JP2005178054A - Liquid developer of alkali development type dry film resist, inkjet head manufactured with use of the liquid developer, manufacturing method for the inkjet head, and inkjet type recording apparatus with the inkjet head - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reduce as much as possible, an amount of residue of a dry film to be left at a part where the dry film is not present in the case where the dry film of an alkali development type is developed and patterned by a liquid developer. <P>SOLUTION: The liquid developer of the alkali development type dry film contains at least one metal compound selected from the group of alkali metal compounds and alkaline-earth metal compounds, and at least one surface active agents. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an apparatus for ejecting or transporting a small amount of liquid, such as an inkjet head of an inkjet recording apparatus or μ-TAS (Micro Total Analysis System). Produced using a developer of an alkaline development type dry film resist used for forming a patterned fine plating structure part for constituting an ink chamber, a reaction chamber, a liquid flow path, and the like. The present invention belongs to a technical field related to an inkjet head, a method of manufacturing the inkjet head, and an inkjet recording apparatus including the inkjet head.

  In general, a structure part for configuring an ink chamber of an inkjet head, a reaction chamber of μ-TAS, a liquid flow path, or the like has a micro structure patterned with high shape accuracy (see, for example, Patent Document 1). .

One of the methods for forming the microstructure portion as described above is a pattern plating method. For example, as shown in FIGS. 7 and 8, a dry film resist (hereinafter abbreviated as DFR) 101 is laminated on a substrate 100, the DFR 101 is exposed through a mask pattern, and then the exposed DFR 101 is formed. By developing with a developer, the DFR 101 is patterned (FIGS. 7 and 8 show a state in which the DFR 101 is patterned), and the DFR 101 is not present on the substrate 100 using the patterned DFR 101 as a mold ( After the plating is performed on the groove portion 102 composed of the substrate 100 and the DFR 101), the patterned DFR 101 used as a mold is removed by dissolution or decomposition to form a patterned micro-plated structure portion. To do. The DFR 101 used in such a plating method is excellent in adhesion to the substrate 100 and requires high heat resistance and chemical resistance. Therefore, an alkaline solution (for example, sodium carbonate (Na ₂ CO ₃₎ as a developer is required. In many cases, an alkali development type DFR which is decomposed and dispersed in (1) an aqueous solution) and developed is used (for example, see Patent Document 2).
JP 2000-6400 A JP-A-6-252535

  However, when the alkali development type DFR 101 is developed with a conventional alkaline developer, the residue 103 of the DFR 101 adheres to the bottom surface (plating formation surface) of the groove 102 as shown in FIGS. There is a problem that the residue 103 cannot be completely removed even by washing. In particular, when the depth of the groove 102 is relatively deep, such as when forming a structure (ink chamber member) for forming an ink chamber of an inkjet head, the residue 103 is further removed. It becomes difficult. When plating is performed with such a residue 103 attached to the plating formation surface, the growth of the plating is hindered to generate cavities (pits) in the plating structure portion, or the plating grows abnormally and the convex portion is formed on the plating surface. Occur.

  When such a pit occurs, there is a problem that liquid leaks from the pit. For example, when a pit is generated between adjacent ink chambers in an ink chamber member, the ink chambers communicate with each other through the pits, so that the inks in the two ink chambers are mixed or crosstalk (adjacent inks). This may cause a serious defect such as occurrence of a change in ejection characteristics due to the vibration of the diaphragm layer or ink in the chamber.

  Moreover, when a convex part generate | occur | produces on the plating surface, when joining another member to the surface, there exists a problem that it will not be made to contact | adhere and a clearance gap will arise. In particular, in electroless plating, the plating surface can be flattened without grinding. For this reason, for example, a flow path pattern is formed on the substrate by electroless plating, and is separated from the flow path (on the plating surface). By adhering the substrate, there is an advantage that a closed flow path can be easily produced at low cost. There is a possibility of leakage into the flow path, and the characteristics of electroless plating cannot be fully utilized.

  The present invention has been made in view of such points, and an object of the present invention is to devise the components contained in the developer when the alkaline developing DFR is developed and patterned with the developer. Accordingly, an attempt is made to reduce as much as possible the amount of DFR residue remaining in the portion where the DFR does not exist.

  In order to achieve the above object, according to the first aspect of the present invention, at least one metal compound selected from the group of alkali metal compounds and alkaline earth metal compounds, and at least 1 A seed surfactant was contained.

  As a result, the surfactant in the developer adheres to the small pieces that become the residue of DFR, and this surfactant makes it difficult for the small pieces to adhere to the portion where the DFR does not exist (plating formation surface). The amount of residue can be reduced. As a result, even if the plating structure portion is formed in a portion where no DFR is present, it is possible to suppress the occurrence of pits in the interior or the occurrence of protrusions on the plating surface.

  In the invention of claim 2, in the invention of claim 1, the total content of the metal compound is 0.1 wt% or more and 5 wt% or less, and the total content of the surfactant is 0.1 wt% or more and 20 wt% % Or less.

  That is, if the total content of the surfactant is less than 0.1% by weight, the amount of the surfactant adhering to the DFR pieces is reduced and the effect of reducing the residual amount cannot be sufficiently obtained. If the amount is more than% by weight, the development characteristics of the DFR by the developer are deteriorated. In addition, if the total content of the metal compound is 0.1 wt% or more and 5 wt% or less, combined with the total content of the surfactant, the deterioration of the DFR development characteristics by the developer is suppressed. However, the effect of reducing the amount of residue can be maximized.

  According to a third aspect of the present invention, an ink chamber that contains ink, an ink discharge port that communicates with the ink chamber, and a plurality of layers including a first electrode layer, a piezoelectric layer, and a second electrode layer are laminated. Thus, the invention is an ink jet head comprising a piezoelectric element that is deformed in the stacking direction so as to reduce the volume of the ink chamber and discharges ink in the ink chamber from the ink discharge port.

  According to the present invention, an ink chamber in which an ink chamber hole for forming the ink chamber is opened on a surface on one side in the stacking direction of the piezoelectric element on a surface opposite to the piezoelectric element side and the piezoelectric element. A nozzle plate having the ink discharge port is joined to a surface of the ink chamber member opposite to the piezoelectric element, and a side wall portion of the ink chamber hole in the ink chamber member is The pattern is formed by plating using an alkali developing type dry film resist patterned so as to correspond to the ink chamber hole position of the ink chamber member on the surface of the element on the ink chamber member side. The alkali-developable dry film resist thus formed is formed on the piezoelectric element before the side wall of the ink chamber hole is formed on the ink chamber member. An alkali development type dry film resist laminated on the entire surface of the chamber member and exposed through a mask pattern, at least one metal compound selected from the group of alkali metal compounds and alkaline earth metal compounds and at least It is formed by developing with the developing solution containing 1 type of surfactant, Comprising: It shall be removed after formation of the said side wall part.

  According to this invention, when developing the alkali development type DFR, the same developer as that of the invention of claim 1 is used, so that there is almost no DFR residue on the surface of the piezoelectric element on the ink chamber member side. As a result, even if the side wall portion of the ink chamber hole in the ink chamber member is formed on the surface by plating, a pit is generated in the side wall portion, or a convex portion is generated on the surface opposite to the piezoelectric element. Can be suppressed. Therefore, problems such as adjacent ink chambers communicating with each other, ink in the ink chambers mixing with each other, crosstalk, and the like are less likely to occur. Further, it is difficult for the convex portion to be formed on the surface of the ink chamber member opposite to the piezoelectric element, and as a result, the problem that ink leaks from the gap between the surface and the nozzle plate is difficult to occur. Therefore, an ink jet head with good quality can be obtained.

  In the invention of claim 4, in the invention of claim 3, the total content of the metal compound in the developer is 0.1 wt% or more and 5 wt% or less, and the total content of the surfactant is 0.1 wt%. % To 20% by weight.

  Thus, the same effect as that of the invention of claim 2 can be obtained, and the quality of the ink jet head can be improved reliably.

  In the invention of claim 5, in the invention of claim 3 or 4, the side wall portion of the ink chamber hole in the ink chamber member is formed by electroless plating.

  That is, if the side wall portion of the ink chamber hole in the ink chamber member is formed by electroless plating, the surface opposite to the piezoelectric element in the ink chamber member can be made flat compared to the electrolytic plating. However, if DFR residue adheres to the surface of the piezoelectric element on the ink chamber member side, a convex portion is formed on the surface of the ink chamber member opposite to the piezoelectric element. Therefore, if the surface is not ground, a gap is formed between the nozzle plate and ink leaks from the gap. However, according to the present invention, since the amount of DFR residue can be reduced, it is difficult for a convex portion to be formed on the surface of the ink chamber member opposite to the piezoelectric element, and a surface with extremely good flatness can be obtained. Can be made unnecessary. Therefore, while reducing the manufacturing cost of the ink jet head, the surface of the ink chamber member opposite to the piezoelectric element and the nozzle plate can be reliably bonded without gaps, and ink ejection variation among the plurality of ink chambers. Can be prevented from occurring.

  According to the sixth aspect of the present invention, an ink chamber containing ink, an ink discharge port communicating with the ink chamber, and a plurality of layers including a first electrode layer, a piezoelectric layer, and a second electrode layer are laminated. Thus, the invention is an invention of a method of manufacturing an ink jet head including a piezoelectric element that is deformed in the stacking direction so as to reduce the volume of the ink chamber and discharges ink in the ink chamber from the ink discharge port.

  In the present invention, at least a first electrode layer, a piezoelectric layer, and a second electrode layer are stacked on the substrate to form a stacked body, and on the surface of the stacked body opposite to the substrate. A step of laminating an alkali-developable dry film resist, a step of exposing the alkali-developable dry film resist to a predetermined pattern through a mask pattern, and an alkali metal compound And developing with a developer containing at least one metal compound selected from the group of alkaline earth metal compounds and at least one surfactant to form a patterned alkaline development type dry film resist And patterning the alkali-developable dry film layer patterned on the surface of the laminate opposite to the substrate. The side wall of the ink chamber hole is formed by plating in the ink chamber member in which the ink chamber hole for forming the ink chamber is opened on the layered body side and the surface opposite to the layered body in the portion where the strike does not exist And the step of forming the ink chamber hole of the ink chamber member by removing the patterned alkaline developing dry film resist after the formation of the side wall portion of the ink chamber hole in the ink chamber member. And, after forming the ink chamber hole of the ink chamber member, joining a nozzle plate having an ink discharge port to the surface of the ink chamber member opposite to the laminate, and removing the substrate. Shall be included.

  According to the present invention, an ink jet head having the same effect as that of the invention of claim 3 can be easily manufactured.

  In the invention of claim 7, in the invention of claim 6, the total content of the metal compound in the developer is 0.1 wt% or more and 5 wt% or less, and the total content of the surfactant is 0.1 wt%. % To 20% by weight.

  Thus, an ink jet head having the same effect as that of the invention of claim 4 can be easily manufactured.

  In the invention of claim 8, in the invention of claim 6 or 7, the formation of the side wall portion of the ink chamber hole in the ink chamber member is performed by electroless plating.

  Thus, an ink jet head having the same effect as that of the invention of claim 5 can be easily manufactured.

  The invention of claim 9 is an invention of an ink jet recording apparatus. In this invention, the ink jet head according to any one of claims 3 to 5 and the relative movement for relatively moving the ink jet head and the recording medium. And a signal supply means for supplying a recording signal to the ink jet head, and the recording signal supplied from the signal supply means when the ink jet head is moved relative to the recording medium by the relative movement means. Accordingly, it is assumed that the recording is performed by discharging the ink in the ink chamber to the recording medium from the ink discharge port of the inkjet head.

  According to the present invention, a high-quality recording apparatus capable of printing a high-definition image can be easily realized.

  As described above, according to the developer of the alkali development type DFR of the present invention, at least one metal compound selected from the group of alkali metal compounds and alkaline earth metal compounds, and at least one surfactant, As a result, the amount of DFR residue adhering to the plating formation surface can be reduced as much as possible.

  Further, according to the ink jet head, the manufacturing method thereof, and the ink jet recording apparatus of the present invention, the DFR is patterned using the developer at the time of forming the mold when forming the ink chamber member, so that they are adjacent to each other. Ink leaks from the gap between the surface of the ink chamber member opposite to the piezoelectric element and the nozzle plate, such as ink chambers communicating with each other and ink in the ink chambers mixing or crosstalk. Thus, the quality of the ink jet head, and hence the quality of the recording apparatus, can be improved.

  Hereinafter, embodiments of the present invention will be described in detail.

(Embodiment 1)
The developer of the alkaline development type DFR according to the embodiment of the present invention is capable of reducing the residual amount of the DFR when the DFR is developed, and is from the group of alkali metal compounds and alkaline earth metal compounds. It contains at least one selected metal compound and at least one surfactant. This developer usually contains water in addition to the metal compound and the surfactant. Accordingly, the metal compound is preferably a water-soluble metal compound such as Na ₂ CO ₃ , and an aqueous solution containing the metal compound is prepared, and the surfactant is added to the aqueous solution to thereby prepare the developer. It can be easily manufactured.

  As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant can be used.

  Specific examples of the anionic surfactant include alkyl sulfonate, polyoxyethylene alkyl ether sulfonate, N-acyl amino acid salt, N-acyl methyl taurate, polyoxyethylene alkyl ether sodium acetate, alkyl sulfo Examples thereof include carboxylates, alkyl sulfonates, polyoxyethylene ether phosphates, and the like.

  Examples of the cationic surfactant include halogenated alkyl quaternary ammonium salts and alkylpyridinium salts.

  Examples of the amphoteric surfactant include alkylbetaine type, alkylimidazole type, and alkylamino acid type.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether type, polyoxyethylene alkyl phenyl ether type, polyoxyethylene polyoxypropylene alkyl ether type, polyoxyethylene glycol fatty acid ester type, sorbitan fatty acid ester type, polyglycerin fatty acid An ester type thing etc. can be mentioned.

  The total content of the metal compound is preferably from 0.1% to 5% by weight, and the total content of the surfactant is preferably from 0.1% to 20% by weight. When the content of this surfactant is less than 0.1% by weight, the amount of the surfactant adhering to the small piece that becomes the residue of the DFR is reduced, and the effect of reducing the amount of residue cannot be sufficiently obtained. If the amount is more than 20% by weight, the development characteristics of the DFR by the developer are deteriorated. In addition, the total content of the metal compound, combined with the total content of the above surfactant, suppresses the decrease in DFR development characteristics due to the developer, and the maximum effect of reducing the residual amount is obtained. Therefore, the content is preferably 0.1% or more and 5% by weight or less.

  Here, a specific example will be described.

First, various types of surfactants were added to an aqueous Na ₂ CO ₃ solution containing Na ₂ CO ₃ as the metal compound to prepare 20 types of developers (Examples 1 to 20). Table 1 shows the types and contents of the surfactants in the developers of Examples 1 to 20. That is, in Examples 1 to 5, the surfactant is an alkyl sulfonate of the anionic surfactant, and in Examples 6 to 10, the halogenated (chlorinated) alkyl quaternary of the cationic surfactant is used. In Examples 11 to 15, the alkylbetaine type of the amphoteric surfactant is used, and in Examples 16 to 20, the polyoxyethylene alkyl ether type of the nonionic surfactant is used. It was. The content of Na ₂ CO ₃ was set to 1 wt% in Examples 1 to 20 all.

For comparison, an aqueous Na ₂ CO ₃ solution containing no surfactant (containing 1 wt% Na ₂ CO ₃ ) was prepared as Comparative Example 1.

  Next, the amount of residual DFR when the alkali development DFR was developed using the developers of Examples 1 to 20 and Comparative Example 1 was examined.

  Specifically, samples for evaluation as shown in FIGS. 1 and 2 were prepared and the amount of DFR residue was examined. That is, a plating start layer 2 made of Ni having a thickness of 0.5 μm is formed on the silicon substrate 1 by a sputtering method, and an alkali development type DFR3 (trade name: AR-340) having a thickness of 40 μm is formed on the entire top surface of the plating start layer 2. , Manufactured by Tokyo Ohka Kogyo Co., Ltd.), and this DFR3 was patterned. That is, the DFR 3 formed on the entire upper surface of the plating start layer 2 is exposed through a mask pattern, and then is swung for 90 seconds in the developers of Examples 1 to 20 and Comparative Example 1 to be unexposed portions. As shown in FIG. 1, it was patterned to have a shape having a circular hole 4 having a diameter of 200 μm at the center of a square having a side of 500 μm.

  Then, after development of the DFR 3, the evaluation sample is washed with pure water so as not to be dried, and then the evaluation sample is dried, and the blue color adhering to the upper surface of the plating start layer 2 in the circular hole 4 is dried. The number of residues 5 (small pieces) of DFR3 was counted with an optical microscope. The results are shown in Table 1.

As is apparent from Table 1, it can be seen that the number of DFR3 residues 5 adhering to the upper surface of the plating start layer 2 can be remarkably reduced by adding a surfactant to the Na ₂ CO ₃ aqueous solution. This is because the surfactant in the developer adheres to the small piece that becomes the residue of DFR 3, and this surfactant makes it difficult for the small piece to adhere to the upper surface of the plating start layer 2.

In the above examples, the content of Na ₂ CO ₃ was set to 1% by weight. However, when the same test as in the above examples was performed while changing the content in the range of 0.1 to 5% by weight, the development time was Although changed, the number of DFR3 residues could be reduced to the same level as in the above example by adding a surfactant.

Further, even if Na ₂ CO ₃ is replaced with another water-soluble alkali metal compound or a water-soluble alkaline earth metal compound (any one kind of metal compound), the same effect as in the above embodiment can be obtained. Even when two or more kinds of metal compounds were contained, the same effects as those in the above examples were obtained by setting the total content to 0.1 to 5% by weight.

  Further, even when two or more kinds of surfactants are contained, the total content is in the range of 0.1 to 20% by weight, and the above examples in the case where one kind of surfactant is added Similar effects were obtained.

  Further, even when the contents of the metal compound and the surfactant were out of the above ranges, respectively, it was confirmed that although the effect of reducing the amount of DFR3 residue was inferior, it was better than the comparative example.

  Therefore, as a developer for an alkali development type DFR, by containing at least one metal compound selected from the group of alkali metal compounds and alkaline earth metal compounds and at least one surfactant, It is possible to reduce the amount of DFR residue remaining in the non-existing portion. As a result, even if the plating structure portion is formed in a portion where no DFR is present, it is possible to suppress the occurrence of pits in the interior or the occurrence of protrusions on the plating surface.

(Embodiment 2)
FIG. 3 shows an ink jet head according to an embodiment of the present invention (note that FIG. 3 is a cross-sectional view of the ink jet head taken along the line III-III in FIG. 4). This ink jet head includes an ink chamber member 8 made of Ni having a thickness of 35 μm, a piezoelectric element 9 in which a first electrode layer 10, a piezoelectric layer 11, and a second electrode layer 12 are sequentially laminated, and stainless steel. The nozzle plate 13 which consists of these. The ink chamber member 8 is provided on one surface of the piezoelectric element 9 in the stacking direction (thickness direction). As shown in FIG. 4, both sides of the ink chamber member 8 in the thickness direction (piezoelectric element 9 side) are provided. A plurality of openings (400 in this embodiment) each having a substantially rectangular shape (length 2 mm × width 35 μm in this embodiment) on the surface (upper surface) and the surface (lower surface) opposite to the piezoelectric element 9. Ink chamber hole 8a. In the present embodiment, the ink chamber holes 8a are arranged in four columns (each corresponding to four colors of ink of black, cyan, yellow, and magenta) × 100 rows, and are adjacent to each other in each column. The pitch between the ink chamber holes 8a is 70 μm.

  Portions of the ink chamber member 8 other than the ink chamber holes 8a constitute side wall portions 8b of the ink chamber holes 8a. The side wall 8b of the ink chamber hole 8a in the ink chamber member 8 is a surface of the piezoelectric element 9 on the ink chamber member 8 side (the ink chamber of the second electrode layer 12), as will be described in the manufacturing method described later. The surface of the member 8 is formed by electrolytic plating using an alkali developing DFR 16 (see FIG. 5) patterned so as to correspond to the position of the ink chamber hole 8a of the ink chamber member 8. . The patterned alkali development type DFR 16 is laminated on the entire surface of the piezoelectric element 9 on the ink chamber member 8 side before the formation of the side wall 8b of the ink chamber hole 8a in the ink chamber member 8, and the mask pattern. The alkaline development type DFR 16 exposed through the step is developed with the developer described in the first embodiment, and is removed after the side wall portion 8b is formed.

  The piezoelectric element 9 is provided on one surface (upper surface) in the thickness direction of the ink chamber member 8, while the nozzle is bonded to the other surface (lower surface) with an epoxy resin on the other surface (lower surface). A plate 13 is provided, and each ink chamber hole 8 a of the ink chamber member 8 is formed as an ink chamber 14 by covering both upper and lower openings with the piezoelectric element 9 and the nozzle plate 13. Is filled with ink.

  The nozzle plate 13 has a plurality of ink discharge ports 13a (nozzle holes) communicating with the ink chambers 14, respectively, and the ink in the ink chambers 14 is discharged from the ink discharge ports 13a to the outside (recording medium). It has come to be. Although not shown, the nozzle plate 13 is provided with a plurality of ink supply paths for supplying ink to the ink chambers 14, and an ink tank (not shown) passes through the ink supply path. Ink is supplied to each ink chamber 14.

  The first electrode layer 10 of the piezoelectric element 9 is made of Pt having a thickness of 0.1 μm, and is patterned to correspond to the position of the ink chamber hole 8a of the ink chamber member 8 to be an individual electrode. ing. On the other hand, the second electrode layer 12 is made of Cu having a thickness of 5 μm and serves as a common electrode, and when the side wall portion 8b of the ink chamber hole 8a of the ink chamber member 8 is formed by electrolytic plating. The plating start layer and the diaphragm layer are also used and are located closest to the ink chamber member 8 side. Note that the second electrode layer 12 is not limited to Cu, and if it is a conductive metal, it has all the functions of the electrode layer, the plating start layer, and the diaphragm layer. Further, a plating start layer may be separately provided between the second electrode layer 12 and the ink chamber member 8 (the vibration plate layer is also used as the second electrode layer or the plating start layer). A layer and a plating start layer (where the plating start layer is located closest to the ink chamber member 8) may be provided separately.

  The piezoelectric layer 11 is made of PZT (Zr / Ti composition ratio Zr / Ti = 53/47) having a thickness of 2 μm. In this embodiment, the piezoelectric layer 11 is not patterned, but may be patterned in the same shape as the first electrode layer 10.

  The piezoelectric element 9 is deformed in the stacking direction by applying a voltage to the piezoelectric layer 11 through the first electrode layer 10 and the second electrode layer 12, thereby forming the ink chamber 14. The ink inside is ejected from the ink ejection port 13a. That is, when a pulse voltage is applied between the first and second electrode layers 10 and 12, the piezoelectric layer 11 contracts in a direction perpendicular to the thickness direction due to the rise of the pulse voltage, whereas the first Since the second electrode layers 10 and 12 do not contract, a portion corresponding to the ink chamber 14 in the piezoelectric element 9 is bent and deformed in a convex shape toward the ink chamber 14 in the stacking direction due to a so-called bimetal effect. Due to this bending deformation, a pressure is generated in the ink chamber 14, and the ink in the ink chamber 14 is discharged to the outside from the ink discharge port 13a by this pressure. Then, the piezoelectric layer 11 expands due to the fall of the pulse voltage and the piezoelectric element 9 returns to the original state. At this time, the ink chamber 14 is filled with ink through the ink supply path.

  Next, a schematic procedure of the inkjet head manufacturing method will be described with reference to FIG.

  First, as shown in FIG. 5A, a first electrode layer 10, a piezoelectric layer 11 and a second layer are formed on a silicon substrate 15 having a diameter of 4 inches (a size capable of simultaneously forming 10 ink jet heads). The electrode layers 12 are laminated in this order to form a laminate 18. That is, first, the first electrode layer 10 (Pt film) is formed by sputtering. At this time, in order to improve the adhesion with the substrate 15, the substrate 15 is heated to 400 ° C., the process pressure is set to 0.5 Pa, and the applied high-frequency power is set to 100W.

  Subsequently, a piezoelectric layer 11 (PZT film) is formed on the first electrode layer 10 by sputtering. When the piezoelectric layer 11 is formed, the substrate 15 is heated to 600 ° C., the process pressure is set to 0.4 Pa, and the applied high frequency power is set to 300 W.

  Next, a second electrode layer 12 (Cu film) is formed on the piezoelectric layer 11 by a sputtering method. When the second electrode layer 12 is formed, the substrate 15 is heated to 100 ° C., the process pressure is set to 1 Pa, and the applied high frequency power is set to 400 W. In this way, a laminated body 18 obtained by laminating the first electrode layer 10, the piezoelectric layer 11, and the second electrode layer 12 on the substrate 15 is obtained.

Next, the 40 μm-thick alkali developing DFR 16 is laminated on the surface of the laminate 18 opposite to the substrate 15 (on the second electrode layer 12) at a temperature of 105 ° C. and a pressure of 0.29 MPa. A predetermined pattern mask (not shown) is installed between the DFR 16 and the 16 W / cm ² exposure machine, and a portion of the DFR 16 corresponding to the position of the ink chamber hole 8a of the ink chamber member 8 is exposed for 10 seconds.

  Subsequently, the exposed DFR 16 is developed while swinging in the developer described in the first embodiment for 1 minute to remove the non-exposed portion. Washing with water is performed to form a patterned DFR 16 having a height (thickness) of 40 μm, a length of 2 mm, and a width of 35 μm, as shown in FIG.

  Next, the natural oxide layer formed on the portion where the DFR 16 does not exist on the second electrode layer 12 is removed with HCl, and then is put into a Ni plating bath at 50 ° C. so as to be plated with the second electrode layer 12. By applying a DC voltage of 10 V to the electrode for 45 minutes for 45 minutes, as shown in FIG. 5C, the DFR 16 is used as a mold in the ink chamber in the portion where the DFR 16 does not exist on the second electrode layer 12. A side wall 8b of the ink chamber hole 8a in the member 8 is formed.

  In general, since electroplating causes variations in thickness and burrs due to variations in electric field strength, the plating surface (surface opposite to the laminate 18 of the side wall portion 8b) is ground to adjust the height, Thereafter, the DFR 16 is removed using an aqueous solution containing 1% by weight of KOH, whereby the ink chamber hole 8a of the ink chamber member 8 is formed. Thereby, as shown in FIG.5 (d), the ink chamber member 8 formed by electrolytic plating is obtained.

Subsequently, as shown in FIG. 5E, the substrate 15 is removed by etching for 5 hours with an aqueous solution containing KOH at a temperature of 80 ° C. and 10 wt%.
Next, as shown in FIG. 5 (f), the nozzle plate 13 in which the ink discharge ports 13 a and the like are formed in advance is bonded to the surface of the ink chamber member 8 opposite to the laminated body 18 with an epoxy resin. To do. The nozzle plate 13 may be joined after the ink chamber hole 8a of the ink chamber member 8 is formed and before the substrate 15 is removed.

  After the substrate 15 is removed, the piezoelectric element 9 is formed by finishing each layer of the laminate 18 in a predetermined shape. In this embodiment, the first electrode layer 10 is patterned so as to correspond to the position of the ink chamber hole 8 a of the ink chamber member 8. Thus, 10 ink jet heads are obtained in a connected state, and 10 ink jet heads are completed simultaneously by cutting and dividing them.

  Here, as Example 21, a total of 100 inkjet heads similar to those in the second embodiment were produced by the same method as in the manufacturing method. At this time, the alkali development type DFR 16 is the same as that used when examining the residual amount when developed with the developers of Examples 1 to 20 and Comparative Example 1 described above. The same as 9. Moreover, the brand name N-100ES (made by Nippon High Purity Chemical Co., Ltd.) was used for the plating solution of the plating rod.

  On the other hand, for comparison, the same DFR16 developer as in Comparative Example 1 in Embodiment 1 above was used, and 100 ink jet heads other than that in Example 21 above were prepared (Comparative Example 2).

  Then, ink is filled in the ink chambers 14 of the inkjet heads of Example 21 and Comparative Example 2, and a voltage is applied between the first and second electrode layers 10 and 12 so that the ink is ejected from the ink ejection port 13a. In the comparative example 2, the ink chambers 14 adjacent to each other communicate with 60 inkjet heads by pits generated in the side wall portion 8b of the ink chamber hole 8a in the ink chamber member 8 during electroplating. I found out that there was a defect. On the other hand, in Example 21, the number of ink jet heads in which such a defect due to pits occurred was three.

  Therefore, the pattern is obtained by developing the alkali developing DFR 16 with a developer containing at least one metal compound selected from the group of alkali metal compounds and alkaline earth metal compounds and at least one surfactant. And forming the side wall portion 8b of the ink chamber hole 8a in the ink chamber member 8 by electrolytic plating using the patterned alkali development type DFR16 as a mold, thereby suppressing the generation of pits in the side wall portion 8b, Adjacent ink chambers 14 communicate with each other and problems such as mixing of inks in the ink chambers 14 and crosstalk are less likely to occur.

(Embodiment 3)
The configuration of the ink jet head according to the present embodiment is basically the same as that of the second embodiment, but the side wall portion 8b of the ink chamber hole 8a in the ink chamber member 8 is not electroplated but Ni electroless. The point which forms by plating and the point which comprises the 2nd electrode layer 12 with the alloy of Ni and Pd differ from the said Embodiment 2. FIG. The second electrode layer 12 (plating start layer) may be a single metal having an autocatalytic action on the plating solution or an alloy containing this metal. In the case of Ni electroless plating, the Ni plating solution Metals having an autocatalytic action are Pd, Ni and Fe.

  The ink jet head manufacturing method of this embodiment is also basically the same as that of the second embodiment, but the formation process of the side wall 8b of the ink chamber hole 8a in the ink chamber member 8 is different. That is, in this side wall portion 8b forming step, the side wall portion 8b is formed by putting it in a Ni plating bath at 80 ° C. and performing electroless plating for 2 hours while adjusting the concentration of the plating solution in the soot. When the side wall portion 8b is formed by electroless plating in this way, the thickness of the ink chamber member 8 becomes uniform throughout, so there is no need to adjust the plating surface height by grinding as in the second embodiment. .

  Here, as Example 22, a total of 100 inkjet heads similar to those in the third embodiment were manufactured by the same method as the above manufacturing method. At this time, the alkali development type DFR 16 is the same as that used when examining the residual amount when developed with the developers of Examples 1 to 20 and Comparative Example 1 described above. The same as 9. Moreover, the brand name N-1000 (made by Japan High-Purity Chemical Co., Ltd.) was used for the plating solution of the plating rod. Furthermore, the plating surface is not ground.

  On the other hand, for comparison, the same DFR16 developer as in Comparative Example 1 in Embodiment 1 was used, and 100 inkjet heads other than that in Example 22 were prepared (Comparative Example 3).

  Then, ink is filled into the ink chambers 14 of the inkjet heads of Example 22 and Comparative Example 3, and the voltage is applied between the first and second electrode layers 10 and 12 so that the ink is discharged from the ink discharge port 13a. In the comparative example 3, the ink chambers 14 adjacent to each other are communicated with 20 ink-jet heads by pits generated in the side wall portion 8b of the ink chamber hole 8a in the ink chamber member 8 during electroless plating. The ink chamber member is caused by a convex portion formed on the plating surface (surface opposite to the piezoelectric element 9 in the ink chamber member 8) due to abnormal growth during electroless plating in 40 inkjet heads. It was found that there was a defect that a gap was generated between the nozzle plate 13 and the nozzle plate 13 and ink leaked from the gap. On the other hand, in Example 22, the two inkjet heads had a defect that the ink leaked due to the convex portion of the plating surface, but there were no inkjet heads that failed due to the pits.

  Therefore, the pattern is obtained by developing the alkali developing DFR 16 with a developer containing at least one metal compound selected from the group of alkali metal compounds and alkaline earth metal compounds and at least one surfactant. By forming the side wall 8b of the ink chamber hole 8a in the ink chamber member 8 by electroless plating using the patterned alkali development type DFR 16 as a mold, generation of pits in the side wall 8b is suppressed. In addition, the occurrence of convex portions on the plating surface is suppressed. As a result, problems such as adjacent ink chambers 14 communicating with each other and ink in the ink chambers 14 mixing and crosstalk are less likely to occur, and opposite to the piezoelectric element 9 in the ink chamber member 8. Even if the side surface is not ground, the problem of ink leakage from the gap between the surface and the nozzle plate 13 is less likely to occur.

(Embodiment 4)
FIG. 6 shows an ink jet recording apparatus according to an embodiment of the present invention, and this ink jet recording apparatus includes an ink jet head 22 similar to that described in the second or third embodiment. The ink in the ink chamber is recorded from the ink discharge port (ink discharge port 13a in the second or third embodiment) provided to communicate with the ink chamber (ink chamber 14 in the second or third embodiment) in the inkjet head 22. The recording is performed by ejecting the recording medium 26 (recording paper or the like).

  The inkjet head 22 is mounted on a carriage 24 provided on a carriage shaft 23 extending in the main scanning direction X, and reciprocates in the main scanning direction X as the carriage 24 reciprocates along the carriage shaft 23. It is configured to move. Thus, the carriage 24 constitutes a relative movement unit that relatively moves the inkjet head 22 and the recording medium 26 in the main scanning direction X.

  In addition, the ink jet recording apparatus includes a plurality of rollers 25 that move the recording medium 26 in the sub-scanning direction Y substantially perpendicular to the main scanning direction X. Thus, the plurality of rollers 25 constitute a relative moving unit that relatively moves the inkjet head 22 and the recording medium 26 in the sub-scanning direction Y. In FIG. 6, Z is the vertical direction.

  The ink jet head 22 is connected to a signal supply means 27 (controller or the like) for supplying a recording signal to the ink jet head 22, and when the ink jet head 22 is moved in the main scanning direction X by the carriage 24, In accordance with the recording signal supplied from the signal supply means 27, ink is ejected from the ink ejection port of the inkjet head 22 onto the recording medium 26 to perform recording. When the one-scan recording is completed, the recording medium 26 is moved by a predetermined amount by the roller 25 to perform the next one-scan recording.

  Therefore, since the ink jet recording apparatus includes the ink jet head 22 similar to that of the second or third embodiment, a high-definition image can be printed and the quality can be improved.

  In the fourth embodiment, the inkjet head 22 is moved in the direction (X direction) perpendicular to the moving direction (Y direction) of the recording medium 26, but the plurality of inkjet heads 22 are moved in the moving direction of the recording medium 26. By arranging them in the entire perpendicular direction, scanning in the arrangement direction (X direction) becomes unnecessary. In this case, the recording medium 26 is supplied from the signal supply unit 27 when the recording medium 26 is moved by the roller 25 (which constitutes a relative moving unit that moves the inkjet head 22 and the recording medium 26 relative to each other). In accordance with the signal, ink may be ejected from the ink ejection port of the inkjet head 22 onto the recording medium 26 to perform recording, and in this way, printing can be performed at high speed.

  The developer of the alkali development type dry film of the present invention has a patterned plating structure for constituting an ink chamber of an inkjet head, a reaction chamber of μ-TAS, a liquid flow path, a micromirror, a microswitch, and the like. Useful when making.

It is a top view which shows the sample for evaluation for evaluating the reduction effect of the residual amount of the alkali development type DFR by the developing solution concerning the embodiment of the present invention. It is the II-II sectional view taken on the line of FIG. It is sectional drawing which shows the inkjet head which concerns on embodiment of this invention. It is a top view which shows the ink chamber member of an inkjet head. It is the schematic which shows the manufacturing method of an inkjet head. 1 is a schematic perspective view showing an ink jet recording apparatus according to an embodiment of the present invention. It is a top view which shows the state patterned into groove shape by developing DFR on a board | substrate with a developing solution. It is the VIII-VIII sectional view taken on the line of FIG.

Explanation of symbols

8 Ink chamber member 8a Ink chamber hole 8b Side wall portion 9 of ink chamber hole Piezoelectric element 10 First electrode layer 11 Piezoelectric layer 12 Second electrode layer 13 Nozzle plate 13a Ink discharge port 14 Ink chamber 15 Substrate 16 Alkali Development type dry film resist 18 Laminate 22 Inkjet head 24 Carriage (relative movement means)
25 Roller (relative movement means)
26 Recording medium 27 Signal supply means

Claims (9)

  An alkaline developing dry film resist developer comprising at least one metal compound selected from the group consisting of alkali metal compounds and alkaline earth metal compounds and at least one surfactant.   The total content of the metal compound is 0.1 wt% or more and 5 wt% or less, and the total content of the surfactant is 0.1 wt% or more and 20 wt% or less. Alkali development type dry film resist developer. An ink chamber containing ink, an ink discharge port communicating with the ink chamber, and a plurality of layers including a first electrode layer, a piezoelectric layer, and a second electrode layer are laminated, and the volume of the ink chamber An inkjet head including a piezoelectric element that is deformed in the laminating direction so as to decrease, and discharges ink in the ink chamber from the ink discharge port,
An ink chamber member having an ink chamber hole for constituting the ink chamber opened on the piezoelectric element side and a surface opposite to the piezoelectric element is provided on a surface on one side in the stacking direction of the piezoelectric elements,
A nozzle plate having the ink discharge port is bonded to the surface of the ink chamber member opposite to the piezoelectric element,
The side wall portion of the ink chamber hole in the ink chamber member is formed on the surface of the piezoelectric element on the ink chamber member side so as to correspond to the ink chamber hole position of the ink chamber member. It is formed by plating using a film resist as a mold,
The patterned alkali development type dry film resist is laminated on the entire surface of the piezoelectric element on the ink chamber member side and formed with a mask pattern before forming the side wall portion of the ink chamber hole in the ink chamber member. The alkali-developable dry film resist exposed through the film is developed with a developer containing at least one metal compound selected from the group of alkali metal compounds and alkaline earth metal compounds and at least one surfactant. An ink jet head formed by performing the steps described above and removed after the side wall portion is formed.   The total content of the metal compound in the developer is from 0.1% by weight to 5% by weight, and the total content of the surfactant is from 0.1% by weight to 20% by weight. Item 4. The inkjet head according to Item 3.   5. The ink jet head according to claim 3, wherein a side wall portion of the ink chamber hole in the ink chamber member is formed by electroless plating. An ink chamber containing ink, an ink discharge port communicating with the ink chamber, and a plurality of layers including a first electrode layer, a piezoelectric layer, and a second electrode layer are laminated, and the volume of the ink chamber A method of manufacturing an ink-jet head comprising: a piezoelectric element that is deformed in the laminating direction so as to decrease and discharges ink in the ink chamber from the ink discharge port,
Forming a laminate by laminating at least a first electrode layer, a piezoelectric layer, and a second electrode layer on a substrate;
Laminating an alkali development type dry film resist on the surface opposite to the substrate of the laminate,
Exposing the alkali-developable dry film resist to a predetermined pattern through a mask pattern;
The exposed alkali development type dry film resist is developed with a developer containing at least one metal compound selected from the group of alkali metal compounds and alkaline earth metal compounds and at least one surfactant. A step of forming a patterned alkali development type dry film resist,
On the surface of the laminate opposite to the substrate, the ink chamber hole for forming the ink chamber is opposite to the laminate and the laminate on the portion where the patterned alkali development type dry film resist is not present. Forming a side wall portion of the ink chamber hole in the ink chamber member opened on the side surface by plating;
Forming the ink chamber hole of the ink chamber member by removing the patterned alkaline developing dry film resist after the formation of the side wall of the ink chamber hole in the ink chamber member;
After forming the ink chamber hole of the ink chamber member, joining a nozzle plate having an ink discharge port to the surface of the ink chamber member opposite to the laminated body and removing the substrate. A method of manufacturing an ink-jet head.   The total content of the metal compound in the developer is from 0.1% by weight to 5% by weight, and the total content of the surfactant is from 0.1% by weight to 20% by weight. Item 7. A method for producing an inkjet head according to Item 6.   8. The method of manufacturing an ink jet head according to claim 6, wherein the side wall portion of the ink chamber hole in the ink chamber member is formed by electroless plating. An inkjet head according to any one of claims 3 to 5;
Relative movement means for relatively moving the inkjet head and the recording medium;
Signal supply means for supplying a recording signal to the inkjet head,
When the ink jet head is moved relative to the recording medium by the relative moving means, the ink in the ink chamber is discharged from the ink discharge port of the ink jet head according to the recording signal supplied from the signal supplying means. An ink jet recording apparatus configured to perform recording by ejecting the ink jet recording apparatus.

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