JPS6216153A - Liquid jet recording head - Google Patents

Abstract

PURPOSE:To provide a precise liquid jet recording head excellent 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 cured by active energy rays formed on a substrate to form the cured regions of the resin composition and uncured regions are removed from said layer to form liquid passages communicated with liquid emitting orifices to the surface of the substrate. Said resin composition consists of (i) a linear polyme of which the glass transition temp. is 50 deg.C or more and the wt. average MW is about 3.0X10<4> or more, (ii) an epoxy resin containing at least one of compounds each having one or more of an epoxy group in the molecule thereof and (iii) a polymerization initiator generating Lewis acid by the irradiation of active energy rays. By using this resin composition, a recording head excellent in the durability of each member and adhesion between members and having a resin cured film layer finely procesesed with good accuracy and excellent in recording characteristics and durability is obtained.

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.

One method for manufacturing a liquid jet recording head with such a configuration is 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 accuracy 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 for the recording head has the following characteristics: (2) Excellent mechanical strength and durability when cured; (3) Excellent sensitivity and resolution when forming patterns using pattern lightning. It is required to have characteristics such as excellent properties.

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. Mechanical strength and durability are insufficient. Therefore, during the manufacturing stage of the print head or during use, for example, the flow of the print liquid in the liquid passage may be obstructed, or the direction of droplet ejection may be made unstable, resulting in deterioration of the print characteristics. This method has the disadvantage that the cured resin film is easily deformed, peeled off from the substrate, and damaged, which significantly impairs the reliability of the recording head.

On the other hand, known 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. Since it is not possible to obtain a high-density pattern, this method has the problem that it is not suitable for use in recording heads that require particularly fine precision machining.

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.

The present invention provides a method in which 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 rays. A liquid jet recording head formed by forming a cured region of a resin composition and removing an uncured region from the layer, wherein the resin composition (i) has a glass transition temperature of 50° C. or higher, and The weight average molecular weight is approximately 3. A linear polymer having an OX of 104 or more.

(ii) an epoxy resin comprising at least one compound having one or more epoxy groups in the molecule;
) A liquid jet recording head comprising a polymerization initiator that generates a Lewis acid upon irradiation with active energy rays.

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.
This is a cross-sectional view taken along line C(:' in Figure (a).

This liquid jet recording head basically includes a substrate 1, a cured resin film 3H provided on the substrate and pattern-exposed in a predetermined shape, and a cover 7 laminated on the cured resin film. These members include an orifice 9 for discharging the recording liquid, and a liquid passage 8 that communicates with the orifice and has a portion on which energy for discharging the recording liquid acts on the recording liquid. 2 and a liquid chamber e-t 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 "8-1" is connected to the through hole 8 provided in the cover. , the supply pipe IO is omitted.

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.

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.

Further, the cover 7 is made of a flat plate made of glass, ceramics, plastic, metal, etc., and is bonded to the resin hardening layer 11 by a bonding method using fusion or adhesive, and the supply pipe 10 is placed in a predetermined position. A through hole 8 is provided for connecting.

In the recording head of the present invention, the cured resin film 3H patterned in a predetermined shape and forming the walls of the liquid passage 6-2 and the liquid chamber e-t is formed on the substrate 1 or on the cover 7. It was obtained by patterning a layer made of a resin composition having the composition described in 1. by 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 has the following properties: (i) a glass transition temperature of 50°C or higher and a weight average molecular weight; is about 3. a linear polymer having OX 10' or more; (11) an epoxy resin comprising at least one compound having one or more epoxy groups in the molecule; and (iii)
) An active energy ray-curable resin composition containing as an essential component a polymerization initiator that generates a Lewis acid when irradiated with active energy rays, and is particularly effective when formed into a cured film on a substrate made of glass, plastic, ceramics, etc. Liquid jet recording has good adhesion to recording liquids such as ink, has excellent mechanical strength and resistance to recording liquids such as ink, and can form precise, high-resolution patterns by patterning with active energy rays. It has excellent properties as a component of a 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.

This active energy ray-curable resin composition provides suitability for maintaining the composition in the form of a solid film when the composition is used as a dry film to form the recording head of the present invention, and is also suitable for curing. In order to impart excellent mechanical strength to the formed pattern, (i) the glass transition temperature is 50°C or higher and the weight average molecular weight is approximately 3. OX10
Contains a linear polymer having a molecular weight of 4 or more as an essential component.

When the glass transition temperature and weight average molecular weight of the linear polymer are less than the above values, for example, when producing a dry film, it is formed as a film-like solid resin layer on a support such as a plastic film. The composition gradually flows during storage, causing wrinkles or uneven layer thickness, making it impossible to obtain a good dry film.

Specifically, such linear polymers include, for example, a homopolymer mainly composed of 7-mer (A), which has relatively rigid properties and can provide the above-mentioned glass transition temperature,
If necessary, as a second component, for example, having hydrophilicity,
CB which can provide even better adhesion to the composition of the present invention)
hydroxyl group-containing acrylic monomer, (C) amine or alkylamino group-containing acrylic monomer, (D) carboxyl group-containing acrylic or vinyl monomer, (E)
Monomers such as N-vinylpyrrolidone or its derivatives, CF) vinylpyridine or its derivatives.

(G) The following general formula 1 can impart high cohesive strength to the active energy ray-curable resin composition and improve its mechanical strength (wherein R1 is hydrogen or an alkyl group having 1 to 3 carbon atoms, R2 (R3 represents an alkyl or phenylalkyl group having 3 to 12 carbon atoms, or a phenyl group.) Examples include thermoplastic copolymer polymers obtained by using monomers represented by the following as components of copolymerization in a range of 40 mol % or less.

Specifically, the monomers used as component (A) include methyl methacrylate, ethyl methacrylate,
Examples include alkyl methacrylates in which the alkyl group has 1 to 4 carbon atoms, such as inbutyl methacrylate and t-butyl methacrylate, acrylonitrile, and styrene. In order to impart the above-mentioned glass transition temperature to the linear copolymer, it is preferable that 60 mol % or more of these hexamers are contained.

Specifically, the monomers (B) to (G) above used as the second component include 2-hydroxyethyl (meth)acrylate (hereinafter referred to as (meth)acrylate) as the hydroxyl group-containing acrylic monomer (B). ), 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate.
Acrylate, 3-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate,
Examples include 6-hydroxyhexyl (meth)acrylate, or a monoester of 1,4-cyclohexane dimetatool and acrylic acid or methacrylic acid,
Product name: Aronix M5700 (manufactured by Toagosei Chemical Co., Ltd.)
, TONE Mloo (caprolactone acrylate,
Union Carbide Co., Ltd.), Light Ester HO-11
PP (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), those known as Light Ester Toro 00A (trade name of 2-hydroxy-3-phenoxypropyl acrylate, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), and dihydric alcohols, e.g. .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.

As the amino or alkylamino group-containing acrylic monomer (C), (meth)acrylamide, KN-
Dimethylamine ethyl (meth)acrylamide, KN
-dimethyl (meth)acrylamide, N, N-dimethylaminepropyl (meth)acrylamide, N, N-
Examples include dibutylaminoethyl (meth)acrylamide.

Examples of the carboxyl group-containing acrylic or vinyl monomer (CD) include (meth)acrylic acid, fumaric acid, itaconic acid, and those known under the trade names of Aronixt 5400 and Aronix M-5500 manufactured by Toagosei Kagaku.

CF) as vinylpyridine or its derivatives,
Examples include 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methylpyridine, 4-vinyl-1-methylpyridine, 2-vinyl-5-ethylpyridine, and 4-(4-pipenylinoethyl)bi-1nodine. be able to.

All of the above monomers (B) to (F) have wood-philicity, and the active energy ray-curable resin composition used in the present invention adheres to a support such as glass, ceramics, or plastic. 1. It provides strong adhesion when applying.

Specifically, the monomer (G) represented by the general formula 1 contains one hydroxyl group in one molecule (α-alkyl)
Examples include (α-alkyl) acrylic esters having one or more urethane bonds in one molecule, which are obtained by reacting an acrylic ester with a monoincyanate compound. Incidentally, R2 in the monomer represented by general formula 1 can be any divalent hydrocarbon group which may have an ether bond therein and may be substituted with a halogen atom, but is preferably As R2, the number of carbon atoms is 2 to
an alkylene group optionally substituted with 12 halogen atoms,
Examples include alicyclic hydrocarbon groups such as 1,4-bismethylenecyclohexane and hydrocarbon groups containing aromatic rings such as bisphenyldimethylmethane.

Containing at least one hydroxyl group in one molecule used when producing the monomer represented by the above general formula 1 (
As meth)acrylic acid esters, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (
meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 5-hydroxypentyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate ) acrylate or light ester HO-11PP (manufactured by Kyoeisha Yushi Kagaku Kogyo ■).

In addition to the above, (α-alkyl)acrylic acid esters containing one hydroxyl group in one molecule include (a) esters of aliphatic or aromatic dihydric alcohols and (meth)acrylic acid, and (b) monoesters. (Meth)acrylic esters of epoxy compounds can likewise be used.

The dihydric alcohol used in (a) above includes 1.
Examples include 4-cyclohexane dimetatool, 1.10-decanediol, neopentyl glycol (2-hydroxyethyl) terephthalate, and addition reaction products of 2 to 10 moles of ethylene oxide or propylene oxide to bisphenol A. In addition, as the monoepoxy compound used in (b) above, Evolite 12
30 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo ■), phenyl glycidyl ether, talesyl glycidyl ether, butyl glycidyl ether, octylene oxide, n-
Examples include butylphenol glycidyl ether.

Further, as the monoisocyanate compound used in producing the monomer represented by general formula 1, alkyl monoisocyanate formed by adding one incyanato group to an alkyl group having 3 to 12 carbon atoms, and phenyl monoisocyanate Examples include isocyanate and talesyl monoisocyanate.

It is preferable that the heptamine represented by the general formula 1 is contained in the linear copolymer polymer in an amount of up to 50 mol%. If the content exceeds 50 mol%, the softening point of the resulting composition will be significantly lowered.

Decreased surface hardness of the pattern obtained by curing.

This causes problems such as deterioration of chemical resistance due to swelling.

The resin composition for forming a cured resin film used in the present invention can be provided in various forms depending on the purpose of use, such as a solution or a solid film, but it is not practical to use it in the form of a dry film. It is particularly advantageous because it is easy to handle and the film thickness can be easily controlled. Of course, there is no problem in using it in the form of a solution.

The case where thermoplastic linear polymers are mainly used has been explained above, but the active energy ray-curable resin composition used in the present invention uses linear polymers that have thermal crosslinkability or photocrosslinkability. You can also do that.

The thermally crosslinkable linear polymer is, for example, a thermoplastic linear polymer having the following general formula II - (where R4 is hydrogen or an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, and RS is hydrogen). or the number of carbon atoms is 1-
Represents an alkyl or acyl group that may have 4 hydroxy groups. ) can be obtained by introducing a thermally crosslinkable heptamer as the second component in copolymerization. The monomer represented by the general formula (3) has not only thermal crosslinkability but also wood-philicity, and due to the thermal crosslinkability, the composition of the present invention has excellent properties as a structural material, such as heat resistance,
It exhibits chemical resistance, mechanical strength, etc., and excellent adhesion to a support due to its hydrophilicity.

Specifically, the monomer represented by the above general formula (■) is N
-Methylol (meth)acrylamide (hereinafter referred to as (meth)
When it is written as acrylamide, it is meant to include both acrylamide and metaacryamide. ),
N-propoxymethyl (meth)acrylamide, N-n
-Butoxymethyl (meth)acrylamide, β-hydroxyethoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-acetoxymethyl (meth)acrylamide, α-hydroxymethyl- N-methylolacrylamide, α-hydroxyethyl-N-butoxymethylacrylamide, α-hydroxypropyl-N-propoxymethylacrylamide, α-ethyl-
Examples include acrylamide derivatives such as N-methylolacrylamide and α-propyl-N-methylolacrylamide.

These monomers represented by the general formula II have not only wood-philic properties but also condensation crosslinking properties by heating, as described above.
In general, at temperatures of 100°C or higher, water molecules or alcohol are released and form crosslinks, and after curing, the linear copolymer polymer itself also forms a network structure, and the pattern obtained by curing has excellent chemical resistance. and provides mechanical strength.

When a thermosetting linear polymer is used, the seven polymers represented by the general formula (■) are 5 to 5.
Preferably, 30 mol% is contained in the linear polymer,
When the content is within the above range, sufficient chemical resistance based on thermosetting is provided. On the other hand, if the content exceeds 30 mol %, problems such as the pattern obtained by curing will become brittle.

In addition to the heptamers represented by the above general formula You can get the same effect as .

A photocrosslinkable linear polymer can be obtained, for example, by introducing a photopolymerizable side chain into a linear polymer, as exemplified below. Examples of such a method include 1. Copolymerizing a monomer containing a carboxyl group, such as (meth)acrylic acid, or a monomer containing an amino group or a tertiary amine group, followed by copolymerization of glycidyl (meth)
Method of reacting with acrylate, etc., (1) 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, amine 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 acid anhydride, and then reacting with glycidyl (meth)acrylate, [Phase] The method of reacting the hydroxyl group of the branch chain with ( Examples include 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.

When the linear polymer contained in the active energy ray-curable resin composition used in the present invention is thermally crosslinkable, the resin composition is heat-treated after forming a pattern by irradiation with active energy rays. On the other hand, even when a photopolymerizable linear polymer is used in the composition, there is no problem in heating within an allowable range in terms of the heat resistance of the support. In fact, it gives a more favorable result.

The linear polymers that can be contained in the active energy ray-curable resin composition used in the present invention can be broadly classified into those without curability, those with photocrosslinkability, and those with thermal crosslinkability. However, in any case, in the curing process of the composition used in the present invention (i.e., pattern formation by active energy ray irradiation and thermal curing as necessary), shape retention is imparted to the composition. It not only enables precise patterning, but also provides excellent adhesion, chemical resistance, and high mechanical strength to the pattern obtained by curing.

The epoxy resin (ii) consisting of one or more compounds containing 1 (11 or more) epoxy groups in one molecule contained in the active energy ray-curable resin compound acid used in the present invention refers to the polymerization initiator (iii) described below. ), the composition used in the present invention exhibits sufficient curability with high sensitivity to active energy rays, and in addition, the resin composition of the present invention 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, 1. For example, when forming a recording head, consideration must be given to the chemical resistance and mechanical strength of the cured 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 a support that includes grooves that serve as liquid passages made of a cured film,
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 and bisphenol F.

Tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol triglycidyl ether, isocyanuric acid triglycidyl ether and the following general compounds m υ U (However, R is an alkyl group or an oxyalkyl group. Examples include polyfunctional epoxy resins such as epoxy urethane resins represented by the following formulas, and mixtures of one or more of these resins.

Incidentally, specific examples of these polyfunctional epoxy resins include the following.

That is, as a bisphenol A type epoxy resin, 1
For example, Epicor) 828, 834, 871.10
01, 1004 (trade name, manufactured by Shell Chemical Co., Ltd.), DE
R331-J, 337-J, 881-J,
1184-J, 81117-J (manufactured by Dow Chemical Co., Ltd.) and Epiclon 800 (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.); examples of novolac type epoxy resins include Epicort 152°154, 172, (trade name, Shell Chemical Co., Ltd.), Araldai) KPM 11
38 (product name, manufactured by Ciba Geigy), DER43
1, 438, and 43S (trade name, manufactured by Dow Chemical Company); examples of alicyclic epoxy resins include Araldite CY-175, -178, -179° -182, -18
4, -192 (product name, manufactured by Ciba Geigy), Chisson Knox 090, 091, 092, 301.313
(Product name, manufactured by Chisso Corporation), Syracure (CYRAC)
URE) 810G, 611O18200 and ERL 4
G90.4817, 225B, 5411 (trade name, manufactured by Union Carbide), etc.; Examples of polyglycidyl ethers of aliphatic polyhydric alcohols include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanethiol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 2,2-dibromo Neopentyl glycol diglycidyl ether, etc.; polyhydric glycidyl ethers derived from aromatic polyhydric alcohols include 2 to 1 of alkylene oxide of bisphenol A.
Examples include diglycidyl ether as a 6 mol adduct, diglycidyl ether as a 2 to 16 mol adduct of bisphenol F with alkylene oxide, and diglycidyl ether as a 2 to 16 mol adduct of bisphenol S with alkylene 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 phenyl glycidyl ether, cyclohexene vinyl monooxide, 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 resin cured film used in the present invention, the epoxy resin (ii) has a Lewis acid generated when the polymerization initiator (iii) described below is irradiated with active energy rays. It has sufficient curability with high sensitivity to active energy rays generated by acting on the epoxy groups of the resin, and not only does this curability enable precise and high-resolution pattern formation, but in addition to this, The inherent thermosetting properties of epoxy resins also provide good adhesion to supports, chemical resistance, dimensional stability, etc.

In the present invention, the polymerization initiator (iii) that generates a Lewis acid upon irradiation with active energy rays, which is contained in the resin composition used for forming a cured resin film, refers to the above-mentioned epoxy resin (ii) due to the action of the Lewis acid. It is a component for curing the resin composition used in the present invention to exhibit sufficient curability with high sensitivity to active energy rays. Aromatic onium salt compounds with photosensitivity containing elements belonging to the Vla group, or Japanese Patent Publication No. 52-14
Aromatic onium salt compounds having photosensitivity containing elements belonging to Group Va as shown in Publication No. 279, or aromatic halonium salts having photosensitivity shown in Japanese Patent Publication No. 52-14277. Can be used.

Both of these aromatic onium salt compounds and aromatic l\ronium 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): [(R6)a (R')b (R8)eX]; [MQ
@]-'-"...(IV) (In the above formula, R6 is a monovalent organic aromatic group, R7 is a monovalent organic aliphatic group selected from an alkyl group, a cycloalkyl group, and a substituted alkyl group, R8 is a polyvalent organic group constituting a heterocyclic or fused ring structure selected from aliphatic groups and aromatic groups; A selected element belonging to Group Va, M represents a metal or metalloid, and Q represents a halogen group,
a is 0 to 3 when X is an element belonging to Group VIa
an integer of 0 to 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 O or 1 when X is an element belonging to group VIa, X is an integer of group V
In the case of an element belonging to group a, f is an integer of O~2, f is M
is an integer from 2 to 7 in valence, 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 In the case of an element belonging to the Va group, examples thereof include compounds represented by 4 and d=ef).

In addition, as photosensitive aromatic halonium salts, the following general V) [(R9)* (R')hX]i' [MQJ
]-"-" ... (V) (In the above formula, R9 is a monovalent aromatic organic group, - is a divalent aromatic organic group, X is a halogen group, M is a metal or metalloid, and Q is each represents a halogen group, g is an integer of O or 2, h is an integer of 0 or l, the sum of g and h is equal to 2 or the valence of X, i is equal to -t, and l is is an integer from 2 to 7 equal to the valence of M, and k is an integer up to 8 that is larger than !).

Specific examples of the photosensitive aromatic onium salt compounds containing elements belonging to Group IVa or Group Va include photosensitive aromatic onium salts of elements belonging to Group VIa, such as can be mentioned.

Moreover, as a specific example of the photosensitive aromatic halonium salt, the following may be mentioned.

In addition, a polymerization initiator (ii) that releases a Lewis acid such as L
In addition to i), curing agents such as polyamines, polyamides, acid anhydrides, boron trifluoride-amine complexes, dicyandiamide, imidazoles, and complexes of imidazole and metal salts, which are generally widely known as curing agents for epoxy resins, can be used. It may be used as necessary.

In the active energy ray-curable resin composition for forming a cured resin film used in the present invention, a linear polymer (i) that is photopolymerizable is used as the linear polymer (i) contained in the composition, and when photopolymerized, When using active energy rays with a wavelength of 250 nm to 450 nm, in addition to the polymerization initiator (iii) referred to in the present invention, a radical polymerization initiator capable of generating right RM separation radicals that can be activated by the action of the active energy rays is used. It is preferable to add the agent into the resin composition,
As this radical polymerization initiator, any known substance having the property of being activated by active energy rays, 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, pentwin-n-butyl ether, benzoin ethyl ether, benzoin methyl ether, etc., benzophenones: benzophenone, 4 .4'-bis(N,N-diethylamino)benzophenone, benzophenone methyl ether, etc., anthraquinones: 2-dithylanthraquinone, 2-t-butylanthraquinone, etc., xanthones: 2,4-dimethylthioxanthone, 2,4-diisopropyl Acetophenones such as thioxanthone: 2,2
-dimethoxy-2-phenylacetophenone, α, α-
Dichloro-4-phenoxyacetophenone, p-te
rt-butyltrichloroacetophenone, p-tert
-butyl dichloroacetophenone, 2,2-jetoxyacetophenone, p-dimethylaminoacetophenone, etc., or hydroxycyclohexylphecol ketone (Irgacure 184 manufactured by Civer Geigy), 1-
(4-impcobylphenyl)-2-hydroxy-2-
Methylpropan-1-one (Darocur 1116 manufactured by MERCK), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Glocure 1
173 Merck Compensation) etc. are preferably used. In addition to these radical polymerization initiators,
An amino compound may be added in addition to a photopolymerization accelerator.

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

The composition ratio of the materials constituting the active energy ray-curable resin composition used in the present invention is such that the content of the linear polymer (i) is L parts by weight, and the content of the epoxy resin (ii) is 8 parts by weight. When L/(L+E) is in the range of 0.2 to 0.8, and the polymerization initiator (ii
i) is 0.2 to 15 per 100 parts by weight of (L+E)
When L/(L+E), which is preferably contained in parts by weight, is smaller than 0.2, the content of the linear polymer in the resin composition decreases, and the linear polymer-based support Inconveniences arise, such as insufficient adhesion with the resin, or when a solvent is used, the drying properties of the solvent deteriorate, resulting in a sticky surface of the pattern obtained by curing. On the other hand, L
/ (L+E) exceeds 0.8, the content of the epoxy resin decreases, the sensitivity to active energy rays decreases, and problems such as a decrease in the solution ('l If) of the formed pattern occur.

In addition, when a radical polymerization initiator that is activated by the action of activation energy rays is used in the resin composition, the polymerization initiator is a linear polymer (i), an epoxy resin (ii)
and a polymerization initiator (iii) that generates a Lewis acid [(i)+(ii)+(iii)] 1100
0.1 to 20 parts by weight, preferably 1 to 10 parts by weight
Parts by weight range.

The solvents used in the present invention include alcohols, Examples include hydrophilic solvents such as glycol ethers and glycol esters. Of course, these wood-philic 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 1-trichloroethane. Incidentally, these solvents can also be used as a developer for the resin 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. Fillers increase the hardness, color, and adhesion of the coating film.

To increase mechanical strength, extender pigments, plastic particles, etc., which are commonly used in paints, are used.

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

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. Examples of film-like substrates used at this time include biaxially stretched films with a thickness of 16 to 100 μs, polyethylene terephthalate film, cellulose triacetate, poly-1-vinyl fluoride, polyvinyl chloride, polyvinylidene chloride, Possible examples include poly-4-methylpentene-1, polyethylene, polypropylene, and laminates or coextruded films thereof. In addition, as a lamination method when producing a dry film by laminating the composition on a film-like base material as described above, a coating method using a roll coater, a bar coater, etc.
Well-known methods such as dipping, spray coating, and coating can be used.

Further, as a method for forming a pattern using such a dry film, for example, on a desired support on which a pattern is to be formed, such as a substrate on which a liquid ejection energy generating element of a recording head is provided or a plate material serving as a cover, After laminating the dry film using elastic rolls such as rubber rolls, the dry film is fixed to the support using a well-known laminating device that can be heated and pressurized, and then the film-like base material of the dry film is laminated. This may be carried out by removing or not removing, masking and irradiating active energy rays, or selectively irradiating 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.

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, for the purpose of imparting resistance to recording liquid, electrical insulation, etc. to the surface of the substrate 1 as necessary, 5iOz, T is applied to the surface of the substrate 1.
a205, may be coated with a protective layer such as glass, and
Although not shown in the ejection energy generating element 2,
The recording signal input electrode is connected.

Next, after cleaning the surface of the substrate 1 obtained through the process 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, about 20-200 mm) was heated at 40-150°C.
For example, 0.5 to Q, 4 f/rai
The substrate is laminated onto the substrate surface IA at a speed of n, under pressure conditions of 1 to 3 Kg/c+s2.

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.

It should be noted that through processes such as alignment 11 of the photomask 4 and the substrate 1, exposure, and development processing, the element 2 is positioned in the liquid passage area that is finally formed. 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, and metal halide lamps that contain a lot of 50r++s light, and the intensity of light in the vicinity of 385 nm is 1 mW/cm2 to 10011 w/c11 at a practically acceptable distance between the irradiated objects.
Although there is no particular limitation on the electron beam irradiation device, which preferably has a dose of about 2.2 M Rad, 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 to t, t, t-
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 the cured resin film 3H remaining on the substrate 1 finally forms a liquid passage as shown in FIGS. 5(a) and 5(b). 6-
2 and a groove that will become the liquid chamber 6-1 is 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. In addition, when the dry film 3 contains a thermosetting linear polymer, the temperature of this heat treatment is preferably at least 100'C.

In addition, in the recording head of this example, the liquid passage 6-2
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 chambers 6-1. The curable resin composition 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 the recording head of the present invention, it is convenient to use a solid film type recording head in terms of handling and the fact that the thickness can be easily and accurately controlled.

In this way, after forming the grooves that will finally constitute the liquid passage 6-2 and the liquid chamber 8-1 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 the flat plate 7 of glass, ceramic, metal, plastic, etc. to a thickness of 3 to 4 mm,
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, e-t is a liquid chamber, 8-2 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. (not shown).

In this way, the resin cured film 3H provided on the substrate l
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 8-2 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 IO 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. At least the liquid passage 6-2 may be connected to the member made of the activated-Nelli radiation-curable resin composition described above.
By removing the portion corresponding to the groove forming the liquid passage, the resin cured film 3H forming the groove forming the liquid passage and the cover 7 are integrated and are both formed from the active energy ray curable resin composition. The recording head may also be formed by forming a recording head and bonding this onto a substrate.

Further, in the recording head described above, the liquid passage 6-2 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 linear polymer (i) and the epoxy resin (ii) as essential components. In other words, the resin composition of wood [Jl] is mainly made of
In addition to the excellent adhesion to the support and mechanical strength provided by the linear polymer (i), the epoxy resin (
It has excellent chemical resistance and one-method stability imparted by i), and by using this composition, it has become possible to obtain a recording head with long-term durability.

Furthermore, when an active energy ray-curable resin composition using a linear polymer having curability is used, liquid jet recording with even better adhesion, mechanical strength, or chemical resistance can be achieved. It is possible to obtain a

〔Example〕

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

Synthesis Example 1 Methyl methacrylate, butyl carbamylethyl methacrylate, and butoxymethyl acrylamide (= 80
/10/10 molar ratio) in toluene to obtain a weight average molecular weight of 1.4 XIO3 and a glass transition temperature of 75°C.
A linear polymer compound with thermal crosslinking properties (this is called LP-2
) was obtained.

Using this LP-2, an active energy ray-curable resin composition having the following composition was prepared.

LP-2100 parts by weight Epicoat toot powder 460/
/ Epicron N-730 request 5 40 〃
Celloxide 2021 50 tt Triphenylsulfonium 11 Tetrafluoroporate 12 Crystal Violet 0.51/Methyl Isobutyl Ketone 200 tt Toluene
100 ttI: Bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. Epoxy equivalent weight, 450-500 Attack 5: Phenol nobotic type epoxy resin manufactured by Dainippon Ink & Chemicals Co., Ltd. Epoxy equivalent weight, 170-180 This composition was applied to a polyethylene terephthalate film (Lumirror T type) with a thickness of 16 scales and a thickness of 75 mm after drying.
Apply with an 8-two tool and heat at 100℃, 1
This was dried for 0 minutes to form a dry film type film having an active energy ray-curable resin composition layer having the above composition, which was used in the subsequent formation of the recording head of the present invention.

Synthesis Example 2 A copolymer was obtained by solution polymerizing methyl methacrylate, acrylic acid, and 2-hydroxyethyl methacrylate (=70/10/20 molar ratio) in toluene. An equivalent amount of glycidyl methacrylate is added thereto, and the reaction is carried out at 80° C. using triethylbenzylammonium chloride as a catalyst to give a weight average molecular weight of 1. A photocrosslinkable linear polymer compound (referred to as LP-3) with a glass transition temperature of 96°C and a glass transition temperature of 96°C was obtained.

Using this LP-3, an active energy ray-curable resin composition having the following composition was prepared.

LP-3100 parts by weight Epicron 83018 80 /
/ Epicote 152 bottles 7 60
//Celoxide 2021 50/
/ diphenyliodonium tetrafluoroporate 12 // crystal violet 0.5 methyl isobutyl ketone 200 tt toluene
100 t6 Bisphenol F type epoxy resin manufactured by Nidai Nippon Ink Chemical Industry Co., Ltd. Epoxy equivalent weight, 170-190 Coating 7: Cresol novolak type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. Epoxy equivalent weight, 172-179 This composition was coated on a 16-inch polyethylene terephthalate film (Lumirror T type) using a bar coater so that the thickness after drying was 75-inch. The coating film is protected by pressure laminating a 25-g polyethylene film thereon to form a dry film type film having an active energy ray curable resin composition layer having the above composition. It was used to form a recording head.

Example 1 Using the dry film produced in Synthesis Example 1, a heating element [hafnium polide (
HfB2) ] An on-demand liquid jet recording head having 10 orifices (orifice dimensions: 75 μs×50 μ, pitch 0.125) was fabricated 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 5i02 layer (thickness: 1.0 μs) was provided as a protective film on the substrate surface on which one heating element was arranged, and after cleaning and drying the surface of the protective layer, it was stacked on the protective layer. 80
The film obtained in Synthesis Example 1 heated to
Lamination was carried out under pressure conditions using a roll temperature of 80° C., a speed of Is/win, and a pressure of 1 Kg/as2ty). In this state, a polyethylene terephthalate film is laminated on the layer made of the active energy ray-curable resin composition laminated on the substrate.

Next, a photomask having a pattern corresponding to the 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, exposure was performed for 50 seconds from the top of the photomask using a high-pressure mercury lamp with an illumination intensity of 34 mW/as2 in the vicinity of 254 ns on the irradiated surface.

After exposure, the polyethylene terephthalate film is peeled off from the pattern-exposed layer (dry film) made of the active energy ray-curable resin composition, and the exposed dry film is coated with 1,1,1-trichloroethane/butyl cellosolve (270,730 wt. ratio) 35 using a mixed solution
Developed by spraying for 60 seconds at ℃,
The unpolymerized (uncured) portion of the dry film was dissolved and removed from the substrate, and the cured dry film film remaining on the substrate formed grooves that would eventually become liquid passages and liquid chambers.

After completing the development process, the cured dry film film on the substrate was heated and dried at 80°C for 10 minutes, and then heated at 10J/c.
112 post-exposures followed by an additional 6 at about 150°C.
This was heated for 0 minutes to fully cure the resin component.

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-coding to a thickness of 3 scales, preheating was performed to B-stage, this was bonded onto a cured dry film, and the adhesive was further cured and fixed to form a bonded body.

Next, 0.150 a is applied to the downstream side of the liquid passage of the bonded body, that is, from the installation position of the ejection energy generating element.
vertically to the liquid path using a commercially available dicing saw (product name: DAD 2H/B type, D 15C).
(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 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 tiles, and the orifice pitch was in the range of 125±5 μs.

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

First, the obtained recording head was subjected to a durability test in which it was immersed in a recording liquid having the following compositions at 80° C. for 1000 hours (environmental conditions comparable to those during long-term use of the recording head).

Recording liquid component 1) H20/diethylene glycol/polyethylene glycol #200/1,3-dimethyl-2-imidazolidinone/C,1, Direct Blue 86°1/Emulgen 931"/PVP K-30" (=f (2/15/1515/310.110.1 parts by weight) pH=8.02) H20/ethylene glycol/
Diethylene glycol/polyethylene glycol #30
0/N-Methyl-2-pyrrolidone/C,1, Food Black 2''/Emulgen 931' 3 (-55/10/2015151510.2 parts by weight)
pH-9,03))120/diethylene glycol/glycerin/triethylene glycol monomethyl ether/C,1, Direct BuJl/-88"/PVP K
-30” (-721515/15/310.1 parts by weight)
pi(-7,04)H20/ethylene glycol/diethylene glycol/polyethylene glycol #300
/Polyethylene glycol #400/N-methyl-2
-pyrrolidone/C, 1, food black 2'2 (=6
5/10/101515/2/3 parts by weight) PH=10
．． 0 Note) ~'' is a water-soluble dye, and caustic soda was used for pH adjustment. is a trade name of 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 subjected to the line test. As a result, 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 10B pulse recording signal was continuously applied to the recording head using the recording liquid for 14 hours to perform printing. A printing test was conducted to perform the following.

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 Using the dry film produced in Synthesis Example 2, the dry film was laminated onto a substrate while peeling off the polyethylene film laminated to the dry film, and pattern exposure was performed at an illuminance of 8 cm on the irradiated surface. Exposure light source for semiconductors (P L
A-501 (manufactured by Canon Co., Ltd.) for 150 seconds, and the exposed dry film was developed by peeling off the polyethylene terephthalate film and developing with 1,1.1-)lichloroethane/ethanol (-70). A liquid jet recording head was prepared in the same manner as in Example 1, except that a mixed liquid of 30% by weight was used and sprayed at 35° C. for 60 seconds.

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 Examples Commercially available dry film Vacrel (trade name of dry film solder mask, manufactured by Dubond Nemo Earth Co., Ltd.) with a film thickness of 75 mm, and commercially available Dry 74 with a film thickness of 50 mm.
A recording head was produced in the same manner as in Example 1, except that Lum Photoc 5R-3000 (trade name, manufactured by Hitachi Chemical Co., Ltd.) was used.

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

During the durability test, the dry film was
When 1 was used, peeling was observed with recording liquids 2) and 4) over a distance of 100 m. Also, in 300 hours, l
) and 3) peeling was observed with the recording liquids.

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

[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. 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 10: Supply pipe Patent applicant: Canon Corporation (a) (b) Figure 1 - Figure 2 Figure 3 - (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 (i) has a glass transition temperature of 50°C. (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. 2) In the resin composition, when the content of the linear polymer (i) is L parts by weight and the content of the resin (ii) is E parts by weight, L/(L+E) is 0. The linear polymer of (i) and the linear polymer of (ii) are in the range of .2 to 0.8.
containing the resin, and the polymerization initiator (iii) above (
The liquid jet recording head according to claim 1, wherein the liquid jet recording head contains 0.2 to 15 parts by weight per 100 parts by weight of L+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.