JPH0911465A - Surface treated ink-jet recording head - Google Patents

Abstract

PURPOSE: To satisfactorily maintain water repellency and abrasion resistance on the face of a ejection port by treating an ink-jet recording head with a surface treatment agent containing fluoroethylene vinyl ether resin and block isocyanate. CONSTITUTION: A treatment agent containing at least fluoroethylene vinyl ether resin and block isocyanate is used as the surface treatment agent of an ink-jet recording head by which the peripheral part of an ink ejection port is applied to surface treatment. Therefore, the ink-jet recording head which is difficult to receive a flaw caused by an extrinsic cause and has excellent ejection stability for long time is easily formed by using the surface treatment agent of one- package liquid that workability is excellent and low temperature hardening is enabled and printability is excellent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording head for ejecting and ejecting a recording liquid, which is generally called ink, as small droplets from a fine port, and recording the ink by adhering the droplets to a recording surface, particularly ink ejection heads. The present invention relates to a surface treatment agent for an inkjet recording head and a surface treatment method for improving the periphery of an outlet.

[0002]

2. Description of the Related Art Generally, it is necessary that the peripheral portion of an ejection port of an ink jet recording head be water-repellent for good ejection stability. In addition, the peripheral portion is always placed in an environment where it is easily scratched by dust, dust, etc. in the air in use, and by a recording material such as paper. For this reason, a process of applying a material having water repellency and a certain degree of abrasion resistance to the peripheral portion is performed.
Conventionally, it is applied. Examples of the water repellent and the method of applying include the following.

[0003] 1. After applying an ultraviolet curable water repellent material, it is cured with ultraviolet light and heat.

[0004] 2. Dissolve the water-repellent organic polymer in the solvent,
After coating, the solvent is dried by heat and brought into close contact.

3. A metal (for example, gold) having water repellency is coated on the peripheral portion by plating.

[0006] 4. Water-repellent particles (for example, Teflon) are dispersed in a nickel plating solution or the like, and the peripheral portion is coated by eutectoid plating.

[0007]

The conventional surface treatment agents and surface treatment methods have the following problems.

The above 1. In general, a material having a high water repellency can be selected by the method (1), but the abrasion resistance is poor.

The above 2. With the method (1), a material having a particularly high water repellency can be selected, but it cannot be said that the abrasion resistance is sufficient and coating is further difficult.

The above 3. Although this method has sufficient abrasion resistance, it cannot select materials with high water repellency.

The above 4. The above method is a comprehensively superior method among the above methods, but the base material of the peripheral portion of the discharge port is limited to one that can be plated.

The inventors also studied the surface treatment agents 5 and 6 consisting of the following main resins until the present invention.

5. The main agent is FEVE (fluoroeth
Yylene vinylether) resin, curing agent is a combination of isocyanate.

6. Special acrylic modified vinylidene fluoride terpolymer However, 5. And 6. Has high water repellency, but 5.
2 liquid type has poor wear resistance. 6. Also has poor abrasion resistance and becomes easier to get wet with ink after being dipped in ink.
The above problems were not solved by any of the conventional techniques.

That is, an object of the present invention is to provide an ink jet recording head having a surface treatment layer which is excellent in water repellency and abrasion resistance and can be easily formed on the ejection port surface.

The present invention provides excellent effects particularly in an ink jet type recording head and a recording apparatus for recording by forming flying droplets by utilizing thermal energy among the ink jet recording systems.

With regard to its typical structure and principle, for example, US Pat. Nos. 4,723,129 and 4,740 are incorporated.
It is preferable to use the basic principle disclosed in the specification of Japanese Patent No. 796. This method can be applied to both the so-called on-demand type and continuous type. In particular, in the case of the on-demand type, liquid (ink)
By applying at least one drive signal corresponding to the recorded information and providing a rapid temperature rise exceeding nucleate boiling to an electrothermal transducer arranged corresponding to the sheet or liquid path in which This is effective because heat energy is generated in the electrothermal transducer, causing film boiling on the heat-acting surface of the recording head, and as a result, air bubbles in the liquid (ink) corresponding one-to-one to this drive signal can be formed. It is. By discharging the liquid (ink) through the discharge opening by the growth and contraction of the bubble, at least one droplet is formed. When the drive signal is formed into a pulse shape, the growth and shrinkage of the bubble are performed immediately and appropriately, so that the ejection of a liquid (ink) having particularly excellent responsiveness can be achieved, which is more preferable.

As the pulse-shaped drive signal, those described in US Pat. Nos. 4,463,359 and 4,345,262 are suitable. If the conditions described in US Pat. No. 4,313,124 of the invention relating to the rate of temperature rise on the heat acting surface are adopted, more excellent recording can be performed.

As the constitution of the recording head, in addition to the combination constitution of the ejection port, the liquid passage, and the electrothermal converter (the linear liquid passage or the right-angled liquid passage) as disclosed in the above-mentioned respective specifications. The present invention also includes configurations using US Pat. No. 4,558,333 and US Pat. No. 4,459,600, which disclose a configuration in which a heat acting portion is arranged in a bending region.

In addition, JP-A-59-123670 discloses a structure in which a common slit is used as a discharge portion of the electrothermal converter for a plurality of electrothermal converters, and a pressure wave of thermal energy is absorbed. The present invention is also effective in a configuration based on Japanese Patent Application Laid-Open No. 59-138461, which discloses a configuration in which an opening corresponds to a discharge portion.

Further, as a full line type recording head having a length corresponding to the maximum recording medium width that can be recorded by the recording apparatus, the length can be increased by combining a plurality of recording heads as disclosed in the above-mentioned specification. The present invention can exert the above-mentioned effects more effectively, although it may have a configuration that satisfies the above requirement or a configuration as one recording head integrally formed.

In addition, by being attached to the apparatus main body, it is possible to electrically connect to the apparatus main body and supply ink from the apparatus main body, which is a replaceable chip type recording head or the recording head itself. The present invention is also effective when a cartridge-type recording head provided with an ink tank is used.

Further, it is preferable to add recovery means for the recording head, preliminary auxiliary means, etc., which are provided as a configuration of the recording apparatus of the present invention, because the effects of the present invention can be further stabilized. If you list these specifically,
Capping means, cleaning means, pressurizing or suction means for the printhead, preheating means using an electrothermal transducer or another heating element or a combination thereof, and a preliminary ejection mode for performing ejection other than recording Is also effective for performing stable recording.

Further, the recording mode of the recording apparatus is not limited to the recording mode of only the mainstream color such as black, but the recording head may be integrally formed or a plurality of combinations may be used. The present invention is also extremely effective for a device provided with at least one of full colors by color mixing.

In the embodiments of the present invention described above, the ink is described as a liquid, but it is an ink that solidifies at room temperature or below and that softens at room temperature, or is a liquid, or the above-mentioned. In the inkjet method, the temperature of the ink itself is generally adjusted within a range of 30 ° C. or higher and 70 ° C. or lower to control the temperature of the ink so that the viscosity of the ink is within a stable ejection range. It may be in a liquid form.

In addition, the temperature rise due to thermal energy is positively prevented by using it as the energy for changing the state of the ink from the solid state to the liquid state, or the ink is solidified in a standing state for the purpose of preventing evaporation of the ink. In some cases, such as ink that is liquefied by being applied with heat energy according to a recording signal and ejected as an ink liquid or that has already started to solidify when it reaches a recording medium. In the present invention, the use of an ink that has the property of liquefying only by heat energy is also applicable. In such a case, the ink is disclosed in JP-A-54-5684.
No. 7 or Japanese Patent Application Laid-Open No. 60-71260, in which the porous sheet is opposed to the electrothermal converter while being held in a liquid or solid state in the concave portions or through holes of the porous sheet. It may be. In the present invention, the most effective one for each of the above-mentioned inks is to execute the above-mentioned film boiling method.

In addition, as a form of the recording apparatus according to the present invention, in addition to the one provided integrally or separately as an image output terminal of information processing equipment such as a word processor or a computer, a copying apparatus combined with a reader or the like, May take the form of a facsimile machine having a transmission / reception function.

[0028]

[Means for Solving the Problems] The means for achieving the object are:
As a surface treatment agent for the ink jet recording head for surface treatment of the peripheral edge of the ink ejection port, a treatment agent containing at least a FEVE resin and a blocked isocyanate is used.

The surface-treating agent of the present invention can be constituted by one liquid, which essentially comprises the above-mentioned two components, and a solvent, a catalyst and a pigment can be added if necessary.

The FEVE resin is an alternating copolymer of fluoroethylene and vinyl ether, and an example of its structural formula is shown below.

[0031]

Embedded image The blocked isocyanate is one that is made inactive at room temperature by reacting isocyanate with an active hydrogen compound.
In the present invention, the isocyanate is used in the form of a polyisocyanate prepolymer which is less volatile at high temperature. Isocyanates that can be used in the present invention include aromatic isocyanates such as TDI (tolylene diisocyanate), MDI (diphenylmethane diisocyanate),
For alicyclic compounds, IPDI (isophorone diisocyanate),
Aliphatic isocyanates include HDI (hexamethylene diisocyanate) and the like. Phenols, oximes, lactams, alcohols and the like can be used as the active hydrogen compound which undergoes an addition reaction with isocyanate.

As the catalyst, tin compounds such as 1,3-diacetoxytetrabutylstannoxane and dibutyltin dilaurate and tertiary amines such as N-methylmorpholine can be used.

As the solvent, a general-purpose solvent can be used, but if used, it is necessary to select a solvent that does not attack the printing material. Examples of organic solvents that can be used include toluene, xylene, hydrocarbon solvents such as xylene, ethyl acetate, ester solvents such as butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ketone solvents such as isophorone, methanol, ethanol,
Typical examples are alcohol solvents such as butanol.

Examples of usable pigments include titanium oxide and alumina.

[0035]

[Operation] 2. The water-repellent organic polymer mentioned as the prior art in the above has a relatively high molecular weight and thus has a good film-forming property.
While the printability is poor, the treating agent containing two components of the FEVE resin and the blocked isocyanate according to the present invention is in an uncrosslinked low molecular weight state at room temperature and thus has excellent printability and can be used as a single liquid because of its workability. Excellent in. After printing, low-temperature heating dissociates the blocked isocyanate to generate an isocyanate group, which reacts with the hydroxy group in the FEVE resin. 5. The two-part type is a room temperature curable type, but the material according to the present invention has a high crosslink density due to thermosetting and forms a film having excellent wear resistance. Further FEV
Since the E resin contains fluorine, it has low surface free energy and is water repellent. Further, since it has a structure in which fluoroethylene and vinyl ether are alternately arranged, the chemically unstable hydrocarbon vinyl ether unit is protected electronically as well as stereochemically, thereby providing ink resistance. Also FEV
Since the E resin has a hydroxy group and a carboxyl group, it has excellent adhesion as a base material.

[0036]

【Example】

 Example 1 As a FEVE resin, Lumiflon LF-200C (Asahi Glass
100 parts, iso as a blocked isocyanate
Desmodur BL4165 which is a cyanate ester
(Manufactured by Bayer) 16.8 parts, 1.3-di as a catalyst
Acetoxy tetrabutyl stannoxane 3.5 × 10E-
4 parts, xylene as a solvent 25 parts, methyl isobutyl ketone
Prepare a surface treatment agent consisting of 75 tons of
Head of BJ cartridge BC-01 of BJ printer
Using the urethane foam around the discharge port of the nozzle
It was applied and cured at 160 ° C. for 20 minutes. Finally the excimer
Use a laser to open the discharge port and use an inkjet nozzle.
completed. Next, the ink tank filled with ink and the above
The ink jet recording head was completed by joining the heads. for
In the FEVE resin, X in the fluoroethylene unit is
F atom, Cl atom or CF_Three The base is vinyl ete
R in le units₁ Through R_Four Is R ₁ , R_Two Is
Alkyl group, R_Three , R_Four Is an alkylene group,
Quisocyanate is an IPDI isocyanurate
The blocking agent used was methyl ethyl ketone oxime.
You.

Example 2 100 parts of Lumiflon LF-200C (manufactured by Asahi Glass Co., Ltd.) as FEVE resin, 16.8 parts of Desmodur AP staple (manufactured by Bayer Co.) which is an isocyanate ester as a blocked isocyanate, and 1,3 as a catalyst. -Diacetoxy tetrabutyl stannoxane 3.5 x 10E-
A surface treating agent composed of 4 parts, 25 parts of xylene as a solvent, and 75 parts of methyl isobutyl ketone was prepared and printed by transfer on the periphery of the nozzle ejection port of the inkjet recording head of Canon BJ printer-BJ880, and the temperature was set to 160 ° C. 2
It was cured for 0 minutes to complete an inkjet recording head.

The FEVE resin used was fluoroethylene unit.
X at the position is F atom, Cl atom or CF_Three In the base
R in the vinyl ether unit₁ Through R_Four Is it
Each R ₁ , R_Two Is an alkyl group, R_Three , R_Four Is an alkylene
Group, the blocked isocyanate is trimethylol
Desmod, a reaction product of 1 mol of lopan and 3 mol of TDI
By reacting 1 mole of Lol with an additional 3 moles of phenol
That is what I got.

Example 3 100 parts of Lumiflon LF-400C (manufactured by Asahi Glass Co., Ltd.) as FEVE resin, 16.8 parts of Millionate AP (manufactured by Hodogaya Chemical Co., Ltd.), which is an isocyanate ester as a block isocyanate, and N-methylmorpholine 3 as a catalyst. A surface treatment agent composed of 5 × 10E-4 parts, 25 parts of xylene as a solvent, and 75 parts of methyl isobutyl ketone was prepared and transferred to the peripheral portion of the ejection port of the nozzle of the inkjet recording head of Canon BJ Printer-BJ880. Printing was performed and curing was performed at 160 ° C. for 20 minutes to complete an inkjet recording head.

The FEVE resin used was fluoroethylene unit.
X at the position is F atom, Cl atom or CF_Three In the base
R in the vinyl ether unit₁ Through R_Four Is it
Each R ₁ , R_Two Is an alkyl group, R_Three , R_Four Is an alkylene
Group and blocked isocyanates are chemically
The same as that used in 2.

Comparative Example 1 Cytop CTL-8 as a perfluorocyclopolymer
07M (manufactured by Asahi Glass Co., Ltd.) is a Canon BJ printer BJ
Urethane foam was applied to the peripheral portion of the ejection opening of the head of the cartridge BC-01, and the coating was dried at 150 ° C. for 1 hour. Finally, the ink jet nozzle was completed by opening the discharge port with an excimer laser. Next, an ink tank filled with ink and the head were joined to complete a BJ cartridge. This is a comparative example in which a resin containing fluorine was used, but it was different from the one defined in the claims, and no block isocyanate was used.

Comparative Example 2 As a special acrylic modified product of vinylidene fluoride terpolymer, Floren C1-25 (manufactured by Japan Synthetic Rubber Co., Ltd.) was transferred and printed on the peripheral portion of the nozzle of the inkjet recording head of Canon BJ printer BJ880. Then, the ink jet recording head was completed by drying at room temperature for 3 days.

This is an example in which similar chemical substances are used, but different from those defined in the claims.

Comparative Example 3 100 parts of Lumiflon LF-200C (manufactured by Asahi Glass Co., Ltd.) as an FEVE resin, 9.3 parts of Millionate T-80 (manufactured by Hodogaya Chemical Co., Ltd.) as an isocyanate, and 3.5 × of dibutyltin dilaurate as a catalyst. 10E-4 parts, xylene 25 parts as solvent, methyl isobutyl ketone 75
A surface treatment agent composed of parts was prepared, printed on the periphery of the ejection opening of the nozzle of the inkjet recording head of Canon BJ printer BJ880, and cured at room temperature for 3 days to complete the inkjet recording head.

This is a comparative example using TDI (tolylene diisocyanate) itself in which the FEVE resin is used but the isocyanate compound is not the blocked isocyanate. Next, a test piece was prepared using the above material and evaluated. The evaluation method is as follows.

Evaluation of abrasion resistance: Pencil hardness was measured by a pencil scratch test for coating film (manufactured by UESHIMA).

Ink resistance evaluation: The following evaluation was performed on the test pieces at the initial stage and after the ink immersion.

1. Contact angle measurement Advancing contact angle θa by contact angle meter (Kyowa Interface Science Co., Ltd.)
And the receding contact angle θR was measured.

2. Ink adhesion test The ink adhesion test was evaluated according to the following criteria.

None: There is almost no ink and only small droplets adhere.

Small: Bead-shaped ink drops adhere.

Medium: Ink adheres to a part of the surface.

Large: Ink adheres to the entire surface.

3. The change in appearance after immersion was visually observed.

The ink is Canon BJ cartridge B.
The ink of C-01 was used.

Ink dipping was evaluated at 60 ° C. after 1, 2 and 3 months.

Table 1 shows the test piece evaluation results.

[0058]

[Table 1] From the above test piece evaluation results, the FEVE resins and blocked isocyanates described in Examples 1 to 3 had a high hardness and a high contact angle, and did not peel off even after immersion. However, the perfluorocyclopolymer shown in Comparative Example 1 had a particularly high contact angle, but peeling occurred after immersion. The special acrylic modified PVDF terpolymer shown in Comparative Example 2 had a decreased contact angle after immersion. The two-component type of the main component FEVE resin and the curing agent isocyanate shown in Comparative Example 3 had low hardness, and peeling occurred after immersion.

Next, in Example 1. The BJ cartridge BC-01 described in 1 above was mounted on a Canon BJ printer BJ-15V and the printing quality was evaluated by continuous printing, but no deterioration in quality was observed. Embodiment 2. FIG. And 3. The head described in 1. was mounted on a Canon BJ printer BJ-880, and the printing quality was evaluated by continuous printing, but no deterioration in quality was observed.

Although the serial type head is produced in the above embodiment, the present invention is also applicable to the full line type head in which a plurality of ejection openings are provided over the entire width of the recording area of the recording medium. Alternatively, the present invention can be applied not only to a single-color head but also to a multi-color ejection port integrally formed. Further, in the above-mentioned embodiment, the example in which the electrothermal converting element is used as the energy generating element has been shown, but the present invention is also effective for an ink jet head having other energy generating elements.

[0061]

As described above, by using the surface treating agent of the present invention which is excellent in workability with one liquid, can be cured at a low temperature, and is excellent in printability as described above, it is difficult to be scratched by an external cause and is stable for a long time. It has become possible to easily form an excellent inkjet recording head.

Claims (5)

[Claims] 1. An inkjet recording head having a peripheral surface of an ink ejection port surface-treated, wherein the inkjet recording head is treated with a treatment agent containing at least a fluoroethylene vinyl ether resin and a blocked isocyanate. Inkjet recording head. 2. The blocked isocyanate is characterized in that the isocyanate is at least one of tolylene isocyanate and isophorone diisocyanate, and the active hydrogen compound is at least one of phenol or methyl ethyl ketone oxime. 1. The inkjet recording head according to 1. 3. The ink jet recording head according to claim 1, wherein the energy generating element of the ink jet recording head is an electrothermal converter for generating heat by applying electric energy to cause the ink to change state and to eject the ink. . 4. The ink jet recording head according to claim 1, wherein the ink jet recording head is a full line type in which a plurality of ejection openings are provided over the entire width of the recording area of the recording medium. 5. The ink jet recording head according to claim 1, wherein the ink jet recording head is integrally formed with ejection ports for multiple colors.