JP2701247B2 - Novel N-acyl-arylsulfonic acid amide and heat-sensitive recording sheet using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel N-acyl-arylsulfonic acid amide and a heat-sensitive recording sheet using the compound as a stabilizer.

[0002]

2. Description of the Related Art Generally, a heat-sensitive recording sheet is prepared by grinding and dispersing a colorless or pale-colored basic colorless dye and an organic color developer such as a phenolic substance into fine particles, and then mixing and dispersing them together. A coating solution obtained by adding an agent, a sensitivity improver, a lubricant and other auxiliaries to a support such as paper, synthetic paper, film, plastic, etc. The color recording is obtained by an instantaneous chemical reaction caused by heating such as described above.

[0003] These thermosensitive recording sheets are used for measuring recorders, computer terminal printers, facsimile,
It has been applied to a wide range of fields such as automatic ticket vending machines and bar code labels, but recently, as these recording devices have been diversified and improved in performance, the required quality of thermal recording sheets has become higher. . For example, it is required that a high-density and vivid color image can be obtained even with a small amount of heat energy accompanying the high-speed recording, and on the other hand, light fastness,
There is a demand for a heat-sensitive recording sheet having excellent storability such as weather resistance and oil resistance.

As a conventional example of a heat-sensitive recording sheet, for example, Japanese Patent Publication No. 43-4160 or Japanese Patent Publication No. 45-1403
No. 9 discloses a heat-sensitive recording material. However, such a conventional heat-sensitive recording material has, for example, low thermal responsiveness, and does not provide a sufficient color density during high-speed recording.

As a method for remedying such a defect, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran is used as a leuco dye (JP-A-49-109120). Dibutylamino-
Highly sensitive dyes such as those using 6-methyl-7-anilinofluoran (JP-A-59-190891) have been developed, and as a color developing agent, a substance having a good coloring property, 1,7-
Bis (4-hydroxyphenylthio) -3,5-dioxaheptane (JP-A-59-106456);
By using 5-bis (4-hydroxyphenylthio) -3-oxaheptane (JP-A-59-116262) and 4-hydroxy-4'-isopropoxydiphenylsulfone (JP-B-63-46067). Techniques for increasing the speed and increasing the sensitivity have been disclosed.

[0006]

However, although these heat-sensitive recording sheets have high sensitivity, they generally have a problem in heat resistance such that when stored at a high temperature, the image density is reduced.

Further, since the storage stability of the recorded image is remarkably poor, water or sebum components adhere to the color image, or come into contact with a plasticizer (DOP, DOA, etc.) contained in a wrap film such as a PVC film. As a result, disadvantages such as a remarkable decrease in image density and decoloration still remain.

[0008] It is an object of the present invention to use a novel N-acyl-aryl sulfonic acid amide and to use this compound as a stabilizer to obtain high sensitivity and heat resistance.
An object of the present invention is to provide a heat-sensitive recording sheet having excellent water resistance and oil resistance.

[0009]

SUMMARY OF THE INVENTION A novel N according to the present invention is disclosed.
-Acyl-arylsulfonic acid amide is represented by the following general formula (I).

Embedded image (Wherein, R _1, R ₂ and R ₃ is a hydrogen atom, a C ₁ -C ₄
An alkyl group, a C ₁ -C ₄ alkoxy group, or hydroxy
R ₄ , R ₅ and R ₆ represent a hydrogen atom, C ₁ -C
_{4 represents} an alkyl group or a hydroxy group . Further, R ₁ and R ₂ or R ₄ and R ₅ may be bonded to each other to form an aromatic ring. A represents a C ₁ -C ₂ saturated or unsaturated hydrocarbon chain. Provided that R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are all
Hydrogen atoms.

This compound can be easily prepared by reacting a substituted or unsubstituted aromatic sulfonamide with an arylalkanoyl chloride.

The present invention solves the above-mentioned problems at a glance by including a specific N-acyl-arylsulfonic acid amide represented by the following general formula ( II ) as a stabilizer in a thermosensitive coloring layer. is there.

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are hydrogen
Atom, an alkyl group of C ₁ -C _4, alkoxy of C ₁ -C ₄
It represents a cyano group, a hydroxy group, a cyano group or a nitro group.
R ₁ and R ₂ or R ₄ and R ₅ are bonded to each other to form an aromatic ring.
It may be formed. A is a saturated or unsaturated hydrocarbon of ₁ or more
Indicates a strand. Provided that all of R ₁ , R ₂ and R ₃ are hydrogen
When it is an atom and A is methylene, R ₄ , R ₅ and
And R ₆ are not hydrogen atoms at the same time. Also, R ₁ and
And R ₂ are both hydrogen atoms and R ₃ is a methyl group
When A is methylene, R ₄ and R ₅ are both hydrogen.
The atom R ₆ cannot be a methoxy group or a nitro group.
No. )

In the present invention, N used as a stabilizer
Examples of the acyl-arylsulfonic acid amide include the following, but are not limited thereto.

N- (4-methylphenylacetyl) benzenesulfonamide, N- (4-ethylphenylacetyl) benzenesulfonamide, N- (4-n-propylphenylacetyl) benzenesulfonamide, N- (4
-Iso-propylphenylacetyl) benzenesulfonamide, N- (4-tert-butylphenylacetyl) benzenesulfonamide, N- (4-diphenylacetyl) benzenesulfonamide, N- (4-hydroxyphenylacetyl) benzenesulfonamide , N-
(4-methoxyphenylacetyl) benzenesulfonamide, N- (3-methylphenylacetyl) benzenesulfonamide, N- (3-iso-propylphenylacetyl) benzenesulfonamide, N- (3-methoxyphenylacetyl) benzenesulfone Amide, N- (4
-Methylphenylacetyl) p-toluenesulfonamide, N- (4-ethylphenylacetyl) p-toluenesulfonamide, N- (4-n-propylphenylacetyl) p-toluenesulfonamide, N- (4-iso
-Propylphenylacetyl) p-toluenesulfonamide, N- (4-tert-butylphenylacetyl)
p-toluenesulfonamide, N- (4-diphenylacetyl) p-toluenesulfonamide, N- (4-hydroxyphenylacetyl) p-toluenesulfonamide, N- (3-methylphenylacetyl) p-toluenesulfonamide, N- (3-ethylphenylacetyl)
p-toluenesulfonamide, N- (3-n-propylphenylacetyl) p-toluenesulfonamide, N-
(3-iso-propylphenylacetyl) p-toluenesulfonamide, N- (3-tert-butylphenylacetyl) p-toluenesulfonamide, N- (3-
Diphenylacetyl) p-toluenesulfonamide, N
-(3-hydroxyphenylacetyl) p-toluenesulfonamide, N- (3-phenylpropionyl) p-
Toluenesulfonamide, N-[(3-methylphenylpropionyl)] p-toluenesulfonamide, N-
(3-ethylphenylpropionyl)) p-toluenesulfonamide, N- [3- (4-hydroxyphenylpropionyl)] p-toluenesulfonamide, N- [3
-(3-hydroxyphenylpropionyl)] p-toluenesulfonamide, N- [3- (4-methoxyphenylpropionyl)] p-toluenesulfonamide, N-
[3- (3-methoxyphenylpropionyl)] p-toluenesulfonamide, N- [3- (4-ethoxyphenylpropionyl)] p-toluenesulfonamide, N
-[3- (3-ethoxyphenylpropionyl)] p-
Toluenesulfonamide, N-cinnamoyl-p-toluenesulfonamide, N- (3-phenylpropionyl) benzenesulfonamide, N- [3- (4-methylphenylpropionyl)] benzenesulfonamide, N
-[3- (3-hydroxyphenylpropionyl)] benzenesulfonamide, N- [3- (4-hydroxyphenylpropionyl)] benzenesulfonamide, N-
[3- (3-methoxyphenylpropionyl)] benzenesulfonamide, N- [3- (4-methoxyphenylpropionyl)] benzenesulfonamide, N- [3-
(3-ethoxyphenylpropionyl)] benzenesulfonamide, N- [3- (4-ethoxyphenylpropionyl)] benzenesulfonamide, N-cinnamoyl-benzenesulfonamide, N-phenylacetyl-p
-Methoxybenzenesulfonamide, N- (4-methylphenylacetyl) p-methoxybenzenesulfonamide, N- (4-hydroxyphenylacetyl) p-ethoxybenzenesulfonamide, N- (4-methoxyphenylacetyl) p-iso -Propoxybenzenesulfonamide, N- (3-methylphenylacetyl) p-methoxybenzenesulfonamide, N- (3-hydroxyphenylacetyl) p-methoxybenzenesulfonamide, N- (3-methoxyphenylacetyl) p-methoxy Benzenesulfonamide, N-phenylacetyl-naphthalenesulfonamide, N- (3-phenylpropionyl) naphthalenesulfonamide, N- [3- (4-methylphenylpropionyl)] naphthalenesulfonamide, N- [3- ( - methyl phenylpropionyl)
Naphthalenesulfonamide, N- [3- (4-hydroxyphenylpropionyl)] naphthalenesulfonamide, N- [3- (4-methoxyphenylpropionyl)] naphthalenesulfonamide, N- [3- (3-ethoxyphenylpropionyl) Naphthalenesulfonamide, N-cinnamoyl-naphthalenesulfonamide,
N- phenylacetylide Le - 4-hydroxy-benzenesulfonamide, N- (4-methylphenyl acetyl) -4-
Hydroxybenzenesulfonamide, N- (3- methylphenyl acetyl) -4- hydroxy-benzenesulfonamide, N- phenylpropionyl - 4-hydroxy-benzenesulfonamide, N- [3- (4-hydroxy -
3,5-di-tert-butylphenyl) propioni
] -4- hydroxy-benzenesulfonamide, N- sheet <br/>N'namoi Le - such as 4-hydroxy-benzenesulfonic amides.

The above-mentioned N-acyl-aryl sulfonic acid amides can be used alone or in combination of two or more as required.

In the present invention, bisphenol A, 4-hydroxybenzoic acid ester, 4-hydroxyphthalic acid diester, phthalic acid monoester, bis- (hydroxyphenyl) sulfide, 4-
Hydroxyphenylarylsulfones, 4-hydroxyphenylarylsulfonates, 1,3-di [2-
(Hydroxyphenyl) -2-propyl] -benzenes, 4-hydroxybenzoyloxybenzoic acid esters, and bisphenolsulfones. Specific examples of these are shown below.

Bisphenol A 4,4'-isopropylidene diphenol (also called bisphenol A) 4,4'-cyclohexylidene diphenol p, p '-(1-methyl-normalhexylidene) diphenol 1,7 -Di (4-hydroxyphenylthio) -3,5-
Dioxaheptane

4-Hydroxybenzoic acid esters Benzyl 4-hydroxybenzoate Ethyl 4-hydroxybenzoate Propyl 4-hydroxybenzoate Isopropyl 4-hydroxybenzoate Butyl 4-hydroxybenzoate Isobutyl 4-hydroxybenzoate 4-Hydroxybenzoate Methyl benzyl

4-Hydroxyphthalic acid diesters Dimethyl 4-hydroxyphthalate Diisopropyl 4-hydroxyphthalate Dibenzyl 4-hydroxyphthalate Dihexyl 4-hydroxyphthalate

Monoesters of phthalic acid Monobenzyl phthalate Monocyclohexyl phthalate Monophenyl phthalate Monomethyl phenyl phthalate Monoethyl phenyl phthalate Monopropyl benzyl phthalate Monohalogen benzyl phthalate Monoethoxy phthalate Benzyl ester

Bis- (hydroxyphenyl) sulfide
S bis - (4-hydroxy -3-tert-butyl-6
Methylphenyl) sulfide bis- (4-hydroxy-2,5-dimethylphenyl)
Sulfide bis- (4-hydroxy-2-methyl-5-ethylphenyl) sulfide bis- (4-hydroxy-2-methyl-5-isopropylphenyl) sulfide bis- (4-hydroxy-2,3-dimethylphenyl)
Sulfide bis- (4-hydroxy-2,5-dimethylphenyl)
Sulfide bis- (4-hydroxy-2,5-diisopropylphenyl) sulfide bis- (4-hydroxy-2,3,6-trimethylphenyl) sulfide bis- (2,4,5-trihydroxyphenyl) sulfide bis- ( 4-hydroxy-2-cyclohexyl-5-methylphenyl) sulfide bis- (2,3,4-trihydroxyphenyl) sulfide bis- (4,5-dihydroxy-2-tert-butylphenyl) sulfide bis- (4- Hydroxy-2,5-diphenylphenyl) sulfide bis- (4-hydroxy-2-tert-octyl-5)
-Methylphenyl) sulfide

[0021] 4-hydroxyphenylaryl sulfone
S 4-hydroxy-4'-isopropoxydiphenylsulfone 4-hydroxy-4'-propoxy diphenyl sulfone 4-hydroxy-4'-n-butyl sulfone 4-hydroxy-4'-n-propoxy diphenyl sulfone

[0022] 4-hydroxyphenylarylsulfona
Over preparative such 4-hydroxyphenyl benzenesulfonate 4-hydroxyphenyl -p- tolyl sulfonate 4-hydroxyphenyl-methylene sulfonate 4-hydroxyphenyl -p- chlorobenzene sulfonate 4-hydroxyphenyl -p-tert-butyl-benzenesulfonyl Nato 4-hydroxyphenyl-p-isopropoxybenzenesulfonate 4-hydroxyphenyl-1'-naphthalenesulfonate 4-hydroxyphenyl-2'-naphthalenesulfonate

1,3-di [2- (hydroxyphenyl)
-2-propyl] benzenes 1,3-di [2- (4-hydroxyphenyl) -2-propyl] benzene 1,3-di [2- (4-hydroxy-3-alkylphenyl) -2-propyl] benzene Benzene 1,3-di [2- (2,4-dihydroxyphenyl)-
2-propyl] benzene 1,3-di [2- (2-hydroxy-5-methylphenyl) -2-propyl] benzene

Resorcinols 1,3-dihydroxy-6 (α, α-dimethylbenzyl) -benzene

[0025] 4-hydroxybenzoyloxybenzoic acid
Ester benzyl 4-hydroxybenzoyloxybenzoate methyl 4-hydroxybenzoyloxybenzoate ethyl 4-hydroxybenzoyloxybenzoate propyl 4-hydroxybenzoyloxybenzoate butyl 4-hydroxybenzoyloxybenzoate isopropyl 4-hydroxybenzoyloxybenzoate 4 Tert-butyl 4-hydroxybenzoyloxybenzoate hexyl 4-hydroxybenzoyloxybenzoate octyl 4-hydroxybenzoyloxybenzoate nonyl 4-hydroxybenzoyloxybenzoate cyclohexyl 4-hydroxybenzoyloxybenzoate 4-hydroxybenzoyloxybenzoate β- Phenethyl 4-hydroxybenzoyloxybenzoate phenyl 4-hydroxybenzoyloxybenzoate α- naphthyl 4-hydroxy-benzoyloxy benzoate β- naphthyl 4-hydroxy-benzoyloxy benzoate sec- butyl

Bisphenolsulfones (I) bis- (3-1-butyl-4-hydroxy-6-methylphenyl) sulfone bis- (3-ethyl-4-hydroxyphenyl) sulfone bis- (3-propyl-4-) (Hydroxyphenyl) sulfone bis- (3-methyl-4-hydroxyphenyl) sulfone bis- (2-isopropyl-4-hydroxyphenyl)
Sulfone bis- (2-ethyl-4-hydroxyphenyl) sulfone bis- (3-chloro-4-hydroxyphenyl) sulfone bis (2,3-dimethyl-4-hydroxyphenyl) sulfone bis (2,5-dimethyl-4) -Hydroxyphenyl) sulfone bis- (3-methoxy-4-hydroxyphenyl) sulfone 4-hydroxyphenyl-2'-ethyl-4'-hydroxyphenylsulfone 4-hydroxyphenyl-2'-isopropyl-4'-
Hydroxyphenylsulfone 4-hydroxyphenyl-3'-isopropyl-4'-
Hydroxyphenylsulfone 4-hydroxyphenyl-3'-secbutyl-4'-
Hydroxyphenylsulfone 3-chloro-4-hydroxyphenyl-3'-isopropyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-aminophenyl -4'-hydroxyphenylsulfone 2-hydroxy-5-t-isopropylphenyl-4 '
-Hydroxyphenylsulfone 2-hydroxy-5-t-octylphenyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-3'-chloro-4'-hydroxyphenylsulfone 2-hydroxy-5-t -Butylphenyl-3'-methyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-3'-isopropyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-3 '-Chloro-4'-hydroxyphenylsulfone2-hydroxy-5-tert-butylphenyl-3'-methyl-4'-hydroxyphenylsulfone2-hydroxy-5-tert-butylphenyl-3'-isopropyl-4'- Hydroxyphenyl sulfone 2-hydroxy-5-t-butyl Eniru 2'-methyl-4'-hydroxyphenyl sulfone

Bisphenolsulfonic acid (II) 4,4'-sulfonyldiphenol 2,4'-sulfonyldiphenol 3,3'-dichloro-4,4'-sulfonyldiphenol 3,3'-dibromo-4,4 '-Sulfonyldiphenol 3,3', 5,5'-tetrabromo-4,4'-sulfonyldiphenol 3,3'-diamino-4,4'-sulfonyldiphenol

Other p-tert-butylphenol 2,4-dihydroxybenzophenone novolak type phenol resin 4-hydroxyacetophenone p-phenylphenol benzyl-4-hydroxyphenylacetate p-benzylphenol

The basic colorless dye used in the present invention is not particularly limited, but is preferably a triphenylmethane type, a fluoran type, a fluorene type, a divinyl type or the like, and specific examples thereof are shown below.

Triphenylmethane leuco dye 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide [also known as crystal violet lactone]

Fluoran leuco dye (I) 3-Diethylamino-6-methyl-7-anilinofluoran 3- (N-ethyl-p-toluidino) -6-methyl-
7-anilinofluoran 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluoran 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluoran 3 -Pyrrolidino-6-methyl-7-anilinofluoran 3-piperidino-6-methyl-7-anilinofluoran 3- (N-cyclohexyl-N-methylamino) -6
Methyl-7-anilinofluoran 3-diethylamino-7- (m-trifluoromethylanilino) fluoran 3-Nn-dibutylamino-6-methyl-7-anilinofluoran 3-Nn-dibutyl Amino-7- (o-chloroanilino) fluoran 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluoran 3-dibutylamino-6-methyl-7- (o, p -Dimethylanilino) fluoran 3- (N-methyl-N-propylamino) -6-methyl-7-anilinofluoran 3-diethylamino-6-chloro-7-anilinofluoran 3-dibutylamino-7- (O-chloroanilino) fluoran 3-diethylamino-7- (o-chloroanilino) fluoran 3-diethylamino-6-methyl-c Lorfluoran 3-diethylamino-6-methyl-fluoran 3-cyclohexylamino-6-chlorofluoran 3-diethylamino-benzo [a] -fluoran 3-n-dipentylamino-6-methyl-7-anilinofluoran 2- ( 4-oxo-hexyl) -3-dimethylamino-
6-methyl-7-anilinofluoran 2- (4-oxo-hexyl) -3-diethylamino-
6-methyl-7-anilinofluoran 2- (4-oxo-hexyl) -3-dipropylamino-6-methyl-7-anilinofluoran

Fluorene leuco dye 3,6,6'-tris (dimethylamino) spiro [fluorene-9,3'-phthalide] 3,6,6'-tris (diethylamino) spiro [fluorene-9,3'- Phthalide]

Fluoran leuco dye (II) 2-methyl-6-p- (p-dimethylaminophenyl)
Aminoanilinofluorane 2-methoxy-6-p- (p-dimethylaminophenyl) aminoanilinofluoran 2-chloro-3-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran 2 -Chloro-6-p- (p-dimethylaminophenyl)
Aminoanilinofluoran 2-nitro-6-p- (p-diethylaminophenyl)
Aminoanilinofluoran 2-amino-6-p- (p-diethylaminophenyl)
Aminoanilinofluoran 2-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluoran 2-phenyl-6-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran 2- Benzyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran 2-hydroxy-6-p- (p-phenylaminophenyl) aminoanilinofluoran 3-methyl-6-p- (p-dimethyl Aminophenyl)
Aminoanilinofluorane 3-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluoran 3-diethylamino-6-p- (p-dibutylaminophenyl) aminoanilinofluoran

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

Other 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2,
2-dinitrileethane 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2-
β-naphthoylethane 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2,
2-Diacetylethane bis- [2,2,2 ', 2'-tetrakis- (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester

These dyes can be used alone or in combination of two or more.

Further, as sensitizers, fatty acid amides such as stearic acid amide and palmitic acid amide, ethylene bisamide, montan wax, polyethylene wax, dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate , P-benzylbiphenyl, phenyl α-naphthyl carbonate, 1,4-diethoxynaphthalene, 1-hydroxy-
2-naphthoic acid phenyl ester, 1,2-di- (3-
Methylphenoxy) ethane, di (p-methylbenzyl) oxalate, β-benzyloxynaphthalene, 4-biphenyl p-tolyl ether, O-xylerin-bis- (phenyl ether), 4- (m-methylphenoxymethyl) biphenyl Etc. can also be added.

As the binder used in the present invention, completely saponified polyvinyl alcohol having a degree of polymerization of 200 to 1900, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol Alcohol, other modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, styrene-maleic anhydride copolymer, styrene-butadiene copolymer and ethyl cellulose, cellulose derivatives such as acetyl cellulose, polyvinyl chloride, polyvinyl acetate,
Examples thereof include polyacrylamide, polyacrylate, polyvinyl butyral polystyrene, and copolymers thereof, polyamide resin, silicone resin, petroleum resin, terpene resin, ketone resin, and cumarone resin. These macromolecules are water, alcohol, ketone,
In addition to dissolving in solvents such as esters and hydrocarbons,
It is used in a state of being emulsified or dispersed in a paste form in water or another medium, and may be used in combination depending on required quality.

In the present invention, a known stabilizer metal salt of p-nitrobenzoic acid (Ca, Zn) or metal salt of monobenzyl phthalate (Ca, Zn) is used as long as the effects of the present invention are not impaired. It is also possible to add.

The filler used in the present invention includes silica,
Examples include inorganic or organic fillers such as calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, tanks, titanium oxide, and aluminum hydroxide.

In addition, a releasing agent such as a fatty acid metal salt, a lubricant such as a wax, a benzophenone-based or triazole-based ultraviolet absorber, a water-proofing agent such as glyoxal, a dispersant, and an antifoaming agent. Can be.

The amounts of the stabilizer and the basic colorless dye used in the present invention and the types and amounts of other various components are determined according to the required performance and recording suitability, and are not particularly limited. 1 to 8 parts of an organic color developer, 0.25 to 2.5 parts of a stabilizer, and 1 to 20 parts of a filler are used for 1 part of a neutral colorless dye, and a binder is 10 to 25% of the total solid content.
Is appropriate.

The desired heat-sensitive recording sheet can be obtained by applying the coating solution having the above composition to any support such as paper, synthetic paper, plastic film, and non-woven fabric.

Further, an overcoat layer of a polymer substance containing a filler can be provided on the thermosensitive coloring layer for the purpose of enhancing the storage stability.

An undercoat layer containing an organic filler or an inorganic filler can be provided below the thermosensitive coloring layer for the purpose of enhancing the storage stability and sensitivity.

The above-mentioned organic developer, basic colorless dye, and optionally added materials are finely divided by a pulverizer such as a ball mill, an attritor, a sand grinder or an appropriate emulsifying apparatus until the particle diameter becomes several microns or less. And a binder and various kinds of additive materials are added according to the purpose to obtain a coating liquid.

[0047]

The reason why the effects of the present invention can be obtained when a specific stabilizer is used in the present invention is considered as follows.

First, what is excellent in dynamic coloring ability is
This is because the melt dissolution / diffusion rate and saturation solubility of the color developer and the dye with respect to the stabilizer of the present invention are high, and a recorded image can be instantaneously formed by instantaneous contact of a high-heat thermal head.

The reason why the recorded image has extremely high stability in terms of heat resistance, water resistance and oil resistance is explained as follows. Generally, thermosensitive recording paper uses a basic colorless dye as an electron donor,
Organic acidic substances such as phenol compounds, aromatic carboxylic acids, and organic sulfonic acids are configured as electron acceptors.
The heat-melting reaction between these basic colorless dyes and the developer is an acid-base reaction based on donation and acceptance of electrons, whereby a metastable "charge transfer complex" is formed and a colored image is obtained. . At this time, by adding a specific N-acyl-aryl sulfonic acid amide to the system, the recorded image is stabilized by the reaction with the leuco dye and the organic developer during the heat melting reaction, so that the recorded image becomes water-soluble. It is considered that the stability of the color image is maintained even when exposed to environmental conditions affected by oil, heat and long term.

[0050]

The present invention will be described below with reference to examples.
In addition, in description, a part shows a weight part.

(Synthesis Example 1) N- (4-methylphenylacetyl) benzenesulfone
Synthesis of amide 17.1 g of benzenesulfonamide and 50 g of toluene were placed in a 200 ml reaction flask equipped with a thermometer, a dropping funnel, a stirrer, and a condenser connected to a hydrogen chloride gas absorber.
And heat it. When the solvent started to reflux, 16.9 g of p-methylphenylacetyl chloride was added from the dropping funnel in one hour. The reaction was continued at this temperature for 6 hours.
Hydrogen chloride gas generated during the reaction was treated by an absorber. After completion of the reaction, water was added, and the contents were washed with water at 60 ° C. until the contents became neutral. After cooling the toluene layer to reflux, white crystals are precipitated by cooling. The precipitated crystals were collected by filtration and dried to obtain 29.1 g of white crystals having a melting point of 103.5 ° C.

(Synthesis Example 2) N- (3-methylphenylacetyl) p-toluenesul
Synthesis of honamide The reaction flask used in Synthesis Example 1 was charged with 17.1 g of p-toluenesulfonamide and 50 g of toluene and heated. In the same manner as in Synthesis Example 1, 16.9 g of m-methylphenylacetyl chloride was reacted and treated. Melting point 12
6 ° C. white crystals were obtained.

Synthesis Example 3 N- (3-phenylpropionyl) benzenesulfone
Synthesis of amide 15.7 g of benzenesulfonamide and 3-phenylpropionyl chloride 16.
By reacting 9 g, white crystals having a melting point of 113 ° C. were obtained.

Synthesis Example 4 N- (3-phenylpropionyl) p-toluenesulfo
17.1 g of p-toluenesulfonamide and 3-phenylpropionyl chloride 1 were prepared in the same manner as in Synthesis Example 1.
6.9 g were reacted to obtain white crystals having a melting point of 113 ° C.

(Synthesis Example 5) Synthesis of N-cinnamoyl-p-toluenesulfonamide In the same manner as in Synthesis Example 1, 17.1 g of p-toluenesulfonamide and 16.8 g of cinnamoyl chloride were reacted to give a slightly yellow crystal. I got Furthermore, white crystals having a melting point of 140 ° C. were obtained by recrystallization with a mixed solvent of toluene and ethanol.

(Synthesis Example 6) Synthesis of N-cinnamoyl-benzenesulfonamide By the same operation as in Synthesis Example 1, 15.7 g of benzenesulfonamide and 16.8 g of cinnamoyl chloride were reacted to obtain pale yellow crystals. Further, white crystals having a melting point of 150 ° C. were obtained by recrystallization with a mixed solvent of toluene and ethanol.

(Synthesis Example 7) N-phenylacetyl-p-methoxybenzenesulfone
Synthesis of amide 18.7 g of p-methoxybenzenesulfonamide and phenylacetyl chloride 1 were prepared in the same manner as in Synthesis Example 1.
By reacting 5.5 g, white crystals having a melting point of 147 ° C. were obtained.

(Synthesis Example 8) N-phenylacetyl-2-naphthalenesulfonamide
According to the same operation as in Synthesis Example 1, 20.7 g of 2-naphthalenesulfonamide and 15.5 g of phenylacetyl chloride were obtained.
Was reacted to obtain white crystals having a melting point of 143 ° C.

Hereinafter, an example of producing a heat-sensitive recording sheet using the N-acyl-arylsulfonic acid amide of the present invention will be described.

Example 1 (Test Nos. 1 to 8) Solution A (Developer dispersion) Developer (see Table 1) 6.0 parts 10% aqueous solution of polyvinyl alcohol 18.8 parts Water 11.2 Part B liquid (dye dispersion liquid) 3- (N-ethyl-N-isoamylamino) -6-methyl-2.0 parts 7-anilinofluoran 10% aqueous polyvinyl alcohol solution 4.6 parts water 2.6 parts C Liquid (Stabilizer dispersion liquid) N-acyl-arylsulfonic acid amide (see Table 1) 4.0 parts 10% aqueous polyvinyl alcohol solution 5.0 parts Water 3.0 parts Average of each liquid of the above composition with a sand grinder Milled to a particle size of 1 micron. Subsequently, the dispersion liquid was mixed at the following ratio to obtain a coating liquid. Liquid A 36.0 parts Liquid B 9.2 parts Liquid C 12.0 parts Kaolin clay (50% dispersion) 12.0 parts Each of the above coating liquids is applied to one surface of a 50 g / m ² base paper 6.0.
g / m ² and dried, and this sheet was treated with a super calender so that the smoothness became 500 to 600 seconds to prepare a heat-sensitive recording sheet.

Example 2 (Test Nos. 12 to 19) Liquid A (Developer dispersion) Developer (see Table 2) 6.0 parts 10% aqueous solution of polyvinyl alcohol 18.8 parts Water 11.2 Part B liquid (dye dispersion liquid) 3- (N-ethyl-N-isoamylamino) -6-methyl-2.0 parts 7-anilinofluoran 10% aqueous polyvinyl alcohol solution 4.6 parts water 2.6 parts C Liquid (Stabilizer dispersion liquid) N-acyl-arylsulfonic acid amide (see Table 2) 4.0 parts 10% aqueous polyvinyl alcohol solution 5.0 parts Water 3.0 parts Average of each liquid of the above composition with a sand grinder Milled to a particle size of 1 micron. Subsequently, the dispersion liquid was mixed at the following ratio to obtain a coating liquid. Liquid A 36.0 parts Liquid B 9.2 parts Liquid C 12.0 parts Kaolin clay (50% dispersion) 12.0 parts Each of the above coating liquids is applied to one surface of a 50 g / m ² base paper 6.0.
g / m ² and dried, and this sheet was treated with a super calender so that the smoothness became 500 to 600 seconds to prepare a heat-sensitive recording sheet.

[Comparative Example 1 (Test Nos. 9 to 11)] Liquid D (Developer dispersion) Developer (see Table 1) 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts Water 11.2 Part B (Dye dispersion) 3- (N-ethyl-N-isoamylamino) -6-methyl-2.0 parts 7-anilinofluoran 10% aqueous polyvinyl alcohol solution 4.6 parts Water 2.6 parts Each liquid of the composition was ground by a sand grinder to an average particle size of 1 micron. Next, a dispersion was mixed at the following ratio to form a coating liquid, and a heat-sensitive recording sheet was prepared in the same manner as in Example 1. Liquid D 36.0 parts Liquid B 9.2 parts Kaolin clay (50% dispersion) 12.0 parts

[Comparative Example 2 (Test Nos. 20 to 22)] Solution E (Developer dispersion) Developer (see Table 2) 5.0 parts 10% aqueous solution of polyvinyl alcohol 18.8 parts Water 11.2 Part B (Dye dispersion) 3- (N-ethyl-N-isoamylamino) -6-methyl-2.0 parts 7-anilinofluoran 10% aqueous polyvinyl alcohol solution 4.6 parts Water 2.6 parts Each liquid of the composition was ground by a sand grinder to an average particle size of 1 micron. Next, a dispersion was mixed at the following ratio to form a coating liquid, and a heat-sensitive recording sheet was prepared in the same manner as in Example 1. E liquid 36.0 parts B liquid 9.2 parts Kaolin clay (50% dispersion) 12.0 parts

Tables 3 and 4 show the results of quality performance tests performed on the heat-sensitive recording sheets obtained in the above Examples and Comparative Examples.

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[Table 1]

[Table 2]

[Table 3]

[Table 4]

Note (1) Dynamic color density; manufactured by Tokyo Shibaura Electric Co., Ltd.
Using thermal facsimile KB-4800, applied voltage 1
The image density recorded at 8.03 V and a pulse width of 3.2 ms was measured with a Macbeth densitometer (RD-914, using an amber filter; the same applies hereinafter).

Note (2) Heat resistance: The thermal paper sample dynamically recorded by the method of Note (1) was subjected to drying at 60 ° C. and dry conditions for 24 hours.
After leaving for a while, the recorded part was measured with a Macbeth densitometer. The residual rate is calculated from the following equation.

(Equation 1)

Note (3) Water resistance: A thermal paper sample dynamically recorded by the method of Note (1) was immersed in cold water at 20 ° C. for 24 hours, dried, and the recorded portion was measured with a Macbeth densitometer. The residual rate is calculated from the following equation.

(Equation 2)

Note (4) Oil resistance; salad oil was dropped on a thermal paper sample dynamically recorded by the method of Note (1), wiped off with a filter paper which rolled 10 seconds later, left at room temperature for 1 hour, and then image density Is measured with a Macbeth densitometer. The residual rate is calculated from the following equation.

(Equation 3)

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【The invention's effect】

(1) Because of its excellent thermal response, a clear high-density image can be obtained even at high speed and high density recording. (High sensitivity) (2) Printed part (colored part) hardly loses color even when it comes into contact with plasticizer, salad oil, vinegar, etc. (Oil resistance) (3) Printed part even when it comes in contact with water Hardly loses color. (Water resistance) (4) The image is stable even under high temperature conditions. (Heat-resistant)

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Ryuzo Mizukami 955 Komatsuri, Yoshitomi-cho, Chikugami-gun, Fukuoka Yoshitomi Pharmaceutical Co., Ltd. Chemicals Research Laboratory (56) References Synth. Commun. (1988), Vol. 18, No. 1, P. 29-35 Tetrahedron Lett. (1986), Vol. 27, No. 2, P. 131-134 Fiziol. Akt, Veshche estva (1976), Vol. 8, p. 86−88

Claims (2)

(57) [Claims] 1. A novel N-type compound represented by the following general formula (I)
Acyl-aryl sulfonamides. Embedded image (Wherein, R _1, R ₂ and R ₃ is a hydrogen atom, a C ₁ -C ₄
An alkyl group, a C ₁ -C ₄ alkoxy group, or hydroxy
R ₄ , R ₅ and R ₆ represent a hydrogen atom, C ₁ -C
_{4 represents} an alkyl group or a hydroxy group . Further, R ₁ and R ₂ or R ₄ and R ₅ may be bonded to each other to form an aromatic ring. A represents a C ₁ -C ₂ saturated or unsaturated hydrocarbon chain. Provided that R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are all
Hydrogen atoms. To 2. A on a support, following a colorless or pale basic colorless dye and an organic developer in the heat-sensitive recording sheet provided with a coloring layer containing as a main component, a heat-sensitive coloring layer stabilizers A heat-sensitive recording sheet comprising at least one N-acyl-arylsulfonic acid amide represented by the general formula (II) . Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are hydrogen
Atom, an alkyl group of C ₁ -C _4, alkoxy of C ₁ -C ₄
It represents a cyano group, a hydroxy group, a cyano group or a nitro group.
R ₁ and R ₂ or R ₄ and R ₅ are bonded to each other to form an aromatic ring.
It may be formed. A is a saturated or unsaturated hydrocarbon of ₁ or more
Indicates a strand. Provided that all of R ₁ , R ₂ and R ₃ are hydrogen
When it is an atom and A is methylene, R ₄ , R ₅ and
And R ₆ are not hydrogen atoms at the same time. Also, R ₁ and
And R ₂ are both hydrogen atoms and R ₃ is a methyl group
When A is methylene, R ₄ and R ₅ are both hydrogen.
The atom R ₆ cannot be a methoxy group or a nitro group.
No. )