JP2887288B2 - Recording material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material, and more particularly to a recording material having excellent coloring properties.

[Conventional technology]

Between a colorless or pale leuco dye and a developer,
Various recording materials utilizing a coloring reaction by heat, pressure and the like have been proposed.

One of the heat-sensitive recording materials does not require complicated processing such as development and fixing, and can be recorded in a short time with a relatively simple device, has less noise, and has further advantages such as lower cost. Thus, it is useful as various recording materials for electronic computers, facsimile machines, ticket vending machines, labels, recorders and the like.

As the color-forming dye used for the heat-sensitive recording material, for example, a colorless or light-colored leuco dye having a lactone, lactam, or spiropyran ring is used. Recording materials using this leuco dye and a developer are widely used because of their high image density and high whiteness of the background.

On the other hand, as the demand for the thermal recording method has increased in recent years,
There has been an increasing demand for faster recording. For this reason, it is strongly desired to develop not only a high-speed recording apparatus but also a recording material that can cope with this.

Also, especially in fields where the reliability of recorded images is important,
It is required to provide an image with high stability to a plasticizer contained in fats and oils, plastics and the like.

[Problems to be solved by the invention]

In order to respond to high-speed recording, as a high-sensitivity developer, for example, p-hydroxybenzoic acid ester is disclosed in JP-A-56-144193 and the like, and hydroxynaphthoic acid ester is disclosed in JP-A-59-22793 and the like. Has been proposed. Furthermore, Japanese Patent Application Laid-Open No. 59-165680 discloses that a thioester compound is used as a color developer, but a recording material using the compound has high fastness to oils and fats in an image area, but has high sensitivity and high sensitivity. Is hard to say. There have also been various proposals for increasing the sensitivity by adding various heat-fusible substances.
For example, a naphthol derivative is proposed in JP-A-58-87094 and the like, and benzylbiphenyl and the like are proposed in JP-A-60-82382 and the like.

However, recording materials using these developers or heat-fusible substances are not yet sufficient in terms of color sensitivity, background whiteness, storability (image fading, generation of white powder, etc.). Hard to say.

Further, in order to enhance the stability of a conventionally recorded image, for example, a heat-sensitive coloring layer containing a large amount of water-resistant and chemical-resistant resin,
A heat-sensitive coloring layer containing a resin that is cured by heat or light or a layer having a resin protective layer formed on the surface has been proposed. However, these methods increase the cost due to complicated processing and increase the thermal response. There is a problem that the property is reduced. On the other hand, as proposals for improving the stability of images by improving color developers, JP-A-58-20493, JP-A-58-82788, and JP-A-59-96
No. 991, No. 60-13852 and the like using a derivative of bisphenol S; Japanese Unexamined Patent Publication No. 58-160191 and the like using trisphenols; and Japanese Unexamined Patent Publication No. 57-6795 and No. 61
There is a method using a metal carboxylate such as -47292, etc., all of which are sufficient in terms of background coloration, background discoloration, background color development by a plasticizer or a solvent, or image stability against oil or a plasticizer. It is hard to say that it is.

The first object of the present invention is to provide a recording material that is excellent in color sensitivity and suitable for high-speed recording, and has a high background whiteness. A second object is to provide an excellent recording material.

[Means for solving the problem]

According to the present invention, in a recording material utilizing a color-forming reaction between a colorless or light-colored leuco dye and a color developer that causes the leuco dye to develop color upon contact, the following general formulas (I) and (I) are used as the color developer. A recording material characterized by using at least one of the phenolic compounds represented by II).

(Wherein R ₁ and R ₂ represent an alkyl group, an alkoxy group, an acyl group, an oxycarbonyl group or a halogen atom, And Represents an aromatic ring, 1 represents an integer of 0 to 3, m represents an integer of 0 to 5, and n represents an integer of 1 to 10, respectively. ) (Wherein R ₁ and R ₂ represent an alkyl group, an alkoxy group, an acyl group, an oxycarbonyl group or a halogen atom, And Represents an aromatic ring, k is 1-2, l is 0-3,
m represents an integer of 0 to 4 and n represents an integer of 1 to 10, respectively. The recording material of the present invention comprises, as a developer, the compound represented by the general formula (I)
By using the compound represented by the formula (1), the color developing sensitivity is excellent and it is suitable for high-speed recording, and by using the compound represented by the formula (II), the image stability is excellent.

The following formulas (I) and (II) used in the present invention
Specific examples of the phenolic compound represented by are shown below, but the present invention is not limited thereto. The compound
Nos. 17 to 19, 26 to 34, and 43 to 45 are reference examples.

The leuco dyes used in the present invention are applied alone or as a mixture of two or more types. As such leuco dyes, those applied to this type of recording material are arbitrarily applied. Leuco compounds of dyes such as methane, fluoran, phenothiazine, auramine, spiropyran and indolinophthalide are preferably used. Specific examples of such leuco dyes include, for example, those shown below.

3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone), 3,3-bis (p-dimethyl Aminophenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) phthalide, 3-cyclohexylamino-6-chlorofurf Oran, 3-dimethylamino-5,7-dimethylfluoran, 3- (N-methyl-N-isobutylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamylamino ) -6-Methyl-7-anilinofluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-7-methylfluora 3-diethylamino-7,8-benzfluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3- (Np-tolyl-N-ethylamino) -6-methyl-7-aniline Linofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 2- {N- (3'-trifluoromethylphenyl) amino} -6-diethylaminofluoran, 2- {3,6-bis (Diethylamino) -9- (o-chloroanilino) xanthyl lactam benzoate, 3-diethylamino-6-methyl-7- (m-trichloromethylanilino) fluoran, 3-diethylamino-7- (o-chloroanilino) fluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran, 3-N-methyl-N-amylamino-6-methyl-7
-Anilinofluoran, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl -7- (2 ', 4'-
Dimethylanilino) fluoran, 3- (N, N-diethylamino) -5-methyl-7-
(N, N-dibenzylamino) fluoran, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindolino-
Pyrirospiran, 6'-bromo-3'-methoxy-benzoindolino-
Pyrirospiran, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'-chlorophenyl) phthalide, 3- (2'-hydroxy-4'-dimethylaminophenyl)- 3- (2'-methoxy-5'-nitrophenyl) phthalide, 3- (2'-hydroxy-4'-diethylaminophenyl) -3- (2'-methoxy-5'-methylphenyl) phthalide, 3- ( 2'-methoxy-4'-dimethylaminophenyl) -3 '-(2'-hydroxy-4'-chloro-5'
-Methylphenyl) phthalide, 3-morpholino-7- (N-propyl-trifluoromethylanilino) fluoran, 3-pyrrolidino-7-trifluoromethylanilinofluoran, 3-diethylamino-5-chloro-7- ( N-benzyl-trifluoromethylanilino) fluoran, 3-pyrrolidino-7- (di-p-chlorophenyl) methylaminofluoran, 3-diethylamino-5-chloro-7- (α-phenylethylamino) fluoran, 3- (N-ethyl-p-toluidino) -7- (α-phenylethylamino) fluoran, 3-diethylamino-7- (o-methoxycarbonylphenylamino) fluoran, 3-diethylamino-5-methyl-7- ( α-phenylethylamino) fluoran, 3-diethylamino-7-piperi Nofuruoran, 2-chloro-3-(N-Mechirutoruijino) -7-
(Pn-butylanilino) fluoran, 3- (N-methyl-N-isopropylamino) -6
Methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluoran, 3,6-bis (dimethylamino) fluorenespiro (9,
3 ')-6'-dimethylaminophthalide, 3- (N-benzyl-N-cyclohexylamino)-
5,6-benzo-7-α-naphthylamino-4′-bromofluoran, 3-diethylamino-6-chloro-7-anilinofluoran, 3-N-ethyl-N- (2-ethoxypropyl) amino -6-methyl-7-anilinofluoran, 3-N-ethyl-N-tetrahydrofurfurylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-mesitidino-
4 ', 5'-benzofluoran, 3- (p-dimethylaminophenyl) -3- {1,1-
Bis (p-dimethylaminophenyl) ethylene-2-yl} phthalide, 3- (p-dimethylaminophenyl) -3- {1,1-
Bis (p-dimethylaminophenyl) ethylene-2-yl} -6-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3- (1-p
-Dimethylaminophenyl-1-phenylethylene-2
-Yl) phthalide, 3- (p-dimethylaminophenyl) -3- (1-p
-Dimethylaminophenyl-1-p-chlorophenylethylene-2-yl) -6-dimethylaminophthalide, 3- (4'-dimethylamino-2'-methoxy) -3
-(1 "-p-dimethylaminophenyl-1" -p-chlorophenyl-1 ", 3" -butadiene-4 "-yl) benzophthalide, 3- (4'-dimethylamino-2'-benzyloxy) -3 -(1 "-p-dimethylaminophenyl-1"
-Phenyl-1 ", 3" -butadiene-4 "-yl) benzophthalide, 3-dimethylamino-6-dimethylamino-fluorene-9-spiro-3 '-(6'-dimethylamino) phthalide, 3,3- Bis {2- (p-dimethylaminophenyl)-
2- (p-methoxyphenyl) ethenyl} -4,5,6,7-
Tetrachlorophthalide, 3-bis {1,1-bis (4-pyrrolidinophenyl) ethylene-2-yl} -5,6-dichloro-4,7-dibromophthalide, bis (p-dimethylaminostyryl) -1-naphthalenesulfonylmethane and the like.

Further, in the present invention, a phenolic compound represented by the above general formula is used as a developer, and further, if necessary, various compounds having an electron accepting property, for example, a phenolic compound, a thiophenolic compound, a thiourea derivative, Organic acids and metal salts thereof can be used in combination, and specific examples thereof include the following.

4,4'-isopropylidenebisphenol, 4,4'-isopropylidenebis (o-methylphenol), 4,4'-secondarybutylidenebisphenol, 4,4'-isopropylidenebis (2-tert-butylphenol), 4,4'-cyclohexylidenediphenol, 4,4'-isopropylidenebis (2-chlorophenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis ( 4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl-)
2-methylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-
Tertiary-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-
Cyclohexylphenyl) butane, 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-diphenolsulfone, 4-isopropoxy-4'-hydroxydiphenylsulfone, 4-benzyloxy-4 '-Hydroxydiphenyl sulfone, 4,4'-diphenol sulfoxide, isopropyl P-hydroxybenzoate, benzyl P-hydroxybenzoate, benzyl protocatechuylate, stearyl gallate, lauryl gallate, octyl gallate, 1,3-bis (4-hydroxyphenylthio) -propane, 1,3-bis (4-hydroxyphenylthio) -2-hydroxypropane, N, N'-diphenylthiourea, N, N'-di (m-chlorophenyl) thiourea , Salicylanilide, 5-chloro-salicylanilide, bis- (4 (Hydroxyphenyl) acetic acid methyl ester, bis- (4-hydroxyphenyl) acetic acid benzyl ester, 1,3-bis (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, 2,4 '-Diphenolsulfone, 2,2'-diallyl-4,4'-diphenolsulfone, 3,4-dihydroxy-4'-methyldiphenylsulfone, zinc 1-acetyloxy-2-naphthoate, 2-acetyl Zinc oxy-1-naphthoate, zinc 2-acetyloxy-3-naphthoate, α, α-bis (4-hydroxyphenyl) -α-methyltoluene, antipyrine complex of zinc thiosilane, tetrabromobisphenol A, Tetrabromobisphenol S and the like.

In order to produce the recording material of the present invention, a leuco dye, a developer and an auxiliary component may be bonded and supported on a support. As the binder in this case, various conventional binders can be appropriately used, and specific examples thereof include the following.

Polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylamide / acrylate copolymer, acrylamide / acrylate /
Water-soluble polymers such as methacrylic acid terpolymer, styrene / maleic anhydride copolymer alkali salt, isobutylene / maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, casein, and polyacetic acid Vinyl, polyurethane, polyacrylate,
Emulsions such as polymethacrylic acid esters, vinyl chloride / vinyl acetate copolymers, ethylene / vinyl acetate copolymers, and latexes such as styrene / butadiene copolymers and styrene / butadiene / acrylic copolymers.

When a thermosensitive recording material is obtained according to the present invention, various heat-fusible substances can be used as a heat sensitivity improver, if necessary, and specific examples thereof include the following compounds.

Fatty acids such as stearic acid and behenic acid, fatty acid amides such as stearic acid amide and palmitic acid amide, fatty acid metal salts such as zinc stearate, aluminum stearate, calcium stearate, zinc palmitate and zinc behenate, p-benzyl Biphenyl, terphenyl, triphenylmethane, benzyl p-benzyloxybenzoate, β-benzyloxynaphthalene, phenyl β-naphthoate, phenyl 1-hydroxy-2-naphthoate, methyl 1-hydroxy-2-naphthoate Ester, diphenyl carbonate, dibenzyl terephthalate, dimethyl terephthalate, 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dibenzyloxynaphthalene, 1,2-bis (phenoxy) ethane , 1,2-bi (3-methylphenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane, 1,4-bis (phenoxy) butane, 1,4-bis (phenoxy) -2-butene, 1,2-bis (4-methoxyphenylthio) ethane, dibenzoylmethane, 1,4-bis (phenylthio) butane, 1,4-bis (phenylthio)
-2-butene, 1,2-bis (4-methoxyphenylthio) ethane, 1,3-bis (2-vinyloxyethoxy)
Benzene, 1,4-bis (2-vinyloxyethoxy) benzene, p- (2-vinyloxyethoxy) biphenyl, p-aryloxybiphenyl, p-propargyloxybiphenyl, dibenzoyloxymethane, 1,3-di Benzoyloxypropane, dibenzyl disulfide,
1,1-diphenylethanol, 1,1-diphenylpropanol, p- (benzyloxy) benzyl alcohol,
3-diphenoxy-2-propanol, N-octadecylcarbamoyl-p-methoxycarbonylbenzene, N
-Octadecylcarbamoylbenzene and the like.

In the case of obtaining a thermosensitive recording material according to the present invention, together with a leuco dye and a developer, if necessary, auxiliary additives commonly used in this type of thermosensitive recording material, such as a filler and a surfactant, are used in combination. can do. In this case, as the filler, for example, other than inorganic fine powder such as calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, surface-treated calcium and silica, etc. Organic fine powder such as urea-formalin resin, styrene / methacrylic acid copolymer, and polystyrene resin. Further, the layer structure may be a single layer or a multilayer, and an over layer, an under layer, and a back layer can be provided as necessary.

The developer in the present invention can also be used as a pressure-sensitive recording material, and a pressure-sensitive recording material using the developer can be easily prepared by a conventionally known method.

〔The invention's effect〕

The recording material according to claim 1, wherein the phenolic compound represented by the general formula (I) is used as a color developer, is excellent in color density and sensitivity and high in background coloration. Further, the recording material of claim (2) using the phenolic compound represented by the general formula (II) is excellent in image stability.

〔Example〕

Next, the present invention will be described in more detail by way of examples. All parts and percentages shown below are based on weight.

Examples 1 to 3 and Comparative Example 1 The following mixtures were each pulverized in a magnetic ball mill for 2 days to prepare [Solution A], [Solution B] and [Solution C].

[A liquid]

3- (N-methyl-N-cyclohexyl) amino-6
-Methyl-7-anilinofluorane 20 parts 10% aqueous solution of polyvinyl alcohol 20 parts Water 60 parts [Solution B] Phenolic compound in Table 1 20 parts 10% aqueous solution of polyvinyl alcohol 20 parts Water 60 parts [Solution C 20 parts of calcium carbonate 20 parts of a 5% aqueous solution of methylcellulose 20 parts of water 60 parts of [solution A] 10 parts, [solution B] 30 parts, [solution C] 30 parts and isobutylene / maleic anhydride copolymer 20% alkali a thermosensitive coloring layer forming liquid by mixing 10 parts of an aqueous solution, which dye deposition amount after drying on a high-quality paper having a basis weight of 50 g / m ² is then applied and dried so that 0.5 g / m ² a thermosensitive coloring layer After the application, the surface of the layer was calendered so that the surface smoothness became 500 to 600 seconds to prepare a heat-sensitive recording material.

The thermal recording material obtained as described above was printed at a voltage of 13.3 V with a thermal printer of Matsushita Electronic Components Co., Ltd., and the density was measured with a Macbeth densitometer RD-914. Table 1 shows the results.

Examples 4 to 6 and Comparative Examples 2 to 3 In the same manner as in Example 1 except that the phenolic compounds described in Table 2 were used instead of the phenolic compounds in [Solution B] in Example 1. A heat-sensitive recording material was prepared.

Next, for the obtained heat-sensitive recording material, manufactured by Toyo Seiki Seisakusho, using a thermal gradient tester, a temperature of 150 ° C., a pressure of 2 kg / cm ² ,
Print under the condition of 1 second, and measure the image density with Macbeth densitometer RD
-914 (filter: W-106), and the printed sample was tested for plasticizer resistance and oil resistance as follows. Table 2 shows these results.

Plasticizer resistance: Reagent adipate di (2) manufactured by Tokyo Chemical Industry Co., Ltd.
-Ethylhexyl) was applied to a printing screen, and the density of the image area after left at room temperature for 1 hour was measured.

Oil resistance: Cotton seed oil was applied to the printing surface, and the density of the image area after storage at 40 ° C. under dry conditions for 24 hours was measured.

In addition, the concentration measurement after each of the above preservation tests was also performed using a Macbeth densitometer RD-914 (filter: W-106).

From the results in Table 1, it can be seen that the heat-sensitive recording material of claim (1) is extremely excellent in high-speed recording properties, and from the results in Table 2, the heat-sensitive recording material of claim (2) is an image. It can be seen that it is an excellent one with less fading due to the plasticizer and oil in the part.

Continuation of the front page (56) References JP-A-57-167296 (JP, A) JP-A-57-146689 (JP, A) JP-A-63-203375 (JP, A) JP-A-58-224787 (JP) , A) JP-A-60-147388 (JP, A) JP-A-63-173687 (JP, A) JP-A-60-248662 (JP, A) JP-B-3-62158 (JP, B2) (58) Surveyed field (Int.Cl. ⁶ , DB name) B41M 5/28-5/34 B41M 5/124-5/165

Claims (2)

(57) [Claims] 1. A recording material utilizing a color-forming reaction between a colorless or pale-colored leuco dye and a color developer which forms a color when the leuco dye is contacted, represented by the following general formula (I). A recording material comprising at least one phenolic compound. (Wherein R ₁ and R ₂ represent an alkyl group, an alkoxy group, an acyl group, an oxycarbonyl group or a halogen atom, Represents an aromatic ring, 1 represents an integer of 0 to 3, m represents an integer of 0 to 5, and n represents an integer of 1 to 10, respectively. ) 2. A recording material utilizing a color-forming reaction between a colorless or light-colored leuco dye and a color developer which forms a color when the leuco dye is contacted, wherein the color developer is represented by the following general formula (II). A recording material comprising at least one phenolic compound. (Wherein R ₁ and R ₂ represent an alkyl group, an alkoxy group, an acyl group, an oxycarbonyl group or a halogen atom, Represents an aromatic ring, k is 1-2, l is 0-3,
m represents an integer of 0 to 4 and n represents an integer of 1 to 10, respectively. )