JPH0549030B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a desensitizing ink for pressure-sensitive recording, and particularly to a desensitizing ink for pressure-sensitive recording that does not undergo image reconversion due to water, has excellent suitability for various types of printing, and has improved desensitizing effect and set-off property. (Prior Art) An electron-donating or proton-accepting colorless organic compound (hereinafter referred to as a color former) and an electron-accepting or proton-releasing solid acid (hereinafter referred to as a color developer)
It has been known for a long time that a colored image can be obtained by a reaction with Pressure-sensitive recording paper (for example, U.S. Pat. No. 2,505,470,
No. 2505489, No. 2550471, No. 2548366, No.
No. 2712507, No. 273045, No. 2730457, No.
3418250, 3672935), thermal recording paper (e.g., Tokko No. 43-4160, 43-7600, 45-14039)
No., U.S. Patent No. 2939009), etc. Furthermore, a printing method is known in which a colored image is obtained by supplying an ink containing a color former to a sheet coated with a color developer (German Patent Application (OLS) No. 1939962). Examples include clays, phenolic resins, and metal salts of aromatic carboxylic acids. Generally, in pressure-sensitive recording paper, a combination of a microcapsule-containing layer containing the above-mentioned coloring agent and a color developer layer is used to obtain a colored image, and these layers are brought into contact with each other to produce a colored image. This is done by destroying the microcapsules and bringing the color forming agent and color developer into contact. Generally, these color developers are applied uniformly over the entire surface of the support and used as a color developer sheet, but depending on the purpose of use of the pressure-sensitive recording paper, an area that does not require recording may be required on the side of the color developer sheet. In such cases, a method of desensitizing the color developer sheet by applying desensitizing ink containing a desensitizer to that portion of the color developer sheet using a printing machine or the like is used. Desensitizers used for this purpose are described in, for example, US Pat.
No. 45-21448, No. 46-22651, No. 46-
No. 29546, JP-A-47-32915, JP-A-47-38201
No. 48-4050, JP-A No. 48-6805, JP-A No. 49-Sho.
−4484, No. 49-19647, No. 49-23008, No. 49
-23850, JP-A-49-43708, JP-A-49-72009,
No. 49-77709, No. 49-77710, No. 49-15513,
No. 49-83509, German patent application (OLS)
No. 2343800, No. 23590759, No. 2361856, Special Publications
It is detailed in No. 58-38119 etc. (Problems to be Solved by the Invention) Desensitizing inks used for the above purpose generally use a composition consisting of a desensitizer, a pigment such as titanium dioxide, a binder, and, if necessary, an organic solvent. However, there is no desensitizing ink that shows excellent desensitizing effects against various color developers, and it was necessary to use them separately for phenolic resins, metal salts of aromatic carboxylic acids, etc. If an attempt was made to maintain the desensitizing effect against various color developers by increasing the amount of ink applied, set-off properties and stains caused by the desensitizing ink would occur, which became a serious problem. Furthermore, with conventional desensitizing inks, if you try to print with another general ink after printing with the desensitizing ink, for example, in the case of offset printing, the desensitizing ink may dissolve in the dampening water and stick to the print, or the general ink paste may become sticky. There were some inconveniences that could be described as bad. Furthermore, when conventional desensitized inks get wet with water, they may cause stains or image reversion, and sometimes do not meet the required performance. Therefore, the object of the present invention is to provide excellent printability for various types of printing.
Another object of the present invention is to provide a desensitizing ink for pressure-sensitive recording paper that can be commonly used with various color developers and has excellent set-off properties. (Means for solving the problem) The above object is achieved by the present invention described below. That is, the present invention provides a desensitizing ink containing a desensitizer, a pigment, and a binder, which is an adduct obtained by adding 5 to 50 moles of butylene oxide to 1 mole of an amine represented by the general formula (1) as a desensitizer, and propylene. An adduct in which 10 to 70 moles of propylene oxide and ethylene oxide are added to 1 mole of the amine of formula (1) is used in combination so that the oxide content is 70 mole% or more, and the use ratio of the butylene oxide adduct is a desensitizing agent. It is a desensitizing ink characterized by having a content of 20 to 90% by weight. H[-NH-(CH ₂ ) ₂ ] _o --NH ₂ (1) n is 1 to 5) If only propylene oxide and ethylene oxide adducts are used as desensitizers, they will be used as offset inks and flexographic inks. When characters are printed with general ink using offset printing, it dissolves in dampening water in the offset unit, making it impossible to obtain a uniform printed area, and it is difficult to reduce only the butylene oxide adduct. When used as a sensitizer, marginal zones tend to occur in offset printing. However, it has been found that by using both adducts in combination, each of the above-mentioned drawbacks can be overcome and a uniform printed area can be obtained. In addition, when used in combination, the balance between set-off properties and desensitization effects is improved, and among the aforementioned color developers, phenolic resins and aromatic carboxylic acid metal salts are commonly used in conventional desensitizing inks. Although none of the inks provided a good desensitizing effect and good set-off properties, the present invention provided a desensitizing ink that can be used in common with both color developers and has excellent desensitizing effects and set-off properties. In the present invention, an adduct of the above general formula (1) to an amine is used, and in the formula (1), n = 1 to 5,
Particularly preferred is n=2 to 3. As the pigment used in the present invention, white pigments such as titanium dioxide, barium sulfate, calcium carbonate, talc, kaolin, and bennite are used. The binders used in the present invention include rosin-modified phenolic resin, ketone resin, polyamide resin, maleic resin, phenolic resin, epoxy resin, alkyd resin, melamine resin, urea resin, nitrocellulose, ethyl cellulose, butyral resin, polyvinyl alcohol, gelatin, Examples include natural or synthetic polymeric compounds such as silica. The desensitizing ink of the present invention can be used with the above composition alone, but an organic solvent may be used as a diluent if necessary. Examples of organic solvents include linseed oil, tung oil, soybean oil, cottonseed oil (0 to 50%, preferably 0 to 20% of these in the desensitizer composition), methanol, ethanol, ethyl acetate, toluene, hexane, methyl ethyl ketone. , methyl isobutyl ketone, polypropylene glycol,
An organic solvent such as polybutylene glycol (contains 0 to 80%, preferably 0 to 20%) The desensitizing ink of the present invention may also contain paraffin wax, microcrystalline wax, carnauba wax, etc. as necessary. waxes, starches,
Anti-set-off agents such as dextrins and the like may be included. The composition can be easily prepared by those skilled in the art by mixing, dissolving, or, if necessary, milling the various components described above using a three-roller mill, a sand mill, or the like. The desensitized ink is supplied to the developer sheet by using a printing press, or in some cases by atomization, such as by spraying, or by handwriting with a crayon or gum-like substance. The amount of desensitizing ink applied is 0.1 to 5.0 g/desensitizer amount.
m ² , preferably 0.2 to 1.0 g/m ² . Specific examples of color developers to which the desensitizer composition of the present invention can be applied include clays (e.g., acid clay, activated clay, attapulgite, kaolin, etc.), phenolic resins, metal salts of aromatic carboxylic acids, etc. be able to. Here, the phenolic resin specifically refers to a phenol-aldehyde polymer (so-called novola ivy type) and a phenolic acetylene polymer. Examples of these compounds include p-phenylphenol formaldehyde polymer, p-fluorophenol-formaldehyde polymer, p-
Chlorophenol-formaldehyde polymer, p
-promophenol-formaldehyde polymer,
p-iodophenol-formaldehyde polymer, p-nitrophenol-formaldehyde polymer, p-carboxyphenol-formaldehyde polymer, o-carboxyphenol-formaldehyde polymer, p-carbalkoxyphenol-formaldehyde polymer, p-alloy ruphenol-formaldehyde polymer, p-lower alkoxyphenol-formaldehyde polymer, p-alkyl ( _C1 - _C12 ) 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-dimethyl-n-amylphenol, p-n-
Octylphenol, p-1,1,3,3-tetramethylbutylphenol, p-isooctylphenol, p-n-nonylphenol, p-isononylphenol, p-1,1,1,3,3-tetra Methyl amylphenol, p-n-decylphenol, p-isodecylphenol, p-n-
A polymer of undecylphenol, p-isoundecylphenol, p-n-dodecylphenol) and formaldehyde, an isomer of the p-alkylphenol (the alkyl group has 1 to 12 carbon atoms),
Also included are copolymers of formaldehyde and mixtures containing two or more of the alkylphenols and their isomers. Further, even if an m-substituent is added to the p-substituted phenol, it behaves in the same manner, and the addition of the m-substituent is not important. Metal salts of aromatic carboxylic acids are described, for example, in US Pat. No. 3,864,146, US Pat. The aromatic carboxylic acid in the above-mentioned metal salt of aromatic carboxylic acid is preferably one having a hydroxyl group at the ortho or para position with respect to the carboxy group, and salicylic acid derivatives are particularly preferred; Particularly preferred are those having a substituent such as an alkyl group, an aryl group, an aralkyl group, etc., and the total number of carbon atoms of the substituents is 8 or more. Examples of particularly preferred aromatic carboxylic acids include:
3,5-di-t-butylsalicylic acid, 3,5-di-t-amylsalicylic acid, 3,5-bis(α,α
-dimethylbenzyl)salicylic acid, 3,5-bis(α-methylbenzyl)salicylic acid, 3-(α-methylbenzyl)-5-(α,α-dimethylbenzyl)salicylic acid, 3,5-di-t-octylsalicylic acid , 3-cyclohexyl-5-(α,α-dimethylbenzyl)salicylic acid and the like. Metals for forming metal salts with the aromatic carboxylic acids include magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, strontium,
Examples include yttrium, zirconium, molybdenum, cadmium, indium, tin, antimony, barium, tungsten, lead, and bismuth. Among these metals, zinc, tin, aluminum, etc. are particularly effective. The most effective of these is zinc. The developer is applied to a support such as paper along with a binder such as a styrene butadiene latex. On the other hand, examples of the color forming agent that causes a color reaction with the color developer include diphenylmethane compounds, triarylmethane compounds, xanthene compounds, and spiropyran compounds. Specific examples of these color formers are shown below. p-tolyl as a diphenylmethane compound
[4,4'-bis-(dimethylamino)-benzhydryl]-sulfone, phenyl-[4,4'-bis-
(dimethylamino)-benzhydryl]-sulfone,
4-chloro-phenyl-[4,4'-bis-(dimethylamino)benzhydryl]-sulfone, 3-nitro-4-methyl-phenyl-[4,4'-bis-(dimethylamino)benzohydryl]-sulfone, esp. 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, i.e., Crystal Bio Rettolactone, 3,3-bis(p-dimethylaminophenyl)phthalide, 3
-(P-dimethylaminophenyl)-3-(1,2
-dimethylindol-3-yl)phthalide, 3
-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, 3-(p
-dimethylaminophenyl)-3-(2-phenylindol-3-yl)phthalide, 3,3-bis-(1,2-dimethylindol-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-phthalide) enylindol-3-yl)-5-dimethylaminophthalide,
As xanthene compounds such as 3-p-dimethylaminophenyl-3-(1-methylpyrrol-2-yl)-6-dimethylaminophthalide, rhodamine B-anilinolactam, rhodamine
Nitroanilinolactam, Rhodamine B-p-chloroanilinolactam, 3-dimethylamino-7
-methoxyfluorane, 3-dimethylamino-7
-methoxyfluorane, 3-diethylamino-6
-methoxyfluorane, 3-diethylamino-7
-Chlorofluorane, 3-diethylamino-7-
Chloro-6-methylfluorane, 3-diethylamino-6,8-dimethylfluorane, 3-diethylamino-7-acetylmethylaminofluorane, 3-diethylamino-7-methylaminofluorane, 3,7-diethylaminofluorane ,3
-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-methylbenzylamino-fluorane, 3-diethylamino-7-
Phenylamino-6-methylfluoran, 3-diethylamino-7-chloroethylmethylaminofluoran, 3-diethylamino-7-dichloroethylaminofluoran, etc.; as thiazine compounds, benzoylleucomethylene blue, p-nitrobenzylleucomethylene blue, etc. ; As spiro compounds, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,
3'-dichloro-spiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-
Examples include (3-methoxy-benzo)-spiropyran, 3-propyl-spiro-dibenzopyran, and mixtures thereof. The color former is dissolved in a solvent and encapsulated, or dispersed in a binder solution and applied to the support. As a solvent, natural or synthetic oils can be used alone or in combination. Examples of solvents include cottonseed oil, kerosene, paraffin, naphthenic oil, alkylated biphenyl, alkylated terphel, chlorinated paraffin, alkylated naphthalene, and the like. Methods for manufacturing capsules include methods using coacervation of hydrophilic colloid sol described in U.S. Patent Nos. 2800457 and 2800458, and British Patent Nos. 867797, 950443, and 989264.
There are interfacial polymerization methods described in No. 1, No. 1091076, etc. [Example] Hereinafter, the present invention will be specifically explained with reference to Examples. Examples 1 to 4 and Comparative Examples 1 to 3 and 7 17 parts by weight of a rosin-modified phenol resin (manufactured by Arakawa Chemical Co., Ltd., Tamanol 135) was added to 40 parts by weight of a desensitizer having the desensitizer composition shown in Table 1. , melted at 150°C. After cooling this melt to 25℃, titanium dioxide 25
18 parts by weight of white spindle oil were added and kneaded in a three-roll mill to obtain a desensitizing ink for offset. Examples 5 to 8 and Comparative Examples 4 to 6 Ethyl cellulose (manufactured by Hercules, N-50) was added to 40 parts by weight of the desensitizer composition shown in Table 1.
10 parts by weight, 25 parts by weight of titanium dioxide, 25 parts by weight of ethanol
Parts by weight were added and kneaded in a ball mill to obtain a desensitizing ink for flexography.

【table】

【table】

【table】

[Table] (Desensitizing ink offset property) Apply desensitizing ink to the developer side of the developer sheet for pressure-sensitive recording paper at a density of 3 g/m ² , and overlap the final coated area to 50 g/m Apply a weight of ² , 35℃, 80%
It was left in RH for 5 days. The stain caused by the desensitized ink on the final coated area was observed and evaluated as follows. ○: No stains were generated. △: Staining occurred, but the characters did not become blurred even when copied over the color former sheet. ×: Severely stained and unsuitable for practical use. (Printing suitability 1) With offset printing machine or flexo printing machine
Printing was carried out for 4000 m, a color former was sprayed onto the printed surface using a color former, and it was observed whether the desensitizing ink was uniformly applied, and the following evaluations were made. ○: Printed uniformly. △: A little unevenness occurred, but due to the coloring agent,
There is no stickiness or coloring, and it is judged that there is no problem in practical use. ×: Severe unevenness, unsuitable for practical use. (Printing suitability 2) After printing desensitized ink with an offset printing machine or flexographic printing machine, offset printing of general ink was performed on the desensitized ink printed area, and the printing finish of the general ink was evaluated as follows. ○: Even when printing at 4000m, the finish was good. △: The finish was good until 2000m printing. x: Offset printing cannot be performed on the desensitized ink printed area. (Desensitizing effect) Desensitizing printing is performed on a developer sheet for pressure-sensitive recording paper using the following developer so that the coating amount of desensitizing ink is 3.0 g/ ^m2 , and color is developed with a black color developer sheet. It was determined whether desensitization had occurred. A; p-phenylphenol resin B; 3,5-ditertiary-butylsalicylic acid zinc salt (reimaging with water) Color developer sheet using 3,5-ditertiarybutylsalicylic acid zinc salt, Print so that the desensitizing ink is 2g/ ^m2 , overlap it with a coloring agent sheet, print with a typewriter, and add 1ml of water to the printing area.
was injected with a dropper. The level of restoration by water was observed and evaluated as follows. ○: There is no reconstruction due to water. △: There is some restoration due to water, but it disappears when the water evaporates. ×: Image is restored by water and does not disappear even if the water evaporates.

【table】

Claims (1)

[Scope of Claims] 1. In a desensitizing ink containing a desensitizer, a pigment, and a binder, butylene containing 5 to 50 moles of butylene oxide added to 1 mole of an amine represented by general formula (1) as a desensitizer. The total number of additions of propylene oxide and ethylene oxide is 10 to 1 mole of the oxide adduct and the amine of general formula (1).
70 moles and a propylene oxide-ethylene oxide adduct in which the number of moles of propylene oxide in the total addition number is 70 mole% or more is used in combination, and the content of the butylene oxide adduct is 20% by weight of the desensitizer. A desensitizing ink for pressure-sensitive recording paper characterized by a content of ~90% by weight. H[-NH-(CH ₂ ) ₂ ] _o --NH ₂ (1) (n is 1 to 5)