JPH10279864A - Hot melt type solid ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hot-melt solid ink excellent in abrasion resistance, which is used for recording by heating and melting at a temperature higher than room temperature in an ink jet recording apparatus. SOLUTION: A hot melt solid ink containing a polyamide resin, a fatty acid amide, a montan ester wax and a coloring material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid-state hot-melt ink at room temperature, that is, a so-called hot melt solid ink. More specifically, the present invention relates to a hot-melt solid ink having excellent abrasion resistance, which is used for recording by heating and melting at a temperature higher than room temperature in an ink jet recording apparatus.

[0002]

2. Description of the Related Art In a conventional ink jet recording system, an aqueous ink using water as a main solvent and an oil-based ink using an organic solvent as a main solvent are generally used. Printed images using water-based inks generally have poor water resistance, whereas oil-based inks can provide printed images having excellent water resistance.

However, these water-based and oil-based inks are liquid at room temperature, and when printed on recording paper, penetrate rapidly because they penetrate rapidly, making it difficult to obtain a sufficient print density. Furthermore, since the ink is always liquid, precipitates such as dye aggregates are likely to be generated from the ink during storage, and these deposits block the ink flow path and the discharge port, and the reliability of the ink jet recording system. Was greatly reduced.

For the purpose of remedying the drawbacks of these conventional solution-type inks, so-called hot-melt type oil-based inks for ink-jet recording have been proposed, which use inks which are solid at normal temperature and melt by heating. Specifically, US Pat. No. 3,653,932 discloses an ink containing a dialkyl sebacate,
U.S. Pat. No. 4,390,369 and JP-A-58-1
No. 08271, an ink containing a natural wax, Japanese Patent Application Laid-Open No. 59-22973, an ink containing a stearic acid, Japanese Patent Application Laid-Open No. 61-83268.
JP-A-62-48774 discloses an ink containing an acid or alcohol having 20 to 24 carbon atoms and further containing a ketone having a relatively high melting point. A thermosetting resin having, a solid organic solvent having a melting point higher than 150 ° C.,
Ink containing a small amount of dye substance
In JP-A-27, a coloring material, a first solvent which is solid at room temperature and liquefies when heated to a temperature higher than room temperature,
JP-A-62-295973 discloses an ink comprising a second solvent which is liquid at room temperature and has a high volatility, which dissolves a solvent of the formula (1), wherein a synthetic wax having a polar group and a dye soluble in the wax are used. Included inks and the like have been proposed.

However, these conventional hot-melt type solid inks, when printed on paper or the like at a melt viscosity that enables good ink discharge, have poor ink penetration into the paper or the like. Rubbed with the ink, the ink is peeled off from the printing surface and adheres to the hand or the like, and it is difficult to maintain good printing quality.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a hot-melt type solid which has excellent melt resistance when printed on paper or the like at a melt viscosity which enables good ink ejection, particularly, good penetration into paper and excellent abrasion resistance. It is intended to provide ink.

[0007]

In order to achieve the above-mentioned object, the present invention relates to a hot-melt type solid ink for an ink jet printer which is solid at ordinary temperature and which is used by heating and melting the polyamide resin, fatty acid amide and montan. It is characterized by containing a series ester wax.

When the basic vehicle of the ink is only a polyamide resin and a fatty acid amide, the coloring material is well dispersed in the ink, and although the adhesion of the ink to the printing medium becomes good, the ink tends to be blocked, and the ink is discharged. When the printed image was rubbed by hand or the like, the ink was peeled off, and the rubbing resistance was poor. Therefore, if the amount of the resin component (such as polyamide resin) is reduced in order to improve the abrasion resistance, the ink easily penetrates into paper or the like, but the melt viscosity required in the ink jet recording method cannot be obtained. In addition, clear printing cannot be obtained. Further, the adhesiveness to a printing medium other than paper, such as a film used for an OHP (overhead projector) or the like, is lost.

When the amount of the polyamide resin added is reduced in order to improve the penetration of the ink into the paper, the melt viscosity of the ink itself becomes low, which causes a problem in ink ejection by an ink jet printer. OHP
For example, the adhesiveness of print media other than paper is also lost.

By adding a montan ester wax to the polyamide resin and the fatty acid amide, it is possible to maintain the melt viscosity required at the time of ink ejection, so that the amount of the resin component in the ink can be reduced.
On the other hand, the ink penetrates the paper well and improves the abrasion resistance. Further, the montan ester wax has good compatibility with other components such as a polyamide resin and a fatty acid amide, and imparts the action of the amide resin, that is, the adhesive property of the ink to the printing paper, and the crystal of the wax. It does not hinder the functions of preventing the formation of the ink and imparting transparency to the ink, and does not hinder the functions of the fatty acid amide, that is, the functions of dispersing the coloring material well.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The polyamide resin used in the present invention is obtained by condensation polymerization of an amine and an acid. As the amine, for example, hexamethylenediamine can be used. For example, adipic acid, sebacic acid, trimellitic anhydride, dimer acid and the like can be used.Furthermore, those having both an amine and an acid include 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. By combining
A polyamide resin having desired characteristics (amine value, acid value, etc.) can be adjusted. Specific examples of commercially available polyamide resins that can be used in the present invention include, for example, the following: Tomide 90, Tomide 9
2, tomide 391, tomide 394, tomide 394N, tomide 395, tomide 397, tomide 509, tomide 535, tomide 558,
Tomide 560, Tomide 575, Tomide 13
10, Tomide 1350 (all manufactured by Fuji Kasei), Polyimide S-40HA, Polymide S-40E, Polymide S-150, Polymide S-52, Polymide S-
185, Polyimide S-1510, Polyimide S-15
25, Polyimide S-1635, Polyimide S-196
2, Polyimide S-2007, Polyimide S-2153
(Manufactured by Sanyo Chemical Co., Ltd.), Versamide 335, Versamide 725, Versamide 744, Versamide 756, Versamide 930, Versamide 940 (Henkel Hakusui) and the like. In the present invention, these may be used alone or in a mixture of two or more.

In the present invention, the total amount of the polyamide resin is 5 to 5 based on the total weight of the ink.
It is used in such an amount as to be in the range of 50% by weight. If the content of the polyamide resin in the ink is less than 5% by weight, not only the melt viscosity sufficient for discharging by the ink jet recording method is not obtained, but also the transparency of the ink and the adhesiveness to the printing medium are reduced. I can't get it. On the other hand, if the content of the polyamide resin in the ink is more than 50% by weight, the melt viscosity of the ink becomes too high, so that it is difficult to discharge the ink at a good operating temperature of the printer head used for inkjet recording. At the same time, the penetration of the ink into the paper when attached to paper or the like becomes worse, and if the printing surface is rubbed with a hand or the like, the ink is peeled off from the paper or the like, so that good printing quality cannot be maintained. . Therefore, the total amount of the polyamide resin is preferably contained in the ink in the range of 10 to 30% by weight.

In the present invention, the fatty acid amide has high compatibility with the above-mentioned polyamide resin and is widely used as a dispersant for the dye, and is used for the purpose of dispersing the coloring material throughout the ink. Specific examples of the fatty acid amide used for this purpose include the following: lauric amide, stearic amide, oleic amide, erucic amide, ricinoleic amide, stearic ester amide, palmitic amide, behen Acid amide, brassic acid amide, N-oleyl stearamide, N-stearyl stearamide, N-oleyl palmitamide, N-stearyl erucamide, and the like. In the present invention, these may be used alone or in a mixture of two or more. Fatty acid amide, based on the total weight of the ink,
The fatty acid amide is used in an amount such that the total amount is in the range of 20 to 80% by weight. Fatty acid amide content in ink is 1
When the amount is less than 0% by weight, the effect of dispersing the above-mentioned fatty acid amide coloring material cannot be sufficiently exhibited. On the other hand, when the amount is more than 80% by weight, the content of the polyamide resin becomes too small, so that the above-mentioned polyamide resin The effect of can not be exhibited.

In the present invention, the montan ester wax compensates for a decrease in the melt viscosity of the ink due to a decrease in the content of the polyamide resin in the ink, while maintaining the melt viscosity required in the ink jet recording system.
When the ink is applied to paper or the like, the ink penetrates the paper to improve the abrasion resistance. The montan-based ester wax used for this purpose is considered to be a hard wax ester derivative obtained by distilling asphalt-based charcoal at a high temperature or extracting with a solvent. For example, from Hoechst, wax E, wax KP, It is available as wax KPS, wax KSL, Hostalve WE4, wax KSS, wax F, wax OP, and wax O. In the present invention, these may be used alone or in a mixture of two or more. The montan ester wax is used in such an amount that the sum of the montan ester wax is in the range of 10 to 30% by weight based on the total weight of the ink. If the content of the montan ester wax in the ink is less than 10% by weight, the effect of the above-mentioned montan ester wax cannot be exerted. On the other hand, if the content is more than 30% by weight, the ink is printed on the printing paper when printing. It becomes difficult to adhere, and good printing quality cannot be maintained.

In the present invention, other waxes may be used in addition to the montan ester wax. As such other wax, a wax having a melting point of 50 ° C to 200 ° C and being stable to heat is used. Specifically, petroleum wax, desirably paraffin wax or microcrystalline wax, or vegetable wax, desirably candelilla wax, carnauba wax, rice wax, or jojoba solid wax, animal wax,
Preferably beeswax, lanolin or spermaceti, mineral waxes, preferably montan wax, synthetic hydrocarbons, preferably Fischer-Tropsch wax or polyethylene wax, hydrogenated waxes, preferably hydrogenated castor oil or hydrogenated castor oil derivatives, Modified wax, preferably a paraffin wax derivative, a microcrystalline wax derivative or a polyethylene wax derivative, or a fatty synthetic wax such as a higher fatty acid, preferably behenic acid, stearic acid, palmitic acid, myristic acid, or lauric acid, or a ketone wax, preferably Is distearyl ketone, higher alcohols, desirably stearyl alcohol, or behenyl alcohol,
Hydroxystearic acid, preferably 12-hydroxystearic acid or 12-hydroxystearic acid derivatives, also ketones, preferably stearone or laurone, amines, preferably dodecylamine, tetradecylamine or octadecylamine, esters, preferably stearin Methyl ester, octadecyl stearate, glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, ethylene glycol fatty acid ester, or polyoxyethylene fatty acid ester, and a polymerization wax, preferably an α-olefin maleic anhydride copolymer wax and the like Any conventionally known wax can be used without any particular limitation. These waxes can be used alone or in combination of two or more. The amount of other wax used in addition to the montan ester wax,
The sum of the montan ester wax and the other wax should not exceed the content described for the montan ester wax.

As the coloring material used in the present invention, any of dyes and pigments conventionally used in oil-based ink compositions can be used. Pigments that are generally used in the technical field of printing, whether organic or inorganic, can be used. Specifically, for example, carbon black, cadmium red, molybdenum red, chrome yellow,
Cadmium yellow, titanium yellow, chromium oxide, viridian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, dioxazine pigment, sulene pigment Conventionally known pigments such as perylene-based pigments, perinone-based pigments, thioindigo-based pigments, quinophthalone-based pigments, metal complex pigments, etc., are particularly limited as long as the primary particle size is in the range of 10 to 100 nm. It can be used without. These pigments can be used in combination. Dyes can be used any of dyes conventionally used in oil-based ink compositions, but azo dyes, disazo dyes, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes,
Oil-soluble dyes such as quinone imine dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, xanthene dyes, phthalocyanine dyes and metal phthalocyanine dyes are preferred. These dyes can be used in combination. In the present invention, both a dye and a pigment can be used as the coloring material, but it is desirable to use a soluble dye having excellent heat stability and solubility with other vehicles. In order for the ink to have sufficient color-forming ability, these coloring materials may be added in the ink in an amount of 0.1%.
It is preferably contained in an amount of from 1 to 10% by weight, and preferably from 0.5 to 8% by weight in consideration of the color developing ability when printing with a printer. Further, as a guarantee that the pigment does not agglomerate, the content is more preferably 1 to 5% by weight.

The vehicle used in the present invention described above,
When using other vehicles or additives, they are all solid at room temperature, so that when preparing the hot melt type solid ink of the present invention, they are all melted at a temperature higher than the melting temperature, It is necessary to mix and disperse well, and if such an object can be achieved, the means for preparing the hot melt type solid ink of the present invention is not limited at all, and any means can be used. Good. The procedure for producing the hot melt type solid ink of the present invention will be described with reference to FIG. Vehicles (1), (3) used in the present invention,
When each of (4) is used in the above-mentioned ratio, and when other vehicles and additives are used, they are used in the container (5) in a ratio which does not impair the performance of the hot melt type solid ink of the present invention. , And a temperature higher than the highest one of the melting temperatures of the vehicle and additives when used, usually 70 ° to 250 ° C, preferably 100 ° to 20 ° C.
The mixture is heated and melted at a temperature of about 0 ° C., and then the coloring material (6) is charged. Once the vehicle, additives if used, etc. have been melted, stirrer (7) is rotated at a speed and for a time sufficient to obtain a homogeneous mixture, typically 200-10,000 RP.
M, preferably at 500 to 5,000 RPM, and usually rotated for several tens of minutes to several hours, preferably for about 1 to 2 hours, to sufficiently stir and mix the mixture. The stirring and mixing are performed until one drop of the mixture is taken on a slide glass and the absence of aggregates is confirmed by an optical microscope (about 200 times). After the completion of the stirring and mixing, the obtained mixture (8) is filtered in a molten state through a filtration device, a heterogeneous substance is filtered off, and the substance that has passed through the filter (9) is filtered into a final hot-melt solid ink ( Obtained as 10).

[0018]

EXAMPLES Specific examples are given below to illustrate the present invention. Example 1 Versamide 335 (manufactured by Henkel Hakusui) as a polyamide resin (1), stearic acid amide (Nikka Amide S: manufactured by Nippon Kasei) as a fatty acid amide (3), Hostalbu WE4 (manufactured by Hoechst) as a montan ester wax (4) and, as an α-olefin maleic anhydride copolymer, Diacarna PA30L (manufactured by Mitsubishi Chemical Corporation)
(5) was charged into the apparatus shown in FIG.
Heat and dissolve at 0 ° C, and then use Neopen Y as a coloring material.
yellow 075 (manufactured by BASF) (6) was loaded. 1,000 RPM by dissolver (7)
For about 1 hour. One drop of the mixture was taken on a slide glass, and it was confirmed by an optical microscope (200 times) that there was no aggregate. The resulting mixture (8) was filtered using a 0.8 μm glass fiber filter GA200 (manufactured by Toyo Roshi Kabushiki Kaisha) (9) with a hot filtration device manufactured by Toyo Roshi Kaisha, Ltd., and the mixture passed through the filter was filtered. Obtained as a hot melt type solid ink (10).

Versamide 335 20 parts by weight Nikka Amide S 48 parts by weight Hostalbu WE4 21 parts by weight Diamond Carna PA30L 9 parts by weight Neopen Yellow 075 2 parts by weight

The obtained hot-melt type solid ink was mounted on an ink-jet printer and printing was performed at an ejection temperature of about 120 ° C. As a result, there was no clogging of the printer head, the ink ejection was good, and the ink was clear on paper. Print was obtained. The ink dot diameter of a sample printed on paper with the ink was measured as follows, and evaluated as the degree of penetration of the ink into the paper. That is, it was evaluated that the larger the dot diameter, the more the ink permeated the paper.

First, one dot printing of ink was performed on paper unified by an ink jet printer. Printing accuracy evaluation system MODELRT-2 from the dot sample
000 (manufactured by Yarman KK) was used to measure the printing surface area, and the dot diameter of one dot was calculated. Result 1
The dot diameter of the dot was 148 μm. The components and amounts (parts by weight) used in this example are listed together with the obtained results in Table 1.

The hot-melt type solid ink obtained in the present example has good ink ejection, and maintains good print quality without shaving the ink even when the print surface is rubbed by hand. Was completed.

Example 2 A hot melt solid ink (10) was obtained using the same components as described in Example 1 in the following amounts and following the same procedure as described in Example 1.

Versamide 335 24 parts by weight Nikka Amide S 47 parts by weight Hostalbu WE4 21 parts by weight Diamond Carna PA30L 6 parts by weight Neopen Yellow 075 2 parts by weight

The obtained hot-melt type solid ink was measured according to the same evaluation method as that described in Example 1, and the dot diameter of one dot was calculated. Result 1
The dot diameter of the dots was 119 μm. The components and amounts (parts by weight) used in this example are listed together with the obtained results in Table 1.

The hot-melt type solid ink obtained in the present example has good ink discharge, and maintains good print quality without being scraped off even if the print surface is rubbed by hand. Was completed.

Comparative Example 1 Versamide 335 (1) as a polyamide resin, Nikkaamide S (3) as a fatty acid amide, and Diacarna PA 30L as an α-olefin maleic anhydride copolymer
(5) and Neopen Yellow 0 as a coloring material
75 (6) in the following amounts and following the same procedure as described in Example 1 for the hot melt solid ink (1
0) was obtained.

Versamide 335 24 parts by weight Nikka Amide S 56 parts by weight Diamond Carna PA30L 18 parts by weight Neopen Yellow 075 2 parts by weight

The obtained hot melt type solid ink was measured according to the same evaluation method as that described in Example 1 to calculate a dot diameter of one dot. Result 1
The dot diameter of the dots was 98 μm. The components and amounts (parts by weight) used in this example are listed together with the obtained results in Table 1.

As is clear from the comparison in Table 1, Comparative Example 1
Ink has a smaller print dot diameter than Examples 1 and 2. In addition, the ink of Comparative Example 1 had good adhesion to a print medium, but was liable to block, and had poor abrasion resistance, such as the ink adhering when rubbed by hand.
Good printing quality could not be maintained.

As can be seen from the above results, Example 1
The hot-melt type solid ink obtained in and 2 is
Compared with the hot-melt type solid ink obtained in Comparative Example 1, the ink permeation into the paper was good, so that it was excellent in abrasion resistance and good print quality could be maintained.

[0032]

[Table 1]

[0033]

According to the present invention, the hot melt type solid ink contains a montanic acid ester wax, so that the ink easily penetrates into paper and the abrasion resistance is improved.

[Brief description of the drawings]

FIG. 1 is a diagram showing a means for preparing a hot melt type solid ink of the present invention.

[Explanation of symbols]

 1, 3, 4 Vehicle 5 Container 6 Colorant 7 Stirrer 9 Filter

Claims (2)

[Claims] 1. A hot melt type solid ink containing a polyamide resin, a fatty acid amide, a montan ester wax and a coloring material. 2. The polyamide resin comprises 5 to 50% by weight, the fatty acid amide comprises 20 to 80% by weight, and the montan ester wax comprises 10 to 30% by weight based on the total weight of the ink.
And the colorant is present in an amount of 0.1 to 10% by weight.
Hot melt type solid ink.