JPS62181361A - Recording material - Google Patents

Abstract

PURPOSE:A recording material useful as pressure-sensitive recording paper, heat-sensitive recording paper, etc., containing a specific phenylenediamine derivative or naphthylenediamine derivative and an acidic substance. CONSTITUTION:The aimed coloring recording material containing (A) a phenylenediamine derivative shown by formula I (ring A-C are benzene ring or naphthalene ring which may contain substituent groups such as halogen, cyano, OH, alkyl, aryl, alkoxy, aryloxy, arylalkoxy, etc.,; H is H atom which is bonded to N atom in parenthesis; R is lower alkyl, aryl or aralkyl which is bonded to N atom in parenthesis; m and n are 0-2 and m+n is 2) or naphthylenediamine (e.g., compound shown by formula II) and (B) an acidic substance (e.g., acid clay, silica gel, zinc chloride, etc.,).

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a recording medium whose main purpose is to be read by a device. In more detail, it relates to historical 3 self-recording bodies that are sensitive to the -long wavelength part of visual rays or near-infrared rays when using self-recording reading devices, and is associated with the Q exhibition of information management systems. This project proposes a recording medium that meets your needs.

and. [Prior art] g. With the recent development of both electronics and information management systems, there is an absorption system that is sensitive to electromagnetic waves with wavelengths ranging from long-wavelength visible light to near-infrared light in 15 minutes. 8 ka, kerah, ah, 1 more yo, 6 oh.

Various proposals have been made for color-forming dyes that are colorless in themselves, but which form pigments that absorb electromagnetic waves in this wavelength range upon contact with acidic substances. That is, as compounds having such properties, phthalide compounds are disclosed in JP-A-51-121,035 and JP-A-51-1.
21,037, JP 51-121,038, JP 55-115.448, JP 55-115,44
No. 9, JP-A-55-115,450, JP-A-55-1
15,451, JP 55-115,452, JP 55-115,456, JP 57-167.97
No. 9, JP-A-58-157.779, JP-A-60-8
．． 364, JP-A No. 60-27,589, thiofluorane-based compounds are known from JP-A-59-148,695, and fluorene-based compounds are known from JP-A-59-199, 757, European Patent Application No. 124377. In addition, the applicant of the present application filed a patent application in 1983 regarding a fluoran compound that forms a dye having the above-mentioned wavelength absorption range.
No. 0-126149 has been filed.

[Problem that the invention seeks to solve]

The present invention converts the dye-forming substance having the above wavelength absorption range into a substance with a much simpler structure than the substances known as color-forming dyes such as phthalide, fluorene, or fluoran dyes. It is something to seek.

[Failure to solve the problem]

The inventors proposed that the general formula (in the formula, ring A, IEJB and ring C are each independently a benzene ring or a naphthalene ring, and they are a halogen atom, a cyano group, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an arylox7 group, arylalkoxy group,
From the group consisting of an alkylcarbonyloxy group, an arylcarbonyloxy group, an amine group, an alkyl-substituted amine group, a pyrrolidino group, a hyphoridino group, an aryl-substituted amine group, and a carbamoyl group which may have an alkyl group or a phenyl group as a substituent It may have one or more selected substituents, H is a hydrogen atom bonded to the nitrogen atom in parentheses, and R is a lower alkyl group, aryl group, or aralkyl group bonded to the nitrogen atom in parentheses. , where m and n are each 0.1″!, only 2 and m + n
The phenylenediamine derivative or naphthylenediamine derivative represented by 2) develops a color when it comes into close contact with an acidic substance, and the coloration occurs because it absorbs electromagnetic waves with wavelengths ranging from the long wavelength region of visible light to the near-infrared region. discovered and carried out the present invention, and the present invention relates to the general formula CI
This is a recording material that contains a phenylene diamine derivative or a naphthylene diamine derivative mixed with ( ) and an acidic substance, and can utilize the color development from the long wavelength region of visible light to the near infrared region that is produced by the reaction between the two. Color development here refers to the production of substances that absorb electromagnetic waves in the wavelength range above.8
I have a stomach ache.

The mechanism by which the compound represented by the general formula m develops color due to acidic substances is currently unknown, but the color becomes darker over time (approximately 50 hours after close contact with acidic substances); Alternatively, since color development is sometimes accelerated by ultraviolet light, it is inferred that some kind of oxidation reaction occurs in the presence of acidic substances.

Examples of acidic substances suitable for coloring the compound represented by the general formula (1) include inorganic acidic substances such as acid clay, activated clay, silica gel, zinc chloride, aluminum chloride, sulfamic acid, etc. Sulfonic acids such as sulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, etc., cylicic acid, tartaric acid, citric acid, palmitic acid, stearic acid, methacrylic acid, maleic acid, fumaric acid, benzoic acid, toluic acid, phthalic acid,
2,6-dichlorobenzoic acid, 4-tert-butylbenzoic acid, 4-hydroxybenzoic acid, salicylic acid, diimpropylsalicylic acid, 3-phenylsalicylic acid, 6-cyclohexylsalicylic acid, 3+5-"-tert-
Butylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3-phenyl-5-(α,α-dimethylbenzyl)
Salicyl l[,3,5-di(2-methylbenzyl)salicylic acid, 3-cumylsalicylic acid, gallic acid, 2-hydroxy-1-benzyl-3-naphthoic acid, 2-acyloxy-1-naphthoic acid, 1- Carboxylic acids such as acyloxy-2-naphthoic acid and 3-anroxy-2-naphthoic acid, salts of these carboxylic acids with metals such as zinc, calcium, magne/lamb, aluminum, and titanium, phthalic anhydride, benzoic anhydride, Toluic anhydride, O- anhydride
Sulfobenzoic acid, O-sulfophthalimide, xanthic acid, water-insoluble polymer having a carboxy group or/and round sulfonic acid group in the molecule, or p-phenylphenol-formalin 1fHLp-butylphenol-
Examples include phenolic resin color developers such as acetylene resin, mixtures of these phenol resin color developers and the above carboxylic acid metal salts, etc. Heat-sensitive recording paper can be produced using fluoran compounds and other conventional color-forming dyes. Phenolic color developers (for example, bisphenol solution, etc.) commonly used during production produce weak color.

The compound represented by the general formula (1) is disclosed in JP-A-54-987
No. 26 or JP-A No. 55-38311, etc., and some of the compounds are commercially available as antioxidants for rubber and the like.

Specific examples of substituents that the compound represented by formula (1) may have are listed below. In the substituents bonded to ring A, ring B and ring C, the alkyl group directly bonded to the six rings, the alkyl carbonyloxy group, and the alkyl group of the alkyl-substituted amino group have a side chain having 1 to 8 carbon atoms. It is an alkyl group which may have a substituent, and the alkoxy group directly bonded to the three rings and the alkoxy group of the arylalkoxy group are alkyl groups which may have a side chain having 1 to 5 carbon atoms. and the aryl group of the aryl group, aryloxy group, arylcarbonyloxy group, and aryl-substituted amine group directly bonded to the three rings is a phenyl group or/and a naphthyl group; an alkyl group optionally having a side chain having 1 to 5 carbon atoms;
An alkoxy group which may have a side chain having 1 to 5 carbon atoms, an amine group which may have an alkyl group which may have a side chain having 1 to 5 carbon atoms as a substituent, a halogen atom, or It is an aryl group which may be substituted with one or more substituents selected from the group consisting of hydroxyl groups. The substituents that may be substituted for the carbamoyl group are the same as above. The lower alkyl group represented by substituent R1 has 1 to 5 carbon atoms.
an alkyl group which may have a side chain of an alkyl group which may have a side chain having 1 to 5 carbon atoms, an alkyl group which may have a side chain having 1 to 5 carbon atoms, and an alkyl group which may have a side chain having 1 to 5 carbon atoms as a substituent. An alkylene group which may be substituted with one or more substituents selected from the group consisting of an amino group, a rogen atom or a hydroxyl group, and an aralkyl group which may have a side chain having 1 to 6 carbon atoms. A phenyl group is bonded to the phenyl group, and the phenyl group is an alkyl group which may have a side chain having 1 to 5 carbon atoms, an alkoxy group which may have a side chain having 1 to 5 carbon atoms, or a carbon It may be substituted with one or more substituents selected from the group consisting of an amino group, a hydrogen atom, or a hydroxyl group. Good too.

Table 1 shows the melting points of some of these compounds and the maximum absorption wavelength of electromagnetic waves absorbed by the color developed by the acidic substance. These colors were developed in Example 1, and the color tones observed with the naked eye were slightly dull pale blue to pale green, and became darker with the passage of time.

1 to NH (cnNH [phase] 155~1
37 7502 Ho-@-+54N1(-@
141-145 ao.

3CH50shaNH-o-NH-ol 26.8~128
．． 08304C2H5 Yurisha 1aT-@148~
157 8305 H>sa+-@ 143°5~146. . 750° horse) Do□sha6NH-@IC16,6~108 69
57 tert-C4H9CO-○-@-NI(-@
-NH 102-106 7208NH2 (瀘1◎-
NH-@ 156.5-160 8669
@-NH-@-+℃zus-<◎ 196.5~1
'? s, 51D [1519CH3 + NH + liver [phase]
145-148 78224 CH30 (Japanese Peso) N
H-@-NH@ 102025 0-NH-
@-NH-@-NH-@-NH@247~249 93
Table 2 shows an example in which the color of the compound represented by formula (1) becomes darker over time due to an acidic substance. Second
The table shows the reflectance (%) at each wavelength (measured using a spectrophotometer-integrating sphere) after 1 hour and 24 hours from the coloring operation in Example 1 for the compounds in Table 1 A4 and Ya8. ). Note that these reflection curves are shown in FIGS. 1 and 2.

Table 2 (820nm) A 4 1h 33.520.520.024.02
4h 14.510.0 10.013.0 (866
nm) Condition 8 1h 56.526.517.024.024
h 13.5 a8 7. Specific forms of recording materials that utilize color development by acidic substances of the compound represented by the general formula (1) of OaO include, for example, pressure-sensitive copying materials, heat-sensitive recording materials, heat-sensitive transfer recording materials, and toners containing acidic substances that are developed. Examples include electrophotographic ultrasonic recording materials, photosensitive recording materials, electron beam recording materials, discharge recording materials, stamping materials, stamp inks, and typewriter ribbons used as agents. As the base material for these recording materials, polymeric materials such as paper, synthetic paper, cloth, nonwoven fabric, synthetic resin film, and synthetic resin plate are often used.

It goes without saying that the compound represented by the general formula (11) can be used alone, but it is also possible to use a mixture of these compounds.
It is also possible to mix and use color-forming dyes that absorb in the near-infrared region during color development as described in the above-mentioned literature.

Conventionally known conventional color-forming dyes include, for example, crystal violet lactone, penzoylliucomethylene blue, 5(or 7)-(1-octyl-2-methylindole-5yl)-5(or 7)-(4-diethylamino -2-ethoxyphenyl) -5,7'-dihibirofuro(3,4-b)-pyridin-7(or 5)-one, a blue coloring dye, 3-diethylamino-5-i
h) I/-7-dibenzylaminofluorane, 3-N-
Green coloring dyes such as inbutyl-ethylamino-7-phenylaminofluorane, 6-diethylamino-6-
Methylfluorane-chlorofluorane, 5-N-inbutyl-
ethylamino-6-methyl-7-chlorofluorane, 6
-cyclohexylamino-6-chlorofluoran/red color-forming dyes such as 6-diethylamino-6-methyl-ph-phenylaminofluoran, 5-N-methyl-cyclohexylamino-6-methyl-7-phenylaminofluoran , 3-N-methyl-n-i ropylamino-6-methyl-7-phenylaminofluorane, 6-N-iso is phthyl-ethylamino-6-methyl-7-phenylaminofluorane, 6-dinithylamino-7- Typical examples include black color-forming dyes such as m-trifluoromethylphenylaminofluorane and 5-di-n-butylamine-7-chlorophenylaminofluorane, but are not limited to these. It's not a thing.

The method for using the compound represented by the general formula (1) in pressure-sensitive copying paper is the same as that for general fluoran compounds, and is disclosed in US Pat. No. 2,548.365, USP No.
No. 548.366, No. 2,800,457, No. 2,8
Pressure-sensitive copying paper can be produced by the method described in Japanese Patent Application Laid-open No. 00,458, Japanese Patent Application Laid-open No. 58-112.041, or Japanese Patent Application Laid-Open No. 58-139,738.

The compound represented by the general formula (1) is, for example,
No. 27,579, Special Publication No. 43-4,160, Special Publication No. 4
5-14,039, JP-A-59-7.087, or JP-A-59-106,992, etc., it can be used for producing thermal recording paper. , the compound represented by general formula (1) and the acidic substance as a color developer do not necessarily have to be contained in the same coating layer, but may be contained separately in two layers stacked one above the other. may be included in

As the color developer, it is preferable to use a substance that is more acidic than the complexion agents used in ordinary heat-sensitive recording paper, such as the acidic substances listed above. Therefore, when manufacturing thermal recording paper using a compound represented by general formula (1) in combination with a normal color-forming dye or/and a color-forming dye that also absorbs in the near-infrared region when coloring, it is necessary to It is desirable that the color dye and the color developer come into direct contact with each other before the coloring operation.
Examples of this method include a method in which the entire color-forming dye is encapsulated in microcapsules, or a method in which the color-forming dye and the color developer are not mixed and are coated on the support as separate layers. A suitable isolation layer may also be provided between the two layers).

As mentioned above, the color development of the compound represented by the general formula (1) by an acidic substance can occur when the acidic substance is a substance commonly used in the production of thermal recording paper, such as bisphenol A. Although it is weak, the color develops in this case as well with the passage of time or sunlight exposure. Therefore, the compound of general formula (1) can be used in combination with a conventional color-forming dye and/or a dye that also absorbs in the near-infrared region at the time of color development, and an acidic substance (for example, bisphenol A) commonly used in the production of thermal recording paper. , p-hydroxybenzoyl, 4-hydroxy-4'
-) -Floboxydiphenylsulfone, 4-human'roxy4'-n-phthoxydiphenylsulfone, his(p-hydroxyphenylthioethoxy)-methylene, etc., but are not limited to these) If heat-sensitive recording paper is manufactured using the compound as a color developer according to the usual method, the compound of general formula (1) will act as an image stabilizer and will be extremely durable against the progress of the purpose or irradiation with light. It is possible to produce thermosensitive recording paper. Since the gradually deepening color of the compound of general formula (1) also has absorption in the near-infrared region, this substance is an image stabilizer for the chromogenic dye having absorption in the near-infrared region described in the above-mentioned literature. It is very effective as It goes without saying that the image stabilizing effect of the compound of general formula (1) can also be utilized in pressure-sensitive copying paper.

In order to use the compound represented by the general formula (1) in thermal transfer, for example, JP-A No. 58-212,985, JP-A No. 59-Sho.
33.185, JP-A-59-42,995, or JP-A-59-225,986; -96,137, JP-A-1 Old 48101.
935 or Japanese Patent Application Laid-open No. 49-11,344, and for example, for use in child photography, the method described in Japanese Patent Application Laid-Open No. 52-24,530 or Japanese Patent Application Publication No. 52-56.9
In addition to the method described in Publication No. 32, for further use in discharge recording, Japanese Patent Application Laid-Open No. 59-79.7-4 or Japanese Patent Application Publication No. 5
It can be used according to the method described in 9-124.888.

Further, in order to use a compound represented by the general formula (11) for photosensitive recording, for example, Japanese Patent Publication No. 38-24188, Japanese Patent Publication No. 4
5-10550, Japanese Patent Publication No. 49-45978, Japanese Patent Publication No. 50-8 (1120), Japanese Patent Publication No. 126228-1980,
JP-A-52-141633 or JP-A-54-14
According to the method described in Publication No. 7829, French Patent No. 2120922 is used for ultrasonic recording, Belgian Patent No. 7959986 is used for electron beam recording, and Japanese Patent Publication No. 49-69'52 is used for electrostatic recording. For use in photosensitive printing materials, it can be used in accordance with the method described in JP-A-48-12104.

The recording paper produced according to these methods can be provided with a storage layer on its surface, if necessary, and can also be provided with an adhesive layer on its back surface to make it convenient to use as a label.

Recording materials produced according to these methods are used, for example, in copies of books, police boxes, etc., electronic computers, facsimile machines, bar codes, ticket vending machines, labels, etc., and are also used to record information input into holes, etc. It can be applied to a wide range of applications such as anti-counterfeiting, anti-copying, unlocking devices, and laser discs, where information on records cannot be seen with the naked eye.

Example 1 0.1,9 of the phenylenediamine derivatives (compound numbers 1 to 25) listed in Table 1 were dissolved in 20 ml of toluene,
Soak the clay-coated base paper for pressure-sensitive copying paper used in pressure-sensitive copying paper made by Fuji Photo Film Co., Ltd. in this solution for 15 seconds, and hang it on a bench for 10 seconds to let the adhering solution flow down. Afterwards, both sides were wiped with filter paper and left to evaporate the solvent. The paper used had a slightly dull pale blue to pale greenish-blue color. Using a spectrophotometer/integrating sphere, the reflection curve of the coloring surface of each coloring paper was measured to determine the maximum absorption wavelength. The values are listed in Table 1.

Example 2 Table 1, phenylenediamine derivatives from Compound Shop Otsu 4.
Ole alkyl diphenylmethane (Nisseki Chemical Co., Ltd.)
Hysol SAS 296 J) 50.09 and diisopropylnaphthalene (Kleno Kagaku Co., Ltd. r
KMC-113J) 36.0 g was mixed and heated to dissolve, stirred at 90°C for 10 minutes, and cooled (Liquid A).

On the other hand, a 10% aqueous solution of sulfonic acid-modified polyvinyl alcohol (Nippon Gosei Kagaku Kogyo Co., Ltd. "GOHSENOL CKS-50J average degree of polymerization about 300, degree of saponification 97%, degree of modification 10% mol%)" 30.O11 ethylene maleic anhydride copolymer (Monsanto Co., Ltd.) Mix 15.0.9 of a 10% aqueous solution of EMA-31J) and 6 ml of water, further add and dissolve 5.0 g of urea and 0.5 g of resorcin, and then adjust to pH 3 using 20 g of aqueous caustic soda solution. , 4 (liquid B).

Add liquid A to Bi and use a homomixer to mix 9.000
Stir at rpm for 2 minutes to form an emulsion, then 3 minutes.
9,000 by adding 5% formalin water soluble i14.0.9
After stirring at rpm for 6 minutes, increase the rotation speed to 8,000.
The stirring was continued at a temperature of 60-65° C. for 60 minutes. After discontinuing stirring with the homomixer and cooling the liquid temperature to 40°C, 28% aqueous ammonia was added to adjust the pH to 75 to obtain a microcapsule suspension.

This suspension (temperature below 30°C) 27.0.9, small starch 3.5, 9.8% small wheat flour liquid 8.5 and water 34
．． A coating solution was prepared by mixing and stirring 0 ml at room temperature using a stirrer for 30 minutes.

This coating solution was applied to white cardboard using a wire bar Ai 12, and dried with warm air at 60° C. for 5 minutes to prepare an upper sheet of pressure-sensitive copying paper.

This upper sheet was placed on a clay-coated lower sheet for pressure-sensitive copying, and color was developed under pressure. The color tone was a slightly dull pale blue.

Example 5 Table 1, 7-unitinediamine derivative 4 of compound A1 14.
OF, 4.5 g of a 15% aqueous solution of polyvinyl alcohol (Kuraray Co., Ltd., "Kran-105J") 41.591 clay (RUW-90J, Engelno Ruto Co., Ltd.) and 40.0 # of pure water were added to glass beads (diameter 1~ 1.5M
) 150.9 in a 250 rILt polyethylene bottle, tightly capped, and shaken using a Red Devi 1 bind conditioner (manufactured by Bay Company) at a frequency of 630 times/min for 5 hours, the glass beads were removed, and the above phenylenediamine derivative was removed. An aqueous suspension was obtained.

This aqueous suspension was applied onto the clay-coated surface of a clay-coated lower paper for pressure-sensitive copying using a wire bar A18 and dried to prepare a heat-sensitive recording paper.

When this thermosensitive recording paper was heated at 150° C. for 5 seconds using a dry heat tester (manufactured by Kinno Kagaku Kikai Co., Ltd.), the heated area developed a slightly dull light green-blue color. After one hour, the reflection spectrum of this colored part was measured, and it was found that the wavelength was 800.
The reflectance at nm was 20.2%.

Example 4 In place of the phenylenediamine derivative 4.0I of Table 1 compound w/) A6 used in Example 2, 5-N-methyl-cyclohexylamino-6-methyl-7-, which is a black coloring dye, was used. A coating liquid containing a microcapsule suspension containing a color-forming dye was prepared in the same manner as in Example 2 using 4.0 g of phenylaminofluorane.

This coating solution was applied onto the clay-coated surface of the clay-coated lower sheet for pressure-sensitive copying paper using a Wire Par & 12 and dried, and then the aqueous suspension prepared in Example 3 was further applied onto that surface. The liquid was applied using a wire parser 18 and dried. When this coated paper was heated using a dry heat tester in the same manner as in Example 3, the heated portion developed a black color, and the near-infrared reflection state was almost the same as in Example 3.

Example 5 Phenyldiamine derivative used in Example 3 14.0
In place of #, phenylenediamine derivative 10.0 of Compound 9 in Table 1 and 3-phenylaminophenylamino-
Production of thermal recording paper in the same manner as in Example 3 using a mixture of 6-methyl-7-chlorofluorane and 4.0.9;
Color development was performed by heating. The color tone was greenish-black. 24
After some time, the reflectance of the colored part was measured, and the reflectance was 8% at 600°C, 8% at 700°C, and 80% at 700°C.
It was 5 cm at 0°C and 3 cm at 900 nm.

Example 6 Table 1, &6 phenylenediamine derivative 0.06g1
Tetrabromomethane 0.066! 0.2 g of acetic acid cellulose and 1.1 g of acetone. It was dissolved in S and P, applied to a transparent polyethylene film, and dried.

Further, the compound shown in Table 1, No. 12 was applied to a polyethylene film in the same manner and dried.

When these polyethylene films were irradiated with a 400 W high-pressure mercury lamp from a distance of 20 cIrL for 1 minute, both of them developed a slightly dull pale blue color.

Table 2 shows the reflectance (correspondence) at various wavelengths of color development.

Table 2 Compound 3 5 4 5 Compound shop 12
6 5 6

[Brief explanation of drawings]

FIG. 1 shows the reflection spectrum of the compound of A4 in Table 1, and FIG. 2 shows the coloring of the compound of A8 in Table 1 with clay (Example 1). In both FIGS. 1 and 2, the curve a is the reflection curve 1 hour after the coloring operation, and the curve b is the reflection curve 24 hours later. Patent applicant: 2 people other than Nippon Sokako Co., Ltd.

Claims (1)

[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, ring A, ring B, and ring C are each independently a benzene ring or a naphthalene ring, and they are halogen atoms,
Cyano group, hydroxyl group, alkyl group, aryl group, alkoxy group, aryloxy group, arylalkoxy group, alkylcarbonyloxy group, arylcarbonyloxy group, amino group, alkyl-substituted amino group, pyrrolidino group, piperidino group, aryl-substituted amino group and a carbamoyl group which may have an alkyl group or a phenyl group as a substituent, and H is a hydrogen atom bonded to the nitrogen atom in the cutlet. , R is a lower alkyl group, aryl group or aralkyl group bonded to the nitrogen atom in the cutlet, m and n
are 0, 1 or 2 respectively and m+n is 2)
A color-forming recording medium containing a phenylenediamine derivative or a naphthylenediamine derivative represented by the formula and an acidic substance.