JP2001315441A - Color former and recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color former, which is excellent in developed color density and image preservability, a recording material using thereof, especially a heat sensitive recording material. SOLUTION: This color former includes a developer containing a specified urea urethane compound, which includes each one or more aliphatic urethane group and urea group, totaling 2 to 10 groups in a molecular construction, and a colorless or light-colored dye precursor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel color former using a specific 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 heat-sensitive 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 composed of a two-component color forming system of a colorless or pale-colored dye precursor and a color developing agent that forms a color in contact with the dye precursor has been known for a long time, and has been widely applied to recording materials. ing. 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.

Until now, pressure-sensitive recording materials using pressure energy have been used very much like 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 microcapsules are composed of an upper paper coated on a support and a lower paper coated with a developer layer containing a developer on another support. The microcapsule-coated surface and the developer-coated surface face each other. Then, by applying a pen pressure or a pressing pressure, the microcapsules are broken, and the inclusions containing the dye precursor are released. This is transferred to the color developer layer and comes into contact with the color developer, thereby producing a color-forming reaction, thereby obtaining image recording.

[0004] In recent years, for example, in various information devices such as facsimile machines, printers, recorders, and the like, a heat-sensitive recording system in which recording is performed by using thermal energy has been widely used. These heat-sensitive recording materials have many excellent properties such as high whiteness, good appearance and feel close to plain paper, good recording suitability such as color sensitivity, and the like. It has advantages such as maintenance-free and no noise generation, and its use has been expanded to a wide range of fields such as measurement recorders, facsimile machines, printers, computer terminals, labels, and automatic ticket vending machines such as tickets. The mainstream of these recording methods is to use a recording material in which a color-forming layer containing a two-component color-forming agent is provided on a support, and to apply heat as recording energy thereto using a heat-sensitive head, a hot stamp, a laser beam, or the like. In this method, heat-sensitive agent components are brought into contact with each other on a recording material to perform color recording. Among them, many use colorless or light-colored electron-donating dye precursors (particularly leuco dyes) and acidic developers such as phenolic compounds as color formers. Recording materials using these leuco dyes include, for example, heat-sensitive paper using crystal violet lactone and 4,4'-isopropylidenediphenol (bisphenol A) as heat-sensitive agents (see US Pat. No. 3,539,375).
And so on.

As the dye precursor and the color developer used for these, an electron donating compound and an electron accepting compound are mainly used, respectively. This is because the reactivity of the dye precursor, which is the electron-donating compound, is high, and by contact with the developer, which is the electron-accepting compound, a color-developed image with a high density can be obtained instantaneously, This is because they have excellent characteristics such as obtaining a close appearance and obtaining various color hues such as red, orange, yellow, green, blue, and black. However, on the other hand, the obtained color-developed image has poor chemical resistance, so that it comes in contact with a plasticizer contained in a plastic sheet or an eraser or a chemical contained in food or cosmetics, and the record is easily lost, or , Due to the poor light resistance of the recorded part, the record fades or disappears in a relatively short exposure to sunlight,
There is a disadvantage that the storage stability of the recording is inferior. Due to this disadvantage, the use of the recording is under certain restrictions at present, and improvement thereof is strongly desired.

In recent years, non-phenolic color developers which are not phenolic compounds represented by bisphenol A have been demanded. As a recording material capable of obtaining a recorded image having good storability in response to such demands, for example, JP-A-59-11587 and U.S. Pat.
No. 93 discloses a recording material comprising a combination of a color former comprising an aromatic isocyanate compound and an imino compound.

[0007] In this publication, various recording materials are exemplified by contacting and reacting two kinds of coloring agents by applying recording energy such as heat, pressure, light and the like. In addition, it is described that various colors such as red, orange, yellow, brown, and brown can be developed by appropriately selecting a coloring agent. However, while a recording material that is widely used at present is particularly required to have a black color, the publication cannot obtain the knowledge. JP-A-8-2111 and JP-A-8-2112 disclose a color-forming layer containing a colorless or pale color dye precursor and a urea compound as examples of a heat-sensitive recording material using a non-phenol type developer. A heat-sensitive recording medium is disclosed, but the color density is low and the preservability is insufficient.

Further, as a colorless or pale-colored dye precursor developer, JP-A-9-99640 discloses a sulfonylurea group in which a nitrogen atom at one end of a urea group is bonded to a sulfur atom of a sulfonyl group. There is an example of a compound having a urethane group as one of the divalent groups selected for allowing a straight-chain alkyl group having 11 or more carbon atoms to be present in the same molecule. JP-A-9-109551 discloses a compound having a urethane group. As an example of the combination of the valent groups, there is a carboxylic acid compound having a urethane group in which an oxygen atom of a urethane group is directly bonded to a carbon atom of a benzene ring, and a carboxylic acid compound having a urea group. Nor was it practical.

[0009]

SUMMARY OF THE INVENTION The present invention relates to a color forming agent which is excellent in solvent resistance, hydrolysis resistance, heat resistance and chemical and physical stability by using a specific urea urethane compound. Another object of the present invention is to provide a novel color former excellent in image storability and color density and a recording material using the same, particularly a heat-sensitive recording material. further,
The present invention relates to a novel color former having a specific urea urethane compound and a dye precursor added with various additives to improve the performance, and a recording material using the same.

[0010]

Means for Solving the Problems As a result of intensive synthesis studies of various color former compounds, the present inventors have found that a specific urea urethane compound exhibits surprisingly excellent performance in combination with a dye precursor. The present invention has been completed. That is, the present invention is as follows. A first aspect of the present invention is that, in a molecular structure, an aliphatic urethane group represented by the formula (I):

[0011]

Embedded image

(Wherein R ₁ and R ₂ each independently represent hydrogen, an aliphatic compound residue, a heterocyclic compound residue or an aromatic compound residue, and R ₁ and R ₂ are And R ₁ and R ₂ may combine to form an alicyclic structure.) Having a urea group represented by the formula (II),

[0013]

Embedded image

The nitrogen atoms at both ends of the urea group are directly bonded to carbon atoms of an aliphatic compound residue, a heterocyclic compound residue or an aromatic compound residue, and the total number of aliphatic urethane groups and urea groups is A developer containing a urea urethane compound having a molecular weight of 2 or more and 10 or less and a molecular weight of 5000 or less, and a color former containing a colorless or pale color dye precursor. A second aspect of the invention is the color former according to the first aspect, wherein the urea group is an aromatic urea group represented by the formula (III).

[0015]

Embedded image

(Wherein the hydrogen atom of the benzene ring may be substituted by an aliphatic compound residue, a heterocyclic compound residue or an aromatic compound residue, and each residue has a substituent. A third aspect of the present invention is that the urea urethane compound is represented by the following formula (I)
The coloring agent according to the first aspect of the invention, which is represented by V).

[0017]

Embedded image

(Wherein, R represents an aliphatic compound residue, and 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. Group, sulfamoyl group,
It may be substituted by 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 R has a substituent. May be. A fourth aspect of the present invention is the color former according to the first aspect, wherein the urea urethane compound is represented by the following formula (V).

[0019]

Embedded image

(Wherein R represents an aliphatic compound residue;
Represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue; α represents an aromatic compound residue, a heterocyclic compound residue, or 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. A fifth aspect of the present invention is that the urea urethane compound is represented by the following formula (VI):
The coloring agent according to the first aspect of the invention, which is represented by

[0021]

Embedded image

(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. And each residue may have a substituent, and γ 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]

Embedded image

Or R ₁ , R ₂
And R ₃ each represents an alkyl group, and n is 1 or 2. A sixth aspect of the present invention is that the urea urethane compound is represented by the following formula (VI)
The color former according to the first aspect of the present invention, which is represented by I).

[0025]

Embedded image

(Wherein, Z and Y each independently represent an aromatic compound residue or a heterocyclic compound residue, β represents an aliphatic compound residue having a valence of 2 or more, and n represents And represents an integer of 2 or more, and each residue may have a substituent.) In a seventh aspect of the present invention, a ureaurethane compound is represented by the following formula (VII):
The color former according to the first aspect of the present invention, which is represented by I).

[0027]

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 ,
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 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. )

An eighth aspect of the invention is the color former according to any one of the first to seventh aspects of the invention, further comprising a sensitizer. A ninth aspect of the invention is the color former according to any one of the first to eighth aspects of the invention, further comprising an isocyanate compound. First of the invention
0 is the color former according to any one of the first to ninth aspects of the invention, which further contains an isocyanate compound and an imino compound. An eleventh aspect of the invention is the color former according to any one of the first to tenth aspects of the invention, further comprising an amino compound. A twelfth aspect of the invention is the first to first aspects of the invention further containing an acidic developer.
2. The color former according to any one of 1. The thirteenth aspect of the invention is:
A recording material comprising a support and a coloring layer containing the coloring agent according to any one of the first to twelfth aspects of the invention. A fourteenth aspect of the present invention is the thirteenth aspect of the invention, wherein the recording material is a thermosensitive recording material.
Recording material.

The urea urethane compound as a developer used in the present invention has an aliphatic urethane group in which an aliphatic carbon atom is bonded to an oxygen atom of a urethane group in one molecule and a specific bond at both ends. Having both urea groups. By using such a urea urethane compound developer (a developer containing a urea urethane compound), a color developer and a heat-sensitive recording material having excellent stability and color developing ability can be obtained. It is desirable that the aliphatic urethane group and the urea group in the color developer exist in close proximity. It is preferable that the aliphatic urethane group and the urea group are adjacent to each other via at least one aromatic compound residue, heterocyclic compound residue, aliphatic compound residue, or the like (hereinafter, such a structural part is referred to as urea group). Urethane structure). Preferably, only one compound residue is present between the aliphatic urethane group and the urea group, and more preferably, the compound residue is an aromatic ring. The bond between the aliphatic urethane group and the compound residue may be the bond between the nitrogen atom of the aliphatic urethane group and the compound residue, or the bond between the carbon atom of the aliphatic urethane group and the compound residue. The former is preferred from the viewpoint of ease of manufacture. Although the aliphatic urethane group and the urea group may be separated to some extent, the molecular weight of one molecule is 5,000.
It must be located within the molecule so as to be within.

At least one such urea urethane structural portion may be present in one molecule, but preferably two or more. More preferably, the number is three or more. The aliphatic urethane group is preferably of the formula (I), wherein an aliphatic carbon atom is bonded to an oxygen atom of the urethane group. By having such a group, the physical and chemical stability of the color developer, particularly the thermal stability, is enhanced. In addition, a relatively inexpensive material can be used. 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. On the other hand, the basic performance required for the color developer such as color development and storage stability is equivalent to the performance obtained when an aromatic carbon atom is bonded to an oxygen atom of a urethane group.

The nitrogen atoms at both ends of the urea group are directly bonded to carbon atoms of an aliphatic compound residue, an alicyclic compound residue, a heterocyclic compound residue, or an aromatic compound residue. Thereby, a color former excellent in color developing ability and storage stability can be obtained. Such a urea urethane structure, a urea urethane compound present in one molecule, has good solvent resistance, hydrolysis resistance, heat resistance, excellent chemical and physical stability, and is a colorless or pale color dye precursor. The coloring agent containing both of them and the recording material using the same have a high coloring density and excellent storage stability.

The mechanism by which the urea urethane compound according to the present invention exhibits an excellent color developing effect is unknown, but the aliphatic urethane group present in the same molecule and the nitrogen atom at both ends are an aliphatic compound residue or a heterocyclic ring. It is presumed to be due to the interaction with the urea group directly bonded to the carbon atom of the compound residue or the aromatic compound residue. One molecule of the urea urethane compound may have other urea groups or urethane groups in addition to the urea urethane structure. The number of aliphatic urethane groups and the total number of urea groups present in the molecular structure of the urea urethane compound is 2 or more, 10 or less, preferably 3 or more, and more preferably 4 or more. The ratio of the aliphatic urethane group to the urea group in one molecule of the urea urethane compound is preferably 1: 3 to 3: 1, and is preferably 1: 3.
2-2: 1 is more preferred, and 1: 1 is even more preferred.
The molecular weight of the urea urethane compound is 5,000 or less,
More preferably, it is 2000 or less. The urea urethane compound is a colorless or pale-colored compound which is usually a solid at room temperature.

The term "aliphatic" as used in the present invention includes an alicyclic compound. The aliphatic compound residue in the present invention is a group bonded by a carbon atom of an aliphatic hydrocarbon moiety in the residue, and the aromatic compound residue is a benzene ring or the like in the residue. And a heterocyclic compound residue is a group that is bonded by a carbon atom forming a heterocyclic ring in the residue. is there.

In preparing a recording material using the urea urethane compound according to the present invention, one kind of the urea urethane compound is used, but if necessary, two or more kinds can be used in combination. Further, a color developer other than the urea urethane compound color developer may be mixed. When the recording material is a heat-sensitive recording material, the melting point of the urea urethane compound as a developer is preferably from 40 ° C. to 500 ° C., and particularly preferably from 60 ° C. to 300 ° C.

The colorless or light-colored dye precursor used in the present invention is not particularly limited, but is preferably an electron-donating dye precursor, more preferably a leuco dye,
Particularly, a triarylmethane leuco dye, a fluoran leuco dye, a fluorene leuco dye, a diphenylmethane leuco dye, or the like is preferable. When constituting the color former of the present invention, a sensitizer, an isocyanate compound, an imino compound, an amino compound, an acidic developer and the like may be added in addition to the color developer and the dye precursor. The recording material of the present invention is one in which a color-forming layer is provided on any support using these color-forming agents.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail. The urea urethane compound according to the present invention refers to an aliphatic urethane group represented by the formula (I) in a molecular structure.

[0038]

Embedded image

(Wherein, R ₁ and R ₂ each independently represent hydrogen, an aliphatic compound residue, a heterocyclic compound residue or an aromatic compound residue, and R ₁ and R ₂ represent a substituent And R ₁ and R ₂ may combine to form an alicyclic structure.) And a urea group represented by the formula (II)

[0040]

Embedded image

Wherein nitrogen atoms at both ends of the urea group are directly bonded to carbon atoms of an aliphatic compound residue, a heterocyclic compound residue, or an aromatic compound residue, and the aliphatic urethane group and the urea group Is 2 or more and 10 or less, and the molecular weight is 5
000 or less. The urea group of the urea urethane compound according to the present invention has both ends directly bonded to carbon atoms of an aliphatic compound residue or a heterocyclic compound residue or an aromatic compound residue,
Preferably, both ends thereof are directly bonded to a carbon atom of a heterocyclic compound residue or an aromatic compound residue, and both ends thereof are more preferably directly bonded to a carbon atom of an aromatic compound residue. Is preferably an aromatic urea group represented by

[0042]

Embedded image

(Wherein, the hydrogen atom of the benzene ring may be substituted by an aliphatic compound residue, a heterocyclic compound residue, or an aromatic compound residue, and each residue has a substituent. The urea urethane compound according to the present invention may be
Formulas (IV), (V), (VI), (VII) and (VII)
The urea urethane compounds represented by I) are preferred.

[0044]

Embedded image

(In the formula, R represents an aliphatic compound residue, and 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. Group, sulfamoyl group,
It may be substituted by 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 R has a substituent. May be. )

[0046]

Embedded image

(Wherein R represents an aliphatic compound residue;
Represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue; α represents an aromatic compound residue, a heterocyclic compound residue, or 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. )

[0048]

Embedded image

(In the formula, each R independently represents an aliphatic compound residue, and 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, and γ 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),

[0050]

Embedded image

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

[0052]

Embedded image

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

[0054]

Embedded image

(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,
β 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. Of these ureaurethane compounds of the formulas (IV) to (VIII), more preferred are the compounds of the formulas (IV), (VI)
Compounds of formula (VIII), particularly preferred are compounds of formulas (VI) and (VIII).

The method for synthesizing a urea urethane compound according to the first aspect of the present invention is characterized in that an aliphatic urethane group and carbon atoms of an aliphatic compound residue, a heterocyclic compound residue, or an aromatic compound residue at both ends of the urea group. There is no particular limitation as long as it is a method capable of forming a directly bonded urea group, but a method of making an isocyanate compound with an alcohol compound and an amine compound is easy and preferable. That is, the urea urethane compound according to the first aspect of the present invention starts with an isocyanate having at least two or more isocyanate groups bonded to a carbon atom, and leaves at least one isocyanate group of the isocyanate other than the other isocyanate group. With an alcohol compound to form an aliphatic urethane group, and then react the remaining isocyanate group with an amine compound to form a urea group. Alternatively, an isocyanate group and an amine compound may be reacted to form a urea group, and then the remaining isocyanate group and an alcohol compound may be reacted to form an aliphatic urethane group.

Further, starting from an isocyanate having two isocyanate groups bonded to carbon atoms, one of the isocyanate groups is reacted with an alcohol compound to form an aliphatic urethane group, and then the remaining isocyanate group and amine A urea urethane compound having two aliphatic urethane groups and two urea groups in total can be obtained by reacting the compounds to form urea groups. Further, starting from an isocyanate having at least two or more isocyanate groups bonded to carbon atoms, an aliphatic urethane group is reacted by reacting an alcohol compound with another isocyanate group while leaving at least one isocyanate group of the isocyanate. Then, the remaining isocyanato groups of the two molecules of the urethane compound are reacted with each other with water to be bonded to each other, whereby a urea urethane compound having a total of at least three aliphatic urethane groups and urea groups can be obtained.

Further, for example, an isocyanate having at least two or more isocyanate groups bonded to a carbon atom is used as a starting material, and another isocyanate group is reacted with an alcohol compound while leaving at least one isocyanate group of the isocyanate. Forming an aliphatic urethane group,
Next, the remaining isocyanate group is reacted with an amine compound having two or more amino groups to form a urea group, and the remaining amino group is reacted with the isocyanate compound, whereby the total number of urea groups and urethane groups is reduced. At least three urea urethane compounds can be obtained.

Further, first, an isocyanate group and an amine compound are reacted to form a urea group, and then the remaining isocyanate group and an alcohol compound having two or more OH groups are reacted to form an aliphatic urethane group. Further, by reacting an isocyanate compound, a urea urethane compound having a total number of aliphatic urethane groups and urea groups of at least 3 can be obtained. At this time, an isocyanate compound having two or more isocyanate groups is used as the isocyanate to be reacted last, and an alcohol compound having the remaining isocyanate group and two or more OH groups or an amino compound having two or more amino groups is used. Can be obtained sequentially to obtain a urea urethane compound in which the total number of aliphatic urethane groups and urea groups is 3 to 10.

In these operations, in order to react only one of two or more groups in one molecule, a substance having two or more groups in one molecule is made a large excess, and the substance to be reacted with the group is added to this. It can be performed by a method of adding little by little.
When adding, it is desirable to stir the system well so that the additives are sufficiently dispersed immediately after the addition. The same applies to other urea urethane compounds exemplified in the present invention. It should be noted that any method can be used as long as a similar result can be obtained, and the method is not limited to this.

Hereinafter, the starting materials will be described in detail. These starting materials may be used alone or in combination of two or more. The starting material isocyanate is not particularly limited as long as it has 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, 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 such as toluene diisocyanate dimer N, N '(4,4
'-Dimethyl-3,3'-diphenyldiisocyanato)
Uretdione (trade name Death Module TT), trimer,
For example, 4,4 ', 4 "-trimethyl-3,3', 3 '
'-Triisocyanato-2,4,6-triphenylcyanurate and the like may be used. 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) Death module L, trade name Coronate L) or an amine adduct body may be used. 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.

Of these, an aromatic isocyanate having an isocyanato group bonded to a benzene ring is preferable, and 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 Death Module 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 preferred, and toluene diisocyanate is particularly preferred. Can be mentioned. Toluene diisocyanate is preferably 2,4-toluene diisocyanate, 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, but this is fine.

The alcohol compound which reacts with the isocyanate which is the starting material of the urea urethane compound to form an aliphatic urethane group may be any alcohol compound having an OH group bonded to a carbon atom of the aliphatic compound. For example, Solvent Handbook (published by Kodansha Scientific, 9th edition, 1989), p.
20, p772-817, for example, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-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, nonyl alcohol, isononyl alcohol, decanol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol , Aliphatic alcohols such as tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol and isostearyl alcohol; unsaturated aliphatics such as allyl alcohol, 2-methyl-2-propen-1-ol, crotyl alcohol and propargyl alcohol Alcohols,

Aliphatic alcohols to which aromatic compound residues such as benzyl alcohol and cinnamyl alcohol are bonded, and heterocyclic compound residues such as 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol and furfurylalcohol are exemplified. Linked fatty alcohols, 2
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 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 Diols such as 1,6-hexanediol, hexylene glycol, 1,9-nonanediol, neopentyl glycol, methylpentanediol, glycerin, castor oil, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, Aliphatic polyols such as α-methylglucoside, sorbitol, and souce rose, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, adipate poly 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 with ethylene oxide and alkylene oxides such as propylene oxide alone or in mixtures. Polyether polyol obtained by addition, 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,
Alkanolamines such as N, N, N ', N'-tetrakis (2-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,
Preferred are diols, aliphatic polyols, polyols having a molecular weight of 2000 or less, and alkanolamines. The amine compound which reacts with the isocyanate to form a urea group 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
-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, trimethyl bromide Phenyl ammonium, 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, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, p -N-propyl aminobenzoate, 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-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, 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,
Aromatic amines such as 1,4-diamino-anthraquinone, 1,4-diamino-2,3-dichloroanthraquinone, and further 3-amino-1,2,4-triazole,
-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 compound amines such as 5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine;

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 amine compounds, aromatic amines are preferable, and an aniline derivative having at least one amino group such as the following formula (IX) or (X) is particularly preferable.

[0072]

Embedded image

(In the formula, R ₁ and R ₂ each independently represent hydrogen, halogen, an alkyl group, an alkoxy group or an amino group.)

[0074]

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 each independently represent Represents an amino group or a group represented by the formula (b),

[0076]

Embedded image

Y ₁ is —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),

[0078]

Embedded image

[0096] Or, the case where no data exists is shown. R ₁ , R ₂
And R ₃ each represents an alkyl group, and n is 1 or 2. As the method for synthesizing the urea urethane compound according to the second aspect of the present invention, the isocyanate compound, the alcohol compound, and the amine compound are the same as the method described in detail in the description of the method for synthesizing the urea urethane compound according to the first aspect of the present invention. The method of making the urea group is easy and preferable, and the urea group has the following formula (III)
An isocyanate compound and an amine compound may be selected so as to be an aromatic urea group.

[0080]

Embedded image

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

That is, as the isocyanate which is the starting material of the urea urethane compound according to the second aspect of the present invention, any aromatic isocyanate having an isocyanate group bonded to a benzene ring may be used. For example, p-phenylenediate Isocyanate, 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) can be used, and toluene diisocyanate is particularly preferred. Can be mentioned. Toluene diisocyanate is preferably 2,4-toluene diisocyanate, 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, but this is fine.

Examples of the amine compound which forms an aromatic urea group by reacting with an aromatic isocyanate which is a starting material of the urea urethane compound according to the second aspect of the present invention include an aromatic amine having an amino group bonded to a benzene ring. Anything is acceptable, 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, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine,
Dianisidine, 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-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'-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'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 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'-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,
B 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, p-
Phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, 4,4'-diaminostilbene-2,2
'-Disulfonic acid, benzylethylaniline, 1,8-
And aromatic amines such as naphthalenediamine, sodium naphthionate, tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, and 1,4-diamino-2,3-dichloroanthraquinone. In particular, an aniline derivative having at least one amino group such as the following formula (IX) or (X) is preferable.

[0087]

Embedded image

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

[0089]

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 each independently represent Represents an amino group or a group represented by the formula (b),

[0091]

Embedded image

Y ₁ is —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),

[0093]

Embedded image

Or, it shows 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. )

The alcohol compound which reacts with the aromatic isocyanate to form an aliphatic urethane group may be any alcohol compound having an OH group bonded to a carbon atom of the aliphatic compound. Published by Kodansha Scientific, ninth printing,
1989), p. 327-420, p. 772-817, and, for example, methanol, ethanol, propanol, isopropanol, n
-Butanol, isobutanol, sec-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, nonyl alcohol, isononyl alcohol, decanol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, isostearyl alcohol, etc. Aliphatic alcohols, 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 bound,

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, and 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 Diols such as 1,6-hexanediol, hexylene glycol, 1,9-nonanediol, neopentyl glycol, methylpentanediol, glycerin, castor oil, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, Aliphatic polyols such as α-methylglucoside, sorbitol, and souce rose, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, adipate poly 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 ethylene oxide or alkylene oxide such as propylene oxide alone or in mixture. Polyether polyols such as polyether polyols obtained by addition, acrylic polyols, fluorinated polyols, polybutadiene polyols, polyhydroxy polyols, castor oil polyols, polymer polyols, halogen-containing polyols, polyols such as phosphorus-containing polyols, N , N-dialkylethanolamine, N, N-dialkylisopropanolamine, N-alkyldiethanolamine, N-A Kill diisopropanolamine, triethanolamine, triisopropanolamine, N, N, N', N'
Alkanolamines such as -tetrakis (2-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,
Preferred are diols, aliphatic polyols, polyols having a molecular weight of 2000 or less, and alkanolamines. The production method of the ureaurethane compound of the formula (IV) according to the third aspect of the present invention is not limited to a production method. For example, an alcohol compound of the following formula (XI), an isocyanate compound of the following formula (XII) and an amine of the following formula (XIII) The compound can be obtained, for example, by reacting the compound according to the following reaction formula (A) or (B).

[0099]

Embedded image

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

[0101]

Embedded image

(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. )

[0103]

Embedded image

(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.)

[0105]

Embedded image

[0106]

Embedded image

The ureaurethane compound of the formula (V) according to the fourth aspect of the present invention is not particularly limited in the production method, but may be, for example, a compound represented by the general formula (X)
It can be obtained by reacting an alcohol compound of I) with an isocyanate compound of the general formula (XIV) and an amine compound of the following general formula (XV), for example, according to the following reaction formula (C) or (D).

[0108]

Embedded image

(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.)

[0110]

Embedded image

(In the formula, α 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, and each residue is It may have a substituent.)

[0112]

Embedded image

[0113]

Embedded image

The ureaurethane compound of the formula (VI) according to the fifth aspect of the present invention is not particularly limited in the production method, but may be, for example, a compound represented by the following formula (X)
It can be obtained by reacting an amine compound of VI) with an isocyanate compound of formula (XII) and an alcohol compound of general formula (XI), for example, according to the following reaction formula (E) or (F).

[0115]

Embedded image

(Wherein the hydrogen atom of the benzene ring is
Compound residue or aliphatic compound residue or heterocyclic compound residue
Group, hydroxyl group, nitro group, carboxyl group, nitroso group,
Nitrile group, carbamoyl group, ureido group, isocyana
Group, mercapto group, sulfamoyl group or halogen atom
And each residue may be a substituent.
May be provided. γ is -SO_Two-, -O-,-
(S) n-,-(CH_Two) N-, -CO-, -CONH
-, -NH-, -CH (COOR₁)-, -C (CF_Three)
_Two-, -CR_TwoR_Three-Or any of the groups represented by formula (a)
One selected from the group consisting of

[0117]

Embedded image

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

[0119]

Embedded image

[0120]

Embedded image

The ureaurethane compound of the formula (VII) according to the sixth aspect of the present invention is not particularly limited in the production method, but includes, for example, an amine compound of the general formula (XVII), an isocyanate compound of the general formula (XIV) and the following general formula: It can be obtained by reacting the alcohol compound of (XVIII) according to, for example, the following reaction formula (G) or (H).

[0122]

Embedded image

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

[0124]

Embedded image

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

[0126]

Embedded image

[0127]

Embedded image

The ureaurethane compound of the formula (VIII) according to the seventh aspect of the present invention is not limited to the production method, but may be, for example, an alcohol compound of the formula (XVIII), an isocyanate compound of the formula (XII) and a compound of the formula (XIII) It can be obtained by reacting an amine compound according to, for example, the following reaction formula (i) or (J).

[0129]

Embedded image

[0130]

Embedded image

The compounds of formulas (XI) to (XVIII) which can be used when synthesizing the ureaurethane compounds represented by the above formulas (IV) to (VIII) will be described in further detail. In addition, the starting materials of these compounds exemplified below may be used alone or in combination of two or more.

As the alcohol compound represented by the general formula (XI), any alcohol compound having an OH group bonded to a carbon atom of an aliphatic compound may be used. For example, a solvent handbook (published by Kodansha Scientific, No. 9)
Printing, 1989), p. 327-420, p. 772-81
7, alcohols such as methanol, ethanol, propanol, isopropanol,
n-butanol, isobutanol, sec-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, nonyl alcohol,
Aliphatic alcohols such as 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 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;

Glycerin, castor oil, trimethylolpropane, trimethylolethane, hexanetriol,
Aliphatic polyols such as pentaerythritol, α-methylglucoside, sorbitol, and souce, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, adipate polyol,
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 alone or in mixtures The resulting polyether polyol, acrylic polyol, fluorinated polyol, polybutadiene polyol, polyhydroxy polyol, castor oil-based polyol, polymer polyol, halogen-containing polyol, polyols such as phosphorus-containing polyols, N, N-dialkylethanolamine,
N, N-dialkylisopropanolamine, N-alkyldiethanolamine, N-alkyldiisopropanolamine, triethanolamine, triisopropanolamine, N, N, N ', N'-tetrakis (2-
Hydroxyethyl) ethylenediamine, N, N, N
And alkanolamines such as', N'-tetrakis (2-hydroxypropyl) ethylenediamine.

Among the above alcohol compounds, monoalcohols having one OH group are preferable, and aliphatic alcohols and glycol ethers having 10 or less carbon atoms are more preferable. As the aromatic isocyanate compound of the formula (XII), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, o-phenylene diisocyanate Nart and the like. Of these, toluene diisocyanate is preferred, and 2,4-toluene diisocyanate is more preferred.

The aromatic amine compound of the formula (XIII) 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 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, oxyamino group, nitroamino group, hydrazino group, ureido group , An isocyanato group, a mercapto group, a sulfo group or a 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, carboxyl-substituted aniline p-aminobenzoic acid, hydroxyl-substituted aniline o-aminophenol, m-aminophenol, p-aminophenol, 2-amino-
4-chlorophenol, 2,3-xylidine, 2,4-
Xylidine, 3,4-xylidine, 2,6-xylidine, nitrile-substituted aniline 4-aminobenzonitrile, anthranilic acid, p-cresidine, halogen-substituted aniline 2,5-dichloroaniline, 2,6-dichloroaniline , 3,4-dichloroaniline, 3,5-
Dichloroaniline, 2,4,5-trichloroaniline,
o-chloroaniline, m-chloroaniline, p-chloroaniline, α-naphthylamine, aminoanthracene,
o-ethylaniline, methyl p-aminobenzoate, p-
Ethyl aminobenzoate, n-propyl p-aminobenzoate, -iso-propyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, p
-Benzyl 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-
Carbamoylanilines such as (2'-methyl-3'-chlorophenyl) carbamoyl] aniline and 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, -Acetylaminoaniline, 2-methoxy-4-
(N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2- (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, 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,

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- Amino-
Aromatic monoamines such as 3-bromo-5-nitrobenzonitrile, and substituents such as carboxyl, nitroso, oxyamino, nitroamino, hydrazino, ureido, isocyanato, mercapto, and sulfo groups Monoamines having 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, 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 ′
-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
Aromatic diamines such as -aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, and 3,3'-dichlorobenzidine. Of these, aromatic monoamines are preferably used, and aniline or an aniline derivative is more preferably used.

The isocyanate compound of the formula (XIV) is not particularly limited as long as it has two or more isocyanato 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 And cyclohexane diisocyanate.

A diisocyanate dimer such as N, N '(4,4) which is a dimer of toluene diisocyanate
'-Dimethyl-3,3'-diphenyldiisocyanato)
Uretdione (trade name Death Module TT), trimer,
For example, 4,4 ', 4 "-trimethyl-3,3', 3 '
'-Triisocyanato-2,4,6-triphenylcyanurate and the like may be used. Also, toluene diisocyanate,
Water adduct isocyanates such as diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4)
-Methylphenyl) urea or a polyol adduct, for example, trimethylolpropane adduct of toluene diisocyanate (trade name Desmodur L, trade name Coronate L) or an amine adduct. In addition, Japanese Patent Application Laid-Open
Among the isocyanate compounds and isocyanate adduct compounds described in US Pat. No. 7,767,757 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 isocyanate group bonded to a benzene ring is preferable, and 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 Death Module 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 preferred, and toluene diisocyanate is particularly preferred. Can be mentioned. Toluene diisocyanate is preferably 2,4-toluene diisocyanate, 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, but this is fine.

The amine compound represented by the general formula (XV) 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'-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,
and aromatic amines such as m-phenylenediamine and p-phenylenediamine. Further, among the above-mentioned amine compounds, an aniline derivative having at least two amino groups such as the following formula (X) is particularly preferable.

[0143]

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 each independently represent Represents an amino group or a group represented by the formula (b),

[0145]

Embedded image

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),

[0147]

Embedded image

[0148] 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 (XVI), 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′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone,
3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, , 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,
Examples include aromatic diamines such as 4'-bis (4-aminophenoxy) diphenyl, dianisidine, and 3,3'-dichlorobenzidine, and those in which γ is a sulfonyl group or a methylene group are preferable.

Examples of the amine compound represented by the general formula (XVII) 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-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,

Methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, p-aminobenzoate
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, 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'-diaminodiphenyl sulfone,

3,3′-diaminodiphenyl sulfone,
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-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, 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-diamino-2,3
Aromatic amines such as -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,
Heterocyclic compound amines such as 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine and the like, among which aromatic monoamines are preferably used.

The alcohol compound of the general formula (XVIII) 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, 1,2-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, hexylene glycol, 1,9- Diols such as nonanediol, neopentyl glycol and methylpentanediol,
Glycerin, castor oil, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, α-methylglucoside, sorbitol, aliphatic polyols such as sucrose,

Polyethylene glycol, polypropylene glycol, polytetramethylene glycol, adipate-based polyol, epoxy-modified polyol, polyetherester polyol, polycarbonate polyol,
Polycaprolactone diol, amine-modified polyol,
Polyether polyols, acrylic polyols, fluorinated polyols, polybutadiene polyols, polyhydroxy polyols obtained by adding a single or mixture of alkylene oxides such as ethylene oxide and propylene oxide to a single or mixture of polyhydric alcohols such as glycerin and propylene glycol, Castor oil-based polyols, polymer polyols, halogen-containing polyols, polyols such as phosphorus-containing polyols, N-alkyldiethanolamine, N-alkyldiisopropanolamine,
Triethanolamine, triisopropanolamine,
Alkanolamines such as N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine, and the like are preferable. Diols, aliphatic polyols, alkanolamines and polyols having a molecular weight of 2000 or less are used.

The urea urethane compound developer (a developer containing a urea urethane compound) according to the present invention preferably contains at least 50% by weight of a urea urethane compound.
More preferably, the content is 0% by weight or more, and even more preferably 70% by weight or more. By using such a urea urethane compound developer together with a colorless or pale color dye precursor, it can be used as a color former for 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.

Further, the content of the urea urethane compound in the urea urethane compound developer according to the present invention is preferably 50% by weight or more. Such a urea urethane compound developer 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. Therefore, excellent performance can be exhibited.
The urea urethane compound may be used alone or in a mixture of two or more kinds including isomers.

Further, a mixture of two or more urea urethane compounds containing isomers may be used for the purpose of improving color sensitivity and storage performance. On the other hand, in the urea urethane compound developer of the present invention, the urea urethane compound can be optionally diluted with a substance that does not inhibit the effects of the present invention. Examples of such a diluent include a heat-fusible substance, an acidic developer, an amine compound, an isocyanate compound, a urea compound, and a urethane compound. 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 or more, from the viewpoint of improving sensitivity. Also,
These diluents may be generated during the synthesis reaction of the urea urethane compound, but 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 urea group and at least one urethane group in the molecular structure and having a total of 2 to 10 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. In order to obtain the urea urethane compound according to the present invention, the desired product can be obtained by mixing and reacting the reactant with the isocyanate in an organic solvent or without a solvent, and then removing the crystals by filtration, crystallization, desolvation, etc. Can be The reactants may be used alone or in combination depending on the purpose. The solvent may be any solvent as long as it does not react with the isocyanate group and the functional group of the reactant. Examples thereof include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and chlorinated aliphatic hydrocarbons. Examples include hydrogen, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, and ketones. Particularly, methyl ethyl ketone, acetone, toluene 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.

As specific examples of the ureaurethane compound of the present invention, the following compounds can be exemplified. ((S
-1) to (S-70))

[0161]

Embedded image

[0162]

Embedded image

[0163]

Embedded image

[0164]

Embedded image

[0165]

Embedded image

[0166]

Embedded image

[0167]

Embedded image

[0168]

Embedded image

[0169]

Embedded image

[0170]

Embedded image

The following are representative examples of typical dye precursors that can be used in the present invention. (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-dimethylaminophenylbenzhydrylbenzyl ether, N-halophenylleucouramine, N-2,4,5-trichlorophenylleucouramine and the like. (3) Xanthene compounds rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-octylaminofluoran, 3-diethylamino-7 -Phenylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-6-chloro-7-methylfluoran, 3-diethylamino-7- (3,4-dichloroanilino) fluoran, 3-diethylamino- 7
-(2-chloroanilino) fluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3- (N
-Ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino-6 Methyl-7-phenethylfluoran, 3-diethylamino-7- (4-nitroanilino) fluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-propyl) amino-
6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-cyclohexyl) amino-6 Methyl-7-anilinofluoran, 3
-(N-ethyl-N-tetrahydrofuryl) amino-6
-Methyl-7-anilinofluoran 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.

Also, 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'-diethylaminophthalide), 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. These colorless or light-colored dye precursors can be used in combination of two or more as necessary.

The urea urethane compound developer is preferably used in an amount of 5 to 1,000 parts by weight, more preferably 20 to 5 parts by weight, based on 100 parts by weight of the colorless or pale color dye precursor.
00 parts by weight. When the amount of the urea urethane compound developer is 5 parts by weight or more, it is sufficient to form a color of the dye precursor, and the coloring density is high. When the amount of the urea urethane compound developer is 1,000 parts by weight or less, an excessive amount of the urea urethane compound developer hardly remains, which is economically advantageous and preferable.

The sensitivity can be improved by adding a heat-fusible substance as a sensitizer to the color former of the present invention. 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, stearamide, palmitamide, N-methylol stearamide, 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-di (m-methylphenoxy) ethane, 1-phenoxy-2- (4-chlorophenoxy) ethane, 1,4-butanediol phenyl ether, dimethyl terephthalate, metaterphenyl, dibenzyl oxalate And oxalic acid di-p-methylbenzyl ester, oxalic acid (p-chlorobenzyl) ester and the like. Furthermore, 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, 4,4'tetramethyldiaminodiphenylmethane, diphenyl carbonate, methyl 4-hydroxybenzoate, 4- (Benzyloxy) phenol, salicylanilide and the like may be used.

Of these, stearic acid amide, 4,
4'-dimethoxybenzophenone, 4,4'tetramethyldiaminodiphenylmethane, diphenyl carbonate, methyl 4-hydroxybenzoate, 4- (benzyloxy) phenol, salicylanilide, di-p-methylbenzyl oxalate, benzyl, diphenylsulfone Are preferable, and benzyl and diphenyl sulfone are more preferable.
The heat-fusible substance may be used alone or as a mixture of two or more kinds. To 300 parts by weight, preferably 2 to 300 parts by weight.
It is more preferable to use 0 to 250 parts by weight.

The storage stability 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 heterocyclic isocyanate compound of a room temperature solid, for example,
One or more of the following isocyanate compounds are used.

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, bilen-3,8-di Isocyanate, 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. is there.

These isocyanates may be used, if necessary, in the form of so-called block isocyanates, which are addition compounds with phenols, lactams, oximes and the like. Diisocyanate dimers, For example, it may be used in the form of 1-methylbenzene-2,4-diisocyanate dimer and trimer isocyanurate, or used as a polyisocyanate adducted with various polyols and the like. Is also possible.
Water adduct isocyanates such as 2,4-toluene diisocyanate and diphenylmethane diisocyanate;
Phenol adduct isocyanate, amine adduct isocyanate, and the like, and isocyanate compounds and isocyanate adduct compounds described in JP-A-10-76757 and JP-A-10-95171 may 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, based on 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 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. Among these, iminoisoindoline derivatives are particularly preferred, and 1,3-diimino-4,5,6,6
7-tetrachloroisoindoline, 3-imino-4,
5,6,7-tetrachloroisoindoline-1-one,
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, based on 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. Also, when 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 that 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, an aniline derivative having at least one amino group represented by the following formula (X) is particularly preferable.

[0184]

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 each independently represent Represents an amino group or a group represented by the formula (b),

[0186]

Embedded image

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),

[0188]

Embedded image

[0189] 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. The amino compound may be used singly or as a mixture of two or more kinds. In order to improve the print preservability in plasticizer resistance, the amino compound is added to 100 parts by weight of a colorless or pale color dye precursor. Preferably it is 500 parts by weight.
When the content of the amino compound is 1 part by weight or more with respect to the urea urethane compound, improvement in print preservability can be obtained. Also, 5
If it is used in an amount of not more than 00 parts by weight, 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 clear color former can be obtained. As the acidic developer when the color former of the present invention is used as a heat-sensitive recording material, generally used electron-accepting substances are used. Alternatively, a metal salt thereof, an N, N-diarylthiourea derivative, a sulfonylurea derivative and the like are preferable. 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, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, 4-hydroxy Phenyl-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.

The salicylic acid derivatives include 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. Examples of the sulfonylurea derivative include 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane and 4,4-bis (o-toluenesulfonylaminocarbonylamino) diphenylmethane 4,4-bis (p-toluenesulfonylaminocarbonyl) Amino) diphenyl sulfide, 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenyl ether, N- (p
Compounds containing one or more arylsulfonylaminoureido groups, such as-(toluenesulfonyl) -N'-phenylurea.

Further, in order to improve the background fog and the 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 coloring of the dye precursor is good and the coloring density is high. When the amount of the acidic developer is 500 parts by weight or less, the acidic developer hardly remains, which is economically advantageous and preferable.

When the color developing agent of the present invention is used as a pressure-sensitive recording material, the image density is improved by adding an acidic developer, and a clear color-developing pressure-sensitive recording material can be obtained. As the acid developer, an electron-accepting substance is also used. Inorganic compounds, 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, 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid, and their metals Salt and the like.

A recording material can be obtained by forming a color-forming layer on any 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, a urea urethane compound, a colorless or pale-colored dye precursor such as a leuco dye, a heat-fusible substance, or the like is coated on a support in the form of a dispersion together with other necessary components, and a heat-sensitive recording layer is formed. It is necessary to The dispersion can be 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 size of each dispersion is 0.1.
It is preferable to set the thickness to 1 to 10 μm, especially around 1 μm. In particular, when the urea urethane compound is wet-pulverized in an aqueous solvent, it is desirable to maintain the liquid temperature of the aqueous solvent at 50 ° C. or lower. 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 wear 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 which 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 for 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 heat-sensitive 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 composed of one layer or a plurality of layers may be provided on the heat-sensitive recording layer, or between the support and the heat-sensitive recording layer.
A layer or an intermediate layer composed of a plurality of layers may be provided. 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 1 to 15 g /
m ² is preferred.

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
No. 7, No. 3,418,250, and the like. 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. Alternatively, an upper paper obtained by dissolving in a solvent composed of a mixture and dispersing the same in a binder, or applying a dispersion liquid contained in microcapsules together with a binder or the like on a support, and a urea urethane compound (and Pressure-sensitive recording paper with the coated surfaces of the lower paper coated with a dispersion of an amino compound and / or a developer) or a dispersion of a urea urethane compound coated on one side and a dye precursor on the other side Pressure-sensitive recording paper with the middle paper coated with the body sandwiched between the upper paper and the lower paper, or the same A dispersion of the above urea urethane compound (and amino compound and / or color developer) and a dispersion containing the above dye precursor, or a multi-layer coated self-type, or a dye precursor, urea urethane compound (and Various forms such as a self-type in which any one of an amino compound and / or a developer is microencapsulated and mixed and applied are possible.

As the method for producing microcapsules, the coacervation method disclosed in US Pat.
9574, 42-446, 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,
96-5074, etc., the melting dispersion cooling method disclosed in U.S. 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 employed.

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 dissolved in a solvent and used or dispersed. In the case of a coloring system containing an amino compound and / or a color developing agent, they are used alone or in combination with a urea urethane compound and an amino compound and, if necessary, dissolved or dispersed in a solvent with a color developing agent. I just need.

In the above-mentioned 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, use a polybasic acid chloride in the oil phase, use a polyamine in the aqueous phase, use a polyamide film in the interface, use a polyhydroxy compound in the water phase, use a polyester film, and use the polyisocyanate in the oil phase. It is known to form a polyurethane film using a polyhydric alcohol or polyhydric phenol in an aqueous phase when a naat is used, and a polyurea film using a polyhydric amine in an aqueous phase. 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 microcapsule 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.
Preparation of the dispersion of the compound without microencapsulation
It can be obtained by finely 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. 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, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, Water solubility of acrylamide / acrylic ester copolymer, acrylamide / acrylic ester / methacrylic acid terpolymer, alkali salt of styrene / maleic anhydride copolymer, alkali salt of ethylene / maleic anhydride copolymer, etc. Binders and latex-based water-insoluble binders such as styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, and the like.

Further, the recording material according to the present invention may contain a hindered phenol compound or an ultraviolet absorber in the recording layer. For example, 1,1,3-tris (3 ′
-Cyclohexyl-4'hydroxyphenyl) butane,
1,1,3-tris (2-methyl-4-hydroxy-5-
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, tetra (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboate.

[0206]

The present invention will be described in more detail with reference to the following examples. The analysis of each substance and the evaluation of each physical property were performed by the following methods. <IR spectrum> FTIR-8100M manufactured by Shimadzu Corporation
Was measured by the diffuse reflection method. <Mass Spectra> Using a 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, and 300 g / cm ² from the top.
, And allowed to stand at 40 ° C. for 24 hours. After the standing, the densities of the printed portion and the unprinted portion (background) were visually evaluated. <Heat resistance> The heat-sensitive recording material was allowed to stand for 24 hours in an environment of 60 ° C. and 25% RH, and the fading density of the print was visually evaluated.

[0207]

Example 1 2,4-Toluene diisocyanate 27.
To 8 g, 111 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, and toluene was added for crystallization.The resulting white crystals were collected by filtration, washed with hexane. After drying overnight under vacuum, 5.4 g of white 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 , 160
^{0cm -1, 1650cm -1, 1670cm -1} , 1700cm -1,
A characteristic peak appeared at 3300 cm ^-1 . The structural formula of the main component of this compound is represented by the aforementioned compound (S-
1) is estimated.

Next, 2 g of this compound was taken, and 2.5% by weight
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.

Also, 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 2000 rpm for 3 hours together with 130 g of a weight% aqueous polyvinyl alcohol solution. In addition, 10 g of calcium carbonate is added to 30 pieces of water.
g and mixed by stirring 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-anilinofluorane 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 further 7 parts by weight of a dry solid content of 15% by weight polyvinyl alcohol (on a dry basis).

This coating solution was applied to a base paper having a weighing of 50 g / m ^{2 using} a bar 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 terms of dry weight. The evaluation result of the sensitivity of the obtained heat-sensitive recording material was as follows.
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.

[0211]

EXAMPLE 2 17 g of 2,4-toluene diisocyanate
To the mixture was added 40 g of methyl ethyl ketone as a solvent, 3.8 g of methanol was added dropwise, and the mixture was reacted at 60 ° C. for 5 hours with stirring. Next, 9.9 g of 4,4'-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
At ° C, the analytical values are as follows: Results of IR measurement: 1220 cm ^-1 , 1550 cm ^-1 , 159
^{0cm -1, 1660cm -1, 1740cm -1} , characteristic peaks appeared in 3300 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.

[0212]

Example 3 3.46 g of aniline was added to 100 m of ethyl acetate
And stirred at room temperature, and a solution of 10 g of trimethylolpropane adduct of toluene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd., 75% ethyl acetate solution) and 50 mL of ethyl acetate was dropped in 1 hour. And further reacted for 30 minutes. The generated crystals were collected by filtration, and dried in vacuo overnight to afford white crystalline compound 5.1.
g was obtained. 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 , 155
^{0cm -1, 1600cm -1, 1700cm -1} , characteristic peaks appeared in 3300 cm ^-1. The structural formula of the main component of this compound is represented by the aforementioned compound (S-3)
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.

[0213]

Comparative Example 1 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 recovered by filtration, washed with hexane, and dried under vacuum overnight to obtain 17 g of a white crystalline compound. The presumed structural formula of the main component of this compound is shown below (C-1).
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. Table 1 summarizes the results
Shown in

[0214]

Comparative Example 2 In 96 g of methanol, 17.4 g of 2,4-toluene diisocyanate was added dropwise over 2 hours while stirring at 25 ° C., and the mixture was further reacted for 1 hour. The precipitated white crystals were collected by filtration, washed with methanol, and then dried in vacuo overnight to obtain 10 g of a white crystalline compound. The presumed structural formula of the main component of this compound is shown below (C-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. Table 1 summarizes the results
Shown in

[0215]

Comparative Example 3 2,4-Toluene diisocyanate
To 100 g of 0 g, 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 give 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. The reaction was performed at 12 ° C. for 12 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 , 163
^{0cm -1, 1710cm -1, 2900cm -1} , characteristic peaks appeared in 3300 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 (C-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.

[0219]

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. Next, 2 g of this compound was added to 50 mL of dioxane, 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. Subsequently, the reaction was carried out at 80 ° C. for 20 hours. After the reaction, the reaction solution 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 , 151
^{0cm -1, 1570cm -1, 1620cm -1} , 1700cm -1,
Characteristic peaks appeared at 2900 cm ^-1 and 3300 cm ^-1 . The presumed structural formula of the main component of this compound is shown below (C-4). 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.

[0219]

Embedded image

[0220]

[Table 1]

[0221]

By using a specific urea urethane compound, a color former and a recording material which are excellent in color sensitivity and image storability and excellent in physical and chemical stability, especially heat resistance can be provided at low cost.

Claims (14)

[Claims] 1. An aliphatic urethane group represented by the formula (I) in a molecular structure: (Wherein, R ₁ and R ₂ each independently represent hydrogen, an aliphatic compound residue, a heterocyclic compound residue, or an aromatic compound residue, and R ₁ and R _{2 each} have a substituent. R ₁ and R ₂ may combine to form an alicyclic structure.) Having a urea group represented by the formula (II): Nitrogen atoms at both ends of the urea group are directly bonded to carbon atoms of an aliphatic compound residue, a heterocyclic compound residue, or an aromatic compound residue, and the total number of aliphatic urethane groups and urea groups is 2 or more. Hereinafter, a color developer containing a urea urethane compound having a molecular weight of 5,000 or less, and a color former containing a colorless or pale color dye precursor. 2. The color forming agent according to claim 1, wherein the urea group is an aromatic urea group represented by the formula (III). Embedded image (In the formula, the hydrogen atom of the benzene ring may be substituted with an aliphatic compound residue, a heterocyclic compound residue, or an aromatic compound residue, and each residue may have a substituent. good.) 3. A urea urethane compound represented by the following formula (I)
The color former according to claim 1, which is represented by V). 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. ) 4. The color former according to claim 1, wherein the urea urethane compound is represented by the following formula (V). 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 represents an aromatic compound residue having a valence of 2 or more. Represents a group, a heterocyclic compound residue or an aliphatic compound residue, n represents an integer of 2 or more, and each residue may have a substituent.) 5. The urea urethane compound represented by the following formula (VI):
The color former according to claim 1, wherein Embedded image (Wherein, R each 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
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 the formula (a), embedded image 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. ) 6. The urea urethane compound represented by the following formula (VI)
The color former according to claim 1, which is represented by I). Embedded image (Wherein, Z and Y each independently represent an aromatic compound residue or a heterocyclic compound residue, β represents an aliphatic compound residue having a valence of 2 or more, and n represents 2 or more. Represents an integer, and each residue may have a substituent.) 7. The urea urethane compound represented by the following formula (VII)
The color former according to claim 1, which is represented by I). Embedded image (Where 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. May be substituted by 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 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.) 8. The color former according to claim 1, further comprising a sensitizer. 9. The color former according to claim 1, further comprising an isocyanate compound. 10. The color former according to claim 1, further comprising an isocyanate compound and an imino compound. 11. The color former according to claim 1, further comprising an amino compound. 12. The method according to claim 1, further comprising an acidic developer.
12. The color former according to any one of to 11. 13. A recording material comprising a support on which a color-forming layer containing the color-forming agent according to claim 1 is provided. 14. The recording material according to claim 13, wherein the recording material is a thermosensitive recording material.