JP4999056B2 - Nozzle plate for ink jet head, head, ink jet recording apparatus and method using the same, ink for ink jet recording - Google Patents

Description

  The present invention relates to a nozzle plate of an inkjet head, a head, an inkjet recording apparatus / method using them, and an inkjet patterning apparatus / method.

In recent years, demands for print quality, hue, saturation, gloss, and the like have become more severe as the image quality improvement technology of OA printers has improved.
Therefore, the present inventor has proposed to use silicone for the ink repellent layer of the nozzle in taking measures to reduce the surface tension of the ink and increase the wettability to paper to improve the color developability.
As a result, the color development can be improved, but the ink repellent layer made of silicone is scratched or worn due to contact with the paper or the wiper blade by a cleaning mechanism, etc. The problems (e.g. ejection stability, cleaning properties) cannot be sufficiently satisfied.

  The present invention has been made in view of the above situation, and in a nozzle plate having an ink repellent layer using silicone, while maintaining ink repellency, it improves mechanical strength such as hardness, and discharge stability. It is an object of the present invention to provide a highly reliable ink jet recording apparatus and method that ensure functions as a nozzle surface, such as a cleaning property and a cleaning property.

In a nozzle plate having an ink repellent layer formed by curing silicone on the ink ejection surface side of the nozzle member, the weight average molecular weight Mw (Pr) of the silicone before curing and the weight average molecular weight Mw of the toluene extract of the silicone after curing ( When Ex) satisfies the relationship of the following formula (1), it is possible to provide a highly reliable ink jet recording apparatus and method that achieve both ink repellency and mechanical strength of the nozzle plate.
In this case, the silicone curing reaction is a condensation reaction between a silanol group and a hydrolyzable silyl group, and particularly effective when the hydrolyzable silyl group is an alkoxysilyl group or an oximesilyl group.
Further, it is effective when the ink is an ink composition containing a pigment as a coloring material and when the ink is an ink composition containing a fluorosurfactant in the ink. This is particularly effective when the fluorosurfactant has a structure represented by the following general formula (2) or general formula (3). Furthermore, when the resin emulsion is contained in the ink, the ink adherence to the nozzle plate and the residual property are improved, so that the nozzle plate of the present invention is effective.

That is, the said subject is solved by (1)-( 10 ) of this invention.
(1) In the nozzle plate comprising an ink repellent layer formed by curing a silicone resin on the ink ejection surface side of the nozzle member, the curing reaction of the silicone resin is a condensation reaction between a silanol group and a hydrolyzable silyl group. The hydrolyzable silyl group is an alkoxysilyl group or an oxime silyl group, and the weight average molecular weight Mw (Pr) of the silicone resin before curing and the weight average molecular weight Mw (tow of the toluene extract of the silicone resin after curing) Ex) is a nozzle plate of an ink jet head, wherein the following equation (1) is satisfied:

」、
（２）「前記第（１）項に記載のノズル板を使用していることを特徴とするインクジェットヘッド」
（３）「前記第（２）項に記載のヘッドを使用していることを特徴とするインクジェット記録装置」
（４）「インクが色材として顔料を含有したインク組成物を用いることを特徴とする前記第（３）項に記載のインクジェット記録装置」
（５）「インク中にフッ素系界面活性剤を含有するインク組成物を用いることを特徴とする前記第（３）項又は第（４）項に記載のインクジェット記録装置」
（６）「インク中のフッ素系界面活性剤が一般式（２）で示した構造であることを特徴とする前記第（５）項に記載のインクジェット記録装置；

"
( 2 ) "Inkjet head using the nozzle plate according to item ( 1 )"
( 3 ) "Inkjet recording apparatus using the head according to item ( 2 )"
( 4 ) "Inkjet recording apparatus according to item ( 3 ), wherein the ink uses an ink composition containing a pigment as a colorant"
( 5 ) "Inkjet recording apparatus according to item ( 3 ) or ( 4 ), wherein an ink composition containing a fluorosurfactant in the ink is used"
( 6 ) "The inkjet recording apparatus according to item ( 5 ), wherein the fluorine-based surfactant in the ink has a structure represented by the general formula (2);

（式中、ｍ＝０〜１０、ｎ＝０〜４０である。）」
（７）「インク中のフッ素系界面活性剤が一般式（３）で示した構造であることを特徴とする前記第（５）項に記載のインクジェット記録装置；

(Where m = 0 to 10 and n = 0 to 40). "
( 7 ) "The inkjet recording apparatus according to item ( 5 ), wherein the fluorine-containing surfactant in the ink has a structure represented by the general formula (3);

（式中、Ｒｆはフッ素含有基を表わす。ｍ，ｎ及びｐは整数を表わす。）」
（８）「インク中に樹脂エマルジョンを含有するインク組成物を用いることを特徴とする前記第（３）項乃至第（７）項のいずれかに記載のインクジェット記録装置」
（９）「前記第（２）項に記載のヘッドを使用して、振動板を変形させることでインクを吐出させることを特徴とするインクジェット記録方法」
（１０）「前記第（２）項に記載のヘッドを使用して、熱エネルギーでインクを吐出させることを特徴とするインクジェット記録方法。

(In the formula, Rf represents a fluorine-containing group. M, n and p represent integers.)
( 8 ) "The ink jet recording apparatus according to any one of ( 3 ) to ( 7 ), wherein an ink composition containing a resin emulsion in the ink is used"
( 9 ) "Inkjet recording method characterized in that ink is ejected by deforming the diaphragm using the head described in the item ( 2 )"
( 10 ) “An ink jet recording method, wherein the head according to the item ( 2 ) is used to eject ink with thermal energy .

  According to the present invention, it is possible to improve the mechanical strength such as hardness while maintaining the ink repellency of the nozzle plate provided with the ink repellent layer formed by curing silicone, and the silicone curing reaction can be improved. It has been found to be particularly effective in specific cases, can provide a highly reliable inkjet head with excellent cleaning performance and ejection stability, and has excellent reliability with respect to cleaning performance and ejection stability. Inkjet recording devices can be provided, and a reliable inkjet recording method with excellent cleaning performance, ejection stability, etc. can be provided, and is effective when pigments are included in the ink. In addition, conventionally, it has been difficult to maintain ink repellency when a fluorosurfactant is contained in the ink. Improved mechanical durability in terms of maintaining sexual and further, are achieved extremely excellent effect that it is effective when it contains a resin emulsion in the ink.

The nozzle plate used in the present invention includes an ink repellent layer formed by curing silicone on the ink ejection surface side.
Silicone is an organopolysiloxane having a siloxane bond made of Si and O as a basic skeleton and having an organic group in the side chain. As a method for forming a silicone layer on the nozzle surface, a liquid silicone solution or dispersion is used. Examples thereof include a method of forming by spin coating, dipping, spray coating, and the like, and an electrodeposition method. When forming the silicone layer, except for electrodeposition, the nozzle holes and the back of the nozzle plate are masked with photoresist, water-soluble resin, etc., and after the silicone layer is formed, the resist is peeled and removed. An ink repellent layer can be formed. However, in the present invention, the method for forming these silicone resin layers is not limited. The thickness of the silicone layer is preferably about 0.1 to 5.0 μm, and particularly preferably 0.5 to 2.0 μm in consideration of nozzle diameter accuracy and the like.

  In the present invention, the ink repellent layer is used by curing a silicone layer. Silicone curing reaction includes dehydration condensation reaction between silanol groups, condensation reaction between silanol group and hydrolyzable silyl group, reaction by methyl peroxide, organic peroxide of vinyl silyl group, addition reaction between vinyl silyl group and hydroxy silyl group The reaction proceeds at room temperature or by heating. In addition, there is a curing reaction using an acrylic group or epoxy group light (ultraviolet light) reaction, and in the present invention, these curing reactions can be selected according to the use conditions, but a condensation reaction between a silanol group and a hydrolyzable silyl group. Curing by is particularly effective. Examples of the hydrolyzable silyl group include an alkoxysilyl group, an oximesilyl group, an acetoxysilyl group, an aminoxysilyl group, a propenoxysilyl group, and the like. Particularly, an alkoxysilyl group and an oximesilyl group are effective.

  In the present invention, it is necessary that the weight average molecular weight Mw (Pr) of the silicone before the curing reaction and the weight average molecular weight Mw (Ex) of the toluene extract of the silicone after the curing satisfy the relationship of the following formula (1).

Here, the weight average molecular weight Mw is determined in terms of standard polystyrene by GPC (gel permeation chromatograph). Further, the cured toluene extract of silicone is obtained by immersing a silicone layer in toluene and irradiating with ultrasonic waves of 38 kHz and 1 W / cm ² for 30 hours or more, and uncured components are extracted. The amount of toluene used for extraction is approximately 2 ml of toluene with respect to 1 cm ² of the ink repellent layer.
Mw (Ex) / Mw (Pr) is an index representing the degree of crosslinking. If Mw (Ex) / Mw (Pr) is small, it indicates that the degree of crosslinking is high. If it is less than 0.08, the curing reaction proceeds. Although the silicone layer has a sufficient hardness, the ink repellency is slightly lowered. On the other hand, if Mw (Ex) / Mw (Pr) is large, the degree of crosslinking is low. If it is larger than 0.12, the curing reaction is insufficient and sufficient hardness cannot be obtained. In general, a higher degree of cross-linking tends to be preferable, but the present invention has found that there is an optimum range shown in the above formula (1) in balance with ink repellency. If the condition of the above formula (1) is satisfied, ink repellency and hardness can be achieved, and the mechanical durability is improved while maintaining the function as a nozzle surface such as ejection stability and cleaning properties. Is possible. Satisfying the relationship of the above formula (1) can be achieved by adjusting curing conditions such as heating conditions.

The ink jet recording apparatus of the present invention uses an piezoelectric head as a pressure generating means for pressurizing ink in an ink flow path as an ink jet head, and deforms a diaphragm that forms the wall surface of the ink flow path to increase the volume in the ink flow path. A so-called piezo type that discharges ink droplets by changing (refer to Japanese Patent Laid-Open No. 2-51734), or a so-called one that generates bubbles by heating ink with thermal energy in an ink flow path using a heating resistor. Thermal type (see Japanese Patent Application Laid-Open No. 61-59911), a diaphragm that forms the wall surface of an ink flow path and an electrode are arranged opposite to each other, and the diaphragm is generated by an electrostatic force generated between the diaphragm and the electrode. It includes any case such as an electrostatic type (see Japanese Patent Laid-Open No. 6-71882) in which ink drops are ejected by changing the volume in the ink flow path by deformation. That.
In particular, a piezoelectric type that deforms the diaphragm and a thermal type that discharges with thermal energy are effective.

An ink jet recording apparatus used in the present invention will be described with reference to FIG.
The ink jet recording apparatus is mounted on the apparatus main body (101), a paper feed tray (102) for loading paper mounted on the apparatus main body (101), and the apparatus main body (101), and an image is recorded (formed). A paper discharge tray (103) for stocking paper is provided. The upper surface of the upper cover (111) of the apparatus main body (101) is a substantially flat surface, and the front surface (112) of the upper cover of the apparatus main body (101) is inclined obliquely rearward with respect to the upper surface. A paper discharge tray (103) and a paper feed tray (102) protruding forward (front side) are provided below (112). Further, an end of the front surface (112) has an ink cartridge loading section (104) that protrudes forward from the front surface (112) and is lower than the upper cover (111). An operation unit (105) such as operation keys and a display is arranged on the upper surface of the unit (104). The ink cartridge loading section (104) has an openable / closable front cover (115) for attaching and detaching the ink cartridge.

As shown in FIGS. 2 and 3, the main body (101) has a carriage (133) as a guide rod (131) and a stay (132) as guide members horizontally mounted on left and right side plates (not shown). It is slidably held in the scanning direction and moved and scanned in the carriage scanning direction of FIG. 3 by a main scanning motor (not shown).
On the carriage (133), a recording head (134) composed of four inkjet heads that eject ink droplets of yellow, cyan, magenta, and black is arranged with a plurality of ink ejection openings in a direction intersecting the main scanning direction. The ink droplet ejection direction is directed downward.
As a head constituting the recording head (134), a piezoelectric actuator such as a piezoelectric element, a thermal actuator using a phase change caused by film boiling of a liquid using an electrothermal transducer such as a heating resistor, and a metal phase change caused by a temperature change. A shape memory alloy actuator using an electrostatic force, an electrostatic actuator using an electrostatic force, or the like as an energy generating means for discharging ink can be used. The carriage (133) is equipped with a sub tank (135) for each color for supplying ink of each color to the recording head (134). Ink is replenished and supplied from the ink cartridge loaded in the ink cartridge loading section (105) to the sub tank (135) via an ink supply tube (not shown).

  On the other hand, the sheet stacking unit (pressure plate) (141) to the sheet (142) serve as a sheet feeding unit for feeding the sheet (142) stacked on the sheet stacking unit (pressure plate) (141) of the sheet feeding tray (103). ) Are separated from each other by a half-moon roller (sheet feeding roller) (143) and a sheet feeding roller (143), and a separation pad (144) made of a material having a large friction coefficient is provided. ) Is biased toward the paper feed roller (143).

  Then, as a transport unit for transporting the paper (142) fed from the paper feed unit on the lower side of the recording head (134), a transport belt (for electrostatically attracting and transporting the paper (142)) 151), a counter roller (152) for conveying the paper (142) sent from the paper supply unit via the guide (145) between the conveyance belt (151), and a substantially vertical upper part. A conveyance guide (153) for changing the direction of the sheet (142) by approximately 90 ° to follow the conveyance belt (151), and a leading edge biased toward the conveyance belt (151) by the pressing member (154). A pressure roller (155). Further, a charging roller (156) which is a charging unit for charging the surface of the conveying belt (151) is provided.

  Here, the transport belt (151) is an endless belt, and is configured to be looped around the transport roller (157) and the tension roller (158) in the belt transport direction. The transport belt (151) is made of, for example, a surface layer that is a sheet adsorbing surface formed of a pure resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, ETFE pure material, and the same material as the surface layer and is made of carbon. It has a back layer (medium resistance layer, ground layer) that has been subjected to resistance control. In addition, a guide member (161) is disposed on the back side of the conveyance belt (151) so as to correspond to a printing area by the recording head (134). Further, as a paper discharge unit for discharging the paper (142) recorded by the recording head (134), a separation claw (171) for separating the paper (142) from the transport belt (151), and paper discharge A roller (172) and a paper discharge roller (173) are provided, and a paper discharge tray (103) is provided below the paper discharge roller (172).

  A double-sided paper feeding unit (181) is detachably attached to the back surface of the apparatus main body (101). This double-sided paper feeding unit (181) takes in the paper (142) returned by the reverse rotation of the transport belt (151), reverses it, and feeds it again between the counter roller (152) and the transport belt (151). . In addition, a manual paper feeding unit (182) is provided on the upper surface of the double-sided paper feeding unit (181).

In the ink jet recording apparatus configured as described above, the paper (142) is separated and fed one by one from the paper feeding unit, and the paper (142) fed substantially vertically upward is guided by the guide (145) and conveyed. The belt (151) and the counter roller (152) are sandwiched and conveyed, and the leading end is guided by the conveying guide (153) and pressed against the conveying belt (151) by the leading pressure roller (155). 90 ° conveyance direction is changed.
At this time, the conveyance belt (151) is charged by the charging roller (156), and the sheet (142) is electrostatically attracted to the conveyance belt (151) and conveyed. Therefore, by driving the recording head (134) according to the image signal while moving the carriage (133), ink droplets are ejected onto the stopped sheet (142) to record one line, and the sheet ( 142), the next line is recorded after a predetermined amount is conveyed. Upon receiving a recording end signal or a signal that the rear end of the paper (142) has reached the recording area, the recording operation is terminated and the paper (142) is discharged onto the paper discharge tray (103).
When the ink remaining amount near end in the sub tank (135) is detected, a required amount of ink is supplied from the ink cartridge to the sub tank (135).
The ink jet recording apparatus according to the present invention is not limited to the above example, and can be applied to a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, etc. in addition to an ink jet printer.

Next, the ink jet head will be described.
4 is an enlarged view of elements of an ink jet head to which the present invention is applied, and FIG.
This ink-jet head has an ink supply port (not shown) (supplying ink from the front surface direction to the back direction (back surface direction of the paper) in FIG. 4) and a frame (engraved to form a common liquid chamber (12) ( 10), a fluid resistance portion (21), a flow path plate (20) in which a carving to be a pressurized liquid chamber (22) and a communication port (23) communicating with the nozzle (31) are formed, and a nozzle (31) A nozzle plate (30) to be formed, a diaphragm (60) having a convex part (61), a diaphragm part (62) and an ink inlet (63), and an adhesive layer (70) on the diaphragm (60) A laminated piezoelectric element (50) joined and a base (40) fixing the laminated piezoelectric element (50) are provided. The base (40) is made of a barium titanate ceramic, and the laminated piezoelectric elements (50) are arranged in two rows and joined.
The laminated piezoelectric element (50) includes a lead zirconate titanate (PZT) piezoelectric layer (51) having a thickness of 10 to 50 μm / layer and a silver / palladium (AgPd) layer having a thickness of several μm / layer. Electrode layers (52) are alternately stacked. The internal electrode layer (52) is connected to the external electrode (53) at both ends.
The laminated piezoelectric element (50) is divided onto comb teeth by half-cut dicing, and is used as a drive unit (56) and a support unit (57) (non-drive unit) one by one (FIG. 5).
The outer end of one of the two external electrodes (53) (connected to one end of the internal electrode layer (52) in the front or back direction (back side of the paper) in the figure) is divided by half-cut dicing. Further, the length is limited by processing such as notches, and these become a plurality of individual electrodes (54). The other is conductive without being divided by dicing, and becomes a common electrode (55).
An FPC (80) is soldered to the individual electrode (54) of the drive unit. Further, the common electrode (55) is provided with an electrode layer at the end of the laminated piezoelectric element, and is wound around and joined to the Gnd electrode of the FPC (80). A driver IC (not shown) is mounted on the FPC (80), thereby controlling application of drive voltage to the drive unit (56).

The diaphragm (60) is an island-shaped convex portion (island) that joins the thin film diaphragm portion (62) and the laminated piezoelectric element (50) that becomes the drive portion (56) formed in the central portion of the diaphragm portion (62). Part) (61), a thick film part including a beam joined to a support part (not shown), and an opening to be an ink inflow port (63) are formed by stacking two Ni plating films by electroforming. . The diaphragm portion has a thickness of 3 μm and a width of 35 μm (one side).
The island-shaped convex part (61) of the diaphragm (60) and the movable part (56) of the laminated piezoelectric element (50), and the coupling of the diaphragm (60) and the frame (10) are bonded layers including a gap material ( 70) is bonded by patterning.

The flow path plate (20) uses a silicon single crystal substrate, is engraved to be a fluid resistance portion (21), a pressurized liquid chamber (22), and a through-hole to be a communication port (23) at a position relative to the nozzle (31). Was patterned by an etching method.
The portion left by etching becomes the partition wall (24) of the pressurized liquid chamber (22). Further, in this head, a portion for narrowing the etching width was provided, and this was used as the fluid resistance portion (21).

The nozzle plate (30) is formed of a metal material, for example, an Ni plating film by an electroforming method, and has a large number of nozzles (31) which are fine discharge ports for causing ink droplets to fly. The inner shape (inner shape) of the nozzle (31) is formed in a horn shape (may be a substantially cylindrical shape or a substantially frustum shape). The diameter of the nozzle (31) is about 20 to 35 μm as the diameter on the ink droplet outlet side. The nozzle pitch of each row was 150 dpi.
The ink discharge surface (nozzle surface side) of the nozzle plate (30) is provided with an ink repellent layer (90). In the present invention, an ink repellent layer formed by curing silicone is formed, and the details are as described above. This ink repellent layer is not limited to silicone alone, but may be a mixture with other components such as resin and metal.

In the ink jet head configured as described above, a driving waveform (pulse voltage of 10 to 50 V) is applied to the driving unit (56) according to the recording signal, thereby causing displacement in the stacking direction in the driving unit (56). The pressurized liquid chamber (22) is pressurized through the nozzle plate (30) to increase the pressure, and ink droplets are ejected from the nozzle (31).
Thereafter, the ink pressure in the pressurized liquid chamber (22) decreases with the end of ink droplet ejection, and negative pressure is generated in the pressurized liquid chamber (22) due to the inertia of the ink flow and the discharge process of the drive pulse. Then, the process proceeds to the ink filling process. At this time, the ink supplied from the ink tank flows into the common liquid chamber (12), passes from the common liquid chamber (12) through the ink inflow port (63), passes through the fluid resistance portion (21), and reaches the pressurized liquid chamber ( 22) is filled.
The fluid resistance portion (21) has an effect on the attenuation of the residual pressure vibration after the discharge, but becomes a resistance against the refilling due to the surface tension. By appropriately selecting the fluid resistance portion, it is possible to balance the attenuation of the residual pressure and the refill time, and to shorten the time (drive cycle) until the transition to the next ink droplet ejection operation.
The ink jet nozzle plate and the ink jet head of the present invention can be effectively applied to these ink jet recording apparatuses (image forming apparatuses). However, the present invention is not limited to this, and is not limited to such devices as color filter, organic EL manufacturing apparatuses, and other various patterning apparatuses. Is also applicable.

Next, the ink composition used in the present invention will be described.
First, the fluorine-based surfactant is incorporated into the ink to stably disperse the coloring material in the ink and improve the wettability of the ink to the paper, thereby providing high color development and blurring. Fewer images can be obtained. The amount added to the ink is 0.05 to 20% by weight, preferably 0.1 to 10% by weight, but is not particularly limited in the present invention. Examples of fluorosurfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, perfluoroalkylamine oxide compounds. The structure shown by the general formula (1) is particularly preferable from the viewpoint of reliability. Further, commercially available fluorine compounds include Surflon S-111, S-112, S-113, S121, S131, S132, S-141, and 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), MegaFuck F-470, F-1405, F474 (Dainippon Ink Chemical Co., Ltd.), Zonyl FS-300, FSN, FSN-100, FSO (DuPont), Ftop EF-351, 352, 801, 802 (Gemco) etc. are easily available. It can be used in the present invention. Of these, Zonyl FS-300, FSN, FSN-100, and FSO (manufactured by DuPont), which are particularly excellent in reliability and color development, can be suitably used. These commercially available products are often a mixture of several kinds of molecular weights (m and n have a distribution in the general formula (2)), but are recognized without any problem in the effects of the present invention.
These can be used alone or in admixture of two or more kinds, and can also be used in admixture with various surfactants such as anionic, cationic and nonionic which will be described later.

  Examples of the ink component of the present invention include a colorant, a wetting agent, a water-soluble organic solvent, a surfactant, and other additives (antiseptic / antifungal agent, rust preventive agent, water-soluble ultraviolet absorber, water-soluble infrared absorber). , PH adjusting agent, etc.), but are not limited thereto.

First, any known colorant can be used as long as it is publicly known, but the present invention is particularly effective in the case of pigment ink.
As the water-soluble dye, dyes classified in the color index into acid dyes, direct dyes, basic dyes, reactive dyes, and food dyes, preferably those having excellent water resistance and light resistance are used. If these dyes are specifically mentioned, as acid dyes and food dyes,
C. I. Acid Yellow 17, 23, 42, 44, 79, 142
C. I. Acid Red 1, 8, 13, 14, 18, 26, 27, 35, 37, 42, 52, 82, 87, 89, 92, 97, 106, 111, 114, 115, 134, 186, 249, 254 289
C. I. Acid Blue 9, 29, 45, 92, 249
C. I. Acid Black 1, 2, 7, 24, 26, 94
C. I. Food yellow 3, 4
C. I. Food Red 7, 9, 14
C. I. Food black 1, 2
As direct dye,
C. I. Direct yellow 1, 12, 24, 26, 33, 44, 50, 86, 120, 132, 142, 144
C. I. Direct Red 1, 4, 9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225, 227
C. I. Direct orange 26, 29, 62, 102
C. I. Direct blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199, 202
C. I. Direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171
As a basic dye,
C. I. Basic yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 64, 65, 67, 70, 73, 77, 87, 91
C. I. Basic Red 2, 12, 13, 14, 15, 18, 22, 23, 24, 27, 29, 35, 36, 38, 39, 46, 49, 51, 52, 54, 59, 68, 69, 70, 73, 78, 82, 102, 104, 109, 112
C. I. Basic blue 1, 3, 5, 7, 9, 21, 22, 26, 35, 41, 45, 47, 54, 62, 65, 66, 67, 69, 75, 77, 78, 89, 92, 93, 105, 117, 120, 122, 124, 129, 137, 141, 147, 155
C. I. Basic black 2,8
As a reactive dye,
C. I. Reactive Black 3, 4, 7, 11, 12, 17
C. I. Reactive Yellow 1, 5, 11, 13, 14, 20, 21, 22, 25, 40, 47, 51, 55, 65, 67
C. I. Reactive Red 1, 14, 17, 25, 26, 32, 37, 44, 46, 55, 60, 66, 74, 79, 96, 97
C. I. Reactive Blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95
Etc. can be used.

  As pigments, inorganic pigments are manufactured by known methods such as contact method, furnace method, thermal method in addition to titanium oxide and iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow. Carbon black can be used. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments). , Dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (eg basic dye chelates, acid dye chelates), nitro pigments, nitroso pigments, aniline black, etc. . Of these pigments, those having good affinity with the solvent are preferably used. The addition amount of the pigment as the color material in the ink composition is preferably about 0.5 to 25% by weight, more preferably about 2 to 15% by weight. In general, when the pigment concentration is increased, the image density is increased and the image quality is improved. However, the reliability such as fixing property, ejection stability, and clogging tends to be adversely affected.

Specific examples of pigments preferably used in the present invention include black for carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black and channel black, or copper, iron (C.I. And CI pigment black 11), metals such as titanium oxide, and organic pigments such as aniline black (CI pigment black 1).
Further, for color use, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 81, 83, 95, 97, 98, 100, 101, 104, 408 109, 110, 117, 120, 138, 150, 153, C.I. I. Pigment orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 ( Cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219, C.I. I. Pigment violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc.

  In addition, 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 be used. Further, a pigment may be included in a microcapsule so that the pigment can be dispersed in water. This can be paraphrased as polymer fine particles containing pigment particles. In this case, it is not necessary for all pigments blended in the ink to be enclosed or adsorbed in the polymer fine particles, and the pigments may be dispersed in the ink as long as the effects of the present invention are not impaired.

  The particle diameter of the pigment is not particularly limited, but it is preferable in the present invention to use a pigment ink having a particle diameter of 20 to 150 nm in terms of the maximum frequency in terms of the maximum number. When the particle diameter exceeds 150 nm, not only the pigment dispersion stability as the ink composition is deteriorated, but also ejection stability is deteriorated, and image quality such as image density is lowered, which is not preferable. If the particle size is less than 20 nm, the storage stability of the ink composition and the jetting characteristics of the printer are stable. However, dispersing to such a fine particle size is complicated by the dispersion operation and classification operation. In particular, it becomes difficult to produce a recording liquid. In the case of dispersing a pigment using a dispersant, any conventionally known one can be used. Examples thereof include a polymer dispersant and a water-soluble surfactant.

Next, wetting agents and water-soluble organic solvents are used as needed for the purpose of making the ink desired properties, preventing the ink from drying, and improving the dissolution stability of the ink. can do.
Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5 pentanediol, 1,6 hexanediol, glycerin, 1,2,6-hexanetriol, 1, Polyhydric alcohols such as 2,4-butanetriol, 1,2,3-butanetriol, petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetra Polyhydric alcohol alkyl ethers such as ethylene glycol monomethyl ether and propylene glycol monoethyl ether, ethylene glycol mono Polyhydric alcohol aryl ethers such as phenyl ether, ethylene glycol monobenzyl ether, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam Nitrogen-containing heterocyclic compounds such as formamide, amides such as N-methylformamide, N, N-dimethylformamide, amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, and triethylamine, dimethyl sulfoxide, Sulfur-containing compounds such as sulfolane and thiodiethanol, propylene carbonate, ethylene carbonate, γ-butyrolactone and the like can be used.

Next, with regard to the surfactant, this can stabilize the dispersion of the coloring material, adjust the surface tension of the ink to improve the permeability to the recording material, and improve the ink wettability to the head member of the ink jet printer. It can be added as needed for the purpose of improving the ejection stability of the ink by improving it.
In particular, the use of a fluorosurfactant has the effect of lowering the ink surface tension and increasing the wettability to paper and improving the color development, but the ink repellency of the nozzle plate is reduced, so the ejection stability and cleaning performance There was a problem that was inferior. However, if the nozzle plate of the present invention is used, ink repellency can be secured and the effect of the fluorosurfactant can be effectively exhibited. However, the present invention is not limited to fluorine-based surfactants, and is also applicable to ordinary hydrocarbon-based surfactants. When these surfactants are classified from the surface-active functional sites, anions And cationic, nonionic, and amphoteric surfactants.

For example, 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 Ether sulfate ester salt, ether carboxylate, sulfosuccinate, α-sulfo fatty acid ester, fatty acid salt, condensate of higher fatty acid and amino acid, naphthenate, etc. That.
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 polyoxy Propylene glycol, glycerin ester, sorbitan ester, sucrose ester, glycerin ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether, sorbitol ester polyoxyethylene ether, 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 like.
Examples of amphoteric surfactants include imidazoline derivatives such as imidazolinium betaine, dimethylalkyl lauryl betaine, alkyl glycine, and alkyldi (aminoethyl) glycine.
The addition amount of these surfactants in the ink composition is 0.01 wt% to 5.0 wt%, preferably 0.5 wt% to 3 wt%. If it is less than 0.01% by weight, there is no effect of addition, and if it is more than 5.0% by weight, the permeability to the recording medium is unnecessarily high, and there is a problem that the image density is lowered and the back-through occurs. The surfactants can be used alone or in combination of two or more.

As other antiseptic and antifungal agents, 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, sodium sorbate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide Examples of the rust preventive agent include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate, dicyclohexyl ammonium nitrite and the like.
As the pH adjuster, any substance can be used as long as it can adjust the pH to a desired value without adversely affecting the ink to be prepared. Examples include hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, carbonates of alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate, quaternary ammonium hydroxides and diethanolamine. And amines such as triethanolamine, ammonium hydroxide, quaternary phosphonium hydroxide and the like.

Further, in addition to the above ink constituent components, a resin emulsion may be included for the purpose of improving image fixability. In such a case, the ink adhesion to the nozzle plate and the persistence are increased. The board is effective.
Here, the resin emulsion is obtained by dispersing resin fine particles in water as a continuous phase, and may contain a dispersant 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, and more preferably 20 to 300 nm, but it is not particularly limited in the present invention.

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. In particular, an acrylic silicon resin is effective, but in the present invention, it is not limited to the types of these resin emulsions, and is for ensuring reliability when a known one is used. It is also possible to use a resin emulsion.
Commercially available resin emulsions include Microgel E-100, E-2002, E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint), Boncoat 5454 (styrene-acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals), Jonkrill 775 (styrene-acrylic resin emulsion, manufactured by Johnson Polymer), SAE1014 (styrene-acrylic resin emulsion, manufactured by Nippon Zeon), Cybinol SK-200 (acrylic resin emulsion, manufactured by Seiden Chemical), Primal AC-22, AC-61 (acrylic resin emulsion, manufactured by Rohm and Haas), Nanoacryl SBCX-2821, 3589 (acrylic-silicone resin emulsion, manufactured by Toyo Ink), # 3070 (methyl methacrylate polymer) Fat emulsion, manufactured by Mikuni Color), and the like.
The content of the resin fine particles in the ink composition is generally 0.1 to 50% by weight, preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight. However, it is not particularly limited.

  In the present invention, in addition to the state in which the resin fine particles and the color material are separately dispersed in the ink composition, the resin fine particles can be used in a state in which a water-insoluble or hardly soluble color material is contained. . The state in which the color material is contained in the resin fine particles represents either or both of the state in which the color material is sealed and the state in which the color material is adsorbed on the surface of the resin fine particles. Water-insoluble or sparingly soluble means that the coloring material does not dissolve 10 parts by weight or more with respect to 100 parts by weight of water at 20 ° C. When it dissolves, separation or precipitation of the coloring material is visually observed on the surface layer or lower layer of the aqueous solution. It means not being able to. Examples thereof include oil-soluble dyes, disperse dyes, and pigments. In the case where the color material is encapsulated in the resin fine particles, the content of the resin fine particles in the ink composition includes the color material component, so about 2 to 30% by weight is preferable. It does not depend on the content.

  The ink composition of the present invention is prepared by dispersing or dissolving the above-described constituents in a medium, and further stirring and mixing as necessary. Dispersion can be performed with a sand mill, homogenizer, ball mill, paint shaker, ultrasonic disperser, etc., and stirring and mixing can be performed with a stirrer using an ordinary stirring blade, a magnetic stirrer, a high-speed disperser, etc. The present invention does not depend on the manufacturing method.

Example 1
On the surface of the Ni electroforming nozzle, a silicone resin (SR 2411 manufactured by Toray Dow Corning Silicone Co., Ltd., hydrolyzable silyl group is an oxime silyl group) was applied by a spray method to form an about 1.0 μm silicone layer. At this time, the nozzle holes and the back surface of the nozzle plate were masked with a water-soluble resin, and formed by peeling and removing after forming a silicone layer. This was left to stand at room temperature for 2 days to be cured to obtain an ink repellent layer.
The nozzle plate thus prepared (ink repellent layer surface area: 4 cm ² ) was immersed in 8 ml of toluene and irradiated with 38 kHz, 1 W / cm ² ultrasonic waves for 30 hours, and the toluene extract was subjected to GPC (gel permeation). The weight average molecular weight Mw (Ex) was measured by injection into an (Analysis Chromatograph) apparatus. On the other hand, the weight average molecular weight Mw (Pr) of the silicone resin SR2411 was also measured by GPC to obtain Mw (Ex) / Mw (Pr). The results are shown in Table 2.
As the evaluation of the prepared nozzle plate, the initial hardness for the following ink and the receding contact angle after wiping 1000 times with a wiper blade (EPDM rubber hardness 70 °) were measured, and the results are shown in Table 1.
<Ink>
Using a carbon black dispersion made of Cabot (sulfon group addition type self-dispersion type), the mixture was stirred with the following formulation, and then filtered through a 0.8 μm polypropylene filter to prepare an ink.
40 parts by weight of black dispersion (CAB-O-JET 200 (sulfone group addition type, manufactured by Cabot))
8 parts by weight of acrylic silicone resin emulsion (Nanocryl SBCX-2821, manufactured by Toyo Ink)
1,3-butanediol 18 parts by weight Glycerin 9 parts by weight 2-pyrrolidone 2 parts by weight Fluorosurfactant FS-300 (manufactured by Du Pont) 2 parts by weight m = 6-8 in the general formula (2), n = 26 or more Proxel LV (manufactured by Avicia) 0.2 parts by weight Ion-exchanged water 20.8 parts by weight

Example 2
In Example 1, the curing condition of the silicone layer was 60 ° C. for 2 hours.
Example 3
In Example 1, the curing condition of the silicone layer was 100 ° C. for 1 hour.
Example 4
In Example 1, the curing condition of the silicone layer was 150 ° C. for 1 hour.
Example 5
In Example 1, the curing condition of the silicone layer was 200 ° C. for 1 hour.

Example 6
On the surface of the Ni electroforming nozzle, a silicone resin (SR 2410 manufactured by Toray Dow Corning Silicone Co., Ltd., hydrolyzable silyl group is alkoxysilyl group) was applied by a spray method to form a silicone layer of about 1.0 μm. At this time, the nozzle holes and the back surface of the nozzle plate were masked with a water-soluble resin, and formed by peeling and removing after forming a silicone layer. This was left as it was at room temperature for 2 days to be cured at room temperature to obtain an ink repellent layer.
Mw (Ex) / Mw (Pr) was calculated | required for the produced nozzle plate similarly to Example 1, and the pencil hardness and the receding contact angle with respect to the following ink were measured.
<Ink>
As a magenta pigment, C.I. I. Pigment magenta 122 was subjected to low-temperature plasma treatment to prepare a pigment into which a carboxylic acid group was introduced. A dispersion in ion-exchanged water was desalted and concentrated with an ultrafiltration membrane to obtain a magenta pigment dispersion having a pigment concentration of 15%. This was mixed and stirred with the following formulation, and then filtered through a 0.8 μm polypropylene filter to prepare an ink.
Magenta dispersion 40 parts by weight Diethylene glycol 20 parts by weight Glycerin 10 parts by weight Fluorosurfactant 1 part by weight In the general formula (3), n = 4, m = 21, p = 4, and Rf = CF ₂ CF ₃
Proxel LV (manufactured by Avicia) 0.5 parts by weight Ion-exchanged water 28.5 parts by weight

Example 7
In Example 6, the curing condition of the silicone layer was 250 ° C. for 1 hour.

Example 8
A head was manufactured using the nozzle plate manufactured in Example 5 and wiped 1000 times, and mounted on the printer (IPSiO G707 manufactured by Ricoh) shown in FIGS. The ejection stability was evaluated by the following method using the ink prepared in (1).
In a chart in which the printing area in the image area is the total area of the paper, and the printing area of each color is 5%, each ink is printed at 100% duty, the recording density is 360 dpi, and after continuous printing of 500 sheets by one-pass printing. No streaks, white spots, or jet turbulence were observed in the 5% chart solid part. That is, the nozzle surface of the present invention maintained sufficient hardness and ink repellency even after wiping 1000 times and passing 500 sheets.

Comparative Example 1
In Example 1, the curing conditions for the silicone layer were 12 hours at room temperature.
Comparative Example 2
In Example 1, the curing condition of the silicone layer was 300 ° C. for 1 hour.
Comparative Example 3
In Example 6, the curing condition for the silicone layer was 12 hours at room temperature.
Comparative Example 4
In Example 6, the curing condition of the silicone layer was 270 ° C. for 2 hours.

FIG. 3 is a perspective explanatory view of the ink jet recording apparatus according to the present invention as viewed from the front side. It is a schematic block diagram explaining the whole structure of the mechanism part of the recording apparatus shown in FIG. FIG. 3 is an explanatory plan view of a main part of the mechanism unit shown in FIG. 2. It is an element enlarged view of the inkjet head used for this invention. FIG. 5 is an enlarged cross-sectional view of a main part in a direction between channels of the head shown in FIG. 4.

Explanation of symbols

101 apparatus main body 102 paper feed tray 103 paper discharge tray 104 ink cartridge loading unit 105 operation unit 111 upper cover 112 front surface 115 front cover 131 guide rod 132 stay 133 carriage 134 recording head 135 sub tank 141 paper placement unit 142 paper 143 paper supply roller 144 Separator Pad 145 Guide 151 Conveyor Belt 152 Counter Roller 153 Conveyor Guide 154 Pressing Member 155 Tip Pressure Roller 156 Charging Roller 157 Conveying Roller 158 Densation Roller 161 Guide Member 171 Separation Claw 172 Discharge Roller 173 Discharge Roller 181 Double-sided Paper Feed Unit 182 Manual paper feed unit 10 Frame 12 Common liquid chamber 20 Channel plate 21 Fluid resistance unit 22 Pressurized liquid chamber 23 Communication port 24 Partition 30 Nozzle plate 31 Nozzle 40 Base 50 Multilayer piezoelectric element 5 DESCRIPTION OF SYMBOLS 1 Piezoelectric layer 52 Internal electrode layer 53 External electrode 54 Individual electrode 55 Common electrode 56 Drive part (movable part)
57 Supporting part 60 Diaphragm 61 Island-like convex part 62 Diaphragm part 63 Ink inlet 70 Adhesive layer 80 FPC
90 Ink repellent layer

Claims (10)

In the nozzle plate comprising an ink repellent layer formed by curing a silicone resin on the ink ejection surface side of the nozzle member, the curing reaction of the silicone resin is a condensation reaction between a silanol group and a hydrolyzable silyl group, The hydrolyzable silyl group is an alkoxysilyl group or an oxime silyl group, and the weight average molecular weight Mw (Pr) of the silicone resin before curing and the weight average molecular weight Mw (Ex) of the toluene extract of the silicone resin after curing are as follows. (1) A nozzle plate of an ink jet head characterized by the relationship of the formula.

An ink-jet head using the nozzle plate according to claim 1 . An ink jet recording apparatus using the head according to claim 2 . 4. The ink jet recording apparatus according to claim 3 , wherein the ink uses an ink composition containing a pigment as a coloring material. An ink jet recording apparatus according to claim 3 or 4, characterized by using the ink composition containing a fluorine-based surfactant in the ink. 6. The ink jet recording apparatus according to claim 5 , wherein the fluorine-based surfactant in the ink has a structure represented by the general formula (2).

(In the formula, m = 0 to 10 and n = 0 to 40.) 6. The ink jet recording apparatus according to claim 5 , wherein the fluorine-based surfactant in the ink has a structure represented by the general formula (3).

(In the formula, Rf represents a fluorine-containing group. M, n and p represent integers.) The ink-jet recording apparatus according to any one of claims 3 to 7, characterized by using the ink composition containing the resin emulsion in the ink. An ink jet recording method, wherein the head according to claim 2 is used to eject ink by deforming a vibration plate. An ink jet recording method, wherein the head according to claim 2 is used to eject ink with thermal energy.

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