JPS629958A - Liquid jet recording head - Google Patents

Abstract

PURPOSE:To provide the precise liquid-jet recording head efficient in durability,by having a substrate and the specific resin cured film layer forming the groove being the passage for liquid. CONSTITUTION:The passage for liquid provided on a substrate is formed by forming the cured region of resin composition material by exposure with active energy line and removing the uncured region. The resin compositional material is a active energy ray cured type resin compositional material having (i) the graft copolymer formed by adding the side chain having the structural units derived from A acrylic monomer containing hydroxide group, B acrylic monomer containing amino or alkyl amino group C acrylic or vinyl monomer containing carboxyl group, D N-vinyl pyrrolidone or its derivative, E vinyl pyridine or its derivative, and F the monomer selected from the group composed of acrylic amide derivative expressed in general formula 1 as its main body to the normal chain having the structural unit derived from not less than one kind of monomers selected from the groups composed of alkyl metaacrylate, acronitrile, and styrene as its main body and (ii) the monomer having ethylenic unsaturated bond. (Where, R<1> represents the alkyl or hydroxy alkyl group of which the atomic number of hydrogen or carbon is 1-3 and R<2> represents the alkyl or acyl group which may have the hydroxy group of which the atomic number of hydrogen or carbon is 1-4.)

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 printing method that allows printing on plain paper without requiring special processing, such as printing on plain paper, and various types of binding have recently been actively researched.

Liquid jet recording method (The recording head section of the recording head used in this method generally includes an orifice (liquid discharge port) for discharging the recording liquid, and an energy source communicating with the orifice to discharge the recording liquid. The liquid passage has a portion that acts on the recording liquid, and a liquid chamber for storing the recording liquid to be supplied to the liquid passage.

At the time of recording, the energy for ejecting the recording liquid is placed in a predetermined section of the part (energy application part) where the ejection energy is applied to the liquid for recording, which forms part of the liquid passage. Ejection energy is often generated by various types of ejection energy generating elements such as heat generating elements and 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 a suitable shape on the flat plate with the grooves. A method including 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 ejection energy generating elements are arranged by a one-step process to form a substrate. A method is known that includes a step of providing a groove to serve as a liquid passage in the grooved plate formed in this way, and joining another flat plate (cover)'@@ to form a liquid passage (for example, a special method). 1977
-43876).

Among these methods for manufacturing liquid jet recording heads, the latter method using photosensitive resin allows for microfabrication of liquid passages with higher precision and higher yield than the former method, and it is also suitable for mass production. This has the advantage that it is possible to provide a liquid jet recording head of good quality and at a lower cost.

The photosensitive resin used in manufacturing such a recording head is one that has been used for pattern formation in printing plates, printed wiring, etc., or a photocurable resin used for glass, metal, ceramic, etc. Materials known as paints and adhesives are used, and from the viewpoint of work efficiency, tri-film type resin has mainly been used.

[Problems to be solved by the invention] In a recording head using a cured film of photosensitive resin, in order to obtain excellent characteristics such as advanced recording characteristics, durability, and reliability, The photosensitive resin has the following properties: (i) In particular, it has excellent contact with the substrate as a cured film, (2) It has excellent mechanical strength and durability when cured, and (3) Pattern exposure. There is a need for a material that has characteristics such as excellent sensitivity and resolution when forming patterns using.

However, currently known photosensitive resins used for forming liquid jet recording heads do not satisfy all of the above-mentioned required characteristics.

That is, printing plates, photosensitive resins for recording heads,
Those used for forming patterns on printed wiring etc. have excellent sensitivity and resolution, but have poor adhesion and adhesion to glass, ceramics, plasti/solifilm, etc. used as substrates.
Moreover, the mechanical strength and durability of hardening (I) are not sufficient. Therefore, during the manufacturing stage of the recording head,
With continued use, the reliability of the recording head may be significantly reduced, for example by obstructing the flow of the recording liquid in the liquid path or by making the direction of droplet ejection unstable. It does have the disadvantage that the cured resin film is easily deformed, peeled off from the substrate, and damaged, which may cause damage.

On the other hand, the adhesives used for glass, full bending, ceramic, YX, etc. (known as photo-curable paints A) have excellent adhesion and rigidity to substrates made of these materials.
Although it has the advantage of providing sufficient mechanical strength and durability, it is inferior in sensitivity and resolution, and requires a higher intensity exposure device and a longer exposure time. Moreover, due to its characteristics, it is not possible to obtain a precise high-density pattern with good resolution, so it has the problem that it is not suitable for use in recording heads that require particularly fine precision machining. ing.

The present invention was developed in view of these problems, and has a liquid passage wall made of a resin cured film layer that satisfies all the required characteristics as described above, and is inexpensive, precise, and reliable. The purpose of the present invention is to provide a liquid jet recording head that is high in quality and has excellent durability.

Another object of the present invention is to provide a liquid jet recording head having a structure in which liquid passages are microfabricated with high accuracy and high yield.

Another object of the present invention is to provide a liquid jet recording head that is highly reliable and has excellent durability even when it is made into a multi-orinoid head.

(Means for Solving the Problems) The above objects can be achieved by the following present invention.

In the present invention, a liquid passage provided on a substrate surface and communicating with one liquid discharge port exposes a layer made of a resin composition that is cured by active energy rays in a predetermined pattern using active energy rays. A liquid jet recording head is formed by forming a cured region of the resin composition and removing an uncured region from the layer, the resin composition comprising: (A) a hydroxyl group-containing acrylic monomer, (8) an amino or alkylamino group-containing acrylic monomer, and (C) a carboxyl group in the backbone chain mainly consisting of structural units derived from one or more monomers selected from the group consisting of styrene. Containing acrylic or donyl monomer, (D) N-
A structural monomer Ω derived from one or more heptads selected from the group consisting of vinylpyridine or its derivatives, (D vinylpyridine or its derivatives, and (F) an acrylamide derivative represented by the following general formula A graft copolymer polymer having a main branch chain added thereto, (wherein R1 is hydrogen or an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, R2 is hydrogen or 1 is a carbon atom number or 1) (2) represents an alkyl or acyl group which may have 7% of hydroxy of 4 to 4) (ii) an active energy ray-curable resin composition comprising a monomer having an ethylenically unsaturated bond; This is a characteristic liquid jet recording head.

That is, the recording head of the present invention includes a substrate and a cured resin film layer that forms at least grooves that serve as liquid passages, and improves the resistance of each member constituting the recording head and the adhesiveness between each member. Moreover, the resin cured film layer is precisely micro-processed, has excellent recording characteristics, and is highly reliable.
Durability during use (This is also an excellent recording head.

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. 3 is a cross-sectional view taken along the line C-C in FIG.

This liquid jet recording basically consists of a substrate 1, a cured resin film 311 provided on the substrate and patterned into a predetermined shape, and a layer 7 laminated on the cured resin film. These members include an orifice 9 for discharging the recording liquid, and a liquid passage communicating with the orifice and having a portion that applies energy to the recording liquid for discharging the recording liquid. 6-2 and a liquid chamber 6-1 for storing recording liquid to be supplied to the liquid passage. Furthermore, in the through hole 8 provided in the cover,
A supply pipe 10 for supplying recording liquid from the outside of the recording head to the liquid chamber 6-1 is connected. Furthermore, Fig. 1(a)
, the supply pipe 10 is omitted.

During recording, the energy for ejecting the recording liquid is generated by a heating element disposed at a predetermined position of the recording liquid (the part on which the ejection energy is applied) forming a part of the liquid passage 6-2. Ejection energy is generated by applying an ejection signal as desired to f! types of ejection energy generating elements 2 such as piezoelectric elements via wiring (not shown) connected to these elements.

A substrate 1 constituting the recording head of the present invention is made of glass, ceramics, plastic, metal, or the like, and a desired number of generating elements 2 are disposed at predetermined positions. In addition, the first
In the example shown in the figure, 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, laminated glass, plastic, metal, etc., and is bonded to the cured resin film by fusing or bonding using an adhesive, and has a predetermined design. A through hole 8 is provided for connecting a supply pipe 10 to the station.

In the recording head of the present invention, a predetermined shape (this patterned cured resin film) forming the walls of the liquid passage 6-2 and the liquid chamber 6-1 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 below by one step of photolithography.

Note that this cured resin film 3 [ ] may be patterned integrally with the cover 7 formed of the resin composition.

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 (i) selected from the group consisting of alkyl methalarylate, acrylonitrile, and styrene; (A) a hydroxyl group-containing acrylic monomer, (B) an amine or alkylamino group-containing acrylic monomer, and (C) a carboxyl group-containing acrylic or vinyl monomer. Monomer, CD) N-
A branched chain mainly consisting of a structural unit derived from one or more monomers selected from the group consisting of vinylpyrrolidone or its derivatives, (E) vinylpyridine or its derivatives, and (F) an acrylamide derivative represented by the following general formula T. A kraft copolymer polymer formed by adding CH2=C---(i) O=CNHCH2O-R' (where R1 is hydrogen or an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, (represents hydrogen or an alkyl or acyl group which may have a hydroxyl group having 1 to 4 carbon atoms) (ii) an active energy ray-curable monomer having an ethylenically unsaturated bond; It is a type resin composition that has good adhesion to substrates made of glass, plastic, ceramics, etc. especially when formed into a cured film, and also has excellent resistance to recording liquids such as ink and mechanical strength. Moreover, it has excellent properties as a component of a liquid jet recording head, in that it can form precise, high-resolution patterns by buttering with active energy rays. Furthermore, this resin composition can be used as a tri-film, in which case the above-mentioned excellent properties are also exhibited.

Hereinafter, the composition of the energy-curable resin composition used to form the recording head of the present invention will be explained in detail.

The (i)/) raft copolymer polymer, which is an essential component of this active energy 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 monomers (A) to ('F) (with addition of branches 11 that exhibit excellent adhesion to the substrate).

The above-mentioned graft copolymerized polymer is composed of (in this case, its branch chain is composed of) monomers of (A) to (F) mentioned above are specifically shown as (A) hydroxyl group-containing acrylic monomer. is 2-hydroxyethyl (meth)acrylate (hereinafter, when referred to as (meth)acrylate, it is meant to include both acrylate and methacrylate), 2-hydroxypropyl (meth)acrylate, 3- /70 rho 2-hydroxyprodol (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-
Hydroxyethyl (meth)allyrylate, or 1,
Examples include monoesters of 4-cyclohexane dimetatool and acrylic acid or methacrylic acid, and the trade names are Aronilaus M5700 (manufactured by Toagosei Chemical Co., Ltd.), TO
NEMloo (made of caprolactone acrylate, union carbide), Light Ester HO-mpp
(manufactured by Kyoeisha Yushi Kagaku Kogyo ■), Light Ester M-6
0OA (trade name of 2-hydroxy-3-phenoxypropyl acrylate, manufactured by Kyoeisha Yushikaji Kogyo ■), dihydric alcohols, such as 1. )0
-deca) diol, neopentyl uricol, bis(2
-Hydroxyethyl) teretulate, 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 amine or alkylamino group-containing acrylic monomer (B) includes (Me/;I) acrylamide,
N-dimethylaminoethyl (meth)acrylamide, N
, N-dimethyl(meth)acrylamide, KN-dimethylaminopropyl(meth)acrylamide, N,N-di-t-butylaminoethyl(meth)acrylamide, and the like.

The carboxyl group-containing acrylic or vinyl monomer (C) is (meth)acrylic acid, nomaric acid, itaconic acid, or (Yo Toagosei Chemical Co., Ltd.) Product name: Aronylaus M-5400, Aronylaus M-5500% I can name some things.

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

All of the monomers (A) to (E) above have hydrophilic properties, and when bonding the resin composition used in the present invention to a substrate such as glass, ceramics, plastic, etc., they provide strong strength. The translator'l is given.

As the acrylamide derivative represented by the general formula (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-
Methyloracrylamide, α-hydroxyethyl-N
-butoxymethylacrylamide, α-hydroxypropyl-N-propoxymethylacrylamide, α-ethyl-N-methylolacrylamide, α-propyl-N
Examples include hydrophilic and thermally crosslinkable monomers such as methylol acrylamide. These monomers (F
) has not only wood-philic properties but also condensation cross-linking properties when heated, and in general, at temperatures of 100°C or higher, the main molecule or alcohol is detached and forms cross-linked bonds, and the graft copolymer polymer itself also hardens. Afterwards, a network structure is formed and the resulting pattern is further improved in chemical resistance, mechanical strength, etc., thereby making the present invention more effective.

In addition, by adding a portion of the monomers (A) to ('') (monomers that undergo thermal ring opening and crosslinking, such as glycidyl (meth)acrylate to form a branch chain, the above (F) The same effect can be obtained as in .

In addition to the above-mentioned thermal crosslinking, it is also effective to introduce a photopolymerizable monomer into some of the branch chains of the graft copolymer and crosslink the craft copolymer with active energy rays for the same purpose. Such methods for imparting photopolymerizability to branch chains include, for example, (1) monomers containing carboxyl groups such as (meth)acrylic acid, or monomers containing amine groups or tertiary amine groups; A method in which a polyisocyanate partial urethane compound having one isocyanate group and one or more acrylic ester groups in one molecule, and a branch A method of reacting the hydroxyl group, amine group, or carboxyl group of the chain; (i<) A method of reacting the hydroxyl group of the branch chain with acrylic acid chlorite; 0) A method of reacting the hydroxyl group of the branch chain with an acid anhydride, and then reacting with glycidyl A method of reacting (meth)acrylate, [Phase] A method of condensing the hydroxyl group of the branch chain with (E) (the condensation crosslinking monomer shown in this example, leaving an auryl amide group on the side chain, ■ A method of reacting the hydroxyl group of the branch chain with glycidyl ( Methods such as the method of reacting meth)acrylate can be used.

When the branch chain of the kraft copolymer polymer is thermally crosslinkable, it is preferable to form a pattern by irradiation with active energy rays and then heat it after p.

On the other hand, even when the branch chain is photopolymerizable, there is no problem in performing h1 heating within a range that is allowable in terms of the heat resistance of the substrate, and in fact gives more favorable results.

Incidentally, the branch chains may be derived from only hydrophilic chains as exemplified in (A) to (F) above, or may be derived from other 1! A branched chain may be used as a component of the copolymerization in an amount of 0 to about 25% by weight of various hydrophobic monomers that exhibit various functions.

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

In addition to those derived only from the above monomers, the backbone chain may be derived from the above monomers, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate,
There may also be a backbone chain comprising n-butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, vinyl acetate, etc. as a copolymer component in an amount of 0 to about 50% by weight.

In the resin composition used to form the record of the present invention, the backbone chain imparts high cohesive strength to the composition. The composition is used in various forms such as a solution or a solid film when forming a recording head, but if it is used for tri-film binding, the composition is maintained in a film form. Therefore, it is preferable to use a relatively rigid backbone having a glass transition temperature of about 50° C. or higher. In this case, the backbone chain used may be composed of two or more types having different glass transition temperatures. Furthermore, if the composition is used in the form of a solution, it is also possible to use a backbone chain with a low glass transition temperature that gives flexibility to the composition. However, in this case as well, in order to obtain a pattern having excellent resistance to recording liquid and high mechanical strength, it is preferable that the backbone chain has a high glass transition temperature.

The kraft copolymer polymer used in the resin composition for forming a cured resin film in the present invention has no curability;
Photocrosslinkable and thermally crosslinkable (these are broadly classified into these, but in either case, in the curing process of the composition (i.e. active energy ray irradiation and thermal curing as necessary) (Seisho 41 Ba 9-
In addition to making it possible to cure the resin, it also provides the pattern obtained by curing with excellent flexibility, chemical resistance, and high mechanical strength.

The above-mentioned graft copolymer polymers can be produced by known methods, and specifically, for example, [Basics and Applications of Polymer Alloys, pp. 110-35 (edited by the Society of Polymer Engineers, published by Tokyo Kagaku Dojin), (1981). Examples of these methods include: 0) chain transfer method, ■ method using radiation, ■ oxidative polymerization method, ■ ion graft polymerization method,
■Ma'7 []] Monomer can be mentioned. For the graft copolymer used in the present invention, the surfactant effect will be more pronounced if the branch chain lengths are uniform, so it is preferable to use the method ① or ②. Among these, the macromonomer method ② is preferable due to material design considerations. Advantageous and particularly preferred. The weight average molecular weight of the graft copolymer is preferably in the range of about 5,000 to 300,000,
When used as a tri-film, the range is preferably from about 30,000 to 300,000.

The monomer (i1) having an ethylenically unsaturated bond, which is another component used in the resin composition for forming a cured resin film in the present invention, is used to make the composition exhibit curability by active energy rays. Various known monomers that preferably have a boiling point of 100°C or higher at atmospheric pressure, have two or more ethylenically unsaturated bonds, and are cured by irradiation with active energy rays. It is possible to use

Specific examples of such monomers having two or more ethylenically unsaturated bonds include (1) acrylic ester or methacrylic acid of a polyfunctional epoxy resin having two or more epoxy groups in one molecule; Esters, ■Acrylic esters or methacrylic esters of alkylene oxide adducts of polyhydric alcohols, ■Polyester acrylates with acrylic ester groups at the molecular chain ends of polyesters with a molecular weight of 500 to 3,000, consisting of dibasic acids and dihydric alcohols. , (2) A reaction product of a polyvalent isocyanate and an acrylic acid monomer having a hydroxyl group. Above ■～
The monomer (2) may be a urethane modified product having a urethane bond within the molecule.

Examples of monomers belonging to category (2) include epoxy resins represented by bisphenol A type, novolac type, and alicyclic type, bisphenol S, bisphenol F, tetrahydroxynoenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, Glycerin triglycidyl ether, pentaerythol triglycidyl ether, isocyanuric acid triglycidyl ether, and acrylic acid or methacrylic acid of epoxy urethane resins represented by the following general formula II (wherein R represents an alkyl group or an oxyalkyl group) Examples include acid esters.

Monomers belonging to category (1) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1.6 hexanediol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. , pentaerythol tri(meth)acrylate, etc., and the product names are KAYARAD HX-220, H
X-620, D-310, D-320, D-330, D
PHA, R-604, DPCA-20, DPCA-3
0, DPCA-60, DPCA-120C or higher, made by Nippon Kajimi), product name N is ester BPE-200, BPE
-500, BPE-1300, A-BPE-4C or higher,
Products such as those manufactured by Shin Nakamura Chemical Co., Ltd.) can be used.

Monomers belonging to category (2) include the product name Aronix M-6.
100, M-6200, M-6250, M-6300,
M-6400, M-7100, M-8030, M-80
60, M-8100 (manufactured by Toagosei Kagaku ■), and the like. For those belonging to category 1 and containing polyester urethane bonds, the product name is Aronix M-110.
0, Aronix M-12[]0 (manufactured by Toagosei Kagaku ■), and the like.

Monomers belonging to category (2) include polyisocyanates such as tolylene diisocyanate, inphorone diisocyanate 1 to 1, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and diphenylmethane diisocyanate. and a hydroxyl group-containing acrylic monomer, and the product names are Sumidur N (biuret derivative of hexamethylene diisocyanate) and Sumidur L (trimethylolpropyl modified derivative of i-lylene diisocyanate) (all of which are produced by Sumidur). A reaction product obtained by adding a (meth)acrylic acid ester containing a hydroxyl group to a polyisocyanate compound known as Bayer Urethane (trade name) etc. can be used. The hydroxyl group-containing acrylic monomer referred to herein is a (meth)acrylic acid ester or a typical 4J monomer, preferably hydro-based diethyl (meth)acrylate or hydroxypropyl (meth)acrylate. In addition, it is also possible to use 1 and other acrylic monomers containing hydroxyl groups as those used in the branch chain of the kraft copolymer polymer in this specification.

In addition to the monomers having two or more ethylenically unsaturated bonds as described above, monomers having only one ethylenically unsaturated bond such as those listed below may also be used. Examples of such monomers having one ethylenically unsaturated bond include carboxyl group-containing unsaturated monomers such as acrylic acid and methacrylic acid, and glycidyl group-containing unsaturated monomers such as glycidyl acrylate and glycidyl metaralarylate. C2-C11 hydroxyalkyl esters of acrylic acid or methacrylic acid such as saturated esters, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl aurylate, hydroxypropyl methacrylate; polyethylene glycol monoacrylate, polyethylene glycol monoacrylate methacrylate, polypropylene glycol]-
Monoesters of acrylic acid or methauric acid and polyethylene glycol or polypropylene glycol such as monoaurylate, polybrobyreciglycol monomethaurylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, Butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, prodol 9-acrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, methauryl C+=C+ of acrylic acid or methacrylic acid such as octyl methacrylate, lauryl methacrylate, and cyurohexyl methacrylate;
Alkyl or cycloalkyl esters, other monomers such as styrene, vinyltoluene, methylstyrene, vinyl acetate, vinyl chloride, vinyl isobutyl ether, acrylonitrile, acrylamide, methacrylamide, acrylic or methacrylic acid adducts of alkyl glycidyl ethers, vinyl Pyrrolidone, dicyclopentenyloxyethyl (meth)acrylate, ε-
Examples include caprolactone-modified hydroxyalkyl (meth)acrylate, tetrahydrofurfuryl acrylate, and phenoxyethyl ararylate.

In any case, by using the above monomer having an ethylenically unsaturated bond, the resin composition for forming a cured resin film of the present invention is imparted with curability by active energy rays.

The active energy ray-curable resin composition for forming a resin cured film in the present invention has a wavelength of 250 as the active energy ray.
When active energy rays of nm to 450 nm are used, it is preferable to add a photopolymerization initiator to the resin composition. As the photopolymerization initiator, any known substance used for photopolymerization can be used without particular limitation.

Specific examples of such photopolymerization initiators include Hensyl,
Henzoin alkyl ether neck: Henzoin isobutyl ether, Henzoin isobrobyl ether, Hesizoin-n-butyl ether, Henzoin ethyl ether,
Hesizoin medyl ether, etc.,
hensono]dinone, 4,4'-bis(K,N-dimethylamino)hendinoenone, hesizophenocymethyl T
=-Ternoids, anthraquinodines 2-ethyl acytraquinone, 2-t-butyl acytraquinone, etc., xanthodes 2,4-dimethyldioxasitone, 2,4-diisopropyldioxanthone, etc., acetophenols: 2
, 2-dimethoxy-2-phenylarethophenone, α,
α-dichloro-4-phenoxyacetophenone, p-t
ert = butyl trililo 1] aretonoenone, p −
tert-butyl dichloroacetophenol, 2,2-jetoxyacetophenone, p-dimethylaminoacetonoenone, etc., or hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Geiki), 1=(4-imbrovir) (noenyl)-2,-hi1-
Roxy 2-methylpropane-1-oxy(daloki)a1
116 Mel'7 (manufactured by VERCK ■), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173 manufactured by Merck ■), and the like are preferably used. In addition to these photopolymerization initiators, an amine compound may be added as a photopolymerization accelerator.

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

The composition ratio of the materials constituting the active energy ray-curable resin composition for forming a resin cured film in the present invention is 20 to 80% by weight of the graft copolymer, preferably 20 to 80% by weight.
50% by weight, monomer 8 having ethylenically unsaturated bonds
0 = 20% by weight, preferably 50 to 80% by weight, and when using a photoinitiator, the photoinitiator is:
0.00 parts by weight per 100 parts by weight of a resin component consisting of a graft copolymer polymer and a monomer having an ethylenically unsaturated bond.
1 to 20 parts by weight, preferably 3 ] or 1 to IO! This is the clause of the i-quantity part.

The solvent used when using the active energy ray-curable resin composition for forming a cured resin film in the present invention in the form of a solution, or when applying it onto a plastic film that is a film base material when forming a dry film, is as follows: Examples include hydrophilic solvents such as alcohols, glycol ethers, and glycol esters. Of course, these hydrophilic solvents are mainly used, and if necessary, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and isobutyl acetate, toluene,
Aromatic hydrocarbons such as xylene and their halogen substituted products,
It is also possible to use an appropriate mixture of chlorine-containing aliphatic solvents such as methylene chloride, 1, 1, 1-trichloroethane, and the like. Incidentally, these solvents can also be used as a developer for the resin composition after pattern exposure.

In addition, in addition to the photopolymerization initiator or solvent described above, the active energy ray-curable resin composition for forming a resin cured film in the present invention may contain, for example, a condensation crosslinking catalyst, a thermal polymerization inhibitor, and a coloring agent (dye and pigment). If necessary, additives such as particulate fillers, accelerators, and plasticizers may be included.

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

Effective adhesion promoters include silane coupling agents as inorganic surface modifiers and low-molecular surfactants.

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

Hereinafter, the method for producing a liquid jet recording sheet of the present invention will be described in detail with reference to the drawings, taking as an example a case in which a tri-film type binder is used to bind 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, as shown in FIG. are arranged individually. In addition, in order to provide the surface of the substrate 1 with resistance to recording liquid, electrical insulation, etc., if necessary, a 5in2, J
a2rl! , may be coated with a protective layer such as glass. Further, although not shown, a recording signal input electrode is connected to the ejection energy generating element 2.

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 described above, the above-described bioenergy ray-curable resin composition 3 of the tri-film type (film thickness, approximately 25 μm to 100 μm) was
For example, 0.5-0.4 by heating to about 150°C.
It is laminated on the substrate surface IA at a speed of f/min and under pressure of l −3 Kq/cm′.

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 tri-film layer 3 provided on the substrate surface IA. Exposure is performed from the top of the mask 4.

The photomask 4 and the substrate 1 are aligned in such a way that the element 2 is placed in the liquid passage area that will be finally formed through steps such as exposure and development.
For example, alignment marks can be drawn in advance on each of the substrate 1 and the mask 4, and alignment can be performed according to the marks.

When exposed in this way, the area other than the area covered by the pattern, that is, the exposed part of the tri-film layer 3, polymerizes and hardens, whereas the unexposed part 1 remains solvent-soluble. Becomes insoluble in solvents.

This pattern exposure (Active energy rays used include ultraviolet rays or electron beams, which have already been widely used in practice.Ultraviolet light sources have wavelengths of 250 nm to 250 nm.
High-pressure mercury lamps, ultra-high-pressure mercury lamps that contain a lot of 450 nm light,
The intensity of light in the vicinity of 365 nm is 1 mW/cm' to I00 mW/cm at a practically acceptable distance between the irradiated objects using a metal halide lamp, etc.
' or something like that is preferable. The electron beam irradiation device is not particularly limited, but a device having a dose in the range of 0.5-.20 M Rad is practically suitable.

After pattern exposure tp of the try film layer 3 is completed, next, the exposed try film 3 is exposed, for example], 1.1
- Development treatment is carried out by immersion in a volatile organic solvent such as trichloroethane, and the unpolymerized (uncured) portion of the solvent-soluble tri-film layer 3 is dissolved and removed from the substrate 1, as shown in FIG. As shown in a) and FIG. 5(b), the substrate 1
The cured resin film 3H remaining above forms grooves that will eventually become the liquid passage 6-2 and the liquid chamber 6-1.

Next (when using an active energy ray-curable resin composition (such as when a thermosetting graft copolymer polymer is used), the cured resin film 3H on the substrate 1 is coated as necessary, for example at 100°C for 5 to 50 minutes.
Further heat for about 10 minutes to thermally polymerize.

In the recording head of this example, an example will be described in which a tri-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 chambers 6-1. However, the active energy ray-curable resin composition that can be used in forming the recording head of the present invention is not limited to solid ones, and of course liquid ones can also be used.

A method for forming a layer made of a liquid resin composition on a substrate using a squeegee, which is used when creating a relief image, for example, 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 viscosity of the resin composition is suitably 100 Cp to 3000 Cp. First, the height of the wall placed around the substrate must be determined in consideration of the reduction in production due to evaporation of the solvent contained in the photosensitive resin composition.

Further, when a solid resin composition is used, it is preferable to use the method of heat-pressing and adhering Trifil 1\ onto the substrate as described above.

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 controlling the thickness easily and accurately.

In this way, after forming the grooves constituting the liquid passage 6-2 and the liquid chamber 6-1 at the end of the bend using the cured resin film 3H,
As shown in FIGS. 6(a) and 6(b), a flat plate 7 serving as a cover for the groove is bonded onto the cured resin film 3 to form a combined body.

In the steps shown in FIG. 6(a) and FIG. 6(b),
A specific method for attaching the cover 7 is, for example, to apply an epoxy resin adhesive to a thickness of 3 to 4 μm on a flat plate 7 made of glass, ceramic, metal, plastic, etc., and then preheat it to form an adhesive layer. There is a method such as making it into a so-called B stage, bonding it on a cured tri-film for 3 days, and then curing the adhesive layer, but thermoplastic resins such as acrylic resin, ABS resin, polyethylene resin, etc. A method that does not use an adhesive, such as directly heat-sealing the resin flat plate 7 onto the cured resin film 3, 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 thermally fused to the cured resin film forming the liquid passage. Also preferable is a method in which the resin composition for forming a cured resin film according to the present invention is used as a binding agent.

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

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

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 region of the liquid path in the present invention refers to the downstream area in the flow direction of the recording liquid when recording is performed using a recording head, specifically (this refers to the downstream region of the ejection energy generating element 2). Refers to the part of the liquid passage downstream from the installation location.

After cutting is finished, the cut surface is polished and smoothed.
By attaching the supply pipe 10 to the through hole 8, a liquid jet recording unit as shown in FIG. 1 is completed.

Note that in the recording mode 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 has such a structure. However, the liquid passage and the liquid chamber may be separately molded. However, in either structure, in the recording head of the present invention, at least a portion of the resin forming the liquid passage is formed using the above-mentioned active energy ray-curable resin composition. be.

〔Effect of the invention〕

The liquid jet recording head of the present invention is mainly composed of a monomer having an ethylenically unsaturated bond contained as an essential component in the active energy ray-curable resin composition that is a component of the head. This resin composition uses a material that has excellent sensitivity and resolution as a pattern forming material, and by using this resin composition, it is possible to obtain a liquid jet recording head with excellent dimensional accuracy at a high yield. became. In addition, the resin composition used in the present invention also has excellent adhesion to the substrate, mechanical strength, and chemical resistance, which are mainly provided by the graft copolymer polymer as an essential component. By using the composition, it has also become possible to obtain a recording head with long-term durability.

In addition, when using an active energy ray-curable resin composition using a graft copolymer polymer having curing 'ilX, the adhesion, mechanical strength, or chemical resistance mentioned above may be
This makes it possible to obtain an excellent liquid jet recording head.

(Example) Hereinafter, the present invention will be further explained in detail with reference to Synthesis Examples and Examples.

Synthesis Example A living polymer (thoxymethyl acrylamide/2-hydroxyethyl methacrylate (=70/30 weight ratio)) obtained by anionic polymerization is reacted with acrylic acid chloride to form a vinyl group at one end of the molecular chain. A macromonomer (bolybutoxymethacrylate acrylate/2-hydroxyethyl methacrylate) having a weight average molecular weight of about 3000 was obtained.

25 parts by weight of this macromonomer, 70 parts by weight of methyl methacrylate and 5 parts by weight of acrylonitrile were polymerized in a methylcerone lubricant to produce a graft copolymer having a weight average molecular weight of 6.8 x group 4 and thermally crosslinked 'l'I. (This is referred to as GP-4) was obtained. Incidentally, the glass transition temperature of the copolymer chain of polymethylmethaurylate chain and polyacrylonitrile chain constituting the main chain of GP-4 is 5°C.

Using this GP-4, an active energy ray-curable resin composition having the following composition was prepared.

G P-4100 parts by weight Acrylic acid ester of triglycidyl ether of trimethylolpropane 1001/urethane acrylate)
-11R4003*3100 Horned copper phthalocyanine 15〃P-toluenesulfonic acid
3 1/Irugakiyua 65+
15 methyl cellosolve 300
Horn *3: Urethane ararylate manufactured by Nagase Kasei Co., Ltd. Next, a mill dispersion of the above resin composition was applied to a 6 μm polyethylene terestate film using a wire bar and dried at 100°C for 20 minutes. , film thickness 75μ
A tri-film according to the present invention having m resin composition layers was prepared.

EXAMPLES Using the tri-film produced in the synthesis example and following the steps shown in FIGS. 1 to 6 previously explained in the specification, a heating element [Hanonium Polyte (H
fB2) ] In orifices (orifice size 1
An ontemant type liquid jet recording head having a size of 75 μm×50 threads and a pitch of 0.125 mm was fabricated as follows. Note that three recording heads of the same shape are used.
I made a prototype for 0 pieces.

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 5iO7 layer (thickness: 1.0 μm) is provided as a protective film on the surface of the substrate on which the heating element is arranged, and after cleaning and drying the surface of the protective layer, it is stacked on the protective layer. 80
A tri-film with a film thickness of 75 μm shown in Reference Example 1 and heated to 1°C was heated to 1 and q
The lamination was carried out under pressure conditions of "/cm".

Subsequently, a photomask having bows corresponding to the shapes of the liquid passages and liquid chambers is superimposed on the tri-film provided on the substrate surface, so that the above-mentioned elements are provided in the liquid passages that are finally formed. After alignment, the try film was exposed for 30 seconds using ultraviolet light with an intensity of 8.2 mW/am' from above the photomask.

Next, the exposed tri-film is divided into l, l, 1-
It is immersed in trichloroethane and developed, and the unpolymerized (uncured) portion of the Trifilm is dissolved and removed from the substrate, and the cured Trifilm film that remains on the substrate ultimately becomes a liquid passage and a liquid chamber. A groove was formed.

After finishing the development process, the cured Trifilm film on the substrate was heated at 150°C for 1 hour, and then
Further faeces were irradiated with ultraviolet rays with an intensity of mW/cm' for 2 minutes.

In this way, grooves that will become liquid passages and liquid chambers are formed on the substrate using the cured tri-film film, and then epoxy is applied to a flat plate with through holes made of soda glass that will cover the formed grooves. A system resin adhesive was laminated onto a tri-film with a thickness of 3 μm (after short-circuiting, preheating to B stage, and curing 1), and further,
The adhesive was fully cured and fixed to form a bonded body.

Next, 0.150 mm downstream of the liquid passage of the bonded body, that is, from the installation position of the extrusion energy generating element.
The area was cut perpendicularly to the liquid path using a commercially available dicing saw (product name: DAD 2H/6 type, manufactured by DISOCO) to form an orifice for discharging the recording liquid.

At a minimum, the cut surface was washed once and dried, and the cut surface was polished to make it smooth. 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 50±5 μm, and the orifice pitch was in the range of 125±5.

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

First, the obtained recording head was subjected to a durability test in which it was immersed in a recording liquid having the following composition at 60° C. for 1000 hours (environmental conditions comparable to those during long-term use of the recording head).

Recording liquid component 1) H20/diethylene glycol/glycerin/C,
1, Direct black + 54' 1 (= 70/2
01515 parts by weight) ' pH = 8.02) H2
O/ethylene glycol/N-methyldoloriton/C,
1, Direct Blue 199'2 (= 60/25/
1015 parts by weight) pH = 9.03) H20/ethylene glycol/triethylene glycol/C,l acidlet 94'1 (= 60/25/1015 parts by weight) pH = 7.04) H2O/diethylene glycol/ C, 1, Direct Black 154 (・75/2015 parts by weight) pH=IO,
Note) '1 to 1 are water-soluble dyes, and caustic soda was used to prepare pi-1.

For each recording liquid, one to five recording spatulas were tested for durability.

After the durability test, we observed the state of bonding between the hardened tri-film film and the hardened substrate and cover of each head that underwent the test. As a result, no peeling or damage was observed in any of the recording heads, indicating good adhesion. It was showing.

Separately, each of the 10 recording heads obtained was attached to a recording device, and the recording liquid was used to continuously record a 10° pulse recording signal for 14 hours. A printing test was conducted in which the voltage was applied and printing was performed. With respect to any of the recording heads, almost no deterioration in recording liquid ejection performance or printing condition was observed immediately after the start of printing and after 14 hours had elapsed, indicating that the recording heads had excellent durability.

Comparative Examples: Commercially available Tri-Film Vacre 1 (trade name of Tri-Film Solder Mask, manufactured by Dubond Nemo Earth) with a film thickness of 75 gm, and commercially available Tri-Film Photoc 5R-3000 (trade name, manufactured by Hitachi Chemical Industries, Ltd.) with a film thickness of 50 gm. ) A recording head was produced in the same manner as in the example except that the following was used.

Durability tests similar to those in the examples were conducted on these recording heads.

During the durability test, Vacrel was used as a tri-film.
When using recording liquids 2) and 4), peeling was observed after 100 hours. Further, after 300 hours, peeling was observed with the recording liquids 1) and 3).

On the other hand, try film rPhotoc 5R-30
When using 001, each of the recording liquids 1) to 4)
Peeling 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. 1: Substrate 2. Discharge energy generating element 3 Resin layer 3 days: Resin cured film 4: Photomask 4P: Mask pattern 6-1 Liquid chamber 6-2 Liquid passage 7: Cover 8: Through hole 9/orifice 10: Supply pipe

Claims (1)

[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. There are kraft copolymer polymers with branched chains mainly derived from the structural units derived from them. (ii) a monomer having an ethylenically unsaturated bond; 1. A liquid jet recording head comprising: 2) The active energy ray-curable resin composition may contain the (i
) 20 to 80 parts by weight of the graft copolymerized polymer, and 80 parts by weight of the ethylenically unsaturated bond-containing monomer (ii)
Claim 1 which contains ~20 parts by weight
The liquid jet recording head described in . 3) The active energy ray-curable resin composition may be
0.1 to 20% by weight of a photopolymerization initiator is blended with 100 parts by weight of the graft copolymerized polymer () and the ethylenically unsaturated bond-containing monomer (ii). A liquid jet recording head according to claim 1 or 2.