RU2245873C2 - New color-forming compositions and recording material - Google Patents

Abstract

FIELD: color-forming compositions and recording material.

SUBSTANCE: claimed composition includes developer containing urea-urethane compound and colorless or light colored leuco dye. Recording material based on this composition also is proposed.

EFFECT: color-forming compositions with improved image conservation ability and increased image intensity.

21 cl, 14 tbl, 153 ex

Description

The present invention relates to a new urea-urethane compound. The present invention also relates to a new color-forming composition, which is obtained using a urea-urethane compound, and a recording material, which is obtained using a color-forming composition.

The color-forming composition of the present invention is used as a color-forming composition for recording materials that use recording energy, such as heat, pressure or the like, and, in particular, the present invention relates to a color-forming composition that is capable of improving the stability of the unpainted portion (the original surface of the recording material) during storage and the developed color image, and to the recording material, in particular to a heat-sensitive recording mat ialu which is obtained by using the color-composition.

BACKGROUND OF THE INVENTION

Various chemical color-forming systems are known that use recording energy, such as heat, pressure or the like. Among these systems, color-forming systems have long been known, usually consisting of a two-component color-forming system containing a colorless or light-colored dye precursor substance and a developer capable of causing color to appear upon contact with the dye precursor substance, and they are typically used in recording materials. For example, there are pressure-sensitive recording materials that record using pressure, heat-sensitive recording materials that record using heat, and photosensitive recording materials that record using light.

Pressure-sensitive recording materials are typically used in planar form, similar to paper. Typically, pressure-sensitive recording material is obtained by dissolving a dye precursor in a suitable solvent, emulsifying the resulting solution to a few microns and molding the emulsion into microcapsules. The first layer of paper (also called top paper here), obtained by coating the substrate with microcapsules, and the second layer of paper (also called here, bottom paper), obtained by coating another substrate with a developing layer containing the developer, are placed on top of each other so that the surface covered with microcapsules, and the surface coated with the developer were facing each other. When pressure is applied to the resulting system by writing, touching, or the like, microcapsules are destroyed to release contents including a dye precursor substance. The dye precursor substance is transferred to the developing layer to interact with the developer, which causes a color development reaction leading to image recording.

In recent years, a heat-sensitive recording method, including recording using thermal energy, has often been used in various information devices, such as facsimiles, printers, recording devices, and the like. The thermosensitive recording material used in the thermosensitive recording method has many excellent characteristics, such as high whiteness, image clarity and sensitivity, which are similar to those of ordinary planar paper, and is ideal for recording, for example, for high-quality color reproduction. The method of heat-sensitive recording is suitable, for example, for those methods in which the device used is small in size, does not require maintenance and does not produce noise. Thus, the field of application of the method of thermosensitive recording in various fields, for example, in recording devices for measuring, facsimiles, printers, computer terminals, labels and automatic machines for trading in railway tickets or the like, is expanding.

In the heat-sensitive recording method, mainly the recording material used is obtained by applying a color-forming layer containing a two-component color-forming composition to the substrate, and the components of the heat-sensitive composition come into contact with each other by treating the recording material with heat supplied as recording energy from the terminal recording head , hot stamp, laser beams or the like, thus, the manifestation of color and recording. Many compositions used as a color-forming composition are prepared by using a colorless or light-colored electron-donor dye precursor (in particular leuko dye) and an acid developer, such as a phenolic compound. An example of recording material obtained by using a dye precursor is thermal paper, obtained by using a combination of crystalline violet lactone and 4,4'-isopropylidene diphenol (bisphenol A) as a heat-sensitive color-forming composition (see US Pat. No. 3,539,375 and so on) .

As the dye and developer precursor substance used in each of the above recording methods, an electron-donor compound and an electron-withdrawal compound, respectively, are predominantly used. This is because the electron-donor compound and the electron-withdrawing compound have, for example, the following excellent characteristics: a dye precursor substance, such as an electron-donor compound, and a developer, such as an electron-withdrawing compound, come into contact with each other to produce an almost immediately high-intensity color image ; and an almost white hue can be obtained, and various colors can be obtained, such as red, orange, yellow, green, blue, black and so on. However, the developed color image is so weak with respect to chemical resistance that the recording easily disappears upon contact with a plasticizer contained in a plastic sheet or eraser, or chemical products contained in food or cosmetics. Also, the color image that appears has such a low storage life that the recording fades or, even worse, disappears under direct sunlight in a relatively short period of time. Thus, color-forming compositions containing a dye precursor and a developer are substantially limited in their application, and their improvement is highly desirable.

In recent years, phenolic compounds represented by bisphenol A are considered unsuitable for use, as they are likely to damage the endocrine system and therefore non-phenolic developers are preferred.

To fulfill this requirement, for example, in Japanese patent JP-A-59-115887 and US patent No. 4521793 as recording materials with a long shelf life are described recording materials containing a combination of color-forming compositions comprising an aromatic isocyanate compound and an imino compound. These references describe various recording materials in which two color-forming compositions come into contact with each other to interact when using recording energy such as heat, pressure, light or the like. The links describe the fact that various colors, such as red, orange, yellow, light brown, dark brown and so on, can be formed with the proper selection of color-forming compositions. However, the inventions described in the references did not show enough black, which is highly desirable with respect to commonly used recording materials.

Japanese Patent JP-A-8-2111 and Japanese Patent JP-A-8-2112 as heat-sensitive recording materials obtained using a non-phenolic developer describe heat-sensitive recording materials that have a color-forming layer containing a colorless or slightly colored dye precursor and urea compound. However, these recording materials give a low staining intensity and have an unsatisfactory shelf life.

Japanese patent JP-A-5-116459 describes a thermosensitive recording material comprising a thermosensitive color-forming layer including a colorless or slightly colored precursor and a sulfonylurea compound. However, this recording material has a low brightness and an unsatisfactory shelf life.

Description of the invention

The present invention relates to a novel urea-urethane compound or urea-urethane composition which exhibits excellent performance when used as a developer in a color-forming composition.

The present invention also relates to a novel color-forming composition having excellent image retention and image intensification ability, and recording material, in particular to heat-sensitive recording material, which is obtained by using a color-forming composition using any of various urea-urethane compounds or urea-urethane compositions.

In addition, the present invention relates to a new color-forming composition having additional improved performance due to the addition of various additives to the urea-urethane compound, or the urea-urethane composition and the dye precursor substance, and the recording material obtained by using said color-forming composition.

The inventors of the present invention thoroughly investigated the synthesis of various compounds for a color-forming composition, and as a result found that certain compounds unexpectedly exhibit excellent performance characteristics, on the basis of which the present invention was created. In addition, the inventors of the present invention have found that certain compounds unexpectedly exhibit excellent performance in combination with a particular dye precursor, on the basis of which the present invention was created.

Thus, the present invention is as follows.

A first aspect of the invention relates to a urea-urethane compound, which is characterized in that it is represented by the following formula (c) and has a molecular weight of 5000 or less:

where R represents the remainder of the aliphatic compound, A ₁ and A ₂ independently represent the remainder of the aromatic compound, the nitrogen atoms of the urea group are directly bonded to the carbon atoms of the aromatic rings A ₁ and A _2, respectively, and R, A ₁ and A ₂ may have one or several deputies. A second aspect of the invention relates to a urea-urethane compound, which is characterized by what is represented by the following formula (d):

where R represents a residue of an aliphatic compound, the hydrogen atom (s) of each benzene ring may (may) be substituted (s) with 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 , carboxyl group, nitroso group, amino group, hydroxy amino group, nitro amino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group or atom halogen, and R may have one or more substituents.

A third aspect of the invention relates to a urea-urethane compound, which is characterized by what is represented by the following formula (e) or (f), and includes at least one urethane group and at least one urea group with a total number of not more than than 10 and not less than 3, and has a molecular weight of 5000 or less:

where R is a residue of an aliphatic compound, Y is a residue of an aromatic compound, a residue of a heterocyclic compound or a residue of an aliphatic compound, α ₁ is a residue of an aromatic, heterocyclic or aliphatic compound that is different from Y and has a valency of 2 or more, n represents an integer of 2 or more, and each of the residues may have one or more substituents; or

where Z ₁ and Y independently represent a residue of an aromatic compound or a residue of a heterocyclic compound, β ₁ represents a residue of an aliphatic compound having a valency of 2 or more, n is an integer of 2 or more, and each of the residues may have one or more substitutes.

A fourth aspect of the invention relates to a urea-urethane compound, which is characterized by what is represented by the formula (g) or (h):

where the hydrogen atom (s) of each benzene ring may (may) be substituted (s) with 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, an amino group , oksiaminogruppoy, nitroamino, hydrazino, ureido, isocyanate group, mercapto group, sulfo group or a halogen atom, β ₁ is the residue of an aliphatic Connections, which has a valence of 2 or more, n represents an integer of 2 or more, and each of the residues may have one or more substituents; or

where R independently represents a residue of an aliphatic compound, the hydrogen atom (s) of each benzene ring may (may) be substituted (s) with a residue of an aromatic compound, a residue of an aliphatic compound or a residue of a heterocyclic compound, each of the residues may have one or more substituents, γ ₁ represents a group selected from the group consisting of -SO ₂ -, -O-, - (S) _n -, - (CH ₂ ) _n -, -CO-, -CONH-, -NH-, -CH (COOR ₁ ) -, -C (CF ₃ ) ₂ -, -CR ₂ R ₃ - and any of the groups represented by formulas (a):

or absent, each of R ₁ , R ₂ and R ₃ represents an alkyl group, and n is 1 or 2.

A fifth aspect of the invention relates to a urea-urethane composition, which is characterized in that it contains a urea-urethane compound and a diluent.

A sixth aspect of the invention relates to a urea-urethane composition according to the fifth aspect of the invention, wherein the diluent is a urea compound and / or a urethane compound.

A seventh aspect of the invention relates to a urea-urethane composition in accordance with a fifth aspect of the invention, wherein the diluent is a compound that is prepared by reacting a polyisocyanate compound with a hydroxy compound or an amino compound.

An eighth aspect of the invention relates to a urea-urethane composition, which is obtained by reacting a polyisocyanate compound with a hydroxy compound and an amino compound, which is characterized in that it comprises 50% by weight or more of a urea-urethane compound containing at least one urea group and at least one urethane group with a total number of 2-10 in the molecular structure and having a molecular weight of 5000 or less.

A ninth aspect of the invention relates to a urea-urethane composition in accordance with the eighth aspect of the invention, wherein the hydroxy compound is a phenolic compound.

A tenth aspect of the invention relates to a urea-urethane composition in accordance with the eighth aspect of the invention, wherein the hydroxy compound is an alcohol compound.

An eleventh aspect of the invention relates to a urea-urethane composition in accordance with any aspect of the invention, starting from the eighth and ending with the tenth, where the amino compound is an aromatic amino compound.

The twelfth aspect of the invention relates to a urea-urethane composition in accordance with any aspect of the invention, starting from the eighth to the eleventh, where the polyisocyanate compound is an aromatic polyisocyanate compound.

A thirteenth aspect of the invention relates to a method for producing a urea-urethane composition, which comprises reacting a polyisocyanate compound and a hydroxy compound so that the ratio of the number of moles of the polyisocyanate compound to the number of hydroxyl equivalents of the hydroxy compound becomes 100 / 1-1 / 2, with the formation of one or more urethane groups from several isocyanate groups of the polyisocyanate compound, and the subsequent addition of an amino compound to react with the remaining isocyanate th group (s) of the polyisocyanate compound to produce one or more urea groups.

A fourteenth aspect of the invention relates to a method for producing a urea-urethane composition, which comprises reacting a polyisocyanate compound and an amino compound so that the ratio of the number of moles of the polyisocyanate compound to the number of amino equivalents of the amino compound becomes 100 / 1-1 / 2, with the formation of one or more urea groups from several isocyanate groups of the polyisocyanate compound, and the subsequent addition of a hydroxy compound to interact with the remaining isocyanate group (s) oh (groups) of the polyisocyanate compound to produce one or more urethane groups.

The fifteenth aspect of the invention relates to a method for producing a urea-urethane composition in accordance with aspects of the invention, starting with the thirteenth and ending with the fourteenth, which consists in the fact that sequentially carry out the interaction to form one or more urethane groups and interaction to form one or more urea groups.

A sixteenth aspect of the invention relates to a method for producing a urea-urethane composition, which comprises reacting an amino compound with a polyisocyanate adduct obtained by reacting a polyisocyanate compound with a hydroxy compound so that the equivalent ratio of the isocyanate group to the amino group becomes 2 / 1-1 / 100, with the formation of one or several urea groups, and subsequent isolation of the unreacted amino compound.

A seventeenth aspect of the invention relates to a method for producing a urea-urethane composition, which comprises reacting a hydroxy compound with a polyisocyanate adduct obtained by reacting a polyisocyanate compound with an amino compound so that the equivalent ratio of the isocyanate group to the hydroxyl group becomes 2 / 1-1 / 100, with the formation one or more urethane groups, and the subsequent isolation of unreacted hydroxy compounds.

The eighteenth aspect of the invention relates to a method for producing a urea-urethane composition in accordance with any aspect of the invention, beginning with the thirteenth and ending with the seventeenth, which consists in the interaction to form one or more urethane groups, and / or interaction to form one or more urea groups, without solvent or by conducting an interaction to form one or more urethane groups, and / or interaction to form one or more groups urea using the same solvent.

The nineteenth aspect of the invention relates to a method for producing a urea-urethane composition in accordance with any aspect of the invention, starting from the thirteenth to the eighteenth, where the interaction for the formation of one or more urethane groups and / or the interaction for the formation of one or more urea groups is carried out at a temperature of 0 to 300 ° C.

A twentieth aspect of the invention relates to a method for producing a urea-urethane composition in accordance with any aspect of the invention, starting from the thirteenth to the nineteenth, where the interaction to form one or more urethane groups and / or the interaction to form one or more urea groups is carried out in the presence of a catalyst .

A twenty-first aspect of the invention relates to a color-forming composition comprising a developer comprising a urea-urethane compound.

A twenty-second aspect of the invention relates to a color-forming composition comprising a developer comprising a urea-urethane compound and a colorless or slightly colored dye precursor.

A twenty-third aspect of the invention relates to a color-forming composition in accordance with the twenty-second aspect of the invention, wherein the colorless or slightly colored dye precursor is a leuco dye.

A twenty-fourth aspect of the invention relates to a color-forming composition in accordance with aspects of the invention, starting from the twenty-first and ending with the twenty-third, where said developer is a urea-urethane compound in accordance with any aspect of the invention, starting from the first and ending with the fourth, urea-urethane a composition in accordance with any aspect of the invention, starting from the fifth to the twelfth, or a composition obtained by using the production method in accordance with any th aspect of the invention, from the thirteenth and twentieth finishing.

A twenty-fifth aspect of the invention relates to a color-forming composition in accordance with either the twenty-third or twenty-fourth aspects of the invention, which is characterized in that the leuco dye is at least one leuco dye selected from triarylmethane type leuco dyes, fluoran type leuco dyes, fluorene leuco dyes type and leuko-dyes of diphenylmethane type.

The twenty-sixth aspect of the invention relates to a color-forming composition in accordance with either the twenty-third or twenty-fourth aspects of the invention, which is characterized in that the leuco dye is a compound represented by the following formula (i):

where both y ₂ and Y ₃ represent alkyl groups or alkoxyalkyl groups, Y ₄ represents a hydrogen atom, an alkyl group or an alkoxy group, and each of Y ₅ and Y ₆ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

A twenty-seventh aspect of the invention relates to a color-forming composition in accordance with either the twenty-third or twenty-fourth aspects of the invention, which is characterized in that the leuco dye is a compound represented by the following formula (j):

where each R ₅ and R ₆ is a group represented by formula (k) or formula (l):

(where each R ₁₁ -R ₁₅ represents a hydrogen atom, a halogen atom, an alkyl group of 1-8 carbon atoms, an alkoxy group of 1-8 carbon atoms or -NR ₁₆ R ₁₇ , where each R ₁₆ and R ₁₇ represents an alkyl group from 1-8 carbon atoms) or

(where each R ₁₈ and R ₁₉ represents a hydrogen atom, an alkyl group of 1-8 carbon atoms, a phenyl group) and each R ₇ -R ₁₀ represents a hydrogen atom, a halogen atom, an alkyl group of 1-8 carbon atoms, an alkoxy group of 1-8 carbon atoms or -NR ₂₀ R ₂₁ where each R ₂₀ and R ₂₁ represents an alkyl group of 1-8 carbon atoms.

The twenty-eighth aspect of the invention relates to a color-forming composition in accordance with any aspect of the invention, starting from the twenty-first and ending with the twenty-seventh, which is characterized in that the melting point of the urea-urethane compound of the developer is not higher than 500 ° C and not lower than 40 ° C .

The twenty-ninth aspect of the invention relates to a color-forming composition in accordance with any aspect of the invention, starting from the twenty-first and ending with the twenty-seventh, which is characterized in that the urea-urethane developer compound comprises a compound selected from compounds represented by the following general formulas (V) or (Vi):

where the hydrogen atom (s) of each benzene ring may (may) be substituted (s) with an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group , mercapto group, sulfo group, sulfamoyl group or halogen atom, each of the residues may have one or more substituents, γ represents a group selected from the group, incl. sistent -SO ₂ -, -O-, - (S) n-, - (CH _{2) n} -, -CO-, -CONH- and any of the groups represented by the formulas (a):

or absent, and n is 1 or 2; and

where the hydrogen atom (s) of each benzene ring may (may) be substituted (s) with 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, an amino group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group or halogen atom, each of the residues may have one or more to the substituents, 5 represents a group selected from the group consisting of —SO ₂ -, —O—, - (S) _n -, - (CH ₂ ) _n -, —CO—, —CONH—, NH—, —CH (COOR ₁ ) -, -C (CF ₃ ) ₂ - and -CR ₂ R ₃ - or is absent, each of R ₁ , R ₂ and R ₃ represents an alkyl group, and n is 1 or 2.

A thirtieth aspect of the invention relates to a color-forming composition in accordance with any aspect of the invention, starting from the twenty-first and ending with the twenty-seventh, which is characterized in that the urea-urethane developer compound includes a compound selected from compounds represented by the following structural formulas (XX) and (XXI):

The thirty-first aspect of the invention relates to a color-forming composition in accordance with any aspect of the invention, from the twenty-first to the thirtieth, which further includes a heat-fusible substance.

The thirty-second aspect of the invention relates to a color-forming composition in accordance with the thirty-first aspect of the invention, which is characterized in that the heat-melting substance is at least one compound selected from β-naphthylbenzyl ether, p-benzylbiphenyl, 1,2-di ( m-methylphenoxy) ethane, dip-p-methylbenzyloxalate, 1,2-diphenoxymethylbenzene, m-terphenyl and stearamide.

The thirty-third aspect of the invention relates to a color-forming composition in accordance with the thirty-first aspect of the invention, where the heat-melting substance is represented by the following structural formula (XVIII):

where Y represents any group from —SO ₂ -, - (S) _n -, —O—, —CO—, —CH ₂ -, —CH (C ₆ H ₅ ) -, —C (CH ₃ ) ₂ - , -COCO-, -CO ₃ -, -COCH ₂ CO-, -COOCH ₂ -, -CONH-, -OCH ₂ - and -NH-, n is 1 or 2, and the hydrogen atom (s) of each benzene ring can (may) be substituted (s) by a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a sulfamoyl group, a sulfonic acid group, an amino group, an aromatic compound residue, an aliphatic compound residue or a hetero group dignia.

The thirty-fourth aspect of the invention relates to a color-forming composition in accordance with the thirty-third aspect of the invention, where the heat-melting substance is represented by the following structural formula (XIX):

where the hydrogen atom (s) of each benzene ring may (may) be substituted (s) by a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a sulfamoyl group, a sulfonic acid group, an amino group, an aromatic residue compounds, the residue of an aliphatic compound or the residue of a heterocyclic compound.

A thirty-fifth aspect of the invention relates to a color-forming composition in accordance with any of the aspects of the invention, starting from the twenty-first to the thirty-fourth, which further includes an isocyanate compound.

The thirty-sixth aspect of the invention relates to a color-forming composition in accordance with any aspect of the invention, starting from the twenty-first and ending with the thirty-fourth, which further includes an isocyanate compound and an imino compound.

A thirty-seventh aspect of the invention relates to a color-forming composition in accordance with any of the aspects of the invention, starting from the twenty-first and ending with the thirty-sixth, which further includes an amino compound.

The thirty-eighth aspect of the invention relates to a color-forming composition in accordance with any aspect of the invention, starting from the twenty-first and ending with the thirty-seventh, where the developer further includes an acid developer.

The thirty-ninth aspect of the invention relates to a color-forming composition in accordance with the thirty-eighth aspect of the invention, characterized in that the acid developer is at least one developer selected from 2,2-bis (4-hydroxyphenyl) propane, 4-isopropyloxyphenyl- 4'-hydroxyphenyl sulfone, bis (3-ally-4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl sulfone and 4,4 '- [oxybis (ethyleneoxy-p-phenylene sulfonyl)] diphenol.

The fortieth aspect of the invention relates to a color-forming composition in accordance with any aspect of the invention, starting from the twenty-first and ending with the thirty-ninth, which further includes fluorescent paint.

The forty-first aspect of the invention relates to a color-forming composition in accordance with any aspect of the invention, starting from the twenty-first and ending with the fortieth, which further includes an agent that confers storage stability.

A forty-second aspect of the invention relates to a recording material comprising a substrate and a color-forming layer formed thereon, said color-forming layer includes a urea-urethane compound in accordance with any aspect of the invention, starting from the first and ending with the fourth, urea-urethane composition in accordance with any aspect of the invention, starting from the fifth to the twelfth, or a color-forming composition in accordance with any aspect of the invention, starting from the twenty-first and ending nd forty-first.

The forty-third aspect of the invention relates to recording material in accordance with the forty-second aspect of the invention, which is characterized in that a protective layer is formed on the color-forming layer for the color-forming layer.

The forty-fourth aspect of the invention relates to recording material in accordance with the forty-third aspect of the invention, which is characterized in that the protective layer includes a water-soluble polymer.

The forty-fifth aspect of the invention relates to recording material in accordance with either the forty-third or the forty-fourth aspects of the invention, which is characterized in that the protective layer includes an inorganic pigment and / or organic pigment.

The forty-sixth aspect of the invention relates to recording material in accordance with any aspect of the invention, starting with the forty-third and ending with the forty-fifth, and is characterized in that the protective layer includes a lubricating agent.

The forty-seventh aspect of the invention relates to recording material in accordance with the forty-second aspect of the invention, which is characterized in that an intermediate layer is formed on the substrate and a color-forming layer is formed on said intermediate layer.

The forty-eighth aspect of the invention relates to recording material in accordance with the forty-seventh aspect of the invention, which is characterized in that the intermediate layer includes a water-soluble polymer.

A forty-ninth aspect of the invention relates to recording material in accordance with either the forty-seventh or the forty-eighth aspects of the invention, which is characterized in that the intermediate layer includes an inorganic pigment and / or organic pigment.

A fiftieth aspect of the invention relates to recording material in accordance with the forty-second aspect of the invention, which is characterized in that the back side coating layer is formed on the substrate from the back side with respect to the side having a color-forming layer formed thereon.

The fifty-first aspect of the invention relates to recording material in accordance with the fiftieth aspect of the invention, which is characterized in that the back coating layer includes a water-soluble polymer.

The fifty-second aspect of the invention relates to recording material in accordance with either the fiftieth or fifty first aspects of the invention, which are characterized in that the back-side coating layer includes an inorganic pigment and / or organic pigment.

The fifty-third aspect of the invention relates to recording material in accordance with any aspect of the invention, starting with the forty-second and ending with the fifty-second, which is characterized by the use of at least one compound selected from water-soluble polymers and anionic surfactants, as a dispersing agent for urea-urethane compounds.

A fifty-fourth aspect of the invention relates to recording material in accordance with any aspect of the invention, starting with the forty-second and ending with the fifty-second, which is characterized by the use of at least one compound selected from polyvinyl alcohol, modified polyvinyl alcohol, methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalenesulfonate, ammonium salts of polycarboxylic acid, water-soluble low molecular weight copolymers and 2-ethylhexyl sulfosu sodium calcinate, as a dispersing agent of the urea-urethane compound.

A fifty-fifth aspect of the invention relates to recording material in accordance with any aspect of the invention, starting with the forty-second and ending with the fifty-fourth, which is characterized by the use of at least one compound selected from water-soluble polymers, nonionic surfactants and anionic surfactants active substances as a dispersing agent for a dye precursor substance.

A fifty-sixth aspect of the invention relates to recording material in accordance with any aspect of the invention, starting from forty-second to fifty-fourth, which is characterized by the use of at least one compound selected from methyl cellulose, hydroxypropyl methyl cellulose, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ether sulfates and sodium 2-ethylhexyl sulfosuccinate, as a dispersing agent for the dye precursor.

The fifty-seventh aspect of the invention relates to recording material in accordance with any aspect of the invention, starting with the forty-second and ending with the fifty-sixth, which is a heat-sensitive recording material.

The fifty-eighth aspect of the invention relates to heat-sensitive recording material in accordance with the fifty-seventh aspect of the invention, which is characterized in that the average particle size of the urea-urethane compound is not more than 5 μm and not less than 0.05 μm.

The fifty-ninth aspect of the invention relates to heat-sensitive recording material in accordance with the fifty-seventh and fifty-eighth aspect of the invention, which is characterized by the fact that the temperature of the liquid during grinding of the urea-urethane compound is 60 ° C or lower.

A sixtieth aspect of the invention relates to heat-sensitive recording material in accordance with any aspect of the invention, starting from the fifty-seventh and ending with the fifty-ninth, which is characterized in that the pH when grinding the urea-urethane compound is from 5 to 10.

The sixty-first aspect of the invention relates to heat-sensitive recording material in accordance with any aspect of the invention, starting from the fifty-seventh and ending with the sixtieth, which is characterized by the use of at least one compound selected from water-soluble polymers and anionic surfactants as dispersing agent for a heat-fusible substance.

A sixty-second aspect of the invention relates to heat-sensitive recording material in accordance with any aspect of the invention, from the fifty-seventh to the sixtieth, which is characterized by the use of at least one compound selected from polyvinyl alcohol, modified polyvinyl alcohol, methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalenesulfonate, ammonium salts of polycarboxylic acids, water-soluble low molecular weight copolymers 2-ethylhexyl sulfosuccinate sodium as a dispersant for teploplavkogo substance.

A sixty-third aspect of the invention relates to heat-sensitive recording material in accordance with any aspect of the invention, starting with the fifty-seventh and ending with the sixty-second, which is characterized in that the urea-urethane compound and the heat-melting substance are finely ground together.

A sixty-fourth aspect of the invention relates to heat-sensitive recording material in accordance with any aspect of the invention, starting from fifty-seventh and ending with sixty-third, which is characterized in that the pH of the surface of the substrate, which is coated with a heat-sensitive recording layer of heat-sensitive recording material, is from 3 to 9.

A sixty-fifth aspect of the invention relates to a method for producing heat-sensitive recording material in accordance with any aspect of the invention, starting from fifty-seventh to sixty-fourth, which is characterized by applying a heat-sensitive coating liquid to the substrate with a pH from 5 to 12 to form a heat-sensitive recording layer of a heat-sensitive recording material.

A sixty-sixth aspect of the invention relates to recording material in accordance with the forty-second aspect of the invention, which is a heat-sensitive magnetic recording material.

A sixty-seventh aspect of the invention relates to a heat-sensitive magnetic recording material in accordance with the sixty-sixth aspect of the invention, which is characterized in that a heat-sensitive recording layer including a urea-urethane developer compound is formed on one side of the substrate, and a magnetic recording layer on the other side.

A sixty-eighth aspect of the invention relates to a train ticket, which is a heat-sensitive magnetic recording material in accordance with the sixty-sixth or sixty-seventh aspect of the invention.

A sixty-ninth aspect of the invention relates to a ticket, which is a heat-sensitive magnetic recording material in accordance with the sixty-sixth or sixty-seventh aspect of the invention.

The seventieth aspect of the invention relates to recording material in accordance with the forty-second aspect of the invention, which is a label for heat-sensitive recording.

The seventy-first aspect of the invention relates to a label for heat-sensitive recording in accordance with the seventieth aspect of the invention, which is characterized in that a heat-sensitive recording layer including a urea-urethane developer compound is formed on one side of the substrate, and the adhesive layer on the other side.

A seventy-second aspect of the invention relates to a label for heat-sensitive recording in accordance with the seventy-first aspect of the invention, which is characterized in that the back side coating layer is formed between the adhesive layer and the substrate.

A seventy-third aspect of the invention relates to a label for heat-sensitive recording in accordance with either the seventy-first or seventy-second aspects of the invention, which is characterized in that an intermediate layer is formed between the heat-sensitive recording layer and the substrate.

A seventy-fourth aspect of the invention relates to a label for heat-sensitive recording in accordance with any aspect of the invention, starting from the seventy-first and ending with seventy-third, which is characterized in that the protective layer is formed on a heat-sensitive recording layer.

A seventy-fifth aspect of the invention relates to recording material in accordance with the forty-second aspect of the invention, which is a color heat-sensitive recording material.

A seventy-sixth aspect of the invention relates to color heat-sensitive recording material in accordance with a seventy-fifth aspect of the invention, where at least two heat-sensitive recording layers are formed on one side of a substrate, said recording material is characterized in that at least one of said heat-sensitive recording material The recording layers include a urea-urethane developer compound.

The seventy-seventh aspect of the invention relates to a color heat-sensitive recording material in accordance with the seventy-sixth aspect of the invention, which is characterized in that the intermediate layer is formed by interthermosensitive recording layers.

The seventy-eighth aspect of the invention relates to a color heat-sensitive recording material, which is characterized in that it includes a substrate and two heat-sensitive recording layers laminated on one side of the substrate, which have different color development temperatures, respectively, and are exposed to color development of different color tones, respectively, the upper heat-sensitive a recording layer that includes either an agent used both as a developer and as a tone a lab agent, or a reverse developer, and a lower heat-sensitive recording layer including a urea-urethane compound of the developer.

A seventy-ninth aspect of the invention relates to color heat-sensitive recording material in accordance with the seventy-eighth aspect of the invention, which is characterized in that their two heat-sensitive recording layers, the upper layer is a low-temperature color-forming layer capable of undergoing color development at low temperature and undergo achromatization at high temperature, and the lower layer is a color-forming layer capable of undergoing color development at high temperatures ur

An eightieth aspect of the invention relates to a laser marking product, which is characterized in that it has a heat-sensitive recording layer on the surface including a urea-urethane developer compound.

The eighty-first aspect of the invention relates to a laser marking product, which is characterized by having a heat-sensitive recording layer on the surface including a colorless or slightly colored dye precursor, a urea-urethane developer compound and an agent that improves recording sensitivity.

The eighty-second aspect of the invention relates to an article for laser marking in accordance with either the eightieth or eighty-first aspects of the invention, which is characterized in that on the heat-sensitive recording layer, a protective layer comprising an aqueous binding agent having a glass transition point of 20-80 ° C.

The eighty-third aspect of the invention relates to an article for laser marking in accordance with the eighty-first aspect of the invention, where the agent that improves the recording sensitivity is at least one compound selected from aluminum hydroxide, muscovite, wollastonite and kaolin.

The eighty-fourth aspect of the invention relates to an article for laser marking in accordance with any aspect of the invention, starting from the eightieth and ending with eighty-third, which is any label, packaging material and container.

An eighty-fifth aspect of the invention relates to a method for producing a laser marking product, which is characterized by applying a color-forming marking composition to a substrate, comprising a urea-urethane developer compound, and drying the substrate thus obtained.

An eighty-sixth aspect of the invention relates to a method for producing a laser marking product, which is characterized by applying to a substrate a color-forming marking composition comprising a colorless or slightly colored dye precursor substance, a urea-urethane developer compound and an agent that improves recording sensitivity, and drying the resulting image of the substrate.

An eighty-seventh aspect of the invention relates to a method for marking an article, which is characterized by irradiating a heat-sensitive recording layer of a laser marking article in accordance with any aspect of the invention, starting from the eightieth and ending with the eighty-fourth, laser beams.

The eighty-eighth aspect of the invention relates to a color-forming composition for marking, which is characterized in that it includes a urea-urethane compound of the developer.

The eighty-ninth aspect of the invention relates to a color-forming composition for marking, which is characterized in that it includes a colorless or light-colored dye precursor substance, a urea-urethane developer compound and an agent that improves recording sensitivity.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is described in further detail below.

Each of the urea-urethane compounds of the aspects of the present invention, starting from the first and ending with the fourth, contains at least one urea group and one urethane group.

In urea-urethane compounds according to aspects of the invention, from the first to the fourth residue of the aliphatic compound is attached to the terminal oxygen atom of the urethane group. Thus, urea-urethane compounds can be obtained as compounds with excellent physical and chemical stability, in particular resistance to heat. Moreover, urea-urethane compounds can be obtained using relatively inexpensive products.

In addition, the starting alcohol compound for the residue of the aliphatic compound attached to the terminal oxygen atom of the urethane group can be easily removed, even if it remains unreacted in the synthesis of the urea-urethane compound. Therefore, urea-urethane compounds can be obtained with a high degree of purity.

Preferred forms at the ends of the urea group may vary depending on the molecular size of the urea-urethane compound. In the urea-urethane compound of formula (c), each end of the urea group must be attached to the remainder of the aromatic compound. The residue of the aromatic compound is preferably the aromatic ring shown in formula (d). In urea-urethane compounds of formulas (e) and (f) having relatively large molecular sizes, the group at each end of the urea group is, for example, the following: in formula (e), the group at each end can be any residue of an aromatic compound, a residue of a heterocyclic compounds and the residue of an aliphatic compound, and in formula (f), the group at each end may be either a residue of an aromatic compound or a residue of a heterocyclic compound. In both formulas (e) and (f), the group at each end of the urea group preferably represents a residue of an aromatic compound. The urea group and the urethane group are adjacent relative to each other, connected through at least one residue of the compound (such a structural fragment is hereinafter referred to as the urea-urethane structural fragment). Preferably, only one residue of the compound is between the urea group and the urethane group. In addition, this residue is preferably an aromatic ring.

Although the specific mechanism by which the urea-urethane compounds of the first to fourth aspects of the invention act as a developer is not known, it is believed that the action occurs by the interaction between the urea group and the urethane group in the urea-urethane structural fragment. In formulas (e) and (f), the number of urea-urethane structural fragments is two or more. On the other hand, in the formula (c) or (d), the number of urea-urethane structural fragments in some cases is unity. In this case, the following is contemplated: in the urea-urethane compound of formula (c) or (d), the residue to be attached to each end of the urea group is limited to the most preferred residue, i.e. the remainder of the aromatic compound so that the compound can act as a developer to some extent; on the other hand, in formulas (e) and (f), the residue that is attached to each end of the urethane group may not always be the residue of an aromatic compound.

It is sufficient that the number of urea-urethane structural fragments present in the molecule is from 1 to 10, preferably from 1 to 5, more preferably from 2 to 4.

In addition to the urea-urethane (s) structural fragment (s), the urea-urethane compound may have one or more other urea groups and urethane groups in the molecule.

The term “aliphatic” as used in the first to fourth aspects of the invention includes the term “alicyclic”.

The term “residue of an aliphatic compound”, which is used in the first to fourth aspects of the invention, means a residue attached via the carbon atom of an aliphatic hydrocarbon moiety in the residue. The term “aromatic compound residue” as used herein means a residue attached via a carbon atom of an aromatic ring, such as a benzene ring. The term “heterocyclic compound residue” as used herein means a residue attached via a carbon atom to form a heterocyclic ring in the residue.

Preferred examples of substituents of an aliphatic compound residue, a heterocyclic compound residue and an aromatic compound residue are alkyl groups, cycloalkyl groups, phenyl group, amide group, alkoxyl groups, nitro group, nyryl group, halogen atoms, formyl group, dialkylamino groups, toluenesulfonyl group and methanesulfonyl group.

In the case where the urea-urethane compounds of the first to fourth aspects of the invention are used as a developer or in heat-sensitive recording material, the total number of one or more aliphatic urethane groups and one or more urea groups that are present in the molecular structure of each urea-urethane compound aspects of the invention, starting from the first and ending with the fourth, is not more than 11 and not less than 2, preferably not more than 11 and not less than 3, more preferred flax is not more than 11 and not less than 4. The ratio of the urethane (s) group (s) to the urea group (s) is preferably from 1: 3 to 3: 1, more preferably from 1: 2 to 2: 1, most preferably 1: 1. The molecular weight of the urea-urethane compounds is 5000 or less, preferably 2000 or less.

In a heat-sensitive recording substance, a compound having a melting point is preferably used. The melting point of the urea-urethane compounds according to the first to fourth aspects of the invention is in the range preferably from 40 ° C to 500 ° C, more preferably from 60 ° C to 300 ° C, most preferably from 60 ° C to 250 ° C.

The synthesis method for each urea-urethane compound of the first to fourth aspects of the invention is not particularly limited. A method in which a urea-urethane compound is synthesized by reacting an isocyanate compound with an alcohol compound and an amino compound is preferred in view of its simplicity.

A method for producing a urea-urethane compound of formula (c) according to the first aspect of the present invention is not limited. This compound can be obtained, for example, by reacting an alcohol compound of the following formula (m) with an isocyanate compound of the following formula (n) and an amino compound of the following formula (o) in accordance with, for example, reaction equation (A ′) or (B ′), presented below:

where R is a residue of an aliphatic compound, which may have one or more substituents;

where A ₁ represents a residue of an aromatic compound which may have one or more substituents; and

where A ₂ represents the remainder of the aromatic compound, which may have one or more substituents.

The process for preparing the urea-urethane compound of formula (d) is not particularly limited to the second aspect of the present invention. This compound can be obtained, for example, by reacting an alcohol compound of the formula (m) with an isocyanate compound of the following formula (p) and an amino compound of the following formula (q) in accordance with, for example, the reaction equation (C ') or (D') represented by below:

where the hydrogen atom (s) of the benzene ring may (may) be substituted (s) by the residue of an aromatic compound, the residue of an aliphatic compound, the residue of a heterocyclic compound, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group or halogen atom and where each residue may have one or more substitutes stiteley; and

where the hydrogen atom (s) of the benzene ring may (may) be substituted (s) with an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue, and each residue may have one or more substituents.

The method for producing the urea-urethane compound of formula (e) in the third aspect of the present invention is not particularly limited. This compound can be obtained, for example, by reacting an alcohol compound of the general formula (m) with an isocyanate compound of the following general formula (r) and an amino compound of the following general formula (s) according to, for example, the reaction formula (E ') or (F' ) presented below:

where Y represents a residue of an aromatic compound, a residue of a heterocyclic compound or a residue of an aliphatic compound, and each residue may have one or more substituents; and

where α ₁ is a residue of an aromatic, aliphatic or heterocyclic compound that has a valency of 2 or more, n is an integer of 2 or more, and each residue may have one or more substituents.

The process for preparing the urea-urethane compound of formula (f) in the third aspect of the present invention is not particularly limited. This compound can be obtained, for example, by reacting an amino compound of the following general formula (t) with an isocyanate compound of the following general formula (r) and an alcohol compound of the general formula (u) in accordance with, for example, the reaction formula (G ′) or (H ′) ) presented below:

where Z ₁ represents a residue of an aromatic compound or a residue of a heterocyclic compound and each residue may have one or more substituents; and

where β ₁ is a residue of an aliphatic compound that has a valency of 2 or more, and may have one or more substituents, and n is an integer of 2 or more.

The process for preparing the urea-urethane compound of formula (g) in the fourth aspect of the present invention is not particularly limited. This compound can be obtained, for example, by reacting an alcohol compound of formula (s) with an isocyanate compound of formula (p) and an amino compound of formula (q) in accordance with, for example, the reaction formula (i ’) or (J’) shown below:

The process for preparing the urea-urethane compound of formula (h) in the fourth aspect of the present invention is not particularly limited. This compound can be obtained, for example, by reacting an amino compound of the following formula (XVII) with an isocyanate compound of the formula (p) and an alcohol compound of the general formula (m) in accordance with, for example, the reaction formula (K ') or (L') represented by below:

where the hydrogen atom (s) of each benzene ring may (may) be substituted (s) with an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group , mercapto group, sulfo group, sulfamoyl group or halogen atom, each residue may have one or more substituents, γ ₁ represents a group selected from the group including -SO ₂ -, -O-, - (S) _n -, - (CH ₂ ) _n -, -CO-, -CONH-, -NH-, -CH (COOR ₁ ) -, -С (CF ₃ ) ₂ -, -CR ₂ Rs- and any group represented by formulas (a):

or absent, each of R ₁ , R ₂ and R ₃ represents an alkyl group and n is 1 or 2.

The compounds of formulas (m) - (u), which can be used in the synthesis of urea-urethane compounds of the above formulas (c) - (h), are further disclosed in more detail.

As the alcohol compound of general formula (m), any alcohol compound may be used provided that it has one or more OH groups attached to one or more carbon atoms of an aliphatic compound, respectively. Examples of the alcohol compound are the alcohols described in Solvent Handbook, Kodansha Scientific Co., Ltd., Ninth Reprint (1989), pp. 327-420 and pp. 772-817. The alcohol compound includes, for example, aliphatic 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, isononyl alcohol, decanol, undecyl decyl tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl vy alcohol, isostearyl alcohol and so on; unsaturated aliphatic alcohols such as allyl alcohol, 2-methyl-2-propen-1-ol, crotyl alcohol, propargyl alcohol and so on; aliphatic alcohols having an aromatic residue attached to them, such as benzyl alcohol, cinnamyl alcohol and so on; aliphatic alcohols having a heterocyclic compound residue attached thereto, such as 2-pyridinomethanol, 3-pyridinomethanol, 4-pyridinomethanol, furfuryl alcohol and so on; halogenated aliphatic alcohols such as 2-chloroethanol, 1-chloro-3-hydroxypropane and so on; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, monopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, monoisobutyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, monopropyl ether, monoisopropyl diethylene glycol ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, monohexyl ether, diethylene glycol monophenyl ether, diethylene 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, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether dipropylene glycol, dipropylene glycol monobutyl ether, m noizobutilovy ether, dipropylene glycol monophenyl ether of dipropylene glycol and so on; diols such as 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-nonanediol, neopentyl glycol, methylpentanediol and so on; aliphatic polyols such as glycerin, castor oil, trimethylol propane, trimethylol ethane, hexantriol, pentaerythritol, α-methyl glucoside, sorbitol, sucrose and so on; polyols such as polyethylene glycols, polypropylene glycols, polytetramethylene glycols, adipate derivatives of polyols, epoxy-modified polyols, polyester ethers of polyols, polycarbonate polyols, polycaprolactone diols, amine-modified polyols, polyethylene polyethylene oxides obtained by the addition of several or two alkylene polyethylene or one to one or a mixture of two or more polyols (glycerin and propylene glycol), acrylic polyols, fluorinated polyols, polyb adienovye polyols, polyhydroxy polyols, polyols derived from castor oil, polymer polyols, halogen-containing polyols, phosphorus-containing polyols and the like; and alkanolamines, such as N, N-dialkylethanolamines, N, N-dialkylisopropanolamines, N-alkyldiethanolamines, N-alkyldiisopropanolamines, triethanolamine, triisopropanolamine, N, N, N ', N'-tetrakis (2-hydroxyethyl, ethyl) N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine and so on.

Of the above, as an example, alcohol compounds, mono alcohols containing one OH group are preferred, and aliphatic alcohols and glycol ethers that contain 10 or less carbon atoms are more preferred.

The isocyanate compound of formula (n) is not particularly limited as long as it is an aromatic isocyanate having two or more isocyanate groups attached to carbon atoms, respectively. The isocyanate compound includes, for example, p-phenylenediisocyanate, m-phenylenediisocyanate, o-phenylenediisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethanediisocyanate, o diisocyanate diphenyl ether, 1,5-naphthylenediisocyanate, dianisidinediisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate, 4,4 ', 4``-triisocyanate , 5-dimethoxytriphenylamine and 4.4 ', 4' '- triisocyanatotriphenylamine. Diisocyanate dimers such as N, N ’- (4,4’-dimethyl-3,3′-diphenyldiisocyanato) urethiodion (Desmodule TT, trade name), toluene diisocyanate dimer; and diisocyanate trimers, such as 4.4 ’, 4’ ’- trimethyl-3.3’, 3 ’’ - triisocyanato-2,4,6-triphenyl cyanurate. Can also be used aqueous adducts of isocyanates selected from toluene diisocyanate, diphenylmethane diisocyanate and the like, such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; polyol adducts such as trimethylolpropane adducts selected from toluene diisocyanate (Desmodule L and Coronate L, trade names); and amino adducts. Compounds having two or more isocyanate groups, including isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patent JP-A-10-76757 and the detailed description of Japanese patent JP-A-10-95171 (the contents of these links are hereby incorporated by reference).

The exemplified isocyanate compounds, aromatic isocyanates having isocyanate groups attached to a benzene ring are preferred. More preferred are p-phenylenediisocyanate, m-phenylenediisocyanate, o-phenylenediisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethanediisocyanate, o-tolidinediisocyanate, diphenyl ether diisocyanate, 1,5-di-phenyl diisocyanate (4,4'-dimethyl-3,3'-diphenyldiisocyanato) urethodion (Desmodule TT, trade name), 4.4 ', 4' '- trimethyl-3.3', 3 '' - triisocyanato-2.4, 6-triphenyl cyanurate, 1,3-bis (3-isocyanato-4-methylphenyl) urea and trimethylolpropane adducts selected from toluene diisocyanate (Desmodule L and Coronate L, t rgovye name). Particularly preferred examples of the isocyanate compound of formula (n) are toluene diisocyanates. Of the toluene diisocyanates, 2,4-toluene diisocyanate is preferred. In addition, 2,4-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, which are widely available on the market and are available at low cost, can also be used as isocyanate compounds of formula (n).

As the amine compound of the general formula (o), for example, aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenethidine, N, N- dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-amnosacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol , p-aminophenol, 2,3-xylidene, 2, 4-xylidene, 3,4-xylidene, 2,6-xylidene, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6- dichloraniline, 3,4-dichloroaniline, 3,5-dichlo aniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoatracene, o-ethylaniline, o-chloraniline, m-chloraniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, acetoacetic anilidine acids, trimethylphenylammonium bromide, 4,4'-diamino-3,3'-diethyl diphenylmethane, 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, these p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzene , 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'-chlorophene il) 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-phenisulfamoyl-2-methoxy-2-methyl-oxylamino-aniline 5-benzylsulfonylaniline, 2-phenoxysul onilaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3- methyl 4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4, 4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidinsulfon, 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'-dithiodi nilin, 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'-tetraaminodiphenylsulfone, 3,3', 4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methylenebis-o-toluidine, 4,4 '- ( p-phenyleneisopropylidene) -bis- (2,6-xylidene), 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-di minophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, methanilic 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-toluylene diamine, 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'-diaminostylben-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, n naphthionate n atria, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2,3-dichlorantraquinoni, etc.

The aromatic isocyanate compound of formula (p) includes 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, o-phenylenediisocyanate and so on. Of these, toluene diisocyanates are preferred, 2,4-toluene diisocyanate is most preferred.

The aromatic amine compound of formula (q) is not particularly limited provided that it has one or more amino groups directly bonded to one or more carbon atoms, respectively, of the benzene ring. In addition, the hydrogen atom (s) of the benzene ring may (may) be substituted with the remainder of the aromatic compound, the remainder of the aliphatic compound, the remainder of the heterocyclic compound, the hydroxyl group, nitro group, nitrile group, carbamoyl group, sulfamoyl group, carboxyl group, nitroso group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group or halogen atom. The aromatic amine compound of formula (q) includes, for example, aromatic monoamines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenethidine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, carboxy substituted anilines (e.g. p-aminobenzoic acid), hydroxyl substituted anilines (e.g. o-aminophenol, m-aminophenol, p-aminophenol and 2-amino-4- chlorophenol), 2,3-xylidene, 2,4-xylidene, 3,4-xylidene, 2,6-xylidene, nitrile substituted anilines (e.g. 4-aminobenzonitrile), anthranyls hydrochloric acid, p-cresidine, halogen-substituted anilines (e.g. 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloranilin, 2,4,5-trichloroaniline, o-chloroaniline, m- chloraniline and p-chloroaniline), α-naphthylamine, aminoatracene, o-ethylaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, 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, carbamoylanilines (e.g. 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 and 2-methoxy-5 - [N- (2'-chlorophenyl) carbamoyl] aniline), 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, sulfamoylanilines (e.g. 4-sulfamoylaniline , 3-sulfamoylaniline, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline and 2,5-dimetho xy-4-N-phenylsulfamoylaniline), 2- (N-ethyl-N-phenylaminocylphosphonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfonyl-2-phenylsulfonylaniliniline, 2-methoxy-5-benzylsulfonylanilonilinilin (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, nitro substituted anilines (e.g. o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chlorine -2-nitroaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine and 2-amino-5-nitrobenzonitrile), sulfanilic acid ota, methanilic 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-3-bromo-5-nitrobenzonitrile and so on; aromatic monoamines having one or more substituents, including carboxyl group, nitroso group, hydroxy amino group, nitro amino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group and so on; and aromatic diamines such as 4,4'-diamino-3,3'-diethyl diphenylmethane, 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, o-tolidinsulfone, 2,4'-diamino biphenyl, 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'-ethylenedian lin, 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 and so on. Of these, monoamines are preferably used, aniline or aniline derivatives are particularly preferred.

The isocyanate compound of formula (r) is not particularly limited provided that it has two or more isocyanate groups attached to carbon atoms, respectively. This compound includes, for example, p-phenylenediisocyanate, m-phenylenediisocyanate, o-phenylenediisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethanediisocyanate, o-tolidine, diisocyanate diphenyl ether, 1,5-naphthylenediisocyanate, dianisidinediisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate triethane isothiocyanate triethane, triethosphate, triethane 4.4 ', 4' '- triisocyanato-2,5-dimethoxytrophenylamine, 4.4 ’, 4’ ’- triisocyanatotriphenylamine, m-xylylenediisocyanate, lysinediisocyanate, dimeric acid diisocyanate, isopropylidene bis-4-cyclohexyl isocyanate, dicyclohexylmethanediisocyanate and methylcyclohexanediisocyanate.

As the isocyanate compound of formula (r), diisocyanate dimers such as N, N ’- (4,4’-dimethyl-3,3′-diphenyldiisocyanato) urethodion (Desmodule) can also be used

TT, trademark), toluene diisocyanate dimer; and diisocyanate trimers, such as 4.4 ’, 4’ ’- trimethyl-3.3’, 3 ’’ - triisocyanato-2,4,6-triphenyl cyanurate. You can also use an aqueous isocyanate adduct selected from toluene diisocyanate, diphenylmethanediisocyanate and the like, such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; polyol adducts such as trimethylolpropane adducts selected from toluene diisocyanate (Desmodule L and Coronate L, trade name); and amine adducts. Compounds having two or more isocyanate groups can also be used, including isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patent JP-A-10-76757 and the detailed description of Japanese patent JP-A-10-95171 (the contents of these links are given here as a reference).

Of the above, as examples, isocyanate compounds, aromatic isocyanates having isocyanate groups attached to a benzene ring are preferred. More preferred are p-phenylenediisocyanate, m-phenylenediisocyanate, o-phenylenediisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethanediisocyanate, o-tolidinediisocyanate, diphenyl ether diisocyanate, 1,5-di-phenyl diisocyanate (4,4'-dimethyl-3,3'-diphenyldiisocyanato) urethodion (Desmodule TT, trade name), 4.4 ', 4' '- trimethyl-3.3', 3 '' - triisocyanato-2.4, 6-triphenyl cyanurate, 1,3-bis (3-isocyanato-4-methylphenyl) urea and trimethylolpropane adducts selected from toluene diisocyanate (Desmodule L and Coronate L, com names). Particularly preferred examples of the isocyanate compound of formula (r) are toluene diisocyanates. Of the toluene diisocyanates, 2,4-toluene diisocyanate is preferred. In addition, in addition to 2,4-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, which are widely available on the market and are available at low cost, can also be used as isocyanate compounds of formula (r).

An amine compound of the general formula (s) is not particularly limited as long as it has two or more amino groups. This compound includes, for example, aromatic amines such as 4,4'-diamino-3,3'-diethyl diphenylmethane, 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 '-diam inobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4 , 4'-diaminobiphenyl, o-tolidinsulfone, 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- diaminopheni ) 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, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine and so on; heterocyclic amines such as guanamine, acetoguanamine, 2,4-diamino-6- [2'-methylimidazole- (1)] ethyl-s-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5 -triaminopyridine, bis (aminopropyl) piperazine and so on; and aliphatic amines such as methanediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,3-diamino-2-hydroxypropane, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine, N-methyl-3, 3'-iminobis (propylamine), hexamethylenediamine, bis (aminomethyl) cyclohexane, isophorondiamine, isopropylidenebis (aminocyclohexane), 4,4'-diaminodicyclohexylmethane, xylylenediamine and so on. Of the above examples, aromatic amines are preferred, and aniline derivatives having at least two amino groups and which are represented by the following formula (VIII) are particularly preferred:

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

and Y ₁ represents any of —SO ₂ -, —O—, - (S) _n -, - (CH ₂ ) _n -, —CO -, - CONH-, -NH-, -CH (COOR ₁ ) - , -C (CF ₃ ) ₂ -, -CR ₂ R ₃ - and a group represented by any of formulas (a)

or absent, each of R ₁ , R ₂ and R ₃ represents an alkyl group, and n is 1 or 2.

The amine compound of general formula (t) includes aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenethidine, 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-xylidene, 2,4-xylidene, 3,4-xylidene, 2,6-xylidene, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloraniline, 3,4 -dichloraniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoatracene, o-ethylaniline, o-chloraniline, m-chloraniline, p-chloraniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl- o-toluidine, acetoacetic acid anilide, trimethylphenylammonium bromide, 4,4'-diamino-3,3'-diethyl diphenylmethane, 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-am nobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminobenzoate, 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-methox i-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-diethylsulfamoyloylaniline, -4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylanyl in, 2-phenoxy-sulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidinsulfone, 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'-thiodianil n, 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-aminophen xi) 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-xylidene), 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-nitrobenzonitri l, methol, 2,4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, methanilic 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-toluylene diamine, 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'-diaminostylben-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediam N, sodium naftionat, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diaminoanthraquinone, 1,4-diamino-2,3-dichloroanthraquinone and so on; and heterocyclic amines such as 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2,4-diamino-6- [2 '-methylimidazole- (1)] ethyl-s-triazine, 2, 3-diaminopyridine, 1, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl ) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine and so on. Of these, aromatic monoamines are most preferably used.

The alcohol compound of general formula (u) is not particularly limited, provided that it is a polyol compound having two or more OH groups.

The alcohol compound includes diols such as 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-nonanediol, neopentyl glycol, methylpentanediol and so on; aliphatic polyols such as glycerin, castor oil, trimethylol propane, trimethylol ethane, hexantriol, pentaerythritol, α-methyl glucoside, sorbitol, sucrose and so on; polyols such as polyethylene glycols, polypropylene glycols, polytetramethylene glycols, adipate polyols, epoxy modified polyols, polyester esters of polyols, polycarbonate polyols, polycaprolactan diols, amine-modified polyols, polyester polyols obtained by the addition of one of ethylene oxide or a mixture of two or propylene oxide) to one of or a mixture of two or more polyols (e.g. glycerol and propylene glycol), acrylic polyols, fluorinated polyols, polybutanediene polyols, polyhydroxypolyols, polyols derived from castor oil, polymer polyols, halogen-containing polyols, phosphorus-containing polyols and so on; and alkanolamines such as N-alkyldiethanolamines, N-alkyldiisopropanolamines, triethanolamine, triisopropanolamine, N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N', N'-tetrakis (2-hydroxypropyl ) ethylenediamine and so on. Of these, diols, aliphatic polyols, alkanolamines and polyols having a molecular weight of 2000 or less are preferably used.

An amine compound of general formula (XVII) includes, for example, aromatic diamines such as 4,4'-diamino-3,3'-diethyl diphenylmethane, 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'-d aminobiphenyl, o-tolidinsulfone, 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'-diamino-diphenyl 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'-diaminodiphene lamin, 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 and so on. Amine compounds of the general formula (XVII) in which γ ₁ is a sulfonyl group or a methylene group are preferred.

To obtain each urea-urethane compound according to aspects of the present invention, the first to fourth isocyanates and the corresponding reagents are mixed to react in an organic solvent or without solvent, after which filtration, crystallization, and desolvation are carried out to collect crystals, thereby obtaining the desired compound. The interaction can be carried out using a method in which a substance having two or more groups in a molecule is used in large excess and another substance interacting with the groups is added in small portions. When using this method, it is possible that only one of two or more groups interacts.

In addition, it is preferable to thoroughly mix the system to obtain a sufficient dispersion of the added substance immediately after addition. The foregoing refers to any of the urea-urethane compounds shown here as examples. The interaction method is not limited to the aforementioned method, and any method can be used provided that the same result as above is obtained. As one of the reagents, one or more compounds may be used depending on the purpose. As the solvent, any solvent may be used provided that it does not interact with the isocyanate group and the functional groups of the reagents. The solvent includes, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons and ketones. Especially preferred are methyl ethyl ketone, toluene and the like, which dissolve isocyanate and in which the reaction products have low solubility. The reaction product obtained by the above reaction is not always a single compound, in some cases it is obtained as a mixture of compounds of different position substituents.

Specific examples of the urea-urethane compounds of the aspects of the invention, starting from the first and ending with the fourth, are the following compounds ((S-1) to (S-70)).

Each urea-urethane composition in accordance with aspects of the fifth to twelfth embodiments of the present invention and urea-urethane compositions obtained by the production method according to aspects of the invention from thirteenth to twentieth preferably include 50 wt.% Or more, more preferably 60 wt.% Or more, even more preferably 70 mass% or more of a urea-urethane compound having in the molecule at least one urethane group (-NHCOO-group) and at least one urea group (-NHCONH-group) with a total number o 2 to 10, and having a molecular weight of 5000 or less.

Such a urea-urethane composition can be used in combination with a colorless or light-colored dye precursor substance in order to obtain a color-forming composition for a heat-sensitive recording substance or a pressure-sensitive recording substance. This color-forming composition is so effective that it is perfect for both color-forming capabilities and for storing the print.

The urea-urethane compound as the main component of the urea-urethane composition has at least one urea group and at least one urethane group in the molecule. The urea group and the urethane group are adjacent relative to each other, connected through at least one residue of the compound (such a structural fragment is hereinafter referred to as the urea-urethane structural fragment). The total number of urethane group (s) and urea group (s) is not more than 10 and not less than 2, preferably not more than 10 and not less than 3, more preferably not more than 10 and not less than 4.

The ratio of the urethane (s) group (s) to the urea group (s) is preferably 1: 3-3: 1, more preferably 1: 2-2: 1, most preferably 1: 1. The molecular weight of the urea-urethane compounds is 5000 or less, preferably 2000 or less.

The content of the urea-urethane compound in each urea-urethane composition in accordance with aspects of the present invention from the fifth to the twentieth is equal to 50 wt.% Or more. Such a urea-urethane composition can be obtained using a relatively simple preparation method. On the other hand, it can exhibit excellent performance due to the high content of the urea-urethane compound, which can exhibit excellent color-forming properties, and storage characteristics that are required for the color-forming composition. In addition, either a single compound or a mixture of two or more compounds, including isomers, can be used as a urea-urethane compound.

In addition, a mixture of two or more compounds, including isomers, can be used as a urea-urethane compound in order to improve color-forming ability, storage characteristics, and the like.

On the other hand, the urea-urethane compound of the present invention may be suitably diluted with a substance that does not affect the action of the present invention. Such diluents include, for example, heat-melting substances, acid developers, amine compounds, isocyanate compounds, urea compounds, urethane compounds and the like, which are described herein above. Of these, urea compounds and urethane compounds are preferred which have a structure similar to the urea-urethane compound, since they improve sensitivity. In addition, compounds that are prepared by reacting a polyisocyanate compound with a hydroxy compound or an amino compound are preferred. Such diluents are preferably contained in the resulting dilution in a proportion of 0.0001 to 50% by weight relative to the total weight of the urea-urethane compound and diluent. To exhibit storage properties, the diluent content is more preferably 40 mass% or less, even more preferably 30 mass% or less. To improve sensitivity, the diluent content is more preferably 0.01 mass% or more, even more preferably 1 mass% or more. In some cases, such a diluent is obtained during the synthesis of a urea-urethane compound. When a diluent is added to improve sensitivity, it is preferable to add it during the synthesis reaction. For example, a urea-urethane composition containing a diluent and a urea-urethane compound having at least one urea group and at least one urethane group with a total number in the molecular structure of 2 to 10 and having a molecular a mass of 5000 or less, which is characterized by a diluent content in a proportion of 0.0001 to 50 mass%. The same effect was observed in the case of compositions in accordance with aspects of the present invention from the eighth to twelfth, and compositions obtained by the method of obtaining in accordance with aspects of the thirteenth to twentieth.

Each urea-urethane composition in accordance with aspects of the fifth to twenties of the present invention is preferably a colorless or light colored solid with a melting point from the point of view of use in a heat-sensitive recording substance. The melting point of the composition is preferably from 40 ° C. to 300 ° C., more preferably from 60 ° C. to 260 ° C.

As a method for producing any urea-urethane composition according to aspects five to twenty, it is preferable to use a method for forming one or more urethane groups from at least one isocyanate group of a polyisocyanate compound and a hydroxyl group of a hydroxy compound and then forming one or more urea groups from the remaining unreacted isocyanate groups (s) of the same polyisociant compound and amino groups (s) of the amino compound; or a method for forming one or more urea groups (groups) from at least one isocyanate group of a polyisocyanate compound and amino groups (s) of an amino compound and then forming one or more urethane (s) group (s) from the remaining unreacted isocyanate groups (s) of the same polyisocyanate compound and the hydroxyl group (s) of the hydroxy compound.

When one or more urethane groups are formed from a polyisocyanate compound and a hydroxy compound, the urea-urethane composition can be efficiently prepared using an polyisociate compound in an excess of the relative hydroxyl group (s) by attaching a polyisocyanate compound to the hydroxy compound in an amount of one molecule per hydroxyl a hydroxy compound group for reacting only one isocyanate group of the polyisocyanate compound, and leaving unreacted, to ayney least one isocyanate group, and then reacting the remaining unreacted isocyanate (second) group (s) with the amino compound to form one or more urea groups. In this case, it is preferable to obtain one or more urethane groups by reacting the polyisocyanate compound with the hydroxy compound such that the ratio of the number of moles of the polyisocyanate compound to the number of hydroxyl equivalents of the hydroxy compound and the ratio of the number of equivalents of the isocyanate group of the polyisocyanate compound to the number of hydroxyl equivalents hydroxy compounds became 1000 / 1-1 / 1.

When adding a hydroxy compound to a polyisocyanate compound, it is preferable to add the hydroxy compound in small portions so that the polyisocyanate compound is always in excess in the reaction system with respect to the hydroxyl (s) groups (e). Such an addition method is preferred, in particular when the reaction is carried out at a ratio of the number of moles of the polyisocyanate compound to the number of hydroxyl equivalents of the hydroxy compound of about 1/1, for example 5 / 1-1 / 2.

Similarly, when one or more urea groups are obtained from a polyisocyanate compound and an amino compound, the urea-urethane composition can be efficiently prepared using an excess amount of the polyisocyanate compound relative to the amino groups (s) by adding one molecule per polyisocyanate compound to the amino compound per amino group of the amino compound for the interaction of only one isocyanate group of the polyisocyanate compound and leaving at least one of the unreacted cyanate group, and then reacting the remaining unreacted isocyanate (second) group (s) with a hydroxy compound to form one or more urethane groups.

In this case, it is preferable to obtain one or more urea groups by reacting the polyisocyanate compound with an amino compound such that the ratio of the number of moles of the polyisocyanate compound to the number of amino equivalents of the amino compound and the ratio of the number of equivalents of the isocyanate group of the polyisocyanate compound to the number of amino equivalents of the amino compound it became 1000 / 1-1 / 1.

When adding the amino compound to the polyisocyanate compound, it is preferable to add the amino compound in small portions so that the polyisocyanate compound is always in excess in the reaction system with respect to the amino groups (e). This addition method is preferred, in particular when the reaction is carried out at a ratio of the number of moles of the polyisocyanate compound to the number of amino equivalents of the amino compound of about 1/1, for example 5 / 1-1 / 2.

In the method for producing any urea-urethane composition according to aspects five to twenty of the present invention, the reaction of the polyisocyanate compound and the hydroxy compound to form one or more urethane groups is preferably carried out without a solvent, adding either dropwise or pouring out the hydroxy compound, either without solvent or diluting the hydroxy compound with a solvent, or dispersing the hydroxy compound in a solvent, either continuously, or in portions, or into a diluted polyisocyanine Noe compound with a solvent or dispersed in a polyisocyanate compound in a solvent. Similarly, the interaction of a polyisocyanate compound with an amino compound to form one or more urea groups can be carried out without a solvent, adding either dropwise or pouring the amino compound, or without a solvent, or diluting the amino compound with a solvent, or dispersing the amino compound in a solvent, either continuously or in portions, or into a dilute polyisocyanate compound with a solvent, or into a dispersed polyisocyanate compound in a solvent.

The above preparation method, comprising adding the hydroxy compound or amino compound to the polyisocyanate compound in small portions, is preferred, in particular, in the following case: during the reaction to obtain the urea-urethane composition at the time when at least one isocyanate group in the polyisocyanate molecules the compound leaves, the other isocyanate group (s) reacts with the hydroxy compound or amino compound to produce one or more urethane groups or urea groups, respectively naturally. In addition, this production method is preferred when a hydroxy compound having two or more hydroxyl groups, or an amino compound having two or more amino groups, is reacted with a polyisocyanate compound having two or more isocyanate groups.

When carrying out the above reaction, it is preferable to thoroughly mix the system so that the hydroxy or amino compound added to the polyisocyanate is dropwise or poured immediately and adequately dispersed into the polyisocyanate. It is preferable to thoroughly mix the reaction system, for example, by adjusting the mixing speed in the reactor, selecting a mixing paddle or baffle.

It is preferable to carry out the interaction with the formation of one or more urethane groups and the interaction with the formation of one or more urea groups separately and sequentially. If they are carried out at the same time, then the content of the urea-urethane compound in the urea-urethane composition is undesirably reduced. Such a urethane group formation reaction and a urea group formation reaction are preferably carried out sequentially. In the method of the present invention, since separation and purification steps are not necessary during the preparation, the preparation can be simplified by carrying out two reaction steps in series.

In preparing any urea-urethane composition in accordance with aspects of the fifth to twentieth invention, when a polyisociate adduct with a hydroxy compound is used, which is an isocyanate already having one or more urethane groups in the molecule, then the urea-urethane composition can be obtained by reacting this adduct with an amino compound. In this case, it is preferable that one or more urea groups is formed by reacting an equivalent ratio of the isocyanate group and the amino group of 2 / 1-1 / 100, and removing the unreacted amino compound.

In the preparation of any urea-urethane composition according to aspects five to twenty of the present invention, when a polyisocyanate adduct with an amino compound is used that already contains one or more urea groups in the molecule, then the urea-urethane composition can be obtained by reacting this adduct with a hydroxy compound . In this case, it is preferable that one or more urethane groups form by reacting with an equivalent ratio of the isocyanate group and the hydroxy group of 2 / 1-1 / 100, and removing the unreacted hydroxy compound.

When a solvent is used in the reaction (s) to produce any urea-urethane composition according to aspects of the present invention from the fifth to the twentieth, the solvent is not specifically organic provided that it does not interact with an isocyanate group and the like. The solvent includes, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, ketones and phosphoric esters. Especially preferred are acetone, methyl ethyl ketone, toluene and the like, which dissolve the isocyanate and in which the reaction product has poor solubility. When a readily soluble isocyanate powder is required, phosphoric esters, in particular trimethyl phosphate, are preferred.

When such a solvent is used, the formation of one or more urethane groups and the formation of one or more urea groups is preferably carried out in the same solvent to facilitate reuse of the solvent, and the reaction is continuously carried out to form the urea group and the reaction to form the urethane group.

The reaction temperature at which the polyisocyanate reacts with a hydroxy compound and / or an amino compound to form one or more urethane groups and / or one or more urea groups is from 0 ° C to 300 ° C, preferably from 5 ° C to 200 ° C, more preferably from 10 ° C to 150 ° C. The reaction temperature is properly set depending on the selected polyisocyanate compound, hydroxy compound and amino compound. It is also possible to carry out the formation of the urethane group and the formation of the urea group at various temperatures suitable for such formations, respectively.

When the polyisocyanate is reacted with a hydroxy compound and / or an amino compound to form one or more urethane groups and / or one or more urea groups, a catalyst can be used. The catalyst includes, for example, tertiary amino compounds such as triethylamine, 1,4-diazabicyclo (2.2.2) octane, and so on; and organic acid salts such as dibutyltin dilaurate and so on. Typically, the concentration of the catalyst is from 1 to 10,000 ppm, preferably from 10 to 2,000 ppm, relative to the isocyanate compound. Among the above catalysts, tertiary amino compounds are most preferred.

A urea-urethane composition containing a urea-urethane compound having a plurality of urea-urethane structural fragments in a molecule may be a repeat of the steps of the preparation method of the present invention two or more times, using, for example, an aline compound having two or more amino groups and a hydroxy compound, having two or more hydroxyl groups. Since a sufficiently high yield can be achieved in each step in the reaction, the production method of the present invention makes it possible to relatively easily obtain a urea-urethane composition having high performance.

The polyisocyanate compound used in each aspect of the fifth to twentieth aspect of the present invention is not particularly limited provided that it has two or more isocyanate groups attached to carbon atoms, respectively. The polyisocyanate compound includes, for example, p-phenylenediisocyanate, m-phenylenediisocyanate, o-phenylenediisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, diisocyanate diphenyl ether, 1,5-naphthylenediisocyanate, dianisidinediisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate triethane isothiocyanate triethane, triethosphate, triethane 4.4 ', 4' '- triisocyanato-2,5-dimethoxy rifenilamin, 4,4 ', 4' '- triizotsianatotrifenilamin, m-xylylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexylisocyanate, dicyclohexylmethane diisocyanate and metiltsiklogeksandiizotsianat. Diisocyanate dimers such as N, N ’- (4,4’-dimethyl-3,3’-diphenyldiisocyanato) urethodion (Desmodule TT, trade name), toluene diisocyanate dimer can also be used as a polyisocyanate compound; and diisocyanate trimers, such as 4.4 ’, 4’ ’- trimethyl-3.3’, 3 ’’ - triisocyanato-2,4,6-triphenyl cyanurate. Can also be used aqueous adducts of isocyanates selected from toluene diisocyanate, diphenylmethanediisocyanate and the like, such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; polyol adducts such as trimethylolpropane adducts selected from toluene diisocyanate (Desmodule L and Coronate L, trade names); and amine adducts. Compounds having two or more isocyanate groups, including isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patent JP-A-10-76757 and the detailed description of Japanese patent JP-A-10-95171 (the contents of these links are hereby incorporated by reference). The above compounds may be used alone or in combination.

Among the above examples of compounds, preferred examples of a polyisocyanate compound are aromatic polyisocyanates having isocyanate groups attached to a benzene ring, such as p-phenylenediisocyanate, m-phenylenediisocyanate, o-phenylenediisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate , o-tolidinediisocyanate, diisocyanate diphenyl ether, 1,5-naphthylenediisocyanate, triphenylmethane triisocyanate, N, N '- (4,4'-dimethyl-3,3'-diphenyldiisocyanato) urethodion (Desmodule TT, trade name ), 4.4 ', 4' '- trimethyl-3.3', 3 '' - triisocyanato-2,4,6-triphenylcyanurate, 1,3-bis (3-isocyanato-4-methylphenyl) urea, trimethylolpropane adducts selected from toluene diisocyanate (Desmodule L and Coronate L, trade names) and so on. Particularly preferred examples of the polyisocyanate compound are toluene diisocyanates. Among the toluene diisocyanates, 2,4-toluene diisocyanate is preferred. In addition to 2,4-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate can also be used as polyisocyanate compounds, which are widely available on the market and are affordable.

As the hydroxy compound which reacts with the polyisocyanate compound to produce one or more urethane groups, phenolic compounds and alcohol compounds may be mentioned.

Phenolic compounds include, for example, phenol, cresol, xylene, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2, 2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) ac tat, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-methylphenyl sulfone, 3-chloro-4 -hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, -isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-isopropoxyphenylsulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dig droxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4- (2-hydroxy) phenyl ) sulfone, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'-chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2- bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4 - (gasoline hydroxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxyisalicylic acid, 4-n-butyloxyisalicylic acid, 3-n-pentyloxyisalicylic acid, 3-n-dodecyloxyisalicylic acid, 3-n-octanoyloxysalicylic acid, 4-p-octanoyloxysalicylic acid 4-n-octanoyloxycarbonylaminosalicylic acid.

The above examples of phenolic compounds, phenol, phenolic derivatives represented by the following formula (w), and diphenolic compounds represented by the following formula (XVI) are preferred.

where the hydrogen atom (s) of each benzene ring may (may) be substituted (s) by an alkyl group, cycloalkyl group, phenyl group, amide group, alkoxy group, nitro group, nitrile group, formyl group, dialkylamino group, methanesulfonyl group or OH group; and

where the hydrogen atom (s) of each benzene ring may (may) be substituted with a substituent, which preferably represents an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue, although the substituent may be a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, sulfamoyl group, carboxyl group, nitroso group, amino group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, with an ulphogroup or a halogen atom, each residue may have one or more substituents, δ represents a group selected from the group consisting of —SO ₂ -, —O—, - (S) _n -, - (CH ₂ ) _n -, —CO -, -CONH-, -NH-, -CH (COOR ₁ ) -, -C (CF ₃ ) ₂ - and-CR ₂ R ₃ - or absent, R ₁ , R ₂ and R ₃ independently represent an alkyl group and n equal to 1 or 2.

The term “aliphatic” as used in the fifth to twentieth aspects of the present invention includes the term “alicyclic”.

The term “aliphatic compound residue”, used in the fifth to twentieth aspects of the present invention, means a residue attached via the carbon atom of an aliphatic hydrocarbon moiety in the residue. The term “aromatic residue”, as used herein, means a residue attached via a carbon atom of an aromatic ring, such as a benzene ring in the residue. The term “heterocyclic compound residue” as used herein means a residue attached via the carbon atom of a heterocyclic ring in the residue.

Preferred examples of the substituent of the aliphatic compound residue, heterocyclic compound residue or aromatic compound residue are alkyl groups, cycloalkyl groups, phenyl group, amide group, alkoxyl groups, nitro group, nitrile group, halogen atom, formyl group, dialkylamino groups, toluenesulfonyl group and methanesulfonyl group.

As the alcohol compound, compounds are indicated having at least one OH group attached to the carbon atom of the aliphatic compound. Examples of the alcohol compound are the alcohols described in Solvent Handbook, Kodansha Scientific Co., Ltd., ninth edition (1989), pp. 327-420 and pp. 772-817. The alcohol compound includes, for example, aliphatic alcohols such as methanol, ethanol, propanol, isopropapol, n-butanol, isobutanol, ses-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, undecyldecyl tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl hydrated alcohol, isostearyl alcohol and so on; unsaturated aliphatic alcohols such as allyl alcohol, 2-methyl-2-propen-1-ol, crotyl alcohol, propargyl alcohol and so on; aliphatic alcohols having an aromatic residue attached to them, such as benzyl alcohol, cinnamyl alcohol and so on; aliphatic alcohols having a heterocyclic compound residue attached thereto, such as 2-pyridinomethanol, 3-pyridinomethanol, 4-pyridinomethanol, furfuryl alcohol and so on; halogenated aliphatic alcohols such as 2-chloroethanol, 1-chloro-3-hydroxypropane and so on; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, monopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, monopropyl ether, monoisopropyl diethylene glycol ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, monohexyl ether, diethylene glycol monophenyl ether, diethylene 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, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether dipropylene glycol, dipropylene glycol monobutyl ether, m noizobutilovy ether, dipropylene glycol monophenyl ether of dipropylene glycol and so on; diols such as 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-nonanediol, neopentyl glycol, methylpentanediol and so on; aliphatic polyols such as glycerin, castor oil, trimethylol propane, trimethylol ethane, hexantriol, pentaerythritol, α-methyl glucoside, sorbitol, sucrose and so on; polyols such as polyethylene glycols, polypropylene glycols, polytetramethylene glycols, adipate polyols, epoxy modified polyols, polyester esters of polyols, polycarbonate polyols, polycaprolactone diols, amine-modified polyols, polyester polyols obtained by the addition of one or two or one or two oxides ethylene oxide and propylene oxide) to one or a mixture of two or more polyhydric alcohols (glycerin and propylene glycol), acrylic polyols, fluorinated polyols, poly utadienovye polyols poligidroksipolioly, polyols derived from castor oil, polymer polyols, halogen-containing polyols, phosphorus-containing polyols and the like; and alkanolamines, such as N, N-dialkylethanolamines, N, N-dialkylisopropanolamines, N-alkyldiethanolamines, N-alkyldiisopropanolamines, triethanolamine, triisopropanolamine, N, N, N ', N'-tetrakis (2-hydroxyethyl, ethyl) N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine and so on.

The above examples are alcohol compounds, aliphatic alcohols having 10 or less carbon atoms, glycol ethers, diols, aliphatic polyols, polyols having a molecular weight of 2000 or less, and alkanolamines are preferred.

The above-mentioned alcohol compounds may be used alone or in combination and the above-mentioned phenolic compounds may also be used alone or in combination.

As the amino compound which reacts with the polyisocyanate compound to produce one or more urea groups, any compound can be used provided that it has one or more amino groups attached to carbon atoms, respectively. An amino compound includes, for example, aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenethidine, 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-dichloraniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthyl min, aminoanthracene, o-ethylaniline, o-chloraniline, m-chloraniline, p-chloraniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-o- toluidine, acetoacetic acid anilide, trimethylphenylammonium bromide, 4,4'-diamino-3,3'-diethyl diphenylmethane, 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-aminobenz oat, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-amino-acetophenone, 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-phenylsulfamoyl-2-methyl-2-methoxy-2-oxylamino-aniline 5-benzylsulfonylaniline, 2-pheno sisulfonylaniline, 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'-dimegil-4,4'-diaminobiphenyl, 2,2'-dichloro-4, 4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidinsulfon, 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) b 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 '- (r-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, meth ol, 2,4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, methanilic 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-toluylene diamine, 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'-diaminostylben-2,2'-disulfonic acid, benzyl ethylaniline, 1,8-naphthalenediamine, naphtha sodium thionate, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diaminoantraquinone, 1,4-diamino-2,3-dichlorantraquinone and so on; amines of heterocyclic compounds such as 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2,4-diamino-6- [2 '-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine and so on; and aliphatic amines such as methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, 3-ethoxypropylamine, propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, tert-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4 -diaminobutane, cyclohexanomethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, hexamethylenediamine and so on.

In addition, of the above, as examples of amino compounds, aromatic amines are preferred, and aniline derivatives having at least one amino group and represented by the following formula (z) or (VIII) are particularly preferred:

where R ₁ and R ₂ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group;

or

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

and Y ₁ represents any group of —SO ₂ -, —O—, - (S) _n -, - (CH ₂ ) _n -, —CO—, —CONH—, —NH—, —CH (COOR ₁ ) -, -C (CF ₃ ) ₂ -, -CR ₂ R ₃ - and a group represented by any formula from formulas (a):

or absent, each R ₁ , R ₂ and R ₃ represents an alkyl group and n is 1 or 2.

Such amine compounds may be used alone or in combination.

The urea-urethane compound used as a developer in each aspect of the present invention, either twenty-first or twenty-second, refers to a compound having at least one urea group (-NHCONH group) and at least one urethane group (-NHCOO-group) in the molecule.

It was known that compounds having one or more urea groups have a color-developing effect, but they are not used in practice, since they have a low color intensity and have inappropriate storage stability. However, unexpectedly, a urea-urethane compound having at least one urea group and at least one urethane group in the molecule is an excellent developer of a colorless or light-colored dye precursor substance, and a color-forming composition comprising a urea-urethane compound, and a dye precursor and recording material obtained using a color-forming composition gives high color intensity and has excellent storage stability.

Although the mechanism by which such a urea-urethane compound exhibits an excellent color-developing effect is unknown, it is believed that the effect is caused by the interaction between the urea group (s) and the urethane group (s) in the molecule.

As the urea-urethane compound used as a developer in each of the aspects of the present invention, either twenty-first or twenty-second, any compound can be used provided that it has at least one urea group (-NHCONH group ), and at least one urethane group (-NHCOO group) in the molecule. The urea-urethane compound is preferably an aromatic compound or a heterocyclic compound. In addition, the urea-urethane compound is preferably a compound in which the residue of an aromatic compound or a residue of a heterocyclic compound is directly attached to each urea group (s) and urethane group (s). More preferably, in addition to the urea group (s) (-NHCONH group (s)) and the urethane group (s) (-NHCOO group (s)), one or more sulfonic acid groups (-SO ₂ ) are present in the molecule - groups), amide groups (—NHCO— groups) or isopropylidene groups (—C (CH ₃ ) ₂ —groups) not directly attached to the urea group (s).

The molecular weight of the urea-urethane compound is preferably 5000 or less, more preferably 2000 or less. The total amount of urea group (s) and urethane (s) group (s) in the urea-urethane compound is preferably 20 or less, more preferably 10 or less. The ratio of the urea group (s) to the urethane (s) group (s) in the molecular structure of the urea-urethane compound is preferably from 1: 3 to 3: 1, in particular from 1: 2 to 2: 1.

When the urea-urethane compound is used in a heat-sensitive recording material, it is preferably a compound that has a melting point. The melting point is preferably in the range from 40 ° C. to 500 ° C., in particular from 60 ° C. to 300 ° C.

A method for producing a urea-urethane compound used as a developer in each of the aspects of the present invention, either twenty-first or twenty-second, is not particularly limited provided that at least one urea group (—NHCONH group) is formed and at least one urethane group (-NHCOO- group). A method in which a urea-urethane compound is formed by reacting an isocyanate compound with a compound containing an OH group and an amine compound is preferred since it is lighter.

In more detail, in the case of the urea-urethane compound used as a developer of the present invention, an isocyanate having at least two isocyanate groups is used as a starting product, and one or more urethane groups are formed by the interaction of all isocyanate groups, except at least one, with a compound containing an OH group, after which one or more urea groups can be formed by reacting the remaining (is) isocyanate group (s) with an amine compound iem. It is also possible to initially form one or more urea groups by reacting all isocyanate groups, except at least one, with an amine compound and then form one or more urethane groups by reacting the remaining (is) isocyanate group (s) with a compound containing OH group.

The starting isocyanate is not particularly limited provided that it has two or more isocyanate groups. The starting isocyanate includes, for example, p-phenylenediisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethanediisocyanate, o-tolidinediisocyanate, diphenyl ether 1,5-diisocyanate, naphthylenediisocyanate, dianisidinediisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethantriisocyanate, tis 4 '' 4 (tris -triisocyanato-2,5-dimethoxytriphenylamine, 4.4 ', 4' '- triisocyanatotriphenylamine, m ililendiizotsianat, lysine diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexylisocyanate, dicyclohexylmethane diisocyanate and metiltsiklogeksandiizotsianat. Diisocyanate dimers, such as N, N ’- (4,4’-dimethyl-3,3’-diphenyldiisocyanato) urethodion (Desmodule TT, trade name), toluene diisocyanate dimer can also be used as starting isocyanate; and diisocyanate trimers, such as 4.4 ’, 4’ ’- trimethyl-3.3’, 3 ’’ - triisocyanato-2,4,6-triphenyl cyanurate. Can also be used aqueous adducts of isocyanates selected from toluene diisocyanate, diphenylmethanediisocyanate and the like, such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; polyol adducts such as trimethylolpropane adduct toluene diisocyanate (Desmodule L, trade name); and amine adducts. Compounds having two or more isocyanate groups may also be used, including isocyanate compounds and isocyanate adducts described in the detailed description of Japanese Patent A-8-225445 and the detailed description of Japanese Patent A-8-250623.

Particularly preferred examples of the starting isocyanate are toluene diisocyanates. Among the toluene diisocyanates, 2,4-toluene diisocyanate is preferred. In addition to 2,4-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate can be used as starting isocyanate, which are widely available on the market and are available at a low price.

As an amine compound that interacts with the starting isocyanate of the urea-urethane compound as a developer to form one or more urea groups, any compound can be used provided that it has one or more amino groups. The amine compound includes, for example, aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenethidine, 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-dichl raniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloraniline, m-chloraniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, acetoacetic acid anilide, trimethylphenylammonium bromide, 4,4'-diamino-3,3'-diethyl diphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diamine , 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p- fenile diamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, mono-amino -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'-chlorof enyl) 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-chlorop-5-N-phenylcylphamoylaniline, 5-N, methoxy -diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-metho si-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2 , 2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidinsulfone, 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'-di minobiphenyl, 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-aminopheno xi) 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-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-toluid in, 2-amino-5-nitrobenzonitrile, methol, 2,4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, methanilic 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-toluylene diamine, 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'-diaminostylben-2,2'-disulfonic acid, benzyl ethylaniline, 1,8-naphthalenediamine, sodium naphthionate, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2,3-dichlorantraquinone and so on; heterocyclic amine compounds such as 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2, 4-diamino-6- [2 '-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine and so on; and aliphatic amines such as methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, 3-ethoxypropylamine, propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, tert-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4 -diaminobutane, cyclohexanomethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, hexamethylenediamine and so on.

Among the above-mentioned, as an example, amine compounds, aniline derivatives having at least one amino group and represented by the following formula (VIII) are particularly preferred:

where r ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group, X ₁ and X ₂ independently represent an amino group or a group represented by the formula (b):

and Y ₁ represents any group from —SO ₂ -, —O—, - (S) _n -, - (CH ₂ ) _n -, —CO—, —CONH— and a group represented by any formula from formulas (a) :

or absent and n is 1 or 2.

As a compound containing an OH group that reacts with an isocyanate to form one or more urethane groups, any compound can be used provided that it contains one or more OH groups. A compound containing an OH group includes, for example, phenols such as phenol, cresol, xylene, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2- allyl phenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2- bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, butyl bis ( 4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'- methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl -4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-isopropoxyphenylsulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3- methylphenyl) sulfide, bis (4- (2-hydroxy) phenyl) sulfone, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, ( 4'-chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3 -hydroxyphthalate, stearyl gallate, lauryl gallate, methyl g allate, 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxyisalicylic acid, 4-n-butyloxyisalicylic acid, 4-n-pentyloxyisalicylic acid, 3-n-dodecyloxyisalicylic acid, 3-n-n-oxyloxytasalicylic acid acid, 4-n-octyloxycarbonylaminosalicylic acid, 4-n-octanyloxycarbonylaminosalicylic acid, and so on. However, phenols, as such having an amino group, are not desirable. Since the amino group is more reactive with respect to the isocyanate group than the OH group, the amino group interacts with the isocyanate group before the OH group, which makes it difficult to obtain the desired compound in some cases.

A compound containing an OH group also includes alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, 2- pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methylcelloblozole, butylcellobolve, methylcarbitol, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinomethanol, phenylcelloblozole, furfuryl alcohol cyclohexylmethanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin, glycerol and so on her; polyester-type polyols such as polypropylene glycols, polytetramethylene glycol ether, adipate polyols, epoxy-modified polyols, polyester polyols, polycarbonate polyols, polycaprolactone diols, phenolic polyols, amine-modified polyols and so on; and polyols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexane glycol, 1 , 9-nonanediol, acrylic polyols, fluorocarbon polyols, polybutanediene polyols, polyhydroxypolyols, trimethylolpropane, trimethyloletane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, polyol ethylene polyols, polyethylene polyols, polyethylene polyols, polyethylene polyols, polyethylene polyols, polyethylene polyols, polyethylene polyols, polyethylene polyols, polyethylene polyols, polyolens, methylgluco id, sorbitol, sucrose, and so on.

The urea-urethane compound used as a developer in each aspect of the present invention, either twenty-first or twenty-second, is preferably a urea-urethane compound having a molecular structure in which the number of urea groups (A) and the number of urethane groups (B ) satisfy the following numerical formula:

10≥ (A + B) ≥ 3

where each A and B is an integer of 1 or more.

A urea-urethane compound in which the number of urea groups (A) and the number of urethane groups (B) satisfy the numerical formula 10≥ (A + B) ≥ 3 (where each A and B is an integer of 1 or more), is a compound, having a molecular structure in which at least one urea group (-NHCONH-group) and at least one urethane group (-NHCOO-group) with a total number of not more than 10 and not less than 3 are present.

Such a connection has not been described and is completely new. This new compound is used in the case of recording materials that use recording energy, such as heat, pressure or the like.

A method of producing a urea-urethane compound in which the number of urea groups (A) and the number of urethane groups (B) satisfy the numerical formula 10≥ (A + B) ≥ 3 (where each A and B is an integer of 1 or more), specifically not limited, provided that at least one urea group (-NHCONH group) and at least one urethane group (-NHCOOH group) are formed with a total number of from 3 to 10. A method in which urea-urethane the compound is obtained by reacting an isocyanate compound with a compound containing an OH group and amine soy dignity is preferred because of its simplicity.

In more detail, as a urea-urethane compound used as a developer in each aspect of the present invention, either in the twenty-first or in the twenty-second, a urea-urethane compound having at least one urea group and, at least one urethane group with a total number of at least 3, for example, when using an isocyanate having at least two isocyanate groups as the starting material, which interacts with all isocyanate groups except at least one, with a compound containing an OH group, with the formation of one or more urethane groups, and then interacting with the remaining isocyanate groups of the two molecules of the formed urethane compound with each other when using water with their addition to each other.

In addition, a urea-urethane compound having at least one urea group and at least one urethane group with a total number of at least 3 can be obtained, for example, using isocyanate having at least two isocyanate groups, as a starting material, interacting with all isocyanate groups, with the exception of at least one, with a compound containing an OH group, to obtain one or more urethane groups, interacting with the remaining isocyanate group (s) (s) with an amine compound having two or more amino groups, with the formation of one or more urea groups and interacting with the remaining amino group (s) with the isocyanate compound.

In addition, a urea-urethane compound having at least one urea group and at least one urethane group with a total number of at least 3 can also be obtained by the reaction of all isocyanate groups, with the exception of at least one with an amine compound, first with the formation of one or more urea groups, by reacting the remaining isocyanate group (s) with a compound containing two or more OH groups, to obtain one or more urethane groups, and then reacting Acquiring compound with an isocyanate compound. In this case, a urea-urethane compound having at least one urea group and at least one urethane group, with a total number of 3-10, can be obtained using an isocyanate compound having two or more isocyanate groups, as isocyanates, which ultimately react, and repeating the procedure for reacting the remaining isocyanate (s) group (s) with a compound containing two or more OH groups, or with an amino compound having two or more amino groups.

The starting isocyanate is not specifically organic, provided that it has two or more isocyanate groups. The starting isocyanate includes, for example, p-phenylenediisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethanediisocyanate, o-tolidinediisocyanate, diphenyl ether 1,5-diisocyanate, naphthylene diisocyanate, dianisidinediisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorondiisocyanate, triphenylmethantriisocyanate, tis 4 ', 4 (tris '-triisocyanato-2,5-dimethoxytriphenylamine, 4.4', 4 '' - triisocyanatotriphenylamine, m silylenediisocyanate, lysinediisocyanate, dimeric acid diisocyanate, isopropylidene bis-4-cyclohexyl isocyanate, dicyclohexyl methanediisocyanate and methylcyclohexanediisocyanate.

Diisocyanate dimers such as N, N ’- (4,4’-dimethyl-3,3’-diphenyldiisocyanato) urethodione (Desmodule TT, trade name), toluene diisocyanate dimer can also be used as the starting isocyanate; and diisocyanate trimers, such as 4.4 ’, 4’ ’- trimethyl-3.3’, 3 ’’ - triisocyanato-2, 4, 6-triphenyl cyanurate. Can also be used aqueous adducts of isocyanates selected from toluene diisocyanate, diphenylmethanediisocyanate and the like, such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; polyol adducts such as trimethylolpropane adduct of toluene diisocyanate (Desmodule L, trade name); and amine adducts. Compounds having two or more isocyanate groups can also be used, including isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patent JP-A-10-76757 and the detailed description of Japanese patent JP-A-10-95171 (the contents of these links are hereby incorporated by reference).

Particularly preferred examples of the starting isocyanate are toluene diisocyanates. Among the toluene diisocyanates, 2,4-toluene diisocyanate is preferred. In addition to 2,4-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, which are widely available on the market and are available at a low price, can also be used as the starting polyisocyanate.

Mixtures of these toluene diisocyanate isomers are liquid at ordinary temperatures.

As the amine compound that reacts with the parent isocyanate to form a urea-urethane compound to form one or more urea groups, any compound can be used provided that it has one or more amino groups. The amine compound includes, for example, aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenethidine, 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-dichl raniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloraniline, m-chloraniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, acetoacetic acid anilide, trimethylphenylammonium bromide, 4,4'-diamino-3,3'-diethyl diphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diamine , 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p- fenile diamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, mono-amino -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'-chlorof enyl) 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-chlorop-5-N-phenylcyclamoyloaniline, 5-m-2 -diethylsulfamoylaniline, 2,5-dimethoxy-4-phenylsulfamoylaniline, 2-labels i-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2 , 2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidinsulfone, 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'-dia inobiphenyl, 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-aminophenol si) 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-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-toluidi n, 2-amino-5-nitrobenzonitrile, methol, 2,4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, methanilic 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'-diaminostylben-2,2'-disulfonic acid, benzyl ilanilin, 1,8-naftalendiamin, naftionat sodium, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diaminoanthraquinone, 1,4-diamino-2,3-dichloroanthraquinone and so on; heterocyclic amine compounds such as 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2,4-diamino-6- (2 '-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine , bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine and so on; and aliphatic amines such as methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine n, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, tert-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanomethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethyl-2-amine -propanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylene riamine, hexamethylenediamine and so on.

Among the above examples of amine compounds, aniline derivatives having at least one amino group and represented by the following formula (VIII) are particularly preferred:

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

and Y ₁ represents any group from —SO ₂ -, —O—, - (S) _n -, - (CH ₂ ) _n -, —CO—, —CONH— and a group represented by any of formulas (a):

or absent and n is 1 or 2.

As a compound containing an OH group that reacts with an isocyanate to form one or more urethane groups, any compound can be used provided that it contains one or more OH groups. A compound containing an OH group includes, for example, phenols such as phenol, cresol, xylene, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2- allyl phenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2- bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, r'-biphenol, 4-cumylphenol, butyl bis ( 4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'- methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl -4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-isopropoxyphenylsulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether p, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3- methylphenyl) sulfide, bis (4- (2-hydroxy) phenyl) sulfone, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, ( 4'-chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3 -hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gall at, 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-p-octyloxy-salicylic acid, 4-n-butyloxy-salicylic acid, 4-n-pentyloxy-salicylic acid, 3-n-dodecyloxy-salicylic acid, 3-n-octalicylocyl salicylic acid acid, 4-n-octyloxycarbonylaminosalicylic acid, 4-n-octanyloxycarbonylaminosalicylic acid, and so on. However, as such, phenols that have an amino group are undesirable. Since the amino group is more reactive with respect to the isocyanate group than the OH group, the amino group interacts with the isocyanate group before the OH group, thereby making it difficult to obtain the desired compound in some cases. Compounds containing an OH group also include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isoheptanol, 2-ethyl-1-hexanol, 1-decanol, 2- pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methylcelloblozole, butylcellobolve, methylcarbitol, allyl alcohol, 2-methyl-2-propep-1-ol, benzyl alcohol, 4-pyridinomethanol, phenylcelloblozole, furfuryl alcohol cyclohexylmethanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin, glycerol and so on her; polyester type polyols such as polypropylene glycols, polytetramethylene ether glycols, adipate derivatives polyols, epoxy modified polyols, polyester ethers polyols, polycarbonate polyols, polycaprolactone diols, phenolic polyols, amine-modified polyols and so on; and polyols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexane glycol, 1 , 9-nonanediol, acrylic polyols, fluorocarbonate polyols, polybutadiene polyols, polyhydroxypolyols, trimethylolpropane, trimethylol ethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, polyethylene polyols, polyethylene polyols, polyethylene polyols, polyethylene polyols methyl glucose Zid, sorbitol, sucrose, etc.

As the urea-urethane compound used as a developer in each aspect of the present invention, either the twenty-first or twenty-second urea-urethane compounds represented by any of the following general formulas (I) to (VII) are also preferred:

where X and Z independently represent a residue of an aromatic compound, a residue of a heterocyclic compound or a residue of an aliphatic compound, each residue may have one or more substituents, and Y ₀ represents a group selected from the group consisting of a tolylene group, a xylylene group, a naphthylene group, a hexamethylene group and -φ —CH ₂ —φ —group, where —φ — represents a phenylene group;

where X and Y independently represent a residue of an aromatic compound, a residue of a heterocyclic compound or a residue of an aliphatic compound, and each residue may have one or more substituents;

where X and Y independently represent a residue of an aromatic compound, a residue of a heterocyclic compound or a residue of an aliphatic compound, α is a residue having a valency of 2 or more, n is an integer of 2 or more, and each residue may have one or more substituents;

where Z and Y independently represent a residue of an aromatic compound, a residue of a heterocyclic compound or a residue of an aliphatic compound, β is a residue having a valency of 2 or more, n is an integer of 2 or more, and each residue may have one or more substituents;

where the hydrogen atom (s) of each benzene ring may (may) be substituted (s) with a substituent, which preferably represents a residue of an aromatic compound, a residue of an aliphatic compound or a residue of a heterocyclic compound, although the substituent may be a nitro group, hydroxyl group, carboxyl group, nitroso group, nitrile a group, a carbamoyl group, a ureido group, an isocyanate group, a mercotapro group, a sulfo group, a sulfamoyl group or a halogen atom, each residue may have one or several substituents, γ represents a group selected from the group consisting of —SO ₂ -, —O—, - (S) _n -, - (CH ₂ ) _n -, —CO—, —CONH— and any group represented by the formulas (a);

or absent and n is 1 or 2;

где атом(ы) водорода каждого бензольного кольца может(могут) быть замещен(ы) заместителем, который предпочтительно представляет остаток ароматического соединения, остаток алифатического соединения или остаток гетероциклического соединения, хотя заместитель может быть гидроксильной группой, нитрогруппой, нитрильной группой, карбамоильной группой, сульфамоильной группой, карбоксильной группой, нитрозогруппой, аминогруппой, оксиаминогруппой, нитроаминогруппой, гидразиногруппой, уреидогруппой, изоцианатной группой, меркаптогруппой, сульфогруппой или атомом галогена, каждый остаток может иметь один или несколько заместителей, δ представляет собой группу, выбранную из группы, включающей -SO₂-, -О-, -(S)n-, -(СН₂)_n-, -СО-, -CONH-, -NH-, -CH(COOR₁)-, -С(СF₃)₂- и -СR₂R₃- или отсутствует, каждый из R₁, R₂ и R₃ представляет собой алкильную группу, и n равно 1 или 2; и

where the hydrogen atom (s) of each benzene ring may (may) be substituted with a substituent, which preferably represents the residue of an aromatic compound, the residue of an aliphatic compound or the residue of a heterocyclic compound, although the substituent may be a hydroxyl group, nitro group, nitrile group, carbamoyl group, sulfamoyl group, carboxyl group, nitroso group, amino group, hydroxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, with an ulphogroup or a halogen atom, each residue may have one or more substituents, δ represents a group selected from the group consisting of -SO ₂ -, -O-, - (S) n-, - (CH ₂ ) _n -, -CO -, -CONH-, -NH-, -CH (COOR ₁ ) -, -C (CF ₃ ) ₂ - and-CR ₂ R ₃ - or is absent, each of R ₁ , R ₂ and R ₃ represents an alkyl group , and n is 1 or 2; and

where X, Y and Z independently represent a residue of an aromatic compound, a residue of a heterocyclic compound or a residue of an aliphatic compound, each residue may have one or more substituents, and each of X, Y and Z preferably represents a residue of an aromatic compound or a residue of a heterocyclic compound.

The urea-urethane compounds of formulas (I) - (VII) are also completely new. These new compounds are used in the case of recording materials that use recording energy, such as heat, pressure or the like.

A method for producing a urea-urethane compound of formula (I), which is used in each of the aspects of the present invention, is either twenty-first or twenty-second, is not limited. This compound can be obtained, for example, by reacting a compound containing an OH group of the following general formula (IX) with an isocyanate compound of the following general formula (X) and an amine compound of the following general formula (XI) in accordance with, for example, reaction formula (A) ) presented below:

where X and Z independently represent a residue of an aromatic compound, a residue of a heterocyclic compound or a residue of an aliphatic compound, each residue may have one or more substituents, and Y ₀ represents a group selected from the group consisting of a tolylene group, a xylylene group, a naphthylene group, a hexamethylene group and -φ —CH ₂ —φ is a group, where -φ is a phenylene group.

The term “aliphatic”, as used herein, includes the term “alicyclic”.

A method for producing a urea-urethane compound of the formula (II) used in each of the aspects of the present invention, either twenty-first or twenty-second, is not limited. This compound can be obtained, for example, by reacting a compound containing an OH group of general formula (IX) with an isocyanate compound of the following general formula (XII) and water in accordance with, for example, reaction formula (B) shown below:

where Y is a residue of an aromatic compound, a residue of a heterocyclic compound or a residue of an aliphatic compound, and each residue may have one or more substituents.

The method for producing the urea-urethane compound of formula (III) used in each of the aspects of the present invention is either twenty-first or twenty-second, is not limited. This compound can be obtained, for example, by reacting a compound containing an OH group of general formula (IX) with an isocyanate compound of general formula (XII) and an amine compound of the following general formula (XIII) in accordance with, for example, reaction formula (C) or (D) presented below:

where α is a residue having a valency of 2 or more, and n is an integer of 2 or more.

The method for producing the urea-urethane compound of formula (IV) used in each of the aspects of the present invention is either twenty-first or twenty-second is not limited. This compound can be obtained, for example, by reacting an amine compound of the general formula (XI) with an isocyanate compound of the general formula (XII) and a compound containing an OH group of the following general formula (XIV) in accordance with, for example, reaction formula (E) or (F) presented below:

where β is a residue having a valency of 2 or more, and n is an integer of 2 or more.

The compounds of general formulas (IX) - (XIV), which are described in more detail below, can be used to obtain the urea-urethane compounds of formulas (I) - (IV) above.

A compound containing an OH group of general formula (IX) is not particularly limited as long as it has one or more OH groups. This compound includes, for example, monophenols such as phenol, cresol, xylene, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4- indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 4-phenylphenol, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 4-isopropylphenyl- 4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-from propropoxy diphenyl sulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'-chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydroxybenzoate ), hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4 -n-pentyloxyisalicylic acid, 3-n-dodecyloxyisalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid one 4-n-oktanoiloksikarbonilaminosalitsilovaya acid and so on. The compound of general formula (IX) also includes diphenols such as 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2- bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, 4,4'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4 -hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, bis (2-allyl-4-hydroxyphenyl) su laphone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4- hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide and so on. However, essentially compounds containing an OH group that have an amino group are undesirable. When an amino group is present together with an OH group (s), the amino group is more reactive with respect to the isocyanate group than the OH group and therefore the amino group interacts with the isocyanate group before the OH group, thereby making it difficult to obtain the desired compound in some cases. The compound of general formula (IX) also includes monohydric alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1- decanol, 2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methylcellobolzol, butylcellobolzol, methylcarbitol, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinomethanol, phenylcelloburzole, alcohol, cyclohexanol, cyclohexylmethanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin, glyc erol and so on. Polyester-type polyols such as polypropylene glycols, polytetramethylene ether glycols, adipate derivatives of polyols, epoxy modified polyols, polyester ethers of polyols, polycarbonate polyols, polycaprolactone diols, phenolic polyols, amine-modified polyols can also be used as compounds of general formula (IX); and polyols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexane glycol, 1 , 9-nonanediol, acrylic polyols, fluorocarbon polyols, polybutadiene polyols, polyhydroxypolyols, trimethylolpropane, trimethylol ethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, polyethylene polyenesols, ethylene polyenesols, methyl polyenesols, polyethylene polyols, polyethylene polyols, methyl glucose d, sorbitol, sucrose, and so on. Of these, monophenols are preferred.

The isocyanate compound of general formula (X) includes 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, m-xylylene diisocyanate and so on. Of these, toluene diisocyanates are preferred.

An isocyanate compound of general formula (XII) is not particularly limited provided that it has two or more isocyanate groups. This compound includes, for example, p-phenylenediisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethanediisocyanate, o-tolidinediisocyanate, 1,5-naphthylene diisocyanate, dianiside 9-ethylcarbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethanediisocyanate, hexamethylenediisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanato) thiophosphate, 4,4 ', 4', 4 ' -2,5-dimethoxytriphenylamine, 4.4 ', 4' '- triisocyanatotriphenylamine, m-xylylene diisocyanate, lysindiisocia atm, dimer acid diisocyanate, isopropylidene bis-4-cyclohexylisocyanate, dicyclohexylmethane diisocyanate and metiltsiklogeksandiizotsianat. Diisocyanate dimers such as N, N ′ - (4,4′-dimethyl-3,3′-diphenyldiisocyanato) urethodione (Desmodule TT, trade name), toluene diisocyanate dimer can also be used as isocyanate compounds of the general formula (XII) ; and diisocyanate trimers such as 4,4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,6-triphenylcyanurate. Aqueous adducts of isocyanates selected from toluene diisocyanate, diphenylmethane diisocyanate and the like can also be used. similar, such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; polyol adducts such as trimethylolpropane adduct toluene diisocyanate (Desmodule L, trade name); and amine adducts.

Compounds having two or more isocyanate groups can also be used, including isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patents JP-A-10-76757 and JP-A-10-95171. A particularly preferred example of an isocyanate compound of the general formula (XII) is toluene diisocyanate.

An amine compound of general formula (XI) is not particularly limited as long as it has one or more amino groups. This compound includes, for example, aromatic monoamines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline 3, 4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6- xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloranilin, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene , o-ethylaniline, o-chloroaniline, m-chl oraniline, p-chloroaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-amino , 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'-chl rphenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 2-methoxy-4- (N-benzoylamino) -5 -methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone, 2-chlorop-5-phenyl-phenyl methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxy-sulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinos lphonyl-4-methylaniline, o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o- nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, sulfanilic acid, methanilic 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-3-bromo-5-nitrobenzonitrile and so on; and aromatic diamines such as 4,4'-diamino-3,3'-diethyl diphenylmethane, 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, o-tolidinsulfone, 2,4'-diamino iphenyl, 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'-ethylenedian lin, 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 and so on. The amine compound of general formula (XI) also includes, for example, heterocyclic amine compounds such as 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε - caprolactam, acetoguanamine, 2,4-diamino-6- [2'-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1- amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine and so on; and aliphatic amines such as methylamine, ethylamine, stearylamine, allylamine, isopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, 3- (diethylamino) propylamine, 3- (dibutylamino) -butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanomethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-b -methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-amine -1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, hexamethylenediamine, and so on. Of these, it is preferable to use aromatic monoamines.

An amine compound of general formula (XIII) is not particularly limited provided that it has two or more amino groups. This compound includes, for example, aromatic amines such as 4,4'-diamino-3,3'-diethyl diphenylmethane, 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'-diamino iphenyl, o-tolidinsulfon, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3, 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4, 4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine and so on. Of the above as examples of amine compounds, aniline derivatives having at least two amino groups and represented by the following formula (VIII) are particularly preferred:

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

and Y ₁ represents any group from —SO ₂ -, —O—, - (S) n—, - (CH ₂ ) _n -, —CO—, —CONH— and a group represented by any of formulas (a):

or absent, and n is 1 or 2.

A compound containing an OH group of general formula (XIV) is not particularly limited as long as it has two or more OH groups. This compound includes, for example, diphenols such as 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, p, p ' biphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4 -gi roxyphenyl) sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'- dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3 methylphenyl) sulfide and so on. However, essentially diphenols that have an amino group are undesirable. Since the amino group has a greater reactivity with respect to the isocyanate group than the OH group, the amino group interacts with the isocyanate group before the OH group, thereby making it difficult to obtain the desired compound in some cases. A compound containing an OH group of general formula (XIV) also includes polyester-type polyols such as polypropylene glycols, polytetramethylene glycol ethers, adipate derivatives polyols, epoxy modified, polyester polyol ethers, polycarbonate polyols, polycaprolactone diols, phenol polyols, phenol polyols, etc; and polyols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexane glycol, 1 , 9-nonanediol, acrylic polyols, fluorocarbon polyols, polybutadiene polyols, polyhydroxypolyols, trimethylolpropane, trimethylol ethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, polyethylene polyenesols, ethylene polyenesols, methyl polyenesols, ethylene polyenesols, methyl polyenesols, polyethylene polyols, methyl glucose Zid, sorbitol, sucrose, and so on.

The method for producing the urea-urethane compound of formula (V) used in each of the aspects of the present invention is either twenty-first or twenty-second is not limited. This compound can be obtained, for example, by reacting a monophenol compound with an aromatic diisocyanate compound and a diamine compound of the following general formula (XV) in accordance with, for example, reaction formula (G) or (H) below:

where the hydrogen atom (s) of each benzene ring may (may) be substituted (s) with a substituent, which preferably represents a residue of an aromatic compound, a residue of an aliphatic compound or a residue of a heterocyclic compound, although the substituent may be a nitro group, hydroxyl group, carboxyl group, nitroso group, nitrile a group, a carbamoyl group, a ureido group, an isocyanate group, a mercotapro group, a sulfo group, a sulfamoyl group or a halogen atom, each residue may have one or several substituents, γ represents a group selected from the group consisting of -SO ₂ -, -O-, - (S) _n -, - (CH ₂ ) _n -, -CO-, -CONH- and any group represented by the formulas (a);

or absent, and n is 1 or 2.

The method for producing the urea-urethane compound of formula (VI) used in each of the aspects of the present invention, is either twenty-first or twenty-second, is not limited. This compound can be obtained, for example, by reacting an aniline derivative with an aromatic diisocyanate compound and a dihydroxy compound of the following general formula (XVI) in accordance with, for example, reaction formula (J) or (K) below:

where the hydrogen atom (s) of each benzene ring may (may) be substituted with a substituent, which preferably represents the residue of an aromatic compound, the residue of an aliphatic compound or the residue of a heterocyclic compound, although the substituent may be a hydroxyl group, nitro group, nitrile group, carbamoyl group, sulfamoyl group, carboxyl group, nitroso group, amino group, hydroxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, with an ulphogroup or a halogen atom, each residue may have one or more substituents, b represents a group selected from the group consisting of —SO ₂ -, —O—, - (S) _n -, - (CH ₂ ) _n -, —CO -, -CONH-, -NH-, -CH (COOR ₁ ) -, -C (CF ₃ ) ₂ - and-CR ₂ R ₃ - or absent, and n is 1 or 2.

The compounds used to prepare the urea-urethane compound of formula (V) or (VI) used in each aspect of the present invention, either the twenty-first or the twenty-second, are described in more detail below.

The phenolic compound used to synthesize the urea-urethane compound of the formula (V) is not particularly limited provided that it has one or more OH groups on the benzene ring. In addition, the hydrogen atom (s) of the benzene ring may be substituted with a substituent other than an OH group, i.e., an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a nitro group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group , an isocyanate group, a mercapto group, a sulfo group, a sulfamoyl group or a halogen atom.

Preferred examples of the phenolic compound are phenols, such as phenol, cresol, xylene, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol , 2-naphthol, nitro-substituted phenols (e.g. p-nitrophenol), halogen-substituted phenols (e.g. o-chlorophenol and p-chlorophenol), 4-phenylphenol, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4- hydroxyphenyl-4'-methylphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, 4-hydroxyp nyl-4 ^/ -benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-isopropoxyphenylsulfone, phenylsalicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'-chlorobenzyl) 3-hydroxyphthalate, 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxyisalicylic acid, 4-n-butyloxyisalicylic acid, 4-n-pentyloxyisalicylic acid, 3-n-dodecyloxyisalicylic acid octanoyloxyisalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, 4-n-octano yloxycarbonylaminosalicylic acid and so on. Compounds having one or more substituents, including a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group, a mercoton group, a sulfo group, a sulfamoyl group and so on can also be used as a phenolic compound. However, essentially phenols that have an amino group are undesirable. Since the amino group has a greater reactivity with respect to the isocyanate group than the OH group, the amino group interacts with the isocyanate group before the OH group, thereby making it difficult to obtain the desired compound in some cases.

The aromatic diisocyanate compound used to prepare the urea-urethane compound of formula (V) or (VI) is not particularly limited provided that it has two isocyanate groups attached to its benzene ring. The aromatic diisocyanate compound includes, for example, p-phenylenediisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate. Particularly preferred examples of the aromatic diisocyanate compound are toluene diisocyanates. Of the toluene diisocyanates, 2,4-toluene diisocyanate is preferred. In addition to 2,4-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, which are widely available on the market and are affordable, can also be used as aromatic diisocyanate. Mixtures of these toluene diisocyanate isomers are liquid at ordinary temperatures.

The diamine compound of general formula (XV) that is used to prepare the urea-urethane compound of formula (V) includes, for example, aromatic diamines such as 4,4'-diamino-3,3'-diethyl diphenylmethane, 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, o-tolidinsulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4 , 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3 , 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone 4.4 ' -diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'- dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine and so on .

The aniline derivative used to prepare the urea-urethane compound of formula (VI) is not particularly limited provided that the aniline compound has one or more amino groups on the benzene ring. In addition, the hydrogen atom (s) of each benzene ring may (may) be substituted (s) with an aromatic compound residue, an aliphatic compound residue or 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 , an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom.

Preferred examples of such an aniline compound are aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenethidine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p- phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, carboxy substituted anilines (e.g. p-aminobenzoic acid), hydroxyl substituted anilines (e.g. o-aminophenol, m-aminophenol, 2- amino-4-chlorophenol and p-aminophenol), 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, nitrile substituted anilines (e.g. 4-aminobenzonite Ryl), anthranilic acid, p-cresidine, halogen-substituted anilines (e.g. 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloranilin, 3,5-dichloraniline, 2,4,5-trichloroaniline, o-chloroaniline , m-chloroaniline and p-chloroaniline), α-naphthylamine, aminoanthracene, o-ethylaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p- aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amine o-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, carbamoylaniline (eg 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 and 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, sulfamoylanilines (e.g. 4-s ulfamoylaniline, 3-sulfamoylaniline, 2-chloro-5-N-phenylsulfamoylanilin, 2-methoxy-5-N, N-diethylsulfamoylaniline and 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) sulfonylanilinilinyl-4-anilonyl-anilonyl-3-anilinonilinilinilinilinilinilinilinilinilinilinilinilinilinilinilinilinilinilinilinilinilinilininilininilin substituted anilines (e.g. o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, o-nitroani lin, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine and 2-amino-5-nitrobenzonitrile), p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline , 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, 2-amino-3-bromo-5-nitrobenzonitrile and so on.

Aniline derivatives can also be used as aniline derivatives having one or more substituents, including a carboxyl group, a nitroso group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group, and so on.

The dihydroxy compound of general formula (XVI), which is used to prepare the urea-urethane compound of formula (VI), includes diphenols such as 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2 , 2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, 4,4'-biphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-tert- butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydride hydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3 methylphenyl) sulfide and so on. However, as such, diphenols that have an amino group are undesirable. Since the amino group is more reactive with respect to the isocyanate group than the OH group, the amino group interacts with the isocyanate group before the OH group, thereby making it difficult to obtain the desired compound in some cases.

The method for producing the urea-urethane compound of formula (VII) used in each of the aspects of the present invention, either twenty-first or twenty-second, is not particularly limited. This compound can be obtained, for example, by reacting a compound containing an OH group of general formula (IX) with an isocyanate compound of general formula (XII) and an amine compound of general formula (XI) in accordance with, for example, the following reaction formula (L).

As the substituent X attached to the urethane group of the urea-urethane compound of general formula (VII), alkyl groups, alkenyl groups, phenyl group, cycloalkyl groups, amide group, alkoxyl groups, nitro group, nitroso group, nitrile group, toluenesulfonyl group, methanesulfonyl, are preferred group, acetyl group, halogen atoms, formyl group, dialkylamino groups and isocyanate group.

Of these urea-urethane compounds of the general formulas (I) to (VII), as a developer, the compounds of the general formulas (II) to (VI) are preferred, and the compounds of the general formulas (V) and (VI) are particularly preferred.

In addition, a compound of the following structural formula (XX) or (XXI) is particularly preferred.

In the case of a urea-urethane compound used as a developer in each of the aspects of the present invention, either twenty-first or twenty-second, and compounds of formulas (I) to (IV) and (VII) as a developer, if a residue attached to them urea group or urethane group, is the residue of an aliphatic compound, the color intensity and color stability during printing in some cases worsen. Thus, the residue attached to the urea group or the urethane group is preferably a residue of an aromatic compound or a residue of a heterocyclic compound. However, the deterioration in color intensity and color stability during printing, which is probably caused by the introduction of the remainder of the aliphatic compound, decreases with an increase in the total number of urea group (s) and urethane group (s). In the case of a compound of formula (III) and formula (IV), even if the residue of the aliphatic compound is among the residues attached to the urea group (s) or urethane group (s), there are practically no difficulties with respect to performance.

The urea-urethane compound used in each aspect of the present invention, either twenty-first or twenty-second, can be obtained by mixing isocyanate with the corresponding reagents in an organic solvent or without solvent, reacting them and then collecting the obtained crystals by filtration. One or more compounds may be used as each reagent, depending on the purpose. As the solvent, any solvent may be used provided that it does not interact with the isocyanate group and the functional groups of the reagents. The solvent includes, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons and ketones. Particularly preferred are methyl ethyl ketone, toluene and the like, which dissolve the isocyanate and in which the reaction product has poor solubility. The reaction product obtained by the above reaction is not always the only compound, and in some cases is formed as a mixture of compounds of different positions of the substituent.

Specific examples of the urea-urethane compound used in each of the aspects of the present invention, either twenty-first or twenty-second, are the following compounds ((E-1) to (E-43)).

The urea-urethane compound used as a developer in the present invention is usually a colorless or light-colored compound that is solid at ordinary temperatures.

The molecular weight of the urea-urethane compound used as a developer in the present invention is preferably 5000 or less, more preferably 2000 or less.

The total number of urea groups (s) and urethane (s) group (s) in the urea-urethane compound used as a developer in the present invention is preferably 20 or less, more preferably 10 or less. The ratio of urea groups (s) to urethane (s) groups (e) in the molecular structure of the urea-urethane compound is preferably from 1: 3 to 3: 1, in particular from 1: 2 to 2: 1.

To obtain recording material using a urea-urethane compound, one type of urea-urethane compound or, if necessary, a combination of two or more types of urea-urethane compounds can be used as a developer.

When used in a heat-sensitive recording material, the urea-urethane compound is preferably a melting point compound. The melting point of the urea-urethane compound used as a developer in the present invention is in the range from 40 ° C to 500 ° C, in particular from 60 ° C to 300 ° C.

A colorless or light-colored dye precursor substance used in the twenty-second aspect of the present invention is a compound well known as a color-forming agent used in pressure sensitive recording materials and heat-sensitive recording materials, and is not particularly limited. As a dye precursor substance, leuco dyes are particularly preferred and triarylmethane type leuco dyes, fluoran type leuco dyes, fluorene type leuco dyes, diphenylmethane type leuco dyes and the like. Typical examples of leuco dyes are given below.

(1) Compounds of the triarylmethane type 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystalline 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-phenylindol-3-yl ) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethyl minophthalide and so on.

(2) Diphenylmethane type compounds

4,4′-bis-dimethylaminophenylbenzhydryl benzyl ester, N-halophenyl leukauramines, N-2,4,5-trichlorophenyl leukauramine and so on

(3) Xanthene type compounds

Rhodamine B anilinolactam, Rhodamine B-p-chloroanilinolactam, 3-dimethylamino-6-methyl-7- (m-trifluoromethylanilino) fluoran, 3-diethylamino-6-methylfluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7- chlorofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7-phenylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-p-methylanilinofluorane, 3-diethylamino-6-chloro-7-methylfluorane, 3-diethylamino-7- (3,4-dichloranilino) fluoran, 3-diethylamino-7- (2- chloranilino) fluorane, 3-diethylamino-6- ethyl 7- (o, p-dimethylanilino) fluoran, 3- (N-ethyl-N-tolyl) amino-6-methyl-7-phenethylfluorane, 3-diethylamino-7- (4-nitroanilino) fluoran, 3-diethylamino -6-methyl-7- (m-trifluoromethylanilino) fluoran, 3-diethylamino-6-methyl-7- (o-chloroanilino) fluoran, 3-diethylamino-6-methyl-7- (p-chloroanilino) fluoran, 3- diethylamino-6-methyl-7- (o-fluoroanilino) fluoran, 3-diethylamino-6-methyl-7- (p-n-butylanilino) fluoran, 3-diethylamino-6-methyl-7-n-octylaminofluorane, 3- diethylamino-6-chloro-7-anilinofluorane, 3-diethylamino-6-ethoxyethyl-7-anilinofluorane, 3-diethylamino-benzo [a] fluoran, 3-diethylamino-benzo [c] fluoran, 3-diet lamino-6-methyl-7-benzylaminofluorane, 3-diethylamino-6-methyl-7-dibenzylaminofluorane, 3-diethylamino-7-di (p-methylbenzyl) aminofluorane, 3-diethylamino-6-methyl-7-diphenylmethylaminofluorane, 3- diethylamino-7-dinaphthylmethylaminofluorane, 10-diethylamino-4-dimethylaminobenzo [a] fluorane, 3-diethylamino-7,8-benzfluorane, 3-diethylamino-6-methyl-7- (m-trichloroanilino) fluorane, 3-diethylamino-7 - (o-chloranilino) fluorane, 3-dibutylamino-7- (o-chloranilino) fluoran, 3-diethylamino-6-methyl-7- (2 ', 4'-dimethylanilino) fluoran, 3- (N, N-diethylamino ) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3-morpholino-7- (N-propyltri fluoromethylanilino) fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7- (N-benzyl trifluoromethylanilino) fluoran, 3-pyrrolidino-7- (di-p-chlorophenyl) methylaminofluorane, 3-diethylamino 5-chloro-7- (α-phenylethylamino) fluoran, 3- (N-ethyl-N-p-toluidino) -7- (α-phenylethylamino) fluoran, 3-diethylamino-7- (o-methoxycarbonylphenylethyl) fluorane, 3 -Diethylamino-5-methyl-7- (α-phenylethylamino) fluoran, 3-diethylamino-7-piperidinoaminofluorane, 2-chloro-3- (N-methyltoluidino) -7- (p-N-butylanilino) fluorane, 3- ( N-ethyl-N-cyclohexylamino) -5,6-benzo-7-α-naphthylamino-4'-bromofluorane, 3-diethyl mino-6-methyl-7-mesitidino-4 ', 5'-benzofluorane, 3-dibutylamino-6-methylfluorane, 3-dibutylamino-6-methyl-7-chlorofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-p-methylanilinofluorane, 3-dibutylamino-6-methyl-7- (o, p-dimethylanilino) fluoran, 3-dibutylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane, 3-dibutylamino-6-methyl-7- (o-chloroanilino) fluoran, 3-dibutylamino-6-methyl-7- (p-chloranilino) fluoran, 3-dibutylamino-6-methyl-7- (o-fluoroanilino) fluoran 3-dibutylamino-6-methyl-7- (p-n-butylanilino) fluoran, 3-dibutylamino-6-methyl-7-n-octylaminofluorane, 3-dibutylam but-6-chloro-7-anilinofluorane, 3-dibutylamino-6-ethoxyethyl-7-anilinofluorane, 3-di-n-pentylamino-6-methyl-7-anilinofluorane, 3-di-n-pentylamino-6-methyl- 7- (o, p-dimethylanilino) fluoran, 3-di-n-pentylamino-6-methyl-7- (m-trifluoromethylanilino) fluoran, 3-di-n-pentylamino-6-methyl-7- (o-chloranilino ) fluorane, 3-di-n-pentylamino-6-methyl-7- (p-chloranilino) fluoran, 3-di-n-pentylamino-6-methyl-7- (o-fluoroanilino) fluorane, 3-pyrrolidino-6 -methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-dimethylamino-5,7-dimethylfluorane, 3- (N-methyl-N-isoamylamino) -6 -met l-7-anilinofluorane, 3- (N-methyl-N-n-propylamino) -6-methyl-7-anilinofluorane, 3- (N-methyl-N-amylamino) -6-methyl-7-anilinofluorane, 3- (N, N-di-n-amylamino) -6-methyl-7-anilinofluorane, 3- (N-methyl-N-isopropylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-n -propylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isopropylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-n-butylamino) -6-methyl- 7-anilinofluorane, 3- (N-ethyl-N-isobutylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-n-hexylamino) -6-methyl-7-p-methylanilinofluorane, 3- (N-ethyl-N-n-hexylamino) -6-methyl-7- (o, p-dimethylanilino) fluoran, 3- (N-ethyl-N-n-hexylamino) -6-me il-7- (N-trifluoromethylanilino) fluoran, 3- (N-ethyl-N-n-hexylamino) -6-methyl-7- (o-chloroanilino) fluoran, 3- (N-ethyl-N-isoamylamino) - 6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamylamino) -6-chloro-7-anilinofluoran, 3- (N-ethyl-N-3-methylbutylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-p-toluidino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-p-toluidino) -6-methyl-7- (p-methylanilino) fluorane, 3 - (N-ethyl-N-p-toluidino) -6-methyl-7- (o, p-dimethylanilino) fluoran, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane, 3- (N-cyclohexyl-N-methylamino) -7-anilino luoran, 3- (N-ethyl-N-3-methoxypropylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-3-ethoxypropylamino) -6-methyl-7-anilinofluorane, 2- (4 -oxyhexyl) -3-dimethylamino-6-methyl-7-anilinofluorane, 2- (4-oxahexyl) -3-diethylamino-6-methyl-7-anilinofluorane, 2- (4-oxahexyl) -3-dipropylamino-6- methyl-7-anilinofluorane, 3,6-bis (diethylamino) fluoran-γ - (2'-nitro) anilinolactam, 3,6-6is (diethylamino) fluoran-γ - (3'-nitro) anilinolactam, 3,6- 6is (diethylamino) fluoran-γ - (4'-nitro) anilinolactam, 3,6-bis (diethylamino) fluoran-γ-anilinolactam and so on.

(4) Thiazine-type compound

Benzoylleukomethylene blue, p-nitrobenzoylleukomethylene blue and so on.

(5) Spiro compounds

3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3-methoxybenzo) spiropiran, 3-propylspirobenzopyran and so on.

Leuco dyes also include, for example, the following compounds that can absorb long-wave infrared waves: 3,6-bis (dimethylamino) fluoren-9-spiro-3 '- (6'-dimethylamino-phthalide), 3-diethylamino-6-dimethylaminofluorene -9-spiro-3 '- (6'-dimethylaminophthalide), 3,6-bis (diethylamino) fluoren-9-spiro-3' - (6'-dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluoren-9-spiro -3 '- (6'-dimethylaminophthalide), 3-dibutylamino-6-diethylaminofluoren-9-spiro-3' - (6'-dimethylaminophthalide), 3,6-bis (dimethylamino) fluorene-9-spiro-3'- (6'-diethylaminophthalide), 3-diet amylamino-6-dimethylaminofluoren-9-spiro-3 '- (6'-diethylaminophthalide), 3-dibutylamino-6-dimethylaminofluoren-9-spiro-3' - (6'-diethylaminophthalide), 3,6-bis (diethylamino) fluoren-9-spiro-3 '- (6'-diethylaminophthalide), 3,6-bis (dimethylamino) fluoren-9-spiro-3' - (6'-dibutylaminophthalide), 3-dibutylamino-6-diethylaminofluorene-9- spiro-3 '- (6'-diethylaminophthalide), 3-diethylamino-6-dimethylaminofluoren-9-spiro-3' - (6'-dibutylaminophthalide), 3,3-bis [2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) ethenyl] -4,5,6,7-tetrachlorophthalide and so on.

The above examples, leuco dyes, triarylmethane type dyes, fluoran type dyes, fluorene type dyes and diphenylmethane type dyes are preferred in terms of sensitivity and plasticizing stability, and compounds having the structure represented by the following chemical formula (i) or ( j):

where both Y ₂ and Y ₃ represent alkyl groups or alkoxyalkyl groups, Y ₄ represents a hydrogen atom, an alkyl group or an alkoxy group, and each Y ₅ and Y ₆ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group; or

where is everyone. R ₅ and R ₆ represents a group represented by formula (k) or formula (1):

(where each R ₁₁ -R ₁₅ represents a hydrogen atom, a halogen atom, a C ₁ -C ₈ alkyl group, a C ₁ -C ₈ alkoxy group or -NR ₁₆ R ₁₇ where each R ₁₆ and R ₁₇ represents a C ₁ -C ₈ alkyl group); or

(where each R ₁₈ and R ₁₉ represents a hydrogen atom, a C ₁ -C ₈ alkyl group or a phenyl group), and each R ₇ -R ₁₀ represents a hydrogen atom, a halogen atom, a C ₁ -C ₈ alkyl group, C ₁ - C ₈ alkoxy

a group or —NR ₂₀ R ₂₁ , where each R ₂₀ and R ₂₁ represents a C ₁ -C ₈ alkyl group.

If necessary, such colorless or light colored dye precursors may be used in combination of two or more of them.

The urea-urethane compound as a developer is used in a proportion, preferably from 5 to 1000 parts by weight, more preferably from 20 to 500 parts by weight per 100 parts by weight of a colorless or light-colored dye precursor substance. As a proportion of the urea-urethane compound as a developer, 5 parts by weight or more are sufficient for the dye precursor to exhibit color. With this proportion, the color intensity is high. When the proportion of the urea-urethane compound as a developer is 1000 parts by mass or less, there is almost no excess urea-urethane compound and this is economically advantageous and therefore preferable.

As the urea-urethane compound or urea-urethane composition used as a developer in the nineteenth aspect of the present invention, any urea-urethane compound of the aspects of the present invention can be used, starting from the first to the fourth, or any urea-urethane composition of the aspects of the present invention, starting with the fifth and ending with the twelfth. The process for preparing these compounds and compositions has already been described in detail in the detailed description of aspects of the present invention, starting from the first to the twelfth.

The incorporation of the isocyanate compound into the color-forming composition of the present invention improves the storage stability of the composition. The isocyanate compound that is incorporated into the color-forming composition of the present invention relates to a colorless or light colored, aromatic or heterocyclic isocyanate compound that is solid at ordinary temperatures. For example, one or more of the following isocyanate compounds are used.

The administered isocyanate compound includes 2,6-dichlorophenyl isocyanate, p-chlorophenyl isocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 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-diethoxy 1-benzene-1,4-diisocyanate, 2,5-dibutoxybenzene-1,4-diisocyanate, azobenzene-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene -1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphtha in-2,7-diisocyanate, 3,3'-dimethyl-biphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane-4 4'-diisocyanate, benzophenone-3,3'-diisocyanate, fluorene-2,7-diisocyanate, anthraquinone-2,6-diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, pyrene-3,8-diisocyanate, naphthalene -1,3,7-triisocyanate, biphenyl-2,4,4'-triisocyanate, 4,4 ', 4' '- triisocyanato-2,5-dimethoxytriphenylamine, 4.4', 4 '' - triisocyanatotriphenylamine, p- dimethylaminophenyl isocyanate, tris (4-phenyl isocyanato) thiophosphate and so on. If necessary, these isocyanates can be used in the form of so-called block isocyanates, that is, an additional compound with phenol, lactam, oxime or the like, they can be used in the form of a diisocyanate dimer, such as 1-methylbenzene-2,4-diisocyanate dimer or a diisocyanurate trimer as isocyanurate, and they can be used in the form of a polyisocyanate obtained as an adduct with various polyols and the like. Can also be used aqueous adducts of isocyanates selected from 2,4-toluene diisocyanate, diphenylmethane diisocyanate and the like, such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; polyol adducts such as a trimethylolpropane adduct selected from toluene diisocyanate (Desmodule L, trade name); phenolic isocyanate adducts; amine adducts of isocyanates; and isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patent JP-A-10-76757 and the detailed description of Japanese patent JP-A-10-95171.

The isocyanate compound is used in a proportion of preferably 5-500 parts by weight, more preferably 20-200 parts by weight, per 100 parts by weight of a colorless or light-colored dye precursor. When the proportion of the isocyanate compound is 5 parts by mass or more, a sufficient improvement in the effect of storage stability can be achieved and the color intensity becomes higher. When the proportion of the isocyanate compound is 500 parts by mass or less, there is almost no excess of the isocyanate compound and this is economically advantageous and therefore preferred.

The incorporation of an imino compound into the color-forming composition of the present invention further improves storage stability.

The imino compound that can be introduced into the color-forming composition of the present invention is a colorless or light-colored compound that has at least one imino group and is solid at ordinary temperatures. Depending on the purpose, two or more imino compounds may be introduced into the combination. As imino compounds can be mentioned compounds described in Japanese patent A-9-142032, and this link is incorporated herein by reference. Of the imino compounds described in the link, iminoisoindoline derivatives are preferred, and 1,3-diimino-4,5,6,7-tetrachloroisoindoline, 3-imino-4,5,6,7-tetrachloroisoindolin-1 and 1,3 β-diimino-4,5,6,7-tetrabromisoindoline are more preferred.

The imino compound is used in a proportion of preferably 5-500 parts by weight, more preferably 20-200 parts by weight, per 100 parts by weight of a colorless or light-colored dye precursor substance. When the proportion of the imino compound is 5 parts by mass or more, an improvement in the effect of storage stability is achieved and the color intensity becomes higher. When the proportion of the imino compound is 500 parts by mass or less, there is almost no excess of the imino compound and this is economically advantageous and therefore preferred.

In addition, the introduction of an amino compound in the color-forming composition of the present invention improves the storage stability of the original surface of the recording material and printing. An amino compound that can be introduced is a colorless or light colored substance having at least one primary, secondary or tertiary amino group. As such an amino compound, a compound described in Japanese Patent JP-A-9-142032 can be mentioned. The amino compounds described in this link, aniline derivatives having at least one amino group and represented by the following formula (VIII) are particularly preferred:

where R ₁ , r ₂ , r ₃ and R ₄ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group, X ₁ and X ₂ independently represent an amino group or a group represented by the formula (b):

and Y ₁ represents any group of —SO ₂ -, —O—, - (S) _n -, - (CH ₂ ) _n -, —CO—, —CONH— and a group represented by any of formulas (a):

or absent and n is 1 or 2.

These amino compounds can be used alone or as a mixture. To improve the safety of the print in the plasticizing additive for stability, the proportion of the amino compound is preferably 1-500 parts by weight per 100 parts by weight of a colorless or light-colored dye precursor substance. When the content of the amino compound is 1 part by mass or more per part of the urea-urethane compound, the security of the print can be improved. When the content is 500 parts by weight or less, the performance of the resulting composition can be sufficiently improved and this content is advantageous in terms of price.

The incorporation of an acidic developer into the color-forming composition of the present invention also improves sensitivity and enables the color-forming composition to produce a brilliant color.

As the acid developer which is used when the color-forming composition of the present invention is used in a heat-sensitive recording material, conventional electron-acceptor substances are used, in particular phenolic derivatives are preferred; derivatives of aromatic carboxylic acids or their metal compounds; derivatives of salicylic acid or their metal salts; N, N-diarylthiourea derivatives; sulfonylurea derivatives; etc. Particularly preferred are phenol derivatives. Specific examples of phenol derivatives are 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-hydroxyphenyl -4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl sulfone, 4-isopropylphenyl-4'-hydroxyphenyl sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, methyl 4 -hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'-chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate and so on. Derivatives of salicylic acid include 4-n-octyloxyisalicylic acid, 4-n-butyloxyisalicylic acid, 4-n-pentyloxyisalicylic acid, 3-n-dodecyloxyisalicylic acid, 3-n-octanoyloxyisalicylic acid, 4-n-octanyloxyisalicylic acid, 4-n-octyloxy salicylic acid, 4-n-octyloxy oxalicylic acid, 4-n-octyloxy salicylic acid, 4-n-octyloxy salicylic acid, 4-n-octoxy oxalicylic acid n-octanoyloxycarbonylaminosalicylic acid and so on. Sulfonylurea derivatives include, for example, compounds containing one or more arylsulfonylamino-ureido groups such as 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane, 4,4-bis (o-toluenesulfonylaminocarbonylamino) diphenylmethane toluenesulfonylaminocarbonylamino) diphenyl sulfide, 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenyl ether, N- (p-toluenesulfonyl) -N'-phenylurea and so on. In addition, 4.4 '- [oxybis (ethyleneoxy-p-phenylene sulfonyl)] diphenol and mixtures mainly containing this compound (for example, D-90 (trade name, manufactured by Nippon Soda Co.) can also be used, for example. , Ltd.)).

Of the above, as examples of acidic developers, 2,2-bis (4-hydroxyphenyl) propane, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenylsulfone are particularly preferred. and 4.4 '- [oxybis (ethyleneoxy-p-phenylene sulfonyl)] diphenol, as they improve sensitivity and make it possible to obtain heat-sensitive recording material capable of giving a brilliant color.

In order to improve haze, thermal reaction, and the like, phenolic compounds such as N-stearyl-N ′ - (2-hydroxyphenyl) urea, N-stearyl-N ′ - (3-hydroxyphenyl) urea, N can also be added. -stearil-N '- (4-hydroxyphenyl) urea, p-stearoilaminofenol, o-stearoilaminofenol, p-lauroilaminofenol, p-butirilaminofenol, m-atsetilaminofenol, o-atsetilaminofenol, p-atsetilaminofenol, o-butilaminokarbonilfenol, o-stearilaminokarbonilfenol n -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-tert-butyl-4-hydroxy -6-methylphenyl) propane, 1,2,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-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, 1,1-bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) butane and so on.

The above acidic developers are used in a proportion of preferably 5-500 parts by weight, more preferably 20-200 parts by weight, per 100 parts by weight of a colorless or light-colored dye precursor. When the proportion of the acid developer is 5 parts by mass or more, the color formation of the dye precursor is satisfactory and the color intensity is high.

When the proportion of the acid developer is 500 parts by mass or less, there is almost no excess acid developer and this is economically advantageous and therefore preferable.

Also, when the color-forming composition of the present invention is used in a pressure-sensitive recording material, introducing an acid developer into the color-forming composition improves the staining intensity and allows the pressure-sensitive recording material to produce a brilliant color.

Also, an electron-acceptor substance is used as an acid developer. An acid developer includes, for example, inorganic compounds such as acid clay, activated clay, attapulgite, bentonite, zeolite, colloidal silica, magnesium silicate, talc, aluminum silicate and so on; phenol, cresol, butylphenol, octylphenol, phenylphenol, chlorphenol, salicylic acid and the like, or novolac aldehyde condensed resin obtained from them, and their metal salts; and salicylic acid derivatives such as 3-isopropylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3,5- di-tert-octylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3,5-di (α, α-dimethylbenzyl) salicylic acid, 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid and so on and their metal salts.

The incorporation of a fluorescent dye into the color-forming composition of the present invention also improves whiteness. Various well-known dyes and the mentioned stilbene derivatives, coumarin derivatives, pyrazoline derivatives, bisstyryl biphenyl derivatives, naphthalimide derivatives, bisbenzoxazolyl derivatives and so on can be used as the fluorescent dye to be introduced into the color-forming composition of the present invention. Although fluorescent dyes are not particularly limited, diaminostylbendisulfonic acid derivatives are particularly preferred.

With respect to the amount of fluorescent dye used, the fluorescent dye is present in an amount of preferably from 0.01 to 3 wt.%, More preferably from 0.1 to 2 wt.%, Based on the total weight (in solid units) of the color-forming composition. When the amount of fluorescent dye used is more than 3 wt.%, Then, in some cases, the color-forming composition becomes colored. When the amount is less than 0.01 mass%, then the effect of the fluorescent dye on whiteness is reduced.

Then, the color-forming composition of the present invention may contain storage stability enhancing agents. The storage stability enhancing agents used in the present invention are additives such as image stabilizing agents, light stabilizers, antioxidants and so on.

By using these storage stability enhancing agents in combination with a urea-urethane developer compound (i.e., the developer includes a urea-urethane compound) and a colorless and light-colored dye precursor, the lightfastness of the color-forming composition can be improved and can be obtained recording material excellent in light resistance.

Image stabilizing agents, as preferred examples of storage stability enhancers used in the present invention, include, for example, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1 , 1, 3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, inhibited phenolic compounds [eg, 4,4'-butylidenebis (2-tert-butyl-5-methylphenol), 4,4'- thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol) and 2,2'-methylenebis (6-tert-butyl-4-methylphenol)], 4-benzyloxy-4 '- (2-methylglycidyloxy) diphenylsulfone, 4,4'- iglitsidiloksidifenilsulfon, 1,4-diglitsidiloksibenzol, sodium 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, 2-propanol derivatives and salicylic acid derivatives. Typically, these image stabilizing agents are used in a proportion of preferably from 5 to 1000 parts by weight, more preferably from 10 to 500 parts by weight, per 100 parts by weight of a colorless or light colored dye precursor. When the proportion of image stabilizing agents is 5 parts by mass or more, lightfastness is suitable and the staining intensity is high. When the proportion of image stabilizing agents is more than 1000 parts by mass, their effect with respect to light resistance is not enhanced and, moreover, such a proportion is economically disadvantageous.

Light stabilizers as preferred examples of storage stability improving agents used in the present invention include, for example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert- butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5- chlorobenzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-ne ntil-2’-hydroxyphenyl) benzotriazole, 2- (3’-tert-butyl-2’-hydroxy-5’-octyloxycarbonylethylphenyl) -5-chlorobenzotriazole and the like; 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-hydroxy-4,4' dimethoxy or 4- (2-ethylhexyloxy) -2-derivatives of hydroxybenzophenone and the like; 4-tert-butylphenyl salicylate, phenyl salicylate, octyl phenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-hexadecyl di-tert-butyl-4-hydroxybenzoate and the like; ethyl α-cyano-β, β-diphenyl acrylate, isooctyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxy cinnamate, methyl α-cyano-β-methyl-p-methoxy cinnamate and the like; bis (2,2,6,6-tetramethyl-4-piperidyl) sebacinate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl 4-piperidyl) sebacinate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacinate, bis (1,2,2,6, b-pentamethyl-4-piperidyl) adipate and the like ; 4,4'-di-octyloxyoxanilide, 2,2'-diethoxyoxyananilide, 2,2'-di-octyloxy-5,5'-di-tert-butyloxanilide, 2,2'-di-dodecyloxy-5,5'- di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxanilide, 2-ethoxy-5-tert-butyl-2'-ethoxyoxanilide and the like; and 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy- 4-propyloxyphenyl-6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethyl-phenyl) -1 , 3,5-triazine, etc. Typically, these light stabilizers are used in a proportion of preferably from 5 to 1000 parts by mass, more preferably from 10 to 500 parts by mass, per 100 parts by mass of a colorless or light colored precursor and dye.When the proportion of light stabilizers is 5 parts by mass or more, light resistance is suitable and the dyeing intensity is high.When the proportion of light stabilizers is more than 1000 parts by mass, their effect with respect to light resistance is no longer enhanced and, moreover, such a proportion is economically disadvantageous.

Antioxidants as preferred examples of storage stability enhancers used in the present invention include, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-4,6-dimethylphenol, 2,6-di tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2 - (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-dinonyl-4-methylphenol, 2,6-di-tert-butyl -4-methoxymethylphenol, 2,4-dimethyl-6- (1'-methyl-undeca-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyl-hept deca-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyl-trideka-1'-yl) phenol and mixtures thereof; 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol and their mixture; 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) adipate and a mixture thereof; 2,4-bis-octyl mercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis (3,5-di tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4 -hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate and the like; 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-ethylidenebis (4,6-di-tert -butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert -butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, ethylene glycol bis [3,3'-bis (3'-tert-butyl-4'- hydroxyphenyl) butyrate] and the like; 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl ) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol and the like. Typically, these antioxidants are used in a proportion of preferably from 5 to 1000 parts by weight, more preferably from 10 to 500 parts by weight, per 100 parts by weight of a colorless or light-colored dye precursor. When the proportion of image stabilizing agents is 5 parts by mass or more, lightfastness is suitable and the staining intensity is high. When the proportion of antioxidants is more than 1000 parts by weight, their effect on lightfastness is not enhanced and, in addition, this proportion is economically disadvantageous.

The color-forming composition of the present invention can be incorporated into the recording material by forming a color-forming layer of the composition on a certain substrate using a method such as coating. The structure of the recording material varies depending on the type of recording material.

The color-forming composition of the present invention can be incorporated into various recording materials, such as heat-sensitive recording materials, pressure-sensitive recording materials, and the like, and are particularly suitable for heat-sensitive recording materials.

When a color-forming composition is used in a heat-sensitive recording material, then a heat-sensitive recording layer capable of producing color when heated is formed on the substrate. In particular, the aforementioned urea-urethane compound, the aforementioned colorless or light-colored dye precursor substance, such as a leuco dye, a heat-melting substance described hereinafter, and the like can be applied to a substrate, each in the form of a dispersion together with other necessary components to form heat sensitive recording layer. The dispersion is obtained by finely grinding one or more compounds as each component described above, in a sand mill or the like, in an aqueous solution containing a compound having dispersion ability, such as water-soluble polymers, surfactants or the like. The particle size of each dispersion thus obtained is preferably set to from 0.1 to 10 μm, in particular up to about 1 μm. Specific examples of dispersion compounds that can be used in the present invention are water-soluble polymers such as poly (vinyl alcohol), poly (vinyl alcohol) modified with carboxylic acid, poly (vinyl alcohol) modified with sulfonic acid, methyl cellulose, hydroxypropyl methyl cellulose hydroxypropyl cellulose and so on; anionic surfactants, such as condensed naphthalenesulfonates, salts of polyoxyethylene alkyl ethers of sulfuric acid (for example, sodium polyoxyethylene lauryl ether sulfates, sodium polyoxyethylene alkyl ether sulfates and sodium polyoxyethylene alkyl phenyl ether sulfate, alkyl sulfate, sulfonate, sulfonate, sulfonate, acids and the like; nonionic surfactants such as polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, polyoxyethylene glycol fatty acid esters and the like; and cationic surfactants such as dicyanamidopolyamines, tertiary amine salts, quaternary ammonium salts and so on. Of these, polyvinyl alcohols, carboxylic acid modified polyvinyl alcohols, sulfonic acid modified polyvinyl alcohols, and methyl cellulose are particularly preferred. The compounds exemplified can be used alone or as mixtures thereof.

When a urea-urethane developer compound in accordance with the present invention is used in a heat-sensitive recording material, the established average particle size of the urea-urethane developer compound is not more than 5 μm and not less than 0.05 μm makes it possible to obtain a heat-sensitive recording material that has sufficient color-forming sensitivity, gives a very stable color image when printing and has good plasticizer resistance. The average particle size is more preferably not more than 3 microns and not less than 0.1 microns. When the average particle size is less than 0.05 μm, the storage stability of the initial surface of the recording material relative to plasticizers is deteriorated. On the other hand, when the average particle size is more than 5 μm, the sensitivity of the heat-sensitive recording material decreases.

In particular, when the urea-urethane compound is wet milled in an aqueous medium, the temperature of the aqueous medium is preferably 60 ° C. or lower. During grinding, the urea-urethane compound of the developer interacts with water in such a way that its urethane (s) group (s) are hydrolyzed, depending on the conditions. Thus, the sensitivity of the heat-sensitive recording material obtained using the urea-urethane developer compound tends to decrease. In particular, when the temperature of the medium during grinding is greater than 60 ° C, the sensitivity decreases significantly. The grinding medium temperature is preferably more than 40 ° C. or lower.

Furthermore, when the urea-urethane compound of the developer is milled, it is preferable to grind it in a neutral pH range of 5 to 10. When the milling pH is lower than 5, the inorganic pigment and the like breaks down when a heat-sensitive coating liquid is obtained, so that the sensitivity tends to decrease . On the other hand, when the pH is greater than 10, the urea-urethane developer compound is hydrolyzed so that the sensitivity is reduced in some cases. Specific examples of dispersing agents used in preparing a dispersion of a urea-urethane developer compound by grinding in the present invention are water-soluble polymers such as poly (vinyl alcohol), poly (vinyl alcohol) modified with carboxylic acid, poly (vinyl alcohol) modified sulfonic acid, methyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose and so on; anionic surfactants such as condensed naphthalenesulfonates, salts of polyoxyethylene alkyl ethers of sulfuric acid (e.g. sodium polyoxyethylene lauryl ether sulfates, sodium polyoxyethylene alkyl ether sulfates and sodium polyoxyethylene alkyl phenyl ether sulfate, sulfonate, sulfonate, sulfonate, etc; nonionic surfactants such as polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, polyoxyethylene glycol fatty acid esters and the like; and cationic surfactants such as dicyanamidopolyamines, tertiary amine salts, quaternary ammonium salts and so on. Of these, water-soluble polymers and anionic surfactants are particularly preferred, since they make it possible to obtain a heat-sensitive recording material that is highly sensitive, regardless of the dispersion conditions of the urea-urethane compound of the developer, and has improved storage stability of the original surface of the recording material relative to plasticizers, regardless of the average particle size of the urea-urethane developer compound. Polyvinyl alcohols, modified polyvinyl alcohols, methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalene sulfonate, ammonium salts of polycarboxylic acids, low molecular weight water soluble copolymers and sodium 2-ethylhexyl sulfosuccinate are more preferred. Of these, methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalene sulfonate and water soluble low molecular weight copolymers are even more preferred, and hydroxypropyl methyl cellulose is most preferred. The dispersing agents listed above as examples may be used alone or as mixtures.

As a dispersing agent used to obtain a dispersion of a colorless or light-colored dye precursor material by grinding according to the present invention, some of the compounds used as a dispersing agent for dispersing a urea-urethane developer compound can be used. Of these, water-soluble polymers, anionic surfactants, and dispersant mixtures of these two kinds of compounds are particularly preferred for improving the heat-sensitive recording agent in terms of sensitivity and stability during storage of the starting surface of the recording material. A mixture of dispersing agents containing methyl cellulose or hydroxypropyl methyl cellulose as a water-soluble polymer and polyoxyethylene alkyl ether sulfate or sodium 2-ethylhexyl sulfosuccinate as an anionic surfactant is more preferred. A mixture of the dispersing agent of hydroxypropyl methylcellulose and sodium 2-ethylhexyl sulfosuccinate is most preferred. The pH of the coating liquid containing a urea-urethane compound and a colorless or light-colored dye precursor is preferably 5 to 12.

The heat-sensitive recording layer may contain, in addition to the components described above, pigments such as diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formaldehyde resin and so on . In addition, the heat-sensitive recording layer may, if necessary, contain metal salts of higher fatty acids, such as zinc stearate, calcium stearate and so on; and waxes such as paraffin, oxidized paraffin, polyethylenes, oxidized polyethylenes, stearamide, cathodic wax, and so on, for example, to prevent head wear and sticking. If necessary, the heat-sensitive recording layer may also contain dispersing agents, such as sodium dioctyl sulfosuccinate and so on; ultraviolet absorbers of the benzophenone type, benzotriazole type and the like; surfactants; fluorescent dyes; etc.

As binders used to form the heat-sensitive recording layer, water-soluble binders such as starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, poly (vinyl alcohol) s, modified poly (vinyl alcohol) can be mentioned, for example. ) s, poly (acrylate) sodium, acrylamide-acrylic ester copolymers, acrylamide-acrylic ester-methacrylic acid copolymers, alkaline salts of styrene-maleic anhydride copolymers, alkaline salts of ethylene copolymers -meleic anhydride and so on; and water-insoluble latex type binders selected from styrene-butadiene copolymers, acrylonthyryl-butadiene copolymers, acrylate-butadiene copolymers and so on.

Paper is mainly used as a substrate for a heat-sensitive recording layer, although depending on the purpose, in addition to paper, various woven materials, nonwovens, synthetic polymer films, laminated papers, synthetic papers, metal foil and composite sheets obtained by combining two or more of them. The weight of the substrate base is preferably from 40 g / m ² to 200 g / m ² . The substrate should preferably be excellent in surface smoothness and flatness, since the heat-sensitive recording material obtained using the substrate should preferably be as flat as possible. Thus, the substrate is preferably subjected to surface treatment by applying heat and pressure through any mechanical calender, soft calender, supercalender and the like.

The surface pH of the substrate is preferably 3-9, more preferably 5-9, more preferably 6-8, when the surface pH of the substrate is lower than 3, a haze appears. When the surface pH of the substrate is higher than 12, the urea-urethane compound of the developer disintegrates so that the staining intensity is reduced in some cases.

The heat-sensitive recording layer may consist of a single layer or two or more layers. The heat-sensitive recording layer may, for example, have a multilayer structure obtained by introducing each color-forming component into one layer. A protective layer consisting of a single layer or two or more layers can be obtained on a heat-sensitive recording layer and an intermediate layer consisting of a single or two or several layers can also be obtained between a substrate and a heat-sensitive recording layer. A heat-sensitive recording layer can be obtained by mixing aqueous dispersions obtained by finely grinding each color-forming component or any other components with a binding agent and the like, applying the resulting mixture to a substrate and drying the mixture. The coating amount of this coating liquid is preferably 1 to 15 g / m ² when the coating liquid is in a dried state.

When the color-forming composition of the present invention is used in a heat-sensitive recording material, the hot-melt material can be introduced into the color-forming composition to improve sensitivity. The hot-melt material is preferably a material with a melting point of 60 ° C.-180 ° C., in particular one with a melting point of 80 ° C.-140 ° C. The hot-melt material includes, for example, benzyl p-benzyloxybenzoate, stearamide or its emulsified product, palmitamide, N-methylolstearamide, β-naphthylbenzyl ether, N-stearylurea, N, N'-distearylurea, phenyl β-naphthoate, phenyl 1-hydroxy-2-naphthoate, 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-butanediolphenyl ether, dimethyl terephthalate, m-terphenyl, dibenzyloxalate and (p-chlorobenzyl) oxalate.

In addition, 4,4'-dimethoxybenzophenone, 4,4'-dichlorobenzophenone, 4,4'-difluorobenzophenone, diphenylsulfone, 4,4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 4,4 'are preferred as the hot melt material. dichlorodiphenyl disulfide, diphenylamine, 2-methyl-4-methoxyphenylamine, N, N'-diphenyl-p-phenylenediamine, 1- (N-phenylamino) naphthalene, benzyl, 1,3-diphenyl-1,3-propanedione and so on , since they very effectively improve sensitivity.

As a hot-melt material, benzyl 4-hydroxybenzoate, 4- (benzyloxy) phenol, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2, 2-bis ( 4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4 hydroxy-3-methyl phenyl) sulfide, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4,4'-thiobisbenzenethiol, salicylanilide, 4,4'-diamino-3,3'-diethyl diphenylmethane, 4,4'-diaminobenzanilide, 3,3'-dichloro- 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 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'-dia minodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, acetoacetic o-chloroanilide, acetoacetic anilide, acetoacetic o-toluidide, acetoacetic acetoacetic acetoacetic -anisidide, acetoacetic m-xylidide and p-acetotoluidide and so on.

Of these, diphenyl sulfone, di-p-methylbenzyloxalate, benzyl, β-naphthylbenzyl ether, p-benzylbiphenyl, 1,2-di (m-methylphenoxy) ethane, 1,2-diphenoxymethylbenzene, m-terphenyl and stearamide are preferably used.

In addition, the use of a hot-melt material of the following formula (XVIII), including the hot-melt materials presented above as examples, in a heat-sensitive recording material is significantly effective for increasing the sensitivity of the recording material and improving the plasticizer stability of the printed part and the heat resistance of the original surface of the recording material. The hot-melt materials represented by structural formula (XIX) below are particularly preferred.

where Y represents any group —SO ₂ -, - (S) _n -, —O—, —CO—, —CH ₂ -, —CH (C ₆ H ₅ ) -, —C (CH ₃ ) ₂ -, —COCO—, —CO ₃ -, —COCH ₂ CO—, —COOCH ₂ -, —CONH—, —OCH ₂ - and —NH—, n is 1 or 2, and the hydrogen atom (s) of each benzene ring can be are substituted by a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a sulfamoyl group, a sulfonic group, an amino group, an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue.

where the hydrogen atom (s) of each benzene ring can be replaced by a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a sulfamoyl group, a sulfonic group, an amino group, an aromatic compound residue, an aliphatic compound residue or heterocyclic compounds.

The heat-melting materials given above as examples can be used independently or as mixtures thereof. In order to achieve a sufficient thermal response, the fusible material is used in a proportion of preferably 10-300 parts by weight, more preferably 20-250 parts by weight, per 100 parts by weight of a colorless or light-colored dye precursor.

As the dispersing agent that can be used to obtain the dispersion of the hot melt material by grinding according to the present invention, some compounds can be used, such as those used as the dispersing agent for dispersions of the urea-urethane developer compound. Of these, in order to improve the heat-sensitive recording substance in terms of stability during storage of the initial surface of the recording material relative to plasticizers, water-soluble polymers and anionic surfactants are particularly preferred. More preferred are poly (vinyl alcohol), modified poly (vinyl alcohol), methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalene sulfonate, ammonium salts of polycarboxylic acids, water-soluble copolymers of low molecular weight and sodium 2-ethylhexyl sulfosuccinate. Of these, modified polyvinyl alcohols, methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalene sulfonate, ammonium salts of polycarboxylic acids are even more preferred, and hydroxypropyl methyl cellulose is most preferred. The dispersing agents listed above as examples may be used alone or as a mixture thereof.

When the urea-urethane developer compound is ground, fine grinding of the developer together with the above-mentioned hot melt material (co-grinding) also improves the sensitivity and storage stability of the heat-sensitive recording material compared to each finely ground compound followed by mixing of the ground compounds. The reasons why these effects occur are not completely clear.

In addition, the moisture resistance of the unprinted portion (the starting surface) of the heat-sensitive recording material can be improved by using at least one dispersant for the urea-urethane developer compound selected from methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalene sulfonate and water-soluble low molecular weight copolymers, at least one dispersing agent for a hot melt material selected from modified polyvinyl industrial alcohols, methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalenesulfonate and ammonium salts of polycarboxylic acids.

The color-forming composition of the present invention can be used in various heat-sensitive recording materials and is particularly suitable for heat-sensitive magnetic recording materials, labels for heat-sensitive recording, color heat-sensitive recording materials for laser marking.

When the color-forming composition of the present invention is used in a heat-sensitive magnetic recording material, the recording material is preferably in the following form: a heat-sensitive recording layer containing a urea-urethane developer compound is formed on one side of the substrate, and a magnetic layer is formed on the other side.

A magnetic recording layer of a heat-sensitive magnetic recording material is obtained by applying a coating material to a substrate obtained with a uniform dispersing ferromagnetic powder, such as barium ferrite, strontium ferrite, Co-γ-Fe ₂ O ₂ , γ-Fe ₂ O ₂ or the like, in an aqueous binder, such as an aqueous emulsified polymer, and drying the coating substrate. In this case, depending on their goals, various additives can be added, such as antistatic agents (for example, carbon graphite), lubricants (for example, wax), color pigments for tone adjustment, film-coated plasticizers [for example, poly (ethylene oxide) ] etc.

The heat-sensitive magnetic recording material of the present invention is suitable as heat-sensitive magnetic recording materials used as train tickets, tickets, franked cards and so on.

When the color-forming composition of the present invention is used as a label for heat-sensitive recording, the label is preferably in the following form: a heat-sensitive recording layer containing a urea-urethane developer compound is formed on one side of the substrate and an adhesive layer is formed on the other side.

The adhesive layer of this heat-sensitive recording material mainly consists of a pressure sensitive adhesive. The pressure sensitive adhesive includes, for example, adhesives such as emulsion based on synthetic rubber, adhesives such as acrylic emulsion, adhesives such as solvent based on natural rubber, adhesives such as acrylic solvent and adhesives such as solvent based on silicone. Of these, acrylic emulsion type adhesives are particularly preferred.

When the back side layer (back side coating), if necessary, is formed between the adhesive layer and the substrate, in the heat sensitive recording label obtained by the method of the present invention, the field is removed to prevent electrostatic charge and the friction coefficient in the label is set for heat sensitive recording. As the components of the coating liquid for the back side layer, the method of applying the coating liquid, and the like, the same components, method, and the like as in the formation of the heat-sensitive recording layer can be used. The dry distribution of the coating liquid is in the range preferably from 0.2 to 10.0 g / m ² .

The order of coverage when receiving a label for heat-sensitive recording is not specifically limited. For example, any order of the following can be used: a heat-sensitive recording layer is formed on one side of the substrate and then a back side coating is formed on the other side, after which an adhesive layer is formed on the back side coating; or a back side coating is formed on one side of the substrate and then a heat-sensitive recording layer is formed on the other side, after which an adhesive layer is formed on the back side coating.

As a method of forming an adhesive layer on the back side coating, the liquid for forming the adhesive layer can be directly applied to the back side coating and dried, or the material obtained before applying the liquid to form the adhesive layer on the cushion paper, followed by drying, can be applied to the back coating side heat-sensitive recording material that does not have a formed adhesive layer.

In addition, the thermal response can be improved by forming an intermediate layer consisting of a single layer or two or more layers between the heat-sensitive recording layer and the substrate. The intermediate layer mainly consists of an organic or inorganic pigment, hollow particles and an aqueous binder, such as a water-soluble polymer or latex. As the organic or inorganic pigment and the aqueous binder, the same organic or inorganic pigment and the aqueous binder can be used as used in the heat-sensitive recording layer. The method for forming the intermediate layer is not particularly limited. As this method, the same method can be used as the method for forming a heat-sensitive recording layer. The dry matter distribution zone of the intermediate layer is preferably in the range of 2.0 to 15.0 g / m ² .

When the color-forming composition of the present invention is used in a color heat-sensitive recording material, this recording material is preferably in the following form: at least two heat-sensitive recording layers are formed on one side of the substrate and at least one of said heat-sensitive recording layers containing urea urethane developer compound.

Synthetic paper obtained by mixing a polyolefin resin and a white inorganic pigment with heating, stamping the mixed product through a mold, stretching the mixed product in the longitudinal direction, laminating one or two films made of a polyolefin resin and a white inorganic pigment can be used as a substrate. on each side of the stretched product, and stretching the resulting system in the transverse direction to make it translucent Do opaque; films obtained by mixing one or a mixture of two or more thermoplastic resins, such as polyethylenes, polypropylenes, ethylene-vinyl acetate copolymer resins, poly (vinyl chloride) s, polystyrenes, polyesters, etc., by heating, compressing the mixed product through a mold and then stretching mixed product in the transverse direction; opaque films obtained by mixing a white inorganic pigment with any of the above examples of resins, followed by longitudinal-transverse stretching; and substrates obtained from cellulose fibers, such as paper without wood pulp, paper with medium wood pulp, paper coated on one side, regenerated paper, coated paper and so on. Substrates made from cellulose fibers are preferably coated with a heat-sensitive layer after the previous formation of the coating layer to improve image uniformity.

The heat-sensitive color-forming layer in accordance with the present invention includes, as main elements, an adhesive and color-forming composition capable of causing a color formation reaction due to contact of materials with each other when heated. Specific examples of a color-forming composition are combinations of a colorless or light-colored dye precursor substance and the aforementioned urea-urethane developer, capable of forming color by the dye precursor substance when heated, and a combination of a diazo compound and a pair capable of producing color by reacting with a diazo compound. If necessary, a crosslinking agent, pigments and heat-melting materials may be included in the color-forming composition. Typically, the amount of coating of the heat-sensitive color-forming layer is preferably from 3 to 15 g / m ² in terms of color formation sensitivity and color intensity.

As a color-forming dye, as already described, a colorless or light-colored dye precursor is used, which can exhibit color when reacted with a urea-urethane developer compound when heated.

On the other hand, in a heat-sensitive recording layer including a diazo compound and a communication element capable of developing color when interacting with the above diazo compound as the main elements, these compounds are a well-known light-degradable diazo compound and a communication element capable of forming a pigment when it interacts with the above diazo compound. If necessary, basic material and the like may be added in order to accelerate the interaction of the diazo compound with the coupling element. The bonding element and the base material are preferably used as a mixture in proportions of from 10 to 1000 parts by weight and from 10 to 2000 parts by weight, respectively, per 100 parts by weight of the diazo compound.

The term “light-degradable diazocompound”, as used herein, means a photosensitive diazotype material capable of forming a pigment when reacted with a bond element when heated, such as a diazonium salt, diazosulfonate compound, diazoamino compound, quinondiazide compound or the like. Diazonium salt refers to a compound represented by the general formula:

Ar-n $\genfrac{}{}{0ex}{}{\text{+}}{\text{2}}$ X ^-

where Ar represents the aromatic part, N $\genfrac{}{}{0ex}{}{\text{+}}{\text{2}}$ represents a diazonium group and X ^- represents a counterion. Such compounds have different absorption wavelength maxima depending on the position and class of the substituent Ar part.

Specific examples of the diazonium compound used in the present invention are 4-dimethylaminobenzenediazonium, 4-diethylaminobenzenediazonium, 4-methylbenzylaminobenzenediazonium, 4-dibenzylaminobenzodiazonodiazenedio-4-di-4-dihydro-benzodiazenediazenedio-2-diazole-4-dihydro-aminobenzenediazonium methylbenzene diazonium, 4-benzoylamino-2,5-diethoxybenzene diazonium, 4-morpholinobenzene diazonium, 4-morpholino-2,5-diethoxybenzene diazonium, 4-morpholino-2,5-dibutoxybenzene diazonium, 4-anilinobenzenediazonium, ilmercapto-2,5-diethoxybenzenediazonium, 4- (N, N-dioctylcarbamoyl) benzenediazonium, 2-octadecyloxybenzenediazonium, 4- (4-tert-octylphenoxy) benzenediazonium, 4- (2,4-di-tert-amylphenoxy) - (4-tert-octylphenoxy) benzenediazonium, 5-chloro-2- (4-tert-octylphenoxy) benzenediazonium, 2,5-bis-octadecyloxybenzenediazonium, 2,4-bis-octadecyloxybenzenediazonium, 4- (N-octyl lauroylamino benzol) etc. Specific examples of the counterion of the diazonium salt used in the present invention are Cl1 / 2Z _n Cl $\genfrac{}{}{0ex}{}{\text{-}}{\text{2}}$ Bf $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ , B (ph) $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , C _n F _{2n + 1} COO ^- (n is 3-9), C _m F _{2m + 1} SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ (m is 2-8), (C _k F _{2k + 1} SO ₂ ) ₂ CH ^- (k is 1-18) and so on.

The diazosulfonate compound used in the present invention is a compound represented by the following general formula:

Ar-N ₂ -SO ₃ Na

where Ar represents the aromatic part. Specific examples of the diazosulfonate compound used in the present invention are sodium benzene diazosulfonates having one or more substituents, including 2-methoxy, 2-phenoxy, 2-methoxy-4-phenoxy, 2,4-dimethoxy, 2-methyl-4- methoxy, 2,4-dimethyl, 2,4,6-trimethyl, 2,4,6-trimethoxy, 2,4-dimethoxy-5-chloro, 2-methoxy-5-nitro, 2-methoxy-5-acetamido, 2-methoxy-5-N, N-diethylsulfonamido, 2-methoxy-5-N-phenylcarbamyl, 3-methyl, 4-methyl, 4-methoxy, 4-ethoxy, 4-phenyl, 4-phenoxy, 4-acetamido and etc; and sodium benzyldiazosulfonates having one or more substituents, including 4- (N-ethyl-N-benzylamino), 4- (N, N-dimethylamino), 4- (N, N-diethylamino), 4- (N, N- diethylamino) -3-chloro, 4- (N-ethylamino) -3-methyl, 4- (N, N-diethylamino) -2-methyl, 4- (N-ethyl-N-β-hydroxyethylamino), 4-pyrrolidino -3-chloro, 4-pyrrolidino-3,5-dichloro, 4-morpholino, 4-morpholino-3-chloro, 4-morpholino-2-methoxy, 4-morpholino-2,5-diethoxy, 4-morpholino-2 5-dibutoxy, 4- (4'-tolyl mercapto) -2,5-dibutoxy, 4- (4'-tolyl mercapto) -2,5-diethoxy, 4- (4'-methoxybenzoylamino) -2,5-dibutoxy, 4-diphenylamino and so on. When any of these diazosulfonate compounds are used, the diazosulfonate compound is preferably activated by light irradiation prior to printing.

The diazoamino compound that can be used in the present invention is a compound prepared by reacting a diazo group with dicyandiamide, sarcosine, methyl taurine, N-ethylanthranilic acid-5-sulfonic acid, monoethanolamine, diethanolamine, guanidine or the like.

The quinondiazides used in the present invention are regarded as the internal salt of the diazonium salt in terms of structure and are, for example, o-quinondiazide or o-naphthoquinondiazide. Quinondiazide includes salts, esters and amides of compounds selected from 1,2-quinondiazid-4-sulfonic acid, 1,2-naphthoquinone diazide-5-sulfonic acid, 1,2-naphthoquinone diazide-4-sulfonic acid, and so on. Specific examples of the quinondiazide used in the present invention are sodium 1,2-quinondiazide-4-sulfonate, sodium 1,2-naphthoquinone diazide-5-sulfonate, sodium 1,2-naphthoquinone diazide-4-sulfonate, p-cumylphenyl 1,2 naphthoquinone diazide-5-sulfonate, p-cumylphenyl 1,2-naphthoquinone diazide-4-sulfonate, methyl 1,2-naphthoquinone diazide-5-sulfonate, ethyl 1,2-naphthoquinone diazide-5-sulfonate, 1,2-naphthoquin dimethylamide -sulfonic acid, esters of 1,2-naphthoquinone diazide-5-sulfonic acid and novolac resin and so on. In addition, these light-decomposing diazo compounds can be used alone or in combination.

The binder used in the present invention is an element that interacts with the diazo compound to form a pigment. For example, conventional paint-forming components capable of forming a yellow pigment are compounds that have a methylene group activated by a carbonyl group adjacent to it and are represented by the general formula RCOCH ₂ CO-R ', where R represents an alkyl group or an allyl group, and R 'is an aromatic amine. Magenta - a binder is, for example, 1) cyanoacetyl - derivatives of cyclic compounds or 2) heterocyclic compounds having an active methylene or any other binding part on a heterocyclic ring. Magenta paint-forming components include, for example, pyrazolone compounds and indazolone compounds. Cyan binders include, for example, phenols and naphthols.

Specific examples of the binder of the present invention are 4- (p-toluenesulfonylamino) -ω-benzoylacetanilide, α-benzoyl-o-methoxyacetanilide, 2-cyanoacetylcumaron, 1- (2,4,6-trichlorophenyl) -3-p-nitroamino-2 -pyrazolon-5-one, resorcinol, phloroglucinol, 2,3-dihydroxynaphthalene, 2,6-dibromo-1,5-dihydroxynaphthalene, N- (o-acetamidophenethyl) -1-hydroxy-2-naphthoamide and so on. In addition, these color-forming components can be used alone or in combination.

For a more uniform passage of the interaction of the diazocompound and the binder in the main atmosphere, the main material is preferably introduced into a heat-sensitive color-forming layer. As the basic material, slightly soluble in water or insoluble in water is used a basic material or a material capable of alkali formation when heated. The basic material includes, for example, nitrogen-containing compounds such as inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, imidazoles, imidazolines, triazoles, morpholines, p , amidines, formamidines, pyridines and so on.

Specific examples of these compounds are tricyclohexylamine, tribenzylamine, octadodecylbenzylamine, stearylamine, allyl urea, thiourea, methylthiourea, allyl thiourea, ethylene thiourea, 2-benzylimidazole, 4-phenylimidazole, 2-phenyl-2-phenyl-2-phenyl-2-phenylimide -2-imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-triphenylguanidine, 1,2-dicyclohexylguanidine, 1,2,3-tricyclohexylguanidine , guanidine trichloroacetate, N, N'-dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetate, 2-aminobenz thiazole, 2-benzoylhydrazinobenzothiazole and so on. These basic materials can be used alone or in combination.

In the present invention, the shelf life can be improved by adding a weak acid, such as citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid or the like to a heat-sensitive color-forming layer formed by a combination of a diazo compound and a binder.

It must be said that the color-forming components used in the present invention can be used in the form of a solid dispersion, which is obtained by dispersing the components in an aqueous solution of a water-soluble polymer, followed by coating and drying, as in the usual method used for heat-sensitive recording materials. It is also possible to improve the stability of green color when sealing a color-forming substance with the formation of microcapsules and prevent the color-forming substance from contacting the developer at ordinary temperatures, using the insulating effect of the capsule walls, as described in Japanese patents JP-A-59-190886, JP-A-60-49991 , JP-A-61-169281 and so on. Microcapsules are characterized in that they allow the color-forming substance and the developer to interact with each other when heated at a certain temperature or higher. The temperature at the beginning of the interaction of the color-forming substance with the developer can be controlled by appropriately selecting the substance of the capsule walls, the main substance of the capsule, additives, and so on.

As the substance for the walls of the microcapsules in the present invention, mention may be made of conventional substances for the walls of the microcapsules, such as polyurethanes, polyurea, polyesters, polycarbonates, urea-formaldehyde resins, melamine resins, polystyrenes, styrene-methacrylate copolymers, gelatin, poly (vinylpyrrolide , poly (vinyl alcohol) s and so on. These polymers can be used alone or in combination.

In the present invention, any water-soluble resins or water-dispersible resins can be used as the adhesive contained in the heat-sensitive color-forming layer. However, when any of these resins is mixed with dispersions of the aforementioned color-forming dye and developer, respectively, the resulting mixture should be without pigment, conglomerates and not be highly viscous. In addition, the coating film formed as a heat-sensitive recording layer should be rigid and should not have a desensitization effect. The adhesive content in the heat-sensitive color-forming layer is preferably from 8 to 20% relative to the amount (in solid units) of the heat-sensitive color-forming layer. A content of less than 8% is unfavorable since the strength of the coating film is reduced. A content of more than 20% causes a problem of sensitivity reduction. To improve the water resistance of the heat-sensitive color-forming layer, a cross-linking agent can be used to cure the resin.

In the color heat-sensitive recording material of the present invention, the formation of an intermediate layer between the heat-sensitive recording layers is effective for improving thermal separation. The intermediate layer includes, as a main component, the same resin as a water-soluble or water-dispersible resin used as an adhesive in heat-sensitive recording layers, and may also include pigments, crosslinking agents, and so on. The coating amount of the intermediate layer is preferably from 1.0 to 5.0 g / m ² . When the coating amount is less than 1.0 g / m ² , a sufficient prophylactic effect on diffusion between the recording layers cannot be obtained, which leads to a deterioration in image quality. When the coating amount is greater than 5.0 g / m ² , the sensitivity is adversely reduced.

As a particularly preferred form, a color heat-sensitive recording material can be mentioned in which two heat-sensitive recording layers have different color developing temperatures and undergo color development in different color tones, respectively, are laminated on one side of the substrate, and from these recording layers, the upper heat-sensitive recording layer contains either an agent used as a developer, or as a tone reducing agent, or a reversible developer, and weakly heat-sensitive recording layer containing a urea-urethane developer compound.

Of these, the agent used as a developer and as a tonic reducing agent in the upper heat-sensitive recording layer is an amphoteric compound having an acid group with a color development function, and a main group with a bleaching function, which perform the function of color development when heated at low temperature and perform discoloration function when heated at high temperatures. A typical example of an acid group is a phenolic hydroxyl group or a carboxyl group. A typical example of a basic group is an amino group. Although the amphoteric compound may have a basic group as a functional group, it preferably has a basic group as part of a salt compound, and in combination with a phenol carboxylic acid compound and an amine compound. Specific examples of such an agent are used both as a developer and as a tonic reducing agent, as described below. The phenol carboxylic acid compound, which is the main part of the agent used both as a developer and as a tone reducing agent, includes 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3, 5-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, gallic acid, bis (4-hydroxyphenyl) acetic acid, 3,3-bis (4-hydroxyphenyl) propionic ki slot and so on.

The amine compound, which together with phenol carboxylic acid forms salts or complex salts, includes octylamine, nonylamine, decylamine, laurylamine, tetradecylamine, heptadecylamine, stearylamine, behenylamine, 3-methoxypropylamine, hexamethylenediamine and so on.

A reversible solvent is, for example, a phenolic compound or a phosphonic acid compound that has an aliphatic hydrocarbon group of 8 or more carbon atoms. Specific examples of such a reversible developer are listed below. A reversible developer is not limited to those mentioned below, and any reversible developer may be used provided that it has a color development function when heated at a low temperature and a decolorization function when heated at a high temperature.

A reversible developer includes 4- (octadecylthio) phenol, 4- (dodecylthio) phenol, 4- (octadecyloxy) phenol, 4- (dodecyloxy) phenol, N-octadecyl-4-hydroxybenzamide, 4'-hydroxydocosananilide, N- (4 -hydroxyphenyl) -N'-n-octadecylurea, docosylphosphonic acid and so on. When recording is performed on a thermal printer or the like using the color heat-sensitive recording material of the present invention, printing by heating at low temperature causes only the low-temperature color-forming layer to appear and printing by heating at high temperature causes discoloration in the low-temperature color-forming layer in the printed part and causes only a high temperature color-forming layer.

The use of a urea-urethane compound makes it possible to obtain a laser marking product that has sufficient dyeing intensity and gives such a stable color image when printing that the image is slightly discolored or faded even when exposed to fats and oils, chemicals, fingerprints and so on. Therefore, use is particularly preferred in terms of long shelf life of records.

The heat-sensitive recording layer of the laser marking product of the present invention preferably contains an agent that improves recording sensitivity.

As an agent that improves the recording sensitivity used here, a compound is used that can absorb the laser beams used for irradiation. Specific examples of such agents are various inorganic compounds such as aluminum hydroxide, wollastonite, bentonite, mica (e.g. muscovite and phlogopite), calcium silicate, talc, kaolin, clay and silicate mineral raw materials (e.g. foyaite, amphibole and albite). Particularly preferred are aluminum hydroxide, muscovite, wollastonite and kaolin. These inorganic compounds may be used alone or as mixtures thereof.

The proportion of the colorless or light-colored dye precursor to the recording sensitivity agent used in the heat-sensitive recording layer of the present invention is not particularly limited and can be appropriately selected depending on the type of dye precursor and the recording sensitivity improving agent used. Typically, an agent that improves recording sensitivity can be used in a proportion of from 10 to 5000 parts by weight, preferably from 100 to 2000 parts by weight, per 100 parts by weight of a color-forming substance.

The content of the dye precursor substance, the urea-urethane compound of the developer and the recording sensitivity improving agent in the heat-sensitive recording layer can be set as follows: based on the total mass (in solid units) of the specified layer, the dye precursor content is in the range from 5 up to 30 wt.%, preferably from 10 to 25 wt.%, the content of the urea-urethane compound of the developer is in the range from 10 to 60 wt.%, preferably from 20 to 50 wt.%, and the content an agent that improves recording sensitivity is in the range from 5 to 40 wt.%, preferably from 10 to 30 wt.%.

Also, incorporation of an acid developer into the heat-sensitive recording layer of the laser marking product of the present invention improves sensitivity and allows the laser marking product to produce a brilliant color. As an acidic developer, the conventional electron-acceptor substances given above are exemplified.

To further improve the sensitivity of the laser marking product of the present invention, a heat-fusible substance can be introduced. The heat-fusible substance is preferably one that has a melting point of 60 ° C to 180 ° C, in particular 80 ° C to 140 ° C.

The color-forming composition for marking of the present invention can be obtained using the colorless or light-colored dye precursor substance, the urea-urethane developer compound, the recording sensitivity enhancer and the aqueous binder and water as the most important components, and mixing various auxiliary substances, if necessary.

The water used in the color-forming composition for marking has a pH in the range of 5 to 12, preferably 6 to 9. When the pH is lower than 5, a haze is formed. When the pH is higher than 12, then undesirable effects, such as a decrease in the color-forming ability of the urea-urethane developer compound, are likely to occur. Water may be used in admixture with a water-soluble organic solvent such as methanol, ethanol or the like.

In addition to the essential components described above, various excipients can, if necessary, be incorporated into the color-forming composition for marking used in the present invention, for example, to facilitate application of the composition to the substrate. Various excipients include, for example, dispersing agents (e.g. sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sodium salt of lauryl alcohol and sulfuric acid and metal salts of fatty acids), shading agents (e.g. titanium oxide), anti-foam agents, viscosity modifiers, and fluorescent dyes, and coloring agents.

The substrate onto which the color-forming marking composition of the present invention is applied is not specifically limited provided that it is necessary for marking. As a substrate, for example, food containers, packaging materials, an electronic component, and the like, and products (e.g., substrates for labeling) applied to them can be pre-divided into parts. As a substrate for labels, depending on the purpose, essentially paper (for example, paper and synthetic paper), synthetic polymer films, plastic, metallized paper and synthetic paper, metalized films, metals, wood and so on are used.

A color-forming composition for marking is prepared as follows. The binding agent is dissolved or dispersed in water or in a solvent consisting mainly of water. Among the components that can be dispersed in water or in a solvent consisting mainly of water are color-forming compounds, a developer, a recording sensitivity enhancer, and the like, which are treated together or independently with water or an aqueous solvent that contains a dispersant, such like poly (vinyl alcohol) using a dispersing apparatus, such as a ball mill, disintegrator, sand mill or the like, to thereby obtain one or more their variances. The average particle size of each component after the dispersion is usually about 2 μ or less, preferably about 1 μ or less. Then the binding agent and the dispersion (s) were mixed to obtain the color-forming labeling composition of the present invention. The solids content of said color-forming composition for marking is from 20 to 70 wt.%, Preferably from about 30 to about 65 wt.%.

The color-forming composition for marking can be applied directly to the substrate, or it can be applied to the substrate, which is previously subjected to surface treatment by applying a substrate or the like. The application may be carried out using a suitable coating device, for example, it may be carried out using a roller coating device, a grooved roller coating device, micro-coating devices of a grooved roller, a knife coating device, a spray coating device or the like. . The thickness of the coating film (heat-sensitive recording layer) obtained by application and drying can usually be set from 1 to 4 μ. When the thickness is less than 1 μ, then the manifestation of color using laser irradiation is insufficient, in addition, the coating film is prone to exfoliation. On the other hand, when the thickness is greater than 4 μ, the drying characteristics and adhesiveness of the label are prone to deterioration. Drying is different depending on the coating conditions, such as conveyor speed, and can be carried out either at room temperature or when heated under conditions that do not cause color formation in the heat-sensitive recording layer.

The protective layer of the laser marking product of the present invention is obtained by applying a clear coating liquid to a heat-sensitive recording layer. The clear coating liquid is an aqueous composition comprising an aqueous binding agent, water and the like.

As the aqueous binding agent used in the transparent coating liquid for the protective layer in the present invention, one can be mentioned that was obtained using as a base a substantially known water-soluble or water-dispersible resin used in the coating material or ink. Such a resin has a hydrophilic group (for example, a carboxyl group or an amino group) optionally added thereto to impart water solubility or water dispersibility. As said resin for an aqueous binding agent, resins having a glass transition temperature in the range of 20 to 80 ° C., preferably 35 to 70 ° C. are used. When the glass transition temperature is lower than 20 ° C., abrasion resistance, chemical resistance, the water resistance and the like of the protective layer is deteriorated. On the other hand, when the glass transition temperature is higher than 80 ° C, the protective layer becomes brittle, weakly elastic, and the like, and easily breaks. Therefore, both such glass transition temperatures are undesirable. If necessary, in addition to the components described above, a leveling agent, glidants, antifoam agents and the like can be added to the above clear coating liquid.

As an aqueous binding agent used in a clear coating liquid, an acrylic resin can be prepared using an alkyl (carbon number: 1 to 24) ester of acrylic acid or methacrylic acid as the main component in combination with any of, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and so on; hydroxy-containing unsaturated monomers such as hydroxyethyl acrylate, hydroxypropyl methacrylate and so on; amino-containing unsaturated monomers such as acrylamide, methacrylamide and so on; and other unsaturated monomers, such as styrene, acrylonitrile, vinyl acetate, vinyl chloride and so on, and copolymerizing acrylic esters with such a comonomer. The polyester resin can be prepared by the ester reaction of a polybasic acid (including acid anhydrides) having two or more carboxyl groups in the molecule, with a polyhydric alcohol having two or more hydroxyl groups in the molecule. The glass transition point of such an aqueous binder can be set for any temperature essentially by choosing the type, combination and proportions of the components that make up the specified binder.

Said clear liquid is obtained by dissolving or dispersing the aforementioned aqueous binding agent in suitable water, and if necessary, administering together with leveling agents, glidants, antifoam agents and the like. The solid component of the specified transparent coating liquid is in the range from 20 to 70 wt.%, In particular from 30 to 60 wt.%.

The specified transparent coating liquid can be printed (deposited) on the surface of the dried film formed as a heat-sensitive recording layer. The printing method (application) is not particularly limited. The application can be carried out using a roller coating device, a coating device for a grooved roller, microdevices for coating a grooved roller, a knife coating device, a spray coating device or the like.

The coating film thickness thus obtained can usually be set from 3 to 10 μ. When the thickness is less than 3 μ, then the protection of the heat-sensitive recording layer with the specified transparent coating is insufficient and resistance to chemical attack, abrasion resistance and the like deteriorate. On the other hand, when the thickness is greater than 10 μ, the drying characteristics and physical characteristics of the coating film are prone to deterioration. The drying of the indicated transparent application liquid varies depending on the coating conditions, such as conveyor speed, and can be carried out either at room temperature or when heated under conditions that do not cause color formation in the heat-sensitive recording layer.

When the heat-sensitive recording layer of the marking product thus obtained is irradiated with laser beams, the irradiated part is heated, thus the urea-urethane compound of the developer and the dye precursor substance interact with each other with the formation of color, which leads to marking. Although the amount of laser light energy used for irradiation is not specifically limited, it is preferably 1.4 J (joule / cm ² ) or less, taking into account the possibility of cracking of the film. On the other hand, although the lower limit of the amount of energy required for the development of color is unknown, since there is no device capable of producing low energy, sufficient manifestation of color occurs even when the amount of energy is 0.4 J / cm ² . Therefore, a suitable amount of irradiation energy for color formation is in the range from 0.4 to 1.4 J / cm ² , in particular from 0.45 to 1.2 J / cm ² . As a laser used for irradiation, a pulsed laser or a scanning laser is suitable. As for the type of laser, any laser can be used, for example gas lasers, excimer lasers and semiconductor lasers. Specific examples of the laser are carbon dioxide lasers, mixed gas lasers, yttrium aluminum garnet lasers, ruby lasers, and so on.

As a method for irradiating a part of a desired shape with laser beams, a method for irradiating a coating film with laser beams through a metal mask may be mentioned to irradiate the coating film with laser beams in accordance with the opening form of the metal mask; and a method for introducing the desired shape into the computer and irradiating the coating film with laser beams in accordance with the desired shape by the so-called one-step drawing method. When the heat-sensitive recording layer is irradiated with laser beams, the temperature in the irradiated part increases to cause color formation caused by melting and mixing of the color-forming components in the heat-sensitive recording layer, which leads to the appearance of letters or numbers that have the exact desired shape. This color change by irradiation can be performed instantly, since the energy density of the laser beams is high.

The label as the laser marking product of the present invention can be obtained by forming a heat-sensitive recording layer and a protective layer by the above methods on a substrate for the label, essentially selected, depending on the purpose, from paper (e.g. paper and synthetic paper), synthetic polymer films, plastic, metallized paper and synthetic paper, metallized films, metals, wood and so on. Although a label thus obtained can be used in all areas of conventional labels, it is preferably used in areas such as food, medicine, perfumery, book publishing, electronics and electronic parts, and so on.

The packaging material as the laser marking product of the present invention is obtained by forming a heat-sensitive recording layer and a protective layer by the above methods on any of various conventional packaging materials, such as boxes, packaging paper and bags, which are obtained using a substrate essentially selected depending on targets made of paper (e.g. paper and synthetic paper), synthetic polymeric films, plastic, metallized paper and synthetic paper, films, metals, wood, and so on. Although a label thus obtained can be used in all areas of conventional labels, it is preferably used in areas such as food, medicine, perfumery, book publishing, electronics and electronic parts, and so on.

The container as a laser marking product of the present invention is obtained by forming a heat-sensitive recording layer and a protective layer on a substrate, such as glass, plastic, metal or the like, by the above methods. This food container can be used as ordinary food containers, such as bottles for drinks and refreshments, rotary food containers, instant food containers, cosmetics containers, medical containers, perfumes and so on.

When the color-forming composition of the present invention is used in a pressure sensitive recording material, the recording material may take, for example, the forms described by US Pat. Nos. 2,504,570, 2,712,507, 2,730,456, 2,730,457 and 3,418,250, and so on. That is, various forms can be used, such as the following: pressure sensitive recording paper obtained by dissolving a dye precursor or a dye precursor mixture in a solvent containing one or a mixture of two or more alkyl naphthalenes, alkyl diphenyls, alkylated diphenylmethanes alkyl diarylethanes, synthetic oils (e.g. chlorinated paraffins), vegetable oils, animal oils, mineral oils and so on, by dispersion rgirovanie the resulting solution in a binding agent or introducing the solution into microcapsules, applying a dispersion to the substrate or applying microcapsules to the substrate together with a binding agent, placing the bottom paper, thus obtained, and the top paper coated with a dispersion of the urea-urethane compound (and the amino compound and / or developer, and so on), on top of each other so that their coated surfaces are facing each other; pressure sensitive recording paper obtained by fixing between the aforementioned top paper and the bottom paper, an intermediate paper coated with a dispersion of a urea-urethane compound on one side and a dye precursor substance on the other moan; mixed type pressure sensitive recording paper obtained by applying the above dispersion of a urea-urethane compound (and an amino compound and / or developer) and the above dispersion containing a dye precursor substance onto one surface of a substrate in the form of a mixture or a multilayer form; and a pressure sensitive mixed-type recording paper obtained by incorporating each dye precursor substance and a urea-urethane compound (and an amino compound and / or developer) into microcapsules and applying a mixture of two kinds of microcapsules on the same substrate surface.

As a method for producing microcapsules, for example, the coacervation method described in US Pat. Nos. 2,800,457 and 2,800,458, the interfacial polymerization method described in JP-B-38-19574, JP-B-42-446, JP-B-42 can be used. -771 and so on, the in situ method described in JP-B-36-9168, JP-B-51-9079 and so on, the method of cooling the molten dispersion described in UK patent No. 952807 and 965074 and so on, and the method spray drying described in US patent No. 3111140, UK patent No. 930422 and so on.

The color-forming composition of the present invention corresponds to a combination of a dye precursor and a developer described in each of the above references and the like.

To form a pressure sensitive recording layer, each component, such as a urea-urethane compound, can be used in the form of a solution or dispersion in a solvent. In the case of a color-forming system further comprising an amino compound and / or a developer, each component can be used in the form of a solution or dispersion in a solvent, or a combination of a urea-urethane compound, an amino compound and optionally a developer can be used in the form of a solution or dispersion in a solvent.

In the above interfacial polymerization methods used to produce microcapsules, a film is formed at the interface using two types of monomers, i.e., an oil monomer and a water-soluble monomer. For example, a method is known in which polybasic acid chloride is used as an oily phase and a polyvalent amine as an aqueous phase, and a polyamide film is obtained at the interface; a method in which polybasic acid chloride is used as an oil phase and a polyhydric hydroxy compound is used as an aqueous phase and a polyester film is formed at the interface; a method in which a polyvalent isocyanate is used as an oil phase and a polyhydric alcohol or a polyhydric phenol as an aqueous phase, and a polyurethane film is formed at the interface; and a method in which a polyvalent isocyanate is used as an oil phase and a polyvalent amine as an aqueous phase, and a polyurethane film is formed on the anise. Thus, when the interfacial polymerization process is used to prepare microcapsules, the isocyanate compound is used in some cases as a reactive monomer to form a film.

In this case, said isocyanate compound is consumed to form a film for microcapsules and does not directly relate to the appearance of a color image, and it is absolutely necessary to use a water-soluble monomer together with the isocyanate compound. In these cases, its use is different from the use of the isocyanate compound of the present invention.

Dispersions of compounds that are not filled with microcapsules are obtained by finely grinding one or more compounds as a component in an aqueous solution containing a compound having a dispersion ability, such as a water-soluble polymer, a surfactant, or the like. The urea-urethane compound may be dispersed together with the amino compound and the acid developer.

The substrate used in the pressure-sensitive recording material is mainly paper, although depending on the purpose, in addition to paper, various woven materials, non-wovens, synthetic polymeric films, laminated papers, synthetic papers, metal foil and composite sheets can be used. obtained by combining two or more of them.

As a binding agent, various binding agents can be used. The binding agent includes, for example, water-soluble binding agents, such as starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, poly (vinyl alcohol) s, modified poly (vinyl alcohol) s, poly (acrylate) sodium, acrylamide-acrylic ester copolymers, acrylamide-acrylic ester-methacrylic acid terpolymers, alkaline copolymers of styrene-maleic anhydride, alkaline copolymers of ethylene-meleic anhydride and so on; and water-insoluble latex type binders selected from styrene-butadiene copolymers, acrylonthyryl-butadiene copolymers, acrylate-butadiene copolymers and so on.

In the recording material of the present invention, the recording layer may comprise a hindered phenol compound or an ultraviolet absorber. Hindered phenol or an ultraviolet absorber includes, 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 and tetra (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarbonate.

A method for producing a color-forming layer is not particularly limited. A color-forming layer is obtained, for example, by applying a coating liquid for the color-forming layer to a substrate with a suitable coating method, such as a free-fall curtain coating, an air knife coating, a Bariber blade coating, a clean blade coating or the like, and drying the substrate thus obtained. The coating amount of coating fluid for the color-forming layer is not particularly limited and is usually set in the range of 1 to 15 g / m ² , preferably about 3 to 10 g / m ² , in units of dry weight.

The thermal response can be improved by forming an intermediate layer between the heat-sensitive recording layer and the substrate. In the case of conventional heat-sensitive recording materials, for example, the sharing of a heat-fusible material in a color-forming layer can be used. Sensitivity improvement by this method is beneficial because fog is prone to form when heated or friction. This facilitates the occurrence of fog, especially in heat-sensitive recording materials obtained using a urea-urethane compound of the developer, excellent in sensitivity of color manifestation. In the case of conventional heat-sensitive recording materials without preserving the print, even if fog forms, it disappears as a print, therefore, in particular, fog in the case of using recording material after long storage was rarely taken into account. However, in the case of heat-sensitive recording materials obtained using a urea-urethane developer compound, which are particularly excellent for long-term print storage, the following problem, characteristic of them, arises in some cases: once fog appears, it persists and therefore accumulates every time the recording material is stored and then used, so that the surface of the recording material becomes dirty when the recording material is used after long storage . In this case, the formation of an intermediate layer can achieve practical sensitivity of color development without using a heat-fusible material or using only a small amount of heat-fusible material, and a heat-sensitive recording material can be obtained that is so excellent in resistance to fog formation by heating or friction that the fog is difficult accumulates even if recording material is used after long-term storage.

The intermediate layer consists mainly of organic or inorganic pigment, hollow particles and an aqueous binding agent, such as a water-soluble polymer or latex. As the organic or inorganic pigment and aqueous binder, the same organic or inorganic pigment and aqueous binder can be used as that used in the heat-sensitive recording layer.

The method for producing the intermediate layer is not particularly limited. As this method, a method for producing a thermally sensitive recording layer can be used. The dry distribution for the intermediate layer is in the range of preferably from 2.0 to 15.0 g / m ² . In this case, the pH on the surface of the intermediate layer obtained on the substrate is preferably from 3 to 9, more preferably from 5 to 9, more preferably from 6 to 8.

In addition, in the present invention, the abrasion resistance of the obtained recording paper, if necessary, can be improved by forming a protective layer, consisting mainly of a water-soluble polymer, on the heat-sensitive recording layer. When a urea-urethane developer compound of the present invention is used which has excellent color development sensitivity and imprint stability during long-term storage, traces of friction can be left due to the high sensitivity. On the other hand, once traces of friction left are stored for an indefinite period of time, and therefore traces of friction are accumulated each time the recording material is stored and then used. Therefore, the paper surface in some cases becomes dirty when the recording paper is used after long-term storage. In this case, when a protective layer is formed, the accumulation of traces of friction can be difficult, even if the recording paper is used after long-term storage. Specific examples of the water-soluble polymer contained in the protective layer are water-soluble polymer binding agents indicated relative to the above heat-sensitive recording layer. The water-soluble polymer can be used in conjunction with a conventional waterproofing agent capable of waterproofing the water-soluble polymer. Specific examples of the waterproofing agent include formaldehyde, glyoxal, chromium alum, melamine, melamine-formaldehyde resins, polyamide resins, polyamide-epichlorohydrin resins, and so on.

In addition, pigments, metal soaps, waxes, cross-linking agents and so on are included in the protective layer with the aim, for example, to improve compliance with the thermal head during printing and to improve the water resistance of the protective layer.

Pigments include zinc oxide, calcium carbonate, barium sulfate, titanium oxide, lithopone, talc, pagodite, kaolin, aluminum hydroxide, quartz, amorphous quartz and so on. The amount of added pigments is from 0.5 to 4 times, preferably from 0.8 to 3.5 times, of the total weight of the polymers. When the amount is below the lower limit of the above region, the pigments are not effective in improving compliance with the thermal head. When the amount is above the upper limit, the sensitivity of the heat-sensitive recording material decreases remarkably so that the commercial value of the recording material decreases.

Metal soaps include, for example, emulsions of metal salts of higher fatty acids, such as zinc stearate, calcium stearate, aluminum stearate and so on. Metal soaps were added in a proportion of from 0.5 to 20 wt.%, Preferably from 1 to 10 wt.%, Based on the total weight of the protective layer. Waxes include, for example, emulsions of solid wax, microcrystalline wax, carnauba wax, methylolstearoamide, polyethylene wax, and so on. Wax was added in a proportion of 1 to 20 wt.%, Preferably 1 to 10 wt.%, Based on the total weight of the protective layer.

When a protective layer is formed on the heat-sensitive recording layer, surfactants are added to the coating liquid to form a protective layer to obtain a uniform coating layer. Surfactants include alkali metal salts of sulfosuccinic acids, fluorine-containing surfactants and so on. Specific examples of surfactants include sodium salt or ammonium salts of di- (2-ethylhexyl) sulfosuccinic acid, di- (n-hexyl) sulfosuccinic acid and so on. In general, any surfactant is effective provided that it is anionic. Conventional auxiliary additives, such as fillers, heat-melting materials (lubricants), surfactants, fluorescent dyes and so on, can also be included in the protective layer. Specific examples of fillers, heat-fusible materials and fluorescent dyes are those indicated relative to the aforementioned heat-sensitive recording layer. The dry distribution for obtaining the protective layer is in the range of preferably from about 0.5 to about 10 g / m ² , in particular from about 1 to about 5 g / m ² .

When a back side layer (back coating layer) is formed on the wrong side of the recording layer of the recording material using the production method of the present invention, if necessary, curling of the obtained recording paper may be difficult. Especially in the case of the urea-urethane compound of the developer of the present invention, the reverse side layer formation is effective for the following reason: said developer is superior to other developers in dispersing ability, which easily gives dispersion with a small particle size, and has high sensitivity, but when the coating liquid obtained by mixing the specified developer with other necessary components is applied to the substrate, the adhesion force of the binding agent increases during height due to the small particle size of the developer, therefore, the recording layer is more easily compressed. As the components of the coating fluid for the back side layer and the coating method for the coating fluid, the same components and method can be used as in the case of the protective recording layer. The dry distribution of the coating liquid is in the range preferably from 2.0 to 10.0 g / m ² .

The present invention is described in more detail in the following examples.

Analysis of substances and assessment of physical properties was carried out by the following methods.

<IR spectrum>

Measured by diffuse reflective spectroscopy using FTIK-8100M, manufactured by Shimadzu Corp.

<Mass spectrum>

Measured using JMS-HX100, manufactured by JEOL LTD., Nitrobesyl alcohol as a matrix and xenon as primary gas.

<Sensitivity of the manifestation of color of thermal paper>

The staining intensity when applying a voltage of 24 V and a pulse duration of 1.5 ms was measured with an optical densitometer using a testing printer manufactured by Ohkura Denki K.K. and a thermal head KJT-256-8MG manufactured by Kyocera Co., Ltd.

<Resistance to plasticizer>

A heat-sensitive recording material was installed between vinyl chloride wrapping films or a vinyl chloride file, and a load of 300 g / cm ² was applied on top of it. After 24 hours at 40 ° C, the staining intensity of the printed part and the unprinted part (the initial surface of the recording material) was visually evaluated. When only a slight decrease in the intensity of the imprint was observed, then the ability to save the imprint was evaluated as optimal.

<Thermal resistance>

The heat-sensitive recording material was left at 60 ° C and a relative humidity of 25% for 24 hours, and the degree of fading of the print was visually evaluated. When the degree of fading was evaluated as low, then the ability to preserve the imprint was assessed as optimal.

In addition, the heat-sensitive recording material was left at 80 ° C and a relative humidity of 25% for 24 hours and the degree of fading of the print was visually assessed. When the degree of fading was evaluated as low, then the ability to preserve the imprint was assessed as optimal. The staining intensity of the initial surface of the recording material was also visually evaluated. When only a slight decrease in color development was observed, then the ability to maintain the original surface of the recording material was evaluated as optimal.

<Intensity of staining of pressure sensitive paper>

The top paper and the bottom paper were placed one on top of the other so that their coated surfaces were in contact. Pressure was applied from above to obtain a color image on the bottom paper. The staining intensity of the resulting color image was measured using a Macbeth RD917 densitometer.

<Solvent Resistance>

Hand cream (Atrix, trade name, manufactured by Kao Corp.) was applied in a thin layer onto a part with a color image obtained by evaluating the intensity of staining, and then left at ambient temperature for 7 days and visually assessed the intensity of staining. When only a slight decrease in the intensity of the imprint was observed, then the ability to save the imprint was evaluated as optimal.

Example 1

To 27.8 g of 2,4-toluene diisocyanate, 111 g of toluene as a solvent was added, after which a solution of 7.4 g of aniline in 37 g of toluene was added dropwise at room temperature for 1 hour, and the reaction was carried out for another 1 hour. A white solid precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuo to give 20 g of white crystals. Then 5 g of the compound thus obtained was added to 50 ml of methanol and the reaction was carried out at 60 ° C for 30 minutes, after which the excess methanol was removed using an evaporator, and toluene was added to the precipitate for crystallization. The resulting white crystals were isolated by filtration, washed with hexane and then dried overnight in vacuo to give 5.4 g of white crystals. The melting point of these white crystals was 196 ° C.

An analytical measurement of these white crystals showed the following.

IR measurement result:

The characteristic peaks were at 1060 cm ^-1 , 1250 cm ^-1 , 1600 cm ^-1 , 1650 cm ^-1 , 1670 cm ^-1 , 1700 cm ^-1 and 3300 cm ^-1 ,

It has been proven that the structural formula of the main component of this compound is the structural formula of the above compound (S-1).

Then a dispersion was obtained by dispersing 2 g of this compound, grinding it together with 8 g of a 2.5 wt.% Aqueous solution of polyvinyl alcohol (Gohseran L-3266, trade name, manufactured by The Nippon Synthetic Chemical Industry Co., Ltd.) in a shaker for paint within 6 hours. The dispersion temperature immediately after the dispersion process was 25 ° C. The diameter of the dispersed particles of the compound was approximately 0.6 μm.

Another dispersion was obtained by dispersing 70 g of 3-dibutylamino-6-methyl-7-anilinofluorane, grinding it together with an aqueous solution of 130 g of 8 wt.% Polyvinyl alcohol in a sand mill (manufactured by AIMEX CO., LTD .; tank volume 400 ml) with a speed of 2000 rpm for 3 hours.

Another dispersion was obtained by dispersing 70 g of diphenyl sulfone, grinding it together with an aqueous solution of 130 g of 5.4 wt.% Polyvinyl alcohol in a sand mill (manufactured by AIMEX CO., LTD .; tank volume 400 ml) with a speed of 2000 rpm min for 3 hours.

Another dispersion was obtained by mixing 10 g of calcium carbonate with 30 g of water and mixing the mixture using a mixer.

The coating liquid was obtained by mixing and mixing the above dispersions and other components in the following proportions (proportions of dry basis); the dispersion of the above compound, calculated on the dry solid: 30 parts by mass, the dispersion of 3-dibutylamino-6-methyl-7-anilinofluoran, calculated on the dry solid: 15 parts by mass, the dispersion of diphenyl sulfone, calculated on the dry solid: 30 parts by mass, the dispersion of calcium carbonate, calculated on the dry solid: 20 parts by mass, the dispersion of zinc stearate (solids content: 16 wt.%), calculated on the dry solid: 10 parts by mass and 15 wt.% poly (vinyl alcohol) in terms of dry t erdoe material: 7 parts by weight.

The coating liquid was applied to the base paper with a base weight of 50 g / m ² using a coating installation to remove excess using a bar with a rod number 10. After drying, supercalendering was performed to obtain a heat-sensitive recording material. The coating amount of coating liquid was 4 g / m ² , calculated on the dry weight.

The result of the sensitivity assessment of the obtained thermally sensitive recording material was so optimal that the optical density was 1.2. The result of evaluating the degree of thermal color change of the initial surface of the recording material (thermal resistance) was so good that the color change was neglected. The thermal fading of the printed portion was preferably weak. The results of these estimates are summarized in table 1.

Example 2

To 17 g of 2,4-toluene diisocyanate, 40 g of methyl ethyl ketone was added as a solvent, after which 3.8 g of methanol was added dropwise thereto, and the reaction was carried out under stirring at 60 ° C. for 5 hours. Then, 9.9 g of 4,4'-diaminodiphenylsulfone was added thereto, and the reaction was carried out with stirring at 60 ° C. for 4 hours. After completion of the reaction, the resulting solution was cooled to room temperature and poured into 800 g of acetonitrile, and the crystalline precipitate obtained by filtration was washed with hexane and then dried overnight in vacuum to obtain 15 g of the compound as white crystals.

The melting point of white crystals was 169 ° C and their analytical measurements were as follows.

IR measurement result:

The characteristic peaks were at 1220 cm ^-1 , 1550 cm ^-1 , 1590 cm ^-1 , 1660 cm ^-1 , 1740 cm ^1- and 3300 cm ^-1 .

Mass spectrum analysis results:

[M + H] ^{+ was} determined at m / z 661.

It has been proven that the structural formula of the main component of this compound is the structural formula of the above compound (S-13).

Then, the heat-sensitive recording material was obtained in the same manner as described in example 1, except that instead of the urea-urethane compound synthesized in example 1, the compound obtained above was used and evaluated. The results obtained are summarized in table 1.

Example 3

3.46 g of aniline were dissolved in 100 ml of ethyl acetate, and the resulting solution was stirred at room temperature. To it was added dropwise a solution of 10 g of trimethylolpropane adduct selected from toluene diisocyanate (Coronate L, trade name, manufactured by Nippon Polyurethane Industry Co., Ltd .; 75% ethyl acetate solution) in 50 ml of ethyl acetate for 1 hour and reacted in for another 30 minutes. The resulting crystals were isolated by filtration and dried overnight in vacuo to give 5.1 g of the compound as white crystals. The melting point of white crystals was 161 ° C and their analytical measurement was as follows. IR measurement result:

The characteristic peaks were at 1070 cm ^-1 , 1220 cm ^1- , 1550 cm ^-1 , 1600 cm ^-1 , 1700 cm ^-1 and 3300 cm ^-1 .

It has been proven that the structural formula of the main component of this compound is the structural formula of the above compound (S-33).

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the compound obtained above was used and evaluated. The results obtained are summarized in table 1.

Example 4

To 10.4 g of 2,4-toluene diisocyanate was added 20 g of methyl ethyl ketone as a solvent, after which a solution of 3.7 g of 4,4'-diaminodiphenyl sulfone diluted in 30 g of methyl ethyl ketone was added dropwise to it, and the reaction was carried out at ambient temperature within 20 hours. After completion of the reaction, methyl ethyl ketone was removed by concentration, and then toluene was added to the precipitate, and a white solid precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuo to obtain 8.8 g of a compound as white crystals. Then, 15 g of phenol and then a small amount of dibutyltin dilaurate were added to 4 g of the obtained compound, and the reaction was carried out at 50 ° C. for 4 hours. After completion of the reaction, toluene was added to the reaction solution, and the crystalline precipitate obtained by filtration was washed with hexane and then dried overnight in vacuo to obtain 5.2 g of a urea-urethane compound as white crystals.

Then, 30 g of toluene to 10 g of 2,4-toluene diisocyanate was added as a solvent, after which 30 g of phenol was added thereto, and the reaction was carried out at 100 ° C for 3 hours. After completion of the reaction, toluene was removed by concentration and hexane was added to the precipitate. The white crystalline precipitate obtained by filtration was washed with hexane and then dried overnight in vacuo to give 15 g of the urethane compound as white crystals.

It has been proven that the structural formula of the main component of this compound is the structural formula of compound (C-2), described hereinafter.

Then, 3 g of the above urea-urethane compound and 2 g of the urethane compound were mixed to obtain a urea-urethane composition. Thereafter, 2 g of the urea-urethane composition was ground together with an aqueous solution of 8 g of 2.5 wt.% Methyl cellulose in a paint shaker for 45 minutes to disperse, thereby obtaining a dispersion.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the compound obtained above was used and evaluated. The results obtained are summarized in table 1.

Example 5

Heat-sensitive recording material was obtained in the same manner as in example 4, except that instead of the urea-urethane composition used in example 4, the urea-urethane composition obtained by mixing 4.5 g of urea-urethane compound and 0.5 g urethane compounds that were synthesized in example 4, and evaluated. The results obtained are summarized in table 1.

Example 6

Heat-sensitive recording material was obtained in the same manner as in example 4, except that instead of the urea-urethane composition used in example 4, 7.4 g of urea-urethane composition obtained as white crystals in the same manner as in Example 4, except that 2.2 g of diphenyl sulfone were added to the reaction system before precipitation by adding toluene after the synthesis of the urea-urethane compound by stirring the resulting mixture, adding toluene to the mixture, according to irradiating the crystalline precipitate by filtration, washing the crystals with hexane and then drying the crystals overnight in vacuo. The heat-sensitive recording material was evaluated. The results obtained are summarized in table 1.

Example 7

To 31.5 g of 2,4-toluene diisocyanate, a solution of 21.5 g of 4,4'-diaminodiphenyl sulfone in 60 ml of MEK at 70 ° C was added dropwise with stirring at 300-500 rpm for 4 hours, and the reaction was carried out in for another 4 hours to obtain a white viscous suspension of the reaction mixture. Then the reaction mixture was cooled to 50 ° C and 17.1 g of phenol was poured into the reaction mixture to dissolve in it, after which 0.015 g of triethylamine was added as a catalyst, and the reaction was carried out for 4 hours to obtain a yellow, transparent and viscous reaction mixtures. This reaction mixture was freed from the solvent and concentrated under reduced pressure to solidify, after which the resulting solid product was crushed and then dried overnight in vacuo to give approximately 70 g of a urea-urethane composition as a light yellow powder.

The melting point of the light yellow powder was 160-180 ° C. In the IR measurement of the powder, a broad peak formed by superimposing the characteristic peaks of the urea group and the urethane group, respectively, is at 1700 cm ^-1 .

The urea-urethane main component content in the urea-urethane composition was 68%, as measured by liquid chromatography.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except for using the above composition instead of the urea-urethane compound synthesized in example 1, and evaluated.

The results obtained are summarized in table 1.

Example 8

To 158.5 g of 2,4-toluene diisocyanate, 240 g of methyl ethyl ketone was added as solvent, and 107.5 g of 4,4'-diaminodiphenyl sulfone in powder form was added thereto at 30 ° C. with stirring at 400 rpm for 8 hours. After 1 hour, 26 g of methyl ethyl ketone was added thereto and stirred for another 15 hours to obtain a white viscous suspension of the reaction mixture. Then, a solution of 89.5 g of phenol in 15.8 g of methyl ethyl ketone was poured into the reaction mixture to dissolve in it, after which 9.3 g of a 1 wt.% Solution of triethylamine in methyl ethyl ketone were added thereto over 2 hours, and the reaction continued within 1 hour. After that, the reaction mixture was cooled to 20 ° C and stirred continuously for 3 hours to obtain a suspension containing slightly yellow precipitated crystals. The suspension was freed from the solvent and concentrated under reduced pressure to solidify, after which the resulting solid product was crushed and then dried overnight in vacuo to give 355 g of a urea-urethane composition as a slightly yellow powder.

The melting point of the slightly yellow powder was 130-170 ° C. In the IR measurement of the powder, the broad peak obtained by superimposing the characteristic peaks of the urea group and the urethane group, respectively, is at 1700 cm ^-1 . The content of the urea-urethane main component in the urea-urethane composition was 65%, as shown by measurement using liquid chromatography.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the compound obtained above was used and evaluated. The results obtained are summarized in table 1.

Example 9

To 27.8 g of 2,4-toluene diisocyanate was added 100 g of toluene as a solvent, after which a solution of 7.4 g of aniline in 37 g of toluene was added dropwise at room temperature for 1 hour, and the reaction was carried out for another 1 hour . A white solid, obtained by filtration, was washed with hexane and then dried overnight in vacuo to give 20 g of white crystals. Then, 5 g of the compound thus obtained were added to 50 ml of methanol, and the reaction was carried out at 60 ° C for 30 minutes, after which the excess methanol was removed using an evaporator, and the residue was dried overnight in vacuo to obtain 5.4 g of urea urethane composition in the form of white crystals. The melting point of the white crystals was 196 ° C. For IR crystal measurements, the characteristic peaks of the urea-urethane compound are at 1670 cm ^-1 and 1700 cm ^-1 . The content of the urea-urethane main component in the urea-urethane composition was 92%, in the form showed the measurement using liquid chromatography.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the compound obtained above was used and evaluated. The results obtained are summarized in table 1.

Example 10

40 g of methyl ethyl ketone was added to 17 g of 2,4-toluene diisocyanate as a solvent, after which 3.8 g of methanol was added dropwise thereto, and the reaction was carried out with stirring at 60 ° C. for 5 hours. Then, 9.9 g of 4,4'-diaminodiphenylsulfone was added thereto, and the reaction was carried out with stirring at 60 ° C. for 4 hours. After completion of the reaction, the methyl ethyl ketone solvent was removed using an evaporator, and the residue was dried overnight in vacuo to give 16 g of a urea-urethane composition as white crystals. The melting point of the white crystals was 169 ° C. In the IR measurement of crystals, the characteristic peaks of the urea-urethane compound are at 1660 cm ^-1 and 1740 cm ^-1 . The urea-urethane main component content in the urea-urethane composition was 52%, as measured by liquid chromatography.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the compound obtained above was used and evaluated. The results obtained are summarized in table 1.

Example 11

27.5 g of 2,4-toluene diisocyanate was dissolved in 253 ml of toluene, after which a solution of 14.7 g of aniline in 85 ml of toluene was added dropwise thereto at 40 ° C with stirring at 200 rpm for 30 minutes, and the interaction was carried out for another 30 minutes. To this white suspension, 18.0 g of 2,2-bis (4-hydroxyphenyl) propane, 262 ml of toluene and 0.42 mg of triethylamine were added as a catalyst, and the stirring speed was increased to 400 rpm. To prevent aggregation of particles in suspension in the initial reaction by controlling the degree of interaction, the interaction was carried out with a gradual increase in the reaction temperature as follows: 60 ° C for 5 h, 65 ° C for 2 h, 70 ° C for 1 h and 75 ° C within 1 hour. Then, 0.42 mg of triethylamine was added, and the reaction was carried out at 80 ° C. for another 8 hours. The reaction mixture was cooled to room temperature and the resulting white crystals were isolated by filtration. The white crystals were dried overnight in vacuo to give 59 g of a urea-urethane composition as white crystals. The melting point of these white crystals was 170 ° C. In the IR analysis of the crystals, the broad characteristic peak of the urea-urethane compound was at 1720 cm ^-1 . The urea-urethane main component content in the urea-urethane composition was 81%, as measured by liquid chromatography.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the compound obtained above was used and evaluated. The results obtained are summarized in table 1.

Examples 12-23

Heat-sensitive recording materials were obtained in the same manner as in example 8, except for the use of 4,4'-dichlorodiphenyl sulfone (example 12), 4,4'-dihydroxydiphenyl sulfone (example 13), 2,4'-dihydroxydiphenyl sulfone (example 14), 4 - (benzyloxy) phenol (example 15), salicylanilide (example 16), 4,4'-diaminodiphenylsulfone (example 17), 4,4'-dichlorobenzophenone (example 18), 4,4'-diaminodiphenylmethane (example 19), 4 , 4'-dimethoxybenzophenone (example 20), diphenyl carbonate (example 21), 4,4'-dimethoxyphenyl sulfone (example 22) or 4,4'-diallyloxyphenyl sulfone ( Example 23) instead of diphenylsulfone, and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 1.

Comparative Example 1

Heat-sensitive recording material was obtained in the same manner as in example 1, except for the use of 2,2-bis (4-hydroxyphenyl) propane instead of the urea-urethane compound synthesized in example 1, and evaluated. The results obtained are summarized in table 1.

Reference Example 2

To 17.4 g of 2, 4-toluene diisocyanate, 5 ml of methyl ethyl ketone was added as a solvent, after which a solution of 3.2 g of methanol in 5 ml of methyl ethyl ketone was added dropwise, and the reaction was carried out with stirring at room temperature for 2 hours. Then, a solution of 7.3 g of n-butylamine in 100 ml of methyl ethyl ketone was added dropwise thereto with stirring at room temperature, and the resulting mixture was stirred for 1 hour. A crystalline precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuo to give 27 g of the compound as white crystals. The melting point of white crystals was 156 ° C, and their analytical measurement was as follows.

IR measurement result:

The characteristic peaks were at 1240 cm ^-1 , 1550 cm ^-1 , 1640 cm ^-1 , 1720 cm ^-1 and 3300 cm ^-1 .

It has been proven that the structural formula of the main component of this compound is the formula (R-1) shown hereinafter.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the compound obtained above was used and evaluated. The results obtained are summarized in table 1.

Reference Example 3

To 10.0 g of 2,4-toluene diisocyanate was added 100 g of toluene.

While mixing the resulting mixture at 25 ° C, a solution of 15.5 g of stearylamine in 100 ml of toluene was added to it, and the reaction was carried out at 25 ° C for 22 hours. After completion of the reaction, a white solid precipitate was obtained by filtration, washed with toluene and then dried overnight in vacuo to obtain 20.4 g of white crystals. Thereafter, 5 g of the compound thus obtained was added in 50 ml of methyl ethyl ketone. While the resulting mixture was stirred at 80 ° C, a solution of 8.6 g of p-hydroxybenzylcarboxylic acid in 20 ml of methyl ethyl ketone and then 5 mg of dibutyltin taurate as a catalyst was added to it, and the reaction was carried out at 80 ° C for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a crystalline precipitate was obtained by filtration, washed with methyl ethyl ketone and then dried overnight in vacuum to obtain 5.6 g of white crystals.

The analytical measurements of these white crystals were as follows.

IR measurement result:

The characteristic peaks were 1220 cm ^-1 , 1520 cm ^-1 , 1630 cm ^-1 , 1710 cm ^-1 , 2900 cm ^-1 and 3300 cm ^-1 .

The result of mass spectroscopic measurement:

[M + H] ^{+ was} determined at m / z 596.

It has been proven that the structural formula of the main component of this compound is the formula (R-2) shown hereinafter.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the compound obtained above was used and evaluated. The results obtained are summarized in table 1.

Reference Example 4

3.0 g of p-aminophenol was added to 100 ml of dioxane. While the resulting mixture was stirred at 50 ° C, a solution of 5.4 g of toluenesulfonyl isocyanate in 30 ml of dioxane was added dropwise to it for 1 hour, and the reaction was carried out at 50 ° C for 5 hours. After completion of the reaction, the reaction solution was concentrated and then poured into hexane for a crystallization effect, and a solid precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuo to obtain 4.9 g of brown crystals. After that, 2 g of the compound thus obtained was added to 50 ml of dioxane. While the resulting mixture was stirred at 80 ° C, a solution of 3.8 g of octadecyl isocyanate in 10 ml of dioxane and then 2 mg of dibutyltin taurate as a catalyst was added to it, and the reaction was carried out at 80 ° C for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a crystalline precipitate was obtained by filtration, washed with dioxane, and then dried overnight in vacuo to obtain 2.7 g of slightly pink crystals.

The analytical measurement of these slightly pink crystals was as follows.

IR measurement result:

The characteristic peaks were at 1230 cm ^-1 , 1470 cm ^-1 , 1510 cm ^-1 , 1570 cm ^-1 , 1620 cm ^-1 , 1700 cm ^-1 , 2900 cm ^-1 and 3300 cm ^-1 .

It has been proven that the structural formula of the main component of this compound is the formula (R-3) shown below.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the compound obtained above was used and evaluated. The results obtained are summarized in table 1.

Reference Example 5

To 10 g of 2,4-toluene diisocyanate was added 50 g of toluene as a solvent, after which 30 g of aniline was added thereto, and the reaction was carried out at 25 ° C for 3 hours. After completion of the reaction, a white solid precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuo to obtain 17 g of the compound as white crystals.

The proposed structural formula for the main component of this compound is the structural formula of compound (C-1) shown hereinafter.

Then 2 g of this compound was ground together with 8 g of an aqueous solution of 2.5 wt.% Polyvinyl alcohol in a paint shaker for 45 minutes to disperse, whereby a dispersion was obtained.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the compound obtained above was used and evaluated. The results obtained are summarized in table 1.

Reference Example 6

To 10 g of 2,4-toluene diisocyanate was added 30 g of toluene as a solvent, after which 30 g of phenol was added thereto, and the reaction was carried out at 100 ° C. for 3 hours. After completion of the reaction, toluene was removed by concentration, and hexane was added to the precipitate, and a white solid precipitate was obtained by filtration, washed with hexane, and then dried overnight in vacuo to obtain 15 g of a compound as white crystals.

The proposed structural formula of the main component of this compound is the structural formula of compound (C-2) shown below.

Then 2 g of the obtained compound was ground together with 8 g of an aqueous solution of 2.5 wt.% Polyvinyl alcohol in a paint shaker for 45 minutes to disperse, whereby a dispersion was obtained.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the compound obtained above was used and evaluated. The results obtained are summarized in table 1.

Reference Example 7

Heat-sensitive recording material was obtained in the same manner as in example 1, except for the use of 1,3-diphenylurea instead of the urea-urethane compound synthesized in example 1, and evaluated. The results obtained are summarized in table 1.

Example 24

While stirring 31.5 g of 2, 4-toluene diisocyanate at 60 ° C, a solution of 21.5 g of 4,4'-diaminodiphenyl sulfone diluted in 120 ml of methyl ethyl ketone was added dropwise thereto over 4 hours, and the reaction was carried out at 60 ° C for another 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature and toluene was added thereto, and a white solid precipitate was obtained by filtration, washed with toluene and then dried overnight in vacuo to obtain 47 g of the compound as white crystals. Then, to 30 g of the obtained compound, 9.5 g of phenol and 95 ml of methyl ethyl ketone were added, after which 30 mg of triethylamine was added thereto, and the reaction was carried out at 25 ° C for 4 hours. After completion of the reaction, toluene was added to the reaction solution, and a crystalline precipitate was obtained by filtration, washed with toluene, and then dried overnight in vacuo to obtain 38.5 g of a compound as white crystals. During IR measurements of these white crystals, characteristic peaks were found at 990 cm ^-1 , 1110 cm ^-1 , 1320 cm ^-1 , 1590 cm ^-1 , 1700 cm ^-1 and 3350 cm ^-1 .

Then, a dispersion was obtained by dispersing 2 g of the obtained compound by grinding them together with 8 g of an aqueous solution of 2.5 wt.% Polyvinyl alcohol in a paint shaker for 6 hours. The dispersion temperature immediately after the dispersion process was 25 ° C. The diameter of the dispersed particles of the compound was 0.6 μm.

Another dispersion was obtained by dispersing 70 g of 3-dibutylamino-6-methyl-7-anilinofluorane by grinding it together with 130 g of an aqueous solution of 5.4 wt.% Hydroxypropyl methylcellulose (Metlose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd. ) in a sand mill (manufactured by AIMEX CO., LTD .; tank volume 400 ml) with a speed of 2000 rpm for 3 hours.

Another dispersion was obtained by dispersing 70 g of diphenyl sulfone by grinding it together with 130 g of an aqueous solution of 8 wt.% Polyvinyl alcohol in a sand mill (manufactured by AIMEX CO., LTD .; tank volume 400 ml) with a speed of 2000 rpm for 3 hours.

Another other dispersion was obtained by mixing 10 g of calcium carbonate with 30 g of water and mixing the mixture using a mixer.

The coating liquid was obtained by mixing and mixing the above dispersions and other components in the following proportions (proportions of dry basis); the dispersion of the above compound, calculated on the dry solid: 20 parts by mass, the dispersion of 3-dibutylamino-6-methyl-7-anilinofluorane, calculated on the dry solid: 10 parts by mass, the dispersion of diphenyl sulfone, calculated on the dry solid: 25 parts by mass, the dispersion of calcium carbonate, calculated on the dry solid: 40 parts by mass, the dispersion of zinc stearate (solid content: 16 wt.%), calculated on the dry solid: 20 parts by mass and 15 wt.% poly (vinyl alcohol) in terms of dry t erdoe substance: 15 parts by weight.

The coating liquid was applied to the base paper with a base weight of 50 g / m ² using a coating unit to remove excess using a bar with a No. 10 rod. The coating amount of the coating liquid was 5 g / m ² , based on the dry weight. After drying, supercalendering was performed to obtain a thermosensitive recording material.

The result of the sensitivity assessment of the obtained thermally sensitive recording material was so optimal that the optical density was 1.3. The ability to preserve the print, which was evaluated using vinyl chloride wrapping films, was optimal. The brightness of the original surface of the recording material was almost 82. The results of these estimates are summarized in table 2.

Examples 25 and 26

Heat-sensitive recording materials were obtained in the same manner as in example 24, except for the use of 3-diethylamino-6-methyl-7-anilinofluorane (example 25) or 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (example 26) instead of 3-dibutylamino-6-methyl-7-anilinofluorane, and evaluated. The results obtained are summarized in table 2.

Examples 27-29

Heat-sensitive recording materials were obtained in the same manner as in example 24, except for the use of methyl cellulose (Metlose M-15, manufactured by Shine-Etsu Chemical Co., Ltd.) (example 27), polyoxyethylene alkyl sulfate (Rebenol WX, manufactured by Kao Corp.) (Example 28) or sodium 2-ethylhexyl sulfosuccinate (Neocol SWC, manufactured by Dai-ichi Koguo Seiyaku Co., Ltd.) (Example 29) instead of the hydroxypropyl methylcellulose used in Example 24 to disperse 3-dibutylamino-6-methyl -7-anilinofluorane, and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 2.

Example 30

A dispersion of a urea-urethane developer compound, a 3-dibutylamino-66-methyl-7-anilinofluorane dispersion, a diphenyl sulfone dispersion, and a calcium carbonate dispersion were obtained in the same manner as in Example 24.

On the other hand, dispersion was obtained by dispersing 70 g of 2,2-bis (4-hydroxyphenyl) propane by grinding it together with 130 g of an aqueous solution of 5.4 wt.% Polyvinyl alcohol in a sand mill (manufactured by AIMEX Co., LTD. ; tank volume 400 ml) with a speed of 2000 rpm for 3 hours.

The coating liquid was obtained by mixing and mixing the above dispersions and other components in the following proportions (proportions of dry basis); the dispersion of the urea-urethane compound, calculated on the dry solid: 10 parts by mass, the dispersion of 3-dibutylamino-6-methyl-7-anilinofluoran, calculated on the dry solid: 10 parts by mass, the dispersion of diphenyl sulfone, calculated on the dry solid: 20 parts by weight, dispersion of 2,2-bis- (4-hydroxyphenyl) propane, calculated on the dry solid: 10 parts by weight, dispersion of calcium carbonate, calculated on the dry solid: 20 parts by weight, zinc stearate dispersion (content solids: 16 wt.%) in pen dry solids: 10 parts by weight and 15 wt.% poly (vinyl alcohol), calculated on dry solids: 10 parts by weight.

Heat-sensitive recording material was obtained in the same manner as in example 24, except for using the coating liquid obtained above, and evaluated. The results obtained are summarized in table 2.

Examples 31-34

Heat-sensitive recording materials were obtained in the same manner as in Example 30, except for the use of 4-isopropyloxyphenyl-4′-hydroxyphenyl sulfone (D-8, trade name, manufactured by Nippon Soda Co., Ltd.), (Example 31), bis ( 3-allyl-4-hydroxyphenyl) sulfone (TG-SA, trade name, manufactured by Nippon Kayaku Co., Ltd.) (Example 32), 2,4'-dihydroxydiphenyl sulfone (24BPS, trade name, manufactured by Nicca Chemical Co. , Ltd.) (Example 33) or a mixture composed mainly of 4,4 '- [oxybis (ethyleneoxy-p-phenylene sulfonyl)] diphenol (D-90, trade name, manufactured by Nippon Soda Co, Ltd.) (Example 34) vm Esto 2,2-bis (4-hydroxyphenyl) propane and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 2.

Examples 35-64

Heat-sensitive recording materials were obtained in the same manner as in examples 30-34, except for the use of β-naphthylbenzyl ether (BON, trade name, manufactured by Ueno Fine Chemicals Industry Ltd.) (examples 35-39), p-benzylbiphenyl (PBBP, trade name, manufactured by Nippon Steel Chemical Co., Ltd.) (Examples 40-44), 1,2-di (m-methylphenoxy) ethane (KS-235, trade name, manufactured by SANKOSHA CO., LTD.) ( Examples 45-49), di-p-methylbenzyloxalate (HS3520, trade name, manufactured by Dainippon Ink and Chemicals, Inc.) (examples 50-54), 1,2-diphenoxymethylbenzene (PMB-2, trade name, manufactured by Nicca Chemical Co., Ltd.) (Examples 55-59 ) or m-terphenyl (mtp, trade name, manufactured by Nippon Steel Chemical Co., Ltd.) (Examples 60-64) instead of diphenyl sulfone, and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 2.

Examples 65-66

Heat-sensitive recording materials were obtained in the same manner as in Example 24, except for using a stearamide-emulsified product (Highmicron G-270, trade name, manufactured by Chukyo Yushi Co., Ltd.) (Example 65) or acetoacetic o-chloroaniline (produced Mitsuboshi Chemical Co., Ltd.) (Example 66) instead of diphenyl sulfone, and evaluated. The results obtained are summarized in table 2.

Example 67

Heat-sensitive recording material was obtained in the same manner as in example 30, except for the addition of a fluorescent dye stilbene type (Kayahol 3BS, trade name, manufactured by Nippon Kayaku Co., Ltd.) in the coating liquid obtained in example 30, in a proportion of 1 part by weight per 100 parts by weight (in terms of dry solid) of the coating liquid and evaluated. The results obtained are summarized in table 2.

Example 68

A dispersion was obtained by dispersing 70 g of 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane by grinding it together with 130 g of an aqueous solution of 5.4 wt.% Polyvinyl alcohol in a sand mill (producing AIMEX CO., LTD .; tank volume 400 ml) with a speed of 2000 rpm for 3 hours.

Then, heat-sensitive recording material was obtained in the same manner as in example 30, except for adding the above 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane dispersion to the coating liquid obtained in example 30 , in a proportion of 10 parts by weight per 100 parts by weight (in terms of dry solid) of the coating liquid and evaluated. The results obtained are summarized in table 2.

Example 69

In 30 g of 2,4-toluene diisocyanate, 30 g of toluene was added as a solvent, after which 3.24 g of phenol was added thereto, and the reaction was carried out at 100 ° C. for 1 hour and 30 minutes. After completion of the reaction, toluene was removed by concentration and hexane was added to the precipitate, and a white solid precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuo to obtain 6.9 g of the compound as white crystals. Then, 100 g of toluene as a solvent was added to 5.0 g of the obtained compound, after which 3.50 g of aniline was added thereto, and the interaction was carried out at 25 ° C for 3 hours. A crystalline precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuo to give 5.5 g of the compound as white crystals. When conducting IR measurements of these white crystals, it was found that the characteristic peaks are at 890 cm ^-1 , 1000 cm ^-1 , 1030 cm ^-1 , 1440 cm ^-1 , 1720 cm ^-1 and 3350 cm ^-1 .

Then, heat-sensitive recording material was obtained in the same manner as in example 68, except for using the compound obtained above instead of the urea-urethane compound used in example 68, and evaluated. The results obtained are summarized in table 2.

Examples 70-75

Heat-sensitive recording materials were obtained in the same manner as in example 68, except for the use of 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane (Adecaarcles DH-43, manufactured by Asahi Denka Kogyo K. K.) (example 70), 4-benzyloxy-4 '- (2, 3-epoxy-2-methylprop-1-yloxy) diphenyl sulfone (NTZ-95, manufactured by Nippon Soda Co., Ltd.), (example 71 ), methylenebis (2-hydroxy-3- (benzotriazol-2-yl) -5-tert-octylphenyl) (Example 72), 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (Adecaarcles DN-13, Asahi Denka Kogyo K.K.) (Example 73), 1,3,5-Tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate (Adecaarcles DH-48, manufact. Asahi Denka Kogyo K.K.) (Example 74) or sodium 2,2-methylenebis (4,6-di-tert-butylphenyl) phosphate (Adecaarcles F-85, manufactured by Asahi Denka Kogyo K.K.) (Example 75 ) instead of 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 2.

Reference Example 8

Heat-sensitive recording material was obtained in the same manner as in example 24, except for the use of 2,2-bis (4-hydroxyphenyl) propane instead of the urea-urethane compound synthesized in example 24, and evaluated. The results obtained are summarized in table 2.

<Erasure Resistance>

The surface of the heat-sensitive recording material was rubbed with a fingernail and visually assessed if there was a color manifestation in the part where it was rubbed. When the recording material showed no noticeable bands, the degree of abrasion resistance was good.

<Accumulation of friction bands>

A cylinder (mass: 2 kg) having a slice with a diameter of 5 cm was moved 50 times in the same 20 cm length of the recording surface of each heat-sensitive recording material obtained at a speed of 20 cm / sec, and then the recording material was left at room temperature for one week. After one week, the readability of the printed image was visually evaluated. When the printed image can be adequately read, the recording material was rated as good.

Example 76

A heat-sensitive coating liquid was obtained in the same manner as in example 24. Then, the coating liquid was applied to the base paper with a base weight of 50 g / m ² using a coating device with a rod number 10. After drying, supercalendering was performed to obtain a heat-sensitive color-forming layer on the substrate. The coating amount of coating fluid was 5 g / m ² , calculated on the dry weight.

Then a dispersion was obtained by dispersing 40 g of kaolin by grinding it together with 60 g of an aqueous solution of 0.7% sodium hexametaphosphate in a sand mill (manufactured by AIMEX CO., LTD .; tank volume 400 ml) with a speed of 2000 rpm for 3 hours.

Received a coating liquid for the formation of a protective layer by mixing and mixing kaolin dispersion and other components in the following proportions (proportions of dry basis); the dispersion of kaolin in terms of dry solid: 20 parts by weight, the dispersion of zinc stearate (solid component: 16 wt.%) in terms of dry solid: 10 parts by weight, an aqueous solution of carboxy-modified polyvinyl alcohol in terms of dry solid substance: 40 parts by weight, and an aqueous solution of a polyacrylamidoepichlorohydrin agent forming cross-links, calculated on the dry solid: 5 parts by weight.

Coating liquid to form a protective layer was applied to a heat-sensitive color-forming layer using a coating device with a No. 5 rod. After drying, supercalendering was performed to obtain a heat-sensitive recording material. The coating amount of liquid to form the protective layer was 2 g / m ² , calculated on the dry weight.

The result of the sensitivity assessment of the obtained thermally sensitive recording material was so good that the optical density was 1.3. The print retention ability evaluated with vinyl chloride wrapping films was good. The surface of the heat-sensitive recording material was rubbed with a fingernail and visually assessed the appearance of color in the part where it was rubbed, and it was found that there were no noticeable signs of scuffing, namely, that the abrasion resistance was good. The result of a long-term test to evaluate the abrasion resistance was so good that the printed image could be adequately read. These evaluation results are summarized in table 3.

Examples 77 and 78

Heat-sensitive recording materials were obtained in the same manner as in Example 76, except for using polyvinyl alcohol (Example 77) or an acrylic copolymer (Example 78) instead of a carboxy-modified polyvinyl alcohol, and evaluated. The results obtained are summarized in table 3.

Examples 79-81

Heat-sensitive recording materials were obtained in the same manner as in example 76, except for the use of aluminum hydroxide (example 79), cross-linking polymethylmethacrylate resin (example 80) or silicon dioxide (example 81) instead of kaolin, and evaluated. The results obtained are summarized in table 3.

Example 82

The coating fluid for the intermediate layer was obtained by mixing and mixing a dispersion of 33 wt.% Calcined kaolin and a latex aqueous dispersion based on 50 wt.% Styrene / butadiene in proportions (proportions of dry base) of 100 parts by weight and 12 parts by weight, respectively .

Then, a coating liquid for the reverse side was obtained by mixing and mixing 20 wt.% Acrylic emulsion and 10 wt.% Silicon dispersion in the form of a fine powder (Fineseal SP-10) in proportions (proportion of dry base) of 100 parts by weight and 7 parts by weight respectively.

The above coating fluid for the intermediate layer was applied on one side of the base paper (50 g / m ² ) in an amount of 10 g / m ² in units of solids and dried, and the heat-sensitive coating fluid obtained in Example 76 was applied on the same side in an amount of 5 g / m ² in units of solid and dried, after which the coating liquid for the protective layer obtained in Example 76 was applied to the same side in an amount of 2 g / m ² in units of solid and dried. Then, the above liquid for coating the reverse side was applied to the uncoated side in an amount of 1 g / m ² in units of solid and dried, and calendaring was performed to obtain a heat-sensitive recording material that was evaluated. The results obtained are summarized in table 3.

Reference Example 9

The heat-sensitive recording material was obtained in the same manner as in Example 76, except that no coating liquid forming a protective layer was applied to the heat-sensitive color-forming layer, and the recording material was evaluated. The results obtained are summarized in table 3.

Example 83

A dispersion was obtained by dispersing 2 g of the compound obtained in Example 24, grinding it together with 8 g of an aqueous solution of 2.5 wt.% Polyvinyl alcohol (Gohsenol KL-05, manufactured by Nippon Syntic Chemical Industry Co., Ltd.) in a dye shaker in within 6 hours. The temperature of the dispersion immediately after the dispersion process was 25 ° C and the pH of the dispersion was 8. The diameter of the dispersed particles of the compound was 0.6 μm.

Another dispersion was obtained by dispersing 70 g of 3-dibutylamino-6-methyl-7-anilinofluorane by grinding it together with 130 g of an aqueous solution of 5.4 wt.% Polyvinyl alcohol in a sand mill (manufactured by AIMEX CO., LTD .; tank volume 400 ml ) with a speed of 2000 rpm for 3 hours.

Another dispersion was obtained by dispersing 70 g of diphenyl sulfone by grinding it together with 130 g of an aqueous solution of 5.4 wt.% Polyvinyl alcohol (Gohsenol KL-05, manufactured by Nippon Syntic Chemical Industry Co., Ltd.) in a sand mill (manufactured by AIMEX CO ., LTD .; tank volume 400 ml) with a speed of 2000 rpm for 3 hours.

Another other dispersion was obtained by mixing 10 g of calcium carbonate with 30 g of water and mixing the mixture using a mixer.

The coating fluid was obtained by mixing and mixing the above dispersions and other components in the following proportions (proportions of dry base); the dispersion of the above compound, calculated on the dry solid: 30 parts by mass, the dispersion of 3-dibutylamino-6-methyl-7-anilinofluoran, calculated on the dry solid: 15 parts by mass, the dispersion of diphenyl sulfone, calculated on the dry solid: 30 parts by mass, the dispersion of calcium carbonate, calculated on the dry solid: 20 parts by mass, the dispersion of zinc stearate (solid component: 16 wt.%), calculated on the dry solid: 10 parts by mass, and 15 wt.% polyvinyl alcohol in dry solid substance: 7 parts by weight. The pH of the coating liquid was 8.2.

Then, the coating liquid was applied to the surface of the paper without wood pulp with a base weight of 50 g / m ² in an amount of 5 g / m ² calculated on the dry weight and dried by supercalendering to obtain a heat-sensitive recording material. The result of the sensitivity assessment of the obtained thermally sensitive recording material was so good that the optical density was 1.3. The print retention ability, evaluated with vinyl chloride wrapping films, was so good that there was no burnout. The results of the assessment are summarized in table 4.

Example 84

A dispersion was prepared by dispersing 2 g of the same urea-urethane compound used in Example 83 and 2 g of diphenyl sulfone by grinding them together with 16 g of an aqueous solution of 2.5 wt.% Modified polyvinyl alcohol (Gohsenol KL-05, manufactured by Nippon Syntic Chemical Industry Co., Ltd.) in a dye shaker for 6 hours.

Then, the heat-sensitive recording material was obtained in the same manner as in Example 83, except for adding the above joint dispersion in a proportion of 60 parts by weight based on the dry solid, instead of the dispersion of the urea-urethane compound used in Example 83 and the diphenyl sulfone dispersion, and recording material was evaluated. The results obtained are summarized in table 4.

Example 85

To 61 g of 2,4-toluene diisocyanate was added 450 g of toluene as a solvent, after which a solution of 26 g of aniline in 150 g of toluene was added dropwise thereto over 6 hours, and the reaction was carried out at 5 ° C. for 7 hours. After completion of the reaction, a white solid precipitate was obtained by filtration, washed with toluene and then dried overnight in vacuo to obtain 70 g of the compound as white crystals. Then, 365 g of toluene was added as a solvent to 30 g of the obtained compound, after which 12.2 g of 2,2-bis (4-hydroxyphenyl) propane and 0.3 mg of triethylamine were added thereto, and the interaction was carried out with stirring at 60 ° С for 4 hours, at 70 ° C for 3 hours and then at 80 ° C for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and a crystalline precipitate was obtained by filtration, washed with toluene, and then dried overnight in vacuo to obtain 42 g of the compound as white crystals. The IR measurements of these white crystals revealed characteristic peaks at 750 cm ^-1 , 840 cm ^-1 , 1020 cm ^-1 , 1500 cm ^-1 , 1600 cm ^-1 , 1720 cm ^-1 and 3320 cm ^-1 .

A dispersion was obtained by dispersing 2 g of this compound and 2 g

diphenylsulfone by grinding them together with 16 g of an aqueous solution of 2.5 wt.% modified polyvinyl alcohol (Gohseran L-3266, manufactured by Nippon Syntic Chemical Industry Co., Ltd.) in a dye shaker for 6 hours.

Then, the heat-sensitive recording material was obtained in the same manner as in Example 83, except for adding a joint dispersion of the above compound and diphenyl sulfone in a proportion of 60 parts by weight based on the dry solid instead of the dispersion of the urea-urethane compound used in Example 83 and the dispersion of diphenyl sulfone , and recording material was evaluated. The results obtained are summarized in table 4.

Example 86

A dispersion was obtained by dispersing 2 g of the compound obtained in Example 69 and 2 g of dimethylbenzyl oxalate by grinding them together with 16 g of an aqueous solution of 2.5 wt.% Modified polyvinyl alcohol (Gohseran L-3266, manufactured by Nippon Syntic Chemical Industry Co., Ltd .) in a dye shaker for 6 hours.

Then, heat-sensitive recording material was obtained in the same manner as in Example 83, except for adding the above joint dispersion of the above compound and dimethylbenzyloxalate in a proportion of 60 parts by weight based on the dry solid instead of the dispersion of the urea-urethane compound used in example 83 and diphenyl sulfone variance and recording material was evaluated. The results obtained are summarized in table 4.

Example 87

A dispersion was obtained by dispersing 2 g of the compound obtained in Example 2, grinding it together with 8 g of an aqueous solution of 2.5 wt.% Methylcellulose (Metlose SM-15, manufactured by Shin-Etsu Chemical Co., Ltd.) in a dye shaker for 6 o'clock.

Then, the heat-sensitive recording material was obtained in the same manner as in Example 83, except for using the dispersion of the above compound instead of the dispersion of the urea-urethane compound used in Example 83, and the recording material was evaluated. The results obtained are summarized in table 4,

Examples 88-92

Heat-sensitive recording materials were obtained in the same manner as in Example 83, except for using the ammonium salt of a polycarboxylic acid (Dispersant 5027, manufactured by Sunnopco Co., Ltd.) (Example 88), a water-soluble low molecular weight copolymer (Discort N14, manufactured by Dai-ichi Koduo Seiyaku Co., Ltd.) (Example 89), sodium 2-ethylhexyl sulfosuccinate (Neocol SWC, manufactured by Dai-ichi Koduo Seiyaku Co., Ltd.) (Example 90), hydroxypropyl methylcellulose (Metlose 60SH-03, manufactured by Shin- Etsu Chemical Co., Ltd.) (Example 91), or condensed sodium naphthalenesulfonate (Roma D, manufactured by Sunnopco Co., Ltd.) (Example 92) instead of poly vinyl alcohol (Gohsenol KL-05, manufactured by Nippon Syntic Chemical Industry Co., Ltd.) used as a dispersing agent for the urea-urethane compound in Example 83, and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 4.

Examples 93-98

Heat-sensitive recording materials were obtained in the same manner as in example 83, except for the use of methyl cellulose (Metlose SM-15, manufactured by Shin-Etsu Chemical Co., Ltd.) (example 93), water-soluble low molecular weight copolymers (Discort N14, manufactured by Dai -ichi Kogyo Seiyaku Co., Ltd.) (Example 94), sodium 2-ethylhexyl sulfosuccinate (Neocol SWC, manufactured by Dai-ichi Koguo Seiyaku Co., Ltd.) (Example 95), hydroxypropyl methylcellulose (Metlose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) (Example 96), condensed sodium naphthalenesulfonate (Roma D, manufactured by Sunnopco Co., Ltd.) (Example 97) or polycarboxylic acid ammonium salt (Dispersant 5027, manufactured by Sunnopco Co., Ltd.) (Example 98) instead of polyvinyl alcohol (Gosenol KL-05, manufactured by Nippon Syntic Chemical Industry Co., Ltd.) used as a dispersant for diphenyl sulfone in Example 83 , and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 4.

Examples 99-101

Heat-sensitive recording materials were obtained in the same manner as in Example 87, except for the use of methyl cellulose (Metlose SM-15, manufactured by Shin-Etsu Chemical Co., Ltd.) (example 99), hydroxypropyl methyl cellulose (Metlose 60SH-03, manufactured by Shin Etsu Chemical Co., Ltd.) (Example 100) or a modified polyvinyl alcohol (Gohseran L-3266, manufactured by Nippon Syntic Chemical Industry Co., Ltd.) (Example 101) instead of polyvinyl alcohol (Gohsenol KL-05, manufactured Nippon Syntic Chemical Industry Co., Ltd.) used as a dispersing agent for diphenyl sulfone in Example 87 and heat-sensitive recording materials We evaluated. The results obtained are summarized in table 4.

Example 102

Heat-sensitive recording material was obtained in the same manner as in Example 99, except for using modified polyvinyl alcohol (Gohseran L-3266, manufactured by Nippon Syntic Chemical Industry Co., Ltd.) instead of methyl cellulose (Metlose SM-15, manufactured by Shin-Etsu Chemical Co., Ltd.) used as a dispersing agent for the urea-urethane compound in Example 99, and the recording material was evaluated. The results obtained are summarized in table 4.

Examples 103 and 104

Heat-sensitive recording materials were obtained in the same manner as in Example 89, except for the use of methyl cellulose (Metlose SM-15, manufactured by Shin-Etsu Chemical Co., Ltd.) (example 103) or hydroxypropyl methyl cellulose (Metlose 60SH-03, manufactured by Shin Etsu Chemical Co., Ltd.) (Example 104) instead of polyvinyl alcohol (Gohsenol KL-05, manufactured by Nippon Syntic Chemical Industry Co., Ltd.) used as a dispersing agent for diphenyl sulfone in Example 89, and heat-sensitive recording materials rated. The results obtained are summarized in table 4.

Examples 105-106

Heat-sensitive recording materials were obtained in the same manner as in example 91, except for the use of methyl cellulose (Metlose SM-15, manufactured by Shin-Etsu Chemical Co., Ltd.) (example 105) or hydroxypropyl methyl cellulose (Metlose 60SH-03, manufactured by Shin Etsu Chemical Co., Ltd.) (Example 106) instead of polyvinyl alcohol (Gohsenol KL-05, manufactured by Nippon Syntic Chemical Industry Co., Ltd.) used as a dispersant for diphenyl sulfone in Example 91, and heat-sensitive recording materials rated. The results obtained are summarized in table 4.

Examples 107 and 108

Heat-sensitive recording materials were obtained in the same manner as in example 104, except for the use of hydroxypropyl methylcellulose (Metlose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) (example 107) or a mixed dispersing agent of hydroxypropyl methylcellulose (Metlose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) and sodium 2-ethylgenxyl sulfosuccinate (Neocol SWC, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (weight ratio: 1/1) (Example 108) instead of polyvinyl alcohol, used as a dispersing agent for 3-dibutylamino-6-methyl-7-anilinofluoran in example 104, and heat ity of recording materials was evaluated. The results obtained are summarized in table 4.

Reference Example 10

A heat-sensitive recording sheet was obtained in the same manner as in Example 83, except for the use of 2,2-bis (4-hydroxyphenyl) propane in place of the urea-urethane compound used in Example 83, and evaluated. The results obtained are summarized in table 4.

Comparative Examples 11 and 12

The same urea-urethane compound used in Example 83 was dispersed in the same manner as in Example 83, except for changing the dispersion time, and the average particle size of the obtained dispersions was measured and it was 0.04 μm (comparative example 11) and 6, 5 μm (comparative example 12). A heat-sensitive recording sheet was obtained in the same manner as in Example 83, except for using each of the above dispersions, and evaluated. The results obtained are summarized in table 4.

Reference Example 13

The same urea-urethane compound used in Example 83 was dispersed in the same manner as in Example 83, except for maintaining the temperature of dispersion at 65 ° C. during the dispersion process. With the exception of using the dispersion thus obtained, a heat-sensitive recording sheet was obtained in the same manner as in Example 83 and evaluated. The results obtained are summarized in table 4.

Reference Example 14

The same urea-urethane compound used in Example 83 was dispersed in the same manner as in Example 83, except for setting the pH of the dispersion medium used in the dispersion process at 4. Except for using the dispersion thus obtained, a heat-sensitive recording sheet was obtained by in the same manner as in example 83, and evaluated. The results obtained are summarized in table 4.

Reference Example 15

The same urea-urethane compound used in Example 83 was dispersed in the same manner as in Example 83, except for setting the pH of the dispersion medium used in the dispersion process at 11. Except for using the dispersion thus obtained, a heat-sensitive recording sheet was obtained by in the same manner as in example 83, and evaluated. The results obtained are summarized in table 4.

Reference Example 16

The pH of the coating liquid obtained in Example 83 was adjusted to 4.0 with 1N sulfuric acid. With the exception of using the coating liquid thus obtained, a heat-sensitive recording sheet was obtained in the same manner as in Example 83 and evaluated. The results obtained are summarized in table 4.

Reference Example 17

The pH of the coating liquid obtained in Example 83 was adjusted at 12.5 with 1N sodium hydroxide. With the exception of using the coating liquid thus obtained, a heat-sensitive recording sheet was obtained in the same manner as in Example 83 and evaluated. The results obtained are summarized in table 4.

Example 109

The coating liquid obtained in Example 83 was applied to paper without wood pulp with a pH on the surface of 3.2 in an amount of 5 g / m ² in units of dry weight and dried, then supercalendering was performed to obtain a heat-sensitive recording material. The result of the sensitivity assessment of the obtained thermally sensitive recording material was so good that the optical density was 1.3. The ability to preserve the print, which was evaluated using vinyl chloride wrapping films, was optimal. The ability to preserve the original surface of the recording material was so good that the surface was barely painted. The results obtained are summarized in table 5.

Examples 110 and 111

Heat-sensitive recording materials were obtained in the same manner as in example 109, except for the use of paper without wood pulp with a surface pH of 5 (example 110) or paper without wood pulp with a surface pH of 6.8 (example 111) instead of paper without wood pulp with pH surface 3.2, and evaluated. The results obtained are summarized in table 5.

Comparative Examples 18 and 19

Heat-sensitive recording materials were obtained in the same manner as in Example 109, except for the use of paper without wood pulp with a surface pH of 2.8 (comparative example 18) or paper without wood pulp with a surface pH of 9.5 (comparative example 19) of paper without wood masses with a surface pH of pH of 3.2, and evaluated. The results obtained are summarized in table 5.

Example 112

A) Obtaining a coating fluid for a magnetic recording layer

A coating fluid for the magnetic recording layer was obtained by dispersing 100 parts by weight of barium ferrite (coercive force: 2700), 25 parts by weight of sodium polyacrylate (20 wt.% Aqueous solution), 100 parts by weight of polyvinylidene chloride (49 wt.% Dispersion) , 15 parts by weight of black coal (36 wt.% Dispersion), 10 parts by weight of paraffin wax (20 wt.% Dispersion obtained using methyl cellulose) and 100 parts by weight of water in a ball mill for 10 hours.

C) Obtaining a coating fluid for a heat-sensitive recording layer

The coating fluid for the heat-sensitive recording layer was obtained in the same manner as in example 24.

Then, the coating liquid for the magnetic recording layer obtained in A) was applied to one side of paper without wood pulp, with a base weight of 150 g / m ² in an amount of 30 g / m ² in units of dry weight and dried to obtain a magnetic recording layer. Then, a coating liquid for a heat-sensitive recording layer obtained in B) was applied to the other side of the substrate having the above magnetic recording layer in an amount of 6 g / m ² in units of dry weight, and dried, then supercalendering was performed to obtain a heat-sensitive magnetic recording material.

The result of evaluating the sensitivity of color manifestation of the heat-sensitive recording layer of the obtained heat-sensitive recording material was so optimal that the optical density was 1.3. The imprintability, which was evaluated using vinyl chloride wrapping films, was so good that the optical density was 1.3. The results obtained are summarized in table 6.

Example 113

C) Obtaining a coating fluid for the protective layer

Twenty parts by weight of zinc stearate, 20 parts by weight of an aqueous solution of 5 wt.% Methyl cellulose and 60 parts by weight of water were mixed and then dispersed in a sand mill for 2 hours. Then, 20 parts by weight of an aqueous solution of 10% by weight of a carboxy-modified polyvinyl alcohol, 1.5 parts by weight of silicon, 6.5 parts by weight of an aqueous solution of 12.5% by weight of polyamidoepichlorohydrin, and 15.0 parts by weight of water were mixed and then dispersed in a sand mill for 2 hours.

Then, 0.7 parts by weight of the zinc stearate dispersion obtained above, 45.0 parts by weight of the silicon dispersion obtained above, and 11.3 parts by weight of water were mixed to prepare a coating liquid for the protective layer. The heat-sensitive magnetic recording material was obtained in the same manner as in example 112, except for applying a protective layer of the above coating liquid for the protective layer to the heat-sensitive recording layer of the heat-sensitive magnetic recording material of example 112 in an amount of 3 g / m ² in units of dry weight, then dried, and heat-sensitive magnetic recording material was evaluated. The results obtained are summarized in table 6.

Example 114

D) Obtaining a coating fluid for the intermediate layer

A coating fluid was prepared for the intermediate layer, which consisted of 80 parts by weight (based on the dry solid) of 48% dispersion of finely ground polystyrene and 20 parts by weight (based on the dry solid) 40% styrene-acrylic ester copolymer emulsion.

The heat-sensitive magnetic recording material was obtained in the same manner as in example 113, except for applying an intermediate layer of the above coating liquid between the heat-sensitive recording layer and the substrate of the heat-sensitive magnetic recording material of example 113 in an amount of 8 g / m ² in units of dry weight, then dried and heat-sensitive magnetic recording material was evaluated. The results obtained are summarized in table 6.

Reference Example 20

A heat-sensitive recording sheet was obtained in the same manner as in Example 112, except for the use of 2,2-bis (4-hydroxyphenyl) propane in place of the urea-urethane compound used in Example 112, and evaluated. The results obtained are summarized in table 6.

Example 115

A) Obtaining a coating fluid for a heat-sensitive recording layer

The coating liquid for the heat-sensitive recording layer was obtained in the same manner as in example 24.

The coating liquid for the heat-sensitive recording layer obtained in A) was applied to the surface of the paper without wood pulp with a base mass of 150 g / m ² in an amount of 7 g / m ² in terms of dry weight and dried, followed by supercalading to obtain a coated sheet heat sensitive recording layer.

B) Obtaining a release film

A pressed release agent in the composition with oily dimethylsilicone was applied to the base paper with a base weight of 40 g / m ² in an amount of 1 g / m ² using a grooved roller coater to form an anti-adhesive layer. Then, a component of the adhesive layer, consisting of 100 parts by weight of chlorinated rubber, 20 parts by weight of ester resin, 120 parts by weight of dibutyl phthalate, was applied to the release layer in an amount of 10 g / m ² .

C) Obtaining labels for heat-sensitive recording

The uncoated surface of the film was covered with a heat-sensitive recording layer, which was obtained in paragraph A) above, and the surface of the anti-adhesive film coated with an adhesive layer obtained in paragraph B) above was glued to each other so that they could be in contact, thus obtaining a label for heat sensitive recording.

The result of evaluating the sensitivity of color development of the obtained label for thermally sensitive recording was so good that the optical density was 1.3. The imprintability, which was evaluated using vinyl chloride wrapping films, was so good that there was no fading. The results obtained are summarized in table 7.

Example 116

D) Obtaining a coating fluid for coating the reverse side

A coating fluid for the backcoat was prepared by mixing 100 parts by weight of a styrene-maleic acid copolymer with 50 parts by weight of kaolin.

A thermally sensitive recording label was obtained in the same manner as in Example 115, except for applying a coating layer on the back side of the above coating liquid on the wrong side with respect to the side coated with the thermally sensitive recording layer. The thermally sensitive label of Example 115 was prepared in an amount of 1 g / m ² in units of dry weight, then dried, and the label was evaluated. The results obtained are summarized in table 7.

Example 117

E) Obtaining a coating fluid for the intermediate layer

Received a coating fluid for the intermediate layer, consisting of 80 parts by weight (in terms of dry solid) of 48% dispersion of crushed polystyrene particles and 20 parts by weight (in terms of dry solid) of a 40% emulsion of styrene-acrylic ester copolymer.

A thermally sensitive recording label was obtained in the same manner as in Example 116, except for applying an intermediate layer of the above-mentioned coating liquid between the thermally sensitive recording layer and the label substrate for the thermally sensitive recording of Example 116 in an amount of 8 g / m ² in units of dry weight, then dried, and the label was rated. The results obtained are summarized in table 7.

Example 118

F) Obtaining a coating fluid for the protective layer

Twenty parts by weight of zinc stearate, 20 parts by weight of an aqueous solution of 5 wt.% Methylcellulose and 60 parts by weight of water were mixed and then dispersed in a sand mill for 2 hours. Then 20 parts by weight of an aqueous solution of 10% by weight of a carboxy-modified polyvinyl alcohol, 1.5 parts by weight of silica, 6.5 parts by weight of an aqueous solution of 12.5% by weight of polyamidoepichlorohydrin and 15.0 parts by weight of water were mixed and then dispersed in a sand mill for 2 hours.

Then 0.7 parts by weight of the above dispersion of zinc stearate, 45.0 parts by weight of the above dispersion and 11.3 parts by weight of water were mixed to obtain a coating liquid for the protective layer. The thermally sensitive recording label was obtained in the same manner as in Example 117, except for applying a protective layer above the obtained coating liquid on the thermally sensitive recording layer. A label for the heat-sensitive recording of Example 117 was obtained in an amount of 3 g / m ² in units of dry weight, then dried, and the label was evaluated. The results obtained are summarized in table 7.

Reference Example 21

A heat-sensitive recording sheet was obtained in the same manner as in Example 115, except for the use of 2,2-bis (4-hydroxyphenyl) propane instead of the urea-urethane compound used in Example 115, and evaluated. The results obtained are summarized in table 7.

Example 119

Coating agents for the heat-sensitive color-forming layer and coating agents for the intermediate layer described below were applied to one side of a 75 micron commercial polyethylene terephthalate film (Lumilar E, trade name, Toray Industries, Inc.) so that multilayer films could form on the substrate as follows order: a heat-sensitive recording layer giving a blue color, an intermediate layer, a heat-sensitive recording layer giving a purple color, an intermediate layer, a heat-sensitive recording a yellow layer and an intermediate layer. The application was carried out using a coating device so that the coating amounts of each thermally sensitive recording layer and each intermediate layer after drying were 6.5 g / m ² and 2.0 g / m ^2, respectively, thereby obtaining a color thermally sensitive recording material .

- Obtaining a coating substance for a heat-sensitive recording layer, giving a blue color

Liquid A (dispersion of heat-sensitive color-developing dye)

Twenty parts by weight of 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 20 parts by weight of a 10% aqueous solution of polyvinyl alcohol and 10 parts by weight of water were mixed and then dispersed and crushed in a sand mill (manufactured by AIMEX CO. , LTD.) To obtain a dispersion having an average particle size of 0.7 μm.

Liquid B (developer dispersion)

The urea-urethane compound was synthesized in the same manner as in Example 24, and a dispersion was obtained by dispersing 30 g of this compound, grinding it together with 120 g of an aqueous solution of 2.5 wt.% Polyvinyl alcohol in a sand mill for 3 hours. The dispersion temperature immediately after the dispersion process was 25 ° C. The diameter of the dispersed particles of the compound was 0.6 μm.

The coating material for the heat-sensitive color-forming layer, giving a blue color, was obtained by mixing 30 parts by weight of liquid A, 120 parts by weight of liquid B, 52 parts by weight of 60% suspension of calcium carbonate, 40 parts by weight of 10% aqueous solution of polyvinyl alcohol, 28 parts by weight SBR latex (L-1537, trade name, ASAHI Chemical Industry, Co., Ltd .; solid component 50%), 11 parts by weight of stearamide (Celozol A-877, trade name, manufactured by Chukyo Yushi Co., Ltd .; solid component 26.5%) and 82 parts by weight of water.

- Obtaining a coating substance for a heat-sensitive recording layer, giving a purple color

Liquid A (dispersion of heat-sensitive color-developing dye)

Twenty parts by weight of 4-N- (2- (2,4-di-tert-amylphenoxy) butyryl) piperazinobenzenediazonium hexafluorophosphate, 20 parts by weight of a 10% aqueous solution of polyvinyl alcohol and 10 parts by weight of water were mixed and then dispersed and ground in a sand mill to obtain a dispersion having an average particle size of 0.7 μm.

Liquid B (dispersion of coupling agent)

Fifty parts by weight of 1- (2'-octylphenyl) -3-methyl-5-pyrazolone, 50 parts by weight of 1,2,3-triphenylguanidine, 50 parts by weight of a 10% aqueous solution of polyvinyl alcohol and 25 parts by weight of water were mixed and then dispersed and ground in a sand mill to obtain a dispersion having an average particle size of 1.0 μm.

The coating material for the heat-sensitive color-forming layer, giving a purple color, was obtained by mixing 30 parts by weight of liquid A, 90 parts by weight of liquid B, 52 parts by weight of 60% suspension of calcium carbonate, 40 parts by weight of 10% aqueous solution of polyvinyl alcohol, 28 parts by weight SBR latex (L-1537, trade name, ASAHI Chemical Industry, Co., Ltd .; solid component 50%), 11 parts by weight of stearamide (Celozol A-877, trade name, manufactured by Chukyo Yushi Co., Ltd .; solid component 26.5%) and 82 parts by weight of water.

- Obtaining a coating substance for a heat-sensitive recording layer, giving a yellow color

Liquid A (dispersion of heat-sensitive color-developing dye)

Twenty parts by weight of 2,5-dibutoxy-4-tolylthiobenzene benzene diazonium hexafluorophosphate, 20 parts by weight of a 10% aqueous solution of polyvinyl alcohol and 10 parts by weight of water were mixed and then dispersed and ground in a sand mill to obtain a dispersion having an average particle size of 0, 7 microns.

Liquid B (dispersion of coupling agent)

Fifty parts by weight of 2-chloro-5- (3- (2,4-di-tert-pentyl) phenoxypropylamino) acetanilide, 50 parts by weight of 1,2,3-triphenylguanidine, 50 parts by weight of a 10% aqueous solution of polyvinyl alcohol and 25 parts by weight of water were mixed and then dispersed and ground in a sand mill to obtain a dispersion having an average particle size of 1.0 μm.

The coating material for the heat-sensitive color-forming layer, giving a yellow color, was obtained by mixing 30 parts by weight of liquid A, 90 parts by weight of liquid B, 52 parts by weight of 60% suspension of calcium carbonate, 40 parts by weight of 10% aqueous solution of polyvinyl alcohol, 28 parts by weight SBR latex (L-1537, trade name, ASAHI Chemical Industry, Co., Ltd .; solid component 50%), 11 parts by weight of stearamide (Celozol A-877, trade name, manufactured by Chukyo Yushi Co., Ltd .; solid component 26.5%) and 82 parts by weight of water.

- Obtaining a coating substance (solid component: 15%) for the intermediate layer

The coating material for the intermediate layer was obtained by mixing 42 parts by weight of a dispersion of kaolin clay (average particle size: 0.6 μm), 200 parts by weight of an aqueous solution of a carboxylic acid-modified polyvinyl alcohol (Gohsenol T-330, trade name, manufactured by Nippon Syntic Chemical Industry Co., Ltd .; solid component 10%), 100 parts by weight of acrylic emulsion (SC-2250, trade name, manufactured by Nippon Shokubai Co., Ltd .; solid component 40%), 33 parts by weight of dimethylurea solution (J-001, trade name, manufactured by Showa Denko K.K .; solid component 30%), 13 frequent th by mass of 40% dispersion of zinc stearate (Highmicron F-930, trade name, manufactured by Chukyo Yushi Co., Ltd .; average particle size of 0.9 μm), 70 parts by weight of heavy calcium carbonate (NS-1000, trade name , manufactured by Nitto Funka Kogyo Co., Ltd.), 25 parts by weight of urethane acrylate emulsion (EM90, trade name, manufactured by Arakawa Chemical Industries Ltd .; solid component 40%), 5 parts by weight polysiloxane (SM7025, trade name, production Dow Corning Toray Silicone Co., Ltd .; solid component 33%) and 40 parts by weight of water.

Example 120

An example of obtaining a two-color heat-sensitive recording material is described below.

(A) Leuco dye for the high temperature color-forming layer: 3- (4’-dibutylamino-2’-hydroxyphenyl) -3- (5’-anilino-4’-methyl-2’-methoxyphenyl) phthalide.

(B) Leuco dye for the low temperature color-forming layer: 3-diethylamino-7-chlorofluorane.

(C) Developer: Urea-urethane compound synthesized in Example 119.

(D) Sensitizer: diphenyl sulfone.

Forty grams of each of the above organic compounds (A) to (D) was mixed with 40 g of a 10% solution of polyvinyl alcohol (degree of polymerization 500 and a degree of saponification of 90%) and 20 g of water, and each composition thus obtained was dispersed in a vertical sand mill ( the sand mill was manufactured by AIMEX CO., LTD.), so as to obtain a particle size of 1 μm, dispersions in the form of liquids (A) - (D) corresponding to compounds (A) - (D), respectively, were obtained.

On the other hand, 40 g of light calcium carbonate (Brilliant 15, manufactured by Shiraishi Industrial Co., Ltd .; average particle size of 0.15 μm) and 60 g of 0.7% sodium hexametaphosphate solution were mixed, and the resulting composition was dispersed in a dispersing device Cowles.

Separately, 21% dispersion of zinc stearate was obtained as a dispersion of a lubricant, a liquid (F) and 10% polyvinyl alcohol (NM11, manufactured by Nippon Syntic Chemical Industry Co., Ltd.) was obtained as an adhesive liquid (G).

- Obtaining a coating fluid (I) for a high temperature color-forming heat-sensitive layer

A coating fluid for a high-temperature color-forming heat-sensitive layer was obtained by mixing the above liquids (A), (C), (D) and (G) so that their mass ratio after drying was as follows: (A): (C): (E) : (G) = 20: 40: 25: 15.

- Obtaining a high-temperature color-forming heat-sensitive layer

A high-temperature color-forming heat-sensitive layer was obtained by applying the above-mentioned coating liquid (I) for a high-temperature color-forming heat-sensitive layer on paper without wood pulp (neutral paper) with a base weight of 60 g / m ² in an amount of 8 g / m ² in dry weight using a device for applying Mayer coatings.

- Obtaining a coating fluid (II) for a low temperature color-forming heat-sensitive layer

The coating fluid for the low-temperature color-forming heat-sensitive layer was obtained by mixing the above liquids (B, (C), (D), (E), (F) and (G) so that their mass ratio after drying was as follows: (B): (C): (D): (E): (F): (G) = 10: 20: 20: 20: 10: 10.

- Obtaining two-color heat-sensitive recording material

Coating liquid (II) for a low-temperature color-forming heat-sensitive layer was applied to the above high-temperature color-forming heat-sensitive layer in an amount of 5 g / m ² in units of dry weight. Then, the Bekk smoothing apparatus (JIS-P8119) of the heat-sensitive recording surface was set at 150 seconds of processing to give smoothness by super calendering, thereby obtaining a two-color heat-sensitive recording material.

Reference Example 22

Color heat-sensitive recording material was obtained in the same manner as in example 119, except for the use of 2,2-bis (4-hydroxyphenyl) propane instead of the urea-urethane compound synthesized in example 119, and evaluated. The results obtained are summarized in table 8.

Reference Example 23

A two-color heat-sensitive recording material was obtained in the same manner as in example 120, except for the use of 2,2-bis (4-hydroxyphenyl) propane instead of the urea-urethane compound used in example 120, and evaluated. The results obtained are summarized in table 8.

- Evaluation of color thermosensitive recording materials

The color heat-sensitive recording materials obtained in examples 119 and 120 and comparative examples 22 and 23 were printed using a commercial thermal printer (NC-1, trade name, manufactured by Fuji Photo Film Co., Ltd.), and image quality and ability Image preservation was evaluated by the following methods.

<Image Quality>

: хорошо,

: почти хорошо,

: средне,

: почти плохо,

: плохо.On 5 sheets of each recording material, visibility, contrast, density of image heterogeneity and the like were visually evaluated and they were evaluated according to the following 5 gradations;

: well,

: almost good,

: medium

: almost bad

: badly.

<Image Capability>

Each recording material was placed between vinyl chloride wrapping films or vinyl chloride files and a force of 300 g / cm ^{2 was} applied from above. After 24 hours at 40 ° C, the staining intensity of the printed portion and the unprinted portion (initial surface of the recording material) was visually evaluated. When the staining intensity was only slightly reduced, the ability to save images was rated as good.

The results obtained are summarized in table 8. Thus, the recording materials of examples 119 and 120 were good in image quality and showed excellent image retention, while the recording materials of comparative examples 22 and 23 were worse than the recording materials of examples 119 and 120.

Example 121

The urea-urethane compound was synthesized in the same manner as in Example 24, and a dispersion was obtained by dispersing 2 g of this compound by grinding it together with 8 g of an aqueous solution of 2.5 wt.% Polyvinyl alcohol in a dye shaker for 6 hours. The temperature of the dispersion immediately after the dispersion process was 25 ° C. The diameter of the dispersed particles of the compound was 0.6 μm.

Another dispersion was obtained by dispersing 70 g of 3-dibutylamino-6-methyl-7-anilinofluorane, grinding it together with 130 g of an aqueous solution of 5.4 wt.% Polyvinyl alcohol in a sand mill (manufactured by AIMEX CO., LTD .; tank volume 400 ml) with a speed of 2000 rpm for 3 hours.

Another dispersion was obtained by dispersing 70 g of diphenyl sulfone, grinding it together with 130 g of an aqueous solution of 5.4 wt.% Polyvinyl alcohol in a sand mill (manufactured by AIMEX CO., LTD .; tank volume 400 ml) with a speed of 2000 rpm within 3 hours.

Another other dispersion was obtained by mixing 10 g of calcium carbonate with 30 g of water and mixing the mixture using a mixer.

On the other hand, an aluminum hydroxide dispersion was obtained by treating a mixture of 60 parts by weight of aluminum hydroxide and 40 parts by weight of an aqueous solution of 12.5 wt.% Polyvinyl alcohol for 2 hours using a sand mill to disperse aluminum hydroxide so that the average particle size was approximately 1 micron.

The coating liquid was obtained by mixing and mixing the above dispersions and other components in the following proportions (proportions of dry basis); the dispersion of the above compound in terms of dry solid: 20 parts by weight, the dispersion of 3-dibutylamino-6-methyl-7-anilinofluoran in terms of dry solid: 10 parts by weight, the dispersion of diphenyl sulfone in terms of dry solid: 25 parts by mass, the dispersion of calcium carbonate, calculated on the dry solid: 40 parts by mass, the dispersion of aluminum hydroxide, calculated on the dry solid: 13 parts by mass, the dispersion of zinc stearate (solids content: 16 wt.%), calculated on the dryVerdi substance: 20 parts by weight and 15% by weight of polyvinyl alcohol, based on the dry solid matter:. 15 parts by weight.

Then, this coating fluid for a heat-sensitive recording layer was applied to aluminized paper at a speed of 50 m / min using a grooved roller coater (200 mesh; cup depth 20 μ). The thus treated aluminized paper was dried at 80 ° C for 3 seconds to obtain a heat-sensitive recording layer 2 μm thick. Then, a clear coating liquid in an aqueous dispersion of an acrylic polymer (consisting mainly of units of methyl methacrylate, units of 2-ethylhexyl acrylate and units of styrene and having a glass transition point of approximately 40 ° C.) was applied to the coated surface of the aluminized paper to a thickness of 8 μ using a device for coating with a roller, and dried at 80 ° C for 10 seconds to obtain metallized laser marking paper in accordance with the present invention.

Metallized paper was irradiated with laser radiation from a carbon dioxide laser. An accurate print can be obtained and the color display was good. The test for resistance to the action of the plasticizer was carried out by placing metallized paper between the wrapping films, and it was found that the resistance to the action of the plasticizer was good, that there was no fog on the printed area. The results obtained are summarized in table 9.

Example 122

The urea-urethane compound was synthesized in the same manner as in Example 85, and a dispersion was obtained by dispersing 2 g of this compound, grinding it together with 8 g of an aqueous solution of 2.5 wt.% Polyvinyl alcohol in a dye shaker for 6 hours.

Then, metallized laser marking paper was obtained in the same manner as in Example 121, except for using a dispersion of the above compound instead of a dispersion of the compound obtained in Example 121, and using diphenyl sulfone instead of aluminum hydroxide, and evaluated. The results obtained are summarized in table 9.

Reference Example 24

Laser marking metallized paper was prepared in the same manner as in Example 121, except for the use of 2,2-bis (4-hydroxyphenyl) propane in place of the urea-urethane compound synthesized in Example 121, and evaluated. The results obtained are summarized in table 9.

<Color Sensitivity>

The product for laser marking was irradiated with laser beams with a dose of 0.6 J / cm ² from a carbon dioxide laser (Unimark, manufactured by USHIO INC.) Through a pattern capable of the appearance of numbers. When a clear trace was obtained and the staining intensity was high, the sensitivity of color development was rated as good.

“Resistance to plasticizer>

Three vinyl chloride wrapping films were placed on each upper and lower surfaces of the marked product for laser marking and the resulting compositions were left under a load of 300 kg / cm ² at 40 ° C for 24 hours. After that, the staining intensity of the printed portion was visually evaluated. When there was only a slight decrease in print density, print retention was rated as good.

Example 123

(1) Getting the top paper

A solution obtained by dissolving 2.5 parts by weight of 3-diethylamino-7-chlorofluorane in 80 parts by weight of NISSEKI HISOL N-296 (oil, trade name, manufactured by Nippon Sekiyu Kagaku K.K.) was emulsified in 100 parts by the mass of an aqueous solution of 5 wt.%, pH 4.0, obtained by dissolving the styrene-maleic anhydride copolymer together with a small amount of sodium hydroxide. On the other hand, when a mixture of 10 parts by weight of melamine, 25 parts by weight of a formaldehyde aqueous solution and 65 parts by weight of water was adjusted to pH 9.0 with sodium hydroxide and heated at 60 ° C, the mixture became transparent after 15 minutes and received melamine-formaldehyde precondensate. The precondensate was added to the emulsion obtained above, and the resulting mixture was successively stirred for 4 hours, maintaining the mixture at 60 ° C, and then cooled at room temperature. The solid component of the resulting microcapsule dispersion was 45%.

The microcapsule dispersion thus obtained was applied to paper and dried to obtain top paper.

(2) Getting the bottom paper

A dispersion was obtained by dispersing 15 g of the composition synthesized in the same manner as in Example 7, grinding it together with 45 g of an aqueous solution of 2 wt.% Polyvinyl alcohol in a paint shaker at ambient temperature for 45 minutes.

Another dispersion was obtained by mixing 60 g of calcium carbonate with 90 g of water and mixing the mixture using a mixer.

A coating fluid was prepared by mixing and stirring 40 parts by weight of a dispersion of the above composition, 125 parts by weight of a dispersion of calcium carbonate and 120 parts by weight of an aqueous solution of 10% by weight of polyvinyl alcohol.

The coating liquid was applied to the base paper with a base weight of 40 g / m ² using a coating device with a core number 10 to obtain a bottom paper.

The result of the evaluation of the color intensity was so good that the optical density was 0.7.

The result of evaluating the resistance to solvent with a hand cream was so good that you could read the written part. The results obtained are summarized in table 10.

Reference Example 25

Pressure-sensitive recording material was obtained in the same manner as in Example 123, except for using activated alumina as a developer instead of the urea-urethane compound used in Example 123, and evaluated. The results obtained are summarized in table 10.

INDUSTRIAL APPLICATION

The use of a particular urea-urethane compound makes it possible to provide at low cost a color-forming composition and recording material that are excellent in image retention and color sensitivity.

Examples 124-134

As described in Example 9, 100 g of toluene as a solvent were added to a flask of 27.8 g of 2,4-toluene diisocyanate in a flask, after which a solution of 7.4 g of aniline in 37 g of toluene was added dropwise at room temperature over 1 hour. The interaction was carried out for another 1 hour. The white solid precipitate obtained by filtration was washed with hexane and then dried overnight in vacuo to give 20 g of white crystals (intermediate (I)). Then 5 g of the intermediate compound (I) thus obtained was added to ethanol (example 124), 1-propanol (example 125), 2-propanol (example 126), n-butyl alcohol (example 127), isobutyl alcohol (example 128) , sec-butyl alcohol (example 129), cyclohexanol (example 130), 1-hexanol (example 131), 1-decanol (example 132), stearyl alcohol (example 133) and benzyl alcohol (example 134), respectively, instead of methanol used as an aliphatic alcohol in Example 9. The reaction was carried out at 60 ° C, after which the excess solvent was removed using using a vaporizer, and then toluene was added. The resulting slurry was filtered to give a white solid on filter paper. The white solid was washed with n-hexane and then dried overnight in vacuo to give the urea-urethane composition as a white powder. The molar ratio of the starting products, the reaction conditions, the purity of the HPLC (area ratio), the melting point and the estimated structure of the main component of the resulting urea-urethane composition in each reaction are presented in table 11.

Then, heat-sensitive recording material was obtained in the same manner as in Example 1, except that instead of the urea-urethane compound synthesized in Example 1, the above compounds (S-1) - (S-11) were used and evaluated. The results obtained are summarized in table 14.

Examples 135-138

As described in Example 9, 100 g of toluene as a solvent was added to 27.8 g of 2,4-toluene diisocyanate in a flask, after which a solution of 7.4 g of aniline in 37 g of toluene was added dropwise at room temperature over 1 hour. The interaction was carried out for another 1 hour. The white solid precipitate obtained by filtration was washed with hexane and then dried overnight in vacuo to give 20 g of white crystals (intermediate (I)). Then, 5 g of the intermediate compound (I) thus obtained were reacted with phenol (example 135), o-methoxyphenol (example 136), p-methylphenol (example 137) and p-chlorophenol (example 138) dropwise as an aromatic alcohol, dissolved in 30 ml of MEK, instead of methanol used in example 9.

The reaction was carried out at 60 ° C, after which the excess solvent was removed using an evaporator, and then toluene was added thereto. The resulting slurry was filtered to give a white solid on filter paper. The white solid was washed with n-hexane and then dried overnight in vacuo to give the urea-urethane composition as a white powder. The molar ratio of the starting products, the reaction conditions, the purity of the HPLC (area ratio), the melting point and the estimated structure of the main component of the resulting urea-urethane composition in each reaction are presented in table 11.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the above compounds (E-1), (E-2), (E-4) were used , (E-5) and evaluated it. The results obtained are summarized in table 14.

Examples 139-144

To 27.8 g of 2,4-toluene diisocyanate in a flask was added 100 g of toluene as a solvent, after which a solution of 7.5 g of phenol in 37 g of toluene at 40 ° C. was added dropwise thereto over 1 hour. Then the interaction was carried out at 40 ° C for another 1 hour. A white solid, obtained by filtration, was washed with hexane and then dried overnight in vacuo to give 20.5 g of white crystals (intermediate (II)). Then, 5 g of the intermediate compound (II) thus obtained were reacted dropwise with the supplied aniline (Example 139), 4-methylaniline (Example 140), 4-chloroaniline (Example 141), 2-methoxy-5-N, N-diethylsulfamoylaniline ( Example 142), ethylamine (Example 143) and 4-methoxybenzene (Example 144) as an amine compound dissolved in 30 ml of MEK. The reaction was carried out at 30 ° C, after which the excess solvent was removed using an evaporator, and then toluene was added thereto. The resulting slurry was filtered to give a white solid on filter paper. The white solid was washed with n-hexane and then dried overnight in vacuo to give the urea-urethane composition as a white powder. The molar ratio of the starting products, the reaction conditions, the purity of the HPLC (area ratio), the melting point and the estimated structure of the main component of the resulting urea-urethane composition in each interaction are presented in table 12.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the above compounds (E-8), (E-10), (E-11) were used , (E-13), (E-44) and (E-9) and evaluated it. The results obtained are summarized in table 14.

Example 145

To 27.8 g of 2,4-toluene diisocyanate in a flask was added 100 g of toluene as a solvent, after which a solution of 9.8 g of p-anisidine in 37 g of toluene was added dropwise at room temperature over 1 hour. Then the interaction was carried out at 40 ° C for another 1 hour. A white solid, obtained by filtration, was washed with hexane and then dried overnight in vacuo to give 22 g of white crystals. Then, 5.6 g of the white crystals thus obtained were reacted with 10 g of phenol in 30 ml of MEK at 60 ° C, after which the excess solvent was removed using an evaporator, and then toluene was added thereto. The resulting slurry was filtered to give a white solid on filter paper. The white solid was washed with n-hexane and then dried overnight in vacuo to give 4.3 g of the urea-urethane composition as a white powder. The purity of the HPLC (area ratio) was 95%, the melting point was 176 ° C, and the estimated structure of the main component of the resulting urea-urethane composition was (E-6).

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the above compound (E-6) was used and evaluated. The results obtained are summarized in table 14.

Example 146

To 27.8 g of 2,4-toluene diisocyanate in a flask was added 100 g of toluene as a solvent, after which a solution of 10.7 g of p-aminoacetophene in 37 g of toluene was added dropwise at room temperature over 1 hour. The interaction was carried out for another 1 hour. A white solid, obtained by filtration, was washed with hexane and then dried overnight in vacuo to give 23 g of white crystals. Then, 5.8 g of the white crystals thus obtained were reacted with 10 g of phenol in 30 ml of MEK at 60 ° C, after which the excess solvent was removed using an evaporator, and then toluene was added thereto. The resulting slurry was filtered to give a white solid on filter paper. The white solid was washed with n-hexane and then dried overnight in vacuo to give 4.5 g of the urea-urethane composition as a white powder.

The purity of the HPLC (area ratio) was 95%, the melting point was 194%, and the estimated structure of the main component of the resulting urea-urethane composition was (E-7).

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the above composition (E-7) was used and evaluated. The results obtained are summarized in table 14.

Example 147

To 39.9 g of 4,4'-diphenylmethane diisocyanate (MDI) instead of 2,4-toluene diisocyanate, as in Example 9, 100 g of toluene was added as a solvent, and then a solution of 7.4 g of aniline in 37 g was added dropwise. toluene at room temperature for 1 hour. The interaction was carried out at room temperature for another 1 hour. The precipitated white solid was recovered by filtration, washed with hexane and then dried overnight in vacuo to give 25.7 g of white crystals. Then, 6.4 g of the crystals thus obtained were reacted with 10 g of phenol in 30 ml of MEK at 60 ° C., after which the excess solvent was removed using an evaporator, and then toluene was added. The resulting slurry was filtered to give a white solid on filter paper. The white solid was washed with n-hexane and then dried overnight in vacuo to obtain 4.8 g of a urea-urethane composition in the form of a white powder. The purity of the HPLC (area ratio) was 95%, the melting point was 210 ° C and the estimated structure of the main component of the obtained urea-urethane composition was (E-15).

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the above composition (E-15) was used and evaluated. The results obtained are summarized in table 14.

Example 148

The same method described in Example 4 was repeated, except that instead of 3.7 g of 4,4'-diaminodiphenylsulfone, 3.7 g of 3,3'-diaminodiphenylsulfone was used to give 5.0 g of a urea-urethane composition as white crystals. The estimated structure of the main component of the resulting urea-urethane composition was (E-21).

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the above composition (E-21) was used and evaluated. The results obtained are summarized in table 14.

Example 149

The same method described in Example 4 was repeated, except that 2.95 g of 4,4'-diaminodiphenylmethane was used instead of 3.7 g of 4,4'-diaminodiphenylsulfone, to give 8.0 g of a urea-urethane composition in the form white crystals. To 3.6 g of these crystals, 15 g of phenol was added to carry out a similar reaction as described in Example 4. 4.7 g of a urea-urethane composition were obtained in the form of a white powder. The estimated structure of the main component of the obtained urea-urethane composition was (E-27).

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the above composition (E-27) was used and evaluated. The results obtained are summarized in table 14.

Examples 150-153

As described in Example 9, 100 g of toluene as a solvent was added to a flask of 27.8 g of 2,4-toluene diisocyanate in a flask, after which a solution of 7.4 g of aniline in 37 g of toluene was added dropwise at room temperature over 1 hour. The interaction was carried out for another 1 hour. The white solid precipitate obtained by filtration was washed with hexane and then dried overnight in vacuo to give 20 g of white crystals (intermediate (I)). Then, intermediate compound (I) thus obtained was reacted with dipropylene glycol (example 150), glycerol (example 151), triethanolamine (example 152) and pentaerythriol (example 153) at 30 ° C in 60 ml of trimethyl phosphate as solvent with catalyst added 5 mg dibutyltin laureate. The reaction mixture was added to distilled water and filtered to give a white solid on filter paper. The white solid was dried overnight in vacuo to give the urea-urethane composition as a white powder. The molar ratio of the starting products, the reaction conditions, the purity of the HPLC (area ratio), the melting point and the estimated structure of the main component of the resulting urea-urethane composition in each reaction are presented in table 13.

Then, heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1, the above compounds (S-31), (S-32), (S-33) were used and (S-35) and evaluated it. The results obtained are summarized in table 14.

fog.

Claims (31)

1. The urea-urethane compound represented by the following compounds (S-1) to (S-70):

2. A urea-urethane composition comprising a urea-urethane compound and a diluent, where the urea-urethane compound is any compound represented by the following formulas (I) to (VII):

where X and Z independently represent a residue of an aromatic compound or a residue of an aliphatic compound, each residue may have one or more substituents; Y ₀ represents a group selected from the group consisting of a tolylene group, a xylylene group, a naphthylene group, a hexamethylene group and –φ-CH ₂ -φ-, where –φ- represents a phenylene group;

where X and Y independently represent a residue of an aromatic compound or a residue of an aliphatic compound, each residue may have one or more substituents;

where X and Y independently represent a residue of an aromatic compound or a residue of an aliphatic compound; α represents a residue with a valency of 2 or more; n is an integer of 2 or more, and each residue may have one or more substituents;

where Z and Y independently represent a residue of an aromatic compound or a residue of an aliphatic compound; β represents a residue with a valency of 2 or more; n is an integer of 2 or more, and each residue may have one or more substituents;

where the hydrogen atoms of each benzene ring can be substituted with a substituent, which preferably is the residue of an aromatic compound, the residue of an aliphatic compound or the residue of a heterocyclic compound, wherein the substituent can be a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, isocyanate group, mercapto group, sulfo group, sulfamoyl group or halogen atom, each residue may have one or several substituents; γ represents a group selected from the group including –SO ₂ -, –O–, - (S) _n -, - (CH ₂ ) _n -, –CO–, –CONH– and any of the groups represented by formulas (a );

or absent; n is 1 or 2.

where the hydrogen atoms of each benzene ring can be replaced by a substituent, which preferably is the residue of an aromatic compound, the residue of an aliphatic compound or the residue of a heterocyclic compound, wherein the substituent can be a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group , amino group, hydroxy amino group, nitroamino group, hydazino group, ureido group, iscyanate group, mercapto group, su lfogroup or halogen atom, each residue may have one or more substituents; δ ο is a group selected from the group consisting of –SO ₂ -, -O-, - (S) _n -, - (CH ₂ ) _n , -CO-, -CONH-, -NH-, -CH (COOR ₁ ) -, -C (CF ₃ ) ₂ - and –CR ₂ R ₃ - or is absent; each R ₁ , R ₂ and R ₃ represents an alkyl group; n is 1 or 2;

where X, Y and Z independently represent a residue of an aromatic compound or a residue of an aliphatic compound, each residue may have one or more substituents, and each X, Y and Z is preferably an aromatic residue, and wherein the diluent is a urea compound and / or a urethane compound obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound. 3. A method for producing a urea-urethane compound of the formulas (I) to (VII) specified in claim 2, which consists in reacting the polyisocyanate compound with a hydroxy compound or an amino compound so that the ratio of the number of moles of the polyisocyanate compound to the number of hydroxyl equivalents of the hydroxy compound or amino equivalents of the amino compound is 100 / 1-1 / 2 with the formation of one or more urethane or ureido groups of several isocyanate groups of the polyisocyanate compound. 4. The method according to claim 3, further comprising the subsequent addition of an amino or hydroxy compound, respectively, for its interaction with the remaining isocyanate groups of the polyisocyanate compound to produce one or more ureido or urethane groups. 5. The method according to claim 3, characterized by sequential interaction with the formation of one or more urethane groups and interaction with the formation of one or more ureido groups. 6. The method according to claim 3, characterized by conducting an interaction with the formation of one or more urethane groups, and / or interaction with the formation of one or more ureido groups without a solvent, or carrying out an interaction with the formation of one or more urethane groups and interaction with the formation of one or more ureido groups using the same solvent, preferably at a temperature of 0-300 ° C and / or preferably in the presence of a catalyst. 7. A method for producing a urea-urethane compound of the formulas (I) to (VII) indicated in claim 2, which comprises reacting an amino compound or a hydroxy compound with a polyisocyanate adduct obtained by reacting a polyisocyanate compound with a hydroxy compound or amino compound so that an equivalent ratio of the isocyanate group to the amino or hydroxyl group became 2/1 - 1/100, with the formation of one or more ureido groups or urethane groups and the subsequent removal of unreacted amino compounds and hydroxy compounds. 8. A color-forming composition comprising a developer containing a urea-urethane compound as defined in claim 2, which is prepared by the method according to any of claims 3 to 7, and, optionally, a colorless or slightly colored dye precursor. 9. The color-forming composition of claim 8, where the colorless or slightly colored dye precursor is a leuco dye, which, for example, is at least one leuco dye selected from triarylmethane type leuco dyes, fluorano type leuco dyes, fluorene type leuco dyes and diphenyl leuco dyes type; for example, the leuco dye is a compound selected from a compound represented by the following formula (i):

where both Y ₂ and Y ₃ represent alkyl groups or alkoxyalkyl groups; Y ₄ represents a hydrogen atom, an alkyl group or an alkoxy group; each of Y ₅ and Y ₆ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, or a compound represented by the following formula (j):

where each of R ₅ and R ₆ is a group represented by formula (k) or formula (l)

where each of R ₁₁ -R ₁₅ represents a hydrogen atom, a halogen atom, a C ₁ -C ₈ alkyl group, a C ₁ -C ₈ alkoxy group or –NR ₁₆ R ₁₇ , where each of R ₁₆ and R ₁₇ represents an alkyl a group of 1-8 carbon atoms, or

where each of R ₁₈ and R ₁₉ represents a hydrogen atom, an alkyl group of 1-8 carbon atoms or a phenyl group; each of R ₇ -R ₁₀ represents a hydrogen atom, a halogen atom, an alkyl group of 1-8 carbon atoms, an alkoxy group of 1-8 carbon atoms or –NR ₂₀ R ₂₁ , where each of R ₂₀ and R ₂₁ represents an alkyl group from 1-8 carbon atoms. 10. The color-forming composition according to claim 8 or 9, characterized in that the melting point of the urea-urethane compound of the developer is not higher than 500 and not lower than 40 ° C. 11. Color-forming composition according to any one of claims 8 to 10, characterized in that the urea urethane compound of the developer includes a compound selected from the group consisting of compounds represented by general formula (V)

where the hydrogen atoms of each benzene ring can be replaced by a residue of an aromatic compound, a residue of an aliphatic compound, a residue of a heterocyclic compound, a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group, a mercapto group, a sulfo group, a sulfo group, halogen, each of the residues may have one or more substituents; γ is a group selected from the group consisting of –SO ₂ -, –O–, - (S) _n -, - (CH ₂ ) _n -, –CO–, -CONH– and any group represented by formulas (a)

or absent; n is 1 or 2, and a compound represented by general formula (VI)

where the hydrogen atoms of each benzene ring can be replaced by 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, an amino group, an oxyamino group, a nitroamino group, a hydrazine group isocyanate group, mercapto group, sulfo group or halogen atom, each of the residues may have one or more substitutions Titel; δ is a group selected from the group consisting of –SO ₂ -, –O–, - (S) _n -, - (CH ₂ ) _n -, –CO–, –CONH–, NH–, –CH (COOR ₁ ) -, –C (CF ₃ ) ₂ - and –CR ₂ R ₃ -, or is absent; each of R ₁ , R ₂ and R ₃ represents an alkyl group; n is 1 or 2, for example, a compound of formula (XX)

and a compound of formula (XXI)

12. Color-forming composition according to any one of paragraphs. 8-11, further comprising a heat-fusible substance, which is, for example, at least one compound selected from β-naphthylbenzyl ether, p-benzylbiphenyl, 1,2-di (m-methylphenoxy) ethane, di-p-methylbenzyloxalate, 1,2-diphenoxymethylbenzene, m-terphenyl and stearamide, or a compound represented by the following structural formula (XVIII):

where Y represents any group from –SO ₂ -, - (S) _n -, -O–, –CO–, –CH ₂ -, –CH (C ₆ H ₅ ) -, –C (CH ₃ ) ₂ - , –COCO–, –CO ₃ -, –COCH ₂ CO–, –COOCH ₂ -, –CONH–, –OCH ₂ - and –NH–; n is 1 or 2, and the hydrogen atoms of each benzene ring can be replaced by a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a sulfamoyl group, a sulfonic acid group, an amino group, an aromatic compound residue, an aliphatic compound radical or a residue , or compounds represented by the following structural formula (XIX):

where the hydrogen atoms of each benzene ring can be replaced by a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a sulfamoyl group, a sulfonic acid group, an amino group, an aromatic compound residue, an aliphatic compound radical or a residue . 13. The color-forming composition according to any one of claims 8 to 12, which further comprises a component selected from the following group: isocyanate compound; isocyanate compound and imino compound; amino compound; an acid developer, wherein the acid developer is, for example, at least one developer selected from 2,2-bis (4-hydroxyphenyl) propane, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (3-allyl-4-hydroxyphenyl ) sulfone, 2,4'-dihydroxydiphenyl sulfone and 4,4 '- [oxybis (ethyleneoxy-p-phenylene sulfonyl)] diphenol; fluorescent paint; and storage stability agent. 14. A recording material comprising a substrate and a color-forming layer formed thereon, wherein said color-forming layer comprises a ureaurethane compound as defined in claim 2, or a color-forming composition as defined in any one of claims. 8-13. 15. The recording material according to 14, characterized in that the color-forming layer has a protective layer for the color-forming layer, which, for example, includes a water-soluble polymer, and / or the protective layer includes an inorganic pigment and / or organic pigment, and / or the protective layer includes a lubricant. 16. The recording material according to claim 14, wherein the intermediate layer is coated with a color-forming layer and the intermediate layer includes a water-soluble polymer and, optionally, the intermediate layer includes an inorganic pigment and / or organic pigment. 17. The recording material according to 14, characterized in that the coating layer of the back side is deposited on the substrate from the back side relative to the side having a color-forming layer formed on it, and the coating layer of the back side includes a water-soluble polymer and, optionally, includes inorganic pigment and / or organic pigment. 18. Recording material according to any one of paragraphs.14-17, characterized in that as a dispersing agent for the urea-urethane compound, it contains at least one compound selected from water-soluble polymers and anionic surfactants, for example polyvinyl alcohols, modified polyvinyl alcohols , methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalene sulfonate, ammonium salts of polycarboxylic acids, water soluble low molecular weight copolymers and 2-ethylhexyl sulfosuccin sodium; as a dispersing agent for a dye precursor contains at least one compound selected from water-soluble polymers, nonionic surfactants and anionic surfactants, for example, methyl cellulose, hydroxypropyl methyl cellulose, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ether sulfates and sodium 2-ethylhexyl sulfosuccinate. 19. The recording material according to any one of paragraphs.14-18, which is a heat-sensitive recording material. 20. The heat-sensitive recording material according to claim 19, characterized in that preferably the average particle size of the urea-urethane compound is not more than 5 μm and not less than 0.05 μm; the temperature of the liquid during grinding of the urea-urethane compound is 60 ° C or lower; the pH when grinding the urea urethane compound is from 5 to 10; as a dispersing agent for a heat-fusible substance, it contains at least one compound selected from water-soluble polymers and anionic surfactants, for example polyvinyl alcohols, modified polyvinyl alcohols, methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalenesulfonate, poly-carboxylic acid ammonium salts and sodium 2-ethylhexyl sulfosuccinate; the urea-urethane compound and the hot-melt substance are thoroughly ground together; The pH of the surface of the substrate, which is coated with a heat-sensitive recording layer of a heat-sensitive recording material, is from 3 to 9. 21. The recording material according to claim 14, which is a heat-sensitive magnetic recording material, for example, one where a heat-sensitive recording layer including a urea-urethane compound of the developer, as defined above, is applied on one side of the substrate, and a magnetic recording layer on the other side. 22. The heat-sensitive magnetic recording material according to item 21, which is a ticket, such as a train ticket. 23. The recording material of claim 14, which is a label for thermally sensitive recording, for example, where a thermally sensitive recording layer including a urea-urethane compound of the developer is applied on one side of the substrate, and an adhesive layer on the other side, and where, optional , the back side coating layer is applied between the adhesive layer and the substrate, and / or the intermediate layer is applied between the heat-sensitive recording layer and the substrate, and / or the protective layer is applied on the heat-sensitive recordings layer. 24. The recording material of claim 14, which is a color heat-sensitive recording material, for example, where at least two heat-sensitive recording layers are deposited on one side of the substrate and at least one of said heat-sensitive recording layers includes a urea urethane compound of the developer as defined above wherein, optionally, an intermediate layer is applied between the heat-sensitive recording layers. 25. The color heat-sensitive recording material according to paragraph 24, characterized in that it includes a substrate and two heat-sensitive recording layers laminated on one side of the substrate, which have different color development temperatures, respectively, and are exposed to color development of different color tones, respectively, the upper heat-sensitive recording layer, including either an agent used both as a developer and as a tone attenuator, or a reverse developer, and a lower temperature sensor a recording layer comprising a urea-urethane compound of the developer, preferably from two heat-sensitive recording layers, the upper layer is a low-temperature color-forming layer capable of undergoing color development at low temperature and achromatizing at high temperature, and the lower layer is a high-temperature color-forming layer capable of undergoing color manifestation at high temperature. 26. A method for producing a heat-sensitive recording material as defined in claim 14, characterized in that a recording layer of a heat-sensitive recording material is applied to a substrate of a heat-sensitive recording liquid for coating with a pH from 5 to 12. 27. An article for laser marking, characterized in that it has a heat-sensitive recording layer on the surface including a urea-urethane compound of the developer as defined in claim 2, and, optionally, a colorless or slightly colored dye precursor substance and an agent that improves recording sensitivity, which is, for example, at least one compound selected from aluminum hydroxide, muscovite, wollastonite and kaolin, and optionally has a protective layer on the heat-sensitive recording layer, including an aqueous binding agent having a glass transition point of 20–80 ° C. 28. The product for laser marking according to item 27, which is any label, packaging material and packaging. 29. A method of obtaining a product for laser marking, which consists in applying to the substrate a color-forming composition for marking, including a urea-urethane compound of the developer, as defined in claim 2, and, optionally, a colorless or slightly colored dye precursor substance and an agent that improves recording sensitivity, and drying thus obtained substrate. 30. The method of marking the product, which consists in irradiating a heat-sensitive recording layer of the product for laser marking in accordance with paragraph 27 or 28 of the laser beams. 31. Color-forming composition for marking, characterized in that it includes a urea urethane compound of the developer, as defined in claim 2, and, optionally, a colorless or light-colored dye precursor substance and an agent that improves recording sensitivity.