JPH05116461A - Thermal recording body - Google Patents

Abstract

PURPOSE:To obtain a thermal recording body forming a color developing image with excellent oil resistance and plasticizer resistance by using N-arylsulfonyl (thio) urea with a specified chem. structure as a color developer and furthermore using in parallel an aziridine compd. or an epoxy compd. with a specified org. compd. which is a curing agent for an epoxy resin. CONSTITUTION:A dye precursor, a color developer, an epoxy compd. or an aziridine compd. and an org. compd. having a primary amino group, a secondary amino group, a carboxyl group or a CO-O-CO structure are incorporated in a heat-sensitive color developing layer of a heat-sensitive recording body. In addition, the above described color developer contains N-arylsulfonyl (thio) urea of formula (wherein X is O or S and R1 is a group selected from arom. groups, lower alkyl groups and benzene ring groups and R2 and R3 are each a group selected from alkyl groups, arom. groups with no substituted group and arom. groups substituted with at least one group selected from alkyl groups etc.,).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosensitive recording medium which is free from image loss and has excellent storage stability of recording. More specifically, the present invention is excellent in oil resistance and plasticizer resistance, and therefore has a high chance of coming into contact with oil and plasticizer, and therefore cash dispenser paper, ticket, commuter pass,
The present invention relates to a recording body suitable for a label such as a POS label, a card such as a prepaid card, a pass ticket, a facsimile paper for a long-term storage, a word processor paper, a CRT image printer paper, and the like.

[0002]

2. Description of the Related Art A heat-sensitive recording material utilizing a heat-coloring reaction between a colorless or light-colored leuco dye and a phenol or an organic acid is disclosed in JP-B-43-4160 and JP-B-45-140.
No. 39, Japanese Examined Patent Publication No. 48-27736, etc., and is widely put into practical use. In recent years, such a thermosensitive recording medium has a merit that a color image is formed by simply heating it, a recording apparatus can be made relatively compact, maintenance is easy, and noise is not generated. Widely used as various information recording materials such as facsimiles, computer output machines, labels, automatic ticket vending machines, CD / ATM, order output machines for family restaurants, data output machines for scientific research equipment, printers, etc. ..

With the expansion of the application range of such a thermal recording material, the thermal recording material may come into contact with a cosmetic cream or oil or a polymer sheet containing a plasticizer, or may be subjected to severe conditions such as high temperature and high humidity. Opportunities to get down are increasing. For example, a conventionally used developer, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), benzyl p-hydroxybenzoate (JP-A-52-140483) or the like was used. For thermal recording media,
When a colored image is placed under high temperature and high humidity, the color density of the image portion is lowered, and when it comes into contact with a plasticizer, oil, etc., the image is erased to an unreadable level.

A large number of techniques have been disclosed for suppressing this decoloring phenomenon while using a coloring system which usually uses a dye mainly composed of a colorless or light-colored lactone ring compound. They are disclosed, for example, in JP-A-60-78782 and JP-A-59.
No. 167,292, JP-A-59-114096, and JP-A-59-93387, a compound containing a phenolic antioxidant in a thermosensitive color-developing layer, as disclosed in JP-A-56-146796. As shown in JP-A-58-199189, a water-soluble polymer compound or a hydrophobic polymer compound emulsion is used on the heat-sensitive color developing layer. As an intermediate layer on which a surface layer of an oil-based paint containing a hydrophobic polymer compound as a resin component is provided, and as seen in JP-A-62-164579 and Japanese Patent Application No. 2-233149. In addition, an epoxy compound or an aziridine compound is contained in the thermosensitive coloring layer.

The color-developed image in the case where the above-mentioned phenolic antioxidant is blended has a slightly improved environmental resistance such as heat resistance and humidity resistance as compared with the image in the case where it is not present, but the oil-resistant (for example, Preservation rate of image density after a certain time when salad oil was brought into contact with the color surface), plasticizer resistance (for example, preservation rate of image density after a certain time when dioctyl phthalate was brought into contact with the color surface) Hardly improved. On the other hand, the color-developed image of the thermosensitive recording medium provided with the protective layer and the surface layer is
It has excellent oil resistance and plasticizer resistance, and the image storability is greatly improved when salad oil or dioctyl phthalate is contacted from the surface. However, when these are contacted from the back surface or end surface of the thermal recording medium, the salad oil and dioctyl phthalate penetrate into the recording medium and the image disappears almost completely, so an essential solution to the above problems. Not really. Further, in the case of containing an epoxy compound or an aziridine compound, a relatively long time is required from the heating color development operation to the stabilization of the color image. For example, if salad oil or dioctyl phthalate is brought into contact with the color image immediately after formation of the color image, a considerable part of the color image is erased.

[0006]

The present invention solves the above-mentioned problems of the prior art, and immediately after the formation of a color image, the color image has high oil resistance and plasticizer resistance, and therefore has excellent storage stability for a long period of time. It is intended to provide a thermosensitive recording medium.

[0007]

Means for Solving the Problems The present inventors have investigated a thermosensitive color developing layer having high oil resistance, plasticizer resistance and high whiteness immediately after forming a color image, and as a result,
N-arylsulfonyl (thio) having a specific chemical structure
It was discovered that a desired thermosensitive coloring layer can be obtained by using a urea derivative as a color developing agent, and further by using in combination with an aziridine compound or an epoxy compound and a specific organic compound known as a curing agent for an epoxy resin, the present invention It came to completion.

The heat-sensitive recording material of the present invention comprises a sheet-shaped substrate,
A substantially colorless dye precursor formed on at least one surface of the sheet-like substrate, a developer that reacts with the dye precursor under heating to develop a color, and at least one aziridinyl group, or A thermosensitive coloring layer containing an organic compound having an epoxy group, wherein the color developer has the general formula (I):

[Chemical 2](However, X represents an oxygen atom or a sulfur atom, and R₁
Is an aromatic group having no substituent, and a lower alkyl group.
Group and at least one member selected from halogen atoms
Represents a member selected from benzene ring groups substituted by
And R₂And R ₃Are each independently a hydrogen atom,
Substituted with an alkyl group, aralkyl group, or aryloxy group
Alkyl group, aromatic group having no substituent, and
Alkyl group, aryl group, aralkyl group, alkyloxy
Group, alkyloxycarbonyl group, aryloxycal
Bonyl group, aralkyloxycarbonyl group, aryls
At least one selected from a sulfonyl group and a halogen atom.
Also represents a member selected from aromatic groups substituted by one member.
Forget ) Is at least one compound represented by
Further, in the thermosensitive coloring layer, at least one
Organic compounds having primary or secondary amino groups, and small
At least one carboxyl group or -CO-O-CO
-At least one selected from organic compounds having a structure
Is contained.

[0009]

The N-of the general formula (I) used in the present invention
Examples of arylsulfonyl (thio) ureas include N-
(P-Toluenesulfonyl) -N′-phenylurea (melting point 165 ° C.), N- (p-toluenesulfonyl) -N ′
-(P-Methoxyphenyl) urea (melting point 155 ° C), N
-(P-toluenesulfonyl) -N '-(o-tolyl)
Urea (melting point 148 ° C), N- (p-toluenesulfonyl) -N '-(m-tolyl) urea (melting point 184 ° C), N
-(P-toluenesulfonyl) -N '-(p-tolyl)
Urea (melting point 149 ° C.), N- (p-toluenesulfonyl) -N ′-(pn-butylphenyl) urea, N-
(P-toluenesulfonyl) -N ′, N′-diphenylurea (melting point 159 ° C.), N- (p-toluenesulfonyl) -N ′-(o-chlorophenyl) urea (melting point 180
C), N- (p-toluenesulfonyl) -N '-(m-chlorophenyl) urea (melting point 193 ° C), N- (p-toluenesulfonyl) -N'-(2,4-dichlorophenyl) urea, N-. (P-toluenesulfonyl) -N'-methyl-N'-phenylurea (melting point 155 ° C), N- (p
-Toluenesulfonyl) -N'-benzylurea (melting point 1
77 ° C), N- (p-toluenesulfonyl) -N'-
(1-Naphthyl) urea (melting point 124 ° C.), (p-toluenesulfonyl) -N ′-(1- (2-methylnaphthyl)) urea, N- (benzenesulfonyl) -N′-phenylurea (melting point 153 ° C. ), N- (p-chlorobenzenesulfonyl) -N'-phenylurea, N- (o-toluenesulfonyl) -N'-phenylurea, N- (p-toluenesulfonyl) -N'-methylurea (melting point 172
C.), N- (p-toluenesulfonyl) -N′-ethylurea (melting point 141 ° C.), N- (p-toluenesulfonyl) -N ′-(2-phenoxyethyl) urea (melting point 19
1 ° C.), N, N′-bis (p-toluenesulfonyl) urea (melting point 155 ° C.), N- (p-toluenesulfonyl)
-N'-phenylthiourea, N- (p-toluenesulfonyl) -N '-(o-diphenyl) urea (melting point 148
C.), N- (p-toluenesulfonyl) -N '-(p-ethoxycarbonylphenyl) urea, and other compounds. These compounds may be used alone or as a mixture of two or more thereof.

Many of the N-arylsulfonyl (thio) ureas of the formula (I) as described above are novel compounds which have not been reported so far, and their synthesis is carried out, for example, by the following reactions (1) to (4). Can be done by.

[Chemical 3]

In the present invention, the color developing property can be improved by using the color developing agent represented by the general formula (I) in combination with other color developing agents. Examples of such a color developer include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1
-Bis (4-hydroxyphenyl) -1-phenylethane, 1,4-bis (1-methyl-1- (4'-hydroxyphenyl) ethyl) benzene, 1,3-bis (1-methyl-1- (4 ') -Hydroxyphenyl) ethyl) benzene, dihydroxydiphenyl ether (JP-A 1-1
80382) Benzyl p-hydroxybenzoate (JP-A-52-140483), bisphenol S, 4-
Hydroxy-4'-isopropyloxydiphenyl sulfone (JP-A-60-13852), 1,1-di (4-
Hydroxyphenyl) cyclohexane, 1,7-di (4
-Hydroxyphenylthio) -3,5-dioxaheptane (JP-A-59-52694), 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone (JP-A-60-208286), etc. Or combinations.

Specific examples of the compound having an aziridinyl group used in the present invention include the following compounds. 2,4-bis (1-aziridinylcarbonylamino) toluene, bis (4- (1-aziridinylcarbonylamino) phenyl) methane, bis (3-chloro-4- (1-aziridinylcarbonylamino)) Phenyl) methane, 2,2-bis (4- (1-aziridinylcarbonyloxy) phenyl) propane, 1,
4-bis (1-aziridinylcarbonyloxy) benzene, 1,4-bis (1-aziridinylcarbonyl) benzene and the like. These compounds may be used as a mixture of two or more thereof.

Examples of the compound having an epoxy group used in the present invention include the following compounds.

[Chemical 4]

[Chemical 5] You may use these compounds in mixture of 2 or more types.

The following compounds may be mentioned as specific examples of the organic compound having a primary or secondary amino group.

[Chemical 6] These compounds may be used as a mixture of two or more thereof.

Further, a carboxyl group or --CO--O--
Specific examples of the organic compound having a CO-structure include:
The following compounds can be mentioned.

[Chemical 7] These compounds may be used as a mixture of two or more thereof.

Examples of the leuco dye used as a dye precursor in the present invention include triphenylmethane-based compounds, fluoran-based compounds and diphenylmethane-based compounds, which can be selected from conventionally known compounds. For example, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, crystal violet lactone, 3- (N-ethyl-N-iso). Pentylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-
7-anilinofluorane, 3-diethylamino-6methyl-7- (o, p-dimethylanilino) fluorane, 3
-(N-ethyl-N-p-toluidino) -6-methyl-
7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-
Methyl-7-anilinofluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-7- (o-chloroanilino) fluorane, 3-diethylamino- 7- (m
-Trifluoromethylanilino) fluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-
Diethylamino-6-methylfluorane, and 3-cyclohexylamino-6-chlorofluorane, 3- (N
-Ethyl-N-hexylamino) -6-methyl-7-
One or more selected from (p-chloroanilino) fluorane and the like can be used.

In the thermosensitive color developing layer of the present invention, the polymeric material used as the binder is polyvinyl alcohol having various molecular weights, starch and its derivatives, methoxycellulose, carboxymethylcellulose, methylcellulose, ethylcellulose and other cellulose derivatives, poly Sodium acrylate, polyvinylpyrrolidone, acrylic acid amide / acrylic acid ester copolymer, acrylic acid amide /
Acrylic ester / methacrylic acid terpolymer, styrene / maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, and water-soluble polymer materials such as casein, and polyvinyl acetate,
Polyurethane, styrene / butadiene copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride / vinyl acetate copolymer, polybutyl methacrylate, ethylene / vinyl acetate copolymer, and styrene / butadiene /
It can be selected from various latexes such as acrylic copolymers.

Further, the thermosensitive coloring layer of the present invention may contain a heat-fusible substance (so-called sensitizer) within a range that does not impair the desired effect. Such a sensitizer has a melting point
Heat-fusible organic compounds of 50-150 C are used, and examples thereof include 1-hydroxy-2-naphthoic acid phenyl ester (JP-A-57-191809) and p-benzylbiphenyl (JP-A-60-82382). ), Benzylnaphthyl ether (JP-A-58-87094), dibenzyl terephthalate (JP-A-58-98285), benzyl p-benzyloxybenzoate (JP-A-57-2016).
91), diphenyl carbonate, ditolyl carbonate (JP-A-58)
-136489) and m-terphenyl (JP-A-57-
89994), 1,2-bis (m-tolyloxy) ethane (JP-A-60-56588), 1,5-bis (p).
-Methoxyphenoxy) -3-oxapentane (JP-A-62-181183), oxalic acid diester (JP-A-64-1583), 1,4-bis (p-tolyloxy)
It can be selected from benzene (JP-A-2-153787).

The thermosensitive coloring layer of the present invention may further contain a hindered phenol compound or an ultraviolet absorber. They are disclosed, for example, in JP-A-57-151394,
JP-A-58-160191, JP-A-58-69096
JP-A-59-2884, JP-A-59-95190
JP-A-60-22288, JP-A-60-2554
85, JP-A-61-44686, JP-A-62-16
9683, JP-A-63-17081, JP-A 1-2
49385 and Japanese Patent Application No. 2-266645, and the like, specifically, for example, 1,1,3-
Tris (3′-cyclohexyl-4′-hydroxyphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,
4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6
-Tris (3,5-ditert-butyl-4-hydroxybenzyl) benzene, 2,2'-dihydroxy-
4,4'-dimethoxybenzophenone, p-octylphenyl salicylate, 2- (2'-hydroxy-5'-
Methylphenyl) benzotriazole, ethyl-2-cyano-3,3'-diphenylacrylate, tetra (2,2,6,6-tetramethyl-4-piperidyl)
It can be selected from 1,2,3,4-butanetetracarboate and the like.

The heat-sensitive color forming layer of the heat-sensitive recording material of the present invention preferably contains waxes, organic or inorganic white pigments, etc., if necessary. As the wax, known waxes such as paraffin, amide wax, bisimide wax, and metal salt of superabsorbent fatty acid can be used.

Examples of organic or inorganic pigments include calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, calcined clay, talc, and surface-treated calcium carbonate and silica. In addition to the above inorganic fine powder, organic fine powder such as urea-formalin resin, styrene / methacrylic acid copolymer, and polystyrene resin can be used.

The content of the dye precursor in the heat-sensitive color forming layer is generally 5 to 20% by weight based on the total dry weight of the heat-sensitive color forming layer. The content of the color developer is generally 5 to 40% by weight.
Is. Further, the content of the aziridine compound or the epoxy compound is 1 to 30% by weight. Further, the content of at least one selected from an organic compound having a primary or secondary amino group and an organic compound having a carboxyl group or a -CO-O-CO- structure is 1 to 30% by weight.

When a sensitizer is contained in the thermosensitive coloring layer,
The content is preferably 10 to 40% by weight. When a hindered phenol compound or an ultraviolet absorber is contained, its content is preferably 1 to 10% by weight. Waxes and white pigments are 5 to 5
The content of the binder is generally 5 to 20% by weight, preferably 20 to 10% by weight.

The support used in the heat-sensitive recording material of the present invention is paper, coated paper having a surface coated with a pigment, latex, etc., synthetic paper having a double layer structure made of polyolefin resin, plastic film or It can be selected from these composite sheets and the like.

At least one of such sheet-like supports
On the surface, apply a coating solution containing a mixture of the above required components,
A thermosensitive coloring material is formed by drying to form a thermosensitive recording material. The coating amount of the coating liquid for the thermosensitive color developing layer is preferably 1 to 15 g / m ² when the coating liquid layer is dried, and ² to 10 g.
/ M ² is more preferable.

[0026]

The present invention will be further described with reference to the following examples. In the examples, "part" and "%" unless otherwise specified.
Represents "parts by weight" and "% by weight", respectively.

Example 1 A thermosensitive recording paper was prepared by the following operation. 1) Preparation Ingredient Quantity of color former dispersion A (parts) 3- (N-ethyl--N--isopentylamino) - 20 6-methyl-7-anilinofluoran polyvinyl alcohol - le 10% solution 10 Water 70 The above composition was pulverized using a sand grinder until the average particle size became 1 μm or less.

[0028] 2) Preparation Ingredients Amount of Developer Dispersion B (parts) N-(p-toluenesulfonyl)-N'-phenylurea 20 Polyvinyl alcohol - sand grinder Le 10% solution 10 Water 70 The composition And was pulverized until the average particle diameter becomes 1 μm or less.

[0029] 3) sensitizer prepared Ingredients Amount of Dispersion C (parts) of oxalic acid di-p-methylbenzyl ester 20 polyvinyl alcohol - using a sand grinder Le 10% solution 10 Water 70 The composition, average particle size It was pulverized until it became 1 μm or less.

A sand grinder Le 10% solution 10 Water 70 The composition - [0030] 4) Preparation Ingredients Amount of Dispersion D (parts) bis (4- (1-aziridinyl carbonylamino) 20 phenyl) methane polyvinyl alcohol It was crushed and crushed until the average particle size became 1 μm or less.

[0031] 5) Dispersion Preparation Ingredients Amount of E (parts) Compound 35) 20 Polyvinyl alcohol - using a sand grinder Le 10% solution 10 Water 70 The composition, average particle size was pulverized to 1μm or less ..

6) Preparation of Pigmented Undercoat Paper 85 parts of calcined clay (trade name Ansilex) in 320 parts of water
40 parts of styrene-butadiene copolymer emulsion (solid content 50%) and 1 part
0% oxidized starch aqueous solution 50 parts were mixed, the resultant coating liquid, the coating amount after drying was coated so as to 7.0 g / m ² on a base paper basis weight of 48 g / m ^2, A pigment primed paper was prepared.

7) Formation of thermosensitive coloring layer 50 parts of the above-mentioned solution A, 100 parts of solution B, 75 parts of solution C, and solution D 40
Parts, and 10 parts of E liquid, 27 parts of calcined clay, 20 parts of 25% zinc stearate dispersion, 10 parts of 30% paraffin dispersion, and 10% of 10% polyvinyl alcohol aqueous solution.
0 parts were mixed and stirred to prepare a coating liquid. This coating solution on one surface of the base paper basis weight of 50 g / m ^2, the coating amount after drying was coated with a 5.0 g / m ² and dried to form a thermosensitive coloring layer, a heat-sensitive recording paper did.

The thermal recording paper prepared as described above is
The surface was processed by a super calendar and the surface smoothness was set to 600 to 1000 seconds.

With respect to the thermal recording paper sample thus obtained, one line recording time was 10 msec and scanning line density was 8 × 8 dots / mm ² by using a dynamic color tester which was a commercial thermal facsimile modified for testing. , Applied energy 0.54
When 64 lines were printed under the condition of mj / dot,
A Macbeth reflection densitometer RD-914 gave a clear black color image with a high density of 1.2 or more.

Then, within 30 minutes after formation of the color image, the salad oil was applied to the color sample with a cotton swab and the mixture was kept at room temperature for 3 minutes.
After standing for 0 minutes, the oil resistance was evaluated by visually observing the residual state of the image. Further, dioctyl phthalate was used instead of salad oil, the same test as in the oil resistance evaluation was conducted, and the residual state of the image was visually observed to evaluate the plasticizer resistance. Table 1 shows the test results
Shown in.

Example 2 The same operation as in Example 1 was performed. However, in the preparation of the E liquid used for forming the thermosensitive coloring layer, the carboxyl group-containing compound of the formula 34) was used instead of the compound 35). The test results are shown in Table 1.

Example 3 The same operation as in Example 1 was performed. However, in the preparation of the liquid B used for forming the thermosensitive coloring layer, N- (p- instead of N- (p-toluenesulfonyl) -N'-phenylurea was used.
Toluenesulfonyl) -N '-(p-tolyl) urea was used to prepare an epoxy group-containing compound of the formula 1) instead of bis (4- (1-aziridinylcarbonylamino) phenyl) methane in the preparation of the liquid D. In addition, in the preparation of solution E, the compound containing a carboxyl group of formula 31) was used in place of compound 35). The test results are shown in Table 1.

Example 4 The same operation as in Example 1 was performed. However, in the preparation of the liquid B used for forming the thermosensitive coloring layer, N- (p- instead of N- (p-toluenesulfonyl) -N'-phenylurea was used.
Toluenesulfonyl) -N ′-(p-tolyl) urea was used, and in the preparation of solution E, the compound having the primary amino group of the formula 19) was used instead of the compound 35). The test results are shown in Table 1.

Example 5 The same operation as in Example 1 was performed. However, in the preparation of the liquid D used for forming the thermosensitive coloring layer, 2,4-bis (1-aziridinylcarbonylamino) toluene was used instead of bis (4- (1-aziridinylcarbonylamino) phenyl) methane. In preparation of solution E, the compound of formula 22) was used in place of compound 35) for the preparation of solution E.
The test results are shown in Table 1.

Example 6 The same operation as in Example 1 was performed. However, the acid anhydride of the formula 28) was used in place of the compound 35) in the preparation of the E liquid used for forming the thermosensitive coloring layer. The test results are shown in Table 1.

Comparative Example 1 The same operation as in Example 1 was performed. However, in the preparation of the liquid B used for forming the thermosensitive coloring layer, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) was used instead of N- (p-toluenesulfonyl) -N'-phenylurea. Using. In preparing the coating liquid, the amount of the liquid A used was 65 parts, the amount of the liquid B used was 105 parts, the amount of the liquid C used was 105 parts, and the liquids D and E were not used. The test results are shown in Table 1.

Comparative Example 2 The same operation as in Example 1 was performed. However, in the preparation of solution B used for forming the thermosensitive coloring layer, 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A) was used instead of N- (p-toluenesulfonyl) -N'-phenylurea. Was used. Further, the liquid E was not used in the preparation of the coating liquid. The test results are shown in Table 1.

Comparative Example 3 The same operation as in Example 1 was performed. However, in the preparation of the liquid B used for forming the thermosensitive coloring layer, N- (p- instead of N- (p-toluenesulfonyl) -N'-phenylurea was used.
Toluenesulfonyl) -N '-(p-tolyl) urea was used. Further, the liquid E was not used in the preparation of the coating liquid. The test results are shown in Table 1.

[0045]

[Table 1]

As is clear from Table 1, the heat-sensitive recording material of the present invention had excellent oil resistance and plasticizer resistance immediately after the formation of a color image.

[0047]

INDUSTRIAL APPLICABILITY The heat-sensitive recording material of the present invention contains N-arylsulfonyl (thio) ureas having a specific chemical structure of formula (I) as a developer in the heat-sensitive color forming layer, and further contains an aziridine compound. Or an epoxy compound, and an organic compound having a primary amino group or a secondary amino group, and at least one selected from an organic compound having a carboxyl group or a —CO—O—CO— structure, so that a color image is formed. It shows excellent oil resistance and plasticizer resistance immediately after formation and is extremely useful in practice.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 17, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1](However, X represents an oxygen atom or a sulfur atom, and R₁
Is an aromatic group having no substituent, and a lower alkyl group.
Group and at least one member selected from halogen atoms
Represents a member selected from benzene ring groups substituted by
And R₂And R ₃Are each independently a hydrogen atom,
Substituted with an alkyl group, aralkyl group, or aryloxy group
Alkyl group, aromatic group having no substituent, and
Alkyl group, aryl group, aralkyl group, alkyloxy
Group, alkyloxycarbonyl group, aryloxycal
Bonyl group, aralkyloxycarbonyl group, aryls
At least one selected from a sulfonyl group and a halogen atom.
Also represents a member selected from aromatic groups substituted by one member.
Forget ) Is at least one compound represented by
Further, in the thermosensitive coloring layer, at least one
Organic compounds having primary or secondary amino groups, and small
At least one carboxyl group or -CO-O-CO
-At least one selected from organic compounds having a structure
A thermosensitive recording medium characterized by containing.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

The heat-sensitive recording material of the present invention comprises a sheet-shaped substrate,
A substantially colorless dye precursor formed on at least one surface of the sheet-like substrate, a developer that reacts with the dye precursor under heating to develop a color, and at least one aziridinyl group, or A thermosensitive coloring layer containing an organic compound having an epoxy group, wherein the color developer has the general formula (I):

[Chemical 2](However, X represents an oxygen atom or a sulfur atom, and R₁
Is an aromatic group having no substituent, and a lower alkyl group.
Group and at least one member selected from halogen atoms
Represents a member selected from benzene ring groups substituted by
And R₂And R ₃Are each independently a hydrogen atom,
Substituted with an alkyl group, aralkyl group, or aryloxy group
Alkyl group, aromatic group having no substituent, and
Alkyl group, aryl group, aralkyl group, alkyloxy
Group, alkyloxycarbonyl group, aryloxycal
Bonyl group, aralkyloxycarbonyl group, aryls
At least one selected from a sulfonyl group and a halogen atom.
Also represents a member selected from aromatic groups substituted by one member.
Forget ) Is at least one compound represented by
Further, in the thermosensitive coloring layer, at least one
Organic compounds having primary or secondary amino groups, and small
At least one carboxyl group or -CO-O-CO
-At least one selected from organic compounds having a structure
Is contained.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

[0009]

The N-of the general formula (I) used in the present invention
Examples of arylsulfonyl (thio) ureas include N-
(P-Toluenesulfonyl) -N′-phenylurea (melting point 165 ° C.), N- (p-toluenesulfonyl) -N ′
-(P-Methoxyphenyl) urea (melting point 155 ° C), N
-(P-toluenesulfonyl) -N '-(o-tolyl)
Urea (melting point 148 ° C), N- (p-toluenesulfonyl) -N '-(m-tolyl) urea (melting point 184 ° C), N
-(P-toluenesulfonyl) -N '-(p-tolyl)
Urea (melting point 149 ° C.), N- (p-toluenesulfonyl) -N ′-(pn-butylphenyl) urea, N-
(P-toluenesulfonyl) -N ′, N′-diphenylurea (melting point 159 ° C.), N- (p-toluenesulfonyl) -N ′-(o-chlorophenyl) urea (melting point 180
C), N- (p-toluenesulfonyl) -N '-(m-chlorophenyl) urea (melting point 193 ° C), N- (p-toluenesulfonyl) -N'-(2,4-dichlorophenyl) urea, N-. (P-toluenesulfonyl) -N'-methyl-N'-phenylurea (melting point 155 ° C), N- (p
-Toluenesulfonyl) -N'-benzylurea (melting point 1
77 ° C), N- (p-toluenesulfonyl) -N'-
(1-Naphthyl) urea (melting point 124 ° C.), (p-toluenesulfonyl) -N ′- [ 1- (2-methylnaphthyl) ] urea, N- (benzenesulfonyl) -N′-phenylurea (melting point 153 ° C. ), N- (p-chlorobenzenesulfonyl) -N'-phenylurea, N- (o-toluenesulfonyl) -N'-phenylurea, N- (p-toluenesulfonyl) -N'-methylurea (melting point 172
C.), N- (p-toluenesulfonyl) -N′-ethylurea (melting point 141 ° C.), N- (p-toluenesulfonyl) -N ′-(2-phenoxyethyl) urea (melting point 19
1 ° C.), N , N′-bis (p-toluenesulfonyl) urea (melting point 155 ° C.), N- (p-toluenesulfonyl)
-N'-phenylthiourea, N- (p-toluenesulfonyl) -N '-(o-diphenyl) urea (melting point 148
C.), N- (p-toluenesulfonyl) -N '-(p-ethoxycarbonylphenyl) urea and other compounds. These compounds may be used singly used rather <br/> I even or as a mixture of two or more thereof.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

Many of the N-arylsulfonyl (thio) ureas of the formula (I) as described above are novel compounds which have not been reported so far, and their synthesis is carried out, for example, by the following reactions (1) to (4). Can be done by.

[Chemical 3]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

In the present invention, the color developing property can be improved by using the color developing agent represented by the general formula (I) in combination with other color developing agents. Examples of such color developers, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1, 1
-Bis (4-hydroxyphenyl) -1-phenylethane, 1,4-bis [ 1-methyl-1- (4'-hydroxyphenyl) ethyl ] benzene, 1,3-bis [ 1-methyl-1- (4 ' -Hydroxyphenyl) ethyl ] benzene, dihydroxydiphenyl ether (JP-A-1-1-1
No. 80382) , benzyl p-hydroxybenzoate (JP-A No. 52-140483), bisphenol S, 4-
Hydroxy-4'-isopropyloxy-diphenylsulfone (JP 60-13852), 1, 1- di (4-
Hydroxyphenyl) cyclohexane, 1, 7- di (4
- hydroxyphenyl thio) -3, 5-dioxaheptane (JP-59-52694), 3, 3'-diallyl -4, alone 4'-dihydroxydiphenyl sulfone (JP 60-208286) Or a combination
Oh it is up.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

[0012] Examples of the compound having an aziridinyl group used in the present invention can be specifically gels Oh the following compounds, for example. 2,4-bis (1-aziridinylcarbonylamino) toluene, bis [ 4- (1-aziridinylcarbonylamino) phenyl ] methane, bis
[ 3-chloro-4- (1-aziridinylcarbonylamino) phenyl ] methane, 2,2-bis [ 4- (1-aziridinylcarbonyloxy) phenyl ] propane, 1,
4-bis (1-aziridinylcarbonyloxy) benzene, 1,4-bis (1-aziridinylcarbonyl) benzene and the like. These compounds may be used as a mixture of two or more thereof.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction content]

Further, a carboxyl group or --CO--O--
Specific examples of the organic compound having a CO-structure include:
The following compounds can be mentioned.

[Chemical 7] These compounds may be used as a mixture of two or more thereof.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

The leuco dye used as a dye precursor in the present invention, triphenylmethane, fluoran, Gerare diphenylmethane-based compounds Oh, can be selected from those known in the art. For example, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, crystal violet lactone, 3- (N-ethyl-N-iso). Pentylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-
7-anilinofluorane, 3-diethylamino-6 - methyl-7- ( 2 ', 4' -dimethylanilino) fluorane, 3- (N-ethyl-N-p-toluidino) -6-methyl-7- Anilinofluoran, 3-pyrrolidino-6-
Methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-
Anilinofluorane, 3-diethylamino-7- (o-
Chloroanilino) fluorane, 3-diethylamino-7
-(M-trifluoromethylanilino) fluorane, 3
-Diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6-methylfluorane, 3-
Cyclohexylamino-6-chloro fluoran, and 3- (N- ethyl--N- hexylamino) -6-methyl-7-(p-chloroanilino) can be used one or more selected from fluoran like.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

A sand grinder Le 10% solution 10 Water 70 The composition - [0030] 4) Preparation Ingredients Amount of Dispersion D (parts) bis [4- (1-aziridinyl carbonylamino) 20 phenyl] methane polyvinyl alcohol It was crushed and crushed until the average particle size became 1 μm or less.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

[0031] 5) Dispersion Preparation Ingredients Amount of E (parts) Compound 37) 20 Polyvinyl alcohol - using a sand grinder Le 10% solution 10 Water 70 The composition, average particle size was pulverized to 1μm or less ..

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

7) Formation of thermosensitive coloring layer 50 parts of the above-mentioned solution A, 100 parts of solution B, 75 parts of solution C, and solution D 40
Parts, and 10 parts of E liquid, 27 parts of calcined clay, 20 parts of 25% zinc stearate dispersion, 10 parts of 30% paraffin dispersion, and 10% of 10% polyvinyl alcohol aqueous solution.
0 parts were mixed and stirred to prepare a coating liquid. This coating solution was applied to one surface of the pigment-undercoated paper so that the coating amount after drying would be 5.0 g / m ^2, and dried to form a thermosensitive coloring layer, to prepare a thermosensitive recording paper.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

Example 3 The same operation as in Example 1 was performed. However, in the preparation of the liquid B used for forming the thermosensitive coloring layer, N- (p- instead of N- (p-toluenesulfonyl) -N'-phenylurea was used.
Toluenesulfonyl) -N '-(p-tolyl) urea was used to prepare an epoxy group-containing compound of the formula 1) instead of bis [ 4- (1-aziridinylcarbonylamino) phenyl ] methane for the preparation of solution D. In addition, in the preparation of solution E, the compound containing a carboxyl group of formula 31) was used in place of compound 35). The test results are shown in Table 1.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Item name to be corrected] 0040

[Correction method] Change

[Correction content]

Example 5 The same operation as in Example 1 was performed. However, in the preparation of the liquid D used for forming the thermosensitive coloring layer, 2,4-bis (1-aziridinylcarbonylamino) toluene was used instead of bis [ 4- (1-aziridinylcarbonylamino) phenyl ] methane. In preparation of solution E, the compound of formula 22) was used in place of compound 35) for the preparation of solution E.
The test results are shown in Table 1. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 1, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

Examples of the compound having an epoxy group used in the present invention include the following compounds.

[Chemical 4]

[Chemical 5] You may use these compounds in mixture of 2 or more types.

Claims (1)

[Claims] 1. A sheet-shaped substrate and a small number of the sheet-shaped substrate.
Dye precursor that is formed on at least one side and is substantially colorless
The body reacts with this dye precursor under heat to develop it
A developer, and at least one aziridinyl group or
Has a thermosensitive coloring layer containing an organic compound having an epoxy group.
However, the developer is represented by the general formula (I):(However, X represents an oxygen atom or a sulfur atom, and R₁
Is an aromatic group having no substituent, and a lower alkyl group.
Group and at least one member selected from halogen atoms
Represents a member selected from benzene ring groups substituted by
And R₂And R ₃Are each independently a hydrogen atom,
Substituted with an alkyl group, aralkyl group, or aryloxy group
Alkyl group, aromatic group having no substituent, and
Alkyl group, aryl group, aralkyl group, alkyloxy
Group, alkyloxycarbonyl group, aryloxycal
Bonyl group, aralkyloxycarbonyl group, aryls
At least one selected from a sulfonyl group and a halogen atom.
Also represents a member selected from aromatic groups substituted by one member.
Forget ) Is at least one compound represented by
Further, in the thermosensitive coloring layer, at least one
Organic compounds having primary or secondary amino groups, and small
At least one carboxyl group or -CO-O-CO
-At least one selected from organic compounds having a structure
A thermosensitive recording medium characterized by containing.