JPH02131947A - Liquid jet recording head - Google Patents

Abstract

PURPOSE:To provide a recording head having a low cost, high accuracy, high reliability and excellent durability by incorporating specific graft copolymerizable polymer, specific linear polymer, compound esterified with acrylic acid at the end of polyurethane molecule chain, and optical initiator. CONSTITUTION:Composition contains graft copolymerizable polymer in which branched chain having a structure unit derived from one type of monomer of monomers represented by formulae x and y is added to backbone chain having a structure unit derived from monomers selected from a group consisting of alkylmethacrylate, acrylonitrile and styrene as a main ingredient, its number- average molecular weight is 5000 or more, and its weight-average molecular weight is 50,000 or less, specific linear polymer, compound esterified with acrylic acid and polyurethane molecule chain end, and optical initiator. In the formulae, R<1> is hydrogen, 1-3C alkyl group or hydroxyalkyl group, R<2> is hydrogen, 1-4C alkyl group or acyl group.

Description

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

[Prior Art] The liquid jet recording method generates small droplets of recording liquid such as ink and attaches them to a recording material such as paper to perform recording, and the noise generated during recording is negligible. It has attracted attention as a recording method that is extremely small and capable of high-speed recording, and can also record on plain paper without the need for special processing such as fixing.Recently, various types of recording methods have been actively researched. There is.

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

During recording, the energy for ejecting the recording liquid is generated by a heating element disposed at a predetermined position in a part (energy application part) that applies ejection energy to the recording liquid, which forms part of the liquid path. In many cases, ejection energy is generated by various types of ejection energy generating elements such as piezoelectric elements.

A method for manufacturing a liquid jet recording head with such a configuration is, for example, to form fine grooves on a flat plate of glass, metal, etc. by cutting or etching, and then to form other suitable grooves on the flat plate with these grooves. A method 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 an ejection energy generating element is arranged by a photolithography process, and forming a liquid passage on the substrate. A method is known that includes a step of forming a groove, 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. 57-1999)
No. 43876). 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. So,
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 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 to be solved by the invention]

In order to obtain excellent characteristics such as advanced recording characteristics, durability, and reliability in a recording head that uses a cured film of photosensitive resin as part of its structure, the photosensitive resin used must have (1) In particular: (2) Excellent mechanical strength and durability when cured; (3) Excellent sensitivity and resolution during patterning using pattern exposure. It is required to have characteristics such as excellent properties.

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

For example, photosensitive resins used for recording heads and for pattern formation in printing plates, printed wiring, etc. have excellent sensitivity and resolution;
It has poor adhesion and adhesion to glass, ceramics, plastic films, etc. used as substrates, and also lacks sufficient mechanical strength and durability when cured. Therefore, during the manufacturing stage of the print head or during use, the print characteristics deteriorate by, for example, obstructing the flow of the print liquid in the liquid passage or making the droplet ejection direction unstable. deformation of the cured resin film or peeling from the substrate, which can significantly impair the reliability of the recording head.
It has the disadvantage of being easily damaged.

On the other hand, known photocuring paints and adhesives used for glass, metals, ceramics, etc. have excellent adhesion and adhesion to substrates made of these materials, and have sufficient mechanical 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.

In addition, in the photosensitive resin compositions used for various conventional purposes, various additive aids such as heterocyclic compounds having the ability to form complexes with metals, or coupling agents, etc. are added to the photosensitive resin. It was added to compositions to improve adhesion to metals, etc. (Special Publications No. 51-5934, No. 58
-24035 etc.). However, this method has the problem that, over a long period of time, the additives mentioned above cause phenomena such as oxidation and corrosion of the composition.

On the other hand, with the aim of obtaining a cured composition that has sufficient adhesion without the addition of such additives, a polymeric substance made of a graft copolymer having polar groups in the branch chain was developed in JP-A-Sho. 61-283645, Japanese Patent Publication No. 61-2836
46. The active energy ray-curable resin composition containing the polymer substance (graft copolymer polymer) disclosed therein does not rely on additives, etc.
It has the advantage of being able to improve adhesion and further improve the durability of the coating film.

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

That is, in general, it is impossible to synthesize the weight average molecular weight of the entire graft copolymer to a desired value over a wide range (approximately 50,000 to 350,000) while keeping the molecular weight and content of the branch chains constant. , which is technically difficult. In other words, in order to improve the development characteristics during pattern formation, that is, the dissolution rate of the unpolymerized part, the swelling property of the polymerized part, and the resulting sensitivity, pattern sharpness, and resolution, it is necessary to use a polymeric material. The average molecular weight should not be too small. In graft copolymer polymers, a large number of technical chains with sufficient length to obtain effective adhesion are bonded to a relatively large molecular weight backbone chain to obtain an average molecular weight that meets the above objectives. is difficult with current synthetic techniques due to steric hindrance.

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

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

Another object of the present invention is to provide a liquid jet recording head having a structure in which liquid passages are microfabricated with 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 to solve the problem]

The above objects can be achieved by the following invention.

The present invention provides a liquid jet recording head that includes a cured product of an active energy ray-curable resin composition as part of its configuration,
The composition has (A) a backbone chain mainly composed of structural units derived from one or more monomers selected from the group consisting of alkyl methacrylate, acrylonitrile, and styrene (hereinafter referred to as "monomer component ■"); A branch having a structural unit derived from at least one monomer (hereinafter referred to as "monomer component ■") selected from the group consisting of a monomer represented by the following general formula (x) and a monomer represented by the following general formula (Y) A graft copolymer polymer having a chain added thereto and having a number average molecular weight of 5,000 or more and a weight average molecular weight of 50,000 or less, and R1 i CH2=C ...(x)0=
C-NH-CH2-0-R2 R1 CH2=C...(y)0=
C-0-R3-OH (wherein, Rl represents hydrogen, or an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and R2
represents hydrogen, or an alkyl group or acyl group having 1 to 4 carbon atoms which may have a hydroxy group,
R3 is an alkyl group having 2 to 6 carbon atoms or a halogen-substituted alkyl group, -C-C H z61o -fc H z-}-= (however, 2≦m10n≦6, n≠ 0, m≠○), and a phenylalkyl group (including cases where 2≦m+n≦4, n=o or m=O). ) (B) Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, t-butyl methacrylate,
Penzyl methacrylate, acrylonitrile, inbornyl methacrylate, isobornyl acrylate,
One or more monomers selected from the group consisting of tricyclodecane acrylate, tricyclodecane methacrylate, tricyclodecane xyethyl methacrylate, styrene, dimethylaminoethyl methacrylate, and cyclohexyl methacrylate (hereinafter referred to as "monomer component") At least one monomer selected from the group consisting of the monomer represented by the general formula (x) and the monomer represented by the general formula (y) (hereinafter referred to as monomer component ◎) However, monomer component ■ and monomer component ■' may have the same composition or different compositions), and have a number average molecular weight of 5. and (C) an oligoester diol or oligoether diol and a divalent isocyanate. It is characterized in that it contains a compound in which the molecular chain end of an esterified polyurethane is converted into an acrylic acid ester (hereinafter abbreviated as photopolymerizable polyurethane) and (D) a photoinitiator.

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

Hereinafter, an example of the liquid jet recording head of the present invention will be 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 line CC in FIG.

This liquid jet recording head basically consists of a substrate 1, a liquid passage wall 3H provided on the substrate and made of a cured resin film patterned into a predetermined shape, and a cover laminated on the liquid passage wall soil. 7, and by means of these members, an orifice 9 for discharging the recording liquid; a liquid that communicates with the orifice and has a portion on which energy for discharging the recording liquid acts on the recording liquid; Passage 6-2
A liquid chamber 6-1 is formed for storing recording liquid to be supplied to the liquid passage. Furthermore, a supply pipe IO for supplying recording liquid from the outside of the recording head to the liquid chamber 6-1 is connected to the through hole 8 provided in the cover. Note that the supply pipe 10 is omitted in FIG. 1(a).

During recording, the energy for ejecting the recording liquid is generated by a heating element or a piezoelectric element disposed at a predetermined position in a part of the liquid passage 6-2 that applies ejection energy to the recording liquid. Wiring (not shown) connected to various types of ejection energy generating elements 2 such as elements, etc.
The ejection signal is generated by applying 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.

The cover 7 is made of a flat plate made of glass, ceramics, plastic, metal, etc., and is bonded to the liquid passage wall 3H by fusing or bonding using an adhesive, and the supply pipe IO is connected at a predetermined position. A through hole 8 for connection is provided.

In this recording head, a liquid passage 6-2 and a liquid chamber 6-
The cured resin film patterned into a predetermined shape constituting the wall 3H of 1 is an active energy ray-curable film containing the above-mentioned components (A) to (D) provided on the substrate 1 or on the cover 7. It is obtained by patterning a layer made of a resin composition using a photolithography process.

Although an example in which a cured film of the resin composition is used in the structure of the liquid passage wall 3}1 has been described above, a cured film (cured product) of the resin composition can be suitably used in other parts of the recording head. It is possible.

For example, as shown in FIGS. 7(a) to 7(h), which are partial cross-sections of the recording head perpendicular to the liquid path, 1. As a cover 7, (a) 2. (b) as the liquid passage wall 3H and the cover 7 (in this case, the liquid passage wall 3H and the cover 7 may be formed integrally, or may be formed separately and then joined.) 3. 4. Adhesive layers 14 (c), (8) and (g) between the liquid passage wall 3H and the cover 7 formed from various resins or the like. (d) and (f) as the liquid passage wall 3H and the adhesive layer 14 between the liquid passage wall 3H and the cover 7; 5. (h) can be used as the adhesive N14 (two-layer structure) between the liquid passage wall 3H and the liquid passage wall 3H and the cover 7. In addition, among the above configurations, the configurations in FIGS. 7(a) to (8), (h) and FIG. 7(f)
A tri-film type can be suitably used to form the liquid passage wall 3H in FIGS. 7(f) and (
For the adhesive layer l4 in G), a type that is used in a liquid state and then cured is preferably used.

Furthermore, the recording head of the present invention is shown in FIGS. 8(a) and (b).
It may also have a structure in which droplets are ejected in a direction perpendicular to the liquid passage (6-2) shown in FIG. The cured film of the resin composition can be suitably used for the same parts as shown in FIG. 7 above, such as the parts shown in ). The active energy ray-curable resin composition containing the above-mentioned components (A) to (D) used in the structure of the recording head of the present invention will be described below. The resin composition has good adhesion to various members such as substrates made of glass, plastic, ceramics, etc., especially when formed into a cured film, and has good resistance to recording liquids such as ink and mechanical strength. Moreover, it has excellent properties as a constituent member of a liquid jet recording head, in that it can form precise and high-resolution patterns by patterning with active energy rays.

Furthermore, this resin composition can be used as a dry film, and the above-mentioned excellent properties are exhibited in that case as well. The graft copolymer polymer (A
The backbone chain of ) is formed using the monomer component (■) mentioned above as a product. As monomers used for branch chains, the monomer components mentioned above ■
In addition, the following polar monomers can be used in combination as necessary. (1) Acrylic monomer containing an amino group or alkylamino group (II) Acrylic or vinyl monomer containing a carboxyl group (III) N-vinylpyrrolidone or a derivative thereof (IV) Vinylpyridine or a derivative thereof;
Hydrophobic monomers may also be used as components of the copolymerization in amounts up to about 25 mole percent.

The graft copolymer polymer (A) is a conventionally known polymer, such as that described on pages 10 to 35 of "Basics and Applications of Polymer Alloys" (edited by The Society of Polymer Engineers, published by Tokyo Kagaku Dojin Co., Ltd., 1981). It can be obtained by various polymerization methods. These methods include: ■ chain transfer method, ■ method using radiation, ■ oxidative polymerization method, ■ ion graft polymerization method,
■There are macromonomer methods. Using these methods,
Polymerization is carried out using the monomer component (■) and monomer component (2) exemplified above, selecting appropriate polymerization conditions so as to obtain a graft copolymer polymer having a number average molecular weight of 5,000 or more and a weight average molecular weight of 50,000 or less. By this, the graft copolymer polymer (A) can be obtained. It should be noted that among the above methods ① to ②, when method ① or ② is used, the copolymer polymer (A
) is preferable because the lengths of the chain branches are the same. In particular, the macromonomer method (2) is a more preferred method.

The linear polymer (B) contained in the resin composition has the above-mentioned monomer component ◎ as a main component, and the above-mentioned monomer component ■' is added, and has a number average molecular weight of 50,000 or more and a weight average molecular weight of 350,000 or less. It can be obtained by polymerizing using a conventionally known method while appropriately selecting polymerization conditions so as to obtain a polymer having a glass transition temperature of 60° C. or higher. In addition, the monomer component ■' is 5 mol% to 30 mol%
It is preferable to add within the range of . If the linear polymer contains more than 30 mol% of this 1,000-mer component ■', the concentration of polar groups in the cured coating film will increase, and the effect of improving adhesion will not increase any further, but the water resistance will increase. This is not desirable because a decrease in Furthermore, if the monomer component (2') in the obtained linear polymer is less than 5 mol %, not only the adhesion to the substrate but also the effect as a binder for the coating film will be insufficient.

giving a high glass transition temperature to the cured film of the resin composition,
For the purpose of increasing water resistance, methyl methacrylate, isopornyl methacrylate, isobornyl acrylate, tricyclodecane methacrylate, tricyclodecane acrylate, etc., as the above-mentioned 1,000-mer component ◎, give particularly favorable results.

Examples of the photopolymerizable polyurethane (C) include oligoester acrylate and oligoether acrylate.

This photopolymerizable polyurethane (C) can be obtained using the materials listed below. ■Divalent isocyanate 00l ■110- [R'-0-R'10]. 10. Oligoether urethane acrylate can be obtained by reacting ■ with ■ and then reacting with ■; oligoether urethane acrylate can also be obtained by reacting ■ with ■ and then reacting with ■. is obtained.

Examples of compound ■ include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexanemethane diisocyanate, and trimethylhexane. Examples include methylene diisocyanate. R4 that forms oligoester diol is a residue of a dihydric alcohol, and dihydric alcohols that can constitute R4 include ethylene glycol, diethylene glycol,
Neopentyl glycol, 1,4-pentanediol,
1.6-hexanediol, bisphenol A, polyethylene glycol, polybrobylene glycol, tetramethylene glycol, polytetramethylene glycol,
Examples include hydroxyl group-terminated liquid rubber and silicone diols.

R' is a residue of a dibasic acid, and dibasic acids that can constitute Rg include adivic acid, phthalic acid, succinic acid, glutaric acid, sebacic acid, vimelic acid, azelaic acid, isophthalic acid, etc. R8 and R7 forming the ether dial are residues of polyether and represent an alkyl chain of a ring-opening polymer of ethylene oxide, brobylene oxide, or tetrahydrofuran.

The photopolymerizable polyurethane (C) that can be obtained by the above method includes, for example, a reaction product obtained from the reaction of 1,10-decane di-olecyl and isophorone diisocyanate, and 2-hydroxybutyl methacrylate. Polyurethane acrylate obtained by reaction: Polyurethane acrylate obtained by further reacting 2-hydroxyethyl acrylate with a reaction product of polyester polyester obtained from pentyl glycol and adivic acid and isophorone diisocyanate; Polyurethane acrylate obtained by reacting 2-hydroxyethyl acrylate with the reaction product of an alcohol compound obtained by adding 2 moles of propylenoxide to 1 mole of bisphenol A and tolylene diisocyanate; hydroxybivalyl and parate Examples include polyurethane acrylates obtained by reacting 3-chloro-2-hydroxybutylene methacrylate with a reaction product of 1,6-hexane di-isocyanate and 1,6-hexane di-isocyanate.

In addition, as a commercially available product, ARO represented by the following general formula
NIX M-1100, M-1200 (manufactured by Toagosei Chemical Industry Co., Ltd.) CH2=CflCOO- R' -00CNH-R-N
}IcOO-polyol--OOCNH-R-
N}ICOO- R' -00CCH=CH2 :NK
Ester U-4-108-A (difunctional polyurethane). NK ester U-4HA (tetrafunctional polyurethane) (all manufactured by Shin-Nakamura Chemical Co., Ltd.), PHTOTMER
6008 (manufactured by SANNOPCO Co., Ltd.).

In addition, a low-viscosity reactive diluent polymer may be further included as an optional component.

Examples of the photoinitiator (D) include benzyl ether, pendyl methyl ketanol (Irgacure 651, manufactured by Ciba Geigy, etc.), penzoin alkyl ethers: benzoin isobutyl ether, penzoin isobutyl ether, penzoin-n-petityl ether, ether, benzoin ethyl ether, benzoin methyl ether, etc., benzophenones: benzophenone, 4.4°-bis(N
, N-diethylamino)penzophenone, penzophenone methyl ether, anthraquinones: 2-tert-butylanthraquinone, 2-tert-butylanthraquinone, etc., xanthone: 2-tert-butylanthraquinone, 2-tert-butylanthraquinone, 2-tert-butylanthraquinone, etc.
．． 4-diisobutylene xanthone, etc., acetophenones: 2,2-dimethoxy-2-phenylacetophenone, α,α-dichloro-4-phenoxyacetophenone, p-tert-butylic acetophenone, p-tert-butylic acetophenone,
2.2-Jetoxyacetophenone, p-dimethylaminoacetophenone, etc., or hydroxyl hexyl phenyl ketone (Irgacure 184, manufactured by Ciba Geigy, etc.), 1-(4-isobrobylphenyl)-
2-Hydroxy-2-methylpropan-1-one (Darocur 1116, manufactured by Merck ■, etc.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173, manufactured by Merck ■), etc. are suitable. It is mentioned as one used for. In addition to these photopolymerization initiators, an amine compound may be added as a photopolymerization accelerator. The amino compounds used as the photopolymerization accelerator include ethanolamine, ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, p-dimethylaminobenebenoic acid n-amyl ester, p-
-dimethylaminobenzoic acid isoamyl ester and the like.

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

For example, a graft copolymer polymer (A.) and a linear polymer (A.)
B) G (7) Weight ratio C (A): (B) = 80:20
A range of ~50:50 is desirable, and within this range good adhesion based on the graft copolymer polymer and good patterning properties based on the linear polymer can be obtained.

The weight ratio of photopolymerizable polyurethane (C) to the total amount of polymeric substances (A) + (B) is (A) + (
The range of B):(C)=100:50 to 100:200 is desirable. The photoinitiator (D) is added to the total amount of the resin (
For A)◆(B) + (C), (A) + (B
) + (C) : (D) = 100: 1 to 10
Use in the range of 0:10.

In addition, when using the photoinitiator (DJ and photopolymerization accelerator (E)), the addition of these ffi {(D) + (E)
) is the total amount of the resin (A) + (B) + (C
) for { (A) + (B) ten (C)) : {(D
)+(E)) = 100: It is desirable to use the range of IN100:10. Furthermore, the active energy ray-curable resin composition may optionally contain a condensation crosslinking catalyst, a thermal polymerization inhibitor, a filler, a coloring agent such as a dye or a pigment, a heat stabilizer such as hydroquinone or paramethoxyphenol, Adhesion promoters, plasticizers, extender pigments such as talc for improving wrinkle strength, leveling agents for imparting coating suitability, etc. may be added.

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

When using the above-mentioned active energy ray-curable resin composition in solution form for producing the liquid jet recording head of the present invention,
Alternatively, when forming a dry film, the solvent used when coating the resin composition on a film base such as a plastic film may include hydrophilic solvents such as alcohols, glycol ethers, and glycol esters. can be mentioned. Of course, these hydrophilic solvents 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 halogenated products, chlorine-containing fats such as methylene chloride and 1,1,1-trichloroethane. It is also possible to use an appropriate mixture of group solvents, etc. still,
These solvents can also be used as a developer for the resin composition of the present invention.

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

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

(2) In the case of forming a layer consisting of a cured coating film in the shape of a desired pattern on a substrate etc. (Part 1) etc. and subsequently evaporated to dryness. Then, the layer consisting of the dried coating film is scanned with a laser beam in a desired pattern, and the unexposed areas are 1, 1. 1
- 1- Form a cured coating layer in a desired pattern shape on a substrate etc. by removing with a suitable solvent such as ethane.

(3) When forming a layer consisting of a cured coating film in a desired pattern shape on a substrate, etc. (Part 2): Apply the active energy ray-curable resin composition in liquid form to a liquid coating film on a substrate, etc. It is then applied to form a powder and then evaporated to dryness. A photomask having a pattern of a desired shape through which active energy rays do not pass is superimposed on the layer of the obtained dry coating film, and the photomask is exposed to active energy rays from above. Then, the unexposed areas are removed using a suitable solvent such as 1.1, i-trichloroethane, and a layer of a cured coating film having a desired pattern shape is formed on the substrate or the like.

(4) When forming a photosensitive dry film and laminating the dry film on a substrate, etc.: Apply the active energy ray-curable resin in liquid form onto a polyethylene terephthalate film to form a liquid film, and then The film is evaporated and dried to obtain a photosensitive dry film on the polyethylene terephthalate film. The dry film is laminated onto a substrate or the like by a conventional lamination method to obtain a laminate. Then, the photosensitive dry film laminated on the substrate etc. is cured by irradiating it with active energy rays in the same manner as method (1) above. When it is desired to form a cured photosensitive film into a desired pattern, the dry film laminated on the support is treated in the same manner as method (2) or (3) described above.

The active energy ray-curable resin composition has the general formula (x)
When containing a monomer represented by
It is desirable to carry out condensation curing by heat treatment at a temperature of 0.000C.

In the process of manufacturing the liquid jet recording head of the present invention, the active energy rays used for curing the active energy ray-curable resin composition or pattern exposure of the resin composition are ultraviolet rays, which have already been widely put into practical use. Another example is an electron beam. As an ultraviolet light source, wavelength 2
Examples include high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps that contain a lot of light in the range of 50 nm to 450 nm.
The intensity of light near nm is 1 mW/cm2 to 100 mW
/cm2 is preferable. The electron beam irradiation device is not particularly limited, but a device having a dose in the range of 0.5 to 20 M Rad is practically suitable.

Hereinafter, a method for manufacturing a liquid jet recording head of the present invention will be described with reference to the drawings, taking as an example a case in which the liquid passage wall 3H is formed using a dry film type cured film obtained from the above-mentioned resin composition. 2 to 6 are schematic diagrams for explaining the manufacturing procedure of the liquid jet recording head of the present invention. In order to form the liquid jet recording head of the present invention, first, as shown in FIG. The number of pieces will be placed. In addition, if necessary, please check the resistance to recording liquid, electrical insulation, etc. of the board. SiO■ is applied to the surface for the purpose of imparting
, Ta2k5, glass, or the like may be coated with a protective layer. Further, although not shown, an electrode for inputting a recording signal 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 shown in FIGS. 3(a) and 3(b), The dry film type (film thickness, about 20 μm to 200 μm) active energy ray-curable resin composition 3 was added to the
Heating to about 0°C, for example, 0.5 to 0. 4 f/
min. The film is laminated onto the substrate surface IA at a speed of 1 to 3 Kg/Cm2 under pressure conditions.

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

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

When exposed in this way, the area other than the area covered by the pattern, that is, the exposed area of the dry film layer 3, polymerizes and hardens, and the unexposed area remains solvent soluble, whereas the solvent Becomes insoluble. The active energy rays used for this pattern exposure are:
Depending on the types of components of the above-mentioned active energy ray-curable composition, a suitable one may be selected and used from conventionally known active energy rays. Specifically, for example, high-pressure mercury lamps, ultra-high pressure Mercury lamp, metal halide lamp,
Examples include carbon arc lamps and electron beams.

For example, as an ultraviolet light source, the wavelength is 250 nm to 450 nm.
Examples include high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps that contain a lot of nm light, and the intensity of light in the vicinity of 365 nm is 1 mW/cm2 to 100 mW/cm at a practically acceptable distance between the irradiated objects. ' is preferable. The electron beam irradiation device is not particularly limited, but a device having a dose in the range of 045 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 a film of, for example, I, 1,
The unpolymerized (uncured) portion of the solvent-soluble dry film layer 3 is dissolved and removed from the substrate 1 by immersion in a volatile organic solvent such as l-trichloroethane, etc. As shown in a) and FIG. 5(b), the cured resin film 3H remaining on the substrate l forms grooves that will eventually become the liquid passage 6-2 and the liquid chamber 6-1.

Next, the cured resin film 3H on the substrate 1 is heated to at least 80°C.
Heat polymerization by heating at the above temperature for about 10 minutes to 3 hours. Note that when a thermosetting graft copolymer polymer is used in the resin composition 3, the heat treatment temperature is at least 100° C. for about 5 to 60 minutes.

In the recording head of this example, an example is described in which a dry film type resin composition, that is, a solid material is used to form the grooves that will become the liquid passage 6-2 and the liquid chamber 6-1. 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 appropriate viscosity of the resin composition is 100 cp to 3000 cp. Also,
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 6-1 using the cured resin film 3H,
As shown in FIGS. 6(a) and 6(b), the flat plate 7 that covers the groove is bonded to the cured resin film 3H with an adhesive to form a bonded body.

In the steps shown in FIG. 6(a) and FIG. 6(b),
A specific method for attaching the cover 7 is 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 in which the adhesive layer is made into a so-called B stage, bonded onto a cured dry film 3H, and then the adhesive layer is fully cured. 7 may be directly heat-sealed onto the cured resin film 3H without using an adhesive.

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 preferred is a method in which active energy rays are irradiated and heated afterwards, ie, a method in which the resin composition for forming a cured resin film of the present invention is used as an adhesive. In FIG. 6, 6-1 is a liquid chamber, 6-2 is a liquid passage, 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) shows a through hole for connecting. In this way, after the bonding between the cured resin yA3H provided on the substrate 1 and the flat plate 7 is completed, this bonded body is moved through the liquid passage 6-- shown in FIGS. 6(a) and 6(b). Cutting is performed along C-C on the downstream side of No. 2 to form an orifice for discharging recording liquid, which is an opening of a liquid passage on the cut surface.

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 is selected as appropriate. During this cutting,
A dicing method or the like commonly used in the semiconductor industry can be used.

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

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

Synthesis Example 1 The following components were prepared as components constituting the active energy ray-curable resin composition used for producing the liquid jet recording head of the present invention.

Graft weight Aw (A) 50 parts by weight of 2-hydroxybutyl methacrylate, N-
Radical chain transfer polymerization was performed using 50 parts by weight of methylol acrylamide, glycolic acid as a chain transfer agent, and azobisisobutyronitrile as a polymerization initiator to produce a oligomer having a carboxy group at the end of the split chain. Obtained.

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

The number average molecular weight of this macromonomer by GPC method is:
It was about 3,000. 20 parts by weight of this macromonomer and 80 parts by weight of methyl methacrylate were solution polymerized in a methyl cellosolve solvent to obtain a thermosetting graft copolymer having a weight average molecular weight of approximately 40,000 and a number average molecular weight of approximately 10,000. Ta.

Xu Lin] L Yao Yul Methyl methacrylate, 2-hydroxybutyl methacrylate, and N-methylol acrylamide, 80:
A linear acrylic copolymer obtained by polymerization at a molar ratio of 10:10. The number average molecular weight of this linear acrylic copolymer is approximately 10
10,000, and its weight average molecular weight is approximately 270,000.

゛'Polyurethane C) A photopolymerizable polyurethane with a molecular weight of 2000 consisting of dicyclohexyl diisocyanate and polypropylene glycol copolymer (molecular weight: 200) components and 2-hydroxyethyl acrylate components'') Irgacure 651 (manufactured by Ciba Geigy) Crystal Violet Next, a liquid active energy ray-curable resin composition was obtained by mixing the above materials in the weight ratio shown below using a normal mixing technique. Ta.

Material Part by weight (A) 50 (B)
50(C)
+20 (D) 7 Dye 0.1 Methyl ethyl ketone 250 Next, a part of the liquid resin composition obtained in this way was applied to a 25 μm polyethylene terephthalate film (Lumirror T type) using a reverse coater. The obtained coating film was dried to obtain a dry coating layer (dry film) having a thickness of 80 μm.

Furthermore, a 40 μm stretched polyethylene film is laminated as a cover film on the dry coating layer, and an active energy ray-curable resin composition layer (thickness: 80 μm) as a dry film is placed between the two films. A laminate having a configuration switched to No. 1 was obtained.

Example 1 The tri-film produced in Synthesis Example 1 was used to carry out the steps shown in FIGS. 1 to 6 previously described in the specification. Therefore, 10 heating elements [hafnium boride (HfBz)] are used as ejection energy generating elements, and orifices provided corresponding to the heating elements (orifice size: 80 gm
An on-demand liquid jet recording head as shown in FIG. 7(d) having a pitch of 120 nm and a pitch of 0.200 mm 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 SiO 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 layered on the protective layer. , 10
The dry film with a thickness of 80 μm obtained in Synthesis Example 1 heated to 0°C was rolled at a roll temperature of 100°C and a peripheral speed of 1. 0m/
min. The polyethylene film was laminated while being peeled off using a rubber roll under these conditions.

Next, a photomask having a pattern corresponding to the shape of the liquid passage and the liquid chamber is superimposed on the dry film provided on the substrate surface, so that the above-mentioned element is provided in the liquid passage that is finally formed. After aligning and vacuum-adhering, the photomask was exposed to light using a highly parallel ultra-high pressure mercury lamp with an ultraviolet intensity of 10 mW/cm'' at around 365 nm from the top of the photomask and a collimation angle of 3 degrees.
The dry film was exposed for seconds.

Next, after the exposure, the polyethylene terephthalate film was peeled off from the dry film on the substrate, and then the dry film was spray developed with 1.1.1-trichloroethane (trade name Eterna Nu) at 20°C for 50 seconds. ,
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 post-irradiated with an ultra-high-pressure mercury lamp (UV post-cure) for 5 minutes under the same conditions as those used for pattern exposure, and further cured at 150°C for 15 hours. A post-curing treatment was performed by performing a heat treatment for 1 minute.

In this way, grooves serving as liquid passages and liquid chambers were formed on the substrate by the walls made of the cured dry film membrane.

On the other hand, the dry film obtained in Synthesis Example 1 was placed on a soda glass flat plate (top plate) in which a liquid chamber was formed and through holes were formed, and a rubber roll was placed under the conditions of a roll temperature of 120°C and a roll speed of lm/min. was used to laminate the polyethylene film while peeling it off. Next, exposure and development were performed under the same conditions as in the process of forming the liquid passage and the liquid chamber, except that a mechanical mask with a film thickness of 10 μm was used, and the portion of the tri-film corresponding to the upper part of the liquid chamber was removed from the flat plate.

Next, the surface of the cured dry film on this flat plate and the surface of the cured film on the substrate obtained earlier were bonded together under pressure, and the surface of the cured dry film on the flat plate was bonded and fixed by irradiating ultraviolet rays (50 mW/cm2, 60 seconds) from the flat plate side. and formed a zygote.

Next, the downstream side of the liquid passage of the bonded body, that is, 0.150 mm downstream from the installation position of the ejection energy generating element.
The area was cut perpendicularly to the liquid path using a commercially available dicing saw (trade name: DAD 2H/6 type, manufactured by DISCO) to form a rift 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 obtained recording heads all had liquid passages and liquid chambers that faithfully reproduced the mask vacuum, and had excellent dimensional accuracy. By the way, the diameter of the rifice is 80±5μm long and 80±5μm wide.
5 μm, and the onofis pitch was in the range of 200±5 μm.

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

First, the obtained recording heads were subjected to a durability test in which they were immersed in recording liquids having the following compositions at 60° C. for 1000 hours (environmental conditions comparable to those during long-term use of recording heads 1 to 1).

Recording liquid component 1) H20/diethylene glycol/l. 3-dimethyl-2-imidazolidinone/C. I. Direct Blue 86'1 (=57/30/10/3 parts by weight) pH=8.02)
H. O/diethylene glycol/N-methyl-2-pyrrolidone/C. I. Direct black +54"2 (・
55/30/10/5 parts by weight) pH・9.03) H20
/diethylene glycol/polyethylene glycol#
400/N-methyl-2-pyrrolidone/C. L Direct Yellow 86”3 (・65/10/10/10/5 parts by weight) pH・7.
04) H20/ethylene glycol/triethylene glycol/triethylene glycol monomethyl ether/C. I. Hood black 2"4 (=67/10/1
5/5/3 parts by weight) pH=lO. Note: 1 to 4 are water-soluble dyes, and caustic soda was used to adjust the pH.

After the durability test, we observed the state of bonding between the base 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. Ta. Separately, each of the obtained 10 recording heads was attached to a recording device, and a recording signal of 1OB pulse 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.

For both 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. [Effect of the invention 1 As explained above, the active energy ray-curable resin composition used in the structure of the liquid jet recording head of the present invention is
Since the graft copolymer polymer (A) is used as a constituent component, it has sufficient adhesion to various members without the addition of additives, etc., and the linear polymer (B) is used as a constituent component. Since it is contained as a compound, it has excellent development characteristics during pattern formation. Also,
At the same time, the cured film has sufficient chemical resistance, durability, etc.

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

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

Further, since the recording head of the present invention has the above-described configuration, it has high reliability and excellent durability even when it is made into a multi-requisition recording head.

[Brief explanation of the drawing]

1 to 6 are schematic diagrams for explaining the liquid jet recording head of the present invention and its manufacturing method, and FIG. 7 and FIG.
8(a) and 8(b) are partial cross-sectional views taken in a plane perpendicular to the liquid path of the recording head, showing the portion where the cured resin film is used.
) and FIG. 9 are diagrams showing other configurations of the recording head. 1: Substrate 2: Discharge energy generating element 3: Resin layer 31 {: Cured resin film (liquid passage wall) 4: Photomask 4P: Mask pattern 6-1 = liquid chamber 6-2. Liquid passage 7: Cover 8: Through hole 9: Rifice 10: Supply pipe 1I; Electrode 12: Upper protective layer 13: Heat generating resistor layer 14: Adhesive layer

Claims (1)

[Scope of Claims] 1) A liquid jet recording head having a cured product of an active energy ray-curable resin composition as part of its structure, wherein the composition comprises (A) alkyl methacrylate, acrylonitrile, and styrene. A group consisting of a monomer represented by the following general formula (x) and a monomer represented by the following general formula (y), with a backbone mainly consisting of a structural unit derived from one or more monomers selected from the group consisting of A graft copolymer polymer to which a branch chain having a structural unit derived from at least one monomer selected from the above is added, and has a number average molecular weight of 5,000 or more and a weight average molecular weight of 50,000 or less; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(x) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(y) [However, R^1 is hydrogen or has 1 to 3 carbon atoms.
represents an alkyl group or a hydroxyalkyl group, R
^2 represents hydrogen, or an alkyl group or acyl group having 1 to 4 carbon atoms which may have a hydroxy group, and R^3 represents an alkyl group having 2 to 6 carbon atoms, or a halogen-substituted alkyl group. Alkyl groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, 2≦m+n≦6, n≠0, m≠0) Alkyl ether groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, 2≦m+n≦4, including cases where n=0 or m=0). ] (B) Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, t-butyl methacrylate,
Benzyl methacrylate, acrylonitrile, isobornyl methacrylate, isobornyl acrylate,
Having a structural unit derived from one or more monomers selected from the group consisting of tricyclodecane acrylate, tricyclodecane methacrylate, tricyclodecaneoxyethyl methacrylate, styrene, dimethylaminoethyl methacrylate, and cyclohexyl methacrylate,
and has a structural unit derived from at least one monomer selected from the group consisting of the monomer represented by the general formula (x) and the monomer represented by the general formula (y), and has a number average molecular weight of 50,000 or more. and a linear polymer having a weight average molecular weight of 350,000 or less and a glass transition temperature of 60°C or higher, and (C) the molecular chain terminal of a polyurethane obtained from an oligoester diol or oligoether diol and a divalent isocyanate. 1. A liquid jet recording head comprising: (D) a photoinitiator; and (D) a photoinitiator. 2) The liquid jet recording head according to claim 1, wherein the weight ratio of the graft copolymer polymer and the linear polymer is 80:20 to 50:50. 3) The weight ratio of the total weight of the graft copolymerized polymer and the linear polymer to the active energy ray-curable oligomer is 100:50 to 100:200.
or 2. The liquid jet recording head according to 2. 4) Any one of claims 1 to 3, wherein the weight ratio of the total weight of the graft copolymer polymer, the linear polymer, and the active energy ray-curable oligomer to the photoinitiator is 100:1 to 100:10. A liquid jet recording head described in .