JP2015136894A - Nozzle plate, liquid ejection head and inkjet recording device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nozzle plate that is highly durable and capable of removing remaining ink attached to the surface of the nozzle in a short period of time even when the nozzle surface is rubbed over a long period of time to remove the remaining ink.SOLUTION: The nozzle plate has a layer formed of a compound containing a perfluoro polyether skeleton in its molecule and arranged on the surface of a droplet-ejection side of a nozzle substrate on which nozzle holes are formed to eject droplets. When the surface of the nozzle plate is measured by X-ray Photoelectron Spectroscopy (XPS) and observed, the ratio of an area of peak 1 to the area of peak 2 ranges from 0.35 to 0.45, where the peak 1 represents peaks observed between 534 eV and 540 eV and the peak 2 represents peaks observed between 528 eV and 534 eV among peaks ascribable to oxygen atom observed between 528 eV and 540 eV.

Description

  The present invention relates to a nozzle plate, a liquid discharge head, and an ink jet recording apparatus.

  In recent years, in an ink jet recording apparatus, as an ink jet head, a piezoelectric element is used as pressure generating means for pressurizing ink in an ink flow path, and a diaphragm that forms the wall surface of the ink flow path is deformed to change the volume of the ink flow path. A so-called piezo-type device that discharges ink droplets is known. In addition, a so-called thermal type that generates bubbles by heating ink in the ink flow path using a heating resistor, and a vibration plate and an electrode that form the wall surface of the ink flow path are arranged to face each other. Also known is an electrostatic type that discharges ink droplets by changing the volume of the ink flow path by deforming the diaphragm by an electrostatic force generated between the two and the like.

  On the other hand, in the ink jet recording method, an ink having high permeability is often used for the purpose of improving the image resolution. However, highly penetrating inks have a problem that they are very wet because of low surface tension, and easily contaminate the nozzle surface of an ink jet head (liquid ejection head).

  In Patent Document 1, an attempt is made to stably jet a water-based ink for inkjet recording by controlling the advancing contact angle and the receding contact angle with respect to the nozzle surface of the inkjet head. Further, Patent Document 1 discloses that a water-repellent film using, for example, a polyimide resin is provided on the nozzle surface of the inkjet head.

  Patent Document 2 discloses an ink jet head including a nozzle forming member in which a water repellent layer is formed on the liquid droplet ejection surface side of a nozzle base material. It is disclosed that both layers having a high molecular weight molecule are formed in a state of being exposed on the surface of the nozzle forming member. As a result, attempts have been made to improve both the durability and water repellency of the water repellent layer of the nozzle forming member.

  In view of these, even when a highly permeable ink is used, contamination of the nozzle surface of the ink jet head is suppressed, and further, the durability and water repellency of the water repellent layer on the droplet discharge surface side of the nozzle substrate are improved. Inkjet heads and nozzle plates that can be used have been desired.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention removes residual ink adhering to the surface, so that even when the nozzle surface is rubbed over a long period of time, the residual ink can be removed in a short time, and a highly durable nozzle plate is provided. The purpose is to provide.

  In order to solve the above-mentioned problems, the present invention forms a layer made of a compound containing a perfluoropolyether skeleton in the molecule on the surface of the nozzle substrate on which the nozzle holes for discharging the droplets are formed. Among the peaks derived from O atoms at 528 to 540 eV, which are observed when the surface of the nozzle plate is measured by X-ray photoelectron spectroscopy (XPS), the peak at 528 to 534 eV is peak 2 When the peak of 534 to 540 eV is peak 1, the area of peak 1 / the area of peak 2 is 0.35 to 0.45.

  According to the present invention, since the residual ink attached to the surface is removed, the residual ink can be removed in a short time even when the nozzle surface is rubbed over a long period of time. Can be provided.

It is the schematic (a) and sectional schematic (b) which show an example of the nozzle plate of this invention. It is a figure which shows an example of the nozzle plate manufacturing process of this invention. It is sectional drawing which shows an example of the liquid discharge head of this invention. It is a figure which shows an example of the inkjet recording device of this invention. It is sectional drawing which shows an example of the inkjet recording device of this invention. It is a spectrum figure which shows an example of a XPS measurement result. It is a spectrum figure which shows the other example of a XPS measurement result. It is the schematic which shows an example of a wiper and a nozzle plate. It is the schematic which shows an example of wiping. It is the schematic which shows an example of the measuring method of ink closing time.

  The present invention is a nozzle plate in which a layer made of a compound containing a perfluoropolyether skeleton in a molecule is formed on the surface of a nozzle substrate on which a nozzle hole for discharging droplets is formed, on the droplet discharge side, Among the peaks derived from O atoms at 528 to 540 eV, which are observed when the surface of the nozzle plate is measured by X-ray photoelectron spectroscopy (XPS), the peak at 528 to 534 eV is the peak, and the peak at 534 to 540 eV is the peak If 1, the area of peak 1 / the area of peak 2 is 0.35 to 0.45.

  Hereinafter, a nozzle plate, a liquid discharge head, and an ink jet recording apparatus according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like can be changed within a range that can be conceived by those skilled in the art, and any aspect is possible. As long as the functions and effects of the present invention are exhibited, the scope of the present invention is included.

(Nozzle plate)
FIG. 1 is a view showing an example of a nozzle plate 2 of the present invention. As shown in FIG. 1A, the nozzle plate 2 has a plurality of nozzle holes 1. The inner shape (inner shape) of the nozzle hole 1 is not particularly limited, but can be formed, for example, in a horn shape (may be a substantially cylindrical shape or a substantially frustum shape). The diameter of the nozzle hole 1 is preferably 10 to 100 μm on the ink droplet outlet side. Moreover, the nozzle pitch of each row can be set to 150 dpi, for example.

  As shown in the enlarged sectional view of the nozzle hole 1 in FIG. 1, the shape may have a sag width 10 and a sag height 11. In this case, the sagging width × the sagging height / 2 can be defined as the sagging amount, and it is preferable that the sagging amount is small. In FIG. 1A, the ink repellent layer 4 is omitted.

  As shown in FIG. 1B, the nozzle plate 2 has a perfluoropolyether skeleton in the molecule on the surface of the nozzle substrate 3 on which the nozzle holes 1 for discharging the droplets are formed, on the droplet discharge side. A layer (hereinafter referred to as an ink repellent layer 4) made of a compound containing it is formed. As shown in the drawing, the ink repellent layer 4 is formed on the ink ejection surface side of the nozzle substrate 3.

Stainless steel can be used as the nozzle substrate 3, but is not limited thereto. For example, Al, Bi, Cr, InSn, ITO, Nb, Nb ₂ O ₅ , NiCr, Si, SiO ₂ , Sn, Ta ₂ O ₅ , Ti, W, ZAO (ZnO + Al ₂ O ₃ ), Zn, and these What was formed into a film on the material can be used as the nozzle substrate 3.

The ink repellent layer 4 is a layer made of a compound containing a perfluoropolyether (hereinafter sometimes referred to as PFPE) skeleton in the molecule.
As the perfluoropolyether, known ones can be used, and are not particularly limited. For example, krytoxFSL (manufactured by Dupont), krytoxFSH (manufactured by Dupont), FomblinZ (manufactured by Solvay Solexis), FLUOROLINKS10 (manufactured by Solvay Solexis), FLUOROLINKC10 (manufactured by Solvay Solexis), Moresco Phosphorol A20H (manufactured by Matsumura Oil Research Co., Ltd.), Moresco Phosphorol ADOH (manufactured by Matsumura Oil Research Co., Ltd.) ), Moresco Phosphorol DDOH (manufactured by Matsumura Oil Research Co., Ltd.), Fluorosurf FG5010 (Fluorotechnology), Fluorosurf FG5020 (Fluorotechnology), Fluorosurf FG5060 (Fluorotechnology), Fluorosurf FG5070 (Fluoro) Technology)).

  The average film thickness of the ink repellent layer 4 is preferably 5 to 30 nm. By setting the thickness to 5 nm or more, the surface is sufficiently covered by the ink repellent layer, and it is possible to prevent the generation of defect holes in the film, thereby obtaining suitable ink repellency. By setting the thickness to 30 nm or less, it is avoided that a partially thickened portion falls off due to wiping and becomes a foreign substance, which is used favorably.

<Nozzle plate manufacturing process>
FIG. 2 shows an example of the manufacturing process of the nozzle plate of the present invention. FIG. 2 shows an upstream process, a pretreatment process, an ink-repellent layer forming process, a post-treatment process, and a downstream process. Hereinafter, a specific example will be described. Although the stainless steel nozzle plate has been described as an example of the nozzle base material 3, it is not limited thereto.

-Upstream process-
The upstream process is a process of polishing the surface of the nozzle substrate 3, that is, a discharge surface that is a surface for discharging ink.

  The surface of the stainless steel nozzle plate in which the nozzle hole 1 is formed is applied to the surface of the stainless steel nozzle plate with a polyurethane pad at a pressure of 10 kPa using, for example, an ultra-precise swing type single-side polishing machine (CMP polishing apparatus, manufactured by EBARA). While holding down, a POLIPLA103 (manufactured by FUJIMI) diluted four times with pure water (volume ratio is POLIPLA103: pure water = 1: 3) is used to polish the stainless nozzle plate at 5 rpm. At this time, the surface roughness Ra of the discharge surface is preferably 0.1 μm or less.

The method for measuring the surface roughness Ra of the discharge surface of the nozzle substrate 3 can be obtained, for example, as follows. As a measuring method of the surface roughness Ra, it can be measured according to JIS 0601. For example, it can be measured using a stylus type surface shape measuring device Dektak 150 (manufactured by ULVAC).
In order to adjust the surface roughness Ra, for example, pressure when pressing the plate surface with a polyurethane pad, rotation speed when rotating the polyurethane pad (rpm: number of rotations per minute), flow rate of polishing liquid, polishing It is possible to adjust by changing the time or the like.

-Pretreatment process-
A pre-processing process is a process of the nozzle base material 3 which grind | polished the surface, and is a process of ultrasonically cleaning. In addition to ultrasonic cleaning, wet cleaning such as scrub cleaning, shower cleaning (high pressure spray cleaning, ultrasonic shower cleaning), immersion cleaning (running water cleaning, jet cleaning, bubbling cleaning), and steam cleaning can also be performed.

  The polished stainless steel nozzle plate is subjected to ultrasonic cleaning with an organic solvent in a wet environment so that the polished surface is not dried. The wet environment is preferably 50% or higher for preventing drying.

  As the organic solvent, alcohols such as acetone, ethanol and isopropanol, and hydrofluoroethers such as Novec (manufactured by Sumitomo 3M), Bertrell (manufactured by Dupont) and Galden (manufactured by Solvay Solexis) can be used. .

-Film formation process of ink repellent layer-
The film forming process of the ink repellent layer 4 is as follows. First, the dipping liquid for forming the ink repellent layer 4 is adjusted. Plasma treatment is performed on the surface of the nozzle substrate 3 after the pretreatment, that is, the ejection surface, which is a surface for ejecting ink. In addition to the plasma treatment, it is also possible to perform dry cleaning such as vacuum cleaning (ion beam cleaning) and normal pressure cleaning (UV ozone cleaning, ice scrubber cleaning, laser cleaning).
Thereafter, the adjusted dipping liquid is applied to the nozzle substrate 3 by the dipping method. After being left at room temperature (about 25 degrees), it is heated and subjected to ultrasonic cleaning for removing excess perfluoropolyether. In the ink repellent layer 4, the film thickness of the perfluoropolyether is preferably adjusted to a monomolecular layer level.

As the dip liquid for the ink repellent layer 4, a solution obtained by diluting a perfluoropolyether derivative with a fluorine-based solvent to 1% by weight or less can be used. The perfluoropolyether derivative preferably has a polar group at the terminal. Examples of the polar group herein include —OH, C═O, —COOH, —NH ₂ , —NO ₂ , —NH ₃ ⁺ , —CN, and the like.
Examples of the fluorine-based solvent include hydrofluoroethers such as Novec (manufactured by Sumitomo 3M), Bertrell (manufactured by Dupont) and Galden (manufactured by Solvay Solexis).

  Furthermore, the oxygen plasma treatment is performed on the discharge surface of the stainless steel nozzle plate at 500 W and 0.0012 g / s for 1 minute using, for example, a plasma processing apparatus PDC-510 (manufactured by Yamato Scientific Co., Ltd.).

The ink-repellent layer 4 is formed by, for example, immersing a stainless nozzle plate in a solution, pulling it up at about 3 mm / sec, then naturally drying it for about 10 minutes in a room temperature environment, and further heat-treating at 100 ° C. for 5 hours for fixing. A method is mentioned. The heating temperature and the heating time can be changed according to the purpose, and details will be described later.
Further, the perfluoropolyether excessively attached to the surface of the discharge surface of the stainless steel nozzle plate can be removed by ultrasonic cleaning in the fluorine-based solvent, for example, for 5 minutes.

-Post-treatment process-
The post-treatment process is as follows. In order to protect the surface of the ink repellent layer 4, the discharge surface is covered with a laminate material (lamination is performed), and the back surface of the nozzle substrate 3, that is, the surface opposite to the discharge surface is subjected to plasma treatment.

The nozzle plate obtained as described above was irradiated with oxygen plasma (0.0012 g) with a plasma cleaner PDC-510 (manufactured by Yamato Kagaku Co., Ltd.) with the nozzle surface protected with plastic tape. / S for 1 minute), the ink repellent layer adhering to the liquid chamber surface and the inner wall of the nozzle hole is removed by reverse sputtering.
As the tape, for example, it is preferable to use an Icros tape (manufactured by Mitsui Chemicals), which is a high clean adhesive plus chip tape for semiconductors.

-Downstream process-
A downstream process is a process performed as needed, and a downstream process is a process which adhere | attaches the nozzle base material 3, the member which comprises a liquid chamber, etc., and strengthens adhesive force by heating.

  The nozzle plate obtained in the post-processing step is bonded using a flow path plate and a low-temperature curing type epoxy adhesive or the like in a downstream bonding step. In order to maintain the adhesive state for a long period of time, it is preferable to bond by heating and pressure bonding. The heating temperature is preferably 80 ° C. or less in order to avoid fatigue of the member due to heat, and the heating / crimping time is preferably 2 to 4 hours from the viewpoint of productivity.

  Examples of the adhesive to be used include a low-temperature curable epoxy adhesive. Preferably, as the room temperature curing type, there is Scotch Weld two-component epoxy room temperature curing adhesive DP-460EG (manufactured by Sumitomo 3M). Examples of the type of adhesive that does not cure at normal temperature and starts to cure at 60 to 100 ° C. include AE901 series (manufactured by Ajinomoto Fine Techno Co., Ltd.).

<X-ray photoelectron spectroscopy (XPS) measurement>
In the present invention, the peak area ratio in the case where the surface of the layer comprising a compound containing a perfluoropolyether skeleton in the molecule is subjected to X-ray photoelectron spectroscopy (XPS) measurement (hereinafter sometimes referred to as XPS measurement) is predetermined. It is necessary to meet the requirements. Details will be described below.

  XPS measurement is known as an analysis method in which a sample is irradiated with X-rays in an ultrahigh vacuum and the energy of emitted photoelectrons is measured with an energy analyzer. The electrons in the sample are bound to a certain strength from the nucleus, and the binding energy of the bound electrons can be calculated from the energy of the irradiated X-rays and the kinetic energy of the photoelectrons emitted when the X-rays are applied. Here, since the binding energy of bound electrons is unique to the element, information on the type, abundance, chemical bonding state, etc. of the element can be obtained by analyzing the energy spectrum of the photoelectrons.

Here, FIG. 6 and FIG. 7 show examples of spectra when XPS measurement is performed. 6 and 7 are examples of the results of XPS measurement on the surface of the nozzle plate on which perfluoropolyether is formed. In FIG. 6, a peak appearing at 528 to 540 eV represents a peak derived from an O atom. At this time, among the peaks derived from O atoms, the peak at 528 to 534 eV is referred to as peak 2, and the peak at 534 to 540 eV is referred to as peak 1.
In FIG. 7, the peak appearing at 282 to 296 eV represents a peak derived from the C atom. At this time, among the peaks derived from C atoms, the peak at 282 to 290 eV is referred to as peak 4, and the peak at 290 to 296 eV is referred to as peak 3.

  Next, a method for obtaining a peak area in a spectrum obtained by XPS measurement will be described. In the present invention, the peak area in the spectrum obtained by XPS measurement is obtained by a fully automatic X-ray photoelectron spectrometer K-alpha (manufactured by Thermo Scientific). As an example of Comparative Example 1 in FIG. 6, the peak rising positions 528eV and 538eV are connected by a straight line (baseline), and the area surrounded by the baseline, peak 1, and peak 2 is indicated by a broken line. The peak area is obtained by integration. For 282 to 296 eV, the base line is determined, the area surrounded by the base line, peak 3 and peak 4 is obtained by integration, and the peak area is obtained.

  In the present invention, the area of peak 1 / the area of peak 2 needs to be 0.35 to 0.45. By setting it to 0.35 or more, the nozzle surface is not contaminated by ink, and the ink drawing time can be shortened. By setting it to 0.45 or less, deterioration against wiping can be prevented, and contamination of the nozzle surface with ink can be avoided.

  In the present invention, the area of peak 3 / the area of peak 4 is preferably 2.5 to 3.5. By setting it to 2.5 or more, it is possible to prevent the nozzle surface from being contaminated by ink. By setting the value to 3.5 or less, deterioration against wiping can be prevented, and contamination of the nozzle surface by ink can be avoided. It is.

The control of the peak area is not particularly limited, but in the film forming process of the ink repellent layer 4 described above, there is a method of changing the heating temperature and the heating time after dipping the dip liquid for forming the ink repellent layer. Can be mentioned.
The heating temperature varies depending on the solvent used for forming the ink-repellent layer 4, and therefore cannot be generally specified, but is preferably 80 ° C to 250 ° C, more preferably 100 ° C to 180 ° C. If it is lower than 80 ° C., the solvent remains in the ink repellent layer 4 and sufficient ink repellency may not be obtained. On the other hand, when the temperature is higher than 250 ° C., the perfluoropolyether is decomposed, and sufficient ink repellency may not be obtained.
The heating time can be changed depending on the solvent used for forming the ink-repellent layer 4 and the heating temperature. Although it cannot be generally stated, 0.5 to 1.0 hours are preferable.

(Liquid discharge head)
Next, a liquid discharge head using the nozzle plate of the present invention will be described with reference to FIG. The liquid discharge head shown in FIG. 3 is configured by fixing a flow path unit 31 and an actuator unit 32 together via a frame 33. In the flow path unit 31, the nozzle plate 2, the chamber plate 35, and the vibration plate 36 are stacked, and the pressure chamber 38 is contracted and expanded by expansion and contraction of each piezoelectric vibrator 37 that is a pressure generating unit of the actuator unit 32. It is comprised so that a droplet may be discharged.

A nozzle hole 1 communicating with the pressure chamber 38 is formed in the nozzle plate 2, and a pressure chamber 38 and a fluid resistance 34 are formed in the chamber plate 35.
The vibration plate 36 is provided so as to face the convex portion 42 that contacts the tip of the piezoelectric vibrator 37, the elastically deformable diaphragm portion 43, and each pressure chamber 38. Further, a liquid supply port 45 from a common liquid chamber 41 provided in the frame 33 is formed. A diaphragm portion 44 similar to the above-described diaphragm portion 43 is also formed in the region facing the common liquid chamber 41.

  The flow path unit 31 is obtained by joining the chamber plate 35, the nozzle plate 2 described above, and the vibration plate 36. The chamber plate 35 can be formed of, for example, stainless steel (SUS), but is not limited thereto. The vibration plate 36 can be elastically deformed by the displacement of the piezoelectric vibrator 37 on the rolled metal plate 48, and has a polymer film 49 such as polyimide (PI) or polyphenylene sulfide (PPS) resin having corrosion resistance to ink. Are laminated. Positioning holes made of through holes are formed at important points, and regions where the diaphragm portions 43 and 44 are to be formed are etched, and the convex portions 42 are formed by the rolled metal plate 48.

The nozzle hole 1 is preferably formed with a diameter of 10 to 100 μm on the ink droplet outlet side corresponding to the pressure chamber 38. Further, the ink repellent layer 4 is formed on the nozzle surface (surface in the discharge direction, ie, the discharge surface) in order to ensure water repellency with the liquid (not shown in FIG. 3).
Then, piezoelectric vibrators 37 as pressure generating means are joined to the outer side of the diaphragm 36 (on the side opposite to the pressure chamber 38) corresponding to each pressure chamber 38. The diaphragm 36 and the pressure vibrator 37 constitute a piezoelectric actuator that deforms the diaphragm 43 that is a movable part of the diaphragm 36.

In this liquid discharge head, the piezoelectric vibrator 37 is formed without being divided by groove processing (slit processing). Further, an FPC cable 50 for giving a driving waveform to each piezoelectric vibrator is connected to one end face of the piezoelectric vibrator 37.
Note that the liquid in the pressure chamber 38 may be pressurized using the displacement in the d33 direction as the piezoelectric direction of the piezoelectric vibrator 37, or the liquid in the pressure chamber using the displacement in the d31 direction as the piezoelectric direction of the piezoelectric vibrator 37. It can also be set as the structure which pressurizes. In the present embodiment, a configuration using displacement in the d33 direction is adopted.

  The base member 51 is preferably formed of a metal material. If the material (material) of the base member 51 is a metal, heat storage due to self-heating of the piezoelectric vibrator 37 can be prevented. The piezoelectric vibrator 37 and the base member 51 are bonded and bonded with an adhesive. However, when the number of channels increases, the temperature rises to near 100 ° C. due to self-heating of the piezoelectric vibrator 37 and the bonding strength is significantly reduced. Become. In addition, the temperature inside the head increases due to self-heating, and the liquid temperature rises. However, when the temperature of the liquid rises, the liquid viscosity decreases and the ejection characteristics are greatly affected. Therefore, by forming the base member 51 from a metal material and preventing heat storage due to self-heating of the piezoelectric vibrator 37, it is possible to prevent deterioration in jetting characteristics due to a decrease in bonding strength and a decrease in liquid viscosity.

The FPC cable 50 is equipped with a plurality of driver ICs 52 for applying drive waveforms (electric signals) for driving each channel (corresponding to each pressure chamber 38).
Further, a frame 33 is bonded around the diaphragm 36 with an adhesive. In the frame 33, a common liquid chamber 41 for supplying liquid from the outside to the pressure chamber 38 is formed so as to be disposed on the opposite side of the driver IC 52 and at least the base member 51. The common liquid chamber 41 communicates with the fluid resistance portion 34 and the pressure chamber 38 via the liquid supply port 45 of the vibration plate 36.
In the common liquid chamber 41, a damper chamber 53 is formed by the diaphragm portion 44, and a pressure wave generated in the common liquid chamber 41 by liquid discharge is attenuated to stabilize liquid discharge.

  In the piezoelectric vibrator 37, the piezoelectric layers (piezoelectric material layers) 54, the internal electrodes 55A and the internal electrodes 55B are alternately stacked, and the common side external electrodes 56 and the individual side external electrodes 57 are provided on both end faces. A plurality of piezoelectric vibrators are formed by slitting (grooving) and inserting grooves.

  In the liquid discharge head configured as described above, the drive unit to which the pulse voltage is applied is selectively applied to the drive unit of the piezoelectric vibrator 37, for example, by applying a drive pulse voltage of 20 to 50V. The diaphragm part can be deformed in the nozzle direction. Thereby, the liquid in the pressure chamber 38 is pressurized by the volume / volume change of the pressure chamber 38, and droplets are ejected (jetted) from the nozzle hole 1.

(Image forming device)
Next, an example of an image forming recording apparatus equipped with the liquid ejection head according to the present invention will be described with reference to FIGS. 4 is an explanatory perspective view of the recording apparatus, and FIG. 5 is an explanatory side view of a mechanism portion of the recording apparatus.

  The image forming recording apparatus includes a carriage that is movable in the main scanning direction inside the recording apparatus main body 81, a liquid ejection head that includes the image forming head that implements the present invention mounted on the carriage, and ink that supplies ink to the liquid ejection head. A paper feed cassette (or a paper feed tray) 84 in which a large number of sheets 83 can be stacked from the front side is inserted into and removed from the lower portion of the apparatus main body 81. It can be freely mounted, and the manual feed tray 85 for manually feeding the paper 83 can be opened, and the paper 83 fed from the paper feed cassette 84 or the manual feed tray 85 is taken in and printed. After a required image is recorded by the mechanism unit 82, the image is discharged onto a discharge tray 86 mounted on the rear side.

  The printing mechanism 82 holds the carriage 93 slidably in the main scanning direction (the direction perpendicular to the paper in FIG. 5) with a main guide rod 91 and a sub guide rod 92 which are guide members horizontally mounted on left and right side plates (not shown). The carriage 93 includes a plurality of liquid discharge heads 94 including the liquid discharge heads according to the present invention that discharge ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). The ink discharge ports (nozzles) are arranged in a direction crossing the main scanning direction, and are mounted with the ink droplet discharge direction facing downward. In addition, each ink cartridge 95 for supplying ink of each color to the liquid discharge head 94 is replaceably mounted on the carriage 93.

  The ink cartridge 95 has an air port that communicates with the atmosphere above, a supply port that supplies ink to the liquid ejection head below, and a porous body filled with ink inside, and a capillary tube for the porous body. The ink supplied to the liquid discharge head by the force is maintained at a slight negative pressure. In addition, although the liquid discharge heads 94 for the respective colors are used here as the liquid discharge heads, a single head having nozzles for discharging ink droplets of the respective colors may be used.

  Here, the carriage 93 is slidably fitted to the main guide rod 91 on the rear side (downstream side in the paper conveyance direction), and is slidably mounted on the sub guide rod 92 on the front side (upstream side in the paper conveyance direction). doing. In order to move and scan the carriage 93 in the main scanning direction, a timing belt 70 is stretched between a driving pulley 98 and a driven pulley 99 that are rotationally driven by a main scanning motor 97, and the timing belt 70 is moved to the carriage 93. The carriage 93 is reciprocally driven by forward and reverse rotations of the main scanning motor 97.

  On the other hand, in order to convey the paper 83 set in the paper feed cassette 84 to the lower side of the liquid discharge head 94, the paper feed roller 101 and the friction pad 102 for separating and feeding the paper 83 from the paper feed cassette 84, and the paper 83 A guide member 103 for guiding, a conveyance roller 104 for reversing and conveying the fed paper 83, a conveyance roller 105 pressed against the peripheral surface of the conveyance roller 104, and a feed angle of the sheet 83 from the conveyance roller 104 are defined. A leading end roller 106 is provided. The transport roller 104 is rotationally driven by a sub-scanning motor 107 through a gear train.

  A printing receiving member 109 is provided as a paper guide member that guides the paper 83 sent from the transport roller 104 below the recording head 94 in accordance with the movement range of the carriage 93 in the main scanning direction. A conveyance roller 111 and a spur 112 that are rotationally driven to send the paper 83 in the paper discharge direction are provided on the downstream side of the printing receiving member 109 in the paper conveyance direction, and the paper 83 is further delivered to the paper discharge tray 86. A roller 113 and a spur 114, and guide members 115 and 116 that form a paper discharge path are disposed.

  During recording, the liquid ejection head 94 is driven in accordance with the image signal while moving the carriage 93 to eject ink onto the stopped sheet 83 to record one line, and after the sheet 83 is conveyed by a predetermined amount Record the next line. Upon receiving a recording end signal or a signal that the trailing edge of the paper 83 has reached the recording area, the recording operation is terminated and the paper 83 is discharged.

  Further, a recovery device 117 for recovering defective ejection of the head 94 is disposed at a position outside the recording area on the right end side in the movement direction of the carriage 93. The recovery device 117 includes a cap unit, a suction unit, and a cleaning unit. The carriage 93 is moved to the recovery device 117 side during printing standby and the head 94 is capped by the capping means, and the nozzle portion is kept in a wet state to prevent ejection failure due to ink drying. Further, by ejecting ink not related to recording during recording or the like, the ink viscosity of all the nozzles is made constant, and stable ejection performance is maintained.

  When ejection failure occurs, the nozzle of the head 94 is sealed with a capping unit, air bubbles and the like are sucked out from the nozzle through the tube with a suction unit, and ink or dust adhering to the nozzle surface is removed by the wiping unit. The ejection failure is recovered. Further, the sucked ink is discharged to a waste ink reservoir (not shown) installed at the lower part of the main body and absorbed and held by an ink absorber inside the waste ink reservoir.

(ink)
Next, the ink jet ink used in the present invention will be described.
Constituents of ink include coloring materials, wetting agents, water-soluble organic solvents, surfactants, and other additives (pH adjusters, antiseptic / antifungal agents, rust preventives, water-soluble UV absorbers, water-soluble infrared absorbers) Agent), resin and the like.

-Color material-
As the color material, known pigments and dyes can be appropriately used. For example, inorganic pigments and organic pigments can be used.
Examples of inorganic pigments include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black produced by known methods such as the contact method, furnace method, and thermal method. Etc. can be used.
Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (eg, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye type chelates, acidic dye type chelates), nitro pigments, nitroso pigments, aniline black, and the like can be used.
Among these, those having good affinity with the solvent are preferable.

In addition to the above, a self-dispersing pigment that can be dispersed in water by adding a functional group such as a sulfone group or a carboxyl group to the surface of the pigment (for example, carbon) can also be used. Further, a pigment may be included in a microcapsule so that the pigment can be dispersed in water.
The addition amount of the pigment as the coloring material in the ink is preferably 0.5 to 25% by weight, more preferably 2 to 15% by weight.

-Water-soluble organic solvent-
Examples of water-soluble organic solvents include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, Polyhydric alcohols such as 1,2,4-butanetriol, 1,2,3-butanetriol, and petriol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Polyhydric alcohol alkyl ethers such as tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether; ethylene glycol Polyhydric alcohol aryl ethers such as nophenyl ether and ethylene glycol monobenzyl ether, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, ε- Nitrogen-containing heterocyclic compounds such as caprolactam; Amides such as formamide, N-methylformamide, N, N-dimethylformamide; Amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine and triethylamine; Dimethyl sulfoxide And sulfur-containing compounds such as sulfolane and thiodiethanol; propylene carbonate, ethylene carbonate, γ-butyrolactone, and the like.

-Surfactant-
The surfactant is added as necessary to increase the cleaning property, increase the mixing stability of the cleaning / filling solution, increase the refilling property after cleaning, and the like.
Examples of the surfactant include a fluorine-based surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.

  Fluorosurfactants include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate ester, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkylamine oxide compounds, Examples thereof include polyoxyalkylene ether polymers having a fluoroalkyl ether group in the side chain, sulfate salts thereof, and fluorine-based aliphatic polymer esters.

  Commercially available fluorosurfactants include Surflon S-111, S-112, S-113, S121, S131, S132, S-141, S-145 (manufactured by Asahi Glass Co., Ltd.), Fullrad FC-93. , FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431, FC-4430 (manufactured by Sumitomo 3M), FT-110, 250, 251, 400S (Neos) Zonyl FS-62, FSA, FSE, FSJ, FSP, TBS, UR, FSO, FSO-100, FSN N, FSN-100, FS-300, FSK (manufactured by Dupont), Polyfox PF-136A PF-156A, PF-151N (manufactured by OMNOVA), and the like.

  As an anionic surfactant, alkyl allyl or alkyl naphthalene sulfonate, alkyl phosphate, alkyl sulfate, alkyl sulfonate, alkyl ether sulfate, alkyl sulfosuccinate, alkyl ester sulfate, alkyl benzene sulfonate, Alkyl diphenyl ether disulfonate, alkyl aryl ether phosphate, alkyl aryl ether sulfate, alkyl aryl ether ester sulfate, olefin sulfonate, alkane olefin sulfonate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl Examples include ether sulfate ester salts, ether carboxylates, sulfosuccinates, α-sulfo fatty acid esters, fatty acid salts, condensates of higher fatty acids and amino acids, and naphthenates. It is.

  Examples of the cationic surfactant include alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, quaternary ammonium salts, alkylpyridinium salts, imidazolinium salts, sulfonium salts, phosphonium salts, and the like.

  Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene glycol ester, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid ester, polyoxyethylene poly Oxypropylene glycol, glycerin ester, sorbitan ester, sucrose ester, polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, polyoxyethylene ether of sorbitol ester, fatty acid alkanolamide, amine oxide, polyoxyethylene alkylamine Glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fat Esters, polyoxyethylene sorbitol fatty acid esters, alkyl (poly) Gurikokishido the like.

  Examples of amphoteric surfactants include imidazoline derivatives such as imidazolinium betaine, dimethylalkyllauryl betaine, alkylglycine, and alkyldi (aminoethyl) glycine.

-Other additives-
Examples of other additives include pH adjusters and antiseptic / antifungal agents.
Examples of pH adjusters include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; quaternary ammonium hydroxides. And amines such as diethanolamine and triethanolamine; ammonium hydroxide and quaternary phosphonium hydroxide.
Examples of antiseptic / antifungal agents include 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, sodium sorbate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, and the like.

-Resin-
The resin is added as necessary for the purpose of improving the image fixing property, improving the image quality, and improving the pigment dispersibility. Examples thereof include hydrophilic polymers such as gum arabic, tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, etc. in natural systems; alginic acid, carrageenan, agar, etc. Seaweed polymers; animal polymers such as gelatin, casein, albumin, collagen; microbial polymers such as xanthene gum and dextran; and fibers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose in semisynthetic systems Organic polymers; starch polymers such as sodium starch glycolate and sodium starch phosphate; seaweed polymers such as sodium alginate and propylene glycol alginate, pure synthetic In the system, polyacrylic acid, polymethacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid alkyl ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid Acid copolymer, styrene-acrylic acid-acrylic acid alkyl ester copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene -Acrylic acid copolymer, acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, Vinyl acetate-maleic acid ester copolymer, acetic acid Cycloalkenyl - crotonic acid copolymer, vinyl acetate - acrylic acid copolymers, and salts thereof.
The addition amount of these resins is appropriately selected in consideration of reliability.

  Recently, in place of a resin that is soluble in a solvent, a so-called resin emulsion dispersed as fine particles in a solvent is often used. The resin emulsion is obtained by dispersing resin fine particles in a solvent as a continuous phase, and may contain a dispersing agent such as a surfactant as necessary.

  The content of the resin fine particles as the dispersed phase component (the content of the resin fine particles in the resin emulsion) is generally about 10 to 70% by weight, and the particle size of the resin fine particles is particularly used for an ink jet recording apparatus. In consideration, the average particle size is preferably 10 to 1000 nm, more preferably 20 to 300 nm, but there is no particular limitation.

  Examples of the resin fine particle component of the dispersed phase include acrylic resins, vinyl acetate resins, styrene resins, butadiene resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, acrylic silicon resins, and the like. An acrylic silicon resin is particularly effective, but is not particularly limited, and is for ensuring reliability when a known resin is used, and a commercially available resin emulsion can also be used. .

  The content of the resin fine particles in the ink is generally 0.1 to 50% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, but is particularly limited. It is not a thing.

-Static surface tension-
As the ink used in the present invention, it is preferable to use an ink containing the fluorine-based surfactant and having a static surface tension of 30 × 10 ⁻³ N / m or less. In order to produce an ink having a static surface tension of 30 × 10 ⁻³ N / m or less, the amount of penetrant, for example, 2-ethyl-1,3-hexanediol, and the amount of fluorine-based surfactant added Can be adjusted. If the static surface tension is greater than 30 × 10 ⁻³ N / m, the ink permeability to the recording medium is poor, and a high-quality image may not be obtained.

The surface tension can be determined by, for example, the Zisman method. According to this, when a liquid having a known surface tension is placed on the ink-repellent layer 4, the contact angle θ is measured, and when the surface tension of the liquid is plotted on the x-axis and cos θ is plotted on the y-axis, a straight line descending to the right is obtained. Obtained (referred to as Zisman Plot). For this straight line, the surface tension when y = 1 (θ = 0 °) can be calculated as the critical surface tension γc.
As other methods other than the above, the critical surface tension can be obtained by using the Fowkes method, the Owens and Wendt method, and the Van Oss method.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these.

(Examples 1-3, Comparative Examples 1-3)
The surface of the discharge surface of a stainless steel nozzle plate with a nozzle hole with a diameter of 25 μm on the ink droplet outlet side is coated with a polyurethane pad using a super-precision swinging single-side polishing machine (CMP polishing machine, manufactured by EBARA). Polishing was performed by rotating POLIPLA103 (manufactured by FUJIMI) 4 times with pure water (volume ratio: POLIPLA103: pure water = 1: 3) while rotating the stainless nozzle plate at 50 rpm while holding it at a pressure of 10 kPa. .
At this time, it was confirmed that polishing was performed until the surface roughness Ra of the discharge surface was 0.1 μm or less. The surface roughness Ra was measured according to JIS 0601 using a stylus type surface shape measuring device Dektak 150 (manufactured by ULVAC).

  Next, the discharge surface of the stainless steel nozzle plate was subjected to oxygen plasma treatment at 500 W and 0.0012 g / s for 1 minute using a plasma treatment apparatus PDC-510 manufactured by Yamato Scientific.

Next, as a perfluoropolyether, fluorosurf Surf FG5020 (manufactured by Fluoro Technology) diluted to 0.2% by weight with a fluorine-based solvent (Novec HFE7100, manufactured by Sumitomo 3M) is formed on the discharge surface of the stainless nozzle plate. Filmed.
The film was formed by immersing the plate in a solution and pulling it up at 3 mm / sec. In the heat fixing after film formation, as shown in Table 1 below, by changing the heating temperature from 25 ° C. to 300 ° C. and changing the heating time, the ink repellent layer 4 of perfluoropolyether having different film quality was formed. Obtained. At this time, the film thickness of the ink repellent layer 4 was 12 nm. Furthermore, after film formation, ultrasonic cleaning with a Novec HFE7100 (Sumitomo 3M) solvent was performed for 5 minutes.

The nozzle plate thus obtained was laminated and protected on the nozzle surface with ICROS tape (manufactured by Mitsui Chemicals) and irradiated with oxygen plasma with a plasma cleaner PDC-510 (manufactured by Yamato Kagaku) (0.0012 g). / S for 1 minute), the ink repellent layer 4 adhered to the liquid chamber surface and the inner wall of the nozzle hole 1 was removed by reverse sputtering. Subsequently, heating and pressure bonding were performed at 70 ° C. for 5 hours through the flow path plate and the low-temperature curing type epoxy adhesive.
As the low-temperature curable adhesive, AE901 series (manufactured by Ajinomoto Fine Techno Co., Ltd.), a type of adhesive that does not cure at room temperature and starts curing at 60 to 100 ° C., was used.
The nozzle plates of Examples 1 to 3 and Comparative Examples 1 to 3 were obtained as described above.

(XPS measurement)
The nozzle plate obtained as described above was subjected to XPS measurement using a fully automatic X-ray photoelectron spectrometer K-alpha (manufactured by Thermo Scientific). The obtained spectrum is shown in FIGS. 6 and 7 (Examples 1 and 3, Comparative Examples 1 and 3). From the obtained spectrum, the area surrounded by the baseline, peak 1 and peak 2 was determined, and the peak area ratio was determined. Similarly, the area surrounded by the baseline, peak 3 and peak 4 was determined, and the peak area ratio was determined. For the baseline, only Comparative Example 1 in FIG. 6 is shown. The results are shown in Table 1 below.

(Evaluation of ink closing time)
Next, the ink drawing time of the nozzle plates obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was measured as follows.

  As shown in FIG. 8, an EPDM (ethylene propylene) rubber blade (wiper 201) having a thickness of 1.2 mm and a width of 30 mm is freely bent by 7 mm out of a length of 20 mm, and one end thereof is fixed by a rubber blade fixing jig 202. Fixed.

  Next, as shown in FIG. 9, the nozzle plate 2 was placed in a container containing the ink 210, and the ejection surface of the nozzle plate 2 was immersed in the ink 210. In this state, while the rubber blade is bent while the discharge surface of the nozzle plate 2 interferes with the nozzle plate 2 by 2 mm (/ 7 mm), as shown in (a) to (d) of FIG. One-way wiping was performed 5000 times at a speed of sec.

  Here, “2 mm (/ 7 mm) interference state” means the length of the portion of the rubber blade (wiper 201) that touches the nozzle plate 2 when the length of the flexible portion is 7 mm as shown in FIG. Represents a state of 2 mm.

  Next, the ink drawing time of the nozzle plate 2 after wiping was measured by a measuring method as shown in FIG. As shown in FIG. 10, half of the chip (nozzle plate 2) is immersed in the ink 210 (FIGS. 10A and 10B) and immediately after being pulled up at a speed of 100 mm / sec (t = 0, FIG. 10). From (c)), the time required for the ink to reach 10% of the area at time t = 0 was measured (FIG. 10E).

(ink)
The following inks were used for measuring the ink draw-off time.
A composition having the following formulation was stirred and dissolved at 60 ° C., allowed to cool at room temperature, adjusted with a 10% aqueous solution of lithium hydroxide so that the pH was 9 to 10, and this was adjusted to 0.22 μm of Teflon (registered trademark). ) [Ink 1] was prepared by filtration through a filter. [Ink 1] had a static surface tension of 30 × 10 ⁻³ N / m or less.

-Formulation of ink 1-
C. I. Direct Black 168 3% by weight
2-pyrrolidone 3% by weight
Diethylene glycol 4% by weight
Glycerin 1% by weight
Alkyl ether carboxylate-based surfactant ECTD-3NEX (surfactant manufactured by Nippon Surfactant Kogyo Co., Ltd.) 0.1% by weight
Nonipol 400 (Sanyo Kasei Kogyo surfactant) 0.5% by weight
Sun Eye Bag P-100 (Anti-fouling and anti-mold agent made by Sanai Oil Co., Ltd.) 0.4%
Ion exchange water

  Table 1 below shows the results of determining the ink drawing time for the nozzle plates obtained in Examples 1 to 3 and Comparative Examples 1 to 3. In Table 1, “0 times” indicates the ink withdrawal time when no wiping is performed, and “5000 times” indicates the ink withdrawal time after 5000 times of wiping. In order to function as the ink repellent layer 4, it is desirable that the ink drawing time is 50 seconds or less.

  From the above, it can be seen that there is a case where ink repellency cannot be secured from the stage before wiping with the change in the shape of the peak derived from O (Comparative Example 3). Further, it can be seen that there are cases where ink repellency is lowered by repeating wiping (Comparative Examples 1 and 2), and the ease with which ink repellency is lowered can be judged from the area ratio of the peak of XPS measurement.

Example 4
A liquid discharge head provided with the nozzle plate obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was manufactured.

(Example 5)
The liquid discharge head obtained in Example 4 was mounted on an ink jet printer (IPSIO GX e3300, manufactured by Ricoh Co., Ltd.) to obtain an ink jet recording apparatus. Ink was ejected using the above [Ink 1], but ink ejection was good.

DESCRIPTION OF SYMBOLS 1 Nozzle hole 2 Nozzle plate 3 Nozzle base material 4 Ink-repellent layer 10 Sagging width 11 Sagging height 31 Flow path unit 32 Actuator unit 33 Frame 34 Fluid resistance part 35 Chamber plate 36 Diaphragm 37 Piezoelectric vibrator 38 Pressure chamber 41 Common liquid Chamber 42 Convex part 43 Diaphragm part 44 Diaphragm part 45 Liquid supply port 48 Rolled metal plate 49 Polymer film 50 FPC cable 51 Base member 52 Driver IC
53 Damper Chamber 55A Internal Electrode 55B Internal Electrode 56 Common Side External Electrode 57 Individual Side External Electrode 81 Device Main Body 82 Printing Mechanism 83 Paper 84 Paper Feed Cassette 85 Manual Tray 86 Paper Discharge Tray 91 Main Guide Rod 92 Subordinate Guide Rod 93 Carriage 94 Liquid discharge head 95 Ink cartridge 97 Main scanning motor 98 Drive pulley 99 Driven pulley 101 Paper feed roller 102 Friction pad 103 Guide member 104 Transport roller 105 Transport roller 106 Front roller 107 Sub-scan motor 109 Print receiving member 111 Transport roller 112 Spur 113 Paper discharge roller 114 Spur 115, 116 Guide member 117 Recovery device 201 Wiper 202 Wiper fixing jig 203 Nozzle plate fixing jig 204 Tweezers 210 Ink

JP 2003-277651 A JP 2010-76422 A

Claims (5)

A nozzle plate in which a layer made of a compound containing a perfluoropolyether skeleton in a molecule is formed on the surface of a nozzle substrate on which a nozzle hole for discharging droplets is formed on the droplet discharge side,
Among the peaks derived from O atoms at 528 to 540 eV, which are observed when the surface of the nozzle plate is measured by X-ray photoelectron spectroscopy (XPS), the peak at 528 to 534 eV is the peak, and the peak at 534 to 540 eV is the peak 1 is a nozzle plate, wherein the area of peak 1 / the area of peak 2 is 0.35 to 0.45.   Among the peaks derived from C atoms at 282 to 296 eV, which are observed when the surface of the nozzle plate is measured by X-ray photoelectron spectroscopy (XPS), the peak at 282 to 290 eV is the peak, and the peak at 290 to 296 eV is the peak 3. The nozzle plate according to claim 1, wherein an area of peak 3 / an area of peak 4 is 2.5 to 3.5.   A liquid discharge head comprising the nozzle plate according to claim 1.   An ink jet recording apparatus comprising the liquid discharge head according to claim 3. The ink jet recording apparatus according to claim 4, comprising an ink containing a fluorine-based surfactant and having a static surface tension of 30 × 10 ⁻³ N / m or less.