JPS6356877B2 - - 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 contact reaction with Pressure-sensitive copying paper (for example, U.S. Pat. No. 2,505,470,
Same No. 2505489, No. 2550471, No. 2548366, Same No.
No. 2712507, No. 2730456, 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 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, thereby desensitizing them. This method is widely used. For desensitizers, see US Patent No. 2777780,
No. 44-27255, No. 45-21448, No. 46-22651,
No. 46-29546, JP-A-47-32915, JP-A No. 47-32915
No. 38201, No. 48-4050, Japanese Patent Publication No. 48-6805, Japanese Patent Publication No. 49-4484, No. 49-19647, No. 49-23008
No. 49-23850, JP-A No. 49-43708, No. 49-
No. 72009, No. 49-77709, No. 49-77710, No. 49
-15513, 49-83509, German patent application (OLS) 2343800, 2359079, 2361856,
For example, 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; Substituted oxazolines such as 2,4,4-trimethyl-2-oxazoline;
Reaction products of diamines or polyamine derivatives having a cyclic structure in the molecule, such as xylene diamine and N-aminopropylpiperidine, and alkylene oxide; polyoxyethylene alkylamine, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene Glycol, polypropylene glycol, polyoxypropylene alkylamine, polymer having glutamic acid-γ-alkyl ester residue,
Examples include spiroacetal diamines, N-(aminoalkyl)-lactams, and glycidyl ether adducts of amines. All of these desensitizers have insufficient desensitizing effects and are not hydrophobic, making it impossible to apply them by an offset printing method that utilizes their repellency with water. For this reason, there has been a strong desire to develop a hydrophobic desensitizer that has a strong desensitizing effect and can be applied using a general-purpose offset printing machine. An object of the present invention is to provide a desensitizing agent that has a strong desensitizing effect, exhibits hydrophobicity, and can be printed and coated using an offset printing machine. As a result of various studies, the present inventors have found that the object of the present invention can be achieved by using a compound having an alcoholic or phenolic hydroxyl group and an alkylene oxide adduct containing at least 40 mol% butylene oxide. I discovered that. Examples of the compound having an alcoholic or phenolic hydroxyl group mentioned here include the following compounds. monoethanolamine, diethanolamine,
Triethanolamine, propyl alcohol, butyl alcohol, octyl alcohol, dodecyl alcohol, stearyl alcohol, oleyl alcohol, isopentyl alcohol, 2-ethylhexanol, cyclopentanol, cyclohexanol, benzyl alcohol, 2-phenylethanol, glycerin, ethylene Glycol, diethylene glycol monomethyl ether, phenol, o-cresol, catechol, bisphenol, p-octylphenol, p-dodecylphenol, n-nonylphenol, and among these compounds, alkanolamines are particularly preferred because of their great desensitizing effect. In the adduct of a compound having a hydroxyl group and an alkylene oxide used in the present invention, the alkylene oxide contains 40 mol% or more of butylene oxide, and may contain alkylene oxides other than butylene oxide. Examples of preferable alkylene oxides other than butylene oxide include ethylene oxide, propylene oxide, styrene oxide, epichlorohydrin, and long-chain α-olefin oxide. Further, the amount of alkylene oxide added per molecule of the compound having a hydroxyl group is preferably 3 to 50 moles, more preferably 5 to 20 moles. The adduct of alkylene oxide used in the present invention uses the above-mentioned compound having an alcoholic or phenolic hydroxyl group and alkylene oxide. Manufactured according to the method described on page 1. Next, specific examples of the alkylene oxide adduct used in the present invention will be shown, but of course the invention is not limited to these. In the structural formula below,

[Formula] Group is B.O

[Formula] group is SO −CH ₂ CH ₂ O− group is EO

[Formula] The group is abbreviated as PO. Moreover, the positional relationship of each alkylene oxide group may be changed. In the present invention, the alkylene oxide includes isomers when the alkylene oxide has isomers. (1)

【formula】 (2)

[Formula] (3) N [CH ₂ CH ₂ O (EO) ₃ (BO) ₂₀ H] ₃ (4) N [CH ₂ CH ₂ O (SO) ₂ (BO) ₈ H] ₃ (5) N [ CH ₂ CH ₂ O (BO) ₄ H〕 ₃ (6) C ₈ H ₁₇ O (BO) ₁₀ (EO) ₂ H (7) C ₄ H ₉ O (PO) ₁₀ (BO) ₉ H (8)

[Formula] (9) (Ten)

[Formula] (11) CH ₃ -O-CH ₂ CH ₂ -O-(BO) ₁₄ H (12) C ₁₈ H ₃₅ O(BO) ₆ H In this specification, what is the desensitizer composition? The composition contains the above-mentioned adduct as a desensitizer component and, if necessary, other desensitizers or various additives. In the desensitizer composition of the present invention, the compound may contain 5 to 60
% (same below by weight), preferably 15 to 50%. Various additives contained in the desensitizer composition of the present invention are "Printing Ink Technology" by EAApps.
LEONARD HILL (LONDON) 1961 issue 2
Examples include materials for general printing ink, etc., which are detailed in Chapters 9 to 9. For example, ketone resin, polyamide resin, maleic acid resin, phenolic resin,
Epoxy resin, alkyd resin, melamine resin,
Natural or synthetic polymeric compounds such as urea resins, polyvinyl alcohol, gelatin, and silicone (these should be present in the desensitizer composition in an amount of 0 to 40%, preferably 5%).
~25%), titanium dioxide, barium sulfate,
Inorganic substances such as calcium carbonate, talc, kaolin, bentonite, organic bentonite (these are included in the desensitizer composition at 0 to 50%, preferably 0.3 to 40%), vegetable oils such as linseed oil, tung oil, soybean oil, cottonseed oil, etc. These heated polymers (these are contained in the desensitizer composition in an amount of 0 to 50%, preferably 0 to 20%), waxes such as paraffin wax, microcrystalline wax, and carnauba wax (these are ~10%, preferably 0-5%), starch, dextrin (these are present at 0-10%, preferably 0-5%).
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, dissolving, or, if necessary, kneading the various components described above using a three-roller mill, kneader, etc. can. The desensitizer composition of the present invention is applied by printing onto a developer sheet using a letterpress, dry offset, or wet offset printing machine. 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 (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 novolac type) and a phenolacetylene polymer. 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, or an aralkyl group at at least one of the ortho or para positions, and the total number of carbon atoms of the substituents is 8 or more. Further, as the metal for forming the metal salt with the aromatic carboxylic acid, zinc, tin, aluminum, etc. are preferable, and among these, zinc is the most effective. The developer is applied to a support such as paper along with a binder such as a styrene butadiene latex. On the other hand, colorless compounds (color formers) that cause a color reaction with a color developer include diphenylmethane compounds, triarylmethane compounds, xanthene compounds,
Examples include spiropyran compounds and thiazine compounds. 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. Preparation of 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. To this, 40 parts of a styrene-butadiene copolymer latex having a styrene content of 60 mol % in solid form and 60 parts of a 10% starch aqueous solution were added to prepare a coating solution of the present invention. This coating solution was coated on a 50 g/m ² base paper so that the solid content was 6 g/m ² and dried to obtain a color developer sheet A. Preparation of 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. Three parts of a styrene-methyl methacrylate copolymer latex having a styrene content of 50 mol % was added to this dispersion to prepare a coating liquid. This is 50g/m ²
A developer sheet B was obtained by coating and drying the base paper so that the solid content was 4 g/m ² . Preparation of color former sheet: 10 parts of acid-treated gelatin with 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 color former oil was prepared by dissolving 2.5% by weight of crystal violet lactone and 2.0% by weight of benzoyl leucomethylene blue in an oil consisting of 4 parts of diisopropylbiphenyl and 1 part of kerosene. 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 continuing to stir, add another 210 parts of water at 30°C.
The pH of the system was adjusted to 4.4 by adding 20% hydrochloric acid. The liquid was further cooled to 8°C while stirring, and then heated to 20°C.
% 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 was obtained by coating 6 g/m ² of the solid content on a paper of 6 g/m ² and drying. Preparation of desensitizer composition Add 15 parts of rosin-modified maleic acid resin (softening point 120°C, acid value 30) to 50 parts of desensitizer (shown in Table 1).
The mixture was heated and dissolved at 150°C for 1 hour. 35 parts of titanium dioxide was added to this and milled in a three-roller mill to obtain a desensitized ink. Test method Each desensitizer composition was applied by printing onto a developer sheet using a small-sized sheet-fed offset printer (manufactured by Ryobi) at a coating amount of 3 g/m ² . For evaluation, first, during printing, the suitability for offset printing was observed as dirt in the non-printed area. Furthermore, the desensitized part of the obtained sample was faced with the coloring agent sheet mentioned above, and a coloring operation was performed by applying a load pressure of 600 kg/ ^cm2 .
RD-514) was used to measure the reflected visual density and evaluate the desensitizing effect. The results are shown in Table 1. In addition, in Table 1 desensitization effect, the lower the value, the higher the desensitization effect, and 0.06 or less indicates complete desensitization.

[Table] Table 1 shows the usefulness of the present invention. That is, although the comparative compound has a relatively high desensitization effect, it cannot be used because of the large amount of staining on the non-printing area during offset printing.
The example compounds have a high desensitization effect and exhibit extremely stable printability without staining non-printing areas even during offset printing.

Claims (1)

[Scope of Claims] 1. A desensitizer composition that reduces or eliminates the function of a color developer that develops color in a colorless compound containing an alkylene oxide adduct of an alkanolamine, wherein the alkylene oxide contains at least 40 mol%. A desensitizer composition comprising butylene oxide. 2. Developing a colorless compound containing an adduct of an alkanolamine and an alkylene oxide containing at least 40 mol % of butylene oxide using an offset printing machine with a desensitizer composition that reduces or eliminates the function of a color developer to develop color. A desensitization method characterized by printing and coating on a sheet of agent.