JPS6216152A - Liquid jet recording head - Google Patents

Abstract

PURPOSE:To provide an inexpensive and precise liquid jet recording head excel lent in durability, by using a specific resin composition in the preparation of the liquid jet recording head. CONSTITUTION:A liquid jet recording head is constituted by a method wherein predetermined pattern exposure using active energy rays is applied to the layer comprising a resin composition provided on a substrate to form cured regions and uncured regions are removed to form liquid passages to the surface of the substrate. Said resin composition consists of (i) a graft copolymer obtained by adding a branched chain based on a structural unit occurring from (A) a hydroxyl group-containing acrylic monomer, (B) an amino or alkylamino group- containing acrylic monomer, (C) a carboxyl group-containing acrylic or vinyl monomer, (D) N-vinyl pyrrolidone or a derivative thereof, (E) vinyl pyridine or a derivative thereof and (F) an acrylamide derivative represented by general formula I to a main chain based on a structural unit occurring monomers of alkyl methacrylate, acrylonitrile and styrene, (ii) and epoxy resin containing a compound having an epoxy group in the molecule thereof and (iii) a polymeri zation initiator generating Lewis acid by the irradiation of active energy rays.

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.

[Conventional 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 extremely small and can be ignored at high speed. It has attracted attention as a recording method that can record on plain paper without requiring any special processing such as fixing, and various types have recently been actively researched.

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. 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 on a flat plate of glass, metal, etc. by cutting or etching, and then to form other suitable grooves on the flat plate with these grooves. A method that includes a step of bonding plates to form a liquid passage, or, for example, forming a groove wall of a cured photosensitive resin on a substrate on which an ejection energy generating element is arranged by a single photolithography step, and forming a liquid passage on the substrate. A method is known that includes a step of providing a groove to serve as a passage, and joining another flat plate (cover) to the thus formed grooved plate to form a liquid passage (for example, Japanese Patent Application Laid-open No. 1983-1999)
No. 43878).

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., and those that have been used 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.

[Problem that the invention seeks to solve]

In a recording head using a cured film of a photosensitive resin, in order to obtain excellent characteristics such as advanced recording characteristics, durability, and reliability, the photosensitive resin used in the recording head is:

(i) Particularly excellent in adhesion to the substrate as a cured film; (2) Excellent in mechanical strength and durability when cured; (3) For pattern formation using pattern exposure. It is required to have characteristics such as excellent sensitivity and resolution.

However, the current situation is that there is no photosensitive resin that satisfies all of the above-mentioned required characteristics among the photosensitive resins used to form hitherto known liquid jet recording heads.

That is, printing plates, photosensitive resins for recording heads,
The materials used for pattern formation in printed wiring etc. have excellent sensitivity and resolution, but have poor adhesion and adhesion to glass, ceramics, plastic films, etc. used as substrates, and moreover, they have poor adhesiveness when cured. Insufficient mechanical strength or durability, which may obstruct the flow of recording liquid in the liquid path or make the direction of droplet ejection unstable during the manufacturing stage of the recording head or during use. This method has the drawback that the cured resin film is easily deformed, peeled off from the substrate, and damaged, which causes a significant loss of reliability of the recording head, such as deterioration of recording characteristics.

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 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, and due to its characteristics, resolution is lower. Since it is not possible to obtain a highly precise, high-density pattern, there is a problem in 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 precision 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 for solving problems]

The above objects can be achieved by the following invention.

In the present invention, a liquid passage provided on a substrate surface and communicating with a liquid discharge port exposes a layer of a resin composition that is cured by active energy rays in a predetermined pattern using active energy Y-rays. a liquid jet recording head formed by forming a cured region of the resin composition and removing an uncured region from the layer, the resin composition comprising (i) alkyl methacrylate, acrylonitrile, and styrene; (A) a hydroxyl group-containing acrylic monomer, (B) an amino or alkylamino group-containing acrylic monomer, and (C) a carboxyl group-containing acrylic monomer in a backbone chain mainly composed of structural units derived from one or more monomers selected from the group consisting of: or derived from one or more monomers selected from the group consisting of vinyl monomers, (D) N-vinylpyrrolidone or its derivatives, (E) vinylpyridine or its derivatives, and (F) an acrylamide derivative represented by the following general formula 1. A graft copolymer polymer formed by adding branch chains mainly composed of structural units, and 0H2=
C---(I)'' 0 = C-NH-CH2-0-R2 (However, R1 is hydrogen or an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, and R2 is hydrogen or an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms. (ii) an epoxy resin comprising at least one compound having one or more epoxy groups in the molecule; and (iii) active energy rays. A liquid jet recording head characterized in that it comprises a polymerization initiator that generates a Lewis acid when irradiated with a polymerization initiator.

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 precisely micro-processed, has excellent recording characteristics, and is highly reliable.
This recording head also has 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. 1(a) is a perspective view of its main parts, and FIG.
FIG. 2 is a cross-sectional view taken along line c-c' in FIG.

This liquid jet recording head basically includes a substrate 1, a cured resin film 3H provided on the substrate and patterned into a predetermined shape, and a cover 7 laminated on the cured resin film. These members form an orifice 9 for discharging a recording liquid, and a liquid passage 6-2 communicating with the orifice and having a portion on which energy for discharging the recording liquid acts on the recording liquid. A liquid chamber 6-1 is formed for storing recording liquid to be supplied to the liquid passage. 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. 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 the ejection signal as desired via the ejection signal.

The substrate l constituting the recording head of the present invention is made of glass, ceramics, plastic, metal, or the like, and a desired number of generating elements 2 are disposed at predetermined positions. In addition, the first
In the illustrated example, 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 onto the cured resin film 3H by fusing or bonding using an adhesive. A through hole 8 for connection is provided.

In the recording head of the present invention, the cured resin 1i3H patterned in a predetermined shape constituting the walls of the liquid passage 6-2 and the liquid chamber 8-1 is placed on the substrate 1 or on the cover 7. It was obtained by patterning a layer made of a resin composition having the composition explained in one step of photolithography.

Note that the cured resin film 3H may be patterned and integrated with a cover made of a resin composition having the composition described below.

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 as follows.

(i) (A) a hydroxyl group-containing acrylic monomer, (B) an amino or alkyl monomer, and (A) a hydroxy group-containing acrylic monomer; Amino group-containing acrylic monomer-1 (C) Carboxyl group-containing acrylic or vinyl monomer, (D) N-
Vinylpyrrolidone modi< is a derivative thereof, a branch mainly consisting of a structural unit derived from one or more monomers selected from the group consisting of (E) vinylpyridine or a derivative thereof, and (F) an acrylamide derivative represented by the following general formula I. A graft copolymer polymer with added chains.

I CH2=C---(I) 0=C-NH-CH2-0-R2 (However, R1 is hydrogen or an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, and R2 is hydrogen or a carbon atom number (ii) an epoxy resin comprising at least one compound having one or more epoxy groups in the molecule;

(iii) a polymerization initiator that generates a Lewis acid upon irradiation with active energy rays; It has good adhesion to substrates, has excellent resistance to recording liquids such as ink, and has excellent mechanical strength, and can also be used to form precise, high-resolution patterns by patterning with active energy rays. It has excellent properties as a component of a liquid jet recording head. 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 (i) graft copolymer, which is an essential component of this active energy ray-curable resin composition, has a relatively rigid backbone suitable for use as a structural material, and the above-mentioned hydrophilic polymer. It is mainly composed of heptamers (A) to (F) and has branch chains added thereto to exhibit excellent adhesion to the support.

When constructing the graft copolymer polymer, the monomers (A) to (F) used to construct the branch chain are specifically shown below. Ethyl (meth)acrylate (hereinafter referred to as (meth)acrylate includes both acrylate and methacrylate), 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (ivy)acrylate, 3-hydroxybutyl (meth)acrylate,
5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, or 1.
Examples include monoesters of 4-cyclohexane dimetatool and acrylic acid or methacrylic acid, including trade names Aroninx M57 (i0 (manufactured by Toagosei Kagaku Co., Ltd.),
TONEMloo (caprolactone acrylate,
Union Carbide v4), Light Ester HO-m
pp (manufactured by Kyoeisha Yushi Kagaku Kogyo ■), those known as Light Ester Toro 00A (trade name of 2-hydro-3-phenoxypropyl acrylate, manufactured by Kyoeisha Yushi Kagaku Kogyo ■), dihydric alcohols 1, etc. 1.1
0-Decanediol, neopentyl glycol, bis(
2-hydroxyethyl) terephthalate, a monoester of an addition reaction product of bisphenol A and ethylene oxide or propylene oxide, and (meth)acrylic acid, etc. can be used.

The amino or alkyl 7-mino group-containing acrylic monomer for (R) includes (meth)acrylamide, N,
N-dimethylaminoethyl (meth)acrylamide, N
, N-dimethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, K N-
Examples include dibutylaminoethyl (meth)acrylamide.

Examples of the carboxyl group-containing acrylic or vinyl monomer (C) include (meth)acrylic acid, fumaric acid, Itacone Ugly, or Toagosei Chemical [one product known under the trade name Aronixt 5400, Aronix M-5500, etc. .

As vinylpyridine or its derivative (E),
Examples include 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methylpyridine, 4-vinyl-1-methylpyridine, 2-vinyl-5-ethylpyridine, 4-(4-pibenylinoethyl)pyridine, etc. .

All of the above monomers (A) to (E) have wood-philic properties, and when the composition of the present invention adheres to a support such as glass, ceramics, plastic, etc.
It provides strong adhesion.

As the acrylamide derivative represented by the general formula 1 of (F), N-methylol (meth)acrylamide, N-
Propoxymethyl (meth)acrylamide, N-n-butoxymethyl (meth)acrylamide, β-hydroxyethoxymethyl (meth)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-
Examples include monomers that are hydrophilic and have thermal crosslinking properties, such as methylol acrylamide. These monomers (F) have not only wood-philic properties but also condensation cross-linking properties when heated, and generally, water molecules or alcohol are released at temperatures of 100°C or higher to form cross-linked bonds, resulting in graft copolymer polymers. After curing, a network structure is formed in the curing material itself, thereby 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 a monomer that is thermally ring-opened and crosslinked, such as glycidyl (meth)acrylate, to the monomers (A) to (F) above to form a branch chain,
The same effect as in (F) above can be obtained.

In addition to the above-mentioned thermal crosslinking, for the same purpose, photopolymerizable side chains are introduced into some of the branch chains of the graft copolymer contained in the resin composition for forming a cured resin film in the present invention. It is also effective to crosslink the graft copolymerized polymer. Examples of methods for imparting photopolymerizability to branch chains include: (1) using monomers containing carboxyl groups, such as (meth)acrylic acid, or monomers containing amino groups or tertiary amino groups; Copolymerize, then glycidyl (meth)
Method of reacting with acrylate etc., ■ Reacting a partial urethane compound of polyisocyanate having one incyanate group and one or more acrylic ester groups in one molecule with a branched hydroxyl group, amino group or carboxyl group. Method: ■Method of reacting acrylic acid chloride with the hydroxyl group of the branch chain; ■Method of reacting the hydroxyl group of the branch chain with an ugly anhydride, and then reacting with glycidyl (meth)acrylate; [Phase] The method of reacting the hydroxyl group of the branch chain with ( Methods such as condensation with the condensation crosslinking monomer exemplified in F) to leave an acrylamide group on the side chain, and (2) reacting the hydroxyl group of the branched chain with glycidyl (meth)acrylate 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 the branch chains derived only from the tree-loving epitome as exemplified in (A) to (F) above, the branch chains may be derived from various hydrophobic epitomes that exhibit various other functions. Branched chains may be used as a component of the copolymerization in an amount up to 25% by weight.

The monomers constituting the backbone chain of the graft copolymerized polymer are methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, t-butyl methacrylate and other furkyl methacrylates in which the alkyl group has 1 to 4 carbon atoms, acrylonitrile, and It is styrene.

The backbone chain is derived from only the above monomers.

For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate,
It may also be a backbone chain comprising vinyl acetate or the like as a copolymer component in an amount of 0 to about 50% by weight.

In this active energy ray-curable resin composition used for forming the recording head of the present invention, the above-mentioned backbone chain imparts high cohesive strength to the composition. The composition is provided in various forms depending on the purpose of use, such as a solution or a solid film when forming a recording head.In order to maintain the composition in a film form, it is necessary to heat the composition at a temperature of about 50°C or higher. It is preferable to use a relatively rigid backbone chain having a glass transition temperature of If the composition is to be used in a form, 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 that are photopolymerizable, and those that are thermally crosslinkable.
In any case, in the curing process of the resin composition used in the present invention (i.e., active energy ray irradiation and thermal curing as necessary), shape retention is imparted to the composition to enable precise patterning. At the same time, 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 Polymer Alloys J, pages 10-35 (edited by the Society of Polymer Engineers, published by Tokyo Kagaku Dojin)" , 1881).

Examples of these methods include: (1) chain transfer method, (2) method using radiation, (2) oxidative polymerization method, (2) ion graph ttrt method, and (2) macromonomer method. The graft copolymer contained in the resin composition used in the present invention has a more pronounced surface active effect when the branch chain lengths are uniform.
It is preferable to use the methods ① and ②, and among them, the macromonomer method ② is advantageous in terms of material design, and it is particularly preferable that the weight average molecular weight of the graft copolymer is about 5000 to 30.
A range of about 10,000 is preferable, and when used as a dry film, a range of about 30,000 to 300,000 is preferable.

The epoxy resin (ii) consisting of one or more compounds containing one or more epoxy groups in one molecule contained in the resin composition used for forming a cured resin film in the present invention is:
In the presence of the polymerization initiator (iii) described below, the resin composition used in the present invention is made to exhibit sufficient curability with high sensitivity to active energy rays, and in addition, the resin composition is
It is used when it is applied in liquid form onto various supports made of glass, plastics, ceramics, etc. and then cured to form a cured film, or by adhering it to various supports in the form of a dry film. In particular, it is a component for imparting better adhesion to a support, water resistance, chemical resistance, dimensional stability, etc. to a cured film made of the resin composition.

As the epoxy resin (ii), any epoxy resin can be used without particular limitation as long as it is made of one or more compounds containing one or more epoxy groups in one molecule. However, for example, when forming a recording head, consideration must be given to the chemical resistance and mechanical strength of the cured resin film obtained by curing this resin composition, high durability as a structural material, etc. Considering the workability and resolution of the formed pattern when forming a pattern on the substrate that includes grooves that serve as liquid passages made of a cured film of
It is preferable to use an epoxy resin made of one or more compounds containing two or more epoxy groups in one molecule.

The above-mentioned epoxy resins containing two or more epoxy groups in one molecule include epoxy resins represented by bisphenol A type, novolak type, and alicyclic type, or bisphenol S, bisphenol F1 tetrahydroxyphenylmethane tetraglycidyl ether, Resorcinol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol triglycidyl ether, incyanuric acid triglycidyl ether, and epoxy urethane resins represented by the following general formula (where R represents an alkyl group or an oxyalkyl group). Examples include functional epoxy resins and mixtures of one or more thereof.

In addition, the following can be mentioned as a specific example of these polyfunctional epoxy resins.

That is, as a bisphenol A type epoxy resin,
For example Epicote 828, 834, 871.100
1, 1004 (trade name, manufactured by Shell Chemical Co., Ltd.), DE
R331-J, 337-J, 881-J,
+3E14-J, 8137-J (manufactured by Dow Chemical Company), Epiclon 800 (trade name, manufactured by Dainippon Ink & Chemicals Co., Ltd.), etc.; Examples of novolac type epoxy resins include Epicort 152.154, 172,
(Product name, manufactured by Shell Chemical Co., Ltd., Araldai) EPN
1138 (product name, manufactured by Ciba Geigy), DE
R431, 438, and 439 (trade name, manufactured by Dow Chemical Company), etc.; Examples of alicyclic epoxy resins include 1, such as Araldite CY-175, -178, -179, -182,
-184, -182 (product name, manufactured by Ciba Geigy), Chissonox [0, 091, 0f32, 301.31
3 (product name, manufactured by Chisso Corporation), Syracure (CYRA)
CURE)8100.611O16200 and ERL
4090.4617.225B, 5411 (product name,
(manufactured by Union Carbide Co., Ltd.); polyglycidyl ethers of aliphatic polyhydric alcohols include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol. Diglycidyl ether, 1,6-hexanesiol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, etc.; aromatic Polyhydric glycidyl ethers derived from polyhydric alcohols include alkylene oxides of bisphenol A,
Examples include diglycidyl ether as an 18 mol adduct, diglycidyl ether as a 2 to 16 mol adduct of bisphenol F and fullkylene oxide, and diglycidyl ether as a 2 to 16 mol adduct of bisphenol S and fullkylene oxide.

Compounds containing one epoxy group in one molecule include olefin oxide, olefin oxide, butyl glycidyl ether, glycidyl methacrylate, acrylic glycidyl ether, styrene oxide, phenyl glycidyl ether, n-butylphenol glycidyl ether, 3-pentadecyl Examples include phenylglycidyl ether, cyclohexene vinylmore oxide, α-pinene oxide, glycidyl ester of tert-carboxylic acid, and mixtures thereof.

These -functional epoxy resins can be used in conjunction with the multifunctional epoxy resins described above, or by themselves.

In the resin composition for forming a cured resin film used in the present invention, the epoxy resin (ii) is a polymerization initiator (
The Lewis acid generated by irradiation with active energy rays in iii) has sufficient curability with high sensitivity to the active energy rays generated by acting on the epoxy groups of the resin, and due to this curability, It not only enables precise and high-resolution pattern formation, but also provides good adhesion to the support, chemical resistance, dimensional stability, etc. due to the inherent thermosetting properties of epoxy resin. It is.

In the present invention, the polymerization initiator (ii) that generates a Lewis acid by irradiation with active energy rays that is combined with the resin composition used for forming a resin cured film is the polymerization initiator (ii) that generates a Lewis acid by the action of the Lewis acid. harden,
It is a component for making the resin composition used in the present invention exhibit sufficient curability with high sensitivity to active energy rays, and preferably belongs to Group VIa as shown in, for example, Japanese Patent Publication No. 52-14278. Aromatic onium salt compounds containing elements and having photosensitivity, or Japanese Patent Publication No. 52-142
Aromatic group nium salt compounds having photosensitivity and containing elements belonging to group Va as shown in Publication No. 711, or aromatic halonium salts having photosensitivity as shown in Japanese Patent Publication No. 14277/1983, etc. can be used.

Both of these aromatic onium salt compounds and aromatic halochloram salts have the property of curing the epoxy resin (ii) by releasing a Lewis acid when irradiated with active energy rays.

The photosensitive aromatic onium salt compound of an element belonging to Group VIa or Group Va above typically has the following general formula (1); [(R3)a (R4)b (R5)eX]; MQ
e]-'-0...(III) (In the above formula, R3 is a monovalent organic aromatic group, R5 is a monovalent organic aliphatic group selected from an alkyl group, a cycloalkyl group, and a substituted alkyl group) is a polyvalent organic group constituting a heterocyclic or fused ring structure selected from aliphatic groups and aromatic groups; M represents a metal or semimetal, and Q represents a halogen group, and a
is an integer of 0 to 3 when X is an element belonging to group Via, and is an integer of 0 to 4 when X is an element belonging to group Va
b is an integer of 0 to 2, C is an integer of 51. VIa
If X is an element belonging to Group Va, an integer of O or l; if X is an element belonging to Group Va, an integer of O~2, f
is the valence of M and is an integer from 2 to 7, 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 When is an element belonging to Group Va, compounds represented by 4 and d=ef) can be mentioned.

In addition, as a photosensitive aromatic halonium salt, the following general ■; [(R6)g (R7)hX]i' [MQJ]
-"-" -(IV) (In the above formula, R6 is a monovalent aromatic organic group, R7 is a divalent aromatic organic group, X is a halogen group, M is a metal or metalloid, and Q is a halogen group. respectively, g is an integer of O or 2, h is an integer of O or 1, the sum of g and h is equal to 2 or the valence of X, i is equal to −A, and ! is an atom of M. 2~
7, and k is an integer greater than 1 and up to 8).

Specific examples of the photosensitive aromatic onium salt compounds containing elements belonging to Group VIa or Group Va include photosensitive aromatic onium salts of elements belonging to Group VIa, such as, and onium Examples include salt.

Moreover, as a specific example of the photosensitive aromatic halonium salt, for example.

etc.

In addition, a polymerization initiator (ii
In addition to i), curing agents such as polyamino, polyamide, acid anhydride, boron trifluoride-amino complex, dicyandiamide, imidazoles, and complexes of imidazole and metal, which are generally widely known as curing agents for epoxy resins, can be used. It may be used as necessary.

The active energy ray-curable resin composition for forming a cured resin film used in the present invention uses a photopolymerizable rat copolymer (i) to be contained in the resin composition, and has a wavelength of 250 ns to When using active energy rays of 450 nm, the polymerization initiator (
In addition to iii), it is preferable to add to the resin composition an organic free radical-generating radical polymerization initiator that can be activated by the action of active energy rays. Any known substance having the property of being activated by radiation, generating organic free radicals, and initiating radical polymerization can be used without particular limitation.

Specific examples of such radical polymerization initiators include benzyl, benzoin alkyl ethers: benzoin isobutyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin ethyl ether, benzoin methyl ether, etc., benzophenones: benzophenone, 4 .4'-bis(N,N-diethylamino)hensiphenone, benzophenone methyl ether, etc., anthraquinones = 2-dithylanthraquinone, 2-t-butylanthraquinone, etc., xanthones + 2.4-dimethylthioxanthone, 2,4-diinpropyl Acetophenones such as thioxanthone = 2.2
-dimethoxy-2-phenylacetophenone, α, α-
Dichloro-4-phenoxyacetophenone, p-te
rt-butyltrichloroacetophenone, p-ter
t-Butyldichloroacetophenone, 2,2-jetoxyacetophenone, P-dimethylaminoacetophenone, etc., or hydroxycyclohexylphenyl ketone (Irgacure 184 manufactured by Ciba Geigy ■), 1
-(4-isopropylphenyl)-2-hydroxy-2
-Methylpropan-1-one (Darocur 1118
Made by MERCK M), 2-1 = Doroxy-2
-Methyl-1-phenyl-propan-1-one (Darocure 1173 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.

Amino compounds used as photopolymerization accelerators include ethanolamino, ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, p-
Examples include dimethylaminobenzoic acid n-amyl ester, p-dimethylaminobenzoic acid inamyl ester, and the like.

The composition ratio of the materials constituting the active energy ray-curable resin composition used in the present invention is the graft copolymer polymer (
When the content of i) is 0 parts by weight and the content of epoxy resin (ii) is 8 parts by weight, G/(G+E) is 0.2 to
0.8, and the polymerization initiator (iii) that generates Lewis acid is in the range of 0.8 to 100 parts by weight of (G+E).
It is preferable to contain 2 to 15 parts by weight of G/(G
When +E) is less than 0.2, the content of the graft copolymer in the resin composition decreases, and sufficient adhesion to the support based on the graft copolymer is no longer exhibited. In addition, when a solvent is used, the drying properties of the solvent deteriorate, resulting in problems such as the surface of the pattern obtained by curing becomes sticky. On the other hand, when G/(G+E) exceeds 0.8, the content of epoxy resin decreases, resulting in disadvantages such as deterioration of sensitivity to active energy rays and reduction in resolution of the formed pattern. .

In addition, in the case where a radical polymerization initiator that is activated by the action of activation energy rays is used in the resin composition, the polymerization initiator includes a graft copolymer polymer (i), an epoxy resin (ii), and a Lewis acid. Polymerization initiator (iii) generated
A resin component consisting of [(i)+(ii)+(iii)]
The amount ranges from 0.1 to 20 parts by weight, preferably from 1 to 10 parts by weight, based on 1,100 parts by weight.

The solvents used in the present invention include alcohols, Examples include hydrophilic solvents such as glycol ethers and glycol esters. Of course, these hydrophilic solvents are the main ones, 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 halogen substituted products, methylene chloride, l, 1. It is also possible to use an appropriate mixture of a chlorine-containing aliphatic solvent such as t-trichloroethane. Furthermore, these solvents.

It can also be used as a developer for the composition.

In addition to the above-mentioned radical polymerization initiator or solvent, the active energy ray-curable resin composition used in the present invention includes, for example, a condensation crosslinking catalyst, a thermal polymerization inhibitor, and a coloring agent (dye and pigment).
, particulate fillers, adhesion promoters, plasticizers, and other additives may be included as necessary.

Examples of the condensation crosslinking catalyst include sulfonic acids typified by para-toluenesulfonic acid, and carboxylic acids such as formic acid. Examples of thermal polymerization inhibitors include hydroquinone and its derivatives, paramethoxyphenol, and phenothiazine.As colorants, oil-soluble dyes and pigments may be added to the extent that they do not substantially prevent the transmission of active energy rays. As the filler, extender pigments, plastic particles, etc., which are commonly used in paints, are used to increase the hardness, color, adhesion, and mechanical strength of the coating film.

As adhesion promoters, silane coupling agents as inorganic surface modifiers and low molecular surfactants are effective for the resin composition used in the present invention.

When the active energy ray-curable resin composition described above is used in the form of a dry film to form the recording head of the present invention, it is generally appropriate to support the composition with a film-like base material. Film-like substrates used at this time include, for example, a biaxially stretched polyethylene terephthalate film with a thickness of 16 μs to 100 tiles, cellulose triacetate, poly-1-vinyl fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride, Examples that can be used include 4-methylpentene-1, polyethylene, polypropylene, and laminates or coextruded films thereof. In addition, lamination methods for producing a dry film by laminating the composition on a film-like substrate as described above include coating methods using a roll coater, bar coater, etc., dipping, spray coating, and brush coating. Well-known methods such as can be used.

Further, as a patterning method when using such a dry film, for example, patterning of a suitable substrate or a plate material serving as a cover is provided with an ejection energy generating element that generates energy for ejecting liquid from the recording head. The dry film is laminated onto the desired support using an elastic roll such as a rubber roll, and then the dry film is laminated onto the support using a well-known laminating device that can be heated and pressurized. fixing and then removing or not removing the film-like substrate of the dry film;
Either masking and irradiating active energy rays,
Alternatively, it may be carried out by a method such as selective irradiation with active energy rays.

The cured resin film 3H of the recording head of the present invention is formed by curing the resin composition having the above composition with active energy rays.

Hereinafter, the method for manufacturing a liquid jet recording head of the present invention will be described in detail with reference to the drawings, taking as an example a case where a dry film type resin composition is used as the resin composition for forming the cured resin film 3H.

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

To form the liquid jet recording head of the present invention.

First, as shown in FIG. 2, a desired number of ejection energy generating elements 2 such as heating elements or piezo elements are arranged on a substrate 1 made of glass, ceramic, plastic, metal, or the like. Incidentally, in order to provide the surface of the substrate 1 with resistance to recording liquid, electrical insulation, etc., if necessary, Si may be applied to the surface of the substrate 1.
It may be covered with a protective layer such as O□, Ta205, or glass.Although not shown, the ejection energy generating element 2 is connected to a recording signal input electrode.

Next, after cleaning the surface of the substrate l obtained through the process shown in FIG. 2 and drying it at, for example, 80 to 150°C, The above-mentioned active energy ray-curable resin composition 3 of dry film type (film thickness, about 20 μs to 200 μs) was added to 40 to 15
Heating to about 0°C, for example, 0.5 to 0.4 f/
The substrate is laminated onto the substrate surface IA at a speed of 1 min, and under a pressure of 1 to 3 Kg/cm2.

Subsequently, as shown in FIG. 4, a photomask 4 having a pattern 4P of a predetermined shape that does not transmit active energy rays is superimposed on the dry film layer 3 provided on the substrate surface IA. Exposure is performed from the top of the mask 4.

Note that the alignment between the photomask 4 and the substrate l is performed so that the element 2 is located in the liquid passage area that is finally formed through steps such as exposure and development. This can be carried out by drawing marks on each of the substrate 1 and the mask 4 in advance and aligning them according to the marks.

When exposed in this way, the area other than the area covered by the pattern, that is, the exposed area of the dry film layer 3, polymerizes and hardens, and the unexposed area remains solvent soluble, whereas the solvent Becomes insoluble.

The active energy rays used for this pattern exposure are:
Examples include ultraviolet rays and electron beams, which have already been widely put into practical use. As an ultraviolet light source, the wavelength is 250 nm to 4
Examples include high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, etc. that contain a lot of 50 nm light, and the intensity of light in the vicinity of 385 r + m at the practically acceptable distance between the objects to be irradiated is 1 ar'd/C112 to 1100 II. /
There is no particular limitation on the electron beam irradiation device, which preferably has a dose of about Cm2, but a device with a dose in the range of 0.5 to 20 M Rad is practically suitable.

After pattern exposure of the dry film layer 3 is completed, next, the exposed dry film 3 is exposed, for example, 1, 1 . I-
A dry film layer 3 that is soluble in a solvent is developed by being immersed in a volatile organic solvent such as trichloroethane.
The unpolymerized (unhardened) portion of the resin is dissolved and removed from the substrate 1, and as shown in FIGS. Grooves that will become the passage 8-2 and the liquid chamber 6-1 are formed.

Next, the cured resin film 3H on the substrate 1 is heated to at least 80°C.
The mixture is heated at the above temperature for about 10 minutes to 3 hours for thermal polymerization. Note that when a thermosetting graft copolymer polymer is used in the resin composition 3, the heat treatment 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 8-1. However, the active energy ray-curable resin composition that can be used in forming the uninvented recording head 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, is a method that corresponds to the thickness of the coating film of the 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 appropriate viscosity of the resin composition is 100 cp to 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, the method of attaching a dry film to the substrate by heat-pressing as described above is suitable.

However, when forming a recording head that has not yet been invented, a solid film type is convenient in terms of handling and the ability to easily and accurately control the thickness.

In this way, after forming the grooves that will finally constitute the liquid passage 6-2 and the liquid chamber 6-1 using the cured resin film 3H,
As shown in FIGS. 6(a) and 6(b), the flat plate 7 that covers the groove is bonded to the cured resin film 3H 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 applying an epoxy resin adhesive to a thickness of 3 to 4 scales on the flat plate 7 of glass, ceramic, metal, plastic, etc.,
The adhesive layer is preheated to a so-called B stage,
There is a method such as bonding this onto the cured dry film 3H and then curing the adhesive layer. A method that does not use an adhesive, such as directly heat-sealing the film, may also be used.

Further, 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 is joined to the liquid passage, and this is heat-sealed to the cured resin film 3H forming the liquid passage. Also preferable is a method in which active energy rays are irradiated and heated afterwards, that is, a method in which the resin composition for forming a cured resin film of the present invention is used as an adhesive.

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

In this way, the cured resin film 3H provided on the substrate 1
After completing the joining of the and flat plate 7, this joined body is shown in Fig. 6 (
A) and along c-c' on the downstream side of the liquid passage 6-2 shown in FIG. form an orifice for

This process involves the ejection energy generating element 2 and the orifice 9.
This is done to optimize the distance between the two, and the area to be cut here is selected as appropriate.

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

Note that the downstream part of the liquid path in the present invention refers to the downstream region in the flow direction of the recording liquid when recording is performed using a recording head, specifically, the installation position of the ejection energy generating element 2. Refers to the part of the liquid passage further downstream.

Once cutting is complete, the cut surface is polished and smoothed.
A supply pipe 10 is attached to the through hole 8 to complete a liquid jet recording head as shown in FIG.

In the example described above, after the cured resin film 3H was formed on the substrate l, the cover 7 was joined to it. A resin that may be joined or formed by removing at least a portion corresponding to the groove forming the liquid passage 2 from a member made of the active energy ray-curable resin composition described above to form the groove that will become the liquid passage. The cured film 3H and the cover 7 may be integrally formed from the active energy ray-curable resin composition, and this may be bonded onto a substrate to form a recording head.

Further, in the recording head described above, the liquid passage 8-2 and the liquid chamber 6-1 are integrally molded by the cured resin film 3H, but the recording head of the present invention is not limited to such a structure. However, in either structure, in the recording head of the present invention, at least a part of the resin forming the liquid passage may be formed by molding the liquid passage and the liquid chamber separately. It is formed using the active energy ray-curable resin composition listed in .

〔Effect of the invention〕

The liquid jet recording head of the present invention includes an active energy ray-curable resin composition that is a component of the head, and an epoxy resin (ii) contained as an essential component in the composition and a polymerization initiator that generates a Lewis acid. (iii) The pattern forming material mainly provided by the method uses a pattern forming material that has very excellent sensitivity and resolution to active energy rays, 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 effectively utilizes the characteristics of the graft copolymer polymer (i) and the epoxy resin (ii) as essential components. That is, the resin composition of the present invention mainly has, in addition to excellent adhesion to the support and mechanical strength provided by the graft copolymer polymer (i),
The epoxy resin (ii) has excellent chemical resistance and dimensional stability, and by using this composition, it has become possible to obtain a recording head with long-term durability.

Furthermore, when using an active energy ray-curable resin composition using a graft copolymer polymer having curability,
It is possible to obtain a liquid jet recording head that has particularly excellent adhesion 1 mechanical strength or chemical resistance.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples and Examples.

Synthesis Example 1 Living polymer obtained by anionic polymerization method (2-hydroxyethyl methacrylate/butyl acrylate (
= 80/20 weight ratio)) and p-vinylbenzyl chloride to form a macromonomer (p-vinylbenzyl poly-2-hydroxyethyl meth) with a weight average molecular weight of about 1800 having a vinyl group at one end of the molecular chain Acrylate/
butyl acrylate) was obtained. This macromonomer 30
part by weight and 70 parts by weight of methyl methacrylate were solution polymerized in methyl cellosolve to obtain a weight average molecular weight of ? ,OX1
04 thermoplastic graft copolymer polymer (this is GP-
1) was obtained. The glass transition temperature of the polymethyl methacrylate chain that constitutes the main chain of GP-1 is 100
It is ℃.

Using this GP-1, an active energy ray-curable resin composition having the following composition was prepared.

G P-1100 parts by weight Epicoat 1001 Agricultural 1 50 /
/ Epicote 1521 20 Heptoxide 2021 3 30 Triphenylsulfonium tetrafluoroporate 10 Crystal Violet Q, 5 tt Hydroquinone Q, 2 tt Toluene
100 tt Methyl ethyl ketone 200 tt Month: Bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. Epoxy equivalent, 450-500 Rice: Epoxy equivalent of Talezol Nopofuku type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. , 172-178 Zero 3: Alicyclic type epoxy resin manufactured by Daicel Chemical Co., Ltd.Epoxy equivalent, 128-145 This composition was applied to a 16-scale polyethylene terephthalate film (Lumirror T type) with a dry thickness of 75- It was applied with a bar coater so that 25JJj on top of that
The coating film was protected by pressure lamination with a polyethylene film, and this was used in the subsequent formation of the recording head of the present invention.

Synthesis Example 2 A living polymer (N-methylol methacrylamide/2-hydroxyethyl methacrylate (=30770 weight ratio)) obtained by anionic polymerization is reacted with p-vinylbenzyl chloride to form a vinyl polymer at one end of one molecular chain. A macromonomer with a weight average molecular weight of about 1500 having a group (
p-vinylbenzyl poly-N-methylol methacrylamide/2-hydroxyethyl methacrylate) was obtained.

30 parts by weight of conomacro monomer and 70 parts by weight of methyl methacrylate were solution-polymerized in methyl cellosolve to obtain a graft copolymer polymer (this will be referred to as CP-2) having a weight average molecular weight of 7.7×104 and having thermal crosslinkability. Obtained. Note that the glass transition temperature of the polymethyl methacrylate chain constituting the main chain of GP-2 is 100°C. This GP-2
An active energy ray-curable resin composition having the following composition was prepared using:

GP-21130 parts by weight Epicoat 828 No. 4 2o Celoxide 2021 20 tt Diphenyliodonium tetrafluoroporate 5 tt Para-toluenesulfonic acid 4 Crystal Violet Q, 5 //Hydroquinone 0.1111,1.1-1 Lichloroethane 200 /1 Methyl cellosolve 200 // Grass 4: Bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. Epoxy equivalent, 183-193 This composition was applied to a 16 μm polyethylene terephthalate film (Lumirror T type) with a dry thickness of The coating time was 75 μs using a bar coater. The coating film was protected by laminating 25 scales of polyethylene film thereon under pressure (1), and this was subsequently used to form the recording head of the present invention.

Synthesis Example 3 A living polymer (butoxymethylacrylamide/2-hydroxyethylmethacrylate (=7G/30 weight ratio)) obtained by anionic polymerization method is reacted with acrylic acid chloride to form a polymer at one end of the molecular chain. A macro-septumer (polybutoxymethylacrylamide acrylate/2-hydroxyethyl methacrylate) having a vinyl group and a weight average molecular weight of about 3000 was obtained.

25 parts by weight of this macro 7mer, methyl methacrylate? Parts of Qi and 5 parts of acrylonitrile were polymerized in methyl cellosolve to obtain a weight average molecular weight e, axto
Graft copolymer polymer having thermal crosslinking property of No. 4 (G
P-4) was obtained. Note that the glass transition temperature of the copolymer chain of polymethyl methacrylate chain and polyacrylonitrile chain constituting the main chain of GP-4 is 105°C. Using this GP-4, an active energy ray-curable resin composition having the following composition was prepared.

GP-440 parts by weight Epicron 828 80 //
Epicron N-730 7 80 1
1 triphenylsulfonium tetrafluorobore) 12//para-toluenesulfonic acid 41/crystal violet Q, 5 tthydroquinone Q, l //methyl cellosolve 300〃ethanol
50 II Zero 7: Dainippon Ink Chemical Industry (
Phenol novolac type epoxy resin manufactured by Co., Ltd. Epoxy equivalent: 170 to 180 This composition was coated on a polyethylene terephthalate film (Lumirror T type) with a thickness of 18 μs to a thickness of 75 μs after drying.
- coated with a bar coater and heated to 100°C.
By drying for 10 minutes, a dry film having an active energy ray-curable resin composition layer having a thickness of 75 mm was formed, which was used in the subsequent formation of the recording head of the present invention.

Synthesis Example 4 Thermoplastic graft copolymer polymer G obtained in Synthesis Example 1
A dry film having an active energy ray curable resin composition layer was formed in the same manner as in Synthesis Example 1, except that P-1 was used and the active energy ray curable resin composition was adjusted to have the following composition. , which was subsequently used in the formation of the recording head of the present invention.

G P-1100 parts by weight Epicote 828 80 tp Epicote 1001 50 // Celoxide 2021 40 // Triphenylsulfonium hexafluoroantimony lO Paratoluenesulfonic acid 4 Crystal Violet Q, 5tt Hydroquinone
0.1〃Methylceronlube 35
Synthesis Example except that the graft copolymer GP-2 having thermal crosslinkability obtained in Synthesis Example 2 was used and the active energy ray-curable resin composition was adjusted to have the following composition. A dry film having an active energy ray-curable resin composition layer was formed in the same manner as in Example 2, and used in the subsequent formation of the recording head of the present invention.

G P-2100 parts by weight Ebiko) 1001 100 //
Diphenyliodonium tetrafluoroporate 1011 para-toluenesulfonic acid 4 tt crystal violet 0.5//hydroquinone
0.1//Methyl cellosolve
350 Example 1 Using the dry film produced in Synthesis Example 1, a heating element [hafnium polide (
HfB2) 110 orifices (orifice dimensions;
An on-demand liquid jet recording head having a diameter of 75Q x 50 mm and a pitch of 0.1251 m was fabricated as follows. In addition, the recording head has the same shape as each 30
I made a prototype for individual use.

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 5i02 layer (thickness: 1.0 μs) as a protective film is provided on the substrate surface 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. 80
The film obtained in Synthesis Example 1 heated to Temperature 80℃, 1m/s
The lamination was carried out at a speed of 1 kg/cm 2 and a pressure of 1 kg/cm 2 . In this state, on the layer made of the active energy ray-curable resin composition laminated on the substrate,
Polyethylene terephthalate film is used.

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 provided in the liquid passage that is finally formed. After alignment, the illuminance at the irradiation surface from the top of this photomask is 8 mW/
The dry film was exposed for 150 seconds using an exposure light source (trade name: PLA-501, manufactured by Canon ■) using a cm2 deep UV lamp.

After exposure, the layer (dry film) made of the pattern-exposed active energy ray-curable resin composition was peeled off, and the colored polyethylene terephthalate film was peeled off, and the exposed dry film was treated with 1,1.1-trichloroethane/ethanol (=70 /30 weight ratio) in an ultrasonic cleaning machine at 35°C for 60 seconds to dissolve and remove the unpolymerized (uncured) portion of the dry film from the substrate. The remaining cured dry film formed grooves that would eventually become liquid passages and liquid chambers.

After finishing the development process, the cured dry film film on the substrate was heated at 80°C for 1 hour, and then lOJ/C1
After performing 12 post-exposures, the film was heated at IEO° C. for 60 minutes to further cure the film sufficiently.

In this way, grooves that will become liquid passages and liquid chambers are formed on the substrate using the cured dry film film, and then an epoxy resin adhesive is applied to a flat plate with through holes made of soda glass that will cover the formed grooves. After spin-cording to a thickness of 3 mm, it was preheated to B-stage, bonded to a cured dry film, and then the adhesive was fully cured and fixed to form a bonded body.

Subsequently, 0.150+
Place a reprinted dicing saw (trade name, [lAD 2H/e type, DI
(manufactured by SCO Corporation) to form an orifice for discharging 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. The resulting recording heads all had liquid passages and liquid chambers that faithfully reproduced the mask pattern, and had excellent dimensional accuracy. Incidentally, the orifice size was in the range of 50±5 scales, and the orifice pitch was in the range of 125±5 μs.

The quality and durability of the thus prototyped recorder during long-term use were tested in the following manner.

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 the recording head).

Recording liquid component 1) H20/ethylene glycol/diethylene glycol/propylene glycol/G, 1. ! Electric Black 154'l/Emarken 931'' (=8
4/201515/810.2 parts by weight) pH-8.0
2) H20/ ) Liethylene glycol/Glycerin/
c, t, hood black 2” 2/emaldan 8
31' 4 /PVP K-30" 5 (-80/15/2/310.110.1 parts by weight) p
H-9,03) H20/ethylene glycol/diethylene glycol/polyethylene glycol #300/tomethyl-2-pyrrolidone/C,1, food black 2″
2/Emulgen 931″4 (= 55710/2G15151510.2 parts by weight)
pH-7,04) H20/diethylene glycol/polyethylene glycol #200/1,3-dimethyl-
2-imidazolidinone/C. 1. direct blue 88
``3/Emaruge y831''/PVP K-30'' (
-62/15/1515/310.110.1 parts by weight)
pH-10.0 Note: 141 to '3 are water-soluble dyes.

Caustic soda was used to adjust the pH. Also.

H4 is the product name, polyoxyethylene nonylphenyl ether manufactured by Kao Soap Company, '45 is the product name,
Polyvinylpyrrolidone manufactured by GAF, USA.

After the durability test, we observed the state of bonding between the substrate and cover and the cured dry film for each head tested, and found that no peeling or damage was observed in any of the recording heads, indicating good adhesion. .

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

With respect to any of the recording heads, almost no deterioration in performance 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.

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

Furthermore, the same durability test and printing test as in Example 1 were conducted for each of the produced recording heads.

After the durability test, we observed the state of bonding between the substrate and cover and the cured dry film for each head tested, and found that no peeling or damage was observed in any of the recording heads, indicating good adhesion. .

In addition, in printing tests, there was almost no decline in the performance of any recording head, both in the recording liquid ejection performance and the printing condition, both immediately after printing started and after 14 hours.
All recording heads had excellent durability.

Example 3 Using the dry film produced in Synthesis Example 3, it was heated using a hot roll laminator (trade name: HRL-24, manufactured by DuPont Co., Ltd.) at a roll temperature of 80°C and a roll pressure of IK.
After laminating the g/c layer 2 on the substrate at a lamination speed of 1 layer/sin, using a high-pressure mercury lamp as the exposure light source, the illuminance near the 2541 layer on the irradiated surface was 34 -
/CC10, and then the polyethylene terephthalate film was peeled off from the pattern-exposed layer (dry film) made of the active energy ray-curable resin composition, and then exposed to 1.1.1-trichloroethane. /butyl cellosolve (-70/30 heavy i
L ratio) was developed by spraying it at 35°C for 80 seconds, and then the cured dry film film on the substrate was heated at 80°C for 10 minutes, followed by post-exposure at 10 J/cm2. A liquid jet recording head was produced in the same manner as in Example 1, except that it was heated at 50° C. for 80 minutes to further cure it sufficiently.

Furthermore, the same durability test and printing test as in Example 1 were conducted for each of the produced recording heads.

After the durability test, we observed the state of bonding between the substrate and cover and the cured dry film for each head tested, and found that no peeling or damage was observed in any of the recording heads, indicating good adhesion. .

In addition, in printing tests, there was almost no decline in the performance of any recording head, both in the recording liquid ejection performance and the printing condition, both immediately after printing started and after 14 hours.
Both recording heads had excellent durability.

Examples 4 and 5 A liquid jet recording head was produced in the same manner as in Example 1, except that the dry films obtained in Synthesis Examples 4 and 5 were used individually.

Furthermore, the same durability test and printing test as in Example 1 were conducted for each of the produced recording heads.

After the durability test, we observed the state of bonding between the substrate and cover and the cured dry film for each head tested, and found that no peeling or damage was observed in any of the recording heads, indicating good adhesion. .

In addition, in printing tests, there was almost no decline in the performance of any recording head, both in the recording liquid ejection performance and the printing condition, both immediately after printing started and after 14 hours.
All recording heads had excellent durability.

Comparative Example A commercially available dry film Vacrel (with a film thickness of 75 μs)
Product name of dry film solder mask, DuPont
In the same manner as in Example 1, except that a commercially available dry film Photec 5R-3000 (trade name, manufactured by Hitachi Chemical Co., Ltd.) with a film thickness of 50 scales was used.
Created a recording head.

A durability test similar to that in Example 1 was conducted on these recording heads.

During the course of the durability test, Vacre was used as a dry film.
When 1 was used, peeling was observed in recording liquids 2) and 4) after 100 hours. Also, in 300 hours, 1)
and 3) Peeling was observed with the recording liquid.

On the other hand, the dry film Phototec 5R-30
When using 00, each recording liquid from 1) to 4)
Peeling was observed at 0 hours.

[Brief explanation of the drawing]

1 to 6 are schematic diagrams for explaining the liquid jet recording head of the present invention and its manufacturing method. Substrate 2: Discharge energy generating element 3: Resin layer 3H: Cured resin film 4: Photomask 4P: Mask pattern 6-1 = Liquid chamber 6-2: Liquid passage 7: Cover 8: Through hole 9 Niorifice 1O: Supply pipe (a) (b) 'IPJ1 Figure Figure 2 (?1) (b) 'Figure 6

Claims (1)

[Claims] 1) A liquid passage provided on the substrate surface and communicating with a liquid discharge port exposes a layer of a resin composition that is cured by active energy rays in a predetermined pattern using active energy rays. A liquid jet recording head formed by forming a cured region of the resin composition and removing an uncured region from the layer, wherein the resin composition comprises (i) alkyl methacrylate, acrylonitrile and (A) a hydroxyl group-containing acrylic monomer, (B) an amino or alkylamino group-containing acrylic monomer, and (C) a carboxyl group in a backbone chain mainly composed of structural units derived from one or more monomers selected from the group consisting of styrene. containing acrylic or vinyl monomer, (D) N-vinylpyrrolidone or its derivative, (E) vinylpyridine or its derivative, and (F) one or more monomers selected from the group consisting of an acrylamide derivative represented by the following general formula I. Graft copolymer polymers with branched chains mainly derived from the structural units derived from them and is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, and R^2 represents an alkyl or acyl group that may have hydrogen or a hydroxy group having 1 to 4 carbon atoms.) (ii) An epoxy group in the molecule. A liquid injection comprising: an epoxy resin containing at least one compound having one or more compounds; and (iii) a polymerization initiator that generates a Lewis acid upon irradiation with active energy rays. recording head. 2) In the resin composition, when the content of the graft copolymer polymer in (i) is G parts by weight and the content of the resin in (ii) is E parts by weight, G/(G+E) is 0. .2~0.
8, contains the graft copolymer polymer of (i) and the resin of (ii), and
The liquid jet recording head according to claim 1, which contains the polymerization initiator i) in an amount of 0.2 to 15 parts by weight based on 100 parts by weight of (G+E). 3) A patent claim in which the polymerization initiator (iii) is composed of an aromatic halonium salt compound or a photosensitive aromatic onium salt compound containing an element belonging to Group VIa or Group Va of the Periodic Table. A liquid jet recording head according to any one of the ranges 1 to 2.