JPS6211680B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to desensitizer compositions. More specifically, the present invention relates to a desensitizer composition that reduces or eliminates the function of a color developer that causes a colorless color former to develop color. 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 contact reaction with. Pressure-sensitive copying paper (for example, US Pat. No. 2,505,470
No. 2505489, No. 2550471, No. 2548366,
Same No. 2712507, No. 2730456, No. 2730457, Same 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 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) No. 1939962). Color developers have the properties defined above and include clays, phenolic resins, metal salts of aromatic carboxylic acids, and the like. Generally, these color developers are applied uniformly over the entire surface of the support, so a composition containing a desensitizer is applied using a printing machine or the like to the areas of the color developer sheet that do not require recording, and desensitized. This method is widely used. Desensitizers include organic amines or quaternary salts thereof (U.S. patent
No. 2777780), monoalkylamine, aralkylamine, or tertiary amine in which ethanolamine and ethylene oxide are chemically bonded (Special Publication No. 1977-
35697), spiroacetal diamines and reaction products of spiroacetal diamines and compounds having an oxirane group (German Patent Publication (OLS) No. 2343800), polyethylene glycols,
Polyhydric alcohols such as polypropylene glycol are known. These will be described later. All of these desensitizers have insufficient desensitizing effects, and in particular, US Pat.
No. 3278327, Special Publication No. 14873, No. 14873, Special Publication No. 14873, No. 48-
It was not effective against the diphenylmethane coloring agents described in No. 95420 and No. 52-148526. That is, when a diphenylmethane color former is brought into contact with the color developer sheet coated with a desensitizer, initially it appears to be desensitized, but a colored image appears over time. Slight improvement is possible by increasing the amount of desensitizer applied, but in this case, if you write or print with colored ink on the desensitizer-coated surface, the printed image of the colored ink will noticeably change and fade. The image may smudge or smudge. Furthermore, if a microcapsule layer containing a color former and a developer sheet coated with a large amount of desensitizer are placed together on pressure-sensitive copying paper, the desensitizer will swell the walls of the microcapsules and, in some cases, In the past, there were drawbacks such as destruction of the wall membrane. Japanese Patent Publication No. 50-29365 discloses the combined use of a desensitizer and titanium oxide, but the desensitizing effect is insufficient in this case as well, and in particular, there is almost no desensitization for diphenylmethane color formers. Shows no effect. An object of the present invention is to provide a desensitizer composition that exhibits sufficient effects even on diphenylmethane color formers. As a result of various studies, the present inventor has found that the above object can be achieved by using (A) at least one of alkaline earth metal oxides, carbonates, or hydroxides and (B) titanium oxide in combination with a desensitizer. I found out what I can achieve.
The alkaline earth metals mentioned here are periodic group metals, including beryllium, magnesium, calcium, strontium, barium, and radium. Among the alkaline earth metals, magnesium, calcium, and barium are particularly desirable, and their oxides and hydroxides are particularly desirable. Specific examples of alkaline earth metal oxides, carbonates, and hydroxides include magnesium oxide, magnesium carbonate, basic magnesium carbonate, magnesium hydroxide, calcium carbonate, calcium oxide, calcium hydroxide,
barium carbonate, barium oxide, barium hydroxide,
Examples include beryllium oxide and beryllium hydroxide. In addition, the alkaline earth metal oxide, carbonate or hydroxide of the present invention is contained in the desensitizer composition in an amount of 0.5 to 35%.
(wt%, the same applies hereinafter) Preferably 2 to 25% is mixed. In addition, titanium oxide is 3 to 45% in the desensitizer composition,
Preferably 5 to 40% is mixed. The desensitizing agent used in the present invention is, for example,
No. 2777780, Special Publication No. 44-27255, No. 45-21448
No. 46-22651, No. 46-29546, Japanese Unexamined Patent Publication No. 1973-
32915, JP 47-38201, JP 48-4050, JP 48-6805, JP 49-4484, JP 49-
19647, 49-23008, 49-23850, JP-A-49-43708, 49-72009, 49-77709
No. 49-77710, No. 49-15513, No. 49-
No. 83509, German Patent Application (OLS) No. 2343800,
The desensitizers described in No. 2359079 and No. 2361856 can be mentioned, and the following specific examples can be given. Quaternary ammonium salts such as dodecyltrimethylammonium chloride and octadecyl ammonium chloride; High molecular weight amines such as dodecylamine; 2, 4, 4
-Substituted oxazolines such as trimethyl-2-oxazoline; Reaction products of alkylene oxides and diamines or polyamine derivatives having a cyclic structure in the molecule such as xylene diamine and N-aminopropylpiperidine; polyoxyethylene alkylamines and polyoxyethylene alkyl Ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol, polypropylene glycol, polyoxypropylene alkylamine, polymers having glutamic acid-γ-alkyl ester residues, spiroacetal diamines, N-(aminoalkyl)-lactams, Examples include glycidyl ether adducts of amines. The compounds of the present invention are particularly useful in systems using alkylene oxide adducts other than ethylene oxide, such as propylene oxide and styrene oxide, as desensitizers. By simultaneously using these desensitizers, alkaline earth metal oxides, carbonates, or hydroxides, and titanium oxide, an improvement in the desensitizing effect on diphenylmethane color formers is observed. The desensitizer composition of the present invention may be composed only of the desensitizer, the alkaline earth metal compound, and titanium oxide, or may further contain other components.
The content of other components is preferably 0 to 80%. Other ingredients contained in the desensitizer composition of the present invention include, for example, "Printing Ink" by EAApps.
Technology” LEONARD HILL (LONDON)
Examples include general printing ink materials detailed in Chapters 2 to 9 published in 1961. for example,
Ketone resin, polyamide resin, maleic acid resin,
Natural or synthetic polymer compounds such as phenolic resins, epoxy resins, alkyd resins, melamine resins, urea resins, nitrocellulose, ethyl cellulose, butyral resins, polyvinyl alcohol, gelatin, and silicone resins (these may be present in the desensitizer composition from 0 to 40% preferably 5 to 25%), barium sulfate, talc, kaolin, bentonite,
Inorganic substances such as organic bentonite (these are contained in the desensitizer composition in an amount of 0 to 50%, preferably 0.3 to 40%),
Vegetable oils such as linseed oil, tung oil, soybean oil, cottonseed oil (these should be present in the desensitizer composition in an amount of 0 to 50%, preferably 0 to 20%)
%), organic solvents such as methanol, ethanol, ethyl acetate, toluene, hexane, methyl ethyl ketone, methyl isobutyl ketone (0 to 60%, preferably 0 to 20%), paraffin wax, microcrystalline Waxes such as wax and carnauba wax (these contain 0 to 10%, preferably 0 to 5%), anti-set-off agents such as starch and dextrin (these contain 0 to 10%, preferably 0 to 5%) 5%) and the like are included in the desensitizer composition. The desensitizer composition of the present invention can be easily prepared by those skilled in the art by mixing and dissolving the above-mentioned components, or milling them using a three-roller mill, a sand mill, etc. as necessary. can. The desensitizer composition is supplied to the color developer sheet by using a printing machine, by atomizing with a spray, or by handwriting with a crayon or eraser-like substance. The coating amount of the desensitizer composition is 0.8 to 10.0 g/m ² , preferably 1.5 to 6.0 g/m ² . Specific examples of color developers to which the desensitizer composition of the present invention can be applied include clays (for example, acid clay, activated clay, attapulgite, kaolin, etc.), phenolic resins, polyvalent metal salts of aromatic carboxylic acids, etc. can be given. Specifically, the phenolic resin is a phenol-aldehyde polymer (so-called novolac type) and a phenolic acetylene polymer. Examples of these compounds include p-phenylphenol formaldehyde polymer, p-fluorophenol-formaldehyde polymer, p-chlorophenol-formaldehyde polymer, p-
Bromophenol-formaldehyde polymer, p
- iodophenol-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 - _C12 ) phenols (e.g. p
-Methylphenol, p-ethylphenol, p
-n-propylphenol, p-isopropylphenol, p-n-amylphenol, p-isoaminephenol, 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- 1,1,3,3-tetramethylamylphenol, p-n-decylphenol, p-isodecylphenol, p-n-undecylphenol, p-isoundecylphenol, p-n-dodecylphenol) and formaldehyde , an isomer of the p-alkylphenol (the alkyl group has 1 to 12 carbon atoms), and 2 of the alkylphenol and its isomer.
Examples include copolymers of formaldehyde and mixtures containing one or more species. In addition, the p-
The addition of m-substituents to substituted phenols behaves similarly, and the addition of m-substituents is not critical. Polyvalent metal salts of aromatic carboxylic acids are disclosed in, for example, US Pat. No. 3,864,146, US Pat.
It is described in Japanese Patent Application No. 3983292, Japanese Patent Application No. 53-25158, etc. The aromatic carboxylic acid in the polyvalent metal salt of an 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; at least on one side of
Particularly preferred are those having a substituent such as an alkyl group, an aryl group, or an aralkyl group, 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. In addition, the metals for forming metal salts with the above-mentioned 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 desensitizer composition of the present invention is effective against diphenylmethane color formers, which have conventionally been difficult to desensitize.
It can be applied very effectively, and of course, it also exhibits sufficient effects on other coloring agents. Next, specific examples of these color formers will be shown. 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)-benzhydryl]-sulfone, the oxime ether form of Michler's hydrol described in JP-A-52-148526, etc., thoria 3,3-bis(pdimethylaminophenyl)-6-dimethioaminophthalide, ie, crystal violet lactone, as a lylmethane compound;
3,3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3
-(1,2-dimethylindol-3-yl)phthalide, 3-bis-(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide,
3,3-bis(1,2-dimethylindole-3
-yl)-6-dimethylaminophthalide, 3.3
-bis(9-ethylcarbazol-3-yl)-
5-dimethylaminophthalide, 3,3-bis-
(2-phenylindol-3-yl)-5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(1-methylvirol-2-yl)-
Examples of xanthene compounds such as 6-dimethyl-aminophthalide include rhodamine B-anilinolactam, rhodamine B-p-nitroanilinolactam, rhodamine B-p-chloroanilinolactam, 3-dimethylamino-7-methoxyfluoran, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-chlorofluoran, 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-fluoran, 3-diethylamino-7-phenylamino-
3-methylfluorane, 3-diethylamino-7
-chloroethylmethylaminofluorane, 3-diethylamino-7-dichloroethylaminofluorane, etc.; as thiazine compounds, benzoyl leucomethylene blue, p-nitrobenzyl leucomethylene blue, etc.; as spiro compounds, 3-
Methyl-spiro-dinaphthopyran, 3-ethyl-
Spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-(3-methoxy-benzo)-spiropyran, 3-propyl-spiro-
Examples include 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. Examples The effects of the desensitizer composition of the present invention were confirmed using the following color developer sheet and color former sheet. Color developer sheet A: 200 parts of activated clay and 800 parts of water (parts by weight, same below)
Then, the pH of the dispersion liquid was adjusted to 10.0 with a 20% aqueous sodium hydroxide solution. A coating solution was prepared by adding 40 parts of a styrene-butadiene copolymer latex having a styrene content of 60 mol % in terms of solid content and 60 parts of a 10% starch aqueous solution. This coating solution was applied to a 50 g/m ² base paper using a coating slot and dried so that the solid content was 6 g/m ² . Color Developer Sheet B 5 parts of acid clay and 1 part of aluminum oxide were added to 20 parts of water, and the pH of the dispersion was adjusted to 10.5 with a 20% caustic soda aqueous solution while stirring. Six parts of a 10% aqueous gelatin solution was added, and then a solution containing 8 parts of water and 0.56 parts of zinc chloride was gradually added. Next, 2 parts of 3,5-di-tert-butylsalicylic acid was added to 20 parts of a 15% caustic soda aqueous solution at 80°C.
The solution was gradually added and reacted. To this dispersion, 3 parts of a styrene-methyl methacrylate copolymer latex having a styrene content of 50 mol% was added as a solid content to prepare a coating liquid. This is 50g/m ²
It was coated on base paper with a coating rod and dried to a solid content of 4 g/m ² . Color developer sheet C 170 parts of paraphenylphenol and 70 parts of a 37% formaldehyde aqueous solution are combined with 10 parts of hydrochloric acid (37%) and water.
In the presence of 50 parts, the mixture was heated to reflux and reacted for 10 hours.
After cooling, the phenolic resin was taken out as a powder. 40 parts of the phenolic resin obtained by the above method and 6 parts of the naphthalene sulfonic acid formalin condensate were mixed with water.
It was put through a ball mill for one day along with 54 copies. next,
100 parts of this phenol resin dispersion, 160 parts of kaolin, and a methyl methacrylate-butadiene copolymer latex with a butadiene content of 50 mol% as a binder were added to 40 parts of solids and 500 parts of water, and mixed with thorough stirring. It was made into a coating liquid. This coating solution was coated on a 50 g/m base paper using a coating rod and dried so that the solid content was 5 g/m ² . Preparation of color former sheet A: 10 parts of acid-treated gelatin having an isoelectric point of 8.0 and 10 parts of gum arabic are dissolved in 60 parts of water at 40°C, and sodium alkylbenzene sulfonate is added as an emulsifier.
0.2 part was added thereto, and 50 parts of color former oil was emulsified therein. The coloring agent oil is an oil consisting of 4 parts diisopropyl biphenyl and 1 part kerosene, and p-tolyl [4.
4′-bis-(dimethylamino)-benzhydryl]
- 3.5% by weight of sulfone dissolved therein. When the size of the emulsified droplets reached an average of 8 microns, 100 parts of water at 40°C 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 liquid was further cooled to 8°C while stirring, and then 1.5 parts of 20% glutaraldehyde was added. Next, 30 parts of 10% carboxymethyl starch solution was poured, and 25% caustic soda was added dropwise after adjusting the pH to 8.5.
The liquid temperature was increased to 30°C to obtain microcapsules with hardened walls. Disperse 10 parts of cellulose floc in this solution,
A color forming agent sheet A was obtained by coating 6 g/m ² of the solid material on a paper of 6 g/m ² . Preparation of color former sheet B 1 part of diisopropylnaphthalene, 1 part of diisopropyl biphenyl and 1-(dimethylphenyl)-
In an oil consisting of 2 parts of 1-phenylethane, 1% by weight of crystal violet lactone, 4% by weight of 3-diethylamino-7-diethylaminofluorane, 4% by weight of 3-diethylamino-7-phenylaminofluorane, 3-diethylamino- 7.8
- Dissolve 3% by weight of benzofluorane, 0.5% by weight of 3,6-bismethoxy-fluoran and 2% by weight of benzoylleucomethylene blue to obtain a color former oil, and produce in the same manner as color former sheet A using 50 parts of this, Color former sheet B was obtained. Preparation of desensitizer composition Add 50 parts of propylene oxide adduct of ethylenediamine (average molecular weight 4100) to 15 parts of rosin-modified maleic acid resin (softening point 120°C, oxidation 150) to 150 parts.
A varnish was prepared by dissolving the mixture by heating at ℃ for 1 hour. Titanium oxide and an alkaline earth metal compound as shown in Table 1 were added to 65 parts of this varnish, respectively, and milled in a three-roll mill to obtain a desensitizer composition.

[Table] Test method The desensitizer compositions obtained above were applied by printing onto the developer sheet at a concentration of 4.0 g/m ² . The part of the obtained sample where the desensitizer composition was applied was opposed to the coloring agent sheet, and a 600 kg/ ^m2 load pressure was applied to perform the coloring operation.
RD-100 model) was used to measure the reflected visual density and evaluate the desensitization effect. Furthermore, the visual density was measured in the same manner after this sample was left in a dark place for one month. The results are shown in Table 2.

[Table] The usefulness of the desensitizer composition of the present invention is clear from Table 2. The numerical values in the table represent the desensitizing effect, and the lower the value, the higher the effect. When titanium oxide is used in combination with alkaline earth metal oxides, carbonates, or hydroxides, it exhibits a strong desensitizing effect even against diphenylmethane-based coloring agents, which could hardly be desensitized in the past. It was never reconstructed.

Claims (1)

[Claims] 1. A desensitizer, (A) at least one oxide, carbonate, or hydroxide of an alkaline earth metal selected from magnesium, calcium, or barium, and (B)
characterized by containing titanium oxide at the same time,
A desensitizer composition that reduces or eliminates the function of a color developer that develops color in colorless compounds.