JPH0444574B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a liquid jet recording head, and more particularly, to a liquid jet recording head that generates droplets of a recording liquid such as ink and attaches them to a recording material such as paper to perform recording. The present invention relates to a recording head for generating droplets of recording liquid used in a recording method. [Prior Art] The liquid jet recording method generates small droplets of recording liquid such as ink and attaches them to a recording material such as paper to perform recording, and the noise generated during recording is negligible. It has attracted attention as a recording method that is extremely small and capable of high-speed recording, and can also record on plain paper without the need for special processing such as fixing.Recently, various types of recording methods have been actively researched. There is. The recording head section of a recording device used in a liquid jet recording method generally has an orifice (liquid discharge port) for discharging recording liquid, and communicates with the orifice, so that the energy for discharging the recording liquid can be used for recording. The recording medium is configured to include a liquid passage having a portion that acts on the recording liquid, and a liquid chamber for storing the recording liquid to be supplied to the liquid passage. During recording, the energy for ejecting the recording liquid is generated by a heating element disposed at a predetermined position in a part (energy application part) that applies ejection energy to the recording liquid, which forms part of the liquid path. In many cases, ejection energy is generated by various types of ejection energy generating elements such as piezoelectric elements. A method for manufacturing a liquid jet recording head having such a configuration is, for example, to form fine grooves in a flat plate of glass, metal, etc. by cutting or etching, and then to inject other materials into the flat plate with these grooves. A method including a step of bonding suitable plates to form a liquid passage, or forming, for example, a groove wall of a cured photosensitive resin on a substrate on which an ejection energy generating element is arranged by a photolithographic process, A method is known that includes a step of providing a groove to serve as a liquid passage on a substrate and bonding another flat plate (cover) to the thus formed grooved plate to form a liquid passage (for example, (Opening No. 57-43876). Among these methods for manufacturing liquid jet recording heads, the latter method using photosensitive resin allows fine processing of liquid passages with higher precision and higher yield than the former method, and is also easier to mass produce. Therefore, it has the advantage that it is possible to provide a liquid jet recording head of good quality and at a lower cost. The photosensitive resins used to manufacture such recording heads are those that have been used for pattern formation in printing plates, printed wiring, etc., or as photocurable paints and adhesives for glass, metals, ceramics, etc. Known resins are used, and dry film type resins have been mainly used from the viewpoint of work efficiency. [Problems to be Solved by the Invention] In a recording head using a cured film of photosensitive resin, in order to obtain excellent characteristics such as advanced recording characteristics, durability, and reliability, it is necessary to The resin has three properties: (1) it has particularly good adhesion to the substrate as a cured film, (2) it has excellent mechanical strength and durability when cured, and (3) it can be used in pattern exposure. It is required to have characteristics such as excellent sensitivity and resolution during patterning. However, at present, no photosensitive resin has been found that satisfies all of the above-mentioned required characteristics among the photosensitive resins used to form the liquid jet recording heads known so far. In other words, as a photosensitive resin for recording heads,
Materials used for pattern formation in printing plates, printed wiring, etc. have excellent sensitivity and resolution, but have poor adhesion and adhesion to glass, ceramics, plastic films, etc. used as substrates, and are difficult to harden. Mechanical strength and durability are not sufficient. Therefore, during the manufacturing stage of the recording head or during use, for example, the flow of the recording liquid in the liquid path may be obstructed, or the direction of droplet ejection may become unstable, resulting in a decrease in recording characteristics. This method has the disadvantage that the cured resin film is easily deformed, peeled off from the substrate, and damaged, which significantly impairs the reliability of the recording head. On the other hand, known photocurable paints and adhesives used for glass, metals, ceramics, etc. have excellent adhesion and adhesion to substrates made of these materials, and have sufficient mechanical strength when cured. Although it has the advantage of being strong and durable, it is inferior in sensitivity and resolution, requiring higher-intensity exposure equipment and longer exposure operations. Since it is not possible to obtain a high-density pattern, this method has the problem that it is not suitable for use in recording heads that require particularly fine precision processing. The present invention was made in view of these problems, and has a liquid passage wall made of a cured resin film that satisfies all the required characteristics as described above, and is inexpensive, precise, and highly reliable. The purpose of the present invention is to provide a liquid jet recording head with excellent durability. Another object of the present invention is to provide a liquid jet recording head having a structure in which liquid passages are microfabricated with high accuracy and high yield. Another object of the present invention is to provide a liquid jet recording head that is highly reliable and has excellent durability even when it is configured with multiple orifices. [Means for Solving the Problems] The above objects can be achieved by the present invention described below. The present invention has a liquid passage communicating with a liquid discharge port, and an ejection energy generating element that generates energy for ejecting the liquid in the liquid passage, wherein at least a portion of the liquid passage is exposed to active energy rays. In a liquid jet recording head formed of a cured region of a resin composition that is cured by (A) hydroxyl group-containing acrylic monomer,
(B) Acrylic monomer containing amino or alkylamino group, (C) Acrylic or vinyl monomer containing carboxyl group, (D) N-vinylpyrrolidone or its derivative, (E) Vinylpyridine or its derivative, and (F) with the following general formula A graft polymer polymer to which a branch chain mainly consisting of a structural unit derived from one or more monomers selected from the group consisting of acrylamide derivatives represented by the above is added; (However, R ¹ is hydrogen or has 1 to 1 carbon atoms.
3 alkyl or hydroxyalkyl group,
R ² represents hydrogen or an alkyl or acyl group having 1 to 4 carbon atoms which may have a hydroxy group. ) () A resin formed by esterifying a part of the epoxy groups present in an epoxy resin containing at least one kind of compound having two or more epoxy groups in the molecule with an unsaturated carboxylic acid. A liquid jet recording head characterized by: That is, the recording head of the present invention includes a substrate and a cured resin film layer that forms at least grooves serving as liquid passages, and improves the durability of each member constituting the recording head and the adhesiveness between each member. Moreover, the cured resin film layer is microfabricated with high precision, and this recording head has excellent recording characteristics, high reliability, and excellent durability during use. Hereinafter, the liquid jet recording head of the present invention will be explained in detail with reference to the drawings. FIG. 1 shows an example of the liquid jet recording head of the present invention, FIG. 1a is a perspective view of its main parts, and FIG.
1 is a cross-sectional view taken along line C-C' in FIG. 1a. This liquid jet recording head basically consists of a substrate 1
, a cured resin film 3H provided on the substrate and patterned in a predetermined shape, and a cover 7 laminated on the cured resin film. An orifice 9 for ejecting a liquid, a liquid passage 6-2 communicating with the orifice and having a portion where energy for ejecting the recording liquid acts on the recording liquid, and a recording liquid to be supplied to the liquid passage. A liquid chamber 6-1 for storage is formed. Furthermore, a supply pipe 10 for supplying recording liquid from the outside of the recording head to the liquid chamber 6-1 is connected to the through hole 8 provided in the cover. Note that the supply pipe 10 is omitted in FIG. 1a. During recording, the energy for ejecting the recording liquid is generated by a heating element or a piezoelectric element disposed at a predetermined position in a part of the liquid passage 6-2 that applies ejection energy to the recording liquid. Ejection energy is generated by applying ejection signals as desired to various types of ejection energy generating elements 2, such as elements, via wiring (not shown) connected to these elements. A substrate 1 constituting the recording head of the present invention is made of glass, ceramics, plastic, metal, etc., and a desired number of generating elements 2 are disposed at predetermined positions. In the example shown in FIG. 1, two generating elements are provided, but the number and arrangement of the heating elements are determined as appropriate depending on the predetermined configuration of the recording head. The cover 7 is made of a flat plate made of glass, ceramics, plastic, metal, etc., and is bonded to the cured resin film 3H by fusing or adhesive bonding, and the supply pipe 10 is connected to a predetermined position. A through hole 8 for connection is provided. In the recording head of the present invention, the liquid passage 6-2
The cured resin film 3H patterned into a predetermined shape constituting the wall of the liquid chamber 6-1 is a layer made of a resin composition having the composition described below provided on the substrate 1 or on the cover 7. It is obtained by patterning using a photolithography process. The cured resin film 3H is integrated with a cover made of a resin composition having the composition described below.
It may be patterned. The resin composition used to form the cured resin film provided on the substrate to constitute at least the portion that becomes the liquid passage is () one selected from the group consisting of alkyl methacrylate, acrylonitrile, and styrene; (A) hydroxyl group-containing acrylic monomer,
(B) Acrylic monomer containing amino or alkylamino group, (C) Acrylic or vinyl monomer containing carboxyl group, (D) N-vinylpyrrolidone or its derivative, (E) Vinylpyridine or its derivative, and (F) with the following general formula A graft copolymer polymer having a branch chain mainly composed of a structural unit derived from one or more monomers selected from the group consisting of acrylamide derivatives; (However, R ¹ is hydrogen or has 1 to 1 carbon atoms.
3 alkyl or hydroxyalkyl group,
R ² represents hydrogen or an alkyl or acyl group having 1 to 4 carbon atoms which may have a hydroxy group. ) () A resin formed by esterifying a part of the epoxy groups present in an epoxy resin containing at least one kind of compound having two or more epoxy groups in the molecule with an unsaturated carboxylic acid. It is an active energy ray-curable resin composition that has good adhesion to substrates made of glass, plastic, ceramics, etc. especially when formed into a cured film, and has good resistance to recording liquids such as ink and mechanical properties. It has excellent properties as a component of a liquid jet recording head, such as having excellent optical strength and being able to form precise, high-resolution patterns by patterning with active energy rays. Furthermore, this resin composition can be used as a dry film, and the above-mentioned excellent properties are exhibited in that case as well. Hereinafter, the composition of the active energy curable resin composition used for forming the recording head of the present invention will be explained in detail. The graft copolymer polymer (), which is an essential component of this active energy ray-curable resin composition, has a relatively rigid backbone that has properties as a structural material, and the above (A) to 3, which have hydrophilic properties. It is mainly composed of the monomer (F) with added branch chains that exhibit excellent adhesion to the substrate. When constituting the graft copolymer polymer, the monomers (A) to (F) above used to constitute the branch chain are specifically shown as (A), the 2-hydroxy Ethyl (meth)acrylate (hereinafter, when referred to as (meth)acrylate, it is meant to include both acrylate and methacrylate), 2-
Hydroxypropyl (meth)acrylate, 3-
Chloro-2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, or 1,4 - Examples include monoesters of cyclohexanedimethanol and acrylic acid or methacrylic acid, and the product name is Aronixx.
M5700 (manufactured by Toagosei Kagaku Co., Ltd.), TONE M100 (caprolactone acrylate, Union Carbide Co., Ltd.)
), Light Ester HO-mpp (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), Light Ester M-600A (trade name of 2-hydroxy-3-phenoxypropyl acrylate, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) Known and dihydric alcohols, e.g. 1,10
-Decanediol, neopentyl glycol, bis(2-hydroxyethyl) terephthalate, an addition reaction product of bisphenol A and ethylene oxide or propyleoxide, and a monoester of (meth)acrylic acid, etc. can be used. The amino or alkylamino group-containing acrylic monomer (B) includes (meth)acrylamide,
N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-di-t-butylaminoethyl (meth)acrylamide, etc. Can be mentioned. Examples of the carboxyl group-containing acrylic or vinyl monomer (C) include (meth)acrylic acid, fumaric acid, itaconic acid, and Toagosei Kagaku Co., Ltd. product names Aronix M-5400 and Aronix M-.
Examples include those known as 5500. (E) vinylpyridine or its derivatives include 2-vinylpyridine, 4-vinylpyridine,
2-vinyl-6-methylpyridine, 4-vinyl-
Examples include 1-methylpyridine, 2-vinyl-5-ethylpyridine, and 4-(4-pipenylinoethyl)pyridine. All of the monomers (A) to (E) above have hydrophilic properties, and when the resin composition used in the present invention is adhered to a support such as glass, ceramics, or plastic, they provide strong adhesion. It gives a sense of gender. Examples of acrylamide derivatives represented by the general formula (F) include N-methylol (meth)acrylamide, N-propoxymethyl (meth)acrylamide, N-n-butoxymethyl (meth)acrylamide, and β-hydroxyethoxymethyl (meth)acrylamide.
Acrylamide, N-ethoxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, α-hydroxymethyl-N-methylolacrylamide, α-hydroxyethyl-N
-Butoxymethylacrylamide, α-hydroxypropyl-N-propoxymethylacrylamide, α-ethyl-N-methylolacrylamide, α-propyl-N-methylolacrylamide, and other hydrophilic and thermally crosslinkable monomers are mentioned. These monomers (F) have not only hydrophilic properties but also condensation crosslinking properties when heated, and generally, water molecules or alcohol are released at temperatures of 100°C or higher, forming crosslinking bonds and forming graft copolymer polymers themselves. This also forms a network structure after curing, further improving the chemical resistance, mechanical strength, etc. of the pattern obtained by curing, thereby making the present invention more effective. In addition, by adding a portion of monomers that ring-open and crosslink by heat, such as glycidyl (meth)acrylate, to the monomers (A) to (F) above to form a branch chain, the monomers (F The same effect as in ) can be obtained. In addition to the above-mentioned thermal crosslinking, a photopolymerizable monomer is introduced into a part of the branch chain of the graft copolymer to be contained in the resin composition used for forming a cured resin film in the present invention for the same purpose. Therefore, it is also effective to crosslink the graft copolymer polymer.
Such methods for imparting photopolymerizability to branch chains include, for example, copolymerizing monomers containing carboxyl groups such as (meth)acrylic acid, or monomers containing amino groups or tertiary amine groups. A partial urethane compound of polyisocyanate having one isocyanate group and one or more acrylic ester groups in one molecule, and a branched hydroxyl group,
A method of reacting with an amino group or a carboxyl group, a method of reacting a branched hydroxyl group with acrylic acid chloride, a method of reacting a branched hydroxyl group with an acid anhydride, and then reacting with glycidyl (meth)acrylate, Methods such as a method of condensing the hydroxyl group of and the condensation crosslinking monomer exemplified in (F) to leave an acrylamide group on the side chain, a method of reacting the hydroxyl group of the branch chain with glycidyl (meth)acrylate, etc. can be used. . When the branch chains of the graft copolymer polymer are thermally crosslinkable, it is preferable to perform heating after forming a pattern by irradiation with active energy rays.
On the other hand, even when the branch chain is photopolymerizable, there is no problem in heating within an allowable range in terms of the heat resistance of the support, and in fact, more favorable results can be obtained. In addition to those derived only from hydrophilic monomers as exemplified in (A) to (F) above, the branch chains may be derived from various hydrophobic monomers that exhibit various other functions.
The branched chain may be used as a component of the copolymerization in the range of up to about 25% by weight. The monomers constituting the backbone chain of the graft copolymer polymer include alkyl groups having 1 to 4 carbon atoms such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate, acrylonitrile, and styrene. It is. In addition to those derived only from the above monomers,
For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, vinyl acetate, etc.
The backbone may be used as a copolymerization component in an amount up to 50% by weight. In the resin composition used to form the recording head of the present invention, the backbone provides high cohesive strength to the composition. The resin composition can be used in the form of a solution, solid film, etc. when forming the recording head.
It is provided in various shapes depending on the purpose of use, but when used as a dry film, in order to maintain the composition in a film form, approximately
It is preferred to use a relatively rigid backbone having a glass transition temperature of 50°C or higher. In this case, the backbone chain used may be composed of two or more types having different glass transition temperatures. Furthermore, if the composition of the present invention is used in the form of a solution, it is also possible to use a backbone chain with a low glass transition temperature that imparts flexibility to the composition. However, even in this case, in order to obtain a pattern with excellent chemical resistance and high mechanical strength, it is preferable that the backbone chain has a high glass transition temperature. The graft copolymer polymers used in the resin composition for forming a cured resin film in the present invention are broadly classified into those without curability, those with photopolymerizability, and those with thermal crosslinkability. However, in the curing process of the resin composition used in the present invention (i.e., irradiation with active energy rays and thermal curing as necessary), it imparts shape retention to the composition and enables precise patterning. It provides excellent adhesion, chemical resistance, and high mechanical strength to the pattern obtained by curing. The above-mentioned graft copolymer polymers can be produced by known methods, and specifically, for example, "Basics and Applications of Polomer Alloys" 10-35
Page (edited by the Society of Polymer Science and Technology, published by Tokyo Kagaku Dojin Co., Ltd., 1981)
It can be produced by various methods such as those described in 2010). Examples of these methods include a chain transfer method, a method using radiation, an oxidative polymerization method, an ion graft polymerization method, and a macromonomer method. The graft copolymer contained in the resin composition for forming a resin cured film used in the present invention has a more pronounced surfactant effect when the branch chain lengths are uniform, so it is recommended to use the method described below. Among these, the macromonomer method is particularly preferred because it is advantageous in terms of material design. The weight average molecular weight of the graft copolymer is preferably in the range of about 5,000 to 300,000, and when used as a dry film, the weight average molecular weight is preferably in the range of about 30,000 to 300,000. One of the epoxy groups present in the epoxy resin composed of one or more compounds containing two or more epoxy groups in one molecule, which is another component contained in the resin composition used for forming a cured resin film in the present invention. The resin () obtained by esterifying half with an unsaturated carboxylic acid (hereinafter referred to as half-esterified epoxy resin) exhibits curability with active energy rays in a resin composition for forming a cured resin film. At the same time, when the resin composition is applied in liquid form onto various supports made of glass, plastic, ceramics, etc. and then cured to form a cured film, or in the form of a dry film, various supports are applied. It is a component for imparting better adhesion to a support, water resistance, chemical resistance, dimensional stability, etc. to the cured film when it is used on a body. This half-esterified epoxy resin () is
A predetermined amount of unsaturated carboxylic acid is added to the epoxy resin.
In the presence of an addition catalyst and a polymerization inhibitor, in the presence or absence of a solvent, a part of the epoxy groups present in the epoxy resin is esterified with carboxylic acid by reaction at a temperature of 80 to 120°C. It can be obtained by a method such as half-esterification. Epoxy resins containing one or more compounds containing two or more epoxy groups in one molecule that can be used to form this half-esterified epoxy resin () include bisphenol A type, novolak type, Epoxy resins represented by ring type, or bisphenol S, bisphenol F, tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, glycerin triglycidyl ether, pentaerythol triglycidyl ether, triglycidyl isocyanurate Ether and the following general formula (However, R is an alkyl group or an oxyalkyl group, R ₀ is

【formula】

〔Effect of the invention〕

The liquid jet recording head of the present invention has a pattern mainly imparted by a half-esterified epoxy resin contained as an essential component in the active energy ray-curable resin composition that is a component of the head. A material having excellent sensitivity and resolution is used as a forming material, and by using the active energy ray-curable resin composition,
It has become possible to obtain a liquid jet recording head with excellent dimensional accuracy at a high yield. In addition, the active energy ray-curable resin composition for forming a cured resin film used in the present invention is provided with properties as an epoxy resin possessed by a graft copolymer polymer and a half-esterified epoxy resin as essential components. It also has excellent adhesion to substrates, mechanical strength, and chemical resistance, and by using this composition, it has become possible to obtain a recording head with long-term durability. In addition, when using an active energy ray-curable resin composition using a curable graft copolymer polymer, a liquid jet recording head having particularly excellent adhesion, mechanical strength, or chemical resistance can be obtained. Is possible. [Example] Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples and Examples. Synthesis example Bing polymer (N
-Butoxymethylacrylamide/2-hydroxyethyl methacrylate (=70/30 weight ratio))
was reacted with acrylic acid chloride to obtain a macromonomer (acrylic acid polybutoxymethylacrylamide/2-hydroxyethyl methacrylate) having a weight average molecular weight of about 3000 and having a vinyl group at one end of the molecular chain. 25 parts by weight of this macromonomer,
70 parts by weight of methyl methacrylate and 5 parts by weight of acrylonitrile are polymerized in methyl cellosolve,
A graft copolymer polymer (referred to as GP-4) having a weight average molecular weight of 6.8×10 ⁴ and having thermal crosslinkability was obtained. Note that the glass transition temperature of the copolymer chain of methyl methacrylate and acrylonitrile that constitutes the main chain of GP-4 is 105°C. Apart from this, Epikote with epoxy equivalent weight 450
1001 (manufactured by Ciel Chemical) in toluene 50% butyl acetate
It was dissolved in a 50% mixed solution to make a 30% solution. After adding 0.5 equivalents of methacrylic acid based on the epoxy groups present, and adding 0.2% of N-nitrosodiphenylamine based on the solid content as a polymerization inhibitor,
LiCl was added as a catalyst in an amount of 0.5% based on the solid content.
The reaction was carried out at 70-80°C for 5 hours. In this way, an epoxy resin in which 0.5 equivalent of 1.0 equivalent of epoxy was esterified with methacrylic acid, that is, a half-esterified epoxy resin was obtained. In addition, the half-esterified epoxy resin obtained here is
It was named HE-1. Using GP-4 and HE-1 thus obtained, an active energy ray-curable resin composition having the following composition was prepared. GP-4 100 parts by weight HE-2 150 〃 Copper phthalocyanine 1 〃 Paratoluenesulfonic acid 3 〃 Triphenylsulfonium tetrafluoroborate 10 〃 Methyl cellosolve 300 〃 Here, the mill dispersion of the resin composition was
By applying it to polyethylene terephthalate film with a wire bar and drying it at 100℃ for 20 minutes,
A dry film having a resin composition layer having a thickness of 75 μm was prepared and used for forming a liquid jet recording head of the present invention as described below. Example Using the dry film produced in the synthesis example, a heating element [hafnium boride (HfB ₂ )] 10 was prepared as an ejection energy generating element according to the steps shown in FIGS. 1 to 6 described earlier in the specification. Orifice (orifice dimensions: 75μm x 50μm, pitch 0.125
An on-demand liquid jet recording head having a diameter of 1 mm) was fabricated as follows. Note that 30 recording heads of the same shape were prototyped for each type. First, a plurality of heating elements were arranged at predetermined positions on a substrate made of silicon, and recording signal application electrodes were connected to these heating elements. Next, _two layers of SiO (thickness: 1.0 μm) are provided as a protective film on the surface of the substrate on which the heating element is arranged, and after cleaning and drying the surface of the protective layer, it is stacked on the protective layer. Film thickness shown in synthesis example heated to 120℃
75μm dry film, roll temperature 120℃,
Lamination was carried out using a laminator HRL-24 (trade name, manufactured by DuPont Co., Ltd.) at a speed of 0.4 f/min. and a pressurized condition of 1 Kg/cm ² . In this state, a polyethylene terephthalate film is laminated on the layer made of the active energy ray-curable resin composition laminated on the substrate. Next, a photomask having a pattern corresponding to the shapes of the liquid passages and liquid chambers is superimposed on the dry film provided on the substrate surface, and the above-mentioned elements are positioned so that they are installed in the liquid passages that are finally formed. After alignment, the dry film was exposed to ultraviolet light at an intensity of 12 mW/cm ² for 60 seconds from the top of the photomask. Next, after peeling off the polyethylene terephthalate film from the exposed dry film, it is immersed in 1,1,1-trichloroethane and developed, and the unpolymerized (uncured) portion of the dry film is removed from the substrate. After dissolution and removal, the cured dry film film remaining on the substrate formed grooves that would eventually become liquid passages and liquid chambers. After the development process was completed, the cured dry film film on the substrate was heated at 150° C. for 1 hour, and further cured by irradiating it with ultraviolet rays at an intensity of 50 mW/cm ² for 3 minutes. In this way, after forming grooves that will become liquid passages and liquid chambers on the substrate using the cured dry film film, epoxy resin is applied to a flat plate with through holes made of soda glass that will cover the formed grooves. After spin-coating the adhesive to a thickness of 3 μm, preheating it to B-stage, bonding it onto the cured dry film, and then fully curing the adhesive and fixing it to form a bonded body. . Next, the downstream side of the liquid passage of the bonded body, that is, the downstream side from the installation position of the discharge energy generating element.
A commercially available dicing saw (product name: DAD2H/6
A mold (manufactured by DISCO) was used to cut it to form an orifice for discharging the recording liquid. Finally, the cut surface was cleaned and dried, and the cut surface was polished to make it smooth, and a recording liquid supply pipe was attached to the through hole to complete the liquid jet recording head. All of the obtained recording heads had excellent dimensional accuracy and had liquid passages and liquid chambers that faithfully reproduced the mask pattern. Incidentally, the orifice dimensions were in the range of 50±5 μm, and the orifice pitch was in the range of 125±5 μm. The quality and durability of the thus prototyped recording head during long-term use were tested as follows. First, the obtained recording head was subjected to a durability test in which it was immersed in a recording liquid having the following composition at 60° C. for 1000 hours (environmental conditions comparable to those during long-term use of a recording head). Recording liquid components (1) H ₂ O / diethylene glycol / 1,3-dimethyl-2-imidazolidinone / CI Direct Blue 86 ^*1 (=57/30/10/3 parts by weight) PH = 8.0 (2) H ₂ O/diethylene glycol/N-methyl-2-pyrrolidone/CI direct black
154 ^*2 (=55/30/10/5 parts by weight) PH=9.0 (3) H ₂ O/diethylene glycol/polyethylene glycol #400/N-methyl-2-pyrrolidone/CI Direct Yellow 86 ^*3 (=65/ 10/10/10/5 parts by weight) PH=7.0 (4) H ₂ O/ethylene glycol/triethylene glycol/triethylene glycol monomethyl ether/CI food black 2 ^*4 (=67/10/15/5/3 Parts by weight) PH=10.0 (Note) ^*1 to ^*4 are water-soluble dyes, and caustic soda was used to adjust the pH. After the durability test, we observed the state of bonding between the substrate and cover and the cured dry film film for each head tested. As a result, no peeling or damage was observed in any of the recording heads, indicating good adhesion. . Then separately 10 of the obtained recording heads
For each head, attach each head to a recording device, and use the recording liquid described above to record a recording signal of ¹⁰⁸ pulses at 14
A printing test was carried out in which printing was performed by applying power to the recording head continuously over time. With respect to any of the recording heads, almost no deterioration was observed in both recording liquid ejection performance and printing condition immediately after printing started and after 14 hours had elapsed, indicating that the recording heads had excellent durability. Comparative Examples A commercially available dry film Vacrel (trade name of dry film solder mask, manufactured by DuPont Nemo Earth Co., Ltd.) with a film thickness of 75 μm, and a commercially available dry film Photoc SR-3000 (trade name, manufactured by Hitachi Chemical Co., Ltd.) with a film thickness of 50 μm A recording head was prepared in the same manner as in the example except that a recording head (manufactured by Co., Ltd.) was used. Durability tests similar to those in the examples were conducted on these recording heads. During the durability test, as a dry film
When Vacrel was used, peeling was observed with recording liquids (2) and (4) after 100 hours. Furthermore, after 300 hours, peeling was observed with the recording liquids (1) and (3). On the other hand, as a dry film, Photoc SR−
3000, each of the recording liquids (1) to (4)
Peeling was observed after 300 hours. Printing test example Hets created in the examples and comparative examples (10
A printing test was carried out by filling the recording liquid of the composition listed above in (4) into each of the test pieces. Next, each head filled with the recording liquid was stored for 200 hours at a temperature of 80° C. and a humidity of 90%, and then a printing test similar to that previously conducted was conducted. As a result, good printing was obtained in all 10 heads obtained in actual practice before and after storage, whereas poor printing was observed in all of the heads in the comparative example. When these defective print areas were observed under a microscope, it was observed that the recording droplets forming the characters were misaligned. Furthermore, when we observed the vicinity of the ejection opening of each head where printing defects occurred, we found that the dry film cured film in that area had peeled off.

[Brief explanation of drawings]

1 to 6 are schematic diagrams for explaining the liquid jet recording head of the present invention and its manufacturing method. 1: Substrate, 2: Discharge energy generating element, 3:
Resin layer, 3H: Resin cured film, 4: Photomask,
4P: Mask pattern, 6-1: Liquid chamber, 6-2:
Liquid passage, 7: cover, 8: through hole, 9: orifice, 10: supply pipe.

Claims (1)

[Scope of Claims] 1. A liquid passageway communicating with a liquid discharge port, and an ejection energy generating element that generates energy for ejecting the liquid in the liquid passageway, wherein at least a portion of the liquid passageway is In a liquid jet recording head formed of a cured region of a resin composition that is cured by active energy rays, the resin composition contains () one or more monomers selected from the group consisting of alkyl methacrylate, acrylonitrile, and styrene. (A) hydroxyl group-containing acrylic monomer,
(B) Acrylic monomer containing amino or alkylamino group, (C) Acrylic or vinyl monomer containing carboxyl group, (D) N-vinylpyrrolidone or its derivative, (E) Vinylpyridine or its derivative, and (F) with the following general formula A graft copolymer polymer having a branch chain mainly composed of a structural unit derived from one or more monomers selected from the group consisting of acrylamide derivatives; (However, R ¹ is hydrogen or has 1 to 1 carbon atoms.
3 alkyl or hydroxyalkyl group,
R ² represents hydrogen or an alkyl or acyl group having 1 to 4 carbon atoms which may have a hydroxy group. ) () A resin formed by esterifying a part of the epoxy groups present in an epoxy resin containing at least one kind of compound having two or more epoxy groups in the molecule with an unsaturated carboxylic acid. A liquid jet recording head characterized by: 2. The liquid jet recording head according to claim 1, wherein the component () is a resin obtained by esterifying 0.30 to 0.70 equivalents of 1.0 equivalents of epoxy groups present in the epoxy resin. 3. The liquid jet recording head according to claim 1, wherein the component () is a resin obtained by esterifying 0.45 to 0.55 equivalents of 1.0 equivalents of epoxy groups present in the epoxy resin. 4. The resin composition that is cured by the active energy rays is a graft copolymer polymer 20 of the above ().
~80 parts by weight, and 80 to 20 parts by weight of the resin () above.
3. The liquid jet recording head according to claim 3. 5. The resin composition that is cured by the active energy rays contains 100 parts by weight of the total amount of the graft copolymer polymer () and the resin ().
A liquid jet recording head according to any one of claims 1 to 4, which contains 0.1 to 20% by weight of a radical polymerization initiator that can be activated by the action of active energy rays. 6. The resin composition that is cured by the active energy rays contains 100 parts by weight of the total amount of the graft copolymer polymer () and the resin ().
Claims 1 to 5 include a photosensitive aromatic onium salt compound containing 0.2 to 15% by weight of an element belonging to Group A or Group A of the Periodic Table. A liquid jet recording head according to any one of the above. 7. A liquid jet recording head according to any one of claims 1 to 6, wherein the ejection energy generating element is a heat generating element.