JP4579937B2 - Inkjet ink - Google Patents

Description

  The present invention relates to an inkjet ink.

  Conventionally, printing presses using plates have been used to produce printed materials that require a certain number of copies, such as regional advertisements, corporate distribution materials, and large posters. In recent years, on-demand printing presses capable of quickly responding to diversifying needs and capable of compressing inventory are being used in place of such conventional printing presses. As such an on-demand printer, an electrophotographic printer using toner or liquid toner and an inkjet printer capable of high-speed and high-quality printing are expected.

  On-demand printing machines use solvent-based inks and solvent-based liquid toners containing pigments and organic solvents, as with printing machines that use plates. In this technique, when a certain number of copies are printed, a non-negligible amount of organic solvent volatilizes. Therefore, there is a problem of atmospheric pollution due to the volatilized organic solvent, and an exhaust facility and a solvent recovery mechanism must be provided.

  On the other hand, in an ink jet printer, solvent-based ink can be handled in a closed system until it is discharged onto a printing surface. Therefore, the problem of atmospheric pollution can be reduced to some extent by taking appropriate exhaust measures. However, unlike ink used in a printing machine using a plate, ink used in an ink jet printer must have fluidity necessary for ejection. Therefore, the ink used must have a sufficiently high solvent concentration, and even with this technique, it is essentially difficult to solve the problem of atmospheric contamination caused by organic solvents.

  In addition, when solvent-based ink is used, the printing surface has a great influence on the image quality. For example, bleeding tends to occur on a permeable printing surface, and fixing of an image is difficult on a non-permeable printing surface. Furthermore, since a certain amount of time is required until the ink layer formed on the printing surface is dried, when forming a dark image on a wide printing surface, the ink layer is liable to be crushed due to its fluidity. . In addition, when solvent-based ink is used, the printing surface may be deteriorated as the ink layer is dried. That is, it is not always easy to obtain a high-quality printed matter with this technique.

  As an effective technique for the solvent problem, photosensitive ink and a printer system using the same have begun to attract attention. The photosensitive ink used is typically one containing a radically polymerizable monomer, a photopolymerization initiator, and a pigment (see, for example, Patent Document 1 and Patent Document 2), and is discharged onto the printing surface. The photosensitive ink is quickly photocured.

  According to this technique, since the ink layer can be made non-fluidized by light irradiation, a printed matter having a relatively high quality can be obtained. However, the photosensitive ink contains many carcinogenic components such as a radical generator, and the volatile acrylic acid derivative used as the radical polymerizable monomer has a large skin irritation and odor. That is, such photosensitive ink requires attention in handling. Furthermore, radical polymerization is significantly inhibited by the presence of oxygen in the air, and exposure light is absorbed by the pigment contained in the ink. As a result, since the exposure amount tends to be insufficient at the deep part of the ink layer, the conventional radical polymerizable ink has low sensitivity to light. Therefore, in order to obtain a high-quality printed matter with this technique, a very large exposure system is required.

  As an ink having a relatively small influence of oxygen, a photo-cation polymerizable photosensitive ink has been proposed (for example, see Patent Document 3). However, since this type of conventional ink contains a solvent, the problem of solvent release to the environment is inevitable. In addition, the cured product is further hardened and has a problem that the head is easily clogged because it is insoluble. Further, a cationic curable photosensitive composition for coating CD-ROM that can be ejected by inkjet has been proposed (see, for example, Patent Document 4). The composition that could actually be ejected by ink jet was mainly composed of vinyl ether and bisphenol A type epoxy having a carcinogenic problem, and the problem of release to the environment was also great.

  Furthermore, an inkjet ink containing a cationic curable monomer having a specific composition ratio has been proposed (see, for example, Patent Document 5). Such an ink also has a similar problem because it contains a specific vinyl ether compound having very high volatility as an essential component. Moreover, the usual vinyl ether compound as described in the above document has a problem of poor polymerizability when it is provided in combination with a pigment.

  In addition, a photosensitive inkjet ink containing a polyvalent vinyl ether compound and an alicyclic epoxy compound has been disclosed (for example, see Patent Document 6). The vinyl ether disclosed in this document has the above-described problems of poor polymerizability and carcinogenicity peculiar to the bisphenol A skeleton, and the combination with an alicyclic epoxy having high solubility and dark reactivity. There were problems with storage stability and resistance of printed materials to solvents.

  In particular, when the printing surface is an absorbing medium, the conventional acrylic photocurable inkjet ink has a problem that it is difficult to be cured inside the absorbing paper surface.

The conventional photocation curable ink jet ink has a problem that its viscosity change is severe. This is due to the fact that once an acid is generated due to changes over time, it is difficult to deactivate and there are many dark reactions of ink. In the case of inkjet ink, this problem is extremely serious because if the viscosity changes, the flying shape of the ink will be disturbed, the print reproducibility will be reduced, and in the worst case, it will easily fall into a fatal state such as ejection failure or ink clogging. It was.
JP-A-8-62841 JP 2001-272529 A Japanese Patent Publication No. 2-47510 (EUP-0071345-A2) Japanese Patent Laid-Open No. 9-183928 JP 2001-220526 A U.S. Pat. No. 5,888,084

  An object of the present invention is to provide an ink-jet ink that does not require the use of an organic solvent and does not require a large exposure system for obtaining a high-quality printed matter. It is another object of the present invention to provide an inkjet ink that solves the problems of low cationic polymerization reactivity and solvent resistance, particularly in a conventional photosensitive inkjet ink mainly composed of a vinyl ether compound.

An inkjet ink according to one embodiment of the present invention contains a photoacid generator that generates an acid by light irradiation, a color component, and an acid polymerizable compound that polymerizes in the presence of an acid. It includes a compound represented by the general formula (1).

(In the general formula (1), R ¹³ is selected from alkoxy and hydroxyl substituents, at least one is an alkoxy group, .R ¹⁴ of at least two is a group having a vinyl ether group or a vinyl ether skeleton A substituted or unsubstituted cyclic skeleton represented by the following general formula (VE1-a) or (VE1-b), and p is an integer of 2 or more.)

(In the above general formula, X 1 and Z 1 are alkylene groups having 1 to 5 carbon atoms, Y 1 is an alkylene group having 1 to 2 carbon atoms, and k is 0 or 1.)
An inkjet ink according to another aspect of the present invention contains a photoacid generator that generates an acid by light irradiation, a color component, and an acid polymerizable compound that polymerizes in the presence of an acid, and the acid polymerizable compound includes: It includes a compound represented by the following general formula (1).

(In the general formula (1), R ¹³ is selected from alkoxy and hydroxyl substituents, at least one is an alkoxy group, .R ¹⁴ of at least two is a group having a vinyl ether group or a vinyl ether skeleton And a cyclic skeleton composed of a substituted or unsubstituted aromatic ring skeleton, and p is an integer of 2 or more.)

  According to one embodiment of the present invention, there is provided an inkjet ink that does not require the use of an organic solvent and does not require a large exposure system for obtaining a high-quality printed matter.

  Embodiments of the present invention will be described below.

  An ink-jet ink according to an embodiment of the present invention contains a photoacid generator that generates an acid by light irradiation, a color component, and a compound that polymerizes in the presence of the acid. That is, the ink-jet ink according to the present embodiment is a chemically amplified photosensitive composition. The “inkjet ink” used herein means a fluid ink at room temperature, specifically, an ink having a viscosity at 25 ° C. of 50 mPa · sec, more preferably 30 mPa · sec or less. Alternatively, the ink may be an ink having a viscosity of 12 mPa · sec at any temperature within a temperature range of about 50 ° C., which is a temperature adjustment range of the inkjet head.

  When such inkjet ink is irradiated with light, an acid is generated from the photoacid generator, and this acid functions as a catalyst for the crosslinking reaction of the polymerizable compound, and the generated acid diffuses in the ink layer. . In the ink layer after exposure, a crosslinking reaction using an acid as a catalyst proceeds, and this crosslinking reaction can be accelerated by heating the ink layer. The crosslinking reaction here is not inhibited by the presence of oxygen, unlike radical polymerization. Therefore, a plurality of cross-linking reactions can be caused by one photon, and high sensitivity can be realized. Moreover, the crosslinking reaction can be rapidly advanced even in the deep part of the ink layer or inside the absorbent medium. Therefore, the obtained ink layer is remarkably excellent in adhesion as compared with the radical polymerization system.

  Hereinafter, each component contained in the inkjet ink concerning embodiment of this invention is demonstrated in detail.

(Photoacid generator)
Examples of photoacid generators that generate acid upon irradiation with light include onium salts, diazonium salts, quinonediazide compounds, organic halides, aromatic sulfonate compounds, bisulfone compounds, sulfonyl compounds, sulfonate compounds, sulfonium compounds, sulfamide compounds, Iodonium compounds, sulfonyldiazomethane compounds, and mixtures thereof can be used.

  Specific examples of these compounds include, for example, triphenylsulfonium triflate, diphenyliodonium triflate, 2,3,4,4-tetrahydroxybenzophenone-4-naphthoquinone diazide sulfonate, 4-N-phenylamino- 2-methoxyphenyldiazonium sulfate, 4-N-phenylamino-2-methoxyphenyldiazonium p-ethylphenyl sulfate, 4-N-phenylamino-2-methoxyphenyldiazonium 2-naphthyl sulfate, 4-N-phenyl Amino-2-methoxyphenyldiazonium phenylsulfate, 2,5-diethoxy-4-N-4'-methoxyphenylcarbonylphenyldiazonium-3-carboxy-4-hydroxyphenylsulfate, 2-methoxy -4-N-phenylphenyldiazonium-3-carboxy-4-hydroxyphenyl sulfate, diphenylsulfonylmethane, diphenylsulfonyldiazomethane, diphenyldisulfone, α-methylbenzoin tosylate, pyrogallol trimesylate, benzoin tosylate, manufactured by Midori Chemical Co., Ltd. MPI-103 (CAS.NO. (87709-41-9)), Midori Kagaku BDS-105 (CAS.NO. (145612-66-4)), Midori Kagaku NDS-103 (CAS.NO. (110098-97-0)), MDS-203 (CAS.NO. (127855-15-5)) manufactured by Midori Chemical Co., Ltd., Pyrogallol tritosylate (CAS.NO. (20032-64-8)) manufactured by Midori Chemical Co., Ltd. Green chemistry DTS-102 (CAS.NO. (75482-18-7)), Midori Chemical DTS-103 (CAS.NO. (71449-78-0)), Midori Chemical MDS-103 (CAS.NO) (127279-74-7)), MDS-105 (CAS.NO. (116808-67-4)) manufactured by Midori Chemical Co., Ltd., MDS-205 (CAS.NO. (81416-37-7) manufactured by Midori Chemical Co., Ltd.) ), BMS-105 (CAS.NO. (149934-68-9)) manufactured by Midori Chemical Co., Ltd. TMS-105 (CAS.NO. (127820-38-6) manufactured by Midori Chemical Co., Ltd.), NB- manufactured by Midori Chemical Co., Ltd. 101 (CAS.NO. (20444-09-1)), Midori Kagaku NB-201 (CAS.NO. (4450-68-4)), Midori Kagaku DNB-10 (CAS. NO. (114719-51-6)), Midori Chemical Co., Ltd. DNB-102 (CAS.NO. (131509-55-2)), Midori Chemical Co., Ltd. DNB-103 (CAS.NO. (132898-35-2)) DNB-104 (CAS.NO. (132898-36-3)), Midori Chemical Co., Ltd., DNB-105 (CAS.NO. (132898-37-4)), Midori Chemical Co., Ltd., DAM-101 (CAS.NO. (1886-74-4)), Midori Kagaku DAM-102 (CAS.NO. (28343-24-0)), Midori Kagaku DAM-103 (CAS.NO. (14159-)) 45-6)), DAM-104 (CAS.NO. (130290-80-1), CAS.NO. (130290-82-3)), Midori Chemical DAM-201 (CAS.NO. (2832-50-1)), CMS-105, Midori Chemical Co., Ltd., DAM-301 (CAS. No. (138529-81-4)), Midori Chemical Co., Ltd. SI-105 (CAS. No. (34694-40-7)), Midori Chemical Co., Ltd. NDI-105 (CAS. No. (133710-62-0)), Midori Chemical Co., Ltd. EPI-105 (CAS. No. (135133-12-9)), and UVACURE1591 manufactured by Daicel UCB.

Moreover, the compound shown below can also be used as a photo-acid generator.

In the above general formula, C ₁ and C ₂ each represent a carbon atom forming a single bond or a double bond, R ₁₀ represents a hydrogen atom, a fluorine atom, a fluorine atom, an alkyl group, or an aryl group, and R ₁₁ and Each R ₁₂ represents a monovalent organic group. R ₁₁ and R ₁₂ may be bonded to each other to form a ring structure.

Furthermore, the following compounds can also be used as the photoacid generator.

(In the above general formula, Z represents an alkyl group.)

As the photoacid generator, it is desirable to use an onium salt. Usable onium salts include, for example, diazonium salts, phosphoniums having a counter ion of a fluoroborate anion, a hexafluoroantimonate anion, a hexafluoroarsenate anion, a trifluoromethanesulfonate anion, a paratoluenesulfonate anion, and a paranitrotoluenesulfonate anion. Mention may be made of salts and sulfonium salts. In particular, the photoacid generator preferably contains an onium salt or a halogenated triazine compound represented by the following general formulas (4) and (5). In this case, both sensitivity and stability are advantageous.

In the above general formula, R6 to R10 each represent an aromatic group and a functional group having a chalcogenide atom and an aromatic group, C1 to C2 each represent a chalcogenide atom, A4 and A5 each represent PF ₆ ⁻ , An anionic species selected from the group consisting of SbF ₆ ⁻ , BF ₄ ⁻ , AsF ₆ ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , and CH ₃ SO ₃ ^— , and m and n are integers Show. Here, the “chalcogenide atom” means a chalcogen atom and an atom that is more positive than the chalcogen atom. The “chalcogen atom” means a sulfur, selenium, tellurium, polonium, or iodine atom.

  The onium salt represented by the general formula (4) or (5) has high curing reactivity and is excellent in stability at room temperature. Therefore, it can suppress that said inkjet ink hardens | cures in the state which is not irradiating light.

When the compound represented by the general formula (4) or (5) is used as a photoacid generator, the chalcogenide atom is preferably a sulfur atom or an iodine atom from the viewpoint of thermal stability and water stability. In this case, the anion species is a non-organic acid, in particular PF ₆ ^- is desirably from the standpoint of acidity and thermal stability. From the viewpoint of thermal stability and photosensitive performance, a hexafluorophosphate compound having a phenylsulfonium skeleton is particularly desirable.

  The photoacid generator may further contain a sensitizing dye. Examples of the sensitizing dye include acridine compounds, benzoflavins, perylene, anthracene, and laser dyes.

  When a quinonediazide compound is used as the photoacid generator, salts such as naphthoquinonediazidesulfonyl chloride and naphthoquinonediazidesulfonic acid can be used.

Organic halide means a compound that forms hydrohalic acid, and examples thereof include compounds described in U.S. Pat. Nos. 3,515,552, 3,536,489, and 3,777,778, and West German Patent Publication No. 2243621. it can. More specifically, for example, carbon tetrabromide, tetra (bromomethyl) methane, tetrabromoethylene, 1,2,3,4-tetrabromobutane, trichloroethoxyethanol, p-iodophenol described in US Pat. No. 3,515,552, p-bromophenol, p-iodobiphenyl, 2,6-dibromophenol, 1-bromo-2-naphthol, p-bromoaniline, hexachloro-p-xylene, trichloroacetanilide, p-bromodimethylaniline, tetrachlorotetrahydronaphthalene, α, α′-dibromoxylene, α, α, α ′, α′-tetrabromoxylene, hexabromoethane, 1-chloroanthraquinone, ω, ω, ω-tribromoquinalidine, hexabromocyclohexane, 9-bromofluorene , Bis (penta (Lolo) cyclopentadiphenyl, polyvinylidene chloride, and 2,4,6-trichlorophenoxyethyl vinyl ether, hexabromoethane, α, α, α-trichloroacetophenone, tribromotrichloroethane, and halomethyl as described in US Pat. No. 3,777,778 -S-triazines can be mentioned. In particular, halomethyl-S-triazines such as 2,4-bis (trichloromethyl) -6-methyl-S-triazine and 2,4,6-tris (trichloromethyl) -S-triazine are preferably used. More preferred organic halides include compounds substituted with vinylhalomethyl-S-triazine disclosed in US Pat. No. 3,987,037. This vinyl halomethyl-S-triazine compound is a photodegradable S-triazine having at least one trihalomethyl group and a group conjugated with a triazine ring by at least one ethylenically unsaturated bond, It is represented by general formula (A).

In the general formula (A), Q is a bromine atom or a chlorine atom, P is -CQ _3, -NH _2, -NHR, a -NR ₂ or -OR radical,, R is phenyl or 6 carbon atoms Wherein n is an integer of 1 to 3, and W is an aromatic ring, a heterocyclic ring, or a group represented by the following general formula (B).

  In the general formula (B), Z represents an oxygen or sulfur atom, and R1 represents a lower alkyl group or a phenyl group.

In the general formula (A), at least one hydrogen atom in the aromatic ring or heterocyclic ring represented by W may be further substituted. In this case, examples of the substituent include a chlorine atom, a bromine atom, a phenyl group, a lower alkyl group having 6 or less carbon atoms, a nitro group, a phenoxy group, an alkoxy group, an acetoxy group, an acetyl group, an amino group, and an alkylamino group. Can be mentioned. Specific examples of the vinylhalomethyl-S-triazine compound represented by the general formula (A) include the compounds shown below.

  In addition to the compounds described above, a compound having a triazine ring in which trihalomethane is introduced into the skeleton can also be suitably used as a photoacid generator. When the triazine ring has 4 or more conjugated double bonds, the photosensitive wavelength becomes longer. Therefore, when a normal high pressure mercury lamp or the like is used as a light source, it is preferable to use such a compound. Examples of such a compound include a triazine having a naphthalene substituent and a condensed triazine compound.

  Furthermore, a photodissociable acid ester or the like can also be suitably used as a photoacid generator. For example, ortho nitrobenzyl ester of aluminum silanol can be mentioned.

  The content of the photoacid generator in the inkjet ink can be determined according to the acid generation efficiency of the photoacid generator used, the amount of the color component to be added, and the like. For example, when the concentration of the pigment is about 5% by weight, the photoacid generator is usually 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the compound polymerized in the presence of the acid contained in the ink-jet ink. Parts, preferably 2 to 8 parts by weight, more preferably 4 to 8 parts by weight. In particular, the more preferable range can improve the storage stability of the ink and reduce the corrosiveness of members such as pipes and heads. When the ratio of the photoacid generator to 100 parts by weight of the acid polymerizable compound is less than 1 part by weight, the sensitivity of the inkjet ink is lowered. On the other hand, if it exceeds 10 parts by weight, the viscosity of the ink with time increases and the coating properties and the hardness of the ink film after photocuring decrease. Further, there is a risk of corrosion of the piping of the recording apparatus and the head member.

(Color component)
The color component in the present invention may contain a pigment and / or a dye. However, in the inkjet ink according to the embodiment of the present invention, since an acid is used for the mechanism, it is desirable to use a pigment rather than a dye that easily fades due to the acid.
The pigment that can be used as the color component is not particularly limited as long as it has an optical coloring and coloring function required for the pigment, and any pigment can be used. The pigment used here may further exhibit other properties such as magnetism, fluorescence, conductivity, or dielectricity in addition to color development / coloring properties. In this case, various functions can be given to the image. Moreover, you may add the powder which can improve heat resistance and physical strength.

  Examples of usable pigments include light-absorbing pigments. Examples of such pigments include carbon-based pigments such as carbon black, carbon refined, and carbon nanotubes, and metal oxides such as iron black, cobalt blue, zinc oxide, titanium oxide, chromium oxide, and iron oxide. Pigments, sulfide pigments such as zinc sulfide, phthalocyanine pigments, pigments composed of salts such as metal sulfates, carbonates, silicates, and phosphates, as well as aluminum powder, bronze powder, and zinc powder Examples thereof include pigments made of such metal powder.

  Further, for example, dye chelates, nitro pigments, aniline black, nitroso pigments such as naphthol green B, azo pigments such as Bordeaux 10B, Lake Red 4R, and chromoftal red (azo lakes, insoluble azo pigments, condensed azo pigments, chelate azos) ), Rake pigments such as peacock blue lake and rhodamine lake, phthalocyanine pigments such as phthalocyanine blue, polycyclic pigments (perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, Organic pigments such as isoindolinone pigments, quinofuranone pigments), selenium pigments such as thioindigo red and indatron blue, quinacridone pigments, quinacridine pigments, and isoindolinone pigments. It is also possible to.

  Examples of pigments that can be used in black ink include Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, manufactured by Colombia, Regal 400R, Regal 330R, Regal 660R, Mogul L, manufactured by Cabot. Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, No. 1 manufactured by Mitsubishi Chemical Corporation. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, No2200B, Degussa Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S150, Color Black S150, Color Black FW200, Color Black FW200, Color Black FW200, Color Black FW200 Carbon blacks such as U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, and Special Black 4 may be mentioned.

  Examples of pigments that can be used in yellow ink include Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 2, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14C, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 73, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 75, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 98, C.I. I. Pigment Yellow 114, Pigment Yellow 180, and the like. Among these yellow pigments, Pigment Yellow 180, which causes little color deterioration with respect to acid, is preferably used.

  Examples of pigments that can be used in magenta ink include C.I. I. Pigment Red 123, C.I. I. Pigment Red 168, C.I. I. Pigment Red 184, C.I. I. Pigment Red 202, C.I. I. Pigment Red 5, C.I. I. Pigment Red 7, C.I. I. Pigment Red 12, C.I. I. Pigment Red 48 (Ca), C.I. I. Pigment Red 48 (Mn), C.I. I. Pigment Red 57 (Ca), C.I. I. Pigment Red 57: 1, C.I. I. Pigment Violet 19 and C.I. I. Pigment Red 112 and the like.

  Further, examples of pigments that can be used in cyan ink include C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15:34, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 1, C.I. I. Pigment Blue 2, C.I. I. Pigment Blue 3, C.I. I. Vat Blue 4, and C.I. I. Vat Blue 60 etc. are mentioned.

  White pigments such as natural clay, lead white, zinc oxide and metal carbonates such as magnesium carbonate, and metal oxides such as barium and titanium are also useful as color components. Ink-jet inks containing a white pigment can be used not only for white printing but also for printing correction and overlaid correction by overwriting.

As the pigment exhibiting fluorescence, either an inorganic phosphor or an organic phosphor may be used. Examples of the inorganic phosphor material include MgWO ₄ , CaWO ₄ , (Ca, Zn) (PO ₄ ) ₂ : Ti ⁺ , Ba ₂ P ₂ O ₇ : Ti, BaSi ₂ O ₅ : Pb ²⁺ , Sr _2. Examples include inorganic acid salts such as P ₂ O ₇ : Sn ²⁺ , SrFB ₂ O _3.5 : Eu ²⁺ , MgAl ₁₆ O ₂₇ : Eu ²⁺ , tungstate and sulfurate. Examples of organic phosphor materials include acridine orange, aminoacridine, quinacrine, anilinonaphthalenesulfonic acid derivatives, anthroyloxystearic acid, auramine O, chlorotetracycline, merocyanine, 1,1′-dihexyl-2, Cyanine dyes such as 2'-oxacarbocyanine, dansylsulfoamide, dansylcholine, dansylgalacside, dansyltrizine, dansyl chloride derivatives such as dansyl chloride, diphenylhexatriene, eosin, ε-adenosine, ethidium bromide, fluorescein Fomycin, 4-benzoylamide-4′-aminostilbene-2,2′-sulfonic acid, β-naphthyl triphosphate, oxonol dye, parinaric acid derivative, perylene, N-phenylnaphthy Amine, pyrene, safranine O, fluorescamine, fluorescein isocyanate, 7-chloronitrobenzo-2-oxa-1,3-diasol, dansylaziridine, 5- (iodoacetamidoethyl) aminonaphthalene-1-sulfonic acid, 5- Iodoacetamidofluorescein, N- (1-anilinonaphthyl4) maleimide, N- (7-dimethyl-4-methylcoumanyl) maleimide, N- (3-pyrene) maleimide, eosin-5-iodoacetamide, fluorescein mercury acetate, 2 -(4 '-(2''-iodoacetamido)) aminonaphthalene-6-sulfonic acid, eosin, rhodamine derivative, organic EL dye, organic EL polymer, crystal, dendrimer and the like can be mentioned.

  Examples of the powder that can improve the heat resistance and physical strength of the ink layer include aluminum, silicon oxide or nitride, filler, silicon carbide, and the like. In order to impart conductivity to the ink layer, powders such as conductive carbon pigment, carbon fiber, copper, silver, antimony, and noble metals may be added. Iron oxide and ferromagnetic powder are suitable for imparting magnetism, and metal oxide powder such as tantalum and titanium having a high dielectric constant can also be blended.

  Moreover, it is possible to add a dye as an auxiliary component of the pigment in the inkjet ink according to the present embodiment. For example, dyes with low acidity and basicity and high solubility in solvents, such as azoic dyes, sulfur (building materials) dyes, disperse dyes, fluorescent brighteners, and oil-soluble dyes, are usually used. Oil-soluble dyes such as azo, triarylmethane, anthraquinone and azine are preferably used. For example, C.I. I. Slovent Yellow-2, 6, 14, 15, 16, 19, 21, 33, 56, 61, 80, etc., Diresin Yellow-A, F, GRN, GG, etc., C.I. I. Solvent Violet-8, 13, 14, 21, 27, etc., C.I. I. Disperse Violet-1, Sumiplast Violet RR, C.I. I. Solvent Blue-2, 11, 12, 25, 35, etc., Diresin Blue-J, A, K, N etc., Orient Oil Blue-IIN, # 603 etc., Sumiplast Blue BG, etc. can be mentioned.

  The pigments and dyes described above may be used alone or as a mixture of two or more. In addition, pigments and dyes can be used in combination in order to enhance light absorbency, saturation, color feeling, and the like. Furthermore, in order to improve the dispersibility of the pigment, bonding with a polymer binder or microencapsulation treatment may be performed.

  The content of the color component is desirably blended in an amount of 1 to 25 parts by weight. When the amount is less than 1 part by weight, it is difficult to ensure a sufficient color density. On the other hand, when the amount exceeds 25 parts by weight, the ink discharge performance is lowered. More preferably, the content of the color component is in the range of 2 to 8 parts by weight.

  Further, the content of the powder component is preferably 1 to 50% by weight. When the content of the powder component is less than 1% by weight, effects such as an increase in sensitivity are insufficient, and when it exceeds 50% by weight, resolution and sensitivity may be lowered.

  In an inkjet ink, it is desirable that the average particle size of color components and powders be as small as possible. In general, the particle size of the color component and the powder is usually 1/3 or less, more preferably about 1/10 or less of the opening diameter of the nozzle that discharges the inkjet ink. This size is typically 10 μm or less, preferably 1 μm or less. In consideration of sedimentation due to poor dispersion, the particle size suitable as a printing inkjet ink is 0.35 μm or less, and usually has an average particle size of 0.1 to 0.3 μm.

(Compound that polymerizes in the presence of acid)
A compound that polymerizes in the presence of an acid is used as a solvent in the inkjet ink according to an embodiment of the present invention. The solvent consists essentially of a polymerizable compound having such characteristics. “The solvent is substantially composed of a polymerizable compound” includes that “the solvent is composed only of the polymerizable compound” and “consisting of a trace amount of impurities inevitably mixed with the polymerizable compound”. . “A trace amount of impurities inevitably mixed in” can be present in all solvents at a concentration of up to 10% by weight. Preferably, the content of “a trace amount of impurities inevitably mixed” is usually 5% by weight or less. If it exceeds this, the remaining solvent is substantially scattered in the air, which may reduce the safety problem or remain in the cured product, thereby reducing the curing performance. The details will be described below by classifying each component.

Vinyl ether compound (essential component)
The inkjet ink according to the embodiment of the present invention includes at least a vinyl ether compound. Furthermore, at least 40 parts by weight of the acid polymerizable compound is occupied by the vinyl ether compound. In the case where the solvent is composed of only the vinyl ether compound, the content thereof is preferably 30% by weight or more, more preferably 40% by weight or more based on the entire inkjet ink. If it is less than 30% by weight, there is a possibility that nozzle clogging may occur or the photosensitivity may decrease.

The vinyl ether compound preferably has a cyclic skeleton from the viewpoints of polymerizability and curing hardness, and specifically includes compounds represented by the following general formula (1).

In the general formula (1), R ¹³ is selected from a vinyl ether group, a group having a vinyl ether skeleton, an alkoxy group, a hydroxyl group-substituted product, and a hydroxyl group, and at least one is a vinyl ether group or a group having a vinyl ether skeleton. R ¹⁴ is a (p + 1) -valent group having a substituted or unsubstituted cyclic skeleton, and p is a positive integer including 0. However, when R ¹⁴ is a cyclohexane ring skeleton and p is 0, an oxygen-containing structure is more preferable from the viewpoint of volatility. Specifically, at least one carbon atom on the ring includes a structure having a ketone structure, a structure substituted with an oxygen atom, or a structure having an oxygen-containing substituent.

  The number of vinyl ether groups introduced into the above-described molecular skeleton is preferably larger from the viewpoint of curability, and is not particularly limited. However, in order to impart re-solubility to the ink layer after curing, at most about 2 to 3 It is desirable that the valence of

Examples of the (p + 1) -valent organic group R ¹⁴ include (p + 1) -valent groups including a substituted or unsubstituted aromatic ring, for example, a benzene ring, a naphthalene ring, and a biphenyl ring. Alternatively, an alicyclic skeleton such as a cycloalkane skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodencan skeleton, a tetracyclododecane skeleton, a terpenoid skeleton, a cholesterol skeleton, or a derived (p + 1) -valent group may be used. . When such an alicyclic skeleton has a crosslinked structure, the hardness of the cured product is increased, which is more desirable. Furthermore, an oxygen-containing structure is more desirable from the viewpoint of volatility. Specifically, a cyclic carbon structure having a ketone structure, a structure in which an oxygen atom is substituted, a structure having an oxygen-containing substituent, or the like.

  The compound represented by the general formula (1) usually has a viscosity of about 1 mPa · sec to 30 mPa · sec. Therefore, the use of these compounds is effective for making the inkjet ink sufficiently low in viscosity. If the content of the low-viscosity vinyl ether compound is 40 parts by weight or more in the total amount of the solvent, the effect can be exhibited.

  Among the compounds represented by the general formula (1), when at least one vinyl ether group is directly bonded to the ring, the cationic curability is excellent, and when the pigment is simultaneously provided, the curability is also excellent. Would be desirable.

  When the cyclic compound includes an aromatic skeleton, it is desirable because it can impart hardness to the cured product and improve the solubility of the photosensitizer and the like. Specific examples of such vinyl ether compounds include compounds in which the hydroxyl group of the following alcohol compound is substituted with vinyl ether or propenyl ether. For example, cumene alcohol represented by the following chemical formula Aro1, vinyloxybenzene represented by the following chemical formula Aro2, hydroquinone represented by the following chemical formula Aro3, 1-carbomethoxy-4-vinyloxybenzene represented by the following chemical formula Aro4, and the following chemical formula Aro5 2-hydroxynaphthalene represented, 1-tertbutyl-4-vinyloxybenzene represented by the following chemical formula Aro6, bisphenol A represented by the following chemical formula Aro7, 1-octyl-4-vinyloxybenzene represented by the following chemical formula Aro8, 1-hydroxy-3,5-dimethylbenzene represented by the chemical formula Aro9, 4-hydroxycumylphenol represented by the following chemical formula Aro10, and 3-isopropylphenol represented by the following chemical formula Aro11 Alcohols such as Le is illustrated in this.

The example of a specific vinyl ether compound is shown in the following chemical formula.

  Further, when the cyclic compound is an alicyclic skeleton, it is preferable to the aromatic vinyl ether from the viewpoint of odor and safety. As the vinyl ether compound having such an alicyclic skeleton, a monocyclic ring having a 4- to 6-membered ring or a alicyclic skeleton having a bridge structure formed by bonding them is desirable. For example, the compound etc. which substituted the hydroxyl group of the following alicyclic alcohol compound with vinyl ether or propenyl ether are mentioned. Cyclopentanemono (di) ol, cyclopentanemono (di) methanol, cyclohexane (di) ol, cyclohexanemono (di) methanol, norbornanemono (di) ol, norbornanemonoolmonomethanol, norbornanemono (di) methanol, tri Such as cyclodecane mono (di) ol, tricyclodecane mono (di) methanol, and adamantane mono (di) ol.

More specifically, the alicyclic skeleton has a structure represented by the following general formula (VE1-a) or (VE1-b).

(In the above general formula, X1 and Z1 are alkylene groups having 1 to 5 atoms, Y1 is an alkylene group having 1 to 2 atoms, and k is 0 or 1.)
Specific examples of the compounds described above include compounds in which the hydroxyl group of the following alcohol compound is substituted with vinyl ether or propenyl ether. For example, 4-cyclohexanediol represented by the following chemical formula Ali1, dicyclopentadienemethanol represented by the following chemical formula Ali2, isoborneol represented by the following chemical formula Ali3, 1-tertbutyl-4-vinyloxycyclohexanol represented by the following chemical formula Ali4 , Trimethylcyclohexanol represented by the following chemical formula Ali5, dihydroxyoctahydrophenyl represented by the following chemical formula Ali6, hydroxytricyclodecane monoene represented by the following chemical formula Ali7, menthol represented by the following chemical formula Ali8, 1, 3 dihydroxycyclohexane, decahydro-2-naphthalenol represented by the following chemical formula Ali10, vinyloxysiloxane represented by the following chemical formula Ali11 Dodecanol, and alcohols such as norbornane diol represented by the following chemical formula Ali12.

Examples of more specific vinyl ether compounds are shown below.

  Among the above compounds, those having an alicyclic skeleton having a crosslinked structure are more desirable because the hardness of the cured product is increased. Further, RAPI-CURE CHVE: cyclohexane dimethanol divinyl ether and RAPI-CURE CHMVE: cyclohexane dimethanol monovinyl ether manufactured by ASP Japan Co., Ltd. are generally known, but such compounds do not have vinyl ether bonded directly to the cyclic skeleton. Therefore, the performance tends to be inferior from the viewpoint of acid polymerization.

  Among the compounds having the alicyclic skeleton, a part of the carbon of the ring is substituted with an oxygen atom, or has an oxygen-containing structure such as an oxygen-containing substituent. Desirable from the viewpoint of dispersibility.

  Examples of the vinyl ether compound having a ring structure having an oxygen-containing substituent include, for example, an alcohol having an alicyclic skeleton in which the cyclic skeleton is a monocyclic ring constituted by 4-6 membered rings or a bridge structure formed by combining them. In the compound, for example, a compound in which at least one hydroxyl group is substituted with ether or ester such as methoxy group, methoxyethoxy group, alkoxy group, acetoxy group or alkyl ester group, and the rest is substituted with vinyl ether or propenyl ether, etc. Can be mentioned. For example, the alcohol compounds include cyclopentanediol, cyclohexanedi (tri) ol, cyclohexanedi (tri) methanol, norbornanedi (tri) ol, norbornanemono (di) olmono (di) methanol, norbornanedi (tri) methanol. , Tricyclodecanedi (tri) ol, tricyclodecanedi (tri) methanol, adamantanedi (tri) ol and the like.

More specifically, a vinyl ether compound having an oxygen-containing substituent represented by the following chemical formula is most desirable.

On the other hand, when an oxygen atom is contained in the alicyclic skeleton, the viscosity stability is further improved, which is more desirable. Examples of such a compound include compounds represented by the following general formula (VE2-a) or (VE2-a).

(In the above general formula, any one of X 2, Y 2 and Z 2 contains at least one oxygen atom, and X 2 and Z 2 are an alkylene group having 1 to 5 atoms or a divalent organic group containing an oxygen atom as an ether bond. Y2 represents an oxygen atom, an alkylene group having 1 to 2 atoms or a divalent organic group containing an oxygen atom as an ether bond, and k is 0 or 1.)
Such a compound has high solubility and dispersibility because the safety of the alicyclic skeleton and excellent curing performance, and the cyclic hydrocarbon skeleton having an oxygen atom as a ring constituent atom exhibits a high surface tension. In order to reduce the phenomenon of ink repelling by a relatively hydrophilic printing medium, a vinyl ether compound sharing these properties is most preferably used.

  As the vinyl ether compound having an alicyclic skeleton having such a structure, a compound having a cyclic ether skeleton in which the cyclic skeleton is a 4-6 membered ring is desirable. For example, the compound etc. which substituted the hydroxyl group of the following alcohol compound with vinyl ether or propenyl ether are mentioned. Specifically, substituted or unsubstituted oxetane monool, substituted or unsubstituted oxetane monomethanol, oxapentane mono (di) ol, oxacyclohexane mono (di) ol, isosorbitol, mannitol, oxanorbornane mono (di) ) Ol, oxanorbornane monool monomethanol, oxanorbornane mono (di) methanol, oxatricyclodecane mono (di) ol, oxaadamantane mono (di) ol, and dioxolanmentanol.

  Among such compounds, in the structure of the cyclic skeleton portion represented by the general formula (VE2-a) or (VE2-b), the ratio of the number of oxygen atoms to the number of carbon atoms (number of oxygen atoms / number of carbon atoms) is: It is preferable to exceed 0.08. When such a vinyl ether compound is used, an ink exhibiting characteristics with physical properties related to polarity such as solubility and wettability with a printing medium can be obtained. (Number of oxygen atoms / number of carbon atoms) is preferably 0.15 or more, and more preferably 0.25 or more.

Specific examples of vinyl ether compounds include CasNo. 22214-12-6, CasNo. 20191-85-9. Like these compounds, compounds having a distorted cyclic ether structure such as an oxetane ring or a hydrofuran ring are desirable because the reactivity is also improved. Of these, the hydrofuran ring is desirable from the viewpoint of volatility. Further, since the curing hardness is increased, such a cyclic structure is most desirable when it has a bridge structure. More specifically, vinyl ethers shown below are most desirable.

  The series of vinyl ether compounds described above are described, for example, in J. Org. Chem. Soc. 1965 (2) 1560-1561 and J.A. Am. Chem. Soc. Vol. 124, no. 8, 1590-1591 (2002) and the like. When such a method is used, the corresponding aromatic alcohol or alicyclic alcohol compound is used as a starting material, and an acetate of vinyl ether or propenyl ether is allowed to act under a catalyst such as iridium halide. As a result, the intended vinyl ether or propenyl ether compound can be easily obtained. For example, menthol vinyl ether (MTVE) can be obtained by heating and stirring menthol and vinyl acetate in a toluene mixed solution of sodium carbonate using an iridium compound as a catalyst under an argon atmosphere.

  This synthesis method is suitable for any compound exemplified in the present application.

(Other acid-polymerizable compounds that can be added)
When the vinyl ether compound is used alone, the curing property is most desirable, but a compound that polymerizes with another acid can be added within a range in which the curing property is not significantly lowered. By such blending, storage stability can be enhanced, solubility of the photosensitizer can be increased, and properties such as flexibility and gloss suitable for printed matter can be imparted.

The polymerizable compound that is polymerized in the presence of an acid that can be added can be used without particular limitation as long as it is generally known as an acid polymerizable compound. For example, a compound having a cyclic ether group such as an epoxy group, an oxetane group, and an oxolane group, an acrylic or vinyl compound having the above-described substituent in the side chain, a carbonate compound, a low molecular weight melamine compound, vinyl carbazoles, Examples thereof include monomers having a vinyl bond capable of cationic polymerization such as styrene derivatives, alpha-methylstyrene derivatives, vinyl alcohol esters including vinyl alcohol and ester compounds such as acrylic and methacryl. These can be used alone or in combination of two or more. However, in all of these compounds, good characteristics are not obtained, and by using a specific combination for a specific application, other characteristics can be improved without impairing the curing characteristics. The details are explained below (epoxy compound)
In addition to the vinyl ether compound represented by the general formula (1), the following compounds can be used. For example, a hydrocarbon group having a divalent aliphatic skeleton or alicyclic skeleton having about 1 to 15 carbon atoms, or one or both of a divalent group partially having an aliphatic chain or alicyclic skeleton. And compounds represented by the following general formula (11) or (12) having an epoxy group or an alicyclic epoxy group. Such compounds also have acid polymerizability.

  In the general formulas (11) and (12), R1 to R3 each represents an epoxy group or an epoxy group having an alicyclic skeleton, and A1 and A2 are divalent aliphatic skeleton or alicyclic having about 1 to 15 carbon atoms. It represents a hydrocarbon group having the formula skeleton, or an aliphatic chain or alicyclic skeleton. Further, some of the carbon atoms of the aliphatic chain and alicyclic ring in such a compound may be substituted with an oxygen atom or have a ketone skeleton.

  The compound represented by the general formula (11) or (12) usually has a viscosity of about 5 mPa · sec to 100 mPa · sec, and is less likely to be damaged by blending. In particular, an alicyclic epoxy compound is desirable when it is desired to improve acid polymerizability or impart solubility of a photosensitizer, but the curing rate tends to decrease, while storage stability and solvent resistance are impaired. Accordingly, the preferred amount of addition of these compounds is in the range of 0% up to 60% of the total acid curable compound.

Moreover, when it is requested | required that flexibility, glossiness, etc. should be provided to the ink after hardening, the epoxy compound represented by following General formula (13) can also be used. The alicyclic epoxy compound represented by the following general formula (13) usually has a high viscosity of 50 mPa · sec to 10,000 mPa · sec or more.

  In the general formula (13), R4 and R5 each represents an epoxy group or an epoxy group having an alicyclic skeleton, and A3 represents a k + 1-valent functional group having at least an alkylene group and / or an alicyclic skeleton (k is a natural number) ).

  For example, when the vinyl ether compound is contained in an amount of 50 parts by weight to 90 parts by weight with respect to 100 parts by weight of the inkjet ink, the above-described high viscosity epoxy compound is added in a ratio of 10 parts by weight to 40 parts by weight. It is hoped that This makes it possible to ensure the minimum fluidity necessary for ejection (viscosity of 50 mPa · sec or less at 50 ° C.). In particular, the weight ratio between the vinyl ether compound and the high viscosity compound is preferably about 1: 1 to 10: 1. When the vinyl ether compound and the high-viscosity epoxy compound are combined in this way, the compound represented by the general formula (4) or (5) is used as the photoacid generator, and the amount of the pigment is 1 part by weight. It is desirable that the amount be 25 parts by weight or less. In particular, when a high viscosity, high molecular weight epoxy compound of 500 mPa · sec or more is added, flexibility and glossiness are excellent. This makes it possible to adjust the ink-jet ink that is suitable for ejection and can obtain the flexibility and glossiness of the cured product.

In addition, when an epoxy compound represented by the following general formula (16) is used in combination with a vinyl ether compound, the storability of the inkjet ink and the flexibility of the ink layer can be improved.

In the general formula (16), R ¹¹ is a glycidyl ether group, R ¹² is an alkylene group having 1 to 6 carbon atoms or a hydroxyl group-substituted alkylene group, or an alicyclic skeleton having 6 to 15 carbon atoms or a hydroxyl group-substituted alicyclic group. An alkylene group having a skeleton, and j is 1 to 3. Among these, from the viewpoints of appropriate viscosity, acid polymerizability, and storage stability, the more specific the diglycidyl ether compound of neopentyl glycol is, the better performance is obtained. However, excessive addition of these compounds causes a decrease in curing performance. For example, when the vinyl ether compound is contained in a proportion of 50 parts by weight to 90 parts by weight with respect to 100 parts by weight of the inkjet ink, It is desirable that the above-mentioned epoxy compound is added in a proportion of 10 to 40 parts by weight.

  Specific examples of the epoxy compound include alicyclic epoxy and epoxy group-containing (meth) acrylates exemplified by Daicel Chemical's Celoxide 2021, Celoxide 2021A, Celoxide 2021P, Celoxide 2081, Celoxide 2000, and Celoxide 3000. Cyclomer A200, which is a compound, Cyclomer M100, methacrylate having a methyl glycidyl group such as MGMA, glycidol, which is a low molecular epoxy compound, β-methylepicholorhydrin, α-pinene oxide, C12 to C14 α-olefin Monoepoxide, C16-C18 α-olefin monoepoxide, epoxidized soybean oil such as Daimac S-300K, epoxidized linseed oil such as Daimac L-500, Epolide G 301, and the like polyfunctional epoxy such as Epolead GT401 can be mentioned.

  Furthermore, alicyclic epoxy of US Dow Chemical, such as Cyracure, a compound in which the hydroxyl end of a hydrogenated and aliphatic low molecular phenol compound is replaced with a group having an epoxy, ethylene glycol, glycerin, neopentyl alcohol Glycidyl ether compounds such as polyhydric aliphatic alcohols / alicyclic alcohols such as hexanediol and trimethylolpropane, compounds having a glycidyl ether group at the end of an ethylene oxide polymer, and terpene compounds having an unsaturated bond A compound obtained by oxidizing and epoxidizing the unsaturated bond, hexahydrophthalic acid, a glycidyl ester of a hydrogenated aromatic polyvalent carboxylic acid, or the like can be used.

(Oxetane compound)
Moreover, an oxetane compound can be used suitably as a part of acid-polymerizable compound. For example, when high-speed printing of several tens of meters per minute is required, or when resistance to a solvent is required, it is preferable to add an oxetane compound. When an oxetane compound is used as a main solvent of a conventional inkjet ink, the viscosity usually increases remarkably and it is difficult to adjust the viscosity with other solvents. However, when used in combination with a vinyl ether compound, since this vinyl ether compound has a very low viscosity, it can be easily converted into an ink.

  The oxetane compound is preferably an aromatic, aliphatic, or alicyclic oxetane compound, and may have an ether bond partially in the structure. Desirable mixing ratio of such compounds is 0 to 40 parts by weight of the aromatic oxetane compound in view of solvent resistance, and 60 parts by weight or more of the vinyl ether compound in view of viscosity suitability. Further, from the viewpoint of curing acceleration, the total amount of the oxetane compound added to the ink is preferably at least 40 parts by weight, and from the viewpoint of curing hardness, the total amount of the compound having an alicyclic skeleton and an aromatic skeleton is sufficient. It is desirable that it is at least 30 parts by weight or more.

  When deviating from these ranges, it may be difficult to sufficiently satisfy all of the characteristics such as curing speed, ejection performance, and solvent resistance.

  Examples of the aliphatic or alicyclic oxetane compound include (di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, [(1-ethyl- One or more oxetane-containing groups are present in the alicyclic ring such as 3-oxetanyl) methoxy] cyclohexane, bis [(1-ethyl-3-oxetanyl) methoxy] cyclohexane, and bis [(1-ethyl-3-oxetanyl) methoxy] norbornane. In addition, an oxetane-containing alcohol such as 3-ethyl-3-hydroxymethyloxetane was dehydrated and condensed with an aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol, or neopentyl alcohol. Ether compounds and the like can also be used.

  Examples of the oxetane compound containing an aromatic skeleton include 1,4-bis ((1-ethyl-3oxetanyl) methoxy) benzene, 1,3-bis ((1-ethyl-3oxetanyl) methoxy) benzene, 4 , 4′-bis ((3-ethyl-3oxetanyl) methoxy) biphenyl, and phenol novolac oxetanes.

  However, excessive addition may increase viscosity and make ejection impossible. For example, when the vinyl ether compound is contained at a ratio of 50 parts by weight to 90 parts by weight with respect to 100 parts by weight of the ink-jet ink. The above-mentioned oxetane compound is preferably added in a proportion of 10 to 60 parts by weight. In particular, when a high viscosity, high molecular weight oxetane compound of 500 mPa · sec or more is added, the resulting printed matter is excellent in flexibility and gloss.

(Cyclic ester, cyclic carbonate acid-polymerizable compound)
Many of the photoacid generators contained as an essential component in the inkjet ink according to the embodiment of the present invention have low solubility in acid polymerizable compounds such as vinyl ether compounds. When the solubility of the photoacid generator in the ink-jet ink is low, the sensitivity at the time of light irradiation is insufficient, and the hardness of the ink cured film may be reduced. Alternatively, the photoacid generator that could not be dissolved may be present as impurities such as coarse particles, which may adversely affect ejection stability.

In such a case, it is effective to contain a cyclic carbonate or cyclic lactone compound that dissolves the photoacid generator very well. For example, propylene carbonate, which is a cyclic carbonate, has a solubility parameter around 27 MPa ^1/2 and tends to be more polar than an acid polymerizable compound. Therefore, even when a photoacid generator that is difficult to dissolve in the acid polymerizable compound is used, the solubility of the photoacid generator can be increased by adding a small amount of propylene carbonate.

  Propylene carbonate has polymerizability. Therefore, even when used for inkjet ink, it is very rarely discharged into the atmosphere as a volatile component after the ink film is cured, and is preferable for use in general for inkjet ink according to embodiments of the present invention. Other cyclic carbonates and cyclic lactone compounds include propylene carbonate propenyl ether, dimethyl carbonate, diphenyl carbonate, and the like. However, excessive mixing of these compounds causes a decrease in curing performance. For example, when the vinyl ether compound is contained in a proportion of 50 to 90 parts by weight with respect to 100 parts by weight of the ink-jet ink, The cyclic compound is desirably added in a proportion of 5 to 40 parts by weight.

(Other acid-polymerizable compounds that can be added)
Furthermore, the following compounds can also be added.

  Examples of the high molecular weight compound include a compound having a molecular weight of 5000 or less having a cyclic ether group such as an epoxy group, an oxetane group or an oxolane group bonded by a long chain alkylene group or the like, and having the above-described substituent in the side chain. Acrylic or vinyl compounds, carbonate compounds, low molecular weight melanin compounds, vinyl ethers and vinyl carbazoles, styrene derivatives, alpha-methyl styrene derivatives, vinyl alcohol esters including vinyl alcohol and acrylic, methacrylic ester compounds, etc. , A monomer having a cationically polymerizable vinyl bond and an oligomer obtained by polymerizing at least one of the monomers.

  In addition to the compounds described above, the solvent may further contain the following compounds. For example, vinyl alcohol homopolymers or copolymers, casein, cellulose-like resins having an acid-reactive / dehydrating-condensable OH group, COOH group, acetal group, etc., and polycarbonate resins having a molecular weight of 5000 or less, A copolymer of polyamic acid, polyamino acid or acrylic acid and a vinyl compound having an acid polymerizable double bond in the side chain, a copolymer of vinyl alcohol and a vinyl compound having an acid polymerizable double bond in the side chain, And methylolated melamine compounds.

(Other compounds that can be added)
The photosensitive composition of the present invention may further contain a basic additive, a dispersant, a surfactant, a radical polymerizable monomer, a radical generator, a special solvent that is not acid polymerizable, and the like. The components are classified and described in detail below.

(Basic compound)
Ink-jet inks are desired to have high ink-jet ejection stability, but generally there is a tendency for viscosity increase over time to be high, and as such, performance can be maintained only for a short period. Therefore, it is desirable to further contain at least one of a basic compound and a compound expressing basicity as a viscosity stabilizer. When carbon black is used as the color component, the effect of such a viscosity stabilizer is more remarkable. Further, such a basic compound simultaneously has an effect of significantly reducing corrosion from the acid inside the ink jet head of the recording apparatus and the metal portion of the ink pipe, and therefore is used for all ink jet inks according to the embodiments of the present invention. Is preferable.

  As the basic compound, any inorganic base and organic base that can be dissolved in a compound that is polymerized with an acid as described above can be used, and an organic base is more preferable because of its solubility. Examples of the organic base include ammonia and ammonium compounds, substituted or unsubstituted alkylamines, substituted or unsubstituted aromatic amines, and organic amines having a heterocyclic skeleton such as pyridine, pyrimidine, and imidazole. More specifically, n-hexylamine, dodecylamine, aniline, dimethylaniline, diphenylamine, triphenylamine, diazabicyclooctane, diazabicycloundecane, 3-phenylpyridine, 4-phenylpyridine, lutidine, 2,6 -Di-t-butylpyridine, 4-methylbenzenesulfonyl hydrazide, 4,4'-oxybis (benzenesulfonyl hydrazide), and sulfonyl hydrazides such as 1,3-benzenedisulfonyl hydrazide.

As the basic compound, an ammonium compound can also be used. A preferred ammonium compound is a quaternary ammonium salt represented by the following general formula (23).

(In the general formula (23), R _a , R _b , R _c , and R _d each represents an alkyl, cycloalkyl, alkylaryl, or aryl group, in which one or more aliphatic CH ₂ groups are represented. (The group may be replaced by an oxygen atom. X3 is a basic anion.)
Examples of the compound represented by the general formula (23), to no R _a R _d are each methyl, ethyl, propyl, isopropyl, butyl, dodecyl, phenyl, benzyl, X3- is hydroxyl ion, ^- OR It is C1 -C4 alkyl ^base, - OCOR '(R' is alkyl, aryl, ^alkylaryl), OCOO ^-, OSOO - anion represented by is preferably used. Particularly preferred are tetramethylammonium hydroxide and tetrabutylammonium hydroxide. These basic compounds can be used alone or in combination of two or more.

  The basicity of the basic compound used as the viscosity stabilizer of the present invention is such that when the vinyl ether compound is used alone or in combination with the oxetane compound, the basic dissociation constant pKb at a temperature of 25 ° C. in an aqueous solution is 3 or more. On the contrary, a compound having a pKb of more than 7 is not very effective. As the compound satisfying such conditions, for example, aliphatic amines and substituted aliphatic amines are suitable.

  However, when the vinyl ether compound of the present invention further contains an epoxy compound at the same time, when an excessively strong basic compound such as imidazole is used, for example, polymerization occurs over time, or photoacid generator There is a risk of causing side reactions such as decomposition. On the other hand, it is difficult for a compound having a very low basicity to obtain a sufficient viscosity stabilizing effect by addition. For example, a basic compound having a base dissociation constant pKb of 4 or more at a temperature of 25 ° C. in an aqueous solution is desirable, and conversely, a compound having a pKb of more than 11 shows little effect. As the compound satisfying such conditions, for example, pyridine derivatives, aniline derivatives, aminonaphthalene derivatives, other nitrogen-containing heterocyclic compounds and derivatives thereof are suitable.

  Examples of the pyridine derivative include 2-fluoropyridine, 3-fluoropyridine, 2-chloropyridine, 3-chloropyridine, 3-phenylpyridine, 2-benzylpyridine, 2-formylpyridine, and 2- (2′-pyridyl). Examples thereof include pyridine, 3-acetylpyridine, 2-bromopyridine, 3-bromopyridine, 2-iodopyridine, 3-iodopyridine, and 2,6-di-tert-butylpyridine.

  Examples of aniline derivatives include aniline, 4- (p-aminobenzoyl) aniline, 4-benzylaniline, 4-chloro-N, N-dimethylaniline, 3-5-dibromoaniline, 2,4-dichloroaniline, N , N-dimethylaniline, N, N-dimethyl-3-nitroaniline, N-ethylaniline, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-iodoaniline, N-methylaniline, 4-methylthio Aniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 4-bromo-N, N-dimethylaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 3-chloro-N, N -Dimethylaniline, 3-nitroaniline, 4-nitroaniline, 2-methoxyaniline, 3 Methoxyaniline, diphenylamine, 2-biphenylamine, o-toluidine, m-toluidine, p-toluidine, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, and 4,4'-bis (4- And aminophenoxy) diphenylsulfone.

  Examples of aminonaphthalene derivatives include 1-amino-6-hydroxynaphthalene, 1-naphthylamine, 2-naphthylamine, diethylaminonaphthalene, and N-methyl-1-naphthylamine.

  Examples of other nitrogen heterocyclic compounds and derivatives thereof include, for example, sinoline, 3-acetylpiperidine, pyrazine, 2-methylpyrazine, methylaminopyrazine, pyridazine, 2-aminopyrimidine, 2-amino-4,6-dimethylpyrimidine, 2-amino-5-nitropyrimidine, 2,4,6-triamino-1,3,5-triazine, pyrrole, pyrazole, 1-methylpyrazole, 1,2,4-triazole, indazole, benzotriazole, quinazoline, quinoline 3-aminoquinoline, 3-bromoquinoline, 8-carboxyquinoline, 3-hydroxyquinoline, 6-methoxyquinoline, 5-methylquinoline, quinoxaline, thiazole, 2-aminothiazole, 3,4-diazaindole, purine, 8-azapurine, indole And it can be exemplified India such as lysine.

Examples of the aliphatic amine and its derivative include amine derivatives represented by the following general formula (21).

In the general formula (21), R ²¹ , R ²² and R ²³ may be the same or different, at least one is a substituted or unsubstituted alkyl group, and the rest are a hydrogen atom, a hydroxyl group, A substituted or unsubstituted alkyl group. Such an amine compound represented by the general formula (21) is preferably used in combination with an oxetane or a vinyl ether compound.

Moreover, when the basic compound mentioned above forms a salt with the anion represented by the following general formula (22) and the acidity of the anion is low, the compound itself acts as a weak base. Therefore, it can be used in the same manner as described above.

In the general formula (22), A ⁻ is a compound having a sulfonate anion or a carboxyl anion, R ²¹ to R ²⁴ may be the same or different, a substituted or unsubstituted aromatic group, a hydrogen atom , Hydroxyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted alkyl group.

  Since the inkjet ink according to the embodiment of the present invention may be heated after exposure, it is desirable that the volatility of the basic compound is as low as possible. Specifically, the boiling point of the basic compound is preferably 150 ° C. or higher, more preferably 180 ° C. or higher at normal temperature.

  The basic compound or the compound that expresses basicity as the viscosity stabilizer is desirably blended in the inkjet ink at a ratio of 1 mol% to 30 mol% with respect to the total molar amount of the photoacid generator. . More preferably, it is 2 mol% or more and 15 mol% or less. Beyond this range, the sensitivity is significantly reduced or the effect of stabilizing the viscosity is lost.

  When a photosensitive basic compound that is decomposed by irradiation with light or radiation is used, it is desirable because a decrease in sensitivity accompanying the addition of a base can be reduced.

As the photosensitive basic compound, a sulfonium compound or an iodonium compound can be preferably used. For example, as the sulfonium compound, compounds represented by the following general formulas (SS1) to (SS4) are exemplified.

(Wherein R ³¹ , R ³² and R ³³ are each an alkyl group, aryl group, heteroaryl group, or alkyl group, alkylaryl group, halogen atom, alkoxy group, phenoxy group, thiophenol group, phenylsulfonyl group. Or an aryl group substituted by a phenylsulfenyl group, and Y is CH ₂ , O, or S. R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ are each an alkyl group, an alkoxy group, or a halogen atom in and, X1 ^- represents a basic anion).
R ³¹ , R ³² and R ³³ are preferably methyl, ethyl, propyl, isopropyl, butyl, phenyl, biphenyl, tolyl, xylyl, chlorophenyl, bromophenyl, methoxy Examples include phenyl group, ethoxyphenyl group, propyloxyphenyl group, butyloxyphenyl group, tert-butyloxyphenyl group, phenoxyphenyl group, thiophenoxyphenyl group, phenoxyphenyl group, thiophenoxyphenyl group, and phenylsulfonylphenyl group. .

R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are preferably an alkyl group, a methoxy group, an ethoxy group, a chlorine atom or a bromine atom.

X1 ^- The, hydroxyl ^ion, - OR is C1~C4 alkyl ^base, - OCOR '(R' is an alkyl group, an aryl group or an alkyl aryl ^group), OCOO ^-, OSOO - include anions represented by.

As the iodonium compound, compounds represented by the following general formulas (IS1) to (IS4) are preferable.

In the above general formula, R ³⁸ and R ³⁹ are each an alkyl group, aryl group, heteroaryl group, or alkyl group, aryl group, halogen atom, alkoxy group, phenoxy group, thiophenol group, phenylsulfonyl group or phenylsulfenyl group. An aryl group mono-, di- or tri-substituted by a group. Y is CH ₂ , O or S, R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ are each an alkyl group, an alkoxy group or a halogen atom, n is 5 or 6, and X 2 ⁻ is a basic group. Anion.

R ³⁸ and R ³⁹ are preferably methyl, ethyl, propyl, isopropyl, butyl, phenyl, biphenyl, tolyl, xylyl, chlorophenyl, bromophenyl, methoxyphenyl, ethoxy Examples include phenyl group, propyloxyphenyl group, butyloxyphenyl group, tert-butyloxyphenyl group, phenoxyphenyl group, thiophenoxyphenyl group, phenoxyphenyl group, thiophenoxyphenyl group, and phenylsulfonylphenyl group.

R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ are preferably an alkyl group, a methoxy group, an ethoxy group, a chlorine atom or a bromine atom.

X2 ^- as preferably hydroxyl ^ion, - OR is C1~C4 alkyl ^base, - OCOR '(R' is an alkyl group, an aryl group, alkylaryl ^group), OCOO ^-, OSOO - include anions represented by .

  Particularly preferable examples of the sulfonium compound and the iodonium compound include triphenylsulfonium acetate, triphenylsulfonium hydroxide, triphenylsulfonium phenolate, tris- (4-methylphenyl) sulfonium hydroxide, and tris- (4-methyl). Phenyl) sulfonium acetate, tris- (4-methylphenyl) sulfonium phenolate, diphenyliodonium hydroxide, diphenyliodonium acetate, diphenyliodonium phenolate, bis- (4-t-butylphenyl) iodonium hydroxide, bis- (4- t-butylphenyl) iodonium acetate, bis- (4-t-butylphenyl) iodonium phenolate, thiophenyl substituted triphenylsulfonium acetate With or, like triphenylsulfonium hydroxide which is thiophenyl substituted.

  In addition to the basic compounds described above, other basic compounds can also be added. When an onium salt is used as the photoacid generator, the photoacid generator and the basic compound are preferably the same type of compound. For example, when both are sulfonium compounds and iodonium compounds, excellent effects can be obtained in terms of sensitivity and storage stability.

  Furthermore, when a compound that is not basic in nature decomposes with time to produce a basic compound, it is desirable because the acid that is gradually generated can be neutralized. As such a compound, a compound that generates a base by heat can be used. For example, carbamate compounds such as NBC-101 (trade name: Midori Chemical Co., Ltd.) and α, α-dimethyl-3,5-dimethoxybenzylcarbamate can be exemplified.

In addition, compounds represented by the following general formulas (TBG1) to (TBG8) can also be suitably used.

In the above chemical formula, R ⁵¹ , R ⁵² And R ⁵⁴ Are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms. R ⁵¹ and R ⁵² , R ⁵¹ and R ⁵⁴ and R ⁵² and R ⁵⁴ may be bonded to each other to form a ring structure. R ⁵³ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁵⁵ is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms A cyclic alkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, M represents iodonium or sulfonium, j represents an integer of 2 to 10, and k represents an integer of 1 to 3; Show.

Examples of the linear or branched alkyl group having 1 to 20 carbon atoms introduced as R ⁵¹ , R ⁵² , R ⁵⁴ , and R ⁵⁵ include a methyl group, an ethyl group, an n-propyl group, and iso- Examples thereof include a propyl group, an n-butyl group, a tert-butyl group, and an n-dodecyl group. Examples of the cyclic alkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclododecyl group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and a pyrenyl group. Examples of the ring structure to be formed include a piperidino group, a pyrrolidino group, a propyleneimino group, and an acetylidino group.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms introduced as R ⁵³ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a tert group. -A butyl group etc. are mentioned.

(Dispersant, surfactant, etc.)
The inkjet ink according to the embodiment of the present invention may further contain a small amount of a dispersant such as a nonionic or ionic surfactant or a charging agent in order to enhance dispersibility of pigments and the like. Polymeric dispersants such as acrylic and vinyl alcohol having similar properties are also preferably used. However, when a cationic dispersant is used as the dispersant, it is desirable to select a compound having a lower acidity than the carboxylic acid. This is because some cationic dispersants promote the curing dark reaction of the ink. In addition, a dispersant or a pigment having a strong basicity may not only lower the sensitivity of the ink but also accelerate the curing dark reaction. Therefore, as such a dispersant, it is desirable to use a neutral or nonionic compound.

(Radically polymerizable monomers, etc.)
When the surface to be printed is strongly basic, or when the pigment or the surface to be printed is easily affected by an acid, the influence can be reduced by adding an appropriate radical polymerizable compound. As the radically polymerizable compound, for example, an acrylic or methacrylic monomer, a styrene monomer, or a compound having a plurality of vinyl polymerizable groups thereof can be used.

  The vinyl ether compound can be radically polymerized alone or in combination with an acrylic monomer. Similarly, when a compound having both cationic polymerizability and radical polymerizability is added, such as Daicel Chemical's CEL2000, glycidyl methacrylate, ester compounds such as vinyl alcohol and acrylic, methacryl, etc., radical polymerization And cationic polymerization advantages can be obtained. In this case, a photoradical polymerization initiator such as Michler's ketone or benzophenone known under the trade name Irgacure, and a photocrosslinking radical generator such as bisazide can be contained at the same time. Such a method can also be applied when it is desired to impart higher chemical resistance to the cured ink layer.

(Other solvents, etc.)
The ink-jet ink according to this embodiment is usually desired to be prepared so as not to contain volatile components such as water or an organic solvent as much as possible. However, for example, an organic solvent used in preparing the raw material such as methyl ethyl ketone, propylene glycol solvent, ethyl lactate, and xylene may be inevitably mixed. For example, when an exhaust mechanism or a solvent recovery mechanism is provided, a small amount of an organic solvent may be included for the purpose of obtaining a desired printed matter. In this case, from the viewpoint of safety, it is desirable to use water, alcohols such as ethanol and propanol, and petroleum components such as isopar and terpene.

  As described above, the present invention has been described in detail by giving examples for each component. Next, characteristics commonly required for inkjet inks will be described.

  When the alicyclic skeleton contained in the acid polymerizable compound as described above has a terpenoid skeleton, the safety of the inkjet ink or the ink layer after curing to the human body and the environment is preferable. For example, in the case of vinyl ether, myrcene, osimene, geraniol, nerol, linalool, citrolenol, citral, menten, limonene, dipentene, terpinolene, terpinene, ferrandrene, sylvestrene, piperitol, terpineol, terpineol, mentenoneol, isopulegol, peralaldehyde , Piperitone, dihydrocarbon, carvone, pinol, ascaridol, zabinene, carene, pymene, bornene, fenken, camphene, carveol, sesquiterpenes, diterpenes, triterpenes, etc. And vinyl ether compounds in which is substituted with a vinyl group.

  Alternatively, an alicyclic oxetane compound in which an alcohol having a skeleton as described above is subjected to dehydration condensation with an alcohol having an oxetane skeleton and ether-bonded is also preferable. On the other hand, a vinyl ether compound, an epoxy compound, and an oxetane compound having a norbornene skeleton that are abundant in nature are favorable in terms of cost, and thus can be suitably used.

Since the inkjet ink according to the embodiment of the present invention is a photosensitive ink that needs to be heated, it is desired that the volatility of the ink is low from the viewpoint of safety and odor. Specifically, the volatilization rate at 80 ° C. after exposure is desirably 0.2 mg / cm ² · min or less. The volatilization amount here indicates the volatilization amount (mg) per minute when a container having an opening area of 10 cm ² is heated, for example. Although this value depends on the opening of the container, it is normally defined as a value when 4 g of ink is contained in a petri dish having a diameter of 6 cm and heated under normal pressure. If the volatilization rate is too high, the safety is impaired and the odor problem becomes significant. On the other hand, in the case of ink with extremely low volatility, for example, 0.00001 mg / cm ² · min or less, the viscosity is usually too high and inkjet ejection is often difficult.

As already described, it is desirable that the ink-jet ink according to the embodiment of the present invention has a fluidity of 30 mPa · sec at least at room temperature. In order to achieve such performance, when n kinds of acid polymerizable compounds including the vinyl ether compound as described above are mixed and contained, η _t represented by the following formula (A) is 3 (mPa · sec). The composition is preferably 30 (mPa · sec) or less and more preferably 5 (mPa · sec) or more and 25 (mPa · sec) or less.

(In the above formula _{(A), χ 1, χ} 2, χ 3, ···, χ n is the weight composition ratio of each _{component, η 1, η 2, η} 3 ···, η n is (The viscosity of each component alone at normal temperature and normal pressure.)
If it deviates from this range, the ejection of the ink becomes extremely difficult, or the image is liable to be disturbed due to the ejection disorder. Furthermore, when such a value is 12 mPa · sec or less at room temperature, since ink jet discharge is possible without heating the head, ink storage stability and volatilization from the head can be reduced, which is more preferable. It becomes.

Moreover, the inkjet ink concerning embodiment of this invention may contain the epoxy compound or oxetane compound whose solubility parameter is (19MPa1 ^{/ 2} ) or more as a part of solvent. By containing such a compound, it is possible to control the properties related to the solubility of the ink, and to further improve the stability of the inkjet ink. For example, effects such as enhancing the solubility of the photoacid generator and enhancing the dispersibility of a pigment as a coloring material can be obtained. In addition, the surface properties of the ink can be improved. If the surface tension is not appropriate under conditions that affect the ink ejection operation such as the surface tension, it is necessary to add a surfactant or the like to adjust the surface tension value. By adding a compound having a predetermined solubility parameter, it is not necessary to add a surfactant.

The vinyl ether compound is easily dissolved in an acid polymerizable compound having a solubility parameter of (19 MPa ^1/2 ) or more, and the solubility parameter can be arbitrarily set within a range where the ink jet discharge operation can be stably performed. The solubility parameter can be determined from the heat of evaporation, surface tension, solubility in a substance having a known solubility parameter, and the like. Examples of such an epoxy compound or oxetane compound include C3000 (limonene dioxide, manufactured by Daicel Chemical Industries), OXT221 (di [1-ethyl (3-oxetanyl)] methyl ether, manufactured by Toagosei Co., Ltd.), and a polyethylene oxide skeleton. And compounds having an oxetane group at the terminal.

  As described above, the inkjet ink according to the embodiment of the present invention relies on the chemical amplification mechanism for its image forming ability. That is, an acid is generated from the photoacid generator by exposure, and this acid diffuses by heating and functions as a catalyst for the crosslinking reaction. For this reason, in this ink-jet ink, the presence of significant basic ions causes a decrease in sensitivity. Therefore, it is desirable to take care not to mix a large amount of basic ions not only in the preparation process of the inkjet ink but also in the manufacturing process of each component.

  As described above, the pigment used in the ink-jet ink according to the embodiment of the present invention has other colors such as magnetism, fluorescence, conductivity, dielectricity, electromagnetic heat generation, etc. It may further indicate properties. When an ink-jet ink containing such a pigment is used, various functions can be imparted to the printed matter. Some examples are shown below.

First, the case where the inkjet ink contains a pigment having magnetism will be described.
First, an ink-jet ink containing magnetic powder as a pigment is prepared. This ink-jet ink includes, for example, magnetic powder such as iron, cobalt, nickel, and alloys and oxides thereof, a photoacid generator, a polymer compound or polymer powder for improving dispersibility, and the like. Can be obtained by adding it into the solvent.

  Next, the inkjet ink is ejected onto a recording medium to draw a pattern such as a barcode pattern. Immediately after ink ejection, the ink layer is irradiated with light such as ultraviolet rays. The irradiation amount at this time can be set in accordance with the content of the pigment in the ink-jet ink and the photosensitivity thereof, and is usually about several hundred mJ to several thousand mJ. Even when the ink layer is in a state immediately after light irradiation, the tackiness and fluidity of the ink layer are lost, but the ink layer can be completely cured by maintaining the temperature in the stocker at room temperature to 60 ° C. Since the cured ink layer has magnetism, secondary information other than image information can be read by a magnetic detection mechanism such as a magnetic head.

Next, the case where the inkjet ink contains a conductive pigment will be described.
First, an inkjet ink containing conductive powder as a pigment is prepared. This inkjet ink is, for example, silver, gold, copper, aluminum, carbon, nickel, iron, cobalt, lead, tin, antimony, alloy powder of any combination thereof, and a composite of them and organic matter It can be obtained by adding the conductive pigment, the photoacid generator, and a polymer or polymer powder for improving dispersibility into the above-described solvent. For the purpose of reducing the resin content in the finally obtained ink layer and increasing the conductivity, the content of the polymerizable compound in the inkjet ink may be reduced and an organic solvent may be added to the inkjet ink.

  This inkjet ink is ejected onto a recording medium such as an insulating substrate to draw a pattern such as a wiring pattern. Immediately after ink ejection, the ink layer is irradiated with light such as ultraviolet rays. The irradiation amount at this time can be set according to the content of the pigment in the ink-jet ink and its photosensitivity, and is usually about several hundred mJ to several hundreds mJ. Even when the ink layer is in a state immediately after light irradiation, the adhesiveness and fluidity of the ink layer are lost, but the ink layer can be completely cured by maintaining the temperature in the stocker at room temperature to 60 ° C. When heat and pressure are applied to the ink layer, the conductivity can be further increased. Further, when an alloy powder having a relatively low melting point is used as the conductive pigment, the conductive layer can be obtained by heating the ink layer to the flow temperature. Since the printed pattern thus obtained has conductivity, it can be used as a circuit pattern or a resistance pattern.

  Furthermore, when an inkjet ink containing a dielectric powder such as barium lead, bismuth, iridium, ruthenium, tantalum, platinum, titanium, strontium, chromium, or an oxide thereof, or a ceramic powder is used, It is also possible to form a dielectric layer of a capacitor or an inductor. In this case, the characteristics may be improved by baking after pattern formation. In addition, when an inkjet ink containing a pigment having a photocatalytic function and a bactericidal ability such as titanium oxide powder is used, it is possible to form a printed pattern having such a function. Examples of the electromagnetic wave exothermic powder include electromagnetic wave exothermic ceramics and silicon resin, and can be used for applications such as selectively heating a printed portion with electromagnetic waves. Such a powder can be used for improving the electromagnetic wave heating property of the inkjet ink according to the embodiment of the present invention.

  Furthermore, by appropriately using the technique described in the present embodiment, it is possible to form overprinting or a relatively thick print pattern. In other words, an image having a raised portion capable of partial correction of printing and tactile image recognition by repeating ejection of inkjet ink and curing of the ink layer obtained thereby in a predetermined area of the recording medium a plurality of times. Can be formed. For example, a print pattern for handicap users such as Braille, a topographic map with a thickness changed corresponding to contour lines, and a part of a device having a thickness of several tens of μm or more are formed. It is also possible to do.

  The inkjet ink according to the embodiment of the present invention can be applied to, for example, an inkjet recording apparatus as shown in FIG. The illustrated inkjet recording apparatus 1 includes a transport mechanism 3 that transports a recording medium 2. An ink jet recording head 4, a light source 5, and a heater 6 as heating means are sequentially arranged from the upstream side to the downstream side along the moving direction of the transport mechanism 3.

  The recording medium (or printed material) 2 is not particularly limited as long as it is a printable medium. As the recording medium 2, for example, paper, an OHP sheet, a resin film, a nonwoven fabric, a porous film, a plastic plate, a circuit board, a metal substrate, and the like can be used.

  For example, the transport mechanism 3 transports the medium 2 so that the recording medium 2 sequentially passes through the front surface of the recording head 4, the light source 5, and the heater 6. Here, the transport mechanism 3 transports the recording medium 2 from the right side to the left side in the drawing. The transport mechanism 3 can be configured by, for example, a belt and / or roller that moves the recording medium 2 and a drive mechanism that drives the belt and / or roller. The transport mechanism 3 may further be provided with a guide member that assists in moving the recording medium 2.

  The recording head 4 ejects ink-jet ink onto the recording medium 2 corresponding to the image signal to form an ink layer. As the recording head 4, for example, a serial scanning type head mounted on a carriage or a line scanning type head having a width equal to or larger than the width of the recording medium 2 can be used. From the viewpoint of high-speed printing, the latter is usually more advantageous than the former. There is no particular limitation on the method of ejecting ink jet ink from the recording head 4. For example, ink droplets can be ejected using the pressure of vapor generated by the heat of the heating element. Alternatively, ink droplets may be ejected using mechanical pressure pulses generated by a piezoelectric element.

  The light source 5 irradiates the ink layer on the recording medium 2 with light to generate an acid in the ink layer. Examples of the light source 5 include a mercury lamp such as a low, medium, and high pressure mercury lamp, a tungsten lamp, an arc lamp, an excimer lamp, an excimer laser, a semiconductor laser, a YAG laser, a laser system that combines a laser and a nonlinear optical crystal, A high frequency induced ultraviolet ray generator, an electron beam irradiation device, an X-ray irradiation device, or the like can be used. In particular, it is desirable to use a high frequency induced ultraviolet ray generator, a high / low pressure mercury lamp, a semiconductor laser, etc., because the system can be simplified. Further, the light source 5 may be provided with a condensing mirror or a running optical system.

  The heater 6 heats the ink layer on the recording medium 2 and promotes a crosslinking reaction using an acid as a catalyst. The ink-jet ink according to the embodiment of the present invention can be cured without necessarily performing post-exposure heating, but it is desirable to perform heating for more rapid curing. As the heater, for example, an infrared lamp, a roller (heat roller) with a built-in heating element, warm air or a blower that blows hot air can be used.

  Using such an apparatus 1, printing can be performed on a recording medium by the following method, for example.

  First, the recording medium 2 is transported from the right side to the left side in the drawing by the transport mechanism 3. The conveyance speed of the recording medium 2 can be set within a range of 0.1 m / min to several hundreds m / min, for example.

  When the recording medium 2 is conveyed to the front of the recording head 4, the recording head 4 ejects the inkjet ink corresponding to the image signal. Thereby, an ink layer is formed on the recording medium 2.

The recording medium 2 on which the ink layer is formed is conveyed to the front of the light source 5. When the recording medium 2 passes in front of the light source 5, the light source 5 irradiates light toward the ink layer formed on the recording medium 2 to generate an acid in the ink layer. The irradiation light intensity at the position on the surface of the ink layer varies depending on the wavelength of the light source used, but is usually in the range of several mW / cm ^{2 to 1} KW / cm ² . The exposure amount to the ink layer can be appropriately set according to the sensitivity of the inkjet ink, the moving speed of the printing surface (conveying speed of the recording medium 2), and the like.

  Subsequently, the recording medium 2 is conveyed into or near the heater 6. When the recording medium 2 passes through or in the vicinity of the heater 6, the heater 6 heats the ink layer formed on the recording medium 2 and promotes a crosslinking reaction in the ink layer. In the apparatus 1 shown in FIG. 1, the heating time by the heater 6 is usually relatively short, from several seconds to several tens of seconds. Accordingly, when the ink layer is cured almost completely by the heater 6, the maximum temperature reaches, for example, about 200 ° C. or less, preferably 80 ° C. to 200 ° C. or preferably 60 ° C. to 180 ° C. Heat to.

  Thereafter, the recording medium 2 is conveyed into a stocker (or container) (not shown). This completes printing.

  The heating means for heating the ink layer is not limited to the heater 6 disposed downstream of the light source as shown in FIG. For example, when the ink layer is exposed, the light source 5 can be used as a heat source by bringing the light source 5 closer to the recording medium 2 to the extent that the printing surface is not damaged. By not providing a heat removal mechanism such as a cold mirror in the light source, the light source may be similarly used as a heat source. In the case of a high-power valve of several hundred watts, since it has a cooling mechanism at the same time, a part of the exhaust heat mechanism is changed to provide a mechanism for intentionally reducing the heat to the paper surface. Accordingly, the ink layer can be heated by heat generated from the light source.

  More specifically, this corresponds to a light source with an output of 100 w or more having a mechanism used for heating by re-introducing an airflow that cools the light source into a paper surface or a transport / holding mechanism. The temperature reached by the recording medium due to the reduction of the heat of the light source may be a temperature at which the same effect as the heating by the heater described above is obtained. The preferred temperature varies depending on the heating time, but is usually at least 60 ° C or higher, more preferably from 80 ° C to 100 ° C. In addition, when the exposure speed is as high as several m / second, it may be heated to about 180 ° C. because it is heated instantaneously.

  For example, when a light source 5 that can generate infrared light in addition to visible light is used, heating can be performed simultaneously with light irradiation. In this case, since hardening can be accelerated | stimulated, it is preferable.

  When the ink layer is irradiated with light, the ink layer is heated by the heat generated from the light source 5, so that the heating means is not necessarily provided as an independent member like the heater 6. However, it takes a long time to completely cure the ink layer by allowing it to stand at room temperature only with heat from the light source 5. Therefore, it is desirable that the standing at room temperature is applied to an application that can secure a sufficiently long time until complete curing. For example, a printed matter such as a newspaper announcement distributed the next day can secure a long time of about one day and night until it is cured, so that it can be completely cured even at room temperature.

  The inkjet ink according to the embodiment of the present invention can also be applied to the inkjet recording apparatus shown in FIG. The inkjet recording apparatus 1 shown in the figure has substantially the same structure as the inkjet recording apparatus 1 shown in FIG. 1 except that a heater is built in the stocker 7.

  The stocker 7 can accommodate a plurality of recording media 2 that have been exposed. The stocker 7 sets the exposed recording medium 2 to a temperature of, for example, about 40 ° C. or higher, preferably about 50 ° C. to 120 ° C., more preferably about 60 ° C. to 100 ° C. or about 50 ° C. to 80 ° C. It can be held for a predetermined time.

  In the apparatus 1 configured as shown in FIG. 1, since the heater 6 is arranged in the middle of the conveyance path of the recording medium 2, it is not easy to heat each recording medium 2 for a long time. On the other hand, in the recording apparatus 1 shown in FIG. 2, since the heater is built in the stocker 7, it is possible to heat each recording medium 2 for a long time. In addition, since a plurality of recording media 2 can be heated together in the stocker 7, it is advantageous from the viewpoint of power consumption. Further, when the individual recording media 2 can be heated for a long time, there are the following advantages.

  That is, depending on the combination of the recording medium 2 and the inkjet ink to be used, reflow may be promoted by heating at a high temperature for a short time, and the image quality may deteriorate. Such a decrease in image quality is caused by reflowing at a high temperature, and can be prevented by heating the ink layer at a relatively low temperature for a long time. For example, by holding the exposed recording medium 2 in the stocker 7 at about 50 ° C. to 80 ° C. for several minutes or more, the ink layer can be almost completely cured without causing deterioration in image quality.

  The stocker 7 is preferably provided with a discharge mechanism for sequentially discharging the recording medium 2 held in a heated state for a predetermined time. The heating and holding time can be set according to the inkjet ink to be used, the heating temperature, and the like. For example, when the heating temperature is 50 ° C. to 100 ° C., the heating and holding time can be about 0.5 to 10 minutes, and when the heating with the heater is not performed, the heating and holding time is several hours. Can be about.

  A heater 6 as shown in FIG. 1 may be further arranged on the upstream side of the stocker 7. If the ink layer is not sufficiently cured before the recording medium 2 is fed into the stocker 7, the recording medium 2 may come into contact with each other in the stocker 7, thereby causing image distortion. By preliminarily heating with the heater 6, the individual recording media 2 can be heated before being accommodated in the stocker 7, so that such image disturbance is less likely to occur.

  As described above, when the ink-jet ink according to the embodiment of the present invention is used, the ink layer is quickly made non-fluidized by irradiating with light and then heating as necessary after being discharged onto the printing surface. can do. That is, it is possible to obtain a high-quality printed material without requiring a large-scale exposure system. The obtained non-flowable film desirably exhibits thermoplasticity (it is reflowable by heat, and the property duration may be short).

  Further, unlike conventional inkjet inks that utilize radical polymerization, such inkjet inks do not require the use of carcinogenic radical generators or radically polymerizable monomers with large skin irritation and odor. Therefore, the inkjet ink according to this embodiment is easy to handle.

  Furthermore, in the inkjet ink according to the embodiment of the present invention, typically, almost the entire solvent is composed of an acid-polymerizable compound. If the ratio of the polymerizable compound to the whole solvent is sufficiently high, the organic solvent hardly volatilizes during printing. Therefore, the problem of atmospheric pollution caused by volatilization of the organic solvent can be prevented, and no exhaust equipment or solvent recovery mechanism is required.

  The ink-jet ink according to the embodiment of the present invention does not require the use of an organic solvent, and the ink layer can be quickly non-fluidized, so that bleeding is almost generated even on various printing surfaces having different properties. The image can be fixed easily without any problem. In addition, the printed surface is hardly deteriorated as the ink layer is dried. Furthermore, since the pigment as the color component can be contained at a high concentration, it is possible to form a clear and excellent weather resistance printing pattern by using the inkjet ink according to the embodiment of the present invention. It was.

Hereinafter, the present invention will be described in more detail with reference to specific examples.
In the following description, the vinyl ether compound is the same as the compound represented by the general formula (1).

First, a vinyl ether compound represented by the following chemical formula was prepared as an acid polymerizable compound.

Using these vinyl ether compounds in the formulations shown in Tables 1 and 2 below, solvents A1 to A13, B1 to B18, C1 to C6, and D1 were obtained.

In addition, the vinyl ether in the said table | surface is the following compounds.
HQDV: p-vinyloxybenzene 4CHDV: 1,4-cyclohexanediol divinyl ether 1,3CHDVE: 1,3-cyclohexanediol divinyl ether IBVE: isoborneol vinyl ether CHMVE: 1,4-cyclohexanedimethanol vinyl ether TBP-VE: 1- tertbutyl-4-vinyloxybenzene M-CHDV: 2-methoxy-1,4-cyclohexanediol divinyl ether MEDVE: methoxy-vinyloxy-cyclohexanemethanol vinyl ether M-NBDV: methoxynorbornane divinyl ether ISB-DVE: isosorbide divinyl ether ONB-DVE: Hydroxymethyl-hydroxyoxanorbornanediol divinyl ether OCN-DVE: Oki Bicyclononane divinyl ether NBDV: Norbornane divinyl ether TBMP-IP: t-butylbenzyl alcohol isopropenyl CHM-IP: Cyclohexane methanol isopropenyl DOM-IP: Dioxolane methanol isopropenyl NBM-IP: Norbornane methanol isopropenyl DCPVE: DCP dimethanol di Vinyl ether In Table 1 above, SR-NPG is a diglycidyl ether compound having a neopentane skeleton (manufactured by Sakamoto Yakuhin Kogyo), OXT221 is an oxetane compound (manufactured by Toagosei), and C3000 is limonene dioxide (Daicel Chemical) DEGV is diethylene glycol monovinyl ether (manufactured by Maruzen Petrochemical).

  To each of the solvents A1 to A13, carbon black (5% by weight) as a pigment and UVACURE 1591 (8% by weight) as a photoacid generator were added, and dispersed with a paint shaker day and night. The mixture after the dispersion treatment was filtered with a 5 μm PTFE filter to obtain inkjet inks (Nos. 1 to 13).

  Carbon black is pre-kneaded with an acrylic resin dispersant to form a mill base, and 200 ppm nonionic surfactant (Sumitomo 3M) and commercially available dispersant (Ajinomoto Fine Techno, product name Ajisper) are added. No. 1 to 13 inkjet inks were obtained. These are all ink jet inks according to an embodiment of the present invention because 40 parts by weight or more of the acid polymerizable compound is a vinyl ether compound having a cyclic skeleton. No. In the same manner as the inks 1 to 13, No. 34-58 inks were made.

  For comparison, a photo radical generating ink jet ink was prepared. First, 50 parts by weight of isobornyl acrylate (IBA), 25 parts by weight of tripropylene glycol diacrylate (TPGDA), and 25 parts by weight of trimethylolpropane ethoxylate triacrylate (TMPETA) were mixed to prepare a solvent. . To this solvent, parts by weight of Irgacure (NO. 2959, Nagase Sangyo), 5 parts by weight of carbon black pigment, a trace amount of acrylic dispersant, and a surfactant were added. The obtained mixture was subjected to a dispersion treatment with a homogenizer for 5 hours, and then filtered through a 5 μm PTFE filter. The photo radical generating ink-jet ink thus obtained was designated No. 14 inkjet inks were obtained.

  Further, a non-cyclic skeleton vinyl ether compound (DEGV) and C3000 were used as solvents, respectively, and a carbon black pigment as a color component was blended in the same manner as described above. 15 and 33 inkjet inks were prepared.

  No. The inkjet inks 14, 15, and 33 are comparative examples because they do not contain a vinyl ether compound having a cyclic skeleton.

  The performance of the obtained inkjet ink was evaluated using the inkjet recording apparatus shown in FIG. A normal glossy paper was used as the recording medium 2 and an ultrahigh pressure mercury lamp with an output of 230 W was used as the light source 5. The heater as the heating means 6 was not provided, and the ink layer was tried to be cured only by ultraviolet irradiation. Recording was performed under these conditions, and the pencil hardness, print quality, solvent resistance, adhesion to the recording medium, and the like of the ink cured film were examined.

  In addition, pencil hardness is the result measured about the ink layer on the following conditions, respectively.

Immediately after exposure: Ink layer immediately after exposure Stocker: Ink layer maintained at a temperature of 80 ° C. for 3 minutes in the stocker after exposure Standing at room temperature: Ink layer left at room temperature (25 ° C.) for 8 hours after exposure An image was visually confirmed and evaluated, and “good” was obtained when there was no omission, and “bad” when there were some omissions.

  The solvent resistance was evaluated as follows by conducting a rubbing test using a cloth impregnated with an organic solvent such as ethanol or acetone.

A (very good): No change B (good): Ink adheres to the cloth C (slightly defective): The color of the ink layer is lightened D (defect): A part of the ink layer is completely peeled off.

  In addition, the cross-cut tape peel test was performed for the adhesion, and the area where the ink film was peeled off was less than 10% of the whole, and the area of 10% or more of the whole was judged as defective.

  First, the influence of the content of the vinyl ether compound in the acid polymerizable compound was examined. No. 1 shown in Table 1 above, except that an epoxy compound (C3000) was blended at a predetermined ratio as a part of the acid polymerizable compound. Various inks were prepared according to the same formulation as the inkjet ink of No. 2. The obtained ink was applied to the recording apparatus shown in FIG. 1, and the pencil hardness and solvent resistance of the ink cured film were examined.

  Similarly, No. 1 shown in Table 1 was used except that an oxetane compound (OXT221) and an epoxy compound (SR-NPG) were blended at a predetermined ratio as a part of the acid polymerizable compound. Various inks were prepared according to the same formulation as the 45 and 46 inkjet inks.

The results are summarized in Tables 3 to 5 below together with the content and exposure amount of the vinyl ether (VE) compound.

  As shown in Tables 4 and 5 above, it is confirmed that when a vinyl ether compound having a cyclic skeleton is contained in an ink solvent, the photosensitivity performance is remarkably improved, and the solvent resistance is excellent. Demonstrated. In addition, as shown in Tables 3 to 5, when the vinyl ether compound having a cyclic skeleton is contained in an amount of 40 parts by weight or more of the acid polymerizable compound, the photosensitivity of the ink is remarkably improved and formed. The solvent resistance of the ink cured film is also good. Even when rubbing with a cloth soaked in an organic solvent such as ethanol or acetone, no change was observed in the cured ink film, and it was confirmed that the ink had excellent solvent resistance.

  Furthermore, recording on a recording medium such as an OHP sheet was performed to attempt ink curing. As a result, it was confirmed that an ink cured film having excellent adhesion strength can be formed by using the inkjet ink according to the embodiment of the present invention.

In Table 6 below, no. The result of having compared the performance of the inkjet ink of 2, 14, and 33 is shown.

As shown in Table 6 above, No. 1 according to the embodiment of the present invention. The ink-jet ink of No. ² can obtain a pencil hardness of H or higher immediately after exposure even with an extremely low exposure amount of 250 mJ / cm ² . In addition, the print quality, solvent resistance, and adhesion to media are all good.

On the other hand, photo radical generation type No. In the case of ink No. 14, the exposure amount was significantly increased to 1750 mJ / cm ² and the ink layer could not be cured when heated in the stocker. In order to cure the ink layer with an exposure amount of 1000 mJ / cm ² , the pigment concentration in the inkjet ink had to be reduced to 3% by weight. The pencil hardness at this time remained at HB, and the obtained prints were light in color but strong in resin gloss and could not be put into practical use.

In addition, No. containing only an epoxy compound as an acid polymerizable compound. In the inkjet ink No. 33, the exposure amount was 250 mJ / cm ² and the pencil hardness was HB. The ink H of 2 is not reached. Further, the obtained print was slightly glossy although the image was good.

  By comparing these inks, No. 1 according to the embodiment of the present invention is obtained. It was confirmed that the ink of No. 2 was able to reach a firm hardness only by ultraviolet irradiation, and was extremely excellent in quick drying.

In Table 7 below, no. The result of having compared the performance of the inkjet ink of 2 and 15 is shown.

  No. In the ink No. 2, the acid polymerizable compound is composed of a vinyl ether compound (4CHDV) having an alicyclic skeleton. In the ink No. 15, an acid polymerizable compound is composed of a vinyl ether compound (DEGV) having a chain skeleton.

As shown in Table 7 above, no. The inkjet ink of No. 2 It can be cured with an exposure amount lower than that of 15 ink by about 150 mJ / cm ² , and the ink cured film obtained has good solvent resistance and adhesion. Such a tendency was also confirmed when an ink was prepared using a vinyl ether compound having another alicyclic skeleton as an acid polymerizable compound. Therefore, it was found that when applied to inkjet ink, it is possible to obtain an ink with extremely high curing performance.

  Based on the above results, in the embodiment of the present invention, at least 40 parts by weight of the acid polymerizable compound is defined as a vinyl ether compound having a cyclic skeleton. Next, the influence of the cyclic skeleton was examined.

In Table 8 below, no. The result of having compared the performance of the inkjet ink of 1 and 2 is shown.

  No. The vinyl ether compound contained in the ink No. 1 has an aromatic ring skeleton (benzene ring) as a cyclic skeleton. The vinyl ether compound contained in the ink No. 2 has an alicyclic skeleton (cyclohexane ring) as a cyclic skeleton. No. No. 2 compared with No. 2 ink. The ink No. 1 can be cured with an equivalent exposure amount, and the obtained cured ink film has the same performance such as curing hardness and adhesion. From the results in Table 8 above, no. It can be seen that the ink No. 1 has very good solvent resistance. This is a characteristic of an ink using a vinyl ether compound having an aromatic ring skeleton, and it has been found that the ink has high resistance to a wide range of chemicals such as ethanol, acetone, oil-based hydrocarbons, and ester-based solvents.

In Table 9 below, no. The result of having compared the performance of the inkjet ink of 4 and 5 is shown.

  No. The vinyl ether compound (IBVE) contained in the inkjet ink of No. 4 does not contain an oxygen atom as a ring constituent atom. The vinyl ether compound (ISB-DVE) contained in the inkjet ink 5 contains an oxygen atom as a ring constituent atom. Due to such a ring structure, ISB-DVE has a very high polarity compared to IBVE.

  In the results shown in Table 9 above, The curing performance of the 4 and 5 inks is comparable, and no difference is observed between these two inks. However, when an image was formed on a recording medium having a relatively high polarity such as a PET film, a phenomenon that wettability was considerably different appeared. No. No. 4 was confirmed to have a bleeding phenomenon in which ink droplets that are difficult to wet on the media surface are repelled. Image quality was reduced compared to ink No. 5. This is due to the difference in polarity of the vinyl ether compound.

Next, an ink jet ink was prepared by changing the blending of IBVE and ISB-DVE, and an image was formed on a PET film using the ink. The obtained image quality is compared and shown in Table 10 below.

  As shown in Table 10, wettability is improved and image quality is improved by blending ISB-DVE. Since the vinyl ether compound having a cyclic skeleton containing an oxygen atom as a ring constituent atom has the same high polarity as ISB-DVE, the same characteristics can be obtained. Therefore, the wettability with the media can be controlled without impairing the ink curing characteristics, and it has been confirmed that the ink is extremely useful as a solvent for inkjet ink.

In Table 11 below, no. The result of having compared the hardening characteristic of the inkjet ink of 2 and 11 is shown. No. No. 11 ink is No. 11 except that it contains a propylene carbonate compound in an amount of 10% by weight of the acid polymerizable compound. The composition is the same as that of ink No. 2.

  As shown in Table 11 above, no. The ink No. 11 has No. 10 characteristics such as printing quality, solvent resistance and adhesion. Although it is equivalent to the ink of No. 2, the hardness of the obtained ink cured film is low. Moreover, since the amount of exposure required is large, it turns out that a sensitivity is also low. Therefore, it cannot be seen from the results in Table 11 that a particularly excellent effect is produced by blending the propylene carbonate compound.

Next, except for changing the content of the photoacid generator, the above-described No. 1 was used. Ink jet inks were prepared with the same composition as 2 and 11, and the curing properties of the ink, the presence or absence of solids precipitation, and the ejection performance were examined. The results obtained are summarized in Table 12 below. In addition, precipitation of solid content was observed visually. The discharge performance was evaluated by visually confirming the printed image, and those having no omission were regarded as good, and those having some omission were regarded as poor.

  As shown in Table 12 above, No. 1 containing no propylene carbonate compound. In the ink of No. 2, when the content of the photoacid generator was 10% or more, the photoacid generator precipitated as a solid in the ink although the curing characteristics did not change. Ink on which the photoacid generator is deposited has a very low ejection performance.

  On the other hand, no. In No. 11 ink, when the addition amount of the photoacid generator was increased, it did not precipitate as a solid content, and the curing characteristics were improved. As a result, good storage stability could be maintained.

  In general, an ink containing a large amount of a photoacid generator has improved curing characteristics, but it has been inevitable that the storability of the ink will decrease. It was confirmed that by adding the propylene carbonate compound, the storage stability was not deteriorated and stable ink performance could be maintained even in the ink stored for a long time.

  The inkjet ink according to the embodiment of the present invention is required to contain a vinyl ether compound that is an acid polymerizable compound. By blending a predetermined compound as a part of the acid-polymerizable compound, desired properties can be imparted to the ink-jet ink.

In Table 13 below, no. The result of having compared the performance of the inkjet ink of 2 and 10 is shown.

  No. No. 10 inkjet ink was No. 10 except that 50 parts by weight of the acid polymerizable compound was oxetane compound (OXT221). The composition is the same as that of ink No. 2. As shown in Table 13 above, by using the oxetane compound together with the vinyl ether compound, the curing hardness can be further increased. Therefore, it was confirmed that it is effective to add an oxetane compound in order to obtain a tougher ink cured film. Furthermore, since the oxetane compound also has the effect of reducing the volatilization rate of the ink, the re-ejecting performance (ejecting performance when performing the ejection operation again without performing ejection for a certain period of time) has been improved.

In Table 14 below, no. The result of having compared the performance of the inkjet ink of 2 and 7 is shown. The flexibility of the ink layer was evaluated by a crack test of the ink cured film. The ink cured film was rapidly cooled from 50 ° C. to −50 ° C., and “good” was obtained when the occurrence of cracks was slightly observed by visual inspection, and “very good” when no crack was observed.

  No. The inkjet ink of No. 7 was No. 7 except that 50 parts by weight of the acid polymerizable compound was a diglycidyl ether compound (SR-NPG). The composition is the same as that of ink No. 2. As shown in Table 14 above, by using the glycidyl ether compound together with the vinyl ether compound, it was possible to improve the flexibility and storability of the ink cured film without any loss of the cured hardness.

Next, the influence which the structure of the vinyl ether compound mix | blended as an acid-polymerizable compound has was investigated. In Tables 15 and 16 below, no. The result of comparing the performance of the inkjet inks 1 to 6 and 34 to 58 is shown.

Among the vinyl ether compounds blended in these ink-jet inks, IBVE (No. 4) and CHMVE (No. 6) are monovalent compounds among the inks in which the vinyl ether compound is a simple substance, and the remaining vinyl ether compounds are divalent. It is. As shown in Table 15 above, the ink (No. 1 to 3, 5, 34 to 39) containing a divalent vinyl ether compound has a low exposure amount of about 100 to several tens of mJ / cm ^2. Photosensitivity can be achieved with an exposure amount, and the pencil hardness of the cured film also tends to be good. Such performance is presumed to be obtained even in the case of a divalent or higher valent vinyl ether compound. Therefore, even when a trivalent vinyl ether compound or a vinyl ether compound having a valence higher than that is paid out, the photosensitivity can be similarly increased.

  In particular, no. The ink No. 34 is extremely excellent in photocuring performance in the ink prepared with a single solvent, and it can be said that the characteristic performance of the solvent ONB-DVE is manifested. It can be seen that even if the oxetane compound is added in 10 inks, it is further excellent in photocuring performance. Ink prepared with a single solvent is not so unique as a material that can provide such a light-sensitive performance, and it has become possible to prepare ink that is superior in cost as well as functioning as an ink.

  No. Inks 40 to 43 are examples of inks prepared with a solvent mixed with a vinyl ether compound. ISB-DVE and ONB-DVE have a structure in which an oxygen atom is contained in an alicyclic skeleton, and M-CHDV and MEDVE have a structure in which a methoxy group that is an oxygen-containing substituent is substituted in the alicyclic skeleton have. The excellent hardness of the cured film, which is a characteristic of these solvents, also appeared in the ink photosensitivity. Furthermore, since it is excellent from the viewpoint of volatility, extremely good discharge operation and stable discharge performance were obtained.

  No. The inks 44 to 51 are inks prepared by mixing ISB-DVE and ONB-DVE as vinyl ether compounds and a solvent of an epoxy compound and an oxetane compound. In addition to showing high photosensitivity, each of No. The 44 and 46 inks are excellent in the flexibility of the cured film. No. It can be seen that the 45 and 47 inks have excellent curing hardness. Furthermore, no. It was found that 48 to 51 inks were also superior in adhesion.

  No. The inks 52 to 55 are inks prepared by mixing ONB-DVE and a solvent of an isopropenyl ether compound. In either case, high photosensitivity performance was obtained, and since the isopropenyl ether compound has relatively low volatility, the ejection performance is stable. Furthermore, it turned out that it is excellent in the solubility of an acid generator.

  No. Inks 56 and 57 are examples using ONB-DVE and a vinyl ether compound having an aromatic ring. These are excellent in photocuring performance and solubility of acid generators. Curing performance was improved by introducing an aromatic ring. Moreover, the polarity increased by introducing a methoxy group. As a result, also in terms of solubility and volatility, evaporation of the solvent could be further suppressed, and more stable ejection performance was obtained. Further, the wettability with the printing medium was improved, and a printed matter with improved image quality could be obtained.

  CHMVE is a vinyl ether compound having a cyclohexyl skeleton. A vinyl ether compound (DCPVE) having an alicyclic complex cyclic skeleton and having a vinyl ether group bonded thereto via a methylene skeleton has better photosensitive characteristics than an ink using CHMVE. This is the ink no. 58 results were confirmed. A vinyl ether compound having a complex cyclic skeleton exhibits better ink characteristics than a vinyl ether compound having an alicyclic structure having a single cyclic skeleton. Such a tendency was observed even when the vinyl ether group was not directly bonded to the alicyclic skeleton.

  In addition, No. In the vinyl ether compounds (HQDV, 4CHDV, 1,3CH-DVE and ISB-DVE) used in 1 to 3 and 5, the vinyl ether group is directly bonded to the cyclic skeleton. The vinyl ether compound (CHMVE) used in 6 has a methylene skeleton. From these comparisons, it can be seen that an ink containing a vinyl ether compound in which a vinyl ether group is directly bonded to a cyclic skeleton is superior in photosensitive characteristics as compared with an ink containing a compound having a methylene skeleton. In particular, performances such as solvent resistance and adhesion are improved. It was recognized that not only the methylene skeleton but also the structure of the bonding part between the vinyl ether group and the cyclic skeleton increased, and the photosensitive property tended to deteriorate. It was confirmed that the vinyl ether compound having a vinyl ether group directly bonded to the cyclic skeleton has extremely excellent characteristics.

  Furthermore, no. 5 or No. ISB-DVE and ONB-DVE used for inks such as 34 are compounds having a distorted cyclic ether structure such as an oxetane ring or a hydrofuran ring. These compounds are considered to have excellent reactivity due to the structure. This is most desirable particularly when such a cyclic structure has a bridged structure.

Next, the influence of the content of the photoacid generator was examined. As shown in Table 17 below, No. 1 was changed except that the addition amount of the photoacid generator was changed. Ink jet ink was prepared according to the same formulation as ink No. 2. Using the obtained ink, a performance test was performed by the ink jet recording apparatus 1 shown in FIG. The exposure amount, viscosity, and discharge state at this time are summarized together with the addition amount of the photoacid generator. The discharge state was judged from the change in the discharge state after a one-week accelerated test by heating at 60 ° C.

As shown in Table 17 above, when the addition amount of the photoacid generator is 1% by weight, an exposure amount of 800 mJ / cm ² is required and the sensitivity is low, while the vicinity exceeds 10% by weight. From this, the increase in viscosity became so large that it became impossible to discharge at all. However, it was confirmed that the addition amount of 2% by weight can maintain the performance such as sufficient curing hardness and solvent resistance, and the photosensitivity of the ink using the vinyl ether compound is extremely high.

  Table 17 also shows the corrosivity when Ni metal is immersed in each ink. Ni metal is generally used for piping and electrodes, and it is desired to avoid corrosion by ink as much as possible. The results in Table 17 show that Ni corrosion increases when the amount of photoacid generator added is 8% by weight or more.

Table 18 below summarizes the relationship between the viscosity of the inkjet ink and the ejection performance. Here, no. Various inks were prepared by adjusting the composition of ink No. 8. The performance was examined by performing an ejection operation using each ink, and the results obtained are shown in Table 18 below. Note that temperature control was not performed during the discharge operation.

  Usually, the ink ejection operation of the head needs to be temperature-controlled to match the viscosity suitable for the driving condition of the head. It can be seen from the results in Table 18 that if the ink has a viscosity of 12 mPa · s or less, the ink can be ejected without temperature control, and the head design becomes easy.

Next, the influence of the solubility parameter (SP value) of the epoxy compound was examined and summarized in Table 19 below. Here, No. 1 is used except that an epoxy compound having a predetermined solubility parameter is blended. A plurality of inks were prepared according to the same formulation as the 12 inks. For these inks, the solubility of the vinyl ether compound and the photoacid generator and the ejection performance were examined, and the results obtained are shown in Table 19 below. In addition, the evaluation of solubility is carried out by visually checking a solution when a predetermined acid polymerizable compound and a photoacid generator are mixed, and those that do not cause turbidity or precipitation at all are good. It was a little difficult to accept. The state between these was considered somewhat good.

As shown in Table 19, the ink containing the epoxy compound having a solubility parameter of 19 MPa ^1/2 or more has good solubility of the vinyl ether compound and the photoacid generator. On the other hand, in the ink containing an epoxy compound having a solubility parameter of less than 19 MPa ^1/2 , the photoacid generator began to precipitate as a solid content and was found to exist as an impurity in the ink. Such impurities have the effect of lowering the ejection performance, lowering the ink sensitivity, and lowering the filtering conditions during the ink manufacturing process, and therefore it is desirable to reduce them as much as possible.

Furthermore, the influence of the viscosity of the epoxy compound was investigated and summarized in Table 20 below. Here, No. 1 is used except that an epoxy compound having a predetermined viscosity is blended. A plurality of inks were prepared according to the same formulation as the 13 inks. The viscosity and ejection performance of these inks were examined, and the results obtained are shown in Table 20 below. As a comparative example, Table 21 also shows the results of inks prepared by blending a low viscosity compound of an epoxy compound instead of a vinyl ether compound.

  As shown in the above table, by using a vinyl ether compound, an ink having excellent compatibility with a high viscosity acid polymerizable compound and a low viscosity can be obtained. In addition, the ejection performance of the obtained ink is good. Since such an ink can be further added with a high-viscosity acid-polymerizable compound, it is possible to impart gloss to the surface of the ink cured film, and the effect of increasing the flexibility of the ink layer can also be obtained. . On the other hand, an ink containing a low-viscosity epoxy compound has been difficult to reduce to a viscosity suitable for ejection conditions, and has poor photosensitivity.

Various ink-jet inks were prepared by blending the solvents A2, A7 and A10 and the respective components according to the formulation shown in Table 22 below.

  Examples of black (BK), yellow (Y), cyan (C), and magenta (M) pigments include carbon black, C.I. I. Pigment Yellow 180, C.I. I. Pigment Blue 15, and C.I. I. Pigment Red 123 was used.

A compound formulated as a photoacid generator is shown in the following chemical formula.

  PAG5 is a 50% propylene carbonate solution of a mixture of PAG1 and PAG2.

Moreover, the compound (BS1-BS7) mix | blended as a viscosity stabilizer is shown to the following chemical formula. The compound was added in a mol% with respect to the net photoacid generator (for example, 8.3 mol% corresponding to about 1 wt% in the combination of BS and PAG5).

  In preparing the ink, first, each pigment was pre-kneaded with an acrylic resin-based dispersant to make a mill base, and 200 ppm nonionic surfactant (manufactured by Sumitomo 3M) and a commercially available dispersant (manufactured by Ajinomoto Fine-Techno, product name) Ajisper) was added. Next, according to the formulation shown in Table 20, a pigment, a photoacid generator, and a viscosity stabilizer were added, and the mixture was dispersed by a paint shaker day and night. By filtering the mixture after the dispersion treatment with a 5 μm PTFE filter, No. 4 was obtained. Inks 16 to 31 were obtained.

  Further, no pigment or viscosity stabilizer was added. No. 32 ink was prepared and no viscosity stabilizer was added as an example. Two inks were used.

  The ink thus prepared is allowed to stand for 6 months under normal temperature conditions, the viscosity is measured, the storage stability is evaluated from the rate of increase in viscosity, and the results are summarized in Table 22 below. The rate of increase in viscosity was evaluated by measuring the viscosity after leaving each ink for 6 months at room temperature to determine the rate of increase in viscosity before and after being left.

A: 10% or less B: 10-20%
C: 20% or more

  As shown in Table 23 above, no. 32 and no. 2, the viscosity increase rate exceeded 10%. Thus, the ink (No. 32, No. 2) which does not contain a viscosity stabilizer has a large increase in viscosity.

Next, each ink after being left for 6 months under the above-mentioned conditions was applied to the ink jet recording apparatus 1 shown in FIG. 2, and the exposure amount and the hardness of the ink cured film were examined. A normal glossy paper was used as the recording medium 2 and an ultrahigh pressure mercury lamp with an output of 230 W was used as the light source 5. As the performance of the ink, the pencil hardness of the ink layer (the hardness of the ink layer maintained at a temperature of 80 ° C. for 3 minutes in the stocker after exposure) and the print quality were measured. The performance of the ink in the initial state before storage was similarly examined, and the results are shown in Table 24 below together with the exposure amount.

  As shown in Table 24 above, no. The ink of No. 2 has a markedly increased viscosity after being allowed to stand for 6 months, and is in a state where it cannot be ejected. In contrast, inks (Nos. 16 to 31) containing a basic compound or basic expression compound as a viscosity stabilizer can be discharged well even after being left for 6 months, and the viscosity is significantly stable. It has become.

  Moreover, when these inks were examined for corrosiveness to nickel metal used for piping and head members, no corrosion was observed. On the other hand, in the ink (No. 32) and the ink (No. 2) not containing the viscosity stabilizer, some corrosion was observed, and it was confirmed that the viscosity stabilizer also functions as an anticorrosive agent.

Next, No. 1 was changed except that the addition amount of the basic compound BS3 as a viscosity stabilizer (mol% relative to the photoacid generator) was changed. Several types of compositions were prepared with the same composition as the 23 inks. For each ink, the pencil hardness and the viscosity increase rate after 6 months were measured, and the obtained results are shown in Table 25 below together with the ratio of the compound BS3.

  As shown in Table 25 above, when the viscosity stabilizer is blended at a ratio of 1 mol% with respect to the amount of the photoacid generator, almost no stabilizing effect can be obtained. On the other hand, if the content exceeds 30 mol%, the curability of the ink is lowered. From this result, it can be seen that the addition amount of the viscosity stabilizer is preferably 1 mol% or more and 30 mol% or less of the photoacid generator.

Furthermore, the influence of pKb of the basic compound was examined. Here, except that the pKb of the basic compound to be added was changed as shown in Table 26 below, Various inks were prepared in the same manner as the 16 inks. These inks were examined for storage stability and photosensitivity, and the results obtained are shown in Table 26.

  Each ink was allowed to stand for 6 months under normal temperature conditions, the viscosity was measured, and the preservability was evaluated as follows from the rate of increase in viscosity before and after being left.

A: 10% or less B: 10-20%
C: 20% or more The photosensitivity was examined by the exposure amount when the pencil hardness of the ink cured film showed H, and was evaluated according to the following criteria.

A: Reaching H when the exposure amount is less than 300 mJ / cm ² B: Reaching H when the exposure amount is 300 mJ / cm ² or more As shown in Table 26 above, a basic compound having a pKb value of 3 or more and 7 or less is added. By doing so, it can be seen that an ink-jet ink having good storage stability and photosensitivity can be obtained.

1 is a schematic view of a recording apparatus that can use an inkjet ink according to an embodiment of the present invention. 1 is a schematic view of a recording apparatus that can use an inkjet ink according to an embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Inkjet recording device, 2 ... Recording medium, 3 ... Conveyance mechanism,
4 ... Inkjet recording head, 5 ... Light source, 6 ... Heater, 7 ... Stocker.

Claims (11)

It contains a photoacid generator that generates an acid upon irradiation with light, a color component, and an acid polymerizable compound that polymerizes in the presence of an acid, and the acid polymerizable compound includes a compound represented by the following general formula (1) An inkjet ink characterized by the above.

(In the general formula (1), R ¹³ is selected from alkoxy and hydroxyl substituents, at least one is an alkoxy group, .R ¹⁴ of at least two is a group having a vinyl ether group or a vinyl ether skeleton A substituted or unsubstituted cyclic skeleton represented by the following general formula (VE1-a) or (VE1-b), and p is an integer of 2 or more.)

(In the above general formula, X 1 and Z 1 are alkylene groups having 1 to 5 carbon atoms, Y 1 is an alkylene group having 1 to 2 carbon atoms, and k is 0 or 1.) The inkjet ink according to claim 1, wherein the compound represented by the general formula (1) is any compound represented by the following chemical formula.

It contains a photoacid generator that generates an acid upon irradiation with light, a color component, and an acid polymerizable compound that polymerizes in the presence of an acid, and the acid polymerizable compound includes a compound represented by the following general formula (1) An inkjet ink characterized by the above.

(In the general formula (1), R ¹³ is selected from alkoxy and hydroxyl substituents, at least one is an alkoxy group, .R ¹⁴ of at least two is a group having a vinyl ether group or a vinyl ether skeleton And a cyclic skeleton composed of a substituted or unsubstituted aromatic ring skeleton, and p is an integer of 2 or more.) 4. The compound represented by the general formula (1), wherein at least one of R ¹³ is a vinyl ether group directly bonded to the cyclic skeleton. 5. Inkjet ink.   The inkjet ink according to any one of claims 1 to 4, wherein the acid-polymerizable compound further contains at least one selected from a cyclic carbonate and a cyclic lactone compound.   The inkjet ink according to any one of claims 1 to 4, wherein the acid-polymerizable compound further contains an oxetane compound.   The inkjet ink according to claim 1, wherein the acid polymerizable compound further contains diglycidyl ether of neopentyl glycol.   The compound represented by the general formula (1) occupies at least 40 parts by weight of the acid polymerizable compound, and the viscosity of the ink at room temperature is 12 mPa · sec or less. The inkjet ink according to item 1. The compound represented by the general formula (1) occupies at least 40 parts by weight of the acid polymerizable compound, and further contains an epoxy compound and / or an oxetane compound having a solubility parameter of 19 MPa ^1/2 or more. The inkjet ink according to any one of claims 1 to 7.   The compound represented by the general formula (1) occupies at least 40 parts by weight of the acid polymerizable compound, and further contains an epoxy compound and / or an oxetane compound having a viscosity at room temperature exceeding 500 mPa · sec. The inkjet ink according to any one of claims 1 to 7.   11. The method according to claim 1, further comprising at least one compound selected from the group consisting of a basic compound and a compound that expresses basicity, and having a pKb of 3 to 7 at 25 ° C. The ink-jet ink according to item.

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