JP4996097B2 - Method for manufacturing ink jet recording head - Google Patents

Description

The present invention relates to the production how the ink jet recording head for recording by discharging a recording liquid to the recording medium.

  The ink jet recording apparatus is based on a recording method in which ink droplets are ejected and directly adhered to an absorptive medium such as paper to perform recording. This apparatus is widely used as an output device for personal computers used in homes and offices because it is capable of high-speed recording and recording on various recording media, and is small and inexpensive. As a typical ink discharge method of an ink jet recording apparatus, there is a method using an electrothermal conversion element as a discharge energy generating element. In this method, an electrothermal conversion element is provided in a pressurizing chamber, and by applying an electrical pulse as a recording signal to this, thermal energy is given to the recording liquid, and when the recording liquid foams due to the phase change of the recording liquid at that time The bubble pressure (at the time of boiling) is used for ejecting recording droplets.

  As an ink jet recording head using this electrothermal conversion system, there is a system (edge shooter) that discharges a recording liquid in parallel to a silicon substrate on which electrothermal conversion elements are arranged. Also, there is a method (side shooter) that discharges a recording liquid perpendicularly to a substrate on which electrothermal conversion elements are arranged.

  FIG. 15 is a cross-sectional view showing an example of a state in which the recording element substrate is mounted on a support member. As shown in FIG. 15, the discharge port plate 104 provided on the surface side of the first recording element substrate 103 has a plurality of discharge ports 104a for discharging the recording liquid. The discharge ports 104a are opened in two rows at positions facing discharge energy generating elements (for example, electrothermal conversion elements) 105 that are recording elements. And the discharge port row | line | column which comprises 1 set by 2 rows is comprised. On the other hand, a recording liquid supply channel 101 a separated by a partition wall 101 b is formed in the support member 101, and this support member 101 is bonded to the first recording element substrate 103. Further, the flow width of the recording liquid supply flow path 101 a of the support member 101 is wider than the opening width of the inlet portion of the recording liquid supply port 106 of the first recording element substrate 103. Therefore, the width of the partition wall 101b is thinner than the interval between the inlet portions of the recording liquid supply ports 106 adjacent to each other.

  Several assembling methods used for manufacturing such a recording element substrate and an ink jet recording head having the same are known.

For example, Patent Document 1 discloses a method for positioning and assembling a recording element substrate with respect to a method for manufacturing an inkjet recording head. In this assembling method, the recording element substrate is accurately positioned by the vacuum suction finger, and the recording element substrate is fixed. As a method of fixing the recording element substrate, a method of bonding with an ultraviolet / thermosetting adhesive is disclosed. Patent Document 2 discloses a method of adhering an orifice plate (discharge port plate) to an ink jet recording head body with an ultraviolet / thermosetting adhesive. Patent Document 3 discloses a method in which a nozzle member is bonded to a liquid discharge head body having a plurality of ink chambers with an ultraviolet / thermosetting adhesive.
Japanese Patent Laid-Open No. 9-188792 JP-A-11-179923 JP-A-11-188873

  However, Patent Document 1 discloses a method for manufacturing an inkjet recording head, but does not disclose a specific formulation of an adhesive. Further, there is no mention of insufficient bonding between the adhesive and the silicon substrate that occurs due to UV (ultraviolet) curing within a few minutes after the adhesive application due to the manufacturing method. This also applies to Patent Document 2 and Patent Document 3.

  Further, as a technique for improving the adhesiveness between the inorganic material and the adhesive, there is a pretreatment in which a diluted solution of a silane coupling agent is applied to the adhesive surface in advance. However, when such pretreatment is performed, the silane coupling agent aqueous solution enters from the ink supply port provided on the back surface of the recording element substrate, adheres to the ink flow path, the discharge port, and the face surface. This is not preferable because it causes warping.

The object of the present invention is to provide a strong adhesive force even when the adhesive is cured in a short time by ultraviolet irradiation when the recording element substrate and the support member are bonded to each other with an adhesive. is never caused color mixing due peeling of the adhesive is to provide a way capable of producing a highly reliable ink jet recording head.

The present invention provides a recording element in which at least a plurality of recording elements for discharging a recording liquid, discharge ports, and ink flow paths are formed, and an ink supply port is disposed on a surface opposite to the discharge port surface. In a method of manufacturing an ink jet recording head, which includes a substrate and a support member that holds and fixes the recording element substrate, and the recording element substrate and the support member are bonded together by an adhesive.
A step of applying an adhesive having a property of being cured by irradiation of ultraviolet rays and a property of being cured by heating to the joint surface of the support member;
Pressing the bonding surface of the recording element substrate and the bonding surface to which the adhesive of the support member is applied, and pressing the adhesive to protrude from the bonding surface;
A step of temporarily fixing the adhesive protruding from the joint surface by irradiating the adhesive with ultraviolet rays and curing the adhesive;
After performing the temporary fixing, irradiating ultraviolet rays from the discharge port surface of the recording element substrate, and curing the adhesive protruding into the ink supply port,
The adhesive has an alkoxysilane group of a silane coupling agent by at least an epoxy resin, a photocationic polymerization initiator, a thermal cationic polymerization initiator, and a reaction accelerator containing acetic acid before the ultraviolet irradiation in the temporary fixing step. Comprising a compound that has been hydrolyzed and converted to a silanol group, wherein the silane coupling agent has an epoxy group,
The method for producing an ink jet recording head, wherein the amount of acetic acid added is 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the silane coupling agent.

In the present invention, an adhesive containing a compound alkoxysilane group of the silane coupling agent by the reaction accelerator containing acetic acid prior to irradiation of ultraviolet rays in the temporary fixing process is converted into a silanol group by hydrolysis. As a result, when the recording element substrate and the support member are bonded with an adhesive, the adhesive strength is strong even when the adhesive is cured in a short time by ultraviolet irradiation, and the adhesive can be used even in severe use environments such as continuous printing. A highly reliable ink jet recording head that does not cause color mixing due to peeling can be obtained.

  The reason why the effects of the present invention can be obtained is as follows.

  First, the inventors investigated the cause of insufficient bonding strength of the adhesive. As a result, when UV irradiation is performed from the discharge port surface in order to temporarily fix the adhesive by UV irradiation or to cure the adhesive that has risen up to the ink supply port, most of the adhesive surface is cured by the UV wraparound. Things turned out. Furthermore, when curing was performed by ultraviolet irradiation, it was found that the silane coupling agent in the adhesive did not perform its original function.

  The silane coupling agent has a reactive functional group (such as an epoxy group or an acryloyl group) that binds to an organic substance in the molecule and an alkoxysilane group. The alkoxysilane group becomes a silanol group by hydrolysis, and the silanol group hydrogen bonds with an inorganic compound such as a silicon substrate. When the heat treatment is further performed, the hydrogen bond portion is dehydrated and condensed to form a stronger covalent bond, and the silane coupling agent and the silicon substrate are firmly bonded. In this heat treatment, the functional group such as an epoxy group of the silane coupling agent also reacts with the main material of the adhesive. Therefore, the silicon substrate is firmly bonded via the silane coupling agent.

  However, when curing is performed by ultraviolet irradiation, epoxy groups and acryloyl groups react with ultraviolet rays, but alkoxysilane groups do not react with ultraviolet rays, so that bonding with a silicon substrate hardly occurs and strong bonding is not achieved.

  Therefore, the inventors decided to add a reaction accelerator (water, acid, etc.), which is a catalyst for hydrolysis reaction, to the adhesive in advance when curing by ultraviolet irradiation. By this reaction accelerator, the alkoxysilane group in the silane coupling agent is hydrolyzed in advance to form a silanol group. Therefore, immediately after the application, hydrogen bonds with the inorganic compound and a good adhesive force can be obtained. The reactivity of this hydrolysis can be confirmed by quantifying the amount of MeOH generated by the reaction by the headspace GC / MS method.

  FIG. 1 to FIG. 6 are explanatory views for explaining each of the preferred head cartridge, recording head, and ink tank and the relationship thereof in which the present invention is implemented or applied. Hereinafter, each component will be described with reference to these drawings.

  The recording head H1001 of the present invention is one constituent element of the recording head cartridge H1000, as can be seen from FIGS. The recording head cartridge H1000 includes a recording head H1001 and an ink tank H1900 (H1901, H1902, H1903, H1904) that is detachably provided on the recording head H1001. The recording head cartridge H1000 is fixedly supported by positioning means and electrical contacts of a carriage (not shown) mounted on the ink jet recording apparatus main body, and is detachable from the carriage. The ink tank H1901 is for black ink, the ink tank H1902 is for cyan ink, the ink tank H1903 is for magenta ink, and the ink tank H1904 is for yellow ink. Thus, each of the ink tanks H1901, H1902, H1903, and H1904 is detachable from the recording head H1001, and each ink tank can be replaced. Thereby, the running cost of image recording by the ink jet recording apparatus is reduced.

  Next, the recording head H1001 will be described in more detail in order for each component constituting the recording head.

<1> Recording Head The recording head H1001 is a bubble jet (registered trademark) side that performs recording using an electrothermal transducer that generates thermal energy for causing film boiling to the ink in response to an electrical signal. This is a recording head that is of a shooter type.

  As shown in the exploded perspective view of FIG. 3, the recording head H1001 includes a recording element unit H1002, an ink supply unit H1003, and a tank holder H2000.

  Further, as shown in the exploded perspective view of FIG. 4, the recording element unit H1002 includes a first recording element substrate H1100, a second recording element substrate H1101, a first plate H1200, an electrical wiring tape H1300, and an electrical contact substrate H2200. , The second plate H1400. The ink supply unit H1003 includes an ink supply member H1500, a flow path forming member H1600, a joint rubber H2300, a filter H1700, and a seal rubber H1800.

<1-1> Recording Element Unit FIG. 5 is a perspective view showing the configuration of the first recording element substrate H1100 in a partially exploded state.

  In the first recording element substrate H1100, for example, an ink supply port H1102 including a long groove-like through-hole as an ink flow path is formed on an Si substrate H1110 having a thickness of 0.5 mm or more and 1 mm or less. Formed by a method such as reactive etching or sandblasting. The electrothermal conversion elements H1103, which are recording elements, are arranged in a staggered pattern on each side across the ink supply port H1102, and the electric heat conversion elements H1103 and Al that supply electric power to the electrothermal conversion elements H1103 are arranged. The electrical wiring is formed by a film forming technique. Furthermore, electrodes H1104 for supplying electric power to the electric wiring are arranged on both outer sides of the electrothermal transducer H1103, and bumps H1105 such as Au are formed on the electrode H1104. On the Si substrate, an ink channel wall H1106 and an ejection port H1107 for forming an ink channel corresponding to the electrothermal conversion element H1103 are formed of a resin material by a photolithography technique, and an ejection port array H1108 is formed. Forming. Accordingly, since the ejection port is provided to face the electrothermal conversion element H1103, the ink supplied from the ink flow path H1102 is ejected by bubbles generated by the electrothermal conversion element H1103.

  FIG. 6 is a perspective view showing the second recording element substrate H1101 in a partially exploded state.

  The second recording element substrate H1101 is a recording element substrate for ejecting ink of three colors, and has three ink supply ports H1102 formed in parallel, and electric is provided on both sides of each ink supply port. A heat conversion element and an ink discharge port are formed. Of course, like the first recording element substrate H1100, an ink supply port, an electrothermal conversion element, an electric wiring, an electrode portion, and the like are formed on the Si substrate, and an ink flow path and an ink discharge are formed on the resin material by photolithography. An exit is formed.

  Similarly to the first recording element substrate, a bump H1105 such as Au is formed on the electrode H1104 for supplying electric power to the electric wiring.

Reference is again made to FIG. The first plate H1200 is made of, for example, an alumina (Al ₂ O ₃ ) material having a thickness of 0.5 mm or more and 10 mm or less. Note that the material of the first plate is not limited to alumina. For example, even if it is made of a material having a linear expansion coefficient equivalent to that of the material of the recording element substrate H1100 and a thermal conductivity equal to or higher than that of the material of the recording element substrate H1100. Good. Examples of the material of the first plate H1200 include silicon (Si), aluminum nitride (AlN), zirconia, silicon nitride (Si ₃ N ₄ ), silicon carbide (SiC), molybdenum (Mo), and tungsten (W). Either may be sufficient. The first plate H1200 has ink supply ports H1201 for supplying black ink to the first recording element substrate H1100 and inks for supplying cyan, magenta, and yellow ink to the second recording element substrate H1101. A supply port H1201 is formed. The ink supply port 1102 of the recording element substrate corresponds to the ink supply port H1201 of the first plate H1200. Further, the first recording element substrate H1100 and the second recording element substrate H1101 are each bonded and fixed to the first plate H1200 with high positional accuracy. The adhesive H1202 (FIGS. 10 to 12) used for bonding is desirably low viscosity, has a low curing temperature, cures in a short time, has a relatively high hardness after curing, and has ink resistance. . As the adhesive H1202, the adhesive of the present invention can be suitably used. The thickness of the adhesive layer is desirably 50 μm or less.

  The electrical wiring tape H1300 applies an electrical signal for ejecting ink to the first recording element substrate H1100 and the second recording element substrate H1101. The electrical wiring tape H1300 has a plurality of opening portions for incorporating the respective recording element substrates, and electrode terminals H1302 corresponding to the electrode portions H1104 of the respective recording element substrates. In addition, it has an electrode terminal portion H1303 for electrical connection with an electrical contact substrate H2200 which is located at the end of the wiring tape and has an external signal input terminal H1301 for receiving an electrical signal from the main unit. The electrode terminal H1302 and the electrode terminal portion 1303 are connected by a continuous wiring pattern of copper foil. In FIG. 4, H1310 indicates a terminal coupling hole.

  The electrical wiring tape H1300, the first recording element substrate 1100, and the second recording element substrate H1101 are electrically connected to each other. For example, the electrode 1104 of the recording element substrate and the electrode terminal H1302 of the electric wiring tape H1300 are electrically bonded by a thermosonic bonding method.

The second plate H1400 is, for example, a single plate-like member having a thickness of 0.5 mm or more and 1 mm or less. This is made of, for example, a ceramic such as alumina (Al ₂ O ₃ ) or a metal material such as Al or SUS. The first recording element substrate H1100 and the second recording element substrate H1101 that are bonded and fixed to the first plate H1200 have openings that are larger than the outer dimensions thereof. Further, the first recording element substrate H1100 and the second recording element substrate H1101 and the electric wiring tape H1300 can be electrically connected in a plane. For this purpose, the second plate is bonded to the first plate H1200, and the back surface of the electric wiring tape H1300 is bonded and fixed by the third adhesive.

  The first recording element substrate H1100, the second recording element substrate H1101, and the electrical connection portion of the electric wiring tape H1300 are composed of a first sealing agent H1307 (FIG. 3 and the like) and a second sealing agent H1308 (FIG. 3 and the like). ). As a result, the electrical connection portion is protected from ink corrosion and external impact. The first sealant mainly seals the back side of the connecting portion between the electrode terminal H1302 of the electric wiring tape and the electrode H1104 of the recording element substrate and the outer peripheral portion of the recording element substrate. The second sealant H1308 seals the front side of the connection portion.

  Further, an electrical contact substrate H2200 having an external signal input terminal H1301 for receiving an electrical signal from the main unit at the end of the electrical wiring tape is thermo-compressed using an anisotropic conductive film or the like to be electrically connected. . Then, the electric wiring tape H1300 is bent at one side surface of the first plate H1200 and bonded to the side surface of the first plate H1200 with a third adhesive. The third adhesive is preferably a thermosetting adhesive mainly composed of an epoxy resin, for example.

<1-2> Ink Supply Unit The ink supply member H1500 is formed by resin molding, for example. As the resin material, it is desirable to use a resin material mixed with a glass filler in an amount of 5% to 40% in order to improve the shape rigidity.

  As shown in FIG. 7, the ink supply member H1500 is a component of the ink supply unit H1003 for guiding ink from the ink tank H1900 to the recording element unit H1002. Here, the ink flow path H1501 is formed by ultrasonic welding of the flow path forming member H1600. Further, a filter H1700 for preventing dust from entering from the outside is joined to the joint portion H1520 engaged with the ink tank H1900 by welding. Further, a seal rubber H1800 is attached in order to prevent ink from evaporating from the joint H1520. In FIG. 7, reference numeral H1502 denotes a tank positioning hole, H1504 denotes a second hole, H1908 denotes a tank positioning pin, H1909 denotes a first claw, 1911 denotes a third claw, and H1912 denotes a movable lever.

  The ink supply member H1500 also has a part of the function of holding the removable ink tank H1900, and has a first hole H1503 for engaging the second claw H1910 of the ink tank H1900.

  Further, as shown in FIG. 4, a mounting guide H1601 for guiding the recording head cartridge H1000 to the mounting position on the carriage of the ink jet recording apparatus main body is provided. Furthermore, an engaging portion for mounting and fixing the recording head cartridge to the carriage by a head set lever is also provided. Further, an abutting portion H1509 in the X direction (carriage scan direction) for positioning at a predetermined mounting position of the carriage, an abutting portion H1510 in the Y direction (recording medium conveyance direction), and an abutting in the Z direction (ink ejection direction) Part H1511 is also provided. Further, a terminal fixing portion H1512 for positioning and fixing the electrical contact substrate H2200 of the recording element unit H1002 is provided. A plurality of ribs are provided around the terminal fixing portion H1512 and its periphery to enhance the rigidity of the surface having the terminal fixing portion H1512. In FIG. 4, reference numeral H1602 denotes an ink supply port.

<1-3> Coupling of recording head unit and ink supply unit As shown in FIG. 3, the recording head H1001 is completed by coupling the recording element unit H1002 to the ink supply unit H1003 and further to the tank holder H2000. The coupling is performed as follows. The ink supply port of the recording element unit H1002 (ink supply port H1201 of the first plate H1200) and the ink supply port of the ink supply unit H1003 (ink supply port of the flow path forming member H1600) are communicated so that ink does not leak. For this reason, each member is fixed with screws H2400 so as to be pressure-bonded via the joint rubber H2300. At the same time, the recording element unit H1002 is accurately positioned and fixed with respect to the reference positions in the X, Y, and Z directions of the ink supply unit.

  The electrical contact substrate H2200 of the recording element unit H1002 is positioned and fixed to one side surface of the ink supply member H1500 by terminal positioning pins H1515 (2 places) and terminal positioning holes H1309 (2 places). In FIG. 4, reference numeral H1516 denotes a terminal coupling pin. The fixing method is, for example, fixing by crimping the terminal coupling pin H1515 provided on the ink supply member H1500, but may be fixed using other fixing means. A completed drawing is shown in FIG.

  Further, the recording head H1001 is completed by fitting the coupling hole and coupling portion of the ink supply member H1500 with the tank holder into the tank holder H2000 and coupling them. The completed drawing is shown in FIG.

<2> Printhead Cartridge FIGS. 1 and 2 are diagrams for explaining mounting of the printhead H1001 and the ink tanks H1901, H1902, H1903, and H1904 constituting the printhead cartridge H1000. The ink tanks H1901, H1902, H1903, and H1904 contain corresponding color inks. As shown in FIG. 7, each ink tank is provided with an ink supply port H1907 for supplying ink in the ink tank to the recording head H1001. For example, when the ink tank 1901H is attached to the recording head H1001, the ink supply port H1907 of the ink tank H1901 is brought into pressure contact with the filter H1700 provided in the joint portion H1520 of the recording head H1001. Then, the black ink in the ink tank H1901 is supplied from the ink supply port H1907 to the first recording element substrate through the first plate H1200 via the ink flow path H1501 of the recording head H1001.

  Then, ink is supplied to the foaming chamber having the electrothermal conversion element H1103 and the discharge port H1107, and is ejected toward a recording sheet as a recording medium by the thermal energy given to the electrothermal conversion element H1103.

  Next, of the manufacturing processes of the recording head having the above-described configuration, a process of bonding the first recording element substrate H1100 to the first plate H1200 (supporting member) using an adhesive will be described.

  10 (a) to 10 (c), 11 (d) and 11 (e), 12 (f) and 12 (g) are cross-sectional views for explaining an embodiment of the method for manufacturing an ink jet recording head of the present invention. It is. 10 to 12 show cross sections obtained by cutting the first recording element substrate H1100 along the longitudinal direction of the ejection port array.

10 to 12, reference numeral H101 denotes a transfer pin for applying the adhesive H1202, and reference numeral H106 denotes a vacuum suction finger for sucking and positioning the recording element substrate.
Reference numerals H110 and H111 denote CCD cameras for recognizing the position of the recording element substrate, and reference numerals H112 and H113 denote ultraviolet irradiation nozzles, respectively.

  In the step of attaching the recording element substrate H1100 made using the silicon substrate as the first element substrate to the plate H1200 made of the first alumina, first, as shown in FIG. An adhesive H1202 is applied to the transfer surface. Subsequently, as shown in FIG. 5A, the transfer surface of the transfer pin H101 is brought into contact with the first plate H1200. Then, as shown in FIG. 3C, when the transfer pin H101 is separated from the first plate H1200, an adhesive H1202 is applied to the joint surface of the first plate H1200.

  At this time, the adhesive H1202 on the first plate H1200 is transferred to a position shifted outward from the position where the first recording element substrate H1100 contacts. This adhesive is an ultraviolet / thermosetting combination type that cures when irradiated with ultraviolet rays or when heat is applied, and uses an adhesive that is resistant to ink and excellent in transferability.

  Next, as shown in FIG. 11D, the surface of the ink flow path wall H1106 that forms the ejection port H1107 of the first recording element substrate H1100 is suction-held by the vacuum suction finger H106. Then, an alignment mark (not shown) of the first recording element substrate H1100 is optically recognized by the CCD cameras H110 and H111, and alignment with the first plate H1200 is performed. Subsequently, as shown in FIG. 11E, the positioned vacuum suction finger H106 is lowered, and the first recording element substrate H1100 is brought into contact with and pressed against the first plate H1200. As a result, the adhesive H1202 protrudes to the end portion in the longitudinal direction of the first recording element substrate H1100 as shown in FIG. In the drawing, it appears that the adhesive H1202 protrudes only outside the ink flow path, but actually the adhesive slightly protrudes also in the ink flow path (particularly in the ink supply port) as described later.

  Then, as shown in FIG. 12F, ultraviolet irradiation is performed by the ultraviolet irradiation nozzles H112 and H113 while the first recording element substrate H1100 is pressed against the first plate H1200. As a result, the adhesive H1202 protruding from the end is cured, and the position of the first recording element substrate H1100 is fixed (temporarily fixed) on the first plate H1200. Further, as shown in FIG. 5G, after the vacuum suction finger H106 is released from the vacuum and moved, the ultraviolet irradiation nozzles H112 and H113 irradiate ultraviolet rays again from the surface of the discharge port H1107. As a result, the adhesive H1202 that slightly protrudes into the ink flow path (especially in the ink supply port) is cured, and the adhesive flows out to the ink flow path and the discharge port to prevent clogging. Further, by further curing the adhesive by heating, a further sufficient bonding strength can be obtained.

  FIG. 13 is a perspective view showing the first recording element substrate H1100 shown in FIG. 11E during the assembly process. As shown in this drawing, the adhesive H1202 protrudes from the longitudinal end portion of the first recording element substrate H1100.

  FIG. 14 is a perspective view showing the second recording element substrate H1101 in the state of FIG. 11E during the assembly process. Thus, the second recording element substrate H1101 is also positioned and fixed on the first plate H1200 in the same process as described above. The adhesive H1202 protrudes from the end portion in the longitudinal direction of the second recording element substrate H1101.

  If the thickness of the adhesive after curing is less than 4 μm, poor adhesion may occur. If the thickness of the adhesive exceeds 10 μm, heat radiation from the recording element substrate to the first plate is hindered, and normal ink is used. Discharging may not be performed. Therefore, it is desirable that the thickness of the adhesive H1202 between the recording element substrates H1100 and H1101 and the first plate H1200 be about 4 μm or more and 10 μm or less.

  In each of the above embodiments, the bubble jet type, particularly the side shooter type, which uses an electrothermal transducer that generates thermal energy as a recording method has been described, but the present invention is not limited thereto. For example, the present invention can also be applied to a so-called piezo discharge method using an electromechanical transducer and an ink jet head of an edge shooter type head.

  Next, the adhesive used in the present invention will be described.

The adhesive used in the present invention contains at least an epoxy resin, a cationic photopolymerization initiator, a thermal cationic polymerization initiator, and an alkoxysilane group of the silane coupling agent that is hydrolyzed by a reaction accelerator before the ultraviolet irradiation in the temporary fixing step. It comprises a compound that has been decomposed and converted into a silanol group.

Examples of the silane coupling agent (before hydrolysis) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (methacryloyloxypropyl) trimethoxysilane, and γ- (methacryloyloxypropyl). ) Triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , Γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-amino Examples thereof include propyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) having a ketimine group having a switching function and an alkoxysilyl group. However, in the present invention, at least a silane coupling agent having an epoxy group is used. Silane coupling agents are those having a crosslinking function of the organic materials and inorganic materials in the same molecule.

  A preferable addition amount of the silane coupling agent varies depending on the type of the silane coupling agent, the surface structure of the adhesion target made of an inorganic material, the type of the adhesive, and the like. In general, 0.1 parts by mass or more and 30 parts by mass or less is preferable with respect to 100 parts by mass of the epoxy resin in the adhesive. Furthermore, 0.1 mass part or more and 10 mass parts or less are especially preferable. The lower limit value of each of the above ranges is significant in that the bridging bond between the inorganic material and the organic material is sufficiently generated. The upper limit is significant in that sufficient bridging bonds are maintained by facilitating the formation of a monomolecular film of a silane coupling agent on the surface to be bonded.

In general, when an adhesive to which a silane coupling agent or a solution thereof is added is stored for about one week after addition and mixing, silanol grouping of alkoxysilane groups in the silane coupling agent proceeds to some extent. However, since it is affected by storage conditions such as temperature, humidity, and the ratio of air in the container, it becomes difficult to manage the reaction rate of the dealcoholization reaction and keep the bonding conditions constant. Therefore, the present inventors paid attention to the hydrolysis reaction of the silane coupling agent and added a substance (reaction accelerator) that accelerates the hydrolysis reaction of the silane coupling agent to the adhesive. Thereby, the alkoxysilane group of a silane coupling agent hydrolyzes, and it becomes the compound by which silanol grouping was carried out before the irradiation of the ultraviolet-ray in a temporary fix | stop process . The adhesiveness is improved by hydrogen bonding between the compound and the substrate made of silicon or the like in a short time after the adhesive is applied to the recording element substrate. Furthermore, a dehydration condensation reaction is performed by a subsequent thermosetting process, and the compound and the substrate become a stronger covalent bond, so that the adhesive force is improved.

At least acetic acid is used as the reaction accelerator . Moreover, it can be preferably used a reaction accelerator containing both acid and water.

  When water is used as the reaction accelerator, the amount of water added is preferably as much as possible from the viewpoint of promoting the hydrolysis reaction. However, if too much water is added, the physical properties of the cured product of the adhesive may be softened, ink resistance may deteriorate, or silanol groups generated in the silane coupling agent may be polymerized to increase viscosity. is there. From such a point, the amount of water added is preferably 10 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the silane coupling agent. If the addition amount of water is 10 parts by mass or more, the effect of promoting the hydrolysis reaction is enhanced. Moreover, if it is 500 mass parts or less, it will become difficult to produce the above problems. In addition, although it is a small amount, the resin etc. which comprise an adhesive agent may contain the water | moisture content. Therefore, it is preferable to measure the amount of water in the resin in advance using a Karl Fischer tester or the like and determine the amount of water added as a reaction accelerator in consideration of the amount of water.

  When water is used as the reaction accelerator, the progress of the hydrolysis reaction is relatively slow. Therefore, for example, it is preferable to add to the adhesive what was left for about one day after adding water to the silane coupling agent.

When using an acid as a reaction accelerator, it is preferable to use an organic acid. Specific examples of the organic acids, formic acid, acetic acid, monocarboxylic acids such as propionic acid, oxalic acid, malonic acid, may be mentioned dicarboxylic acids such as succinic acid, in view of the particularly toxic and volatile in the present invention A reaction accelerator containing acetic acid is used . The acetic acid, since it is considered to replace the methoxy groups of the silane coupling agent at an earlier acetoxy group reactive, the greatest effect as a promoter of the silane coupling agent. Incidentally, hydrochloric, although it is possible for 併 also inorganic acids such as nitric acid, or impair the insulating properties caused migration of ions such as chlorine ions, because it may lead to corrosion, a special attention in adhesion of electronic materials Cost.

  The reason that the acid promotes the hydrolysis is considered to be that the chemical equilibrium is shifted from the alkoxysilane group to the silanol group by making the pH acidic because the silanol group is weakly acidic and stable. Therefore, an acid may be added to the silane coupling agent in advance and then added to the adhesive, but it is preferable to make the pH of the adhesive acidic in order to maintain the converted silanol groups.

In the present invention uses at least acetic acid as a reaction accelerator, but the addition amount of acetic acid may be a small amount compared to water. Acetic acid is because components fulfill such catalytic functions described above in the hydrolysis reaction. Amount of acetic acid with respect to 100 parts by weight silane coupling agent, 0.05 parts by mass or more and 5 parts by mass or less. If the addition amount of acetic acid is 0.05 part by mass or more, it is possible to shift the chemical equilibrium by pH decrease in the adhesive sufficiently. Further, if more than 5 parts by weight, polymerization of the epoxy resin in the corrosion and the adhesive member by volatilization of acetic acid is less likely to occur.

  Epoxy resins generally have good photocation reactivity, and are superior in alkali ink resistance as compared with radical polymerizable acrylic resins and the like, and thus are preferable as an adhesive constituting the flow path. Among these, alicyclic epoxy resins are most suitable for the present invention because of their good photocationic polymerizability. If the photoreactivity is good, it is cured instantaneously after irradiation with ultraviolet rays, and the positional accuracy in the temporary fixing process is improved. Further, if the alkali ink resistance is good, no problem occurs even if the adhesive forms a flow path.

  Specific examples of the alicyclic epoxy resin include polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring; cyclohexene obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an oxidizing agent. Examples thereof include an oxide structure-containing compound or a cyclopentene oxide structure-containing compound; a vinylcyclohexane oxide structure-containing compound obtained by epoxidizing a compound having a vinylcyclohexane structure with an oxidizing agent. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane Metadioxane, bis ( 3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, Methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, Epoxy hexahydrophthalic acid di-2-ethylhexyl etc. are mentioned.

  Furthermore, in order to adjust the physical properties of the cured product, for example, an aromatic epoxy resin, an aliphatic epoxy resin, an epoxy-modified butadiene resin, a polyhydric alcohol, an acid anhydride, or the like can be added to the alicyclic epoxy resin.

  As the aromatic epoxy resin, for example, a polyhydric phenol having at least one aromatic ring or a polyglycidyl ether of an alkylene oxide adduct thereof can be used. Specific examples thereof include glycidyl ether, epoxy novolac resin, bisphenol A novolak diglycidyl ether, bisphenol F novolac diglycidyl ether, and the like obtained by adding bisphenol A, bisphenol F or an alkylene oxide thereto.

  Specific examples of aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, and aliphatic long-chain unsaturated hydrocarbons oxidized with an oxidizing agent. Examples thereof include epoxy-containing compounds, glycidyl acrylate or glycidyl methacrylate homopolymers, glycidyl acrylate or glycidyl methacrylate copolymers, and the like. Representative compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, dipentaerythritol. Hexaglycidyl ether of Toll, Polyglycol diglycidyl ether, Polypropylene glycol diglycidyl ether and other polyhydric alcohol glycidyl ethers; Propylene glycol, Glycerin and other aliphatic polyhydric alcohols with one or more alkylene oxides Polyglycidyl ether of polyether polyol obtained by addition; diglycidyl ester of aliphatic long-chain dibasic acid. Furthermore, monoglycidyl ethers of higher aliphatic alcohols, phenols, cresols, butylphenols, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy stearin Also included are octyl acid, butyl epoxy stearate, and epoxidized linseed oil.

  Examples of the epoxy-modified butadiene resin include BF-1000 manufactured by Asahi Denka Kogyo Co., Ltd., EPB-13 and EPB-1054 manufactured by Nippon Soda Co., Ltd., and E-700-3 manufactured by Nippon Petrochemical Co., Ltd. 5, E-700-6.5, E-1000-3.5, E-1000-6.5, E-1000-8, E-1800-6.5 (all are trade names) and the like. .

  Examples of the photocationic polymerization initiator used for the adhesive include aromatic onium salts (see J. POLYMER SCI: Symposium No. 56, 383-395 (1976)), Irgacure (registered trademark) 261 manufactured by Ciba Geigy, Asahi Denka Kogyo Co., Ltd. SP-150 (trade name), SP-170 (trade name) and the like.

  As the thermal cationic polymerization initiator used for the adhesive, for example, San-Aid (registered trademark) SI-60L, SI-80L, SI-100L, manufactured by Sanshin Chemical Industries, Ltd., SI-100L, manufactured by Asahi Denka Kogyo Co., Ltd. CP-66 (trade name), CP-77 (trade name), or a combination of an aromatic onium salt and a reducing agent (Japanese Patent Laid-Open No. 54-102394, J. POLYMER SCI: Polymer Chemical Edition Vol. 121, 97) -109 (1983)).

  Hereinafter, the present invention will be described in more detail with reference to examples. In the following, “part” means “part by mass”.

<Example 1>
First, an adhesive having the following composition (before addition of a silane coupling agent) was prepared.

The product names in Table 1 indicate the following products.
Celoxide 2021: (Daicel UCB, alicyclic epoxy resin).
EponSU 8: (Bisphenol type epoxy resin, manufactured by SHELL Chemical Co.).
Adekaoptomer SP-170: (Asahi Denka Co., photocationic polymerization initiator).
Adeka Optron CP-66: (Asahi Denka Co., Ltd., thermal cationic polymerization initiator).

  The amount of water contained in the two resins and two polymerization initiators constituting this adhesive was 0.21%.

  To this adhesive, 3 parts of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane, manufactured by Toray Dow Corning Co., Ltd., trade name SH6040) is mixed, and while stirring, 0.2 part of acetic acid is slowly added as a reaction accelerator. And stirred for 1 hour to obtain an adhesive.

<Example 2>
An adhesive was prepared in the same manner as in Example 1 except that the amount of acetic acid added was changed to 0.05 part.

<Example 3>
An adhesive was prepared in the same manner as in Example 1 except that the amount of acetic acid added was changed to 5 parts.

< Reference Example 4>
First, 100 parts of the silane coupling agent similar to Example 1 was put in the bottle, and 10 parts of water was slowly added dropwise as a reaction accelerator while stirring. Thereafter, the mixture was stirred for 1 hour, the inside of the bottle was purged with nitrogen, and left at room temperature for 1 day. An adhesive was prepared in the same manner as in Example 1 except that 3 parts of the silane coupling agent solution thus obtained was added to the same adhesive as in Example 1 (before addition of the silane coupling agent).

< Reference Example 5>
A silane coupling agent solution was prepared in the same manner as in Reference Example 4 except that 50 parts of water was used as a reaction accelerator, 10 parts of the adjusted silane coupling agent solution was added, and adhesion was performed in the same manner as in Example 1. An agent was prepared.

<Example 6>
An adhesive was prepared in the same manner as in Example 1 except that the amount of the silane coupling agent was changed to 30 parts and 1 part of acetic acid and 5 parts of water were used in combination as a reaction accelerator.

< Reference Example 7>
An adhesive was prepared in the same manner as in Example 1 except that the amount of the silane coupling agent was changed to 30 parts and 0.5 part of oxalic acid was used as the reaction accelerator.

<Comparative Example 1>
An adhesive was prepared in the same manner as in Example 1 except that no reaction accelerator (acetic acid) was added.

<Preparation of Inkjet Recording Head H1001 and Ink Supply Unit H1003>
Using the adhesives prepared in Examples 1 to 7 and Comparative Example 1, the recording element substrate and the support member were bonded according to the steps described above.

That is, first, the adhesives prepared in Examples 1 to 7 and Comparative Example 1 were applied to the bonding surface of the recording element substrate (first recording element substrate H1100). Next, the recording element substrate and the support member (first plate H1200) were pressed against each other, and the adhesive H1202 protruded from the joint surface between the two. The pressure at that time was about 10 g / mm ² . Further, the recording element substrate was positioned and fixed with respect to the support member, and thereafter, the adhesive protruding from the joint surface was irradiated with ultraviolet rays to be temporarily cured by temporarily curing the adhesive. The ultraviolet irradiation conditions at the time of temporary fixing were 500 mW and 10 J (values at 365 nm attachment). Next, the adhesive protruding from the ink supply port was cured by irradiating ultraviolet rays from the discharge port surface of the recording element substrate. The ultraviolet irradiation conditions at this time were 500 mW and 7.5 J (values at 365 nm attachment). The illuminance is a value at a light receiver 365 nm of the illuminometer. Thereafter, heat curing was further performed. The heating conditions were 150 ° C. and 3 hours.

  Furthermore, in accordance with the method for manufacturing a recording element unit described above, a predetermined electrical wiring process and a sealing process were performed. The produced recording element units were joined by the above method to obtain an ink supply unit.

<Evaluation>
(1) Continuous printability:
The ink supply unit produced using the adhesives of Examples 1 to 7 and Comparative Example 1 was subjected to 1 × 10 ⁸ pulse printing continuously using an inkjet printer (trade name BJF850 manufactured by Canon Inc.), After that, a nozzle check pattern was printed to confirm the presence or absence of color mixing.

(2) Adhesiveness of adhesive:
In order to evaluate the adhesiveness of each adhesive prepared in Examples 1 to 7 and Comparative Example 1, these adhesives were applied to a silicon bare wafer with a scaler (thickness of about 50 μm), and 150 ° C. for 180 minutes. A solid film was obtained by heating and curing under conditions. This solid film was immersed in magenta ink for inkjet, and then exposed to a steam atmosphere at 121 ° C. and 2 atm for 10 hours. The residual film ratio of this coating film was determined, the adhesiveness was evaluated according to the following criteria, and the results are shown in Table 2.
“AA”: Remaining film ratio exceeds 80%.
"A": Remaining film ratio is 60% or more and 80% or less.
“C”: Remaining film ratio is less than 60%.

(3) Preservability of adhesive:
100 ml of the prepared adhesive was placed in a light-shielding container for 100 ml and left for 1 month at 25 ° C. and 60% humidity. The state of the adhesive after standing was evaluated.
“AA”: No change.
“A”: viscosity increase within 10%.
"C": There is a viscosity increase exceeding 10%.

FIG. 2 is a perspective view showing a state in which a recording head and an ink tank are combined in an embodiment of the recording head cartridge of the present invention. FIG. 2 is a perspective view illustrating a state in which the recording head and the ink tank are separated from each other according to the embodiment of the recording head cartridge of the present invention. FIG. 2 is an exploded perspective view of the recording head cartridge shown in FIG. 1 and the like. FIG. 4 is an exploded perspective view of the ink supply unit and the recording element unit shown in FIG. 3. FIG. 5 is a perspective view showing the first recording element substrate shown in FIG. 4 with a part thereof broken. FIG. 5 is a perspective view showing the second recording element substrate shown in FIG. 4 with a part thereof broken. FIG. 2 is a cross-sectional view of the recording head cartridge shown in FIG. 1 and the like. FIG. 2 is a perspective view showing a combined body of a recording element unit and an ink supply unit in the recording head cartridge shown in FIG. 1 and the like. FIG. 2 is a perspective view illustrating a bottom surface of the recording head cartridge illustrated in FIG. 1 and the like. It is sectional drawing for demonstrating one Embodiment of the manufacturing method of the inkjet recording head of this invention. It is sectional drawing for demonstrating one Embodiment of the manufacturing method of the inkjet recording head of this invention. It is sectional drawing for demonstrating one Embodiment of the manufacturing method of the inkjet recording head of this invention. FIG. 12 is a perspective view showing the first recording element substrate shown in FIG. 11E during the assembly process. FIG. 12 is a perspective view showing the second recording element substrate shown in FIG. 11E during the assembly process. FIG. 6 is a cross-sectional view illustrating an example of a state in which a recording element substrate is mounted on a support member.

Explanation of symbols

H101 Transfer pin H106 Vacuum suction finger H110, H111 CCD camera H112, H113 UV irradiation nozzle H1000 Recording head cartridge H1001 Recording head H1002 Recording element unit H1003 Ink supply unit H1100, H1100 ′ First element substrate H1101 Second element substrate H1102 Ink Supply port H1103 Electrothermal conversion element H1104 Electrode H1105 Bump H1106 Ink channel wall H1107 Ejection port H1108 Ejection port array H1110 Si substrate H1200 First plate H1201 Ink supply port H1202 Adhesive H1300 Electric wiring tape H1301 External signal input terminal H1302 Electrode terminal H1303 Electrode terminal portion H1307 First sealant H1308 Second sealant H1309 End Positioning hole H1310 Terminal coupling hole H1400 Second plate H1500 Ink supply member H1501 Ink flow path H1502 Tank positioning hole H1503 First hole H1504 Second hole H1509 X abutting part H1510 Y abutting part H1511 Z abutting part H1512 terminal Fixing portion H1515 Terminal positioning pin H1516 Terminal coupling pin H1520 Joint portion H1600 Flow path forming member H1601 Mounting guide H1602 Ink supply port H1700 Filter H1800 Seal rubber H1900 Ink tank H1901 Black ink tank H1902 Cyan ink tank H1903 Magenta ink tank H1904 Yellow ink tank H1907 Ink Supply port H1908 Tank positioning pin H1909 First claw 1910 2nd claw H1911 3rd claw H1912 Movable lever H2000 Tank holder H2200 Electrical contact substrate H2300 Joint rubber H2400 Screw 101 Support member 101a Recording liquid supply channel 101b Bulkhead 103 First recording element substrate 104 Discharge port plate 104a Discharge port 105 Discharge energy generating element 106 Recording liquid supply port

Claims (4)

A plurality of recording elements for discharging a recording liquid, discharge ports and ink flow paths are formed, and a recording element substrate in which an ink supply port is disposed on a surface opposite to the discharge port surface; A method of manufacturing an ink jet recording head, comprising: a support member for holding and fixing a recording element substrate, wherein the recording element substrate and the support member are bonded together by an adhesive;
A step of applying an adhesive having a property of being cured by irradiation of ultraviolet rays and a property of being cured by heating to the joint surface of the support member;
Pressing the bonding surface of the recording element substrate and the bonding surface to which the adhesive of the support member is applied, and pressing the adhesive to protrude from the bonding surface;
A step of temporarily fixing the adhesive protruding from the joint surface by irradiating the adhesive with ultraviolet rays and curing the adhesive;
After performing the temporary fixing, irradiating ultraviolet rays from the discharge port surface of the recording element substrate, and curing the adhesive protruding into the ink supply port,
The adhesive has an alkoxysilane group of a silane coupling agent by at least an epoxy resin, a photocationic polymerization initiator, a thermal cationic polymerization initiator, and a reaction accelerator containing acetic acid before the ultraviolet irradiation in the temporary fixing step. Comprising a compound that has been hydrolyzed and converted to a silanol group, wherein the silane coupling agent has an epoxy group,
A method for producing an ink jet recording head, wherein the amount of acetic acid added is 0.05 to 5 parts by mass with respect to 100 parts by mass of the silane coupling agent.   2. The method of manufacturing an ink jet recording head according to claim 1, wherein the reaction accelerator contains acetic acid and water.   2. The method for producing an in-jet recording head according to claim 1, wherein the reaction accelerator is acetic acid and water.   4. The method of manufacturing an ink jet recording head according to claim 1, wherein the recording element substrate is a silicon substrate.

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