JP4862341B2 - Ink for inkjet recording - Google Patents

Description

  The present invention relates to an ink for ink jet recording having excellent storage stability and ejection stability, high color developability on plain paper and glossy paper, and high glossiness and fixability on glossy paper.

  As inks for ink jet recording, those using dyes and pigments as color materials are in widespread use. In the ink using a pigment, a method using a surfactant as a means for dispersing the pigment in water (see Patent Document 1), a method using a dispersion polymer having a hydrophobic part and a hydrophilic part (see Patent Document 2), or A method of coating the surface of the pigment with a polymer has been studied, and as an example, a method using a phase inversion emulsification reaction or an acid precipitation method has been studied (see Patent Document 3).

JP-A-1-301760 JP-A-6-306317 Japanese Patent Laid-Open No. 10-140065

  However, in any case, since a polymer containing styrene as a main constituent is used as a method for dispersing the pigment, the fixability is not so much, and yellowing is easily caused by long-term storage of the printed matter. Further, in the normal case, when a substance having a hydrophilic part and a hydrophobic part such as a surfactant or glycol ether is present, there is a problem that adsorption / desorption tends to occur and storage stability is inferior. Conventional water-based inks require a substance having a hydrophilic part and a hydrophobic part such as a surfactant and glycol ether in order to reduce bleeding on paper. Ink that does not use these substances has insufficient permeability to paper, and there is a problem that the type of paper is limited in order to perform uniform printing, which tends to cause a reduction in the printed image.

  Further, for example, additives for improving printing quality (acetylene glycol surfactant, acetylene alcohol surfactant, silicon surfactant, di (tri) ethylene glycol monobutyl ether or 1,2-alkylene) are added to conventional dispersions. Long-term storage stability cannot be obtained when using a glycol or a mixture thereof, and in the case of pigment inks, the re-dissolvability is poor, so that the ink dries and easily becomes clogged with the nozzles of the inkjet head, and the head is configured. It has problems such as attacking a material such as an adhesive used for the substance to reduce the adhesive strength to deteriorate the discharge stability.

  In addition, in the pigment ink dispersed by such a general dispersant, the residue of the dispersant remains in the ink, and the dispersant does not contribute sufficiently to the dispersion and is detached from the pigment and has a high viscosity. There was a problem that it would end up. When the viscosity is increased, the amount of the coloring material such as pigment is limited, and there is a problem that sufficient print quality cannot be obtained particularly on plain paper.

  The ink for inkjet recording of the present invention comprises water and at least 50% by weight or more of benzyl acrylate, 10% by weight or more of epoxy (meth) acrylate and / or urethane (meth) acrylate as a polymer component, and 15% by weight or less. (Meth) acrylic acid is polymerized and includes a pigment dispersed using a polymer having a weight average molecular weight of 20,000 to 120,000 and having an acid value of 50 mgKOH / g to 120 mgKOH / g.

  The ink for ink jet recording of the present invention is excellent in storage stability and ejection stability, and provides ink for ink jet recording having high color developability on plain paper and glossy paper, and high glossiness and fixability on glossy paper. Has a good effect.

  The ink for ink-jet recording of the present invention is excellent in storage stability and ejection stability, has high color development on plain paper and glossy paper, has fixing properties in addition to sufficient gloss on glossy paper, This is due to the result of intensive studies in view of the demand for characteristics such as excellent ink ejection stability.

  The ink for inkjet recording of the present invention comprises water and at least 50% by weight or more of benzyl acrylate, 10% by weight or more of epoxy (meth) acrylate and / or urethane (meth) acrylate as a polymer component, and 15% by weight or less. (Meth) acrylic acid is polymerized and includes a pigment dispersed using a polymer having a weight average molecular weight of 20,000 to 120,000 and having an acid value of 50 mgKOH / g to 120 mgKOH / g.

  In the present invention, a polymer in which 50% by weight or more of benzyl acrylate and 15% by weight or less of (meth) acrylic acid are polymerized is preferable. However, when benzyl acrylate is less than 50% by weight, the fixing property is lowered. Therefore, the preferable range is 50% by weight or more, but the case of less than 50% by weight is not denied. Therefore, it is preferably 50% by weight or more, more preferably 60% by weight or more. Furthermore, polymerization with 15% by weight or less of (meth) acrylic acid is preferable, but if it exceeds 15% by weight, the color developability of plain ink for ink jet recording tends to be lowered. However, polymerization exceeding 15% by weight is not denied, and a more preferable range is 10% by weight or less. When methacrylic acid and acrylic acid are compared, it is more preferable to use acrylic acid from the viewpoint of fixability.

  Furthermore, the present invention is characterized in that 10% or more by weight of epoxy (meth) acrylate and / or urethane (meth) acrylate is used as a constituent component of the polymer, thereby improving fixability and glossiness. it can. If it is 10% by weight or less, the fixability deteriorates. More preferably, it is 15% by weight or more.

  In the present invention, the polymer in which the pigment is dispersed preferably has a weight average molecular weight of 20,000 to 200,000. If the weight average molecular weight is less than 20,000, the long-term storage stability, thermal stability and fixability as an ink for ink jet recording deteriorate, and if it exceeds 200,000, the viscosity as an ink for ink jet recording increases and the dispersion stability. Tends to be worse, and the ejection stability tends to be lower.

  The pigment used in the present invention is, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper oxide, iron oxide (C CI pigment black 11), metals such as titanium oxide, organic pigments such as aniline black (CI pigment black 1), etc., but carbon having a relatively low specific gravity for ink jet recording is difficult to settle in water. Black is preferred. Further, for color use, C.I. I. Pigment Yellow 1 (Fast Yellow G), 3, 12 (Disazo Yellow AAA), 13, 14, 17, 24, 34, 35, 37, 42 (Yellow Iron Oxide), 53, 55, 74, 81, 83 (Disazo Yellow HR), 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 153, 180, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22 (Brilliant First Scarlet), 23, 31, 38, 48: 2 (Permanent Red 2B (Ba)), 48: 2 (Permanent Red 2B (Ca)), 48 : 3 (Permanent Red 2B (Sr)), 48: 4 (Permanent Red 2B (Mn)), 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81 (Rhodamine 6G rake), 83, 88, 101 (Bengara), 104, 105, 106, 108 (Cadmium red), 112, 114, 122 (Quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 202, 209, 219, 254, . I. Pigment violet 19, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue G), 15: 4, 15: 6 (phthalocyanine blue E), 16, 17: 1, 56 , 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc. can be used.

  The added amount of the pigment is preferably 0.5 to 30% by weight, more preferably 1.0 to 12% by weight. If the addition amount is 0.5% by weight or less, the print density cannot be secured, and if the addition amount is 30% by weight or more, the viscosity of the ink increases and structural viscosity is generated in the viscosity characteristics, and the ejection stability of the ink from the inkjet head Tends to get worse.

  The polymer used for dispersion of the pigment in the present invention is a commercially available styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, polyethylene glycol ( A combination of one or more selected from a (meth) acrylate- (meth) acrylic acid copolymer, a vinyl acetate-maleic acid copolymer, a styrene-maleic acid copolymer, and the like can also be used. However, it is preferable that at least 80% or more is a polymer obtained by copolymerization of acrylate and acrylic acid. Examples of the acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl carbitol acrylate, phenol EO-modified acrylate, N-vinyl pyrrolidone, Commercially available acrylates such as isobornyl acrylate, benzyl acrylate, paracumylphenol EO-modified acrylate, and 2-hydroxyethyl-3-phenoxypropyl acrylate can be used. Further, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, acrylic acid dimer or the like can be used instead of acrylic acid.

  Moreover, what has epoxy (meth) acrylate and urethane (meth) acrylate in a side chain as an example of the epoxy (meth) acrylate and / or urethane (meth) acrylate used for this invention is mentioned. What has epoxy (meth) acrylate is obtained by, for example, addition-reacting (meth) acrylic acid to what copolymerized methyl (meth) acrylate and glycidyl (meth) acrylate. Moreover, what has urethane (meth) acrylate is, for example, a copolymer of methyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate, tolylene diisocyanate or isophorone diisocyanate and (meth) acrylic acid 2 -It can be obtained by addition reaction of hydroxyethyl reacted at a molar ratio of 1.

  Examples of the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, and glycidyl ether such as polypropylene glycol and polytetramethylene glycol. And an adduct of (meth) acrylic acid.

  Examples of urethane (meth) acrylates include polyisocyanates such as tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, polypropylene glycol, ethylene oxide / propylene oxide copolymer, polytetramethylene glycol, adipic acid and ethylene glycol, and diethylene glycol. An isocyanate prepolymer obtained by reacting a polycondensation product with a polyol such as 1,4-butanediol or 1,6-hexanediol, a polyol such as polycaprolactone, 2-hydroxyethyl (meth) acrylate, 2- Hydroxyl-containing acrylics such as hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. It includes adducts of over bets.

  Next, examples of the polymerizable monomer having a (meth) acryloyl group include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, and mixtures thereof. Examples of monofunctional (meth) acrylates include 2- Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) arylate, ethoxydiethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide adduct of nonylphenol (meth) Acrylates, propylene oxide adducts of nonylphenol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopente (Meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Examples include (meth) acrylate.

  Moreover, it is preferable that the dispersion method using the polymer used by this invention is phase inversion emulsification. By using the phase inversion emulsification method, the ink becomes stable and the color developability of plain paper is improved.

  In addition, the ink of the present invention has 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol, 3,6-dimethyl-4-octyne-3, 6-diol, 2, 4, 7 1 or more selected from alkylene oxide adducts of 9-tetramethyl-5-decyne-4,7-diol and alkylene oxide adducts of 3,6-dimethyl-4-octyne-3,6-diol The addition amount is preferably 0.05 to 1.0% by weight. If it is less than 0.05% by weight, bleeding on plain paper increases, which is not preferable. On the other hand, if it exceeds 1% by weight, the storage stability as an ink for ink jet recording deteriorates, and long-term storage becomes difficult. More preferably, it is 0.1 wt% or more and 0.7 wt%.

  The 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl An alkylene oxide adduct of -5-decyne-4,7-diol is commercially available, Surfynol 104, Surfinol 82, Surfinol 2502, Surfinol 420, Surfinol 440, Surfinol 465, manufactured by Nissin Chemical Co., Ltd. It can be obtained as Surfynol 485, acetylenol EOO, acetylenol E40, acetylenol E100 manufactured by Kawaken Fine Chemical Co., Ltd.

  The ink of the present invention preferably contains 1,2-alkylene glycol. Among the 1,2-alkylene glycols, 1,2-hexanediol and 4-methyl-1,2-pentanediol are particularly preferable. By using the pigment dispersion of the present invention and further using these, ink jet recording ink can be discharged. Stability is improved and bleeding is reduced when printing on plain paper.

  The ink of the present invention is one kind selected from di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether, di (tri) ethylene glycol monopentyl ether and di (tri) ethylene glycol monohexyl ether. It is preferable to comprise the above. By using the pigment dispersion of the present invention and further using these glycol ethers, bleeding when printed on plain paper by the inkjet method is further reduced, and the printing quality is improved.

  The ink of the present invention preferably contains 2-butyl-2-ethyl-1,3-propanediol, and the pigment dispersion of the present invention is used to make 2-butyl-2-ethyl-1,3 -Further use of propanediol improves glossiness on glossy paper and improves color developability on plain paper.

  The polymer in the present invention has a carboxyl group, and preferably contains triethanolamine and / or tripropanolamine as a counter ion. By using triethanolamine and / or tripropanolamine, clogging of ink for ink jet recording hardly occurs even in a dry state. Similarly, the ink of the present invention contains at least one selected from glycerin, trimethylolethane, trimethylolpropane, tetrasaccharide, pentasaccharide, and hexasaccharide so that the inkjet head is less likely to be clogged. Is preferred.

  In the polymer polymerization method of the present invention, an alcohol solvent, a ketone solvent, an ether solvent, or a glycol ether solvent can be used as a solvent. However, since it is an aqueous pigment dispersion, it is necessary to be able to remove the above-mentioned solvent later. Therefore, the following can be used as such a solvent. Examples of the alcohol solvent include methanol, ethanol, isopropanol, 1-butanol, tertiary butanol, isobutanol, diacetone alcohol and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ether solvent include dibutyl ether, tetrahydrofuran, dioxane and the like. Furthermore, examples of the glycol ethers include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, and butyl cellosolve.

  Moreover, as a radical polymerization initiator for polymerizing a polymer, t-butyl peroxy (2-ethylhexanoate), di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyoct Organic peroxides such as ate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2′-azobisbutyrate, 2, Azo compounds such as 2′-azobis (2-methylbutyronitrile), potassium persulfate, sodium persulfate, and the like can be used, but are not limited to these, and start other than the above as long as radical polymerization is possible. An agent can also be used. The amount of radical polymerization initiator used is preferably 0.01 mol% or more and 5 mol% or less with respect to the monomer used in the polymerization. The polymerization temperature is not particularly limited, but is usually in the range of 30 to 100 ° C, and preferably in the range of 40 to 90 ° C. When the polymerization temperature is too low, it is necessary to take a long time for the polymerization of the monomer, and in some cases, the polymerization rate may decrease and a large amount of monomer may remain.

  Further, the ink of the present invention may further comprise a dispersant, a surface tension adjusting agent or a penetrating agent (surfactant), a wetting / drying preventing agent, an antiseptic, a bactericidal agent, a pH adjusting agent, a rust preventing agent, and a moisturizing agent. Other additives may be used. These may be used alone or in combination of two or more.

  The above-mentioned high-pressure disperser is not particularly limited, but it is preferable to use a medialess disperser from the viewpoint of contamination contamination and dispersion stability. Examples thereof include a microfluidizer (Microfluidics) and an optimizer. (Sugino Machine), wet jet mill (Genus), Nanomizer (Nanomizer) and the like.

  The pressure at the time of dispersion by the high-pressure disperser used for preparing the pigment dispersion used in the ink of the present invention may be any as long as it can reach the desired pigment particle diameter, but is preferably 100 MPa to 300 MPa. If it is less than 100 MPa, the dispersed particle size tends to be large, it takes time to disperse, and unless the number of passes is extremely increased, a stable dispersion is unlikely to be economical. Moreover, when it exceeds 300 MPa, it is easy to become overdispersed, and it is difficult to obtain the stability of the dispersion. If the desired pigment particle diameter cannot be reached, the dispersion may be carried out by increasing the number of dispersions or increasing the pressure within the aforementioned pressure range.

  Further, in the method for producing an ink for ink jet recording of the present invention, an alkali solution is added to the polymer composition of the ink for ink jet recording that has been polymerized and heated, and then the solvent is removed, and ion exchange water or the like. A polymer composition solution of an ink for ink jet recording substituted with the above may be used.

  Further, the solvent of the ink-jet recording ink, which has been polymerized, is removed by distillation under reduced pressure, the solid matter of the ink-jet recording ink polymer obtained is crushed, and ion-exchanged water, an alkali solution, etc. are added and heated. You may use the polymer solution of the ink for inkjet recording obtained by melt | dissolving. In this case, thereafter, it is not necessary to remove the organic solvent and the like from the obtained pigment dispersion.

  Examples of the alkali used in the alkali solution include tertiary alkyl alkanolamines such as triethanolamine, tripropanolamine, and ethyldiethanolamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. .

(Example)
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples, and various modifications can be made without departing from the gist of the present invention.

The inside of a 2000 ml separable flask equipped with a stirrer, a reflux tube, a thermometer, and a dropping funnel was purged with nitrogen, and then 200.0 parts by weight of diethylene glycol monomethyl ether was placed in the separable flask and heated to 80 ° C. while stirring. . Next, 200.0 parts by weight of diethylene glycol monomethyl ether, 363.0 parts by weight of benzyl acrylate, 120 parts by weight of urethane acrylate (Ebecr y CL1039: manufactured by Daicel Cytec Co., Ltd.), 50.4 parts by weight of acrylic acid and t- 4.8 parts by weight of butyl peroxy (2-ethylhexanoate) was added and reacted dropwise at 80 ° C. over 4 hours in a separable flask. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour, 0.8 parts by weight of t-butylperoxy (2-ethylhexanoate) was added, and the reaction was further carried out at 80 ° C. for 1 hour. Thereafter, diethylene glycol monomethyl ether was removed by distillation under reduced pressure. Then, 600.0 parts by weight of methyl ethyl ketone was added to obtain a polymer composition solution having a resin solid content of 50%. A part of the polymer composition solution thus obtained was taken and dried for 1 hour in an oven at 105 ° C., and then the acid value of the obtained polymer was 65 mgKOH / g, and the weight average molecular weight was 34000. Met.

  Next, 3.0 parts by weight of a 30% aqueous sodium hydroxide solution is added to 120.0 parts by weight of the polymer composition solution thus prepared, and the mixture is stirred with a high-speed disper for 5 minutes. Further, Cyanine Blue G- 480.0 parts by weight of 500 pure-A (CI PB15: 1; manufactured by Sanyo Dye Co., Ltd.) was added, and the mixture was stirred with a high-speed disper for 1 hour to obtain a pigment dispersion slurry. Then, the pigment dispersion slurry was continuously dispersed 10 times at a pressure of 200 MPa with an ultrahigh pressure homogenizer (Microfluidizer, manufactured by Mizuho Kogyo Co., Ltd.) to obtain a pigment dispersion.

  Further, methyl ethyl ketone and a part of water were distilled off from the pigment dispersion thus obtained by vacuum distillation using an evaporator, and centrifuged at 5000 rpm for 30 minutes with a centrifuge (05P-21, manufactured by Hitachi, Ltd.). After the separation, ion-exchanged water was added so that the pigment concentration was 15% by weight to prepare a pigment dispersion. And it filtered under pressure using a 5.0 micrometer membrane filter (made by Advantech). Then, the ink for inkjet recording of the ink composition example 1 shown in Table 2 was created.

Instead of 50.4 parts by weight of acrylic acid, 13.2 parts of methacrylic acid, 36.5 parts by weight of acrylic acid, and 120 parts of urethane acrylate (Ebecr y CL1039: manufactured by Daicel Cytec Co., Ltd.) are used as epoxy acrylate (NK). Oligomer EA-6320 (manufactured by Shin-Nakamura Chemical Co., Ltd.) The same procedure as in Example 1 was conducted except that the amount was changed to 120 parts, and an ink for inkjet recording of Composition Example 2 shown in Table 2 was produced. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high temperature drier, the acid value of the polymer of the obtained ink for inkjet recording is 60 mgKOH / g, and the weight average molecular weight is 32000. Met.

Instead of 50.4 parts by weight of acrylic acid, 42.6 parts by weight of acrylic acid is used, and 120 parts of urethane acrylate (Ebecr y CL1039: manufactured by Daicel Cytec Co., Ltd.) is used as epoxy acrylate (NK oligomer EA-6320: manufactured by Shin-Nakamura Chemical). ) The same procedure as in Example 1 was carried out except that the amount was changed to 120 parts, and an inkjet recording ink of Composition Example 3 shown in Table 2 was produced. Further, after taking a part of the polymer composition solution and drying for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 55 mgKOH / g, and the weight average molecular weight is 48000. Met.

Instead of 50.4 parts by weight of acrylic acid, 77.5 parts by weight of acrylic acid is used, and 120 parts of urethane acrylate (Ebecr y CL1039: manufactured by Daicel Cytec Co., Ltd.) is used as epoxy acrylate (NK oligomer EA-6320: manufactured by Shin-Nakamura Chemical). ) The same procedure as in Example 1 was conducted except that the amount was changed to 120 parts, and an inkjet recording ink of Composition Example 4 shown in Table 2 was produced. Further, after taking a part of the polymer composition solution and drying it for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 100 mgKOH / g, and the weight average molecular weight is 29000. Met.

Instead of 50.4 parts by weight of acrylic acid, 93.0 parts by weight of acrylic acid is used, and 120 parts of urethane acrylate (Ebecr y CL1039: manufactured by Daicel Cytec Co., Ltd.) is added as epoxy acrylate (NK oligomer EA-6320: manufactured by Shin-Nakamura Chemical). The ink for ink jet recording of Composition Example 5 shown in Table 2 was prepared in the same manner as in Example 1 except that the amount was changed to 120 parts. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 120 mgKOH / g, and the weight average molecular weight was 34000. Met.

  Table 2 shows the same procedure as in Example 1 except that 480.0 parts by weight of Cyanine G-500 pure-A having a pigment concentration of 25% by weight was replaced by Monarch 880 (CI PBk7: manufactured by Cabot). An ink for ink jet recording of composition example 13 shown in FIG. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 34000. Met.

  The same procedure as in Example 2 was conducted except that Monarch 880 (CI PBk7: manufactured by Cabot) was used instead of 480.0 parts by weight of Cyanine G-500 pure-A having a pigment concentration of 25% by weight. An ink for ink jet recording having the composition example 14 shown was prepared. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high temperature drier, the acid value of the polymer of the obtained ink for inkjet recording is 60 mgKOH / g, and the weight average molecular weight is 32000. Met.

  Instead of 120.0 parts by weight of Cyanine G-500 pure-A, the same as Example 1 except that 120.0 parts by weight of Pigment Violet GC227-A (CI PV19; manufactured by Sanyo Pigment Co., Ltd.) was used. Then, an ink for ink jet recording of Composition Example 19 shown in Table 2 was prepared. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 34000. Met.

  The same procedure as in Example 2 was conducted except that 120.0 parts by weight of Pigment Violet GC227-A was used in place of 120.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 20 shown in Table 2 Ink was made. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high temperature drier, the acid value of the polymer of the obtained ink for inkjet recording is 60 mgKOH / g, and the weight average molecular weight is 32000. Met.

  Instead of 120.0 parts by weight of Cyanine G-500 pure-A, 120.0 parts by weight of Fast Yellow 7413-A (CI PY74; manufactured by Sanyo Dye Co., Ltd.) was used in the same manner as in Example 1. Then, an ink for ink jet recording of Composition Example 25 shown in Table 2 was prepared. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 34000. Met.

  Instead of 120.0 parts by weight of Cyanine G-500 pure-A, 120.0 parts by weight of Fast Yellow 7413-A (CI PY74; manufactured by Sanyo Color Co., Ltd.) was used in the same manner as in Example 2. Then, an ink for inkjet recording of Composition Example 26 shown in Table 2 was prepared. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high temperature drier, the acid value of the polymer of the obtained ink for inkjet recording is 60 mgKOH / g, and the weight average molecular weight is 32000. Met.

(Comparative Example 1)
The same procedure as in Example 1 was carried out except that 363.0 parts by weight of benzyl acrylate and 120 parts by weight of urethane acrylate were changed to 483.0 parts by weight of benzyl acrylate, and the ink for inkjet recording of Composition Example 6 shown in Table 2 was used. Created. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 29000. Met.

(Comparative Example 2)
An ink for inkjet recording of Composition Example 7 shown in Table 2 was produced in the same manner as in Example 1 except that 116.3 parts by weight of acrylic acid was used instead of 50.4 parts by weight of acrylic acid. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 150 mgKOH / g, and the weight average molecular weight was 34000. Met.

(Comparative Example 3)
An ink for inkjet recording of Composition Example 8 shown in Table 2 was prepared in the same manner as in Example 1 except that 155.0 parts by weight of acrylic acid was used instead of 50.4 parts by weight of acrylic acid. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for inkjet recording was 200 mgKOH / g, and the weight average molecular weight was 29000. Met.

(Comparative Example 4)
The same as Example 1 except that t-butylperoxy (2-ethylhexanoate) was changed to 4.8 parts by weight and t-butylperoxy (2-ethylhexanoate) was changed to 20.0 parts by weight. Then, an ink for ink jet recording of Composition Example 9 shown in Table 2 was prepared. Further, after taking a part of the polymer composition solution and drying it for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 65 mgKOH / g, and the weight average molecular weight is 10,000. Met.

(Comparative Example 5)
The same as Example 2 except that 15.0 parts by weight of t-butylperoxy (2-ethylhexanoate) was used instead of 4.8 parts by weight of t-butylperoxy (2-ethylhexanoate). The ink for inkjet recording of the composition example 10 shown in Table 2 was produced. Further, after taking a part of the polymer composition solution and drying for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 60 mgKOH / g, and the weight average molecular weight is 18000. Met.

(Comparative Example 6)
Example 1 except that 4.8 parts by weight of t-butylperoxy (2-ethylhexanoate) was replaced with 3.1 parts by weight of t-butylperoxy (2-ethylhexanoate). The ink for inkjet recording of the composition example 11 shown in Table 2 was produced. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 130,000. Met.

(Comparative Example 7) Instead of 50.4 parts by weight of acrylic acid, 23.3 parts by weight of acrylic acid was used, and 120 parts of urethane acrylate (Ebecr y CL1039: manufactured by Daicel Cytec Co., Ltd.) was added to epoxy acrylate (NK oligomer EA-6320). : Shin-Nakamura Chemical Co., Ltd.) Except for changing to 120 parts, the same procedure as in Example 1 was carried out to prepare an ink jet recording ink of Composition Example 12 shown in Table 2. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high temperature drier, the acid value of the polymer of the obtained ink for inkjet recording is 30 mgKOH / g, and the weight average molecular weight is 33000. Met.

(Comparative Example 8)
Cyanine G G-500 pure-A Instead of 480.0 parts by weight, Monarch 880 (CI PBk7: manufactured by Cabot) was replaced with 480.0 parts by weight. An ink for ink jet recording of Composition Example 15 shown was prepared. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 34000. Met.

(Comparative Example 9)
Cyanine Blue G-500 pure-A Instead of 480.0 parts by weight, Monarch 880 (CI PBk7: manufactured by Cabot) was replaced with 480.0 parts by weight. The ink for inkjet recording of the composition example 16 shown was produced. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high temperature drier, the acid value of the polymer of the obtained ink for inkjet recording is 60 mgKOH / g, and the weight average molecular weight is 32000. Met.

(Comparative Example 10)
Cyanine G G-500 pure-A Instead of 480.0 parts by weight, Monarch 880 (CI PBk7: manufactured by Cabot) was replaced with 480.0 parts by weight. An ink for ink-jet recording having the composition example 17 shown was prepared. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 130,000. Met.

(Comparative Example 11)
Cyanine Blue G-500 pure-A Instead of 480.0 parts by weight, the same procedure as in Comparative Example 7 was carried out except that Monarch 880 (CI PBk7: manufactured by Cabot) was changed to 480.0 parts by weight. The ink for inkjet recording of the composition example 18 shown was produced. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high temperature drier, the acid value of the polymer of the obtained ink for inkjet recording is 30 mgKOH / g, and the weight average molecular weight is 33000. Met.

(Comparative Example 12)
The same procedure as in Comparative Example 1 was performed except that 480.0 parts by weight of Pigment Violet GC227-A was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 21 shown in Table 2 Ink was made. Further, after taking a part of the polymer composition solution and drying for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 130 mgKOH / g, and the weight average molecular weight is 29000. Met.

(Comparative Example 13)
The same procedure as in Comparative Example 5 was conducted except that Pigment Violet GC227-A 480.0 parts by weight was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 22 shown in Table 2 Ink was made. Further, after taking a part of the polymer composition solution and drying for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 60 mgKOH / g, and the weight average molecular weight is 18000. Met.

(Comparative Example 14)
The same procedure as in Comparative Example 6 was conducted except that Pigment Violet GC227-A 480.0 parts by weight was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 23 shown in Table 2 Ink was made. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 130,000. Met.

(Comparative Example 15)
The same procedure as in Comparative Example 7 was conducted except that Pigment Violet GC227-A 480.0 parts by weight was used instead of 480.0 parts by weight of Cyanine G-500 pure-A 48. Inkjet recording of Composition Example 24 shown in Table 2 Ink was made. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high temperature drier, the acid value of the polymer of the obtained ink for inkjet recording is 30 mgKOH / g, and the weight average molecular weight is 33000. Met.

(Comparative Example 16)
The same procedure as in Comparative Example 1 was conducted except that 480.0 parts by weight of Fast Yellow 7413-A was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 27 shown in Table 2 Ink was made. Further, after taking a part of the polymer composition solution and drying for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 130 mgKOH / g, and the weight average molecular weight is 29000. Met.

(Comparative Example 17)
The same procedure as in Comparative Example 5 was conducted except that 480.0 parts by weight of Fast Yellow 7413-A was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 28 shown in Table 2 Ink was made. Further, after taking a part of the polymer composition solution and drying for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 60 mgKOH / g, and the weight average molecular weight is 18000. Met.

(Comparative Example 18)
The same procedure as in Comparative Example 6 was conducted except that 480.0 parts by weight of Fast Yellow 7413-A was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 29 shown in Table 2 Ink was made. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 130,000. Met.

(Comparative Example 19)
The same procedure as in Comparative Example 7 was conducted except that 480.0 parts by weight of Fast Yellow 7413-A was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 30 shown in Table 2 Ink was made. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high temperature drier, the acid value of the polymer of the obtained ink for inkjet recording is 30 mgKOH / g, and the weight average molecular weight is 33000. Met.

(Evaluation test 1: Evaluation method of abrasion resistance)
The inks for inkjet recording according to Examples 1 to 11 and Comparative Examples 1 to 19 were solid-printed on PM photo paper (Seiko Epson Corporation) with an inkjet printer (EM-930C, Seiko Epson Corporation), and a test specimen Got. The print mode was paper: photo print paper, print quality: photo, color correction: none, print direction: bidirectional. Thereafter, a fixing property evaluation test was performed by rubbing the test specimen with a line marker on which 300 g of fruit juice was applied. The fixability evaluation test is performed by a method of observing the degree of ink peeling when the printed surface and the back surface are moved at a speed of 1 m / s by overlapping with a load of 300 g using the above test body (PM photographic paper). It was. In Table 2, S does not peel at all even if moved 3 times, AA does not peel at all even if moved 2 times, but slightly peels off when moved 3 times, A does not peel at all Although there is no peeling, slight peeling occurs when moved twice, B is peeling slightly, C is peeling and transferred to the back surface, and D is considerably peeled and transferred to the back surface.

(Evaluation Test 2: Evaluation Method for Colorability of Plain Paper)
The inkjet recording inks according to Examples 1 to 11 and Comparative Examples 1 to 19 were solid-printed on XeroxP paper (manufactured by Fuji Xerox Co., Ltd.) using an inkjet printer (EM-930C, manufactured by Seiko Epson Corporation), and tested. Get the body. The print mode was paper: plain paper, print quality: super fine, color correction: none, print direction: bidirectional. And it is by measuring the OD value of each color using GRETAGMACBETH SPECTROSCANSP50 (made by Gretag (USA)). The results are shown in Table 1 as OD values.

(Evaluation Test 3: Glossiness Evaluation Method)
The inks for inkjet recording according to Examples 1 to 11 and Comparative Examples 1 to 19 were solid-printed on PM photo paper (Seiko Epson Corporation) with an inkjet printer (EM-930C, Seiko Epson Corporation), and a test specimen Got. The print mode was paper: photo print paper, print quality: photo, color correction: none, print direction: bidirectional. The 20 degree gloss of this test specimen was measured with a gloss meter (HG-268, manufactured by Suga Test Instruments Co., Ltd.). The results are shown in Table 1.

(Evaluation Test 4: Particle Size Evaluation Method)
The average particle diameter of the particles in the inks for inkjet recording according to Examples 1 to 11 and Comparative Examples 1 to 19 was measured with a laser particle size analyzer (Zeta Sizer 3000, manufactured by Malvern, UK).

(Evaluation Test 5: Evaluation Method for Storage Stability)
The initial viscosity of the pigment dispersion of the ink jet recording ink used in Examples 1 to 11 and Comparative Examples 1 to 19 and the viscosity after standing at 70 ° C. for 1 week were measured using a rolling ball viscometer (AMVn, Anton Pearl ( (Germany)). The results are shown in Table 1 as storage stability: viscosity (mPa · s) / initial viscosity (mPa · s) after standing at 70 ° C. for 1 week.

  Table 1 also shows the monomer composition, the polymerization initiator and the pigment, and the ink composition for ink jet recording that were used when the ink for ink jet recording was produced.

The abbreviations shown in Tables 1 and 2 are as follows.
BZA: benzyl acrylate AA: acrylic acid MAA: methacrylic acid BPEH: t-butylperoxy (2-ethylhexanoate)
URA: Urethane acrylate (Ebecr y CL1039: manufactured by Daicel Cytec Co., Ltd.)
EPA: Epoxy acrylate (NK oligomer EA-6320: manufactured by Shin-Nakamura Chemical)
PBk7: C.I. I. Pigment Black 7 (Carbon Black)
PB15: 1: C.I. I. Pigment Blue 15: 1 (trichlorophthalocyanine)
PV19: C.I. I. Pigment Violet 19 (Quinacridone)
PY74: C.I. I. Pigment Yellow 74 (Condensed Azo Pigment)
DEGmBE: diethylene glycol monobutyl ether TEGmBE: triethylene glycol monobutyl ether PGmBE: propylene glycol monobutyl ether DPGmBE: dipropylene glycol monobutyl ether BEPD: 2-butyl-2-ethyl-1,3-propanediol 1,2-HD: 1, 2-Hexanediol TMP: Trimethylolpropane

As can be seen from the results in Tables 1 and 2, when the inks for ink jet recording according to Examples 1 to 11 are used, the evaluation tests 1 to 5 are all good results, but the ink jet recordings according to Comparative Examples 1 to 19 are used. When the ink for use is used, good results are not obtained in any of the evaluation tests 1 to 5 or a plurality of items.

Claims (5)

  Water and at least 50% by weight or more of benzyl acrylate, 10% by weight or more of epoxy (meth) acrylate and / or urethane (meth) acrylate and 15% by weight or less (meth) acrylic acid are polymerized as a polymer component, An ink for ink jet recording comprising: a pigment dispersed using a polymer having an acid value of 50 mgKOH / g to 120 mgKOH / g and having a weight average molecular weight of 20000 to 120,000.   0.05% to 1% by weight of 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7 The ink for inkjet recording according to claim 1, comprising at least one selected from alkylene oxide adducts of diols.   The ink for inkjet recording according to claim 1, comprising 1,2-alkylene glycol.   The ink for inkjet recording according to any one of claims 1 to 3, comprising at least one selected from di (tri) ethylene glycol monobutyl ether and (di) propylene glycol monobutyl ether. The ink for inkjet recording according to claim 1, comprising 2-butyl-2-ethyl-1,3-propanediol.