JPH0518872B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to printing inks. More specifically, the present invention relates to a printing ink with a new composition that does not form an oxidized polymer film during storage or before application, and does not dry out a thin film after printing. Conventional printing inks contain manganese, cobalt, cerium, zirconium, lead, iron, zinc, vanadium,
Metals such as calcium and barium, naphthenic acid, octylic acid, linseed oil acid, soybean fatty acid, tall oil,
Contains an oil-soluble carboxylic acid metal salt such as rosin as a desiccant. However, depending on the type and amount of these desiccants added, an oxidized polymer film may be formed on the ink surface when exposed to air before printing, and during printing, the oxidized polymer film (hereinafter referred to as a thick film) may form in the ink print film. ) may be mixed in, making it impossible to achieve a beautiful print finish, or the drying of the thin film after printing may be slow, resulting in poor printing efficiency. In particular, cobalt-based desiccants are widely used because they allow thin films to dry very quickly after printing, but they also have the disadvantage that thick films dry too quickly during storage or before printing. In order to prevent this drawback, anti-skinning agents have conventionally been added, but if the amount added is too small, the effect will be lost, and if too much, the drying of the thin film after printing will be delayed, so the proportion of the added amount should be adjusted accordingly. It was difficult to get it right. The present invention eliminates the drawbacks of conventional printing inks, and provides a printing ink that dries slowly during storage or in the preparation state before printing, does not form a thick film, and does not dry slowly in a thin film after printing. The purpose is to provide As a result of intensive research to achieve the above object, the present inventors have found that, without using the cobalt-based desiccant that has been most widely used in the past, we have added appropriate amounts of iron-based desiccant and manganese-based desiccant, and at the same time We have found that by combining these organic reducing agents, it is possible to delay the drying of a thick film during storage or before printing without delaying the drying of a thin film after printing. The present invention was completed based on this knowledge. The gist of the present invention is to provide an iron carboxylate drying agent in an amount of 0.002 to 0.5% by weight as iron, and a manganese carboxylate drying agent in an amount of 0.002 to 0.3% by weight as manganese, based on the solid weight of the printing ink. agent,
and 0.001 to 0.5 of the reducing agent represented by the general formula below.
A printing ink characterized by containing % by weight. general formula However, R ₁ is

[Formula] OH, NH ₂ , NH・CH ₃ , NH・C ₂ H ₅ ,

【formula】

[Formula] NH--CH ₂ OH or NHC ₂ H ₅ OH or a neutralized salt thereof, R ₂ , R ₃ , R ₄
is H, F, Cl, Br, I, alkyl group having 1 to 4 carbon atoms, CH ₂ OH, OH, NH ₂ , NHCH ₃ ,
_{NHC2H5 ,}

【formula】

[Formula] NH- Represents CH ₂ OH or NHC ₂ H ₄ OH, or a neutralized salt thereof. )It is in. The blending amount of the iron-based desiccant and manganese-based desiccant used in the present invention is 0.002 to 0.002% of the solid weight of the printing ink, respectively.
0.3% by weight, preferably 0.005-0.15% by weight, manganese desiccant 0.002-0.3% by weight, preferably
It is necessary that the content be within the range of 0.01 to 0.15% by weight. Outside this range, as will be described later, there will be a drawback that the balance between the drying time of the thin film and the drying time of the thick film will be lost. Optionally, 0.01 to 0.5% by weight of a calcium, barium, zinc, or zirconium desiccant may be added. In addition to these metal desiccants, it is necessary to blend a reducing agent represented by the general formula above. The mixing ratio thereof needs to be in the range of 0.001 to 0.5% by weight based on the solid weight of the printing ink. Next, the thin film drying time and thick film drying time in the case where no reducing agent is blended and in the case where the blending amount of the reducing agent is changed are as follows.

[Table] As this result shows, when a reducing agent is added,
Thin film drying time can be accelerated or thick film drying time can be increased without slowing down. If the reducing agent exceeds 0.5% by weight, the thick film drying time becomes longer, but the thin film drying time also becomes longer. If less than 0.001% by weight is added, the drying time for a thin film is fast, but the drying time for a thick film is shortened, making it easier to form a thick film. Further, the relationship between the blending amount of the desiccant and the drying time for thin films and thick films is as follows.

【table】

[Table] As is clear from the results in 9 to 14 above, if the iron content is less than 0.002% by weight, thin film drying becomes too slow, and if it exceeds 0.5% by weight, a problem arises in that thick film drying becomes faster. Further, as is clear from the results of Nos. 15 to 20, if the manganese content is less than 0.002% by weight, thin film drying becomes too slow, and if it exceeds 0.3% by weight, thick film drying becomes too fast. Examples of the reducing agent compound represented by the general formula used in the present invention include 1-phenyl-3-pyrazolidone, paradioxybenzene, orthodioxybenzene,
2,6-dioxyphenol, 3,5-dit-tertiarybutyl-4-hydroxytoluene, para-aminophenol, ortho-aminophenol, para-phenylene diamine, ortho-phenylene diamine,
Monomethyl para-aminophenol, monomethyl meta-aminobutyl, 2,4-diaminophenol,
2-chloro-4-oxyphenol, 4-amino-N,N-diethylaniline, 4-amino-N,
Examples include N-dimethylaniline, 4-amino-N,N-diethylaminomethatoluidine, and neutralized salts thereof. Examples of the metal carboxylic acid (Fe, Mn) of the desiccant include compounds of monocarboxylic acids with or without branching having 6 to 22 carbon atoms, or aliphatic monocarboxylic acids having 6 to 10 carbon atoms. . Examples of the compound include 2-ethylbutanoic acid,
2,2-dimethylpentanoic acid, 2-ethylpentanoic acid, 2-ethyl-4-methylpentanoic acid, 2-
Ethylhexanoic acid, isooctanoic acid, isononanoic acid, neononanoic acid, isodecanoic acid, neodecanoic acid, 2-ethyldecanoic acid, isotridecanoic acid, isotetradecanoic acid, n-octanoic acid, n-dodecanoic acid, cyclopentanoic acid, methylcyclopentanoic acid, Examples include metal salts of cyclohexanoic acid, methylcyclohexanoic acid, 1,2-dimethylcyclohexanoic acid, and cycloheptanoic acid. Among them, acids suitable for the production of metal salts include, for example, 2-ethylhexanoic acid, isooctanoic acid, 2,2-diethylhexanoic acid, 2-methyl-2ethylheptanoic acid,
2,2-dimethyloctanoic acid, 2-propylheptanoic acid, 3,5,5-trimethylhexanoic acid, 3
-ethyloctanoic acid, isononanoic acid, isodecanoic acid, isododecanoic acid, 2-ethyldodecanoic acid, tall oil fatty acid, naphthenic acid, cyclopentanoic acid,
Examples include cyclohexanoic acid, cycloheptanoic acid, and methylcyclohexanoic acid. However, the salt is not limited to these, and any iron or manganese salt that forms a carboxylic acid metal salt and acts as a desiccant may be used. The iron in the iron salt may be either trivalent or divalent, but trivalent iron is preferred since it improves the slow drying properties of thick films. However, if it is not colored, divalent iron is used. Ink forming components in printing ink include:
A dry or semi-drying oil component that hardens by oxidative polymerization is blended in an amount of 1% by weight or more, preferably 2.5% by weight or more based on the total amount of the printing ink. For example, alkyd resin, urethane resin, polyester resin, unsaturated polyester resin, epoxy resin, phenol resin, rosin phenol resin, rosin ester resin, rosin modified maleic acid resin, melamine resin, urea melamine resin, acrylic resin, petroleum resin, xylene Examples include resin. Also, naturally occurring dry or semi-dry oils such as tung oil, linseed oil, eno oil, safflower oil,
Included are hempseed oil, soybean oil, cottonseed oil, corn oil, rubber oil, rapeseed oil, bran oil, squid oil, fish oil, whale oil, and fatty acids obtained therefrom. Furthermore, modified oils of naturally occurring oils such as dehydrated castor oil, dehydrated castor oil fatty acids, tall oil fatty acids, hydien fatty acids (manufactured by Soken Kagaku Co., Ltd.), Pamolici (manufactured by Hercules Corp.), or polybutadiene with an average molecular weight of 2500 or less. Synthetic drying oils such as polyisoprene and the like may also be used. Of course, mixtures of two or more of the above may also be used. Further, a non-oxidative polymerizable resin may be mixed with these. Non-oxidative polymerizable resins include rosin ester,
Non-oxidative polymerization of rosin salts, maleated rosins and their ester resins, rosin phenolic resins, alkyl phenolic resins, rosin modified xylene resins, petroleum resins, gilsonite, cyclized gums, ketone resins, vinyl resins, acrylic resins, epoxy resins, etc. Examples include mold resin. The film coating agent contains, as necessary, solvent components such as diesel oil, spindle oil, ink solvent, and machine oil, which are usually mixed with oil-based paints and printing inks, waxes, coloring materials, extender pigments, consumables, and leveling agents. Mix modifiers, anti-skin agents, thickeners, etc. Example 1 A dryer and a reducing agent were added to an ink base having the following composition, and the thick film drying time and thin film drying time were measured. The results are as follows. Composition of ink base material (% represents weight%) Linseed oil modified alkyd resin 25%, rosin phenol resin 25%, No. 5 solvent for ink 29%, pigment 20
% mixed.

[Table] The drying time for a thick film was measured by placing 10 g of printing ink on a glass plate to a thickness of 0.5 cm, placing it in a thermostatic chamber at 25°C, and measuring the time until the surface was no longer touched by fingers. The drying time of the thin film was measured by spreading 0.4 ml of printing ink on high-quality paper using an RI tester, placing it in a constant temperature room at 25°C, and measuring the time until the surface could no longer be touched by fingers. From the above results, it can be seen that the printing ink of the present invention has an excellent effect of increasing the drying time of thick films without increasing the drying time of thin films. In addition, by including carboxylic acid metal salts of iron and manganese within a specific range as desiccants, and at the same time using a specific reducing agent in an amount within a specific range, the printing ink properties can be improved due to their synergistic effect. was obtained by improving as described above.

Claims (1)

[Claims] 1. As iron relative to the solid weight of printing ink.
An iron carboxylate desiccant in an amount of 0.002 to 0.5% by weight, a manganese carboxylate desiccant in an amount of 0.002 to 0.3% by weight as manganese, and a reducing agent represented by the following general formula in an amount of 0.001 to 0.5% by weight. % printing ink. general formula However, R ₁ represents [Formula] OH, NH ₂ , NH・CH ₃ , NH・C ₂ H ₅ , [Formula] [Formula] NH・CH ₂ OH or NHC ₂ H ₄ OH, or a neutralized salt thereof. , R ₂ , R ₃ , R ₄
is H, F, Cl, Br, I, alkyl group having 1 to 4 carbon atoms, CH ₂ OH, OH, NH ₂ , NHCH ₃ ,
NHC ₂ H ₅ , [Formula] [Formula] NH- Represents CH ₂ OH or NH·C ₂ H ₄ OH, or a neutralized salt thereof. )