JPS63251244A - Liquid jet recording head - Google Patents

Abstract

PURPOSE:To obtain a liquid jet recording head sufficient in durability with raised reliability, by providing a substrate and a resin setting film layer for forming a groove to serve as at least a liquid passage. CONSTITUTION:A liquid jet recording head is composed of a substrate 1, a resin setting film 3H processed by patterning to a specific form installed thereon, and a cover 7 laminated further thereon. Then, an orifice 9 for discharging recording liquid, liquid passages 6-2, which is interconnected to the orifice 9, having parts where energy for discharging recording liquid acts on the recording liquid, and liquid chambers 6-1 for reserving the recording liquid to be supplied to the liquid passages 6-2 are formed. Further, a supply tube 10 for providing the recording liquid to the liquid chambers 6-1 from the outside of the recording head is connected to a through hole 8.

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 small droplets of recording liquid such as an ink droplet 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 a recording liquid such as ink and attaches them to a recording material such as paper to perform recording, and the noise generated during recording is extremely small and can be ignored at high speed. It has attracted attention as a recording method that can record on plain paper without requiring any special processing such as fixing, and various types of recording methods have been actively researched recently.

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

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

A method for manufacturing a liquid jet recording head having such a configuration is, for example, to form fine grooves on a flat plate of glass, metal, etc. by cutting or etching, and then to attach other suitable plates to the flat plate with the grooves formed thereon. Alternatively, for example, a groove wall of a cured photosensitive resin is formed on a substrate on which an ejection energy generating element is arranged by a single photolithography process, and a liquid passage is formed 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. 57-4
No. 3876).

Among these methods for manufacturing liquid jet recording heads, the latter method using photosensitive resin is superior to the former method in that it allows for more accurate liquid passages and better yields (can be finely processed and mass-produced). Since it is easy to use, it has the advantage that it is possible to provide a liquid jet recording head of good quality and at a lower cost.

The photosensitive resins used to manufacture such recording heads are those that have been used for pattern formation in printing plates, printed wiring, etc., and those that have been used as photocurable paints and adhesives for glass, metals, ceramics, etc. Known resins are used, and dry film type resins have been mainly used from the viewpoint of work efficiency.

[Problem that the invention seeks to solve]

In a recording head using a cured film of a photosensitive resin, in order to obtain excellent characteristics such as advanced recording characteristics, durability, and reliability, the photosensitive resin used for the recording head has the following characteristics: Excellent adhesion to the substrate as a film.

(2) Excellent mechanical strength and durability when cured.

(3) Excellent sensitivity and resolution when forming patterns using pattern exposure.

It is required to have the following characteristics.

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

That is, printing plates, photosensitive resins for recording heads,
Materials used for pattern formation in printed wiring etc. have excellent sensitivity and resolution, but have poor adhesion and adhesion to glass, ceramics, plastic films, etc. used as substrates, and have poor mechanical properties when cured. Insufficient strength and durability. Therefore, during the manufacturing stage of the print head or during use, for example, the flow of the print liquid in the liquid passage may be obstructed, or the direction of droplet ejection may be made unstable, resulting in deterioration of the print characteristics. It has the disadvantage that it is susceptible to deformation of the cured resin, peeling from the substrate, damage, etc., which significantly impairs the reliability of the recording head.

On the other hand, known photo-curing paints and adhesives used for glass, metals, ceramics, etc., have excellent adhesion and adhesion to substrates made of these materials, and have sufficient mechanical properties when cured. Although it has the advantage of being strong and durable, it is inferior in sensitivity and resolution, so it requires a higher intensity exposure device and a longer exposure operation, and due to its characteristics, Since it is not possible to obtain a precise high-density pattern with good resolution, there is a problem in that it is not suitable for use in recording heads that require particularly fine precision processing.

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

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

Another object of the present invention is to provide a liquid jet recording head that is highly reliable and has excellent durability even when it has multiple orifices.

[Means for solving problems]

The above objects can be achieved by the following invention.

In the present invention, a layer made of a resin composition that is hardened by active energy rays is exposed in a predetermined pattern using active energy rays, and the liquid passages that are provided on the substrate surface and communicate with the liquid discharge ports are exposed in a predetermined pattern using the active energy rays. forming a cured resin composition;
A liquid jet recording head is formed by removing an uncured region from the layer, and the resin composition has a number average molecular weight of about io, oo.

The above butadiene polymer (a) and an average of 1 acryloyl group and/or methacryloyl group in the molecule
．． A liquid jet recording head characterized in that it is an active energy ray-curable resin composition comprising at least one type (b) of liquid polybutadiene having five or more polybutadienes.

That is, the recording head of the present invention includes a substrate and a cured resin film layer forming at least grooves serving as liquid passages,
The durability of each member that makes up the recording head and the adhesion between each member are excellent, and the cured resin film layer is microfabricated with high precision, resulting in excellent recording properties and high reliability. This is a recording head with excellent durability.

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

FIG. 1 shows an example of the liquid jet recording head of the present invention, FIG. 1(a) is a perspective view of its main parts, and FIG.
FIG. 2 is a cross-sectional view taken along line c-c' in FIG.

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

Furthermore, a supply pipe 10 for supplying recording liquid from the outside of the recording head to the liquid chamber 6-1 is connected to the through hole 8 provided in the cover. Note that the supply pipe 10 is omitted in FIG. 1(a).

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

The substrate 1 constituting the recording head of the present invention is made of glass.

Made of ceramics, plastic, metal, etc.
A desired number of generating elements 2 are arranged at predetermined positions.

In the example shown in FIG. 1, 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.

In addition, the cover 7 is made of glass, ceramics, or plastic.

It is made of a flat plate made of plastic or metal, and is bonded to the cured resin film 3H by fusing or bonding using an adhesive, and is provided with a through hole 8 at a predetermined position for connecting the supply pipe 10. ing.

In the recording head of the present invention, the cured resin film 3H patterned into a predetermined shape and forming the walls of the liquid passage 6-2 and the liquid chamber 6-1 is formed on the substrate l or on the cover 7. It was obtained by patterning a layer made of a resin composition having the composition described in one step of photolithography. Note that this cured resin film 3H 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 a butadiene polymer (a) having a number average molecular weight of about 10,000 or more. ) and at least one liquid polybutadiene having an average of 1.5 or more acroyl groups and/or methacryloyl groups in the molecule (b)
An active energy ray-curable resin composition comprising: a resin composition having good adhesion to a substrate made of glass, plastic, ceramics, etc., especially when formed into a cured film;
It also has excellent resistance to recording liquids such as ink and mechanical strength, and has excellent properties as a component of liquid jet recording heads, such as being able to form precise, high-resolution patterns by patterning with active energy rays. It is something. 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 above-mentioned component (a), which primarily characterizes the present invention, is a butadiene polymer having a number average molecular weight of about 10,000 or more, and any conventionally known components can be used in the present invention. For example, specific examples include 1,2-polybutadiene, trans-1,4-polybutadiene, cis-1,4-polybutadiene, acrylonitrile-butadiene copolymer, and styrene-butadiene copolymer. Furthermore, when these butadiene-based polymers have functional groups such as hydroxyl groups and carboxyl groups at both ends, those whose chain length is extended by utilizing these functional groups are also useful.

For example, in the case of polybutadiene having a hydroxyl group or a carboxyl group at both ends, the chain length of the polybutadiene can be extended using a diincyanate compound, a jepoxy compound, or the like.

Examples of diisocyanate compounds used for such chain lengthening include hexamethylene diisocyanate, inphorone diisocyanate methylene bis(4-phenyl isocyanate), xylylene diisocyanate, water-added xylylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), and the like. Any diisocyanate compound can be used.

Examples of the jepoxy compound include polyethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, neohentyl glycol diglycidyl ether, 1,6-hexashiol diglycidyl ether, methylenebis(4-cyclohexylglycidyl ether)nol F1 tetra Hydroxyphenylmethane tetraglycidyl ether, resorcinol glycidyl ether, glycerin triglycidyl ether, pentaerystol triglycidyl ether, isocyanuric acid triglycidyl ether and the following general formula (m) (However, R in the above formula is an alkyl group or oxyalkyl The group Ro represents a group, (-C)-CH2+) or an alkyl group. ) Examples include (meth)acrylic acid esters of epoxy urethane resins represented by:

Component (a) constituting the resin composition of the present invention as described above needs to have a number average molecular weight of about 10,000 or more, and preferably has a number average molecular weight of about 20,000 to 200,000. By using component (a) having such a number average molecular weight, when the resin composition of the present invention is used, for example, as a dry film, it is possible to impart an aptitude for maintaining the resin composition in the form of a solid film. It is also possible to impart excellent mechanical strength, chemical resistance, water resistance, etc. to the formed pattern. On the other hand, if the number average molecular weight of component (a) is less than 10,000, even if a dry film can be formed, it will be difficult to stably hold this dry film on the support. For example, it is undesirable because it may gradually flow during storage, causing wrinkles or non-uniform layer thickness.

The component (b), which is another essential component constituting the resin composition of the present invention, is a liquid polybutadiene having an average of 1.5 or more (meth)acryloyl groups in one molecule.

Hereinafter, the composition of the active energy curable composition used for forming the recording head of the present invention will be explained in detail. In the present invention, the terms "(meth)acryloyl group", "(meth)acrylate" and "(meth)acrylic" refer to "acryloyl group and methacrylic group", "acrylate and methacrylate", "acrylic and methacrylic group", respectively. ”.

Such component (b) can be easily prepared, for example, by the following method. Note that these methods are merely examples, and it is obvious that component (b) may be prepared by other methods.

(a) A method of reacting about 2 moles of a diisocyanate compound per mole of polybutadiene having hydroxyl groups at both ends to prepare a prepolymer having NGO groups at both ends, and reacting this with a hydroxyl group-containing (meth)acrylate.

(b) A method of reacting a polybutadiene containing carboxyl groups at both ends with a (meth)acrylate having an epoxy group.

(c) β- at the tertiary carbon position of l,2-polybutadiene
A method of adding ene to an unsaturated carboxylic acid anhydride and reacting it with a hydroxyl group-containing (meth)acrylate to form Hafestel.

The diisocyanate compound used in the above is the same diisocyanate compound as mentioned above, and the (meth)acrylate compound having an epoxy group is, for example, glycidyl (meth)acrylate, glycidylethyl (meth)acrylate, glycidyl butyl (meth)acrylate, etc. Examples of hydroxyl group-containing (meth)acrylate compounds include 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and pentaerythritol monohydroxy. Any conventionally known hydroxyl group-containing (meth)acrylates such as tri(meth)acrylate and dipentaerythritol-monohydroxypenta(meth)acrylate can be used.

As described above, component (b), which is an essential component constituting the resin composition of the present invention, is obtained, but the number of (meth)acryloyl groups per molecule can be changed arbitrarily depending on the selection of the raw materials used. However, for the purpose of the present invention, 1
It is desirable to have about 1.5 or more (meth)acryloyl groups per molecule; if the number of (meth)acryloyl groups is less than 1.5, the crosslinking rate by active energy rays is insufficient and Therefore, it is difficult to form a high-resolution pattern. On the other hand, if the number of (meth)acryloyl groups is too large, the flexibility of the formed film will decrease, which is not preferable (therefore, the number of (meth)acryloyl groups per molecule of component (b) in the present invention is About 1.5 to 10 is preferable.

Component (a) and component (b) as described above are blended in such a proportion that component (a) accounts for 20 to 80% by weight and component (b) accounts for 80 to 20% by weight of the total weight of both. is preferable. If the content of component (a) is less than 20% by weight, the resin composition before curing will have low viscosity and fluidity, requiring careful handling before curing, and the mechanical strength exhibited by component (a). This results in insufficient use of the resin composition of the present invention as a structural member or protective coating.

On the other hand, when the proportion of component (a) exceeds 80% by weight,
That is, when the amount of component (b) decreases, the crosslinking rate by active energy rays decreases, and a sufficient crosslinking density cannot be achieved, resulting in non-overlapping formation of a pattern with high density and high resolution. Most preferably, the object of the present invention is best achieved when component (a) is 30 to 70% by weight and component (b) is 7% by weight.
The composition ratio is 0 to 30% by weight.

The essential components of the active energy ray-curable resin composition of the present invention are the above components (a) and (b), and the resin composition consisting of these two components is easily crosslinked and cured by high energy rays such as electron beams. However, when curing is performed using ultraviolet rays or infrared rays, it is preferable to incorporate a radical polymerization initiator.

For UV curing, for example, benzyl, benzophenone, benzoin, isopropyl ether, anthracene,
Any conventionally known photopolymerization initiator such as P-dimethylaminoacetophenone can be used, and in addition to these radical polymerization initiators, it is also preferable to use a photopolymerization accelerator such as triethylamine or tributylamine.

In addition, when sufficient crosslinking by unsaturated bonds of polybutadiene is required, radical polymerization initiators that can be activated by the action of heat, such as benzoyl peroxide, methyl isobutyl ketone peroxide, dicumyl peroxide, Cumene hydroperoxide, ter
It is preferable to use a conventionally known radical polymerization initiator such as t-butylcumyl peroxide.

The radical polymerization initiator as described above is about 0.1 to 2 parts by weight per 100 parts by weight of the total amount of components (a) and (b).
It is preferable to blend it in a proportion of 0 parts by weight.

Furthermore, in order to further promote and improve the efficiency of curing of the resin composition of the present invention by active energy rays, it is preferable to incorporate a monomer having an ethylenically unsaturated bond. The mechanical strength of the coating and the high resolution of the pattern can be further improved.

Monomers having such ethylenically unsaturated bonds include styrene, methyl (meth)acrylate, butyl (
meth)acrylate, hexyl(meth)acrylate,
Any conventionally known vinyl monomer can be used, such as pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and the like.

The monomer having such an ethylenically unsaturated bond has a total amount Zo of the components (a) and (b).

It is preferable to mix it in a ratio of 1 to 100 parts by weight per part by weight, and when the number of (meth)acryloyl groups in the component (b) is relatively small, a relatively large amount is added.
When the number of (meth)acryloyl groups in the component is relatively large, it is preferable to use a relatively small amount. If the amount used is too large, the crosslinking rate of the resin composition will increase, but this is not preferable because the excellent chemical resistance, water resistance, mechanical strength, etc. possessed by component (a) will be impaired.

Furthermore, the active energy ray-curable resin composition of the present invention may contain other additives, such as organic and inorganic fillers, colorants, plasticizers, antistatic agents, reactive polymers, organic solvents, etc., as necessary. Depending on the use, they can be blended within a range that does not interfere with achieving the objectives of the present invention.

When using the active energy ray-curable resin composition of the present invention as described above in the form of a solution or when coating it on a plastic film that is a film base material when forming a dry film, the solvent used is 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, 1,1.1-)lychloroethane, etc. It is also possible to use an appropriate mixture of group solvents and the like. Incidentally, these solvents can also be used as a phenomenon liquid for the resin composition after pattern exposure.

Also, effective adhesion promoters include silane coupling agents and low molecular weight surfactants as inorganic surface modifiers.

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

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

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

In order to form the liquid jet recording head of the present invention, first, as shown in FIG. 2, glass and ceramics are used.

A desired number of ejection energy generating elements 2 such as heating elements or piezo elements are arranged on a substrate l made of plastic or metal. In addition, if necessary, resistance to recording liquid,
For the purpose of imparting electrical insulation or the like to the surface of the substrate 1, the surface may be coated with a protective layer of SiO2, Ta20B, glass, or the like. 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 l obtained through the process shown in FIG. 2 and drying it at, for example, 80-150°C, The dry film type (film thickness, about 25 μm N 100 μm) active energy ray-curable resin composition 3 was added to the
Heating to about 0℃, e.g. 0℃~0.4f/m
The substrate is laminated onto the substrate surface IA at a speed of 1 in. and a pressure of 1 to 3 kg/crrr.

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

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

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

The active energy rays used for this pattern exposure are:
Examples include ultraviolet rays and electron beams, which have already been widely put into practical use. As an ultraviolet light source, the wavelength is 250 nm to 4
A high-pressure mercury lamp that contains a lot of 50nm light.

Examples include ultra-high pressure mercury lamps, metal halide lamps, etc., and the distance between the lamp and the irradiated object is 3.
The intensity near 65 nm is 1 mW/cI ~ 100 mW/
It is preferable that the amount is about crrr. 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.

After pattern exposure of the dry film layer 3 is completed, next, the exposed dry film 3 is exposed to light, for example.

1.1-) The unpolymerized (unhardened) portion of the dry film layer 3, which is soluble in the solvent, is dissolved and removed from the substrate l by developing it by immersing it in a volatile organic solvent such as lycrylic ethane. As shown in FIGS. 5(a) and 5(b), the cured resin film 3H remaining on the substrate 1 forms grooves that will eventually become the liquid passage 6-2 and the liquid chamber 6-1.

Next, if necessary, the cured resin film 3H on the substrate 1 is further heated, for example, at 100 to 150° C. for about 5 to 30 minutes to thermally polymerize.

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. 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 needs to be determined by taking into account the reduction in number 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), a flat plate 7 serving as a cover for the groove is bonded onto the cured resin film 3H 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 spin-code 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 acrylic resin is made into a so-called B stage, bonded onto a cured dry film 3H, and then the adhesive layer is fully cured.

A method that does not use an adhesive may also be used, such as directly heat-sealing a flat plate 7 of thermoplastic resin such as ABS resin or polyethylene onto the cured resin film 3H.

Further, a resin layer made of the resin composition for forming a cured resin film according to the present invention is provided on the side of the cover 7 that is joined to the liquid passage, and this is heat-sealed to the cured resin film 3H forming the liquid passage. Also preferable is a method in which active energy rays are irradiated and heated afterwards, that is, a method in which the resin composition for forming a cured resin film of the present invention is used as an adhesive.

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

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

This process involves the ejection energy generating element 2 and the orifice 9.
This is done to optimize the distance between the two, and the area to be cut here is selected as appropriate. For this cutting, a dicing method or the like commonly employed in the semiconductor industry can be employed.

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

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.

Note that in the recording head described above, the liquid passage 6-2 and the liquid chamber 6-1 are integrally molded by resin curing H, but the recording head of the present invention is limited to such a structure. Instead, the liquid passage and the liquid chamber may be separately molded. However, in either structure, the recording head of the present invention is such that at least a portion of the resin forming the liquid passage is formed using the active energy ray-curable resin composition mentioned above. be.

〔Effect of the invention〕

In the liquid jet recording head of the present invention, the active energy ray-curable resin composition that is a constituent member of the head is mainly provided by a monomer having an ethylenically unsaturated bond, which is contained as an essential component in the composition. A material having excellent sensitivity and resolution as a pattern forming material is used, and by using this resin composition, it has become possible to obtain a liquid jet recording head with excellent dimensional accuracy at a high yield. In addition, the resin composition used in the present invention mainly includes a butadiene polymer Ca) having a number average molecular weight of about 10,000 or more as essential components and an average of 1.5 acryloyl groups and/or methacryloyl groups in the molecule. It also has excellent adhesion to the substrate, mechanical strength, and chemical resistance provided by at least one type (b) of the liquid polybutadiene having the above properties, and by using the composition, it has long-term durability. It also became possible to obtain a recording head.

In addition, a towable butadiene polymer (a) having a number average molecular weight of about 10,000 or more and an acryloyl group and/or methacryloyl group in the molecule on average of 1.
At least one liquid polybutadiene having 5 or more (
When using the active energy ray-curable resin composition using b), it is possible to obtain a liquid jet recording head particularly excellent in the above-mentioned adhesion, mechanical strength, or chemical resistance.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples and Examples. In the text, parts or % are based on weight unless otherwise specified.

Synthesis Example 1 (1) Synthesis of a butadiene polymer having a number average molecular weight of about 10,000 or more.

1,2-polybutadiene containing hydroxyl groups at both ends (M n=
2,000) Put 200g into the Mitsuro flask,
It was dissolved in 200 g of butyl acetate. 0.1 g of hydroquinone was added as a polymerization inhibitor, and the temperature of the solution was raised to 100°C. Methylene bis(4-
26.2 g of dichlorohexyl isocyanate) was added dropwise over 10 hours. The mixture was further stirred at 100°C for 10 hours to allow the reaction to proceed. Disappearance of unreacted isocyanate compounds was confirmed by IR method. The obtained polymer solution had high viscosity. The number average molecular weight determined by GPC method was 50,000, and the weight average molecular weight was 190,000. It was confirmed that evaporation of butyl acetate resulted in a tack-free product.

(2) Synthesis of acryloylated polybutadiene 1,2-polybutadiene containing hydroxyl groups at both ends (M n 700 )
70g was put into a Mitsuro flask and dissolved with 450g of butyl acetate. Hydroquinone 0.05 as a polymerization inhibitor
g was added thereto, and the temperature of the solution was raised to 90°C. Using a dropping funnel, 52.4 g of methylene bis(4-cyclohexyl isocyanate) was added dropwise over 5 hours. The mixture was further stirred at 90° C. for 5 hours to allow the reaction to proceed. Disappearance of unreacted hydroxyl groups was confirmed by IR method.

23.2 g of 2-hydroxyethyl acrylate was added dropwise to the solution of polybutadiene containing isocyanate at both terminals using a dropping funnel at 90° C. over 5 hours. 90 more
The reaction was continued with stirring for 5 hours at a temperature of 100°C.

Disappearance of incyanate groups was confirmed by IR method.

Example 1 60 g of the butadiene polymer obtained in (1) of Synthesis Example 1.

Acryloylated polybutadiene 30 obtained in the same (2)
g and 10 g of 1,2,4-trivinylcyclohexane
was dissolved in 400 g of methyl ethyl ketone. 5 g of benzophenone and 1 g of mifilaz ketone as photoinitiators
, and 2 g of benzoyl peroxide was added as a thermal polymerization initiator.

Next, the above resin composition was applied to a 16 μm polyethylene terephthalate film using a wire bar, and heated at 100°C.
By drying for 20 minutes, a dry film according to the present invention having a resin composition layer with a thickness of 75 μm was produced.

Using the above dry film, a heating element [hafnium polide (HfB2)] 10 is used as an ejection energy generating element according to the steps shown in FIGS. 1 to 6 previously explained in the specification.
orifice (orifice dimensions: 75 μm x 50 μm
An on-demand liquid jet recording head having a pitch of 125 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 SiO2 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 dry film having a thickness of 75 μm shown in the synthesis example heated to 0.degree. C. was laminated at a speed of 0.4 f/min and under pressure of 1 Kg/crrf.

Next, a photomask having a pattern corresponding to the shape of the liquid passage and the liquid chamber is superimposed on the dry film provided on the substrate surface, so that the above-mentioned element is provided in the liquid passage that is finally formed. After alignment, the dry film was exposed from above the photomask for 30 seconds using ultraviolet light with an intensity of 8.2 mW/crrf.

Next, the exposed dry film is immersed in 1,1.1-trichloroethane and developed, and the unpolymerized (uncured) portion of the dry film is dissolved and removed from the substrate, leaving no residue on the substrate. The cured dry film membrane formed grooves that would eventually become liquid passages and liquid chambers.

After finishing the development process, the cured dry film film on the substrate was heated at 150°C for 1 hour, and then heated at 50mW/
It was further cured by irradiating it with ultraviolet light with an intensity of c% for 2 minutes.

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

Subsequently, 0,150 yen is applied to the downstream side of the liquid passage of the bonded body, that is, from the installation position of the ejection energy generating element.
m vertically to the liquid path using a commercially available dicing saw (product name: DAD 2H/6 type, DIS
(manufactured by CO) to form an orifice for discharging the recording liquid.

Finally, the cut surface was cleaned and dried, and the cut surface was polished to make it smooth, and a recording liquid supply pipe was attached to the through hole to complete the liquid jet recording head. The resulting recording heads all had liquid passages and liquid chambers that faithfully reproduced the mask pattern, and had excellent dimensional accuracy. Incidentally, the orifice dimensions were in the range of 50±5 μm and the orifice pitch was in the range of 125±5 μm.

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

First, the obtained recording head was subjected to a durability test in which it was immersed in a recording liquid having the following compositions at 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 Plaque 15 (=70/201515 parts by weight) pH=8.0
2) H20/ethylene glycol/N-methylpyrrolidone/C,I Direct Blue 199” (=60/25
/1015 parts by weight) pH=9.03) H20/ethylene glycol/triethylene glycol/C,1,
Acid Red 94*5 (=60/25/1015 parts by weight) pH=7.04) H20/diethylene glycol/C,1, Direct Black 154 (=75/2015 parts by weight) pH=lo, 0Note) $ 1 to $S are water-soluble dyes, and caustic soda was used to adjust the pH.

For each recording liquid, five recording heads were subjected to a durability test.

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

Separately, each of the 10 recording heads obtained was attached to a recording device, and a recording signal of 10' pulses was continuously applied to the recording head for 14 hours using the recording liquid. A printing test was conducted. With respect to any of the recording heads, almost no deterioration 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.

Synthesis Example 2 (1) Synthesis of a butadiene polymer having a number average molecular weight of about 10,000 or more.

1,2-polybutadiene containing carboxyl groups at both ends (
150 g of Mnl, 500) was placed in a Mitsuro flask and dissolved with 180 g of butyl acetate. 0.07 g of t-butylhydroquinone was added as a polymerization inhibitor, and the temperature of the solution was 1.
The temperature was raised to 10°C. 1.6 using a dropping funnel
23 g of -hexanethiol diglycidyl ether was added dropwise over 5 hours, and the mixture was further stirred at 110° C. for 10 hours to react. Disappearance of unreacted epoxy groups was confirmed by IR method. The obtained polymer solution had high viscosity.

The number average molecular weight determined by GPC method is 45,000,
The weight average molecular weight was 230,000. When the butyl acetate was evaporated, a tack-free resin coating was confirmed.

(2) Synthesis of methacryloylated polybutadiene.

1,2-polybutadiene containing carboxyl groups at both ends (
Mn 1,000) 100g was put into a Mitsuro flask and dissolved with 400g of butyl acetate. 0.1 g of t-butylhydroquinone was added as a polymerization inhibitor, and the temperature of the solution was raised to 100°C. Using a dropping funnel, 25.6 g of glycidyl methacrylate was added dropwise over 5 hours. Further, stirring was continued for 5 hours at 100°C to cause reaction.

Disappearance of unreacted epoxy groups was confirmed by IR method.

Example 2 65 g of the butadiene polymer obtained in Synthesis Example 2 (1).

Methacryloylated polybutadiene 2 obtained in the same (2)
The same procedure as in Example 1 was performed except that 0 g and 5 g of 1,2-polybutadiene (Mn 1,500) having carboxyl groups at both ends, 5 g of 1.4-divinylbenzene, and 5 g of methacrylic acid were dissolved in 400 g of methyl ethyl ketone. .

The obtained orifice size was in the range of 50±6 μm, and the orifice pitch was in the range of 125±6 μm.

The quality and durability of the recording head prototyped using the above composition and long-term use were also satisfactory, similar to those in Example 1.

Synthesis Example 3 (1) Synthesis of a butadiene polymer having a number average molecular weight of about 10,000 or more Same as (1) of Synthesis Example 1.

(2) Synthesis of acryloylated and methacryloylated polybutadiene 1,2-polybutadiene containing hydroxyl groups at both ends (M nl
, 000) was put into a Mitsuro flask and dissolved with 450 g of butyl acetate. 0.05 g of hydroquinone was added as a polymerization inhibitor, and the temperature of the solution was raised to 90°C. Using a dropping funnel, 52.4 g of methylene bis(4-cyclohexyl isocyanate) was added dropwise over 5 hours. The mixture was further stirred at 90° C. for 5 hours to allow the reaction to proceed. Disappearance of unreacted hydroxyl groups was confirmed by IR method.

11.6 g of 2-hydroxyethyl acrylate and 13.0 g of 2-hydroxyethyl methacrylate were added dropwise to the above-mentioned solution of polybutadiene with isocyanate terminals using a dropping funnel at 90 DEG C. over 5 hours. The mixture was further stirred at 90 degrees for 5 hours to allow reaction. Disappearance of isocyanate groups was confirmed by IR method.

Example 3 65 g of the butadiene polymer obtained in (1) of Synthesis Example 1.

Acryloylated polybutadiene 25 obtained in the same (2)
g and 10 g of 1,2,4-trivinylcyclohexane
The same operations as in Example 1 were carried out except that the following were dissolved in 400 g of methyl ethyl ketone.

The obtained orifice size was in the range of 50±5 μm, and the orifice pitch was in the range of 125±5 μm.

The quality and durability of the recording head prototyped using the above composition and long-term use were also satisfactory, similar to those in Example 1.

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

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

During the durability test, Vacrel was used as a dry 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, as a dry film, Photoc 5R-3
When using 000, each of the recording liquids l) to 4)
Peeling was observed at 00 hours.

[Brief explanation of the drawing]

1 to 6 are schematic diagrams for explaining the liquid jet recording head of the present invention and its manufacturing method. 1・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・Board 2...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・Discharge energy generating element 3・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・Resin layer 3H・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・Resin cured film 4・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・Photomask 4
P・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・Mask pattern 6
-1・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・Liquid chamber 6-2・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・Liquid passage 7・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・Cover 8・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・Through hole 9・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
Orifice 10・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・ Supply pipe lθ (b) ■Figure 1 (b> Figure 6)

Claims (5)

[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 the active energy rays to A liquid jet recording head formed by forming a cured region of a composition and removing an uncured region from the layer, wherein the resin composition has a number average molecular weight of about 10.
,000 or more, and at least one liquid polybutadiene (b) having an average of 1.5 or more acryloyl groups and/or methachlor groups in the molecule. A liquid jet recording head characterized by: (2) In the active energy ray-curable resin composition, the weight ratio of component (a) to component (b) is (a) component: (
The liquid jet recording head according to claim 1, wherein the component b) is 20 to 80:80 to 20. (3) In the active energy ray-curable resin composition, 0 parts by weight of the total of components (a) and (b)
．． Claim 1 containing 1 to 20 parts by weight of a radical polymerization initiator that can be activated by active energy rays.
) or 2. The liquid jet recording head according to item 2. (4) With respect to 100 parts by weight of the total amount of components (a) and (b) in the active energy ray-curable resin composition,
The liquid jet recording head according to any one of claims 1 to 3, which contains 0.1 to 15 parts by weight of a radical polymerization initiator that can be activated by the action of heat. (5) In the active energy ray-curable resin composition (
For 100 parts by weight of the total amount of component a) and component (b),
The liquid jet recording head according to any one of claims 1 to 4, containing 1 to 100 parts by weight of a monomer having an ethylenically unsaturated bond.