JP2979339B2 - Metallic glossy ink for marking pens - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a metallic glossy ink for a marking pen. More specifically, the present invention relates to a low-toxic metallic luster color ink for marking pens, comprising a vehicle containing a resin soluble in at least one solvent selected from lower aliphatic alcohols and glycol ethers.

2. Related Art Metallic glossy ink for marking pens is disclosed in
No. 27624, JP-A-57-28176 and the like.

The inks disclosed in the above-mentioned conventional publications and the like were treated with a fatty acid or a fatty acid salt in a vehicle containing a solvent dissolved in these solvents using a solvent such as an aromatic or aliphatic hydrocarbon, a ketone, or an ester. This is an ink in which metal powder is dispersed.

When active acid groups, moisture, and the like are present in the vehicle, the metal powder easily undergoes orientational substitution with these and becomes familiar with the vehicle (wet), causing loss of leafing properties (floating properties) and deterioration due to surface oxidation. That is, in order to avoid these problems, the above-mentioned nonpolar solvent is applied.

Problems to be Solved by the Invention Solvents such as aromatic hydrocarbons, ketones, esters and the like conventionally applied do not always satisfy recent social demands from the viewpoint of toxicity and safety. Even if it satisfies safety if it is based on water, it has clear metallic luster,
In a situation where stability over time cannot be obtained, the present invention relates to a vehicle comprising a combination of a specific resin selected from resins dissolved in the solvent using a solvent selected from alcohols, glycol ales and the like. Enthusiastically pursue,
A low-toxic metallic luster color ink for marking pens that satisfies the metallic luster, aging stability, ink outflow properties, and writing performance.

Means for Solving the Problems The metallic luster color ink for a marking pen of the present invention is a fine metal powder selected from aluminum, copper, zinc, and copper alloy surface-treated with a fatty acid or a fatty acid salt, and an organic resin in which a resin is dissolved. In the metallic luster color ink for a marking pen dispersed in a solvent, (a) the resin is at least one resin selected from a phenol resin, a hydrocarbon resin having a hydroxyl group, and a polyvinyl butyral resin, and (b) the organic solvent is , At least one solvent selected from lower aliphatic alcohols and glycol ethers.

In the above, as the fatty acid or fatty acid salt for treating the metal powder, a saturated or unsaturated fatty acid having 16 to 24 carbon atoms or an aluminum salt thereof is effective. The metal powder has an average particle size of 1 to 25 μm passed through a 400 mesh sieve, and is mixed in a range of 4 to 35% by weight based on the total weight of the ink.

In the above, when the metal powder is 3% by weight or less, a handwriting of a clear metallic glossy color having a concealing property cannot be obtained. On the other hand, when it exceeds 35% by weight, the ink outflow from the pen tip deteriorates remarkably. , 5 to 30% by weight is preferred. Also, if the average particle size of the metal powder is small, it is effective in terms of ink spillability from the pen tip, but if the average particle size is too small, the metallic gloss color tends to be extremely reduced, The average particle diameter of the powder is preferably in the range of 3 to 20 μm, and the pen body of the marking pen (for example, a bundle of fiber bundles, the above-mentioned resin processed body, felt material, a plastic porous body having continuous pores, a plastic rod) Etc.) and the handwriting performance is satisfied.

In order to give leafing metal powder, carbon
While those surface treated with ~ 18 saturated fatty acid is effective, that the surface treatment is performed on directly the metal surface, of course, prior to the processing, C ₁₂ or more higher fatty family amine, preferably a straight-chain saturated aliphatic amine C ₁₆ -C ₁₈ (primary or secondary) in the base, the metal surface to adsorb the amine, to form the surface state of the unoxidized, the A system in which a fatty acid is reacted to form a film of a fatty acid salt of an aliphatic amine is more rich in metallic luster and excellent in corrosion resistance. In addition, the aliphatic amine can be blended in a vehicle to reduce familiarity (wetting) with metal powder, improve leafing properties, and prevent discoloration by oxidation by binding to an active acid group such as a free acid. Etc. can be contributed.

The solvent applied to the present invention is selected from lower aliphatic alcohols and / or glycol ethers. Specifically, aliphatic-hydric alcohols having 2 to 4 carbon atoms, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like are exemplified.

The resin is specifically a phenolic resin such as a novolak type phenol resin, a novolak type alkylphenol resin, a paravinyl phenol resin, a polyvinyl butyral resin, a hydrocarbon resin having a hydroxyl group, a dicyclopentadiene hydrocarbon resin, an aromatic resin. Hydrocarbon resin,
Examples thereof include aliphatic-aromatic copolymerized hydrocarbon resins.

The resin is used in the ink composition in a range of 2 to 35% by weight, and is dissolved in the above-mentioned solvent to form a vehicle. The dispersion stability of the metal powder, the adhesion to the surface to be written, and the glossiness of the handwriting To work effectively to give.

The ink of the present invention is 5 to 70 mPa.S in terms of ink outflow from the pen body of the marking pen, handwriting performance, and easy re-dispersibility of the ink in the marking pen barrel by the stirring ball.
(Preferably 10 to 60 mPa.S).

Incidentally, in the ink of the present invention, CI solvent dyes such as spirit soluble dyes, insoluble azo dyes, phthalocyanine pigments, thioindigo pigments, sullen pigments, quinacridone pigments, disazo pigments, etc. Can be blended. In addition, aluminum powder is substituted for part of the bronze powder within the range that maintains the gold color, and the properties of aluminum powder (excellent in weather resistance, lower in specific gravity, less sedimentation and redispersibility than bronze powder) Can be effectively expressed and modified.

Action The vehicle of the present invention appropriately disperses a metal powder surface-treated with a fatty acid or a fatty acid salt, does not cause thickening, deterioration, or discoloration over time, and satisfies the ink outflow property from the pen tip of the marker. It shows good wettability on various objects to be written and can be written sharply, and functions effectively to give handwriting of metallic luster color with excellent adhesion.

In a system in which the surface treatment of the metal powder is performed by using an aliphatic amine and a fatty acid in combination, particularly in a system in which the aliphatic amine is adsorbed on the metal powder surface in advance and then the fatty acid is reacted, the fatty acid salt of the aliphatic amine is used. By forming a film of, the metal glossiness is further enhanced and the effect is exhibited in terms of corrosion resistance. In a system in which an aliphatic amine is blended in a vehicle, the leafing property is improved by reducing the familiarity (wetting) with the metal powder, and the bond with an active acid group such as a free acid in the vehicle is made, thereby deteriorating due to surface oxidation. Does not occur.

Examples Example inks of the present invention are described below in comparison with comparative example inks. The present invention is not limited to this example, and copper powder, zinc powder, or a system of these bronze powders can be prepared according to the examples.

 Table 1 shows the ink composition and test results.

(1) Preparation of Example Inks and Comparative Example Inks A resin was added to a solvent, stirred for about 1 hour with a disper, then a metal powder was added, and stirring was continued for about 2 hours at room temperature.

(2) Test method and evaluation criteria Viscosity: Measured at about 20 ° C with an ELD viscometer.

Color tone (glossiness): Handwriting on the glass plate is judged visually with the C light source and the distance of clear vision.

○: good color tone (gloss) △: slightly poor color (gloss) ×: extremely poor color (gloss) Marker redispersibility: The sample ink is filled into the marker, and the ink is once applied from the pen body. After draining it to make it writable, put on the cap, put it upright (pen point up) and invert (pen point down), leave it at 50 ° C for 7 days, and leave it A 3 mm line was drawn on the transparent polyester film of 100 μm, and the unreadable state of the printed characters on the paper placed below was evaluated as “good concealment” (standard).

○: Marker with good concealment property after writing with no shaking of the marker or pumping operation of the pen tip. △: Marker “Twice shaking operation → twice pumping operation of the pen tip → writing. "" As one cycle, the "hiding property" recovers after 1 to 2 cycles x .... "Hiding property" recovers by 3 or more cycles of operation Remarks ... The marker is a pen body (fiber bundle) Resin body) is slidably inserted in the axial direction, the rear end of the pen body is connected to a valve mechanism mounted on the front of the barrel, and ink is stored in the barrel at the rear of the valve mechanism. The stirrer balls loosely inserted into the storage portion are rotated by the shaking of the shaft portion so that the ink stored in the shaft portion can be stirred. The front end is intermittently pressed to activate the valve mechanism connected to the rear end of the pen body So, the writing tip direction refers an operation for deriving the ink) has a configuration which can control the flowage amount of the ink from the pen body by.

Details of the ink raw materials are described below according to the note numbers.

Leafing type bronze powder (average particle size: 5 μm) manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd. Leafing type aluminum paste manufactured by Toyo Aluminum Co., Ltd. [solvent: mineral terpene, stearylamine (2% by weight in the paste), Surface treated with stearic acid (4% by weight in paste) (average particle size
15 μm), solid content about 60%) Leafing type aluminum paste manufactured by Toyo Aluminum Co., Ltd. [solvent: treated with mineral terpene, stearic acid (about 3% by weight in the paste), average particle size 15 μm, solid content about 65%] Non-leafing type aluminum paste manufactured by Toyo Aluminum Co., Ltd. [solvent: Mineral turn, treated with oleic acid, average particle size 13 μm, solid content approx. 66%] Arakawa Chemical Co., Ltd., novolak type pure phenol resin Nippon Petrochemical Co., Ltd., dicyclopentadiene hydrocarbon resin [hydroxyl value: 240-260 (mgKOH / g)] Arakawa Chemical Co., Ltd., novolak type alkylphenol resin Maruzen Petrochemical Co., Ltd., paravinylphenol resin [hydroxyl value: 120 (mg KOH / g)] Nippon Petrochemical Co., Ltd., C ₉ fraction as a raw material hydrocarbon resin [hydroxyl value: 120 (mg KOH / g)] Kawa Chemical Co., Ltd., Ketone resin Arakawa Chemical Co., Ltd., Rosin maleic acid resin Nippon Shellac Co., Ltd., Shellac resin Sekisui Chemical Co., Ltd., Butyral resin Nippon Alcohol Sales Co., Ltd., Industrial ethanol Effect The metallic luster color ink of the present invention can be obtained by using an aliphatic alcohol and / or
Alternatively, a vehicle in which glycol ether is used as a solvent and a specific resin compatible with these is selected and blended is used, so that it is lower than a conventional system in which aromatic hydrocarbons, ketones, esters, etc. are used as a solvent. A toxic marking pen ink can be provided. The obtained ink satisfies the ink outflow property from the pen tip of the marker without causing viscosity increase, deterioration and discoloration over time, shows good wettability to various types of object to be printed, and writes sharply. Can, wear resistance,
It has robustness such as weather resistance.

Further, since the metallic glossy ink of the present invention has good re-dispersibility, the ink can be easily re-dispersed by shaking the barrel of the marker (a stirring effect of a stirring ball inserted into the barrel). In this way, uniform ink can flow out of the pen tip to maintain desired writing performance.

Claims (1)

(57) [Claims] 1. A fine metal powder selected from aluminum, copper, zinc and copper alloy surface-treated with a fatty acid or a fatty acid salt,
In a metallic luster color ink for a marking pen dispersed in an organic solvent in which a resin is dissolved, (a) the resin is at least one resin selected from a phenol resin, a hydrocarbon resin having a hydroxyl group, and a polyvinyl butyral resin; b) The metallic glossy ink for marking pens, wherein the organic solvent is at least one solvent selected from lower aliphatic alcohols and glycol ethers.