JPH05246145A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material with high color development density and good storing property of color-developed image by providing a heat-sensitive color development layer contg. an electron donating colorless dye and an electron receiving compd. consisting of a specified compd. on a substrate. CONSTITUTION:A coating liq. for a heat-sensitive color developing layer is prepd. by dissolving or dispersing each specified amt. of an electron donating colorless dye, a compd. of formula I (wherein Ar is a phenyl group and a naphthyl group each having a halogen atom, an alkyl group, a cycloalkyl group, a carbamoyl group, an acylamino group, an acrylamino group or a sulfone amide group as a substd. group or no substd. group; X is a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an aralkyl group, an aryl group, an allyl group or an alkoxy group) or a polyvalent metal salt thereof and a binder in a solvent or a dispersing medium. A substrate such as a paper and a plastic sheet is coated with this coating liq. and is dried to laminate a heat- sensitive color development layer and to obtain thereby a heat-sensitive recording material.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a recording material. In particular, the present invention relates to a recording material utilizing a novel electron-accepting compound in a recording material utilizing a color reaction of an electron-donating colorless dye and an electron-accepting compound. The electron-accepting compound according to the present invention is a particularly useful compound as an electron-accepting compound for pressure-sensitive recording materials and heat-sensitive recording materials, and an electrically conductive heat-sensitive recording sheet, a photosensitive recording sheet, an electrostatic recording sheet, It is a compound that can be applied to marking materials and ballpoint pen inks.

[0002]

Use of various salicylic acid compounds or polyvalent metal salts thereof as electron-accepting compounds for pressure-sensitive recording materials or heat-sensitive recording materials is disclosed in JP-A-48-9891.
4, Japanese Patent Publication No. 49-10856, Japanese Patent Publication No. 52-1327,
JP-A-62-25086, JP-A-63-186729,
It is disclosed in JP-A-2-85231, JP-A-2-91042, JP-A-2-142747 and the like.

[0003]

However, these salicylic acid compounds or their polyvalent metal salts are not always satisfactory electron-accepting compounds. That is, the color density when used in combination with an electron-donating colorless dye is insufficient, the density of the color image after recording decreases with time, and the surface concentration of a white powdery material called so-called powder blowing may occur. There are problems such as occurrence.

[0004]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to use a novel electron-accepting compound in combination with an electron-donating colorless dye to obtain a sufficient color density and to improve the storage stability in raw and aging. To provide a recorded material. The object of the present invention is achieved by a recording material using an electron-donating colorless dye and an electron-accepting compound, which uses a compound represented by the following general formula (I) or a polyvalent metal salt thereof as the electron-accepting compound. Was done.

General formula (I)

[Chemical 2]

In the above formula, Ar represents a substituted or unsubstituted phenyl group or naphthyl group, and the substituents are a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group and carbamoyl. Group, an acylamino group or a sulfonamide group, and X represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an aralkyl group, an aryl group, an allyl group or an alkoxy group.

The present invention will be described in detail below. Since the color-developing reaction of the electron-accepting compound for the recording material is generally carried out in an organic medium having a relatively small polarity, the solubility in the medium is the most important property required for the color-developing agent.

Although these solubilities are closely related to the structure of the general formula (I), Ar is an alkyl group, an aralkyl group, or the like in consideration of the difficulty of obtaining raw materials and the performance of the salicylic acid compound obtained. A phenyl group or a naphthyl group substituted with an alkoxy group, an alkoxycarbonyl group or an acylamino group is preferable. Furthermore, the polyvalent metal salt of the salicylic acid compound represented by the general formula [I], especially the zinc salt, is well dissolved in an organic solvent having a small polarity and has a large color developing action. There are great advantages in color speed.

The characteristics of the electron-accepting compound according to the present invention are as follows. (1) In combination with an electron-donating colorless dye, a high-density color image is provided. (2)
Preservation of the ground and color image is good. (3) It is stable without sublimation. Further, in order to further improve these characteristics, a divalent, trivalent or tetravalent metal compound, for example, an oxide of a metal selected from zinc, magnesium, barium, calcium, aluminum, tin, titanium, manganese, iron and the like. , Hydroxide, carbonate, silicate, or sulfate is preferably used in combination.

Specific examples of the electron-accepting compound of the general formula (I) of the present invention are shown below, but the present invention is not limited thereto. 5- (4-t-amylphenoxysulfonyl) salicylic acid, 5- (4-octylphenoxysulfonyl) salicylic acid, 5- (4-t-octylphenoxysulfonyl) salicylic acid, 5- (3,5- Dimethylphenoxysulfonyl) salicylic acid, 5- (2,4-di-t
-Amylphenoxysulfonyl) salicylic acid, 5- (4
-T-butylphenoxysulfonyl) salicylic acid, 5-
(3,5-di-t-butylphenoxysulfonyl) salicylic acid, 5- (2-methyl-5-isopropylphenoxysulfonyl) salicylic acid, 5- (4-cyclohexylphenoxysulfonyl) salicylic acid, 5- ( 4-phenylphenoxysulfonyl) salicylic acid, 5- (4-benzylphenoxysulfonyl) salicylic acid, 5- (4-cumylphenoxysulfonyl) salicylic acid, 5- (4-ethoxyphenoxysulfonyl) salicylic acid, 3-chloro-5- (4-t-amylphenoxysulfonyl) salicylic acid, 3-methyl-5- (2,4-di-t-amylphenoxysulfonyl) salicylic acid, 3-methoxy-5-
(4-t-butylphenoxysulfonyl) salicylic acid,
3-nitro-5- (4-octylphenoxysulfonyl) salicylic acid, 3-allyl-5- (4-phenylphenoxysulfonyl) salicylic acid, 5- (4-octyloxycarbonylphenoxysulfonyl) salicylic acid, 5
-(2-dodecanoylaminophenoxysulfonyl) salicylic acid, 5- (4-butoxy-1-naphthoxysulfonyl) salicylic acid, 5- (3-N, N-dibutylcarbamoyl-2-naphthoxysulfonyl) salicylic acid and the like.

These may be used alone or in a mixture or in a mixture with other electron-accepting compounds (eg, bisphenol A, 3,5-bis- (α-methylbenzyl) salicylate zinc, activated clay, etc.). As the electron-donating colorless dye used in the present invention, triarylmethane compounds, diphenylmethane compounds, xanthene compounds, thiazine compounds, spiropyran compounds, etc. are used. Some of these are exemplified by triarylmethane compounds as 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (that is, crystal violet lactone) and 3- (p-dimethylaminophenyl). Phenyl) -3- (2-methylindol-3-yl) phthalide and the like, and as the diphenylmethane compound,
There are 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, and the like, and xanthene compounds include rhodamine-B-
There are anilinolactam, rhodamine B (p-chloroanilino) lactam, 2-anilino-6-diethylaminofluorane, 2- (3,4-dichloroanilino) -6-diethylaminofluorane and the like, and as thiazine compounds, There are benzoyl leuco methylene blue, p-nitrobenzyl leuco methylene blue and the like, and spiro compounds include 3-methyl-spiro-dinaphthopyran, 3,
3'-dichloro-spiro-dinaphthopyran and the like. These may be used alone or as a mixture.

The electron-accepting compound according to the present invention can be synthesized by reacting salicylic acid sulfochloride with the corresponding phenol compound in a solvent in the presence of a dehydrochlorinating agent. Further, the polyvalent metal salt, for example, zinc salt, can be easily synthesized by a usual method in which a sulfosalicylic acid compound is neutralized with an alkaline aqueous solution and then a zinc sulfate solution is added. The pressure-sensitive copying paper according to the present invention is disclosed in US Pat. Nos. 2,505,470 and 2,50.
5,471, 2,505,489, 2,54
8,366, 2,712,507, 2,73
0,456, 2,730,457, 3,41
It can take various forms as described in the prior patents such as 8,250. Most commonly it consists of at least a pair of sheets containing separately the electron-donating colorless dye and the electron-accepting compound according to the invention. That is, an electron-donating colorless dye is used alone or mixed and dissolved in a solvent (synthetic oil such as alkylated naphthalene, alkylated diphenyl, chlorinated paraffin) and dispersed in a binder or contained in a microcapsule. After that, the color developing agent sheet is applied by coating it onto a support such as paper or a plastic sheet, and the electron-accepting compound according to the present invention is used alone or mixed, or together with another electron-accepting compound, a styrene-butadiene latex. A developer sheet is obtained by dispersing it in a binder such as polyvinyl alcohol and applying it to a support such as paper or a plastic sheet.

The amount of the electron-donating colorless dye and the electron-accepting compound used depends on the desired coating thickness, the form of the pressure-sensitive copying paper, the capsule manufacturing method, and other conditions, and may be appropriately selected according to the conditions. Is desirably adjusted in the range of 5 to 500 parts by weight, preferably 10 to 50 parts by weight, relative to 10 parts by weight of the electron-donating colorless dye. For the method of manufacturing capsules, see US Pat. No. 2,800,4.
57, 2,800,458, the method utilizing coacervation of hydrophilic colloid sol, British Patents 867,797, 950,443, 98.
9, 264, 1,091,076 and the like, such as the interfacial polymerization method.

The heat-sensitive recording material comprises a liquid prepared by dissolving or dispersing a binder in a solvent or a dispersion medium, and an electron-donating colorless dye, an electron-accepting compound according to the present invention and, if necessary, a heat-fusible agent as a recording sensitivity improving agent. The substance is pulverized and mixed sufficiently finely, and an oil absorbing pigment such as kaolin, talc, wax, calcium carbonate, and cellulose filler is added to prepare a coating liquid. If necessary, paraffin wax emulsion, latex binder, UV absorber,
Etc. can be added.

The coating liquid is applied and dried on a support such as paper or a plastic sheet. When preparing a solution, all the components may be mixed and pulverized simultaneously from the beginning, or they may be pulverized and dispersed separately in an appropriate combination and then mixed. The amount of each component constituting the heat-sensitive recording material is 1 to 1
2 parts by weight, electron accepting compound 1 to 6 parts by weight, heat fusible substance 0 to 30 parts by weight, pigment 0 to 15 parts by weight, binder 1
-15 parts by weight and small amounts of other additives and dispersants.

As the heat-fusible substance, caproic acid amide, stearic acid, stearic acid amide, benzanilide, N-octadecylurea, 1-hydroxy-2-naphthoic acid phenyl ester, terephthalic acid dibenzyl ester and the like are used. .. These substances are colorless solids at room temperature and have a sharp melting point at a temperature suitable for the heating temperature for copying, that is, around 70 to 160 ° C.

[0017]

EXAMPLES Examples will be shown below, but the present invention is not limited to these examples.

Example 1 1. Preparation of color former sheet 2-anilino-3-methyl- which is an electron-donating colorless dye
1 g of 6-diethylaminofluorane was dissolved in 30 g of alkylated naphthalene. This solution was added to 50 g of water, in which 6 g of gelatin and 4 g of arabic gum were dissolved, with vigorous stirring to emulsify to form oil droplets having a diameter of 1 μ to 10 μ,
250 g of water was added. Add acetic acid in small amounts to bring the pH to about 4
Then, coacervation was caused to form a wall of gelatin and gum arabic around the oil drop, and after adding formalin, the pH was raised to 9 and the wall was hardened.

The yield thus obtained weighed 50 g / m ² coloring agent sheet by coating and drying on the paper so that the solid coating amount of the microcapsule dispersion is 1 m ² per 7 g. 2. Preparation of Developer Sheet The zinc salt of the electron-accepting compound 4-t-amylphenoxy-sulfosalicylic acid according to the present invention was synthesized by the following method.

After dissolving 17.9 g of salicylic acid in 35.3 g of chlorosulfonic acid at 3 ° C. or lower, the mixture was heated at 60 ° C. for 1 hour. This was cooled to 15 ° C. or lower, poured into crushed ice and the precipitated white crystals were collected by filtration, washed with cold water and dried to obtain 19.2 g (yield 63%) of 5-sulfochlorosalicylic acid. .. Chloroform 550 m was obtained by adding 11.1 g of 4-t-amylphenol and 41.1 g of triethylamine.
1-soluble in 5-liter, 5-sulfochloro salicylic acid 1
After adding 9.2 g and reacting at room temperature for 12 hours, the mixture was concentrated under reduced pressure, and tetrahydrofuran (80 ml) and 10% hydrochloric acid (50 ml) were added.
Was added and extracted with ether. Remove ether and remove 17.
2-g-yield 70%, 4-t-amylphenoxy-sulfosalicylic acid (carboxylic acid content 99.6), melting point 157 ° C.
%) Was obtained. After 7.3 g of this was neutralized with 1N sodium hydroxide, 6.5 g of 25% zinc sulfate solution was added, and the precipitated colloidal precipitate was collected by filtration and dried to obtain 7.6 g (yield 96%) of zinc salt. Obtained. Zinc content is 8.00% (theoretical value is 8.25)
%)Met.

5 g of the zinc salt of 4-t-amylphenoxy-sulfosalicylic acid may be dispersed in 50 g of a 5% aqueous solution of polyvinyl alcohol (saponification number: 99%, degree of polymerization: 1000), and 5 g of kaolin (Georgia kaolin) may be added. It was dispersed and used as a coating liquid. Weigh obtained coating solution such that the zinc salt is 1 m ² per 0.7 g 50 g / m ²
Was coated on the above paper and dried to obtain a color developer sheet. The color-developing agent sheet and the color-developing agent sheet thus prepared are overlapped to each other for 600 k.
Color was developed under a load pressure of g / cm ² to obtain a black image. By measuring the absorption maximum of the visible absorption spectrum of the coloring surface, 1.
A color density of 22 was obtained.

Example 2 3,5-di-t-butyl having a melting point of 158 ° C. was used in the same manner as in Example 1 except that 20.6 g of 3,5-di-t-butylphenol was used instead of 4-t-butylphenol. 26.8 g of phenoxysulfosalicylic acid was obtained. 66% yield,
The carboxylic acid content was 98.6%. Similarly, 3.5
A zinc salt of -di-t-butylphenoxy-sulfosalicylic acid was obtained. The yield was 97% and the zinc content was 7.38% (theoretical amount: 7.46%). The zinc salt in a similar manner using the zinc salt 5.5g was obtained coated dried color developer sheet to paper weighing 50 g / m ² so as to be 1 m ² per 0.77 g.
The color developer sheet thus prepared and the color developing agent sheet of Example 1 were superposed, and color was developed under a load pressure of 600 kg / cm ² to obtain a black printed image. The color density was 1.19.

Example 3 2-anilino-3-methyl-, an electron-donating colorless dye
5 g of 6-N-methyl-N-cyclohexylaminofluorane was dispersed with a 5% aqueous solution of polyvinyl alcohol (50 g) in a ball mill overnight. On the other hand, 10 g of a zinc salt of 4-t-amylphenoxy-sulfosalicylic acid, which is an electron-accepting compound, was added to 100% of a 5% polyvinyl alcohol aqueous solution.
The mixture was dispersed in a ball mill for 24 hours with a ball mill, and after mixing these two kinds of dispersions, 20 g of kaolin was added and well dispersed, and 5 g of a 50% dispersion of paraffin wax emulsion was added to obtain a coating liquid. Solid amount of coating liquid is 1m
^A coated paper was obtained by coating the paper at a weight of 50 g / m ² so that the weight was 6 g per ² and drying at 60 ° C. for 1 minute. The coated paper was heated and colored with a facsimile machine at a heating energy of 40 mJ / mm ² to obtain a black printed image. Color density is 1.47
Met.

Example 4 The same as Example 3 except that the zinc salt of 4-t-amylphenoxy-sulfosalicylic acid was replaced by the zinc salt of 3,5-di-t-butylphenoxy-sulfosalicylic acid. A thermosensitive recording paper was obtained. This is Example 3
In the same manner as above, color development was performed by heating to obtain a black image. The color density was 1.45.

Comparative Example 1 Same as Example 1 except that zinc salt of 3,5-bis (α-methylbenzyl) salicylic acid was used in place of zinc salt of 4-t-amylphenoxy-sulfosalicylic acid. A pressure sensitive recording paper was obtained. This was color-pressed in the same manner as in Example 1 to obtain a black image. Color density is 1.
It was 18.

Comparative Example 2 A thermosensitive recording paper was obtained in the same manner as in Example 3 except that bisphenol A was used in place of the zinc salt of 4-t-amylphenoxy-sulfosalicylic acid. This was heated and color-developed in the same manner as in Example 3 to obtain a black image.
The color density was 1.25. After exposing these color-developing sheets to sunlight for 1 hour, the absorption maximum of the visible absorption spectrum of the color-developing surface was measured to determine the density. The light resistance was calculated from these values by the following formula and is shown in Table 1. Lightfastness value = [(concentration of color former after exposure to sunlight) / (concentration of color former before exposure to sunlight)] × 100 (%). H. Under high temperature conditions for 24 hours, and at 40 ° C., 90% R.C. H. After standing for 24 hours under high humidity conditions, the absorption maximum of the visible absorption spectrum of the color development surface was measured to determine the concentration, and the heat resistance value and humidity resistance value were calculated in the same manner as the above light resistance value, and the results are shown in Table 1. .. Further, the degree of fogging of the blank area at that time was evaluated, and the results are shown in Table 1.

[0027]

[Table 1]

[0028]

As is clear from the results shown in Table 1, the recording material according to the present invention is an excellent recording material having a high color density, good storability of a color image, and little background fog.

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[Procedure amendment]

[Submission date] August 14, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[0002]

Use of various salicylic acid compounds or polyvalent metal salts thereof as electron-accepting compounds for pressure-sensitive recording materials or heat-sensitive recording materials is disclosed in JP-A-48-9891.
4, Japanese Patent Publication No. 49-10856, Japanese Patent Publication No. 52-1327,
JP-A-62-25086, JP-A-63-186729,
It is disclosed in JP-A-2-85231, JP-A-2-91042, JP-A-2-142747, JP-A-3-15587 and the like.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

These may be used alone or in a mixture or in a mixture with other electron-accepting compounds (eg, bisphenol A, 3,5-bis- (α-methylbenzyl) salicylate zinc, activated clay, etc.). As the electron-donating colorless dye used in the present invention, triarylmethane compounds, diphenylmethane compounds, xanthene compounds, thiazine compounds, spiropyran compounds, etc. are used. Some of these are exemplified by triarylmethane compounds as 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (that is, crystal violet lactone) and 3- (p-dimethylaminophenyl). Phenyl) -3- (2-methylindol-3-yl) phthalide and the like, and as the diphenylmethane compound,
4,4' bis-dimethylamino-benzhydryl Le benzylidene <br/> ether, N- Harofueniru - has leucoauramine, etc., as the xanthene compounds, rhodamine -B-
There are anilinolactam, rhodamine B (p-chloroanilino) lactam, 2-anilino-6-diethylaminofluorane, 2- (3,4-dichloroanilino) -6-diethylaminofluorane and the like, and as thiazine compounds, benzoyl leuco methylene blue, have p- Nitorobe <br/> down along Le leuco methylene blue, etc., as the spiro compounds, 3-methyl - spiro - dinaphthopyran,
3,3'-dichloro-spiro-dinaphthopyran and the like. These may be used alone or as a mixture.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

The electron-accepting compound according to the present invention is a salicylic acid sulfochloride and a corresponding phenol compound or a sodium compound.
It can be synthesized by reacting a phthalol compound in a solvent in the presence of a dehydrochlorinating agent. Further, the polyvalent metal salt, for example, zinc salt, can be easily synthesized by a usual method in which a sulfosalicylic acid compound is neutralized with an alkaline aqueous solution and then a zinc sulfate solution is added. The pressure-sensitive copying paper according to the present invention is disclosed in US Pat.
5,470, 2,505,471, 2,50
No. 5,489, No. 2,548,366, No. 2,71
2,507, 2,730,456, 2,73
It can take various forms as described in the prior patents such as 0,457 and 3,418,250. Most commonly, it consists of at least a pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound according to the present invention. That is, an electron-donating colorless dye alone or in combination,
Solvent (alkylated naphthalene, alkylated diphenyl,
Dissolve it in a synthetic oil such as chlorinated paraffin) and disperse it in a binder, or after it is contained in microcapsules, it is applied to a support such as paper or a plastic sheet to form a color former sheet, The electron-accepting compound according to the present invention is used alone or as a mixture, or together with another electron-accepting compound, dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol,
Obtain a developer sheet by applying it to a support such as paper or plastic sheet

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0019

[Correction method] Change

[Correction content]

The yield thus obtained weighed 50 g / m ² coloring agent sheet by coating and drying on the paper so that the solid coating amount of the microcapsule dispersion is 1 m ² per 7 g. 2. An electron-accepting compound according to Preparation invention of the developer sheet 5- (4-t- Amirufuenokishi - sulfonyl) zinc salts of salicylic acid was synthesized in the following manner.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

After dissolving 17.9 g of salicylic acid in 35.3 g of chlorosulfonic acid at 3 ° C. or lower, the mixture was heated at 60 ° C. for 1 hour. This was cooled to 15 ° C. or lower, poured into crushed ice and the precipitated white crystals were collected by filtration, washed with cold water and dried to obtain 19.2 g (yield 63%) of 5-sulfochlorosalicylic acid. .. Chloroform 550 m was obtained by adding 11.1 g of 4-t-amylphenol and 41.1 g of triethylamine.
1-soluble in 5-liter, 5-sulfochloro salicylic acid 1
After adding 9.2 g and reacting at room temperature for 12 hours, the mixture was concentrated under reduced pressure, and tetrahydrofuran (80 ml) and 10% hydrochloric acid (50 ml) were added.
Was added and extracted with ether. Remove ether and remove 17.
Was obtained - (sulfonyl Le 4-t-Amirufuenokishi) salicylic acid (99.6% carboxylic acid content) 2 g (70% yield), mp 157 ° C. of 5. After 7.3 g of this was neutralized with 1N caustic soda, 6.5 g of 25% zinc sulfate solution was added,
The precipitated colloidal precipitate was collected by filtration and dried to obtain 7.6 g (yield 96%) of zinc salt. The zinc content was 8.00% (theoretical value 8.25%).

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

[0021] The 5-(4-t-Amirufuenokishi - scan <br/> sulfo sulfonyl) 5% zinc salt 5g of salicylate polyvinyl alcohol (saponification value of 99%, polymerization degree: 1000) solution 5
Dispersed in 0 g and further kaolin (Georgia Kaolin)
5 g was added and well dispersed to obtain a coating liquid. The resulting coating liquid is weighed 5 so that the zinc salt is 0.7 g per 1 m ^2.
A 0 g / m ² paper was applied and dried to obtain a developer sheet. The color-developing agent sheet thus prepared and the color-developing agent sheet were overlapped to develop a color under a load pressure of 600 kg / cm ² to obtain a black image. The absorption maximum of the visible absorption spectrum of the coloring surface was measured to obtain a coloring density of 1.22.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

[0022] In Example 2 Example 1, 4-t-Ami Rufuenoru instead of 3,5-di -t- butylphenol 20.6g of Likewise melting point 158 ° C. using 5- (3,5-di t- butyl phenoxyethanol sulfonyl) give the salicylic acid 26.8 g.
The yield was 66% and the carboxylic acid content was 98.6%. Similarly, 5- (3.5-di-t-butylphenoxy-sulfo)
A zinc salt of ( nyl) salicylic acid was obtained. The yield was 97% and the zinc content was 7.38% (theoretical amount: 7.46%). The zinc salt in a similar manner using the zinc salt 5.5g was obtained coated dried color developer sheet to paper weighing 50 g / ^{m 2} so as to be 1 m ² per 0.77 g. The color developer sheet thus prepared and the color developer sheet of Example 1 were stacked,
Color was developed under a load pressure of 0 kg / cm ² to obtain a black printed image. The color density was 1.19.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

Example 3 2-anilino-3-methyl-, an electron-donating colorless dye
5 g of 6-N-methyl-N-cyclohexylaminofluorane was dispersed with a 5% aqueous solution of polyvinyl alcohol (50 g) in a ball mill overnight. On the other hand, it is an electron-accepting compound 5- (4-t- amyl off enoki Sea sulfonyl)
10 g of zinc salt of salicylic acid was dispersed with 100 g of 5% aqueous solution of polyvinyl alcohol in a ball mill for a whole day and night, and after mixing these two kinds of dispersion liquid, 20 g of kaolin was added and well dispersed, and 5 g of 50% dispersion liquid of paraffin wax emulsion was added. As a coating liquid. Weighing a coating solution so that the solid content coating amount is 1 m ² per 6 g 50 g / ^{m 2}
The coated paper was obtained by applying the coated paper to the above paper and drying at 60 ° C. for 1 minute.
Heating of coated paper by facsimile 40 mJ /
Color development was performed by heating at ² to obtain a black image. The color density was 1.47.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

Example 4 In Example 3, 5- (4-t-amylphenoxy-
Alternatively 5- (3-sulfonyl) zinc salts of salicylic acid,
5-di t- Buchirufuenokishi - except using sulfonyl) zinc salt of salicylic acid in the same manner as in Example 3 to obtain a heat-sensitive recording paper. This was heated and color-developed in the same manner as in Example 3 to obtain a black image. Color density was 1.45

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

Comparative Example 1 In Example 1, 5- ( 4-t-amylphenoxy-
Except using sulfonyl) 3,5-bis (alpha-methylbenzyl) zinc salts of salicylic acid in place of zinc salt of salicylic acid to obtain a pressure-sensitive recording paper in the same manner as in Example 1. This was color-pressed in the same manner as in Example 1 to obtain a black image. The color density was 1.18.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Comparative Example 2 In Example 3, 5- (4-t-amylphenoxy-
Except for using the bisphenol A in place of the sulfonyl) zinc salt of salicylic acid to obtain a heat-sensitive recording paper in the same manner as in Example 3. This was heated and color-developed in the same manner as in Example 3 to obtain a black image. The color density was 1.25. After exposing these color-developing sheets to sunlight for 1 hour, the absorption maximum of the visible absorption spectrum of the color-developing surface was measured to determine the density. The light resistance was calculated from these values by the following formula and is shown in Table 1. Lightfastness value = [(concentration of color former after exposure to sunlight) / (concentration of color former before exposure to sunlight)] × 100 (%). H. Under high temperature conditions for 24 hours, and at 40 ° C., 90% R.C. H. After standing for 24 hours under high humidity conditions, the absorption maximum of the visible absorption spectrum of the color development surface was measured to determine the concentration, and the heat resistance value and humidity resistance value were calculated in the same manner as the above light resistance value, and the results are shown in Table 1. .. Further, the degree of fogging of the blank area at that time was evaluated, and the results are shown in Table 1.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

[0027]

[Table 1]

Claims (1)

[Claims] 1. A recording material using an electron-donating colorless dye and an electron-accepting compound, wherein at least one compound represented by the following general formula (I) or a polyvalent metal salt thereof is used as the electron-accepting compound. A recording material characterized by the above. General formula (I): In the above formula, Ar represents a substituted or unsubstituted phenyl group or naphthyl group, and the substituent is a halogen atom,
There are alkyl groups, cycloalkyl groups, aralkyl groups, aryl groups, alkoxy groups, alkoxycarbonyl groups, carbamoyl groups, acylamino groups or sulfonamide groups, and X is a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an aralkyl group, aryl. Represents a group, an allyl group or an alkoxy group.