JP4599053B2 - Inkjet recording head - Google Patents

Description

  The present invention relates to an ink jet recording head, an ink jet recording apparatus using the same, and a polymerizable composition for water repellency treatment. In particular, the periphery of the ink discharge portion of the head is subjected to ink repellency treatment and is excellent in water repellency and wear resistance. The present invention relates to a recording head excellent in print quality of an obtained image.

  2. Related Art An ink jet recording apparatus that performs recording by discharging ink (recording liquid) from a discharge port of a recording head is known as an excellent recording apparatus in terms of quietness and high speed recording. The print quality of the image obtained by the recording head greatly depends on the positional accuracy of the dots formed by ink droplets on the recording paper. The dot position accuracy depends on the flying direction of the ink droplets ejected from the ejection port of the recording head. In order to keep the flying direction constant, it is important to make the peripheral edge of the ejection port uniform and stable during ink droplet ejection. Specifically, the surface of the recording head including the peripheral edge of the ejection port is water repellent ( It is useful to perform an (ink repellent) treatment. Further, when a foreign matter such as ink or paper adheres to the peripheral edge of the discharge port subjected to the water repellent treatment, a scraping operation is performed with a cleaning member such as a blade. At this time, the water repellent treatment is required to have durability against ink or chemical components contained therein and durability against friction such as rubbing operation.

  As a water repellent treatment method, there is an example in which the periphery of the recording head discharge port is treated with fluoroalkylalkoxysilane to make it water repellent (for example, see Patent Document 1). In such a case, a treatment that may destroy the material forming the discharge port, such as heating for a long time or in a high-pH solution, is required, and durability against friction such as a wiping operation is insufficient. In order to enhance the durability, as a method for strengthening the fixation of the silane coupling agent, an intermediate layer formed from an organosol containing fine oxide particles is provided between the base material and the silane coupling agent to provide durability. An example of imparting water repellency (see, for example, Patent Document 2) has been proposed, but the problem of requiring high temperature in the treatment process has not been solved.

  In addition, as the water repellent layer by applying and drying the fluoropolymer solution, a material having high water repellency can be generally selected, but the durability is poor because the strength of the film itself is insufficient. By forming a water-repellent layer in which inorganic fine particles are added to a water-repellent material as a lower layer, and further forming a water-repellent layer with a similar water-repellent material that does not contain an inorganic material in the upper layer, the effect of the inorganic fine particles with high hardness An example of increasing durability by increasing the film hardness (see, for example, Patent Document 3) is shown. When a resin having a high fluorine content is used to enhance the water repellency, the upper layer and the lower layer The adhesion was poor and it was difficult to achieve both high water repellency and durability.

In addition, there is an example of treatment with a treating agent containing a fluorine-containing resin and a blocked isocyanate (see, for example, Patent Document 4), and high scratch resistance has been reported, but the reactivity of the blocked isocyanate is poor. Since the heat treatment for a long time at a high temperature (160 ° C.) is necessary, there are problems such as destroying the constituent material of the head as in the above example. Due to the low bifunctionality and short distance between reactive groups, it is difficult to increase the cross-linking density of the film according to the amount of blocked isocyanate added. It was difficult to manufacture.
Further, there is an example of a polymer film having a fluorine-containing polymer chain, in which the fluorine-containing polymer chain forms a physical aggregate (for example, see Patent Document 5), and has high water repellency. It has been reported. However, in order to give strength by crosslinking, it is necessary to increase the content of reactive groups such as epoxy groups and hydroxyl groups, which inevitably makes the cured film hydrophilic, so strength and water repellency It was difficult to achieve both.

  On the other hand, when inorganic materials are blended with organic materials, in applications such as adhesives, exterior paints, hard coats, and anti-reflective coatings, there are improvements in scratch resistance, strength of cured products, and adhesion to other materials that come into contact. It is being considered. Among these, in combination with polymerization-curing organic materials, alkoxysilanes containing a polymerization group and / or hydrolysis condensates thereof have attracted attention. For example, a combination of a specific polyalkoxypolysiloxane and a polymerizable silane coupling agent has been proposed (see, for example, Patent Document 6), but the reaction between the polyalkoxypolysiloxane and the polymerizable silane coupling agent is sufficient. Since it is difficult to perform and the introduction ratio of the polymerizable group is low, the scratch resistance and strength of the cured product are not sufficient, and the storage stability of the composition liquid is not sufficient.

In short, the currently proposed technology has not yet proposed an ink jet recording head that has both friction resistance and water repellency (ink repellency) as required. There is a demand for the development of an ink jet recording head having excellent print quality and excellent long-term friction resistance.
JP 56-895669 A Special No. 3161106 JP-A-9-11495 Special No. 3382416 JP 2001-233972 A JP-A-9-169847

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention provides a polymerizable resin composition for forming a water repellent resin film that can be easily formed at a temperature of 120 ° C. or less on the discharge port surface, and a repellent composition comprising the polymerizable resin composition. An object of the present invention is to provide an ink jet recording head excellent in water resistance and abrasion resistance.

As a result of intensive studies to solve the above problems, the inventors of the present invention form a hydrophobic film using a polymerizable resin composition comprising a substance derived from a specific organosilane and a fluorine-containing compound. It has been found that the above object can be achieved.
That is, the means for solving the above problems are as follows.
(1) In an ink jet recording head having an ejection port for ejecting a recording liquid and having an ink repellent treatment at least around the ejection port, the ink repellent treatment portion of the recording head includes:
(A) a hydrolyzate of organosilane containing a radical polymerizable group and / or a partial condensate thereof;
(B) viewing including the crosslinked fluorine-containing compound and contains at least a polymerizable resin composition,
The hydrolyzate of organosilane and / or its partial condensate containing a radically polymerizable group (a) has a mass average molecular weight of 1000 to 20000 when the mass average molecular weight is 300% by mass or more. An ink jet recording head , wherein the component is 80% by mass or more and the value of T3 / T2 is a value of 0.2 to 3.0 .
(T3 / T2 represents the ratio of the peak area (T3) when no silanol group remains and the peak area (T2) when one silanol group remains, calculated from the peak intensity of silicon NMR.)
(2) In an ink jet recording head that has a discharge port for discharging a recording liquid and at least a portion around the discharge port is subjected to ink repellent treatment, the ink repellent treatment portion of the recording head includes:
(A) 'a polyorganosiloxane containing radically polymerizable groups;
(B) viewing including the crosslinked fluorine-containing compound and contains at least a polymerizable resin composition,
The polyorganosiloxane containing the (a) ′ radical polymerizable group has a weight average molecular weight of 300 or more as 100% by weight, and a weight average molecular weight of 1000 to 20000 is a component of 80% by weight or more. An ink jet recording head having a T3 / T2 value of 0.2 to 3.0 .
(T3 / T2 represents the ratio of the peak area (T3) when no silanol group remains and the peak area (T2) when one silanol group remains, calculated from the peak intensity of silicon NMR.)
( 3 ) The inkjet recording head according to (1) or (2) , wherein the organosilane containing the radical polymerizable group is a compound represented by the following general formula (1).

(R ²¹ represents hydrogen or a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, fluorine or chlorine. Y represents a single bond or an ester group, an amide group, an ether group or a urea group. L represents a divalent linkage. Represents a chain, n represents 0 or 1. R ²² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and Xh represents a hydroxyl group or a hydrolyzable group.
( 4 ) The inkjet recording head according to any one of (1) to ( 3 ), wherein the polymerizable resin composition further contains inorganic fine particles.
( 5 ) The inkjet recording head according to any one of (1) to ( 4 ), wherein the fluorine-containing compound is a polymerizable group-containing fluoropolymer.
( 6 ) An ink jet recording apparatus equipped with an ink jet head, wherein the ink jet head is the ink jet head according to any one of (1) to ( 5 ).
( 7 ) (a) Hydrolyzate of organosilane containing radical polymerizable group and / or partial condensate thereof, or (a) polyorganosiloxane containing radical polymerizable group, and (b) fluorine-containing compound A polymerizable resin composition for water repellent treatment, comprising at least (c) inorganic fine particles.
( 8 ) In the method of manufacturing an ink jet recording head according to any one of (1) to ( 6 ), a solvent and (a) an organosilane containing a radical polymerizable group are added to the ink-repellent treatment portion of the recording head. Applying a polymerizable resin composition containing at least a decomposition product and / or a partial condensate thereof, or (a) a polyorganosiloxane containing a radical polymerizable group and (b) a fluorine-containing compound; and A method for producing an ink jet recording head, comprising a step of applying an activation energy ray or heat to a coating film formed by evaporating a solvent after coating to form a crosslinked body of a polymerizable polymer.

The ink jet recording head of the present invention is excellent in water repellency and abrasion resistance, and has high print quality. In particular, when inorganic fine particles are included, the wear resistance is maintained for a long time.
The polymerizable resin composition for forming a water-repellent resin film of the present invention can easily form a resin film on the discharge port surface of an ink jet recording head at a temperature of 120 ° C. or lower.

The ink jet recording head of the present invention will be described below.
First, for the polymerizable resin composition of the present invention used in the inkjet recording head of the present invention, (a) a hydrolyzate of organosilane containing a polymerizable group and / or a partial condensate thereof, (a) 'polymerizability The polyorganosiloxane containing a group, (b) a fluorine-containing compound, and other components will be described in this order.
In addition, in this specification, () [] in a chemical formula represents a repeating unit, and the subscript of () [] represents a mass composition ratio.

[(A) Hydrolyzate of organosilane containing polymerizable group and / or partial condensate thereof, (a) 'polyorganosiloxane containing polymerizable group]
In the present invention, (a) a hydrolyzate of an organosilane containing a polymerizable group and / or a partial condensate thereof, or (a) a polyorganosiloxane containing a polymerizable group is used.
(A) 'Polyorganosiloxane containing a polymerizable group is a hydrolyzed portion of an organosiloxane containing a polymerizable group or an organosilane containing a functional group capable of introducing a polymerizable group after the production of the polyorganosiloxane. Represents a condensate.
(A) and (a) ′ are so-called sol components, and are collectively referred to herein as “polymerizable group-containing sol components” (or “sol components”).
The polymerizable group is a functional group other than a silanol group that is polymerized or reacted by a conventionally known initiation reaction such as radical polymerization, cationic polymerization, anionic polymerization, polyaddition, condensation polymerization, and the like. Are preferred, and radically polymerizable groups are particularly preferred.
The organosilane containing a radical polymerizable group is an organosilane compound containing a radical polymerizable functional group (such as a methacryloyl group, an acryloyl group, or a vinyl group), and is preferably represented by the following general formula (1). A compound.

In the general formula (1), R ²¹ represents hydrogen or a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, fluorine, or chlorine. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. Hydrogen or methyl group, methoxy group, methoxycarbonyl group, cyano group, fluorine and chlorine are preferred, hydrogen or methyl group, methoxycarbonyl group, fluorine and chlorine are more preferred, and hydrogen or methyl group is particularly preferred.

Y represents a single bond or an ester group, an amide group, an ether group, or a urea group. A single bond, an ester group or an amide group is preferred, a single bond or an ester group is more preferred, and an ester group is particularly preferred.
L represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) inside, and a linking group inside. A substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an alkylene group having a linking group therein is preferred, an unsubstituted alkylene group, an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferred, and an unsubstituted alkylene group and an alkylene group having an ether or ester linking group inside are particularly preferred. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

n represents 0 or 1. When a plurality of Xh are present, the plurality of Xhs may be the same or different. n is preferably 0.
R ²² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, t-butyl, sec-butyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
The substituent contained in R ²² is not particularly limited except that it is other than a radically polymerizable group, but a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (Methyl, ethyl, i-propyl, propyl, t-butyl, etc.), aryl groups (phenyl, naphthyl, etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl, etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, etc.) , Hexyloxy, etc.), aryloxy (phenoxy, etc.), alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), acyloxy groups (acetoxy, propanoyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, etc.) ), Aryloxycarbonyl group (pheno Cicarbonyl etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl etc.), acylamino groups (acetylamino, benzoylamino, acrylamino, methacrylamino, etc.), etc. These substituents may be further substituted.
Xh represents a hydroxyl group or a hydrolyzable group, and examples of the hydrolyzable group include an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group and an ethoxy group), a halogen atom (for example, Cl , Br, I, etc.), or R ²³ COO (R ²³ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, more preferably a methoxy group or an ethoxy group. Particularly preferred is a methoxy group.

  Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

An organosilane containing no polymerizable group, which will be described later, may be added to the organosilane containing the polymerizable group. The amount used at this time can be made the same as the range of amounts used later.
That is, a sol component containing a polymerizable group is obtained by hydrolyzing or partially condensing a mixture of an organosilane containing a polymerizable group and an organosilane containing no polymerizable group (hereinafter referred to as “other organosilane”). You may let them. The other organosilane is preferably a compound represented by the following general formula (2).

General formula (2)
_{^{(R 22) m -Si (Xh}} ) 4-m

In the general formula (2), R ²² has the same meaning as in the general formula (1) and represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, t-butyl, sec-butyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.

Xh is synonymous with the general formula (1) and represents a hydroxyl group or a hydrolyzable group, preferably a halogen atom, a hydroxyl group or an unsubstituted alkoxy group, and chlorine, a hydroxyl group or an unsubstituted alkoxy group having 1 to 6 carbon atoms. Are more preferable, a hydroxyl group and an alkoxy group having 1 to 3 carbon atoms are more preferable, and a methoxy group is particularly preferable.
m represents an integer of 1 to 3. When R ²² or Xh there are a plurality, it may be different even multiple R ²² or Xh same respectively. m is preferably 1 or 2, particularly preferably 1.

Specific examples of the compound represented by the general formula (2) include methyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Although silane etc. are mentioned, this invention is not limited to these.

  In order to obtain the desired effect of the present invention, the content of the organosilane containing the polymerizable group is preferably 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass. 70 mass% to 100 mass% is more preferable, and 90 mass% to 100 mass% is particularly preferable. If the content of the organosilane containing a polymerizable group is less than 30% by mass, solid content is generated, the liquid becomes cloudy, the pot life is deteriorated, or the molecular weight is difficult to control (increase in molecular weight). Further, since the content of the polymerizable group is small, it is not preferable because it is difficult to improve the performance (for example, the scratch resistance of the ink repellent portion) when the polymerization treatment is performed.

The weight average molecular weight of the polymerizable group-containing sol component is preferably from 1000 to 20000, more preferably from 1000 to 10,000, and even more preferably from 1100 to 5000, when a component having a weight average molecular weight of less than 300 is excluded. 1200 to 3000 is more preferable, and 1200 to 2000 is more preferable. When the mass average molecular weight is in the above range, the solubility in an organic solvent is excellent, and the desired performance is obtained.
Furthermore, when the component having a mass average molecular weight of 300 or more is defined as 100% by mass, the mass part of the component having a mass average molecular weight of 1000 to 20000 is 80% by mass or more. In view of storage stability, it is preferably 85% by mass or more, more preferably 90% by mass or more, still more preferably 94% by mass or more, and 96% by mass or more. Particularly preferred.

  Here, the mass average molecular weight is a molecular weight expressed in terms of polystyrene by solvent THF and differential refractometer detection using a GPC analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all manufactured by Tosoh Corporation). Yes, the content is calculated by converting each peak area% in the molecular weight range to 100% by mass when the peak area of a component having a mass average molecular weight of 300 or more is 100% by mass.

  The dispersity (mass average molecule / number average molecular weight) is preferably 3.00 to 1.05, more preferably 2.50 to 1.10, still more preferably 2.00 to 1.10, and 1.49. ˜1.10 is particularly preferred.

  In addition, it is essential that silanol groups remain in the polymerizable group-containing sol component. When no silanol groups remain, there is no interaction with the inorganic fine particles to be added and the substrate (electrostatic attractive force or covalent bond formation due to reaction of silanol groups), and the crosslinked product of the polymerizable resin composition This is not preferable because the strength and performance deteriorate.

Here, as a measure of the remaining silanol group, it is calculated from the peak intensity of silicon NMR. In the case of the sol of the compound of the general formula (1), T3 has no silanol group remaining, T2 has one silanol group remaining, and two silanol groups remain with respect to the silicon atom. This is referred to as T1, and the one in which three silanol groups remain is referred to as T0.
When the total peak area is 100%, the polymerizable group-containing sol component used in the present invention is preferably 5% or less of T0 that is not condensed only by hydrolysis and 10% or less of the T1 component. Since the T2 and T3 components are the main components, the value of T3 / T2 is used as a measure of the silanol group. That is, if the T3 component having no silanol group increases, the value of T3 / T2 increases, and in the case of all T3, it becomes infinite. In the present invention, the value of T3 / T2 is preferably 0.2 to 3.0, more preferably 0.4 to 2.0, and particularly preferably 0.4 to 1.5. When the value of T3 / T2 is smaller than 0.2, there is a concern that there are many changes in the sol component containing a polymerizable group due to a large amount of non-polymerized T0 component or an increase in the content of the reactive component, If the value of T3 / T2 is greater than 3.0, the content of silanol groups is small, and particularly when inorganic fine particles are used in combination, the strength and performance of the crosslinked product of the polymerizable resin composition deteriorates. It is not preferable.

  The hydrolysis / condensation reaction of organosilane can be carried out without solvent or in the presence of an organic solvent. Preferred organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, tetrahydrofuran, 1,4-dioxane and the like. The organic solvent used here is preferably used as a coating solution as it is in the process, and when a fluorine-containing compound is added later, one that dissolves this fluorine-containing compound is preferable. The hydrolysis / condensation reaction is preferably performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds of the metal alkoxides with ethyl acetoacetate, acetylacetone and the like.

In the hydrolysis / condensation reaction, 0.3 to 2 mol, preferably 0.5 to 1 mol of water is added to 1 mol of the alkoxy group of the organosilane, in the presence or absence of the solvent, and Preferably, it is carried out by stirring at 25 to 100 ° C. in the presence of a catalyst. The usage-amount of a catalyst is 0.01-10 mol% with respect to an alkoxy group, Preferably it is 0.1-5 mol%. The reaction conditions are preferably adjusted as appropriate depending on the reactivity of the organosilane.
In this hydrolysis / condensation reaction, first, an alkoxy group of organosilane reacts with water to hydrolyze the alkoxy group to produce a silanol group. Subsequently, two silanol groups are dehydrated and condensed to form a siloxane bond. Therefore, the product of this reaction varies in proportion depending on the amount of water added and other reaction conditions, but contains unreacted alkoxy groups, silanol groups, and siloxane bonds. In the present invention, a partial condensate of organosilane means that all alkoxy groups of organosilane do not form silanol bonds via silanol groups, some of the alkoxy groups form silanol bonds, and the rest are unreacted or The one in the silanol group state.

  The solution obtained from the hydrolysis and / or condensation reaction of organosilane, that is, the sol component, preferably does not contain a solid, and more preferably has no fog.

[(B) Fluorine-containing compound]
The fluorine-containing compound is used for imparting water repellency. The fluorine-containing compound may be either a low-molecular compound such as a fluorine-containing silane coupling agent or a surfactant, or a fluorine-containing oligomer to a polymer (hereinafter collectively referred to as “fluorinated polymer”). From the viewpoint of durability of the water repellent effect, a fluorine-containing polymer is preferable.
In order to increase the strength of the water-repellent film in the wet state and the strength against scratching of the water-repellent film, the fluorinated polymer contains a sol component containing a polymerizable group or an inorganic particle surface used as necessary. It preferably contains a functional group, a functional group having reactivity with respect to a crosslinking agent added as necessary, or a radical polymerizable group, and has a radical polymerizable group (hereinafter referred to as a fluorine-containing polymerizable polymer). Is more preferable.

(Fluorine-containing polymerizable polymer)
The fluorine-containing polymerizable polymer is preferably a polymer containing a structural unit containing fluorine and a structural unit containing a radical polymerizable group. The fluorine-containing polymerizable polymer may be one of the following polymers (I) and (II) from the viewpoint of increasing the ink repellency and increasing the durability of the water-repellent resin film after the crosslinking reaction. preferable.
(I) A structural unit containing a fluorine-containing structural unit and a radically polymerizable group, and optionally other structural units arranged randomly (hereinafter also referred to as a fluorine-containing polymerizable polymer (I) of the present invention) .)
(II) A structure in which a structural unit containing fluorine and a structural unit containing a radical polymerizable group are separated, that is, a first segment which is a polymer chain having a structural unit containing fluorine and a radical polymerizable group And a second segment, which is a polymer chain having a structural unit to form, and a fluorine-containing structural unit represented by any one of the following general formulas 3a to 3d (hereinafter referred to as a fluorine-containing polymerizable polymer (II Also called)

Further, in the fluorine-containing polymerizable polymer (II), a linear or branched structure containing at least one of the first segment and the second segment is more preferable, and the first segment, the second segment, Is more preferable, and a branched structure having the first segment in a branch portion is more preferable, and a linear structure including at least one of the first segment and the second segment is Particularly preferred.
The fluorine-containing polymerizable polymer contained in the fluorine-containing polymerizable polymer may be one kind or plural kinds.

As the structural unit containing fluorine, the atoms forming the main chain may be only carbon or may contain atoms other than carbon such as oxygen. It is preferable to introduce the fluorine-containing vinyl monomer so that the fluorine content in the fluorine-containing polymerizable polymer is 20 to 60% by mass, more preferably 25 to 55% by mass, particularly preferably 30 to This is the case of 50% by mass. By setting the fluorine content within the above range, sufficient water repellency and crosslinkability can be achieved.
Preferable forms of the structural unit containing fluorine include structural units represented by the following general formulas 3a to 3d.

In General Formula 3a, Rf ⁰ represents a fluorine atom, a C 1-8 perfluoroalkyl group, or an —ORf ¹ group. When Rf ⁰ is a perfluoroalkyl group, from the viewpoint of polymerization reactivity of the corresponding monomer, a perfluoroalkyl group having 1 to 4 carbon atoms, specifically, a perfluoromethyl group, a perfluoroethyl group, A perfluoropropyl group and a perfluorobutyl group are more preferable. Rf ¹ represents a fluorinated aliphatic group having 1 to 22 carbon atoms, preferably a fluorinated aliphatic group having 1 to 12 carbon atoms. Specifically, for example, a perfluoroalkyl group having 1 to 8 carbon _{atoms, -CH 2 F, -CHF 2,} -CH 2 CF 3, - (CH 2) 2 C 2 F 5, -CH 2 CF 2 CF 2 _{CFH 2, -CH 2 (CF 2} ) 4 H, -CH 2 (CF 2) 8 CF 3, even _{-CH 2 CH 2 (CF 2)} 4 H , etc.), a branched structure (e.g., CH (CF _{3 2} ), CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.), and an alicyclic structure (Preferably a 5-membered or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group or an alkyl group substituted therewith) or a fluorine-containing aliphatic ether bond group (for example,- _{CH 2 OCH 2 CF 2 CF 3} , -CH 2 CH 2 OCH 2 C 4 F 8 H, -CH 2 CH 2 OC _{2 CH 2 C 8 F 17,} -CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H, -CF 2 CH 2 OCH 2 CF 3, - (CF 2) 2 (CH 2) 2 OCH (CF 3) 3 Etc.).

In the general formula 3b, R ⁰ represents a hydrogen atom, a fluorine atom, a methyl group or a cyano group, preferably a hydrogen atom or a methyl group.

L1 represents — (covalent bond, ie, a state in which C and Rf ² are directly bonded), —O—, —S—, —CO—, —COO—, —CONR ⁵⁰ —, —OCO—, —OCONR. ^{51 -, - NR 52 CO -} , - NR 53 COO -, - NR 54 CONR 55 -, - SO -, - SO 2 -, - SO 2 NR 56 -, - NR 57 SO 2 -, - SiR 58 R 59 ^{-, - PR 60 -, -} PO (OR 61) O -, - OPO (OR 62) -, - PO (OR 63) NR 64 -, - NR 65 PO (OR 66) -, - NR 67 PO (NR ⁶⁸ R ⁶⁹ ) NR ⁷⁰ -and -NR ^71- . Among them, -O -, - S -, - CO -, - CONR 50 -, - OCO -, - OCONR 51 -, - NR 52 CO -, - NR 53 COO -, - NR 54 CONR 55 -, - SO- _{, -SO 2 -, - SO 2} NR 56 -, - NR 57 SO 2 -, - SiR 58 R 59 -, - PR 60 -, - PO (OR 61) O -, - OPO (OR 62) -, - PO (OR ⁶³ ) NR ⁶⁴ —, —NR ⁶⁵ PO (OR ⁶⁶ ) —, —NR ⁶⁷ PO (NR ⁶⁸ R ⁶⁹ ) NR ⁷⁰ —, —NR ⁷¹ — are preferred, —O—, —S—, —CO —, —OCO—, —OCONR ⁵¹ —, —NR ⁵² CO—, —NR ⁵³ COO—, —NR ⁵⁴ CONR ⁵⁵ —, —SO—, —SO ₂ — are more preferred, —O—, —OCO—, —OCONR ⁵¹ —, —NR ⁵² CO—, and —NR ⁵³ COO— are more preferable, and —O— is particularly preferable. Here, R ⁵⁰ to R ⁷¹ represent H or a substituted or unsubstituted alkyl group, preferably H or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and H or 1 to 3 carbon atoms. An unsubstituted alkyl group is particularly preferred.

Rf ² represents a hydrocarbon group in which part or all of the CH bond is substituted with fluorine, and may be linear or branched, may have a ring structure, O, N , S may have a hetero atom selected from S in the linking group, and may have a substituent such as a hydroxyl group or an alkoxy group. Preferred are perfluoroalkyl groups having 1 to 20 carbon atoms, 1H, 1H-perfluoroalkoxy groups having 2 to 18 carbon atoms, 1H, 1H, 2H, 2H-perfluoroalkoxy groups having 3 to 18 carbon atoms, A perfluoroalkyl group having 3 to 20 carbon atoms, 1H, 1H-perfluoroalkoxy group having 3 to 18 carbon atoms, 1H, 1H, 2H, 2H-perfluoroalkoxy group having 4 to 18 carbon atoms is more preferable. 1H, 1H-perfluoroalkoxy group having 6 to 18 carbon atoms, 1H, 1H, 2H, 2H-perfluoroalkoxy group having 6 to 18 carbon atoms is more preferred, 1H, 1H, 2H, 2H-carbon atom A perfluoroalkoxy group of the number 6 to 18 is particularly preferred.
In General Formula 3c, R ¹ and R ² may be the same or different and each represents a fluorine atom or a —C _v F _{2v + 1} group. Here, v represents an integer of 1 to 4, a represents 0 or 1, b represents an integer of 2 to 5, and c represents 0 or 1. When a and / or c is 0, each represents a single bond.
In the general formula 1d, R ³ and R ⁴ each represent a fluorine atom or a —CF ₃ group. a is the same as in the above general formula 3c. d represents 0 or 1, k represents 0 or an integer of 1 to 5, l represents 0 or an integer of 1 to 4, and m represents 0 or 1. When d, k, l and / or m is 0, each represents a single bond. Here, (k + l + m) is an integer in the range of 1-6.

Specific examples of the monomer forming the structural unit represented by the general formula 3a include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, etc.), complete or partial fluorination Mono- or divinyl ethers, fluoro-substituted cyclic ethers (for example, hexafluoroepoxypropane, 3-perfluorohexyl-1,2-epoxypropane, 3- (1H, 1H, 5H-octafluoropentyloxy) -1,2- Epoxy propane etc.).
Specific examples of the monomer forming the structural unit represented by the general formula 3b include a (meth) acrylic acid moiety or a fully fluorinated alkyl ester derivative (for example, Biscoat 6FM (trade name, manufactured by Osaka Organic Chemical Co., Ltd.), M- 2020 (trade name, manufactured by Daikin) and the like, and fully or partially fluorinated mono- or divinyl ethers.
Preferred examples of the structural unit represented by the general formula 3c include the following (f-1) to (f-8) and the like. Preferred examples of the structural unit represented by the general formula 3d include (F-9) to (f-16) and the like.

  As an example of the main chain including a fluorine-containing structural unit when the atoms forming the main chain include atoms other than carbon, for example, as shown in the following specific examples, a plurality of structural units are linked by oxygen atoms, respectively. Such a structure is mentioned.

The radical polymerizable group is a compound having a polymerizable double bond that is solidified by applying energy such as ultraviolet rays, heat, or an electron beam, or adding an active radical. Examples of radically polymerizable groups include acryloyl groups, methacryloyl groups, allyl groups, vinyl groups (vinyl esters, vinyl ethers, styrene derivatives, etc.), internal double bond groups (maleic acid, etc.), acryloyl groups, methacryloyl groups. A vinyl group is preferable, and an acryloyl group and a methacryloyl group are more preferable, and an acryloyl group is particularly preferable because of high polymerization reactivity.
If the composition ratio of the structural unit containing a radical polymerizable group is increased, the film strength is improved, but the adhesion with the lower layer tends to be weakened. Therefore, although it varies depending on the type of the fluorine-containing vinyl monomer polymerization unit, it is generally preferable that the structural unit containing a radical polymerizable group occupies 10 to 70 mol% in the fluorine-containing polymerizable polymer, and occupies 20 to 60 mol%. It is more preferable to occupy 30 to 60 mol%.
A preferred form of the structural unit containing a radical polymerizable group is a structural unit represented by the following general formula 4.

In General Formula 4, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a chlorine atom, or a fluorine atom, preferably a hydrogen atom or a fluorine atom, and particularly preferably a hydrogen atom.
R ¹² represents a hydrogen atom, a chlorine atom, a fluorine atom, an optionally substituted alkyl group or a carboxyl group, preferably a hydrogen atom or a fluorine atom, and particularly preferably a hydrogen atom.
L3 represents a linking group having 1 to 20 carbon atoms, which may be linear or branched, may have a ring structure, and is a heteroatom selected from O, N and S. You may have in a coupling group and you may have substituents, such as a hydroxyl group and an alkoxy group. An alkylene group having 2 to 8 carbon atoms, an alkylene group containing a cyclic structure therein, a phenylene group, an alkylene group having O and N as a linking group in the alkylene chain, and an alkylene group having a substituent such as a hydroxyl group or an alkoxy group are preferred. , An alkylene group having 2 to 4 carbon atoms, an alkylene group containing a cyclic structure having 6 to 10 carbon atoms, a phenylene group, an alkylene chain having 3 to 10 carbon atoms as a linking group, O, N An alkylene group having 3 to 10 carbon atoms, and an alkylene group having a substituent such as an alkoxy group having 3 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms and 3 to 10 carbon atoms. The alkylene chain has a substituent such as an alkylene group having O or N as a linking group, a hydroxyl group having 3 to 10 carbon atoms, or an alkoxy group. Alkylene group is particularly preferred that.
L2 and L4 are each independently synonymous with L1 described in 1b of General Formula 1.
p is 0 or 1.
X represents a hydrogen atom or a fluorine atom, a methyl group or a cyano group, and from the viewpoint of appropriate curing reactivity, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable.
Specific examples of the structural unit represented by the general formula 4 are illustrated below.

A structural unit containing a radically polymerizable group can be produced by polymerization of a monomer having a radically polymerizable group in the side chain, but when the radically polymerizable group in the side chain reacts during the polymerization reaction. Since it is easy to become an insoluble gel, it is preferable to form a copolymer having no radical group in the side chain in advance and then introduce a polymerizable group.
As a method for introducing a radical polymerizable group, a (meth) acryloyl group will be described as an example. The introduction method is not particularly limited. For example, (1) after synthesizing a polymer having a nucleophilic group such as a hydroxyl group or an amino group, (meth) acrylic acid chloride, (meth) acrylic anhydride, ( A method in which a mixed acid anhydride of meth) acrylic acid and methanesulfonic acid is allowed to act, (2) a method in which (meth) acrylic acid is allowed to act on the polymer having the nucleophilic group in the presence of a catalyst such as sulfuric acid, (3 ) A method of causing a compound having both an isocyanate group such as methacryloyloxypropyl isocyanate and a (meth) acryloyl group to act on the polymer having the nucleophilic group, and (4) synthesizing a polymer having an epoxy group and then reacting with (meth) acrylic acid. (5) A compound having both an epoxy group such as glycidyl methacrylate and a (meth) acryloyl group is allowed to act on a polymer having a carboxyl group. That method, and a method of performing dehydrochlorination after obtained by polymerizing a vinyl monomer having a (6) 3-chloropropionic acid ester moiety.

  Among these, in the present invention, in particular, a method of introducing a radical polymerizable group by the method of (1) or (2), (3) for a polymer containing a hydroxyl group, and (4) for a polymer containing a glycidyl group. The method of introducing a radical polymerizable group by the method of) and the method of introducing a radical polymerizable group by the method of (5) are preferred, and the polymer containing a hydroxyl group by the method of (1) or (3) ( A method for introducing a (meth) acryloyl group, a method for introducing a (meth) acryloyl group to the polymer containing a glycidyl group by the method (4), and a method for introducing a (meth) acryloyl group by the method (5) Is more preferable.

In addition to the structural unit containing fluorine and the structural unit containing the radical polymerizable group, the fluorine-containing polymerizable polymer has adhesion to a base material, Tg of the polymer (contributes to film hardness), dustproof / antifouling Other structural units (a structural unit constituting another segment or a structural unit serving as a connecting portion of segments) and the like may be appropriately included from various viewpoints such as properties.
The monomer constituting the other structural unit is not particularly limited, and any monomer can be used as long as it can be copolymerized with the structural unit containing the fluorine and the structural unit containing the radical polymerizable group. Yes, it may or may not contain a functional group.
Further, when the fluorine-containing polymerizable polymer is the fluorine-containing polymerizable polymer (II) of the present invention (in the case of a structure that can be separated into the first segment and the second segment), the fluorine is contained in the first segment. Other structural units that do not contain a radical polymerizable group (hereinafter referred to as “structural unit A”) may be included in addition to the structural units. The structural unit A may or may not contain a functional group other than a radical polymerizable group, but does not have a hydrophilic functional group (for example, a hydroxyl group, a carboxyl group, etc.) from the viewpoint of not hindering water repellency. Those are preferred.

  Furthermore, the second segment may include other structural units not containing the radical polymerizable group (hereinafter referred to as “structural unit B”) in addition to the structural unit containing the radical polymerizable group. Any structural unit B may be used as long as it is copolymerizable with the raw material monomer of the structural unit containing the radical polymerizable group or with the raw material monomer of the structural unit before the radical polymerizable group is introduced. The structural unit B may contain a functional group other than a radically polymerizable group, but may contain a functional group capable of reacting with an adhesive having adhesiveness to a substrate or a curing reactive agent. Is preferred.

  Among the examples of monomers constituting the other structural units, those having no functional group include olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, ethyl acrylate). , 2-ethylhexyl acrylate, acrylate having polydimethylsiloxane at the ester site), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, allyl methacrylate, methacrylate having polydimethylsiloxane at the ester site), styrene derivatives (Styrene, p-methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.) Acrylamides (N, N-dimethylacrylamide, N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile, etc., olefins, acrylic acid Esters (acrylates having an ester group of 4 or more carbon atoms, acrylates having a polydimethylsiloxane at the ester site), methacrylates (methacrylates having an ester group of 4 or more carbon atoms, methacrylates having a polydimethylsiloxane at the ester site, etc. ), Styrene derivatives and vinyl ethers are particularly preferred.

As functional group-containing compounds, epoxy group-containing vinyl monomers (glycidyl acrylate, methacrylates containing 1,2-epoxycyclohexyl groups, glycidyl vinyl ether, etc.), hydroxyl group-containing vinyl monomers (2-hydroxyethyl methacrylate, 2,3- Dihydroxypropyl acrylate, N-hydroxyacrylamide, p-hydroxymethylstyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), silane coupling group-containing vinyl monomers (3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl methacrylate, etc.) Amino group-containing vinyl monomers (3-dimethylaminopropyl acrylate, 3-aminopropyl acrylamide, etc.), carboxyl group-containing vinyl monomers ( Acrylic acid, crotonic acid, maleic acid, and itaconic acid, etc.) and the like.
A plurality of the monomers constituting the other structural units may be combined depending on the purpose. When the other structural units are used, the total of the other structural units is within a range of 65 mol% or less in the fluorine-containing polymerizable polymer. It is preferably introduced in the range of 40 mol% or less, more preferably 30 mol% or less.

  The number average molecular weight of the fluorine-containing polymerizable polymer is preferably 1500 to 500,000, and the degree of polymerization is preferably 10 to 1,000. More preferably, the average molecular weight is 1500 to 200,000 and the degree of polymerization is 10 to 500. In particular, the average molecular weight is preferably 1500 to 100,000, and the degree of polymerization is preferably 10 to 200.

  Specific examples of the fluorine-containing polymerizable polymer (I) of the present invention are shown below. As described above, the fluorine-containing polymerizable polymer (I) of the present invention is a polymer having a structure that cannot be divided into a first segment and a second segment, respectively. Subsequently, specific examples of the fluorine-containing polymerizable polymer (II) of the present invention will be shown. As described above, the fluorine-containing polymerizable polymer (II) of the present invention is a polymer that is divided into the first segment and the second segment described above.

The synthesis of the fluorine-containing compound used in the present invention (including the above-mentioned fluorine-containing polymerizable polymer (I) (II)) can be carried out by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, After synthesizing a precursor such as a hydroxyl group-containing polymer by emulsion polymerization, it can be carried out by introducing a (meth) acryloyl group or the like by the polymer reaction. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.
The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masato Kinoshita, “Experimental Methods for Polymer Synthesis” Published in 1972, p. 124-154.
Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Solvents used in the solution polymerization method are, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, A single organic solvent such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol, or a mixture of two or more thereof may be used, or a mixed solvent with water may be used.

  The blending ratio of the sol component and the (b) fluorine-containing compound is set to 2000 to 50 parts by mass of the (b) fluorine-containing compound with respect to 100 parts by mass of the sol component. From the viewpoint of property, it is more preferably set to 1000 to 500.

[(C) Inorganic fine particles]
The polymerizable resin composition of the present invention preferably contains inorganic fine particles.
In the ink jet recording head of the present invention, the sol component is preferable because it exhibits an effect particularly when inorganic fine particles are used in combination. Even when mixed with a water-repellent polymer, the silane coupling site contained in the sol component or the like is adsorbed and / or reacted on the surface of the inorganic fine particle, and the affinity between the inorganic fine particle and the organic material is improved. An ideal dispersed state can be expected due to the compatibility between the sol component and the like and the lipophilic group of the polymer, and the film has excellent mechanical properties due to affinity or interaction even after drying and curing.
The shape of the inorganic fine particles is not particularly limited, and for example, any of a spherical shape, a plate shape, a fiber shape, a rod shape, an indefinite shape, a hollow shape, and the like are preferably used. Further, the kind of the inorganic fine particles is not particularly limited, but an amorphous one is preferably used, and is preferably made of a metal oxide, nitride, sulfide or halide. Particularly preferred. As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb, Ni and the like.
It is preferably in a range of 30% by mass or less, more preferably in a range of 20% by mass or less, and in a range of 10% by mass or less with respect to the total solid content in the polymerizable resin composition for forming a resin film. It is particularly preferred.

A dispersion stabilizer may be used in combination for the purpose of suppressing aggregation and sedimentation of the inorganic fine particles. Dispersion stabilizers include polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivatives, polyamides, phosphate esters, polyethers, surfactants, and sol components containing the above radical polymerizable groups, silane coupling agents, titanium couplings An agent or the like can be used. The addition amount of the dispersion stabilizer is not particularly limited, but for example, it is preferably set to a value of 1 part by mass or more with respect to 100 parts by mass of the inorganic fine particles. Further, the method for adding the dispersion stabilizer is not particularly limited.
The average particle size of the inorganic fine particles is preferably 0.001 to 2 μm, more preferably 0.001 to 0.5 μm, still more preferably 0.001 to 0.2 μm, 0.005 to A thickness of 0.05 μm is particularly preferable. The particle diameter of the fine particles is preferably as uniform (monodispersed) as possible.

Next, the polymerizable resin composition will be described.
[Polymerizable resin composition]
The polymerizable resin composition used in the ink jet recording head of the present invention has the above-mentioned (a) hydrolyzate of organosilane and / or its partial condensate containing a polymerizable group, or (a) a polymerizable group. It is a composition obtained by dissolving or emulsifying and dispersing a polyorganosiloxane to be contained, (b) a fluorine-containing compound, and (c) inorganic fine particles used as necessary in a solvent, and further appropriately selected as necessary. It contains other ingredients.

-Solvent-
The solvent contained in the polymerizable resin composition is not particularly limited as long as the sol component or the fluorine-containing compound is uniformly dissolved, emulsified, or dispersed without causing precipitation, and two or more kinds of solvents are used in combination. You can also
It is preferable to use a highly safe one. A solvent having high safety is a solvent having a high management concentration (an index indicated by a work environment evaluation standard), preferably 100 ppm or more, and more preferably 200 ppm or more. Furthermore, in order to form a film in an appropriate time, those which volatilize by heating from room temperature to 150 ° C. are preferable. Preferred examples include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), alcohols (methanol, ethanol, isopropyl). Alcohol, 2-butanol, ethylene glycol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), water and the like.

-Other ingredients-
The polymerizable composition for forming a resin film of the present invention is usually in the form of a liquid, and the sol component containing the polymerizable group is an essential constituent, and if necessary, a polymerization initiator, a storage stabilizer, and various It is prepared by dissolving the additive in a suitable solvent. At this time, the concentration of the solid content is appropriately selected according to the use, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably 1% to 20% by mass. %.

1) Polymerization initiator and sensitizer The polymerization initiator may be in any form that generates radicals by the action of heat or generates radicals by the action of light.
The photopolymerization initiator is not particularly limited as long as radicals generated by light and other active species react with the polymerizable double bond in the monomer, but acetophenone derivatives, benzophenone derivatives, benzyl derivatives, benzoin Derivatives, benzoin ether derivatives, benzyldialkyl ketal derivatives, thioxanthone derivatives, acylphosphine oxide derivatives, metal complexes, p-dialkylaminobenzoic acids, azo compounds, peroxide compounds, etc. are generally known, acetophenone derivatives, benzyl derivatives, benzoin Ether derivatives, benzyl dialkyl ketal derivatives, thioxanthone derivatives, and acyl phosphine oxide derivatives are preferred, and acetophenone derivatives, benzoin ether derivatives, benzyl dialkyl ketal derivatives, Le phosphine oxide derivatives are particularly preferable.

  Specifically, acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, benzophenone, p, p'-dichlorobenzophenone, p, p'-bisdiethylaminobenzophenone, Michler's ketone, Benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin-n-propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1-hydroxy-cyclohexyl phenyl ketone, tetramethylthiuram monosulfide, thioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2,2-dimethylpropioyl diphenylphosphine oxide, 2-methyl-2-ethylhexanoyl Diphenylphosphine oxide, 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,6-dimethoxybenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)- 2,4,4-trimethylpentylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,3,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-tri Methoxybenzoyl-diphenylphosphine oxide, 2,4,6-trichlorobenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl naphthyl phosphonate, bis (η5-2, 4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -finyl) titanium, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, azobisiso Examples include butyronitrile, 1,1′-azobis (1-acetoxy-1-phenylethane), benzoin peroxide, and di-tert-butyl peroxide.

Furthermore, as an example of a photopolymerization initiator, p. The photoinitiator described in 65-148 etc. can be mentioned.
These photopolymerization initiators can be used alone or in combination of two or more, and may be used in combination with a sensitizer.

The sensitizer is not activated by light irradiation alone, but when used together with the photopolymerization initiator, it is more effective than the photopolymerization initiator used alone, and amines are generally used. The addition of amines increases the curing rate, primarily because hydrogen is supplied to the photopolymerization initiator by the action of hydrogen abstraction, and secondly, the generated radicals are combined with oxygen molecules in the atmosphere and are reactive. This is because the amine has an action of trapping oxygen dissolved in the composition.
Sensitizers include amine compounds (aliphatic amines, amines containing aromatic groups, piperidine, reaction products of epoxy resins and amines, triethanolamine triacrylate, etc.), urea compounds (allylthiourea, o-tolylthiourea, etc.) ), Sulfur compounds (sodium diethyldithiophosphate, soluble salts of aromatic sulfinic acid, etc.), nitrile compounds (N, N-diethyl-p-aminobenzonitrile, etc.), phosphorus compounds (tri-n-butylphosphine, sodium diethyl) Dithiophosphide, etc.), nitrogen compounds (Michler ketone, N-nitrisohydroxylamine derivative, oxazolidine compound, tetrahydro-1,3-oxazine compound, formaldehyde or a condensate of acetaldehyde and diamine), chlorine compound (carbon tetrachloride, Kisa chloroethane, etc.), and the like.
Although the sensitizer is not necessarily a component that must be used, the amount used is usually 10% by mass or less, preferably 0.1 to 10% by mass, and preferably 0.2 to 5% by mass in the total solid content. Particularly preferred. The selection and combination of the photoinitiator and the sensitizer, and the blending ratio may be appropriately selected depending on the ultraviolet curing monomer used and the apparatus used.
The addition amount of the polymerization initiator may be an amount capable of initiating the polymerization of the carbon-carbon double bond, but is generally 0.1% relative to the total solid content of the polymerizable resin composition for resin film formation. -15 mass% is preferable, More preferably, it is 0.5-10 mass%, Most preferably, it is a case of 2-5 mass%.

2) Storage stabilizer The storage stabilizer is used to suppress undesired polymerization during storage, and is used that dissolves in the composition. Examples include quaternary ammonium salts, hydroxyamines, cyclic amides, nitriles, substituted ureas, heterocyclic compounds, organic acids, hydroquinones, hydroquinone monoethers, organic phosphines, copper compounds, etc. Specific examples include benzyltrimethylammonium chloride, diethylhydroxylamine, benzothiazole, 4-amino-2,2,6,6-tetramethylpiperidine, citric acid, hydroquinone monomethyl ether, hydroquinone monobutyl ether, and copper naphthenate.
The amount used is preferably adjusted as appropriate based on the activity of the polymerization initiator used, the polymerizability of the vinyl polymerizable group, and the type of storage stabilizer, but is generally preferably 0.005 to 1% by mass. 01-0.5 mass% is still more preferable, and 0.01-0.2 mass% is especially preferable. Storage stability improves by setting it as 0.005 mass% or more, and the polymerization reaction (curing) after film formation occurs smoothly by setting it as 1 mass% or less.

3) Additives From the viewpoint of interfacial adhesion to the substrate, etc., polyfunctional (meth) acrylate compounds, reactive groups (epoxy groups, oxetane groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiro orthoester groups , Compounds having two or more vinyl ether groups, isocyanate groups, etc., reactive silane coupling agents, curing agents such as aminoplasts, polybasic acids or their anhydrides, or conductive fine particles (InO doped with ITO (SnO _{2)) 2} O ₃ ), ATO (Sb-doped SnO ₂ ), Sb ₂ O ₃ , SbO ₂ , In ₂ O ₃ , SnO ₂ , conductive ZnO, AZO (AL-doped zinc oxide), antimony zinc oxide, etc. Conductive metal oxide fine particles, conductive nitrides such as titanium nitride, zirconium nitride and hafnium nitride, metal particles such as gold, silver and copper) It can also be added. When adding these, it is preferably in the range of 30% by mass or less, more preferably in the range of 20% by mass or less, based on the total solid content in the polymerizable resin composition for resin film formation, A range of 10% by mass or less is particularly preferable.
When a compound containing a reactive group other than a radically polymerizable group is used as an additive, or when the fluorine-containing polymerizable polymer contains a reactive group other than a radically polymerizable group, not only a polymerization initiator that generates radicals. It is preferable to use a cationic polymerization initiator and a crosslinking reaction accelerator in combination.
In addition, for the purpose of further enhancing properties such as antifouling properties and water resistance, known silicone-based or fluorine-based antifouling agents, slipping agents, and the like can be appropriately added. When these additives are added, it is preferably added in a range of 20% by mass or less, more preferably in a range of 10% by mass or less, based on the total solid content of the polymerizable resin composition for resin film formation. Particularly preferably 5% by mass or less.

  As described above, the above-described polymerizable resin composition is used in the ink jet recording head of the present invention. The polymerizable resin composition of the present invention preferably further contains the storage stabilizer in the sol component and the fluorine-containing compound.

Next, a method for manufacturing the ink jet recording head of the present invention will be described.
The method for producing an ink jet recording head of the present invention comprises a step of applying a polymerizable resin composition containing at least a solvent, a sol component, and (b) a fluorine-containing compound to an ink repellent treatment portion of a recording head; and The coating film formed by evaporating the solvent after coating is subjected to a step of forming a polymerized polymer crosslinked body by applying an activation energy ray or heat to form a resin film by the crosslinked body. .
(Resin film forming method)
A method for forming the resin film will be described.
In order to form a resin film using the above-described polymerizable resin composition, a film of the polymerizable resin composition for forming a resin film is formed on the surface of the nozzle plate by coating or dip coating, and then activated energy rays or heat. A cross-linking reaction is performed. As the material of the nozzle plate used, conventionally known materials such as metal, ceramics, silicon, glass and plastic can be used.
As the active energy ray, α ray, γ ray, X ray, ultraviolet ray, visible ray, electron beam and the like can be used. Of these, ultraviolet rays and visible rays are preferably used from the viewpoint of cost and safety, and ultraviolet rays are more preferably used.
As a light source for irradiating ultraviolet rays or visible light, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a xenon lamp, a chemical lamp, or the like can be used.
Usually, the polymerization reaction of vinyl polymerizable groups by radicals is inhibited by oxygen, but the polymerizable composition for forming a resin film of the present invention introduces a vinyl polymerizable group into the side chain, thereby improving the mobility of the polymerizable group. Since it is excellent in polymerizability due to the retained point and an appropriate content, sufficient curing is possible even with polymerization reactivity under air at normal temperature. However, it is also possible to carry out the polymerization reaction under conditions where the oxygen concentration is lowered or heated.
In the case of heating, a temperature range of about 30 to 200 ° C is preferable, more preferably 30 to 150 ° C, still more preferably 30 to 120 ° C, and particularly preferably 30 to 100 ° C. The heating time is preferably in the range of 30 seconds to 100 hours, more preferably 1 minute to 1 hour, and particularly preferably 2 minutes to 15 minutes.
In addition, processes other than each process mentioned above can be performed according to the manufacturing method of the conventional inkjet recording head.

  The ink jet recording head of the present invention is an ink jet recording head having an ejection port for ejecting a recording liquid, and has an ink repellent treatment portion of the recording head formed by ink repellent treatment at least around the ejection port. The ink-repellent treatment part is a cross-linked product of the polymerizable resin composition. That is, the ink repellent treatment part comprises a crosslinked product obtained by crosslinking the above-described polymerizable resin composition. Here, the crosslinked product obtained by crosslinking the polymerizable resin composition is obtained by applying active energy rays, heat, or the like to the resin film formed by applying the polymerizable resin composition and then drying to evaporate the solvent. It means a crosslinked product formed by forming a crosslinked structure by polymerizing a polymerizable polymer in the polymerizable resin composition.

<Formation of ink repellent treatment part>
The ink-repellent treatment part is preferably constructed by applying a coating solution of the polymerizable resin composition directly on a substrate described later or via another layer.
The coating solution is prepared by mixing and diluting a solution of the above-described polymerizable resin composition, and if necessary, an ultrafine particle dispersion of an inorganic compound or an additive in a coating dispersion medium to a predetermined concentration.
The coating solution is preferably filtered before coating. As a filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within a range in which components in the coating solution are not removed. For the filtration, a filter having an absolute filtration accuracy of 0.1 to 100 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 25 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, it is preferable to perform filtration at a filtration pressure of 15 kgf / cm ² or less, more preferably 10 kgf / cm ² or less, and further 2 kgf / cm ² or less.
The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filter member of the wet dispersion of an inorganic compound mentioned above is mentioned.
It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.
In the present invention, the resin film is a dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, micro gravure coating method on the substrate described later. It can be produced by coating with a known thin film forming method such as an extrusion coating method or the like, and drying, irradiating with light and / or heat. Preferably, curing by light irradiation is advantageous from rapid curing. Furthermore, it is also preferable to perform heat treatment in the latter half of the photocuring treatment.

The light source for light irradiation may be any ultraviolet light region or near-infrared light. Ultraviolet, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, metal halide lamps may be used as ultraviolet light sources. Xenon lamps, sunlight, etc. Various available laser light sources having a wavelength of 350 to 420 nm may be irradiated as a multi-beam. Further, examples of the near-infrared light source include a halogen lamp, a xenon lamp, and a high-pressure sodium lamp. Various available laser light sources having a wavelength of 750 to 1400 nm may be irradiated in a multi-beam form.
When a near infrared light source is used, it may be used in combination with an ultraviolet light source, or light may be irradiated from the substrate surface side opposite to the resin film coating side. Film curing in the depth direction in the coating layer proceeds without delay with the vicinity of the surface, and a uniform cured resin film is obtained.
In the case of radical polymerization, it can be carried out in air or in an inert gas, but the oxygen concentration should be reduced as much as possible in order to shorten the polymerization induction period of the radical polymerizable monomer or to sufficiently increase the polymerization rate. It is preferable that the atmosphere is as described above. The irradiation intensity of ultraviolet rays to be irradiated in the case of photopolymerization, preferably about 0.1~500mW / cm ^2, irradiation amount on the coating film surface is preferably 100~1000mJ / cm ^2. Further, the temperature distribution of the coating film in the light irradiation step is preferably as uniform as possible, preferably within ± 3 ° C., and more preferably controlled within ± 1.5 ° C. In this range, the polymerization reaction in the in-plane and in-layer depth directions of the coating film proceeds uniformly, which is preferable.

<Ink repellent part of ink jet recording head>
The ink jet recording head of the present invention may be any liquid discharge head that ejects a conventionally known minute droplet. For example, Pond Stephen F. "Inkjet Technology and Product Development Strategies" (TorreyPines, 2000), Takeshi Amari "Inkjet Printer Technology and Materials" (CMC, 1998), ("Inkjet Recording and Printer Recording Method") And the development of print heads "(CMC Co., Ltd., published in 2000), etc. Specific examples of the recording system head include a charge control type, a pressure vibration type and other continuous methods, and an electric- Examples include on-demand methods such as a mechanical conversion method (piezo type, etc.), an electro-thermal conversion method (bubble jet type), an electrostatic suction method, and an ultrasonic method.
The peripheral portion where the ink repellent treatment portion is formed is preferably at least the periphery of the ink droplet discharge port of the various recording heads as described above. For example, an ink jet recording head having an ejection port for ejecting ink and an ink path communicating with the ejection port, a recording head unit having an ink supply member for supplying ink to the ink path, and the ink supply member In the ink jet recording head having an ink tank portion for storing ink supplied to the ink path, for example, the peripheral portion at the tip of the nozzle hole of the ejection portion (nozzle) forming member is used as the ink repellent treatment portion. Is preferred. However, the present invention is not limited to this by the recording method, the head structure, and the like.

[Method of forming ink repellent portion]
The ink repellent treatment may be performed at any time before or after the nozzle is drilled in the nozzle plate.
The nozzle diameter perforated in the nozzle plate is such that the size of the ink droplet ejection port is preferably 15 to 100 μm, more preferably 20 to 60 μm.
Examples of methods for drilling these nozzles include press working, electroforming, excimer laser processing, and photofabrication methods.
In addition, when ink repellent treatment is performed after nozzle perforation, a method in which the inside of the nozzle hole is closed with a resist and the resist is removed after the treatment, a method in which a gas flow is passed through the nozzle, and the like are preferably performed. A masking method is also preferable as a method for precisely controlling the position and amount of the polymerizable resin composition for ink repellent treatment entering from the ink droplet discharge port into the nozzle hole.
Further, when the nozzle plate is bonded to the head portion after the ink repellent treatment, it is preferable that the back surface of the plate is not subjected to the ink repellent treatment.
The thickness of the ink-ink-treated portion (cured film) of the present invention is not particularly limited, but is preferably 0.01 to 100 μm, more preferably 0.1 to 10 μm, and particularly preferably 0.5 to 5 μm.

  A conventionally known substrate is used for the nozzle plate used in the present invention. For example, it is made of metal, ceramics, silicon, glass, plastic or the like. For example, titanium, chromium, iron, cobalt, nickel, copper, zinc, tin, gold or other single or nickel-phosphorus alloy, tin-copper-phosphorus alloy (phosphor bronze), copper-zinc alloy, stainless steel 40, etc. Organic resin materials with heat curing, solvent resistance, chemical resistance and heat resistance (for example, thermosetting polyimide, polyethersulfone, polyphenylene, polycarbonate, polysulfone, ABS resin (acrylonitrile, butadiene, styrene copolymerization) ), Polyethylene terephthalate, polyethylene naphthalate, polyacetal, sulfide, etc.) and materials formed of various photosensitive resins.

Further, these materials can be used by being laminated together. For example, the rigidity of the entire nozzle plate can be increased by bonding an organic resin material and a highly rigid inorganic material such as metal or ceramics. That is, the Young's modulus of the organic resin material is about 100 to 300 / mm ^2, a metal 8000~15000Kg / mm ^2, when compared to 10000~20000Kg / mm ² ceramics, much smaller, only the organic resin material The ink may be deformed following the driving pressure of the ink jet, resulting in a pressure loss and a drop in the ink drop velocity Vj. However, a high-rigidity material is bonded to the resin material with a thin film adhesive (adhesive layer). To improve the overall rigidity.
The thickness of the plate is preferably about 30 to 50 μm in view of processing strength, energy load required for processing, lightness as a head, and the like.

The surface shape before the ink repellent treatment of the surface of the substrate on which the resin film of the ink repellent treatment portion is formed, that is, the surface to which the polymerizable resin composition is applied in the ink repellent treatment portion may be uneven. The adhesion with the resin film is maintained by the anchor effect with the resin film of the ink repellent treatment portion, and the strength of the resin film is improved, which is preferable.
The surface shape of the surface of the substrate on which the resin film of the ink repellent treatment part is formed is such that the arithmetic average roughness (Ra) of surface irregularities based on JISB0601-1994 is 0.5 μm or less and the ten-point average roughness (Rz). It is preferable that the ratio (Ra / Rz) is 0.1 or more, the maximum height (Ry) is 0.5 μm or less, and the average surface roughness (Sm) is 0.005 to 1 μm. More preferably, Ra is 0.01 to 0.3 μm or less, the ratio (Ra / Rz) to the ten-point average roughness (Rz) is 0.15 or more, the maximum height (Ry) is 0.5 μm or less, and the surface An uneven | corrugated average space | interval (Sm) is 0.001-0.5 micrometer.
Within this range, it is preferable because the uniform coatability and adhesiveness of the resin film of the ink repellent treatment part can be maintained well.
Furthermore, instead of directly forming the resin film of the ink repellent treatment portion on the substrate, an uneven shape was imparted to the surface of the intermediate layer on which the resin film of the ink repellent treatment portion was formed even when an intermediate layer described later was passed through. It is preferable to coat the polymerizable resin composition later. A preferable surface uneven state is the same range as described above.

<Intermediate layer>
The ink repellent treatment portion may be provided with at least one intermediate layer between the nozzle plate (substrate) and the resin film formed by the ink repellent treatment. The intermediate layer preferably has functions such as adhesion, hard coat properties, primer properties, and conductivity.
The intermediate layer preferably has adhesiveness, and may be any of an inorganic layer, an organic layer, and an inorganic-organic hybrid layer, and is appropriately selected depending on the combination of the substrate and the ink repellent treatment portion from the viewpoint of adhesiveness. The intermediate layer preferably has a hard coat property (a layer having a pencil hardness of 2 or more, preferably 3 or more). Furthermore, it is preferable that conductivity is imparted.
In the case of an organic layer or an inorganic-organic hybrid layer, the intermediate layer is preferably formed by a crosslinking reaction or a polymerization reaction of a light and / or heat curable compound. For example, a coating composition containing a polyester (meth) acrylate, polyurethane (meth) acrylate, a polyfunctional monomer, a polyfunctional oligomer, or a hydrolyzable functional group-containing organometallic compound is coated on a transparent support, and a crosslinking reaction, or It can be formed by a polymerization reaction.
The curable functional group is preferably a photopolymerizable functional group, and the hydrous functional group-containing organometallic compound is preferably an organic alkoxysilyl compound. Further, the hard coat property is improved by appropriately using the fine particles of the polymerizable resin composition in the ink repellent treated portion. Furthermore, electroconductivity can be provided by containing the said electroconductive fine particles.
The film thickness of the intermediate layer is preferably 0.001 to 2 μm, and more preferably 0.01 to 0.5 μm.

When the intermediate layer is a layer immediately below the ink repellent portion of the present invention, it is preferable that the surface of the layer has irregularities.
Due to the anchor effect with the resin film of the ink repellent treatment portion, the adhesion with the resin film is maintained, and the strength of the ink repellent resin film is improved.
A preferable surface shape of the intermediate layer is in the same range as the surface shape value of the surface of the substrate on which the resin film of the ink repellent portion is formed.

[Method of imparting uneven shape]
A method for forming such a fine concavo-convex shape on the surface of the substrate or intermediate layer on which the resin film of the ink-repellent treatment part is formed is a method for modifying the shape of the surface of a conventionally known substrate. It is possible to use a method of forming an intermediate layer in which the surface state becomes fine irregularities when formed, or a combination thereof.

Examples of the method for modifying the shape of the substrate surface include a dry etching method, and in the case where the substrate is an organic layer, an embossing method in which irregularities are further transferred from the embossing plate or the sheet for pasting to the film surface.
As a dry etching method, for example, Hiroshi Mizumachi, Mitsuru Tobayama, “Surface Treatment Technology Handbook-From Bonding / Painting to Electronic Materials”, Volume 2, Section 3 (NTS, Inc., published in 2000) ), Shigeo Tatsuki et al., “Beam Processing of Polymers-Utilization of Light / Plasma / Radiation” (CMC Inc., published in 1986), supervised by Eiji Kamijo, “Plasma / Ion Beam Application and Nanotechnology” No. 1 Examples include glow discharge etching, flame plasma etching, corona discharge etching, electron beam energy irradiation etching, and the like described in Chapters to Chapter 4 (CMC Co., Ltd., published in 2002).
As an embossing method, any of a flat plate press, a continuous belt plate press, and a roll plate press can be adopted. Among these, continuous belt plate press and roll plate press are most preferable as continuous processing of the belt-like material, and roll plate press is most preferable from the viewpoint of the degree of freedom of press pressure and press temperature.

  Examples of the intermediate layer having surface irregularities include a metal oxide film obtained by applying a sol-gel reaction product obtained by hydrolysis of a hydrolyzable group-containing organometallic compound, and heating or plasma irradiation. And / or a cured film obtained by coating with a composition containing a thermosetting compound and fine particles.

<Characteristics of ink-repellent treatment part>
(Surface shape)
The shape of the surface of the ink repellent treatment portion, that is, the surface having the nozzle orifices, has an arithmetic average roughness (Ra) of surface unevenness of 1 μm or less, a maximum height (Ry) of 3 μm or less, and an average surface unevenness interval ( Sm) is preferably in the range of 15 μm or less. Furthermore, it is preferable that (Ra) is 0.01 to 0.5 μm, the maximum height (Ry) is 2 μm or less, and the average surface unevenness (Sm) is 0.02 to 10 μm or less.
By adopting such a surface state, the ink repellency of the ink repellent portion is sufficiently maintained with respect to wiping that wipes the nozzle opening surface using a wiper made of rubber or cloth.

(Antistatic property)
When charged voltage is applied to the surface of the ink repellent treatment portion and the attenuation is measured, the time required for the charge amount to be ½ of the initial charge (hereinafter referred to as charged voltage half-life) is 60 seconds or less. The anti-static effect after the ink-repellent treatment portion is provided is sufficient, and the dust adhesion preventing effect in wiping operation or the like does not decrease, which is preferable.
In particular, when the charged half-life is 30 seconds or less, the effect is high and desirable.
A specific method for measuring the charged half-life is described below. First, the surface is charged by DC corona discharge while monitoring the charged voltage on the surface of the article with an electrostatic potentiometer. Since the charged voltage rises with the discharge and is saturated at a certain potential, this potential is set as the saturated voltage, the discharge is stopped, and the time from the moment until the charged voltage becomes 1/2 of the saturated voltage is measured.

<Inkjet recording apparatus>
The polymerizable resin composition can be used for forming an ink repellent treatment portion of an ink jet recording head that ejects fine droplets. The ink jet recording head having such an ink repellent treatment part can be used for any ink jet recording type recording head. Specifically, the contents described in the publications described in the section of the recording head described above can be given.
Furthermore, the present invention is an appropriate apparatus for ejecting fine droplets through a small nozzle other than the ink jet recording apparatus, and can be applied to an appropriate apparatus that requires liquid repellency on the nozzle plate. These liquids include paints (varnishes), solvents, pharmaceutical fluids and the like.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “%” represents “% by mass” unless otherwise specified.

(Synthesis example)
<Preparation of polymerizable group-containing sol liquid a-1>
To a reactor equipped with a stirrer and a reflux condenser, 48 g of acryloyloxypropyltrimethoxysilane, 0.84 g of aluminum diisopropoxide ethyl acetoacetate, 60 g of methyl ethyl ketone, 0.06 g of hydroquinone monomethyl ether, and 11.1 g of water were mixed. After reacting at 60 ° C. for 4 hours, it was cooled to room temperature to obtain a transparent sol liquid a-1.
The mass average molecular weight was 1700, the component having a mass average molecular weight of 1000 to 20000 was 100% when the component equal to or higher than the oligomer component was 100%, and the value of T3 / T2 was 1.1. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

<Preparation of polymerizable group-containing sol liquid a-2>
A reactor equipped with a stirrer and a reflux condenser, 29.5 g of acryloyloxypropyltrimethoxysilane, 62.5 g of ethanol, 3.4 g of ion-exchanged water and 3 g of 2N hydrochloric acid were added and mixed, and then reacted at 40 ° C. for 3 hours. After cooling to room temperature, 30 g of ethanol was added to obtain a transparent sol solution a-2. The mass average molecular weight was 1300, the component having a mass molecular weight of 1000 to 20000 was 100%, and the value of T3 / T2 was 0.6. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

<Preparation of polymerizable group-containing sol liquid a-3>
A reactor equipped with a stirrer and a reflux condenser, 161 g of acryloyloxypropyltrimethoxysilane, 123 g of oxalic acid, and 415 g of ethanol were added and mixed. After reacting at 70 ° C. for 4 hours, the solution was cooled to room temperature and a clear sol solution a -3 was obtained.
The mass average molecular weight was 1600, the component having a mass average molecular weight of 1000 to 20000 was 100% when the component equal to or higher than the oligomer component was 100%, and the value of T3 / T2 was 0.9. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

<Preparation of polymerizable group-containing sol liquid a-4>
In preparation of sol composition a-1 of organosilane, 29.5 g of acryloyloxypropyltrimethoxysilane was changed to a mixture of 19.5 g of acryloyloxypropyltrimethoxysilane and 10.0 g of glycidoxypropyltrimethoxysilane. A transparent sol solution a-4 was obtained in the same manner as in the preparation of the organosilane sol composition a-1. The mass average molecular weight was 1400, the component having a mass average molecular weight of 1000 to 20000 was 100% when the component equal to or higher than the oligomer component was 100%, and the value of T3 / T2 was 1.0. Further, from the gas chromatography analysis, no organosilane as a raw material remained at all.

<Preparation of polymerizable group-containing sol liquid a-5>
To a reactor equipped with a stirrer and a reflux condenser, 40 g of acryloyloxypropyltrimethoxysilane, 50.6 g of methyl isobutyl ketone, 0.05 g of hydroquinone monomethyl ether, 9.2 g of water and 0.17 g of sulfuric acid were added and mixed. After reacting at 0 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a transparent sol solution. A mixed solution of 50 g of water and 0.13 g of sodium hydroxide was added to the sol solution, and the mixture was vigorously stirred so that the whole became cloudy, and then allowed to stand to remove the separated aqueous phase. Subsequently, it was washed with 40 g of saturated saline, and further dehydrated with anhydrous magnesium sulfate.
The mass average molecular weight was 1700, the component having a mass average molecular weight of 1000 to 20000 was 100% when the component equal to or higher than the oligomer component was 100%, and the value of T3 / T2 was 2.5. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

<Preparation of Sol Solution a-6>
In the preparation of the sol liquid a-3, except that the reaction conditions were changed to 70 ° C. and 4 hours were changed to 100 ° C. and 9 hours, the white turbid comparative sol liquid b-2 was obtained in the same manner as the preparation of the sol liquid a-1. It was. As for the mass average molecular weight, the component having a broad molecular weight distribution of 520,000 was 25%, the component having the mass average molecular weight of 1800 was 75%, and the value of T3 / T2 was 1.8. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

<Preparation of Sol Solution a-7>
To a reactor equipped with a stirrer and a reflux condenser, 40 g of acryloyloxypropyltrimethoxysilane, 50.6 g of methyl isobutyl ketone, 0.05 g of hydroquinone monomethyl ether, 9.2 g of water and 0.17 g of sulfuric acid were added and mixed. After reacting at 0 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a transparent sol solution. A mixed solution of 50 g of water and 0.15 g of sodium hydroxide was added to the sol solution, and the mixture was vigorously stirred so that the whole became cloudy, and then allowed to stand to remove the separated aqueous phase. Subsequently, it was washed with 40 g of saturated saline, and further dehydrated with anhydrous magnesium sulfate.
The mass average molecular weight is 1800, the mass part of the component having a mass average molecular weight of 1000 to 20000 is 100, and the value of T3 / T2 is 4.2. It was. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

<Preparation of sol liquid b-1 for comparison>
In the preparation of the sol liquid a-1, a transparent comparative sol liquid b-1 was prepared in the same manner as the preparation of the sol liquid a-1, except that acryloyloxypropyltrimethoxysilane was replaced with 3-acetoxypropyltetramethoxylane. Obtained. The mass average molecular weight was 1400, the component having a mass average molecular weight of 1000 to 20000 was 100% when the component equal to or higher than the oligomer component was 100%, and the value of T3 / T2 was 0.9. Moreover, from gas chromatography analysis, the raw material 3-acetoxypropyltetramethoxylane did not remain at all.

(Polymerizable resin composition)
Mixing methoxyphenol (storage stabilizer) as a component common to the components shown in the following table to 0.02% by mass with respect to the solid content, diluting with methyl ethyl ketone, and filtering through a polypropylene filter having a pore size of 1 μm. Thus, a polymerizable resin composition was prepared.

SI: MEK-ST (trade name: manufactured by Nissan Chemical Co., Ltd., silica sol 30% methyl ethyl ketone dispersion with an average particle size of about 15 nm) Inorganic fine particles
IRG907: Irgacure 907 (trade name: manufactured by Ciba Geigy) Photo radical polymerization initiator
IRG1870: Irgacure 1870 (trade name: manufactured by Ciba Geigy) Photo radical polymerization initiator
DETX: Kayacure-DETX (trade name: manufactured by Nippon Kayaku Co., Ltd.) Photosensitizer
EDA: N-ethyldiethanolamine polymerization accelerator
U: Urea film properties control
D110N: Takenate D110N (Product name: Takeda Pharmaceutical Co., Ltd., polyfunctional isocyanate compound) Control of membrane properties
TGE: Trimethylolpropane triglycidyl ether Control of membrane properties
PET4A: Pentaerythritol tetraacrylate (polyfunctional acrylate compound) Control of film properties
PAA: acrylic acid-butyl acrylate copolymer (copolymerization molar ratio 20:80, molecular weight 6000) Control of film properties
P2-1: Hexafluoropropylene / hydroxypropyl vinyl ether copolymer (molar ratio 1: 1)
P2-2: Macromonomer / glycidyl methacrylate copolymer (60/30 mass ratio) having a poly (1H, 1H-perfluorooctyl acrylate) structure

Example 1
The ink jet recording head shown in FIG. 1 was created. Here, FIG. 1 is a partially enlarged sectional view showing a main part of the ink jet recording head of the present invention. The ink jet recording head shown in FIG. 1 has a water-repellent resin film 3 placed on the surface of a nozzle plate 1 in which nozzle holes 2 are arranged. Specifically, in this embodiment, the nozzle hole portion of the nozzle plate 1 is previously protected from the back side of the plate with a positive resist, and the resin film forming polymerizable composition is applied to the surface of the nozzle plate 1. The film thickness after drying was applied to 1.5 μm, UV irradiation was performed with a metal halide lamp at 300 mJ / cm ² , heat treatment as shown in Table 2 was performed to create a cured film, and then the resist was removed. Manufactured. In this embodiment, the water-repellent resin film is installed after the nozzle holes are created in advance, but the nozzle holes may be provided after the water-repellent resin film is installed on the nozzle plate having no nozzle holes.

  The inkjet head using the manufactured nozzle plate was confirmed to eject ink droplets stably from all nozzles. Further, the following durability test was conducted.

Durability: As an evaluation of durability, the surface of the nozzle plate was wet wiped with urethane rubber, and scratches and peelings were observed. A sample having no scratches or peelings was designated as A, a sample having slight scratches but no peelings was designated as B, and those having peelings were designated as C.
Ink repellency: The ink was immersed in an ink at 55 ° C. for 3 days to investigate the ink repellency. A was the same as before immersion, A was slightly deteriorated in ink repellency but could be used practically, and B was ink repellency significantly deteriorated and could not be used practically.

  As is apparent from the results in Table 2, by using the polymerizable composition for forming a resin film of the present invention, no heat treatment or gentle heat treatment at 100 ° C. or lower can be carried out, so that ejection suitability and durability, A water-repellent resin film having excellent ink properties can be formed, and particularly when inorganic fine particles are added or the fluorine-containing polymer is a radical polymerizable polymer, it has excellent durability.

(Example 2)
After providing an intermediate layer with an epoxy resin in advance on the surface of the nozzle plate 1 in FIG. 1, a polymerizable composition P-32 was applied, and a heat treatment at 90 ° C. for 20 minutes was performed to form a water-repellent resin film. . When the evaluation was performed in the same manner as in Example 1, it was found that dischargeability was excellent, and adhesion and ink repellency were excellent as A.

FIG. 1 is a partially enlarged cross-sectional view showing the main part of the ink jet recording head of the present invention.

Explanation of symbols

1 Nozzle plate 2 Nozzle hole 3 Water-repellent resin film

Claims (8)

In an ink jet recording head having an ejection port for ejecting a recording liquid, and at least the periphery of the ejection port being subjected to ink repellent treatment, the ink repellent treatment portion of the recording head includes:
(A) a hydrolyzate of organosilane containing a radical polymerizable group and / or a partial condensate thereof;
(B) viewing including the crosslinked fluorine-containing compound and contains at least a polymerizable resin composition,
The hydrolyzate of organosilane and / or its partial condensate containing a radically polymerizable group (a) has a mass average molecular weight of 1000 to 20000 when the mass average molecular weight is 300% by mass or more. An ink jet recording head , wherein the component is 80% by mass or more and the value of T3 / T2 is a value of 0.2 to 3.0 .
(T3 / T2 represents the ratio of the peak area (T3) when no silanol group remains and the peak area (T2) when one silanol group remains, calculated from the peak intensity of silicon NMR.) In an ink jet recording head having an ejection port for ejecting a recording liquid, and at least the periphery of the ejection port being subjected to ink repellent treatment, the ink repellent treatment portion of the recording head includes:
(A) 'a polyorganosiloxane containing radically polymerizable groups;
(B) viewing including the crosslinked fluorine-containing compound and contains at least a polymerizable resin composition,
The polyorganosiloxane containing the (a) ′ radical polymerizable group has a weight average molecular weight of 300 or more as 100% by weight, and a weight average molecular weight of 1000 to 20000 is a component of 80% by weight or more. An ink jet recording head having a T3 / T2 value of 0.2 to 3.0 .
(T3 / T2 represents the ratio of the peak area (T3) when no silanol group remains and the peak area (T2) when one silanol group remains, calculated from the peak intensity of silicon NMR.) An ink jet recording head according to claim 1 or 2 organosilane containing the radical polymerizable group is characterized in that a compound represented by the following general formula (1).

(R ²¹ represents hydrogen or a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, fluorine or chlorine. Y represents a single bond or an ester group, an amide group, an ether group or a urea group. L represents a divalent linkage. Represents a chain, n represents 0 or 1. R ²² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and Xh represents a hydroxyl group or a hydrolyzable group. The polymerizable resin composition, the ink-jet recording head according to any one of claims 1 to 3, characterized in that it further contains inorganic fine particles. The fluorine-containing compound, an ink jet recording head according to any one of claims 1-4, characterized in that the polymerizable group-containing fluoropolymer. An ink jet recording apparatus equipped with an ink jet head, wherein the ink jet head is the ink jet head according to any one of claims 1 to 5 .   (A) hydrolyzate of organosilane containing a radical polymerizable group and / or partial condensate thereof, or (a) polyorganosiloxane containing a polymerizable group, (b) a fluorine-containing compound, (c) ) A polymerizable resin composition for water-repellent treatment, comprising at least inorganic fine particles. In the manufacturing method of the inkjet recording head in any one of Claims 1-6 ,
In the ink repellent portion of the recording head, a solvent, (a) a hydrolyzate of organosilane containing a radical polymerizable group and / or a partial condensate thereof, or (a) a polyorgano containing a radical polymerizable group A step of applying a polymerizable resin composition containing at least siloxane and (c) a fluorine-containing compound, and applying an activation energy ray or heat to the coating film formed by evaporating the solvent after coating. A method for producing an ink jet recording head, comprising a step of forming a crosslinked body of a polymerizable polymer.

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