JP5569794B2 - Ink composition for inkjet recording - Google Patents

Description

Background of the Invention

FIELD OF THE INVENTION The present invention relates to an ink composition for ink jet recording, and more particularly to an ink composition for ink jet recording which is excellent in abrasion resistance and dry cleaning properties and also in discharge stability.

BACKGROUND ART Pigments are used as colorants for ink jet recording inks because of their excellent fastness such as water resistance and light resistance. Since the pigment has poor solubility in water, a dispersing agent such as a surfactant or a polymer is added to the ink to improve the dispersion stability of the pigment. As the dispersant, a resin having both a hydrophobic part and a hydrophilic part, for example, a styrene-acrylic copolymer resin is generally used.

  By the way, the ink used for ink jet recording has various printing such as no bleeding, good drying, uniform printing on various recording media, and adjoining colors in multicolor printing. Quality is required. In order to improve the printing quality, various additives are usually added to the ink. For example, glycol ethers such as diethylene glycol monobutyl ether are added to the ink in order to improve the permeability to the recording medium and reduce bleeding (US Pat. No. 5,156,675: Patent Document 1). An acetylene glycol surfactant is added (US Pat. No. 5,183,502: Patent Document 2), or both are added (US Pat. No. 5,196,056). Patent Document 3).

  However, in the ink to which the pigment dispersant is added, if the above surfactants or glycol ethers are present in the ink, the dispersion resin is likely to be adsorbed and desorbed from the pigment, and the storage stability of the ink is insufficient. There was a case. Further, when the dispersant detached from the pigment remains in the ink, the ink viscosity is increased, and the ink ejection stability may be insufficient.

  So far, an inkjet ink composition containing a crosslinked polyurethane dispersion with improved washing fastness of inkjet printed fabric has been disclosed (Japanese Patent Publication No. 2007-522285: Patent Document 4). It can be said that there is still a demand for the development of an ink composition that is further excellent in stability and fixing properties, particularly for textiles.

US Pat. No. 5,156,675 US Pat. No. 5,183,502 US Pat. No. 5,196,056 Special table 2007-522285

  The present inventors recently added a specific resin to an ink composition containing a specific pigment dispersion, and as an ink composition for inkjet recording, particularly for textiles, has improved abrasion resistance and dry cleaning properties. The inventors have obtained knowledge that an ink composition for ink jet recording that is excellent in discharge stability as well as excellent can be realized. The present invention is based on such knowledge.

  Accordingly, an object of the present invention is to provide an ink composition for ink jet recording which is excellent in abrasion resistance and dry cleaning properties and also excellent in ejection stability.

（上記式中、Ｎは１〜６の整数を表す）、

（上記式中、Ｏ＋Ｐ＋Ｑの値は０〜６の整数を表す）。 The ink composition for ink jet recording according to the present invention is an ink composition for ink jet recording comprising at least a dispersion in which a pigment can be dispersed in water, water, and a polyurethane resin,
The dispersion contains a self-dispersing pigment, the dispersion has an average particle size of 20 to 300 nm, and the polyurethane resin is represented by the following formula (I) or / and formula (II) as a constituent component: An ink composition for ink jet recording comprising the following compound:

(In the above formula, N represents an integer of 1 to 6),

(In the above formula, the value of O + P + Q represents an integer of 0 to 6).

  According to the ink composition of the present invention, it is possible to realize an ink for ink jet recording which is excellent in abrasion resistance and dry cleaning property as well as in ejection stability, particularly as an ink composition for ink jet recording for textiles.

Detailed description of the invention

  An ink composition according to the present invention is an ink composition for ink jet recording comprising at least a dispersion in which a pigment can be dispersed in water, water, and a polyurethane resin, and the dispersion contains a self-dispersing pigment. An ink composition for ink jet recording, wherein the average particle size of the dispersion is 20 to 300 nm, and the polyurethane resin contains a compound represented by the following formula (I) or / and formula (II) as a constituent component: In particular, it is preferably used for inkjet printing. Hereinafter, each component contained in the ink composition for inkjet recording of the present invention will be described.

Polyurethane resin The ink composition for inkjet recording of the present invention comprises a polyurethane resin, and the polyurethane resin comprises a compound represented by the above formula (I) or / and formula (II) as a constituent component thereof. It contains.

  The compound represented by the formula (I) is more preferably a compound having N = 2 to 4 among the compounds represented by the formula (I). In the formula (I), the compound of N = 2 to 4 can realize an ink composition for ink jet recording which is further excellent in abrasion resistance and dry cleaning property and also excellent in ejection stability.

  The compound represented by the formula (II) is more preferably a compound represented by O + P + Q = 0 to 3 among the compounds represented by the formula (II). In the formula (II), by using O + P + Q = 0 to 3, it is possible to realize an ink composition for ink jet recording which is further excellent in abrasion resistance and dry cleaning property and also excellent in ejection stability.

(Polyisocyanate)
The ink composition of the present invention contains polyisocyanate as a constituent component of the polyurethane resin. The polyisocyanate that can be used in the ink composition of the present invention is a compound containing two or more isocyanate groups, such as diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,6-bis (isocyanatomethyl) decahydronaphthalene, lysine triisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-tolidine Diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl ether diisocyanate, 3- (2'-isocyanate cyclohexyl) Propyl isocyanate, tris (phenyl isocyanate) thiophosphate, isopropylidenebis (cyclohexyl isocyanate), 2,2'-bis (4-isocyanatoenyl) propane, triphenylmethane triisocyanate, bis (diisocyanatotolyl) phenylmethane, 4,4 ', 4 "-triisocyanate-2,5-dimethoxyphenylamine, 3,3'-dimethoxybenzidine-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'- Diisocyanatobiphenyl, 4,4′-diisocyanato-3,3′-dimethylbiphenyl, dicyclohexylmethane-4,4′-diisocyanate, 1,1′-methylenebis (4-isocyanatobenzene), 1,1′-methyle Bis (3-methyl-4-isocyanatobenzene), m-xylylene diisocyanate, p-xylylene diisocyanate, 1,3-bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1- Isocyanate-1-methylethyl) benzene, 1,3-bis ((2-isocyanato-2-propyl) benzene, 2,6-bis (isocyanatomethyl) tetrahydrodicyclopentadiene, bis (isocyanatomethyl) dicyclopentadiene Bis (isocyanatomethyl) tetrahydrothiophene, bis (isocyanatomethyl) thiophene, 2,5-diisocyanatomethylnorbornene, bis (isocyanatomethyl) adamantane, 3,4-diisocyanatoselenophane, 2,6-diisocyanate-9- Serenavi Cyclonona , Bis (isocyanatomethyl) selenophan, 3,4-diisocyanate, -2,5-diselenolane, dimer acid diisocyanate, 1,3,5-tri (1-isocyanatohexyl) isocyanuric acid, 2,5-di Isocyanatomethyl-1,4-dithiane, 2,5-bis (isocyanatomethyl-4-isocyanato-2-thiabutyl) -1,4-dithiane, 2,5-bis (3-isocyanato-2-thiapropyl) 1 , 4-dithiane, 1,3,5-triisocyanatocyclohexane, 1,3,5-tris (isocyanatomethyl) cyclohexane, bis (isocyanatomethylthio) methane, 1,5-diisocyanato-2-isocyanatomethyl- 3-thiapentane, 1,2,3-tris (isocyanatoethylthio) propane, 1,2,3- (i Cyanatomethylthio) propane, 1,1,6,6-tetrakis (isocyanatomethyl) -2,5-dithiahexane, 1,1,5,5-tetrakis (isocyanatomethyl) -2,4-dithiapentane, 1, Examples thereof include 2-bis (isocyanatomethylthio) ethane and 1,5-diisocyanate-3-isocyanatomethyl-2,4-dithiapentane. Examples thereof include dimers of these polyisocyanates by a bullet-type reaction, cyclized trimers of these polyisocyanurates, and adducts of these polyisocyanates and alcohols or thiols. Furthermore, the compound which changed a part or all of the isocyanate group of the said polyisocyanate into the isothiocyanate group can be mentioned. These can be used alone or in admixture of two or more.

（上記式中、Ｌは３〜１０の整数を表す）。 According to a preferred embodiment of the present invention, the polyisocyanate contained as a constituent component of the polyurethane resin is preferably a compound represented by the following formula (III) among the polyisocyanates described above:

(In the above formula, L represents an integer of 3 to 10).

  The compound represented by the formula (III) is more preferably a compound having L = 4 to 7 among the compounds represented by the formula (III). In the formula (III), the compound of N = 4 to 7 can realize an ink composition for ink jet recording which is further excellent in abrasion resistance and dry cleaning properties and excellent in ejection stability.

(Polyol)
The ink composition of the present invention contains a polyol as a constituent component of the polyurethane resin. A polyol is a compound containing two or more hydroxyl groups, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,2-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene Glycol, polyethylene glycol, polypropylene glycol, 1,8-octanediol, 1,2-octanediol, linear aliphatic glycol such as 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol , 2- Til-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, Aliphatic branched glycols such as 2-methyl-1,8-octanediol, alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, glycerin, trimethylolethane, trimethylolpropane, tributy Examples thereof include polyfunctional glycols such as roll propane, pentaerythritol, and sorbitol, and these may be used alone or in combination of two or more.

  In the present invention, a polyester polyol can also be used. For example, it can be obtained by a known method such as dehydration condensation of a glycol or ether listed below with a divalent carboxylic acid or carboxylic anhydride. Here, the specific compound used for preparation of the polyester polyol which can be used for the ink composition of this invention is mentioned. Examples of the saturated or unsaturated glycols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,2- Pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene Linear aliphatic glycols such as glycol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol; neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1 , 3-Pro Diol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, 2-methyl-1,8 -Aliphatic branched glycols such as octanediol, alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, glycerin, trimethylolethane, trimethylolpropane, tributyrolpropane, pentaerythritol, sorbitol And various glycols such as polyfunctional glycols.

  Examples of ethers include alkyl glycidyl ethers such as n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether, and monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester.

  Examples of the divalent carboxylic acid and acid anhydride include adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, Examples thereof include dibasic acids such as azelaic acid, sebacic acid, and suberic acid, or acid anhydrides corresponding thereto, dimer acid, castor oil, and fatty acids thereof. In addition to polyester polyols obtained by dehydration condensation using these, polyester polyols obtained by ring-opening polymerization of a cyclic ester compound are also included.

  The polyester polyol that can be used in the present invention is, for example, poly [3-methyl-1,5-pentanediol] -alt- (adipic acid obtained by dehydration condensation of 3-methyl-1,5-pentanediol and adipic acid. ]] (Kuraray polyol P2010, manufactured by Kuraray Co., Ltd.) and the like are commercially available.

  Further, the polycarbonate polyol that can be used in the present invention is generally a demethanol condensation reaction of a polyhydric alcohol and dimethyl carbonate, a dephenol condensation reaction of a polyhydric alcohol and diphenyl carbonate, or a deethylene condensation of a polyhydric alcohol and ethylene carbonate. It is produced through a reaction such as a glycol condensation reaction. Examples of the polyhydric alcohol used in these reactions include 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and pentane. Various saturated or unsaturated glycols such as diol, 3-methyl-1,5-pentanediol, octanediol, 1,4-butynediol, dipropylene glycol, tripropylene glycol, polytetramethylene ether glycol, 1,4 -Cycloaliphatic diglycol, alicyclic glycols such as 1,4-cyclohexanedimethanol, and the like.

  As the polycarbonate polyol that can be used in the present invention, for example, those based on 1,6-hexanediol (PES-EXP815, manufactured by Nippon Polyurethane Industry Co., Ltd.) are commercially available.

  In addition, as polytetramethylene ether glycol, for example, tetrahydrofuran is opened to one or more polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, and neopentyl glycol. What is obtained by addition by polymerization is mentioned. These cyclic ethers can be used alone or in combination of two or more, and those using two or more of the above cyclic ethers can also be used. For example, what consists of tetrahydrofuran and neopentyl glycol (PTXG-1800, the Asahi Kasei company) etc. are marketed.

  Furthermore, examples of the polyol that can be used in the present invention include Actol EP3033 (manufactured by Mitsui Chemicals Urethane Co., Ltd.), PREMINOL 7003 (manufactured by Asahi Glass Co., Ltd.), PREMINOL 7001 (manufactured by Asahi Glass Co., Ltd.), Adeka Polyether AM302 (manufactured by Asahi Denka Co., Ltd.) and the like. Is commercially available.

（上記式中、Ｍは３〜１０の整数を表し、ｎは２〜１４の整数を表す）。
上記式(IV)で表される化合物は、単一の化合物でもよく、Ｍが３〜１０の整数で、ｎが２〜１４の整数の範囲内において異なる値を有する二種以上の化合物を含んでいてもよい。 According to a preferred embodiment of the present invention, the polyol contained as a constituent component of the polyurethane resin is preferably a compound represented by the following formula (IV) among the polyols described above:

(In the above formula, M represents an integer of 3 to 10, and n represents an integer of 2 to 14).
The compound represented by the above formula (IV) may be a single compound, and includes two or more compounds having different values within a range where M is an integer of 3 to 10 and n is an integer of 2 to 14. You may go out.

  The compound represented by the formula (IV) is more preferably a compound having M = 5 to 7 among the compounds represented by the formula (IV). In the formula (IV), the compound of M = 5 to 7 can realize an ink composition for ink jet recording which is further excellent in abrasion resistance and dry cleaning properties and excellent in ejection stability.

  According to a preferred embodiment of the present invention, in the raw material composition of the polyurethane resin, the ratio of the number of OH groups of the compound of the formula (II) to the number of NCO groups of the polyisocyanate (the number of OH groups of the compound of the formula (II) / The number of NCO groups possessed by the polyisocyanate) is preferably 0.75 or less. When the ratio is 0.75 or less, it is possible to realize an ink composition for ink jet recording which is further excellent in abrasion resistance and dry cleaning properties and also excellent in ejection stability.

  The polyurethane resin used in the ink composition for ink jet recording according to the present invention is obtained by polymerizing a monomer component containing at least a compound represented by the formula (I) and a compound represented by the formula (II). Is.

  The polyurethane resin obtained by polymerizing the above monomers preferably has a glass transition temperature of 30 ° C. or lower. By using a polyurethane resin having a glass transition temperature of 30 ° C. or lower, an ink composition for ink jet recording that is excellent in abrasion resistance and dry cleaning properties and excellent in discharge stability can be realized. A more preferable glass transition temperature is 25 ° C. or lower. The glass transition temperature means a value measured according to JIS K6900.

  Further, the polyurethane resin used in the present invention has an acid value of 100 mgKOH / g or less. By using a polyretane resin having an acid value of 100 mgKOH / g or less, it is possible to realize an ink composition for ink jet recording that is excellent in abrasion resistance and dry cleaning properties and also excellent in ejection stability. A preferable acid value is 60 mgKOH / g or less.

  The average particle size of the polyurethane resin is preferably 20 to 300 nm. By using the polyurethane resin having such an average particle size, the ink jet recording has excellent abrasion resistance and dry cleaning properties, and excellent discharge stability. The ink composition for use can be realized. A more preferable average particle diameter of the polyurethane resin is 30 to 200 nm. In the present invention, the average particle diameter is a volume average particle diameter that can be measured by a dynamic light scattering method, and can be measured using, for example, Microtrac UPA150 (Microtrac Inc.).

  Although it does not specifically limit as a solvent used for superposition | polymerization with each above-mentioned monomer, A ketone solvent and an ether solvent can be mentioned. However, since it is an aqueous pigment dispersion, it is preferable that the solvent can be removed later. As such a solvent, the following can be used. That is, examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of ether solvents include dibutyl ether, tetrahydrofuran, dioxane and the like.

  The polyurethane resin used in the present invention is preferably contained in a larger amount than the pigment dispersion on a mass basis. By adding more polymer fine particles than the pigment dispersion in mass units, the fixability of the pigment is improved, particularly as an inkjet recording ink for textiles.

Pigment Dispersion The ink composition according to the present invention comprises a dispersion in which a pigment can be dispersed in water. This pigment dispersion contains a self-dispersing pigment, and the average particle diameter of the dispersion is 20 to 300 nm. This average particle diameter is a volume average particle diameter that can be measured by a dynamic light scattering method, and can be measured using, for example, Microtrac UPA150 (Microtrac Inc.). The dispersion in which the pigment is dispersible in water includes not only a dispersion in which the pigment is dispersed in water, but also a dispersion in which the pigment is dispersed without containing water.

  Self-dispersing pigments are pigments that can be dispersed and / or dissolved in an aqueous medium without a dispersant. Here, “dispersed and / or dissolved in an aqueous medium without a dispersing agent” means that the surface is stably present in the aqueous medium due to the hydrophilic group on the surface without using a dispersing agent for dispersing the pigment. The state that is.

  The ink containing the self-dispersing pigment as a colorant does not need to contain a dispersant in order to disperse a normal pigment. Therefore, there is almost no foaming due to a decrease in defoaming property due to the dispersant, and an ink excellent in ejection stability can be easily prepared. In addition, since a significant increase in viscosity due to the dispersant can be suppressed, it is possible to contain more pigment, and the printing density can be sufficiently increased.

In the ink composition of the present invention, the dispersion in which the pigment is dispersible in water is a self-dispersing pigment having a hydrophilic group on the surface of the pigment, and the hydrophilic group includes -OM, -COOM, -CO-, _{-SO 3 M, -SO 2 M,} -SO 2 NH 2, -RSO 2 M, -PO 3 HM, -PO 3 M 2, -SO 2 NHCOR, -NH 3, and -NR ₃ (M in the formula Represents a hydrogen atom, an alkali metal, ammonium, a phenyl group which may have a substituent, or organic ammonium, and R may have an alkyl group having 1 to 12 carbon atoms or a substituent. It is preferably one or more hydrophilic groups selected from the group consisting of: (which represents a good naphthyl group).

  The self-dispersing pigment contained in the pigment dispersion is produced, for example, by bonding (grafting) the hydrophilic group to the surface of the pigment by subjecting the pigment to physical treatment or chemical treatment. Examples of the physical treatment include vacuum plasma treatment. Examples of the chemical treatment include a wet oxidation method of oxidizing with an oxidizing agent in water, a method of binding a carboxyl group via a phenyl group by binding p-aminobenzoic acid to the pigment surface, and the like.

  In the present invention, the pigment used as the raw material for the self-dispersing pigment contained in the pigment dispersion is a high-quality self-dispersing pigment having the above hydrophilic group via a phenyl group on the pigment surface. This is preferable in terms of color development. As the surface treatment means for bonding a hydrophilic group to the pigment surface via a phenyl group, various known surface treatment means can be applied, and sulfanilic acid, p-aminobenzoic acid, 4-aminosalicylic acid, etc. Examples thereof include a method of bonding a hydrophilic group via a phenyl group. For black inks, self-dispersed pigments surface-treated by oxidation treatment with hypohalous acid and / or hypohalite, oxidation treatment with ozone, or oxidation treatment with persulfuric acid and / or persulfate Is preferable in terms of high color development.

  As a pigment that can be used in the ink composition of the present invention, for black ink, for example, carbon black produced by a known method such as a contact method, a furnace method, or a thermal method can be used. Specific examples of preferred carbon black in the present invention include No. 2300, 900, MCF88, no. 20B, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, No2200B (Mitsubishi Chemical Corporation), Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Pretex 35, U, V, 140U, Special Black 6 5, 4A, 4, 250 (above Degussa), Conductex SC, Raven 1255, 5750, 5250, 5000, 3500, 1255, 700 (above Columbia Carbon), Regal 400R, 330R, 660R, Mogul L , Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, Elftex 12 (manufactured by Cabot Corporation), and the like. These carbon blacks may be used alone or as a mixture of two or more.

  For color inks, in addition to pigments such as pigment yellow, pigment red, pigment violet, pigment blue, and pigment black described in the color index, phthalocyanine, azo, anthraquinone, azomethine, and condensed ring systems And the like. Further, organic pigments such as yellow No. 4, No. 5, 205, 401; orange No. 228, 405; blue No. 1, 404, etc., titanium oxide, zinc oxide, zirconium oxide, iron oxide, ultramarine blue, bitumen, Examples thereof include inorganic pigments such as chrome oxide. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42, 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 150, 153, 155, 174, 180, 198, C.I. I. Pigment red 1,3,5,8,9,16,17,19,22,38,57: 1,90,112,122,123,127,146,184, C.I. I. Pigment Bio Red 1,3,5: 1, 16, 19, 23, 38, C.I. I. And CI pigment blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, and 16. In particular, the organic pigment contained in the yellow ink composition is C.I. I. Pigment Yellow 74, 109, 110, 128, 138, 147, 150, 155, 180, and 188. The organic pigment contained in the magenta ink composition contains at least one selected from the group consisting of C.I. I. Pigment red 122, 202, 207, 209, and C.I. I. The organic pigment containing at least one selected from the group consisting of CI pigment violet 19 and contained in the cyan ink composition is C.I. I. It is preferable to include at least one selected from the group consisting of CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, and 16. Moreover, it is also possible to utilize a commercial item, and CAB-O-JET250C, CAB-O-JET260M, CAB-O-JET270Y (above, Cabot company make) etc. are mentioned.

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

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

<Water and other ingredients>
The ink composition according to the present invention comprises water as a main solvent. As the water, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used. In addition, the use of water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is preferable because generation of mold or bacteria can be prevented when the ink composition is stored for a long period of time.

  The ink composition according to the present invention preferably further comprises 1,2-alkylene glycol. By adding 1,2-alkylene glycol, bleeding is reduced, print quality is improved, and color development is also improved by using the polymer fine particles and the dispersion resin together. 1,2-alkylene glycol includes 1,2-alkylene having 5 or 6 carbon atoms such as 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol, and the like. Glycol is preferred. Among these, 1,2-hexanediol and 4-methyl-1,2-pentanediol having 6 carbon atoms are more preferable. The amount of 1,2-alkylene glycol added is preferably 0.3 to 30% by weight, more preferably 0.5 to 10% by weight, based on the entire ink.

  In addition, the ink composition according to the present invention is compatible with water, and is a water solution that stably dissolves or holds a pigment contained in the ink composition, as well as a pH adjuster and various components described later. It is preferable that an organic solvent is included.

  Preferred examples of the water-soluble organic solvent include improved solubility of glycol ethers having low solubility in water and other components, further improved permeability to a recording medium (for example, paper), and nozzle clogging. As a function that can be expected to prevent water, alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl Ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, die Lenglycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1- Methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether , Glycol ethers such as dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, formamide, acetamide, dimethyl sulfoxide, sorbit, sorbitan, acetin, diacetin, triacetin , Sulfolane, and mixtures thereof.

  In the present invention, among the permeable organic solvents described above, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol monopentyl ether, triethylene glycol monopentyl ether, diethylene glycol monohexyl Ether or triethylene glycol monohexyl ether is more preferable. By using the above-mentioned polymer and polymer dispersant together with these glycol ethers, bleeding can be further reduced and printing quality is improved.

  Furthermore, saccharides can be used for the same purpose. Examples include monosaccharides and polysaccharides, in addition to glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitol, maltose, cellobiose, sucrose, trehalose, maltotriose, etc. Alginic acid and its salts, cyclodextrins, and celluloses can be used. The amount added may be appropriately determined, but is preferably 0.05% by weight or more and 30% by weight or less. By being in the above range, even when the ink composition is dried at the tip of the head, the clogging can be easily recovered, and the viscosity of the ink composition capable of stable printing can be easily realized. Can do. According to a preferred embodiment of the present invention, more preferable addition amount of glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitolose, maltose, cellobiose, sucrose, trehalose, maltotriose is 3-20. % By weight. In addition, since addition of alginic acid, its salt, and cellulose tends to increase the viscosity of the ink composition, attention must be paid to the addition amount.

  The ink composition according to the present invention preferably contains a surfactant in order to control its permeability. The surfactant to be added is preferably compatible with other components in the ink composition. Further, a surfactant having high penetrability and stability is preferable. As the surfactant, amphoteric surfactants and nonionic surfactants are preferably used.

  Preferred examples of amphoteric surfactants include lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and others Examples include imidazoline derivatives.

  Preferred examples of nonionic surfactants include acetylene glycol surfactants, acetylene alcohol surfactants, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl. Ethers such as allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene distearic acid ester , Sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxye Examples include ester surfactants such as lenmonooleate and polyoxyethylene stearate, silicon surfactants such as dimethylpolysiloxane, fluorine-containing surfactants such as other fluorine alkyl esters and perfluoroalkyl carboxylates, and the like. In particular, acetylene glycol surfactants and acetylene alcohol surfactants are preferred. When these surfactants are added to the ink composition, they are preferable because they have less foaming properties and have an excellent antifoaming function. Specific examples of the acetylene glycol surfactant and the acetylene alcohol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne- 3,6-diol, 3,5-dimethyl-1-hexyn-3ol and the like are available, and are also commercially available. For example, Surfynol 61, 82, 104, 465 manufactured by Air Products (UK) , 485, TG, Olphine STG from Nissin Chemical Industry Co., Ltd., Olfin E1010, and the like.

  The addition amount of the surfactant is preferably 0.01% by weight or more and 3% by weight or less with respect to the total amount of the ink composition, the more preferable upper limit value is 2.0% by weight, and the preferable lower limit value is 0.05% by weight.

  In the present invention, among the surfactants described above, it is preferable to use 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. The acetylene glycol surfactant and / or acetylene alcohol surfactant used in the present invention is 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-. Alkylene oxide adducts of tetramethyl-5-decin-4,7-diol and alkylene oxide adducts of 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol 1 or more types selected from are preferred. These acetylene glycol surfactants and / or acetylene alcohol surfactants are available as E series such as Olfin 104 series and Olfine E1010 from Air Products, Surfinol 465 or Surfinol 61 from Nissin Chemical Industry Co., Ltd. Is possible. Addition of these improves the drying property of printing, and enables high-speed printing.

  In addition, the ink composition according to the present invention includes 1,2-alkylene glycol and acetylene glycol surfactant and / or acetylene alcohol surfactant, glycol ether and acetylene glycol surfactant and / or acetylene alcohol surfactant. Bleeding is further reduced by using a plurality of agents.

  The ink composition according to the present invention may be added with a pH buffer, an antioxidant, an ultraviolet absorber, an antiseptic or antifungal agent, a chelating agent, and the like, if necessary. Specific examples of the pH buffering agent include collidine, imidazole, phosphoric acid, 3- (N-morpholino) propanesulfonic acid, tris (hydroxymethyl) aminomethane, boric acid and the like.

  Specific examples of antioxidants or ultraviolet absorbers include allophanates such as allophanate and methyl allophanate, biurets such as biuret, dimethylbiuret and tetramethylbiuret, L-ascorbic acid and its salts, etc. manufactured by Ciba Geigy Tinuvin 328, 900, 1130, 384, 292, 123, 144, 622, 770, 292, Irgacor 252, 153, Irganox 1010, 1076, 1035, MD1024, or the like, or a lanthanide oxide or the like.

  Specific examples of preservatives or fungicides include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazoline-3- ON (Proxel GXL, Proxel XL-2, Proxel LV, Proxel AQ, Proxel BD20, Proxel DL from Arch Chemicals) and the like. Specific examples of the chelating agent include ethylenediaminetetraacetic acid (EDTA).

<Method for producing ink composition>
The ink composition according to the present invention may be prepared by supplying and dispersing the above-described components to a dispersing / mixing machine (for example, a ball mill, a sand mill, an attritor, a basket mill, a roll mill, etc.). According to a preferred embodiment of the present invention, it is preferable to filter the ink stock solution obtained by the above-described dispersing / mixing device using a filter such as a membrane filter or a mesh filter to remove coarse particles.

<Inkjet recording method and apparatus>
The ink composition according to the present invention is not particularly limited as long as it is used in an ink jet recording method, but is particularly preferably used in an ink jet textile printing method. The ink jet recording method using the ink composition according to the present invention is to perform printing by ejecting droplets of the ink composition and attaching the droplets to a heated recording medium. As an example of a method for ejecting ink composition droplets, for example, an electrostrictive element is used to convert an electrical signal into a mechanical signal, and ink stored in the nozzle head portion is intermittently ejected onto the surface of the recording medium. A method of recording characters and symbols, ink heated in the nozzle head portion is heated rapidly at a location very close to the discharge portion, bubbles are generated, and the ink is intermittently discharged by the volume expansion caused by the bubbles, and characters are printed on the surface of the recording medium. And a method of recording symbols. In the present invention, ejection is preferably performed by a method using an electrostrictive element that does not depend on heating, such as a piezo element. When a heating element such as a thermal head is used, the added resin or the like may change in quality and discharge may become unstable. In particular, when a large amount of ink is ejected over a long period of time, such as an inkjet ink for textiles, it is preferably ejected by a method using an electrostrictive element that does not depend on heating.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Preparation of carbon black dispersion 1 100.0 g of commercially available carbon black (# 44: manufactured by Mitsubishi Chemical Corporation) and 900.0 g of water were mixed, and the bead filling rate was 70% with an Eiger Motor Mill M250 (manufactured by Eiger Japan). And dispersed for 2 hours under the condition of a rotational speed of 5000 rpm. To this dispersion, 1500.0 g of sodium hypochlorite (effective chlorine concentration: 12%) was added dropwise and reacted for 5 hours while stirring with an Eiger motor mill, then the temperature was controlled at 100 ° C. and stirred for 8 hours. . Subsequently, the obtained slurry was filtered and washed with water, and the carbon black concentration was adjusted to 15% by mass to obtain a surface-treated carbon black dispersion.
The particle size was measured using a Microtrac particle size distribution analyzer UPA250 (manufactured by Nikkiso), and it was 180 nm.

Preparation of Carbon Black Dispersion 2 Similar to the carbon black dispersion 1, a commercially available carbon black (# 44: manufactured by Mitsubishi Chemical Corporation) was used to prepare one having a particle size exceeding 300 nm. When the particle size was measured in the same manner as in the carbon black dispersion 1, it was 350 nm. This dispersion was designated as carbon black dispersion 2.

Preparation of resin dispersion 1 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube, 230.0 g of polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)}, 126.3 g of acetone and 0.06 g of DBTL (dibutyltin dilaurate) were added and the contents were heated to 40 ° C. and mixed well. Thereafter, 87.5 g of HDI (hexamethylene diisocyanate) was added to the reaction vessel over 60 minutes at 40 ° C. using a dropping device. Residual HDI was flushed from the dropping apparatus into the reaction vessel with 7.5 g of acetone.
The temperature of the reaction vessel was raised to 50 ° C. and held for about 30 minutes. Thereafter, 22.2 g of DMPA (dimethylolpropionic acid) and then 12.6 g of triethylamine were respectively added to the reaction vessel from the dropping device. The dropping apparatus was washed with 8.0 g of acetone. Thereafter, the temperature of the reaction vessel was again raised to 50 ° C. and held for 60 minutes.
At a temperature of 50 ° C., 532.0 g of ion-exchanged water was added over 10 minutes, and 268.0 g of 10% TMP (trimethylolpropane) 10% aqueous solution was added over 5 minutes from the dropping device. Thereafter, the dropping device was washed with 30.0 g of ion-exchanged water. The mixture was then held at 50 ° C. for 1 hour and then cooled to room temperature. Acetone was removed under reduced pressure to obtain a resin dispersion 1 having a resin solid content of about 30% by mass.
The exact solid content of the resin dispersion was measured using a Sartorius electronic moisture meter MA100 (Sartorius Mechatronics Japan). Moreover, the THF insoluble content of the resin was measured by the following method. In a centrifuge tube whose mass has been accurately measured, 1 g of resin dispersion 1 and 30 g of THF are precisely weighed and collected and mixed. After the mixture was centrifuged at 17,000 rpm for 2 hours, the upper liquid phase was removed to obtain a gel remaining at the bottom of the container. The centrifuge tube was placed in an oven and dried at 110 ° C. for 2 hours. Subsequently, in order to measure the mass of the remaining gel, the mass of the centrifuge tube was measured again. The THF-insoluble content of the resin was determined by the following formula (1).
THF insoluble matter (%) = (ab) * 100 / (c * d / 100) Formula (1)
a: Mass of centrifuge tube + insoluble gel (g)
b: Mass of the centrifuge tube (g)
c: Mass of resin dispersion (g)
d: Solid content of resin dispersion (%)
Specifically, the mass of an empty centrifuge tube was measured in advance to determine the mass (b) of the centrifuge tube in the above formula (1). A known 1 g (c) resin dispersion having a solid content (d) and 30 g of THF were placed in a centrifuge tube and mixed at 25 ° C. Next, the mixed THF solution was centrifuged at 17,000 rpm for 2 hours, and then the upper liquid phase was removed. The centrifuge tube in which the insoluble gel remained at the bottom was placed in an oven, dried at 110 ° C. for 2 hours, and then weighed again to determine the sum (a) of the mass of the centrifuge tube and the mass of the insoluble gel.
The THF insoluble content of the resin dispersion 1 determined by the above method was 60% by mass.

Preparation of resin dispersion 2 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen inlet tube, 230.0 g of polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)}, 126.3 g acetone and 0.06 g DBTL were added and the contents were heated to 40 ° C. and mixed well. Thereafter, 87.5 g of HDI was added to the reaction vessel over 60 minutes at 40 ° C. using a dropping device. Residual HDI was flushed from the dropping apparatus into the reaction vessel with 7.5 g of acetone.
The temperature of the reaction vessel was raised to 50 ° C. and held for about 30 minutes. Thereafter, 22.2 g of DMPA and then 12.6 g of triethylamine were respectively added to the reaction vessel from the dropping device. The dropping apparatus was washed with 8.0 g of acetone. Thereafter, the temperature of the reaction vessel was again raised to 50 ° C. and held for 60 minutes.
Next, at a temperature of 50 ° C., 471.0 g of ion-exchanged water was added over 10 minutes, 134.0 g of 10% TMP aqueous solution was added over 5 minutes from the dropping device, and then 75.0 g of TEG (triethylene glycol) was added. ) A 20% aqueous solution was added over 5 minutes. Thereafter, the dropping device was washed with 140.0 g of ion exchange water. The mixture was then held at 50 ° C. for 1 hour and then cooled to room temperature. Acetone was removed under reduced pressure to obtain a resin dispersion 2 having a resin solid content of about 30% by mass.
The THF insoluble content of the resin dispersion 2 obtained by the same method as that for the resin dispersion 1 was 53% by mass.

Preparation of resin dispersion 3 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube, 230.0 g of polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)}, 126.3 g acetone and 0.06 g DBTL were added and the contents were heated to 40 ° C. and mixed well. Thereafter, 115.4 g of IPDI (isophorone diisocyanate) was added to the reaction vessel over 60 minutes at 40 ° C. using a dropping device. Residual IPDI was flushed from the dropping apparatus into the reaction vessel with 7.5 g of acetone.
The temperature of the reaction vessel was raised to 50 ° C. and held for about 30 minutes. Thereafter, 22.2 g of DMPA and then 12.6 g of triethylamine were respectively added to the reaction vessel from the dropping device. The dropping apparatus was washed with 8.0 g of acetone. Thereafter, the temperature of the reaction vessel was again raised to 50 ° C. and held for 60 minutes.
At a temperature of 50 ° C., 596.0 g of ion exchange water was added over 10 minutes, and 268.0 g of TMP 10% aqueous solution was added over 5 minutes from the dropping device. Thereafter, the dropping device was washed with 30.0 g of ion-exchanged water. The mixture was then held at 50 ° C. for 1 hour and then cooled to room temperature. Acetone was removed under reduced pressure to obtain a resin dispersion 3 having a resin solid content of about 30% by mass.
The THF-insoluble content of the resin dispersion 3 obtained by the same method as that for the resin dispersion 1 was 55% by mass.

Preparation of Resin Dispersion 4 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube, 90.0 g of polyester carbonate diol {DESMOPHENE C200 (Bayer)}, 245 .5 g of polytetramethylene ether glycol {TERATHANE 1400 (Invista)}, 140.0 g of acetone and 0.04 g of DBTL were added and the contents were heated to 40 ° C. and mixed well. Thereafter, 108.3 g of IPDI was added to the reaction vessel over 60 minutes at 40 ° C. using a dropping apparatus. Residual IPDI was washed from the dropping apparatus into the reaction vessel with 5.8 g of acetone.
The temperature of the reaction vessel was raised to 50 ° C. and held for about 30 minutes. Thereafter, 22.3 g of DMPA and then 12.6 g of triethylamine were respectively added to the reaction vessel from the dropping device. The dropping apparatus was washed with 12.5 g of acetone. Thereafter, the temperature of the reaction vessel was again raised to 50 ° C. and held for 60 minutes.
At a temperature of 50 ° C., 787.0 g of ion-exchanged water was added over 10 minutes, and 49.0 g of 6.25% TETA (triethylenetetraamine) 6.25% aqueous solution was added over 5 minutes from the dropping device. Thereafter, the dropping device was washed with 40.0 g of ion exchange water. The mixture was then held at 50 ° C. for 1 hour and then cooled to room temperature. Acetone was removed under reduced pressure to obtain a resin dispersion 4 having a resin solid content of about 34% by mass.
The THF-insoluble content of the resin dispersion 4 obtained by the same method as that for the resin dispersion 1 was 8% by mass.

Preparation of Resin Dispersion 5 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube, 699.2 g of polyester carbonate diol {DESMOPHENE C200 (Bayer)}, 280 0.0 g acetone and 0.06 g DBTL were added and the contents were heated to 40 ° C. and mixed well. Thereafter, 189.1 g of IPDI was added to the reaction vessel over 60 minutes at 40 ° C. using a dropping apparatus. Residual IPDI was washed from the dropping apparatus into the reaction vessel with 15.5 g of acetone.
The temperature of the reaction vessel was raised to 50 ° C. and held for about 30 minutes. Thereafter, 44.6 g of DMPA and then 25.2 g of triethylamine were respectively added to the reaction vessel from the dropping device. The dropping apparatus was washed with 15.5 g of acetone. Thereafter, the temperature of the reaction vessel was raised again to 50 ° C., and kept at 50 ° C. until NCO% became 1.14% or less.
NCO% was used as a measure of the progress of the polyurethane reaction. The NCO-containing prepolymer was reacted with a dibutylamine solution of known concentration, and the residual amine was back titrated with HCl, and NCO% was determined by dibutylamine titration.
At a temperature of 50 ° C., 1498.0 g of ion-exchanged water was added over 10 minutes, and a mixture of 97.5 g of EDA (ethylenediamine) 6.25% aqueous solution and 29.7 g of TETA 6.25% aqueous solution was added from a dropping device. Added over 5 minutes. Thereafter, the dropping device was washed with 80.0 g of ion exchange water. The mixture was then held at 50 ° C. for 1 hour and then cooled to room temperature. Acetone was removed under reduced pressure to obtain a resin dispersion 5 having a resin solid content of about 35% by mass.
The THF insoluble content of the resin dispersion 4 obtained by the same method as that for the resin dispersion 1 was 5% by mass.

Preparation of Resin Dispersion 6 A reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube was charged with 335.0 g of polyester carbonate diol {DESMOPHENE C200 (Bayer)}, 142 0.0 g acetone and 0.04 g DBTL were added and the contents were heated to 40 ° C. and mixed well. Then, 99.0 g of IPDI and 29.5 g of hexamethylene diisocyanate dimer (40% by mass), trimer (60% by mass) mixture {DESMODUR N3400 (Bayer)} over 60 minutes at 40 ° C. using a dropping device Was added to the reaction vessel. The residue was washed from the dropping device into the reaction vessel with 10.0 g of acetone.
The temperature of the reaction vessel was raised to 50 ° C. and held for about 30 minutes. Thereafter, 23.4 g of DMPA and then 13.6 g of triethylamine were respectively added to the reaction vessel from the dropping device. The dropping apparatus was washed with 10.0 g of acetone. Thereafter, the temperature of the reaction vessel was raised again to 50 ° C., and kept at 50 ° C. until NCO% was 2.3% or less.
NCO% was used as a measure of the progress of the polyurethane reaction. NCO% was calculated | required by the method similar to the resin dispersion 5.
At a temperature of 50 ° C., 700.0 g of ion-exchanged water was added over 10 minutes, and 174.0 g of EDA 6.25% aqueous solution was added over 5 minutes from the dropping device. Thereafter, the dropping device was washed with 40.0 g of ion exchange water. The mixture was then held at 50 ° C. for 1 hour and then cooled to room temperature. Acetone was removed under reduced pressure to obtain a resin dispersion 6 having a resin solid content of about 34% by mass.
The THF-insoluble content of the resin dispersion 4 obtained by the same method as that for the resin dispersion 1 was 39% by mass.

Preparation of resin dispersion 7 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube, 230.0 g of polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)}, 126.3 g acetone and 0.06 g DBTL were added and the contents were heated to 40 ° C. and mixed well. Thereafter, 87.5 g of HDI was added to the reaction vessel over 60 minutes at 40 ° C. using a dropping device. Residual HDI was flushed from the dropping apparatus into the reaction vessel with 7.5 g of acetone.
The temperature of the reaction vessel was raised to 50 ° C. and held for about 30 minutes. Thereafter, 22.2 g of DMPA and then 12.6 g of triethylamine were respectively added to the reaction vessel from the dropping device. The dropping apparatus was washed with 8.0 g of acetone. Thereafter, the temperature of the reaction vessel was raised again to 50 ° C., and kept at 50 ° C. until NCO% became 1.14% or less.
NCO% was used as a measure of the progress of the polyurethane reaction. NCO% was calculated | required by the method similar to the resin dispersion 5.
At a temperature of 50 ° C., 560.0 g of ion-exchanged water was added over 10 minutes, and a mixture of 97.5 g of EDA (ethylenediamine) 6.25% aqueous solution and 29.7 g of TETA 6.25% aqueous solution was added from a dropping device. Added over 5 minutes. Thereafter, the dropping device was washed with 80.0 g of ion exchange water. The mixture was then held at 50 ° C. for 1 hour and then cooled to room temperature. Acetone was removed under reduced pressure to obtain a resin dispersion 7 having a resin solid content of about 30% by mass.
The THF insoluble content of the resin dispersion 7 obtained by the same method as that for the resin dispersion 1 was 5% by mass.

Preparation of resin dispersion 8 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube, 230.0 g of polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)}, 126.3 g acetone and 0.06 g DBTL were added and the contents were heated to 40 ° C. and mixed well. Thereafter, 115.4 g of IPDI was added to the reaction vessel over 60 minutes at 40 ° C. using a dropping device. Residual IPDI was flushed from the dropping apparatus into the reaction vessel with 7.5 g of acetone.
The temperature of the reaction vessel was raised to 50 ° C. and held for about 30 minutes. Thereafter, 22.2 g of DMPA and then 12.6 g of triethylamine were respectively added to the reaction vessel from the dropping device. The dropping apparatus was washed with 8.0 g of acetone. Thereafter, the temperature of the reaction vessel was again raised to 50 ° C. and held for 60 minutes.
At a temperature of 50 ° C., 620.0 g of ion-exchanged water was added over 10 minutes, and a mixture of 97.5 g of EDA (ethylenediamine) 6.25% aqueous solution and 29.7 g of TETA 6.25% aqueous solution was added from the dropping device. Added over 5 minutes. Thereafter, the dropping device was washed with 80.0 g of ion exchange water. The mixture was then held at 50 ° C. for 1 hour and then cooled to room temperature. Acetone was removed under reduced pressure to obtain a resin dispersion 8 having a resin solid content of about 30% by mass.
The THF-insoluble content of the resin dispersion 8 obtained by the same method as that for the resin dispersion 1 was 14% by mass.

Preparation of resin dispersion 9 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube, 240.0 g of a polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)} 89.1 g HDI and 260.0 g MEK (methyl ethyl ketone) were added and mixed. Then, it heated at 75 degreeC and hold | maintained for 3 hours.
Next, a mixture solution consisting of 9.4 g of MEK, 13.4 g of DMPA, and 10.1 g of triethylamine was added to the reaction vessel from the dropping device. The dropping device was washed with 8.0 g of MEK, and the temperature of the reaction vessel was again raised to 75 ° C. and held for 2 hours.
Thereafter, the content temperature of the reaction vessel was cooled to 30 ° C., and 671.0 g of a 4% TMP aqueous solution was added dropwise. The dropping device was washed with 180.0 g of ion exchange water. Subsequently, after stirring and stirring for 1 hour, MEK was removed under reduced pressure at 50 ° C. to obtain a resin dispersion 9 having a resin solid content of about 30% by mass.
The THF-insoluble content of the resin dispersion 8 obtained by the same method as that for the resin dispersion 1 was 58% by mass.

Preparation of resin dispersion 10 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen inlet tube, 240.0 g of polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)}, 89.1 g HDI and 260.0 g MEK (methyl ethyl ketone) were added and mixed. Then, it heated at 75 degreeC and hold | maintained for 3 hours.
Next, a mixture solution consisting of 9.4 g of MEK, 13.4 g of DMPA, and 10.1 g of triethylamine was added to the reaction vessel from the dropping device. The dropping device was washed with 8.0 g of MEK, and the temperature of the reaction vessel was again raised to 75 ° C. and held for 2 hours.
Thereafter, the content temperature of the reaction vessel was cooled to 30 ° C., and 751.0 g of a 6% aqueous solution of TEG was added dropwise. The dropping device was washed with 150.0 g of ion exchange water. Subsequently, after stirring and stirring for 1 hour, MEK was removed under reduced pressure at 50 ° C. to obtain a resin dispersion 9 having a resin solid content of about 30% by mass.
The THF-insoluble content of the resin dispersion 8 obtained by the same method as that for the resin dispersion 1 was 52% by mass.

Preparation of resin dispersion 11 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube, 240.0 g of polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)}, 89.1 g HDI and 260.0 g MEK (methyl ethyl ketone) were added and mixed. Then, it heated at 75 degreeC and hold | maintained for 3 hours.
Next, a mixture solution consisting of 9.4 g of MEK, 13.4 g of DMPA, and 10.1 g of triethylamine was added to the reaction vessel from the dropping device. The dropping device was washed with 8.0 g of MEK, and the temperature of the reaction vessel was again raised to 75 ° C. and held for 2 hours.
Thereafter, the content temperature of the reaction vessel was cooled to 30 ° C., and 805.0 g of a 4% TMP aqueous solution was added dropwise. The dropping device was washed with 60.0 g of ion exchange water. Next, after stirring and stirring for 1 hour, MEK was removed under reduced pressure at 50 ° C. to obtain a resin dispersion 11 having a resin solid content of about 30% by mass.
The THF-insoluble content of the resin dispersion 11 obtained by the same method as that for the resin dispersion 1 was 60% by mass.

Preparation of resin dispersion 12 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube, 240.0 g of polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)}, 89.1 g HDI and 260.0 g MEK (methyl ethyl ketone) were added and mixed. Then, it heated at 75 degreeC and hold | maintained for 3 hours.
Next, a mixture solution consisting of 9.4 g of MEK, 13.4 g of DMPA, and 10.1 g of triethylamine was added to the reaction vessel from the dropping device. The dropping device was washed with 8.0 g of MEK, and the temperature of the reaction vessel was again raised to 75 ° C. and held for 2 hours.
Thereafter, the content temperature of the reaction vessel was cooled to 30 ° C., and an aqueous solution containing 513.3 g of TMP 1.5% and TEG 7% was added dropwise. The dropping device was washed with 392.0 g of ion exchange water. Subsequently, after stirring and stirring for 1 hour, MEK was removed under reduced pressure at 50 ° C. to obtain a resin dispersion 12 having a resin solid content of about 30% by mass.
The THF-insoluble content of the resin dispersion 12 obtained by the same method as that for the resin dispersion 1 was 55% by mass.

Preparation of resin dispersion 13 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature regulator and a nitrogen introduction tube, 240.0 g of polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)}, 89.1 g HDI and 260.0 g MEK (methyl ethyl ketone) were added and mixed. Then, it heated at 75 degreeC and hold | maintained for 3 hours.
Next, a mixture solution consisting of 9.4 g of MEK, 13.4 g of DMPA, and 10.1 g of triethylamine was added to the reaction vessel from the dropping device. The dropping device was washed with 8.0 g of MEK, and the temperature of the reaction vessel was again raised to 75 ° C. and held for 2 hours.
Thereafter, the content temperature of the reaction vessel was cooled to 30 ° C., and 827.5 g of a TMP 6% aqueous solution was dropped. The dropping device was washed with 106.0 g of ion exchange water. Subsequently, after stirring and stirring for 1 hour, MEK was removed under reduced pressure at 50 ° C. to obtain a resin dispersion 13 having a resin solid content of about 30% by mass.
The THF insoluble content of the resin dispersion 13 obtained by the same method as that for the resin dispersion 1 was 69% by mass.

Preparation of resin dispersion 14 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube, 240.0 g of polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)}, 138.0 g of hydrogenated MDI (4,4′-dicyclohexylmethane diisocyanate) and 260.0 g of MEK (methyl ethyl ketone) were added and mixed. Then, it heated at 75 degreeC and hold | maintained for 3 hours.
Next, a mixture solution consisting of 9.4 g of MEK, 13.4 g of DMPA, and 10.1 g of triethylamine was added to the reaction vessel from the dropping device. The dropping device was washed with 8.0 g of MEK, and the temperature of the reaction vessel was again raised to 75 ° C. and held for 2 hours.
Thereafter, the content temperature of the reaction vessel was cooled to 30 ° C., and 671.0 g of a 4% TMP aqueous solution was added dropwise. The dropping device was washed with 300.5 g of ion exchange water. Subsequently, after stirring and stirring for 1 hour, MEK was removed under reduced pressure at 50 ° C. to obtain a resin dispersion 14 having a resin solid content of about 30% by mass.
The THF-insoluble content of the resin dispersion 14 obtained by the same method as that for the resin dispersion 1 was 57% by mass.

Preparation of resin dispersion 15 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube, 240.0 g of polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)}, 89.1 g HDI and 260.0 g MEK (methyl ethyl ketone) were added and mixed. Then, it heated at 75 degreeC and hold | maintained for 3 hours.
Next, a mixture solution consisting of 9.4 g of MEK, 13.4 g of DMPA, and 10.1 g of triethylamine was added to the reaction vessel from the dropping device. The dropping device was washed with 8.0 g of MEK, and the temperature of the reaction vessel was again raised to 75 ° C. and held for 2 hours.
Thereafter, the content temperature of the reaction vessel was cooled to 30 ° C., and 516.0 g of a 4% aqueous solution of DETA (diethylenetriamine) was added dropwise. The dropping device was washed with 320.7 g of ion exchange water. Subsequently, after stirring and stirring for 1 hour, MEK was removed under reduced pressure at 50 ° C. to obtain a resin dispersion 15 having a resin solid content of about 30% by mass.
The THF-insoluble content of the resin dispersion 15 obtained by the same method as that for the resin dispersion 1 was 38% by mass.

Preparation of resin dispersion 16 In a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, a stirrer, a temperature adjuster, and a nitrogen introduction tube, 240.0 g of polycarbonate polyol {Duranol ^TM T5651 (Asahi Kasei Chemicals)}, 89.1 g HDI and 260.0 g MEK (methyl ethyl ketone) were added and mixed. Then, it heated at 75 degreeC and hold | maintained for 3 hours.
Next, a mixture solution consisting of 9.4 g of MEK, 13.4 g of DMPA, and 10.1 g of triethylamine was added to the reaction vessel from the dropping device. The dropping device was washed with 8.0 g of MEK, and the temperature of the reaction vessel was again raised to 75 ° C. and held for 2 hours.
Thereafter, the content temperature of the reaction vessel was cooled to 30 ° C., and a mixture of 97.5 g of EDA 6.25% aqueous solution and 29.7 g of TETA 6.25% aqueous solution was added dropwise. The dropping device was washed with 660.0 g of ion exchange water. Subsequently, after stirring and stirring for 1 hour, MEK was removed under reduced pressure at 50 ° C. to obtain a resin dispersion 16 having a resin solid content of about 30% by mass.
The THF-insoluble content of the resin dispersion 16 obtained by the same method as that for the resin dispersion 1 was 40% by mass.

Preparation of Ink for Inkjet Printing Tables 2 and 4 show examples of compositions suitable for ink jet recording ink. The ink for inkjet recording of the present invention was prepared by mixing the vehicle components shown in Tables 2 and 4 using the carbon black dispersion and the resin dispersion prepared by the above method. 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.
In Tables 2 and 4, the unit is mass%, the ink composition (mass%) of the carbon black dispersion is represented by the solid content concentration of the carbon black, and the ink composition (mass%) of the resin dispersion is It represents by solid content concentration of each resin, S-104 represents Surfinol 104 (Nisshin Chemical Co., Ltd.), and S-465 represents Surfinol 465 (Nisshin Chemical Co., Ltd.). In Tables 1 and 3, OH group / NCO group is represented by the ratio of the number of OH groups of the compound represented by formula (II) to the number of NCO groups of polyisocyanate in the resin raw material.

For the preparation of the sample for the abrasion resistance test and the dry cleaning test test, the ink for inkjet printing was used, and PX-A650 manufactured by Seiko Epson Corporation was used as an inkjet printer. The test sample was solid printed on a cotton cloth. 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. Tables 1 and 3 show the results of the abrasion resistance test and the dry cleaning test.

Test of ejection stability Using PX-A650 manufactured by Seiko Epson Corporation as an ink jet printer using the ink jet printing ink described above, a character size of 11 in Microsoft Word on a Xerox P paper A4 size manufactured by Fuji Xerox Co., Ltd. at 35 ° C. and 35% atmosphere. Standard, MSP Gothic, and printed and evaluated 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 Tables 1 and 3 as D.

Claims (8)

An ink composition for ink jet recording, comprising at least a dispersion in which a pigment can be dispersed in water, water, and a polyurethane resin,
The dispersion contains a self-dispersing pigment, the dispersion has an average particle size of 20 to 300 nm, and the polyurethane resin comprises, as a constituent , a compound represented by the following formula (I) and the following formula (II Ink composition for inkjet recording, comprising a compound represented by:

(In the above formula, N represents an integer of 1 to 6),

(In the above formula, the value of O + P + Q represents an integer of 0 to 6).   In the raw material composition of the polyurethane resin, the ratio of the number of OH groups of the compound represented by the formula (II) to the number of NCO groups of the polyisocyanate is 0.75 or less. The ink composition as described. The ink composition according to claim 1 or 2, wherein the polyisocyanate comprises a compound represented by the following formula (III):

(In the above formula, L represents an integer of 3 to 10). The ink composition according to any one of claims 1 to 3, wherein in the raw material composition of the polyurethane resin, the polyol comprises a compound represented by the following formula (IV):

(In the above formula, M represents an integer of 3 to 10, and n represents an integer of 2 to 14).   The ink composition according to claim 1, further comprising 1,2-alkylene glycol.   The ink composition according to any one of claims 1 to 5, further comprising an acetylene glycol surfactant and / or an acetylene alcohol surfactant.   The ink composition for ink jet recording according to any one of claims 1 to 6, which is used for ink jet textile printing.   An ink jet textile printing method using the ink composition according to any one of claims 1 to 7.