JPH01306275A - Ink ribbon - Google Patents

Abstract

PURPOSE:To remarkably eliminate the corrosion of a printing wire, with elongating the life of a printing head and improviding the reliability thereof, by mixing a corrosion suppressing agent of adherion type of a predetermined concentration into a ribbon ink. CONSTITUTION:A corrosion suppressing agent of adhesion type is mixed into ink of an ink ribbon by 0.1 to 10 weight parts for 100 weight parts of the ink. The corrosion suppressing agent of adhesion type is physically or chemically adhered to the metal surface of a printing wire which is subjected to corrosion, so that the area where the corrosion reaction progresses in the metal surface can be considerably reduced. As a result of this, the breakage or the like of the printing wire due to the corrosion can be extraordinarily reduced.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to an ink ribbon.

(Prior art) In recent years, impact printers, which are cost-effective and capable of high-speed printing on a variety of media, have been used in a wide variety of applications, including peripheral terminal devices for information processing systems as man-machine interfaces. In particular, there is a high demand for high-speed printing.

Impact printers that print at high speeds stably process large amounts of information, so one of the important issues is that the print head has high reliability. And especially the printing wire,
Stable operation over a long period of time without causing corrosion or abrasion or damage to the ink ribbon is strongly desired.

For example, there is a printing wire using a wear-resistant alloy such as cemented carbide (Japanese Patent Application Laid-open No. 79766).

However, even these printing wires had a major drawback in that the metal components of the printing wires could be chemically corroded after long-term use.

By the way, the above-mentioned corrosion of the printing wire depends on the ink components contained in the ink ribbon.

The black ink of the conventional ink ribbon is, for example,
- Contains carbon black as a coloring material as disclosed in Japanese Patent No. 60956, that is, carbon black as a coloring material and an oil-soluble dye are added to vegetable oil and mineral oil as a vehicle, and further auxiliary agents such as a dispersant are added. The composition is

Usually, the above carbon black contains 2 to 30% impurities.
Contains 5% by weight of ash, as well as sulfur oxides, chlorine ions, etc., and these impurities chemically corrode the metal components of the print wire surface layer in the presence of moisture and oxygen in the atmosphere, causing print head wear and tear. This causes serious problems such as broken print wires.

(Problems to be Solved by the Invention) In order to solve these problems, it is possible to use a purified product of carbon black with an ash content of 1% or less, or to remove impurities from the carbon blank at the ribbon ink manufacturing stage. A method was taken. However, refined products of carbon black are usually very expensive, and removing impurities at the ribbon ink manufacturing stage increases the number of steps, significantly increasing the manufacturing cost of the ink ribbon.

SUMMARY OF THE INVENTION The object of the present invention is to eliminate the drawback of severe corrosion of the printing wire and to provide an inexpensive ink ribbon.

(Means for Solving the Problems) The present invention provides an ink containing the formula R-NH in an ink ribbon.
z, RR'-NO, RR'R"-N (1 in the formula?,
R', R'' represent an alkyl group), thiourea and its derivatives, benzotriazole and its derivatives, thiazole, thioamides, or thiosemicarbazide.
It is mixed in an amount of 0.1-10 parts by weight.

(Function) In the present invention, the adsorptive corrosion inhibitor (hereinafter also referred to as an additive) added to the ink is physically adsorbed or chemically adsorbed on the metal surface of the printing wire that is subject to corrosion. Significantly reduces the area where corrosion reactions can proceed,
As a result, breakage of the printing wire due to the above-mentioned corrosion is drastically reduced.

(Example) Next, the present invention will be specifically explained using examples.

Note that parts in the following description are parts by weight.

Comparative Example 1 30 parts of vegetable oil and 3 parts of mineral oil were used as vehicles as shown in the table below.
0 parts 1 15 parts of carbon black and 15 parts of oil-soluble dye as a coloring material, and 10 parts of sorbitan fatty acid ester as a dispersant are premixed in a planetary mixer, and this mixture is uniformly kneaded with three rolls to form a ribbon ink. was prepared.

The ink ribbon base fabric is made of polyamide fibers such as nylon 6 or nylon 66, or polyester fibers with a length of 50 m, a width of 13 mm, and a thickness of 0.12 m++.
An endless ribbon of Möbius ring (+) was used as a base fabric, and 12 g of the above ribbon ink was uniformly applied and impregnated per each ribbon. The obtained ink ribbon was attached to an impact printer together with a print head using a print wire made of a wear-resistant alloy, and printing was performed. The operating conditions were a printing stress of 14 kg/-, a printing speed of 180 times/sec, an ink ribbon feeding speed of 30 m/sec, and a printing rate of 1 per printing wire.
Five copies were printed 00,000 times and left in the atmosphere at room temperature for one week with the ribbon ink attached to the printing wire.

Now, regarding the degree of corrosion of the printing wire, we analyzed the cobalt on the surface of the printing wire before printing and after leaving it for one week after printing using an SEM using an electron microscope, and calculated the respective cobalt content ratios (hereinafter, this ratio is referred to as the corrosion rate). On the other hand, the surface condition of the printed wire was observed using an electron microscope.The result was that the corrosion value was 0.o2.
As for the surface condition, a large number of cobalt corrosions were observed as schematically shown in FIGS. 2 and 3.

Next, when this print head was used to print an additional 150,000 times, several print wires broke in the corroded portion, resulting in unprinted pixels.

Comparative Example 2 30 parts of vegetable oil, 28.99 parts of mineral oil, 15 parts of carbon black, 15 parts of oil-soluble dye, 10 parts of sorbitan fatty acid ester, and 0.01 part of dodecyldimethylamine, which is a type of amine, were mixed as an additive. An ink was obtained in the same manner as in Comparative Example 1, and an ink ribbon was manufactured using this ink. Comparative example 1: Attach this to the printer and start printing.
was evaluated.

As a result, the corrosion value was 0.15, and when the printing operation was performed in the same manner, several of the printing wires were similarly broken at the corroded portions, resulting in unprinted pixels.

Example 1 31 parts of vegetable oil, 28.9 parts of mineral oil, 1 part of carbon black
5 parts, oil-soluble dye 15 parts, sorbitan fatty acid ester 1
0 parts, and 0.1 dodecyldimethylamine as an additive
The ink was mixed in the same manner as in Comparative Example 1, and an ink ribbon was manufactured using the ink. This was attached to a printer, and the printing operation was performed to perform the same evaluation as in Comparative Example 1. As a result, the corrosion value was 0.72, which is close to 1, and observation of the surface condition using an electron microscope showed that almost no corrosion was observed, which was good. After that, the printing operation continued in the same manner, but no printing wires were broken, and no unprinted pixels were observed. In addition, almost no deterioration was observed in the printed pixel quality in terms of sharpness and one hue.

Example 2 An ink was prepared in the same manner as in Comparative Example I by mixing 30 parts of vegetable oil, 25 parts of mineral oil, 15 parts of carbon black, 15 parts of oil-soluble dye, 10 parts of sorbitan fatty acid ester, and 5 parts of dodecyldimethylamine as an additive. This was used to produce an ink ribbon.

This was installed in a printer, and a printing operation was carried out, and evaluation was conducted in the same manner. As a result, the corrosion value was 0.89, which was even closer to 1, and as a result of surface observation using an electron microscope, almost no corrosion was observed. After that, printing was performed in the same manner, but no printing wires were broken and no unprinted pixels were observed.

Instead of the above dodecyldimethylamine, one or a mixture of two or more of dodecylamine and oleylamine as the primary amine, dioleylamine as the secondary amine, and octadecyldimethylamine as the tertiary amine was used, but the results were almost the same. I got the result.

Example 3 Ink was prepared in the same manner as in Comparative Example 1 by mixing 25 parts of vegetable oil, 25 parts of mineral oil, 15 parts of carbon blank, 15 parts of oil-soluble dye, 10 parts of sorbitan fatty acid ester, and 10 parts of dodecyldimethylamine as an additive. This was used to produce an ink ribbon. This was attached to a printer and printed in the same manner for evaluation. As a result, the corrosion value was 0.94, and as a result of surface observation using an electron microscope, almost no corrosion was observed. After that, the printing operation continued in the same manner, but no printing wires were broken, and no unprinted pixels were observed. Also, the quality of printed pixels did not deteriorate in sharpness or in one hue.

Example 4 13 parts of oil-soluble binder 1, 12 parts of dodecyldimethylamine
The same procedure as in Example 3 was carried out except that the parts were used as parts. The results of the evaluation are
The corrosion value was 0.95, and as a result of surface observation using an electron microscope, almost no corrosion was observed. Further printing operation
However, there was no breakage of the printing wire, no unprinted pixels were observed, and the quality of the printed pixels did not deteriorate in sharpness or in one hue.

Based on the results of Comparative Example 1 to Example 4, the corrosion value versus concentration of dodecyldimethylamine is graphed and shown in FIG. This figure shows that when dodecyldimethylamine is added, the corrosion value of the printing wire rapidly approaches 1 and increases as the concentration increases, but does not increase significantly when the concentration exceeds 10 parts.

Example 5 The same procedure as in Example 2 was repeated except that 5 parts of thiourea was used instead of dodecyldimethylamine. As a result, the corrosion value was 0.8
2, and as a result of surface observation using an electron microscope, almost no corrosion was observed, and the quality of printed pixels did not deteriorate in sharpness or hue.

Similar results were obtained using thiourea M'S form instead of the above-mentioned thiourea.

Example 6 The same procedure as in Example 2 was repeated except that 5 parts of benzotriazole was used instead of dodecyldimethylamine. As a result, the corrosion value was 0.87, and as a result of surface observation using an electron microscope, almost no corrosion was observed, and the quality of printed pixels did not deteriorate in sharpness or in one hue. Similar results were obtained using benzotriazole derivatives other than the above benzotriazole.

Example 7 The same procedure as in Example 2 was repeated except that 5 parts of thiazole was used instead of dodecyldimethylamine. As a result, the corrosion value was 0.86
As a result of surface observation using an electron microscope, almost no corrosion was observed, and the quality of printed pixels did not deteriorate in sharpness or two hues.

Example 8 The same procedure as in Example 2 was repeated except that 5 parts of the thioamide was used instead of dodecyldimethylamine. As a result, the corrosion value was 0.7
9, and as a result of surface observation using an electron microscope, almost no corrosion was observed, and the quality of printed pixels did not deteriorate in sharpness or in one hue.

Example 9 The procedure was the same as in Example 2 except that 5 parts of thiosemicarbazide was used instead of dodecyldimethylamine. As a result, the corrosion value was 0.81, and as a result of surface observation using an electron microscope, almost no corrosion was observed, and the quality of printed pixels did not deteriorate in sharpness or in one hue.

-1= From the explanation and the results in the -L table, it is clear that in addition to dodenyldimethylamine, thiourea and its derivatives, benzotriazole and its derivatives, thiazole, thioamides, or thiosemicarbazide are used, although there are some differences. It is also clear that the corrosion value is close to 1, which is a good result.

Example 10 The same procedure as in Example 1 was carried out except that the 5 parts of the additives in Examples 5 to 9 were reduced to 0.1 part each. As a result, the corrosion value was generally the same as in Example 1. As a result of surface observation using an electron microscope, very slight corrosion was observed, but no printing wires were broken during subsequent printing operations, and no unprinted pixels were observed.

Example 11 The same procedure as in Example 2 was carried out except that 5 parts of thiourea was added in addition to 5 parts of dodecyldimethylamine. As a result, the corrosion value was 0.
94, and as a result of surface observation using an electron microscope,
No corrosion was observed, and the print pixel quality was clear 3.
There was no deterioration in hue.

In addition, when a mixture of two or more of the above-mentioned additives was added, good results were obtained in which corrosion of the printing wire was similarly reduced without deteriorating the quality of the printing pixels.

It should be noted that the various additives exemplified in the above explanation are generally called adsorption type corrosion inhibitors, and it goes without saying that the same effects can be obtained by using other adsorption type corrosion inhibitors in the present invention. stomach.

(Effects of the Invention) As described in detail above, according to the present invention, adsorption type corrosion inhibition of amines, thiourea and its derivatives, benzotriazole and its derivatives, thiazole, thioamides, thiosemicarbazide, etc. By mixing the agent, corrosion of the printing wire caused by the ribbon ink can be significantly reduced, making it possible to extend the life of the print head and improve reliability. In addition, the material cost of the ink ribbon is reduced, there are no unprinted pixels, and the printing quality is significantly improved.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the corrosion value versus dodecyldimethylamine concentration, FIG. 2 is a diagram of the corrosion state of the printing wire, and FIG. 3 is an enlarged view of a portion of the same. Figure 3

Claims (2)

[Claims] (1) An ink ribbon comprising a ribbon base material and ink, characterized in that the ink ribbon contains 0.1 to 10 parts by weight of an adsorption type corrosion inhibitor per 100 parts by weight of the ink. (2) The adsorption type corrosion inhibitor has the formula R-NH_2, RR
'-NH, RR'R''-N (in the formula, R, R', R'' represent an alkyl group) amines, thiourea and its derivatives, benzotriazole and its derivatives, thiazole, thioamides, thio Semicarbazide 1 or 2
The ink ribbon according to claim 1, wherein the ink ribbon is a mixture of more than one species.