JPH09221620A - Coating material for ink jet printer head - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water repelling coating material at a low cost, having good adhesiveness to various materials and causing no liquid accumulation even in use for a long time. SOLUTION: This coating material for an ink jet printer head comprises a polymer A which comprises 20-80wt.% of a fluorine-containing monomer (a) having a carbon to carbon double bond and a perfouroalkyl group and 80-20wt.% of a monomer (b) having the carbon to carbon double bond and a self-crosslinking functional group and a polymer (B) which comprises 30-100wt.% of the monomer (b) having the carbon to carbon double bond and the selfcrosslinking functional group, 0-40wt.% of a monomer (c) having the carbon to carbon double bond and an acidic group and 0-70wt.% of a monomer (d) having the carbon to carbon double bond, and contains 0.1-10wt.% of the fluorine containing monomer (a) based on the total coating material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating material for an ink jet printer head.

[0002]

2. Description of the Related Art As one of recording apparatuses, an ink jet printer which is low in noise and high in speed is known. The printer prints by ejecting ink from an ink ejection port. For example, the ink ejection port described in JP-A-2-30540 is made of silicon, glass, and a photosensitive resin film for bonding them. Different materials are used in combination. In the case of normal ink, among the above three types of materials, ink leaked from the glass having the lowest interfacial tension with the ink, causing a phenomenon of liquid pool covering the periphery of the ink ejection port with ink. When this liquid pool occurs, the ejecting direction of the ejected ink becomes unstable, and printing stains occur, and in some cases, ink ejection becomes impossible.

For this reason, it has been proposed to apply various water-repellent paints such as silicone oil to the vicinity of the discharge port. However, these water-repellent paints have a problem in adhesiveness to the above-mentioned materials and have a problem that they peel off when used for a long time. In addition, the methods described in JP-A-59-176059 and JP-A-63-3963 and attempts to use the above-mentioned fluoropolymers have been made, but expensive fluoropolymers must be used in large amounts, and the cost is low. There was a problem in terms of.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a water-repellent coating which has good adhesiveness to various materials, does not cause liquid pooling even after long-term use, and is inexpensive. is there.

[0005]

DISCLOSURE OF THE INVENTION The present invention comprises 20 to 80% by weight of a fluorine-containing monomer (a) having a carbon-carbon unsaturated double bond and a perfluoroalkyl group, and a carbon-carbon unsaturated double bond. Monomer (b) 8 having self-crosslinking functional group
Polymer (A) consisting of 0 to 20% by weight, and monomer (b) having a carbon-carbon unsaturated double bond and a functional group capable of self-crosslinking
30 to 100% by weight, and a monomer (d) 0 having a carbon-carbon unsaturated double bond and an alkyl group or a phenyl group
Up to 70% by weight of polymer (B), polymer (A)
And the fluorine-containing monomer (a) in the total amount of the polymer (B)
Is 0.1 to 10% by weight.

Further, the polymer (B) is a monomer (b) 30 having a carbon-carbon unsaturated double bond and a functional group capable of self-crosslinking.
˜99.9% by weight, a monomer having a carbon-carbon unsaturated double bond and an acidic group (c) 0.1 to 40% by weight, a carbon-carbon unsaturated double bond and an alkyl group or a phenyl group The monomer (d) is 0 to 69.9% by weight.
The paint for inkjet printer heads described above. Moreover, the self-crosslinking functional group of the monomer (b) having a carbon-carbon unsaturated double bond and a self-crosslinking functional group is an alkoxysilyl group, an isocyano group, an epoxy group, an N-methylol group, or N -The present invention relates to the coating material for inkjet printer head, which is at least one functional group selected from the group consisting of alkoxymethyl groups. Furthermore, for the inkjet printer head, the monomer (e) having two or more carbon-carbon unsaturated double bonds is contained in an amount of 10 to 900% by weight based on the total amount of the polymer (A) and the polymer (B). Regarding paints.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-containing monomer (a) having a carbon-carbon unsaturated double bond and a perfluoroalkyl group of the present invention is used for imparting a water-repellent effect to a paint.
Specifically, 2-perfluoroisononylethyl (meth) acrylate, 2-pa-fluorononylethyl (meth) acrylate, 2-pa-fluorodecylethyl (meth) acrylate, 2-pa-fluorobutylethyl (meth) ) Acrylate, perfluorooctylmethyl (meth) acrylate, perfluorodecylmethyl (meth)
Acrylate, perfluoropropylpropyl (meth)
Acrylate, perfluorooctylpropyl (meth)
Acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth)
Perfluoroalkylalkyl (meth) having a perfluoroalkyl group having 1 to 20 carbon atoms such as acrylate
Examples thereof include perfluoroalkylethylene such as acrylate, perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene. These may be used alone or in combination of two or more depending on the required performance. Monomer (a) is 2 relative to polymer (A)
It is used in a copolymerization ratio of 0 to 80% by weight, preferably 40 to 70% by weight. If it is less than 20% by weight, sufficient water repellency cannot be obtained, and if it is more than 80% by weight, sufficient hardness of the coating film cannot be obtained.

The monomer (b) having a carbon-carbon unsaturated double bond and a self-crosslinking functional group used in the present invention is used for crosslinking after coating to form a hard coating film. . Examples of the self-crosslinking functional group include an alkoxysilyl group, an isocyano group, an epoxy group, an amino group, a hydroxy group and an alkoxy group. Examples of the monomer (b) having an alkoxysilyl group include (meth) acryloxyalkylsilanes such as γ- (meth) acryloxypropyltrimethoxysilane and γ- (meth) acryloxypropylmethyldimethoxysilane, ( (Meth) acryloxyalkoxysilane, (meth) acryloxyalkylalkoxysilane, trimethoxyvinylsilane, dimethoxyethylsilane, triethoxyvinylsilane, triethoxyallylsilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltris (2-methoxy) Ethoxy) silane and the like.

Further, a monomer (b) having an isocyano group
Examples of (meth) acryloyloxyethylisocyanate, (meth) acryloyloxypropylisocyanate, etc., as well as hydroxy (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxyputyl (meth) acrylate, Examples thereof include those obtained by reacting with a polyisocyanate such as toluene diisocyanate, isophorone diisocyanate, and Coronate L. Examples of the monomer (b) having an epoxy group include glycidyl methacrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, vinylcyclohexane monoepoxide, 1,3-butazinene monoepoxide and the like. In addition, examples of the monomer (b) having an N-methylol group or an N-alkoxymethyl group include N-
N-monoalkoxymethyl groups such as methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide (Meth) acrylamide, N, N-dimethylol (meth) acrylamide, N, N-di (methoxymethyl) (meth)
Acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide, N, N-di (propoxymethyl)
(Meth) acrylamide having an N, N-dialkoxymethyl group such as (meth) acrylamide and N, N-di (butoxymethyl) (meth) acrylamide.

From these, one kind or a mixture of two or more kinds can be used depending on the required performance. Further, the one used in the polymer (A) and the one used in the polymer (B) are not necessarily required to be the same. The monomer (b) is used in the polymer (A) at a copolymerization ratio of 80 to 20% by weight. If less than 20% by weight,
If sufficient hardness is not obtained and it is more than 80% by weight,
Water repellency decreases. Further, in the polymer (B), 30 to
It is used in a copolymerization ratio of 100% by weight, preferably 30 to 99.9% by weight. If it is less than 30% by weight, sufficient hardness cannot be obtained.

The monomer (c) having a carbon-carbon unsaturated double bond and an acidic group used in the present invention is used for improving hardness. Specific examples thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, styrenesulfonic acid, maleic anhydride and the like. You may use 2 or more types of these. The monomer (c) is used in an amount of 0.1 to 40% by weight based on the polymer (B). If it is more than 40% by weight, sufficient adhesion to the substrate cannot be obtained. Further, the compatibility with the polymer (A) decreases, and a uniform and good coating film cannot be obtained.

The monomer (d) having a carbon-carbon unsaturated double bond and an alkyl group or a phenyl group used in the present invention is used for imparting physical properties such as hardness and toughness. Specific examples include esters of (meth) acrylic acid such as methyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, styrene, and the like. Two or more of these may be used. The monomer (d) is 0 relative to the polymer (B).
˜70 wt%, and when the monomer (c) is used, it is used at 0 to 69.9 wt%. If it is more than 70% by weight, sufficient adhesion to the substrate cannot be obtained. Also,
The compatibility with the polymer (A) decreases, and a uniform and good coating film cannot be obtained.

The polymer (A) and the polymer (B) can be obtained by a known method such as solution polymerization. As the solvent used, methanol, ethanol, propanol, butanol, ethylene glycol methyl ether, alcohols such as diethylene glycol methyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclopropanone, tetrahydrofuran,
Ethers such as dioxane, ethylene glycol dimethyl ether, ethylene glycol dimethyl ether,
Hydrocarbons such as hexane, heptane and octane, aromatics such as benzene, toluene, xylene and cumene, and esters such as ethyl acetate and butyl acetate can be used. The solvent may be a mixture of two or more. The charged concentration of the monomer at the time of synthesis is preferably 1 to 80% by weight.

As the polymerization initiator, a usual peroxide or azo compound, for example, benzoyl peroxide, azoisobutylvalenonitrile, azobisisobutyronitrile, di-t-butylperoxide, t-butylperbenzoate, T-butyl peroctoate, cumene hydroxyperoxide, etc. are used, and the polymerization temperature is 50 to 140.
° C, preferably 70 to 140 ° C. The preferred average molecular weight of the obtained polymer is 2,000 to 100,000 for both the polymer (A) and the polymer (B).

In the present invention, various catalysts may be added to accelerate the crosslinking of the self-crosslinking functional group in the composition. When a monomer (b) having an alkoxysilyl group is used as a typical catalyst, aluminum triacetylacetonate, iron triacetylacetonate,
Metal complex compounds such as manganese tetraacetylacetonate, nickel tetraacetylacetonate, chromium hexaacetylacetonate, titanium tetraacetylacetonate and cobalt tetraacetylacetonate, aluminum ethoxide, aluminum propoxide, aluminum butoxide, titanium ethoxide. , Metal alkoxides such as titanium propoxide, titanium butoxide, sodium acetate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate,
Metal salt compounds such as lead naphthenate, cobalt naphthenate, dibutyltin dioctate, dibutyltin dilaurate and dibutyltin malate, formic acid, acetic acid, propionic acid, p-
Toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, phosphoric acid ester of β-hydroxyethyl (meth) acrylate, monoalkyl phosphorous acid, dialkyl phosphorous acid and other acidic compounds can be mentioned. . In particular, tin compounds such as dibutyltin diacetate dibutyltin dioctate, dibutyltin dilaurate and dibutyltin dimalate, and p-toluenesulfonic acid are preferable.

Further, a monomer (b) having an isocyano group
Is used, triethylamine, N, N, N ′,
N'-Tetramethyl-1,3-butanediamine, diethanolamine, dibutyltin dilaurylate, dibutyltin di (2-ethylhexoate) and the like are preferable. Also,
In the case of the monomer (b) having an epoxy group, sodium hydroxide, lithium chloride, diethyl zinc, tetra (n-butoxy) titanium, triethylamine, N, N-
Dimethylbenzylamine and the like are preferable. When a monomer (b) having an N-methylol group or an N-alkoxymethyl group is used, p-toluenesulfonic acid, phthalic anhydride, benzoic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, formic acid, Itaconic acid, oxalic acid, maleic acid, and their ammonium salts, lower amine salts, polyvalent metal salts and the like are preferable. The amount of these catalysts used is in the range of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on 100% by weight of the paint.

Further, in the present invention, a silane coupling agent (C) can be used if necessary. Specific examples of the silane coupling agent include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane and γ-methacryloyloxy. Propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-morpholinopropyl Trifunctional silane such as trimethoxysilane, and further difunctional silane in which a part of the above trifunctional silane is substituted with an alkyl group, a phenyl group, a vinyl group or the like, for example, dimethyldimethoxysilane, phenylmethyldimethoxysila. , Vinyl methyl dimethoxy silane, .gamma.-chloropropyl methyl dimethoxy silane, such as .gamma.-glycidoxypropylmethyldimethoxysilane and the like. In addition, hydrolysates and partial condensates of these compounds can be used. The silane coupling agent (C) is used in an amount of 1 to 40% by weight, preferably 3 to 20% by weight, based on the total amount of the polymer (A) and the polymer (B).

Further, in the present invention, the organosilica sol (D) can be further used if necessary. The organosilica sol is a colloid solution in which colloidal silica is stably dispersed in an organic solvent. As typical ones, for example, trade names IPA-ST, MIBK-ST, MA-ST-M, EG manufactured by Nissan Chemical Industries, Ltd.
-ST, EG-ST-ZL, NPC-ST, DMAC-
ST, DMAC-ST-ZL, XBA-ST, methanol silica sol and the like are listed. The organosilica sol is used in an amount of 0 to 80% by weight, preferably 20 to 60% by weight, based on the total amount of (A), (B) and (C) of the present invention. If it is less than this range, the effect of improving water repellency is small, and if it exceeds this range, the adhesion to the substrate is impaired.

Further, the coating material comprising the polymer (A) and the polymer (B) used in the present invention is further prepared by adding a monomer (e) having two or more carbon-carbon unsaturated double bonds. , UV curability and flowability can be improved. Specific examples of the monomer (e) include monomers in which a part or all of the polyol is substituted with (meth) acrylic acid ester, allyl ether, vinyl ether or the like.

Examples of such a polyol include dihydric or higher aliphatic polyols such as ethylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol, or their polyalkylene glycol, epichlorohydrin or caprolactone modified products. , Phthalic acid, hexahydrophthalic acid, succinic acid, malonic acid, hexanedioic acid,
Polyalkylene glycols of divalent or higher valent carboxylic acids such as citric acid and pyromellitic acid, or epichlorohydrin modified products, polyalkylene glycols of bisphenol A derivatives, or epichlorohydrin modified products, polyalkylene glycol modified products of isocyanuric acid derivatives, catechol, resorcin , A divalent or higher phenol such as hydroquinone, phloroglucin, and pyrogallol. In addition, examples of the monomer (e) include bicyclohexene, bismaleimide, and divinylbenzene. Usually, the number of ethylenically unsaturated bonds in one molecule is preferably 2 to 6.

Such a monomer (e) is a polymer (A).
It is preferable to add 10 to 900% by weight based on the total of the polymer (B). If it exceeds 900% by weight, sufficient water repellency cannot be obtained. In case of UV curing, add 0.01% UV initiator to the whole paint.
It is necessary to add 10 to 10 weight. Examples of such UV initiators include camphorquinone, benzophenone, diacetyl, benzyl, Michler's ketone, diaryliodonium salts, and polyhalogen compounds. Further, various sensitizing dyes may be added. The UV light source is not particularly limited, and a mercury lamp, a xenon lamp, a fluorescent lamp, an incandescent lamp, and various lasers are preferably used.

In the present invention, a filler, a thixotropy-imparting agent, a coloring pigment, an extender pigment, a dye, an antioxidant, an antioxidant, an antistatic agent, a flame retardant, if necessary, as long as the effects of the present invention are not impaired. Various additives such as a thermal conductivity improver, a plasticizer, an anti-sagging agent, an antifouling agent, a preservative, a bactericide, an antifoaming agent, a leveling agent, and a curing agent may be added.

The coating composition of the present invention comprises a polymer (A), a polymer (B), and optionally a silane coupling agent (C), an organosilica sol (D), a monomer (e), a catalyst, and an additive as a solvent. It is obtained by mixing and dissolving in. The mixing method is not particularly limited, but normally, the polymer solution used at the time of polymerization may be directly mixed and stirred with a stirring blade, a permeation stirrer, a rotary stirrer or the like. In order to improve coatability and the like, a solvent may be further added or concentrated. Further, the mixing ratio of the polymer (A) and the polymer (B) is such that the fluorine-containing monomer (a) is 0.1 in the total amount of the polymer (A) and the polymer (B).
It is necessary to set it to 10% by weight. If it is less than 0.1% by weight, a sufficient water repellent effect cannot be obtained, and 10
If it is more than wt%, sufficient coating film hardness cannot be obtained,
Also, the cost is high. The paint thus obtained is applied to an inkjet printer head. The application method is not particularly limited, but application can be made by dip coating, spray coating, brush coating, or the like. A tough water-repellent coating film can be obtained by air-drying or heating the applied coating material at 30 to 220 ° C. for several seconds to several weeks.

[0024]

Hereinafter, the present invention will be described in detail with reference to examples. (Synthesis Example A1) 50 g of 2- (perfluorooctyl) ethyl methacrylate, 50 g of γ-methacryloxypropyltrimethoxysilane, and 200 g of ethyl acetate were charged into a four-necked flask equipped with a cooling tube, a stirrer, and a thermometer, and a nitrogen gas flow was applied. The temperature was raised to 80 ° C. with stirring under reduced pressure, 1.6 g of azobisisobutyronitrile was added, polymerization was carried out for 2 hours, and 0.4 part of azobisisobutyronitrile was further added, and polymerization was carried out for 2 hours. Weight average molecular weight of about 15,000
Thus, a polymer (A1) solution was obtained.

(Synthesis Example A2) 50 g of 2- (perfluorooctyl) ethyl methacrylate, 45 g of γ-methacryloxypropyltrimethoxysilane, 5 acrylic acid
g, 200 g of isopropyl alcohol were charged into a four-necked flask equipped with a cooling tube, a stirrer, and a thermometer, heated to 80 ° C. with stirring under a nitrogen stream, and added with 1.6 g of azobisisobutyronitrile. The polymerization reaction was carried out for 2 hours, 0.4 part of azobisisobutyronitrile was further added, and the polymerization was carried out for 2 hours to obtain a polymer (A2) solution having a weight average molecular weight of about 12,000.

(Synthesis Example A3) 50 g of 2- (perfluorooctyl) ethyl methacrylate, 50 g of 2-methacryloxyethyl isocyanate and 200 g of ethyl acetate were placed in a four-necked flask equipped with a condenser, a stirrer and a thermometer, and nitrogen was introduced. While stirring under an air stream, the temperature was raised to 80 ° C., 1.6 g of azobisisobutyronitrile was added, and a polymerization reaction was carried out for 2 hours.
And polymerized for 2 hours to give a weight average molecular weight of about 15.0.
Thus, a polymer (A3) solution of No. 00 was obtained.

(Synthesis example A4) 45 g of 2- (perfluorooctyl) ethyl methacrylate, 55 g of glycidyl methacrylate and 200 g of ethyl acetate were placed in a four-necked flask equipped with a cooling tube, a stirrer and a thermometer, and stirred under a nitrogen stream. Meanwhile, the temperature was raised to 80 ° C., 1.6 g of azobisisobutyronitrile was added and a polymerization reaction was performed for 2 hours, 0.4 part of azobisisobutyronitrile was further added and polymerization was performed for 2 hours, and a weight average molecular weight was obtained. About 13,000 polymer (A4) solution was obtained.

(Synthesis example A5) 45 g of 2- (perfluorooctyl) ethyl methacrylate, 55 g of N, N-di (methoxymethyl) methacrylamide and 200 g of isopropyl alcohol were equipped with a cooling pipe, a stirrer and a thermometer.
The temperature was raised to 80 ° C. with stirring, 1.6 g of azobisisobutyronitrile was added, polymerization was carried out for 2 hours, and 0.4 part of azobisisobutyronitrile was further added. Polymerization for about 1 hour, weight average molecular weight about 1
8,000 polymer (A5) solutions were obtained.

(Synthesis Example B1) 100 g of γ-methacryloxypropyltrimethoxysilane, 200 g of ethyl acetate
Was charged into a four-necked flask equipped with a condenser, a stirrer, and a thermometer, and heated to 80 ° C. while stirring under a nitrogen stream, 1.6 g of azobisisobutyronitrile was added, and the polymerization reaction was performed for 2 hours. And azobisisobutyronitrile 0.1.
4 parts were added and polymerized for 2 hours to obtain a weight average molecular weight of about 10,
000 of the polymer (B1) was obtained.

(Synthesis example B2) 80 g of γ-methacryloxypropyltrimethoxysilane, 20 g of methacrylic acid,
200 g of isopropyl alcohol, a cooling tube, a stirrer,
A 4-necked flask equipped with a thermometer was charged, the temperature was raised to 80 ° C. with stirring under a nitrogen stream, 1.6 g of azobisisobutyronitrile was added, and a polymerization reaction was performed for 2 hours. 0.4 parts of ronitrile was added and polymerization was carried out for 2 hours to obtain a polymer having a weight average molecular weight of about 14,000 (B
2) A solution was obtained.

(Synthesis Example B3) 98 g of γ-methacryloxypropyltrimethoxysilane, 2 g of acrylic acid and 200 g of isopropyl alcohol were placed in a four-necked flask equipped with a cooling tube, a stirrer and a thermometer, and stirred under a nitrogen stream. While the temperature was raised to 80 ° C, 1.6 g of azobisisobutyronitrile was added and a polymerization reaction was carried out for 2 hours, 0.4 part of azobisisobutyronitrile was further added and polymerization was carried out for 2 hours, and a weight average molecular weight of about A polymer (B3) solution of 11,000 was obtained.

(Synthesis Example B4) 100 g of γ-methacryloxypropyltrimethoxysilane and 200 g of isopropyl alcohol were placed in a four-necked flask equipped with a cooling tube, a stirrer and a thermometer, and stirred at 80 ° C. under a nitrogen stream.
Then, 1.6 g of azobisisobutyronitrile was added, polymerization was carried out for 2 hours, and 0.4 part of azobisisobutyronitrile was further added, polymerization was carried out for 2 hours, and the weight average molecular weight was about 9,000. A polymer (B4) solution was obtained.

(Synthesis Example B5) 50 g of 2-methacryloxyethyl isocyanate, 50 g of butyl methacrylate
g and 200 g of ethyl acetate were placed in a four-necked flask equipped with a condenser, a stirrer, and a thermometer, and heated to 80 ° C. while stirring under a nitrogen stream, and 1.6 g of azobisisobutyronitrile was added. A polymerization reaction was carried out for 2 hours, and 0.4 part of azobisisobutyronitrile was further added, followed by polymerization for 2 hours to obtain a polymer (B5) solution having a weight average molecular weight of about 14,000.

(Synthesis example B6) 50 g of glycidyl methacrylate, 50 g of butyl methacrylate, 20 ethyl acetate
0 g was charged into a four-necked flask equipped with a condenser, a stirrer, and a thermometer. The temperature was raised to 80 ° C. while stirring under a nitrogen stream, and 1.6 g of azobisisobutyronitrile was added. And further add 0.4 parts of azobisisobutyronitrile, and polymerize for 2 hours to obtain a weight average molecular weight of about 1
7,000 polymer (B6) solutions were obtained.

(Synthesis example B7) N, N-di (methoxymethyl) methacrylamide 30 g, methyl methacrylate 7
0 g and 200 g of isopropyl alcohol were charged into a four-necked flask equipped with a cooling tube, a stirrer, and a thermometer, the temperature was raised to 80 ° C. with stirring, 1.6 g of azobisisobutyronitrile was added, and the polymerization reaction was performed for 2 hours. Was further added, and 0.4 parts of azobisisobutyronitrile was added, followed by polymerization for 2 hours to obtain a polymer (B7) solution having a weight average molecular weight of about 20,000.

(Comparative Synthesis Example A6) 1 g of 2- (perfluorooctyl) ethyl methacrylate, 99 g of γ-methacryloxypropyltrimethoxysilane and 200 g of isopropyl alcohol were used in the same composition ratio as in Example 1.
Charge 4 g to a four-necked flask equipped with a cooling tube, a stirrer, and a thermometer, raise the temperature to 80 ° C. with stirring under a nitrogen stream, add 1.6 g of azobisisobutyronitrile, and perform a polymerization reaction for 2 hours. Then, 0.4 part of azobisisobutyronitrile was added, and the mixture was polymerized for 2 hours to give a weight average molecular weight of about 1
A 5,000 solution of polymer (A6) was obtained. (Examples 1 to 7) The respective solutions of the polymer (A) and the polymer (B) were mixed so that the solid content conversion would be the ratio shown in Table 1, and the mixture was stirred overnight with a rotary shaker. The catalysts shown in Table 1 were added, further diluted with a solvent to 5%, and applied to an uncoated inkjet printer head by a dip coating method. After that, leave it at room temperature for 30 minutes, then 200 ℃
It was heated for 10 minutes at room temperature, and then left at room temperature for 1 day. A printing test was performed using the inkjet printer head thus coated with water repellent. The printing status is JIS No. 1
Printing all kanji of the standard is counted as 1 time and 10
00th, 5000th, 10000th and 150th
The state of printing 00 times was evaluated by the amount of deviation from the visual impact point. Table 1 shows the results.

Comparative Example 1 A printing test similar to that of the example was carried out using an ink jet printer head not coated with a water repellent coating, and the results are also shown in Table 2. (Comparative Example 2) Instead of the polymer (A1) and the polymer (B1), only the solution of the polymer (A6) was used, and the same operation as in Example 1 was carried out except that a printing test was conducted. Table 2 shows the results.

Table 1 ────────────────────────────────── Example Polymer (A) Polymer (B ) Catalyst (g) (g) (g) ─────────────────────────────────── 1 Polymer A1 0.2 Polymer B1 9.8 Paratoluenesulfonic acid 0.1 2 Polymer A1 0.2 Polymer B2 9.8 Paratoluenesulfonic acid 0.1 3 Polymer A1 0.2 Polymer B3 9.8 Paratoluenesulfonic acid 0.1 4 Polymer A2 0.2 Polymer B4 9.8 Paratoluenesulfonic acid 0.1 5 Polymer A3 0.2 Polymer B5 9.8 Dibutyltin dilaurate 0.1 6 Polymer A4 0.2 Polymer B6 9.8 Triethylenetetramine 1.2 7 Polymer A5 0.2 Polymer B7 9.8 Paratoluenesulfonic acid 0.1 Comparative Example 2 Polymer A6 1.0-para Toluenesulfonic acid 0.1 ─────────── ────────────────────────

(Example 8) The polymer (A
1) 0.2 g, polymer (B1) 4.8 g, and trimethylolpropane triacrylate 2 g were mixed with each solution and the monomer (e), and benzophenone, 0.2 g
Was added, and the mixture was stirred overnight in a dark place with a rotary shaker, and then applied to an uncoated inkjet printer pad by a dip coating method in a dark place. After that, Toshiba UV-20
1 at a conveyor speed of 15 m / min with a 00 UV irradiation device
I passed it. After that, the same printing test as in Example 1 was performed. The results are shown in Table 2. Table 2 ────────────────────────────────── Example Printing status 1000 times 5000 times 10000 times 15000 times ─ ───────────────────────────────── 1 ○ ○ ○ ○ 2 ○ ○ ○ ○ 3 ○ ○ ○ ○ 4 ○ ○ ○ ○ 5 ○ ○ ○ △ 6 ○ ○ ○ △ 7 ○ ○ ○ △ 8 ○ ○ ○ △ Comparative example 1 ○ × × × 2 ○ × × × ─────────────── ─────────────────── ○ = Good, △ = Slightly bad, × = Poor

By using the water repellent coating composition of the present invention, an ink jet printer head can be obtained which has a very small amount of fluorine and can be stably used for a long period of time without ink pooling in the discharge port.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C09D 133/26 PFW C09D 135/00 135/00 143/04 PGL 143/04 PGL B41J 3/04 103Z

Claims (6)

[Claims] 1. A fluorine-containing monomer (a) having a carbon-carbon unsaturated double bond and a perfluoroalkyl group (20 to 80% by weight), and a carbon-carbon unsaturated double bond and a self-crosslinking functional group. Polymer (A) consisting of 80 to 20% by weight of monomer (b), 30 to 100% by weight of monomer (b) having a carbon-carbon unsaturated double bond and a self-crosslinking functional group, and carbon The polymer (B) is composed of 0 to 70% by weight of a monomer (d) having a carbon unsaturated double bond and an alkyl group or a phenyl group, and is added to the total amount of the polymer (A) and the polymer (B). The ratio of the fluorinated monomer (a) occupying is 0.1 to 10
A coating material for an inkjet printer head, which is characterized in that the content is% by weight. 2. The polymer (B) is a monomer (b) 30-9 having a carbon-carbon unsaturated double bond and a self-crosslinking functional group.
9.9% by weight, 0.1 to 40% by weight of a monomer (c) having a carbon-carbon unsaturated double bond and an acidic group, and a monomer having a carbon-carbon unsaturated double bond and an alkyl group or a phenyl group. The coating composition for an inkjet printer head according to claim 1, which comprises 0 to 69.9% by weight of the monomer (d). 3. The self-crosslinking functional group of the monomer (b) is
Alkoxysilyl group, isocyano group, epoxy group, N-
The coating composition for an inkjet printer head according to claim 1 or 2, which is at least one functional group selected from a methylol group and an N-alkoxymethyl group. 4. The inkjet printer head according to claim 1, further comprising 1 to 40% by weight of the silane coupling agent (C) based on the total amount of the polymer (A) and the polymer (B). paint. 5. The monomer (e) having 2 or more carbon-carbon unsaturated double bonds is further contained in an amount of 10 to 900% by weight based on the total amount of the polymer (A) and the polymer (B). Item 1
5. A paint for an inkjet printer head according to any one of 4 to 4. 6. The coating material for an ink jet printer according to claim 1, further comprising an organosilica sol (D).