JPH05345872A - Recording medium which is solid at ordinary temperature and method for recording - Google Patents

Abstract

PURPOSE:To obtain a recording medium, which is a solid at ordinary temperature, excellent in fixing properties of recorded images and capable of providing the images good in light resistance and a method for recording. CONSTITUTION:The recording medium is used for a method for recording in which the recording medium is discharged from a discharge orifice to carry out the recording by applying heat energy thereto. This recording medium is a solid at ordinary temperature and comprises at least an ultraviolet ray absorber and a colorant, a nickel complex-based ultraviolet stabilizer and the colorant or a hindered amine-based light stabilizer and the colorant. Furthermore, the objective method for recording is to thermally melt this recording medium which is the solid at ordinary pressure, discharge the recording medium from the discharge orifice and perform the recording by applying heat energy according to a recorded signal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a room temperature solid recording medium and a recording method using the same, and more particularly to a room temperature solid recording medium used in an ink jet recording method and a recording method using the same.

[0002]

2. Description of the Related Art An ink jet recording method is one in which droplets of a recording medium (ink) are ejected and adhered to a recording material such as paper for recording. In particular, the applicant disclosed in Japanese Patent Publication No. 61-59911, Japanese Patent Publication No. 69-59912, and Japanese Patent Publication No. 61-59914.
According to the method in which the electrothermal converter is used as the ejection energy supply means and the thermal energy is applied to the ink to generate the bubbles to eject the droplets, it is possible to easily realize the high density multi-orifice of the recording head, High-resolution and high-quality images can be recorded at high speed.

[0003]

However, conventional inks generally contain water as a main component and a water-soluble high-boiling point solvent such as glycol for the purpose of preventing drying and clogging. , When using such ink to record on so-called plain paper such as copy paper, report paper, notebook, notepaper, etc., which are often used in office, the ink does not dry and fix quickly and the characters immediately after printing are printed. There was a problem that when touching with a hand, ink came into contact with the hand, characters were rubbed and the print quality was degraded.

In addition to the above problems, the light resistance of recorded images often becomes a problem. That is, when a recorded image is exposed to sunlight, a fluorescent lamp, or the light source of a projector, the recorded image may disappear, become difficult to read, or discolor during a long-term storage. It was hoped that there would be some improvement.

In response to such a request, Japanese Patent Laid-Open No. 3-372
Japanese Patent Laid-Open No. 78 discloses a recording method in which a recording medium that is solid at room temperature is heated and liquefied, and droplets are ejected from an orifice by a foaming force generated by applying thermal energy. According to this method, the recording medium instantly undergoes a phase change from a liquid state to a solid state on the paper, so that the fixing property of the recording medium can be improved.

However, as the coloring material in the recording medium, an oil-soluble dye is mainly used because of its colorability and long-term storage stability of the recording medium. Therefore, in general, oil-soluble dyes, like water-soluble dyes, cannot be said to have sufficient light resistance, and therefore the light resistance of recorded images is still unsatisfactory.

Therefore, a main object of the present invention is to provide a recording medium which solves the problems of the conventional recording medium as described above, that is, an image having excellent light fastness as well as excellent fixing property of a recorded image. It is to provide an excellent recording medium that gives

[0008]

That is, the first invention of the present invention is a recording medium used in a recording method for recording by ejecting a recording medium from an ejection orifice by applying thermal energy, It is a room-temperature solid recording medium containing at least an ultraviolet absorber and a colorant.

Further, according to the present invention, a recording medium which is solid at room temperature and contains at least an ultraviolet absorber and a colorant is used, and the recording medium is heated and melted, and then thermal energy corresponding to a recording signal is applied to the recording medium to eject the recording medium. A recording method is characterized in that the recording medium is discharged from an orifice to perform recording.

Further, according to the present invention, an ordinary temperature solid recording medium containing at least an ultraviolet absorber and a colorant is used, and after the recording medium is heated and melted, an ejection orifice for ejecting the recording medium, and the ejection orifice. The bubble generated by the ejection energy applying unit is formed by using a recording head having a liquid passage communicating with the recording medium and an ejection energy generating unit that supplies thermal energy for ejecting the recording medium in the liquid passage. Communicating with the outside air through the discharge orifice,
A recording method is characterized in that recording is performed by ejecting the recording medium.

A second invention of the present invention is a recording medium used in a recording method for recording by ejecting a recording medium from a discharge orifice by applying heat energy, and a nickel complex type ultraviolet stabilizer and a coloring agent. The recording medium is a solid at room temperature, which contains at least an agent.

Further, according to the present invention, a recording medium which is solid at room temperature and contains at least a nickel complex type ultraviolet stabilizer and a colorant is used, the recording medium is heated and melted, and heat energy corresponding to a recording signal is applied. Thus, the recording medium is discharged from the discharge orifice to perform recording.

Further, the present invention uses a recording medium which is solid at room temperature and which contains at least a nickel complex type ultraviolet stabilizer and a colorant, and an ejection orifice for ejecting the recording medium after heating and melting the recording medium. A recording head provided with a liquid path communicating with the discharge orifice and a discharge energy generating means for supplying thermal energy for discharging the recording medium in the liquid path is generated by the discharge energy applying means. A recording method is characterized in that a bubble is communicated with the outside air from the discharge orifice and the recording medium is discharged to perform recording.

A third aspect of the present invention is a recording medium for use in a recording method for recording by ejecting a recording medium from a discharge orifice by applying thermal energy, which is a hindered amine light stabilizer and a colorant. A recording medium that is solid at room temperature, containing at least:

Further, according to the present invention, a room temperature solid recording medium containing at least a hindered amine light stabilizer and a colorant is used, and the recording medium is heated and melted, and further heat energy according to a recording signal is applied. The recording method is characterized in that the recording medium is discharged from the discharge orifice to perform recording.

Furthermore, the present invention uses a recording medium which is a solid at room temperature and contains at least a hindered amine light stabilizer and a colorant, and a discharge orifice for discharging the recording medium after heating and melting the recording medium, Bubbles generated by the ejection energy applying means using a recording head provided with a liquid passage communicating with the ejection orifice and an ejection energy generating means for supplying thermal energy for ejecting the recording medium in the liquid passage. Is communicated with the outside air from the discharge orifice, and the recording medium is discharged to perform recording.

The present invention will be described in detail below. The room-temperature solid recording medium of the first invention of the present invention is a solid-state recording medium containing an oil-soluble dye at room temperature, which contains an ultraviolet absorber, whereby an image formed by using the ultraviolet absorber is light-resistant. The recording medium is excellent and the fixing property of the recording medium can be improved because the recording medium instantly undergoes a phase change from a liquid state to a solid state on paper.

The ultraviolet absorber to be contained in the recording medium which is solid at room temperature according to the first aspect of the present invention is harmful to 300 to 40.
It absorbs ultraviolet rays in the vicinity of 0 mμ and re-radiates the energy as harmless heat energy to prevent deterioration of the coloring material. As an ultraviolet absorber,
Although various compounds can be used, preferred examples include, for example, phenyl salicylate (melting point 42 ° C.), p-te.
rt-Butylphenyl salicylate (melting point 63 ° C.), p
Salicylic acid-based UV absorbers such as octylphenyl salicylate (melting point 73 ° C.), 2-hydroxy-4-dodecyloxybenzophenone (melting point 37 ° C.), 2-hydroxy-4-octoxybenzophenone (melting point 48 ° C.), 2
-Hydroxy-4-methoxybenzophenone (melting point 63
C.), 2,2′-dihydroxy-4-methoxybenzophenone (melting point 69 ° C.), a benzophenone-based ultraviolet absorber, 2- (2′hydroxy-5′-methylphenyl) benzotriazole (melting point 129 ° C.), 2- Examples thereof include cyanoacrylate-based ultraviolet absorbers such as (2 ′ hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole (melting point 153 ° C.).

The ultraviolet absorber as described above is contained in the recording medium in an amount of 0.1 to 10% by weight, preferably 0.5 to 5%.
It is used by being dissolved or dispersed in an amount of wt%.

Depending on the amount of the ultraviolet absorber used, the melting speed of the recording medium may slow down, which may affect the start-up property of the recording apparatus. Therefore, the melting point should be set to a temperature lower than the heating temperature (operating temperature) of the recording head. It is preferable to use an ultraviolet absorber having the same.

The room temperature solid recording medium of the second invention of the present invention is used by incorporating a nickel complex ultraviolet stabilizer into a room temperature solid recording medium containing an oil-soluble dye. The image thus formed has excellent light resistance, and furthermore, the recording medium instantaneously undergoes a phase change from a liquid state to a solid state on paper, so that the fixing property of the recording medium can be improved.

The nickel complex type ultraviolet stabilizer contained in the recording medium of the second aspect of the present invention is a quencher action, that is, an action of absorbing the ultraviolet rays and returning the excited coloring material to the original ground state. This is to prevent deterioration of the coloring material. In general, many organic nickel compounds exhibit such an action, and various compounds can be used, but preferable examples include nickel dibutyldithiocarbamate and nickel complex-3,5-ditert-butyl-4-hydroxy. Benzyl phosphoric acid monoethylate, nickel bis (octylphenyl) sulfide, [2,2′-thiobis (4-tert-octylphenolate)]-n-butylamine nickel, ethyl-2-cyano-3,3′-diphenyl acrylate,
Tinuvin-120 (trade name, Ciba-Geig
y company), Sanol LS-770 (trade name, manufactured by Sankyosha) and the like.

The nickel complex type ultraviolet stabilizer as described above is used by dissolving or dispersing in the recording medium in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

The room temperature solid recording medium of the third invention of the present invention is used by incorporating a hindered amine light stabilizer into a room temperature solid recording medium containing an oil-soluble dye. The formed image has excellent light resistance, and furthermore, the recording medium undergoes a phase change from a liquid state to a solid state on paper instantaneously, so that the fixing property of the recording medium can be improved.

The hindered amine light stabilizer contained in the recording medium of the third invention of the present invention is a radical scavenger,
It has a function as a hydroperoxide decomposer and prevents deterioration of the coloring material. Although various kinds of these can be used, preferred examples include, for example, MARK-LA57, MARK-LA62, and MA.
RK-LA63, MARK-LA67, MARK-LA
68, MARK-LA77, MARK-LA82, MA
RK-LA87 (above, trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Tinuvin 944LD, Tinuvin
765, Tinuvin 622LD, Tinuvin
144, Cyasorb UV-3346 (above, trade name, manufactured by Ciba Geigy), Sanol LS-77
0, Sanol LS-2626 (trade name, manufactured by Sankyosha)
Etc.

The hindered amine light stabilizer as described above is used after being dissolved or dispersed in the recording medium in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

With respect to the color materials used in the recording medium which is solid at room temperature according to the first to third inventions of the present invention, most of the color materials described in the color index can be used. In addition, even those not listed in the color index can be suitably used in many cases. In particular, an organic solvent-soluble type oil-soluble dye is generally preferably used. For example, the oil-soluble dyes described in the following color index are listed.

C. I. Solvent Yellow
1,2,3,4,6,7,8,10,12,13,1
4,16,18,19,21,25,25: 1,28,
29, 30, 32, 33, 34, 36, 37, 38, 4
0, 42, 43, 44, 47, 48, 55, 56, 5
8, 60, 62, 64, 65, 72, 73, 77, 7
9, 81, 82, 83, 83: 1, 85, 88, 89,
93, 94, 96, 98, 103, 104, 105, 1
07,109,112,114,116,117,12
2,123,124,128,129,130,13
1,133,134,135,138,139,14
0, 141, 143, 146, 147, 148, 14
9,150,151,152,153,157,15
8,159,160: 1,161,162,163,1
64, 165, 167, 168, 169, 170, 17
1,172 etc.

C. I. Solvent Red 1,
2, 3, 4, 7, 8, 13, 14, 17, 18, 19,
23, 24, 25, 26, 27, 29, 30, 33, 3
5,37,39,41,42,43,45,46,4
7,48,49,49: 1,52,68,69,72,
73,74,80,81,82,83,83: 1,8
4,84: 1, 89, 90, 90: 1, 91, 92, 1
06,109,111,117,118,119,12
2,124,125,127,130,132,13
5,138,140,143,145,146,14
9,150,151,152,155,160,16
4,165,166,168,169,172,17
5,176,177,179,180,181,18
2,185,188,189,195,198,20
2,203,204,205,206,207,20
8,209,210,212,213,214,21
5,216,217,218,219,220,22
1,222,223,224,225,226,22
7,228,229 etc.

C. I. Solvent Blue 2,
4,5,7,10,11,12,22,25,26,3
5,36,37,38,43,44,45,48,4
9,50,51,59,63,64,66,67,6
8, 70, 72, 79, 81, 83, 91, 94, 9
5,97,98,99,100,102,104,10
5,111,112,116,117,118,12
2,127,128,129,130,131,13
2,133,134 etc.

C. I. Solvent Black
3,5,6,7,8,13,22,22: 1,23,2
6,27,28,29,33,34,35,39,4
0, 41, 42, 43, 45, 46, 47, 48, 4
9,50 mag

The content of these colorants is determined depending on the properties required of the recording medium and is not particularly limited, but generally it is about 0.2 to 3% by weight in the recording medium.
0%, preferably 0.5-20%, more preferably 1%
It is a ratio of 10%.

As the heat-fusible substance used together with the colorant, beeswax, lanolin, carnauba wax, candelilla wax, montan wax, ceresin wax having a melting point of 36 ° C. to 150 ° C. are preferable.
Paraffin wax, microcrystalline wax,
Oxidized wax, ester wax, waxes such as low molecular weight polyethylene, higher fatty acids such as palmitic acid and stearic acid, aliphatic alcohols, esters, amides, lactones, lactams, aromatic alcohols, ethers, Esters, amides, ketones, polycyclic compounds and heterocyclic compounds are used. In addition, based on the above components, a polyamide resin, a polyurethane resin, a polyester resin, an epoxy resin, a polyolefin resin, a polyacrylic resin, a polyvinyl chloride resin, a polyvinyl acetate resin, a cellulose resin, Polyvinyl alcohol-based resin, petroleum-based resin, phenol-based resin, polystyrene-based resin and the like may be appropriately mixed and used.

Further, the recording medium of the present invention is required to be excellent in the function of converting heat energy into ejection energy in addition to various characteristics required for the ink jet recording method. The main constituents of the substance have a melting point of 36 ° C to 150 ° C and a boiling point of 15 ° C.
Those having a temperature of 0 ° C or higher and 340 ° C or lower can be suitably used. More specifically, for example, the following substances are used.

Acetamide, vanillin, dibenzyl, m
-Acetotoluidine, phenyl benzoate, 2,6-dimethylquinoline, 2,6-dimethoxyphenol, p-methylbenzyl alcohol, p-bromoacetophenone,
Homocatechol, 2,3-dimethoxybenzaldehyde, 2,4-dichloroaniline, dichloroxylylene,
3,4-dichloroaniline, 4-chloro-m-cresol, p-bromophenol, dimethyl oxalate, 1-naphthol, dibutylhydroxytoluene, 1,3,5-
Trichlorobenzene, p-tert-pentylphenol, durene, dimethyl-p-phenylenediamine, tolan, styrene glycol, propionamide, diphenyl carbonate, 2-chloronaphthalene, acenaphthene, 2-
Bromonaphthalene, indole, 2-acetylpyrrole, dibenzofuran, p-chlorobenzyl alcohol,
2-methoxynaphthalene, tiglic acid, p-dibromobenzene, 9-heptadecane, 1-tetradecanamin,
1,8-octanediamine, glutaric acid, 2,3-dimethylnaphthalene, imidazole, 2-methyl-8-hydroxyquinoline, 2-methylindole, 4-methylbiphenyl, 3,6-dimethyl-4-octyne-diol, 2,5-Dimethyl-3-hexyne-2,5-diol, 2,5-dimethyl-2,5-hexanediol, ethylene carbonate, methyl carbamate, ethyl carbamate, butyl carbamate and the like.

The recording medium which is solid at room temperature according to the first to third inventions of the present invention may optionally contain an organic solvent which is liquid at room temperature, such as 1-hexanol, 1-heptanol, 1-hexanol.
Alcohols such as octanol, ethylene glycol,
Polyhydric alcohols such as propylene glycol and triethylene glycol, and other substances such as glycol ethers, ketones, keto alcohols, amides, ethers and esters may be contained. These organic solvents greatly grow bubbles generated in the recording medium. The content of the organic solvent is preferably 0 to 10% by weight with respect to the recording medium, and the boiling point is preferably 150 ° C or higher.

In addition to the above, the recording medium of the present invention may contain various additives such as an antioxidant, a dispersant and a rust preventive.

The recording medium of the present invention is obtained by mixing the above materials in a heated state. Next, a recording method using the recording medium that is a solid at room temperature according to the first to third aspects of the present invention will be described. FIG. 1 shows an example of a recording device used in the present invention. As shown in FIGS. 2A and 2B, the recording head 6 is provided with a wall 68 arranged in parallel on the substrate 61 and a wall 69 forming a liquid chamber 65. Furthermore, the wall 6
A transparent top plate 64 is arranged on the surfaces 8 and 69. Figure 2
In (a), in order to make the inside of the recording head 6 easier to see,
The top plate 64 is shown separated from the walls 68,69. Top 6
An ink supply port 67 is formed in
The molten recording medium flows into the liquid chamber 65. The nozzles 62 through which the molten recording medium passes are provided between the walls 68 and 68 and between the walls 69 and 68, and heat is generated on the recording medium on the substrate 61 in the middle of each nozzle 62 according to the recording signal. A heater 63 for providing energy is provided. Bubbles are generated in the recording medium by the thermal energy from the heater 63, and the recording medium is ejected from the ejection orifice 62a of the nozzle 62.

The recording head 6 is provided with a heating means 7 so that the recording head 6 has a temperature of 10 to 20 higher than the melting point of the recording medium.
The recording medium is kept in a molten state by heating to a temperature higher by ℃. Reference numeral 5 is a head drive circuit, and 8 is an external power supply.

Next, another recording method using the recording medium of the present invention will be described. 3 and 4 show the recording principle of the recording method of the present invention.

The recording head used here has a heater 12
Is provided at a position close to the direction of the orifice 15. This is the simplest method for communicating bubbles with the outside air. However, it is not possible to satisfy the above conditions for allowing the bubbles to communicate with the outside air simply by bringing the heater close to the discharge port. Therefore, in order to satisfy the above conditions of the invention, the amount of heat energy generated by the heater (heater configuration, forming material, driving conditions, area, heat capacity of the substrate on which the heater is provided, etc.), ink physical properties, recording head By selecting the size of each part (the distance between the discharge port and the heater, the width and height of the discharge port and the liquid path) as desired, the bubble can be communicated with the outside air in a desired state.

3 (a) and 4 (a) show the state before foaming. First, an electric current is applied to the heating heater 18,
The entire recording head is heated to dissolve the solid ink. After the solid ink is liquefied, an electric current is momentarily applied to the heater 12 to heat the ink near the heater in a pulsed manner.
No. 3 suddenly boiled and bubbles 16 generated vigorously,
Expansion starts (see FIG. 3 (b) and FIG. 4 (b)). The bubble continues to expand, grows particularly toward the orifice side having a small inertance (inertia), penetrates through the orifice, and communicates with the outside air (see FIGS. 3C and 4C). The ink on the orifice side of the bubble jumps forward due to the momentum given by the bubble up to this moment, and eventually becomes an independent droplet 17 and flies to a recording medium such as paper (FIG. 3).
(D) and FIG. 4 (d)). The void formed at the tip of the orifice side is filled with new ink due to the surface tension of the ink behind and the wetting of the nozzle wall, and the state before ejection is restored. Here, in the above-described recording method of the present invention, the recording head can have a structure with a small inertance in the direction of the discharge port from the heater, and the momentum of the generated bubble can be efficiently converted into droplets. As the physical properties of the ink, those having a slow ejection speed in the conventional recording method, for example, a solid ink at room temperature, which has a physical property of a liquid which is liquefied by being heated to a melting point or higher is used for the ejection of droplets. Even if it is not preferable (for example, viscosity is high), stable and high-speed ejection is possible with the recording method of the present invention.

Further, in the present invention, when the bubble generated by the discharge energy applying means is communicated with the outside air from the discharge port, the generation of ink mist is completely suppressed and the communication efficiency of the bubble with the outside air is improved. Therefore, more preferably,
The present inventors have already proposed Japanese Patent Laid-Open No. 2-112832.
Japanese Patent Laid-Open No. 2-112833, Japanese Patent Laid-Open No. 2-1
It is preferable that the bubbles communicate with the outside air from the discharge ports under the conditions described in Japanese Patent No. 12834.

The apparatus shown in FIG. 5 is an apparatus for carrying out the recording method of the present invention. The recording medium accommodated in the tank 41 is supplied to the recording head 6 through the supply passage 42. The recording head 6 is the same as that described with reference to FIGS. The tank 41, the supply path 42, and the recording head 6 are provided with heating means 40 and 7, and the recording medium in the apparatus is kept in a liquid state by the heat of the heating means 40 and 7 when the recording apparatus is driven. The heating means 40 and 7 are set to a predetermined temperature by the temperature control means 46. A recording signal is sent from the drive circuit 45 to the recording head 6, and the heater 63 of the recording head 6 is caused to generate heat in accordance with the recording signal.

In this way, the recording medium in the tank 41 is supplied to the recording head 6 while being kept in a liquid state, and is ejected into small droplets from the ejection orifice of the recording head according to the recording signal to eject the recording paper. A recorded image is formed on 44.

[0046]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples.

Records containing ultraviolet absorbers and colorants
Medium After liquefying each component shown below by heating above its melting point,
After mixing and stirring for 3 hours, the insoluble matter was removed using a filter to obtain recording media of the present invention (Examples 1 to 5).

Example 1 Ethylene carbonate (melting point 39 ° C.) 50% by weight 1,12-dodecanediol 42% by weight 2-hydroxy-4-methoxybenzophenone 3% by weight C.I. I. Solvent Black 3 5% by weight

Example 2 Acetamide 50% by weight Stearic acid (melting point 67 ° C.) 43% by weight p-tert-butylphenyl salicylate 4% by weight C.I. I. Solvent Red 37 3% by weight

Example 3 Acetamide (melting point: 82 ° C.) 45% by weight Cetyl alcohol 42% by weight 2-hydroxy-4-octoxybenzophenone 5% by weight C.I. I. Solvent Yellow 14 5% by weight

Example 4 Ethyl carbamate (melting point 50 ° C.) 51% by weight Myristic acid (melting point 54 ° C.) 10% by weight Stearyl alcohol 28% by weight 2,2′-Dihydroxy-4-methoxybenzophenone 6% by weight C.I. I. Solvent Blue 38 5% by weight

Example 5 p-methoxyphenol 49% by weight 12-hydroxystearic acid (melting point 78 ° C.) 28% by weight lauric acid (melting point 45 ° C.) 13% by weight ethyl-2-cyano-3,3′-diphenylacrylate 6 Wt% C.I. I. Solvent Red 49 4% by weight

Comparative Example 1 2-hydroxy-4-containing the recording medium of Example 1
Except for methoxybenzophenone, its content is 1,12
The component substituted with decanediol was treated in the same manner as in Example 1 to obtain a recording medium of Comparative Example 1.

Comparative Example 2 Comparative Example 2 was carried out in the same manner as in Example 1 except that p-tert-butylphenyl salicylate contained in the recording medium of Example 2 was removed and the content was replaced by stearic acid.
The recording medium of

Comparative Example 3 2-Hydroxy-4-4 contained in the recording medium of Example 3
A recording medium of Comparative Example 3 was obtained by treating the components except that octoxybenzophenone was replaced with cetyl alcohol, in the same manner as in Example 1.

Comparative Example 4 A component in which 2,2'-dihydroxy-4-methoxybenzophenone contained in the recording medium of Example 4 was removed and the content was replaced with myristic acid was treated in the same manner as in Example 1. A recording medium of Comparative Example 4 was obtained.

Comparative Example 5 Ethyl-2-cyano-contained in the recording medium of Example 5
A recording medium of Comparative Example 5 was obtained by treating in the same manner as in Example 1 except that 3,3′-diphenylacrylate was removed and the content thereof was replaced with lauric acid.

○ Nickel complex type ultraviolet stabilizer and colorant
Recording medium containing Example 6 Dimethyl oxalate 41% by weight Palmitic acid (melting point 62 ° C.) 51% by weight Nickel dithiocarbamate 2% by weight C.I. I. Solvent Black 3 6% by weight

Example 7 Acetamide 52% by weight Paraffin wax (melting point 69 ° C.) 42% by weight (trade name, HNP-11 Nippon Seiko Co., Ltd.) Nickel bis (octylphenyl) sulfide 1% by weight C.I. I. Solvent Black 46 5% by weight

Example 8 Methyl carbamate (melting point 54 ° C.) 42% by weight Stearyl alcohol 51% by weight Tinuvin-120 2% by weight C.I. I. Solvent Black 47 5% by weight

Example 9 Dibutylhydroxytoluene 49% by weight Candelilla wax (melting point 70 ° C.) 44% by weight (trade name, Candelilla special name, Noda Wax Co., Ltd.) Sanol LS-770 2% by weight C.I. I. Solvent Black 3 5% by weight

Example 10 Ethylene carbonate (melting point 39 ° C.) 50% by weight 1,12-dodecanediol 45% by weight Tinuvin-120 3% by weight C.I. I. Solvent Black 3 4% by weight

Comparative Example 6 The recording medium of Comparative Example 6 was obtained by treating the recording medium of Example 1 with the exception of nickel dithiocarbamate and substituting palmitic acid for the content thereof in the same manner as in Example 6. It was

Comparative Example 7 The nickel bis (octylphenyl) sulfide contained in the recording medium of Example 7 was removed, and a component in which the content was replaced with paraffin wax was treated in the same manner as in Example 6 to prepare the composition of Comparative Example 7. A recording medium was obtained.

Comparative Example 8 Tinuvin-12 contained in the recording medium of Example 8
A recording medium of Comparative Example 8 was obtained by treating components in which the content of the stearyl alcohol was replaced by 0, except for 0, in the same manner as in Example 6.

Comparative Example 9 Sanol LS-7 contained in the recording medium of Example 9
A recording medium of Comparative Example 9 was obtained by treating components except for 70, the content of which was replaced with candelilla wax, in the same manner as in Example 6.

Comparative Example 10 Tinuvin-1 contained in the recording medium of Example 10
Comparative Example 10 was carried out by treating components except 20, except that the content was replaced with 1,12-dodecanediol, in the same manner as in Example 6.
The recording medium of

○ Hindered amine light stabilizers and colorants
Recording medium containing 11 Example 11 ethylene carbonate (melting point 39 ° C.) 45% by weight 1,10-decanediol 47% by weight MARK-LA77 (trade name) 2% by weight C.I. I. Solvent Yellow 33 6% by weight

Example 12 Diphenyl carbonate 54% by weight Stearic acid (melting point 67 ° C.) 40% by weight MARK-LA68 (trade name) 1% by weight C.I. I. Solvent Blue 36 5% by weight

Example 13 Dimethyl oxalate 47% by weight Candelilla wax (melting point 70 ° C.) 46% by weight (trade name, Candelilla special name, Noda Wax Co., Ltd.) MARK-LA63 (trade name) 2% by weight C.I. I. Solvent Black 46 5% by weight

Example 14 3,4-Xylidine (melting point: 51 ° C.) 51% by weight Cetyl alcohol 42% by weight Tinuvin 622LD (trade name) 2% by weight C.I. I. Solvent Red 1 5% by weight

Example 15 Ethyl carbamate (melting point: 50 ° C.) 49% by weight Stearyl alcohol 44% by weight Tinuvin 144 (trade name) 3% by weight C.I. I. Solvent Black 3 4% by weight

Comparative Example 11 MARK-LA77 contained in the recording medium of Example 11
Except that the component whose content was replaced by 1,10-decanediol was treated in the same manner as in Example 11 to obtain a recording medium of Comparative Example 11.

Comparative Example 12 MARK-LA68 contained in the recording medium of Example 12
Except that the component whose content was replaced by stearic acid was treated in the same manner as in Example 11 to obtain a recording medium of Comparative Example 12.

Comparative Example 13 MARK-LA63 contained in the recording medium of Example 13
Except that the component whose content was replaced by candelilla wax was treated in the same manner as in Example 11 to obtain a recording medium of Comparative Example 13.

Comparative Example 14 Tinuvin 6 contained in the recording medium of Example 14
A recording medium of Comparative Example 14 was obtained by treating the components except 22LD except that the content was replaced with cetyl alcohol in the same manner as in Example 11.

Comparative Example 15 Tinuvin 1 contained in the recording medium of Example 15
A recording medium of Comparative Example 15 was obtained by treating components having the same content as those of Example 11 except that 44 was replaced with stearyl alcohol.

The recording media obtained in the above Examples 1 to 15 were ejected from the recording head 6 by the recording apparatus shown in FIG.
Recording was performed on commercially available copy paper. The recording head is a BJ130J recording head manufactured by Canon Inc., and
The same recording head as shown in FIG. 6 was used. The recording head includes a wall 99 arranged on a substrate 91 so as to separate each liquid flow path 92, and a glass transparent top plate 94 in contact with the wall 99.
And a heater 93 provided in each liquid flow path 92. The heater 93 is energized by an electrode (not shown) according to an image signal. The size of the nozzle composed of the liquid passage 92, the heater 93, and the orifice 92a is 26 μm in height,
The width is 38 μm, the size of the heater is 30 μm width × length 42
μm, the heater position is 22 μm from the end on the most orifice side to the orifice, and 4 per inch.
44 nozzles were arranged at a density of 00 nozzles. The recording head has a heater voltage of 15.5 V and a pulse width of 2.5 μse.
c. The recording head of the BJ130J is driven at a driving frequency of 1 kHz, the heater voltage is 28.5 V, and the pulse width is 7 μse.
c, the driving frequency was 100 Hz.

Further, as shown in FIG. 5, the temperature control means 4
6, the tank 41, the supply path 42 and the recording head 6 are
Heated to ° C. Further, recording was carried out on a commercially available copy paper, and the fixability and light resistance of the obtained recorded matter were evaluated. The evaluation method is shown below.

* 1 Fixability evaluation Image signals are applied to 16 heaters so as to form a checkered pattern for each pixel, a recording medium is ejected, and recording is performed on copy paper. After 10 seconds, the printing unit is changed to a filter paper (product name). : No5C, manufactured by Toyo Roshi Kaisha, Ltd., and evaluated by rubbing.

* 2 Evaluation of Light Resistance of Recorded Image 3 × 3 cm on commercially available copy paper using the above-mentioned recording apparatus.
A solid printed matter was prepared and irradiated with a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) for 35 hours, and the color difference before and after irradiation was determined to evaluate the light resistance. The evaluation results are shown in Tables 1 to 3.

On the other hand, the same recording heads as those used in the recording mediums of Comparative Examples 1 to 15 obtained in Example were used, and a heating head was used as a discharge energy source of the recording medium. The recording medium was held and liquefied and discharged, and the above-mentioned fixing property and light resistance were evaluated. The evaluation results are shown in Table 1
3 shows.

[0083]

[Table 1]

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

As described above, according to the recording medium of the first aspect of the present invention and the recording method using the same, since the recording medium is in a solid state at room temperature and further contains an ultraviolet absorber. Not only the fixability of the recording medium is good, but also a high-quality recorded image having excellent light resistance can be obtained.

According to the recording medium of the second aspect of the present invention and the recording method using the same, the recording medium is in a solid state at room temperature and further contains a nickel complex type ultraviolet stabilizer, so that the recording medium is fixed. It is possible to obtain a high-quality recorded image having not only good properties but also excellent light resistance.

According to the recording medium of the third invention of the present invention and the recording method using the same, since the recording medium is in a solid state at room temperature and further contains a hindered amine light stabilizer, the fixability of the recording medium is improved. It is possible to obtain a high-quality recorded image having excellent light resistance as well as excellent image resistance.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a recording apparatus capable of observing a foaming state of a recording medium according to the present invention.

FIG. 2 is a schematic diagram showing a recording head used in the recording apparatus of FIG.

FIG. 3 is a schematic diagram showing an example of a discharge state of the recording method of the present invention.

FIG. 4 is a schematic diagram showing another example of the ejection state of the recording method of the present invention.

FIG. 5 is a schematic view showing an example of a recording apparatus using the recording medium of the present invention.

FIG. 6 is a schematic diagram of a recording head used in an example of the present invention.

[Explanation of symbols]

 1 Microscope 2 Strobe 6 Recording Head 7 Heating Means 11 Substrate 12, 63, 93 Heater 13 Ink 14 Top Plate 15 Orifice 16 Bubbles 17 Droplets 18 Heating Heater 41 Tank 42 Supply Channel 44 Recording Paper 46 Temperature Control Means 62 , 92 nozzles 62a, 92a ejection orifices 67, 97 ink supply ports

Claims (12)

[Claims] 1. A recording medium for use in a recording method for recording by ejecting a recording medium from a discharge orifice by applying thermal energy, characterized by containing at least an ultraviolet absorber and a colorant. A recording medium that is solid at room temperature. 2. The room temperature solid recording medium according to claim 1, wherein an ultraviolet absorber having a melting point equal to or lower than the heating temperature of the recording head is used. 3. A recording medium that is solid at room temperature and contains at least an ultraviolet absorber and a coloring agent is used, and the recording medium is heated and melted, and thermal energy corresponding to a recording signal is applied to the recording medium from the ejection orifice. A recording method characterized in that recording is performed by ejecting a medium. 4. The recording method according to claim 3, wherein an ultraviolet absorber having a melting point equal to or lower than the heating temperature of the recording head is used. 5. A recording medium which is solid at room temperature and contains at least an ultraviolet absorber and a colorant is used, and after the recording medium is heated and melted, a discharge orifice for discharging the recording medium and a liquid communicating with the discharge orifice. A recording head provided with a discharge path and a discharge energy generating means for supplying thermal energy for discharging the recording medium in the liquid path, and bubbles generated by the discharge energy generating means are discharged from the discharge orifice to the outside air. A recording method in which the recording medium is ejected to perform recording. 6. The recording method according to claim 5, wherein an ultraviolet absorber having a melting point equal to or lower than the heating temperature of the recording head is used. 7. A recording medium for use in a recording method for recording by ejecting a recording medium from a discharge orifice by applying thermal energy, comprising at least a nickel complex ultraviolet stabilizer and a colorant. Characteristic solid recording medium at room temperature. 8. An ejection orifice by using a recording medium which is solid at room temperature and which contains at least a nickel complex ultraviolet stabilizer and a colorant, by heating and melting the recording medium, and further applying thermal energy according to a recording signal. A recording method, wherein the recording medium is ejected from the recording medium to perform recording. 9. An ejection orifice for ejecting the recording medium after the recording medium is heated and melted by using a recording medium which is a solid at room temperature containing at least a nickel complex type ultraviolet stabilizer and a coloring agent, and the ejection orifice A recording head provided with a liquid passage communicating with the discharge energy generating means for supplying thermal energy for discharging the recording medium in the liquid passage is used to discharge the bubble generated by the discharge energy generating means. A recording method, wherein the recording medium is discharged by communicating with outside air through an orifice to perform recording. 10. By applying thermal energy,
A recording medium used in a recording method in which recording is performed by discharging a recording medium from a discharge orifice, which is a solid recording medium at room temperature characterized by containing at least a hindered amine light stabilizer and a colorant. 11. A normal temperature solid recording medium containing at least a hindered amine light stabilizer and a colorant is used.
A recording method, wherein the recording medium is heated and melted, and thermal energy corresponding to a recording signal is applied to discharge the recording medium from an ejection orifice to perform recording. 12. An ejection orifice for ejecting the recording medium after the recording medium is heated and melted by using a recording medium which is a solid at room temperature and which contains at least a hindered amine light stabilizer and a colorant, and communicates with the ejection orifice. Using a recording head having a liquid passage for discharging and a discharge energy generating means for supplying thermal energy for discharging the recording medium in the liquid passage, and the bubble generated by the discharge energy generating means is used for the discharge orifice. Communicating with the outside air,
A recording method for ejecting the recording medium to perform recording.