JPS61249765A - Preparation of liquid jet recording head - Google Patents

Abstract

PURPOSE:To provide an inexpensive ink jet recording head having high accuracy, good quality and high reliability, by providing a material which acts on the connection part of a cured resin film forming a liquid (ink) passage and a substrate to lower the close adhesiveness of both of them, therebetween to alleviate various stresses. CONSTITUTION:After the surface of a substrate wan purified and dried, for example, at 80-150 deg.C, the surface thereof is primarily treated at first with a silane coupling agent represented by formula I (wherein m is an integer of 1 or 2, R<1> is one or more of a group selected from a group consisting of an amino group, a vinyl group, a methacryl group, an epoxy group or a mercapto group, R<3> is chloro group, a methoxy group, an ethoxy group, an acetoxy group or a beta-methoxyethoxy group and R<3> is a methyl group or an ethyl group). After the treatment of the primary coupling agent was finished, the primarily treated surface of the substrate is succeedingly subjected to secondary treatment according to the same technique as the primary treatment by using a silane coupling agent represented by formula II (wherein n is an integer of 1-3, R<4> is one or more of a group selected from a group consisting of an amino group, a vinyl group, a methacryl group, an epoxy group, an ethoxy group, an acetoxy group or a beta-methoxyethoxy group). Next, a dry photoresist film is applied to the substrate surface having received the treatments of the first and second silane coupling agents.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a liquid jet recording head, specifically, a liquid jet recording head that generates ink droplets and attaches them to a recording material such as paper to perform recording. The present invention relates to a method of manufacturing a recording head for generating ink droplets used in a jet recording method.

[Conventional technology]

The liquid jet recording (inkjet recording) method, in which small droplets of recording liquid such as ink are generated and recorded by adhering them to a recording material such as paper, is extremely sensitive to the noise generated during recording, to the extent that it can be seen clearly. It has attracted attention as a recording method that is small and capable of high-speed recording, and can record on plain paper without the need for special processing such as fixing, and various types have been actively researched recently. .

The recording head section of a recording device used in the inkjet recording method generally includes an orifice (liquid ejection opening) for ejecting ink, and a part that communicates with the orifice and where energy for ejecting the ink acts on the ink. The ink passage (liquid passage) has an ink passage (liquid passage) and an ink chamber for storing ink to be supplied to the ink passage.

During recording, the energy for ejecting ink is generated by a heating element, a piezoelectric element, etc. arranged at a predetermined position in a part of the ink passage that applies ejection energy to the ink (energy application part). energy generating elements of various types.

A method for manufacturing an inkjet recording head having such a configuration is, for example, to form fine grooves on a flat plate of glass, metal, etc. by cutting or etching, and then to attach another suitable plate to the flat plate with the grooves formed thereon. For example, a groove may be formed by laminating a groove wall of a cured photosensitive resin on a substrate on which an ejection energy generating element is arranged using a photolithography process. A method is known that includes a step of joining another flat plate (cover) to the thus formed grooved plate to form an ink passage (for example, Japanese Patent Laid-Open No. 57-43878).

Among these methods for manufacturing inkjet recording heads, the latter method using photosensitive resin is superior to the former method (forming grooves on the substrate by cutting or etching), because it allows the ink passages to be formed with greater precision and yield. Since it can be finely processed and mass-produced easily, it has the advantage that it is possible to provide a high-quality and inexpensive inkjet recording head.

[Problem that the invention seeks to solve]

However, in the recording head formed by the conventional method using photosensitive resin as described above, peeling between the substrate and the photosensitive resin cured film forming the ink passage occurs during the manufacturing process.
Or, this often occurs during long-term use, and as a result, the predetermined shape of the ink passage or orifice is disturbed, resulting in the ink flow within the predetermined ink passage or the direction of ink droplet ejection from the orifice. In some cases, the normal ejection state is impaired, and it is not possible to obtain good recording characteristics (for example, impact point accuracy), which causes a decrease in the reliability of the recording head.

This deterioration in the recording characteristics of the recording head is a problem that must be solved in order to meet the various demands for inkjet recording systems to provide images with higher resolution and higher quality.

These problems are caused by, for example, 1) a method of curing the photosensitive resin on the substrate by treating it with light or heat to form the ink passages; therefore, when the resin is cured, the resin may shrink; , stress remains in the cured resin film on the substrate, and this stress acts in a direction that reduces the adhesion between the substrate and the cured resin film, and may even reach the point where the substrate and the cured resin film separate.

2) In order to form the orifice, there is a step of cutting the downstream side of the ink flow path of a laminate formed by laminating a substrate, a photosensitive resin cured film that forms an ink passage on the surface of the substrate, and a cover for the passage. 3) If the ink comes into contact with the joint between the cured resin film and the substrate for a long time, the resin at this joint will peel. The adhesion of the cured film to the substrate gradually decreases, and when exposed to temperature changes due to repeated operation and rest of the recording device, the decrease in adhesion is exacerbated, and peeling as described above is likely to occur. It is thought that this occurs due to an organic combination of factors such as .

Although various studies have been made to prevent such peeling between the cured resin film and the substrate, no solution having sufficient effects has yet been found.

The present invention has been made in view of these problems, and its purpose is to provide an inkjet recording head that is highly accurate, of good quality, inexpensive, and highly reliable.

Another object of the present invention is to provide a method for manufacturing an inkjet recording head that has excellent durability during long-term use and can always maintain good initial recording characteristics.

[Means for solving problems]

The above object can be achieved by the following method of the invention.

A method of manufacturing a liquid jet recording head according to the present invention includes forming a liquid passage communicating with an ejection port on a substrate provided with a liquid ejection energy generating element, and coating at least a part of the wall of the liquid passage with a photosensitive resin cured film. When manufacturing a liquid jet recording head composed of: the surface of the substrate on which the photosensitive resin cured film is laminated;

Prior to laminating the photosensitive resin to form the photosensitive resin cured film on several surfaces, the following general formula (1); % formula % () [In the above formula, m represents an integer of 1 or 2, R
1 represents a group having one or more selected from the group consisting of an amino group, a vinyl group, a methacrylic group, an epoxy group, and a mercapto group, and R2 represents a chloro group, a methoxy group, an ethoxy group, an acetoxy group, or a β-methoxyethoxy group. R3 represents a methyl group or an ethyl group] After the first treatment with a silane coupling agent represented by the following general formula % formula , R4 represents a group having one or more selected from the group consisting of an amino group, a vinyl group, a methacrylic group, an epoxy group, and a mercapto group, and R5 represents a chloro group, a methoxy group,
1. A method for manufacturing a liquid jet recording head, comprising performing a secondary treatment with a silane coupling agent represented by the following formula: ethoxy group, acetoxy group, or β-methoxyethoxy group.

That is, in the method of the present invention, prior to laminating a photosensitive resin for forming a photosensitive resin cured film on several surfaces of the substrate, the substrate surface is treated with a coupling agent as described above,
By alleviating the various stresses that act on the joints between the cured resin film and the substrate that form the liquid (ink) passages and reduce their adhesion, we also improve the ink resistance at these joints. The above-mentioned problems are solved by arranging a layer that prevents peeling of the cured resin film by improving the properties of the cured resin film.

Hereinafter, an example of the method for manufacturing an inkjet recording head of the present invention will be explained in detail with reference to the drawings.

FIGS. 1 to 9 are schematic diagrams for explaining the manufacturing procedure of the inkjet recording head of the present invention.

In the method of the present invention, first, as shown in FIG. 1, a desired number of ink ejection energy generating elements 1-2 such as heating elements or piezo elements are placed on a flat plate 1-1 made of glass, ceramic, plastic, or metal. 5i02, Ta205. A substrate 1 is formed by covering with a protective layer 1-3 such as glass. Note that, although not shown, a recording signal input electrode is connected to the ink ejection energy generating element 1-2.

Next, after cleaning the surface of the substrate l obtained through the steps shown in FIG. 1 and drying it at, for example, 80 to 150°C,
This surface is first treated with a silane coupling agent represented by the general formula (I).

Surface treatment with a silane coupling agent can be carried out by, for example, immersing the surface to be treated in a solution in which a predetermined amount of the silane coupling agent is dissolved in an appropriate solvent for a predetermined time, spraying a predetermined amount of the solution onto the surface to be treated, or This can be carried out by applying the coating to a predetermined thickness using a spinner coater or the like.

When the surface of the substrate 1 is treated with the silane coupling agent in this way, the substrate surface and the silane coupling agent react, and a first silane coupling agent layer 2-
1 is formed.

In addition, in order to promote the reaction between the substrate surface and the silane force/sampling agent, after surface treatment, it was heated at 80°C for 10 minutes.
It is best to heat it for about a minute.

In this first treatment, as mentioned above, the general formula (I)
The silane coupling agents shown in are used, and specific examples thereof include those categorized and exemplified on the main functional group side below.

1) Those having a vinyl group 1 a) Vinyldimethylethoxysilane (H2C=CHSi(CH:+hOC:2Hs) b)
Vinylethyldichlorosilane CHzC=CH3jCCH2CH3”)C12:)C)
Vinylmethyldiacetoxysilane (H7C=CHSi(CH3)(OCCH3)2)d)
Vinylmethyldichlorosilane CH2C=CH3i (CH3E A 2 )e) Vinylmethyldie) xysilane (H7C=CHSi(OH3) (OCR7CH3h )
f) Vinyldimethylchlorosilane CH2C=CH3l (CH3)2C father] g) Allylmethyldichlorosilane (H2C=CHCH25l (OL) 0 children 2] h) Allyldimethylchlorosilane (H2C=CHC:H2S i (CH3)2CA )
l) 7-octynyldimethylchlorosilane (JI2C=
CH(CH7)6si(C:H3), Cff1)J)5
-hexenyldimethylchlorosilane (H2C=CH(C
H2)+5i(CH3)2Gffi)2) Those having a methacryl group; a) 3-methacryloxypropyl-dimethylchlorosilane (H2C=C(CH3)GO(CH2)3s:(CH3
)2cR)b) 3-methacryloxypropyl-dimethylethoxysilanec) 3-methacryloxypropyl-methyljethoxysilane (H2C=C(CH3)Go(CHz)3Si(CH3
)(OCHzCH3h)d) 3-methacryloxypropyl- methyldichlorosilane (H2C=C(CH:+)Go(GH2hSi(CH3
) Cj! 2) 3) Those having an epoxy group; a) 3-glycidoxypropyl-dimethylethoxysilane b) 3-glycidoxypropyl-methyldimethoxysilane 4) Those having a mercapto group; a) 3-mercaptopropyl-methyl Dimethoxysilane C H2CH2C H2 CH2S i (OCl3
)20H3)5) Those having an amino group; a) W-β-(aminoethyl)-γ-aminopropyl-methyldimei-xysilane (H2NCH2 CH2N H(CH'2) 3S
i (CH3) (OCH3) 2 ) b) 4-7 Minobutyldimethylmethoxysilane CH2N (GHz) 4
si(OCH3)(CH3h)c) 3-aminopropyldimethylethoxysilane('H2N(CH2)
3S i (OCl2 CH3) (GH3')2)
d) 3-aminopropylmethyljethoxysilane C
H2N (GH2hS i (OCl(2 0H3)
2C I(3)e) 2-(2-aminoethylthioethyl)-jethoxymethylsilane (H2NcH2cH2scn2cH,, sI(cHs)
(ocu2cn3)2) When the above primary coupling agent treatment is completed, the surface of the substrate that has undergone the primary treatment is treated with the silane coupling agent represented by the general formula (TI). Secondary processing is performed using the same method as the next processing.

As the silane coupling agent used in this secondary treatment, the following examples can be listed based on a wide range of main functionalities, and an appropriate one selected from these can be used. The coupling agent used preferably has a functional group that reacts with the photosensitive resin layered on the substrate 2, and is capable of forming a highly adhesive bonding surface with the photosensitive resin.

1) Those having a vinyl group; a) Vinyltrichlorosilane (CH2=CH3iCJj
3] b) Vinyltrimethoxysilane CCH2= CH81 (CCH3) 3 ) C) Vinyltriethoxysilane (CH2=CH8i (QC2)+s) 3: ] d) Vinyltriacetoxysilane (CH2= CH8i (OCGH3) 3 ) e ) vinyl) Lis(β-methoxyethoxy)-silane (CH2=CH3i(QC:1bcH20cH3)3)
f) N-β-(N-vinylbenzylaminoethyl)-
γ-Aminopropyltrimethoxysilane (C:H2):
+Si(OCH3) 3 :] 2) Those having a methacryl group; a) γ-methacryloxypropyltrimethoxysilane CCH2=C-GO(CH2)3Si(OCH3h)
b) γ-methacryloxypropyl-tris-(β-methoxyethoxy)silane 3CO (CH2=C-Go(CH2):+Si(OCH2CH
20'CH3)3) 3) Those having an epoxy group: a) β-(3,4-epoxycyclohexyl)-b) γ
-glycidoxypropyltrimethoxysilane 4] Those having a mercapto group; a) γ-mercaptopropyltrimethoxysilane (HS
CH2(j(2CH2S i(OCH3)3)5) having an amino group; a) γ-aminopropyltrimethoxysilane (NH2C
H2C: H2CH2Si(OCH3)3 ) b) γ-Aminopropyltriethoxysilane C NH2C: H2
CH2C H2 Si (QC7 HS )3 )c
) N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane (NH2(CH2) 2NH(C:HzhS j
(OCH3)3)d) γ-[bis(β-hydroxyethyl)]-aminopropyltriethoxysilane ((HOCH2CH2)2N (CH2)3S
i (QC2 HS ) 3 ) e) γnyreidopropyltriethoxysilane (N) 1cONH (CHz) 3S
i(OC2Hs)3:]f) γ-anilinopropyltrimethoxysilaneg) CToO CCH2 CH2N
H(CH2)2N H(CH2) 3S i (OC
H3)3)6) Those having a methyl group; a) Methyltrichlorosilane (CH3SiCA 3
) b) Dimethyldichlorosilane ((CH3)2si(
:12)c)) Listylchlorosilane C (CH
3)3SiGffi)d) Methyltrimethoxysilane (CH3S i (OCH3)3 )e) Methyltriethoxysilane (CH3Si(OC2Hsh) f) Hexamethyldisilazane (((lH3)3siNHsi(CH3)3)7) Chloro Those having a group; a) γ-chloropropyltrimethoxysilane (Cl (
CH3)3Si(OCH3h)8) Those having a phenyl group; a) Phenyltrimethoxysilane c Qs (DC:H3) 3) b) Phenyltriethoxysilane Also in this secondary treatment, the substrate surface and the silane After surface treatment to promote reaction with coupling agent,
It is best to heat this at 80°C for about 10 minutes.

When the second silane coupling agent treatment is completed,
As shown in FIG.
A second silane coupling agent layer 2-2 having a surface with good adhesion to the photosensitive resin side to be further laminated is formed thereon.

The silane coupling agent layer formed in this way mainly consists of a first layer that has excellent adhesion to the substrate side and relieves the stress acting from the outside as described above, and a photosensitive layer. The second layer, which has excellent adhesion to the photosensitive resin cured film side, functions comprehensively to improve the adhesion between the substrate and the photosensitive resin cured film, and to alleviate stress acting on this part. This prevents these peelings as seen in conventional recording heads.

Next, a dry film photoresist I.3 (film thickness, approximately 251 i
ffI-100μ) at 0.5 to 0.4 f/min,
lamination at a speed of 1 to 3 Kg/cI113.

Subsequently, as shown in FIG. 3, a photomask 4 having a pattern of a predetermined shape that does not transmit light is superimposed on the dry film photoresist 3 provided on the surface of the substrate 1. Exposure (arrows in the figure) is carried out from the second part.

The photomask 4 and the substrate 1 are aligned so that the element 2 is provided in the ink passage area that will be finally formed through steps such as exposure and development.
For example, alignment marks can be drawn in advance on each of the substrate 1 and the mask 4, and alignment can be performed according to the marks.

When the exposure is performed in this way, the area other than the area covered by the pattern, that is, the exposed part of the photoresist 3 is polymerized and hardened, and the unexposed area remains solvent-soluble, whereas it becomes solvent-insoluble. becomes.

After completing the pattern exposure of photoresist 3, next
The exposed photoresist 3 is developed by immersing it in a volatile organic solvent such as trichloroethane to obtain a dry film photoresist 3 that is soluble in the solvent.
The unpolymerized (uncured) portion of is dissolved and removed from the substrate 1, and $
As shown in FIG. 4, the hardened photoresist film 3P remaining on the substrate 1 forms a groove 7 that will eventually become an ink passage and an ink supply chamber (not shown in FIG. 4).

Next, the hardened photoresist film 3P on the substrate l is
For the purpose of improving the ink resistance of
Further heat polymerization by heating at 8C to 25Q'C for about 30 minutes to 6 hours, or add 50 to 200mW/C11 to this.
Since the strength is 2, it is further cured by irradiation with ultraviolet rays.

Note that it is more effective to use these methods in combination.

Note that in the example of the method of the present invention described above, grooves that will become ink passages and ink supply chambers are formed.

Although a dry film type, that is, a solid type photosensitive resin (photoresist) is used, the photosensitive resin that can be used in the method of the present invention is not limited to solid type. Of course, liquid ones can also be used.

As a method for forming a photosensitive resin film on a substrate, when using a liquid photosensitive resin composition, 1. For example, a method using a squeegee used when creating a relief image, that is, a coating film of a desired photosensitive resin cured film. Examples of methods include providing a wall with a height corresponding to the thickness of the substrate around the substrate and removing excess resin composition with a squeegee.

In this case, the viscosity of the photosensitive resin composition is 100 cp to 3
00cp is appropriate. Further, the height of the walls placed around the substrate must be determined in consideration of the amount of weight loss due to evaporation of the solvent contained in the photosensitive resin composition.

On the other hand, when using a solid photosensitive resin, it is preferable to adhere the photosensitive resin sheet onto the substrate by heat-pressing it.

Among these, those applicable to the method of the present invention are:
A solid film type material is convenient for handling and for controlling the thickness easily and accurately.

Examples of such solid materials include permanent polymer coatings such as RISTON.
) Solder mask 730S, 740S, 730
FR1 740FR, SM 1, Kapton (KAP
TON) XA-A3, XA-83, XA-AI
, XA-M3, XA-03 (manufactured by DuPont); Photoc PHT series, SR series (manufactured by Hitachi Chemical), DFRE-15, P-2
5. P-38, T-50 (manufactured by Asahi Kasei); NEOTOROCK E type, T type (manufactured by Nitto Denko Corporation); Thioko
l) Those commercially available under trade names such as Laminar GT, Laminar GSI, and Laminar TO1 TA (manufactured by Tokyo Ohka Co., Ltd.) can be used.

In addition, in the method of the present invention, many of the photosensitive resins used in the field of ordinary photolithography can be used, such as diazoresin, P-diazoquinone, or A photopolymerizable photopolymer using a vinyl monomer etc. and a polymerization initiator, an engineered photopolymer using a polyvinyl cinnamate etc. and a sensitizer, a mixture of ornaphthoquinone diazide and a novolac type phenolic resin,
Mixtures of polyvinyl alcohol and diazo resins, polyether type photopolymers made by copolymerizing 4-glycidyl ethylene oxide with benzophenone or glycidyl chalcone, copolymers of N,N-dimethylmethacrylamide with e.g. acrylamide benzophenone, unsaturated polyesters. Photosensitive resins [e.g., APR (manufactured by Asahi Kasei), Tevista (manufactured by Kijinsha), Sonne (manufactured by Kansai Paint Co., Ltd.)]
, unsaturated urethane oligomer-based photosensitive tung fat, photosensitive resin composition in which a photopolymerization initiator and polymer are mixed with bisensitized acrylic monomer, dichromic acid-based photoresist, non-chromium-based water-soluble photoresist, polysilane Examples include acid vinyl photoresists, cyclized rubber-azide photoresists, and the like.

In this way, after forming the grooves 7 that will finally constitute the ink passages and ink supply chambers using the hardened photoresist film 3P, as shown in FIG. It is adhesively fixed onto the membrane 3P using an adhesive 5 to form a bonded body.

Note that before fixing the flat plate 6 on the hardened photoresist film 3P, the coupling agent layer 2 on the substrate surface of the groove 7 is subjected to oxygen plasma ashing because it may affect the function of the ink ejection energy generating element. It is preferable to remove it from the substrate 1 by processing or the like as shown in FIG.

In the process shown in FIG. 6, the specific method for attaching the cover 6 is as follows: 1) Spinning epoxy resin adhesive to a thickness of 3 to 4 μs on a flat plate 6 made of glass, ceramic, metal, plastic, etc. After coding, the adhesive layer 5 is preheated and the so-called B
There are methods such as 2) thermoplastic resin such as acrylic resin, ABS resin, polyethylene, etc. A resin flat plate 6 is placed on the hardened photoresist film 3P,
A method that does not use an adhesive, such as direct heat-sealing, may also be used.

Here, the appearance of the joined body after the process shown in FIG. 6 is completed is shown in the schematic perspective view of FIG. 7. In Figure 7, ? -1 is an ink supply chamber, 7-2 is an ink passage, 8 is an ink supply chamber 7-1
2 shows a through hole for connecting an ink supply pipe (not shown) for supplying ink from the outside of the recording head to the inside.

In this way, after the bonding between the substrate l on which the grooves 7 are formed and the flat plate 6 is completed, this bonded body is cut along c-c', which is the downstream side of the ink passage in FIG. An orifice for ejecting ink, which is an opening of an ink passage in the surface, is formed.

This process is performed using the ink ejection energy generating element 1-2 and the orifice shown in FIG. This is done in order to optimize the distance from -3, and the area to be cut here is selected as appropriate. For this cutting, a dicing method or the like commonly used in the semiconductor industry can be used.

Note that the downstream part of the ink passage in the present invention refers to the downstream region in the flow direction of ink when recording is performed using a recording head, specifically, the downstream region of the ink path in the flow direction of the ink when recording is performed using the recording head, specifically, the downstream region of the ink passage
Refers to the part of the ink passage downstream from the installation position of -2.

Once cutting is complete, the cut surface is polished and smoothed.
Insert the ink supply tube 9 into the through hole 8 to complete the ink jet recording head 6. Note that in the recording head shown in FIG. 9, the ink passage 7-2 and the side wall of the ink supply chamber 7-1 are Although the ink passage and the ink supply chamber are integrally molded using the cured photoresist film 3P, the method of the present invention can also be applied to a recording head in which the ink passage and the ink supply chamber are molded separately and then joined together.

〔Example〕

Hereinafter, the method of the present invention will be explained in more detail according to Examples and Comparative Examples.

Example 1 According to the method of the present invention previously explained in the specification with reference to FIGS. 1 to 9, ten orifices were prepared using a heat generating element [Hafcolampolide (HfB2)] as an ink ejection energy generating element. (Orifice dimensions, 75ulX5
An on-demand inkjet recording head having a pitch of 0.01Llfi and a pitch of 0.125 am was fabricated as follows.

First, a plurality of heat generating elements are arranged at predetermined positions on a substrate made of silicon, electrodes for applying recording signals are connected to these, and then a protective film is applied to the surface of the substrate on which the heat generating elements are arranged. A 5i02 layer (thickness 1.0 μs) was applied, and the surface of the protective layer was cleaned and dried at 80° C. for 10 minutes.

Next, on the surface of the protective layer, a solution of 3-mercaptopropylmethyldimethoxysilane dissolved in ethanol at a concentration of 1% by weight was sprayed, and then the sprayed surface was heated at 80°C for 1 hour.
The protective layer was heated for 0 minutes, and the surface of the protective layer was treated with a primary silane coupling agent.

Subsequently, γ-glycidoxyprobyltrimethoxysilane was further added to the surface of the first-treated protective layer in ethanol.
After spraying a solution dissolved at a concentration of □% by weight, the sprayed surface was heated at 80° C. for 10 minutes to perform a second silane coupling agent treatment.

On the surface of the protective layer treated in this way, a first layer consisting of 3-mercaptopropylmethyldimethoxysilane and a second layer consisting of γ-glycidoxypropyltrimethoxysilane are formed from the protective layer side. Ta.

After the coupling agent treatment was completed, Linston (RI
STON) 73'OS tri-film photoresist (trade name, manufactured by DuPont) at 0.4f/ll1n,
The lamination was carried out at a speed of 1 kg/cm3 under pressure conditions.

Next, a photomask having a pattern corresponding to the shape of the ink passage ink supply chamber is superimposed on the dry film photoresist provided on the substrate surface, and a photomask is placed in the ink passage area to be finally formed. After alignment was performed so that the elements would be provided, the photoresist was exposed to ultraviolet light with an intensity of 8.2 mW/am 2 from above the photomask.

Next, the exposed photoresist is immersed in trichloroethane and developed, and the unpolymerized (unhardened) portion of the photoresist is dissolved and removed from the substrate, resulting in the cured photoresist film remaining on the substrate. Grooves that would eventually become ink passages and ink supply chambers were formed.

After completing the development process, the cured photoresist on the substrate was heated at 250°C for 1 hour, and then heated at 50 n+
It was further cured by irradiating it with ultraviolet rays with an intensity of W/cm2 for 2 minutes.

In this way, after forming grooves that will become ink passages and ink supply chambers on the substrate using the cured photoresist film,
The coupling agent layer on the substrate surface within the groove was removed from substrate 1-4= by oxygen plasma ashing treatment.

Next, apply epoxy resin adhesive to a thickness of 3 mm on a flat plate made of soda glass with through holes that will cover the formed grooves.
After spin-coding the wire, it was preheated to form a CB stage, and this was bonded to a hardened photoresist, and the adhesive was further cured and fixed to form a bonded body.

Next, the downstream side of the ink passage of the bonded body, that is, 0.15 mm downstream from the installation position of the ejection energy generating element.
1/B, a commercially available dicing saw (product name: DAD 2)
(manufactured by C:0) to form an orifice for ejecting ink.

Finally, the cut surface was polished and smoothed, and an ink supply tube was attached to the through hole to complete the Infusiera I recording head.

The quality of the recording head thus produced by the method of the present invention and its durability during long-term use were tested as follows.

First, the orifice-forming surfaces of the 20 recording heads obtained were observed using a metallurgical microscope (manufactured by Olympus Corporation) to determine whether peeling occurred between the cured photoresist film and the substrate.

Table 1 shows the number of recording heads in which peeling was observed.

Next, for the recording heads for which no peeling was observed, the operation of heating and cooling the recording heads to -30°C and +80°C was repeated at 30-minute intervals, and the recording head was heated back and forth for 100 cycles.・Conducted a link test. It was examined in the same manner as above to determine whether or not peeling occurred between the cured photoresist film and the substrate in the recording heads after the test, and the number of recording heads in which peeling was observed is shown in Table 1.

Separately, the formed recording head was attached to a recording device, and a recording signal of 108 pulses was continuously recorded for 14 hours using ink consisting of 20% by weight of water, % by weight of ethylene glycol, and % by weight of black dye. The ink was applied to the head to perform printing, and the accuracy of the ink landing point immediately after the start of printing and after 14 hours had elapsed was measured and compared to evaluate durability during long-term continuous use.

In the recording head obtained in this example, ±12 JLIII/yHI11 throughout the period of continuous use.
Flight distance and good impact point accuracy were maintained.

Note that the ink landing point accuracy was measured as follows.

First, the recording head is fixed so that the orifice arrangement direction is perpendicular, and the recording head is set perpendicularly at a distance of 2 mm from the orifice, and in a direction perpendicular to the orifice arrangement direction.
That is, 0.25m/see in the horizontal direction.

The ink was simultaneously ejected from every other five orifices at 2.0 kHz onto the paper surface to be scanned.

Next, the impact point error was calculated from the obtained recorded matter.

That is, the direction corresponding to the arrangement direction of the orifices of the obtained recording material was defined as the X axis, and the direction perpendicular to this was defined as the Y axis, and an arbitrary dot on the paper was taken as the origin, and the XY coordinates were set. Next, the X-coordinate value of each recorded dot within this coordinate is determined from the arithmetic average value of the X-coordinate values at both ends of each dot, and the same operation is performed in the Y-coordinate direction to determine the X-Y The coordinate values were determined and used as the impact point. Then, calculate the difference in the X coordinate values of the impact points of two dots adjacent to each other in the X-axis direction, and calculate the difference between this and twice the orifice pitch, that is, 0.
．． The difference from 25+nm was defined as the landing point error in the X-axis direction. Further, the difference between the Y coordinate values of two adjacent drums in the X-axis direction was defined as the impact point error in the Y-axis direction. These calculations, ■
The test was carried out for 50 pulses of dots on the head.

The maximum values of the landing point errors obtained for each head were averaged for 20 heads.

Examples 2 to 12 The material of the protective layer and the type of coupling agent were changed as shown in Table 2, and in Examples 9 to 12, a piezo vibrator [PbZ r03] was used as the ejection energy generating element.
An inkjet recording head was prepared in the same manner as in Example 1 except that -PbT i03 series (manufactured by Tohoku Kinzoku ■) was used, and the quality and durability of the recording head were evaluated in the same manner as in Example 1.

Table 1 shows the number of recording heads in which peeling was observed.

Regarding the impact point accuracy in durability evaluation, the recording heads obtained in these examples all maintained good impact point accuracy with a flight distance of ±12 to ±18 gm/mm throughout the period of continuous use. Ta.

Comparative Examples 1 to 4 Inkjet recording heads were prepared in the same manner as in Examples 1 to 3 and Example 12, except that the cut surface was not treated with a coupling agent. The quality and durability of the product were evaluated.

Table 1 shows the number of recording heads in which peeling was observed.

Regarding the impact point accuracy in durability evaluation, the recording heads obtained in these comparative examples had a flight distance of about ±10 to ±18 scales/ff1B at the beginning of printing, but after continuous printing The flight distance decreased to about ±40 to ±112 tiles/mm.

〔Effect of the invention〕

According to the method for manufacturing an inkjet recording head of the present invention as described in (2) below, it is possible to provide an inkjet recording head with high precision, good quality, and low cost.

Moreover, according to the method for manufacturing an inkjet recording head of the present invention, a two-layer silane coupling agent layer is provided between the substrate and the cured photosensitive resin film forming the ink passage by treating the surface of the substrate. This improves not only the adhesion between the substrate and the photosensitive resin cured film, but also the ink resistance of this area, which improves the bond between the substrate and the photosensitive resin, which was observed in recording heads formed by conventional methods. There is no deformation of the predetermined shape of the orifice or ink passage due to peeling from the cured film, and there is no deterioration in recording performance such as impact point accuracy, and durability allows the initial good impact point accuracy to be maintained even during long-term use. It is possible to provide an inkjet recording head with excellent performance and high reliability.

[Brief explanation of drawings]

FIGS. 1 to 9 are schematic diagrams for explaining the method of manufacturing an inkjet recording head of the present invention. Substrate 1-2: Discharge energy generating element 1-3: Protective film 2-1 = First silane coupling agent layer 2-2: Second silane coupling agent layer 3 Nidrifilm photoresist 3P: Cured photoresist film 4: Photomask 5: Adhesive layer 6: Cover 7: Groove forming ink passage 7-1 = Ink supply chamber 7-2: Ink passage 7-3 = Orifice 8: Ink supply hole 9: Ink Supply pipe Figure 1 Figure 2 Figure 3 Figure 39 Figure 4 Figure 5

Claims (1)

[Scope of Claims] 1) A liquid in which a liquid passage communicating with an ejection port is formed on a substrate provided with a liquid ejection energy generating element, and at least a part of the wall of the liquid passage is made of a photosensitive resin cured film. When manufacturing an ejection recording head, the surface of the substrate on which the photosensitive resin cured film is laminated is prepared using the following general formula (I ); R^1SiR^2_3_-_mR^3_m(I) [In the above formula, m represents an integer of 1 or 2, and R^1
represents a group having one or more selected from the group consisting of an amino group, a vinyl group, a methacrylic group, an epoxy group, and a mercapto group, and R^2 represents a chloro group, a methoxy group, an ethoxy group, an acetoxy group, or a β-methoxy group. represents an ethoxy group, R^3 represents a methyl group or an ethyl group], and then the following general formula (II); In the above formula, n represents an integer of 1, 2 or 3, R^4 represents a group having one or more selected from the group consisting of an amino group, a vinyl group, a methacrylic group, an epoxy group and a mercapto group, R^S represents a chloro group, a methoxy group, an ethoxy group, an acetoxy group, or a β-methoxyethoxy group.