JPH02131944A - Liquid jet recording head - Google Patents

Abstract

PURPOSE:To provide a recording head having a low cost, high accuracy, high reliability and excellent durability by incorporating specific graft copolymerizable polymer, specific epoxy resin, and polymerization initiator for generating Lewis acid by radiating it with active energy beam. CONSTITUTION:Composition contains graft copolymerizable polymer in which branched chain having a structure unit derived from one type of monomer of a group of monomers represented by formulae x and y is added to backbone chain having a structure unit derived from monomer of alkylmethacrylate, acrylonitrile and styrene as a main ingredient, its number-average molecular weight is 5000 or more, and its weight-average molecular weight is 50,000 or less, specific linear polymer, resin esterified with unsaturated carboxylic acid from part of epoxy resin containing compound having tow or more epoxy groups in its molecule, and polymerization initiator for generating Lewis acid by radiating it with active energy beam. In the formulae x and y, R<1> is 1-3 alkyl groups or hydroxyalkyl groups, R<2> is alkyl group or acyl group, R<3> is specific phenylalkyl group.

Description

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

[Second, K technology]

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 so small that it can be ignored. It has been noted as a recording method that enables high-speed recording and does not require special processing such as fixing on feeding paper, and has recently been actively researched into various types. There is.

The recording head section of a recording device used in the liquid jet recording method generally has an orifice (
a liquid passage communicating with the orifice and having a portion where energy for ejecting the recording liquid acts on the recording liquid; and a liquid for storing the recording liquid to be supplied to the liquid passage. It is configured with a chamber.

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. , piezoelectric elements, and other types of ejection energy generating elements.

As a method for manufacturing a liquid jet recording head having such a configuration, an example λ. For example, fine grooves are formed in a flat plate of glass, metal, etc. by cutting or etching, and a liquid passage is formed by joining another suitable plate to the flat plate with these grooves formed. Alternatively, for example, groove walls of a cured photosensitive resin are formed on a ζ plate in which ejection energy generating elements are arranged by a photolithography process, and grooves serving as liquid passages are provided in the substrate. A method is known that includes the step of joining another flat plate (cover) to the grooved plate formed by the method to form a liquid passage (for example, Japanese Patent Laid-Open 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 better accuracy and higher yield than the former method, and is also easier to mass-produce. Since it is simple, 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., and those that have been used as photocurable paints and adhesives for glass, metals, ceramics, etc. Known resins have been used, and dry film type resins have been mainly used due to reasons such as work efficiency.

[Problem to be solved by the invention]

In order to obtain excellent characteristics such as advanced recording characteristics, durability, and reliability in a recording head that uses a cured film of a photosensitive resin as part of its structure, the photosensitive resin used must have (1) In particular: (2) Excellent mechanical strength and durability when cured; (1) Sensitivity and resolution during patterning using pattern exposure. They are required to have excellent characteristics.

However, at present, there are few photosensitive resins that have been used to form known liquid jet recording heads that satisfy all of the above-mentioned required characteristics.

For example, photosensitive resins used for recording heads and for pattern formation in printing plates, printed wiring, etc. have excellent sensitivity and resolution;
It has poor adhesion and adhesion to glass, ceramics, plastic films, etc. used as substrates, and furthermore, its mechanical strength and durability when cured are not as good as 70%. Therefore, during the manufacturing stage of the recording head or during use, printing problems may occur, such as impeding the flow of the recording liquid in the liquid path or destabilizing the direction of droplet ejection, thereby reducing the recording characteristics. Deformation of the cured resin film and 'i+' from the board can significantly impair the reliability of the head.
+ a. It has the disadvantage of being easily damaged.

On the other hand, known photocuring paints and adhesives used for glass, metals, ceramics, etc. have excellent adhesion and adhesion to substrates made of these materials, and have sufficient mechanical properties when cured. Although it has the advantage of being strong and durable, it has poor sensitivity and resolution, so
For recording heads that require higher-intensity exposure equipment and longer exposure operations, and because their characteristics make it impossible to obtain high-resolution, precise, high-density patterns, particularly fine precision processing is required. The problem is that it is not suitable as a

In addition, in the photosensitive resin compositions used for various conventional purposes, various additives such as heterocyclic compounds having the ability to form complexes with metals, or coupling agents, etc. are added to the photosensitive resin. It was added to compositions to improve adhesion to metals, etc.
8-24035 etc.). However, this method has a problem in that, over a long period of time, the additives and the like cause phenomena such as oxidation and corrosion of the composition.

On the other hand, for the purpose of obtaining a cured composition with a 4-i degree of adhesion without the addition of such additives, etc., a polymer material consisting of a graft co-merchandising having polar groups in the branch chain. is JP-A-61-2113F! 45, Unexamined Japanese Patent Publication No. 1986 1-
28:+646. Contains the disclosed polymer f\JA quality (graft copolymer polymer)''
1-The active energy ray-curable resin composition improves adhesion without relying on additives or the like. Furthermore, it has the advantage of being able to improve the durability of the membrane.

However, in this composition, there still remains the problem that the molecular design of the polymer substance (graft copolymer polymer) is difficult.

That is, in general, while keeping the molecular weight and content of branch chains constant, the ffi! of the entire graft copolymer is determined. It is technically difficult to synthesize the average molecular weight over a wide range (approximately 50,000 to 350,000) to a desired value.

In other words, in order to improve the development characteristics during pattern formation, that is, the dissolution rate of the unpolymerized part, the swelling property of the polymerized part, and the resulting sensitivity, pattern sharpness, and resolution, it is necessary to use a polymeric material. The average molecular weight of should not be too small. In a graft copolymer polymer, a large number of branch chains having sufficient length to obtain effective adhesion are bonded to a relatively large molecular weight trunk chain to obtain an average molecular weight that meets the above objectives. is difficult with current synthetic techniques due to steric hindrance.

In other words, if the average molecular weight of the polymeric substance is too low,
There are certain limitations on the development characteristics of pattern-forming materials using it, that is, the dissolution rate of unpolymerized parts, the swelling f of polymerized parts, and the resulting sensitivity, pattern sharpness, and resolution adjustment. be.

The present invention has been made in view of the above-mentioned problems, and its objects are to have sufficient adhesion without the addition of additives, excellent development characteristics during pattern formation, and liquid jet recording. We use an active energy ray-curable resin composition whose properties can be easily controlled to obtain good properties as a component of the head, and it is inexpensive, dense, and highly reliable.
The objective is to provide a 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 good roughness 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 has multiple orifices.

[Means to solve the problem]

The above objects can be achieved by the following invention.

The present invention provides a liquid jet recording head in which a cured product of an active energy ray-curable resin composition is partially incorporated,
(A) A backbone mainly composed of structural units derived from one or more monomers selected from the group consisting of alkyl methacrylate, acrylonitrile, and styrene (hereinafter referred to as heptanomer component ■), which has the following general formula: At least one monomer selected from the group consisting of the heptanomer represented by (x) and the monomer represented by the following general formula (y) (hereinafter referred to as heptanomer component ■) has a branch chain having the m-position in the structure and a graft co-merchandising polymer having a number average molecular weight of 5,000 or more and a weight average molecular weight of 50,000 or less, and R1 CH2 = C.
・・(x)0=C-NH-CH2 -0-R2 RI CH2 =C ・-(
y) 0=C-0-R3 -OH [However, Rl represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group, and R2
represents hydrogen, or an alkyl group or acyl group having 1 to 4 carbon atoms which may have a hydroxy group,
R3 is an alkyl group having 2 to 6 carbon atoms, or a halogen-substituted alkyl group, -{- C H 2-), O -10C H -2-
) m-(tatashi, 2≦m+n≦6, n≠0, m≠0)
They are an alkyl ether group represented by the following formula, and a phenylalkyl group represented by the following formula (including cases where 2≦m, n≦4, n=o or m=O). ] (B) Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, t-butyl methacrylate,
Hensyl methacrylate, acrylonitrile, isobornyl methacrylate, isobornyl acrylate,
Derived from one or more monomers selected from the group consisting of tricyclodecane acrylate, tricyclodecane methacrylate, tricyclodecaneoxyethyl methacrylate, styrene, dimethylaminoethyl methacrylate, and cyclohexyl methacrylate (hereinafter referred to as monomer component ■) At least one monomer (hereinafter referred to as monomer component :However, monomer component 0 and monomer component (C) at least one kind of compound having two or more epoxy groups in the molecule; (D) an initiator that generates a Lewis acid upon irradiation with a single line of active energy; This is a liquid jet recording head.

The liquid jet recording head of the present invention can have various configurations as desired, but at least a cured product of the resin composition described above is used as a part of the configuration.

Hereinafter, an example of the liquid jet recording head of the present invention will be described in detail with reference to the drawings.

FIG. 1 shows an example of the liquid jet recording head of the present invention, FIG. 1(a) is a perspective view of its main parts, and FIG.
FIG. 3 is a cross-sectional view taken along line CC in FIG.

This liquid jet recording head basically consists of a substrate 1, a liquid passage wall 311 made of a cured resin film provided on the substrate and patterned into a predetermined shape, and a liquid passage wall 311 laminated on the liquid passage wall. Through these members, an orifice 9 for discharging recording liquid is communicated with the orifice, and the energy for discharging the recording liquid strikes the part that acts on the recording liquid. liquid passage 6-
2 and a liquid chamber 6-1 for storing recording liquid to be supplied to the liquid passage. Further, 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 four through holes 8 provided in the cover.

Note that the supply pipe IO is omitted in FIG. 1(a).

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. Wiring (not shown) connected to various types of ejection energy generating elements 2 such as elements, etc.
The ejection signal is generated by applying an ejection signal as desired via the ejection signal.

A substrate 1 constituting the recording head 1 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 addition, in the example of FIG. 1, two generating elements are provided, but
The number and arrangement of 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 liquid passage wall 311F by fusing or bonding using an adhesive, and the supply pipe 10 is connected at a predetermined position. A through hole 8 is provided for this purpose.

In this recording head, a liquid passage 6-2 and a liquid chamber 6-
The Sawada resin cured film patterned in a predetermined shape constituting the wall 311 of 1 is an active energy ray-curable film containing the above-mentioned components (A) to (D) provided on the substrate 1 or on the cover 7. It is formed by patterning a layer made of a resin composition using a photolithography process.

Hereinafter, an example in which a cured film of the resin composition is used in the structure of the liquid passage wall 311 has been described, and a cured film (cured product) of the resin composition can be suitably used in other parts of the recording head. obtain.

For example, 1. As cover 7 (a) 2. (b) as the liquid passage wall 311 and the cover 7 (in this case, the liquid passage wall 311 and the cover 7 may be formed integrally, or may be formed separately and then joined) 3. Liquid passage wall 311 and cover 7 made of various resins, etc.
4. as the adhesive layer 14 (c), (e) and (g) with. (d) and (f) as the adhesive layer 14 between the liquid passage wall 3H and the liquid passage wall 311 and the cover 7; 5. (h) can be used as the adhesive layer I4 (two-layer structure) between the liquid passage wall 3H and the liquid passage wall 311 and the cover 7. In addition, among the above configurations, the configurations in FIGS. 7(a) to (6), (h) and FIG. 7(f)
For forming the liquid passage wall 3H in FIGS. 7(f) and 7(f), a dry film type may be preferably used.
For the adhesive layer 14 in G), a type that is used in a liquid state and then cured is preferably used.

Historically, the recording head of the present invention is shown in FIGS. 8(a) and (b).
It may also have a structure that discharges droplets in a direction perpendicular to the liquid passage (6-2) shown in FIG. A cured film of the resin composition can be suitably used for the same parts as shown in FIG. 7 above, such as the part shown in b).

Hereinafter, an active energy ray-curable resin composition containing the above-mentioned constituent components (A) to (D) used in the configuration of the recording head of the present invention will be described.

The resin composition has good adhesion to various members such as substrates made of glass, brass, ceramics, etc., especially when formed into a cured film, and has good resistance to recording liquids such as ink and mechanical strength. Furthermore, it has excellent properties as a component of a liquid jet recording head, such as being able to form a dense, high-resolution pattern by patterning with active energy rays.

Furthermore, this resin composition can be used as a dry film, and in that case also exhibits the excellent properties listed in -F.

In forming the trunk button of the graft copolymer polymer (A) contained in the tree composition, the monomer component (2) described above is used as a soil component (R).

As for the monomers used for the branch 3n, in addition to the above-mentioned monomer components (■), the following polar monomers may be added as necessary.
-It is necessary.

(I) Acrylic monomer containing an amine group or alkylamino group (II) Acrylic or vinyl monomer containing a carboxyl group (III) N-vinyl pyrrolitone or its derivative (IV) Vinyl pyridine or its conductor Also, a hydrophobic monomer of about It can be used as a component of copolymerization within the range of 25 mol % or less.

As a polymerization method for graft copolymerization polymer F (8), for example, "Bolimer Alloy Basics and Ogawa" (Ichiryo, The Society of Polymer Science,
Various conventionally known methods can be used, such as those described on pages 10 to 35 of Tokyo Kagaku Gakujin (Published by Tokyo Kagaku Gakujin, 1981). These methods include: ■ chain transfer method, ■ method using radiation, ■ oxidative polymerization method, ■ ion craft polymerization method, and macromonomer method. and monomer ■, number average molecular weight 5,000 or more, city [11 average molecular weight 5
as appropriate to obtain less than 10,000 grafts of covalent polymers.
By carrying out polymerization while selecting the 1i polymerization conditions, the kraft copolymerization polymer f(A) constituting the composition of the present invention can be obtained.

Note that among methods ■ to ■, if method ■ or ■ is used, the lengths of the branch chains of the copolymer (A) will be the same, so method ■ is especially easy to select materials (design). It is more preferable from the viewpoint of safety.

``--The linear polymer CB) has the above-mentioned monomer component ① as the main component, uses the above-mentioned monomer component ⑛, has a number average molecular weight of 50,000 or more, and a weight average molecular weight of 350,000 or more, 11! using a conventionally known method while appropriately selecting the coalescence conditions so as to obtain a 1fc coalescence with a glass transition temperature of 60°C or higher. You can get what you want by combining them. In addition, it is preferable to add the heptanomer component ゜ in a range of 5 mol % to 30 mol %. If the monomer component in the linear polymer exceeds 30 mol%, the concentration of polar groups in the cured coating film will increase, and the adhesion promoter effect will increase. This is not preferable because it may result in a decrease in water resistance.

Furthermore, if the monomer component (1) is less than 5 mol %, the effect of improving adhesion and acting as a binder for the coating film will be insufficient.

Gives a high glass transition temperature to the created cured film,
For the purpose of increasing water resistance, particularly favorable results can be obtained by using methyl methacrylate, isobornyl methacrylate, isobornyl acrylate, tricyclodecane methacrylate, tricyclotecan acrylate, etc. as the above-mentioned monomer component (2).

1 Epoxy in one molecule contained in the composition↓
Resin (C) obtained by esterifying a part of the epoxy groups present in an epoxy resin consisting of one or more compounds containing two or more [ with an unsaturated carboxylic acid (hereinafter referred to as half-esterified epoxy resin) ) means that the composition exhibits sufficient curability with high sensitivity to active energy rays in the presence of the polymerization initiator (D) described below, and in addition, the composition can be used to cure glass, plastics, etc. When it is applied in liquid form to various supports L made of materials, ceramics, etc. and then hardened to form a cured film, or when it is used by adhering to various supports L in the form of a dry film. It is a component for imparting better adhesion to the support, water resistance, chemical resistance, dimensional stability, etc. to the cured film made of the resin composition.

This half-esterified epoxy resin (C) cannot be obtained by a normal method. An unsaturated carboxylic acid is reacted with an addition catalyst and a polymerization inhibitor in the presence or absence of a solvent at a temperature of 80 to 120°C to convert some of the epoxy groups present in the epoxy resin. Esterification with carboxylic acid (half esterification), etc.
It can be obtained by commonly used methods.

Examples of epoxy resins containing one or more compounds containing two or more epoxy groups in one molecule that can be used to form the half-esterified epoxy resin (C) include bisphenol A type, nopolac type, and alicyclic type. Epoxy resins represented by the following types, or hisphenol S, hisphenol F, tetrahypoxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, glycerin 1-lycricidyl ether, bentaerythol triglycidyl ether, isocyanuric acid Triglycyl ether, polyfunctional epoxy resins such as epoxyurethane resins represented by the following general formula (I) (where n4 represents an alkyl group or an oxyalkyl group), and mixtures of one or more of these. I can puke.

Incidentally, examples of IL forms of these polyfunctional epoxy resins include the following. That is, as a bisphenol A type epoxy resin,
For example, Ebicoat 828. 834, 871, 10
01. 1004 (product name, manufactured by Shell Chemical Co., Ltd.),
DER: ] 31-J, 337-J, 661-. 1
, 664-. J, 687-. J (manufactured by Tau Chemical Co., Ltd.) and Ebikuron B00 (trade name, large 11 r
Nki Kagaku-[manufactured by Gyosha Co., Ltd.] etc.: Examples of the Noholac type epoxy resin include Epikote 152, +54, !
72, (trade name, manufactured by Shell Chemical Co., Ltd.), Araldite EP
N 1138 (product name, manufactured by Chiha Geigy), D
ER 431, 438, and 439 (trade name, manufactured by Dow Chemical Company), etc.; Examples of alicyclic epoxy resins include Araldite CY-175, -176, -179,
-182, -184, -192 (product name, manufactured by Ciba Geigy), Chisson Knox 090, 091, 09
2, 301, 313 (product name, manufactured by Chisso ■), Syracure (cyH8CIIRE) 6 100, 61
10, 6200 and ERI 4090, 4617,
2256, 54+1 (trade name, manufactured by Union Carbide): Examples of polyglycidyl ethers of aliphatic polyhydric alcohols include ethylene glycol siglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and Bolibro. Pyrene glycol diglycidyl ether, neobentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolbroband triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 2,2-dibromo Neobentyl glycol diglycidyl ether, etc.; polyhydric glycidyl ethers derived from aromatic polyhydric alcohols include diglycidyl ethers of 2 to 16 mol adducts of alkylene oxides of bisphenol A, and 2 to 16 moles of alkylene oxides of bisphenol F; Examples include diglycidyl ether as a 16 mol adduct, and diglycidyl ether as a 2 to 16 mol adduct of alkylene oxide of bisphenol S.

Various unsaturated carboxylic acids can be used to half-esterify the epoxy group of the epoxy resin mentioned above, but it is desirable to impart curability to the resin composition with better activation energy. In order to
A basic unsaturated carboxylic acid having an acrylic or methacrylic vinyl group at least at one end of the molecule and a carboxyl group at the other end can be preferably used.

Representative examples of such unsaturated carboxylic acids include acrylic acid and methacrylic acid, or monoesters obtained by reacting dicarboxylic acids with (meth)acrylic esters having one hydroxyl group. Compounds can also be used.

-Dicarphonic acids of letter L include phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, isosebacic acid, and tetrahydrophthalic acid. Examples include acids and anhydrides thereof.

In addition, as the methacrylic acid ester having one and 1-roxyl J, (1-), 2-human xibucyl (meth)acrylate, 3-chloro2-human xibucyl (meth)acrylate, Acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)
Acrylate, 5-human xybentyl (meth)acrylate and 6-hydroxy l\xyl (meth)acrylate, etc. can be mentioned.

Examples of addition reaction catalysts that can be used in the half-esterification reaction of epoxy resins include metal halides such as zinc chloride and lithium chloride, sulfide compounds such as dimethyl sulfide and methyl phenyl sulfite, and dimethyl sulfoxide, methyl Compounds of the sulfoxide class such as ethyl sulfoxide, e.g.
, N-dimethylaniline, pyridine, triethylamine, pencyldimethylamine and other tertiary amine compounds, and their hydrochlorides or bromates, such as tetramethylammonium chloride, trimethyltodecylpencylammonium chloride, triethylbenzylammonium chloride, etc. Examples of quaternary ammonium salts include compounds of sulfonic acids such as para-toluenesulfonic acid and compounds of mercabutanes such as ethylmercabutane and probylmercabutane.

Historically, examples of conjugation inhibitors that can be used in half-esterification include hydroquinone, alkyl- or aryl-substituted hydroquinone, tertiary butylcatechol,
Mention may be made of pyrogallol, naphthylamine, β-naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, N-nitrosodiphenylamine and nitrobenzene.

Furthermore, examples of solvents that can be used when half-esterification is carried out in the presence of a solvent include toluene, xylene, methyl isobutyl ketone, methyl ethyl ketone, ethyl acetate, butyl acetate, and isobutyl acetate.

The amount of epoxy resin and carboxylic acid used during half-esterification is such that the ratio of the epoxy group of the epoxy resin to the carboxyl group of the carbonic acid is preferably 1:0.3 to 1.
:0.7, more preferably 1 :0.45~] :0
．． 55, as appropriate.

In other words, if the esterification rate of the epoxy group by unsaturated carboxylic acid in the half-esterified epoxy resin is higher than the above range, the good chemical resistance and dimensional stability derived from the epoxy resin will be effective for the resin composition. Moreover, if it is lower than the above range, the resin composition will not have high resolution and sufficient curability due to the action of active energy rays based on the methacrylic acid ester group.

As described above, the active energy ray-curable resin composition used in the present invention has the high sensitivity of the half-esterified epoxy resin (C), the curability due to the action of active energy rays based on the acrylic acid ester group, and the epoxy group. This resin composition is cured by irradiating it with active energy rays, and then heated at 80°C or higher for about 10 minutes to 3 hours to further heat cure it. Good chemical resistance, dimensional stability, etc. derived from the half-esterified epoxy resin are more effectively imparted to the cured film.

The polymerization initiator (D) that generates a Lewis acid upon irradiation with active energy rays, which is contained in the resin composition, is a polymerization initiator (D) that cures the half-esterified epoxy resin (C) mentioned above by the action of the Lewis acid. It is a component for making the composition exhibit sufficient curability with high sensitivity to active energy rays, and is preferably a photosensitive material containing an element belonging to group VTa as disclosed in Japanese Patent Publication No. 52-14278. Aromatic onium salt compound having
Aromatic onium salt compounds with photosensitivity containing elements belonging to group Va as shown in Japanese Patent Publication No. 14279, or aromatic octaronium salts with photosensitivity as shown in Japanese Patent Publication No. 14277/1983 You can also use something like Both of these aromatic onium salt compounds or aromatic halonium salts release Lewis acids when irradiated with active energy rays, resulting in half-esterified epoxy resins (
C) has the property of curing.

Photosensitive aromatic onium salt compounds having elements belonging to Group VTa or Group Va of Group F are typically those of Formula II. [(R3)a(R')b(1 yen.X]d" [M
Qe de la-1)...- (I1) (1 In the two notations, R3 is a monovalent organic aromatic group, and R4 is a monovalent organic aliphatic group selected from an alkyl group, a cycloalkyl group, and a substituted alkyl group) group, R5 is a polyvalent organic group constituting a heterocyclic or fused ring structure selected from aliphatic groups and aromatic groups, X is Group Vla selected from sulfur, selenium and tellurium, or nitrogen, phosphorus, arsenic, antimony and An element belonging to Group Va selected from bismuth, M represents a metal or t metal, and Q represents a halogen group, and a represents O when X is an element belonging to Group VTa.
An integer of 3, 0 if X is an element belonging to Group Va
an integer of ~4, b is an integer of 0 to 2, C is an integer of 0 or 1 when X is an element belonging to group Vla, X is an integer of group V
If the element belongs to group a, an integer of 0 to 2, f is M
The valence of 2 to 7! 5 number, e is an integer greater than f and less than or equal to 8, and the sum of a, b, and C is 3 if X is an element belonging to group Vla, and X is an element belonging to group Va. 4 and d=ef].

Further, as the photosensitive aromatic octaronium salt, the following general formula (2); [(R'). (R7)hX]i”[MQj]-L
k-"-(I[I)(1-In the formula, R6 is one aromatic organic group, R7 is a divalent aromatic organic group, X is a halogen group, M is a metal or a metal, and Q is each represents a halogen group, g is an integer of 0 or 2, and h is 0 or 1
an integer in which the sum of g and h is equal to 2 or the valence of X, i is equal to k-1, j is an integer from 2 to 7 and equal to the cost of M, and k is greater than l8 )
Examples include compounds represented by:

Specific examples of the photosensitive aromatic onium salt compounds containing elements belonging to Group Vla or Group Va include photosensitive aromatic onium salts of elements belonging to Group Via, such as; Examples include photosensitive aromatic salts of elements belonging to Group Va such as. Further, as specific examples of photosensitive aromatic halonium salts, for example, the above-mentioned Lewis acid-releasing initiator (D)
In addition, polyamines, polyamides, acid anhydrides, boron acid fluorides, which are generally widely known as curing agents for epoxy resins, -amine complexes, imidazoles, etc.
A curing agent such as a complex of midazole and a metal salt may be used if necessary.

The active energy ray-curable resin composition used for producing the liquid jet recording head of the present invention described above is one that can be cured by active energy rays, or is one that can be cured by active energy rays.
Synthetic polymer (A) and/or linear polymer r- (B)
When using light 1 [α-characteristic as the active energy ray and using an active energy line with a wavelength of 250 na+ to 450 nm as the active energy ray, it is possible to generate radicals that can be activated by the action of the active energy ray. It is preferable to add a polymerization starting material to the resin composition.

Specific examples of such radical 1 synthesis initiators include penzoin alkyl ether such as benzoin isobutyl ether, henzoin isobutyl ether, hensoin-1-butyl ether, benzoin ethyl ether, and henzoin methyl ether. Ethers; benzophenone, 4,4'-bis(N,N-diethylamino)benzophenone, penzophenone methyl ether and other henzophenones; 2-ethylanthraquinone, 2
- anthraquinones such as tert-butylanthraquinone, 2,4-dimethylthioxanthone, 2,4-
Xanthone such as diisopropylthioxanthone: 2
．． 2-dimethoxy-2-7enylacetophenone 2α,
α-cyclo-4-phenoxyacetophenone, p-
tert-butyltolic oral acetophenone, p-
terL-butyl dichloroacetophenone, 2.2-
Acetophenones such as diethoxyacetophenone and ρ-dimethylaminoacetophenone; or hydroxyl phenyl ketone (Irgacure 184
11-(4-isobrobylphenyl)-2-hydroxy-2-methylbroban-1-one (manufactured by Chiha Geigy ■)
Darocure 1116 manufactured by MERCK:
2-Hydroxy-2-methyl-1-phenylbropan-l-one (Darocur 117: manufactured by Merck ■) and the like are preferably used. In addition to these radical polymerization initiators, an amino compound may be added as a photopolymerization accelerator.

Examples of amino compounds used as photopolymerization accelerators include ethanolamine, acyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, p-
Examples include dimethylaminobenzoic acid n-amyl ester and p-dimethylaminobenzoic acid isoamyl ester.

Next, the blending ratio of each of the above components is appropriately selected depending on the location or purpose of use of the active energy ray-curable resin composition containing these components in the liquid jet recording head of the present invention.

For example, a graft copolymer polymer (A) and a linear polymer (B
) is (A):(B)=80:20~5
A range of 0:50 is desirable, and within this range, good adhesion to gas based on the graft copolymer polymer and good buttering properties based on the linear polymer can be obtained.

The weight ratio of half-esterified epoxy resin (C) to the total increase in polymeric substances (^) + (B) is ((^)
+(B)):((:) = 100:50~+00:
A range of 200 is desirable. The polymerization initiator (D) is {(8)÷ with respect to the total amount of the resin (8)+(B)÷(C)
(B)+(C)}:([1)=+00:l~10
It is desirable to use the ratio in the range of 0:10.

In addition, when using the above radical polymerization initiator (F.) and/or amino compound (F) as a photonail synthesis accelerator, the amount added ((E) + (F)) [(E)・0
, (F)・0] is the total amount of resin (A
) +CI1)+(C), <(A) + (B
) + (C)l : ((E)÷(F)l = 10
It is desirable to use it in the range of 0.l to too:10.

Historically, the active energy ray-curable resin composition used in the present invention may contain, if necessary, a condensation crosslinking catalyst, a heat exchanger, a coloring agent such as a dye or a pigment, a filler, hydroquinone or paramethoxyphenol. Heat stabilizers such as adhesion promoters, plasticizers, bodies such as silica and talc, pigments such as τ pigments, and lehering agents that impart coating suitability may be added.

For example, examples of the condensation crosslinking catalyst include sulfonic acids represented by valatoluenesulfonic acid, carboxylic acids such as formic acid, and the like. Examples of the thermal polymerization inhibitor include hydroquinone and its derivatives, paramethoxyphenol, and phenothiazine. As the colorant, oil-soluble dyes and pigments may be added to the extent that they do not substantially prevent the transmission of active energy rays. The filler increases the hardness of the coating film by -F, coloring it,
In order to increase adhesion and mechanical strength, extender pigments, plastic particles, etc. commonly used in paints are used. Examples of adhesion promoters include silane coupling agents as inorganic surface modifiers, low molecular weight surfactants, and the like.

When using the above-mentioned active energy ray-curable resin composition in the form of a solution or applying it to a plastic film or the like as a film base material when forming a dry film for producing the liquid jet recording head of the present invention, Examples of the solvent used for this include hydrophilic solvents such as alcohols, glycol ethers, and glycol esters. Of course, these hydrophilic solvents are mainly used, and if necessary, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate 5 isobutyl acetate, aromatic hydrocarbons such as toluene and xylene, and their halogen substituted substances It is also possible to use an appropriate mixture of chlorine-containing aliphatic solvents such as , methylene chloride, and 1,1.1-trichloroethane. Incidentally, these solvents can also be used as a developer for the resin composition.

When using the active energy ray-curable resin composition in the form of a solution for producing the liquid jet recording head of the present invention,
Alternatively, when forming a dry film, the solvent used when coating the resin composition on a film base such as a plastic film may include hydrophilic solvents such as alcohols, glycol ethers, and glycol esters. can be mentioned. Of course, these hydrophilic solvents can be used as soil bodies, and if necessary, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone, esters such as ethyl acetate and isobutyl acetate, aromatic hydrocarbons such as toluene and xylene and their halogenated products, chlorine-containing fats such as methylene chloride and 1,1.1-trichloroethane. It is also possible to use an appropriate mixture of group solvents and the like.

Incidentally, these solvents can also be used as a developer for the resin composition.

In producing the liquid jet recording head of the present invention, the resin composition can be used to form a cured layer on a substrate or the like by a conventional method.

For example, (1) When forming a layer consisting of a cured coating film on a substrate etc., apply the active energy ray-curable resin composition in liquid form to the substrate etc. to form a liquid coating film, This is followed by evaporation to dryness. Then, the obtained dry coating film is cured by irradiating active energy rays to form a layer consisting of a cured coating film.

(2) In the case of forming a layer consisting of a cured coating film in the shape of a desired pattern on a substrate, etc. (this is the case); etc. and subsequently evaporated to dryness. Then, by scanning the layer consisting of the dried coating film with a laser beam in a desired pattern and removing the unexposed areas with an appropriate solvent such as 1.1.1-tricloethane, the desired pattern is formed on the substrate, etc. Form a cured coating layer with a shape.

(3) When forming a layer consisting of a cured coating film in a desired pattern shape on a substrate, etc. (Part 2): On a substrate, etc., apply the active energy ray-curable resin composition described in (g) in liquid form. It is applied to form a coating followed by evaporation drying.

A photomask having a pattern of a desired shape through which active energy rays do not pass is superimposed on the layer consisting of the obtained dry coating film, and the photomask is exposed to active energy rays from a photomask. Then, the unexposed area is 1.1.1-
It is removed using a suitable solvent such as trichlorethane to form a layer of a cured coating film in a desired pattern shape on a substrate or the like.

(4) When forming a photosensitive tri-film and laminating a surface dry film on a substrate etc.: Applying the active energy ray-curable resin in a liquid state to a polyethylene terephthalate film L to form a liquid film, Subsequently, the film is evaporated and dried to obtain a photosensitive dry film on the polyethylene terephthalate film. The dry film is layered on a substrate or the like by a conventional lamination method to obtain a laminate. Then, the photosensitive dry film laminated on the substrate or the like is cured by irradiating it with active energy rays in the same manner as method (1) above.

When it is desired to form the cured photosensitive film into a desired pattern, the tri-film laminated on the support is treated in the same manner as in method (2) or (3).

The active + [energy ray curable resin composition has the general formula (x
), if it contains a monomer represented by
The cured film obtained by the methods (1) to (4) above was heated to 80°C
It is desirable to carry out condensation curing by heat treatment at a temperature of 200°C.

In the process of manufacturing the liquid jet recording head of the present invention, the active energy rays used for curing the active energy single-line curable resin composition or pattern exposure of the resin composition have already been widely put into practical use. Examples include ultraviolet rays and electric f-rays. As an ultraviolet light source, wavelength 2
Examples include high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, etc., which contain a large amount of wavelength from 50r++t+ to 450nm.
The intensity of light in the vicinity of 365 nm at a practically acceptable distance between objects to be irradiated is 1 mW/cm2 ~ IO
It is preferable that it be about OmW/cm2. There are no particular limitations on the electric f-ray irradiation device, but 0.5 to 20M Rad
A device with a dose in the range of is practically suitable.

Hereinafter, the method for manufacturing a liquid jet recording head of the present invention will be described with reference to the drawings, taking as an example a case in which the liquid passage wall 3+1 is formed using a dry film type cured film obtained from the above-mentioned resin composition.

? 2 to 6 are schematic diagrams for explaining the manufacturing procedure of the liquid jet recording head of the present invention.

In order to form the liquid jet recording head of the present invention, first, as shown in FIG. The number of pieces will be placed. In addition, in order to provide the surface of the substrate 1 with resistance to recording liquid, electrical insulation, etc., if necessary, SiO2, T
A205, a protective layer such as glass may be coated. Further, although not shown, an electrode for recording signal manually is connected to the ejection energy generating element 2.

Next, after cleaning the surface of the substrate 1 obtained through the steps shown in FIG. 2 and drying it at, for example, 80 to 150°C,
As shown in FIGS. 3(a) and 3(b), the above-mentioned active energy ray-curable resin composition 3 of dry film type (film thickness, approximately 20 μ to 200 scales) was added to
For example, 0.5 to 0.4 f/mi by heating to about ℃.
n. The film is laminated onto the substrate surface IA at a speed of 1 to 3 κg/cm 2 under pressure conditions.

Subsequently, as shown in FIG. 4, a dry film layer 3.1-. After a photomask 4 having a pattern 4P of a predetermined shape that does not transmit active energy rays is superimposed on the photomask 4, exposure is performed from the F portion of the photomask 4.

The photomask 4 and the substrate 1 are aligned so that the L element 2 is located in the liquid passage area that will be finally formed through steps such as exposure and development. This can be carried out by drawing alignment marks in advance on each of the substrate 1 and the mask 4, and performing {i2 alignment according to the marks.

When exposure is carried out in this way, the area other than the area covered by the pattern, that is, the exposed part of the tri-film layer 3 is cured, and the unexposed part remains soluble in the solvent. It becomes insoluble in solvents.

After pattern exposure of the try film layer 3 is completed, next, the exposed dry film 3 is exposed, for example! ．． 1.1-
A dry film layer 3 that is soluble in a solvent is developed by being immersed in a volatile solvent such as trichloroethane.
The unpolymerized (unhardened) portion of the resin is dissolved and removed from the substrate 1F, and as shown in FIGS. 6-2 and a groove that will become the liquid chamber 6-1.

Next, the cured resin film 311 on the substrate 1 is coated with at least 80%
The mixture is heated at a temperature of 10° C. or higher for about 10 minutes to 3 hours for thermal polymerization. In addition, when a thermosetting graft copolymer polymer is used in the resin composition 3, the heat treatment temperature is
The temperature is at least 100°C for about 5 to 60 minutes.

In addition, in the recording head of this example, an example is described in which a dry film type resin composition, that is, a solid material is used to form the grooves that will become the liquid passage 6-2 and the liquid chamber 6-t. However, the active energy ray-curable resin composition that can be used in forming the recording head of the present invention is not limited to solid ones, and of course liquid ones can also be used.

A method for forming a layer made of a liquid resin composition on a substrate using a squeegee, which is used when creating a relief image, for example, corresponds to J7 of a coating film of a desired resin composition. For example, a method may be used in which a wall with a certain height is provided around the substrate and excess resin composition is removed using a squeegee. In this case, the viscosity of the resin composition is suitably between IOO cp and 3000 cp. Further, the height of the wall placed around the substrate must be determined in consideration of the amount of weight loss due to evaporation of the solvent contained in the photosensitive resin composition.

In addition, when using a solid resin composition, it is preferable to apply a dry film to the substrate by heat-pressing it as described below.

However, when forming the recording head of the present invention, a solid film type recording head is convenient in terms of handling and the fact that the thickness can be easily and accurately controlled.

After forming the grooves that will finally constitute the liquid passage 6-2 and the liquid chamber 6-1 using the cured resin film 311 in this way, as shown in FIGS. 6(a) and 6(b), Then, the flat plate 7 that covers the groove is bonded to the cured resin film 31jl with an adhesive to form a bonded body.

In the steps shown in FIG. 6(a) and FIG. 6(b),
A specific method for attaching the cover 7 is, for example, after coating the flat plate 7 of glass, ceramic, metal, plastic, etc. with an epoxy resin adhesive to a thickness of 3 to 4 scales,
The adhesive layer is preheated to a so-called B stage,
There is a method of bonding this to a cured dry film 3 11 4- and then curing the adhesive layer. It is also possible to use a method that does not use an adhesive, such as directly heat-sealing it onto the film 3.

In addition, a resin layer made of the resin composition for forming a cured resin film according to the present invention is provided on the side of the cover 7 that joins with the liquid passage, and this is thermally fused to the cured tree film 31 that forms the liquid passage. A method in which the resin composition for forming a cured resin film of the present invention is then used as an adhesive is also preferred.

In FIG. 6, 6-1 is a liquid chamber, 6-2 is a liquid passage, and 8 is a supply pipe for supplying recording liquid from the outside of the recording head (not shown) to the inside of the recording head. A through hole is shown for connecting (not shown in A).

In this way, the cured resin film 3t provided on the substrate 1
1 and the flat plate 7, this joined body is cut along C-C on the downstream side of the liquid passage 6-2 shown in FIGS. 6(a) and 6(b). , an orifice for discharging the recording liquid is formed, which is the opening of the liquid passage during cutting.

This process involves the ejection energy generating element 2 and the orifice 9.
This is done in order to normalize the distance between the two, and the area to be cut here is generally selected.

For this cutting, a dicing method or the like commonly used in the conductor industry can be employed.

Note that the downstream part of the liquid path in the present invention refers to the downstream area in the flow direction of the recording liquid when recording is performed using a recording head, specifically, the area where the ejection energy generating element 2 is installed. Based on the position, it refers to the part of the F flow liquid passage.

After cutting is finished, the cut surface is polished and smoothed.
A supply pipe IO is attached to the tT through hole 8 to complete a liquid jet recording head as shown in FIG.

In addition, in the example explained above, the resin cured film 3B is formed on the substrate 1.
Although the cover 7 was bonded to the cover 7 after forming the cover 7, it is also possible to form a resin cured film 311 on the cover 7 side and then bond this to the substrate 1. Further, the liquid passage 6-2 and the liquid chamber 6-1 may be formed separately.

/ 7/'' 7/ / / / / / [Examples] The present invention will be explained in more detail with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.

Synthesis Example 1 The components shown below were used as components of the active energy single-line curing resin composition used in the construction of the recording head of the present invention.

Using 80 parts by weight of 2-hydroxyethyl methacrylate and 20 parts by weight of butyl acrylate, using thioglycolic acid as a chain transfer agent and azobisisobutylnitrile as a market initiator, An oligomer with a carboxy group at the end of the molecular chain was obtained by radical chain transfer.

By reacting this oligomer with glycidyl methacrylate, a macromonomer with a methacryloyl group at one end of the molecular chain was obtained.

The number average molecular field of this macromonomer by GPC method is
It was about 3,000. 1 part of this macromonomer 30i1iq and 70 parts by weight of methyl methacrylate were solution polymerized in a methyl cellosolve solvent, and the weight average molecular fflt was about 5.
A graft copolymer polymer having a number average molecular weight of about 12,000 was obtained.

70:2 of methyl methacrylate, isobornyl methacrylate and 2-hydroxyethyl methacrylate
Linear acrylic aggregate obtained by polymerization at a ratio of 0:10 (mole ratio). The number average molecular weight is about 70,000, and the weight average molecular weight is about 250,000.

Half ester epoxy C Orthocresol novolak type epoxy resin (condensation degree 6
~7) 50% acrylic acid ester compound Kaitatetomo Ichime”L
) The following two polymerization initiators (D)-1, (D)-2
prepared.

(D)-1. The aforementioned photosensitive aromatic onium salt compound (1) (UVE-1014, manufactured by GE) (D)-2. Irgacure 65l (manufactured by Ciba Geigy) Next, the above materials (A) to (D)-2 were mixed in the Ichikawa ratio shown below by a conventional method to obtain an active energy ray-curable composition. .

Material Weight part A 80B
20C 100D
-1 6D -2
6 Methylene Blue 1 Methyl Cellosolve 200 Methyl Ethyl Ketitone +00 Synthesis Example 2 The following components of the active energy ray-curable resin composition used in the construction of the recording head of the present invention are as follows:
α was done.

M 2-hydroxyethyl methacrylate 50TTL 14 parts, butoxymethyl acrylamide 50i[j! A macromonomer having a methacryloyl group at one end of 1-'f3n was obtained in the same manner as in Example 1 using part i1. The number average molecular weight of this macromonomer by GPC method was about 2,000.

30 parts by weight of this macromonomer and 70 parts by weight of methyl methacrylate were solution polymerized in a solvent of methyl cellosolve: methyl ethyl ketone (MEκ) = 60:40 (weight ratio), and the number average molecular weight was about 6,000 and the weight average molecular weight was about 6,000. 40,050
1,000 thermosetting graft copolymer polymers were obtained.

Methyl methacrylate, tricyclodecane methacrylate, and N-methylol acrylamide at 60:
A linear acrylic copolymer obtained by polymerization at a molar ratio of 30:10. The number average molecular weight is approximately 60,000, and the weight average molecular weight is approximately 260,000.

Half ester epoxy C) Phenol novolak type epoxy resin (contraction degree 5-6)
50% acrylic acid ester of 150% excretion μ》 2 m combination initiators (D)-1, (D)-2
prepared.

(0)−+. The aforementioned photosensitive aromatic onium salt compound (m) (D) -2. Darocure+173 (manufactured by Merck & Co.)
Next, an active energy ray-curable composition was obtained by mixing the above-mentioned materials (A) to (D)-2 in the weight ratio shown below using a conventional method.

Material Weight part 850 B 50C1
00 D-1 6 D-2 6 Methylene Blue I Methyl Cellsolve 200 Methyl Ethyl Ketone 100 Next, each of the resin composition solutions obtained in Synthesis Examples 1 and 2 above was coated with 25 polyethylene terephthalate films (Lumirror T type) using a reverse coater. ), and applied it so that the intra-abdominal pressure after drying was 50μ. A 40μ stretched polyethylene film was used as the cover film. As described above, a dry film having a structure in which the active energy ray resin-curable composition layer was sandwiched between two films was obtained.

Example 1 Using the tri-film produced in Synthesis Example 2, ten heating elements [hafnium boride (HfB, )] and an orifice provided corresponding to the heating element (orifice dimensions: 70μ x 50μ,
An on-demand liquid jet recording head as shown in FIG. 7(d) having a pitch of 0.12 mII+) was prepared as follows. Incidentally, 30 recording heads each having the same shape were prototyped.

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, a second layer of Sin (thickness: 1.0. Sleep, 12
The dry film with a thickness of 50μ obtained in Synthesis Example 2 heated to 0°C was rolled at a roll temperature of 95°C and a peripheral speed of 1 m/min.
The polyethylene film was laminated while being peeled off using a rubber roll under these conditions.

Next, a photomask having a pattern corresponding to the shape of the liquid passage and the liquid chamber is superimposed on the dry film provided on the substrate surface, so that the above-mentioned element is placed in the liquid passage that is finally formed. After alignment and vacuum sealing, the UV intensity in the vicinity of 365 nm from the F part of this photomask was 7 mW/cl12, and the collimation {35° using a highly parallel ultra-high-pressure mercury lamp with an angle of 3° The dry film was exposed for seconds.

Next, after exposure, the dry film was heated with Eterna Nu at 20°C.
Spray development treatment for 50 seconds to dissolve and remove the unpolymerized (uncured) portion of the dry film from the substrate, and the cured dry film film remaining on the substrate forms grooves that will eventually become liquid passages and liquid chambers. did.

After completing the development process, the cured dry film film on the substrate was post-irradiated (UV post-cure) with an ultra-high pressure mercury lamp for 5 minutes under the same conditions as those used for pattern exposure, and further heated at 150°C. A heat treatment was performed for 15 minutes and a post-curing treatment was performed.

On the other hand, the dry film obtained in Synthesis Example 2 was placed on a flat plate made of soda glass in which a liquid chamber was formed and a through hole was provided.
Roll temperature 95°C, peripheral speed lm/min. The polyethylene film was laminated while being peeled off using a rubber roll under these conditions. Next, exposure and development were performed under the same conditions as in the formation of the liquid passage and the liquid chamber, except that a mechanical mask was used, and the dry film on the (4JL chamber) was removed.

The surface of the cured dry film on the substrate and the surface of the cured dry film on the substrate are bonded together under pressure, and bonding is achieved by irradiating ultraviolet rays (50 ml/cm2, 60 seconds) from the κ plate side. It was fixed and a zygote was formed.

Next, the distance is 0.150 m from the downstream side of the liquid passage of the bonded body, that is, from the installation position of the ejection energy generating element.
Place m squarely against the liquid passage, city! Saka no dicing saw (product name: DAD 2H/6 type, DISC
(manufactured by O Company) to form an orifice for discharging recording liquid.

Finally, the cut surface was cleaned and dried, and the cut surface was polished to smooth it, and a recording liquid supply pipe was attached to the through hole to complete the liquid jet recording head. The resulting recording heads all had liquid passages and liquid chambers that faithfully reproduced the mask pattern, and had excellent performance. By the way, the orifice 1 method is 50±5u+ vertically and 7 horizontally.
0±5 doors, orifice pitch is! It was in the range of 20±5μ1.

The quality and durability of the thus prototyped recording head during long-term use were tested as follows.

First, for each of the following sets of recording heads obtained? A durability test was conducted in which the recording head was immersed for 1000 hours at 60° C. (environmental conditions comparable to those during long-term use of a recording head).

Recording liquid component 1) I1■0/diethylene glycol/l,3-dimethyl-2-imidazolidinone/C. I. Direct Blue 86” (・57/30/10/: l11! parts) pH-8.
02) I+,0/diethylene glycol/N-methyl-2-pyrrolidone/C.I. T. Direct black +54
”(-55/:10/10/5 parts by weight) pH-9.
03) 11■0/diethylene glycol/polyethylene glycol $400/N-methyl-2-pyrrolidone/
II:. 1. Direct Yellow 86″3 (・65/10/10/10/5 parts by weight) pl1-7
．． 04) H20/ethylene glycol/triethylene glycol/triethylene glycol monomethyl ether/C. l. Hood black 2"4 (-67/10/
15/5/3 parts by weight) I) I1-10.0 Note) $
1 to 64 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 tri-film film for each head tested, and found that no peeling or damage was observed in all recording heads, indicating good adhesion. It was showing.

Separately, each of the obtained 10 recording heads was attached to a recording device, and a recording signal of 108 pulses was continuously applied to the recording head for 14 hours using a recording liquid. A printing test was conducted.

With respect to any of the recording heads, there was hardly any deterioration in performance in both the recording liquid ejection performance and the printing condition immediately after the start of printing and after 14 hours had elapsed, and the recording heads were excellent in durability.

Example 2 A recording head was produced in the same manner as in Example 1, except that the dry film of Synthesis Example 1 was used instead of the dry film of Synthesis Example 2 used in Example 1.

The obtained recording head had a good degree of sag as in Example 1, and the same good results were obtained in the durability test and the printing test.

(Effects of the Invention) As explained below, since the active energy ray-curable resin composition used in the structure of the liquid jet recording head of the present invention contains the graft copolymer polymer (A) as a constituent component,
It has sufficient adhesion to various members without the addition of additives, etc., and contains linear polymer (83) as a component, so it can return to the development characteristics during pattern formation. The cured film has sufficient chemical resistance, durability, etc.

Historically, since the composition uses a combination of a graft copolymer polymer and a linear polymer as its constituent polymer materials, it is difficult to use only the graft copolymer polymer as the polymer material. A coating film that is resistant to developing solutions and solvents can be created with less active energy ray irradiation than would be the case. As a result, the properties of the patterning process are improved, such as high sensitivity, increased resolution, and the ability to form patterns regardless of the type or condition of the member, and the range of working conditions is expanded.

Therefore, by using the cured product of the composition as a part of its structure, the recording head of the present invention is inexpensive, precise, highly reliable, and has excellent durability. Furthermore, if the liquid passage wall is formed of a cured film of the composition, a recording head having a finely machined liquid passage with good quality and high yield can be obtained.

Furthermore, since the recording head of the present invention has the above-described configuration, it has high reliability and excellent durability even when it is configured with multiple orifices.

[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, and FIG.
Figure 0 is a partial cross-sectional view taken in a plane perpendicular to the liquid path of the recording head, showing the portion where the cured resin film is used, and Figures 8 (a) and (b).
) and FIG. 9 are diagrams showing other configurations of the recording head. 1. 2. Substrate 2. Discharge energy generating element 3. Resin layer 311: Resin cured film (liquid passage wall) 4: Photomask 4P: Mask pattern 6-1/Liquid chamber 6-2: Liquid passage 7: Cover 8: Through hole 9: Orifice 10: Supply pipe 11: Electrode 12: Protective layer I3: Heat generating resistance layer l4: Adhesive layer

Claims (1)

[Scope of Claims] 1) A liquid jet recording head having a cured product of an active energy ray-curable resin composition as part of its structure, wherein the composition comprises (A) alkyl methacrylate, acrylonitrile, and styrene. A backbone mainly consisting of a structural unit derived from one or more monomers selected from the group consisting of a monomer represented by the following general formula (x) and a monomer represented by the following general formula (y). A graft copolymer polymer having a branched chain having a structural unit derived from at least one monomer derived from the above, and having a number average molecular weight of 5,000 or more and a weight average molecular weight of 50,000 or less; , chemical formulas, tables, etc.▼...(x) ▲Mathematical formulas, chemical formulas, tables, etc.▼...(y) [However, R^1 is hydrogen or has 1 to 3 carbon atoms.
represents an alkyl group or a hydroxyalkyl group, R
^2 represents hydrogen, or an alkyl group or acyl group having 1 to 4 carbon atoms which may have a hydroxy group, and R^3 represents an alkyl group having 2 to 6 carbon atoms, or a halogen-substituted alkyl group. Alkyl groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, 2≦m+n≦6, n≠0, m≠0) Alkyl ether groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, 2≦m+n≦4, including cases where n=0 or m=0). ] (B) Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, t-butyl methacrylate,
Benzyl methacrylate, acrylonitrile, isobornyl methacrylate, isobornyl acrylate,
Having a structural unit derived from one or more monomers selected from the group consisting of tricyclodecane acrylate, tricyclodecane methacrylate, tricyclodecaneoxyethyl methacrylate, styrene, dimethylaminoethyl methacrylate, and cyclohexyl methacrylate,
and has a structural unit derived from at least one monomer selected from the group consisting of monomers represented by the general formula (x) and the general formula (y), and has a number average molecular weight of 50,000 or more, and has a weight Existing in an epoxy resin comprising a linear polymer having an average molecular weight of 350,000 or less and a glass transition temperature of 60°C or more, and (C) at least one compound having two or more epoxy groups in the molecule. (D) a polymerization initiator that generates a Lewis acid upon irradiation with active energy rays. 2) The weight ratio of the graft copolymer polymer (A) and the linear polymer (B) is (A):(B)=80:20 to 50.
2. The liquid jet recording head according to claim 1, wherein: :50. 3) The weight ratio of the total weight (A) + (B) of the graft copolymer polymer (A) and the linear polymer (B) to the epoxy resin (C) is {(A) + (B)} :(C)=10
3. The liquid jet recording head according to claim 1, wherein the ratio is 0:50 to 100:200. 4) Total weight (A)+(B) of the graft copolymer polymer (A), the linear polymer (B), and the resin (C)
The weight ratio of +(C) and the polymerization initiator (D) is {(A)+
(B)+(C)}:(D)=100:1~100:10
The liquid jet recording head according to any one of claims 1 to 3. 5) The polymerization initiator (D) is one selected from the group consisting of aromatic halonium salt compounds and photosensitive aromatic onium salt compounds containing elements belonging to Group VIa or Group Va of the Periodic Table. The liquid jet recording head according to any one of claims 1 to 4, which is the above.