JP5839098B2 - Ink composition - Google Patents

Description

  The present invention relates to an ink composition which is excellent in color developability, stability and fixability, and particularly excellent as an inkjet recording ink for textiles.

  Ink used for inkjet recording has no bleeding, good drying properties, can be printed uniformly on the surface of various recording media, and can be used for multi-color printing such as color printing. Characteristics such as the fact that adjacent colors do not mix in printing are required.

  In conventional inks, many of the inks that use pigments, in particular, have been studied to ensure the print quality by suppressing ink wetting on the paper surface mainly by suppressing penetrability and keeping ink droplets near the paper surface. Made and put to practical use. However, with ink that suppresses wetting of paper, there is a large difference in bleeding due to differences in the type of paper, and especially with recycled paper that contains various paper components, there is bleeding due to differences in the wetting characteristics of each component. Occur. In addition, such an ink has a problem that it takes time to dry the printing, and there is a problem that adjacent colors are mixed in multicolor printing such as color printing, and further, a pigment is used as a coloring material. Ink also has a problem that the abrasion resistance deteriorates because the pigment remains on the surface of paper or the like.

  In order to solve such problems, attempts have been made to improve the permeability of ink into paper. Addition of diethylene glycol monobutyl ether (see Patent Document 1), Surfynol 465, which is an acetylene glycol-based surfactant. The addition of Nissin Chemical (see Patent Document 2) or the addition of both diethylene glycol monobutyl ether and Surfynol 465 (see Patent Document 3) has been studied. In addition, the use of diethylene glycol ethers for ink has been studied (see Patent Document 4).

  In addition, in an ink using a pigment, it is generally difficult to improve the permeability of the ink while ensuring the dispersion stability of the pigment, and since the range of selection of the penetrant is narrow, as a combination of a conventional glycol ether and a pigment, There are also examples using triethylene glycol monomethyl ether as a pigment (see Patent Document 5) and examples using ethers of ethylene glycol, diethylene glycol or triethylene glycol (see Patent Document 6).

  Furthermore, as textiles, there are, for example, those using dyes (see Patent Document 7) and those relating to binders (see Patent Document 8).

  In addition, the applicant of the present invention uses a specific water-dispersed pigment as a water-based ink composition having either or both of low bleeding and high color development on plain paper and sufficient color development and fixing on special paper. Patent Document 9 discloses an ink composition containing a polymer-coated pigment coated with a functional polymer.

US Pat. No. 5,156,675 US Pat. No. 5,183,502 US Pat. No. 5,196,056 US Pat. No. 2,083,372 Japanese Patent Application Laid-Open No. 56-147861 Japanese Patent Laid-Open No. 9-111165 Japanese Patent Application Laid-Open No. 2007-515561 Japanese Patent Laid-Open No. 2007-126635 JP-A-2005-272790

  However, conventional water-based inks have insufficient print quality, particularly as ink-jet recording inks for textiles, have insufficient fixability, and insufficient color density and color developability. In addition, conventional pigment dispersions have low storage stability and are unstable, and when a substance having a hydrophilic part and a hydrophobic part such as a surfactant or glycol ether is present, the adsorption and desorption of the polymer from the pigment is likely to occur. There is a problem that the storage stability of the ink is poor. Ordinary 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, additives used in the present invention for conventional pigment dispersions (acetylene glycol and acetylene alcohol surfactants, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether or 1,2- If alkylene glycol or a mixture thereof is used, there is a problem that long-term storage stability cannot be obtained, and ink re-dissolvability is poor, so that the ink is dried and easily clogged at the tip of an inkjet head nozzle or the like. It was.

  Accordingly, the present invention solves such problems, and the object thereof is excellent in color developability, stability and fixability, particularly excellent as an inkjet recording ink for textiles, and ink from an inkjet head. Another object of the present invention is to provide an ink composition having excellent ejection stability.

The ink composition of the present invention is as follows.
(1) A dispersion having an average particle diameter of 50 nm or more and 300 nm or less capable of dispersing the pigment in water, and polymer fine particles having a glass transition temperature of −10 ° C. or less and an acid value of 100 mgKOH / g or less An ink composition comprising:
(2) The ink according to (1), wherein the polymer fine particles are polymerized using 70% by weight or more of alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate as a constituent component. Composition.
(3) The polymer fine particles are polymerized using 70% by weight or more of alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate and 5% by weight or more and 25% by weight or less of styrene as components. The ink composition as described in (1) above, wherein
(4) The alkyl (meth) acrylate and / or the cyclic alkyl (meth) acrylate is an alkyl (meth) acrylate having 1 to 24 carbon atoms and / or a cyclic alkyl (meth) acrylate having 3 to 24 carbon atoms. The ink composition as described in (2) or (3) above.

(5) The ink composition as described in (1) above, further comprising a polyalkylene wax having a melting point of 80 ° C. or higher.
(6) The dispersion according to any one of (1) to (5), wherein the dispersion has an average particle diameter of 50 nm or more and 300 nm or less that allows carbon black dispersed without a dispersant to be dispersed in water. The ink composition as described.
(7) The dispersion is dispersed using a polymer polymerized using 50% by weight or more of benzyl acrylate and 15% by weight or less of methacrylic acid and / or acrylic acid as constituents. The ink composition according to (1) above.
(8) The dispersion has an average particle diameter of 50 nm to 300 nm that enables the organic pigment to be dispersed in water with a polymer, and the polymer has a styrene-equivalent weight average molecular weight by gel permeation chromatography (GPC). The ink composition according to any one of (1) to (7), which is 10,000 or more and 200,000 or less.

(9) The dispersion includes an organic pigment including a water-insoluble polymer obtained by copolymerizing a monomer mixture containing a salt-forming group-containing monomer and a macromer and / or a hydrophobic monomer, and
The ink composition as described in (1) above, wherein the polymer fine particles are obtained by polymerizing at least ethyl acrylate and (meth) acrylic acid as constituent components.
(10) The dispersion includes an organic pigment included in a resin layer formed by emulsion polymerization, and
The ink composition as described in (1) above, wherein the polymer fine particles are obtained by polymerizing at least ethyl acrylate and (meth) acrylic acid as constituent components.

(11) The ink composition according to any one of (1) to (10), wherein the polymer fine particles have a styrene-converted weight average molecular weight of from 100,000 to 1,000,000 by gel permeation chromatography (GPC).
(12) The ink composition according to any one of (1) to (11), comprising 1,2-alkylene glycol.
(13) The ink composition according to any one of (1) to (12), comprising an acetylene glycol surfactant and / or an acetylene alcohol surfactant.
(14) The ink composition according to any one of (1) to (13), wherein a content (% by weight) of the polymer fine particles is larger than a content (% by weight) of the pigment.
(15) The ink composition as described in any one of (1) to (14) above, which is used in an ink jet recording system.

  The present invention is based on the results of intensive studies in view of demands for characteristics such as excellent color developability, stability, and fixability, and particularly excellent as an inkjet recording ink for textiles.

Preferred embodiment (a) of the present invention
The ink composition of the present invention comprises a dispersion having an average particle diameter of 50 nm or more and 300 nm or less capable of dispersing a pigment in water, a glass transition temperature of −10 ° C. or less, and an acid value of 100 mgKOH / g or less. It is characterized by comprising molecular fine particles.

  First, the pigment dispersion and polymer fine particles contained in the ink composition of the present invention (hereinafter simply referred to as “the ink of the present invention”), and additives that may optionally be contained will be described.

  The average particle diameter of the pigment dispersion and the polymer fine particles is measured by a light scattering method. If the average particle size of the pigment dispersion by the light scattering method is less than 50 nm, the color developability decreases. On the other hand, if it exceeds 300 nm, the fixability is lowered. Preferably they are 60 nm-230 nm, More preferably, they are 70 nm-230 nm, More preferably, they are 80 nm-130 nm.

  On the other hand, the particle size of the polymer fine particles is preferably from 50 nm to 500 nm, more preferably from 60 nm to 300 nm. When the particle size of the polymer fine particle is less than 50 nm, the fixing property is lowered, and when it exceeds 500 nm, the ejection from the inkjet head tends to be unstable.

  In addition, the glass transition temperature of the polymer fine particles contained in the ink of the present invention is preferably −10 ° C. or less, and particularly the fixability of the pigment as a textile ink is improved. When the temperature exceeds -10 ° C, the fixability of the pigment gradually decreases. More preferably, it is -15 degrees C or less, More preferably, it is -20 degrees C or less, More preferably, it is -25 degrees C or less, Most preferably, it is -30 degrees C or less.

  Furthermore, the acid value of the polymer fine particles is preferably 100 mgKOH / g or less, and when the acid value exceeds 100 mgKOH / g, the fastness to washing when printed on textiles is lowered. More preferably, it is 50 mgKOH / g or less, More preferably, it is 30 mgKOH / g or less.

  The molecular weight of the polymer fine particles is preferably 100,000 or more, and more preferably 200,000 or more. If it is less than 100,000, the fastness to washing when printed on textiles for textiles is lowered.

  The dispersion comprising the ink of the present invention preferably has an average particle diameter of 50 nm or more and 300 nm or less that allows carbon black dispersed without a dispersant to be dispersed in water. By using carbon black dispersed without a dispersant, the color developability of the printed matter is improved. As a method of dispersing in water without a dispersant, there is a method of oxidizing the surface of carbon black with ozone or sodium hypochlorite. The average particle size of the carbon black is preferably 50 nm to 150 nm. If it is less than 50 nm, it is difficult to obtain color developability. On the other hand, if it exceeds 150 nm, the fixing property is lowered. A preferred particle size is 60 nm to 130 nm, a more preferred particle size is 70 nm to 130 nm, and even more preferred is 80 nm to 120 nm.

  Further, the dispersion comprising the ink of the present invention has an average particle diameter of 50 nm to 300 nm, which enables the organic pigment to be dispersed in water with a polymer, and is determined by gel permeation chromatography (GPC) of the polymer. It is preferable that the styrene conversion weight average molecular weight is 10,000 or more and 200,000 or less. When the weight average molecular weight in terms of styrene is 10,000 or more and 200,000 or less, fixability of a pigment as a textile ink is improved, and storage stability of the pigment ink is also improved. In addition, it is preferable that at least 70% or more, preferably at least 80% or more of the polymer used for dispersing the pigment is a polymer obtained by copolymerization of (meth) acrylate and (meth) acrylic acid.

  In addition to the dispersant, a water-dispersible or water-soluble polymer or surfactant may be added as a dispersion stabilizer in order to stabilize the dispersion.

  The weight average molecular weight in terms of styrene by gel permeation chromatography (GPC) of the polymer fine particles comprising the ink of the present invention is preferably 100,000 or more and 1,000,000 or less. When the weight average molecular weight in terms of styrene is 100,000 or more and 1,000,000 or less, fixability of a pigment particularly as an ink for textiles is improved.

  The ink of the present invention preferably uses 1,2-alkylene glycol. By using 1,2-alkylene glycol, bleeding is reduced and print quality is improved. Examples of 1,2-alkylene glycols are 1,2-alkylene glycols having 5 or 6 carbon atoms such as 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol. Is preferred. Among them, 1,6-hexanediol and 4-methyl-1,2-pentanediol having 6 carbon atoms are preferable. The addition amount of these 1,2-alkylene glycols is preferably 0.3% by weight (hereinafter sometimes simply referred to as “%”) to 30%, more preferably 0.5% to 10%.

  The ink of the present invention preferably uses glycol ether. As the glycol ether, it is preferable to use one or more selected from diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether. The addition amount of glycol ether is preferably 0.1% to 20%, more preferably 0.5% to 10%.

  The ink of the present invention preferably uses an acetylene glycol surfactant and / or an acetylene alcohol surfactant. By using an acetylene glycol surfactant and / or an acetylene alcohol surfactant, bleeding is further reduced and printing quality is improved. In addition, the addition of these improves the dryness of printing, and enables high-speed printing.

  Acetylene glycol surfactants and / or acetylene alcohol surfactants are 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5. Selected from alkylene oxide adducts of decyne-4,7-diol, 2,4-dimethyl-5-decyn-4-ol and alkylene oxide adducts of 2,4-dimethyl-5-decyn-4-ol One or more are preferred. These are available as Air Products (UK) Olfin 104 series, Olfin E1010 and other E series, Nissin Chemical's Surfynol 465, Surfynol 61, and the like.

  Further, the ink of the present invention comprises 1,2-alkylene glycol and acetylene glycol surfactant and / or acetylene alcohol surfactant, glycol ether and acetylene glycol surfactant and / or acetylene alcohol surfactant. Thus, the use of a plurality reduces the bleeding.

  In the ink of the present invention, the content (% by weight) of the polymer fine particles is preferably larger than the content (% by weight) of the pigment. By adding more polymer fine particles by weight than the pigment, the fixability of the pigment, particularly as a textile ink, is improved. Furthermore, for textiles, the process of washing with water or water containing a surfactant after printing on the cloth is added, so that the water-soluble components in the ink are washed away, so that the fine polymer particles can be fixed on the cloth. It becomes firm and can further improve the abrasion resistance.

  In the present invention, it is preferable to use at least water, a coloring material and a humectant.

  In this way, by preparing the ink jet recording ink, it is possible to obtain an ink jet recording ink that is excellent in color development, stability, and fixability, and particularly excellent as a textile ink jet recording ink.

  As the pigment that can be used in the present invention, carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black and the like are particularly preferable for black ink, but copper oxide, iron Oxides (CI Pigment Black 11), metals such as titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1) can also be used.

  For color ink, 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, 155, 180, 185, 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, 206, 09,219, C. I. Pigment violet 19, 23, C.I. I. Pigment orange 36, 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. Thus, various pigments can be used as the colorant.

  Moreover, although the said pigment disperse | distributes using a disperser, various commercially available dispersers can be used as a disperser. However, non-media distribution is preferable from the viewpoint of low contamination. Specific examples thereof include a wet jet mill (Genus), a nanomer (Nanomer), a homogenizer (Gorin), an optimizer (Sugino Machine), and a microfluidizer (Microfluidics).

  The addition amount of the pigment used in the ink of the present invention is preferably 0.5% to 30%, more preferably 1.0% to 15%. If the addition amount is less than 0.5%, the print density cannot be secured. If the addition amount exceeds 30%, the viscosity of the ink increases and structural viscosity is produced in the viscosity characteristics, and the ejection stability of the ink from the inkjet head is poor. Tend to be.

  In addition, the ink of the present invention has a humectant, a dissolution aid, a permeation agent for the purpose of ensuring its standing stability, for stable ejection from an inkjet head, for improving clogging, or for preventing ink deterioration. Add various additives such as control agents, viscosity modifiers, pH adjusters, dissolution aids, antioxidants, preservatives, antifungal agents, corrosion inhibitors, chelates to capture metal ions that affect dispersion You can also

  In addition, the ink of the present invention is preferably ejected by a method using an electrostrictive element such as a piezo element that does not heat. When heating such as a thermal head occurs, the added polymer The polymer used for dispersing fine particles and pigments is likely to be deteriorated and discharge becomes unstable. In particular, when a large amount of ink is ejected over a long period of time, such as an inkjet ink for textiles, a heating head is not preferable.

  The ink of the present invention is particularly excellent as an inkjet recording ink for textiles, but besides this, it can be applied to writing instruments and the like in addition to inkjet inks such as consumer business inkjet ink and industrial inkjet ink. is there.

Other Preferred Embodiments of the Present Invention The ink of the present invention can be made into various preferred embodiments as described below based on the configuration described in the above-described embodiment (a).

Preferred embodiment (b) of the present invention
The ink of the present invention has a dispersion having an average particle diameter of 50 nm or more and 300 nm or less, in which the pigment can be dispersed in water, a glass transition temperature of −10 ° C. or less, an acid value of 100 mgKOH / g or less, and It is characterized by comprising polymer fine particles containing 70% by weight or more of alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate as a constituent component. Dry and wet friction when printed on textiles for textiles by including polymer fine particles containing 70% by weight or more of alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate as a constituent component The friction fastness is improved.

  The alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate is preferably an alkyl (meth) acrylate having 1 to 24 carbon atoms and / or a cyclic alkyl (meth) acrylate having 3 to 24 carbon atoms. As methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, lauryl (meth) acrylate, isoboronyl (meth) acrylate Cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) ) Acrylate and behenyl (meth) acrylate.

Preferred embodiment (c) of the present invention
Further, in the ink of the present invention, the polymer fine particles are further added to 70% by weight or more of alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate described in the preferred embodiment (b) of the present invention. It is preferable that 5% by weight or more and 25% by weight or less of styrene is contained as a constituent component. With this configuration, the friction fastness of dry friction and wet friction is improved, and the ejection stability when used as a component of inkjet ink is improved.

Preferred embodiment (d) of the present invention
The ink of the present invention includes a dispersion having an average particle diameter of 50 nm to 300 nm and a glass transition temperature of −10 ° C. or lower and an acid value of 100 mgKOH / g or lower. It comprises fine particles and a polyalkylene wax having a melting point of 80 ° C. or higher. Thereby, it can be set as the ink for inkjet recording which was more excellent in abrasion resistance. In particular, the improvement in abrasion resistance, which is a characteristic required for textile inks, becomes remarkable. Usually, in the case of textile pigment inks, a process of pre-treating a cloth with a pre-treatment agent to improve the color developability, and after printing, a step of further improving the abrasion resistance with the post-treatment agent is performed. However, when printing with the ink of the present invention, even if there is no pre-treatment and post-treatment, the color developability is high and the abrasion resistance is excellent, and the process can be greatly simplified. Water and cleaning agents can be eliminated.

  As described above, the melting point of the polyalkylene wax used in the present invention is preferably 80 ° C. or higher, more preferably 100 ° C. or higher from the viewpoint of improving the abrasion resistance. The polyalkylene wax is preferably polyethylene wax or polypropylene wax. Examples of the polyalkylene wax include a copolymer type of unsaturated monomers such as propylene, ethylene oxide, acrylic acid, methacrylic acid, vinyl acetate or maleic anhydride, in addition to a homopolymer system of ethylene or propylene. Also, a mixture with polytetrafluoroethylene or the like can be used to reduce the friction coefficient. Many types are commercially available from manufacturers such as Mitsui Chemicals, Honeywell, Shamrock Technology, Sanyo Chemical, Eastman Chemical, Allied Signals, and Clariant.

Preferred embodiment (e) of the present invention
The ink of the present invention uses a polymer in which 50% by weight or more of benzyl acrylate and 15% by weight or less of methacrylic acid and / or acrylic acid are polymerized as a constituent component to disperse the pigment in water. A dispersion having an average particle size of 50 nm to 300 nm, and polymer fine particles having a glass transition temperature of −10 ° C. or less and an acid value of 100 mgKOH / g or less. Benzyl acrylate provides a high color developability as compared with the case of using other acrylic esters due to the polymer Tg and the refractive index. When benzyl acrylate is less than 50% by weight, the fixing property is lowered. Therefore, the preferable range of the blending amount is 50% by weight or more. More preferably, it is 60 weight% or more, More preferably, it is 70 weight% or more. Polymerization with 15% by weight or less of methacrylic acid and / or acrylic acid is preferred. When it exceeds 15% by weight, the color developability of the inkjet ink is lowered. A more preferable range is 10% by weight or less. Further, when methacrylic acid and acrylic acid are compared, it is more preferable to use acrylic acid from the viewpoint of fixability.

Preferred embodiment (f) of the present invention
The ink of the present invention comprises a dispersion containing an organic pigment contained in a water-insoluble polymer obtained by copolymerizing a monomer mixture containing a salt-forming group-containing monomer and a macromer and / or a hydrophobic monomer, and at least as a constituent component Ethyl acrylate and (meth) acrylic acid are polymerized, and include polymer fine particles having a glass transition temperature of −10 ° C. or lower and an acid value of 100 mgKOH / g or lower.

  It is preferable to use at least ethyl acrylate and (meth) acrylic acid as constituents of the polymer fine particles. The blending amount of ethyl acrylate in preparing the polymer fine particles is preferably 60% by weight to 80% by weight (hereinafter sometimes simply referred to as “%”). By setting the blending ratio of ethyl acrylate in the polymer fine particle within the above range, the performance under both dry and wet conditions can be suitably maintained in the abrasion resistance when printed on the fabric.

  Further, as other constituents of the polymer fine particles, those which can be copolymerized with ethyl acrylate and (meth) acrylic acid, and the polymer fine particles to be prepared satisfy the above-mentioned conditions of the glass transition temperature and the acid value. Any selection is possible. In particular, it is preferable to blend an unsaturated vinyl monomer having a group having a “bulky” molecular structure such as an aromatic group, an alicyclic hydrocarbon group, or a heterocyclic group. Aromatic groups include benzyl, phenyl and naphthyl groups, and alicyclic hydrocarbon groups include cycloalkyl, cycloalkenyl, isobornyl, dicyclopentanyl, dicyclopentenyl and adamantane groups. Examples of the heterocyclic group include a tetrahydrofuran group and the like. By introducing these components having a “bulky” group, the mechanical strength of the polymer fine particles can be increased, and the abrasion resistance of the printed matter can be improved.

  In this embodiment (f), the glass transition temperature of the polymer fine particles is preferably −50 ° C. to 0 ° C., and particularly the fixability of the pigment as a textile ink is improved. When the temperature exceeds 0 ° C., the fixability of the pigment gradually decreases, and when the temperature is less than −50 ° C., ejection from the inkjet head tends to become unstable. More preferably, it is -25 degreeC--5 degreeC, Most preferably, it is -25 degreeC--10 degreeC. The acid value of the polymer fine particles is preferably 50 mgKOH / g or less, and if the acid value exceeds 50 mgKOH / g, the fastness to washing when printed on a cloth for textiles is lowered. More preferably, it is 30 mgKOH / g or less. The acid value can be calculated from the structural unit of the polymer. Alternatively, it can also be determined by a method in which a polymer is dissolved in an appropriate solvent (for example, methyl ethyl ketone) and titrated. Furthermore, the molecular weight of the polymer fine particles is preferably 100,000 or more, more preferably 200,000 or more. If it is less than 100,000, the fastness to washing when printed on textiles for textiles is lowered.

  The dispersion comprising the ink of the present invention is characterized by using a water-insoluble polymer (A). The water-insoluble polymer (A) is used for improving the color developability.

  Here, the water-insoluble polymer means that when the polymer is dried at 105 ° C. for 2 hours and then dissolved in 100 g of water at 25 ° C., the dissolution amount is 10 g or less, preferably 5 g or less, more preferably 1 g or less. Is a polymer. When the polymer has a salt-forming group, the dissolution amount is a dissolution amount when the salt-forming group of the polymer is neutralized 100% with acetic acid or sodium hydroxide depending on the type.

  The water-insoluble polymer (A) contained in the ink of the present invention comprises (a) a salt-forming group-containing monomer (hereinafter sometimes referred to as “(a) component”) and (b) a macromer (hereinafter referred to as “(b) component”. And / or (c) a hydrophobic monomer (hereinafter also referred to as “component (c)”) and a monomer mixture (hereinafter also referred to as “monomer mixture”). It is a water-insoluble polymer. This water-insoluble polymer has a structural unit derived from the component (a), a structural unit derived from the component (b) and / or a structural unit derived from the component (c).

  (A) The salt-forming group-containing monomer is used from the viewpoint of enhancing the dispersion stability of the resulting dispersion. Examples of the salt-forming group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, and an ammonium group.

  (A) Examples of the salt-forming group-containing monomer include a cationic monomer and an anionic monomer. Examples thereof include those described in JP-A-9-286939, page 5, line 24 to column 8, line 29.

  Representative examples of the cationic monomer include unsaturated amine-containing monomers and unsaturated ammonium salt-containing monomers. Among these, N, N-dimethylaminoethyl (meth) acrylate, N- (N ′, N′-dimethylaminopropyl) (meth) acrylamide and vinylpyrrolidone are preferable.

  Typical examples of the anionic monomer include unsaturated carboxylic acid monomers, unsaturated sulfonic acid monomers, unsaturated phosphoric acid monomers, and the like.

  Examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid. Examples of the unsaturated sulfonic acid monomer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylate, and bis- (3-sulfopropyl) -itaconate. Examples of unsaturated phosphoric acid monomers include vinylphosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxy Examples thereof include ethyl phosphate.

  Among the anionic monomers, unsaturated carboxylic acid monomers are preferable, and acrylic acid and methacrylic acid are more preferable from the viewpoints of dispersion stability and ejection stability.

  (B) The macromer is used from the viewpoint of enhancing the dispersion stability of the polymer (A) when the polymer (A) includes a pigment. Examples of the macromer include a macromer which is a monomer having a polymerizable unsaturated group having a molecular weight of 500 to 100,000, preferably 1000 to 10,000. In addition, the molecular weight of this polymer here is a styrene conversion weight average molecular weight by gel permeation chromatography (GPC).

  (B) Among macromers, from the viewpoint of dispersion stability of the polymer (A). Styrenic macromers and aromatic group-containing (meth) acrylate macromers having a polymerizable functional group at one end are preferred.

  Examples of the styrenic macromer include a styrene monomer homopolymer or a copolymer of a styrene monomer and another monomer. Examples of the styrene monomer include styrene, 2-methylstyrene, vinyl toluene, ethyl vinyl benzene, vinyl naphthalene, chlorostyrene, and the like. Examples of the aromatic group-containing (meth) acrylate-based macromer include a homopolymer of an aromatic group-containing (meth) acrylate or a copolymer thereof with another monomer. As the aromatic group-containing (meth) acrylate, an arylalkyl group having 7 to 22 carbon atoms, preferably 7 to 18 carbon atoms, more preferably 7 to 12 carbon atoms, which may have a substituent containing a hetero atom. Alternatively, it may have a substituent containing a hetero atom. A (meth) acrylate having an aryl group having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and the substituent containing a hetero atom includes a halogen atom, an ester group, and an ether. Group, hydroxy group and the like. Examples include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, and benzyl (meth) acrylate is particularly preferable.

  The polymerizable functional group present at one end of these macromers is preferably an acryloyloxy group or a methacryloyloxy group, and the other monomer to be copolymerized is preferably acrylonitrile.

  The content of the styrene monomer in the styrene macromer or the aromatic group-containing (meth) acrylate in the aromatic group-containing (meth) acrylate macromer is preferably 50% by weight from the viewpoint of increasing the affinity with the pigment. Above, more preferably 70% by weight or more.

  (B) The macromer may have a side chain composed of another structural unit such as an organopolysiloxane. This side chain can be obtained, for example, by copolymerizing a silicone macromer having a polymerizable functional group at one end represented by the following formula (1).

_{CH 2 = C (CH 3)} -COOC 3 H 6 - [Si (CH _{3) 2} O] _t -Si (CH _{3) 3}
... Formula (1)

(In the formula, t represents a number of 8 to 40.)
Examples of commercially available styrenic macromers as component (b) include Toa Gosei Co., Ltd. trade names, AS-6 (S), AN-6 (S), HS-6 (S), and the like. It is done.

  (C) The hydrophobic monomer is used from the viewpoint of improving color developability and gloss. Examples of the hydrophobic monomer include alkyl (meth) acrylate and aromatic group-containing monomer.

  As the alkyl (meth) acrylate, those having an alkyl group having 1 to 22 carbon atoms, preferably 6 to 18 carbon atoms are preferable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meta) ) Acrylate, (iso or tertiary) butyl (meth) acrylate, (iso) amyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) Examples include decyl (meth) acrylate, (iso) dodecyl (meth) acrylate, (iso) stearyl (meth) acrylate, and the like.

  In the present specification, “(iso or tertiary)” and “(iso)” mean both the case where these groups are present and the case where these groups are not present. Indicates. “(Meth) acrylate” represents acrylate, methacrylate, or both.

  The aromatic group-containing monomer may have a substituent containing a hetero atom, and is preferably a vinyl monomer having an aromatic group having 6 to 22 carbon atoms, preferably 6 to 12 carbon atoms. Examples thereof include styrene monomers (component c-1) and the above-mentioned aromatic group-containing (meth) acrylates (component c-2). Examples of the substituent containing a hetero atom include those described above.

  Among the components (c), styrenic monomers (component c-1) are preferable from the viewpoint of glossiness and color developability, and the above-mentioned ones are mentioned as styrenic monomers, and styrene and 2-methylstyrene are particularly preferable. The content of the component (c-1) in the component (c) is preferably 10% by weight to 100% by weight (hereinafter sometimes simply referred to as “%”), from the viewpoint of color development and gloss improvement. Preferably, it is 20% to 80%.

  Moreover, the above-mentioned thing is mention | raise | lifted as an aromatic group containing (meth) acrylate (c-2) component, A benzyl (meth) acrylate, a phenoxyethyl (meth) acrylate, etc. are preferable. The content of the component (c-2) in the component (c) is preferably 10% to 100%, more preferably 20% to 80%, from the viewpoint of improving glossiness. Moreover, it is also preferable to use (c-1) component and (c-2) component together.

  The monomer mixture may further contain (d) a hydroxyl group-containing monomer (hereinafter sometimes referred to as “component (d)”). (D) The hydroxyl group-containing monomer exhibits an excellent effect of enhancing dispersion stability.

  (D) As a component, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethyleneglycol (n = 20-30, n shows the average addition mole number of an oxyalkylene group. The same hereafter. ) (Meth) acrylate, polypropylene glycol (n = 2 to 30) (meth) acrylate, poly (ethylene glycol (n = 1 to 15) / propylene glycol (n = 1 to 15) (meth) acrylate, and the like. Among these, 2-hydroxyethyl (meth) acrylate, polyethylene glycol monomethacrylate, and polypropylene glycol methacrylate are preferable.

  The monomer mixture may further contain (e) a monomer represented by the following formula (2) (hereinafter sometimes referred to as “(e) component”).

CH ₂ = C (R ¹ ) COO (R ² O) _p R ³ Formula (2)

(In the formula, R ¹ is a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, R ² is a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a hetero atom, and R ³ is a hetero atom. A monovalent hydrocarbon group having 1 to 30 carbon atoms which may have an integer, p means an average number of added moles and represents a number of 1 to 60, preferably 1 to 30.)

  The component (e) exhibits an excellent effect of improving the color developability and glossiness of the ink.

  In the formula (2), examples of the hetero atom include a nitrogen atom, an oxygen atom, a halogen atom, and a sulfur atom.

Preferable examples of R ¹ include methyl group, ethyl group, (iso) propyl group and the like.

Preferred examples of R ² O include an oxyethylene group, an oxy (iso) propylene group, an oxytetramethylene group, an oxyheptamethylene group, an oxyhexamethylene group, and a combination of two or more of these oxyalkylenes having 2 to 2 carbon atoms. 7 oxyalkylene groups.

Preferable examples of R ³ include aliphatic alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, alkyl groups having 7 to 30 carbon atoms having an aromatic ring, and 4 to 30 carbon atoms having a heterocyclic ring. Of the alkyl group.

  Specific examples of the component (e) include methoxypolyethylene glycol (1 to 30: the value of p in the formula (2) is the same hereinafter) (meth) acrylate, methoxypolytetramethylene glycol (1 to 30) ( (Meth) acrylate, ethoxy polyethylene glycol (1-30) (meth) acrylate, octoxy polyethylene glycol (1-30) (meth) acrylate, polyethylene glycol (1-30) (meth) acrylate 2-ethylhexyl ether, (iso) Propoxy polyethylene glycol (1-30) (meth) acrylate, butoxy polyethylene glycol (1-30) (meth) acrylate, methoxypolypropylene glycol (1-30) (meth) acrylate, methoxy (ethylene glycol / propylene glycol) Polymerization) (1 to 30, ethylene glycol therein: 1-29) (meth) acrylate and the like. Among these, octoxypolyethylene glycol (1-30) (meth) acrylate and polyethylene glycol (1-30) (meth) acrylate 2-ethylhexyl ether are preferable.

  Specific examples of commercially available (d) and (e) components include Shin-Nakamura Chemical Co., Ltd. polyfunctional acrylate monomer (NK ester) M-40G, 90G, 230G, and Nippon Oil & Fats Co., Ltd. BLEMMER series, PE-90, 200, 350, PME-100, 200, 400, 1000, PP-500, 800, 1000, AP-150, 400, 550, 800 , 50PEP-300, 50POEP-800B and the like.

  The components (a) to (e) can be used alone or in admixture of two or more.

  The content of the components (a) to (e) in the monomer mixture at the time of producing the water-insoluble polymer (content as an unneutralized amount; the same applies hereinafter) or (a) to (e) in the water-insoluble polymer Content of the structural unit derived from a component is as follows.

  The content of component (a) is preferably 2% to 40%, more preferably 2% to 30%, and still more preferably 3% to 20%, from the viewpoint of dispersion stability of the resulting dispersion.

  The content of the component (b) is preferably 1% to 25%, more preferably 5% to 20%, particularly from the viewpoint of enhancing the interaction with the colorant.

  The content of the component (c) is preferably 5% to 98%, more preferably 10% to 60%, from the viewpoints of glossiness and image clarity.

  The weight ratio ((a) / [(b) + (c)]) of the components (a), (b) and (c) in the water-insoluble polymer is preferably from the viewpoint of glossiness and image clarity. It is 01 to 1, more preferably 0.02 to 0.67, still more preferably 0.03 to 0.50.

  The content of component (d) is preferably 5% to 40%, more preferably 7% to 20%, from the viewpoint of dispersion stability of the resulting dispersion.

  The content of component (e) is preferably 5% to 50%, more preferably 10% to 40%, from the viewpoint of dispersion stability of the resulting dispersion.

  The total content of [(a) component + (d) component] in the monomer mixture is preferably 6% to 60%, more preferably 10% to 50%, from the viewpoint of dispersion stability of the resulting dispersion. is there. The total content of [component (a) + component (e)] is preferably 6% to 75%, more preferably 13% to 50%, from the viewpoint of dispersion stability of the resulting dispersion. Further, the total content of [(a) component + (d) component + (e) component] is preferably 6% to 60%, more preferably 7% to from the viewpoint of dispersion stability of the resulting dispersion. 50%.

Preferred embodiment (g) of the present invention
The ink of the present invention is obtained by polymerizing a dispersion containing an organic pigment contained in a resin layer formed by emulsion polymerization, and at least ethyl acrylate and (meth) acrylic acid as constituent components, and a glass transition temperature of −10. And polymer fine particles having an acid value of 100 mgKOH / g or less.

  As the polymer fine particles contained in the ink of the present invention, the polymer fine particles described in the above embodiment (f) can be preferably used.

  The dispersion comprising the ink of the present invention is characterized by containing an organic pigment included in a resin layer formed by emulsion polymerization. By including the organic pigment in the resin layer by emulsion polymerization, the dispersion stability of the pigment is improved.

  In emulsion polymerization for forming the resin layer containing the organic pigment of the present invention, a general non-reactive surfactant can be used, but an ionic polymerizable surfactant is preferably used. If a surfactant having polymerizability, that is, reactivity is used, the surfactant itself becomes a constituent component of the resin layer, so that the amount of the surfactant remaining in the prepared dispersion can be reduced. Thereby, the process of removing the remaining surfactant from the dispersion can be omitted. Furthermore, the effect that the dispersion stability of the dispersion is improved by the ionic group derived from the ionic polymerizable surfactant is also exhibited.

  The ionic polymerizable surfactant is a surfactant having an ionic group, a hydrophobic group, and a polymerizable group. Examples of the ionic group include an anionic group and a cationic group, and are appropriately determined depending on the use of the dispersion and required properties. The ionic polymerizable surfactant is referred to as an anionic polymerizable surfactant or a cationic polymerizable surfactant, respectively, depending on whether the ionic group has an anionic group or a cationic group.

  Preferred examples of the anionic group include those selected from the group consisting of a sulfone group, a sulfinic group, a carboxyl group, a phosphoric acid group, a sulfonic acid ester group, a sulfinic acid ester group, a phosphoric acid ester group, and salts thereof. . Examples of the salt include Na salt, K salt, Ca salt, organic amine salt and the like.

As the cationic group, a cationic group selected from the group consisting of a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation, and a quaternary ammonium cation is preferable. The primary ammonium cation is a monoalkylammonium cation (RNH ₃ ⁺ ), the secondary ammonium cation is a dialkylammonium cation (R ₂ NH ₂ ⁺ ), and the tertiary ammonium cation is a trialkylammonium cation (R ₃ NH). ⁺ ) And the like, and examples of the quaternary ammonium cation include (R ₄ N ⁺ ) and the like. Here, R is a hydrophobic group, and examples thereof include the following. Examples of the counter anion of the cationic group include Cl ⁻ , Br ⁻ , I ⁻ , CH ₃ OSO ₃ ⁻ , C ₂ H ₅ OSO ₃ ^{—, and the} like.

  The hydrophobic group is preferably one or two or more selected from the group consisting of an alkyl group having 8 to 16 carbon atoms and an aryl group such as a phenyl group and a phenylene group, and the alkyl group and the aryl group in the molecule. You may have both.

  The polymerizable group is preferably an unsaturated hydrocarbon group capable of radical polymerization, and specifically selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. It is preferred that Especially, an allyl group, a methacryloyl group, and an acryloyl group are preferable.

  Specific examples of the anionic polymerizable surfactant used in the present invention include anionic allyl derivatives described in JP-B-49-46291, JP-B-1-24142, or JP-A-62-104802. Anionic propenyl derivatives described in JP-A-62-221431, anionic acrylic acid derivatives described in JP-A-62-34947 or JP-A-55-11525, and JP-B-46-34898 And an anionic itaconic acid derivative described in JP-A No. 51-30284.

  Examples of the anionic polymerizable surfactant used in the present invention include the following general formula (31):

(In the formula, R ²¹ and R ³¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z ¹ is a carbon-carbon single bond, or a group represented by the formula:
—CH ₂ —O—CH ₂ —
M is an integer of 2 to 20, and X is a formula:
-SO ₃ M ¹
M ¹ is an alkali metal, an ammonium salt, or an alkanolamine. Or a compound represented by the following general formula (32):

(Wherein R ²² and R ³² are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and D is a carbon-carbon single bond, or a group represented by the formula:
—CH ₂ —O—CH ₂ —
N is an integer of 2 to 20, and Y is a formula:
-SO ₃ M ²
M ² is an alkali metal, an ammonium salt, or an alkanolamine. ) Is preferred.

  Examples of the anionic polymerizable surfactant represented by the formula (31) include compounds described in JP-A-5-320276 or JP-A-10-316909. By appropriately adjusting the value of m in the formula (31), it is possible to adjust the fresh water on the surface of the resin layer including the pigment particles. As a preferable polymerizable surfactant represented by the formula (31), a compound represented by the following formula (310) can be exemplified. More specifically, compounds represented by the following formulas (31a) to (31d) can be given.

(Wherein R ³¹ , m, and M ¹ are the same as the compound represented by formula (31).)

A commercial item can also be used as said anionic polymerizable surfactant. Adekaria Soap SE-10N manufactured by Asahi Denka Kogyo Co., Ltd. is a compound represented by the formula (310), wherein M ¹ is NH ₄ , R ³¹ is C ₉ H ₁₉ , and m = 10. . Similarly, Adekari Soap SE-20N is a compound represented by the formula (310), wherein M ¹ is NH ₄ , R ³¹ is C ₉ H ₁₉ , and m = 20.

  Examples of the anionic polymerizable surfactant used in the present invention include the following general formula (33):

(In the formula, p is 9 or 11, q is an integer of 2 to 20, A is a group represented by —SO ₃ M3, and M3 is an alkali metal, an ammonium salt, or an alkanolamine.)

  The compound represented by these can also be mention | raise | lifted. Preferred examples of the anionic polymerizable surfactant represented by the formula (33) include the following compounds.

  (Wherein r is 9 or 11, and s is 5 or 10)

  A commercial item can also be used as said anionic polymerizable surfactant. Examples of commercially available products include Aqualon KH series (Aqualon KH-5 and Aqualon KH-10) (above, trade names) from Daiichi Kogyo Seiyaku Co., Ltd., and the like. Aqualon KH-5 is a mixture of a compound in which r is 9 and s is 5 and a compound in which r is 11 and s is 5 in the above formula (33). Aqualon KH-10 is a mixture of a compound in which r is 9 and s is 10 and a compound in which r is 11 and s is 10 in the above formula (33).

  In addition, examples of the anionic polymerizable surfactant used in the present invention include compounds represented by the following general formula (34).

(In the formula, R is an alkyl group having 8 to 15 carbon atoms, n is an integer of 2 to 20, X is a group represented by —SO ₃ B, and B is an alkali metal, ammonium salt or alkanol. Amine.)

A commercial item can also be used as said anionic polymerizable surfactant. Examples of commercially available products include Adeka Soap SR Series (Adeka Soap SR-10, SR-20, SR-1025) (above, trade names) manufactured by Asahi Denka Kogyo Co., Ltd., and the like. The ADEKA rear soap SR series is a compound in which B is NH ₄ in the above formula (34), SR-10 is n = 10, and SR-20 is n = 20.

  In addition, examples of the anionic polymerizable surfactant used in the present invention include compounds represented by the following general formula (A).

In (the above formula (A), R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, l is an integer of 2 to 20, M ⁴ represents an alkali metal, an ammonium salt or an alkanolamine, .)

  A commercial item can also be used as said anionic polymerizable surfactant. As a commercial item, the Aqualon HS series (Aqualon HS-10, HS-20, and HS-1025) (above, a brand name) of Dai-ichi Kogyo Seiyaku Co., Ltd. is mentioned, for example.

  In addition, examples of the anionic polymerizable surfactant used in the present invention include alkylallylsulfosuccinic acid sodium salt represented by the following general formula (35).

  A commercial item can also be used as said anionic surfactant. As a commercial item, the Elemiol JS-2 of Sanyo Chemical Industries Ltd. can be mention | raise | lifted, for example. This is a compound represented by m = 12, in the general formula (35).

  Examples of the anionic polymerizable surfactant used in the present invention include methacryloyloxypolyoxyalkylene sulfate sodium salt represented by the following general formula (36). In the following formula, n is 1-20.

  A commercial item can also be used as said anionic surfactant. As a commercial item, the Elemiol RS-30 of Sanyo Chemical Industries Ltd. can be mention | raise | lifted, for example. This is a compound represented by n = 9 in the general formula (36).

  In addition, examples of the anionic polymerizable surfactant used in the present invention include a compound represented by the following general formula (37).

  A commercial item can also be used as said anionic surfactant. As a commercial item, Antox MS-60 of Nippon Emulsifier Co., Ltd. can be mentioned, for example.

  The anionic polymerizable surfactants exemplified above can be used alone or as a mixture of two or more.

The cationic polymerizable surfactants include, for example, the general formula _{R [4- (l + m +} n)] R 1 l R 2 m R 3 n N + · X - can be exemplified represented by compound (In the above general formula, R is a polymerizable group, R ¹ , R ² and R ³ are each an aryl group such as an alkyl group having 8 to 16 carbon atoms and a phenylene group, and X ⁻ is Cl ⁻ , Br. _{^{-, I -, CH 3 OSO}} 3 -, C 2 H 5 OSO 3 - and is, l, m and n are respectively 1 or 0). Here, examples of the polymerizable group include those described above.

  Specific examples of the cationic polymerizable surfactant used in the present invention include dimethylaminoethyl methacrylate salt, dimethylaminoethyl octyl chloride salt, dimethylaminoethyl cetyl methacrylate salt, dimethylaminoethyl decyl chloride methacrylate. Salt, dimethylaminoethyl dodecyl chloride salt of methacrylic acid, dimethylaminoethyl tetradecyl chloride salt of methacrylic acid and the like. The cationic polymerizable surfactants exemplified above can be used alone or as a mixture of two or more.

  In the emulsion polymerization for forming the resin layer containing the organic pigment of the present invention, it is also possible to use a hydrophobic monomer as a constituent component of the resin layer. The hydrophobic monomer refers to a compound having at least a hydrophobic group and a polymerizable group in its structure, and the hydrophobic group is selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The selected one can be exemplified.

  Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, and a propyl group, and examples of the alicyclic hydrocarbon group include a cyclohexyl group, a dicyclopentenyl group, an isobornyl group, and the like as an aromatic hydrocarbon group. Includes benzyl group, phenyl group, naphthyl group and the like.

  Examples of the polymerizable group of the hydrophobic monomer include the same as those described for the ionic polymerizable surfactant.

  Specific examples of the hydrophobic monomer include styrene derivatives such as styrene, methylstyrene, vinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, t-butylstyrene, bromostyrene, and p-chloromethylstyrene; methyl acrylate, acrylic acid Ethyl, isopropyl acrylate, n-butyl acrylate, butoxyethyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, benzyl acrylate, phenyl acrylate , Phenoxyethyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, Cyclopentenyloxyethyl acrylate, tetrahydrofuryl acrylate, and isobornyl acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxydipropylene glycol acrylate, phenoxy polyethylene glycol acrylate Monofunctional acrylic acid esters such as nonylphenol EO adduct acrylate, isooctyl acrylate, isomyristyl acrylate, isostearyl acrylate, 2-ethylhexyl diglycol acrylate, octoxypolyethylene glycol polypropylene glycol monoacrylate, methyl methacrylate, Ethyl tacrylate, isopropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate , Stearyl methacrylate, isodecyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, methoxydiethylene glycol methacrylate, polypropylene glycol monomethacrylate, benzyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate, tetrahydromethacrylate Furfuryl, t-butylcyclo Monofunctional methacrylates such as hexyl methacrylate, behenyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, butoxymethyl methacrylate, and isobornyl methacrylate, octoxy polyethylene glycol polypropylene glycol monomethacrylate Allyl compounds such as allylbenzene, allyl-3-cyclohexanepropionate, 1-allyl-3,4-dimethoxybenzene, allylphenoxyacetate, allylphenylacetate, allylcyclohexane, and allyl polycarboxylate; fumaric acid, malee Acids and unsaturated esters such as itaconic acid; radically polymerizable groups such as N-substituted maleimides and cyclic olefins Monomer or the like having the like.

  In the emulsion polymerization for forming the resin layer containing the organic pigment of the present invention, as a constituent component of the resin layer, in addition to the various surfactants and the hydrophobic monomer, other components may be used as long as the effects of the present invention are not impaired. A polymerizable monomer component can be used. Examples of other polymerizable monomers that can be used in the present invention include crosslinkable monomers. By adding a crosslinkable monomer to the polymerization component and copolymerizing with the hydrophobic monomer, the mechanical strength, heat resistance, solvent resistance, etc. of the polymer can be improved. Thereby, for example, in the ink for inkjet recording, the dispersibility of the pigment particles, the storage stability and the discharge property of the ink can be improved.

  Examples of the crosslinkable monomer that can be used in the present invention include two or more unsaturated hydrocarbon groups selected from a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. The compound which has is mention | raise | lifted. Specific examples of the crosslinkable monomer include, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, allyl acrylate, and bis (acryloxyethyl) hydroxyethyl isocyanurate. Bis (acryloxy neopentyl glycol) adipate, 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, 2-hydroxy-1 , 3-Diacryloxypropane, 2,2-bis [4- (acryloxy) phenyl] propane, 2,2- [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy polyethoxy) phenyl] propane, hydroxypentylglycol diacrylate, dipentaerythritol hexaacrylate, dipenta Erythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, tetrabromobisphenol A diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol Dimethacrylate, triethylene glycol dimethacrylate, tetraethyleneglycol Dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- (methacryloxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2- Bis [4- (methacryloxyethoxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxypolyethoxy) phenyl] propane, tetrabromobisphenol A dimethacrylate , Dicyclopentanyl dimethacrylate, dipentaerythritol hexamethacrylate, glycerol dimethacrylate, hydroxypentylglycolate dipentaerythritol monohydroxypentamethacrylate, ditrimethylolpropane tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol Examples include tetramethacrylate, triglycerol dimethacrylate, trimethylolpropane trimethacrylate, tris (methacryloxyethyl) isocyanurate, allyl methacrylate, divinylbenzene, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, and diethylene glycol bisallyl carbonate.

  The emulsion polymerization reaction for forming the resin layer containing the organic pigment of the present invention can be performed using a known polymerization initiator. Specific examples of the polymerization initiator include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,3- Dimethylbutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,3,3-trimethylbutyronitrile), 2,2′-azobis (2-isopropyl) Butyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile 4,4′-azobis (4-cyanovaleric acid), and dimethyl-2,2′-azobisisobutyrate, or peroxide compounds such as butyl peroxide, Pyrperoxide, butyryl peroxide, benzoylisobutyryl peroxide, and benzoyl peroxide, or water-soluble polymerization initiators such as potassium persulfate, ammonium persulfate, sodium persulfate, 2,2′-azobis (2-methylpropionamidine ) Dihydrochloride, 4,4′-azobis (4-cyanovaleric acid) and the like. In addition, a redox initiator in which potassium persulfate, ammonium persulfate, sodium persulfate, and the like are combined with sodium sulfite, sodium hyposulfite, ferrous sulfate, or the like can also be used.

Hereinafter, the present invention will be described more specifically. The present invention is not limited to the following examples.
The following Example A corresponds to the preferred embodiment (a) described above.

[Example A]
(Example A-1)
(1) Production of Pigment Dispersion A1 As the pigment dispersion A1, Monarch 880 manufactured by Cabot Corporation of the United States, which is carbon black (Pigment Black 7), was used. The surface of carbon black was oxidized by the same method as in JP-A-8-3498 to make it dispersible in water, thereby preparing dispersion A1. The particle diameter was measured using a Microtrac particle size distribution analyzer UPA250 (manufactured by Nikkiso), and it was 110 nm.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.2 parts of potassium is added, 0.05 parts of sodium lauryl sulfate, 4 parts of glycidoxy acrylate, 15 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of tetrahydrofurfuryl acrylate in 7 parts of ion-exchanged water Then, a monomer solution containing 5 parts of butyl methacrylate and 0.02 part of t-dodecyl mercaptan is dropped at 70 ° C. and reacted to prepare a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 25 parts of methyl acrylate, 6 parts of butyl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared and designated as Emulsion A (EM-A). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). When the solvent was measured as THF using gel permeation chromatography (GPC) of L7100 system manufactured by Hitachi, Ltd., the molecular weight in terms of styrene was 150,000. The acid value was 20 mgKOH / g. The acid value was measured by the following method. It collects in the state before sodium hydroxide neutralization of the said polymer fine particle aqueous dispersion, The solid content density | concentration is correctly measured with a thermobalance (TG-2121 by Seiko Electronic Industry). Next, about 10 g of this polymer fine particle aqueous dispersion is accurately weighed, put into a stoppered Erlenmeyer flask, and 100 ml of 2-propanol-tetrahydrofuran mixture (1: 2) is added and dissolved. As an indicator, and titrating with a 0.1 mol / L 2-propanol potassium hydroxide solution until a pale red color lasting 30 seconds is obtained. The acid value is determined by the formula (1).

Acid value (mgKOH / g) = (5.611 × a × f) / S (1)
S: Sample collection amount (g)
a: Consumption of 0.1 mol / L 2-propanol potassium hydroxide solution (ml)
f: Factor of 0.1 mol / L 2-propanol potassium hydroxide solution where a is the titration value (ml) -blank value (ml)

(3) Preparation of inkjet recording ink Table 2 shows examples of compositions suitable for inkjet recording ink. The ink for inkjet recording of the present invention was prepared by using the dispersion A1 prepared by the above method and mixing with the vehicle components shown in Table 2. In addition, 0.05% of the top side 240 (manufactured by Permachem Asia Co., Ltd.) is used for the remaining amount of water in Examples and Comparative Examples of the present invention to prevent ink corrosion, and benzotriazole is used to prevent ink jet head member corrosion. 0.02%, and EDTA (ethylenediaminetetraacetic acid) .2Na salt in an amount of 0.04% was added to ion-exchanged water in order to reduce the influence of metal ions in the ink system.

(4) Scratch resistance test and dry cleaning test Using the ink of Example A-1 and using a PX-V600 manufactured by Seiko Epson Corporation as an ink jet printer, a sample solidly printed on cotton is prepared. The sample was subjected to friction fastness by rubbing 100 times with a load of 200 g using a Gakushin type friction fastness tester AB-301S manufactured by Tester Sangyo Co., Ltd. Two levels of dry and wet were evaluated according to Japanese Industrial Standard (JIS) JIS L0849, which confirms the degree of ink peeling. Similarly, the dry cleaning test was evaluated by the method B of JIS L0860. Table 1 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using PX-V600 manufactured by Seiko Epson Corporation as an inkjet printer, MSX Gothic, a standard for character size 11 in Microsoft Word on XeroxP paper A4 size manufactured by Fuji Xerox Co., Ltd. at 35 ° C and 35% atmosphere. Evaluation was performed by printing 100 pages at a rate of 4000 characters / page. AA when there is no printing disorder at all, A with printing disorder at one place, B with printing disorder at 2-3 places, C at 4-5 printing disorders, and 6 or more printing disorders The results are shown in Table 1 with D as the result.

(Example A-2)
(1) Production of Pigment Dispersion A2 First, Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used as Pigment Dispersion A2. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 75 parts of benzyl acrylate, 2 parts of acrylic acid, and 0.3 part of t-dodecyl mercaptan were added and heated to 70 ° C. separately. Disperse polymer while adding 150 parts of benzyl acrylate, 15 parts of acrylic acid, 5 parts of butyl acrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 1 part of sodium persulfate to the reaction vessel over 4 hours. Was subjected to a polymerization reaction. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 40%. A portion of this polymer was taken out and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC, manufactured by Seiko Denshi).

  Further, 40 parts of the dispersion polymer solution, 30 parts of Pigment Blue 15: 3, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 30 parts of methyl ethyl ketone were mixed. Then, using an ultra-high pressure homogenizer (Ultimizer HJP-25005 manufactured by Sugino Machine Co., Ltd.), it was dispersed by passing 15 passes at 200 MPa. Then, it moved to another container, 300 parts of ion-exchange water was added, and also it stirred for 1 hour. And the whole amount of methyl ethyl ketone and a part of water were distilled off using the rotary evaporator, and it neutralized with 0.1 mol / L sodium hydroxide, and adjusted to pH9. Then, it filtered with a 0.3 micrometer membrane filter, adjusted with ion-exchange water, and was set as pigment dispersion A2 whose pigment concentration is 15%. The particle diameter was measured by the same method as in Example A-1.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.2 parts of potassium have been added, 0.05 parts of sodium lauryl sulfate, 19 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of tetrahydrofurfuryl acrylate, 5 parts of butyl methacrylate and t -A monomer solution containing 0.02 part of dodecyl mercaptan is dropped and reacted at 70 ° C to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 25 parts of methyl acrylate, 16 parts of butyl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared to obtain Emulsion B (EM-B). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). When the molecular weight was measured in the same manner as in Example 1, it was 200,000. The acid value was 20 mgKOH / g. The acid value was measured by the same method as in Example A-1.

(3) Preparation of inkjet recording ink Table 2 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared in the same manner as in Example A-1 by using the dispersion A2 prepared by the above method and mixing with the vehicle components shown in Table 2.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example A-2, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example A-1. Table 1 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example A-2, ejection stability was measured by the same method and the same evaluation method as Example A-1. Table 1 shows the measurement results of the discharge stability.

(Example A-3)
(1) Production of Pigment Dispersion A3 First, Pigment Dispersion A3 was prepared in the same manner as Pigment Dispersion A2 using Pigment Violet 19 (Quinacridone Pigment: Clariant), and was used as Pigment Dispersion A3. The particle diameter was measured by the method used in Example A-1 to be 90 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example A-2 were used.

(3) Preparation of inkjet recording ink Table 2 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example A-1 by using the dispersion A3 prepared by the above method and mixing with the vehicle components shown in Table 2.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example A-3, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example A-1. Table 1 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example A-3, ejection stability was measured by the same method and the same evaluation method as Example A-1. Table 1 shows the measurement results of the discharge stability.

(Example A-4)
(1) Production of Pigment Dispersion A4 First, Pigment Dispersion A4 was prepared in the same manner as Pigment Dispersion A2 using Pigment Yellow 14 (azo pigment: manufactured by Clariant) to obtain Pigment Dispersion A4. The particle diameter was measured by the method used in Example A-1 to be 115 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example A-2 were used.

(3) Preparation of inkjet recording ink Table 2 shows examples of compositions suitable for inkjet recording ink. The ink for inkjet recording of the present invention was prepared and evaluated in the same manner as in Example 1 by using the dispersion A4 produced by the above method and mixing with the vehicle components shown in Table 2.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example A-4, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example A-1. Table 1 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example A-4, ejection stability was measured by the same method and the same evaluation method as Example A-1. Table 1 shows the measurement results of the discharge stability.

(Comparative Example A-1)
Comparative Example A-1 was the same as Example A-1 except that polymer fine particles having a glass transition temperature of 0 ° C. were used except that a part of ethyl acrylate was changed to styrene in Example A-1. Similarly, inks were produced and evaluated. An emulsion prepared using the polymer fine particles was named Emulsion B (EM-B). The ink composition is shown in Table 2. The rubbing resistance test, dry cleaning test and ejection stability test were performed in the same manner as in Example A-1. The results are shown in Table 1.

(Comparative Example A-2)
Comparative Example A-2 was the same as Example A-2 except that polymer fine particles having a glass transition temperature of 10 ° C. were used except that a part of ethyl acrylate and butyl acrylate was changed to styrene in Example A-2. Ink was prepared and evaluated in the same manner as in 2. An emulsion produced using these polymer fine particles was designated as Emulsion C (EM-C). The ink composition is shown in Table 2. The rubbing resistance test, dry cleaning test and ejection stability test were performed in the same manner as in Example A-1. The results are shown in Table 1.

(Comparative Example A-3)
In Comparative Example A-3, an ink was prepared and evaluated in the same manner as in Example A-3 except that a dispersion having a pigment particle size of 350 nm and 45 nm was prepared in Example A-3. The particle size was measured by the same method as in Example A-1. The dispersion having a particle size of 350 nm was designated as pigment dispersion A3A, and the dispersion having a particle size of 45 nm was designated as pigment dispersion A3B. The ink composition is shown in Table 2. The rubbing resistance test, dry cleaning test and ejection stability test were performed in the same manner as in Example A-1. The results are shown in Table 1.

(Comparative Example A-4)
Comparative Example A-4 was prepared and evaluated in the same manner as in Example A-4 except that the acid value of the polymer fine particles to be added was changed to 120 mgKOH / g and 150 mgKOH / g in Example A-4. An emulsion prepared using polymer fine particles having an acid value of 120 mgKOH / g is referred to as emulsion D (EM-D), and an emulsion prepared using polymer fine particles having an acid value of 120 mgKOH / g is emulsion E (EM-E). It was. The ink composition is shown in Table 2. The rubbing resistance test, dry cleaning test and ejection stability test were performed in the same manner as in Example A-1. The results are shown in Table 1.

(Example A-5)
(1) Production of Pigment Dispersion A5 As the pigment dispersion A5, MA100 manufactured by Mitsubishi Chemical Industries, Ltd., which is carbon black (PBk7), was used. The surface of carbon black was oxidized by the same method as in JP-A-8-3498 to make it dispersible in water, thereby preparing dispersion A5. The particle diameter was measured by the method used in Example A-1 to be 120 nm.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.3 parts of potassium has been added, 0.05 parts of sodium lauryl sulfate, 20 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of lauryl acrylate, 5 parts of butyl methacrylate and t-dodecyl in 7 parts of ion-exchanged water A monomer solution containing 0.02 part of mercaptan is dropped and reacted at 70 ° C. to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 25 parts of butyl acrylate, 16 parts of lauryl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared to obtain an emulsion G (EM-G). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured with a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). The molecular weight was measured by the same method as in Example 1 and found to be 180,000. The acid value was 18 mgKOH / g. The acid value was measured by the same method as in Example 1.

(3) Preparation of Inkjet Recording Ink Table 4 shows examples of compositions suitable for inkjet recording ink. The ink for inkjet recording of the present invention was prepared and evaluated in the same manner as in Example A-1 by using the dispersion A5 prepared by the above method and mixing with the vehicle components shown in Table 4.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example A-5, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example A-1. Table 3 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example A-5, ejection stability was measured by the same method and the same evaluation method as Example A-1. Table 3 shows the measurement results of the discharge stability.

(Example A-6)
(1) Production of Pigment Dispersion A6 First, Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used as Pigment Dispersion A6. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was replaced with nitrogen, and then 45 parts of styrene, 30 parts of polyethylene glycol 400 acrylate, 10 parts of benzyl acrylate, 2 parts of acrylic acid, 0.3 part of t-dodecyl mercaptan And heated to 70 ° C., and separately prepared 150 parts of styrene, 100 parts of polyethylene glycol 400 acrylate, 15 parts of acrylic acid, 5 parts of butyl acrylate, 1 part of t-dodecyl mercaptan and 5 parts of sodium persulfate are placed in a dropping funnel. Then, the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, water was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 40%. A part of this polymer was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi), and it was 45 ° C.

  Also, 40 parts of the above dispersion polymer solution, 30 parts of pigment and blue 15: 3, and 100 parts of 0.1 mol / L sodium hydroxide aqueous solution are mixed and dispersed using an Eiger mill using zirconia beads for 2 hours. . Then, it transfers to another container, 300 parts of ion-exchange water is added, and also it stirs for 1 hour. And it neutralizes with 0.1 mol / L sodium hydroxide and adjusts to pH9. Then, it filtered with a 0.3 micrometer membrane filter, and was set as the dispersion A6 whose solid content (dispersion polymer, pigment, and blue 15: 3) is 20%. The particle diameter was measured by the method used in Example A-1 to be 100 nm. It was 210,000 when molecular weight was measured by the same method as Example A-1.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.3 parts of potassium is added, 0.05 parts of sodium lauryl sulfate, 20 parts of ethyl acrylate, 25 parts of butyl acrylate, 6 parts of lauryl acrylate, 5 parts of butyl methacrylate and t-dodecyl are added to 7 parts of ion-exchanged water. A monomer solution containing 0.02 part of mercaptan is dropped and reacted at 70 ° C. to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 20 parts of ethyl acrylate, 20 parts of butyl acrylate, 20 parts of lauryl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared to obtain Emulsion F (EM-F). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured with a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). It was 200000 when the molecular weight was measured by the same method as Example A-1. The acid value was 18 mgKOH / g. The acid value was measured by the same method as in Example A-1.

(3) Preparation of Inkjet Recording Ink Table 4 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example A-1 by using the dispersion 1 prepared by the above method and mixing it with the vehicle components shown in Table 4.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example A-6, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example A-1. Table 3 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example A-6, ejection stability was measured by the same method and the same evaluation method as Example A-1. Table 3 shows the measurement results of the discharge stability.

(Example 7)
(1) Production of Pigment Dispersion A7 First, Pigment Dispersion A7 was prepared in the same manner as Pigment Dispersion A2 using Pigment Red 122 (Dimethylquinacridone Pigment: Clariant). The particle diameter was measured by the same method as in Example A-1.

(2) Production of polymer fine particles The same polymer fine particles as in Example A-6 were used.

(3) Preparation of Inkjet Recording Ink Table 4 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example A-1 by using the dispersion A7 prepared by the above method and mixing with the vehicle components shown in Table 4.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example A-7, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example A-1. Table 3 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example A-7, ejection stability was measured by the same method and the same evaluation method as Example A-1. Table 3 shows the measurement results of the discharge stability.

(Example A-8)
(1) Production of Pigment Dispersion A8 First, Pigment Dispersion A8 was prepared in the same manner as Pigment Dispersion A2 using Pigment Yellow 180 (Benzimidazolone Disazo Pigment: Clariant). The particle diameter was measured by the method used in Example A-1 to be 130 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example A-6 were used.

(3) Preparation of Inkjet Recording Ink Table 4 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example A-1 by using the dispersion A8 prepared by the above method and mixing with the vehicle components shown in Table 4.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example A-8, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example A-1. Table 3 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example A-8, ejection stability was measured by the same method and the same evaluation method as in Example A-1. Table 3 shows the measurement results of the discharge stability.

(Reference Example A-5)
In Reference Example A-5, an ink was prepared and evaluated in the same manner as in Example A-5 except that the molecular weight of the polymer fine particles added in Example A-5 was changed to 90000 and 1100000. An emulsion having a molecular weight of 90000 was designated as Emulsion H (EM-H), and an emulsion having a molecular weight of 90000 was designated as Emulsion I (EM-I). The ink composition is shown in Table 4. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example A-5. The results are shown in Table 3. The measurement of the particle diameter of the polymer fine particles was performed in the same manner as in Example A-1.

(Reference Example A-6)
Reference Example A-6 was prepared and evaluated in the same manner as in Example A-6 except that 1,2-hexanediol as 1,2-alkylene glycol was replaced with glycerin in Example A-6. The ink composition is shown in Table 4. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example A-5. The results are shown in Table 3.

(Reference Example A-7)
Reference Example A-7 was prepared and evaluated in the same manner as in Example A-7, except that glycerin was substituted for the acetylene glycol surfactant and acetylene alcohol surfactant in Example A-7. did. The ink composition is shown in Table 4. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example A-5. The results are shown in Table 3.

(Reference Example A-8)
Reference Example A-8 was prepared and evaluated in the same manner as in Example A-8, except that the amount of the polymer fine particles added was 80% and 50% in pigment ratio in Example A-8. . The ink composition is shown in Table 4. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example A-5. The results are shown in Table 3.

Next, examples of other preferred embodiments according to the present invention will be described.
[Example B]
Example B below corresponds to other preferred embodiment (b).
(Example B-1)
(1) Production of Pigment Dispersion B1 For the pigment dispersion B1, Monarch 880 manufactured by Cabot Corporation of the United States, which is carbon black (Pigment Black 7), was used. The surface of carbon black was oxidized by the same method as in JP-A-8-3498 to make it dispersible in water. The particle diameter was measured using a Microtrac particle size distribution analyzer UPA250 (manufactured by Nikkiso), and it was 110 nm.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.2 parts of potassium is added, 0.05 parts of sodium lauryl sulfate, 4 parts of glycidoxy acrylate, 15 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of tetrahydrofurfuryl acrylate in 7 parts of ion-exchanged water Then, a monomer solution containing 5 parts of butyl methacrylate and 0.02 part of t-dodecyl mercaptan is dropped at 70 ° C. and reacted to prepare a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 25 parts of methyl acrylate, 6 parts of butyl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared and designated as Emulsion A (EM-A). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). When the solvent was measured as THF using gel permeation chromatography (GPC) of L7100 system manufactured by Hitachi, Ltd., the molecular weight in terms of styrene was 150,000. Moreover, the acid value by the titration method was 20 mgKOH / g.

(3) Preparation of inkjet recording ink Table 6 shows examples of compositions suitable for the inkjet recording ink. The ink for inkjet recording of the present invention was prepared by using the dispersion B1 prepared by the above method and mixing with the vehicle components shown in Table 6. In addition, 0.05% of the top side 240 (manufactured by Permachem Asia Co., Ltd.) is used for the remaining amount of water in Examples and Comparative Examples of the present invention to prevent ink corrosion, and benzotriazole is used to prevent ink jet head member corrosion. 0.02%, and EDTA (ethylenediaminetetraacetic acid) .2Na salt in an amount of 0.04% was added to ion-exchanged water in order to reduce the influence of metal ions in the ink system.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example B-1, using a PX-V600 manufactured by Seiko Epson Corporation as an ink jet printer, a sample solidly printed on a cotton cloth was created, and the sample was at 150 ° C. Heat for 5 minutes. The sample was subjected to friction fastness by rubbing 100 times with a load of 200 g using a Gakushin type friction fastness tester AB-301S manufactured by Tester Sangyo Co., Ltd. Two levels of dry and wet were evaluated according to Japanese Industrial Standard (JIS) JIS L0849, which confirms the degree of ink peeling. Similarly, the dry cleaning test was evaluated by the method B of JIS L0860. Table 5 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using PX-V600 manufactured by Seiko Epson Corporation as an inkjet printer, MSX Gothic, a standard for character size 11 in Microsoft Word on XeroxP paper A4 size manufactured by Fuji Xerox Co., Ltd. at 35 ° C and 35% atmosphere. Evaluation was performed by printing 100 pages at a rate of 4000 characters / page. AA when there is no printing disorder at all, A when there is printing disorder at A, B at 2 to 3 printing disorder B, C at 4 to 5 printing disorder, 6 or more printing disorder The results are shown in Table 5 with D being the presence.

(Example B-2)
(1) Production of Pigment Dispersion B2 Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used as the pigment dispersion B2. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 75 parts of benzyl acrylate, 2 parts of acrylic acid, and 0.3 part of t-dodecyl mercaptan were added and heated to 70 ° C. separately. Disperse polymer while adding 150 parts of benzyl acrylate, 15 parts of acrylic acid, 5 parts of butyl acrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 1 part of sodium persulfate to the reaction vessel over 4 hours. Was subjected to a polymerization reaction. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 40%. A portion of this polymer was taken out and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC, manufactured by Seiko Denshi).

  Further, 40 parts of the dispersion polymer solution, 30 parts of Pigment Blue 15: 3, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 30 parts of methyl ethyl ketone were mixed. Then, using an ultra-high pressure homogenizer (Ultimizer HJP-25005 manufactured by Sugino Machine Co., Ltd.), it was dispersed by passing 15 passes at 200 MPa. Then, it moved to another container, 300 parts of ion-exchange water was added, and also it stirred for 1 hour. And the whole amount of methyl ethyl ketone and a part of water were distilled off using the rotary evaporator, and it neutralized with 0.1 mol / L sodium hydroxide, and adjusted to pH9. Then, it filtered with a 0.3 micrometer membrane filter, adjusted with ion-exchange water, and was set as the pigment dispersion B2 whose pigment concentration is 15%. The particle diameter was measured by the method used in Example B-1 to be 80 nm.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.2 parts of potassium have been added, 0.05 parts of sodium lauryl sulfate, 19 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of tetrahydrofurfuryl acrylate, 5 parts of butyl methacrylate and t -A monomer solution containing 0.02 part of dodecyl mercaptan is dropped and reacted at 70 ° C to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 25 parts of methyl acrylate, 16 parts of butyl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared to obtain Emulsion B (EM-B). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). The molecular weight was measured in the same manner as in Example B-1. Moreover, the acid value by the titration method was 20 mgKOH / g.

(3) Preparation of inkjet recording ink Table 6 shows examples of compositions suitable for the inkjet recording ink. The ink for inkjet recording of the present invention was prepared in the same manner as in Example B-1 by using the dispersion B2 prepared by the above method and mixing with the vehicle components shown in Table 6.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example B-2, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example B-1. Table 5 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example B-2, the ejection stability was measured by the same method and the same evaluation method as Example B-1. Table 5 shows the measurement results of the discharge stability.

(Example 3)
(1) Production of Pigment Dispersion B3 Pigment Dispersion B3 was prepared in the same manner as Pigment Dispersion B2 using Pigment Violet 19 (Quinacridone Pigment: Clariant), and was used as Pigment Dispersion B3. The particle diameter was measured by the method used in Example B-1 to be 90 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example B-2 were used.

(3) Preparation of inkjet recording ink Table 6 shows examples of compositions suitable for the inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example B-1 by using the dispersion B3 prepared by the above method and mixing with the vehicle components shown in Table 6.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example B-3, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example B-1. Table 5 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example B-3, the ejection stability was measured by the same method and the same evaluation method as Example B-1. Table 5 shows the measurement results of the discharge stability.

(Example B-4)
(1) Production of Pigment Dispersion B4 Pigment Dispersion B4 was prepared in the same manner as Pigment Dispersion B2 using Pigment Yellow 14 (azo pigment: manufactured by Clariant) to obtain Pigment Dispersion B4. The particle diameter was measured by the method used in Example B-1 to be 115 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example B-2 were used.

(3) Preparation of Inkjet Recording Ink Table 4 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example B-1 by using the dispersion B4 produced by the above method and mixing with the vehicle components shown in Table 4.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example B-4, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example B-1. Table 5 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example B-4, the ejection stability was measured by the same method and the same evaluation method as Example B-1. Table 5 shows the measurement results of the discharge stability.

(Comparative Example B-1)
Comparative Example B-1 was the same as Example B-1 except that the total amount of ethyl acrylate (45 parts) was changed to 45 parts of benzyl methacrylate, except that polymer fine particles having a glass transition temperature of 0 ° C. were used. An ink was prepared and evaluated in the same manner as in Example B-1. An emulsion produced using these polymer fine particles was designated as Emulsion C (EM-C). The ink composition is shown in Table 6. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example B-1. The results are shown in Table 5.

(Comparative Example B-2)
Comparative Example B-2 has a glass transition temperature of 10 ° C. in the same manner as in Example B-2 except that the total amount of ethyl acrylate (49 parts) is changed to benzyl methacrylate and 10 parts of butyl acrylate is changed to 10 parts of benzyl methacrylate. An ink was prepared and evaluated in the same manner as in Example B-2 except that the polymer fine particles were used. An emulsion produced using these polymer fine particles was designated as Emulsion D (EM-D). The ink composition is shown in Table 6. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example B-1. The results are shown in Table 5.

(Comparative Example B-3)
In Comparative Example B-3, an ink was prepared and evaluated in the same manner as in Example B-3 except that a dispersion having a pigment particle size of 350 nm and 45 nm was prepared in Example B-3. The particle size was measured by the same method as in Example B-1. The dispersion having a particle size of 350 nm was designated as pigment dispersion B3A, and the dispersion having a particle size of 45 nm was designated as pigment dispersion B3B. The ink composition is shown in Table 6. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example B-1. The results are shown in Table 5.

(Comparative Example B-4)
Comparative Example B-4 was prepared and evaluated in the same manner as in Example B-4, except that the acid value of the polymer fine particles to be added was changed to 120 mgKOH / g and 150 mgKOH / g in Example B-4. An emulsion prepared using polymer fine particles having an acid value of 120 mgKOH / g is called Emulsion E (EM-E), and an emulsion prepared using polymer fine particles having an acid value of 120 mgKOH / g is Emulsion F (EM-F). It was. The ink composition is shown in Table 6. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example B-1. The results are shown in Table 5.

(Reference Example B-5)
In Reference Example B-5, 42 parts of ethyl acrylate in the polymer fine particles were replaced with 42 parts of styrene, and the total amount of butyl methacrylate and 15 parts of methyl acrylate were replaced with 2-ethyl-hexyl acrylate in Example B-2. The addition amount is adjusted so that the glass transition temperature is -17 ° C., and 70% by weight or more of alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate is not contained as a constituent (65.3%). An ink was prepared and evaluated in the same manner as in Example B-2 except that polymer fine particles were prepared. An emulsion produced using these polymer fine particles was designated as Emulsion G (EM-G). The ink composition is shown in Table 6. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example B-1. The results are shown in Table 5.

(Reference Example B-6)
In Reference Example B-6, in Example B-2, 40 parts of ethyl acrylate of the polymer fine particles were replaced with 40 parts of styrene, the total amount of methyl acrylate was replaced with lauryl acrylate, and 15 parts of butyl acrylate was also 15 parts of lauryl acrylate. Instead, the addition amount is adjusted so that the glass transition temperature becomes -17 ° C., and 70% by weight or more of alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate is not contained as a component (66.9). %) An ink was prepared and evaluated in the same manner as in Example B-2 except that polymer fine particles were prepared. An emulsion produced using these polymer fine particles was designated as Emulsion H (EM-H). The ink composition is shown in Table 6. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example B-1. The results are shown in Table 5.

(Example B-5)
(1) Production of Pigment Dispersion B5 For the pigment dispersion B5, MA100 manufactured by Mitsubishi Chemical Industries, Ltd., which is carbon black (PBk7), was used. The surface of carbon black was oxidized by the same method as in JP-A-8-3498 to make it dispersible in water, thereby preparing Dispersion B5. The particle diameter was measured by the method used in Example B-1 to be 120 nm.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.3 parts of potassium has been added, 0.05 parts of sodium lauryl sulfate, 20 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of lauryl acrylate, 5 parts of butyl methacrylate and t-dodecyl in 7 parts of ion-exchanged water A monomer solution containing 0.02 part of mercaptan is dropped and reacted at 70 ° C. to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 25 parts of butyl acrylate, 16 parts of lauryl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared to obtain Emulsion I (EM-I). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured with a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). The molecular weight was measured by the same method as in Example B-1. Moreover, the acid value by the titration method was 18 mgKOH / g.

(3) Preparation of inkjet recording ink Table 8 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example B-1 by using the dispersion B5 prepared by the above method and mixing it with the vehicle components shown in Table 8.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example B-5, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example B-1. Table 7 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example B-5, ejection stability was measured by the same method and the same evaluation method as Example B-1. Table 7 shows the measurement results of the discharge stability.

(Example B-6)
(1) Production of Pigment Dispersion B6 Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used as Pigment Dispersion B6. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was replaced with nitrogen, and then 45 parts of styrene, 30 parts of polyethylene glycol 400 acrylate, 10 parts of benzyl acrylate, 2 parts of acrylic acid, 0.3 part of t-dodecyl mercaptan And heated to 70 ° C., and separately prepared 150 parts of styrene, 100 parts of polyethylene glycol 400 acrylate, 15 parts of acrylic acid, 5 parts of butyl acrylate, 1 part of t-dodecyl mercaptan and 5 parts of sodium persulfate are placed in a dropping funnel. Then, the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, water was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 40%. A part of this polymer was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi), and it was 45 ° C.

  Also, 40 parts of the above dispersion polymer solution, 30 parts of Pigment Blue 15: 3 (copper phthalocyanine pigment: Clariant) and 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution are mixed, and an Eiger mill using zirconia beads is used. Disperse over 2 hours. Then, it transfers to another container, 300 parts of ion-exchange water is added, and also it stirs for 1 hour. And it neutralizes with 0.1 mol / L sodium hydroxide and adjusts to pH9. Then, it filtered with a 0.3 micrometer membrane filter, and was set as the dispersion 5 whose solid content (dispersion polymer, pigment, and blue 15: 3) is 20%. The particle diameter was measured by the method used in Example B-1 to be 100 nm. It was 210,000 when the molecular weight was measured by the same method as Example B-1.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.3 parts of potassium is added, 0.05 parts of sodium lauryl sulfate, 20 parts of ethyl acrylate, 25 parts of butyl acrylate, 6 parts of lauryl acrylate, 5 parts of butyl methacrylate and t-dodecyl are added to 7 parts of ion-exchanged water. A monomer solution containing 0.02 part of mercaptan is dropped and reacted at 70 ° C. to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 20 parts of ethyl acrylate, 20 parts of butyl acrylate, 20 parts of lauryl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared and designated as Emulsion J (EM-J). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured with a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). Moreover, the acid value by the titration method was 18 mgKOH / g.

(3) Preparation of inkjet recording ink Table 8 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example B-1 by using the dispersion B6 prepared by the above method and mixing it with the vehicle components shown in Table 8.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example B-6, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example B-1. Table 7 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example B-6, ejection stability was measured by the same method and the same evaluation method as Example B-1. Table 7 shows the measurement results of the discharge stability.

(Example B-7)
(1) Production of Pigment Dispersion B7 Pigment Dispersion B7 was prepared in the same manner as Pigment Dispersion B2 using Pigment Red 122 (Dimethylquinacridone Pigment: Clariant). The particle diameter was measured by the method used in Example B-1 to be 80 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example B-6 were used.

(3) Preparation of inkjet recording ink Table 8 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example B-1 by using the dispersion B7 prepared by the above method and mixing with the vehicle components shown in Table 8.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example B-7, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example B-1. Table 7 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example B-7, ejection stability was measured by the same method and the same evaluation method as Example B-1. Table 7 shows the measurement results of the discharge stability.

(Example B-8)
(1) Production of Pigment Dispersion B8 Pigment Dispersion B8 was prepared in the same manner as Pigment Dispersion B2 using Pigment Yellow 180 (Benzimidazolone-based disazo pigment: Clariant). The particle diameter was measured by the method used in Example B-1 to be 130 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example B-6 were used.

(3) Preparation of inkjet recording ink Table 8 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example B-1 by using the dispersion B8 prepared by the above method and mixing with the vehicle components shown in Table 8.

(4) Abrasion resistance test and dry cleaning property test Using the ink of Example B-8, an abrasion resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example B-1. Table 7 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example B-8, ejection stability was measured by the same method and the same evaluation method as Example B-1. Table 7 shows the measurement results of the discharge stability.

(Reference Example B-7)
In Reference Example B-7, an ink was prepared and evaluated in the same manner as in Example B-5 except that the molecular weight of the polymer fine particles added in Example B-5 was changed to 90000 and 1100000. An emulsion having a molecular weight of 90000 was designated as Emulsion K (EM-K), and an emulsion having a molecular weight of 90000 was designated as Emulsion L (EM-L). The ink composition is shown in Table 8. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example B-5. The results are shown in Table 7. The measurement of the particle diameter of the polymer fine particles was performed in the same manner as in Example B-1.

(Reference Example B-8)
Reference Example B-8 was prepared and evaluated in the same manner as in Example B-6 except that 1,2-hexanediol as 1,2-alkylene glycol was replaced with glycerin in Example B-6. The ink composition is shown in Table 8. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example B-5. The results are shown in Table 7.

(Reference Example B-9)
Reference Example B-9 was prepared and evaluated in the same manner as in Example B-7 except that glycerin was substituted for the acetylene glycol surfactant and acetylene alcohol surfactant in Example B-7. did. The ink composition is shown in Table 8. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example B-5. The results are shown in Table 7.

(Reference Example B-10)
Reference Example B-10 was prepared and evaluated in the same manner as in Example B-8, except that the amount of polymer fine particles added was changed to 80% and 50% in pigment ratio in Example B-8. . The ink composition is shown in Table 8. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example B-5. The results are shown in Table 7.

[Example C]
Example C below corresponds to another preferred embodiment (c).
(Example 1)
(1) Production of Pigment Dispersion C-1 For the pigment dispersion C1, Monarch 880 manufactured by Cabot Corporation of the United States, which is carbon black (Pigment Black 7), was used. The surface of carbon black was oxidized by the same method as in JP-A-8-3498 to make it dispersible in water, thereby preparing dispersion C1. The particle diameter was measured using a Microtrac particle size distribution analyzer UPA250 (manufactured by Nikkiso), and it was 110 nm.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.2 parts of potassium is added, 0.05 parts of sodium lauryl sulfate, 15 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of tetrahydrofurfuryl acrylate, 5 parts of butyl methacrylate and t -A monomer solution containing 0.02 part of dodecyl mercaptan is dropped and reacted at 70 ° C to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 15 parts of 2-ethyl-hexyl acrylate A reaction solution consisting of 10 parts of styrene, 6 parts of butyl acrylate, 5 parts of acrylic acid, and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by neutralization with sodium hydroxide. An aqueous dispersion of polymer fine particles that had been adjusted to pH 8 to 8.5 and filtered through a 0.3 μm filter was prepared as Emulsion A (EM-A). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). When the solvent was measured as THF using gel permeation chromatography (GPC) of L7100 system manufactured by Hitachi, Ltd., the molecular weight in terms of styrene was 150,000. Moreover, the acid value by the titration method was 20 mgKOH / g. The proportion of styrene in the solid content of this emulsion A is 9.3%.

(3) Preparation of inkjet recording ink Table 10 shows examples of compositions suitable for inkjet recording ink. The ink for inkjet recording of the present invention was prepared by using the dispersion C1 prepared by the above method and mixing with the vehicle components shown in Table 10. In addition, 0.05% of the top side 240 (manufactured by Permachem Asia Co., Ltd.) is used for the remaining amount of water in Examples and Comparative Examples of the present invention to prevent ink corrosion, and benzotriazole is used to prevent ink jet head member corrosion. 0.02%, and EDTA (ethylenediaminetetraacetic acid) .2Na salt in an amount of 0.04% was added to ion-exchanged water in order to reduce the influence of metal ions in the ink system.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example C-1 and using PX-V600 manufactured by Seiko Epson Corporation as an ink jet printer, a sample solidly printed on a cotton cloth was created at 150 ° C. Heat for 5 minutes. The sample was subjected to friction fastness by rubbing 100 times with a load of 200 g using a Gakushin type friction fastness tester AB-301S manufactured by Tester Sangyo Co., Ltd. Two levels of dry and wet were evaluated according to Japanese Industrial Standard (JIS) JIS L0849, which confirms the degree of ink peeling. Similarly, the dry cleaning test was evaluated by the method B of JIS L0860. Table 9 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using PX-V600 manufactured by Seiko Epson Corporation as an inkjet printer, MSX Gothic, a standard for character size 11 in Microsoft Word on XeroxP paper A4 size manufactured by Fuji Xerox Co., Ltd. at 35 ° C and 35% atmosphere. Evaluation was performed by printing 100 pages at a rate of 4000 characters / page. AA when there is no printing disorder at all, A when there is printing disorder at A, B at 2 to 3 printing disorder B, C at 4 to 5 printing disorder, 6 or more printing disorder The results are shown in Table 9 where D is D. (Example C-2)

(1) Production of Pigment Dispersion C2 First, Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used as the pigment dispersion C2. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 75 parts of benzyl acrylate, 2 parts of acrylic acid, and 0.3 part of t-dodecyl mercaptan were added and heated to 70 ° C. separately. Disperse polymer while adding 150 parts of benzyl acrylate, 15 parts of acrylic acid, 5 parts of butyl acrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 1 part of sodium persulfate to the reaction vessel over 4 hours. Was subjected to a polymerization reaction. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 40%. A portion of this polymer was taken out and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC, manufactured by Seiko Denshi).

  Further, 40 parts of the dispersion polymer solution, 30 parts of Pigment Blue 15: 3, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 30 parts of methyl ethyl ketone were mixed. Then, using an ultra-high pressure homogenizer (Ultimizer HJP-25005 manufactured by Sugino Machine Co., Ltd.), it was dispersed by passing 15 passes at 200 MPa. Then, it moved to another container, 300 parts of ion-exchange water was added, and also it stirred for 1 hour. And the whole amount of methyl ethyl ketone and a part of water were distilled off using the rotary evaporator, and it neutralized with 0.1 mol / L sodium hydroxide, and adjusted to pH9. Then, it filtered with a 0.3 micrometer membrane filter, adjusted with ion-exchange water, and was set as the pigment dispersion C2 whose pigment concentration is 15%. The particle diameter was measured by the method used in Example C-1 to be 80 nm.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.2 parts of potassium is added, 0.05 parts of sodium lauryl sulfate, 9 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of tetrahydrofurfuryl acrylate, 5 parts of butyl methacrylate and t -A monomer solution containing 0.02 part of dodecyl mercaptan is dropped and reacted at 70 ° C to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 15 parts of 2-ethyl-hexyl acrylate Then, a reaction solution consisting of 10 parts of styrene, 16 parts of butyl acrylate, 5 parts of acrylic acid, and 0.5 part of t-dodecyl mercaptan was added at 70 ° C. with stirring, followed by neutralization with sodium hydroxide. An aqueous dispersion of polymer fine particles that had been adjusted to pH 8 to 8.5 and filtered through a 0.3 μm filter was prepared as Emulsion B (EM-B). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). The molecular weight was measured in the same manner as in Example C-1. Moreover, the acid value by the titration method was 20 mgKOH / g. The proportion of styrene in the solid content of this emulsion B is 9.0%.

(3) Preparation of inkjet recording ink Table 10 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared in the same manner as in Example C-1 by using the dispersion C2 prepared by the above method and mixing with the vehicle components shown in Table 10.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example C-2, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example C-1. Table 9 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example C-2, the ejection stability was measured by the same method and the same evaluation method as in Example C-1. Table 9 shows the measurement results of the discharge stability.

(Example C-3)
(1) Production of Pigment Dispersion C3 First, Pigment Dispersion C3 was prepared in the same manner as Pigment Dispersion C2 using Pigment Violet 19 (Quinacridone Pigment: Clariant) to obtain Pigment Dispersion C3. The particle diameter was measured by the method used in Example C-1 to be 90 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example C-2 were used.

(3) Preparation of inkjet recording ink Table 10 shows examples of compositions suitable for inkjet recording ink. The ink for inkjet recording of the present invention was prepared and evaluated in the same manner as in Example C-1 by using the dispersion C3 prepared by the above method and mixing with the vehicle components shown in Table 10.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example C-3, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example C-1. Table 9 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example C-3, ejection stability was measured by the same method and the same evaluation method as Example C-1. Table 9 shows the measurement results of the discharge stability.

(Example C-4)
(1) Production of Pigment Dispersion C4 First, Pigment Dispersion C4 was prepared in the same manner as Pigment Dispersion C2 using Pigment Yellow 14 (azo pigment: manufactured by Clariant) to obtain Pigment Dispersion C4. The particle diameter was measured by the method used in Example C-1 to be 115 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example C-2 were used.

(3) Preparation of inkjet recording ink Table 10 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example C-1 by using the dispersion C4 produced by the above method and mixing with the vehicle components shown in Table 10.

(4) Abrasion resistance test and dry cleaning property test Using the ink of Example C-4, an abrasion resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example C-1. Table 9 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example C-4, ejection stability was measured by the same method and the same evaluation method as Example C-1. Table 9 shows the measurement results of the discharge stability.

(Comparative Example C-1)
Comparative Example C-1 was the same as Example C-1 except that the total amount of ethyl acrylate (45 parts) was changed to 45 parts of benzyl methacrylate, except that polymer fine particles having a glass transition temperature of 0 ° C. were used. An ink was prepared and evaluated in the same manner as in Example C-1. An emulsion produced using these polymer fine particles was designated as Emulsion C (EM-C). Table 10 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example C-1. The results are shown in Table 9.

(Comparative Example C-2)
Comparative Example C-2 has a glass transition temperature of 10 ° C. in the same manner as in Example C-2 except that the total amount of ethyl acrylate (49 parts) is changed to benzyl methacrylate and 10 parts of butyl acrylate is changed to 10 parts of benzyl methacrylate. An ink was prepared and evaluated in the same manner as in Example C-2 except that the polymer fine particles were used. An emulsion produced using these polymer fine particles was designated as Emulsion D (EM-D). Table 10 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example C-1. The results are shown in Table 9.

(Comparative Example C-3)
Comparative Example C-3 was prepared and evaluated in the same manner as in Example C-3 except that a dispersion having a pigment particle size of 350 nm and 45 nm was prepared in Example C-3. The particle size was measured by the same method as in Example C-1. The dispersion with a particle size of 350 nm was designated as pigment dispersion C3A, and the dispersion with a particle size of 45 nm was designated as pigment dispersion C3B. Table 10 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example C-1. The results are shown in Table 9.

(Comparative Example C-4)
Comparative Example C-4 was prepared and evaluated in the same manner as in Example C-4 except that the acid value of the polymer fine particles to be added was changed to 120 mgKOH / g and 150 mgKOH / g in Example C-4. An emulsion prepared using polymer fine particles having an acid value of 120 mgKOH / g is called Emulsion E (EM-E), and an emulsion prepared using polymer fine particles having an acid value of 120 mgKOH / g is Emulsion F (EM-F). It was. Table 10 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example C-1. The results are shown in Table 9.

(Reference Example C-5)
In Reference Example C-5, the total amount of ethyl acrylate and a part of butyl acrylate were replaced with 30 parts of styrene, and the total amount of butyl methacrylate and a part of methyl acrylate were replaced with 2-ethyl-hexyl acrylate in Example C-2. Then, an ink was prepared and evaluated in the same manner as in Example C-2 except that the addition amount was adjusted so that the glass transition temperature was −17 ° C. An emulsion produced using these polymer fine particles was designated as Emulsion G (EM-G). Table 10 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example C-1. The results are shown in Table 9. The proportion of styrene in the solid content of this emulsion G is 36.0%.

(Reference Example C-6)
In Reference Example C-6, in Example C-2, 10 parts of styrene was replaced with 5 parts of styrene and 5 parts of methyl methacrylate, and a part of butyl acrylate was also replaced with ethyl acrylate, so that the glass transition temperature was −17 ° C. An ink was prepared and evaluated in the same manner as in Example C-2 except that the amount added was adjusted. An emulsion produced using these polymer fine particles was designated as Emulsion H (EM-H). Table 10 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example C-1. The results are shown in Table 9. The proportion of styrene in the solid content of this emulsion H is 4.5%.

(Example C-5)
(1) Production of Pigment Dispersion C5 The pigment dispersion C5 used was MA100 manufactured by Mitsubishi Chemical Corporation, which is carbon black (PBk7). The surface of carbon black was oxidized by the same method as in JP-A-8-3498 to make it dispersible in water, thereby preparing dispersion C5. The particle diameter was measured by the method used in Example C-1 to be 120 nm.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.3 parts of potassium has been added, 0.05 parts of sodium lauryl sulfate, 20 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of lauryl acrylate, 5 parts of butyl methacrylate and t-dodecyl in 7 parts of ion-exchanged water A monomer solution containing 0.02 part of mercaptan is dropped and reacted at 70 ° C. to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 15 parts of 2-ethyl-hexyl acrylate A reaction solution consisting of 10 parts of styrene, 16 parts of lauryl acrylate, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by neutralization with sodium hydroxide. An aqueous dispersion of polymer fine particles that had been adjusted to pH 8 to 8.5 and filtered through a 0.3 μm filter was prepared as Emulsion I (EM-I). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured with a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). The molecular weight was measured by the same method as in Example C-1. Moreover, the acid value by the titration method was 18 mgKOH / g. The proportion of styrene in the solid content of this emulsion I is 8.2%.

(3) Preparation of inkjet recording ink Table 12 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example C-1 by using the dispersion C5 prepared by the above method and mixing with the vehicle components shown in Table 12.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example C-5, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example C-1. Table 11 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example C-5, ejection stability was measured by the same method and the same evaluation method as Example C-1. Table 11 shows the measurement results of the discharge stability.

(Example C6)
(1) Production of Pigment Dispersion C6 First, Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used as Pigment Dispersion C6. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was replaced with nitrogen, and then 45 parts of styrene, 30 parts of polyethylene glycol 400 acrylate, 10 parts of benzyl acrylate, 2 parts of acrylic acid, 0.3 part of t-dodecyl mercaptan And heated to 70 ° C., and separately prepared 150 parts of styrene, 100 parts of polyethylene glycol 400 acrylate, 15 parts of acrylic acid, 5 parts of butyl acrylate, 1 part of t-dodecyl mercaptan and 5 parts of sodium persulfate are placed in a dropping funnel. Then, the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, water was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 40%. A part of this polymer was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi), and it was 45 ° C.

  Further, 40 parts of the above dispersion polymer solution and 30 parts of Pigment Blue 15: 3 and 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution are mixed and dispersed using an Eiger mill using zirconia beads for 2 hours. Then, it transfers to another container, 300 parts of ion-exchange water is added, and also it stirs for 1 hour. And it neutralizes with 0.1 mol / L sodium hydroxide and adjusts to pH9. Then, it filtered with a 0.3 micrometer membrane filter, and was set as the dispersion C6 whose solid content (dispersion polymer and pigment blue 15: 3) is 20%. The particle diameter was measured by the method used in Example C-1 to be 100 nm. The molecular weight was measured by the same method as in Example C-1.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.3 parts of potassium is added, 0.05 parts of sodium lauryl sulfate, 10 parts of ethyl acrylate, 25 parts of butyl acrylate, 6 parts of lauryl acrylate, 5 parts of butyl methacrylate and t-dodecyl are added to 7 parts of ion-exchanged water. A monomer solution containing 0.02 part of mercaptan is dropped and reacted at 70 ° C. to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 20 parts of ethyl acrylate, 15 parts of 2-ethyl-hexyl acrylate A reaction solution consisting of 10 parts of styrene, 15 parts of lauryl acrylate, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by neutralization with sodium hydroxide. An aqueous dispersion of polymer fine particles that had been adjusted to pH 8 to 8.5 and filtered through a 0.3 μm filter was prepared as Emulsion J (EM-J). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured with a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). Moreover, the acid value by the titration method was 18 mgKOH / g. The proportion of styrene in the solid content of this emulsion J is 9.0%.

(3) Preparation of inkjet recording ink Table 12 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example C-1 by using the dispersion C6 prepared by the above method and mixing with the vehicle components shown in Table 12.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example C-6, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example C-1. Table 11 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example C-6, ejection stability was measured by the same method and the same evaluation method as in Example C-1. Table 11 shows the measurement results of the discharge stability.

(Example C-7)
(1) Production of Pigment Dispersion C7 First, Pigment Dispersion C7 was prepared in the same manner as Pigment Dispersion C2 using Pigment Red 122 (Dimethylquinacridone Pigment: Clariant). The particle diameter was measured by the method used in Example C-1 to be 80 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example C-6 were used.

(3) Preparation of inkjet recording ink Table 12 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example C-1 by using the dispersion C7 prepared by the above method and mixing with the vehicle components shown in Table 12.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example C-7, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example C-1. Table 11 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example C-7, ejection stability was measured by the same method and the same evaluation method as Example C-1. Table 11 shows the measurement results of the discharge stability.

(Example C-8)
(1) Production of Pigment Dispersion C8 First, Pigment Dispersion C8 was prepared in the same manner as Pigment Dispersion C2 using Pigment Yellow 180 (Benzimidazolone Disazo Pigment: Clariant). The particle diameter was measured by the method used in Example C-1 to be 130 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example C-6 were used.

(3) Preparation of inkjet recording ink Table 12 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example C-1 by using the dispersion C8 prepared by the above method and mixing with the vehicle components shown in Table 12.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example C-8, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example C-1. Table 11 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example C-8, ejection stability was measured by the same method and the same evaluation method as in Example C-1. Table 11 shows the measurement results of the discharge stability.

(Reference Example C-7)
Reference Example C-7 was prepared and evaluated in the same manner as in Example C-5, except that the molecular weight of the polymer fine particles added in Example C-5 was changed to 90000 and 1100000. An emulsion having a molecular weight of 90000 was designated as Emulsion K (EM-K), and an emulsion having a molecular weight of 90000 was designated as Emulsion L (EM-L). The ink composition is shown in Table 12. The rubbing resistance test, dry cleaning test and ejection stability test were conducted in the same manner as in Example C-5. The results are shown in Table 11. The measurement of the particle diameter of the polymer fine particles was performed in the same manner as in Example C-1.

(Reference Example C-8)
Reference Example C-8 was prepared and evaluated in the same manner as in Example C-6 except that 1,2-hexanediol as 1,2-alkylene glycol was replaced with glycerin in Example C-6. The ink composition is shown in Table 12. The rubbing resistance test, dry cleaning test and ejection stability test were conducted in the same manner as in Example C-5. The results are shown in Table 11.

(Reference Example C-9)
Reference Example C-9 was prepared and evaluated in the same manner as in Example C-7, except that in Example C-7, the acetylene glycol surfactant and the acetylene alcohol surfactant were replaced with glycerin. did. The ink composition is shown in Table 12. The rubbing resistance test, dry cleaning test and ejection stability test were conducted in the same manner as in Example C-5. The results are shown in Table 11.

(Reference Example C-10)
Reference Example C-10 was prepared and evaluated in the same manner as in Example C-8 except that the amount of polymer fine particles added was changed to 80% and 50% in pigment ratio in Example C-8. . The ink composition is shown in Table 12. The rubbing resistance test, dry cleaning test and ejection stability test were conducted in the same manner as in Example C-5. The results are shown in Table 11.

[Example D]
Example D below corresponds to other preferred embodiment (d).
(Example D-1)
(1) Production of Pigment Dispersion D1 As the pigment dispersion D1, Monarch 880 manufactured by Cabot Corporation of the United States, which is carbon black (Pigment Black 7), was used. The surface of carbon black was oxidized by the same method as in JP-A-8-3498 to make it dispersible in water, thereby preparing dispersion D1. The particle diameter was measured using a Microtrac particle size distribution analyzer UPA250 (manufactured by Nikkiso), and it was 110 nm.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.2 parts of potassium is added, 0.05 parts of sodium lauryl sulfate, 4 parts of glycidoxy acrylate, 15 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of tetrahydrofurfuryl acrylate in 7 parts of ion-exchanged water Then, a monomer solution containing 5 parts of butyl methacrylate and 0.02 part of t-dodecyl mercaptan is dropped at 70 ° C. and reacted to prepare a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 25 parts of methyl acrylate, 6 parts of butyl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared and designated as Emulsion A (EM-A). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). When the solvent was measured as THF using gel permeation chromatography (GPC) of L7100 system manufactured by Hitachi, Ltd., the molecular weight in terms of styrene was 150,000. The acid value was 20 mgKOH / g. The acid value was measured by the following method. It collects in the state before sodium hydroxide neutralization of the said polymer fine particle aqueous dispersion, The solid content density | concentration is correctly measured with a thermobalance (TG-2121 by Seiko Electronic Industry). Next, about 10 g of this polymer fine particle aqueous dispersion is accurately weighed, put into a stoppered Erlenmeyer flask, and 100 ml of 2-propanol-tetrahydrofuran mixture (1: 2) is added and dissolved. As an indicator, and titrating with a 0.1 mol / L 2-propanol potassium hydroxide solution until a pale red color lasting 30 seconds is obtained. The acid value is determined by the formula (1).

Acid value (mgKOH / g) = (5.611 × a × f) / S (1)
S: Sample collection amount (g)
a: Consumption of 0.1 mol / L 2-propanol potassium hydroxide solution (ml)
f: Factor of 0.1 mol / L 2-propanol potassium hydroxide solution where a is the titration value (ml) -blank value (ml)

  As the polyalkylene wax, Nopcoat PEM-17 (polyalkylene wax manufactured by San Nopco Co., Ltd.) was used. The melting point is 103 ° C.

(3) Preparation of inkjet recording ink Table 14 shows the composition of the inkjet recording ink. The ink for inkjet recording of the present invention was prepared by using the dispersion D1 prepared by the above method and mixing with the vehicle components shown in Table 14. In addition, 0.05% of the top side 240 (manufactured by Permachem Asia Co., Ltd.) is used for the remaining amount of water in Examples and Comparative Examples of the present invention to prevent ink corrosion, and benzotriazole is used to prevent ink jet head member corrosion. 0.02%, and EDTA (ethylenediaminetetraacetic acid) .2Na salt in an amount of 0.04% was added to ion-exchanged water in order to reduce the influence of metal ions in the ink system.

(4) Abrasion resistance test and dry cleaning property test Using the ink of Example D-1, a sample printed solid on cotton using PX-V600 manufactured by Seiko Epson Corporation as an inkjet printer is prepared. The sample was subjected to friction fastness by rubbing 100 times with a load of 200 g using a Gakushin type friction fastness tester AB-301S manufactured by Tester Sangyo Co., Ltd. Two levels of dry and wet were evaluated according to Japanese Industrial Standard (JIS) JIS L0849, which confirms the degree of ink peeling. Similarly, the dry cleaning test was evaluated by the method B of JIS L0860. Table 13 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using PX-V600 manufactured by Seiko Epson Corporation as an inkjet printer, MSX Gothic, a standard for character size 11 in Microsoft Word on XeroxP paper A4 size manufactured by Fuji Xerox Co., Ltd. at 35 ° C and 35% atmosphere. Evaluation was performed by printing 100 pages at a rate of 4000 characters / page. AA when there is no printing disorder at all, A with printing disorder at one place, B with printing disorder at 2-3 places, C at 4-5 printing disorders, and 6 or more printing disorders The results are shown in Table 13 with D as the result.

(Example D-2)
(1) Production of Pigment Dispersion D2 First, Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used as the pigment dispersion D2. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 75 parts of benzyl acrylate, 2 parts of acrylic acid, and 0.3 part of t-dodecyl mercaptan were added and heated to 70 ° C. separately. Disperse polymer while adding 150 parts of benzyl acrylate, 15 parts of acrylic acid, 5 parts of butyl acrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 1 part of sodium persulfate to the reaction vessel over 4 hours. Was subjected to a polymerization reaction. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 40%. A portion of this polymer was taken out and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC, manufactured by Seiko Denshi).

  Further, 40 parts of the dispersion polymer solution, 30 parts of Pigment Blue 15: 3, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 30 parts of methyl ethyl ketone were mixed. Then, using an ultra-high pressure homogenizer (Ultimizer HJP-25005 manufactured by Sugino Machine Co., Ltd.), it was dispersed by passing 15 passes at 200 MPa. Then, it moved to another container, 300 parts of ion-exchange water was added, and also it stirred for 1 hour. And the whole amount of methyl ethyl ketone and a part of water were distilled off using the rotary evaporator, and it neutralized with 0.1 mol / L sodium hydroxide, and adjusted to pH9. Then, it filtered with a 0.3 micrometer membrane filter, adjusted with ion-exchange water, and was set as the pigment dispersion D2 whose pigment concentration is 15%. The particle diameter was measured by the method used in Example D-1 to be 80 nm.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.2 parts of potassium have been added, 0.05 parts of sodium lauryl sulfate, 19 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of tetrahydrofurfuryl acrylate, 5 parts of butyl methacrylate and t -A monomer solution containing 0.02 part of dodecyl mercaptan is dropped and reacted at 70 ° C to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 25 parts of methyl acrylate, 16 parts of butyl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared to obtain Emulsion B (EM-B). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). The molecular weight was measured in the same manner as in Example D-1. The acid value was 20 mgKOH / g. The acid value was measured by the same method as in Example D-1. Moreover, Mitsui High Wax 2203A (polyalkylene wax manufactured by Mitsui Chemicals, Inc.) was used as the polyalkylene wax. The melting point is 117 ° C.

(3) Preparation of inkjet recording ink Table 14 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared in the same manner as Example D-1 by using the dispersion D2 prepared by the above method and mixing with the vehicle components shown in Table 14.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example D-2, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example D-1. Table 13 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example D-2, the ejection stability was measured by the same method and the same evaluation method as Example D-1. Table 13 shows the measurement results of the discharge stability.

(Example D-3)
(1) Production of Pigment Dispersion D3 First, Pigment Dispersion D3 was prepared in the same manner as Pigment Dispersion D2 using Pigment Violet 19 (Quinacridone Pigment: manufactured by Clariant) to obtain Pigment Dispersion D3. The particle diameter was measured by the method used in Example D-1 to be 90 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example D-2 were used.

(3) Preparation of inkjet recording ink Table 14 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example D-1 by using the dispersion D3 prepared by the above method and mixing with the vehicle components shown in Table 14.

(4) Abrasion resistance test and dry cleaning property test Using the ink of Example D-3, an abrasion resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example D-1. Table 13 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example D-3, the ejection stability was measured by the same method and the same evaluation method as Example D-1. Table 13 shows the measurement results of the discharge stability.

(Example D-4)
(1) Production of Pigment Dispersion D4 First, Pigment Dispersion D4 was prepared in the same manner as Pigment Dispersion D2 using Pigment Yellow 14 (azo pigment: manufactured by Clariant) to obtain Pigment Dispersion D4. The particle diameter was measured by the method used in Example D-1 to be 115 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example D-2 were used.

(3) Preparation of inkjet recording ink Table 14 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example D-1 by using the dispersion D4 produced by the above method and mixing with the vehicle components shown in Table 14.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example D-4, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example D-1. Table 13 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example D-4, the ejection stability was measured by the same method and the same evaluation method as Example D-1. Table 13 shows the measurement results of the discharge stability.

(Comparative Example D-1)
Comparative Example D-1 was carried out in the same manner as in Example D-1, except that a part of ethyl acrylate was changed to styrene, and polymer fine particles having a glass transition temperature of 0 ° C. were used, and polyethylene wax was not added. An ink was prepared and evaluated in the same manner as in Example D-1. An emulsion prepared using the polymer fine particles was named Emulsion B (EM-B). The ink composition is shown in Table 14. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example D-1. The results are shown in Table 13.

(Comparative Example D-2)
Comparative Example D-2 was the same as Example D-2 except that a part of ethyl acrylate and butyl acrylate was changed to styrene, and polymer fine particles having a glass transition temperature of 10 ° C. were used, except that no polyethylene wax was added. Were prepared and evaluated in the same manner as in Example D-2. An emulsion produced using these polymer fine particles was designated as Emulsion C (EM-C). The ink composition is shown in Table 14. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example D-1. The results are shown in Table 13.

(Comparative Example D-3)
Comparative Example D-3 was prepared in the same manner as in Example D-3 except that a dispersion having pigment particle sizes of 350 nm and 45 nm was prepared in Example D-3, and polyethylene wax was not added. evaluated. The particle size was measured by the same method as in Example D-1. The dispersion with a particle size of 350 nm was designated as pigment dispersion D3A, and the dispersion with a particle size of 45 nm was designated as pigment dispersion D3B. The ink composition is shown in Table 14. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example D-1. The results are shown in Table 13.

(Comparative Example D-4)
Comparative Example D-4 was the same as Example D-4 except that the acid value of the polymer fine particles to be added was 120 mgKOH / g and 150 mgKOH / g, and no polyethylene wax was added. And evaluated. An emulsion prepared using polymer fine particles having an acid value of 120 mgKOH / g is referred to as emulsion D (EM-D), and an emulsion prepared using polymer fine particles having an acid value of 120 mgKOH / g is emulsion E (EM-E). It was. The ink composition is shown in Table 14. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example D-1. The results are shown in Table 13.

(Example D-5)
(1) Production of Pigment Dispersion D5 As the pigment dispersion D5, MA100 manufactured by Mitsubishi Chemical Corporation, which is carbon black (PBk7), was used. The surface of carbon black was oxidized by the same method as in JP-A-8-3498 to make it dispersible in water, thereby preparing dispersion D5. The particle diameter was measured by the method used in Example D-1 to be 120 nm.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.3 parts of potassium has been added, 0.05 parts of sodium lauryl sulfate, 20 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of lauryl acrylate, 5 parts of butyl methacrylate and t-dodecyl in 7 parts of ion-exchanged water A monomer solution containing 0.02 part of mercaptan is dropped and reacted at 70 ° C. to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 25 parts of butyl acrylate, 16 parts of lauryl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared to obtain an emulsion G (EM-G). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured with a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). The molecular weight was measured by the same method as in Example D-1. The acid value was 18 mgKOH / g. The acid value was measured by the same method as in Example D-1.

(3) Preparation of inkjet recording ink Table 16 shows examples of compositions suitable for inkjet recording ink. The ink for inkjet recording of the present invention was prepared and evaluated in the same manner as in Example D-1 by using the dispersion D5 prepared by the above method and mixing with the vehicle components shown in Table 16.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example D-5, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example D-1. Table 15 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example D-5, ejection stability was measured by the same method and the same evaluation method as Example D-1. Table 15 shows the measurement results of the discharge stability.

(Example D-6)
(1) Production of Pigment Dispersion D6 First, Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used as the pigment dispersion D6. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was replaced with nitrogen, and then 45 parts of styrene, 30 parts of polyethylene glycol 400 acrylate, 10 parts of benzyl acrylate, 2 parts of acrylic acid, 0.3 part of t-dodecyl mercaptan And heated to 70 ° C., and separately prepared 150 parts of styrene, 100 parts of polyethylene glycol 400 acrylate, 15 parts of acrylic acid, 5 parts of butyl acrylate, 1 part of t-dodecyl mercaptan and 5 parts of sodium persulfate are placed in a dropping funnel. Then, the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, water was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 40%. A part of this polymer was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi), and it was 45 ° C.

  Further, 40 parts of the above dispersion polymer solution and 30 parts of Pigment Blue 15: 3 and 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution are mixed and dispersed using an Eiger mill using zirconia beads for 2 hours. Then, it transfers to another container, 300 parts of ion-exchange water is added, and also it stirs for 1 hour. And it neutralizes with 0.1 mol / L sodium hydroxide and adjusts to pH9. Then, it filtered with a 0.3 micrometer membrane filter, and was set as the dispersion D6 whose solid content (dispersion polymer and pigment blue 15: 3) is 20%. The particle diameter was measured by the method used in Example D-1 to be 100 nm. It was 210000 when the molecular weight was measured by the same method as Example D-1.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.3 parts of potassium is added, 0.05 parts of sodium lauryl sulfate, 20 parts of ethyl acrylate, 25 parts of butyl acrylate, 6 parts of lauryl acrylate, 5 parts of butyl methacrylate and t-dodecyl are added to 7 parts of ion-exchanged water. A monomer solution containing 0.02 part of mercaptan is dropped and reacted at 70 ° C. to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 20 parts of ethyl acrylate, 20 parts of butyl acrylate, 20 parts of lauryl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared to obtain Emulsion F (EM-F). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured with a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). It was 200000 when the molecular weight was measured by the same method as Example D-1. The acid value was 18 mgKOH / g. The acid value was measured by the same method as in Example D-1.

(3) Preparation of inkjet recording ink Table 16 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example D-1 by using the dispersion D6 prepared by the above method and mixing with the vehicle components shown in Table 16.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example D-6, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example D-1. Table 15 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example D-6, the ejection stability was measured by the same method and the same evaluation method as Example D-1. Table 15 shows the measurement results of the discharge stability.

(Example D-7)
(1) Production of Pigment Dispersion D7 First, Pigment Dispersion D7 was prepared in the same manner as Pigment Dispersion D2 using Pigment Red 122 (Dimethylquinacridone Pigment: Clariant). The particle diameter was measured by the method used in Example D-1 to be 80 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example D-6 were used.

(3) Preparation of inkjet recording ink Table 16 shows examples of compositions suitable for inkjet recording ink. The ink for inkjet recording of the present invention was prepared and evaluated in the same manner as in Example D-1 by using the dispersion D7 prepared by the above method and mixing with the vehicle components shown in Table 16.

(4) Abrasion resistance test and dry cleaning property test Using the ink of Example D7, an abrasion resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example D-1. Table 15 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example D-7, ejection stability was measured by the same method and the same evaluation method as Example D-1. Table 15 shows the measurement results of the discharge stability.

(Example D-8)
(1) Production of Pigment Dispersion D8 First, Pigment Dispersion D8 was prepared in the same manner as Pigment Dispersion D2 using Pigment Yellow 180 (Benzimidazolone Disazo Pigment: Clariant). The particle diameter was measured by the method used in Example D-1 to be 130 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example D-6 were used.

(3) Preparation of inkjet recording ink Table 16 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example D-1, using the dispersion D8 prepared by the above method and mixing with the vehicle components shown in Table 16.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example D-8, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example D-1. Table 15 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability The ejection stability was measured by the same method and the same evaluation method as in Example 1 using the ink of Example D-8. Table 15 shows the measurement results of the discharge stability.

(Reference Example D-5)
In Reference Example D-5, ink was prepared and evaluated in the same manner as in Example D-5 except that the molecular weight of the polymer fine particles added in Example D-5 was 90000 and 1100000, and polyethylene wax was not added. An emulsion having a molecular weight of 90000 was designated as Emulsion H (EM-H), and an emulsion having a molecular weight of 90000 was designated as Emulsion I (EM-I). The ink composition is shown in Table 16. The rubbing resistance test, dry cleaning test and ejection stability test were performed in the same manner as in Example 5. The results are shown in Table 15. The measurement of the particle diameter of the polymer fine particles was performed in the same manner as in Example D-1.

(Reference Example D-6)
Reference Example D-6 is the same as Example D-6 except that 1,2-hexanediol as 1,2-alkylene glycol was replaced with glycerin and polyethylene wax was not added. Fabricated and evaluated. The ink composition is shown in Table 16. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example D-5. The results are shown in Table 15.

(Reference Example D-7)
Reference Example D-7 is the same as Example D-7 except that acetylene glycol-based surfactant and acetylene alcohol-based surfactant are replaced with glycerin and polyethylene wax is not added in Example D-7. An ink was prepared and evaluated. The ink composition is shown in Table 16. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example D-5. The results are shown in Table 15.

(Reference Example D-8)
Reference Example D-8 was the same as Example D-8 except that the amount of polymer fine particles added was 80% and 50% in terms of pigment ratio, and polyethylene wax was not added. Fabricated and evaluated. The ink composition is shown in Table 16. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example D-5. The results are shown in Table 15.

(Reference Example D-9)
Reference Example D-9 was evaluated by preparing two levels of ink in the same manner as in Example D-2 except that a commercially available melting point of 43 ° C. (wax A) and 68 ° C. (wax B) was added. The results are shown in Table 15.

[Example E]
Example E below corresponds to another preferred embodiment (e).
(Example 1)
(1) Production of Pigment Dispersion E-1 Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used as the pigment dispersion E1. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 75 parts of benzyl acrylate, 2 parts of acrylic acid, and 0.3 part of t-dodecyl mercaptan were added and heated to 70 ° C. separately. Disperse polymer while adding 150 parts of benzyl acrylate, 15 parts of acrylic acid, 5 parts of butyl acrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 1 part of sodium persulfate to the reaction vessel over 4 hours. Was subjected to a polymerization reaction. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 40%. A portion of this polymer was taken out and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC, manufactured by Seiko Denshi).

  Further, 40 parts of the dispersion polymer solution, 30 parts of Pigment Blue 15: 3, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 30 parts of methyl ethyl ketone were mixed. Then, using an ultra-high pressure homogenizer (Ultimizer HJP-25005 manufactured by Sugino Machine Co., Ltd.), it was dispersed by passing 15 passes at 200 MPa. Then, it moved to another container, 300 parts of ion-exchange water was added, and also it stirred for 1 hour. And the whole amount of methyl ethyl ketone and a part of water were distilled off using the rotary evaporator, and it neutralized with 0.1 mol / L sodium hydroxide, and adjusted to pH9. Thereafter, it was filtered through a 0.3 μm membrane filter and adjusted with ion exchange water to obtain a pigment dispersion E1 having a pigment concentration of 15%. It was 80 nm when the particle size was measured using a Microtrac particle size distribution analyzer UPA250 (manufactured by Nikkiso).

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.2 parts of potassium have been added, 0.05 parts of sodium lauryl sulfate, 19 parts of ethyl acrylate, 15 parts of butyl acrylate, 6 parts of tetrahydrofurfuryl acrylate, 5 parts of butyl methacrylate and t -A monomer solution containing 0.02 part of dodecyl mercaptan is dropped and reacted at 70 ° C to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 25 parts of methyl acrylate, 16 parts of butyl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared to obtain Emulsion A (EM-A). A portion of this aqueous polymer fine particle dispersion was taken and dried, and the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). When the solvent was measured as THF using gel permeation chromatography (GPC) of L7100 system manufactured by Hitachi, Ltd., the molecular weight in terms of styrene was 200000.

(3) Preparation of Inkjet Recording Ink Table 18 shows examples of compositions suitable for inkjet recording ink. The ink for inkjet recording of the present invention was prepared by using the dispersion E1 prepared by the above method and mixing with the vehicle components shown in Table 18. In addition, 0.05% of the top side 240 (manufactured by Permachem Asia Co., Ltd.) is used for the remaining amount of water in Examples and Comparative Examples of the present invention to prevent ink corrosion, and benzotriazole is used to prevent ink jet head member corrosion. 0.02%, and EDTA (ethylenediaminetetraacetic acid) .2Na salt in an amount of 0.04% was added to ion-exchanged water in order to reduce the influence of metal ions in the ink system.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example E-1, a sample printed solid on cotton is created using PX-V630 manufactured by Seiko Epson Corporation as an ink jet printer. The sample was subjected to friction fastness by rubbing 100 times with a load of 200 g using a Gakushin type friction fastness tester AB-301S manufactured by Tester Sangyo Co., Ltd. Two levels of dry and wet were evaluated according to Japanese Industrial Standard (JIS) JIS L0849, which confirms the degree of ink peeling. Similarly, the dry cleaning test was evaluated by the method B of JIS L0860. Table 17 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example E-1 and using PX-V630 manufactured by Seiko Epson Corporation as an inkjet printer, Microsoft Word on XeroxP paper A4 size manufactured by Fuji Xerox Co., Ltd. at 35 ° C. and 35% atmosphere. Evaluation was performed by printing 100 pages at a rate of 4000 characters / page with a standard of character size 11 and MSP Gothic. AA when there is no printing disorder at all, A with printing disorder at one place, B with printing disorder at 2-3 places, C at 4-5 printing disorders, and 6 or more printing disorders The results are shown in Table 17 with D as the result.

(Example E-2)
(1) Production of Pigment Dispersion E2 First, Pigment Dispersion E2 was prepared in the same manner as Pigment Dispersion E1 using Pigment Violet 19 (Quinacridone Pigment: manufactured by Clariant) to obtain Pigment Dispersion E2. The particle diameter was measured by the method used in Example E-1 to be 90 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example E-1 were used.

(3) Preparation of Inkjet Recording Ink Table 18 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example E-1 by using the dispersion E2 prepared by the above method and mixing with the vehicle components shown in Table 18.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example E-2, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example E-1. Table 18 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example E-2, ejection stability was measured by the same method and the same evaluation method as Example E-1. Table 17 shows the measurement results of the discharge stability.

(Example E-3)
(1) Production of Pigment Dispersion E3 First, Pigment Dispersion E3 was prepared in the same manner as Pigment Dispersion E1 using Pigment Yellow 14 (azo pigment: manufactured by Clariant) to obtain Pigment Dispersion E3. The particle diameter was measured by the method used in Example E-1 to be 115 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example E-1 were used.

(3) Preparation of Inkjet Recording Ink Table 18 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example E-1 by using the dispersion E3 produced by the above method and mixing with the vehicle components shown in Table 18.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example E-3, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example E-1. Table 17 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example E-3, ejection stability was measured by the same method and the same evaluation method as Example E-1. Table 17 shows the measurement results of the discharge stability.

(Comparative Example E-1)
Comparative Example E-1 was the same as Example E-1 except that a part of ethyl acrylate was changed to styrene in Example E-1, and polymer fine particles having a glass transition temperature of −10 ° C. were used. Ink was prepared and evaluated in the same manner as described above. An emulsion prepared using the polymer fine particles was named Emulsion B (EM-B). Table 18 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example E-1. The results are shown in Table 17.

(Comparative Example E-2)
Comparative Example E-2 was prepared and evaluated in the same manner as in Example E-2 except that a dispersion having a pigment particle size of 350 nm was prepared in Example E-2. The particle size was measured by the same method as in Example E-1. A dispersion having a particle size of 350 nm was designated as pigment dispersion E2A. Table 18 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example E-1. The results are shown in Table 17.

(Comparative Example E-3)
In Comparative Example E-3, an ink was prepared and evaluated in the same manner as in Example E-3 except that the acid value of the polymer fine particles to be added was changed to 120 mgKOH / g and 150 mgKOH / g. An emulsion prepared using polymer fine particles having an acid value of 120 mgKOH / g was designated as Emulsion C (EM-C), and an emulsion prepared using polymer fine particles having an acid value of 150 mgKOH / g was designated as Emulsion D (EM- D). Table 18 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example E-1. The results are shown in Table 17.

(Example E-4)
(1) Production of Pigment Dispersion E4 First, Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used as the pigment dispersion E4. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was replaced with nitrogen, and then 80 parts of benzyl acrylate, 5 parts of methacrylic acid, 2 parts of acrylic acid, and 0.3 part of t-dodecyl mercaptan were added to 70 ° C. Heat and separately prepare 150 parts of benzyl acrylate, 15 parts of methacrylic acid, 5 parts of acrylic acid, 1 part of t-dodecyl mercaptan and 5 parts of sodium persulfate in a dropping funnel while dropping into the reaction vessel over 4 hours. The polymer was polymerized. Next, water was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 40%. A part of this polymer was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi), and it was 45 ° C.

  Also, 40 parts of the above dispersion polymer solution, 30 parts of Pigment Blue 15: 3 (copper phthalocyanine pigment: Clariant) and 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution are mixed, and an Eiger mill using zirconia beads is used. Disperse over 2 hours. Then, it transfers to another container, 300 parts of ion-exchange water is added, and also it stirs for 1 hour. And it neutralizes with 0.1 mol / L sodium hydroxide and adjusts to pH9. Then, it filtered with a 0.3 micrometer membrane filter, and set it as the dispersion E4 whose solid content (dispersion polymer and pigment) is 20%. The particle diameter was measured by the method used in Example E-1 to be 100 nm. It was 210,000 when the molecular weight was measured by the same method as Example E-1.

(2) Preparation of polymer fine particles A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.3 parts of potassium is added, 0.05 parts of sodium lauryl sulfate, 20 parts of ethyl acrylate, 25 parts of butyl acrylate, 6 parts of lauryl acrylate, 5 parts of butyl methacrylate and t-dodecyl are added to 7 parts of ion-exchanged water. A monomer solution containing 0.02 part of mercaptan is dropped and reacted at 70 ° C. to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 20 parts of ethyl acrylate, 20 parts of butyl acrylate, 20 parts of lauryl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. An aqueous dispersion of polymer fine particles filtered through a 3 μm filter was prepared and used as Emulsion E (EM-E). A portion of this polymer fine particle aqueous dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC, manufactured by Seiko Denshi).

(3) Preparation of inkjet recording ink Table 20 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example E-1 by using the dispersion E4 prepared by the above method and mixing it with the vehicle components shown in Table 20.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example E-4, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example E-1. Table 19 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example E-4, the ejection stability was measured by the same method and the same evaluation method as Example E-1. Table 19 shows the measurement results of the discharge stability.

(Example E-5)
(1) Production of Pigment Dispersion E5 First, Pigment Dispersion E5 was prepared in the same manner as Pigment Dispersion E4 using Pigment Red 122 (Dimethylquinacridone Pigment: Clariant). The particle diameter was measured by the method used in Example E-1 to be 80 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example E-4 were used.

(3) Preparation of inkjet recording ink Table 20 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example E-1 by using the dispersion E5 prepared by the above method and mixing with the vehicle components shown in Table 20.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example E-5, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example E-1. Table 19 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example E-5, the ejection stability was measured by the same method and the same evaluation method as Example E-1. Table 19 shows the measurement results of the discharge stability.

(Example E-6)
(1) Production of Pigment Dispersion E6 First, Pigment Dispersion E6 was produced in the same manner as Pigment Dispersion E4 using Pigment Yellow 180 (Benzimidazolone Disazo Pigment: Clariant). The particle diameter was measured by the method used in Example E-1 to be 130 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example E-4 were used.

(3) Preparation of inkjet recording ink Table 20 shows examples of compositions suitable for inkjet recording ink. The inkjet recording ink of the present invention was prepared and evaluated in the same manner as in Example E-1 by using the dispersion E6 prepared by the above method and mixing with the vehicle components shown in Table 20.

(4) Scratch resistance test and dry cleaning property test Using the ink of Example E-6, a scratch resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example E-1. Table 19 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Example E-6, ejection stability was measured by the same method and the same evaluation method as Example E-1. Table 19 shows the measurement results of the discharge stability.

(Reference Example E-4)
(1) Production of Pigment Dispersion E7 Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used as the pigment dispersion E7. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was replaced with nitrogen, and then 45 parts of styrene, 30 parts of polyethylene glycol 400 acrylate, 10 parts of benzyl acrylate, 2 parts of acrylic acid, 0.3 part of t-dodecyl mercaptan And heated to 70 ° C., and separately prepared 150 parts of styrene, 100 parts of polyethylene glycol 400 acrylate, 15 parts of acrylic acid, 5 parts of butyl acrylate, 1 part of t-dodecyl mercaptan and 5 parts of sodium persulfate are placed in a dropping funnel. Then, the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, water was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 40%.

  Also, 40 parts of the above dispersion polymer solution, 30 parts of Pigment Blue 15: 3 (copper phthalocyanine pigment: Clariant) and 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution are mixed, and an Eiger mill using zirconia beads is used. Disperse over 2 hours. Then, it transfers to another container, 300 parts of ion-exchange water is added, and also it stirs for 1 hour. And it neutralizes with 0.1 mol / L sodium hydroxide and adjusts to pH9. Then, it filtered with a 0.3 micrometer membrane filter, and was set as the dispersion E7 whose solid content (dispersion polymer and pigment) is 20%. The particle diameter was measured by the method used in Example E-1 to be 100 nm.

(2) Production of polymer fine particles The same polymer fine particles as in Example E-4 were used.

(3) Preparation of Ink for Inkjet Recording Using Dispersion E7 produced by the method described above, mixing with the vehicle components shown in Table 20 produced and evaluated in the same manner as Example E-1.

(4) Abrasion resistance test and dry cleaning property test Using the ink of Reference Example E-4, an abrasion resistance test and a dry cleaning property test were performed by the same method and the same evaluation method as Example E-1. Table 19 shows the results of the abrasion resistance test and the dry cleaning test.

(5) Measurement of ejection stability Using the ink of Reference Example E-4, the ejection stability was measured by the same method and the same evaluation method as Example E-1. Table 19 shows the measurement results of the discharge stability.

(Reference Example E-5)
Reference Example E-5 was prepared in the same manner as Reference Example E-4 except that Pigment Dispersion E8 was prepared in the same manner as Pigment Dispersion E7 using Pigment Red 122 (dimethylquinacridone pigment: Clariant). Fabricated and evaluated. The ink composition is shown in Table 20. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example E-1. The results are shown in Table 19.

(Reference Example E-6)
Reference Example E-6 was prepared in the same manner as Pigment Dispersion E7 using Pigment Yellow 180 (Benzimidazolone Disazo Pigment: Clariant), except that Pigment Dispersion E9 was used. An ink was prepared and evaluated. The ink composition is shown in Table 20. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example E-1. The results are shown in Table 19.

(Reference Example E-7)
Reference Example E-7 was prepared and evaluated in the same manner as in Example E-4, except that the molecular weight of the polymer fine particles added in Example E-4 was changed to 90000. An emulsion having a molecular weight of 90000 was designated as Emulsion F (EM-F). The ink composition is shown in Table 20. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example E-1. The results are shown in Table 19. The measurement of the particle diameter of the polymer fine particles was performed in the same manner as in Example E-1.

(Reference Example E-8)
In Reference Example E-8, an ink was prepared and evaluated in the same manner as in Example E-5, except that the molecular weight of the polymer fine particles added in Example E-5 was changed to 1100000. An emulsion having a molecular weight of 1100000 was designated as Emulsion G (EM-G). The ink composition is shown in Table 20. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example E-1. The results are shown in Table 19. The measurement of the particle diameter of the polymer fine particles was performed in the same manner as in Example E-1.

[Example F]
Example F below corresponds to other preferred embodiment (f).

(Example F-1)
(1) Production of polymer (A-1) A reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was sufficiently purged with nitrogen, and then 20 parts by weight of methyl ethyl ketone (hereinafter sometimes simply referred to as “parts”). And 0.03 part of a polymerization chain transfer agent (2-mercaptoethanol), 11 parts of methacrylic acid, 10 parts of styrene macromer AS-6 (S) (Toagosei Co., Ltd.), 39 parts of styrene, 10 parts of benzyl methacrylate, BLENMER PP- 10% of 100 parts of each monomer total of 800 parts (Nippon Yushi Co., Ltd.) was added and stirred to obtain a mixed solution.

  Next, the remaining 90% of the monomer is put into a dropping funnel, and 0.27 part of the polymerization chain transfer agent, 60 parts of methyl ethyl ketone and a radical polymerization initiator (2,2′-azobis (2,4-dimethylvaleronitrile) are added. )) 1.2 parts were added and mixed, and the atmosphere was sufficiently replaced with nitrogen to obtain a mixed solution.

  Under a nitrogen atmosphere, the mixed solution in the reaction vessel was heated to 65 ° C. while stirring, and the mixed solution in the dropping funnel was gradually dropped over 3 hours. After completion of the dropwise addition, the mixture was kept at 65 ° C. for 2 hours, a solution in which 0.3 part of the radical polymerization initiator was dissolved in 5 parts of methyl ethyl ketone was added, and the mixture was further aged at 65 ° C. for 2 hours and 70 ° C. for 2 hours. -1) was obtained.

(2) Production of pigment dispersion F1 40 parts of the polymer solution (A-1) and 30 parts of Pigment Blue 15: 3 (copper phthalocyanine pigment: Clariant), 100 parts of 0.1 mol / L sodium hydroxide aqueous solution, 30 parts of methyl ethyl ketone was mixed. Then, using an ultra high pressure homogenizer (Ultimizer HJP-25005 manufactured by Sugino Machine Co., Ltd.), it was dispersed by passing 15 passes at 200 MPa. Then, it moved to another container, 300 parts of ion-exchange water was added, and also it stirred for 1 hour. And the whole amount of methyl ethyl ketone and a part of water were distilled off using the rotary evaporator, and it neutralized with 0.1 mol / L sodium hydroxide, and adjusted to pH9. Thereafter, the mixture was filtered through a 0.3 μm membrane filter and adjusted with ion exchange water to obtain a pigment dispersion F1 having a pigment concentration of 15%. The particle size was measured using a Microtrac particle size distribution analyzer UPA250 (Nikkiso Co., Ltd.) and found to be 100 nm.

(3) Preparation of polymer fine particles A reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, charged with 100 parts of ion-exchanged water and stirred with a nitrogen atmosphere at 70 ° C., a superoxide of polymerization initiator 0.2 parts of potassium is added, 40 parts of 100 parts of each monomer of 16 parts of styrene, 71 parts of ethyl acrylate, 11.5 parts of butyl acrylate and 1.5 parts of methacrylic acid, 7 parts of ion-exchanged water A monomer solution containing 0.05 part of sodium lauryl sulfate and 0.02 part of t-dodecyl mercaptan is dropped at 70 ° C. and reacted to prepare a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, the remaining 60% of the monomer, t-dodecyl mercaptan, 0. Polymer reaction by adding 5 parts of the reaction liquid with stirring at 70 ° C., neutralized with sodium hydroxide, adjusted to pH 8 to 8.5, and filtered through a 0.3 μm filter. Was prepared as Emulsion A (EM-A). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC, manufactured by Seiko Denshi). When the solvent was measured as THF using gel permeation chromatography (GPC) of L7100 system manufactured by Hitachi, Ltd., the molecular weight in terms of styrene was 200000.

  The acid value was measured by the following method. It collects in the state before sodium hydroxide neutralization of the said polymer fine particle aqueous dispersion, The solid content density | concentration is correctly measured with a thermobalance (TG-2121 by Seiko Electronic Industry). Next, about 10 g of this polymer fine particle aqueous dispersion is accurately weighed, put into a stoppered Erlenmeyer flask, and 100 ml of 2-propanol-tetrahydrofuran mixture (1: 2) is added and dissolved. As an indicator, and titrating with a 0.1 mol / L 2-propanol potassium hydroxide solution until a pale red color lasting 30 seconds is obtained. The acid value is determined by the formula (1).

Acid value (mgKOH / g) = (5.611 × a × f) / S (1)
S: Sample collection amount (g)
a: Consumption of 0.1 mol / L 2-propanol potassium hydroxide solution (ml)
f: Factor of 0.1 mol / L 2-propanol potassium hydroxide solution where a is the titration value (ml) -blank value (ml)
The acid value of EM-A determined by the above method was 10 mgKOH / g.

(4) Preparation of inkjet recording ink Table 22 shows examples of compositions suitable for the inkjet recording ink. The ink for inkjet recording of the present invention was prepared by using the dispersion F1 prepared by the above method and mixing it with the vehicle components shown in Table 22. In addition, 0.05% of the top side 240 (manufactured by Permachem Asia Co., Ltd.) is used for the remaining amount of water in Examples and Comparative Examples of the present invention to prevent ink corrosion, and benzotriazole is used to prevent ink jet head member corrosion. 0.02%, and EDTA (ethylenediaminetetraacetic acid) .2Na salt in an amount of 0.04% was added to ion-exchanged water in order to reduce the influence of metal ions in the ink system.

(5) Scratch resistance test and dry cleaning property test Using the ink of Example F-1, a sample printed solid on cotton is created using PX-V630 manufactured by Seiko Epson Corporation as an inkjet printer. The sample was subjected to friction fastness by rubbing 100 times with a load of 200 g using a Gakushin type friction fastness tester AB-301S manufactured by Tester Sangyo Co., Ltd. Two levels of dry and wet were evaluated according to Japanese Industrial Standard (JIS) JIS L0849, which confirms the degree of ink peeling. Similarly, the dry cleaning test was evaluated by the method B of JIS L0860. Table 21 shows the results of the abrasion resistance test and the dry cleaning test.

(6) Measurement of ejection stability Using the ink of Example F-1, using PX-V630 manufactured by Seiko Epson Corporation as an inkjet printer, Microsoft Word on XeroxP paper A4 size manufactured by Fuji Xerox Co., Ltd. at 35 ° C. and 35% atmosphere. Evaluation was performed by printing 100 pages at a rate of 4000 characters / page with a standard of character size 11 and MSP Gothic. AA when there is no printing disorder at all, A when there is printing disorder at A, B at 2 to 3 printing disorder B, C at 4 to 5 printing disorder, 6 or more printing disorder The results are shown in Table 21 with D being “D”.

(Example F-2)
Example F-2 was the same as Example F-1, except that Pigment Violet 19 (quinacridone pigment: manufactured by Clariant) was used as the pigment, and Pigment Dispersion F2 prepared in the same manner as Pigment Dispersion F1 was used. An ink was prepared by adding EM-A and evaluated. The particle size of Pigment Dispersion F2 was 110 nm as measured by the same method as in Example F-1. The ink composition is shown in Table 22. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example F-1. The results are shown in Table 21.

(Example F-3)
Example F-3 was the same as Example F-1, except that Pigment Yellow 14 (azo pigment: manufactured by Clariant) was used as the pigment, and Pigment Dispersion F3 produced in the same manner as Pigment Dispersion F1 was used. Ink was prepared by adding EM-A to and evaluated. The particle size of the pigment dispersion F2 was 140 nm as measured by the same method as in Example F-1. The ink composition is shown in Table 22. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example F-1. The results are shown in Table 21.

(Example F-4)
Example F-4 was prepared by changing the raw material monomer composition of polymer fine particles to 16 parts of styrene, 66 parts of ethyl acrylate, 7 parts of butyl acrylate, 2 parts of methacrylic acid, and 9 parts of ethyl carbitol acrylate. Ink was prepared and evaluated in the same manner as in Example F-1, except that Emulsion B (EM-B) was used. The glass transition temperature of the polymer fine particles of emulsion B was −16 ° C. Moreover, the acid value calculated | required by the same method as Example F-1 was 10 mgKOH / g. The ink composition is shown in Table 22. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example F-1. The results are shown in Table 21.

(Example F-5)
Example F-5 is a polymer fine particle emulsion C prepared by changing the raw material monomer composition of polymer fine particles to 16 parts of styrene, 68 parts of ethyl acrylate, 11.5 parts of butyl acrylate, and 4.5 parts of methacrylic acid. An ink was prepared and evaluated in the same manner as in Example F-2 except that (EM-C) was used. The glass transition temperature of the polymer fine particles of emulsion C was -11 ° C. Moreover, the acid value calculated | required by the same method as Example F-1 was 30 mgKOH / g. The ink composition is shown in Table 22. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example F-1. The results are shown in Table 21.

(Example F-6)
Example F-6 is an emulsion D (EM-D) of polymer particles prepared by changing the raw material monomer composition of polymer particles to 5 parts of styrene, 85 parts of ethyl acrylate, 8 parts of butyl acrylate, and 2 parts of methacrylic acid. ) Was used and evaluated in the same manner as in Example F-1. The glass transition temperature of the polymer fine particles of emulsion D was −21 ° C. Moreover, the acid value calculated | required by the same method as Example F-1 was 10 mgKOH / g. The ink composition is shown in Table 22. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example F-1. The results are shown in Table 21.

(Comparative Example F-1)
In Comparative Example F-1, the raw material monomer composition of the polymer fine particles was changed to 16 parts of styrene, 66 parts of ethyl acrylate, 6 parts of butyl acrylate, and 12 parts of 2-hydroxyethyl methacrylate, and the emulsion E ( An ink was prepared and evaluated in the same manner as in Example F-1, except that EM-E) was used. The glass transition temperature of the polymer fine particles of Emulsion E was −6 ° C. Moreover, the acid value calculated | required by the same method as Example F-1 was 10 mgKOH / g. The ink composition is shown in Table 22. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example F-1. The results are shown in Table 21.

(Comparative Example F-2)
In Comparative Example F-2, an ink was prepared by adding EM-A in the same manner as in Example F-2 except that a pigment dispersion having a particle diameter of 350 nm was prepared and used in Example F-2. evaluated. The particle size was measured by the same method as in Example F-1. A dispersion having a particle size of 350 nm was designated as Pigment Dispersion F2A. The ink composition is shown in Table 22. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example F-1. The results are shown in Table 21.

(Comparative Example F-3)
Comparative Example F-3 is a polymer fine particle emulsion H (EM-H) produced by changing the raw material monomer composition of the polymer fine particles to 40 parts of styrene, 47 parts of ethyl acrylate, 6 parts of butyl acrylate, and 7 parts of methacrylic acid. ) Was used and evaluated in the same manner as in Example F-2. The glass transition temperature of the polymer fine particles of emulsion H was 13 ° C. Moreover, the acid value calculated | required by the same method as Example F-1 was 10 mgKOH / g. The ink composition is shown in Table 22. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example F-1. The results are shown in Table 21.

(Comparative Example F-4)
In Comparative Example F-4, an ink was prepared and evaluated in the same manner as in Example F-1, except that the polymer fine particles were not added. The ink composition is shown in Table 22. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example F-1. The results are shown in Table 21.

[Example G]
Example G below corresponds to another preferred embodiment (g).
(Example G-1)
(1) Production of Pigment Dispersion G1 30 parts of Pigment Blue 15: 3 (copper phthalocyanine pigment: Clariant) and 3 parts of anionic polymerizable surfactant KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) and ion-exchanged water The mixture was mixed and dispersed in 15 passes at 200 MPa using an ultra-high pressure homogenizer (Ultimizer HJP-25005 manufactured by Sugino Machine). Then, it moved to another container, 300 parts of ion-exchange water was added, and also it stirred for 1 hour. To this, 50 parts of 2-ethylhexyl methacrylate, 20 parts of benzyl methacrylate and 10 parts of butyl acrylate were added and mixed with stirring. This was put into a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel sufficiently purged with nitrogen. After raising the internal temperature of the reaction vessel to 80 ° C., an aqueous solution in which 0.4 g of potassium persulfate was dissolved as a polymerization initiator was added dropwise to 20 g of ion-exchanged water, and nitrogen was introduced into the reaction vessel at 80 ° C. The reaction was performed for 6 hours. After completion of the reaction, the pH was adjusted to 8 with a 1 mol / l aqueous potassium hydroxide solution. Next, this was subjected to ultrafiltration by a cross flow method using an ultrafiltration apparatus, and then the pigment concentration was adjusted to 15% with ion-exchanged water to obtain a pigment dispersion G1. It was 105 nm when the particle size was measured using Microtrac particle size distribution analyzer UPA250 (Nikkiso Co., Ltd.).

(3) Preparation of polymer fine particles A reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, charged with 100 parts of ion-exchanged water and stirred with a nitrogen atmosphere at 70 ° C., a superoxide of polymerization initiator 0.2 parts of potassium is added, 40 parts of 100 parts of each monomer of 16 parts of styrene, 71 parts of ethyl acrylate, 11.5 parts of butyl acrylate and 1.5 parts of methacrylic acid, 7 parts of ion-exchanged water A monomer solution containing 0.05 part of sodium lauryl sulfate and 0.02 part of t-dodecyl mercaptan is dropped at 70 ° C. and reacted to prepare a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, the remaining 60% of the monomer, t-dodecyl mercaptan, 0. Polymer reaction by adding 5 parts of the reaction liquid with stirring at 70 ° C., neutralized with sodium hydroxide, adjusted to pH 8 to 8.5, and filtered through a 0.3 μm filter. Was prepared as Emulsion A (EM-A). A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC, manufactured by Seiko Denshi). When the solvent was measured as THF using gel permeation chromatography (GPC) of L7100 system manufactured by Hitachi, Ltd., the molecular weight in terms of styrene was 200000.

  The acid value was measured by the following method. It collects in the state before sodium hydroxide neutralization of the said polymer fine particle aqueous dispersion, The solid content density | concentration is correctly measured with a thermobalance (TG-2121 by Seiko Electronic Industry). Next, about 10 g of this polymer fine particle aqueous dispersion is accurately weighed, put into a stoppered Erlenmeyer flask, and 100 ml of 2-propanol-tetrahydrofuran mixture (1: 2) is added and dissolved. As an indicator, and titrating with a 0.1 mol / L 2-propanol potassium hydroxide solution until a pale red color lasting 30 seconds is obtained. The acid value is determined by the formula (1).

Acid value (mgKOH / g) = (5.611 × a × f) / S (1)
S: Sample collection amount (g)
a: Consumption of 0.1 mol / L 2-propanol potassium hydroxide solution (ml)
f: Factor of 0.1 mol / L 2-propanol potassium hydroxide solution where a is the titration value (ml) -blank value (ml)
The acid value of EM-A determined by the above method was 10 mgKOH / g.

(4) Preparation of inkjet recording ink Table 24 shows examples of compositions suitable for the inkjet recording ink. The ink for inkjet recording of the present invention was prepared by using the dispersion G1 prepared by the above method and mixing with the vehicle components shown in Table 24. In addition, 0.05% of the top side 240 (manufactured by Permachem Asia Co., Ltd.) is used for the remaining amount of water in Examples and Comparative Examples of the present invention to prevent ink corrosion, and benzotriazole is used to prevent ink jet head member corrosion. 0.02%, and EDTA (ethylenediaminetetraacetic acid) .2Na salt in an amount of 0.04% was added to ion-exchanged water in order to reduce the influence of metal ions in the ink system.

(5) Abrasion resistance test and dry cleaning property test Using the ink of Example G-1, a sample printed solid on cotton using PX-V630 manufactured by Seiko Epson Corporation as an inkjet printer is prepared. The sample was subjected to friction fastness by rubbing 100 times with a load of 200 g using a Gakushin type friction fastness tester AB-301S manufactured by Tester Sangyo Co., Ltd. Two levels of dry and wet were evaluated according to Japanese Industrial Standard (JIS) JIS L0849, which confirms the degree of ink peeling. Similarly, the dry cleaning test was evaluated by the method B of JIS L0860. Table 23 shows the results of the abrasion resistance test and the dry cleaning test.

(6) Measurement of ejection stability Using the ink of Example G-1 and using PX-V630 manufactured by Seiko Epson Corporation as an inkjet printer, Microsoft Word on XeroxP paper A4 size manufactured by Fuji Xerox Co., Ltd. at 35 ° C. and 35% atmosphere. Evaluation was performed by printing 100 pages at a rate of 4000 characters / page with a standard of character size 11 and MSP Gothic. AA when there is no printing disorder at all, A when there is printing disorder at A, B at 2 to 3 printing disorder B, C at 4 to 5 printing disorder, 6 or more printing disorder The results are shown in Table 23.

(Example G-2)
Example G-2 was the same as Example G-1, except that Pigment Violet 19 (quinacridone pigment: manufactured by Clariant) was used as the pigment, and Pigment Dispersion G2 prepared in the same manner as Pigment Dispersion G1 was used. An ink was prepared by adding EM-A and evaluated. The particle size of the pigment dispersion G2 was 120 nm as measured by the same method as in Example G-1. Table 24 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example G-1. The results are shown in Table 23.

(Example G-3)
Example G-3 was the same as Example G-1, except that Pigment Yellow 14 (azo pigment: manufactured by Clariant) was used as the pigment, and Pigment Dispersion G3 produced in the same manner as Pigment Dispersion G1 was used. Ink was prepared by adding EM-A to and evaluated. The particle size of the pigment dispersion G2 was 145 nm as measured by the same method as in Example G-1. Table 24 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example G-1. The results are shown in Table 23.

(Example G-4)
Example G-4 was prepared by changing the raw material monomer composition of polymer fine particles to 16 parts of styrene, 66 parts of ethyl acrylate, 7 parts of butyl acrylate, 2 parts of methacrylic acid, and 9 parts of ethyl carbitol acrylate. Ink was prepared and evaluated in the same manner as in Example G-1 except that Emulsion B (EM-B) was used. The glass transition temperature of the polymer fine particles of emulsion B was −16 ° C. Moreover, the acid value calculated | required by the same method as Example G-1 was 10 mgKOH / g. Table 24 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example G-1. The results are shown in Table 23.

(Example G-5)
Example G-5 is a polymer fine particle emulsion C prepared by changing the raw material monomer composition of polymer fine particles to 16 parts of styrene, 68 parts of ethyl acrylate, 11.5 parts of butyl acrylate, and 4.5 parts of methacrylic acid. An ink was prepared and evaluated in the same manner as in Example G-2 except that (EM-C) was used. The glass transition temperature of the polymer fine particles of emulsion C was -11 ° C. Moreover, the acid value calculated | required by the same method as Example G-1 was 30 mgKOH / g. Table 24 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example G-1. The results are shown in Table 21.

(Example G-6)
Example G-6 is a polymer fine particle emulsion D (EM-D) prepared by changing the raw material monomer composition of polymer fine particles to 5 parts of styrene, 85 parts of ethyl acrylate, 8 parts of butyl acrylate, and 2 parts of methacrylic acid. Ink was produced and evaluated in the same manner as in Example G-1, except that the above was used. The glass transition temperature of the polymer fine particles of emulsion D was −21 ° C. Moreover, the acid value calculated | required by the same method as Example G-1 was 10 mgKOH / g. Table 24 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example G-1. The results are shown in Table 23.

(Comparative Example G-1)
Comparative Example G-1 was prepared by changing the raw material monomer composition of the polymer fine particles to 16 parts of styrene, 66 parts of ethyl acrylate, 6 parts of butyl acrylate, and 12 parts of 2-hydroxyethyl methacrylate. An ink was prepared and evaluated in the same manner as in Example G-1, except that EM-E) was used. The glass transition temperature of the polymer fine particles of Emulsion E was −6 ° C. Moreover, the acid value calculated | required by the same method as Example G-1 was 10 mgKOH / g. Table 24 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example G-1. The results are shown in Table 23.

(Comparative Example G-2)
Comparative Example G-2 was prepared by adding EM-A in the same manner as in Example G-2 except that a pigment dispersion having a particle size of 350 nm was prepared and used in Example G-2. evaluated. The particle size was measured by the same method as in Example G-1. The dispersion having a particle diameter of 350 nm was designated as pigment dispersion G2A. Table 24 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example G-1. The results are shown in Table 23.

(Comparative Example G-3)
Comparative Example G-3 is a polymer fine particle emulsion H (EM-H) prepared by changing the raw material monomer composition of the polymer fine particles to 40 parts of styrene, 47 parts of ethyl acrylate, 6 parts of butyl acrylate, and 7 parts of methacrylic acid. ) Was used and evaluated in the same manner as in Example G-2. The glass transition temperature of the polymer fine particles of emulsion H was 13 ° C. Moreover, the acid value calculated | required by the same method as Example G-1 was 10 mgKOH / g. Table 24 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example G-1. The results are shown in Table 23.

(Comparative Example G-4)
Comparative Example G-4 was prepared and evaluated in the same manner as in Example G-1, except that no polymer fine particles were added. Table 24 shows the ink composition. The rubbing resistance test, the dry cleaning test and the discharge stability test were performed in the same manner as in Example G-1. The results are shown in Table 23.

Claims (10)

And the average particle size is 50nm or more 300nm following dispersion pigment was dispersible in water, a glass transition temperature of -10 ° C. or less, Ri and the name and a polymer fine particles is not more than 100 mg KOH / g acid number The dispersion has an average particle diameter of 50 nm to 300 nm in which carbon black dispersed without a dispersant can be dispersed in water, and the polymer fine particle is 70% by weight or more as a constituent component. An ink composition which is polymerized using an alkyl (meth) acrylate and / or a cyclic alkyl (meth) acrylate.   A dispersion having an average particle size of 50 nm or more and 300 nm or less capable of dispersing the pigment in water, and polymer fine particles having a glass transition temperature of −10 ° C. or less and an acid value of 100 mgKOH / g or less, The dispersion has an average particle diameter of 50 nm to 300 nm in which an organic pigment can be dispersed in water with a polymer, and the polymer has a styrene-converted weight average molecular weight of 10,000 to 200,000 by gel permeation chromatography (GPC). An ink composition, wherein the polymer fine particles are polymerized using 70% by weight or more of alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate as a constituent component.   A dispersion having an average particle diameter of 50 nm to 300 nm, a fine particle having a glass transition temperature of −10 ° C. or less and an acid value of 100 mgKOH / g or less, and a melting point of 80 ° C. Comprising the above polyalkylene wax, wherein the polymer fine particles are polymerized using 70% by weight or more of alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate as a constituent component An ink composition. The polymer fine particles are polymerized using 70% by weight or more of alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate and 5% by weight or more and 25% by weight or less of styrene as components. The ink composition according to any one of claims 1 to 3, wherein the ink composition is any one of the above. The alkyl (meth) acrylate and / or the cyclic alkyl (meth) acrylate is an alkyl (meth) acrylate having 1 to 24 carbon atoms and / or a cyclic alkyl (meth) acrylate having 3 to 24 carbon atoms. The ink composition according to any one of claims 1 to 4 . The ink composition according to any one of claims 1 to 5 , wherein the polymer fine particles have a styrene-converted weight average molecular weight of from 100,000 to 1,000,000 by gel permeation chromatography (GPC). The ink composition according to any one of claims 1 to 6 , comprising 1,2-alkylene glycol. The ink composition according to any one of claims 1 to 7 , comprising an acetylene glycol surfactant and / or an acetylene alcohol surfactant. The ink composition according to any one of Claims 1 to 8 , wherein the content (% by weight) of the polymer fine particles is larger than the content (% by weight) of the pigment. The ink composition according to any one of claim 1 to 9, characterized in that for use in ink-jet recording systems.