JP2000026575A - Fluorine-containing epoxy resin composition and surface improvement, recording head for ink jet and ink-jet recording device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of easily forming a cured film of desired pattern excellent in adhesion, and provide an ink jet recording head having discharge nozzle excellent in ink repellency. SOLUTION: The above-described discharge nozzle is obtained by applying the resin composition comprising a fluorine-containing aliphatic epoxy resin having one or more perfluoroalkyl groups of 6 to 12 carbons and two or more epoxy groups in the molecule, a cationic polymerization catalyst and a compatibilizer having an epoxy group and a fluoromethyl group, to the nozzle of the ink-jet recording head, and forming a cured film by irradiating the applied nozzle with an active energy ray in the predetermined pattern to afford the ink repellency to the above-mentioned discharge nozzle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polymerizable resin composition capable of water-repellent and ink-repellent treatments in a desired pattern, and more particularly to a method of polymerizing by irradiation of ultraviolet rays to form a coating film in a desired pattern. It relates to possible resin compositions. Also,
The present invention relates to a surface modification method using the composition, an ink jet recording head treated with an ink repellent using the composition, and an ink jet recording apparatus using the same.

[0002]

2. Description of the Related Art In various fields, it is generally known to apply a water-repellent paint to a member requiring water resistance and ink repellency to obtain these properties. Paints are being developed.

[0003] As the water- and oil-repellent paint, fluorine resin and silicone resin paint are most common. That is,
Fluoroolefins and fluorine-based paints having perfluoro groups are extremely stable both thermally and chemically, and have excellent weather resistance, water resistance, chemical resistance, solvent resistance, etc. It has excellent friction and water repellency, and is widely used for various purposes. Silicone resin is excellent in water repellency and oil repellency, but because of its low hardness, acrylic resin, epoxy resin, urethane resin, etc.
In many cases, the composition of the coating material is constituted by combination or modification with another resin system.

On the other hand, in an ink jet (liquid ejection) recording head which discharges liquid as small droplets from a discharge port and adheres to paper or the like to perform recording or image formation, it is necessary to improve recording characteristics. , Smaller droplets, higher drive frequency, and higher number of orifices. Therefore, a surface treatment for facilitating always maintaining the surface of the discharge port in the same surface state is becoming more and more important.

[0005] However, it is difficult to selectively or precisely treat the surface of the ejection port surface using an existing water- and oil-repellent material as described above so that ink does not adhere thereto. The reasons are as follows: (1) In order to have a property like a photoresist, a substance having a photosensitive functional group must be mainly used, but such a compound must have water repellency and ink repellency at the same time. It is not easy to design a molecule in terms of synthetic technology.

[0006] (2) The surface treatment of the ink jet recording head requires several μm so as not to hinder the function of fine nozzles.
It is necessary to have a very thin film thickness of less than m.
This is because it is difficult to control the existing paint to such a film thickness.

When the surface treatment is achieved with an existing fluorine-based material, it is necessary to design the coating film structure so that the surface properties can be maintained for a long time. However, most water- and oil-repellent materials have low coating hardness and poor friction durability, and when contamination occurs, the water- and oil-repellency decreases and it is often difficult to recover. Outlet surface treatment materials are not always satisfactory.

[0008] At present, it is desired that the ink ejection port used in the ink jet recording system in which the ink is jetted into small liquid droplets to perform recording has the following performance.

That is, (1) the ink remaining on the ink column that has been turned into droplets is promptly re-stored in the discharge port. (2) The ink droplets adhered to the surface are easily swept out by the cleaning operation. 3) The ejection surface of the recording head is excellent in abrasion resistance during cleaning operation and paper transport. (4) In repeated droplet formation and ink refill, a meniscus is formed at the ejection port surface position. (5) Meniscus method (6) The ink has a sufficient interfacial tension, that is, a contact angle, that can form a meniscus even when the ink has a low surface tension or a low negative pressure state. (7) Ink recording liquids are often adjusted to a basic pH of 7 to 11 for dissolution stability,
Use structural materials with excellent alkali resistance and hydrolysis properties of the members.

The reason why these required performances are required is that, in an ink jet recording head, if a recording liquid such as ink adheres to the periphery of the ejection port, the ejection (flying) of the droplet ejected from the ejection port. This is because it is directly related to the printing performance in which deviation occurs in the direction and printing with high precision cannot be performed.

The prior art relating to the present invention includes a lacquer type fluororesin coating, a fluorine type ultraviolet curing type coating, a thermosetting type fluororesin coating, a fluorine type silane coupling agent, and an epoxy resin composition in which fluororesin particles are dispersed. There is a document which discloses that a resin thin film is polymerized from an air layer to form a film.

For example, JP-A-2-39944 discloses that an ink-repellent treatment is performed using a polymer having a fluoroacetyl group and a silazane group.

However, with these coating materials, the durability of the water-repellent coating film may not always be compatible. JP-A-3-7781 discloses an ink-repellent treating agent using glycidyl ether derived from a fluorine-based diol. Since the fluorine-based epoxy resin disclosed here is used after being cured, the durability of the coating film is good, but the ink repellency is not sufficiently satisfactory.

Japanese Patent Application Laid-Open No. 6-328698 discloses a method and a material for forming a hole by an excimer laser which is a collapsible active energy ray. The method disclosed herein can achieve excellent processing accuracy, and thus is suitable for manufacturing an inkjet recording head suitable for this. However, the ink repellent ink using a photolithography method for performing more precise processing is useful. It is difficult to apply to processing.

[0015]

As described above, when the conventional materials and methods are employed, a sufficiently satisfactory water-repellent and ink-repellent surface treatment which requires precision and is durable can be obtained. The fact is that there is no room for improvement and there is room for improvement.

An object of the present invention is to provide a water-repellent resin composition having the above-mentioned properties as a coating film.

Another object of the present invention is to provide a water-repellent agent or a water-repellent agent to be applied to a solution or a substance containing a component that impairs the film-forming property or adhesion of a water-repellent agent, such as a polar organic solvent, or to a place where there is a chance of contact with a substance. It is an object of the present invention to provide a fluorine-containing epoxy resin composition suitable as a water-based paint, and to provide an ink jet recording head provided with good ink repellency by using the composition and an ink jet recording apparatus using the head.

[0018]

A first aspect of the resin composition of the present invention is a fluorine-containing resin having at least one perfluoroalkyl group having 6 to 12 carbon atoms and at least two epoxy groups in one molecule. A fluorine-containing epoxy resin composition comprising at least an aliphatic epoxy resin and a cationic polymerization catalyst. In the present invention, the “perfluoroalkyl group” means a group in which all hydrogens of an alkyl group have been substituted with fluorine.

The fluorinated aliphatic epoxy resin used in the present invention is represented by the following general formula (A-1) or (A-
At least one of the compounds represented by 2) is preferably used.

[0020]

[Outside 5] R ₁ and R ₂ are aliphatic atomic groups.

The second embodiment of the resin composition of the present invention comprises a main chain containing an alicyclic hydrocarbon group having at least one perfluoroalkyl group having 6 to 12 carbon atoms and at least two epoxy groups in a side chain. A fluorinated epoxy resin composition characterized by containing at least a fluorinated polyether resin contained in the above and a cationic polymerization catalyst.

The fluorinated polyether resin according to the second embodiment of the resin composition of the present invention has a general formula (D-1) (D-
The epoxy structural unit represented by 2) and the general formula (D-
3) A polymer containing a perfluoro structural unit represented by (D-4) is preferably used.

[0023]

[Outside 6] However, the total number of the structural units is 3 to 28.

The fluorine-containing epoxy resin composition of the present invention may further contain, if necessary, at least one compound represented by the following formula (C-1) or (C-2) as a compatibilizer. be able to.

[0025]

[Outside 7]

[0026] Still another object of the present invention is to provide a fluorinated epoxy resin composition of the present invention which is applied to a substrate and dried.
A second step of irradiating the active energy ray in a pattern through a mask, a third step of dissolving and removing the non-irradiated part of the active energy ray with a liquid capable of dissolving the composition, if necessary. It is an object of the present invention to provide a surface treatment method characterized by selectively performing a surface treatment on a substrate in the order of a fourth step of performing post-curing.

[0027] Still another object of the present invention is to provide a first method comprising applying the above-mentioned fluorine-containing epoxy resin composition of the present invention to a substrate and drying the composition.
The second step of polymerizing and curing the entire surface of the composition by irradiation with heat or active energy rays; and selectively removing the cured composition by selectively irradiating collapsible active energy rays. It is an object of the present invention to provide a surface treatment method characterized by selectively performing a surface treatment on a substrate in the order of a third step to be performed and a fourth step of performing post-curing as necessary.

Still another object of the present invention is to provide an ink jet recording head having a discharge port for discharging a recording liquid, wherein at least the discharge port opening has a cured film made of the above-mentioned fluorine-containing epoxy resin composition of the present invention. It is an object of the present invention to provide an ink jet recording head characterized by being coated, and an ink jet recording apparatus having the ink jet recording head.

Since the resin composition of the present invention is an epoxy resin, it can provide a cured product which has excellent adhesion to various members, can be cured even at a relatively low temperature, and has excellent physical properties as a structure. Further, by containing an epoxy compound having a perfluoro group at the terminal, the resistance to a water-soluble organic solvent, particularly a polar organic solvent, is greatly improved.
And the compatibility of the components is given by the action of the compatibilizer, and the range of the material constitution can be widened.

The fluorinated epoxy resin composition of the present invention comprises:
It is useful as a material applied to a solution containing a component that impairs the adhesion of a water repellent, such as a polar organic solvent, or a place where there is a chance of contact with a substance. The water-repellent agent or water-repellent paint used for such a portion is particularly suitable for water-repellent and ink-repellent treatment of the ejection port surface of the inkjet recording head.

In the ink jet recording apparatus of the present invention, the selective surface modification utilizing photopolymerizability is used to achieve excellent processing accuracy, and the cured film is formed using a specific material. It has a water-repellent or ink-repellent portion having excellent strength.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The fluorinated aliphatic epoxy resin according to the first aspect of the present invention has one or more perfluoroalkyl groups and two or more epoxy groups in one minute, and the epoxy groups react with each other. Also, since the perfluoroalkyl group is located relatively outside the molecule, the surface of the resin maintains a high density of fluorine atoms. It is thought that this makes it possible to form a layer exhibiting water repellency, oil repellency and ink repellency on the surface while the inside is a hard resin layer.

In the present invention, as the above-mentioned fluorinated aliphatic epoxy resin, at least one of the compounds represented by the following formula (A-1) or (A-2) is preferably used.

[0035]

[Outside 8]

Specific examples of the compound represented by the general formula (A-1) include the following compounds.

[0037]

[Outside 9]

The above compound can be obtained by reacting epichlorohydrin with a perfluoroalkyl compound having a hydroxyl group at a terminal.

Further, specific examples of the compound represented by the general formula (A-2) include the following compounds.

[0040]

[Outside 10]

The fluorinated polyether resin used in the fluorinated epoxy resin composition of the second aspect of the present invention has one or more perfluoroalkyl groups and two or more epoxy groups in a side chain, Even if the epoxy group reacts, the surface of the resin maintains a high density of fluorine atoms due to the perfluoroalkyl group relatively outside the molecule. It is thought that this makes it possible to form a layer exhibiting water repellency, oil repellency and ink repellency on the surface while the inside is a hard resin layer.

In the present invention, the fluorinated polyether resin includes an epoxy structural unit (D-1) (D
-2) and perfluoro structural unit (D-3-1) to
A polymer containing (D-4-2) and having a total number of units of from 3 to 28 is preferably used. Here, the weight ratio between the epoxy structure unit and the perfluoro structure unit is as follows: epoxy structure unit: perfluoro structure unit = 30: 70-
80:20 (parts by weight).

[0043]

[Outside 11]

[0044]

[Outside 12]

Specifically, for example, P1 to P9 shown in Table 1
And the like.

[0046]

[Table 1]

The unit structures may be introduced randomly, or the same units may be introduced in a chain.

The epoxy resin composition of the present invention contains a cationic polymerization catalyst (polymerization initiator) as a catalyst for curing the same. The compound used for such purpose is selected from the substances known as curing agents for epoxy resins. Since the composition of the present invention is an epoxy resin composition, it is possible to add aromatic and aliphatic amines and acid anhydrides and polymerize by heating and curing. However, in the present invention, the surface treatment is designed so that the reactivity to the onium salt of the Lewis acid activated by the active energy ray that enables low-temperature curing is increased, and the surface treatment is selectively performed by photolithography. Therefore, it is suitable for performing surface modification on a substrate that is difficult to maintain at a high temperature. As the cationic polymerization catalyst used in the present invention, bis (4-tert-
Butylphenyl) iodonium salt, and “Optoma-SP-150” and “Optoma-SP1” represented by the following structural formulas.
70 "(made by Asahi Denka Kogyo KK) or the like.

[0049]

[Outside 13]

Further, "Irgacure 261" (manufactured by Ciba Specialty Co.) represented by the following structural formula can be used.

[0051]

[Outside 14]

The fluorine-containing epoxy resin composition of the present invention may further contain, if necessary, at least one compound represented by the following formula (C-1) or (C-2) as a compatibilizer. be able to.

[0053]

[Outside 15]

Specific examples of the compatibilizer include compounds represented by the following structural formulas.

[0055]

[Outside 16]

Although the compatibilizer has a fluorine atom, it mainly has a fluoromethyl group, and has a short chain length, so that its surface energy lowering effect as a molecule is small,
The ink repellency is not great. However, it is effective to increase the compatibility between the fluorinated aliphatic epoxy resin or fluorinated polyether resin and the cationic polymerization catalyst. That is, in the present invention, when the compatibilizer is used in combination, the onium salt of the Lewis acid as the cationic polymerization catalyst has a high polarity, so that the compatibility with the fluorinated aliphatic epoxy resin or fluorinated polyether resin to be used. This is a case where it is necessary to overcome practical difficulties such as poor performance and difficulty in obtaining leveling properties during coating.

The epoxy resin composition of the present invention is basically classified into the following two embodiments. (1) A resin containing A: a fluorinated aliphatic epoxy resin, B: a cationic polymerization catalyst, and if necessary, C: a compatibilizer. (2) D: Fluorine-containing polyether resin B: Cationic polymerization catalyst, and if necessary, C: Compatibilizer.

In the case of the composition (1), these A, B,
The preferred compounding ratio of each component of C in the composition is as follows.

Component B is based on 100 parts by weight of the total amount of the epoxy resin component (component A when component C is not used and component A and component C when component C is used in combination).
It is in the range of 0.1 to 10 parts by weight. The range of the ratio is the thickness of the layer, the precision of the required pattern, the degree of crosslinking of the polymerized coating film, the development stability when performing the development processing,
In the case where only the curing treatment is performed, it is determined from factors such as the reaction speed. Taking such factors into account, the usual amount of the cationic polymerization catalyst used is 10% of the total amount of the epoxy resin component.
0.1 to 7 parts by weight, more preferably 0.3 to 5 parts by weight, based on 0 parts by weight.

When component C, which is a compatibilizer, is used in combination, component A: component C = 100: 10 to 100: 60.
(Weight ratio).

In the case of the composition (2), the preferred compounding ratio of each of the components D, B and C in the composition is as follows.

Component B is based on 100 parts by weight of the total amount of the epoxy resin component (component D when component C is not used and component D and component C when component C is used in combination).
It is in the range of 0.1 to 10 parts by weight. The range of the ratio is the thickness of the layer, the precision of the required pattern, the degree of crosslinking of the polymerized coating film, the development stability when performing the development processing,
When only the curing treatment is performed, it is determined from the requirements such as the reaction speed. Taking such factors into account, the usual amount of the cationic polymerization catalyst used is the total amount of the epoxy resin component of 1
The amount is 0.1 to 7 parts by weight, more preferably 0.3 to 5 parts by weight, based on 00 parts by weight.

When component C which is a compatibilizer is used in combination, component D: component C = 100: 10 to 100: 100
(Weight ratio). That is, component A must be at least 50% by weight of the epoxy resin component.

Examples of the composition of the composition of the present invention are shown below. Hereinafter, the ratio indicates the weight ratio of the solid content. (Composition example 1); A-1-1: B-2 = 99: 1 (composition example 2); A-1-2: B-2 = 96: 4 (composition example 3); A-1 -2: B-1 = 95: 5 (composition example 4); A-2-1: B-2 = 96.5: 3.
5 (composition example 5); A-2-1: B-3 = 95: 5 (composition example 6); A-1-3: B-2: C-2-1 = 6
7: 3: 30 (composition example 7); A-1-3: B-1: C-1-1 = 6
4: 1: 35 (composition example 8); A-2-2: B-1: C-1-1 = 6
2: 2: 36 (composition example 9); A-2-2: B-3: C-2-1 = 7
0: 3: 27 (composition example 10) P1: B-2 = 98: 2 (composition example 11) P2: B-2 = 97: 3 (composition example 12) P3: B-1 = 96: 4 (Composition Example 13) P4: B-3 = 95: 5 (Composition Example 14) P6: B-2: C-1 (p = 0) = 6
5: 4: 35 (Composition Example 15) P7: B-2: C-1 (p = 0) = 7
0: 3: 30 (Composition Example 16) P8: B-1: C-2 (q = 1) = 6
4: 1: 35 (composition example 17) P9: B-1: C-2 (q = 2) = 5
0: 2: 48 (Composition Example 18) P10: B-3: C-2 (q = 0) =
50: 3: 47 (Composition Example 19) P10: B-3: C-2-2 = 50:
3:47

Other polymers can be added to the fluorine-containing epoxy resin composition of the present invention as needed. For example, a polymer that functions as a binder can be used because it enhances the applicability of the composition of the present invention and also improves the workability as a dry coating film that enhances the drying property after evaporation of the solvent. Such combined use of a binder substance is preferable when the composition of the present invention is exposed in a pattern to obtain a desired pattern.

Examples of the binder polymer that can be added to the fluorine-containing epoxy resin composition of the present invention include an alicyclic epoxy resin oligomer and an acrylic copolymer obtained by copolymerizing an acrylic monomer having no fluorine atom group but having an epoxy group in a side chain. Resin, vinyl polymer obtained by polymerizing a vinyl monomer having an alicyclic hydrocarbon group having an epoxy group in a side chain, polyether polymer having an alicyclic hydrocarbon group having an epoxy group in a side chain (for example, Daicel Chemical Industries, Ltd. "EHP
E3150 ”) is most suitable as an epoxy polymer that can itself participate in a crosslinking reaction. When a polymer having no such epoxy group is used, the polymer is selected for the purpose of adjusting physical properties according to the application to which the polymer is applied. Examples of such a substance include “PK” manufactured by Union Carbide, which is a polymer of a bisphenol-type epoxy resin.
General-purpose coating polymer compounds such as “HC” and “PKHJ”, ethylene / vinyl acetate copolymer, phenol resin, polycarbonate resin, polyester resin, polyamide resin, and soluble polyimide resin can be used.

In the composition of the present invention, when such other polymer is used in combination, component A and component C are used.
Weight ratio of component A: component C = 100: 10 to 10
0:60 (weight ratio). The weight ratio of component D to component C is as follows: component A: component C = 100: 10 to 100: 100
(Weight ratio). Component B is contained in an amount of 0.1 to 10 in the total amount (100 parts by weight) of the composition containing the binder polymer.
It is contained in a ratio of parts by weight.

A specific method for using the composition in the present invention will be exemplified. When performing active energy ray curing, as described above, a cationic photopolymerization catalyst that releases a Lewis acid by light is used as a catalyst. In the case of heat curing, a Lewis acid such as a boron trifluoride amine catalyst may be added for use.

<Coating Film Forming Method> The fluorinated epoxy resin composition of the present invention is used in a state of being dissolved in an organic solvent such as an aromatic, aliphatic hydrocarbon, ester, ether or fluorine solvent. Can be When the coating thickness is as small as several μm, a normal precision coating device such as a roll coater, a spin coater, and a spray coater can be used.

A first method of performing a surface treatment in a pattern is a first step in which the fluorine-containing epoxy resin composition of the present invention is applied to a substrate (object to be treated) and dried. A second step of selectively curing the composition by irradiating rays in a pattern, and a third step of dissolving and removing the non-irradiated portion of the active energy ray in the second step by a developing treatment using a developer. Are sequentially performed. The basic steps are the same as in photolithography, but it is necessary to select a solvent suitable for the resin composition as a developer. As the developing solution, aromatic hydrocarbons, ketones, esters, glycol ethers, and the like, and a mixture thereof are used. In order to complete the reaction of the resin composition, it is desirable to further perform heating and irradiation with active energy rays (fourth step) after the development.

A second method of performing a surface treatment in a pattern is a first step of applying the fluorinated epoxy resin composition of the present invention to a substrate and drying the same, and irradiating the entire surface with heat or active energy rays for promoting polymerization. And a third step of irradiating collapsible active energy rays so as to selectively remove a desired portion of the cured portion.

In order to complete the reaction also in the second method, it is desirable to perform heat treatment and irradiation with a polymerizable active energy ray (fourth step) in any stage.

As the active energy ray for promoting the polymerization, an ultraviolet ray source rich in light having a wavelength of 250 to 480 nm is used. Light having a wavelength of 210 nm or less, an excimer laser, or the like is used as the collapsible active energy ray.

As described above, the fluorinated epoxy resin composition of the present invention can be applied to a solution containing a component which impairs the adhesion of a water repellent such as a polar organic solvent, or a water repellent applied to a place where there is a chance of contact with a substance. Agent or water-repellent paint, as well as water-repellent, ink-repellent,
Processing can be suitably performed.

According to the surface modification method of the present invention, water-repellent and oil-repellent treatments with excellent adhesion to the substrate and surface hardness can be performed, so that modification with excellent durability can be performed.

As an application in an ink jet recording head, by treating the surface of the discharge port with the composition of the present invention, a strong release of ink does not occur and a surface having good releasability which can be easily wiped off by a cleaning treatment. Is formed. Many of the cleaning mechanisms mounted on the ink jet recording head include wiping with a rubber blade, suction with a pump, and performing idle discharge at a position outside the recording paper. But in either of these ways,
When the ink column pulled out by the ejection pressure becomes a droplet, not all the ink becomes a droplet, so that it is not possible to completely eliminate the extra small droplets of the ink from adhering around the ejection port. It is. Therefore, if these drops spontaneously, are re-sucked into the ejection openings, or are easily eliminated, the effect on ink ejection is eliminated.

The fluorine-containing epoxy resin composition of the present invention comprises
It can be cured even at a relatively low temperature to provide a cured product having excellent water and oil repellency, adhesion, chemical resistance and friction resistance.

FIGS. 1 and 2 show a main part of an example of the structure of an ink jet recording head to which the fluorine-containing epoxy resin composition of the present invention can be applied. FIG. 1 is a cross-sectional view along the flow path, and FIG. 2 is a perspective view.

This recording head 13 forms a cured product of a thermosetting resin composition and / or an active energy ray-curable resin composition into a predetermined pattern on a substrate 15 on which ejection energy generating elements and the like are arranged. Then, at least a member 14 for forming a flow path is laminated and joined.
The substrate 15 includes a heat storage layer 19, a heating resistor layer 18 formed of metal, and electrodes 17a and 17 made of aluminum or the like on a surface of a base 20 made of a material having good heat radiation such as alumina.
b and the protective layer 16 are laminated in this order, and the electrodes 17a and 17b are energized to form a portion of the heating resistor layer 18 where the electrodes are not laminated (a portion within a region indicated by n). The discharged energy generating element generates heat, and thermal energy acts on the recording liquid positioned above the element.

At the time of recording, the recording liquid 21 is applied to the member 1
Discharge port (orifice) 22, which is a fine opening at the end of the flow path 4
Up to the electrode 1 in that state in response to the recording signal.
When electricity is supplied to the electrodes 7a and 17b, the area indicated by n rapidly generates heat, and bubbles are generated by the film boiling in the recording liquid 21 in contact with the area. The droplets are ejected as small droplets 24 and fly toward the recording medium 25.

In the ink jet recording head of the present invention,
A cured product of the fluorinated epoxy resin composition is applied as a water-repellent and ink-repellent agent to at least the discharge port opening of the discharge surface 29, and droplets adhere to this surface, which causes a shift in the droplet discharge direction. Is prevented. Moreover, the cured product of the fluorinated epoxy resin composition not only has excellent adhesion, but also does not impair the water repellency and adhesion even if the recording liquid contains an organic solvent, particularly a polar organic solvent. .

In FIG. 2, reference numeral 26 denotes a discharge port, 27 denotes a member having a liquid flow path, 28 denotes a substrate on which a discharge energy generating element and the like are disposed, and 29 denotes a discharge surface.

FIG. 3 shows an example of an ink jet recording apparatus incorporating the multi-head as shown in FIG. In FIG. 3, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to be a fixed end, and forms a cantilever.
The blade 61 is provided at a position adjacent to the recording area with respect to the recording head, and in this example, is held in a form protruding into the movement path of the recording head. Reference numeral 62 denotes a cap, which is disposed at a home position adjacent to the blade 61, and has a configuration in which the cap moves in a direction perpendicular to the moving direction of the recording head to abut on the ejection port to perform capping. 6 more
Reference numeral 3 denotes an ink absorber provided adjacent to the blade 61 and, similarly to the blade 61, held in a form protruding into the movement path of the recording head. The blade 61, the cap 62, and the ink absorber 63 constitute an ejection recovery section 64, and the blade 61 and the ink absorber 63 remove moisture, dust, and the like from the ink ejection port surface.

Reference numeral 65 denotes a recording head which performs recording by an ink jet system, and has a structure for discharging a recording liquid such as ink by thermal energy as shown in FIGS. 1 and 2, for example. Reference numeral 66 denotes a carriage for mounting the recording head 65 and moving the recording head 65. The carriage 66 is slidably connected to a guide shaft 67, and a part of the carriage 66 is a belt 6 driven by a motor 68.
9 (not shown). Thereby, the carriage 6
6 is a movement along the guide shaft 67, that is, the recording head 65.
Can be moved to the recording area and the adjacent area.

Reference numeral 51 denotes a paper feed unit for inserting a recording medium, and reference numeral 52 denotes a paper feed roller driven by a motor (not shown). With these configurations, the recording medium is fed to a position facing the discharge port surface of the recording head, and is discharged via the discharge rollers 53 as the recording proceeds.

In the above configuration, when the recording head 65 returns to the home position at the end of recording, the head recovery unit 64
Is retracted from the moving path of the recording head, while the blade 61 protrudes into the moving path. As a result, the ejection port surface of the recording head 65 is wiped.
Further, when capping is performed by contacting the cap 62 with the ejection opening surface of the recording head 65, the cap 62 moves so as to protrude into the moving path of the recording head.

When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the position at the time of wiping described above. As a result, even in this movement, the ejection surface of the recording head 65 is wiped.

The above-described movement of the print head to the home position is not only at the end of printing and at the time of ejection recovery, but also at a predetermined interval while the printing head moves through the printing area for printing. Position, and the wiping is performed along with the movement.

In the ink jet recording apparatus, color recording can be performed using a recording head in which ejection ports for cyan, magenta, yellow and black are arranged in one head. Further, the recording heads of the respective colors may be independently arranged and used in parallel.

In these cases, the discharge of each color may be performed from one discharge port, or the discharge for each color may be performed simultaneously from a plurality of discharge ports, so that two or more droplets of the same color adhere to the recording medium at the same time. You may make it.

The recording head of the present invention is subjected to a surface treatment with an ink-repellent material having the material configuration described above.
Since it has the chemical properties as shown in the following examples, the ink-jet ink adheres little and the adhered ink is very easily removed by the cleaning wiper blade. Therefore, the substantial durability of the printing is dramatically improved.

[0092]

The present invention will be described in more detail with reference to the following examples.

(Examples 1 to 19) The above composition examples 1 to 1
A 30 to 40% by weight solution of 19 in a mixed solvent of diethylene glycol dimethyl ether / toluene (1: 1) was prepared. This was wet-coated on a silicon wafer substrate having a thermal oxide film having a thickness of 5 μm to a thickness of 1 μm to 3 μm using a spinner. Then, the substrate was dried on a hot plate at 110 ° C. for 5 minutes to remove the solvent. The substrate was irradiated with an integrated amount of ultraviolet rays of ² J / cm ^{2 by} an ultraviolet irradiation apparatus using a high-pressure mercury lamp. Then 150
Heating was carried out in an oven at 150 ° C. for 15 minutes to complete the curing reaction.

The following measurement was performed using the prepared substrate.

T1: Measurement of Contact Angle Pure water, 10% by weight aqueous solution of oleic acid, glycerin 20
Wt% aqueous solution, surfactant 1 wt% aqueous solution [polyoxyethylene nonyl phenyl ether: HLB (Hydro
phobic-Liphobic-Balance)
= 10], the static contact angle was measured at room temperature.

T2: Measurement of Contact Angle after Dipping into Dye Aqueous Solution A substrate treated with ink repellent was immersed in a 3% by weight aqueous solution (pH = 10.3) of water-soluble dye direct black 163 at 60 ° C. for 7 days. Thereafter, the substrate was washed with pure water and dried, and the contact angle of the ink was measured again.

T3 As shown in FIG. 4A, a positive photoresist 42 is formed on a base material 41 on which ejection energy generating elements and the like are previously provided.
("PMER AR-900" manufactured by Tokyo Ohka Kogyo Co., Ltd.)
Spin coat to 0 μm, and 90
Prebaking was performed at 40 ° C. for 40 minutes to form a resist layer.
Thereafter, as shown in FIGS. 4B and 4C, patterning was performed using a mask 43 to obtain a resist pattern 4. On the resist pattern 44, as shown in FIG. 4D, as a material for forming a flow path, a curing agent (modified aliphatic amine, "Fuji Cure FXK" manufactured by Fuji Kasei Kogyo Co., Ltd.)
830 ”) was calculated as follows: base agent / hardener = 100/50 (weight ratio)
And laminated with a layer thickness of 100 μm.

[0098]

[Table 2]

After laminating the flow path forming material layer 45,
After standing for 24 hours, a heat curing treatment was further performed at 100 ° C. for 2 hours. Next, 3% by weight of the thus obtained laminate was
Then, the resist pattern 44 was dissolved and removed, washed and dried to form a liquid flow path 46 (FIG. 4E) to obtain an ink jet recording head.

The fluorinated epoxy resin compositions of Examples 1 to 19 were individually applied to the ejection orifice surface of the ink jet recording head thus obtained, and this was exposed to an ultraviolet ray of 8 J / cm ² and heated at 150 ° C. for 1 hour. Cured by heating.

Further, a predetermined electric wiring is provided to the ink jet recording head and incorporated into a printer, and pure water / glycerin / food black 2 (water-soluble black dye) / N-methylprolidone = 70/15/3/12 ( (Parts by weight) using a long term printing durability test.

In the printing durability test, 100 sheets of a document and a pattern for evaluating the landing accuracy were printed, and the final printed sample was evaluated for dot disorder. This result was set to T3-1. Evaluation A: There is no disturbance in the dot position, and the characters are clear. Evaluation B: The dot position is slightly disturbed, but the influence on the character quality is slight. Evaluation C: The dot positions are considerably disturbed, and the sharpness of the characters is also reduced. Evaluation D: Missing dots and significant deterioration in character quality occurred.

Further, the surface of the used recording head was observed to evaluate the amount of ink adhered. This result was set to T3-2. Evaluation A: Almost no ink droplets on the ejection port surface. Evaluation B: Small ink droplets are observed on the surface of the discharge port. Evaluation C: There is a large ink droplet near the ejection port.

The above results are summarized in Tables 2 and 3 below.

(Comparative Example 1) Instead of the fluorine-containing epoxy resin composition of the present invention, a fluororesin paint (“Fluorad FC-722” manufactured by Sumitomo 3M Limited) was used and dried at 100 ° C. for 30 minutes. As the curing conditions, the evaluations of T1 to T3 were performed in the same manner as in the above examples.

(Comparative Example 2) The same coating and curing conditions as in the example were used except that the following composition using a compound represented by the following structural formulas E-1 and E-2, which is a fluorine-containing epoxy resin, was used. T1 to T
Each evaluation of No. 3 was performed.

[0107]

[Outside 17]

[0108]

[0109]

[Table 3]

[0110]

[Table 4]

As described above, the film made of the fluorine-containing epoxy resin composition of the present invention has a high contact angle and good durability. Further, it can be seen that even if the ink is in contact for a long period of time, there is no adhesion of the ink on the surface of the recording head, and as a result, the dot landing accuracy is good and the print quality can be maintained for a long time.

(Embodiment 20) Embodiments 10, 11, 14,
Each of the compositions 18 and 19 was applied to a polyethersulfone molded plate with a spinner to a thickness of about 2 μm after the solvent was evaporated. A total of 10 J / cm ^{2 was applied} to this substrate from a high-pressure mercury lamp.
And the polymerization was carried out. Next, the substrate was irradiated with an excimer laser beam having a wavelength of 195 nm converged to a beam diameter of 5 μm from above the coating film, and a discharge port was formed. Drilling was performed favorably and the edge was in a processed state with little decomposition residue. From this, the composition of the present invention is:
It can be seen that it has excellent suitability for processing by ultraviolet laser.

[0113]

As described above, the fluorine-containing epoxy resin composition of the present invention can be cured at a low temperature, has good adhesion, and can easily form a film having a desired pattern shape.
It is understood that a surface modification treatment for imparting good water repellency is possible. Therefore, according to the present invention, it is possible to provide an ink jet recording apparatus in which an ink jet recording head having good ink repellency is disposed at an ejection port, and which can perform high-precision printing.

[Brief description of the drawings]

FIG. 1 is a sectional view of a main part of a configuration example of an ink jet recording head to which the present invention is applied.

FIG. 2 is a perspective view of a main part of the inkjet recording head of FIG.

FIG. 3 is a diagram illustrating an example of an inkjet recording apparatus incorporating the inkjet recording head of FIG. 2;

FIG. 4 is a diagram illustrating a process of manufacturing an ink jet recording head according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 13 Ink jet recording head 14 Member in which liquid flow path was formed 15 Substrate 16 Protective layer 17a, 17b Electrode 18 Heating resistor 19 Heat storage layer 20 Base 21 Recording liquid 22 Discharge port 23 Meniscus of recording liquid 24 Small droplet 25 Recording medium 26 Discharge port 27 Member with liquid flow path formed 28 Substrate on which discharge energy generating element and the like are disposed 29 Discharge surface 41 Base material 42 Positive photoresist 43 Mask 44 Resist pattern 45 Liquid flow path forming material 46 Liquid flow Road 51 Paper feed unit 52 Paper feed roller 53 Paper discharge roller 61 Blade 62 Cap 63 Ink absorber 64 Discharge recovery unit 65 Recording head 66 Carriage 67 Guide shaft 68 Motor 69 Belt

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 163/00 C09K 3/18 102 C09K 3/18 102 G03F 7/038 503 G03F 7/038 503 C09D 5 / 00C // C09D 5/00 B41J 3/04 103N (72) Inventor Isao Imamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Tamaki Sato 3-chome Shimomaruko, Ota-ku, Tokyo 30 No. 2 Canon Inc.

Claims (10)

[Claims] 1. A fluorinated aliphatic epoxy resin having at least one perfluoroalkyl group having 6 to 12 carbon atoms and at least two epoxy groups per molecule, and at least a cationic polymerization catalyst. A fluorine-containing epoxy resin composition. 2. The fluorinated epoxy resin composition according to claim 1, wherein the fluorinated aliphatic epoxy resin is at least one compound represented by the following general formula (A-1) or (A-2). [Outside 1] R ₁ and R ₂ are aliphatic atomic groups. 3. A compound represented by the following general formula (C-
The fluorinated epoxy resin composition according to claim 1, comprising at least one compound represented by (1) or (C-2). [Outside 2] 4. A fluorinated polyether resin having in its main chain an alicyclic hydrocarbon group having at least one perfluoroalkyl group having 6 to 12 carbon atoms and at least two epoxy groups in a side chain, and cationic polymerization. A fluorine-containing epoxy resin composition comprising at least a catalyst. 5. The epoxy resin according to claim 1, wherein said fluorine-containing polyether resin is an epoxy structural unit represented by formulas (D-1) and (D-2) and a perfluoro compound represented by formulas (D-3) and (D-4). The fluorine-containing epoxy resin composition according to claim 4, which is a polymer containing a structural unit. [Outside 3] However, the total number of the structural units is 3 to 28. 6. A compound represented by the following general formula (C-
The fluorine-containing epoxy resin composition according to claim 4 or 5, comprising at least one compound represented by (1) or (C-2). [Outside 4] 7. A first step of applying and drying the fluorine-containing epoxy resin composition according to claim 1 or 4 on a substrate, a second step of irradiating active energy rays in a pattern via a mask, A third step of dissolving and removing the non-irradiated portion of the active energy ray with a liquid capable of dissolving the hardening composition; A surface treatment method comprising performing a surface treatment. 8. A first step of applying and drying the fluorine-containing epoxy resin composition according to claim 1 or 4 on a substrate, and a step of polymerizing and curing the entire surface of the composition by irradiation with heat or active energy rays. Step 2, Step 3 for selectively removing the cured composition by selectively irradiating collapsible active energy rays, and Step 4 for performing post-curing as necessary. 3. A surface treatment method characterized by selectively performing a surface treatment on a substrate. 9. An ink jet recording head having a discharge port for discharging a recording liquid, wherein at least the discharge port opening is covered with a curing wire comprising the fluorine-containing epoxy resin composition according to claim 1 or 4. An inkjet recording head. 10. An ink jet recording apparatus comprising the ink jet recording head according to claim 9.