JP4727690B2 - Inkjet recording device - Google Patents

Description

  The present invention relates to a recording apparatus, and more particularly to an ink jet recording apparatus.

  Conventionally, printing presses using plates have been used for producing printed materials that require a certain number of copies, such as regional advertisements and company distribution materials. 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 printing machine, an inkjet printer capable of high-speed and high-quality printing is expected.

  As a technique for printing a high-definition image with an inkjet printer, it is known to use a solvent-based ink or a solvent-based liquid toner containing a pigment and an organic solvent, as in a printing machine using a plate. However, in such a technique, when a certain number of copies are printed, a non-negligible amount of organic solvent volatilizes. Therefore, there has been a problem of atmospheric contamination due to the volatilized organic solvent, and it was necessary to provide an exhaust facility and a solvent recovery mechanism.

  As an effective technique for the above problems, photosensitive ink and a printer system using the same have begun to attract attention. This technique quickly cures the photosensitive ink discharged on the printing surface. As the photosensitive ink to be used, one containing a radical polymerizable monomer, a photopolymerization initiator and a pigment as essential components is typical.

  Since the ink layer can be made non-fluidized by light irradiation, a relatively high quality printed matter can be obtained by such a method. However, the ink used contains a large amount of carcinogenic components such as a radical generator, and the volatile acrylic acid derivative used as a radical polymerizable monomer has a large skin irritation and odor. That is, the above ink requires attention in handling. Further, radical polymerization is significantly inhibited by the presence of oxygen in the air, and the pigment contained in the ink absorbs exposure light. For this reason, the exposure amount tends to be insufficient in the deep part of the ink layer. For this reason, the photosensitive ink described above has low sensitivity to light, and a very large exposure system is required to obtain a high-quality printed material with this system.

  As a solution to these problems, cationic curable inks that are cured by irradiation with active energy rays have been proposed (see, for example, Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4). For example, the cationic curable ink is ejected from an ink jet print head to form an ink layer corresponding to an image on a recording medium. Thereafter, the ink layer is cured by irradiating active energy rays such as ultraviolet rays or electron beams.

However, a common problem with photocationic curable inkjet inks is that the change in viscosity over time is severe. This is due to the fact that there are many dark reactions of ink. When the viscosity changes, in the case of inkjet ink, the flying shape of the ink is disturbed and the print reproducibility is reduced. In the worst case, this problem is extremely serious because it tends to be fatal such as ejection failure or ink clogging. An effective means for solving the problem of viscosity increase of inkjet ink has not yet been obtained.
Japanese Patent Laid-Open No. 9-183928 JP 2001-220526 A JP 2002-188025 A JP 2002-317139 A

  Photocationic curable ink-jet inks containing oxirane group-containing compounds, oxetane ring-containing compounds, vinyl ether compounds, pigments, pigment dispersants, photoacid generators, and other additives have many dark reactions. Change (thickening) is large, ink storage stability is poor and life is short.

  SUMMARY An advantage of some aspects of the invention is that it provides an ink jet recording apparatus that can stably produce high-quality printed matter with high reproducibility.

An ink jet recording apparatus according to an aspect of the present invention includes a colored ink container that contains a colored ink containing a solvent that polymerizes in the presence of an acid and a color component dispersed in the solvent.
Photoacid generator which generates an acid by light irradiation to accommodate a reaction solution formed by adding to the solvent, the reaction liquid container that will be stored by the lower color ink container temperature,
A stirring container for obtaining a recording ink by mixing the colored ink and the reaction liquid;
A pump for supplying colored ink that supplies the colored ink from the colored ink container to the stirring container at a volume S1;
A reaction liquid supply pump for supplying the reaction liquid from the reaction liquid container to the stirring container at a volume S2 (S2 <S1);
An ink jet recording head that discharges the recording ink onto a recording medium, and a supply pipe that supplies the recording ink in the stirring container to the ink jet recording head are provided.

  According to one embodiment of the present invention, there is provided an ink jet recording apparatus that can stably produce a high-quality printed matter with high reproducibility.

  Embodiments of the present invention will be described below.

  The ink-jet ink according to the embodiment of the present invention is composed of two types of solutions prepared separately and stored separately. The first solution contains a solvent that polymerizes in the presence of an acid and a color component dispersed in the solvent, and the second solution contains a photoacid generator that generates an acid upon irradiation with light. Being done.

  When used in the ink jet recording apparatus according to the embodiment of the present invention, these two kinds of solutions are separated and stored in separate containers, and are mixed immediately before being supplied to the ink jet recording head. After thorough mixing by stirring, ink composed of a mixture of two solutions is supplied to an ink jet recording head and ejected onto a recording medium. In the present specification, the ejected ink is referred to as “recording ink”.

  The recording ink is ejected onto the recording medium, and an ink layer corresponding to the image is formed. By irradiating the ink layer 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. Further, the generated acid diffuses in the ink layer. Moreover, the acid diffusion and the acid-catalyzed crosslinking reaction can be accelerated by heating. Unlike the radical polymerization, this crosslinking reaction is not inhibited by the presence of oxygen. Therefore, a plurality of cross-linking reactions can be caused by one photon, and high sensitivity can be realized. In addition, the crosslinking reaction can be rapidly advanced even in the deep part of the ink layer or inside the absorbent medium.

  Therefore, when such a recording ink is used, the ink layer can be quickly made non-fluid by performing light irradiation and heating after forming the ink layer by discharging it onto the printing surface. That is, a high-quality printed matter can be obtained without requiring a large-scale exposure system.

  Furthermore, in the present embodiment, the above-described polymerizable compound is used as at least a part of the solvent, and typically almost the entire solvent is composed of the polymerizable compound. Therefore, if the ratio of the polymerizable compound in the solvent is sufficiently high, the organic solvent hardly volatilizes during printing. Therefore, it is possible to prevent the problem of atmospheric pollution caused by the volatilization of the organic solvent, and an exhaust facility and a solvent recovery mechanism are not required.

  In addition, in the present embodiment, it is not necessary to use an organic solvent, and the ink layer can be quickly non-fluidized. For this reason, it is possible to easily fix an image to various printing surfaces having different properties with almost no bleeding, and it is difficult to cause deterioration of the printing surface due to drying of the ink layer. . Furthermore, since the inkjet ink according to the present embodiment can contain a pigment at a high concentration as a color component, it is possible to form a print pattern that is clear and has excellent weather resistance.

  Hereinafter, each solution constituting the inkjet ink according to the embodiment of the present invention will be described in detail.

  The first solution contains a solvent that polymerizes in the presence of an acid and a color component dispersed in the solvent, and is referred to as a colored ink.

  The solvent that is polymerized in the presence of an acid is a compound having a viscosity of 30 mPa · s or less at normal temperature and pressure and a boiling point of 150 ° C. or more, more preferably a compound having a boiling point of 180 ° C. or more, as follows: Compounds. That is, a compound having a molecular weight of 1000 or less having at least a cyclic ether group such as an epoxy group, an oxetane group or an oxolane group is preferred. Furthermore, acrylic or vinyl compounds, carbonate compounds, low molecular weight melanin compounds, vinyl ethers and vinyl carbazoles, styrene derivatives, alphamethyl styrene derivatives, vinyl alcohol and acrylic, methacrylic esters having the above-mentioned substituents in the side chain Monomers having a vinyl bond capable of cationic polymerization such as vinyl alcohol esters including compounds may be used in combination.

  In particular, when the polymerizable compound that crosslinks in the presence of an acid has an aliphatic skeleton or an alicyclic skeleton, the addition of the above-described other components in addition to the polymerizable compound increases the transparency of the recording ink during exposure. Appropriate thermoplasticity and re-dissolvability can be imparted to the ink layer after curing. As a result, sensitivity, fixability, transferability and maintainability are improved. In particular, when the polymerizable compound is an epoxy compound having an alicyclic skeleton, a certain degree of high boiling point and low viscosity can be achieved in addition to reactivity.

  On the other hand, when a curing speed is particularly required for the ink according to the embodiment of the present invention, for example, when high-speed printing of several tens of meters per minute is required, it is preferable to add an oxetane compound. . Since this oxetane compound has an action of accelerating and accelerating curing, primary curing can be accelerated. However, in this case, since the thermoplasticity is lowered, the thermal transfer performance tends to decrease according to the addition amount. Therefore, the amount of oxetane compound added is desirably in the range of 10 to 40 parts by weight of the total solvent. If this range is exceeded, curing will not be accelerated, or nozzles or thermoplasticity will tend to occur.

  Examples of oxetane compounds that can be used 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, phenol novolac oxetane, oxetanylsilsesquioxane, Aron oxetane OXT-101, OXT-102, 1,4-bis [(1 -Ethyl-3 oxetanyl) methoxy] cyclohexane, 1,4-bis [(3-ethyl-3oxetanyl) methoxy] cyclohexane, 1,2-bis [(1-ethyl-3oxetanyl) methoxy] norbornane, 2 or more Aliphatic or alicyclic compounds having an oxetane group, acrylics having an oxetane group in the side chain , And the like methacrylic compound.

  Further, when a decrease in viscosity is required in addition to an improvement in the curing rate, it is preferable to further add a vinyl ether compound. By containing the vinyl ether compound, it is possible to increase the curing speed and extremely reduce the viscosity of the ink without extremely increasing the volatility.

  Examples of such vinyl ether compounds include p + 1 valent groups including a benzene ring, a naphthalene ring, and a biphenyl ring, a cycloalkane skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodencan skeleton, a tetracyclododecane skeleton, a terpenoid skeleton, a cholesterol skeleton, and the like. Examples thereof include a compound in which a vinyl group is bonded to an induced p + 1 valent group via an ether bond. More specific examples include polyvinyl etherified compounds such as cyclohexane, norbornane, tricyclodecane, adamantane, benzene, and naphthalene.

  In the ink according to the embodiment of the present invention, it is preferable to add a compound having an aromatic skeleton when the printed matter requires resistance to a solvent such as alcohol. Thereby, since hardening can be accelerated | stimulated and accelerated, tolerance improves. Among these, addition of an oxetane compound or a vinyl ether compound containing a divalent or higher aromatic skeleton is desirable. Examples of such oxetane compounds include 1,4-bis [(1-ethyl-3oxetanyl) methoxy] benzene, 1,3-bis [(1-ethyl-3oxetanyl) methoxy] benzene, 4,4′-bis [ Examples include (3-ethyl-3oxetanyl) methoxy] biphenyl, phenol novolac oxetane, and alicyclic compounds having two or more oxetane groups.

  The first solution may contain a small amount of a highly viscous compound as part of the solvent. For example, it is a compound that has a relatively high molecular weight and is solid at room temperature. When such a component is further contained, the flexibility of the ink layer after curing and the dispersibility of the pigment can be improved. Moreover, when a highly reactive compound having a large valence is used, the hardness and solvent resistance of the cured product can be increased.

  Examples of such a 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, and an acrylic having the above substituent in the side chain. Or vinyl compounds, carbonate compounds, low molecular weight melanin compounds, vinyl ethers and vinyl carbazoles, styrene derivatives, alpha-methylstyrene derivatives, vinyl alcohol esters including vinyl alcohol and acrylic, methacrylic ester compounds, etc. Examples include a monomer having a cationically polymerizable vinyl bond and an oligomer obtained by polymerizing at least one of the monomers.

  In addition to the above-mentioned compounds, the solvent in the first solution includes an acid-reactive / dehydrating-condensable OH group, COOH group, acetal group, etc., such as vinyl alcohol alone or a copolymer, casein, and cellulose. A resin having a molecular weight of 5000 or less, a polycarbonate resin having a molecular weight of 5000 or less, a polyamic acid, a polyamino acid or a copolymer of acrylic acid and a vinyl compound having an acid-polymerizable double bond in the side chain, vinyl alcohol and an acid in the side chain You may further contain the copolymer with the vinyl compound which has a polymerizable double bond, and the methylol-ized melamine resin.

Since the ink in the embodiment of the present invention is a photosensitive ink that needs to be heated, the volatility of the ink is preferably low from the viewpoint of safety and odor. For example, it is desired that the volatilization rate at 80 degrees after exposure is 0.2 mg / cm ² · min or less. The volatilization amount here indicates the volatilization amount (mg) per minute when, for example, a container having an opening area of 10 cm ² is heated. Although this value depends on the opening of the container, it is usually defined as a value when 4 g of ink is taken in a petri dish having a diameter of 6 cm and heated under normal pressure. A composition that deviates from this range has a too high volatilization rate at the time of heating, which impairs safety and causes a significant odor problem. 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 high, and ink jet ejection is often difficult.

  If the cured ink layer has sufficient thermoplasticity and re-solubility, the recording ink is ejected onto the image carrier to form an ink layer, and then the ink layer is applied onto the recording medium. Can be transferred. That is, the recording ink is ejected onto the image carrier to form an ink layer, and the ink layer is cured or precured by light irradiation and heating. Further, the ink layer is reflowed or plasticized by applying pressure or pressure and heat in a state where the recording medium is in contact with the ink layer. Thus, the image can be transferred onto a recording medium. On the other hand, when the recording ink is directly ejected onto the recording medium, first, an ink layer is formed on the recording medium and cured or precured by light irradiation and heating. Furthermore, the ink layer can be permanently cured by applying heat to be fixed on the recording medium.

  If the polymerizable compound described above contains an aliphatic skeleton or alicyclic skeleton having a cyclic ether group such as an epoxy group, an oxetane group or an oxolane group, it is basically suitable for a cured ink layer. Thermoplasticity and re-solubility can be imparted. In particular, it is desirable to use an epoxy group having an excellent acid polymerizability. Examples of such a compound include a hydrocarbon group having a divalent aliphatic or alicyclic skeleton having about 1 to 15 carbon atoms, or a divalent having a part of an aliphatic chain or alicyclic skeleton. A compound having an epoxy group or an alicyclic epoxy group in one or both of the groups can be exemplified.

The number of epoxy groups introduced into the molecular skeleton is not particularly limited. However, in order to impart flexibility and re-solubility to the ink layer after curing, the valence should be about 2 to 3 at most. Is desirable. Examples of such a polymerizable compound include compounds represented by the following general formulas (1) and (2).

In the general formulas (1) and (2), R1 to R5 each represents an epoxy group or an epoxy group having an alicyclic skeleton, and A1 and A2 represent functional groups.
These compounds represented by the general formulas (1) and (2) usually have a low viscosity of about 1 cP to 30 cP. Therefore, blending such a low viscosity compound is effective in sufficiently reducing the viscosity of the ink.

In addition, the alicyclic epoxy compound represented by the following general formula (3) usually has a high viscosity of about 20 cP to 500 cP. Therefore, by using this high-viscosity compound, flexibility or hardness can be imparted to the cured ink layer.

  In the general formula (3), R4 and R5 each represent an epoxy group or an epoxy group having an alicyclic skeleton, and A3 represents a k + 1-valent functional group (k + 1) having at least an alkylene group and / or an alicyclic skeleton. Indicates a natural number).

  It is preferable that at least one of the low-viscosity compound and the high-viscosity compound described above is mixed and used. For example, when 100 parts by weight of the first solution is added at a ratio of 5 to 90 parts by weight of the low-viscosity compound and 1 to 40 parts by weight of the high-viscosity compound, the minimum required for ejection This is advantageous for realizing the limited fluidity (viscosity of 30 cP or less at 50 ° C.). In particular, the weight ratio of the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3) is preferably about 1: 1 to 10: 1.

  Examples of the aliphatic epoxy compounds described above include alicyclic epoxies exemplified by Celoxide 2021, Celoxide 2021A, Celoxide 2021P, Celoxide 2081, Celoxide 2000, and Celoxide 3000 manufactured by Daicel Chemical Industries, and (meth) acrylates having an epoxy group. 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 T301, and the like polyfunctional epoxy such as Epolead GT401. In addition, US Dow Chemical's alicyclic epoxy such as Cyracure, hydrogenated and aliphatic low molecular weight phenolic compounds with hydroxyl groups substituted with epoxy groups, ethylene glycol, glycerin, neopentyl alcohol Further, glycidyl ether compounds such as aliphatic alcohols / alicyclic alcohols such as hexanediol and trimethylolpropane, hexahydrophthalic acid, and glycidyl esters of hydrogenated aromatic polycarboxylic acids can be used. In addition, in order to improve the chemical resistance of the image, epoxidized polybutadiene such as Epelod PB3600 and PB3600M manufactured by Daicel Chemical Industries, transparent liquid epoxy resin having high weather resistance such as EHPE3150 and EHPE3150CE, and the like are added. Also good. Alternatively, in addition to these, a lactone-modified alicyclic epoxy resin may be added. For example, Daicel's Plaxels GL61, GL62, G101, G102, G105, G401, G402, and G403X can be exemplified.

  Among these, compounds obtained by modifying Celoxide 2000, Celoxide 3000, α-pinene oxide ethylene glycol, glycerin, neopentyl alcohol or hexanediol alcohol with glycidyl ether are desirable from the viewpoints of viscosity and volatility.

  When the alicyclic skeleton contained in the epoxy compound described above has a terpenoid skeleton, the safety of the ink or the cured ink layer with respect to the human body and the environment is improved. Such epoxy compounds include, for example, myrcene, ocimene, geraniol, nerol, linalool, citrolenol, citral, menten, limonene, dipentene, terpinolene, terpinene, ferrandrene, sylvestrene, piperitol, terpineol, terpineol, menthene monool, Terpene compounds having an unsaturated bond such as isopulegol, peralaldehyde, piperitone, dihydrocarbon, carvone, pinol, ascaridol, zabinene, carene, pymene, bornene, fenken, camphene, carbeol, sesquiterpenes, diterpenes, triterpenes A compound obtained by oxidizing and epoxidizing the unsaturated bond is preferable. In addition, an epoxy compound obtained by oxidizing a naturally occurring norbornene compound is favorable in terms of cost.

  In addition, for oxidation to epoxy, for example, many oxidation techniques in which an oxidizing agent such as peracetic acid acts can be used. Among these, an air oxidation method using N hydroxyphthalimide and a rare earth catalyst as shown in JP-A-11-49764 is most preferably used.

  The compound that polymerizes in the presence of an acid as described above can be selected according to the photoacid generator contained in the second solution described later. In this case, what is necessary is just to adjust the quantity of each component so that it may become predetermined | prescribed content in the state used as recording ink. For example, 30 to 70 parts by weight of an alicyclic epoxy compound having a terpenoid skeleton or a norbornane skeleton, and 30 to 70 parts by weight of an epoxy compound having an aliphatic skeleton having two or more glycidyl ether groups within 6 carbon atoms. When a compound that is polymerized in the presence of an acid in the first solution is constituted by a mixture with parts by weight, the color component can be blended in a proportion of 1 to 10 parts by weight. As the photoacid generator in the second solution, a hexafluorophosphate compound having a phenylsulfonium skeleton is used so that the content of the photoacid generator in the recording ink is 1 to 10 parts by weight. It is preferable to mix the first solution and the second solution. In this case, in addition to the photosensitive performance, hardness, adhesion and transferability are particularly satisfactory.

  Examples of alicyclic epoxy compounds that can be used include limonene (di) oxide, (di) oxabicycloheptane, and substituted compounds thereof. Epoxy compounds having 6 or less carbon atoms include neopentyl glycol diglycidyl ether, ethylene glycol. Examples thereof include diglycidyl ether, glycerol di (tri) glycidyl ether, 1,6-hexanediol diglycidyl ether and the like. Of these, the combination of limonene dioxide and neopentyl glycol diglycidyl ether is most preferred. When the number of carbons exceeds 6, the hardness, adhesion, and transferability may be reduced.

  When an epoxy compound is used in the combination described above, the cured ink layer is reflowed from a temperature of at least 50 ° C., preferably about 80 ° C., so that fixing and transfer can be performed satisfactorily. Further, in this case, the cured ink layer is redissolved in the liquid ink, or is relatively soluble in an organic solvent composed of a low-boiling petroleum component such as lower alcohol such as ethanol or Isopar. Therefore, the occurrence of nozzle clogging can be suppressed, and even when nozzle clogging occurs, the nozzle clogging can be easily eliminated. That is, the head maintenance performance is significantly improved.

  However, the characteristics required for the printed matter differ depending on the application. For example, when the printed matter is used for the exterior of a can or a plastic bottle or the exterior of a container made of an oily material, the first solution contains a compound having a phenolic hydroxyl group, such as bisphenol A, in addition to the epoxy compound described above. Glycidyl ether compounds, glycidyl ether compounds of phenolic oligomers such as phenol novolac and polyhydroxystyrene, general aromatic epoxy compounds such as styrene oxide, oxetane compounds having an aromatic skeleton, and crosslink density In order to improve the above, a trivalent or higher polyvalent epoxy compound or a trivalent or higher polyvalent vinyl ether compound may be added.

  A first solution is prepared by dispersing the color component in a polymerizable solvent in the presence of an acid as described above.

As the color component, a pigment and / or a dye can be contained. However, in the embodiment of the present invention, since an acid is used, a pigment is preferable to a dye that easily fades with an 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. The pigment used here may further exhibit other properties such as magnetism, fluorescence, conductivity, dielectricity, etc. in addition to coloring and coloring properties. In this case, various functions can be given to the image. In addition, powder capable of improving heat resistance and physical strength can be added.

  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.

  Examples of pigments include dye chelates (basic dye type chelates, acidic dye type chelates, etc.), nitro pigments, nitroso pigments such as aniline black and naphthol green B, Bordeaux 10B, Lake Red 4R, and chromoftal red. Azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), lake 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, isoindolinone pigments, quinofuranone pigments), selenium pigments such as thioindigo red and indatron blue, quinacridone pigments, quina It is also possible to use organic pigments such as lysine pigments, and isoindolinone pigments.

  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 black such as U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, Special Black 4, and the like.

  Examples of pigments that can be used in yellow ink include Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 151, 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, C.I. I. Pigment and the like.

  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 Red 112 and the like.

  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, C.I. I. Vat Blue 60 etc. are mentioned.

  Further, white pigments such as natural clay, metal white oxides such as white lead, zinc white and magnesium carbonate, and metal oxides such as barium and titanium are also useful. The recording ink containing a white pigment can be used not only for white printing but also for print 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 the organic phosphor material include acridine orange, aminoacridine, quinacrine, anilinonaphthalene sulfonic acid derivative, 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-diazol, 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 capable of improving the heat resistance and physical strength of the ink layer include aluminum and silicon oxides or nitrides, fillers, and silicon carbide. In order to impart conductivity to the ink layer, powders such as conductive carbon pigment, carbon fiber, copper, silver, antimony, or noble metals may be added. Iron oxide and ferromagnetic powder are suitable for imparting magnetism, and metal oxide powders such as tantalum and titanium having a high dielectric constant can also be blended.

  It is also possible to add a dye as an auxiliary component of the pigment. For example, dyes having low acidity and basicity and high solubility in epoxy, such as azoic dyes, sulfur (building materials) dyes, disperse dyes, fluorescent brighteners, and oil-soluble dyes, are usually used. Of these, oil-soluble dyes such as azo, triarylmethane, anthraquinone, and azine are preferably used. For example, as an example, C.I. I. Slovel 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.

  The pigments and dyes described above may be used alone or as a mixture of two or more. Further, both pigments and dyes may be added in order to increase the 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 pigment content in the ink according to the embodiment of the present invention is preferably 1% by weight to 25% by weight. When the pigment content is less than 1% by weight, the color density is low, and when it exceeds 25% by weight, the ink dischargeability is lowered. Further, the content of the powder component in the ink is desirably 1% by weight 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 the recording ink obtained by mixing with the second solution, the content in the first solution may be appropriately selected so that the pigment and the like are contained within such a range.

  The average particle diameter of the pigment or powder used is desirably as small as possible. The average particle diameter of these pigments and powders is usually 1/3 or less, preferably about 1/10, of the opening diameter of the nozzle for discharging the recording ink. This size is typically 10 μm or less, preferably 5 μm or less. A particle size suitable as a printing ink is 0.35 μm or less.

  A small amount of a nonionic or ionic surfactant or a charging agent such as a charging agent can be added to the first solution in order to enhance the dispersibility of the pigment or the like. In addition, polymer 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 one having an acidity lower than that of the carboxylic acid. This is because some cationic dispersants promote the curing dark reaction of the ink. In addition, dispersants and pigments having strong basicity not only reduce the sensitivity of the ink, but may also promote the curing dark reaction, so these dispersants are close to neutral or nonionic. desirable.

  It is preferable to add at least one of a basic compound and a compound for adjusting basicity to the first solution containing a color component 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. These basic compounds can be used alone or in combination of two or more.

  However, when an extremely strong basic compound such as imidazole is used, there is a possibility that, for example, polymerization with time occurs or a side reaction such as decomposition of the photoacid generator is likely to occur. 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 a suitable 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.

  Among these, when such a basic compound is an aniline derivative, it is particularly desirable in terms of viscosity stability, volatility, basicity, and low side reactivity.

  However, since the aniline compound described above has low basicity, the compound itself is generally not desirable in combination with a monomer having an oxetane group having basicity. The oxetane compound is preferably a more basic compound having a pKb at 25 ° C. of 7 or less and 3 or more. For example, a basic compound such as an amine having an aliphatic skeleton or an amine having an alicyclic skeleton can be preferably used.

  Since the ink according to the embodiment of the present invention is heated after exposure, the volatility of the basic compound is desirably as low as possible. Specifically, the boiling point is desirably 150 ° C. or higher, more preferably 180 ° C. or higher at room temperature.

  In order to obtain the effect of stabilizing the viscosity without significantly reducing the sensitivity, the content of the basic compound or the compound for adjusting the basicity is equal to the total molar amount of the content of the photoacid generator in the recording ink. On the other hand, the ratio is preferably 30 mol% or less and 1 mol% or more. More preferably, the content of the basic compound or the compound for adjusting basicity is 15 mol% or less and 2 mol% or more with respect to the photoacid generator. What is necessary is just to adjust content and mixing ratio in a 1st solution so that it may become in such a range after mixing with a 2nd solution.

  In addition, when a photosensitive basic compound that is decomposed by irradiation with light or radiation is used, it is desirable because a decrease in sensitivity associated with the addition of a base can be reduced. As such a photosensitive basic compound, a sulfonium compound or an iodonium compound can be preferably used.

  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 the photoacid generator used is an onium salt, the photoacid generator and the basic compound are preferably the same type of compound. For example, when both are sulfonium compounds and iodonium compounds, more excellent effects can be obtained in terms of sensitivity and storage stability.

  The first solution may further contain a radical polymerizable compound. The radically polymerizable compound can reduce the influence when the printing surface is strongly basic, or when the pigment or the printing surface is easily affected by the acid. Examples of such compounds include acrylic or methacrylic monomers, styrene monomers, or compounds having a plurality of their vinyl polymerizable groups. In particular, when a compound having both cationic polymerizability and radical polymerizability such as CEL2000 manufactured by Daicel Chemical Industries, ester compound such as glycidyl methacrylate, vinyl alcohol and acrylic, methacryl is added, radical polymerizability and cationic polymerizability. The benefits of 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 also be contained at the same time. These techniques can also be used when it is desired to impart high chemical resistance to the ink layer after curing.

  Next, the second solution will be described.

  The second solution is obtained by dissolving a photoacid generator that generates acid upon irradiation with light in a solvent, and is referred to as a reaction solution.

  Examples of the photoacid generator 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-hydroxyphenylsulfate, diphenylsulfonylmethane, diphenylsulfonyldiazomethane, diphenyldisulfone, α-methylbenzoin tosylate, pyrogallol trimesylate, benzoin tosylate, manufactured by Midori Chemical Co., Ltd. MPI-103 (CAS.NO. [87709-41-9]), Midori Chemical Co., Ltd. BDS-105 (CAS.NO. [145612-66-4]), Midori Chemical Co., Ltd. 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]), DTS-103 (CAS.NO. [71449-78-0]) manufactured by Midori Chemical, MDS-103 (CAS.NO manufactured by Midori Chemical) [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.) ), Midori Kagaku BMS-105 (CAS.NO. [149934-68-9]), Midori Kagaku TMS-105 (CAS.NO. [127820-38-6]), Midori Kagaku NB- 101 (CAS.NO. [20444-09-1]), Midori Chemical Co., Ltd. NB-201 (CAS.NO. [4450-68-4]), Midori Chemical Co., Ltd. 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]), DAM-102 (CAS.NO. [28343-24-0]) manufactured by Midori Chemical Co., Ltd., DAM-103 (CAS.NO. [14159-] manufactured by Midori Chemical Co., Ltd.) 45-6]), DAM-104 (CAS.NO. [130290-80-1], CAS.NO. [130290-82-3]), Midori Chemical Co., Ltd. DAM-201 (CAS.NO. [2832-50-1]), Midori Chemical Co., Ltd. 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]), UVACURE1591 manufactured by Daicel UCB, and the like.
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 R ₁₂ each 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 fluoroborate anion, hexafluoroantimonate anion, hexafluoroarsenate anion, trifluoromethanesulfonate anion, paratoluenesulfonate anion, and 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 an aromatic group and a chalcogenide atom, and A4 and A5 Are respectively anionic species selected from the group consisting of PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , AsF ₆ ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , and CH ₃ SO ₃ ⁻ . m and n are integers. 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 salts represented by the general formulas (4) and (5) have high curing reactivity and excellent stability at room temperature. Therefore, it can suppress that the recording ink hardens | cures in the state which is not irradiating light.

When the compounds represented by the general formulas (4) and (5) are used as a photoacid generator, the chalcogenide atom described above is a sulfur atom or an iodine atom from the viewpoint of thermal stability and moisture stability. preferable. 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. When a hexafluorophosphate compound having a phenylsulfonium skeleton is used, the photosensitivity can be improved, which is particularly desirable.

  In some cases, the photoacid generator may further contain a sensitizing dye. Examples of such sensitizing dyes 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.

An organic halide that can be used as a photoacid generator means a compound that forms hydrohalic acid. 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 2,243,621. 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. Among them, halomethyl-S-triazines such as 2,4-bis (trichloromethyl) -6-methyl-S-triazine and 2,4,6-tris (trichloromethyl) -S-triazine are preferable. More preferred organic halides include compounds substituted with vinyl halomethyl-S-triazine as 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 above general formula (A), Q represents a bromine or chlorine atom, P represents a —CQ ₃ , —NH ₂ , —NHR, —NR ₂ , or —OR group, and R represents phenyl or a carbon number of 6 The following lower alkyl groups are shown, 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 above general formula (B), Z represents an oxygen or sulfur atom, and R1 represents a lower alkyl group or a phenyl group.

The aromatic ring or heterocyclic ring represented by W in the above general formula (A) may be further substituted. Examples of the substituent in this case 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, a compound having a triazine ring in which trihalomethane is introduced into the skeleton can also be suitably used as a photoacid generator. Further, 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. In addition, as a compound mentioned above, the triazine and condensed triazine compound which have a naphthalene substituent can be mentioned, for example.

  Furthermore, a photodissociable acid ester or the like can also be suitably used as a photoacid generator. Examples of such a compound include ortho nitrobenzyl ester of aluminum silanol.

  The content of the photoacid generator in the recording ink can be set according to the acid generation efficiency of the photoacid generator to be used, the amount of the color component to be added, and the like. For example, when the concentration of the color component in the recording ink is about 5% by weight, the content of the photoacid generator is usually 1 with respect to 100 parts by weight of the total solid content contained in the recording ink. The amount can be from 10 to 10 parts by weight. If the ratio of the photoacid generator to the total solid content of 100 parts by weight is less than 1 part by weight, the sensitivity of the liquid ink is low, and if it exceeds 10 parts by weight, the ink thickens over time and the coating film becomes intense. Or the hardness of the ink film after photocuring may be reduced. The content of the photoacid generator is preferably 2 to 8 parts by weight, more preferably 2 to 4 parts by weight. What is necessary is just to adjust content of the photo-acid generator in a 2nd solution so that the recording ink after mixing with a 1st solution may contain a photo-acid generator within such a range.

  As the solvent for dissolving the photoacid generator as described above, for example, the same solvent as in the case of the first solution can be used.

  As with the first solution described above, it is usually desirable to prepare the second solution 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, and ethyl lactate may be inevitably mixed. For example, when an exhaust mechanism and a solvent recovery mechanism are provided, a small amount of an organic solvent may be contained 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.

  The first and second solutions as described above are used in the ink jet recording apparatus according to the embodiment of the present invention, and are mixed immediately before being supplied to the ink jet recording head. Thus, the resulting recording ink 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 or decomposition reaction. For this reason, in this recording ink, the presence of 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 recording ink but also in the manufacturing process of each component.

  FIG. 1 shows a schematic diagram of an ink jet recording apparatus according to an embodiment of the present invention.

  Recording ink is supplied from the ink stirring container 2 to the inkjet head 20 at a water head pressure. The supplied ink is ejected on the recording medium M conveyed by a conveying means (not shown) in accordance with the image information to form an image. The ink stirring container 2 is supplied with the first solution as the colored ink and the second solution as the reaction liquid so as to have a predetermined mixing ratio. The mixing ratio (S2 / S1) between the second solution and the first solution in the ink stirring container 2 is usually about (1/32). As described above, the first solution contains a solvent that polymerizes in the presence of an acid and a color component, and is supplied from the colored ink container 5 via the colored ink supply pump 6. From the viewpoint of ink storage stability, the first solution preferably contains a basic compound. On the other hand, the second solution contains a photoacid generator and is supplied from the reaction solution container 3 through the reaction solution supply pump 4.

  Since the amounts of the first and second solutions supplied to the ink stirring container 2 are different, the capacities of the two containers (the colored ink container 5 and the reaction liquid container 3) that store these two types of solutions are also different. The ratio (V2 / V1) between the capacity (V2) of the reaction liquid container 3 and the capacity (V1) of the colored ink container 5 is preferably smaller than the mixing ratio (S2 / S1) of the solution in the ink stirring container. Thereby, the replacement frequency of the colored ink container 5 is reduced from the replacement frequency of the reaction liquid container 3. Opportunities to stop the printing operation to replace the colored ink container 5 are reduced, and productivity can be increased. As will be described later, it has been found by the present inventors that the increase in the viscosity of the ink is caused by the thermal decomposition of the photoacid generator, and the colored ink alone does not increase in viscosity. Therefore, the first solution stored in the colored ink container 5 does not affect the increase in viscosity even when the storage period is extended, and the image is not deteriorated.

  In the ink stirring container 2, a stirring blade 8 connected to a motor 7 is installed, and the reaction liquid and the colored ink are stirred and mixed to obtain an ink for ink jet recording. In the vicinity of the ink stirring container 2, the reaction liquid container 3, and the colored ink container 5, a recording ink remaining amount detection sensor 9, a reaction liquid remaining amount detection sensor 10, and a colored ink remaining amount detection sensor 11 are provided. Yes. These sensors are configured as follows. Transparent windows are provided on the side surfaces of the ink agitation container 2, the reaction liquid container 3, and the colored ink container 5, and light from an LED or the like is irradiated on the windows. The reflected light of this light is detected, and the remaining amount of ink is detected based on the change in the amount of reflected light. Further, the ink remaining amount detection sensor 9 can detect not only the presence / absence of the remaining amount of ink in the ink stirring container 2 but also the remaining amount at several levels.

  Further, a cooling fan 12 is provided in the vicinity of the reaction liquid container 3, and the storage temperature of the reaction liquid is kept below a predetermined temperature. The present inventors have found that an increase in the viscosity of an inkjet ink occurs because the photoacid generator is decomposed under high temperature conditions to generate an acid. Therefore, the generation of acid can be reduced by storing the reaction liquid container 3 at a low temperature, and the increase in the viscosity of the recording ink after mixing can be further suppressed. The ratio of the second solution as the reaction liquid is as small as about 3 parts by weight with respect to 100 parts by weight of the recording ink after mixing. For this reason, when the volume of the reaction solution container 3 is reduced, the frequency of replenishment is low and productivity does not decrease. Further, because of the small capacity, even if a cooling means using a fan or a Peltier element is used, it can be stored at a low temperature with a small amount of power.

  A light source 13 and a heating device 14 are sequentially disposed downstream of the inkjet head 20 in the recording medium conveyance direction.

  The light source 13 irradiates the ink layer on the recording medium M with light to generate an acid in the ink layer. Examples of the light source 13 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, An electron beam irradiation apparatus, an X-ray irradiation apparatus, etc. can be used. In particular, it is desirable to use a high-pressure mercury lamp or a semiconductor laser because the system can be simplified.

  The heating device 14 heats the ink layer on the recording medium M and promotes a crosslinking reaction using an acid as a catalyst. As the heating device 14, for example, an infrared lamp, a blower for blowing hot air or hot air, a roller (heat roller) with a built-in heating element, and the like can be used.

  As shown in the figure, a control device 101 that controls the operation of the ink jet recording apparatus 1 is connected to the ink jet recording head 20. Further, a power source 103 that drives the ink jet recording head 20 and an image data processing storage device 102 that stores and processes image data formed by the ink jet recording head 20 are connected to the control device 101.

  FIG. 2 shows a block diagram of the ink jet recording apparatus 1. Signals from the remaining ink sensors 9, 10, and 11 are input to the control device 101. Further, a signal for controlling the operation of the reaction liquid supply pump 4, the colored ink supply pump 6, the motor 7, and the cooling fan 12 is output from the control device 101.

  The first solution and the second solution are supplied to the ink stirring container 2 under the following control. When the ink remaining amount detection sensor 9 detects that no recording ink is present in the ink stirring container 2, a predetermined amount of the second solution (reaction liquid) is discharged from the reaction liquid container 3 by the reaction liquid supply pump 4. The ink is supplied to the ink stirring container 2. At the same time, a predetermined amount of the first solution (colored ink) is supplied from the colored ink container 5 to the ink stirring container 2 by the colored ink supply pump 6.

  The supply amount of each solution is preferably adjusted as follows. That is, it is desirable to supply two types of solutions so that the amount of the photoacid generator in the ink after mixing in the ink stirring container 2 is 1 part by weight or more and 10 parts by weight or less. As a result, an increase in the viscosity of the ink can be reduced and sufficient curing hardness can be obtained.

  From the time when the second solution (reaction solution) and the first solution (colored ink) start to be mixed in the ink stirring vessel 2, the viscosity of the recording ink increases. The longer the time that the ink stays in the ink stirring container 2, the greater the rate of increase in viscosity. If the capacity of the ink agitation container 2 is reduced to shorten the time during which the mixed ink stays, the increase in viscosity can be suppressed. However, when the amount of the solution to be mixed is small, the solution supply operation from the two containers and the stirring / mixing operation in the ink stirring container 2 are frequently performed, resulting in a decrease in printing productivity. End up.

  It is preferable to adjust the amount of recording ink mixed in the ink stirring container 2 according to the frequency of the printing operation. For example, when the frequency of the printing operation is high, the amount of the recording ink to be prepared is increased to reduce the frequency of the supply operation and the stirring / mixing operation. As a result, a decrease in printing productivity can be suppressed. On the other hand, when the frequency of the printing operation is low, the amount of the recording ink is decreased to shorten the time that remains in the ink stirring container 2. This can reduce the increase in viscosity and avoid image degradation.

  Such an operation is performed as follows. First, when a print command is given together with information such as the name of the data to be printed, the number of copies, etc., to the control device 101, the data size and print rate (ink ink) of the image data stored in the instructed image data processing / storage device 102 are given. The ratio of the number of ejected pixels) and the amount of ink consumed determined from the number of printed sheets and the remaining amount of ink from the recording ink remaining amount detection sensor 9 are used to supply the reaction liquid supply pump 4 and the colored ink. The drive time of the pump 6 is controlled. For example, when the amount of ink used for printing is large and the remaining amount of ink in the ink agitation container 2 is small, the color ink and the reaction liquid are agitated by the reaction liquid supply pump 4 and the color ink supply pump 6. Supply to container 2. Conversely, when the amount of ink consumed for printing is small and the remaining amount of ink in the ink agitation container 2 is large, the reaction liquid supply pump 4 and the colored ink supply pump 6 are not operated.

  By controlling the supply amount of each solution in this way, the supply operation from both containers and the stirring / mixing operation in the ink stirring container 2 can be executed in parallel with the printing operation. In addition, the printing operation is not stopped, and a decrease in printing productivity is suppressed. Further, the increase in the viscosity of the recording ink is also reduced, and the deterioration of the image can be avoided.

  In the following, embodiments of the present invention will be described in more detail with specific examples. Unless it deviates from the technical idea of this invention, this invention is not limited to the Example shown below.

  In the embodiment of the present invention, two types of solutions are mixed and a recording ink is prepared immediately before being supplied to the ink jet recording head. In the recording ink thus obtained, the color component is preferably blended in the range of 1 to 25% by weight with respect to 100% by weight of the solvent. In order to investigate an appropriate range of the content of the photoacid generator in the colored ink, the following experiment was conducted.

First, EP1 and EP2 shown below were prepared as solvents for polymerization in the presence of an acid.

  A first solution was prepared by mixing 50% by weight of the epoxy compound EP1 with 5% by weight of carbon black as a color component.

As a photoacid generator, a solution (PAG3) prepared by dissolving PAG1 and PAG2 shown below in equal amounts in propylene carbonate was prepared. This photoacid generator is commercially available as UVACURE1591 manufactured by Daicel UCB.

A second solution (B1 to B7) was prepared by mixing PAG3 as a photoacid generator at a ratio shown in Table 1 below with respect to 50% by weight of the epoxy compound EP2.

  By mixing the first solution prepared in advance and the second solution, ink samples (1 to 7) are obtained.

  The obtained ink samples were examined for curability and storage stability by the following method.

Evaluation of curability:
First, an ink sample was dropped on a transparent film such as a PET film with a disposable syringe. This ink was stretched to a film thickness of about 4 μm by a bar coater, and irradiated with ultraviolet rays of 1500 mW / cm ² by a fusion UV irradiator (HP-6) at a transport speed of 25 m / min. Then, the ink cured film was produced by heating at 100 degreeC for 1 minute.

  About the obtained ink cured film, pencil hardness was evaluated by the scratch hardness method (pencil method) (JIS K 5600-5-4). Here, “F” or higher is indicated by “◯”, HB is indicated by “Δ”, and B or lower is indicated by “X”.

Evaluation of storage stability:
Evaluation was made by an accelerated test. Specifically, it was stored at 65 ° C. for 11 days, and the subsequent viscosity was measured at 45 ° C. using an E-type viscometer manufactured by Toki Sangyo Co., Ltd. Based on the increase from the initial viscosity, the evaluation was as follows.

  In addition, the preservability was evaluated for two types, one in which the first solution and the second solution were separated and stored, and one in which these were mixed and stored.

○: Less than 20% Δ: 20% or more and less than 25% ×: 25% or more, or precipitates are generated. The results obtained are summarized in Table 2 below.

  If the pencil hardness is H or higher, it is acceptable, and if the storage stability is “Δ” or higher, it is a practical level.

  As shown in Table 2, in the ink stored after mixing the first solution and the second solution, the addition amount of the photoacid generator is 2 to 4 in order to achieve both curability and storage stability. % Range. On the other hand, when the two solutions are separated and stored, even if the photoacid generator is contained in an addition amount of 2 to 20%, these characteristics can be achieved.

An increase in viscosity after mixing two types of solutions can be avoided by adding a basic compound as a viscosity stabilizer. The following compounds were prepared as basic compounds.

Ink samples 8 to 13 were prepared by blending the above-described epoxy compound, color component, photoacid generator, and basic compound in the formulation shown in Table 3 below.

The obtained ink sample was evaluated for curability and storage stability by the same method as described above, and the results are summarized in Table 4 below.

  As shown in Table 4, when the basic compound is not contained (addition amount 0 wt%), the storage stability is poor, but the storage stability is improved by adding the basic compound at a ratio of 0.2 wt% or more. Can be increased. However, since the curability deteriorates when the addition amount of the basic compound is 1 wt% or more, the addition amount is preferably in the range of 0.2 to 0.8 wt%. This addition amount has been confirmed to be a ratio with respect to the photoacid generator, and is preferably 2.5 to 10 wt% with respect to the photoacid generator.

  Based on the above results, the amounts of photoacid generator and basic compound added to the recording ink were determined.

(Experiment 1)
The chronological viscosity of a cation-curable recording ink containing a polymerizable compound that crosslinks in the presence of an acid as at least a part of a solvent, a photoacid generator that generates an acid by light irradiation, and a color component. In order to investigate the cause of the increase, the following experiment was conducted.

  First, the aforementioned compounds EP1 and EP2 were mixed at the same weight to obtain an epoxy resin component a.

  On the other hand, carbon black as a color component was kneaded with an acrylic resin as a dispersant, and 200 ppm nonionic surfactant (manufactured by Sumitomo 3M) was added to obtain a color component mixture.

Samples b, c, and e were obtained by blending the above-described epoxy resin component a, the color component mixture, and PAG3 as a photoacid generator in the proportions (% by weight) shown in Table 5 below. Samples b and e were prepared by mixing the components and dispersing and treating with a paint shaker day and night.

  In Table 5, the ratio (% by weight) of the color component mixture indicates the amount of carbon black relative to the entire sample.

  The four types of samples thus obtained were stored in a dark place at 65 ° C., and the increase in viscosity over time was examined.

  The rate of increase in viscosity is due to the phenomenon that the polymerization reaction starts due to the influence of the acid generated by decomposition. For this reason, the increase rate of viscosity and the polymerization (reaction) rate are closely related. In order to quickly obtain the viscosity when stored at 25 ° C. for 6 months, an accelerated test using high temperature storage is used. The viscosity was measured at a measurement temperature of 45 ° C. using an E-type viscometer manufactured by Toki Sangyo Co., Ltd. The obtained results are shown in the graph of FIG.

  As shown in FIG. 3, the viscosity of Sample c and Sample e is increased. It is presumed that the photoacid generator was added to these samples, and the viscosity increased due to the reaction between the photoacid generator and the polymerizable compound. On the other hand, in samples a and b, there is no increase in viscosity. From this, it was confirmed that the reaction causing the viscosity increase did not occur in the polymerizable compound alone or the sample in which the pigment was dispersed in the polymerizable compound.

  From the above results, the photoacid generator and the polymerizable compound that polymerizes in the presence of acid are stored separately, and both are mixed to form a recording ink before image formation. It can be seen that if the ink is ejected, a recording ink having a stable viscosity can always be supplied to the ink jet recording head, and a stable printing characteristic can be obtained.

  In order to confirm this, the following experiment was conducted.

(Experiment 2)
Samples shown in Table 6 below were prepared using the same epoxy resin component (a), color component mixture and photoacid generator as those described above. In Table 6, the ratio (% by weight) of the color component mixture indicates the amount of carbon black relative to the entire sample.

  For sample g, PAG3 (UVACURE1591 manufactured by Daicel UCB) as a photoacid generator was used alone.

These samples were each stored in the dark at 65 ° C. Ten days later, the sample f and the sample g were mixed at a ratio (% by weight) shown in Table 3 below to obtain a sample h. The sample h was further stored in a dark place at 65 ° C. The sample h has the same configuration as the sample e and has a composition of a cation curable recording ink. That is, it is a cation curable recording ink prepared by mixing a separately stored photoacid generator and a polymerizable compound that polymerizes in the presence of an acid containing a color component.

  During this period, the viscosity of sample f was measured until day 10, sample h was measured from day 10 to day 31, and sample e was measured until day 31. The measurement results are shown in the graph of FIG.

  As in the case of Experiment 1, the viscosity of the sample f containing the epoxy resin component and the color component and not including the photoacid generator was not confirmed over 10 days.

  As shown in the graph of FIG. 4, the sample h has no change in viscosity during the initial 10 days. For this reason, the rate of increase in the viscosity of the sample h as a whole is reduced to about ½ that of the sample e.

(Experiment 3)
Next, a basic compound as a viscosity stabilizer and / or a compound for adjusting basicity were blended in the colored ink, and then the viscosity with time of the ink mixed with the photoacid generator was measured.

Samples i, g, and e were prepared by blending the same epoxy resin component (a), color component mixture, photoacid generator, and basic compound (B1) as described above in the proportions (% by weight) shown in Table 8 below. did.

These samples were each stored in the dark at 65 ° C. Ten days later, sample i and sample g were mixed at a ratio (% by weight) shown in Table 9 below to obtain sample j, and this sample j was further stored in a dark place at 65 ° C.

  During this period, the viscosity of sample i was measured until day 10, sample j was measured from day 10 to day 21, and sample e was measured until day 21. The obtained results are shown in the graph of FIG.

  Similar to FIG. 3 showing the results of Experiment 1, the sample i containing the epoxy composition not containing the photoacid generator, the carbon black dye, and the basic compound did not increase in viscosity over time for 10 days. .

  The sample j has the same configuration as the sample e and has a composition of a cation curable recording ink. That is, it is a cation curable recording ink formed by mixing separately stored photoacid generators and a polymerizable compound that polymerizes in the presence of an acid containing a color component. Sample h has no change in viscosity during the initial 10 days. For this reason, the rate of increase in the viscosity of the sample h as a whole is reduced to about ½ that of the sample e. Moreover, the increasing rate of the viscosity from the 11th day is lower than the increasing rate of the viscosity from the 0th day of the sample e.

  This is because the acid decomposed from the photoacid generator and the basic compound are neutralized, and curing of the polymerizable compound as a solvent is suppressed. However, if the photoacid generator and the basic compound are mixed from the beginning, neutralization proceeds, and even when UV light or the like is irradiated, the amount of acid generated decreases, and there are cases where sufficient curing cannot be achieved.

  For this reason, it is desirable to store the photoacid generator and the basic compound separately and to mix them before discharging them with an inkjet head. That is, the basic compound is blended in a colored ink containing a color component and stored in a colored ink container. As a result, neutralization does not proceed, and acid is efficiently generated by irradiation with UV light or the like, and sufficient curing hardness is obtained. According to the embodiment of the present invention, the increase in viscosity can be reduced to ½ or less of the conventional one. As a result, even when the ink was stored for a long time inside the ink jet recording apparatus, a good image with little decrease in image density was obtained.

(Experiment 4)
The ink stored for a predetermined number of days in a dark place at 65 ° C. was examined for curability by the same method as described above. The obtained results are shown in Table 10 below.

  As described above, samples h and i were able to reduce the increase in viscosity over time to about ½ or less of sample e. At the same time, it was confirmed that the curing performance was not deteriorated.

  Since the increase in viscosity is reduced, the samples h and i can be supplied to the ink jet recording head without causing any inconvenience. In the ink jet recording apparatus 1 shown in FIG. 1, even when the colored ink and the reaction liquid are stored in respective containers and stored, the increase in viscosity is reduced and can be similarly supplied to the ink jet recording head. It was. Since the viscosity does not increase, the ink jet recording head can be ejected in a stable amount.

  The graph of FIG. 6 shows the relationship between the rate of change in viscosity of the recording ink and the rate of change in discharge volume. The rate of change of the viscosity and the rate of change of the volume are almost proportional. When the viscosity increases by 20%, the discharge volume decreases by 7 to 8%. When the viscosity of the ink increases by storage and reaches 20%, the volume ejected from the ink jet recording head decreases by 7 to 8%. As a result, the image density is reduced as compared with the state before the viscosity increases. As described above, in the embodiment of the present invention, the increase in the viscosity of the recording ink can be reduced to about 1/2 of the conventional one. As a result, even if the ink is stored for a long time inside the ink jet recording apparatus, it is possible to obtain a good image with little decrease in image density.

  The effect of storage temperature on the viscosity increase of the recording ink is shown in the graph of FIG. The aforementioned sample e was stored at three temperatures of 25 ° C., 45 ° C., and 65 ° C., and the change in viscosity over time was measured. It was confirmed that the increase in viscosity increases as the storage temperature increases, and that the increase in viscosity can be suppressed by storing at a low temperature.

  Here, FIG. 8 shows a conventional inkjet recording apparatus 200. In the conventional inkjet recording apparatus 200, ink is supplied from the ink container 201 to the inkjet head 20. The printing operation, light irradiation, and heating are performed in the same manner as in the recording apparatus shown in FIG. 1, except that the ink container 201 contains a photoacid generator, a solvent that polymerizes in the presence of an acid, and a color component. All containing ink is contained. When the ink is stored for a long time in such a state, the viscosity increases under the same conditions as those of the sample e described above. When ink having increased viscosity is supplied to the ink jet recording head 20, a discharge failure occurs.

  Further, the ink container 201 in the conventional ink jet recording apparatus 200 has a large capacity, and a large amount of electric power is required to keep it at a low temperature. Moreover, an increase in the size of the apparatus is inevitable. By reducing the capacity of the ink container 201, it becomes possible to keep it at a low temperature with electric power, but it is necessary to replenish ink frequently. As a result, there arises a problem that printing productivity is greatly reduced.

  In the recording apparatus according to the embodiment of the present invention, the reaction liquid containing the photoacid generator is accommodated in a small-capacity container. For this reason, it is possible to avoid the increase in the viscosity of the ink by cooling the reaction liquid container without causing any inconvenience as described above.

1 is a schematic view of an ink jet recording apparatus according to an embodiment of the present invention. FIG. 2 is a block diagram illustrating a control system of the ink jet recording apparatus illustrated in FIG. 1. FIG. 5 is a graph showing the increase in viscosity of recording ink over time. FIG. 5 is a graph showing the increase in viscosity of recording ink over time. FIG. 5 is a graph showing the increase in viscosity of recording ink over time. FIG. 4 is a graph showing the relationship between the ink viscosity change rate and the ink ejection volume change rate. The graph showing the influence of the temperature which acts on the viscosity change of a composition. Schematic diagram of a conventional inkjet recording apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Inkjet recording device, M ... Recording medium, 20 ... Inkjet recording head 2 ... Ink stirring container, 3 ... Reaction liquid container, 4 ... Reaction liquid supply pump, 5 ... Colored ink container 6 ... Colored ink supply pump, 7 DESCRIPTION OF SYMBOLS Motor, 8 ... Stirring blade 9 ... Recording ink residual quantity detection sensor, 10 ... Reaction liquid residual quantity detection sensor 11 ... Colored ink residual quantity detection sensor, 12 ... Cooling fan, 13 ... Light source, 14 ... Heater 101 ... Control part , 102 ... Image data processing storage device, 103 ... Power source 200 ... Inkjet recording device, 201 ... Ink container.

Claims (7)

A colored ink container containing a colored ink containing a solvent that polymerizes in the presence of an acid and a color component dispersed in the solvent;
Photoacid generator which generates an acid by light irradiation to accommodate a reaction solution formed by adding to the solvent, the reaction liquid container that will be stored by the lower color ink container temperature,
A stirring container for obtaining a recording ink by mixing the colored ink and the reaction liquid;
A pump for supplying colored ink that supplies the colored ink from the colored ink container to the stirring container at a volume S1;
A reaction liquid supply pump for supplying the reaction liquid from the reaction liquid container to the stirring container at a volume S2 (S2 <S1);
An ink jet recording apparatus comprising: an ink jet recording head that discharges the recording ink onto a recording medium; and a supply pipe that supplies the recording ink in the stirring container to the ink jet recording head. An ink jet recording apparatus according to claim 1, characterized that you include a cooling fan for cooling the reaction vessel. The volume (V2) of the reaction liquid container is smaller than the volume (V1) of the colored ink container, and the ratio of the volume of the containers (V2 / V1) is the mixing of the reaction liquid and the colored ink in the stirring container. 3. The ink jet recording apparatus according to claim 1, wherein the ratio is smaller than a ratio (S2 / S1) . A device for storing and processing image data,
A recording ink remaining amount detection monitor for detecting the remaining amount of the recording ink in the stirring container; and
Further comprising a control device,
Image information from the image data storage / processing device and remaining amount information from the colored ink remaining amount detection monitor are input to the control device and supplied to the colored ink supply pump and the reaction liquid supply pump. 4. An ink jet recording apparatus according to claim 1, wherein information is output . Wherein such recording ink is contained in an amount of 1 to 20% by weight of the photoacid generator, of claims 1 to 4 wherein the colored ink and the reaction liquid is supplied to the serial stirred vessel, characterized in Rukoto The ink jet recording apparatus according to any one of the above. The recording ink is an ink jet recording apparatus according to any one of from more claims 1, characterized that you containing at least one basic compound and compound that modulates a basic 5. At least one of the compounds that modulate the basic compound and a basic ink-jet printing apparatus according to claim 6, characterized in Rukoto be contained in the recording ink in a proportion of 0.1 to 0.8 wt% .

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