KR101320780B1 - Liquid discharge recording head and liquid discharge apparatus - Google Patents

Abstract

The liquid discharge type recording head for discharging a liquid is provided with a liquid discharge energy generating element, and comprises a substrate constituting a part of a flow path for supplying liquid, and an orifice provided on the substrate, constituting a part of the flow path and discharging the liquid. It includes a coating resin layer comprising a, the coating resin layer is composed of an oxetane resin composition having an oxetane compound having at least one oxetanyl group in the molecule and a photo cationic polymerization initiator as an essential component.

Liquid discharge type recording head, liquid discharge device, flow path, substrate, liquid discharge port, coating resin layer, oxetanyl group, oxetane resin composition

Description

Liquid ejecting recording head and liquid ejecting device {LIQUID DISCHARGE RECORDING HEAD AND LIQUID DISCHARGE APPARATUS}

1 is a perspective view of an inkjet printer device according to an embodiment of the present invention.

Fig. 2 is a perspective view of a head cartridge installed in the ink jet printer apparatus.

3 is a cross-sectional view of the same head cartridge.

4 is a perspective view showing a portion of an ink jet recording head according to an embodiment of the present invention.

Fig. 5 is a sectional view of the inkjet recording head.

Fig. 6A is a sectional view schematically showing the inkjet recording head in a state where bubbles are generated on the discharge energy generating element.

Fig. 6B is a sectional view schematically showing the inkjet recording head in a state where ink is discharged from a nozzle.

7 is a cross-sectional view of a substrate on which discharge energy generating elements are installed.

8 is a cross-sectional view showing a state in which an ink flow path pattern is formed of a resin soluble on a substrate;

9 is a cross-sectional view illustrating a state in which a first coating resin layer is formed on an ink flow path pattern.

10 is a cross-sectional view showing a state of irradiating an active energy ray to a first coating resin layer.

11 is a cross-sectional view showing a state in which a first coating resin layer is formed in a pattern.

12 is a cross-sectional view showing a state in which a product produced by forming an ink flow path pattern and a first coating resin layer on a substrate is cut with a dicer;

Fig. 13 is a cross-sectional view showing a state in which an ink flow path pattern is formed to dissolve and remove a soluble resin;

Fig. 14 is a side view illustrating a part of the inkjet printer apparatus as viewed through a perspective view.

DESCRIPTION OF THE REFERENCE NUMERALS

1: inkjet printer device 2: head cartridge

3: device body 11: ink cartridge

21: cartridge body 22: mounting portion

23: inkjet recording head 24: head cap

31: common flow path 32: ink supply member

33: first substrate 33a: discharge energy generating element

34: individual flow path 35: nozzle

36: 1st coating resin layer 36a: discharge surface

37: second substrate 38: second coating resin layer

39: upper plate 40: supply port

41: ink euro pattern 42: mask

43: active energy ray 44: dicer

This invention contains the subject matter of patent application JP 2005-229902 for which it applied to Japan Patent Office on August 8, 2005, The content is taken in here as a reference as a whole.

The present invention relates to a liquid discharge type recording head having satisfactory low stress and chemical resistance and having a high precision flow path formed by pattern molding by ultraviolet irradiation or the like, and a liquid discharge apparatus including the same.

An example of the liquid ejecting apparatus is an inkjet printer apparatus employing an inkjet recording method (liquid ejection recording method) for ejecting ink, for example, as a liquid. This ink jet printer apparatus is provided with an ink jet recording head for discharging ink. The inkjet recording head is provided with a plurality of constituent units comprising a discharge port (i.e., an orifice) for discharging ink in the form of fine droplets, a flow path communicating with the discharge port, and an ink discharge pressure generating element provided in part of the flow path. In order to obtain a high quality image with such an ink jet recording head, it is preferable that droplets of ink discharged from the orifice are always discharged from each orifice at the same volume and discharge rate.

As an ink jet recording head which realizes such discharge conditions, for example, Japanese Patent Application Laid-Open No. 56-123869, Japanese Patent Application Laid-Open No. 57-208255, and Japanese Patent Application Laid-Open No. 57-208256 There are inkjet recording heads described in the back and the like. The ink jet recording heads described in Japanese Patent Laid-Open No. 56-123869, Japanese Patent Laid-Open No. 57-208255, and Japanese Patent Laid-Open No. 57-208256 include an ink discharge pressure generating element. The nozzle which consists of an ink flow path and an orifice part is formed on the board | substrate with which the pattern of photosensitive resin material or photoresist is formed, and the cover, such as a glass plate, is bonded on the member which has an ink flow path and a nozzle. As the photosensitive resin material or photoresist, for example, a reaction of a sensitizer with a photopolymer, polyvinyl cinnamate or the like using polymerization of a diazo resin, P-diazoquinone, or a vinyl monomer in the presence of a polymerization initiator is used. Dimerized photopolymer, mixture of orthoquinone diazide with phenol novolak resin, mixture of polyvinyl alcohol and diazo resin, polyether type copolymerized with 4-glycidyl ethylene oxide and benzophenone or glycidyl chalcone Photopolymers, photopolymers of N, N-dimethylmethacrylamide with, for example, acrylamidebenzophenone, unsaturated polyester photosensitive resins, unsaturated urethane photosensitive resins, and bifunctional acrylic monomers, in which photopolymerization initiators and polymers are mixed. Compositions, Dichromate Photoresists, Non-Chrome-Based Water Soluble Photoresists, and Polyvinyl Cinnamate Photoresists The like are used.

Another inkjet recording head which realizes the above discharge condition is an inkjet recording head obtained by the manufacturing method described in Japanese Patent Laid-Open No. 61-154947. In the method for manufacturing an inkjet recording head described in Japanese Patent Laid-Open No. 61-154947, a pattern of the ink flow path is formed of a resin that is soluble in a portion of the ink flow path on a substrate, and the pattern of the ink flow path is an epoxy resin. The inkjet recording head is provided by dissolving and dissolving the soluble resin forming the pattern of the ink flow path after coating the substrate and cutting the substrate.

Japanese Patent Laid-Open No. 56-123869, Japanese Patent Laid-Open No. 57-208255, Japanese Patent Laid-Open No. 57-208256, and Japanese Patent Laid-Open No. 61-154947 In the inkjet recording head, for example, a heat generating resistor serving as an ink discharge pressure generating element provided in a part of the ink flow path is provided in parallel with the direction in which the ink flows. Each orifice for ejecting ink is provided at the end of the corresponding ink flow path, and is installed perpendicular to the direction in which the ink flows. In such an inkjet recording head, the orifice is positioned almost perpendicular to the heat generating resistor. As a result, the ejecting direction of the ink becomes perpendicular to the growth direction of the bubbles formed on the heat generating resistor. That is, the bubble growth direction and the ink discharge direction are different.

In such an inkjet recording head, a part of the orifice located at the end of the corresponding ink flow path is formed at the end of the substrate, so that the distance between the ink discharge pressure generating element and the orifice is set by cutting the substrate. For this reason, the cutting precision of a board | substrate becomes very important in control of the distance between an ink discharge pressure generation element and an orifice. Cutting of the substrate is generally performed by mechanical means such as a dicing saw, and it is difficult to realize high precision by such mechanical means.

Further, Japanese Patent Laid-Open No. 56-123869, Japanese Patent Laid-Open No. 57-208255, Japanese Patent Laid-Open No. 57-208256, and Japanese Patent Laid-Open No. 61-154947 Unlike the ink jet recording head described in the above, in another ink jet recording head, for example, an electrothermal conversion element and an orifice, which are ink discharge pressure generating elements, are provided to face each other. Therefore, the growth direction of the bubbles formed on the electrothermal conversion element and the discharge direction of the ink are almost the same. Such inkjet recording heads are described in, for example, Japanese Patent Laid-Open No. 58-8658 and Japanese Patent Laid-Open No. 62-264957. In the inkjet recording head described in Japanese Patent Application Laid-Open No. 58-8658, a dry film serving as an orifice plate is bonded to a substrate having an electrothermal conversion element through a separate dry film patterned, and electrothermal conversion An orifice is formed on a dry film that becomes an orifice plate by photolithography at a location opposite the device. In the ink jet recording head described in Japanese Patent Laid-Open No. 62-264957, a substrate having an ink discharge pressure generating element is bonded to an orifice plate produced by electroforming through a patterned dry film.

The inkjet recording heads described in Japanese Patent Application Laid-Open No. 58-8658 and Japanese Patent Laid-Open No. 62-264957 have an orifice plate that is thin, for example, 20 µm or less in thickness, and is uniformly orifice plate. It is difficult to manufacture. In addition, even if an orifice plate can be manufactured in this inkjet recording head, the bonding process with the substrate having the ink discharge pressure generating element becomes very difficult to perform due to the fragility of the orifice plate.

In addition, with respect to the ejection condition in the inkjet recording head, in addition to the ejection condition for ejecting ink at the same volume and ejection speed from the orifice, it is necessary to eject minute ink droplets at the correct positions. It is preferable that the inkjet recording head has a shorter distance (hereinafter referred to as "OH distance") between the electrothermal converting element and the orifice provided in the ejection energy generating section in order to eject the ink at the correct position.

As a manufacturing method of an inkjet recording head having a high accuracy OH distance, there is a manufacturing method as described in Japanese Patent Laid-Open No. 6-286149. Japanese Patent Laid-Open No. 6-286149 discloses a step of forming an ink flow path pattern that becomes an ink flow path with a soluble resin on a substrate having an ink discharge pressure generating element, and a coating containing a solid epoxy resin at room temperature. The process of forming the coating resin layer which becomes an ink flow path wall on a soluble resin layer by solvent-coating the solution manufactured by dissolving resin in a solvent on the soluble resin layer which forms the ink flow path pattern, and generation of ink discharge pressure The manufacturing method of the inkjet recording head which has the process of forming an orifice in the coating resin layer of the upper side of an element, and the process of eluting and removing the soluble resin layer which forms the ink flow path pattern are described. In the manufacturing method of the inkjet recording head disclosed in Japanese Patent Laid-Open No. 6-286149, a cationic polymer of an alicyclic epoxy resin is used as a coating resin in terms of forming a high aspect ratio pattern and ink resistance. .

In addition, the following problems arise newly in the inkjet recording head by using the methods and materials described in Japanese Patent Laid-Open No. 6-286149 and Japanese Patent Laid-Open No. 7-214783.

The hardened | cured product manufactured by cationic polymerization of these alicyclic epoxy resins is excellent in the adhesive force with the base substrate. However, since the internal stress of the cured product is high, peeling from the substrate on which the coating resin layer made of the cured product is based occurs. In addition, in the cured product produced by cationic polymerization of an alicyclic epoxy resin, cracks (film cracking) occur particularly at corners such as the pattern edge of the resin film where stress is concentrated, which greatly reduces the reliability as an inkjet recording head. In addition, some of these materials have insufficient patterning performance and do not provide the fine patterning performance required to form the structure for the inkjet recording head.

In the inkjet recording head, in particular, in the case where the coating resin layer serving as the ink flow path wall is formed in a long shape or the thickness becomes thick, furthermore, when the structure of the ink flow path becomes minute and complicated, the coating resin layer is easily peeled off or on the coating resin layer. Easy to crack In addition, in the inkjet recording head, the head surface from which ink is discharged is subjected to head cleaning to maintain image quality, thereby removing excess ink adhering to the head surface. In the inkjet recording head, the head surface may be wiped by a cleaning member or the like when the head is cleaned, so that a mechanical load is applied to the head surface, which may promote the peeling of the coating resin layer from the substrate.

An object of the present invention is to provide a liquid discharge type recording head having a low stress and having a coating film which can be formed accurately and easily by patterning by ultraviolet irradiation or the like and a liquid discharge device including the same.

A liquid discharge type recording head according to one embodiment of the present invention discharges liquid, in which a liquid discharge energy generating element is formed, which forms a part of a flow path for supplying liquid, and is formed on the substrate, It has a coating resin layer which comprises a part and has an orifice which discharges a liquid. The coating resin layer of this liquid discharge type recording head is formed of an oxetane resin composition having an oxetane compound having at least one oxetanyl group in a molecule and an optical cationic polymerization initiator as essential components.

Further, the liquid ejecting apparatus according to one embodiment of the present invention includes the liquid ejecting recording head.

Further, a liquid discharge type recording head according to another embodiment of the present invention is a liquid supply member for discharging a liquid, the liquid supply member having a recess forming a part of a common flow path for supplying liquid; A first substrate joined to one side of the concave portion of the liquid supply member, the end face of which comprises a part of the common flow path, on which a liquid discharge energy generating element is provided; A first coating resin layer provided on the first substrate, the first coating resin layer having a separate flow path for supplying a liquid supplied from a common flow path to the periphery of the liquid discharge energy generating element and a liquid discharge orifice for discharging the liquid; A second substrate joined to the other side of the recess of the liquid supply member and having a cross section forming a part of the common flow path; A second coating resin layer provided on the second substrate; And an upper plate provided on the first coating resin layer and the second coating resin layer to close the discharge surface side of the common flow path. The first coating resin layer of the liquid discharge type recording head is formed of an oxetane resin composition containing an oxetane compound having at least one oxetanyl group and a photocationic polymerization initiator as essential components in a molecule.

Also, a liquid ejecting apparatus according to another embodiment of the present invention includes the liquid ejecting recording head.

According to one embodiment of the present invention, a part of the flow path constitutes a coating resin layer having an orifice or a first coating resin layer having individual flow paths and orifices is formed of an oxetane resin composition. Due to the properties as a low stress material possessed by the oxetane compound, the coating resin layer can be made low in stress, cracks can be prevented, peeling from the substrate can be prevented, and excellent durability can be provided. Further, according to the embodiment of the present invention, chemical resistance can be provided by forming the coating resin layer or the first coating resin layer from the oxetane resin composition. Therefore, according to the embodiment of the present invention, manufacturing yield and quality are improved, and high reliability is obtained over a long term.

A liquid ejecting recording head and a liquid ejecting apparatus according to an embodiment of the present invention will be described with reference to the drawings. The liquid ejecting apparatus is an inkjet printer apparatus for ejecting ink, for example, as a liquid, and an inkjet recording head which is a liquid ejecting recording head is provided in this printer apparatus.

An inkjet printer apparatus (hereinafter referred to as a printer apparatus) 1 is an inkjet printer head cartridge (hereinafter referred to as a head cartridge) that ejects ink i to an object, for example, a recording sheet P, as shown in FIG. 2) and a main body 3 on which the head cartridge 2 is mounted. This printer apparatus 1 is a so-called la-doll printer apparatus in which one or more ink orifices (nozzles) are arranged substantially in a line in the width direction of the recording paper P, that is, the arrow W in FIG. In the printer device 1, the head cartridge 2 is detachable from the main body 3.

First, the head cartridge 2 constituting the printer device 1 will be described. The head cartridge 2 discharges ink i, for example using an electrothermal conversion heating element as a pressure generating element, and deposits ink i on the main surface of the recording sheet P. As shown in FIG. As shown in Figs. 2 and 3, the head cartridge 2 is attached with an ink cartridge 11, which is a container in which the ink i is accommodated. The ink cartridge 11 is yellow ink, magenta ink, cyan ink, and black ink, for each color of the yellow ink, the ink cartridge 11y for the yellow ink, the ink cartridge 11m for the magenta ink, the ink cartridge 11c for the cyan ink, and the black. An ink cartridge 11k of ink is provided. The ink cartridge 11 is formed in the rectangular shape which makes the dimension substantially the same as the dimension of the width direction of the recording paper P. As shown in FIG. More specifically, the ink cartridge 11 has an ink container 12 containing ink i, as shown in Fig. 3, and a cartridge of the head cartridge 2 on the lower surface of the ink container 12. An ink supply part 13 for discharging ink i is provided in the body 21.

The ink receiving portion 12 is provided with an external communication hole 14 serving as a hole for introducing external air into the central portion of the upper surface. In the ink cartridge 11, when ink i is supplied to the cartridge body 21, air corresponding to the reduced amount of ink i is introduced through the external communication hole 14.

The ink supply part 13 is provided in the substantially center part of the lower side of the ink accommodating part 12. FIG. This ink supply part 13 is a nozzle of the substantially protruding shape in communication with the ink containing part 12. The tip of this nozzle is fitted to the connecting portion 25 of the head cartridge 2 described later, thereby connecting the ink containing portion 12 of the ink cartridge 11 to the cartridge body 21 of the head cartridge 2. .

The ink supply unit 13 is provided with a supply port for supplying ink i to the cartridge body 21 side at the bottom surface side of the ink cartridge 11, and opens the supply port by a valve mechanism (not shown in detail). , Or occlude. The ink cartridge 11 is attached to the cartridge body 21. When the ink supply portion 13 and the connection portion 25 of the head cartridge 2 are connected, the valve is separated from the supply port to open the supply port. Therefore, ink i is supplied to the head cartridge 2 side.

The head cartridge 2 to which the ink cartridge 11 is attached has a cartridge body 21, as shown in Figs. The cartridge body 21 includes an attachment portion 22 to which the ink cartridge 11 is attached, an inkjet recording head 23 for ejecting ink i, and a head cap 24 for protecting the inkjet recording head 23. Equipped.

In the center of the longitudinal direction of the attachment part 22, the connection part 25 connected with the ink supply part 13 of the ink cartridge 11 attached to the attachment part 22 is provided. This connection portion 25 ink is supplied to the inkjet recording head 23 which discharges the ink i installed on the bottom surface of the cartridge body 21 from the ink supply portion 13 of the ink cartridge 11 attached to the attachment portion 22. It becomes a supply path which supplies (i). The connection part 25 adjusts the supply of the ink i from the ink cartridge 11 to the inkjet recording head 23 with a valve mechanism.

An ink jet recording head 23 to which ink i is supplied from the connecting portion 25 is provided along the bottom surface of the cartridge body 21. The inkjet recording head 23 has a nozzle 35, which is an orifice for discharging ink i supplied from the connecting portion 25, which is described later in the line direction in the width direction of the recording paper P, that is, the arrow W in FIG. It is added together. The inkjet recording head 23 discharges the ink i from each nozzle line without moving in the width direction of the recording sheet P. FIG.

As shown in Figs. 4 and 5, the ink jet recording head 23 is provided with an ink supply member 32 provided with a recess 32a constituting a part of the common flow path 31, and of the ink supply member 32. A first coating resin layer provided on one side of the recessed portion 32a, provided on the first substrate 33 and having a separate flow path 34 and a nozzle 35 thereon (the first coating resin layer ( 36, a second substrate 37 provided on the other side of the recessed portion 32a of the ink supply member 32, having the same height as the first substrate 33, and provided on the second substrate 37. , The second covering resin layer 38 having the same height as the first covering resin layer 36, and the first covering resin layer 36 and the second covering resin layer 38, which are provided on the common flow passage 31. Has a top plate (39) for closing.

The inkjet recording head 23 includes an ink supply member 32, a cross section of the first substrate 33, a cross section of the first covering resin layer 36, a cross section of the second substrate 37, and a second covering resin layer 38. ), And a separate flow path having a common flow path 31 surrounded by an upper plate 39 and a liquid chamber surrounding the discharge energy generating element 33a by the first substrate 33 and the first coating resin layer 36. 34 is formed. In the inkjet recording head 23, ink i from the ink cartridge 11 is supplied to the common flow path 31, and ink i supplied from the common flow path 31 is supplied to each individual flow path 34. .

 The ink supply member 32 constituting a part of the common flow path 31 is formed of ink resistant resin or the like, and the recess 32a constituting a part of the common flow path 31 is formed on the ink supply member 32. It is provided.

The 1st board | substrate 33 is a silicon substrate, for example, The electrothermal conversion element which acts as the some discharge energy generating element 33a in the predetermined location of the surface of the 1st board | substrate 33 is provided by the semiconductor process. . In addition, the first substrate 33 is provided with a control circuit 33b for controlling the discharge energy generating element 33a. A cross section of the first substrate 33 adjacent to the common flow passage 31 forms part of the common flow passage 31. As for the 1st board | substrate 33, the surface in which the discharge energy generation element 33a was provided comprises the bottom surface of the individual flow path 34. As shown in FIG. The discharge energy generating element 33a is not limited to an electric heat conversion element, and may be an electromechanical conversion element such as a piezoelectric element.

The first coating resin layer 36 is patterned on the first substrate 33. The 1st coating resin layer 36 discharges the individual flow path 34 which supplies the ink i from the common flow path 31 around each discharge energy generating element 33a provided on the 1st board | substrate 33, and It has the nozzle 35 which discharges ink i in the position which opposes the energy generating element 33a. The individual flow path 34 is provided with respect to the corresponding discharge energy generating element 33a, and is concave in the direction orthogonal to the depth direction of the common flow path 31. The supply port 40 for connecting with the common flow path 31 is formed in the edge part of the individual flow path 34 adjacent to the common flow path 31 side.

The nozzle 35 is connected with the corresponding individual flow path 34. The nozzle 35 discharges the ink i in the individual flow path 34 heated and pressed by the energy generated in the discharge energy generating element 33a.

Specifically, the first coating resin layer 36 includes an oxetane compound having at least one oxetanyl group in the molecule and an oxetane resin composition containing photocationic polymerization initiator as essential components on the first substrate 33. It forms by pattern-forming on the surface in which (33a) is provided, and hardening an oxetane resin composition.

Here, the oxetane resin composition which forms the 1st coating resin layer 36 is demonstrated. The oxetane compound in the oxetane resin composition has a four-membered ring in which one carbon is increased in the oxirane ring of the epoxy. This oxetane compound is excellent in cation curability compared with an epoxy compound. The cation hardened | cured material of this oxetane compound has much larger molecular weight than epoxy hardened | cured material, shows the reliable mechanical strength which is toughness and elongation resistance, and shows the outstanding water resistance and chemical-resistance. The characteristic of the cation hardened | cured material of this oxetane compound differs significantly from the characteristic of hard and brittle epoxy hardened | cured material. Moreover, the cation hardened | cured material of an oxetane compound does not have the mutagenicity derived from the 4-membered ring oxetanyl group, and this oxetane compound is superior to the low molecular weight photocurable epoxy resin with respect to safety.

The oxetane compound includes a monofunctional oxetane compound having one oxetanyl group in a molecule and a polyfunctional oxetane compound having two or more oxetanyl groups in a molecule. The monofunctional oxetane compound is represented by the following formula (1).

In formula (1), R ¹ is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group, such as an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group or a thienyl group . R ² is an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1 Alkenyl group having 2 to 6 carbon atoms, such as butenyl group, 2-butenyl group or 3-butenyl group, group having aromatic ring such as phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group or phenoxyethyl group, ethylcarbonyl group , C2-C6 alkylcarbonyl group such as propylcarbonyl group or butylcarbonyl group, C2-C6 alkoxycarbonyl group such as ethoxycarbonyl group, propoxycarbonyl group or butoxycarbonyl group, or ethylcarbamoyl group, propylcarbamoyl group, butylcarbon C2-C6 N-alkyl carbamoyl groups, such as a barmoyl group or a pentyl carbamoyl group.

The bifunctional oxetane compound having two oxetanyl groups is represented by the following formulas (2) and (3).

In the formula 2, each R ¹ is the same as R ¹ in formula (I).

In the formula 3, each R ¹ is the same as R ¹ in formula (I). R ³ is a linear or branched saturated hydrocarbon having 1 to 12 carbon atoms, a linear or branched unsaturated hydrocarbon having 1 to 12 carbon atoms, an aromatic hydrocarbon represented by the following Formulas 8, 9, 10, 11 and 12, Formula 13 and It is group which has two valences chosen from linear or cyclic alkylene containing the carbonyl group represented by 14, and aromatic hydrocarbons containing the carbonyl group represented by General formula (15) and (16). Other bifunctional oxetane compounds include cardo-type, naphthalene-type compounds and the like.

In formula (8), (9), (10), (11), or (12), R ₄ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group, and R ₅ represents -O-, -S-, -CH ₂ —, —NH—, —SO ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ —, and each R ₆ represents a hydrogen atom or 1 to C The alkyl group of 6 is shown.

In Chemical Formula 13, n represents an integer of 1 or more.

Examples of the trifunctional or higher functional oxetane compound include a phenol novolak oxetane compound represented by the following formula (4), a cresol novolak oxetane compound represented by the following formula (5), an oxetane compound having a triazine skeleton represented by the following formula (6), and The oxetane compound shown can be mentioned. As another trifunctional or more than trifunctional oxetane compound, etherified with resin which has hydroxyl groups, such as poly (hydroxy styrene), a calix arene, or silicone resins, such as a silsesquioxane, the unsaturated monomer which has an oxetane ring, and alkyl The copolymer with (meth) acrylate, etc. are mentioned.

In the formula (4) to formula (V), each R ₁ is the same as R ¹ in formula (1) and, n represents an integer of 1 or more. It is preferable that such a novolak-type oxetane compound has the number average nuclide number of 3-10 (that is, n is 1-8). This is because if the number average nucleus number exceeds 10, the viscosity is increased and the crosslinking density does not increase due to steric hindrance.

In the formula (6), each R ₁ is the same as R ¹ in formula (I).

In formula (7), R ₁ is the same as in formula (1), R ₇ is a branched alkylene group having 1 to 12 carbon atoms as shown in the following formula (17), (18) or (19), aromatic represented by formula (20), (21) or (22) Hydrocarbons, n represents the number of functional groups represented by the formula (7) bonded to R ₇ .

In formula (22), R ₈ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group.

These oxetane compounds can be used individually or in mixture of 2 or more types of compounds. In order to obtain stronger chemical resistance or durability, a polyfunctional oxetane compound is preferably selected for use. If the desired viscosity is not obtained with the use of the polyfunctional oxetane compound, the polyfunctional oxetane compound may be diluted with the monofunctional oxetane compound.

The oxetane compound finally provides a cured product having a high degree of cation cure. By adding an epoxy compound, a vinyl ether compound, etc. in an appropriate quantity, the hardening rate of a hardening reaction initial stage can be improved. In this case, it is preferable that the addition amount is 5 to 95 weight% with respect to an oxetane compound.

In addition, since the 1st coating resin layer 36 is formed from the hardened | cured material structure obtained by hardening an oxetane resin composition, in addition to an oxetane compound, a cationic polymerization initiator is contained in an oxetane resin composition. When patterning an oxetane resin composition by irradiating active energy lines, such as an ultraviolet-ray, a photocationic polymerization initiator is used. Photocationic polymerization initiator can be used individually or in combination of 2 or more types of initiators.

Commercially available photo cationic polymerization initiators include, for example, CYRACURE UVI-6950 and UVI-6970 manufactured by Union Carbide Corporation; Optomers SP-150, SP-151, SP-152, SP-170, and SP-171 manufactured by Adeka Corporation; CI-2855 manufactured by Nippon Soda Co., Ltd .; And triarylsulfonium salts such as Degacere KI 85 B manufactured by Degussa, unsubstituted or substituted aryldiazonium salts, and diaryliodonium salts. Examples of the sulfonic acid derivatives include PAI-101 manufactured by Midori Kogaku Co., Ltd., and the like.

As a compounding quantity of a photocationic polymerization initiator, 2-40 weight part is suitable for 100 weight part of oxetane compounds. When the amount is smaller than 2 parts by weight, the acid generated by the irradiation of the active energy ray is small, making pattern formation difficult. On the other hand, when the amount is larger than 40 parts by weight, the sensitivity tends to be lowered by the light absorption of the photocationic polymerization initiator itself. When it is desired to improve the degree of curing, a thermal polymerization cation initiator or a photo cationic sensitizer can be used in combination.

The 1st coating resin layer 36 is formed of the oxetane resin composition which has an oxetane compound which has at least one oxetanyl group in a molecule | numerator, and a photocationic polymerization initiator as an essential component. It is possible to exhibit highly reliable mechanical strength having toughness and elongation resistance, so that problems such as peeling or cracking of the first coating resin layer 36 from the first substrate 33 can be prevented from occurring.

In addition to the oxetane resin composition comprised of the oxetane compound and the photocationic polymerization initiator mentioned above, various additives etc. can be added to the 1st coating resin layer 36 suitably as needed to the 1st coating resin layer 36. As shown in FIG. It is preferable to add a coupling agent as an additive especially in order to further improve the adhesive force with the oxetane resin composition and the base 1st board | substrate 33. As a coupling agent, an aluminate type, a titanate type, a zirconate type, a silane type etc. can be selected. Of these, the silane coupling agent is most preferred.

Examples of the aluminate coupling agent include acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethylacetoacetate, aluminum trisethylacetoacetate, aluminum trisacetylacetonate, and the like.

Examples of titanate-based coupling agents include isopropyltristearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecyl Phosphate) Titanate, Tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) Ethylene titanate, and the like.

Examples of the zirconate-based coupling agent include zirconium tetrakisacetylacetonate, zirconium dibutoxybisacetylacetonate, zirconium tetrakisethylacetoacetate, zirconium tributoxy monoethylacetoacetate, zirconium tributoxyacetylacetonate, and the like. Can be.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercapto Propyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. Can be mentioned.

Among the silane coupling agents, the amine coupling agent is not preferable because it absorbs the acid generated from the photocationic polymerization initiator and causes a decrease in sensitivity. In addition, the addition amount of an additive is 0.1 weight% or more and less than 1 weight% with respect to the whole material which forms the 1st coating resin layer 36 containing an oxetane resin composition etc .. As shown in FIG. If the added amount is less than 0.1% by weight, the effect on the adhesion is not sufficient. If the addition amount is 1% by weight or more, the development speed may be remarkably lowered, resulting in developing residues or reduced resolution.

In the 1st coating resin layer 36, adhesive strength in the interface of the 1st board | substrate 33 which an inorganic component mainly uses and the oxetane resin composition which is an organic material by using a suitable additive, ie, a silane coupling agent, etc. Increases. Therefore, the adhesion of the first coating resin layer 36 to the first substrate 33 can be maintained even in the state of being exposed to the ink i, thereby improving the reliability of the inkjet recording head 23.

When forming the 1st coating resin layer 36, in order to use an oxetane resin composition, it can melt | dissolve in a solvent. By dissolving an oxetane resin composition in a solvent, in forming the 1st coating resin layer 36 on the 1st board | substrate 33 to a required film thickness, optimal viscosity and application | coating characteristic can be obtained.

Any solvent capable of dissolving the oxetane compound and other additives can be used. Examples of the solvent include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and tetramethylbenzene, cellosolve and methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol and butyl Glycol ethers such as carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether, ethyl acetate or butyl acetate, cellosolve acetate, butyl cellosolve acetate, Acetates such as carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl acetate, and dipropylene glycol monomethyl ether acetate, alcohols such as ethanol and propanol, ethylene glycol, and propylene glycol, aliphatic such as decane and decane Hydrocarbons, stone There may be mentioned ether, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum-based solvents, such as terpenes, such as limonene, such as solvent naphtha. These solvents provide good solubility of the oxetane resin composition. Among these, a solvent capable of dissolving the oxetane resin composition without dissolving the ink flow path pattern 41 of the soluble resin layer used to form the pattern of the individual flow paths 34 of the inkjet recording head 23 described later. As the aliphatic hydrocarbons and petroleum solvents can be used. In petroleum solvents, solubility is low with respect to the soluble resin layer used for forming the pattern of the individual flow paths 34, and therefore, the deformation of the shape of the ink flow path pattern 41 does not occur easily.

As described above, the first coating resin layer 36 is formed of an oxetane resin composition having an oxetane compound having at least one oxetanyl group and a photocationic polymerization initiator as essential components in a molecule. Therefore, it is possible to exhibit low mechanical stress and high mechanical strength with high toughness and elongation resistance, so that problems such as peeling or cracking of the first coating resin layer 36 from the first substrate 33 occur. Can be prevented. In the inkjet recording head 23 having such a first coating resin layer 36, the production yield and quality can be improved, and high reliability can be obtained over a long period of time.

The 1st coating resin layer 36 is formed of the hardened | cured material of an oxetane resin composition. Since the hardened | cured material of an oxetane resin composition has a small stress compared with the hardened | cured material of an epoxy resin, since the 1st coating resin layer 36 was formed from the hardened | cured material of an epoxy resin, it is a 1st coating from the 1st board | substrate 33. Peeling of the resin layer 36 can be reliably prevented. In addition, the 1st coating resin layer 36 has water resistance and chemical-resistance with an oxetane compound.

In addition, in the 1st coating resin layer 36, since it is formed with the oxetane resin composition, the 1st coating resin layer 36 can be formed in a long shape or thick. Therefore, the complicated and fine individual flow path 34 and the nozzle 35 can also be formed accurately and easily.

In addition, when the first coating resin layer 36 contains an optimal additive in addition to the oxetane resin composition, that is, a silane coupling agent or the like, the adhesion with the first substrate 33 can be further improved. Therefore, peeling of the 1st coating resin layer 36 from the 1st board | substrate 33 can be prevented more reliably.

The second substrate 37 bonded to the other side of the recess 32a of the ink supply member 32 is bonded to the ink supply member 32 with an adhesive. This 2nd board | substrate 37 is provided in order to make the height of one side and the other side of the recessed part 32a to which the 1st board | substrate 33 joined were equal. The second substrate 37 is provided to have the same thickness as the first substrate 33. This second substrate 37 can be formed of a silicon substrate similarly to the first substrate 33, and the material is not limited.

The second coating resin layer 38 is formed on the second substrate 37 by spin coating or the like. The second coating resin layer 38 includes one side (first side) of the recess 32a of the ink supply member 32 having the first coating resin layer 36 and the second coating resin layer 38. It is provided in order to make the height of the other side (2nd side) to be the same. The second coating resin layer 38 is provided to have the same thickness as the first coating resin layer 36. This second coating resin layer 38 can be formed of an oxetane resin composition similarly to the first coating resin layer 36, and the material is not limited. The member provided on the second side of the recess 32a used to equally adjust the height of the first side and the height of the second side is not limited to the second substrate 37 and the second coating resin layer 38. Do not. The material and configuration of the member are not limited as long as the height of the second side of the recess 32a can be the same height as the height of the first side of the recess 32a.

The upper plate 39 is bonded on the discharge surface 36a and the second coating resin layer 38 on the side from which the ink i is discharged from the first coating resin layer 36. The upper plate 39 closes the opening portion on the discharge surface 36a side of the common flow passage 31 and constitutes a part of the common flow passage 31.

In the inkjet recording head having the above structure, the first substrate 33 and the first coating resin layer 36 are provided on the first side of the recess 32a of the ink supply member 32, and the recess 32a is provided. The 2nd board | substrate 37 and the 2nd coating resin layer 38 are provided in the 2nd side of (). Furthermore, the upper plate 39 is provided on the first covering resin layer 36 and the second covering resin layer 38. The inkjet recording head 23 includes an ink supply member 32, a cross section of the first substrate 33, a cross section of the first covering resin layer 36, a cross section of the second substrate 37, and a second covering resin layer 38. ), And a common flow path 31 surrounded by the top plate 39. Furthermore, the individual flow path 34 which forms the liquid chamber surrounding the discharge energy generating element 33a by the 1st board | substrate 33 and the 1st coating resin layer 36 is provided continuously with the common flow path 31. As shown in FIG. In this inkjet recording head 23, ink i from the ink cartridge 11 is supplied to the common flow path 31, and ink i supplied to the common flow path 31 is supplied to each individual flow path 34. do.

In the inkjet recording head 23, the ink i is supplied from the ink cartridge 11 to the common flow path 31, and the ink i flows from the common flow path 31 through the supply port 40 to the individual flow path 34. Supplied to. The supplied ink i is heated and pressurized by the discharge energy generating element 33a, and is discharged from the nozzle 35 with the ink i in the droplet state.

Specifically, in the inkjet recording head 23, as shown in FIG. 6A, when the pulse current is supplied to the discharge energy generating element 33a, and the discharge energy generating element 33a is rapidly heated, the discharge energy generating element 33a Bubble b is generated in ink i in contact with Then, the inkjet recording head 23 pressurizes the ink i as the bubble b expands as shown in Fig. 6B, and ejects the pressurized ink i from the nozzle 35 in the form of droplets. After the inkjet recording head 23 discharges the ink i in the droplet state, the ink i is supplied from the ink cartridge 11 to the common flow path 31, and the individual flow path 34 is supplied through the supply port 40. ) Is supplied with ink i). Therefore, the inkjet recording head 23 returns to the state before discharge again. This is repeated to discharge the ink i continuously.

Next, the manufacturing method of this inkjet recording head 23 is demonstrated.

First, as shown in FIG. 7, a silicon (Si) substrate is prepared as the first substrate 33. On the surface of the first substrate 33, an electrothermal conversion element as the discharge energy generating element 33a is formed at a predetermined position by a semiconductor process or the like.

Next, a positive resist (mainly a novolak resin) as a dissolvable resin layer on the surface on which the discharge energy generating element 33a of the first substrate 33 is provided (Tokyo Okagyo Co., Ltd. (Tokyo) PMER-P-LA900PM) manufactured by Ohka Kogyo Co., Ltd.) is applied while adjusting the rotation speed of the spin coater. Then, it is prebaked on a hot plate for 6 minutes at 110 ° C, for example. The pattern exposure of the individual flow paths 34 is performed with a Canon projection aligner exposure machine (MPA-600FA) or the like. Therefore, as shown in FIG. 8, the ink flow path pattern 41 is formed in the part which becomes the individual flow path 34 with a soluble resin layer. The exposure amount at this time is 800 mJ / cm <2>, for example.

Next, the resist is developed. The development is performed by, for example, a dip development with a P-7G exclusive developer (TMAH (tetramethylammonium hydroxide solution) 3%), and the first substrate 33 is washed with pure water. An ink flow path pattern 41 formed of this soluble resin is formed to provide an individual flow path 34 provided between the common flow path 31 and the discharge energy generating element 33a. On the other hand, it is formed so that the film thickness of the positive resist after image development may be about 10 micrometers.

Next, the above-described oxetane resin composition is dissolved at a concentration of about 50% by weight in petroleum naphtha or the like which does not dissolve the ink flow path pattern 41 formed of the positive resist, to thereby prepare a solution containing an additive or the like. As shown in FIG. 9, this solution is then spin-coated, and is apply | coated on the ink flow path pattern 41, and the photosensitive 1st coating resin layer 36 containing an oxetane resin composition, an additive, etc. is formed. This photosensitive 1st coating resin layer 36 is formed so that the film thickness on the ink flow path pattern 41 may be about 20 micrometers, for example.

Next, as shown in FIG. 10, pattern exposure is performed in order to form the nozzle 35 and the ink supply port 40 with the Canon mirror projection aligner exposure machine (MPA-600FA). When performing pattern exposure, the active energy ray 43 is irradiated to the first coating resin layer 36 through the patterned mask 42 so that the portions corresponding to the nozzle 35 and the ink supply port 40 are not exposed. do. In this step, the exposure dose is, for example, 800 mJ / cm 2, and afterbaking is performed at 65 ° C. for about 60 minutes.

Next, as shown in FIG. 11, the part of the photosensitive 1st coating resin layer 36 which was not exposed is performed with petroleum naphtha. Thereafter, the first substrate 33 is immersed and cleaned in isopropyl alcohol (IPA) to remove the development residue. Thus, the first coating resin layer 36 of the unexposed portion is removed to form the nozzle 35 and the ink supply port 40. The nozzle 35 is about 15 μm in diameter. In this step, since the ink flow path pattern 41 is not dissolved in petroleum naphtha, the ink flow path pattern 41 is hardly dissolved and remains.

On the 1st board | substrate 33, the 1st coating resin layer 36 of several same or different shape is collectively formed. In this step, the first substrate 33 is cut into pieces by a dicer 44, for example, DAD-561 manufactured by Disco Corporation as shown in FIG. Since the ink flow path pattern 41 still remains at this stage as described above, it is possible to prevent contaminants generated at the time of cutting the first substrate 33 from entering the individual flow paths 34.

Next, the cut substrate is placed on a chip tray or the like. A propylene glycol monomethyl ether acetate solution is used, for example, as a polar solvent which can dissolve the positive resist. This material is immersed in the propylene glycol monomethyl ether acetate solution with ultrasound. As a result, as shown in Fig. 13, the remaining ink flow path pattern 41 is dissolved and removed.

Then, postcure is performed at 150 degreeC for about 1 hour, and the photosensitive 1st coating resin layer 36 is hardened completely.

Next, as shown to FIG. 4 and 5, the 1st board | substrate 33 which has the 1st coating resin layer 36 is bonded to one side of the recessed part 32a of the ink supply member 32, and to the other side, The second substrate 37 having the second covering resin layer 38 is bonded. Moreover, the upper plate which closes the discharge surface 36a side of the ink supply member 32 to the discharge surface 36a of the 1st coating resin layer 36, and the discharge surface 36a side of the 2nd coating resin layer 38. (39) is bonded. Thus, the ink jet recording head 23 can be manufactured.

The head cap 24 for protecting the ejection surface 36a of the inkjet recording head 23 does not eject ink i, and forms the ejection surface 36a of the inkjet recording head 23 while not printing. By closing, the nozzle 35 is protected from drying. When printing, the head cap 24 wipes the excess ink i attached to the discharge surface 36a with the cleaning roller 24a shown in Fig. 14 when moving from the bottom surface of the head cartridge 2 and discharges it. The face 36a is cleaned.

In the inkjet recording head 23, the first coating resin layer 36 is formed of an oxetane resin composition having toughness and elongation resistance. As a result, when the discharge surface 36a is cleaned with the cleaning roller 24a, even if a load is applied to the discharge surface 36a, it is possible to prevent the first coating resin layer 36 from being peeled from the first substrate 33. Can be.

In the main body 3 to which the head cartridge 2 is attached, as shown in FIG. 1, the head cartridge 2 is attached to the head cartridge attachment portion 51. In addition, the main body 3 is provided with a paper feed tray 53 in which recording papers P before being printed on the paper feed ports 52 provided below the front surface are stacked. The main body 3 is attached with a delivery tray 55 for storing the recording paper P printed on the paper delivery opening 54 provided on the upper front side.

As shown in FIG. 14, the main body 3 has a head for opening and closing a paper feed / discharge mechanism 56 for conveying the recording paper P and a head cap 24 provided on the discharge surface 36a of the head cartridge 2. The cap opening and closing mechanism 57 is provided.

According to the structure as described above, the printer apparatus 1 is based on the print data input from the information processing apparatus installed in the outside, the paper feeding / discharging mechanism 56, the head cap opening and closing mechanism 57, and the inkjet recording head 23 It is controlled by the control part provided in the control circuit which controls the electric current supplied to.

Specifically, in the printer apparatus 1, first, when a print start command is sent to the control unit by the operation of the operation button 3a provided in the main body 3, the paper feeding / discharging mechanism 56 is controlled by the control signal from the control unit. And the head cap opening and closing mechanism 57 are driven so that the printer device 1 is ready for printing as shown in FIG.

In the printer device 1, the head cap 24 is moved by the head cap opening and closing mechanism 57 to the front side where the paper feed tray 53 and the discharge tray 55 are installed with respect to the head cartridge 2. Accordingly, in the printer apparatus 1, the nozzle 35 provided on the discharge surface 36a of the inkjet recording head 23 is exposed to the outside, so that the ink i can be discharged.

In the paper feeding / discharging mechanism 56 of the printer apparatus 1, the pair of separation rollers 62a and 62b are pulled out from the paper feed tray 53 by the paper feed roller 61 and rotated in opposite directions. 1 sheet of recording paper P drawn out by the above) is conveyed to the reversing roller 63 to reverse the conveying direction. Then, the recording paper P is conveyed by the conveyance belt 64 provided at the position facing the discharge surface 36a of the inkjet recording head 23. In the printer apparatus 1, the recording paper P conveyed by the conveyance belt 64 is supported by the flat plate 65 at a predetermined position, and the recording paper P is opposed to the discharge surface 36a.

Next, in the printer apparatus 1, the discharge energy generating element 33a provided in the inkjet recording head 23 is heated based on the control signal of the print data. In the printer apparatus 1, when the discharge energy generating element 33a is heated, ink i drops from the nozzle 35 with respect to the recording paper P conveyed to the printing position, as shown in Figs. 6A and 6B. It is discharged in a state. Therefore, an image, a character, etc. which consist of ink dots are printed on the recording paper P. FIG.

In the printer apparatus 1, when the ink droplet i is ejected from the nozzle 35, the same amount of ink i as the amount of ejected ink i is jetted from the ink cartridge 11 through the connection portion 25 from the ink cartridge 11. The recording head 23 is replenished.

Next, in the printer apparatus 1, the conveyance belt 64 which rotates the printed recording paper P in the direction of the discharge port 54, and the discharge medium provided on the discharge port 54 side opposite to the conveyance belt 64. The recording paper P is supplied to the discharge port 54 by the roller 66.

In the printer apparatus 1, printing is performed on the recording sheet P as described above. In the printer apparatus 1, the 1st coating resin layer 36 which comprises the individual flow path 34 and the nozzle 35 of the inkjet recording head 23 is formed of the oxetane resin composition. Accordingly, the first coating resin layer 36 becomes low in stress and can exhibit high mechanical strength with high toughness and elongation resistance, so that the first coating resin layer is peeled off or cracked from the first substrate 33. Such problems can be prevented from occurring. In the printer apparatus 1, since the shape of the individual flow path 34 can be prevented from being deformed, the ink i can be discharged from the nozzle 35 in a predetermined direction at the same volume and discharge rate.

In addition, in the printer apparatus 1, by forming the 1st coating resin layer 36 using an oxetane resin composition, water resistance and chemical-resistance are obtained.

In addition, when the first coating resin layer 36 of the printer device 1 contains an optimal additive, ie, a silane coupling agent or the like, in addition to the oxetane resin composition, adhesion to the first substrate 33 can be further improved. Can be. Therefore, peeling of the 1st coating resin layer from the 1st board | substrate 33 can be prevented more reliably.

As a result, in the printer apparatus 1, high quality printed matter can be obtained, and high reliability over a long period of time can also be obtained.

On the other hand, the printer apparatus 1 described above has been described taking an example in which an electrothermal conversion element is used as the discharge energy generating element 33a. However, the discharge energy generating element 33a is not limited to this. For example, the printer device 1 may have an electromechanical conversion method in which ink i is discharged electromechanically from a nozzle by an electromechanical conversion element such as a piezoelectric element.

In addition, although embodiment demonstrated the printer apparatus as an example, the application field of this invention is not limited to this. The invention is widely applicable to other liquid ejection devices, for example facsimile machines or copiers.

Although the line type printer apparatus 1 was demonstrated as an example in embodiment, the application of this invention is not limited to this. For example, the present invention is applicable to a serial printer apparatus in which a head cartridge moves in a direction substantially orthogonal to the traveling direction of the recording sheet P. FIG.

<Examples>

The physical properties of the oxetane resin composition constituting the first coating resin layer and the ink resistance and the print quality of the inkjet recording head having the first coating resin layer using the oxetane resin composition were evaluated.

<Review of physical properties of oxetane resin composition>

In order to confirm about the problem in resin, ie, the internal stress after hardening of resin, the following experiment was done. The internal stress is confirmed by observing the film thickness before curing of the resin and the film thickness after curing. When the film thickness after resin hardening is the same as the film thickness before resin hardening, it can be considered that the internal stress by the volume change according to hardening of resin is very small.

&Lt; Example 1 >

In Example 1, the solution containing the oxetane resin composition shown in following Table 1 was spin-coated on the wafer whose diameter is 6 inches. In this step, after prebaking at 90 ° C. for 5 minutes on a hot plate, the solution was applied such that the layer had a thickness of 20 μm. Then, 1 J / cm <2> was exposed to the wafer by the mirror projection aligner exposure machine (MPA-600FA: Canon company make). The wafer was postbaked at 90 ° C. for 5 minutes on a hot plate, and then cured at 200 ° C. for 1 hour to obtain a cured film of an oxetane resin composition.

Phenolic novolac type
Oxetane compound
(Average number of nuclei 3) 100 parts by weight Photo cationic polymerization initiator
(SP-170: made in Adeka) 2 parts by weight Silane coupling agent
(2- (3,4-epoxycyclohexyl)
Ethyltrimethoxysilane 0.5 parts by weight Organic solvent
(Oil Naphtha: Ifsol 150:
Manufacture of Idemitsu Kosan Co., Ltd. 100 parts by weight

&Lt; Comparative Example 1 &

In Comparative Example 1, a cured film of an alicyclic epoxy resin composition was obtained in the same manner as in Example 1 using a solution containing the alicyclic epoxy resin composition shown in Table 2 below.

Alicyclic epoxy resin
(EHPE-3150: Daicel Chemical Industries
(Daicel Chemical Industries, Ltd.) manufacture 100 parts by weight Photo cationic polymerization initiator
(SP-170: made in Adeka) 2 parts by weight Silane coupling agent
(2- (3,4-epoxycyclohexyl)
Ethyltrimethoxysilane 0.5 parts by weight Organic solvent
(xylene) 100 parts by weight

The film thickness after hardening at 200 degreeC on the hotplate for 1 hour using the cured film obtained in Example 1 and Comparative Example 1 was measured. As a result of the measurement, the film thickness was not reduced in the cured film containing the oxetane resin composition shown in Table 1. On the other hand, in the cured film containing the alicyclic epoxy resin composition shown in Table 2, the film thickness was reduced.

In addition, the stress of the cured film was measured with the thin film stress measuring apparatus. According to the result, the stress of the cured film containing the oxetane resin composition shown in Table 1 was significantly lower than the cured film containing the alicyclic epoxy resin composition shown in Table 2.

<Evaluation of Ink Resistance and Print Quality of Inkjet Recording Heads>

<Example 2>

In Example 2, the inkjet recording head 23 as shown in Fig. 4 was manufactured as follows. First, on the first substrate 33 having the discharge energy generating element 33a shown in FIG. 7, a positive resist having a novolak resin as a main component as a dissolvable resin layer (manufactured by Tokyo Okagyo Co., Ltd.) PMER-P-LA900PM) was applied. Then, the positive resist was prebaked on a hot plate for 6 minutes at 110 ° C. The pattern exposure of the individual flow path 34 was performed with the Canon mirror projection aligner exposure machine (MPA-600FA). As a result, as shown in FIG. 8, the ink flow path pattern 41 was formed in the part which becomes the individual flow path 34 with the soluble resin layer. The exposure amount of this step was 800 mJ / cm <2>.

In order to develop the resist, a dip development was carried out with a P-7G exclusive developer (TMAH (tetramethylammonium hydroxide solution) 3%), and the first substrate 33 was washed with running water of pure water. The film thickness of the positive resist after image development was 10 micrometers.

Next, the solution which melt | dissolved the oxetane resin composition shown in Table 1 in the density | concentration of about 50 weight% in petroleum naphtha which does not melt the ink flow path pattern 41 was prepared. As shown in FIG. 9, this solution was apply | coated on the ink flow path pattern 41 by spin coating, and the photosensitive 1st coating resin layer 36 which consists of the oxetane resin composition shown in Table 1 was formed. The film thickness deposited on the ink flow path pattern 41 of this first covering resin layer 36 was 20 µm.

Next, as shown in FIG. 10, with the Canon projection mirror aligner exposure machine (MPA-600 FA) with respect to the 1st coating resin layer 36, for formation of the nozzle 35 and the ink supply port 40, Pattern exposure was performed. When performing pattern exposure, the active energy ray 43 is irradiated to the first coating resin layer 36 through the patterned mask 42 so that the portions corresponding to the nozzle 35 and the ink supply port 40 are not exposed. do. In this step, the exposure amount was 800 mJ / cm 2, and afterbaking was performed at 65 ° C. for 60 minutes.

Next, as shown in FIG. 11, the image development of the part of the photosensitive 1st coating resin layer 36 which was not exposed by petroleum naphtha was performed. Thereafter, the first substrate 33 was immersed in the IPA to remove the developer residue, and then washed. Thereby, the nozzle 35 and the ink supply port 40 were formed by removing the 1st coating resin layer 36 of the unexposed part. In addition, the nozzle 35 was 15 micrometers in diameter. In this step, the ink flow path pattern 41 remained almost undissolved.

In addition, as shown in FIG. 12, the 1st board | substrate 33 was cut | disconnected to the predetermined magnitude | size by the dicer 44 (DAD-561 by DISCO Corporation). In this step, since the ink flow path pattern 41 still remained, contaminants generated at the time of cutting the first substrate 33 were prevented from entering the individual flow path 34.

Next, the cut substrate was placed on a chip tray or the like, and a propylene glycol monomethyl ether acetate solution was used as a polar solvent, for example, capable of dissolving the positive resist. Substrates were immersed in propylene glycol monomethyl ether acetate solution while giving ultrasound. As a result, as shown in FIG. 13, the remaining ink flow path pattern 41 was dissolved and removed.

Next, after 1 hour of curing at 150 ° C., the photosensitive first coating resin layer 36 was completely cured.

Next, as shown to FIG. 4 and FIG. 5, the 1st board | substrate 33 which has the 1st coating resin layer 36 is bonded to one side of the recessed part 32a of the ink supply member 32, and the other On the side, the second substrate 37 having the second covering resin layer 38 was bonded. Furthermore, the inkjet recording head 23 was manufactured by bonding the upper plate 39 on the discharge surface 36a of the first coating resin layer 36 and on the second coating resin layer 38.

Comparative Example 2

In Comparative Example 2, the first coating resin layer 36 was prepared from the alicyclic epoxy resin composition shown in Table 2, and the same as in Example 2 except that xylene was used for the development of the first coating resin layer 36. The inkjet recording head 23 was manufactured.

The ink immersion test was conducted by immersing the inkjet recording head 23 prepared in Example 2 and Comparative Example 2 in black ink at 60 캜 for one week. As the black ink, an ink for an LPR-5000 printer device composed of pure water, ethylene glycol, a black dye, or the like was used.

As a result of performing an ink immersion test, in the inkjet recording head 23 of Example 2 using the oxetane resin composition shown in Table 1 as a material of the first coating resin layer 36, the number of first coatings from the first substrate 33 was measured. No change such as the layer 36 peeled off was observed at all. On the other hand, in the inkjet recording head 23 of Comparative Example 2 using the alicyclic epoxy resin composition shown in Table 2 as the material of the first coating resin layer 36, a part of the first coating resin layer 36 after being immersed in ink. The peeling which is considered to be the cause of stress by hardening was seen.

Print quality evaluation was performed as follows. The inkjet recording head 23 of Example 2 or Comparative Example 2 was attached to the printer apparatus described above, and recording was performed using an ink having a composition of pure water / diethylene glycol / black dye = 80 / 17.5 / 2.5. In the inkjet recording head 23 of Example 2, stable printing could be performed, and the obtained printed matter was of high quality. On the other hand, in the inkjet recording head 23 of Comparative Example 2, the print quality was not satisfactory in some cases. In the inkjet recording head 23 of Comparative Example 2, the head was observed with an optical microscope after long-term use, and as a result, interference fringes that appeared to be produced by peeling of the coating resin were observed.

According to one embodiment of the present invention, a part of the flow path constitutes a coating resin layer having an orifice or a first coating resin layer having individual flow paths and orifices is formed of an oxetane resin composition. Due to the properties as a low stress material possessed by the oxetane compound, the coating resin layer can be made low in stress, cracks can be prevented, peeling from the substrate can be prevented, and excellent durability can be provided. Further, according to the embodiment of the present invention, chemical resistance can be provided by forming the coating resin layer or the first coating resin layer from the oxetane resin composition. Therefore, according to the embodiment of the present invention, manufacturing yield and quality are improved, and high reliability is obtained over a long term.

It should be understood by those skilled in the art that various modifications, combinations, subcombinations and modifications may occur depending on design requirements and other factors, so long as they are within the scope of the appended claims or their equivalents.

Claims (28)

A substrate provided with a liquid discharge energy generating element and constituting a part of a flow path for supplying a liquid, and A coating resin layer provided on the substrate to constitute a part of the flow path and having an orifice for discharging the liquid, Here, the coating resin layer is a liquid discharge type recording head comprising an oxetane compound having two or more oxetanyl groups in a molecule, an oxetane resin composition having a photocationic polymerization initiator and a silane coupling agent as essential components. The liquid ejecting recording head according to claim 1, wherein the oxetane compound having two oxetanyl groups is represented by the following formula (2). <Formula 2>

(In Formula 2, R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluoro benzyl group, methoxy benzyl group or phenoxy ethyl group.) The liquid ejecting recording head according to claim 1, wherein the oxetane compound having two oxetanyl groups is represented by the following formula (3). <Formula 3>

In Formula 2, R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluorobenzyl group, methoxy benzyl group or phenoxy ethyl group, and R ₃ is a linear or branched saturated hydrocarbon having 1 to 12 carbon atoms, and carbon number Linear or branched unsaturated hydrocarbons of 1 to 12, aromatic hydrocarbons represented by the following formulas 8, 9, 10, 11 and 12, linear or cyclic alkylenes containing a carbonyl group represented by the formulas 13 and 14, formula 15 And a group having two valences selected from aromatic hydrocarbons including a carbonyl group represented by 16. Further, in the following formulas 8, 9, 10, 11, and 12, R ₄ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and aryl Group or an aralkyl group, R ₅ represents -O-, -S-, -CH _2- , -NH-, -SO _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , Or —C (CF ₃ ) ₂ —, and each R ₆ is a hydrogen atom or an alkyl having 1 to 6 carbon atoms Represents a group) (8)

&Lt; Formula 9 >

&Lt; Formula 10 >

&Lt; Formula 11 >

&Lt; Formula 12 >

&Lt; Formula 13 >

&Lt; Formula 14 >

&Lt; Formula 15 >

<Formula 16>

The liquid ejecting recording head according to claim 1, wherein the oxetane compound having three or more oxetanyl groups is represented by the following formulas (4) to (6). &Lt; Formula 4 >

&Lt; Formula 5 >

(6)

(In Formulas 4 to 6, each R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluoro benzyl group, methoxy benzyl group or phenoxy ethyl group.) The liquid ejecting recording head according to claim 1, wherein the oxetane compound having three or more oxetanyl groups is represented by the following formula (7). &Lt; Formula 7 >

(Formula 7, R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluoro benzyl group, methoxy benzyl group or phenoxy ethyl group, R ₇ is carbon number shown in the following formula 17, 18 or 19 Branched alkylene groups of 12 to 12, aromatic hydrocarbons represented by the formula (20), 21 or 22, n represents the number of functional groups represented by the formula (7) bonded to R ₇ , in the formula (22), R ₈ is hydrogen An atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group) &Lt; Formula 17 >

&Lt; Formula 18 >

(19)

<Formula 20>

&Lt; Formula 21 >

(22)

The liquid discharge type recording head according to claim 1, wherein the content of the silane coupling agent is 0.1% by weight or more and less than 1% by weight. The liquid discharge type recording head according to any one of claims 1 to 6, wherein the orifices for discharging liquid are arranged in a line shape. A liquid supply member having a recess forming a part of a common flow path for supplying a liquid; A first substrate joined to one side of the concave portion of the liquid supply member, the end face of which forms part of a common flow path, and on which a liquid discharge energy generating element is provided; A first coating resin layer provided on the first substrate and having an individual flow path for supplying a liquid supplied from a common flow path to the periphery of the liquid discharge energy generating element and an orifice for discharging the liquid; A second substrate joined to the other side of the recess of the liquid supply member, the cross section of which forms part of the common flow path; A second coating resin layer provided on the second substrate; And It is provided on the 1st coating resin layer and the 2nd coating resin layer, and has an upper plate which closes the discharge surface side of a common flow path, Wherein the first coating resin layer comprises an oxetane compound having two or more oxetanyl groups in a molecule, an oxetane resin composition containing an optical cationic polymerization initiator and a silane coupling agent as essential components. The liquid ejecting recording head according to claim 8, wherein the oxetane compound having two oxetanyl groups is represented by the following formula (2). <Formula 2>

(In Formula 2, R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluoro benzyl group, methoxy benzyl group or phenoxy ethyl group.) The liquid ejecting recording head according to claim 8, wherein the oxetane compound having two oxetanyl groups is represented by the following formula (3). <Formula 3>

In Formula 2, R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluorobenzyl group, methoxy benzyl group or phenoxy ethyl group, and R ₃ is a linear or branched saturated hydrocarbon having 1 to 12 carbon atoms, and carbon number Linear or branched unsaturated hydrocarbons of 1 to 12, aromatic hydrocarbons represented by the following formulas 8, 9, 10, 11 and 12, linear or cyclic alkylenes containing a carbonyl group represented by the formulas 13 and 14, formula 15 And a group having two valences selected from aromatic hydrocarbons including a carbonyl group represented by 16. Further, in the following formulas 8, 9, 10, 11, and 12, R ₄ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and aryl Group or an aralkyl group, R ₅ represents -O-, -S-, -CH _2- , -NH-, -SO _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , Or —C (CF ₃ ) ₂ —, and each R ₆ is a hydrogen atom or an alkyl having 1 to 6 carbon atoms Represents a group) (8)

&Lt; Formula 9 >

&Lt; Formula 10 >

&Lt; Formula 11 >

&Lt; Formula 12 >

&Lt; Formula 13 >

&Lt; Formula 14 >

&Lt; Formula 15 >

<Formula 16>

The liquid ejecting recording head according to claim 8, wherein the oxetane compound having three or more oxetanyl groups is represented by the following formulas (4) to (6). &Lt; Formula 4 >

&Lt; Formula 5 >

(6)

(In Formulas 4 to 6, each R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluoro benzyl group, methoxy benzyl group or phenoxy ethyl group.) The liquid ejecting recording head according to claim 8, wherein the oxetane compound having three or more oxetanyl groups is represented by the following formula (7). &Lt; Formula 7 >

(Formula 7, R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluoro benzyl group, methoxy benzyl group or phenoxy ethyl group, R ₇ is carbon number shown in the following formula 17, 18 or 19 Branched alkylene groups of 12 to 12, aromatic hydrocarbons represented by the formula (20), 21 or 22, n represents the number of functional groups represented by the formula (7) bonded to R ₇ , in the formula (22), R ₈ is hydrogen An atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group) &Lt; Formula 17 >

&Lt; Formula 18 >

(19)

<Formula 20>

&Lt; Formula 21 >

(22)

The liquid discharge type recording head according to claim 8, wherein the content of the silane coupling agent is 0.1% by weight or more and less than 1% by weight. The liquid discharge type recording head according to any one of claims 8 to 13, wherein the orifices for discharging the liquid are arranged in one or more rows in parallel. A substrate provided with a liquid discharge energy generating element and constituting a part of a flow path for supplying a liquid, and A coating resin layer provided on the substrate to constitute a part of the flow path and including an orifice for discharging the liquid, Wherein the coating resin layer comprises a liquid discharge type recording head for discharging a liquid consisting of an oxetane compound having two or more oxetanyl groups in a molecule, and an oxetane resin composition containing an optical cationic polymerization initiator and a silane coupling agent as essential components. Liquid discharge device. The liquid ejecting apparatus according to claim 15, wherein the oxetane compound having two oxetanyl groups is represented by the following formula (2). <Formula 2>

(In Formula 2, R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluoro benzyl group, methoxy benzyl group or phenoxy ethyl group.) The liquid ejecting apparatus according to claim 15, wherein the oxetane compound having two oxetanyl groups is represented by the following formula (3). <Formula 3>

In Formula 2, R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluorobenzyl group, methoxy benzyl group or phenoxy ethyl group, and R ₃ is a linear or branched saturated hydrocarbon having 1 to 12 carbon atoms, and carbon number Linear or branched unsaturated hydrocarbons of 1 to 12, aromatic hydrocarbons represented by the following formulas 8, 9, 10, 11 and 12, linear or cyclic alkylenes containing a carbonyl group represented by the formulas 13 and 14, formula 15 And a group having two valences selected from aromatic hydrocarbons including a carbonyl group represented by 16. Further, in the following formulas 8, 9, 10, 11, and 12, R ₄ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and aryl Group or an aralkyl group, R ₅ represents -O-, -S-, -CH _2- , -NH-, -SO _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , Or —C (CF ₃ ) ₂ —, and each R ₆ is a hydrogen atom or an alkyl having 1 to 6 carbon atoms Represents a group) (8)

&Lt; Formula 9 >

&Lt; Formula 10 >

&Lt; Formula 11 >

&Lt; Formula 12 >

&Lt; Formula 13 > &Lt; Formula 14 >

&Lt; Formula 15 >

<Formula 16>

The liquid discharge apparatus according to claim 15, wherein the oxetane compound having three or more oxetanyl groups is represented by the following Chemical Formulas 4 to 6. &Lt; Formula 4 >

&Lt; Formula 5 >

(6)

(In Formulas 4 to 6, each R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluoro benzyl group, methoxy benzyl group or phenoxy ethyl group.) The liquid ejecting apparatus according to claim 15, wherein the oxetane compound having three or more oxetanyl groups is represented by the following formula (7). &Lt; Formula 7 >

(Formula 7, R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluoro benzyl group, methoxy benzyl group or phenoxy ethyl group, R ₇ is carbon number shown in the following formula 17, 18 or 19 Branched alkylene groups of 12 to 12, aromatic hydrocarbons represented by the formula (20), 21 or 22, n represents the number of functional groups represented by the formula (7) bonded to R ₇ , in the formula (22), R ₈ is hydrogen An atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group) &Lt; Formula 17 >

&Lt; Formula 18 >

(19)

<Formula 20>

&Lt; Formula 21 >

(22)

The liquid discharge device according to claim 15, wherein the content of the silane coupling agent is 0.1% by weight or more and less than 1% by weight. The liquid ejecting apparatus according to any one of claims 15 to 20, wherein an orifice for ejecting liquid is provided in a line shape. A liquid supply member having a recess forming a part of a common flow path for supplying a liquid; A first substrate joined to one side of the concave portion of the liquid supply member, the cross section of which constitutes a part of the common flow path, and on which a liquid discharge energy generating element is provided; A first coating resin layer provided on the first substrate and having an individual flow path for supplying a liquid supplied from a common flow path to the periphery of the liquid discharge energy generating element and an orifice for discharging the liquid; A second substrate joined to the other side of the concave portion of the liquid supply member, the cross section of which forms part of the common flow path; A second coating resin layer provided on the second substrate; And It is provided on the 1st coating resin layer and the 2nd coating resin layer, and includes the upper board which closes the discharge surface side of a common flow path, Here, the first coating resin layer is a liquid discharge type recording which discharges a liquid composed of an oxetane compound having two or more oxetanyl groups in a molecule, an oxetane resin composition containing an optical cationic polymerization initiator and a silane coupling agent as essential components. Liquid ejecting device comprising a head. The liquid ejecting device according to claim 22, wherein the oxetane compound having two oxetanyl groups is represented by the following formula (2). <Formula 2>

(In Formula 2, R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluoro benzyl group, methoxy benzyl group or phenoxy ethyl group.) The liquid ejecting device according to claim 22, wherein the oxetane compound having two oxetanyl groups is represented by the following formula (3). <Formula 3>

In Formula 2, R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluorobenzyl group, methoxy benzyl group or phenoxy ethyl group, and R ₃ is a linear or branched saturated hydrocarbon having 1 to 12 carbon atoms, and carbon number Linear or branched unsaturated hydrocarbons of 1 to 12, aromatic hydrocarbons represented by the following formulas 8, 9, 10, 11 and 12, linear or cyclic alkylenes containing a carbonyl group represented by the formulas 13 and 14, formula 15 And a group having two valences selected from aromatic hydrocarbons including a carbonyl group represented by 16. Further, in the following formulas 8, 9, 10, 11, and 12, R ₄ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and aryl Group or an aralkyl group, R ₅ represents -O-, -S-, -CH _2- , -NH-, -SO _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , Or —C (CF ₃ ) ₂ —, and each R ₆ is a hydrogen atom or an alkyl having 1 to 6 carbon atoms Represents a group) (8)

&Lt; Formula 9 >

&Lt; Formula 10 >

&Lt; Formula 11 >

&Lt; Formula 12 >

&Lt; Formula 13 >

&Lt; Formula 14 >

&Lt; Formula 15 >

<Formula 16>

The liquid ejecting device according to claim 22, wherein the oxetane compound having three or more oxetanyl groups is represented by the following Chemical Formulas 4 to 6. &Lt; Formula 4 >

&Lt; Formula 5 >

(6)

(In Formulas 4 to 6, each R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluoro benzyl group, methoxy benzyl group or phenoxy ethyl group.) The liquid ejecting device according to claim 22, wherein the oxetane compound having three or more oxetanyl groups is represented by the following formula (7). &Lt; Formula 7 >

(Formula 7, R ₁ represents a group having an aromatic ring of a phenyl group, benzyl group, fluoro benzyl group, methoxy benzyl group or phenoxy ethyl group, R ₇ is carbon number shown in the following formula 17, 18 or 19 Branched alkylene groups of 12 to 12, aromatic hydrocarbons represented by the formula (20), 21 or 22, n represents the number of functional groups represented by the formula (7) bonded to R ₇ , in the formula (22), R ₈ is hydrogen An atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group) &Lt; Formula 17 >

&Lt; Formula 18 >

(19)

<Formula 20>

&Lt; Formula 21 >

(22)

The liquid discharge device according to claim 22, wherein the content of the silane coupling agent is 0.1% by weight or more and less than 1% by weight. The liquid discharge device according to any one of claims 22 to 26, wherein the orifices for discharging the liquid are arranged in a line shape.

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