JPS6054198B2 - color developing ink - Google Patents

Description

[Detailed description of the invention] The present invention relates to a color developing ink.

More specifically, the present invention relates to a color developing ink that reacts with a substantially colorless organic compound to obtain a colored product. It has been known for a long time that a colored image can be obtained through a contact reaction between an electron-donating colorless organic compound (hereinafter referred to as a color former) and an electron-accepting solid acid (hereinafter referred to as a color developer). .

Pressure-sensitive copying paper (
For example, US Patent Nos. 2,505,470 and 2,505,489
No. 2550471, No. 2548366, No. 27
No. 12507, No. 2730456, No. 2730457
No. 341825 Gin, No. 3672935), thermal recording paper (for example, Tokko No. 43-4160, No. 43-76)
No. 00, No. 45-1403, U.S. Patent No. 293,900), etc. Furthermore, a printing method is also known in which a colored image is obtained by supplying ink containing a color former to a sheet coated with a color developer (German patent application (OLS) 193996).

Generally, developer sheets are coated with developer over the entire surface of the paper, so desensitizing ink must be printed and applied to areas where copying is not desired to prevent color development, which is extremely uneconomical. . For this reason, color developer inks have been put on the market to print and apply color developer only to the necessary areas, but all of them use low-boiling point organic solvents and are limited to flexo or gravure printing methods, making them in general use. It could not be applied to letterpress or offset printing machines. Recently, Japanese Patent Publication No. 51-68307
Letterpress type color developing inks were announced in No. 51-8o4m and No. 51-94308, but all of them had low color density and insufficient light fastness of the colored images, so they were not practical.

The first object of the present invention is to provide a color developing ink that can be applied to letterpress or offset type printing machines.

The second object is to provide a color developing ink that can obtain sufficient color density. The third object is to provide a color developing ink with strong light fastness of color images. As a result of various studies, the present inventors found that
At least one selected from phenol resins, aromatic carboxylic acids, or metal salts thereof, and the following general formula (I)
It has been found that the above objects can be achieved by a color developing ink containing the biphenyl derivative shown in the following formula or its hydrogenated product.

General formula (1) In the formula, Rl, R2, R3, R4, R5 are each H or C1
- represents a C6 alkyl group, and 2 represents H or a phenyl group.

The phenolic resin used in the color developing ink of the present invention is
Specifically, they are phenolic aldehyde polymers (so-called novolak type) and phenolic acetylene polymers.

Examples of these compounds include p-phenylphenol-formaldehyde polymer, p-fluorophenol-formaldehyde polymer, p-chlorophenol-formaldehyde polymer, p-promophenol-formaldehyde polymer, and p-iodophenol-formaldehyde polymer. Formaldehyde polymer, p-nitrophenol-formaldehyde polymer, p-carboxyphenol-formaldehyde polymer, o-carboxyphenol-formaldehyde polymer, p-carbalkoxyphenol-formaldehyde polymer, p-aroylphenol - formaldehyde polymer, p-lower alkoxyphenol -formaldehyde polymer, p-alkyl (C1-Cl2) phenol (e.g., p-methylphenol, p-ethylphenol, p-n-propylphenol, p-isopropylphenol, p-n-amylphenol, p-isoamylphenol, p-cyclohexylphenol, p
-1,1-dimethyl-n-propylphenol, p-n
-hexylphenol, p-isohexylphenol,
p-1,1-dimethyl-n-butylphenol, p-1
, 2-dimethyl-n-butylphenol, p-n-heptylphenol. p-isoheptylphenol, p-
5,5-dimethyl-n-amylphenol, p-1,1
monodimethyl-n-amylphenol, p-n-octylphenol, p-1,1,3,3-tetramethylbutylphenol, p-isooctylphenol, p-n-nonylphenol, p-isononylphenol, p-1,
1,3,3-tetramethylamylphenol, p-n-
Decylphenol, p-isodecylphenol, p-n
- undecylphenol, p-isoundecylphenol, p-n-dodecylphenol) polymers with formaldehyde, isomers of the p-alkylphenols (alkyl group has 1 to 12 carbon atoms), and the alkylphenols and their isomers Examples include copolymers of formaldehyde and mixtures containing two or more of these compounds.
Further, even if an m-substituted group is added to the p-substituted phenol, it behaves in the same manner, and the addition of the m-substituted group is not important. ) Specific examples of aromatic carboxylic acids used in the color developing ink of the present invention include benzoic acid, chromium benzoic acid (0,
m, p), nitrobenzoic acid (0, m, p), toluic acid (0, m, p), 4-methyl-3-nitrobenzoic acid, 2
-Chloro-4-nitrobenzoic acid, 2,3-dichlorobenzoic acid, 2,4-dichlorobenzoic acid, p-isopropylbenzoic acid, 2,5-dinitrobenzoic acid, p-Tert-
Butylbenzoic acid, N-phenylanthranilic acid, 4-methyl-3-nitrobenzoic acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 3,5-dinitrosalicylic acid, 5-Tert-butylsalicylic acid, 3
-phenylsalicylic acid, 3-methyl-5-tert-butylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-di-tert-amylsalicylic acid, 3-
Cyclohexylsalicylic acid, 5-cyclohexylsalicylic acid, 3-methyl-5-isoamylsalicylic acid, 5-isoamylsalicylic acid, 3,5-di-Sec-butylsalicylic acid, 5-nonylsalicylic acid, 2-hydroxy-3-
Methylbenzoic acid, 2-hydroxy-5-Tert-butylbenzoic acid, 2,4-cresotic acid, 5,5-methylenedisalicylic acid, acetaminobenzoic acid (0, m, p),
2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, anacardic acid, 1-naphthoic acid, 3,5-di-α,α-dimethylbenzylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, 2-naphthoic acid , 1-
Examples include hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-1-naphthoic acid, thiosalicylic acid, and 2-carboxybenzaldehyde. The metal of the phenolic resin or aromatic carboxylic acid metal salt used in the color developing ink of the present invention includes:
These include copper, lead, magnesium, calcium, zinc, tin, nickel, and aluminum.

Specific examples of biphenyl derivatives or hydrogenated products thereof used in the color developing ink of the present invention are shown below.

biphenyl, 2-methylbiphenyl, 3-methylbiphenyl, 4-methylbiphenyl, 2,2''-dimethylbiphenyl, 3,3''-dimethylbiphenyl, 4,4'-dimethylbiphenyl, 2,4-dimethylbiphenyl, 2,
6-dimethylbiphenyl, 2,4,6-trimethylbiphenyl, 2,4,6,2″,4″,6″-hexamethylbiphenyl, 0-terphenyl, m-terphenyl, p
-terphenyl, cyclohexylbenzene, 4-cyclohexylbiphenyl, 2-isopropylbiphenyl, 3
-isopropylbiphenyl, 4-isopropylbiphenyl, etc. Among biphenyl derivatives, those having a melting point of 70° C. or lower are particularly desirable.

It is appropriate that the phenol resin, aromatic carboxylic acid or metal salt thereof be contained in the ink in an amount of 20 to 80%, preferably 30 to 70%.

The biphenyl derivative or its hydrogenated product is contained in the ink from 5 to
A suitable content is 60%, preferably 10 to 50%. The color developing ink of the present invention comprises (4) a phenolic resin;
The aromatic carboxylic acid or its metal salt and (B) the biphenyl derivative may be the essential components, and materials for general letterpress or offset ink may also be added. General letterpress or offset ink materials, etc. are E. A. RP written by Apps
rintjngInkTechnOlOgyJLEON
ARDH1LL (LONDON) 2~ published in 1961
Examples include printing ink materials detailed in Chapter 9. For example, binders such as ketone resins, polyamide resins, maleic acid resins, rosin-modified phenolic resins, epoxy resins, rosin esters, petroleum resins, urethane resins, alkyd resins (these are
0%, preferably 0 to 25%), titanium dioxide, barium sulfate, calcium carbonate, talc, kaolin, acid clay, bentonite, organic bentonite, zinc oxide, aluminum hydroxide, and other inorganic materials. Drying oil or semi-drying oil such as linseed oil, tung oil, soybean oil, fish oil, synthetic drying oil, etc. used in the color developer ink, 0 to 40%, preferably 0 to 30%, petroleum fractions such as kerosene, machine oil, and ink oil, or solvents such as isopropylnaphthalenes or biphenylmethanes shown in JP-A No. 51-94308 (these are used in color developing inks, waxes such as paraffin wax, microcrystalline wax, and carnauba wax (0 to 80%, preferably 0 to 5%) in the developing ink. Set-off preventive agents such as (used), starch, and dextrin (these are used in color developing inks, O to 10
%, preferably used from 0 to 5%), etc. may be included in the developer ink. Furthermore, a photosensitive resin such as a prepolymer of a photosensitive acrylic acid derivative or a polyfunctional acrylic monomer may be introduced to produce a photocurable color developing ink. The color developing ink of the present invention can be easily prepared by those skilled in the art by mixing and dissolving the above-mentioned components and, if necessary, kneading them using a three-roller mill or the like. can.

The color developing ink coating amount of the present invention is 0.5yI to 5.0f1
A suitable resistance is preferably 0.7y1 to 4.0y'.

The color forming agent to which the color developing ink of the present invention can be applied is not particularly limited, but specific examples of compounds are as follows.

3,3-bis(p-
dimethylaminophenyl)-6-dimethylaminophthalide or crystal violet lactone, 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(p-
dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindole-3-
yl)phthalide, 3-(p-dimethylaminophenyl)
-3-(2-phenylindole-3-yl)phthalide, 3,3-bis(1,27-dimethylindole-3)
-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazol-3-yl) )-5-dimethylaminophthalide, 3
,3-bis(2-phenylindo-3-yl)-
5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(1-methylpyrrol-2-yl)-6
-dimethyl-aminophthalide, etc.; diphenylmethane compounds such as 4,4-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl leuco auramine, N-2,4,5-trichlorophenyl leuco auramine; Rhodamine B as a xanthene compound
-Anilinolactam, Rhodamine B-p-nitroanilinolactam, Rhodamine B-p-chloroanilinolactam, 3-dimethylamino-7-methoxyfluoran, 3
-diethylamino-7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7
-chloro-6-methylfluorane, 3-dimethylamino-6,8-dimethylfluorane, 3-diethylamino-7-acetylmethylaminofluorane, 3-diethylamino-7-methylaminofluorane, 3,7-diethylaminofluorane oran, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-methylbenzylaminofluorane, 3-diethylamino-7
-phenylamino-3-methylfluorane, 3-diethylamino-7-chloroethylmethylaminofluorane,
3-diethylamino-7-dichloroethylaminofluorane, etc.; Thiazine compounds such as benzoylleucomethylene blue, p-nitrobenzylleucomethylene blue, etc.; Spiral compounds such as 3-methyl-spirodinaphthopyran, 3-ethyl-spiro dinaphthopyran,
Examples include 3,3''-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 39methyl-(3-methoxybenzo)-spiropyran, 3-propyl-spirodibenzopyran, or mixtures thereof. The color former is dissolved in a solvent and encapsulated, or dispersed in a binder solution and applied to the support.
As the solvent, natural or synthetic oils can be used alone or in combination. Examples of solvents include cottonseed oil, kerosene, paraffins, naphthenic oils, alkylated biphenyls, alkylated terfels, chlorinated paraffins, alkylated naphthalenes, and the like. Regarding the method for manufacturing capsules, see US Pat.
A method using coacervation of a hydrophilic colloid sol described in No. 8, British Patent No. 867797, British Patent No. 95
There are interfacial polymerization methods described in No. 0443, No. 989264, No. 1091076, and the like. The performance of the color developing ink of the present invention was tested using the following color former sheet.

Adjustment of Color Former Sheet A 10 parts of acid-treated gelatin having an isoelectric point of 8.0 and 10 m of gum arabic were dissolved in 4 parts (6 parts) of water, and 0.2 part of sodium alkylbenzenesulfonate was added as an emulsifier. 50 parts of color former oil was emulsified.

1 The color former oil is an oil consisting of 4 parts diisopropyl biphenyl and 1 part kerosene, 2.5% by weight of crystal violet lactone, and 2.5% by weight of benzoylleucomethylene blue.
It is obtained by dissolving the slag weight%.

40 when the size of the emulsified droplets reaches an average of 8 microns.
100 parts of water at ℃ was added to suppress the progress of emulsification. While stirring, 210 parts of water at 30°C was further added, and 20% hydrochloric acid was added to adjust the pH of the system to 4.4.

The mixture was further cooled to 8°C while stirring, and then 1.5 parts of 20% glutaraldehyde was added. Then 10%
A portion of the carboxymethyl starch solution was poured, and 25% sodium hydroxide was added dropwise to adjust the pH to 8.5, and the liquid temperature was heated to 30'C to obtain microcapsules with hardened walls. Cellulose floc 1 was dispersed in this liquid, and 6fId was applied as a solid onto a 40f1w1 paper to obtain a color former sheet A.

Next, an example will be described.

Note that the blending ratios in the examples indicate parts by weight. Example 1 To 70 parts of 3,3''-dimethylbiphenyl was added (up to) parts of zinc 3,5-di-ter-shaributylsalicylate, and 1
A developing ink was obtained by heating and melting at 60°C.

This ink was applied to high-quality paper using a letterpress printing machine in an amount of 1.8y.
It was printed and coated so that it became 'd. Example 2 To a mixed solvent of 30ml of 3-isopropylbiphenyl and 2 parts of 14-isopropylbiphenyl, 35 parts of rose phenylphenol formaldehyde resin (CKM-525, manufactured by Showa Union) was added and completely dissolved at 160°C to produce a varnish.

10 m of titanium oxide was added to this varnish and milled in a three-roll mill to obtain a color developing ink. The amount of this ink applied to high-quality paper using an offset printing machine is 1.8 f! It was printed and applied so that it became 1d. Example 3 Orthoterphenyl addition part, hydrogenated orthoterphenyl head part, ester resin (Ester Gum AA Top 1 manufactured by Arakawa Chemical,
6 parts (softening point 82'C) and 9 parts of 3,5-di-α,α-dimethylbenzyl salicylic acid were uniformly stirred and heated.

Next, w part of zinc oxide was added to this and milled in a three-roll mill to obtain a color developing ink. This ink was printed and coated on high-quality paper using a letterpress printing machine so that the coating amount was 1.8y1rf1. Comparative Example 1 A printed coated paper was obtained in the same manner as in Example 1 except that the same amount of diisopropylnaphthalene was used in place of 3,3''-dimethylbiphenyl D part.

Comparative Example 2 Same as Example 2 except that (a) part of methylphenylxylylmethane was used instead of (8) parts of 3-isopropylbiphenyl and 20 parts of 4-isopropylbiphenyl. After processing, a printed coated paper was obtained.

Comparative Example 3 In Example 3, Ink Solvent 45 was used instead of orthoterphenyl 30S and hydrogenated orthoterphenyl nodule.
The treatment was carried out in the same manner as in Example 3, except that (4) parts of No. No. Solvent, boiling point 276°C to 311°C, manufactured by Nisseki Chemical Co., Ltd. were used. It did not dissolve uniformly and could not be made into an ink.

Printed coated paper performance comparison test Color former sheet A was placed opposite the developer printed coated papers obtained in Examples and Comparative Examples, and the density and light fastness of the copied images were compared by writing with a ballpoint pen.

The results are shown in Table 1. From the results in Table 1, it can be seen that the color developer ink of the present invention exhibits superior copy image density and copy image light fastness compared to the comparative color developer ink.

Claims (1)

[Claims] 1. At least one selected from phenolic resins, aromatic carboxylic acids, or metal salts thereof, and the following general formula (I
) A color developing ink comprising a biphenyl derivative or a hydrogenated product thereof. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1, R_2, R_3, R_4, R_5 each represent H or an alkyl group from C_1 to C_6, and R_6
represents H or a phenyl group.