JP2003277472A - Epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition having water repellency and suitable as a water repellent or a water-repellent coating material applied to a site having contacting chance with a solution or material containing a component damaging film-forming properties and adhesive properties of the water repellent. <P>SOLUTION: The epoxy resin composition comprises at least (i) a first epoxy resin having at least one water repellency-imparting group and two or more alicyclic epoxy groups in one molecule, and also having 8,000-22,000 number average molecular weight and 3.5-5.0 degree of dispersion, (ii) a second epoxy resin having at least one water-repellency-imparting group and two or more alicyclic epoxy groups in one molecule, and also having 2,500-8,000 number average molecular weight and 1.5-3.0 degree of dispersion, and (iii) a cationic polymerization catalyst. <P>COPYRIGHT: (C)2004,JPO

Description

Description: BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention
Or surface treatment to impart ink repellency
Curable epoxy resin composition, especially UV
Forming a coating film by irradiation
Epoxy resin composition, surface treatment method using the same
Method, ink-repellent treatment using the epoxy resin composition
Liquid jet recording head and liquid jet recording apparatus using the same
About. 2. Description of the Related Art Conventionally, in various fields, water resistance and repellency have been improved.
Apply water-repellent paint to members that require ink
Methods for imparting water-repellency and ink repellency are generally known.
In addition, resin materials and paints used in the method have been developed.
For example, it has a fluoropolyolefin or perfluoro group.
Coatings made of fluorinated paints, both thermally and chemically
Extremely stable, weather resistance, water resistance, chemical resistance, solvent resistance
Excellent releasability, excellent releasability, friction resistance and water repellency
It is widely used for various purposes. On the other hand, a small amount of liquid such as ink is
Discharge as droplets and attach to paper etc. to form records and images
Liquid jet recording heads that perform
Smaller droplets, higher drive frequency
The number and the number of nozzles continue to improve. Follow
To maintain the nozzle surface always in the same surface condition.
Is becoming increasingly important. However, using existing materials, the nozzle table
Selectively or putter to prevent ink from adhering to the surface
It is difficult to perform a surface treatment precisely in the shape of a circle. The reason
The reason is that the fluorine-based paint has properties like photoresist
In order to provide
Material, but such compounds must be
Sometimes molecular design to have water and ink repellency
First, there is great difficulty. [0005] If a surface treatment is performed using an existing fluorine-based material,
Even if it does, the surface properties can be maintained for a long time
Thus, it is necessary to design the coating structure. Such
Patterned surface treatment materials with performance are described below
Liquid jet recording head (inkjet printing
Is very valuable for surface treatment. That is, the ink is made to fly in small droplets,
In the inkjet recording system that performs recording, the ejection port
(Hole) is designed to have the following performance
Preferably. (1) The remaining ink in the ink column that has been turned into droplets quickly
Re-stored in the nozzle. (2) Ink droplets adhering to the surface of the ejection port
That can be easily swept out by the operation. (3) Scratch resistance in cleaning operation and paper conveyance
Be superior. (4) Repeated droplet formation and ink refill
To the meniscus (see Figs. 1, 2 and 3)
) Is formed. (5) Make sure that the normal direction of the meniscus is the discharge direction.
When. (6) Even if the ink has low surface tension or negative pressure
Low enough to form a meniscus
Having an adequate interfacial tension, that is, a contact angle. These various required performances are required for the discharge port.
The reason is that, in the liquid jet recording head,
If recording liquid such as ink has adhered to the
Displacement occurs in the ejection (flying) direction of the ejected droplets, resulting in high accuracy
Directly related to the printing performance, which makes it impossible to print with
Because. Discharge port that causes such displacement in the discharge direction
An outlet is formed to prevent liquid from adhering to the vicinity.
There is known a method of performing a water repellent treatment on an exposed surface. [0008] As prior art related to these, for example,
For example, polymers having fluoroacetyl groups and silazane groups
It is known to perform ink repellent processing on
Reference 1). On the other hand, a printer that applies the liquid jet recording method
With the high demand for image recording by
The characteristics required for are also becoming higher.
Such a recording liquid is capable of dissolving or dispersing the contents.
In order to further improve the qualification, the pH is adjusted to 7 to 11 with a base.
Is often adjusted for the
Adopts structural material with excellent alkali resistance and hydrolysis
Is preferred. [0009] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2-39944 [0010] However, there is a problem with polarity.
Recording liquids containing organic solvents or high pH
When recording liquid is used, it is ejected for the purpose described above.
Water repellent applied to the surface treatment of the mouth is used for the recording liquid
Solvent components, especially polar organic solvent components.
Therefore, the film-forming properties of the water-repellent film and the adhesion to the applied members
The water-repellent coating is peeled off, and the water-repellency of the discharge port surface is reduced.
Sometimes lost. [0011] Accordingly, the object of the present invention is to provide a polar solvent
In addition, solutions containing components that impair the film-forming properties and adhesion of the water-repellent agent
Water repellents or repellents that apply where there is a chance of contact with the substance
Epoxy resin composition suitable for use as a water-based paint
To provide. Also, the purpose of the present invention is to always use the same surface
Epoxy resin set capable of surface modification that can maintain its state
It is to provide a product. Another object of the present invention is to
Using such an epoxy resin composition, a position on the surface of the article is
To provide a surface treatment method for selectively imparting water repellency.
It is in. [0012] Still another object of the present invention is to provide such an ePO.
By performing the surface treatment of the substrate with the xylene resin composition, the nozzle
The surface can always be maintained in the same surface condition, and the recording medium
Ink adheres to the print head surface even when touching
No dots, resulting in good dot landing accuracy and print quality
Jet recording head and liquid jet recording head capable of maintaining ink for a long time
Recording device. [0013] The above object is achieved by the present invention as described below.
Achieved by That is, [1] the epoxy tree of the present invention
The fat composition comprises: (i) at least one water-repellent group and a ring in one molecule;
Number average molecular weight having two or more aliphatic aliphatic epoxy groups
8,000-22,000 and degree of dispersion 3.5-5.
(Ii) at least one water-repellent group and ring in one molecule
Number average molecular weight having two or more aliphatic aliphatic epoxy groups
2,500-8,000 and dispersity 1.5-3.0
At least a second epoxy resin; and (iii) a cationic polymerization catalyst.
It is characterized by. In the present invention, the [2] water repellency-imparting group may be
Selected from fluoroalkyl groups and alkylsiloxane groups
At least one of the above epoxy resin compositions
is there. The present invention also relates to [3] (i) First Epoxy
Each of the silicone resin and (ii) the second epoxy resin has the following structure.
A monomer unit represented by Formula (a), and the following structural formula
(B) a small amount selected from the monomer units represented by (d)
At least two monomer units of at least one monomer unit
The epoxy resin described above, which is composed of
A composition. In the above formula (a), R ₁ Is a hydrogen atom or a group having 1 to 3 carbon atoms.
R represents an alkyl group; _Two Is an alkylene having 1 to 3 carbon atoms
Z represents a cycloaliphatic epoxy group; In the above formula (b), R _Four Is a hydrogen atom or a group having 1 to 3 carbon atoms.
R represents an alkyl group; _Five And R ₆ Is a methyl group or phenyl
And represents R ₇ ~ R ₉ Are each independently a hydrogen atom, or
Represents an alkyl group having 1 to 3 carbon atoms, n ₁ Is an integer from 1 to 5
The number, x represents an integer from 2 to 100; In the above formula (c), R _Ten , R ₁₁ , R ₁₆ And R ₁₇ Is German
First, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or nitro
R is a group represented by R ₁₂ ~ R ₁₅ Is independently a hydrogen atom,
Or an alkyl group having 1 to 3 carbon atoms, n _Two , N _Three , N
_Five And n ₆ Represents an integer of 1 to 5 each independently; _Four Is
Represents an integer from 2 to 200; In the above formula (d), R ₁₈ Is a hydrogen atom or 1 to 3 carbon atoms
Represents an alkyl group of ₇ Represents an integer of 1 to 5,
Rf represents a fluoroalkyl group. The present invention also relates to [4] an epoxy resin composition
Has the following general formulas (1) and (2):
At least one selected from compounds represented by
The above epoxy resin composition is contained. Further, the present invention provides a method of (5) selectively treating the surface of an article.
(I) applying a film of the epoxy resin composition to the surface of an article
Forming the film; (II) irradiating the film with active energy rays selectively.
(III) dissolving the non-irradiated portion of the coating in the active energy ray.
Irradiating the coating with active energy rays using a dissolvable liquid
Removing part of the article;
This is a surface treatment method. Further, the present invention provides a method for selectively treating the surface of an article.
(I) applying a film of the epoxy resin composition to the surface of an article
A step of forming; (II) a step of polymerizing and curing the coating; and (III) a step of selecting the cured coating obtained in the step (II).
Selectively removing the article.
This is a surface treatment method. The present invention also provides [7] ejection for ejecting liquid.
A liquid jet recording head having a mouth,
The area around the discharge port is covered with a cured film of the epoxy resin composition described above.
A liquid jet recording head,
You. Further, the present invention provides [8] the liquid jet recording head described above.
A liquid jet recording apparatus comprising: A coating comprising the epoxy resin composition of the present invention
(Cured product) has excellent adhesion to various parts and is relatively low temperature
But it can be cured and has excellent physical properties
You. Furthermore, an epoxy resin having a water repellency-imparting group is contained.
This allows the coating to form a water-soluble organic solvent,
The resistance to an organic solvent is greatly improved. Soshi
When a compatibilizer is further included, the
To provide compatibility between the components of the resin composition according to the present invention.
The range of the material composition of the resin composition can be widened. Applying and drying the epoxy resin composition of the present invention
The film formed by drying is activated by active energy rays.
Contains onium salt of activated Lewis acid as catalyst
It is possible to cure in a pattern and
Pattern the surface of the article by removing the coating on the part
Surface treatment is possible. The method of treating the surface in a pattern is, for example,
If the epoxy resin composition is applied to the substrate and dried to form a film
Is formed, and a mask having a desired pattern is formed on the film.
And irradiate with active energy rays, and then use a developer.
To remove uncured portions of the coating.
And can be performed by This pattern processing
Basic process is the same as photolithography
However, as a developing solution, suitable for a coating composed of a resin composition
Select a solvent or solvent composition. Aroma as a developer
Group hydrocarbons, ketones, esters, glycol-A
Ters and the like and mixtures thereof are used. Using the epoxy resin composition of the present invention,
If the method of treating the surface in the shape of
After development, the coating is
Heating the film or further irradiating with active energy rays,
It is desirable to perform so-called post cure. In addition, the present invention
Epoxy resin compositions have relatively high water repellency-imparting groups.
(I) having a first epoxy resin and a relatively low molecular weight
(Ii) a second epoxy resin having a water repellency-imparting group
Excellent film-forming properties,
Excellent patterning characteristics (high resolution and pattern profile
High water repellency) at the same time. Thus, the epoxy resin set of the present invention
Products impair the adhesion of water repellents like polar organic solvents
Apply to a solution or substance that contains
As a water-repellent agent or water-repellent paint
Water-repellent / ink-repellent treatment of the ejection port surface of the head is preferably used
be able to. That is, a book for an ink jet recording apparatus
The effect of the application of the epoxy resin composition of the present invention is that
Selective surface modification used, processing accuracy, and cured film
Durability as a device due to its solid strength and frictional strength,
Water-repellent and ink-repellent properties are based on the water-based ink meniscus.
Retention, cleaning, accuracy of droplet ejection direction, continuous
Characteristics such as persistence in ejection and suitability for starting printing after pausing
It leads to improvement of the nature. Where meniscus holding power
Is the surface tension of the ink at the nozzle tip
And the meniscus during repeated droplet ejection
It refers to the property of recovering and holding the waste in a predetermined position.
If this holding power is low, ink will seep out from the nozzle tip
Or ink droplets ejected with the meniscus retracted
If the volume of the ink is reduced or in extreme cases,
This leads to defects such as loss. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, preferred embodiments will be described.
The present invention will be described in more detail. Epoxy according to the present invention
The resin composition comprises: (i) at least one water repellency-providing group and one ring per molecule;
Number average molecular weight having two or more aliphatic aliphatic epoxy groups
8,000-22,000 and degree of dispersion 3.5-5.
(Ii) at least one water-repellent group and ring in one molecule
Number average molecular weight having two or more aliphatic aliphatic epoxy groups
2,500-8,000 and dispersity 1.5-3.0
At least a second epoxy resin; and (iii) a cationic polymerization catalyst.
You. In the present invention, (i) a first epoxy resin
Fat is a relatively high molecular weight, epoxy resin of the present invention
For coating liquids containing the composition,
Gives good coating suitability to dry films after solvent evaporation
To improve workability. On the other hand, (ii) the second epoki
Since the resin has a relatively low molecular weight, it is considered as an oligomer.
Act, comprising the epoxy resin composition according to the present invention.
Provides excellent patterning properties to the coating. That is,
When the film is patterned, high resolution and professional
The file can get a good pattern. This
(I) the first epoxy resin that acts as a binder
(Ii) a second epoxy that acts as fats and oligomers
The resin must be used in combination and both have water repellency-imparting groups.
This gives the final cured film excellent water repellency
Can be obtained. In the present invention, "minute"
"Diffusivity" means Mw / Mn (Mn = number average molecular weight, Mw = weight)
Weight average molecular weight). In the epoxy resin composition of the present invention,
(I) a first epoxy resin and (ii) a second epoxy resin
The resin is particularly limited as long as it meets the above conditions.
Although not specified, the water repellency-imparting group is
And at least one selected from alkyl siloxane groups
It is preferably a group. Contains such groups
(I) a first epoxy resin and (ii) a second epoxy resin
The fats are each independently represented by the following structural formula (a)
A monomer unit and represented by the following structural formulas (b) to (d)
At least one monomer unit selected from monomer units
Of at least two types of monomer units
It is preferably a oxy resin. [0029] In the above formula (a), R ₁ Is a hydrogen atom or a group having 1 to 3 carbon atoms.
R represents an alkyl group; _Two Is an alkylene having 1 to 3 carbon atoms
Z represents a cycloaliphatic epoxy group. Charcoal
Examples of the alkyl group having a prime number of 1 to 3 include a methyl group and an ethyl group.
Group, propyl group and isopropyl group. Carbon number
Examples of the alkylene group of 1 to 3 include a methylene group,
Examples include ethylene group, propylene group, and isopropylene group.
It is. As the cycloaliphatic epoxy group, epoxycyclo
An alkyl group, specifically, for example, represented by the following structural formula
Epoxycyclohexyl groups such as
Lopentyl group, epoxycyclobutyl group, etc.
You. [0030] In the above formula (b), R _Four Is a hydrogen atom or a group having 1 to 3 carbon atoms.
R represents an alkyl group; _Five And R ₆ Is a methyl group or phenyl
And represents R ₇ ~ R ₉ Are each independently a hydrogen atom, or
Represents an alkyl group having 1 to 3 carbon atoms, n ₁ Is an integer from 1 to 5
The number and x represent an integer of 2 to 100. [0031] In the above formula (c), R _Ten , R ₁₁ , R ₁₆ And R ₁₇ Is German
First, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or nitro
R is a group represented by R ₁₂ ~ R ₁₅ Is independently a hydrogen atom,
Or an alkyl group having 1 to 3 carbon atoms, n _Two , N _Three , N
_Five And n ₆ Represents an integer of 1 to 5 each independently; _Four Is
Represents an integer of 2 to 200. [0032] In the above formula (d), R ₁₈ Is a hydrogen atom or 1 to 3 carbon atoms
Represents an alkyl group of ₇ Represents an integer of 1 to 5,
Rf represents a fluoroalkyl group. Rf is good
Preferably, it has 6 to 12 carbon atoms, more preferably 8 to 1 carbon atoms.
0 linear or branched fluoroalkyl groups
Among such fluoroalkyl groups,
Fluoroalkyl groups are particularly preferred. In the epoxy resin composition of the present invention,
(I) The number average molecular weight of the first epoxy resin is 8,000
~ 22,000, especially 8,500-20,000.
The surroundings are preferable from the viewpoint of the durability of the water-repellent film. In the epoxy resin composition of the present invention,
(Ii) The number average molecular weight of the second epoxy resin is 2,500
The range of -8,000 is the point of patterning property of the cured film.
Is preferred. Then, (i) specific examples of the first epoxy resin
As examples, the structural formulas (A1-1) and (A1-2)
And (ii) the following specific examples of the second epoxy resin:
Shown in the structural formula (A2-1): (I) First epoxy resin used in the present invention
Fat and (ii) the second epoxy resin are each monomer
The monomers corresponding to the units (a) to (d) are prepared according to a conventional method.
It is obtained by copolymerizing at an appropriate monomer ratio.
For example, an epoxy resin containing monomer units (a) and (b)
If it is a fat, a monomer of the following structural formula (a-1) and the following structure
Obtained by copolymerizing a monomer of the formula (b-1)
be able to. In the above formula (a-1), R ₁ Is a hydrogen atom or a carbon number of 1 to
3 represents an alkyl group; _Two Is alk having 1 to 3 carbon atoms
And Z represents a cycloaliphatic epoxy group.
You. [0037] In the above formula (b-1), R _Four Is a hydrogen atom or a carbon number of 1 to
3 represents an alkyl group; _Five And R ₆ Is a methyl group or
A phenyl group; ₇ ~ R ₉ Is independently a hydrogen atom,
Or an alkyl group having 1 to 3 carbon atoms, n ₁ Is 1-5
And x represents an integer of 2 to 100. An epoxy containing the above (a) and (c)
In the case of a resin, the presence of the monomer represented by the above (a-1)
Below, the monomer represented by the following (c-1) is polymerized.
And can be synthesized. In the above formula (c-1), R _Ten , R ₁₁ , R ₁₆ And R ₁₇ Is each
Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or
A nitrile group, R ₁₂ ~ R ₁₅ Are independently hydrogen sources
And represents an alkyl group having 1 to 3 carbon atoms, _Two ,
n _Three , N _Five And n ₆ Represents an integer of 1 to 5 each independently
Then n _Four Represents an integer of 2 to 200. The above formula (c-
1) Medium, R ₁₉ ~ R _{twenty two} Is R _Ten , R ₁₁ , R ₁₆ And R ₁₇ Same as
Righteous, n ₈ And n ₉ Is n _Two , N _Three , N _Five And n ₆ Synonymous with
It is. X is a halogen atom. The compound represented by the formula (c-1) is an example
For example, the method described in Japanese Patent Publication No.
Can be achieved. That is, the following equation (c-1-1) is used.
Diamine and the following formulas (c-1-2) and (c-1-
It can be obtained by reacting with dihalide shown in 3).
Can be. [0040] The above formulas (c-1-1), (c-1-2) and (c-1-
The substituent in 3) is as described in the above section (c-1).
It is. Further, an epoxy resin containing the above (a) and (d)
If it is a resin, the monomer represented by the above formula (a-1)
And a monomer represented by the following formula (d-1)
Can be obtained. In the above formula (d-1), R ₁₈ Is a hydrogen atom or 1 carbon atom
Represents an alkyl group of 3 to 3; ₇ Represents an integer of 1 to 5
And Rf represents a fluoroalkyl group. The epoxy resin composition of the present invention comprises:
(1) an epoxy resin, (ii) a second epoxy resin,
(Iii) The main component is a cationic polymerization catalyst.
Further, it is preferable to further include (iv) a compatibilizer. This
Examples of the compatibilizer (iv) include the following general formula (1) and
And compounds represented by the following general formula (2).
And the epoxy resin composition of the present invention has the following general formula
(Iv) at least one of the compatibilizers (1) and (2)
It is preferable that one of them is included. As a preferred specific example corresponding to the above formula, p = 0
Compound, that is, 2,2-bis (4-glycidyloxy
Phenyl) hexafluoropropane
You. [0043] A preferable specific example corresponding to the above formula is q = 0.
Compound, ie, m-bis- [1- (2,3-epoxy
(Ropoxy) -2,2,2-trifluoro-1- (trif
Fluoromethyl) ethyl] benzene. Formulas (1) and (2)
Although the compound has a fluorinated alkyl group, its chain length
The surface energy of the formed film
Use is small, and water repellency and ink repellency are not great. The above one
The compounds represented by the general formulas (1) and (2) are all
The compounds at both ends of the compounds represented by the general formulas (1) and (2)
Divalent alcohols corresponding to compounds excluding groups containing a oxy group
And epichlorohydrin in a conventional manner.
Is synthesized. The epoxy resin composition of the present invention comprises
(Iii) containing a cationic polymerization catalyst for curing
I have. Compounds used for such purposes are usually
Choose from substances commonly known as curing agents for epoxy resins
Is done. Is the composition of the present invention an epoxy resin composition?
Curing agents such as aromatic and aliphatic amines and acid anhydrides
And can be cured by heating or the like.
However, the composition of the present invention enables particularly low temperature curing.
Lewis activated by active energy rays
Resin to increase reactivity with onium salt of acid
The composition is designed. Then, using the resin composition
Selective substrate surface by photolithography
Especially at high temperatures.
Surface modification of difficult article surface, specifically water repellency of article surface
Designed to be suitable for processing
You. Therefore, in the present invention, the epoxy resin composition is cured.
Cations such as those listed below
A polymerization catalyst is used. Catalysts that can be used in the present invention include:
For example, bis (4-tert-butylphenyl) iodine
Salt, trade name "OPTMER SP-150", "OP
Tomer SP-170 "," Optomer SP-172 ",
"Opton CP-66" and "Opton CP-77"
(All manufactured by Asahi Denka Kogyo). (Iii) Among the cationic polymerization catalysts,
The chemical structure of “Putomer SP-150” is represented by the following formula.
You. Further, the above-mentioned "Optomer SP-170" is formed.
The chemical structure is represented by the following formula. Further, a product name “IRGA” represented by the following structural formula
Click here for "Cure 261" (made by Ciba Specialty)
It can be used as an on polymerization catalyst. The epoxy resin composition of the present invention comprises (i)
Other than the first epoxy resin and (ii) the second epoxy resin
Epoxies on the side chains that function as binder polymers
Acrylic tree copolymerized with acrylic monomer having di-group
Fats, vinyl monomers having cycloaliphatic epoxy groups in side chains
-Polymerized vinyl polymer, cycloaliphatic epoxy
Polyether polymer having a thio group (for example, EHPE
3150; product of Daicel Chemical Industries)
Epoxy polymers that can participate in the bridge reaction may be used in combination.
No. If such a polymer without epoxy group is used,
If used, the physical properties according to the application to which it is applied
It needs to be selected with the intention of adjustment. Such a substance
For example, a bisphenol-type epoxy resin polymer
, The product names "PKHC" and "PKHJ" (Union
Carbide products), poly (ethylene / vinyl acetate)
), Phenolic resin, polycarbonate resin, polyether
Steal resin, polyamide resin, soluble polyimide resin, etc.
A general-purpose polymer compound for paint can be used. As described above, the epoxy resin composition of the present invention
Contains (i) a first epoxy resin; (ii) a second epoxy resin; (iii) a cationic polymerization catalyst; and, if necessary, (iv) a compatibilizer. In the epoxy resin composition of the present invention,
The preferred proportions of these components are as follows. First, (iii) the cationic polymerization catalyst
For the total amount of the epoxy resin composition of 100 parts by weight,
It is preferably in the range of 0.5 to 7 parts by mass. (I)
Combination of first epoxy resin and (ii) second epoxy resin
The proportion depends on the respective softening point and glass transition temperature
So there is no general range. However, in general (i): (ii)
= 10: 90 to 90:10 (mass ratio)
Good. When these compounds have low compatibility with each other
And (iii) the Lewis acid of the cationic polymerization catalyst.
(Iv) Use a compatibilizer because the salt is highly polar
It is often advantageous. (Iv) The compatibilizing agent of the present invention
0 to 100 parts by mass of the total amount of the epoxy resin composition,
Preferably, it is used in the range of 80 parts by mass. The epoxy resin composition of the present invention may be heated or
Performs surface treatment of articles by irradiation with active energy rays.
Can be used to Specifically, the resin of the present invention
The composition is aromatic, aliphatic hydrocarbon, ester,
Dissolved in ether-based, fluorine-based solvent, etc.
ー, spin coater, spray coater, die coater
(Direct coater), screen printing, gravure printing
Apply to the substrate surface using various coating / printing methods such as printing.
Can be. After applying to the substrate surface, heat or activate
Coating formed by irradiation with energy rays
To cure. Active energy ray source used for curing
The emission line spectrum in the wavelength range of 200 to 480 nm
Lamps, laser beams, electron beams, etc. containing large amounts of
You. The epoxy resin composition of the present invention is preferably
Contains a binder component as described above and is a dry solid
Was prepared to give a film of
Perform the same patterning as in the case, and
Water repellent treatment of the position can be easily performed. In this case
Is a coating liquid containing the epoxy resin composition of the present invention,
Apply to the surface by coating etc., remove the solvent and dry the film.
After that, a mask having an appropriate pattern
Irradiate with energy rays or apply a pattern to the coating
Irradiation of active energy rays in the shape of
The developing process is performed in a solvent system capable of dissolving the film. Patterned
If irradiation with energy rays is not sufficient for curing,
It is desirable to perform post-cure curing after the treatment.
Good. Energy sources include heat and microphones
Heat treatment such as wave, active energy such as electron beam and ultraviolet ray
Irradiation is used. According to the surface treatment method of the present invention as described above.
If the coating has excellent adhesion to the substrate and excellent hardness of the coating surface
Water-repellent and oil-repellent treatments provide excellent durability
There is a great advantage that the material can be modified. Also, things
Other methods of position-selectively treating the surface of articles
As described, the epoxy resin composition of the present invention
After forming a film of the product and curing it to form a cured film,
The cured film is cured using an excimer laser or the like.
There is a method of selectively removing the coating. Liquid jet recording head (ink jet recording
Example of application of epoxy resin composition of the present invention to head)
As the nozzle surface of the liquid jet recording head of the present invention.
Nozzle table by treating with epoxy resin composition
No strong adhesion of ink to the surface
Wipe off attached ink easily by cleaning process
An example of forming a surface having good releasability is given. Mounted on a normal liquid jet recording apparatus
As the cleaning mechanism, there are known a method of wiping ink with a rubber blade, a method of suctioning ink with a pump, and a method of performing idle discharge of ink at a position outside the recording paper. But any of these
Method, the ink column drawn by the ejection pressure is a droplet
Since all the ink does not turn into droplets when
Extra small droplets of ink adhere around the nozzle
Cannot be completely eliminated. So these spontaneously
Dropped or re-sucked inside the nozzle, or easily
If eliminated, there will be no effect on ink ejection, so
is there. According to the epoxy resin composition of the present invention,
It cures even at relatively low temperatures, and has water and oil repellency,
Provides a cured film with excellent adhesion, chemical resistance, and friction resistance
It becomes possible. FIGS. 1 and 2 show the epoxy resin composition of the present invention.
Of the main part of the configuration of a liquid jet recording head to which the present invention is applicable
Is shown. FIG. 1 is a cross-sectional view along the ink flow path,
FIG. 2 is a diagram illustrating a discharge port surface. The recording head 13 generates a discharge energy.
A thermosetting resin composition is formed on a substrate 15 on which a raw device and the like are arranged.
Of a product and / or an active energy ray-curable resin composition
Objects, etc. into a predetermined pattern and at least the flow path
It has a configuration in which members to be formed are laminated and joined. The substrate 15 is made of a material having good heat radiation, such as alumina.
Heat storage layer 19, formed of metal on the surface of a substrate 20 made of a material
Heating resistor layer 18, electrode made of aluminum or the like
17-1, 17-2 and the protective layer 16 were laminated in this order.
It has a configuration, and is configured to energize the electrodes 17-1 and 17-2.
Therefore, the portion of the heating resistor layer 18 where the electrodes are not stacked
Discharge energy formed in a portion (a portion in a region indicated by n).
The heat generating element generates heat, causing ink located above
Heat energy is applied. At the time of recording, the ink 21 is
Filled up to the discharge port (orifice) 22 which is a fine opening
In this state, the electrodes 17-1 and 17-1 correspond to the recording signal.
When electricity is supplied to 7-2, the area indicated by n rapidly generates heat.
Then, bubbles due to film boiling are generated in the ink 21 in contact therewith.
When the ink 21 is generated, the ink 21
It is discharged as 24 and flies toward the recording medium 25
You. In the liquid jet recording head according to the present invention,
At least around the discharge port opening 22 on the discharge surface 29 (FIG. 2)
In the cured film comprising the epoxy resin composition of the present invention,
Applied as a water-repellent / ink-repellent agent, droplets adhere to this surface
To prevent a shift in the droplet ejection direction.
You. Moreover, the curing comprising the epoxy resin composition of the present invention
The coating not only has excellent adhesion to the ejection surface 29.
The ink contains organic solvents, especially polar organic solvents.
The water repellency and adhesion may be impaired
There is no. FIG. 3 shows a multi-head as shown in FIG.
FIG. 2 is a diagram illustrating an example of a liquid jet recording apparatus incorporating the device.
In FIG. 3, reference numeral 61 denotes a blade as a wiping member
One end of which is held by a blade holding member.
To form a fixed end and form a cantilever. blade
61 is located at a position adjacent to the recording area from the recording head 65.
In the case of this example, the moving path of the recording head 65 is provided.
It is held in a protruding form. 62 is a cap
At the home position adjacent to the blade 61.
Moves in the direction perpendicular to the direction of movement of the recording head 65,
A structure is provided in which the capping is performed in contact with the discharge port. Further, 63 is provided adjacent to the blade 61.
Ink absorber, and, like the blade 61,
The pad 65 is held in a protruding form in the movement path of the pad 65. Up
The blade 61, the cap 62, and the ink absorber 63
The ejection recovery section 64 is constituted by the
Moisture and dust from the ink ejection port surface by the ink absorber 63
Is removed. Reference numeral 65 denotes recording for recording by a liquid jet method.
In the head, for example, heat energy as shown in FIGS.
And discharges a liquid such as ink. 6
6 mounts the recording head 65 and moves the recording head 65.
This is a carriage for performing. The carriage 66 is a guide
It is slidably engaged with the shaft 67, and a part of the carriage 66 is
Connected to a belt 69 driven by a motor 68 (not shown).
Shown). As a result, the carriage 66 moves the guide shaft 6
7, the recording area by the recording head 65
And an area adjacent thereto. Reference numeral 51 denotes a paper feed for inserting a recording medium.
And 52, a paper feed roller driven by a motor (not shown).
Is a dealer. With these configurations, the recording head 65
The recording medium is fed to the position facing the ejection port surface,
As the paper advances, the paper is discharged via the paper discharge roller 53.
You. In the above configuration, the recording head 65 performs recording.
When returning to the home position at the end of
Of the print head 65
Although the blade 61 is retracted from the movement path,
Protruding inside. As a result, the ejection port of the recording head 65
The surface is wiped. The cap 62 is a recording head.
When performing capping by contacting the discharge port surface of No. 65,
The cap 62 projects into the movement path of the recording head 65
To move. When the recording head 65 starts recording from the home position,
When moving to the recording start position, the cap 62 and the blade
61 is located at the same position as the position during wiping described above.
You. As a result, even in this movement, the ejection of the recording head 65 is performed.
The exit surface is wiped. The above-mentioned recording head 65
Move to the home position when recording ends or when ejection is recovered.
Instead, the recording head 65 moves the recording area for recording.
Home position adjacent to the recording area at a predetermined interval while moving
And the wiping is performed with this movement.
Is In the ink jet recording apparatus, color recording
In the case of, for one head, for cyan, magenta,
A print head with low and black ejection ports arranged in parallel
It can be performed using: Independent recording heads for each color
And may be used in parallel. In these cases, each
Discharge of color may be performed from one discharge port, or for each color.
About two or more discharge ports at the same time
Even if droplets of the same color adhere to the recording medium at the same time,
Good. The liquid jet recording head according to the present invention
The repellent comprising the epoxy resin composition of the present invention described so far.
Surface treated with ink treatment material,
Has the chemical properties shown,
Cleans very little or very little ink
Removed by the wiping blade. Therefore the printing
Real sustainability is dramatically increased. When using the epoxy resin composition of the present invention,
A specific method will be described below. Book
Applying a film comprising the epoxy resin composition of the present invention to the active energy
In the case of curing with a negative wire, as described above,
Add photocationic polymerization catalyst that releases Lewis acid by light
Add and use. If heat curing, use boron trifluoride.
A Lewis acid such as an amine catalyst may be added for use. <Coating Method> The present invention used in this method
Epoxy resin composition is dissolved in an organic solvent
Used as a coating solution. When the film thickness is as thin as several μm
In case, roll coater, spin coater, spray coater
And die coaters (direct coaters)
Coating liquid can be applied using the precision coating equipment
You. Also, once apply the above coating solution on release paper and form a film.
Into a dry film, and laminating the dry film
To form a coating on the surface of the substrate
It is also possible. The first method for treating the substrate surface in a pattern
The method comprises: (I) forming a coating on the surface of the article as described above.
Process, and then (II) locating an active energy ray on the film
Selective (e.g., a mask having the desired pattern on the coating)
(III) and then the above active energy
Using a liquid (developer) that can dissolve the non-irradiated part of the energy beam
Removing the active energy ray non-irradiated portion of the coating
(Development processing). these
Basic process is the same as photolithography
However, as a developer, the epoxy resin composition of the present invention
A solvent or solvent composition appropriate for the coating
is necessary. As the developer, for example, aromatic hydrocarbon
Elements, ketones, esters, glycol ethers, etc.
And mixtures thereof. The above coating
Heat or activate after development to complete the reaction.
It is desirable to further perform irradiation with energy rays. A second method of treating the surface of the substrate in a pattern
The method comprises the steps of (I) applying the coating liquid to a substrate, drying the coating liquid,
First step of film formation, (II) Active energy promoting polymerization
The coating is cured by a method such as irradiation of
Second step, (III) Select desired part of cured film
(E.g., irradiation with collapsing active energy rays)
By performing the third step in this order.
Do it. The wavelength of the active energy ray that promotes polymerization is
UV light with abundant light of 250-480 nm is used
You. As a decaying active energy ray, the wavelength is 210
nm or less, an excimer laser, or the like is used. The above
In order to complete the curing of the coating in the method 2 as well,
At any stage, heat treatment of the coating or the active energy of polymerization
It is desirable to irradiate radiation. Thus, the epoxy resin composition of the present invention
Is a component that impairs the adhesion of the water repellent, such as a polar organic solvent.
Repellent applied where there is a chance of contact with liquids or substances containing
Use as a liquid agent or water-repellent paint,
Suitable for water-repellent and ink-repellent treatment of the discharge port surface
Can be. EXAMPLES Next, the present invention will be further described with reference to Examples and Comparative Examples.
explain in detail. It should be noted that "%" in the text is not particularly noted
Unless otherwise indicated, it is based on mass. Examples of the composition of the composition of the present invention are as follows.
Shown below. The following ratio indicates the mass ratio of the solid content. (Composition Example 1) Resin A1-1: A2-1: Catalyst 1 = 32: 64: 4 (actual
(Used in Example 1) (Composition Example 2) Resin A1-1: A2-1: Catalyst 2 = 47: 47: 6 (actual
(Used in Example 2) (Composition Example 3) Resin A1-2: A2-1: Catalyst 2 = 33: 65: 2 (actual
(Used in Example 3) (Composition Example 4) Resin A1-1: A2-1: C-1: catalyst 2 = 35: 3
0: 30: 5 (used in Example 4) (provided that the above C-1 is represented by the general formula (1) where p =
0, that is, 2,2-bis (4-glycidyloxy
Phenyl) hexafluoropropane. The catalysts 1 and 2 were as follows:
Was used. A1-1, A1-2 and A used above
2-1 has the following structure. (Examples 1 to 4)
Each was treated with the solvent diethylene glycol dimethyl
-Toluene / toluene mixed solvent (mass ratio 1: 1)
After dissolution, a solution having a concentration of 30 to 40% was prepared. these
The solution was made of a silicon having a thermal oxide film of 5 μm thickness.
To a thickness of 1 to 3 μm on the wafer substrate
The coating was performed using a spinner. The substrate is then
Dry on a hot plate for 5 minutes to remove the solvent.
Was. An ultraviolet irradiation device using a high-pressure mercury lamp was applied to these four substrates.
2 J / cm ^Two Of the amount of ultraviolet rays was irradiated. next
Heat in a 150 ° C oven for 15 minutes to complete the curing reaction
Thus, four substrates of Examples 1 to 4 were obtained. (Evaluation) The four sheets of Examples 1-4 obtained above were evaluated.
The following measurements were performed using the substrate and evaluated respectively.
Table 2 shows the measurement results. <T1: Measurement of contact angle> Pure water, 10% aqueous solution of oleic acid
Solution, glycerin 20% aqueous solution, and surfactant 1% aqueous solution
Liquid (polyoxyethylene nonyl phenyl ether; HL
B = 10), the cured film of each substrate was
The static contact angle was measured using a contact angle meter (trade name: CAX-15).
0; Kyowa Interface Science Co., Ltd.) at room temperature. <T2: Contact angle after immersion in dye aqueous solution
(Advance contact angle, receding contact angle)> Water-soluble dye (die
Rec Black 168) (pH = 10.
In 3), each of the substrates was immersed at 60 ° C. for 7 days. afterwards
After washing and drying each substrate with pure water,
Then, for each of the same liquids used for the measurement of T1,
Advancing contact angle and receding contact angle using the contact angle meter described above.
And measured. Also, the measurement of these contact angles is
Method was used. <T3: Long-Term Printing Durability> As shown in FIG.
As shown in FIG.
A positive photoresist is formed on the substrate 41 to be processed.
(Product name: PMER AR-900, manufactured by Tokyo Ohka Kogyo)
Is spin-coated to a film thickness of 30 μm, and oven
Prebake at 90 ° C for 40 minutes in the resist
Layer 42 was formed. Next, as shown in FIG.
Exposure through desired mask 43 to make exposed part soluble in developer
And develop it with a predetermined developer to develop the resist film.
As shown in FIG. 4 (c), a portion that will later become a discharge port (flow path)
44 remained. Next, on the resist pattern 44, FIG.
As shown in (d), as a material for forming a flow path,
Composition of main agent and curing agent (Fujicure FXK830, modified
Aliphatic amine, manufactured by Fuji Kasei Kogyo Co., Ltd.)
Agent = 100/50 (mass ratio)
The channel forming material layer 45 was laminated with a layer thickness. [0084] After laminating the flow path forming material layer 45 (FIG. 4)
(D)), left at 25 ° C. × 24 hours, and further 100 ° C. × 2
The heat curing treatment was performed for a long time. Then, obtained this way
Soak the laminate in a 3% aqueous sodium hydroxide solution
Dissolve and remove the strike pattern 44, wash and dry
A body jet recording head was obtained. The liquid jet record thus obtained
Epoxy resin composition of Examples 1 to 4 on ejection surface of recording head
Objects were applied individually, and this was applied to 8 J / cm ^Two UV exposure and
At 150 ° C. for 1 hour. Further, a predetermined voltage is applied to the liquid jet recording head.
Perform wiring and install it in the printer.
/ Food black 2 (water-soluble black dye) / N-methyl
Pyrrolidone = 70/15/3/12 (parts by mass)
Long-term printing durability test was conducted using inkjet ink.
Was. In the long-term printing durability test, the impact between the document and the ink
A pattern for evaluating accuracy was printed on 100 sheets.
Then, reduce the dot disorder for the final print sample.
The evaluation was based on the above criteria. This result was set to T3-1. Evaluation A: There is no disturbance in the dot position, and the characters are clear. Evaluation B: Although the dot position is slightly disturbed, character quality is improved.
Has a minor effect. Evaluation C: Disturbance in dot position is considerable, and characters are clear
Is declining. Evaluation D: Missing dots and significant deterioration of character quality occurred
ing. The pre-print after use in the long-term printing durability test
Observe the print head surface and determine the amount of ink
Was evaluated. This result was set to T3-2. Evaluation A: Almost no ink droplets on the nozzle surface. Evaluation B: Small ink droplets are seen on the nozzle surface. Evaluation C: There is a large ink droplet near the nozzle orifice. Comparative Example 1 Epoxy used in Example 1
Instead of the resin composition, Fluorad (Fluorad) ^TM )
FC-722 (fluoro coating agent; Sumitomo 3E)
Is applied to the discharge port surface and dried at 100 ° C for 30 minutes.
To perform a surface treatment. The substrate is made under these curing conditions.
And the obtained substrate is the same as in Example 1.
T1 to T3 were evaluated by the method. Table 2 shows the results.
It was shown to. Comparative Example 2 Epoxy used in Example 1
Instead of a resin composition, a fluorine-containing structure represented by the following formula
Other than using epoxy resin bisphenol AF
In the same manner as in Example 1, a substrate was obtained. Soshi
Then, the obtained substrates were evaluated for T1 to T3.
Was. The results are shown in Table 2. [0091] [0092] As described above, as shown in Table 2, the epoch of the present invention
The coating film of the example comprising the xy resin composition has a high contact angle,
In addition, the durability is good. Also, ink and length
Ink on the print head surface
No landing, resulting in good dot landing accuracy, printed products
It turns out that the position can be maintained for a long time. (Example 5) Composition used in Examples 1 and 3
Examples 1 and 3 were applied to molded polyethersulfone plates.
Use a pinner to adjust the film thickness after solvent evaporation to about 2 μm.
And dried. High pressure mercury on these substrates
10 J / cm in total from the lamp ^Two Irradiation of light to cure the film
Was performed. Next, the beam converges on this substrate to a beam diameter of 5 μm.
Excimer laser light having a wavelength of 195 mm
Irradiation was performed from above to perform a nozzle boring process. Drilling
Is performed well, there is no decomposition residue at the edge,
It was in a processed state. As a result, the composition of the present invention
Excellent suitability for X-ray laser processing
I understand. As described above, according to the present invention,
Solutions and substances containing components that impair the film-forming properties and adhesion of the water repellent
Water-repellent or water-repellent coating applied to places where there is contact with
A resin composition suitable as a material is provided. Also, in the present invention
According to this, a surface modification treatment that can always maintain the same surface state
A possible resin composition is provided. Further, according to the present invention, such a resin composition
Nozzle surface is always the same by treating the substrate surface with
The surface condition can be maintained.
There is no ink adhesion on the print head surface, resulting in
Good dot landing accuracy and long print quality
Inkjet recording head and liquid jet recording device
Provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a main part of an example of a configuration of a liquid jet recording head. FIG. 2 is a diagram illustrating a discharge port surface. FIG. 3 is a diagram illustrating an example of a liquid jet recording apparatus incorporating a multi-head. FIG. 4 is a diagram illustrating a surface treatment method of the present invention. [Description of Signs] 13: Recording head 14: Ink groove 15: Substrate 16: Protective layers 17-1, 17-2: Electrode 18: Heating resistor layer 19: Heat storage layer 20: Base 21: Ink 22: Orifice 23: Meniscus 24: Small droplet 25: Recording medium 29: Discharge surface 41: Substrate 42 to be processed: Resist layer 43: Mask 44: Resist pattern 45: Flow path forming material layer 46: Discharge port surface 51: Feeding section 52: Paper feed roller 53: Discharge roller 61: Wiping member 62: Cap 63: Ink absorber 64: Discharge recovery unit 65: Recording head 66: Carriage 67: Guide shaft 68: Motor 69: Belt

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Hiromichi Noguchi             3-30-2 Shimomaruko, Ota-ku, Tokyo             Within Non Corporation F-term (reference) 2C057 AF93 AG07 AP60                 4J015 AA02                 4J027 AF05 BA07 CB09 CC02 CD08                 4J036 AA05 AK08 GA22 HA01 JA01                       JA15 KA01                 4J100 AL08P AL08Q BA81Q BB18Q                       BC54P CA04 DA01 DA04                       JA01

Claims (1)

Claims: 1. (i) having at least one water repellency-providing group and two or more cycloaliphatic epoxy groups in one molecule;
A first epoxy resin having a number average molecular weight of 8,000 to 22,000 and a dispersity of 3.5 to 5.0; (ii) at least one water repellency-providing group and cycloaliphatic epoxy group in one molecule Having a number average molecular weight of 2,500 to 8,000 and a dispersity of 1.5 to 3.0.
An epoxy resin composition comprising at least: a second epoxy resin; and (iii) a cationic polymerization catalyst.