COPOLYMER, WATER INK, AND INK CARTRIDGE

专利摘要:
copolymer, aqueous ink, and ink cartridge. a copolymer contains repeating units represented by the following chemical formulas 1 and 2: where, r represents a hydrogen atom or a cation; x represents an alkylene group having 2 to 18 carbon atoms; y represents a single bond, an oxycarbonyl group [(x) -o-co- (z)], a carbonyloxy group [(x) -co-o- (z)], an ether group (-o-), or an imido group [(x) -n-co- (co) - (z)]; and z represents a biphenyl group or a naphthyl group.
公开号:BR102014000803B1
申请号:R102014000803-9
申请日:2014-01-13
公开日:2020-09-24
发明作者:Shigeyuki Harada；Tamotsu Aruga；Hiroshi Gotou；Hidetoshi Fujii
申请人:Ricoh Company, Ltd.；
IPC主号:

专利说明:

[0001] [001] The present invention relates to a new copolymer that is useful as a binder resin or an aqueous paint pigment dispersion resin; and an aqueous ink and an ink cartridge that includes the copolymer. Background of the technique
[0002] [002] The inkjet engraving system is advantageous in that, compared to other engraving systems, the process is simple, color printing is achieved easily, and high resolution images can be obtained even with a device which has a simple configuration. For this reason, the inkjet engraving system is becoming common and spreading from personal use to office and commercial printing and industrial printing fields. In such an inkjet engraving system, aqueous compositions containing water-soluble dyes as colorants are mainly used. However, water-soluble dyes have the disadvantages of having insufficient water resistance and insufficient light resistance. Appropriately, pigment inks that contain water-insoluble pigments instead of water-soluble pigments are being studied.
[0003] [003] In inkjet printing for use in offices, conventional sheets of paper are used mainly as a recording medium and high image density is required. In general, when printing is done to apply pigment ink to a conventional sheet of paper, the pigment does not stay on the surface of the sheet of paper and permeates to the sheet of paper; and, as a result, the pigment density on the paper surface becomes low and the image density becomes low. By increasing the pigment concentration of the ink, the image density can be increased. However, the viscosity of the paint is increased and the discharge stability is degraded.
[0004] [004] Immediately after the pigment ink is discharged onto a conventional sheet of paper, water in the ink causes the surface of the paper sheet to swell and the difference in the extension ratios of the front and back surfaces of the paper sheet becomes resulting in a paper curl problem. This phenomenon disappears when the paper sheet dries. Appropriately, the phenomenon was not considered to be a problem in high-speed printing. However, with the increase in print speed, recording medium that remains in a wavy state due to the printing that needs to be transported. As a result, a paper jam problem can be caused. In order to avoid this, a method of adding a penetrating agent to the ink can be effective to allow rapid water permeation to the sheets of paper, however, the ink becomes hydrophobic and thus it becomes difficult to guarantee stability ink storage; in addition, the permeability of the pigment to the recording medium is also increased and the image density is further increased.
[0005] [005] In order to solve such problems, several techniques to make the pigment stay on the surfaces of paper sheets have been proposed. For example, JP-2009- 513802-A proposes an inkjet ink that contains a liquid carrier, a colorant, and a polymer that has at least one functional group that has a specific calcium index. This proposal states that a monomer that forms the polymer is 4-methacrylamido-1-hydroxybutane-1,1-diphosphonic acid; when the colorant is placed in contact with a sheet of paper, the colorant is destabilized by the group of polymer diphosphonic acid and Ca salts on the sheet of paper to thereby improve the images. However, the ink has a problem with low storage stability.
[0006] [006] JP-2012-051367-A proposes an inkjet engraving method to manufacture a reception solution containing a Ca salt adheres to sheets of paper and performs printing with an ink containing a pigment which a group containing phosphorus is bonded, a resin emulsion, and a surfactant. This proposal states that the Ca salt of the reception solution reacts with the group containing phosphorus to achieve improvements in terms of fixation and plumage. However, when embossing conventional sheets of paper, the effect of increasing image density is not sufficiently provided.
[0007] [007] In the fields of commercial printing and industrial printing, there is a demand for techniques that allow the stable formation of images that have higher resolution and definition at a higher speed. The recording medium used is, for example, conventional sheets of paper, coated sheets of paper, sheets of art paper, and waterproof films such as PET films. Appropriately, there is a demand for ink that has high versatility for such recording medium.
[0008] [008] When images that have high resolution and definition are formed at a high speed in various recording media, in particular, slightly permeable media such as coated paper sheets and sheets of art paper or waterproof films, edges (inequalities) tend to be caused. To solve this, JP-H3-160068-A proposes a paint that has a minimum film formation temperature of 40 ° C or more and at least contains, as fixing agents, wax emulsion, resin emulsion, latex, organic ultrafine particles and inorganic ultrafine particles.
[0009] [009] JP-2006-188624-A proposes an inkjet ink containing at least water, an organic solvent, and a polymer, in which the polymer contained in the ink or ink from which a portion of water has been evaporated shows phase separation of the UCST type in the range of 0 ° C to 100 ° C.
[0010] [0010] JP-2008-536963-A proposes a paint that contains a vehicle that can be blasted; a plurality of pigment solids self-dispersed in the vehicle; and a half of maleic styrene anhydride ester (SMA) dispersed in the vehicle.
[0011] [0011] In addition, JP-2012-52027-A proposes a method to change the rheological behavior of paint in response to pH change through the use of a polymer that responds to pH including plural hydrophilic segments in side chains and segments that respond to pH which become hydrophilic and hydrophobic in response to pH values.
[0012] [0012] However, when the existing inks described above are used, it is difficult to form images on various recording media at a high speed without causing edges (inequalities).
[0013] [0013] As in the inkjet engraving system described above, aqueous pigment inks that contain pigments as colorants in writing implements such as marking pens, spherical pens, and drawing pens have a problem of exhibiting low color density on conventional sheets of paper, in particular, on conventional white sheets of paper, compared with dye inks. In order to address this problem, JP-2005-298802-A proposes an aqueous pigment ink containing oil-in-water emulsion of water-insoluble (meth) acrylic resin and / or styrene- (meth) acrylic acid having a size average particle size of 50 to 200 nm and a minimum film formation temperature of 50 ° C or more, urea or a derivative of urea, water, pigment, an aqueous resin, and a phosphate surfactant. However, the effect of increasing the color density is not sufficiently provided. SUMMARY
[0014] [0014] The present invention provides a copolymer that contains repeating units represented by the following chemical formulas 1 and 2:
[0015] [0015] Various other objects, functionalities and advantages of the present invention will be more fully realized as it becomes better understood from the detailed description when considered in conjunction with the accompanying drawings in which similar reference characters designate similar corresponding parts through the same and where:
[0016] [0016] FIG. 1 is a graph illustrating the infrared absorption spectrum (Kbr pellet method) of Copolymer 1 according to an embodiment of the present invention;
[0017] [0017] FIG. 2 is a graph illustrating the infrared absorption spectrum of Copolymer 2 according to an embodiment of the present invention;
[0018] [0018] FIG. 3 is a graph illustrating the infrared absorption spectrum of Copolymer 3 according to an embodiment of the present invention;
[0019] [0019] FIG. 4 is a graph illustrating the infrared absorption spectrum of Copolymer 4 according to an embodiment of the present invention;
[0020] [0020] FIG. 5 is a graph illustrating the infrared absorption spectrum of Copolymer 5 according to an embodiment of the present invention;
[0021] [0021] FIG. 6 is a graph illustrating the infrared absorption spectrum of Copolymer 6 according to an embodiment of the present invention;
[0022] [0022] FIG. 7 is a graph illustrating the infrared absorption spectrum of Copolymer 7 according to an embodiment of the present invention;
[0023] [0023] FIG. 8 is a graph illustrating the infrared absorption spectrum of Copolymer 8 according to an embodiment of the present invention;
[0024] [0024] FIG. 9 is a graph illustrating the infrared absorption spectrum of Copolymer 9 according to an embodiment of the present invention;
[0025] [0025] FIG. 10 is a graph illustrating the infrared absorption spectrum of Copolymer 10 according to an embodiment of the present invention;
[0026] [0026] FIG. 11 is a graph illustrating the infrared absorption spectrum of Copolymer 12 according to an embodiment of the present invention;
[0027] [0027] FIG. 12 is a graph illustrating the infrared absorption spectrum of Copolymer 13 according to an embodiment of the present invention;
[0028] [0028] FIG. 13 is a schematic view illustrating an example of the ink cartridge according to an embodiment of the present invention;
[0029] [0029] FIG. 14 is a schematic view illustrating an example of the ink cartridge of FIG. 13 and its accommodation; and;
[0030] [0030] FIG. 15 is a diagram illustrating grades from A to E at the edge fold. DETAILED DESCRIPTION
[0031] [0031] The present invention is to provide a copolymer that is useful as a binder resin or an aqueous paint pigment dispersion resin.
[0032] [0032] The copolymer includes repeating units represented by chemical formulas 1 and 2 described above. In chemical formula 2, R represents a hydrogen atom or a cation. When R represents a cation, oxygen close to the cation is present as O-. Examples of the cation include sodium ion, potassium ion, lithium ion, tetramethyl ammonium ion, tetraethyl ammonium ion, tetrapropyl ammonium ion, tetrabutyl ammonium ion, tetrapentyl ammonium ion, tetrahexyl ammonium ion, triethyl methyl ammonium, tributyl methyl ammonium ion, trioctyl methyl ammonium ion, 2-hydroxyethyl trimethyl ammonium ion, tris (2-hydroxyethyl) methyl ammonium ion, propyl trimethyl ammonium ion, hexyl trimethyl ammonium ion, octyl ion trimethyl ammonium, nonyl trimethyl ammonium ion, decyl trimethyl ammonium ion, dodecyl trimethyl ammonium ion, tetradecyl trimethyl ammonium ion, hexadecyl trimethyl ammonium ion, trimethyl ammonium octadecyl trimethyl ammonium ion, didodecyl trimethyl ammonium ion , dihexadecyl dimethyl ammonium ion, dioctadecyl dimethyl ammonium ion, ethyl hexadecyl dimethyl ammonium ion, ammonium ion, dimethyl ammonium ion, trimethyl ammonium ion, monoethanolammonium ion, diethanolammonium ion, triethanolamine ion, methyl ethanolammonium, methyl diethyl ethanolammonium ion, dimethyl ethanolammonium ion, monopropanolammonium ion, dipropanolammonium ion, tripropanolammonium ion, isopropanolamonium ion, morpholium ion, N-methyl morpholium ion, N-methyl-2-pyronium ion and 2-pyrrolidonium ion.
[0033] [0033] X represents an alkylene group having 2 to 18 carbon atoms; Y represents a single bond, an oxycarbonyl group ((X) -O-CO- (Z)], a carbonyloxy group [(X) -CO-O- (Z)], an ether group (-O-), or an imido group [(X) -N-CO- (CO) - (Z)]; and Z represents a biphenyl group or a naphthyl group.
[0034] [0034] Specifically, in chemical formula 2, the end group Z which is a biphenyl group or a naphthyl group is linked via Y and X which serves as linking groups for the carboxyl group. Such a biphenyl group or a naphthyl group present at the end has a high pigment adsorption capacity due to stacking Π-Π with the pigment that serves as a colorant in the aqueous ink (hereinafter, sometimes referred to as the ink). Appropriately, through the contact of such a group with pigment in a printing medium during printing, pigment aggregation occurs quickly on the surface of the printing medium in order to suppress the edge (inequalities). In particular, Z in formula 2 preferably represents a naphthyl group from the point of view of the adsorption pigment capacity.
[0035] [0035] A copolymer according to the present invention, which includes repeating units represented by chemical formulas 1 and 2 described above, can additionally include a repeating unit represented by chemical formula 3 described above.
[0036] [0036] By adding a repetition unit represented by chemical formula 3, the glass transition temperature of the copolymer is decreased; after an ink droplet containing this copolymer is discharged to a recording medium, while the ink permeates the paper sheet and the water evaporates, pigment aggregation occurs more quickly to provide images with high resolution and definition in this way without edging (unevenness) in high speed printing. In chemical formula 3, R1 represents a hydrogen atom or a methyl group and R2 represents an alkyl group having 2 to 23 carbon atoms, preferably a butyl group.
[0037] [0037] When a pigment dispersion containing pigment dispersed in water is prepared with a copolymer according to the present invention, the copolymer has a biphenyl group or a naphthyl group at the end of a side chain and thus tends to adsorb on the pigment surface in order to provide a dispersion that is stable and has a high dispersion capacity.
[0038] [0038] The composition ratio of repetition units represented by chemical formulas 1 and 2 that make up a copolymer according to the present invention preferably satisfies, from the point of view of the ability to adsorb pigment, chemical formulas 1: 2 = 1 : 1 to 10: 1, more preferably 1: 1 to 5: 1, even more preferably 1: 1 to 3: 1.
[0039] [0039] The composition ratio of the repeating units represented by chemical formulas 1 to 3 that make up a copolymer according to the present invention preferably satisfies, from the point of view of the ability to adsorb pigment, in the case of chemical formulas 1: 2 = 1: 1 to 10: 1, chemical formulas 1 and 2 (total amount): chemical formula 3 = 0.5: 1 to 30: 1, more preferably 1: 1 to 10: 1.
[0040] [0040] A copolymer according to the present invention preferably has a numerical average molecular weight of 500 to 10,000 and a mass average molecular weight of 1500 to 30,000 in terms of polystyrene.
[0041] [0041] A copolymer according to the present invention may include, in addition to the repeating units represented by chemical formulas 1 to 3, a repeating unit derived from another monomer that can be polymerized.
[0042] [0042] Such another monomer that can be polymerized is not particularly limited and can be appropriately selected according to the purpose: for example, a hydrophobic monomer that can be polymerized, a hydrophilic monomer that can be polymerized, or a surfactant that can be polymerized.
[0043] [0043] Examples of the hydrophobic monomer that can be polymerized include unsaturated ethylene monomers that have aromatic rings such as α-methyl styrene, 4-t-butyl styrene, and 4-chloromethyl styrene; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, dimethyl maleate, dimethyl itaconate, dimethyl fumarate, lauryl (meth) acrylate (C12), tridecyl (meth) acrylate (C13), tetradecyl (meth) acrylate (C14), pentadecyl (meth) acrylate (C15), hexadecyl (meth) acrylate (C16), heptadecyl (meth) acrylate (C17), nonadecyl (meth) acrylate (C19), eicosil (meth) acrylate (C20), hyenosyl (meth) acrylate (C21), and docosyl (meth) acrylate (C22); and unsaturated ethylene monomers having alkyl groups such as 1-heptene, 3,3-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 1-octene, 3,3-dimethyl-1-hexene, 3,4-dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 1-nonene, 3,5,5-trimethyl-1-hexene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, and 1-docosene. These monomers can be used alone or in combination of two or more of them.
[0044] [0044] Examples of the hydrophilic monomer that can be polymerized include anionic unsaturated ethylene monomers such as (meth) acrylic acid or salts thereof, maleic acid or salts thereof, monomethyl maleate, itaconic acid, monomethyl itaconate, fumaric acid, 4 -sulfonic styrene, and 2-acrylamide-2-methylpropane sulfonic acid; and nonionic unsaturated ethylene monomers such as 2-hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, ( met) acrylamide, N-methylol (meth) acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, acrylamide, N, N-dimethylacrylamide, Nt-butylacrylamide, N-octylacrylamide, and Nt-octylacrylamide.
[0045] [0045] One or more selected from such hydrophobic monomers that can be polymerized and hydrophilic monomers that can be polymerized can be used in an amount of 5% to 100% by weight relative to the total amount of the monomers that form the units repetition represented by chemical formulas 1 to 3.
[0046] [0046] The surfactant that can be polymerized is an anionic or non-ionic surfactant having at least one unsaturated double bond group that can be radical polymerized intramolecularly.
[0047] [0047] Examples of the anionic surfactant include a hydrocarbon compound having a sulfate group such as an ammonium sulfate group (-SO3-NH4 +) and an allyl group (-CH2-CH = CH2); a hydrocarbon compound having a sulfate group such as an ammonium sulfate group (-SO3-NH4 +) and a methacrylic group [CO-C (CH3) = CH2]; and an aromatic hydrocarbon compound having a sulfate group such as an ammonium sulfate group (-SO3-NH4 +) and a 1-propenyl group (-CH = CH2CH3). Specific examples of the surfactant include ELEMINOL JS-20 and RS-300 (manufactured by Sanyo Chemical Industries, Ltd.); and AQUALON KH-10, AQUALON KH-1025, AQUALON KH-05, AQUALON HS-10, AQUALON HS-1025, AQUALON HS-0515, AQUALON BC-10, AQUALON BC-1025, AQUALON BC-20, and AQUALON BC- 2020 (manufactured by DAI-ICHI KOGYO SEIYAKU CO. LTD.).
[0048] [0048] The nonionic surfactant can be a hydrocarbon compound or aromatic hydrocarbon compound having a 1-propenyl group (-CH = CH2CH3) and a polyoxyethylene group [- (C2H4O) n-H]. Specific examples of the non-ionic surfactant include AQUALON RN-20, AQUALON RN-2025, AQUALON RN-30 and AQUALON RN-50 (manufactured by DAI-ICHI KOGYO SEIYAKU CO. LTD.); and LATEMUL PD-450 (manufactured by Kao Corporation).
[0049] [0049] One or more of such surfactants that can be polymerized can be used in an amount of 0.1% to 10% by weight reactive to the monomers that form the repetition units represented by chemical formulas 1 to 3.
[0050] [0050] A copolymer according to the present invention can be synthesized by, for example, a synthesis method 1 or a synthesis method 2 below. Synthesis Method 1
[0051] [0051] As illustrated with the following formulas, naphthalenocarbonyl chloride (A-1) and an excess of a diol compound are subjected to a condensation reaction in the presence of an acid receptor such as an amine or pyridine to provide a hydroxyalkyl naphthalene carboxylate (A-2).
[0052] [0052] A styrene-maleic anhydride copolymer (A-3) and an excess of (A-2) above are then subjected to an addition reaction to provide a copolymer (A-4) according to the present disclosure.
[0053] [0053] As illustrated with the chemical formulas, a reaction between maleic anhydride (A-5) and a hydroxyalkyl naphthalene carboxylate (A-2) is made to provide a monomer of maleic acid ester (A-6). This (A-6) and styrene (A-7) are subsequently copolymerized in the presence of a radical polymerization initiator to provide a copolymer (A-4) according to the present disclosure.
[0054] [0054] As in synthesis method 2, the monomer of maleic acid ester (A-6) is synthesized.
[0055] [0055] As illustrated with the following formulas, this (A-6), styrene (A-7), and methyl methacrylate (A-8) are copolymerized in the presence of a radical polymerization initiator to provide a copolymer (A- 9) in accordance with the present disclosure.
[0056] [0056] The radical polymerization initiator described above is not particularly limited and can be selected appropriately according to the purpose. Examples of the radical polymerization initiator include peroxy quetal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxy ester, cyano which are azobisisbutyronitrile, azobis (2-methylbutyronitrile) and azobis (2,2'-isovaleronitrile), and one non-cyan initiator which is dimethyl-2,2'-azobisisobutyrate. Of these, as molecular weight control is easily achieved and the decomposition temperature is low, organic peroxides and azo compounds are preferred; and, in particular, azo compounds are preferred.
[0057] [0057] The content of the radical polymerization initiator is not particularly limited and can be selected appropriately according to the purpose. The content of the radical polymerization initiator is preferably 1% to 10% by weight relative to the total amount of monomers that can be polymerized.
[0058] [0058] For the purpose of adjusting the molecular weight of the polymer, a chain transfer agent can be added in an appropriate amount.
[0059] [0059] Examples of the chain transfer agent include mercapto acetic acid, mercapto propionic acid, 2-propanethiol, 2-mercaptoethanol, thiophenol, dodecylmercaptan, 1-dodecanethiol, and thioglycerol.
[0060] [0060] The polymerization temperature is not particularly limited and can be selected appropriately according to the purpose. The polymerization temperature is preferably 50 ° C to 150 ° C, more preferably 60 ° C to 100 ° C. The polymerization time is also not particularly limited and can be selected appropriately according to the purpose. The polymerization time is preferably 3 to 48 hours.
[0061] [0061] Specific non-limiting examples of a copolymer according to the present disclosure include the following compounds. In formulas, "n" represents an integer from 2 to 18; "m" represents 0 or 1; and "k" represents 1 to 22.
[0062] [0062] An aqueous ink dye according to the present disclosure can be pigment or dye. The copolymer described above has a higher dye adsorption capacity than dye; from the point of view of water resistance and light resistance, the pigment is preferred.
[0063] [0063] The pigment is not particularly limited and can be selected appropriately according to the purpose. Examples of the pigment include organic or inorganic pigments for black and other colors. These pigments can be used alone or in combination with two or more of them.
[0064] [0064] Examples of inorganic pigments include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black produced by a publicly known method such as a contact process, an oven process, or a thermal process.
[0065] [0065] Examples of the black color pigment include carbon blacks (Pigment Black 7 C.I.) such as oven black, lamp black, acetylene black, and channel black; metals such as copper and iron (Pigmento Preto 11 C.I.); metal oxides such as titanium oxide; and organic pigments such as aniline black (Pigmento Preto 1 C.I.).
[0066] [0066] The carbon black described above is preferably a carbon black which is produced by an oven process or a channel process, has a primary particle size of 15 to 40 nm, a BET specific surface area of 50 at 300 m2 / g, an oil absorption of DBP of 40 to 150 mL / 100 g, a volatile content of 0.5% to 10%, and a pH of 2 to 9.
[0067] [0067] Examples of organic pigments include azo pigments (including, for example, azo lake, insoluble azo pigments, azo condensation pigments, and azo chelate pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, pigments perinone, anthraquinone pigments, quinacridone pigments, dioxazin pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments), dye chelates (for example, basic dye chelates and acid dye chelates), nitro pigments, nitrous pigments, and aniline black.
[0068] [0068] Of these pigments, in particular, pigments that have a high affinity for water are preferably used.
[0069] [0069] Such azo pigments include, for example, azo lake, insoluble azo pigments, condensation azo pigments, and azo chelate pigments.
[0070] [0070] Such polycyclic pigments include, for example, phthalocyanine pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazin pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments, and pigments rhodamine lake B.
[0071] [0071] Such dye chelates include, for example, basic dye chelates and acid dye chelates.
[0072] [0072] The yellow pigment is not particularly limited and can be selected appropriately according to the purpose. Examples of the pigment include Yellow Pigment CI 1, Yellow Pigment CI 2, Yellow Pigment CI 3, Yellow Pigment CI 12, Yellow Pigment CI 13, Yellow Pigment CI 14, Yellow Pigment CI 16, Yellow Pigment CI 17, Yellow Pigment CI 73, Yellow Pigment CI 74, Yellow Pigment CI 75, Yellow Pigment CI 83, Yellow Pigment CI 93, Yellow Pigment CI 95, Yellow Pigment CI 97, Yellow Pigment CI 98, Yellow Pigment CI 114, Yellow Pigment CI 120, Yellow Pigment CI 128, Yellow Pigment CI 129, Yellow Pigment CI 138, Yellow Pigment CI 150, Yellow Pigment CI 151, Yellow Pigment CI 154, Yellow Pigment CI 155, Yellow Pigment CI 174, and Yellow Pigment CI 180.
[0073] [0073] The pigment for magenta is not particularly limited and can be selected appropriately according to the purpose. Examples of the pigment include Pigment Red CI 5, Pigment Red CI 7, Pigment Red CI 12, Pigment Red CI 48 (Ca), Pigment Red CI 48 (Mn), Pigment Red CI 57 (Ca), Pigment Red CI 57: 1 , Pigment Red CI 112, Pigment Red CI 122, Pigment Red CI 123, Pigment Red CI 146, Pigment Red CI 168, Pigment Red CI 176, Pigment Red CI 184, Pigment Red CI 185, Pigment Red CI 202, and Pigment Violet 19 .
[0074] [0074] The pigment for cyan is not particularly limited and can be selected appropriately according to the purpose. Examples of the pigment include Pigment Blue CI 1, Pigment Blue CI 2, Pigment Blue CI 3, Pigment Blue CI 15, Pigment Blue CI 15: 3, Pigment Blue CI 15: 4, Pigment Blue CI 15:34, Pigment Blue CI 16 , Blue Pigment CI 22, Blue Pigment CI 60, Blue Pigment CI 63, Blue Pigment CI 66, Blue Vat CI 4, and Blue Vat CI 60.
[0075] [0075] The use of Pigment Yellow CI 74 as a yellow pigment, Pigment Red CI 122 and Pigment Violet CI 19 as magenta pigments, and Pigment Blue CI 15: 3 as cyan pigment can provide excellent balanced inks in terms of tone and color. resistance to light.
[0076] [0076] An ink according to the present disclosure can include a pigment that is produced recently for the present disclosure.
[0077] [0077] From the point of view of color development of images to be provided, a self-dispersed pigment can be used and an anionic self-dispersed pigment is preferably used. The anionic self-dispersed pigment denotes a pigment in which an anionic functional group is introduced to the pigment surface either directly or through another atomic group so that dispersion stabilization is achieved.
[0078] [0078] Examples of such a pigment to be treated for stabilizing the dispersion include various pigments known publicly as listed in International Publication No. 2009/014242.
[0079] [0079] The anionic functional group denotes a functional group in which half or more of the hydrogen ions dissociate at a pH of 7.0. Specific examples of the anionic functional group include a carboxyl group, a sulfo group, and a phosphonic group. Of these, from the point of view of increasing the optical density of the images to be provided, a carboxyl group or a phosphonic group are preferred.
[0080] [0080] The method for introducing an anionic functional group to the pigment surface is, for example, a method for subjecting carbon black to an oxidation treatment.
[0081] [0081] Specific examples of the oxidation treatment method include treatment methods include methods of treatment with a hypochlorite, ozonized water, hydrogen peroxide, a chloride, nitric acid, or the like; and surface treatment methods using diazonium salts described in JP 3808504 (JP-H10-510861-A), JP 2009-515007 and JP 2009-506196.
[0082] [0082] Examples of commercially available pigments having a surface hydrophilic functional group include CW-1, CW-2 and CW-3 (these manufactured by ORIENT CHEMICAL INDUSTRIES CO. LTD.); and CAB-O-JET300 and CAB-O-JET400 (manufactured by Cabot Corporation).
[0083] [0083] The pigment content in the aqueous ink is not particularly limited and can be selected appropriately according to the purpose. The pigment content is preferably 0.5% to 20% by weight, more preferably 1% to 10% by weight.
[0084] [0084] The dye described above can be selected from dyes classified as acid dyes, direct dyes, basic dyes, reactive dyes and food dyes in the Color Index.
[0085] [0085] Specifically, for example, acid dyes and food dyes include Acid Black CI 1, 2, 7, 24, 26, and 94, Acid Yellow CI 17, 23, 42, 44, 79, and 142, Acid Blue CI 9, 29, 45, 92, and 249, Acid Red CI 1, 8, 13, 14, 18, 26, 27, 35, 37, 42, 52, 82, 87, 89, 92, 97, 106, 111 , 114, 115, 134, 186, 249, 254, and 289, Food Black CI 1 and 2, Food Yellow CI 3 and 4, and Food Red CI 7, 9 and 14; direct dyes include Direct Black CI 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, (168), and, 171, Direct Yellow CI 1, 12, 24, 26, 33, 44, 50, 86, 120, 132, 142, and 144, Direct Blue CI 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199, 202, Direct Red CI 1, 4, 9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225, 227, and Direct Orange CI 26, 29, 62, and 102; basic dyes include Basic Black CI 2 and 8, Basic Yellow CI 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 64, 65, 67, 70, 73, 77, 87, and 91, Basic Blue CI 1, 3, 5, 7, 9, 21, 22, 26, 35, 41, 45, 47, 54, 62, 65, 66, 67, 69, 75, 77, 78, 89, 92, 93, 105, 117, 120, 122, 124, 129, 137, 141, 147, and 155, and Basic Red CI 2, 12, 13, 14, 15, 18, 22, 23, 24, 27, 29, 35, 36, 38, 39, 46, 49, 51, 52, 54, 59, 68, 69, 70, 73 , 78, 82, 102, 104, 109, and 112; and reactive dyes include Reactive Black CI 3, 4, 7, 11, 12 and 17, Reactive Yellow CI 1, 5, 11, 13, 14, 20, 21, 22, 25, 40, 47, 51, 55, 65 , and 67, Reactive Blue CI 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, and 95, and Reactive Red CI 1, 14, 17, 25, 26, 32, 37, 44, 46, 55, 60, 66, 74, 79, 96, and 97.
[0086] [0086] An aqueous ink according to the present disclosure preferably includes a water-soluble organic solvent so that the penetration capacity of the aqueous ink for conventional paper sheets, coated paper sheets, and the like is enhanced to further suppress the occurrence of dents and the wetting effect is used to prevent the paint from drying out.
[0087] [0087] The water-soluble organic solvent is not particularly limited. Examples of the water-soluble organic solvent include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butanediol, 3-methyl -1,3-butanediol, trimethylolethane, trimethylolpropane, 1,5-pentanediol, 1,6-hexanediol, hexylene glycol, glycerin, 1,2,3-butanotriol, 1,2,4-butanotriol, 1,2,6- hexanotriol, isopropylidene glycerol, and petriol; alkyl polyhydric alcohol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dietylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; aryl polyhydric alcohol ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, and γ-butyrolactone; amides such as formamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethyl-β-methoxypropionamide, and N, N-dimethyl-β-butoxypropionamide; amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, and thiodiethanol; 3-ethyl-3-hydroxymethyloxetane, propylene carbonate, and ethylene carbonate. These solvents can be used alone or in combination with two or more of them.
[0088] [0088] Of these, from the point of view of suppressing curl of conventional paper sheets, 3-ethyl-3-hydroxymethyloxetane, isopropylidene glycerol, N, N-dimethyl-β-methoxypropionamide, and N, N-dimethyl are preferred -β-butoxypropionamide.
[0089] [0089] Diethylene glycol, triethylene glycol, 1,3-butanediol, 2,2,4-trimethyl-1,3-pentanediol, and glycerin are excellent in terms of suppressing the discharge failure caused by water evaporation.
[0090] [0090] Examples of a water-soluble organic solvent that has relatively low wetting capacity and penetration capacity include 2-ethyl-1,3-hexanediol [solubility: 4.2% (25 ° C)] and 2.2 , 4-trimethyl-1,3-pentanediol [solubility: 2.0% (25 ° C)].
[0091] [0091] Other examples of water-soluble organic solvent include aliphatic diols such as 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl- 1,3-propanediol, 3,3-dimethyl-1,2-butanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, and 5-hexene-1,2 -diol.
[0092] [0092] Another water-soluble organic solvent that can be used in combination with the water-soluble organic solvent described above can be appropriately selected according to the purpose from alkyl or aryl ethers of polyhydric alcohols such as diethylene monobutyl ether glycol, propylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, ethylene glycol monoalyl ether, and tetraethylene glycol chlorophenyl ether; and lower alcohols such as ethanol.
[0093] [0093] An aqueous ink according to the present disclosure preferably includes a surfactant so that the penetration and wetting capacity of the aqueous ink for conventional paper sheets, coated paper sheets, and the like are improved and the occurrence of dents is suppressed.
[0094] [0094] Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, anionic surfactants, non-ionic surfactants, and betaine-based surfactants. These surfactants can be used alone or as a mixture of two or more of them. Of these, fluoride-based surfactants and silicone-based surfactants are preferred as the surface tension can be reduced to 30 mN / m or less.
[0095] [0095] Examples of fluorine-based surfactants include non-ionic fluorine-based surfactants, anionic fluorine-based surfactants, amphoteric fluorine-based surfactants, and oligomer fluorine-based surfactants. In such a fluorine-based surfactant, the number of carbon atoms replaced by fluorine atoms is preferably 2 to 16, more preferably 4 to 16. When this number of carbon atoms is less than 2, the specific effect of surfactants based on in fluorine it is not provided in some cases; and when this number of carbon atoms is greater than 16, problems in terms of storage capacity and the like can be caused.
[0096] [0096] Examples of non-ionic fluorine-based surfactants include perfluoroalkyl phosphoric ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups as side chains. Of these, polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups as side chains are preferred because of the low foaming; and fluorine-based surfactants are most preferred represented by the following chemical formula (α). CF3CF2 (CF2CF2) m-CF2CF2 (CF2CF2) nH (α) (where m represents 0 to 10 and n represents 0 to 40)
[0097] [0097] Examples of anionic fluorine-based surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, phosphoric perfluoroalkyl ester compounds, and polyoxyalkylene ether polymer compounds that have perfluoroalkyl ether groups as side chains.
[0098] [0098] Examples of perfluoroalkyl sulfonic acid compounds include perfluoroalkyl sulfonic acids and perfluoroalkyl sulfonic acid salts.
[0099] [0099] Examples of perfluoroalkyl carboxylic acid compounds include perfluoroalkyl carboxylic acids and salts of perfluoroalkyl carboxylic acids.
[0100] Examples of the perfluoroalkyl phosphoric ester compounds include phosphoric perfluoroalkyl esters and perfluoroalkyl phosphoric ester salts.
[0101] [00101] Examples of polyoxyalkylene ether polymer compounds that have ether groups as side chains include polyoxyalkylene ether polymer that have ether groups as side chains, polyoxyalkylene ether polymer sulfates that have ether groups as side chains, and salts of polyoxyalkylene ether polymer that have ether groups as side chains.
[0102] [00102] Examples of salt ions in such fluorine-based surfactants include Li, Na, K, NH4, NH3CH2CH2OH, NH2 (CH2CH2OH) 2, and NH (CH2CH2OH) 3.
[0103] [00103] Examples of commercially available fluorine-based surfactants include SURFLON S-111, S-112, S-113, S-121, S-131, S-132, S-141 and S-145 (these are manufactured by Asahi Glass Co. Ltd.); Fluorad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430 and FC-431 (these are manufactured by Sumitomo 3M Limited); MEGAFACE F-470, F-1405 and F-474 (these are manufactured by Dainippon Ink and Chemicals); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, and UR (these are manufactured by E. I. du Pont de Nemours and Company); FTERGENT FT-110, FT-250, FT-251, FT-400S, FT-150, and FT-400SW (these are manufactured by NEOS COMPANY LIMITED), and PolyFox PF-136A, PF-156A, PF151N, PF-154 and PF-159 (these are manufactured by OMNOVA Solutions Inc.).
[0104] [00104] Of these, FS-300 (manufactured by EI du Pont de Nemours and Company), FT-110, FT-250, FT-251, T-400S, FT-150, and FT-400SW ( manufactured by NEOS COMPANY LIMITED), and PolyFox PF-151N (manufactured by OMNOVA Solutions Inc.) since good image quality is achieved and, in particular, the color development and color level capability for paper sheets are considerably improved.
[0105] [00105] Silicone-based surfactants are not particularly limited and can be selected appropriately according to the purpose. Examples of the silicone-based surfactants include modified side chain polydimethylsiloxanes, modified end polydimethylsiloxanes, modified single-ended polydimethylsiloxanes, and modified end-chain polydimethylsiloxanes. In particular, polyether-modified silicone-based surfactants which have a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group as a modifying group are preferred as the surfactants exhibit good properties as aqueous surfactants.
[0106] [00106] Silicone-based surfactants are readily available from, for example, BYK Japan KK, Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., NIHON EMULSION Co., Ltd., or Kyoeisha Chemical Co., Ltd.
[0107] [00107] Examples of anionic surfactants include polyoxyethylene alkyl ether acetates, dodecylbenzenesulfonates, laurates, and polyoxyethylene alkyl ether sulfate salts.
[0108] [00108] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl amines, and polyoxyethylene alkyl amides.
[0109] [00109] If necessary, an aqueous paint according to the present disclosure may suitably include another component such as a pH-adjusting agent, an antiseptic fungicide, an anti-corrosion agent, an antioxidant, a UV absorber, an oxygen absorber, or a light stabilizer.
[0110] [00110] The pH adjusting agent is not particularly limited and can be selected appropriately according to the purpose as long as it allows the pH to be adjusted to 8.5 to 11 without adversely affecting the prepared ink. Examples of the pH adjusting agent include alcohol amines, alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, and alkali metal carbonates. Examples of the alcohol amines include diethanolamine, triethanolamine, and 2-amino-2-ethyl-1,3-propanediol. Examples of the hydroxides of alkali elements include lithium hydroxide, sodium hydroxide and potassium hydroxide. Examples of ammonium hydroxides include ammonium hydroxide and quaternary ammonium hydroxide. Examples of phosphonium hydroxides include quaternary phosphonium hydroxide. Examples of alkali metal carbonates include lithium carbonate, sodium carbonate and potassium carbonate.
[0111] [00111] Examples of the antiseptic fungicide include sodium dehydroacetate, sodium sorbate, sodium 2-pyridinetiol-1-oxide, sodium benzoate, and sodium pentachlorophenol.
[0112] [00112] Examples of the anticorrosive include acid sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitride, pentaerythritol tetranitride, and dicyclohexylammonium nitride.
[0113] [00113] Examples of the antioxidant include phenol-based antioxidants (including hidden phenol-based antioxidants), amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.
[0114] [00114] Examples of the UV absorber include benzophenone-based UV absorbers, benzotriazole-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, and nickel complex salt-based UV absorbers.
[0115] [00115] An aqueous ink according to the present disclosure can be produced, for example, by dispersing or dissolving, in an aqueous medium, water, a water-soluble organic solvent, a pigment, the copolymer described above, and optionally another component and by stirring or mixing the solution. The copolymer can be used as a pigment dispersion resin during the preparation of a pigment dispersion.
[0116] [00116] The dispersion can be carried out with, for example, a sand mill, a homogenizer, a spherical mill, a paint stirrer, or an ultrasonic dispersion apparatus. Stirring and mixing can be carried out, for example, with a stirrer having a normal impeller, a magnetic stirrer, or a high speed dispersion apparatus.
[0117] [00117] During production, coarse particles are optionally filtered with a filter, a centrifuge, or the like and degassing is preferably carried out.
[0118] [00118] Properties of an aqueous paint according to the present disclosure are not particularly limited and can be selected appropriately according to the purpose. For example, the viscosity and surface tension of the aqueous paint are preferably within the following ranges.
[0119] [00119] The viscosity of the aqueous paint at 25 ° C is preferably 3 to 20 mPa.s. When viscosity is 3 mPa.s or more, the effects of increasing print density and improving character quality are provided. When the viscosity is 20 mPa.s or less, the ink discharge capacity can be guaranteed.
[0120] [00120] Viscosity can be measured with, for example, a viscometer (RL-550, manufactured by Toki Sangyo Co. Ltd.) at 25 ° C.
[0121] [00121] The surface tension of the aqueous paint at 25 ° C is preferably 40 mN / m or less.
[0122] [00122] An ink cartridge according to the present disclosure contains the aqueous ink described above in a container and optionally includes another member which is selected in an appropriate manner.
[0123] [00123] The container is not particularly limited. For example, the shape, structure, size or material of the container can be selected appropriately according to the purpose. For example, the container preferably includes at least one ink pouch formed from a laminated aluminum film, a resin film or the like.
[0124] [00124] The ink cartridge will be described with reference to FIGS. 13 and 14. FIG. 13 illustrates an example of the ink cartridge. FIG. 14 illustrates the ink cartridge in FIG. 13 and its case (wrapper). In the ink cartridge 200, the ink is loaded through an ink inlet 242 to an ink pouch 241; the gas is vented from the ink pouch 241; and the ink inlet 242 is then fused. At the time of use, a needle into the body of the device is inserted through an ink outlet 243 formed by a rubber member to allow delivery to the device. The ink pouch 241 is formed of a packaging member such as a gas-impermeable aluminum laminate film. As illustrated in FIG. 14, in general, this ink pouch 241 is contained in a cartridge case 244 formed of plastic and is used in the state of being detachably attached to various inkjet engraving devices. EXAMPLES
[0125] [00125] Hereinafter, the present disclosure will be described specifically further with reference to the Examples. However, the present disclosure is not limited to these Examples. In the Examples, "parts" and "%" denote "parts by weight" and "% by weight" unless otherwise specified.
[0126] [00126] The molecular weight of the copolymers obtained in the Examples and in the Comparative Examples were obtained as follows: Measurement of the Molecular Weight of the Copolymer
[0127] - Instrumento de medição: GPC-8020 (fabricado por Tosoh Corporation) - Coluna: TSK G2000 HXL e G4000 HXL (fabricado por Tosoh Corporation) - Temperatura: 40°C - Solvente: tetra-hidrofurano (THF) - Velocidade de fluxo: 1,0 mL/minuto 1 mL de um copolímero que possui uma concentração de 0,5% em peso foi vertido para a coluna e o peso molecular médio numérico Mn e o peso molecular médio mássico Mw do copolímero medido foram calculados usando a curva de calibração de peso molecular preparada por uma amostra de poliestireno de dispersão simples.[00127] The molecular weight was increased by a gel permeation chromatography (GPO) under the following condition: - Measuring instrument: GPC-8020 (manufactured by Tosoh Corporation) - Column: TSK G2000 HXL and G4000 HXL (manufactured by Tosoh Corporation) - Temperature: 40 ° C - Solvent: tetrahydrofuran (THF) - Flow rate: 1.0 mL / minute 1 ml of a copolymer having a concentration of 0.5% by weight was poured into the column and the numerical average molecular weight Mn and the mass average molecular weight Mw of the measured copolymer were calculated using the molecular weight calibration curve prepared by a sample of polystyrene of simple dispersion.
[0128] [00128] Ethylene glycol (15.6 g, 252 mmol) was dissolved in 100 ml of methylene chloride. To this solution, 3.49 g (44 mmol) of pyridine was added and the solution was cooled with water ice. To this solution being stirred, a solution containing 8.00 g (42 mmol) of 2-naphthalenocarbonyl chloride dissolved in 80 ml of methylene chloride was added over one hour. This solution was stirred for 2 hours and subsequently further stirred at room temperature for 6 hours. The resulting reaction solution was rinsed with water, the organic phase was then separated and dried over magnesium sulfate, and the solvent was distilled. The residue was purified by silica gel column chromatography with a methylene chloride / methanol (97/3) solvent mixture that serves as an eluent to provide 6.88 g of 2-naphthoic acid 2-hydroxyethyl ester.
[0129] [00129] Subsequently, 0.2 g of a styrene - maleic anhydride copolymer [SMA1000P, manufactured by KAWAHARA PETROCHEMICAL CO. LTD., Mass average molecular weight (Mw): 5500, numerical average molecular weight (Mn): 2000] and 0.64 g (3 mmol) of 2-naphthoic acid 2-hydroxyethyl ester was dissolved in 8 ml of dry dimethylformamide and stirred at 120 ° C for 12 hours. The resulting reaction solution was diluted with toluene and the solvent was distilled. The residue was purified with a recycling HPLC (LC-9201, manufactured by Japan Analytical Industry Co., Ltd., development solvent: tetrahydrofuran, flow rate: 3.5 mL / min) to provide 0.17 g of Copolymer 1 having a mass molecular weight (Mw) of 5700 and a molecular weight number (Mn) of 2200.
[0130] [00130] The infrared absorption spectrum (Kbr pellet method) of Copolymer 1 is illustrated in FIG. 1. Example 2
[0131] [00131] As in example 1, 4-hydroxyethyl ester of 2-naphthoic acid was obtained except that ethylene glycol was replaced by 1,4-butanediol.
[0132] [00132] Subsequently, in the same way as in Example 1, Copolymer 2 having a mass molecular weight (Mw) of 5700 and a molecular weight number (Mn) of 2200 was obtained.
[0133] [00133] The infrared absorption spectrum (Kbr pellet method) of Copolymer 2 is illustrated in FIG. 2. Example 3
[0134] [00134] As in example 1, 6-hydroxyethyl ester of 2-naphthoic acid was obtained except that ethylene glycol was replaced with 1,6-butanediol.
[0135] [00135] Subsequently, in the same manner as in Example 1, Copolymer 3 having a mass molecular weight (Mw) of 5800 and a molecular weight number (Mn) of 2300 was obtained.
[0136] [00136] The infrared absorption spectrum (Kbr pellet method) of Copolymer 3 is illustrated in FIG. 3. Example 4
[0137] [00137] As in example 1, 12-hydroxyethyl ester of 2-naphthoic acid was obtained except that ethylene glycol was replaced by 1,12-dodecanediol.
[0138] [00138] Subsequently, in the same manner as in Example 1, Copolymer 2 having a mass molecular weight (Mw) of 5800 and a molecular weight number (Mn) of 2300 was obtained.
[0139] [00139] The infrared absorption spectrum (Kbr pellet method) of Copolymer 4 is illustrated in FIG. 4. Example 5
[0140] [00140] To a solvent mixture of 80 ml of dry toluene and 15 ml of dry pyridine, 5.59 g (30 mmol) of 1,8-naphthalenedicarboxylic anhydride and 3.52 g (30 mmol) of 6-amino- 1-hexanol was added. This solution was refluxed for 16 hours and then cooled to room temperature. Subsequently, the solvent was distilled off and the residue was purified by silica gel column chromatography with a mixture of toluene / ethyl acetate (7/3 to 5/5) which serves as an eluent to provide 7.67 g of an imide compound. Subsequently, as in Example 1, this imide compound and the SMA1000P described above were used to provide Copolymer 5 having a mass molecular weight (Mw) of 5700 and a molecular weight number (Mn) of 2200.
[0141] [00141] The infrared absorption spectrum (Kbr pellet method) of Copolymer 5 is illustrated in FIG. 5. Example 6
[0142] [00142] In the same way as in Example 1, 6-hydroxyethyl ester of 2-naphthoic acid obtained in example 3 and a copolymer of styrene - maleic anhydride [SMA2000P, manufactured by KAWAHARA PETROCHEMICAL CO. LTD., Mass molecular weight (Mw): 7500, numerical average molecular weight (Mn): 3000] were used to provide Copolymer 6 having a mass molecular weight (Mw) of 7700 and a numerical molecular weight (Mn) of 3200.
[0143] [00143] The infrared absorption spectrum (Kbr pellet method) of Copolymer 6 is illustrated in FIG. 6. Example 7
[0144] [00144] In the same way as in Example 1, 6-hydroxyethyl ester of 2-naphthoic acid obtained in example 3 and a copolymer of styrene - maleic anhydride [SMA3000P, manufactured by KAWAHARA PETROCHEMICAL CO. LTD., Mass molecular weight (Mw): 9500, numerical average molecular weight (Mn): 3800] were used to provide Copolymer 7 having a mass molecular weight (Mw) of 9900 and a numerical molecular weight (Mn) of 4100.
[0145] [00145] The infrared absorption spectrum (Kbr pellet method) of Copolymer 7 is illustrated in FIG. 7. Example 8
[0146] [00146] To 80 mL of methyl ethyl ketone, 9.05 g (50 mmol) of 4-hydroxybiphenyl, 10.20 g (60 mmol) of 6-bromo-1-hexanol, and 20.7 g (150 mmol) of potassium carbonate were added. This solution was refluxed for 24 hours and then cooled to room temperature. This solution was diluted with 200 ml of methylene chloride and rinsed with water three times. The organic phase was then separated and dried over magnesium sulfate, and the solvent was distilled. The residue was dissolved in toluene and purified by recrystallization to provide 10.25 g of 6- (4-phenylphenoxy-hexane-1-ol.
[0147] [00147] Subsequently, 0.72 g (2.7 mmol) of 6- (4-phenylphenoxy) hexane-1-ol and 1.0 g of a copolymer of styrene - maleic anhydride [SMA 3024, manufactured by KAWAHARA PETROCHEMICAL CO . LTD., Mass average molecular weight (Mw): 24000] was dissolved in 1 ml of dry dimethylacetamide and stirred under reflux for 2 hours. The resulting reaction solution was diluted with toluene and the solvent was distilled. The residue was purified with a recycling HPLC (LC-9201, manufactured by Japan Analytical Industry Co. Ltd., development solvent: tetrahydrofuran, flow rate: 3.5 mL / min) to provide 1.16 g of Copolymer 8 having a mass molecular weight (Mw) of 24300 and a numerical molecular weight (Mw) of 10000.
[0148] [00148] The infrared absorption spectrum (Kbr pellet method) of Copolymer 8 is illustrated in FIG. 8. Example 9
[0149] [00149] To a solvent mixture of 130 ml of dry toluene and 30 ml of dry pyridine, 9.91 g (50 mmol) of 2,3-naphthalenedicarboxylic anhydride and 5.86 g (50 mmol) of 6-amino- 1-hexanol was added. This solution was refluxed for 12 hours and then cooled to room temperature. Subsequently, the solvent was distilled and the residue was purified by silica gel column chromatography with a mixture of toluene / ethyl acetate (7/3 to 5/5) which serves as an eluent to provide 11.34 g of an imide compound.
[0150] [00150] Subsequently, 0.80 g (2.7 mmol) of the imide compound and 1.0 g of the SMA3024 described above was dissolved in 1 ml of dry dimethylacetamide and stirred under reflux for 3 hours. The resulting reaction solution was diluted with toluene and the solvent was distilled. The residue was purified with a recycling HPLC (LC-9201, manufactured by Japan Analytical Industry Co., Ltd., development solvent: tetrahydrofuran, flow rate: 3.5 mL / min) to provide 1.21 g of Copolymer 9 having a mass molecular weight (Mw) of 24200 and a numerical molecular weight (Mw) of 10000.
[0151] [00151] The infrared absorption spectrum (Kbr pellet method) of Copolymer 9 is illustrated in FIG. 9. Example 10
[0152] [00152] In a solvent mixture of 150 ml of tetrahydrofuran and 30 ml of methylene chloride, 10.0 g (19.4 mmol) of 1.16-hexadecanediol were dissolved and 1.54 g (19.4 mmol) of pyridine was added. To this solution being stirred, a solution containing 3.70 g (38.8 mmol) of 2-naphthalenocarbonyl chloride dissolved in 50 mL 150 mL of tetrahydrofuran was added for 2 hours. This solution was then further stirred for one hour. The solvent was distilled from the resulting reaction solution. The residue was rinsed with methanol, then rinsed with water, and dried; and this residue was purified by silica gel column chromatography with a methylene chloride / methanol (95/5) solvent mixture that serves as an eluent to provide 2.06 g of acid ester 16-hydroxyhexadecane 2 -naphthotic.
[0153] [00153] Subsequently, 0.32 g (0.78 mmol) of 16-hydroxyhexadecane of 2-naphthoic acid ester and 0.30 g of the SMA3024 described above was dissolved in 1 ml of dry dimethylacetamide and stirred under reflux for 2 hours. The resulting reaction solution was diluted with toluene and the solvent was distilled. The residue was purified with a recycling HPLC (LC-9201, manufactured by Japan Analytical Industry Co., Ltd., development solvent: tetrahydrofuran, flow rate: 3.5 mL / min) to provide 0.47 g of Copolymer 10 having a mass molecular weight (Mw) of 24,400 and a numerical molecular weight (Mw) of 10,000.
[0154] [00154] The infrared absorption spectrum (Kbr pellet method) of Copolymer 10 is illustrated in FIG. 10. Example 11
[0155] [00155] Copolymer 7 (1.37 g) obtained in Example 7 was dissolved in 3 ml of Equamide M100 (manufactured by Idemitsu Kosan Co. Ltd.). Tetraethylammonium hydroxide (0.294 g) was dissolved in 12 ml of deionized water. To the resulting aqueous solution under vigorous stirring, the Equamide M100 solution of the copolymer was added. After the addition was completed, the solution was stirred for about an hour and the solvent was distilled. The residue was rinsed with deionized water and dried under reduced pressure to provide Copolymer 11 (copolymer in which Copolymer 7 carboxyl groups were changed to tetraethylammonium carboxylate) having a mass molecular weight (Mw) of 9900 and a numerical molecular weight ( 4100 Mw). Example 12
[0156] [00156] As in Example 1, 2-hydroxyethyl ester of 2-naphthoic acid was obtained. After that, 10.3 g (25 mmol) of maleic anhydride and 6.81 g (25 mmol) of 6-hydroxyethyl ester of 2-naphthoic acid were dissolved in 50 ml of methyl ethyl ketone and refluxed by heating for 6 hours. The resulting reaction mixture was concentrated. The residue was purified by silica gel column chromatography with a mixture of methylene chloride / methanol solvent (volume ratio: 9/1) which serves as an eluent to provide 8.1 g of a compound having a represented structure by the following formula [hereinafter referred to as Maleic Derivative 1].
[0157] [00157] Subsequently, 3.20 g (8.6 mmol) of Maleic Derivative 1 were dissolved in 1.80 g (17.3 mmol) of styrene. To this solution, 5.0 g of deionized water, 0.15 g of AQUALON KH-10 (anionic reactive surfactant manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD.), And 0.05 g of ammonium persulfate was added and treated with a homomixer to provide the pre-emulsion. Subsequently, 0.1 g of AQUALON KH-10 was added to 5.0 g of deionized water and heated to 80 ° C under a stream of argon. To this solution, 10% of the pre-emulsion was added and subjected to initial polymerization for 30 minutes. Subsequently, the rest of the pre-emulsion was dripped for 2 hours to cause polymerization. After that, the polymerization was additionally caused at 80 ° C for 2 hours. This solution was cooled, then filtered, and neutralized with aqueous ammonia to provide Copolymer 12 having a solids content concentration of 30% with a mass molecular weight (Mw) of 17000 and a numerical molecular weight (Mw) of 9000.
[0158] [00158] After the water was distilled from Copolymer 12 in the emulsion state under a stream of hot air, drying under reduced pressure was performed to provide Copolymer 12. The infrared absorption spectrum of Copolymer 12 is illustrated in FIG . 11. Example 13
[0159] [00159] Maleic derivative 1 (3.08 g (8.32 mmol)) and 0.64 g (4.99 mmol) of butyl acrylate was dissolved in 1.73 g (16.6 mmol) of styrene. To this solution, 5.0 g of deionized water, 0.15 g of AQUALON KH-10 (anionic reactive surfactant manufactured by DAI-ICHI KOGYO SEIYAKU CO. LTD.), And 0.05 g of ammonium persulfate were added and treated with a homomixer to provide the pre-emulsion. Subsequently, 0.1 g of AQUALON KH-10 was added to 5.0 g of deionized water and heated to 80 ° C under a stream of argon. To this solution, 10% of the pre-emulsion was added and subjected to initial polymerization for 30 minutes. Subsequently, the rest of the pre-emulsion was dripped for 2 hours. This solution was cooled, then filtered, and neutralized with aqueous ammonia to provide Copolymer 13 having a solids content concentration of 30% with a mass molecular weight (Mw) of 2800 and a molecular weight number (Mn) of 10000.
[0160] [00160] The infrared absorption spectrum (Kbr pellet method) of Copolymer 13 is illustrated in FIG. 12.
[0161] [00161] The structures of the Copolymers in Examples 1 to 13 above are summarized in Table 1.
[0162] [00162] In Example 11, in the salt of specific Example 1, "*" for R denotes a tetraethylammonium salt.
[0163] [00163] In Example 13, in Specific Example 12, m represents 0 and n represents 6. Comparative Example 1
[0164] [00164] A styrene-maleic anhydride copolymer [0.2 g, SMA1000P, manufactured by KAWAHARA PETROCHEMICAL CO., LTD., Mass average molecular weight (Mw): 5500, numerical average molecular weight (Mn): 2000] and 0 , 30 g (3 mmol) of 1-hexanol was dissolved in 8 mL of dry dimethylformamide and stirred to react at 120 ° C for 12 hours. The resulting reaction solution was diluted with toluene and the solvent was distilled. The residue was purified with a recycling HPLC (LC-9201, manufactured by Japan Analytical Industry Co. Ltd., development solvent: tetrahydrofuran, flow rate: 3.5 mL / min) to provide 0.21 g of Comparative copolymer 1 having a mass molecular weight (Mw) of 5600 and a molecular weight number (Mn) of 2100. Comparative Example 2
[0165] [00165] Maleic anhydride (10.3 g (25 mmol) and 2.55 g (25 mmol) of 1-hexanol were dissolved in 50 mL of methyl ketone ketone and refluxed under heating to react for 6 hours. The residue was purified by silica gel column chromatography with a methylene chloride / methanol solvent mixture (volume ratio: 9/1) which serves as an eluent to provide 8.7 g of a compound which has a structure represented by the following formula [hereinafter referred to as Maleic Derivative 2].
[0166] [00166] Comparative Copolymer 2 which has a solids content concentration of 30% with a mass molecular weight (Mw) of 17000 and a numerical molecular weight (Mn) of 7000, was obtained as in Example 12 except that the Maleic Derivative 1 was replaced by Maleic Derivative 2. Example 31 Preparation of Pigment Dispersion
[0167] [00167] Copolymer 1 (5.0 parts) was dissolved in 8.0 parts of tetrahydrofuran. To this solution, 70.0 parts of deionized water and a neutralizer (sodium hydroxide solution) in an amount that corresponds to 100% of the acid value of the copolymer were added to the neutralization achieved. After that, 20.0 parts of carbon black (NIPEX150, manufactured by Degussa) were added and stirred. The resulting mixture was subjected to the dispersion circulation with a disc type bead mill (manufactured by SHINMARU ENTERPRISES CORPORATION, KDL type medium: zirconia spheres having a diameter of 0.1 mm) at a peripheral speed of 10 m / s for an hour. Subsequently, the solvent was distilled off with an evaporator under reduced pressure. The residue was filtered with a membrane filter that has a pore size of 1.2 pm and mixed with an adjustment amount of deionized water to provide 95.0 parts of Pigment dispersion 31 (concentration of pigment solids content: 20%). Preparation of the paint
[0168] [00168] Pigment dispersion 31 (40.0 parts), 20.0 parts of 1,3-butanediol, 10.0 parts of glycerin, 1.0 part of 2,2,4-trimethyl-1,3-pentanediol , 2.0 parts of Zonyl FS-300 (manufactured by EI du Pont de Nemours and Company, fluoride-based surfactant, solid content: 40% by mass), and 26.0 parts of deionized water were mixed, stirred by hour, and then filtered with a membrane filter having a pore size of 1.2 pm to provide the aqueous Paint 31 according to the present disclosure. Example 32
[0169] [00169] Pigment dispersion 32 was obtained as in Example 31 except that Copolymer 1 used in the preparation of the pigment dispersion was replaced by Copolymer 2.
[0170] [00170] Subsequently, the aqueous Paint 32 according to the present disclosure was obtained as in Example 31 except that the Pigment Dispersion 31 used in the Preparation of the Ink was replaced by the Pigment Dispersion 32. Example 33
[0171] [00171] Pigment dispersion 33 was obtained as in Example 31 except that Copolymer 1 used in the preparation of the pigment dispersion was replaced by Copolymer 3.
[0172] [00172] Subsequently, the aqueous Ink 33 according to the present disclosure was obtained as in Example 31 except that the Pigment Dispersion 31 used in the Preparation of the Ink was replaced by the Pigment Dispersion 33. Example 34
[0173] [00173] Pigment dispersion 34 was obtained as in Example 31 except that the carbon black (NIPEX150, manufactured by Degussa) used in the preparation of the pigment dispersion was replaced by Pigment Blue 15: 3 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. CHROMOFINE BLUE, cyan pigment).
[0174] [00174] Subsequently, the aqueous Paint 34 according to the present disclosure was obtained as in Example 33 except that the Pigment Dispersion 33 used in the Preparation of the Ink was replaced by the Pigment Dispersion 34. Example 35
[0175] [00175] Pigment dispersion 35 was obtained as in Example 33 except that the carbon black (NIPEX150, manufactured by Degussa) used in the preparation of the pigment dispersion was replaced with Pigment Red 122 (manufactured by Clariant, Magenta Toner EO02, magenta pigment ).
[0176] [00176] Subsequently, the aqueous Paint 35 according to the present disclosure was obtained as in Example 33 except that the Pigment Dispersion 33 used in the Preparation of the Ink was replaced by the Pigment Dispersion 35. Example 36
[0177] [00177] Pigment dispersion 34 was obtained as in Example 31 except that the carbon black (NIPEX150, manufactured by Degussa) used in the preparation of the pigment dispersion was replaced by Yellow Pigment (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., FAST YELLOW 531, yellow pigment).
[0178] [00178] Subsequently, the aqueous Paint 36 according to the present disclosure was obtained as in Example 33 except that the Pigment Dispersion 33 used in the Preparation of the Ink was replaced by the Pigment Dispersion 36. Example 37
[0179] [00179] Pigment dispersion 37 was obtained as in Example 31 except that Copolymer 1 used in the preparation of the pigment dispersion was replaced by Copolymer 4.
[0180] [00180] Subsequently, the aqueous Ink 37 according to the present disclosure was obtained as in Example 31 except that the Pigment Dispersion 31 used in the Preparation of the Ink was replaced by the Pigment Dispersion 37. Example 38
[0181] [00181] Pigment dispersion 38 was obtained as in Example 31 except that Copolymer 1 used in the preparation of the pigment dispersion was replaced by Copolymer 5.
[0182] [00182] Subsequently, the aqueous Paint 38 according to the present disclosure was obtained as in Example 31 except that the Pigment Dispersion 31 used in the Preparation of the Ink was replaced by the Pigment Dispersion 38. Example 39
[0183] [00183] Pigment dispersion 39 was obtained as in Example 31 except that Copolymer 1 used in the preparation of the pigment dispersion was replaced by Copolymer 6.
[0184] [00184] Subsequently, the aqueous Paint 39 according to the present disclosure was obtained as in Example 31 except that the Pigment Dispersion 31 used in the Preparation of the Ink was replaced by the Pigment Dispersion 39. Example 40
[0185] [00185] Pigment dispersion 40 was obtained as in Example 31 except that Copolymer 1 used in the preparation of the pigment dispersion was replaced by Copolymer 7.
[0186] [00186] Subsequently, the aqueous Ink 40 according to the present disclosure was obtained as in Example 31 except that the Pigment Dispersion 31 used in the Preparation of the Ink was replaced by the Pigment Dispersion 40. Example 41
[0187] [00187] Pigment dispersion 41 was obtained as in Example 31 except that Copolymer 1 used in the preparation of the pigment dispersion was replaced by Copolymer 8.
[0188] [00188] Subsequently, the aqueous Paint 41 according to the present disclosure was obtained as in Example 31 except that the Pigment Dispersion 31 used in the Preparation of the Ink was replaced by the Pigment Dispersion 41. Example 42
[0189] [00189] Pigment dispersion 42 was obtained as in Example 31 except that Copolymer 1 used in the preparation of the pigment dispersion was replaced by Copolymer 9.
[0190] [00190] Subsequently, the aqueous Ink 42 according to the present disclosure was obtained as in Example 31 except that the Pigment Dispersion 31 used in the Preparation of the Ink was replaced by the Pigment Dispersion 42. Example 43
[0191] [00191] Pigment dispersion 43 was obtained as in Example 31 except that Copolymer 1 used in the preparation of the pigment dispersion was replaced by Copolymer 10.
[0192] [00192] Subsequently, the aqueous Ink 43 according to the present disclosure was obtained as in Example 31 except that the Pigment Dispersion 31 used in the Preparation of the Ink was replaced by the Pigment Dispersion 43. Example 44
[0193] [00193] Pigment dispersion 44 was obtained as in Example 31 except that Copolymer 1 used in the preparation of the pigment dispersion was replaced by Copolymer 11.
[0194] [00194] Subsequently, the aqueous Ink 44 according to the present disclosure was obtained as in Example 31 except that the Pigment Dispersion 31 used in the Preparation of the Ink was replaced by the Pigment Dispersion 44. Example 45
[0195] [00195] The following materials were mixed and stirred for 30 minutes to prepare aqueous Solution 1. 2- ethyl-1,3-hexanediol 2.00 parts Glycerol 10.00 pieces 3- methoxy-N, N-dimethylpropanoamide 15.00 parts 3-butoxy-N, N-dimethylpropanoamide 15.00 parts 2- (cyclohexylamino) ethane sulfonic acid 0.05 part 2,4,7,9-tetramethyl-4,7-decanedium 0.50 part Zonyl FS-300 (fluoride-based surfactant, manufactured by EI du Pont de Nemours and Company) 0.25 part Diethanolamine 0.01 part deionized water 12.93 parts
[0196] [00196] Subsequently, 50 g of dry carbon black, 100 ml of deionized water, and 15.5 g (50 mmol) were mixed followed by heating to 60 ° C while being stirred at 300 rpm. 50 mmol of 20% aqueous sodium nitride solution was added in 15 minutes. Then, the resultant was stirred at 60 ° C for three hours. The contents were diluted with 75 ml of deionized water followed by filtration. Deionized water was added in such a way that the concentration of the solid portion was 20.0% to prepare the Pigment Dispersion 45 of carbon black.
[0197] [00197] Subsequently, to Aqueous Solution 1, 37.50 parts of Pigment dispersion 45 were added and stirred for 30 minutes; and 6.67 parts of Copolymer 12 (solids content concentration: 30%) were added additionally and stirred for 30 minutes. This solution was filtered with a membrane filter that has a pore size of 1.2 gm to provide the aqueous Ink 45 in accordance with the present disclosure.
[0198] [00198] Example 46
[0199] [00199] The following materials were mixed and stirred for 30 minutes to prepare aqueous Solution 2. 2- ethyl-1,3-hexanedium 12.00 parts Glycerol 10.00 pieces 3- methoxy-N, N-dimethylpropanoamide 20.00 parts 3-butoxy-N, N-dimethylpropanoamide 20.00 parts 2- (cyclohexylamino) ethane sulfonic acid 0.05 part 2,4,7,9-tetramethyl-4,7-decanediol 0.50 part Zonyl FS-300 (fluoride-based surfactant, manufactured by EI du Pont de Nemours and Company) 0.25 part Diethanolamine 0.01 part deionized water 17.93 parts
[0200] [00200] Subsequently, 4.50 g of p-aminobenzoate was added to 150 g of deionized water heated to 60 ° C followed by stirring for minutes at 8000 rpm. Next, a solution in which 1.80 g of sodium nitride was dissolved in 15 g of deionized water was added to this mixture. Immediately thereafter, 20 g of copper phthalocyanine pigment PB 15: 4 (manufactured by Sun Chemical Corporation) was added to it followed by a one hour mixture at 8500 rpm. In addition, 4.5 g of p-aminobenzoate was dissolved in 15 g of deionized water was added to this mixture followed by a three hour mixture at 8500 rpm at 65 ° C. The reaction mixture thus obtained was filtered through a 200 nm mesh. Subsequent to washing with water, the cyan pigment thus obtained was dispersed in water. Coarse particles were removed by a centrifuge and deionized water was added in such a way that the concentration of the solid portion was 20.0% to obtain Pigment dispersion 46 of the cyan pigment which was treated on the surface with p-aminobenzoate.
[0201] [00201] Subsequently, to Aqueous Solution 2, 22.50 parts of Pigment dispersion 46 was added and stirred for 30 minutes; and 6.67 parts of Copolymer 13 (solids content concentration: 30%) was added additionally and stirred for 30 minutes. This solution was then filtered with a membrane filter that has a pore size of 1.2 gm to provide aqueous Paint 46 in accordance with the present disclosure. Example 47
[0202] [00202] As in Example 45, Aqueous Solution 1 was prepared.
[0203] [00203] Subsequently, 4.50 g of sulfanilic acid were added to 150 g of deionized water heated to 60 ° C followed by stirring for 10 minutes at 8000 rpm. Next, a solution in which 1.80 g of sodium nitride was dissolved in 15 g of deionized water was added to this mixture. Immediately thereafter, 20 g of magenta pigment PR 122 (manufactured by Sun Chemical Corporation) was added to it followed by a one hour mixture at 8500 rpm. In addition, 4.5 g of sulfanilic acid was dissolved at 8500 rpm at 65 ° C. The reaction mixture thus obtained was filtered through a 200 nm mesh. Subsequent to washing with water, the cyan pigment thus obtained is dispersed in water. Coarse particles were removed by a centrifuge and deionized water was added in such a way that the concentration of the solid portion was 20.0% to obtain the pigment dispersion of the magenta pigment which had the surface treated with sulfanilic acid.
[0204] [00204] Subsequently, to aqueous solution 1, 22.50 parts of Pigment dispersion 47 was added and stirred for 30 minutes; and 6.67 parts of Copolymer 13 (solids content concentration: 30%) was added additionally and stirred for 30 minutes. This solution was then filtered with a membrane filter that has a pore size of 1.2 μm to provide the aqueous ink 47 in accordance with the present disclosure. Example 48
[0205] [00205] As in Example 46, Aqueous Solution 2 was prepared. To Aqueous Solution 2, 37.50 parts of Pigment dispersion 34 (cyan pigment, solids content: 20.0%) prepared in Example 34 were added and stirred for 30 minutes; and 6.67 parts of Copolymer 13 (solids content concentration: 30%) were then added and stirred for 30 minutes. This solution was then filtered with a membrane filter having a pore size of 1.2 μm to provide aqueous Paint 48 in accordance with the present disclosure. Comparative Example 21
[0206] [00206] Comparative pigment dispersion 21 was obtained as in Example 31 except that Copolymer 1 used in the Preparation of the pigment dispersion was replaced by Comparative Copolymer 1.
[0207] [00207] Subsequently, Comparative Aqueous Ink 21 was obtained as in Example 31 except that the Pigment Dispersion 31 used in the Preparation of the ink was replaced by the Comparative Pigment Dispersion 21. Comparative Example 22
[0208] [00208] Comparative pigment dispersion 22 was obtained as in Example 34 except that Copolymer 3 used in the Preparation of the pigment dispersion was replaced by Comparative Copolymer 1.
[0209] [00209] Subsequently, the Comparative Aqueous Ink 22 was obtained as in Example 34 except that the Pigment Dispersion 34 used in the Preparation of the ink was replaced by the Comparative Pigment Dispersion 22. Comparative Example 23
[0210] [00210] Comparative pigment dispersion 23 was obtained as in Example 35 except that Copolymer 1 used in the Preparation of the pigment dispersion was replaced by Comparative Copolymer 1.
[0211] [00211] Subsequently, Comparative Aqueous Ink 23 was obtained as in Example 35 except that the Pigment Dispersion 35 used in the Preparation of the ink was replaced by the Comparative Pigment Dispersion 23. Comparative Example 24
[0212] [00212] Comparative pigment dispersion 24 was obtained as in Example 36 except that Copolymer 3 used in the Preparation of the pigment dispersion was replaced by Comparative Copolymer 3.
[0213] [00213] Subsequently, Comparative Aqueous Ink 24 was obtained as in Example 36 except that the Pigment Dispersion 36 used in the Preparation of the ink was replaced by the Comparative Pigment Dispersion 24. Comparative Example 25
[0214] [00214] As in Example 46, Aqueous Solution 2 was prepared. To aqueous solution 2, 22.50 parts of Pigment dispersion 46 (cyan pigment, solids content: 20.0%) prepared in Example 46 was added and stirred for 30 minutes. This solution was then filtered with a membrane filter having a pore size of 1.2 μm to provide comparative aqueous paint 25. Comparative Example 26
[0215] [00215] As in Example 47, Aqueous Solution 1 was prepared. To Aqueous Solution 1, 37.50 parts of Pigment Dispersion 47 (magenta pigment, solids content: 20.0%) prepared in Example 47 was added and stirred for 30 minutes. This solution was then filtered with a membrane filter having a pore size of 1.2 μm to provide comparative aqueous paint 26. Comparative Example 27
[0216] [00216] As in Comparative Example 22, Comparative Pigment Dispersion 22 was prepared. To Comparative Pigment Dispersion 22, 6.67 parts of Comparative Copolymer 2 (solids content concentration: 30%) was added and stirred for 30 minutes. This solution was then filtered with a membrane filter having a pore size of 1.2 μm to provide the comparative aqueous ink 27.
[0217] [00217] The characteristics of the aqueous Paints prepared in the Examples and Comparative Examples were evaluated by methods described below. The results are summarized in Table 2. Image density
[0218] [00218] In an environment at 23 ° C and 50% relative humidity, each ink was loaded into an inkjet printer (manufactured by Ricoh Company, Ltd., IPSiO GX5000); a graphic of the general symbol (64 points) of JIS X 0208 (1997), 2223 formed with Microsoft Word 2000 (manufactured by Microsoft Corporation) was printed on Sheet of plain paper 1 (XEROX4200, manufactured by Xcrox Corporation) and Sheet of paper normal 2 (MyPaper, manufactured by Ricoh Corporation, Ltd.); the symbol regions on the printing surfaces were measured by colorimetry with X-Rite938 (manufactured by X-Rite, Incorporated) and evaluated using degrees described below.
[0219] [00219] The printing mode used was the "Plain Paper - Fast Standard" mode, which was changed to "No Color Correction" in the Plain Paper User Configuration with the driver attached to the printer.
[0220] A: 1,25 ou mais B: 1,20 ou mais e menos do que 1,25 C: 1,10 ou mais e menos do que 1,20 D: menos do que 1,10 [00220] JIS X 0208 (1997), 2223 described above represents a symbol that has a square shape entirely filled with paint. Degrees of assessment A: 1.25 or more B: 1.20 or more and less than 1.25 C: 1.10 or more and less than 1.20 D: less than 1.10
[0221] [00221] E: pigment is not dispersed in the ink due to freezing and printing has not reached Ink Storage Stability
[0222] [00222] Each ink was loaded into an ink cartridge and stored at 60 ° C for one week. The ratio of change from a viscosity after storage to a viscosity before storage was determined with the following formula and evaluated using degrees described below.
[0223] [00223] Viscosity change ratio (%) = (Paint viscosity after storage / Paint viscosity before storage) x 100
[0224] [00224] In the measurement of viscosity, a viscometer (RE80L, manufactured by Toki Sangyo Co. Ltd.) was used and a viscosity at 25 ° C was measured at 50 revolutions.
[0225] A: razão de alteração da viscosidade está dentro de +8% B: razão de alteração da viscosidade está além de +5% e dentro de +8% C: razão de alteração da viscosidade está além de +8% e dentro de +10% D: razão de alteração da viscosidade está além de +10% e dentro de +30% E: razão de alteração da viscosidade está além de +30% (avaliação não é alcançada devido ao congelamento) [00225] Degrees of evaluation A: viscosity change ratio is within + 8% B: viscosity change ratio is beyond + 5% and within + 8% C: viscosity change ratio is beyond + 8% and within + 10% D: viscosity change ratio is over + 10% and within + 30% E: viscosity change ratio is over + 30% (rating is not achieved due to freezing)
[0226] A: Nenhum rebordo observado B: Rebordo observado de 0% a 20% de toda a imagem C: Rebordo observado de 21% a 40% de toda a imagem D: Rebordo observado de 41% a 90% de toda a imagem E: Rebordo observado por toda a imagem F: Pigmento não foi disperso na tinta devido ao congelamento e a impressão não foi alcançada
[0227] [00227] As described above, the present disclosure can provide a new copolymer that is useful as a binder resin or an aqueous paint pigment dispersion resin.
[0228] [00228] That is, through the use of a copolymer according to the invention as a binder resin in an aqueous ink, images that have high resolution and definition in various print media can be obtained at a high speed.
[0229] [00229] By using a copolymer according to the present disclosure as a dispersion resin for a pigment, a pigment dispersion that is stable and has a high dispersion capacity can be obtained.
[0230] [00230] The use of an aqueous ink that contains a copolymer according to the present disclosure allows high image density even when engraving on conventional sheets of paper. Aqueous ink has high storage stability and does not cause bumps (unevenness) even when printing at high speed.
[0231] [00231] Now having fully described the modalities of the present invention, it will be apparent to one skilled in the art that many changes and modifications can be made to it without departing from the spirit and scope of the modalities of the invention as defined here.

权利要求:
Claims (8)
[0001]
Copolymer characterized by the fact that it comprises: repetition units by the following chemical formulas 1 and 2:
[0002]
Copolymer according to claim 1, characterized by the fact that a ratio of the repetition units represented by chemical formulas 1 and 2 satisfies chemical formulas 1: 2 = 1: 1 to 3: 1.
[0003]
Copolymer according to claim 1 or 2, characterized by the fact that Z in chemical formula 2 represents a naphthyl group.
[0004]
Copolymer according to any one of claims 1 to 3, characterized in that it additionally comprises a repetition unit represented by the following chemical formula 3
[0005]
Aqueous ink characterized by the fact that it comprises: Water; a colorant; and a copolymer, wherein the copolymer is the copolymer as defined in claims 1 to 4.
[0006]
Aqueous paint according to claim 5, characterized by the fact that the colorant is a pigment.
[0007]
Aqueous paint according to claim 5 or 6, characterized in that it additionally comprises at least one soluble organic solvent or a surfactant.
[0008]
Ink cartridge characterized by the fact that it comprises: an ink container; and the aqueous ink as defined in claims 5 to 7 accommodated in the ink container.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

JP2867491B2|1989-11-17|1999-03-08|セイコーエプソン株式会社|Image recording ink|

---

IL154538A|1994-12-15|2009-12-24|Cabot Corp|Reaction of carbon black with diazonium salts, resultant carbon black products and their uses|

---

EP0861855B1|1996-09-18|2006-06-21|AZ Electronic Materials USA Corp.|Light-absorbing polymer, method for synthesizing the same, and film-forming composition and antireflection film prepared using said polymer|

---

EP0889102A3|1997-06-30|1999-01-20|Elf Atochem North America, Inc.|Pigment dispersion for the preparation of aqueous inks|

---

JP4714363B2|2001-03-29|2011-06-29|東洋インキＳｃホールディングス株式会社|Recording liquid and method for producing the same|

---

JP4119166B2|2002-05-28|2008-07-16|三井化学株式会社|Thermosetting powder coating composition|

---

JP4133090B2|2002-08-02|2008-08-13|日信化学工業株式会社|Dispersant composition|

---

JP4722462B2|2003-12-03|2011-07-13|株式会社サクラクレパス|Water-based pigment ink composition|

---

US8946320B2|2004-03-22|2015-02-03|Hewlett-Packard Development Company, L.P.|Ink system containing polymer binders|

---

JP4577630B2|2004-08-09|2010-11-10|日東工業株式会社|Feeder chip high-speed transfer and surface improvement rate improvement means by the continuous supply method|

---

US7172276B2|2004-12-10|2007-02-06|Xerox Corporation|Heterogeneous low energy gel ink composition|

---

US7202883B2|2004-12-10|2007-04-10|Xerox Corporation|Heterogeneous reactive ink composition|

---

JP4687110B2|2005-01-07|2011-05-25|コニカミノルタホールディングス株式会社|Ink jet ink and ink jet recording method|

---

KR101298330B1|2005-08-31|2013-08-20|캐보트 코포레이션|Process for preparing modified pigments|

---

AU2006308951A1|2005-10-31|2007-05-10|Cabot Corporation|Modified colorants and inkjet ink compositions comprising modified colorants|

---

EP2173824A4|2007-07-23|2016-08-03|Canon Kk|Ink jet recording ink, ink jet image-forming method and ink jet recording apparatus|

---

CN101835850A|2007-10-25|2010-09-15|富士胶片株式会社|Organic pigment microparticle, process for production of the organic pigment microparticle, pigment-dispersed composition, photocurable composition or ink-jet ink comprising the organic pigment microparticle, color filter comprising the pigment-dispe|

---

JP4642892B2|2007-11-09|2011-03-02|富士フイルム株式会社|Pigment composition, aqueous pigment dispersion, method for producing aqueous pigment dispersion, water-based ink for inkjet recording|

---

JP2012051367A|2010-08-02|2012-03-15|Mitsubishi Plastics Inc|Polyester film for supporting interlayer insulating material|

---

JP2012036287A|2010-08-06|2012-02-23|Ricoh Co Ltd|Inkjet recording ink, ink cartridge, and image forming apparatus|

---

JP2012052027A|2010-09-01|2012-03-15|Ricoh Co Ltd|Aqueous inkjet ink composition and inkjet image forming device|

---

JP2012149108A|2011-01-17|2012-08-09|Panasonic Corp|Method of producing polybasic acid vinyl monomer copolymer|

---

JP5435054B2|2012-02-09|2014-03-05|Ｊｎｃ株式会社|Ink jet ink and cured film forming method obtained from the ink|

---

JP6183051B2|2013-08-21|2017-08-23|株式会社リコー|Copolymer|JP6183051B2|2013-08-21|2017-08-23|株式会社リコー|Copolymer|

---

JP2016020469A|2013-09-13|2016-02-04|株式会社リコー|Ink for inkjet, ink set, ink cartridge, inkjet recording device, inkjet recording method and ink recorded article|

---

JP2015214674A|2014-04-15|2015-12-03|株式会社リコー|Ink for inkjet recording, ink housing container, inkjet recording device, and recorded matter|

---

JP6503938B2|2014-07-16|2019-04-24|株式会社リコー|Novel copolymer, aqueous ink, ink cartridge, setting of aqueous ink and coated paper, and recording method|

---

JP6344123B2|2014-07-31|2018-06-20|株式会社リコー|Novel copolymer, water-based ink, and ink cartridge|

---

JP6344172B2|2014-09-16|2018-06-20|株式会社リコー|Novel copolymer, water-based ink, and ink cartridge|

---

JP6425190B2|2014-10-10|2018-11-21|株式会社リコー|Novel copolymer, aqueous ink, and ink cartridge|

---

JP2016094498A|2014-11-12|2016-05-26|株式会社リコー|Ink, ink cartridge, inkjet recording device, and copolymer|

---

US9777091B2|2014-12-12|2017-10-03|Ricoh Company, Ltd.|Copolymer, ink, and ink container|

---

JP6555586B2|2014-12-12|2019-08-07|株式会社リコー|Copolymer, ink and ink container|

---

US10280321B2|2015-01-29|2019-05-07|Ricoh Company, Ltd.|Ink, ink container, inkjet recording device, and recorded matter|

---

WO2016125473A1|2015-02-02|2016-08-11|Ricoh Company, Ltd.|Novel copolymer, aqueous ink, and ink cartridge|

---

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---

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---

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---

US10190007B2|2015-05-14|2019-01-29|Ricoh Company, Ltd.|Ink, ink container, image forming method, image forming apparatus, and image formed matter|

---

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---

US10131805B2|2015-06-23|2018-11-20|Ricoh Company, Ltd.|Ink, ink stored container, inkjet recording apparatus, and printed matter|

---

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---

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---

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---

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---

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---

US10000656B2|2015-12-16|2018-06-19|Ricoh Company, Ltd.|Ink, recorded matter, ink container, recording device, and recording method|

---

US9873252B2|2015-12-25|2018-01-23|Ricoh Company, Ltd.|Printing device and printing method|

---

JP6642156B2|2016-03-17|2020-02-05|株式会社リコー|Ink and manufacturing method thereof, ink container, recording method, and recording apparatus|

---

US10233345B2|2016-03-17|2019-03-19|Ricoh Company, Ltd.|Ink set, recording device, and method of recording|

---

JP2017190424A|2016-04-15|2017-10-19|竹本油脂株式会社|Vinyl copolymer|

---

CN109923182A|2016-10-31|2019-06-21|卡博特公司|Polymer for ink jet ink composition|

---

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---

WO2019003594A1|2017-06-30|2019-01-03|東洋インキＳｃホールディングス株式会社|Water-based ink-jet ink and production method for printed matter|

---

US10807377B2|2018-03-07|2020-10-20|Ricoh Company, Ltd.|Ink, ink cartridge, image forming method, and printed matter|

法律状态:
2014-11-25| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|

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2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-07-14| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-09-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/01/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2013-004959|2013-01-15|

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JP2013004959|2013-01-15|

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JP2013-130578|2013-06-21|

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JP2013130578|2013-06-21|

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JP2013-181632|2013-09-02|

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JP2013181632|2013-09-02|

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JP2013236884|2013-11-15|

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JP2013-236884|2013-11-15|

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