JP2018154668A - Curable composition and liquid discharge head - Google Patents

Abstract

The present invention provides a curable composition in which the obtained cured product has excellent ink resistance. A curable composition comprising a methoxy group-containing silane-modified bisphenol-type epoxy resin (A), a polythiol compound (B) having two or more thiol groups in the molecule, and a resin composition containing an imidazole compound (C). Composition. (1 ≦ k <6; j is 0 or 1; R1 to R3 are independently H, alkyl, etc .; R4 is alkylene, CH2CH2COO, etc .; R5 is H, alkyl, aryl, etc. when k is 1, 2 ≦ k <In the case of 6, hydrocarbon group) [Selection figure] None

Description

  The present invention relates to a curable composition and a liquid discharge head.

  2. Description of the Related Art Conventionally, as an image forming apparatus such as a printer, a facsimile machine, a copying apparatus, a plotter, or a composite machine thereof, for example, a liquid discharge recording type image forming apparatus having a liquid discharge head is known.

  The liquid discharge head (hereinafter also referred to as “inkjet head”) includes a nozzle that discharges ink droplets and a liquid chamber (“pressure chamber”, “discharge chamber”, “pressure chamber”) that communicates with the nozzle. And a pressurizing liquid chamber), and pressure generating means for pressurizing ink in the liquid chamber (also referred to as “driving means” or “energy generating means”). The pressure generating means is driven to pressurize ink in the liquid chamber and eject ink droplets from the nozzle, and a flow path substrate for forming a flow path such as the liquid chamber and a nozzle plate having the nozzle Are joined together to form the inkjet head.

Bonding of the members constituting the ink-jet head includes adhesive bonding such as wet adhesive, film adhesive, etc., and when a silicone substrate is used for a liquid chamber substrate or a nozzle plate, direct bonding or common via a metal material. In the case of using crystal bonding or a metal material, anodic bonding or the like is performed.
In the ink jet head, the end portion of the bonding portion is exposed to ink, and ink discharge pressure is applied between the members. Since these discharge cycles are several kHz and are members that receive high-frequency pressure fluctuations, the deterioration of the bonded portion is likely to proceed. Therefore, liquid resistance is required rather than general adhesion.

  By the way, when joining two members generally, there exists a request | requirement that components precision must be maintained and highly reliable joining must be implement | achieved. However, in the inkjet head, there are many parts that are in contact with the ink, and the contact with the ink causes the adhesive to swell and the Young's modulus to decrease, thereby reducing the liquid chamber generated from the piezoelectric element. Pressure may drop and discharge failure may occur. Further, the contact with the ink causes a serious problem in terms of reliability, such as degrading the resin layer itself made of an adhesive or penetrating the bonding interface to cause peeling. For this reason, it is desired that the resin layer has resistance to the ink used and has sufficient bonding strength by suppressing permeation deviation to the bonding interface as much as possible. There was no agent present, and it was extremely difficult to select a low-degradation adhesive for a specific ink.

On the other hand, in recent years, household ink jet printers and industrial ink jet plotters have become widespread, so the opportunity to discharge water-based inks and oil-based inks has increased, and adhesives corresponding to these inks have also been found.
For example, an adhesive composition (for example, refer to Patent Document 1) in which the ink resistance is improved by increasing the crosslink density, and an adhesive composition (for example, an ink jet print head that exhibits excellent resistance to UV ink (for example, Patent Document 2) has been proposed.
In addition, a resin composition used for a liquid discharge head having excellent initial adhesiveness and adhesive reliability has been proposed (see, for example, Patent Document 3).

  An object of the present invention is to provide a curable composition in which the obtained cured product is excellent in ink resistance.

The curable composition of the present invention as a means for solving the above problems includes a methoxy group-containing silane-modified bisphenol type epoxy resin (A), a polythiol compound (B) having two or more thiol groups in the molecule, and A resin composition containing the imidazole compound (C) represented by the general formula (1) is contained.
However, in said general formula (1), k is 1 or more and less than 6. j is 0 or 1. R ₁ , R ₂ , and R ₃ each independently represent any of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group. R ₄ represents any one of an alkylene group having 1 to 20 carbon atoms, an arylene group, and —CH ₂ CH ₂ COO—. R ₅ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cyanomethyl group when k is 1, and has 1 to 20 carbon atoms when k is 2 or more and less than 6. Represents a hydrocarbon group.

  According to the present invention, it is possible to provide a curable composition in which the obtained cured product is excellent in ink resistance.

FIG. 1 is a cross-sectional view showing an example of the liquid discharge head of the present invention. FIG. 2 is an enlarged cross-sectional view showing an example of a portion A in FIG. FIG. 3 is an enlarged cross-sectional view showing another example of the portion A in FIG. FIG. 4 is an explanatory diagram for explaining film formation on a member having irregularities by the ALD method. FIG. 5 is an explanatory view showing an example of a cross-sectional observation photograph of a sample in which a surface treatment film in which Ta is introduced into SiO ₂ by an ALD method is formed on a Si substrate having a flow path pattern formed by etching. FIG. 6 is an explanatory diagram for explaining film formation on a member having unevenness by a sputtering method. FIG. 7 is an explanatory diagram showing an example of the result of XPS comparing impurities in a processing layer formed on a Si substrate by sputtering. FIG. 8 is an explanatory diagram showing an example of a result of XPS comparing impurities in a processing layer formed on the Si substrate by the ALD method. FIG. 9 is a schematic view showing an example of the liquid discharge head of the present invention. FIG. 10 is a schematic view showing another example of the liquid discharge head of the present invention. FIG. 11 is a schematic view showing another example of the liquid discharge head of the present invention. FIG. 12 is a schematic side view of a mechanism unit showing an example of an image forming apparatus equipped with the liquid discharge head of the present invention. FIG. 13 is an explanatory plan view of a main part of a mechanism portion showing an example of an image forming apparatus equipped with the liquid discharge head of the present invention. FIG. 14 is an explanatory front view showing an example of the head unit.

(Curable composition)
The curable composition of the present invention includes a methoxy group-containing silane-modified bisphenol-type epoxy resin (A), a polythiol compound (B) having two or more thiol groups in the molecule, and an imidazole represented by the following general formula (1) It contains a resin composition containing compound (C), and further contains other components as necessary.

However, in said general formula (1), k is 1 or more and less than 6. j is 0 or 1. R ₁ , R ₂ , and R ₃ each independently represent any of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group. R ₄ represents any one of an alkylene group having 1 to 20 carbon atoms, an arylene group, and —CH ₂ CH ₂ COO—. R ₅ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cyanomethyl group when k is 1, and has 1 to 20 carbon atoms when k is 2 or more and less than 6. Represents a hydrocarbon group.

In the curable composition of the present invention, in the conventional adhesive composition, when the SP value of the solvent of the ink used in the inkjet head is out of the range of 9.5 to 15.0, the adhesive swells and the Young This is based on the knowledge that there is a problem that the rate drops and a droplet discharge failure occurs.
Further, the curable composition of the present invention is based on the knowledge that the adhesive composition used in the conventional ink jet print head has a problem of causing a decrease in bonding strength with respect to the water-based ink. is there.
Furthermore, the curable composition of the present invention is based on the knowledge that it is required to be superior to the ink resistance of the obtained cured product as compared with the resin composition used in the conventional liquid discharge head.

<Resin composition>
The resin composition is represented by a methoxy group-containing silane-modified bisphenol type epoxy resin (A) (epoxy compound), a polythiol compound (B) having two or more thiol groups in the molecule, and the general formula (1). Imidazole compound (C), and other components as necessary.

<< Methoxy group-containing silane-modified bisphenol type epoxy resin (A) >>
The methoxy group-containing silane-modified bisphenol type epoxy resin (A) is not particularly limited and may be appropriately selected depending on the intended purpose. However, a hydrolyzable methoxysilane derived from a bisphenol type epoxy compound and methyltrimethoxysilane. The partial condensate is preferably obtained by a demethanol reaction.

  The methoxy group-containing silane-modified bisphenol type epoxy resin (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,3-bis (4- (2- (4-oxirane- 2-ylmethoxy) propan-2-yl) phenoxy) propan-2-yltrimethoxysilicate and the like.

  The content of the methoxy group-containing silane-modified bisphenol type epoxy resin (A) is preferably 10 parts by mass or more and 100 parts by mass or less, and more preferably 30 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the epoxy compound. . When the content of the methoxy group-containing silane-modified bisphenol-type epoxy resin (A) is 10 parts by mass or more and 100 parts by mass or less, it is preferable in terms of excellent balance between heat resistance and chemical resistance.

  The resin composition preferably contains an epoxy compound represented by the following general formula (2).

However, the general formula (2), R ₆ is, indicates a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

  As content of the epoxy compound represented by the said General formula (2), 10 to 80 mass parts is preferable with respect to 100 mass parts of epoxy compounds. The content of the epoxy compound represented by the general formula (2) is preferably 10 parts by mass or more and 80 parts by mass or less from the viewpoint of excellent ink resistance.

  The resin composition preferably contains an epoxy compound represented by the following general formula (3) from the viewpoint of excellent balance between workability and adhesiveness.

  As content of the epoxy compound represented by the said General formula (3), 5 to 30 mass parts is preferable with respect to 100 mass parts of epoxy compounds. The content of the epoxy compound represented by the general formula (3) is preferably 5 parts by mass or more and 30 parts by mass or less from the viewpoint of excellent balance between workability and adhesiveness.

  In addition to the epoxy compound, the resin composition can contain various epoxy compounds depending on the purpose. For example, mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds: dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1, 3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra 4-hydroxyphenyl) ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, polyglycidyl ether compounds of polynuclear polyphenol compounds such as terpenephenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol Polyglycidyl ethers of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, Azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, te Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as lahydrophthalic acid, hexahydrophthalic acid and endomethylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate; N, N-diglycidylaniline , Epoxy compounds having a glycidylamino group such as bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentanediene epoxide, 3,4-epoxy Cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adip Epoxides of cyclic olefin compounds such as epoxides; Epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers; heterocyclic compounds such as triglycidyl isocyanurate; or prepolymers of these end isocyanates And those obtained by high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). These may be used individually by 1 type and may use 2 or more types together.

  The epoxy compound is not particularly limited and may be appropriately selected depending on the intended purpose. The epoxy equivalent is preferably 70 or more and 3,000 or less, and more preferably 90 or more and 2,000 or less. There is an advantage that sufficient curability can be obtained when the epoxy equivalent is in the range of 70 to 3,000.

<< Polythiol Compound (B) >>
The polythiol compound (B) is not particularly limited as long as it is a compound having two or more thiol groups in the molecule, and can be appropriately selected according to the purpose. For example, trimethylolpropane tris (thioglycolate) , Pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris (β-thiopropionate), pentaerythritol tetrakis (β-thiopropionate), dipentaerythritol poly (β-thioproprote) Examples thereof include polythiol compounds that do not require the use of a basic substance in the production process, such as thiol compounds obtained by esterification reaction of polyols such as pionate) and mercapto organic acids.

  Furthermore, as said polythiol compound (B), alkyl polythiol compounds such as 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol; terminal thiol group-containing polyether; terminal thiol group-containing polythioether A thiol compound obtained by reaction of an epoxy compound with hydrogen sulfide; a thiol compound having a terminal thiol group obtained by reaction of a polythiol compound and an epoxy compound; Examples of materials used include polythiol compounds that have been subjected to dealkalization treatment and have an alkali metal ion concentration of 50 ppm or less.

  Examples of the dealkalizing treatment method of the polythiol compound produced using a basic substance as the reaction catalyst include, for example, dissolving the polythiol compound to be treated in an organic solvent such as acetone and methanol, and then acid such as dilute hydrochloric acid and dilute sulfuric acid. And a method of removing the produced salt by extraction, washing, etc., a method of removing by adsorption using an ion exchange resin, a method of separating and purifying a polythiol compound by distillation, and the like.

  Among the polythiol compounds (B), dipentaerythritol hexa (3-mercaptobutyrate) and 1,3,5-tris (3-mercaptopropyl) -1,3,5-triazine-2,4,6 At least one selected from (1H, 3H, 5H) -trione is preferable because of excellent balance between storage stability and curability.

  The mixing ratio of the epoxy compound and the polythiol compound (B) is the number of thiol equivalents / the number of epoxy equivalents, preferably 0.2 to 2.0, more preferably 0.5 to 1.5. When the mixing ratio is 0.2 or more, sufficient rapid curability is obtained, and when it is 2.0 or less, physical properties of the cured product such as heat resistance are obtained.

<< Imidazole Compound (C) >>
As the imidazole compound (C), a compound represented by the following general formula (1) is used.

  In the said General formula (1), k is 1 or more and less than 6, and 1 or 2 is preferable. j is 0 or 1, and 1 is preferable.

In Formula _{(1), R 1, R} 2, and _{R 3} each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and any aryl group.
Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-pentyl, and hexyl. Group, isohexyl group, octyl group, 2-ethylhexyl group, tert-octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. It is done. Examples of the aryl group include a phenyl group and a naphthyl group. These groups may be substituted with a halogen, a hydroxy group or the like.
R ₁ , R ₂ , and R ₃ are preferably any one of a hydrogen atom, a methyl group, an ethyl group, and a phenyl group.

In the general formula (1), R ₄ represents any one of an alkylene group having 1 to 20 carbon atoms, an arylene group, and —CH ₂ CH ₂ COO—.
Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane- Examples include 1,5-diyl group, hexane-1,6-diyl group, octane-1,8-diyl group, 2-methyl-hexane-1,6-diyl group, decane-1,10-diyl group and the like. . Examples of the arylene group include a phenylene group and a naphthylene group. These groups may be substituted with a halogen, a hydroxy group or the like.
R ₄ is preferably a methylene group or —CH ₂ CH ₂ COO—.

In the general formula (1), when k is 1, R ₅ is any one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, and a cyanomethyl group, and k is 2 or more and 6 If it is less than 1, it represents a hydrocarbon group having 1 to 20 carbon atoms.
As said C1-C20 hydrocarbon group, a C1-C20 alkyl group, an aryl group, etc. are mentioned, for example.
Examples of the alkyl group having 1 to 20 carbon atoms and the aryl group include the same groups as those described above for R ₁ , R ₂ , and R ₃ .

  Examples of the imidazole compound represented by the general formula (1) include compounds represented by the following structural formula.

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<IM-2>

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<IM-5>

<IM-6>

<IM-7>

<IM-8>

<IM-9>

<IM-10>

<IM-11>

<IM-12>

<IM-13>

<IM-14>

<IM-15>

<IM-16>

<IM-17>

<IM-18>

<IM-19>

<IM-20>

<IM-21>

<IM-22>

<IM-23>

<IM-24>

  Moreover, 2-methyl-N-ethyl-phenylimidazole can also be suitably used as the imidazole compound (C) represented by the general formula (1).

  There is no restriction | limiting in particular as content of the imidazole compound (C) represented by the said General formula (1), Although it can select suitably according to the objective, 1 mass with respect to 100 mass parts of said epoxy compounds. Part to 5 parts by mass is preferable.

  It is preferable from the point which improves the adhesive strength that the said resin composition contains the silane coupling agent represented by following General formula (4).

In the general formula (4), R ₇ and R ₈ each independently represents an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.

In the general formula (4), R ₉ represents any one of an alkylene group having 1 to 20 carbon atoms and an arylene group.
Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane- Examples include 1,5-diyl group, hexane-1,6-diyl group, octane-1,8-diyl group, 2-methyl-hexane-1,6-diyl group, decane-1,10-diyl group and the like. . Examples of the arylene group include a phenylene group and a naphthylene group. These groups may be substituted with a halogen, a hydroxy group or the like.

In the general formula (4), R ₁₀ represents any one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group.
Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-pentyl, and hexyl. Group, isohexyl group, octyl group, 2-ethylhexyl group, tert-octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. It is done. Examples of the aryl group include a phenyl group and a naphthyl group. These groups may be further substituted with an aryl group, heterocycle, amine, amide, imine, halogen, hydroxy group and the like.

  Examples of the silane coupling agent represented by the general formula (4) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, N -(2-aminoethyl) aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane and the like can be mentioned.

The resin composition may contain a silane coupling agent other than the silane coupling agent represented by the general formula (4), a titanate coupling agent, and an aluminate coupling agent.
Examples of the other silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, N-2 (-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 (-aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2 (-aminoethyl ) -3-Aminopropyltrimethoxysilane, N-2 (-aminoethyl) -3-aminopropyltriethoxysilane, (1,3-dimethyl-butylidene) -propylamine, N-phenyl-3-aminopropyltrimethoxy Silane, N, N-bis (3- (trimethoxysilyl) propyl) ethyl Diamine, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N- (2- (vinylbenzidineamino) ) Ethyl) -3-aminopropyltrimethoxysilane hydrochloride, 1,2-ethanediamine, N- {3- (trimethoxysilyl) propyl} -N-{(ethenylphenyl) methyl} derivative hydrochloride 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc. Is mentioned.
Regarding the organic group of the silane coupling agent, those having a functional group that reacts with an epoxy resin are preferable, and the above-mentioned coupling agent is one example. These can be purchased from Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Co., Ltd. and Chisso Corporation.

Examples of the titanate and aluminate coupling agents include tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, di- i-propoxy bis (acetylacetonato) titanium, poly (di-i-propoxy oxytitanium), poly (di-n-butoxy oxytitanium), di-n-butoxy bis (triethanolaminato) titanium , Diisopropoxy bis (triethanolaminato) titanium, isopropyltri (N-amidoethyl / aminoethyl) titanate, acetoalkoxyaluminum diisopropylate and the like.
The titanate and aluminate coupling agents improve the adhesive strength by improving the wettability of the adhesive by forming a polymer organic coating on the inorganic surface. It is an example of the titanate coupling agent and is not limited. These can be purchased from Mitsubishi Gas Chemical Co., Ltd., Nippon Soda Co., Ltd., and Ajinomoto Fine Techno Co., Ltd.
The coupling agent is preferably an epoxy group or a coupling agent having an amine group. In order to exert the effect by adding the coupling agent to the epoxy adhesive, it is at normal temperature during the effective period of the adhesive. From the viewpoint that the reaction does not proceed, an epoxy group coupling agent is more preferable.

-Other ingredients-
Examples of the other components include curing catalysts; reactive or non-reactive diluents (plasticizers) such as monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar; glass fibers, carbon fibers, Fillers or pigments such as cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely divided silica, titanium dioxide, carbon black, graphite, iron oxide, bituminous substances; candelilla wax, carna Lubricants such as uba wax, wax, wax, honey wax, lanolin, whale wax, montan wax, petroleum wax, fatty acid wax, fatty acid ester, fatty acid ether, aromatic ester, aromatic ether; silane coupling material; thickening Agent; thixotropic agent Antioxidants; light stabilizers; ultraviolet absorbers; flame retardants; antifoaming agents; rust inhibitors; may contain conventional additives such as colloidal silica and colloidal alumina, and also xylene resins, petroleum resins, etc. Adhesive resins can also be used in combination.

  The said resin composition can be manufactured by mixing the said epoxy resin (A), the said polythiol compound (B), the said imidazole compound (C), and another component as needed further by a conventional method.

(Liquid discharge head)
The liquid discharge head according to the present invention includes a flow path including a first member, a resin layer, and a second member, and further includes other members as necessary.

<Resin layer>
The resin layer comprises a methoxy group-containing silane-modified bisphenol-type epoxy resin (A), a polythiol compound (B) having two or more thiol groups in the molecule, and an imidazole compound (C) represented by the following general formula (1) A cured product of a resin composition containing
However, in said general formula (1), k is 1 or more and less than 6. j is 0 or 1. R ₁ , R ₂ , and R ₃ each independently represent any of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group. R ₄ represents any one of an alkylene group having 1 to 20 carbon atoms, an arylene group, and —CH ₂ CH ₂ COO—. R ₅ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cyanomethyl group when k is 1, and has 1 to 20 carbon atoms when k is 2 or more and less than 6. Represents a hydrocarbon group.

  As the resin composition, the same resin composition as that in the present invention can be used.

  A cured product is obtained by heating the resin composition. The curing temperature is preferably 60 ° C to 100 ° C, and the curing time is preferably 10 minutes to 4 hours.

About the epoxy compound which comprises the said resin layer, the hardened | cured material which comprised the three-dimensional bridge | crosslinking is obtained by using the polyfunctional compound which has an epoxy group. The epoxy compounds can be classified into glycidyl ethers, glycidyl esters, glycidylamines, etc., depending on the bonding site of the glycidyl group, and a wide variety of compounds are obtained depending on the compound serving as the bonding matrix.
In order to suppress the permeability to the ink and eliminate the swelling, it is necessary to reduce the hydrophilicity of the epoxy compound and increase the three-dimensional crosslinking. Therefore, a polyfunctional epoxy compound such as a glycidylamine type or a novolak resin glycidyl ether compound is preferred for swelling. However, it is necessary to consider the wettability and adsorbability to the member, and a plurality of mixtures may be used. In addition, glycidyl ether of bisphenol A is preferable from the viewpoint of hydrogen bonding to metal, and the resin structure may be more elastic as the molecular weight increases. However, since there are swelling with respect to ink and cleavage of hydrogen bonds, it is necessary to mix them appropriately. Is possible.
The said epoxy compound is marketed by many including Mitsubishi Chemical Corporation, Shikoku Kasei Kogyo Co., Ltd., ADEKA Co., Ltd., DIC Corporation, etc., and can be purchased from any of them.

As an epoxy adhesive containing the said epoxy compound, a solventless thing may be sufficient and it can also be diluted with a dilution solvent so that it may become a moderate viscosity. As the diluting solvent, a solvent having no active hydrogen is preferable from a solvent having an active hydrogen reactive with an epoxy group from the viewpoint of storage stability of the adhesive, but it is free from the viewpoint of wettability to a member, drying speed, viscosity, and the like. If the resin layer is formed at the time of drying even in a dispersed state rather than a completely dissolved state, it can be used without any problem.
Regarding the drying of the solvent, room temperature and heating within a range where no reaction occurs are also possible. Moreover, it is also possible to dry under reduced pressure, and it is possible to dry without making the said epoxy resin react even if a high boiling point solvent is used by performing reduced pressure drying.
The solvent that can be used can be freely selected according to the epoxy compound, the curing agent, and other additives, but a solvent in which impurities are controlled is preferable in order to proceed the curing reaction stably.

  The epoxy adhesive may contain a filler, other binder resins, a viscosity modifier, and the like in addition to the epoxy compound, the curing agent, the solvent, and the coupling agent. The filler may be inorganic particles such as silica and alumina, or resin fine particles of melamine resin or acrylic resin. It is also possible to add a higher fatty acid amide or the like as a viscosity modifier to adjust the viscosity to a suitable one by applying an adhesive. In addition, a foam suppressor or an antifoaming agent may be added to prevent coating spots from being generated due to foam in the coating film.

  In general, an epoxy structure having a high crosslinking density as described above has a very high Young's modulus, and it has been difficult to obtain a sufficient adhesive force when the thickness of the resin layer is reduced. By defining the thickness of the resin layer to be greater than 0.5 μm, it is possible to ensure the necessary adhesive force. In order to control the thickness of the resin layer, a gap agent, for example, a silica filler having a controlled particle size or a filler obtained by polymerizing a resin can be used. The filler as described above can be purchased from Sekisui Chemical Co., Ltd., Ube Industries, Ltd., ADEKA Co., Ltd. and the like.

The resin layer is a methoxy group-containing silane-modified bisphenol type epoxy resin (A), a polythiol compound (B) having two or more thiol groups in the molecule, and an imidazole compound (C) represented by the general formula (1) For example, the main skeleton is grasped by pyrolysis GC / MS method and GC / TOFMS, and further analysis is performed by adding information on structure and functional group by using FTIR method and NMR method. be able to.
The conditions for resin layer analysis by the pyrolysis GC / MS method are described below. In this method, a minute amount of sample is directly exposed to high temperature to cause thermal decomposition instantaneously, and the gas components generated at that time are guided to the GC / MS apparatus and analyzed. In addition, although an analysis condition is described below as an example, it is not limited to the following conditions. The analysis conditions can be changed as needed according to the composition and state of the analyte, and analysis can be performed while examining optimum conditions.
-Equipment configuration and measurement conditions-
GC / MS device: QP-5000 manufactured by Shimadzu Corporation
・ Pyrolysis device: Py-2020D, manufactured by Frontier Laboratories
・ Heating temperature 300 ℃
Column UA5 (L = 30 m, ID = 0.25 mm, Film = 0.25 μm)
-Column temperature rise 50 ° C-350 ° C (20 ° C / min temperature rise)
・ Ionization method EI method (70 eV)
・ Split 1: 100

In addition, since the GC / MS measurement is mainly performed by structure estimation by library search, it is difficult to analyze a substance that is not registered in the database to be searched. Therefore, in order to perform structural analysis of components whose structure could not be estimated by GC / MS, it is possible to perform GC / TOFMS measurement that provides accurate mass information of molecules or fragments.
In addition, accurate mass measurement by chemical ionization (CI method) that facilitates observation of molecular ions can also be performed.
-Equipment configuration and measurement conditions-
・ GC / TOFMS: Waters GCT Premier
Column: DB5-MS (30m x 0.25mm, 0.25µm)
-Temperature rising conditions: 50 ° C. (1 min) → 10 ° C./min→320° C. (10 min)
Carrier gas: He, 1.0 mL / min (constant flow rate)
Injection method: split 50: 1
・ Inlet: 280 ° C

"CI ionization conditions"
・ Ionization method: PCI method (methane, isobutane, no gas)
・ Electron energy: 40 eV
・ Ionization current: 200μA

In addition to this information, functional groups obtained from FT-IR analysis, Raman spectroscopic analysis, and ¹³ C, ¹ H, ¹⁴ N, and ³³ S-NMR analysis using the ATR method used for general chemical analysis. By combining information and element ratios, the resin layer has the methoxy group-containing silane-modified bisphenol-type epoxy resin (A), the polythiol compound (B) having two or more thiol groups in the molecule, and the general formula ( It can be analyzed that the imidazole compound (C) represented by 1) is contained. From this, the resin layer is represented by the methoxy group-containing silane-modified bisphenol type epoxy resin (A), the polythiol compound (B) having two or more thiol groups in the molecule, and the general formula (1). It can be proved that it contains a cured product of a resin composition containing the imidazole compound (C).

  The resin composition is not particularly limited and can be used for various applications. For example, paints or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc .; Adhesive tape for packaging, adhesive label, frozen food label, removable label, POS label, adhesive wallpaper, adhesive for adhesive flooring; art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copier, impregnated paper Processed paper such as natural fibers, synthetic fibers, glass fibers, carbon fibers, metal fibers, etc., fiber treatment agents such as fraying prevention agents, processing agents, etc .; building materials such as sealing materials, cement admixtures, waterproofing materials; Examples thereof include sealing agents for electronic / electrical devices.

Next, in order to increase the adhesive strength, it is effective to cause the anchor agent to act on the resin layer interface and firmly fix the resin layer, the first member, and the second member by ionic bond or covalent bond. When the first member and the second member are made of metal, the oil-based ink is firmly fixed by hydrogen bonding, but the water-based ink is broken by water penetrating the adhesion interface. As a result, the adhesive strength is significantly reduced. For this purpose, it is preferable to provide a covalent bond between the resin layer and the first and second members.
In order to bond the metal and the resin composition by a covalent bond, it is effective to use a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent. The coupling agent may be directly treated on the surface of the metal member to be bonded, or a strong bond can be obtained even if the coupling agent treatment is performed after the surface treatment for improving the coupling property of the coupling agent.
As the surface treatment performed before the coupling treatment, for the silane coupling agent, an oxide containing silicone such as SiO ₂ , SiOC, SiTaOx, SiZrOx is very effective. Processes that can easily form thin films such as sputtering, chemical vapor deposition, and atomic layer deposition are effective. TiO ₂ and TiN treatments are effective not only for titanate coupling agents but also for silane coupling agents. It is. These pretreatments are preferably thin layers as much as possible because the strength of the treatment layer affects the adhesive strength when the pretreatment is performed thickly.

<First member>
The first member is preferably a nozzle plate in which a discharge port for discharging a liquid is formed.
The nozzle plate has a nozzle substrate and a water repellent film on the nozzle substrate.
There is no restriction | limiting in particular about the shape, a magnitude | size, a material, a structure, etc. as said nozzle substrate, According to the objective, it can select suitably.
Examples of the material of the nozzle substrate is not particularly limited and may be appropriately selected depending on the purpose, for example, stainless steel, Al, Bi, Cr, InSn , ITO, Nb, Nb 2 O 5, NiCr, Si, _{SiO 2, Sn, Ta 2 O} 5, Ti, W, ZAO (ZnO + Al 2 O 3), Zn and the like. These may be used alone or in combination of two or more. Among these, stainless steel is preferable from the viewpoint of rust prevention.
The number, arrangement, interval, opening shape, opening size, opening cross-sectional shape, and the like of the discharge holes are not particularly limited and can be appropriately selected according to the purpose.

<Second member>
The second member is preferably a flow path plate having an individual liquid chamber communicating with the discharge port.
The individual liquid chamber is formed by joining the first member and the second member via a resin layer. That is, it is preferable to have a resin layer between the first member and the second member.
The average thickness of the resin layer is preferably 1.0 μm or more and 2.5 μm or less. Adhesion reliability can be secured when the average thickness of the resin layer is 2.5 μm or less. By setting the average thickness of the resin layer to 1.0 μm or more, a high initial strength can be obtained, so that it is possible to ensure both adhesion reliability and initial adhesion.
The average thickness of the resin layer may be processed so that a bonded section can be embedded in an epoxy resin and a desired cross section can be observed with a polishing machine. For the observation, for example, it can be measured by an electron microscope (SEM: Scanning Electro Microscope).

The surface in contact with the resin layer of at least one of the first member and the second member has a treatment layer, the treatment layer is an oxide containing Si, and the oxide is the first member. It is preferable that the transition metal which forms a passive layer is included in either of the member of this, and the 2nd member.
The treatment layer preferably contains at least one transition metal selected from Group 4 and Group 5.
The treatment layer preferably contains at least one selected from Hf, Ta, and Zr.
By introducing at least one of Hf, Ta, and Zr into the SiO ₂ film, the transition metal species binds very strongly to O and forms a passive layer. At this time, in addition to improving the filling property of the film, the function of the passive layer is present in the treatment layer 112, so that the corrosion reaction when contacting with both acidic and alkaline liquids can be strongly suppressed. Thereby, an oxide having resistance to acidic and alkaline liquids can be formed.

<Other members>
Examples of the other member include a stimulus generating member.
The stimulus generating member is a member that generates a stimulus to be applied to the liquid (ink).
There is no restriction | limiting in particular as a irritation | stimulation in the said irritation | stimulation generating member, According to the objective, it can select suitably, For example, heat | fever (temperature), a pressure, a vibration, light, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.
Examples of the stimulus generating member include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, and a light. Specific examples of the stimulus generating member include a piezoelectric actuator such as a piezoelectric element, a thermal actuator that uses a phase change caused by liquid film boiling using an electrothermal transducer such as a heating resistor, and a metal phase change caused by a temperature change. Shape memory alloy actuators using electrostatic force, electrostatic actuators using electrostatic force, and the like.

When the stimulus is “heat”, thermal energy corresponding to the recording signal is applied to the liquid (ink) in the liquid ejection head using, for example, a thermal head. Examples include a method in which bubbles are generated in the ink by the thermal energy, and the ink is ejected as droplets from the nozzles 4 of the nozzle plate 1 by the pressure of the bubbles.
When the stimulus is “pressure”, for example, by applying a voltage to the piezoelectric element bonded to the position called the pressure chamber in the ink flow path in the liquid ejection head, the piezoelectric element bends. . As a result, the volume of the pressure chamber shrinks, and the liquid (ink) is ejected as droplets from the nozzle 4 of the liquid ejection head.
Among these, a piezo method in which a voltage (applied to a piezo element and a liquid (ink) is allowed to fly is preferable.

  Here, FIG. 1 is a cross-sectional explanatory view for explaining the liquid discharge head of the present invention. FIG. 2 is an enlarged cross-sectional explanatory view showing an example of a portion A in FIG. FIG. 3 is an enlarged cross-sectional explanatory view showing another example of the portion A of FIG.

The liquid discharge head 100 includes a nozzle plate 102 on which nozzles 101 for discharging droplets are formed, a flow path plate 104 that forms a flow path (pressure chamber) 103 that communicates with the nozzles 101, and a wall surface of the pressure chamber 103. The diaphragm 105 to be formed is laminated. Here, the nozzle plate 102, the flow path plate 104, and the vibration plate 105 are flow path forming members that are joined by the resin layer 113 to form a flow path.
A piezoelectric actuator including an electromechanical transducer 140 is provided on the surface of the diaphragm 105 opposite to the pressure chamber 103.

  The electromechanical conversion element 140 is formed by sequentially laminating an oxide electrode 141 as an adhesion layer, a first electrode (lower electrode) 142, an electromechanical conversion film 144, and a second electrode (upper electrode) 145 on the diaphragm 105. Formed.

  The first electrode 142 and the second electrode 145 are formed of a highly conductive material such as Pt or Au, for example. The electromechanical conversion film 144 is made of PZT. The channel plate 104 is made of silicone, and the nozzle plate 102 is made of SUS, nickel, polyimide, or the like.

  Next, details of the joint portion of the liquid discharge head will be described with reference to FIGS. 2 and 3 are enlarged cross-sectional explanatory views of part A of FIG. 1 showing different examples.

The nozzle plate 102 and the flow path plate 104 are joined by a resin layer 113.
Here, the treatment layers 112 are formed on the surfaces of the nozzle plate 102 and the flow path plate 104 including the adhesion surface of the resin layer 113. 2 shows an example in which the treatment layer 112 is not formed on the exposed surface of the resin layer 113, and FIG. 3 shows an example in which the treatment layer 112 is formed on the exposed surface of the resin layer 113. The form shown in FIG. 3 can be obtained by depositing the treatment layer 112 after the nozzle plate 102 is bonded using a surface reaction such as an ALD (Atomic Layer Deposition) method.

The treatment layer 112 is an oxide containing Si, and the oxide contains a transition metal that forms a passive layer.
Here, the processing layer 112 is a complex oxide of Si that has high ink-reliability and improves the adhesion between the transition metal species forming the passive layer and the resin layer 113.

  Since the resin layer 113 is an organic thin film, it transmits moisture. Therefore, when the processing layer 112 does not have ink resistance reliability, the ink corrodes the processing layer 112 through the resin layer 113 and peels off the entire resin layer 113.

  However, since the transition metal species can form a stable oxide, it can withstand ink by maintaining a stable state even in an aqueous solution.

  Further, the oxide containing Si has good compatibility with the anionic curing agent and silane coupling agent contained in the resin layer 113, and improves the adhesion between the treatment layer 112 and the resin layer 113.

  Thus, the treatment layer is formed on the surface of the flow path forming member, and the treatment layer is an oxide containing Si, and the oxide is one of the first member and the second member. By adopting a structure that includes a transition metal that forms a passive layer, it is possible to improve both the adhesion at the interface between the treatment layer 112 and the resin layer 113 and the ink reliability.

That is, by containing SiO _2, a high adhesion to the member, and also adhesion to the resin layer, it can secure high adhesion water resistance by using an amine-based curing agent and a silane coupling agent. Further, by forming a passive layer, the treatment layer 112 forms a stable corrosion-resistant film on the surface, so that even if it is in contact with a liquid, it is stable for a long time.

  In addition, transition metals can take a plurality of oxidation numbers by having vacant orbits in inner orbitals such as d or f orbitals. Therefore, by including a transition metal species in the processing layer 112, the tolerance to the excess or deficiency of oxygen atoms is increased by increasing the compatibility with the oxidation number of the entire film, and the oxygen number deficiency or excess in the film is increased. High stability is exhibited.

  When the transition metal is not included, defects in the treatment layer 112 due to excess or deficiency of oxygen atoms are generated, and the defects are easily dissolved because they have a high energy state. On the other hand, the defect of a process layer can be reduced by containing a transition metal, the stability of an oxide rises, and the solubility to a liquid can be reduced.

Among such transition metals, when a metal that forms a passive layer such as a valve metal is used, the solubility of the treatment layer 112 can be further reduced.
As the metal for forming the passive layer, tantalum, niobium, titanium, hafnium, zirconium, and tungsten, which are transition metals having high compatibility with the oxidation number, are preferable.

  In addition, tantalum, niobium, hafnium, and zirconium form a very stable oxide regardless of whether the pH of the liquid in contact is acidic or alkaline, so that the state can be maintained regardless of acidity or alkalinity. is there.

In other words, the treatment layer 112 preferably contains a Group 4 and Group 5 transition metal that forms a passive layer. The Group 4 and Group 5 transition metals that form the passive layer have electron orbits similar to those of Group 4 Si, and are similar to those of Group 4 Si when introduced into the SiO ₂ film. It has an electron orbit, Si and the metal species can be strongly bonded via O, the film filling property is improved, and a dense film can be formed.

  Further, in addition to the improvement of the filling property, by causing a strong bond to be present in the treatment layer by the Si—O bond, it is possible to suppress the corrosion reaction when contacting the liquid. Thereby, an oxide having resistance to liquid can be formed, sufficient resistance can be secured, and the reliability of the head can be improved.

  In this case, the Group 4 and Group 5 transition metal forming the passive layer preferably contains at least one of Hf, Ta, and Zr.

  In addition, the treatment layer 112 is preferably completely oxidized. As a result, the crystal structure of the treatment layer 112 becomes amorphous, and when exposed to a liquid, there are almost no crystal grain boundaries that are likely to be corroded, and a high resistance to the liquid can be exhibited.

  In the processing layer 112, it is preferable that Si is contained in the film by 17 at% or more. By containing 17 at% or more of Si in the processing layer 112, a complete transparent film can be formed, and preferably 20 at% or more.

  This makes it possible to form a uniform film that is in an amorphous state with little uneven distribution of metal species, avoids the presence of crystals or the like partially, and reduces areas that are locally weak against liquids. can do. When the Si content in the film is small, other metal species aggregate and crystallize, resulting in uneven film quality. If there is a bias, a battery effect may be produced between Si and other metal species when a liquid is touched, and a corrosion reaction may occur.

  Here, whether or not the alloy film forming the treatment layer 112 is completely oxidized can be determined based on whether or not visible light can be transmitted since the film is in an amorphous state. For example, using a multi-wavelength type ellipsometer, it can be judged that the film is completely oxidized when the attenuation coefficient (k) is at least 0.1 or less, preferably 0.03 or less in the wavelength range of 400 nm to 800 nm. it can.

  In the treatment layer 112, the transition metal is preferably contained in the film at 2 at% or more. Thereby, the density of the treatment layer 112 is reliably improved, and the resistance to the liquid is improved. More preferably, it is 3.5 at% or more and 13.5 at% or less. As a result, the treatment layer 112 can have a structure with few defects and a high filling rate, so that resistance to ink can be easily obtained.

As a method for confirming the state of the film, it can be confirmed by using an ellipsometer that the refractive index is a constant value. For example, since the refractive index of a single film is 1.4 for a SiO ₂ film and 2.1 for a Ta ₂ O ₅ film, the refractive index is 1. when the treatment layer 112 is completely oxidized. The value is between 4 and 2.1. However, when the metal species in the treatment layer 112 is not completely oxidized, the transmittance is decreased and the refractive index is increased. Therefore, the desired film quality can be obtained by managing both the refractive index and the transmittance. Can do.

  That is, when the refractive indexes of the metal oxides constituting the treatment layer 112 are different, the alloy ratio can be managed by the refractive index. Thereby, non-destructive and high-speed measurement in the atmosphere is possible, and the condition management of the processing layer 112 is facilitated even in an actual mass production process.

  Next, as a method for forming the treatment layer 112, for example, a method that can easily form a thin film, such as a vapor deposition method, a sputtering method, a CVD (Chemical Vapor Deposition) method, an ALD (Atomic Layer Deposition) method, or the like can be used. In particular, when the flow path forming member is formed of a material that is deformed by heat treatment, it is preferable to form the film by a sputtering method or an ALD method at 160 ° C. or lower, preferably 120 ° C. or lower.

  In particular, since the ALD method is a method in which a film formation reaction is completed for each atomic layer, a very dense film with few defects can be formed as compared with a normal CVD method or vapor deposition method. In addition, since a film can be formed at a location where gas can be adsorbed to the member, the film can be uniformly formed on a member having a vertical wall or an edge portion.

  Further, since the sputtering (PVD) method knocks out the metal species of the target with Ar ions, a film with few impurities can be formed. In addition, since the film is formed by knocking out ions in vacuum, a film having high adhesion to the substrate can be formed. Furthermore, since heat is not used for the reaction, the member can be cooled, and the film can be formed even at a temperature close to room temperature. Therefore, even when a material whose temperature is difficult to raise is used for the flow path forming member, resistance to the liquid can be obtained.

  In addition, the flow path forming member is preferably coated with the treatment layer 112 on the surface in contact with the liquid other than the bonding surface. By adopting such a configuration, it becomes difficult to elute parts having low liquid resistance and an adhesion improving material, and thus a highly reliable configuration can be provided.

  In this case, the film thickness of the treatment layer 112 is preferably 10 nm or more, more preferably 25 nm or more, at the thinnest portion. When the film thickness becomes too thin, it is difficult to cover the defective portion when the flow path forming member is defective.

  In addition, when the treatment layer 112 is formed on the surface of the diaphragm 105 as a flow path forming member, it is not preferable that the film be a thick film that affects the operating characteristics of the diaphragm 105. Therefore, the treatment layer 112 is preferably 200 nm or less, and more preferably 50 nm or less.

  When the treatment layer 112 having the above-described film thickness is formed on the surface that becomes the flow channel wall surface of the flow channel forming member, as described above, the film may be formed by the ALD method at 160 ° C. or lower, preferably 120 ° C. or lower. preferable. The ALD method can be controlled at a monomolecular layer level and forms a very uniform film even on a member having a vertical wall or inclined wall as shown in FIG. can do.

FIG. 5 shows an example of a cross-sectional observation of a sample in which a treatment layer 112 in which Ta is introduced into SiO ₂ is formed on an Si substrate on which a flow path pattern is actually formed by etching using an ALD method. As can be seen from FIG. 5, it was confirmed that a uniform film was formed on the side wall of the etched pattern.

In addition, the reactivity varies depending on the type of source gas used, and in the case of film formation at 160 ° C. or lower, functional groups coordinated around the metal are —C ₂ H ₅ , —Cl, — (N (CH ₃ ) ₂ ) and the like. In many cases, amino gases such as — (N (CH ₃ ) ₂ ) are excellent in reactivity at low temperatures.

Further, as the gas to be reacted, typically _{O 2} plasma, _{H 2} O and the like. In the case of O ₂ plasma, the reactivity is high, but since O ₃ formed in the plasma decomposes the source gas, by-products are likely to be generated. In the case of a low temperature treatment of 160 ° C. or lower, the by-product tends to be reattached to the inside of the apparatus chamber or the component substrate, which may cause generation of particles and cause a decrease in yield.

In contrast, H ₂ O can suppress the generation of by-products because the reaction is only hydrolysis. In addition, during the reaction, OH groups are easily generated on the surface of the treatment layer, and when the source gas is introduced in the next film formation cycle, it is possible to promote the attachment of the source gas to the substrate. Is particularly advantageous. When pentadimethylamide tantalum (PDMA-Ta) is used as the source gas, uniform film formation is possible even at 80 ° C. However, since the film formation rate is slow, it is preferable to carry out batch processing in which a plurality of parts are processed simultaneously during mass production.

  By performing the low-temperature treatment, the treatment layer 112 can be formed without damaging the adhesion layer even in the bonded portion.

  Next, a sputtering method is used as a method for forming the treatment layer 112. In this case, as shown in FIG. Bias occurs.

Further, since the sputtering method uses a reactive sputtering method in which metal ions are oxidized by implanting Ar ions into a metal target and simultaneously introducing O ₂ gas, impurities are hardly taken into the processing layer 112. Therefore, a pure oxide with a small amount of impurities can be formed.

  Here, FIG. 7 (sputtering method) and FIG. 8 (ALD method) show the results of XPS comparing impurities in the processing layer 112 formed on the Si substrate by sputtering and ALD (temperature is 100 ° C.). ing.

  In the case of the ALD method, carbon of about 5 at% to 10 at% was detected. On the other hand, when the sputtering method was used, no impurities were detected in the film. Since impurities are likely to gather at crystal grain boundaries, when etching is caused by a liquid, there is a possibility that the portion where the impurities are aggregated is the starting point. Since a film with a small amount of impurities can obtain higher ink reliability, corrosion resistance can be ensured even with a thinner film thickness.

  Here, an example of the liquid discharge head of the present invention will be described with reference to FIGS. FIG. 9 is an external perspective view illustrating the liquid discharge head, FIG. 10 is a cross-sectional explanatory view in a direction (liquid chamber longitudinal direction) perpendicular to the nozzle arrangement direction of the liquid discharge head, and FIG. 11 is a nozzle arrangement direction of the liquid discharge head. It is a cross-sectional explanatory drawing (liquid chamber short direction).

  In the liquid discharge head, the nozzle plate 1, the flow path plate 2, and the vibration plate member 3 are laminated and joined. And the piezoelectric actuator 11 which displaces the diaphragm member 3 and the frame member 20 as a common liquid chamber member are provided.

  The nozzle plate 1, the flow path plate 2, and the vibration plate member 3, an individual liquid chamber 6 that communicates with a plurality of nozzles 4 that discharge droplets, a fluid resistance unit 7 that supplies liquid to the individual liquid chamber 6, and a fluid A liquid introduction part 8 communicating with the resistance part 7 is formed.

  The liquid is supplied from the common liquid chamber 10 of the frame member 20 to the plurality of individual liquid chambers 6 through the filter portion 9 formed in the diaphragm member 3 through the liquid introduction portion 8 and the fluid resistance portion 7.

  Here, the nozzle plate 1 forms a nozzle 4 having a diameter of 10 μm to 35 μm, for example, corresponding to each individual liquid chamber 6, and is joined to the flow path plate 2 with a resin layer. Further, a water repellent layer is provided on the droplet discharge side surface (surface in the discharge direction: discharge surface or the surface opposite to the liquid chamber 6 side) of the nozzle plate 1.

  The flow path plate 2 is formed by etching the single crystal silicone substrate to form grooves that constitute the individual liquid chamber 6, the fluid resistance portion 7, the liquid introduction portion 8, and the like. The flow path plate 2 can be formed, for example, by etching a metal plate such as a SUS substrate with an acidic etching solution, or performing mechanical processing such as pressing.

  The diaphragm member 3 also serves as a wall member that forms the wall surface of the individual liquid chamber 6 of the flow path plate 2 and a filter member that forms the filter portion 9. The diaphragm member 3 has a multi-layer structure including three layers (two layers or four or more layers) of the first layer 3A, the second layer 3B, and the third layer 3C from the individual liquid chamber 6 side. A deformable vibration region 30 is formed in a portion corresponding to the individual liquid chamber 6 in the first layer 3A.

  A piezoelectric actuator 11 including an electromechanical conversion element as a drive element (actuator means, pressure generating means) for deforming the vibration region 30 of the diaphragm member 3 is disposed on the opposite side of the diaphragm member 3 from the individual liquid chamber 6. doing.

  The piezoelectric actuator 11 has a plurality of laminated piezoelectric members 12 adhesively bonded onto a base member 13 made of a metal member. The piezoelectric member 12 is grooved by half-cut dicing and is applied to one piezoelectric member 12. Thus, the required number of piezoelectric pillars 12A and 12B are formed in a comb shape at a predetermined interval.

  The piezoelectric columns 12A and 12B of the piezoelectric member 12 are the same, but a piezoelectric column that is driven by applying a driving waveform is a driving piezoelectric column (driving column, also referred to as “driving element” hereinafter) 12A, and no driving waveform is applied. The piezoelectric pillars used as simple pillars are distinguished as non-driving piezoelectric pillars (non-driving pillars) 12B.

  The drive column 12A is joined to a convex portion 30a which is an island-shaped thick portion formed in the vibration region 30 of the diaphragm member 3. Further, the non-driving column 12 </ b> B is joined to the convex portion 30 b that is a thick portion of the diaphragm member 3.

  The piezoelectric member 12 is formed by alternately laminating piezoelectric layers and internal electrodes. The internal electrodes are respectively drawn out to the end faces, and external electrodes are provided to transmit a drive signal to the external electrodes of the drive column 12A. The 1st wiring member 15 which consists of FPC etc. as a flexible wiring board which can be bent is connected. Connected to the first wiring member 15 is a second wiring member 16 made of FFC with a metal shield member as a flexible wiring board.

  The frame member 20 is formed by injection molding with, for example, epoxy resin or thermoplastic resin such as polyphenylene sulfite, and a common liquid chamber 10 is formed in which liquid is supplied from a head tank or a liquid cartridge (not shown).

  In the liquid discharge head configured as described above, for example, the drive column 12A contracts by lowering the voltage applied to the drive column 12A from the reference potential, and the vibration region 30 of the diaphragm member 3 descends to separate the individual liquid chamber 6. As the volume of the liquid expands, the liquid flows into the individual liquid chamber 6.

  Thereafter, the voltage applied to the drive column 12A is increased to extend the drive column 12A in the stacking direction, the vibration region 30 of the diaphragm member 3 is deformed in the nozzle 4 direction, and the volume of the individual liquid chamber 6 is contracted. The liquid in the individual liquid chamber 6 is pressurized, and droplets are ejected (jetted) from the nozzle 4.

  Then, by returning the voltage applied to the drive column 12A to the reference potential, the vibration region 30 of the diaphragm member 3 is restored to the initial position, and the individual liquid chamber 6 expands to generate a negative pressure. The liquid is filled into the individual liquid chamber 6 from the liquid chamber 10. Therefore, after the vibration of the meniscus surface of the nozzle 4 is attenuated and stabilized, the operation proceeds to the next droplet discharge.

  Note that the driving method of the head is not limited to the above example (drawing-pushing), and striking or pushing can be performed depending on the direction of the drive waveform.

(Liquid discharge device)
The liquid discharge apparatus includes the liquid discharge head of the present invention, and further includes other means as necessary.

<Liquid>
The liquid is not particularly limited as long as it is a liquid that can be discharged by the liquid discharge head, and can be appropriately selected according to the purpose. For example, ink, inkjet ink, photopolymerizable ink, pretreatment liquid, Fixing treatment liquid, resist, pattern forming material and the like can be mentioned. Among these, inkjet ink is particularly preferable.

<Other means>
Examples of the other means include control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

(Image forming device)
The image forming apparatus includes an ink storage unit and the liquid discharge head according to the present invention, and further includes other units as necessary.

<Ink storage means>
The ink containing means is means for containing ink jet ink, and examples thereof include a tank and an ink cartridge.
The ink cartridge contains the ink-jet ink in a container, and further includes other members appropriately selected as necessary.
There is no restriction | limiting in particular as said container, The shape, a structure, a magnitude | size, a material, etc. can be suitably selected according to the objective, For example, it has an ink bag etc. which were formed with the aluminum laminate film, the resin film, etc. A thing etc. are suitable.

<Liquid discharge head>
The liquid discharge head is means for applying a stimulus to the ink-jet ink and causing the ink to fly to record an image on a recording medium.
The liquid discharge head of the present invention is used as the liquid discharge head.

  The ink-jet ink mainly includes water-based ink using water as a main solvent, photopolymerizable ink using a reactive organic compound as a solvent, oil-based ink using a solvent that does not volatilize at 200 ° C. or lower as a main solvent, and volatile solvents. Any solvent ink used as a solvent can be used.

<< Water-based ink >>
The water-based ink contains at least water and a water-soluble organic solvent, and further contains other components as necessary.

-Water-soluble organic solvent-
Examples of the water-soluble organic solvent include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, and carbonic acid. Ethylene is mentioned. The following solid wetting agents can also be used as a kind of water-soluble organic solvent.
Among these, at least one selected from triols having 4 or less carbon atoms, polyethylene glycol ethers of triols having 4 or less carbon atoms, polyethylene glycols, and 1,3-propanediol because of the high equilibrium water content. These water-soluble organic solvents are preferred.
As content of the said water-soluble organic solvent, 20 mass% or more is preferable with respect to the water-soluble organic solvent whole quantity, and 30 mass%-70 mass% are more preferable.
When the content is less than 20% by mass, the ink moisturizing power is reduced, so that it is easy to dry, causing precipitation of dissolved components in the ink due to drying and aggregation of the dispersed components at the head meniscus, causing ejection. May be defective.

Examples of the triol having 4 or less carbon atoms include 1,2,3-butanetriol, 1,2,4-butanetriol, and glycerin.
Examples of the polyethylene glycol ether of triol having 4 or less carbon atoms include polyoxyethylene glyceryl ether, polyoxyethylene-1,2,3-butanetriol ether, and polyoxyethylene-1,2,4-butanetriol ether. , Etc.
Examples of the polyethylene glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and PEG200.
Among these, since glycerin has a very high equilibrium water content of 49% by mass in an environment of 23 ° C. and a relative humidity of 80%, it is easy to suppress drying of the ink, and the viscosity decrease when containing water is large. This is preferable because it is excellent in ensuring the ejection stability from the head, suppressing the increase in the viscosity of the waste ink in the head maintenance device, and preventing the waste ink from sticking to the maintenance device.

  In addition to such an organic solvent having a high equilibrium moisture content and excellent moisture retention, other water-soluble organic solvents can be used as necessary. Examples of the other water-soluble organic solvents include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, cyclic ethers, amines, amides, sulfur-containing compounds, propylene carbonate, and carbonic acid. Examples include ethylene.

  Examples of the polyhydric alcohols include 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5- Pentanediol, 2-methyl-2,4-pentanediol, hexylene glycol, 1,6-hexanediol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 3-methyl-1,3- Examples include hexanediol and propylpropylene diglycol.

  Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monoethyl ether. And triethylene glycol dimethyl ether.

  Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

  Examples of the cyclic ethers include epoxies, oxetanes, tetrahydrofurans, tetrahydropyrans, and crown ethers. Among these, oxetanes and tetrahydrofurans are preferable, and oxetanes are more preferable from the viewpoint of water solubility.

  Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiglycol and the like.

  Examples of the amines include monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylmonoethanolamine, N-methyldiethanolamine, N-methylethanolamine, N-phenylethanolamine, and 3-aminopropyldiethylamine. Is mentioned.

  Examples of the amide compounds include 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, β-methoxy-N, N-dimethyl. Examples include propionamide and β-butoxy-N, N-dimethylpropionamide. Among these, water-soluble amide compounds described below are preferable.

The water-soluble amide compound is a polar solvent capable of dissolving many organic compounds and inorganic salts, and can be widely mixed from water to an organic solvent. Therefore, the effect of improving the wettability and solubility with respect to the recording medium and the mixing stability of other components can be obtained.
Moreover, the amide compound shown with the following structural formula which is 1 type of an acyclic amide compound is also contained.

  The amide compound has different hydrophilicity depending on the length of the alkyl group, and is miscible with water or an organic solvent.

  The amide compound in which the alkyl group is a methyl group has a high boiling point of 216 ° C., a high equilibrium water content of 39.2% by mass in an environment of 23 ° C. and 80% relative humidity, and a liquid viscosity of 1 in an environment of 25 ° C. Very low, 48 mPa · s. Furthermore, since it is very easy to dissolve in a water-soluble organic solvent and water, the viscosity of the ink can be reduced, and it is very preferable as a water-soluble organic solvent used in the ink. The ink containing the amide compound becomes an ink having good storage stability and ejection stability and is gentle to the maintenance / recovery device.

  The amide compound in which the alkyl group is a butyl group is freely soluble in water and has a solubility of liquid paraffin and n-hexane, has a high boiling point of 252 ° C., and is used as an ink penetration improver or solubilizer. It is possible to add.

  All of these amide compounds have high solubility and high solubility with respect to conventional adhesives, making it difficult to increase the amount added to water-based inks. Therefore, in a head using an adhesive such as a laminated head, the amount of amide compound added to the ink used is 10% by mass or less, and a large amount of addition attacks the adhesive interface between the layers, and is sufficient. There was a problem that a sufficient strength could not be obtained.

In the case of the liquid ejection head of the present invention, it is possible to add 20% by mass or more as the content of the amide compound in the aqueous ink.
The content of such an amide compound is preferably 20% by mass or more from the viewpoint of the solid uniformity of the printed image. When the content exceeds 60% by mass, the dryness on the paper surface is inferior and the character quality on plain paper is further deteriorated. Sometimes.

  As the solid wetting agent, saccharides and the like are preferable. Examples of the saccharide include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides, and the like. Specific examples include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like.

Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature such as α-cyclodextrin and cellulose.
Derivatives of these saccharides include reducing sugars (for example, sugar alcohols (general _{formula: HOCH 2 (CHOH) nCH 2} OH ( where, n is represented by an integer of 2-5). ), Oxidized sugar (eg, aldonic acid, uronic acid, etc.), amino acid, thioic acid and the like.

Among these, sugar alcohol is preferable. Examples of the sugar alcohol include maltitol and sorbit.
The content of the water-soluble organic solvent is preferably 10% by mass to 50% by mass and more preferably 15% by mass to 40% by mass with respect to the total amount of the aqueous ink. When the content is 10% by mass or more, excellent ejection stability is obtained, and when it is 50% by mass or less, drying property on the paper surface is obtained and drying and fixing do not take time.

-Colorant-
As the colorant, both a pigment and a dye can be used, but it is preferable to use a pigment from the viewpoint of light fading.
As the pigment, an organic pigment or an inorganic pigment can be used. Moreover, although it may contain a dye simultaneously for the purpose of color tone adjustment, it can be used within a range in which the weather resistance is not deteriorated. From the viewpoint of weather resistance, pigments are mainly preferably used. However, for the purpose of adjusting the color tone, a dye may be contained at the same time as long as the weather resistance is not deteriorated.

  As the inorganic pigment, for example, it was produced by a known method such as titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, contact method, furnace method, thermal method and the like. Carbon black etc. are mentioned.

  Examples of the organic pigment include azo pigments (eg, azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (eg, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone). Pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (eg basic dye chelates, acid dye chelates), nitro pigments, nitroso pigments, aniline black It is done. Among these, those having good affinity for water are preferably used.

  Among these pigments, a preferable form is one that has been surface-modified so that at least one hydrophilic group is bonded to the surface of the pigment directly or through another atomic group. For that purpose, a specific functional group (functional group such as a sulfone group or a carboxyl group) is chemically bonded to the surface of the pigment, or wet oxidation treatment is performed using hypohalous acid and / or a salt thereof. The method is used. Among these, a preferable form is a form in which carboxyl groups are bonded to the surface of the pigment and dispersed in water. In this case, since the pigment is surface-modified and the carboxyl group is bonded, not only the dispersion stability is improved, but also high-quality printing quality is obtained and the water resistance of the recording medium after printing is further improved. .

  This form of ink is excellent in redispersibility after drying, so printing is paused for a long period of time, and even when ink moisture near the nozzles of the inkjet head evaporates, clogging does not occur and a simple cleaning operation makes it easy. Printing can be performed. Further, this self-dispersing pigment has a particularly large synergistic effect when combined with a surfactant and a penetrating agent, which will be described later, and it is possible to obtain a more reliable and high-quality image.

  It is also possible to use a polymer emulsion in which a pigment is contained in fine polymer particles in addition to the pigment in the above form. The polymer emulsion containing a pigment is one in which a pigment is encapsulated in polymer fine particles and / or a pigment adsorbed on the surface of the polymer fine particles. In this case, it is not necessary that all the pigments are encapsulated and / or adsorbed, and the pigments may be dispersed in the emulsion. Examples of the polymer that forms the polymer emulsion include vinyl polymers, polyester polymers, polyurethane polymers, and the like. Among these, vinyl polymers and polyester polymers are preferable.

  In addition, it is possible to use not only the pigment but also a water-soluble dye, and the water-soluble dye is preferably an acid dye or a direct dye.

  The content of the colorant is preferably 1% by mass to 15% by mass and more preferably 3% by mass to 12% by mass with respect to the total amount of the aqueous ink.

-Surfactant-
The surfactant is not particularly limited as long as it does not impair the dispersion stability depending on the combination of the type of colorant, the wetting agent, and the water-soluble organic solvent, and can be appropriately selected according to the purpose. , Anionic surfactants, nonionic surfactants, amphoteric surfactants, acetylene glycol surfactants, fluorine surfactants, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, oxalate sulfonate, laurate, and polyoxyethylene alkyl ether sulfate salt.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene polyoxypropylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, Examples thereof include oxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine, and polyoxyethylene alkyl amide.

  Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine. Examples of the amphoteric surfactant include lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, dihydroxyethyl lauryl amine oxide, polyoxyethylene coconut oil alkyl dimethyl amine oxide, dimethyl alkyl (coconut) betaine, and dimethyl lauryl. Examples include betaine.

  Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, And acetylene glycols such as 5-dimethyl-1-hexyn-3-ol (Surfinol 104, 82, 465, 485 or TG manufactured by Air Products (USA), etc.). Among these, Surfynol 465, 104, or TG is preferable from the viewpoint of showing good print quality.

Examples of the fluorosurfactant include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, and perfluoroalkylamine oxide. Examples thereof include a compound, a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain or a sulfate ester salt thereof, and a fluorine-based aliphatic polymer ester.
Commercially available products can be used as the fluorosurfactant. Examples of the commercially available products include Surflon S-111, S-112, S-113, S121, S131, S132, S-141, and S-. 145 (all manufactured by Asahi Glass Co., Ltd.), Fullrad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431, FC-4430 (all Manufactured by Sumitomo 3M), FT-110, 250, 251, 400S (all manufactured by Neos), Zonyl FS-62, FSA, FSE, FSJ, FSP, TBS, UR, FSO, FSO-100, FSN N , FSN-100, FS-300, FSK (all manufactured by Dupont), Polyfox PF-136A, PF-156A, PF- 151N (both manufactured by OMNOVA).

  The content of the surfactant is preferably 0.01% by mass to 5% by mass and more preferably 0.5% by mass to 2% by mass with respect to the total amount of the water-based ink from the viewpoint of exhibiting a penetrating effect. preferable. When the content is less than 0.01% by mass, there is no effect of adding a surfactant. When the content exceeds 5% by mass, the permeability to the recording medium is unnecessarily high, and the image density decreases. This is more preferable in order to deal with plain paper having many physical properties.

-Penetration agent-
The penetrant preferably contains at least one polyol compound having a solubility in water at 20 ° C. of 0.2% by mass or more and less than 5.0% by mass.

Among such polyol compounds, examples of the aliphatic diol include 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, and 2 , 2-Diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl -2,5-hexanediol, 5-hexene-1,2-diol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, etc. Can be mentioned.
Among these, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol are preferable.

  Examples of other penetrants that can be used in combination include diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, and tetraethylene glycol chlorophenyl ether. Examples thereof include alkyl and aryl ethers of monohydric alcohols, lower alcohols such as ethanol, and the like, but are not limited thereto as long as they can be dissolved in ink and adjusted to desired physical properties.

  Even if the penetrant has a low solubility in water, it can be used as a penetrant as long as it is solubilized with the amide compound and does not precipitate from the ink. The conventional ink has a small solubilizing effect because the addition amount of the amide compound is small. However, since the above-described ink can add a large amount of the amide compound, it can also add a hardly soluble organic substance that could not be used conventionally. For this reason, it is possible to penetrate into coated paper for printing which has been difficult to penetrate.

The content of the penetrant is preferably 0.1% by mass to 4.0% by mass with respect to the total amount of the aqueous ink. When the content is less than 0.1% by mass, a fast-drying property cannot be obtained and a blurred image may be obtained. When the content exceeds 4.0% by mass, the dispersion stability of the colorant is impaired, and the nozzle May become clogged easily, or the permeability to the recording medium may become higher than necessary, causing problems such as a decrease in image density and occurrence of show-through.
Further, since the penetrant is an organic substance having a strong hydrophobic property, it has a high affinity with respect to the resin layer of the head and easily penetrates. In a head using an adhesive such as a laminated head, there is a problem in that a large amount of penetrating agent attacks the adhesive interface through the resin layer between the laminates and a sufficient strength cannot be obtained.
In the case of the head using the treatment layer of the present invention, a large amount of penetrating agent can be added in order to improve the durability of the adhesive interface.

-Water dispersible resin-
Examples of the water-dispersible resin include condensation-type synthetic resins (for example, polyester resins, polyurethane resins, polyepoxy resins, polyamide resins, polyether resins, silicon resins, etc.), addition-type synthetic resins (for example, polyolefin resins, polystyrene). Resin, polyvinyl alcohol resin, polyvinyl ester resin, polyacrylic acid resin, unsaturated carboxylic acid resin, etc.), natural polymers (eg, celluloses, rosins, natural rubber, etc.). The water-dispersible resin may be used as a homopolymer, may be used as a copolymer and used as a composite resin, and any of a single-phase structure type, a core-shell type, and a power feed type emulsion can be used. .

  As the water-dispersible resin, those having a hydrophilic group in the resin itself and having a self-dispersibility can be used, and the resin itself having no dispersibility and imparted with a surfactant or a resin having a hydrophilic group can be used. . In particular, an emulsion of resin particles obtained by emulsification and suspension polymerization of an ionomer or an unsaturated monomer of a polyester resin or a polyurethane resin is optimal. In the case of emulsion polymerization of unsaturated monomers, in order to obtain a resin emulsion by reacting with water added with unsaturated monomers, polymerization initiators, surfactants, chain transfer agents, chelating agents, pH adjusters, etc. Thus, a water-dispersible resin can be easily obtained, and the desired properties can be easily produced because the resin configuration can be easily changed.

  Usable unsaturated monomers include, for example, unsaturated carboxylic acids, (meth) acrylic acid ester monomers, (meth) acrylic acid amide monomers, aromatic vinyl monomers, vinyl cyanide. Compound monomers, vinyl monomers, allyl compound monomers, olefin monomers, diene monomers, oligomers having unsaturated carbon, and the like can be used alone or in combination. By combining these monomers, the properties can be flexibly modified, and the properties of the resin can be modified by performing a polymerization reaction or a graft reaction using an oligomer type polymerization initiator.

  It is possible to modify the properties of the water-dispersible resin flexibly by using unsaturated monomers alone or in combination, and resinating them with a polymerization initiator. Such water-dispersible resins are strongly alkaline and strongly acidic, so that molecular breakage such as dispersion breakage and hydrolysis is caused. Therefore, the pH is preferably 4 to 12, and the pH is preferably miscible with the water-dispersible colorant. Is more preferably 6 to 11, and a pH of 7 to 9 is still more preferable.

  The particle size of the water-dispersible resin is related to the viscosity of the dispersion. When the composition is the same, the smaller the particle size, the larger the viscosity at the same solid content. The average particle size of the water-dispersible resin is preferably 50 nm or more so as not to have an excessively high viscosity when converted into an ink. In addition, when the average particle size is several tens of μm, it becomes larger than the nozzle opening of the ink jet head and cannot be used. It is known that even if the particle size is smaller than the nozzle diameter, the ejection property is deteriorated if particles having a large particle size are present in the ink. The average particle diameter is preferably 500 nm or less and more preferably 150 nm or less in order not to inhibit the ink discharge properties.

  The water-dispersible resin has a function of fixing the water-dispersible colorant on the paper surface, and is preferably formed into a film at room temperature to improve the fixability of the color material. Therefore, the minimum film forming temperature (MFT) is preferably room temperature or lower, and more preferably 20 ° C. or lower.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected as necessary. For example, a pH adjuster, antiseptic / antifungal agent, chelating agent, rust inhibitor, antioxidant, ultraviolet absorber, oxygen Examples include absorbents, light stabilizers, and antifoaming agents.

The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 to 11 without adversely affecting the recording ink to be prepared, and can be appropriately selected according to the purpose. Examples include alcohol amines, alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, alkali metal carbonates, and the like.
If the pH is less than 7 or more than 11, the amount of the ink jet head or ink supply unit that melts out is large, and problems such as ink deterioration, leakage, and ejection failure may occur.

Examples of the alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
Examples of the ammonium hydroxide include ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, and the like.
Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

  Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol and the like.

  Examples of the chelating agent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of the antioxidant include phenolic antioxidants (including hindered phenolic antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.

  Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a nickel complex ultraviolet absorber.

Examples of the antifoaming agent include a silicone antifoaming agent, a polyether antifoaming agent, and a fatty acid ester antifoaming agent. When using a general antifoaming agent in combination with a large amount of inorganic fine particles from the viewpoint of enhancing the bubble breaking effect, the recording ink using the antifoaming agent has a particle size of 0.5 μm. Since the above coarse particles contain 3.0 × 10 ⁷ (pieces / 5 μL) or less and the amount of particles having a particle size of 1 μm or more and less than 5 μm needs to be 1% by number or less, the inorganic What is necessary is just to remove fine particles suitably as needed.

  The water-based ink comprises a colorant, a water-soluble organic solvent (wetting agent), a surfactant, a penetrating agent, a water-dispersible resin and water, and if necessary, other components dispersed or dissolved in an aqueous medium, Manufacture by stirring and mixing as necessary.

  The dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, and the like. Stirring and mixing is performed with a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, and the like. It can be carried out.

  There is no restriction | limiting in particular as a physical property of the said water-based ink, According to the objective, it can select suitably, For example, it is preferable that a viscosity, surface tension, etc. are the following ranges.

The viscosity of the water-based ink at 25 ° C. is preferably 3 mPa · s to 20 mPa · s.
By setting the ink viscosity to 3 mPa · s or more, the effect of improving the printing density and the character quality can be obtained. On the other hand, by suppressing the ink viscosity to 20 mPa · s or less, it is possible to ensure the discharge performance. Here, the said viscosity can be measured at 25 degreeC, for example using a viscometer (RL-550, the Toki Sangyo Co., Ltd. make).

  The surface tension of the water-based ink is preferably 35 mN / m or less, more preferably 32 mN / m or less at 25 ° C. When the surface tension exceeds 35 mN / m, leveling of the ink on the recording medium is difficult to occur, and the drying time may be prolonged.

<< Photopolymerizable ink >>
The photopolymerizable ink contains a polymerizable compound, and further contains other components as necessary.
As content of the said polymeric compound, 10 mass%-70 mass% are preferable with respect to the photopolymerizable ink whole quantity. The compounds that can be used differ depending on the photocuring reaction, and are classified into radical polymerization photocurable compounds using photoradical generation initiators and cationic polymerization photocurable compounds using photoacid generation initiators. The radical polymerization photocurable compound and the cationic polymerization photocurable compound can be mixed and used, and can be arbitrarily designed according to the curing characteristics, adhesion strength, and image forming process. .

-Radical polymerization photocurable compound-
Examples of the radical polymerization-based photocurable compound include compounds having an unsaturated hydrocarbon chain as a reactive functional group. Examples of the reactive functional group include a vinyl group, an isopropenyl group, an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, a propioyl group, and a maleoyl group.

  Examples of the compound having a monofunctional group include 2-ethylhexyl (meth) acrylate (EHA), 2-hydroxyethyl (meth) acrylate (HEA), 2-hydroxypropyl (meth) acrylate (HPA), caprolactone-modified tetrahydrofur Examples include furyl (meth) acrylate.

  Examples of the compound having a bifunctional group include tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol hydroxy Examples include pivalic acid ester di (meth) acrylate (MANDA).

  Examples of polyfunctional groups include trimethylolpropane tri (meth) acrylate (TMPTA), pentaerythritol tri (meth) acrylate (PETA), dipentaerythritol hexa (meth) acrylate (DPHA), triallyl isocyanate, and ε-caprolactone. Examples thereof include (meth) acrylates of modified dipentaerythritol.

  Examples of the oligomer include polyester resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, ether resins, acrylates such as polyhydric alcohols, and methacrylates.

  Examples of the curable polymer include a water-soluble resin having a polymerizable functional group, and an emulsion type photocurable resin.

  At least one selected from the photopolymerizable compounds of the radical polymerization system, or a mixture of two or more can be used.

  Examples of the photo radical polymerization initiator include a molecular cleavage type photo polymerization initiator and a hydrogen abstraction type photo polymerization initiator.

  Examples of the molecular cleavage type photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- Examples include 1-one and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one.

  Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone compounds such as benzophenone, methylbenzophenone, methyl-2-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl sulfide, and phenylbenzophenone; 2,4-diethyl; Examples include thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, and 1-chloro-4-propylthioxanthone.

  In addition, an amine compound can also be used together as a polymerization accelerator. Examples of the amine compound include ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid-2-ethylhexyl, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and p-dimethylaminobenzoic acid. Examples include butoxyethyl.

-Cationically polymerizable photocurable compound-
Examples of the cationic polymerization-based photocurable compound include vinyl aromatics, vinyl ethers, N-vinyl amides, compounds having an epoxy group, and compounds having an oxetanyl group.

  Examples of the vinyl aromatics include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, Examples thereof include 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinylnaphthalene, 4-methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene and the like.

  Examples of the vinyl ethers include isobutyl vinyl ether, ethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether, p-methoxyphenyl vinyl ether, α-methylphenyl vinyl ether, β-methylisobutyl vinyl ether, β-chloroisobutyl vinyl ether, ethylene glycol diether. Examples include vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, hydroxybutyl vinyl ether, propylene ether of propylene glycol, and the like.

  Examples of the N-vinylamides include N-vinylcarbazole, N-vinylpyrrolidone, N-vinylindole, N-vinylpyrrole, N-vinylphenothiazine, N-vinylacetanilide, N-vinylethylacetamide, and N-vinylsuccinimide. , N-vinylphthalimide, N-vinylcaprolactam, N-vinylimidazole and the like.

  Examples of the compound having an epoxy group include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy-1-methylcyclohexyl-3,4. -Epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate and the like.

  Examples of the compound having an oxetanyl group include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4- Examples include fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, and the like.

Examples of the other cationically polymerizable compounds include oxolane compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran, cyclic acetal compounds such as trioxane, 1,3-dioxolane, and 1,3,6-trioxane cyclooctane, β- Cyclic lactone compounds such as propiolactone and ε-caprolactone, thiirane compounds such as ethylene sulfide and thioepichlorohydrin, thietane compounds such as 1,3-propyne sulfide and 3,3-dimethylthietane, and cyclic thioethers such as tetrahydrothiophene derivatives Examples thereof include spiro orthoester compounds obtained by reaction of compounds and epoxy compounds with lactones.
A mixture of at least one or two or more selected from the cationic polymerization-based photocurable compounds can be used.

-Cationic photopolymerization initiator-
As the cationic photopolymerization initiator, a photoacid generator generally used for photocationic polymerization can be used, and examples thereof include a double salt that is an onium salt that releases a Lewis acid, or a derivative thereof. It is done.

Examples of the onium salt include organic compounds for atoms or atomic groups selected from S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. A cation having a group (at least one of which has an aromatic ring), tetrafluoroborate (BF ₄ ) ⁻ , tetrakis (pentafluorophenyl) borate (B (C ₆ F ₅ ) ₄ ) ⁻ , hexafluoro Examples thereof include a salt formed of any one of phosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate (AsF ₆ ) ⁻ , and hexachloroantimonate (SbCl ₆ ) ⁻ .

  A sulfonated product that generates sulfonic acid, a halide that generates hydrogen halide, and an iron allene complex can also be used as a photocationic polymerization initiator.

  If necessary, the ink can contain a colorant. As the colorant for the photopolymerizable ink, known inorganic pigments and organic pigments can be used. As the pigment, a material having the same structure as that of the water-based ink can be used.

  Unlike the water-based ink, the pigment is dispersed in oil, and a pigment dispersant is used to improve the dispersibility of the pigment.

Examples of the pigment dispersant include polyamide resins, hydroxyl group-containing carboxylic acid esters, salts of long chain polyaminoamides and high molecular weight acid esters, salts of high molecular weight polycarboxylic acids, salts of long chain polyaminoamides and polar acid esters, High molecular weight unsaturated acid ester, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxy Examples thereof include ethylene nonyl phenyl ether and stearylamine acetate.
The pigment dispersant is preferably a polyester polyamide resin having a number average molecular weight of 700 to 15,000.
The content of the pigment dispersant is preferably 0.1% by mass to 15% by mass and more preferably 0.5% by mass to 10% by mass in the photopolymerizable ink from the viewpoint of improving pigment dispersibility.

  As the pigment dispersant, commercially available products can be used. Examples of the commercially available products include Solsperse 32000, Solsperse 32500, Solsperse 32600, Solsperse 33500, Solsperse 34750, Solsperse 35100, Solsperse 37500, manufactured by Lubrizol; Examples include BYK9077 manufactured by the company.

  Further, as required, 4-methoxy-1-naphthol, methylhydroquinone, hydroquinone, t-butylhydroquinone, di-t-butylhydroquinone, methoquinone, 2,2'-dihydroxy-3,3'-di (α-methyl) (Cyclohexyl) -5,5'-dimethyldiphenylmethane, p-benzoquinone, di-t-butyldiphenylamine, phenothiazine, 9,10-di-n-butoxycyantracene, 4,4 '-[1,10-dioxo-1, 10-decanediylbis (oxy)] bis [2,2,6,6-tetramethyl] -1-piperidinyloxy and other polymerization inhibitors, higher fatty acid surfactants, silicone surfactants, fluorine surfactants Agents, polar group-containing polymer pigment dispersants and the like can be used.

  As the photopolymerizable ink, when the photopolymerization initiator, polymerizable monomer, colorant and the like are added, the viscosity is too high, and it may be difficult to eject the ink as an inkjet ink. In that case, it is preferable to dilute with a solvent.

The dilution solvent preferably has a boiling point in the range of 160 ° C to 190 ° C. When the boiling point exceeds 190 ° C., the curability is inhibited, and when the boiling point is less than 160 ° C., the ink is dried, for example, the ink may be hardened in an inkjet nozzle.
Examples of the dilution solvent include ether, ketone, aromatic, xylene, ethyl ethoxypropionate, ethyl acetate, cyclohexanone, diethylene glycol monomethyl ether, diethylene glycol, monoethyl ether, γ-butyllactone, ethyl lactate, cyclohexane methyl ethyl ketone, toluene, Examples thereof include ethyl ethoxypropionate, polymethacrylate or propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, diethylene glycol, triethylene glycol monobutyl ether.

  The viscosity of the photopolymerizable ink is preferably 3 mPa · s to 40 mPa · s at 25 ° C., more preferably 3 mPa · s to 35 mPa · s. Alternatively, at 60 ° C., 7 mPa · s to 15 mPa · s is preferable, and 10 mPa · s to 12 mPa · s is more preferable.

  The viscosities at 25 ° C. and 60 ° C. were measured by setting the temperature of the constant temperature circulating water at 25 ° C. and 60 ° C. with a cone plate type rotational viscometer manufactured by Toki Sangyo Co., Ltd. and VISCOMETER TV-22. VISCOMATE VM-150III was used to adjust the temperature of the circulating water. The temperature of 25 ° C. assumes a general room temperature environment, and the temperature of 60 ° C. assumes the specifications of a commercially available inkjet discharge head that can be heated, such as GEN4 manufactured by Ricoh Printing Systems. is there.

  The static surface tension at 25 ° C. of the photopolymerizable ink is preferably 20 mN / m to 40 mN / m, and more preferably 28 mN / m to 35 mN / m. The static surface tension was measured at 25 ° C. using a static surface tension meter (manufactured by Kyowa Interface Science Co., Ltd., CBVP-Z type). The static surface tension is assumed to be a specification of a commercially available inkjet discharge head such as GEN4 manufactured by Ricoh Printing Systems.

  When the colorant is composed of an inorganic pigment or an organic pigment, the average primary particle size of the pigment particles is preferably 20 nm to 200 nm, and more preferably 50 nm to 160 nm. If the average primary particle size is less than 20 nm, the fineness of the particles may result in lack of light resistance of the printed matter, and if it exceeds 200 nm, the fineness of the printed matter may be lacked. The average primary particle size is a value measured using, for example, an electron microscope (JEM-2010, manufactured by JEOL Ltd.).

<< Oil-based ink >>
The oil-based ink contains an organic solvent, a pigment, a dispersant, and other additives, and the same pigment and dispersant as the photopolymerizable ink can be used.

  As the organic solvent, an organic solvent such as an ester solvent, an alcohol solvent, a higher fatty acid solvent, a hydrocarbon solvent, or ether can also be used. These may be used singly or in combination of two or more.

  Examples of the ester solvent include methyl laurate, isopropyl laurate, isopropyl myristate, isopropyl palmitate, isooctyl palmitate, isostearyl palmitate, methyl oleate, ethyl oleate, isopropyl oleate, butyl oleate, linole Methyl acid, isobutyl linoleate, ethyl linoleate, isopropyl isostearate, soybean oil methyl, soybean oil isobutyl, tall oil methyl, tall oil isobutyl, diisopropyl adipate, diisopropyl sebacate, diethyl sebacate, propylene glycol monocaprate, tri Examples thereof include triethylolpropane 2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, and the like.

Examples of the alcohol solvent include isomyristyl alcohol, isopalmityl alcohol, isostearyl alcohol, oleyl alcohol, and the like.
Examples of the higher fatty acid solvent include isononanoic acid, isomyristic acid, isopalmitic acid, oleic acid, and isostearic acid.

  Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, and the like.

  Examples of the aliphatic hydrocarbon solvent and alicyclic hydrocarbon solvent include, for example, “Teclean N-16, Teclean N-20, Teclean N-22, No. 0 Solvent L, No. 0 Solvent M, manufactured by Nippon Oil Corporation. No. 0 Solvent H, AF-4, AF-5, AF-6, AF-7 (all trade names), “Nisseki Isozol, Naphthezol” (all trade names), ExxonMobil "IsoparG, IsoparH, IsoparL, IsoparM, ExxolD40, ExxolD80, ExxolD100, ExxolD140, ExxolD140" (all are trade names), etc. are mentioned.

  Examples of the ether solvent include diethyl glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol dibutyl ether and the like.

  As content of the said organic solvent, 60 mass% or more of oil-based ink whole quantity is preferable, and 70 mass%-98 mass% are more preferable.

<< solvent ink >>
The solvent ink contains an organic solvent, a pigment, a pigment dispersant, and a binder resin, and contains other components as necessary.
As the organic solvent, a volatile organic solvent used in ordinary solvent-based inks can be used.

  Examples of the organic solvent include alcohols, glycols, glycol ethers, esters, ketones, aromatic compounds, nitrogen-containing compounds, and the like.

  Examples of the alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tridecyl alcohol, cyclohexyl alcohol, 2-methylcyclohexyl alcohol and the like.

  Examples of the glycols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and glycerin.

  Examples of the glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol diethyl ether, and ethylene glycol dimethyl ether.

  Examples of the esters include ethyl acetate, isopropyl acetate, n-butyl acetate, methyl lactate, ethyl lactate, and butyl lactate.

Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, diacetone alcohol, and the like.
Examples of the aromatic compound include toluene and xylene.

  Examples of the nitrogen-containing compound include acetonitrile, γ-butyrolactone, γ-valerolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and the like.

  From these, various solvents are selected from the viewpoints of compatibility with the characteristics of the head nozzle during printing, safety, and drying properties, and a plurality of solvents can be mixed and used as necessary.

  The solvent ink preferably contains glycol ethers as an organic solvent.

  Examples of the glycol ethers include diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, Examples include diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

  The binder resin used in the solvent ink may be a binder resin commonly used in ordinary ink compositions, and is not particularly limited and can be appropriately selected according to the purpose. For example, a polyester resin, an acrylic resin , Vinyl chloride resin, epoxy resin, phenol resin, novolak resin, rosin modified phenolic resin, melamine, benzoguanamine and other amino resins, polyamide resin, cellulose diacetate, cellulose triacetate, nitrocellulose, cellulose nitrate, cellulose propionate, cellulose acetate butyrate Cellulose ester resins such as rate, methylcellulose, ethylcellulose, benzylcellulose, tritylcellulose, cyanethylcellulose, carboxymethylcellulose, carboxyethylcellulose , And cellulose ether resin, such as amino ethyl cellulose. Among these, it is preferable to include a polyester resin, an acrylic resin, and a vinyl chloride resin because adhesion with a base material when printed is improved.

  As the polyester resin, both saturated polyester and unsaturated polyester resin can be used. The polyester resin is obtained by a condensation reaction between a polybasic acid and a polyhydric alcohol. The number average molecular weight of the polyester resin is preferably 1,000 to 50,000, and more preferably 2,000 to 20,000.

As the acrylic resin, those obtained by copolymerizing a commonly used radical polymerizable monomer can be used.
Examples of the radical polymerizable monomer include (meth) acrylic acid esters: methyl acrylate, ethyl acrylate, isopropyl acrylate, nbutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Examples include isopropyl methacrylate, nbutyl methacrylate, isobutyl methacrylate, tbutyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate.

  Examples of the vinyls include styrene, vinyl toluene, α-methyl styrene, vinyl acetate, vinyl propionate, vinyl pyrrolidone, vinyl chloride, vinylidene chloride, vinylidene fluoride, ethyl vinyl ether, and isobutyl vinyl ether.

Examples of α-olefins include ethylene and propylene.
Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, mono-n-butyl maleate, mono-n-butyl fumarate, mono-n-butyl itaconate, and crotonic acid. .

  Examples of the hydroxyl group-containing (meth) acrylic acid esters include 2 hydroxyethyl (meth) acrylate, 2 hydroxypropyl (meth) acrylate, 3 hydroxypropyl (meth) acrylate, 4 hydroxybutyl (meth) acrylate, (2-hydroxymethyl) ethyl acrylate, (2-hydroxymethyl) butyl acrylate, (meth) acrylic acid (4-hydroxymethylcyclohexyl) methyl, glycerol mono (meth) acrylate, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate , 2-hydroxy 3-phenoxypropyl (meth) acrylate and the like.

  Examples of amide group-containing monomers include acrylamide, methacrylamide, maleic acid amide, diacetone acrylamide, and the like.

Examples of the glycidyl group-containing monomer include glycidyl methacrylate and allyl glycidyl ether.
Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.

Examples of dienes include butadiene and isoprene.
Examples of the hydroxyl group-containing allyl compound include allyl alcohol and 2-hydroxyethyl allyl ether.
Examples of the tertiary amino group-containing monomer include dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.

  Examples of the alkoxysilyl group-containing monomers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltris (β-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and vinyl. Examples include dimethylmethoxysilane, vinyldimethylethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane.

  Further, monomers having two or more unsaturated bonds in one molecule, for example, diallyl phthalate, divinylbenzene, allyl acrylate, trimethylolpropane trimethacrylate and the like can be mentioned.

  These monomers may be used alone or in combination of two or more.

  Examples of the vinyl chloride resin include copolymer resins of vinyl chloride and other monomers such as vinyl acetate, vinylidene chloride, acrylic, and maleic acid. Among these, a vinyl chloride / vinyl acetate copolymer resin is preferable, and a copolymer resin having a weight average molecular weight of 30,000 or less.

  These resins can be used in combination, and the content of the resin is preferably 1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass.

There is no restriction | limiting in particular as coloring of an ink, According to the objective, it can select suitably, Yellow, magenta, cyan, black etc. are mentioned.
When recording is performed using an ink set in which two or more of these colorings are used in combination, a multicolor image can be formed. When recording is performed using an ink set in which all colors are combined, a full color image is formed. be able to.

-Recording media-
The recording medium is not particularly limited and may be appropriately selected from known media. For example, plain paper, glossy paper, special paper, thread, fiber, fabric, leather, metal, plastic, glass, wood , Ceramics, OHP sheet, film and the like.

<Other means>
Examples of the other means include a cleaning means and a control means.

-Cleaning means-
The cleaning means is means for wiping the liquid discharge surface of the nozzle plate of the liquid discharge head with a blade.
There is no restriction | limiting in particular about the magnitude | size, a material, a shape, a structure, etc. as said blade, According to the objective, it can select suitably.
There is no restriction | limiting in particular as a magnitude | size of the said blade, According to the objective, it can select suitably.
Examples of the material of the blade include rubber and elastomer from the viewpoint of wiping the surface of the water-repellent film 4 of the nozzle plate 1.
The shape of the blade is not particularly limited as long as wiping treatment can be performed, and can be appropriately selected according to the purpose. Examples thereof include a plate shape and a plate shape.

  The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  Here, an example of an ink jet recording apparatus which is an image forming apparatus equipped with the liquid discharge head of the present invention will be described with reference to FIGS. 12 is an explanatory side view of the mechanism of the apparatus, FIG. 13 is an explanatory plan view of the main part of the mechanism, and FIG. 14 is an explanatory front view of an example of the head unit.

  This image forming apparatus is a serial type image forming apparatus, and a carriage 233 is slidably held in a main scanning direction by main and slave guide rods 231 and 232 which are guide members horizontally mounted on left and right side plates 221A and 221B. . Then, the main scanning motor (not shown) moves and scans in the direction indicated by the arrow (carriage main scanning direction) via the timing belt.

  As shown in FIG. 12, the carriage 233 is mounted with a head unit in which a recording head 234 including a liquid discharge head according to the present invention and a tank 235 for storing ink supplied to the head 234 are integrated. . The recording head 234 is mounted with a nozzle row composed of a plurality of nozzles arranged in the sub-scanning direction orthogonal to the main scanning direction and the ink droplet ejection direction facing downward.

  Each recording head 234 has two nozzle rows. Then, one nozzle row of one recording head 234a discharges black (K) droplets, and the other nozzle row discharges cyan (C) droplets. Also, one nozzle row of the other recording head 234b discharges magenta (M) droplets, and the other nozzle row discharges yellow (Y) droplets. Here, a configuration in which droplets of four colors are ejected in a two-head configuration is used, but it is also possible to arrange four nozzle rows per head and eject each of the four colors with one head.

  Further, the ink of each color is replenished and supplied from the ink cartridge 210 of each color to the tank 235 of the recording head 234 via the supply tube 236 of each color.

  On the other hand, as a paper feeding unit for feeding the paper 242 stacked on the paper stacking unit (pressure plate) 241 of the paper feed tray 202, a half-moon roller (feeding) that separates and feeds the paper 242 one by one from the paper stacking unit 241. Paper roller) 243 and a separation pad 244 facing the paper feed roller 243.

  A guide 245 for guiding the paper 242, a counter roller 246, a conveyance guide member 247, and a tip pressure roller 249 are used to feed the paper 242 fed from the paper feeding unit to the lower side of the recording head 234. And a pressing member 248 having Furthermore, a transport belt 251 is provided as a transport unit for electrostatically attracting the fed paper 242 and transporting it at a position facing the recording head 234.

  The conveyor belt 251 is an endless belt, and is configured to wrap around the conveyor roller 252 and the tension roller 253 so as to circulate in the belt conveyance direction (sub-scanning direction). Further, a charging roller 256 for charging the surface of the conveying belt 251 is provided. The charging roller 256 is disposed so as to come into contact with the surface layer of the conveyor belt 251 and to rotate following the rotation of the conveyor belt 251. The transport belt 251 rotates in the belt transport direction when the transport roller 252 is rotationally driven through timing by a sub-scanning motor (not shown).

  As a paper discharge unit for discharging the paper 242 recorded by the recording head 234, a separation claw 261 for separating the paper 242 from the conveying belt 251, a paper discharge roller 262, and a paper discharge roller 263 are provided. A paper discharge tray 203 is provided below the paper roller 262.

  A duplex unit 271 is detachably mounted on the back surface of the apparatus main body. The duplex unit 271 takes in the paper 242 returned by the reverse rotation of the transport belt 251, reverses it, and feeds it again between the counter roller 246 and the transport belt 251. The upper surface of the duplex unit 271 is a manual feed tray 272.

A maintenance / recovery mechanism 281 for maintaining and recovering the state of the nozzles of the recording head 234 is disposed in the non-printing area on one side in the scanning direction of the carriage 233.
The maintenance / recovery mechanism 281 includes caps 282 a and 282 b for capping the nozzle surfaces of the recording head 234. The maintenance / recovery mechanism 281 includes a wiper member 283 for wiping the nozzle surface. The maintenance / recovery mechanism 281 includes a blank discharge receptacle 284 that receives droplets when performing blank discharge for discharging droplets that do not contribute to recording in order to discharge the thickened recording liquid.

  Further, in the non-printing area on the other side in the scanning direction of the carriage 233, there is an empty space for receiving a liquid droplet when performing an empty discharge for discharging a liquid droplet that does not contribute to the recording in order to discharge the recording liquid thickened during the recording. A discharge receiver 288 is disposed. The idle discharge receiver 288 includes an opening 289 along the nozzle row direction of the recording head 234 and the like.

  In this image forming apparatus configured as described above, the sheets 242 are separated and fed one by one from the sheet feeding tray 202 and guided by the guide 245, and are nipped between the conveying belt 251 and the counter roller 246 and conveyed. The Further, the leading edge of the sheet 242 is guided by the conveying guide 237 and pressed against the conveying belt 251 by the leading end pressing roller 249, and the conveying direction is changed by approximately 90 °.

  When the paper 242 is fed onto the charged transport belt 251, the paper 242 is attracted to the transport belt 251, and the paper 242 is transported in the sub-scanning direction by the circular movement of the transport belt 251.

  Therefore, by driving the recording head 234 according to the image signal while moving the carriage 233, ink droplets are ejected onto the stopped paper 242 to record one line, and after the paper 242 is conveyed by a predetermined amount, Record the next line. Upon receiving a recording end signal or a signal that the trailing edge of the paper 242 has reached the recording area, the recording operation is finished and the paper 242 is discharged onto the paper discharge tray 203.

As described above, since the image forming apparatus includes the liquid discharge head according to the present invention as a recording head, a high-quality image can be stably formed.
The “paper” is not limited to paper, but includes “so-called recording medium, recording medium, recording paper, recording paper” and the like. In addition, image formation, recording, printing, printing, and printing are all synonymous. The “liquid ejecting apparatus” means an apparatus that includes an image forming apparatus and ejects liquid onto a medium.
In addition, the “image” is not limited to a planar image, and includes an image given to a three-dimensionally formed image and an image formed by three-dimensionally modeling a solid itself.
Further, the image forming apparatus includes both a serial type image forming apparatus and a line type image forming apparatus, unless otherwise limited.

The drive element is not limited to a piezoelectric actuator, and an electrostatic actuator composed of a diaphragm and a counter electrode can also be used.
In the above, the liquid discharge head according to the present invention is applied to the ink jet head. However, a liquid discharge head for discharging a liquid other than ink, for example, a liquid resist for patterning, a liquid discharge head for discharging a gene analysis sample, and the like. It can also be applied to.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by these Examples.

(Synthesis example 1 of methoxy group-containing silane-modified bisphenol type epoxy resin (A))
<Synthesis of methoxy group-containing silane-modified bisphenol type epoxy resin (A)>
In a reactor equipped with a stirrer, a water separator, a vacuum pipe, a thermometer, and a nitrogen gas introduction pipe, 100 g of bisphenol type epoxy resin (trade name: JER834, manufactured by Mitsubishi Chemical Corporation) and 22.70 g of diethylene glycol dimethyl ether are added. In addition, it was dissolved at 100 ° C. 95.1 g of methyltrimethoxysilane partial condensate (trade name: MTMS-A, average number of Si per molecule is 3.2, manufactured by Tama Chemical Co., Ltd.) and 0.03 g of dioctyltin laurate as a catalyst were added. And methanol removal reaction at 100 ° C. for 6 hours. Diethylene glycol dimethyl ether and methanol were removed by cooling to 80 ° C. and stirring under reduced pressure to obtain a methoxy group-containing silane-modified bisphenol type epoxy resin (A).

(Examples 1-2 and Comparative Examples 1-2)
-Preparation of resin composition and cured product (resin layer)-
An epoxy compound, a curing agent, a curing catalyst, and a coupling agent shown in Table 1 below were added, and the resin composition before curing was obtained by stirring for 15 minutes while cooling.
Next, the glass transition temperature (Tg) and the liquid to be discharged may be discharged as the resistance to the liquid to be discharged, which is important for the liquid discharge apparatus, since it may be heated and discharged to reduce the swelling rate and the viscosity of the liquid. The elution amount of the resin composition component was evaluated. The results are shown in Table 1 below.

-Preparation of resin layer evaluation sample-
Resin compositions having a width of 10 mm, a length of 500 mm, and a thickness of 1 mm are obtained by filling the molds with the resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 and then curing them by heating at 80 ° C. for 3 hours. A cured product (resin layer) of the product was produced.

<Swellability test>
The cured product of the resin composition was immersed in an evaluation test solution in which N-methylpyrrolidone and pure water were mixed at a ratio of 1: 1 (50 ° C., 40 hours, ultrasonic), before and after immersion in the test solution. The swelling rate was calculated from the following formula from the weight.
[Formula 1]
Swelling ratio (%) = [(weight after test−initial weight) / initial weight] × 100
[Evaluation criteria]
○: Swelling rate is less than 3% Δ: Swelling rate is 3% or more and less than 10% ×: Swelling rate is 10% or more

<Measurement of glass transition temperature (Tg)>
The glass transition temperature (Tg) of the cured product of each resin composition cured at 80 ° C. is measured by measuring the temperature at which the heat capacity changes by the DSC method (manufactured by Rigaku Corporation, thermal analyzer Thermo plus). Was evaluated according to the following criteria.
[Evaluation criteria]
○: Glass transition temperature is 100 ° C. or higher Δ: Glass transition temperature is 80 ° C. or higher and lower than 100 ° C. ×: Glass transition temperature is lower than 80 ° C.

<Elution amount test>
Each cured product cured at 80 ° C. for 3 hours is immersed in an evaluation test solution in which N-methylpyrrolidone and pure water are mixed at a volume ratio of 1: 1 (60 ° C., 1 week), and then into the test solution. The absorption spectrum before and after the immersion was measured by U-3310 manufactured by Hitachi, Ltd., and the elution amount was calculated from the difference (Δ) and evaluated according to the following criteria.
[Evaluation criteria]
◎: Elution amount is less than 0.3 abs ○: Elution amount is 0.3 abs or more and less than 0.5 abs △: Elution amount is 0.5 abs or more and less than 1.0 abs ×: Elution amount is 1.0 abs or more

(Examples 3-4 and Comparative Examples 3-4)
-Evaluation of ink swellability, initial adhesion, and adhesion reliability-
The ink swellability test was performed as follows. The results are shown in Table 5 below. In addition, as a function of maintaining the position of the resin layer, members (nozzle plate and flow channel plate) were bonded to each other, and initial adhesiveness and adhesion reliability were evaluated as follows. The results are shown in Table 5 below.

<Manufacture example 1-2 of a processing layer>
As shown in Table 2 below, the surface treatment was applied to the peel test sample and the ink swelling test sample.
As the treatment layer, Zr was introduced into the SiO ₂ film, and the element ratio of Si and Zr was fixed at 2: 1 for evaluation. As the metal species to be introduced into the SiO ₂ film, the film forming method uses a multi-source sputtering method, sets Si and Zr targets, introduces O ₂ as a reactive gas, and controls the power of each target. The element ratio was fixed.

* Elements other than the above in the treatment layer are 10at% or less

<Peel test specimen>
Single-crystal Si having a width of 17 mm and a thickness of 400 μm is formed by forming slits having a width of 140 μm and a length of 2,000 μm at a pitch of 150 dpi, and this slit group is arranged in four rows and the slit positions are shifted by a pitch of 42.3 μm. A processed specimen (adhesive area ratio of 64.7%) was used as a peel test piece.

<Surface treatment>
Each peel test piece was surface treated. The surface treatment was evaluated by introducing Ta into the SiO ₂ film and the SiO ₂ film. As a film forming method, a multi-source sputtering method was used to form a film on the sample. The conditions for the treatment layer are shown in Table 2 above.

<Joint>
The resin composition described in Table 5 was applied to the adhesion surface of the peel test piece so as to have a coating thickness of 2.5 μm, and the rolled SUS flat plate having a width of 19 mm and a thickness of 20 μm was manufactured in Production Example 1 or 2. The treated layer was superposed on the sample formed and heated while being pressurized at 10 cN · m, and adhesively cured at 80 ° C. for 3 hours. It adjusted so that the average thickness of the resin layer after joining might be set to 1.5 micrometers. As described above, each sample for peel test was prepared.

<Preparation of ink swellability test sample>
As a sample for ink swellability test, each resin composition shown in Table 1 was filled in a mold, heated at 80 ° C. for 3 hours and cured, and then released, and then 10 mm in width, 500 mm in length, and thickness. A cured product of 1 mm resin composition was prepared.

(Evaluation ink preparation examples 1-2)
<Preparation of evaluation inks 1 and 2>
As described in Tables 3 and 4 below, an amide type wetting agent was mixed and stirred for 1 hour to obtain a uniform mixed solution. Next, a coloring material and an antifoaming agent are added to the mixed solution and stirred for 1 hour, and then this dispersion is subjected to pressure filtration with a 0.8 μm cellulose acetate membrane filter to remove coarse particles and dust. The ink was removed and used as an evaluation ink.

In Table 3, the trade names of the components and the names of the manufacturing companies are as follows.
Pigment resin dispersant: manufactured by Cabot Corporation, trade name: REGAL660R dispersion liquid, N-methyl-2-pyrrolidone: manufactured by Mitsubishi Chemical Corporation, glycerin: manufactured by Sakamoto Pharmaceutical Co., Ltd., 1,3-butanediol: Tokyo Chemical Industry 1,2-hexanediol, manufactured by Tokyo Chemical Industry Co., Ltd., silicone surfactant: manufactured by BYK Japan, Inc., trade name: BYK-348

In Table 4, the trade names of the components and the names of the manufacturing companies are as follows.
・ C. I. Pigment Black 7: manufactured by Mitsubishi Chemical Corporation, Solsperse 37500: manufactured by Lubrizol Corporation, ethylene glycol-n-butyl ether acetate: manufactured by Tokyo Chemical Industry Co., Ltd., amyl propionate: manufactured by Tokyo Chemical Industry Co., Ltd., cyclohexanone: Tokyo Chemical Industry Co., Ltd. Company-made dipropylene glycol monomethyl ether: Tokyo Kasei Kogyo Co., Ltd. N-methyl-2-pyrrolidone: Mitsubishi Chemical Co., Ltd. Fluorosurfactant: Big Chemie Japan Co., Ltd., trade name: BYK-340
Methyl methacrylate / butyl methacrylate copolymer: manufactured by Rohm and Haas, trade name: Paraloid B60

<Ink swelling test>
The prepared ink swelling test samples (cured products of the resin composition) are immersed in the inks described in Tables 3 and 4 (50 ° C., 40 hours, ultrasonic), and immersed in the inks. The swelling rate was calculated from the following formula 1 from the weight before and after, and the swelling property was evaluated according to the following criteria.
[Formula 1]
Swelling ratio = [(weight after test−initial weight) / initial weight] × 100
[Evaluation criteria]
A: Swelling rate is less than 3% B: Swelling rate is 3% or more and less than 5% C: Swelling rate is 5% or more and less than 10% D: Swelling rate is 10% or more

<Initial adhesiveness>
The peel strength when each sample for peel test was peeled 5 mm at a rate of 1 mm / min in 90 ° direction peel strength measurement with a desktop material testing machine (Orientec Co., Ltd., Tensilon STA-1150) was measured 5 times. The average peel strength was determined and the initial adhesion was evaluated according to the following criteria.
[Evaluation criteria]
A: Average peel strength is 1.2 N or more B: Average peel strength is 1.0 N or more and less than 1.2 N C: Average peel strength is 0.5 N or more and less than 1.0 N D: Average peel strength is less than 0.5 N An average peel strength of 0.5 N or more (A to C) is a required specification.

<Adhesion reliability>
Each sample after the peel strength test was subjected to an ink resistance test (ink immersion, 60 ° C., 60 days) in which the ink described in Tables 3 and 4 was immersed, and then a peel test was performed.
The peel strength when each sample after the ink resistance test was peeled by 5 mm at a rate of 1 mm / min at 90 ° direction peel strength measurement with a desktop material tester (Orientec Co., Ltd., Tensilon STA-1150). The measurement was performed 5 times to determine the average peel strength, and the adhesion reliability was evaluated according to the following criteria.
[Evaluation criteria]
A: Average peel strength is 1.2 N or more B: Average peel strength is 1.0 N or more and less than 1.2 N C: Average peel strength is 0.5 N or more and less than 1.0 N D: Average peel strength is less than 0.5 N The average peel strength was 0.5N or more (A to C) as the required specification.

As an aspect of this invention, it is as follows, for example.
<1> Contains a methoxy group-containing silane-modified bisphenol-type epoxy resin (A), a polythiol compound (B) having two or more thiol groups in the molecule, and an imidazole compound (C) represented by the following general formula (1) It is a curable composition characterized by containing the resin composition to do.
However, in said general formula (1), k is 1 or more and less than 6. j is 0 or 1. R ₁ , R ₂ , and R ₃ each independently represent any of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group. R ₄ represents any one of an alkylene group having 1 to 20 carbon atoms, an arylene group, and —CH ₂ CH ₂ COO—. R ₅ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cyanomethyl group when k is 1, and has 1 to 20 carbon atoms when k is 2 or more and less than 6. Represents a hydrocarbon group.
<2> The curable composition according to <1>, wherein the resin composition further contains an epoxy compound represented by the following general formula (2).
However, the general formula (2), R ₆ is, indicates a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
<3> The curable composition according to any one of <1> to <2>, wherein the resin composition further contains an epoxy compound represented by the following general formula (3).
<4> The polythiol compound (B) is dipentaerythritol hexa (3-mercaptobutyrate) and 1,3,5-tris (3-mercaptopropyl) -1,3,5-triazine-2,4. , 6 (1H, 3H, 5H) -trione is the curable composition according to any one of <1> to <3>.
<5> The curable composition according to any one of <1> to <4>, wherein the resin composition further contains a silane coupling agent represented by the following general formula (4).
In the general formula (4), _{R 7} and _{R 8} represents an alkyl group having 1 to 4 carbon atoms. R ₉ represents any one of an alkylene group having 1 to 20 carbon atoms and an arylene group. R ₁₀ represents any one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group.
<6> The silane coupling agent represented by the general formula (4) is 3-aminopropyl-trimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, The curable composition according to <5>, which is at least one selected from N- (2-aminoethyl) aminopropylmethyldimethoxysilane and 3-phenylaminopropyltrimethoxysilane.
<7> From <1> to <6, wherein the content of the imidazole compound (C) represented by the general formula (1) is 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the epoxy compound. > The curable composition according to any one of the above.
<8> The curable composition according to any one of <1> to <7>, wherein an epoxy equivalent of the methoxy group-containing silane-modified bisphenol type epoxy resin (A) is 70 or more and 3,000 or less.
<9> The curable composition according to <8>, wherein an epoxy equivalent of the methoxy group-containing silane-modified bisphenol-type epoxy resin (A) is 90 or more and 2,000 or less.
<10> The polythiol compound (B) is dipentaerythritol hexa (3-mercaptobutyrate) and 1,3,5-tris (3-mercaptopropyl) -1,3,5-triazine-2,4. , 6 (1H, 3H, 5H) -trione is the curable composition according to any one of <1> to <9>.
<11> A liquid discharge head having a flow path composed of a first member, a resin layer, and a second member,
The liquid ejection head is characterized in that the resin layer contains a cured product of the curable composition according to any one of <1> to <10>.
<12> The liquid ejection head according to <11>, wherein the first member is a nozzle plate in which an ejection port for ejecting liquid is formed.
<13> The liquid discharge head according to <12>, wherein the nozzle plate includes a nozzle substrate and a water-repellent film on the nozzle substrate.
<14> The liquid discharge head according to any one of <12> to <13>, wherein the second member is a flow path plate having an individual liquid chamber communicating with the discharge port.
<15> The liquid ejection head according to any one of <11> to <14>, wherein a resin layer is provided between the first member and the second member.
<16> The liquid ejection head according to any one of <11> to <15>, wherein the resin layer has an average thickness of 1.0 μm to 2.5 μm.
<17> The liquid ejection head according to any one of <11> to <16>, further including a stimulus generating member.
<18> The above <11> to <17>, wherein the stimulus generating member is at least one selected from a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, and a light. It is a liquid discharge head of description.
<19> A liquid discharge apparatus comprising the liquid discharge head according to any one of <11> to <18>.
<20> An image forming apparatus comprising: an ink containing unit; and the liquid discharge head according to any one of <11> to <18>.

  The curable composition according to any one of <1> to <10>, the liquid ejection head according to any one of <11> to <18>, the liquid ejection device according to <19>, and the The image forming apparatus according to <20> can solve the above-described problems and achieve the object of the present invention.

Japanese Patent No. 4804774 JP, 2015-030273, A Japanese Patent Laying-Open No. 2015-221541

Claims (7)

Resin composition containing a methoxy group-containing silane-modified bisphenol-type epoxy resin (A), a polythiol compound (B) having two or more thiol groups in the molecule, and an imidazole compound (C) represented by the following general formula (1) A curable composition comprising a product.
However, in said general formula (1), k is 1 or more and less than 6. j is 0 or 1. R ₁ , R ₂ , and R ₃ each independently represent any of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group. R ₄ represents any one of an alkylene group having 1 to 20 carbon atoms, an arylene group, and —CH ₂ CH ₂ COO—. R ₅ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cyanomethyl group when k is 1, and has 1 to 20 carbon atoms when k is 2 or more and less than 6. Represents a hydrocarbon group. The curable composition according to claim 1, wherein the resin composition further contains an epoxy compound represented by the following general formula (2).
However, the general formula (2), R ₆ is, indicates a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The curable composition according to claim 1, wherein the resin composition further contains an epoxy compound represented by the following general formula (3).
  The polythiol compound (B) is dipentaerythritol hexa (3-mercaptobutyrate) and 1,3,5-tris (3-mercaptopropyl) -1,3,5-triazine-2,4,6 ( The curable composition according to any one of claims 1 to 3, which is at least one of 1H, 3H, 5H) -trione. The curable composition according to any one of claims 1 to 4, wherein the resin composition further contains a silane coupling agent represented by the following general formula (4).
In the general formula (4), _{R 7} and _{R 8} each independently represent an alkyl group having 1 to 4 carbon atoms. R ₉ represents any one of an alkylene group having 1 to 20 carbon atoms and an arylene group. R ₁₀ represents any one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group.   The silane coupling agent represented by the general formula (4) is 3-aminopropyl-trimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, N- ( The curable composition according to claim 5, which is at least one selected from 2-aminoethyl) aminopropylmethyldimethoxysilane and 3-phenylaminopropyltrimethoxysilane. A liquid discharge head having a flow path composed of a first member, a resin layer, and a second member,
A liquid discharge head, wherein the resin layer contains a cured product of the curable composition according to claim 1.