styrene / maleic anhydride copolymer alkali salts, ethylene / maleic anhydride copolymer alkali salts, and styrene Latex-based water-insoluble binders such as styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, and methyl acrylate / butadiene copolymer.

As the support of the heat-sensitive recording layer, paper is mainly used. In addition to paper, various woven fabrics, non-woven fabrics, synthetic resin films, laminated paper, synthetic paper, metal foil, or composite sheets obtained by combining these are used. It can be used arbitrarily according to the purpose. The basis weight of this support is 40 g / m
^{2 to} 200 g / m ² is desirable, and as the heat-sensitive recording material is desired to have as high a flatness as possible, it is desirable to use a material having excellent surface smoothness and flatness. It is preferable to apply pressure to perform surface treatment. Further, the surface pH of the support is preferably from 3 to 9, more preferably from 5 to 9, and furthermore, p
H6 to 8 are particularly preferred. Surface pH of support
If it is less than 3, background covering tends to occur, and if it exceeds pH 12, the urea urethane compound color developer may decompose and the color density may decrease.

The thermosensitive recording layer may be composed of a single layer or a plurality of layers. For example, each color forming component may be contained one layer at a time to form a multilayer structure. Further, a protective layer consisting of one or more layers may be provided on the heat-sensitive recording layer, or an intermediate layer consisting of one or more layers may be provided between the support and the heat-sensitive recording layer. Good. This heat-sensitive recording layer can be obtained by mixing each aqueous dispersion obtained by finely pulverizing each color-forming component or other components, a binder and the like, applying the mixture on a support, and drying. The coating amount is preferably from 1 to 15 g / m ² in a state where the coating liquid is dried.

When the color former of the present invention is used as a thermosensitive recording material, a heat fusible substance can be contained in the color former to improve the sensitivity. The heat-fusible substance preferably has a melting point of 60C to 180C, and particularly preferably has a melting point of 80C to 140C. For example, benzyl p-benzyloxybenzoate, stearic acid amide or an emulsified product thereof, palmitic acid amide, N-methylol stearic acid amide, β-naphthylbenzyl ether, N-stearyl urea, N, N′-distearyl urea, β -Naphthoic acid phenyl ester, 1-hydroxy-2-naphthoic acid phenyl ester, β-naphthol (p-methylbenzyl) ether, 1,4-dimethoxynaphthalene, 1-methoxy-4-benzyloxynaphthalene, N-stearoylurea, p-benzylbiphenyl, 1,2-diphenoxyethane, 1,2-di (m
-Methylphenoxy) ethane, 1,2-bis (3,4-
Dimethylphenyl) ethane, 1-phenoxy-2- (4
-Chlorophenoxy) ethane, 1,4-butanediol phenyl ether, dimethyl terephthalate, metaterphenyl, dibenzyl oxalate, di-p-methylbenzyl oxalate, oxalic acid (p-chlorobenzyl)
ester.

Further, 4,4'-dimethoxybenzophenone, 4,4'-dichlorobenzophenone, 4,4'-
Difluorobenzophenone, diphenylsulfone, 4,
4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 4,4'-dichlorodiphenyldisulfide, diphenylamine, 2-methyl-4-
Methoxydiphenylamine, N, N'-diphenyl-p
-Phenylenediamine, 1- (N-phenylamino) naphthalene, benzyl, 1,3-diphenyl-1,3-propanedione and the like are preferred because of their high effect of improving sensitivity.

Also, benzyl 4-hydroxybenzoate,
4- (benzyloxy) phenol, 2,4-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4,4′-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenyl sulfone,
Bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl-4'-
Methylphenyl sulfone, bis (2-methyl-3-te
rt-butyl-4-hydroxyphenyl) sulfide,
4,4'-dihydroxydiphenyl ether, 4,4 '
-Thiodiphenol, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine,
Bis (4-hydroxy-3-methylphenyl) sulfide, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4,4'-thiobisbenzenethiol, salicylanilide, 4,4'-diamino-3,3'- Diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-thiodianiline, , 2 '
-Dithiodianiline, 4,4'-dithiodianiline,
4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3 , 4'-Diaminodiphenyl sulfone, 3,3 '
-Diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 3,3'-diaminobenzophenone,
4,4′-diaminobenzophenone, o-chloroanilide acetoacetate, anilide acetoacetate, o-acetoacetate
-Toluidide, acetoacetate p-toluidide, acetoacetate o-anisidide, acetoacetate m-xylidide,
p-acetotoluidide or the like may be used.

Of these, diphenyl sulfone, di-p-methylbenzyl oxalate, benzyl, β-naphthylbenzyl ether, p-benzylbiphenyl, 1,2-di (m-methylphenoxy) ethane, 1,1, 2-Diphenoxymethylbenzene, metaterphenyl, and stearamide are used. Moreover,
Among these, the use of a heat-fusible substance represented by the following structural formula (XVIII) for a heat-sensitive recording material improves its sensitivity, and also improves the plasticizer resistance of the printed portion and the heat resistance of the background. Great effect. In particular, the following structural formula (XI
The heat-fusible substances represented by X) are particularly preferred.

[0361]

Embedded image

(Where Y is -SO ₂ -,-(S) _n -,-
O -, - CO -, - CH 2 -, - CH (C 6 H 5) -, -
_{C (CH 3) 2 -,} - COCO -, - CO 3 -, - COC
_{H 2 CO -, - COOCH 2} -, - CONH -, - OCH
_It represents either-or -NH-. n is 1 or 2. The hydrogen atom of the benzene ring includes a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanato group, an isothiocyanato group, a mercapto group, a sulfamoyl group, a sulfone group, an amino group, an aromatic compound residue, and an aliphatic compound. It may be substituted by a residue or a heterocyclic compound residue. )

[0363]

Embedded image

(The hydrogen atom of the benzene ring in the formula is a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group,
Isocyanato group, isothiocyanato group, mercapto group,
It may be substituted by a sulfamoyl group, a sulfone group, an amino group, an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue. The heat-fusible substance may be used alone or as a mixture of two or more kinds. In order to obtain a sufficient thermal response, 100 parts by weight of a colorless or light-colored dye precursor is used. 10-3
00 parts by weight, preferably 20 to 25 parts by weight.
It is more preferable to use 0 parts by weight.

As the dispersant which can be used in the present invention to pulverize the heat-fusible substance to form a dispersion, the same compound as the dispersant used for dispersing the urea urethane compound developer can be used. Can be. Among them, a water-soluble polymer and an anionic surfactant are particularly preferable in order to improve the storability of the heat-sensitive recording material against the plasticizer. , Ammonium polycarboxylates, water-soluble low molecular weight copolymers and sodium 2-ethylhexylsulfosuccinate are preferred. Of these, modified polyvinyl alcohol, methylcellulose, hydroxypropylmethylcellulose, condensed sodium naphthalenesulfonate, and ammonium polycarboxylate are preferred, and hydroxypropylmethylcellulose is particularly preferred. These dispersants can be used alone or in combination.

When the urea urethane compound color developer is pulverized, it is pulverized simultaneously with the above-mentioned heat-fusible substance (co-pulverization).
By doing so, the sensitivity of the heat-sensitive recording material is further improved and the plasticizer resistance is improved as compared with the case where each compound is individually pulverized and then mixed. Further, as a dispersant for the urea urethane compound developer, at least one selected from methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalenesulfonate and a water-soluble low molecular weight copolymer is used, and a dispersant for a heat-fusible substance is used. By using at least one selected from modified polyvinyl alcohol, methylcellulose, hydroxypropylmethylcellulose, condensed sodium naphthalenesulfonate and ammonium polycarboxylate, the moisture resistance of the unprinted portion (background) of the thermosensitive recording material Can be improved.

The color former of the present invention can be used as various heat-sensitive recording materials.
It is suitable as a thermosensitive label, a multicolor thermosensitive recording material, and a thermosensitive recording material for laser marking. When the heat-sensitive recording material is a heat-sensitive magnetic recording material, it is preferable to provide a heat-sensitive recording layer containing a urea urethane compound developer on one surface of the support and a magnetic recording layer on the other surface. The magnetic recording layer in the thermosensitive magnetic recording material is, for example, barium ferrite, strontium ferrite, Co
Coating -γ-Fe ₂ O _2, the ferromagnetic powder such as γ-Fe ₂ O ₂ paint was uniformly dispersed in the aqueous binder such as an aqueous emulsion resin on a support, a magnetic recording layer and dried I do. At this time, various additives such as an antistatic agent such as carbon graphite, a wax as a lubricant, a color pigment for adjusting a hue, and a polyethylene oxide as a coating softener may be added according to the purpose.

The thermosensitive magnetic recording material of the present invention is suitable as a thermosensitive magnetic recording material for a ticket, a ticket, a prepaid card, and the like. When the heat-sensitive recording material is a heat-sensitive recording label, a form in which a heat-sensitive recording layer containing a urea urethane compound color developer is provided on one surface of the support and an adhesive layer is provided on the other surface is preferable. The pressure-sensitive adhesive layer of the heat-sensitive recording material contains a pressure-sensitive adhesive as a main component, and examples of the pressure-sensitive adhesive include a synthetic rubber-based emulsion-type adhesive, an acrylic emulsion-type adhesive, a natural rubber-based solvent-type adhesive, Acrylic solvent-based pressure-sensitive adhesives and silicone-based solvent-based pressure-sensitive adhesives can be mentioned, and acrylic emulsion-based pressure-sensitive adhesives are particularly preferable.

The thermosensitive recording label produced by the method of the present invention may be provided with a back layer (backcoat layer) between the pressure-sensitive adhesive layer and the support, if necessary, to correct the curl of the thermosensitive recording label and charge the thermosensitive recording label. Prevention and friction coefficient adjustment.
The same method as the method for forming the heat-sensitive recording layer can be used for the coating solution component, coating method, and the like of the back surface layer. The dry coating amount is preferably in the range of 0.2 to 10.0 g / m ² . The order of application in producing the label for heat-sensitive recording is not particularly limited. For example, after a heat-sensitive recording layer is provided on a support, a back coat layer is provided on another surface, and an adhesive layer is further provided. Alternatively, after the back coat layer is provided on the support, a thermosensitive recording layer may be provided on the other side, and an adhesive layer may be provided on the back coat layer.

As a method for providing an adhesive layer on the back coat layer, the adhesive layer liquid may be applied directly on the back coat layer and dried, or the adhesive layer liquid may be applied to release paper in advance and dried. And the back coat layer side of the heat-sensitive recording material before providing the pressure-sensitive adhesive layer.
Furthermore, an intermediate layer comprising one or more layers may be provided between the heat-sensitive recording layer and the support to improve the thermal responsiveness. The intermediate layer is mainly composed of organic and inorganic pigments, hollow particles, and a water-based binder such as a water-soluble polymer and latex. The same organic and inorganic pigments and water-based binder as those used in the heat-sensitive recording layer can be used. The method for forming the intermediate layer is not particularly limited, and a method similar to the method for forming the heat-sensitive recording layer can be used. Dry coating amount is 2.0 ~
A range of 15.0 g / m ² is preferred.

When the heat-sensitive recording material is a multicolor heat-sensitive recording material, at least two heat-sensitive recording layers are provided on one surface of the support, and at least one of the heat-sensitive recording layers is provided with a urea urethane compound developer. Is preferred. The support to be used is prepared by heating and kneading a polyolefin resin and a white inorganic pigment, extruding from a die, and stretching in the longitudinal direction, laminating one or two layers per side of a film composed of a polyolefin resin and a white inorganic pigment on both surfaces, Synthetic paper manufactured by making it translucent or opaque by stretching it in the transverse direction, and by heating thermoplastic resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer resin, polyvinyl chloride, polystyrene, polyester alone or a mixture Knead,
Films extruded from a die and biaxially stretched, opaque films obtained by mixing these resins with a white inorganic pigment and biaxially stretching, as well as high-quality paper, medium-quality paper, roll paper, recycled paper, Those manufactured from pulp fibers, such as paper, can be used. In order to improve the uniformity of the image, the support made of pulp fibers is preferably provided with a coating layer in advance and then coated with a heat-sensitive layer.

The heat-sensitive coloring layer of the present invention contains, as main components, a coloring agent and an adhesive which cause a coloring reaction upon contact of a substance by heating. As the color former, specifically, a colorless or pale-colored dye precursor and the urea urethane developer described above, which develops the color of the dye precursor by heating, or a coupler that reacts with a diazo compound and the diazo compound to form a color And the like. Further, a crosslinking agent, a pigment, and a heat-fusible substance can be added as needed. The coating amount of the heat-sensitive coloring layer is generally 3 to 15 in terms of coloring sensitivity and coloring density.
g / m ² is preferred. As the color-forming dye, the above-mentioned colorless or light-colored dye precursor which can react with a urea urethane compound developer under heating to form a color is used.

On the other hand, the compound used in the heat-sensitive recording layer containing, as a main component, a diazo compound and a coupler which forms a color by reacting with the diazo compound is a known photodegradable diazo compound or a dye which reacts with the diazo compound. And a basic substance or the like can be added as necessary to promote the reaction between the diazo compound and the coupler. The coupler is 10 to 1000 parts by weight, and the basic substance is 10 to 20 parts by weight based on 100 parts by weight of the diazo compound.
It is preferable to mix and use at a ratio of 00 parts by weight. The photo-decomposable diazo compound in the present invention means a diazo photosensitive material which reacts with a coupling component when heated to form a dye, such as a diazonium salt, a diazosulfonate compound, a diazoamino compound or a quinonediazide compound. The diazonium salt is a compound represented by the general formula Ar—N ₂ ⁺ · X ⁻ (where Ar represents an aromatic moiety, N ₂ ⁺ represents a diazonium group, and X ⁻ represents a counter anion). These have various maximum absorption wavelengths depending on the position and type of the substituent in the Ar portion.

The diazonium compound used in the present invention
A specific example is 4-dimethylaminobenzenediazoni.
, 4-diethylaminobenzenediazonium, 4-
Dipropylaminobenzenediazonium,
Nzilaminobenzenediazonium, 4-dibenzyla
Minobenzenediazonium, 4-ethylhydroxyethyl
Ruaminobenzenediazonium, 4-diethylamino-
2-methoxybenzenediazonium, 4-dimethyl-3
-Methylbenzenediazonium, 4-benzoylamino
-2,5-diethoxybenzenediazonium, 4-mol
Holinobenzenediazonium, 4-morpholino-2,5
-Diethoxybenzenediazonium, 4-morpholino-
2,5-dibutoxybenzenediazonium, 4-anili
Nobenzenediazonium, 4-toluylmercapto-
2,5-diethoxybenzenediazonium, 4- (N,
N-dioctylcarbamoyl) benzenediazonium,
2-octadecyloxybenzenediazonium, 4-
(4-tert-octylphenoxy) benzenediazo
And 4- (2,4-di-tert-amylphenoxy)
B) benzenediazonium, 2- (4-tert-octane)
Tylphenoxy) benzenediazonium, 5-chloro-
2- (4-tert-octylphenoxy) benzenedi
Azonium, 2,5-bis-octadecyloxybenze
Diazonium, 2,4-bis-octadecyloxybe
Nzendiazonium, 4- (N-octylteuroylua
Mino) benzenediazonium and the like.
Specific examples of the counter anion of the diazonium salt used in the present invention
For example, Cl 1/2 ZnCl_Two ^-, BF_Four ^-, PF₆ ^-,
B (Ph)_Four ^-, C_nF_{2n + 1}COO^-(N represents 3 to 9
), C _mF_{2m + 1}SO_Three ^-(M represents 2 to 8), (C_kF
_{2k + 1}SO_Two)_TwoCH- (k represents 1 to 18) and the like
be able to.

The diazosulfonate compound used in the present invention is a compound represented by the general formula Ar—N ₂ —SO ₃ Na (wherein Ar represents an aromatic moiety). Specific examples of the diazosulfonate compound used in the present invention include 2-methoxy, 2-phenoxy, 2-methoxy-4-phenoxy, 2,4-dimethoxy, 2-methyl-4-methoxy, 2,4-dimethyl, 2,4,6-
Trimethyl, 2,4,6-trimethoxy, 2,4-dimethoxy-5-chloro, 2-methoxy-5-nitro, 2-
Methoxy-5-acetamide, 2-methoxy-5-N,
N-diethylsulfonamide, 2-methoxy-5-N-
Sodium benzenediazosulfonate having a substituent such as phenylcarbamyl, 3-methyl, 4-methyl, 4-methoxy, 4-ethoxy, 4-phenyl, 4-phenoxy, 4-acetamide, or 4- (N- Ethyl-N-benzylamino), 4- (N, N-dimethylamino), 4- (N, N-diethylamino), 4- (N, N
-Diethylamino) -3-chloro, 4- (N-ethylamino) -3-methyl, 4- (N, N-diethylamino)
-2-methyl, 4- (N-ethyl-N-β-hydroxyethylamino), 4-pyrrolidino-3-chloro, 4-pyrrolidino-3,5-dichloro, 4-morpholino, 4-morpholino-3-chloro , 4-morpholino-2-methoxy, 4-morpholino-2,5-diethoxy, 4-morpholino-2,5-dibutoxy, 4- (4'-tolylmercapto) -2,5-dibutoxy, 4- (4 ' -Tolylmercapto) -2,5-diethoxy, 4- (4'-methoxybenzoylamino) -2,5-dibutoxy, 4-diphenylamino and the like. When using these diazosulfonate compounds, it is desirable to activate the diazosulfonate by irradiating the diazosulfonate with light before printing.

As the diazoamino compound usable in the present invention, the diazo group is coupled with dicyandiamide, sarcosine, methyltaurine, N-ethylanthranic acid-5-sulfonic acid, monoethanolamine, diethanolamine, guanidine or the like. Compound. The quinonediazide used in the present invention is structurally also considered to be an inner salt type diazonium salt, for example, o-quinonediazide, o-naphthoquinonediazide and the like, and 1,2-quinonediazide-4-sulfonic acid, It contains salts, esters, amide compounds and the like of 2-naphthoquinonediazide-5-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid and the like. Specific examples of the quinonediazide used in the present invention include sodium 1,2-quinonediazide-4-sulfonate, sodium 1,2-naphthoquinonediazide-5-sulfonate, sodium 1,2-naphthoquinonediazide-4-sulfonate, 1,2-naphthoquinonediazide-5
Sulfonic acid-p-cumylphenyl, 1,2-naphthoquinonediazide-4-sulfonic acid-p-cumylphenyl,
Methyl 1,2-naphthoquinonediazide-5-sulfonate, ethyl 1,2-naphthoquinonediazide-5-sulfonate, 1,2-naphthoquinonediazide-5-sulfonate-dimethylamide, 1,2-naphthoquinonediazide-5
-Esters of sulfonic acids and novolak resins. Furthermore, two or more of these photodegradable diazo compounds may be used in combination.

The coupler used in the present invention reacts with a diazo compound to form a dye. For example, a typical coupler that produces a yellow dye is one in which a methylene group is activated by an adjacent carbonyl group, and has the general formula RCOCH ₂ CO-R ′ (where R is an alkyl group or an allyl group. , R ′ represents an aromatic amine). Further, as a magenta coupler, 1)
Cyanoacetyl derivatives of cyclic compounds, or 2) heterocyclic compounds having an active methylene or other coupling moiety in the heterocycle, such as pyrazolone compounds and indazolone compounds. Examples of the cyan coupler include phenols and naphthols.

Specific examples of the coupler used in the present invention include 4- (p-toluenesulfonylamino) -ω-
Benzoylacetanilide, α-benzoyl-o-methoxyacetanilide, 2-cyanoacetyl-coumarone,
1- (2,4,6-trichlorophenyl) -3-p-nitroamino-2-pyrazolone-5-one, resorcinol,
Phloroglucin, 2,3-dihydroxynaphthalene,
Examples thereof include 2,6-dibromo-1,5-dihydroxy-naphthalene and N- (o-acetamidophenethyl) -1-hydroxy-2-naphthamide. Further, two or more of these couplers can be used in combination.

The coupling reaction between the diazo compound and the coupler proceeds more smoothly in a basic atmosphere. Therefore, it is desirable to add a basic substance to the thermosensitive coloring layer. As the basic substance, a poorly water-soluble or water-insoluble basic substance or a substance that generates an alkali by heating is used. For example, inorganic and organic ammonium salts,
Organic amines, amides, ureas and thioureas and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, formamidines, And nitrogen-containing compounds such as pyridines.

Specific examples thereof include tricyclohexylamine, tribenzylamine, octadodecylbenzylamine, stearylamine, allylurea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, and 4-phenylimidazole. , 2-phenyl-4-methylimidazole, 2-undecylimidazoline, 2,4,5-trifuryl-2-
Imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-triphenylguanidine, 1,2-dicyclohexylguanidine, 1,2,3-tri Cyclohexylguanidine, guanidine trichloroacetate, N,
N'-dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetate, 2-aminobenzothiazole, 2-benzoylhydrazinobenzothiazole and the like. Two or more of these basic substances may be used in combination.

In the present invention, the thermosensitive coloring layer formed of a combination of a diazo compound and a coupler is added with a weakly acidic substance such as citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid or the like to improve the storage stability. Can be improved.
The color-forming component used in the present invention is used in the form of a solid dispersion obtained by dispersing in an aqueous solution of a water-soluble polymer and coating and drying, as is generally used in thermal recording materials. Of course you can. Also, JP-A-59-19088
No. 6, JP-A-60-49991, JP-A-61
As described in JP-A-169281, the color former is microencapsulated to prevent the contact between the color developer and the developer at room temperature by the isolation effect of the capsule wall, and to improve the raw preservability. it can. The microcapsules have a property that the color former and the developer can come into contact only while being heated to a certain temperature or higher. The temperature at which the contact between the color former and the developer starts can be controlled by appropriately selecting the capsule wall material, the capsule core substance, the additives, and the like.

As the wall material of the microcapsules in the present invention, conventionally known materials such as polyurethane, polyurea, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, gelatin, polyvinylpyrrolidone, and polyvinyl alcohol can be used. Microcapsule wall materials. Further, two or more of these polymers may be used in combination. In the present invention, as the adhesive contained in the thermosensitive coloring layer, any of a water-soluble resin and a water-dispersible resin can be used. However, it is necessary that the mixture does not develop color, aggregate, or become highly viscous when mixed with each dispersion of the color-forming dye and the developer, and the formed heat-sensitive recording layer The film is tough,
It is necessary that there is no desensitizing effect. The amount of the adhesive in the thermosensitive coloring layer is preferably 8 to 20% based on the solid content of the thermosensitive coloring layer.
If it exceeds 0%, there is a problem that the sensitivity is reduced. In order to improve the water resistance of the heat-sensitive coloring layer, a crosslinking agent for curing the resin can be used.

In the multicolor heat-sensitive recording material of the present invention, it is effective to provide an intermediate layer between the heat-sensitive recording layers in order to improve the thermal separability. The intermediate layer contains, as a main component, the same water-soluble resin and water-dispersible resin used as an adhesive in the heat-sensitive recording layer, and may further contain a pigment, a crosslinking agent, and the like. The coating amount of the intermediate layer is 1.0 to 5.0.
g / m ² is preferred. If the coating amount is less than 1.0 g / m ^2, there is no sufficient effect of preventing diffusion between the recording layers, which causes deterioration in image quality. If the coating amount exceeds 5.0 g / m ² , there is a disadvantage that the sensitivity is reduced.

As one particularly preferred form of the multicolor heat-sensitive recording material of the present invention, two heat-sensitive recording layers having different coloring temperatures and different colors are formed on one surface of a support by laminating them. A multicolor heat-sensitive recording material in which the upper heat-sensitive recording layer contains a developer or reversible developer and the lower heat-sensitive recording layer contains a urea urethane compound developer. Among these, the color-reducing agent used in the upper heat-sensitive recording layer expresses a color-developing function at low-temperature heating and a color-decoloring function at high-temperature heating. It is an amphoteric compound having a basic group that has a color function. The acidic group is typically a phenolic hydroxyl group or a carboxyl group, and the basic group is typically an amino group. The basic group may be present as a functional group, but is preferably present as a part of a salt compound such as a complex of a phenol carboxylic acid compound and an amine compound. Specific examples of such a color reducing agent include, for example, those shown below. Examples of the phenol carboxylic acid compound constituting the color-reducing agent include 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and 2,3. -Dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid,
2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, gallic acid, bis (4-hydroxyphenyl)
Acetic acid, 3,3-bis (4-hydroxyphenyl) propionic acid and the like can be mentioned.

Examples of the amine compound which forms a salt or a complex salt with the phenol carboxylic acid compound include octylamine, nonylamine, decylamine, laurylamine, tetradecylamine, heptadecylamine, stearylamine, behenylamine, 3-methoxypropylamine,
Hexamethylene diamine and the like. The reversible developer is, for example, a phenolic compound or a phosphonic acid compound having an aliphatic hydrocarbon group having 8 or more carbon atoms. Specific examples of such a reversible color developer include, for example, those shown below, as long as they exhibit a color developing function at low-temperature heating and have a color erasing function at high-temperature heating. However, the present invention is not limited to this.

4- (octadecylthio) phenol, 4
-(Docosylthio) phenol, 4- (octadecyloxy) phenol, 4- (docosyloxy) phenol, N-octadecyl-4-hydroxybenzamide,
4'-Hydroxydocosaneanilide, N- (4-hydroxyphenyl) -N'-n-octadecylurea, docosylphosphonic acid and the like. When recording is performed by a thermal printer or the like using the multicolor heat-sensitive recording material of the present invention, only the low-temperature coloring layer develops color in low-temperature heating printing, and the low-temperature coloring layer in the printed portion is decolorized in high-temperature heating printing to remove the high-temperature coloring layer. Only color develops. In addition, by using a urea urethane compound, the color density is sufficient, and the recorded image formed is extremely stable,
An article for laser marking which hardly causes discoloration even with oils, fats, chemicals, fingerprints, etc. can be obtained, which is particularly advantageous from the viewpoint of long-term storage of records.

In the article for laser marking of the present invention,
The thermosensitive recording layer preferably contains a recording sensitivity improver. As the recording sensitivity improver which can be used, those having absorptivity of laser light used for irradiation are used, and specific examples thereof include aluminum hydroxide, wollastonite, bentonite, mica (white mica, gold And various inorganic compounds such as silicate minerals such as mica), calcium silicate, talc, kaolin, clay and fayalite, horn blends, and part-timers. Particularly preferred are aluminum hydroxide, white mica, wollastonite and kaolin. These inorganic compounds can be used alone or in combination of two or more.

The ratio of the colorless or pale color dye precursor to the recording sensitivity improver in the heat-sensitive recording layer used in the present invention is as follows:
The dye precursor to be used can be appropriately selected depending on the type of the recording sensitivity improver, and is not particularly limited. In general, the recording sensitivity improver is 100 parts by weight based on the color former. 10 to 5000 parts by weight, preferably 100 to
It can be used within the range of 2000 parts by weight. The ratio of the dye precursor, the urea urethane compound color developer, and the recording sensitivity improver in the heat-sensitive recording layer is 5 to 30% by weight, preferably 10 to 25% by weight, based on the total solid content in the layer. %, The urea urethane compound developer is 10 to 60% by weight,
Preferably, the content is 20 to 50% by weight, and the recording sensitivity improver is 5 to 4% by weight.
0% by weight, preferably in the range of 10 to 30% by weight.

By adding an acidic developer to the heat-sensitive recording layer of the article for laser marking of the present invention, the sensitivity is improved and an article for laser marking with vivid color is obtained. As the acidic developer, the above-mentioned generally used electron-accepting substances are used. In order to further improve the sensitivity of the article for laser marking of the present invention, the heat-sensitive recording layer may contain a heat-fusible substance. The heat-fusible substance preferably has a melting point of 60C to 180C, and particularly preferably has a melting point of 80C to 140C. The color-forming marking agent of the present invention has the above colorless or light-colored dye precursor, a urea urethane compound developer, a recording sensitivity improver, an aqueous binder and water as essential components,
Further, it can be obtained by mixing various auxiliaries as needed. The water used for the color marking agent is pH 5-1.
2, preferably in the range of pH 6-9. pH
If the pH is 5 or less, fog may occur, and if the pH is 12 or more, the urea urethane compound developer may have an adverse effect such as disappearance of the color developing ability. Water may be used as a mixture with a water-soluble organic solvent such as methanol or ethanol.

The color-forming marking agent used in the present invention may contain various auxiliaries, if necessary, in addition to the above-mentioned essential components in order to facilitate coating on a substrate. As various auxiliaries, for example, dispersants such as sodium dioctyl sulfosuccinate, sodium dodecylbenzene sulfonate, sodium salt of lauryl alcohol sulfate, fatty acid metal salts, concealing agents such as titanium oxide, antifoaming agents, viscosity modifiers , Fluorescent dyes, coloring agents and the like.

Printing (coating) the coloring agent of the present invention
The base material to be marked is not particularly limited as long as it requires marking, and is, for example, a predetermined portion of a food container, a packaging material, an electronic component, or the like, or an article such as a label base material to be affixed thereto. Is raised. Label base materials include paper, paper such as synthetic paper, synthetic resin film,
Plastics, metal-deposited paper and synthetic paper, metal-deposited films, metals, wood, and the like are appropriately used depending on the application. To prepare a coloring marker,
For example, the following may be performed. The binder is dissolved or dispersed in water or a solvent containing water as a main component. Color former,
For those that need to be dispersed in water or a solvent containing water as a main component, a developer, a recording sensitivity improver, and the like, use a dispersing machine such as a ball mill, an attritor, and a sand grinder, for example, using a dispersant such as polyvinyl alcohol. Each component is treated together or separately in water or a water-containing solvent to form a dispersion. The average particle size of each component after dispersion is usually about 2 μ or less, preferably about 1 μ or less. Next, the color-forming marking agent of the present invention is obtained by mixing the binder and the dispersion. The solid content of the color marking agent is 20 to 70% by weight, preferably 3% by weight.
It is about 0 to 65% by weight.

The color-forming marking agent may be applied directly to the substrate, or may be applied to the substrate which has been subjected to a surface treatment or undercoating in advance. The coating can be performed using an appropriate coating device such as a roll coater, a gravure coater, a microgravure coater, a knife coater, a spray coater, and the like. The thickness of the coating film (heat-sensitive recording layer) obtained after coating and drying can be generally from 1 to 4 μm. When the thickness is more than 4 μm, there is a tendency that the drying property, suitability for labeling, and the like are reduced. Drying depends on the coating conditions such as the line speed, and may be performed at room temperature, or may be performed by heating under conditions where the heat-sensitive recording layer does not develop color.

The protective layer of the article for laser marking of the present invention is provided by applying a transparent clear coat liquid on the heat-sensitive recording layer. This clear coat liquid is an aqueous composition composed of an aqueous binder, water and the like.
The aqueous binder used in the clear coat liquid of the protective layer of the present invention is based on a water-soluble or water-dispersible resin known per se used in paints or inks. In order to make each of these resins water-soluble or water-dispersible, a hydrophilic group such as a carboxyl group or an amino group is introduced into the molecule as necessary. As the resin for an aqueous binder, those having a glass transition temperature in the range of 20 to 80C, preferably 35 to 70C are used. When the glass transition temperature is lower than 20 ° C., the scratch resistance, chemical resistance, water resistance, etc. of the protective layer are reduced. Are not preferred. The clear coat solution may further contain, if necessary, a leveling agent, a slipperiness imparting agent, an antifoaming agent, and the like, in addition to the above components.

In the aqueous binder used for the clear coating solution, the acrylic resin contains an alkyl (C1-24) ester of acrylic acid or methacrylic acid as a main component, and further includes an unsaturated resin such as acrylic acid, methacrylic acid or maleic acid. Carboxylic acids; hydroxyl-containing unsaturated monomers such as hydroxyethyl acrylate and hydroxypropyl methacrylate; amino-containing unsaturated monomers such as acrylamide and methacrylamide; and other unsaturated monomers such as styrene, acrylonitrile, vinyl acetate, and vinyl chloride. It is obtained by combining and polymerizing. In addition, the polyester resin contains 2 per molecule.
It can be obtained by subjecting a polybasic acid (including acid anhydride) having at least two carboxyl groups to an ester reaction with a polyhydric alcohol having at least two hydroxyl groups in one molecule. The glass transition point of these aqueous binders can be arbitrarily adjusted depending on the types of components constituting the binder, the combination thereof, and the composition ratio.

The clear coat solution is prepared by dissolving or dispersing the above-mentioned aqueous binder in appropriate water, and further blends a leveling agent, a slipperiness imparting agent, an antifoaming agent and the like as required. The solid content of the clear coat solution is 20 to 70% by weight, particularly 30% by weight.
It is preferably in the range of 〜60% by weight. The clear coating solution can print (coat) the dried thermosensitive recording layer on the coated surface. The method is not particularly limited, and for example, coating can be performed by a roll coater, a gravure coater, a microgravure coater, a spray coater, or the like. Its film thickness can generally be 3-10 μm,
When the thickness is less than 3 μm, the protection of the heat-sensitive recording layer by the clear coat is inferior, and the chemical resistance and the friction resistance are lowered,
Conversely, when the thickness is more than 10 μm, the drying property and physical performance of the coating film tend to decrease. Drying of the clear coating solution depends on coating conditions such as line speed and can be performed at room temperature, but may be performed by heating under conditions where the heat-sensitive recording layer does not develop color.

By irradiating the heat-sensitive recording layer on the marking article thus formed with a laser beam,
The irradiated portion is heated, and the urea urethane compound color developer and the dye precursor act to form a color and mark.
The energy amount of the laser for irradiation is not particularly limited, but is preferably 1.4 J (joule) / cm ² or less in consideration of the possibility of destruction of the coating film. On the other hand, the lower limit of color development is unknown because there is no apparatus for generating low energy, but color development is sufficient even with an energy of 0.4 J / cm ² .
Therefore, the irradiation energy range for coloring is
0.4-1.4 J / cm ² , especially 0.45-1.2 J /
A range of cm ² is appropriate. The laser to be irradiated is preferably a pulsed laser or a scanning laser, and the type of laser may be, for example, a gas laser, an excimer laser, or a semiconductor laser. Lasers, mixed gas lasers, YAG lasers, ruby lasers and the like can be mentioned.

As a method of partially irradiating a laser beam to a desired shape, a method of irradiating a coating film with a laser beam through a metal mask to irradiate the coating film with a laser beam corresponding to the shape of a gap portion of the metal mask, There is a method in which a desired desired shape is input to a computer, and a laser beam is irradiated in a so-called one-stroke manner according to the shape. When the laser beam is irradiated to the heat-sensitive recording layer, the temperature rises, and the color is formed by melting and mixing the color-forming components in the heat-sensitive recording layer, and characters and figures having a clear desired shape appear. Discoloration due to this irradiation can be performed instantaneously due to the high energy density of the laser light.

Labels as laser marking articles of the present invention include paper such as paper and synthetic paper, synthetic resin films, plastics, metal-deposited paper and synthetic paper, metal-deposited films, It can be manufactured by forming a heat-sensitive recording layer and a protective layer by the above-described method on a label base material appropriately using metals and the like according to the use, and the use of the obtained label is conventionally used. All areas, but food, pharmaceuticals,
Fields such as toiletries, publications, electronic and electrical components are particularly preferred.

The packaging material as an article for laser marking according to the present invention may be made of paper such as paper and synthetic paper, synthetic resin film, plastics, metal-deposited paper and synthetic paper, metal-deposited paper as a base material. Films, metals,
Various kinds of commonly used packaging materials such as boxes, wrapping paper, packages, etc. appropriately using glass, wood, etc. according to the application,
A heat-sensitive recording layer and a protective layer are provided by the method described above. Although the use of the packaging material is directed to all the fields conventionally used, the fields of foods, pharmaceuticals, toiletries, publications, electronic and electric parts and the like are particularly preferable. Further, the containers as the laser marking article of the present invention, glass, plastic, metal as a base material,
These substrates are provided with a heat-sensitive recording layer and a protective layer by the method described above. The food container can be applied to all conventionally used fields such as bottles of alcoholic beverages and soft drinks, retort food containers, instant food containers, cosmetic containers, pharmaceutical containers, and toiletry products.

When the recording material is a pressure-sensitive recording material, for example, US Pat. Nos. 2,505,470 and 27125
Nos. 07, 2730456 and 273045
7 and 3,418,250 can be employed. That is, the dye precursors are used alone or in combination, and synthetic oils such as alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated diarylethane, and chlorinated paraffin, and vegetable oils, animal oils, and mineral oils alone are used. Or an upper paper obtained by dissolving in a solvent composed of a mixture and dispersing the same in a binder, or by applying a dispersion liquid contained in microcapsules on a support together with a binder or the like, and a urea urethane compound ( Pressure-sensitive recording paper on which the coated surfaces of the lower paper coated with a dispersion of a urea urethane compound are further applied, and the dye is coated on the other surface. The middle paper coated with the precursor is placed on the pressure-sensitive recording paper sandwiched between the upper paper and the lower paper, or on the same surface of the support as the urethane. Urethane compound (and an amino compound and / or developer)
The dispersion liquid containing the dye precursor and the dispersion liquid containing the above-mentioned dye precursor are mixed or multi-layered, or the dye precursor and the urea urethane compound (and the amino compound and / or the developer) are both microcapsules. It is possible to use various types of self-types, such as self-types which have been mixed and applied.

The method for producing microcapsules includes the coacervation method disclosed in US Pat. Nos. 2,800,457 and 2,800,458, and JP-B-38-1.
9574, 42-446 and 42-77
No. 1, JP-B-36-91.
No. 68, Japanese Patent Publication No. 51-9079, the in-situ method disclosed in British Patent No. 952807,
Japanese Patent No. 96-5074 discloses a melting dispersion cooling method, US Pat. No. 3,111,140, and British Patent No. 930.
For example, a spray drying method disclosed in Japanese Patent No. 422 or the like can be adopted. The color former of the present invention corresponds to the dye precursor and the developer in the above publications and the like. In forming the pressure-sensitive recording layer, each component such as a urea urethane compound may be used by dissolving it in a solvent or by dispersing it. In the case of a coloring system including an amino compound and / or a color developing agent, the color developing system may be used alone, or a urea urethane compound and an amino compound may be used in combination, and if necessary, a developer may be used in combination with dissolving or dispersing in a solvent. Just fine.

In the above-described interfacial polymerization method used in the formation of microcapsules, a film is formed at the interface using two types of oil-based and water-soluble monomers. For example, a polybasic acid chloride is used in the oil phase, a polyamide film is used in the interface using a polyvalent amine in the aqueous phase, a polyester film is used in the aqueous phase using a polyhydroxy compound, and a polyvalent film is used in the oil phase. It is known that a method of forming a polyurethane film by using a polyhydric alcohol or a polyhydric phenol in an aqueous phase when an isocyanate is used and a method of forming a polyurea film by using a polyvalent amine in an aqueous phase are used. When the interfacial polymerization method is used for producing microcapsules, an isocyanate compound may be used as one of the reactive monomers for forming a film.

In this case, the isocyanate compound is consumed for forming the film of the microcapsules, and is not directly involved in the color image, and the use of another water-soluble monomer is indispensable. This is distinguished from the use of the isocyanate compound used in the present invention. A dispersion of a compound without microencapsulation is prepared by pulverizing one or more of each compound in an aqueous solution containing a compound having a dispersing ability such as a water-soluble polymer or a surfactant. Can be The urea urethane compound may be dispersed simultaneously with the amino compound and the acidic developer.

As the support used for the pressure-sensitive recording material, paper is mainly used. In addition to paper, various woven fabrics, non-woven fabrics,
A synthetic resin film, a laminated paper, a synthetic paper, a metal foil, or a composite sheet combining these can be used arbitrarily according to the purpose. As the binder, various binders that are usually used can be used.For example, starches, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin,
Casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, acrylamide / acrylate copolymer, acrylamide / acrylate / methacrylic acid terpolymer, alkali salt of styrene / maleic anhydride copolymer, ethylene / Water-soluble binder such as alkali salt of maleic anhydride copolymer, and styrene / butadiene copolymer, acrylonitrile /
Latex-based water-insoluble binders such as butadiene copolymer and methyl acrylate / butadiene copolymer are exemplified.

Further, in the recording material according to the present invention,
The recording layer may contain a hindered phenol compound or an ultraviolet absorber. For example, 1,1,3-tris (3′-cyclohexyl-4′hydroxyphenyl) butane,
1,3-tris (2-methyl-4-hydroxy-5-t
tert-butylphenyl) butane, 4,4'-thiobis (3-methyl-6-tert-butylphenol),
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, p-octylphenyl salicylate, 2- (2'-hydroxy-5'-methylphenyl)
Benzotriazole, ethyl-2-cyano-3,3'-
Diphenyl acrylate and tetra (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarbonate.

The method for forming the color-forming layer is not particularly limited, and the coating solution for the color-forming layer may be appropriately coated by, for example, free-fall curtain, air knife coating, variver blade coating, pure blade coating, short dwell coating, or the like. It is formed by a method of coating and drying on a support by a method. In the case of the coating solution for the coloring layer,
The coating amount is not particularly limited, and is usually 1 to 15 by dry weight.
g / m ^2, it is preferably adjusted in the range of about 3 to 10 g / m ^2.

Further, an intermediate layer can be provided between the heat-sensitive recording layer and the support to improve the thermal responsiveness. Also,
In conventional heat-sensitive recording materials, a technique has been used to improve the color-forming sensitivity by using a heat-fusible substance in combination with the color-forming layer. There is a problem that fogging is likely to occur. In particular, in the case of a heat-sensitive recording material using a urea urethane compound developer excellent in color sensitivity, background fogging tends to occur. In the case of the conventional heat-sensitive recording material having no print storability, even if background fogging occurs, it disappears in the same manner as printing, so that background fogging, especially when stored and used for a long period of time, is rarely a problem. However, in the case of a thermal recording material using a urea urethane compound developer excellent in long-term preservability of printing, once the background covering occurs, the background covering is preserved. Accumulates, and there is a case where a peculiar problem occurs that the paper surface becomes dirty when stored and used for a long time. In such a case, by providing an intermediate layer,
Even if a heat-fusible substance is not used, or even if a small amount of the heat-fusible substance is used, practical coloring sensitivity can be obtained, and it is excellent in heat and friction resistance to the ground, and can be used for a long period of time. It is possible to obtain a heat-sensitive recording material in which background fogging is unlikely to accumulate.

The intermediate layer is mainly composed of organic and inorganic pigments, hollow particles, and a water-based binder such as a water-soluble polymer and latex. Can be. The method for forming the intermediate layer is not particularly limited, and a method similar to the method for forming the heat-sensitive recording layer can be used. Dry coating amount is 2.0
A range of 〜15.0 g / m ² is preferred. In this case, the surface pH of the intermediate layer provided on the support is also preferably from 3 to 9, more preferably from 5 to 9, and even more preferably from 6 to 8.

In the present invention, if necessary, a protective layer containing a water-soluble polymer as a main component is provided on the heat-sensitive recording layer, whereby the scratch resistance of the recording paper can be improved. In addition, when the urea urethane compound developer of the present invention, which is excellent in color sensitivity and long-term storage resistance of printing, is used, the rubbing trace is high and the rubbing trace once generated is stored forever. In addition, rubbing traces accumulate each time storage and use are performed, and when stored and used for a long time, the paper surface may become dirty. In such a case, by providing a protective layer, it is possible to make it difficult to accumulate rubbing traces even when stored and used for a long time. Specific examples of the water-soluble polymer contained in the protective layer include the water-soluble polymer binder exemplified in relation to the heat-sensitive recording layer. The water-soluble polymer can be used together with a conventional water-proofing agent for making it water-resistant,
Specific examples of the water-proofing agent include, for example, formaldehyde, glyoxal, chrome alum, melamine, melamine-formaldehyde resin, polyamide resin, polyamide-epichlorohydrin resin and the like.

Further, a pigment, a metal soap, a wax, a crosslinking agent, etc. are added to the protective layer for the purpose of improving the matching property with the thermal head at the time of printing and improving the water resistance of the protective layer. Pigments include zinc oxide, calcium carbonate, barium sulfate, titanium oxide, lithopone, talc, lime, kaolin,
Aluminum hydroxide, silica, amorphous silica, etc., and the amount of addition thereof is 0.5 to 4 of the total weight of the polymer.
Times, particularly preferably 0.8 to 3.5 times. If the amount is less than the lower limit of the above range, it is ineffective for improving the head matching property. If the amount is more than the upper limit, the sensitivity of the heat-sensitive recording material is remarkably reduced, and its commercial value is impaired.

Examples of the metal soap include emulsions of higher fatty acid metal salts such as zinc stearate, calcium stearate, and aluminum stearate, and the like. It is added in proportions. Waxes include emulsions of paraffin wax, microcrystalline wax, carnauba wax, methylol stearamide, polyethylene wax, etc., added in an amount of 1 to 20% by weight, preferably 1 to 10% by weight of the total weight of the protective layer. Is done.

In forming the protective layer on the heat-sensitive layer, a surfactant is added to the coating liquid for forming the protective layer in order to form a uniform coating layer. Surfactants include sulfosuccinic acid-based alkali metal salts, fluorine-containing surfactants, etc.
Specific examples include di- (2-ethylhexyl) sulfosuccinic acid and sodium or ammonium salts such as di- (n-hexyl) sulfosuccinic acid. Generally, any anionic surfactant is effective. It is. Conventional auxiliary additives such as fillers, heat-fusible substances (lubricants), surfactants, fluorescent dyes, and the like can be contained. Those exemplified in relation to the recording layer can be mentioned. The dry coating amount of the protective layer is 0.5 to 1
Is preferably about 0 g / m ^2, in particular the amount of about 1 to 5 g / m ² is preferred.

The recording material produced by the method of the present invention may be provided with a back layer (back coat layer) on the surface opposite to the recording layer, if necessary, so that the recording paper is less likely to curl. Can be. In particular, the urea urethane compound developer of the present invention is excellent in dispersibility as compared with other developers, a dispersion having a small particle diameter can be easily obtained, and the sensitivity is high, but it is mixed with other necessary components. When a coating liquid is applied on a support, the binder has a large cohesive force during drying due to the small particle size, and the recording layer is easily shrunk and curled. Therefore, the back layer is effective. The coating liquid component of the back layer, coating method, etc.
It may be the same as in the case of the protective layer. 0.2-1 dry coating amount
A range of 0.0 g / m ² is preferred.

Hereinafter, the present invention will be described in more detail by way of examples. In addition, analysis of each substance and evaluation of each physical property were performed by the following methods. <IR spectrum> Measured by a diffuse reflection method using FTIR-8100M manufactured by Shimadzu. <Mass Spectrum> Using JMS-HX100 manufactured by JEOL, matrix was measured using nitrobenzyl alcohol, and primary gas was measured using xenon. <Color Sensitivity of Thermal Paper> Using a printing tester manufactured by Okura Electric Co., Ltd., the color density at an applied voltage of 24 V and a pulse width of 1.5 msec was measured with an optical densitometer using KJT-256-8MGF1 manufactured by Kyocera. <Plasticizer resistance> The heat-sensitive recording material is sandwiched between vinyl chloride wraps or vinyl chloride files, applied with a load of 300 g / cm ² from the top, left at 40 ° C. for 24 hours, and then printed and unprinted portions (background) ) Was visually evaluated, and those with little decoloration of print density were regarded as having good print storability.

<Heat resistance> The heat-sensitive recording material was heated at 60 ° C. and 25%
After leaving for 24 hours in an environment of RH, the fading density of the print was visually evaluated. Further, the heat-sensitive recording material was subjected to 24 hours in an environment of 80 ° C. and 25% RH.
After leaving for a time, the fading density of the print was visually evaluated. In addition, the color density of the background was visually evaluated, and those having less color development were evaluated as having good background preservability. <Pressure Sensitive Paper Color Density> The upper paper and the lower paper were superposed so that the coated surfaces faced each other and pressed to obtain a color image on the lower paper. The density of the color image was measured using a densitometer Macbeth RD917. <Solvent resistance> Hand cream (product name: Atrix (manufactured by Kao Corporation)) is applied to the color image area obtained by the evaluation of the color density.
Was coated thinly and allowed to stand at room temperature for 7 days, and then the density of the printed portion was visually evaluated.

[0416]

Example 1 2,4-Toluene diisocyanate 27.
To 8 g, 111 g of toluene (δ value: 8.9) as a solvent was added, and at room temperature, 7.4 g of aniline dissolved in 37 g of toluene was added dropwise over 1 hour, and the mixture was further reacted for 1 hour. The precipitated white solid was collected by filtration, washed with hexane, and dried under vacuum overnight to obtain 20 g of white crystals.
Next, 5 g of this compound was added to 50 mL of methanol, and
After reacting at 0 ° C. for 30 minutes, excess methanol was removed with an evaporator, and toluene was added for crystallization. The resulting white crystals were collected by filtration, washed with hexane, and dried in vacuo overnight to give 5.4 g of crystals were obtained. The melting point of this white crystal was 196 ° C. The analytical values of the white crystals are as follows. Results of IR measurement: 1060 cm ⁻¹ , 1250 cm ⁻¹ , 1
600 cm ^-1 , 1650 cm ^-1 , 1670 cm ^-1 , 17
Characteristic peaks appeared at 00 cm ^-1 and 3300 cm ^-1 . The structural formula of the main component of this compound is the aforementioned compound (S-1)
It is estimated to be.

Next, 2 g of this compound was taken, and 2.5% by weight was obtained.
8 g of an aqueous solution of polyvinyl alcohol (Gohselan L-3266 (trade name), manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was ground and dispersed with a paint shaker for 6 hours to obtain a dispersion. The liquid temperature of the dispersion immediately after the dispersion was 25 ° C. Also,
The dispersed particle size of this compound was about 0.6 μm. Further, a sand grinder (vessel capacity of 40 g) was used together with 70 g of 3-dibutylamino-6-methyl-7-anilinofluoran and 130 g of an 8% by weight aqueous solution of polyvinyl alcohol.
0 ml, manufactured by Imex Co., Ltd.) and crushed and dispersed at a rotation speed of 2000 rpm for 3 hours to obtain a dispersion.

Further, 70 g of diphenyl sulfone was added to 5.4 g
A dispersion was obtained by pulverizing and dispersing with a sand grinder (Vessel capacity: 400 ml, manufactured by IMEX Co., Ltd.) at a rotation speed of 2,000 rpm for 3 hours together with 130 g of an aqueous solution of polyvinyl alcohol by weight. In addition, 10 g of calcium carbonate is added to 30 pieces of water.
g and mixed with a stirrer to obtain a dispersion. These dispersions were dried at a solids content of 3.
0 parts by weight, 15 parts by weight of dry solids of 3-dibutylamino-6-methyl-7-anilinofluoran dispersion, 30 parts by weight of dry solids of diphenylsulfone dispersion, 20 parts of dry solids of calcium carbonate dispersion Parts by weight, and a dry solid content 1 of a zinc stearate dispersion having a solid content concentration of 16% by weight.
The coating liquid was obtained by stirring and mixing 0 parts by weight and 7 parts by weight of a dry solid content of 15% by weight polyvinyl alcohol (dry basis).

This coating solution was applied to a base paper having a weighing of 50 g / m ^{2 using} a rod coater rod No. 10. After drying, it was treated with a super calender to obtain a heat-sensitive recording material. The coating amount of the coating liquid was 4 g / m ² in dry weight. The evaluation result of the sensitivity of the obtained heat-sensitive recording material showed that the optical density was 1.
2 was good. The evaluation result of the degree of discoloration (heat resistance) of the background due to heat was good with little discoloration. In addition, fading due to heat in the printed portion was small and good. Table 1 summarizes the results of these evaluations.

[0420]

EXAMPLE 2 17 g of 2,4-toluene diisocyanate
Methyl ethyl ketone (δ value: 9.3) 40 as a solvent
g of methanol, 3.8 g of methanol was added dropwise, and the mixture was reacted at 60 ° C. for 5 hours with stirring. Next, 4,4'-
9.9 g of diaminodiphenylsulfone was added and reacted at 60 ° C. for 4 hours with stirring. After the reaction, the reaction solution was cooled to room temperature, poured into 800 g of acetonitrile, and the precipitated crystals were collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 15 g of a white crystalline compound. The melting point of this white crystal is 169 ° C., and the analytical values are as follows. Results of IR measurement: 1220 cm ⁻¹ , 1550 cm ⁻¹ , 1
590 cm ^-1 , 1660 cm ^-1 , 1740 cm ^-1 , 33
A characteristic peak appeared at 00 cm ^-1 . Mass spectrum measurement result: [M + H] at m / z 661
+ Was detected. The structural formula of the main component of this compound is represented by the aforementioned compound (S-1)
3) is estimated. Subsequently, except that the above compound was used instead of the urea urethane compound synthesized in Example 1,
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1. The results are summarized in Table 1.

[0421]

Example 3 3.46 g of aniline was added to ethyl acetate (δ value:
8.6) Dissolve in 100 mL, stir at room temperature, 10 g of toluenediisocyanate trimethylolpropane adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd., 75% ethyl acetate solution) and 50 m of ethyl acetate
The L solution was added dropwise over 1 hour, and the mixture was further reacted for 30 minutes.
The generated crystals were collected by filtration and dried under vacuum overnight to obtain 5.1 g of a compound as white crystals. The melting point of this white crystal is 161 ° C., and the analytical values are as follows. Results of IR measurement: 1070 cm ⁻¹ , 1220 cm ⁻¹ , 1
550 cm ⁻¹ , 1600 cm ⁻¹ , 1700 cm ⁻¹ , 33
A characteristic peak appeared at 00 cm ^-1 . The structural formula of the main component of this compound is estimated to be the aforementioned compound (S-33).
Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above compound was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0422]

Example 4 2,4-Toluene diisocyanate
To 4 g, 20 g of methyl ethyl ketone was added as a solvent, and 3.7 g of 4,4'-diaminodiphenylsulfone was diluted with 30 g of methyl ethyl ketone and added dropwise.
The reaction was performed for 0 hours. After the reaction, methyl ethyl ketone was concentrated and removed, and then toluene was added. The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 8.8 g of a white crystalline compound. Next, 4 g of this compound was taken, 15 g of phenol was added, and a small amount of dibutyltin dilaurate was further added, followed by reaction at 50 ° C. for 4 hours.
After the reaction, toluene was added, and the precipitated crystals were collected by filtration, washed with hexane, and vacuum-dried overnight to obtain 5.2 g of a ureaurethane compound as white crystals.

Next, 30 g of toluene as a solvent was added to 10 g of 2,4-toluene diisocyanate, 30 g of phenol was added thereto, and the mixture was reacted at 100 ° C. for 3 hours. After the reaction, toluene was concentrated and removed, and then hexane was added. The precipitated white solid was collected by filtration, washed with hexane and dried in vacuo overnight to obtain a urethane compound as white crystals (15 g). The deduced structural formula of the main component of this compound is compound (C-2) described later.

Then, 3 g of the above urea urethane compound and 2 g of the urethane compound were taken and mixed to obtain a urea urethane composition. Subsequently, 2 g of the urea urethane composition was taken and pulverized and dispersed with a paint shaker for 45 minutes together with 8 g of a 2.5% by weight aqueous methylcellulose solution to obtain a dispersion. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the dispersion of the above composition was used instead of the dispersion of the compound obtained in Example 1. The results are summarized in Table 1.

[0425]

Example 5 Instead of the urea urethane composition used in Example 4, a urea urethane composition obtained by mixing and mixing 4.5 g of the urea urethane compound synthesized in Example 4 and 0.5 g of the urethane compound was used. A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 4 except for using the same. The results are summarized in Table 1.

[0426]

Example 6 Instead of the urea urethane composition used in Example 4, after the synthesis reaction of the urea urethane compound synthesized in Example 4, 2.2 g of diphenyl sulfone was added to the reaction system before adding toluene to precipitate. Example 4 was repeated except that toluene was added, and the precipitated crystals were collected by filtration, washed with hexane, washed with hexane, and vacuum-dried overnight to obtain 7.4 g of a white crystalline ureaurethane composition. A heat-sensitive recording material was prepared and evaluated in the same manner as described above. The results are summarized in Table 1.

[0427]

Example 7 2,4-Toluene diisocyanate
4,4 ′ dissolved in 60 mL of methyl ethyl ketone in 5 g at 70 ° C. while stirring at 300 to 500 rpm.
21.5 g of -diaminodiphenyl sulfone was added dropwise over 4 hours, and the mixture was further reacted for 4 hours to obtain a white viscous slurry reaction solution. Next, the mixture was cooled to 50 ° C., 17.1 g of phenol was added and dissolved, 0.015 g of triethylamine was added as a catalyst, and the mixture was reacted for 4 hours to obtain a yellow transparent viscous reaction solution. This was concentrated by removing the solvent under reduced pressure to solidify, then pulverized, and vacuum dried overnight to obtain about 70 g of a urea urethane composition as a pale yellow powder.

The melting point of this pale yellow powder is 130 to 170 ° C.
According to IR measurement, a broad peak in which characteristic peaks of a urea group and a urethane group overlapped appeared at 1700 cm ^-1 . The urea urethane main component content in this urea urethane composition was 68% by liquid chromatography. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0429]

Example 8 2,4-Toluene diisocyanate 15
To 8.5 g, 240 g of methyl ethyl ketone as a solvent was added, and while stirring at 30 ° C. and 400 rpm, 107.5 g of 4,4′-diaminodiphenyl sulfone was added as a powder over 8 hours, and 1 hour later, methyl ethyl ketone was added. After adding 26 g, the mixture was further stirred for 15 hours to obtain a white viscous slurry reaction liquid. Next, 89.5 g of phenol dissolved in 15.8 g of methyl ethyl ketone was added,
After dissolving, 9.3 g of a 1% by weight triethylamine / methyl ethyl ketone solution was added as a catalyst over 2 hours, and the reaction was continued for 1 hour. A slurry liquid was obtained. This was concentrated by removing the solvent under reduced pressure to solidify, then pulverized, and vacuum dried overnight to obtain 355 g of a urea urethane composition as a slightly yellow powder.

The melting point of this slightly yellow powder is 160 to 180 ° C.
According to IR measurement, a broad peak in which characteristic peaks of a urea group and a urethane group overlapped appeared at 1700 cm ^-1 . The urea urethane main component content in this urea urethane composition was 65% by liquid chromatography. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0431]

Example 9 2,4-Toluene diisocyanate 27.
To 8 g, 100 g of toluene as a solvent was added, and at room temperature, 7.4 g of aniline dissolved in 37 g of toluene was added dropwise over 1 hour, and the mixture was further reacted for 1 hour. The precipitated white solid was collected by filtration, washed with hexane, and dried under vacuum overnight to obtain 20 g of white crystals. Next, this compound 5
g was added to 50 mL of methanol and reacted at 60 ° C. for 30 minutes. Then, excess methanol was removed by an evaporator, followed by vacuum drying overnight to obtain 5.4 g of a urea urethane composition as white crystals. The melting point of this white crystal is 196
° C., and 1670 cm ⁻¹ , 1700
A characteristic peak of the urea urethane compound appeared at cm ^-1 .
The urea urethane main component content in this urea urethane composition was 92% by liquid chromatography. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0432]

Example 10 5.6 g of a white crystalline ureaurethane composition was obtained in the same manner as in Example 9 except that the reaction was carried out using ethanol instead of methanol used in Example 9. The melting point of this white crystal was 195 ° C., and a characteristic peak of the urea urethane compound appeared at 1700 cm ⁻¹ by IR measurement. The urea urethane main component content in this urea urethane composition is determined by liquid chromatography,
92%. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0433]

Example 11 2-propanol (150 ml) was used in place of methanol used in Example 9,
5.8 g of a urea urethane composition having white crystals was obtained in the same manner as in Example 9 except that the reaction was carried out for an hour. The melting point of this white crystal was 220 ° C.
A characteristic peak of the urea urethane compound appeared at cm ^-1 .
The urea urethane main component content in this urea urethane composition was 93% as measured by liquid chromatography. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0434]

Example 12 The procedure of Example 9 was repeated, except that 35 ml of n-butyl alcohol was used in place of methanol used in Example 9, and the reaction was carried out at 60 ° C. for 1 hour. Was obtained in an amount of 4.1 g. The melting point of this white crystal is 165 ° C.
A characteristic peak of the urea urethane compound appeared at m ^-1 . The urea urethane main component content in this urea urethane composition was 92% by liquid chromatography.
Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0435]

Example 13 100 ml of isobutyl alcohol was used in place of methanol used in Example 9,
5.3 g of a urea urethane composition having white crystals was obtained in the same manner as in Example 9 except that the reaction was carried out for an hour. The melting point of this white crystal was 189 ° C.
A characteristic peak of the urea urethane compound appeared at cm ^-1 .
The urea urethane main component content in this urea urethane composition was 96% as measured by liquid chromatography. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0436]

Example 14 2,4-Toluene diisocyanate 2
100 g of toluene as a solvent was added to 7.8 g, and at room temperature, 7.4 g of aniline dissolved in 37 g of toluene was added thereto.
Was added dropwise over 1 hour, and the mixture was further reacted for 1 hour. The precipitated white solid was collected by filtration, washed with hexane, and dried under vacuum overnight to obtain 20 g of white crystals. Next, 5.9 g of this compound was added to 60 ml of trimethyl phosphate,
Next, after adding 0.6 g of glycerin and 5 mg of dibutyltin dilaurate as a catalyst and reacting at 25 ° C. for 100 hours, the reaction solution was poured into a large amount of water, and the generated white crystals were collected by filtration and dried under vacuum overnight. Thus, 5.4 g of the urea urethane composition was obtained as white crystals. The urea urethane main component content in this urea urethane composition was 62% as measured by liquid chromatography. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0437]

Example 15 0.99 g of triethanolamine was used in place of glycerin used in Example 14, and zinc 2-ethylhexanoate was used as a catalyst instead of dibutyltin dilaurate (Octop-Zn: trade name, manufactured by Hope Pharmaceutical Co., Ltd.) Except that the reaction was carried out at 25 ° C. for 23 hours.
In the same manner as in Example 14, 5.6 g of a urea urethane composition having white crystals was obtained. The urea urethane main component content in this urea urethane composition was 73% as measured by liquid chromatography. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0438]

Example 16 In place of glycerin used in Example 14, 0.62 g of pentaerythritol was used.
Except for performing the reaction for 20 hours, 5.0 g of a ureaurethane composition of white crystals was obtained in the same manner as in Example 14. The urea urethane main component content in this urea urethane composition was 63% by liquid chromatography. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0439]

Example 17 2,4-Toluene diisocyanate 17
40 g of methyl ethyl ketone as a solvent was added to 3.8 g, and 3.8 g of methanol was added dropwise.
For 5 hours. Next, 9.9 g of 4,4′-diaminodiphenylsulfone was added, and the mixture was stirred at 60 ° C. for 4 hours.
Allowed to react for hours. After the reaction, methyl ethyl ketone as a solvent was removed with an evaporator, followed by vacuum drying overnight to obtain 16 g of a urea urethane composition as white crystals. The melting point of this white crystal was 169 ° C., and 1660 cm
Characteristic peaks of the urea urethane compound appeared at ^-1 and 1740 cm ^-1 . The urea urethane main component content in this urea urethane composition was determined by liquid chromatography to be 5%.
2%. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0440]

Example 18 2,4-Toluene diisocyanate 2
7.5 g was dissolved in 253 mL of toluene,
While stirring at 0 rpm, 14.7 g of aniline dissolved in 85 mL of toluene was added dropwise thereto over 30 minutes, and the mixture was further reacted for 30 minutes. In the obtained white slurry liquid, 2,
2-bis (4-hydroxyphenyl) propane 18.0
g, 262 mL of toluene and 0.42 mg of triethylamine as a catalyst were added, and the stirring speed was increased to 400 rpm. In order to control the reaction rate and prevent agglomeration of slurry particles at the beginning of the reaction, 5 hours at 60 ° C, 2 hours at 65 ° C, 70 ° C
For 1 h and at 75 ° C. for 1 h while gradually increasing the temperature, adding 0.42 mg of triethylamine, and further adding
The reaction was carried out at 0 ° C. for 8 hours. After cooling to room temperature, white crystals were collected by filtration. This was vacuum-dried overnight to obtain 59 g of a urea urethane composition as white crystals. The melting point of this white crystal was 170 ° C.
A broad characteristic peak of urea urethane appeared at m ^-1 . The urea urethane main component content in this urea urethane composition was 81% as measured by liquid chromatography.
Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0441]

Example 19 2,4-Toluene diisocyanate 11
123 g of ethyl acetate and 62.7 g of phenol (δ value: 11.4) were added to 1 g as a solvent,
While stirring at 0 rpm, 75.3 g of 4,4′-diaminodiphenyl sulfone was added as a powder over 1 hour,
A white slurry reaction was obtained. Next, ethyl acetate 320
Then, 18.6 g of a 10% by weight solution of triethylamine as a catalyst in ethyl acetate was added dropwise over 30 minutes while stirring at 30 ° C. and 400 rpm, and the mixture was reacted for 18 hours to obtain a white slurry reaction solution. After deconcentrating the solvent under reduced pressure and solidifying it, it was vacuum-dried overnight to obtain about 240 g of a urea urethane composition as a white powder.

The melting point of this white powder was 130 to 170 ° C., and a broad peak in which characteristic peaks of a urea group and a urethane group overlapped appeared at 1700 cm ⁻¹ by IR measurement. The urea urethane main component content in this urea urethane composition was 65% by liquid chromatography. The urea urethane compound (E
-41 is considered. ) Was 5%, and the compound considered to be C-2 described later was 11%. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0443]

Example 20 2,4-Toluene diisocyanate 11
To 0.5 g was added 124 g of ethyl acetate as a solvent,
At 4 ° C. while stirring at 200 rpm.
75.3 g of diaminodiphenyl sulfone was added as a powder over 8 hours, and the mixture was further stirred for 15 hours to obtain a white slurry reaction solution. Next, 257 g of ethyl acetate and 62.7 g of phenol were charged and dissolved, and 10% by weight of a catalyst was used.
Then, 5.6 g of a 1,4-diazabicyclo (2,2,2) octane / ethyl acetate solution of the above was added over 30 minutes, and the reaction was continued for 23 hours to obtain a white slurry-like reaction solution. This was concentrated under reduced pressure to remove the solvent, and dried under vacuum overnight to obtain 360 g of a white powdered ureaurethane composition.

The melting point of this white powder was 130 to 170 ° C., and a broad peak in which characteristic peaks of a urea group and a urethane group overlapped at 1700 cm ⁻¹ appeared by IR measurement. The urea urethane main component content in this urea urethane composition was 60% as measured by liquid chromatography. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0445]

Example 21 2,4-Toluene diisocyanate 11
In 1 g, 346 g of phenol was added as a solvent,
While stirring at 200 rpm, 75.3 g of 4,4'-diaminodiphenylsulfone was added as a powder over 1 hour to obtain a white viscous slurry reaction solution. Next, 40
While stirring at 200 ° C. at 200 ° C., 28 mg of triethylamine was added as a catalyst, and the mixture was reacted for 4.5 hours to obtain a white viscous slurry-like reaction liquid. This was concentrated by removing the solvent under reduced pressure and solidified, followed by vacuum drying overnight to obtain about 150 g of a urea urethane composition as a white powder.

The melting point of this white powder was 130 to 170 ° C., and a broad peak in which characteristic peaks of a urea group and a urethane group overlapped at 1700 cm ⁻¹ appeared by IR measurement. The urea urethane main component content in this urea urethane composition was 55% by liquid chromatography. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above composition was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0447]

Examples 22 to 33 Instead of diphenylsulfone used in Example 8, 4,4'-dichlorodiphenylsulfone (Example 22), 4,4'-dihydroxydiphenylsulfone (Example 23), 2,4 '-Dihydroxydiphenylsulfone (Example 24), 4- (benzyloxy) phenol (Example 25), salicylanilide (Example 26), 4,4'-diaminodiphenylsulfone (Example 27), 4,4' -Dichlorobenzophenone (Example 28), 4,4'-diaminodiphenylmethane (Example 29), 4,4'-dimethoxybenzophenone (Example 30), diphenyl carbonate (Example 31), 4,
4'-dimethoxydiphenyl sulfone (Example 32),
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 8, except that 4,4'-diallyloxydiphenyl sulfone (Example 33) was used. The results are summarized in Table 1.

[0448]

Comparative Example 1 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea urethane compound synthesized in Example 1. Was done. The results are summarized in Table 1.

[0449]

Comparative Example 2 2,4-Toluene diisocyanate
To 4 g, 5 mL of methyl ethyl ketone was added as a solvent, and 3.2 g of methanol dissolved in 5 mL of methyl ethyl ketone was added.
Was added dropwise, and reacted at room temperature for 2 hours with stirring. Next, 7.3 g of n-butylamine dissolved in 100 mL of methyl ethyl ketone was added dropwise thereto at room temperature while stirring, and the mixture was stirred for 1 hour. The precipitated crystals were collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 27 g of a white crystalline compound. The melting point of this white crystal is 156
At ° C, the analytical values are as follows: IR measurement results: 1240 cm ^-1 , 1550 cm ^-1 , 1
640cm ^-1, 1720cm ^-1, characteristic peaks appeared in 3300 cm ^-1. The putative structural formula of the main component of this compound is shown below (R-1). Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above compound was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0450]

Comparative Example 3 2,4-Toluene diisocyanate
To 100 g of toluene, 100 mL of toluene was added, and the mixture was stirred at 25 ° C. To this, 15.5 g of stearylamine dissolved in 100 mL of toluene was added, followed by reaction at 25 ° C for 22 hours. After the reaction, the precipitated white solid was collected by filtration, washed with toluene, and dried in vacuo overnight to obtain a white crystal 2.
0.4 g was obtained. Next, 5 g of this compound was added to 50 mL of methyl ethyl ketone and stirred at 80 ° C., 8.6 g of p-hydroxybenzyl carboxylic acid dissolved in 20 ml of methyl ethyl ketone was added, and 5 mg of dibutyltin laurate was further added as a catalyst. 12 at ° C
Allowed to react for hours. After the reaction, the mixture was cooled to room temperature, and the precipitated crystals were collected by filtration, washed with methyl ethyl ketone, and dried in vacuo overnight to obtain 5.6 g of white crystals.

The analytical values of the white crystals are as follows. Results of IR measurement: 1220 cm ⁻¹ , 1520 cm ⁻¹ , 1
630 cm ⁻¹ , 1710 cm ⁻¹ , 2900 cm ⁻¹ , 33
A characteristic peak appeared at 00 cm ^-1 . Mass spectrum measurement result: [M + H] at m / z 596
+ Was detected. The putative structural formula of the main component of this compound is shown below (R-2). A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above compound was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0452]

Comparative Example 4 3.0 g of p-aminophenol was added to 100 mL of dioxane, stirred at 50 ° C., and 5.4 g of toluenesulfonyl isocyanate dissolved in 30 mL of dioxane was added dropwise over 1 hour. In addition, the reaction was continued at 50 ° C. for 5 hours. After the reaction, the reaction solution was concentrated and poured into hexane for crystallization. The precipitated solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 4.9 g of brown crystals. Then 50 mL of dioxane
2 g of this compound was added thereto, and the mixture was stirred at 80 ° C., 3.8 g of octadecyl isocyanate dissolved in 10 mL of dioxane was added thereto, and 2 mg of dibutyltin laurate was further added as a catalyst.
For 20 hours. After the reaction, the mixture was cooled to room temperature, and the precipitated crystals were collected by filtration, washed with dioxane, and dried in vacuo overnight to obtain 2.7 g of slightly pink crystals.

The analytical values of the white crystals are as follows. IR measurement results: 1230 cm ⁻¹ , 1470 cm ⁻¹ , 1
510 cm ^-1 , 1570 cm ^-1 , 1620 cm ^-1 , 17
^{00cm -1, 2900cm -1, 3300cm -1} , characteristic peaks appeared. The putative structural formula of the main component of this compound is shown below (R-3). A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the above compound was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

[0454]

Embedded image

[0455]

Comparative Example 5 2,4-Toluene diisocyanate 10 g
Was added with 50 g of toluene as a solvent, and aniline 3 was added thereto.
0 g was added and reacted at 25 ° C. for 3 hours. The white solid precipitated after the reaction was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 17 g of a white crystalline compound. The deduced structural formula of the main component of this compound is represented by the following compound (C-1)
It is. Next, 2 g of this compound was taken and pulverized and dispersed with 8 g of a 2.5% by weight aqueous solution of polyvinyl alcohol on a paint shaker for 45 minutes to obtain a dispersion. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that a dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 1. The results are summarized in Table 1.

[0456]

Comparative Example 6 10 g of 2,4-toluene diisocyanate
To the mixture was added 30 g of toluene as a solvent, 30 g of phenol was added thereto, and the mixture was reacted at 100 ° C. for 3 hours. After the reaction, the toluene was concentrated and removed, and then hexane was added. The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 15 g of a white crystalline compound. The deduced structural formula of the main component of this compound is the following compound (C-2). Next, 2 g of this compound was taken, and together with 8 g of a 2.5% by weight aqueous solution of polyvinyl alcohol, a paint shaker was used to prepare
The mixture was ground and dispersed for 5 minutes to obtain a dispersion. Subsequently, Example 1
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the dispersion of the above compound was used instead of the dispersion of the compound obtained in 1. The results are summarized in Table 1.

[0457]

Embedded image

[0458]

Comparative Example 7 Except that 1,3-diphenylurea was used instead of the urea urethane compound synthesized in Example 1,
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1. The results are summarized in Table 1.

[0459]

[Table 1]

[0460]

Example 34 2,4-Toluene diisocyanate 3
1.5 g was stirred at 60 ° C., and 21.5 g of 4,4′-diaminodiphenylsulfone was diluted with 120 ml of methyl ethyl ketone and added dropwise over 4 hours.
The reaction was performed at 0 ° C. for 2 hours. After the reaction, the mixture was cooled to room temperature, and toluene was added. The precipitated white solid was collected by filtration, washed with toluene, and dried in vacuo overnight to obtain 47 g of a white crystalline compound. Next, 30 g of this compound was taken, 9.5 g of phenol and 95 ml of methyl ethyl ketone were added, and 30 mg of triethylamine was further added.
Allowed to react for hours. After the reaction, toluene was added, and the precipitated crystals were collected by filtration, washed with toluene, and dried in vacuo overnight to obtain 38.5 g of a white crystalline compound. The results of IR measurement of this white crystal were 990 cm ^-1 , 1110 cm ^-1 ,
1320 cm ^-1 , 1590 cm ^-1 , 1700 cm ^-1 , 3
A characteristic peak appeared at 350 cm ^-1 .

Next, 2 g of this compound was taken, and 2.5% by weight
The mixture was crushed and dispersed for 6 hours with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. The liquid temperature of the dispersion immediately after the dispersion was 25 ° C. The dispersed particle size of this compound was 0.6 μm. In addition, 70 g of 3-dibutylamino-6-methyl-7-anilinofluoran was added to an aqueous solution 1 of 5.4% by weight of hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metrose 60SH-03).
Sand grinder (vessel capacity 400) with 30g
ml, manufactured by Imex Co., Ltd.), 3 at 2000 rpm
The mixture was pulverized and dispersed for an hour to obtain a dispersion.

Also, 70 g of diphenyl sulfone was pulverized and dispersed together with 130 g of an 8% by weight aqueous solution of polyvinyl alcohol in a sand grinder (vessel capacity: 400 ml, manufactured by Imex) for 3 hours at a rotation speed of 2000 rpm to obtain a dispersion. In addition, 10 g of calcium carbonate was mixed with 30 g of water, and the mixture was stirred and dispersed with a stirrer to obtain a dispersion. These dispersions were treated with 20 parts by weight of dry solids of the above compound dispersion, 10 parts by weight of dry solids of 3-dibutylamino-6-methyl-7-anilinofluoran dispersion, and dry solids of diphenylsulfone dispersion. 25 parts by weight, 40 parts by weight of a dry solid content of the calcium carbonate dispersion, and a solid content concentration of 16
The coating liquid was obtained by stirring and mixing at a ratio of 20 parts by weight of the dry solid content of the zinc stearate dispersion of 15% by weight and 15 parts by weight of the dry solid content of 15% by weight of polyvinyl alcohol (on a dry basis).

This coating solution was applied to base paper having a weighing of 50 g / m ^{2 using} a bar coater rod No. 10. The coating amount of the coating liquid was 5 g / m ² in terms of dry weight. After drying, it was treated with a super calender to obtain a heat-sensitive recording material. The evaluation result of the sensitivity of the obtained heat-sensitive recording material was as good as the optical density of 1.3. In addition, the print preservability with the vinyl chloride wrap was good. The whiteness of the background was 82, which was good. Table 2 shows the results of these evaluations.

[0464]

Examples 35 to 52 In place of 3-dibutylamino-6-methyl-7-anilinofluoran used in Example 34, 3-diethylamino-6-methyl-7-anilinofluoran (Example 35) ), 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (Example 36), 3-diethylamino-7- (2-chloroanilino) fluoran (Example 37), 3- (N- Ethyl-
Np-Toluidino) -6-methyl-7-anilinofluoran (Example 38), 3-dibutylamino-7- (o
-Chloroanilino) fluoran (Example 39), 3-di-n-pentylamino-6-methyl-7-anilinofluoran (Example 40), 3- (N-methyl-NNn-propylamino) -6 -Methyl-7-anilinofluoran (Example 41), 3- (N-ethyl-N-iso-amylamino) -6-methyl-7-anilinofluoran (Example 42), 3- (N- Cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran (Example 43), 3-dibutylamino-7- (o-fluoroanilino) fluoran (Example 44), 3-diethylamino- 6-methyl-7-m-methylanilinofluoran (Example 45), 3-diethylamino-6-methyl-7
-(2,4-xyridino) fluoran (Example 46),
3-Diethylamino-6-methyl-7- (2,6-xyridino) fluoran (Example 47), 3- (N-ethyl-N-isobutylamino) -6-methyl-7-anilinofluoran (Example) 48), 3-Diethylamino-7-
(O-fluoro) anilinofluoran (Example 49),
3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluoran (Example 5
0), 3- (N-ethyl-N-ethoxypropylamino) -6-methyl-7-anilinofluoran (Example 5
1) A thermosensitive recording material was prepared and evaluated in the same manner as in Example 34 except that 3-diethylamino-7-trifluoromethylanilinofluoran (Example 52) was used. Table 2 summarizes the results.

[0465]

Example 53 In place of 3-dibutylamino-6-methyl-7-anilinofluoran used in Example 34, 3
Same as Example 34 except that 1-dibutylamino-6-methyl-7-anilinofluoran and 3-di-n-pentylamino-6-methyl-7-anilinofluoran were used in a 1: 1 mixture. Then, a heat-sensitive recording material was prepared and evaluated. Table 2 summarizes the results.

[0466]

Example 54 Instead of 3-dibutylamino-6-methyl-7-anilinofluoran used in Example 34, 3
-Dibutylamino-6-methyl-7-anilinofluoran and 3- (N-ethyl-N-iso-amylamino)-
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 34 except that 6-methyl-7-anilinofluorane was used in a 1: 1 mixture. Table 2 summarizes the results.

[0467]

Example 55 Instead of 3-dibutylamino-6-methyl-7-anilinofluoran used in Example 34, 3
-(N-ethyl-N-iso-amylamino) -6-methyl-7-anilinofluoran and 3- (N-ethyl-N
Example 34 except that -iso-amylamino) -6-methyl-7-anilinofluoran was used in a 2: 1 mixture.
A heat-sensitive recording material was prepared in the same manner as described above and evaluated. Table 2 summarizes the results.

[0468]

Examples 56 to 58 In place of hydroxypropylmethylcellulose used in the dispersion of 3-dibutylamino-6-methyl-7-anilinofluoran in Example 34, methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metrose M-1) was used.
5) (Example 56), polyoxyethylene alkyl ether sulfate (Revenol WX, manufactured by Kao Corporation) (Example 5)
7) A thermosensitive recording material was prepared and evaluated in the same manner as in Example 34 except that sodium 2-ethylhexylsulfosuccinate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neocol SWC) (Example 58) was used. Table 2 summarizes the results.

[0469]

Example 59 Urea urethane compound developer dispersion liquid, 3
-Dibutylamino-6-methyl-7-anilinofluoran dispersion, diphenylsulfone dispersion and calcium carbonate dispersion were prepared in the same manner as in Example 34. Also, 2,
70 g of 2-bis (4-hydroxyphenyl) propane was pulverized with 130 g of a 5.4% by weight aqueous solution of polyvinyl alcohol in a sand grinder (400 ml vessel volume, manufactured by Imex Co., Ltd.) for 3 hours at a rotation speed of 2000 rpm.
It was dispersed to obtain a dispersion.

These dispersions were prepared by adding 10 parts by weight of a dry solid content of a urea urethane compound dispersion to 3-dibutylamino-6
-Methyl-7-anilinofluoran dispersion 10% by weight of dry solids, diphenylsulfone dispersion 2
0 parts by weight, 10 parts by weight of dry solids of 2,2-bis (4-hydroxyphenyl) propane dispersion, 20 parts by weight of dry solids of calcium carbonate dispersion, and solids concentration of 16 parts
The coating liquid was obtained by stirring and mixing 10 parts by weight of the dry solid content of the zinc stearate dispersion of 10% by weight and 10 parts by weight of the dry solid content of 15% by weight of polyvinyl alcohol (dry basis). Using this coating solution, a thermosensitive recording material was prepared and evaluated in the same manner as in Example 34. Table 2 summarizes the results.

[0471]

Examples 60 to 63 In place of 2,2-bis (4-hydroxyphenyl) propane used in Example 59, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone (Nippon Soda Co., Ltd., D-8: (Product name) (Example 6)
0), bis (3-allyl-4-hydroxyphenyl) sulfone (manufactured by Nippon Kayaku Co., Ltd., TG-SA: trade name) (Example 61), 2,4′-dihydroxydiphenyl sulfone (manufactured by Nika Chemical Co., Ltd.) 24BPS: trade name) (Example 6)
2), 4,4 '-[oxybis (ethyleneoxy-p-
(Phenylenesulfonyl)] a mixture containing diphenol as a main component (manufactured by Nippon Soda Co., Ltd., D-90: trade name) (Example 6)
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 59 except that 3) was used. Table 2 summarizes the results.

[0472]

Examples 64 to 93 In place of diphenylsulfone used in Examples 59 to 63, β-naphthylbenzyl ether (BON: trade name, manufactured by Ueno Pharmaceutical Co., Ltd.) (Examples 64 to 68), p-benzylbiphenyl (PBBP: trade name, manufactured by Nippon Steel Chemical Co., Ltd.) (Examples 69 to 73), 1, 2
-Di (m-methylphenoxy) ethane (KS, manufactured by Sanko Co., Ltd.)
-235: trade name) (Examples 74 to 78), oxalic acid di-p-methylbenzyl ester (manufactured by Dainippon Ink and Chemicals, HS3520: trade name) (Examples 79 to 83),
1,2-diphenoxymethylbenzene (manufactured by Nichika Chemical Co., Ltd.
Examples 59 to 6 except that PMB-2: trade name) (Examples 84 to 88) and metaterphenyl (manufactured by Nippon Steel Chemical Co., Ltd., mtp: trade name) (Examples 89 to 93) were used, respectively.
In the same manner as in Example 3, a thermosensitive recording material was prepared and evaluated.
The results are summarized in Tables 2 and 3.

[0473]

Examples 94 to 100 In place of diphenylsulfone used in Example 34, an emulsified product of stearamide (manufactured by Chukyo Yushi Co., Ltd., Himicron G-270: trade name) (Example 9)
4), o-chloroanilite acetoacetate (manufactured by Samsung Chemical Industry Co., Ltd.) (Example 95), 1,2-di (m-methylphenoxy) ethane (manufactured by Sanko Co., KS-235: trade name) (Example) 96), oxalic acid di-p-methylbenzyl ester (manufactured by Dainippon Ink and Chemicals, HS3520: trade name)
(Example 97), 1,2-diphenoxymethylbenzene (manufactured by Nika Chemicals, PMB-2: trade name) (Example 9)
8), metaterphenyl (manufactured by Nippon Steel Chemical Co., Ltd., mtp: trade name) (Example 99), diphenoxyethane (Example 1)
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 34 except that (00) was used. Table 3 summarizes the results.

[0474]

Example 101 Example 101 was repeated except that 1 part by weight of a stilbene-based fluorescent dye (Kayahole 3BS, trade name, manufactured by Nippon Kayaku Co., Ltd.) was added to 100 parts by weight of the dry solid content of the coating solution. A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 59. Table 3 summarizes the results.

[0475]

Example 102 1,1,3-Tris (2-methyl-4
-Hydroxy-5-tert-butylphenyl) butane 70 g
Was ground and dispersed together with 130 g of a 5.4% by weight aqueous solution of polyvinyl alcohol in a sand grinder (400 ml vessel volume, manufactured by IMEX Co., Ltd.) at a rotation speed of 2000 rpm for 3 hours to obtain a dispersion. Next, 10 parts by weight of the 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane dispersion was added to 100 parts by weight of the dry solid content of the coating solution of Example 59. A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 59 except that was added. Table 3 summarizes the results.

[0476]

Example 103 2,4-Toluene diisocyanate 3
To 0 g, 30 g of toluene as a solvent was added, and 3.24 g of phenol was added thereto, followed by a reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added. The precipitated white solid was collected by filtration, washed with hexane, and vacuum-dried overnight to obtain 6.9 g of a compound as white crystals. Next, 5.0 g of this compound was taken, 100 g of toluene was added as a solvent, and 3.50 g of aniline was added thereto.
The crystals precipitated after the reaction at 3 ° C. for 3 hours were collected by filtration, washed with hexane, and dried in vacuo overnight to give a white crystalline compound5.
5 g were obtained. The result of IR measurement of this white crystal was 89
0 cm ^-1 , 1000 cm ^-1 , 1030 cm ^-1 , 1440
cm ^-1, 1720cm ^-1, characteristic peaks appeared in 3350 cm ^-1. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 102 except that the above compound was used instead of the urea urethane compound used in Example 102. Table 3 summarizes the results.

[0477]

Embodiments 104 to 109
Instead of 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane (Asahi Made by Denka Kogyo Co., Ltd., Adeka Arculs DH-43) (Example 104), 4-benzyloxy-4 ′-(2,3-epoxy-2-methylprop-1)
-Yloxy) diphenyl sulfone (Nippon Soda Co., Ltd., N
TZ-95) (Example 105), methylene bis (2-hydroxy-3- (benzotriazol-2-yl) -5
-Tert-octylphenyl) (Example 106), 2- (2
'-Hydroxy-5'-methylphenyl) benzotriazole (made by Asahi Denka Kogyo Co., Ltd., Adeka Cruz DN-1)
3) (Example 107), 1,3,5-tris (2,6-
Dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate (Adeka Chemicals DH-48, manufactured by Asahi Denka Kogyo KK) (Example 108), sodium-
Example 10 except that 2,2-methylenebis (4,6-di-tert-butylphenyl) phosphate (Adeka Chemicals F-85, manufactured by Asahi Denka Kogyo KK) (Example 109) was used.
In the same manner as in Example 2, a heat-sensitive recording material was prepared and evaluated. Table 3 summarizes the results.

[0478]

Example 110 2,4-Toluene diisocyanate 4
To 100 g of toluene, 100 g of toluene was added as a solvent, and 4.28 g of aniline was diluted with 40 g of toluene and added dropwise.
The reaction was carried out at a temperature of 1 hour. The white solid precipitated after the reaction was recovered by filtration, washed with hexane, and dried in vacuo overnight to obtain 12.2 g of a white crystalline compound. Then 4 g of this compound
And 40 g of methyl ethyl ketone was added as a solvent, and 4.23 g of phenol was added to 10 g of methyl ethyl ketone.
Then, the mixture was reacted at 90 ° C. for 3 hours, cooled at 5 ° C., and the precipitated crystals were collected by filtration and dried in vacuo overnight to obtain 2.58 g of a white crystalline compound. The analytical values of the white crystals are as follows. Result of IR measurement: 880cm ^-1, 1000cm ^-1, 10
^{40cm -1, 1440cm -1, 1720cm -1} , 172
0 cm ^-1, characteristic peaks appeared in 3300 cm ^-1. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 34 except that the above compound was used instead of the urea urethane compound used in Example 34. Table 3 summarizes the results.

[0479]

Examples 111-115 Instead of 3-dibutylamino-6-methyl-7-anilinofluoran used in Example 110, 3- (N-ethyl-Np-toluidino)-
6-methyl-7-anilinofluoran (Example 11
1), 3-Di-n-pentylamino-6-methyl-7-anilinofluoran (Example 112), 3- (N-methyl-NN-propylamino) -6-methyl-7-anilino Fluoran (Example 113), 3- (N-ethyl-N
-Iso-amylamino) -6-methyl-7-anilinofluoran (Example 114), 3-diethylamino-6
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 110 except that -methyl-7- (2,6-xyridino) fluoran (Example 115) was used. Table 3 summarizes the results.

[0480]

Examples 116 to 120 Instead of diphenylsulfone used in Example 110, β-naphthylbenzyl ether (BON: trade name, manufactured by Ueno Pharmaceutical Co., Ltd.) (Example 116)
p-benzylbiphenyl (PBBP: manufactured by Nippon Steel Chemical Co., Ltd.)
Trade name) (Example 117), 1,2-di (m-methylphenoxy) ethane (manufactured by Sanko Co., KS-235: trade name)
(Example 118), di-p-methylbenzyl oxalate (manufactured by Dainippon Ink and Chemicals, HS3520: trade name) (Example 119), stearamide amide emulsified product (manufactured by Chukyo Yushi, Himicron G-) 270: product name)
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 110 except that (Example 120) was used. The results are summarized in Tables 3 and 4.

[0481]

Examples 121 to 160 Example 1 was repeated in place of the urea urethane compound used in each of Examples 111 to 120.
Urea urethane compounds synthesized in (Examples 121 to 13)
0), the urea urethane compositions synthesized in Example 12 (Examples 131 to 140), the urea urethane compositions synthesized in Example 14 (Examples 141 to 150), Example 103
(Examples 151 to 16)
A thermosensitive recording material was prepared and evaluated in the same manner as in Examples 111 to 120 except that each of 0) was used. The results are summarized in Table 4.

[0482]

Comparative Example 8 Instead of the urea urethane compound synthesized in Example 34, 2,2-bis (4-hydroxyphenyl) was used.
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 34 except that propane was used. Table 4 summarizes the results
Shown in

[0483]

[Table 2]

[0484]

[Table 3]

[0485]

[Table 4]

<Scratch Resistance> It was visually evaluated whether or not a trace of rubbing was formed when the surface of the heat-sensitive recording material was strongly rubbed with a nail. Those with no noticeable rubbing marks were regarded as having good scratch resistance. <Test for Accumulation of Rubbing Traces> A cylinder having a surface of 5 cm in diameter (weight 2 kg) was placed on a recording surface of the produced thermosensitive recording material at a speed of 20 cm / sec at a speed of 20 cm / sec.
After being moved twice, it was left at room temperature for one week. One week later, the readability of the recorded image was visually evaluated, and the one in which the recorded image was sufficiently legible was evaluated as good.

[0487]

Example 161 A heat-sensitive coating liquid was obtained in the same manner as in Example 34. Subsequently, this coating solution was applied on a base paper having a weighing of 50 g / m ² with a rod coater rod No. 10. After drying, it was treated with a super calender to form a thermosensitive coloring layer on the support. The coating amount of the coating liquid was 5 g / m ² in terms of dry weight. Next, 40 g of kaolin and 60 g of a 0.7% sodium hexametaphosphate aqueous solution were sand-grindered (vessel capacity 400 ml, manufactured by Imex Co., Ltd.) at a rotation speed of 2
The mixture was pulverized and dispersed at 000 rpm for 3 hours to obtain a dispersion.

20 parts by weight of a dry solid content of this kaolin dispersion, 10 parts by weight of a dry solid content of a zinc stearate dispersion having a solid concentration of 16% by weight, 40 parts by weight of a dry solid content of an aqueous solution of carboxyl-modified polyvinyl alcohol, polyacrylamide Dry solid content of aqueous solution of epichlorohydrin crosslinking agent 5
The mixture was stirred and mixed in a ratio of parts by weight (on a dry basis) to obtain a coating liquid for forming a protective layer. The coating liquid for forming the protective layer was applied on the thermosensitive coloring layer with a rod number 5 of a bar coater. After drying, it was treated with a super calender to obtain a heat-sensitive recording material. The coating amount of the protective layer forming coating liquid was 2 g / m ² in terms of dry weight.

The evaluation result of the sensitivity of the obtained thermosensitive recording material was as good as the optical density of 1.3. The print preservability with the vinyl chloride wrap was good. In addition, it was visually evaluated whether or not a rubbing trace formed when the surface was strongly rubbed with a nail was visually evaluated. In addition, the results of the long-term scratch resistance test were satisfactory because the recorded images could be read sufficiently. Table 5 summarizes these evaluation results.
Shown in

[0490]

Examples 162 to 163 The procedure of Example 161 was repeated, except that the carboxyl-modified polyvinyl alcohol used in Example 161 was replaced with polyvinyl alcohol (Example 162) and an acrylic copolymer (Example 163). To prepare a heat-sensitive recording material for evaluation. Table 5 summarizes the results.

[0490]

Examples 164-166 Instead of kaolin used in Example 161, aluminum hydroxide (Example 164),
Crosslinkable polymethyl methacrylate resin (Example 165);
Example 1 except that silicon dioxide (Example 166) was used.
A thermosensitive recording material was prepared in the same manner as in No. 61 and evaluated. Table 5 summarizes the results.

[0492]

Example 167 33% by weight calcined kaolin dispersion 100
The mixture was stirred and mixed at a ratio of 12 parts by weight of an aqueous dispersion of 50 parts by weight of a 50% by weight styrene / butadiene latex to obtain a coating liquid for an intermediate layer. Next, 100 parts by weight of an acrylic emulsion of 20% by weight and 10 parts by weight of a fine powder dispersion of silica (Fine Seal SP-10) were stirred and mixed at a ratio of 7 parts by weight (dry basis) to obtain a back coat coating liquid. .

Subsequently, one side of the base paper (50 g / m ² ) was coated with the above-mentioned intermediate layer coating solution so as to have a solid content of 10 g / m ² , dried, and dried on the same surface as in Example 161. The prepared heat-sensitive coating solution was applied so as to have a solid content of 5 g / m ² , dried, and the protective layer coating solution prepared in Example 161 was coated on the same surface with a solid content of 2 g / m ² . Coated and dried to form.
Further, the above-mentioned back coat coating solution was applied to the uncoated surface so as to have a solid content of 1 g / m ² , dried and calendered to prepare a heat-sensitive recording material and evaluated. Was. Table 5 summarizes the results.

[0494]

Comparative Example 9 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 161, except that the coating liquid for forming a protective layer was not applied on the thermosensitive coloring layer. Table 5 summarizes the results.

[0495]

[Table 5]

[0496]

Example 168 2 g of the compound obtained in Example 34 was taken and pulverized and dispersed in a paint shaker for 6 hours together with 8 g of a 2.5% by weight aqueous solution of polyvinyl alcohol (Gosenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). A dispersion was obtained. The temperature of the dispersion immediately after dispersion is 25 ° C., and the pH of the dispersion is
Was 8. The compound has a dispersed particle size of 0.6.
μm.

Further, 3-dibutylamino-6-methyl-
70 g of 7-anilinofluorane and 130 g of a 5.4% by weight aqueous solution of polyvinyl alcohol were pulverized and dispersed in a sand grinder (vessel capacity: 400 ml, manufactured by IMEX Co., Ltd.) at a rotation speed of 2,000 rpm for 3 hours to obtain a dispersion. Also, a sand grinder (Vessel capacity 400 ml, manufactured by Imex Co.) with 70 g of diphenyl sulfone and 130 g of an aqueous solution of 5.4 wt% polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry: Gohsenol KL-05),
The mixture was pulverized and dispersed at 2,000 rpm for 3 hours to obtain a dispersion. In addition, 10 g of calcium carbonate was mixed with 30 g of water, and the mixture was stirred and dispersed with a stirrer to obtain a dispersion.

These dispersions were prepared by adding 30 parts by weight of the solid dispersion of the above compound dispersion to 3-dibutylamino-6-methyl-
15 parts by weight of dry solid content of 7-anilinofluorane dispersion, 30 parts by weight of dry solids of diphenylsulfone dispersion, 20 parts by weight of dry solids of calcium carbonate dispersion, and stearic acid having a solids concentration of 16% by weight The coating liquid was obtained by stirring and mixing at a ratio of 10 parts by weight of the dry solid content of the zinc dispersion and 7 parts by weight of the dry solid content of 15% by weight polyvinyl alcohol (on a dry basis). The pH of this coating solution was 8.2.

Next, this coating liquid was applied on a high-quality paper surface having a basis weight of 50 g / m ² to a dry weight of 5 g / m ² , dried and processed by a super calender to prepare a heat-sensitive recording material. The evaluation result of the coloring sensitivity of the obtained heat-sensitive recording material was as good as the optical density of 1.3. Further, the print preservability of the vinyl chloride wrap was good without fading. Table 6 summarizes the results.

[0500]

Example 169 2 g of the urea urethane compound synthesized in Example 168 was added, and 2 g of diphenylsulfone was added thereto.
The resulting mixture was crushed and dispersed together with g in a paint shaker for 6 hours to obtain a dispersion. Subsequently, heat-sensitive recording was performed in the same manner as in Example 168 except that the above co-dispersion was added in a proportion of 60 parts by weight of dry solid content instead of the dispersion of the compound obtained in Example 168 and the diphenyl sulfone dispersion. Materials were prepared and evaluated. Table 6 summarizes the results.

[0501]

Example 170 2,4-Toluene diisocyanate 6
To 1 g was added 450 g of toluene as a solvent, and
26 g of aniline dissolved in 150 g of ene are dropped in 6 hours
And reacted at 5 ° C. for 7 hours. After the reaction, precipitated
A white solid is recovered by filtration, washed with toluene,
After vacuum drying overnight, 70 g of a white crystalline compound was obtained. next
Using 30 g of this compound as a solvent and 365 g of toluene
In addition to this, 2,2-bis (4-hydroxyphenyl)
Add 12.2 g of propane and 0.3 mg of triethylamine.
For 4 hours at 60 ° C with stirring, then 3 hours at 70 ° C
During the reaction, the temperature was further increased and the reaction was carried out at 80 ° C. for 3 hours. reaction
Thereafter, the reaction solution was cooled to room temperature, and the precipitated crystals were collected by filtration.
After recovering, wash with toluene and dry under vacuum overnight to form white
42 g of crystalline compound were obtained. The result of IR measurement of this white crystal was
Fruit is 750cm^-1, 840cm^-1, 1020cm^-1,
1500cm^-11600cm^-1, 1720cm^-1, 3
320cm ^-1, A characteristic peak appeared.

Next, 2 g of this compound was taken, 2 g of diphenyl sulfone was added thereto, and 2.5% by weight of modified polyvinyl alcohol (Goseilan L-3 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
266) Pulverized and dispersed in a paint shaker together with 16 g of the aqueous solution for 6 hours to obtain a dispersion. Subsequently, Example 168
A heat-sensitive recording material was prepared in the same manner as in Example 168 except that a co-dispersion of the above compound and diphenyl sulfone was added in a proportion of 60 parts by weight of dry solid content instead of the dispersion of the compound obtained in the above and the dispersion of diphenyl sulfone. Created and evaluated. Table 6 summarizes the results.

[0503]

Example 171 2 g of the compound obtained in Example 103 was taken, 2 g of dimethylbenzyl oxalate was added thereto, and a 2.5% by weight aqueous solution of modified polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd .: Goselan L-3266) was used. 16
The resulting mixture was crushed and dispersed together with g in a paint shaker for 6 hours to obtain a dispersion. Subsequently, instead of the dispersion of the compound obtained in Example 168 and the dispersion of diphenylsulfone, a co-dispersion of the above compound and di-p-methylbenzyl oxalate was added at a ratio of 60 parts by weight of dry solids. Except for the above, a thermal recording material was prepared and evaluated in the same manner as in Example 168. Table 6 summarizes the results.

[0504]

Example 172 2 g of the compound obtained in Example 2 was taken and pulverized and dispersed in a paint shaker for 6 hours together with 8 g of a 2.5% by weight aqueous solution of methylcellulose (Shin-Etsu Chemical Co., Ltd .: Metrolose SM-15) to give a dispersion. I got Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 168 except that a dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 168. Table 6 summarizes the results.

[0505]

Examples 173 to 177 Instead of polyvinyl alcohol (Gosenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) used as a dispersant for the urea urethane compound of Example 168, ammonium polycarboxylate (manufactured by Sannopco: Disper) Santo 5027) (Example 173),
Water-soluble low molecular weight copolymer (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Discoat N14) (Example 174), 2-ethylhexyl sulfosuccinate sodium (Daiichi Kogyo Seiyaku Co., Ltd .: Neocol S)
WC) (Example 175), hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .: Metroz 60SH-0)
3) A thermosensitive recording material was prepared and evaluated in the same manner as in Example 168 except that condensed sodium naphthalenesulfonate (Roman D, manufactured by San Nopco) (Example 177) was used (Example 176). Table 6 summarizes the results.

[0506]

Examples 178 to 183 Instead of polyvinyl alcohol (Gosenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) used as a dispersant for diphenyl sulfone in Example 168, methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .: Metroze SM-15) was used. ) (Example 178), water-soluble low molecular weight copolymer (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: DISCOAT N14) (Example 179), sodium 2-ethylhexylsulfosuccinate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neocol SWC) (Example) 18
0), hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .: Metroose 60SH-03) (Example 18)
1), condensed sodium naphthalene sulfonate (manufactured by San Nopco: Roma D) (Example 182), ammonium polycarboxylate (manufactured by San Nopco: Dispersant 502)
7) A thermosensitive recording material was prepared and evaluated in the same manner as in Example 168 except that (Example 183) was used. Table 6 summarizes the results.

[0507]

Examples 184 to 186 Instead of polyvinyl alcohol (Gosenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) used as a dispersant for diphenylsulfone in Example 172, methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .: Metroze SM-15) was used. ) (Example 184), hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .: Metroz 60)
SH-03) (Example 185), modified polyvinyl alcohol (Goseiran L-326, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
6) A thermosensitive recording material was prepared and evaluated in the same manner as in Example 172 except that (Example 186) was used. Table 6 summarizes the results.

[0508]

Example 187 In place of methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .: Metrolose SM-15) used as a dispersant for the urea urethane compound of Example 184, modified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Goselan L-)
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 184 except that 3266) was used. Table 6 summarizes the results.

[0509]

Examples 188 to 189 Instead of polyvinyl alcohol (Gosenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) used as a dispersant for diphenylsulfone in Example 174, methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .: Metroze SM-15) was used. ) (Example 188), hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .: Metroz 60)
Example 1 except that SH-03) (Example 189) was used.
A heat-sensitive recording material was prepared and evaluated in the same manner as in No. 74. Table 6 summarizes the results.

[0510]

Examples 190 to 191 Instead of polyvinyl alcohol (Gosenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) used as a dispersant for diphenyl sulfone in Example 176, methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metrose SM-15) was used. ) (Example 190), hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .: Metroz 60)
Example 1 except that SH-03) (Example 191) was used.
In the same manner as in No. 76, a thermosensitive recording material was prepared and evaluated. Table 6 summarizes the results.

[0511]

Examples 192 to 193 Instead of polyvinyl alcohol used as a dispersant for 3-dibutylamino-6-methyl-7-anilinofluoran in Example 189, hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metrose 60SH) was used. -03) (Example 192), hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .: Metroose 60SH-03) and sodium 2-ethylhexylsulfosuccinate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neocol SWC)
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 189 except that the mixed dispersant (weight ratio 1/1) (Example 193) was used. Table 6 summarizes the results.

[0512]

Comparative Example 10 A thermosensitive recording sheet was prepared and evaluated in the same manner as in Example 168 except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea urethane compound synthesized in Example 168. Was done. Table 6 summarizes the results.

[0513]

Comparative Examples 11 to 12 The urea urethane compound synthesized in Example 168 was dispersed in the same manner as in Example 168 except that the dispersion time was changed, and the average particle size was measured.
(Comparative Example 11) and 6.5 μm (Comparative Example 12).
A heat-sensitive recording sheet was prepared and evaluated in the same manner as in Example 168 except that each of these dispersions was used. Table 6 summarizes the results.

[0514]

Comparative Example 13 The urea urethane compound synthesized in Example 168 was dispersed in the same manner as in Example 168. However,
During the dispersion, the liquid temperature was kept at 65 ° C. A heat-sensitive recording sheet was prepared and evaluated in the same manner as in Example 168 except that this dispersion was used. Table 6 summarizes the results.

[0515]

Comparative Example 14 The urea urethane compound synthesized in Example 168 was dispersed in the same manner as in Example 168. However,
The pH of the dispersion used for dispersion was adjusted to 4.
A heat-sensitive recording sheet was prepared and evaluated in the same manner as in Example 168 except that this dispersion was used. Table 6 summarizes the results.

[0516]

Comparative Example 15 The urea urethane compound synthesized in Example 168 was dispersed in the same manner as in Example 168. However,
The pH of the dispersion used for dispersion was adjusted to 11. A heat-sensitive recording sheet was prepared and evaluated in the same manner as in Example 168 except that this dispersion was used. Table 6 summarizes the results.

[0517]

Comparative Example 16 To the coating solution of Example 168, 1N-sulfuric acid was added to adjust the pH to 4.0. A thermosensitive recording sheet was prepared in the same manner as in Example 168 except that this coating liquid was used.
An evaluation was performed. Table 6 summarizes the results.

[0518]

Comparative Example 17 To the coating solution of Example 168, 1N-sodium hydroxide was added to adjust the pH to 12.5. A heat-sensitive recording sheet was prepared and evaluated in the same manner as in Example 168 except that this coating liquid was used. Table 6 summarizes the results.

[0519]

[Table 6]

[0520]

EXAMPLE 194 The coating solution of Example 168 having a pH of paper surface of 3.
2 was coated on a high-quality paper at a dry weight of 5 g / m ² , dried and treated with a super calender to prepare a heat-sensitive recording material. The evaluation result of the coloring sensitivity of the obtained heat-sensitive recording material was as good as the optical density of 1.3. Further, the print preservability of the vinyl chloride wrap was good without fading. In addition, background preservability was good with little coloring. Table 7 summarizes the results.

[0521]

Examples 195 to 196 The paper p used in Example 194
In the same manner as in Example 194 except that high-quality paper having a paper surface pH of 5 (Example 195) and high-quality paper having a paper pH of 6.8 (Example 196) were used instead of the high-quality paper having H of 3.2. To prepare a heat-sensitive recording material and evaluated. Table 7 summarizes the results
Shown in

[0522]

Comparative Examples 18 to 19 Instead of the high-quality paper having a pH of 3.2 used in Example 194, high-quality paper having a pH of 2.8 (Comparative Example 18) and a high-quality paper having a pH of 9.5 are used. (Comparative Example 1
A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 194 except that 9) was used. Table 7 summarizes the results.

[0523]

[Table 7]

[0524]

Example 197) A) Preparation of coating solution for magnetic recording layer 100 parts by weight of barium ferrite (coercive force 2700)
25 parts by weight of sodium polyacrylate (20% by weight aqueous solution), 100 parts by weight of polyvinylidene chloride (49% by weight dispersion), 15 parts by weight of carbon black (36% by weight dispersion), paraffin WAX (methyl cellulose dispersion, 20% by weight) (Dispersion) A mixture of 10 parts by weight of water and 100 parts by weight of water was dispersed in a ball mill for 10 hours to prepare a coating solution for the magnetic recording layer. B) Preparation of coating solution for heat-sensitive recording layer A coating solution for heat-sensitive recording layer was obtained in the same manner as in Example 34. next,
The magnetic recording layer coating solution prepared in A) was applied onto a high-quality paper surface having a basis weight of 150 g / m ² to a dry weight of 30 g / m ² and dried to obtain a magnetic recording layer. Next, the heat-sensitive recording layer coating solution prepared in B) is applied to the other surface of the support having the magnetic recording layer so that the dry weight thereof is 6 g / m ^2, and after drying, treated with a super calender. Thus, a thermosensitive magnetic recording material was obtained. The evaluation result of the coloring sensitivity of the thermosensitive recording layer of the obtained thermosensitive magnetic recording material was as good as the optical density of 1.3. Further, the print preservability of the vinyl chloride wrap was good without fading. Table 8 summarizes the results.

[0525]

Example 198 C) Preparation of Coating Solution for Protective Layer 20 parts by weight of zinc stearate, 20 parts by weight of a 5% by weight aqueous solution of methylcellulose and 60 parts by weight of water were mixed and dispersed by a sand grinder for 2 hours. Next, 20 parts by weight of a 10% by weight aqueous solution of carboxy-modified polyvinyl alcohol, 1.5 parts by weight of silica, 12.5 parts by weight of polyamide epichlorohydrin
6.5 parts by weight of a 1% by weight aqueous solution and 15.0 parts by weight of water were mixed and dispersed by a sand grinder for 2 hours. Next, 0.7 parts by weight of the above zinc stearate dispersion and 45 parts of the silica dispersion.
0 parts by weight and 11.3 parts by weight of water were mixed to prepare a coating solution for the protective layer, and this coating solution was applied onto the thermosensitive recording layer of the thermosensitive magnetic recording material of Example 197 to a dry weight of 3 g / m ² . A thermosensitive magnetic recording material was prepared and evaluated in the same manner as in Example 197 except that a protective layer was formed by coating and drying as described above. Table 8 summarizes the results.

[0526]

EXAMPLE 199 D) Preparation of Coating Solution for Intermediate Layer An intermediate comprising a ratio of 80 parts by weight of dry solids of a 48% polystyrene fine particle dispersion and 20 parts by weight of dry solids of a 40% styrene / acrylate copolymer emulsion. A layer coating solution was prepared. The weight of the coating solution was 8 g when dried between the thermosensitive recording layer of the thermosensitive magnetic recording material of Example 198 and the support.
/ M ² , a thermosensitive magnetic recording material was prepared in the same manner as in Example 198 except that an intermediate layer was formed by coating and drying.
An evaluation was performed. Table 8 summarizes the results.

[0527]

Comparative Example 20 A heat-sensitive recording sheet was prepared and evaluated in the same manner as in Example 197 except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea urethane compound synthesized in Example 197. Was done. Table 8 summarizes the results.

[0528]

[Table 8]

[0529]

Example 200 A) Preparation of coating solution for heat-sensitive recording layer A coating solution for heat-sensitive recording layer was obtained in the same manner as in Example 34. next,
The heat-sensitive recording layer coating solution prepared in A) is applied and dried on a high-quality paper surface having a basis weight of 150 g / m ² so as to have a dry weight of 7 g / m ^2, and treated with a super calender to obtain a heat-sensitive recording layer coated sheet. Created. B) Preparation of Release Sheet To a base paper having a basis weight of 40 g / m ² , a release agent composed of oily dimethyl silicone was added in an amount of 1 g / g using a gravure coater.
m ^{2 was} applied to provide a release layer. Then, on the release layer,
An adhesive layer component consisting of 100 parts by weight of chlorinated rubber, 20 parts by weight of ester gum, and 120 parts by weight of dibutyl phthalate
g / m ² .

C) Preparation of Label for Thermosensitive Recording The non-coated surface of the coated sheet of the thermal recording layer prepared in A) above and the adhesive layer coated surface of the release sheet prepared in B) above were adhered so as to face each other. In addition, a thermosensitive recording label was produced. The evaluation result of the coloring sensitivity of the obtained label for thermal recording was as good as the optical density of 1.3. Further, the print preservability of the vinyl chloride wrap was good without fading. Table 9 summarizes the results.

[0531]

Example 201 D) Preparation of coating liquid for back coat layer 100 parts by weight of a styrene-maleic acid copolymer and 50 parts by weight of kaolin were mixed to prepare a coating liquid for a back coat layer.
This coating solution was dried on the surface of the heat-sensitive recording label of Example 200 opposite to the surface on which the heat-sensitive recording layer was applied, and weighed 1 g / m2 when dried.
^A label for heat-sensitive recording was prepared and evaluated in the same manner as in Example 200 except that a back coat layer was formed by coating and drying to obtain No. 2. Table 9 summarizes the results.

[0532]

Example 202 E) Preparation of Coating Solution for Intermediate Layer An intermediate consisting of 80 parts by weight of dry solids of a 48% polystyrene fine particle dispersion and 20 parts by weight of dry solids of a 40% styrene / acrylate copolymer emulsion. A layer coating solution was prepared. The weight of the coating solution when dried between the heat-sensitive recording layer of the heat-sensitive recording label of Example 201 and the support was 8 g.
/ M ² , a thermosensitive recording label was prepared in the same manner as in Example 201, except that the intermediate layer was formed by coating and drying.
An evaluation was performed. Table 9 summarizes the results.

[0533]

Example 203 F) Preparation of Coating Solution for Protective Layer 20 parts by weight of zinc stearate, 20 parts by weight of a 5% by weight aqueous solution of methylcellulose and 60 parts by weight of water were mixed and dispersed by a sand grinder for 2 hours. Next, 20 parts by weight of a 10% by weight aqueous solution of carboxy-modified polyvinyl alcohol, 1.5 parts by weight of silica, 12.5 parts by weight of polyamide epichlorohydrin
6.5 parts by weight of a 1% by weight aqueous solution and 15.0 parts by weight of water were mixed and dispersed by a sand grinder for 2 hours. Next, 0.7 parts by weight of the above zinc stearate dispersion and 45 parts of the silica dispersion.
0 parts by weight and 11.3 parts by weight of water were mixed to prepare a coating solution for the protective layer. The coating solution was dried on the heat-sensitive recording layer of the heat-sensitive recording label of Example 202 to a dry weight of 3 g / m ² . A thermosensitive recording label was prepared and evaluated in the same manner as in Example 202 except that a protective layer was formed by coating and drying as described above. Table 9 summarizes the results.

[0534]

Comparative Example 21 A thermosensitive recording sheet was prepared and evaluated in the same manner as in Example 200 except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea urethane compound synthesized in Example 200. Was done. Table 9 summarizes the results.

[0535]

[Table 9]

[0536]

Example 204 On one surface of a commercially available polyethylene terephthalate film having a thickness of 75 μm (trade name: Lumirror E, manufactured by Toray Industries Co., Ltd.), the following thermosensitive coloring layer and intermediate layer paint were applied in order from the support side. Layer, magenta coloring thermal recording layer, intermediate layer, yellow coloring thermal recording layer,
Multi-layer coating was performed so as to form an intermediate layer. The coated amounts of the heat-sensitive recording layer and the intermediate layer after drying were 6.5 g / m ² , respectively.
A bar coating was performed so as to obtain 2.0 g / m ² to obtain a multicolor heat-sensitive recording material.

Preparation of coating material for cyan coloring thermosensitive recording layer Liquid A (thermosensitive coloring dye dispersion) 20 parts by weight of 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide and 10% polyvinyl alcohol 20 parts by weight of an aqueous solution and 10 parts by weight of water are mixed,
It was dispersed and pulverized with a sand grinder (manufactured by Imex Co., Ltd.) to prepare an average particle size of 0.7 μm. Liquid B (Developer dispersion liquid) A urea urethane compound was synthesized in the same manner as in Example 34, and 30 g of this compound was taken and pulverized and dispersed in a sand grinder for 3 hours together with 120 g of a 2.5% by weight aqueous polyvinyl alcohol solution, followed by dispersion. A liquid was obtained. The liquid temperature of the dispersion immediately after the dispersion was 25 ° C. The dispersed particle size of this compound was 0.6 μm. A liquid 30 parts by weight, B liquid 120
Parts by weight, 52 parts by weight of 60% calcium carbonate slurry, 1
40% by weight of 0% polyvinyl alcohol aqueous solution, SBR latex (solid content: 50%, Asahi Kasei, trademark: L-153)
7) 28 parts by weight of stearamide (solid content 26.5)
%, Manufactured by Chukyo Yushi Co., Ltd., trade name: Cellsol A-877) and 11 parts by weight of water and 82 parts by weight of water were mixed to obtain a cyan-colored thermosensitive coloring layer coating.

Preparation of paint for magenta coloring heat-sensitive recording layer Liquid A (thermosensitive coloring dye dispersion) 4-N- (2- (2,4-di-tert-amylphenoxy) butyryl) piperazinobenzenediazonium hexafluoro 20 parts by weight of phosphate, 20 parts by weight of a 10% aqueous polyvinyl alcohol solution, and 10 parts by weight of water were mixed, dispersed and pulverized with a sand glider to prepare an average particle size of 0.7 μm. Liquid B (coupler dispersion liquid) 1- (2'-octylphenyl) -3-methyl-5-pyrazolone 50 parts by weight, 1,2,3-triphenylguanidine 50 parts by weight, 10% polyvinyl alcohol aqueous solution 50 parts by weight , Water and 25 parts by weight of water, and dispersed and pulverized with a sand glider to prepare an average particle size of 1.0 μm. Solution A 30 parts by weight, Solution B 90 parts by weight, 60% calcium carbonate slurry 52 parts by weight, 10% polyvinyl alcohol aqueous solution 40 parts by weight, SBR latex (solid content 5
0%, 28 parts by weight of Asahi Kasei, trademark: L-1537), 11 parts by weight of stearic acid amide (solid content: 26.5%, manufactured by Chukyo Yushi Co., Ltd., trademark: Cellol A-877), and 82 parts by weight of water were mixed, and magenta was mixed. This was a coloring heat-sensitive coloring layer paint.

Preparation of coating material for yellow-colored thermosensitive recording layer Liquid A (thermosensitive dye-dispersing solution) 2,5-dibutoxy-4-tolylthiobenzenebenzenediazonium hexafluorophosphate 20 parts by weight, 10% polyvinyl alcohol aqueous solution 20 Parts by weight,
10 parts by weight of water were mixed, dispersed and pulverized with a sand glider to prepare an average particle size of 0.7 μm. Liquid B (coupler dispersion) 50 parts by weight of 2-chloro-5- (3- (2,4-di-tert-pentyl) phenoxypropylamino) acetoacetanilide, 1,2,3-triphenylguanidine 5
0 parts by weight, 50 parts by weight of a 10% aqueous polyvinyl alcohol solution and 25 parts by weight of water were mixed, dispersed and pulverized with a sand glider to prepare an average particle size of 1.0 μm. Solution A 30 parts by weight, Solution B 90 parts by weight, 60% calcium carbonate slurry 52 parts by weight, 10% polyvinyl alcohol aqueous solution 40 parts by weight, SBR latex (solid content 50
%, Asahi Kasei, trademark: L-1537) 28 parts by weight, stearamide (solid content: 26.5%, manufactured by Chukyo Yushi, trademark:
11 parts by weight of cellosol A-877) and 82 parts by weight of water were mixed to prepare a yellow coloring thermosensitive coloring layer coating.

Preparation of paint for intermediate layer paint (solid content 15%) 42% by weight of 60% kaolinite clay (average particle size 0.6 μm) dispersion, carboxylic acid-modified polyvinyl alcohol aqueous solution (solid content 10%, Nihon Gosei) 200 parts by weight, manufactured by Kagaku Co., Ltd., trademark: Gohsenal T-330, acrylic emulsion (solid content: 40%, manufactured by Nippon Shokubai Co., Ltd., trademark: SC
-2250) 100 parts by weight, dimethylol urea solution (solid content 30%, manufactured by Showa Denko KK, trademark: J-001) 3
3 parts by weight, 40% zinc stearate dispersion (average particle size 0.9 μm, manufactured by Chukyo Yushi Co., Ltd., trademark: Himicron F
-930) 13 parts by weight, heavy calcium carbonate (manufactured by Nitto Powder Chemical Co., Ltd., trade name: NS-1000) 70 parts by weight, urethane acrylate emulsion (solid content 40%, Arakawa Chemical Co., trade name: EM90) 25 weight parts Parts, polysiloxane (solid content 33%, manufactured by Toray Dow Corning Silicone, trademark:
SM7025), and 5 parts by weight of water and 40 parts by weight of water were mixed to prepare an intermediate layer coating.

[0541]

Example 205 An example of producing a two-color heat-sensitive recording material is described below. (A) Leuco dye for high-temperature coloring layer: 3- (4'-dibutylamino-2'-hydroxyphenyl) -3- (5'-anilino-4'-methyl-2'-methoxyphenyl) phthalide (B) Low temperature Leuco dye for coloring layer: 3-diethylamino-
7-Chlorofluorane (C) Developer: urea urethane compound synthesized in Example 204 (D) Sensitizer: Diphenyl sulfone 40 g of each of the above organic compounds (A) to (D) is a 10% solution of polyvinyl alcohol (Polymerization degree 500, saponification degree 9
0%) and 20 g of water, and each of these compositions was separately prepared using a vertical sand mill (manufactured by Imex Corporation,
(Sand grinder) so as to have a particle size of 1 μm, and liquids (A) to (D) corresponding to compounds A to D were prepared from the respective dispersions.

Also, 40 g of light calcium carbonate (Brilliant 15, manufactured by Shiraishi Kogyo Co., Ltd., having an average particle size of 0.15 μm) and 60 g of a 0.7% sodium hexametaphosphate solution were mixed, and this composition was dispersed using a Cowles disperser. Separately, a 21% zinc stearate dispersion was prepared as a lubricant dispersion (F) solution, and a 10% polyvinyl alcohol (NM11, manufactured by Nippon Synthetic Chemical Industry) was prepared as an adhesive (G) solution.

Preparation of High Temperature Color Sensitive Thermal Coating Liquid (I) The weight ratio of the above (A), (C), (D) and (G) liquids after drying was (A) :( C): (E): (G) = 2
0: 40: 25: 15 was added to prepare a coating solution for a high-temperature coloring heat-sensitive layer. -Formation of high-temperature coloring heat-sensitive layer The heat-sensitive layer coating solution (I) was weighed 6 using a Mayer bar.
It was coated on a high-quality paper (neutral paper) of 0 g / m ² at a coating amount of 8 g / m ² (dry) to form a high-temperature coloring heat-sensitive layer.

Preparation of low-temperature coloring heat-sensitive layer coating solution (II) Further, the above-mentioned solutions (B), (C), (D), (E), (F) and (G) were weighed after drying. The ratio is (B) :( C):
(D): (E): (F): (G) = 10: 20: 20:
A low-temperature coloring heat-sensitive layer coating liquid was prepared by blending at a ratio of 20:10:10. Preparation of two-color heat-sensitive recording material A low-temperature color-forming layer coating liquid (II) was applied on the high-temperature color-forming heat-sensitive layer so that the coating amount was 5 g / m ² (dry). Thereafter, a smoothing process using a super calender is performed to increase the Beck smoothness (JIS-P8119) of the heat-sensitive recording surface to 150.
Adjusted to seconds, a two-color heat-sensitive recording material was obtained.

[0545]

Comparative Example 22 A multicolor heat-sensitive recording material was prepared in the same manner as in Example 204 except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea urethane compound synthesized in Example 204. , Was evaluated. The results are summarized in Table 10.

[0546]

Comparative Example 23 A two-color heat-sensitive recording material was prepared in the same manner as in Example 205 except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea urethane compound used in Example 205. , Was evaluated. The results are summarized in Table 10. Evaluation of multicolor heat-sensitive recording material The multicolor heat-sensitive recording materials obtained in Examples 204 to 205 and Comparative Examples 22 to 23 were recorded with a commercially available heat-sensitive printer (trade name: NC-1 manufactured by Fuji Photo Film Co., Ltd.). Image quality when performing,
Image storability was evaluated by the following method. <Image Quality> Regarding the recording materials, five images were visually evaluated for sharpness, contrast, image density unevenness, and the like, and evaluated on a five-point scale. (Good: Good, Good-Good: Good, Good: Good, Good-Good: Somewhat bad, Good: Bad)

<Image preservability> The recording material was sandwiched between vinyl chloride wraps or vinyl chloride files,
g / cm ² and left at 40 ° C. for 24 hours.
After standing, the density of the printed portion and the unprinted portion (background) were visually evaluated, and those with little decoloration of the printed density were regarded as having good image storability. The results are as shown in Table 10;
Comparative Example 22 to 23 exhibited excellent image storability, whereas Comparative Examples 22 to 23 exhibited Examples 204 to 205.
Inferior.

[0548]

[Table 10]

[0549]

Example 206 A urea urethane compound was synthesized in the same manner as in Example 34, and 2 g of this compound was taken and pulverized and dispersed for 6 hours with a paint shaker together with 8 g of a 2.5% by weight aqueous solution of polyvinyl alcohol to obtain a dispersion. . The liquid temperature of the dispersion immediately after the dispersion was 25 ° C. The dispersed particle size of this compound was 0.6 μm. Also, 70 g of 3-dibutylamino-6-methyl-7-anilinofluoran was pulverized together with 130 g of a 5.4% by weight aqueous solution of polyvinyl alcohol in a sand grinder (400 ml vessel volume, manufactured by IMEX Co., Ltd.) for 3 hours at a rotation speed of 2000 rpm.
It was dispersed to obtain a dispersion.

In addition, 70 g of diphenyl sulfone was added to 5.4 g
A dispersion was obtained by pulverizing and dispersing with a sand grinder (Vessel capacity: 400 ml, manufactured by IMEX Co., Ltd.) at a rotation speed of 2,000 rpm for 3 hours together with 130 g of an aqueous solution of polyvinyl alcohol by weight. In addition, 10 g of calcium carbonate is added to 30 pieces of water.
g and mixed with a stirrer to obtain a dispersion. Also, a mixture of 60 parts by weight of aluminum hydroxide and 40 parts by weight of a 12.5% by weight aqueous solution of polyvinyl alcohol is treated with a sand grinder for 2 hours to disperse the average particle size to about 1 μm, and a dispersion of aluminum hydroxide is prepared. I got

These dispersions were prepared by adding 20 parts by weight of the solid dispersion of the above compound dispersion to 3-dibutylamino-6-methyl-
10 parts by weight of dry solids of 7-anilinofluorane dispersion, 25 parts by weight of dry solids of diphenylsulfone dispersion, 40 parts by weight of dry solids of calcium carbonate dispersion, 13 parts by weight of aluminum hydroxide dispersion 20 parts by weight of a zinc stearate dispersion having a solids concentration of 16% by weight and a dry solids content of 15 parts by weight of 15% by weight of polyvinyl alcohol (20 parts by weight), and further mixed by stirring. A liquid was obtained.

Next, this thermosensitive recording layer coating solution was applied onto aluminum-evaporated paper at a rate of 50 m / min using a gravure coater (200 mesh, plate depth 20 μ). This was dried at 80 ° C. for 3 seconds to obtain a heat-sensitive recording layer having a thickness of 2 μm. Then, a clear coat solution composed of an aqueous dispersion of an acrylic resin (mainly composed of methyl methacrylate, 2-ethylhexyl acrylate and styrene, and having a glass transition point of about 40 ° C.) was applied to the coated surface to a thickness of 8 μm by a roll coater. And dried at 80 ° C. for 10 seconds to obtain a vapor deposited paper for laser marking of the present invention. The vapor-deposited paper was irradiated with a laser beam by a carbon dioxide laser. A clear mark was obtained, and the coloring was good. Further, this was sandwiched between wraps and a plasticizer resistance test was carried out. As a result, no fading of the printed portion was observed and the printing was good. Table 11 summarizes the results.

[0553]

Example 207 A urea urethane compound was synthesized in the same manner as in Example 170, and 2 g of this compound was taken and pulverized and dispersed with a paint shaker for 6 hours together with 8 g of a 2.5% by weight aqueous polyvinyl alcohol solution to obtain a dispersion. . Subsequently, in the same manner as in Example 206 except that a dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 206, and diphenyl sulfone was used instead of aluminum hydroxide, a vapor-deposited paper for laser marking was used. Was prepared and evaluated. Table 11 summarizes the results.

[0554]

Comparative Example 24 A vapor deposited paper for laser marking was prepared in the same manner as in Example 206 except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea urethane compound synthesized in Example 206. , Was evaluated. Table 11 summarizes the results. <Coloring sensitivity> A laser beam of 0.6 J is applied to a laser marking article using a carbon dioxide laser (Ushio Inc., Unimark) using a stencil that produces numbers.
/ Cm ² energy. Clear marks were obtained, and those with high coloring density were evaluated as good. <Plasticizer resistance> A vinyl chloride wrap film was stacked three by three on the marketed article for laser marking and left at 40 ° C for 24 hours under a load of 300 g / cm ² . After the standing, the density of the printed portion was visually evaluated, and those with little decoloration of the print density were regarded as having good print storability.

[0555]

[Table 11]

[0556]

Example 208 (1) Preparation of upper paper 3-Diethylamino-7-chlorofuran was added to 100 parts by weight of a 5% aqueous solution of pH 4.0 in which a styrene-maleic anhydride copolymer was dissolved together with a small amount of sodium hydroxide. Eighty parts by weight of Nisseki Hisol N-296 (trade name, oil manufactured by Nippon Petrochemical) in which 2.5 parts by weight of orane were dissolved were emulsified. On the other hand, 10 parts by weight of melamine, 25 parts by weight of a 37% formalin aqueous solution, and 65 parts by weight of water were adjusted to pH 9.0 with sodium hydroxide, and heated to 60 ° C., which became transparent in 15 minutes, and a melamine-formalin precondensate was gotten. This initial condensate was added to the above emulsion, and stirring was continued for 4 hours while maintaining the temperature at 60 ° C., followed by cooling to room temperature. The solid content of the obtained microcapsule dispersion was 45%. The microcapsule dispersion thus obtained was applied to paper and dried to obtain an upper paper.

(2) Preparation of lower paper 15 g of the composition synthesized in the same manner as in Example 7 was taken, and
The mixture was crushed and dispersed with a 45% by weight aqueous solution of polyvinyl alcohol in a paint shaker at room temperature for 45 minutes to obtain a dispersion. Further, 60 g of calcium carbonate was mixed with 90 g of water, and the mixture was stirred and dispersed with a stirrer to obtain a dispersion. The coating liquid was obtained by mixing and stirring 40 parts by weight of the above compound dispersion, 125 parts by weight of calcium carbonate dispersion, and 120 parts by weight of a 10% by weight aqueous solution of polyvinyl alcohol.
This coating solution was applied to a base paper having a weighing of 40 g / m ² with a bar coater rod No. 10 to obtain a lower paper. The evaluation result of the coloring density was as good as the optical density of 0.7. The evaluation result of the solvent resistance with the hand cream was good because the printed portion could be read. Table 12 summarizes the results.

[0558]

Comparative Example 25 A pressure-sensitive recording material was prepared in the same manner as in Example 208 except that activated terra clay as a color developer was used in place of the urea urethane composition used in Example 208.
An evaluation was performed. Table 12 summarizes the results.

[0559]

[Table 12]

[0560]

By using a specific urea urethane compound, a color former and a recording material having excellent image storability and color sensitivity can be provided at low cost.

Continued on front page F-term (reference) 2H026 AA07 AA11 AA24 AA28 BB02 BB24 CC05 DD42 DD53 EE03 FF01 FF07 FF29 4H006 AA01 AA03 AB99 RA38 RA42 RA50 RA54 RA56 TA02 TB13 4H056 BA02 BB05 BB14 BD01 BF02BF28F26F

Claims (94)

[Claims] 1. A compound represented by the following formula (c) having a molecular weight of 500:
A urea urethane compound characterized by being 0 or less. Embedded image (Wherein, R represents an aliphatic compound residue, A ₁ and A ₂ each independently represent an aromatic compound residue, and the nitrogen atom of the urea group is a carbon atom of the aromatic ring of A ₁ or A _2. Directly connected to
Further, R, A ₁ and A ₂ may have a substituent. ) 2. A urea urethane compound represented by the following formula (d): Embedded image (Wherein, R represents an aliphatic compound residue, and a hydrogen atom of a benzene ring represents an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, or a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, or a sulfamoyl group. Group, carboxyl group, nitroso group, amino group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanato group,
It may be substituted by a mercapto group, a sulfo group or a halogen atom, and R may have a substituent. ) 3. A urea represented by the following formula (e) or (f), wherein the total number of urethane groups and urea groups is 3 or more and 10 or less, and the molecular weight is 5000 or less. Urethane compounds. Embedded image (Wherein, R represents an aliphatic compound residue, Y represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, and α ₁ has a valence of 2 or more different from Y. Represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, n represents an integer of 2 or more, and each residue may have a substituent.) ] (Wherein, Z ₁ and Y each independently represent an aromatic compound residue or a heterocyclic compound residue, β ₁ represents an aliphatic compound residue having a valence of 2 or more, and n represents 2 It represents the above integer, and each residue may have a substituent.) 4. A urea urethane compound represented by the following formula (g) or (h): Embedded image (Wherein the hydrogen atom of the benzene ring is an aromatic compound residue or an aliphatic compound residue or a heterocyclic compound residue or a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group , An oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanato group, a mercapto group, a sulfo group or a halogen atom, and β ₁ is an aliphatic compound residue having a valence of 2 or more. And n represents an integer of 2 or more, and each residue may have a substituent.) (Wherein, R independently represents an aliphatic compound residue, and the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue; Each residue may have a substituent, γ
_{1 -SO 2 -, - O -,} - (S) n -, - (CH 2)
_n- , -CO-, -CONH-, -NH-, -CH (C
OOR ₁ ) —, —C (CF ₃ ) ₂ —, —CR ₂ R ₃ —, and one selected from the group consisting of groups represented by formula (a): Or the case where none is present, wherein R ₁ , R ₂ and R ₃ each represent an alkyl group, and n is 1 or 2. ) 5. A urea urethane composition comprising a urea urethane compound and a diluent. 6. The urea urethane composition according to claim 5, wherein the diluent according to claim 5 is a urea compound and / or a urethane compound. 7. The urea urethane composition according to claim 5, wherein the diluent according to claim 5 is a compound obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound. 8. A urea urethane composition obtained by reacting a polyisocyanate compound with a hydroxy compound and an amino compound, wherein at least one urea group and at least one urethane group are present in the molecular structure in a total of 2 to 10 Have
A urea urethane composition comprising 50% by weight or more of a urea urethane compound having a molecular weight of 5,000 or less. 9. The urea urethane composition according to claim 8, wherein the hydroxy compound is a phenol compound. 10. The urea urethane composition according to claim 8, wherein the hydroxy compound is an alcohol compound. 11. The urea urethane composition according to claim 8, wherein the amino compound is an aromatic amino compound. 12. The urea urethane composition according to claim 8, wherein the polyisocyanate compound is an aromatic polyisocyanate compound. 13. A polyisocyanate compound and a hydroxy compound, wherein the ratio of the number of moles of the polyisocyanate compound / the number of hydroxyl equivalents of the hydroxy compound is 100/1 to 1/2.
After forming a urethane group from a part of the isocyanate group of the polyisocyanate compound,
A method for producing a urea urethane composition, comprising adding an amino compound and reacting the remaining isocyanate group of the polyisocyanate compound with the amino compound to form a urea group. 14. The polyisocyanate compound is reacted with the polyisocyanate compound under the condition that the molar ratio of the polyisocyanate compound / the amino group equivalent number of the amino compound is 100/1 to 1/2. After forming a urea group from a part of the isocyanate group of the compound, a hydroxy compound is added, and the remaining isocyanate group of the polyisocyanate compound is reacted with the hydroxy compound to form a urethane group. A method for producing a urethane composition. 15. The method for producing a urea urethane composition according to claim 13, wherein the reaction for forming a urethane group and the reaction for forming a urea group are performed continuously. 16. Urea by reacting a polyisocyanate adduct obtained by reacting a polyisocyanate compound with a hydroxy compound and an amino compound at an isocyanato group / amino group equivalent ratio of 2/1 to 1/100. A method for producing a urea urethane composition in which an unreacted amino compound is removed after forming a group. 17. A urethane group obtained by reacting a polyisocyanate adduct obtained by reacting a polyisocyanate compound with an amino compound with a hydroxy compound at an isocyanate group / hydroxyl equivalent ratio of 2/1 to 1/100. A method for producing a urea urethane composition in which unreacted hydroxy compound is removed after the formation. 18. A reaction for forming a urethane group and / or
Alternatively, the reaction for forming a urea group is performed without a solvent, or the reaction for forming a urethane group and the reaction for forming a urea group are performed using the same solvent. A method for producing a urea urethane composition. 19. A reaction for forming a urethane group and / or
Alternatively, the reaction for forming a urea group is performed at a temperature of 0 to 300.
The method for producing a urea urethane composition according to any one of claims 13 to 18, which is carried out at a temperature of 0 ° C. 20. A reaction for forming a urethane group and / or
20. The method for producing a urea urethane composition according to claim 13, wherein the reaction for forming a urea group is performed in the presence of a catalyst. 21. A reaction for forming a urethane group and / or
21. The method for producing a urea urethane composition according to claim 13, wherein the reaction for forming a urea group is performed using a solvent having a solubility parameter value (δ) of 7 to 15. 22. The solubility parameter value (δ) is 7 to
The method for producing a urea urethane composition according to claim 21, wherein the reaction is carried out using the solvent of 8.8. 23. The method for producing a ureaurethane composition according to claim 22, wherein the reaction is carried out using a solvent having a solubility parameter value (δ) of 8.9 to 21 in combination. 24. A color former containing a color developer containing a urea urethane compound. 25. A developer containing a urea urethane compound,
And a color former containing a colorless or pale color dye precursor. 26. The color former according to claim 25, wherein the colorless or pale color dye precursor is a leuco dye. 27. The urea urethane compound according to any one of claims 1 to 4, the urea urethane composition according to any one of claims 5 to 12, or the color developing agent,
The color former according to any one of claims 24 to 26, which is a composition produced by the production method according to any one of claims 3 to 23. 28. The leuco dye is at least one selected from a triarylmethane leuco dye, a fluoran leuco dye, a fluorene leuco dye, and a diphenylmethane leuco dye.
28. The color former according to any one of claims 27 to 27. 29. The color former according to claim 26, wherein the leuco dye is a compound represented by the following formula (i-1). Embedded image (Here, Y ₂ and Y ₃ both represent an alkyl group or an alkoxyalkyl group, Y ₄ represents a hydrogen atom, an alkyl group, or an alkoxy group. Further, Y ₅ and Y ₆ represent a hydrogen atom, a halogen atom, Represents an alkyl group or an alkoxy group.) 30. The color former according to claim 26, wherein the leuco dye is a compound represented by the following formula (i-2). Embedded image (Here, P ₂ and P ₃ both represent an alkyl group or an alkoxyalkyl group, and at least one of P ₂ and P ₃ is a group having 5 or more carbon atoms. P ₄ is a hydrogen atom, an alkyl group And P ₅ and P ₆ represent a hydrogen atom, a halogen atom, an alkyl group, a halogen-substituted alkyl group or an alkoxy group.) 31. The color former according to claim 26, wherein the leuco dye is a compound represented by the following formula (i-3). Embedded image (Here, Q ₂ and Q ₃ both represent an alkyl group or an alkoxyalkyl group, Q ₄ represents a hydrogen atom, an alkyl group, or an alkoxy group. Q ₅ and Q ₆ represent a hydrogen atom or a halogen atom. , An alkyl group, a halogen-substituted alkyl group or an alkoxy group, and at least one of Q ₅ and Q ₆ is a halogen atom, an alkyl group or a halogen-substituted alkyl group.) 32. A leuco dye represented by the following formula (j):
28. Any of claims 26 to 27, which is a compound
A color former according to any one of the preceding claims. Embedded image[Where R_TwoAnd R_ThreeIs given by equation (k) or equation (l)
Shows any of the groups shown. Embedded image(Where R₁₁~ R₁₅Is a hydrogen atom, a halogen atom, C
₁~ C₈An alkyl group of C ₁~ C₈An alkoxy group, -NR
₁₆R₁₇Is shown. R₁₆, R₁₇Is an alkyl having 1 to 8 carbons
Group. )(Where R₁₈, R₁₉Is a hydrogen atom, and C 1-8
It represents a rualkyl group or a phenyl group. ) Also, R₇~ R_TenIs
A hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms,
An alkoxy group having 1 to 8 carbon atoms, -NR₂₀R_{twenty one}Is shown.
R₂₀, R_{twenty one}Is an alkyl group having 1 to 8 carbon atoms. ] 33. The color former according to claim 24, wherein the urea urethane compound developer has a melting point of 40 ° C. or more and 500 ° C. or less. 34. The method according to claim 24, wherein the urea urethane compound developer contains any one selected from the following general formulas (V) and (VI). Color former. Embedded image (Wherein, the hydrogen atom of the benzene ring is an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanato group. , A mercapto group, a sulfo group, a sulfamoyl group or a halogen atom, and each residue may have a substituent, and γ is -SO _2- , -O-,-(S ) _N −,
— (CH ₂ ) _n —, —CO—, —CONH— and formula (a)
One selected from the group consisting of any of the groups represented by: Or n is absent, and n is 1 or 2. ),
And (Wherein, the hydrogen atom of the benzene ring is an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, and an amino group. , Oxyamino group, nitroamino group, hydrazino group, ureido group,
It may be substituted with an isocyanato group, a mercapto group, a sulfo group or a halogen atom, and each residue may have a substituent, and δ is -SO _2- , -O-,-
(S) _n -,-(CH ₂ ) _n- , -CO-, -CONH
-, - NH -, - CH (COOR 1) -, - C (CF 3)
₂ - and -CR ₂ R ₃ - one selected from the group consisting of or indicates the absence, R _1, R ₂ and R ₃ each represents an alkyl group, n is 1 or 2. ) 35. The method according to claim 24, wherein the urea urethane compound developer contains any one selected from the following structural formulas (XX) and (XXI). Color former. Embedded image Embedded image 36. The color former according to claim 24, further comprising a heat-fusible substance. 37. The heat-fusible substance is β-naphthylbenzyl ether, p-benzylbiphenyl, 1,2-di (m
-Methylphenoxy) ethane, oxalic acid di-p-methylbenzyl ester, 1,2-diphenoxymethylbenzene, metaterphenyl, and stearamide. Item 36. The color former according to Item 36. 38. The heat-fusible substance has the following structural formula (XVI)
37. The color former according to claim 36, which is represented by II). Embedded image (Wherein, Y is _{-SO 2 -, - (S)} n -, - O -, - CO
_{-, - CH 2 -, -} CH (C 6 H 5) -, - C (CH 3) 2
-, - COCO -, - CO 3 -, - COCH 2 CO -, -
_{COOCH 2 -, - CONH -,} - OCH 2 -, - NH-
Indicates one of n is 1 or 2. The hydrogen atom of the benzene ring includes a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanato group, an isothiocyanato group, a mercapto group, a sulfamoyl group, a sulfone group, an amino group, an aromatic compound residue, and an aliphatic compound. It may be substituted by a residue or a heterocyclic compound residue. ) 39. The heat-fusible substance has the following structural formula (XI)
The color former according to claim 38, which is represented by X). Embedded image (The hydrogen atom of the benzene ring in the formula is a halogen atom, hydroxyl group, nitro group, nitroso group, nitrile group, isocyanato group, isothiocyanato group, mercapto group, sulfamoyl group, sulfone group, amino group, aromatic compound residue, fatty acid May be substituted with a group compound residue or a heterocyclic compound residue.) 40. The color former according to claim 24, further comprising an isocyanate compound. 41. The color former according to claim 24, further comprising an isocyanate compound and an imino compound. 42. The color former according to claim 24, further comprising an amino compound. 43. The color former according to claim 24, wherein the color developer further comprises an acidic color developer. 44. An acidic developer comprising 2,2-bis (4-hydroxyphenyl) propane, 4-isopropyloxyphenyl-4′-hydroxyphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone,
2,4'-dihydroxydiphenyl sulfone, 4,4
Any one selected from '-[oxybis (ethyleneoxy-p-phenylenesulfonyl)] diphenol
The color former according to claim 43, wherein the number is at least one. 45. The method according to claim 2, further comprising a fluorescent dye.
45. The color former according to any one of 4-44. 46. The color former according to claim 24, further comprising a preservative. 47. The urea urethane compound according to any one of claims 1 to 4, or the urea urethane composition according to any one of claims 5 to 12, or 24 to 46.
A recording material comprising a support and a color-forming layer containing the color-forming agent according to any one of the above. 48. The recording material according to claim 47, wherein a protective layer for the coloring layer is provided on the coloring layer. 49. The recording material according to claim 48, wherein the protective layer contains a water-soluble polymer. 50. The recording material according to claim 48, wherein the protective layer contains an inorganic pigment and / or an organic pigment. 51. The recording material according to claim 48, wherein the protective layer contains a lubricant. 52. The recording material according to claim 47, wherein an intermediate layer is provided on the support, and a coloring layer is provided on the intermediate layer. 53. The recording material according to claim 52, wherein the intermediate layer contains a water-soluble polymer. 54. The recording material according to claim 52, wherein the intermediate layer contains an inorganic pigment and / or an organic pigment. 55. A back surface of the support provided with the color-forming layer,
The recording material according to claim 47, further comprising a backcoat layer. 56. The recording material according to claim 55, wherein the back coat layer contains a water-soluble polymer. 57. The back coat layer contains an inorganic pigment and / or an organic pigment.
6. The recording material according to any one of 6. 58. The method according to claim 47, wherein at least one selected from a water-soluble polymer and an anionic surfactant is used as a dispersant for the urea urethane compound.
58. The recording material according to any one of -57. 59. A dispersing agent for a urea urethane compound, which includes polyvinyl alcohol, modified polyvinyl alcohol, methylcellulose, hydroxypropylmethylcellulose, condensed sodium naphthalenesulfonate, ammonium polycarboxylate, a water-soluble low molecular weight copolymer and sodium 2-ethylhexylsulfosuccinate. 58. A method using at least one selected from the group consisting of:
The recording material according to any one of the above. 60. The method according to claim 47, wherein at least one selected from a water-soluble polymer, a nonionic surfactant and an anionic surfactant is used as a dispersant for the dye precursor. 60. The recording material according to any one of items 59. 61. As the dispersant for the dye precursor, any one or more selected from methyl cellulose, hydroxypropyl methyl cellulose, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether sulfate, and sodium 2-ethylhexyl sulfosuccinate are used. The recording material according to any one of claims 47 to 59, wherein: 62. The recording material according to claim 47, wherein the recording material is a thermosensitive recording material. 63. The heat-sensitive recording material according to claim 62, wherein the urea urethane compound has an average particle size of 0.05 μm or more and 5 μm or less. 64. The heat-sensitive recording material according to claim 62, wherein the liquid temperature at the time of grinding the urea urethane compound is 60 ° C. or less. 65. The heat-sensitive recording material according to claim 62, wherein the pH at the time of grinding the urea urethane compound is 5 to 10. 66. The method according to claim 62, wherein at least one selected from a water-soluble polymer and an anionic surfactant is used as a dispersant for the heat-fusible substance. The heat-sensitive recording material as described. 67. Polyvinyl alcohol, modified polyvinyl alcohol, methylcellulose, hydroxypropylmethylcellulose, condensed sodium naphthalenesulfonate, ammonium polycarboxylate, water-soluble low molecular weight copolymer and 2-ethylhexyl sulfosuccinic acid as a dispersant for a heat-fusible substance The heat-sensitive recording material according to any one of claims 62 to 65, wherein at least one selected from soda is used. 68. The urea urethane compound and the heat-fusible substance are pulverized at the same time.
7. The heat-sensitive recording material according to any one of 7. 69. The heat-sensitive recording material according to claim 62, wherein the surface of the support on which the heat-sensitive recording layer of the heat-sensitive recording material is coated has a pH of 3 to 9. 70. The heat-sensitive material according to claim 62, wherein the heat-sensitive coating solution for forming the heat-sensitive recording layer of the heat-sensitive recording material is coated on the support at a pH of 5 to 12. Manufacturing method of recording material. 71. The recording material according to claim 47, wherein the recording material is a thermosensitive magnetic recording material. 72. The method according to claim 71, wherein a heat-sensitive recording layer containing a urea urethane compound developer is provided on one surface of the support, and a magnetic recording layer is provided on the other surface. Thermosensitive magnetic recording material. 73. A ticket which is the thermosensitive magnetic recording material according to claim 71. 74. A ticket ticket which is the thermosensitive magnetic recording material according to claim 71. 75. The recording material according to claim 47, wherein the recording material is a label for thermal recording. 76. The thermosensitive recording medium according to claim 75, wherein a thermosensitive recording layer containing a urea urethane compound developer is provided on one surface of the support, and an adhesive layer is provided on the other surface. Label for recording. 77. A heat-sensitive recording label according to claim 76, wherein a back coat layer is provided between the pressure-sensitive adhesive layer and the support. 78. A heat-sensitive recording label according to any one of claims 76 to 77, wherein an intermediate layer is provided between the heat-sensitive recording layer and the support. 79. A label for thermal recording, wherein a protective layer is provided on the thermal recording layer of the label for thermal recording according to any one of claims 76 to 78. 80. The recording material according to claim 47, wherein the recording material is a multicolor heat-sensitive recording material. 81. The multicolor heat-sensitive recording material according to claim 80, wherein at least two heat-sensitive recording layers are provided on one surface of the support, and at least one of said heat-sensitive recording layers has a urea urethane compound developer. A multicolor heat-sensitive recording material comprising: 82. The multicolor heat-sensitive recording material according to claim 81, wherein an intermediate layer is provided between the heat-sensitive recording layers. 83. On one surface of a support, two heat-sensitive recording layers each having a different coloring temperature and a different color tone are formed by lamination, and the upper and lower heat-sensitive recording layers are provided with a color-reducing agent or a reversible colorant. 1. A multicolor heat-sensitive recording material comprising a color developer and a urea urethane compound developer in a lower heat-sensitive recording layer. 84. The two heat-sensitive recording layers, wherein the upper layer is a low-temperature coloring layer that develops color at low temperature and decolorizes at high temperature, and the lower layer is a high-temperature coloring layer that develops color at high temperature.
2. The multicolor heat-sensitive recording material described in 1. above. 85. An article for laser marking, comprising a heat-sensitive recording layer containing a urea urethane compound developer on the surface of the article. 86. An article for laser marking, comprising a heat-sensitive recording layer containing a colorless or pale color dye precursor, a urea urethane compound developer, and a recording sensitivity improver on the surface of the article. 87. A glass transition point of 20 on the heat-sensitive recording layer
87. The article for laser marking according to any one of claims 85 to 86, further comprising a protective layer containing an aqueous binder at a temperature of from -80C. 88. The article for laser marking according to claim 86, wherein the recording sensitivity improver is at least one selected from aluminum hydroxide, white mica, wollastonite, and kaolin. 89. The article for laser marking according to claim 85, wherein the article for laser marking is a label, a packaging material, and a container. 90. A method for producing an article for laser marking, comprising applying a color-forming marking agent containing a urea urethane compound developer to a base material and drying. 91. A laser marking method comprising applying a colorless or pale-colored dye precursor, a urea urethane compound color developer, and a recording sensitivity improver to a base material and drying the color marking agent. Article manufacturing method. 92. A method for marking an article, comprising irradiating the heat-sensitive recording layer of the article for laser marking according to claim 85 with a laser beam. 93. A color-forming marking agent comprising a urea urethane compound color developer. 94. A color-forming marking agent comprising a colorless or pale-colored dye precursor, a urea urethane compound developer, and a recording sensitivity improver.