JP3135310B2 - Ejection recording method, room temperature solid recording medium used for this recording method, and ejection recording apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a jet recording method in which a recording medium solid at room temperature is caused to fly on a recording material to perform recording, a recording medium of room temperature solid used in this recording method, and an jet recording apparatus. Things.

[0002]

2. Description of the Related Art In a jet recording method, recording is performed by causing small droplets of a recording medium (ink) to fly and adhere to a recording material such as paper. Among the jet recording methods, the applicant of the present invention discloses Japanese Patent Publication No. 61-59911 and Japanese Patent Publication No. 61-59912.
No., JP-B-61-59914, using a liquid ink at room temperature, applying thermal energy to the ink to generate bubbles in the ink, and discharging the droplets by the bubbles generated in the ink. According to the method of discharging from the orifice, it is possible to easily realize a high-density multi-orifice of the recording head, and to record a high-resolution and high-quality image at a high speed.

[0003] In addition to the above-mentioned methods, there are the following methods for liquid jet recording using a liquid ink at normal temperature.

In Japanese Patent Application Laid-Open No. 54-161935, as shown in FIG.
A method is disclosed in which a gas 1 is gasified and the gas 32 is ejected from an ejection port together with an ink droplet 33. According to this method, clogging of the orifice can be prevented by ejecting the gas 32 from the nozzle. In addition, 35 is an electrode.

Japanese Patent Application Laid-Open No. 61-185455 discloses a plate-like member 4 having a small opening 40 as shown in FIG.
The liquid ink 44 filled in the minute gap 43 between the heating element head 1 and the heating element head 42 is heated by the heating element head (FIG. 2).
1 (a), (b)), the ink droplets 46 fly from the small openings 40 by the generated bubbles 45, and the gas forming the bubbles is also ejected from the small openings 40 (FIG. 2).
1 (c)) There is a description about a recording method for forming an image on recording paper.

In Japanese Patent Application Laid-Open No. 61-249768, as shown in FIG. 22, thermal energy is applied to liquid ink 50 to form bubbles, and ink droplets 58 are formed and fly based on the expansion force of the bubbles. At the same time, there is described a recording method in which the gas forming the bubbles is also ejected into the atmosphere from the large opening 52. In addition, 51 is a heating element.

Japanese Unexamined Patent Publication No. 61-197246 discloses a plurality of holes 6 provided in a film 60 as shown in FIG.
The recording method is such that the ink 62 filled in 1 is heated by a recording head 64 having a heating element 63 to generate bubbles 67 in the ink 62, and the ink droplets 65 fly on a recording medium 66.

On the other hand, the ink used in the jet recording method quickly dries and fixes on the recording material, but does not dry easily in the nozzle and does not easily clog the nozzle.
Contradictory characteristics are required.

In response to this requirement, conventional room temperature liquid inks generally contain water as a main component and contain a water-soluble high-boiling solvent such as glycol for the purpose of preventing drying and clogging. However, when recording is performed on plain paper using such ink, the ink does not quickly dry and fix, and when touching the character immediately after printing by hand, the ink gets on the hand or the character is rubbed, and the print quality deteriorates. There was such a problem.

In addition, since the permeability of the ink greatly differs depending on the type of recording paper, there has been a problem that when a conventional ink containing water as a main component is used, only a specific recording paper can be used. In particular, in recent years, it has been demanded that good recording can be performed on so-called plain paper such as copy paper, report paper, notebooks, and stationery which are often used in offices.

In response to this request, US Pat.
No. 170, JP-A-58-108271 and JP-A-61-108
83268, JP-A-61-159470, JP-A-61-159470
JP-A-2-48774 or JP-A-55-54368 discloses a jet recording method in which a solid hot-melt type ink is heated and melted at normal temperature to fly.

[0012]

However, even when heated and melted at room temperature, the ink which is solid at room temperature has a higher viscosity than a water-based ink which is liquid at room temperature, and has a large resistance to the generation and expansion of bubbles. For this reason, according to the conventional ejection recording method using solid ink at normal temperature, even if bubbles are generated in the ink, sufficient ejection energy cannot be obtained and the ink ejection speed is slow, or the shape of the bubbles is not good. It became even. As a result, the ink droplets did not accurately adhere to a predetermined position on the recording material, or the volume of the ejected droplets became uneven. In the worst case, the ink may not be ejected from the ejection port.

Further, in order to prevent the ink from rising on the recording material, JP-A-1-242672 and JP-A-2-51570 disclose ordinary temperature solid inks to which a supercooling agent is added. I have.

However, conventional inks at room temperature, to which a supercooling agent has been added, can prevent swelling of the ink, but it takes time to completely fix the ink, and if sufficient time is not provided after forming a recorded image, There has been a problem that a hand becomes dirty or a recorded image is disturbed by the recorded image.

Conventional inks at room temperature which are used in the jet recording method are described in JP-A-1-236.
287, JP-A-1-263170 and JP-A1-2
No. 63171 discloses inks containing xylenol, diacetamide, and 2,2-dimethyl-1-propanol as main components, respectively. However, these conventional solid inks are left unheated without recording. In addition, the physical properties of the ink are likely to change, nozzle clogging is likely to occur, and a recording image may blur depending on recording paper.

According to the present invention, there is provided an ink jet recording method in which bubbles grow large even when a solid recording medium is used at room temperature, and therefore the ejection speed is high, and the volume of ejected droplets is always constant and ejection is reliably performed. The purpose is to provide.

Further, the present invention provides a room temperature solid recording medium which is excellent in fixing property of a recorded image, can obtain a high quality recorded image without swelling of ink and does not bleed, and can efficiently convert thermal energy into ejection energy. The purpose is to provide.

Still another object of the present invention is to provide a recording apparatus which melts a solid recording medium at normal temperature and ejects the recording medium as small droplets.

[0019]

According to the jet recording method of the present invention, a recording medium which is a solid at room temperature is heated and melted, and thermal energy is applied in accordance with a recording signal to generate bubbles in the recording medium. When recording is performed by discharging the recording medium from a discharge port with the bubbles, the internal pressure of the bubbles is changed to an external pressure.
When the following is true, the foam communicates with the outside air.

Further, according to the jet recording method of the present invention, a room-temperature solid containing a colorant and a heat-fusible solid substance having a melting point Tm of 40 to 150 ° C. and a boiling point Tb of 260 to 340 ° C. Using a recording medium, the recording medium is heated and melted, and thermal energy is further applied in accordance with a recording signal to discharge the recording medium from an ejection port to perform recording.

The room temperature solid recording medium of the present invention is a recording medium used in an ejection recording method in which a recording medium is ejected from an ejection port to perform recording by applying thermal energy. Tm is 40 ° C or more and 150 ° C or less,
It contains a hot-melt solid substance having a boiling point Tb of 260 ° C. or more and 340 ° C. or less.

Further, the room temperature solid recording medium of the present invention is characterized in that bubbles are generated in the recording medium by applying thermal energy, and the bubbles are communicated with the outside air to discharge the recording medium from a discharge port. The recording medium used for the recording method,
The relationship between the colorant and the melting point Tm and the solidification temperature Tf is Tm-T
and a heat-fusible solid substance satisfying f ≦ 30 ° C.

Further, the room temperature solid recording medium according to the present invention is characterized in that bubbles are generated in the recording medium by applying thermal energy, and the bubbles are communicated with the outside air to discharge the recording medium from a discharge port. The recording medium used for the recording method,
The relationship between the colorant, the first heat-fusible solid substance having a melting point Tm of 36 ° C. or more and 150 ° C. or less, and the boiling point Tb of 150 ° C. or more and 370 ° C. or less, and the relationship between the melting point Tm and the solidification temperature Tf is Tm−Tf.
≦ 30 ° C. and a heat-fusible solid substance.

Further, according to the present invention, there is provided an ejection recording apparatus comprising: a recording head having a heater for generating thermal energy in accordance with a recording signal; and a discharge port for discharging a molten recording medium of a room temperature solid; A tank to store,
Heating means for melting the recording medium in the recording head and in the tank, wherein the recording head and the
Recording head with tank by integrally configuring the recording tank
When the recording head with tank is made replaceable,
In the bubbles generated in the thermal energy is provided the heater near the discharge port which causes communicate ambient air communicating, further
A heater for generating heat energy according to the recording signal; and
Has an ejection port for ejecting molten medium solid recording medium
A recording head for storing the recording medium of the room temperature solid.
And a tank for replenishing a normal temperature solid recording medium to the tank.
An ink cartridge, and
Heating means for melting the recording medium in the tank.
The heater is provided near the discharge port to provide the heat
The bubbles generated in the energy are communicated with the outside air .

As will be described in detail later, the jet recording method of the present invention heats and melts a solid recording medium (ink) at normal temperature (5 ° C. to 35 ° C.) and heats the molten recording medium in accordance with a recording signal. By applying energy, the recording is performed by discharging from the discharge port (orifice).

When thermal energy corresponding to a recording signal is applied to a recording medium in a molten state, bubbles are generated in the recording medium, and the generation of the bubbles generates discharge energy for discharging the recording medium from a discharge port.

The apparatus shown in FIG. 1 is an apparatus for carrying out the recording method of the present invention (to be described in more detail later). A recording medium contained in a tank 21 is supplied to a recording head 23 through a supply path 22. Is done. As the recording head 23, the recording head shown in FIG. 2 can be used. In the tank 21, the supply path 22, and the recording head 23, the recording medium in the apparatus is kept in a liquid state by the heat of the heating means 20 and 24. The heating means 20 and 24 are set to a predetermined temperature by the temperature control means 26. The heating means 20 and 24 may be set at a temperature higher by 10 ° C. to 20 ° C. than the melting point of the recording medium. A print signal is sent from the drive circuit 25 to the printhead 23, and the ejection energy generating means (for example, a heater) of the printhead 23 is driven according to the print signal.

The head 23 is, as shown in FIG.
Walls 8 arranged in parallel above, and wall 1 forming liquid chamber 10
4 are provided. Further, the top plate 4 is arranged on the walls 8 and 14. In FIG. 2A, the top plate 4 is shown separated from the walls 8 and 14 so that the inside of the recording head can be easily seen. An ink supply port 11 is formed in the top plate 4, and a molten recording medium flows into the liquid chamber 10 from the ink supply port 11. Between the walls 8 is a nozzle 15 through which the molten recording medium passes. On the substrate 1 in the middle of each nozzle 15, a heater 2 for applying thermal energy to the recording medium in accordance with a recording signal is provided. Is provided. Bubbles are generated in the recording medium by the heat energy from the heater 2, and the recording medium is discharged from the discharge port 5 of the nozzle 15.

In the recording method of the present invention, when the bubble generated on the recording medium by application of thermal energy expands and reaches a predetermined size, the bubble penetrates through the discharge port 5 and communicates with the outside air.
Hereinafter, this point will be described.

FIG. 3 is a cross section of one nozzle 15 provided in the recording head 23, and FIG. 3A shows a state before foaming. First, an electric current is applied to the heating means 24 to melt the solid recording medium 3 at room temperature. After the recording medium 3 is liquefied, when an electric current is instantaneously applied to the heater 2 to heat the recording medium 3 near the heater 2 in a pulsed manner, the recording medium 3 suddenly boils, vigorously generates bubbles 6, and expands. Start (Fig. 3
(B)). The foam 6 continues to expand, grows to the discharge port 5 side with particularly low inertance (inertia), and penetrates from the discharge port 5 to communicate with the outside air (FIG. 3C). The recording medium 3 on the ejection port 5 side of the bubble 6 jumps forward due to the momentum given by the bubble 6 up to this moment, and eventually becomes an independent droplet 7.
And fly to a recording material such as paper (FIG. 3D).
After the recording medium 3 jumps out, the gap formed at the tip of the nozzle 15 is filled with a new recording medium 3 due to the surface tension of the recording medium 3 at the rear and leakage from the nozzle wall, and returns to the state before ejection.

The recording head 23 is provided at a position where the position of the heater 2 is closer to the direction of the discharge port 5 than the conventional recording head. This is the simplest configuration to allow the bubbles to communicate with the outside air. The amount of thermal energy generated by the heater 2, the physical properties of the ink, and the size of each part of the recording head 23 (the distance between the discharge port 5 and the heater 2, the discharge port 5 and the nozzle 1
(Width and height of 5) can be selected as desired, so that the bubbles can be communicated with the outside air.

Although it cannot be said unconditionally how close the heater 2 should be to the discharge port 5 to communicate the bubbles with the outside air, the distance from the discharge port side end of the heater 2 to the discharge port 5 (shown in FIG. 9) In the case of a recording head, the distance from the surface of the heater 2 to the discharge port 5) is 5 μm or more and 80 μm or more.
Hereinafter, the thickness is more preferably 10 μm or more and 60 μm or less.

In order to ensure that the bubbles communicate with the outside air, the height H of the discharge port (see FIG. 2A) is preferably equal to or smaller than the width W of the nozzle measured at the heater.

In order to allow the bubbles to communicate with the outside air, the width of the heater 2 is preferably 50% to 95%, more preferably 70% to 90% of the width of the nozzle. Furthermore, heating means 2
According to 4, the viscosity of the ink in the molten state is preferably 100 cps or less. It is also desirable that the bubbles be in communication with the outside air when the bubbles have a maximum volume or a volume of at least 70%, more preferably at least 80% of the maximum volume of the bubbles that would be reached if the bubbles do not communicate with the outside air. It is preferred.

In the present invention, since the bubbles generated in the recording medium communicate with the outside air, substantially all of the recording medium between the bubbles and the discharge port 5 is discharged. Therefore, the volume of the ejected droplet is always constant. In the conventional jet recording method, bubbles generated in the recording medium usually do not communicate with the outside air, and shrink and disappear after growing to the maximum. When bubbles generated in the recording medium do not communicate with the outside air as in the related art, all of the recording medium between the bubbles and the discharge port 5 does not discharge, but only partially discharges.

In the jet recording method in which the bubble grows to the maximum without communicating with the outside air and then contracts, the bubble sometimes shrinks but does not completely disappear and remains on the heater. If small bubbles remain on the heater in this way, at the time of the next droplet discharge,
There is a problem that foam generation and growth are not performed correctly due to small bubbles remaining on the heater. In this regard, in the jet recording method of the present invention in which bubbles communicate with the outside air, all the recording medium between the bubbles and the discharge port is discharged, so that no small bubbles remain on the heater.

In the recording method of the present invention, since the inertance from the heater 2 to the discharge port 5 of the recording head 23 is small, the generated momentum of the generated bubbles is efficiently enjoyed by the droplets 7. For this reason, it is possible to stably eject even a high-viscosity one such as a recording medium which is difficult to eject in the conventional recording method, that is, a solid recording medium which is heated to a temperature equal to or higher than its melting point and liquefied at normal temperature. In the recording method of the present invention,
Since the bubbles generated in the recording medium communicate with the outside air when the recording medium is ejected, the ejection speed of the recording medium becomes extremely high. For this reason, the droplets of the recording medium accurately adhere to the target point on the recording material, and also adhere to the solid recording medium thinly without rising on the recording material. The advantage that the solid recording medium adheres thinly on the recording material is as follows.
This is particularly effective when a recording medium is overlaid on a recording material to form a multicolor image.

In the present invention, when the bubbles generated by the heater 2 communicate with the outside air from the discharge port 5, it is preferable that the bubbles be communicated under the condition that the internal pressure of the bubbles is equal to or less than the outside pressure.

FIG. 4 is a graph showing the relationship between the internal pressure of the foam (graph a) and the volume of the foam (graph b). However, FIG.
Is a graph when bubbles do not communicate with the outside air. In FIG. 4, when a pulse current is applied to the heater 2 at time T = t ₀ , bubbles are generated in the recording medium, and the internal pressure of the bubbles rapidly increases. Bubbles begin to expand as they occur.

The expansion of the foam does not end immediately after the current application to the heater 2 ends, but continues for a while. As a result the internal pressure of the bubble is below the outside pressure at time T = t ₁ decreases rapidly. After the foam has expanded to some extent, it shrinks and disappears.

Therefore, as shown in FIG. 5, time T = t ₁
If the bubbles are allowed to communicate with the outside air at _a subsequent time, for example, at time ta, the internal pressure of the bubbles immediately before the communication becomes equal to or less than the outside pressure.

If the bubbles are communicated with the outside air and the droplets are ejected under the condition that the internal pressure of the bubbles is equal to or lower than the external pressure, the mist-like recording medium unnecessary for recording can be prevented from being scattered, and the recording material or the like can be prevented. Does not stain the inside of the device.

Conventionally, in a jet recording method, a sprayed mist-like recording medium (hereinafter referred to as "splash" or "mist") is frequently ejected in addition to the droplet for recording, which has been a problem. ADVANTAGE OF THE INVENTION According to this invention, a splash and a mist can be prevented by making the internal pressure of a bubble lower than external pressure, when communicating a bubble with external air.

Since it is difficult to directly measure the internal pressure of the foam, the magnitude relationship between the internal pressure of the foam and the external pressure may be determined as follows.

That is, by measuring the volume V _b of the foam from the time when the recording medium starts foaming to the time when the foam communicates with the outside air, the second derivative of V _b , d ² V _b / dt ^2, is obtained. The relationship between the internal pressure of the foam and the external pressure can be known.
If d ² _Vb / dt ² > 0, the internal pressure of the foam is higher than the external pressure, and if d ² _Vb / dt ² ≦ 0, the internal pressure of the foam is equal to or lower than the external pressure. Referring to FIG. 6, from the start of foaming T = t ₀ to T = t ₁ , the internal pressure of the foam is higher than the external pressure and d ² V _b /
dt ^2> 0, and the internal pressure of the bubble until the time T = t _a until the foam from T = t ₁ is communicated with the outside air is below ambient air pressure, d ²
_Vb / dt ² ≦ 0. It is possible to know the magnitude relation between the internal pressure and the outside pressure of the bubbles by determining the second derivative d ² V _b / dt ² of V _b as described above.

Instead of measuring the above-mentioned _Vb , the discharge port is provided between the time when the bubble is generated and the time when the droplet of the recording medium flies (between (a) to (c) in FIG. 3). recording medium 3a protruding from 5 (see FIG. 3 (b). hereinafter, the recording medium discharge portion 3a) by measuring the V _d of, V _d of the second derivative d ² V _d
By determining / dt ² , the magnitude relationship between the internal pressure of the foam and the external pressure can also be known. That is, d ² V _d / dt ² >
If 0, the internal pressure of the foam is higher than the external pressure, and d ² V _d / d
If t ² ≦ 0, the internal pressure of the foam is equal to or lower than the external pressure.

The volume of the recording medium protrusion 3a at each time is observed with a microscope 201 while illuminating the recording medium protrusion 3a with pulsed light using a light source 200 such as a strobe, an LED, or a laser as shown in FIG. Can be measured. That is, by causing a recording head that continuously ejects small droplets at a constant frequency to emit pulse light in synchronization with the driving pulse and with a predetermined delay time, the recording medium is ejected at a predetermined time. The projected shape of the portion 3a can be measured. At this time, the measurement can be performed more accurately if the pulse width of the pulse light is as small as possible within a range in which a sufficient light amount for the measurement can be secured. The volume of the recording medium protrusion 3a can be roughly estimated from measurement in one direction, but in order to obtain it more accurately, as shown in FIG. In addition, it is desirable to simultaneously measure the projected shape of the recording medium protrusion 3a from two directions y and z orthogonal to each other. At this time, one of the measurement directions y and z in the microscope 201 is desirably a direction parallel to the direction in which the discharge ports 5 are arranged. FIG. 8 (a) shows the images measured from the two directions as described above.
Then, as shown in FIG. 8B, the widths a (x) and b (x) of the recording medium protrusion 3a with respect to the x coordinate value are measured. By calculating from these values in accordance with the following equation, the volume Vd of the recording medium protruding portion 3a at a predetermined time can be obtained. Note that the following equation is obtained by calculating y− of the recording medium protrusion 3a.
The z-section is approximated by an ellipse, and can be obtained with sufficient accuracy for calculating the volume of the recording medium protrusion 3a and the bubble 6.

V _d = (π / 4) ∫a (x) · b (x) dx Thus, by changing the lighting delay time of the pulse light from the light source 200 in order from 0, the bubble is generated. The change in Vd before the droplet of the recording medium flies can be obtained.

The measurement of the foam volume _Vb in the nozzle 15 can also be performed by applying the method shown in FIG. However, in order to measure the bubble volume _Vb , it is necessary to form a part of the recording head with a transparent member so that the bubbles can be observed from outside the recording head.

In order to observe the behavior of the recording medium protruding portion 3a and the bubble 6, a time resolution of about 0.1 μsec is required. Therefore, the pulse light source 200 is preferably an infrared LED, and the pulse width of the light source is 50 nsec is preferred. It is preferable to connect an infrared camera to the microscope 201 and capture an image.

Further, by causing the bubbles to communicate with the outside air from the discharge ports 5 under the condition that the first derivative of the moving speed of the tip of the bubbles in the direction of the discharge ports 5 is negative, ink mist and splash can be further prevented.

Further, referring to FIG. 3 (b), bubbles 6 are discharged from the end of the heater 2 serving as the discharge energy generating means on the discharge port 5 side.
The distance 1 _a from the end opposite to the outlet 5 of the heater 2 to the distance 1 _b from the end opposite to the outlet 5 of the heater to the end of the heater 2 on the side of the air outlet 5 By setting 1 _a / 1 _b ≧ 1, preferably 1 _a / 1 _b ≧ 2, and more preferably 1 _a / 1 _b ≧ 4 immediately before communication with the ink, a void formed near the ejection port after ejection of the recording medium Therefore, the time until a new recording medium is filled can be shortened, and higher-speed recording can be performed. 1 _a / 1 _b increases if brought close to the discharge opening 5 the position of, for example, the heater 2.

FIG. 9 shows another example of the recording head.
The discharge port 5 is provided in the lateral direction of the nozzle 15. FIG.
The bubble 6 communicates with the outside air also in the case where the recording head of FIG. 3 is used. That is, from the state before foaming shown in FIG. 9A, after the recording medium 3 is melted by the heating means 24, when the heater 2 is energized, bubbles 6 are generated on the heater 2 (FIG. 9B). Thereafter, the bubbles 6 continue to expand (FIG. 9C), and the bubbles 6 and the outside air communicate with each other, so that the small droplets 7 fly out of the discharge ports 5 (FIG. 9D).

Next, a recording medium (ink) which is solid at normal temperature (5 ° C. to 35 ° C.) will be described.

In the present invention, as described in detail above, the recording medium which is solid at room temperature is heated and melted, and heat is applied to the melted recording medium in accordance with a recording signal so that the recording medium is discharged from the discharge port to perform recording. Do. Therefore, the room-temperature solid recording medium of the present invention contains at least a heat-fusible solid substance and a colorant, and further contains an additive for adjusting physical properties as needed, or an organic solvent liquid at room temperature such as alcohol, etc. It contains.

The recording medium of the present invention has a melting point of 36 ° C.
Those in the range of 200 ° C. are desirable. If the temperature is lower than 36 ° C., the recording medium may be melted and stain hands and the like depending on the change in room temperature. If the temperature is higher than 200 ° C., a large amount of energy is required to liquefy the recording medium. More preferably, the melting point is in the range of 36 ° C to 150 ° C.

Examples of the heat-fusible solid substance contained in the recording medium of the present invention, which is a solid at room temperature, include, for example, acetamide, p-vanillin, o-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-heptadecanone, 1-tetradecanamine, 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,
1,8-octanediol, 1,1-diethylurea, p
Butyl-hydroxybenzoate, methyl 2-hydroxy-naphthoate, 8-quinolinol, stearylamine acetate, 1,3-diphenyl-1,3-propanedione, methyl m-nitrobenzoate, dimethyl oxalate, phthalide, 2, One or a mixture of two or more of 2-diethyl-1,3-propanediol, 8-quinolinol, N-tert-butylethanolamine, glycolic acid, diacetyl monooxime, and acetoxime can be used.

The above-mentioned heat-fusible solid substance has various characteristics, such as a substance having particularly excellent ejection characteristics, a substance having particularly excellent storability, and an extremely little bleeding on a recording material, depending on the kind. . Therefore, it is preferable to appropriately select from the above-mentioned heat-meltable solid substances according to the purpose of use and use them for the recording medium.

The melting point of the heat-fusible solid substance is defined as Tm and the boiling point (1
Boiling point at atmospheric pressure. When Tb is used, when a heat-fusible solid material that satisfies both of the following formulas (A) and (B) among the above-described heat-fusible solid materials is used, the fixing property of a recorded image is excellent and the thermal energy is improved. , A recording medium of a room temperature solid which can efficiently convert the recording medium into ejection energy can be obtained.

36 ° C. ≦ Tm ≦ 150 ° C. (A) 150 ° C. ≦ Tb ≦ 370 ° C. (B) The boiling point Tb is more preferably 200 ° C. ≦ Tb ≦ 340 ° C.

Further, if 40 ° C. ≦ Tm ≦ 150 ° C. and 2
Since the recording medium containing the heat-fusible solid material satisfying the condition of 60 ° C. ≦ Tb ≦ 340 ° C. can convert heat energy into ejection energy very efficiently, the recording method described with reference to FIGS. That is, the jet recording method in which bubbles generated in the recording medium do not communicate with the outside air, that is, bubbles generated in the recording medium continue to expand, reach a maximum size without communicating with the outside air, and then contract and disappear. Even when used in the ejection recording method described above, the ejection speed of small droplets is high, and the ejection of small droplets is reliably performed without clogging of nozzles.

Hereinafter, the ejection characteristics of the recording medium will be described in detail.

When thermal energy is applied to a normal temperature solid recording medium in a molten state in accordance with a recording signal, bubbles are generated in the recording medium. Occurs. The discharge energy changes variously depending on the bubble generation state. The present inventor has studied the ejection characteristics of the recording medium using the apparatus shown in FIG. The recording apparatus shown in FIG. 10 is adapted to observe a foaming state in a recording medium. Using this apparatus, the correlation between the foaming state and the ejection state of the recording medium (ejection quality) was examined.

The recording head 123 is manufactured by Canon B
A J130J recording head was used. This recording head 12
3 is almost the same as that shown in FIGS. 2A and 2B, but since the heater 2 is located at a position away from the discharge port 5,
The recording medium is discharged without causing bubbles generated in the recording medium to communicate with the outside air. The nozzle of the print head of BJ130J is
As shown in FIG. 18, the discharge port 5 is narrower than the flow path. The dimensions of the nozzle and the dimensions of the discharge port 5 shown in FIG. 18 are as follows. A = 135 μm, B = 27 μ
m, C = 120 μm, D = 50 μm, E = 30 μm, F
= 30.5 μm.

The BJ130J print head has 48 nozzles arranged at a density of 360 nozzles per inch.

A microscope 16 is arranged above the recording head 123 so that the inside of the nozzle 15 can be observed through a transparent top plate as shown in FIG. Microscope 16
A strobe 17 is attached to the, and the foaming state of the recording medium can be observed only when the strobe 17 emits light. The strobe 17 emits light after a delay time that can be set arbitrarily after the heater 2 starts applying heat by the strobe drive circuit 18 and the delay circuit 19.

The recording head 123 is provided with a heating means 24. The recording head 123 is heated to a temperature higher by 10 ° C. to 20 ° C. than the melting point of the recording medium to keep the recording medium in a molten state. 28 is a head drive circuit and 29 is an external power supply.

In this way, the liquid chamber 10 of the recording head 123 was filled with the molten recording medium, and a pulse was applied to the heater 2 to observe bubbles generated on the heater 2 while changing the delay time of strobe light emission. The recording medium used in the examination of the ejection characteristics does not contain a coloring agent,
Or, even if it was contained, it was made a very small amount. This is because if the coloring agent is contained in a large amount, the bubbles become difficult to see. Further, in the apparatus shown in FIG.
Pulse width 7 μS, applied voltage 25-30 V, drive frequency 1
00 Hz.

As a result of examination of the ejection characteristics, when the size of the heater 2 is 10 μm to 150 μm in width and 10 μm to 200 μm in length, if the ejection of the recording medium is good, as shown in FIG.
When the bubble 80 becomes the largest, the area of the heater 2 becomes 1
It was found that a single bubble covered more than / 2, and more than 3/4 (hereinafter, single boiling). As shown in FIG. 12, the generated foam 81 covers only a small part of the area of the heater 2, or as shown in FIG. 13, a plurality of small bubbles 82 cover the heater 2. When not covering more than 1/2, the ejection energy was not sufficiently generated, and the recording medium did not eject from the ejection port.

As a result of studying single boiling by changing the heat fusible solid material of the recording medium in various ways, the heat fusible solid material having a single boiling point has a boiling point of 150 ° C. or more and 37 ° C.
0 ° C or lower, especially 200 ° C or higher and 340 ° C or lower, further 260 ° C
It turned out that what was more than 340 degreeC was preferable. When the boiling point of the heat-fusible solid substance is 150 ° C. or more and 370 ° C. or less, particularly 260 ° C. or more and 340 ° C. or less, the amount of the recording medium evaporated from the recording head decreases, and the physical properties of the recording medium change. It was also found that the nozzle was not clogged.

The recording medium of the present invention is at room temperature (5 ° C. to 35 ° C.)
It is solid. Therefore, according to the recording medium of the present invention, the fixability of the recorded image is good, and a high-quality recorded image can be obtained even when recording on plain paper. In the present invention, in order to solidify the recording medium at room temperature, a heat-meltable solid substance having a melting point of 36 ° C. or higher, particularly 40 ° C. or higher, and more preferably 50 ° C. or higher is used. In consideration of heat energy for heating and melting the recording medium, the melting point of the heat-fusible solid substance is preferably 150 ° C. or lower, more preferably 120 ° C. or lower.

Examples of the heat-meltable solid substance having a melting point of 40 ° C. to 150 ° C. and a boiling point of 260 ° C. to 340 ° C. include acenaphthene, 2-bromonaphthalene, 2,2
6-dimethylquinoline, vanillin, dibutylhydroxytoluene, diphenyl carbonate, m-acetotoluidine, phenyl benzoate, 1-naphthol and the like are preferred. The recording medium using such a heat-fusible solid substance can reliably discharge small droplets not only by the jet recording method described with reference to FIGS. 3 and 9 but also by the jet recording method in which bubbles do not communicate with the outside air.

When the solidification temperature of the heat-fusible solid substance is Tf, the melting point Tm and the solidification temperature Tf satisfy the following condition: Tm−Tf ≦ 30 ° C. (C) When a solid substance is used, it is possible to obtain a recording medium which is excellent in fixability of a recorded image and which is solid at room temperature without causing blurring of the recorded image. Further, a heat-fusible solid substance having Tm−Tf ≦ 15 ° C. is preferable.

When a heat-fusible solid material having a temperature Tm−Tf> 30 ° C. is used, depending on the type of the recording material, the recording medium may unnecessarily penetrate into the recording material before it is solidified. Will be.

Further, it is preferable to use a heat-fusible solid substance having Tm−Tf ≧ 7 ° C., since the swelling of the recording medium on the surface of the recording material is reduced.

The solidification temperature Tf is 36 ° C. or more and 150 ° C. or less,
Further, the temperature is preferably from 40 ° C to 150 ° C.

In the present invention, the melting point Tm and the solidification temperature Tf were measured as follows.

(Measurement device) Differential scanning calorimeter DSC-
7 (manufactured by PerkinElmer) (Measurement conditions) Heating rate 5 ° C / min Cooling rate 5 ° C / min

With the above measuring device and measuring conditions, the melting point Tm
Is the peak value at the time of temperature rise, and the solidification temperature Tf is the peak value at the time of temperature decrease.

FIG. 14 shows a measurement example of the melting point Tm and the solidification temperature Tf using the recording medium of the present invention having the following composition. Dibenzofuran 9.5 g Varifast Black # 3820 0.5 g In FIG. 14, point A is the melting point Tm, and point B is the solidification temperature Tf.

As long as the content of the colorant is not extremely large, there is no change in the physical properties of the recording medium between the case where the colorant is contained and the case where the colorant is not contained.

Examples of the heat-fusible solid substance satisfying Tm−Tf ≦ 30 ° C. include 1,8-octanediol,
2,5-dimethyl-2,5-hexanediol, imidazole, 4-methylbiphenyl, 9-heptadecanone,
Indole, 2-acetylpyrrole, dibenzofuran,
2-methoxynaphthalene, tiglic acid, p-dibromobenzene, styrene glycol, 1,1-diethylurea,
butyl p-hydroxybenzoate, methyl 2-hydroxy-naphthoate, 8-quinolinol, stearylamine acetate, 1,3-diphenyl-1,3-propanedione, methyl m-nitrobenzoate, dimethyl oxalate, glutaric acid, etc. Is preferred.

The recording medium of the present invention may contain an organic solvent which is liquid at room temperature, such as 1-hexanol,
-Alcohols such as heptanol and 1-octanol,
It may contain alkylene glycols such as ethylene glycol, propylene glycol, and triethylene glycol, and other ketones, keto alcohols, amides, and ethers. These organic solvents cause bubbles generated in the recording medium to grow greatly.

The organic solvent preferably has a boiling point of 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 inhibitor.

The recording medium of the present invention can be obtained by mixing the above materials in a heated state.

From the above description, as the heat-fusible solid substance used for the ordinary temperature solid recording medium, the above formula (A)
Although those satisfying both (B) and (C) are preferable, the types of the heat-fusible solid substance satisfying all of the formulas (A), (B) and (C) are limited. Therefore,
In the following manner, the heat-fusible solid substance used in the recording medium of the present invention can be selected from a wide range of materials. That is, a first heat-fusible solid material satisfying the formulas (A) and (B) and a second heat-fusible solid material satisfying the formula (C) are mixed, and the heat used in the present invention is mixed. What is necessary is just to make it a fusible solid material.

In this case, the first heat-meltable solid substance satisfying the formulas (A) and (B) includes, for example, 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, dichloroxylerin, 3,4-dichloroaniline, 4-chloro-m-cresol, p-bromophenol, dimethyl oxalate, 1-naphthol, dibutylhydroxytoluene, , 3,5-trichlorobenzene, p
-Tert-pentiphenol, durene, dimethyl p
Phenyldiamine, tolan, styrene glycol, propionamide, diphenyl carbonate, 2-chloronaphthalene, acenaphthene, 2-promonaphthalene, indole, 2-acetylpyrrole, dibenzofuran, p-chlorobenzyl alcohol, 2-methoxynaphthalene, tiglic acid, p -Dibromobenzene, 9-heptadecanone,
1-tetradecanamine, 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 and the like can be used.

As the second heat-fusible solid substance satisfying the formula (C), for example, 1,8-octanediol, 2,5
-Dimethyl-2,5-hexanediol, imidazole, 4-methylbiphenyl, 9-heptadecanone, indole, 2-acetylpyrrole, dibenzofuran, 2-
Methoxynaphthalene, tiglic acid, p-dibromobenzene, styrene glycol, 1,1-diethylurea, p-
Butyl benzoate, methyl 2-hydroxy-naphthoate,
8-quinolinol, stearylamine acetate, 1,
3-Diphenyl-1,3-propanedione, methyl m-nitrobenzoate, dimethyl oxalate, glutaric acid and the like can be used. Further, waxes such as carnauba wax, paraffin wax, sasol wax, microcrystalline wax and ester wax can be used. , Stearic acid,
Fatty acids of paumitic acid, higher alcohols such as cetyl alcohol and stearyl alcohol, diols such as hexanediol, octanediol, decanediol and dodecanediol, and other aromatic compounds such as fatty acid esters, aromatic esters and aromatic alcohols , Polyamide resins, polyester resins, polyurethane resins, epoxy resins, polyolefin resins, polyacryl resins, and the like.

The first heat-meltable solid substance is preferably ethylene carbonate. In this case, the second heat-meltable solid substance has 2 to 8 hydroxyl groups in the molecule, particularly 2 to 5 hydroxyl groups. It is preferable to use a substance (for example, a polyhydric alcohol and its partially esterified product, a saccharide and its partially esterified product). When ethylene carbonate is used as the first heat-fusible solid substance, the hydroxyl value of the second heat-fusible solid substance is 300 or more and 1 or more.
000 or less, more preferably 330 or more and 960 or less. Further, when ethylene carbonate is used as the first heat-fusible solid substance, the melting point of the second heat-fusible solid substance is 50 ° C or more and 120 ° C or less, particularly 60 ° C or more and 110 ° C.
The following is preferred. When ethylene carbonate is used as the first heat-fusible solid substance, the second heat-fusible solid substance specifically includes 1,12-dodecanediol, 1,1
0-decanediol, 1,8-octanediol, glycerin mono 12-hydroxystearate or 9.1
It is preferred to use 0-dihydroxystearic acid methyl ester.

Further, a solubilizer (a surfactant or the like) may be contained for the purpose of improving the compatibility between the first heat-fusible solid substance and the second heat-fusible solid substance.

Further, at least one of the first heat-fusible solid substance and the second heat-fusible solid substance is Tm-Tf
If ≧ 7 ° C., the rise of the recording medium on the surface of the recording material is reduced, which is preferable.

The more preferable ranges of the melting point Tm and the boiling point Tb of the first heat-fusible solid material satisfying the formulas (A) and (B) have been described above in the description of the formulas (A) and (B). Same as range. Further, a relation T between the melting point Tm of the second heat-fusible solid material satisfying the formula (C) and the solidification temperature Tf.
Regarding m-Tf, a more preferable range is as follows:
Is the same as the range described in the description.

As the colorant contained in the recording medium of the present invention, various dyes and pigments such as conventionally known direct dyes, acid dyes, basic dyes, disperse dyes, vat dyes, sulfur dyes and oil-soluble dyes are effective. It is. Particularly preferable dyes include oil-soluble dyes described in the following color index.

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, etc. I. Solvent Orange 1,2,3
4,4: 1,5,6,7,11,16,17,19,2
0,23,25,31,32,37,37: 1,38,
40, 40: 1, 45, 54, 56, 59, 60, 6
2,63,67,68,71,72,73,74,75
Etc. C. I. Solvent Red 1,2,3,4
7, 8, 13, 14, 17, 18, 19, 23, 24,
25, 26, 27, 29, 30, 33, 35, 37, 4
1,42,43,45,46,47,48,49,4
9: 1, 52, 68, 69, 72, 73, 74, 80,
81 etc. C.I. I. Solvent Violet 2,3,8,
9,10,11,13,14,21,21,1,24
31, 32, 33, 34, 36, 37, 38, 45, 4
6, 47, etc. I. Solvent Blue 2,4,5,7,
10, 11, 12, 22, 25, 26, 35, 36, 3
7, 38, 43, 44, 45, 48, 49, 50, 5
1, 63, 64, 66, 67, 68, 70, etc. I. Solvent Green 1,3,4
5,7,8,9,20,26,28,29,30,3
2,33 etc. C.I. I. Solvent Brown 1,1: 1,
2,3,4,5,6,12,19,20,22,25,
28, 29, 31, 37, 38, 42, 43, 44, 4
8, 49, 52, 53, 58, etc. I. Solvent Black 3,5,6
7, 8, 13, 22, 22: 1, 23, 26, 27, 2
8, 29, 33, 34, 35, 39, 40, 41, 4
2,43,45,46,47,48,49,50 etc.

Further, inorganic pigments such as calcium carbonate, barium sulfate, zinc oxide, lithopone, titanium oxide, chrome yellow, cadmium yellow, nickel titanium yellow, naples yellow, yellow iron oxide, red iron oxide, cadmium red, cadmium red, cadmium mercury sulfide, navy blue and ultramarine blue Organic pigments such as carbon black, azo pigments, phthalocyanine pigments, triphenylmethane pigments, and bad pigments are also preferably used. The color indexes of the pigments that can be preferably used are shown below. C. I. Pigment Yellow 1, 2, 3,
5, 12, 13, 14, 15, 17, 83 C.I. I. Vat Yellow 1, C.I. I. Pigment Orange 1, 5, 1
3, 16, 17, 24 C.I. I. Vat Orange 3 C.I. I. Pigment Red 1, 2, 3, 4,
5, 7, 9, 12, 22, 23, 37, 38, 48, 4
9, 50, 51, 53, 57, 58, 60, 63, 8
1, 83, 88, 112 C.I. I. Pigment Violet 1, 3, 1
9, 23 C.I. I. Vat Violet 2 C.I. I. Pigment Blue 1, 2, 15, 1
6, 17 C.I. I. Vat Blue 4 C.I. I. Pigment Green 2, 7, 8, 1
0 C.I. I. Pigment Black 1

In the recording medium of the present invention, the content of the heat-fusible solid substance is 50 to 99% by weight based on the recording medium.
Further, the content is preferably 60 to 95% by weight.

In the case where the heat-fusible solid material is a mixture of the first heat-fusible solid material and the second heat-fusible solid material, the first heat-fusible solid material is heat-fusible. It is preferably contained in an amount of 30% by weight or more and 90% by weight or less, more preferably 40% by weight or more and 70% by weight or less based on the whole solid substance.

The content of the colorant is 1 to 10 with respect to the recording medium.
20% by weight, more preferably 3 to 15% by weight.

The organic solvent, if necessary, is preferably contained in an amount of 0 to 10% by weight based on the recording medium.

Hereinafter, a recording apparatus for performing the recording method of the present invention will be described.

FIG. 15 is a perspective view of a recording apparatus for performing the recording method of the present invention. 100, 101, 102 and 10
Reference numeral 3 denotes a recording head with a tank, for example, 16 heads / mm
44 nozzles at a pitch of By the recording heads 100, 101, 102, and 103 with the tanks, a recording medium of a normal temperature is ejected toward the recording material 105 to perform recording. The recording apparatus shown in FIG. 15 has four recording heads 100 having the same structure for performing multi-color recording,
101, 102 and 103 are provided on a carriage 104. Recording heads 100, 101, 1 with each tank
From 02 and 103, recording media of different colors, for example, yellow, magenta, cyan, and black recording media are ejected.

In the recording head with a tank shown in FIG. 15, a tank for accommodating a recording medium and a recording head are integrally formed, as will be described in detail later. That is, FIG.
The recording head with a tank shown in FIG.
And the recording head 23 are integrated.

The recording heads with tanks 100, 101,
102 and 103 respectively have a heater 100 for temperature control.
a, 101a, 102a, and 103a are attached to heat the recording head with the tank and keep the recording medium in the recording head with the tank in a molten state. That is, the temperature control heaters 100a, 101a, 102
a and 103a correspond to the heating means 20 and 24 in FIG.

The carriage 104 is mounted on the guide rail 10
6 and 107 are slidably supported. An endless belt 110 hung on a motor pulley 108 and a tension pulley 109 is fixed to the carriage 104. A carriage motor 111 is attached to the rotation center of the motor pulley 108, and the carriage motor 111 is driven by a scanning signal. When driven, the motor pulley 108 rotates. As a result, the endless belt 110 rotates, and the carriage 104 scans along the guide races 106 and 107 as the endless belt 110 rotates. That is, the carriage 104
Scans according to a scanning signal.

The recording material 105 is held and held by the paper feed roller 112 and the paper feed pinch roller 113, and further by the tension roller 114 and the tension pinch roller 115, respectively. The rotational force of a motor 119 is transmitted to the paper feed roller 112 and the tension roller 114 via gears 116, 117 and 118,
The recording material 105 is fed in the direction of arrow P in accordance with the rotation of No. 9.

A platen 120 is provided at a position facing the recording heads 100, 101, 102, and 103 with the tank via the recording material 105. The distance between an ejection port (not shown) of the recording head with a tank and the recording material 105 is maintained at, for example, 0.5 mm.

As described above, the carriage 104 moves along the guide rails 106 and 107, and
The recording material is fed in the direction of the arrow P in synchronization with the movement of the recording medium, whereby recording is sequentially performed on the recording material.

Recording heads with tanks 100, 101, 1
Reference numerals 02 and 103 denote a tank 122 for storing the recording medium 3 in a molten state and a recording head 121, as shown in FIG.
And are integrated. The configuration of the recording head 121 is the same as that shown in FIGS.

The heater 1 for controlling the head temperature in the tank 122
00a, 101a, 102a, and 103a melt the recording medium through the ink supply pipe 121a.
The liquid is supplied to the liquid chamber 121b and discharged from the discharge port 121c. The supply of the recording medium 3 from the tank 122 to the recording head 121 is performed by the surface tension of the recording medium 3 and the wetting between the recording head member and the recording medium 3. 140
Is a lid of the ink supply port 122a. For example, when ink shortage in the tank 122 is detected by an ink amount sensor (not shown), the lid 140 is opened to supply a solid recording medium. As the shape of the room-temperature solid recording medium, a columnar shape, a pellet shape, a granule shape, a powder shape, and the like can be used.

The supply of the recording medium is performed as shown in FIG. 17 in order to facilitate handling and prevent the hands and the periphery of the apparatus from being stained during the supply.
May be used.
In FIG. 17, the ink cartridge 124 is filled with the granular recording medium 3. When the ink shortage in the tank 122 is detected, the lid 125 is opened, and a predetermined amount of the granular recording medium 3 is supplied into the tank 122. When the recording medium in the ink cartridge 124 runs out, the ink cartridge 124 is replaced with a new ink cartridge and mounted.

The entire recording head with a tank shown in FIG. 16 may be replaced with a recording head cartridge. In this case, the recording head 121 and the temperature control heater 10
Energization of the power supply lines 0a, 101a, 102a, and 103a may be performed such that the electric connection portion provided on the carriage 104 and the electric connection portion provided on the recording head cartridge are connected when the cartridge is mounted. .

The recording apparatus of the present invention can be used as a printer for a personal computer or a word processor. Further, as shown in FIG. 19, it can be used as a facsimile printer 139. In FIG. 19, a controller 131 controls the image reading unit 130 and the printer 139. The whole controller 131 is a CP
It is controlled by U137. The read data from the image reading unit 130 is transmitted to the partner station through the transmission circuit 133. Data received from the partner station is sent to the printer 139 through the receiving circuit 132. The image memory 136 stores predetermined image data. The printer controller 138 controls the printer 139. 134 is a telephone.

The image information received from the line 135 is demodulated by the receiving circuit 132, and is sequentially stored in the image memory 136. When the image of at least one page is stored in the memory 136, the image of the page is recorded. The CPU 137 reads out one page of image information from the memory 136 and sends out one page of image information to the printer controller 138. Printer controller 138
The printer 13 receives the image information of one page from the CPU 137 and records the image information of the page.
9 is controlled.

The CPU 137 receives the next page during recording by the printer 139.

Hereinafter, the present invention will be described with reference to examples.

Example 1 Using the same recording head as that shown in FIG. 2, an image was formed by the apparatus shown in FIG. A microscope 16 was installed in the recording apparatus shown in FIG. 1 with the configuration shown in FIG. 10, and bubbles generated in the recording medium were observed.

The recording head is provided on the substrate 1 with each liquid flow path 1
5, a transparent top plate 4 made of glass in contact with the wall, and a heater 2 provided in each liquid flow path 15.
It is composed of The heater 2 is energized by an electrode (not shown) according to an image signal. The nozzle composed of the liquid path 15, the heater 2, and the orifice 5 has a height of 27μ.
m, the width is 40 μm, the heater size is 32 μm in width, the length is 40 μm, the position of the heater 2 is 20 μm from the end closest to the orifice 5 to the orifice 5, and the density of 400 nozzles per inch is 44 μm. Nozzles are arranged.

C. I. Solvent Black 3 5.0 parts by weight acetamide (Tm = 82 ° C., T _f = 37 ° C., T _b = 22
2) 73.0 parts by weight paraffin wax (T _m = 69 ° C., T _f = 65 ° C.)
2.0 parts by weight (HNP-11, manufactured by Nippon Seiro Co., Ltd.)

The above components were stirred at 95 ° C. in a container, uniformly mixed and dissolved, filtered with a Teflon filter having a pore size of 0.45 μm while heating, and then cooled to obtain a solid ink. The ink was supplied from an ink supply port while the recording head was heated to 95 ° C., and ejection was attempted.

The conditions for energizing the heater 2 of the recording head were an applied voltage of 16.0 V, a pulse width of 2.5 μsec, and a driving frequency of 1 kHz.

First, the situation where ink was ejected from the continuous 16 nozzles was observed from above the transparent top plate 4 using a pulse light source and a microscope, and it was found that bubbles were communicating with the outside air about 3 μsec after the start of foaming. confirmed. The droplet discharge speed was about 9 m / sec.

Then, an image signal was applied to the 16 heaters 2 so as to form a checkerboard pattern for each pixel, and the ink was ejected and adhered to plain paper (commercially available copy paper). Was short, and no stain was generated even when the image was rubbed with a hand 5 seconds after recording.

Example 2 An image was formed under the same conditions as in Example 1 under the same recording head, recording apparatus, and power supply to the recording head.

C. I. Solvent Black3
3.0 parts by weight ε-caprolactam (T _m = 69 ° C., T _f > 30 ° C.) 8
1.0 parts by weight microcrystalline wax (T _m = 84 ° C., T _f = 7
16.0 parts by weight (9 ° C.) (Hi-Mic 1080 manufactured by Nippon Seiro Co., Ltd.)

The above components were stirred at 100 ° C. in a container, uniformly mixed and dissolved, filtered with a Teflon filter having a pore size of 0.45 μm while heating, and then cooled to obtain a solid ink. The ink was supplied from an ink supply port while the recording head was heated to 100 ° C., and ejection was attempted.

First, first. Observation of the state where the ink was ejected from the continuous 16 nozzles from above the transparent top plate 4 using a pulsed light source and a microscope confirmed that bubbles were communicating with the outside air about 3 μsec after the start of firing. Further, the discharge speed of the droplet was about 8 m / sec.

Then, an image signal was applied to the 16 heaters 2 so as to form a checkerboard pattern for each pixel, and ink was ejected and adhered to plain paper (commercial copy paper). The image was short, and no stain was generated even when the image was rubbed by hand 5 seconds after recording.

Example 3 An image was formed under the same recording head, recording apparatus, and power supply conditions to the recording head as in Example 1.

C. I. Solvent Black3
3.0 parts by weight N-oxymethylacetamide ( _Tm = 51 ° C., _Tf = 3
_{2 ℃, T b = 205 ℃} ) 87.0 parts by weight acetamide _{(T m = 82 ℃, T} f = 37 ℃, T b = 22
2 ° C) 10.0 parts by weight

The above-mentioned components were stirred in a container at 95 ° C., uniformly mixed and dissolved, and filtered while filtering with a Teflon filter having a pore diameter of 0.45 μm, and then cooled to obtain a solid ink. The ink was supplied from an ink supply port while the recording head was heated to 95 ° C., and ejection was attempted.

First, the state where ink was ejected from the continuous 16 nozzles was observed from above the transparent top plate 4 using a pulse light source and a microscope, and it was found that bubbles were communicating with the outside air approximately 3 μsec after the start of foaming. confirmed. Further, the discharge speed of the droplet was about 11 m / sec.

Then, an image signal was applied to the 16 heaters 2 so as to form a checkered pattern for each pixel, and ink was ejected and adhered to plain paper (commercial copy paper). It was short, and no stain was generated even if the image was rubbed with a hand 5 seconds after recording.

Example 4 Using the same four recording heads as in Example 1, a color image was formed using the recording apparatus shown in FIG. Each recording head was supplied with yellow, magenta, cyan, and black inks. The constituent materials of each ink are shown below.

Yellow C.I. I. Solvent Yellow116 3.
0 parts by weight acetamide (T _m = 82 ° C., T _f = 37 ° C., T _b = 22
2 ° C.) 80.0 parts by weight Paraffin wax (T _m = 69 ° C., T _f = 65 ° C.)
7.0 parts by weight Magenta C.I. I. Solvent Red 218 4.0 parts by weight acetamide (T _m = 82 ° C., T _f = 37 ° C., T _b = 22
2 ° C.) 80.0 parts by weight Paraffin wax (T _m = 69 ° C., T _f = 65 ° C.)
6.0 parts by weight cyan C.I. I. Solvent Blue 70 5.0 parts by weight acetamide (T _m = 82 ° C., T _f = 37 ° C., T _b = 22
2 ° C.) 80.0 parts by weight Paraffin wax (T _m = 69 ° C., T _f = 65 ° C.)
5.0 parts by weight black C.I. I. Solvent Black 3 4.0 parts by weight acetamide (T _m = 82 ° C., T _f = 37 ° C., T _b = 22
2 ° C.) 80.0 parts by weight Paraffin wax (T _m = 69 ° C., T _f = 65 ° C.)
6.0 parts by weight

The components of the above inks were each heated to 95 ° C.
The mixture was stirred in a container, uniformly mixed and dissolved, and filtered with a Teflon filter having a pore size of 0.45 μm while heating.
Upon cooling, a solid state ink was obtained. 9 for each recording head
In the state where the temperature was raised to 5 ° C., ink of each color was supplied from the ink supply port, and ejection was attempted. The conditions for energizing the heater 2 of each recording head were an applied voltage of 16.0 V and a pulse width of 2.5 μsec.
c, the driving frequency was 1 kHz.

First, when the ejection state of each ink was observed using a pulse light source and a microscope, it was confirmed that bubbles were communicated with the outside air about 3 μsec after the start of foaming for each ink. The droplet discharge speed was about 11 m / yellow.
sec, magenta about 9 m / sec, cyan about 9 m / sec
c, black was about 10 m / sec.

Next, ink was ejected using four recording heads and allowed to adhere to plain paper (commercial copy paper) to form a full-color image. As a result, stable high-quality color image recording was achieved. Obtained. Further, the fixing time of this image was short, and no stain occurred even when the image was rubbed with the hand 5 seconds after recording.

Example 5 Acenaphthene (melting point: 95 ° C.,
(Solidification temperature 77 ° C., boiling point 279 ° C.)
Melted by heating to ℃, Varifast Black as dye
# 3820 (VALIFAST Black # 382
And 0.5 parts by weight of Orient Chemical Industry Co., Ltd.), and after stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 6 9.5 parts by weight of 2-chloronaphthalene (melting point: 60 ° C., solidification temperature: 56 ° C., boiling point: 256 ° C.) was melted by heating to 80 ° C., and as a dye, VALIFAST Black # 3820 was used. 3
820, manufactured by Orient Chemical Industry Co., Ltd.), and after stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 7 9.5 parts by weight of 2-bromonaphthalene (melting point 59 ° C., solidification temperature 52 ° C., boiling point 282 ° C.) was heated and melted at 80 ° C., and as a dye, VALIFAST Black # 3820 was used. 38
20, and Orient Chemical Industry Co., Ltd.), and after stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 8 2,6-Dimethylquinoline (melting point: 60 ° C .; solidification temperature: 30 ° C. or higher; melting point: 267 ° C.)
8.0 parts by weight and 1.5 parts by weight of paraffin wax (HNP11, made of Japanese wax, melting point 69 ° C., solidification temperature 65 ° C.) are heated to 80 ° C. and melt-mixed, and further, Varifast Black # 3820 ( VALIFAST Bl
After adding 0.5 parts by weight of ACK # 3820 (manufactured by Orient Chemical Industry Co., Ltd.), the mixture was stirred for 1 hour, and the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 9 2,6-Dimethoxyphenol (melting point: 56 ° C., solidification temperature: 32 ° C. or higher, boiling point: 258 ° C.)
9.5 parts by weight were heated and melted at 80 ° C., and as a dye, Varifast Black # 3820 (VALIFAST BL1) was used.
After adding 0.5 parts by weight of ACK # 3820 (manufactured by Orient Chemical Industry Co., Ltd.), the mixture was stirred for 1 hour, and the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 10 9.5 parts by weight of vanillin (melting point: 83 ° C., solidification temperature: 37 ° C., boiling point: 284 ° C.) was heated to 110 ° C.
And melted, and dyed as Balifast Black #
3820 (VALIFAST Black # 382
And 0.5 parts by weight of Orient Chemical Industry Co., Ltd.), and after stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 11 Dibutylhydroxytoluene (melting point 70 ° C., solidification temperature 30 ° C. or higher, boiling point 265 ° C.)
9.5 parts by weight were heated and melted at 100 ° C., and Varifast Black # 3820 (VALIFAST B) was used as a dye.
rack # 3820, manufactured by Orient Chemical Industry Co., Ltd.)
Was added for 0.5 hour, and the mixture was stirred for 1 hour, and the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

(Example 12) Diphenyl carbonate (melting point: 83)
8.5 ° C., solidification temperature 50 ° C., boiling point 302 ° C.)
-1.0 g of octanol was heated to 110 ° C and melt-mixed. Further, Varifast Black # 382 was used as a dye.
0 (VALIFAST Black # 3820, manufactured by Orient Chemical Industry Co., Ltd.) was added, and after stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 13 9.5 m-acetotoluidine (melting point 66 ° C., solidification temperature 30 ° C. or more, boiling point 303 ° C.) 9.5
A part by weight is heated and melted at 90 ° C., and Varifast Black # 3820 (VALIFAST Blac) is used as a dye.
k # 3820, manufactured by Orient Chemical Industry Co., Ltd.)
After adding 5 parts by weight and stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 14 Phenyl benzoate (melting point 7)
6.5 parts by weight, stearic acid (melting point 70 ° C, solidification temperature 66 ° C), 1 ° C, solidification temperature 30 ° C or more, boiling point 315 ° C)
0 parts by weight and 1.0 g of diethylene glycol at 100 ° C.
And heat-mixed, and then varifast as a dye
Black # 3820 (VALIFASTBlack
(# 3820, manufactured by Orient Chemical Industry Co., Ltd.) was added in an amount of 0.5 part by weight, and the mixture was stirred for 1 hour. Then, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 15 1-Naphthol (melting point: 96)
℃, solidification temperature 80 ° C, boiling point 279 ° C)
Heated and melted at 20 ° C., and used as a dye Varifast Black # 3820 (VALIFAST Black # 38)
20, Orient Chemical Industry Co., Ltd.) was added, and after stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Using the recording media prepared in Examples 5 to 15, recording was performed on recording paper (commercially available copy paper) using the same recording apparatus as in Example 1. The recording head and the conditions for energizing the recording head were the same as in Example 1.

Further, the tank 21, the supply path 22, and the recording head 23 were heated by the temperature control means 26 to the temperatures shown in Table 1 by the recording medium used. Recording was performed by continuously ejecting the recording medium from 16 consecutive nozzles of the recording head 23 for one hour. A microscope 16 was installed in the recording apparatus shown in FIG. 1 with the configuration shown in FIG. 10, and bubbles generated in the recording medium were observed.

Thus, the ejection state of the recording medium was evaluated. Table 1 shows the evaluation results. In Table 1, the ejection state indicates how many of the 16 nozzles eject the recording medium (16/16 indicates that the recording medium ejects from all nozzles, and 0/16 indicates that the recording medium ejects. Indicating that there is no nozzle for ejecting the medium).

After the printing was completed, the apparatus was left for 12 hours without printing while driving the temperature control means 26, and then printing was again performed to evaluate the ejection state (evaluation of clogging). Table 1 shows the evaluation results.

[0154]

[Table 1]

In Examples 5 to 15, it was confirmed that the bubbles communicated with the outside air about 3 μsec after the start of foaming. In Examples 5 to 15, the ejection was stable, the fixing was fast, and high-quality recording was possible.

Examples 16 to 24 Using the recording media of Examples 5, 7, 8, and 10-15,
Recording was performed on recording paper (commercially available copy paper) using the apparatus shown in FIG. 1 equipped with a J130J recording head. The conditions for energizing the heater of the recording head were as follows: applied voltage 28.5
V, the pulse width was 7 μsec, and the driving frequency was 100 Hz.

Further, the temperature control means 26 heated the tank 21, the supply path 22, and the recording head 23 to the temperatures shown in Table 2 depending on the recording medium used. The recording was performed by continuously discharging the recording medium from all the continuous 24 nozzles of the recording head 26 for one hour. A microscope 16 was installed in the recording apparatus shown in FIG. 1 with the configuration shown in FIG. 10, and bubbles generated in the recording medium were observed.

Thus, the foaming state in the recording medium and the ejection state of the recording medium were evaluated. Table 2 shows the evaluation results.
In Table 2, the ejection state indicates how many nozzles out of the 24 nozzles eject the recording medium (24/24).
Indicates that the recording medium is ejected from all nozzles, and 0/24 indicates that there is no nozzle that ejects the recording medium).

After the printing was completed, the recording medium was left for 24 hours without printing while the temperature control means 26 was driven, and then printing was performed again to evaluate the ejection state (evaluation of clogging). Table 2 shows the evaluation results.

Comparative Example 1 2,2-dimethyl-1-propanol (melting point: 56 ° C., solidification temperature: 35 ° C., boiling point: 114
9.5 parts by weight are heated and melted at 80 ° C., and Varifast Black # 3820 (VALIFAST) is used as a dye.
Black # 3820, Orient Chemical Industry Co., Ltd.
Was added and the mixture was stirred for 1 hour, and the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Comparative Example 2 Diacetamide (mp 79
C., solidification temperature 45.degree. C., boiling point 218.degree. C.)
Melted by heating to ℃, Varifast Black as dye
# 3820 (VALIFAST Black # 382
And 0.5 parts by weight of Orient Chemical Industry Co., Ltd.), and after stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Comparative Example 3 2-Naphthyl phenyl ketone (melting point: 83 ° C., solidification temperature: 70 ° C., boiling point: 398 ° C.) 9.5
Parts by weight is heated and melted at 110 ° C., and varifast black # 3820 (VALIFAST Bla) is used as a dye.
After adding 0.5 parts by weight of ck # 3820 (manufactured by Orient Chemical Industry Co., Ltd.) and stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

The recording medium obtained in Comparative Example 1-3 was recorded on recording paper under the same recording head recording apparatus and recording conditions as in Example 16. Table 2 shows the evaluation results.

[0164]

[Table 2]

Example 25 Phthalide (T _m = 75)
C, T _f > 30 ° C.), 70 parts by weight and paraffin wax (HNP-9, manufactured by Nippon Seiro Co., Ltd., T _m = 76 ° C., T _f =
72 ° C.) 27 parts by weight were heated and melt-mixed.
I. Solvent Black 3 3 parts by weight,
After stirring for 3 hours, the mixture of the above components was added to a pore size of 1 μm.
m. After that, the liquid was cooled to room temperature to obtain a recording medium.

(Example 26) 2,2-Diethyl-1,3
-Propanediol ( _Tm = 62 ° C, _Tf = 38 ° C) 60
Weight and 37 parts by weight of an ester wax (Hoechst wax E, manufactured by Hoechst Co., Ltd., T _m = 81 ° C., T _f = 74 ° C.) were heated and melt-mixed. I. Solvent Bla
After adding 3 parts by weight of ck3 and stirring for 3 hours, the mixture of the above components was filtered with a 1 μm pore size filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 27 8-Quinolinol (T _m =
75 ° C., T _f = 38 ° C.) 82 parts by weight and microcrystalline wax (Hi-Mic 1080, Nippon Seiro Co., Ltd.)
( _Tm = 84 ° C., T _f = 79 ° C.) was heated and melt-mixed. I. Solvent Black3
Was added to the mixture, and the mixture was stirred for 3 hours, and then the mixture of the above components was filtered with a 1 μm pore size filter. afterwards,
The filtrate was cooled to room temperature to obtain a recording medium.

Example 28 60 parts by weight of N-tert-butylethanolamine (T _m = 42 ° C., T _f > 30 ° C.) and candelilla wax (Candelilla specialty, _Tm = 70 manufactured by Noda Wax Co., Ltd.) C., T _f = 66 ° C.) 37 parts by weight were heated and melt-mixed. I. Solvent B
After adding 3 parts by weight of lac3 and stirring for 3 hours, the mixture of the components was filtered with a filter having a pore size of 1 μm. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

(Example 29) o-Vaniline (T _m = 44)
68 ° C., T _f > 30 ° C.) and 68 parts by weight of candelilla wax (Candelilla special name, T _m = 70 manufactured by Noda Wax Co., Ltd.)
C., T _f = 66 ° C.) 29 parts by weight are heated and melt-mixed,
Further, C.I. I. Solvent Black 3 (3 parts by weight) was added, and the mixture was stirred for 3 hours. Then, the mixture of the above components was filtered with a 1 μm pore size filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 30 Glycolic acid (T _m = 76)
68 ° C., T _f = 33 ° C.) and ester wax (Hoechst wax E, manufactured by Hoechst wax, T _m = 81)
C., T _f = 74 ° C.) 29 parts by weight are heated and melt-mixed,
Further, C.I. I. Solvent Black 3 (3 parts by weight) was added, and the mixture was stirred for 3 hours. Then, the mixture of the above components was filtered with a 1 μm pore size filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 31 Diacel monooxime (T
80 parts by weight of _m = 76 ° C., T _f = 71 ° C.) and 16 parts by weight of microcrystalline wax (Hi-MiC1080, manufactured by Nippon Seiro Co., Ltd., T _m = 84 ° C., T _f = 79 ° C.) Melt-mixed, and further C.I. I. Solvent Bl
After adding 4 parts by weight of ack3 and stirring for 3 hours, the mixture of the above components was filtered with a 1 μm pore size filter.
Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 32 Acetoxime (T _m = 6)
68 parts by weight of paraffin wax (HNP-9, manufactured by Nippon Seiro Co., Ltd., _Tm = 76 ° C, _Tf = 2 ° C, _Tf = 59 ° C)
(72 ° C.) 29 parts by weight were heated and melt-mixed.
I. Solvent Black 3 and 3 parts by weight
After stirring for a period of time, the mixture of
And filtered. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Using the recording medium prepared in Examples 25-32, recording was performed on recording paper (commercially available copy paper) using the same recording apparatus as in Example 1. The recording head and the conditions for energizing the recording head were the same as in Example 1.

In the case of any of the recording media of Examples 25-32, the temperature control means 26 controls the tank 21 and the supply path 22.
And the recording head 23 was heated to 90 ° C. Recording was performed by continuously discharging the recording medium from 24 consecutive nozzles of the recording head 23 for one hour. As a result, Example 25-
No nozzle clogging occurred in any of the 32 cases.

After the printing was completed, the recording medium was left for 24 hours without printing while driving the temperature control means 26, and printing was performed again to evaluate the ejection state. As a result, Example 2
In any of the samples 5-32, no nozzle clogged after standing for 24 hours.

Further, the recorded image formed on the recording medium of Examples 25-32 was rubbed with a filter paper (trade name: No. 5C, manufactured by Toyo Roshi Kaisha, Ltd.), and the fixability was evaluated. As a result, in each case of Examples 25 to 32, fixing was completely completed within 10 seconds, and no stain was generated even when the recorded image was rubbed with filter paper.

Example 33 Dibenzofuran (melting point: 83
° C., boiling point _{287 ℃, T m -T f =} 13 ℃) 9.5 parts by weight of heated and melted in 95 ° C., burrs Fast Black # 3820 (VALIFAST BLACK # 3 as the dye
820, manufactured by Orient Chemical Industry Co., Ltd.), and after stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 34 6.5 parts by weight of 2-acetylpyrrole (melting point 90 ° C., boiling point 220 ° C., T _m -T _f = 29 ° C.) was heated and melted at 100 ° C. to obtain paraffin wax H.
NP-11 (manufactured by Nippon Seiro, melting point 69 ° C, solidification temperature 65
C.) 3.0 parts by weight, and Varifast Black # 3820 (VALIFAST BLACK) as a dye.
(# 3820, manufactured by Orient Chemical Industry Co., Ltd.) was added in an amount of 0.5 part by weight, and the mixture was stirred for 1 hour. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 35 9.5 parts by weight of 4-methylbiphenyl (melting point 50 ° C., boiling point 267 ° C., T _m -T _f = 8 ° C.) was heated and melted at 65 ° C., and Varifast Black # 3820 was used as a dye. (VALIFAST BLACK #
3820, manufactured by Orient Chemical Industry Co., Ltd.), and after stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 36 Dimethyl oxalate (melting point: 5)
(3 ° C., boiling point 164 ° C., T _m −T _f = 12 ° C.) 9.0 parts by weight were heated and melted at 65 ° C., and VALIFAST BLACK # 3820 was used as a dye.
3820, manufactured by Orient Chemical Industry Co., Ltd.) and 0.5 part by weight of 1-octanol were added, and the mixture was stirred for 1 hour. Then, the mixture of the components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 37 Glutaric acid (melting point: 97 ° C.,
(Boiling point 303 ° C., T _m −T _f = 14 ° C.)
Heated and melted at 5 ° C., and used as dye as VALIFAST BLACK # 3820
20, manufactured by Orient Chemical Industry Co., Ltd.), and after stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 38 Homocatechol (melting point 65)
° C., boiling point _{251 ℃, T m -T f =} 35 ℃) melted by heating 9.5 parts by weight 75 ° C., burrs Fast Black # 3820 (VALIFAST BLACK # 3 as the dye
820, manufactured by Orient Chemical Industry Co., Ltd.), and after stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 39 Cetyl alcohol (melting point: 5
(0 ° C., T _m −T _f = 5 ° C.) 9.5 parts by weight were heated and melted at 65 ° C., and Varifast Black # 3820 was used as a dye.
(VALIFASTBLACK # 3820, manufactured by Orient Chemical Industry Co., Ltd.) was added in an amount of 0.5 part by weight, and after stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

(Example 40) Ethylene carbonate (melting point 39 ° C, solidification temperature 30 ° C or more, boiling point 238 ° C) 4.8
Parts by weight, 1,12-dodecanediol (melting point 82 ° C, T
_m -T _f = 5 ℃) 4.8 parts by weight of heated and melted in 95 ° C., burrs Fast black as a colorant # 3820 (VA
0.4 parts by weight of LIFAST BLACK # 3820 (manufactured by Orient Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 1 hour. Then, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 41 Acetamide (melting point: 82
6.8 parts by weight of stearic acid (melting point 70 ° C., T _m −T _f = 4 ° C.) are heated and dissolved at 95 ° C. Fast
Black # 3820 (VALIFAST BLACK
# 3820, manufactured by Orient Chemical Industry Co., Ltd.)
After adding 1 part by weight and stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 42 Tigulinic acid (melting point: 65 ° C.)
7.2 parts by weight of solidification temperature 53 ° C., boiling point 198 ° C.), 2.4 parts by weight of ester wax (melting point 81 ° C., T _m −T _f = 7 ° C., Hoechst wax E, manufactured by Hoechst) are heated and melted at 95 ° C. And Varifast Black # 38 as colorant
20 (VALIFAST BLACK # 3820, manufactured by Orient Chemical Co., Ltd.)
After stirring for an hour, the mixture of the components was filtered off. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 43 Lupine (melting point 69 ° C., solidification temperature 49 ° C., boiling point 162 ° C.) 6.8 parts by weight, 1,2-
Dodecanediol (melting point 58 ° C, _Tm - _Tf = 17 ° C)
2.8 parts by weight are heated and dissolved at 80 ° C., and Varifast Black # 3820 (VALIFAST) is used as a coloring agent.
BLACK # 3820, Orient Chemical Industry Co., Ltd.
Was added, and the mixture was stirred for 1 hour, and the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 44 o-Terphenyl (melting point: 5
8 ° C, solidification temperature 40 ° C, boiling point 332 ° C) 7.2 parts by weight,
2.4 parts by weight of pentacosane (melting point: 54 ° C., T _m −T _f = 4 ° C.) are dissolved by heating at 65 ° C., and Varifast Black # 3820 (VALIFASTBLACK) is used as a colorant.
# 3820, manufactured by Orient Chemical Industry Co., Ltd.)
After adding 1 part by weight and stirring for 1 hour, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 45 6.8 parts by weight of 9-heptadecanone (melting point 53 ° C., solidification temperature 45 ° C., boiling point 252 ° C.), dimethyl isophthalate (melting point 69 ° C., T _m −T _f = 2)
2.8 parts by weight are heated and dissolved at 80 ° C., and Varifast Black # 3820 (VALIFA) is used as a colorant.
After adding 0.4 parts by weight of ST BLACK # 3820, manufactured by Orient Chemical Industry Co., Ltd., and stirring for 1 hour,
The mixture of the components was filtered off. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 46 Acetamide (melting point: 82
℃, solidification temperature 37 ° C, boiling point 213 ° C) 6.8 parts by weight, 8
-Quinolinol (melting point 75 ° C, _Tm - _Tf = 37 ° C) 2.
8 parts by weight are heated and melted at 95 ° C., and as a coloring agent, VARIFAST BL # 3820 (VALIFAST BL)
ACK # 3820 (manufactured by Orient Chemical Industry Co., Ltd.) was added in an amount of 0.4 part by weight, and the mixture was stirred for 1 hour. Then, the mixture of the components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Example 47 4.8 parts by weight of aralkyl alcohol (melting point 65 ° C., solidification temperature 48 ° C., boiling point 369 ° C.), 1,12-dodecanediol (melting point 82 ° C., T _m −
(T _f = 8 ° C.) 4.8 parts by weight were heated and dissolved at 95 ° C., and Varifast Black # 3820 (VAL) was used as a colorant.
0.4 parts by weight of IFAST BLACK # 3820 (manufactured by Orient Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 1 hour. Then, the mixture of the above components was filtered with a filter. Thereafter, the filtrate was cooled to room temperature to obtain a recording medium.

Using the recording medium prepared in Examples 33-47, recording was performed on the five types of recording paper shown in Table 3 using the same recording apparatus as in Example 1. The recording head and the conditions for energizing the recording head were the same as in Example 1 except for the recording medium of Example 47. In the case of the recording medium of Example 47, the same recording head as that of Example 1 was used, but the conditions for energizing the recording head were an applied voltage of 18.0 V and a pulse width of 2.5.
μsec and a driving frequency of 1 kHz.

[0193]

[Table 3]

Further, the temperature control means 26 controls the tank 21,
The recording medium using the supply path 22 and the recording head 23 was heated to the temperature shown in Table 4.

[0195]

[Table 4]

As a result of recording using the recording media of Examples 33 to 47 as described above, the ejection from the nozzles was successfully performed without clogging in any of the recording media.

On the other hand, the following results were obtained for the bleeding and swelling of the recorded image. (I) In the recording media of Examples 33-37, 40-45, and 47, neither bleeding nor swelling occurred on any of the recording papers (1) to (5). (Ii) Blurring of the recorded image slightly occurred in the recording media of Examples 38 and 46. The bleeding occurred on the recording papers (4) and (5), but there was no practical problem. In the recording papers (1) to (3), bleeding was hardly noticeable. (Iii) The swelling of the recorded image slightly occurred in the recording medium of Example 39. The swell is on the recording paper (1)-
Although it occurred in all of (5), there was no practical problem.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing an example of a recording apparatus used for a recording method of the present invention.

FIG. 2 is a schematic diagram illustrating an example of a recording head used in the recording apparatus illustrated in FIG.

FIG. 3 is a cross-sectional view showing an example of a recording head to which a recording medium has been supplied in order to show the principle of the recording method of the present invention.

FIG. 4 is a graph showing an example of a change in the internal pressure of the foam and a change in the volume of the foam when the foam does not communicate with the outside air.

FIG. 5 is a graph showing an example of a change in the internal pressure of the foam and a change in the volume of the foam when the foam communicates with the outside air.

FIG. 6 is a graph showing an example of a change in the internal pressure of the foam, a change in the volume of the foam, and a rate of a change in the volume of the foam when the foam communicates with the outside air.

FIG. 7 is a perspective view illustrating an example of a method for measuring a volume of a recording medium protruding from an ejection port.

8 is a diagram illustrating an example of a measurement result obtained by the measurement method illustrated in FIG.

FIG. 9 is a cross-sectional view showing another example of a recording head to which a recording medium is supplied in order to show the principle of the recording method of the present invention.

FIG. 10 is a schematic diagram illustrating an example of a recording apparatus that enables observation of a foaming state and a discharge state of a recording medium.

FIG. 11 is a plan view showing an example of a foamed state observed using the apparatus of FIG.

FIG. 12 is a plan view showing another example of a foaming state observed using the apparatus of FIG. 10;

FIG. 13 is a plan view showing another example of the foaming state observed using the apparatus of FIG.

FIG. 14 is a graph showing an example of a melting point and a solidification temperature of a recording medium which is solid at room temperature.

FIG. 15 is a perspective view illustrating an example of a recording apparatus that performs the recording method of the present invention.

FIG. 16 is a cross-sectional view showing an example of a recording head with a tank for performing the recording method of the present invention.

FIG. 17 is a cross-sectional view showing another example of a recording head with a tank for performing the recording method of the present invention.

FIG. 18 is a perspective view illustrating an example of a nozzle shape of a recording head that performs the recording method of the present invention.

FIG. 19 is a block diagram illustrating an example of a facsimile using the recording apparatus of the present invention.

FIG. 20 is a sectional view showing an example of a conventional recording method.

FIG. 21 is a sectional view showing another example of a conventional recording method.

FIG. 22 is a cross-sectional view showing another example of a conventional recording method.

FIG. 23 is a sectional view showing another example of the conventional recording method.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Substrate 2 Heater 3 Ink 4 Top plate 5 Orifice 6 Bubble 7 Small droplet 8 Wall 10 Liquid chamber 11 Ink supply port 14 Wall 15 Nozzle 16, 201 Microscope 17 Strobe 18 Strobe drive circuit 19 Delay circuit 20, 24 Heating means 21 Tank 22 Supply path 23 Recording head 25 Drive circuit 26 Temperature control means 27 Recording paper 80, 81, 82 Foam 100, 101, 102, 103 Recording head with tank 104 Carriage 106, 107 Guide rail 120 Platen 200 Light source

Continuation of the front page (31) Priority claim number Japanese Patent Application No. 3-225363 (32) Priority date August 12, 1991 (1991.12.12) (33) Priority claim country Japan (JP) (56) References JP-A-62-135375 (JP, A) JP-A-61-249768 (JP, A) JP-A-61-185455 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) B41J 2/05 B41J 2/01 B41J 2/015 C09D 11/00-11/02

Claims (16)

(57) [Claims] 1. A recording medium, which is a solid at room temperature, is heated and melted, and thermal energy is further applied in accordance with a recording signal to generate bubbles in the recording medium, and the recording medium is discharged from the discharge port by the bubbles. when recording Te, of the foam
The jet recording method , wherein when the pressure is equal to or lower than the external pressure, the bubbles communicate with the external air. 2. A colorant having a melting point Tm of 40 ° C. or more and 150 or more.
° C. or less, using a normal temperature solid recording medium containing a hot-melt solid substance having a boiling point Tb of 260 ° C. or more and 340 ° C. or less,
An ejection recording method, wherein the recording medium is heated and melted, and thermal energy corresponding to a recording signal is further applied to eject the recording medium from an ejection port to perform recording. 3. A recording medium used in an ejection recording method in which recording is performed by ejecting a recording medium from an ejection port by applying thermal energy, wherein a colorant and a melting point Tm are 40 ° C. or more and 150 ° C. or less. An ordinary temperature solid recording medium comprising a heat-fusible solid substance having a boiling point Tb of 260 ° C. or more and 340 ° C. or less. Claim 3 relationship between melting point Tm and the solidifying temperature Tf of the heat fusible solid material is Tm-Tf ≦ 30 ° C.
The recording medium of the normal temperature solid described. 5. The normal temperature solid recording medium according to claim 4 , wherein the relationship between the melting point Tm and the solidification temperature Tf is Tm−Tf ≧ 7 ° C. Wherein said thermally fusible solid material is a first heat-fusible solid substances, the melting point Tm- solidification temperature Tf ≦ 30 ° C. The fill of claim 3, wherein the containing second thermofusible solid material Room temperature solid recording medium. 7. A method according to claim 1, wherein at least one of said first heat-fusible solid substance and said second heat-fusible solid substance has a melting point T.
The medium-temperature solid recording medium according to claim 6, which satisfies m-solidification temperature Tf ≧ 7 ° C. 8. A recording medium used in an ejection recording method in which bubbles are generated in a recording medium by applying thermal energy, and the bubbles are communicated with outside air to discharge the recording medium from a discharge port. A room-temperature solid recording medium, comprising: an agent; and a heat-fusible solid substance having a relation between a melting point Tm and a solidification temperature Tf of Tm−Tf ≦ 30 ° C. 9. The room temperature solid recording medium according to claim 8 , wherein the relationship between the melting point Tm and the solidification temperature Tf is Tm−Tf ≧ 7 ° C. 10. A recording medium used in an ejection recording method in which bubbles are generated in a recording medium by applying thermal energy, and the bubbles are communicated with outside air to discharge the recording medium from an ejection port. Agent and melting point Tm 36 ° C or higher 1
A first heat-fusible solid material having a boiling point Tb of 150 ° C. or more and 370 ° C. or less at 50 ° C. or less, and a second heat-fusible solid material having a relationship between a melting point Tm and a solidification temperature Tf of Tm−Tf ≦ 30 ° C. And an ordinary temperature solid recording medium comprising: 11. The room-temperature solid recording medium according to claim 10, wherein at least one of the first heat-fusible solid material and the second heat-fusible solid material satisfies a melting point Tm−solidification temperature Tf ≧ 7 ° C. . 12. using ethylene carbonate as the first heat-fusible solid substance, of the second in the molecule as a heat-meltable solid material a substance having two or more hydroxyl groups 8 or less claim 10, wherein Room temperature solid recording medium. 13. The room-temperature solid recording according to claim 10 , wherein ethylene carbonate is used as the first heat-fusible solid substance, and a substance having a hydroxyl value of 300 to 1,000 is used as the second heat-fusible solid substance. Medium. 14. The first heat-fusible solid substance is ethylene carbonate, and the second heat-fusible solid substance is 1.12-dodecanediol, 1.10-decanediol, 1.8-octanediol. The recording medium according to claim 10 , wherein said recording medium is selected from the group consisting of glycerol mono-12-hydroxystearate and 9.10-dihydroxystearic acid methyl ester. 15. A recording head having a heater for generating thermal energy according to a recording signal and a discharge port for discharging a recording medium of a room temperature solid, a tank for storing the recording medium of the room temperature solid, and the recording head. Heating means for melting the recording medium in the tank and in the tank, wherein the recording head and the recording tank are integrally configured.
To the recording head with tank
An ejection recording apparatus , wherein the ink cartridge is replaceable, and the heater is provided near the discharge port to communicate bubbles generated in the recording medium with outside air. 16. A recording head having a heater for generating thermal energy in accordance with a recording signal and a discharge port for discharging a molten normal temperature solid recording medium, a tank containing the normal temperature solid recording medium, and Room temperature solid record
An ink cartridge for replenishing the recording medium; and a heating unit for melting the recording medium in the recording head and the tank. An ejection recording apparatus characterized in that generated bubbles are communicated with outside air.