JPH11255736A - Compound for pressure-sensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound having excellent image-preservability, color-developing sensitivity and black color developing performance and usable as a color developing agent for a pressure-sensitive recording material by constituting the compound with a specific isocyanate adduct. SOLUTION: The objective compound is composed of an isocyanate adduct having a melting point of >=40 deg.C, preferably >=50 deg.C, more preferably >=60 deg.C. The isocyanate adduct is preferably e.g. an adduct of an isocyanate of formula I or formula II ((n) is 1 or 2; (m) is 0-5; H on the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue, and each residue may have substituent; X1 and X2 are each SO2 , O, CO or the like or absent). The isocyanate adduct compound can be produced e.g. by reacting an isocyanate with water to effect the dimerization, trimerization, or the like, through urea bond, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive recording material which develops color by applying pressure to the surface using a ball-point pen or a dot printer or the like, and can be used as a recording material. Specifically, the present invention relates to a compound that can be used for a pressure-sensitive recording material, a color former using the compound, and a pressure-sensitive recording material. In particular, it relates to a compound for a pressure-sensitive recording material having excellent image storability, color-forming sensitivity, and black color development, and a color-forming agent and a pressure-sensitive recording material using the same.

[0002]

2. Description of the Related Art Conventionally, many chemical color forming systems using recording energy such as light and pressure are known. Among them, a color forming system composed of a two-component color forming system of a colorless or pale color dye precursor and a color developing agent which forms a color in contact with the dye precursor has been known for a long time, and has been widely applied to recording materials. ing. In particular, a pressure-sensitive recording material using pressure energy has been very commonly used as if it were plain paper.

In general, a pressure-sensitive recording material is prepared by dissolving a dye precursor in an appropriate solvent, emulsifying the solution to several microns, and then performing microencapsulation. The microcapsules consist of an upper paper coated on a support and a lower paper coated with a developer layer containing a color developer on another support. The microcapsule-coated surface and the developer-coated surface face each other. Then, by applying a pen pressure or a pressing pressure or the like, the microcapsules are broken and the inclusions containing the dye precursor are released. This transfers to the color developer layer and comes into contact with the color developer, thereby producing a color development reaction, thereby obtaining image recording.

As a dye precursor and a color developer used in a pressure-sensitive recording material, an electron-donating compound and an electron-accepting compound are mainly used, respectively. This is because the reactivity of the dye precursor, which is the electron-donating compound, is high, and by contact with the developer, which is the electron-accepting compound, a color-developed image with a high density can be obtained instantaneously, This is because they have excellent characteristics such as obtaining a close appearance and obtaining various color hues such as red, orange, yellow, green, blue, and black. However, on the other hand, the obtained color-developed image has poor chemical resistance, so that it comes in contact with a plasticizer contained in a plastic sheet or an eraser or a chemical contained in food or cosmetics, and the record is easily lost, or However, since the light resistance of the recorded portion is inferior, the recording has a disadvantage that the storage stability of the recording is inferior, such as fading or even disappearing of the recording by exposure to sunlight for a relatively short period of time. At present, certain restrictions are imposed on applications, and improvements are strongly desired.

As a pressure-sensitive recording material capable of obtaining a recorded image having good storability in response to such demands, for example, Japanese Patent Application Laid-Open No.
9-115887 and U.S. Pat. No. 452179.
No. 3 discloses a recording material comprising a combination of a color former comprising an aromatic isocyanate compound and an imino compound. These publications exemplify various recording materials by contacting and reacting two types of color forming agents by applying recording energy such as heat, pressure, and light. Further, it is described that various colors such as red, orange, yellow, brown, and brown can be developed by appropriately selecting a coloring agent. However, while black color is particularly demanded in recording materials widely used at present, the knowledge described in the invention described in the publication cannot be obtained.

[0006] Japanese Patent Application Laid-Open No. 64-1580 discloses that
A color former comprising a dye precursor and an aromatic isocyanate compound is disclosed, but the color density and the recording stability are insufficient.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a compound for a pressure-sensitive recording material having excellent image storability and color-forming sensitivity, and a color former and a pressure-sensitive recording material using the same. Furthermore, black color can be formed, and the color density,
An object of the present invention is to provide a pressure-sensitive recording material having excellent recording stability and a color former and a compound used for the material.

It is another object of the present invention to provide a pressure-sensitive recording material whose material is easily available and easy to manufacture, and a color former and a compound used for the material.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies on the improvement of the performance of a pressure-sensitive recording material, and as a result, the use of a specific isocyanate compound as a color former of the pressure-sensitive recording material has led to surprisingly excellent results. The inventors have found that performance is exhibited, and have completed the present invention. That is, the present invention is as follows.

A first aspect of the present invention is a compound for a pressure-sensitive recording material, which is an isocyanate adduct having a melting point of 40 ° C. or higher. In a second aspect of the present invention, the isocyanate adduct is represented by the following formula (I):
The compound according to the first aspect of the present invention, which is an adduct of an isocyanate represented by the formula:

[0011]

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(Here, n represents an integer of 1 to 2. The hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent.) In the third aspect of the invention, an isocyanate adduct is represented by the following formula (I)
The compound according to the first aspect of the present invention, which is an adduct of isocyanate represented by I).

[0013]

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(Wherein, m is an integer of 0 to 5, n is 1 or 2. The hydrogen atom of the benzene ring is substituted by an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent, and X ₁ and X ₂ are each independently —SO ₂
-, - O -, - ( S) q -, - (CH 2) q -, - CO
-, - CONH -, - CH (C 6 H 5) -, - C (CH
_{3) 2} - shows the case where either or not present. q
Is 1 or 2. A fourth aspect of the present invention is a compound for a pressure-sensitive recording material represented by any of the following formulas (III) to (XII).

[0015]

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(Where R ₁ is the value of the formula (a) or the formula (b)
Represents The same applies to the following formulas (IV) to (XII).

[0017]

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(Here, n represents an integer of 1 to 2. The hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent.)

[0019]

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(Wherein m is an integer of 0 to 5, n is 1 or 2. The hydrogen atom of the benzene ring is substituted by an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue. Each residue may have a substituent, and X ₁ and X ₂ are each independently —SO ₂
-, - O -, - ( S) q -, - (CH 2) q -, - CO
-, - CONH -, - CH (C 6 H 5) -, - C (CH
_{3) 2} - shows the case where either or not present. q
Is 1 or 2. ))

[0021]

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[0022]

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(R ₂ represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. Each residue may have a substituent. The following formula (VI): (V
Same in II) and (VIII). )

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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(R ₃ represents an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue. Each residue may have a substituent.)

[0030]

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(R ₄ is an aromatic compound residue which may have a substituent, a heterocyclic compound residue which may have a substituent or an aliphatic compound residue or an inorganic compound residue which may have a substituent. Represents a group.)

[0032]

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(R ₅ and R ₆ each independently represent an aromatic compound, a heterocyclic compound or an aliphatic compound residue.
Each residue may have a substituent. R ₅ and R ₆ may form a cyclic structure with each other. A fifth aspect of the present invention is the fourth aspect of the present invention, wherein R ₁ is represented by the following formula (c) or (d).
The compound according to the above.

[0034]

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[0035]

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A sixth aspect of the present invention is a color former containing a colorless or pale-color electron-donating dye precursor and the compound according to any one of the first to fifth aspects of the present invention. A seventh aspect of the present invention is the color former according to the sixth aspect, which comprises an amino compound. Eighth of the invention is:
The color former according to any one of the sixth to seventh aspects of the invention, which contains a hydroxyl group-containing compound.

According to a ninth aspect of the present invention, there is provided a pressure-sensitive recording material provided with a color-forming layer containing the color-forming agent according to any one of the sixth to eighth aspects of the invention on a support. Hereinafter, the present invention will be described in detail. The compound for a pressure-sensitive recording material of the present invention is an isocyanate adduct compound having a melting point of 40 ° C. or higher. Surprisingly, the above-mentioned problem can be solved by using this as a coloring agent of a thermosensitive recording material.

In the isocyanate adduct compound of the present invention, at least one isocyanate group of the isocyanate is used as a reactive group, and the isocyanate is dimerized or trimerized via a urea bond or a biuret bond by reaction with water. Or a method of derivatizing to a corresponding substituted urea or substituted biuret by an addition reaction with an amine compound, or a method of dimerization by heat or a method of deriving to a substituted urethane or a substituted allohanate by an addition reaction with an OH group-containing compound Or an addition reaction method with a compound having active hydrogen, or the like. Further, an isocyanate adduct compound obtained by carrying out any of the above-mentioned reactions using an isocyanate adduct compound obtained by the above method such as carbodiimide-modified MDI or polyol-modified MDI as a starting material may be used.
The starting isocyanate is not particularly limited as long as it has two or more isocyanate groups. For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,2 4-toluene diisocyanate, 2,6-toluene diisocyanate,
Diphenylmethane diisocyanate, o-tolidine diisocyanate, 1,5-naphthylene diisocyanate,
Dianisidine diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3′-dimethyl-
4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate 4,4 ′, 4 ″ -triisocyanatotriphenylamine, triphenylmethanetriisocyanate, tris (4-phenylisocyanate The isocyanate adduct compound of the present invention is a colorless or pale color solid at room temperature and has a melting point of 40.
C. or higher, and preferably 40 ° C. or higher and 500 ° C. or lower. However, depending on the structure of the compound, it may be decomposed or deteriorated at a temperature lower than the melting point to show no melting point. The melting point is preferably at least 50 ° C, more preferably at least 60 ° C. The melting point of the adduct compound is 40
If the temperature is lower than ℃, when it is used as a color forming agent, problems are apt to occur in heat resistance and moisture resistance, which are often not preferable in practical use. Further, an isocyanate adduct compound obtained by further performing any one of the above-mentioned reactions using an isocyanate adduct compound as a starting material may be used. That is, by using this technology, by increasing the melting point to 40 ° C. or higher by increasing the molecular weight, heat resistance, moisture resistance, etc. are improved, and there is no practical problem as a color former, and excellent performance can be exhibited. .

In particular, the isocyanate adduct compound is an isocyanate adduct represented by the above formula (I) or (II) or a compound of the above formulas (III) to (XI)
The isocyanate compound represented by I) is preferred. The adduct compound of the aromatic isocyanate represented by the above formula (I) refers to an isocyanate represented by the above formula (I), preferably at least one isocyanate group of the toluene diisocyanate starting from toluene diisocyanate. And is an isocyanate compound having at least one isocyanate group. As the toluene diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate are generally commercially available, and can usually be obtained at a low price as a mixture thereof.

The toluene diisocyanate isomer mixture itself is a liquid at normal temperature (100% 2,4-toluene diisocyanate and a melting point of 19.5 ° C. to 2 ° C.).
1.5 ° C, 65% 2,4-toluene dissocyanate /
(A 35% mixture of 2,6-toluene diisocyanate having a melting point of 3.5 ° C. to 5.5 ° C.) It is practically difficult to use this form as a color former in this state.

The isocyanate adduct compound represented by the formula (II) is an aromatic isocyanate represented by the formula (II) or polymethylene polyphenyl polyisocyanate (hereinafter referred to as cr.MDI) or diphenylmethane. It refers to a new isocyanate compound obtained by performing an addition reaction to diisocyanate (hereinafter, MDI).

The above cr. MDI or MDI itself is generally commercially available and can usually be obtained at low cost. However, for example, cr. MDI is a normal temperature brown liquid, and MDI has a freezing point of 38 ° C., and using it as it is as a color former has a practical problem. The aromatic isocyanate compound represented by the above formula (I) which can be used in the present invention may be any compound having two or more NCO groups on a benzene ring, such as p-phenylene diisocyanate, m- Phenylene isocyanate,
Toluene diisocyanate, 1,3-dimethylbenzene-4,6-diisocyanate, 1,4-dimethylbenzene-2,5-diisocyanate, 1-methoxybenzene-2,5-diisocyanate, 1- Ethoxybenzene
2,4-diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,5-diethoxybenzene-1,4-diisocyanate, 2,5-dibutoxybenzene-1,4 -Diisocyanates and the like. Particularly preferred is toluene diisocyanate, and toluene diisocyanate may be 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or a mixture thereof.

The aromatic isocyanate represented by the above formula (II) which can be used in the present invention includes, for example, dianisidine diisocyanate, diphenyl ether diisocyanate, orthotrizine diisocyanate, bis [4- (m -Isocyanatophenoxy) phenyl] sulfone, bis [4- (p-isocyanatophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-isocyanatophenoxy) phenyl] sulfone, 3,3'-dimethoxy- 4,4'-diisocyanatobiphenyl, 3,
3'-dimethyl-4,4'-diisocyanatobiphenyl, 2,2'-dichloro-4,4'-diisocyanato-
5,5'-dimethoxybiphenyl, 2,2 ', 5,5'
-Tetrachloro-4,4'-diisocyanatobiphenyl, 2,4'-diisocyanatobiphenyl, 2,2'-
Diisocyanatobiphenyl, 4,4'-diisocyanatobiphenyl, 2,2'-dichloro-4,4'-diisocyanatobiphenyl, 3,3'-dichloro-4,4'-diisocyanatobiphenyl, , 2'-dimethyl-4,
4'-diisocyanatobiphenyl, 4,4'-diisocyanatodiphenylether, 3,3'-diisocyanatodiphenylether, 3,4'-diisocyanatodiphenylether, 3,4'-diisocyanatodiphenylmethane, bis ( 3-isocyanato-4-chlorophenyl)
Sulfone, bis (3,4-diisocyanatophenyl) sulfone, bis (4-isocyanatophenyl) sulfone,
Bis (3-isocyanatophenyl) sulfone, 3,4 '
Diisocyanatodiphenylsulfone, 3,3'-diisocyanatodiphenylmethane, 4,4'-diisocyanato-3,3'-dichlorodiphenylmethane, 1,4-bis (4-isocyanatophenoxy) benzene, 1,3-
Bis (4-isocyanatophenoxy) benzene, 1,3
-Bis (3-isocyanatophenoxy) benzene, 2,
2-bis (4-isocyanatophenoxyphenyl) propane, 4,4'-bis (4-isocyanatophenoxy)
Examples thereof include diphenyl, 3,3 ', 4,4'-tetraisocyanatodiphenyl ether, 3,3', 4,4'-tetraisocyanatodiphenylsulfone and the like. These aromatic isocyanate or polymethylene polyphenyl polyisocyanate (cr.MDI) or diphenylmethane diisocyanate (MDI) may be used alone or in a mixture thereof.

As the reactant for forming these isocyanate adducts, in addition to water, for example, aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-
Dimethylaniline, N, N-diethylaniline, N, N
-Dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid , O-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylysine, 2,
4-xylidine, 3,4-xylidine, 2,6-xylidine, acetanilide, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloro Aniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-
Chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N
-Butylaniline, N, N-diglycidylaniline,
N, N-diglycidyl-o-toluidine, acetoacetic anilide, trimethylphenylammonium bromide,
4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether,
3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2- Chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, iso-propyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N- Methylbenzamide, 3-
Amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p
-[N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl]
Aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- ( 2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2
-Methoxyaniline, 4-acetylaminoaniline, 4
-(N-methyl-N-acetylamino) aniline, 2,
5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, 4- Sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4
-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [ 4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy)
Phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diamino Biphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,
4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,
2'-dichloro-4,4'-diaminobiphenyl, 3,
3'-dichloro-4,4'-diaminobiphenyl, 2,
2'-dimethyl-4,4'-diaminobiphenyl, 4,
4'-thiodianiline, 2,2'dithiodianiline, 4,
4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone,
Bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,
4-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4 '
-Diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4 -Aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, 3,3 ', 4,4'-tetraaminodiphenyl ether, 3, 3 ', 4,4'-tetraaminodiphenyl sulfone, 3,3'4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-
Methylenebis-O-toluidine, 4,4 '-(p-phenyleneisopropylidene) -bis- (2,6-xylysine), o-chloro-p-nitroaniline, o-nitro-
p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2 -Methyl-4-
Nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, methol, 2,4-
Diaminophenol, p-hydroxyphenylglycine, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanylic acid, 4B acid, C
Acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m- Toluylenediamine, 2-aminothiophenol, 2-amino-
3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine , 4,4 '
-Diaminostilbene-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthonic acid, tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1, Aromatic amines such as 4-diamino-2,3-dichloroanthraquinone, 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε -Caprolactam, acetoguanamine, 2,4-diamino-6- [2'-methylimidazolyl- (1)] ethyl-S-triazine, 2,
3-diaminopyridine, 2,5-diaminopyridine,
Heterocyclic compounds such as 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine Amines,
Methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine,
2-ethylhexylamine, ethanolamine, 3-
(2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, t
-Butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4
-Diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine,
2-bromoethylamine, 2-methoxyethylamine,
Aliphatic such as 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane and 2-aminoethanethiol Amines, tetrakis (1,2,2,6,6-pentamethyl-
4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, , 2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, β, β, β ′, β′-tetramethyl-
3,9- (2,4,8,10-tetraoxaspiro [5,5] undecanediethanol condensate,
3,4-butanetetracarboxylic acid ・ 2,2,6,6-tetramethyl-4-piperidinol ・ β, β, β ′, β ′
-Tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecanediethanol condensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino- 1,3,5-triazine-2,4-diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2,2,6,6-tetramethyl-4- Piperidyl) imino}], N, N'-bis (3-aminopropyl) ethylenediamine-2,4-
Bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,
3,5-triazine condensate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid-bis (1,2,2,6,6-pentamethyl-4 −
Hindered amine compounds such as piperidyl) and succinic acid-bis (2,2,6,6-tetramethyl-4-piperidienyl) ester.

Further, examples of the OH group-containing compound which can be used as a reactant for forming an isocyanate adduct include phenol, cresol, xylenol, and the like.
p-ethylphenol, o-isopropylphenol,
Resorcinol, p-tert-butylphenol, pt
ert-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 (hydroxy Phenols such as phenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol and 4-cumylphenol (however, these phenols It is not preferable that the compounds have an amino group. When the amino group is present, the reactivity with the isocyanate group is higher than that of the OH group, so that the amino group reacts first and the target compound cannot be obtained.) , Methanol, ethanol, propanol, butanol, pen Tanol, hexanol, heptanol, octanol, isopropanol, 2-pentanol, 3-hexanol, tert-butanol, t
ert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol,
2-methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, phenylcellosolve, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane ,
Alcohols such as glycerin and glycerol, polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenol polyol, and amine modified polyol , Ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 6-hexane glycol, 1,9-nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxypoly Lumpur, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol, polymer polyol, methyl pentanediol, halogen-containing polyols, phosphorus-containing polyols,
Polyols such as ethylenediamine, α-methylglucoside, sorbitol, and soucrose, and other compounds having active hydrogen that reacts with isocyanate include dimethyl malonate, diethyl malonate, ethyl acetoacetate, butyl mercaptan, thiophenol, tert-dodecyl Mercaptan, acetanisidide, acetate amide, benzamide, p-toluenesulfonamide, o-toluenesulfonamide, p-chlorobenzenesulfonamide,
Imino compounds such as benzenesulfonamide, hydrazine, hydroxylamine, succinimide, maleic imide, acetanilide, imidazole, methylethylketoxime, acetoaldoxime, sodium bisulfite, urea, ammonia, 3-iminoisoindoline, iminobenzophenone, And imine compounds such as piperidine, ethyleneimine and piperazine.

In order to obtain the isocyanate adduct compound used in the present invention, the reactant is mixed with the isocyanate in an organic solvent or in the absence of a solvent, and the excess isocyanate is removed by filtration or distillation under reduced pressure. The desired product can be obtained. A single or a plurality of reactants may be used depending on the purpose. The solvent may be any solvent that does not cause a reaction with the isocyanate group and the functional group of the reactant,
Examples include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, and the like. In particular, cyclohexane, ethylcyclohexane, toluene, and the like which dissolve the isocyanate and have low solubility of the product are preferable. The product obtained by the above reaction operation is not necessarily a single product, but a mixture of a compound having different substituent positions, a mixture of a substituted urea and a substituted biuret, a mixture of a substituted urethane and a substituted allohanate, and further an addition reaction proceeds. It may be obtained as a mixture of those having a molecular weight, but this is also acceptable. The target product can also be obtained by reacting the reaction agent with the product obtained by the above reaction operation as a starting material.

The adduct ratio in the isocyanate is
It is at least 30%, preferably at least 50%, more preferably at least 80%. Most preferred is 100
%. The melting point of the isocyanate adduct compound thus obtained may be 40 ° C. or higher, preferably 5 ° C.
The temperature is 0 ° C. or higher, more preferably 60 ° C. or higher.
When the melting point of the adduct compound is less than 40 ° C., when it is used as a coloring agent, problems are likely to occur in heat resistance, moisture resistance and the like, which is not preferable in practical use. The upper limit of the melting point is 500 ° C.
The following is preferred. However, depending on the structure of the compound, the compound may decompose or degrade at a temperature lower than the melting point to show no melting point, but in this case, there is no problem in performance as long as the lower limit of the melting point is satisfied.

These isocyanate compounds may be added to phenols, lactams, oximes and the like, if necessary, to mask the isocyanate, and dissociate when heat is applied to regenerate the isocyanate. It may be used in the form of isocyanate. The isocyanate adduct compound or the isocyanate compounds (III) to (XII) used in the present invention are preferably colorless or light-colored solids at room temperature. In preparing the pressure-sensitive recording material, one type or a mixture of the isocyanate compound, the isocyanate adduct compound or the isocyanate compounds (III) to (XII) is used, but if necessary, two or more types may be used in combination. it can.

The isocyanate compounds (III) to (XI)
I) can be obtained by converting the corresponding amine compound into an isocyanate by a phosgene reaction, but can also be easily obtained by the above-mentioned method of producing an adduct compound. The color former obtained by adding a colorless or light-colored electron-donating dye precursor to the isocyanate adduct compound of the present invention, and the pressure-sensitive recording material using the same are, surprisingly, an isocyanate conventionally used as a color former. The compound 4,
Compared with those using 4 ', 4''-triisocyanato-2,5-dimethoxytriphenylamine, the color development sensitivity is high, the color is black, and the print storability is extremely excellent.

The colorless or light-colored electron-donating dye precursor that can be used in the color-forming agent of the present invention is a compound already known as a color-forming agent used in pressure-sensitive recording materials, and is not particularly limited. The following are mentioned. (1) Triarylmethane compound 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide, 3- ( p-dimethylaminophenyl) -3-
(1,2-dimethylindol-3-yl) phthalide,
3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindole-
3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindole-3-
Yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5 -Dimethylaminophthalide, 3-
p-dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide and the like.

(2) Diphenylmethane compounds 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, N-halophenylleucouramine, N-2,4,5-trichlorophenylleucouramine and the like. (3) Fluoran compounds Rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-octylaminofluoran, 3-diethylamino-7 -Phenylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-6-chloro-7-methylfluoran, 3-diethylamino-7- (3,4-dichloroanilino) fluoran, 3-diethylamino- 7
-(2-chloroanilino) fluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3- (N
-Ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino-6 Methyl-7-phenethylfluoran, 3-diethylamino-7- (4-nitroanilino) fluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-propyl) amino-
6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-cyclohexyl) amino-6 Methyl-7-anilinofluoran, 3
-(N-ethyl-N-tetrahydrofuryl) amino-6
-Methyl-7-anilinofluoran, and the like.

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

The colorless or pale-color electron-donating dye precursor is used in an amount of 5 to 50 based on the isocyanate adduct compound.
0% by weight, more preferably 2% by weight.
0 to 200% by weight. When the amount of the colorless or light-colored electron-donating dye precursor is 5% by weight or less, color development is insufficient. If the colorless or light-colored electron-donating dye precursor is 500% by weight or more, an unreacted electron-donating dye precursor remains excessively, which is not economically preferable.

It is preferable to include an amino compound in the color former according to the present invention. Thereby, higher image density and higher image storability can be obtained. The amino compound that can be used in the present invention is a colorless or pale-colored substance having at least one primary, secondary, or tertiary amino group. Specific examples of these amino compounds include tallow or coconut oil-derived aliphatic amines, cetylamine, stearylamine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, p-aminobenzoic acid-i
so-propyl, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o
-Aminobenzophenone, m-aminoacetophenone,
p-aminoacetophenone, m-aminobenzamide,
o-aminobenzamide, p-aminobenzamide, p
-Amino-N-methylbenzamide, 3-amino-4-
Methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p-
(N-phenylcarbamoyl) aniline, p- [N-
(4-chlorophenyl) carbamoyl] aniline, p-
[N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl)
Aniline, 2-methoxy-5- [N- (2'-methyl-
3'-chlorophenyl) carbamoyl] aniline, 2-
Methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2,5 -Diethoxy-4- (N-benzoylamino) aniline, 2,5
-Dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5
-Methylaniline, 4-sulfamoylaniline, 3-
Sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-N -Phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2 -Phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-amino Phenoxy) phenyl] sulfone, bis [ -Methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,
4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diamino Biphenyl, 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, bis (4-amino Phenyl) sulfone, bis (3-aminophenyl) sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4 '
-Ethylenedianiline, 4,4'diamino-2,2'-
Dimethyldibenzyl, 4,4'-diamino-3,3'-
Dichlorodiphenylmethane, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4
-Bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4
-Aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, 3,3 ', 4,
4'-tetraaminodiphenyl ether, 3,3 ',
4,4'-tetraaminodiphenyl sulfone, 3,3 '
4,4'-tetraaminobenzophenone, 4-aminobenzonitrile, 3-aminobenzonitrile, p-phenylenediamine, m-phenylenediamine, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-diaminodiphenylmethane, , 4'-Methylenebis-O-
Aniline derivatives such as toluidine, 4,4 ′-(p-phenyleneisopropylidene) -bis- (2,6-xylysine), and acetoguanamine, 2,4-diamino-
6- [2'-methylimidazolyl- (1)] ethyl-S
-Triazine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine,
Heterocyclic compounds such as 2,5-diaminopyridine and 2,3,5-triaminopyridine, and tetrakis (1,
2,2,6,6-pentamethyl-4-piperidyl)-
1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3 4-butanetetracarboxylic acid ・ 1,
2,2,6,6-pentamethyl-4-piperidinol
β, β, β ′, β′-tetramethyl-3,9- (2,
4,8,10-tetraoxaspiro [5,5] undecanediethanol condensate, 1,2,3,4-butanetetracarboxylic acid · 2,2,6,6-tetramethyl-4-piperidinol · β, β , Β ', β'-tetramethyl-3,
9- (2,4,8,10-tetraoxaspiro [5,
5] undecanediethanol condensate, poly [$ 6-
(1,1,3,3-tetramethylbutyl) amino-1,
3,5-triazine-2,4-diyl {(2,2,
6,6-tetramethyl-4-piperidyl) imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N'-bis (3-aminopropyl) ethylenediamine 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, 2- (3 Bis- (1,5-Di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid
Hindered amine compounds such as 2,2,6,6-pentamethyl-4-piperidyl) and bis- (2,2,6,6-tetramethyl-4-piperidienyl) succinate are mentioned.

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

[0056]

Embedded image

(Wherein R ₇ , R ₈ , R ₉ and R ₁₀ are
Each independently represents a hydrogen, a halogen, an alkyl group, an alkoxy group or an amino group; X ₃ and X ₄ each independently represents an amino group or a formula (e);

[0058]

Embedded image

Y ₁ is —SO ₂ —, —O—, — (S)
_{n -, - (CH 2)} n -, - CO -, - CONH-, or of formula (f),

[0060]

Embedded image

Or, the case where it does not exist is shown. n is 1 or 2. The amino compound may be used alone or as a mixture. In order to improve the print preservability in plasticizer resistance, the amino compound is used in an amount of 1 to 5 with respect to the isocyanate adduct compound.
It is preferably 00% by weight. If the content of the amino compound is less than 1% by weight based on the isocyanate compound, sufficient print storability cannot be obtained. Further, even if it is used in an amount exceeding 500% by weight, the performance is not improved, and the cost is disadvantageous.

In the color former according to the present invention, it is preferable to add a hydroxyl group-containing compound. Thereby, the image density is improved, and a pressure-sensitive recording material having high image storability can be obtained. Examples of the hydroxyl group-containing compound include a phenol derivative, an aromatic carboxylic acid derivative or a metal compound thereof, a salicylic acid derivative or a metal salt thereof, in addition to an electron-accepting substance generally used in a pressure-sensitive recording material. Specifically, an inorganic compound such as acid clay, activated clay, attapulgite, benite, zeolite, colloidal silica, magnesium silicate, talc, aluminum silicate, or phenol, p-ethylphenol, o-isopropylphenol, resorcinol, p
-Tert-butylphenol, p-tert-octylphenol, 2-naphthol, β-oxynaphthoic acid, p-nitrophenol, o-chlorophenol, p
-Chlorophenol, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 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, bis (4-hydroxyphenyl) ) Butyl acetate, bis (4-hydroxyphenyl) benzyl acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4′-methylphenylsulfone, 3- Chloro-4-hydroxy Eniru 4'-methylphenyl sulfone, 3,4-dihydroxy-4'-methyl phenyl sulfone, 4-isopropylphenyl-4 '
-Hydroxyphenylsulfone, 4-isopropyloxyphenyl-4′-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone,
-Hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, bis (2-methyl-3-ter
t. -Butyl-4-hydroxyphenyl) sulfide;
Methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), 1,2-bis (4'-hydroxybenzoic acid)
Ethyl, 1,5-bis (4′-hydroxybenzoic acid) pentyl, 1,6-bis (4′-hydroxybenzoic acid) hexyl, 3-hydroxyphthalic acid dimethyl, stearyl gallate, lauryl gallate, salicylic acid, etc. Or an aldehyde condensed novolak resin derived therefrom and a metal salt thereof, 3-isopropylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid,
3,5-di-t-butylsalicylic acid, 3-n-octyloxysalicylic acid, 3-n-butyloxysalicylic acid,
3-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octylaminosalicylic acid, 3-n-octanoylaminosalicylic acid, 4-methyloxycarbonylaminosalicylic acid, 4-n-butyloxycarbonylaminosalicylic acid 4-n-heptyloxycarbonylaminosalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, 4-n-nonyloxycarbonylaminosalicylic acid, 5-n-octyloxycarbonylaminosalicylic acid, 6-n-octyloxycarbonylaminosalicylic acid 3,5-di (α-methylbenzyl) salicylic acid, 3,5-di-t-octylsalicylic acid, 3-methyl-5-benzylsalicylic acid,
3,5-di (α, α-dimethylbenzyl) salicylic acid,
3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid and the like, and metal salts thereof.

For producing a pressure-sensitive recording material, for example, US Pat. Nos. 2,505,470, 2,712,507, and 273 can be used.
Nos. 4,456, 2,730,457, 3,418,250, and the like. In general, dye precursors are used alone or in combination to form synthetic oils such as alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated diarylethane, chlorinated paraffin, and vegetable oils, animal oils, and mineral oils. Or the like, or by dissolving it in a solvent consisting of a single or mixture thereof and dispersing it in a binder, or applying a dispersion liquid contained in microcapsules on a support together with a binder or the like to obtain an upper paper. Also, a dispersion of an isocyanate adduct compound (and an amino compound and / or a hydroxyl group-containing compound) is applied, and the dispersion containing the dye precursor is applied on the other surface. The above isocyanate adduct compound (and an amino compound and / or a hydroxyl group-containing compound)
A mixture of the dispersion liquid containing the dye precursor and the dispersion liquid containing the above-mentioned dye precursor, or a multi-layer coating, and a dye precursor, an isocyanate adduct compound (and an amino compound and / or a hydroxyl group-containing compound) are both micro-sized. Various forms such as a self-type encapsulating and mixed and applied can be adopted.

The method for producing microcapsules includes the coacervation method disclosed in US Pat. Nos. 2,800,457 and 2,800,458, and JP-B-38-1.
9574, 42-446, 42-77
No. 1, JP-B-36-91.
No. 68, Japanese Patent Publication No. 51-9079, the in-situ method disclosed in British Patent No. 952807,
96-5074, etc., the melting dispersion cooling method disclosed in U.S. Pat. No. 3,111,140, and British Patent No. 930.
For example, a spray drying method disclosed in Japanese Patent No. 422 or the like can be employed.

When microcapsules are formed from a colorless or pale-colored electron-donating dye precursor and an isocyanate adduct compound, they may be used by dissolving them in a solvent or by dispersing them. In the case of a coloring system including an amino compound and / or a hydroxyl group-containing compound, it may be used alone or in combination with an isocyanate adduct compound and an amino compound and / or a hydroxyl group-containing compound, which are dissolved or dispersed in a solvent. Good.

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

In this case, the isocyanate compound is consumed not only for the pressure-sensitive recording material but also for the formation of a film of a general microcapsule, and is not directly involved in a color image. Use is essential, and in these respects, it is distinguished from the use of the isocyanate adduct compound of the present invention. A dispersion of a compound without microencapsulation can be prepared by pulverizing one or more of each compound in an aqueous solution containing a compound having a dispersing ability such as a water-soluble polymer or a surfactant. Can be The isocyanate adduct compound is an amino compound and / or an alcoholic compound,
It may be dispersed simultaneously with the hydroxyl group-containing compound.

As the support used for the pressure-sensitive recording material according to the present invention, paper is mainly used. In addition to paper, various woven fabrics, nonwoven fabrics, synthetic resin films, laminated paper, synthetic paper, metal foil, Can be arbitrarily used according to the purpose. As the binder, various commonly used binders can be used, for example, starches, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohol,
Modified polyvinyl alcohol, sodium polyacrylate, acrylamide / acrylate copolymer, acrylamide / acrylate / methacrylic acid terpolymer, alkali salt of styrene / maleic anhydride copolymer,
Water-soluble binders such as alkali salts of ethylene / maleic anhydride copolymers, and latex-based water-insoluble binders such as styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, and methyl acrylate / butadiene copolymers. Can be

An embodiment of the pressure-sensitive recording material according to the present invention will be specifically described with reference to sectional views. FIG. 1 is a sectional view showing a pressure-sensitive recording material according to the present invention. A is an upper paper comprising a microcapsule-containing pressure-sensitive layer 2 on which a base material 1 is microencapsulated with either a dye precursor or an isocyanate adduct compound (and an amino compound or / and a color developer). FIG. 2 is a cross-sectional view showing a combination of a lower sheet and a pressure-sensitive receiving layer 5 in which another substance is applied in the form of fine particles to a substrate 4.

B is the substrate 6 between the upper and lower sheets of A.
3 is a cross-sectional view of a set of three sheets in which medium sheets provided with 5 and 2 coating layers on both sides of the sheet are combined. C is a self-color-forming layer obtained by microencapsulating one of a dye precursor and an isocyanate adduct compound (and an amino compound and / or a color developer) on the same surface of the base material 8 and mixing and coating the other in the form of fine particles. 7 shows a cross-sectional view of a self-type consisting of 7.

D shows a self-type in which the self-color-forming layer 7 was separated and applied to the microcapsule-containing layer 9 and the reaction layer 10 in C. E indicates a self-label type provided with an adhesive layer 12 for C and F for D. G is a dye precursor, an isocyanate adduct compound (and an amino compound or /
And a color developer are microencapsulated, and the other is provided with a pressure-sensitive transfer layer 13 formed by mixing and coating the other in the form of fine particles. H shows a cross-sectional view in which the pressure-sensitive transfer layer is separated into a microcapsule-containing layer 9 and a reaction layer 10 in G and combined with plain paper 14.

[0072]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples. In addition, each physical property was evaluated by the following methods. <Coloring density> A color image was obtained on the lower paper by applying pressure while overlapping the upper and lower papers so that the coated surfaces of the upper and lower papers face each other. The density of the color image was measured using a densitometer Macbeth RD917. <Solvent resistance> Hand cream (product name: ATRIX (manufactured by Kao Corporation)) on the color image area obtained by the evaluation of color density
Was coated thinly and allowed to stand at room temperature for 7 days, and then the density of the printed portion was visually evaluated. <Melting point> Melting point measuring machine YAZAWA TYPE BY-
Using No. 2, the temperature was raised at a rate of about 1 ° C./min while observing under a microscope, and the temperature at which melting began was visually judged. <Infrared absorption spectrum> Measured using IR-810 manufactured by JASCO Corporation.

[0073]

Example 1 Preparation of Top Paper 3-Diethylamino-7-chlorofluorane 2.5 in 100 parts by weight of a 5% aqueous solution of pH 4.0 in which a styrene-maleic anhydride copolymer was dissolved together with a small amount of sodium hydroxide. 80 parts by weight of an oil (trade name: Nisseki Hisol N-296, manufactured by Nippon Petrochemical Co., Ltd.) in which parts by weight were dissolved were emulsified. On the other hand, 10 parts by weight of melamine, 25 parts by weight of a 37% formalin aqueous solution, and 65 parts by weight of water were adjusted to pH with sodium hydroxide.
When the temperature was adjusted to 9.0 and heated to 60 ° C., the mixture became transparent in 15 minutes, and a melamine-formalin precondensate was obtained. This initial condensate was added to the above emulsion, and stirring was continued for 4 hours while maintaining the temperature at 60 ° C., followed by cooling to room temperature. The solid content of the obtained microcapsule dispersion was 45%.

The microcapsule dispersion thus obtained was applied to paper and dried to obtain an upper paper. Preparation of lower paper 360 g of toluene was added as a solvent to 100 g of 2,4-toluene diisocyanate, and 30 g of water was added thereto.
The reaction was performed at 0 ° C. for 7 hours. The precipitated white solid was collected by filtration, washed with hexane, and vacuum dried overnight to obtain 90 g of a white crystalline compound. The melting point and infrared absorption spectrum of this compound were measured. The melting point was 190 ° C. The infrared absorption spectrum was 1590, 1650, 2290c
A characteristic sharp peak was observed around m ^-1 .

Next, 15 g of this compound was taken and pulverized and dispersed together with 45 g of a 2% by weight aqueous solution of polyvinyl alcohol at room temperature for 45 minutes using a paint shaker to obtain a dispersion.
Further, 60 g of calcium carbonate was mixed with 90 g of water, and the mixture was stirred and dispersed with a stirrer to obtain a dispersion. The coating liquid was 40 parts by weight of the above compound dispersion, 125 parts by weight of a calcium carbonate dispersion, and a 10% by weight aqueous solution of polyvinyl alcohol 1
20 parts by weight were obtained by mixing and stirring.

This coating solution was applied on a base paper having a basis weight of 40 g / m ² with a bar coater rod No. 10 to obtain a lower paper. The evaluation result of the coloring density was as good as the optical density of 0.7. The evaluation result of the solvent resistance with the hand cream was good because the printed portion could be read. The results are summarized in Table 1.

[0077]

Example 2 2,4-Toluene diisocyanate 140
g was dissolved in 200 g of toluene, 74 g of aniline was gradually added, and the mixture was reacted at room temperature for 1 hour to precipitate white crystals. The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to give compound 95 as white crystals.
g was obtained. The melting point was 170 ° C. Further, in the infrared absorption spectrum, characteristic sharp peaks were observed around 1600, 1650 and 2290 cm ^-1 .

Next, 15 g of this compound was taken and pulverized and dispersed together with 45 g of a 2% by weight aqueous solution of polyvinyl alcohol at room temperature for 45 minutes using a paint shaker to obtain a dispersion.
Subsequently, a pressure-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that a dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 1. The results are summarized in Table 1.

[0079]

Example 3 2,4-Toluene diisocyanate 100
g and 100 g of pyridine were dissolved in 33 g of toluene and reacted at room temperature for 24 hours. After the generated precipitate was filtered, the precipitate was washed with hexane and dried under vacuum overnight to obtain 40 g of an off-white compound. Melting point was 160 ° C. In the infrared absorption spectrum, characteristic sharp peaks were observed at around 1760 and 2290 cm ^-1 .

Next, 15 g of the compound was taken and pulverized and dispersed together with 45 g of a 2% by weight aqueous solution of polyvinyl alcohol at room temperature for 45 minutes using a paint shaker to obtain a dispersion.
Subsequently, a pressure-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that a dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 1. The results are summarized in Table 1.

[0081]

Example 4 2,4-Toluene diisocyanate 100
g and 27 g of phenol were dissolved in 160 g of toluene, and the temperature was gradually raised from room temperature to 100 ° C., and the mixture was reacted at 100 ° C. for 1 hour. After concentrating the reaction solution, hexane was added, whereby a white precipitate was formed. After the generated precipitate was filtered, the precipitate was washed with hexane and dried in vacuo overnight to give a white compound 77.
g was obtained. The melting point was 70 ° C. In the infrared absorption spectrum, characteristic sharp peaks were observed around 1550, 1700, and 2990 cm ^-1 .

Next, 6 g of this compound was taken, and 2.5% by weight
The mixture was pulverized and dispersed for 45 minutes with a paint shaker together with 24 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. Subsequently, a heat-sensitive recording sheet was prepared and evaluated in the same manner as in Example 1 except that the dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 1. The results are summarized in Table 1.

[0083]

Examples 5 to 7 40 g of 3,3'-diaminodiphenylsulfone was added to a 10% by weight aqueous solution of polyvinyl alcohol 16
0 g, and added to a sand grinder (vessel capacity 40).
0 ml, manufactured by IMEX Co., Ltd.) and pulverized at a rotation speed of 2000 rpm for 3 hours to obtain a dispersion. A pressure-sensitive recording material was prepared in the same manner as in each example, except that the obtained dispersion was added in a proportion of 50 parts by weight to the coating liquid for the lower paper described in Examples 1 to 3 to prepare a lower paper. And evaluated. The results are summarized in Table 1.

[0084]

Examples 8 to 9 70 g of 4,4'-dihydroxydiphenylsulfone as a color developing agent was added to 130 g of a 5.4% by weight aqueous solution of polyvinyl alcohol, and a sand grinder (400 ml vessel volume, manufactured by Imex Co.) was used. For 3 hours to obtain a dispersion. A pressure-sensitive recording material was prepared in the same manner as in each example except that the obtained dispersion was added to the coating solution of the lower paper described in Examples 1 and 5 at a ratio of 25 parts by weight to prepare lower paper. , Was evaluated. The results are summarized in Table 1.

[0085]

Comparative Examples 1 to 3 Except that 4,4 ′, 4 ″ -triisocyanato-2,5-dimethoxytriphenylamine was used in place of the isocyanate compound used in Examples 1, 5, and 8, A pressure-sensitive recording material was prepared and evaluated in the same manner as in each example. The results are summarized in Table 1.

[0086]

Comparative Examples 4 to 5 Pressure-sensitive recording materials were prepared and evaluated in the same manner as in each of the examples except that the isocyanate compound used in the examples 1 and 5 was not used. The results are summarized in Table 1.

[0087]

Comparative Example 6 A pressure-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that activated clay was used as a developer instead of the isocyanate compound used in Example 1. The results are summarized in Table 1.

[0088]

[Table 1]

[0089]

According to the present invention, a color former and a pressure-sensitive recording material of a pressure-sensitive recording material having excellent image storability, black coloring and excellent color sensitivity can be obtained.

[Brief description of the drawings]

FIG. 1 shows an example of an embodiment of a pressure-sensitive recording material using the compound of the present invention.

FIG. 2 shows an example of an embodiment of a pressure-sensitive recording material using the compound of the present invention.

[Explanation of symbols]

 Reference Signs List 1 base material 2 microcapsule-containing pressure-sensitive layer 3 microcapsule 4 base material 5 pressure-sensitive receiving layer 6 base material 7 self-color-forming layer 8 base material 9 microcapsule-containing layer 10 reaction layer 11 base material 12 adhesive layer 13 pressure-sensitive transfer layer 14 plain paper

Claims (9)

[Claims] 1. A pressure-sensitive recording material compound which is an isocyanate adduct having a melting point of 40 ° C. or higher. 2. The compound according to claim 1, wherein the isocyanate adduct is an isocyanate adduct represented by the following formula (I). Embedded image (Here, n represents an integer of 1 to 2. The hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. May have a substituent.) 3. The compound according to claim 1, wherein the isocyanate adduct is an isocyanate adduct represented by the following formula (II). Embedded image (In the formula, m represents an integer of 0 to 5, n represents 1 or 2. Further, the hydrogen atom of the benzene ring is substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent, and X ₁ and X ₂ are each independently —SO ₂ —, —O—,
-(S) _q -,-(CH ₂ ) _q- , -CO-, -CON
_{H -, - CH (C 6} H 5) -, - C (CH 3) 2 - shows the case where either or not present. q is 1 or 2
It is. ) 4. A compound for a pressure-sensitive recording material represented by any of the following formulas (III) to (XII). Embedded image (Here, R ₁ represents the formula (a) or the formula (b). The same applies to the following formulas (IV) to (XII). (Here, n represents an integer of 1 to 2. The hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. May have a substituent.) (In the formula, m represents an integer of 0 to 5, n represents 1 or 2. Further, the hydrogen atom of the benzene ring is substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent, and X ₁ and X ₂ are each independently —SO ₂ —, —O—,
-(S) _q -,-(CH ₂ ) _q- , -CO-, -CON
_{H -, - CH (C 6} H 5) -, - C (CH 3) 2 - shows the case where either or not present. q is 1 or 2
It is. )) Embedded image (R ₂ represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. Further, each residue may have a substituent. The following formulas (VI) and (VII) , (V
Same in III). ) Embedded image Embedded image Embedded image Embedded image (R ₃ represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. Each residue may have a substituent.) (R ₄ represents an aromatic compound residue which may have a substituent, a heterocyclic compound residue which may have a substituent, or an aliphatic compound residue or an inorganic compound residue which may have a substituent. )) (R ₅ and R ₆ each independently represent an aromatic compound, a heterocyclic compound, or an aliphatic compound residue. Each residue may have a substituent. R ₅ and R ₆ are mutually cyclic. A structure may be formed.) 5. The method according to claim 1, wherein R ₁ is the following formula (c) or the following formula (d):
The compound according to claim 4, which is represented by the formula: Embedded image Embedded image 6. A color former containing a colorless or light-colored electron-donating dye precursor and the compound according to claim 1. 7. The color former according to claim 6, comprising an amino compound. 8. The composition according to claim 6, which contains a hydroxyl group-containing compound.
7. The color former according to any one of 7. 9. A pressure-sensitive recording material provided with a color-forming layer containing the color-forming agent according to claim 6 on a support.