JPH0156109B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a metallic luster color ink for marking pens. Specifically, it provides ink for marking pens that is effective in giving clear, opaque, and robust handwriting with metallic luster such as gold, silver, and copper color to various substrate surfaces. be. Conventionally, various techniques have been disclosed and put into practical use regarding metallic gloss color inks for printing. However, there is no disclosure of technology that satisfies the practicality of writing instruments, and there are various practical problems. For example, the ink for writing instruments disclosed in Japanese Patent Publication No. 53-27975 uses crushed ultra-fine pieces (size 0.3 to 20μ, thickness 0.4 ~1.5μ, specific gravity 1
~2), and even if it satisfies performance such as clarity and reflectivity to some extent, it is insufficient in terms of depiction performance and robustness on various substrate surfaces, and
In order to obtain crushed ultra-fine pieces of the metal vapor-deposited foil, as disclosed in the same publication, an undercoat layer capable of metal vapor deposition is provided on a predetermined plastic base film, and on this, a metal-depositable undercoat layer is formed. Accordingly, a metal vapor deposited layer of a predetermined thickness is formed in a high vacuum region and a high temperature region, a top coat layer is further provided on top of the metal vapor deposited layer, the obtained metal vapor deposited foil layer is peeled off and collected, and the peeled pieces are then crushed. You have to go through the process of
It is extremely expensive and has problems in practical use.
Furthermore, the ink disclosed in JP-A No. 50-27624 consists of metal powder with an average particle size of 20μ or less, an organic solvent, a resin, and benzotriazole dissolved in alcohol, and the ink does not flow out from the pen tip. Even if it is possible to write on it, it is difficult to sufficiently develop a clear and reflective metallic luster, and furthermore, it has not been possible to eliminate problems such as deterioration and discoloration in terms of storage stability over time. The ink of the present invention improves the above-mentioned conventional defects and provides a highly practical metallic luster color ink for marking pens. The ink of the present invention (a) has smooth ink flow from various marking pens, and (b) exhibits good wettability to various photographic materials as a quick-drying ink;
(c) clear metallic luster color and concealability with no deterioration or discoloration, both initially and over time; (d)
It has robustness such as abrasion resistance and weather resistance, and also has (v) easy dispersibility during ink production and practical use. The ink of the present invention can be applied to various types of pen bodies, such as pen bodies made of bundled fibers, pen bodies processed with resin,
It is applied to marking pens with felt materials, plastic porous bodies with continuous pores, plastic rods with axially perforated holes, etc. In addition, the marking pen structure is such that ink is supplied from the ink storage part to the pen body by operating the valve body by pressing operation, and there are also marking pens that are configured to supply ink from the ink storage part to the pen body by interposing a helical or similar guide core from the ink storage part. A structure in which a highly porous ink storage body is connected to a pen body, etc. are applicable. Further, a structure in which a stirring ball is incorporated in the ink storage section or a stirring blade or the like is inserted to promote redispersion during practical use may be used as appropriate. In order to maintain smooth and homogeneous ink flow from these marking pens and desired handwriting performance, the viscosity of the ink must satisfy 50 centipoise or less. The inventors of the present invention have satisfied the above-mentioned performance and, as a result of intensive studies considering the suitability of ink for marking pens, have found that the ink has sufficient metallic luster even in a relatively low viscosity region such as 50 centipoise or less. In order to obtain concealment properties, the metal powder itself must be small enough to pass through a 400-mesh sieve, and a leafing type must be used that has the characteristic that metal powder particles float on the surface of the coating film and are arranged in parallel. was found to be an essential condition. Furthermore, since the leafing type uses a surface treated with a lubricating substance such as palmitic acid, stearic acid, or oleic acid, the apparent specific gravity of the metal powder particles is relatively small and tends to be difficult to settle. Even if it settles, it is considerably larger than general dyes, organic pigments, and titanium white, etc., and the particle size is distributed in the range of 3 to 40μ, and the particles are surface-treated with a moisturizing substance. It is extremely easy to redisperse with a slight mechanical impact. Furthermore, in order to extend the writing life of a marking pen, the particle size of the metal powder must be in the range of 5 to 10 μm, with an average particle size that passes through a 400 mesh sieve.
It has been found that it is effective that the cumulative distribution ratio of particles of 15μ or less is 80% or more. If the metal powder is made finer than the above range, the ink flowability will be improved, but the metallic luster will be extremely reduced, which is not preferable. On the other hand, if the size of the metal powder particles exceeds the above range, clogging will easily occur in the pen body during writing, and the writing life will be extremely shortened. The metal powder used in the ink of the present invention has a color tone,
From the point of view of gloss and concealment, it is essential to use leafing-type ink such as smooth scaly powder, but when filling a marking pen with ink and writing, ink made of leafing-type metal powder is indispensable. The abrasion resistance is not sufficient because the metal powder particles float on the surface of the writing coating and are arranged in parallel. Therefore, it is possible to use the non-leafing type in combination in a range of 10 to 200% by weight of the leafing type to assist in wear resistance. Combines contradictory properties of wear resistance and gloss,
Considering practicality, the non-leafing type is
It is more preferable to use the amount in the range of 30 to 60% of the amount used for the leafing type. That is, in the non-leafing type, the metal powder is uniformly dispersed and arranged in the coating film, so the gloss is inferior to the leafing type, but the abrasion resistance is improved. Among the metal powders used in the ink of the present invention, aluminum powder is used in the form of a paste moderately moistened with mineral spirits, naphtha, or an aromatic solvent in consideration of storage risks. The amount used can range from 1 to 50% by weight in the ink. In order to maintain viscosity, color tone, and gloss, it is more preferable to use it in an amount of 10 to 30% by weight in the ink. Any resin can be used for the ink of the present invention as long as it does not have a high acid value that degrades leafing properties, but the metal powder used for the ink of the present invention has leafing properties that are slightly inferior in abrasion resistance. Since the type is the main component, it is preferable to use an air-drying resin that has sufficient adhesion and tackiness to metals, glass, and plastics, and that does not separate and agglomerate in the vehicle. These resins include hydrocarbon resins (thermoplastic resins obtained by polymerizing olefinic and diolefinic unsaturated hydrocarbons, or thermoplastic resins obtained by hydrogenating this) or xylene resins, which have polar functional groups. It is suitable because it does not inhibit the leafing property of the metal powder or change its quality, and if necessary, methacrylate resin, polyacrylate resin, phenol resin, polyamide resin, polyester resin, alkyd resin can be used. , ketone resin, etc. can be used in combination in small amounts. The hydrocarbon resin or xylene resin can be used in an amount of 20 to 200% by weight based on the amount of metal powder used, but it is more preferably in a range of 50 to 100% by weight. Next, the rust preventive will be explained. The rust inhibitor used in the ink of the present invention is a C ₁₂ to C ₂₂ saturated aliphatic amine and/or a C ₈ to _{C 22} alkyl mercaptan, and the amine and alkyl mercaptan are mixed in a ratio of 1:0.1 to 1:0.1.
It has been found that it is effective to use them together at a weight ratio of 2.0. In particular, it is effective in the case of golden luster-colored ink using brass powder, and it not only suppresses deterioration and deterioration of the color tone and glossiness of the ink stock solution over time, but also prevents deterioration, deterioration, and discoloration of handwriting over time. succeeded in preventing it. In the above, in the case of a C ₈ or less system, both the aliphatic amine and the alkyl mercaptan tend to have an affinity with the metal powder, which tends to inhibit the leafing property of the metal powder, and also tends to evaporate, reducing the rust prevention effect.
On the other hand, when _C22 is exceeded, the ability of the resin in the vehicle to neutralize acid groups tends to decrease significantly. Therefore,
The amines and mercaptans are preferably C ₁₂
to _C18 . The rust preventive used in the ink of the present invention can be used in an amount of 0.01 to 10% by weight of the metal powder used, but is preferably used in an amount of 0.5 to 5% by weight. Next, it is important to avoid the use of polar solvents in order to maintain the leafing properties of the solvent used in the ink of the present invention. Examples include solvents such as organic solvents, ketones, and esters. Specifically, xylol, toluol, swazol, naphthas, normal hexane, alkylcyclohexane, heptane, cyclohexanes, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, and the like can be mentioned. In the ink of the present invention, pigments such as azo lake red pigments, polyazo yellow pigments, and cyanine green pigments, acid dyes, metal-containing complex salt dyes, phthalocyanine blue dyes, etc. may be added to the ink of the present invention in addition to the metal powder. It is also possible to obtain metallic colors by color matching. Examples of the ink of the present invention are illustrated in Tables (1) and (2) below. Without being limited to this example, in the case of copper powder, zinc powder, or a blend thereof,
It can be prepared as described above. The performance of the example ink is as illustrated in Table (3). After applying the ink of the present invention to a marking pen equipped with a fiber resin-treated pen body, etc., and leaving the pen body facing upward for a long period of time, When we observed the handwriting performance at the beginning of writing, we found that it had the expected color tone, glossiness, and concealment properties. Furthermore, it goes without saying that it has sustained handwriting performance even after continuous writing. The above-mentioned development has an effective performance not found in conventional dispersible marking pen inks made of organic pigments or inorganic pigments such as titanium oxide. This performance is believed to be due to the composition of the ink of the present invention, in which leafing-type metal powder treated with fatty acids or fatty acid salts is effectively dispersed in as small a size as possible to have a scale-like shape within the range of having a metallic luster color. . That is, this is because the apparent specific gravity of the metal powder particles is relatively small compared to the vehicle, and furthermore, they are floating and arranged in parallel over the entire surface of the pen body, which is one of the features of the ink of the present invention. It is one.

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Claims (1)

[Scope of Claims] 1 (a) Aluminum surface-treated with 10 to 30% by weight of fatty acid or fatty acid salt based on the total amount of ink;
A fine metal powder selected from copper, zinc, and copper alloys and having a cumulative distribution ratio of particles of 15μ or less that passes through a 400-mesh sieve is 80% or more; (b) a hydrocarbon resin containing 20 to 200% by weight of the metal powder; or xylene resin, (c) an organic solvent selected from aromatic hydrocarbons, aliphatic or alicyclic hydrocarbons, ketones, and esters for dissolving the resin, as an essential component, and optionally (d) a rust preventive; (e) A metallic gloss colored ink for marking pens containing a coloring agent and having a viscosity of 50 centipoise or less. 2. The metallic gloss color ink for marking pens according to claim 1, wherein the fatty acid or fatty acid salt is a saturated fatty acid having 16 to 18 carbon atoms or an aluminum salt thereof.